CHEMISTRY

SECTION
 ATOMS, MOLECULES AND
STOICHIOMETRY

Relative masses of atoms you need to be able to distinguish between

There are more than 100 chemical elements, terms that relate to the masses of elements and
and each element is made up of atoms. The compounds.
atoms of different elements differ in size, and Relative atomic mass, Ar, is defined as the mass
hence have different masses. of one atom of an element relative to 1/12 of
the mass of an atom of carbon-12, which has a
mass of 12.00 atomic mass units.

Relative isotopic mass is like relative atomic

mass in that it deals with atoms. The difference
is that we are dealing with different forms of
the same element. Isotopes have the same
number of protons, but different numbers of
neutrons. Hence, isotopes of an element have
different masses.

Relative molecular mass, Mr, is defined as the

mass of one molecule of an element or
compound relative to 1/12 of the mass of an
Atoms of hydrogen, helium and carbon
atom of carbon-12, which has a mass of 12.00
You can also see that the atoms are made up atomic mass units.
of different sorts and numbers of particles.
Relative formula mass is used for substances
There is more about this in the section on
that do not contain molecules, such as sodium
atomic structure. For now you should be able to
chloride, NaCl, and is the sum of all the relative
identify:
atomic masses of the atoms present in the
● two types of particle in the nucleus, which is formula of the substance.
in the middle of the atom. The two particles in
It is important to remember that since these
the nucleus are protons and neutrons. Both
are all relative masses, they have no units.
have the same mass but a proton has a single
positive charge and a neutron has no charge. The mole
● another type of particle that circles the Individual atoms cannot be picked up or
nucleus. These particles are called electrons. An weighed, so we need to find a way to compare
electron has almost no mass, but carries a atomic masses. One way is to find the mass of
single negative charge the same number of atoms of different types.
Even so, the mass of an atom is so small that we
need a huge number of atoms of each element
to weigh. This number is called the Avogadro
constant. It is equal to 6.02 × 1023 atoms and is
also referred to as one mole. You may wonder
why such a strange number is used. It is the When heated in an inert solvent, tin metal
number of atoms of a substance that make up reacts with iodine to form a single orange-red
the relative atomic mass, Ar, in grams. The mass solid compound. In an experiment, a student
is measured relative to one-twelfth of the mass used 5.00g of tin metal in this reaction. After
of a carbon atom, 12C. filtering and drying, the mass of crystals of the
orange compound was 26.3g. Using the data,
Mole calculations work out the formula of the orange compound.
You should be able to work out how many Answer
moles a given mass of an element or compound First you need to calculate how much iodine
represents. In order to do that you need to was used in the reaction. Do this by subtracting
know the relative atomic mass, Ar, of the the mass of tin from the final mass of the
element (or elements) present. You can get this compound:
information from the periodic table.

The abbreviation for mole is ‘mol’. mass of iodine used = 26.3g - 5.00g = 21.3g

Empirical and molecular formulae Next, convert the masses of tin and iodine into
The empirical formula of a compound is its the number of moles of each. Do this by
simplest formula. It shows the ratio of the dividing each mass by the relevant atomic mass:
number of atoms of different elements in a
compound. You need to know how to use the moles of tin = 5.00/119 = 0.0420mol
composition by mass of a compound to find its moles of iodine = 21.3/127 = 0.168mol
empirical formula:
● divide the mass (or percentage mass) of each As you can see, the ratio of the number of
element by its Ar moles shows that there are four times as many
● use the data to calculate the simplest whole moles of iodine as there are tin in the
number ratio of atoms compound. Therefore, the formula of the
orange-red crystals is SnI4.
By contrast, the molecular formula of a
compound shows the actual number of atoms Volumes of gases reacting or produced
of each element present in the compound. The Not all chemical reactions involve solids. For
molecular formula is always a multiple of the those reactions in which gases are involved it is
empirical formula. more convenient to measure volumes than
masses. We need a way of linking the volume of
Calculations using equations and the a gas to the number of particles it contains — in
mole other words a way to convert volume to moles.
There are three main types of calculation you In the early nineteenth century, Avogadro
might be expected to perform of which in each stated that equal volumes of gases at the same
of these you will need to use balanced chemical temperature and pressure contain equal
equations and the mole concept for quantities numbers of molecules. We now know that one
of chemical compounds: mole of a gas occupies 24dm3 at room
temperature (25°C) and a pressure of 101kPa
Reacting masses (from formulae and (1atm), or 22.4dm3 at standard temperature
equations) (273 K) and the same pressure (s.t.p.).
Example
 This means that if we measure the volume of
gas in dm3 in a reaction at room temperature
and pressure, it can be converted directly to the
Volumes and concentrations of solutions of
number of moles present simply by dividing by chemicals reacting
24. The basic principles of the calculations are
the same as those covered already, the only
The easiest way to see how this method complication being that the reactants are in
works is to look at an example. Take the solution. This means that instead of dealing
reaction between hydrogen and chlorine to with masses, we are dealing with volumes of
form hydrogen chloride: solution of known molarity.

Another way of dealing with this is to see how

many moles of substance are dissolved in 1dm3
It would not be easy to measure the reacting of solution. This is known as the molar
masses of the two gases. We could, however, concentration. Do not confuse this with
measure their volumes. When this is done, we concentration, which is the mass of substance
find that there is no overall change in volume dissolved in 1dm3.
during the reaction. This is because there are
two moles of gas on the left-hand side of the Think about a 0.1moldm-3 solution of sodium
equation and two new moles of gas on the hydroxide. The mass of 1mole of sodium
right-hand side. hydroxide is (23 + 16 + 1) or 40g. So a
0.1moldm-3 solution contains 0.1mol (40 × 0.1 =
Some reactions produce gases as well as 4.0g) per dm3 of solution.
liquids, and in others gases react with liquids to
form solids, and so on. In these cases, we can If you know the molar concentration of a
use the above method combined with the solution and the volume that reacts with a
method of the first calculation. known volume of a solution containing another
reactant, you can calculate the molar
For example, 2.0g of magnesium dissolves in concentration of the second solution using the
an excess of dilute hydrochloric acid to produce equation for the reaction.
hydrogen:
Example
In a titration between dilute sulfuric acid and
0.1 molar sodium hydroxide, 21.70cm3 of the
The equation shows that for every mole of sodium hydroxide was needed to neutralise
magnesium used, 1 mole of hydrogen gas is 25.00 cm3 of the dilute sulfuric acid. Knowing
formed. the equation for the reaction, we can calculate
Since 2.0g of magnesium is 2.0/24.3 moles, the molar concentration of the acid in moldm-3:
this means that 2.0/24.3 moles of hydrogen gas
should be formed.

Each mole of hydrogen occupies 24dm3 at

room temperature and pressure:
Answer
volume of hydrogen produced = (2.0/24.3) × From the equation you can see that 1 mole of
24dm3 = 1.98dm3 sulfuric acid requires 2 moles of sodium
hydroxide for complete reaction.
number of moles of sodium hydroxide used =
(21.70× 0.1)/1000 7. In the direct reaction of silicon with Cl2 the
This would neutralise (21.70 × 0.1)/ (1000 × 2) yield of SiCl4 is 50. %. How many grams of
moles of sulfuric acid silicon must be reacted with excess chlorine in
This number of moles is contained in 25.00cm3 order to obtain 17 g SiCl4?
sulfuric acid. A. 1.4 g B. 2.8 g C. 5.6 g D. 17 g
To get the number of moles in 1dm3, multiply E. 28 g
this number by 1000/25.00
This gives (21.70 × 0.1 × 1000)/ (1000 × 2 × 8. In the reaction of Fe3O4 with carbon to form
25.00) = 0.0434moldm-3 carbon dioxide and iron, the number of moles
of carbon required to convert 23 g of Fe3O4 to
REVIEW QUESTIONS products is
1. What is the mass of one mole of A. 0.05 B. 0.1 c. 0.2 D. 0.3 E.
acetylsalicylic acid (aspirin), C9H8O4? 0.4
A. 29 g B. 108 g C. 196 g D. 180. g
E. none of the above 9. A 20.0 mL sample of an element with a
density of 3.0 g/mL contains 4 x 1023 atoms.
2. Determine the number of moles of aluminum What is the atomic weight of this element?
in 2.154 x 10-1 kg of Al. A. 300 B. 40 C. 60 D. 90 E. none
a. 5816 mol b. 7.984 mol c. 6.02 x of the above
1023 mol d. 4.801 mol e. 8.783 mol
3. How many grams of zinc are there in 22.7 g of 10. How many moles of oxygen gas will react
ZnCl2? with 12.4 mol aluminum?
A. 0.35 g B. 0.17 g C. 10.9 g D. Equation: 4Al + 3O2 → 2Al2O3
1476 g E. 0.32 g A. 0.24 mol B. 0.42 mol C. 4.8 mol
D. 9.3 mol E. 16.8 mol
4. A compound with a composition of 87.5 % N
and 12.5 % H was recently discovered. What is
the empirical formula for this compound?
A. NH2 B. N2H3 C. NH D. N2H2 E.
N2H

5. This equation is unbalanced: PCl3 + H2O →

H3PO3 + HCl When it is correctly balanced, the
coefficients are, respectively
a. 1,3,1,1 b. 1,1,1,3 c. 1,3,1,3 d.
2,3,2,3 e. none of the above

6. Given 6 mol of each reactant, which one

would be limiting in the following reaction?
4Au + 8NaCN + O2 + 2H2O → 4NaAu(CN)2 +
4NaOH
A. Au B. NaCN C. O2 D. H2O E.
There is no limiting reactant.
 ATOMIC STRUCTURE AND You might be surprised to see sodium
as an anion, Na-, but it is theoretically possible
PERIODIC TRENDS (though very unlikely!).

Table below shows another way in

Subatomic Particles And Their Properties which the numbers of subatomic particles can
Atoms are made up of three different vary.
types of particle — protons, neutrons and
electrons. You should remember that only the
protons and neutrons have significant mass,
and that the proton carries a single positive
charge while the electron carries a single
negative charge. You also need to remember
that protons and neutrons are found in the In this case, it is the number of
nucleus of the atom and that electrons neutrons that changes while the element stays
surround the nucleus. the same. These forms of an element are called
Look at the numbers of subatomic isotopes. In Table 2.2, the three are all isotopes
particles in the three particles shown in Table of magnesium.
below. What is the major difference between The standard way of writing these
these three species?
particles in ‘shorthand’ form is MPXY.

In this form the element symbol is X, M

is the nucleon or mass number (the number of
protons plus neutrons in the nucleus), P is the
proton or atomic number (the number of
protons in the nucleus) and Y is the charge (if
The difference is in the number of any) on the particle.
electrons each particle possesses, and hence
the overall charge on the species. Since A has Arrangement Of Electrons In Atoms
one more proton than electron, it has a single As the number of protons in the
positive charge. In B the numbers of protons nucleus increases, the mass of an atom of the
and electrons are the same so it is uncharged element increases. After hydrogen, this increase
(neutral). In C there is one more electron than in mass is also due to the neutrons in the
proton, so it has a single negative charge. nucleus. The addition of electrons to form new
Notice that since all species have the same atoms is not quite so straightforward because
number of protons (proton number), they are they go into different orbitals — regions in
all forms of the same element, in this case space that can hold a certain number of
sodium. The two charged species are called electrons, and which have different shapes. The
ions: electrons also exist in different energy levels
●● a positive ion is called a cation (sometimes called shells) depending on how
●● a negative ion is called an anion close to, or far away from, the nucleus they are.

The number of protons in the nucleus

determines what the element is. However, it is
the arrangement of electrons that determines
the chemistry of an element and how it forms Groups Of The Periodic Table And Their
bonds with other elements. So, for example, Characteristics
metal atoms tend to lose electrons forming We will use the electron configurations
positive ions, and non-metal atoms tend to of the atoms to predict their chemical
accept electrons forming negative ions.As the properties, including their reactivity and
number of protons increases, the electron bonding patterns with other atoms.
energy levels fill up in the following sequence:

Sequence of filling orbitals with

electrons

Figure above illustrates some key points

in the arrangement of electrons in atoms. These
are things you should remember:
● The electrons are arranged in energy levels
(or shells) from level 1, closest to the nucleus.
On moving outwards from the nucleus, the
shells gradually increase in energy.
● Most energy levels (except the first) contain
sub-levels (or sub-shells) denoted by s, p and d.
● Different sub-levels contain different
numbers of orbitals, with each orbital holding a
maximum of two electrons.
● When filling up the energy levels in an atom,
electrons go into the lowest energy level first.
● In sub-levels containing more than one
orbital, each of the orbitals is filled singly before
any are doubly-filled.
● If you study Figure 2.1 there is one strange
entry — the 4s-orbital has lower energy than Recall that each horizontal row in the
the 3d-orbital. periodic table is called a period, and each
vertical column is called a group (or family).
Within any group in the periodic table, all of the
elements have the same number of electrons in
their outermost shell. For instance, the
elements in Group II all have two electrons in obtain a stable octet, generally as an M+ or M2+
their outermost shell. Electrons in an atom’s cation.
outermost shell are called valence electrons, Similarly, the halogens (ns2np5) require
and it’s the valence electrons that are primarily only a single electron to achieve a stable octet.
responsible for an atom’s properties and To achieve this state in their elemental form,
chemical behavior. halogens naturally exist as diatomic molecules
Some groups (families) have special (e.g., F2) where one electron from each atom is
names. shared in a covalent bond. When combined
with other elements, the halogens behave as
powerful oxidizing agents (that is, gain
electrons); they can become stable either as X−
anions or by sharing electrons with other
nonmetals.
Reactions between elements on
opposite sides of the periodic table can be quite
violent. This occurs due to the great degree of
stability gained for both elements when the
valence electrons are transferred from the
metal to the nonmetal. The relative reactivities
within these and all other groups can be further
explained by the periodic trends detailed in the
The valence-shell electron configuration next section.
determines the chemical reactivity of each
group in the table. For example, in the noble
gas family each element has eight electrons in
its outermost shell (ns2np6). Such a closed-shell
(fully-filled valence shell) configuration is called
an octet and results in great stability (and
therefore low reactivity) for an atom. For this
reason, noble gases do not generally undergo
chemical reactions, so most group VIII elements
are inert. Helium is inert as well, but has a Summary of periodic trends
closed shell with a stable duet (1s2) of electrons. Shielding
Other elements experience similar
Each filled shell between the nucleus
increases in stability upon reaching this stable
and the valence electrons shields— or
octet electron configuration, and most chemical
“protects”—the valence electrons from the full
reactions can be regarded as the quest for
effect of the positively charged protons in the
atoms to achieve such closed-shell stability. The
nucleus. This is called nuclear shielding or the
alkali metals and alkaline earth metals, for
shielding effect. As far as the valence electrons
instance, possess one (ns1) or two (ns2)
are concerned, the electrical pull by the protons
electrons in their valence shells, respectively,
in the nucleus is reduced by the negative
and behave as reducing agents (i.e., lose
charges of the electrons in the filled shells in
valence electrons) in redox reactions in order to
between; the result is an effective reduction in
the positive elementary charge, from Z to a
smaller amount denoted by Zeff (for effective configuration will always be very large. (For
nuclear charge). example, the ionization energy of neon is 4
times greater than that of lithium.) The second
Atomic And Ionic Radius ionization energy (IE2) of an atom, X, is the
With progression across any period in energy required to remove the least tightly
the table, the number of protons increases, and bound electron from the cation X+. Note that IE2
hence their total pull on the outermost will always be greater than IE1.
electronsincreases, too. New shells are initiated
only at the beginning of a period. So, as we go Electron Affinity
across a period, electrons are being added, but The energy associated with the addition
new shells are not; therefore, the valence of an electron to an isolated atom is known as
electrons are more and more tightly bound to the atom’s electron affinity (often abbreviated
the atom because they feel a greater effective EA). If energy is released when the electron is
nuclear charge. Therefore, as we move from left added, the usual convention is to say that the
to right across a period, atomic radius electron affinity is negative; if energy is
decreases. required in order to add the electron, the
electron affinity is positive. The halogens have
However, with progression down a
large negative electron affinity values, since the
group, as new shells are added with each
addition of an electron would give them the
period, the valence electrons experience
much desired octet configuration. So they
increased shielding. The valence electrons are
readily accept an electron to become an anion;
less tightly bound since they feel a smaller
the increase in stability causes energy to be
effective nuclear charge. Therefore, as we go
released. On the other hand, the noble gases
down a group, atomic radius increases due to
and alkaline earth metals have positive electron
the increased shielding.
affinities, because the added electron begins to
If we form an ion, the radius will fill a new level or sublevel and destabilizes the
decrease as electrons are removed (because the electron configuration. Therefore, anions of
ones that are left are drawn in more closely to these atoms are unstable. Electron affinities
the nucleus), and the radius will increase as typically become more negative as we move to
electrons are added. So, in terms of radius, we the right across a row or up a group (noble
have X+ < X < X−; that is, cation radius < neutral- gases exempted), but there are anomalies in
atom radius < anion radius. this trend.

