Chemistr Uni 5 Note

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Topi 16 - Red Equilibri

1) Electrode potential: When a metal such as magnesium or copper is placed in water,

there is a very small tendency for the metal atoms to lose electrons and go into solution
as positive ions:
M (s) → Mn+ (aq) + ne-
(Where M = M or Cu)
The electrons will remain on the surface of the metal. In a very short time, there will be
a build-up of electrons on the surface of the metal and the resulting negative charge
attracts positive ions. In this way, a layer of positive ions is formed surrounding the
metal. Some of the positive ions will regain their electrons from the surface of the metal
and return to form part of the metal surface.
Mn+ (aq) + ne- → M (s)

Eventually, a dynamic equilibrium will be established in which the rate at which ions are
leaving the surface of the metal to go into solution is the same as the rate at which the
ions are joining the surface of the metal from the solution. This is equilibrium is
represented by the equation:

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 The difference between magnesium and copper is that the equilibrium
position will be further to the left-hand side for magnesium than for copper,
because the tendency of magnesium to release electrons is greater than that
of copper. So, with magnesium there will be a greater negative charge on the
metal, and more positive ions in solution.

In the case of both magnesium and copper, there is a potential difference

between the metal and the solution. However, the potential difference is
greater with magnesium than with copper. In each case, we would like to
measure the potential difference between the metal and the solution. This is
called the absolute potential difference.

However, it is not possible to measure the absolute potential difference

between a metal electrode and its solution. The reason is that although it is a
simple matter to connect the metal electrode to one terminal of a voltmeter,
the other terminal would have to be connected to the solution and the only
way of doing this is to dip another piece of metal into the solution. This second
piece of metal would create its own potential difference. So, you would be
measuring the potential difference between the two pieces of metal, and not
between the original metal and the solution.

The way to solve this problem is to create a reference electrode and then
measure the difference in potential between this reference electrode and the
metal electrode.
2) Standard electrode potential: If a metal rod is immersed into a solution of its ions of
concentration of 1 moldm-3 at 25°C, then the potential acquired under these conditions
is the standard electrode potential.
The standard electrode potential of an electrode is denoted by Eo.
For example: Cu2+ + 2e- ⇋ Cu; Eo = +0.34V
Or, standard electrode potential of copper electrode,

For example: Zn2+ + 2e- ⇋ Zn; E0 = -0.76V

Or, standard electrode potential of zinc electrode.

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3)

E0 cell = R - O = +0.34V - (-0.76V) = +1.10V

● The electrode at which oxidation occurs is known as anode.
● The electrode at which reduction occurs is known as cathode.
The salt bridge makes an electrical connection between the two halves of the cell,
allowing ions to flow while preventing the solutions from mixing.
At its simplest, a salt bridge consists of a strip of filter paper soaked in saturated KNO3
solution and folded over each of the two beakers. All potassium salts and all nitrates are
soluble. So, the salt bridge does not react to produce precipitates with any of the ions in
the half cells.
4) In an electrochemical cell, the salt bridge maintains electroneutrality and allows current
to flow. Otherwise, there would be a pile up of electrons and current would stop
flowing.
Ions do not flow through a salt bridge but the ions flow out of it. The cations flow out at
the cathode to counter the excess negative charges and the anions flow out at the
anode to counter the surplus positive charges. The current produced by the salt bridge is
the sum of the flow of cations and the flow of anions.
When the electric current flows through the wire, electrons are transported through the
wire from one half-cell (anode) to the other half-cell (cathode). This leaves a deficiency
of negative charge on the anode side and produces a surplus of negative charge on the
cathode side.
As the figure shows, the cell is gaining Zn2+ at the anode. So, it needs NO3- ions from the
salt bridge to keep the solution electrically neutral. Likewise, the cell is losing Cu2+ ions at
the cathode. So, it needs K+ ions to keep the solution electrically neutral.
The standard electromotive force (emf) of a cell can be determined by the following
equation:

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 Eo cell = E0R - EoO
Where, EoR = standard reduction potential
of the electrode where reduction
occurs,
o
E O = standard reduction potential
of the electrode where oxidation
occurs.
5) Standard hydrogen electrode:

● The standard electrode potential of a hydrogen electrode is assigned as zero.

● Using hydrogen electrode, the unknown potential of an electrode can be
determined.
Assuming oxidation to be occurring at the hydrogen electrode,
Eo cell = Eo unknown - Eo H+/H2
Since, Eo H+/H2 = 0V
Therefore, Eo cell = Eo unknown.
The hydrogen electrode must be controlled to the negative (-ve) terminal of the
voltmeter.
6) Standard electrode potential: The standard electrode (reduction) potential, Eo, of a
standard half-cell is the emf of that half-cell relative to a standard hydrogen electrode
under standard condition. Standard electrode potentials are sometimes called standard
redox potentials.
7) Thermodynamic feasibility of a redox reaction: If the standard cell emf of a redox
reaction is positive, the reaction is said to be feasible.

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 The reaction may not occur due to non-standard conditions (must specify which) or due
to a high activation energy.
If the standard cell emf of a redox reaction is negative, the reaction is not feasible but
the reaction may occur due to non-standard conditions (must specify which).

8) Standard electrode potential: The standard electrode (reduction) potential, Eo, of a

standard half-cell is the emf of that half-cell relative to a standard hydrogen electrode
under standard conditions.
9) Making a half-cell:
Example 1: Fe2+ (aq) + 2e- ⇋ Fe (s)
Iron metal is immersed into a solution of iron (II) ions at 1 moldm-3.
Electrode: Iron.

Example 2: Fe3+ (aq) + e- ⇋ Fe2+ (aq)

A mixture of iron (II) and iron (III) ions at 1M each.
Electrode: Platinum.

Example 3: Cl2 (g) + 2e- ⇋ 2Cl- (aq)

Chlorine gas at 100kPa is bubbled through a solution of chloride ions at 1M.
Electrode: Platinum.

