Physical Chemistry Module

PHYSICAL
CHEMISTRY
MODULE
ZIMBABWE
SCHOOL OF
MINES
PHYSICAL CHEMISTRY
TABLE OF CONTENTS.
CHAPTER 1
1.0 INTRODUCTION TO THERMODYNAMICS……………………………..…………….5
1.1. Importance of thermodynamics……………………………………………..……….......5
1.2. Limitations of thermodynamics…………………………………………………..……....5
1.3 THERMODYNAMIC TERMS…………………………………………………..………...6
1.4. ENTHALPY OR HEAT CONTENT (H)……………………………………………..….10
1.5. WORK, HEAT AND ENERGY……………………………………………………...…..10
1.6. HEAT CAPACITY………………………………………………………………….……..10
1.7. FIRST LAW OF THERMODYNAMICS…………………………………………………10
1.8. THE SECOND LAW OF THERMODYNAMICS……………………………..…………13
1.8.1.Defination………………………………………………………………………………...13
1.8.2.Entropy…………………………………………………………………………………...14
1.8.3. Chemical reactions as dispersers of energy………………………………………….....14
1.8.4.Entropies of Substances………………………………………………………………….14
1.8.5.Changes of Entropy ………………………………………………………………….....15
1.8.6.Change of entropy in the surroundings………………………………………………....15
1.8.7.The Gibbs Free Energy function( ∆G)……………………………………………..…..16
1.8.8.Uses of the Gibbs function......................................................................................16
1.9. COMMERCIAL EXTRACTION OF METALS……………………………………..……17
1.9.1. Energetic stability...........................................................................................................17
1.9.2.Variation of the Gibbs function with temperature…………………………………...…17
1.10. THERMOCHEMISTRY…………………………………………………………………22
1.10.1 Definition……………………………………………………………………………….22
1.10.2. Standard enthalpy changes……………………………………………………………22
1.10.3 First law of thermodynamics………………………………………………………….23
1.10.4. The energetic of crystals...............................................................................................25
1.10.5 Enthalpy of solution……………………………………………………………………27
1.10.7 The temperature dependence of reaction enthalpies………………………………….28
1.10.8 Chemical equations…………………………………………………………………....29
1.10.9 Bond enthalpies………………………………………………………………………..29
1.10.10 Determination of bond energies……………………………………………………..31
CHAPTER 2
2.0. CHEMICAL EQUILIBRIA………………………………………………………........32
2.1 Reversible Reactions………………………………………………………………………32
2.2 Chemical Equilibrium…………………………………………………………………….32
2.3. Homogeneous and Heterogeneous equilibrium…………………………………………33
2.4 Experimental determination of equilibrium constant……………………………………34
2.5 Dalton’s law of partial pressure. ……………………………………………………........37
2.6 Uses of equilibrium constants……………………………………………………………..38
2.7 Le Chatelies Principle……………………………………………………………...…........38
ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 2

PHYSICAL CHEMISTRY
2.8. Effects of Conditions………………………………………………………………………38

2.9.Factors affecting yield of Ammonia………………………………………………….……40
2.10 .CONTACT PROCESS……………………………………………………………..….…41
CHAPTER 3
3.0. REACTION KINETICS……………………………………………. ……………………43
3.1. Measurement of reaction rates…………………………………………………………...43
3.2. Factors that affect the rate of chemical reactions……………………………………….44
3.3 Order of a reaction…………………………………………………………………………45
3.4.Integrated and Differential Rate Laws……………………………………………………46
3.5. Second order reaction…………………………………………………………………….47
3.6. Application of rate laws………………………………………………………………….49
3.7. Determination of orders of reactions…………………………………………………….49
3.8. Reaction mechanism……………………………………………………………………..50
3.9. Activation energy, Collision theory and catalysis……………………………………….51
CHAPTER 4
4.0 ELECTROCHEMISTRY...............................................................................................57
4.1 ELECTRO-MOTIVE FORCE (E.M.F.) OF CELLS……………………………………...
4.2. Equilibria in complex ion system. ……………………………………………………….65
CHAPTER 5
5.0 IONIC EQUILIBRIA……………………………………………………………………69
5.1. ACIDS AND BASES…………………………………………………………………….69
5.1.1. Water and amphoteric behavior……………………………………………………......69
5.1.2. Ionic product water……………………………………………………………………..70
5.1.3. Salt hydrolysis…………………………………………………………………………...71
5.2. STRENGTH OF ACIDS AND BASES……………………………………………………72
5.2.1. Hydrogen Halides……………………………………………………………………….72
5.3. Organic acids………………………………………………………………………….......73
5.4. Acid – base titrations…………………………………………………………………......74
5.5. Indicators…………………………………………………………………………………..81
5.5.1. Choice of indicators……………………………………………………………………..81
5.6.1. Acid Buffers……………………………………………………………………………..82
5.6.2. Basic Buffers…………………………………………………………………………….82
5.6.3. Action of an acid buffer……………………………………………………………......83
5.7. Sparingly soluble salts……………………………………………………………………83
5.7.1. Solubility and Solubility product………………………………………………………83
5.7.2. Relationship between solubility and Ksp……………………………………………...85
5.7.3. Common ion effect………………………………………………………………….….85
CHAPTER 6
6.0. ELECTROLYSIS………………………………………………………………………...86
6.1.0.Faraday’s 1stlaw of electrolysis…………………………………………………………86
6.1.1. Faraday ‘s2nd law of electrolysis………………………………………………………..86
PHYSICAL CHEMISTRY
6.2. Mechanism of electrolysis…………………………………………………………….......88

6.4. Electrode process at the anode…………………………………………………………….89
6.5. Concentration effect……………………………………………………………………….90
6.6. Overvoltage effect…………………………………………………………………….......90
6.7. Alternative electrode at the anode…………………………………………………….….90
6.8. The industrial importance of electrolytic methods……………………………………....90
CHAPTER 7
7.0.PHASE EQUILIBRIA…………………………………………………………………......91
7.1. Phase (p)……………………………………………………………………………….......91
7.2. Component(c)……………………………………………………………………………..91
7.3. Degrees of freedom (f)/variance ………………………………………………………….91
7.4. Phase equilibrium involving a single system…………………………………………….91
7.5. Phase diagrams…………………………………………………………………………….92
7.6. Vapour pressure of ideal solutions…………………………………………………….....93
7.7. Variation of total pressure with mole fraction…………………………………………...94
7.8. Boiling point –composition diagram for ideal solutions………………………………..96
7.10 Industrial distillation ………………………………………………………………….....98
7.11. Non- Ideal mixtures………………………………………………………………………103
7.12. SOLID-LIQUID PHASE DIAGRAMS: TIN AND LEAD…………………………….107
7.13.The phase diagram……………………………………………………………………….112
7.14. Ice and Salt……………………………………………………………………………......118
8.0. References…………………………………………………………………………………121
CHAPTER 1

PHYSICAL CHEMISTRY
1.0 INTRODUCTION TO THERMODYNAMICS
Thermodynamics means the branch of science which deals with the conversion of heat into
mechanical work and vice versa. Thermodynamics can also be defined as energy changes that
accompany a process. In chemical thermodynamics, the study is confined to energy changes
accompanying chemical reactions.
1.1 Importance of Thermodynamics
In engineering the use of thermodynamics lies in its ability to predict the maximum efficiency of
various types of heat engines and maximum work obtainable from a given fuel i.e., in problems
of combustion and power.
(i) It helps to predict the feasibility of a physical or chemical process under a given
set of conditions.
(ii) It helps to predict the extent to which a reaction would take place before the
attainment of equilibrium. It is also possible to predict the yields of products with
the help of certain mathematical relations derived from the knowledge of
thermodynamics.
(iii) From the Laws of thermodynamics, some important generalization of physical
chemistry can be deduced.
For example:
a) Raoult’s law of lowering of vapour pressure
b) Expressions for elevation in boiling point, depression in freezing point
c) Nernst distribution law
d) Phase rule
e) Law of chemical equilibrium e.t.c. can all be deduced from the laws of
thermodynamics.
1.2 Limitations of Thermodynamics
(i) Thermodynamics helps to predict the feasibility of a process but does not tell
anything about the rate at which the process would proceed or the time taken for
the process to complete (which is a province of chemical kinetics).
(ii) It throws no light on the mechanisms of a process to individual atoms or
molecules but are applicable only to matter in bulk.
1.3 THERMODYNAMIC TERMS

PHYSICAL CHEMISTRY
1.3.1. System : It is defined as the part of the universe which is selected for study and is
separated from the rest of the universe by a definite boundary.
1.3.2. Types of Systems
There are two broad classes which depend on :
a) Homogeneity
b) How it interacts with surroundings
a) (i) Homogeneous System:

It is uniform throughout and consist of only one phase. For example, a system
consisting of pure mixture of gases.
(ii)Heterogeneous System:
It is not uniform throughout and consists of more than one phase. There exist a sharp
boundary between different phases. For example, a mixture of two immiscible
liquids.
b) There are three different types on the interaction with the surroundings.
(i) Open System: Exchange of both matter and energy is possible. Due to these
exchanges matter and energy do not remain constant in open systems. For
example, liquid taken in a beaker.
(ii) Closed System: A system which can exchange energy but not matter with the
surroundings. Thus, in a closed system matter remains constant and only the
energy changes. For example, hot liquid taken in a closed metallic flask.
(iii) Isolated System: It is a system where there is no interaction with the
surrounding. Both mater and energy of such systems remain constant, for
example a Dewar flask.

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1.3.3. Surroundings
The rest of the universe, other than the system is known as surroundings, system and
surroundings may or may not be in a position to exchange energy or matter.
1.3.4.Properties of a System
a) Extensive property of a system depends on the amount of substance present in the

system. For example, volume, mass, internal energy, free energy, enthalpy energy,
entropy energy and heat capacity.
b) Intensive property of a system does not depend upon the amount of substance present in a
system. For example, density, temperature, molar entropy, molar heat capacity and other
molar properties.
1.3.5.State Variables
These are the measurable properties of s system, which completely define the state of asystem.
These are also called thermodynamic variables. For example, pressure, volume, temperature and
concentration. State variables are directly measureable from experiments and are interrelated by
an equitation of state.

PHYSICAL CHEMISTRY
pV= nRT P = pressure V = Volume n = number of moles R = Gas Constant

T = temperature
A thermodynamic system is said to be in a definite state when the state variables have definite
values. Any change in the value of these variables will change the state of the system. Change
in the state of the system is completely defined when the initial and the final states are specified.
In other words the current state of a system is independent of how that state has been prepared
(route used) or arrived at butdepends on the initial and final state of the system.
1.3.6. Process: A thermodynamic process is defined as a method of operation with the help of
which a system changes from one state to another. A process can be endothermic or exothermic.
An endothermic process uses up energy from the surroundings, whereas an exothermic process
releases energy to the surroundings
1.3.7.Other processes
a) Isothermal process: this type of process is carried out at constant temperature.
b) Adiabatic process: this type of process is carried out in a system which is closed by
adiabatic walls, where there is no heat exchange between system and surroundings.
c) Diathermic process: a process which allows energy transfer through its walls.
d) Isochoric process: the volume of the system does not change
e) Isobaric process: this type of process is carried out under conditions of constant pressure
f) Reversible process
A reversible change in thermodynamics is a change that can be reversed by an
infinitesimal modification of a variable. The system is said to be in equilibrium with its
surroundings if a small change in the conditions in opposite directions results in opposite
changes in its state. Two bodies are said to be in thermal equilibrium if the temperatures
will result in energy transfer in one direction and vice versa. If a gas is confined by a
piston and that the external pressure pex is set equal to the pressure of the confined gas
(pressure p), such a system is in mechanical equilibrium with its surroundings.A small
change in external pressure in either direction cause change in volume in opposite
direction.
g) Irreversible process
If the external pressure is very large compared to the internal pressure, then changing it
slightly will not decrease it below the pressure of the gas and so will not change the

PHYSICAL CHEMISTRY
direction of the process. The system is not in mechanical equilibrium with its
surroundings and hence the compression is thermodynamically irreversible.
1.3.8.Thermodynamicequilibrium
A system in which the observable properties of the system do not undergo any change
with time is said to be in thermodynamic equilibrium. It implies the existence of the
following type of equilibrium.
a) Thermal equilibrium: When the temperature remains the same in all parts of the
system and there is no flow of heat from one part of the system to another.
b) Chemical equilibrium: When the composition of the system (products and reactants)
remains constant and uniform throughout.
1.3.9 Internal energy (U)
The internal energy of a system is the sum of the internal energies of its constituent molecules,
which include:-
(i) Translational energy – associated with the translational motion of a molecule.

This is only significant for atoms and molecules in the gaseousand liquid
phase.
(ii) Rotational energy - associated with rotation of molecule about a centre of
gravity. Monatomic gases do not have rotational energy
(iii) Vibrational energy - associated with vibrational motions of the atoms within a
molecule. This is possessed by all polyatomic molecules in the gaseous,
liquid and solid states.
(iv) Electronic energy – associated with the electrostatic interactions between the
various charged particles that make up the molecule.Internal energy is denoted
by U and is a state function, as well as an extensive property. It can be
expressed in Joules or in ergs (1J = 107ergs). The absolute value of internal
energy cannot be measured but changes in internal energy accompanying a
process is measureable.
∆U = U final- U initial
Measurement of internal energy are done at constant volume conditions. If a system transfers
energy to the surroundings (exothermic reaction) then ∆U is negative. If the system gains heat
from the surrounding (endothermic reaction) the ∆U is positive.

PHYSICAL CHEMISTRY
1.4. ENTHALPY OR HEAT CONTENT (H)
This is the heat of reaction, which takes into account the work done when a system expand or
contracts during a reaction at constant pressure. It is related to the internal energy through a
mathematical equation namely:-
H = U + PV
Enthalpy is a state function. It has definite values which depend on the state of the system and is
independent of the path by which the state is reached at constant pressure.
∆ H = ∆U + P ∆V.
But p∆V = ∆nRT.
Therefore: ∆H = ∆U + ∆nRT.
1.5. WORK, HEAT AND ENERGY
Work, heat and energy are the basic concepts of thermodynamics and of these the most
fundamental is work. The amount of work is measured by the force multiplied by the distance.
Work is done during a process if the process could be used to bring about a change in the height
of a weight in the surroundings. In molecular terms, work is the transfer of energy that makes
use of organized motion. Energy is the capacity of a system to do work. When the energy of a
system, changes, as a result of temperature differences between it and its surrounding then
energy has been transferred as heat. The energy of a system can be increased by transferring
heat to it or by increasing its temperature.
1.6. HEAT CAPACITY
It is defined as the amount of heat (q) required to increase the temperature of the system from the
lower temperature (T1) to the higher temperature T2 divided by the temp difference (T2 – T1).
q q
C =T =
2−T 1
∆T
Heat capacity of a system is the quantity of heat required to raise the temperature of the whole
mass of it through 1o C .
Specific heat capacity is the quantity of heat required to raise the temperature of unit mass of it
through 1oC.
1.7. FIRST LAW OF THERMODYNAMICS
1) It is basically law of conservation of energy, which states that energy can neither be
created nor destroyed although it can be converted from one form to another.