Ionization Energy Electronegativity

Because the atom’s positively charged Electronegativity is a measure of an
nucleus is attracted to the electrons in the atom’s ability to pull electrons to itself when it
atom, it takes energy to remove an electron. forms a covalent bond; the greater this
The amount of energy necessary to remove the tendency to attract electrons, the greater the
least tightly bound electron from an isolated atom’s electronegativity. Electronegativity
atom is called the atom’s (first) ionization generally behaves as does ionization energy;
energy (often abbreviated IE or IE1). As we that is, as we move from left to right across a
move from left to right across a period, or up a period, electronegativity increases. As we go
group, the ionization energy increases since the down a group, electronegativity decreases. You
valence electrons are more tightly bound. The should know the order of electronegativity for
ionization energy of any atom with a noble- gas the nine most electronegative elements:
 F > O > N > Cl > Br > I > S > C ≈ H D. The yz plane divides the electron
probability distribution into two identical mirror
Acidity image halves.
Acidity is a measure of how well a E. The nucleus is located at a node.
compound donates protons, accepts electrons,
or lowers pH in a chemical system. A binary acid 4. The electronic configuration of the element
has the structure HX, and can dissociate in whose atomic number is 26 is:
water in the following manner: HX → H+ + X−. A. 1s2 2s2 2p6 3s2 3p6 4s0 3d8
Stronger acids have resulting X− anions that are B. 1s2 2s2 2p6 3s2 3p6 3d6 4s2
likely to separate from H+ because they are C. 1s2 2s2 2p6 3s2 3p6 4s2 3d6
stable once they do. With respect to the D. 1s2 2s2 2p6 3s2 3p6 4s2 3d4 4p2
horizontal periodic trend for acidity, the more E. none of the above
electronegative the element is (X−) the more
stable the anion will be. Therefore acidity 5. Which of the following has the largest radius?
increases from left to right across a period. A. F B. N C. C D. O E. Ne
However, the vertical trend for acidity depends
on the size of the anion. The larger the anion, 6. Which of the following elements has the
the more the negative charge can be largest ionization energy?
delocalized and stabilized. Therefore, acidity A. Na B. Ne C. F D. K E. Rb
increases down a group or family in the periodic
table. 7. Which of the following has the greatest
electron affinity (most negative value)?
REVIEW QUESTIONS
A. Cl B. K C. He D. Na E. Rb
1. What value or values of ml are allowable for
an orbital with l = 2?
8. Which of the following species is not
A. 0 B. 2 C. -1 D. none of the
isolectronic with any of the others?
above E. all of the above
A. V3+ B. Ca2+ C. Ar D. Cl- E. S2-
2. According to Bohr Theory, which of the
9. In Bohr's model of the hydrogen atom, the
following transitions in the hydrogen atom will
radius of an orbit
give rise to the least energetic photon?
A. is proportional to n2
Use the equation: En = (-2.18 x 10-18 J)(1/n2)
B. is smallest for the highest energy
A. n = 5 to n = 3 B. n = 6 to n = 1 C.
state.
n = 4 to n = 3 D. n = 5 to n = 4 E. n = 6 to n =
C. increases when a photon of light is
5
emitted from an excited atom.
D. can have any value that is larger than
3. Consider a 3dxz orbital. Which of the
the ground-state radius.
following statements is incorrect?
E. none of the above
A. The xz plane is a nodal surface.
B. The xz plane divides the electron
10. Which of the following atoms is not a one-
probability distribution into two identical
electron system?
mirror-image halves.
A. H B. He+ C. Li2+ D. Be2+ E. O7+
C. The xy plane divides the electron
probability distribution into two identical
mirror-image halves.
11. Which of the following statements about
periodic properties is incorrect?
A. Both electron affinity and ionization
energy decrease down a group.
B. Atomic size increases to the right
across a period.
C. Ionization energy increases to the
right across a period.
D. Atomic size increases down a group.
E. Electron affinity increases to the right
across a period.
BONDING AND INTERMOLECULAR repulsive forces between ions of the same
charge, but because these are longer range they
FORCES are weaker.

Chemical reactions depend on the

breaking of existing bonds and the formation of
new bonds. In order to understand this process,
you need to be aware of the different types of
bonds and forces between atoms and
molecules.

Ionic (Electrovalent) Bonding

Ions are formed when atoms react and
lose or gain electrons. Metals usually lose
electrons to form positively charged cations — Covalent And Coordinate (Dative)
for example sodium forms Na+. Hydrogen also Bonding
loses its electron to form H+; the ammonium The major difference between ionic
ion, NH4+, is another example of a non-metallic (electrovalent) and covalent bonding is that in
cation. ionic (electrovalent) bonding electrons are
transferred from one element to another to
Non-metallic elements gain electrons to create charged ions, while in covalent bonding
form negatively charged anions — for example, the electrons are shared between atoms in
chlorine forms Cl-. Groups of atoms, such as the pairs.
nitrate ion, NO3-, also carry negative charges.
It is important to remember that the
In forming cations or anions, the electrons do not ‘circle around the nucleus’, but
elements tend to lose or gain outer electrons to exist in a volume of space surrounding the
attain the electron configuration of the nearest nucleus where there is a high probability of
noble gas, since this is very stable. We can see finding the electron. These are known as
this when sodium reacts with chlorine to form orbitals. A covalent bond is formed due to the
sodium chloride: overlap of orbitals containing electrons and the
attraction of these bonding electrons to the
nuclei of both atoms involved.

It is not necessary to have atoms of

Ionic crystals
different elements to form covalent bonds, so it
In the solid state, cations and anions
is possible for an element to form molecules
come together to form ionic crystals. These
that have a covalent bond between the atoms,
consist of a giant three-dimensional lattice of
e.g. chlorine, Cl2.
ions. The structure of these crystals depends on
the relative sizes of the anion and cation, and
on the stoichiometry of the compound
concerned. The three-dimensional structure
within the crystal is held together by the net
attractive forces between the oppositely
charged ions. There are also longer-range
 Boron trichloride

Covalent bonding in chlorine Coordinate or dative covalent bonds are

formed when both electrons in a pair come
Dot-and-cross diagrams from the same atom, for example in NH4+. Once
These are diagrams that represent the formed, the bond is not distinguishable from
movement of electrons in the formation of both the other covalent bonds in the ion.
electrovalent and covalent bonds, with the
electrons from one atom represented by ‘dots’
and those from the other atom by ‘crosses’. The
electrons are, of course, identical, but this
system helps to visualise what is happening
when the bond is formed.

In an electrovalent bond, one or more

electrons are transferred from one element
(usually a metal) to another element (usually a
non-metal). The transfer in the formation of
magnesium oxide is shown in Figure below.

The ammonium ion

There are plenty of other examples of

this type of covalent bonding — for example, in
carbon monoxide, CO, and in the nitrate ion,
NO3-, and particularly in the formation of
transition metal complexes.

It is possible to have multiple covalent

Electron transfer in the formation of bonds, depending on the number of pairs of
magnesium oxide electrons involved. This can occur in simple
The bonded atoms in a covalent bond molecules such as oxygen, O2, but is particularly
usually have a ‘share’ of an octet of electrons important in carbon compounds such as
associated with each atom, but this is not ethene, C2H4.
always the case. For example in boron
trichloride, BCl3, there are only six electrons
associated with the boron atom.
 (a) Multiple covalent bonding in (a)
oxygen and (b) ethene

Simple molecular shapes

Unlike ionic (electrovalent) bonds that
have no particular direction, covalent bonds are
directional. This means that covalently bonded
molecules have distinctive shapes depending on
the number of bonds, since the pairs of
electrons in the bonds repel any other pairs.
Figure below shows the basic shapes that
molecules containing up to four electron pairs
can adopt. Shapes of molecules

In some circumstances more than four

pairs of electrons can be involved, as in the case
of sulfur hexafluoride, SF6. The repulsion effect
still applies. In this case the molecule is
octahedral.

In addition, any non-bonded pairs of

electrons will repel bonded pairs, but occupy
rather more space. This means that the bond
angles are widened. We can see this effect if we
compare three molecules, each with four pairs
of electrons — methane, CH4, ammonia, NH3,
and water, H2O. The normal tetrahedral angle is
109.5°, but ammonia has a lone pair of
electrons that squeezes the H N H bond angle to
107°. In water, the two lone pairs of electrons
present squeeze the H-O-H bond angle even = 350kJmol-1; E(C=C) = 610kJmol-1 and E(C C) =
more, reducing it to 104.5°. This is shown in 840kJmol-1.
Figure below.
Bond length is defined as the distance
between the middle of the atoms at either end
of the bond. The length of a bond depends on a
number of factors, particularly the number of
pairs of electrons making up the bond. So for
the three carbon bonds described above, the
Bond angles in methane, ammonia and bond lengths are C-C, 154 pm; C=C, 134 pm and
C C, 120 pm.
water
Since most covalent bonds are between
Giant molecular structures
different atoms, and different nuclei have a
As well as forming simple molecules like
different attraction for the electrons, it follows
those shown on the page opposite, it is possible
that the electrons in a covalent bond are pulled
to form giant molecular structures. In this
closer to one atom than the other. The degree
syllabus, these are confined to different
of attraction depends on the nature of the two
structural forms of carbon (diamond and
atoms involved. This effect of unequal sharing
graphite) and silicon dioxide, which is similar to
of electrons is called bond polarity. The
diamond.
measure of this tendency to attract a bonding
Bond energies, bond lengths and bond pair of electrons is called electronegativity. You
polarities need to remember that:
When two atoms join to form a ● electronegativity increases from left to right
covalent bond the reaction is exothermic — across a period
energy is given out. It therefore follows that to ● electronegativity decreases down a group
break that covalent bond energy must be ● small atoms with many protons in the nucleus
supplied. The bond energy is defined as the have high electronegativity
average standard enthalpy change for the ● the greater the difference in electronegativity
breaking of one mole of bonds in a gaseous of the two atoms, the more polar the bond will
molecule to form gaseous atoms: be

Orbital overlap: σ-bonds and π-bonds

At the start of the section on covalent
It follows from this that bond energy is bonds we talked about them being formed by
an indication of the strength of the forces the overlap of electron orbitals on each atom.
holding the atoms together in a covalent Most covalent bonds are found in compounds
molecule. Bond energies can vary from around of carbon, and it is important to understand
150kJmol-1 for molecules with weak bonds, how such bonds are formed.
such as I-I, to 350–550kJmol-1 for stronger In carbon, the 2s- and 2p-orbitals are
bonds, such as C-C and O-H, to around quite close in energy. This means that it is
1000kJmol-1 for very strong bonds such as N-N. possible to promote one of the 2s-electrons to
Bond energy increases with the number of the empty 2p-orbital. The energy required for
electron pairs making up the bond. Thus, E(C-C) this promotion is more than compensated for
by the energy released when four bonds are
formed (compared with the two bonds that forming a π-bond. The bonding in ethene can be
could have been formed from the two 2p- seen in Figure below.
orbitals that each contained a single electron).
This can be seen in below.

Bonding in ethane

A similar bonding pattern occurs in

Energy benefit in forming four carbon – molecules of benzene, C6H6. However, in
hydrogen bonds benzene the carbon atoms are arranged in a
The four electrons form four identical hexagonal ring. The 2p-orbitals overlap above
orbitals that have some s and some p and below the ring forming circular molecular
characteristics. These are known as sp3 hybrid orbitals, as shown in Figure below. The
orbitals. In forming methane, CH4, they overlap electrons are said to be delocalised since they
with the s-orbitals of hydrogen atoms. Bonds no longer belong to individual carbon atoms.
formed from the overlap of orbitals with some s
character are called sigma bonds (σ-bonds).
Bonds formed by the overlap of p-orbitals are
called pi-bonds (π-bonds).

There are two other ways in which the

orbitals on carbon can be hybridised. First the s-
orbital may be hybridised with two of the p-
orbitals to form three sp2-orbitals leaving the
remaining 2p-orbital unchanged. The three sp2-
orbitals lie in a plane 120° apart, with the 2p- Bonding in benzene
orbital at right angles to this. This is the type of
hybrid orbital formed by the carbon atoms in Intermolecular Forces
ethene and benzene. Van der Waals forces
Look at the structure of ethene. One These are the weakest of the forces.
pair of sp2-orbitals overlap forming a σ-bond. They act between all particles whether they are
This brings the 2p-orbitals on the two carbons polar or non-polar. They exist due to the
close enough together for them to overlap movement of electrons that in turn causes
instantaneous dipoles. These induce dipoles in Hydrogen bonding in water
neighbouring molecules.
Metallic Bonding
Permanent dipole–dipole interactions Metals have distinctive properties,
These occur between polar covalent many of which are based on the fact that
molecules, i.e. those containing different metals possess a regular lattice of atoms, in
elements. An example is the forces between the much the same way as an ionic (electrovalent)
dipoles in a molecule such as H–Cl crystal. The main difference is that all of the
atoms in a metallic lattice are the same and the
outer electrons are not held by the atoms but
are delocalised throughout the lattice. It is
these mobile electrons that give metals their
electrical conductivity.
Dipole–dipole interactions in hydrogen
chloride

Hydrogen bonds
This is a particular sort of comparatively
strong dipole–dipole interaction between
molecules containing hydrogen with nitrogen,
oxygen or fluorine. These bonds result from the
lone pairs of electrons on the nitrogen, oxygen
or fluorine atoms, so the hydrogen atom can be Metallic bonding
considered as acting as a ‘bridge’ between two
Bonding And Physical Properties
electronegative atoms.
The type of bonding in a substance
This form of bonding can have affects its physical properties. Ionic
significant effects on the physical properties of (electrovalent) compounds, which are formed
the compound concerned. For example, based of giant lattices of oppositely charged ions, tend
on its molecular mass, water would be expected to have high melting and boiling points; they
to exist as a gas at room temperature. The fact usually dissolve in water and they conduct
that it exists as a liquid at room temperature is electricity when molten. Covalently bonded
due to the hydrogen bonding present. As a compounds tend to be gases, liquids or low
result of hydrogen bonding, water possesses melting point solids; they dissolve in covalent
surface tension, which enables some insects to solvents and are electrical insulators. Metals
walk on its surface. Finally, the fact that ice is have a giant lattice structure with a ‘sea’ of
less dense than liquid water and floats on the mobile electrons. In general, metals have high
surface is also a result of hydrogen bonding. melting points, can be bent and shaped, andare
good electrical conductors.

