PERIODIC TABLE AND PERIODIC PROPERTIES

1
Chemistry-XI

PERIODIC TABLE AND

PERIODIC PROPERTIES
STUDENT LEARNING OUTCOMES [C-11-B-01 to C-11-B-18]

Explain the arrangement of elements in the periodic table. (Understanding)

Identify the positions of metals, nonmetals and metalloids in the periodic table.
(Understanding)
Explain that the periodic table is arranged into four blocks associated with the four
sublevels s, p, d, and f. (Understanding)
Recognize that the period number (n) is the outer energy level that is occupied by electrons.
(Understanding)
Deduce the electron configuration of an atom from the element’s position on the periodic
table, and vice versa (based on s, p, d and f subshells). (Understanding)
State that the number of the principal energy level and the number of the valence electrons
in an atom can be deduced from its position on the periodic table. (Knowledge)
Deduce the nature, possible position in the Periodic Table and identity of unknown elements
from given information about physical and chemical properties. (Understanding)
Predict the characteristic properties of an element in a given group by using knowledge of
chemical periodicity. (Application)
Explain that vertical and horizontal trends in the periodic table exist for atomic radius,
ionic radius, ionization energy, electron affinity and electronegativity. (Understanding)
Explain the trends in the ionization energies and electron affinities of the Group 1 and
Group 17 elements. (Understanding)
Recognize that trends in metallic and non- metallic behavior are due to the trends in
valence electrons. (Understanding)
Suggest the types of chemical bonding present in the chlorides and oxides from observations
of their physical and chemical properties. (Understanding)
Describe (including writing equations for) the reactions, if any, of the oxides (acidic and
basic) with water (including the likely pHs of the solutions obtained). (Understanding)
Explain with the help of equations for, the acid / base behavior of the oxides and the
hydroxides NaOH, Mg(0H)2 including, where relevant, amphoteric behavior in reactions
with acids and bases (sodium hydroxide only) (Understanding)
Explain with equations for, the reactions of the chlorides with water including the likely
pHs of the solutions obtained. (Understanding)
Explain the variation in the oxidation number of the oxides and chlorides (NaCI, MgCI2

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

in terms of their outer shell (valence shell) electrons. (Understanding)

Write equations for the reactions of Na and Mg with oxygen, chlorine and water.
(Application)
Explain the variations and trends in terms of bonding and electronegativity. (Understanding)

It is accurate to refer to the periodic table of elements as the “Symbol of Chemistry.” It

is a vital and thorough source of chemical knowledge and much more than just a simple
chart. It would be difficult to explore and comprehend the enormous area of chemistry
without its systematic categorization and arrangement of elements. One of the most
important turning points in the history of science was the creation of the periodic table,
which led to many important innovations. Elements are arranged in tabular form in the
current periodic table based on their atomic number, electrical configuration, and recurrent
chemical characteristics. It provides the foundation for comprehending 118 elements
and their properties, making it a crucial tool in chemistry. The creation of the periodic
table, which offers a framework for researching the periodic behaviors, is a significant
accomplishment in scientific history.

1.1 HISTORICAL BACKGROUND

It is interesting to note that just three centuries ago, less than a
dozen elements were known to humanity. By 1700 A.D., only
12 elements—Gold, Silver, Copper, Iron, Lead, Tin, Mercury,
Phosphorus, Sulfur, Carbon, Zinc, and Arsenic—were recognized.
Over time, more elements were discovered, prompting scientists
to organize them systematically. Up to the end of 18th century,
Antoine Lavoisier attempted to classify known elements as metals
and nonmetals. In 1829, Döbereiner grouped the elements into
triads (a group of three) with similar properties, noting that the
atomic weight of the middle element was roughly the average of Dmitri Mendeleev
the other two. Examples of such triads include lithium, sodium, arranged elements
according to their atomic
and potassium (7Li2,Na3,7K) . masses and his table was
the first most notable effort
English chemist John Newlands, in 1864, first time observed in the classification of
periodicity in the 62 known elements, noticing that the properties elements
of every eighth element were similar when arranged by the
increasing order of their atomic masses. He classified the elements into groups so that
every eight element resembled the first element in properties.
In 1869, Russian chemist Dmitri Mendeleev, considered the father of the Periodic Table,
arranged 63 elements into eight vertical columns by increasing atomic mass, aligning
elements with similar properties into vertical groups. The success of his table was hidden
in leaving gaps for undiscovered elements and predicting their atomic mass and properties,
which proved accurate when these elements were practically found.

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

In the same year, Lother Meyer developed his famous curves by ploting a graph b/w the
at weight and at volumes of elements. These curves also showed periodicity. In the same
year Lother mayer developed his famous curves by plotting a graph between the atomic
weights and atomic volumes of elements. These curves also showed periodic periodicity.
In 1913, Moseley determined the exact atomic numbers of known elements using X-ray
emission, resolving flaws and discrepencies in Mendeleev’s table by arranging the elements
by atomic numbers instead of atomic masses. This significant breakthrough led Moseley
to modify the Periodic Law to state that the properties of elements are periodic functions
of their atomic numbers.

1.2 MODERN PERIODIC TABLE - FEATURES AND

SIGNIFICANCE
The classification of elements in the modern periodic table helps in the easier understanding
of their properties. Following are some of the main features of the modern periodic table:
Presently, 118 elements are grouped in the table in ascending order of their respective
atomic numbers.
There are seven horizontal rows called periods and eighteen vertical columns called
groups. (In older versions of the table, there were 8 vertical groups were divided into
two types of groups: Eight A-Groups and Ten B-Groups.
In the periodic table, elements within the same group exhibit similar chemical roperties
ecause they have the same number of valence electrons. However, they show a gradual
change in physical properties from top to bottom in a group.
Elements in a period show a gradual change in properties moving from left to right in
periods.

Other than groups and periods in the periodic there are different ways of grouping the
elements into various blocks, families and categories just to enhance understanding.

1.3 METALS, NON-METALS AND METALLOIDS

Elements can be broadly classified as metals, nonmetals and metalloids. Metals are elements
which tend to lose electrons to form positive ions. Examples are iron, copper, gold and
silver. On the other hand, non-metals are elements which tend to gain electrons to form
negative ions. The examples are chlorine, sulfur and phosphorous. The metalloids separate
the metals and nonmetals on a periodic table. The metalloids exhibit some properties of
metals and some of non-metals. Mostly periodic tables have a “stair-step line” on the table
identifying the element groups. The line begins at boron (B) and extends down to polonium
(Po) including Si, Ge, As, Sb and Te. Elements to the left of the line are considered metals.
Elements just to the right of the line exhibit properties of both metals and nonmetals and
are termed as metalloids or semimetals. Elements to the far right of the periodic table
are nonmetals. The exception is hydrogen, the first element on the periodic table.

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

GROUP
1 18
1 Alkali Metals Non-metals 78 Atomic Number 2

PERIOD
H He
1
Pt
Alkaline Earth Metals Halogens
Symbol
Hydrogen
1.008 2 Transition Metals Noble Gases 13 14 15 16 17 Helium
4.003
3 4 5 6 7 8 9 10
Platinum Name

Li Be B C N O F Ne
Other Metals Lanthanides
195.1 Average Atomic Mass
2 Metalloids Actinides
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
6.94 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18

3 Na Mg Al Si P S Cl Ar
Sodium
22.99
Magnesium
24.31 3 4 5 6 7 8 9 10 11 12 Aluminium
26.98
Silicon
28.09
Phosphorus
30.97
Sulfur
32.06
Chlorine
35.45
Argon
39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

4 K
Potassium
Ca
Calcium
Sc
Scandium
Ti
Titanium
V
Vanadium
Cr Mn Fe
Chromium Manganese Iron
CoCobalt
Ni
Nickel
Cu Zn Ga Ge As
Copper Zinc Gallium Germanium Arsenic
Se
Selenium
Br
Bromine
Kr
Krypton
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.64 74.92 78.96 79.90 83.79
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

5 Rb
Rubidium
Sr
Strontium
Y
Yttrium
Zr
Zirconium
Nb Mo Tc
Niobium Molybdenum Technetium
Ru Rh Pd Ag Cd
Ruthenium Rhodium Palladium Silver Cadmium
In
Indium
Sn Tin
Sb
Antimony
Te
Tellurium
I
Iodine
Xe
Xenon
85.47 87.62 88.91 91.22 92.91 95.96 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86

6 Cs Ba
Caesium Barium
57-71
Lanthanides
Hf
Hafnium
Ta
Tantalum
W
Tungsten
Re Os
Rhenium Osmium
Ir
Iridium
Pt
Platinum
Au Hg
Gold Mercury
Tl
Thallium
PbLead
Bi
Bismuth
Po
Polonium
At Rn
Astatine Radon
132.9 137.3 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.5 204.38 207.2 209.0 (209) (210) (222)
87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118

7 Fr
Francium
Ra
Radium
89-103
Actinides
Rf
Rutherfordium
Db Sg Bh Hs Mt Ds Rg Cn Nh
Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium
Fl
Flerovium
Mc
Moscovium
Lv
Livermorium
Ts Og
Tennessine Oganesson
(223) (226) (265) (268) (271) (270) (277) (276) (281) (280) (285) (284) (289) (288) (293) (294) (294)

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71

La
Lanthanum
Ce
Cerium
Pr
Praseodymium
Nd Pm Sm Eu Gd Tb Dy Ho
Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium
Er Tm Yb
Erbium Thulium Ytterbium
Lu
Lutetium
138.9 140.1 140.9 144.2 (145) 150.4 152.0 157.2 158.9 162.5 164.9 167.3 168.9 173.0 175.0
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Ac Th
Actinium Thorium
Pa
Protactinium
U
Uranium
Np Pu Am Cm Bk
Neptunium Plutonium Americium Curium Berkelium
Cf
Californium
Es Fm Md No
Einsteinium Fermium Mendelevium Nobelium
Lr
Lawrencium
(227) 232.0 231.0 238.0 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262)

American Chemical Society Fig 1.1: Modern periodic table www.acs.org/outreach

1.4 BLOCKS IN PERIODIC TABLE

Elements in the periodic table can be classified based on the subshells containing their
valence electrons. For instance, the valence electrons of elements in the first two groups
are in the “s” subshells, placing these elements in the s-block.

p Block
s Block

d Block

f Block

Figure 10.2: Blocks in periodic table

Similarly, transition elements belong to the d-block, and the elements in the two series at
the bottom of the table (known as Lanthanides and Actinides) are categorized as f-block
elements. The remaining elements in groups 13 to 18, including the inert gases in the last
group, belong to the p-block. Knowing the block to which an element belongs provides
valuable information about its characteristics, chemical reactivity, oxidation states and
other properties such as electronegativity and ionization energy,electron filling, etc..

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

1.5 FAMILIES IN PERIODIC TABLE

Elements may be categorized according to element families. An element family is a set of
elements sharing common properties. There are five famous families of elements in the
periodic table:
Alkali metals (Li, Na, K, Rb, Cs, Fr)
Alkaline earth metals (Be, Mg, Ca, Ba, R.)
Transition metals (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn)
Chalcogens (O, S,Se, Te, Po)
Halogens (F, Cl, Br, I, At, Ts)
Noble gases (He, Ne, Ar, Kr, Xe, Rn, Og)
i) Alkali Metals
Elements in the group 1 of the periodic table are known as alkali metals because they produce
alkalis when they react with water. Sodium and potassium are notable examples of these
elements. Alkali metals are characterized by one valence electron, low densities, relatively
low melting points, and low ionization energies. These are the most reactive metals.
ii) Alkaline Earth Metals
Group 2 elements are metals primarily found in the earth and form alkalis; hence they
are referred to as alkaline earth metals. Examples include calcium and magnesium. These
elements have two electrons in their valence shell, making them divalent. They are metallic
solids that are harder and denser than alkali metals. Easily oxidized, with high thermal and
electrical conductivities.
iii) Transition Elements
The transition metals make up the largest family of elements in the middle of periodic
table. They include four series of d-block elements, as well as the lanthanides and actinides
(f-block elements) found in the two rows below. They exhibit high thermal and electrical
conductivities, high melting points, high density, and variable oxidation states. They
mostly from coloured compounds.
iv) Chalcogens
The group 16 elements are called Chalcogens because most ores of copper (Greek chalkos)
are oxides or sulfides. In this group, oxygen & sulphar are non-metals, Se, Te, Po are
metaloids and Rivernorium is a metal.
v) Halogens
Elements in group 17, known as halogens, are nonmetallic. The term “halogen” means
“salt-former” because these elements easily react with alkali metals and alkaline earth
metals to form stable halide salts. Examples are fluorine, chlorine, bromine. Halogens are
highly reactive nonmetals with high electron affinities. Halogens can easily accept one
electron to complete their outermost shell.

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

vi) Noble Gases

The noble gases are a group of unreactive elements Keep in Mind
present at the extreme right of the periodic table
in Group 18. Examples include helium and Although, noble gases are unreactive,
however they have some compound. An
argon. Due to their stable electron configuration
example is compounds of xenon such as
(complete outermost shell), they are almost entirely xenon hexafluoroplatinate (XePtF6), the
unreactive under normal conditions and rarely form word inert gases was changed to noble
compounds with other elements. These elements gases.
are monoatomic in nature.
Quick Check 1.1
a) Why are the elements in Groups 1 and 2 known as s-block elements?
b) Name the elements in the chalcogen family. Give their two characteristics.

1.6 PERIODIC ARRANGEMENT AND ELECTRONIC

CONFIGURATION
Understanding the periodic arrangement of elements in the periodic table offers valuable
insight into their physical properties, such as their physical state and atomic radii, as well
as their electronic structure and chemical reactivity.
The period number indicates the principal quantum number (n), representing the
number of electron shells surrounding the nucleus. For example, an element X in the
3rd period has three electron shells, with its valence electrons located in the 3rd shell.
The specific subshell where the valence electrons are found, depends on the element’s
block (azimuthal quantum number). If an element X in the 3rd period is in the s-block,
its valence electrons are in the 3s subshell.
Additionally, the group number indicates the number of valence electrons; for instance,
an element X in the 3rd period and group 2 has two valence electrons in its outermost
shell. Thus, the element Z in the 3rd period and group 2 (s-block) has two valence
electrons in the 3s subshell, which means that X would be magnesium (Mg).
Here is another example to relate period number and group number with electronic
configuration and position of element in period table.

X belongs to group 13 and period 3

In above example, the element X belongs to group 13 of periodic table so it has 3 valence
electrons; and it is found in period 3 so it has three shells around its nucleus.
It means that the 3 valence electron are in the 3rd shell. The configuration will be:
1s2 2s2 2p6 3s2 3p1

1st shell 2nd shell 3rd shell
Understanding the periodic arrangement of elements provides an explanation of an
element’s electronic configuration, which is essential for understanding its chemical

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

properties and behavior.

Quick Check 1.2

a) X belongs to group 14 and period 2

i. Write electronic configuration of the element X.
ii. Identify block of the element. Identify this element from periodic table.
b) Identify an element that is in Period 4 and Group 17?

1.7 PERIODICTY OF PROPERTIES

The Modern Periodic Law states: “The physical and chemical properties of elements are
periodic functions of their atomic numbers.” The atomic number corresponds to the number
of protons in an atom. This law is the “cornerstone” of the periodic table, indicating that
elements with similar properties appear at certain intervals. For instance, when elements
are arranged by increasing atomic numbers, sodium, potassium, and cesium exhibit many
physical and chemical characteristics similar to lithium, as they are all placed in the same
group of the table. However, due to the gradual increase in the number of protons in the
nucleus and the addition of new electron shells, the physical and chemical properties of
elements vary systematically within a group and a period.

1.7.1 Variation in Atomic Radius

atomic size decreases
The atomic radius is a measure of the
size of an atom. it is half of the distance 1 2 3 4 5 6 7 8
between two identical atoms bonded 11 He
together. The atomic radius can vary Li Be B C N O
atomic size increases

depending on the type of bond It is F Ne

half of the distance b/w two identical Na Mg Al Si P S Ci
Ar
atoms bonded togather, (cova metalics
& vander waals force) or the state of the K Ca Ga Gc As Sc Br Kr

atom. For example, the radius can be

different in a covalent bond compared Rb Sr ln Sn Sb Tc I Xc

to an ionic bond. The atomic radius is

typically measured in picometers (pm) Cs Ba Tl Pb Bi Pa At Rn
or Angstroms (Å).
Fig 1.4: Variation in atomic radius across
Periodic trends in atomic periods and down the groups
radius:
The factors affecting the atomic radius are: atomic number, effective nuclear charge and
shielding effect of inner electrons. Generally, atomic radius decreases across a period
(from left to right) in the periodic table due to increasing nuclear charge, which pulls the
electron cloud closer. Conversely, atomic radius increases down a group (from top to

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

bottom) because additional electron shells are added, so more sheilding makes the atom
larger despite the increase in nuclear charge ( which is outweighed) .
1.7.2 Variation in Ionic Radius
The ionic radius is a measure of the size of an ion in a crystal lattice. It’s typically defined
as the distance from the nucleus of an ion to the outermost electron shell, measured in
picometers (pm) or angstroms (Å). When an atom loses one or more electrons to become
a positive ion, it generally becomes smaller than the neutral atom. This is because the loss
of electrons reduces electronic repulsion and allows the remaining electrons to be pulled
closer to the nucleus. Contrarily when an atom gains one or more electrons to become an
anion, it generally becomes larger than the neutral atom. This is because the addition of
electrons increases electronic repulsion, as a result the nuclear pull on electrons decreases
and the electron cloud expands.
As you move across a period from left to right, the ionic radius of cations decreases due
to the increasing nuclear charge which pulls the electrons closer. For anions, the ionic
radius also decreases across a period because the increasing nuclear charge also pulls the
electrons closer to the nucleus.
On the other hand, both cations and anions increase in size as we move down a group.
This is because the principal quantum number (n) increases, leading to an increase in
the number of electron shells. Consequently, the distance between the nucleus and the
outermost electrons becomes larger, outweighing the effect of increased nuclear charge.
The additional electron shells make the ions larger.

Li+ Be2+ N3- O2- F-

60 31 171 140 136
152 111 70 66 64

Na+ Mg2+ S2- CI-

95 65 AI3+ 50 184 181
186 160 143 104 99

K+ Ca2+ Ga3+ Se2- Br-

133 99 62 198 185
231 197 122 117 114

Rb+ Sr2+ Te2- I-

113 In
3+
148 81 221 216
244 215 162 137 133

Fig. 1.5: Variation in Ionic Radius (Ions are coloured red and blue; parent atoms brown. Radii are in picometers)
Quick Check 1.5
a) Which factors affect atomic and ionic radii?
b) Using your knowledge of Period 3 elements, predict and explain the relative sizes of:
i. the atomic radii of lithium and fluorine ii. a lithium atom and its ion, Li+
iii. an oxygen atom and its ion, O2− iv. a nitride ion, N3−, and a fluoride ion, F−.

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1.7.3 Variation in Ionization Energy

“The energy needed to remove one electron from each atom in one mole of atoms of
the element in the gaseous state to form one mole of gaseous 1+ ions is known as 1st
ionization energy (ΔHi1).”
Na(g) Na+ (g) + e– ΔHi1 = 494 kJ mol–1
Ca(g) Ca+(g) + e–º­ ΔHi1 = 590 kJ mol–1
If a second electron is removed from each ion in a mole of gaseous 1+ ions, we call it the
2nd ionization energy, ΔHi2. Again, using calcium as an example:
Ca+(g) Ca2+(g) + e–º ΔHi2 = 1150 kJ mol–1.
Removal of a third electron from each ion in a mole of gaseous 2+ ions is corresponds to
the 3rd ionization energy. Again, using calcium as an example:
3rd ionisation energy:
Ca2+(g) Ca3+(g) + e– ΔHi3 = 4940 kJ mol–1
An element can have several ionization energies; the exact number corresponds to its
atomic number.
Factors affecting the ionization energy
The magnitude of the ionisation energy of an element depends upon the following factors:
i) Nuclear charge
Greater the effective nuclear charge, greater is the electrostatic force of attraction, more
difficult is the removal of an electron from the atom. For this reason, ionisation energy
increases with an increase in the effective nuclear charge.
ii) Size of the atom or ion
In bigger atoms force of attraction between the nucleus and the outermost electrons is
weaker. Therefore, the ionization energy decreases as the size of the atom increases and
vice-versa.

iii) Electronic arrangement

It is observed half-filled and completely-filled orbitals are found to be more stable.
Therefore, the ionisation energy is higher when an electron is to be removed from a fully-
filled or half-filled-shells.
(a) Noble gases have highest ionisation energies in their respective periods. It is due to
highly stable fully-filled shells (ns2 np6).
(b) Oxygen has lower ionisation energy than nitrogen. The electronic configuration of
oxygen and nitrogen are:

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7N = 1s2 2s0 2px1 2py1 2pz1 ΔHi1 = 1403 kJ mol–1

8O = 1s2 2s2 2px1 2py1 2pz0 ΔHi1 = 1365 kJ mol–1
Although, nitrogen has one unit less positive charge in its nucleus than oxygen, but due to
the extra-stability of the half-filled sub-shell of nitrogen it is difficult to remove an electron
from N atom.
iv) Shielding effect
Greater the shielding, easier it is to remove the valence electrons from an atom. Larger the
number of inner electrons, greater is the screening effect, therefore, lower is the ionization
energy.
v) Spin–Pair Repulsion
When electrons are spin-paired in the same orbital, the repulsion between them can lead
to a slightly lower ionization energy compared to removing an unpaired electron. This is
because the paired electrons experience increased repulsion, making it slightly easier to
remove one of the paired electrons.
Oxygen (O) has two spin-paired electrons in its 2p orbital. The ionization energy to
remove one of these paired electrons is relatively lower due to the increased repulsion
between the paired electrons. Nitrogen (N) has three unpaired electrons in its 2p orbitals.
Removing one of these unpaired electrons requires more energy due to the absence of spin-
pairing repulsion.
Periodic trends in ionization energy
Going down in a group, the
nuclear charge increases but as the
size of the atom and the number
of electrons causing the shielding
effect also increases therefore
ionization energy decreases from
top to bottom. In Group I, the
ionization energies decrease in
the following order: Li > Na > K
> Rb > Cs. For example, the 6s
valence electron of Cs is farther
from the nucleus and thus easier
to remove compared to the 5s
valence electron of Rb.
As you move from left to right
across a period, no. of shells remains unchanged while the effective nuclear charge
increases, making it more difficult to remove an electron. Although the number of
electrons also increases across a period, the shielding effect within the same shell is same
so not considered. Consequently, the ionization energy increases. So, the ionization energy
increases.
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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

The trend of ionization energies of period (1-3) is shown in Figure 1.6 The figure also
reveals that noble gases have the highest values of ionization energy due to complete
outermost shell in them, the removal of electron is extremely difficult, whereas alkali
metals have lowest values of ionization energy.

Quick Check 1.6

a) Explain with reasoning following facts about ionization energy:
i. 1st ionization energy of Boron is lesser than Beryllium.
ii. 1st ionization energy of Aluminum is lower than Magnesium.
b) What trend is observed in ionization energy as you go down group 3? Give reason.

1.7.4 ELECTRON AFFINITY (ΔHea

°)
° ), is the enthalpy change involved when 1 mole of
The first electron affinity, (ΔHea1
electrons is added to 1 mole of gaseous atoms to form 1 mole of gaseous uni-negative ions
under standard conditions.
Electron affinity of chlorine atom.
Cl(g) + e– Cl–(g) ° = –348.8 kJ mol–1
ΔHea1
This is amount of energy released when 6.02 × 1023 atoms of chlorine in the gaseous state
are converted into Cl–(g) ions. Since, energy is released, so first electron affinity carries
negative sign.
°
The second electron affinity, ΔHea2 is the amount of energy required to add electrons to
1 mole of uni-negative gaseous ions to form 1 mole of gaseous 2- ions under standard
conditions. For example, when first electron is added to a neutral oxygen atom, 141 kJ
mol‒1 energy is released.
O(g) + e‒ O‒(g) ° = ‒141 kJ mol‒1
ΔHea1
But 798 kJ mol‒1 of energy is absorbed on adding second electron to a uni-negative (O‒)
ion.
O‒(g) + e‒ O2‒(g) ° = +798 kJ mol‒1
ΔHea2
The net enthalpy change for the formation of the oxide ion (O2–) can be calculated by
adding the first and second electron affinities
O(g) + 2e– O2–(g)
° + ΔH ° = (–141) + (+798) = +657 kJ mol–1
ΔHea1 ea2

Factors affecting electron affinity

Important factors affecting the magnitude of electron affinity values of elements are as follows:
i) Size of atom
For small sized atoms the attraction of the nucleus for the incoming electron is stronger.

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

Thus, smaller is the size of the atom, greater is its electron affinity.
ii) Nuclear charge
Greater the magnitude of nuclear charge of an element stronger is the attraction of its
nucleus for the incoming electron. Thus, with the increase in the magnitude of nuclear
charge, electron affinity also increases.
iii) Electronic configuration of atom
The electron affinity is low when the electron is added to a half filled sub-shell than that
for partially filled one. Electron affinity values of ‘N’ and ‘P’ group-15 (V-A), atoms are
very low. This is because of the presence of half-filled ‘np’ orbitals in their valence shell
(N = 2s2 2p3, P = 3s2 3p3). These half-filled p-subshells, being very stable, have very little
tendency to accept any extra electron to be added to them. Noble gases group-18 (VIII-A)
have stable ns2 np6 configuration and hence the atoms of these gases, do not accept any
extra electron, This is evident from their positive 1st electron affinities.

1.7.5 Periodic trends in electron affinity

As the atomic size increases down the group, the larger electron cloud causes the incoming
electron to experience less attraction from the nucleus. Consequently, electron affinity
generally decreases down the group. This trend is observed in the halogens (At < I < Br
< F < Cl). Generally, electron affinities become more negative as we move from left to
right period. This is firstly due to increase in the nuclear charge, which attracts additional
electrons more strongly and secondly due to decreasing atomic radius.
Table 1.1: Electron Affinities (KJ/Mol) for Group 1 and Group 17
ELEMENT ELECTRON AFFINITY ELEMENT ELECTRON AFFINITY
(kJ/Mol) (kJ/Mol)
Fluorine -328.0 Lithium -60.0
Chlorine -349.0 Sodium -53.0
Bromine -324.0 Potassium -48.0
Iodine -295.0 Rubidium -47.0
Astatine -270.1 Cesium -46.0

Quick Check 1.7

Explain with reasoning following facts about electron affinity:
a) 1st electron affinity of Oxygen is -141KJ/mol but 2nd electron affinity is +844.0 KJ/mol.
b) Which of nitrogen and phosphorus has the higher electron affinity? Justify with reason.
c) F has lower electron affinity than Cl although its size is smaller. Explain why?

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1.7.6 Variation in Electronegativity

Electronegativity is the power of an atom to attract shared Did You Know!
pair of electrons toward itself in a molecule Linus Pauling,
Linus Pauling is the only person
an American chemist, developed a scale of dimensionless
to have received two unshared
electronegativity values, which range from just below one
Nobel Prizes, one for chemistry
for alkali metals to a maximum of four for fluorine. Higher
in 1954 for his work on the nature
electronegativity values signify a stronger attraction for of chemical bond and one for
electrons compared to lower values. peace in 1962 for his opposition
to weapons of mass destruction.
Factors Affecting Electronegativity
i) Atomic size
A larger atomic size will result in a lower value of electronegativity. This is because
electrons being far away from the nucleus will experience a weaker force of attraction. For
example, the electronegativities of halogens in group 17 are in the order:
F > Cl > Br > I
ii) Effective nuclear Charge
A higher value of the effective nuclear charge will result in a greater value of
electronegativity, because an increase in nuclear charge causes greater attraction to the
bonded electrons. This is why the electronegativity in a period increases from left to right.
The electronegativity of Li in period 2 is 1.0 and F has a value of 4.0.

1.7.7 Periodic Trends in Electronegativity

When we move from left to right along the period, the electronegativity increases. this
is due to increasing nuclear charge Electronegativity
and decreaing size. In the groups, H
2.1
it decreases from top to bottom this increases
is due to the increse in size due to
the addition of shells and increasing Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
shielding effect. For example, in the
halogen group, the electronegativity Na Mg Al Si P S Cl
value decreases from fluorine (4.0) 0.9 1.2 1.5 1.8 2.1 2.5 3.0

to iodine (2.5) as shown in a part of

Electronegativity

K Ca Br
the periodic table in Fig 1.8. 0.8 1.0 2.8
increases

Normally, metals being on the left Rb Sr I

0.8 1.0 2.5
side of the periodic table, possess
lower electronegativity values than
Fig 1.8: Variation of electronegativity in groups and periods
those of non-metals. Hence, metals
are electropositive and non-metals are electronegative, relatively.
Figure 1.9 provides a summary of all the variation trends in various physical properties of
elements in the periodic table.

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

Ionization energy

Electon affinity
Atomic radius

er

Ionization energy
Electron affinity
c c h aract
etall i
Nonm ter
l i c c harac
l
Meta

Atomic radius

Fig. 1.9: Trends in various physical properties in the periodic table

1.7.8 Variation in Metallic Character

The metallic character of elements
is typically their tendency to lose increasing metallic character

increasing nonmetallic character

increasing metallic character

electrons. We find that elements

on the left side of the periodic
table have a greater tendency to
lose their outermost electrons to
achieve noble gas configuration. Metallic Character
In contrast, elements on the right
side of the table tend to gain
electrons. Therefore, elements on
increasing nonmetallic character
the left side of the periodic table
are metals that form positive ions, Fig 1.3: General trends for the metallic character of elements
while elements on the right side,
particularly in the right corner, are nonmetals that form negative ions. Hence one can
conclude that the metallic character of an element largely depends on its valence shell
electronic configuration.
Consequently, the metallic character of the elements decreases. In other words, the
increase in nuclear charge pulls the electron cloud closer to the nucleus, making it more
difficult for the atom to lose electrons and thereby decreasing across the period, the nuclear
charge increases while the at size decreases, which results in stronger attraction to the
valence electrons making its difficult. Therefore, m.c decrees from left to right. Its metallic
character. Thus, metallic character decreases across a period from left to right.
Contrarily metallic character increases as one moves down in a group of the periodic
table. This is due to the increases in at size and the shielding effect. Which reduce the

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

nuclear attraction on the valence electrons. The increase in metallic character (ease of
losing electron) makes the element more reactive. Hence Cesium is far more reactive and
electropositive than sodium or lithium.
Quick Check 1.3
a) Illustrate how does the metallic character vary in group 14
b) Identify semi metals in groups 14, 15 and 16. Why they are semi metals?

1.8 REACTIONS OF Na AND Mg WITH WATER, OXYGEN

AND CHLORINE:
1.8.1 With water
Sodium is more reactive than magnesium towards
water. Na reacts vigorously with water to form sodium
hydroxide and hydrogen while Mg reacts more slowly in
forming magnesium hydroxide and hydrogen. However
magnesium reacts with steam more vigorously to make
magnesium oxide and hydrogen gas.
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)
Mg(s) + 2H2O(l) Mg(OH)2(aq) + H2(g)
Mg(s) + 2H2O(g) MgO(s) + H2(g)
1.8.2 With Oxygen
Sodium burns in oxygen with a golden yellow flame
to produce a white solid mixture of sodium oxide and
sodium peroxide. Sodium is kept under kerosene oil to Magnesium powder burns very
prevent its reaction with air. It reacts vigorously with rapidly with an intense white
oxygen in open air to form peroxide. flame. This has led to its use in
fireworks and S.O.S. flares
2Na(s) + O2(g)   2Na2O2(s)
Under special conditions like limited O2 or high temperature, sodium oxide is formed.
4Na(s) + O2(g)   2Na2O(s)
Magnesium burns in oxygen with an intense white flame to give white solid magnesium
oxide.
2Mg(s) + O2(g)     2MgO(g)It
1.8.3 With Chlorine
Chlorine reacts with both metals to give soluble salts. It reacts exothermically with sodium,
golden yellow flame is seen and white solid, sodium chloride is formed. Magnesium also
reacts with chlorine to give white solid, magnesium chloride.

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2Na(s) + Cl2(g) 2NaCl(s)

Mg(s) + Cl2(g) MgCl2(s)
Quick Check 1.4
(a) What is the nature of oxides and hydroxides of Na and Mg?
(b) What could you predict about the reactivity of Ca, a group 2 element, when reacted with water and
oxygen?

1.9 TRENDS IN BONDING IN OXIDES AND CHLORIDES

OF PERIOD 3
Oxides of group 1, 2 & 3 (e.g., Na₂O) have more ionic character. These oxides exist
as giant ionic lattices with strong electrostatic forces between oppositely charged ions.
Oxides of group 4, 5, 6 & 7 (e.g., SO₂) are more covalent. These oxides exist as covalent
molecules with weak intermolecular forces. This transition is a result of the increasing
electronegativity and decreasing ionic character.
Similar to oxides, chlorides of group 1, 2 and 3 (e.g., NaCl) are predominately ionic.
Chlorides of elements from group 4, 5, 6 and 7 (e.g., PCl₅) are covalent. The covalent
character in chlorides increases due to decrease in difference of electronegativity between
the halogen and the other atom.
1.9.1 Classification of Oxides
i) Oxides
Oxides are binary compounds formed by the reaction of oxygen with other elements. The
classification of oxides is done into neutral, amphoteric and basic or acidic based on their
characteristics.

ii) Basic Oxides

A basic oxide is an oxide that when combined with water gives off an alkali. Metals react
with oxygen to give basic oxides. These oxides are usually ionic in nature. Group 1 and
2 form basic oxides when react with oxygen. Examples are: Na2O, CaO, BaO. Group
2 hydroxides solubility increases down the group so alkalinity also increases down the
group.
Na2O(s) + H2O(l) 2NaOH(aq)
CaO(s) + H2O(l) Ca(OH)2(aq)
iii) Amphoteric Oxides
Amphoteric oxides are oxides that can react with both acids and bases. This means they have
the ability to behave as either an acid or a base, depending on the conditions. Aluminum
oxide (Al₂O₃) is insoluble in water but reacts with hydrochloric acid to form aluminium
chloride and water, and with sodium hydroxide to form sodium aluminate and water.
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Al2​O3(s) ​+ 6HCl(aq) 2AlCl3(s) ​+ 3H2​O(l)

Al2​O3(s) ​+ 2NaOH(aq) Na2​Al2​O4(s) ​+ H2​O(l)

iv) Acidic Oxides:

An acidic oxide is an oxide that when combined with water gives off an acid. Non-metals
react with oxygen to form acidic oxides which are held together by covalent bonds. Silicon
dioxide is acidic oxide as it can react with bases. Examples of acidic oxides in period 3 are:
P2O3, P2O5, SO3, SO2

P2O3(s) + H2O(l) H3PO3(aq)

SO2(g) + H2O(l) H2SO3(aq)
Reactions of theses oxides with bases are given below:
SiO2(s) + 2NaOH(aq) Na2SiO3(aq) + H2O(l)
P2O3(s) + 6NaOH(aq) 2Na3PO3(aq) + 3H2O(l)
SO2(g) + 2NaOH(aq) Na2SO3(aq) + H2O(l)

1.9.2 Classification of Chlorides

Chlorine forms compounds with other elements known as chlorides. These chlorides
show characteristic behavior when we add them into water, resulting in solutions that can
be acidic or neutral.
i) Neutral Chlorides
Neutral chlorides are salts that, when dissolved in water, produce a neutral solution with
a pH close to 7. At the start of period 3, chloride sodium and magnesium do not react
with water. The solutions formed contain the positive metal ions and negative chloride
ions surrounded by water molecules. These ions are now known as hydrated ions and this
process is known as hydration. For example,
NaCl(S) Na+(aq) + Cl−(aq) (pH=7)
MgCl2(S) Mg+2(aq) + 2Cl−(aq) (pH=6.5)
Group 1 and group 2 chlorides are also neutral with few exceptions.
ii) Acidic Chlorides:
If we move in period 3, from alumium to sulphur all chlorides react with water to make
acidic solution with pH less than 7 this process is called hydrolysis. When AlCl3 is added
to water, aluminium and chloride ions in solution. Al3+ ion is hydrated and casues a water
molecule to lose an H+ ion, this process is hydrolysis. This turns the solution acidic. The
following reaction occurs:
AlCl3(s) + 3H2O(l) Al(OH)3(s) + 3HCl(aq)
Other examples of acidic chlorides are given below.

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SiCl4(l) + 2H2O(l) SiO2(s) + 4HCl(aq)

PCl3(l) + 3H2O(l) H3PO3(s) +3 HCl(aq)
Quick Check 1.8
a) ZnO reacts with HCl to give ZnCl2 and with NaOH to give Na2ZnO2. Give equations and also
predict the type of this oxide?
b) Why AlCl3 is an acidic halide, but NaCl not?
c) Predict whether the chlorides PCl5, NCl3 would be acidic or basic, give reason.
d) Would SO2 and P2O5 react with HCl and H2SO4 or with NaOH?

1.10 VARIATION IN OXIDATION NUMBER IN OXIDES

AND CHLORIDES
The oxidation number of an atom is the formal charge on that atom in a molecule or ion.
The oxidation number is also referred to as the oxidation state. In ionic compounds the
oxidation number of an atom is defined as the charge which appears on the, ions.
Let’s examine the oxidation numbers in oxides and chlorides of the third period.
The oxidation number of an element of 3rd Period in its oxide or chloride corresponds
to the number of electrons used for bonding and is always positive because oxygen and
chlorine are more electronegative than any of these elements. The oxidation number
matches the group number, reflecting the total number of valence electrons. Consider the
following table (Table 1.2) for oxidation states of various elements of the periodic table.
In the oxides, the oxidation number increases from +1 in Na to +6 in S. In chlorides, the
oxidation number increases from +1 in Na to +5 in P. Phosphorus and sulfur exhibit several
oxidation numbers because they can expand their octet by exciting electrons.
Table 1.2: Oxidation Numbers in Oxides and Chlorides of 3rd Period elements
Oxide Oxidation Number Chloride Oxidation Number
Na in Na2O +1 Na in NaCl +1
Mg in MgO +2 Mg in MgCl2 +2
Al in Al2O3 +3 Al in AlCl3 +3
Si in SiO2 +4 Si in SiCl4 +4
P in P4O10/ P in P4O6 +5/+3 P in PCl5 +5
S in SO3 +6 P in PCl3 +3
S in SO2 +4 S in SCl2 -2

into empty 3d orbitals. For instance, in SO2, sulfur has an oxidation number of +4 because
only four electrons are used for bonding, while in SO3, sulfur has an oxidation number of
+6 because all six electrons are used for bonding.

Quick Check 1.9

a) Calculate the oxidation number of sulphur in SO2 and SO3.
b) Why some p block elements show variable oxidation state.

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. Which scientist first time observed the periodicity in the elements?
a) J. Newlands b) L. Meyer
c) J.W. Döbereiner d) D. I. Mendeleev
II. Recognize the element if it has 3 electron shells, belongs to “s” block and has 2
electrons in its outer most shell.
a) Calcium b) Sodium
c) Magnesium d) Potassium
III. Which one do you think is correct about metallic character?
a) It decreases from top to bottom in a group.
b) It increases from top to bottom in a group.
c) It remains constant from left to right in a period.
d) It increases from left to right in a period.
IV. Which one is the correct statement among the following?
a) Anionic radius is generally smaller than atomic radius.
b) Cationic radius is generally bigger than atomic radius.
c) Cationic ionic radius is generally smaller than atomic radius.
d) Both anionic and cationic radii are smaller than atomic radius.
V. Which property increases as you go down a group in the periodic table?
a) Atomic radius b) Electron Affinity
c) Electronegativity d) Ionization energy
VI. Which set of the following conditions results in higher ionization energy?
a) Smaller atom and greater nuclear charge.
b) Smaller atom and smaller nuclear charge
c) larger atom and greater nuclear charge
d) larger atom and the smaller nuclear charge
VII. Which of the following atoms show more than one (variable) oxidation states?
a) Sodium b) Magnesium
c) Aluminum d) Phosphorous
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VIII. Which is the correct general trend in the variation of electron affinity in
a group?
a) It becomes less negative from top to bottom.
b) It becomes more negative from top to bottom.
c) It remains the same.
d) It has no definite trend and changes irregularly.
IX. What is the oxidation state of sulfur in the sulfate ion (SO42-).
a) + 4 b) + 2
c) + 6 d) 0
X. Which is the correct trend in variation of electronegativity along a period of the
periodic table?
a) It decreases from left to right across a period.
b) It increases from left to right across a period.
c) It remains constant.
d) It has no definite trend.
XI. The atomic radius generally…….. across a period in the periodic table.
a) Increases b) Decreases
c) Remains constant d) First increases then decreases
XII. Which one of the following elements has the highest ionization energy?
a) Sodium (Na) b) Magnesium (Mg)
c) Aluminium (Al) d) Argon (Ar)
SHORT ANSWER QUESTIONS
Q.2 Attempt the following short-answer questions:
a. What is 1st ionization energy? Give an example.
b. Explain why sulfur has a lower first ionization energy than phosphorus.
c. Why the elements in Group 13 to 17 are called p-block elements?
d. What are the factors that affect electronegativity?
e. What factors are responsible for the the increasing reactivity of alkali metals as you
move down the group?
f. Why some of the elements show variable oxidation numbers while others do not?
g. Identify the element which is in period 5 and group 15?
h. Why oxides of sodium and magnesium are more ionic than the oxides of nitrogen and
phosphorous?

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 PERIODIC TABLE AND PERIODIC PROPERTIES Chemistry-XI

i. Give reason for the different chemical reactivities of Na and Mg toward oxygen and
chlorine.
j. Why the ionization energy of lithium is much lower than that of helium despite the fact
that the nuclear charge of lithium is +3 and that of helium is +2.
k. The ionization energy of Be (atomic no. 4) is higher than that of B (atomic no. 5),
despite the fact that the nuclear charge of Be is +4 and that of B is +5.
l. What is common in Na+, Mg2+, Al3+, Ne0 and F−? Arrange them in increasing order
of sizes.
m. Consider the chlorides of sodium, magnesium, and phosphorus(V): NaCl, MgCl2, and
PCl5
(i) Classify each of these chlorides as acidic, basic, or neutral.
(ii) For each chloride, briefly explain the reason for your classification, referring to
their behavior when dissolved in water.

DESCRIPTIVE QUESTIONS
Q.3 Write equations for the reactions of Na and Mg with oxygen, chlorine, and water.
Compare the reactivity of both elements with these in terms of metallic character.
Q.4 Explain with the help of equations acidic and basic behavior of oxides and chlorides.
Q.5 Describe the factors affecting and periodic trends of electron affinity.
Q.6 Describe the factors affecting and periodic trends of ionization energy.

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 ATOMIC STRUCTURE

2
Chemistry-XI

ATOMIC
STRUCTURE
STUDENT LEARNING OUTCOMES [C-11-A-01 to C-11-A-25]

Describe protons, neutrons, and electrons in terms of their relative charge and relative
masses. (Understanding)
Recognize that the terms atomic and proton number represent the same concept.
(Understanding)
Recognize that the terms mass and nucleon nuclear represent the same concept.
(Understanding)
Explain the change in atomic and ionic radius across a period and down a group.
(Understanding)
Describe the behaviour of beams of protons, neutrons and electrons moving at the same
velocity in an electric field. (Understanding)
Determine the number of protons, neutrons, and electrons present in both atoms and ions
given atomic or proton number, mass/or nucleon number and charge. (Knowledge)
Relate Quantum Numbers to electronic distribution of elements. (Understanding)
Account for the variation in successive ionization energies of an element. (Understanding)
Define terms related to electronic configuration (some examples include: shells, sub-
shells, orbitals, principal quantum number (n), ground state). (Knowledge)
Describe the order of increasing energy of the sub-shells (s. p, d, and f). (Understanding)
Describe that, each atomic shell and sub-shell are further divided into degenerate orbitals
having the same energy. (Understanding)
Apply Aufbau principle, Pauli’s exclusion principle and Hund’s rule to write the electronic
configuration of elements. (Application)
Describe the number of orbitals making up s, p, d, and f sub-shells, and the number of
electrons that can fill s, p, d, and f sub-shells. (Understanding)
Describe the shapes of s, p, and d orbitals. (Understanding)
Determine the electronic configuration of elements and their ions with proton numbers.
(Knowledge)
(Some examples include: a. simple configuration e.g., 2, 8.
b. Sub-shells e.g., 1s², 2s², 2p6, 3s¹.
c. students should be able to determine both of these from periodic table and are not
required to memorize these.

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 ATOMIC STRUCTURE Chemistry-XI

d. Students should understand that chemical properties of an atom are governed by valence
electrons).
Explain the electronic configurations to include the number of electrons in each shell, sub-
shell and orbitals. (Understanding)
Explain the electronic configurations in terms of energy of the electrons and Inter-electron
repulsion. (Understanding)
Determine the electronic configuration of atoms and ions given the proton or electron
number and charge. (Understanding)
Describe free radical as a species with one or more unpaired electrons. (Understanding)
Illustrate the importance of electronic configurations and development of new materials for
electronic devices. (For example, semiconductors such as silicon has a specific electronic
configuration that makes them ideal for their use in electronic devices) (Understanding)
Deduce the electronic configurations of elements using successive ionization energy data.
(Application)
Deduce the position of an element in the periodic table using successive ionization energy
data. (Application)
Explain that ionization energies are due to the attraction between the nucleus and the outer
electrons. (Understanding)
Explain how ionization energy helps account for the trends across the period and down a
group of the periodic table. (Understanding)
Explain the factors influencing the ionization energies of elements in terms of nuclear
charge, atomic/ionic radius, shielding by inner shells and sub-shells and spin pair repulsion.
(Understanding)

2.1 ATOMIC NUMBER, PROTON NUMBER AND

NUCLEON NUMBER; IDENTITY OF AN ELEMENT
1n 1913, Moseleyv observed that when different elements were bombarded with cathode
rays, the X-rays of some characteristic frequencies were produced. It was found that the
square root of the frequency of the X-rays was directly proportional to the atomic number
of an element Z.
frequency (ν) α Z
He concluded that this number, i.e. the atomic number Z was a fundamental property of
an element. It is also called proton number. The number of protons and neutrons in the
nucleus of an atom is collectively called its nucleon number (A), also called mass number.
Atomic number is related to the mass number by the following equation
A=Z+N
For example, an atom of an element X having atomic number Z and mass number A is
A 27
described as Z X , e.g. 13 Al . Number of neutrons in an atom can be calculated as
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 ATOMIC STRUCTURE Chemistry-XI

N = A- Z
27
Let us consider 13 Al ,
Atomic number/ proton number (Z) = 13
Mass number/ nucleon number (A) = 27
N = 27-13 = 14
Similarly, the number of electrons, protons, and neutrons can be justified for an ion as in
the following example:
27
13 Al atom loses three electrons to form Al3+, then;
No. of protons = 13
No. of neutrons =14
No of electrons = 13 – 3 = 10
Similarly, gains an electron to form Cl- ion;
No. of protons = 17
No. of neutrons =18
No of electrons = 17+1 = 18 2-
In case electron gain happens by the neutral atoms, say 16 O to 8O , 31P to P3- and 32 S to
8 15 15 16
S2-, the number of neutrons, protons and electrons are as follows.
16

Table 2.1 Number of protons, electrons and neutrons in different ions

Species Neutrons Protons Electrons
O 2- 8 8 10
S2- 16 16 18
P3- 16 15 18

Thus the atomic number and proton number represent the same concept.
2.2 EFFECT OF ELECTRIC FIELD ON FUNDAMENTAL
PARTICLES:
The behaviour of particles in an electric field depends upon their mass and charge. If we
allow the beams of electrons, protons and neutrons to pass one by one at the same speed
through an electric field, they show their behaviour as follows.
1. Neutrons being neutral are not deflected but travel in a straight path perpendicular to
the direction of electric field.
2. Protons being positively charged are deflected towards the negative plate.
3. Electrons being negatively charged are deflected towards the positive plate, to greater
1
extent since they are times lighter than protons.
1836

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Figure 2.1 Behaviour of proton, electron and neutron in the electric field
The amount of deviation from its original direction of movement is measured in two ways.

(i) Angle of deflection charge (ii) Radius of deflection mass

mass charge
This is possible if we imagine that after deflection, the particle moves in a circular path.
Hence, the factors affecting the radius of deflection are reciprocal to that for the angle of
deflection.
2.2.1 Properties of fundamental particles:
The Table (2.2) shows the properties of three fundamental particles electron, proton and
neutron present in an atom.
Table 2.2 Properties of three fundamental particles

Relative
Particle Charge (coulomb) Mass (kg) Mass (amu)
charge
Proton +1.6022 ´ 10-19 +1 1.6726 ´ 10-27 1.0073
Neutron 0 0 1.6750 ´ 10-27 1.0087
Electron -1.6022 ´ 10-19 -1 9.1095 ´ 10-31 5.4858 ´ 10-4

Quick Check 2.1

a) Calculate the number of neutrons in the following elements.
39
19 K , 35 40
17 Cl , 18 Ar

2.3 EXPERIMENTAL EVIDENCES FOR THE

ELECTRONIC CONFIGURATION
The modern theory of electronic structure originates from the Bohr Model of atom.
Evidence for this and later models of the atoms derives principally from two sources;
atomic spectra and ionization energies.

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2.4.1 Atomic Spectra

When an element in its gaseous state is heated to high temperatures or subjected to
electrical discharge, radiation of certain wavelengths is emitted. The spectrum of this
radiation contains coloured lines and is called atomic emission spectrum. The atomic
emission spectrum of hydrogen is shown in Figure 2.2 (a).
When a beam of white light is passed through a gaseous sample of an element in cold
state, certain wavelengths are absorbed. The wavelengths of the white light that has been
absorbed by the atoms show up as dark lines on the spectrum. The spectrum of this radiation
is called an atomic absorption spectrum. The atomic absorption spectrum of hydrogen is
shown in Figure 2.2 (b). The wavelengths of the dark lines in the absorption spectrum are
exactly the same as those of coloured lines in the emission spectrum.

Figure 2.2 (a) atomic emission spectrum of hydrogen (b) atomic absorption spectrum of hydrogen
Each element has a unique arrangement of electrons and thus a unique range of fixed
energy levels. It follows that the wavelengths and frequencies of the radiation absorbed
or emitted when electrons jump from one energy level to another must also be unique.
This uniqueness convinces us to conclude that every element has its own characteristic
spectrum. Therefore, every element is identified by its characteristic spectrum. Hence,
we can say that atomic spectra are the finger prints of the elements. Figure 2.3 shows the
emission spectra of some elements.
656 nm 486 nm 434 nm 410 nm

Figure 2.3 Spectral series of various elements as plotted by a spectrometer

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2.3.2 Relation between ionization energy and energy levels (electronic

shells)
A major difference between electrons in different types of shells is their energy. We can
investigate the electronic configuration of the atoms by measuring experimentally the
energies of the electrons with in them. This can be done by measuring ionization energies.
Ionization energies are used to investigate the electronic configurations of elements in two
ways.
i. Successive ionization energies of the same element
ii. First ionization energies for different element
i) Successive Ionization Energies of the Same Element
We can look at an atom of a particular element and measure the energy required to
remove each of its electrons, one by one.
X X + + e- ΔHi1
X+ X2+ + e- ΔHi2
X2+ X3+ + e- ΔHi3
We can continue to remove electrons from an atom until only the nucleus is left. We call
this sequence of ionization energies, successive ionization energies. The successive
ionization energies show clearly the arrangement of electrons in shells around the nucleus.
If we take the
magnesium atom as an
example, and measure
the energy required to
remove successively
the first electron, the
second, the third, and so
on. We obtain a graph
when the ionization
energies values are
plotted against number
of electrons as in Figure
2.4. This plot shows that
successive ionization
energies increase when
we move from the
valence shell to the
inner shells. First two
electrons are removed Figure 2.4 A plot of the successive ionization energies of Mg
from the outermost
shell and require lower energy for their removal. But, a large increase occurs when the

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third electron is removed. This is because when two electrons of the outer shell have
been removed, the next has to be removed from the shell that is very much closer to the
nucleus. The next seven electrons are removed successively from the second shell and a
gradual increase in ionization energy is observed. A similar but much more enormous jump
occurs when the eleventh and twelfth electrons are removed. These electrons are removed
from the first, innermost shell, right next to the nucleus. Hence, over all, we observe two
large jumps in the successive ionization energies. These two large jumps in the series of
successive ionization energies are very good evidence that the electron in the magnesium
atoms exist in three different shells.
ii) First Ionization Energies of Different Atoms
The second way in which ionization energies show us the details of electronic configuration
is to look at how the first ionization energies of elements vary with atomic numbers. The
following figure Figure 2.5 shows a plot for the first 88 elements.
This graph tells us the following:

All ionization energies are strongly endothermic; it takes energy to separate an electron
from an atom.

As we go down a particular group, for example, from helium to neon to argon, or

from lithium to sodium to potassium, ionization energies decrease. The larger the
atom, the easier is to separate an electron from it. Actually, down the group, number of
shells increases, hold of nucleus on the valence electrons decreases, hence removal of
electrons becomes easier.

The ionization energies generally increase on going across a period. The group 1
elements, the alkali metals, have the lowest ionization energy within each period, and
the noble gases have the highest. It is due to the reason that across the period shell
number remains same. As the proton number increases, electrons are added in the
same shell. Therefore, nucleus attracts the valence electrons more strongly. As a result,
ionization energy increases across the period.

Figure 2.5 A plot of the ionization energies of first 88 elements against atomic number
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Quick Check 2.2

a) Write equations that describe:
i. the 1st ionisation energy of calcium
ii. the 3rd ionisation energy of potassium
iii. the 2nd ionisation energy of lithium
iv. the 5th ionisation energy of sulfur.
b) For the element aluminium (Z = 13), draw a sketch graph between the log10 of the successive
ionisation energies (y-axis) against the number of electrons removed (x-axis).
c) The first ∆Hi1 and the second ∆Hi2 ionisation energies (kJ / mol) of a few elements are given
in table.
Element ∆Hi1 ∆Hi2
I 2372 5251
II 520 7300
III 900 1760
IV 1680 3380

Which of the above element is likely to be:

i. a reactive metal,
ii. a reactive non-metal,
iii. a noble gas
iv. a metal that forms a stable binary halide of the formula AX2 (X = halogen).

e electron can be found.

2.5 QUANTUM NUMBERS

The Bohr model was a one-dimensional model that used one quantum number to describe
the distribution of electrons in the atom. The only important information was the size and
energy of the orbit, which was described by the n-quantum number. Since Schrodinger’s
model allowed the electron to occupy three-dimensional space, therefore, it required three
coordinates, or three quantum numbers, to describe the orbitals in which electrons can be
found. The three quantum numbers that come from Schrödinger’s wave equations are the
principal (n), angular (l), and magnetic (m) quantum numbers. These quantum numbers
describe the size, shape, and orientation in space of the orbitals in an atom.
2.5.1 Principal Quantum Number (n)
The principal quantum number, n, can have positive integral values 1,2,3,4… designated
by K, L, M, N…, and it corresponds the quantum number (number of orbit) in Bohr’s
model of the hydrogen atom. This quantum number, n, describes the size and energy of the
orbital. The collection of orbitals with the same values of n is called an electron shell. The
larger ‘n’ is, the greater the average distance of an electron in the orbital from the nucleus
and therefore the larger the orbital. An increase in ‘n’ also means that the electron has a
higher energy and is therefore less tightly bound to the nucleus.

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The principal Quantum number, n, can also be used to

calculate the maximum number of electrons in a shell
by the formula 2n2. Therefore shells K, L, M and N can
accommodate maximum electrons. 2,8,18, 32 respectively.
2.5.2 Azimuthal Quantum Number ()
Azimuthal a.nl also called Angular Momentum Quantum Number,l, can have integral
values 0 to (n- 1) for each value of n. This quantum number describes the shape of the
orbital. The values of ‘l’ are integers that depend on the value of the principal quantum
number. If n= 1, there is only one possible value of ‘l’, i.e, l =0 (n-1, where n = 1). If
n=2, there are two values of ‘l ’ i.e 0 and l. If n=3 there are, three values of ‘l’ i.e 0,1 and
2. Similarly, if n=4, there are four values of ‘l’, i.e. 0, 1, 2 and 3. The values of ‘l ’ are
designated by the letters s,p,d, and f, with which stand for sharp, principal, diffused and
fundamental, respectively. These are the spectral terms used to describe certain features
of spectral lines.
The set of orbitals that have the same n and  values is called a subshell. The number of
electrons in a subshell can be calculated by the formula 2(2l+1) as given in the Table 2.3.
Table 2.3 Shapes of orbital

Value of l 0 1 2 3
Obital designation s p d f
shape of orbital spherical polar (dumb bell) cloverleaf (double complicated
dumbbell)
No. of electrons in 2 6 10 14
a subshell, 2(2l +1)
The number of subshells in a shell is equal to its shell number. For example 1st, 2nd, 3rd,
and 4th shells have one, two, three and four subshells respectively.
Table 2.4 Relationship between n, l and subshells
Shell Principal Quantum (Azimzzuthal) Subshells No. of
number Quantum Number (l) subshells in
n a shell
K 1 0 1s 1
0 2s
L 2 2p 2
1
0 3s
M 3 1 3p 3
2 3d
0 4s
1 4p
N 4 2 4
4d
3 4f
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2.5.3 Magnetic Quantum Number (m)

The magnetic quantum number ‘m’ describes the orientation of an orbital in space. Within
a subshell, the value of m depends on the value of l. For a certain value of l there are (2l
+ 1) integral values of m as follows:
-l…………0………..+l
The values of m indicate the number of orbitals Did you Know!
Splitting of small fine lines in the presence of
in a subshell. If l = 0, (s-subshell) there is only maginatic field and there three dimensional
one possible value of m, i.e. 0. It means s-subshell orientation in space indicate the presence of
has only 1 orbital. If l=1, (p-subshells) there orbitals in subshells.
are three values of m; -1,0 and +1. It means
p-subshells has three orbitals.
If l=2, (d-subshell), there are five values of m, namely, - 2, - 1, 0, + 1 and + 2. It means
d-subshells have 5 orbitals.
If  =3, (f-subshell) there are seven values of m: i.e. -3, -2, -1, 0, +1, +2, +3. It means f-subshells
have 7 orbitals.
Orbitals of the same subshell have same energy and are called degenerate orbitals. These
degenerate orbitals are differentiated from each other in the presences of magnetic field,
hence the name of this quantum number, i.e. magnetic quantum number. The relationship
between the magnetic quantum numbers is provided in Table 2.5.
Table 2.5 Relationship between l and m
Subshell Azimuthal / angular Magnetic Quantum Number of
Quantum number (l) number (m) degenerate orbitals
(-l----- 0---- l+ ) (2l+1)

s 0 0 One orbital
-1
Three degenerate
p 1 0
p-orbitals
+1
+2
+1 Five degenerate
d 2 0
-1 d-orbitals
-2
+3
+2
+1 Seven degenerate
f 3 0
-1 f-orbitals
-2
-3

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Spin Quantum Number (s)

Electrons are thought of spinning around their own
axes, as the Earth does. According to electromagnetic
theory, a spinning charge generates a magnetic field.
It is this motion that causes an electron to behave like
a magnet. Figure 2.8 shows the two possible spinning
motions of an electron. One is clockwise and the other
is anticlockwise. To take the electron spin into account,
it is necessary to introduce a fourth quantum number
called the electron spin quantum number (s). Its values
1 1 (a) (b)
are + and – , as in Figure 2.8. Figure 2.4 (a) clockwise (b)
2 2 counterclockwise spins of an
electron.
The clockwise spin is represented by an arrow ( ) pointing upwards, while the clockwise
spin is represented by an arrow ( ) pointing downwards. Each orbital can accommodate at
the most two electrons provided the two electrons have opposite spins.
Thus it takes three quantum numbers to
describe an orbital but forth quantum number to Did you Know?
differentiate between the two electrons that can In the nth principal quantum number,
there are n subshells consisting of n2
occupy an orbital.
orbitals with a maximum number of
2n2 electrons.

Quick Check 2.3

a) What information about an electron in an atom can be obtained from:
i. Principal quantum number
ii. Azimuthal quantum number
iii. Magnetic quantum number
iv. Spin quantum number
b) For an electron(s):
i. If n=2 and  = 1, how many orientations in space are possible?
ii. If n=3 and = 2, which shell and subshell does the electron belong to?
iii. If =2, find all possible values of m and maximum number of electrons for m.

2.6 SHAPES OF ATOMIC ORBITALS

An atomic orbital is defined as the three dimensional region in space around the nucleus in
which the probability of finding the electron is maximum.
Let us discuss the different orbitals one by one.
2.6.1 s-orbital
The shape of an ‘s’ orbital is spherical. The electronic density around the nucleus in an s
orbital is uniformly distributed in all directions. With the increase in the principal quantum
number, the size of s orbital also becomes larger.
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z
z
y y

x
x

1s
2s
(a) n = 1, l = 0, m = 0 (b) n = 2, l = 0, m = 0

Figure 2.5 The boundary surface for, (a) 1s (b) 2s.

2.6.2 p-orbitals
The distribution of electron density for a 2p orbital is shown in Figure 2.6. The electron
density is not distributed in a spherically symmetric fashion as in an s orbital. Rather,
a p orbital has two lobes on any of the axis. The p orbitals are named as px, py, and pz
accordingly to their exes.

Figure 2.6 Thee 2p orbitals shapes of 2P orbitals

2.6.3 d and f orbitals

In a given shell, ‘d’ orbitals have different shapes and orientations in space. The dxy, dxz,
and dyz lie in the xy, xz, and yz planes, respectively. The lobes of the dx2 - y2 lie along the x
and y axes. The dz2 orbital has two lobes along the z-axis and a “doughnut” in the xy plane.
The shapes for the five d orbitals ( = 2,) are shown in Figure 2.7.

Fig. 2.7 The shapes of the five 3d orbitals

An f subshell has seven orientations in space, i.e. there are seven f orbitals. However, the
shapes of f orbitals are very complicated.

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Quick Check 2.4

a) What does an orbital represent according to the wave mechanical model of atom?
b) There are three orientations of p-orbital due to three values of magnetic quantum number. Justify it.

2.7 ELECTRONIC CONFIGURATION

Electronic configuration is the distribution of electrons among available shells, subshells,
or orbitals of an atom or ion. In case of subshells, the electronic configuration is described
by a notation that lists the subshell symbols, one after the other. Each symbol has a
superscript on the right. This gives the number of electrons in the subshell. For example,
the configuration of 94Be atom with two electrons in the ‘1s’ subshell and two electrons in
the ‘2s’ subshell is written 1s22s2.
Each group of orbitals in a subshell is labeled by its subshell notation. An electron in an
orbital is shown by an arrow. The arrow points upward, when s = +½ and downward when
s = -½. The orbital diagram of boron (115B) is as follows
11B = 1s 2s 2px 2py 2pz
5

2.7.1 Electronic Configuration in Shells

The electronic configuration of an atom describes the distribution of electrons in its atomic
shells. The shells, denoted as K, L, M, N, and so on, correspond to the principal quantum
number (n) of the orbitals.
Shell capacities each shell has a specific capacity for electrons:
K shell (n=1): 2 electrons maximum (1s orbital)
L shell (n=2): 8 electrons maximum (2s and 2p orbitals)
M shell (n=3): 18 electrons maximum (3s, 3p, and 3d orbitals)
N shell (n=4): 32 electrons maximum (4s, 4p, 4d, and 4f orbitals)
For example:
- Hydrogen (H): 1s¹ (K shell) - Helium (He): 1s² (K shell)
- Sodium (Na): 1s² 2s² 2p⁶ 3s¹ (K, L, and M shells)
2.7.2 Distribution of Electrons in sub shells orbitals
Following rules are applied to fill the orbitals of multi-electron atoms.
Aufbau principle
Aufbau principle is also known as the building up principle. This principle says that the
subshells in an atom are filled with electrons in an increasing order of their energy values.
Now, question arises that how to arrange the subshells energy wise.
Since, the energy of a subshell in the absence of any magnetic field, depends upon
the principal quantum number (n) and the azimuthal quantum number (l), hence the
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order of filling subshells with electrons may be obtained from the summation (n + l).
(n + l) values are given in Table 2.6.

Table 2.6 (n + l) values of various sub-shells.

Principal Azimuthal Subshell (n + )
quantum no. quantum no. Value
(n) ()
1 0 1s (1 + 0) = 1
2 0 2s (2 + 0) = 2
1 2p (2 + 1) = 3
3 0 3s (3 + 0) = 3
1 3p (3 + 1) = 4
2 3d (3 + 2) = 5
4 0 4s (4 + 0) = 4
1 4p (4 + 1) = 5
2 4d (4 + 2) = 6
3 4f (4 + 3) = 7
a) The subshell having lower (n + ) value has lower energy and is filled first. For
example, 4s orbital has (n + ) = 4 + 0 = 4 and 3d orbital has (n + ) = 3+2 = 5. Since
(n + ) value of 4s orbital is lower than that of 3d, hence 4s subshell has lower energy
than 3d and 4s will be filled first.
b) In case there are two subshells are having equal (n + ) values, then the subshell with
lower ‘n’ value will be filled first. For example, both 4p and 3d subshells have n+l
value equal to 5 (4p=4+1=5) and (3d = 3+2=5); 3d subshell will be preferred to be
filled because of its low n value.
According to this rule the energy wise arrangement of orbitals should be.
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s

Fig 2.12 The diagram shows the energy of each subshell. Each box on the diagram represents an atomic orbital.
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So, the order of filling of various subshells with electrons obtained by this rule is given
below Figure 2.12.

2.7.2 Pauli’s exclusion principle:

According to this principle. No two electrons in an atom can have the same values for
all the four quantum numbers or, “Two electrons in an orbital will always have opposite
spins”.
In the first shell of helium (He) atom, there are two electrons. They are present in 1s
orbital. According to the concept of quantum numbers and Pauli’s exclusion principal, the
values of their quantum numbers are:
Table 2.6 values of quantum numbers of two electrons in the same orbital
Electron n l m s
1
Electron 1 1 0 0 +
(clockwise)
2
1
Electron 2 1 0 0 –
2 (anticlockwise)
The two electrons having the same values of ‘n’, ‘l’ and ‘m’ can have different values of
‘s’. It means that their spins are in the opposite directions.
2.7.4 Hund’s rule
This rule gives an idea for filling electrons into the orbitals having equal energies. For
example, three p-orbtials, i.e., px, py and pz have equal energy. To understand it, let us take
an example in which three electrons are to be filled into three p-orbitals. There are two
different ways to do this as shown below:
px py pz px py pz

I (wrong) II (right)
Which of the two is correct? The answer is given by Hund’s rule, which states that,
When degenerate orbitals are available and more than two electrons are to be placed in
them, they should be placed in separate orbitals with the same spin rather than in the same
orbital with opposite spins.
According to the Hund’s rule, the correct way of filling three electrons in three p orbitals
is that in which each orbital is singly occupied.
2.7.5 Filling the Orbitals
A useful way of representing electronic configurations is a diagram that places electrons
in boxes Figure 2.13.

Each box represents an atomic orbital.

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The boxes (orbitals) can be arranged in order of increasing energy from bottom to top.

An electron is represented by an arrow.

The direction of the arrow represents the ‘spin’ of the
electron.
When there are two electrons in an orbital, the ‘spins’ of the
electrons are opposite, so the two arrows in this box point
in opposite direction.
Electrons in the same region of space repel each other
because they have the same charge. So wherever possible,
electrons will occupy separate orbitals in the same subshell
to minimize this repulsion. These electrons have the same
Figure 2.13 The electronic
‘spins’ in different orbitals. Electrons are only paired when
there are no more empty orbitals available within a subshell. configuration of boron in
Figure 2.14 shows the electronic structures of carbon, nitrogen and oxygen to illustrate
these points.

2Px 2Py 2Pz 2Px 2Py 2Pz 2Px 2Py 2Pz

Figure 2.14 When adding electrons to a particular subshell, the electrons are only paired when no more
empty orbitals are available.
The electron configurations of some elements of the periodic table in the light of the above-
mentioned principles are given in Table 2.7
Table 2.7 Electronic configuration of ground states of elements Z = 1 –36.
Z Element Configuration Z Element Configuration
1. H 1s1 19. K 1s22s22p63s23p64s1
2. He 1s2 20. Ca 1s22s22p63s23p64s2
3. Li 1s22s1 21. Sc 1s22s22p63s23p63d14s2
4. Be 1s22s2 22. Ti 1s22s22p63s23p63d24s2
5. B 1s22s22p1 23. V 1s22s22p63s23p63d34s2
6. C 1s22s22p2 24. Cr 1s22s22p63s23p63d54s1
7. N 1s22s22p3 25. Mn 1s22s22p63s23p63d54s2
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8. O 1s22s22p4 26. Fe 1s22s22p63s23p63d64s2

9. F 1s22s22p5 27. Co 1s22s22p63s23p63d74s2
10. Ne 1s22s22p6 28. Ni 1s22s22p63s23p63d84s2
11. Na 1s22s22p63s1 29. Cu 1s22s22p63s23p63d104s1
12. Mg 1s22s22p63s2 30. Zn 1s22s22p63s23p63d104s2
13. Al 1s22s22p63s23p1 31. Ga 1s22s22p63s23p63d104s24p1
14. Si 1s22s22p63s23p2 32. Ge 1s22s22p63s23p63d104s24p2
15. P 1s22s22p63s23p3 33. As 1s22s22p63s23p63d104s24p3
16. S 1s22s22p63s23p4 34. Se 1s22s22p63s23p63d104s24p4
17. Cl 1s22s22p63s23p5 35. Br 1s22s22p63s23p63d104s24p5
18. Ar 1s22s22p63s23p6 36. Kr 1s22s22p63s23p63d104s24p6

2.8 ELECTRONIC CONFIGURATION AND THE

PERIODIC TABLE
We have seen that the electron configurations of elements are related to their position in
the periodic table. The periodic table is structured so that elements with the same pattern
of outer-shell (valence) electron configuration are arranged in same groups.
You can easily write the electron configuration of an element based on its location in the
periodic table. The pattern is summarized in Figure 2.15. Notice that the elements can be
grouped in terms of the type of orbital into which the electrons are placed.
On the left are two columns of elements. These elements, known as the alkali metals
and alkaline earth metals (groups 1 and 2), are those in which the outer-shell s orbitals
are being filled. We see that the group 1 and 2 elements all have ns1 and ns2 outer
configurations respectively. When we jump to group 13 elements, we find that they have
ns2np1 configuration. On the right is a block of six columns. These are the elements in
which the outermost ‘p’ orbitals are being filled. In the middle of the table is a block of ten
columns that contain the transition metals. In these, the d orbitals are being filled. Below
the main portion of the table are two rows that contain fourteen columns. These elements
are often referred to as the f-block elements. These are the ones in which the ‘f’ orbitals are
being filled. Recall that the numbers 2, 6, 10, and 14 are precisely the number of electrons
that can fill the s, p, d, and f subshells, respectively.
Quick Check 2.5
a) With the help of periodic table, write the electronic configurations for the following elements
by giving the appropriate noble-gas inner core plus the electrons beyond it (i) 48Cd; (ii) 57La.
b) Write the complete electron configuration for antimony (Sb) with atomic number 51.
c) How many unpaired electrons are there in each atom of 51Sb?

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2.8.1 Valence electrons:

The electrons in an atom in the outermost shell are called valence electrons. These are
such electrons that are primarily involved in chemical reactions. The similarities among
the configurations of valence electrons account for similarities of the chemical properties
among groups of elements.
Figure 2.15 shows a periodic table which include the valence shell configurations included.
Note the similarity in electron configuration within any group (column) of elements.

Figure 2.15 The electronic distribution of elements of modern periodic table

2.8.2 Classification of elements of periodic table

The main-group or representative elements all have valence-shell configurations nsa npb.
They have some choice of ‘a’ and ‘b’. In other words, the outer ‘s’ or ‘p’ subshell is being
filled. Similarly, in the d-block transition elements, a ‘d’ subshell is being filled. In the
f-block transition elements or inner-transition elements, an ‘f’ subshell is being filled.
There is a definite pattern to the order of filling of the subshells as we go through the
elements in the periodic table. From this we can write down the building-up order. The
overall sketch of periodic table is given in Figure 2.16. This shows the blocks of elements.

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Figure 2.16 Modern periodic table showing s, p, d and f-block elements.

Figure 2.16 shows a periodic table indicating this pattern. For example, in the blue colored
area, an ‘ns’ subshell is being filled. In the green colored area, an np subshell is being
filled. In the yellow area, an (n – 1) d subshell is being filled. In the light golden area and
(n–2) f subshell is being filled.
We start building-up order by starting with the first period, in which the ‘1s’ subshell
is being filled. In the second period, we have ‘2s’; then staying in the same period but
jumping across, we have ‘2p’. In the third period, we have ‘3s’ and ‘3p’; in the fourth
period, ‘4s’, ‘3d’ and then ‘4p’. This pattern should become clear enough to visualize with
a periodic table.
The classification of elements of periodic table has been done into metals, non-metals,
representative, transition elements, periods, groups and blocks (s, p, d, f). This division
is done on the basis of electronic configuration and their valence electrons. The chemical
properties of various categories of elements discussed above can be easily assessed.
Quick Check 2.6
a) An element has the electronic configuration
1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p5.
i. Which block in the Periodic Table does this element belong to?
ii. Which group does it belong to?
iii. Which period does it belong to?
iv. Identify this element.
b) Which block in the periodic table does the element with the electronic configuration
1s2 2s2 2p6 3s2 3p6 3d5 4s1 belong to?

2.9 ELECTRONIC CONFIGURATION OF IONS AND

FREE RADICALS
2.9.1 Ions
Positive ions are formed when electrons are removed from atoms. The sodium ion, Na+
(proton number = 11), has 10 electrons. So, its electronic configuration is 1s2 2s2 2p6.
Note that this is the same as the electronic configuration of neon, the element with 10
electrons
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Negative ions are formed when atoms gain electrons. The sulfide ion, S2– (proton number
= 16), has 18 electrons. Its electronic configuration is 1s2 2s2 2p6 3s2 3p6, which is the same
as argon, the element with 18 electrons in each atom.
Note that, in general, electrons in the outer subshell are removed when metal atoms form the
positive ions. However, the d-block elements behave slightly differently. Reading across
the Periodic Table from potassium to zinc, the 4s subshell fills before the 3d subshell. But
when atoms of a d-block element lose electrons to form ions, the 4s electrons are lost first.
For example:
Ti atom: 1s2 2s2 2p6 3s2 3p6 3d2 4s2
Ti2+ ion: 1s2 2s2 2p6 3s2 3p6 3d2
Cr atom: 1s2 2s2 2p6 3s2 3p6 3d5 4s1
Cr3+ ion: 1s2 2s2 2p6 3s2 3p6 3d3
2.9.2 Free radicals
“A free radical is a species that has one or more unpaired electrons”.
An example of a simple free radical is free chlorine atom . The electron configuration
2 2 6 2 5
of this radical is 1s 2s 2p 3s 3p . In the 2p subshell, two orbitals have paired electrons
whereas, the third one contains a single unpaired electron. The unpaired electron is shown
by a single dot as in Cl . Apart from single atoms, groups of atoms can also be free radicals.
For example, OH , CH3, etc.

Quick Check 2.7

Write electronic configurations for the following ions and free radicals:
. .
i. Al (Z = 13) ii. O2– (Z = 8) iii. Fe3+ (Z = 26) iv. Cu2+ (Z = 29) v. Cu (Z = 29)

2.10 ELECTRONIC CONFIGURATION AND THE

FORMATION OF SEMICONDUCTORS
Semiconductors are materials that can conduct electricity under some conditions. They are
used in many electronic devices, including smartphones, laptops, and cars.
Example of the elements that can act as semiconductors are silicon, germanium and arsenic etc. The
formation of semiconductors is possible because of a unique electronic configuration of these elements.
Let us consider the example of Si and explore how it can be converted into a p-type and n-type
semiconductors.
The electron configuration of 14Si = 2, 8,4; meaning that it has 4 electrons in its valence shell. In the pure
crystalline form, each Si atom is bonded to four other Si atoms. In this form, there is no possibility of
electronic conduction through the Si crystal.

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 ATOMIC STRUCTURE Chemistry-XI

Figure 2.17 A crystal of pure silicon

P-type and N-type semiconductors are formed by “doping” a pure semiconductor material
with impurity atoms, where adding trivalent impurities (like boron or aluminum) creates
a P-type semiconductor, while adding pentavalent impurities (like phosphorus or arsenic)
creates an N-type semiconductor. The difference lies in whether the added impurity
creates “holes” (positive charge carriers) in the lattice, leading to P-type, or extra electrons
(negative charge carriers) leading to N-type.
2.11.1 P-type semiconductor formation:
Impurity atoms with three valence electrons (like Al) are added to the pure semiconductor.
Some of the trivalent atoms take place of the Si atoms in the crystals. The silicon atoms
cannot make four bonds due to the lack of electrons. For this reason, there are created holes
in the crystal lattice, which act as positive charge carriers as shown in Figure 1.15. This
process creates a positive-type semiconductor or N-type semiconductor. Electrons from an
external current source can move through the semiconductor and it can act as a conductor.
2.11.2 N-type semiconductor formation:
When impurity atoms with five valence electrons (like phosphorus) are added to the pure
semiconductor, some of Si atoms are replaced with the pentavalent phosphorus atoms. The
Si atoms in the vicinity of these atoms can make four bonds and the fifth electron is an
extra electron. These impurity atoms contribute extra electrons to the crystal lattice, which
become free to move and act as negative charge carriers as in Figure 1.15. The result is an
N-type semiconductor that can conduct electricity when connected to an external source.