10) Non-standard conditions: If the conditions are not standard, the value of the electrode
potential will alter.
11) Changes in concentration: If the concentration of Cr2O72- (dichromate ions) or H+ ions is
increased, the position of equilibria is driven to the right, which causes the value of
electrode potential to increase and vice-versa.
12) Changes in pressure: A change in pressure affects gaseous substances only.
For example: O2 (g) + H2O (l) + 4e- ⇋ 4OH- (aq) ; Eo = +0.40V
An increase in pressure drives the equilibrium to the right which causes the value of E0
to increase and vice-versa.

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13) Changes in temperature: the effects of a change in temperature depends on whether
the redox half-equation is exothermic or endothermic.
For example: Cl2 + 2e- ⇋ 2Cl- (aq) ; ΔH = (-)ve ; Eo = +1.36V
● If temperature increases, equilibrium moves to the left. So, E0 decreases.
● If temperature decreases, equilibrium moves to the right. So, Eo increases.
14)

15)

Procedure:
1. 25cm3 of KIO3 solution is pipetted into a conical flask.
2. Excess KI solution followed by excess dilute H2SO4 solution are added to the
solution in the flask. (This liberates iodine and thus the solution turns brown).
IO3- (aq) + 5I- (aq) + 6H+ (aq) → 3I2 (aq) + 3H2O (l)
This liberated iodine is titrated with standard sodium thiosulfate solution.
2S2O32- (aq) + I2 (aq) → S4O62- (aq) + 2I- (aq)

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 3. The sodium thiosulfate solution is added from the burette to the iodine solution
until the original brown color of the iodine changes to pale yellow.
4. A few drops of starch solution is added to the pale yellow solution to produce a
blue-black coloration.
5. Sodium thiosulfate solution is then added drop by drop until the blue-black
solution turns colorless.
6. The titration is repeated until at least two concordant titres are obtained.

If starch were not added, it would be very difficult to detect the end point. The color of
the iodine solution becomes very faint towards the end of the reaction and this makes it
difficult to accurately assess when the end point has been obtained.
If the starch is added too early, an insoluble starch-iodine complex forms which results in
an inaccurate titre.

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16)

Potassium manganate (VII) is a powerful oxidising agent. It is used for the quantitative
estimation of many reducing agents, especially compounds of iron (II) and for
ethanedioic acid and its salts.
The general method for titrating the standard solution of potassium manganate (VII)
with a reducing agent is as follows:
● A sample of known volume, usually 25.0cm3, of the reducing agent is pipetted
into a conical flask.
● Approximately 25cm3 of dilute sulfuric acid is added.
● A burette is filled with a standard solution of potassium manganate (VII).
● Potassium manganate (VII) is added steadily, with swirling, until the purple
color disappears slowly.
● The potassium manganate (VII) is then added dropwise, until the solution
becomes slightly pink.
● The titration is repeated until at least two concordant titres are obtained.
No indicator is required in potassium manganate (VII) titrations. On adding the
potassium manganate (VII) solution from a burette, the purple MnO4- ions change
rapidly to the very pale, pink Mn2+ ions which look colorless in dilute solution. At the end
point, one drop of excess MnO4- is sufficient to produce a permanent pale pink color.

In an alkaline solution, potassium manganate (VII) yields manganese (IV) oxide as a

brown precipitate, and this interferes with the end point color. For this reason,
therefore, potassium manganate (VII) is almost always used in solutions that are
sufficiently acidic to prevent the formation of manganese (IV) oxide.

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17) Titration of potassium manganate (VII) with iron (II) ions:

In this reaction, the iron (II) ions are oxidised and the manganate (VII) ions are reduced.
The ionic half-equations involved are:

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18) Titration of potassium manganate (VII) with ethanedioic acid:

In this reaction, the ethanedioic acid/ ethanedioate ions are oxidised and the manganate
(VII) ions are reduced. The ionic half-equations involved are:

19) Chemistry of vanadium:

Oxidation number Formula Name Color of aqueous
solution

+2 V2+ Vanadium (II) Purple

+3 V3+ Vanadium (III) Green

+4 VO2- Oxovanadium (IV) Blue

+5 VO2+ Dioxovanadium (V) Yellow

The usual source of vanadium with oxidation number +5 is the compound ammonium
vanadate (V) which is a colorless liquid, but when added to water, the solution is
yellow. This is because of the reaction:

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 Addition of acid drives the equilibrium to the right and the yellow color becomes more
intense. This is not a redox reaction because vanadium is in the +5 oxidation state in
both VO3- and VO2+.
If excess zinc is added to a solution of dioxovanadium (V) ions, a series of color changes
is observed.
Yellow → Green → Blue → Green → Purple
The solution containing yellow VO2+ ions first turns green. This is caused by a mixture of
yellow VO2+ ions and blue VO2+ ions. The solution turns blue when all the VO2+ ions
have been reduced to blue VO2+ ions, then green again as V3+ ions are formed and
finally purple when reduction to V2+ is complete.
20)

21)

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22)

23) Chemistry of chromium:

Reaction of chromium (III) complexes with aqueous sodium hydroxide:

Reaction of chromium (III) with aqueous ammonia:

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24) Redox reactions of chromium:

Reduction of dichromate (VI) to chromium (III):

Reduction of chromium (III) to chromium (II):

Oxidation of chromium (III) to chromate (VI):

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25) Interconversion of dichromate (VI) and chromate (VI):

26) Reaction of cobalt (II) complex with concentrated hydrochloric acid:

27) Reaction of copper (II) complex with concentrated hydrochloric acid:

When the acid is added slowly and continuously, the color gradually changes from blue
to green due to a mixture of [Cu(H2O)6]2+ and [CuCl4]2- and finally to yellow.
28) Fuel cells: Fuel cells are electrochemical cells in which the chemical energy of a fuel is
directly converted into electrical energy. Fuel cells differ from typical electrochemical
cells, such as dry cells and lead - acid cells, in having a continuous supply of reactants
from which to produce a steady electric current. Fuel cells use a variety of fuels including
hydrogen, hydrocarbons and alcohols. Inside a fuel cell, energy from the redox reaction
between a fuel and oxygen is used to create a potential difference. Hydrogen and
alcohol fuel cells have been used in the development of electric cars and in space
exploration.

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29) Advantages of hydrogen-oxygen fuel cells:
● They offer an alternative to the direct use of fossil fuels such as petrol and diesel.
● Unlike fossil fuels, their products do not include pollutants, such as carbon
monoxide, carbon dioxide and oxides of nitrogen.
● They are lighter and more efficient than engines that use fossil fuels.
● quiter.