PHYSICAL CHEMISTRY
2) The total energy of a system and its surroundings must remain constant although the
energy can be changed from ne form to the other. (the energy of a system depends on the
volume temperature, pressure, mass and composition).
1.7.1 Mathematical expression:
If a system whose internal energy is U absorbs amount of heat (q) and work(w) done on the
system, then the internal energy increases by and becomes
U1 + q + w = U2..
Thus: U2 = U1 +q + w
U2 - U1 = q + w
∆U=q+w
Change in internal energy = heat added to system + work done on the system.
Note: q and w are not state functions but are path functions. They depend on the path followed.
For the work done on the surrounding by the system w is negative.
∆U = q – w or q = ∆ U + w.
If the reaction is carried out at constant volume no work is done since p∆V = - w
Therefore ∆U = qv at constant volume.
If only pressure – volume work is done and the pressure is constant and equal to atmospheric
pressure then w = - p ∆V = - p (V2 – V1).
∆U = q – w
U2 – U1 = q – (p∆V)
U2 – U1 = q – (pV2 – pV1)
U2 – U1 = q – pV2 + pV1
U2 + pV2 – (U1 + pV1) = qp
H 2 – H 1 = qp
∆H = qp
Where q is heat absorbed at constant pressure denoted by qp.
Therefore :∆H = qpat constant pressure. ∆H is change in enthalpy or heat content (H).
dq
Heat capacity : C=
dT

PHYSICAL CHEMISTRY
Heat capacity at constant volume CV =

d qv dU
dT
=
dT ( ) v
Heat capacity at constant pressure Cp =

d q p dH
dT
=
dT ( ) p
The heat given to a system is needed partly to do work and change the internal energy.
1.7.2 Relationship between Cp and Cv
The Cp is usually greater than the Cv because at constant pressure part of the heat added to a
substance may be used for expansion work, whereas at constant volume all the heat is used to
raise the temperature so we divide by a larger ∆T (dT).
Cp – Cv= ( dH
dT )p-(
dT )
dU
v (i)
H = U + PV
Therefore: ( dH
dT ) p=(
dU
dT ) p+ P (
dT )
dV
p (ii)
dH
( )
Substitute value of dT p in equation (i)
Then
dU
( ) ( ) ( )
dV dU
Cp– Cv = dT p+ P dT p− dT v (iii)
Internal energy is a function of temperature and volume

U = f(T,V)
( dU )
dU= dT vdT + dV TdV ( dT ) (iv)
dU = CvdT + dV TdV ( dU ) (v)

Dividing both side of equitation (iv) by dT and keeping the pressure constant.

PHYSICAL CHEMISTRY
( dU
dT )
p=(
dT )( dT ) ( dV ) ( dT )
dU dT
+
dU dV
T p (vi)
dU
( )
Putting the value of dT p from (vi) in equitation (iii)
dU
( ) ( ) ( dVdT ) p+ P ( dVdT ) p−( dU
dU
Cp -Cv = dT v+ dV T
dT )
v .
=( dT ) p [( dV )T + P ]
dV dU
(vii)
For ideal gases ( dU

dV )
T =0
Therefore Cp – Cv= P ( dVdT ) p (viii)
But pV= nRT and V= ( nRTp )

( dVdT ) p=( nRp ) (ix)
From equation (viii) and (ix)
Cp – Cv = P x nR
P
Therefore Cp – Cv =nR for ideal gases
1.8. THE SECOND LAW OF THERMODYNAMICS
1.8.1.Defination

PHYSICAL CHEMISTRY
1) States that the entropy of an isolated system increases in the course of a spontaneous
change.
∆Stotal¿ 0
S is the total entropy of all parts of the isolated system. The units are JK -1. Sm○ is the standard
molar entropy. The units are JK -1mol-1
2) Heat cannot pass from a cooler body to a warmer body.

3) Heat cannot be completely converted into work, without leaving changes either in the
system or in the surroundings.
4) It is impossible to convert heat from a source by a cyclic process, without transferring it
to a colder sink. The second law deals with natural direction of change i.e. why a
reaction runs in one direction and not the other.
1.8.2.Entropy
Entropy is a measure of the randomness or disorder of the molecule of the system. It is a

thermodynamic state quantity i.e. ∆ S = Sf – Si.
For spontaneous process Sf¿Si or ∆ S¿ 0
The standard molar entropy is the entropy of a unit amount of a substance when it is in dispersal
its standard state at a specified temperature.
All natural changes are accompanied by an increase in the dispersal of energy. Energy that is not
dispersed is thought to be confined to a small location as dispersed energy is spread more widely.
For example, the cooling of a hot metal to the temperature of the surroundings. In chemistry the
concern is on the natural direction of chemical reactions, that is whether chemical reactions are
spontaneous or not.
1.8.3. Chemical reactions as dispersers of energy
The rusting of iron is exothermic and disperses energy into the surroundings. The decomposition
of dinitrogentetraoxide is endothermic and uses up energy from the surroundings.
1) 4Fe(s) + 3O→2Fe2O3(s) ∆ H =-1648KJ mo1 -1

2) N2O4(g) ↔2NO2(g) ∆ H = +57.2 KJ mol-1
The natural direction of change in the reaction is from the bonds holding the metal and in the
molecules of Oxygen (O2) to produce the products whereas some energy remains in a highly
ionized solid iron (iii) oxide, 1648 KJ of energy, for every mole of iron (iii)oxide produced has

PHYSICAL CHEMISTRY
dispersed and spread into the surroundings. The second reaction is endothermic. For every mole
of nitrogen dioxide formed 57.2 KJ are absorbed from the surroundings.
1.8.4.Entropies of Substances
The molar entropies of gases at 1atmosphre at 25 oC are roughly the same but are larger than
those of solids. The energy of a solid is confined to a small region (the volume is occupies).
Entropies of complex molecules are high for example, sucrose molecules have many atoms and
the energy is dispersed among them.
Standard Molar entropies are in the order.
Gases ¿ Liquids ¿ Solids
1.8.5.Changes of Entropy
The entropies of the products is equal to the sum of the molar entropies of the products minus the
sum of the molar entropies of the reactants.
∆Sreaction=∑S0products -∑Soreactants
CaCO3(s) → CaO(s) + CO2(g)
S0(298K)/JK-1mol-1 +92.9 +39.7 +213.6
∆Sreac=(39.7+213.6) -92.9
= +160.4JK-1mol-1
There is an increase in entropy from +92.9Jk-1 mol-1 to +160.4 JKI-1 mol-1. This is because of the
formation of the gaseous product carbon dioxide, i.e. an increase in disorderliness.
4Fe(s) + 3O2 → 2Fe2O3(s) ∆ H =-1648KJ mo1 -1
S0(298K)/JK-1mol-1 27.3 205 87.4
∆S0(298K) = 2(87.4)-[ 4 ( 27.3 )−3 ( 208 ) ]

= -594 JK-1
-594JK -1 is a large decrease in entropy. This is because a highly dispersed oxygen molecule O 2
reacts to form a more compact solid.
1.8.6.Change of entropy in the surroundings
The change of entropy in the surroundings can be expressed in terms of the enthalpy change of
reaction and absolute temperature. The heat that enters the surroundings at constant pressure is
qpwhich is equal to ∆H.
∆H = qp
q' ∆H
∆Ss= Therefore ∆S= - exothermic reaction
T T

PHYSICAL CHEMISTRY
For rusting of iron. 1648 KJ are dispersed to the surrounding.
( )
3
∆H −1648 x 10
Therefore: ∆S(surroundings) = - =− =5529 J K −1
T 298
For dinitrogentetraoxide 57,7KJ are taken from the surroundings.
Therefore: ∆S(surrounding) = - ( ∆TH ) = - 57.7 x 103

298
= - 192JK-1
Spontaneous exothermic reactions are given by large quantities of entropies they generate in the
surroundings. Whilst spontaneous endothermic reactions are given by large quantities of
entropies they generate in the reaction mixture itself.Exothermic reactions increase the entropy
of the surroundings, while endothermic reactions decrease the entropy of the surroundings.
∆Stotal = ∆Ssurrounding+ ∆Ssystem
∆H
=- + ∆Ssystem
T
- T∆Stotal = ∆H - T∆Ssystem
∆G = ∆H - T∆S
1.8.7.The Gibbs Free Energy function( ∆G)
It is defined as:
∆G = ∆H - T∆S
Where: ∆G is the Gibbs’ free energy, ∆H is the enthalpy change, ∆S is the entropy change and
T is the temperature
Gibbs free energy is a state function and it is also an extensive property of the system. It is
dependent on the quantity of the matter and on the nature of the system.
Standard molar Gibbs’ function of formation ∆G ◦f,m. is the change of Gibbs function when one
mole of a substance of a compound is formed from its elements all species at their standard state
at the specified temperature.
1.8.8.Uses of the Gibbs function
1.8.8.1. Spontaneity of chemical reactions.
The Gibbs function tells us at a glance whether or not a reaction has a tendency to occur. A
reaction has a natural tendency if the change in Gibbs function is large and negative (i.e. the
equilibrium lies in favour of the products). In an endothermic reaction the enthalpy change is

PHYSICAL CHEMISTRY
positive and the reaction will only be spontaneous if T∆S is large enough. But for an exothermic
reaction the enthalpy change is negative and so the reaction is always spontaneous.
1.8.8.2.Position of equilibrium
The change in standard molar Gibbs’ function is used to predict the composition at which the
reaction mixture has no further tendency to change (i.e. it can be used to predict the equilibrium
constant (K) of the reaction).
∆G = - R T InK
1.8.8.3.Determination of maximum work (electrical)
The change in Gibbs function is equal to the maximum quantity of electrical work that can be
obtained by using the process.
∆G = W, e(max).
Electrical cells and fuel cells produce electricity and are therefore sources of electrical work. If
the Gibbs’ function is known for a reaction going on inside a cell, the maximum electrical work
can be work out.
The Gibbs energy change of formation can be calculated by addition the Gibbs energies of
formation of all the products and subtracting the sum of the Gibbs energies of formation of all
the reactants:
∆G0 = ∑∆Gf0(products) - ∑∆Gf0(reactants)
1.9. COMMERCIAL EXTRACTION OF METALS
1.9.1. Energetic stability
Standard Gibbs free energy indicate energetic stability of different compounds. Energy stability
is of crucial importance when it comes to the extraction of metals from their ores. The reduction
of a metallic oxide, MO by a reducing agent R can be represented by the general equitation.
MO + R → RO + M.
Since R and M are elements (∆G of (298K) = 0) the overall free energy change for the reaction
will depend on the values of ∆Gf0(298K) for the two oxides RO and MO.
Consider the Thermit process – reduction of chromium oxide (Cr2O3) by Aluminum (Al).
Cr2O3(s) + 2 Al(s)→ Al2O3(s) + 2Cr(s)
∆Gf0(298K)/KJmol-1 -1047 0 -1582 0
∆G0(298K) for reaction = -1582-(-1047)
= -535 KJmol-1

PHYSICAL CHEMISTRY
The reaction is energetically feasible, but for kinetic reasons it should be initiated by heating.
The general point is that an element will reduce an oxide if its own oxide is more stable than the
one being reduced. The information can be obtained from tables of ∆ G 0 values.
Consider the reaction to reduce Aluminum oxide with sodium at 298K.
Al2O3(s) +6Na(s)→ 3Na2O(s) + 2Al(s)

∆ G0f(298K)/KJmol-1 -1582 0 3x(-377) 0
∆ G0(298K) for the reaction = -1131 +1582
= +451KJmol-1
The reaction can occur at 298K since ∆ G0 is positive, but is feasible at elevated temperatures.
(The Hall electrolytic process).
1.9.2.Variation of the Gibbs function with temperature.
0
-200
0
∆G 2Mg(s) + O(g) 2MgO(s)
/kjmol-1 -400 Si(s) + O2(g)  SiO2(S)
-600
-800
B
-1000 b.p. Mg
m.p. Mg
-1200
500 1000 1500 2000 2500 Temperature/K
Fig.1.2 Variation of free energy change (ΔG )with temperature.

PHYSICAL CHEMISTRY
2Mg(s) + O2(g) 2MgO(s)

2Si(s) + O2(g) SiO2(s)
From the above diagram it is clear that Mg can reduce SiO 2 to Silicon at a temperature below
2000K. At a temperature above 2000K Silicon can reduce magnesium oxide to magnesium. Free
energy diagrams of this kind are known as ELLINGHAM diagrams. A more comprehensive
diagram is shown in fig.1.3. Below.
4Au + 3O2 2Au2O3

0----------------------------------------------------------------------------------∆G 0 =0
2Zn +O  2ZnO
2
-200 2CO +O  2CO

2 2
2H +O  2H O
2 2 2
-400
Free energy
C +O  CO
2 2
Change b.p.Z.n,
0
∆G /kjmol
-
-600 2C +O 2 CO
2
m.p. Zn
-800
4 2
Al +¿ O2 Al2O3
3 3
-1000
-1200
0 500 1000 1500 2000 2500
Temperature/K
Fig 1.3 Variation of the energy change with temp for several systerms.
Fig1.3 shows a few interesting points. 1. Gold (iii) oxide, Au2O3, a positive free energy of
formation, therefore gold is found in the native state. 2. Carbon has two oxides, and carbon
monoxide becomes more stable as the temperature increases. Commercially this mean that
almost all metallic oxides can be reduced with coke at high enough temperature. However

PHYSICAL CHEMISTRY
cheapness of coke should be balanced against the high cost of maintaining plant at high
temperatures. 3. Hydrogen is not particularly a good reducing agent since its line runs roughly
parallel with most metallic oxides. 4. The reduction of zinc oxide is carried out at a temperature
above the boiling point of zinc. This causes problems on cooling, since the reaction:
ZnO(s) + C(s)Zn(g) + CO(g)
reverses and the zinc becomes coated with a film of zinc oxide. A plant operating at increased
pressure is required which raises the boiling point of zinc above the required to achieve reduction
of the oxide with carbon.
Many metals are found as sulphides, rather oxides, e.g. zinc sulphide, lead sulphide, and
copper(ii) sulphide, but the reaction
2MS + C → 2M +CS2
is very unfavourable energetically because of the instability of carbon disulphide
(ΔG0f(298K)=+63.6 kjmol-l ). For this reason, roasting of the sulphide ore in air to convert it into
the oxide is generally the first stage in the extraction of metals from their sulphide ores.
The diagram below shows ELLINGHAM for several systems.