REVIEW QUESTIONS
1. Which one of the following is most likely to
be an ionic compound?
A. HNF2 B. H2CO C. N2H4 D.
CaCl2 E. CH3Cl
 E. an sp2 and sp2 overlapping and 2p
2. In which of the following processes does the orbitals overlapping
enthalpy change (ΔH) directly represent the
magnitude of the lattice energy of KCl(s)? 8. Which of the following molecules has sp3
A. Cl2(g) + 2K(s) → 2KCl(s) hybridization and a dipole moment?
B. KCl(s) → K+(aq) + Cl-(aq) A. SiH4 B. BF3 C. NH3 D. BrF3 E.
C. KCl(s) → K+(g) + Cl-(g) PCl5
D. KCl(s) → K(s) + Cl-(g)
E. KCl(s) → K(s) + Cl(g) 9. In the molecular orbital description of
bonding in benzene (C6H6), how many
3. Order the following by increasing bond electrons occupy delocalized MOs?
strength: N≡N, N=N, N-N A. 2 B. 3 C. 4 D. 5 E. 6
A. N≡N, N=N, N-N B. N≡N, N-N, N=N
C. N-N, N=N, N≡N 10. In which of the following species is the octet
D. N=N, N-N, N≡N E. N=N, N≡N, N-N rule violated by the central atom?
A. CH4 B. SF4 C. PCl4+ D. SO2 E.
4. Which of the following compounds has the NH3
greatest bond polarity?
A. PH3 B. NH3 C. HF D. H2S E. 11. The number of electron dots in the Lewis
CH4 symbol for an element equals the
A. number of outermost p electrons.
5. Which of the following is not planar? B. number of electrons needed to fill
A. BCl3 B. ClF3 C. PCl3 D. XeF4 E. the outermost p orbital.
C2H4 C. period number that contains the
element.
6. Use VSEPR theory to predict the ideal bond D. number of outermost s and p
angles around the two carbon atoms in electrons.
acetaldehyde, CH3CHO. (The first carbon has E. number of outermost s electrons.
single bonds to three H atoms and one C atom;
the second carbon has single bonds to C and H,
and a double bond to O.)
A. 109°, 109° B. 109°, 120° C. 120°,
109°
D. 120°, 90° E. 105°, 105°

7. In a carbon-carbon triple bond, what is the

nature of the bonding between the carbons?
A. two 2s orbitals overlapping
B. two 2p orbitals overlapping
C. two sp orbitals overlapping, two 2py
overlapping and two 2pz overlapping d.
an sp and sp2 overlapping and 2p
orbitals overlapping
 CHEMICAL ENERGETICS ● the temperature is specified (usually 298K,
25°C)

Almost all chemical reactions are Enthalpy Changes

accompanied by energy changes as bonds are In textbooks you will see references
broken and/or formed. Usually the energy made both to energy changes and to enthalpy
changes involve heat, but they can also involve changes, and it is important to understand the
sound, light or even electrical energy. We are difference in the way these are used in
most familiar with reactions that give out heat questions and in the syllabus. Enthalpy changes
— a test tube gets warmer or a fuel is burned. always refer to particular sets of conditions,
These are called exothermic reactions. A these are usually referred to as standard
smaller number of reactions take in energy enthalpy changes, which means they refer to
overall, and these are known as endothermic the heat absorbed or given out at 298K and
reactions. standard pressure (usually 1 atmosphere or
100kPa, although some textbooks refer to 1
atmosphere as 101kPa). The examples that
follow outline the particular enthalpy changes
you need to know about.
The sorts of reactions for which you
may need to measure or calculate the enthalpy
change are as follows:
● Formation — the enthalpy change when
Energy change in an exothermic and an 1mole of substance is formed from its elements
endothermic reaction under standard conditions, for example:

The vertical (y) axes in Figure above

represent the enthalpy (see below) of the ● Combustion — the enthalpy change when
compounds. So you can see that in an 1mole of substance is completely burned in
exothermic reaction the enthalpy change is in a excess oxygen under standard conditions, for
negative direction. This is worth remembering example:
since exothermic reactions always show a
negative enthalpy change. It follows that ● Hydration — the enthalpy change when
endothermic reactions show a positive enthalpy 1mole of gaseous ions become hydrated under
change, and this is borne out in the Figure 5.1. standard conditions, for example:
Enthalpy changes are measured in kJmol-1.

In order to make sense of what takes ● Solution — the enthalpy change when 1mole
place in a chemical reaction, we need to of substance is completely dissolved, under
consider standard conditions. Using standard standard conditions, in enough solvent so that
conditions means that the results of no further heat change takes place on adding
measurements are reproducible. Standard more solvent, for example:
conditions are:
● all reagents and products are in their most ● Neutralisation — the enthalpy change when
stable state an acid is neutralised by an alkali to produce
● the pressure is 1 atmosphere 1mole of water under standard conditions. This
can also be thought of as the enthalpy change
when 1mole of hydrogen ions reacts with 1mole
of hydroxide ions:

● Atomisation — the enthalpy change for the

formation of 1mole of gaseous Hess’s law
atoms from an element under standard In simple terms, Hess’s law states that
conditions, for example: the enthalpy change for the chemical process X
→ Y is the same whichever route is taken from
X to Y provided that the states of X and Y are
Another enthalpy change you need to the same in all routes. Using standard
understand is bond energy. This was talked enthalpies avoids this problem since the states
about as the energy needed to break a bond, so of X and Y are defined.
it was energy supplied. This means that ∆H is
²This means that when it is difficult to
positive.
measure enthalpy changes experimentally,
The final enthalpy change you need to other data can be used. For example, the
be aware of is lattice energy. You need to enthalpy of reaction can be calculated using
remember that this is the formation of a lattice enthalpies of formation:
from gaseous ions, so energy is released:

The lattice energy depends on a

number of factors since it is effectively a
measurement of the strength of the (usually) A is (sum of the enthalpies of formation of the
ionic (electrovalent) bond between the reactants)
particles. This depends on both the size of the B is (sum of the enthalpies of formation of the
particles and the charges they carry. The size products)
also affects the arrangement of particles in the C is therefore (B - A)
lattice.

You can see how this works in practice,

with the following example.

It can be seen that as the ionic radius of

either ion increases, the lattice energy
decreases. The effect of changing the charge on This shows how the enthalpy change for
one of the ions is shown in Table below. This the combustion of methane, CH4, can be found
shows that the lattice energy increases rapidly using the enthalpies of formation of methane,
as the charge on the ions increases. carbon dioxide and water
 You need to remember something else
important about reactions. Even with strongly
exothermic reactions, such as the burning of
magnesium, the reaction does not happen
immediately magnesium is exposed to air. In
order to start the reaction the magnesium has
to be heated, i.e. it has to be provided with
Reverse calculations to determine the enthalpy energy. This is called the activation energy.
of formation of a compound using enthalpy of
Reactions can be summarised in
combustion data can be performed.
diagrammatic form, as shown in Figure below.
Average bond energies
Hess’s law can also be used to find
approximate values of DHo for a reaction using
average bond energies (sometimes referred to
as mean bond enthalpies). These average bond
energies are determined from bonds in a
variety of molecules. There is a list of those you
are likely to need in the Data Booklet (also to be
found at the end of the syllabus).
The Hess’s law diagram for use with
bond energies is shown below. Activation energy

Some energy changes are more

complicated than others. Take for example the
energy of formation of an ionic (electrovalent)
solid such as sodium chloride. A number of
enthalpy changes are involved in converting the
A is (sum of the bond energies of the
two elements into a solid crystal lattice. These
reactants)
changes can be shown diagrammatically in a
B is (sum of the bond energies of the
Born–Haber cycle, which uses Hess’s law
products)
C is therefore (A - B)

Note that bond energies are always

endothermic, i.e. they are positive.When using
bond energies it is useful to remember the
following:
● Show the reaction using structural
formulae so that you can see all the bonds
present.
● Ignore bonds or groups of bonds that
are unchanged in the reaction.
● Remember to change the sign of the
bond energy for any bonds formed.
 Born–Haber cycle for the enthalpy of a. 3.0 x 103 kJ
formation of sodium chloride b. 36 J
c. 2.5 x 103 kJ
d. 2.5 x 106 kJ
e. 25 kJ

3. Data:
ΔH°f values: CH4(g), -74.8 kJ; CO2(g), -393.5 kJ;
H2O(l), -285.8 kJ.
Using the ΔH°f data above, calculate ΔH°rxn for
the reaction below.
Reaction: CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
A. -604.2 kJ
B. 890.3 kJ
C. -997.7 kJ
D. -890.3 kJ
E. none of the above

4. Data:
2Ba(s) + O2(g) → 2BaO(s) ΔH° = -
1107.0 kJ
Ba(s) + CO2(g) + ½O2(g) → BaCO3(s) ΔH° = -822.5
kJ
Given the data above, calculate ΔH° for the
reaction below.
Reaction: BaCO3(s) → BaO(s) + CO2(g)
REVIEW QUESTIONS A. -1929.5 kJ
1. Data: B. -1376.0 kJ
(1) H2(g) + ½O2(g) → H2O(g) ΔH = -241.8 kJ C. -284.5 kJ
(2) H2(g) + ½O2(g) → H2O(l) ΔH = -285.8 kJ D. 269.0 kJ
On the basis of the above data, which of the E. 537 kJ
following statements is false?
A. Reaction (1) is exothermic. 5. Which of the following is not a state
B. Reaction (2) is the formation reaction function?
for H2O(L). A. ΔE B. ΔH C. q D. P E. V
C. The reverse of reaction (2) is
endothermic. 6. Two solutions (the system), each of 25.0 mL
D. The energy content of H2O(G) is lower volume and at 25.0 °C, are mixed in a beaker. A
than H2O(L). reaction occurs between them, causing the
E. ΔH for the reaction: H2O(L) → H2O(G) is temperature to drop to 20.0 °C. After the
+ 44 kJ/mol. products have equilibrated with the
surroundings, the temperature is again 25.0 °C
2. What is the amount of heat necessary to and the total volume is 50.0 mL. No gases are
raise the temperature of 8.5 kg of water from involved in the reaction. Which one of the
12.5 °C to 84 °C?
following relationships concerning the change
from initial to final states (both at 25.0 °C) is 11. Sodium carbonate can be made by heating
correct? sodium hydrogen carbonate:
A. ΔE = 0 B. ΔH = 0 C. ΔE < 0 D. w 2NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(g)
= 0 E. q = 0 For this reaction, ΔH° = 128.9 kJ and ΔS° = 321
7. Which one of the following processes is J/K. At approximately what temperature will K =
exothermic? 1?
A. H2(l) → H2(g) A. 401.6 K
B. CO2(s) → CO2(g) B. 401.6º C
C. H2O(g) → H2O(l) C. 33.1 K
D. 16CO2(g) + 18H2O(l) → 2C8H18(l) + D. 33.1º C
25O2(g) E. none of the above
E. H2(g) → 2H(g)

8. Predict the signs of ΔH°, ΔS°, and ΔG° for the

vaporization of liquid water at 150°C.
A. ΔH° > 0, ΔS° > 0, ΔG° > 0
B. ΔH° < 0, ΔS° < 0, ΔG° < 0
C. ΔH° > 0, ΔS° < 0, ΔG° > 0
D. ΔH° > 0, ΔS° > 0, ΔG° < 0
E. none of the above

9. Which of the following substances has the

lowest standard molar entropy (S°) at 25°C?
A. CH3OH(l)
B. CO(g)
C. MgO(s)
D. H2O(l)
E. CaCO3(s)

10. When crystalline solid barium hydroxide

octahydrate and crystalline solid ammonium
nitrate are mixed in a beaker at room
temperature, a spontaneous reaction occurs.
The temperature of the beaker contents rapidly
falls to below 0º C. Use this information to
decide whether the reaction is exothermic or
endothermic and what the signs of ΔH and ΔS
are.
A. endothermic; ΔH > 0;Δ S > 0
B. exothermic; ΔH < 0;Δ S > 0
C. endothermic; ΔH < 0;Δ S < 0
D. endothermic; ΔH < 0;Δ S > 0
E. exothermic; ΔH > 0;Δ S < 0
 ELECTROCHEMISTRY
Redox Processes What is the change in oxidation number
The word redox comes from two of sulfur?
familiar words — reduction and oxidation —
and refers to what happens in chemical
reactions when electrons are gained or lost.
When a metal is oxidised, it loses electrons, for
example:
As you can see from the diagram, you
simply measure the distance between the two
oxidation states.In working out oxidation
When magnesium is burned in air, the numbers there are some simple rules:
electrons are picked up by oxygen, reducing it ● Atoms of uncombined elements have an
to the oxide ion: oxidation number of zero.
● Simple ions have an oxidation number equal
to the charge on the ion.
Oxidation and reduction do not only ● In complex ions, the sum of the oxidation
occur with elements — for example, ions such numbers in all the elements present equals the
as iron(II) ions can be oxidised to iron(III) ions: overall charge on the ion.

Electrode Potentials
There are two aspects to
Reduction of one ion to form another electrochemistry; the first, electrolysis, involves
ion can also occur, such as in a manganate(VII) using electricity to bring about chemical
titration: reactions. The second, electrode potentials,
relies on chemical reactions to generate an
electric current. It is important that you learn
two definitions linked to electrode potentials.
You may be given equations and asked
for the change in oxidation state or oxidation Standard electrode potentials
number of one of the elements present. In A standard electrode (redox) potential
these cases, it is often easier to think of is defined as the electrode potential measured
oxidation states/numbers on a line as shown in under standard conditions (temperature 298 K,
the diagram below: 1 atmosphere pressure, 1mole of the redox
participants of the half-reaction) against a
standard hydrogen electrode.

Using this idea, if you place the reduced

and oxidised species at the correct points on
the line, you can see the change in oxidation
number, or the number of electrons lost or
gained.Consider the oxidation of hydrogen
sulfide to form sulfur dioxide:
 A standard hydrogen electrode
Apparatus for determining the standard
Below you can see how the standard cell potential
electrode potential of another electrode can be
The cell potential has a contribution
measured using the hydrogen electrode.
from the anode, which is a measure of its ability
to lose electrons — its oxidation potential. The
cathode has a contribution based on its ability
to gain electrons — its reduction potential. The
cell potential can then be written as:

As with oxidation numbers, to calculate

the overall cell potential it helps to work using a
linear scale from negative to positive:

Measuring a standard electrode potential In the cell shown in Figure above, the oxidation
potential of the zinc anode is +0.76 volts, and
Standard cell potentials the reduction potential of the copper cathode is
A standard cell potential is the potential +0.34 volts.
produced when two standard electrodes are
connected to form a cell such as that in Figure
below.
Care must be taken to change the signs given in
electrode potential tables to reflect what is
happening. These data are given in terms of the
reduction of the ions concerned. When you are
showing a cell, remember to show the reactants
with oxidation occurring on the right and
reduction on the left. This means that in the cell
described above we would write:

because the zinc metal is oxidised and the

copper ions are reduced.

Non-metallic electrodes
Measuring the standard electrode
potential of a non-metallic element presents
different problems from using metals. However,
A cell formed using ions of the same
we have already seen one way of overcoming
element
this in the hydrogen electrode. The cell shown
in Figure below shows how two non-metallic
elements can form a cell.
Predicting reactions
As well as using electrode potentials to
calculate the voltage a particular combination
of electrodes will produce under standard
conditions, electrode potentials can also be
used to predict how likely a given chemical
reaction is to occur.