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30) Problems associated with hydrogen-oxygen fuel cells:
● Hydrogen is explosive, so great care has to be taken when transporting it.
● Requires larger storage tanks.
● Needs to be stored under high pressure, so there is a risk of explosion.
31) Alcohol fuel cells:

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 Topi 17 - Transitio Metal & eir Chemistr

Pleas Rea Mai Note rs Befor Readin es

1) Transition metal element:

● D-block element
● At least one stable ion with an incompletely filled d-subshell.
2) Transition metals and their chemistry:
D-block element: It is an element in which the last electron goes to fill the d-orbital. The
elements between group 2 and group 3 are d-block elements.
Transition metal element: It is a d-block element which has at least one stable ion with
an incompletely filled d-subshell.
For example:
1. Sc (z = 21) = [Ar] 3d1 4s2
Sc3+ (z = 21) = [Ar] 3d0 4s0
Therefore, Sc is not classified as a transition metal element.
2. Zn (z = 30) = [Ar] 3d10 4s2
Zn2+ (z = 30) = [Ar] 3d10 4s0
Therefore, Zn is not classified as a transition metal element.
When a d-block element loses electrons and forms a positive ion, the outer s-electrons
are always lost before any d-electrons. Losing all the 4s electrons makes the ion smaller
than if it had lost its 3d electrons. This means that the lattice energy and the hydration
enthalpy are more exothermic. Therefore, in a reaction, the overall ΔH is more
energetically favorable than if the 3d electrons had been lost.
3) Properties of transition metals:
1. Form ions with different oxidation numbers.
2. Form colored ions and colored compounds.
3. Form complex ions and complex compounds.
4. Have high melting and boiling temperatures.
5. Some transition metals and their compounds can act as catalysts.

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4) Successive ionisation of d-block elements:

The energy levels of the 3d and 4s electrons are very similar in d-block elements, so the
big jump comes after all the 4s and 3d electrons have been removed.
5) The reason for variable oxidation states is that the successive ionisation energy increases
steadily. For example, the extra energy required to remove a third electron from
chromium is regained in the stronger ionic bonding involving the Cr3+ ion compared with
the weaker ionic bonding by the less charged Cr2+ ion.
It can be seen that the highest common oxidation number increases from Sc3+ to Mn7+
as all the 4s and 3d electrons become involved in bonding. From Fe to Zn, the increasing
nuclear charge means that the electrons are attracted more strongly and are less likely
to be involved in bonding. Therefore, ions with higher oxidation numbers are less
common.
6) Complex ions/ complex compounds: It is an ion or a compound, in which molecules or
ions (ligans) form dative covalent bonds with the central metal atom or ion. A complex
ion can either be positively charged, negatively charged or neutral.
7) Coordination number: It is the number of near neighbouring atoms (number of dative
covalent bonds) bonded to the central ion.
8) Ligands: An ion or a molecule which forms dative covalent bonds with the central metal
atom or ion in a complex is known as a ligand.
A ligand can either be negative or neutral.
9) Monodentate ligand: One atom in a molecule or ion forms dative covalent bond with the
central metal atom or ion. For example: H2O, NH3, OH-, Cl-, Br-, I-, CN-, etc.

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10) Bidentate ligand: Two atoms in a molecule or ion form dative covalent bonds with the
central metal atom or ion. For example:

11) Hexadentate ligands: Six atoms in a molecule or ion can form dative covalent bonds with
the central metal atom or ion. For example:

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12)
Ligand Type Example Name of the
complex

H2O Aqua [Cu(H2O)6]2+ Hexaaquacopper

(II) ion

NH3 Ammine [Cu(NH3)4]2+ Tetramminecopper

(II) ion

Cl- Chloro [CuCl4]2- Tetrachlorocuprate

(II) ion

OH- Hydroxo [Zn(OH)4]2- Tetrahydroxozincate

(II) ion

CN- Cyano [Fe(CN)6]4- Hexacyanoferrate

(II) ion

CO Carbonyl [Ni(CO)4]o Tetracarbonylnickel

Cl-, NH3 Mixed [Co(NH3)Cl2]+ Tetraamminedichlo

rocobalt (II)

OH-, H2O Mixed [Fe(OH)2(H2O)4]+ Tetraaquadihydroxo

iron (II)

13) Shapes of complexes:

Coordination number Shape of the complex

6 Octahedral

4 Tetrahedral

2 Linear
For example: [Cu(H2O)6]2+

The shape is octahedral as there are six ligands/ 6 dative bonds formed. Similarly,
[Cr(H2O)6]3+, [Cr(OH)6]3-, [Cr(NH3)6]3+ are also octahedral.

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 Another example: [CuCl4]2-

The shape is tetrahedral as there are four ligands/ 4 dative bonds formed. Similarly,
[NiBr4]2-, [CoCl4]2- are also tetrahedral.
Another example: Pt(NH3)2Cl2

Other examples:

14) Origin of color in transition metal ions:

In an isolated metal atom or ion, the 5 d-orbitals are degenerate, that is, all 5 d-orbitals
are at the same energy level.
In a complex ion, d-orbitals differ slightly in energy as a result of overlapping differently
with the ligands, that is, the d-orbitals become non-degenerate.

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 Electrons move from the lower energy d-orbital to higher energy d-orbital by absorbing
energy from the light and if the frequency of light absorbed in these energy transitions is
in the visible region, only then ions appear colored. The color of the ions is
complementary to the colors absorbed.
15) Effects of ligands on color: A strong ligand splits the d-orbitals in the complex ion to a
greater extent than a weak ligand does.

Relatively, weaker ligands like H2O are replaced by stronger NH3 ligands. The absorption
moves from orange towards yellow and the color of the complex changes from blue to
violet-blue.
16) Effect of oxidation number of the transition metal ion on color:
An ion with a high charge density will attract a ligand strongly, so the splitting of the
d-orbitals will be greater.
17) Effect of change in coordination number on color:
The splitting of d-orbitals differ with changes in coordination number and thus the color
will also change.