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Figure 2.18 Dpoing and the formation of P-type and N-type semiconductor

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 ATOMIC STRUCTURE Chemistry-XI

EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. The quantum number ‘m’ of a free gaseous atom is associated with:
a) the effective volume of the orbital
b) the shape of the orbital
c) the spatial orientation of the orbital
d) the energy of the orbital in the absence of a magnetic field
II. When 3d subshell is completely filled, the next entering electron goes into:
a) 4f b) 4s
c) 4p d) 4d
III. Quantum number values for 2p orbitals are:
a) n = 2, l = 1 b) n = 1, l = 2
c) n = 1, l = 0 d) n = 2, l = 0
IV. An electron having the set of values: n = 4, l = 0, m = 0 and s = +1/2 lies in:
a) 2s b) 3s
c) 4s d) 5s
V. The quantum number values for the fourth electron of 49Be atom are:
a) 1, 0, 0 b) 2, 0, 0
c) 2, 1, 0 d) 1, 1, 1
VI. The correct order of first ionization energies is:
a) F > He > Mg > N > O b) He > F > N > O > Mg
c) He > O > F > N > Mg d) N > F > He > O > Mg
VII. A p orbital has a characteristic shape with how many lobes?
a) 1 b) 2
c) 3 d) 4
VIII. The three p orbitals in a given energy level are oriented:
a) Along the same axis.
b) At 45∘ to each other.
c) Mutually perpendicular to each other along the x, y, and z axes.
d) In a complex tetrahedral arrangement.
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 ATOMIC STRUCTURE Chemistry-XI

IX. How many d orbitals are there in a given energy level?

a) 1 b) 3
c) 5 d) 7
X. Which of the following species is predicted to have the highest bond order?
a) N2 b) O2
c) F2 d) Ne2
XI. Which of the following species has a zero bond order according to MOT?
a) H21+​ b) He21+
c) He22+ d) He2
XII. Which of the following molecular geometries has bond angles of approximately
120o?
a) Tetrahedral b) Trigonal planar
c) Bent (V-shaped) d) Trigonal pyramidal
SHORT ANSWER QUESTIONS
Q.2 Attempt the following short-answer questions:
a. There are three orientations of p-orbital due to three values of magnetic quantum
number. Justify it.
b. Size of Mg is bigger than Al, but ionization energy of Mg is more than that of Al.
Why?
c. ‘I3’ of Mg is much bigger than its ‘I2’. Justify.
d. Among the elements Li, K, Ca, S and Kr which one has the lowest first ionization
energy? Which has the highest first ionization.
e. Consider the electronic configuration of the potassium atom (atomic number 19).
f. (i) Write the full electronic configuration of potassium using the s, p, d, f notation.
g. (ii) Explain why the 4s subshell is filled before the 3d subshell in potassium, even
though the principal quantum number of the 3d subshell is lower.
h. i) An atom of element X has an atomic number of 17 and a mass number of 35.
Determine the number of protons, neutrons, and electrons in this atom.
i. (ii) If this element forms an ion with a charge of -1, how many protons, neutrons, and
electrons will be present in the ion?
j. In the ground state of mercury 80Hg:
i. How many electrons occupy atomic orbitals with n = 3?
ii. How many electrons occupy 4d atomic orbitals?
iii. How many electrons occupy 4pz atomic orbital?

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 ATOMIC STRUCTURE Chemistry-XI

iv. How many electrons have spin “up” (s = -½)?

k. The successive ionization energies for an unknown element are
I1 = 896 kJ/mol, I2 = 1752 kJ/mol
I3 = 14,807 kJ/mol I4 = 17,948 kJ/mol
To which family in the periodic table, does the unknown element most likely belong?
l.
Consider the following ionization energies for aluminum:
Al(g) → Al+ (g) + e− I1 = 580 kJ/mol
Al+(g) → Al2+(g) + e− I2 = 1815 kJ/mol
2+
Al (g) → Al (g) + e 3+ − I3 = 2740 kJ/mol
3+
Al (g) → Al (g) + e 4+ − I4 = 11,600 kJ/mol
(i) Account for the trend in the values of the ionization energies.
(ii) Explain the large increase between I3 and I4.
(iii) List the four aluminum ions given in order of increasing size, and
explain your ordering.
m. (a) State the general order of filling orbitals up to the 4p subshell.
(b) Explain why the 4s subshell is filled before the 3d subshell, according to the Aufbau
principle.
n. Draw the orbital box diagram for the valence electrons of a phosphorus atom (atomic
number 15), ensuring that your diagram adheres to Hund’s rule and the Pauli Exclusion
Principle.
DESCRIPTIVE QUESTIONS
Q.3 What are quantum numbers? Describe briefly principal and spin quantum
numbers.
Q4. Draw the shapes of s, p and d-orbitals. Justify these by keeping in view the
azimuthal and magnetic quantum numbers.
Q.5 What do you mean by successive ionization energies? How the electronic shell
structure of magnesium (Mg) is derived from the successive ionization energies?

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 CHEMICAL BONDING

3
Chemistry-XI

CHEMICAL BONDING
STUDENT LEARNING OUTCOMES [C-11-A-26 to C-11-A-46]

Analyze the formation of dative bond in CO, ozone and H3O+ ion (resonance structures are
not required). (Understanding)
Recognize that molecular ions/polyatomic ions can have expanded octets e.g., sulphate
and nitrate. (Understanding)
Use the differences in Pauling electronegativity values to predict the formation of ionic
and covalent bonds. (Application)
Use the concept of electronegativity to explain bond polarity and dipole moments of
molecules. (Understanding)
Explain the importance of VSEPR theory in the field of drug design by discussing how the
shape and bond angles of the molecules help chemist predict their interactions in the body.
(Understanding)
Describe the shapes and bond angles in molecules using VSEPR theory (including
describing sketching). (Understanding)
Explain valence bond theory. (Understanding)
Predict the shapes, and bond angles in molecules and ions. (Understanding)
Describe covalent bonding in molecules using the concept of hybridization to describe sp,
sp2, and sp3 orbitals. (Understanding)
Explain hybridization and types of hybridization. (Understanding)
Explain the salient features of molecular orbital theory. (Understanding)
Explain the paramagnetic nature of oxygen molecule in the light of MOT. (Understanding)
Calculate bond order of N2, O2, F2, and He2. (Understanding)
Describe the types of van der Waals forces. (Understanding)
Describe hydrogen bonding limited to molecules including ammonia and water.
(Understanding)
Use the concept of hydrogen bonding to explain the anomalous properties of water.
(Understanding)
Use bond energy values and the concept of bond length to compare the reactivity of
covalent molecules. (Application)
State that, in general, ionic, covalent, and metallic bonding are stronger than intermolecular
forces. (Understanding)
Define electronegativity as the power of an atom to attract electrons to itself. (Knowledge)
Explain the factors influencing the electronegativities of elements in terms of nuclear
charge, shielding by inner shells and subshells. (Understanding)
Explain the trends in electronegativity across a period and down a group of the periodic
table. (Understanding)

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 CHEMICAL BONDING Chemistry-XI

A chemical bond is the force that holds together two or more atoms, molecules or ions.
The properties of a substance depend on the type of the chemical bond between its atoms.
The term chemical bond includes ionic, covalent, dative, metallic bonds, as well as inter-
molecular forces, i.e. van der Waals forces. However, being weak enough, van der Waals
forces are usually not termed as pure chemical bonds. In this chapter, we shall discuss
the types of bonds in the light of electronegativity and its effect on the nature of bonding,
dipole moment, and polarity. Then, the modern bonding theories such as VSEPR, VBT,
Hybridization, and MOT will be discussed in detail. The intermolecular forces, i.e. van der
Waals forces will also be taken into account. Finally, a comparison of the chemical bonds
and intermolecular forces will be presented in terms of bond energies.

NaCl has ionic bond and is solid, but water is a covalent compound and liquid

3.1 LEWIS CONCEPT OF BONDING

Lewis concept of bonding gives a simple explanation of the formation of all types of
bonds. According to this theory, atoms make bonds to complete their outermost shells to
have noble gas-like configuration. This is mostly attained through the formation of an octet
in the valence shell.
3.1.1 Ionic Bond
According to the Lewis theory, the ionic bond is formed by the complete transfer of
electrons from an atom with low ionization energy to another atom with high electron
affinity. The Na atom (11Na = 2,8,1) tends to lose the outermost electron to form Na+(2, 8)
ion, which has the electron configuration of 10Ne, a noble gas nearest to it. Chlorine atom
Cl (2,8,7) gains one electron to form the chloride ion, Cl- (2,8,8) , also gaining the next
noble gas electron arrangement. The oppositely charged Na+ and Cl- ions are held together
by strong ionic bond in the crystal of NaCl.
A similar type of bond is expected between group 1and 2 metals and groups 16 and 17
elements.

Figure 3.1: Ionic bond formation between Na and Cl

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3.1.2 Covalent Bond (electron pair bond)

A covalent bond is formed by the mutual sharing of electrons between two atoms. While
sharing electrons, each atom completes its valence shell and attains the nearest noble gas
configuration. The bond formation between two Cl atoms is shown below (Fig. 3.2). A
covalent bond may be non-polar or polar in character. The bond between two Cl atoms is
purely covalent and non-polar. The electronegativity of the two atoms is exactly the same,
due to which, the bonded atoms remain electrically neutral and there is no charge on either
atom. The other such molecules are H2 F2, Br2 and I2 . Examples of polar covalent bonds
are H–Cl, H-Br, H2O, etc.

Figure 3.2: formation of a covalent bond between two Cl atoms

3.13 Dative bond (Coordinate Covalent Bond)

A dative bond is formed between two
atoms when the shared pair of electrons is H
O
donated by one of the bonding atoms. Let (a) H O
us consider the example of bond formation H H H H
+
between H2O and a proton (H ). H2O has
two covalent bonds and there are two lone
pairs of electrons on the oxygen atom.
On the other hand, the proton is deficient (b)
C O C O
in electrons. Therefore, the oxygen atom Lewis
can donate its lone pair of electrons to structure
the acceptor H+, and this results in the
formation of a dative bond as in the O
following diagram (Figure 3.3(a)). (c) O O O O O
oxygen
Carbon monoxide also contains a dative
free readical
bond between oxygen and carbon atoms.
Oxygen shares its two valence shell Figure 3.3: Dative bond formation (a) oxonium
(hydronium) ion, (b) ozone molecule (c) carbon
electrons with the carbon atom to make a monoxide
normal double covalent bond. However,
the valency of carbon is not satisfied with these bonds. It needs one more pair of electrons
to complete its octet. Oxygen atom donates one of its lone pairs for the formation of
a covalent bond, which is a dative bond as exhibited in Figure 3.3(b). The structure of
ozone molecule is presented in Figure 3.3(c). It is formed by a reaction between the
oxygen molecule with an oxygen atom (a free radical (O)). One of the oxygen atoms in
the molecule donates a pair of electrons to make a coordinate covalent bond with this free
radical. Therefore, the central atom has total three bonds including a double covalent bond
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 CHEMICAL BONDING Chemistry-XI

on one side and a coordinate covalent bond on the other. It carries a positive charge, while
the oxygen atom that accepts the lone pair carries a negative charge.
Quick Check 3.1
a) Draw the Lewis structures of N2 and CS2 molecules?
b) How many electrons are there in the valence shell of B in BF3? Does it have the ability to accept
a lone pair of electrons?
c) Show the formation of a dative bond between NH3 and BF3.

3.1.4 Expanded Octet in Polyatomic Ions

Polyatomic ions are the ions composed of more than one type 2
of atoms. There formal charge is the net charge on them which O
is calculated based on the number of electrons in their valence
shells after the formation of bonds. With the exception of O S O
ammonium ion (NH4+), these ions mostly carry a negative
charge, for example the carbonate (CO32-), sulfate (SO42–),
and nitrate (NO33–) ions. In some polyatomic ions, the central O
atom violates the octet rule by expanding its electron density sulfate ion
to the higher orbitals. These are said to have expanded octets.
Some prominent examples are SO42–, ClO4-, PO43-.
From the Lewis structures of SO42–, we can calculate the number of electrons around the
central S atom.
The number of electrons in the valence shell of S atom can be calculated as:
No of valence electrons = 2 × (double bond electrons) + 2 × (single bond electrons)
= 2 (4) + 2(2) = 12
Thus, S has 12 electrons in its valence shell and it exceeds the octet by 4 electrons. The
expansion of octet is caused by the involvement of the d orbital in bonding, which can
accommodate the extra electrons. The following electronic configuration of native S(0)
atom shows that it has two unpaired electrons in the p orbitals. The presence of d-orbital
allows this configuration to extend to 4 unpaired electrons by the transfer of one electron
from the 3p pair. It explains not only the variable oxidation states of S, but also the
possibility of accepting extra electrons in its d orbital.

3S 3P 3d

3S 3P 3d
In the same way, we can calculate the number of valence electrons around the central
iodine atom in the tri-iodide ion. The Lewis structure of the ion is given by:

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I I I

The number of valence electrons of the central atom can be calculated as follows,
No of valence electrons = 2 × (no. of single bond electrons) + 2 × (no. of lone pairs)
= 2 (2) + 2 (3)
= 10
The central iodine atom in tri-iodide ion (I3-) has 10 electrons in the valence shell and the
octet expands by two electrons.
Quick Check 3.2
a) Can the elements of period 2 of the periodic table have expanded octet? Explain why or why not?
c) Predict and explain the expanded octets in the following ions: ClO3−, PO43−.

3.2 ELECTRONEGATIVITY AND THE TYPE OF BOND

The concept of electronegativity has been discussed in detail in chapter 1. Here we
will discuss the effect of electronegativity on the type of bonding. The difference
in electronegativity of two bonded atoms provides an approximate measure of the bond
polarity and an indication of the type of bond. When this difference is very small or zero,
the bond is covalent and nonpolar. When it is large, the bond is polar covalent or ionic. The
following figure graphically depicts the change in the nature of bond with electronegativity
difference. Two atoms having electronegativity difference less than 0.4 are said to make a pure
covalent bond. An electronegativity difference between 0.4 and 1.8 corresponds to a polar
covalent bond, whereas, above this value the bond between two atoms will be ionic in nature.
The electronegativity differences between the atoms in the bonds such as H–H, H–Cl, and
NaCl are 0 (nonpolar), 0.9 (polar covalent), and 2.1 (ionic), respectively. This is why H-H bond
is purely non-polar, H-Cl a polar covalent bond, whereas NaCl is an ionic compound.
Difference of electronegativity
between bonded atoms Bond type

Zero Pure Covalent Covalent character

increases

< 1.8 Polar Covalent

Covalent character
> 1.8 Ionic decreases

Quick Check 3.3

a) Predict with the
Figure 3.4:help of electronegativity
Variation values
of the nature of bondwhether
with thethe bonds in these difference
electronegativity compounds would
be non-polar covalent, polar covalent, or ionic.
HF, KI, CaF2, ICl, Br2
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Dipole Moment and Polarity of Molecules

In compounds such as HF, where the bonded atoms are from different elements, the electronic
distribution between the atoms is uneven. Due to this reason, one atom carries causes partial
positive and the other negative charge. A molecule with δ+ charge on one part and δ- charge
on the other part is called a dipole and such a molecule is said to have a dipole moment. It
is a quantitative measurement of the polarity of a bond or a molecule. The dipole moments of
diatomic molecules like HF, HCl, HBr, HI, NO, etc. are directed from the positive ends (δ+) to
negative ends (δ-) as in Fig. 3.5. Dipole moment is measured in Debye unit (D). Higher dipole
moment indicates high polarity in a molecule.

H F

H nucleus F nucleus
Figure 3.5: Electron density in HF is higher near the F atom and the dipole moment is directed from H to F
For compounds having more than two atoms, the dipole moment depends on the structure
of the molecule. The dipole moment of water is 1.85 D which is directed from the end
having two hydrogen atoms to the end with the oxygen atom as in the structure shown
in Fig. 3.6. A linear H2O molecule (H-O-H) would have zero dipole moment. The non-
zero dipole moment value shows that water is a non-linear molecule. Experiments reveal
that the water molecule has a v-shaped structure. In contrast, SO2 has a dipole moment
of 1.61 D and in opposite direction to that in water. H2S is also a non-linear molecule as
the individual bonds are polar, but they don’t cancel each other’s dipole moment and the
overall molecule has some dipole moment.

P = 1.85 D P = 1.61 D

Figure 3.6: Vector addition of individual bond moments in angular H2O and SO2 molecules
However, some molecules have zero dipole moments as the symmetry in their structures
causes the cancellation of the individual bond moments. For example, BeCl2 is a linear
molecule having two similar Cl atoms on both sides of the central atom at 180°. The
individual Be-Cl bond moments are cancelled out as they are opposite in direction and
equal in amount. Similarly, CCl4 has four C-Cl bonds which are expected to have high
polarity due to a large electronegativity difference between C and Cl atoms. The bond
moments associated to the four C-Cl bonds are directed in such a way that they cancel
each other. The net dipole moment of the CCl4 molecule is zero making it a non-polar

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molecule. The CCl4 molecule is perfectly tetrahedral. Similarly, BF3 has a trigonal planar
symmetrical structure and its dipole moment is also zero. As a rule, the molecules that have
same ligands (atoms or groups of atoms with the central atom) in a regular geometry, the
individual dipole moments may not be zero, but overall molecule has zero dipole moment.
Such a molecule is said to be non-polar.

Figure 3.7: The individual bond moments in symmetrical molecules; BeCl2, BF3 and CH4 are cancelled out to
give zero net dipole moment. δ-
Quick Check 3.4
a) Can you explain why CO has a dipole moment but CO does not have any?
2
b) Do you think that individual bonds δ-
in CCl4 are polar? Explain in terms of the electronegativity
difference. What about the polarity of overall CCL4 molecule?
c) Are these molecules polar or non-polar? Briefly give reasons. HF, CH2Cl2, O2, H2S

3.3.2 VALENCE SHELL ELECTRON PAIR REPULSION MODEL

(VSEPR)
The VSEPR model describes the shapes of molecules based on the electron pairs that
surround the central atom. This model was presented by Sidgwick and Powell in 1940.
It is based on the assumption that a molecule will take a shape such that the electronic
repulsions among the valence electrons of that atom are minimum. In order to have the
minimal repulsions, the electron pairs arrange themselves at farthest possible distances.
This arrangement of the electron pairs determines the geometry of the resulting molecule.
Postulates:
i. Both the lone pairs (non-bonded) as well as the bond pairs participate in determining
the geometries of molecules.
ii. The electron pairs are arranged around the central atom so as to remain at maximum
distance apart to avoid repulsions.
iii. The electrons of lone pairs occupy more space than the bond pairs. As a result, the
non- bonding electron pairs exert greater repulsive forces on bonding electron pairs
and, thus, tend to compress the bond pairs. The magnitude of repulsions between the
electron pairs in a given molecule decreases in the following order:
74 pm
Lone pair- lone pair (lp-lp) > lone pair -bond pair (lp-bp) > bond pair -(pm)
bond pair (bp-bp)

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An electron pair shared by two nuclei occupies less space thank a lone pair bound by a single nucleus

iv. The two electron pairs of a double bond and three electron pairs of a triple bond,
contain a higher electronic charge density, but they are regarded as single pairs.
v. The presence of highly electronegative atoms with the central atom results in decreased
electronic repulsions between the bond pairs, but stronger repulsion by the lone pair.
Predicting the Shapes of Molecules:
In order to illustrate this model, the central atom is named ‘A’. The electron pairs around
‘A’ are designated as ‘B’. There may be different number of electron pairs around the
central atom depending upon its valency. It gives rise to various types of molecules, such
as AB2, AB3, AB4, etc. The electron pair geometry of a molecule is determined by the
total number of electron pairs around ‘A’. Whereas, the actual shape of the molecule is
determined by the atoms excluding the lone pairs. Following Table (3.1) gives the possible
shapes of different types of molecules having varying numbers of bond and lone pairs.
Table 3.1: Geometries and shapes of different systems of covalently bonded compounds

No. of No. of Electron Shape with respect Angular Examples

electron lone pair to atoms separation
pairs around pairs geometry of atoms
central atom
2 0 linear linear 180° CO2, BeCl2

3 0 trigonal trigonal 120° BCl3, SO3

Less than
3 1 trigonal Angular, v- shaped SO2 , SnCl2
120°
4 0 tetrahedral tetrahedral 109.5° CH4, CCl4
Less than
4 1 tetrahedral pyramidal NH3, H3O+
109.5°
Less than
4 2 tetrahedral Angular, v-shaped H2O, OF2
109.5°
Trigonal
5 0 Trigonal 120°, 90° PCl5, I3-
bipyramidal
6 0 octahedral octahedral 90° SF6
Steps to Determine the shapes of molecules.
The following steps are followed to predict the shape of a molecule.
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The least electronegative atom or the element with the least number of atoms is mostly
selected as the central atom. For example, in CCl4, the carbon atom is the central atom.
The total number of electron pairs around the central atom are
counted (including bond pairs and lone pairs). For example in CCl4,
the total number of bond pairs around the C atom are 4 and it has no
lone pair.

The total number of electron pairs determines the electron pair

geometry (as in the above table) of the molecule. For example, CCl4 has total four
electron pairs and its geometry is tetrahedral.

Finally, the actual shape of the molecule is determined excluding the lone pairs (if
any).
AB2 type Molecules (Linear geometry)
In such molecules, two electrons pairs around the central atom are arranged at an angle of
180o to minimize repulsions between them. Thus, they form a linear geometry as shown in
Figure 3.9. BeCl2 molecule is of AB2 type with Be as the central atom and two bond pairs
around it, but no lone pair. .

Figure 3.9: Linear shape of the BeCl2 molecule

AB3 type (Trigonal planar geometry)
In AB3 type molecules, the central atom is surrounded by three electron pairs, which are
arranged at maximum distance apart at an angle of 120° giving a trigonal geometry. For
example, BF3 molecule has a trigonal planar shape with each F-B-F bond angle of 120°
Figure 3.10. The similar geometries are expected in the hydrides of group 3 (III-A), i.e.
AlH3, GaH3, BH3, etc.

Figure 3.10: BF3 is an AB3 system having triangular planar geometry

In SnCl2, the Sn atom has 4 electrons in its outermost shell. It makes two bonds with two
Cl atoms and the remaining two electrons exist as a lone pair (Figure 3.11 below). One of
the corners of the triangle is occupied by this lone pair, giving rise to a distorted trigonal
electron pair geometry (in vapour phase). The actual shape of SnCl2 is v-shaped and bond
angle less than 120° due to the presence of a lone pair on Sn atom.

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AB3-Type with Multiple Bonds

The molecule of SO3 has all the three regions occupied
by S=O bonds. The structure of SO3 is perfectly trigonal
with each angle equal to 120°. On the other hand, in
SO2, one corner of the triangle is occupied by a lone
pair and the other two corners each by a double bond
(S=O). Thus, it makes an angular or v-shaped structure
just as SnCl2 does as in Fig 3.12. Figure 3.12: Shapes of multiply
bonded SO2 and SO3
AB4 Type (Tetrahedral geometry)
In this type of molecules, the charge clouds due to four electron pairs avoid their electrostatic
repulsions by being farthest apart to form the shape of a regular tetrahedron. Each of the
bond angles is of 109.5°. For instance, each of the four valence electrons of carbon pair
up with the sole electron of a hydrogen atom in methane. The four bonded electron pairs
are directed from the center towards the corners of a regular tetrahedron, as following
Fig 3.13 with each corner representing a hydrogen nucleus. This arrangement permits a
non-planar geometry of electron pairs. Each H-C-H bond angle is perfectly 109.5°. On the
same grounds, SiH4, GeH4, CCl4 possess the similar shape.

Figure 3.13: Regular tetrahedral shape of the CH4 molecule

Extend your knowledge

The tetrahedral shape has four corners, four faces, six edges and six bond angles. Ideally it has bond
angles of 109.5° each.

In the ammonia molecule (NH3), there are three atoms attached to the nitrogen atom
having one lone pair. Due to a lone pairs the ideal angel 109.5° is reduce to 107° as in
Figure 3.14. This effect compels ammonia to assume a triangular pyramidal shape with
reduced bond angles, instead of a tetrahedral. The substitution of hydrogen in NH3 with
electronegative atoms like F or Cl further reduces the bond angles. Take the example of
NF3, which contains three highly electronegative F atoms bonded to the N atom. The
bond angles are further compressed to 102.5°. The first reason being the strong polarity
of N-F bond, due to which N atom pulls the lone pair closer to its nucleus. This, in turn,
exerts a stronger repulsion over bonding electrons. Moreover, the bond pairs (N-F bonds)
are closer to F atoms than N atom. The increased distances in these bond pairs make their
repulsions weaker and allow the bonds to come closer.
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Figure 3.14: Distorted geometry and pyramidal shape of the NH3 molecule
Experiments reveal that the water molecule (H2O) is angular or v-shaped, although it has four
electron pairs around the central atom. Two of the corners of the tetrahedron are occupied by
two lone pairs and the remaining two by bond pairs. But, due to the greater repulsions of the
lone pairs, the bond angle is reduced to 104.5° as in Fig 3.15.

Figure 3.15: Water molecule has two lone pairs and is v-shaped with suppressed bond angle
The VSEPR model also explains the shapes of ions. The hydronium ion [H3O]+ is formed
when a water molecule captures a proton. The hydronium ion belongs to AB4 type with one
lone pair and possesses a trigonal pyramidal shape just like the ammonia molecule. The amide
ion [NH2]– is also AB4 type as it is surrounded by two lone pairs and two bond pairs. Its
geometry is tetrahedral, but it has a bent shape (v-shape) similar to the water molecule
(Figure 3.16).

Figure 3.16: Shapes of hydronium (H3O+) and amide ions (NH2-)

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Quick Check 3.5

a) Calculate the number of bond pairs and lone pairs in SiH4, H2Se, and PH3.
b) Predict the shapes and angles in SiH4, H2Se, and PH3.
c) Predict how the bond angle in H2S would be different from that in H2O.

AB5 type (Trigonal Bipyramid Geometry)

In AB5 type molecules, repulsions between the five electron pairs can be minimized by an
even distribution of electrons among the corners of a trigonal bipyramid. In a trigonal
bipyramid, three positions lie along the corners of the planar triangle, whereas, the other
two positions lie along an axis perpendicular to the plane. This is evident from the geometry
of the PCl5 molecule given in Figure 3.17. The angles within the plane are 120° and that
between the axial atom and a planar atom is 90°.

Figure 3.17 Lewis structure and shape of PCl5 molecule

Just as in the AB3 and AB4 types, the presence of lone pairs in 180°
AB5 system also changes the shape and the angles, but the change
in this case is more dramatic. Tri-iodide ion [I3]- is linear, although
it is an AB5 system. The central atom in this ion is the iodine atom.
There are five electron pairs around the iodine atom including
two bond pairs and three lone pairs. Therefore, it is an AB5 type
molecule with three lone pairs and possesses trigonal bipyramidal
geometry. The lone pairs occupy the corners of the trigonal region
Figure 3.18: Shape of tri-
and the iodine atoms occur on the apices, one being above and the iodide ion ([I3])
second below the plane. However, excluding the three lone pairs,
the actual shape of the tri-iodide ion is linear and the iodine atoms are farthest apart at an
angle of 180° as in Figure 3.18.
AB6 type molecules (Octahedral Geometry)
AB6 type molecules have 6 electron pairs around the central atom. The repulsions between
the electron pairs can be minimized by assuming an octahedral geometry. In this geometry,
four electron pairs are at the corners of a planar square and the other two lie along an axis
perpendicular to the square. All the ABA angles in this type of geometry are of 90°. The
Lewis structure of SF6 is given in Figure 3.19, it shows that this is an AB6 type molecule.

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F F
F F 90°
F F F F
S
S F S
F
F F F 90° F
F F
F

Figure 3.19: Lewis structure and octahedral shape of SF6 with each angle of 90°
XeF4 is an AB6 type molecule with four bond pairs and two lone pairs. the two lone pairs
remain at farthest distance at angle of 180°. Excluding the lone pairs, the actual shape of
XeF4 is square planar with all F-P-F angles equal to 90°.

lone pair is farthest at 180°

F F F 90°
F F
Xe Xe F
F Xe
F F F F
F

Figure 3.20: Lewis structure and square planar shape of XeF4

Quick Check 3.6

Draw the Lewis structures for IF3 and IF5 and predict their geometry with reference to the VSEPR model.

3.3.3. Applications of VSEPR Model in Drug Designing

Drugs are chemical substances
that prevent, diagnose, or treat
a disease. Drugs interact with
human body at specific points,
or with specific processes called
targets or substrates, through
their bioactive molecules called
ligands. A receptor is mostly
a protein that receives and
responds to a ligand through
binding. The examples of targets
in the body are receptors, such as
enzymes, proteins, nucleic acids,
and cellular pathways. Each
drug interacts with a specific target in the body to a different degree, this feature is called
specificity of a drug or a ligand.
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Molecular shape is an important feature that determines how a drug interacts with a
biological target. Only the ligands with suitable shape can fit in the active sites of a
biological target as a specific key fits in a specific lock. VSEPR model is successfully
applied in determining the shapes of various biological systems, such as substrate
recognition, ligand specificity or selectivity, and antibody recognition. For example,
Aspirin is an analgesic drug (painkiller) used for relief from pain as a primary medicine. It
interacts with an enzyme COX (cyclooxygenase) by binding to its active site through the
acetyl group (-OCCH3).
The shape of COX active site and that of
acetyl group on Aspirin are compatible
with each other as in fig. 3.21 . Therefore,
the binding is successful to block COX,
which is a cause of the pain in the body.

3.4 VALENCE BOND

THEORY (VBT)
The VSEPR model predicts and explains
the shapes of molecules but does not give
reasons for the formation of bonds. VBT
is concerned with both the formation of
bonds and the shapes of molecules. This
method of describing a covalent bond Figure 3.21: An interaction of Aspirin with
considers a molecule as a combination of COX (Published after permission from Tulane
atoms. The postulates of VBT are given University Press)
below

A covalent bond is formed when half-filled orbitals in the valence shells of two atoms
with similar energy overlap.

A greater overlap of the orbitals results in a stronger bond.

Covalent bonds are directional. The direction of the bond is determined by the shape
and mode of the overlapping orbitals.
3.4.1 Formation of Sigma Bond
A sigma bond is formed by the linear overlap of two half-filled atomic orbitals on adjacent
atoms. The orbitals approach each other on the nuclear axis. Both s and p orbitals can
overlap head-on to form sigma bonds.
s-s Overlap
The ‘s’ orbital of one atom overlaps with the s-orbital of the other to give a bond orbital.
This type of overlap occurs during the formation of the H2 molecule, where each hydrogen
atom has a half-filled ‘s’ orbital.
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After the bond formation, the electrons are paired up and the electron density in this
molecule is symmetrical around the two nuclei as in Figure 3.22.

Symmetrical Electron
Density
Hydrogen Hydrogen
Figure 3.22: Overlap between s orbitals of two hydrogen atoms to form the H2 molecule

s-p Overlap
The s orbital of one atom can overlap with the p orbital of the other to form a covalent bond (σ).
For example, in HCl molecule, a half-filled s orbital of hydrogen overlaps with a half-
filled p orbital of chlorine as shown in Figure 3.23. The electron density is higher close to
the Cl atom due to its higher electronegativity value. This is why HCl is a polar molecule.

H Cl H Cl

Fig. 3.23: Formation of σ bond by s-p overlap

p – p Overlap
An example of this type of overlap is the formation of the Cl2 molecule where ‘p’ orbitals
of two chlorine atoms overlap on the nuclear axis. The electron density is symmetrical
around the nuclei of the two Cl atoms because both have same value of electronegativity.

Cl Cl

Molecule

Figure 3.24: Overlap of p and p orbitals to form Cl2 molecule according to VBT
The H2S molecule is a non-linear molecule which
Interesting Information!
is formed by the combination of one sulfur and
two hydrogen atoms. The two 3p (say 3py and 3pz) The bond angle in H2O is 104.5°,
orbitals of sulfur containing one electron each can whereas in H2S, it is 92°. This is
overlap with the 1s orbitals of two hydrogen atoms. because the orbitals of S are larger
A v-shaped molecule is thus formed having a bond and the lone pair exerts a stronger
angle of 92° as in Fig. 3.25. repulsion.

S
H 92º H
60 Fig. 3.25: The formation of H2S molecule by H and S orbitals overlap

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Formation of π bond:
Consider the formation of a double covalent bond
between oxygen atoms (O=O). There are two unpaired
electrons on each atom in perpendicular p orbitals (say
Px and Py). The px orbitals on the two oxygen atoms are
oriented in such a way that they overlap end-to-end
linearly. The linear overlap of the px orbitals gives a σ
bond. However, the py orbitals on both atoms are aligned
parallel to each other. They overlap in a parallel way
so that the two p lobes overlap above the plane of the
nuclei and the other two lobes below the plane as shown
in Figure 3.26. This results in the formation of π bond.
O O
the oxygen atoms are doubly bonded through σ and π Figure 3.26: Formation of double bond (σ
bonds. and π) between oxygen atoms
Quick Check 3.7
a) Draw the orbital structures of H2O and N2 molecules.
b) Draw the orbital overlap to show the formation of F2 and HF molecules

3.5 ATOMIC ORBITAL HYBRIDIZATION AND SHAPES

OF MOLECULES
A process in which atomic orbitals of slightly different energies and shapes are mixed
together to form a new set of equivalent orbitals of same energy and same shape is called
hybridization.

Keep in Mind
• Hybridization is a process of mixing of orbitals in a single atom (or ion).
• Only orbitals of comparable (relatively close) energies can be mixed to form hybrid orbitals.
• The number of mixing orbitals is always equal to the number of the resulting hybrid orbitals.

3.5.1 Types of Hybridization

sp3 Hybridization
In sp3 hybridization, one s-orbital (low energy and spherical) and three p-orbitals (high
energy and dumbbell shaped), intermix to give a new set of four orbitals of same energy
and same shape. Each of these hybrid orbitals is a sp3 hybrid orbital. These hybrid orbitals
are arranged in the tetrahedral geometry as shown in the example of CH4 as in Fig. 3.27.
The electronic configurations of valence shell of 6C in its excited and hybridized states are
given as follows:

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6Cground = Ground

2s 2px 2py 2pz

Cexcited = Excited Chybridized = hybridized

2s 2px 2py 2pz Sp3 Sp3 Sp3 Sp3

The energies of hybrid orbitals are lower than unhybrid orbitals. Figure 3.27 shows the
outermost four atomic orbitals of carbon mix up to give four hybrid orbitals of same energy
and same shape.

Figure 3.27: Formation of sp3 hybrid orbitals of C in methane

Did you Know?

Each sp3 hybrid orbital consists of two lobes, one larger and the other smaller. For the sake of simplicity,
the smaller lobe is usually not shown while representing sp3 hybrid orbitals together.

The four new hybrid orbitals of equal energy have a tetrahedral geometry with carbon
nucleus at the center. The methane molecule is formed by the overlap of sp3 hybrid orbitals
of carbon with 1s orbitals of four hydrogen atoms separately to form four sigma bonds.
The four C-H bonds, which result from sp3-s overlaps, are directed towards the corners of
a regular tetrahedron.

sp2 HYBRIDIZATION:
In sp2 hybridization, one s and two p atomic orbitals of an atom intermix to form three
orbitals called sp2 hybrid orbitals. The three half-filled sp2 hybrid orbitals are arranged in
a trigonal planar geometry with bond angles of 120°.

Figure 3.29: Formation of sp2 hybrid orbitals from atomic orbitals

The sp2 hybridization explains the geometry of planar molecules such as BF3. Electronic
configuration of 5B is:

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5Bground = Ground

2s 2px 2py 2pz

Bexcited = Excited Bhybridized = hybridized

2s 2px 2py 2pz sp2 sp2 sp2

The three outermost orbitals of B mix

together to give three sp2 hybrid orbitals.
On the other hand, one of the p orbitals
of fluorine is half filled (e.g. 2pz). BF3
is formed by the overlap of three half-
filled sp2 hybrid orbitals of boron with
2pz orbitals of three fluorine atoms. The
structure is triangular planer with bond
angles equal to 120°, each. Figure 3.30: Formation of BF3 molecule through sp2-p overlap

sp Hybridization
In sp hybridization, one s (low energy and spherical) and one p orbital (high energy and
dumb-bell shaped), intermix to give a new set of two orbitals of same energy and same
shape called sp hybrid orbitals. These sp hybrid orbitals are arranged in linear geometry and
oriented at 180º. The electronic configuration of the outermost shell of Be is as follows:
4Beground = Ground

2s 2px 2py 2pz

Beexcited = Excited Behybridized = hybridized

2s 2px 2py 2pz sp sp

The two sp hybrid orbitals lie linearly as in the following diagram Fig. 3.32. The sp
hybridization explains the geometry of linear molecules such as beryllium chloride, BeCl2.
It is formed when two sp hybrid orbitals of Be atom overlap with the half-filled p-orbitals
of chlorine atoms.

Figure 3.32: Mixing of s and p orbitals to give two hybrid sp orbitals and the formation of BeCl2

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3.6 MOLECULAR ORBITAL THEORY (MOT)

The molecular orbital approach explains the results of quantum mechanical calculations
for covalent bonding. The postulates of this theory are:
• During the formation of a molecule, the atomic orbitals of the combining atoms overlap
to form new orbitals called ‘molecular orbitals’, which are characteristic of the whole
molecule.
• The atomic orbitals overlap with the lobe having suitable sign of the wave function of
the orbital. For example, one lobe of a p orbital is given the ‘+’ sign and the other is
marked with ‘-‘ sign.
• Two atomic orbitals overlap to form two molecular orbitals. When same sign orbitals
overlap, the bonding molecular orbital (σ or π) is formed that has lower energy
than the parent atomic orbital, while with opposite signs, high energy anti-bonding
molecular orbital (σ* or π*) is formed, that has higher energy than the parent atomic
orbitals.
• The number of bonds formed between two atoms after the atomic orbitals overlap,
is called the bond order and is taken as half of the difference between the number of
bonding electrons (say a) and anti-bonding electrons (say b).
a–b
Bond order =
2
s-s Overlap
In the formation of H2 molecule, two s orbitals of H atoms combine to give two molecular
orbitals. The bonding molecular orbital is symmetrical about the axis joining the nuclei of
the bonded atoms (nuclear axis), while the anti-bonding molecular orbital has the electron
density away from the nuclei of the overlapping atoms as in Fig 3.34.

σ* 1s
σ* 1s
antibonding
molecular
orbital

σ 1s
bonding
σ 1s molecular orbital

Figure 3.34: Formation of bonding and anti-bonding orbitals for the H2 molecule
The p orbitals of an atom can combine to give
a) Head on approach
Here, the p-orbitals of the two atoms approach along the same axis (say x-axis) as shown
in Figure 3.35. This combination of atomic orbitals gives rise to σ (2px) bonding and σ*
(2px) antibonding molecular orbitals.
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b) Sideways Approach
When the axes of two p-orbitals (i.e py or pz orbitals) are parallel to each other, they
interact to form π molecular orbitals as shown in the diagram Figure 3.35. The bonding
molecular orbitals π(2py) or π(2pz) have zero electron density on the nuclear axis (called
the nodal plane). On the other hand, anti-bonding molecular orbitals π * (2py) and π * (2pz)
have the least electron density in the inter-nuclear region

Figure 3.35: Formation of ẟ and π MOs from px, py and pz orbitals

3.6.1 Molecular orbital diagrams of some diatomic molecules and their

bond orders
i) Helium
The electron configuration of He is
1s2. For a successful formation of He2
molecule, 1s orbitals of two He atoms
must combine to form bonding (ẟ1s) and
anti-bonding (ẟ*1s) orbitals as shown in
Figure 3.36. Out of four electrons, two
enter the bonding molecular orbital ẟ
(ls) and the remaining two occupy the
antibonding ẟ*(1s) molecular orbital.
But on calculation we discover that the
bond order for He2 is zero. Hence, He2
molecule is not formed. Figure 3.36: Molecular orbital diagram of He2 molecule

2–2
Bond order of He2 = =0
2

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ii) Nitrogen (N2)

Electronic configuration of N is,
7N: 1s2, 2s2, 2px1, 2py1, 2pz1
The molecular orbital diagram
of N2 based on this electron
configuration is shown in the
figure below (Figure. 3.37).
The valence shell 2s on both N
atoms give σ2s and σ* 2s orbitals;
whereas, 2p orbitals give six
molecular orbitals which are
arranged in the increasing order
of energy as:
σ2s < σ* 2s < π2py = π2pz < σ
2px <π*2py = π*2pz < σ* 2sPx
The bond order for N2 can be Fig 3.37: Molecular orbital diagram of N2
calculated from its orbital diagram molecule
as:
6–0
Bond order of N2 = =3
2
Therefore, there are three covalent bonds between the nitrogen atoms in this molecule.
One of these is a σ bond while the other two are π bonds. Nitrogen molecule has a triple
bond between its atoms.
iii) Oxygen, O2
The formation of molecular orbitals in oxygen molecule is shown as follows in figure 36.
The bond energy of the MOs can be arranged as
σ2s < σ* 2s < σ 2px < π2py = π2pz <π*2py = π*2pz <
σ* 2Px
The bond order of oxygen is 2( ), which shows the
presence of one σ and one π bond between the oxygen
atoms, i.e. they are linked by a double bond (O=O).
Oxygen molecule is paramagnetic in nature, which
means it is attracted by a magnetic field. Paramagnetic
substances have one or more unpaired electrons in them.
A substance with large number of unpaired electrons is
strongly paramagnetic. MOT successfully explains the
paramagnetic behavior of oxygen molecule. Liquid oxygen is attracted and
gets suspended between the poles
of a strong magnet
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The MO diagram of oxygen shows the presence of two unpaired electrons, one in π*(2py)
and π*(2pz) each. Due to the presence of these unpaired electrons, oxygen molecule has a
net magnetic field, which interacts with the external magnetic field.

Figure 3.38: Molecular orbital diagram of O2 molecule

3.7 INTERMOLECULAR FORCES

Intermolecular forces are also considered as binding forces just like chemical bonds.
However, the attraction between the molecules is much weaker than the chemical bonds.
These forces are believed to exist between all kinds of atoms and molecules when they
are sufficiently close to each other. Such intermolecular forces are called van der Waals
forces. These intermolecular forces bring the molecules close together and give particular
physical properties to the substances in gaseous, liquid, and solid states.
Three types of such forces are mentioned here:
i) Instantaneous dipole-induced dipole forces or London dispersion forces
ii) Permanent dipole-permanent dipole forces
iii) Hydrogen Bonding
The detailed discussion on these forces will be made in the chapter on states and phases
of matter

3.9 BOND ENERGY AND BOND LENGTH

The bond energy is the average amount of energy required to break all bonds of a particular
type in one mole of a substance. It is determined experimentally by measuring the heat
involved in a chemical reaction and its unit is kJ mol-1. Bond energy is a measure of the

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strength of a bond and its reactivity. The strength of a bond depends upon the following
factors.

• Electronegativity difference of bonded atoms

• Size of atoms.
The bond energies/enthalpies of some bonds are presented in Table 3.2.
Table 3.2 Average bond energies of some selected bonds in kJ mol-1

Single bonds Multiple bonds

H-H 432 C-I 240 F-F 154 C=C 614
H-F 565 C-Cl 339 Cl-Cl 239 C C 839
H-Cl 427 C-N 305 Br-Br 193 O=O 495
H-Br 363 C-O 358 I-I 149 C=O 745
H-I 295 N-H 391 S-S 266 N N 941
C-H 413 N-O 201 Si-Si 340 C N 615
C-C 347 O-H 467 Si-O 452 N=O 607

Let us consider the role played by electronegativity difference. Look at the bond energies
of H-X type of compounds, where X=F, Cl, Br, I. The data show that the bond energy of a
bond rises with the increasing electronegativity difference between the bonded atoms. As
the difference in electronegativity increases, the bond polarity also becomes greater and
this gives rise to additional attractive force for binding the atoms. This is why the bond
energy for HF is higher (565 kJ mol-1) than for HI (295 kJ mol-1). It may be noted that
energies of multiple bonds are greater than those of single bonds
C ≡ C > C=C> C-C
Bond length is the distance between the nuclei of two atoms forming a covalent bond.
The bond lengths are experimentally determined by physical techniques, such as electron
diffraction, X-ray diffraction, or spectral studies. The bond length of a bond is governed by
many factors including electronegativity, size, and the nature of the covalent bond (single,
double, or triple). Some selected bond lengths are given in Table 3.3.
Table 3.3 Bond lengths of some selected bonds
Bond Bond length (pm) Bond Bond length (pm)
H-H 74 Si-F 155
H-Br 144 C-F 135
C-C 154 C-Cl 180
C=C 133 C-Br 196
C C 120 C-I 214
C=O 122 B-F 130
Si-H 146 B-Cl 175

With an increase in size of the atoms, the covalent bond length also increases. The C-Cl
bond length is about 180 pm, whereas the C-F bond length is 135. This is because the
Cl atom is much larger. With the rise in electronegativity difference between the bonded
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atoms, the bond becomes shortened. For example, Si-F bond length in SiF4 is found to
be near 155 pm, whereas the calculation of Si-F bond from the covalent radii of Si and
F (Si=117 pm and F=64 pm) is 181 pm. The electronegativity difference causes an ionic
character in the covalent bond. The ionic character results in shortening of the bond length
due to the additional attraction between the bonded atoms.
Quick Check 3.10
• HI is a stronger acid and a robust reducing agent, whereas HF is a weaker acid. Explain.
• Acetylene (HC≡CH) is more stable than ethene (HC=CH). Can you explain why?

3.10 A COMPARISON AMONG IONIC, COVALENT,

METALLIC BONDS AND INTERMOLECULAR FORCES
Chemical bonds, i.e. ionic, covalent, and metallic Table 3.4 Relative strengths of chemical
bond are usually termed as true chemical bonds, bonds and intermolecular forces
as they affect the chemical properties of a BondBondEnergyBond Energy
Energy Bond Energy
substance. This is because of certain reasons. Bond
BondType
TypeBond TypeBond Type -1 -1
(kJ mol ) (kJ) mol(kJ
(kJ mol -1
) mol-1)
Firstly, chemical bonds result in the formation
of new species through transfer and sharing of Ionic
Ionicbond inIonic
bond NaCl bond
Ionicinbond
in NaCl NaClin NaCl
760 760 760 760
electrons. Whereas, intermolecular forces act to O-H
O-Hbond in O-H
bond water bond
in waterO-Hinbond
waterin water
464 464 464 464
bring molecules closer and influence the physical
properties. However, such a clear distinction Hydrogen
Hydrogen bonding
Hydrogen
bonding Hydrogen
bondingbonding
20-5020-50 20-50 20-50
between the chemical bonds and intermolecular Permanent
Permanentdipole-dipole
PermanentPermanent
dipole-dipole
dipole-dipole force dipole-dipole
force force
5-20 5-20
force 5-20 5-20
forces is not possible. The distinctive feature of Van
VanderderWaals
Vanforces
Waals der
Van
Waals
forcesder forces
Waals forces
1-20 1-20 1-20 1-20
the chemical bonds and intermolecular forces is
their bond strength. The strength of a force is
measured by the bond energy. Table 3.4 provides a comparison among different chemical
bonds and intermolecular forces.
The bond energy of ionic bond (sodium chloride, 760 kJ mol-) is highest, followed by
covalent bond (O-H = 464 kJ mol-), and average hydrogen bond energy (20-25 kJ mol-).
It shows that the ionic bond is the strongest form of chemical bonding. It also reveals that
chemical bonds are generally much stronger than intermolecular forces. The permanent
dipole-dipole forces (5-20 kJ mol-) and London dispersion forces (1-20 kJ mol-) are even
weaker as indicated by their low bond energies.
The metallic bond is mostly elaborated in terms of electrostatic forces, although some
theories suggest that it may be of covalent nature. In any case, the metallic bond is weaker
than both the ionic and covalent bonds. The average bond energy of the metallic bond is
100-150 kJ mol-. A satisfactory argument for the low strength of metallic bond is extensive
delocalization of electrons within the metallic crystal.

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KEY POINTS
EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. Chemical bond formation takes place when
a) force of attraction are equal to the force or repulsion
b) force of repulsion is greater than force of attraction
c) force of attraction overcomes force of repulsion
d) none of these
II. An ionic compound A+B- is most likely to be formed when
a) the ionization energy of A is high and electron affinity of B is low.
b) the ionization energy of A is low and electron affinity of B is high.
c) both the ionization energy of A and electron affinity of B are high.
d) both the ionization energy of A and electron affinity of B are low.
III. Which of the following molecules has zero dipole moment?
a) NH3 b) CHCl3
c) H2O d) BF3
IV. The numbers of σ and π bonds in the N2 molecule are:
a) one σ and one π bonds
b) one σ and two π bonds
c) three σ bonds only
d) two σ and one π
V. Which of the following species has unpaired electrons in antibonding molecular
orbitals?
a) O22+ b) N22-
c) B d) F2
VI. The shape of ICl3 according to the VSEPR model is:
a) Tetrahedral b) Trigonal planar
c) Trigonal bipyramidal d) T-shape
VII. Which of the following shows incorrect bond polarity?
a) Hδ+Fδ- b) Br δ+Br δ-
c) Clδ+Oδ- d) Cδ+Oδ-
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VIII. Which of the following molecules has a dipole moment?

a) CO2 b) CS2
c) SO2 d) CCl4
IX. How many electrons are present in the valence shell of P in PO43-?
a) 8 b) 10
c) 12 d) 14
X. How many extra electrons than a normal octet are there in the valence shell of I
in ICl5?
a) 2 b) 3
c) 4 d) 5
XI. What is the type and shape of [ICl4]- according to the VSEPR model?
a) AB4, tetrahedral b) AB4, pyramidal
c) AB5, trigonal bipyramidal d) AB6, square planar
XII. Which type of hybridization of C occurs in CO2?
a) sp3 b) sp2
c) sp d) dsp2
XIII. Which of the following molecules has a central atom with sp3 hybridization
and a tetrahedral electron pair geometry?
(a) BF3​ b) SO2​
(c) CCl4 d) PCl5​
XIV. Which of the following species contains a dative bond?
a) CH4​ b) NaCl
c) NH4 +​ d) O2​

SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. Define the following:
(i) Dipole (ii) Bond order (iii) Permanent dipole- permanent dipole force
(iv) London dispersion force
b. Draw the Lewis (electron dot) structures for the following species:
(i) HCN (ii) NCl3 (iii) CO (iv) O3 (v) NO2
c. Xenon ist a noble gas (group 18); xenon trioxide has the following structure:
Xe
O O
O

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i. By counting electron pairs around the central atom, explain why xenon trioxide
has this shape.
ii Draw a structure of xenon trioxide showing partial charges on the atoms and the
direction of the dipole in the molecule.
d. Explain the difference between the formation of σ and π bonds.
e. The structure of propanone (acetone) is:
O

H3C CH3

i. Show how the central carbon atom forms σ and π bonds through hybridization.
ii. Can propanone make a hydrogen bond with water when both are intermixed?
f. Predict the shapes of sulfate ([SO4]2-, borate ([BH4]-) and tri-iodide ions ([I3]-)
according to the VSEPR model.
g. Sketch the molecular orbital pictures of π(2p) and π*(2p).
h. Sketch the hybrid orbitals and bond formation in PCl3, SiCl4, and NH4+.
i. The structures of PF3 and SiF4 are given below. Redraw these with partial charges and
state which is polar and which is non-polar.
P F
F F F Si F
F F
j. Draw the orbital structures of the CO2 molecule in terms of VBT.
k. Draw the Lewis structures and tell whether these ions involve expanded octets?
i) ClO4- ii) ICl4− iii) NH4+ iv) I3-
l. The bond between K and Cl is ionic but that between Si and Cl is polar covalent.
Explain why.
m. SO2 is a polar molecule but SO3 not. Justify.
n. Which of O22+, and O22- would be paramagnetic? Give reason in the light of MOT.
o. Which of the following bonds would be most polar?
i) C-Cl ii) Si-F iii) Se-F
p. What are necessary conditions for the hydrogen bond to form?
q. Compare the bond energies of single, double, and triple bonds between the same two
atoms (e.g., H-H, O=O, O≡O). Explain the trend in terms of the number of shared
electrons.

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DESCRIPTIVE QUESTIONS
Q.3 How the bonding in the following molecules can be explained with respect to
valence bond theory?
(i) Cl2 (ii) O2 (iii) N2 (iv) HF (v) H2S
Q.4 What are the postulates of VSEPR model? Discuss the structures of the following
species with reference to this theory.
(i) CH4 (ii) NH3 (iii) H3O+ (iv) PCl5 (v) SO2 (vi) SF6
Q.5 Explain the orbital hybridization for CH4, NH3, BF3, and BeCl2.
Q.6 Draw the molecular orbital diagrams of the following molecules. Calculate their
bond orders?
(i)H2 (ii) He2 iii) N2 (iv) O2
Q.7 Discuss the formation of F2 molecule in the light of Lewis concept, VBT, and
MOT.

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4
Chemistry-XI

STOICHIOMETRY
STUDENT LEARNING OUTCOMES [C-11-A-47 to C-11-A-56]

Derive measurements of mass, volume, and number of particles using moles. (Application)
State the volume of one mole of a gas at STP. (Knowledge)
Use the volume of one mole of gas at STP to solve mole-volume problems. (Knowledge)
Calculate the gram molecular mass of a gas from density measurements at STP. (Application)
Express balanced chemical equations in terms of moles, representative particles, masses, and
volumes of gases at STP. (Application)
Explain the concept of limiting reagents. (Understanding)
Calculate the maximum amount of product and amount of any unreacted excess reagent. (Application)
Calculate theoretical yield, actual yield, and percentage yield when given appropriate information.
(Application)
Calculate the quantities of reactants and products involved in a chemical reaction using stoichiometric
principles. (Some examples include calculations involving reacting masses, volumes of gases,
volumes, and concentrations of solutions, limiting reagent and excess reagent, percentage yield
calculations). (Application)
Explain with examples, the importance of stoichiometry in the production and dosage of medicine.
(Understanding)

Stoichiometry is derived from Greek words stoicheion means element and metron means
measure. Collectively, stoichiometry means quantitative measure of reactants and products.
Stoichiometry (pronounced as stoy-key-om.eh-tree) is the branch of chemistry in which
the relationship between the amounts of reactants and products in a balanced chemical
equation is studied.
The balanced chemical equation has the same number of atoms of each type on both sides
of equation. It has definite ratios of reactants and products just as compounds have definite
ratios of elements. Such ratios are used to calculate the mass or mole of other substances.
Stoichiometric calculations obey law of conservation of mass and law of definite
proportions. According to the law of conservation of mass, “matter (mass) can neither be
created nor destroyed”. It states in terms of stoichiometry that the total mass of reactants is
equal to the total mass of products in a balanced equation. According to the law of definite
proportions, a pure compound always contains the same element combined in the same
ratio by mass.
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4.1 CONCEPT OF MOLE

The mole is the amount of a substance which contains as many elementary entities as
there are atoms in 0.012 kg (12 g) of carbon-12. The elementary entities may be atoms,
molecules, ions, electrons, and other particles. It is represented by n. The number of entities
present in one mole of a substance is a constant number named Avogadro’s Number, i.e.
6.02 x 1023. It is represented by NA. This value is attributed to an Italian scientist Amedo
Avogadro (1776-1856).

Did you Know?

Avogadro’s number is a physical constant representing the molar number of entities. The exact value
of it is 6.02214179 x 1023 mol‑. In calculations we use the rounded off value 6.02 x 1023.

Examples are given below:

1 mole of 12C contains 6.02 x 1023 atoms of 12C.

1 mole of H2O contains 6.02 x 1023 molecules of H2O.

1 mole of NaCl contains 6.02 x 1023 formula units of NaCl.

1 mole of Na+ contains 6.02 x 1023 ions of Na+.

The chemists use the mole as the SI unit to weigh and count atoms, molecules, formula
units or ions.
The mass of one mole of a substance (element, compound or ionic species) is equal to the
atomic mass, molecular mass, formula mass or ionic mass of a substance when expressed
in grams and is known as molar mass, represented by M. The mass of one mole of a
substance expressed in grams is called molar mass. The unit of molar mass is g/mol. The
molar mass is the sum of the masses of the component atoms.
The mass of one mole of CCl4 can be found by adding the masses of carbon and chlorine present.
Molar mass of CCl4 = Molar mass of one C + Molar mass of Cl x 4
= 12.0 x 1 + 35.5 x 4
Molar mass of CCl4 = 12.0 + 142.0 = 154.0 g

Other Examples
1 mole of carbon atoms is 12.0 g.
1 mole of CO2 molecule is 44.0 g.
1 mole of CaO formula units is 56.1 g.

1 mole of CO32- ions is 60.0 g.

The number of moles of a substance can be calculated by dividing mass in grams by molar
mass. The formula for number of moles is:
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Given mass
Number of moles =
Molar mass
m
n=
M
Sample Problem 4.1
Calculate the number of moles present in 20 g of NaOH.
Solution:
Given mass
Number of moles =
Molar mass
20
n= = 0.5 mol
40
Sample Problem 4.2
Calculate the mass of 0.5 moles of HCl.
Solution:
Mass of HCl = Number of moles x Molar mass
= 0.5 x 36.5 = 18.3 mol
Sample Problem 4.3
Calculate the mass of 10-3 mol of MgSO4.
Solution:
Molar mass of MgSO4 = 24 + 96 = 120 g mol-1
Number of moles of MgSO4 = 10-3
Mass of MgSO4 = 10-3 mol ´ 120 g mol-1 = 120 ´ 10-3 = 0.12 g
Quick Check 4.1
a. Calculate the molar mass of KMnO4.
b. Calculate the number of moles in 0.23 g of sodium.
c. Calculate the mass of 1.5 moles of Ca(OH)2.
d. The given mass of KCIO3 is 24.5 g. Calculate the number of moles of potassium chlorate.
e. How many molecules are present in 1.75 g of H2O2?
f. How many atoms are present in 15 g of gold ring?

4.2 RELATIONSHIP BETWEEN MOLE, MOLAR MASS

AND AVOGADRO’S NUMBER
A sample of 12.0 grams of natural carbon contains the same number of atoms as 4.0 grams
of natural helium. Both samples contain 1 mole of atoms i.e., 6.02 x 1023.
It is interesting to know that different masses of elements have the same number of atoms.

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1.0 g of hydrogen = 1 mol of hydrogen = 6.02 x 1023 atoms of H

23.0 g of sodium = 1 mol of Na = 6.02 x 1023 atoms of Na
238.0 g of uranium = 1 mol of U = 6.02 x 1023 atoms of U
An atom of sodium is 23 times heavier than an atom of hydrogen. In order to have equal
number of atoms, sodium should be taken 23 times greater in mass than hydrogen.
18.0 g of H2O = 1 mol of water = 6.02 x 1023 molecules of water
180.0 g of glucose = 1 mol of glucose = 6.02 x 1023 molecules of glucose
Hence, one mole of different compounds has different masses but the same number of
molecules.
Similarly, the number of ions in one mole of different ionic species is always the same, i.e
Avogadro’s number.
96.1 g of SO42- = 1 mole of SO42-= 6.02 x 1023 ions of SO42-
62.0 g of NO31- = 1 mole of NO31- = 6.02 x 1023 ions of NO1-
3
One can calculate the number of moles by dividing the number of particles by Avogadro’s
number.
No. of particles of a substance
Number of moles =
Avogadro’s Number
The relationship between amounts of substances in terms of their moles and the number of
particles (atoms, molecules, ions, electrons or particles) is given below:
Mass of subtance x NA
Number of particles =
Molar Mass

Molar x x Avogadro’s
Mass in mass number No. of
Moles
grams Particles

Sample Problem 4.4

A sample of glucose, contains 3.76 x 1024 molecules of glucose. What is the number of
moles in this quantity?

3.76 x 1024 molecules

Solution: No. of moles of glucose =
6.02 x 1023 molecules mol–1

= 6.25 moles
Sample Problem 4.5
How many atoms are there in a sodium metal that contains 2.3 g?

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Solution:
2.3
Number of moles of sodium = = 0.1 mol
23.0

Number of atoms of sodium = Number of moles of sodium x NA

= 0.1 x 6.02 x 1023
= 0.602 x 1023 atoms
Sample Problem 4.6
Juglone, is a dye and is produced from the husks of black walnuts. The formula for juglone
is C10H6O3.
a) Calculate the molar mass of juglone.
b) Calculate number of moles in 0.87 g of a sample of juglone extracted from black
walnut husks.

Interesting Information!
Juglone, is a natural herbicide (weed killer). It kills off competitive plants around the black walnut tree
but does not affect grass and other noncompetitive plants.

Solution:
a) C10H6O3
10 ´ Ar (C) + 6 ´ 1.0 Ar (H) + 3 ´ Ar (O)
(10 ´ 12.0) + (6 ´ 1.0) + (3 ´ 16.0)
120 + 6 +48 = 174 g/mol
Mass of 1 mol of C10H6O3 = 174 g/mol

Mass 0.87 g
b) Moles of juglone = = = 0.005 mol
Molar Mass 174 g mol-1
Quick Check 4.2
a) A copper wire contains 27.10 ×1025 atoms of copper. Calculate the number of moles of
copper.
b) Calculate the molecules of 1x10-6 g of isopentyl acetate, C7H14O2 which are released in
a typical bee sting. How many atoms of carbon, hydrogen and oxygen are present in it?

Interesting Information!
Isopentyl acetate (C7H14O2) is the compound responsible for the scent of bananas. Interestingly,
bees release about 1 mg (1 × 10-6 g) of this compound when they sting. The resulting scent attracts
other bees to join the attack.

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4.3 MOLAR VOLUME

The volume of one mole of an ideal gas at STP (Standard temperature and pressure) is
called molar volume. Its value is equal to 22.414 dm3. The value of molar volume is
commonly rounded to 22.4 dm3. It is denoted by Vm. By using molar volume relationship,
mass or mole of a gas at STP can be converted into volume, and vice versa.
According to Avogadro’s law, “Equal volumes of all ideal gases at the same temperature
and pressure contain equal numbers of molecules’’. This statement is indirectly the same
when we say that one mole of an ideal gas at 273.16 K and one atm pressure has a volume
of 22.414 dm3. Since one mole of a gas has Avogadro’s number of particles, so 22.414 dm3
of various ideal gases at STP will have Avogadro’s number of molecules i.e., 6.02 × 1023.
22.4 dm3 of a gas at STP = Molar mass of a gas =6.02 x 1023 particles of a gas= 1 mole of
a gas

22.4 dm3 of CO2 at STP = 44.0 g of CO2 = 6.02 x 1023 molecules of CO2 =1mole of CO2
22.4 dm3 of any gas at STP = molar mass in grams = 6.02 x 1023 molecules = 1mole
22.4 dm3 of H2 gas at STP = 2 g = 6.02 x 1023 molecules = 1mole

22.4 dm3 of NH3 gas at STP = 17 g = 6.02 x 1023 molecules= 1mole

If the number of moles of a gas is known, one can calculate the volume of a gas by
multiplying number of moles of the gas by molar volume.
Volume of a gas = Number of moles x Molar volume
V = n x Vm
Sample Problem 4.7
Determine the volume of 2.5 moles of chlorine molecules at STP.
Solution:
The formula for volume determination at STP
V= n x Vm
2.5 mole of Cl2 occupy a volume = 22.4 dm3 x 2.5 = 56.0 dm3
Sample Problem 4.8
What is the volume in dm3 of 4.75 mol of methane (CH4) gas at STP?
Solution:
The formula for volume determination at STP
V= n x Vm
Volume of methane in dm3 at STP = 4.75 x 22.4 = 106.4 dm3

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4.4 MOLAR MASS AND DENSITY OF GASES

Density is defined as the mass per unit volume of a substance.
Mass
Density =
Volume
m
d=
V
As molar mass of all the gases occupies same volume at STP, therefore, density of a gas
depends on its molar mass. A gas having higher molar mass will have higher density and
vice versa. If the density of gas at STP is determined, its molar mass can be calculated.
Sample Problem 4.9
Calculate the molar mass of a gas which has density of 1.97 g/dm3 at STP.
Solution
m =dxV
Mass of gas at STP = 1.97 x 22.4 = 44.1g mol-1
Quick Check 4.3
Calculate the molar mass of a gas which has density of 1.34 g/dm3 at STP.

4.5 MOLAR CONCENTRATION

Molar concentration of solutions is given as mol/dm3, which is the number of moles of a
substance (reactant or product) dissolved per volume of a solution in dm3. The relationship
between number of moles and molar concentration is given by
n=CxV
n
C=
V
Number of moles
MolarofConcentration
where C is the molar concentration and V is the volume the solution. = Volume in dm3

Mass Volume 0.2 mol

C= = 0.2 mol dm-3
Molar mass Molar Volume 1 dm3

Number
of
moles

No. of particles
Conc. × Volume
Avogadro’s no.

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Sample Problem 4.10

Calculate the molar concentration of a substance containing 27.64 g of K2CO3 dissolved
in 1 dm3 of the given solution.
Solution:
Mass of K2CO3 = 27.64 g
Molar mass of K2CO3 = 138.2 g mol-1
Given mass
Number of moles =
Molar mass
m
n=
M
27.64
n=
138.2
Volume of solution = 1 dm3
Number of moles
Molar Concentration =
Volume in dm3
0.2 mol
C= = 0.2 mol dm-3
1 dm3

Quick Check 4.4

Calculate the molar concentration of a solution containing 7.9 g of KMnO4 dissolved in 1 dm3 of the
given solution. The molar mass of KMnO4 is 158 g mol-1.

4.6 STOICHIOMETRY
Stoichiometry is a branch of chemistry which tells us the quantitative relationship between
reactants and products in a balanced chemical equation. With the knowledge of mole,
Avogadro’s number, molar mass, molar volume, and molar concentration, we can establish
quantitative relationships between reactants and products using the balanced chemical
equations.

STOICHIOMETRIC RELATIONSHIPS
The following types of relationship can be studied with the help of a balanced chemical
equation involving quantities of reactant(s) and product(s).
i. Mole-Mole Relationship
ii. Mass-mass relationship
iii. Volume-Volume Relationship
iv. Mole-Mass Relationship
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v. Mole-Volume Relationship
vi. Mass-Volume Relationship
To understand these relationships, we need to interpret information hidden in a balanced
chemical equation which is used to make stoichiometric calculations. For example:
N2(g) + 3H2(g) 2NH3(g)
This equation can be described in three different ways;
i. 1 mole of N2 reacts with 3 moles of H2 to form 2 moles of NH3.
ii. 1 molecule of N2 reacts with 3 molecules of H2 to form 2 molecules of NH3.
iii. 22.4 dm3 of N2 reacts with 67.2 dm3 of H2 to form 44.8 dm3 of NH3
iv. 28.0 g of N2 react with 6 g of H2 to form 34.0 g of NH3.

Keep in Mind!
The following assumptions must be made while performing stoichiometric calculations:
1) All the reactants are completely converted into the products.
2) Law of conservation of mass and law of definite proportions are obeyed.
3) No side reaction occurs.

APPROACH TO DO STOICHIOMETRIC CALCULATIONS

Mass of known solid or volume of a known gas, or molar concentration of known
solution

Calculate number of moles of known solid or volume of a known gas, or molar

concentration of known solution using the relevant formula

Find the ratio of the known and the unknow reactant or product from the balanced
chemical equation

Calculate the number of moles of the unknown reactant or product using the relevant
formula

Convert the number of moles of the unknown to mass, volume, or concentration of

the substance

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Sample Problem 4.11 (Mole-Mole Conversion)

When 3.3 mole of nitrogen reacts with hydrogen to form ammonia, how many moles of
hydrogen are consumed in the process? The equation for this reaction is
N2(g) + 3H2(g) 2NH3(g)
Solution:
Number of moles of N2 = 3.3 mol
Number of moles of H2 =?
1 mole of N2 needs H2 to produce NH 3 = 3 =3mol
1
3.6 moles of N2 needs H2 to produce NH3 = 3 × 3.3 = 9.9 mol
Quick Check 4.5
How many moles of carbon dioxide are produced when 2.25 moles of glucose are used by a person? The
oxygen is in excess. The equation for the reaction is:
C6 H12 O6(s ) +6O 2( g ) ¾¾
® 6CO 2( g ) + 6H 2 O(l )

Sample Problem 4.12 (Mass-Mass Conversion)

Calculate the mass of Al needed to react completely with 32.0 g of iron (III) oxide according
to the equation given below:
2Al(s) + Fe2O3(s) Al2O3(s) + 2Fe(s).
Solution:
Molar mass of Fe2O3, M = 159.6 g mol-1
m
Number of moles of Fe2O3 (n) =
M
32.0 g
=
159.6 g mol-1
= 0.02 mol
From the balanced equation, 1 mol of Fe2O3 reacts with 2 moles of Al, therefore,
number of moles of Al that reacts with 0.02 mole of Fe2O3= 2 x 0.02 = 0.04 mol
Mass of A = n x M
= 0.04 mol x 27 g mol-1
= 1.08 g
Quick Check 4.6
Fe2O3, an ore of iron is called Hematite. CO can reduce it to get free Fe as below:
Fe2O3(s) + 3CO(g) ¾¾® 2Fe(s) + 3CO2(g)
How much Fe can be produced from 160 g of Fe2O3?

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Sample Problem 4.13 (Volume-Volume)

Calculate volume of ammonia that can be produced by the reaction of 100 dm3 of hydrogen
with excess of nitrogen at STP? The balanced chemical equation for the reaction is:
N2(g) + 3H2(g) 2NH3(g)
Solution:
Volume of hydrogen = 100 dm3
Volume of ammonia =?
67.2 dm3 (3 mol) of H2 produce ammonia = 44.8 dm3 (2 mol)
44.8 2
1 dm3 of H2 produce ammonia = =
67.2 3
2
100 dm3 of H2 produce ammonia = x 100 = 66.7 dm3
3
So, the volume of ammonia produced by the reaction of 100 dm3 of H2 with excess nitrogen
is 66.7 dm3.
Quick Check 4.7
Calculate the volume of carbon dioxide produced at STP when 4.5 dm3 of methane is burnt by a person.
The oxygen is in excess. The equation for the reaction is:
CH4(g) + 2O2(g) à CO2(g) + 2H2O(g)

Sample Problem 4.14 Mole-Mass calculations

Solid lithium hydroxide LiOH is used in space vehicles. It is employed to remove exhaled
carbon dioxide from the living environment by forming solid lithium carbonate and liquid
water. Calculate the mass of Li2CO3 that can be produced by 20.0 mol of LiOH.
2LiOH(s) + CO2(g) ¾¾® Li2CO3(s) + H2O(l)
Solution:
According to the given balanced chemical equation,
2 moles of LiOH produces = 1 mole Li2CO3
1
20.0 moles of LiOH produces = ´ 20.0 = 10.0 mol Li2CO3
2
Mass of Li2CO3 produced = No. of mole ´ Molar mass
Mass of Li2CO3 produced = 10.0 mol ´ 73.9 g mol–1= 739.0 g
Thus, 739.0 g Li2CO3 will be produced from 20.0 moles of LiOH.

Quick Check 4.8

Calculate the mass of sodium hypochlorite (NaOCl), a household bleach, produced by the
reaction of 2.25 moles of chlorine with excess sodium hydroxide. The balanced equation is
2 NaOH(aq) + Cl2(g) NaOCl(aq) + NaCl(aq) + H2O().

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Sample Problem 4.15 (Mass-mole calculations)

Baking soda (NaHCO3) acts as an antacid. It can neutralize excess hydrochloric acid (HCl)
secreted by the stomach according to equation.
NaHCO3 (g) + HCl(aq) ¾¾® NaCl(aq) + H2O(l) + CO2(aq)
How many moles of HCl will be neutralized by 2.1 g of baking soda
Solution:
Molar mass of NaHCO3 = 84.0 g mol-1
2.1 g
Moles of NaHCO3 = = 0.025 mol
84.0 g mol-1
Stoichiometrically, the mole ratio of HCl and NaHCO3 is 1 : 1.
Hence moles of HCl used = 0.025 mol
Thus 2.1 g of NaHCO3 will neutralize 0.025 moles of HCl.

Sample Problem 4.16 (Mass-Volume Conversion)

What volume of hydrogen at STP will be produced when 7.0 g of iron are reacted with an
excess of sulphuric acid?

Fe(s) + H2SO4(aq) ¾¾® FeSO4(aq) + H2(g)

Solution:
Molar mass of Fe (M) = 55.8 g/mol
m
Number of moles of iron (n) =
M
7.0 g
=
55.8 gmol-1
= 0.125 mol
From the balanced equation, 1 mol of iron produces 1 mole of hydrogen.
So, number of moles of H2 = 0.125 mol
Volume of H2 in dm3 = molar volume x moles of H2
= 22.4 dm3 mol-1 x 0.125 mol
= 2.8 dm3
4.7 LIMITING AND EXCESS REACTANT
In many chemical processes, the quantities of the reactants are usually not present in the
proportions indicated by the balanced chemical equation. Frequently, a large amount of
inexpensive reactant is supplied because of the following reasons:
a. To ensure that whole of the mass of the expensive reactant is completely converted to
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the desired product

b. To produce maximum amount of product
c. To increase the rate of reaction
We know that a large quantity of oxygen in a chemical reaction makes things burn more
rapidly. In this way, excess of oxygen is left behind at the end of reaction and the other
reactant, i.e. fuel, is consumed earlier. This reactant which is consumed earlier is called
the limiting reactant. In this way, the amount of product that forms is limited by the
reactant that is completely used. Once this reactant is consumed, the reaction stops and no
additional product is formed. The reactant which controls the amounts of products formed
in a chemical reaction and is consumed earlier is called the limiting reactant or reagent.
The maximum amount of the product formed depends upon the amount of limiting reactant in
the reaction mixture.

4.7.1 Strategy for the identification of limiting reactant:

To identify a limiting reactant, the following three steps are performed.
i. Calculate the number of moles from the given amounts of reactants.
ii. Find out the number of moles of product with the help of a balanced chemical equation.
iii. Identify the reactant which produces the least amount of product as limiting reactant
and the other as an excess reactant.

Did You Know?

Fire is a combustion reaction in which fuel and oxygen, O2, combine, usually at high temperatures,
to form water and carbon dioxide. Once the fire has started, it is self-supporting. An effective way to
quench a fire is smothering, which reduces the amount of available oxygen below the level needed to
support combustion. In other words, smothering decreases the amount of the excess reactant. Foams,
inert gas, and CO2 are effective substances for smothering.

Following numerical problem will make the idea clear.

Sample Problem 4.17 (Limiting Reactant)
Calculate the mass of N2 produced from 1.81 g of NH3 (molar mass = 17.0 g mol-1) and
90.4 g of CuO (molar mass = 79.5 g mol-1) according to following balanced equation:
2NH3(g) + 3CuO(s) ¾¾® N2(g) + 3Cu(s) + 3H2O(g)
Solution:
Moles of NH3 = 18.1 g of NH3/ 17.0gmol-1 = 1.06 mol
Moles of CuO = 90.4g of CuO/79.5gmol-1 = 1.14 mol
In balanced equation, CuO : N2
3 : 1
1.14 : 1 ´ 1.14 = 0.38 mol
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NH3 : N2
2 : 1
1 : 1
2
1.06 : 1 ´ 1.06 = 0.53 mol
2
Thus, CuO is the limiting reactant and the number of moles of N2 produced will be 0.38
mol.
Hence, mass of N2 produced = n x M
= 0.38 mol x 17.0 g mol-1
= 9.0 g

Sample Problem 4.18 (Limiting Reactant)

When aqueous solutions of Na2SO4 and Pb(NO3)2 are mixed, PbSO4 precipitates down.
Calculate the mass of PbSO4 formed when 1.25 dm3 of 0.05 mol dm-3 Pb(NO3)2 and 2.00
dm3 of 0.025 mol dm-3 Na2SO4 are mixed.
Na2SO4(aq) + Pb(NO3)2(aq) PbSO4(s) + NaNO3(aq)
Solution:
The net ionic equation is
Pb+2(aq) + SO4-2(aq) ¾¾® PbSO4(s)
Since 0.05 mol dm-3 Pb(NO3)2 contains 0.05 mol dm-3 Pb2+ ions.
The formula : No. of moles = Concentration (mol dm-3 ) x Volume (dm3)
n = CV
3
moles of Pb2+ ions = 0.05 mol dm-3´ 1.25 dm = 0.0625 mol
Thus, 0.025 mol dm-3 Na2SO4 solution contains 0.025 mol dm-3 SO4-2 ions.
-2 3
moles of SO4 ions = 0.025 mol dm-3 ´ 2.00 dm = 0.05 mol
As Pb2+ and SO4-2 react in a 1 : 1 ratio, here, SO42- (0.05 mol) will be consumed earlier
than Pb2+ (0.0625 mol). The amount of SO4-2 will be limiting. The reason is that 0.05 mole
of SO4-2 is less than 0.0625 mole of Pb2+. Since the Pb2+ ions are present in excess, only
0.05 mole of solid PbSO4 will be formed. The mass of PbSO4 formed can be calculated
using the molar mass of PbSO4 (303.3 g mol-1):
Mass of PbSO4 = 0.05 mol ´ 303.3 g mol-1= 15.2 g

4.7.2 Maximum Amount of Product and Amount of Any Unreacted Excess

Reagent
The reactants which are in larger amounts (according to stoichiometry of reaction)
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and remain unreacted at the end of the reaction are called “excess reagents” (or excess
reactants). “The reactant that is left unreacted after the completion of reaction is called
non-limiting or excess reactant”.
Consider the reaction between hydrogen and oxygen to form water.
2H2(g) + O2(g) ¾¾® 2H2O(l)
When we take 2 moles of hydrogen (4 g) and allow it to react with 2 moles of oxygen
(64 g), then we will get only 2 moles (36 g) of water. Actually, we will get 2 moles
(36 g) of water because 2 moles (4 g) of hydrogen react with 1 mole (32 g) of oxygen
according to the balanced equation. Since less hydrogen is present as compared to
oxygen, so hydrogen is a limiting reactant.