A cell formed using two non-metallic

elements
In Table above, the half-reactions with a
The same basic technique can be used for ions high negative Eo do not take place readily (think
of the same element in different oxidation of the reactions of the alkali (Group I) metals
states. The set-up can be seen in Figure below. with water). By contrast, those with a high
The electrodes chosen in each case are positive Eo take place spontaneously (think of
platinum, although in the laboratory you may manganate(VII) as an oxidising agent).
have used carbon.
The half-equations can be used to
construct full chemical equations, by making
sure that the numbers of electrons balance and
that the overall cell potential is positive. There
are some key points that help you to get this
right:
● Write the half-equation with the more
negative Eo first.
● Remember that the more positive Eo will be a You have already seen examples of this in the
reduction. chemical industry, at the start of this section.
● Draw anti-clockwise arrows to help predict
Like all chemical reactions, it is possible
the overall reaction.
to calculate quantities of materials used or
produced in such a process. In the case of
For example, consider the reaction electrolysis we know, for example, how many
between Fe2+ ions and chlorine gas. The two electrons are needed to produce one atom of
half-equations are: aluminium:

The quantity of electricity needed to

produce 1 mole of aluminium depends on the
Reversing the first equation and adding gives:
number of electrons needed, the charge on the
electron and the number of atoms. The
magnitude of the charge per mole of electrons
Eo cell is positive. Therefore, when chlorine gas is known as the Faraday constant and is
oxidises iron(II) ions to iron(III) ions, it is generally quoted as 96500C mol-1. This is
reduced to chloride ions. expressed as:
The effects of non-standard conditions
For most of the work you will do with
electrode potentials, you can assume that the where L is the Avogadro constant and e the
conditions are standard, but you do need to charge on the eletron
know the effects of changing the concentration
of the aqueous ion. Example
What mass of copper is produced at the
Think of the half-cell reaction: cathode when 2.40A are passed through a
solution of copper(II) sulfate for 25minutes?

Le Chatelier’s principle predicts that if Answer

the concentration of Mn+(aq) is increased, then First, calculate the number of coulombs of
the equilibrium should move to the right. If this charge passed. Remember that charge equals
were the case, the electrode should become current in amps multiplied by time in seconds:
more positive with respect to the solution. 2.40 × 25 × 60 = 3600C
Hence, the electrode potential should also
become more positive. This also means that the Next, calculate how many moles of electrons
halfcell would become a better oxidising agent. this corresponds to:
Reducing the concentration of Mn+(aq) would (3600/96500) = 3.73 × 10-2mol
have the opposite effect.
Since copper(II) ions have a charge of +2 this
Electrolysis corresponds to:
The converse of using chemical
(3.73 × 10-2/2)mol of copper
reactions to generate electricity is to use
electricity to bring about chemical reactions. Therefore the mass of copper produced is
(3.73 × 10-2 × 63.5)/2 = 1.18g than sodium ions. On the other hand, chlorine is
produced at the anode because chloride ions
For the electrolysis of a solution of
are present in a higher concentration than
sodium sulfate, Na2SO4, or sulfuric acid, H2SO4,
hydroxide ions.
the product at the cathode is hydrogen gas.
Instead of using mass with hydrogen, we can
use the volume as a fraction of the molar
volume of a gas, 24dm3. REVIEW QUESTIONS
1. Which of the following statements is
A value for the Avogadro constant can incorrect?
be determined using electrolysis. This method A. In an electrolytic cell, reduction
requires the measurement of the mass of an occurs at the anode.
element, such as copper, produced in a fixed B. Aluminum metal would form at the
period of time and at a constant known current, cathode during the electrolysis of
to be measured as accurately as possible. molten AlBr3.
Knowing the charge on the copper(II) ion we C. The cathode is labeled "+" in a voltaic
can then use F = Le to determine L, the cell.
Avogadro constant. D. Oxidation occurs at the anode in a
Some exam questions may ask you to predict voltaic cell.
what substances are liberated at a given E. Electrons flow from the anode to the
electrode. To answer this you need to check if cathode in all electrochemical cells.
the electrolysis is taking place in the molten salt
or in aqueous solution, and consider the 2. Consider the following notation for an
electrode potentials and concentrations of the electrochemical cell
ions. Zn/Zn2+ (1M)//Fe2+ (1M), Fe3+ (1M)/Pt
What is the balanced equation for the cell
● If it is a molten salt there can only be one reaction?
element discharged at each electrode. A. Zn(s) + 2Fe3+(aq) → 2Fe2+(aq) + Zn2+(aq)
● If it is an aqueous solution it is possible for B. Zn2+(aq) + 2Fe2+(aq) → Zn(s) + 2Fe3+(aq)
hydrogen to be discharged at the cathode and C. Zn(s) + 2Fe2+(aq) → 2Fe3+(aq) + Zn2+(aq)
oxygen at the anode: D. Zn(s) + Fe3+(aq) → Fe2+(aq) + Zn2+(aq)
E. Zn(s) + Fe2+(aq) → Fe(s) + Zn2+(aq)

3. Consider the following half-reactions and

select the strongest oxidizing agent present:
Sr2+(aq) + 2e- → Sr(s) E° = -2.89 V
In order to decide which ions are discharged, 2+ -
Cr (aq) + 2e → Cr(s) E° = -0.913 V
you need to compare Eo for the half-cell 2+ - (s)
Co (aq) + 2e → Co E° = -0.28 V
reactions above with those of the other ions in
A. Cr2+(aq) B. Sr2+(aq) C. Co2+(aq) D. Sr(s)
solution.
E. Co(s)
Think about the electrolysis of a
concentrated solution of sodium chloride. 4. In an electrolytic cell, how many grams of Cu
Hydrogen is produced at the cathode because could be plated out of a CuSO4 solution at a
hydrogen ions accept electrons more easily
current of 5.00 A for 2.00 min? (F = 96500 O2(g) + 4H+(aq) + 4e- → 2H2O(l)
C/mol) E° = +1.23 V
A. 318 g B. 0.395 g C. Cu2+(aq) + 2e- → Cu(s)
-3
0.329 x 10 g D. 0.198 g E. 5.31 g E° = +0.34 V
SO4 (aq) + 4H+(aq) + 2e- → H2SO3(aq) + H2O(l)
2-

5. A voltaic cell is based on the following two E° = 0.20 V

half-reactions: 2H (aq) + 2e- → H2(g)
+

Ni+2(aq) + 2e- → Ni(s) E° = -0.25 V E° = 0.00 V

+3 -
Cr (aq) + 3e → Cr(s) E° = -0.74 V A. H2, O2, H+ B. Cu, O2, H+ C. Cu,
Sketch the cell and then select the correct H2 D. H2, H2SO3, H2O E. H2SO3, H2O,
statement about it. O2, H+
A. Cr serves as the cathode.
B. The direction of electron flow 8. A constant current was passed through a
through the external wire is from the Ni solution of KAuCl4 between gold electrodes.
to the Cr electrode. Over a period of 20.00 min, the cathode
C. Anions in solution will migrate increased in mass by 2.664 g. What was the
toward the Ni+2/Ni electrode. current in amperes? (F = 96500 C/mol)
D. The net cell reaction is 3Ni+2(aq) + Cathode half-reaction: AuCl4-(aq) + 3e- → Au(s) +
2Cr(s) → 3Ni(s) + 2Cr+3(aq) 4Cl-(aq)
E. E°cell = 0.99 V A. 1.08 A B. 3.26 A C. 2.17
A D. 6.52 A E. 3.48 A
6. Consider the following two electrode
reactions and their standard electrode 9. A voltaic cell is constructed from the
potentials: following half-cells, linked by a KCl salt bridge:
Al+3(aq) + 3e- → Al (s) E° = -1.66 V (a) an Fe electrode in 1.0 M FeCl2 solution
+2 -
Cd (aq) + 2e → Cd(s) E° = -0.40 V (b) a Ni electrode in 1.0 M Ni(NO3)2 solution
Write the cell reaction for a voltaic cell based on Use the table of standard electrode potentials
these two electrodes, and calculate the in your textbook to decide which one of the
standard cell potential, E°cell. following statements is correct.
A. 2Al+3(aq) + 3Cd+2(aq) → 2Al(s) + 3Cd(s) a. The Ni electrode is the anode.
E°cell = 2.10 V b. Electrons flow from the iron
B. 2Al(s) + 3Cd+2(aq) → 2Al+3(aq) + 3Cd(s) electrode to the nickel electrode.
E°cell = 1.26 V c. The iron electrode is positively
C. 2Al(s) + 3Cd+2(aq) → 2Al+3(aq) + 3Cd(s) charged.
E°cell = 3.78V d. The iron electrode will gain mass
D. 2Al (aq) + 3Cd(s) → 2Al(s) + 3Cd+2(aq)
+3
when current flows.
E°cell = 1.26 V e. The salt bridge conducts electrons
E. 2Al+3(aq) + 3Cd(s) → 2Al(s) + 3Cd+2(aq) through solution.
E°cell = 2.10 V
10. Which one of the following reactions must
7. Use the following standard electrode be carried out in an electrolytic cell, rather than
potentials to predict the species formed at the a voltaic cell?
electrodes in the electrolysis of aqueous CuSO4. A. Zn + Cd2+ → Cd + Zn2+
B. Al + 3/2Br2 → Al3+ + 3Br-
 C. 2Al3+ + 3Fe → 2Al + 3Fe2+
D. H2 + I2 → 2H+ + 2I-
E. 2H2 + O2 → 2H2O

11. How many minutes does it take to plate

0.800 g of silver metal onto a serving tray from
an aqueous solution of AgNO3 at a current of
2.50 A? (F = 96500 C/mol)
A. < 2 minutes
B. 2.38 minutes
C. 4.77 minutes
D. 9.54 minutes
E. 23.8 minutes
 EQUILIBRIA a general rule to help predict the change in the
position of equilibrium. You should learn the
Factors Affecting Chemical Equilibria rule, but think carefully when you apply it in
You probably think you know what the exam questions.
word ‘equilibrium’ means, and you may have Le Chatelier’s principle states that if a
used it in physics to mean ‘forces in balance’ or closed system at equilibrium is subject to a
something similar. In chemistry it has a similar change, then the system will adjust in such a
meaning, but here it is chemical reactions that way as to minimise the effect of the change.
are in balance. The sign used to represent The factors that can be changed easily
a reaction in equilibrium. What exactly does the are concentration, temperature and pressure.
word mean in a chemical context? You might also have suggested ‘using a catalyst’
— this possibility is looked at later.Consider the
First, you need to understand that all
following general reaction:
chemical reactions are reversible, given enough
energy. In a reversible reaction at equilibrium,
If we increase the concentration of
the rates of the forward and reverse reactions
either of the reactants A or B, more of the
are the same. In other words, the amount of
products C and D will be produced. The general
reactants forming products in a given time is
reaction shown above is an exothermic
the same as the amount of products breaking
reaction. If we increase the Temperature, there
down to give reactants in the same time. These
will be less of the products formed. The reverse
are generally referred to as dynamic equilibria.
would be true for an endothermic reaction. The
An example of a dynamic equilibrium in influence of pressure is only relevant for gas
the gas phase is the reaction of nitrogen and phase reactions. Think back to the Haber
hydrogen to form ammonia in the Haber process for making ammonia:
process:
There are fewer molecules on the right-
hand side of the equation. This means that if we
Dynamic equilibria can also take place in the increase the pressure, the equilibrium will shift
liquid phase: to produce more ammonia, reducing the total
number of molecules in the system and
therefore reducing the pressure.
In order to see what effect adding a
In a dynamic equilibrium:
catalyst might have, we have to think about the
● the forward reaction takes place at the same
processes taking place. Look at Figure below,
rate as the reverse reaction
which shows the energy profile of an
● there is no net change in the concentration of
equilibrium reaction with and without a catalyst
each substance
present.
● the equilibrium compositions of the
Figure below shows that the catalyst
substances can be approached from either
has lowered the activation energy for the
reactants or products
forward reaction. Consider the reverse reaction
— the activation energy for this has also been
Le Chatelier’s principle lowered by the same amount. In other words,
The French chemist Henri Le Chatelier the presence of a catalyst does not change the
studied many dynamic equilibria and suggested
position of equilibrium; it enables equilibrium Let’s look at how these two constants are
to be established more quickly calculated.Consider the reaction between
ethanol and ethanoic acid

In an experiment, 0.100mol of ethanol and

0.200mol of ethanoic acid were mixed together
and the mixture was allowed to reach
equilibrium. The acid was then titrated with
1.00moldm-3 sodium hydroxide and 115cm3
were needed to neutralise the acid. This volume
of sodium hydroxide contains:
Reaction profile with and without a
catalyst (1.0 × 115)/1000 = 0.115mol of sodium
hydroxide
Equilibrium constants and calculations
This means that there were 0.115mol of
For any equilibrium in the liquid state, an
ethanoic acid present at equilibrium.Now let’s
equilibrium constant, Kc, can be defined in
look at the other species present
terms of concentration. For our general
equation:

The quantities in square brackets represent the We have to divide by the total volume, V, since
concentrations of the different species at we are using concentrations.We can deduce
equilibrium. It is important to remember that that (0.200 - 0.115) mol of ethanoic acid have
equilibrium constants depend on temperature. been used. Hence the same amount of ethanol
will have reacted. So, at equilibrium, the moles
For gas phase reactions, partial present are:
pressures (in atmospheres) of the species
involved in the equilibrium are used. To
distinguish this from reactions in solution the
symbol Kp is used for the equilibrium constant.
So, for the reaction between hydrogen and
iodine to form hydrogen iodide: Substituting into the expression for Kc, since
there are the same number of molecules on
each side of the equilibrium, the V terms cancel
out:

where p represents the partial pressure of each

of the species
We can use a similar process to
calculate Kp for reactions taking place in the gas
phase. To do this we need to understand what
is meant by partial pressure. The partial donating protons (H+) and a base as a
pressure of a gas is defined as its mole fraction substance capable of accepting them:
multiplied by the total pressure. Suppose we
think of air as consisting of one-fifth oxygen and
four-fifths nitrogen at a total pressure of
100kPa. Then: Here hydrogen chloride is acting as an
acid by donating a proton to ammonia, which is
partial pressure of oxygen, p(O2) = 1/5 × acting as a base. In the reverse of this reaction,
100kPa = 20kPa the chloride ion can accept a proton from the
ammonium ion. This means that the ammonium
partial pressure of nitrogen, p(N2) = 4/5 ×
ion would be acting as an acid in donating the
100kPa = 80kPa
proton to the chloride ion, which would be
Together this gives the total pressure of acting as a base. In this reaction, the chloride
100kPa. ion is known as the conjugate base of hydrogen
chloride and the ammonium ion as the
Let’s consider the dissociation of hydrogen
conjugate acid of ammonia. It is also important
iodide at 700 K:
to know how substances behave with water,
the common solvent. Hydrogen chloride reacts
with water as follows:
If the value of Kp under these conditions is
0.020, and the reaction started with pure
hydrogen iodide at a pressure of 100kPa, what
Here water is acting as a base, accepting a
will be the partial pressure of hydrogen, x, at
proton from hydrogen chloride; the H3O+ion is
equilibrium?
its conjugate acid. Water also reacts with
ammonia:

Water is acting as an acid, donating a proton to

ammonia; the OH- ion is its conjugate base.

Strong and weak acids and bases

It is really important to understand the
difference between dilute and weak, and
concentrated and strong when you are talking
about acids and bases:
● A strong acid or strong base is completely
ionised in solution.
● A weak acid or weak base is only partially
Ionic Equilibria ionised in solution.
Bronsted–Lowry acids and bases ● A concentrated acid or concentrated base
The Bronsted–Lowry theory is the most has a large number of moles per unit volume of
commonly used description of acidity. It the acid or base concerned.
describes an acid as a substance capable of ● A dilute solution has a small number of moles
relative to the solvent.
 pH = -log (10-7) = 7
Examples of strong and weak acids and bases
The numbers are not always this simple.
are shown in Table below.
Suppose that in a given solution [H+(aq)] = 8.6 ×
10-9moldm-3.

To calculate the pH of this solution you need to

understand how to take the logarithm of this
sort of number:

pH = -log [H+(aq)]
pH values are given to the nearest whole
number for 0.1moldm-3 solutions. = -log (8.6 × 10-9) = -((log 8.6) - 9) = -(0.9345
- 9) = 8.0655 or 8.07 to 3 s.f.
The categories 'strong' and 'weak' are
qualitative. To be accurate we need to be able We can also calculate [H+(aq)] given the pH of a
to make quantitative comparisons using solution. Suppose there is an acidic solution
dissociation constants or the pH of solutions of with a pH of 2.73 and we want to calculate its
the compounds. hydrogen ion concentration:

When an acid HA dissolves in water, the pH = 2.73 = -log [H-(aq)]

following equilibrium is established:
log [H-(aq)] = -2.73 = 1.862 × 10-3 = 1.86 × 10-3 to
3 s.f.