PHYSICAL CHEMISTRY

PHYSICAL CHEMISTRY
1.10. THERMOCHEMISTRY
1.10.1 Definition
This is the study of heat effects that accompanies chemical reactions. For example the formation
of solutions, changes in state of aggregation, like melting or vaporization.
Chemical reactions are either exothermic or endothermic. The enthalpy change for an exothermic
reaction is negative whereas the enthalpy change for an endothermic reaction is positive.
(compare with exergomic and endergonic systems).
1.10.2. Standard enthalpy changes
The standard state of a substance at a specific temperature is its pure form at 1 bar (1 bar =
105Pa). The standard conditions of temperature and pressure for thermo-chemical measurements
are 298k (25oc) and 1 atmosphere respective). Any enthalpy changes measured under these
conditions is described as a standard enthalpy change the symbols ∆H is used or ∆H0298.
The standard enthalpy change is defined as the amount of heat absorbed or evolved when the
molar quantities of reactions as stated in the equation, react together under standard conditions.
i.e. at a pressure of 1 atmosphere, and at a temperature of 298k, with substances in their normal
physical states under these conditions and solutions having unity activity (effectively 1.0 mol-1).
Standard enthalpy change of formation of a substance is the heat evolved or absorbed when one
mole of the substances is formed from its elements under standard conditions.
The symbol is ∆H0f.
∆H0f(MgO(s)) = -602 KJmol-1
Relates to the formation of 1 mole MgO from 1 mol of Mg and ½ O2.
Mg(s) + ½ O2→MgO(s)
The standard enthalpy of formation of an element in its normal physical state under standard
conditions is zero.
Cu(s) → Cu(s) ∆H0f =0
H2 (g) → H2 (g) ∆H0f =0
Standard enthalpy change of atomization of an element is the enthalpy change,

when one mole of gaseous atoms is formed from the element under standard conditions.
½ H2(g) → H(g) ∆H0at = +218 KJmol-1

PHYSICAL CHEMISTRY
Standard enthalpy of combustion is the enthalpy change when one mole of the substance is
completely burnt in oxygen under standard conditions.
CH3CH2OH + 3/2 O2 (g)→2CO2(g) + 3H2O(l) ∆H0c = 1368 KJmol-1
1.10.3 First law of thermodynamics.
∆U = q +w
q = energy transferred w = work done
The change in internal energy is not entirely shown in the form of hear but; it may also be shown
by the performance of work on or by the system. ∆U= q + w. ∆U= state function. ∆H which is
related to ∆U as follows ∆H = U + P∆V is also a state function. The value of ∆H is
independent of the way in which the reaction is brought about.
Cyclic process:
Route A -xkj mol-1
H2(g) + O2(g) H2O(l) +½O2(g)
-ykj mol-1 Route B -zkj mol-1
H2O2
-x= -y +(-z)
In each case the initial and the final states are the same and the enthalpy change is also the same;
if different then creation or destruction of energy becomes possible.
The standard enthalpies of route A and B are identical. The first law can be summarized in
Hess’s Law of constant heat summation, which states that:
- The change in enthalpy accompanying a chemical reaction is independent of the pathway

between the initial and final states or the standard enthalpy of an overall reaction is the
sum of the standard enthalpies of the individual reaction into which a reaction may be
divided.

PHYSICAL CHEMISTRY
Energy level diagram to illustrating Hess’s law
Standard 0 H2(g) + O2(g)

o -
Enthalpy ∆H (298K) = -187.6kjmol
0 -1
Change _ ∆H (298K) = -285.9kjmol
H2O2(I)
0 -1
∆H (298K) = -98.3kjmol
H20(l) + ½ 02(g)
Example: Fig 1.4 Two routes for the formation of water.
Most enthalpies of formation cannot be measured directly so Hess’s law helps us to measure
such enthalpies.
e.g. Calculate the standard enthalpy of formation of methane from the following standard
enthalpies of combustion.
C(graphite) + O2(g) → CO2(g) ∆Ho1(298k) = -393 KJmol-1
2H2(g) + O2(g) → 2H2O(l) ∆Ho2(298K) = -286 KJmol-1
CH4(g) +2O2(g) → CO2(g) + H2O(l) ∆Ho3(298K) = -890KJmol-1
Required reaction is:
C(graphite) + 2H2(g) → CH4(g) ∆Ho4(298K) = xKJmol-1
Enthalpy cycle: ∆Ho3(298K)

CH4(g) +2O2(g) CO2(g) + 2H2O(l)
∆Ho4(298K) ∆Ho1(298K) + ∆Ho2(298K)
C(graphite) + 2H2(g)
Applying Hess’s law:

PHYSICAL CHEMISTRY
∆Ho4(298K) + ∆Ho3(298K) = ∆Ho1(298K) + ∆Ho2(298K)
∆Ho4(298K) = -∆Ho3(298K) + ∆Ho1(298K) + ∆Ho2(298K)
∆Ho4(298K) = -(-890) + (-393) + (-286)
= -75KJmol-1
State Symbols
A state symbol should be attached to all the formulae given in an equation
2H2(g) + O2(g) → 2H2O(l) ∆Ho(298K) = -286 KJmol-1
2H2(g) + O2(g) → 2H2O(g) ∆Ho(298K) = -241.8 KJmol-1
For substance with more than one allotropic forms, this should be specified.
C(graphite) + O2(g) → CO2(g) ∆Ho(298k) = -393.5 KJmol-1
C(diamond) + O2(g) → CO2(g) ∆Ho(298k) = -395.4 KJmol-1
What is the energy change for C(diamond) ↔C(graphite)?
Substance in aqueous solution are denoted by (aq), solid form (s), liquid form (l) and gaseous
form (g)
1.10.4. The energetic of crystals
The lattice energy of an ionic crystal is the enthalpy for the general process;
nAm+(aq) + mBn-(aq) → AnBm(s)
Lattice enthalpy (energy) is defined as the energy released when one mole of an ionic compound
is formed from its constituent gaseous ions.
Lattice enthalpies cannot be determined directly, so Hess’s Law can be applied. The above
reaction can be broken down into several hypothetical stages. These give a cycle with the sum
enthalpy changes equal to zero. Such a cycle is called a Born-Haber cycle. E.g. sodium
chloride(NaCl).
Na+(aq) + Cl-(aq) → NaCl(s)

PHYSICAL CHEMISTRY
The Born- Haber cycle for sodium chloride.
+ 800 Na+(g) + e + Cl(g)
+700 stage 4 ∆Ho4
+ 600 Na+(g) + Cl-(g)
+ 500 stage 3 ∆Ho3
+400 Na(g) + Cl(q)
Standard +300 Stage 2 ∆Ho2
1
Enthalpy +200 Na(g) + Cl2(g)
2
Change +100 Stage 1 ∆Ho1
∆Ho(298K)/KJmol-1 Na(s) + ½ Cl2(g)(initial state)
-100
-200 Stage 5 ∆Ho5
- 300 Stage 6 ∆Ho6
-400
-500 Na+Cl-(s)
Fig 1.5 Born Haber cycle for sodium chloride.
∆Ho1+∆Ho2 +∆Ho3 +∆Ho4 +∆Ho5 = ∆Ho6
Where ∆Ho5 is the lattice enthalpy. This value can be calculated by substituting the enthalpies
for stages 1, 2, 3, 4 and 6 in the above equation.
Stage 1 The enthalpy of atomization for sodium. Na(s) →Na(g) ∆Ho1 = + 108.4KJmol-1
Stage 2 The enthalpy of atomization of chlorine. ½Cl2(g) → Cl(g) ∆Ho2 = + 121.1KJmol-1
Stage 3 The ionization energy for sodium. Na(g) → Na+(g) + e ∆Ho3 = + 496 KJmol-1
Stage 4 The electron affinity of chlorine. Cl(g) + e → Cl- (g) ∆Ho4 = -348 KJmol-1

PHYSICAL CHEMISTRY
Stage 5 The lattice energy which is to be determined. Na+(g) + Cl-(g) → NaCl(s) ∆Ho5
Stage 6 The standard enthalpy of formation of sodium chloride. Na(s) +1/2Cl2(g)→NaCl(s)
Substituting:
+108.4 +121.1 +496 -348 + ∆Ho5 = -411
+377.5 + ∆Ho5 = -411
∆Ho5 = -788.5 KJmol-1
1.10.5 Enthalpy of solution
The enthalpy change which takes place when one mole of a solute is completely dissolved in
enough solvent so that no further heat change takes place on adding more solvent. Under such
conditions the solution is said to be at infinite dilution.
When ionic solids dissolve in water, heat is usually evolved or absorbed. For sodium chloride the
overall change is as follows:
NaCl(s) → Na+(aq) + Cl-(aq) ∆Hosoln= +5KJmol-1
The change involves enthalpies of change of solution, hydration and lattice ;
Enthalpy change of solution of NaCl is given by :
(i) NaCl(s) → Na+(g) + Cl-(g) - ∆Holattice = 776 KJmol-1
(ii) Na+(g) + Cl-(g) + (aq) → Na+(aq) + Cl-(aq) ∆Hohydration = -771KJmol-1
Equation (i) is endothermic
(ii) is exothermic. It is the solution of ions.( called hydration when water is the solvent)
The sign for the enthalpy of solution depends on the endothermic and the exothermic process for
NaCl. The endothermic process is slightly greater and hence a positive charge: The enthalpy
change of solution can either be positive or negative.
The relationship between lattice enthalpy, hydration energy and solution enthalpy can be given
by the following energy cycle diagram:

PHYSICAL CHEMISTRY
Na+(g) + Cl-(g)
-∆Holattice ∆Hohydration
NaCl(s) Na+(aq) + Cl-(aq)
∆Hosolution
Therefore : ∆Hosolution = -∆Holattice+ ∆Hohydration
1.10.6 Convention :
The enthalpy of formation of the cation H+ i.e. the process.
½H2(g) → H+(g) + e is zero i.e. ∆Hof (H+ (aq)) = 0 at all temperatures.
The enthalpy of hydration of H+(g)+ (aq)→ H+(aq) ≈ 1090 KJmol-1. This enables other enthalpies of
ions to be calculated.
1.10.7 The temperature dependence of reaction enthalpies
Enthalpy changes are usually quoted at standard temperature (quite arbitrary). In practice many
enthalpy changes cannot be measured at 298 K. Variation of ∆H with temperature was derived
by Kirchhoff. Kirchhoff Law.
A substance heated from T1 to T2, enthalpy changes from H1 to H2
d (∆ H )
. = ∆Cp
dT
Where ∆Cp is the difference in heat capacities of the products and the reactants at constant
pressure. On integration, this becomes:
T2
∆H2 - ∆H1 =∫ ∆ CpdT

T1

PHYSICAL CHEMISTRY
Variation of Cp with temperature can be expressed in the form :
Cp =a + bT + cT2 + ……..
a, b and c are constants for a particular reaction. In practice average heat capacities are used in
other temperature ranges of interest. Therefore :
∆H2 - ∆H1 = ∆Cp (T2 – T1)
Example
The standard enthalpy of formation of gaseous H2O at 25oc is -241.82 KJ mol-1. Estimate its
value at 100oC given the following values of the molar heat capacities at constant pressure.
H2O(g) = 33.58 JK-1mol-1
H2(g) = 28.84 JK-1mol-1
O2(g) = 29.37 JK-1mol-1
Assume heat capacities are independent of temperature. The ∆Cp evaluates to ∆Cp( T2 – T1).
The integral, therefore becomes:
∆H(T2) = ∆H(T1) + ∆Cp(T2 – T1)
1.10.8 Chemical equations
∆Cp = Cp(products) – Cp(reactants)
1
H2(g)+ O → H2O(g)
2 2(g)
∆Cp = 33.58 – 28.84- 29.37
= -9.94 JK-1
Therefore : ∆H2 = -241.82 + -9.94(75)
= -242.6 KJmol-1
1.10.9 Bond enthalpies
When a bond is formed or broken a particular amount of energy is released or absorbed from the
surrounding respectively.

PHYSICAL CHEMISTRY
For example:
Cl – Cl 242KJmol-1
H–H 436KJmol-1
H – Cl 431KJmol-1
From these values we can calculate the enthalpy of formation of HCl:
H2(g) + Cl2(g) → 2HCl(g)
Energy required to break bonds (H-H, Cl-Cl) = 436 + 242 = 678 KJmol-1
Energy gained on forming bonds (2 x HCl) = 2 x (-431) = -862 KJmol-1
Overall enthalpy change ∆Ho(298K) = +678 + (-862) Kjmol-1 = -184 KJ mol-1
(The accepted value is 184.6 KJmol-1 for 2mols of HCl)
Bond dissociation enthalpy ∆H (A - B) is the standard reaction enthalpy for the breaking of the
A – B bond
A- B (g) → A(g) + B(g) ∆H(A-B)
Where A and B may be atoms or groups of atoms, as in CH3OH→CH3(g) + OH(g)
∆H(CH3−OH)= +380KJmol-1
Mean bond enthalpy – is the bond dissociation enthalpy of the A – B bond averaged over a series
of related compounds.
e.g O – H is calculated from data from H2O and similar compound such as CH3O – H and has a
value of 437 KJ mol-1
Methane. (CH4)
CH4(g) → CH3(g) + H(g) 425 KJmol-1
CH3(g) →CH2(g) + H(g) 470KJmol-1
CH2(g) → CH(g) + H(g) 416KJmol-1
CH(g) → C(g) + H(g) 335KJmol-1
The average bond is 1646/4 = 412 KJ mol-1

PHYSICAL CHEMISTRY
Table 1.1 Bond enthalpies.
Bond ∆Ho (298kl/kJmol-1 Bond ∆Ho (298kl/kJmol-1

H- H 436 C-H 413
C–C 346 N-H 388
O-O 146 0-H 436
F-F 158 F-H 562
Cl-Cl 242 Cl-H 431
Br-Br 193 Br-H 366
I –I 151 1-H 299
1.10.10 Determination of bond energies
- Spectroscopic method
- Electro impact method
- Thermo-chemical methods
Factors affecting average bond energies:-
a) Effect of bond length
b) Effect of number of bonding electrons e.g. C−C, C═C and C≡C
(Compare similar species not C═O with the above)
c) Effect of bond polarity.