When 1 mole of O2 and 1 mole of H2 are mixed, all the H2 will react completely and
O2 will be left unreacted because for 1 mole of H2, ½ mole of O2 is required. The
remaining 1 mole will be excess.
2
Sample Problem 4.19 (Excess Reactant)
Natural gas consists primarily of methane (CH4). The complete combustion of methane
(CH4) gives carbon dioxide (CO2) and water.
Ignition
CH 4(g) +2O 2(g) ¾¾¾® CO 2(g) +2H 2 O(g)

a) How many grams of CO2 can be produced when 30 g of CH4 and 50 g of O2 are allowed
to combine?
b) How many grams of excess reagent are left unreacted after the completion of reaction?
Solution (a):
Step 1: Write balanced chemical equation.
Step 2: Convert the given mass of both the reactants into their moles.

given mass of CH 4 30g

Moles of CH 4 = = =1.875mol
molar mass of CH 4 16gmol-1

given mass of O 2 50g

Moles of O 2 = = =1.563mol
molar mass of O 2 32gmol-1
Step 3: Calculate the number of moles of product from each reactant.
Compare the number of moles of CH4 with those of CO2. From the balanced chemical
equation.
1 mole of methane produces CO2 = 1mol
1.875 mole of methane produces CO2 = 1×1.875 mol = 1.875 mol of CO2
Compare the number of moles of O2 with those of CO2. From the balanced chemical

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equation, we know:
2 moles of oxygen produces CO2 = 1 mol
1.563 moles of oxygen produce CO2 = 0.5 × 1.563 mol = 0.7815 moles of CO2
From the above calculation, it is clear that the limiting reactant is O2 because it produces
lesser amount (moles) of product (CO2) than CH4.
Step 4: Convert the moles of the product into mass.
Mass of CO2 in grams = Moles of CO2 × Molar mass of CO2
= 0.7815 moles × 44 g mol-1= 34.39 g
Step 5: The quantity of limiting reactant can also be used to calculate the quantity of excess
reactant used:
2 moles of O2 reacts with moles of CH4 = 1 mol
1.563 moles of O2 reacts with moles of CH4= 1 ´1.563mol = 0.7815 mol
2
Step 6: The mass of methane (excess reagent) is equal to the starting quantity minus the
amount used during the reaction.
Number of moles of CH4 = Quantity taken – Quantity used
= 1.875 mol - 0.7815 mol =1.0935 mol
Mass of CH4 (excess reagent) = 1.0935 × 16.0 = 17.5 g

Quick Check 4.9

Which of the following reaction mixtures could produce the greatest amount of product when they
combine according to the reaction given below?
N 2( g ) + 3H 2( g ) ¾¾
® 2NH 3(g)
a) 1 mole of N2 and 3 moles of H2
b) 2 moles of N2 and 3 moles of H2
c) 1 mole of N2 and 5 moles of H2
d) 3 moles of N2 and 3 moles of H2
e) Each produces the same amount of product.

4.8 THEORETICAL YIELD, ACTUAL YIELD, AND

PERCENTAGE YIELD
The amount of the products obtained in a chemical reaction is called the actual yield of
that reaction. The amount of the products calculated from the balanced chemical equation
represents the theoretical yield. The theoretical yield is the maximum amount of the
product that can be produced by a given amount of a reactant, according to balanced
chemical equation.
In most chemical reactions the amount of the product obtained is less than the theoretical yield.
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There are following reasons for that:

The processes like filtration, separation by distillation, separation by a separating

funnel, washing, drying and crystallization, if not properly carried out, decrease the
actual yield.

Some of the reactants might take part in a competing side reaction and reduce the
amount of the desired product. So, in most of the reactions the actual yield is less than
the theoretical yield.

A reaction may be reversible. Therefore, the amount of the product will be reduced by
the backward reaction
A chemist is usually interested in the efficiency of a reaction. The efficiency of a reaction
is expressed by comparing the actual and theoretical yields in the form of percentage (%)
yield. Actual yield
% Yield = ´ 100
Theoretical yield
Greater the % age yield, higher will be the efficiency of reaction and vice versa.
Sample Problem 4.20 (% age Yield)
Aspirin (C9H8O4) is prepared by heating salicylic acid, C7H6O3 (molar mass 138.12 gmol-
1) and acetic anhydride, C H O (molar mass 163.93 gmol-1).
4 6 3
C7H6O3 + C4H6O3 ¾¾® C9H8O4 + CH3COOH
Calculate the theoretical yield of aspirin, (molar mass 180.16 gmol-1) when 3.00 g of
salicylic acid is heated with 6.00 g of (CH3CO)2O. What is % yield when actual yield is
3.15 g?
Solution:
C7H6O3 + C4H6O3 ¾¾® C9H8O4 + CH3COOH
Salicylic acid Acetic anhydride Aspirin
1 mol 1 mol 1 mol
138.12 g 163.93 g 180.16 g
1mole of Salicylic acid produces aspirin = 1 mol
Mass of Salicylic acid = 3.00 g
Number of moles of Salicylic acid = 3.00 g/ 138.12 gmol-1 = 0.022 mol
Mass of Salicylic acid = 6.00 g
Number of moles of Salicylic acid = 6.00 g/ 163.93 gmol-1 = 0.037 mol
Here, salicylic acid is limiting reactant while acetic anhydride is an excess reactant. The
amount of salicylic controls the yield of product i.e., aspirin.

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0.022 mole of Salicylic acid produces aspirin = 0.22 mol

Number of moles of Salicylic acid = Mass of Salicylic acid/ Molar mass of Salicylic acid
= 3.00/138.12 = 0.022 mol
0.022 mol Salicylic acid produces Aspirin =0.022 mol
Mass of Aspirin = 0.021 mol x 180.16 g mol-1 = 3.96 g
Theoretical yield = 3.96
Actual yield = 2.85
% age yield = 2.85/3.96 x 100 = 71.97 %

Quick Check 4.10

When limestone (CaCO3) is roasted, quicklime (CaO) is produced according to the following equation.
CaCO3 CaO + CO2
The actual yield of CaO is 2.5 kg, when 4.5 kg of limestone is roasted. What is the percentage yield of
this reaction?

4.9 IMPORTANCE OF STOICHIOMETRY IN PRODUCTION

AND DOSAGE OF MEDICINE
While preparing required dose of a medicine, the optimum amount of the active ingredient
in a medicine is essential to produce desired effects in the patient. Stoichiometry ensures
the accuracy of drug synthesis. Any deviation can result in incomplete reaction or
contamination with un-reacted reactants or by-products. Stoichiometry allows chemists to
precisely control chemical reactions to produce drugs, to ensure its efficiency, effectiveness
and safe use.
4.9.1 Significance of Stoichiometry in Medicine
Stoichiometry is very important in the field of medicine and is used to:
1. In the preparation of antibiotics, the stoichiometry ensures that each dose matches the
active ingredient and target bacteria.
2. To determine the cholesterol level in the blood of patients. Cholesterol is a form of fat
that is not all bad. However, cholesterol can have harmful effects.
3. To determine the glucose level in the blood of diabetic patient. Use of insulin relies on
the stoichiometry to precise control of blood sugar levels.
4. To determine the steroid and other stimulants in the urine of athletes. Athletes use
steroids and other stimulants to enhance performance and increase strength.
5. To determine the concentration of viral antigens in the preparation of vaccine for
effective results.
6. To determine the amount and number of drugs to give a dosage to a patient. The
medicine has no effect when given in small amounts and can cause toxic state or death
when given in large amounts. Paracetamol is used as a pain killer and to decrease fever.
An overdose may result a blood thinning, organ damage and severe liver damage.
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EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. Which one of the following statements is incorrect?
a) One mole of nitrogen gas contains Avogadro’s number of molecules
b) One mole of ozone gas contains Avogadro’s number of molecules
c) One mole of ozone contains Avogadro’s number of O atoms
d) One mole of hydrogen gas contains Avogadro’s number of molecules
II. Which one of the following has maximum mass?
a) 0.5 mol of N2 b) 0.5 mol of NH3
c) 0.5 mole of He d) 0.5 mol of CO
III. Which one of the following gases will have maximum volume at STP?
a) 22 g of CO2 b) 88 g of N2O
c) 28 g of CO d) 28 g of N2
IV. Which of the following contains same number of atoms as present in 12 g of
carbon?
a) 28 g of iron (Atomic mass of Fe = 56)
b) 48 g of magnesium (Atomic mass of Mg = 24)
c) 32 g of S8 molecules (Atomic mass S = 32)
d) 28 g of carbon monoxide (molar mass of CO = 28)
V. Volume at S.T.P. of 22 g of CO2 is same as that of:
a) 2 g of hydrogen b) 8.5 g of NH3
c) 64 g of gaseous SO2 d) 7 g of CO
VI. 4.0 g of NaOH (molar mass 40 g mol-1) contains same number of sodium ions as
are present in:
a) 10.6 g of Na2CO3, (molar mass 106) b) 58.5 g of NaCl (molar mass 58.5)
c) 76 g Na2SO4 (formula mass 142) d) 85 g of NaNO3 (molar mass 85)
VII. A container holds 0.5 moles of an ideal gas at STP. What is the volume of the gas
in dm³?
a) 11.2 dm³ b) 22.4 dm³
c) 44.8 dm³ d) 12.2 dm³

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VIII. A solution contains 4.0 g of sodium hydroxide (NaOH, molar mass = 40.0 g
mol⁻¹) in 250 cm³ of solution. What is the molar concentration of this solution?
a) 0.10 mol dm⁻³ b) 0.20 mol dm⁻³
c) 0.40 mol dm⁻³ d) 0.80 mol dm⁻³
IX. A solution contains 10.0 g of an unknown solute in 250 cm³ of solution. If the
molar concentration of the solution is 0.20 mol dm⁻³, what is the molar mass of
the solute?
a) 50 g mol⁻¹ b) 100 g mol⁻¹
c) 200 g mol⁻¹ d) 400 g mol⁻¹
X. A sample of nitrogen gas (N2​, molar mass = 28.0 g mol⁻¹) has a mass of 14.0 g. How
many nitrogen atoms are present in this sample?
a) 3.01 × 10²³ atoms b) 6.02 × 10²³ atoms
c) 1.20 × 10²⁴ atoms d) 2.40 × 10²⁴ atoms
XI. A gas has a density of 1.43 g dm⁻³ at STP. What is the molar mass of the gas?
(Molar volume at STP = 22.4 dm³ mol⁻¹)
a) 14.3 g mol⁻¹ (b) 22.4 g mol⁻¹
c) 32.0 g mol⁻¹ (d) 64.0 g mol⁻¹
XII. A gas has a density of 1.96 g dm⁻³ at STP (0 °C and 1.00 atm). What is its
molecular mass? (Molar volume at STP = 22.4 dm³ mol⁻¹)
a) 11.2 g mol⁻¹ b) 22.4 g mol⁻¹
c) 44.0 g mol⁻¹ d) 88.0 g mol⁻¹
SHORT-ANSWER QUESTIONS
Q.2 Attempt the following short-answer questions:
a. How is the concept of mole derived from Avogadro’s number?
b. Define the following terms with one example in each case.
(a) Molar mass (b) Molar volume (c) Molar concentration
c. What do you mean by molar volume of a gas? How Avogadro’s number is related with
molar volume?
d. 39 g of potassium and 56 g of iron have equal number of atoms in them. Justify.
e. 4 g of He, 17 g of NH3 and 64 g of SO2 occupy separately the volumes of 22.414 dm3
although the sizes and masses of molecules of three gases are very different from each
other.
f. Do you think that 1 mole of H2 and 1 mole of NH3 at 0 oC and 1 atm will have
Avogadro’s number of particles?
g. What is stoichiometry? Give the basic assumptions of stoichiometric calculations.
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h. What is a limiting reactant? How does it control the quantity of the product formed?
i. Differentiate theoretical and actual yields. How is the percentage yield of a reaction
calculated?
j. What are the factors which are mostly responsible for the low yield of the products in
chemical reactions?
DESCRIPTIVE QUESTIONS
Q. 3 Differentiate limiting and non-limiting reactants. How a limiting reactant is
determined from a balanced chemical equation and given data?
Q4. Differentiate actual and theoretical yields. Why the theoretical yield is always
greater than actual yield?
(NUMERICAL PROBLEMS)
Q.5 A solution of sodium hydroxide (NaOH) is prepared by dissolving 2.00 g of solid
sodium hydroxide in water to make a final volume of 250 cm3.
a) Calculate the number of moles of sodium hydroxide used.
b) Determine the molar mass of sodium hydroxide.
c) Calculate the concentration of the sodium hydroxide solution in mol dm-3.
d) If more water is added to the above solution to raise the volume of solution to
500 cm3, what would be the concentration now?
Q.6 Ammonia gas (NH3​) reacts with oxygen gas (O2​) according to the following
balanced equation:
4NH3​(g)+5O2​(g) ⟶ 4NO(g)+6H2​O(g)
In an experiment, 34.0 g of ammonia is reacted with 80.0 g of oxygen.
a) Determine the limiting reactant.
b) Calculate the maximum mass of nitrogen monoxide (NO) that can be formed.
c) Calculate the mass of the excess reactant remaining after the reaction is
complete. (Relative atomic masses: H = 1.0, N = 14.0, O = 16.0)
Q.7 When iron(III) oxide (Fe2​O3​) reacts with carbon monoxide (CO) in a blast
furnace, iron metal (Fe) is produced according to the following equation:
Fe2​O3​(s) + 3CO(g) ⟶ 2Fe(s) + 3CO2​(g)
If 1.00 kg of iron(III) oxide is reacted with excess carbon monoxide, and 650 g of
iron is obtained, what is the percentage yield of iron?(Ar of O = 16.0, Fe = 55.8)
Q.8 PbSO4 is precipitated when aqueous solutions of Na2SO4 and Pb(NO3)2 are
mixed. Calculate the mass of PbSO4 formed when 1.25 dm3 of 0.05 M Pb(NO3)2
and 2 dm3 of 0.025 M Na2SO4 are mixed.

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5
Chemistry-XI

STATES AND PHASES

OF MATTER
STUDENT LEARNING OUTCOMES [C-11-A-79 to C-11-A-92]

Describe the physical properties of gases (including compressibility, expandability, and

pressure exerted by gases). (Understanding)
Origin of pressure in terms of collisions between molecules and the walls of container,
Understand that ideal gas have zero partial volume, State and use the ideal gas equation
PV=nRT in Calculations including determination of Mr. (Understanding)
Describe simple properties of liquids e.g., diffusion, compression, expansion, motion of
molecules, spaces between them, intermolecular forces and kinetic energy based on kinetic
molecular theory. (Understanding)
Describe types of intermolecular forces. (Understanding)
Explain the strength and applications of dipole-dipole forces, hydrogen bonding and
London forces. (Understanding)
Describe physical properties of liquids such as evaporation, vapor pressure, boiling point,
viscosity and surface tension. (Understanding)
Apply the concept of hydrogen bonding to explain the properties of water (specifically
high surface tension, high specific heat, low vapor pressure, high heat of vaporization, and
high boiling point). (Application)
Define molar heat of fusion and molar heat of vaporization. (Knowledge)
Describe how heat of fusion and heat of vaporization affect the particles that make up
matter. (Understanding)
Outline the importance of heat of fusion in the study of glaciers and ice sheets (particularly
while studying polar ice caps). (Understanding)
Describe liquid crystals and give their uses in daily life. (Understanding)
Differentiate liquid crystals from pure liquids and crystalline solids. (Understanding)
Describe simple properties of solids e.g., compression, expansion, motion of molecules
inter-particle space, intermolecular forces and kinetic energy based on kinetic molecular
theory. (Understanding)
Differentiate between amorphous and crystalline solids. (Knowledge)
Describe properties of crystalline solids like geometrical shape, melting point, habit of a
crystal, cleavage, and crystal growth. (Understanding)

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Matter exists in four states i.e., solid, liquid, gas and plasma. The simplest form of matter
is the gaseous state and most of matter around us is in the solid state. Liquids are less
common than solids, gases and plasmas. The reason is that the liquid state of any substance
can exist only within a relatively narrow range of temperature and pressure.
Let us look at the general properties of gases, liquids, and solids. Kinetic molecular theory
of gases can help us to understand their properties.

5.1 PROPERTIES OF GASES

i. Gases do not have a definite shape and volume. The volume of a gas is the volume of
the container.
ii. Ideal gases have zero particle volume.
iii. The molecules of gases are widely separated from one another and most of the volume
of the gas is empty space (nearly 99.9%). That is why gases can be compressed
easily. When sudden expansion of gases occurs cooling takes place. It is called Joule-
Thomson effect.
iv. Pressure of a gas is due to the collisions of gas molecules with the walls of the container.
v. There are negligible intermolecular forces in ideal gases.

5.2 IDEAL GAS EQUATION

It is a matter of common observation that when external conditions of temperature and
pressure are changed, the volume of a given quantity of a gas is affected. The gas laws
describe the relationships between volume of a given amount of gas and the prevailing
conditions of temperature and pressure.
While describing Boyle’s and Charles’ laws, some of the variables are held constant during
the changes produced in the gases. According to Boyle’s law.
1
V ∝ (when ‘n’ and ‘T’ are held constant) …… (1)
P
According to Charles’ law
V∝T (when ‘n’ and ‘P’ are held constant)…....… (2)
According to Avogadro’s law volume of the given gas at constant temperature and pressure
is directly proportional to the number of moles.
V∝n (when P and T are held constant) …… (3)
If we think for a moment that none of the variables are to be kept constant, then all the
above three relationships can be joined together as:
nT
V∝
P
nT
V = constant
P

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The constant suggested is ‘R’ which is called Ideal gas constant. Its value is 0.0821 atm dm3
K-1 mol-1.
nT
Hence V = R
P
PV = nRT ……… (4)
The equation (4) is called the ideal gas equation.
Calculation of Relative Molecular Mass (Mr ) of a Gas
Equation (4) can be employed to calculate the relative molecular mass of a gas whose P, T,
V and mass in grams are known. This is achieved by rearranging equation (4)
Putting n = m/M in equation (4)
Where m= mass in g and M = molar mass of the gas
PV = mRT …….. (5)
M
Now rearranging equation (5)
M = mRT …… (6)
PV
At molecular level, the molar mass becomes relative molecular mass of a compound,
therefore, we can write
mRT
Mr = PV ......... (7)
Sample Problem 5.1
The volume of 134 g of a gas at -73 ℃ under 10 atm pressure is 5 dm3. Determine the
relative molecular mass of the gas.
Solution: The molecular mass of the gas can be calculated by using the formula:
mRT
M=
PV
(134 g)(0.0821 atm dm3 mol-1 K-1)(200 K)
M=
(10 atm)(5 dm3)
M = 44 g mol-1
Therefore, the relative molecular mass of the gas is 44 amu.

Quick Check 5.1

a) Explain why gases can be compressed easily?
b) What is Joule-Thomson effect
c) The volume of 21g a gas is 8 dm3 at -90 ºC under 7 atm pressure. Calculate the relative
molecular mass of the gas.

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5.3 PROPERTIES OF LIQUIDS

i. Liquids also diffuse like gases, however the rate of diffusion in liquids is much lower
than that in gases.
ii. There are little spaces among liquid molecules because of relatively stronger
intermolecular forces.
iii. Liquids are 105 times less 1 atm
compressible than gases,
but about 10 times more 2 atm 1 atm 2 atm
compressible than solids.
iv. The molecules of a liquid are
in constant random motion,
but their speed of movement
is lower than gases. Diffusion Air Air Water Water
(Gas) (Gas)
among the miscible liquids is
an evidence for the free motion (a) (a) (b) (b)
of liquid molecules. Similarly, (a) Volume of gas is (b) Volume of a liquid
liquids can flow because of reduced to half when changes by about 0.0045%
the free movement of their pressure is doubled when pressure is doubled.
molecules. Figure 5.1 Effect of pressure on the volumes of gases and liquids.
v. Liquids expands when their
temperature is increased. However, this expansion is negligible compare to that in
gases .
vi. According to kinetic molecular theory, molecules of a liquid are in constant motion,
therefore they possess a certain amount of kinetic energy at any temperature. The KE of
the molecules may increase or decrease by the rise or fall in temperature respectively.
For example, a liquid is converted into a solid by decreasing its kinetic energy (on
cooling) and converted into vapour by increasing kinetic energy (on heating)

5.4 INTERMOLECULAR FORCES

The intermolecular forces among the molecules of a liquid are reasonably stronger. Three
types of such forces are mentioned here.
i. Instantaneous dipole-induced dipole forces (id-id) (London dispersion forces)
ii. Permanent dipole- permanent dipole forces
iii. Hydrogen bonding
5.4.1 Instantaneous dipole-induced dipole forces (id-id)
The momentary force of attraction between an instantaneous dipole and an induced dipole
is called instantaneous dipole-induced dipole force.
These are only forces that exist among the molecules of non-polar compounds. The strength
of these forces depend upon the following factors
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i. Molecular mass and size:

When the molecular mass (Mr) of a compound is greater, the id-id forces are stronger
and vice versa. This is because in a larger atom or molecule the dispersion of electronic
cloud and polarisation is relatively easier. This factor operates in the halogen and noble
gas families. The physical state changes in the halogen family from top to bottom due to
the increase in size and polarizability. The first two members in the halogen family (F2 and
Cl2) are gases, but bromine is a liquid and iodine a solid (b.p. = 458 K). The boiling points
of noble gases in group 18 also increase from helium (He) to xenon (Xe) as in Table 5.1.
Table 5.1 Molar masses and boiling points of group 17 and 18 of periodic table.

17 Molecular Boiling points 18 Molecular Boiling points

(VII-A) Mass (K) VIII mass (K)
F2 38 85 He 4.003 4.22
Cl2 71 239 Ne 20.18 27.1
Br2 159 333 Ar 39.95 87.3
I2 253.8 458 Kr 83.8 120
Xe 131.3 165
ii. Surface area (shape of molecule)
A molecule with larger surface area has more number of contacts for a nearby molecule.
Thus the forces among the molecules of a compound having larger surface area are stronger.
Consider saturated hydrocarbons. These have chains of carbon atoms linked with hydrogen
atoms. Compare the length of the chains in C2H6 and C6H14. They have the boiling points
−88.6°C and 68.7°C, respectively. It is evident that the molecules with larger chain length
experiences stronger attractive forces. The reason is that longer molecules have more
places along the length where they can be attracted to other molecules. Boiling points of
some hydrocarbons are given in Table 5.2.
Table 5.2 Boiling points and physical states of some hydrocarbons

Physical
B.P. oC B.P. oC Physical state
Name state at Name
(1 atm) (1 atm) at S.T.P
S.T.P.
Methane (CH4) -164 Gas Pentane (C5H12) 36.1 Liquid
Ethane (C2H6) -88.6 Gas Hexane (C6H14) 68.7 Liquid
Propane (C3H8) -42.1 Gas Decane (C10H22) 174.1 Liquid
Butane (C4H10) -0.5 Gas Isodecane 327 Solid
(C20H42)
Three isomers of pentane have the same relative molecular mass (Mr), however, they differ
in their surface areas. Straight chain pentane has largest surface area and so is its boiling
point among the three isomers of pentane. 2-Methylbutane (Isopentane) has smaller
surface area than n-pentane but larger than 2,2-Dimethylpropane (Neopentane). Therefore,
the forces among 2-Methylbutane molecules are intermediate and the least strong forces

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occur in 2,2-Dimethylpropane. The isomers of pentane alone with their boiling points are
given in Figure 5.2.
CH3 CH3
H2 H2
C C CH3
H 3C C CH3 H 3C C H 3C CH3
H2 H2 H 3C

pentane 2-Methylbutane 2,2-Dimethylpropane

(n-pentane) (iso-pentane) (neo-pentane)
36.2 °C 28 °C 9.5 °C

Figure 5.2 The three isomers of pentane have different structures, surface areas and intermolecular forces

Quick Check 5.2

a) To improve the quality of gasoline(petrol), straight chain hydrocarbons in the gasoline
fraction of petroleum are converted to branched chain ones? What could be the possible
reason?
b) Which forces are present among the molecules of the following substances? CCl4, SiF4
c) Differentiate id-id and pd-pd forces with examples.

5.4.2 Permanent dipole-permanent dipole forces (pd-pd)

The force of attraction between the positive
end of a polar molecule and the negative end of
a nearby polar molecule is called permanent
dipole-permanent dipole force. Whenever the
HCl molecules are close to each other (as in
liquid state), they tend to line up as in Figure
5.3. Similar type of forces is present among the
molecules of chloroform (CHCl3).
The molecule of chloroform has a positive center
at the H atom and the negative center on the end
with Cl atoms. Figure 5.3 Permanent dipole-permanent

5.4.3 Hydrogen Bonding dipole forces in HCl and chloroform

Hydrogen bond is a special type of dipole-dipole force. It is the strongest force among
intermolecular forces, but is weaker than all the major types of bond, i.e. ionic, metallic,
and covalent bonds. A hydrogen bond is formed when the following conditions are fulfilled:
i. The hydrogen atom is connected to a highly electronegative atom, such as F, O, or N
ii. The electronegative atom must have a lone pair of electrons on it.
The covalent bond between a highly electronegative atom and hydrogen is highly polarized.
It means the hydrogen atom carries a sufficient δ+ charge and the electronegative atom

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δ- charge. The presence of lone pair on the electronegative allows the partial positively
charged hydrogen atom to make a bond with F, O, or N called a hydrogen bond. This bond
is represented by a dotted line (…) and its strength is one tenth of an ordinary covalent
bond. The number of hydrogen bonds a molecule can form on average depends on:
The number hydrogen atoms bonded to the electronegative atom
The number of lone pairs present on F, O, or N
A water molecule contains two hydrogen atoms and two lone pairs on oxygen. Therefore,
it can form two bonds on average. This is why
water molecules are extensively hydrogen – –

bonded with one another. This unique feature +

O +
O +
+
of water is responsible for its characteristic H H H H
properties, e.g. high boiling point of water (100
℃). The water molecules in liquid form are
O – +
arranged three dimensionally as shown in Fig. +

42. This bonding acts as a bridge between two

+
H H +
H
–
H
–

electronegative oxygen atoms. O O

+
On the other hand, ammonia can form only one H H
+

hydrogen bond per molecule despite having three

hydrogen atoms. This is due to the availability of Figure 5.4 Hydrogen bonding in water
only one lone pair on the N atom as shown in
Figure 5.4. The hydrogen bonding in liquid
ammonia is much weaker than water. This is why its boiling point is much lower (-33℃).
HF is even more distinct than water and ammonia. It has three lone pairs on the F atom
which allows it to form three H-bonds. However, it has only one H atom and due to this
reason, it is restricted to form only one bond again. Nevertheless, its hydrogen bond is
strong enough compared to NH3, which owes to its high electronegativity. Thus, its b.p
(19.9℃) is much higher than ammonia (–33.5℃).
+
The molecules of HF join with one H +
other in a zig-zag manner in solid form +
F
due to the presence of the hydrogen H +

+ F
bonds. The exceptional low acidic H
strength of HF molecule as compared
to HCl, HBr and HI is attributed
to this strong hydrogen bonding,
because the partial positively charged
hydrogen is entrapped between two
highly electronegative atoms (Figure
5.5). Figure 5.5: Hydrogen bonding in NH3 and HF

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5.4.4 Influence of Hydrogen Bonding on the Properties of Water

i. Structure and low density of ice
The molecules of water have tetrahedral structure. Two lone pairs of electrons on oxygen
atom occupy two corners of the tetrahedron. When the temperature of water is decreased
and ice is formed, the molecules become more regular and this regularity extends
throughout the whole structure. Empty spaces are created in the extensively hydrogen-
bonded structure as shown in the following diagram (Figure 5.6). This is why, when water
freezes, it occupies 9% more space and its density decreases. For this reason, ice floats on
water. Due to this so called anomalous behavior of ice, the fish and other living creatures
survive under the frozen lakes and oceans. The ice blanket covers the water surface due to
its low density and the water beneath is insulated from the environment.

Figure 5.6: Extensive hydrogen bonding This part of a glacier is floating on the
in ice and spaces among molecules surface due to low density of ice
ii. High Heat Capacity
Water has a high specific heat capacity. This is due to its unique molecular structure which
allows strong hydrogen bonds.
iii. Anomalous heat of vaporization and boiling point
The general trend of enthalpy change of vaporization of group 16 hydrides is a regular
increase from H2S to H2Po (Figure 5.7). This is because the molecules of these compounds
are bound by weak London dispersion forces.

Figure 5.7: A graphical expression of variation in enthalpy of vaporization and B.Ps of group 16 hydrides

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With the increasing atomic size down the group, from S to Po, the van der Waals forces
also become stronger. If water had followed this trend, the heat of vaporization of water
would be the lowest among the group members. However, water has the highest enthalpy
change of vaporization (41 kJ mol-) in the group. This is because water is exceptionally
hydrogen bonded, which makes it difficult to break forces among water molecules and
vaporize it. The boiling point of water is also remarkably higher than the rest of group 16
hydrides. Simply, the energy required to break the water molecules apart is very high due
to extensive hydrogen bonding in it. It needs high temperatures to provide so much energy
as to boil water into its vapor.
iv. Surface tension and viscosity
The surface tension and viscosity of water are also very high. Surface tension is a downward
pull of water molecules at the surface, making the water surface stretched and strained.
This downward pull is due to the attraction of inner molecules through hydrogen bonds.
Viscosity is the resistance by a liquid to its flow. Water has higher viscosity than many
of liquids including lower hydrocarbons and alcohols (e.g. hexane and ethanol. The high
viscosity of water is also due strong hydrogen bonds among the molecules. Alcohols can
make hydrogen bonds, but the strength and extent of hydrogen bonding is far less than that
in water. Hydrocarbons lack the ability to make the hydrogen bond.
Quick Check 5.4
a) Can the CHF3 molecule make a hydrogen bond? Explain why or why not?
b) Show a hydrogen bond between two molecules of ethanol
c) Describe which forces are present in the following and arrange them in increasing order of
boiling point.
i. CH3CH2CH3 ii. CH3CH2OH iii. CH3CH2Cl
d) The boiling point difference in each of the following pairs is given
i. CH3CH3 (-89 ℃) and CH3OH (65 ℃), difference = 154 ℃
ii. CH3CH2CH2CH4 (0 ℃) and CH3CH2CH2OH (97 ℃), difference = 97 ℃
e) Explain why the difference decreases as the size of the molecules increases.
f) Molecules of ethanoic acid (acetic acid) exist in the form of dimers in pure form but not in
aqueous solution. How hydrogen bond can explain this?

5.5 SURFACE TENSION

OF LIQUIDS
Surface tension is a property of liquids that
describes the force acting along the surface of a
liquid, causing it to behave like an elastic sheet.
This force arises due to the intermolecular forces
between the molecules at the surface.
Mosquitos can float on surface on water
due to high surface tension
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Molecules at the surface experience a net force inward due to intermolecular forces, leading
to a "skin" on the surface. Liquids tend to minimize their surface area due to surface
tension, which explains why droplets form spheres. Surface tension influences various
phenomena, such as, capillary action, wetting of surfaces and formation of droplets and
bubbles.
Factors Affecting Surface Tension
i) Temperature: Surface tension typically decreases with increasing temperature.
ii) Intermolecular forces: Stronger intermolecular forces lead to higher surface tension.
Table 5.3 Surface tension of some liquids at 20 °C in Nm–1

γ (10–3 Sr.
Sr. No. Liquid Liquid γ (10–3 Nm–1)
Nm–1) No.
Acetone
1 Water H2O 72.75 4 23.70
(CH3)2CO
Ethyl alcohol
2 22.75 5 Benzene C6H6 28.85
CH3CH2OH
Carbon
Methyl alcohol
3 22.61 6 tetrachloride 26.95
CH3OH
CCl4
‘γ’ are values multiple of 10−3 = 1/1000. It means ‘γ’ value of the water (H2O) at 20oC =
72.75 × 10−3 Nm−1 or 72.75 dynes cm−1.

5.6 VISCOSITY OF LIQUIDS

In order to understand the term viscosity, let us take water in a beaker. It is stirred with a
glass rod, and left undisturbed for some time. Its swirling motion subsides after a while.
Now, observe this process carefully, you will see that the liquid layer adjacent to the walls
of the beaker comes to rest first and layer near the centre stops last. It can be concluded that
stationary layer of walls of beaker slows down the motion of layer touching it immediately.
This slowed layer in touch with container also slows the next inner layer, but to less extent.
This means that a slow moving layer of a liquid tends to slow down the fast moving layer
adjacent to it. This is a frictional force operating between adjacent layers. This resistance
to the flow of a liquid is termed as viscosity.
In international system (SI), unit of viscosity is in kg m−1 s−1. In CGS system, the unit of
viscosity is poise (P).
5.6.1 Factors affecting viscosity:
The factors affecting viscosity are as follows:
i. An increase of temperature increases the average kinetic energy of molecules. This
allows the molecules to overcome the attractive forces. This lowers the viscosity.
ii. The stronger the intermolecular forces, the greater the viscosity of liquids because
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liquid molecules cannot move around each other freely, so the resistance to flow
increases.

Quick Check 5.5

a) Arrange the following liquids is increasing order of surface tension, give reason:
Acetone (CH3COCH3), ethanol (C2H5OH), methoxy methane (dimethyl ether, CH3OCH3)
b) Why do you think tetracholro methane (carbon tetrachloride, CCl4) has higher viscosity
than chlroform (CHCl3) but less than ethanol (C2H5OH)?
c) Drugs with higher viscosity are not oxidized easily, justify.
d) The viscosity of honey is higher than water, explain why.
e) Which of the following is more viscous: glycerine (CH2OHCH2OHCH2OH) or hexane
(C6H6)? Why?

5.7 EVAPORATION
Evaporation is the spontaneous conversion of a liquid into vapour at any temperature.
When high energy molecules leave the liquid and low energy molecules are left behind,
the temperature of the liquid falls. The heat moves from the surrounding to the liquid and
then the temperature of the surrounding also falls. This phenomenon helps to understand
that evaporation causes cooling.
A person after bath feels a sense of cooling due to evaporation of water from his body
when exposed to air. The molecules of H2O take away the energy of body. Earthenware
vessels keep water cooler under the same phenomenon. Earthenware vessels are porous.
The water molecules having sufficient K.E to overcome inter molecular forces come
out of these pores and evaporate. This process of evaporation keeps on taking place and
energy required for this process comes from the liquid. Thus, the average K.E of remaining
water molecules decreases which results in decrease in temperature of the liquid. Hens,
earthenware vessels keep water cool.

5.8 VAPOUR PRESSURE:

The molecules of a liquid which leave the open surface are mixed up with air above the
liquid. If the vessel is open these molecules go on leaving the surface of liquid. But if we
close the system the molecules of liquid start gathering above the surface. These molecules
collide with the walls of the container, and also with the surface of the liquid as well. There
are chances that these molecules are recaptured by the surface of liquid. This process is
called condensation. The two processes, i.e., evaporation and condensation continue till a
stage reaches when the rate of evaporation becomes equal to the rate of condensation Fig
(5.11).

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The pressure exerted by the liquid vapour in equilibrium with its liquid at a given
temperature is called vapour pressure.
evaporation
Liquid Vapour
condensation
The magnitude of vapour pressure does not depend upon the amount of liquid in the
container or the volume of container. It does not depend on surface area of a liquid. The
larger surface area presents a larger target for returning the molecules, so the rate of
condensation also increases.

Vacuum Vapour Vapour

(a) (b) (c)

Figure. 5.8 Attainment of equilibrium when the evaporation of liquid is carried out in an evacuated closed vessel.
(a) Initial state, with evacuated space above the liquid, (b) intermediate state, and (c) equilibrium state, when the
rate of evaporation is equal to the rate of condensation.

Quick Check 5.6

a) Which of the liquids in each of the following pairs has a higher vapour pressure?
i) Alcohol, glycerine ii) Petrol, kerosene, iii) Mercury, water?
b) Which one in each of the following pairs is more viscous: Glycerine, kerosene?
c) Separate portions of acetone and water at the same temperature are poured on your hands.
The acetone feels colder. Account for this in terms of attractive forces.
d) Why evaporation gets faster at higher temperatures?

5.9 BOILING POINT Normal boiling points

34.6 C
0
78.30C 1000C
When a liquid is heated, its vapour pressure 800
goes on increasing. A stage reaches when 760

the vapour pressure of the liquid becomes 600

Diethyl
Ethyl alcohol Water
ether
Vapour pressure

equal to the atmospheric or external (ethanol)

400
pressure. At this temperature the liquid
starts boiling. The reason for this is that the 200
bubbles of vapour which are formed in the Ethylene
glycol
interior of the liquid have greater internal
pressure than atmospheric pressure on the 0 20 40 60 80 100
Temperature
surface of liquid. This makes the bubbles to Figure 5.9 Vapour pressures (torr) of four common
liquids shown as a function of temperature.
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come out of the liquid and burst at the surface. A constant stream of bubbles comes out at
the boiling point of the liquid.
When a liquid is heated, the kinetic energy of its molecules increases. This causes the
increase of the temperature. At the boiling point, the kinetic energy of the molecules
becomes maximum. Any further heating at this stage will not increase the temperature.
This further heating is utilized to break the intermolecular forces and convert the liquid
into its vapour. The boiling points of some commonly available liquids at one atmospheric
pressure are shown in the Table (5.9).
The Figure 5.9 shows the variation of vapour pressure of water, ethyl alcohol, ethylene
glycol and diethyl ether with temperature. The graphs show that the liquids reach upto
their boiling points when their vapour pressures are equal to 760 torr at sea level.
5.9.1 Factors affecting boiling points of liquids
The boiling point of a liquid is affected by the factors given below.
1) Strength of intermolecular forces
Stronger the intermolecular forces, lower will be the vapour pressure and higher will be the
boiling point. Higher boiling point of H2O indicates stronger intermolecular forces than
that of ethanol and methanol, Table 5.4.
Table 5.4 Boiling points of some common liquids at 760 torr (1 atm.)

Liquids Formula B.P (°C) Liquids Formula B.P (°C)

Acetic acid CH3COOH 118.50 Carbon tetrachloride CCl4 76.50
Acetone CH3COCH3 56.00 Ethanol C2H5OH 78.30
Benzene C6H6 80.15 Naphthalene C10H8 218.00
Carbon CS2 46.30 Water H2O 100.00
disulphide
2) External pressure
As already explained that when vapour pressure of a liquid becomes equal to the external
pressure then the liquid boils. It means that when external pressure is changed, its boiling
point will also change. When the external pressure is high the liquid requires greater
amount of heat to equalize its vapour pressure to external pressure. In this way boiling
point is raised. Similarly, at a lower external pressure a liquid absorbs less amount of heat
and it boils at a lower temperature.
For example, water shows B.P of 120°C at 1489 torr pressure and boils at 25°C at 23.7 torr.
Water boils at 98°C at Murree hills due to external pressure of 700 torr while at the top of
Mount Everest water boils at only 69oC at 323 torr.
We can increase the external pressure artificially on the surface of boiling water by using a
pressure cooker. Pressure cooker is a closed container. The vapour of water formed is not
allowed to escape. In this way, it exerts they develop more pressure on the water surface
in the cooker and the boiling temperature increases. As more heat is absorbed in water, so
food is cooked quickly under increased pressure.
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Quick Check 5.7

a) Why food cooking is difficult in the areas with high altitudes?
b) The food cooks fatser in the pressure cooker, explain.
c) Why the boiling point of water (100 ℃) is higher than that of ethanol (78 ℃), although oth
have hydrogen bonds?

5.10 ENERGETIC OF PHASE CHANGES

Whenever, matter undergoes a physical change, it is always accompanied by an energy
change. This change in energy is the quantitative measurement of the difference in the
strength of intermolecular forces.
Molar heat of fusion (∆Hf)
The amount of heat absorbed by one mole of a solid to melt it into the liquid at its melting
point at 1 atmospheric pressure is called molar heat of fusion.

H2O(s) H2O(l) ∆Hf = 4.6 kJ mol–1

Molar heat of vaporization (∆Hv)
The amount of heat absorbed by one mole of a liquid to convert it into one mole of vapour
at its boiling point at 1 atmospheric pressure is called molar heat of vapourization.
The molar heats of vaportization depends upon the strength of intermolecular forces. When
one mole H2O is converted to vapour at 100oC, then heat absorbed is 40.6 kJ mol–1.

H2O(l) H2O(g) ∆Hv = 40.6 kJ mol–1

NH3 and HCl only need 21.7 and 15.6 kJ mol−1 respectively to become vapour at their
boiling points. This difference is due to the stronger intermolecular forces in water.
Effect of Molar heat of vaporization and fusion on matter particles
The molar heat of fusion and vaporization affect the particles that make up matter
by providing them with enough energy. Due to this, the particle move away from one
another and change the state of the substances from solids to liquids and liquids to gases
respectively. Particles gain more freedom to move and rotate in the liquid and gas phase.

SOLIDS
Solids are those substances which are rigid, hard, have definite shape and definite
volume. The atoms, ions and molecules that make up a solid are closely packed. They are
held together by strong cohesive forces. The constituent atoms, ions or molecules of solids
cannot move at random.

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5.11 General properties of solids

i) Compression of solids
The atoms, molecules or ions of a solid substance are closely packed. The particles of
solids cannot move closer to each other unlike gases. It is true for metallic solids that their
atoms are spherically symmetrical. So, when such particles are arranged, they can give
birth to hexagonal and cubic close-packed structures. Here outer boundaries of constituent
particles touch each other but due to their spherical shapes, they cannot occupy more than
74% space. It means the compression of solids is not possible.

ii) Expansion of solids

The expansion is the property in which spaces between constituent particles are increased.
In case of solids the forces of attractions are so strong that increase of temperature hardly
affects their relative positions. The particles in a solid have vibrational motions about their
mean positions. Increase in temperature of solids hardly increases their volume. No doubt,
there are parameters like coefficient of linear and cubic expansions of various solids, but
these are negligible as compared to liquids and gases.

iii) Motion of particles in solids

The constituent particles of a solid do not undergo translatory motion, and neither rotational
ones. They only vibrate about their mean positions. These vibrations become more intense
at higher temperature.
iv) Inter-particle space in solids
The interpaticle spaces in solids are far less than liquids. This is due to the stronger forces
among their particles. Due to closely packed atoms, molecules, and ions, solids are mostly
hard, have high melting points and high stability.

v) Inter-particle forces in solids

In solids, the particles (atoms, ions, molecules) are held together by ionic, covalent,
metallic or van der Waals forces. These forces are strong enough to fix the particles at their
places thus allowing these particles to just vibrate about their mean positions.

vi) Kinetic energy based on KMT

Kinetic energy is due to the motion of constituent particles of a solid. Solid particles have
only vibratory motion and they do not have translational or rotational motion. Therefore,
the only kinetic energy that solids possess is vibrational kinetic energy.

5.12 TYPES OF SOLIDS

There are two types of solids on the basis of the way their particles are arranged;
i. Crystalline solids
ii. amorphous solids.

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5.12.1 Crystalline Solids

Crystal Lattice
The regular arrangement of ions, atoms, or molecules in three dimensional space is called
the crystall lattice.
The solids which have definite regular and three dimensional geometric shapes are called
crystalline solids. For example, diamond, sodium chloride, ice, etc.

Properties of crystalline solids

i. Geometrical shape
All the crystalline solids have a definite, distinctive geometrical shape due to definite and
orderly arrangement of atoms, ions or molecules in three-dimensional space. For a given
crystal, the interfacial angles, at which the surfaces intersect, are always the same no
matter in which shape they are grown. The faces and angles remain characteristic even
when the material is ground to a fine powder.
ii. Melting points
Crystalline solids have sharp melting points. They can be identified from their definite
melting points.
iii. Cleavage planes
Whenever the crystalline solids are broken they do so along definite planes. These planes
are called the cleavage planes and they are inclined to one another at a particular angle
for a given crystalline solid. The value of this angle varies from one solid to another solid.

iv. Growing of a crystal

When we have a saturated or super saturated solution of a crystalline material in a suitable
solvent, it can give us same types of crystals by arranging atoms, ions or molecules.
This happens through the process called growth of crystals. This can be done by slow
evaporation of the solvent or by seeding process from saturated solution.
For example, the solubility of sodium thiosulphate (Na2S2O3) in water at 100oC is 231g/100
cm3. At room temperature solubility is 50 g / 100 cm3. In case, we have saturated solution
of Na2S2O3 at 100oC, on cooling slowly no growth of crystal happens. It means that super
saturated solution is not in equilibrium with solid substance. Now, if small crystal of
Na2S2O3 is added to super saturated solution, the crystallization happens rapidly.
v. Habit of a crystal
The shape of a crystal in which it usually grows is called habit of a crystal. If the conditions
for growing a crystal are maintained, then the shape of the crystal always remains the
same. If the conditions are changed the shape of the crystal may change. For example, a
cubic crystal of NaCl becomes needle like when 10% urea is present in its solution as an
impurity.
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5.12.2 Amorphous solids

Amorphous solids, contrary to the crystalline solids, do not possess regular three
dimensional geometrical shapes. The examples of amorphous solids are glass, wood,
amorphous sulphur (plastic sulphur), charcoal, coal, coke, etc.
Properties of amorphous solids:
i. The amorphous solids can have small regions where orderly arrangement of particles
is found, but they do not have long range of regularity. The regions where orderly
arrangement of particles is present are known as crystallites.
ii. Amorphous solids like glass melts over a wide temperature range.
iii. They can be molded and blown to form different shapes.
iv. Amorphous solids do not have definite value of heat of fusion.
Table 5.5 Comparison of crystalline and amorphous solids.

Property Crystalline solids Amorphous solids

1. Geometry of Crystalline solids show Amorphous solids generally appear
solid characteristic geometrical in lump or in a fine powder form.
shapes.
2. Melting of Crystalline solids melt Amorphous solids do not have sharp
solid sharply at their melting melting points and they melt over a
points. range of temperature.
3. Directional Crystalline solids are Amorphous solids are isotropic.
character of the anisotropic in nature. It means Their properties do not depend upon
properties that their properties depend the direction of measurement.
upon the direction along
which the measurements are
made.
4. Order of Crystalline solids have long- In amorphous solids, long-range
particles in solid range order. order is absent.
Quick Check 5.8
a) Why solids have very low compressibility and expansion?
b) What is meant by habit of a crystal.
c) Why solids do not undergo translatory motion?
d) Why most of solids can not be compressed easily?

5.13 LIQUID CRYSTALS

We know that the distinction between liquids and solids is clear-cut. Moreover, the phase
transition between them is always sharply defined. However, at certain temperature, many
substances exist in a phase that is neither fully liquid nor fully solid. The molecules in
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these substances can move around, as in viscous liquids, but have a restricted range of
motion, as in solids. These substances are called liquid crystals.

Crystalline solid → Cloudy liquid (liquid crystal) → Clear liquid
In most liquid crystals, the molecules have a rigid, rod-like shape with a length four to
eight times greater than their diameter. When packed together, the molecules tend to orient
with their long axes roughly parallel, like logs in a stack of firewood. Individual molecules
can migrate through the fluid. They can spin around their long axis, but they can’t rotate
end over end.
5.13.1 General properties of liquid crystals:
The general properties of liquid crystals are as follows:

Liquid crystals
i. have parallel ordered arrangement.
ii. are elongated, rod-like and linear.
iii. flow like liquids
iv. show viscosity like liquids.
v. show optical properties like crystals.
vi. are somewhat rigid.
vii. are always anisotropic.

5.13.2 Uses of liquid crystals in daily life

The main application area of liquid crystals is in electro-optic devices. These are
electrically controlled devices that modulate light in a desired way. Liquid crystals have
many uses in daily life.

i) In diagnostics
Special liquid crystal devices can be used to diagnose the tumors and infections in the
human body. This is because often physical problems, such as tumors, have a different
temperature than the surrounding tissue. When cholesteric liquid crystals are applied to the
breast, a tumor is located because of being warmer than the other parts. This technique is
successfully applied to diagnose breast cancer in the early stage.

ii) Characteristic higher temperature determination

Liquid crystal temperature sensors can also be used to find faulty connections on a circuit
board by detecting the characteristic higher temperature. As temperature sensors, they are
be used in thermometers.

iii) Liquid crystal displays (LCDs)

The most common application of liquid crystal technology is liquid crystal displays (LCDs.).

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Examples of liquid crystal screens are oscillograph and TV, laptops, cell phone displays.
Liquid crystals are used in TV displays, computer screens, calculators and watches, etc.
As new properties and types of liquid crystals are investigated and researched, these
materials are sure to gain increasing importance in industrial and scientific applications.

Quick Check 5.9

a) Name the properties of liquid crystals in which they resemble solids.
b) Mention the properties of liquid crystals in which they resemble liquids.
c) Which property of liquid crystals make it possible to use them in temperature sensing
devices?

EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. London dispersion forces are the only forces present among:
a) molecules of water in liquid state
b) atoms of helium in gaseous state at high temperature
c) molecules of solid iodine
d) molecules of hydrogen chloride gas
II. When the vapour pressure of a liquid equals the external pressure, what
phenomenon occurs?
a) Sublimation b) Condensation
c) Boiling d) Freezing
o
III. When water freezes at 0 C, its density decreases due to:
a) cubic structure of ice
b) empty spaces present in the structure of ice
c) decrease in volume
d) decrease in viscosity
IV. Which of the following options is wrong about hydrides of groups 14, 15, 16, and
17 elements?
a) All the hydrides show H-bonding.
b) Only H2O, NH3 and HF show H-bonding.
c) The molecules of CH4 are non-polar.
d) H2S is a gas at room temperature but H2O is liquid.
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V. Which of following is the correct sequence of increasing ∆Hv values of substances

mentioned?
a) H2O > NH3 > F2 b) F2 > NH3 > H2O
c) NH3 > H2O > F2 d) H2O > F2 > NH3
VI. Surface tension of a liquid is due to:
a) inward pull of surface molecules b) upward pull from the surface
c) collision of molecules d) repulsive forces
VII. Amorphous solids:
a) have sharp melting points
b) undergo clean cleavage when cut with knife
c) have perfect arrangement of atoms
d) do not have definite geometric shape
VIII. Which change of state involves overcoming only London dispersion forces?
a) Melting of ice (H₂O(s) → H₂O(l))
b) Boiling of ethanol (CH₃CH₂OH(l) → CH₃CH₂OH(g))
c) Sublimation of iodine (I₂(s) → I₂(g))
d) Dissolving sodium chloride in water
IX. In which of the following substances are London dispersion forces the only
significant intermolecular forces present?
a) Ammonia (NH₃) b) Water (H₂O)
c) Methane (CH₄) d) Hydrogen fluoride (HF)
X. Which of the following is a characteristic property of crystalline solids?
a) They have a range of melting points.
b) They are isotropic.
c) They have a definite and sharp melting point.
d) They lack a regular arrangement of particles.
XI. Which of the following liquids would you expect to have the highest viscosity at a
given temperature?
a) Water (H₂O) b) Ethanol (CH₃CH₂OH)
c) Diethyl ether (CH₃CH₂OCH₂CH₃) d) Glycerol (CH₂(OH)CH(OH)CH₂(OH))
XII. Which type of intermolecular force is present in all types of molecule regardless
of their polarity?
a) Dipole-dipole forces b) Hydrogen bonds
c) London dispersion forces d) Ion-dipole forces
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XIII. Liquid crystals exhibit properties:

a) Only like solids. b) Only like liquids.
c) Between solids and liquids. d) Unlike solids or liquids.

SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. Explain, at a molecular level, why evaporation leads to a cooling effect.
b. Explain why liquids with stronger intermolecular forces tend to have lower rates of
evaporation at a given temperature compared to liquids with weaker intermolecular
forces.
c. One feels sense of cooling under the fan after bath.
d. Dynamic equilibrium is established during evaporation of a liquid in a closed vessel at
constant temperature.
e. The boiling point of water is different at Lahore and Murree hills.
f. Discuss two significant consequences of the lower density of ice compared to liquid
water in natural environments.?
g. Why B.P of a liquid increases when the external pressure rises?
h. Mention four items in which liquid crystals are used.
i. How do you differentiate between crystalline solids and amorphous solids?
j. Propanone (CH3COCH3), propanol (CH3CH2CH2OH) and butane (CH3CH2CH2CH3)
have very similar relative molecular masses. List them in the expected order of
increasing boiling points. Explain your answer.
k. Discuss how hydrogen bonding is responsible for the relatively high surface tension
of water.
l. What type of intermolecular forces will dominate in the following liquids?
(i) NH3 (ii) Ar (iii) CH3COCH3 (iv) CH3OH
m. The boiling points and molar masses of hydrides of some first-row elements are
tabulated below:
Substance Boiling Point (K) Molar Mass (g
mol−1)
CH4 109 16
NH3 240 17
H2O 373 18
Suggest reasons for the difference in their boiling points in terms of the type of
molecules involved and the nature of the forces present between them.

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DESCRIPTIVE QUESTIONS
Q.3. What are London dispersion forces? Give examples, and discuss the factors
affecting these forces.
Q.4 Hydrogen bonding is present in H2O, NH3, HF, (CH3)2CO and CHCl3
molecules. Sketch structures and discuss briefly.
Q.5 Discuss the structural changes when water turns into ice. Justify the empty
spaces in its crystals as compared to H2O at 4oC and lower density of ice.
Q.6 How liquid crystals resemble liquids and solids? Give their uses in daily life.
Q.7 Describe the following properties of crystalline solids.
i) Geometrical shape ii) Melting point
iii) Cleavage plan iv) Habit of a crystal

NUMERICAL PROBLEMS
Q8. A sample of an unknown gas has a mass of 0.560 g. It occupies a volume of 2.87 ×
10⁻⁴ m³ at a temperature of 300 K and a pressure of 1.01 × 10⁵ Pa. Calculate the
molar mass of the gas. (Gas constant, R=8.31JK−1mol−1)
Q9. In a laboratory experiment, 150 cm³ of a volatile liquid was completely vaporized
at 98 °C and a pressure of 1.01 × 10⁵ Pa. The mass of the vapor was found to be
0.495 g. Determine the molecular mass of the liquid (R = 8.314 J K⁻¹ mol⁻¹).

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 CHEMICAL ENERGETICS

6
Chemistry-XI

CHEMICAL
ENERGETICS
STUDENT LEARNING OUTCOMES [C-11-A-93 to C-11-A-123]

Describe those chemical reactions are accompanied by enthalpy changes and these changes
can be exothermic (ΔΗ° is negative or endothermic ΔH° is positive). (Understanding)
Interpret a reaction pathway diagram, in terms of the reaction and of the activation energy.
(Understanding)
Define terms such as standard conditions, enthalpy change, reaction, formation, combustion
and neutralization. (Understanding)
Explain that energy transfer occurs during chemical reactions because of the breaking and
making of bonds. (Understanding)
Calculate the bond energies for the enthalpy change of reaction ΔΗ°. (Understanding)
Describe that some bond energies are exact and some bond energies are approximate.
(Understanding)
Calculate enthalpy changes from approximate experimental results, including the use of
the relationships q = mcdT and ΔH° = - mcdT/n. (Application)
Define terms such as enthalpy change of atomization, lattice energy, ΔΗ°, first electron
affinity, EA. (Knowledge)
Use terms such as enthalpy change of atomization, lattice energy, first electron affinity.
(Application)
Construct Born Haber’s Cycles for ionic solids. (Application)
Perform calculations involving Born- Haber cycles. (Understanding)
Explain the effect of ionic charge and ionic radius on the numerical magnitude of lattice
energy. (Understanding)
Apply enthalpy change with reference to hydration and solution. (Application)
Construct an energy cycle involving enthalpy change of solutions and enthalpy change of
hydration. (Application)
Perform calculations involving energy cycles. (Application)
Explain the effect of ionic charge and ionic radius on the numerical magnitude of an
enthalpy change of hydration. (Understanding)
Define the term entropy, S, as the number of possible arrangements of the particles and
their energy in a given system. (Understanding)
Explain the sign of entropy changes that occur during a change in state, temperature
change and a reaction in which there is a change in the number of gaseous molecules.
(Understanding)
Calculate the entropy change for a reaction, ΔS°, given the standard entropies, S, of the
reactants and the products. (Application)
Explain the concept of heat as a form of energy. (Understanding)
Explain the relationship between temperature and kinetic energy of particles.
(Understanding)
State that total energy is conserved in chemical reactions. (Understanding)
Explain the concept of standard conditions and standard states in measuring energy
changes. (Understanding)
Explain Hess’s Law. (Understanding)

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Apply Hess’s Law to calculate enthalpy changes in a reaction carried out in multiple steps.
(Application)
Explain the relationship between bond formation energy and bond breaking energy.
(Understanding)
Explain Gibbs free energy. (Understanding)
Apply the concept of Gibbs free energy to solve problems. (Application)
Outline how enthalpy change relates to the calorie concept of the food we eat. (Application)
Explain factors affecting the electron affinities of elements. (Understanding)

Thermochemistry is the study of the quantity of heat energy absorbed or evolved during
physical or chemical changes. That is why it is also called energetics and is largely based
on the first law of thermodynamics. Hess’ law, a special case of Ist law of thermodynamics,
is a remarkable tool in a chemist’s hand and finds numerous applications in analytical
chemistry. Moreover, thermodynamics allows us to predict whether a particular reaction
can occur under specified conditions i.e., it discusses the spontaneity of a reaction.

6.1 ENTHALPY CHANGE

The energy possessed by a substance due to its structure (types of bonds) and physical
state is called its heat content or enthalpy denoted by H. Every substance possesses a
characteristic amount of enthalpy. This is the reason that the total enthalpy of products (HP)
is never equal to that of reactants (HR). Hence during a chemical reaction, when reactants
are converted into products, there occurs a change in enthalpy denoted as ΔH. In other
words, enthalpy change is the net energy, which is either evolved or absorbed in the form
of heat.
Mathematically,
ΔH = (Heat content of products, HP) – (Heat content of reactants, HR)
There are two cases:
i. HP ˂ HR: such reactions involve a lowering of enthalpy and always take place with the
evolution of heat which is equal to HP – HR and ΔH carries negative sign.
“A chemical reaction or a physical change in which heat is evolved from the system to
surroundings is called exothermic process.”
ii. HP > HR: such reactions involve an increase in enthalpy and always take place by the
absorption of heat which is equal to HP – HR and ΔH carries positive sign.
“A chemical reaction or a physical change in which heat is absorbed by the system from
surroundings is known as endothermic process.”
Following Figure 6.1 shows the enthalpy diagram of exothermic and endothermic
reactions.

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reactants products
HR HP
HR Hp HR Hp
ΔH = negative ΔH = positive
Enthalpy Enthalpy

products reactants
HP HR

Progress of Reaction Progress of Reaction

(a) (b)

Figure 6.1: Enthalpy diagram of (a) Exothermic Reaction and (b) Endothermic Reaction
For example, combustion of carbon in oxygen is an exothermic reaction.
C(s) + O2(g) CO2(g) ΔH = ̶ 393.7 kJ mol-1
The dissolution of ammonium chloride (NH4Cl) in water is an endothermic process.
H2O()
NH4Cl(s) NH4+(aq) + Cl‒(aq) ΔH = +16.2 kJ mol-1

Interesting information
The dissolution of ammonium chloride (NH4Cl) in water
is an endothermic reaction. This reaction is used in cold
packs (or ice packs) to treat internal injuries. When the
pack is kneaded, water and NH4Cl crystals mix and energy
is absorbed from the surroundings, producing a cooling
sensation.

6.2 ENERGY PROFILE DIAGRAM:

All chemical reactions involve the breaking of bonds in the reactant molecules before the
formation of new bonds. This can be achieved only if the reactant molecules collide with
sufficient amount of energy to overcome an energy barrier. This minimum amount of energy
required by the
reactant molecules
just to cross that
Ea
energy barrier is HP products
HR Enthalpy
called energy of Enthalpy reactants
activation denoted ΔH Ea ΔH
by Ea. The energy
profile diagram HP
products
HR
reactants
of exothermic
and endothermic Progress of Reaction Progress of Reaction
reactions are given Figure 6.2 Energy profile diagram in terms of ΔH and Ea
in Figure 6.2.
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Quick Check 6.1

Draw the energy profile diagrams for the following reactions:
i. CH4(g) + 2 O2(g) CO2(g) + 2 H2O() ΔH = ̶ 890.3 kJ mol-1
ii. CaCO3(s) CaO(s) + CO2(g) ΔH = +572 kJ mol-1

6.3 STANDARD ENTHALPY CHANGES

The enthalpy of a substance not only depends upon its physical state but also on the pressure
and temperature. Hence, we must specify these conditions while writing an equation.
Therefore, when making accurate comparisons of enthalpy changes for various reactions,
ΔH is determined under certain standard conditions, which are summarized below:
a) Temperature: 25 °C or 298 K
b) Pressure: 1 atm or 101 kPa

Did you Know

The standard state of an element is its most stable form at 298 K and 1atm pressure.
For example, the standard state of C is graphite not diamond. By definition, the
standard enthalpy change of formation of any element in its standard state is zero.

6.3.1 Enthalpy Change of reaction (ΔHr)

The standard enthalpy of a reaction is the enthalpy change involved when stoichiometric
amounts of reactants in their standard states react together completely to form products
under standard conditions.
For example, consider the reaction between hydrogen and oxygen gases to form 1 mole
of water:
H2(g) + ½ O2(g) H2O() ΔHr = –286 kJ mol‒1

6.3.2 Enthalpy Change of Combustion (ΔHºC)

The standard enthalpy change of combustion of a substance is the enthalpy change involved
when one mole of the substance is completely burnt in excess of oxygen, under standard
conditions.
It is always exothermic. For example, standard enthalpy of combustion ΔHºC of ethanol is
̶ 1368 kJ mol‒1.
C2H5OH() + 3 O2(g) 2 CO2(g) + 3 H2O() ΔHºC = ̶ 1368 kJ mol‒1
Enthalpy change of combustion is useful in calculating calorie content of foods and fuels.

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6.3.3 Enthalpy Change of Formation (ΔHºf)

Standard enthalpy change of formation of a compound is the enthalpy change involved
when one mole of the compound is formed from its elements under standard conditions.
It can be exothermic or endothermic. For instance, ΔH°f for methane is given below.

C(s) + 2H2(g) CH4(g) ΔH°f = –74.8 kJ mol-1

6.3.4 Enthalpy Change of Atomization (ΔH°at)

“The standard enthalpy change of atomization of an element is the enthalpy change
involved when one mole of gaseous atoms is formed from the element, under standard
conditions.”
H2(g) 2H(g) EH-H = +436 kJ mol‒1
½ H2(g) H(g) ΔHºat = +218 kJ mol‒1

6.3.5 Enthalpy Change of Neutralization (ΔH°n)

The standard enthalpy change of neutralization is the enthalpy change involved when one
mole of water is formed by the reaction of an acid with an alkali under standard conditions.
It is always exothermic. For example, the enthalpy of neutralization of NaOH by HCl is
‒57.1 kJ mol‒1.
When these solutions are mixed together during the process of neutralization, the only
change that occurs is the formation of water molecules leaving Na+ and Cl‒ as free ions in
solution. Thus, the enthalpy of neutralization is merely the heat of formation of one mole
of liquid water from its ionic components and the actual neutralization reaction is:
H+(aq) + OH‒ (aq) H2O() ΔHºn = ‒57.1 kJ mol‒1
For all strong acid-base reactions ΔHºn is always near -57.1 kJ mol‒1.

6.3.6 Electron Affinity (ΔH°ea)

The first electron affinity is the enthalpy change involved when 1 mole of electrons is
added to 1 mole of gaseous atoms to form 1 mole of gaseous uni-negative ions under
standard conditions.
Electron affinity of chlorine atom.
Cl(g) + e− → Cl−
∆H = −348.8 kJ mol−1
Since, energy is released, so first electron affinity carries negative sign.
Note: A detailed discussion of electron affinity is given in chapter 1.

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Quick Check 6.2

a) Write equations, including state symbols, that represent the enthalpy change of atomization
of: (i) Oxygen (ii) Barium (iii) Bromine
b) Classify the enthalpy change in each of the following reactions:
i) C(graphite) + O2(g) CO2(g)
ii) HCl(g) + NH3(g) NH4Cl(s)
iii) H2(g) + ½ O2(g) H2O()
c) The first electron affinity of sulfur is ‒200 kJ mol-1 and the second electron affinity +640 kJ
mol -1. Calculate the value for the enthalpy change of the following reaction:
S(g) + 2e‒ → S2‒(g)

6.4 BOND ENERGY (BOND DISSOCIATION ENERGY)

AND ENTHALPY CHANGES
Chemical reactions involve the breaking and making of chemical bonds. When a bond is
formed between two atoms, energy is released. The same amount of energy is absorbed
when the bond is broken to form neutral atoms; we call this, bond dissociation energy
which is defined as, "The average amount of energy required to break (dissociate) one
mole of a particular bond in a substance.”
Table 6.1. Average Bond Energies of Some Important Bonds (kJ mol-1)
H‒ C– C= C≡ N‒ N= N≡ O– O= F‒ Cl‒ Br‒ I‒
H 436 413 391 463
C 413 348 615 812 292 615 891 351 728
N 391 292 615 891 161 418 945 222 607
O 463 351 728 222 607 139 498
S 339 259 477 347 327 251 213
F 563 441 270 185 159 255
Cl 432 328 200 203 243 218 209
Br 366 276 192 180
I 299 240 201 151

It may be denoted as E. If we are determining bond energy of a particular bond in a

particular substance, we call this exact bond energy.
This is to be noted that bonds between the same pair of atoms usually have different B.E.
values, in all of their compounds. Actually, B.E. is affected by other atoms in a molecule.
For example, C‒C bonds usually have B.E. values of approximately 350 to 380 kJ/mol.
In ethane: [H3C―CH3] ; EC-C = 376 kJ mol-1
In propane: [H3C―CH2―CH3] ; EC-C = 356 kJ mol-1

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In butane: [H3C―CH2―CH2―CH3] ; EC-C = 352 kJ mol-1

In these examples, Ec-c for ethane is exact bond energy. Similarly for propane and butane,
Ec-c are exact bond in the change. When we take average of all Ec-c in different molecules,
we obtain average C-C bond energy. Practically, average bond energy is used instead of
exact bond energies. Average bond energies of some bonds are given in Table 6.1.

6.5 ENTHALPY CHANGE OF REACTION (ΔHr) AND

CHEMICAL BONDS
A chemical reaction is defined as a process during which old bonds are broken and new
bonds are formed. Therefore, the enthalpy change (ΔHr) in a chemical reaction actually
comes from the breaking and forming of chemical bonds.
A chemical bond represents a form of energy known as chemical energy (which, like the
others, is interconvertible into all forms of energy). Bond breaking absorbs energy (ΔH
= +ve) while bond formation releases it (ΔH = ̶ ve) and their difference will decide the
overall sign of ΔH. That is whether a reaction is exothermic or endothermic is determined
by the net change.
Overall reaction is exothermic if the energy released in making of new bonds is greater
than that absorbed in bond breaking. The reverse is true for an endothermic reaction.
For example, in the formation of water, energy is needed to break the H―H bonds (of
hydrogen molecules) and the O=O bonds (of oxygen molecules) while energy is released
in the making of the H―O bonds (of water). However, the net reaction is exothermic
because more energy is released in forming the H―O bonds than is absorbed in breaking
the H―H and O=O bonds (Figure 6.5). Thus,
2 H2(g) + O2(g) → 2 H2O(g) ∆Hr = -ve

Sample Problem 6.1

With the help of the following bond energy data; calculate the enthalpy change of the
following reaction:
EH ̶ H = 436 kJ mol-1 ; EO=O = 495 kJ mol-1 and EH ̶ O = 463 kJ mol-1
H2(g) + ½ O2(g) H2O(g)
O
Solution: H ̶ H + ½ O=O
H H
436 + ½(495) 2 × (463)
(bond breaking energy) (bond forming energy)
⸪ ΔHºr = ∑ ER – ∑ EP
= [EH-H + EO=O ] – [2 EH-O]
= [436 + 247.5] – [2(463)]
ΔHºr = ‒242.5 kJ mol-1
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6.6 MEASUREMENT OF ENTHALPY CHANGE OF A

REACTION
The amount of heat evolved or absorbed during a physical or chemical change can be
measured by an instrument called calorimeter, which generally measures the change
in temperature during the process. At its simplest, a calorimeter consists of an insulated
vessel, a stirrer and a thermometer. There are various types of calorimeters but here we will
describe only “Glass Calorimeter”.
Calorimetry relies on the fact that it takes 4.18J of energy to increase temperature of 1g
of the water by 1°C. The amount of heat energy required to raise the temperature of a
substance of mass 1kg through 1K (or 1°C) is known as specific heat capacity, c, of the
liquid. So the specific heat capacity of water is 4.18 J g-1 K-1(or J g-1 °C-1).
The energy is transferred as heat and is shown by relationship
q = c × m × ΔT
Where,
q = heat transferred in Joules
m = mass of water/solution in grams
c = specific heat of water = 4.184 J/g °C
ΔT is the temperature change in °C
Here, (ΔT = Tf – Ti )
6.6.1 Glass Calorimeter
A glass calorimeter is suitable for measuring heat-flow for reactions in solutions. However,
it cannot be used for reactions involving gases which would escape from the vessel, nor it
would be appropriate for reactions in which the products reach high temperatures.
It consists of a beaker, a stirrer, a thermometer and a
loose-fitting lid to keep the contents at atmospheric
pressure as shown in Figure 6.3. The outside walls
of the calorimeter (beaker) are insulated using cotton
wool to minimize the exchange of heat with the
surrounding air. The reaction is carried out inside the
beaker and the heat evolved or absorbed is measured
by the temperature change. Since the pressure
inside the calorimeter is constant, the temperature Figure 6.3 Glass calorimeter to measure
measurement makes it possible to calculate the enthalpy change of reactions
enthalpy change ΔH during the reaction.
ΔH is calculated as follows:
As all the heat evolved during the reaction remains within the calorimeter and absorbed
by water, so
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i) q = mwater × cwater × ΔT
ii) Convert into kJ by dividing with 1000.
iii) Calculate ΔH for the reaction using relation:
ΔH = ‒q/n kJmol-1 (for exothermic reaction)
or = ‒mcΔT/n kJmol-1 (n = no. of moles)
The solutions we are using here are so dilute that almost all of their mass consists of water,
therefore, we can simply use specific heat capacity of water. Such a calorimeter could be
used to measure the heat of neutralization (Δ) as explained in the following example.
Sample Problem 6.2
Neutralization of 100 cm3 of 0.5 moldm-3 NaOH at 25°C with 100 cm3 of 0.5 moldm-3
HCl at 25°C raised the temperature of the reaction mixture to 28.5°C. Find the enthalpy of
neutralization. Specific heat of water = 4.2 J g-1K-1
Solution
Density of H2O is around 1gcm-3, so total volume of solution which is 200 cm3 ≈ 200 g
Rise in temperature, ΔT = 28.5 ‒ 25.0 = 3.5°C = 3.5 K
⸪ Amount of total heat evolved, q = m × c × ΔT
= 200 × 4.2 × 3.5 = 2940 J
= 2.94 kJ
Quick Check 6.3
Calculate ∆Hºn of the reaction of 50 cm3 of HNO3 with 50 cm3 of 1.5 mol/dm3 of NaOH. The
change in temperature is 4 ºC,

Calculation of n (no. of moles of H2O formed)

Using mole = Concentration(mol/dm3) x Volume (dm3)
n(HCl) = n(NaOH)= 0.5 x 100/1000 = 0.05 mol
Using equation, Number of moles of water formed, n(H2O) = 0.05 mol
Heat evolved in the formation of 0.05 mole of water, q = ‒2.94 kJ
ΔHºn = q/n = ‒2.94 kJ / 0.05 mol
So, Enthalpy of neutralization, ΔHºn = ‒58.8 kJ mol-1

6.7 ENTHALPY CHANGE AND CALORIE CONTENT OF

FOOD
In this section, we will look at foods as fuels. When food is digested, the chemical energy
stored in the food (also called calorie content) is released as heat energy. In other words,
digestion of food releases same amount of energy as it is burned outside the body. So,

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the overall enthalpy of combustion is the same as the heat of combustion, which can be
determined in a calorimeter (typically in a bomb calorimeter).
Calorie content: The calorie content of food is a measure of the energy ‘released’ when
the food is completely consumed in the body. This energy is typically expressed in units of
kilocalories (k cal) or joules (J).
6.7.1 Relation between Enthalpy Change and Calorie Content
The enthalpy of combustion of a food (ΔHc) is the calorie content of that food when it is
translated or converted into kilocalories per gram.
Look at the energy provided from glucose.
C6H12O6(s) + 6O2(g) 6CO2(g) + 6H2O() ΔH°= ̶ 2803 kJ mol‒1
The calorie content of glucose can be calculated as follows: First, we find ΔH per gram of
glucose. Molar mass of glucose is 180gmol-1. Above equation shows that;
mol (180.0 g) of glucose burns to produce energy = 2803 kJ
2803 kJ/g Energy Expenditure
1.0 g of Glucose = Energy Intake
180 g/mol

= 15.57 kJ/g
Using the relation,
ΔH (kJ/g) = – 4.184 × calorie content
Calories
ΔH (kJ/g)
calorie content = –
4.184 (kJ/kcal)
Negative Energy Balance
15.57 kJ/g Remember, the calorie content we take from food must
=– be balanced by working, exercising and doing positive
4.184 (kJ/kcal) activities. Otherwise, our bodies will have imbalanced
growth and maintenance
calorie content = – 3.72 kcal/g

6.8 HESS’ LAW OF HEAT SUMMATION

First law of thermodynamics is actually a manifestation of law of conservation of energy,
which states, “Energy can neither be created nor destroyed, but can be converted from one
form to another.”
Germain Henri Hess applied the law of conservation of energy to enthalpy changes. There
are many reactions, for which ΔH cannot be measured directly by calorimetric method. For
example, tetrachloromethane CCl4 cannot be prepared directly by combining carbon and
chlorine. Hess’s Law helps us calculating the enthalpy changes for such reactions or
processes. It states:
“The total enthalpy change in a chemical reaction is independent of the route by which
the chemical reaction takes place as long as the initial and final conditions are the same.”