Another piece of information that is helpful is

The position of the equilibrium
the ionic product of water, Kw. This is the
indicates the strength of the acid. For a strong
product of the [H+(aq)] and [OH-(aq)], and at 298 K
acid, the equilibrium favours the products, and
is equal to 10-14mol2dm-6. This enables us to
the reaction goes almost to completion. For a
calculate [OH-(aq)] as well as [H+(aq)] in aqueous
weak acid the equilibrium favours the reactants
solutions.
with a relatively small amount of H+(aq)
produced. Choosing indicators for titrations
On carrying out a titration it is the
A more precise indication of the
change in pH of the solution at the end point
position of equilibrium can be obtained by using
that is critical when choosing a suitable
an equilibrium constant:
indicator. Two main factors need to be
considered when choosing an indicator:

● The colour change should be sharp, i.e. no

Values of Ka are small, and it is usual to convert more than one drop of acid or alkali should give
them to a logarithm (to base 10) of their value a distinct colour change.
(pKa), as with [H+(aq)] and pH.
● The end point should occur when the solution
+
Consider water at 298 K. The [H (aq)] present is contains the same number of hydrogen ions as
10-7moldm-3: hydroxide ions.

pH = log [H+(aq)] Plotting graphs of the change in pH with

the addition of the titrating solution, produces
different curves for combinations of weak and
strong acids with weak and strong bases, as
Figure below shows. Since it is a weak acid, [H+(aq)] = [A-(aq)]
and is very small. If a small amount of alkali is
added, the OH- ions react with the H+ ions,
removing them from the solution as water
molecules. This disturbs the equilibrium. By Le
Chatelier’s principle, more HA will dissociate to
restore the equilibrium and thus maintaining
the pH. On the other hand, if we add acid, the
H+ ions will react with the A- ions forming more
HA. Unfortunately [A-(aq)] is very small and
would soon be used up. This problem is solved
by adding more A- ions in the form of a salt of
the acid HA, such as Na+A-. There would,
therefore, be plenty of A- ions to mop up any
added H+ ions. So a buffer solution consists of a
weak acid and a salt of that weak acid. In the
case of the buffer system in blood, the
equilibrium is:

Addition of H+ ions moves the

equilibrium to the right, forming more carbon
dioxide and water, while the addition of OH-
ions removes H+ ions, causing the equilibrium to
move to the left releasing more H+ ions.To
calculate the pH of a buffer we can use the
expression:

Buffer solutions
Buffer solutions are able to resist a In other words, we need to know the pKa of the
change in acidity or alkalinity, maintaining an acid, together with the concentration of the
almost constant pH when a small amount of acid and its salt in the solution.
either substance is added. One important
Solubility Product
example of such a system occurs in blood, the
A final application of equilibria is in
pH of which is kept at around 7.4 by the
looking at the solubility of sparingly soluble
presence of hydrogencarbonate ions, HCO3-.
salts. All the applications looked at so far have
Buffers rely on the dissociation of weak been in homogeneous equilibria (all the
acids. Consider the weak acid HA, which substances in the same phase). With solubility
dissociates as follows: there are heterogeneous equilibria to consider,
with one component in the solid phase and the This same method can be used to
remainder in the aqueous phase. calculate the concentration of one ion if we
know
For example, in a saturated solution of silver
that of the other ion and the Ksp. It is important
chloride the following equilibrium exists:
to remember to write out the equilibrium
because not all salts have a 1 : 1 ratio of ions.
If a substance is added that has an ion
The equilibrium constant for this system can be in common with a sparingly soluble salt, the
written as concentration of that ion affects the
equilibrium. This is known as the common ion
effect. So, if sodium chloride solution is added
to a saturated solution of silver chloride more
However, it is not possible to change the solid is precipitated. This is because the extra
concentration of the solid, so a new equilibrium chloride ions react with silver ions in solution.
constant is defined that allows for this. This is The silver chloride has become less soluble in
called the solubility product, Ksp, and is the the new mixture.
product of the concentrations of the ions
present in solution: REVIEW QUESTIONS
1. The pH of a CH3COOH solution is < 7 because
when this compound is added to water:
In this case, the units of Ksp are mol2dm-6. A) CH3COOH donates H+, making [H+] >
[OH−].
Example B) CH3COOH loses OH−, making [H+] <
Suppose we want to know if a precipitate will [OH−].
form when we mix equal quantities of a C) CH3COO− deprotonates H2O,
solution of silver nitrate and a solution of increasing [OH−].
potassium chloride. We need to know the D) CH3COOH dissociation increases [H+],
thereby increasing Kw.
concentrations of the ions in each solution in
moldm-3 and Ksp for silver chloride. Let’s
2. All of the following are amphoteric EXCEPT:
assume that the concentration of potassium A) HCO3−
chloride is 1.0 ×10-3moldm-3 and that of silver B) H2PO4−
nitrate is 1.0 × 10-5moldm-3.The Ksp of silver C) SO42−
chloride at 298 K is 1.8 ×10-10mol2dm-6. D) HOOCCOO−

Answer 3. A graph depicting a titration of a weak acid

On mixing equal quantities of the two solutions, with a strong base will start at a:
each concentration is halved. Substituting the A) high pH and slope downwards with
numbers into the expression for Ksp gives: an equivalence pH equal to 7.
Ksp = [Ag+(aq)][Cl-(aq)] B) high pH and slope downwards with
[Ag+(aq)] [Cl-(aq)] = 5.0 × 10-6 × 5.0 × 10-4mol2dm-6 an equivalence pH below 7.
C) low pH and slope upwards with an
= 2.5 × 10-9 mol2dm-6
equivalence pH equal to 7.
This is greater than Ksp so a precipitate will
D) low pH and slope upwards with an
form. equivalence pH above 7.
4. List the following compounds by increasing D) Decreasing the temperature to from
pKa: 298 K to 273 K
I. H2SO4 II. NH3 III. CH3CH2COOH
IV. HF 9. A group of scientists is studying the dynamics
A) I < III < II < IV of the acetic aciddissociation below and bring
B) I < IV < III < II the process to equilibrium under standard
C) III < I < IV < II conditions. If the scientists then add 35 g of
D) II < III < IV < I sodium acetate to the reaction container, which
of the following will be true?
5. The amino and carboxyl terminals of alanine
lose protons according to the following
equilibrium: A) Q > Keq and the reaction will move in
reverse.
B) Q < Keq and the reaction will move
forward.
C) Q > Keq and the reaction will move
Which of the following indicators would be best
forward.
used to determine the second equivalence
D) Q < Keq and the reaction will move in
point when alanine is titrated with sodium
reverse.
hydroxide?
A) Methyl violet (pKb = 13.0)
10. Given the following equilibrium:
B) Methyl yellow (pKb = 10.5)
C) Thymol blue (pKb = 12.0)
D) Phenolphthalein (pKb = 4.9)
How would an increase in temperature affect
the concentration of N2 at equilibrium?
6. The Ka of HSCN is equal to 1 × 10−4. The pH of
A) The concentration of N2 will increase
a HSCN solution:
because of an increase in Keq.
A) will be approximately 4.
B) The concentration of N2 will decrease
B) will be approximately 10.
because of an increase in Keq.
C) will increase as [HSCN] increases.
C) The concentration of N2 will increase
D) cannot be determined from the
because of a decrease in Keq.
information given.
D) The concentration of N2 will remain
unchanged.
7. A 25.0 mL solution of 0.2 M acetic acid (pKa =
4.76) is mixed with 50 mL of 1.0 M sodium
11. Na2SO4 is soluble in water. If NaCl(s) is
acetate (pKb = 9.24). What is the final pH?
added to a solution of Na2SO4(aq) so that the
A) 4.8 B) 5.8 C) 9.2 D) 10.2
concentration of Na+ doubles, then the:
A) solubility constant of Na2SO4
8. Which of the following manipulations is
increases while that of NaCl decreases.
capable of changing the Keq of the reaction
B) solubility constants of Na2SO4 and
shown below?
NaCl both decrease.
C) solubility of Na2SO4 and NaCl both
A) Doubling the concentrations of N2(g), decrease.
H2(g), and NH3(g) D) solubility of Na2SO4 decreases while
B) Tripling the volume of the reaction that of NaCl increases.
container
C) Increasing the pressure from 1 to 2
atm
12. The equilibrium expression below A) A small amount of NaCl(s) would
corresponds to which of the following precipitate.
reactions? B) There will be a 6 M aqueous solution
of NaCl.
C) Enthalpy and entropy would
increase.
D) The resulting solution would be
slightly basic.

13. Which of the following salts is least soluble

in water?
A) PbI2 (Ksp = 7.9 × 10−9)
B) Mg(OH)2 (Ksp = 6.3 × 10−10)
C) Zn(IO3)2 (Ksp = 3.9 × 10−6)
D) SrF2 (Ksp = 2.6 × 10−9)

14. The water solubility of MgSO4 is

approximately 25 g/100 mL at 20°C. Compared
to a 0.25 g/mL solution of MgSO4 prepared at
20°C, a 0.25 g/mL solution prepared at 37°C
will:
A) dissolve faster and have the same
concentration of ions in solution.
B) dissolve faster and have a higher
concentration of ions in solution.
C) dissolve slower and have a lower
concentration of ions in solution.
D) dissolve slower and have the same
concentration of ions in solution.

15. If the Ksp of KI is 1.45 × 10−6 in propanol at

25°C, what would the Ksp of KI be in propane at
the same temperature?
A) 1.84 B) 2.90 × 10−3
6
C) 1.81 × 10− D) 7.56 × 10−23

16. The Ksp of NaCl in water is 35.9 at 25°C. If

500 mL of 12 M NaOH(aq) and 500 mL of 12 M
HCl(aq) solution both at 25°C are combined,
what would best describe the resulting
solution?
 REACTION KINETICS
Simple Rate Equations
You know from your practical work that
the rate of a chemical reaction is affected by
three main conditions:
● temperature
● concentration
● presence of a catalyst
you need to be able to explain the
effects of changes in these conditions using
collision theory. It is important that you learn
Boltzmann distribution
the correct terms to use when describing how
reactions are influenced. There are a number of points to remember
about this graph:
A reaction cannot take place unless the
● The distribution always goes through the
reacting particles collide with sufficient energy.
origin.
Not all collisions result in reaction and the
● The curve approaches the x-axis but does not
minimum energy required is called the
touch it.
activation energy, Ea. Increasing the
● The peak represents the most probable
temperature will increase the proportion of
energy.
successful collisions. Increasing the
● The area under the curve represents the total
concentration increases the chance of collisions
number of particles.
taking place. In the presence of a catalyst, a
● Ea represents the activation energy (the
reaction has a different mechanism, i.e. one of
minimum energy needed for reaction).
lower activation energy giving more successful
collisions. At AS you need to be able to link
these observations to the distribution of The shaded portion represents the
molecular energies and to explain the effects. number of particles with energy greater than or
equal to the activation energy (E ≥ Ea).
Boltzmann distribution of energies
The energy of molecules is directly The effect of temperature
proportional to their absolute temperature. The An increase in temperature changes the
graph below shows a typical distribution of shape of the Boltzmann distribution curve
energies at constant temperature. This is known
as the Boltzmann distribution.
 Boltzmann distribution at different It is important to remember that catalysts do
temperatures not change the Boltzmann distribution for the
temperature concerned. The position of Ea
Notice that only the temperature has changed,
simply moves to the left increasing the
so the area under the two curves is the same.
proportion of particles with E ≥ Ea as shown in
The graph shows that at the higher
Figure below.
temperature, T2:
● there are fewer particles with lower energy
(the curve is flatter)
● the most probable energy is higher
● more particles have E ≥ Ea

So, at higher temperature a greater proportion

of the particles have sufficient energy to react,
and hence the rate of reaction increases. The
reverse is true at a lower temperature.

The effect of concentration

Position of Ea in the presence and
The Boltzmann distribution is not
absence of a catalyst
relevant here. The explanation given at the
beginning of the chapter in terms of increasing Orders of reaction
the chances of collision is adequate. It is worth When the rate relationships in a
remembering that increasing the pressure of a reaction are described mathematically, the rate
gas phase reaction has the same effect as equation is in the form:
increasing concentration in the liquid phase.
rate = k[A]m[B]n
The effect of a catalyst
You should remember that catalysts Here, k is the rate constant for the reaction
speed up chemical reactions without being between substances A and B, and mand n are
permanently changed themselves. In the the powers to which the concentrations of
presence of a catalyst a reaction has a different these substances are raised in the
mechanism of activation energy, Ecat. experimentally determined rate equation. They
are also known as the orderwith respect to each
substance.

It is important to remember that not all

reactions take place in a single step. For multi-
step reactions one step will always be slower
than all the others. This is called the rate-
determining step, since it is on this that the
overall reaction rate depends.

It is easier to understand what this means by

looking at some examples. Consider the
reaction:
Activation energy in the presence and
absence of a catalyst A + B → products
If we measure the way in which the rate of this has no effect on the rate. This tells us that the
reaction changes with the concentrations of A reaction is first order with respect to B and zero
and B, we might find that if we double the order with respect to A. In other words, A does
concentration of A then the rate doubles. We not feature in the rate equation. We can now
might also find that if we double the calculate
concentration of B then the rate also doubles.
the rate constant:
This tells us that the order with respect to A is
1, and that the order with respect to B is also 1; rate = k[B]
the overall order of the reaction is 2. The rate
equation could be written as: 2.5 × 10-2 mol s-1 = k × 2.0mol

rate = k[A]1[B]1 Hence k = 1.25 × 10-2 s-1

However, we do not need to show m and n Deducing order from graphs

when they equal 1, so: Another way of deducing the order of a
reaction with respect to a given reagent is to
rate =k[A][B] look at the graph of concentration against time.
It is possible that in this reaction the rate does Zero-order and first-order reactions have
not depend on B reacting with A, but on A characteristic shapes.
breaking down and B then reacting with the
products. When this is the case, the rate
equation is:

rate = k[A][B]0

Remember that anything to the power 0 equals

1, so this rate equation should be written as:

rate = k[A]

Deducing order by the initial rates method Concentration–time graph for (a) a zero-
Most kinetic studies are based on order reaction and (b) a first order
experimental work. Consider a reaction for reaction
which the rate of reaction can be measured at It is also possible to compare graphs of
the start. Data from such an experiment are rate against concentration
given in Table below.