18) Hydroxides on transition metal cations:

If a small amount of NaOH/ KOH/ NH3 solution is added to a solution of transition metal
cations, a precipitate is formed.
If more NaOH/ KOH/ NH3 solution is added to the precipitate, some of the precipitates
dissolve.

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19)
Cations Formula of Color of Reaction with Reaction with
precipitate precipitate excess NaOH excess NH3

Cr3+ (aq) Cr(OH)3 Green [Cr(OH)6]3- (aq) [Cr(NH3)6]3+ (aq)

(Green) (Green)

Mn2+ (aq) Mn(OH)2 Beige/ Off-white - -

Fe2+ (aq) Fe(OH)2 Mud-green - -

Fe3+ (aq) Fe(OH)3 Red-brown - -

Co2+ (aq) Co(OH)2 Blue (turns pink - [Co(NH3)6]2+ (aq)

on standing) (Brown)

Ni2+ (aq) Ni(OH)2 Green - [Ni(NH3)6]2+ (aq)

(Pale blue)

Cu2+ (aq) Cu(OH)2 Blue - [Cu(NH3)4]2+ (aq)

(Deep/royal blue)

Zn2+ (aq) Zn(OH)2 White [Zn(OH)4]2- (aq) [Zn(NH3)4]2+ (aq)

(Colorless) (Colorless)
● The beige/ off-white precipitate turns brown on standing. Mn(OH)2 is oxidised to
MnO2 (brown) by the oxygen in air.
● The mud-green/ dirty-green precipitate turns red-brown at the surface as
Fe(OH)2 is oxidised to Fe(OH)3 (red-brown) by the oxygen in air.
● Cr(OH)3 and Zn(OH)2 are amphoteric and that is why they can react with excess
NaOH despite being bases.
20)

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 The position of the 2nd equilibrium lies to the left. A small amount of precipitate
appears in the solution due to the hydrolysis shown above. Due to the hydrolysis of the
complex, some oxonium ions are formed and hence, the solution becomes acidic.
If an alkali, that is, NaOH solution is added to this solution, the OH- ions react with the
oxonium ions (H3O+) and form water. So, the position of both the equilibria shift from left
to right and the precipitate of Cu(OH)2(H2O)4 appears.
As the alkali neutralises oxonium ions, this type of reaction is called a neutralisation
reaction.
OH- ions also remove protons from coordinated water molecules and thus this type of
reaction is called a deprotonation reaction.
21)

Type of reaction: Deprotonation reaction

High charge density of a cation in a complex allows it to withdraw electrons from the
coordinated water molecules which makes the hydrogen atom more electropositive and
thus the hydrogen atom can be removed more easily by water molecules/ hydroxide
ions outside the coordination.
22) When a small amount of ammonia solution is added to a solution of copper (II) ions,
deprotonation occurs.

23) If excess ammonia solution is added to the blue precipitate of Cu(OH)2(H2O)4, the
precipitate dissolves to form a deep blue solution.

Type of reaction: Ligand exchange.

24) Reaction of transition metal cations with NaOH/ KOH (aq):
Chromium (III), Cr3+:

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Manganese (II), Mn2+:

Iron (II), Fe2+:

Iron (III), Fe3+:

Cobalt (II), Co2+:

Zinc (II), Zn2+:

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25) Reaction of transition metal cations with ammonia solution:
Chromium (III), Cr3+:

Manganese (II), Mn2+:

Iron (II), Fe2+:

Iron (III), Fe3+:

Cobalt (II), Co2+:

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 Nickel (II), Ni2+:

Copper (II), Cu2+:

Zinc (II), Zn2+:

26) Solution of iron (II) ions:

27) Solution of iron (III) ions:

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 If Na2CO3 is added to a solution of iron (III) ions, effervescence of CO2 gas is observed
and red-brown precipitate of Fe(OH)3(H2O)3 appears.
If Na2CO3 solution is added to a solution of iron (II) ions, no effervescence is observed
and a green precipitate of FeCO3 appears.
The iron (III) ions have a higher charge density, the electrons in the water molecules are
pulled towards the highly polarising Fe3+ ion, making it easier for the water molecules
linked to the iron ion to give away protons. It is a strong acid to form CO2 when added to
a solution of sodium carbonate.
28) A transition metal can act as a catalyst because its incompletely filled d-orbitals/ its
energetically available d-orbitals can accept electrons from a reactant molecule or its
d-electrons can form a bond with a reactant molecule.
Transition metal ions/ compounds make good catalysts because they can change
oxidation number by gaining or losing electrons within their d-orbitals.
29) Heterogeneous catalysts: A heterogeneous catalyst is in a different phase from the
reactants and the reaction occurs on the surface of the catalyst. Many industrial
processes use transition metals or their compounds as heterogeneous catalysts. For
example: In the Haber process, iron in the solid state is used to catalyse the reaction
between hydrogen and nitrogen gases.
30) How a solid heterogeneous catalyst works:
1. Reaction occurs on the surface of the catalyst.
2. Reactant molecules bind to the surface of the catalyst at specific points known as
active sites.
3. Binding of the reactant molecules with the catalytic surface makes the covalent
bonds within the reactant molecules become weaker, as a result, less energy is
required to break the bonds, that is, activation energy is lower.
4. Products form and leave the catalytic surface.
31) Stages in heterogeneous catalysts:
1. Adsorption
2. Reaction
3. Desorption
32) Transition metal catalysts work by providing active sites onto which the reactant
molecules can bond.
Some heterogeneous catalysts work because of the variable oxidation state of the
transition metal. For example: Vanadium (V) oxide is used as the catalyst in the oxidation
of sulfur dioxide to sulfur trioxide in the manufacture of sulfuric acid by the contact
process. The sulfur dioxide is oxidised by the vanadium (V) oxide, which is reduced to
vanadium (IV) oxide.
33) Homogeneous catalysts: Homogeneous catalysts are in the same phase as the reactants.