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Hess’s law can be illustrated by drawing enthalpy cycles, M+N

often called energy cycles or Hess cycles. Let A be converted ΔH1 Indirect route 1 ΔH2
to ‘B’ directly in a single step, which is the direct route; or
ΔHr
in a series of two or three steps designated as indirect route A B
1 and indirect route 2 respectively as shown in Figure 6.8. Direct route

The products formed in these routes (M, N and X, Y, Z) are ΔH3 ΔH5
called reaction intermediates. Indirect route 2

Then according to Hess’ law, X Y+Z

ΔH4
For the indirect route 1, we can write: ΔHr = ΔH1 + ΔH2 Figure 6.4 Hess’ cycle

For the indirect route 2, we can write: ΔHr = ΔH3 + ΔH4 + ΔH5
Below are few examples of it.

i) Calculating Enthalpy of Formation (ΔHºf) using Enthalpy of Combustion (ΔHºc)

Sample problem 6.3
Calculate the enthalpy change of formation of CO using Hess cycle with the help of
following combustion data.
C(graphite) + O2(g) CO2(g) ΔH = ‒393.5 kJ mol-1
CO(g) + ½ O2(g) CO2(g) ΔH2 = ‒283 kJ mol-1
C(graphite) + ½ O2(g) CO(g) ΔH1 = ?
Solution: Applying Hess’ law, we can write
ΔH = ΔH1 + ΔH2 ΔH
ΔH1= ΔH - ΔH2 C + O2 CO2
ΔH1 ΔH2
= ‒393.5 – (‒283)
C + O2
= ‒110.5 kJ mol-1

ii) Calculating Enthalpy Change of Reaction (∆Hºr) using Enthalpies of

formation (∆Hºf)
Sample Problem 6.4 Calculate the enthalpy change of reaction of
C2H4 + HCl C2H5Cl
Using Hess cycle with the help of following combustion data.
ΔHºf of C2H4 = + 52.2 KJ mol-1
ΔH
C2H4(g) + HCI (g) C2H5CI(g)
ΔHºf of HCl = -92.3 KJ mol-1
ΔHºf of C2H5Cl = -109 KJ mol-1 +52.2 -92.3 -109
= -109-[+52.2+(-92.3)]
= -68.9 KJ mol-1 1 1
2C(s) 2 H (g) + CI2(g)
2 2 2

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Quick Check 6.4

Calculate the standard enthalpy change for the formation of methane:
6C(s) + 3H2(g) C6H6(l) ΔHf° = ?
The standard enthalpies of combustion of C(s), H2(g) and C6H6(l) are –394 kJ mol-1, –286 kJ mol-1
and –3267 kJ mol-1 respectively.

iv) Calculating Enthalpy Change of Formation of a substance (ΔHf°) using

Enthalpy of Combustion and Enthalpies of Formation of other substances
Sample problem 6.6 Propane (C3H8(g)) burns in oxygen according to the equation:
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(g)
When 14.64 g of propane is burned in an excess of oxygen in a calorimeter at 25 °C and
1 atm pressure, 678.6 kJ of heat is evolved. Calculate the standard enthalpy of formation
of propane. The standard enthalpies of formation of CO2(g) and H2O(g) are –393.51 kJ mol-1
and –241.82 kJ mol-1 respectively.
Solution: The first step is to find the enthalpy change when one mole of propane is burned.
Molar mass of propane, C3H8 = 3(12.011) + 8(1.0079) = 36.033 + 8.0632 = 44.096
No. of moles of propane = 14.64/44.096 = 0.3320 mol
So, 0.3320 mol propane evolves heat = 678.6 kJ
1.0 mol propane evolves heat = 678.6/0.3320 kJ mol-1 = ‒2044 kJ mol-1
According to Hess’ law:
ΔHr = [3 × ΔHºf (CO2) + 4 × ΔHºf (H2O)] ‒ [1 × ΔHºc (C3H8) + 5 × ΔHºc (O2)]
‒2044 kJ = [3×(‒393.51) + 4 ×(‒241.82)] ‒ [1 × ΔHºf (C3H8) + 5 ×(0)]
Taking the heat of combustion of O2(g) to be zero and solving this equation for ΔHºf (C3H8)
gives,
ΔHºf (C3H8) = ‒104 kJ mol-1

Quick Check 6.5

Draw enthalpy cycle of sample problem 6.6 according to Hess’ law to validate above calculation.

v) Calculating Enthalpy Change of Reactions (ΔHr) using Bond Energies

A special case of Hess’ law involves the use of bond energies to estimate heats of reaction
for gas-phase reactions. In the first step, the bonds in all the reactant molecules are broken
to give free atoms in the gas phase. The enthalpy change for this step can be calculated by
adding the bond enthalpies from Table 6.1. In the second step, the product molecules are
formed. The enthalpy change for this step can again be estimated from the bond enthalpies
of Table 6.1, which must now be taken with minus sign because the bonds are being formed

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instead of broken. In general, the heat of reaction for any gaseous chemical reaction can be
calculated from average B.E.’s by use of the following version of Hess’ law:
ΔHºrxn
Reactants Products

E(R) E(P)
Atoms
Figure 6.4 Hess Cycle; showing the relationship between B.E.’s and ΔHr. = ∑n ER – ∑n EP

Sample problem 6.7 In the case of formation of HCl(g) from H2(g) and Cl2(g), use B.E. data
from Table 6.1 to estimate ΔH for the reaction:
H2(g) + Cl2(g) 2 HCl(g)
And finally calculate the heat of formation of HCl.
We replace this reaction by a hypothetical two-step process. The bonds in all the reactant
molecules are first broken, and then the atoms are combined to make the products.
First Step:
H2(g) + Cl2(g) 2 H + 2 Cl(g)
EH-H = 436 kJ mol-1 ; ECl-Cl = 242 kJ
mol-1

ER = 1 mol × 436 kJ 1 mol × 242 kJ

+
mol mol

= 436 kJ + 242 kJ
= 478 kJ

Hess’ Cycle; showing the relationship between B.E.’s and ΔH.

Second Step:
2 H(g) + 2 Cl(g) 2 HCl(g)
EH-Cl = 431 kJ mol-1
EP = 2 mol × 431 kJ mol-1 = 862 kJ
The standard enthalpy change in the reaction is obtained by the following formula:
ΔHr° = ∑ ER – ∑ EP ΔHr°
H2(g) + Cl2(g) 2HCl(g)
ΔHr° = 678 – 862
ΔHr° = –184 kJ (for 2 mol of HCl) 2H(g) + 2Cl(g)
Enthalpy of formation of HCl, = –184/2 kJ = –92 kJ mol-1
The energy cycle is shown below:

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Quick Check 6.6

a) The reaction for the Haber process is:
N2(g) + 3H2(g) → 2NH3(g)
The relevant bond energies are:
EN≡N = 945 kJ mol–1 , EH-H = 436 kJ mol–1, EN-H = 391 kJ mol–1.
Calculate the enthalpy change of the above reaction.
b) Calculate the enthalpy change for the following reaction
C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l)
The bond energies of various bonds (in kJ mol-1 ) are given below:
EC-C = +347, EC-H = +410, EC-O = +336, EO=O = +496, EC=O = +805, EO-H = +465

6.9 ENERGETICS OF SOLUTION

The process of dissolving a solute in a solvent is called dissolution. It is assumed that the
formation of a solution, takes place in three steps.
i. Overcoming the intermolecular forces in the solvent to make room for the solute
(expanding the solvent).
ii. Breaking up the solute into individual components (expanding the solute).
iii. Allowing the solute and solvent to interact to form the solution
In this process heat is either given out or taken in. Standard enthalpy change of solution is
used to describe it.
Standard enthalpy Change of Solution (ΔHºsol)
“The standard enthalpy of solution is the amount of heat absorbed or evolved when one
mole of a substance is dissolved in a solvent to give an infinitely dilute solution.”
It is denoted by ΔHºsol and it may be exothermic or endothermic. The enthalpy changes
of solution of sodium carbonate and ammonium chloride are described by the equations
below:
Na2CO3(s) + aq 2 Na+(aq) + CO32–(aq) ΔHºsol = –25 kJ mol–1
NH4Cl(s) + aq NH4+(aq) + Cl–(aq) ΔHºsol = +16.2 kJ mol–1
In Table 6.2 are given values of heats of solution of Table 6.2 Heats of solution of some
important ionic solids (kJ mol-1)
different ionic solids in water at infinite dilution. The
Substance Heat of Solution
magnitude of heat of solution gives information regarding
the strength of intermolecular forces of attraction between NaCl 4.98
components which mix to form a solution. KCl 17.8
An ionic compound consists of oppositely charged ions, KBr 19.9
held together by strong electrostatic forces. Two factors KI 21.4
govern the process of dissolution NH4Cl 16.2
NH4NO3 26.0
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i. Hydration energy (accounts for the attraction of solute ions with water molecules)
ii. Lattice energy (controls the breaking of the ionic compounds)

6.9.1 Hydration
When ionic compounds are
dissolved in water, they are
dissociated into ions, which
are then surrounded by water
molecules. “The process in which
water molecules surround and
interact with the solute ions is
called hydration.”. The forces are
created between water molecules
and the ions which are called ion-
dipole forces as shown in Figure
6.5. And as a result, all the ions
in aqueous solution are said to be Figure 6.5 Dissolution of an ionic compound through the
hydrated. The energy of attraction process of hydration.
due to an ion-dipole force is known as enthalpy of hydration, defined as follows:
“The enthalpy change involved when one mole of a solute is dissolved in excess of water to
make infinitely dilute solution under standard conditions.”
It is denoted by ΔHhyd. This energy is always released as it is formation of ion-dipole bond.

Factors Affecting the magnitude of Hydration Energy

The heat of hydration depends on following factors:

i. Charge on the ion

ii. Size of the ion
We use a combined term for these two factors i.e., “charge density” defined as charge per
unit area. If greater charge is present on smaller ion, the charge density is large and vice
versa. And large value of charge density means that ions are strongly attracted by water
molecules during the process of hydration, thereby increasing the hydration energy values.
For example, enthalpies of hydration of following ions are in the order:

Na+ < Mg2+ < Al3+

Mg2+
< Ca2+
< Sr2+

On the same basis we can explain the hydration energy of anions.

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6.9.2 Lattice Energy (ΔHlatt)

“The lattice energy of an ionic crystal is the enthalpy change involved when one mole of the
ionic compound is formed from gaseous ions under standard conditions.”
Na+(g) + Cl–(g) NaCl(s) ΔHºlatt = –787 kJ mol–1

Factors Affecting the magnitude of Lattice Energy

The lattice energy depends on following factors:
–1100
i. Charge on the ion Li+

ii. Size of the ion –1000

Lattice enthalpy / kJ mol–1

Lattice energy and size of the ions –900 Na+

Figure 6.6 show the values of lattice energies –800

K+

of alkali metal halides. It is clear from the data Rb+

that lattice energy decreases with the increase –700

Cs+

in the size of the cation/anion. With the

increase in the size of either cations or anions, –600

the packing of oppositely charged ions become

0 F– Cl– Br– I–
less and less tight.
Figure 6.6 Lattice energies of alkali metal halides
Lattice energy and charge on the ions
Lattice energies is directly proportional to the charges on the ions i.e., greater the magnitude
of the charge on an ion, greater is its lattice energy and vice versa. Let us try to understand
this fact by comparing lithium fluoride, LiF, with magnesium oxide, MgO.
These compounds have the same arrangement of ions in their lattice structure and
comparative sizes of cations and anions are same in both compounds.
The major physical difference between LiF and MgO is the ionic charge, which affects the
lattice energy.
Magnesium oxide ΔHlatt [MgO] = –3923 kJ mol–1 is a greater than lithium fluoride ΔHlatt [LiF]
= –1049 kJ mol–1
The doubly-charged Mg2+ and O2– ions in MgO attract each other more strongly than the
singly-charged ions of the same size in LiF. For ions of similar size, the greater the ionic
charge, the higher the charge density. This results in stronger ionic bonds being formed.

Solubility trends of Group II hydroxides and sulphates:

ΔHºsol depends on both lattice energy and hydration enthalpy.

Look at the solubility trends of group II metal hydroxides. Both hydration energy and
lattice enthalpy decreases down the group due to decrease in charge density of group
2 cations. But it is observed that the lattice energy decreases more rapidly in the series
Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2 than does the energy of hydration in ions

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Mg2+, Ca2+, Sr2+ and Ba2+. For this reason, the lattice energy factor dominates this
solubility trend. ΔHºsol becomes more exothermic so solubility increase.

Now look at the solubility trends of group II metal sulphates. Because the SO42+ is much
larger than the OH-, the decrease in lattice energy going through the series of sulphates
from MgSO4 to BaSO4 is less, but the energy of hydration of the cation decreases by
a greater amount. Now the energy of hydration dominates the solubility trend, and
the solubility decreases from MgSO4 to BaSO4. ΔHºsol becomes more endothermic so
solubility increase.

6.9.3 Calculating Enthalpy Change of Solution (ΔHºsol )

We can calculate the enthalpy change of solution or the enthalpy change of hydration by
constructing an enthalpy cycle and using Hess’ law (Figure 6.7).
lattice energy
gaseous ions ionic solid
ΔH ºlatt

enthalpy change of enthalpy change

hydration of cation of solution
and anion, ΔH ºhyd
ΔH ºhyd

ions in aqueous
solution
Figure 6.7 Energy cycle of formation of an aqueous solution of an ionic solid using Hess’ law
We can see from this enthalpy cycle that:
ΔH lºatt + ΔH sol
º = ΔH hyd
º
We can use this energy cycle to calculate:

Sample problem 6.8

Determine the enthalpy change of solution (ΔH hyd
º of sodium fluoride (NaF) using the
following data:
Lattice energy of sodium fluoride (NaF) = –902 kJ mol–1
Heat of hydration of sodium ions (Na+) = –406 kJ mol–1
Heat of hydration of fluoride ions (F‒) = –506 kJ mol–1

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Solution:
Step 1: Draw the enthalpy cycle
ΔH lºatt = –902 kJ mol–1
Na+(g) + F– (g) NaF(s)

ΔH hºyd [Na+] = –406 kJ mol–1

+aq ΔH sol
º
ΔH hºyd [F–] = –506 kJ mol–1

Na+(aq) + F– (aq)
Step 2: Rearrange the equation and substitute the values to find Δ
ΔH lºatt + ΔH sºol = ΔH hºyd
ΔH sºol = (–406) + (–506) – (–902)
ΔH hºyd [NaF] = –10 kJ mol–1

6.10 BORN-HABER CYCLE

It is impossible to determine the lattice energy of a compound by a single direct experiment.
We can, however, calculate the value for ΔH lºatt using several experimental data and an
energy cycle called the Born–Haber cycle. Born-Haber cycle is an application of Hess’
law. Let us consider calculation of lattice energy of sodium Chloride using hess’s law and
Born-Haber cycle.
ΔHºf
Na(s) + ½ Cl2(g) Na+Cl‒(g)

ΔHx ΔHºlatt

+ + Cl ‒
Na(g) (g)

Figure 6.8 Enthalpy cycle of sodium chloride

where,
ΔHºf : standard enthalpy of formation of NaCl can be measured conveniently in a calorimeter.
ΔHx : Total energy involved in changing sodium and chlorine from their standard physical
states to gaseous ions. Applying Hess’ law on the above energy cycle, we can write

ΔHx + ΔHºlatt = ΔHºf

The above energy triangle has been extended to show the various stages involved in
finding ΔHx. The complete energy cycle is called the Born-Haber cycle and it is presented
in Figure 6.9.

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Na+(g) + e– + Cl2(g)

ΔHat of Cl2(g) = + 121 kJ mol–1 ΔHea of Cl = – 349 kJ mol–1

Na+(g) + e– + 1/2 Cl2(g)

Na+(g) + Cl–(g)
ΔHi of Na(g) = + 496 kJ mol–1

Na+(g) + 1/2 Cl2(g)

ΔHat of Na(g) = + 108 kJ mol–1

ΔHlatt of Na+Cl–(s)= ?
(Lattice Energy of NaCl)
Na(s) + 1/2 Cl2(g)
(REACTANTS)
ΔHf of Na+Cl–(s) = – 411 kJ mol–1

Na+Cl–(s)
(FINAL PRODUCT)
Figure 6.9 Born Haber cycle of sodium chloride (not according to scale)
Calculation of ΔHx
From above cycle we have,
ΔHx = ΔHat (Na) + ΔHi1 (Na) + ΔHat (Cl2) + ΔHea1 (Cl2)
ΔHx = 376 kJ mol-1--------------(ii)
Using, ΔHºlatt = ΔHºf ‒ ΔHx
ΔHºlatt = ‒787 kJ mol-1
Sample problem 6.9 Calculate the heat of formation of sodium fluoride, which crystallizes
in the sodium chloride lattice. The heat of atomization of Na(s) is 109 kJ/mol, half the bond
energy of F2(g) is 79 kJ/mol, the ionization energy of sodium atoms is 494 kJ/mol, the
electron affinity of fluorine atoms is –328 kJ/mol, and the lattice energy is –939 kJ/mol.
Solution: Values are given for all the quantities in the Born-Haber cycle, so we can apply
Hess’ law:
ΔHºf = ΔHºlatt + ΔHºat (Na) + ΔHº1i (Na) + ΔHºat (F2) + ΔHº1ea (F)
= ( –939 + 109 + 494 + 79 – 328 ) kJ mol-1
Δ = –585 kJ mol-1

Quick Check 6.7

a) Draw Born-Haber cycle for sample problem 6.8.
b) Calculate the heat of formation of lithium fluoride. The heat of atomization of Li(s) is 161
kJ/mol, half the bond energy of F2(g) is 79 kJ/mol, the ionization energy of lithium atoms is
520 kJ/mol, the electron affinity of fluorine atoms is –328 kJ/mol, and the lattice energy is
1107 kJ/mol.

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6.11 ENTROPY
Entropy is a measure of the number of ways energy can be distributed within a system at a
specific temperature. When the energy is distributed in more ways, a system is more stable.
Entropy can also be thought of as a measure of the randomness or disorder of a system.
The higher the randomness or disorder, the greater the entropy of the system. The system
becomes energetically more stable when it becomes more disordered.
6.11.1 Entropy, Diffusion and Number of Ways of Arrangement
We can show that the molecules in a vapour diffuse by chance by thinking about the
probability of finding them at one place at any one time. Consider the simplified model
shown in Figure 6.10 below. partition

1 2 3

gas jar A gas jar B

Figure 6.10 Diffusion and number of possible arrangements
There are 8 different ways for these molecules to arrange themselves in two jars by
diffusion from Jar A to jar B. that is
This is calculated as under
Number of molecules in A =3
Number of Jars =2
Number of possible arrangements = 23 = 8
Similarly, if there were 5 molecules initially in jar A, the possible ways of arrangement
will be 25, i.e. 32. And if there were 100 molecules, the probability will be 2100. A general
formula xy can be written for the calculation of probability, where x is the number of places
and y is the number of particles to be arranged.
Diffusion happens because there is a large number of ways of arranging the molecules. The
concept of the ‘number of ways’ of arrangement either particles or the energy within these
particles helps predict whether it can happen or not.
6.11.2 Comparison of Entropy Values
Entropies of different substances can be compared based on the number of particles, physical
properties, and state.
Small number of particles means low entropy and vice versa, for example CaCO3 has
higher standard entropy (92.9 JK-1mol-1) than CaO (39.7 JK-1mol-1). This is because the
number of possible arrangements is lower when the number of particles is smaller.
The entropy of substances having similar chemical nature is dictated by their hardness.
Harder substances have lower entropy than softer ones. Diamond has lower entropy than
graphite because it is much harder. Stronger forces result in limited vibrations in harder
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substances which decrease the probability of disorder.

A substance has lower entropy in solid state than in
liquid and gaseous states. The entropy of ice near
its melting point is 48.0 JK-1mol-1, for water, it is
69.9 JK-1mol-1; whereas water vapour just above the
boiling point is 188.7 JK-1mol-1.

Dissolution of sugar in tea increases the

entropy of both the solute and solvent

Quick Check 6.8

Explain the difference in the entropy of each of the following pairs of substances in terms of
their states and structures.
i. Br2() SO = 151.6 J K–1 mol–1 and I2(s) SO = 116.8 J K–1 mol–1
ii. H2(g) SO = 130.6 J K–1 mol–1 and CH4(g) SO = 186.2 J K–1 mol–1
iii. Hg() SO = 76.00 J K–1 mol–1 and Na(s) SO = 51.20 J K–1 mol–1
iv. SO2(g) SO = 248.1 J K–1 mol–1 and SO3() SO = 95.60 J K–1 mol–1

6.11. 3 Entropy Changes In Reactions

In a chemical reaction, if we compare the entropies of the reactants and products, we
can try to explain the magnitude of the entropy change and whether or not it increases or
decreases. The following rules must be followed to know about the change in entropy of
a reaction
When a solid is converted to a liquid or a gas in the product, the entropy change is positive.
If no. of moles in the products are more the entropy change is positive.
If there is a change in the number of gaseous molecules in a reaction, due to high values
of entropy are associated with gases. The more gas molecules, there are, the greater is the
number of ways of arranging them and the higher the entropy.
For example:
CaCO3(s) CaO(s) + CO2(g)
There is an increase in entropy of the above system because the a gas is being produced
(high entropy) but the reactant, calcium carbonate, is a solid (low entropy). Such reactions
are spontaneous.
Also, consider the reaction:
2N2O5(g) 4NO2(g) + O2(g)
We should expect an increase of entropy of the system because there are a greater number
of moles of gas molecules in the products (5 molecules) than in the reactants (2 molecules).
This is also a spontaneous process.

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The sign of Entropy Change and Spontaneity of a Process

The entropy of a substance is always positive, however, when the entropy changes it may
have positive or negative value.
A positive entropy change value (ΔSo = +ve) means a spontaneous process
A negative entropy change value(ΔSo = -ve) implies more ordered molecules and a decrease
in disorder
For some reactions, however, the entropy change fails to tell about the spontaneity of the
reaction and we need another quantity called free energy.
Quick Check 6.9
a) What do you expect about the entropy value of the following reactions, whether it would be
positive or negative?
i) N2(g) + 3H2(g) 2NH3(g) ii) 2HI(g) H2(g) + I2(g)
b) Which of the following changes are likely to be spontaneous?
i. The smell from an open bottle of aqueous ammonia diffusing throughout a room
ii. Water turning to ice at -10 °c iii. Ethanol vaporising at 20 °c
iv. Water mixing completely with salt
v. Limestone (calcium carbonate) decomposing at room temperature

6.11.4 Calculating the Entropy Change of the System (Reaction)

In order to calculate the entropy, change of the system we use the relationship:
ΔSOsystem = SOproducts – SO reactants
Let us calculate the entropy change of the system for the reaction:
2Ca(s) + O2(g) 2CaO(s)
The standard entropy values are:
SO[Ca(s)] = 41.40 J K–1 mol–1
S O[O2(g)] = 205.0 J K–1 mol–1
SO[CaO(s)] = 39.70 J K–1 mol–1,
As ΔSOsystem = SOproducts– SOreactants
= 2 × SO[CaO(s)] – {2 × SO[Ca(s)] + SO[O2(g)]}
= 2 × 39.70 – {(2 × 41.40) + 205.0}
= 79.40 – 287.8
ΔSOsystem = –208.4 J K–1 mol–1
The negative value for the entropy change shows that the entropy of the system has
decreased. We know, however, that calcium reacts spontaneously with oxygen. So the
entropy of the surroundings must also play a part because the total entropy change must be
positive for the reaction to be feasible.
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6.12 FREE ENERGY (G)

The heat content, or enthalpy (H) of any system is a combination of the following:
i. That, which is free to be converted to other forms of energy and is called Gibbs free
energy, G.
ii. That, which is necessary to maintain the system at the specified temperature, and this
is unavailable for conversion (T x S).
This can be expressed as,
H = G + TS
It follows from the equation that all of the enthalpy of a system would be available only if
the system were at zero kelvin temperature.
The following equations can be written to express the enthalpies of two different states:
ΔH = ΔG + Δ(TS)
For a process occurring at constant temperature,
ΔH = ΔG + TΔS (at constant T)
or ΔG = ΔH ‒ TΔS (constant T)
The sign of change in free energy (ΔG) of a process can be used to predict the spontaneity
of that process.
i. If ΔG < 0 (‒ve), the given process may occur spontaneously
ii. If ΔG > 0 (+ve), the indicated process cannot occur spontaneously; instead, the reverse
of it may occur.
iii. If ΔG = 0, neither the indicated process nor reverse of it can occur spontaneously. The
system is in a state of equilibrium
6.12.1 Calculating ΔG° for a Reaction
Sample Problem 6.12
For the reaction:
CaSO4(s) Ca2+(aq) + SO42-(aq)
Calculate ΔH°, ΔS° and ΔG° at 25 °C using the following data; and discuss its spontaneity.
Heat of Formation:
ΔH°f [CaSO4(s)] = -1432.7 kJ, ΔH°f [Ca2+(aq)] = -543.0 kJ, ΔH°f [SO42-(aq)]= -907.5 kJ
Standard entropy:
S°[CaSO4(s)] = 106.7 J/K, S°[Ca2+(aq)] = –55.2 J/K , S°[SO42-(aq)] = +17.2 J/K
Solution
ΔH° = ∑ ΔHf (products) ‒ ∑ ΔHf (reactants) = [–543.0 –907.5] – [–1432.7] = –17.8 kJ
ΔS° = ∑S°(products) ‒ ∑S°(reactants) = [(–55.2 + 17.2) – (106.7)] J/K = –1447 J/K
ΔS° = –0.1447 kJ/K

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ΔG° = ΔH° – T ΔS° = (–17.8 kJ) – (298 K) × (–0.1447 kJ/K) = + 25.3 kJ

Result: We conclude that this process is nonspontaneous at standard conditions at 25 °C
Sample Problem 6.13
What is the standard free-energy, ΔG° for the following reaction (Haber’s process) at 25°C?
N2(g) + 3 H2(g) 2 NH3(g)
Also discuss its spontaneity.
Heat of Formation: ΔH°f [N2(g)] = 0 kJ, ΔH°f [H2(g)] = 0 kJ, ΔH°f [NH3(g)]= –45.9 kJ
Standard entropy: S°[ N2(g] = 191.5 J/K, S°[H2(g)] = 130.6 J/K , S°[ NH3(g)] = +193 J/K
Solution
ΔH° = ∑ ΔHf (products) ‒ ∑ ΔHf (reactants) = [2 × (–45.9)] – [0 + 0] = –91.8 kJ
ΔS° = ∑nS°(products) ‒ ∑mS°(reactants) = [2 × (193)] – [191.5 + 3 × 130.6] J/K = –197 J/K
ΔS° = –0.197 kJ/K
ΔG° = ΔH° – T ΔS° = (–91.88 kJ) – (298 K) × (–0.197 kJ/K) = –33.1 kJ
Result
Since ΔG° is a negative value, thus it is concluded that Haber’s process is spontaneous at
standard conditions , i.e. at 25 °C.

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. Which of the following equations represents standard heat of formation of C2H4?
a) 2C (diamond) + 2H2(g) C2H4(g)
b) 2C (graphite) + 2H2(g) C2H4(g)
c) C (graphite) + H2(g) ½ C2H4(g)
d) 2C (diamond) + 4H(g) C2H4(g)
II. Which of the following equations correctly defines lattice energy of MgCl2?
a) Mg(s) + Cl2(g) MgCl2 b) Mg2+(g) + 2Cl‒(g) MgCl2(g)
c) Mg2+(s) + 2Cl‒ (g) MgCl2(s) d) Mg2+
(g) + 2Cl‒
(g) MgCl2(s)
III. Suppose there are 100 molecules of a gas initially in jar A, which is connected to an
evacuated jar B. When the stopcock is opened the possible ways of arrangement
of molecules will be:
a) 100 b) 1/100
c) 2100 d) 1/2100

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IV. For a reaction to occur spontaneously,

a) (ΔH ‒ TΔS) must be negative b) (ΔH + TΔS) must be negative.
c) ΔH must be negative. d) ΔS must be negative.
V. The calorie content of food, often expressed in Calories (kcal), is fundamentally
related to which thermodynamic quantity during its metabolism or combustion?
a) Entropy change (ΔS) b) Gibbs free energy change (ΔG)
c) Enthalpy change (ΔH) d) Specific heat capacity (c)
VI. Which of the following quantities is NOT typically determined using Hess’s Law?
a) Enthalpy change of formation b) Enthalpy change of combustion
c) Activation energy d) Enthalpy change of reaction
VII. Which of the following factors would lead to a greater enthalpy change of
hydration (more exothermic)?
a) A larger ionic radius and a smaller charge
b) A smaller ionic radius and a smaller charge
c) A larger ionic radius and a larger charge
d) A smaller ionic radius and a larger charge
VIII. The enthalpy of solution can be expressed in terms of which of the following
enthalpy changes?
a) ΔH lattice + ΔH hydration ​ b) ΔH lattice − ΔH hydration
c) −ΔH lattice + ΔH hydration d) −ΔH lattice − ΔH hydration

IX. Which of the following reactions has an enthalpy change that is equal to the
standard enthalpy of formation of water, ΔHof​[H2​O(l)]?
a) 2H(g) + O(g) → H₂O(l) b) H₂(g) + ½O₂(g) → H₂O(g)
c) H₂(g) + ½O₂(g) → H₂O(l) d) 2H⁺(aq) + O²⁻(aq) → H₂O(l)
X. The enthalpy change for a reaction depends on:
a) Pathway taken from reactants to products
b) Presence of a catalyst
c) Initial and final states of the reactants and products
d) Rate of the reaction
XI. Which of the following processes would typically result in an increase in entropy
of the system?
a) Freezing of water b) Condensation of steam
c) Dissolving a solid in a liquid
d) Formation of a crystal from a saturated solution

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XII. Consider a reaction with ΔH>0 and ΔS<0. This reaction will be:
a) Spontaneous at all temperatures b) Non-spontaneous at all temperatures
c) Spontaneous only at high temperatures d) Spontaneous only at low temperatures

SHORT-ANSWER QUESTIONS
Q.2Attempt the following short-answer questions:
a. Differentiate between exothermic and endothermic reactions.
b. What do you understand by the enthalpy of a system?
c. Differentiate clearly between entropy (S) and Gibbs free energy (G).
d. Distinguish clearly between standard enthalpy of reaction and standard enthalpy of
formation.
e. Define the following enthalpies and give one example of each.
(i) Standard enthalpy of solution (ii) Standard enthalpy of hydration
(iii) Standard enthalpy of atomization (iv) Standard enthalpy of combustion
f. Explain why the lattice enthalpy of an ionic compound is typically a large negative
value.
g. What factors influence the magnitude of the lattice enthalpy?
h. Explain why the enthalpy of hydration is always an exothermic process for gaseous
ions. What are the main interactions responsible for the release of energy during
hydration?
i. For the reaction CH4​(g)+2O2​(g) → CO2​(g)+2H2​O(g), identify all the bonds that need to be
broken and all the bonds that need to be formed to carry out a bond energy calculation
of ΔH.
j. For a reaction to be spontaneous, what is the required sign of the Gibbs free energy
change (ΔG)? Under what conditions of enthalpy change (ΔH) and entropy change
(ΔS) will a reaction always be spontaneous?
k. The enthalpy of solution can be either positive or negative. Explain what a positive
ΔHsol​ and a negative ΔHsol​ indicate about the energy changes during the dissolution
process.
l. Consider two ions with similar charges but different sizes, or similar sizes but different
charges. Explain how the concept of charge density can be used to predict which ion
will have a more exothermic enthalpy of hydration and why.

DESCRIPTIVE QUESTIONS
Q.3 State and explain Hess’ law. Give its two applications.
Q.4 What is lattice energy? How does Born-Haber cycle help to calculate the lattice
energy of NaCl?
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NUMERICAL PROBLEMS
Q.5 (a) When 0.400 g NaOH is dissolved in 100.0 g of water, the temperature rises
from 25.00 to 26.03°C. Calculate: (i). qwater , (ii). ΔH for the solution process
Q.6 By applying Hess’ law, calculate the enthalpy change for the formation of an
aqueous solution of NH4Cl from NH3 gas and HCl gas. The results for the various
reactions are as follows.
(i) NH3(g) + aq NH3(aq) ∆ H= –35.16 kJ mol-1
(ii) HCl(g) + aq HCl(aq) ∆ H= –72.41 kJ mol-1
(iii) NH3(aq) + HCl(aq) NH4Cl(aq) ∆ H= –51.48 kJ mol-1
Q.7 Calculate the heat of formation of ethyl alcohol from the following information
(i) Heat of combustion of ethyl alcohol is –1367 kJ mol-1
(ii) Heat of formation of carbon dioxide is –393.7 kJ mol-1
(iii) Heat of formation of water is –285.8 kJ mol-1
Q8 Using the information given in the table below, calculate the lattice energy of
potassium bromide.
Reactions ΔH/ kJ mol-1
K(s) + ½ Br2(l) K+Br– –392
K(s) K(g) +90
K(s) K+(g) + e‒ +420
½ Br2(l) Br(g) +112
Br + e ‒ Br‒ –342
Q.9 Calculate the entropy change of the surroundings ΔS°surrounding for the reaction at
298K :
2Ca(s) + O2(g) 2CaO(s) ΔHOreaction = –1270.2 kJ mol–1
Q.10 For the reaction: CaSO4(s) Ca2+(aq) + SO42-(aq)
Calculate ΔH°, ΔS° and ΔG° at 25 °C using the following data; and discuss its
spontaneity.
Enthalpy of Formation:
ΔH°f (CaSO4(s)) = -1432.7 kJ, ΔH°f (Ca2+(aq)) = -543.0 kJ, ΔH°f (SO42-(aq))= -907.5 kJ
[Standard entropy: S°(CaSO4(s)) = 106.7 J/K, S°(Ca2+(aq)) = –55.2 J/K, S°(SO42-(aq))=
+17.2 J/K]

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7
Chemistry-XI

REACTION KINETICS
STUDENT LEARNING OUTCOMES [C-11-A-124 to C-11-A-134]

Explain the rate of reaction, and rate constant. (Understanding)

Use experimental data to calculate the rate of a chemical reaction. (Application)
Use the Boltzmann distribution curve to explain the effect of temperature on the rate of a
reaction. (Understanding)
Describe the effect of temperature change on the rate constant and rate of reaction.
(Understanding)
Explain the concept of activation energy and its role in chemical reactions. (Understanding)
Explain the concept of catalyst and how they increase the rate of a reaction by lowering the
activation energy. (Understanding)
Interpret reaction pathway diagrams, including in the presence and absence of catalysts.
(Application)
Use rate equations, including orders of reaction and rate constant. (Application)
Calculate the numerical value of a rate constant using the initial rates and half-life method.
(Application)
Suggest a reaction mechanism that is consistent with a given rate equation and rate
determining step. (Understanding)
Explain the relationship between Gibbs free energy change, ΔG° and the feasibility of a
reaction. (Understanding)

It is a common observation
that rates of different chemical
reactions differ greatly for
example, the reaction of NaCl
with AgNO3 is very fast. The
hydrolysic of ester proceeds at a
moderate rate. Whereas, rusting
of iron is a slow process.
Reaction kinetics is the study An explosion is a swift reaction that happens
of the rates of chemical within a fraction of a second, the rusting of iron is
reactions. It includes a variety a slow process that may take days or months. The
of experimental methods for rates of reactions occuring during the explosion
measuring reaction rates, orders are enormous.
and mechanisms of reactions.
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The rates of reactions and their control are often important in industry. They might be
the deciding factors that determine whether a certain chemical reaction may be used
economically or not. Many factors influence the rate of a chemical reaction. It is important
to discover the conditions under which the reaction will proceed most economically.
7.1 COLLISION THEORY
Collision theory explains how reactions occur. According to this theory, for a chemical
reaction to take place, the particles atoms, ions or molecules of reactants must form a
homogeneous mixture and collide with one another. These collisions may be effective or
ineffective depending upon the energy of the colliding particles. When these collisions are
effective, they give rise to the products, otherwise the colliding particles just bounce back.
The effective collisions can take place only when the colliding particles possess certain
amount of energy and they approach each other with the proper orientation. The minimum
amount of energy, required for an effective collision between the reacting species, is called
activation energy. Most of the reactions are slow, showing that all the collisions are not
equally effective.
The process can be understood with the help of a graph between the path of reaction
and the potential energy of the reacting molecules. If the collision is effective, then the
molecules flying apart are chemically different otherwise the same molecules just bounce
back. The reactants reach the peak of the curve to form the activated complex. Only, the
colliding molecules with proper activation energy, will be able to climb up the hill and give
the products.
Quick Check 7.1
a) The collision frequency and the orientation of molecules are necessary conditions a reaction
to occur. Justify the statement.
b) What role does the activation energy play in chemical reactions?
c) How does the activation energy affect the rate of reaction?

7.2 RATE OF REACTION

During a chemical reaction, reactants
are converted into products. So, the
concentration of the products increases
with the corresponding decrease in the
concentration of the reactants as they are
being consumed. The rate of a reaction is
defined as the change in the concentration
of a reactant or a product divided by the
time taken for the change.

Figure 7.1 Change in the concentration of reactants

and products with time for the reaction A → B
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change in concentration of the substance

Rate of reaction =
time taken for the change

Δx
Rate of reaction =
Δt
Where Δx is a very small change in the concentration of a r e a c t a n t o r a product in
a very small t i m e interval Δt.
The situation is explained graphically in Figure 7.1. for the reactant A which is changing
irreversibly to the product B.
A B
The slope of the graph for the reactant or the product is steepest at the beginning. This
shows a rapid decrease in the concentration of the reactant and consequently, a rapid
increase in the concentration of the product. As the reaction proceeds, the slope becomes
less steep indicating that the reaction is slowing down with time, ultimately both the
curves become parallel. It means that the rate of a reaction is changing every moment.
This is the stage of completion of reaction.
The rate of reaction has the units -3 of concentration divided by time. Usually, the
concentration is expressed in mol dm and the time in second, thus the units for the
reaction rate are mol dm-3s-1.
mol.dm-3
Rate of reaction = = mol.dm-3 s-1
seconds
However, for a slow reaction the units may be mol dm-3 min-1 or even mol dm-3 h-1. For a gas
phase reaction, units of pressure are used in the place of molar concentrations.
The rate of a general reaction, A → B, can be expressed in terms of rate of disappearance
of the reactant A or the rate of appearance of the product B mathematically, where [A] and
[B] are the concentrations of A and B, respectively.
Δ[A] Δ[B]
Rate of reaction = – = +
Δt Δt
The negative sign with indicates a decrease in the concentration of the reactant A. Since
the concentration of product increases with time, the sign in rate expression involving the
change of concentration of product is positive.
7.2.1 Instantaneous and Average Rate
The rate at any one instant during the interval is called the instantaneous rate. Whereas
the average rate of reaction is defined as, “The rate of reaction between two specific time
intervals or the rate over a time period”. The average rate and instantaneous rate are equal
for only one instant in any time interval. At first, the instantaneous rate is higher than the
average rate. At the end of the interval the instantaneous rate becomes lower than the
average rate.
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Sample Problem 7.1

The reaction for the formation of ammonia in Haber process is:
N2(aq) + 3H2(g) → 2NH3(g)
i. Calculate the instantaneous rate after 1.0 min
ii. What is the average rate of production of ammonia for the system, between 1.0 and
4.0 minutes?
Solution
The instantaneous rate at 1.0 min can be calculated as
∆C 2.7 mol.dm-3
Instantaneous Rate = = 2.7 mol.dm-3min-1
∆t 1 min
If the concentration of ammonia is 3.5 mol. dm-3 after 1.0 min and 6.2 mol.dm-3 after
4.0 minutes?
Solution
∆C = ∆[NH3] = (6.2-3.5) mol.dm-3 ; ∆c = 2.7 mol. dm-3
∆t = (4.0 – 1.0) ; ∆t = 3.0 min
∆C ∆[NH3] 2.7 mol.dm-3
Rate of formation of NH3 = = = = 0.90 mol dm-3min-1
∆t ∆t 3 min
The rate of production of NH3 gas over the given time interval is 0.90 mol dm3 min1.
Quick Check 7.2
The reaction of hydrogen and iodine to make hydrogen iodide at a particular temperature,
H2(g) + I2(g) → 2HI(g) was studied at various times. At 100.0 s after the start of the reaction,
the iodine concentration had fallen from 0.010 mol dm-3 to 0.0080 mol dm-3. What is the
average rate of reaction during this period?

7.2.2 Measuring the Rate of A Chemical Reaction

The measurement of rate of a chemical reaction Table 7.1 Change in concentration
involves the determination of the concentration of of HI with regular intervals
2HI(g)→H2(g)+I2(g)
reactants or products at regular time intervals as the
Concentration of Time (s)
reaction progresses. HI (mol dm-3)
To determine the rate of reaction for a given length of 0.100 0
time, a graph is plotted between time on x-axis and 0.0716 50
concentration of a reactant on y-axis, whereby a curve 0.0558 100
is obtained. To illustrate it, let us investigate the 0.0457 150
decomposition of HI to H2 and I2 at 500°C. By using 0.0387 200
the data, a graph is plotted as shown in Fig (7.3). The 0.0336 250
graph is between time on x-axis and concentration of 0.0296 300
HI in mol dm-3 on y-axis. Since HI is a reactant, so it is
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a falling curve. The steepness of the concentration-time curve reflects the progress of
reaction. Greater the slope of curve near the start of reaction, greater is the rate of reaction.
In order to measure the rate of reaction, draw
X
a tangent say, at 100 seconds, on the curve and 0.10
measure the slope of that tangent. The slope of 0.09
the tangent is the rate of reaction at that point 0.08
i.e., after 100 seconds. A right-angled triangle
0.07
ABC is completed with a tangent as hypotenuse. A
Figure 7.2 shows that in 100 sec, the change in [H1] 0.06
0.04 mol dm–3
concentration is 0.04 mol.dm-3. The rate is then 0.05

calculated by using the following expression. 0.04

C B
∆C 0.03
Rate of reaction =
∆T 0.02

rate = 0.04 mol.dm-3 0.01

= 4×10-4 mol dm-3 s-1
100 sec 0
0 50 100 150 200 250 300 350 Y
This value of rate means that the concentration Time (s)
of HI is decreasing by 2.5 moles per dm-3 every Figure 7.2 The change in the HI
second during the given interval. concentration with time to the reaction
2HI(g) H2(g) +I2(g) at 508ºC
If we plot a graph between time on x-axis and
concentration of any of the products i.e H2 or I2, then a rising curve is obtained. The value
of the tangent at 100 seconds will give the same value of rate of reaction as 4x10-4 mol
dm-3 s-1.

Quick Check 7.3

a) Plot the data in Table 7.1 for HI.
b) Calculate the rate after 300 sec (when the concentration is 0.03 mol dm–3) by drawing a
tangent.
c) Use the same method to calculate the rate of reaction at HI concentrations of 0.10 mol
dm–3, 0.050 mol dm–3 and 0.02 mol dm–3.
d) What do you deduce about the rate of the reaction with time from these calculations?
e) At which concentration, the rate is highest, and lowest?

7.2.3 Measurement of Concentration

The change in concentrations of reactants or products can be determined by both physical
and chemical methods depending upon the type of reactants or products involved.
a) Chemical Method
This is particularly suitable for reactions in solution. In this method, we do the chemical
analysis of a reactant or a product. The acid hydrolysis of an ester (ethyl acetate) in the
presence of a small amount of an acid is one of the best examples.

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H+
CH3COO2H5() + H2O() CH3COOH() + C2H5OH()
In case of hydrolysis of an ester, the solution of ester in water and the acid acting as a
catalyst are allowed to react. After some time, a sample of reaction mixture is withdrawn
by a pipette and run into about four times its volume of ice-cold water. The dilution and
chilling stop the reaction. The acid formed is titrated against a standard alkali, say NaOH,
using phenolphthalein as an indicator.
The analysis is repeated at various time intervals after the start of reaction. This would
provide an information about the change in concentration of acetic acid formed during the
reaction at different time intervals.
b) Physical Methods
Some of the methods used for the measurement of concentration are as follows:
i) Spectrophotometry or colorimetry
This method is applicable if a reactant or a
product absorbs ultraviolet, visible or infrared
radiation. The rate of reaction can be measured
by measuring the amount of radiations
absorbed. For the reaction shown in Figure
7.3, the concentration can be measured using
the colorimetry.
ii) Electrical conductivity method
The rate of a reaction involving ions can be Figure 7.3 The concentration change for this
studied by electrical conductivity method. The reaction can be determined using colorimetry.
conductivity of such a solution depends upon the rate of change of concentration of the
reacting ions or the ions formed during the reaction. The conductivity will be proportional
to the rate of change in the concentration of such ions.
iii) Volume change method
This method is useful for those reactions,
which involve changes in volumes of gases as
shown in Figure 7.4. The volume change is
directly proportional to the extent of reaction,
and changes in concentration.

Figure 7.4 Rate of reaction can be followed by

measuring the change in volume of a gas given
off in a reaction.

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Interesting Information
The rates of some very fast reactions can be monitored using stopped-flow spectrophotometry. In
this technique, very small volumes of reactants are driven at high speed into a mixing chamber.
From here they go to an observation cell, where the progress of the reaction is monitored (usually
by measuring the transmission of ultraviolet radiation through the sample). A graph of rate of
reaction against time can be generated automatically.

7.3 FACTORS AFFECTING RATE OF A CHEMICAL

REACTION
In general, the rates at which reactants are consumed and products are formed during
chemical reactions vary greatly. Even a chemical reaction involving the same reactants
may have different rates under different conditions. The factors affecting the rates of
reactions are
i. Concentrations of the reactants Did You Know?
ii. Temperature of the system In the case of reactions that involve gaseous
iii. Surface area reactants, an increase in pressure increases the
concentration of the gases which leads to an
iv. Catalyst increase in the rate of reaction. However, pressure
change has no effect on the rate of reaction if the
reactants are either solids or liquids.
7.3.1 Concentration
According to the law of mass action, a) b)
the greater the concentration of the
reactants, the more rapidly the reaction
proceeds. When the concentration of
one or more reactants increases, rate
of reaction increases. This is because
increasing the concentration results in
more collisions between the reacting
particles, which speeds up the reaction.
Figure 7.5 The reaction in box a) will occur faster than that in,
7.3.2 Temperature b) due to the higher concentration.

(Maxwell-Boltzmann distribution curve)

Increase in temperature increases the reaction rate. It has been observed that rate either
doubles or triples for every 10 °C rise in temperature. Temperature usually has a major
effect on the rate of reaction. Molecules at higher temperatures have more thermal energy.
So, they collide more frequently and with greater energy.
The Boltzmann distribution curve is a graph that shows the distribution of energies at
certain temperature. In a reaction, a few particles will have very low energy, a few
particles will have very high energy, and many particles will have energy in between.
The distribution of energies at a given temperature can be shown on a graph as shown in
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Figure7.6, this is called the Boltzmann distribution. As you know that the activation
energy is the minimum energy required for colliding particles fruitfully to convert into the
product. The shaded area under the graph as shown in Figure 7.6 represents the proportion
of molecules that have enough energy to cause a chemical change when they collide. The
area under the curve represents the number of particles. The shaded area shows the number
of particles with energy greater than the activation energy, Ea.
Number of molecular

Ea– at and above this energy the molecules

have enough energy to collide effectively

E
a

0
0 Molecular energy
Figure 7.6 The Boltzmann distribution of molecular energies showing the activation energy
As the temperature of a reaction mixture is raised, the average kinetic (movement) energy
of the particles increases. The reacting particles move around more quickly at a higher
temperature, resulting in more frequent collisions. Therefore, the proportion of successful
collisions also increases greatly as shown in Figure 7.8. The curve showing the Boltzmann
distribution at the higher temperature flattens and the peak shifts to the right. For 10 °C
rise in temperature, the shaded area under the curve approximately doubles. In conclusion,
increasing the temperature increases the rate of a reaction.

Figure 7.7 The Boltzmann distribution of molecular energies at temperatures T1 and T2

Quick Check 7.4

a) What is the Boltzmann distribution curve?
b) Explain why a 10 °C rise in temperature approximately doubles the rate of a reaction.

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7.3.3 Catalyst
A catalyst is defined as a substance which alters the rate of a chemical reaction, but remains
chemically unchanged at the end of the reaction. A catalyst is often present in a very
small amount. For example, the reaction between H2 and O2 to form water is very slow at
ordinary temperature, but proceeds more rapidly in the presence of platinum. Platinum acts
as a catalyst. Similarly, KClO3 decomposes much more rapidly in the presence of a small
amount of MnO2. HCl is oxidized to Cl2 in the presence of CuCl2.
Pt
2 H 2 + O2  → 2 H 2O
MnO2
2 KClO3 
# → 2 KCl + 3O2
CuCl2
4 HCl + O2   → 2 H 2O + 2Cl2
The process, which takes place in the presence of a catalyst, is called catalysis. A catalyst
provides a new reaction path with a low activation energy barrier, as shown in Figure
7.8. A greater number of molecules are now able to get over the new energy barrier and
reaction rate increases.

Figure 7.8 The energy path diagram for an uncatalyzed and a catalyzed reaction

Types of Catalysis
i) Homogeneous Catalysis
In this process, the catalyst and the reactants are in the same phase and the reacting system
is homogeneous throughout. The catalyst is distributed uniformly throughout the system.
For example:
i. The formation of SO3(g) from SO2(g) and O2(g) in the contact process for the manufacture
of sulphuric acid, needs NO(g) as a catalyst. Both the reactants and the catalyst are
gases.
NO
2SO2 (g) + O2 (g) 2SO3(g)
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ii. Esters are hydrolyzed in the presence of H2SO4. Both the reactants and the catalyst are
in the solution state.
H+
CH3COOCH2CH3() + H2O() CH3COOH() + CH3CH2OH()
Ethyl ethanoate Ethanoic acid Ethanol

Did you Know!

Biochemical catalysts, commonly known as enzymes (nature’s catalyst) are essential molecules
in living organisms’ function by lowering the activation energy required for a chemical reaction
to proceed, thereby increasing the reaction rate. Enzymes are typically proteins. Factors such as
pH, temperature, and the concentration of substrate molecules can influence enzyme activity.

ii) Heterogeneous Catalysis

In such systems, the catalyst and the reactants are in different phases. Mostly, the catalysts
are in the solid phase, while the reactants are in the gaseous or liquid phase. For example:
Oxidation of ammonia to NO in the presence of platinum gauze helps us to manufacture
HNO3.
Pt, 800ºc
4NH3(g) + 5O2(g) 4NO(g)+ 6H2O(g)

Hydrogenation of unsaturated organic compounds are catalysed by finely divided Ni, Pd

or Pt.
Ni, 150ºC
C2H4(g) + H2(g) C2H6(g)

Interesting Information
Vitamins are organic compounds that act as catalysts in biochemical reactions, especially when
they function as coenzymes. Coenzymes are organic molecules that help enzymes catalyze
reactions more efficiently. For example, Vitamin K, is necessary for blood clotting. Low levels
of vitamin K can cause bleeding diathesis. A lack of vitamins can disrupt metabolic balance in
cells and organisms. Vitamin deficiency is an example of a cofactor deficiency.

Quick Check 7.5

a) Can a catalyst be consumed in a chemical reaction? Why or why not?
b) Explain whether the reaction below is an example of heterogeneous or homogeneous
catalysis:
2SO2(g) + O2(g) 2SO3(g)
c) Draw an energy profile diagram to show a typical uncatalysed reaction and an enzyme-
catalysed reaction.
On your diagram show:
i) the activation energy for the catalysed and
ii) uncatalysed reactions

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7.4 RATE LAW, RATE CONSTANT AND ORDER OF

REACTION
7.4.1 Rate Law and Rate Constant
The rate of a chemical reaction at a given temperature may depend on the concentration
of one or more reactants and products. The representation of rate of a reaction in terms of
concentration of the reactants is known as rate law. A rate law is an equation that relates
the rate of a reaction to the concentrations of reactants raised to various powers according
to the experimental data.
For a general reaction between A and B where ‘a’ moles of A and ‘b’ moles of B react to
form ’c’ moles of C and ’d’ moles of D.
aA + bB cC + dD
We can write the rate equation as:
Rate = k [A]x [B]y
Where x and y are the experimentally determined values that may or may not be equal to
the coefficient of reactants in the balanced chemical equation, as ‘a’ and ‘b’ in the above
equation. This expression is called rate equation. The brackets [ ] represent the molar
concentrations and the proportionality constant k is called rate constant for the reaction.
If [A] = 1 mol dm-3 and [B] = 1 mol dm-3
Rate of reaction = k × 1x × 1y = k
The rate constant can be defined as “The specific rate constant of a chemical reaction is
the rate of reaction when the concentrations of the reactants are unity”. Under the given
conditions, k remains constant, but it changes with temperature.
7.4.2 Reaction Order
The exponents ’x’ or ‘y’ in the above equation give the order of reaction with respect to
the individual reactants. “The order of a reaction with respect to a specific reactant is
the exponent applied to that reactant’s concentration within the rate equation”. Thus, the
reaction is of order ‘x’ with respect to A and of order ‘y’ with respect to B. The overall
order of reaction is (x+y). The order of a reaction defines how the reactant concentration
influences its rate. For a single-reactant, the order is simply the concentration’s power in
the rate equation.
The chemical reactions are classified as zero, first, second and third order reactions. The
order of reaction provides valuable information about the mechanism of a reaction.
It is crucial to differentiate between the order concerning a single reactant and the overall
reaction order.
Take equation for the reaction of nitrogen (II) oxide (NO) with H2 and oxygen:
2H2(g) + 2NO(g) N2(g) + H2O (g)

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rate = k[H₂][NO]²
This reaction is:
i. first-order with respect to H₂
ii. second-order with respect to NO
iii. third-order overall (1 + 2 = 3)

Keep in Mind
The order of reaction is given by the sum of all the exponents to which the concentrations in the
rate equation are raised. It is important to note that the order of a reaction is an experimentally
determined quantity and cannot be inferred simply by looking at the reaction equation. The sum
of the exponents in the rate equation may or may not be the same as in a balanced chemical
equation.

Quick Check 7.6

a) How order of reaction is derived from the rate law?
b) Explain what is meant by the specific rate (rate constant) of a reaction and how it is
represented in rate equation.

7.4.3 Types of Reaction Order

Zero Order Reaction
The rate of a zero order reaction is independent of the concentration of the reactants. A
change in the concentration has no effect on the speed of the reaction.
For the general reaction: A → Product
Rate = k [A]0
Examples:
i) H2(g) + Cl2 2HCl(g)
Rate = k [H2]0[Cl2]0 = k
ii) 2NH3 N2 + 3H2
Rate = k [NH3]0 = k
Photochemical reactions are usually zero order.
First Order Reaction
In these reactions, there may be multiple reactants present, but concentration of only one
reactant will change during the reaction. Examples of a first order reaction is:
Decomposition of nitrogen pentoxide involves the following equation.
2N2O5(g) 2N2O4(g) + O2(g)

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The experimentally determined rate equation for this reaction is as follows:

Rate = k[N2O5] (n = 1)
This equation suggests that the reaction is first order with respect to the concentration of
N2O5.
Second Order Reaction
A reaction for which sum of the exponents of the concentrations in the rate equation is 2.
A second order reaction is a reaction whose rate depends either on the concentration of
one reactant raised to the second power or on the concentrations of two different reactants,
each raised to the first power. The simpler type of reaction involves one kind of reactant
molecule.
Rate =k[A]2 (n = 2)
Rate = k [A]1[B]1 (n = 1+1 = 2)
Oxidation of nitric oxide with ozone has been shown to be first order with respect to NO
and first order with respect to O3. The sum of the individual orders gives the overall order
of reaction as two.
NO(g) + O3(g) NO2(g) + O2(g) Rate = k[NO][O3]
Third Order Reaction
A third order reaction is the reaction for which sum of the exponents of the concentrations
in the rate equation is three.
Rate =k[A]3 (n = 3)
or Rate = k [A]2[B]1 (n = 2+1 = 3)
or Rate = k [A]1[B]1[C]1 (n = 1+1+1 = 3)
2FeCl3(aq) + 6KI(aq) 2FeI2 (aq) + 6KCI(aq) + I2
This reaction involves eight reactant molecules but experimentally it has been found to be
a third order reaction.
Rate = k[FeCl3][KI]2
also, the following reaction is third order
2NO(g) + O2(g) 2NO2(g) Rate = k[NO]2[O2]1
Fractional Order Reaction
A reaction in which the sum of exponents of rate equation is in fraction, is called the
fractional order reaction. For example, consider the formation of carbon tetrachloride from
chloroform.
CHCl3(l) + Cl2(g) CCl4(l) + HCl(g)
Rate =k[CHCl3] [Cl2] 1/2 n =1 + 1/2 = 1.5
Reactions involving free radicals frequently exhibit fractional orders.
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7.4.4 Units of Rate Constant

The rate constant is specific for a particular reaction at a certain temperature. Since
concentrations are in mol dm-3 and the reaction rate is in units of mol dm-3 s-1. The units
for k depend on the order of the reaction and the units of time.
General Equation:

Rate = k[Reactants]n where n = order of reaction

Rate (mol dm -3) s-1
k= =
(Rectants)n (mol dm -3)n

or k = (mol.dm-3)1-n s-1
or k = (concentration)1-n s-1
This equation can be used to determine units of any order of reaction.
For a zero order reaction (n = 0),
k = (mol.dm-3)1-0 s-1
k = mol.dm-3 s-1
For a first order reaction (n = 1), the rate is directly proportional to the concentration of
one reactant.
k = (mol.dm-3)1-1 s-1
k = (mol.dm-3)0 s-1
k = s-1
Therefore, the units of k for a first order rate constant are s-1.
For a second order reaction (n = 2),
k = (mol dm-3)1-2 s-1
k = mol-1 dm3 s-1
k = dm3 mol-1 s-1
The units of k for a second order rate constant are dm3 mol-1 s-1.
For a third order reaction (n = 3),
k = (mol dm-3)1-3 s-1
k = mol-2 dm6 s-1
k = dm6 mol-2 s-1
Therefore, the units of k for a third order rate constant are dm6 mol-2 s-1.

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Quick Check 7.7

a) Calculate the overall order of reactions which have the rate expressions:
i) rate = k[NO]2 [NH3]0
ii) rate = k[BrO3][Br–][H+]2
b) Why do you think chemists want to know the order of a reaction and the rate constant for
a reaction?
c) Why the sum of the coefficients of a balanced chemical equation is not necessarily
important to give the order of a reaction?

7.5 DETERMINATION OF RATE CONSTANT

The rate constant (k) of a reaction can be calculated using the following two methods:
7.5.1 Initial Concentration Method
In the presence of hydrogen ions, hydrogen peroxide, H2O2, reacts with iodide ions to form
water and iodine:
H2O2(aq) + 2I–(aq) + 2H+(aq) 2H2O(l) + I2(aq)
The rate equation for this reaction is:
k[H2O2]
rate of reaction =
[I–]
The progress of the reaction can be followed by measuring the initial rate of formation of
iodine. Table 7.2 shows the rates of reaction obtained using various initial concentrations
of each reactant.
The procedure for calculating k is shown below, using the data for experiment 1.
Step 1 Write out the rate equation.

k[H2O2]
rate of reaction =
[I–]
Step 2 Rearrange the equation in terms of k

rate × [I–]
k=
[H2O2]
Step 3 Substitute the values

3.50 × 10–6 × (0.0100)

k=
(0.0200)

k = 1.75 × 10–2 dm3 mol–1 s–1

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Table 7.2: Effect of change in concentrations of reactants on the rate of reaction

Experiment [H2O2]/ [I–]/ moldm–3 [H+]/ Initial rate of
moldm–3 moldm–3 reaction/moldm–3
s–1
1 0.0200 0.0100 0.0100 3.5 × 10– 6
2 0.0300 0.0100 0.0100 5.3 × 10–6
3 0.0050 0.0200 0.0200 1.75 × 10–6

The concentration of hydrogen ions is ignored because [H+] does not appear in the rate
equation. The reaction is zero order with respect to [H+].
7.5.2 Half-Life Method
“Half-life, t1/2
, is the time taken for the concentration of a reactant to fall to half of its
original value”. Calculating the rate constant (k) using the half-life method involves
measuring the time it takes for the concentration of a reactant to decrease by half.
If the reaction is first-order, then the rate constant and the half-life of the reaction are
related in the following way:
k = 0.693/t1/2
Here is an example to help you understand how the process is done. A sample of hydrogen
peroxide has a half-life of 2 hours. It decomposes in a first-order reaction. Calculate the
rate constant, k, for this reaction.
To calculate k, we first need to convert the half-life, which is 2 hours, into seconds:
2 × 60 × 60 = 7200 s
We then simply substitute this value into the equation:
0.693
k=
7200 s
k = 9.6 × 10-5 s -1
Sample Problem 7.2
The first-order reaction cyclopropane to propene, for which the half-life is 17.0 min,
Calculate the rate constant of this reaction.
Solution:
Step 1 convert minutes to seconds
Step 2 substitute the half-life into the expression:
0.693
k=
t 1/2

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0.693
k=
17 × 60 s
= 6.79 × 10–4 dm3 mol–1 s–1
Quick Check 7.8
Consider a first-order reaction with a half-life of 15 minutes. If the initial concentration of the
reactant is 0.100 mol dm-3, calculate the rate constant (k) for the reaction.

7.6 REACTION MECHANISM

A reaction mechanism is a detailed, step by step description of how a chemical reaction
occurs at the molecular level to yield the product(s). Unlike the overall balanced chemical
equation, which only shows the reactants and products, the reaction mechanism reveals the
actually happening individual steps (called elementary steps) that lead to the formation of
products. Each of these steps represents a single molecular event, such as the breaking or
forming of bonds.
Many reactions do not occur in a single step, but rather proceed through a series of steps.
Each step is called an elementary reaction and is directly caused by the collision of atoms,
ions or molecules. The number of reactant molecules involved in an elementary step is
called its molecularity.
A unimolecular elementary reaction involves only a single reactant molecule. The example
of a unimolecular reactions is the decomposition of N2O5.
N2O5(g) NO2(g) + NO3(g)
An elementary reaction that involves two atoms, ions or molecules and is called
bimolecular. For example;
CO(g) + NO3(g) NO2(g) + CO2(g)
NO(g) + O3(g) NO2(g) + O2(g)
A termolecular reaction step involves the simultaneous reaction of three molecules. Such
reactions are rare. An example is the reaction between oxygen molecules and atomic
oxygen to form ozone in the stratosphere or during smog formation.
2O2(g) + O(g) O3(g) + O2(g)
Intermediates are short lived species (ions or free radicals) that are produced in one step
of the mechanism and consumed in a subsequent step. They do not appear in the overall
balanced equation because they are not stable products.
Rate Determining Step
In many reaction mechanisms, one step is significantly slower than all the others, this
step is called the rate-determining step. This step controls the overall rate of the reaction
because it limits the speed at which the reaction can proceed. The balanced equation for the
overall reaction is equal to the net result of all the individual steps. In a chemical reaction,

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any step that occurs after the rate-determining step will not affect the rate, provided that
it is compared with the rate-determining step. So the atoms, ions or molecules taking part
in the mechanism after the rate-determining step do not appear in the rate expression. All
reactants that appear in the rate-determining step will also appear in the rate equation.
Because the rate-determining step limits the rate of the overall reaction, the order of a
reaction can be deduced from the rate determining step.
Lets consider the following reaction:
2NO(g) + 2H2(g) 2H2O(g) + N2(g)
Table 7.2 shows the results of six experiments. In the first three experiments theconcentration
of H2 is increased by keeping the concentration of NO constant. By doubling the
concentration of H2, the rate is doubled and by tripling the concentration of H2, the rate is
tripled. So, the rate of reactionis directly proportional to the first power of concentration of
H2.
Table 7.3: Effect of change in concentrations
Rate ∝ [H2] of reactants on the rate of reaction
In the next three experiments, the [NO] in [H2] in Initial rate
concentration of H2 is kept constant. By (mol dm-) (atm min-)
(mol dm-)
doubling the concentration of NO, the rate
increases four times and by tripling the 0.0063 0.0013 0.0251
concentration of NO the rate is increased 0.006 0.002 0.050
nine times. So, the rate is proportional to the 0.006 0.003 0.0075
square of concentration of NO. 0.001 0.009 0.0063
2
Rate ∝ [NO] 0.002 0.009 0.025
The overall rate equation of reaction is, 0.003 0.009 0.056
Rate ∝ [H2][NO]2
or Rate = k[H2]1[NO]2
Hence, the reaction is a third order one. This final equation is the rate law for this reaction.
It should be kept in mind that rate law cannot be predicted from the balanced chemical
equation. The possible mechanism consisting of two steps for the reaction is as follows.
Slow
Step 1: 2NO(g) + H2(g) N2(g)+ H2O2(g) (rate determining step)
Fast
Step 2: H2O2 (g)+ H2(g) 2H2O(g)
The step 1 is slow and rate determining.
Another example is the reaction between nitrogen dioxide and fluorine gas:
2NO2(g) + F2(g) 2NO2F(g)
This reaction is first order in NO2, first order in F2 and second order overall. The
experimental rate law is first order in NO2 and in F2:
Rate = k [NO2][F2] (Observed)
The accepted mechanism for the reaction is:
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Slow .
Step 1: NO2(g) + F2 NO2F(g) + F(g) Rate = k1[NO2][F2]
. Fast .
Step 2: NO2(g) + F (g) NO2F(g) Rate = k2[NO2][F ]
The first step is slow and determines the rate, in agreement with the observed rate
expression. The second and fast step does not affect the reaction rate because fluorine
atoms react with NO2 as soon as they are produced.
Quick Check 7.9
An acidified solution of hydrogen peroxide reacts with iodide ions.
H2O2(aq) + 2H+(aq) + 2I–(aq) 2H2O(l) + I2(aq)
The rate equation for this reaction is
rate = [H2O2] [I–]
The mechanism below has been proposed for this reaction.
Slow
H2O2 + I– H2O + IO–
Fast
H+ + IO– HIO
Fast
HIO + H+ + I– I2 + H2O
Explain why this mechanism is consistent with the rate equation.

EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. The rate of reaction:
a) Increases as the reaction proceeds
b) Decreases as the reaction proceeds
c) Remains the same as the reaction proceeds
d) May decrease or increase as the reaction proceeds
II. Increasing the temperature of a chemical reaction increases the rate of reaction
because:
a) Both the collision frequency and collision energies of reactant molecules increase
b) Collision frequency of reactant molecules increases
c) Activation energy increase
d) Activation energy decrease

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III. Consider two reactions with different activation energies at the same temperature.
The reaction with the lower activation energy will have:
a) A smaller rate constant b) A larger rate constant
c) The same rate constant
d) A rate constant that depends on the enthalpy change
IV. The order of a chemical reaction, that is independent of concentration is:
a) Second order reaction b) First order reaction
c) Zero order reaction d) Pseudo first order reaction
V. On a Boltzmann distribution curve, the area under the curve represents:
a) Activation energy of the reaction.
b) Total number of molecules in the sample.
c) Average kinetic energy of the molecules.
d) Rate constant of the reaction.
VI. On a Boltzmann distribution curve, the activation energy (Ea) is represented by:
a) The height of the peak
b) The area under the entire curve
c) A vertical line drawn at a specific kinetic energy value
d) The difference between the peak and the X-axis
VII. If we double the concentration of a reactant, the rate increases by four times,
the reaction is:
a) Second order b) First order
c) Third order d) Zero order
VIII. The rate determining step in a multi-step reaction is:
a) Always the first step b) Always the last step
c) The slowest step d) The fastest step
IX. The reaction NO2 + CO → NO + CO2 occurs in two steps. What is the rate law
equation for this reaction?
2NO2 → NO + NO3 (k1) slow
NO3 + CO → CO2 + NO2 (k2) fast
a) R = k1 [NO2]3 b) R = k2 [NO3][CO]
c) R = k1 [NO2] d) R = k1 [NO2]2

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X. How does the presence of a catalyst affect the rate of a chemical reaction?
a) It always decreases the rate of the reaction.
b) It always increases the rate of the reaction.
c) It increases the rate of the forward and decreases the rate of the reverse reaction.
d) It increases the rate of both the forward and reverse reactions.
XI. On an energy profile diagram, the presence of a catalyst is represented by:
a) A higher peak representing the activation energy.
b) A lower peak representing the activation energy.
c) A change in the energy level of the reactants or products.
d) A shift in the equilibrium position.
XII. The units of the rate constant (k) for a reaction depend on the:
a) Activation energy of the reaction
b) Temperature of the reaction
c) Overall order of the reaction
d) Stoichiometry of the balanced chemical equation
XIII. A first-order reaction has a half-life (t1/2​) of 20 minutes. What is the value of its
rate constant (k)?
a) 0.05 min-1 b) 0.693 min-1
c) 0.0347 min-1 d) 13.86 min-1
SHORT ANSWER QUESTIONS
Q.2 Attempt the following short-answer questions:
a. What do you understand by the rate of a reaction?
b. Give the difference between enthalpy change of reaction and energy of activation of
reaction
c. Differentiate clearly between order and molecularity of a reaction.
d. Why the instantaneous rate changes during a reaction?
e. Briefly summarize the effects of temperature and surface area on the rates of reactions.
f. Justify that the radioactive decay is always a first order reaction.
g. A reaction is second order with respect to a reactant. How is the rate of reaction affected
if the concentration is doubled and reduced to half?
h. What is meant by half-life and what is it used for?
i. Why does wood burn more rapidly in pure oxygen than in air?
j. A catalyst lowers the activation energy of a chemical reaction. Illustrate it.
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k. The rate constant for a certain reaction is 3.5×10−4 s−1 at 25∘C.

l. What is the order of the reaction.? Explain based on the units of the rate constant.
m. If the initial concentration of the reactant is 0.50 mol dm−3, calculate the initial rate
of the reaction.
n. How would the rate of this reaction change if the concentration of the reactant were
doubled?
o. A certain first-order reaction has a rate constant of 2.5×10−3 s−1. Calculate the half-life
of the reaction in minutes.
p. A radioactive isotope decays by a first-order process with a half-life of 12 hours.
Calculate the rate constant for the decay in s−1.
DESCRIPTIVE QUESTIONS
Q.3 Relate the order of a reaction to the rate law for the reaction. How do you
distinguish between zero order, first order and second order reaction?
Q.4 How do you find the numerical value of a rate constant by initial and half-life
methods?
Q.5 How does the activation energy profile of an uncatalyzed reaction compare with
that of the catalyzed reaction?
Q. 6 The reaction between hydrogen peroxide (H2​O2​) and iodide ions (I−) in acidic
solution is believed to occur via the following mechanism:
Step 1: H2​O2​+ I− ⟶ H2​O + OI− (slow)
Step 2: OI− + H+ ⟶ HOI (fast)
Step 3: HOI + I− + H+ ⟶ H2​O + I2​ (fast)
i) Write the overall balanced equation for the reaction.
ii) Identify any intermediates and catalysts in this mechanism.
iii) What is the rate-determining step?
iv) Write the rate equation for the reaction, expressing it in terms of the
reactants in the overall reaction.
NUMERICAL PROBLEMS
Q.6 Calculate the reaction rate if the concentration of A is 0.5 M, the concentration
of B is 0.2 and the rate constant k is 4.0M-2s-1. Given the rate law for a reaction:
Rate = k[A][B]2.
Q.7 A first order reaction is found to have a rate constant, k = 5.5 × 10-14 s-1. Find the
half-life of the reaction.

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Q.8 Three experiments that have identical conditions were performed to measure
the initial rate of the reaction. 2HI(g) → H2(g) + I2(g)
Experiment [HI] (M) Rate (M/s)
1 0.015 1.1×10-3
2 0.030 4.4×10-3
3 0.045 9.9×10-3
Write the rate law for the reaction. Find the value and units of the specific rate
constant, k.

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CHEMICAL EQUILIBRIUM

8
Chemistry-XI

CHEMICAL EQUILIBRIUM
STUDENT LEARNING OUTCOMES [C-11-A-135 to C-11-A-148]

Describe the microscopic events that occur when a chemical system is in equilibrium. Define with
examples. (Understanding)
Differentiate between microscopic and macroscopic events in a chemical reaction. (Understanding)
Propose microscopic that account for observed macroscopic changes that take place during a shift in
equilibrium. (Understanding)
Describe what is meant by a reversible reaction and dynamic equilibrium in terms of the rate of
forward and reverse reactions being equal and the concentration of reactants and products remaining
constant. (Understanding)
Define dynamic equilibrium between two physical states. (Knowledge)
Deduce the equilibrium constant expression [Kc] from an equation for homogeneous reaction.
(Understanding)
Determine the relationship between different equilibrium constants (Kc) for the same reaction at the
same temperature. (Understanding)
Write the equilibrium expression for a given chemical reaction in terms of concentration, Kc, partial
pressure Kp, number of moles Kn and mole fraction Kx. (Application)
State the necessary conditions for equilibrium and the ways that equilibrium can be recognized.
(Knowledge)
State Le Chatelier’s Principle and be able to apply it to systems in equilibrium with changes in
concentration, pressure, temperature, or the addition of catalyst. (Knowledge)
Determine if Kc will increase or decrease when temperature is changed, given the equation for the
reaction. (Understanding)
Explain industrial applications of Le Chatelier’s Principle using Haber’s process and the contact
process as an example. (Understanding)
Discuss the industrial applications of chemical equilibria and how it can be used to optimize chemical
reactions to maximize yields and minimize waste products. (Understanding)
Use of concept of hydrolysis to explain why aqueous solutions of some salts are acidic or basic.
(Application)

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The reactions in which the reactants are completely consumed and converted into products
are called irreversible reactions. Such reactions stop when the limiting reactant is used
up. However, some reactions continue in both directions, i.e., forward and reverse, without
changing the concentration of reactants and products under the existing conditions. Such
reactions never stop and are called reversible reactions. When a reversible chemical
reaction takes place in a container which prevents the entry or escape of any of the
substances involved in the reaction, the quantities of these components change as some are
consumed and others are formed. These reactions eventually reach a stage called chemical
equilibrium. At this point, the concentrations of reactants and products become constant
and the rates of the forward and reverse reactions become equal.
This chapter will deal with the equilibria of reversible processes, both physical and
chemical changes. Examples of some reversible reactions are given below :
N2(g) + 3H2(g) 2NH3(g)
2NO2(g) N2O4(g)
PCl5(g) PCI3(g) + Cl2(g)
The double arrow tells that the reaction is reversible.
8.1 MACROSCOPIC EVENTS AND MICROSCOPIC EVENTS
8.1.1 Macroscopic Events
Macroscopic events refer to the phenomena that can be observed with the naked eye
without considering the individual particles or molecules involved in the process. Change
in colour, the evolution or absorption of heat, the formation of precipitate, evolution of a
gas, change in volume or pressure, change in the composition of a substance in a chemical
reaction are examples of macroscopic properties.
8.1.2 Microscopic Events
Microscopic events refer to the phenomena that cannot be observed with the naked eye.
The collisions between molecules, breaking and forming bonds, rearrangement of atoms in
molecules, loss. or gain of electrons are examples of microscopic events.

8.2 REVERSIBLE REACTIONS, MICROSCOPIC EVENTS

AND DYNAMIC EQUILIBRIUM
When a reversible reaction is at equilibrium, it would apparently seem to be static.
However, at microscopic level, the reaction never stops and molecules are continuously
under change. The reactant molecules convert into products, while at the same time, the
reverse process happens. To study at micro scale that affect the macroscopic properties of
the system.
Consider the reaction between steam and carbon monoxide under appropriate conditions.
On mixing these gases, macroscopic changes are observed (e.g., changes in concentration).
Suppose that the reaction is started with same number of moles of both reactants. When
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steam and carbon monoxide are mixed, a maximum number of collisions per second
between them will occur as microscopic events. Bonds in CO and H2O are broken and new
bonds are formed to produce H2 and CO2. Therefore, the forward reaction has its maximum
rate at the beginning. This leads to a decrease in the concentration of the reactants. As H2O
and CO are gradually used up, the forward reaction slows down.
H2O(g) + CO(g) H2(g) + CO2(g)
As the molecules of H2 and CO2 accumulate, the
reverse reaction also starts. With the increase in
the concentration of H2 and CO2, more and more [CO] or [H2O]

Concentration
collisions per second between these molecules will
occur as microscopic events. As bonds in H2 and CO2 Equilibrium
are broken, the bonds in CO and H2O are formed.
[CO2] or [H2]
This means that forward reaction starts with maximum
rate and gradually slows down, whereas at the start, the Time
rate of the reverse reaction is low, gradually increases, Figure 8.1 Plot of concentration vs time
and finally becomes constant.
H2(g) + CO2(g) H2O(g) + CO(g)
Eventually, a time comes when both reactions proceed at the same rate. The reaction at this
stage is said to be in chemical equilibrium and the concentration of reactants and products
become constant.
H2O(g) + CO(g) H2(g) + CO2(g)
Unless the system is somehow disturbed, no further changes in the concentrations will occur.
The state of a reversible reaction at which composition of the reaction mixture does not change
and forward and reverse rates are equal is called the state of chemical equilibrium.
The plots of the concentrations of reactants and products versus time for a general
reaction are shown in Figure 8.1. Suppose the reactant A is converted into the product
B in a chemical reaction. The graphs in the figure show different possibilities after the
equilibrium is established. At the equilibrium position, the concentrations of the reactant
and the product may be equal as shown in Figure 8.1 (a), or the amount of reactant may
be lower or greater than that of the product as shown in Figure 8.1 (b and c). However, for
all of these graphs, it is clear that after the equilibrium is established, the concentrations
become constant.
a) b) c)
A
A A
Concentration
Concentration

Equilibrium
Concentration

Equilibrium
Equilibrium

B B B

Time Time Time

Figure 8.1 Plot of concentration vs time (a) Reactant = Product (b) Reactant < Product
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 CHEMICAL EQUILIBRIUM Chemistry-XI

(c) Reactant > Product

When the concentrations of reactants and products become constant, the reaction may
apparently seem to have stopped. But it is not true. At the microscopic level, there is intense
activity. The individual molecules of the reactants continue to react. Individual product
molecules also react to combine to go back to the reactants. The rate of forward process,
is exactly equal to the rate of the reverse process. Therefore, it is a dynamic equilibrium.
The system is dynamic because the individual molecules are constantly reacting, but the
rates of forward and reverse reactions are the same.

8.3 RELATION BETWEEN MACROSCOPIC AND

MICROSCOPIC EVENTS
Macroscopic events are the result of multiple simultaneous microscopic events.
Understanding the microscopic events helps us to explain and predict the observed
macroscopic changes in the equilibrium system.
When a change in equilibrium occurs in a chemical reaction, the microscopic events that
explain the observed changes in equilibrium are the collisions and formation of new bonds
between particles or molecules. These collisions change the rates of forward and reverse
reactions, which are affected by activation energy and external factors. These microscopic
events collectively appear as macroscopic changes which are observable by naked eye.
Quick Check 8.1
a) Differentiate between macroscopic and microscopic events
b) The equilibrium is dynamic in nature, explain in terms of microscopic events.
c) In the reaction H2O(g) + CO(g) H2(g) + CO2(g), the concentration
of the products is higher at the equilibrium stage.
i. Plot a graph between concentrations of reactants and products and time.
ii. Plot a graph between rate of the reaction with respect to time.