Look at runs 1 and 2. If we double the

concentration of B and keep the concentration
of A constant, then the rate doubles. Look at
runs 2 and 3. Doubling the concentration of A
and keeping the concentration of B constant
 Rate–concentration graph of (a) a zero- If the first mechanism is correct we would
order reaction and (b) a first -order predict that the reaction is first order with
reaction respect to C4H9Br and to OH-. If the second
mechanism is correct we would predict that the
The graphs show that in a zero-order
reaction is first order only with respect to
reaction the rate is independent of
C4H9Br, since this is the rate determining step.
concentration and gives a horizontal line. For
Practical evidence suggests that the first
the first-order reaction, the reaction shows a
mechanism is correct
constant time for the concentration of reactant
to halve. This is known as the half-life of the REVIEW QUESTIONS
reaction and is similar to the half-life used in 1. In the reaction A + 2 B → C, the rate law
radioactive decay.The half-life can be used to is experimentally determined to be rate =
calculate the rate constant of a reaction. Look k[B]2. What happens to the initial rate of
at the following reaction: reaction when the concentration of A is
CH3N2CH3(g) → CH3CH3(g) + N2(g) doubled?
A) The rate doubles.
When the compound is heated it decomposes B) The rate quadruples.
into the two gases shown. No other reactants C) The rate is halved.
are needed so: D) The rate is unchanged.
rate = k[CH3N2CH3(g)]
2. Which of the following statements is
The half-life at 500 K is about 1750s. This means always true about the kinetics of a chemical
that if the starting concentration is 0.10moldm- reaction?
3
, after 1750s the concentration will have A) The rate law includes all reactants
halved to 0.05moldm-3. In another 1750s, the in the balanced overall equation.
concentration will have halved to 0.025moldm- B) The overall order equals the sum
3
, and so on. of the reactant coefficients in the
Half-life can be used to calculate the rate overall reaction.
constant, k. For a first-order reaction: C) The overall order equals the sum
of the reactant coefficients in the
slow step of the reaction.
D) The structure of the catalyst
For the examination you need to be able to remains unchanged throughout the
predict the order of a reaction from a given reaction progress.
mechanism (and vice versa).Consider the
following reaction: 3. Which of the following is represented by
C4H9Br + OH- → C4H9OH + Br a localized minimum in a reaction
coordinate diagram?
This could occur in one step as shown above or A) Transition state B) Product
in two steps: C) Activated complex D)
slow step: C4H9Br → C4H9+ + Br Intermediate

fast step: C4H9+ + OH- → C4H9OH 4. Which factor always affects both
thermodynamic and kinetic properties?
 A) Temperature
B) Transition state energy level
C) Reactant coefficients of the
overall reaction
D) No single factor always affects When this reaction is observed at the
both thermodynamics and kinetics. macroscopic level, it appears as though
nothing is happening, yet one can detect
5. Which of the following best describes the trace amounts of CO2 and H2O being
role of pepsin in the process of proteolysis? formed. These observations are best
A) It stabilizes the structure of the explained by the fact that the reaction is:
amino acid end products. A) thermodynamically favorable but
B) It lowers the energy requirement not kinetically favorable.
needed for the reaction to proceed. B) kinetically favorable but not
C) It increases the Keq of thermodynamically favorable.
proteolysis. C) neither kinetically nor
D) It lowers the free energy of the thermodynamically favorable.
peptide reactant. D) both kinetically and
thermodynamically favorable.
6. Based on the reaction mechanism shown
below, which of the following statements is
correct?

A) Step 1 is the rate-determining

step and the rate of the overall
reaction is k[N2O2].
B) Step 1 is the rate-determining
step and the rate of the overall
reaction is k[NO]2.
C) Step 2 is the rate-determining
step and the rate of the overall
reaction is k[NO2]2.
D) Step 2 is the rate-determining
step and the rate of the overall
reaction isk[N2O2][O2].

7. When table sugar is exposed to air it

undergoes the following reaction:
ORGANIC CHEMISTRY bond, are more acidic than the hydrogen atoms
in ethylene (C2H4), a molecule that has a single
double bond.
A. FUNDAMENTALS

2. FORMULAE
1. BACKGROUND AND INTRODUCTION It is important to understand and know when to
Carbon is central to organic chemistry. use the different ways of representing organic
Because carbon is an electroneutral atom, its molecules. Read the examples carefully so that
bonding to more electronegative atoms you are in no doubt.
generates polar bonds (dipoles) that formulate
Molecular formula
potential sites of chemistry. We will see this
A molecular formula summarises the numbers
point over and over. With an atomic number of
and types of atom present in a molecule. The
six, carbon has four electrons that participate in functional group is shown separately from the
the generation of covalent bonds as shown hydrocarbon chain — for example, C2H5OH
below. Recall that the orbitals of valence rather than C2H6O.
electrons combine to form new hybrid orbitals.
Be familiar with how hybridization of orbitals Structural formula
A structural formula requires the minimum
and molecular shapes are related.
detail to provide an unambiguous structure for
a compound. For example, CH3CH2CH2OH is
acceptable for propan-1-ol whereas C3H7OH is
not.

Displayed formula
A displayed formula shows the correct
Single bonds are known as sigma bonds positioning of the atoms and the bonds
(σ) and double bonds are also called pi bonds between them. For example ethanoic acid,
(π) bonds. A double bond contains one σ and which has the structural formula CH3CO2H, has
one π bond. A triple bond contains one σ and the displayed formula:
two π bonds.
There are a few points regarding
hybridization that are important to know:
1) The greater the s character, the greater the
bond dissociation energy.
2) The greater the s character, the shorter and
You may be asked for ‘partially displayed
stronger the bond.
formulae’. This means that you have to show
3) Therefore, carbon-carbon triple bonds are
the positions of atoms and the bonds between
shorter than double bonds, but require more them at the site of a reaction.
energy to dissociate as they have higher bond
dissociation energies. Skeletal formula
4) Acidity is inversely proportional to s This is a simplified representation of an organic
molecule that concentrates on the carbon
character. Thus, the hydrogen atoms in
‘backbone’ of a molecule, together with any
acetylene (C2H2), a molecule that has a triple
functional groups. Bonds to hydrogen atoms are ● How to name hydrocarbon chains
not normally shown, unless they form part of a ● How to name the functional groups in organic
functional group. The skeletal formula for chemistry
butan-2-ol is shown below: ● How to indicate the positions of functional
groups in the molecule
There are some simple rules that will help you.

The hydrocarbon chain

The key thing to remember is that the
prefix indicates the number of carbon atoms
For more complex structures, where the three- present in the main chain
dimensional structure of the molecule may be
important, a ‘partial-skeletal’ formula may be
used. This shows the geometry of key bonds to
hydrogen (and other) atoms in the molecule, as
shown below:

Hydrocarbon molecules do not have only

straight chains, they can be branched. For a
Three-dimensional structures branched molecule, look at the number of
There are times when you need to be able to carbon atoms in the branch and count the
show the three-dimensional structures of number of the carbon to which the branch is
relatively simple molecules, — for example, joined (remember to count from the end that
showing a pair of optical isomers. The gives the lower number). Some examples are
convention of using a solid wedge to represent shown below. Remember to use the longest
a bond coming ‘out of the paper’ and a dashed continuous carbon chain as the basic
line for one going ‘behind the paper’ is used, as hydrocarbon.
shown below: Alkanes are a family of hydrocarbons
that contain only C C single bonds and C H
bonds. Alkanes are relatively unreactive, except
to combustion and they form the major fuels
that we use. All of the examples given above
are alkanes.

Alkenes are a family of hydrocarbons

that have a reactive functional group, the C C
double bond. The double bond makes alkenes
3. NAMES AND FUNCTIONAL GROUPS more reactive and they are important organic
It is important that you know: compounds.
 In alkenes, it is the position of the C C
double bond that is indicated. So, CH3CH2CH
CHCH2CH3 is called hex-3-ene and (CH3)2C
CHCH2CH3 is called 2-methylpent-2-ene (the
double bond is in the second possible position
and there is a methyl group branching from
 x represents the number of hydrogens
carbon atom 2).
and any monovalent atoms (such as
Arenes are a family of hydrocarbons the halogens: F, Cl, Br, or I).
that contain a benzene ring made up of six  Since the number of oxygens has no
carbons. effect, it is ignored.
 For nitrogen-containing compounds,
replace each N by 1 C and 1 H when
using this formula.

One degree of unsaturation indicates the

presence of one π bond or one ring; two
In a benzene ring the carbon atoms are degrees of unsaturation means there are two π
numbered clockwise from the uppermost atom. bonds (two separate double bonds or one triple
You only need to use this numbering system if bond), or one π bond and one ring, or two rings,
there is more than one group attached to the and so on. The presence of heteroatoms can
ring. also affect the degree of unsaturation in a
molecule.

5. ISOMERISM
Isomers are compounds that have the same
molecular formula (same chemical composition)
but different structural formulae. You need to
know about three main types of isomerism —
structural, geometrical and optical.

Structural isomerism
Chain isomerism
In chain isomerism, the isomers arise due to
branching of the carbon chain. So C4H10 can
4. CALCULATIONS have both a straight chain form and a branched
Degrees of unsaturation chain form:
The number of double bonds and/or rings in a
compound is referred to as its
degrees (or units) of unsaturation. This can be
figured out given the molecular formula of the
compound. The branched chain is three carbons long and
has a methyl group on the second carbon atom.
Position isomerism These two forms are different because the
In position isomerism, the carbon chain is fixed, double bond prevents the rotation needed to
but the position of substituent groups can vary. make the two forms identical. Notice that there
The alcohols propan-1-ol and propan-2-ol show is another isomer, but this time it is a position
this: isomer, rather than a cis-trans isomer.

Changing the position of a group can affect how

easily it reacts, as well as its physical properties,
Optical isomerism and chiral centres
such as boiling point. Propan-1-ol has a boiling
The final type of isomerism you need to be able
point of 97°C whereas propan-2-ol has a boiling
to recognise and explain is optical isomerism.
point of 82°C.
This gets its name from the effect an optical
Functional group isomerism isomer has on the plane of plane-polarised light.
In functional group isomerism the nature of the One isomer rotates the polarised light
functional group within the molecule is clockwise, and the other isomer rotates it an
different. This is important because it changes equal amount anti-clockwise. This occurs when
the chemical reactions that the molecule there is a carbon with four different groups
undergoes. The formula C3H6O can represent attached to it — this is called a chiral carbon. An
three molecules, each with a different example was shown on page 120 and another
functional group example, butan-2-ol, is shown below:

Notice that the two molecules are mirror-

Geometric or cis-trans isomerism images, and that the central carbon atom has
Geometric isomerism occurs where there is four different groups attached. When you draw
restricted rotation around a bond, such as in these structures it is important to check that
alkenes. It also needs two groups, one on each your diagrams make chemical ‘sense’. Take the
end of the double bond, such as in 1,2- structure of 2-aminopropanoic acid for
dichloroethene: example. It is important to show the ‘acid’
group joined to the central carbon the right way
round.
 split in two ways. In homolytic fission one
electron goes to each fragment:

Identifying chiral carbon atoms can be tricky,

particularly in complex or skeletal molecular
structures. You have to work out whether or In heterolytic fission both electrons go to one
not a given carbon atom has two (or more) fragment and none to the other:
identical groups attached to it. Look at the
skeletal structure below:

2. Free radical reactions

Free radicals are usually highly reactive
It contains three non-terminal carbon atoms
species consisting of an atom or fragment of a
numbered 2, 3 and 4. Look at each of these in
molecule with an unpaired electron. In
turn. Carbon 2 has two bonds attached to
equations, it is usual to show the unpaired
methyl groups, carbon 4 has two bonds
electron as a ‘dot’. These free radicals may be
attached to hydrogen atoms (not shown), and
formed by the action of ultraviolet light (such as
carbon 3 is attached to four different groups.
in the upper atmosphere) or by the breakdown
Therefore, carbon 3 is chiral. You may be asked
of a very unstable organic compound.
to examine a complex molecule and state the
number of chiral carbon atoms (or perhaps In general, free radical reactions take place
circle them). An example of such a molecule, in three distinct steps — initiation, propagation
the synthetic form of the hormone testosterone and termination. The reaction you will study is
the reaction of methane with chlorine in the
presence of ultraviolet light.

Step 1: initiation Free radicals are formed by

the breaking of a bond by homolytic fission:

Step 2: propagation The free radicals formed

begin a chain reaction in which as each free
B. ORGANIC REACTIONS radical is used another is formed:
1. Fission of bonds
Organic compounds are held together by
covalent bonds, so you no longer need to worry
about ionic reactions (except in a few rare
cases). In organic molecules, a given bond can
Step 3: termination These are reactions in as in nucleophilic substitution. Both
which free radicals combine and hence end that nucleophiles and electrophiles can take part in
part of the chain reaction: substitution reactions.

Elimination
An elimination reaction involves the
removal of atoms from two adjacent carbon
atoms to leave a double bond. It is the reverse
of the electrophilic addition reaction

Hydrolysis
This is a reaction, usually in aqueous
3. Nucleophilic and electrophilic reactions media, between one organic molecule and
Nucleophilic reagents ‘like’ positive charges water or acid or alkali which leads to the
and electrophilic reagents ‘like’ areas of formation of at least two products. Two
electron density. It follows that the reagents examples are:
themselves are the opposite of what they seek.

Nucleophiles
Nucleophiles include halide ions, hydroxyl
ions, cyanide ions and molecules containing Oxidation
lone pairs, such as water and ammonia, or even In general, this refers to the oxidation
ethanol. A typical nucleophilic substitution of a C OH group to form a C O group in an
reaction is: aldehyde, ketone or carboxylic acid. Such
oxidations are often brought about by warming
the organic compound with acidified potassium
Electrophiles dichromate(VI). This can produce complicated
Electrophiles are electron-deficient equations, and in organic reactions it is
species, generally positively charged ions such permissible to show the oxidising agent as [O]:
as H+, Cl+, Br+, I+, NO2+, CH3+, CH3CO+. An
example of an electrophilic addition reaction is:
Reduction
This is the opposite of oxidation and, in
general, applies to compounds containing a C O
Other types of reaction group. Reduction may be brought about by
Addition several reducing agents including tin and dilute
Addition refers to an increase in hydrochloric acid, sodium in ethanol and lithium
saturation, in other words adding a molecule to aluminium hydride. In organic reduction
a C C double bond as in the above reaction. The reactions, the reducing agent is usually
molecule achieves this by interacting with the represented by [H], as shown in the example
π-electrons in the double bond below:

Substitution
Substitution refers to the replacement
of one group in an organic molecule by another
 C. HYDROCARBONS Addition reactions
1. Alkanes Because alkenes have a double bond, it
is reasonable to expect addition reactions to be
Combustion
particularly important.
Due to their general lack of reactivity,
the single most important use of alkanes is as With hydrogen
fuels. You may already know about the Ethene reacts with hydrogen at a
importance of crude oil, and the ‘cracking’ of temperature of about 150°C in the presence of
less useful fractions to form more useful finely-divided (powdered) nickel. The hydrogen
products (this is covered on the next adds across the double bond forming ethane:
pages).Ethane is used as an example of an
alkane, noting that it has the formula C2H6 and
that the general formula for alkanes is CnH2n+2. With steam
Ethane reacts differently with oxygen Water, in the form of steam, can be
depending on how much oxygen is available. added across ethene's double bond to form
ethanol. This is carried out industrially at a
temperature of about 300°C and a pressure of
about 60atm in the presence of a phosphoric(V)
acid catalyst.
For alkenes other than ethene, there is
the possibility of adding the hydrogen to two
Restricting the amount of oxygen reduces the
different carbons. In propene, for example, the
amount by which the carbon in ethane is
hydrogen can be added to either the end
oxidised until it cannot be oxidised at all. The
carbon or to the middle carbon, forming
midway point produces poisonous carbon
propan-2-ol and propan-1-ol respectively
monoxide, which has been known to kill people
using faulty gas heaters.

Substitution reactions Markovnikoff’s rule (worth learning) states that

Alkanes react with difficulty with both
when a molecule of the form HX is added across
chlorine and bromine. In order to react, alkanes a double bond, the hydrogen usually becomes
need energy from ultraviolet light (sunlight) attached to the carbon that is already attached
and, as you might expect, chlorine reacts more to the most hydrogen atoms. This means that in
easily than bromine. Taking ethane as the
the above reaction, propan-2-ol is favoured.
example, the hydrogen atoms are replaced one
at a time in substitution reactions:
With hydrogen halides
If a gaseous alkene is bubbled through,
or a liquid alkene is shaken with, either a
concentrated aqueous solution of hydrogen
bromide or hydrogen bromide dissolved in a
non-polar solvent, the hydrogen bromide is
2. Alkenes added across the double bond. The reaction is
Ethene is used as an example of an alkene, similar to the addition of water and follows
noting that it has the formula C2H4 and that the Markovnikoff’s rule:
general formula for alkenes is CnH2n.
With halogens
Ethene reacts with halogens by adding
across the double bond. Therefore, with
bromine at room temperature the reaction
forms 1,2-dibromoethane:
When the acidified manganate(VII) ions oxidise
the alkene, two C O double bonds are formed:
Chlorine, being more reactive, reacts faster
than bromine. Iodine reacts more slowly. The
reaction above refers to ethene reacting with
the pure halogen. Often, as in testing for
A compound that contains a C O functional
alkenes using bromine water, a competing
group is known as a carbonyl compound. A
reaction can take place:
carbonyl compound with two hydrocarbon
groups is called a ketone. If one of the R groups
Oxidation reactions is hydrogen, the carbonyl compound formed is
Alkenes react with oxidising agents such called an aldehyde and this can be oxidised
as acidified manganate(VII) ions. The extent of further by acidified manganate(VII) to form a
the reaction, and hence the nature of the carboxylic acid:
products, depends on the concentration of the
oxidising agent and the temperature.