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 Homogeneous catalysts work by combining with the reactants to form an intermediate
species which then reacts to form the products and reform the catalyst.
34) Haemoglobin:

● Haemoglobin consists of three main parts, the largest of which is protein (the
‘globin’ part).
● Within the protein, there are four haem groups that are made up mostly of
carbon and hydrogen atoms.
● Inside each haem group, there are four nitrogen atoms that hold an Fe2+ ion by
forming dative bonds with it in a square planar structure.
● There is a fifth dative bond from the protein to the Fe2+ ion.
● When blood passes through the lungs, haemoglobin collects oxygen molecules
and transports them to cells, where it is released.
● When haemoglobin collects oxygen, the oxygen molecule acts as a ligand by
using one of its lone pairs of electrons to form a dative bond with one of the Fe2+
ions.
35) Haemoglobin and carbon monoxide:
A carbon monoxide molecule has a lone pair of electrons on its carbon atom that
enables it to act as a ligand. The strength of the dative bond between oxygen and
haemoglobin is not particularly strong, but the advantage of this is that the oxygen
molecule is relatively easily released when it is needed.

Unfortunately, a much stronger dative bond forms between carbon monoxide and
haemoglobin, and so any carbon monoxide breathed in is very likely to replace the
oxygen already bound to haemoglobin - this is a ligand substitution reaction. Once the
carbon monoxide has formed carboxyhaemoglobin, the dative bond is so strong that it
does not break easily. This means that if enough haemoglobin molecules are converted
to carboxyhaemoglobin, there may be too little oxygen transported to support
Life.

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 Oxygen + Haemoglobin ⇋ Oxyhaemoglobin
Carbon monoxide + Haemoglobin → Carboxyhaemoglobin
36) The oxidation of ethandioic acid by manganate (VII) ions:
5(COOH)2 + 2MnO4- + 6H+ (aq) → 10CO2 (g) + 2Mn2+ (aq) + 8H2O (l)
The reaction is very slow at room temperature but it is catalysed by Mn2+ ions. The Mn2+
ions are not present initially, so the reaction starts off extremely slowly at room
temperature. As soon as it is produced in a catalytic amount, the rate of reaction
increases. This phenomenon is known as autocatalysis, in which a reaction is catalysed
by one of its products.

37) Platin, Pt(NH3)2Cl2:

The platinum complex bonds to adjacent guanine molecules in one strand of DNA in
cancer cells by a ligand exchange reaction. Each of the chloride ligands is replaced by
one of the nitrogen atoms in guanine. This prevents replication of the DNA. The
damaged cancer cell is then destroyed by the body’s immune system.
Cis-platin has a number of side effects including kidney damage and the inhibition of
hair growth.
Trans-platin is much less effective in cancer treatment than cis-platin. It is also more
toxic. So, it is important to use only the cis-isomer in the cancer treatment.
38) Stability constant: The extent to which ligand exchange reactions occur is measured by
the stability constant.

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The stability constant for complexes with bidentate and poly-dentate ligands is higher
because of greater changes in entropy of the system.

ΔSsystem becomes more positive down the reactions (1-3) as the difference in the number
of particles increases.

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 Topi 18 - Arene

Pleas Rea Mai Note rs Befor Readin es

1) The structure of benzene, C6H6:

2) Problem with Kekule’s structure:

1. The Kekule structure is expected to decolorise bromine water but benzene does
not decolorise bromine water.
2. Benzene favors substitution over addition reaction.
3. Comparison of IR spectra of aromatic compounds with those of aliphatic
compounds containing a C=C shows slight difference. The C-H absorption in
benzene is 3036cm-1 and that for C=C is 1479cm-1. The equivalents in an aliphatic
compound such as cyclohexene are 3023cm-1 and 1438cm-1.
4. X-ray diffraction of benzene revealed that all the C-C are of the same length.
C-C (Alkane) → 0.154nm
C=C (Alkene) → 0.133nm
C-C (Benzene) → 0.139nm
5. If the Kekule structure is correct, there should be 4 isomers with the molecular
formula C6H4Br2.

However, only three are known to exist. So, the two isomers with adjacent
carbon atoms are identical. This suggests that the bonds between the carbon
atoms in the benzene ring are the same.

32
 6. The enthalpies of hydrogenation are not as would be expected if benzene would
have 3 separate double bonds.
3) The best representation of a benzene molecule is six carbon atoms in a hexagonal plane
bonded to each other and each bonded to a hydrogen atom by σ-bonds. The fourth
valence electron on each carbon atom is in a p-orbital at right angles to the plane of the
six carbon atoms. The p-orbital of one carbon atom overlaps equally with the pz-orbitals
of both adjacent carbon atoms, forming a continuous π-bond above and below the ring
of carbon atoms. These six p-electrons are delocalised over the ring. This gives the
molecule greater stability compared with a theoretical molecule in which the
π-electrons are localised between individual atoms. The gain in stability is called the
resonance stabilization energy. In benzene, its value is 152kJmol-1.
4) Reactions of benzene:
Nitration of benzene/ reaction of benzene with nitrating mixture:
Nitrating mixture: Mixture of concentrated HNO3 and concentrated H2SO4.
Replacement of one or more hydrogen atoms of benzene by an equivalent number of
-NO2 groups is known as nitration.
A mixture of concentrated H2SO4 and concentrated HNO3 is known as the nitrating
mixture.
Benzene is mixed with the nitrating mixture and the mixture is heated under reflux at
55°C.
The organic product is nitrobenzene.

If the mixture is heated under reflux at 95°C, the organic product is 1,3-dinitrobenzene.

33
5)

Benzene favors substitution over addition. Substitution enables benzene to preserve its
delocalisation and thus retain the extra stability.
Addition causes benzene to lose its delocalisation which results in the loss of extra
stability.
6) Reaction of benzene with chloroalkanes/ Alkylation of benzene/ Friedel-Crafts alkylation:
Reagent: Chloroalkane
Catalyst: Anhydrous aluminium chloride
Organic product: Alkylbenzene
Mechanism and type: Electrophilic substitution

34
7) Reaction of benzene with acyl chloride/ Alkylation of benzene/ Friedel-Crafts alkylation:
Acyl chloride: Acyl chloride
Catalyst: Anhydrous aluminium chloride
Organic product: Ketone (phenylalkanone)
Mechanism and type: Electrophilic substitution

35
8) Reaction of benzene with bromine:
Catalyst: Anhydrous AlCl3/ FeCl3/ FeBr3/ AlBr3
Condition: Heat under reflux
Organic product: Bromobenzene
Mechanism and type: Electrophilic substitution

Benzene also reacts with excess bromine in presence of iron and forms bromobenzene.
Iron reacts with bromine and forms FeBr3 which catalyses the reaction between benzene
and bromine.