8.4 DYNAMIC EQUILIBRIUM BETWEEN TWO PHYSICAL

STATES
Dynamic equilibrium is a state in a reversible process where the rate of change in one
direction is equal to the rate of change in the opposite direction. In other words, although
there are continuous changes taking place, no net change in the system as a whole is
observed. When a reversible phase change takes place for a substance, there is also a
dynamic equilibrium between the two physical states. For example, at 0 ℃, ice and water
coexist in equilibrium. Water changes into ice whereas ice converts back into water at the
same rate.
Relationship between dynamic equilibrium and vapor pressure
Studying the behaviour of liquids and their vapour pressures is a significant concept in
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chemistry. When a liquid is placed in a closed container, some of the liquid molecules near
the surface have enough energy to escape into the gaseous phase. This process is called
evaporation. As more molecules escape into the gaseous phase, the pressure exerted by
the gas molecules on the walls of the vessel increases. At the same time, molecules in
vapour phase can also collide with the liquid surface and be captured again by the liquid,
a process known as condensation.
Evaporation
Liquid Gas
Condensation
As evaporation and condensation continue, the rate of these processes will eventually
become equal, and a state of dynamic equilibrium is achieved. In this state, the number
of liquid molecules transforming into the gas phase equals the number of gas molecules
returning to the liquid phase. At dynamic equilibrium, the vapor pressure remains constant
at a given temperature, as long as the system is undisturbed.
As the temperature increases, the average kinetic energy of the liquid molecules also
increases. This leads to a higher rate of evaporation, which in turn increases the vapor
pressure. Also, the rate of condensation increases at the higher temperature. Finally, the
system will reach a new state of dynamic equilibrium, with a higher equilibrium vapor
pressure. In short, dynamic equilibrium in terms of the vapor pressure of a liquid describes
the state at which the rates of evaporation and condensation are equal.
Quick Check 8.2
a) The dynamic equilibrium exists between water and its vapour at 100℃. Justify the statement.
b) Do you think that dynamic equilibrium exists between ice and water at 0℃? If yes, explain.

8.5 CONDITIONS FOR EQUILIBRIUM

The equilibrium should be studied when the following conditions are fulfilled:
1. The state of equilibrium only applies to reversible reactions.
2. The equilibrium can be established only if the reaction vessel is closed. No part of the
reactants and products is allowed to escape out.

a) b)

CaCO3(s) CaO(s) + CO2(g) CaCO3(s) CaO(s) + CO2(g)

CaCO3(s) CaO(s) CO2(g)
Figure 8.2 (a) Equilibrium is established when the system is closed
(b) Equilibrium can not be established in the open system.
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8.6 CHARACTERISTICS OF CHEMICAL EQUILIBRIUM

Important features of equilibrium are as follows:
1. At the stage of chemical equilibrium, the concentrations of reactants and products
remain constant.
2. The state of equilibrium in a reversible reaction can be approached from either side
whether we start with reactants or products.
3. A catalyst does not change the equilibrium position and the equilibrium constant of the
reaction. It helps to attain the equilibrium earlier.
4. The value of equilibrium constant does not depend upon the initial concentrations of
reactants, rather it is constants and depends on temperature only.

Keep in Mind!
If pure solids or pure liquids are involved in an equilibrium system, their concentrations are not included in
the equilibrium constant expression. This is because the change in concentration of any pure solid or liquid
has no effect on the equilibrium constant.

8.7 TYPES OF EQUILIBRIUM

With respect to the physical states of reactants and products, there are two types of chemical
equilibrium.
8.7.1 Homogeneous Equilibrium
An equilibrium system in which all of the reactants and products are in the same phase.
The following are examples of homogeneous equilibria:
N2(g) + 3H2(g) 2NH3(g)
2SO2(g) + O2(g) 2SO3(g)
CH3COOH(l)+ C2 H5OH(l) CH3COOC2H5(l) + H2O(l)
Heterogeneous Equilibrium
An equilibrium in which the reactants and products are in more than one phases is called
heterogeneous equilibrium. The following are examples of heterogeneous equilibrium:
CaCO3(s) CaO(s) + CO2(g)
C(s) + H2O(g) CO(g) + H2(g)
3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)

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Quick Check 8.3

a) Differentiate between homogeneous and heterogeneous equilibria
i. Condition for this equilibrium requires the closed cap of the bottle. Why?
ii. When the cap of the bottle is removed, to which direction the equilibrium shifts?
b) Why do the rates of forward reactions slow down when a reversible reaction approaches the equilibrium
stage?
c) In soda water bottles, gaseous CO2 is in equilibrium with the aqueous CO2 (HCO3– and H+).
CO2(g) + H2O(l) HCO3-(aq) + H+(aq)

8.8 EQUILIBRIUM CONSTANT AND POSITION OF

EQUILIBRIUM
The position of equilibrium refers to the relative amounts of products and reactants present
in an equilibrium mixture.
In 1864, the Norwegian chemists C. Guldberg (1836–1902) and P. Waage (1833–1900)
carefully measured the compositions of many reaction systems at equilibrium. They
discovered that for any reversible reaction, the ratio of the product of the equilibrium
concentrations of the products (raised to their coefficients in the balanced chemical
equation) to the product of the equilibrium concentrations of the reactants (raised to their
coefficients in the balanced chemical equation) is always a constant under a given set of
conditions.
Consider the general reaction:
aA + bB cC + dD
where A and B are reactants, C and D are products, and a, b, c, and d are the stoichiometric
coefficients in the balanced chemical equation.
[C]c [D]d
Kc =
[A]n [B]b

The rate of the chemical reaction is directly proportional to the active masses of the
reactants, raised to the coefficients present in the balanced equation. By the term active
mass, we mean the molar concentration. It is expressed in moles dm−3. This concentration
is expressed by square brackets [ ].
Let us consider a general reaction
A+B C+D
According to the Law of mass action,
Rate of forward reaction α [A][B]
= kf [A][B]
‘kf’ is the proportionality constant, and is known as forward rate constant.
Rate of reverse reaction α [C][D]
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= kr [C][D]
‘kr’ is the proportionality constant and is known as reverse rate constant.
At the equilibrium stage, the forward and the reverse rates are equal. Hence,
kf[A][B] = kr[C][D]
kf [C][D]
=
kr [A][B]
The left side of this equation is the ratio of two rate constants, so it gives another constant
called the equilibrium constant (Kc).
k
Kc = f
kr
[C][D]
So, Kc =
[A][B]

This equation is known as equilibrium constant expression.

Consider the following reversible reaction,
aA + bB cC + dD
where a, b, c and d are the coefficients of balanced equation.
[C]c [D]d
Then Kc =
[A]a [B]b
8.8.1 Equilibrium Constant Expressions of Some Important Reactions
(i) N2 (g) + 3H2 (g) 2NH3 (g)
[NH3]2
Kc =
[N2] [H2]3
(ii) 2N2O5 (g) 4NO2 (g) + O2 (g)
4
Kc = [NO2] [O2]
[N2O5]2
Sample Problem 8.1
Ethanol reacts with ethanoic acid to form ethyl ethanoate and water.
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
Ethanoic acid Ethanol Ethyl Ethanoate Water
500 cm3 of the reaction mixture at equilibrium contained 0.235 mol of ethanoic acid and
0.0350 mol of ethanol together with 0.182 mol of ethyl ethanoate and 0.182 mol of water.
Use this data to calculate a value of Kc for this reaction.
Step 1 Write out the balanced chemical equation with the concentrations beneath each
substance.
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CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)

0.235 mol 0.0350 mol 0.182 mol 0.182 mol
0.5 dm3 0.5 dm3 0.5 dm3 0.5 dm3
0.470 mol dm–3 0.070 mol dm–3 0.364 mol dm–3 0.364 mol dm–3
Step 2 Write the equilibrium constant for this reaction in terms of concentrations.
[CH3COOC2H5] [H2O] (0.364 mol dm-3) (0.0364 mol dm-3)
Kc = =
[CH3COOH] [C2H5OH] (0.470 mol dm-3) (0.070 mol dm-3)
Step 3 Substitute the equilibrium concentrations into the expression
Kc = 4.03 (to 3 significant figures)
Step 4 Add the correct units by referring back to the equilibrium expression: The units of
mol dm–3 cancel out, so Kc has no units. Therefore, Kc = 4.03.
Sample Problem 8.2
Propanone reacts with hydrogen cyanide as follows:
CH3COCH3 (l) + HCN (g) CH3C(OH)(CN)CH3 (l)
Propanone Hydrogen cyanide Product
A mixture of 0.0500 mol dm–3 propanone and 0.0500 mol dm–3 hydrogen cyanide is left to
reach equilibrium at room temperature. At equilibrium the concentration of the product is
0.0233 mol dm–3. Calculate Kc for this reaction.
Solution:
Step 1 Write out the balanced chemical equation with all the data underneath:

CH3COCH3 (l) + HCN (g) CH3C(OH)(CN)CH3 (l)

Step 2 Calculate the equilibrium concentrations of the reactants. The chemical equation
shows that for every mole of product formed, 1 mole of CH3COCH3 and 1 mole of HCN
are consumed. So the equilibrium concentrations are as follows:
CH3COCH3; 0.0500 – 0.0233 = 0.0267 mol dm–3
HCN; 0.0500 – 0.0233 = 0.0267 mol dm–3
Step 3 Write the equilibrium constant for this reaction in terms of concentrations:
[CH3C(OH)(CN)CH3] (0.0233 mol dm-3)
Kc = =
[CH3COH3] [HCN] (0.05 mol dm-3) (0.05 mol dm-3)
Step 4 Substitute the equilibrium concentrations into the expression

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Kc = 32.7 mol dm–3

Quick Check 8.4

a) Write Kc for the following reactions:
i. Sn2+(aq) + 2Fe3+(aq) Sn4+(aq) + 2Fe2+(aq)
ii. 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
iii. PCl5(g) PCl3(g) + Cl2(g)
b) Calculate the value of Kc for the following reaction using the information below:
H2(g) + CO2(g) H2O(g) + CO(g)
Initial conc. of H2(g) = 10.00 mol dm–3.
Initial conc. of CO2(g) = 10.00 mol dm–3.
Equilibrium conc. of CO(g) = 9.47 mol dm–3.

8.8.2 Units of Equilibrium Constants

When the number of moles of reactants and products in balanced chemical equations
are equal, then units are canceled out, and equilibrium constant does not have any unit.
The ester formation reaction happens in solution state, and number of moles of reactants
and products are equal. The Kc will have no units.
CH3COOH(aq) + C2H5OH(aq) CH3COOC2H5(aq) + H2O(l)
[CH3COOC2H5] [H2O] mol dm–3 × mol dm–3
Kc = = = no umits
[CH3COOH(aq)] [C2H5OH(aq)] mol dm–3 × mol dm–3
When the number of moles are unequal, then value of equilibrium constant depend
upon the units of reactants and products used. In the synthesis of NH3 by Haber’s
process, the units of reactants and products are not cancelled.
N2(g) + 3H2(g) 2NH3(g)
[NH3(g)]2 [mols dm–3]2
Kc = =
[N2(g)] [H2(g)]3 [mol dm–3] [mol dm–3]3

1
=
[mol dm–3]2

= mol–2 dm6
8.9 RELATIONSHIPS BETWEEN VARIOUS EQUILIBRIUM
CONSTANTS
There are four different types of quantities which may be used to calculate the equilibrium
constants of reversible reaction. Let the general reaction be,
aA + bB cC + dD
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(1) When the concentrations of reactants and products are in mole dm−3, then equilibrium
constant is written as:
[C]c [D]d
Kc = (1)
[A]a [B]b
Square brackets [ ] are used for mole dm−3.
(2) When the concentrations are expressed in terms of partial pressures (p) for gaseous
reactants and products, then
pCc . pdD
Kp = (2)
pAa . pBb
(3) When the concentrations are expressed in terms of number of moles, then
nCc . nD
d
Kn = (3)
nAa . nbB
(4) When the concentrations are expressed in terms of mole fractions, (X) then
XcC . XdD
Kx = (4)
XAa . XbB
The relationships between these equilibrium constants are as follows:
Kp = Kc (RT)∆n (5)
Kp = Kx (P) ∆n (6)
Kp = Kn (N) ∆n (7)
Where:
R = General gas constant
T = Absolute temperature of the system
P = Pressure of the system
N = Total number of moles of reactants and products
∆n = Difference of number of moles of products and reactants in the balanced chemical
equation
It depends upon the value of ‘∆n’ that which of the equilibrium constants is bigger or
smaller than the other. Anyhow, if the number of moles of reactants and products in a
balanced chemical equation are equal, and all the constants have equal values.
That is,
∆n = 0 then Kp = Kc = Kx = Kn
Hence, whichever concentration units are used, the equilibrium constants are same.
Sample Problem 8.3
N2(g) and H2(g) combine to form NH3(g). The value of Kc at 500°C is 6.0 × 10−2. Calculate

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the numerical value of Kp for this reaction.

Solution:
N2(g) + 3H2(g) 2NH3(g)
Kc = 6.0 × 10−2
T = 500°C + 273 = 773 K
R = 0.0821 dm3 atm K−1 mol−1
Kp = ?
The formula for conversion of Kc to Kp is,
Kp = Kc(RT)∆n
∆n = Number of moles of product − Number of moles of reactants
∆n = 2 − 4 = −2
Substituting these values in the expression
Kp = 6.0 × 10−2 (0.0821 dm3 atm K−1 mol−1 × 773 K)−2
= 6.0 × 10−2 (63.5 dm3 atm mol−1)−2
6.0 × 10–2 0.06
Kp = =
(63.5)2 4032.25
Kp = 1.4 × 10–5
So, the value of Kp is less than Kc.
Sample Problem 8.4
In the reaction
2SO2(g) + O2(g) 2SO3(g)
the equilibrium partial pressures at constant temperature are SO2 = 1.0 x 106 Pa, O2 = 7.0
x 106 Pa, SO3 = 8.0 x 106 Pa. Calculate the value of Kp for this reaction.
Solution
Step 1 Write the equilibrium expression for the reaction in terms of partial pressures.
P2SO
3
Kp = 2
P SO × PO
2 2

Step 2 Substitute the equilibrium concentrations into the expression.

(8.0 × 106)2
Kp = = 9.1 x 10–6 Pa–1
(1.0 × 106)2 × 7.0 × 106

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Quick Check 8.5

a) Decide the comparative magnitudes of Kc and Kp, for the following reversible reactions.
i) Ammonia synthesis b) Dissociation of PCl5
(b) Nitrogen reacts with hydrogen to form ammonia.
N2(g) + 3H2(g) 2NH3(g)
The pressure exerted by this mixture of hydrogen, nitrogen and ammonia at constant temperature is 2.0 x
107 Pa. Under these conditions, the partial pressure of nitrogen is 1.5 x 107 Pa and the partial pressure of
hydrogen is 0.4 x 107 Pa. Calculate the value of Kp for this reaction.

8.10 POSITION OF EQUILIBRIUM AND REACTION

CONDITIONS
The position of equilibrium refers to the relative amounts of products and reactants present
in an equilibrium mixture.
If a system in equilibrium is disturbed.

If the concentration of products is increased relative to the reactants, we say that the
position of equilibrium has shifted to the left.

If the concentration of products is decreased relative to the reactants, we say that the
position of equilibrium has shifted to the right.

8.11 LE-CHATELIER’S PRINCIPLE

Le-Chatelier’s principle can be stated as follows:
“If a system in equilibrium is disturbed, it behaves in such a way as to nullify the effect of
that disturbance”.
Le-Chatelier’s principle describes what happens to a Henry-Louis Le Chatelier
system when something momentarily takes it away from
equilibrium.
8.11.1 Applications of Le-Chatelier’s Principle
Some of the most common applications of this principle
with reference to certain physical and chemical equilibria
are discussed below:

i) Effect of change in concentration

ii) Effect of change in pressure

(1850-1936)
iii) Effect of change in temperature. A French chemist of the late 19th and
early 20th centuries. He proposed the
iv) Effect of catalyst on equilibrium. Le-Chatlier Principle, a significant
achievement in chemistry

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8.12 THE EFFECT OF CHANGE OF CONCENTRATIONS

If the system is at the equilibrium position and a certain amount of one of the reactants or
products is added or removed, the equilibrium position is disturbed.
There are four possibilities for the change in concentrations of reactants and products.
(I) Hydrolysis of BiCl3
Consider the following reversible reaction in which BiCl3 reacts with water to give a white
insoluble compound, BiOCl.
BiCl3 + H2O BiOCl + 2HCl
The expression for this reaction can be written as
[BiOCl] [HCl]2
Kc =
[BiCl3] [H2O]
When water is added in BiCl3 solution, it becomes cloudy due to the formation of white
precipitate ofBiOCl. At equilibrium, a certain amount of BiOCl and HCl has been produced
and certain number of moles of BiCl3 are left behind. If a few moles of BiCl3 are added at
equilibrium, the reaction is pushed to the forward direction.
The addition of BiCl3 or H2O disturbs the equilibrium position. To re-establish the
equilibrium, more BiOCl and HCl are produced. In other words, the reaction is pushed to
the forward direction. Kc remains constant, but equilibrium position has changed.
The addition of BiOCl or HCl, or both disturbs the equilibrium position. To re-establish the
equilibrium, more BiCl3 is produced and the reaction moves in the reverse direction. The
Kc remains the constant, but position of equilibrium changes.
If a certain amount of BiCl3 is removed at equilibrium stage, the reaction will move in the
reverse direction to compensate that change. A new equilibrium position is established, Kc
being constant.
If a certain amount of BiOCl or HCl or both is removed at equilibrium stage, the reaction
will move in the forward direction to compensate that change. A new equilibrium position
is established; however, Kc remains constant.

8.13 THE EFFECT OF CHANGE IN PRESSURE OR VOLUME

The effect of change of volume or pressure is not applicable when
(a) The system does not involve gaseous components.
(b) The number of moles of reactants and products are equal in gaseous phase homogeneous
equilibrium.
n reactants = n products
This effect can only be discussed if the gaseous moles of reactants and products are unequal.
n reactants ≠ n products

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In order to explain this effect, let us consider the synthesis of ammonia by Haber’s process.
N2(g) + 3H2(g) 2NH3(g)
a) Increase in pressure or decrease in volume:
For the forward reaction, the number of moles and hence volume decreases. At equilibrium
stage the volume occupied by the mixture is less than the volume at the initial stage under
the given conditions. So, if pressure is increased at equilibrium, more ammonia is produced.
It means, that reaction is shifted to the forward direction.
b) Decrease in pressure or increase in volume:
If the pressure is decreased or volume is increased, the reaction will move to that side,
where the reaction occupies greater volume. Ammonia synthesis is shifted to the reverse
direction.
Quick Check 8.6
The change of volume or pressure for the following reactions only changes the equilibrium position but not the
equilibrium constant. How the direction of reaction changes for each of the following reactions.
2H2(g) + O2(g) 2H2O(g) (Increasing P )
2CO(g) + O2(g) 2CO2(g) (Increasing V)
N2O4(g) 2NO2(g) (Increasing P)
2SO2(g) + O2(g) 2SO3(g) (Increasing V)

8.14 THE EFFECT OF CHANGE IN TEMPERATURE

Le Chatelier’s Principle can be used to predict the direction of a reaction with a change
in temperature. Temperature is the only factor that also affects the value of equilibrium
constant (Kc).
For an exothermic reaction, an increase in temperature (adding heat) favours the reverse
reaction. A decrease in temperature (removing heat) favours the forward reaction.
The equation for the conversion of SO2 to SO3 is given below:
2SO2(g) + O2(g) 2SO3(g) ∆H°= –198 kJ
According to the Le-Chatelier’s principle, an increase in temperature will shift the reaction
from right to left.
2SO2(g) + O2(g) 2SO3(g)
As a result of this change, the concentration of SO3 will decrease and concentrations of
SO2 and O2 will increase. Therefore, the value of the equilibrium constant will decrease.
The equilibrium will shift towards left. The decrease in temperature will favour the forward
reaction and the formation of the product. The production of SO3 is favoured at a lower
temperature. On the other hand, an increase in temperature will shift the reaction from left
to right.
2SO2(g) + O2(g) 2SO3(g)
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Due to this change, the concentration of SO3 will increase and concentrations of SO2 and
O2 will decrease. Therefore, the value of the equilibrium constant will increase.
The equilibrium will shift towards right. The increase in temperature will favour the
reverse reaction and the formation of the reactants. The production of SO3 is not favoured
at a higher temperature. Kc for this reaction is 2.8 x 102 at 1000 K; whereas, at 298 K the
value of Kc is 1 x 1026.
For an endothermic reaction, an increase in temperature (adding heat) favours the
forward reaction. A decrease in temperature (removing heat) favours the reverse reaction.
The equation for the conversion of N2O4 to NO2 is given below:
N2O4(g) 2NO2(g) ∆H°= +57.2 kJ
According to the Le-Chatelier’s Principle, an increase in temperature will shift the reaction
from left to right.
N2O4(g) 2NO2(g)
As a result of this change, the concentration of N2O4 will decrease and concentration of
NO2 will increase. Therefore, the value of the equilibrium constant (Kc) will increase. The
equilibrium will shift towards right. The increase in temperature will favour the forward
reaction and the formation of the product.
On the other hand, a decrease in temperature will shift the reaction from right to left. The
decrease in temperature will favour the reverse reaction and the formation of the reactant.
N2O4(g) 2NO2(g)
Kc for this reaction is 7.7 x 10-5 at 273 K, whereas 0.4 at 373 K.

8.15 EFFECT OF CATALYST ON EQUILIBRIUM

A catalyst is that substance which increases y

the rate of a chemical reaction without

itself being consumed in the reaction. The activated state
Energy

catalyst does not change the equilibrium

position and the equilibrium constant of a
Ea (uncatalyzed reaction)
chemical reaction. It speeds up the rate at
which equilibrium is attained. It means that
the yield of the chemical reaction remains activated state

the same.
E'a (catalyzed reaction)
A catalyst provides new path of lower
activation energy for a reaction. If we plot H
Reactants Products
a graph between reaction coordinate on
O
x-axis and potential energy of the chemical Reaction coordinate X

reaction on y-axis, then the maxima of the Figure 8.3 Effect of a catalyst on Reversible Reactions.
Fig (8.3): Effect of a catalyst on Reversible Reactions.

curve become lower in the presence of a catalyst as shown in Figure 8.3.

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8.16 INDUSTRIAL APPLICATIONS OF CHEMICAL

EQUILIBRIUM
8.16.1 Synthesis Of Ammonia By Haber’s Process
It is one of the basic needs of industry to have maximum yield of the product. We can
apply the concept of equilibrium in order to have the maximum yield from the industrial
synthesis of ammonia.
Ammonia synthesis from nitrogen and hydrogen is a reversible process.
N2(g) + 3H2(g) 2NH3(g) ∆H = − 46.11 kJ mol−1
The maximum yield of ammonia can be achieved by the following ways:
1. Decrease the concentration of ammonia by removing it from the reaction vessel from
time to time. Equilibrium will shift to the forward direction in accordance with Le-
Chatelier’s principle.
2. Since, four moles of reactants combine to give two moles of products, reaction happens
with the decreasing volume. High pressure will shift the equilibrium position to the
right to give more and more ammonia.
3. This is an exothermic reaction. By decreasing temperature, it will shift to the forward
direction according to Le-Chatelier’s principle.
When we look at the Table 8.2 given below and the Figure 8.3, then it becomes clear that
the effect of pressure and temperature on the yield of ammonia is very prominent. The
most complete conversion is 98.3% at 473 K (200°C) and 1000 atmospheric pressure.

100
Table (8.1):
Effect of Temperature 90
1000 atm
on Kc for Ammonia Synthesis. 80
70 600 atm Industrial
Yield of NH3 (%)

T(K) Kc conditions
60
200 7.15 × 1015 50
300 atm

300 2.69 × 108 40

30
400 3.94 × 104 100 atm
20
500 1.72 × 102 10 10 atm
0
600 4.53 × 100 200 250 300 350 400 450 500 550 600 650 700

700 2.96 × 10−1 (°C)

Fig (8.4) : Percent yield of ammonia vs. Temperature(°C)
800 3.96 × 10−2 at five different operating pressures. At very high pressure
and low temperature (top left), the yield is high, but the
rate of formation is low. Industrial conditions (circle) are
between 200 and 300 atm at about 400°C

At 200°C, the yield is being favoured but the rate of reaction becomes very slow and the
process becomes uneconomical. So, the temperature is raised to a moderate level i.e. 400
ºC and a catalyst is used to increase the rate. If we want to achieve the same rate without a

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catalyst then we require much higher temperature, which lowers the yield.
Optimum conditions to get best yield of ammonia
The most suitable conditions to get maximum yield of ammonia are:
a) Pressure between 200-300 atmospheres
b) Temperature around 673 K (400°C)
c) Pieces of iron crystals present in a fused mixture of MgO, Al2O3 and SiO2, as catalyst
8.16.2 PREPARATION OF SULPHUR TRIOXIDE
To manufacture H2SO4, sulphur trioxide gas is produced from SO2 and O2, in a reversible
process.
2SO2(g) + O2(g) 2SO3(g) ∆H = −97.9 kJ mol−1
According to Le-Chatelier’s principle, a high pressure and low temperature are the essential
conditions to have better yield of SO3. At low temperature, the equilibrium constant for the
formation of SO3 is large, but equilibrium is achieved very slowly. As the temperature is
raised, the rate increases but the yield of SO3 drops off.
The following Table 8.2 helps us to understand the parameters, when pressure is maintained
at 1 atmosphere.
Table 8.2 Effect of temperature on equilibrium position of SO3 formation

1. Temperature (°C) 200 300 400 500 600 700

2. Kc 5500 690 160 55 25 13
3. Mole % of SO3 98 91 75 61 46 31

Optimum conditions
In order to have a best yield of SO3, within a reasonable time, a mixture of SO2(g) and O2(g)
(air) at one atmospheric pressure is passed over a solid catalyst, such as V2O5, But due to
the exothermic reaction, the temperature of the gas increases to 600 °C. The equilibrium
mixture is recycled at low temperature of 400-500 °C to increase the yield of SO3(g).

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Quick Check 8.6

Look at the information given in the table below:

i) How does the proportion of ammonia in the N2/H2/NH3 system change as the temperature increases?
ii) What is the value of ∆Hº for this reactions
N2(g) + 3H2(g) 2NH3(g)
What is the value of Kp for the raection at 400 K?
iii) Use Le Chatelier's principle to predict the effect of increasing temperature on Kp for the reaction in part ii.

EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. For which system, does the equilibrium constant, Kc has units of (concentration)−1?
a) N2 + 3H2 2NH3 b) H2 + I2 2HI
c) 2NO2 N2O4 d) 2HF H 2 + F2
II. Which statement about the following equilibrium is correct?
2SO2(g) + O2(g) 2SO3(g) ∆H = −197.9 kJmol−1
a) The value of Kp falls with a rise in temperature.
b) The value of Kp falls with increasing pressure.
c) Adding V2O5 catalyst increase the equilibrium yield of sulphur trioxide.
d) The value of Kp is equal to Kc.

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III. 2SO3(g) 2SO2(g) + O2(g)

The conventional equilibrium constant expression (Kc) for the system as
described by the above equation is:
a) [SO2]2/[SO3] b) [SO2]2[O2]/[SO3]2
c) [SO3]2/[SO3]2[O2] d) [SO2][O2]
IV. A saturated solution represents a dynamic equilibrium. Macroscopically, the
concentration of dissolved solute is constant. Microscopically, this occurs because:
a) No more solute particles are dissolving.
b) The rate of dissolution of solute is zero.
c) Solute particles are dissolving and precipitating at the same rate.
d) All solute particles have dissolved.
V. Which of the following statements correctly describes the effect of temperature
on the equilibrium constant?
a) Kc is directly proportional to temperature.
b) Kc is inversely proportional to temperature.
c) Kc depends on the enthalpy change of the reaction.
d) Temperature has no effect on the value of Kc.
​
VI. Consider the gas-phase equilibrium system represented by the equation:
2H2O(g) 2H2(g) + O2(g)
Given that the forward reaction is endothermic, which of the following changes
will decrease the equilibrium amount of H2O?
a) Adding more oxygen
b) Adding a solid phase catalyst
c) Decreasing the volume of the container (the total pressure increases)
d) Increasing the temperature at constant pressure
VII. Kc = 0.040 for the reaction given below at 450 oC:
PCl5(g) PCl3(g) + Cl2(g)
Evaluate Kp for the reaction at 450 oC.
a) 0.40 b) 0.64
c) 2.4 d) 0.052
VIII. In which of the following gaseous equilibria, pressure has no effect on the
equilibrium position?
a) 2NO2(g) ⇌ N2O4(g) b) PCl5(g) ⇌ PCl3(g) + Cl2(g)
c) CO(g)+H2O(g) ⇌ CO2(g) + H2(g) d) 2SO2(g) + O2(g) ⇌ 2SO3(g)
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IX. Consider the equilibrium 2H2​(g)+O2​(g) ⇌ 2H2​O(g). If the concentration of H2O(g)

is increased, the concentrations of H2​(g) and O2​(g) will:
a) Increase. b) Decrease.
c) Remain the same. d) Change irregularly
X. For a specific reaction, the value of the equilibrium constant, Kc:
a) always remains the same at different reaction conditions.
b) increases if the concentration of one of the products is increased.
c) changes with changes in the temperature.
d) increases if the concentration of one of the reactants is increased.
XI. For a saturated solution of a salt in water, a dynamic equilibrium is between:
a) The dissolved ions and the undissolved solid salt
b) The solute and the solvent molecules
c) The solid salt and the water molecules
d) The hydrated ions and the water molecules in the bulk solvent

SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. What is meant by the state of chemical equilibrium?
b. Define reversible reaction. Give an example.
c. Decide the comparative magnitudes of Kc and Kp, for the following reversible reactions.
(i) Ammonia synthesis (ii) Dissociation of PCl5
d. The change of volume disturbs the equilibrium position for some of the gas phase
reactions but not the equilibrium constant.
e. Mention the characteristics of chemical equilibrium.
f. Reversible reaction attains the position of equilibrium which is dynamic in nature and
not static. Explain it.
g. Why do the rates of forward reactions slow down when a reversible reaction approaches
the equilibrium stage?
h. Why ice at 0 °C can be melted by applying pressure without supply of heat from
outside?
i. Write two conditions of equilibrium constant.
j. At 445 oC, Kc for the following reaction is 0.020.
2HI(g) H2(g) + I2(g)
A mixture of H2, I2, and HI in a vessel at 445 oC has the following concentrations:
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[HI] = 2.0 M, [H2] = 0.50 M and [I2] = 0.10 M. Which one of the following statements
concerning the reaction quotient, Qc, is TRUE for the above system?
i) Qc = Kc; the system is at equilibrium.
ii) Qc is less than Kc; more H2 and I2 will be produced.
iii) Qc is less than Kc; more HI will be produced.
iv) Qc is greater than Kc; more H2 and I2 will be produced.
k. The reversible reaction:
2SO2(g) + O2(g) 2SO3(g)
has come to equilibrium in a vessel of specific volume at a given temperature. Before
the reaction began, the concentrations of the reactants were 0.060 mol/dm3 of SO2
and 0.050 mol/dm3 of O2. After equilibrium is reached, the concentration of SO3 is
0.040 mol/ dm3. What is the equilibrium concentration of O2?

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 ACID-BASE CHEMISTRY

9
Chemistry-XI

ACID-BASE
CHEMISTRY
STUDENT LEARNING OUTCOMES [C-11-A-149 to C-11-A-165]
Define conjugate acid base pairs. (Understanding)
Identify conjugate acid base pairs in reactions. (Understanding)
Distinguish that Lewis acids accept lone pair, and Lewis bases donate lone pair to make a
coordinate covalent bond. (Understanding)
Define mathematically the terms Kw, pH, Ka and pKa and use them in calculations. (Application)
(Kb and the equation K w = Ka × Kb will not be tested).
Calculate [H+(aq) and pH values for: (Application)
(a) strong acids (b) strong alkalis (c) weak acids (d) weak alkalies.
Calculate the [H3O+] given the Ka and molar concentration of weak acid. (Application)
Apply the concept of the common ion effect to describe why the solubility of a substance
changes when it is dissolved in a solution containing a common ion. (Application)
Calculate the pH of buffer solutions in given appropriate data. (Application)
Construct an expression for Ksp. (Application)
Demonstrate the ability to comprehend and effectively apply the concept of solubility
product. (Ksp). (Application)
Perform calculations using Ksp values and concentration of a common ion. (Application)
Calculate concentrations of ions of slightly soluble salts. (Application)
Calculate Ksp from concentrations and vice versa. (Application)
Use the concept of hydrolysis to explain why aqueous solutions of some salts are acidic or
basic. (Understanding)
Apply the concept of conjugate acid and conjugate base on salt hydrolysis. (Application)
Select suitable indicators for acid-alkali titration, given appropriate data (pKa values will
not be used). (Understanding)
Perform acid-base titration to calculate molarity and strength of given sample solutions.
(Application)

From the earliest days of experimental chemistry, scientists have recognized acids and
bases that have distinct characteristic properties. Acids have a sour taste; bases are bitter.
Also, acids and bases change the color of certain dyes called indicators, such as litmus and
phenolphthalein. Acids change litmus from blue to red and basic phenolphthalein from
pink to colorless. Bases change litmus
from red to blue and phenolphthalein Interesting Information
from colorless to pink. As you can see Acidity in our stomachs is due to excess HCl. It is
from these color changes, acids and treated by taking mild bases such as, baking soda
bases neutralize each other. During
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neutralization, acids and bases react with each other to produce ionic substances called
salts.

9.1 BRONSTED-LOWRY CONCEPT

In 1923, the Danish chemist J.N. Bronsted and the English chemist T.M. Lowry
independently expanded the Arrhenius theory of acid-base. The limitations of Arhenius
theory is that it describes the reaction of an acid and base only in the aqueous medium.
There are many reactions that occur in solvents other than water or in the absence of
any solvent. Bronsted-Lowry pointed out that acid–base reactions can be seen as proton-
transfer reactions and that acids and bases can be defined in terms of this proton (H+)
transfer. According to the Bronsted–Lowry concept, an acid is the species donating a
proton in a proton-transfer reaction and a base is the species accepting the proton.
When HCl dissolves in water, an H+ ion (a proton) is transferred from HCl to water, where
it becomes attached to a lone pair of electrons on the O atom and forms H3O+. In effect,
HCl (the acid) has donated the H+ and H2O (the base) has accepted it.
HCl(g) + H2O() H3O+(aq) + Cl–(aq)
Proton donor Proton acceptor Conjugate acid Conjugate base
A species formed after a Bronsted base accepts a proton from the acid is called the conjugate
acid. The hydronium ion (H3O+) is the conjugate acid of water. A species formed when an
acid donates a proton to a base is called the conjugate base. HCl-Cl- and H2O-H3O+ are
conjugate acid-base pairs.
When ammonia dissolves in water, proton transfer also occurs. An H+ from H2O attaches to
the N atom’s lone pair and NH4+ and OH– are formed . With fewer H+, the water molecule
becomes OH- ion:
NH3(g) + H2O () OH-(aq) + NH4+ (aq)
Base Acid Conjugate base Conjugate base
In this case, H2O (the acid) has donated the proton and NH3 (the base) has accepted it.
NH3-NH4+ and H2O-OH- are conjugate acid-base pair.
The above examples show that H2O is amphoteric in nature because it acts as a base in one
case and as an acid in the other. An amphoteric substance is a species that can act as either
an acid and a base (it can lose or gain a proton), depending on the other reactant.
The Bronsted-Lowry theory can be applied to acids in solvents other than water or even
solventless reactions. The reaction between gaseous ammonia and HCl gives solid NH4Cl.
HCl(g) + NH3(g) NH4Cl(s)
HCl is an acid because in the reaction it donates a proton to the NH3 molecule. The NH3
acts as a base, even though hydroxide ion OH- is not present, and accepts a proton from
the HCl molecule.

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Table 9.1 Conjugate Acid-Base Pairs of Common Species

Acid Base Conjugate Acid Conjugate Base
HNO3 + H2O H3O+ + NO3-
H2SO4 + H2O H3O+ + HSO4-
H 2O + CO32- HCO3- + OH-

9.2 LEWIS CONCEPT OF ACIDS AND BASES

In 1923, G.N. Lewis proposed a generalized definition of acid-base behavior in which
acids and bases are identified by their ability to accept or to donate a pair of electrons and
form a coordinate covalent bond.
A Lewis acid is any species (molecule or ion) that can accept a pair of electrons, and a
Lewis base is any species (molecule or ion) that can donate a pair of electrons. A Lewis
acid-base reaction occurs when a base donates a pair of electrons to an acid.
In the following reaction, each of two ammonia molecules, Lewis bases, donates a pair of
electrons to a positively charged silver ion, the Lewis acid. The sum of charges on the left
side is +1, so the acid-base adduct on the right hand side must carry a charge of +1:
+
H H H

2 H N + Ag+ H N Ag N H

H H H
Lewis base Lewis acid Alcid base adduct

The boron atom in boron trifluoride, BF3, has only six electrons in its valence shell. Since
the boron atom has an incomplete octet, it can behave as an electron pair acceptor. As a
result, BF3 is a very good Lewis acid and reacts with many Lewis bases; a fluoride ion is
the Lewis base in this reaction, donating one of its lone pairs:

F F
–
F + B F F B F

F F
Lewis base Lewis acid Acid base adduct

The negative charge on the adduct is the sum of charges on the left hand side of the
equation is -1, the sum of charges on the right hand side must also be -1.

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Quick Check 9.1

a) Identify the conjugate acid-base pairs in the following reactions:
i. HCN(g) + H2O(l) H3O+(aq) + CN– (aq)
ii. CH3COOH(l) + H2O(l) H3O+ (aq) + CH3COO– (aq)
iii. H2S(g) + H2O(l) H3O (aq) + HS– (aq)
+

iv. HCl(g) + -
HCO3 (aq) H2CO3 (aq) + Cl (aq)–
b) Identify the Lewis acid and Lewis base in the reaction between:
i. SO3 and O2–
ii. HCl and H2O
iii. BF3 and NH3
Also write down the balanced chemical equation for the reaction and explain.

9.3 IONIC PRODUCT OF WATER

Pure water is a poor conductor of electricity but its conductance is measurable. Water
undergoes self-ionization reversibly as follows,
H2O() + H2O () H3O+(aq) + OH-(aq)
Net reaction H2O() H+ (aq) + OH–(aq)
The equilibrium constant for this reaction can be written as follows:
[H+] [OH–]
Kc = =1.8 ×10–16 mol dm–3
[H2O]
The concentration of H2O, i.e., [H2O] in pure water may be calculated to be 1000 g dm-3
divided by 18 g mol-1 giving 55.5 mol dm-3. Since, water is present in very large excess and
very few of its molecules undergo ionization, so its concentration remains effectively
constant. Constant concentration of water is taken on L.H.S. and multiplied with Kc to get
another constant called Kw.
Kc[H2O] = [H+] [OH–]
or 1.8 × 10-16 × 55.5 = 1.01 × 10-14 = [H+] [OH-]
This 1.01 x 10-14 is called Kw of water at 25oC.
Kc [H2O] = [H+] [OH-]
So, Kw [H2O] = [H+] [OH-] =10-14 at 25oC
Kw is called ionic product of water or dissociation constant of water. The value of Kw
increases almost 75 times when temperature is increased from 0oC to 100oC.
For neutral water
[H+] = [OH-]
or [H+][H+] = 10-14
[H+]2 = 10-14 (at 25 oC)

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[H+] = 10-7mol dm-3 Table 9.2 Kw at various

temperature.
and [OH-] = 10-7mol dm-3
Temp. Kw
The effect of temperature on Kw is shown in Table 9.2.
(ºC)
Whenever some quantity of acid or base is added to water,
then Kw remains the same, but [H+] and [OH-] are no more 0 0.11 × 1014
equal. 10 0.30 × 1014
In case of addition of small amount of acid. 25 1.0 × 1014
[H+] > [OH-] 40 3.00 × 1014
While in the case of addition of few drops of a base. 100 7.5 × 1014

[OH-] > [H+]

During both of these additions, the values of Kw will remain the same, i.e. 10-14 at 25 oC.

9.4 pH AND pOH

+ -
In all the aqueous solutions, the concentration of H and OH are too low to be conveniently
expressed and used in calculations. In 1909, Sorenson, a Danish biochemist, introduced the
term pH and pOH. So, the scales of pH and pOH were developed. These two quantities can
be calculated as:
pH = -log[H+] Interesting Information!
pOH = -log[OH-] Solutions of negative pH and having
For neutral water, pH = -log[10-7] = 7
values more than 14 are also known.
pOH = -log[10-7] = 7
Also, pH + pOH = 14
O
The value of pH normally varies between 0 →14 at 25 C.
The pH values of some familiar aqueous solutions are shown in Figure 9.1. This table can
help you to understand the acidic or basic nature of commonly used solutions.

Figure 9.1 pH Values of some common substances

Sample Problem 9.1

In a solution, the pH is 9.2. Determine the ionic product of water Kw​ at 25oC.
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Solution
Calculate the pOH from the pH:
pOH = 14− pH
pOH = 14−9.2
pOH = 4.8
Find the concentration of H+ and OH-,
Taking antilog of pH and pOH
antilog pH = antilog (9.2)
[OH-] = 10-pH
[H+] = 10-9.2
[OH-] ≈ 6.3 × 10-10 M
Similarly, antilog pOH = antilog (4.8)
[OH-] = 10-pOH
[OH-] = 10-4.8
[OH-] ≈ 1.6 × 10-5 M
Sample Problem 9.2
The ionic product of water at a certain temperature is Kw = 1.0 × 10−14 at 25 ºC. If the
concentration of H+ ions in a solution is 1.0 × 10−7M.
Calculate the concentration of OH− ions, the pH and pOH of the solution.
Solution
Use the expression for Kw:
Kw = [H+][OH-]
Substitute the known values of Kw and the concentration of H+:
1.0×10-14 = (1.0 × 10-7) [OH–]
Solve for the concentration of OH–
1.0 × 10–14
[OH–] = =1.0×10–14
1.0 × 10–7
Calculate the pH:
pH = -log[H+]
pH = -log(1.0 × 10-7) = 7
Calculate the pOH:
pOH = −log[OH−]

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pOH = −log (1.0×10−7)

pOH = 7

Calculate Kw: 9.2

Quick Check
K +] [OH-]
w – [H is
a) A solution prepared by mixing equal volumes of two solutions: one with a pH of 4.0 and
another with×a 10
Kw = (6.3 pH-10
of) 10.0.
× (1.6Calculate
× 10-5) the Kw​for this mixture at 25°C.
b) At a specific temperature, the ionic product of water Kw is 1.0 × 10−14. If the concentration
Kw =− 1.008 × 10-14
of OH ions in a solution is 2.5×10−8 M. Calculate the concentration of H+ ions and the pH
So, the of
ionic product of water at the given temperature is ≈ 1.01 × 10-14 .
the solution.
c) Copper-plate etching solutions is prepared by diluting concentrated HNO3 to 0.30 M HNO3.
Calculate [H+], pH, [OH–] and pOH of this solutions at 25 ºC.

9.5 IONIZATION CONSTANTS OF ACIDS (Ka)

Acids and bases, when dissolved in water, may or may not be completely dissociated.
Many acids are weak electrolytes and ionize to an extent which is much less than 100%. The
value of Ka called the dissociation constant of an acid, is the quantitative measure of the
strength of the acid. Suppose we have an acid HA dissolved in water,
HA + H2O H3O+ + A–
Kc for the reversible reaction will be written as follows:
[H3O+] [A–]
KC =
[HA] [H2O]
[H3O+] [A–]
Kc [H2O] =
[HA]
Let Kc [H2O]= Ka
[H3O+] [A–]
Hence Ka =
[HA]
This equation can be used to calculate Ka for any acidic solution if we know the pH or [H+]
of that solution and the initial concentration of the dissolved acid [HA]. This can also be
used to calculate the equilibrium concentration of H3O+ and A- produced if we know the
initial concentration of acid HA and its Ka value.
When Ka < 10–3 acid is weak.
Ka = 1 to 10–3 acid is moderately strong.
Ka> 1 acid is strong.

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The values of Ka for some acids are given in Table 9.3.

Table 9.3 The values of Ka for some acids

Acid Dissociation Ka Relative

strength
HCI HCI H+ + CI– very large (10–2) Very strong

HNO3 HNO3 H+ + NO3– very large (10–5) Very strong

H2SO4 H2SO4 H+ + HSO4– Large (10–2) Very strong

HSO–4 HSO4 H+ + SO42– 1.3 x 10–4 Strong

HF HF H + + F– 6.7 x 10–5 Week

CH3COOH CH3COOH H+ + CH3COO– 1.85 x 10–5 Week

H2CO3 H2CO3 H+ + HS– 4.4 x 10–7 Week

H2S H2S H++ HS– 1.0 x 10–7 Week

NH41 NH4 H+ + NH5 5.7 x 10–10 Week

HCO3– HCO3 H+ + CO32 4.7 x 10–12 Week

H 2O H2O H+ + OH– 1.8 x 10–15 Very week

9.5.1 Calculating H3O+ ions from ka and Molar Concentration of Weak

Acid
The weak acids do not completely dissociate in water. Therefore, the concentration of
hydronium ions is not equal to the initial concentration of the acid. So, the equilibrium
expression is used to calculate the H3O+ concentration.
For a weak acid HA, the dissociation in water can be represented as:
HA(aq) H+(aq) + A–(aq)
In water, H+ combines with water to form H3O+:
H+(aq) + H2O (l) H3O+(aq)
So, the equilibrium equation in terms of H3O+(aq) is:
HA(aq) H3O+(aq) + A–(aq)
Let the initial concentration of the weak acid HA be C mol dm-3.
At equilibrium:
[H3O+] = x; [A–] = x and [HA] = C–x

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The expression for the acid dissociation constant (Ka) is:

[H3O+] [A–]
Ka =
[HA]
Substitute the equilibrium concentrations into this expression:
x×x x2
Ka = =
C–x C–
For weak acids, x is usually very small compared to C, so C –x ≈ C. Therefore, the
expression simplifies to:
x2
Ka ≈
C

Taking the square root of both sides:

Thus, the concentration of H3O+ is given by:

Sample Problem 9.3

Calculate the concentration of [H3O+] in a 0.1 M (mol dm–3) solution of acetic acid
[CH3COOH], given that the acid dissociation constant Ka is 1.8 × 10-5.
Solution
[H3O+]≈
[H3O+] ≈ 1.8 × 10-5 × 0.1
[H3O+] ≈ 0.18 × 10-6
[H3O+] ≈ 1.34 × 10-3 M (mol dm–3)
The concentration [H3O+] in the solution is approximately 1.34 × 10-3 mol dm–3.

Quick Check 9.3

a) The pH of a 0.10 M solution of formic acid, HCOOH, at 25°C is 2.38. Calculate Ka for formic
acid at this temperature.
b) Calculate the concentration of [H3O+] in a 0.1 M solution of nitrous acid [HNO2], given that the
acid dissociation constant Ka is 4 × 10-4.
c) A vinegar sample is found to have 0.837 M CH3COOH. Its hydronium ion concentration is
found to be 3.86 x 10−3 mol dm-3. Calculate Ka for acetic acid.

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9.6 COMMON ION EFFECT

The suppression of ionization of a weak electrolyte by adding a common ion to it is called
common ion effect. We are familiar with purification of sodium chloride by passing
hydrogen chloride gas through brine (saturated solution of NaCl). Sodium chloride is fully
ionized in the solution. Equilibrium constant expression for this process can be written as
follows:
NaCl(s) Na+(aq) + Cl–(aq)
[Na+][Cl–]
Kc=
[NaCl]
HCl also ionizes in solution:
HCl(g) (s) H+(aq) + Cl-(aq)
On passing HCl gas, concentration of Cl– ion is increased, therefore NaCl crystallizes out
of the solution to maintain the constant value of the equilibrium constant. This type of
effect is called the common ion effect. The addition of a common ion to the solution of a
less soluble electrolyte suppresses its ionization and the concentration of unionized species
increases, which may come out as a precipitate.
Na+(aq) + Cl–(aq) NaCl(s)
More Examples of Common Ion Effect
i. The solubility of a less soluble salts KClO3 in water is suppressed by the addition of a
more soluble salt KCl by common ion effect. K+ is a common ion. The ionization of
KClO3 is suppressed and it settles down as precipitate.
KClO3(s) K+(aq) + ClO–(aq)
KCl(s) K+(aq) + Cl–(aq)
ii. Similarly, the dissociation of a weak acid H2S in water can be suppressed by the
addition of stronger acid HCl. H+ is a common ion. H2S becomes less dissociated in
acidic solution. In this way, low concentration of S2– ion is produced.
H2S (g) 2H+(aq) + S2-(aq)
This low concentration of S2- ions helps to do the precipitation of radicals of second group
basic radicals during salt analysis.
HCl (aq) H+ (aq) + Cl– (aq)
iii. An addition of NH4Cl in NH3 solution suppresses the concentration of OH– due to the
presence of a large excess of NH+4 from NH4Cl. Actually, NH4Cl is a strong electrolyte.
The combination of these two substances is used as a group reagent in third group
basic radicals for salt analysis.

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NH4Cl(aq) NH4+(aq) + Cl-(aq)

NH3 + H2O (aq) NH4+(aq) + OH-(aq)
Common ion effect finds extensive applications in the qualitative analysis and the
preparation of buffers.

9.7 BUFFER SOLUTIONS

The solutions which resist the change in their pH when a small amount of an acid or a base
is added to them, are called buffer solutions. They have a specific constant value of pH and
their pH values do not change on dilution and on keeping for a long time.
Buffer solutions are mostly prepared by mixing two substances.
i. By mixing a weak acid and its salt with a strong base. Such solutions give acidic
buffers with pH less than 7. Mixture of acetic acid and sodium acetate is one of the best
examples of acidic buffers.
ii. By mixing a weak base and its salt with a strong acid. Such solutions will give basic
buffers with pH more than 7. Mixture of NH4OH and NH4Cl is one of the best examples
of basic buffers.
Let us take the example of an acidic buffer consisting of CH3COOH and CH3COONa.
CH3COOH being a weak electrolyte undergoes very little dissociation. When CH3COONa,
which is a strong electrolyte, is added to CH3COOH solution, then the dissociation of
CH3COOH is suppressed, due to common ion effect of CH3COO.–
CH3COOH(aq) + H2O() CH3COO-(aq) + H3O+(aq)
CH3COONa(aq) CH3COO-(aq) + Na+(aq)
If one goes on adding CH3COONa in CH3COOH solution, then the added concentrations
of CH3COO– decrease the dissociation of CH3COOH and the pH of solution increases.
The Table 9.4 tells us how the pH value of a mixture of two compounds is maintained.
Greater the concentration of acetic acid as compared to CH3COONa, lesser is the pH of
solution.
Table 9.4 Effect of addition of acetate ions on the pH of acetic acid solution

[CH3COOH] [CH3COO–] % Dissociation pH

(mol dm–3) (mol dm–3)
0.10 0.00 1.3 2.89
0.10 0.05 0.036 4.44
0.10 0.10 0.018 4.74
0.10 0.15 0.012 4.92

Actually, a buffer mentioned above is a large reservoir of CH3COOH and CH3COO-

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components. When an acid or H3O+ ions are added to this buffer, they will react with
CH3COO- to give back acetic acid and hence the pH of the solution will almost remain
unchanged. The reason is that CH3COOH being a week acid will prefer to remain
undissociated. Similarly, the buffer solution consisting of NH4Cl and NH4OH, can resist
the change of pH and pOH, when acid or base is added from outside. When a base or OH–
ions are added in it, they will react with H3O+ to give back H2O and the pH of the solution
again will remain almost unchanged.
9.7.1 Calculating the pH of a Buffer
Let us try to learn, how a buffer of definite pH
Interesting Information!
can be prepared. Consider a weak acid HA
and its salt NaA with a strong base say NaOH. The body’s blood buffering system,
The reversible reactions for dissociation of involving bicarbonates, helps maintain a
HA and NaA are as follows:
HA H+ + A-
NaA Na+ + A-
pH of a buffer solution can be calculated by
using Henderson equation as given below:
[Acid ]
pH = pKa – log
[Salt]
Interchanging the numerator and denominator,
the sign of log changes.
[Salt ]
pH = pKa + log
[Acid]
This relationship is called Henderson’s equation. This equation shows that two factors
evidently govern the pH of a buffer solution. First is the pKa of the acid used and the
second is the ratio of the concentrations of the salt and the acid. The best buffer is prepared
by taking equal concentration of salt and acid. So, pH is controlled by pKa of the acid. For
example, for acetic acid – sodium acetate buffer, if
[CH3COOH] = [CH3COONa]
[CH3 COONa]
Then pH =pKa + log
[CH3 COOH]
pH =pKa + log (1)
So, pH =pKa+0 = pKa
pH = 4.74.
It means that the pH of this buffer is just equal to the pKa of the acid.

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Quick Check 9.4

a) Explain the impact of common ion effect on solubility.
b) To a saturated solution of AgCl, some of NaCl solution was added.
i. State the effect of the concentration of Ag+ on the equilibrium.
ii. Explain your answer with respect to the common ion effect.
c) How does a buffer maintain pH stability?
d) Calculate the pH of a buffer consisting of 0.50 M HF and 0.45 M of a fluoride (F–) salt before
and after addition
of 0.40 g NaOH to 1.0 dm3 of the buffer (Ka of HF = 6.8 x 10-4).
e) Calculate the pH of a buffer solution in which 0.11 molar CH3COONa and 0.09 molar acetic
acid solutions are present. Ka for CH3COOH is 1.85 x 10-5

9.8 SOLUBILITY PRODUCT

(For slightly soluble ionic compounds)
When a soluble ionic compound is dissolved in water, like NaCl, it dissociates completely
into ions. But for slightly soluble salts the dissociation is not complete at equilibrium
stage. For example, when PbSO4 is shaken with water the solution contains Pb2+, SO42–
and undissociated PbSO4. It means that equilibrium exists between solid solute, PbSO4
and the dissolved ions, SO42– and SO42–.

Lead sulphate is a well-known sparingly soluble compound and it dissociates to a very

small extent like PbCl2.
H 2O
PbSO4(s) Pb2+(aq) + SO42-(aq)
[Pb2+][SO42-]
Kc =
[PbSO4]
Being a sparingly soluble salt, the concentration of lead sulphate (PbSO4) almost remains
constant. Bring [PbSO4] on L.H.S. with Kc.
Kc [PbSO4] = [Pb2+ ][SO42– ]
if Kc [PbSO4] = Ksp
then Ksp =[Pb2+][SO42– ]= 1.6 × 10-8 at 25oC
Ksp is called the solubility product of PbSO4. It is the product of molar solubilities of two
ions at equilibrium stage.
Similarly, for another sparingly soluble salt, PbCl2. Ksp = [Pb2+][Cl–]2
Ksp is usually a very small quantity at room temperature. The value of Ksp is temperature
dependent. So, the solubility product is the product of the concentrations of ions raised
to an exponent equal to the co-efficient of the balanced equation. The value of Ksp is a
measure of the dissociation of sparingly soluble salt.
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The following Table 9.5 shows the Ksp values of some slightly soluble ionic compounds.
Table 9.5 Ksp values for some ionic compounds

Salt Ion Product Ksp Salt Ion Product Ksp

AgBr [Ag+] [Br–] 5.0x10-13 CuS [Cu2+] [S2+] 8x10–34

AgCl [Ag+] [Cl–] 1.8x10-10 Fe2S3 [Fe3+]2 [S2–]3 1.4x10–85
AI(OH)3 [AI3+] [OH–]3 3x10–34 MgCO3 [Mg2+][CO32–] 3.5x10–8
BaSO4 [Ba] [CO42–] 1.1x10–10 MnS [Mn2+] [S2–] 3x10–11
CaCO3 [Ca2+] [Ca32–] 3.3x10–9 PbCrO4 [Pb2+][CrO42–] 2.3x10–13
CaF2 [Ca2+] [F–]2 3.2x10–11 PbSO4 [Pb2+][SO42–] 1.6x10–8

9.8.1 Applications of solubility product

a) Determination of Solubility from Ksp
For this purpose, we need the formula of the compound and Ksp value. Then the unknown
molar solubility S is calculated and the concentration of the ions is determined. Table 9.6
shows the relationship between the Ksp values and the solubility of some sparingly soluble
compounds.
Table 9.6 The relation between solubility and solubility products of some salts

Formula No. of KSP

Solubility gdm–3
ions
PbSO4 2 1.69 x 10–4 1.3 x 10–4
Ca(OH)2 3 6.5 x 10–6 1.175 x 10–2
CaF2 3 3.2 x 10–11 2.0 x 10–4
Ag2CrO4 3 2.6 x 10–12 8.7 x 10–5

Sample Problem
Ca(OH)2 is a sparingly soluble compound. Its solubility product is 6.5 x 10–6. Calculate
the solubility of Ca(OH)2.
Solution
Let the solubility be represented by S in terms of mol dm–3.
The balanced equation is:
Ca(OH)2(aq) Ca2+(aq) + 2OH–(aq)
Ca(OH)2(aq) 0 + 0 Initial stage
Ca(OH)2 S + S Equilibrium stage
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The concentration of OH- is double than the concentration of Ca2+, so

Ksp = [Ca2+][OH-]2 = S x (2S)2
4S3 = 6.5 x 10-6
6.5 x 10-6
S3 =
4
S = (1.625)1/3 x10-2
S = 1.18 x10–2 mol dm–3
Hence, at equilibrium stage 1.18 x10–2 mol dm–3 mol dm–3 of Ca2+ and 2 x 1.18 x10–2
mol dm–3 = 2.36 x 10–2 mol dm–3 OH– are present in the solution. In this way, we have
calculated the individual concentrations of Ca2+ and OH– ions from the solubility product
of Ca(OH)2.
b) Common Ion Effect
The presence of a common ion decreases the solubility of a slightly soluble ionic compound.
In order to explain it, consider a saturated solution of PbCrO4, which is a sparingly soluble
ionic salt.
PbCrO4 (aq) Pb2+(aq) + CrO42–(aq)
Now add Na2CrO4 which is a soluble salt. CrO42– is the common ion. It combines with Pb2+
to form more insoluble PbCrO4. So equilibrium is shifted to the left to keep Ksp constant.

c) Predicting Precipitation
The solubility product can also help in predicting whether the precipitation of a salt will
occur or not. For example, the solubility product of CaSO4 is 2 x 10-5. If we add 10-2 mol
dm-3 solution Ca2+ to10-2 mol dm-3 solution of SO42- ions at 25 °C. The concentrations of
each ionic species can be calculated as
10-2
[Ca2+]=[ SO42-] = = 5.0 x 10-3 mol dm-3
2
[Ca2+][ SO42-] = 5.0 x 10-3 mol dm-3 x 5.0 x 10-3 mol dm-3
= 2.5 x 10-5 mol2 dm-6
= 2.5 x 10-5 mol2 dm-6 > Ksp of CaSO4
As the product of concentrations is greater than Ksp, therefore CaSO4 will precipitate out.
Ionic Product Type of Solution Precipitation
> Ksp Supersaturated Yes
= Ksp Saturated No
< Ksp Unsaturated No

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Quick Check 9.5

a) The solubility product constant (Ksp) of silver chloride (AgCl) is 1.77×10−10 at 25 °C. A
solution already contains 0.10 M of sodium chloride (NaCl). Find the solubility of AgCl in a
solution that contains 0.10 NaCl.
b) Predict whether CaSO4 will be precipitated or not when 10-3 mol dm-3 of each of Ca2+ and
SO42- is mixed together.
c) Will the aqueous solution of ammonium oxalate be acidic or basic? Explain your answer by
giving equation.
d) Solution of potassium carbonate is basic.
i. Explain why the solution is alkaline.
ii. Also give the equation for the hydrolysis of the above salt.

Interesting Information!
The shell of this nautilus is composed mainly of calcium
carbonate. The nautilus adjusts conditions so shell material is
formed when the concentration of calcium ions and carbonate
ions in seawater are high enough to precipitate calcium
carbonate.

9.8 SALT HYDROLYSIS

When a salt dissolves in water, it dissociates into its constituent ions. These ions can
interact with water, affecting the solution’s pH depending on the nature of the acid and
base from which the salt is derived.
9.8.1 Salts of Strong Acids and Strong Bases
For salts derived from strong acids and strong bases (e.g., sodium chloride,
NaCl), the conjugate base of a strong acid (e.g., Cl− from HCl) is very weak and does not
significantly react with water. The conjugate acid of a strong base (e.g., Na+ from NaOH)
is also very weak and does not significantly react with water.
NaCl(s) H2O Na+(aq)+ Cl−(aq)
Na+ is the conjugate acid of NaOH (a strong base) and does not affect the pH.
Cl− is the conjugate base of HCl (a strong acid) and does not affect the pH.
The solution remains neutral.
9.8.2 Salts of Strong Acids and Weak Bases
For salts derived from strong acids and weak bases (e.g., ammonium chloride, NH4Cl),
The conjugate base of the strong acid (e.g., Cl−) does not react with water. The conjugate
acid of the weak base (e.g., NH4+ from NH3​) reacts with water to produce H3O+ ions,
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making the solution acidic.

NH4Cl(s) NH4+(aq) + Cl−(aq)

NH4+is the conjugate acid of NH3 (a weak base) and reacts with water:
NH4+(aq) + H2O(l) NH3(g) + H3O+(aq)
Cl− is the conjugate base of HCl (a strong acid) and does not affect the pH.
The solution is acidic due to the NH4+ ion.
9.8.3 Salts of Weak Acids and Strong Bases
The example of salt of weak acid and strong base is sodium acetate.
CH3COONa(s) + H2O(l) CH3COO−(aq) + Na+(aq)
CH3COO− is the conjugate base of CH3COOH (a weak acid) and reacts with water:
CH3COO−(aq) + H2O(l) CH3COOH (aq) + OH−(aq)
Na+ is the conjugate acid of NaOH (a strong base) and does not affect the pH. The solution
is basic due to the CH3COO− ion.
9.8.4 Salts of Weak Acids and Weak Bases
For salts derived from weak acids and weak bases (e.g., ammonium acetate, NH4CH3COO):
The conjugate acid (NH4+​) and the conjugate base (CH3COO−) both affect the pH.
NH4CH3COO(aq) NH4+(aq) + CH3COO−(aq)
NH4+ hydrolyzes to produce H3O+.
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
CH3COO− hydrolyzes to produce OH−.
CH3COO−(aq) + H2O(aq) CH3COOH(aq) + OH−(aq)
The resultant pH of the solution depends on the relative strengths of the conjugate acid and
conjugate base. The solution may be acidic, basic, or nearly neutral, depending on which
reaction is more dominant.

9.9 ACID–BASE INDICATORS

An indicator is a substance that changes color to mark a titration’s endpoint. Acid-base
indicators exhibit one color in acid and another in base. Most indicators used in acid-base
titration are weak organic acids or weak organic bases. In solution, a weak-acid indicator
(HIn) can be represented by the equation below.
HIn H+ + In-
In− is the symbol of the anion part of the indicator. Because the reaction is reversible, both
HIn and In− are present. The colors displayed result from the fact that HIn and In− have
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different colors.
In acidic solutions, any In− ions that are present act as Brønsted bases and accept protons
from the acid. The indicator is then present in largely unionized form, HIn. In basic
solutions, the OH− ions from the base combine with the H+ ions produced by the indicator.
The indicator molecules further ionize to equalize the loss of H+ ions. The indicator is thus
present largely in the form of its anion, In−. The solution now shows the base-indicating
color, which for litmus is blue.

Figure 9.1 Unionized acid-base indicators and their ionised forms exist in an equilibrium
Different indicators change color at different pH values. The color depends on the relative
amounts of HIn and In- at a given pH. For example, methyl red changes from red to yellow
between pH 4.4 and 6.2. At pH 4.4, the indicator exists mostly as HIn molecules, which
appear red in the solution. The indicator ranges are given below for some of the indicators
commonly used.

Figure 9.2 Range and color changes of some common Acid-Base indicators

9.9.1 Selecting a Suitable Indicator

The two general criteria for an indicator to be used in a titration are:
The pH at the end of the titration should be close to the indicator’s neutral point.
The indicator should indicate a sharp color change near the equivalence point of the
titration.
Each pH indicator changes color over a defined range of pH, known as the indicator range.
An indicator changes color over a range of about 2 pH units.
9.9.2 Titration Curve and Equivalence Point
A pH curve is a graph of the pH of the solution verses the volume of titrant added. The
equivalence point is the point at which the amount of titrant added is just enough to
neutralize the analyte solution completely.
Titration curves show how the pH of an acidic or basic solution changes as
a basic or acidic solution is added to it. We can use the titration curve to choose an indicator
that will show when the titration is complete and we reach the equivalence point. The end
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point of the titration occurs when the indicator changes color. We choose an indicator with
an end point close to the equivalence point.
1. Strong Acid-Strong Base Titration Curve
As an example of a strong acid–strong
base titration, let’s consider the titration
of HCl with NaOH. Initially, the solution
contains only the strong acid. Since the
acid is strong, it completely dissociates,
leading to a high concentration of H+
ions and the pH is very low.
As NaOH is added, OH- ions from
NaOH begin to neutralize the H+ ions
from HCl and pH of the solution rises.
The equivalence point is reached
when the amount of OH- added is
stoichiometrically equal to the amount
of H+ originally present in the acid.
The pH at the equivalence point in a
strong acid-strong base titration is 7.0. Figure 9.3 Strong acid-strong base titration curve
The titration curve at this stage shows
a steep rise in pH, changing quickly from acidic to neutral. The pH value at the endpoint
changes about from 4.0 to 10.0. These titrations have a pH of 7.0 at equivalence, so, such
phenolphthalein as indicator can be used as they show different colours in this range.
2. Strong Acid-Weak Base Titration Curve
Consider the titration of aqueous NH3
with HCl. Initially, the solution contains
only the weak base and it only partially
dissociates, with a lower concentration of
OH- ions compared to a strong base. The
initial pH will be greater than 7 but lower
than the pH of a strong base. As HCl is
added, the concentration of OH- decreases,
causing a further decrease in pH.
Before reaching the equivalence point, the
solution is in a buffer-like region where the
pH changes more gradually. The presence
of the weak base and its conjugate acid
(from the salt formed) creates a buffering
effect, which helps to moderate the pH
Figure 9.4 strong acid-weak base titration curve
change as the base is added.

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The pH at the equivalence point will be less than 7 (pH = 5.27) because the conjugate acid
slightly dissociates, releasing H+ ions making the solution acidic (NH4+ → NH3 + H+).
After the equivalence point, the pH of the solution decreases rapidly. This is because the
strong acid dissociates completely in water, providing a high concentration of hydrogen
ions (H+), which significantly lowers the pH. Methyl orange has its colour change in this
range, therefore, it can be used as an indicator for strong acid-weak base titrations.
Table 9.7 pH ranges of common indicators

Indicators Acid color Base color pH Range Type of Titration

Methyl orange orange yellow 3.2-4.5 strong acid-strong base
strong acid-weak base
Phenolpthalein colorless red 8.2-10.0 weak acid-strong base

Quick Check 9.6

a) Differentiate end point and equivalent point.
b) Explain how an indicator changes its colour in acidic and basic solution.
c) Suggest a suitable indicator for weak acid and strong base titration.
d) Suggest a suitable indicator for weak acid and weak base titration.

EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. Given the following reaction:
NH3 (g) + H2O (l) → NH4+(aq) + OH-(aq)
a) NH3 is the acid, H2O is the base b) NH3 is the base, H2O is the acid
c) NH4+ is the base, OH- is the acid d) H2O is the base, OH- is the acid
II. The pH of 10-3 mol dm-3 of an aqueous solution of H2SO4 is:
a) 3.0 b) 2.7
c) 2.0 d) 1.5
III. The solubility product of AgCl is 2.0 x 10-10 mol dm-6. The maximum concentration
of Ag+ ions in the solution is:
a) 2.0 × 10-10 mol dm-3 b) 1.41 × 10-5 mol dm-3
c) 1.0 × 10-10 mol dm-3 d) 4.0 × 10-20 mol dm-3

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IV. Which indicator is typically used for titrations involving strong acids and strong
bases?
a) Methyl red b) Phenolphthalein
c) Bromothymol blue d) Litmus solution
V. Which of the following is the conjugate base of water?
OH-(aq) b. H+(aq) c. H2O(l) d. H3O+(aq)
Which of the following is a Lewis acid but not a Bronsted-Lowry acid?
a) HCl b) NH₃
c) AlCl₃ d) H₂O
VI. In an acid-base titration, the equivalence point is reached when:
a) pH of the solution is 7.0.
b) The indicator changes color.
c) Equal volumes of acid and base have been added.
d. The reaction stops.
VII. If the concentration of Cl⁻ ion in a solution is increased, the solubility of silver
chloride (AgCl) will:
a) Decrease b) Increase
c) Remain unchanged d) Become zero
VIII. Which of the following pairs of substances can act as a conjugate acid-base pair
according to the Bronsted-Lowry theory?
a) HCl and NaOH b) NH₃ and NH4+
c) H₂O and H₂SO₄ d) H₂O and CH₄
IX. If the pH of a solution is 11, what is the [OH−] concentration in the solution?
a) 1 × 10-3 M b) 1 × 10-11 M
c) 1 × 10-2 M d) 1 × 10-14 M
X. Which of the following pairs forms a buffer solution?
a) Hydrochloric acid (HCl) and sodium chloride (NaCl)
b) Sodium acetate (CH₃COONa) and acetic acid (CH₃COOH)
c) Sodium hydroxide (NaOH) and hydrochloric acid (HCl)
d) Ammonia (NH₃) and sodium sulfate (Na₂SO₄
XI. What is the purpose of a titration acid-base curve?
a) To measure the volume of acid or base used
b) To determine the pH at various points during the titration

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c) To calculate the concentration of the titrant

d) To identify the endpoint of the titration

SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. Define the following with an example for each:
i) Ionization constant ii) Solubility product
ii) Common ion effect iv) Acid-base Indicator
b. Differentiate between:
i) Hydrolysis and dissolution ii) Acidic and basic buffer solutions
c. Explain the concept of conjugate acid-base pairs. How are they related in terms of
proton transfer?
d. What is the relationship between the strength of an acid and the strength of its conjugate
base?
e. For the following three reactions, identify the reactants that are Arrhenius bases,
Bronsted-Lowry bases, and/or Lewis bases. State which type(s) of bases each reactant
is. Explain your answers.
i) NaOH(s) ⎯→ Na+(aq) + OH−(aq) i) HF(aq) + H2O(l) ⎯→ F−(aq) + H3O+(aq)
ii) H+(aq) + NH3(aq) ⎯→ NH4 + (aq)
f. An amphoteric substance can behave as either an acid or a base. Identify whether water
behaves as an acid or a base in each of the following reactions.
i) H2​O + HCl → H3​O+ + Cl− ii) NH3 ​+ H2​O → NH4+ ​+ OH−
iii) HNO3 + H2O → H3O+ + NO3- iv) CH3​COOH+ H2​O ↔ CH3​COO− + H3​
O+
g. Which salt would you expect to dissolve more readily in acidic solution: Barium
sulfate or Barium fluoride? Explain.
h. Why does common ion effect decrease solubility of a less soluble salt?
i. State the basic principle of solubility product. Mention factors affecting solubility
product.
j. What is the main reason that titration of weak acids with weak bases are not performed
for volumetric analysis?
k. Prove by equations what happens when Na2CrO4 is added to saturated solution of
PbCrO4.
l. According to the Lewis acid-base concept, Boron trifluoride (BF3) can act as an acid.
Is this statement correct?

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m. If the concentration of hydrogen ions in a solution is 1 x 10-5 M, what is the pH of the

solution?

DESCRIPTIVE QUESTIONS
Q.3 Describe the Bronsted-Lowry theory of acids and bases. Provide examples of
conjugate acid-base pairs and explain clearly their relationship.
Q.4 Define the Lewis theory of acids and bases. How does this theory differ from the
Bronsted-Lowry theory? Give examples of Lewis acids and bases that do not
involve proton transfer.
Q.5 Discuss applications and implications of the common ion effect in various fields.
Q.6 What is the solubility product for sparingly soluble salts. Give its two applications.
Q.7 Describe the general shape of a titration curve for a strong acid titrated with a
strong base. How can you identify the equivalence point on a titration curve for
a strong acid-strong base titration?

NUMERICAL PROBLEMS
Q.8 A buffer solution has a pH of 5.0. It is made from a weak acid HA with a pKa​
of 4.8. What is the ratio of the concentration of the conjugate base [A−] to the
concentration of the weak acid [HA] in this buffer?
Q.9 Calculate the solubility of a sparingly salt lead (II) iodide (PbI2) in water. It has
Ksp= 1.4 × 10-8.
Q.10 The molar solubility of silver chromate (Ag2​CrO4​) in pure water at 298 K is
6.5×10−5moldm−3. Calculate the Ksp​of silver chromate at this temperature.

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 ELECTROCHEMISTRY

10
Chemistry-XI

ELECTROCHEMISTRY
STUDENT LEARNING OUTCOMES [C-11-A-56 to C-11-B-78]
Define the terms redox, oxidation, reduction, and disproportionation (in terms of electron
transfer and changes in oxidation number). (Knowledge)
Apply the concept of oxidation numbers in identifying oxidation and reduction reactions.
(Application)
Identify the oxidizing and reducing agents in a redox reaction. (Knowledge)
Describe the role of oxidizing and reducing agents in the redox reaction. (Understanding)
Apply the concept of changes in oxidation numbers to balance chemical equations.
(Application)
Explain how electrolytic cells convert electrical energy to chemical energy, with oxidation
at the anode and reduction at the cathode. (Understanding)
Predict the identities of substances liberated during electrolysis based on the state of the
electrolyte, position in the redox series, and concentration. (Knowledge)
Apply the relationship between the Faraday constant, Avogadro constant, and the charge
on the electron to solve problems. (Application)
Calculate the quantity of charge passed during electrolysis and the mass or volume of
substance liberated during electrolysis. (Application)
Deduce the Avogadro constant by an electrolytic method. (Application)
Define the terms standard electrode potential and standard cell potential. (Knowledge)
Describe the standard hydrogen electrode (SHE) and methods used to measure standard
electrode potentials. (Understanding)
Calculate the standard cell potentials by combining the potentials of two standard electrodes
and then use these to predict the feasibility of a reaction and the direction of electron flow
in a simple cell. (Application)
Deduce the relative reactivity of elements compounds, and ions as oxidizing agents or
reducing agents from their electrode potential values. (Application)
Construct redox equations using relevant half- equations. (Application)
Explain how voltaic (galvanic) cells convert energy from spontaneous, exothermic
chemical processes to electrical energy, with oxidation at the anode and reduction at the
cathode. (Understanding)
Explain how voltaic cells convert chemical energy from redox reactions to electrical
energy using Cu-Zn galvanic cell as an example. (Understanding)
Explain how electrode potentials vary with the concentrations of aqueous ions and use the
Nernst equation to predict this quantitatively. (Understanding)

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Explain the concept of the activity series of metals and how it relates to the ease of
oxidation. (Understanding)
Deduce the feasibility of redox reactions from activity series or reaction data.
(Understanding)
Explain the merits of photovoltaic cells as sustainable ways of meeting energy demands by
making reference to the photovoltaic principle. (Understanding)
Explain the use of the Winkler Method to measure biochemical oxygen demand (BOD)
and its use as a measure of water pollution. (Understanding)

The branch of chemistry which deals with inter conversion of electrical and chemical
energy i.e., electrical energy into chemical energy and chemical energy into electrical
energy is called electrochemistry.

10.1 OXIDATION, REDUCTION, AND REDOX

REACTIONS
Oxidation is a process involving loss of electron or electrons.
Fe +2 → Fe +3 + e
Zn → Zn +2 + e
Here Fe+2 and Zn0 have lost electrons, therefore they are oxidized.
Reduction is a process involving gain of electron or electrons.
Cl 0 + e → Cl −1
Cu +2 + 2e → Cu 0
In these examples, Cl0 and Cu+2 have gained electrons; therefore, they are reduced.
Oxidation and reduction always take place together. The reactions in which this happens
is called redox reactions.

Interesting Information
Photosynthesis is a redox reaction which provides food for the entire planet, and another one
is respiration that keeps you alive, both are redox reactions.

There are two ways of finding out whether or not a substance has been oxidized or reduced
during a chemical reaction:
Electron transfer
Changes in oxidation number

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10.2 OXIDATION NUMBER AND ITS SIGNIFICANCE

The oxidation numbers are also called oxidation states. An oxidation number is a number
given to each atom or ion in a compound that shows us its degree of oxidation. Oxidation
numbers can be positive, negative or zero. The + or – sign must always be included. It is
the apparent charge on an atom (per atom) of an element in a molecule or an ion. Higher
positive oxidation numbers mean that an atom or ion is more oxidized. Higher negative
oxidation numbers mean that an atom or ion is more reduced.
10.2.1 Oxidation Number Rules
The oxidation number of any atom or ion can be deduced by using oxidation number rules.
It is important to note that an oxidation number refers to a single atom in a compound.
i. The oxidation number of any uncombined element is zero. For example, the oxidation
number of each atom in S8, H2, Cl2, Na, Mg and Zn is zero.

ii. In either a compound or an ion, the more electronegative element is given the negative
oxidation number. In HF, fluorine has -1 oxidation number.
iii. In compounds, many atoms or ions have fixed oxidation numbers, group 1 alkali metals
are always +1, group 2 alkaline earth elements are always +2, group 17 halogens in
binary compounds are always –1, hydrogen is +1 (except in metal hydrides, such as
NaH, where it is –1), oxygen is –2 (except in peroxides, where it is –1, and in F2O,
where it is +2).

iv. The oxidation number of an element in a mono-atomic ion is always the same as the
charge on the ion, for example, Cl– is –1, Al3+ is +3.

v. The sum of the oxidation numbers in a compound is zero. In neutral molecules, the
algebraic sum of the oxidation numbers of all the elements is zero. HCl and NaCl.
vi. In ions, the algebraic sum of oxidation number equals the charge on the ion.
For examples CO3-2 and SO4-2.
While applying the oxidation number rules in the following examples, ‘Ox. No.’ as an
abbreviation for oxidation number is used.