With cold, dilute, acidified manganate(VII) ions

Under these conditions ethene is oxidised to
the diol 1,2-dihdroxyethane.

With hot, concentrated, acidified

manganate(VII) ions
There is one further complication that occurs
Acidified manganate(VII) is such a strong
when there are no R groups at one end of the
oxidising agent that in concentrated solution
double bond. The carboxylic acid formed under
and with heat the carbon-to-carbon double
those circumstances (methanoic acid) is itself
bond of the alkene is ruptured. You may not
oxidised by the acidified manganate(VII) ions to
think that this is a very useful reaction, but by
form carbon dioxide and water:
looking at the products the position of a double
bond in an unknown alkene can be determined.
The symbol R is used to represent a
hydrocarbon group or a hydrogen atom. So, any
alkene can be represented by the following
formula: Here are some simple rules that might help you
to work out the structure of the original alkene:

● Think about each end of the double bond

separately.
● If there are two hydrocarbon groups at one Second, the carbocation is attacked rapidly by
end of the bond, that part of the molecule will the remaining Br- ion to form the dibromide
give a ketone.

● If there is one hydrocarbon group and one

hydrogen atom at one end of the bond, that
part of the molecule will give a carboxylic acid.

● If there are two hydrogen atoms at one end 3. Arenes

of the bond, that part of the molecule will give You need to know about two arenes — benzene
carbon dioxide and water. and methylbenzene:
● Combine the information to work back to the
structure of the original alkene.

Polymerisation
Carbon is one of the few elements to
form rings and extended chains of atoms.
Alkenes can join together to form long chains,
or polymers. This does not apply only to Although you might not think these
hydrocarbon alkenes but also to substituted molecules are very different, the presence of a
alkenes such as chloroethene (CH2 CHCl) which side chain in methylbenzene means that it is
is used to make PVC. able to undergo an additional set of reactions
compared to benzene.
Electrophilic addition
You saw in the previous chapter that Substitution reactions
halogens behave as electrophiles, and you know Benzene
that alkenes have a concentration of electrons Benzene reacts at room temperature with
round the double bond. For the examination, chlorine or bromine in the presence of a
you need to understand the mechanism of catalyst. One of the hydrogen atoms in the ring
electrophilic addition, with the specific example is replaced by a chlorine or bromine atom. A
of bromine reacting with ethene. The reaction typical catalyst is the aluminium halide of the
takes place in two stages. halogen being substituted, or iron (which reacts
with the halogen to form the iron(III) halide
First, as the bromine molecule approaches the which then acts as the catalyst):
ethene molecule, the π-electrons in ethene
induce a dipole on the bromine molecule. A
bond is formed between the carbon and the
bromine forming a positively charged species
called a carbocation: In the presence of ultraviolet light (or sunlight),
but without a catalyst, benzene undergoes
addition reactions with both chlorine and
bromine, with six halogen atoms added to the
ring
As you might expect, the reaction is faster with
chlorine than with bromine.
Methylbenzene
With methylbenzene there are two
different types of substitution, depending on
whether a ring hydrogen or a methyl hydrogen
is substituted.
As with benzene, substitution of a ring
hydrogen occurs at room temperature in the
presence of an aluminium halide or iron
catalyst. There is an additional complication of
where the halogen atom goes in relation to the
methyl group. Methyl groups direct further
substitution to the 2- or 4- positions in the ring Nitration
(the 1-position is that occupied by the methyl This is the only reaction of arenes for
group). This reaction with either chlorine or which you need to know the mechanism.
bromine under these conditions results in the Benzene
formation of a mixture of 2-halo- and 4- When benzene is treated with a mixture of
halomethylbenzene: concentrated nitric acid and concentrated
sulfuric acid at a temperature lower than 50°C,
yellow nitrobenzene is gradually formed. The
sulfuric acid acts as a catalyst.

At higher temperatures, or with prolonged

reaction even at 50 °C, further nitration occurs
with a second nitro group being substituted into
the ring. The second nitro group goes into the
3-position:
When boiling methylbenzene is reacted
with chlorine or bromine in the presence of
ultraviolet light, the methyl hydrogen atoms are
substituted. Provided sufficient halogen is
present, all three hydrogen atoms are
eventually substituted:

Compare this with the methyl group in

methylbenzene. It is possible to get a further
nitro group in the 5-position, but the presence As with the halogens, a mixture of the 2- and 4-
of a nitro group ‘deactivates’ the benzene ring, nitro substituted arenes is formed:
making it much less likely to react.

The mechanism for the mononitration of

benzene is an example of electrophilic
substitution. The nitrating mixture of
concentrated nitric and concentrated sulfuric
acids produces the electrophile — the
nitronium ion, NO2+:

The NO2+ ion approaches the delocalised

electrons in benzene and two of these form a
bond with the positive charge now spread over Side-chain oxidation
the rest of the atoms in the ring: This applies only to methylbenzene
(and other arenes with alkyl side chains). Alkyl
groups in alkanes are usually fairly unreactive
towards oxidising agents. However, when
attached to a benzene ring they are relatively
easily oxidised. Heating methylbenzene (or any
alkylbenzene) with alkaline potassium
manganate(VII) solution, followed by
acidification with dilute sulfuric acid, gives
The HSO4- ion produced in the nitrating mixture benzoic acid:
now removes a hydrogen atom, re-forming the
sulfuric acid catalyst:

D. Halogen and hydroxy compounds

Methylbenzene
Halogen derivatives
In nitration, methylbenzene reacts Halogenoalkanes behave differently depending
about 25 times faster than benzene. This means on which other groups are attached to the
that a lower temperature (around 30°C rather carbon that the halogen is attached to (you will
than 50°C) has to be used to prevent more than see this trend with other functional groups).
one nitro group being substituted. Apart from
that, the reaction is the same and the same ● If there are only hydrogen atoms attached to
nitrating mixture of concentrated sulfuric and the carbon, it is a primary (1°) halogenoalkane,
nitric acids is used. for example CH3CH2Br.
● If there is one alkyl group attached as well as
the halogen, it is a secondary (2°)
halogenoalkane, for example (CH3)2CHBr

● If there are no hydrogen atoms, only alkyl

groups and the halogen, it is a tertiary (3°)
With a tertiary halogenoalkane, the mechanism
halogenoalkane, for example (CH3)3CBr
is still nucleophilic substitution:
The C-Hal bond is polar due to the difference in
electronegativity between the carbon atom and
the halogen atom. Except when bonded to
iodine, the carbon atom is relatively positive, However, in this mechanism, only one molecule
making it susceptible to nucleophilic attack by is present in the rate-determining or slow step.
lone pairs of electrons or negative ions. This is an SN1 mechanism, although there are
still two stages:
Nucleophilic substitution
Halogenoalkanes undergo a number of
nucleophilic substitution reactions. The syllabus
requires you to know about three of these using
bromoethane as a starting compound.
However, you should be able to recognise this
type of reaction with different halogenoalkanes
and different nucleophilic reagents.

Hydrolysis
When bromoethane, a primary
halogenoalkane, is heated under reflux with For a secondary halogenoalkane, the
sodium hydroxide in a solvent of aqueous mechanism is a combination of SN1 and SN2.
ethanol, the bromine is substituted by the There is another reaction that can take place
hydroxyl group and ethanol is formed: when halogenoalkanes react with hydroxide
ions.

Formation of nitriles
When a halogenoalkane is heated
You also need to know the mechanism for this
under reflux with cyanide ions dissolved in
reaction, which can be represented in two
ethanol, the cyanide ion is substituted for the
ways. The first way is as follows:
halogen and a nitrile is formed:

This is an important reaction because a carbon

The reaction is described as SN2, because there atom has been added to the carbon chain and
are two reactants in the rate determining or the nitrile group can be reacted further.
slow step. The other way of representing this
Secondary and tertiary halogenoalkanes react in
reaction is to show it as a two-stage process:
a similar way, but the mechanism may be
different.
Formation of primary amines ● Higher temperatures
When a halogenoalkane is heated with ● A concentrated solution of sodium or
ammonia, a reflux process cannot be used potassium hydroxide
because the ammonia would escape as gas. This ● Pure ethanol as the solvent
reaction has to be carried out in a sealed tube.
The reaction takes place in two steps: Hydroxy compounds

In just the same way as with primary,

secondary and tertiary halogenoalkanes, there
However, in a sealed tube the reaction does not are primary, secondary and tertiary alcohols.
stop with the formation of a primary amine. It
continues replacing successive hydrogens on Reactions of alcohols
the nitrogen to give secondary and tertiary Combustion
amines, and finally a quaternary ammonium Like most organic compounds, alcohols
salt. are flammable. You may remember this from
using a spirit burner. The equation for the
Elimination of hydrogen bromide complete combustion of ethanol is:
Under similar conditions to those
needed for nucleophilic substitution, it is
possible to get an elimination reaction to take
place. If, instead of aqueous ethanol, a Substitution to form halogenoalkanes
concentrated hydroxide solution in pure Halogenoalkanes can be hydrolysed to
ethanol is used, HBr is eliminated and a double give alcohols, and alcohols can be converted
bond is formed: into halogenoalkanes, but by different reagents.

One way of carrying out the

substitution is to use the appropriate hydrogen
halide. This method works for the bromo- and
It is important to remember that different
iodoalkanes if the hydrogen halide is generated
halogenoalkanes favour one type of reaction
in the reaction flask. Sodium bromide with
over the other
concentrated sulfuric acid can be used for the
bromoalkane, but sodium iodide and
concentrated phosphoric(V) acid have to be
used for the iodoalkane because sulfuric acid
would oxidise any HI formed. The equations for
the formation of bromoethane and iodoethane
For a given halogenoalkane, to favour are as follows:
substitution use:
● Lower temperatures
● More dilute solutions of sodium or potassium
hydroxide
● More water in the solvent mixture The following method only works with tertiary
alcohols, forming the tertiary chloroalkane:
To favour elimination use:
For other chloroalkanes we have to use
phosphorus trichloride, PCl3, phosphorus
pentachloride, PCl5, or thionyl chloride, SOCl2:

● On refluxing a secondary alcohol with

acidified dichromate(VI), a ketone is formed,
which is not oxidised further. Again the mixture
turns from orange to blue-green:

Reaction with sodium

When a small piece of sodium is
dropped into ethanol it dissolves, producing
bubbles of hydrogen gas. It leaves a colourless
solution which, if evaporated to dryness,
produces a white solid. This white solid is
sodium ethoxide, CH3CH2O-Na+: ● With a tertiary alcohol, there are no hydrogen
atoms on the carbon atoms that can be
oxidised, so there is no reaction.

This reaction is sometimes used to dispose of

small amounts of old sodium because it is much
less violent than reacting sodium with water. It
can also be used as a test for an alcohol. The
ethoxide ion (like the hydroxide ion) is a strong
base and a good nucleophile.
Provided that an aldehyde and a ketone can be
Oxidation reactions distinguished between, these oxidation
In the presence of an oxidising agent reactions can be used to detect primary,
such as acidified dichromate(VI) solution, secondary or tertiary alcohols. There are
whether or not an alcohol is oxidised depends relatively simple tests for aldehydes that use
on its structure. A positive test for oxidation is Fehling’s solution or Tollens’ reagent
that the dichromate(VI) solution turns from
orange to blue-green. Dehydration
Strong acids such as phosphoric(V) and
● On warming a primary alcohol with acidified sulfuric can be used to dehydrate alcohols to
dichromate(VI), an aldehyde is first formed. If form alkenes:
this is not removed from the reaction vessel it is
further oxidised to a carboxylic acid. The
mixture turns from orange to blue-green:
Forming esters
If an alcohol is warmed with an organic acid in
the presence of H+ ions, an ester is formed with
the elimination of water:

The presence of the benzene ring makes phenol

behave differently from alcohols.
This is an equilibrium reaction and it is often
quite slow. The reaction can be speeded up by Reactions with bases
using another compound containing the RC O Phenol is a weakly acidic compound. Its
group. Suitable compounds include acyl acidity stems from the fact that it ionises in
chlorides or acid anhydrides. water:

With ethanoyl chloride and ethanol, the

following reaction occurs:

With ethanoic anhydride and ethanol, this

reaction takes place
Because phenol is a very weak acid, the
equilibrium lies over to the left. It can lose a
proton because the remaining negative charge
In naming esters the convention is to give the
is delocalised over the benzene ring, making the
fragment of the alcohol first and then the anion
phenoxide ion more stable. There is evidence
name of the acid. So the esters shown above
for this behaviour because phenol reacts with
are all ethyl ethanoate (rather strangely they
sodium hydroxide to give a colourless product:
are usually drawn with the acid fragment first!

The tri-iodomethane (iodoform) reaction

This reaction is quite specific for a
particular structural arrangement in an alcohol.
It detects the presence of the CH3CH(OH)–
group. The test is carried out by adding iodine
solution to the alcohol and then adding just
But phenol is neither acidic enough to turn blue
enough sodium hydroxide to remove the colour
litmus paper red, nor to release carbon dioxide
of the iodine. On standing, or more usually on
from sodium carbonate. It does produce
warming, a pale yellow precipitate of tri-
hydrogen when heated with sodium:
iodomethane is formed if the group is present.

Phenol
Phenol is an aromatic hydroxyl compound:
Nitration
Phenol behaves differently from E. Carbonyl compounds
benzene in its reaction with nitric acid. It reacts Formation
in the cold with dilute nitric acid, whereas The oxidation of alcohols by acidified
benzene requires a nitrating mixture of dichromate(VI).
concentrated nitric and sulfuric acids. The
● With a primary alcohol, an aldehyde is first
reason for this is that the presence of the OH
formed. If this is not removed from the reaction
group makes the ring much more reactive. It
vessel, it is further oxidised to give a carboxylic
also directs reaction to the 2- and 4-positions
acid:
on the ring. With dilute nitric acid, 4-
nitrophenol is formed:

With concentrated nitric acid, 2,4,6- ● With a secondary alcohol, a ketone is formed.
trinitrophenol is formed: This is not oxidised further:

Bromination Reactions
When bromine water is added to phenol, there
Reduction
is a similar effect to nitration. The activated ring
This is the reverse of the oxidation reactions
gives an almost instantaneous white precipitate
used in the preparation of carbonyl compounds.
of 2,4,6-tribromophenol:
It is carried out using sodium
tetrahydridoborate (sodium borohydride),
NaBH4.