9) Reaction of benzene with fuming sulfuric acid: Fuming sulfuric acid reacts with benzene
and forms benzenesulfonic acid. This reaction is known as sulfonation.

36
 Fuming sulfuric acid (oleum) is concentrated sulfuric acid which contains additional SO3
(sulfur trioxide) molecules with which benzene reacts readily since SO3 is an effective
electrophile.
Condition: Warm at 40°C

10) Reaction of benzene with oxygen:

Complete combustion of benzene requires a large volume of O2. When benzene burns,
there may be insufficient O2 which results in the formation of some unburnt carbon
which makes the flame yellow and smoky.
Benzene has a high C:H ratio and thus, probability of combustion is also low.

11) Position of a substituent on a mono-substituted benzene:

37
 ● If the existing substituent (G1) is an electron-releasing group, then the new
substituent (E) is directed towards 2,4,6-positions of the benzene ring.
● If the existing substituent (G2) is an electron withdrawing group, then the new
substituent (E) is directed towards 3,5-positions of the benzene ring.
12) Reaction of benzene (containing a side-chain):

13) Properties of phenol:

1. Phenol is a white solid.
2. Phenol can form hydrogen bonds with other phenol molecules and also has
stronger dispersion forces and hence, has a higher melting temperature than
benzene.
3. Phenol dissolves in H2O, since it can form hydrogen bonds with water molecules.
4. Solubility is low due to the large hydrophobic benzene ring.

5.

38
 The lone pair of electrons on the oxygen atom gets incorporated into the ring.
This increases the electron density inside the ring, making it more susceptible to
electrophilic attacks, that is, it can be more easily attacked by an electrophile.
6. Pulling the lone pair of electrons from the oxygen atom causes the H atom to be
more electropositive than it is in aliphatic alcohols. This means the hydrogen
atom is much more easily lost from phenol than that in aliphatic alcohols. Thus,
phenol has stronger acidic properties than aliphatic alcohols.
14) Phenol is an acidic compound and thus, it can donate H+ ions when it is dissolved in
water, that is,

15) Reaction of phenol with bromine water:

Organic product: 2,4,6-tribromophenol
Observation:
● Yellow to colorless
● Formation of white precipitate with an antiseptic smell.

39
 Topi 19 - Organi Compound : Amine , Amide , Amin Acid & Protein

Pleas rea Mai Note rs Befor Readin es

1) Amines: Amines are organic derivatives of ammonia. If one or more hydrogen atoms of
ammonia are replaced by an equivalent number of alkyl or aryl groups, then the
resulting compound is an amine.
2) Types of amines:

3) Properties of amines:
1. The lower members of the homologous series of alkyl amines are either gases or
volatile liquids.
2. Primary and secondary amines are able to form intermolecular hydrogen bonds.
3. Hydrogen bonding is not possible in tertiary amines (as there is no hydrogen
atom or nitrogen). Permanent dipole force and dispersion forces exist between
tertiary amine molecules and thus, tertiary amines have a lower boiling
temperature than primary and secondary amines.
4. Aryl amines, such as phenyl amines are much less volatile and are usually liquids
at room temperature. They are only slightly soluble in water because the
hydrophobicity of the benzene ring outweighs the tendency of the -NH2 group to
form hydrogen bonds with water but they do dissolve in organic and non-polar
solvents.
5. Amines are soluble in water as hydrogen bonds can be formed with H2O
molecules.
4) Preparation of amines (primary):
Reduction of nitriles:
Reducing agent: LiAlH4
Conditions:
● Dry ethoxyethane (ether)
● Acid hydrolysis (dilute)

40
 Organic product: Primary amine

5) Reaction of halogenoalkane with concentrated ammonia:

A mixture of concentrated ammonia (dissolved in ethanol) and halogenoalkane is heated
in a sealed tube.
The organic product is a primary amine when ammonia is taken in excess.

If ammonia is not in excess, a mixture of organic products are obtained.

41
6) Preparation of aromatic amines:
Phenylamine (an aromatic amine) is made by the reduction of nitrobenzene.
Reducing agent: Tin and concentrated HCl
Condition: Heat under reflux

The phenylamine formed reacts with acid (HCl) and forms phenylammonium ion.

The reaction is cooled to room temperature and an excess of NaOH solution is added.

The mixture is then steam distilled to remove the phenylamine from the sludge of tin
hydroxides.
7) Reaction of primary amines with aqueous hydrogen ions:
Ammonia is a base since it can accept a proton, that is,

Primary aliphatic amines are stronger bases than NH3 because alkyl groups are electron
releasing and thus the nitrogen atom in primary amines can accept a proton more easily
than that in NH3.

Phenylamines are weaker weaker bases than NH3 as the lone pair of electrons on the
nitrogen atom interacts with the delocalised π system in the ring. And as a result, the
lone pair on the nitrogen atom is less available. This reduces the ease of acceptance of
protons by the -NH2 group.

42
8) Order of basicity:

9) An aqueous solution of amine is alkaline.

Phenylamine is almost insoluble in water but soluble in dilute acid solution.

The benzene ring in phenylamine is hydrophobic which makes phenylamine almost
insoluble in water.
Phenylamine reacts with acid and forms a cation which attracts the δ- oxygen atoms of
H2O molecules more strongly.

10) Reaction of phenylamines with nitrous acid:

Phenylamine reacts with sodium nitrite and concentrated hydrochloric acid between 0°C
to 5°C and forms benzenediazonium ion.
NaNO2 reacts with concentrated HCl and forms nitrous acid (HNO2) which then reacts
with phenylamine.
HNO2 is unstable and hence, it is prepared whenever it is required.

43
11) Structure of benzenediazonium ion:

● Above 5°C, this ion decomposes giving nitrogen gas (N2).

● Below 0°C, the reaction is too slow or the reaction does not occur. So, a suitable
temperature is maintained using an ice-bath.
12) Reaction of benzenediazonium ion with phenol:
Organic product: Azo dye
Condition: Dilute NaOH (or any alkaline solution)

44
 Azo dyes can form hydrogen bonds with groups in cotton and wool and so bind strongly
to the fabric. This makes benzenediazonium compounds useful in dyes.
13) Reaction of amines with acid: Amines react with strong acids to form ionic salts.