Keep in Mind!
• Hydrogen shows -1 oxidation state with all metals.
• Hydrogen shows +1 oxidation state with all non-metals.
• Oxygen shows negative oxidation state with all metals.
• Oxygen shows negative oxidation state with all non-metals except fluorine
• Oxygen shows -2, -1 and -1/2 in H2O, Na2O2, and KO2 respectively.

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10.2.2 Finding Oxidation Number of an Element in a Compound or a

Radical
The oxidation number or state of any atom of an element present in a compound or a
radical can be determined by making use of the above-mentioned rules.
Compounds of a metal with a non-metal
A metal always has the positive Ox. No. and nonmetals have the negative Ox. state
For example, in sodium sulfide, Na2S:
2(+1) + S = 0
+2 +S =0
S = -2
Compounds of a non-metal with a non-metal
In compounds containing two different non-metals, the sign of the Ox. No. depends on
the electronegativity of each atom. The most electronegative element is given the negative
sign.
Sample Problem 10.1
Find the oxidation No. of S in Sulfur dioxide, SO2.
Ox. No. of each O atom = –2
For two oxygen atoms = 2 × (–2) = –4
SO2 has no charge, so the total Ox. No. is zero. So,
S + 2(-2) = 0
S-4=0
S = +4
Ox. No. of S = +4
Compound ions
Compound ions are ions with two or more different atoms. Examples are the sulfate ion,
SO42–, and the nitrate ion, NO3–.
Sample Problem 10.2
Calculate the oxidation number (Ox. No.) of sulphur in SO42-.
Solution
[Ox. No. of S] + 4 [Ox. No. of O] = -2
S + 4 (-2) = -2
S = +6
Thus, the oxidation number of sulphur in SO42- is +6.

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Sample Problem 10.3

Calculate the oxidation number (Ox. No.) of manganese in KMnO4.
Solution
(Ox. No. of K) + (Ox. No. of Mn) + 4 (Ox. No. of O) = 0
+1 + Mn +4 (-2) = 0
(+1) + Mn – 8 = 0
Or Mn = + 7
Thus, the oxidation number (Ox. No.) of Mn in KMnO4 is + 7.
Quick Check 10.1
a) Define oxidation and reduction in terms of electron transfer with examples.
b) Define oxidation and reduction in terms of change in oxidation number with examples.
c) Determine Ox. No. of:
i) Oxygen (N) in Na2O ii) Iodine (I) in ICl3
iii) Nitrogen (N) in NO31– iv) Chromium (Cr) in K2Cr2O7

10.3 DISPROPORTIONATION REACTION

A disproportionation reaction is a chemical reaction where a single substance acts as
both the oxidizing and reducing agent, resulting in two different products with different
oxidation states. This type of reaction involves the simultaneous oxidation and reduction
of the same element.
For example, the decomposition of hydrogen peroxide (H2O2) to form water (H2O) and
oxygen (O2) is a disproportionation reaction:
2H2O2 → H 2O2−1 + O20
Oxidation number of oxygen in H2O2 = -1
Oxidation number of oxygen in H2O = -2 (Oxygen is reduced from -1 to -2)
Oxidation number of oxygen in O2 = 0 (Oxygen is oxidized from -1 to 0)
Similarly
6 NaOH ( aq ) + 3Cl20 ( g ) → 5 NaCl −1( aq ) + NaCl +5O3 ( aq ) + 3H 2O
Oxidation number of chlorine atoms in Cl2 =0
Oxidation number of chlorine in NaCl = _1 (Cl is reduced from 0 to -1)
Oxidation number of chlorine in NaClO3 = +5 (Cl is oxidized from 0 to +5)
Disproportionation reactions can occur where ions or molecules can exist in multiple
oxidation states in a reaction.

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10.4 OXIDIZING AGENT (OXIDANT) AND REDUCING

AGENT (REDUCTANT)
An oxidizing agent (atom, ion or molecule) is that substance which oxidizes some other
substance, and is itself reduced to a lower oxidation state by gaining one or more electrons,
while, a reducing agent (atom, ion or molecule) is that substance which reduces some other
substance, and is itself oxidized to a higher oxidation state by losing one or more electrons.
If an element M gains one or more electrons and is converted into M- anion, the element
M is said to be acting as an oxidizing agent, since it withdraws an electron from the other
atom, in this process oxidation number of M has decreased that is:
For oxidizing agent X + e- X-
[Ox. No.= 0] [Ox. No. = -1]
(Higher Oxidation State) (Lower Oxidation State)
For example, Cl + e- Cl-
On other hand, if an element M loses one electron and is converted to M+ cation, the
element M is said to be acting as a reducing agent, since it is providing electrons, it gets
higher oxidation state. Thus,
For reducing agent M M+ + e-
[Ox. No. = 0 [Ox. No. = +1]
(Lower Ox. No.) (Higher Ox. No.)
For example, Na Na+ + e-
Quick Check 10.2
a) Identify the oxidized species and reduced species in the following equation. Also identify
the oxidizing and reducing agents on the reactant side.
i. Fe2O3(s)+CO(g) → Fe(s)+CO2(g) ii. CH₄(g) + 2O₂(g) → CO₂(g) + 2H₂O(l)
b) Identify the species in the following reaction which undergoes both oxidation and reduction.
i. 3HNO₂(aq) HNO₃(aq) + 2NO(g) + H₂O(l)
ii. P₄(s) + 3OH⁻(aq) + 3H₂O(l) → PH₃(g) + 3H₂PO₂⁻(aq)

10.5 BALANCING OF REDOX EQUATIONS BY

OXIDATION NUMBER METHOD
Carry out the following steps for balancing of redox equations by oxidation number
method:
i. Write down the skeleton equation of the redox reaction under consideration.
ii. Identify the elements, which undergo a change in their oxidation number during the
reaction.
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iii. Record the oxidation number above the symbols of the element, which have undergone
a change in the oxidation number.
iv. Indicate the change in oxidation number by arrows joining the atoms on both sides of
the equation. It shows number of electrons gained or lost.
v. Equate the increase or decrease in the oxidation number, i.e., electrons gained or lost
by multiplying with a suitable digit.
vi. Balance the rest of the equation by inspection (hit and trial) method.

Did you know!

Sequence of the balancing the chemical equation using inspection (hit and trial) method.
Firstly, balance atoms of all elements except nitrogen, oxygen and hydrogen. Secondly,
balance atoms of nitrogen (if in the equation).
Thirdly, balance atoms of oxygen (if in the equation).
Lastly, balance atoms of hydrogen (if in the equation).

Keep in Mind!
a) If an element in a species undergoes only increase in oxidation number or decrease in
oxidation number in a reaction. The specie containing such element is written once on the
RHS of the equation.
Zn(s) + HCl (aq) ZnCl2(aq) + H2 (g)
b) If an element in a species undergoes both increase in oxidation number or decrease in
oxidation number simultaneously in a reaction (as in case of self-redox or disproportionation
reaction). The specie containing such element is written twice on the RHS of the equation.
First for increase in oxidation number while second is written for decrease in oxidation
number.
Cl2 + NaOH + Cl2 NaCl + H2O + NaOCl
c) If an element in a species undergoes increase or decrease in oxidation number as well
as no change in oxidation number in a reaction. The specie containing such element is
also written twice. First, for change in oxidation number while second is for no change in
oxidation number.
HNO3 + Cu+ HNO3 Cu(NO3)2 + H2O + NO2
HCl + K2Cr2O7 + HCl Cl2 + KCl + CrCl3 + H2O

Sample Problem 10.4

Balance the following equation by oxidation number method.
K 2Cr2O7 + HCl → KCl + CrCl3 + Cl2 + H 2O
Solution:
1- Write down the skeleton of chemical equation.
K2Cr2O7 + HCl Cl2 + KCl + CrCl3 + H2O

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2- Write down the oxidation number of each element.

K1+2Cr6+2O2-7 + H1+Cl1- → Cl02 + K1+Cl1- + Cr3+Cl1-3 + H1+2O2-
3- Identify the elements that show change in oxidation number on both sides.
6e-
K1+ 6+ 2- 1+ 1- → Cl0 + K1+Cl1- + Cr3+Cl1- + H1+ O2- ......... (i)
2 Cr 2 O 7 + H Cl 2 3 2

2e-
Here, Cr undergoes a change in oxidation state from +6 to +3 and it is reduced (acts as
an oxidizing agent) while Cl undergoes a change in oxidation state from -1 to 0 and it is
oxidized (acts as a reducing agent).
4. Write two half reactions separately i.e., reduction and oxidation reactions
K2Cr6+2O7 2Cr3+Cl3 Half reduction reaction ....... (ii)
2HCl1- Cl02 Half oxidation reaction ........ (iii)
Decrease in Ox. No. of Cr is 6 units for one molecule of K2Cr2O7.
Increase in Ox. No. of Cl is 2 units for 2 molecules of HCl.
Eq. (iii) is multiplied by 3 in order to equalize the loss of electrons and the gain of electrons
i.e., 6 electrons in this equation.
3 x 2HCl 3Cl2
6HCl 3Cl2 ......... (iv)
Now eq. (i) becomes:
K2Cr2O7 + 6HCl 3Cl2 + KCl + 2CrCl3 + H2O
5. Rest of the following equation is balanced by inspection method:
K2Cr2O7 + 6HCl 3Cl2 + 2KCl + 2CrCl3 + H2O
To balance Cl and K, 14 molecules of HCl and 2 KCl molecules are required, therefore,
we add 8 HCl to left hand side
8HCl + K2Cr2O7 + 6HCl 2CrCl3 + 3Cl2 + 2KCl + H2O
To balance hydrogen and oxygen, 6H2O are added to RHS.
Hence, the balanced equation is,
K2Cr2O7 + 14HCl 2KCl + 2CrCl3 + 3Cl2+ 7H2O

Quick Check 10.3

Balance the given equations by oxidation number method.
i. Fe2O3(s)+CO(g) → Fe(s)+ CO2(g)
ii. MnO2 + HCl → MnCl2 + H2O + Cl2
iii. Fe2+ 4–
(aq) + MnO(aq) → Fe3+ 2+
(aq) + Mn (aq)
iv. K2Cr2O7 (aq)+ FeSO4 (aq) + H2SO4 (aq) → Cr2(SO4)3 (aq) + Fe2(SO4)3(aq) + K2SO4(aq) + H2O(l)

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10.6 ELECTROLYTIC CELL

An electrolytic cell is a device that converts electrical energy into chemical energy through
a process called electrolysis. It consists of two electrodes, typically made of metal or
another conductive material, which are immersed in an electrolyte-a substance containing
free ions that carry electric current.
When a direct electric current is applied,
one electrode becomes negatively charged
(the cathode) and the other positively
charged (the anode).
In an electrolytic cell, positive ions
in the electrolyte migrate towards the
cathode, where they gain electrons (a
reduction process), while negative ions
move towards the anode, where they
lose electrons (an oxidation process).
This movement of ions and transfer of Figure 10.1 Main parts of an electrolytic cell
electrons results in chemical changes at the electrodes, effectively converting electrical
energy into chemical energy.
Electrolytic cells are used in the electrolysis of sodium chloride to produce sodium metal
and chlorine gas, the refining and plating of metals, and the production of chemicals like
caustic soda. Electrolysis is also used to produce non-metals such as chlorine and to purify
metals. Electrolysis is generally carried out in an electrolysis cell as shown in Figure 10.1.
In the electrolysis cell,
the electrolyte is the compound that is decomposed; it is either a molten ionic compound
or a concentrated aqueous solution of ions
the electrodes are, made from either carbon (graphite) or metal, which conduct
electricity to and from the electrolyte – the anode is the positive electrode – the cathode
is the negative electrode
the power supply must be direct current.
The actual structure of the cell will vary according to the element extracted.

10.7 REDOX REACTIONS IN ELECTROLYSIS

During electrolysis, the positive ions (cations) move to the cathode. When they reach the
cathode, they gain electrons from the cathode.
For example,
Cu2+ (aq)+ 2e– Cu(s)
2H+(aq)+ 2e– H2(g)
Gain of electrons is reduction and it always occurs at the cathode. If metal atoms are
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formed, they may be deposited as a layer of metal on the cathode. Alternatively, they may
form a molten layer in the cell. If hydrogen gas is formed, it bubbles off.
The negative ions (anions) move to the anode. When they reach the anode, they lose
electrons to the anode. Loss of electrons is oxidation. Oxidation always occurs at the anode.
For example:
2Cl–(aq) Cl2(g) + 2e–
4OH–(aq) O2(g) + 2H2O(l) + 4e–
Electrolysis is a redox reaction. For example, when molten zinc chloride (ZnCl2) is
electrolyzed, the electrode reactions are:
Cathode: Zn2+(l) + 2e– Zn(s) (Reduction)
Anode: 2Cl–(l) Cl2(s) + 2e– (Oxidation)
The electron loss at the anode balances the electron gain at the cathode. The overall reaction
is ZnCl2(l) Zn(s) + Cl2(g)

Quick Check 10.4

Molten copper (II) bromide (CuBr2) is electrolyzed using inert electrodes.
i. Which ions are present in this solution?
ii. Name the electrode on which the formation of copper metal occurs?
iii. Give the half-equation that represents the formation of copper metal.
iv. Write the half-equation for the formation of bromine on the other electrode.

10.8 MASS OF A SUBSTANCE DEPOSITED DURING

ELECTROLYSIS
The mass of a substance produced at an electrode during electrolysis is proportional to the
time over which a constant electric current pass and the strength of the electric current.
Combining current and time, we get the relationship:
Q=Ixt
Where Q = Charge (in coulombs, C)
I = Current (in amperes, A)
t = Time (in seconds, s)
The mass of a substance produced at (or removed from) an electrode during electrolysis is
proportional to the quantity of electricity (in coulombs) which passes through the electrolyte.
The quantity of electricity is often expressed in terms of a unit called the Faraday
(symbol F). 1 Faraday is the quantity of electric charge carried by 1 mole of electrons
or 1 mole of singly charged ions. Its value is 96500 C mol–1.
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During the electrolysis of silver nitrate solution, silver is deposited at the cathode.
Ag+(aq) + e– Ag(s)
1 mol 1 mol 1 mol
1 Faraday of electricity (96500 C) is required to deposit 1 mole of silver. During the
electrolysis of copper(II) sulfate solution, copper is deposited at the cathode.
Cu2+(aq) + 2e– Cu(s)
1 mol 2 mol 1 mol
The equation shows that 2 moles of electrons are needed to produce 1 mole of copper
from Cu2+ ions. So, it requires 2 Faradays of electricity (2 × 96500 C) to deposit 1 mole
of copper.
No. of Faraday = No. of moles of electrons gained or lost

10.9 AMOUNT OF SUBSTANCE PRODUCED DURING

ELECTROLYSIS
The value of F can be used to calculate the mass of substance deposited at an electrode and
the volume of gas produced at an electrode.
Sample Problems 10.5
Calculate the mass of lead (Pb) deposited at the cathode during electrolysis when a current
of 1.50 A flows through molten lead(II) bromide (PbBr2) for 20.0 min. (relative atomic
mass, Ar value: [Pb] = 207; F = 96500 C mol–1)
Solution:
Step 1 Write the half-equation for the reaction.
Pb2+(aq) + 2e– Pb(s)
Step 2 Find the number of coulombs required to deposit 1 mole of product at the electrode.
2 moles of electrons are required per mole of Pb formed = 2F
= 2 × 96500
= 193000 C mol–1
Step 3 Calculate the charge transferred during the electrolysis.
Q =I×t
= 1.50 × 20 × 60
= 1800 C
Step 4 Calculate the mass by simple proportion using the relative atomic mass.
193000 C deposits 1 mole Pb, which is 207 g Pb
so, 1800 C deposits = 1.93 g Pb

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10.10 AVOGADRO’S CONSTANT BY THE

ELECTROLYTIC METHOD
The Avogadro constant, L, is the number of specified particles (atoms, molecules, or ions)
in 1 mole. An electrolytic method can be used to find a value for the Avogadro constant by
calculating the charge associated with 1 mole of electrons.
Charge on 1 mole of electrons
L=
Charge on 1 electron
The charge on the electron can be calculated by experiment. The results show us that the
charge on the electron is approximately 1.60 × 10–19 C.
10.10.1 Finding the Charge on 1 Mole of Electrons
The charge on 1 mole of
electrons can be found from a
simple electrolytic experiment.
The apparatus for this is shown
in Figure 10.2.
The procedure is to weigh the pure
copper anode and pure copper
cathode separately arrange the
apparatus during the electrolysis
of aqueous copper(II) sulfate
as shown in Figure 10.2. The
variable resistor is used to keep
the current constant pass about Figure 10.2 Apparatus for calculating the mass of copper deposited
0.2 amperes. Pass a constant electric current for a measured time interval, e.g., 40 min.
Remove the cathode and anode and wash and dry them with distilled water and then with
propanone. Reweigh the cathode and anode.
The cathode increases in mass because copper is deposited. The anode decreases in mass
because the copper goes into solution as copper ions. The decrease in the mass of the anode
is measured. This is preferred because the copper does not always stick to the cathode very
well.
10.10.2 Calculating charge on an electron
A sample calculation is shown below, using a current of 0.20 A for 34 min.
mass of anode at start of the experiment = 56.53 g
mass of anode at end of experiment = 56.40 g
mass of copper removed from anode = 0.13 g
quantity of charge passed Q =I×t
= 0.20 × 34 × 60
= 408 C
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As the amount of copper removed is 0.13 g

So, 0.13 g of copper requires = 408 C
408
1 g of copper requires =
0.13
408
63.5 g of copper requires = x 63.5
0.13
= 99646 C
But the equation for the electrolysis shows that 2 moles of electrons are needed to produce
1 mole of copper:
Cu2+(aq) + 2e– Cu(s)

63.5
The charge on 1 mole of electrons = × 408 C = 99646 C
0.13
If the charge on one electron is 1.60 × 10–19 C,
99646
L = × 10–19 = 6.2 × 1023 mol–1
1.60
This is in good agreement with the accurate value of 6.02 × 1023 mol–1.

Quick Check 10.5

a) An aqueous solution of silver nitrate is electrolysed. Calculate the mass of silver deposited
at the cathode when the electrolysis is carried out for exactly 35 min using a current of 0.18
A. (Ar [Ag] = 108; F = 96 500 C mol–1)
b) An electric current of 1.04 A was passed through a solution of dilute sulfuric acid for 6.00
min. The volume of hydrogen produced at STP was 41.5 cm3.
i. How many coulombs of charge were passed during the experiment?
ii. How many coulombs of charge are required to liberate 1 mole of hydrogen gas? (F = 96
500 C mol–1)

10.11 ELECTRODE POTENTIALS

(Ease of oxidation and reduction)
During the redox processes, a redox equilibrium exists between two chemically related
species that are in different oxidation states. When a metal is put into a solution of its
ions, an electric potential (voltage) is established between the metal and the metal ions
in solution. This is called electrode potential and it indicates the ease of oxidation or
reduction of a substance. For example, when a copper rod is placed in contact with an
aqueous solution of its ions, the following equilibrium exists:
Cu2+(aq) + 2e– Cu(s)

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There are two opposing reactions in this equilibrium.

a) Metal atoms from the rod entering the solution as metal ions. This leaves electrons
behind on the surface of the electrode.
Cu(s) Cu2+(aq) + 2e–
b) Ions in solution accepting electrons from the metal rod and get deposited as metal
atoms on the surface of the electrode.
Cu2+(aq) + 2e– Cu(s)
The redox equilibrium is established when the rate of electron gain equals the rate of
electron loss.
For unreactive metals such as copper, if this equilibrium is compared with the equilibrium
set up by other metals, the equilibrium set up by copper lies further over to the right.
Cu2+(aq) + 2e– Cu(s)
Cu2+(aq) ions are therefore relatively easy to reduce. They gain electrons readily to form
copper metal.
For reactive metals such as vanadium, the equilibrium lies further over to the left.
V2+(aq) + 2e– V(s)
V2+(aq)ions are therefore relatively difficult to reduce. They gain electrons much less
readily by comparison. The position of equilibrium differs for different combinations of
metals placed in solutions of their ions.

10.11.1 Electrical Double Layer

It is thought that the absolute electrode
potentials cannot be measured due to the
formation of an electrical double layer,
when an element is placed in a solution of
its ions. For example, when zinc is placed
in a solution containing zinc ions, a tiny
number of zinc atoms on the surface of the
metal is converted to zinc ions, which go into
solution. This leaves an excess of electrons
on the surface of the zinc. Figure 10.3 Formation of electrical double layer
The solution around the metal now has excess Zn2+ ions. Some of these cations near the
surface of the zinc are attracted to its surface. So, an electrical double layer is formed. This
buildup of charge causes an electric potential (voltage) between the metal and the metal
ions in solution as shown in Figure 10.3.
Due to the formation an electrical double layer, the potential cannot directly be measured.
But the difference in potential between the metal/metal ion system and another system can
be measured. We call this value the electrode potential, E. Electrode potential is measured
in volts. The system we use for comparison is the standard hydrogen electrode (SHE).
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10.12 STANDARD HYDROGEN ELECTRODE

The standard hydrogen electrode is one of several types of half-cell that can be used as
reference electrode. Figure 10.4 shows a standard hydrogen electrode.
This electrode consists of:
Hydrogen gas at 101 kPa pressure, in equilibrium with H+ ions of concentration 1.00
mol dm–3
A platinum electrode covered with platinum black in contact with the hydrogen gas
and the H+ ions.
The platinum black is finely divided
platinum, which allows close contact of Hydrogen gas supply
hydrogen gas and H+ ions in solution at 1 atm pressure
so that equilibrium between H2 gas
and H+ ions is established quickly. The
platinum electrode is inert so it does Platinum wire
not take part in the reaction. Standard
electrode potential EO values for all
half-cells are measured relative to this Glass ‘bell’ with H+ (1mol/dm+3)
electrode. a hole in for H2 to
bubble out
When connected to another half-cell, Platinum electrode
the value read on the voltmeter gives
the standard electrode potential for that Figure 10.4 Standard hydrogen electrode (SHE)

half-cell. The half-equation for the hydrogen electrode can be written:

2H+(aq) + 2e– H2(g) Eº = 0.00 V
or
2H+(aq) + 2e– H2(g) Eº = 0.00 V
The way that the half-equation is balanced makes no difference to the value of EO. The
equation does not affect the tendency for the element to gain electrons. Its voltage is
arbitrarily fixed at 0.00 V.

10.13 STANDARD ELECTRODE POTENTIAL

The voltage of an electrochemical cell will also depend on concentration, temperature,
and pressure of the gas. Therefore, we should use standard conditions when comparing
electrode potentials.
These are:
concentration of ions at 1.00 mol dm–3
a temperature of 25 °C (298 K)
any gases should be at a pressure of 1 atmosphere (101 kPa)
the value of the electrode potential of the half-cell is measured relative to the standard
hydrogen electrode.
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Under these conditions, the electrode potential we measure is called the standard electrode
potential. This has the symbol, EO. It is spoken of as ‘E standard’.
“The standard electrode potential for a half-cell is the voltage measured under standard
conditions with a standard hydrogen electrode (SHE) as the other half-cell”.

10.14 MEASURING STANDARD ELECTRODE

POTENTIALS
There are three main types of half-cell whose EO value can be obtained when connected to
a standard hydrogen electrode (SHE):
metal/metal ion half-cell (Cu2+/Cu0)
non-metal/non-metal ion half-cell (Cl1-/Cl2)
ion/ion half-cell. (Fe2+/Fe3+)
Figure 10.5 shows how to measure the EO value for a Cu2+/Cu half-cell. The Cu2+/Cu half-
cell is connected to the SHE and the voltage measured. The voltage is +0.34 V. The copper
is the positive terminal (positive pole) of the cell and the SHE is the negative terminal. The
two half-equations are:

Figure 10.5 Measuring the standard electrode potential of a Cu2+/Cu half-cell

Cu2+(aq) + 2e– Cu(s) EO = +0.34 V

H+(aq) + e– 1/2 H2(g) EO = 0.00 V
The EO values show us that Cu2+ ions are easier to reduce than H+ ions (they have a more
positive EO value). Cu2+ ions are more likely to gain electrons than H+ ions. So Cu2+ ions
will accept electrons from the H+/H2 half-cell and H2 will lose electrons to the Cu2+/Cu
half-cell.
Figure 10.6 shows how to measure the EO value for a Zn2+/Zn half-cell. The voltage of the
Zn2+/Zn half-cell is –0.76 V. Zinc metal is the negative terminal (negative pole) of the cell
and the hydrogen electrode is the positive terminal.

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The two half-equations are:

H+(aq) + e– 1/2 H2(g) EO = 0.00 V
Zn2+(aq) + 2e– Zn(s) EO = –0.76 V
The EO values show us that Zn2+ ions are more difficult to reduce than H+ ions (they have
a more negative E O value). Zn2+ ions are less likely to gain electrons than H+ ions. So, Zn
will lose electrons to the H+/H2 half-cell and H+ ions will gain electrons from the Zn2+/Zn
half-cell.

Figure 10.6 Measuring the standard electrode potential of a Zn2+/Zn half-cell

From these two examples, we can see that:
Reduction takes place at the positive terminal of the cell. For example, in the Zn2+/Zn;
H+/H2 cell:
2H+(aq) + 2e– 1 H2(g)
Oxidation takes place at the negative terminal of the cell. For example, in the Zn2+/Zn;
H+/H2 cell:
Zn(s) Zn2+(aq) + 2e–

Quick Check 10.6

a) Explain the following keeping in view the standard electrode potential values (Eº Cl2/2Cl–
= +1.36 V EoBr2/2Br– = +1.07 V, Eo I2/2I– = +0.54 V)
i. The aqueous solution of iodine can be oxidized with bromine of iodide ions.
ii. Why bromine does not react with chloride ions.
b) Give answers using Eo values (EoAg+/Ag = + 0.80 V, EoCr2+/Cr = - 0.91 V, EoFe2+/Fe = - 0.44 V
i. Which of Ag+, Cr2+ and Fe+2 , is the strongest oxidizing agent? Which is the least
oxidizing?
Explain with reason.
ii. Arrange Ag, Cr and Fe in increasing order of their reducing powers.

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10.15 ELECTROCHEMICAL CELL (GALVANIC CELL)

A cell in which the conversion of chemical energy into electrical energy takes place
spontaneously in exothermic redox process with oxidation at anode and reduction at
cathode. A galvanic cell is designed to take advantage of spontaneous transfer of electrons.
A Galvanic Cell, is also known as a Voltaic Cell. For example: Daniel cell and dry cell
etc.
For example: Zn2+(aq) + 2e– Zn(s) voltage = –0.76 V
In order to measure the electrode potential relating to the half-equation
Cu2+(aq) + 2e– Cu(s)
A pure copper rod is placed in a solution of Cu2+
(aq) ions (for example copper(II) sulfate

solution). This Cu2+/Cu system is called a half-cell.

The following standard conditions are used to make the half-cell:
the Cu2+(aq) ions have a concentration of 1.00 mol dm–3
the temperature is 25 °C (298 K)
the copper rod must be pure.
If we connect two half-cells together, we have made an electrochemical cell. We can
measure the voltage between these two half-cells. Figure 10.7 shows a Cu2+/Cu half-cell
connected to a Zn2+/Zn half-cell to make a complete electrochemical cell.
Half-cells are connected together using:
wires connecting the metal rods in each half-cell to a high-resistance voltmeter; the
electrons flow round this external circuit from the metal with the more negative (or
less positive) electrode potential to the metal with the less negative (or more positive)
electrode potential
a salt bridge to complete
the electrical circuit
allowing the movement of
ions between the two half-
cells so that ionic balance
is maintained; a salt
bridge does not allow the
movement of electrons.
A salt bridge can be made
from a strip of filter paper (or
other inert porous material)
soaked in a saturated
solution of potassium nitrate.
The voltages for the half- Figure 10.7 An electrochemical cell, made by connecting a
cells in Figure 10.7 can be Cu2+/Cu half-cell to a Zn2+/Zn half-cell.
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represented by the following half-equations:

Cu2+(aq) + 2e– Cu(s) Eº = +0.34 V
Zn2+(aq) + 2e– Zn(s) Eº = –0.76 V
An electrochemical cell is made by connecting a Cu2+/Cu half-cell to a Zn2+/Zn half-cell.
The relative values of these voltages tell us that Zn2+ ions are more difficult to reduce than
Cu2+ ions. The voltage generated by this cell is +1.10 V.
Eºcell = Eºred + Eºoxi = + 0.34 - (-0.76) = +1.10
In a Cu-Zn galvanic cell, zinc (Zn) serves as the anode, and copper ions (Cu²⁺) in solution
serve as the cathode.
At the anode, zinc undergoes oxidation, losing electrons to form zinc ions:
Zn(s) Zn2+(aq)+2e−
These electrons travel through an external circuit to the cathode, where copper ions gain
electrons and are reduced to form copper metal:
Cu2+(aq) + 2e-− Cu(s)
The overall cell reaction can be represented as:
Zn(s) + Cu2+(aq) Zn2+(aq)+Cu(s)
This process effectively converts the chemical energy of the redox reaction into electrical
energy, which can be connected to perform work.

10.16 CALCULATION OF STANDARD POTENTIAL (EºCell )

We can use EO values to calculate the voltage of an electrochemical cell made up of
two half-cells, even when neither of them is a standard hydrogen electrode. The voltage
measured is the difference between the EO values of the two half-cells. we call this value
the standard cell potential (EºCell).
For the electrochemical cell shown in Figure 10.8 (a), the two relevant half-equations are:
Ag+(aq) + e– Ag(s) E O = +0.80 V
Zn2+(aq) + 2e– Zn(s) E O = –0.76 V
The voltage of this cell is +0.80 – (–0.76) = +1.56 V as in Figure 10.8 (b).

Figure 10.8 (a) An Ag+/Ag, Zn2+/Zn electrochemical cell, (b) The difference between +0.80 V and –0.76 V is +1.56 V.
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Quick Check 10.7

i) What is the function of salt bridge in the voltaic cell?
ii) Calculate the voltage of a cell having iron and copper electrodes.
Fe(s) Fe2+
(aq) + 2e
– Eo = – 0.44 V

2+
Cu (aq) + 2e– Cu(s) Eo = – 0.44 V

The E O value for the Ag+/Ag half-cell is more positive than for the Zn2+/Zn half-cell. So,
the Ag+/Ag half-cell is the positive pole and the Zn2+/Zn half-cell is the negative pole of
the cell.

10.17 APPLICATIONS OF Eº VALUES

10.17.1 Direction of Electron Flow
We can deduce the direction of electron flow in the wires in the external circuit by
comparing the EO values for the two half-cells which make up the electrochemical cell.
For example, in Figure 10.9 these voltages are:
Ag+(aq) + e– Ag(s) EO = +0.80 V
Zn2+(aq) + 2e– Zn(s) EO = –0.76 V
The relative values of these voltages tell us that Zn2+ ions are more difficult to reduce than
Ag+ ions. So, Zn metal will lose electrons to the Ag+/Ag half-cell and Ag+ ions will accept
electrons from the Zn2+/Zn half-cell. The electrons move through the wires in the external
circuit. They do not travel through the electrolyte solution. So, the electron flow is from the
Zn2+/Zn half-cell to the Ag+/Ag half-cell. In other words, the flow is from the negative pole
to the positive pole. Remember that the more positive pole attracts the negative electrons.
10.17.2 Feasibility of A Reaction Using Eo Values
Standard electrode potential values, EO, give us a measure of how easy or difficult it is
to oxidize or reduce a species. The EO values are listed in order of increasingly negative
values. For each half-equation, the more oxidized form is on the left and the more reduced
form is on the right.
The more positive the value of EO, the greater the tendency for the half-equation to
proceed in the forward direction, and the easier it is to reduce the species on the left of
the half-equation.
The less positive the value of EO, the greater the tendency for the half-equation to
proceed in the reverse direction, and the easier it is to oxidize the species on the right
of the half-equation.
To check the feasibility of reaction between Mg2+ and Ag
Mg2+ + Ag ?

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We need half cell equations and E° values

Mg2+ + 2e- Mg E° = -2.32 V
Ag+ + 1e- Ag E° = +0.80 V
Mg2+ are supposed to be reduced here and Ag is supposed to get oxidized, So calculating
E° cell gives us
E°cell = E°red - E°ox
= (-2.32) - (+0.80)
= -1.52V
Negative value of E°cell indicates the reaction is not feasible. On the other hand reaction
between Ag+ and Mg is feasible as for this reaction E°cell will be positive as given below.
E°cell = E°red - E°ox
= (-0.80) - (-2.32)
= +1.52V

Figure 10.9 Standard electrode potentials for some oxidizing and reducing agents
Zn has a greater tendency to lose electrons than Cu, so the chemical reaction that proceeds
in this half-cell is in the reverse direction:
Zn(s) Zn2+(aq) + 2e–
We can combine these two half-equations to show the direction of the reaction in the
electrochemical cell as a whole.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
This is the reaction taking place in the electrochemical cell. The reaction between zinc
metal and copper ions is feasible. If the forward reaction is feasible, the reverse reaction
(between Cu metal and zinc ions) is not feasible.
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If a piece of copper metal is placed directly into a 1.00 mol dm–3 solution of Zn2+ ions,
no reaction takes place. The half-equations, the direction of the reaction is given by a
clockwise pattern reactant, product, reactant, product) starting from the top left as shown
in Figure 10.10 for the cell made from the two half-cells Cu2+/Cu and Zn2+/Zn.

Figure 10.10 A reaction occurs in a direction so that the stronger

oxidizing agent reacts with the stronger reducing agent.

Quick Check 10.8

a) Explain the following keeping in view the standard electrode potential values (Eo Cl2/2Cl-
= +1.36 V Eo (Br2/2Br-) = +1.07 V, Eo (I2/2I-) = +0.54 V)
i. The aqueous solution of iodine can be oxidized with bromide or iodide ions.
ii. Why bromine does not react with chloride ions?

10.17.3 Oxidising and Reducing Agents Using Eo Values

Look back at Figure 10.11. Note the following as the values of EO for each of these
reduction reactions gets more negative.
The species on the left of the equation become weaker oxidizing agents. They accept
electrons less readily.
The species on the right of the equation become stronger reducing agents. They release
electrons more readily.
Cu will not reduce Zn2+ ions to Zn. So how can we reduce Zn2+ ions? The answer is to
react the Zn2+ ions with a stronger reducing agent, which should have an E O value more
negative than the EO value for Zn2+/Zn. In Figure 10.13 we see that the half-equation Mg2+/
Mg has a more negative E O value. So, Mg is a suitable reducing agent.
Zn2+(aq) + e– Zn(s) EO = –0.76 V
Mg2+(aq) + 2e– Mg(s) EO = –2.38 V

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Zn2+ is the better oxidizing agent. It is more likely to accept electrons than Mg2+ ions. Mg
is the better reducing agent. It is more likely to release electrons than Zn.
Compounds can also act as oxidizing and reducing agents. For example KMnO4 (+0.54V)
K2Cr2O7 (+1.33V) are oxidizing agent because of there higher E° values. Whereas, KI and
FeSO4 are reducing gents due to their lower E° values.
Few compounds, such as H2O2 can act both has oxidizing as well as reducing agents.

10.18 VARIATION OF EO VALUE WITH ION

CONCENTRATION
The position of an equilibrium reaction is affected by changes in concentration, temperature
and pressure. If we change the concentration or temperature of half-cell X, the electrode
potential also changes. Under these non-standard conditions we use the symbol E for the
electrode potential. Let us take an example of a metal/metal ion equilibrium:
Table 10.1 Variation of Potential with Ion Concentration

[Fe3+] (mol dm –3) [Fe2+] (mol dm –3) EO (V) Effect

˃ 1.00 1.00 + 0.85 More positive

˂ 1.00 1.00 + 0.70 Less positive

1.00 ˃ 1.00 +0.70 Less positive

1.00 ˂ 1.00 +0.85 More positive

Zn2+(aq) + e– Zn(s) EO = –0.76 V
If [Zn2+] is greater than 1.00 mol dm–3, the value of E becomes less negative / more
positive (say −0.61 V).
If [Zn2+] is less than 1.00 mol dm–3, the value of E becomes more negative / less
positive (say −0.80 V).
Le-Chatelier’s principle can be applied to redox equilibria. If we increase the concentration
of the species on the left of the equation, the position of equilibrium will shift to the right.
So, the value of E becomes more positive / less negative change in contraction of ions and
its effect on Eº is shown in Table 10.1. If two different ions are present in the half-cell, we
have to consider both ions. Let us take the equilibrium between Fe3+ ions and Fe2+ ions as
an example.
Fe3+ + e– Fe2+ EO = +0.77 V
1.00 mol dm–3 1.00 mol dm–3

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10.19 NERNST EQUATION

If we consider a cell made up from a silver/silver ion electrode and a copper/copper(II) ion
electrode, the reaction taking place is:
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s) EO = +0.46 V
When Eºcell is ploted againest 0.5
concentration we obtain a graph as 0.46 V E cell
shown in Figure 10.11. 0.4

Note that we have plotted the value 0.3

Ecell /V
of Ecell (non-standard conditions
0.2
for the cell as a whole) against
the logarithm of the silver ion 0.1
concentration. The above redox
0
cell reaction makes the value of –8 –7 –6 –5 –4 –3 –2 –1 –0
Ecell more positive. log [Ag+]

The effect of concentration and Figure 10.11 Increasing the concentration of silver ions in the cell reaction
temperature on the value of Ecell
can be deduced using the Nernst equation. For a given electrode, e.g., a Cu(s)/Cu2+(aq)
electrode, the relationship is:
RT [oxidized form]
E = Eº + n
zF [reduced form]
where,
E is the electrode potential under non-standard conditions
EO is the standard electrode potential
R is the gas constant, 8.314 J K–1 mol–1
T is the kelvin temperature
z is the number of electrons transferred in the reaction
F is the value of the Faraday constant in C mol–1
ln is the natural logarithm
[oxidized] refers to the concentration of the oxidized form in the half-equation
[reduced] refers to the concentration of the reduced form in the half-equation.
Fortunately, for a metal/metal ion electrode, we can simplify this equation in three ways:
The natural logarithm, ln, is related to log to the base 10 by the relationship
ln x = 2.303 log10 x
At standard temperature the values of R, T and F are constant
The equation then becomes
0.059 [oxidized form]
E = Eº + og 235
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Sample problem
What is the eloectrode potential of a Zn electrode dept in a solution containing Zn2+ ions
(0.1M), The e° value of Zn2+ / ZnO is -0.76V
Using Half equation and E°,
Zn2+ + 2e- Zn E° = -0.76V
8.31×298
E = (-0.76) + n (0.1)
2×96500
E = -0.76 + (-0.029) = -0.78 V
Since, Concentration of Zn2+ is decreased to shift equilibrium backward and electrode
potential decreases to -0.78 V

10.20 ACTIVITY SERIES OF METALS AND EASE OF

OXIDATION
The activity series of metals is a ranking of metals based on their reactivity, particularly
their tendency to lose electrons and undergo oxidation. Metals higher in the activity series
have more negative standard reduction potentials, meaning they are more likely to lose
electrons and undergo oxidation. Hence such metals act as reducing agents. Metals at the
top of the series are the most reactive with water, oxygen and acid. For example, alkali
metals like cesium and sodium are highly reactive and oxidize readily, reacting vigorously
with substances like water to form ions and release hydrogen gas.
In contrast, metals lower in the activity series, such as noble metals like gold and silver,
do not oxidize easily. They are less reactive and do not readily lose electrons, that is why
they do not react with water.
Metals at the bottom of the series are the least reactive with water, oxygen and acid. Thus,
the position of a metal in the activity series directly correlates with its ease of oxidation
and overall reactivity. Conversely, metals lower in the activity series have more positive
standard reduction potentials, indicating a greater tendency to gain electrons and undergo
reduction. Hence such metals act as oxidizing agents.
Activity series of metals is actually reactivity series.
Thus, the activity series can be understood in terms of standard reduction potentials: metals
with more negative potentials are more reactive and oxidize more readily, while those with
more positive potentials are less reactive and oxidize less readily as given in Table 10.2.

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Table 10.2 Activity Series of Metals

Metals Ions E0 (V) Reaction Occurring Trend

Li Li1+ -3.05
K K1+ -2.93
Ba Ba2+ -2.90 React with cold water,
replacing hydrogen
Sr2+

decreasing ease of oxidation, reactivity and acting as reducing agent

Sr -2.89 2M(s) +2H2O(l) 2MOH(aq) + H2(g)
Ca Ca2+ -2.87
Na Na1+ -2.71
Mg Mg2+ -2.37
Al Al3+ -.1.66
React with steam, but
Zn Zn2+ -0.76 not cold water, replacing
hydrogen.
Cr Cr3+ -0.74
M(s) +H2O(l) MO(aq) + H2(g)
Fe Fe2+ -0.44
Cd Cd2+ -O.40
Co Co2+ -0.28
Ni Ni2+ -0.25 Do not react with water.
React with acids, replacing
Sn Sn2+ -0.14
hydrogen.
M(s) +HCl(aq) MCl(aq) + H2(g)
Pb Pb2+ -0.13

H2 H+ 0.00 Included as reference

Cu Cu2+ +0.34
Hg Hg2+ +0.92
Unreactive with water or
Ag Ag1+ +0.80
acids.
Pt Pt2+ +1.18
Au Au3+ +1.50

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10.21 FEASIBILITY OF REDOX REACTIONS FROM

ACTIVITY SERIES OR REACTION DATA
The activity series is actually a reactivity series of metals, in order of reactivity from
highest to lowest. It is used to determine the products of single displacement reactions;
whereby metal M1 will replace another metal M2 in a solution if M1 is higher in the series.
From the activity series of metals, we can determine whether the reaction is feasible or not.
We sum up the potentials of half reactions, if potential of the cell is positive, the reaction
is possible if negative, the reaction is not feasible. Let us see the reactions:
Fe2+
(aq) + 2e
- Fe(s) Eº(ox)= – 0.44 V
Ag+(aq) + 1e- Ag(s) Eº(ox)= + 0.080 V
The ovelall reaction is
Fe(s) + 2Ag+(aq) Fe2+(aq) + 2Ag(s) Eº(cell)= 0.080 – (–0.44) = + 1.24 V
The cell potential is positive; hence the reaction is feasible.
Consider another example:
From the activity series of metals, we have
Al3+
(aq) + 3e
– Al (s) Eº(red) = -1.66 V
Ag+(aq) + 1e- Ag(s) Eº(ox)= + 0.080 V
Al3+
(aq) + Ag(s) Al (s) + Ag+(aq) Eº(red) = -1.66 + 0.080 = – 0.86 V
The sum of EO values of the two half-cell reactions is negative. Hence the reaction is not
feasible.

Quick Check 10.9

a) State the Nernst equation, why is it significant in electrochemistry.
b) What is the effect of variation in ion concentration on the standard electrode potential of a
half reaction?
c) Give answers using Eo values (EoAg+/Ag = + 0.80 V, EoCr2+/Cr = - 0.91 V, EoFe2+/Fe
= - 0.44 V
i. Which of Ag+, Cr2+ and Fe2+, is the strongest oxidizing agent? Which is the least
oxidizing? Explain with reason.
ii. Arrange Ag, Cr and Fe in increasing order of their reducing powers.
d) What is the electrode potential of a Cu electrode dipped in a solution containing Cu2+ ions
(0.01 M), The Eo value of Cu2+/Cu0 is +0.34 V.

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10.22 PHOTOVOLTAIC CELLS

The word ‘photovoltaic’ is composed of photo (light) and volt (electrical potential). The
cell which converts light energy into electrical energy is called photovoltaic cell.
10.22.1 Principle of Photovoltaic Cells
The central principle behind the operation of PV cells is the photovoltaic effect, which
involves the generation of voltage and electric current in a material upon exposure to light.
The photovoltaic effect involves the excitation of electrons from the valence band to the
conduction band in semiconductors, facilitated by the energy from photons. This process
is improved by the presence of a PN junction, which separates the electrons and holes,
creating a voltage that drives an electric current.
10.22.2 Merits of Photovoltaic Cell as Sustainable Source of Energy
i. The photovoltaic effect continues as long as light is present, making it a sustainable
method for generating electricity.
ii. A photovoltaic system is a renewable energy source that converts sunlight into electrical
energy.
iii. The photovoltaic systems use the sun’s energy, making them a sustainable energy
source that is independent of fossil fuels.

10.27 WINKLER METHOD, BOD AND DO

Biochemical oxygen
demand (BOD) is the Disolved
capacity of organic matter Oxygen
in natural water to consume
Concentraction

oxygen within a period of

five days. The value of BOD
is the amount of oxygen
consumed as a result of BOD
biological oxidation of
dissolved organic matter in Direction of Flow of River
the sample. The oxidation Figure 10.12 Inverse relationship between BOD and DO
reaction is catalyzed by microorganisms which are already present in the natural water. It
is measured experimentally through Winkler method by calculating the concentration of
oxygen at the beginning and at the end of five days period, in which a sealed water sample
is maintained in the dark at constant temperature at 25°C.
Dissolved oxygen (DO) is defined as the amount of oxygen dissolved in water. It is
dissolved either from the atmosphere or released by plants during photosynthesis in water.
Its concentration is between 5 to 8 mg/dm3. The minimum level of DO should be 5 mg/
dm3. Below 5 mg/dm3, the water supposed to be polluted.

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Dissolved Oxygen (DO) and Biochemical Oxygen Demand (BOD) have an inverse
relationship as shown in Figure 10.12. As bacteria consume oxygen in the water while
decomposing organic matter, BOD increases, leading to lower dissolved oxygen (DO)
level.

Winkler method
Winkler method is a technique used to measure the amount of dissolved oxygen (DO) in
water samples. It is based on the idea that dissolved oxygen (DO) in the sample solution,
has oxidizing properties and reacts with KI. The amount of iodine formed is measured by
titrating with sodium thiosulfate using starch as an indicator which turns the solution dark
blue, indicating the endpoint. The amount of iodine formed is proportional to the amount
of dissolved oxygen in the solution.

EXERCISE
MULTIPLE CHOICE QUESTIONS
Q.1 Four choices are given for each question. Select the correct choice.
I. The activity series of metals arranges metals in order of their:
a) Atomic mass b) Density
c) Ease of oxidation d) Ease of reduction
II. According to the activity series, which of the following metals would most readily
displace hydrogen gas from dilute acids?
a) Copper (Cu) b) Silver (Ag)
c) Magnesium (Mg) d) Platinum (Pt)
III. The salt bridge allows transfer of ------------ in Zn-Cu voltaic cell.
(a) Zn2+ ions b) SO42- ions
(c) Both d) None of these
IV. If Zn-Cu galvanic cell works ideally after complete discharge, both compartments
will have:
a) CuSO4 solution b) ZnSO4 solution
c) Cu+2 ions d) Zn solid
V. Which of the following half-reactions represents a reduction process?
a) Zn(s) → Zn2+(aq) + 2e− b) Fe2+(aq) → Fe3+(aq)+ e−
c) Cl2​(g) + 2e−→ 2Cl−(aq) d) 2H+(aq) + 2e− → H2​(g)

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f. Which of the following half-reactions represents the oxidation process occurring

in the disproportionation of Cu+?
a) Cu2+(aq)+2e−→ Cu(s) b) Cu+(aq)+ e−→ Cu(s)
c) Cu+(aq) → Cu2+(aq)+ e− d) 2Cu+(aq)→ Cu2+(aq) + Cu(s)
VII. If salt bridge is not used between two half cells in a Galvanic cell, then the voltage
a) Decrease slowly b) Decrease rapidly
c) Does not change d) Drop to zero
VIII. In an electrolysis experiment, if a charge of 96,500 Coulombs is passed through
a solution, the amount of substance liberated or deposited at the electrode is
directly related to:
a) Mass number of the ion
b) One mole of electrons being transferred
c) Avogadro’s number of ions being discharged
d) Standard electrode potential of the metal ion
IX. The experimental determination of Avogadro’s number through electrolysis
typically involves measuring:
a) The current and voltage applied.
b) The mass of the substance deposited or liberated by a known charge.
c) The conductivity of the electrolytic solution.
d) The temperature changes during electrolysis.
X. The principle of measuring DO by Wrinkler’s Method is based on
a) Iodimetry b) Iodometry
c) Acid-Base titration d) Complexometry
XI. A positive value for the standard electrode potential (E°) of a metal ion/metal
half-cell (e.g., Cu2+/Cu) indicates that:
a) The metal is a strong reducing agent. b) The metal ion is readily oxidized.
c) The metal ion is readily reduced.
d) The metal will readily displace hydrogen from dilute acids.
XII. Which of the following changes would typically lead to an increase in the rate
of electrolysis?
a) Decreasing the concentration of the electrolyte
b) Increasing the distance between the electrodes
c) Decreasing the surface area of the electrodes
d) Increasing the current passed through the electrolytic cell

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SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. How and why electrical double layer is formed?
b. Why electrode potential of Cu is called reduction potential?
c. What are the advantages of salt bridge in a galvanic cell?
d. How can we predict the feasibility of a chemical reaction using the cell voltage?
e. During electrolysis of aqueous NaCl, why Na is not liberated at the cathode?
f. Calculate the Ox. No. of chromium (Cr) in the following compounds:
(i) CrCl3 (ii) Cr2(SO4)3 (iii) Cr2O72-
g. The order of decreasing reactivity of metals based on their position is K > Mg > Zn >
Fe > Cu. Write balanced chemical equations for the reactions that would occur (if any)
when:
i) Copper is added to a solution of magnesium sulfate.
ii) Iron is added to a dilute solution of hydrochloric acid.
h. Explain why some metals higher in the activity series can displace hydrogen from
acids, while others lower in the series cannot.
i. Calculate Number of Faradays required to deposit 108 g of Ag1+, 63.5 g of Cu2+ and
27 g of Al3+.
j. In an electrolysis experiment, a current of 0.500 A was passed through a solution of
AgNO3​for 30.0 minutes. The mass of silver deposited on the cathode was found to be
0.503 g. Given that the molar mass of silver is 107.87 g mol-1 and the charge on a silver
ion is +1. Calculate the value of Avogadro’s number (NA​) from this data.
k. A cell is set up with a standard nickel electrode (Ni2+(aq) + 2e− ⇌ Ni(s) EO =−0.25 V)
and a standard cobalt electrode (Co2+(aq) +2e−⇌Co(s), EO = −0.28 V).
i) Identify which metal will be the anode and which will be the cathode. Justify
your answer.
ii) Write the balanced overall cell reaction.
iii) Calculate the standard cell potential (E°cell ​).

DESCRIPTIVE QUESTIONS
Q.3. How electrode potential varies with concentration of an aqueous solution? Use
the NERST equation to explain this variation.
Q.4. How Avogadro’s number can be derived using an electrolytic cell?
Q.5. Describe the construction and working principle of the Zn-Cu Galvanic cell.
Q.6 What is meant by Standard Hydrogen Electrode (SHE)? How it is used to
measure the electrode potential of another electrode?
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NUMERICAL PROBLEMS
Q.7 Calculate the electrode potential for a zinc electrode immersed in a 0.010 mol
dm⁻³ solution of zinc sulfate (ZnSO4​) at 298 K. The standard electrode potential
(E°) for Zn2+(aq)+2e− ⇌ Zn(s) is -0.76 V. (Gas constant, R = 8.31 J K⁻¹ mol⁻¹, Faraday
constant, F = 96500 C mol⁻¹)
Q.8 A constant current of 2.00 A is passed through a solution of copper(II) sulfate
(CuSO4​) for 30.0 minutes. Calculate the mass of copper deposited at the cathode.
(Molar mass of Cu = 63.5 g mol⁻¹, Faraday constant, F = 96500 C mol⁻¹)
Q.9 A galvanic cell consists of a standard hydrogen electrode (SHE) and a Ni2+(aq)
/Ni(s) half-cell. The measured cell potential at 298 K is 0.25 V, and the nickel
electrode is the negative terminal.
a) Write the balanced overall cell reaction.
b) Determine the standard electrode potential (E°) of the Ni2+(aq)/Ni(s) half-cell.
c) Identify which electrode is the anode and which is the cathode.

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11
Chemistry-XI

HYDROCARBONS
STUDENT LEARNING OUTCOMES [C-11-D-01 to C-11-D-17]
Classify hydrocarbons as aliphatic and aromatic. (Understanding)
Describe the nomenclature of alkanes and cycloalkanes. (Understanding)
Explain the shapes of alkanes and cycloalkanes exemplified by ethane and cyclopropane.
(Understanding)
Explain the unreactive nature of alkanes towards polar reagents. (Understanding)
Define homolytic and heterolytic fission, free radical initiation, propagation and
termination. (Understanding)
Describe the mechanism of free radical substitution in alkanes exemplified by methane
and ethane. (Understanding)
Identify organic redox reactions. (Understanding)
Explain the nomenclature of alkenes. (Understanding)
Explain the shape of the ethene molecule in terms of s and p C-C bonds. (Understanding)
Describe the structure and reactivity of alkenes as exemplified by ethene. (Understanding)
Explain with suitable examples the terms isomerism, stereoisomerism, and structural
isomerism. (Understanding)
Explain the dehydration of alcohols and dehydrohalogenation of RX for the preparation of
ethene. (Understanding)
Describe the chemistry of alkenes by the following reactions of ethene: hydrogenation,
hydrohalogenation, hydration, halogenation, halo hydration, epoxidation, ozonolysis, and
polymerization. (Understanding)
Explain the concept of conjugation in alkenes having alternate double bonds.
(Understanding)
Describe the mechanism of electrophilic addition in alkenes, using bromine/ ethene and
hydrogen bromide propene as examples. (Understanding)
Use the IUPAC naming system for alkenes. (Understanding)
Explain the inductive effects of alkyl groups on the stability of primary, secondary and
tertiary cations formed during electrophilic addition (this should be used to explain
Markovnikov addition). (Understanding)

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Hydrocarbons is a class of organic compounds that consists of only carbon and hydrogen.
Hydrocarbons are abundantly found in petroleum and natural gas. They are frequently used
as domestic and industrial fuels. Generally, hydrocarbons have many synthetic applications.
Unsaturated hydrocarbons, especially alkenes, are used as the starting materials for a
number of industrial products. Most of the products in the form of medicines, plastics,
perfumes, polymers have their origins in hydrocarbons. Hydrocarbons are broadly divided
into two classes that is aliphatic and aromatic hydrocarbons.

11.1 ALIPHATIC AND AROMATIC HYDROCARBONS

The compounds that are not aromatic are called aliphatic hydrocarbons. Aliphatic
compounds may be open chain and cyclic, also they may be saturated or unsaturated. If
there are only carbon and hydrogen atoms in an aliphatic compound, it is called aliphatic
hydrocarbon. Alkanes are acyclic aliphatic hydrocarbons, whereas cycloalkanes are
cyclic aliphatic hydrocarbons. Alkenes and alkynes are acyclic and unsaturated aliphatic
hydrocarbons. Figure 11.1 shows some examples of aliphatic hydrocarbons.

H H H H H
H C H H C C H C C H C C H

H H H H H
Methane Ethane Ethene Ethyne
H2 H2
H2 C C
C H2C CH2 H2C CH2
H 2C CH2

H2C CH2 H2C CH2 H2C CH2

H2C CH2
C
H2
Cyclopropane Cyclobutane Cyclopentane Cyclohexane

Figure 11.1: Aliphatic hydrocarbons

Aromatic hydrocarbons is a special class of cyclic hydrocarbons that have high carbon
to hydrogen ratio and are based on benzene (C6H6) or resembling compounds. Benzene
is the basic aromatic compound and other compounds such as toluene and phenol are its
derivatives. Figure 11.2 presents the structures of some aromatic hydrocarbons.
CH3 CH2 - CH3
H
C C C Interesting Information!
HC CH HC CH HC CH
The term aromatic was derived from
HC CH HC CH
the Greek word ‘aroma’ meaning
HC CH
C
“fragrant” and is used in organic
C C
H H H chemistry for a special class of
compounds (aromatic compounds)
Benzene Methylbenzene Ethylbenzene
having characteristic odour.
Figure: 11.2 Some aromatic hydrocarbons

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11.2 NOMENCLATURE
11.2.1 Alkanes or Paraffins
Alkanes are saturated hydrocarbons with the general Did You Know?
formula CnH2n+2. Methane (CH4) is the simplest member Butane is a fuel used in
of this family. The homologous series of alkanes with lighters. Isobutane is used as a
propellant in products such as
condensed structural formulae and molecular formulae shaving gel.
are shown in Table 11.1.
Table 11.1 Condensed structural formulae and molecular formulae of alkanes

IUPAC Molecular Condensed structure

Name formula
Methane CH4 CH4
Ethane C2H6 CH3 CH3
Propane C3H8 CH3 CH2 CH3
Butana C4H10 CH3 CH2 CH2 CH3
Pentane C5H12 CH3 CH2 CH2 CH2 CH3
Hexane C6H14 CH3 CH2 CH2 CH2 CH2 CH3
Heptane C7H10 CH3 CH2 CH3 CH2 CH2 CH2 CH3
Octane C8H18 CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH3
Nonane C9H20 CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3
Decane C10H22 CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3
What we obtain after the removal of one hydrogen atom from an alkane is called an alkyl
group. The resulting alkyl groups are named by replacing –ane of the alkanes with –yl.
Few examples are shown in Table 11.2 & Table 11.3.
Table 11.2 alkyl groups, their names and abbreviations

Alkane Alkyl group Abbreviation

CH4 CH3- Me–
Methane Methyl
CH3-CH3 CH3-CH2- Et–
Ethane Ethyl
For alkanes with more than two carbon atoms, more than one alkyl groups can be derived.

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Table 11.3 alkyl groups, straight chain and branched and their names

Alkane Possible Alkyl Groups

CH3CH2CH3 CH3 CH2CH2 ––––– CH3CHCH3

Propane n-Propyl group iso-Propul group
(Propyl) (1-Methylethyl)

CH3CH2CH2CH2 –– CH3CH2CHCH3 CH3CHCH2–– CH3CCH3

H3CH0CH2CH3
CH3 CH3
n-Butyl group sec-Butyl group Iso-Butyle group tert-Butyl group
(Butyl) (1-Methylpropyl) (2-Methylpropyl) (1,1-Dimethylpropyl)

11.2.2 Nomenclature of alkanes

Branched chain alkanes are named according to the following rules.
1. Locate the longest continuous chain of carbon atoms; this chain determines the parent
name for the alkane. We designate the following compound as a hexane because the
longest continuous chain contains six carbon atoms, that is, a bent change.

The longest continuous chain may not always be obvious from the way the formula is
written. Notice, for example, that the following alkane is designated as a heptane because
the longest chain contains seven carbon atoms.

2. Number the longest chain beginning from the end nearest to the substituent. Applying
this rule, we number the two alkanes shown above in the following way.

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3. Use the numbers obtained by the application of rule 2 to designate the location of the
substituent group. The parent name is placed last, and the substituent group, preceded
by the number designating its location on the chain, is placed first. For example:

4. When two or more substituents are present, give each substituent a number
corresponding to its location on the longest chain. For example, we designate the
following compound as 4-Ethyl-2-methylhexane.

The substituent groups should be listed alphabetically (i.e. ethyl before methyl). While
deciding on alphabetical order ignored multiplying prefixes such as “di” and “tri”.
5. When two substituents are present on the same carbon atom, use that number twice.

6. When two or more substituents are identical, indicate this by the prefixes di, tri, tetra,
and so on. Then make certain that each and every substituent has a number.

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Application of these six rules allows us to name most of the alkanes that we shall encounter.
Two other rules, however, may be required occasionally.
7. When two chains of equal length compete for selection as the parent chain, choose the
chain with the greater number of substituents.

8. When branching first occurs at an equal distance from either end of the longest chain,
choose the name that gives the lower number at the first point of difference.

11.2.3 Nomenclature of cycloalkanes

Cycloalkanes are named by attaching the prefix ‘cyclo’ to the names of the alkanes
possessing the same number of carbon atoms. Figure 11.3
1 2 CH3 CH2 CH2 CH3
CH2 CH3
H3C CH CH3

4
3

2
1

Common name: Isopropylcyclohexane H3C CH3 Common name: n-Propylcyclohexane

Ethylcyclohexane IUPAC name: 1-Methylethylcyclohexane 1,1,4-Trimethylcyclohexane IUPAC name: Propyclcyclohexane

Figure 11.3 Naming cycloalkanes

Quick Check 11.1
a) Write down the structural formulas for 2-methylbutane and 2,2-dimethylpropane.
b) Write down displayed formula of 2,3,3-trimethylhexane and methylcyclohexane.
c) Give two differences between molecules of cyclopentane and pentane?c)
d) Eicosane is a straight chain alkane whose molecules contain 20 carbon atoms. What is the
molecular formula of eicosane?

11.2.3 Shapes of Alkanes and Cycloalkanes

The carbon atom in an alkane has four sp3 hybridized orbitals and forms four single bonds
that are equidistant from each other Figure 11.4. Alkane molecules have a tetrahedral
shape around carbon atoms.

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Carbon atoms in alkane molecules form sigma bonds with surrounding carbon and
hydrogen atoms.
As a result, carbon atoms in
alkanes are surrounded by 4
pairs of bonding electrons which
equally repel each other to form
109.5o bond angles and a C-C
bond length of 1.54 Å. The
shapes of organic molecules are
generally represented using ball
and stick formula. The shapes
of some straight chain alkanes Figure 11.4 Sp3 hybridised methane and ethane
are shown (Table 11.4).
Table 11.4 Shapes of some straight chain alkanes
IUPAC name &
Molecular Structural formula 3D Structure
formula
H

Methane CH4 H C H

H
H H

Ethane C2H6 H C C H

H H
H H H

Propane C3H8 H C C C H

H H H

H H H H

Butane C4H10 H C C C C H

H H H H

Cycloalkanes are cyclic, meaning that the carbon atoms of the molecule are arranged in the
form of a ring. Cycloalkanes are also saturated, meaning that all of the carbons atoms that
make up the ring are singly bonded to other atoms. The structural shapes of cyclopropane,
cyclobutane and cyclopentane are shown below (Table 11.5)

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Table 11.5 Shapes of few cycloalkanes

IUPAC name &

Molecular Structural formula 3D Structure
formula
H2
Cyclopropane C
C3H6
H2C CH2
H 2C CH2
Cyclobutane
C4 H 8
H 2C CH2
CH2
Cyclopentane H2C C
C4H10 H2
H2C CH2

11.2.4 Physical Properties of Alkanes

1. Alkanes containing upto four carbon atoms are colourless, odourless, gases while
pentane to heptadecane (C5 to C17) are colourless, odourless liquids. The higher
members from C18 onwards are waxy solids which are also colourless and odourless.
2. Alkanes are non-polar or very weakly polar and are insoluble in polar solvents like
water, but soluble in non-polar solvents, such as hexane, benzene, ether, etc.
3. Their physical constants, e.g. boiling points, melting points, density, etc increase with
the increase in number of carbon atoms, whereas solubility decreases with the increase
in molecular mass. The boiling points of alkanes having branched chain structures
are lower than their isomeric normal chain alkanes, e.g. straight change butane has a
higher boiling point -0.50 ºC than 2-Methylpropane (isobutane, -11.7 °C).
Quick Check 11.2
a) Why do branched alkanes have lower boiling points than the straight-chain alkanes?
b) Explain why alkanes have a tetrahedral shape.
c) Draw the shapes of cyclopropane and cyclopentane.

11.3 REACTION MECHANISM AND MODES OF BOND

BREAKING
Reaction mechanism is the series of steps that take place in the course of the overall
reaction. Like all chemical reactions, organic reactions involve the breaking of chemical
bonds. There are two ways in which covalent bonds can break.

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(a) Homolytic Fission Homolytic Cleavage

Homolytic fission occurs when the
covalent bond breaks evenly to produce A Homolysis A + B
B
free radicals. Free Radical is a species Free radicals
that contains an unpaired electron and is
very reactive. Free radicals are extremely hv Cl + Cl
Cl Cl
reactive because of the tendency of Free radicals
unpaired electrons to become paired.
Figure 11.5 Homolytic fission and free radical formation
(b) Heterolytic Fission
Heterolytic fission occurs when the
covalent bond breaks in such a way
that the originally shared pair of
electrons is gained by one atom only
and oppositely child ions are produced.
This bond fission is shown by full
curly arrows in mechanisms.

11.4 UNREACTIVE
NATURE OF ALKANES Figure 11.6 Heterolytic fission and formation of radical ions
TOWARDS POLAR REAGENTS
The alkanes or paraffins (Latin: parum =
little, affins = affinity) are inert towards Did You Know?
acids, alkalis, oxidizing and reducing Hydrocarbon combustion produces
agents under ordinary condition. The CO₂, a greenhouse gas contributing to
lack of reactivity of alkanes under normal climate change. Incomplete combustion
conditions may be explained on the basis can release carbon monoxide (CO) and
of the non-polarity of the bonds forming particulate matter, which have serious
them. The electronegativity values of health and environmental consequences.
carbon (2.5) and hydrogen (2.1) do not
differ appreciably and the bonding electrons between C–H and C–C are equally shared
making them almost non-polar and generally unreactive.

The unreactive nature of alkanes can also be explained on the basis of inertness of a sigma
bond. In a sigma bond the electrons are very tightly held between the nuclei which makes
it a very stable bond. A lot of energy is required to break it.

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11.5 REACTIONS OF ALKANES

Under high temperature or suitable conditions, alkanes undergo two types of reactions.
i. Thermal and Catalytic Reactions ,e.g. Combustion and cracking
ii. Free radical substitution reactions are the reactions that involve replacement of one
atom, or group of atoms by another through the free radical mechanism.
11.5.1 Free radical Substitution Reactions
Substitution reactions of alkanes take place in the presence of light energy through the
formation of highly reactive free radicals. An example is the substitution of a halogen
atom with a hydrogen of an alkane, called halogenation. Alkanes react with chlorine and
bromine in the presence of sunlight or UV light resulting in the successive replacement
of hydrogen atoms with halogens. The extent of halogenation depends upon the amount
of halogen used. Reaction of alkanes with fluorine is highly violent and results in a
mixture of carbon, fluorinated alkanes and hydrofluoric acid. Iodine does not substitute
directly because the reaction is too slow and reversible. The order of reactivity of halogens
is:
F2 > Cl2 > Br2 > I2
Halogenation involves the following three steps.

i) Initiation step is the first step in the mechanism of free radical substitution of alkanes
by halogens. It involves the breaking of the halogen-halogen bond using energy from the
UV light.

hv Cl + Cl
Cl Cl
ii) Propagation step is the second step in the free radical substitution in which the initially
formed radicals attack the alkane molecule generating more free radicals.
H H

H C H + Cl H C + H Cl

H H
H H

H C + Cl Cl H C Cl + Cl

H H

iii) Termination step is the final step in a free radical substitution in which two free
radicals react together to form a product. The termination may take place in different ways.
The chloride and alkyl radicals may combine to form an chloroalkanes or two chloride
radicals may also react to make the chlorine molecule. Another termination mode is
the formation of alkane with double number of carbon atoms which takes place when
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two alkyl radicals merge together. This type of termination is rare and the alkanes with
double carbon atoms are formed in traces. However, its presence is evident of free radical
substitution mechanism.
H H

i) H C + Cl H C Cl

H H
H H H H

ii) H C + C H H C C H

H H H H

iii) Cl + Cl Cl Cl

By repetition of step (ii), propagation step, a mixture of halogen substituted products

(chloroalkanes) is obtained. The more the chlorine gas in reaction mixture to start with, the
greater the proportions of chlorine atoms in the chloroalkane molecules formed.
Trichloromethane is also known as chloroform and tetrachloromethane is also known as
carbon tetrachloride.

Interesting Information!

Haloalkanes are anaesthetic in nature. The anesthetic power of a haloalkane increases with the
number of halogen atoms. Use of these as organic solvents in lab is strictly monitored due to
their toxic nature.

Further substitution Further substitution Further substitution

with Cl radical with Cl radical with Cl radical

Cl Cl Cl
CH3Cl CH2Cl2 CHCl3 CCl4
Chloromethane Dichloromethane Trichloromethane Tetrachloromethane

Quick Check 11.3

a) Explain why alkanes have high stability?
b) What are major types of reactions that alkanes undergo?
c) How the termination step occurs in the halogenation of alkenes?
d) State the conditions under which a mixture of halogenoalkanes is obtained from the
halogenation of alkanes.
e) Predict the products of the free radical chlorination of ethane.

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11.6 ALKENES
11.6.1 Nomenclature of Alkenes:
Alkenes are unsaturated hydrocarbons, unsaturated hydrocarbons are compounds of
hydrogen and carbon only whose molecules contain carbon to carbon double bonds (or
triple bonds). Alkenes have two hydrogen atoms less than the corresponding saturated
hydrocarbons.
The IUPAC rules for naming alkenes are similar in many respects to those for naming
alkanes.
1. Select the longest continuous chain that contains the C = C as the parent chain. Change
the ending of the name of the alkane of identical length from — ane to — ene, e.g.,

2. Number the chain so as to include both carbon atoms of the double bond. Numbering
begins from the end nearer to the double bond.

3. Designate the location of the double bond by using the number of the first atom of the
double bond as a prefix.

4. Indicate the locations of the substituent groups by the numbers of the carbon atoms to
which they are attached.

5. If the parent chain contains more than one double bonds, they are alkadienes for two,
alkatrienes for three and so on.

11.6.2 Preparation of Alkenes

Alkenes are prepared by the removal of small atoms (H,OH,X) from the adjacent carbon
atoms of the saturated compounds, so as to create a double bond between carbon atoms.
These reactions are known as elimination reactions. In such reactions, a small molecule
such as H2O or HCl, is removed from adjacent carbons in an organic molecule. Preparation
of ethene through various methods is being discussed below.
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i) Dehydration of Alcohols
Ethene is prepared by heating a mixture of ethanol and excess of concentrated sulphuric
acid at 180°C. The reaction involves the removal of a water molecule from the alcohol
molecule.
H2SO4
CH3CH2OH CH2=CH2 + H2O
Ethanol heat Ethene water

In the first step, ethyl hydrogen sulphate is formed which decomposes on heating to
produce ethene.
180ºC
CH3–CH2OH + H2SO4 CH3–CH2 – OSO3H + H2O
heat
CH3–CH2OSO3H H2C=CH2 + H2SO4
ii) Dehydrohalogenation of Alkyl Halides
On heating, ethyl bromide with alcoholic KOH, ethene is formed. Removal of hydrogen
and halogen takes place from adjacent carbon atoms to create a double bond.
heat
H3C–CH2–Br + KOH(alcoholic) H2C=CH2 + KBr + H2O

11.6.2 Physical Properties

i. First three members i.e. ethene, propene and butene are gases at room temperature
while C5 to C15 are liquids and the higher members are solids.
ii. They are insoluble in water but soluble in alcohol.
iii. They have characteristic smell and burn with luminous flame.
iv. Unlike alkanes, they show weakly polar properties because of sp2 hybridization
Quick Check 11.4
a) Give the reactions of propanol with H2SO4, wright down all the reaction involved.
b) Name the following alkenes
i) CH3C(CH3)=CH-CH3 ii) CH2=CHCH(CH3)2
c) Draw the structural formulas of the following alkenes.
i) 3-Methyl-2-butene ii) 2-Methyl-4-ethyl-2-pentene
d) Give the dehydrohalogenation reaction of bromopropane?
e) Can propanaol undergo dehydration? If yes give reactions involving dehydration.

11.7 STRUCTURE AND REACTIVITY OF ALKENES

11.7.1 Structure of Alkenes
Ethene (C2H4) is the simplest alkene. Each carbon atom in ethene is sp2 hybridized and
forms three equivalent sp2 hybrid orbitals which lie in the same plane. The unhybrid p-
orbital lies perpendicular (90º) to the plane of hybrid orbitals shown in Figure 11.8.
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These sp2orbitals are formed by mixing of the 2s orbital with two 2p orbitals leaving one
unhybrid p orbital. In ethene, each carbon uses two sp2 orbitals to form two C–H bonds
each. The remaining sp2 orbital on each carbon is used to form a carbon-carbon σ bond by
linear overlap as in Figure 11.9.
The unhybrid p-orbitals of each Interesting Information!
carbon atom which are parallel Plants produce ethene as a natural
to each other overlap laterally ripening hormone. For efficiency
to form another carbon-carbon harvesting and transportation to
bond. This bond formed by the market, fruits and vegetables are often
lateral overlap of p-orbitals is picked unripe and exposed to ethane
called a π bond. so they could ripen in short time.

z IS IS
Unhybrid p y 2pz 2pz
orbital sP2

x sP2 sP2

Hybrid sp2 sP2

The set of orbitals sp2 + P IS IS

Fig.11.8: sp2 hybrid & unhybrid orbitals of C Fig.11.9: Bond formation of carbons in ethene

The two carbon atoms forming a double bond and the four atoms attached directly to them
lie in the same plane. The remaining p-orbital on each carbon is used to form the π bond.
The sp² hybridization results in a trigonal planar arrangement
around each carbon atom. The bond angles are approximately
120o, leading to a planar molecule as shown in Figure 11.10.
11.7.1 Reactivity of π bond
Alkenes are more reactive than alkanes due to the presence
of the double bond. The probability of finding electron is Figure 11.10 Structure of ethene
away from the line joining the two nuclei. Due to this reason
π-electrons are less firmly held between the nuclei. A π bond is, therefore, a weak bond as
compared to a σ-bond. During a reaction it breaks comparatively easily rendering alkenes
as reactive group of compounds. Moreover, the loosely held π-electrons are more exposed
to attack by the electrophilic reagents. Alkenes, therefore, undergo electrophilic addition
reactions very easily.

Did You Know?

Electrophile is a species that can act as electron pair acceptor, it is represented by E+.
Alkenes act as nucleophile because they contains pi electrons. Nucleophile is a species that
can act as a donor of a pair of electrons, it is represented by Nu..-.

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Quick Check 11.5

a) How does an alkane differ from an alkene in stability?
b) Which of the following species is likely to act as a nucleophile?
i) H2 ii) H+ iii) OH-
c) Explain your answer to (d).
d) Which of the following species is likely to act as an electrophile?
i) H2 ii) H+ iii) OH-
e) Explain your answer to (f).

The reactions of alkenes mostly proceed through the formation of carbocations. Therefore,
before studying the addition reactions of alkenes, the concept of carbocations and their
stability is very important.
11.7.2 Carbocation Stability and Inductive effect of Alkyl group
Carbocation is an alkyl group with a single positive charge on one of its carbon atoms.
Carbocations are classified into following types.
i. Carbocation which is bonded to H only is named as methyl carbocation.
ii. If carbocation is bonded to one C or alkyl substituent then it is named as primary 1º
carbocation.
iii. If it is bonded to 2 carbons (alkyl substituent) directly, then it is named as secondary
2º carbocation.
iv. If it is named as tertiary 3º carbocation if it is directly bonded to 3 carbons (alkyl
substituent).
The inductive effect of alkyl groups plays an important role in the stability of carbocation.
The polarization of a σ bond due to electron withdrawing or electron donating effect of
adjacent groups or atoms is referred to as inductive effect. Alkyl groups have a slightly
electron donating Inductive effect. Electron donating species, are said to have positive
inductive effect(+I), whereas electron withdrawing species, such as a halogen atom, have
a negative inductive effect (-I).
The alkyl groups attached to the positively charged carbon atoms are electron donating
groups. Due to the positive charge on the carbon atom, carbocation is electrophile. The
inductive effect is shown by the arrowheads on the bonds to show the alkyl groups pushing
electrons towards the positively charged carbon.
H H R R

H C + R C + R C + R C +

H H H R
Methyl: No alkyl group 1º: One alkyl group 2º: Two alkyl groups 3º: Three alkyl groups
donating electrons donating electrons donating electrons donating electrons
Stability increases

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As a result of this, the carbocation become less positively charged which makes it
energetically more stable. The stability of carbocation ions increases with a number of alkyl
groups due to their +I effect. This means that tertiary carbocation is the most stable as they
have three electron-donating alkyl groups which energetically stabilize the carbocation
Figure 11.11.
11.7.3 Electron withdrawing inductive effect
Electron withdrawing groups, such as a halogen atom, have a negative inductive effect
(-I). Halogen withdraws bonded electrons from carbon to carbon bond and thus displays
negative inductive effect. This causes a permanent dipole to arise in the molecule wherein
the halogen atom holds a negative charge and carbon become partial positive Figure 11.12.
Less positive charge than C1
Less electronegative
++ ++ –
C C C C Cl
4 3 2 1
More electronegative
Electron deficient C1 pulling
electrons from C1-C2 covalent bond
Figure 11.12 Inductive effect: Polarization of sigma bond

11.8 REACTIONS OF ALKENES

Alkenes are unsaturated hydrcarbons and they undergo electrophilic addition reactions
mostly. Other minor types of reactions include oxidation, combustion and polymerization
reactions.
11.8.1 Electrophilic Addition Reactions
The reactions in which an electrophile is added to the double bond of an alkene is called
electrophilic addition reaction.
Mechanism of electrophilic addition in alkenes
The C=C in alkenes is a + electrophile
X
region of high electron density
H H H H
making susceptible to attack by
electrophiles. Alkenes reacts C C X C C+
carbocation
with an electrophile to give a H H H H
carbocation intermediate that –
Y nucleophile
then reacts with a nucleophile.
H H H H
In the generalized mechanism
+
Figure 11.13, X represents an X C C+ X C C Y
-
electrophile and Y represents a H H H H
nucleophile. Figure 11.13 Generalized mechanism of electrophilic addition

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Quick Check 11.6

a) How do alkenes react with an electrophile?
b) Why the order of stability of carbocation is 3° > 2° > 1°?