PHYSICAL CHEMISTRY
CHAPTER 2
2.0. CHEMICAL EQUILIBRIA
2.1 Reversible Reactions
It is likely that all chemical reactions can take place in both directions but in many cases the
extent of the reverse direction is small and negligible. When the conditions are such that the
forward and backward reactions can occur to a noticeable extent, the process is a reversible
reaction. In a closed system ( vessel) the products of such a reaction do not escape and the
reactants cannot combine completely, the reaction does not go to completion in either direction.
For example,
(a) homogenous gaseous reactions:
I2(g) + H2(g) → 2HI(g)
N2(g) + 3H2(g) → 2NH2(g)
(b) Homogeneous liquid reaction:
CH3COOH(l) + CH3CH2OH(l) → CH3COOCH2CH3(l) + H2O(l)
2.2 Chemical Equilibrium
After the passage of sufficient interval of time all reversible reactions reach a state of
equilibrium. That is a state in which no further change in the composition with time can be
detected, provided that the temperature and pressure are kept constant. A state of dynamic
equilibrium is reached when the forward reaction will be taking place at the same rate as the
backward reaction.
2.2.1The Law of mass action (The law of chemical equilibrium)
The velocity of a chemical reaction is proportionate to the product of the active masses of the
reacting substances.Active mass is the concentration expressed in moles per litre (mol-1/ moldm-
3
).
Consider:
r1
A+B C+D
r2
r1= rate for the forward reaction and r2 = rate for the backward reaction

PHYSICAL CHEMISTRY
The rate of conversion of A and B is proportional to the concentrations
r1∝ [A][B] square brackets imply concentration.
r1 = K1[A][B] where K1 is the rate constant for the forward reaction.
Similarly: r2 ∝ [C][D]
r2 =K2[C][D] where K2 is the rate constant for the backward reaction.
At equilibrium r 1 = r2
K 1 [ C ] [D]
Therefore : K1[A][B] = K2[C][D] =
K 2 [ A ] [B]
[ C ] [D ] K1
Therefore : K= where K = andK is the equilibrium constant for the reaction.
[ A ] [ B] K2
The equilibrium constant K is defined as the ratio of the product of the concentration of the
products to the product of the concentration of the reactants, all raised to their stoichiometric
ratios.
In general chemistry reactions involve a number of molecules. For example:
aA+bB↔cC + dD
[C]c [D] d
Therefore: K= a b K can be given various standard states:
[ A ] [ B]
(i) in terms of concentration (moldm-3) Kc
(ii) in terms of partial pressure (p) Kp
(iii) in terms of mole fraction (x) Kx
The equilibrium constant of a reaction varies with temperature of the reaction. At each
temperature the equilibrium constant value depends on the nature of the reaction.
2.3. Homogeneous and Heterogeneous equilibrium
2.3.1. Homogeneous equilibrium
In homogeneous equilibrium, the reactants and the products are in the same phase. This can
either be gas or liquid since we rarely have reactions taking place in the solid state.For example,

PHYSICAL CHEMISTRY
I2(g) + H2(g)↔ 2HI(g)
N2(g) + 3H2(g) ↔ 2NH3(g)
P 2NH 3
Kp =P P3H 2
N2
CH3COOH(l) + CH3CH2OH(l)↔ CH3COOCH2CH3(l) + H2O(l)
[CH ¿¿ 3 COOH ][CH 3 CH 2 OH ]

K= ¿
[ CH ¿ ¿ 2 COOCH 2 CH 3 ][H 2 ]¿
2.3.2. Heterogeneous equilibrium
When a reaction involves one or more solids in addition to a gas or liquid phase, the reaction is
said to be heterogeneous.
For example:
CaCO3(s) ↔CaO(s) +CO2(g)
K= [CaO]¿ ¿ ¿
By convention the concentration of a solid is a constant [ CaO ]=K1 and [CaCO3] = K11
K1
11 = Kc
K
Therefore the equilibrium expression simplifies to :
Kc = [CO2] in terms concentration in mol per litre or Kp = Pco2 in terms of partial pressure.
A large K means that the reaction proceeds extensively from left to right. A small K means that
very little reaction occurs from left to right.
2.4 Experimental determination of equilibrium constant.
The experiment is carried out by sealing known amount of the acid and alcohol in a number of
glass tubes which are then heated in a temperature of 373k (100oC) until equilibrium is attained.
The tubes are then rapidly cooled to freeze the mixture (i.e. the reactions are said to be arrested).
The amount of acid left is determined by titration with a standard alkali. The assumption made is

PHYSICAL CHEMISTRY
that the equilibrium does not shift position significantly during analysis. From the amount of
acid left the other concentrations can be determined.
For example:
One mole of ethanoic acid was mixed with eight moles of ethanol, at equilibrium 0.966 mol of
ethylethanoate were formed. Calculate the equilibrium constant Kc.
CH3COOH(l) + CH3CH2OH(l) → CH3COOCH2CH3(l) + H2O(l)
1.00 8.00 0 0
Initial conc/moldm-3
v v vv
0.034 7.034 0.966 0.966

Equilibrium conc/moldm-3
v v v v
( 0.966 ) ( 0.966)
2
(v ) (v ) (0.966)
Equilibrium constant Kc = = = 3.900 (no units)
(0.034) (7.034) ( 0.3034 ) (7.034)
(v ) (v)
The equilibrium constant remains constant even if the relative concentration of the participating
substances are altered. Table 2.0
Ethanol acid Ethanol Ethylethanoate Kc

1) 1.00 0.18 0.171 3.910
2) 1.00 0.33 0.293 3.380
3) 1.00 0.50 0.414 3.401
4) 1.00 1.00 0.667 4.010
The above results illustrates that the position of equilibrium can be altered by varying relative
concentration of the participating substance, but the equilibrium constant itself remains constant
unless the temperature is altered.
Table 2.1 show the reaction of hydrogen and iodine.

H2(g) + I2(g) ↔ 2HI(g) at 730.6K (45.76oC)
Initial conc. x 103/moldm-3 Equilibrium conc.x103/moldm-3 Kc

H2 I2 HI H2 I2 HI
11.967 6.9436 0 5.617 0.5936 12.70 48.37
12.281 9.964 0 3.841 1.524 16.87 48.61
0 0 4.573 1.696 1.696 1.181 48.48

PHYSICAL CHEMISTRY
0 0 3.866 1.433 1.433 1.000 48.71
Example:
Suppose that a moles of hydrogen moles of iodine and 0 moles of hydrogen iodide are used in an
experiment. If x moles of hydrogen are used up in the reaction then clearly x moles of iodine are
also consumed and 2x moles of HI formed. At equilibrium the number of moles of the three
species will be resp. (a – x) (b- x) and 2x. If the total volume is Vdm3, then the initial and
equilibrium concentration are given below:-
H2 + I2(g) ↔ 2HI(g)
Initial conc./moldm-3 a/v b/v 0/v
(a−x) (b−x ) 2 x
Equilibrium conc.moldm- 3
v v v
2
2 (2 x /v)
[HI ] (4 x¿¿ 2)
Equilibrium constant Kc = = (a−x) (b−x ) = ¿
[ H ¿¿ 2][ I 2 ]¿ ( a−x ) ( b−x )
v v
Equilibrium between dinitrogen oxide and nitrogen oxide.
N204 ↔ 2N02
Colourless dark brown
The reaction involves an increase in the number of moles
N204 ↔ 2N02
Initial moles 1 0
Equilibrium moles 1-x 2x
( 1−x ) 2 x
Equilibrium conc./moldm-3
v v

PHYSICAL CHEMISTRY
2
(2 x)
[ N 02] v2 4x
2
Equilibrium constantKc = = =
[ N ¿ ¿ 2 04 ]¿ (1−x) ( 1−x ) v
v
In order to calculate Kc we need toknow the values of x and v. This can be determined as
follows:-
1
1 – x + 2x→ 1 + x total equilibrium mixture. The ratio is given by :
(1+ x)
1
=
(1+ x)
Observed relative molecular mass(R . M . M .)for equilibrium mixture
calculated relative molecular mass for N 2 0 4
The observed R.M.M. for the equilibrium mixture at 323K and 1atmosphere is 65.7. Therefore
the value of x is given by:
1 65.7
= Therefore x= 0.4
(1+ x) 92
The total equilibrium mixture is 1+ 0.4 = 1.4 moles, 1mol of gas occupies22.4 dm3 at 273K
Therefore 1.4 moles of the equilibrium mixture should have a volume of 1.4 x 22.4 dm3 at 1atm
and 273K. The temp of the equilibrium mixture is 323K, thus the volume will be given by:
1.4 x 22.4 x 323

V = =37.1dm3
273
2
4 (0.4)
The equilibrium constant Kc = =0.029 moldm-3
( 1−x ) 37.1
What is the effect of halving the volume (i.e. increasing the pressure) on the equilibrium mixture.
2
4x
Kc= 0.029 = This simplifies to: 4 x 2 + 0.532x - 0.532 = 0.
( 1−x ) 18.55
Using the equation.
−b ± √ b2−4 ac
x=
2a
x = 0.3 or -0.44 (discarded)
The effect of halving the volume is seen to decrease the number of moles of N02 from 0.8 to 0.6
the equilibrium shift from right to left.

PHYSICAL CHEMISTRY
When reactions are in the gaseous phases it is more appropriate to use pressure units. As a
measure of concentration.
N204(g) ↔ 2N02(g)
Initial moles 1 0
Equilibrium moles 1–x 2x total pressure
Partial pressure ( 1−x

1+ x ) p (
1+x )
2x
p (1+ x)
2.5 Dalton’s law of partial pressure.
When two or more gases which do not react together chemically are present in the same
container, the total pressure exerted by a mixture is the sum of the partial pressure of each
constituent gas.
If PN02 and PN2 04 are the equilibrium pressures of the two gases then the Kp is given by :
2 2
4x p
P 2N 02 (1+ x)
2
4 x2 P
Kp = = which simplifies to Kp =
N 204 1−x (1−x 2 )
⌊ ⌋P
1+ x
2.6.Uses of equilibrium constants
1) Determination of the direction of a chemical reaction:
When K is large the products are favoured and when K is small the reverse reaction is
predominant over the forward reaction.
(ii) Determination of equilibrium composition
Once the value of the equilibrium constant is determined from a single set of
measurements at a given temperature, it is possible to calculate the composition of a
system at equilibrium or any specified initial states at the same temperature.
2.7 Le Chatelies Principle
If a constraint is applied to a system in equilibrium the system will adjust itself so as to nullify
the effect of the constraint. The principle can be used to make predictions on chemical shifts in
equilibrium if it is slightly disturbed.
2.8. Effects of Conditions
2.8.1. Temperature

PHYSICAL CHEMISTRY
a)Endothermic Reactions
If an endothermic reaction has reached equilibrium and temperature of the system is raised Le
Chatelier’s principle requires a response that will tend to lower the temperature that is the
equilibrium moves (shifts) in favour of the endothermic reaction which proceeds with the
absorption of heat. Therefore an endothermic reaction is favoured by raising the temperature and
is inhibited by fall in temperature. Also a rise in temperature increases the rate of a reaction and
therefore usually no catalyst is employed.
N2(g) + O2(g) ↔2NO(g)
C(s) + 2S(s)↔CS2(g)
3O2( g) ↔2O3(g)
b)Exothermic Reaction
If an exothermic reaction has reached equilibrium and the temperature is lowered. Le Chatelier’s
principle requires a response that will tend to raise the temperature therefore the equilibrium
moves in the direction that favours the exothermic reaction which proceeds with liberation of
heat that raises the temperature. Therefore an exothermic reaction is favoured by lowering
temperature and is inhibited by raising temperature. The lowering of temperature reduces the
rate of a chemical reaction hence a catalyst is usually used.
2.8.2.Effects of pressure
If reaction proceeds with no change in volume it is independent of pressure. (Kp or Kc no units).

Pressure effects are more significant in gaseous reactions. If a reaction proceeds with a reduction
in volume ie. a decrease in the number of molecules, has reached equilibrium and pressure is
increased at constant temperature, Le Chatelier’s principle requires a response that will tend to
lower the pressure i.e the forward reaction is favoured as it proceeds with the lowering of
volume. A gaseous reaction which proceeds with an increase in volume is favoured by
lowering pressure.
3O2(g)↔2O3(g)
H2(g) + N2(g) ↔ 2NH3(g)
2.8.3.Effects of Concentration
If A and B react to reach equilibrium under given conditions and then more of A is added, Le
Chatelier’s principle requires a response that will tend lower the concentration of A, hence a
process moves to use more of A. For example:

PHYSICAL CHEMISTRY
2SO2(g) + O2(g) ↔ 2SO3(g)
If the proportion of oxygen increase more than the ratio 2:1 more SO3 is produced.
2.8.4.Some other effects
1. Pressure in thermal dissociation
NH4Cl(S) ↔ NH3(g) + HCl(g)
This will normally be favoured by lowering of pressure as the number of molecules increase.
This process also obeys Le Chateliers principle.
2. Temperature and Solubility
a) Solids
Most solids dissolve in water in the absorption of heat. If a solution is in equilibrium with solid
solute at a certain temperature and the solution is warmed, more solid will dissolve absorbing
heat and tend to lower temperature therefore most solids increase their solubility in water when
temperature rises.
Solution↔Solid solute
b) Gases
Gases liberate heat when they dissolve in water so they are less soluble in hot water. When
pressure is increased gases dissolve more.
3) Melting
If a solid melts with a decrease in volume, therefore increasing pressure will increase melting.
Ice ↔ water.
For example,
I2(g) + H2(g) → 2HI(g)
N2(g) + 3H2(g) → 2NH2(g)

PHYSICAL CHEMISTRY
CH 3COOH(l) + CH3CH2OH(l) → CH3COOCH2CH3(l) + H2O(
This reaction involves reaching nitrogen and hydrogen together at a high pressure( at least 200
atm) in the presence of an iron catalyst and a temperature of around 700 k. Under these
conditions about 15% of the equilibrium mixture is ammonia
H2(g) + N2(g) ↔ 2NH3(g) ∆H(298K)= -92KJ mol-1
2.9.Factors affecting yield of Ammonia.
2.9.1.Temperature
The formation of ammonia form is elements is reversible process.
N2(g) + 3 N2(g) ↔ 2NH3(g)
In which the forward reaction is accompanied by the evolution of heat (energy) and is said to be
an exothermic reaction.The reverse reaction absorbs heat and is said to be endothermic. If the
temperature of an equilibrium mixture of N2, H2 and NH3 is increased, then the reaction which
absorbs heat will be favoured and so ammonia will decompose.
Table2.3 The effect of temp on the yield of ammonia.
Temperature/K %ntage molar yield of ammonia

1273 Negligible
723 15
473 88
Why is a temperature of 700 K used ? This is because at 473the reaction takes place at a slower
rate and equilibrium takes a longer time to achieve.
Calculate the Kp value for ammonia at 15% yield.
2.9.2. Pressure:
An increase in pressure will move equilibrium to the right and thus increasing the percentage
yield of ammonia. Also the reaction reaches equilibrium faster at higher and higher pressures
since the number of gaseous collisions increases. However, with increasing pressure the cost of
industrial plant becomes more expensive, e.g. pipes have to made thicker to withstand the
pressure. A compromise is reached between high yield at high cost and a lower yield at lower
cost.