14) Reactions of 1° amines with ethanoyl chloride:

Organic product: Secondary amide

15) Reaction of primary amines with aqueous copper (II) ions:

Reaction with butylamine:

45
 Reaction with phenylamine:

16) Amino acids: Amino acid molecules contain at least one -NH2 group and one -COOH
group. Amino acids are amphoteric, that is, they have both acidic and basic properties.
17) Amino acids can be divided into three types:
1. Neutral amino acids: A molecule of a neutral amino acid contains only one basic
-NH2 group and one acidic -COOH group.
2. Acidic amino acids: A molecule of an acidic amino acid contains two -COOH
groups and one -NH2 group.
3. Basic amino acids: A molecule of a basic amino acid contains two -NH2 groups
and one -COOH group.
18) Amino acids are solid at room temperature. This is because the molecules form
zwitterions. The -COOH group in one molecule protonates the -NH2 group in another
molecule forming a species that has a positive charge at one end and a negative charge
at the other. The positive charge on one zwitterion is strongly attracted to the negative
charge of an adjacent zwitterion. The -COOH group is weakly acidic and -NH2 group is
weakly basic, so the formation of the zwitterion and the neutral molecule are present.

19) Glycine (aminoethanoic acid): Glycine is optically inactive because it does not have a
chiral center. The carbon atom next to the -COOH group has two hydrogen atoms
bonded to it. So, it cannot be chiral. Therefore, a solution of glycine has no effect on the
plane of polarisation of plane-polarised light.

46
20) Condensation: When two amino acid molecules join together, they undergo a
condensation reaction and lose one molecule of water. The resulting bond is called a
peptide bond and the resulting molecule is called a dipeptide.

When two amino acids combine together to form a dipeptide, there are always two
possibilities. For example: When glycine reacts with alanine, the -O-H could be last from
either molecule as shown below:

When one molecule of each of three different amino acids react together to form a
tripeptide, six different tripeptides are formed.

47
21) Reaction of amino acids with acids:

22) Reaction of amino acids with base:

23) Optical activity: All natural amino acids except glycine are optically active. The carbon
atom next to the -COOH group is a chiral center because it has four different groups
attached to it.
For example: Alanine (2-aminopropanoic acid) has two optical isomers.

24) Condensation polymers: Polyamides are polymers in which the monomers are linked by
an amide bond.
1. proteins: Proteins consist of a number of amino acids joined together by
peptides.

48
 Structure of proteins: The primary structure is the order of the amino acids in the
chain. They are organised into a secondary structure of which there are two
types:
● α-helix: The peptide is coiled in a spiral and the structure is held together
by intramolecular hydrogen bonds.
● ß-pleated sheet: The polypeptide chains are almost fully extended and
are held by hydrogen bonds to other polypeptide chains. The result is
rather like a stack of corrugated cardboard.
2. Nylon:
Monomers:

There are different types of nylon. This example is described as nylon-6,6

because both of the monomers contain six carbon atoms.
3. Kevlar:
Monomers:

49
25) Addition polymers:
Poly(propenamide)
Monomer: Propenamide

Poly(ethenol)
Poly(ethenol) is made by polmerising ethenyl ethanoate.

Poly(ethenyl ethanoate) is reacted with methanol in a transesterification reaction to

produce poly(ethenol).

This polymer is water soluble because of the many hydrogen bonds that can form
between the -OH groups that occur on alternate carbons atoms and water molecules.
This polymer is used to make disposable laundry bags for use in hospitals. Beddings and
clothes that might be infected with microorganisms from patients are put into laundry
bags and then the bags can go directly into the washing machine without the laundry
worker touching the possibly infected fabrics. During the washing cycle, the bag
dissolves completely and then the clothes are washed clean.

Poly(ethenol) is also used to make the liquid detergent capsules (liquitabs) which
contains measured quantities of detergent for use in washing machines. The capsules
break down and dissolve in water because the polymer chains contain many -OH groups
which form hydrogen bonds with water molecules.

50
 Topi 20 - Organi Synthesi

Pleas Rea Mai Note rs Befor Readin es

1)

Using these eight pieces of apparatus, you can create a wide variety of experimental
set-ups.
Heating is needed in many experiments. You can do this using a Bunsen burner, but
often an electric heating mantle or a hot water bath or hot oil bath is preferred for
safety reasons.
2) Simple distillation: If there is a large enough difference in the boiling temperatures of
organic substances present in a mixture, then distillation can be used to separate them.
The essential points about the apparatus are:
● A round-bottomed or pear-shaped flask containing the mixture.
● A still-head fitted with a thermometer, the bulb of which must be positioned
level with the outlet of the still-head.
● A condenser with the water going in at the bottom and leaving at the top.
● An open receiving vessel, such as a beaker, or an adaptor open to the air joined
to a flask.
● The flask is heated using an electric heater, a water or oil bath or sand tray.
● The mixture is carefully heated and the vapour that comes over at +/- 2°C of the
boiling temperature (obtained from a data book) of the particular substance is
condensed and collected.

51
3) Advantages and disadvantages of simple distillation: The advantages of using simple
distillation, rather than fractional distillation, are that it is easier to set up and is quicker.
The disadvantage is that it does not separate the liquids as well as fractional distillation.
It should only be used if the boiling temperature of the liquid being purified is very
different from the other liquids in the mixture, ideally a difference of more than 25°C.
4) Drying: A damp organic liquid can be dried by adding anhydrous sodium sulfate or
anhydrous calcium chloride or anhydrous magnesium sulfate. The initial mixture will be
cloudy but as the water is removed the liquid goes clear. The organic liquid can then be
filtered off/ decanted.
5) A drying agent removes water physically.
6) A dehydrating agent removes water chemically.
7) Boiling temperature determination: The purity of a liquid can be tested by measuring its
boiling temperature. The liquid is placed in a distillation apparatus and heated. If the
substance is pure it will boil at a constant temperature which should be that obtained
from a data book. If it is impure, it will boil over a significant range of several degrees.
8) Pure liquid → +/- 1°C or +/- 2°C
9) Impure liquid → Boils over a large temperature.
10) Safety issues:
Safety precautions and the reasons behind them include the following:
● Distillation and heating under reflux must be carried out in a fume cupboard if
the vapour of one of the reactants or products is harmful, poisonous (toxic) or
irritant. This applies to halogens, hydrogen halides, halogenoalkanes and
ammonia.
● If a mixture is being heated under reflux or distilled, there must be some outlet
to the air. If there is not, pressure will build up in the apparatus, which will then
fly apart, spraying hot, flammable, and often corrosive, liquid around.
● Gloves must be worn when corrosive substances are used. Such substances must
always be handled with care. This applies to concentrated acids and alkalis.