In this chapter, only the mechanism of halogen addition and hydrogen halide addition will
be learnt.

1. Halogenation
Halogenation means addition of halogens like chlorine or bromine. When bromine water
(a solution of bromine in water having red-brown colour) is added to ethene in an inert
solvent like carbon tetrachloride, its reddish brown colour is discharged at once. This
reaction is used to identify the unsaturation of an organic compound.
CH2 =CH2 + Br2 → Br-CH2-CH2-Br
Mechanism
The above reaction proceeds through a three–steps mechanism as given below:
i) Bromine (Br2) is a non-polar molecule, however, when a bromine molecule gets closer
to the double bond of an alkene, the high electron density in the double bond repels the
electron pair in Br-Br away from the Br atom. As a result of this, the Br atom closest
to the double bond is slightly positive and acts as an electrophile.
H H Electrophile

C C + –
Br Br:
H H Induced Dipole
The double bond repels the electrons
High area of electron density away from the closest Br atom
Non-polar molecule

ii) The + bromine of Br2 is attacked by the π electrons in the double bond and the partial
positive bromine accepts a pair of electrons from the C=C bond in the alkene. This
results in the formation of a highly reactive carbocation intermediate.
iii) This carbocation intermediate reacts with the Br- (nucleophile) to make the product.
Mechanism is shown below Figure 11.14.
Mechanism: Primary
carbocation
H H H H H H
+ – Room Temp.
C C Br Br H C C H H C C H
+
H H Br – Br Br
:Br
1,2–Dibromoethane
Donates electrons pair to Br+

Figure 11.14 Electrophilic addition mechanism of ethene and Br2

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2. Hydrohalogenation
When an alkene reacts with dry gaseous hydrogen halide at room temperature, the product
is a halogenoalkane.
CH2 = CH2 + HBr CH3–CH2–Br
Ethene Bromoethane
Hydrogen halides are among the simplest examples of polar substances having permanent
dipoles that add to alkenes Figure 11.15. All hydrogen halides (HBr,HCl,HI,HF) give this
reaction and add across C=C exactly the same way. But, the rate of reaction increases from
HF to HI. The actual product formed depends upon whether the alkene is symmetrical or
unsymmetrical.

H Br
Electrophile Pulls the electrons more
strongly towards itself
Has lower electronegativity than
Br so is electron deficient
Figure 11.15 HBr molecule polarity
i) Addition to symmetrical alkenes: When the alkene (e.g. ethene) is symmetrical
only one product is theoretically possible. Let us look at the mechanism of addition of HBr
to ethene.
Mechanism:
i. Nucleophilic pi-bond attacks the hydrogen in hydrogen halide. Hydrogen bromide
gives a bromide ion (Br–). Ethene is converted to carbocation by adding hydrogen to
one of the double bonded carbons.
ii. The bromide ion (nucleophile) attacks the carbocation to give the addition product
Figure 11.16.
H H H H H H

C C H Br H C C H H C C H

H H H H Br
:Br 1-Bromoethane
Alkyl halide

Figure 11.16 Electrophilic addition mechanism of HBr to ethene

ii) Addition to unsymmetrical alkenes: When the alkene is unsymmetrical, two
products are theoretically possible. For example, the addition of HBr to propene can give
two products. But experimentally, it has been found that under these conditions, the major
product is 2-bromopropane and the minor product is 1-bromopropane.

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Markovnikov’s Rule is applicable for addition reactions in alkenes. According to this

rule, “When a polar reagent adds to an unsymmetrical alkene, the negative part of the
reagent attach to the double bonded carbon which bears the lesser number of hydrogen.”
Mechanism
Propene reacts with HBr in two ways. The mechanism of this reaction involves the
following steps.
i. The pi electrons of C=C attacks on partial positive end of H-Br. Hydrogen bromide
breaks heterolytically creating bromide ion (electrophile) and hydrogen is added to
double bonded carbon with more number of hydrogen, creating a 2o carbocation.
ii. The bromide ion attacks the secondary carbocation to give the major product. The
minor product is formed by the attack on primary carbocation Figure 11.17.

H Br
H H H H H H H H H
Room Temp
H C C C H C C C H H C C C H

H H H H H Br H
Propene :Br 2-Bromopropane
Secondary Carbocation (Major Product)
Room Temp.
H H H H H H

H C C C H H C C C H

H H :Br H H Br
1-Bromopropane
Primary Carbocation (Minor Product)
Figure 11.17 Electrophilic addition mechanism of HBr to propene
Quick Check 11.7
a) Compare and explain the relative rates of addition to alkenes (reactivities) of HCl, HBr and HI
b) Explain the difference between an addition reaction and an elimination reaction?
c) How alkene react with an electrophile?
d) Explain how Markovnikove’s rule is applied in addition of HBr to 2-pentene.

3. Hydrogenation
Hydrogenation means addition of molecular hydrogen to an alkene in the presence of a
catalyst (Ni/ Pt) to form a saturated compound at 250-300 0C.
Ni
H2C = CH2 + H2 H3C –CH3
250–300 ºC
On industrial scale, this reaction is used to convert vegetable oil into margarine (Banaspati
ghee).
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Ni
Oil + H2 Margarine (Banaspati ghee)
4. Hydration
Gaseous alkenes react with steam at high temperature and pressure in the presence of
concentrated acid (H₂SO₄) as the catalyst to form alcohols.
H2SO4
H2C = CH2 + H2O C2H5OH
Similar to hydrohalogenation, the alkene forms a carbocation intermediate, which is then
attacked by OH-.
5. Halohydration
Halohydration is a reaction where an alkene reacts with a halogen (such as bromine or
chlorine) in the presence of water to form a halohydrin. For ethene (C₂H₄), the reaction
specifically produces a bromohydrin or chlorohydrin, depending on the halogen used.
Br
H2C = CH2+Br 2​+ H 2​O CH3–CH
OH
1-Bromo-2-ethanol
6. Epoxidation
The epoxidation of alkenes gives an oxygen-containing three-membered cyclic ether called
epoxide. In the case of ethene (C₂H₄), this reaction can be accomplished using various
oxidizing agents. Ethene can also be converted to ethylene oxide using molecular oxygen
and metal catalysts. A transition metal catalyst facilitates the reaction, forming an epoxide
directly from the alkene. The epoxides can be converted in to diols by acid hydrolysis.
OH
H H H H
Ag C C H+/H O
2
C C + O2 H2C CH2
H H
H H O OH
Epoxide Ethane-1,2-diol
7. Ozonolysis
Ozonolysis is a method of oxidatively cleaving alkenes using ozone (O3), a reactive
allotrope of oxygen. This reaction is often used to identify the structure of unknown
alkenes by breaking them down into smaller, more easily identifiable pieces. Alkenes react
with ozone (O₃) to form ozonides, which can be further reduced to carbonyl compounds
(aldehydes or ketones), and ultimately to alcohols.
C2H4+O3 C2H4O3 2CH2O

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O O
O O
O3 Zn/H2O
H 3C CH CH2 +
HC CH2
H3C H3C H H H
O
1-Propene Ethanal Methanal

reduction

H 3C CH2 OH CH3 OH
Ethanol Methanol

Quick Check 11.8

a) Write the equation for the ozonolysis of ethene.
b) Give the epoxidation reaction of 2-Butene.
c) How ozonolysis can indicate the position of a double bond in an alkene? Explain with the
help of an example.

8. Polymerization
Polymerization is the formation of extremely long molecules (polymers) from small
reactive molecules that join together (monomers). Addition polymerization is one of the
most important addition reactions of alkenes which form the basis of the plastics industry.
Addition polymerization is the reaction in which many monomers containing at least one
C=C double bond form long chains of polymers as the only product.
Just like in other addition reactions of alkenes, the π-bond in each C-C bond breaks and
then the monomers link together to form new C-C single bonds. A polymer is a long-chain
molecule that is made up of many repeating units.

H H H H
Polymerization Interesting Information!
n C C C C Alkenes, like ethene and propene,
are used to create plastics through
H H polymerization. Ethene, for
H H n
instance, is polymerized to make
Ethene Poly (ethene) polyethylene, one of the world’s
Monomer Polymer most common plastics used in bags,
bottles, and packaging.
H Cl H C

n Polymerization
C C C C

H H H H n
Chloroethene Poly(chloroethene) (PVC) This ball pen is
Monomer Polymer made of PVC

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Deducing repeating units

• A repeating unit is the smallest group of atoms that when connected one after the other
make up the polymer chain. It is represented by square brackets in the displayed and
general formula.
• In poly(alkenes) (such as poly(ethene)) and substituted poly(alkenes) (such as PVC)
made of one type of monomer, the repeating unit is the same as the monomer except
that the C-C double bond is changed to a C-C single bond.

H H H H H H H

n C C C C C C C C

H H H H H H H H
n
Repeating unit
Ethene Poly (ethene)
Monomer Polymer

Quick Check 11.9

i. Ethene is a monomer used in the polymerization process to create polyethylene.
(a) Discuss how the chemical structure of ethene makes it suitable for polymerization.
(b) Discuss the change in hybridization and bond angle during this reaction.
ii. Explain why an addition reaction increases the saturation of a molecule.

11.9 CONJUGATED DIENES

As the name indicates, a diene is a molecule containing two double bonds between carbon
atoms. In a Conjugated diene, the double bonds in the carbon chain are separated by a single
bond. The adjacent double bonds in conjugated dienes allow for the overlap of p-orbitals
on three or more adjacent atoms. This overlap leads to a delocalization of electrons, which
can stabilize the molecule and affect its reactivity. In conjugated dienes pi-bond overlap
extends over the entire system.

C C C C

Delocalization of pie electrons

of the conjugated bonds
Conjugated alkenes are an important class of compounds in organic chemistry, featuring
unique properties due to the arrangement of their double bonds. Conjugated dienes like
1,3-butadiene are used in the production of synthetic rubber. The conjugated structure
allows for polymerization, leading to long chains that exhibit rubber-like properties.

Quick Check 11.10

a) Draw the structure of simple conjugated dienes such as Buta-1,3-diene.
b) Illustrate the delocalization of electrons in conjugated dienes.
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11.10 ISOMERISM
The concept of isomerism is an important feature of organic compounds. Two or more
compounds having the same molecular formula but different structural formulas and
properties are said to be isomers and the phenomenon is called isomerism. The structural
formula of a compound shows the arrangement of atoms and bonds present in it.
The simplest hydrocarbon to have structural isomers is butane (C4H10). If we study the
structural formula of butane or other higher hydrocarbons of the alkane family, we will
observe that it is possible to arrange the atoms present in the molecule in more than one
way to satisfy all valencies. This means that it is possible to have two or more different
arrangements for the same molecular formula. For example, chlorobutane molecule can
have two different arrangements as represented by the following structural formulas:
CH3CH2CH2CH2Cl and CH3CHClCH2CH3
1-Chlorobutane 2-Chlorobutane
This fact has been supported by an experimental evidence that there are two compounds with
different physical properties but with the same molecular formula of C4H9Cl. Isomerism is
not only possible but common if the compound contains more than three carbon atoms. As
the number of carbon atoms in a hydrocarbon increases, the number of possible isomers
increase very rapidly. The five carbon compound, pentane, has three isomers.
11.10.1 Types of Isomerism
A. Structural Isomerism
The structural isomerism is not confined to hydrocarbons only. In fact, all classes of
organic compounds and their derivatives show the phenomenon of structural isomerism.
The structural isomerism arises due to the difference in the arrangement of atoms within
the molecule. The structural isomerism can be exhibited in five different ways.
1. The Chain Isomerism
This type of isomerism arises due to the difference in the nature of the carbon chain. For
example, for pentane (C5H12) and butane (C4H10), the following arrangements are possible.

CH3 CH2 CH2 CH3 CH3 CH CH3

CH3
Butane 2-Methylpropane CH3
(Isobutane)
CH3 CH2 CH2 CH2 CH3 CH3 CH2 CH CH3 CH3 C CH3

CH3 CH3
Pentane 2-Methylbutane 2,2-Dimethylpropane
(Isopentane) (Neopentane)

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2. Position Isomerism
This type of isomerism arises due to the difference in the position of the same functional
group on the carbon chain. The arrangement of carbon atoms remains the same. For
example: chloropropane and butene (C4H8) can have two positional isomers.

CH3 CH2 CH2 Cl CH3 CH CH3

Cl
1-Chloropropane 2-Chloropropane

CH3 CH2 CH CH2 CH3 CH CH CH3

But-1-ene But-2-ene
3. Functional Group Isomerism
The compounds having the same molecular formula but different functional groups are
said to exhibit functional group isomerism. For example, thereare two compounds having
the same molecular formula C2H6O , but different arrangement of atoms.
H3C O CH3 H3C CH2 OH
Methoxy methane Ethanol
4. Metamerism
This type of isomerism arises due to the unequal distribution of carbon atoms on either
side of the functional group. Such compounds belong to the same homologous series. For
example, diethyl ether and methoxy methane.
H3C H2C O CH2 CH3 H3C O CH2 CH2 CH3
Ethoxy ethane Methoxy propane
For a ketonic compound having the molecular formula C5H10O, the following two metamers
are possible.
O O

H3C H2C C CH2 CH3 H3C C CH2 CH2 CH3

3-Pentanonone 2-Pentanone
5. Tautomerism
This type of isomerism arises due to shifting of proton from one atom to another in the
same molecule. This is commonly seen in amino acids. They exist as zwitterions which
are formed when a proton is shifted from the carboxylic acid end of amino acid molecule
to the amine group.
COOH COO

R C NH2 R C NH3

H H
Amino acid Zwitterion
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B. Stereoisomerism
Stereoisomers are such compounds which possess the same structural formula, but differ
with respect to the positions of the identical groups in space. It is part of class 12 syllabus
and will be covered there.
There are two types of stereoisomerism;
i. Geometrical or cis trans isomerism
ii. Optical isomerism

11.11 ORGANIC REDOX REACTIONS

Oxidation-Reduction reactions that involve organic compounds are called organic redox
reactions. These reactions are characterized by the addition or removal of atoms/bonds.
Normally, during organic oxidation, oxygen is added or hydrogen is removed. During
organic reduction, hydrogen is added or oxygen is removed. Some examples of oxidation
and reduction reactions are given below:
11.11.1 Oxidation
Oxidation of organic compounds involving reaction with oxygen is usually the combustion
reaction:
C2H6 + 2O2 2CO2 + 3H2
Reactions of organic compounds with oxidizing agents.e.g.
i) Ozonolysis is a method of oxidatively cleaving alkenes using ozone (O3).

ii) The epoxidation of alkene is also example of oxidation reaction. In this reaction various
oxidizing agents can be used like molecular oxygen and metal catalysts.

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iv) Reaction of primary alcohols with acidified K2Cr2O7 to make carboxylic acids, detail
will be discussed in class 12 syllabus.
C2H5OH + 2[O] CH3COOH + H2O
a) Reduction
Addition of hydrogen to carbon-carbon double bond to form alkane is an example of
organic reduction reaction.

Various reducing agents are used in Organic synthesis. e.g; LiAlH4, NaBH4, Sn + conc.HCl.
Reduction of nitriles to amines, amides to amines, carboxylic acid to primary alcohols,
nitrobenzene to phenylamine are all examples of reduction and will be studied in class 12
syllabus.
O OH
LiAlH4
H3C–C–H + 2[H] CH3–CH2
∆
Quick Check 11.9
a) Draw the displayed formula and name an isomer of C4H8 that could be an example of
positional isomerism?
b) What type of isomers are ethoxy methane ether and propanol?
c) What are the different types of structural isomerism in alkenes?
d) Write down different isomers of the compound C4H9NH2.

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. An alkene undergoes ozonolysis followed by reduction with zinc dust and water
to yield propanone and methanal. The alkene is:
a) 1-Butene b) 2-Butene
c) 2-Methylpropene d) 2-Methyl-2-butene

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II. Which of the following reagents is typically used for the acid-catalyzed hydration
of alkenes to form alcohols?
a) H2​/Ni b) O3​followed by Zn/H2​O
c) Dilute H2​SO4​ d) Br2​in CCl4​
III. Halogenation of alkanes is an example of:
a) Electrophilic substitution  b) Nucleophilic substitution
c) Free-radical substitution d) Oxidation
IV. Which of the following reactions can an alkane undergo?
a) Addition b) Substitution
c) Polymerization d) Nitration
V. What is the first step in the electrophilic addition reaction of alkenes?
a) Formation of a carbocation
b) Attack by a nucleophile
c) Attack by an electrophile on the double bond
d) Formation of a free radical
VI. The addition of unsymmetrical reagent to an unsymmetrical alkene is in
accordance with the rule/principle?
a) Markovnikov’s Rule b) Hund’s Rule
c) Le Chatelier’s Principle d) Aufbau Principle
VII. The most stable carbonium ion among the following is:
a) CH3+   b) CH3CH2+  
c) (CH3)2CH+   d) (CH3)3C+
VIII. Markownikov’s rule is applicable to :
a) CH2 = CH2 b) CH3 — CH2 — CH3
c) CH3 — CH = CH—CH3 d) (CH3)2 — C = CH2
IX. What intermediate is formed during the electrophilic addition of HBr to an
alkene?
a) Carbocation b) Carbanion
c) Radical d) Epoxide
X. The enhanced stability of conjugated dienes compared to isolated dienes is
primarily attributed to:
a) Inductive effects of the double bonds.
b) Increased s-character of the hybridised orbitals.
c) Delocalisation of π electrons across the conjugated system.
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d) Steric hindrance between the double bonds.

XI. Which of the following carbocations would be the least stable?
a) (CH3​)2​CH+ b) CH3​CH2+​
c) CH3+​ d) (CH3​)3​C+
XII. Which of the following is the repeating unit in the polymer poly(ethene)
(polyethylene)?
a) −CH2​CH3​− b) −CH=CH−
c) −CH2​CH2​− d) −CH(CH3​)CH2​−
XIII. Which type of structural isomerism involves differences in the arrangement of
the carbon skeleton?
a) Chain isomerism b) Positional isomerism
c) Metamerism d) Stereoisomerism

SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. Define the following:
i) Cycloalkanes ii) Isomerism iii) Conjugated dienes iv) Inductive effect
b. Differentiate between:
i) Aliphatic and Aromatic hydrocarbons
ii) Homolytic and Heterolytic Fission
iii) Electrophile and Nucleophile
c. Explain why alkanes do not undergo addition reactions.
d. How elimination reaction is considered the opposite of an addition reaction.
e. Compare the carbocation stability in propene and 2-butene.
f. Given the molecular formula C₅H₁₀, list all possible structural isomers that are alkenes.
g. When propene (C₃H₆) undergoes electrophilic addition with HBr, it forms 2-bromopropane
as the major product. Explain why 2-bromopropane is favored over 1-bromopropane, using
the concept of carbocation stability.
h. Explain why conjugated alkenes may show different reactivity compared to isolated
alkenes.
i. Explain how inductive effects from alkyl groups stabilize carbocations in alkenes.
j. Write the equation for each reaction.
i. CH3CH2CH=CH2 with H2 (Ni catalyst)
ii. CH3CH=CH2 with Cl2

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iii. CH3CH2CH=CHCH2CH3 with H2O (H2SO4 catalyst)

k. Write structural formulas for each of the following compounds.
i) Isobutylene ii) 2,3,4,4-Tetramethyl-2-pentene
iii) 2 ,5-Heptadiene iv) 4,5-Dimethyl-2-hexene
v) Vinylacetylene vi) 1,3-Pentadiene
vii) 1-Butyne viii) 3-n-Propyl-1, 4-pentadiene
ix) Vinyl bromide x) But-1 -en.3 -yne
xi) 4-Methyl-2-pentyne xii) Isopentane
l. Write down names of the following compounds according to IUPAC-System.

DESCRIPTIVE QUESTIONS
Q.3 Describe the free radical halogenation of methane using Cl2 as an example.
Q.4 Describe the following methods for the preparation of alkenes:
i) Dehydrohalogenation of alkyl halides
ii) Dehydration of alcohols
Q.5 Describe the mechanism of electrophilic addition of hydrogen halides to alkenes.
Discuss Markovnikov’s Rule in the context of hydrogen halide addition.
Q.6 Explain the following reactions of alkenes with examples:
a) Halogenation b) Ozonolysis
c) Epoxidation d) Polymerization

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 NITROGEN AND SULFUR

12
Chemistry-XI

NOTROGEN
AND SULFUR
STUDENT LEARNING OUTCOMES [C-11-B-30 to C-11-B-41]
Explain the lack of reactivity of nitrogen due to its triple bond strength and lack of polarity.
(Understanding)
Describe the basicity of ammonia using the Bronsted-Lowery theory. (Understanding)
Identify the structure of the ammonium ion and explain how it is formed by an acid-base
reaction. (Understanding)
Describe how ammonia can be displaced from ammonium salts through an acid-base
reaction. (Understanding)
Describe natural and man-made occurrences of oxides of nitrogen and their catalytic
removal from exhaust gases of internal combustion gases. (Understanding)
Explain the role of NO and NO2 in the formation of photochemical smog, specifically
in the reaction with unburned hydrocarbons to form peroxyacetyl nitrate (PAN).
(Understanding)
Differentiate between nitrification and de-nitrification. (Knowledge)
Explain the lack of reactivity of sulfur, with reference to its bonding and stability of its
compounds. (Understanding)
Describe the different oxidation states of sulfur and their relative stability. (Understanding)
Describe the properties and uses of sulfuric acid, including its production and industrial
applications. (Understanding)
Describe the chemical reactions and processes involving sulfur, such as combustion and
oxidation. (Understanding)
Explain the uses of sulfur compounds in industry and everyday life, such as in fertilizers,
gunpowder, and rubber, and in synthetic organic chemistry, including the synthesis of
dyes, drugs, and fragrances. (Understanding)

NITROGEN
Nitrogen belongs to group 15 of the periodic table. In industrial processes, nitrogen is
typically obtained by cooling air until it becomes a liquid. Liquid nitrogen is commonly
used for rapid cooling purposes. In laboratory settings, nitrogen can be generated by slowly
heating a solution of ammonium nitrite.

NH4 NO2(aq) N2(g)+ H2O(l)

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Table 12.1 Physical properties of nitrogen

Atomic number 7 Ionic radius (3-) 171 pm

Relative atomic mass 14.007 Da 1st Ionization energy 1402 kJ/mol
Physical appearance Colourless Gas Electronegativity 3.0
Electronic configuration [He] 2s2 2p3 Electron affinity -8.0 kJ/mol
Melting point -210 ○C Density 0.001145 g/cm3
Boiling point -195.8 ○C Principal oxidation 3+ and 5+
Covalent radius 74 pm states

12.1 REACTIVITY OF NITROGEN (N2)

Nitrogen is a significant component of the air,
known for its low reactivity due to its small size,
symmetrical electronic cloud, and nonpolar
triple bond. With an electronic configuration N N N≡N
of 1s2 2s2 2p3, nitrogen requires three electrons
to complete its octet, forming a triple bond by
sharing three electrons with another nitrogen Figure 12.1 Bonding in N2 molecule
atom as shown in Figure 12.1. This bond has
a bond enthalpy of +944 kJmol−1. High energy is required to break this bond to form new
bonds, making N2 very unreactive. The second reason for its lack of reactivity is the non-
polarity of its bond. Both the atoms are the same having zero electronegativity difference.
This causes equal sharing of the three bonded electrons between the two atoms making the
bond nonpolar.

Interesting Information!
The high concentration of nitrogen in the air serves to dilute oxygen, preventing every spark in our
atmosphere from igniting a massive fire. In the case of large shipments of hydrocarbons or edible oils, it
is crucial to utilize blankets of Nitrogen or any other inert gas on ships to safeguard them from oxygen
and moisture. It is also used in laboratory to carry out the reactions which require inert atmosphere.

12.2 AMMONIA (NH3)

Ammonia (NH3) is an important industrial compound of nitrogen, which is mainly used as
a fertilizer. zzIt is prepared industrially by Haber-Bosch process.

N2(g) + 3H2(g) 2NH3(g)

12.2.1 Basicity of Ammonia
Ammonia behaves as a Lowry-Brønsted base by accepting a proton (H+) from an acid to
form ammonium:
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NH3(aq) + H+1(aq) NH41+(aq)

It dissolves in water to form ammonium hydroxide (NH4OH) and equilibrium is established
between ammonia molecules and ammonium ions in the solution.
NH3(aq) + H2O(l) 1+ + OH 1-
NH4(aq) Kb=1.8×10-5
(aq)

Ammonia solution is a weak base due to the low basicity constant (Kb) and the equilibrium
position being towards the far left side.
H
12.2.2 Structure of Ammonium (NH41+) +
Ammonia molecule has pyramidal shape due to lone
N N
H H H H
pair of nitrogen. But when nitrogen atom in ammonia
utilizes this lone pair of electrons to form ammonium, H H
this ion adopts a tetrahedral shape in which all the Figure 12.2 Pyramidal and tetrahedral
bonds are of equal length and strength, as depicted in shapes of ammonia and ammonium
Figure 12.2.
12.2.3 Synthesis of Ammonia from Ammonium salts
In the laboratory, ammonia gas can be synthesized by heating an ammonium salt such as
ammonium chloride (NH4Cl) with a base like calcium hydroxide (Ca(OH)2) as shown in
Figure 12.3.
NH4Cl(s)+ Ca(OH)2(aq) NaCl(aq) + H2O(l) + NH3(g)

In this acid-base reaction, NH4+ acts

as an acid by donating H+ ions, while
OH- acts as a base by accepting H+ ions.
This reaction displaces ammonia gas
from the ammonium salt and produces
salt and water. It is commonly used to
identify ammonium in salt analysis. If a
gas with a pungent smell is released and
turns moistend red litmus paper blue, it
indicates the presence of ammonium in
the compound.
Figure 12.3 Synthesis of ammonia gas
Quick Check 12.1
a) Why N2 gas is used in food packaging?
b) Both CO and N2 have triple bonds in their molecules. Why do you think CO is more reactive than N2?
c) Ammonium salts such as (NH4)2SO4 or (NH4)2NO3 are commonly used as fertilizers. Why a farmer
wouldn’t treat a field with an ammonium fertilizer at the same time as using lime? What would be the
chemical reactions?
d) If magnesium ribbon is ignited and placed in a jar containing N2O, it continues to burn brightly.
Explain this observation with reason.

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12.3 OXIDES OF NITROGEN

Oxides of nitrogen are NO, N2O, NO2, N2O4 and N2O5 in which oxidation states range from
I+ to V+. N2O4 and N2O5 decay quickly to other oxides. NO and NO2 are collectively called
as NOx. The structures, properties and uses of these oxides are given in Table 12.2.
Table 12.2 Properties of some common oxides of nitrogen
Formal
Name and
Structure oxidation Properties Uses
formula of oxide
state
Dental
Colourless gas,
Nitrous oxide/ anaesthetic,
water-soluble,
Nitrogen oxide propellant for
N N O neutral, sweet
(Laughing gas) 1+ whipped ice
smelling, helps in
N2O cream, synthesis
combustion
of NaN3
Colourless
gas, slightly Biochemical
water-soluble, messenger
N O neutral, NO is (Lowers blood
Nitic oxide,
2+ paramagnetic pressure and
Nitrogen dioxide
N N while N2O2 is role in other
NO, N2O2 O O diamagnetic, body functions),
oxidising as well synthesis of
as reducing in nitrosyl carbonyls
nature
Nitrogen N 4+ NO2 is a reddish- Rocket
dioxide/Nitrogen O O brown gas, propellant, HNO3
peroxide, paramagnetic, and formation by
Nitrogen O O reacts with water Ostwald process,
tetraoxide to form HNO3 and explosives
N N
NO2, N2O4 HNO2, N2O4 is
Cool
O O colourless liquid
2NO2 N 2O 4 or solid
Brown Heat Colouriess

Did you know?

Another recommended name for ammonia by the International Union of Pure and Applied Chemistry
(IUPAC) is Azane and for ammonium is Azanium. These names have been derived from Azote, a Greek
name for nitrogen, meaning “no life”. These names are used in naming derivatives of ammonia and
ammonium e.g. sodium azide (NaN3).

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12.4 SOURCES OF OXIDES OF NITROGEN

Here are the main categories of NOx sources.
12.4.1 Natural Sources
Natural sources include lightning, volcanoes, biological decay, forest fires, soil
microorganisms, oceans, etc. NO is produced when N2 and O2 in the air react during
lightning. It is produced by microorganism using air N2.
12.4.2 Anthropogenic (Man-made) Sources
The main anthropogenic sources of NOx are the combustion of fossil fuels in vehicles and
power plants. Other sources include chemical plants, biomass burning, welding, etc.

12.5 ROLE OF NO & NO2 IN SMOG & PAN FORMATION

NOx is responsible for numerous harmful effects on living organisms.
12.5.1 Photochemical Smog
Photochemical smog (Los Angeles smog) forms in the atmosphere from NOx and volatile
organic compounds (VOCs) in the sunlight. It is oxidising in nature. Photochemical
oxidants, such as NO2, ozone, and peroxyacyl nitrates (PANs) can react and oxidise
specific compounds in the atmosphere. Photochemical smog is becoming more common
than classical smog (London smog) due to increasing NOx emissions. The formation of
photochemical smog involves the following chemical reactions.

N2(g) + O2(g) 2NO(g)

Did you know?
2NO(g) + O2(g) 2NO2(g) Lahore smog consists of volatile organic
hυ compounds (VOCs), NOx, ground level ozone
NO2(g) NO(g)+ O(g)
(O3), particulate matter PM2.5, CO and SO2.
O(g) + O2(g) O3(g)

RCH=RCH(g)+ O3(g) RCO•3(g)+ RCH•2(g)→→→RC(O)OONO2

12.5.2 Formation of Peroxyacyl Nitrates (PANs) O

NOx take part in a series of reactions leading to
the formation of ozone (O3), aldehydes, peroxyacyl C O O
nitrates (PANs) and peroxybenzoyl nitrate (PBN). R O N
PAN is one of the members of peroxyacyl nitratesas O
shown in Figure 12.4. Figure 12.4 General structure of PANs
The R group in peroxyacetyl nitrate is CH3, but other hydrocarbon chains may also be
present.

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The formation of PAN is illustrated in Figure 12.5. The main component of oxidizing smog
is ozone, which oxidizes hydrocarbon to produce aldehyde. The aldehyde then reacts with
hydroxyl radical to produce acyl radical. The acyl radical reacts with oxygen to produce
peroxyacyl radical, which finally reacts with nitrogen peroxide to form peroxyacyl nitrate.

Reactive Hydrocarbon

O3

RCH2 O2
RCH3
RCH2O
NO

NO2 + HO RCH2O + NO2

NO
HO2 + RCHO O2
OH
RC =O
O2
O
RC–=O
O
NO2

O
RC–=O
ON
O
3

Figure 12.5 Mechanism of PAN formation

Quick Check 12.2

a) Draw the structures of the following oxides of nitrogen. Also, briefly explain their bonding.
i) N2O ii) NO iii) NO2
b) What does PAN stand for? Give its general formula.
c) Write down the formulas of the compounds responsible for the formation of PAN.
d) If magnesium ribbon is ignited and placed in a jar containing N2O, it continues to burn brightly, how
does the product form in this reaction confirm the structure of N2O?

12.6 CATALYTIC CONVERTER

A catalytic converter is a ceramic or metallic monolith with a honeycomb-like structure, as
shown in Figure 12.6. Its inner channels have a layer of alumina to provide a high surface
area. Noble expensive metals such as Pt (Platinum), Pd (Palladium), and Rh (Rhodium) are
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dispersed on the alumina.

These metals catalyze three redox reactions H2O, CO2, N2 washcoat with
to remove the half harmful exhaust gases. catalyst inside the
monolith channel
The three-way converter converts harmful
CO, NO, and hydrocarbons into CO2, N2,
and water. These precious metals can also be
recycled.
HC, CO, Nox
Reduction
Figure 12.6 Three-way catalytic converter
Pt / Rd
2NO(g) + 2CO(g) N2(g) + 2CO2(g)
Oxidation
Pt/Rh
2CO(g) + O2(g) 2CO2(g)
Pt/Rd
2C2 H4 + 6O2(g) 4CO2(g) + 4H2O(g)

12.7 NITRIFICATION AND DENITRIFICATION

Nitrification and denitrification are the two phases of the nitrogen cycle. Nitrification
involves the conversion of ammonium (NH41+) to nitrite (NO21-) and nitrate (NO31-),
while denitrification involves the conversion of nitrate (NO31-) to Nitrogen (N2). These
two processes are also involved in the wastewater treatment to remove nitrogen. Some
differences between nitrification and denitrification are given in Table 12.2.

Table 12.3 Differences between nitrification and denitrification

Nitrification Denitrification
Ammonia NH3/ NH41+ is converted Nitrite (NO2 and nitrate (NO31-) are
1-)

into nitrite (NO21-) and nitrate (NO31-). converted back to N2 that is released into
the atmosphere.

Nitrifying bacteria aerobic conditions, pH Denitrifying bacteria anaerobic

6.5 – 8.0, optimum temperature 20 ○C–30 conditions, pH 7.0–9.0, optimum
○C. temperature 26 ○C – 38 ○C.
Plants absorb these nitrites and nitrates for It is important in wastewater treatment
their nutrition as they cannot assimilate and useful for aquatic life, to oxidize
nitrogen directly from the atmosphere. NH4+ with NO2− to form N2 gas.
Oxidation of nitrogen Reduction of nitrogen
NH4+ → NO2– → NO3– NO3– →NO2– → NO → N2O → N2
1+ + 3O
2NH4(aq) 1- +4H + +2H O
→ 2NO2(aq) 1– + 10e– + 12H + →N
2NO3(aq) + 6 H2O(l)
2(aq) (aq) 2 (l) (aq) 2(g)
1- + O
2NO2(aq) 1-
→ 2NO3(aq)
2(aq)

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Quick Check 12.3

a) Write down the reduction and oxidation reactions that occur in the catalytic converter in the vehicle
exhausts.
b) What is the basic principle of catalytic converter? Describe the role of catalyst in the catalytic converter.
c) Do hybrid and electric cars have catalytic converters? Explain why or why not.

12.8 SULFUR
Sulfur is a member of group 16 which is also called the Chalcogen family. Some physical
properties of sulfur are listed in Table 12.3.
Table 12.4 Physical properties of Sulphur

Atomic number 16 Ionic radius 184 pm

Relative atomic 32.06 a.m.u. 1st Ionization 1000 kJ/mol

mass energy

Physical Solid Yellow Electronegativity 2.5

appearance

Electronic [Ne] 3s2 3p4 Electron affinity -200 kJ/mol

configuration

Melting point 113 ○C (honey- Density 2.07 g/cm3

yellow)

Boiling point 445 ○C (dark Common oxidation 4+ and 6+

brown) states
Common Bonding Covalent
Covalent radius 104 pm
bond
12.8.1 Reactivity of Sulfur
S
Sulfur usually forms single bonds with other S S
sulfur atoms instead of double bonds due to S S
poor overlapping of the orbitals. As a result, it
forms larger molecules and structures through S
a process called catenation. S8 is a crown-like
molecule, as shown in Figure 12.7. S S
Figure 12.7 Cyclo-octasulfur, (S8) crown molecule
12.8.2 Oxidation States of Sulfur
Sulfur exhibits oxidation states of −2, 0, +2, +4, and +6. The electronic configuration of
sulfur is depicted in Figure 12.8, where the oxidation state is determined by the number of
unpaired electrons. Under standard conditions, sulfur and oxygen react to produce sulfur

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dioxide (SO2) in which sulphur has an oxidation state of +4. However, to form sulfur
trioxide (SO3) with an oxidation state of +6, high energy is required.

Figure 12.8 Electronic configurations of sulfur for attaining different oxidation states

12.9 STABILITY OF OXIDATION STATES OF SULPHUR

The Stability of oxidation states of sulphur is explained by Frost diagram in which an
element X is a plot of nE⁰ vs oxidation state (n) for the redox couple X(n)/X(0) as shown in
Figure 12.9. It tells about the relative stabilities of different oxidation states of an element
at two extreme pH values (pH=0 and pH=14) i.e. acidic and basic conditions. It can also
be regarded as a plot between standard reaction Gibb’s free energy (∆G°) versus oxidation
state (n) because oxidation state(n) is directly proportional to ∆G° as shown below.
₋∆G° = nFE⁰
or ₋∆G° = nE⁰
F
Here E⁰ is the standard reduction potential, F is the Faraday constant and n is the number
of transferred electrons in a redox half reaction.
The more stable oxidation state has a lower 2 acidic solution SO42–
SO2(aq)
nE⁰ value or more negative Gibb’s free energy. 1 S2–

Therefore, the more stable oxidation state is 0

S8
at the lowest position in the diagram. Further, H2S(g)
nE–0(V)

–1
a couple with a more positive slope is a good –2
SO32–
oxidising agent, while a couple with a more –3 basic solution
negative slope is a good reducing agent. –4 SO42–
In the diagram for sulfur, +6 (SO4 2-)
is the –5

most thermodynamically stable oxidation -II 0 II IV VI

state, completely non-oxidising under extreme Oxidation state (n)

basic conditions, while under extreme acidic Figure 12.9 Frost diagram for oxidation states
conditions, it is shown to be very unstable. of sulfur

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It can be seen that in basic environments, the oxidized sulfur states are all more stable than
the elemental form but under acidic conditions all the oxidized sulfur states are less stable
than the elemental form.
Quick Check 12.4
a) Determine the oxidation state of S in the following species.
i. SO3 ii. H2SO4 iii. SO42- iv. S2O32-
b) Which oxidation states of sulphur are the most common? Explain your answer with reason.
c) Explain the involvement of d orbital in variable oxidation states of S in its compounds.

12.10 REACTIONS OF SULFUR

Sulfur can combine with many elements to form a wide variety of inorganic and organic
compounds. It is unreactive to water under normal conditions, dilute non-oxidising acids,
and noble gases. Its ability to catenate allows it to form ring structures and linear chains.
Here are some important reactions of sulfur:
i. Sulfur burns in the air to form SO2 with a blue colour flame. The other main sulphur
oxide is SO3 which requires higher temperature and a catalyst for its formation.
S(s) + O2(g) SO2(g)

2SO2(g) + O2(g)2SO3(g)
Pt
Sulfur can be oxidised by nitric acid to produce NO2 and H2SO4.
S(s) + 6HNO3(l) H2SO4(l)+ 6NO2(g) + 2H2O(l)
ii. When sulfur reacts with elements that have lower electronegativity, it acts as an
oxidizing agent and forms their sulfides. It tarnishes Ag, Cu, and Zn by forming a
coating of metal sulfide. Sulfur does not react with Au and Pt.
2Ag(s) + S(s) Ag2 S(s)
Hg(l) + S(s) HgS(s)
2Cu(s) + S(s) Cu2S(s)
iii. Sulfur converts cyanide into thiocyanate which is also known as pseudohalide. It is
used to analyse Fe3+.

KCN(s)+S(s) KSCN(s)
iv. Sulfur reacts directly with F2 to form SF4 and SF6. Sulfur hexafluoride (SF6) is a gas
and is very unreactive. It is used as an insulator gas in electric devices. Sulfur readily
reacts with Cl2 to form S2Cl2 (yellow liquid) which further reacts with Cl2 to form SCl2
(red liquid).

S(s) + 3F2(g) SF6(g)

2S(s)+ Cl2(g) S2Cl2(l)

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12.11 USES OF SULFUR AND ITS COMPOUNDS

12.11.1 Vulcanisation
S S
Sulphur is used as a cross linker for the rubber molecular
chains. This is called vulcanisation and it improves the strength
of rubber as shown in Figure 12.10.
S S
12.11.2 Fertilizer S S

Sulfur is an essential nutrient for plant growth. When soils

become depleted in sulfate, sulfur can be restored in soil by
applying sulfur containing N/P fertilizers, or sulfur-coated
S
fertilizers such as sulfur-coated urea. Soil components and S

microbes convert elemental sulfur into soluble forms for the

use of plants. Gypsum (CaSO4 . 5H2O) is also used as a fertilizer.
Figure 12.10 S-S cross-linkages
12.11.3 Gun powder between polymer chains
Gun powder is a coarse blend of 75% potassium nitrate (KNO3), 15% wood charcoal,
and 10% sulfur. Charcoal carbon is the main fuel, nitrate is the oxidiser and sulfur is the
additional fuel that burns the powder faster. The following reaction in burning takes place:

10KNO3(s) + 3S(s) + 8C(s) 2K2CO3(s) + 3K2SO4(s) + 6CO2(g) + 5N2(g)

Quick Check 12.5
a) What is the function of SO2 and sulfite (SO32-) salt in preserving the food?
b) Give the reaction of S with HCl acid and NaOH.

12.12 ROLE OF SULFUR IN ORGANIC SYNTHESIS OF

DRUGS, DYES AND FRAGRANCES
Carbon-Sulfur bonds are prevalent in a wide range of compounds with biological,
pharmaceutical, and material properties. These bonds form a large number of organic
compounds containing a variety of functional groups such as thiols or mercaptans,
thioethers, sulfoxides, sulfones, etc.
12.12.1 Drugs
Sulfa drugs are the antibacterial sulfonamides such as penicillins and cephalosporins
contain sulfur. The common drug omeprazole, used in GERD (Gastroesophageal reflux
disease) contains sulfoxide group.
12.12.2 Dyes
Sulfur dyes are synthesised by the process of thionation or sulfurization of organic
compounds that contain nitro or amino groups. These compounds contain sulfur linkages.
They generally give black, brown, khaki, blue, and green colours.
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Some examples are sulfur black 1, sulfur blue and sulfur brilliant green.
12.12.3 Odorants/Fragrances
Mercaptans are used to give odour to natural gas. Some thiols have pleasant odours on high
dilution, for example, thioterpineol is the key ingredient in the aroma of grapefruit. cis-
glabanum oxathiane is a fragrant compound. It is used in fine fragrances, soaps, shampoos
and shower gels. Many naturally occurring odorants are produced synthetically and also
applied as flavouring agents.

12.13 SULPHURIC ACID (H2SO4)

The major portion of sulfur, around 85%is used for the production of sulphuric acid (H2SO4). It
has tetrahedral structure with two S−O and two S=O bonds as shown in Figure 12.11.

Figure 12.11 Structure of H2SO4

12.13.1 THE CONTACT PROCESS

Sulphuric acid is produced by the contact process. A flow sheet diagram of the contact
process is shown in Figure 12.12.

Figure 12.12 Contact process for the industrial production of sulphuric acid
The Contact process can be divided into the following stages.

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Sulfur/pyrite Burners
The process starts with the combustion of molten sulphur or by heating pyrites such as iron
pyrite (FeS) in excess of air to produce sulfur dioxide SO2.
S(s) + O2(g) SO2(g) ∆H = -297.03 kJ/mol

4FeS(s) + 6O2(g) 2Fe2O3(s) + 4SO2(g)

Purification Unit
If pyrite ore is used as a sulfur source, the SO2 gas formed may contain contaminants like
dust particles, vapours, and arsenic oxide. These contaminants affect the efficiency of the
catalyst. Hence, the gas needs to pass through the purification unit. In an arsenic purifier,
gelatinous ferric hydroxide Fe (OH)3 present in horizontal shelves, absorbs arsenic oxide
As2O3.

As2O3(g) + 2Fe(OH)3(l) 2FeAsO3(l) + 3H2O(l)

Contact Tower and Heat Exchangers

Purified SO2 and air, preheated at 420 °C– 450 °C, are fed to the first converter stage of
the contact tower at 1–2 atm pressure. Here, these gases come in contact with vanadium
pentoxide (V2O5) catalyst.
1
SO2(g) + O2(g) SO3(g) ∆H= -98.98 kJmol-1
2
The catalyst works in two steps:
Oxidation of SO2 into SO3 by V5+:
SO2(g) + V2O5(s) SO3(g) + 4V2O4(s)
Oxidation of V4+ back into V5+ by oxygen (catalyst regeneration):
1
V2O4(s) + O2(g) V2O5(s)
2
Quick Check 12.6
a) Why is high temperature and catalyst needed to form SO3?
b) Figure
Write down 12.16: The
dehydration contact
reactions oftower
conc.containing
H2SO4 withcatalyst
starch beds with heat
and oxalic exchangers
acid
c) How does the catalyst V2O5 function in the conversion of SO2 to SO3.

Absorption Tower
Sulfur trioxide is cooled and can be converted to sulphuric acid by reacting with water.
H2O(l) + SO3(g) H2SO4(l) ∆H = -176.6 kJ/mol
Mixing SO3 with water is not feasible because the reaction is extremely exothermic and
acidic vapour or mist is produced rather than a liquid solution. Mainly, sulfur trioxide is
dissolved in recirculating hot 98.5% sulphuric acid. The term fuming sulphuric acid or
oleum is used for the mixtures of sulfur trioxide with 100 percent sulphuric acid.
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Oleum undergoes a reaction with water to make a highly concentrated solution of H2SO4
whose concentration can be adjusted.
H2SO4(l) + SO3(g) H2S2O7(l)

H2S2O7(l) + H2O(l) 2 H2SO4(l)

12.13.2 Physical Properties
Sulphuric acid is soluble in water and hygroscopic in nature. It readily absorbs water vapour
from the air. Anhydrous H2SO4 is a very polar liquid. It is highly corrosive to various
materials. On contacting the skin, it causes chemical burns. Some physical properties of
sulphuric acid are given in Table 12.4.
Table 12.5 Physical properties of Sulphuric acid
Molar mass 98.08 g/mol
Physical appearance colourless viscous liquid
Odour odourless
Melting point 10 ○C
Boiling point 290 ○C
Specific gravity (15 °C) 1.83 g/cm3
Viscosity 25.24 centipoise
Vapour pressure (25 °C) 0.001 torr
Sulphuric acid is a highly corrosive
substance. It can badly burn cloths, plastic,
rubber and injured the human skin, eyes,
etc,. Handle it very carefully.

12.13.3 CHEMICAL PROPERTIES

i. It self-ionizes or undergoes autoprotolysis as follows.
H2SO4(l) +H2SO4(l) H3SO1+
4 (aq)
+ HSO41-(aq) K = 2.7 × 10-4
The equilibrium constant value is greater than that of water which makes it to be used as a
non aqueous protic solvent.
Sulphuric acid is a strong acid as shown by its pKa1 value:

H2SO4(aq) H3O+(aq) + HSO4(aq)

1- (pKa1 = –2)
But hydrogensulfate (HSO41-) is a far weaker acid due to a positive pKa2 value:

HSO4(aq)1- + H2O(l) H3O+(aq) + SO4(aq)

2- (pKa2 = 1.92)
ii. Concentrated sulphuric acid is a powerful dehydrating agent that removes water from many
substances such as sucrose, starch, wood, and paper to produce carbon, steam, and heat.

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Interesting Information!
A common laboratory demonstration is the dehydration of table sugar, where a black porous carbon
mass called carbon snake protrudes out of the apparatus.
C12H22O11(s) + H2 SO4(l) 12C(s) + 11H2O(g) + H2SO4(aq)

It also dehydrates ethyl alcohol to ethene or ethoxyethane depending upon the reaction
conditions.
C2H5OH(l) + H2SO4(l) C2H4(s)+ H2O(l) + H2SO4(aq)
iii. Hydrochloric acid (HCl) gas, is formed when sulphuric acid reacts with sodium
chloride
NaCl(s) + H2SO4(l) NaHSO4(s) + HCl(g)
iv. Reactions of sulphuric acid with metals depend upon the metal, concentration of
the acid, and temperature. Metals that are above hydrogen in electrochemical series
such as Fe, Al, Zn, Mn, Ni, and Mg react directly with dilute sulphuric acid to
produce hydrogen gas and metal sulfates.But with cold conc. H2SO4, they liberate SO2
and formsulfates.
Zn(s) + H2SO4(aq) H2(g) + Zn2+
(aq)
+ SO2-
4 (aq)

Zn(s) + H2SO4(l) SO2(g) + Fe2+

(aq)
+ SO2-
4 (aq)
+ 2H2O(l)
v. Metals like Cu, Ag, and Hg react with hot conc.H2SO4 to form metal sulfates. Sulphuric
acid is not regarded as a typical oxidising agent due to the stability of SO42- anion. This
anion is weakly oxidising. However hot concentrated sulphuric acid is a moderately
strong oxidising agent due to high temperature, high concentration of protons (H+),
and formation of nascent oxygen. Hot concentrated sulphuric acid oxidises Cu, as
given below:
Cu(s) + 2H2SO4(l) SO2(g) + 2H2O(l) + SO42–(aq + Cu(aq)
2+

Quick Check 12.7

a) Write down dehydration reactions of conc. H2SO4 with starch and oxalic acid.
b) How does conc. H2SO4 react with NaCl? What is the importance of this reaction?
c) What is the difference between the oxidizing power of cold and hot sulphuric acid?
12.13.4 Uses and Industrial Applications
Sulphuric acid is considered a king of chemicals and its consumption is an indicator of the
industrial progress of a country.
1. A major portion of the acid is used in making fertilizers, normally 77.67 % is used to
digest the phosphate rock containing calcium phosphate (Ca3(PO4)2.
2. It is used in the extraction of metals from ores such as Cu, Ni, steel etc.
3. It is utilized as a catalyst in oil and coal refining, polymers, synthetic rubber, and
plastic industries.
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4. It is used in the pulp and paper industry and involved in the production of pesticides,
insecticides, herbicides, varnishes, dyes, pharmaceuticals, soaps and detergents.
5. It is used for nitration in making explosives such as trinitrotoluene (TNT), nitro-
glycerine, picric acid, nitrocellulose, etc.
6. It is involved in the food industry for making sugar, starch, and corn syrup.
7. It is used in the paint industry for making titanium dioxide (TiO2) pigment.
8. It is used to dry gases in industrial processes.
9. 35.67% acid is used in lead storage batteries.
10. It is used as a laboratory reagent.
Even though it is used in various industries, it is rarely contained in the final product.

Did You Know?

Fluorapatite (Ca5(PO4)3F) to make single superphosphate Ca(H2PO4)2 and phosphoric acid (H3PO4).
H3PO4 is further used to make double and triple superphosphates and ammonium phosphate. Sulphuric
acid also reacts with ammonia to make ammonium sulfate fertilizer.

EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. Despite being the most abundant gas in the Earth’s atmosphere, nitrogen does not
readily participate in combustion reactions because:
a) It is denser than oxygen.
b) It has a high specific heat capacity.
c) Breaking the N≡N bond requires a large amount of energy.
d) It is a noble gas.
II. A student heats a solid ammonium salt with a solution of a strong alkali. The gas
produced turns damp red litmus paper blue and has a characteristic pungent
smell. The gas is:
a) Hydrogen (H2​) b) Carbon dioxide (CO2​)
c) Ammonia (NH3​) d) Sulfur dioxide (SO2​)
III. The shape of ammonium is
a) pyramidal b) triangular planar
c) tetrahedral d) linear

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IV. In a catalytic converter, the conversion of nitrogen oxides (NOx​) into nitrogen gas
(N2​) and oxygen gas (O2​) is a process of:
a) Oxidation. b) Reduction.
c) Combustion. d) Neutralization.
V. PAN formation starts when______ reacts with the hydrocarbon.
a) NO b) NO2
c) O3 d) HO•
VI. Nitrification is the process by which:
a) Atmospheric nitrogen is converted into ammonia.
b) Nitrate is converted into nitrogen gas.
c) Ammonia is converted into nitrite and then nitrate.
d) Organic nitrogen is converted into ammonia.
VII. The most stable species in an acidic environment is
a) SO42- b) SO2
c) H2S d) S
VIII. Which gas is used in separating hard water from normal water?
a) SO2 b) H2S
c) NH3 d) NO2
IX. The oxidation state of sulfur in H2SO4 is
a) +1 b) +2
c) +4 d) +6
X. In a Frost diagram, a species that lies above the line connecting its neighbors is:
a) Thermodynamically stable. b) A strong oxidizing agent.
c) Prone to disproportionation. d) A poor reducing agent.
XI. Sulfur dioxide (SO2) produced from the combustion of sulfur can be further
oxidized to sulfur trioxide (SO3) under specific conditions, such as in the presence
of a:
a) Catalyst (e.g., vanadium(V) oxide) and high temperature.
b) Catalyst (e.g., iron) and low temperature.
c) Strong reducing agent and high pressure.
d) Dilute acid and room temperature.
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XII. Sulfur trioxide (SO3​) is not directly dissolved in water to produce sulfuric acid
in the Contact Process because this reaction is:
a) Too slow.
b) Reversible and would result in a low yield.
c) Highly exothermic and produces a mist of sulfuric acid.
d) Requires very high pressures.

SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. List two reasons for the inertness of N2.
b. How is nitrogen isolated from air?
c. Why ammonia (NH3) is a weak base?
d. How does NO2 catalyze the formation of SO3?
e. Write down the reactions of photochemical smog formation.
f. What is the construction and function of a catalytic converter?
g. Why sulfur is quite unreactive at room temperature?
h. Which are the most stable oxidation states of sulphur in water at pH=0 and pH=14?
i. How does sulfur react with halogens?
j. Draw the structures of cyclo-octasulfur (S8) and sulfuric acid.
k. What is the role of sulfur in the vulcanization of rubber?
l. What is the composition and the chemical reaction of gunpowder combustion?
m. What is the importance of disulfide bridges?
n. Write down self-ionization equation of sulfuric acid and its ionization in water.
o. Give two examples where sulfuric acid acts as a dehydrating agent.
p. How does V2O5 catalyze the formation of SO3?
q. What is purpose of formation of oleum?

DESCRIPTIVE QUESTIONS
Q.3 Explain the preparation and basicity of ammonia.
Q.4 How oxides of nitrogen (NOx) cause the formation of photochemical smog and
PAN? Give its mechanism.
Q.5 Frost diagram explains the stabilities of different oxidation states of sulfur. Which
oxidation states of sulphur are the most stable at acidic and basic conditions?
Q.6 Discuss sulfuric acid as an oxidizing agent and a dehydrating agent with three
reactions for each.

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13
Chemistry-XI

HALOGENS
STUDENT LEARNING OUTCOMES [C-11-B-19 to C-11-B-41]
Describe the colours and the trends in volatility of chlorine, bromine, and iodine.
(Understanding)
Describe the trend in bond strength of halogen molecules. (Understanding)
Interpret the volatility of the elements in terms of instantaneous dipole-induced dipole
forces. (Understanding)
Describe the relative reactivity of halogen elements as oxidizing agents. (Understanding)
Describe the reactions of elements with hydrogen and explain their relative reactivity in
these reactions. (Understanding)
Describe the relative thermal stabilities of hydrogen halides and explain these in terms of
bond strength. (Understanding)
Describe the relative reactivity of halide ions as reducing agents. (Understanding)
Explain the reactions of halide ions with aqueous silver nitrate and concentrated sulphuric
acid. (Understanding)
Describe the reactions of halides with aqueous silver ions followed by aqueous ammonia.
(Understanding)
Interpret the reaction of Chlorine with cold and hot aqueous sodium hydroxide as
disproportion reactions. (Understanding)
Explain the use of chlorine in water purification, including the production of the active
species HOCI and CIO- which kill bacteria. (Understanding)

Elements present in Group 17 or VIIA of the periodic table are termed as halogens. It
includes fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At) and tennessine
(Ts). The halogen elements form a group of very reactive non-metals and are quite similar
to each other in their chemical properties. First four elements are the common elements
of the halogen family but last two astatine (At) and tennessine (Ts) are very rare and
radioactive elements.
Halogens exist as diatomic molecules in all phases (gas, liquid or solid). Fluorine (F2)
and chlorine (Cl2) are gases of pale yellow and greenish yellow colours respectively at
room temperature and pressure. Bromine (Br2) is a volatile liquid of reddish-brown colour
at room temperature. It has corrosive and toxic fumes. Iodine (I2) is shiny greyish black
solid at room temperature. It sublimes directly from solid to a violet vapor. The colors of
halogens (X2) darken progressively from chlorine to iodine. The trends of colour changes
from chlorine to iodine is due to changes in the absorption of light as a result of electron
transitions within the molecules of respective halogens.
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Figure 13.1 The greenish yellow chlorine (left), orange bromine (middle) and purple iodine (right)

Did You Know!

The name halogen comes from the Greek words “halos”, meaning “salt”, and “gen”, meaning “to
make.” The first halogen to be isolated and recognized as an element was chlorine. Despite the fact
that chlorine is poisonous, small amount is essential to human health and life in the form of chloride.
Table 13.1 Atomic and Physical properties of the common halogens.

Element Fluorine Chlorine Bromine Iodine

Proton number 9 17 35 53

Electron shell structure 2, 7 2, 8, 7 2, 8, 18, 7 2, 8, 18, 18, 7

Outer shell electron configuration 2s22p5 3s23p5 4s24p5 5s25p5

Relative atomic mass 19.0 35.5 79.9 126.9

Physical state at of 20 ºC gas gas liquid solid

Colour pale yellow pale green red–brown dark gray

Melting point/ºC –220 –101 –7 113

Boiling point/ºC –188 –35 59 183

Enthalpy change of vaporisation +3.3 +10.2 +15 +30

/kJ mol–1
Solubility/g per 100g of water at reacts readily 0.59 (reacts 3.6 0.018
20ºC with water slightly)

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13.1 VOLATILITY OF CHLORINE, BROMINE AND IODINE

Chlorine being a liquid is very volatile at room temperature and it disperses quickly in
the air. Bromine being a liquid is less volatile than chlorine but more volatile than iodine.
It evaporates readily releasing toxic fumes at room
temperature. Iodine is the least volatile among Interesting Information
the three. At room temperature, its solid states
show lower volatility as compared to chlorine Bromine liquid evaporates easily at
and bromine. Generally, volatility decreases from room temperatures emitting an orange
vapor. Bromine has a very strong and
chlorine to iodine. This trend is due to the increasing
bad odor. It gets its name from the Greek
molecular mass, increase in size of outer shell and word “bromos” which means “stench.”
stronger intermolecular forces (London dispersion
forces) as we move down the group in the periodic table.

13.2 TREND IN VOLATILITY OF THE HALOGENS

Halogens are non-polar and instantaneous dipole-induced forces play a significant role
in determining the volatility of halogens. The forces depend on factors like molecular
size, shape and polarizability, with stronger forces leading to lower volatility and higher
boiling points. Substances with weak id-id forces, smaller and less polarizable molecule
have lower boiling points and higher volatility. Larger, more polarizable molecules with
stronger London dispersion forces have higher boiling points and lower volatility.
Volatility is inversely related to the boiling point of a substance. A more volatile substance
will have a lower boiling point. Stronger intermolecular forces require more energy to
separate the molecules from the liquid phase to the gaseous phase. A summary is given in
Table 13.2.
Table 13.2 Effect of London forces on physical properties

Size Polarizability Instantaneous Boiling Point Volatility

dipole-induced
dipole forces
Small Small Weak Lower Higher
Large High Strong Higher Lower

The first two halogens, i.e, fluorine (colourless or very light green) and chlorine (greenish
yellow) are gases due to weaker id-id forces. Bromine is a liquid as its size is bigger
and it possesses stronger intermolecular forces than fluorine and chlorine. Iodine has the
strongest forces among the group, so it is in solid state at room temperature.
Quick Check 13.1
a) Which halogens elements are radioactive?
b) What is the reason behind the different colours of halogens?
c) Why chlorine is more volatile than bromine and iodine?

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13.3 THE BOND STRENGTH OF HALOGEN MOLECULES

Bond strength in halogens decreases as we move
down the group from chlorine to iodine. This is due to
the increase in the atomic size down the group which
results in longer bond lengths and weaker bonds.
Moving from top to bottom in group 17, the bond
energy of halogens decreases gradually from chlorine
to iodine. However, fluorine is an exception in this F F
group. In the case of fluorine, the bond strength is
relatively weak because fluorine atoms are very small.
Due to the small size, there is significant electron–
electron repulsion between the lone pairs on the Figure. 13.1 F2 molecule with lone
fluorine atoms, which weakens the bond despite the pairs of electrons
high electronegativity of fluorine. The bond energy of halogens is listed in Table 13.3.
Table 13.3 Bond energies of halogen molecules
Halogen Molecule Bond Energy (kJmol-1)
F2 156
Cl2 243
Br2 193
I2 151

13.4 RELATIVE REACTIVITIES OF THE HALOGENS AS

OXIDIZING AGENTS
All the free halogens act as oxidizing agents when they react with metals and most of
non-metals. On forming ionic compounds with metals, the halogens gain electrons and are
converted to negative halide ions.

2Na(s) + Cl2(g) 2NaCl(s)

The oxidizing power of halogens decreases down the group. Fluorine has the highest
oxidizing power and iodine the least. The order of decreasing power as an oxidizing agent
is:
F2> Cl2> Br2> I2.
The reactivity of halogens is directly related to their ability to acquire an electron and
form halide ions (F-, Cl-, Br- and I-) when they react with other elements. Fluorine has the
highest tendency to acquire an electron and form fluoride. Fluorine molecule can oxidize
and displace all the halide ions from their solutions (Cl-, Br- and I-) to free halogens.
1–
F2(g) + Cl(aq) 1– + Cl
F(aq) 2(g)
1
F2(g) + Br(aq)– 1–
F(aq) + Br2(g)
1–
F2(g) +I(aq) 1– + I
F(aq) 2(g)
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Similarly, chlorine can oxidize and displace Br- and I-. Bromine can oxidize and displace
I-. Iodine cannot oxidize any halide ion.
The oxidizing power of halogens can be Table 13.4 Standard electrode potential E ̊ (X2/X-)
related to standard electrode potential
Halogen Molecule Standard Reduction
(Eo) values. Fluorine is the most reactive
(X2) Potential, E ̊ (V)
halogen and the most powerful oxidizing
agent. The standard electrode potential F2 + 2.87
-
E ̊ (X2/X ) for halogens shown in Table Cl 2 +1.36
13.4 become less positive from fluorine Br2 +1.07
to iodine. This reflects the decreasing I2 +0.54
oxidizing power. The oxidizing power of
halogens depends upon various factors,
i.e., energy of dissociation, electron affinity of atoms, hydration energies of ions, and heats
of vaporization (for Br2 and I2). A halogen having low energy of dissociation, high electron
affinity and higher hydration energy of its ions, will have a high oxidizing power.
Quick Check 13.2
a) The F-F bond is weaker than Cl-Cl bond although fluorine is the most electronegative element, Explain.
b) Is the reaction between NaCl aq and F2 gas possible?
i) Give reason whether yes or no.
ii) If yes, write the equation for this reaction.
c) What is the relationship between the oxidizing power of halogens and their standard reduction
potential values?

13.5 REACTIONS OF THE HALOGENS WITH HYDROGEN

When halogen elements react with hydrogen, they produce hydrogen halides.
H2 + X2 2HX Where X2 = F2, Cl2, Br2 and I2
Hydrogen halides are colourless gases that dissolve in water to form hydrohalic acid.
When we move down the group from fluorine to iodine, the reactivity of halogens with
hydrogen decreases.
F2 ˃ Cl2 ˃ Br2 ˃ I2
At low temperature and in the dark, fluorine reacts explosively with hydrogen.
H2(g) + F2(g) 2HF(g)
When this gas is dissolved in water, it forms hydrofluoric acid.
In the presence of UV light or a spark, chlorine reacts readily with hydrogen and produces
colourless HCl gas which forms hydrochloric acid in water.
H + CI hv 2HCI
2(g) 2(g) (g)
Hydrogen bromide (HBr) gas is produced when bromine reacts with the hydrogen upon
heating. HBr gas is less reactive than HCl and HF. It forms a strong hydrobromic acid in
water. This is an exothermic reaction.

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H2(g) + Br2(g) 2HBr(g)

At high temperature and in presence of a catalyst, iodine reacts with hydrogen to form
hydrogen iodide (HI) gas, which forms hydroiodic acid in water.
catalyst
H2(g) + I2(g) 2HI(g)

This is a reversible reaction and occurs very slowly.

13.6 RELATIVE THERMAL STABILITIES OF HYDROGEN

HALIDES IN TERMS OF THEIR BOND STRENGTH
As we move down the halogen group from fluorine to iodine, the thermal stabilities of
hydrogen halides (H-X) decrease due to decrease in bond dissociation energies as given in
Table 13.5. The order of thermal stability of HX is as follows:
HF˃ HCl ˃ HBr ˃ HI
Bond strength between the hydrogen and the halogen atom in the H-X molecule explain
this trend. Hydrogen fluoride (HF) is the most thermally stable hydrogen halide. Due to the
high electronegativity of fluorine and its small atomic radius, a strong overlap of orbitals
produces a very strong H-F bond. The bond dissociation energy of H-F (569 kJ/mol) is the
highest among the hydrogen halides. Hydrogen chloride (HCI) is less thermally stable than
hydrogen fluoride but more stable than other hydrogen halides. Due to the larger atomic
radius of chlorine than fluorine H-CI bond is weaker than H-F bond. Its bond dissociation
energy is less than that of H-F. Its bond dissociation energy is 431 KJ/mol. Hydrogen
bromide (H-Br) bond is weaker than H-F and H-Cl due to the larger atomic radius of
bromine. There is a reduced overlapping of orbitals. Its bond dissociation energy is 366
kJ/mol. Among the common hydrogen halides, hydrogen iodide (HI) is the least thermally
stable. Atomic radius of iodine is very large leading to poor orbital overlap due to which
hydrogen iodide bond is the weakest among H-F, HCl and HBr. The bond dissociation
energy of hydrogen iodide is 299 kJ/mol.
Table 13.5 Bond dissociation energy of H-X bonds
Hydrogen halide (HX) Bond dissociation energy (kJmol-1)
H-F 569
H-Cl 431
H-Br 366
H-I 299

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Quick Check 13.3

a) What is the relationship between the oxidizing power of halogens and their standard reduction
potential values?
b) The reaction between H2 and F2 is explosive but that between H2 and I2 is slow and reversible.
Explain why.
c) Refer to Table 13.4 and 13.5 to predict which of the following reactions would be more exothermic.
Explain your answer.
H2 (g) + Cl 2 (g) 2HCl (g) and H2 (g) + Br 2 (g) 2HBr (g)
d) How thermal stability of hydrogen halides is related to their bond dissociation energies?
e) HF is the most thermally stable hydrogen halide. Give reasons.

13.7 RELATIVE REACTIVITY OF HALIDE IONS AS

REDUCING AGENTS
The reducing ability of halide ions increases as we move down the group from fluorine to
iodine. This trend is mostly due to the decreasing electronegativity and increasing atomic
radius down the group. This result in lower charge density and greater ease of electron
donation. Fluoride ion is the weakest reducing agent while iodide is the strongest reducing
agent among the halides.
The order of decreasing power as a reducing agent is I- > Br- > Cl- > F-. The following is
an explanation of this trend in terms of their properties.
The high electronegativity of fluorine and the strong bond between the fluorine atom and
its extra electron make it difficult for fluoride ion (F-) to donate electrons. The small size
of fluoride ion results in a high charge density, further stabilizing the fluoride ion and
reducing its tendency to lose an electron.
Chloride ion (Cl-) is a stronger reducing agent than fluoride but still weaker than bromide
and iodide. This is due to its larger size and lower electronegativity.
Bromide (Br-) is a stronger reducing agent than chloride. Bromine is less electronegative
than chlorine. Bromide ion (Br-) has a larger ionic radius and lower charge density due to
which it easily loses an electron and act as a reducing agent.
Iodide (I-) is much stronger reducing agent than both chloride and bromide. Electronegativity
of iodine is much lower than chlorine and bromine. Iodide ion (I-) is large in size. This
results in a lower charge density and a tendency to donate an electron by the iodide ion,
making it strong reducing agent.

13.8 REACTIONS OF HALIDES WITH AQUEOUS SILVER

ION FOLLOWED BY AQUEOUS AMMONIA
13.8.1 Reactions of halides with aqueous silver ion
Insoluble silver halides (AgX) are formed when halide ions react with aqueous silver
nitrate (AgNO3). These reactions are used in qualitative analysis to identify halides ions.
The general reaction is given below:
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1– + Ag 1–
X(aq) 2AgX(s)
(aq)

No reaction is visible when silver ions and fluoride ions are mixed in the aqueous medium.
As silver fluoride is soluble in water, Fluoride (F-) does not form precipitate as silver
fluoride.
When silver ions and chloride ions are mixed in the aqueous medium a white precipitate
of silver chloride forms, which is soluble in dilute ammonia.
Ag1+ 1–
(aq) + Cl(aq) AgCl(s)
On mixing of aqueous silver ions with
aqueous Bromide ions, a cream-coloured
precipitate of silver bromide forms. This
precipitate of silver bromide is sparingly
soluble in concentrated ammonia.
1+ + Br 1-
Ag(aq) AgBr(s)
(aq)

A yellow precipitate of silver iodide forms Figure 13.2 Colours of the silver halide
precipitates: silver chloride (left), silver bromide
(middle) and silver iodide (right).
on mixing aqueous silver Ion with aqueous
halide solution. The product AgI is insoluble in ammonia.
1+ + I 1-
Ag(aq) Agl(s)
(aq)

This type of reactions is used to identify halide ions and is called silver nitrate test.
13.8.2 Reaction of silver halides (AgX) with aqueous ammonia
Addition of aqueous ammonia tests the solubility of initially formed silver halide
precipitates.
AgF is soluble in water so it does not form precipitate, so ammonia has no effect. Silver
chloride dissolves in dilute ammonia to form diamminesilver(1) complex. The white
precipitate of AgCl dissolves in dilute ammonia forming a colourless solution.
AgCl(s)+2NH3(aq) 1-
[Ag(NH3)2]+(aq) + Cl(aq)
The cream-coloured precipitate of AgBr dissolves in concentrated ammonia, forming a
colourless solution.
AgBr(s) + 2NH3(aq) +
[Ag(NH3)2](aq) 1-
+Br(aq)
The yellow precipitate of silver iodide (AgI) does not dissolve in both dilute and
concentrated ammonia, so there is no change in the presence of ammonia.
The below sequence of reactions in Table 13.6 provides a systematic way to differentiate
between halide ions using their solubility with aqueous silver ions and ammonia.
Quick Check 13.4
a) F- is a weaker reducing agent than Cl-. Explain why.
b) What is the cause of the different solubilities of silver halides in ammonia?
c) Write down the equation for the reaction of KI with Ag+ followed by NH3. What would you \
observe at the completion of this reaction?
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Table 13.6 Action of Ag+ followed by ammonia on silver halides

Halide ion Action of aq. Ag+ ion Action of Aqueous Ammonia

Fluoride ion (F-) No precipitate No reaction with aq. NH3

Chloride ion (Cl-) White precipitate (AgCl) Soluble in dil. aq. NH3

Bromide ion (Br-) Cream colour precipitate (AgBr) Soluble in conc. aq. NH3

Iodide ion (I-) Pale yellow precipitate( Agl) Insoluble in aq. NH3

13.9 REACTIONS OF HALIDES (X-) WITH CONCENTRATED

SULFURIC ACID
The reactions of different halide ions with concentrated sulfuric acid are different from one
another. The nature of the product and nature of reaction changes down the group from
fluoride to iodide.
Fumes of hydrogen fluoride gas are produced when concentrated sulfuric acid reacts with
NaF. HF is a weak reducing agent, therefore, it does not react with H2SO4 further.
NaF(s) + H2SO4() NaHSO4() + HF(g)
When concentrated sulfuric acid reacts with sodium chloride, fumes of hydrogen chloride
gas are produced.
NaCl(s) + H2SO4() NaHSO4() + HCl(g)
In case of Br1- ion, steamy fumes of hydrogen bromide (HBr) gas and brown fumes of
bromine (Br2) are produced along with the smell of sulfur dioxide (SO2). It is a redox
reaction. Hydrogen bromide acts as a reducing agent by reducing sulfuric acid to sulfur
dioxide and is self-oxidized to bromine.
NaBr + H2SO4() NaHSO4(l) + HBr(g)
2HBr(s) + H2SO4() Br2(g) + 2SO2(g) + 2H2O()
When concentrated sulfuric acid reacts with sodium iodide, fumes of hydrogen iodide gas,
purple fumes of solid iodine I2 and smell of H2S gas produced. HI acts as a strong reducing
agent. It reduces H2SO4 to H2S and is itself oxidized to I2.
NaI(aq) + H2SO4() NaHSO4() + HI(g)
8HI(s) + H2SO4() 4I2(s) + H2S(g) + 4H2O()
The trend of increasing reducing power of the halide ions (X-) from fluoride to iodide,
leads to more complex reactions with concentrated sulfuric acid.

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13.10 REACTIONS OF CHLORINE WITH COLD AND HOT

AQUEOUS SODIUM HYDROXIDE
Those reactions in which a single element undergoes both oxidation and reduction
simultaneously are known as disproportionation reactions. When chlorine reacts with cold
and hot aqueous sodium hydroxide (NaOH), it undergoes disproportion and form different
products according to the temperature of the reaction.
13.10.1 Reaction with cold aqueous sodium hydroxide
Chlorine undergoes disproportion when it reacts with cold aqueous sodium hydroxide
(NaOH) forming sodium chloride (NaCl) and sodium chlorate (I) (NaCIO).
Cl2(g) + 2NaOH(aq) NaCl(aq) + NaClO(aq) + H2O(l)
Oxidation states of chlorine in the above reaction are given below:
Chlorine in Cl2 = 0
Keep in Mind!
Chlorine in NaCl = -1
Sodium chlorate (I) is previously
Chlorine in NaClO = +1 called sodium hypochlorite.

Chlorine in Cl2 is oxidized from 0 to +1 in NaOCl. Chlorine in Cl2 is reduced from 0 to 1

in NaCl.
The above reaction shows the simultaneous oxidation and reduction of chlorine and is
example of disproportionation reaction.
13.10.2 Reaction with hot aqueous sodium hydroxide
When chlorine reacts with hot aqueous sodium hydroxide (NaOH), it forms sodium chloride
(NaCl) and sodium chlorate (V) (NaClO3). It is another example of disproportionation
reaction.

3Cl2(g) + 6NaOH(aq) NaCl(aq) + NaClO3(aq) + 3H2O(l)

Chlorine in Cl2 = 0

Chlorine in NaCl = -1

Chlorine in NaCIO3 = +5

Chlorine is oxidized from 0 to +5 in NaCIO3. Chlorine is reduced from 0 to -1 in NaCl

This disproportionation reaction shows how the temperature of the reaction influences the
products formed, demonstrating the versatility of chlorine in undergoing redox reactions.

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Quick Check 13.5

a) How would KI react with conc. H2SO4. What does this reaction indicate about the reducing
power of iodide?
b) Show that the reaction of Cl2 with cold and hot aqueous KOH is a disproportionation reaction.
c) HI acts as strong reducing agent. Explain it with chemical reactions.

13.11 USE OF CHLORINE IN WATER PURIFICATION

Chlorine gas is very poisonous. However, in small quantities, they are harmless to
humans but poisonous to the bacteria which cause diseases. Due to its strong disinfectant
properties, chlorine is widely used at the treatment plants for water purification. The
process involves adding chlorine to water, where it forms active species that kill bacteria
and other pathogens. Water in the swimming pools is also chlorinated with slightly higher
concentrations of chorine because there is likely to be a higher concentration of bacteria
in the water. The primary active species are chloric (I) acid or hypochlorous acid (HOCI)
and the chlorate (I) or hypochlorite ions (OCl-). Chlorination is a relatively inexpensive
method of water disinfections.
13.11.1 Chlorine addition to water
When chlorine gas (Cl2) is added to water, it undergoes hydrolysis to form a mixture of
hydrochloric acid (HCl) and chloric (I) acid (HCIO).
Cl2(g) + H2O(l) HCl(aq) + HClO(aq)
Chloric (I) acid (HOCI) is a weak acid and partially dissociate in water to form hydrogen
ions (H+) and chlorate (I) ion (OCl-).
13.11.2 Disinfection Activity
HOCl and OCI- are effective disinfectants, but HOCl is more effective due to its neutral
charge. The neutral charge of HOCl allows to penetrate the cell walls of micro-organisms
easily. Essential cellular components such as proteins and lipids are oxidized by HOCl and
OCI-, which disrupt the cell function leading to cell death. HOCI and OCI can oxidize and
inactivate enzymes that are crucial for survival and replication of bacteria.

Interesting Information
Nucleic acids (DNA and RNA) can be oxidized by HOCI and OCl- and thus preventing bacteria
from replicating and vital cellular functions.

13.11.3 Factors affecting disinfection

pH
1. At pH around 6-7.5, HOCI predominates and makes the disinfection process more
effective.

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2. At higher pH (above 7.5), OCl- predominates, its less effective but still provides
disinfection.
Chorine dose
The higher the amount of chlorine, the more effective the disinfection. Sufficient chlorine
must be added to get enough HOCI and OCI- to kill bacteria.
Contact time
Contact time of water with chlorine must be long enough, to allow the disinfectants to
penetrate and kill bacteria, viruses and protozoa.
Quick Check 13.6
a) Why HOCl is more effective disinfectant than OCl- to kill bacteria in water?
b) What are the factors that affect disinfection of bacteria in water?
c) What are the primary active species in the chlorination of water? Give equation that shows their
production.