PHYSICAL CHEMISTRY
Table 2.2 The effect of pressure on the yield of ammonia.
Pressure/ atm %ntage molar yield of ammonia

1 Negligible
100 7
1000 41
2.10 .CONTACT PROCESS
This evolves the reaction of highly purified sulphurdioxideandoxygen in the presence of

vanadium pentoxide catalyst (V205) at a temperature of about 450c.
2S02(g) + 02(g) ↔ 2S03(g) ∆H(298K) = -189KJmol-1
What are the conditions which would favour a high yield of SO3?
As in the Haber Process there is a decrease in the number of moles as the reaction proceeds from
left to right, hence an increase in pressure will result in a larger yield of sulphur trioxide. The
reaction is exothermic so high temps gives lower yields. The actual temp employed is about
723K. The sulphur trioxide is converted to sulphuric acid by dissolving in 98% acid
S03+ H2S04 → H2S207 + H2 0→2H2S04
The oxidation of S02 is a reversible process.
2S02(g) + 02(g) ↔ 2S03(g)
Calculate the value of the equilibrium constant, Kp at 1000k from the following equilibrium
pressures.
Partial pressures/atm
PSO2 PO2 PS03

0.273 0.402 0.325
If the above equilibrium mixture was obtained by starting with a mixture of sulphur dioxide and
oxygen in a sealed vessel at 1000k, what were the initial concentrations of these two gases i.e.
initial partial pressures?

PHYSICAL CHEMISTRY
CHAPTER 3
3.0. REACTION KINETICS
Reaction kinetics is the study of the factors that affect rates of chemical reactions. These studies
lead to reaction mechanisms. The number of reacting species (molecules, atoms, ions free
radicals) that take part in a rate determining step is the molecularity of the step. (e.g.
unimolecular, bimolecular, trimolecular). The section basically deals with the speed at which a
compound is formed or decomposes.
Rate of reaction is the change in concentration of reactants or products with time. The units are
moldm-3s-1.
3.1. Measurement of reaction rates.
The concentration of a selected reactant is followed as the reaction proceeds. The concentration is plotted
against time and the gradient evaluated at certain times. This gives reaction rate at that particular time.
Products
Concentration
(moldm-3) Gradient(gives reaction rate at a particular time)

PHYSICAL CHEMISTRY
Reactants
Time
Fig. 3.1 Change of concentration with time.
The technique used for measuring concentration depends on how quickly it changes.
3.1.1. Spectroscopic Method
This is used for very fast reactions and the readings are recorded electronically.
3.1.2. Colourimetic Method
This is suitable for coloured reactants such as Bromine as the intensity of its colour is
usually proportional to the concentration.
3.1.3. Titration Method
Suitable for moderately slow reactions. A little of the reaction mixture is withdrawn at
various times and diluted rapidly (quenched) such that the reaction stops. Each sample is
analysed using a suitable titrant. For acid base reactions the hydrogen ion concentration
is measured using a pH meter.
3.1.4. Conductivity Method
If the reaction produces or removes ions during the reaction, its electrical conductivity
changes during the reaction and can be measured at suitable intervals using a
conductivity meter.
3.1.5. Pressure or volume measurements
This is suitable for gaseous reactions or reaction producing gases. The reaction can be
followed by measuring the pressure or volume of the gas present at suitable intervals.
3.2. Factors that affect the rate of chemical reactions.
3.2.1. Physical State of Reactants
A reduction of the particle size of the reactant tends to lead to an increase in the rate of a
reaction. For example when Calcium Carbonate (CaCO3) is used as a powder with Hydochloric

PHYSICAL CHEMISTRY
acid the reaction is faster than when marble chips are used. The fine powder has a greater
surface area and exposes more particles for reaction with acid.
2) Concentration of the reactants
Increasing the number of particles per unit volume causes more frequent collisions and hence an
increase in the rate of reaction.
3) The temperature of reactants
At low temperatures particles move relatively slowly and there are few productive collisions
(collusions leading to products). As temperature increases the particles move more rapidly as
their kinetic energy increases.
The rate of collisions will be increased, as a result the number of collusions leading to products
increase.
4) Presence of catalyst
The catalyst increases the rate increases the rate of a chemical reaction by providing an
alternative route with a lower activation energy.
Rate Laws and Rate Equations
3.3 Order of a reaction
In general it is an experimental determined quantity which is seldom in any way connected with
the stoichiometry of the particular reaction. Overall order of a reaction is the sum of the orders
of the components in the rate law
3.3.1.Zero order reaction
For a zero order reaction, the rate of reaction is independent of the concentration of a particular
reactant. The reactant will not appear in the rate equation.
For example:
Rate =∝[A]0 0 order reaction

Rate = K[A]0 but [A] 0 = 1
Rate = K
The order of a reaction with respect to some component, is the power to which the concentration
of that component is raised in the rate law.
3.3.2.First Order

PHYSICAL CHEMISTRY
Let us suppose that a first order reaction may be represented by the general equitation.
A → products
The rate of the reaction is proportional to the concentration of A.
Rate ∝[A]1
Rate = K[A]1
K is the rate constant or coefficient and 1 is the order of the reaction with respect to the
concentration of A (first order reaction). K depends on the temperature and it is a constant for a
particular reaction.
3.4.Integrated and Differential Rate Laws
The differential rate laws show how the rates of reaction depend on the concentration of
reagents. Integrated rate laws show how the rates of reaction depend on the time.
3.4.1. Differential Rate Laws
For example, the decomposition of dinitrogenpentoxide.
1
N2O5 →2NO2 + O2
2
The reaction is first order with respect to the concentration of N2O5.
The general equation can be given as follows
aA + bB → cC + dD.
The relationship between the various derivatives is :
−1 d [ A] −1 d [B ] 1d [C ] 1 d [D ]
= = +
adt bdt cdt ddt
The rate of change of N2O5 is given by:
d [N ¿ ¿ 2O5 ] d [N ¿ ¿ 2O5 ]
− ¿ =K[N2O5] where – ¿ is the rate which depends on the
dt dt
concentration of N2O5.
The various derivatives are connected by the following algebraic relationship:

PHYSICAL CHEMISTRY
d [N ¿ ¿ 2O5 ] d [ NO2 ] [O¿¿ 2]

− = =2 d ¿¿
dt 2 dt dt
Since one mole of dinitrogenpentoxide decomposes to give two moles of nitrogen dioxide, the
rate of change of NO2 is only half relative to N2O5.
3.4.2. Integrated rate laws.

Let [A] be the concentration of N2O5
−d [ A ]
=¿K[A]
dt
Rearranging and taking integrals:
Atd ¿¿
− ∫ ¿
Ao
-ln[A]t = Kt + constant when t =0 -ln[A]0 = constant
Therefore: -ln[A]t = Kt - ln[A]0
[ A]t
ln =−¿Kt (i)
[ A]0
Raising to the power e: -ln[A]t = Kt - ln[A]0

[A]t= [A]0e-Kt
From equation (1) A plot of In (A)t as a function of t will give a straight line whose slope is –K.
this show first order kinetics.
Half life t1/2
This is the time needed for the first order reaction to the half completed i.e.
[ A]o
[A]t =
2
[ A ]0
=¿
From equation (i) substitute ln [ A ] o Kt1/2
2
[ A ]0 x2
ln =¿ Kt1/2
[ A]0

PHYSICAL CHEMISTRY
ln 2 0.6939
Therefore: t1/2 = =
k k
The time for the reaction to be half completed is independent of the initial concentration [A]oThis
also proves that the reaction is first order.
3.5. Second order reaction
If a reaction is second order the time dependence of the reactant concentration is different. For
example the dimerization of butadiene C4 H6.
C4H6(g) → ½ C8H12(g)
which follows the second order differential rate law:
[C ¿ ¿ 4 H 6 ]
−d =¿ ¿K[C4H6]2
dt
Let C be the concentration.
−dC
=¿KC2
dt
−dC
Rearranging: =¿Kdt
C2
C t
dC
Taking integrals −∫ 2 =∫ Kdt
Co C 0
1 1
=Kt + constant when t=0 =costant
C C0
1 1 1 1
Therefore: =Kt + Which gives: − =Kt
C C0 C C0
1
The second order kinetics a plot of as a function of time (t) should be a straight line with a
C
−1
slope K and intercept.
C0
Half life for second order kinetics.
1 1
− =Kt
C C0

PHYSICAL CHEMISTRY
1 1
− =¿
C0 Co Kt1/2
2
1
Therefore: t1/2=
KC 0
The half life for a second order reaction depends on the initial concentration. (Compare with
half-life for first order reaction).
Summary Second order
Rate First order
Zero order
Concentration
Fig. 3.2. Summary of orders of reactions
3.6. Application of rate laws
1) Practical application is that once the rate law and rate constant are known, the rate of the
reaction can be predicted from the composition mixture. Rate =K[A][B]
2) Theoretical application is that is a guide to the mechanism of the reaction and any proposed
mechanism must be consistent with the observed rate law.
3.7. Determination of orders of reactions
The oxidation of aqueous hydrochloric acid by hydrogen peroxide is second order reaction. The
stoichiometric is as follows:-
H202(l) + 2H+(aq) + 2H+(aq) + 2I(aq) → 2H20 + I2

PHYSICAL CHEMISTRY
The equation t= (
1 −1 1
+
K C0 C )
does not apply To this equation. The initial rate method is
employed. In this method a series of experiments is carried out in which initial acid and iodide
concentrations are kept constant, but the hydrogen peroxide contraction is varied. In the
subsequent experiments the concentration of the acid is varied while the other two reagents are
kept constant and then finally the concentration of the iodide is varied, while the other two
reagents are kept constant. Rate =K[H2O2]n[I-]m[H+]p
Results are given as follows :
Table 3.1.Initial rate method.
Experiment Initial Initial Initial conc Initial rate

number concentration of concentration of
H202 moldm-3 iodide ions (I-)
moldm-3 Moldm-3 Moldm-3
1 0.1 0.1 0.1 0.0001
2 0.2 0.1 0.1 0.0002
3 0.2 0.2 0.1 0.0004
4 0.2 0.2 0.2 0.0004
5 0.2 0.2 0.4 0.0004
When the concentration of H2O2 is doubled, iodide ions and acid constant, the initial rate
doubles. It is directly proportional to the concentration of the peroxide, hence first order with
respect to the peroxide.
When the concentration of the iodide ions are double peroxide and acid kept constant the initial
rate double hence first order with respect to iodide ions.
Then the concentration of the acid is doubled, peroxide and iodide ions kept constant, the initial
rate does not change, hence zero order with respect to H+ ions. Therefore the rate law is given as
follows:
Rate =K[H202][I- ] [H+]0
= K[H2O2][I-] Therefore n=1, m=1, and p=0
Alternatively the orders of reaction can be calculated using the formula of ratios. For Hydrogen
peroxide experiments 1 and 2 can be used.
Rate 2
=¿ ¿where n is the order of the reaction.
Rate 1

PHYSICAL CHEMISTRY
( )( )
n
0.0002 0.2
=
0.0001 0.1
2=2n
Therefore: n= 1
Rate 2
Also by taking logarithms log =logn ¿ ¿ ¿
Rate 1
Then solve for n.
3.8. Reaction mechanism
The study of reaction rates makes possible to study reaction mechanism. Most chemical
reactions which proceed at a measurable rate are believed to take place in a series of simple steps
and rarely according to the stoichiometric equation. The series of steps is known as the
mechanism.
For example :-
4HBr + O2 → 2H2O2 + 2Br2
Rate Law : Rate = K[HBr][O2]
The overall reaction must take place in a series of steps which satisfies both the reaction rate and
the stoichiometric equation.
Simple steps.
HBr+ O2→HBrOO step 1 slow
HBrOO + HBr→ 2HBrO step 2 fast
HBr + HBr→H2O + Br2 step 3 fast
HBr + HBr→H2O + Br2 step 4 fast ____________
Overall 4HBr + O2→2H2O + 2Br2

PHYSICAL CHEMISTRY
The first step is the slowest and it involves the collision of two molecules. Therefore therate is
proportional to both the concentration [O2] and [HBr]. That is the rate = K[HBr][O2]. The
formation of HBrOO is the one which dictates the rate and its called the rate determining step,
step 1.
It is the slowest step in the reaction mechanism.
Oxidation of an acidified solution of iodine with H2O2
H2O2 + 2H+ + 2I-→ I2 +2H2O
Reaction is first order with respect to both H2O2 and I-
H2O2 + I-→ H2O + OI- step 1 slow
OI- + H+→ HIO step 2 fast
HIO + I- + H+→ H2O +I2 step 3 fast
The rate controlling step must the first one. The rate law is:
Rate = K[H2O2][I-]
3.9. Activation energy, Collision theory and catalysis.
Chemical reactions take place as a result of molecular collisions. A reaction will only occur if the
colliding particles posses more than a certain minimum amount of energy. This minimum
amount of energy is the activation energy. The activation energy enables chemical bonds to
stretch and break a rearrangement of atoms, ions and electrons to occur as the reaction proceeds.
3.9.1. Activation energy
The reaction can proceed as follows:
Exothermic reaction.
Ea=Activation energy
Increasing reactants ∆H=Enthalpy change

of
reaction
products
Energy

PHYSICAL CHEMISTRY
Reaction ordinate
Fig. 3.3. An exothermic reaction
Endothermic reaction
Ea=Activation
Increasing energy
products
Energy
∆H=Enthalpy of
reaction
reactants
Reaction ordinate
Fig. 3.4.An endothermic reaction.
3.9.2. Collision theory
Distribution of particle energy
no of particles
With energy E