With aldehydes such as ethanal the reaction is

as follows, forming a primary alcohol:
 carbon and a partial negative charge on the
oxygen:

With ketones such as propanone the reaction is

very similar. A secondary alcohol is formed:
Mechanism of addition of hydrogen cyanide to
an aldehyde
The reaction starts with an attack by the
nucleophilic cyanide ion on the slightly positive
carbon atom:

Nucleophilic addition of hydrogen cyanide

In just the same way that alkenes can react by
adding a molecule across a C=C double bond,
carbonyl compounds can add a molecule across
the C=O double bond. You need to know the
mechanism for this reaction, using hydrogen
cyanide as the nucleophile. You may think that The negative ion formed then picks up a
this is a strange reactant, but as we saw earlier hydrogen ion. It could come from a hydrogen
it adds a carbon atom to the chain, which is cyanide molecule or from the water or the
often an important step in a reaction. The H3O+ ions present in the slightly acidic solution:
reactions can be summarised in simple
equations:

Mechanism of addition of hydrogen cyanide to a

ketone
The mechanism for ketones is similar to that for
aldehydes. The first stage is a nucleophilic
attack by the cyanide ion on the slightly positive
Hydrogen cyanide itself is not used in the carbon atom:
reaction because it is a highly toxic gas. Instead,
sodium or potassium cyanide is added to the
carbonyl compound followed by a small amount
of sulfuric acid. This produces hydrogen cyanide
in the reaction vessel but also forms cyanide
ions, which are important as you will see when
The negative ion formed then picks up a
we look at the mechanism.
hydrogen ion to give the hydroxynitrile
The first thing to remember is that the C O bond
is polarised with a partial positive charge on the
 If the nitrile is heated under reflux with an alkali
such as sodium hydroxide solution, the sodium
Distinguishing between aldehydes and salt of the carboxylic acid is formed and
ketones ammonia is released, for example:

To obtain the carboxylic acid, a strong acid such

as hydrochloric acid is added and the carboxylic
acid is distilled off

Reactions of carboxylic acids

Formation of salts
Carboxylic acids are generally relatively weak
acids (although there are exceptions). They
behave as acids because of their ability to
donate protons:
F. Carboxylic acids and their
derivatives
Carboxylic acids
The reaction is reversible with the equilibrium
Formation of carboxylic acids
well over to the left. Ethanoic acid is never
There are three main methods for preparing more than around 1% ionised resulting in
carboxylic acids (although, strictly, one is a step solutions with a pH of between 2 and 3.
in another process).
As a result, carboxylic acids can form salts in a
Formation of carboxylic acids number of ways (although there are some
From an alcohol exceptions). Ethanoic acid is used as the
example in all the equations shown.

● Aqueous solutions of carboxylic acids react

with the more reactive metals such as
magnesium to form the salt:

From an aldehyde

● Aqueous solutions of carboxylic acids react

with metal hydroxides such as sodium
hydroxide to form the salt:

From a nitrile
If the nitrile is heated under reflux with a dilute
acid, such as dilute hydrochloric acid, a
carboxylic acid is formed, for example:
● Aqueous solutions of carboxylic acids react replaced by a –Hal group. You might wonder
with carbonates and hydrogen carbonates why this is an important reaction, but acyl
liberating carbon dioxide: chlorides are very reactive and are useful in
preparing a range of new materials.

There is very little difference between these

reactions and those with other acids. If,
however, you chose to use a marble chip as the
carbonate, the reaction would be noticeably
slower. Acyl chlorides
Hydrolysis
● Ethanoic acid reacts with ammonia in just the
same way as other acids, forming the
ammonium salt:

Reaction with alcohols and phenols

Formation of esters
Here, we are considering a single
reaction — the formation of an ester from a
carboxylic acid and an alcohol. An ester is
formed when a carboxylic acid is heated with an
alcohol in the presence of an acid catalyst,
usually concentrated sulfuric acid. The reaction
is slow and reversible, for example:

Reaction with primary amines

A primary amine is an ammonia
molecule in which one of the hydrogen atoms
In the laboratory this is achieved by warming
has been replaced by an alkyl group:
the carboxylic acid and alcohol together with a
few drops of concentrated sulfuric acid in a
water bath for 10–15 minutes and then pouring
the contents into a small beaker of cold water.
The ester can be detected by its fruity smell. If a
sample is required, it can be distilled off from
the reaction mixture. Ethyl ethanoate, the most
Primary amines react with acyl chlorides by
common ester you will come across, can be
substitution, replacing the chlorine atom and
prepared in this way.
joining via the nitrogen atom, for example:
Formation of acyl chlorides
To form an acyl halide from a carboxylic
acid, the –OH group in the acid has to be
  Margarine production
 Soap making
 Solvents

G. Nitrogen compounds
Primary amines
Formation
Alkyl amines
Esters The reaction to use for the formation of an alkyl
Hydrolysis amine is the reduction of a nitrile using lithium
You will remember that to form an tetrahydridoaluminate(III) (lithium aluminium
ester, an alcohol (or phenol) is reacted with a hydride). The reaction takes place in
carboxylic acid and water is formed as a by- ethoxyethane solution and the amine is
product. Hydrolysis is the reverse of this produced on adding a small amount of dilute
process and can be achieved in either of two acid. This does not work with NaBH4:
ways.

Acid hydrolysis
In acid hydrolysis, the ester is heated This reaction can also be achieved by heating
under reflux with either dilute hydrochloric or the nitrile in hydrogen gas in the presence of a
dilute sulfuric acid: platinum, palladium or nickel catalyst:

As in the formation of an ester, the reaction is

reversible. We try to make the reaction as Phenylamine
complete as possible by having an excess of Phenylamine is prepared from nitrobenzene in
water present. a two-stage process. First, nitrobenzene is
heated under reflux in a boiling water bath with
Base hydrolysis
a mixture of tin and concentrated hydrochloric
Base hydrolysis is the more usual way of
acid. Because of the acidic conditions, rather
hydrolysing esters because the reaction goes to
than getting phenylamine directly, the
completion, rather than forming an equilibrium
nitrobenzene is reduced to phenylammonium
mixture:
ions. The lone pair on the nitrogen in the
phenylamine picks up a hydrogen ion from the
acid:
Although this forms the sodium salt of the
carboxylic acid, it is still relatively easy to
separate the products. First, the alcohol is
distilled off and then an excess of a strong acid
(dilute hydrochloric or dilute sulfuric acid) is
added. This forms the carboxylic acid which is
only slightly ionised and can be distilled off. The second stage is to add sodium hydroxide
solution to remove the hydrogen ion:
Commercial uses
 Perfumes and flavours
The phenylamine is then extracted by steam
This is an example of electrophilic substitution
distillation.
of the benzene ring.
Basicity
With nitrous acid
When considering the basic properties
Phenylamine undergoes different reactions with
of alkyl amines, it is easiest to think of them as
nitrous acid depending on the temperature of
substituted ammonia molecules. If you
the reaction mixture. At low temperatures
remember that bases are proton acceptors it is
(<10°C) phenylamine is dissolved in cold
not too difficult to make the comparison.
hydrochloric acid and then a solution of cold
Compare the two equations:
sodium nitrite is added slowly. The slow
addition is so that the reaction mixture remains
around 5°C. A solution containing
benzenediazonium ions is obtained
The same rule applies to secondary and tertiary
amines, with alkyl groups substituting hydrogen
atoms on the nitrogen atom:

Note that when drawing the structure of a

Amines are generally stronger bases than
benzenediazonium salt, the positive charge is
ammonia. This is because alkyl groups are
shown on the nitrogen atom closest to the
electron donating, pushing negative charge
benzene ring.
onto the nitrogen atom and strengthening the
attraction to the proton. The more alkyl groups The benzenediazonium salt is not isolated, but
there are attached to the nitrogen, the stronger is often reacted by adding a cold solution of
the base formed. phenol in sodium hydroxide to the mixture:

By contrast, phenylamine is a much weaker

base than ammonia. This is because the lone
pair of electrons on the nitrogen atom is
delocalised with the π-electrons on the benzene
ring and is thus no longer as available to attract The result is a yellow, orange or red dye, the
hydrogen ions. colour of which depends on the nature of the
phenol used. With naphthalen-2-ol (2
Reactions of phenylamine naphthol), the following compound is formed:
With aqueous bromine
With bromine water, phenylamine gives a fairly
instant white precipitate of 2,4,6-
tribromophenylamine at room temperature
At temperatures above 10°C, a reaction takes This means that the monomers have to be
place that produces a complex organic mixture diamines and dicarboxylic acids.
containing mainly phenol. Nitrogen gas is
evolved:
H. Polymerisation
Addition polymerisation
Amides Poly(ethene)
Formation from acyl halides Addition polymerisation takes place
acyl halides react with primary amines. They when molecules containing a C C double bond
also react with ammonia to form amides. This is are joined together to form a long chain. The
normally carried out by adding the acyl halide simplest of these reactions is the
to a concentrated solution of ammonia. The polymerisation of ethene:
reaction is violent, producing clouds of
ammonium chloride:

In this reaction, the conditions needed are a

temperature of around 200°C, a pressure of
Hydrolysis around 2000 atmospheres and a small amount
Amides are hydrolysed by heating with aqueous of oxygen to initiate the reaction. Under these
acids or aqueous alkalis: conditions the chain could be made up of
anything between 2000 and 20000 molecules.
This reaction produces a form of poly(ethene)
called low-density poly(ethene) due to the fact
that the chains are branching and do not allow
The second reaction is sometimes used as a test close packing. This polymer is used to make
for amides, because the ammonia produced is plastic bags and for other low-strength sheet
easily detected applications.
Formation of polyamides Another form of poly(ethene), high-density
Polyamides are a very important group of poly(ethene), can be produced but the
polymers that include nylon and Kevlar®. The conditions used are very different. The
polymerisation reaction involves two temperature is much lower at around 60 °C, the
monomers that react by condensation to form pressure is only a few atmospheres and a
an amide bond between them: catalyst is required. These conditions cause the
chains to grow in a much more ordered way
enabling them to pack together much more
closely, hence increasing the density of the bulk
polymer. This polymer is used to make plastic
containers, washing-up bowls and some plastic ● In general, polyalkenes are not
pipes. biodegradable, so burying them in landfill sites
is useless. Plastic bags and bottles can prove
Poly(chloroethene)
harmful to wildlife. Even fish have been found
Chloroethene is similar to ethene, but
to have tiny particles of plastic in their
has one hydrogen atom replaced by a chlorine
stomachs. New biodegradable polymers have
atom. The double bond is still present and so
been developed for use in some types of
the molecule can be polymerised:
packaging, such as plastic bags.

● There is a large amount of hydrocarbons

locked in the polyalkenes that are thrown away.
This polymer is still called after the old name for This is wasting a precious resource — crude oil.
chloroethene — vinyl chloride — so you will see In some parts of the world, some plastics are
it referred to as polyvinylchloride or PVC. sorted and some used to fuel power generation
Although the reaction is the same, it is usual to plants. It is important that this use is seen as a
draw the molecules showing the chlorines to replacement for oil because simply incinerating
one side of the chain as below: the polyalkenes to dispose of them would add
to the carbon dioxide put into the atmosphere.

● There are so many different types of polymer

used that it is not easy to sort them quickly for
future use, either for recycling or as a fuel.
The equation to show this is as follows: Indeed some polyalkenes, such as PVC, produce
toxic gases such as hydrogen chloride and
dioxins when they are burned.

Condensation polymerization
Characteristics of condensation
polymerisation
The points to remember about
Poly(chloroethene) is used to make a wide
condensation polymerisation are as follows:
range of products including guttering and
plastic window frames. It can be rather hard ● A small molecule, such as water, is eliminated
and rigid. Chemicals called plasticisers can be as each monomer is added.
added to increase the flexibility. This increases
the range of uses — for example, electrical ● You need two different monomers (usually
cable insulation, sheet materials for flooring, but not always, e.g. nylon-6)
footwear and clothing. ● The properties of the polymer depend on the
monomer molecules used.
Disposal of polyalkenes
The use of polyalkenes has become so Polyamides
widespread that we are now faced with the the polyamides nylon-6, nylon-6,6 and
disposal of thousands of tonnes of waste polypeptides and proteins are formed by
polyalkenes each year. This causes a number of condensation polymerisation. There is nothing
problems: new to learn here — simply remember that in
condensation polymerisation small molecules
(often, but not necessarily, water) are 3. Which molecule has the largest dipole
eliminated as the polymer grows. moment?
a. HCl
Polyesters
b. CCl4
another group of condensation
c. H2S
polymers — polyesters in the form of Terylene®
d. CO2
— could be formed by condensation
polymerisation. There is nothing new to learn
4. What are the hybridizations of carbons
here.
1 and 2 respectively in the following
Identifying polymers structure?
The last part of this section of the syllabus
outlines what you might be asked to deduce
about a given polymer. You may be asked to:

● predict the type of polymerisation reaction

for a given monomer or pair of monomers

● deduce the repeat unit of a polymer obtained

from a given monomer or pair of monomers

● deduce the type of polymerisation reaction 5. How many total resonance structures
that produces a given section of a polymer can be drawn for the following anion
molecule (include those without separation of
charge)?
● identify the monomer(s) present in a given
section of a polymer molecule

REVIEW QUESTIONS:

1. The hybridization of the central carbon

in CH3C≡N and the bond angle CCN are

6. . The correct geometry around oxygenin

2. Which of the following statements CH3OCH3 is
about an sp hybridized carbon is FALSE? A. linear.
a. It is divalent. B. bent.
b. It forms bonds that are linear. C. tetrahedral.
c. It has two p orbitals. D. trigonal planar
d. It always forms triple bonds to
carbon. 7. Determine the relationship between
the two molecules shown.
 A. constitutional isomers
B. enantiomers
C. diastereomers
D. identical molecules

8. What is the correct name for this 11. . Which of the following may be
molecule? separated by ordinary physical
methods?
A. a pair of identical molecules
B. a pair of enantiomers
C. a pair of diastereomers
D. a pair of identical atoms

a. (2R,3R)-2-bromo-3-chlorobutane 12. . Which of the following molecules is

b. (2S,3R)-2-bromo-3-chlorobutane trans-1, 2-dimethylcyclohexane?
c. (2S,3S)-2-bromo-3-chlorobutane
d. (2R,3S)-2-bromo-3-chlorobutane

9. . Which of the following physical

properties differ for each of a pair of
enantiomers?

A. solubility in ethanol
B. direction of rotation of plane-
polarized light
C. boiling point and melting point
D. index of refraction

10. Determine the double bond

stereochemistry (E or Z) for the
following molecules.

13. What is the IUPAC name of the

following molecule?
14. Which compound has the highest
melting point?

a. decane
b. 2,2,3,3-tetramethylbutane
c. 2,2,3-trimethylpentane
d. 4-methylnonane

15. Which of the following alkanes will have

the lowest boiling point?

19. Which of the following occurs during

the initiation stage of a
radicalmechanism?

a. Nonradicals are formed from radicals.

b. Radicals are formed from other
radicals.
c. Radicals are formed from nonradicals.
16. The balanced equation for the
d. Nonradicals are formed from other
combustion of pentane is
nonradicals.

20. What is the product of the following

reaction?
17. Which of the following cycloalkanes has
the MOST strain energy?

18. What is the major product of the

following reaction?
 24. The Williamson ether synthesis
produces ethers by reacting an
a. alcohol with a metal.
b. alkoxide with a metal.
c. alkoxide with an alkyl halide.
d. alkyl halide with an aldehyde.

25. Ozonolysis (O3 in CH2Cl2) of compound

A under reducing conditions (Zn /acetic
acid) gives formaldehyde, 2-butanone,
and compound B. Catalytic
21. Which version of the radical hydrogenation (H2/Pd) of A gives 2,7-
halogenation of an alkane is MOST dimethylnonane. What is a possible
selective? structure for compound A?
a. fluorination
b. chlorination
c. bromination
d. iodination
26. Which of the following compounds
22. Which of the following will NOT convert does NOT give a tertiary alcohol upon
1-butanol into 1-chlorobutane in one reaction with methylmagnesium
step? bromide?
a. SOCl2
b. PCl3
c. HCl
d. CCl4
27. Supply the correct words to complete
23. Give the major product of the following this sentence: Electron-withdrawing
reaction. groups such as nitro _________ the
basicity of anilines, especially when
substituted _______________.
28. . Which of the following amines is a
tertiary amine?

29. What is the name of the following

compound?

30. . What is the sequence of reagents that

will accomplish the synthesis of the
following aromatic amine from
benzene?