EXERCISE
MULTIPLE CHOICE QUESTIONS
Q.1 Four choices are given for each question. Select the correct choice.
I. Which halogen molecule has the strongest bond?
a) F2 b) Br2
c) I2 d) Cl2
II. The volatility of the halogens (Group 17) generally _________ as you move down
the group (from Fluorine to Iodine).
a) Increases b) Decreases
c) Remains the same d) Fluctuates unpredictably
III. Which one of the following halogen molecules has strongest oxidizing power?
a) Br2 b) F2
c) I2 d) Cl2
IV. The decreasing thermal stability of the halogens down the group is primarily due
to the:
a) Increasing electronegativity of the atoms.
b) Decreasing bond length between the halogen atoms.
c) Increasing atomic radius, leading to a weaker covalent bond.
d) Increasing strength of van der Waals forces

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V. Which one of the following halides has strongest reducing power?

a) F- b) Cl-
b) Br- d) I-
VI. Which statement about the reaction between halogens and hydrogen is correct?
a) Iodine reacts most vigorously with hydrogen
b) Chlorine and hydrogen explode in darkness
c) Fluorine combines explosively with hydrogen even in cold and dark conditions
d) Bromine and hydrogen do not react at all
VII. How does the acidic strength of hydrogen halides change as you move down
the group?
a) It remains constant. b) It decreases from HF to HI.
c) It increases from HF to HI. d) It fluctuates erratically
VIII. Why is fluorine the most reactive halogen?
a) Bond length in the halogen molecule
b) Bond strength in the halogen molecule
c) Electronegativity of the halogen
d) Number of electrons in the halogen molecule
IX. When aqueous silver nitrate is added to a solution containing bromide ions, a
cream precipitate forms. What is the solubility of this precipitate in ammonia
solution?
a) Soluble in dilute ammonia solution.
b) Partially soluble in dilute ammonia solution.
c) Insoluble in dilute ammonia solution.
d) Soluble only upon heating with ammonia.
X. Concentrated sulfuric acid is added to solid sodium chloride. What is the initial
observation?
a) Reddish-brown fumes are evolved.
b) A purple vapor is evolved.
c) Steamy white fumes of hydrogen chloride are evolved.
d) A black solid is formed.

SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. Which halogen is the least reactive, which is the most? Why?
b. The ionic equation for a reaction is:
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Br2 + 2I– →Br– + I2.

c. Explain which species is oxidized in this reaction. Why?
d. What is role of London dispersion forces in the trend of volatility of halogens?
e. How does the reactivity of halogens with hydrogen vary?
f. Which halogen is used as an antiseptic? How does it work?
g. What is the colour change when chlorine displaces bromine?
h. How the halogen acids are ionized in water?
i. Why HF is weaker acid than HCl?
j. Describe a simple chemical test that could be used to distinguish between aqueous
solutions of potassium bromide and potassium iodide. Include the reagents and
expected observations.
k. Explain the chemical principles behind the use of chlorine as a disinfectant in water
purification. Include relevant chemical equations in your explanation.
l. Describe one significant disadvantage associated with the use of chlorine in water
purification.
m. What is disproportionation reaction? Give an example.
n. Chlorine gas reacts differently with sodium hydroxide solution depending on the
temperature and concentration.
o. Write balanced chemical equations for the reaction of chlorine (Cl2) with:
i) Cold, dilute sodium hydroxide (NaOH).
ii) Hot, concentrated sodium hydroxide (NaOH).
p. For each reaction in question l), identify the oxidation states of chlorine in the reactant
(Cl2) and in each of the chlorine-containing products. Use these oxidation states to
explain why both reactions are classified as disproportionation reactions.

DESCRIPTIVE QUESTIONS
Q.3 Describe and explain the relative thermal stabilities of the halogen hydrides in
terms of bonds strength.
Q 4. Discuss the relative reactivity of the halogen elements as oxidizing agents.
Arrange F2, Cl2, Br2, I2 in increasing order of the oxidizing power.
Q 5. Describe the reactions that occur when chlorine is bubbled through
(i) Cold and (ii) Hot, aqueous sodium hydroxide (NaOH).
Q.6 Discuss the reducing power of halide ions with relevant reactions. Also explain
the factors affecting it.

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14
Chemistry-XI

ATMOSPHERE
STUDENT LEARNING OUTCOMES [C-11-C-01 to C-11-B-14]
Identify the properties and composition of the atmosphere. (Include the concept of 4 layers
of atmosphere and their composition. (Understanding)
Describe the sources and understand the effect of air pollution, (this can include both
natural and human caused pollutants including Greenhouse gases (such as carbon dioxide,
methane, and nitrous oxide), Chlorofluorocarbons (CFCs), and Ozone (O3) and other
ozone-depleting substances, Volatile organic compounds (VOCs), Polycyclic aromatic
hydrocarbons (PAHs), Persistent organic pollutants (POPs), Heavy metals such Lead (Pb),
Mercury (Hg), Cadmium (Cd). (Understanding)
Describe the impact on human activities on the atmosphere including the effects of burning
fossil fuels and deforestation. (Understanding)
Identify the chemical reactions and processes that occur in the atmosphere (some examples
include the formation of smog and acid rain). (Understanding)
Identify the global scale problems of air pollution, such as global warming and the
greenhouse effect. (Understanding)
Describe the factors that affect air quality. (Understanding)
Explain the link between air quality and human health. (Understanding)
Evaluate the potential health risks associated with air pollution. (Understanding)
Familiarize with use of methods and techniques to measure and monitor air quality.
(Understanding)
Design experiments and collect data to test hypotheses about air quality. (Application)
Analyze data and interpret air quality measurements and trends. (Understanding)
Explain the technologies and strategies used to reduce air pollution and improve air quality,
such as emissions control and renewable energy sources. (Understanding)
Identify the laws and regulations related to air quality and the measures used to control air
pollution. (Understanding)
Analyze the economic, social, and political issues related to air pollution and air quality
management and demonstrate through answers. (Understanding)

The atmosphere is a sphere of different gases around the earth. The component of the
atmospheres may be divided into major, minor and trace components. Major components
are nitrogen (78.00%) and oxygen (21.01%). Minor components are argon (0.93%),
carbon dioxide (0.04%). Trace components are methane, hydrogen, neon, helium,
krypton, and xenon.

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14.1 LAYERS OF THE ATMOSPHERES

The atmosphere has four distinct layers which are determined by the change in temperature
that is observed with increasing altitude.
i) Troposphere
It is the lowest region of the atmosphere which
extends up to 12 km. It includes all the major gases
present in the atmosphere i.e., nitrogen, oxygen,
and carbon-dioxide, etc. In this region, temperature
decreases from 17 oC to -58 oC regularly. It is the
densest layer of the atmosphere. It is the layer in
which major events such as rain, lightening, and
hurricanes occur.
ii) Stratosphere Figure 14.1 Layers of the atmosphere

Above the troposphere, the stratosphere lies which is at a distance of 12-50 km above the
earth surface. Temperature increases from -58oC to -2oC. Stratosphere can also be divided
into three regions according to the distribution of ultraviolet radiations from the Sun. Since
ozone in the upper layer absorbs high energy ultraviolet radiations from the Sun. It breaks
down into monoatomic oxygen and diatomic oxygen.
O hυ O +O
3 (g) 2 (g) (g)

The middle stratosphere has less ultraviolet radiations passing through it. Here, monoatomic
oxygen and diatomic oxygen recombine to form ozone which is an exothermic reaction
due to which formation of ozone layer takes place.
O2 (g) + O (g) O3 (g)
The lower stratosphere receives very low ultraviolet radiations, thus monoatomic oxygen
is not found here and ozone is not formed here.
iii) Mesosphere
It extends to a height of about 50 – 85 km from the ground. Here, the temperature decreases
with altitude from -2oC to -93oC. The coldest region of the atmosphere is located in this layer.
iv) Thermosphere
It extends from 85 km to 600 km above the earth surface. This is the region where the
temperature increases as the altitude increases. The increase in the temperature is caused
due to the absorption of energetic ultra-violet (UV) and X-rays. Temperature in the upper
thermosphere can range from 500 oC to 2000 oC or higher.

14.2 AIR POLLUTANTS

Pollutants are substances (gases, liquids and solids) that are harmful to the environment. Air
pollutants can be classified as primary and secondary. Primary pollutants are substances
directly produced or emitted, such as ash from a volcanic eruption or carbon monoxide gas

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from a motor vehicle exhaust. Secondary pollutants are formed due to chemical reactions
of primary pollutants.
The most important pollutants are mentioned below:
1. Oxides of Carbon (CO and CO2)
2. Oxides of Nitrogen (NO and NO2) collectively known as NOx
3. Oxides of Sulphur (SO2 and SO3) collectively known as SOx
4. Hydrocarbons (Methane, Ethane)
5. Low altitude Ozone (O3)
6. Chlorofluorocarbons (CFCs)
7. Polycyclic Aromatic Hydrocarbon (PAHs)
8. Persistent Organic Pollutant (POPs)
9. Volatile Organic Compounds (VOCs)
10. Particulate Matter (PM)
11. Heavy Metals (Pb, Hg and Cd)

14.3 SOURCES OF AIR POLLUTION

There are broadly two main sources of air pollution.
14.3.1 Natural sources
Naturally occurring particulate matter (PM) include dust from earth’s surface, and
biological materials in the form of pollens, spores and animal debris. Volcanic eruptions can
introduce very large quantities of gases and particulate matter (PM) into the atmosphere.
Thunderbolt produces significant quantities of oxides of nitrogen (NOx).
Other natural sources of air pollution are algae on the surface of the oceans, which gives
out hydrogen sulphide (H2S), wind erosion which introduces PM, and humid zones such as
swamps, peat-bags or little deep lakes, which produce methane (CH4).
14.3.2 Human-made sources
Such sources can be classified as either mobile (cars, trucks, air planes, marine engines) or
point sources (factories, electric power plants etc.). The combustion of fossil fuels (coal,
fuel oils, and natural gas) in vehicle engines, factories and power plants produce carbon
dioxide (CO2) carbon-monoxide (CO), and hydrocarbons (CH4). The burning of wood as a
domestic fuel and coal in brick kilns are also the sources of air pollutants.

Quick Check 14.1

a) Mention important air pollutants.
b) Give the equations for the formation and depletion of ozone in the stratosphere.
c) Write down the names and approximate height of different layers of atmosphere.

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14.4 SOURCES OF AIR POLLUTANTS

14.4.1 Oxides of Carbon
There are two oxides of carbon i.e., carbon monoxide (CO) and carbon dioxide (CO2).
Carbon monoxide (CO)
Carbon monoxide (CO) is produced mainly due to incomplete combustion of fossil fuels.
2C(S) + O2(g) 2CO(g)

Did You Know?

Carbon monoxide is highly poisonous gas and cause suffocation if inhale. It binds blood
hemoglobin more strongly than oxygen thus excluding oxygen from normal respiration. The
CO poisonous can be reversed by giving high pressure oxygen.

Carbon dioxide (CO2)

Carbon dioxide is the key greenhouse gas emitted by human activities like combustion
of fossil fuels. Carbon dioxide (CO2) is a primary greenhouse gas that traps heat in the
atmosphere, leading to global warming.
C(S) + O2(g) CO2(g)

14.4.2 Oxides of Nitrogen (NOx)

The gases like nitric oxide (NO) and nitrogen dioxide (NO2) are represented by NOx. It is
generally produced from burning fossil fuels. NOx is produced as a result of the following
chemical reactions:
high temp
N 2(g) + O 2(g)  → 2NO(g) (Nitric oxide)
2NO(g) + O 2 → 2NO 2 (Nitrogen-Dioxide)

Natural sources of N2O include microbial processes in soil and oceans where bacteria break
down nitrogen compounds. Human activities include agricultural activities (synthetic
fertilizers) and industrial processes (combustion of fossil fuels). It depletes the ozone layer.
The increased levels of N2O contribute to climate change and can also affect air quality.
14.4.3 Oxides of Sulphur (SOx)
There are two oxides of sulphur i.e., sulphur dioxide (SO2) and sulphur trioxide
(SO3) which are collectively called SOx. These gases are emitted primarily
by burning coal and oil. When SOx combine water vapour, it causes acid rain
that damages ecosystem. SO2 is the major source of acid deposition in the air.
14.4.4 Hydrocarbons
Hydrocarbons are produced naturally in various environmental processes like vegetation,
wildfire, volcanoes, and seeps. Anthropogenic activities like incomplete burning of fossil
fuels, oil spills, industrial and vehicle emission are sources of hydrocarbons. Automobiles
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are the major source of hydrocarbon emission. Methane is the most common hydrocarbon
and air pollutant.
14.4.5 Low-Altitude Ozone (O3)
Ozone is a powerful oxidizing agent. It is non-toxic in small concentrations, but above 100
parts per million (ppm), it is toxic. It is harmful to humans, plants and other materials i.e.,
rubber, fabric dyes, and durability and appearance of paints.
14.4.6 Chlorofluorocarbons (CFCs)
The decrease in the concentration of ozone in stratosphere is called depletion of
ozone. This depleting of ozone has been caused by certain organic compounds called
chlorofluorocarbons (CFCs). These compounds exist as gases or low boiling liquids at
room temperature and are used as aerosols or refrigerants.
Chlorofluorocarbons are known to diffuse into the stratosphere
.
where they are broken
down by UV radiation creating chloride free radical (C ). The chloride free radical breaks
down the Ozone molecule as shown in the following reactions.
UV .
CFC3 CFC2 + C
. .
C + O3 C O + O2
. .
C O + O2 C + O2
The formation of another chlorine free radical in the last step that can further break down
another molecule of O3. The 2nd and the 3rd steps are repeated many times.

Interesting Information
Chlorofluorocarbons are used as propellants for aerosols and as coolant in refrigerators
and air conditions. CFCs are 100,000 times more effective than CO2 at preventing heat from
especially from the earth’s atmosphere. The decomposition of one molecule of CFCs can
destroy up to 100,000 molecules of ozone.

14.4.7 Polycyclic Aromatic Hydrocarbon (PAHs)

Polycyclic aromatic hydrocarbon (PAHs), composed of fused multiple aromatic rings
are common environmental pollutants. Naphthalene, anthracene and phenanthracene are
examples of PAHs. They are generated primarily during the incomplete combustion of
fossil fuels (coal, oil, petrol, and wood), vehicle emissions, industrial processes and even
grilled foods. Some PAHs in the environment originate from the natural sources such
as open burning, natural loss or seepage of petroleum and coal deposits. Naphthalene,
anthracene and phenanthracene are examples of PAHs. They have potential toxicity and
carcinogenic properties.
14.4.8 Persistent Organic Pollutants (POPs)
These are organic compounds that are resistant to degradation through chemical, biological
and photolytic processes. These are toxic and adversely affect human health and the

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environment, traveled by wind and water. Most POPs are generated in one country can
affect people and wildlife far from where they are used and released.
Owing to their persistence, they accumulate in the environment and can have significant
adverse effects on human health. Some POPs are given in Table 14.1 below:
Table 14.1 Some POPs with their uses

Names of POPs Uses

Polychlorinated Biphenyls Used in electrical equipment, surface coating ink,

(PCBs) adhesives and paints
Dichlorobiphenyl
tri-chloroethane (DDT) Used as an insecticide in agriculture

14.4.9 Volatile Organic Compounds (VOCs)

A large group of organic compounds that easily evaporates at room temperature. VOCs
are emitted as gases from certain solids or liquids. Liquid fuels are major sources of VOCs
that impact outdoor air quality. Vehicle exhaust and burning liquid fossil fuels, wood and
garbage all release VOCs into the atmosphere.
Exposure to VOCs can cause a variety of health effects including eye, nose and throat
irritation, headache, nausea are short term exposures and damage to the liver, kidney
and central nervous system are long term exposures. They are significant air pollutants
contributing to indoor and outdoor air pollution Some common VOCs are benzene, xylene,
toluene, ethanol, formaldehyde and acetone etc,.

14.4.10 Particulate Matter (PM)

The term “particulate matter (PM)” refers to the wide variety of tiny substances that float
in the air in the form of either solid particles or liquid droplets or both.
Particulate matter (PM) is all the dust, smoke, and haze particles suspended in ambient
air. Particulate matter (PM) comprises acids, organic chemicals, metals, and soil or dust
particles. Sources of PM are both natural and anthropogenic. Natural sources include
volcanoes, fires, dust storms, and aerosolized sea salt. Man-made sources of particulate
matter PM include combustion in mechanical and industrial processes, vehicle emissions,
and tobacco smoke.
14.4.11 Heavy Metals (Lead, Mercury and Cadmium)
Heavy metal like lead, mercury and cadmium can indeed be significant air pollutants.
They are released into the atmosphere from various industrial process, transportation and
other human activities. Metallurgy, battery waste and incineration are their major sources.

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14.5 IMPACT OF HUMAN ACTIVITIES ON THE

ATMOSPHERE
Human activities have significant impact on the atmosphere, primarily through the burning
fossil fuels and deforestation. These activities contribute to climate change, air pollution,
poor air quality and other environmental issues.
In urban areas, most air pollution comes from human-made sources. Such sources can
be classified as either mobile (cars, trucks, air planes, marine engines) or point sources
(factories, electric power plants etc.)
14.5.1 Impact of Burning Fossil Fuels on the Atmosphere
The burning of fossil fuels is the primary cause of current climate change, altering the
earth ecosystem and causing human and environment health problems. The burning of
fossil fuels affects the earth system in a variety of ways. Some of these ways include
greenhouse gas emission, air pollution, volatile organic compounds.

Figure 14.2 Impacts of air pollutants on the atmosphere

14.5.2 Impact of Deforestation on the Atmosphere

Deforestation is purposeful cleaning or thinning of forests by humans. Deforestation
represents one of the largest issues in global climate. Forests absorb GHGs like CO2 and clean
air for us. In short, deforestation has a wide range of negative impact on the environment,
including loss of biodiversity climate change, soil degradation, and water cycle disruption.

Quick Check 14.2

a) Mention man-made sources of air pollution.
b) How do polycyclic aromatic hydrocarbons (PAHs) primarily enter the atmosphere?
c) How do volatile organic compounds (VOCs) affect air quality?
d) What are major sources of heavy metals in the atmosphere?

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14.6 EFFECTS OF AIR POLLUTANTS

The most important and commonly effects of air pollutants are formation of Smog and
Acid Rain.
14.6.1 Formation of Smog
Smog is a type of air pollution
typically characterized by a
thick haze. It primarily occurs in
urban areas and is often caused
by emissions from vehicle,
industrial activities and other
sources of pollution. It consists
of fine dust or soot particles,
condensed water vapor,
poisonous gases like SO2, NOx,
O3, CO and CO2, secondary
pollutants like O3, unburned
hydrocarbons, VOCs and PM
10-2.5 micron. Figure 14.3 Smog around Lahore Fort
Types of Smog
i) Industrial or Classical Smog (London Smog)
ii) Photochemical smog (Los Angeles Smog)

i) Classical or Sulphurous Smog

Sulfurous or Industrial smog also called as “Reducing smog or Classical Smog” usually
results from high quantities of sulfur oxides (SOx) being released into the air. It is also
called London smog.

ii) Photochemical smog

Photochemical smog is a type in
which primary air pollutants like
nitrogen oxides (NOx), VOC and
unburned hydrocarbons undergo
photochemical reactions in the
presence of sunlight and form
secondary pollutants like ozone
and peroxyacetyl nitrates (PAN).
This type of smog is considered
more dangerous as it can cause
heart palpitations, pneumonia
and even lung cancer.
Figure 14.4 Illustration of Photochemical smog

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14.6.2 Acid Rain

When rain water has pH less than 5-6, it is known as acid rain refers to precipitation (rain,
snow sheet or hail). Burning of fossil fuels releases SOx and NOX into the atmosphere.
These gases mix with the moisture in the air and form acids. Wind can carry these acidic
droplets to huge distance. Finally, these droplets return to the ground as acid rain, acid hail,
snow and even fog. Acid rain looks, feels and tastes like clean rain. Its corrosive nature
causes widespread damage to the environment. The most important chemical reactions are
following:

2SO2( g ) + O2( g ) → 2 SO3( g )

SO3( g ) + H 2O(l ) → H 2 SO4( aq )

SO2 from fossil fuels is oxidized to SO3 which then reacts with water to form sulphuric
acid.
Nitrogen oxide reacts with water to produce nitric acid and nitrous acid.
NO(g) + H2O( HNO3(aq) + HNO2(aq)
)
14.7 GREENHOUSE EFFECT AND GLOBAL WARNING
Global warming refers to the long-term rise in the Earth’s average surface temperature
due to human activities, primarily the emission of greenhouse gases (GHGs) released by
burning fossil fuels. The progressive warming up of the earth’s surface due to blanketing
effect of greenhouse gases in the atmosphere is called the greenhouse effect.

Figure 14.5 Mechanism of Global Warming 313

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It is a global scale problem of air pollution. Carbon dioxide and water vapour in the
atmosphere transmit short wavelength solar radiations but reflect back the longer
wavelength heat radiation coming from warmed surface of the earth.
The greenhouse effect is a phenomenon which is based on the gases to absorb infra-
red radiations. In the day, heat from the sun (in the form of infrared) passes through the
atmosphere heating up the earth. At night, the earth radiate heat to the outer space. Some
atmospheric gases trap the heat from the sun, thus, preventing the loss of heat. Higher
the concentration of carbon dioxide gas and other gases, greater will be the absorption of
thermal radiations and greater will be the increase of global temperature.

Quick Check 14.3

a) Differentiate classical and photochemical smog.
b) Name greenhouse gases (GHGs). How do these gases cause global warming?
c) Write a balanced equation, including state symbols, showing the formation of sulfuric acid
from atmospheric sulfur trioxide, SO2.

14.8 AIR QUALITY

Air quality is measured in terms of Air Quality Index (AQI). AQI is a measure of the
concentrations of pollutants present in the air at a particular location. When the air quality
is good, the air is clear and contains only small amount of solid particles and chemical
pollutants. Poor air quality, which contain high level is often hazy and dangerous to health
and the environment.
An AQI value under 50 is considered good in quality. This means, it is safe for you to
spend time outdoor without posing a risk to your health. An AQI over 300 is considered
hazardous. Children under 18, adult over 65, people with chronic heart, and lung diseases
are under high-risk. Outdoor workers are at higher risk because of the prolonged exposure.
14.8.1 Factors Affecting Air Quality
Air quality is influenced by several key factors or sources.
i) Emission sources
Burning of wood and fossil fuels can increase local pollution level. Factories and power
plants use fossil fuels that release dangerous pollutants in air like SOx and NOx. Vehicles
release CO, PM and VOCs.

ii) Meteorological conditions

Wind, temperature, and humidity affect pollutant dispersion and concentration. A layer of
warm air trapping pollutants near the ground can lead to poor air quality.

iv) Natural Events

Wild fires can release large amounts of smoke and PM into the atmosphere. Natural dust
storms can significantly lower air quality.
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v) Seasonal Changes
Temperature variations, such as heating or cooling of buildings in different seasons can
increase emissions of pollutants. Seasonal pollen concentration can contribute to poor air
quality.
Table 14.2 AQI and level of health concern

Air Quality Index (AQI) Values Levels of Health Concern Colour

0 to 50 Good Green
51 to 100 Moderate Yellow
101 to 150 Unhealthy for Sensitive Orange
Groups
151 to 200 Unhealthy Red
201 to 300 Very Unhealthy Purple
301 to 500 Hazardous Maroon

14.9 LINK BETWEEN AIR QUALITY AND HUMAN

HEALTH
The link between air quality and human health is well-documented and significant. Poor
air quality can have immediate and long-term health impacts.
14.9.1 Major Air Pollutants and their Health Effects
i) Particulate matter (PM)
Particular matter (PM) consists of tiny particles suspended in the air, including dust, dirt,
soot and smoke ranging from diameter of 2.5 micrometer to 10.0 micrometer. Inhalation
of these particulate matter (PM) can cause inflammation and irritation of airways, leading
to conditions such as asthma and bronchitis.
ii) Nitrogen Dioxide (NO2) and Sulphur Dioxide (SO2)
The short-term exposures of NO2 and SO2 can irritate the respiratory system, while long-
term exposure can increase the risk of respiratory infection, asthma and bronchitis.

14.10 POTENTIAL HEALTH RISK ASSOCIATED WITH

AIR POLLUTION
Air pollution poses significant health risks to humans. The potential health effects can be
acute or chronic and vary depending on the type and concentration of pollutants, duration
of exposure and individual weakness.
14.10.1 Main Health Risks Associated with Air Pollutions
i) Respiratory Diseases
Air pollutants such as ozone, particular matters (PM) and nitrogen dioxide (NO2) can
increase asthma symptoms and trigger asthma attack.
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Long term exposure may lead to chronic cough and respiratory infections like pneumonia.
ii) Cardio–Vascular Diseases
Exposure to particular matters and other pollutants can increase the risk of heart attack by
causing inflammation, blood vessel damage, high blood pressure and finally heart stroke.

iii) Cancer
Prolonged exposure to certain air pollutants especially particulate matter (PM) and
carcinogenic compounds (benzene formation) cause lung cancer.

iv) Reproductive and Developmental Effects

Exposure to air pollution may negatively impact reproductive health and fertility in both
man and women. Premature birth and developmental problems in children may occur.

Quick Check 14.4

a) Explain the impact of particulate matter (PM) on the air quality.
b) What is AQI? How does it measure air quality?
c) What are different levels of AQI. Mention the safest and the most hazardous ranges of AQI.

14.11 METHODS & TECHNIQUES TO MEASURE &

MONITOR AIR QUALITY
Measuring and monitoring air quality involves a combination of methods and techniques
to assess the concentration of various pollutants in the air. These pollutants can include
particulates matter (PM), nitrogen dioxides (NO2), sulphur dioxide (SO2), carbon monoxide
(CO), ozone (O3) and volatile organic compounds (VOCs). There are various methods are
techniques used by environmental engineers to measure air quality accurately.
The instrument used to measure air quality index (AQI) is nephelometer. This is an
instrument used to monitor PM such as dust, smoke, mist and fumes. Nephelometer, also
known as photometer, detects particles by measuring the total amount of light they scatter.
14.11.1 Direct measurement methods
i) Continuous Emission Monitoring System (CEMS)
Continuous emission monitoring system (CEMS) can usually monitor gas like CO, O3,
SO2, NO2, VOCs and PM at industrial sites .
ii) Air Quality Monitoring Stations (AQMS)
Fixed monitoring stations are equipped with various sensors and analyzers to measure
pollutant level in real time located in urban areas and industrial zones.
iii) Remote Sensing Techniques
Satellites equipped with sensors can measure atmospheric pollutants over large areas,
providing valuable data on regional and global air quality.
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14.12 EXPERIMENTS AND DATA COLLECTION TO

TEST HYPOTHESIS ABOUT AIR QUALITY
The design of experiments to test hypothesis about air quality involves careful planning,
data collection and analysis. Following steps should be done about the air quality.
i) Hypothesis
As a first step, a hypothesis is developed to design an experiment. For example, the
hypothesis, “The concentration of airborne particulate matters (PM 2.5) and nitrogen
dioxide (NO2) in urban areas is higher during peak traffic hours as compared to non-peak
hours” can be tested by collecting air quality data at different time of the day.
ii) Designing the experiment
The detail of the experiment including the variables and method of data collection is
planned. Busy roads sites and residential areas are selected for monitoring.

iii) Data Collection

The data on traffic volume during rush hours and non-rush hours is collected and finally
compared. The reliable instruments and methods to collect air quality data are used.

14.13 ANALYZE DATA AND INTERPRET AIR QUALITY

The collected data is analyzed to confirm the truth or falseness of the hypothesis. The
results of the analysis are interpreted and concluded.
Analyzing and interpreting air quality data involves understanding the concentration of
various pollutants, identifying trends overtime and assessing the implications for public
health and environmental Policy. General approach to analyze and interpret air quality
measurements and trends are follows.
By carefully designing experiments, collecting and analyzing data, a hypothesis about air
quality can be tested and the strategies for improving air quality can be made.

14.14 STRATEGIES USED TO REDUCE AIR POLLUTION

A variety of technologies is used to reduce air pollution and improve air quality. The
following five types of technologies we can be used to control emission of air pollutants.

i) Catalytic convertor (CC)

Oxides of nitrogen and other undesirable gases such as CO and various unburnt hydrocarbon
are emitted by the vehicle engines. The most cars are equipped with catalytic convertors
to convert the harmful pollutants to harmless substances. CO is oxidized to CO2 . NOx are
reduced to N2. The unburnt hydrocarbon is converted to CO2 and H2O.

ii) Diesel Particulate Filter (DPF)

Diesel particulate filter (DPF) is incorporated in modern diesel engines to reduce the

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emission of harmful particulate matter (PM) from the exhaust gases. The primary function
of diesel particulate filter is to capture and store soot particles from the exhaust gases.
iii) Selective catalytic reduction (SCR)
SCR is used in diesel engines to remove pollutants from the emission gases. It reduces NOx
to N2 and oxidizes CO and hydrocarbons to CO2 and water vapour using catalysts, such as
TiO2, zeolites, etc.

Figure 14.6 Selective Catalytic Reduction

iv) Scrubbers
Scrubbers can be used to control wide range of pollutants including particulate matters,
SO2, HCl, NH3 and VOCs. Scrubbers use liquids (e.g. H2O) to remove pollutants such as
SO2, PM from the industrial exhaust gases.

14.15 LAWS AND REGULATIONS RELATED TO ATMOSPHERE

14.15.1 Laws and Regulations
Common rules and regulations to control air pollution in Pakistan is given below:
i) Pakistan Environmental Protection Act (PEPA 1997)
ii) Natural Environmental Quality Standard (NEQS)
iii) Punjab Environmental Protection (Amendment) Act 2012
14.15.2 Measures to Control Air Pollutions
i. Vehicle Emission Standard: Enforcement of this standard is to reduce pollution from
motor vehicles. The promotion of cleaner fuels such as compressed natural gas (CNG),
liquid petroleum gas (LPG) and sticker regulation on fuel quality.
ii. Industrial Emission Control: To reduce emission from industrial resources and the
encouragement of industries to adopt cleaner production techniques and pollution
control technologies.
iii. Public Awareness Campaigns: Educating the public about the sources and effect of
air pollution and ways to reduce personal contributions to air pollution also promote
the use of public transport carpooling and non-motorized transport such as cycling and
walking.
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iv. Urban Planning and Green Infrastructure: Development of green belts and parks
in urban / areas to improve air quality. Implementation of urban planning measures to
reduce traffic congestion and promote sustainable transport options.
v. Smog Control Measures: Specific measures to control smog particularly during the
winter months when air quality deteriorates significantly, Restrictions the burning of
crop residues, which is a major contributes to smog and should use smog towers and
other technologies to reduce particulates matter in the air.
vi. Prohibition of the use of open fire: for the disposal of domestic and industrial waste.
Using open fire to bulk domestic and industrial waste can produce dust, smoke and
significant amount of air pollutants.
vii. Use of low-Sulphur Diesel Reduction of permissible level of sulphur in diesel.
Through these regulations and measures, Pakistan aims to improve air quality and
minimize the adverse effects of air pollutions on public health and the environment.

14.16 ECONOMIC, SOCIAL & POLITICAL ISSUES

Air pollution and bad air quality is responsible for huge economic costs, social and
potential issues.
14.16.1 Economic Issues
• Poor air quality can reduce worker productivity due to illness and absenteeism.
• Air pollution and air quality can damage crops reducing agricultural yield and
increasing food prices.
• Air pollution leading to acid rain can degrade buildings, bridges and other infrastructure.
14.16.2 Social Issues
• Vulnerable populations, such as children, the elderly, and low-income communities are
disproportionately affected by air pollution.
• Chronic exposure to polluted air reduces the overall quality of life. This affects social
well-being and community health.
• Severe air pollution can force people to migrate from the unhealthy polluted areas to
places with better air quality, leading to social displacement and associated challenges.
14.16.3 Political Issues
• Implementing effective air quality regulations can be challenging due to political and
economic interests.
• Air pollution is not confined to borders and effective management requires international
corporation.
• Implementing air quality regulations requires strict governance, which might slow
down industrial growth and economic development and leads to political conflicts.
• Addressing air pollution requires a multi-faceted approach, balancing socio-economic,
and technological considerations.
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EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. Which gas causes yellow color in photochemical smog?
a) CO b) SO3
c) NO2 d) SO2
II. The depletion of Ozone in stratosphere region is mainly due to the reaction of O3
with:
a) CO2 b) SO2
c) O2 d) CFCs
III. Which particulate matter size is considered the most harmful to human health?
a) PM 10.0 b) PM 5.0
c) PM 2.5 d) PM 1.0
IV. Which of the following is a natural factor that can improve air quality?
a) Wildfire b) Urbanization
c) Rainfall d) Industrial emission
V. What is a common human activity that led to increased level of carbon monoxide
in the atmosphere?
a) Tree planting b) Gasoline driven vehicles
c) Using electric appliances d) Solar panel installation
VI. Chlorofluorocarbons (CFCs) have been primarily used in …….
a) Fertilizers b) Refrigerants and aerosol propellants
c) Pharmaceuticals d) Pesticides
VII. What are the primary chemical processes that removes carbon dioxide from the
atmosphere?
a) Combustion b) Photosynthesis
c) Respiration d) Volcanic activity
VIII. An AQI value between 51 and 100 typically indicates which level of air quality?
a) Good b) Moderate
c) Unhealthy d) Fatal

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IX. Acid rain is primarily caused by the release of which of the following gases into
the atmosphere?
a) Carbon dioxide (CO₂) and methane (CH₄)
b) Sulfur dioxide (SO₂) and nitrogen oxides (NOₓ)
c) Chlorofluorocarbons (CFCs) and halons
d) Ozone (O₃) and carbon monoxide (CO)
X. In the presence of sunlight and nitrogen oxides (NOx), ​VOCs can contribute to the
formation of:
a) Acid rain b) Ozone depletion
c) Photochemical smog d) Greenhouse gases
XI. Primary pollutants like nitrogen oxides (NOx ) and volatile organic compounds
(VOCs) react in the presence of sunlight to form a key component of photochemical
smog, which is a:
a) Primary pollutant. b) Secondary pollutant.
c) Naturally occurring atmospheric gas. d) Harmless byproduct of combustion.
XII. A key component that distinguishes photochemical smog from industrial smog
is the presence of:
a) High concentrations of sulfur dioxide.
b) A significant amount of ozone and other photochemical oxidants like PAN
(peroxyacetyl nitrate).
c) Reduced visibility due to fog and smoke particles.
d) Formation primarily during the early morning hours.

SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. Identify and briefly explain three major natural sources of air pollutants.
b. How can deforestation impact air quality?
c. Explain the reasons for the temperature trends observed in the troposphere and the
stratosphere.
d. Describe four significant anthropogenic (human-caused) activities that contribute to
the deterioration of air quality. For each activity, name at least one major pollutant
released.
e. What are the environmental impacts of persistent organic pollutants (POPs)?
f. How does polycyclic aromatic hydrocarbon (PAHs) affect human health?
g. What is photochemical smog? Under what conditions, it forms?

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h. What type of data do air quality index (AQI) system provide?

i. Distinguish between PM10​ and PM2.5​, specifying the size ranges and describing why
PM2.5​is generally considered more harmful to human health.
j. What are the main chemical processes involved in the formation of acid rain?
k. What are the specific measures to control smog?
l. How does a catalytic converter reduce harmful vehicle emissions?
m. Describe the sources of lead and mercury pollution.

DESCRIPTIVE QUESTIONS
Q.3 Discuss sources and effects of following air pollutants on environment:
i) Heavy metals ii) VOCs iii) PAHs iv) POPs
Q.4 Write short notes on the following:
i) CFCs and ozone layer depletion ii) Greenhouse effect and global warming
Q.5 How the fossil fuel burning causes acid rain? Discuss in detail with chemical
reactions.
Q.6 What is meant by air quality AQI? Describe the factors affecting the air quality.

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15
Chemistry-XI

BASIC SEPARATION
TECHNIQUES
STUDENT LEARNING OUTCOMES [C-11-E-01 to C-11-E-08]
Define important terms associated with creating chemical solutions: Solvent, Solute, Solution,
Residue and Filtrate. (Knowledge)
Explain methods of separation and purification: (Understanding)
a) Filtration b) Crystallization
c) Simple Distillation d) Fractional Distillation
Identify substances and assess their purity using melting and boiling point information. (Application)
Suggest suitable separation and purification techniques given information about the substances
involved and their usage in daily life. (Application)
Describe how paper chromatography is used to separate mixtures of soluble substances using suitable
solvent. (Understanding)
Describe use of locating agents when separating mixtures containing colorless substances.
(Understanding)
Interpret simple chromatograms to identify unknown substances by comparison with known
substances pure and impure substances. (Application)
State and use for Rf. (Knowledge)

Analytical chemistry is the science of chemical characterization. A complete chemical

characterization of a compound must include both qualitative and quantitative analyses. In
qualitative analysis, the chemist is concerned with the detection or identification of the
elements present in a compound, whereas in quantitative analysis, the relative amounts
of elements in compounds are determined.
A complete quantitative determination generally consists of four major steps
1. Obtaining a sample for analysis
2. Separation of the desired constituent
3. Measurement, and calculation of results
4. Drawing conclusion from the analysis.
In this chapter, some basic separation techniques are discussed here to practice in the lab.

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15.1 METHODS OF SEPARATION OF MIXTURES

The components of a mixture can be separated by any of the following physical methods.
1. Filtration 2. Crystallization
3. Simple distillation 4. Fractional distillation
5. Paper Chromatography

15.1 Filtration
This process is used to separate one of the components
of a two-component heterogeneous mixture from a
solution. The first step is to select a suitable solvent
in which one of the components dissolves completely
while the other remains practically insoluble. For
example, let us take a mixture of common salt and
sand.
Dissolve this mixture in distilled water. The common
salt will distribute itself through out water to give a
homogeneous mixture. This homogenous mixture is Figure 15.1 The process of filtration
called a solution of common salt in water.
Common salt in this solution is called a solute while water is called a solvent. In a solution,
the solvent is that component which is present in excess as co‑mpared to the solute. While
common salt disappears in water, the other component, sand remains undissolved and after
some time settles down at the bottom of solution.
The process of filtration is used to separate sand from the above solution. It can be
performed with several types of filter media. Nature of the precipitate and other factors
dictate which filter medium must be used. The most convenient ways of filtration are
either through a filter paper or through a filter crucible.
a) By using Filter Paper
Folding of filter paper is important and is done in two ways.
1. Filtration by a glass funnel and filter paper is usually a slow process. As the mixture
is poured onto the filter paper, the solvent (water) passes through leaving behind
the suspended particles on the filter paper. Filter papers are available in a variety of
porosites (pore sizes). Which pore size is to be used, depends upon the size of particles
in the precipitate. The filter paper should be large enough so that it is one-fourth to
one-half full of precipitate at the end of filtration. In this way, the filtrate runs down the
side of beaker without splashing. A complete filtration assembly is shown in Figure
15.1.

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First fold Second fold Forming the cone

Fig 15.2 a Folding of filtration paper

The folded filter paper may then be inserted into 60-degree funnel, moistened with water
and firmly pressed down.
2. The rate of filtration through conical funnel can be considerably increased using a
Fluted Filter Paper, for preparation of such a paper ordinary filter paper in folded
in such a way that a fan like arrangement with alternate elevations and depressions at
various folds is obtained Fig (15.2 b).

Filter disk

Fold in half Fold in half again

Open filter cone This is the Fold to crease the Fold to crease the quarter
“accordion” shape eight section section

Fig 15.2 b Fluttled filter paper

After filtration, the liquid which is obtained in the conical flask underneath the funnel is
called the filtrate. The sand left behind on the funnel is called the residue.
b) By using Crucible
Another convenient way to filter a precipitate is by suction through a crucible. Two types
of crucibles are generally used.
1. Gooch crucible is made of porcelain having a perforated bottom which is covered
with paper pulp or a filter paper cut to its size as shown in Figure 15.3. Quick filtration
can be done by placing such crucible in a suction filtering apparatus. It is useful for the
filtration of precipitates, which need to be ignited at high temperature. If its perforations
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are covered with asbestos mat, it may be used to filter solutions that react with paper
e.g. concentrated HCl and KMnO4 solutions.

Figure 15.3 Gooch crucible Fig 15.4 Sintered glass crucible

2. Sintered glass crucible is a glass crucible with a porous glass disc sealed into the
bottom. It is very convenient to use because no preparation is needed as with the Gooch
crucible as shown in Figure 15.4.

Quick Check 15.1

a) Name different filter media used in filtration?
b) What are the components of the filtration process?
c) Differentiate gravity filtration and vacuum filtration.
d) Different shade Gooch and sintered glass crucible.

15.2 CRYSTALLIZATION
The basic principle of crystallization is the fact that the solute should be soluble in a
suitable solvent at high temperature and the excess amount of the solute is thrown out as
crystals when it is cooled. The process of crystallization involves the following steps.
Choice of a Solvent
An ideal solvent should have the following features.
i. It should dissolve a large amount of the substance at its boiling point and only a small
amount at the room temperature.
ii. It should not react chemically with the solute.
iii. It should either not dissolve the impurities or the impurities should not crystallize from
it along with the solute.
iv. On cooling, it should deposit well-formed crystals of the pure compound.
v. It should be inexpensive, safe to use and easily removable.

Keep in Mind!
During crystallization, sometimes the crystals start to appear during the process of filtration. This result in
choking the filter paper or the funnel. To avoid this a hot water funnel may be used.

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The solvents which are mostly used for crystallization are, water, absolute ethanol,
chloroform, carbon tetrachloride and acetic acid.
If none of the solvents is found suitable for crystallization, a combination of two or more
miscible solvents may be employed. If the solvent is inflammable, then precaution should
be taken while heating the solution so that it does not catch fire. In such cases, water bath
is used for heating purpose.
15.4.1. Steps of crystallization
i. Prepare a saturated solutions of the substance in a suitable solvent at the temperature
of the experiment.
ii. The insoluble impurities in the saturated solution are then removed by filtering the
hot saturated solution. This avoids the premature crystallization of the solute on the
filter paper or in the funnel stem. If necessary, hot water funnel should be used for this
purроse.
iii. The hot filtered solution is then cooled at a moderate rate so that medium sized crystals
are formed.

Keep in Mind!
Sometimes during the preparation of a crude substance, the colouring matter or resinous products
affect the appearance of product. Such impurities are conveniently removed by boiling the substance
in the solvent with the sufficient quantity of finely powdered animal charcoal and then filtering the
hot solution. The coloured impurities are adsorbed by animal charcoal and the pure decolourized
substance crystallizes out from the filtrate on cooling.

iv. When the crystallization is complete, the mixture of crystals and the mother liquor is
filtered through a Gooch crucible using a vacuum pump.
v. The crystals may be air-dried are dried in an oven. The crystals are dried in an oven
provided the substance does not melt or decompose on heating at 100° C.

Filter off excess

solid

Filter
paper

Transfer hot Crystals formed

Solution of Evaporating dish Evaporate to liquid to after leaving to cool
one solid, reduce volume of dish until solution is
and insoluble solution saturated
impurity
Figure 15.5 Different steps involved in crystallization
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A safe and reliable method of drying crystals is through a vacuum desiccator. In this
process the crystals are spread over a watch glass and kept in a vacuum desiccator for
several hours. The drying agents used in a desiccator are CaCl2, silica gel or phosphorus
pentaoxide Figure 15.9.

Quick Check 15.2

a) What is the basic principle of crystallization?
b) How a suitable solvent is selected for the process of crystallization?
c) Mention the important steps of crystallization.

15.3 SEPARATION THROUGH DISTILLATION

If a two-component mixture is a solution containing a solid compound dissolved in water
or in any other suitable solvent, then that mixture can be separated by simple distillation.
Sea water is not drinkable because it is a mixture of many soluble inorganic compounds in
water. To get rid of these compounds, sea water is distilled to make it drinkable.
The process of fractional distillation is another type of distillation used to separate two liquids
which are soluble or miscible with each other. For example, a mixture of water and ethyl alcohol
can be separated by heating the mixture in a distillation flask.
15.2.1 Distillation Process
1. Simple distillation
It is used to separate solvent from solution. For example, take 100 cm3 sea water. Set up
the apparatus as shown in the Figure 15.5. Add a few pieces of boiling chips to prevent
bumping of the liquid in the flask. Make whole apparatus air tight to prevent vapors to
escape.
Heat the flask gently with the help of a Bunsen burner. Turn on the tap to allow cold water
to circulate slowly around the condenser. Water or alcohol will evaporate as its boiling
point is reached, and its vapours will pass through the condenser. The water circulating
around the condenser will condense these vapours back into the liquid form. This is called
distillate and it will be collected in the receiving flask. The components left behind in the
distillation flask are collectively called the residue.
2. Fractional distillation
Separating the two miscible liquids in this way is called fractional distillation. The process
of fractional distillation will be successful only if the difference in the boiling points of the
two liquids being separated, is around 25°C. The distillation column is a glass equipment
used in the distillation of mixture of liquids to separate it into its components depending
upon their boiling points. The distillation column is filled with glass beads to increase the
surface area available for condensing the vapor as shown in Figure 15.7.

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Thermometer Cold water in

Thermometer reading
Condenser

100ºC Fractionating
column
Water distils
78ºC
Water out
Ethanol distils Distilling
flask

Vapor
time Distillate
Figure. 15.6 Fractional distillation of
ethanol / water mixture
Figure 15.7 Fractional distillation setup

For example, when a mixture of ethyl alcohol and water is heated first ethyl alcohol will be
distilled over because its boiling point is 78 °C less than that of water whose boiling point
is 100 oC. As long as the alcohol is being distilled over, the temperature of the thermometer
will remain at 78 oC. As soon as the temperature starts rising above 78 oC, replace the
receiving flask with a new one as shown in Figure 15.7.
Start heating again. When the temperature of the thermometer rises to 100 oC, water
will start boiling and is collected in the receiving flask after condensation as the second
distillate. In this way both the components will be obtained in pure form.

Interesting Information!
Petroleum in natural form is a mixture of many compounds which are commonly used as fuels. Example
of such fuels are petrol, diesel, kerosene oil and furnace oil. These components have boiling points not
very different from one another. These components are separated as fractions by fractional distillation
using a fractionating or distillation column.

Quick Check 15.3

a) What is the difference between simple distillation and fractional distillation?
b) Give some daily-life applications of fractional filtration?

15.3. CHROMATOGRAPHY
Chromatography is a method used primarily for the separation of a sample of mixture. It
involves the distribution of a solute (mixture) between a stationary phase and a mobile
phase. The stationary phase may be a solid or a liquid supported as a thin film on the
surface of an inert solid. The mobile phase flowing over the surface of the stationary phase
may be a gas or a liquid.
Chromatography in which the stationary phase is a solid, is classified as adsorption
chromatography. In this type, a substance leaves the mobile phase to become adsorbed
on the surface of the solid phase. Examples of adsorption chromatography are thin layer
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chromatography (TLC) and column chromatography.

Chromatography in which the stationary phase is a liquid, is called partition
chromatography. In this type, the substances being separated are distributed throughout
both the stationary and mobile phases. Examples of partition chromatography are paper
chromatography and gas liquid chromatography.
15.3.1. PAPER CHROMATOGRAPHY
It is a type of partition chromatography. The entrapped water in cellulose fibers of paper
and mobile phase which passes over the
paper are immiscible, The mobile phase is
usually an organic liquid.
There are three common ways of carrying
out paper chromatography namely (i)
ascending (ii) descending (iii) radial /
circular. Only the ascending type will be
discussed here. In this technique, the
solvent travels upwards by capillary action.
A solvent mixture, specially composed in
accordance with the sample to be separated, Figure 15.8 Paper chromatagraphy
is poured into the chromatographic tank
Figure 15.7, Cover the tank to homogenize its inner atmosphere. Take about 20 cm strip
of Whatmann’s chromatographic paper No.1 and draw on it a thin pencil line about
2.5 cm from one end. Spot a point, on the pencil line, with the sample mixture solution.
To facilitate identification of the components
of the mixture, spots of the known compounds
may also be placed alongside.
Water
When the spots have dried, suspend the paper
spol of indicator
with clips so that the impregnated end dips into
solvent mixture to a depth of 5-6 mm. Cover Chromatography
the tank. As the solvent front passes the spots, paper
the solutes begin to move upward. Different spot of indicator
components of solute will move at different Water
rates. This separates the mixture. When the
solvent front has risen to about length of the ascending method descending method
Figure 15.9 Ascending and descending paper chromotography
paper, remove the strip, mark the solvent front
with a pencil and allow the strip to dry.
15.3.2 Locating agents colorless substances.
Once the paper is dried, the pattern on the paper is called a chromatogram. The different
components of the mixture, if coloured, can visually be identified. If colourless, the
chromatogram has to be developed by chemical methods or physical techniques used to
identify the spots.

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A very convenient way of visualizing the colourless chromatogram is to see it under the
light of a UV lamp. The spots look coloured under UV light. Alternatively, a locating agent
like ninhydrin can be used to locale the spots. A locating agent is generally a chemical
that reacts with the colourless substances like amino acids to give coloured products that
are visible for inspection.
15.3.3 Use of Retardation Factor
Each component has a specific retardation factor called Rr value. The Rf value is given by:

Distance travelled by a component from the original spot

Rf =
Distance travelled by solvent from the original spot

With reference to Figure 15.10 the

chromatogram shows that the sample x
A contains both components B and C. R f ( B) =
y
The Rf values for B and Care given 1
x
by: R f (C ) =
y 1
Paper chromatography is a convenient A B C
way of checking if a substance Figure 15.10 Chromatogram
formed in a chemical reaction is pure
or impure using a suitable solvent in which the substance dissolves. A pure substance
produces one spot on the chromatogram while an impure substance produces more than
one spot.
A paper chromatogram can also be used to identify substances by comparing them with
known samples of pure substances. Two substances are likely to be identical have the same
Rf values.

Interesting Information!
Whatmann filter paper which are used in paper chromatography are made from specially selected
cotton cellulose. Whatmann’s filter paper No. 1 is used for routine applications and it has medium
retention and medium flow rate. Its pore size is 11 μm.

In this chromatogram shown in Figure 15.10, the impure substance has two components
present in it corresponding to two coloured spots it has shown. The spots in the impure
substance have travelled the same distance as the reference’s pure compounds. The Rf
value is always the same for a particular substance if we use the same stationary phase and
the same mobile phase.
15.3.4 Applications of Paper Chromatography
i. The techniques of chromatography are very useful in organic synthesis for separation,
isolation and purification of the products. They are equally important in qualitative and

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quantitative analyses and for determination of the purity of a substance.

ii. Chromatography is very useful for identifying complicated chemicals such as dyes,
drugs and pesticides.

Quick Check 15.4

a) On which basis the components of a mixture are separated from one another in paper
chromatography?
b) What are the stationary and mobile phases in paper chromatography?
c) How the purity of a substance is determined by using paper chromatography?

15.4 HOW TO CHECK THE PURITY OF THE PRODUCT?

Separate methods are applied to purify compounds if they exist in liquid or solid states
under normal conditions. Liquids are generally purified by distilling them at normal
pressure or under vacuum. Purity of liquids can be checked by comparing their boiling
points with those mentioned in the literature.
Aspirin is prepared by reacting salicylic acid with an excess of acetic anhydride in the
presence of a few drops of concentrated H2SO4. Aspirin is a very important analgesic and
antipyretic.
After the reaction is over, water is added in the reaction mixture to precipitate out aspirin.
The mixture is then filtered to get aspirin as a crude product. It is then crystallized in water
as polar solvent.
i. Aspirin obtained in the above process O C OH O
C
OH
O
may be mixed with the unreacted starting OH O C
(CH CO) O
material, salicylic acid. To check whether the 3 2
3
CH
product is pure or impure, its melting point is H PO)
3 4
Heat
determined. If the product melts sharply, in Salicylic Acid AcetylSalicylic Acid
Aspirin
this case at exactly 136°C then the product is
considered as pure. If the product shows a melting point which is not sharp rather it
melts within a range of temperature, it is considered as an impure product.
ii. Another way of assessing the purity of the product is to get the mixed melting point. In
such a case the product is mixed with a pure sample of aspirin and the melting point is
then determined. If it still shows a sharp melting point then it is a pure product.
iii. Another way of checking the purity of aspirin is to run paper chromatography of this
sample along with the pure samples of both aspirin and salicylic acid and matching the
Rf value.

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Quick Check 15.5

a) How does melting point of a substance indicate its purity?
b) Which technique (filtration, crystallization and distillation) is suitable for the separation of the
following mixtures?
i) Petroleum and water ii) NaCl and NaNO3
iii) activated charcoal and sodium chloride iv) Methanol, ethanol and propanol

EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. After the crystals are formed, they are typically separated from the mother liquor
by:
a) Evaporation. b) Decantation or filtration.
c) Sublimation. d) Distillation.
II. The comparative rates at which the solutes move in paper chromatography
depend on:
a) The size of filter paper b) Rf values of solutes
c) Temperature d) Size of the chromatographic jar
III. The method that can be used to separate two solid compounds with different
solubilities in a solvent is:
a) Distillation b) Isolation
c) Crystallization d) Filtration
IV. It is suspected that a hand-written legal document has been changed by over
writing some crucial figures. Which technique you will use to check the inks used
at suspected places?
a) Distillation b) Chromatography
c) Solvent Extraction d) Crystallization
V. In chromatography, the components of the mixture are separated based on:
a) Their molecular masses
b) The interaction of the components with stationary as well as mobile phones
c) The type of solvent used
d) The filter paper used

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VI. The porous material used to separate the solid from the liquid during filtration
is called the:
a) Filtrate b) Residue
c) Filter medium d) Solvent
VII. The key difference between simple distillation and fractional distillation is the
presence of a:
a) Condenser with a larger surface area. b) More powerful heat source.
c) Fractionating column. d) Vacuum pump.
VIII. The essential requirement for separating two liquids by simple distillation is
that their boiling points should differ by at least:
a) 5 °C b) 10 °C
c) 25 °C d) 50 °C
IX. In chromatography, a locating agent is used to:
a) Dissolve the sample for separation.
b) Carry the separated components along the stationary phase.
c) Make colorless separated components visible for identification.
d) Prevent the sample from interacting with the stationary phase.

SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. Why is there a need to crystallize a crude product?
b. What is the function of fluted filter paper?
c. What is the difference between a Gooch crucible and sintered glass crucible?
d. What type of mixtures are filtered through a Gooch crucible?
e. What is function of fractionating column during fractional distillation?
f. What is the stationary phase in the paper chromatography?
g. What will happen during paper chromatography if the components of the mixture have
a comparable attraction for the stationary phase?
h. What is the meant by the term “developing the chromatogram” in paper
chromatography?
i. What is the basic principle of paper chromatography?
j. Why water is not generally used as a solvent in paper chromatography?
k. Differentiate between adsorption and partition chromatography.
l. How can you check the purity of a compound with the help of paper chromatography?
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m. You have prepared a solid sample of glucosazone in the laboratory. How will you
proceed to check the purity of the sample?

DESCRIPTIVE QUESTIONS
Q.3 Differentiate simple distillation and fractional distillation in construction and
applications.
Q.4 Describe the criterion to choose the suitable solvent in the process of
crystallization?
Q.5 What is the basic principle of paper chromatography? Give its three practical
life applications.

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS

16
Chemistry-XI

LAB SAFETY AND

PRACTICAL SKILLS
STUDENT LEARNING OUTCOMES [C-11-F-01 to C-11-F-21]
Identify the chemical hazards in the lab in the context of the experiment being conducted.
(Knowledge)
Test that the equipment is working properly without any potential risk of injury before conducting
an experiment. (Knowledge)
Ensure that work space for conducting the experiment is not crowded with apparatus as to be
hazardous. (Knowledge)
Ensure that safe distance space is kept at all times from other investigators who may handling lab
apparatus. (Knowledge)
Identify what bodily harm could occur from physical, chemical, biological and safety hazards in
context of the experiment being conducted. (Knowledge)
Recognize that it is always better to ask for help from the lab instructor when unaware of how to use
new apparatus. (Knowledge)
Identify the proper waste disposal system for chemicals being used. (Knowledge)
Set up apparatus following instructions given in written or diagrammatic form. (Understanding)
Use apparatus to collect an appropriate quantity of data. (Understanding)
Make observations including subtle differences in colour, solubility or quantity of materials.
(Understanding)
Make measurements using pipettes, burettes, measuring cylinders, thermometers, and other common
laboratory apparatus. (Understanding)
Decide how many tests or observations to perform. (Understanding)
Identify where repeated readings or observations are appropriate. (Understanding)
Replicate readings or observations as necessary, including where an anomaly is suspected.
(Understanding)
Identify where confirmatory tests are appropriate and the nature of such tests. (Understanding)
Select reagents to distinguish between given ions. (Knowledge)
Carry out procedures using simple apparatus in situations where the method may not be familiar to
the candidate. (Application)
Describe acid base titration to include the use of a burette, volumetric pipette and suitable indicator.
(Understanding)
Describe how identify the end point of a titration using an indicator. (Understanding)
Describe tests to identify the anions: (a) CO32-, (b) Cl1-, Br1- and I1- (c) NO31-(d) SO42- (e) SO32-
(Understanding)
Describe tests using aqueous NaOH and aqueous NH3 to identify the aqueous cations: (a) Al3+(b)
NH4+(c) Ca2+ (d) Cr3+ (e) Cu2+ (f) Fe2+(g) Fe3+ and (h) Zn2+ (Understanding)

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

A chemistry laboratory is a chemist workshop. It is a place where a student is trained

to observe the physical and chemical characteristics of substances by following definite
procedures. Before starting the laboratory work, a student should get himself familiarized
with the layout of the laboratory and various fittings provided on the laboratory table as
well as the side shelves.

16.1. GENERAL INSTRUCTIONS TO THE STUDENTS.

i. Students are expected to conduct themselves in a responsible manner at all times in
the lab.
ii. They are advised not to work alone in the lab. Experiments should be performed in the
presence of lab instructor and other laboratory staff.
iii. Students should always wear lab coat and safety goggles while working in the lab.
Girls must tie up their scarves and hair before start working in the lab.
iv. Determine the potential hazards related to any equipment or the experiment before
beginning any work. Appropriate safety precautions must be observed at all cost.
v. There must not be any crowding in the lab and students should stick to their work
places at a safe distance from each other.
vi. Don’t bring any food items in the lab. Never taste or smell any compound or a gas.
vii. Any accident or breakage of glassware must be reported to the incharge of the
laboratory immediately.
viii. If you cannot handle an instrument or an equipment properly then you must seek
help from the instructor.
ix. Do not pour chemicals down the drains and do not utilize the sewer for chemical
waste disposal.
x. Follow the warning sign displayed in the lab.

16.2 COMMON TYPES OF HAZARDS IN A LABORATORY

Most hazards which we might face while working in the laboratory fall into three categories,
physical, chemical and biological hazards.
16.2.1 Physical Hazards
The most common physical hazards are slips and falls when working on wet floor. A
worker must take all types of precautions to avoid accidents related to physical hazards
such as slipping, pulling, falling etc.
A worker should wear cut-resistant gloves while handling the broken glassware to prevent
cuts, abrasions and skin damage. It should be mandatory for the laboratory staff to dispose
off broken glassware in special container to prevent injury.

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

Figure 16.2 Pictogram of chemical hazards

16.2.2 Chemical Hazards

A laboratory worker must use the chemicals according to the standard procedures keeping
in view the particular hazards and precautions required for the safe use.

16.2.3 Biological Hazards

The most common biological hazards arc allergens,
infectious diseases which are transferred from
animals to humans and viral diseases.

16.3 WASTE DISPOSAL SYSTEM

FOR CHEMICALS Figure 16.3 Some biological hazards

Chemical waste cannot be disposed of in bins or sewer system. Most chemical wastes
must be disposed of keeping in view the following rules and regulation of Environmental
Protection Agency (EPA).
1. Store chemical wastes in proper containers.
2. Label the chemical waste containers with the types of wastes, the date of waste and
place of origin.
3. These containers are then transferred to the allocated site where these are appropriately
treated to dispose them off.
i. Chemical treatment of wastes involves neutralization, precipitation, ion exchange,
oxidation or reduction.

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

16.4 FIRST AID IN LABORATORY

Every laboratory must have a first aid box. Common accidents and their first aid treatments
are given in the Table 16.1 below:
Table 16.1 Accidents and their First Aid treatment

Type of Accident First Aid Treatment

1 Cuts
Minor cuts • Remove the glass piece if any, apply a little methylated
spirit or tincture iodine with a piece of cotton. Both act
Serious cuts as disinfectant.
• Apply pressure on the cut for about 10 minutes to
stop bleeding. Consult a doctor.
2 Eye Injuries
Acid in the eye • Wash thoroughly with water and then with 1%
sodium bicarbonate solution.
Alkali in the eye
• Wash with water followed by 1% boric acid solution.
Foreign particle in the eye
• Do not rub the eyes. Remove the particle carefully
Soreness in the eye with soft handkerchief then wash with water.
• Put a drop of olive oil in the eyes and keep them
closed for some time.
3 Burns
Burns with dry heat (flame, • Apply burnol or mustard oil.
hot object) • Wash freely with ice cold water. Then wash with a
Burns causing blisters saturated solution of sodium bicarbonate and again
with water.
Acid burns
• Wash freely with water and then with 1% acetic
Alkali burns acid solution and again with water, dry the skin and
Bromine burns apply the burnol.
• Wash fully with 2% ammonia solution and apply
glycerin. Wipe off glycerin after sometime and
apply burnol.
4 Poisons
Poisons swallowed Spit immediately, wash mouth with water repeatedly.
Acid swallowed • Drink a lot of water or lime water or milk of
magnesia.
Caustic alkalies swallowed
• Drink a lot of water; drink a glass of lemon or
Salt of heavy metals orange juice.
swallowed.
• Take milk or white part of the egg.

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

5 Fire • Do not run. Wrap with blanket or with dry cotton

i) Clothes catch fire cloth. Lie down on the floor.
ii) Beaker containing • Cover the beaker with a duster or damp cloth. This
inflammable liquid. will cut off the supply of oxygen.
catches fire. • Throw a mixture of sand and sodium bicarbonate.
iii) Spirit or oil catches Do not throw water. It will simply spread the fire.
fire. • Switch off the electric supply immediately and
iv) Electric parts catch throw sand. Do not throw water in such cases to
fire. extinguish fire.

Quick Check 16.1

a) Mention common types of hazard. b) How chemical waste is disposed off?
c) How H2SO4 burn is treated in the lab? d) What are different types of burns?

16.5 ACID-BASE TITRATION

Volumetric analysis is used to find the concentrations of solutions by means of a technique
known as titration. In this technique a solution of unknown concentration is combined
slowly and carefully with a known volume of a standard solution until a colour change
shows the completion of the reaction. The substance which indicates the completion of
reaction by the change in its colour is called an indicator. The moment at which the
indicator changes colour is called the end point. Either solution can be taken in a burette
with the other solution taken in a conical or a titration flask.

Did you know!

Phenolphthalein solution is prepared by adding one gram of the indicator in 500 cm3 of 50% ethanol. Use
only one to two drops in 10 cm3 of the solution to be titrated. The color change is from pink to colorless
as the pH decreases. The light pink color which marks the end point tends to fade gradually due to the
interference of atmospheric carbon dioxide which slowly dissolves in the solution.

Materials Required
Burette, pipette, funnel, conical flask, HCI solution, NaOH solution, phenolphthalein.
Procedure of Titration
i. Rinse the pipette first with distilled water and then with the given NaOH solution.
ii. Rinse the conical flask with distilled water only.
iii. Pipette out 10 cm3 of NaOH solution into a conical flask.
iv. Add one to two drops of phenolphthalein indicator into it. The solution turns
pink.
v. Rinse the burette first with distilled water and then with the given HCl solution.

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

vi. Fix the burette on a clamp stand in an upright position.

vii. Fill it with the given HCl solution with the help of a funnel. Remove funnel from the
burette.
viii. Using the tap at the base of the burette, allow the acid to flow into a beaker to remove
any air bubble present in the nozzle.
ix. Note the burette reading as an initial reading using an anti-parallax card or a white
paper.
x. During titration, place the conical flask on a white paper under the burette to see the
color change of the indicator clearly. Check that the burette does not leak.
xi. Carry out a rough titration by adding hydrochloric acid solution from the burette drop
wise to the conical flask.
xii. The contents of the flask must be swirled adding of acid for thorough mixing.
xiii. Keep on adding acid till the colour of solution becomes light pink persistently. This
will be the end point of the reaction.
Again, note down the burette reading, this will be the final reading. The difference of final
and initial readings of burette will give the volume of the acid used.

Figure 16.6 Procedure of titration

Repeat the titration to get accurate and concordant readings. Take at least three concordant
readings which agree with one another within 0.1 cm3.
Observations
Titration number Rough Reading 1 2 3
Final reading x
Initial reading y
Volume of acid used (cm3) (x-y)

Volume of HCl solution used = ________cm3

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

Chemical Equation
NaOH ( aq ) + HCI ( aq ) → NaCI ( aq ) + H 2O( I )
Calculation
Find out the molarity of NaOH solution by using the following molarity equation:
Acid Base
M 1V1 M 2V2
=
M1 = Molarity of acid solution n1 n2
V1 = Volume of the acid used
n1 = No. of moles of the acid in the balanced chemical equation
M2 = Molarity of base solution
V2 = Volume of base solution used
n2 = No. of moles of the base in the balanced chemical equation
M 1V1 n2
M2
= ×
n1 V2
Molarity of the given base solution is ____M.
Quick Check 16.2
a) Define indicator and endpoint in a titration. b) What is meant by concordant reading?
c) d)

16.6 TESTS FOR IDENTIFICATION OF ANIONS

a) Identification of carbonate CO32− radical
Experiment Observation Inference
Take about 2 g of solid Effervescence takes place
2−
carbonate sample in a clean during which a gas evolves Carbonate ( CO3 ) are
test tube and then add about briskly, that turns lime indicated ions.
5 cm3 of dilute HCl solution. water turns milky.
Pass the gas evolved in the
above step through a solution
of lime water.

Reactions involved in the above steps

CO32(−aq ) + 2H (+aq ) → H 2 O(  ) + CO 2( g )

Ca(OH) 2(aq) + CO 2(g) → CaCO3(s) + H 2 O(l)

Lime water (white ppt)

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

(b) Identification of chloride (Cl1-), Bromide (Br1-) and Iodide (I1-) radicals
Experiment Observation Inference
–1
Take 2 g of solid sample in a test tube and A thick white precip- Cl ions are
add 5 cm3 of distilled water to make the itate is formed which indicated.
aqueous solution. Add a few drops of dil. dissolves in aq.NH3.
HNO3 solution to acidify the solution of the
salt, finally add about 5 cm3 of aqueous Ag
NO3.
Take 2 g of solid sample in a test tube and A thick cream-yellow Br1- ions are
add 5 cm3 of distilled water to dissolve the precipitate is formed. indicated.
salt. Add a few drops of dil. HNO3 to acidify
the above solution. Finally add 5 cm3 of
aqueous AgNO3.
Take 2 g of solid sample and dissolve it in A bright yellow I1- ions are
3
5 cm of distilled waler. Add a few drops of precipitate is formed. indicated.
dil. HNO3 to make it acidic. Finally add 5
cm3 aqueous AgNO3.

Reactions involved in the above tests Did you know?

Ag +
(aq) + Cl −
(aq) → AgCl(s) In the above tests for the detection of halide
white ppt
ions, dilute nitric acid is added to prevent the
Ag (aq)
+
+ Br(aq)
−
→ AgBr (s)
precipitation of carbonate ions along-with
cream yellow ppt halide ions.

Ag (aq)
+
+ I(aq)
−
→ AgI (s)
bright yellow ppt

Figure 16.7 Observation of reactions of halide ions with AgNO3

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

c) Identification of Nitrate ( NO1-3 ) radical

Experiment Observation Inference

Take 2 g of solid sample in a A characteristic smell of NO31– ions are indicated.

clean test tube and dissolve it NH₃ gas is felt near the
in 5 cm3 distilled water. Add to mouth of test tube. This
it 5 cm3 of sodium hydroxide gas turns red litmus paper
solution. Finally add 3 g of blue.
powdered aluminium metal.

Aluminium metal reduces nitrate ions to

ammonium ions which then react with aqueous
NaOH to evolve ammonia gas. The reduction of
NO31− with aluminium metal is a redox reaction
in which Al metal acts as a cathode and reduces
nitrate ions to ammonia gas.

- 1-
3NO1-3(aq) + 8Al(s) + 5OH (aq) + 18H 2 O( ) → 3NH 3(q) + 8  Al(OH) 4(aq) 

(d) Identification of Sulphate ( SO42− ) radical

Experiment Observation Inference
Take 3 g of solid sample in A heavy white precipitate of SO 2− ions are indicated
4
a clean test tube. Dissolve it BaSO4 is formed.
in 5 cm3 of distilled water.
Acidify the solution with
a few drops of dil. HNO3
and then add 5 cm3 barium
nitrate solution.

SO 2-4 + Ba (aq)
2+
→ BaSO 4
 Did you know?
(aq) (s)
white ppt Dilute nitric acid is added to destroy any carbonate
ions present in the solution as an impurity.

Quick Check 16.3

a) Distinguish carbonate (CO32-) and bicarbonate (HCO31-) radicals.
b) What is ring test? Give equation for this test.
c) Give names and formulas of some water insoluble sulphates.
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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

16.7 TESTS FOR IDENTIFICATION OF BASIC RADICALS

a) Identification of Aluminium ( Al 3+ ) radical
Take 4 g of solid sample in a clean test tube. Dissolve it in about 10 cm3 distilled water.
Divide this solution into two parts for further tests.
Experiment Observation Inference
To one part, add about 5 A white gelatinous
cm3 NaOH solution. precipitate is formed. Al 3+ ions are indicated.
To the second part of A white precipitate is
the above solution, add formed. Al 3+ ions are indicated
a few drops of aqueous
ammonia.

Al3(aq)
+
+ 3OH1(aq)
−
→ Al(OH)3( s )
white ppt
1+
b) Identification of Ammonium ( NH ) radical 4

Experiment Observation Inference

Take 4 g of sample in a clean Ammonia gas is evolved
1+
test tube. Dissolve it in 10 cm3 with a distinct smell. NH 4 ions are indicated.
distilled water. Add NaOH Ammonia gas turns moist
solution and gently heat it. red litmus blue.

NH14+(aq) + OH1(aq)
−
→ NH3( g ) + H 2 O( )

2+
c) Identification of Calcium ( Ca ) radical
Take 4 g solid sample in a clean test tube. Dissolve it in 10 cm3 distilled water.
Make two parts of this solution for further tests.
Experiment Observation Inference
To one part, add NaOH White precipitate is formed Ca2+
ions are indicated.
solution. which does not dissolve in
excess of NaOH solution.
To the second part of Only a slight turbidity Ca2+ ions are indicated.
the above solution, add appears or No precipitate
aqueous ammonia. is formed.
2+
Ca (aq) + 2OH (aq)
−
→ Ca(OH) 2(s)
white ppt

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

d) Identification of Chromium radical (Cr3+)

Add 4 g sample in a clean test tube. Dissolve it in 10 cm3 distilled water. Make two parts
of the above solution for further tests.
Experiment Observation Inference
To one part, add NaOH A green precipitate appears Cr3+ ions are indicated.
solution. which turns into green
solution when excess of
NaOH is added
To the second part of A green precipitate appears Cr3+ ions are indicated.
the above solution, add which is insoluble in excess
aqueous ammonia. of aqueous ammonia.

3+
Cr(aq) + 3OH (aq)
−
→ Cr(OH)3(s)
Green ppt

e) Identification of Copper radical (Cu2+)

Add 4g solid sample in a clean test tube. Dissolve it in 10cm3 of distilled water. Make two
parts of the above solution for further tests.
Experiment Observation Inference
To first part, add NaOH A light-blue precipitate is Cu2+ ions are indicated.
solution. formed.
To the second part of Deep blue solution is Cu2+ ions are indicated.
the above solution, add formed.
aqueous ammonia.
2+
Cu (aq) + 2OH (aq)
−
→ Cu(OH) 2(s)
Blue ppt

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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

f) Identification of Iron (II) radical (Fe2+)

Take 4 g sample in a clean test tube. Dissolve it in 10 cm3 of distilled water. Make two
portions of the solution for further tests.
Experiment Observation Inference
2+
To one portion, add NaOH A green precipitate is Fe ions are indicated.
solution. formed which is turned into
orange brown precipitate
after some time.
To second portion of A white gelatinous Fe2+ ions are indicated.
the above solution, add precipitate of Fe(OH)2
aqueous ammonia. is formed which quickly
oxidizes to form red brown
precipitate of Fe(OH)3.
2+
Fe(aq) + 2OH (aq)
−
→ Fe(OH) 2
Green ppt

f) Identification of Fe(III) radical (Fe3+)

Take 2 g FeCl3 in a clean test tube. Dissolve it in 10 cm3 of distilled water. Make two
portions of the solution for further tests.
Experiment Observation Inference
To one portion, add NaOH Orange brown precipitate Fe3+ ions are indicated.
solution. is formed.
To the second portion of Orange brown precipitate Fe3+ ions are indicated.
the above solution, add is formed.
aqueous ammonia.
3+
Fe(aq) + 3OH (aq)
−
→ Fe(OH)3(s)
Orange brown ppt

g) Identification of Zinc radical (Zn2+)

Take 4 g solid sample in a clean test tube. Dissolve it in 10 cm3 of distilled water. Make
two portions of the above solution for further tests.
Experiment Observation Inference
To one portion add NaOH White precipitate is formed Zn2+ ions are indicated.
solution. which is soluble in excess
of NaOH solution.
To second portion of White precipitate is formed Zn2+ ions are indicated.
the above solution add which dissolves in excess
aqueous ammonia. of ammonia.
2+
Zn (aq) + 2OH (aq)
−
→ Zn(OH) 2 (s)
white ppt
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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

Quick Check 16.4

a) What is lake test? Give equation. b) How ammonium ion is indicated?
c) How will you distinguish ferrous (Fe2+)
and ferric (Fe3+) radicals?
d) What happens when aq. NH3 is added to Cu2+ solution in limited and excess quantities?

EXERCISE

MULTIPLE CHOICE QUESTIONS

Q.1 Four choices are given for each question. Select the correct choice.
I. While taking a reading with a burette, why it is always advisable to read the
lower meniscus for the colorless liquids and the upper meniscus for the coloured
liquids?
a) because it is more convenient
b) because colorless liquids have more surface tension than colored liquids
c) because lower meniscus does not exist for colored liquids
d) because of the parallax effect
II. Why phenolphthalein indicator is more appropriate to use during the titrations
which involve a strong acid and a strong base?
a) because it is itself weakly acidic
b) because the pH at the equivalence point as well as the pH over where the colour of
phenolphthalein changes match each-other.
c) because the solution at the end of titration is acidic.
d) because the solution at the end of titration is basic.
III. Which cation gives a white gelatinous precipitate upon the addition of aqueous
ammonia?
a) Cr3+ b) Cr2+
c) Zn2+ d) Al3+
IV. Addition of NH4OH to an aqueous solution of a cation gives a green precipitate
which turns brown upon standing. Which basic radical is indicated?
a) Cu2+ b) Cr3+
c) Fe2+ d) Fe3+
V. On dry heating test for salt analysis, the evolution of a colorless, odorless gas that
turns limewater milky suggests the presence of:
a) Chloride ion (Cl−) b) Sulfate ion (SO42−)
c) Carbonate ion (CO32−) d) Nitrate ion (NO3−)
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 IDENTIFYING HAZARDS AND DESIGNING SAFE EXPERIMENTS Chemistry-XI

VI. The chromyl chloride test is a specific confirmatory test for:

a) Bromide ions (Br−) b) Iodide ions (I−)
c) Chloride ions (Cl−) d) Sulfate ions (SO42−​)
VII. The brown ring test is a confirmatory test for which acid radical?
a) Chloride (Cl−) b) Nitrate (NO3−​)
c) Sulfate (SO42−​) d) Carbonate (CO32−​)

SHORT ANSWER QUESTIONS

Q.2 Attempt the following short-answer questions:
a. For which type of titration, methyl orange is used as an indicator?
b. Explain why phenolphthalein is a suitable indicator for the titration of a weak acid with
a strong base but not for the titration of a strong acid with a weak base.
c. Explain why different indicators change color over different pH ranges.
d. It is always advisable to use dilute solutions while performing experiments in
volumetric analysis? Give a reason.
e. White precipitates are formed when Ca2+, Al3+ and Zn2+ all react separately with NaOH
solution. How will you detect which basic radical is present?
f. How Fe2+ can be distinguished from Fe3+ chemically?
g. Why Ca2+ does not give precipitate with aqueous ammonia?
h. How will you find out the concentration of acetic acid in vinegar solution?
i. What precautions you need to observe while diluting a concentrated acid?
j. Why does an aqueous solution of Na2CO3 behave like a base?
k. If an aqueous solution of NaOH is kept in an open container, what changes do you
expect to take place with the passage of time?

DESCRIPTIVE QUESTIONS
Q.3 Describe common types of the Chemistry lab hazards with two examples in each
case.
Q.4 What are common accidents in the Chemistry lab? How they are managed in
first aid treatment.
Q.5 How the following acid radicals are indicated and confirmed in salt analysis:
i) CO32- ii) Cl- iii) NO3- iv) SO42-
Q.6 How the following basic radicals are indicated and confirmed in salt analysis:
i) Cu2+ ii) Al3+ iii) Fe3+ iv) Zn2+

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