PHYSICAL CHEMISTRY
Kinetic energy Eact
Fig. 3.5.Energy distribution of particle in a system.
The above shows how the energy of the particles are distributed within a system. The particles
with energy ≥Eact are the particles which when colliding results in chemical reactions. The
fraction of these particles is given by the cross hatched area beneath the curve. This fraction is
given by;
− Ea/ ¿RT ¿
e
This suggests that at a given temperature the reaction rate is proportional toe− Ea/ ¿ RT ¿
. The
reaction proportional to the rate constant K
Therefore K∝ e−Ea /¿ RT ¿
K= Ae− Ea/ ¿ RT ¿
Which is the Arrhnius equation
The Arrhnius constant is regarded as the collision frequency and orientation factor in the
− Ea/ ¿ ¿
equation and e is the activation factor.
RT
Taking logs to the base e in K= Ae− Ea/ ¿ ¿ RT
lnK=lnA+lne− Ea/ ¿ RT ¿
Ea
lnK=lnA-
RT
Ea
A graph of lnK against 1/T give a straight line of gradient - with lnA intercept.
R
lnA
EA
-
T

PHYSICAL CHEMISTRY
lnK
1 -1
/K
T
3.9.3. Catalysis.
There is another way of increasing the exponential factore− Ea/ ¿ ¿ apart from increasing
RT
temperature; a reduction in Eact would have the same effect as in increasing temperature.
Catalysts enable Eact to be reduced.
3.9.3.1.Catalysts:
a) provide an alternative route of lower activation energy. They are reformed at the end of the
reaction.
b) They catalyse both the forward and the backward reactions to the same extent in a reversible
reaction and thus have no effect on the equilibrium constant.
c) They are generally highly specific, i.e. a particular catalyst for one reaction is not necessarily a
catalyst for another reaction.
Positive and negative catalysts
3.9.3.2. Homogeneous catalysis.
In homogeneous, the catalyst, reactants and the products are in the same phase. Consider the
reaction:
2I- (aq) + S2O8= → I2 + 2SO4=(aq)
The addition of a small amount of either Fe2+(aq) or Fe3+(aq) considerably quickens the rate of the
reaction.
The reaction is catalysed as follows;
2Fe3+(aq) + 2I-(aq) → I2 + Fe2+(aq)
2Fe2+(aq) + S2O8=→ 2Fe3+(aq) + 2SO4=(aq)
The reaction takes place via ions of opposite charges. If ions of similar charges are to react the
activation energy will be high and the reaction rate slow. An intermediate compound is usually
formed.

PHYSICAL CHEMISTRY
A + catalyst → A-------catalyst
A------catalyst + B→ A____B + catalyst.
This is illustrated below:
Euncat= activation energy for the uncatalysed
reaction.
Increasing Ecat = activation energy for the catalysed
reaction
Energy. Reactants A +B + catalyst
Products A__B + catalyst
Reaction ordinate
Fig. 3.7. Energy changes as the reaction proceeds.
3.9.3.3. Heterogeneous catalysis
In the type of catalysis the, catalyst, reactants and products are not necessarily in the same phase.
For example the Haber process and the Contact process, the catalysis is at solid surface. Another
example is the hydrogenation of ethane at a nickel surface at a temperature of about 400 K. The
overall reaction is:
CH2=CH2(g) + H2(g) → CH3__CH3(g)
Both ethane and hydrogen can bond to the surface of nickel by a process called chemisorption.
The mechanism is visualized in terms of a collision between hydrogen atom on the catalyst
surface and one end of a bonded ethene molecule. If the collision is favourable the fragment
CH3__CH2_ is formed which remains bonded to the nickel surface. Collision with another
favourably placed hydrogen atom forms CH3__CH3 which breaks from the metal surface. The
sequence of events are shown below.

PHYSICAL CHEMISTRY
H2C__CH2 H H2C__CH3
__
Ni__Ni__Ni__Ni__Ni__Ni_ → __
Ni__Ni__Ni__Ni__Ni__Ni__
(a) (b)
H3C__CH3 H H2C__CH3
__
Ni__Ni__Ni__Ni__Ni__Ni_ ← __
Ni__Ni__Ni__Ni__Ni__Ni_
(d) (c)
Fig.3.8. Catalytic hydrogenation of ethene.

PHYSICAL CHEMISTRY
CHAPTER 4
4.0 ELECTROCHEMISTRY
Zn →Zn2+ + 2e
Zinc is tending to pass into solution as hydrated zinc ions leaving a surplus of electrons on the
electrode.
Ag →Ag+ + e
The tendency for silver to form hydrated ions is lower than for that of zinc and there is a deficit
of electrons on the silver electrode. An electron pressure difference (potential difference) is
established between the two electrodes and when the circuit is completed with salt bridge, a cell
is formed and a current flows. The greater the difference in ion forming tendencies of the two
half reactions the larger the potential difference.
Redox reactions can also involve the half-reactions between ion of the same metal in two
different oxidation states.
For example:
Ag+(aq) + Fe2+(aq) ↔ Ag(s) + Fe3+(aq)
Fe3+(aq) + e ↔ Fe2+(aq)
For such reactions an inert electrode, such as platinum (Pt) is used.

PHYSICAL CHEMISTRY
Fe2+/Fe3+ ions
Pt
Fig 4.0 Showing an inert electrode.
Other examples where inert electrodes are used:
Sn4+(aq) + 2e ↔ Sn2+(aq)
Ce4+(aq) + 2e ↔ Ce2+(aq)
4.1 ELECTRO-MOTIVE FORCE (E.M.F.) OF CELLS
When the cell is connected via a salt bridge and an external connection wire, a current begins to
flow. The reaction;
2Ag+(aq) + Zn(s) ↔ Ag(s) + Zn2+(aq)
starts to take place and the free energy change will decrease until at equilibrium ∆G= 0 and the
cell is run down. The reaction proceeds slowly but irreversible. This means that the reaction is
not continually in equilibrium with the surroundings and the measured potential difference
between the electrodes, while the current is following, always less than the e.m.f of the cell if no
current is taken from the cell the potential difference(p.d.) between the electrodes will be
maximum and will be equal to the e.m.f of the cell. Under the conditions i.e. temperature of
298K and unit effective concentration for the solution, the e.m.f is called standard e.m.f. of the
cell and is given the symbol E○.
4.1.1. Convections
The conventions for symbolizing cell and for assigning a sign to the e.m.f. of a cell are those
recommended by International Union for Pure and Applied Chemistry (IUPAC).

PHYSICAL CHEMISTRY
Daniel Cell

PHYSICAL CHEMISTRY
Zn(s)/Zn2+(aq) Cu2+(aq)/ Cu(s)
Electrodes are represented by a solid line / and the salt bridge by a dotted line .
If an inert electrode is used it will be shown as follows:-
Pt/Fe2+(aq),Fe3+(aq) that fora platinum electrode immersed in Fe2+ /Fe3+ ions.
The e.m.f. of zinc –silver cell has a value of 1.56 V and the conventional representation of this
cell is as follows:
Zn(s)/Zn2+(aq) Ag+(aq)/Ag(s) E○ = 1.56V
The oxidized half- cell is on the left hand side and the reduced half -cell is on the right hand side.
4.1.2. The e.m.f. and Gibbs free energy change.

PHYSICAL CHEMISTRY
The e.m.f measured under reversible condition represents the maximum work
Maximum work =- nEF
Where n is the number of moles of electrons transferred and F is the Faraday’s constant.
The e.m.f..of the Daniell cell operating under standard conditions is 1.10V, therefore the
maximum amount of work obtainable from the cell reaction is:
Max work = nFE = -2 96500 x 1.10
= - 212.3 kJ.
The maximum work that can be derived from a chemical reaction is equal to the free energy
change for the reaction.
∆G = - n FE= Max work
If the free energy is negative the reaction can occur spontaneously.
Other relationships for Gibbs free energy: ∆G○ = ∆H○ - T∆S○
∆G○ = -RTlnK
The absolute values for the standard electrode cannot be measured. So a standard is chosen
which is given an arbitrary of 0.0V.
Fig 4.2The Standard Hydrogen Electrode.

PHYSICAL CHEMISTRY
The standard electrode potential for the system Mn+(ag)/M(s)is found by connection it to a S.H.E.
via a salt bridge (NH4N03, KCl ) and reading the potential difference developed on a high
resistance volt under (with negligible current flowing).
The potentials for: Zn2+(aq)/Zn(s) = -0.76V
Cu2+(aq)/Cu(s) = +0.34V
The zinc is the negative electrode and copper is the positive electrode. The half-cell reactions
given are written as reduction process and it is important to remember this.
AgCl(aq) + e ↔ Ag(s) + Cl-(aq) E○=0.80V Hg2Cl2 + 2e ↔ 2Hg(l) + 2Cl- E○ = 0.280V
Fig.4.3. Glass electrode and Calomel electrode.
If the standard electrode potentials are known then the e.m.f. for cell can be calculated then the
Gibbs free energy and the equilibrium constant (Kc ) can also be calculated.
A reaction which is energetically feasible may not be observed in practice if it occurs at too slow
a rate.

PHYSICAL CHEMISTRY
Al3+(aq) + 3e ↔ Al(s) E○ = -0.166V
Pb2+(aq) + 2e ↔ Pb(s) E○ = -0.13V
2H+(aq) + 2e ↔ H2(g) E○ = 0.00V
The reaction of lead with H+(aq) is feasible but kinetically too slow to be observed al forms a layer
of Al2O3which prevents it from reacting but if the layer is removed then the normal and expected
reactivity is observed.E○ values apply only to reactions aqueous solution under
standardconditions.
4.1.3. Effect of Concentration and temperature
If we consider the half-cell reaction:-

PHYSICAL CHEMISTRY
Mn+(aq) + ne ↔ M(s)
An increase in the concentration of Mn+ ions would shift the equilibrium to right. This makes
the E○ value more positive. The system becomes a stronger oxidizing agent. A decrease in
Mn+(aq) concentration would have the opposite effect, the system becomes a better reducing agent.
Two copper cells of equal concentration, 1 mold-3 then the concentration of the ions in the left
half- cell is reduced by dilution to 0.01moldm-3.
Flow of electrons
Salt bridge
Copper electrode Copper electrode
0.01M CuSO4 1.00M CuSO4
More negative half-cell
Fig. 4.4.Concentration cell for copper.
The left electrode becomes negative and more copper goes into solution.The reaction Cu(s)→
Cu (aq)+ 2e becomes predominant.The effect is to increase the concentration of Cu until a new
2+ 2+
equilibrium is reached.
At other electrode Cu2+(aq) + 2e→ Cu(s) reaction is predominant and the effect is to reduce the
Cu2+concentration hence a new equilibrium will be reached and cell potential falls to zero. For
copper each ten- fold dilution gives an increment of 30 mV.If copper is replaced by the silver
each ten-fold dilution is replaced by 60mV increment.These findings, are rationalized in the
Nernst equation
RT [oxidised ]
E = E○ + ln
nF [reduced ]
RT
For copper this reduces to E = 0.34 + ln[ Cu2+]
2F
RT
For silver this reduces to E = 0.80 + ln[ Ag+]
F
RT
For Fe3+/ Fe2+ , the equation is E= 0.77 + ln¿ ¿ ¿
F
The Nernst equation applies to non- standard conditions.

PHYSICAL CHEMISTRY
4.1.4.Effect of pH.
If the redox half-equation involves H+ or OH- ions then its electrode potential will depend on the
pH of the solution. For example:
MnO4-(aq) + 8H+(aq) + 5e ↔ Mn2+(aq) + 4H2O(l)
RT
E = E○+ ln¿ ¿ ¿
5F
At unit concentration the E=E○ = 1.52V the E cell can be calculated, when the concentration of
H+ = 10-3 M and 10-6 M.
Comment on the E cell values and decide which species can be oxidized from the least below:-
½I2(s) + e ↔ I-(aq) E○ = 0.54V
½Br2(l) + e ↔ Br-(aq) E○ = 1.07V
½Cl-(g) + e ↔ Cl-(aq) E○ = 1.36V
4.1.5. Measurement of pH.
The concept of concentration cells is used in pH measurement. So a pH meter is simply an

electrochemical cell whose e.m.f. is related to the hydrogen ion concentration, or pH of one half-
cell. The meter itself is an electronic voltmeter, a device which draws very little current, and is
calibrated in pH units.
4.2. Equilibria in complex ion system.
A complex (or coordination compound ) is formed when one or more species with a lone-pair of
electrons (either negative or neutral) forms a coordinate bond with a positively charged metal ion
(usually a transition metal ion). E.g.
Fe3+(aq) + 6CN-(aq) ↔ [Fe(CN)6]3-(aq)
Hexacyanoiron(iii) ion (Hexacyano ferric ion).
The negative ion or neutral molecule which form a coordinate bond with the metal ion is known
as the ligand. The number of lone pairs on the ligand which become bonded to the metal ion is
called the coordination umber of the complex. The group comprising the metal-ion and the
ligands is called the coordination sphere.
Complexes may be ions of either charge, e.g.
Fe3+(aq) + 6F-(aq) ↔[ FeF6]3-(aq)

PHYSICAL CHEMISTRY
Ni2+(aq) + 6NH3(aq) ↔ [Ni(NH3)6]2+(aq)
or they may be neutral molecules which, being covalent compounds, are usually insoluble in
aqueous solution:
Cu2+(aq) + 2NH2CH2COO-(aq) → Cu(NH2CH2COO)2(s)
Complexes may also be formed between ligands and uncharged metal atom. Note that the
Fe(s) + 5CO(g) → Fe(CO)5(l)
bonding in theses complexes is not of a simple co-ordinate type.
Complex formation
Since the metal ion has vacant ‘d’ orbitals the ligands form dative bonds by donating into the
vacant ‘d’ orbital
Examples of aqua complexes:-
Ni2+(aq) + 6H20(l) ↔ [Ni(H20)6]2+(aq)
Cu2+(aq) + 4H20(l) ↔ [Cu(H20)4]2+(aq)
The can be replaced with other ligands
[ Cu(H20)4]2+(aq) + NH3(aq) ↔[Cu(H20)3(NH3)]2+(aq) + H20(l)
Blue deep blue colour
The extend of replacement depends on the relative stabilities of the complexes. If [Cu(NH3)4]2+(aq)
isstronger, then the replacement becomes complete.
4.2.1. Ligands Classes:
Ligands are according to the number of dative bonds they can form. Monodentate ligands form
only one coordinate bond, bidentate ligands form two, tridentate form three and polydentate
form many bonds.
Ethylene diaminetetraacetic acid (EDTA) is a hexadentate ligand. It forms six coordinate bonds.