52
 ● The flask should never be heated with a naked Bunsen flame. This is because
almost all organic substances are flammable and if the liquid being heated were
to spill over or the flask to crack, a fire would result.
11)

1. A solvent is chosen in which the solid is soluble in the hot solvent and insoluble
in the cold solvent.
2. The impure solid is dissolved in a minimum volume of hot solvent (in order to
make a saturated solution so that upon cooling, maximum amount of crystals can
be obtained).

3. The solution is filtered hot through a fluted filter paper, using a warmed stemless
funnel, into a conical flask. This removes insoluble impurities.

4. The solution is then allowed to cool so that crystals form.

5. The crystals are filtered off using a Büchner funnel and the filtration is carried out
under reduced pressure. Reduced pressure is achieved by the use of a suction
pump. This removes insoluble impurities.

53
 6. The crystals are then washed with a small amount of cold solvent in ogre to
remove soluble impurities from the crystal surface.

7. The crystals are then dried in a dessicator.

● It is preferable to dry solids in a dessicator rather than heating in an oven
as some solids decompose at high temperatures.
● When the saturated solution cools down, the soluble impurities do not
crystallise since the solution was saturated with the desired materials, not
with the impurities.
12) Solvent extraction is used to separate an organic compound from inorganic substances.
For example: The reaction of pentan-1-ol with PCl3

POCI3 has a boiling temperature of 105°C and 1- chloropentane has a boiling

temperature of 108°C.
Since the boiling temperature of the two substances are similar, it is not possible to
separate the substances by distillation or fractional distillation.
The organic product is separated by adding ethoxyethane.
The solvent dissolves 1-chloropentane but not POCI3.
The ethoxyethane layer is separated from the POCI3 layer using a separating funnel.
The solution of 1-chloropentane in ether is then washed with aqueous Na2CO3 solution
and then with water. Na2CO3 neutralizes any HCI in 1-chloropentane and water washes
off any salt or Na2CO3. The aqueous layer is discarded from the separating funnel.
It is then dried with anhydrous CaCl2 and the ether is distilled off by gentle warming.
13) Steam distillation is used to extract a volatile liquid that is immiscible with water. It is
particularly useful for obtaining a substance that would decompose at its boiling point. It
is used to extract perfumes from fruits and flowers.

54
14) Boiling temperature determination:
The boiling temperature of an organic liquid can be determined and the value compared
with those in a database. The apparatus for measuring the boiling temperature is shown
in the figure. If large amounts are available, the boiling temperature can be measured
using standard distillation apparatus.

Procedure:
● Place a small amount of the test liquid in the ignition tube and, using a rubber
band, attach it to the thermometer.
● Place the capillary tube in the liquid, with its open end below the surface.
● Clamp the thermometer in the beaker of water.
● Slowly heat the water, stirring all the time. When the stream of bubbles coming
out of the capillary tube is rapid and continuous, note the temperature and stop
heating.

55
 ● Allow the beaker of water to cool, stirring continuously. Note the temperature
when bubbles stop coming out of the capillary tube and the liquid begins to suck
back into the capillary tube.
● The average of these two temperatures is the boiling temperature of the liquid.
15) Melting temperature determination:

Procedure:
● Insert some of the pure solid into a capillary tube and then attach the tube open
end upwards to a thermometer with a rubber band.
● Place the thermometer into a bath of liquid. The liquid must boil at a higher
temperature than the melting temperature of the solid being tested.
● Slowly heat the liquid bath, with constant stirring, and observe the solid in the
capillary tube. Note the temperature when the solid melts.
A test for purity is that a solid has a sharp melting temperature rather than melting over
a range of temperatures.
16) Increase in carbon chain-length:
1. Reaction of halogenoalkanes with KCN:
Reagent: KCN
Conditions:
● Ethanoic medium
● Heat under reflux
Mechanism and type: Nucleophilic substitution

2. Reaction of carbonyl compounds with HCN:

Mechanism and type: Nucleophilic addition

56
 3. Friedel-Craft alkylation/ Acylation:
Reagent: Halogenoalkane/ Acyl chloride
Condition: Anhydrous AlCl3 (catalyst)
Mechanism and type: Electrophilic substitution

17) Decrease in carbon chain-length:

1. Reaction of 1° amide with bromine and alkali:
Condition: Heat under reflux
Organic product: 1° amine with 1 carbon less than the corresponding amide

2. Reaction of carbonyl compounds with HCN:

Mechanism and type: Nucleophilic addition

18) Iodoform reaction:

Reagents: Iodine solution and NaOH solution.

57
19) Preparation of Grignard’s reagent: Magnesium metal is added to a solution of a
halogenoalkane dissolved in dry ethoxyethane and the mixture is heated under reflux.
The magnesium reacts vigorously and dissolves to form a compound, alkyl magnesium
halide.

● Grignard reagents are unstable and must be prepared immediately before use.
● Grignard reagents react with water, so they are both made and used in a solvent
of dry ether.

Once a Grignard reagent has been made, it can then be converted into a range of
organic compounds, depending on the reagent used.
20)
Grignard reagent with Organic Product

Carbon dioxide Carboxylic acid

Methanol Primary alcohol

Any other aldehyde Secondary alcohol

Ketone Tertiary alcohol

58
21) Reaction of Grignard reagent with carbon dioxide:

22) Reaction of Grignard reagent with methanol:

59
23) Reaction of Grignard reagent with aldehyde:

24) Reaction of Grignard reagent with ketone:

60