PHYSICAL CHEMISTRY
EDTA
EDTA complex where M is the metal ion and the lines to the metal ion are the six coordinate
bonds.
4.2.2. Stability constants
The formation of a complex in solution occurs in several steps. More stable complexes are
preferentially formed. The standard electrode potential are affected by complexing. The
equilibrium between metal ion and aqueous ions is given by:
Cu2+(aq) + 4H20(l) ↔ [Cu(H20)4]2+(aq)
The equilibrium constant is given by the following expression:
[ Cu ( H 20 ) 4 ] 2+( aq)
K=
[ Cu ] 2+ [ H 20 ] 4
The effect of adding a ligand to the metal ion solution is to remove the aqueous ionsMn+from
solution. The position of the equilibrium changes to produce more aqueous metal ions and at the
same time more electrons. Therefore the metal electrode become more negative (more reducing).

PHYSICAL CHEMISTRY
Electrode reaction Eo/V
Cu2+(aq) +2e ↔ Cu(s) 0.34
Cu(NH3)42+(aq) + 2e ↔ Cu(s) + 4NH3(aq) -0.05
Au+(aq) + e ↔ Au(s) 1.70
Au3+(aq) + 3 e ↔ Au(s) 1.38
[Au(CN)2]-(aq) + e ↔ Au(s) + 2CN- 0.60
Zn2+(aq) + 2e ↔Zn(s) -0.7
Industrial application cynide complexes.(Cynidationof gold).
Gold can be oxidized by air in the presence of cynide ion.
2[Au(CN)2]-(aq) + Zn(s) ↔ 2Au(aq) + [Zn(CN)4]2-(aq)
Addition of zinc to the complex results in the deposition of gold because zinc forms a more
stable complex with cynide.

PHYSICAL CHEMISTRY
CHAPTER 5
5.0 IONIC EQUILIBRIA
5.1. ACIDS AND BASES
Arrhenius defined an acid as a substance which when dissolved in water gives the H+ ions as the
only positive ions. A base as a substance which when dissolved in water would give the OH-
ions as the only positive ions.This are limiting definition because there are some reaction which
do not involve the OH- ions which are classified as bases.
Bronsted and Lowry defined an acid as a substance which donate a proton to a base. A base as a
substance which can accept a proton from a acid.
HA + B- ↔ HB + A-
Acid Base
A base is usually a negative ion or neutral molecule with a lone pair of electrons. When an acid
loses a proton to a base it forms a base itself similarly when a base accepts a proton it becomes
an acid itself. Every acid has its conjugate base and every base has its conjugate acid.
Acid1 + Base2 ↔ Acid2 + Base1
HCl + H20 ↔ H30+ + Cl-
HCl+ NH3↔ NH4+ + Cl-
Lewis defined an acid as a substance which can accept a pair of electrons and a base a substance
which donate an electron pair.
Examples of Lewis acids and bases:
Bases: :
NH3, Cl-, CH2NH2, H2O
Acids: NH4+, BF3, AlCl3, and transition metal in complex formation (Mn+)
5.1.1. Water and amphoteric behavior
Water can act as both an acid base.
HCl + H20 ↔ H30+ + Cl-
Acid 1 Base2 acid2 base1
H2O + NH3 ↔ H30+ + OH-

PHYSICAL CHEMISTRY
Acid1 base2 acid2 + base1
A substance that acts both as a base or an acid is called an amphoteric substance.
HCl in aqueous solution liberates H2 from Mg.In dry methylbenzene (toulene) anhydrous HCl
does not react with Mg to liberate to liberate H2.Explain the above phenomenon.
5.1.2. Ionic product water
Water ionizes to very small extent.
H2O(l)↔ H+ (aq) + OH- (aq)
Applying the equilibrium law.
K =¿ ¿ → K[H2O] = [H+][OH-] where K[H2O]= Kw
Kw = [H+][OH-]
Kw is the ionic product of water and has a value of 10-14 mol2dm6 at 298K. For a neutral
solution the concentration of H+ ions and OH- ions should be equal. Therefore:
[H+] = [OH-] = 10-7 moldm-3
If the solution is acid then [H+] ≥ [OH-]
If the solution is basic then [H+] ≤ [OH-]
The ionic product remains the same unless temp is changed.
Table 5.0 Change of Kw with temp.
Examples Kw/mol2dm-6 Kw values increases as

Temp/K temperature increases.
273 0.11 x 10-14
283 0.30 x 10-14
293 0.68 x 10-14
298 1.00 x 10-14
373 51.3 x 10-14 More water ionizes at higher
temps.

PHYSICAL CHEMISTRY
pH Scale: helps us to avoid the use of negative indices
pH is the negative log to the base ten of the hydrogen ion concentration. pH= -log[H+]
10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 10-12 10-13 10-14
Increasing acidity neutral increasing alkalinity
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
It is also possible to define pOH as follows: pOH = -log [OH]and therefore at 298k it is possible
to convert equation. Kw = [H+][OH-] into a relationship.
10-14 = [H+][OH-]
Taking logs -log10-14 =-log [H+](-log[OH-] )
14= pH + pOH also pkw = -log Kw
pkw= pH + pOH
5.1.3. Salt hydrolysis
In pure water the concentration of the H+(q) and OH-(aq)ions are the same. Certain salt which are
not classified as acid or bases can disturb this balance when they are dissolved in water. The
phenomenon is known as salt hydrolysis. The highly charged small cations of metals e.g. those
of transition metals, are strongly hydrated in aqueous solution. Furthermore the small highly
charged cations exert a considerable attraction on the oxygen atoms of the water molecules,
thereby polarizing the bond between the hydrogen and oxygen. Under these conditions solvent
water molecules are able to act as a base and thus give rise to an acidic solution.
FeCl3, NiSO4 , Cu(NO3)2 and Aluminum Salts.
[Fe(H2O)6]3+ + H20 ↔[Fe(H20)5(0H)]2+(aq) + H30(aq)
There is a little tendency for the chloride, sulphate and nitrate anions to detach hydrogen ions
from water molecules they are poor proton acceptors.
The carbonates and ethanoates of potassium and sodiumshow alkaline reaction in aqueous
solution. This is due to fact that both CO32- and CH3COO- function as bases in aqueous solution.
Their conjugate acids, ethanoic, and carbonic acids are weak acids. Strong bases form weak
conjugateacids and strong acids form weak conjugate bases.

PHYSICAL CHEMISTRY
CO32-(aq) + H20(l) ↔ HCO3-(aq) + 0H-(aq)
Base1 acid2 acid1 base2
5.2. STRENGTH OF ACIDS AND BASES
When an acid dissolves in water the following equilibrium is established.
HA(aq) + H2O(l) ↔ H+(aq) + A-(aq)
The position of equilibrium is an indication of the strength of the acid in question. For a strong
acid such as HCl and H2SO4 the reaction goes virtually into completion.
HCl(aq) + H20(aq) → H+(aq) + Cl-(aq)
For acids such as ethanoicacid, the position of equilibrium favours the reactants.
CH3COOH(aq) + H2O(l) ↔ CH3COO-(aq) + H+(aq)
The precise position is shown by the equilibrium constant.
K = ¿¿¿
K[H2O] = ¿ ¿ ¿= Ka. Therefore Ka =¿ ¿ ¿
Ka is the acid dissociation constant. Like in pH, pKa = - log Ka. The more positive the pKa
value the weaker is the acid.
e.g Acid (aq pKa conjugate base (aq
increasing HCL -7 Cl– increasing
acidic H3PO4 2.1 H2PO-4 basic strength
strength CH3COOH 4.8 CH3COO-
HCN 9.3 CN-
H2O 15.7 OH-
Reaction for water with a base.
B(aq) + H2O(aq)↔ HB+(aq) + OH-

PHYSICAL CHEMISTRY
Kb = ¿ ¿ ¿
Kb = is called the based dissociation constant.Similarly Kb can be defined in the same manner
as the pH.pKb = - log Kb.
Ethanoic Acid
Ka = ¿ ¿ ¿
For its conjugate baseCH3COO-
CH3COO- + H2O(aq ) ↔ CH3COOH(aq)+ OH-(aq)
Kb = [CH ¿¿ 3 COOH ]¿¿ ¿ ¿ Where K[H2O] = Kb
Ka x Kb = ¿ ¿ ¿= [H+][OH-] = Kw ionic product of water.
5.2.1. Hydrogen Halides
HI>HBr>HCl> HF
→ decreasing acidic strength →
The more electronegative the atom in association with the acidic Hydrogen the stronger is the
acid.
HF HCl HBr HI
Ka calculated in moldm-3 10- 3 108 1010 1011
The H - F bond energy is very high. The enthalpy of solution of HF is also very high due to H-
bonds.
HF↔ H+ + F- The equilibrium lies far to the left hand side.
Methonic acid is used. In water the acids have equal strength.
5.3. Organic acids.
R-COOH general formula.
The strength of organic carboxylic acid depends on the ability of the RCOO- group to attract
electrons away from the hydrogen atom and thus allows its release as a proton.
RCOOH(aq) + H2O(l) ↔ RCOO-(aq) + H+(aq)
This depends particularly on the nature of the R - group.
Example 1

PHYSICAL CHEMISTRY
Calculate the degree ionization of ethanoic acid of concentration 0.1M using.
(a) Ostwald’s dilution law.
(b) the approximate form of the dilution law.
Example 2
Calculate the part and hence the pH of a 0.1M solution of aqueous ammonia given that Kb =
1.8x10-5 moldm-3 at 298 K.
Examples
Acid Formula R –gp pKa
Ethanoic CH3COOH CH3 - 4.76
Chloroethanoic CH2ClCOOH CH2Cl- 2.86
Dichloroethanoic CHCl2COOH CHCl2-1.29
Trichloroethanoic CCl3COOH CCl3- 0.65
The chlorine atom is powerfully electron- attracting by comparison with the hydrogen atom.
This results in the OH oxygen atom in the acid being more ∂+ than in the parent acid ethanoic.
This facilitates the removal of a proton and leads to an increase in acid strength. The chlorine
atom has a negative inductive effect as compared to the Hydrogen atom.
5.4. Acid – base titrations
5.4.1. The equivalence point of a titration
When you carry out a simple acid-base titration, you use an indicator to tell you when you have
the acid and alkali mixed in exactly the right proportions to "neutralise" each other. When the
indicator changes colour, this is often described as the end pointof the titration.
In an ideal world, the colour change would happen when you mix the two solutions together in
exactly equation proportions. That particular mixture is known as the equivalence point.
For example, if you were titrating sodium hydroxide solution with hydrochloric acid, both with a
concentration of 1 mol dm-3, 25 cm3of sodium hydroxide solution would need exactly the same
volume of the acid - because they react 1 : 1 according to the equation.
PHYSICAL CHEMISTRY
In this particular instance, this would also be the neutral point of the titration, because sodium
chloride solution has a pH of 7.
But that isn't necessarily true of all the salts you might get formed.
For example, if you titrate ammonia solution with hydrochloric acid, you would get ammonium
chloride formed. The ammonium ion is slightly acidic, and so pure ammonium chloride has a
slightly acidic pH.
That means that at the equivalence point (where you had mixed the solutions in the correct
proportions according to the equation), the solution wouldn't actually be neutral. To use the term
"neutral point" in this context would be misleading.
Similarly, if you titrate sodium hydroxide solution with ethanoic acid, at the equivalence point
the pure sodium ethanoate formed has a slightly alkaline pH because the ethanoate ion is slightly
basic.
5.4.2. Titration curves for strong acid v strong base
We'll take hydrochloric acid and sodium hydroxide as typical of a strong acid and a strong base.
Running acid into the alkali

PHYSICAL CHEMISTRY
You can see that the pH only falls a very small amount until quite near the equivalence point. Then
there is a really steep plunge. If you calculate the values, the pH falls all the way from 11.3 when
you have added 24.9 cm3 to 2.7 when you have added 25.1 cm3.
5.4.2.1. Running alkali into the acid
This is very similar to the previous curve except, of course, that the pH starts off low and increases
as you add more sodium hydroxide solution.
Again, the pH doesn't change very much until you get close to the equivalence point. Then it
surges upwards very steeply.

PHYSICAL CHEMISTRY
5.4.3. Titration curves for strong acid v weak base
This time we are going to use hydrochloric acid as the strong acid and ammonia solution as the
weak base.
5.4.3.1.Running acid into the alkali
Because you have got a weak base, the beginning of the curve is obviously going to be different.
However, once you have got an excess of acid, the curve is essentially the same as before.
At the very beginning of the curve, the pH starts by falling quite quickly as the acid is added, but
the curve very soon gets less steep. This is because a buffer solution is being set up - composed of
the excess ammonia and the ammonium chloride being formed.
Notice that the equivalence point is now somewhat acidic ( a bit less than pH 5), because pure
ammonium chloride isn't neutral. However, the equivalence point still falls on the steepest bit of
the curve. That will turn out to be important in choosing a suitable indicator for the titration.
5.4.3.2. Running alkali into the acid
At the beginning of this titration, you have an excess of hydrochloric acid. The shape of the curve
will be the same as when you had an excess of acid at the start of a titration running sodium
hydroxide solution into the acid.

PHYSICAL CHEMISTRY
It is only after the equivalence point that things become different.
A buffer solution is formed containing excess ammonia and ammonium chloride. This resists any
large increase in pH - not that you would expect a very large increase anyway, because ammonia is
only a weak base.
Titration curves for weak acid v strong base
We'll take ethanoic acid and sodium hydroxide as typical of a weak acid and a strong base.
5.4.3.3. Running acid into the alkali
For the first part of the graph, you have an excess of sodium hydroxide. The curve will be exactly
the same as when you add hydrochloric acid to sodium hydroxide. Once the acid is in excess, there
will be a difference.

PHYSICAL CHEMISTRY
Past the equivalence point you have a buffer solution containing sodium ethanoate and ethanoic
acid. This resists any large fall in pH.
Running alkali into the acid
The start of the graph shows a relatively rapid rise in pH but this slows down as a buffer solution
containing ethanoic acid and sodium ethanoate is produced. Beyond the equivalence
point (when the sodium hydroxide is in excess) the curve is just the same as that end of the HCl -
NaOH graph.

PHYSICAL CHEMISTRY
5.4.4. Titration curves for weak acid v weak base
The common example of this would be ethanoic acid and ammonia.
It so happens that these two are both about equally weak - in that case, the equivalence point is
approximately pH 7.
Running acid into the alkali
This is really just a combination of graphs you have already seen. Up to the equivalence point it is
similar to the ammonia - HCl case. After the equivalence point it is like the end of the ethanoic
acid - NaOH curve.
Notice that there isn't any steep bit on this graph. Instead, there is just what is known as a "point of
inflexion". That lack of a steep bit means that it is difficult to do a titration of a weak acid against a
weak base.
Calculate the pH values of the solution obtained by addition of varying amounts of 0.1M
NaOH(ag)
Initial pH
pH = - log (H+) = - log(0.1)
= 1
Add x less than 25 cm3

PHYSICAL CHEMISTRY
25-x unneutralised
Volume 25 + x
( 25−x ) 10−1
Concentration of H =
+
where x is the added volume.
(25+ x)
5.5. Indicators
Acid- base titrations are carried out in order to establish the equivalent amount of acid and base
which are required to neutralize each other. The most convenient method of locating the end
point is by use of an indicator which change colour at the end point of the titration.The indicator
must identify the end point of the titration, not necessarily the point at which the solution has pH
of 7. The end point at which the pH is 7 is only for strong acid – strong base pairs.
An indicator is a weak acid which has different colours in the ionized and unionized form.
e.g Hln(aq) + H2O(aq)↔ H+(aq) + ln-(aq)
Colour 1 Colour 11
In a strongly acidic form the unionized form predominates (cf Le chatelier’s principle). In a
strongly alkaline solution there will be a preponderance of In- ions. The colour will change
according to the pH of the solution. Atintermediate pH values the equation
pH = pKin + log¿ ¿ ¿ is used.
When [In-] = [Hln] then pH = pKin. Note that, the small amount of indicator added to the
solution does not affect the pH.Its actually the pH of the solution which determines the
equilibrium point of the indicator.
The colour are detected by the eye when one form of the indicator is about ten times the
concentration of the other form. i.e. when [Hln(aq)] = 10[ln-]
1
The pH = pKin +
10
The colour detection is only possible when the change in pH of approximately 2 has occurred.
This range is known as the theoretical working range of the pH.
5.5.1. Choice of indicators
Two considerations are important.
(i) pKin value should be close to the value of the pH of the solution at the end point, so that the
colour change occurs as closely as possible to the equivalence point.

PHYSICAL CHEMISTRY
(ii) the indicator working range should lie on the vertical part of the pH curve.
Working Range of indicators
Indicator pKin pH Range Colour Change

Colur in acid ColourAlkacid
Thymol blue 1.7 1.2 – 2.8 Red Yellow
Methyl orange 3.7 3.2 – 4.2 Red Yellow
Bromophenol 4.0 2.8 – 4.6 Yellow Blue
blue
Methyl red 5.1 4.2 – 6.3 Red Yellow
Bromothymol 7.0 6.0 – 7.6 Yellow Blue
blue
Phenolphthlein 9.3. 8.2 – 10.00 Colourless Red
Thymolphthalein 9.7 8.3 -10.5 Colourless Blue
5.6. Buffers
The progress of many reactions are affected by the pH of the solution in which they take part. A
buffer solution is able to counteract the effect of relatively small quantities of acid or alkali on
the pH of the solution. For example blood maintains a pH of about 7.4. a change in pH of 0.4
units could be fatal.
- Buffers can resist change in pH and can maintain pH within narrow ranges.
- Buffers can be designed to provide solutions of a particular pH.
Buffers are of two types
5.6.1. Acid Buffers
These have a pH less than 7 and are a combination of weak acids and their salts e.g. ethanoic
acid and sodium ethanoate.
5.6.2. Basic Buffers
Have a pH greater than 7 and are made from a weak bases and their salts.e.g.NH4Cl and NH3.
Buffer Capacity is defined as the number of equivalents of a strong base or acid that causes 1.0
litre of a buffer to undergo a 1 unit change in pH.
5.6.3. Action of an acid buffer
CH3COOH ↔CH3COO- + H+
CH3COO- Na+ ↔ CH3COO- + Na+

PHYSICAL CHEMISTRY
When a small quantity of acid is added.
CH3COO- + H+ ↔CH3COOH + H2O
When OH- ions are added.
H+ + OH →H2O.
The buffering capacity is highest when the pH is equal to the pKa value of the acid, i.e. when
half of the acid has been neutralized.
pH= pKa + log¿ ¿ ¿
pH
pH = pKa
Volume of base added.
5.6.4. Calculation pH of a buffer
The equation
[salt ]
pH= pKa + log
[acid]
is used to calculate the pH of an acidic buffer, for the basic buffer the following equation is used:
[salt ] [salt ]
pOH = pKb + log or pH = 14 – pKb + log
[base ] [base ]
5.7. Sparingly soluble salts
5.7.1. Solubility and Solubility product
A solid in contact with it’s a saturated solution is in dynamic equilibrium. The equilibrium law
can also be applied.
For example.
AgCl(aq) ↔ Ag+(aq) + Cl-(aq)
K = ¿¿¿ Therefore K[AgCl(s)] = [Ag+][Cl-] = Ksp

PHYSICAL CHEMISTRY
Ksp is the solubility product is of the concentration in solution of the ions of a sparingly soluble
salt.Ksp only applies to low concentrations where there is minimum ionic interference, since
they are so dilute.Solution of 0.01 moldm-3and less. The solubility product of an sparingly
soluble salt is a constant provided that the temperature is kept constant.
Some values of Ksp of sparingly soluble electrolytes
Compound Formula Ksp (25 °C)
Silver(I) acetate AgCH3COO 1.94×10-3
Silver(I) arsenate Ag3AsO4 1.03×10-22
Silver(I) bromate AgBrO3 5.38×10-5
Silver(I) bromide AgBr 5.35×10-13
Silver(I) chloride AgCl 1.77×10-10
Silver(I) chromate Ag2CrO4 1.12×10-12
Silver(I) cyanide AgCN 5.97×10-17
Aluminium hydroxide Al(OH)3 3×10-34
Aluminium phosphate AlPO4 9.84×10-21
Barium sulfate BaSO4 1.08×10-10
Calcium carbonate(aragonite) CaCO3 6.0×10-9
Calcium hydroxideCa(OH)2 5.02×10-6
Zinc hydroxide Zn(OH)2 3×10-17
5.7.2. Relationship between solubility and Ksp
PbI2(s) ↔ Pb2+(aq) + 2I-(aq)
Initial concentration 1 0 0
Equilibrium concentration 1-x x 2x

PHYSICAL CHEMISTRY
Solubility product Ksp = [Pb2+][I-]2
= (x)(2x)2
= 4x3 where x is the solubility.
Given the Ksp then the solubility is given by:
x= √3 Ksp
(i) Calculate the solubility product of PbI2 given that its solubility products is 1.21 x10-3 moldm-3
(ii) Calculate the solubility of PbCl3 in gdm-3 given that the solubility product is 2.0 x 10-5
mol3dm-9.
5.7.3. Common ion effect
The solubility of an ionic compound is decreased if the solution already contained one of the
ions. For example the solubility of AgCl in HCl is less than in pure water because of the Cl-
ions from HCl. (cf L Chateliers principle.)
AgCl(aq) ↔ Ag+(aq) + Cl-(aq)
(i) What happens when we add more AgCl to the solution.
(ii) What happens when we add more Cl- or Ag+ iron to the solution?
How are solubility product determined? Application in gravimetric analysis.
BaSO4(aq) ↔ Ba2+(aq) + SO42-(aq)
Calculate the solubility of BaSO4 in (a) water (b) in 0.1M H2SO4 given, that its solubility
product is 1.0 x 10-10 mol2dm-6.
CHAPTER 6
6.0. ELECTROLYSIS
Electrochemistry deals with equilibrium in redox systems. Michael Faraday (1834) described
conduction by electrolytes (molten substance and solutions) as electrolytic conduction. The
changes which took place were called electrochemical conduction. The vessel in which an
electrochemical change took place was called a cell.
6.1.0.Faraday’s 1stlaw of electrolysis.

PHYSICAL CHEMISTRY
The mass of a substance liberated at or discharged from an electrode is proportional to the

quantity of electricity passed.
6.1.1. Faraday ‘s2nd law of electrolysis.
When the same quantity of electricity is passed through different electrolytes, equivalent masses
of elements are deposited at the electrodes, or the same quantity of electricity is required to
liberate one mole of any univalent element during electrolysis
The second law can be verified using a combination of a coulometer and a voltammeter.
Coulometer is a cell in which charge measurements can be made and masses of substances
liberated or dissolved from electrodes determined.
Voltammeter is a cell to allow evolved gas to be collected and their volume measured.
Cell 1 Cell2 Cell3 Unit 4

AgNO3(aq), CuSO4(aq), Cr2(SO4)3(aq), Is a Hofmann Voltameter
Ag electrodes, Cu electrodes. Cr electrodes. containing dilute H2SO4.
reservor
dilute
H2SO4

PHYSICAL CHEMISTRY
1 2 3 4
Platinum
Electrodes
Ammeter Battery or DC power supply
Fig 6.1. To illustrate equivalents.Coulometer and voltmeter.
In the above experiment , 40.0mA flowed for 2 hours the masses dissolved from the anodes are
as follows: silver = 0.322g copper = 0.0948g chromium = 0.0518g.
The volume of gases were as at room temp and pressure (r.t.p.) follows:
Hydrogen = 35.8 cm oxygen = 17.9cm3 (gas molar volume at r.t p. is 24.0 dm 3)
Quantity of electricity passed Q = current (A) x time(s)

= 40 x 10-3 x 2 x 60 x 60
= 288C
Quantity of charge required to discharge one mole of each substance.
108 x 288
Silver 0.322g ---> 288C = 96.5 x103C
0.322
108g ---> ?
63.5 x 288
Copper 0.0948g ---> 288C = 193 x 103C
0.0948
63.5g ---> ?
52.0 x 288
Chromium 0.051g ---> 288C = 289 x103C
0.0518
52.0g ---> ?
2400 x 288
Hydrogen 35.8sm 3 ---> 288C = 193x103C
35.8
2400cm3 ---> ?
2400 x 288
Oxygen 17.9cm 3 ---> 288C = 386 x 103C
17.9
PHYSICAL CHEMISTRY
2400cm3 ---> ?
Amounts of substances deposited are:
1 1
Silver, one (1) mole, copper, half ( ) of a mole, chromium, one third ( ) of amole,
2 3
1 1
hydrogen, one half ( ) of a mole and oxygen, one quarter ( ) of a mole. Therefore the
2 2
equivalence directly relates to valence ratios. In general the amount of elements discharged, are
given by:
no of moles of electrons
Amounts of elements=
no of charges on one ion of theelement .
Faradays’ constant( F) has a numerical value of 96500C. One faraday is a charge carried by one
mole of electrons each with a charge of 1.62 x 10-19C or one mole of single charged ions.
F= Avogadros’ constant(L) x charge on an electron(e).
Therefore F = Le
F = 6.02 x1023 x 1.62 x 10-19 C
F= 96500C.
6.2. Mechanism of electrolysis
Ions which are free to move and hence produce electricity are produced in three ways:
(i) Breaking up an ionic crystal by melting it.
(ii) Breaking up an ionic crystal by dissolving it in water.
(iii) Allowing non-ionic substances to react with water.( If the energy released by the
reaction of non-ionic substance with water is greater than the energy required to break
the bonds and separate the ions, the substance may ionise on contact with water.
HCl(g) + H2O(l) → H+(g) + Cl-(aq))
When a liquid containing positive and negative ions is electrolyzed with direct current(d.c.), the
flow of electrons from the battery ( electron pump) is at the cathode to convert cations to free
metal (or hydrogen). At the anode, negatively charged anions give up their electrons to the
positive electrode. Thus an electric current flows.
Flow of electrons BATTERY Flow of electrons

(electron pump)
Electrolyte ionizes(sodium chroride)

NaCl

PHYSICAL CHEMISTRY
Na+Cl-
Anode(+) Anions Cations Cathode(-)
Requires electrons Supplying Requiring Supplies electrons
Electrons Electrons
Fig6.2 Showing the mechanism of electrolysis.
6.3. Discharge at the cathode.

When there are two or more different types of cations, the cation discharged is the one which can
gain electrons more readily, that is preferential discharge.
K+(aq)
Ca2+(aq)
Na+(aq)
Mg2+(aq)
Al3+(aq) increasing ease of discharge at cathode.
Zn2+(aq)
Fe2+(aq)
Sn2+(aq)
Pb2+(aq)
H+(aq)
Cu2+(aq)
Ag+(aq)
Au+(aq)
6.4. Electrode process at the anode.

If two or more anions are present in aqueous solution they are discharged in the order shown:
I-(aq)
OH-(aq)
Cl-(aq) increasing ease of discharge at anode
NO (aq)
3-
SO42-
Other large anions
6.5. Concentration effect.
When one metallic ion Xm+(aq) is present in a much higher concentration than the other metallic
ion Yn+(aq), then Xm+(aq) may be discharged at the same time as Yn+(aq) even though in a normal
situation metallicXm+(aq) would have been discharged. For example Zn2+ and Cu2+ are discharged
at the same time when zinc ions are present in much higher concentration. This is how the alloy
brass is produced.
With Cl- and OH-, oxygengas(O2) is liberated at moderate concentration. At high Cl-
concentrations chlorine gas (Cl2) is liberated.
PHYSICAL CHEMISTRY
6.6. Overvoltage effect.

Hydrogen ion are discharged easily at platinum electrodes, but when other electrodes are used
such lead, zinc, tin, aluminum and especially mercury, they not easily discharged as indicated by
its position in the electrochemical series.
6.7. Alternative electrode at the anode.
If the atoms of the anode can lose electrons and pass into solution as hydrated ions more easily
than hydrated anions can be discharged they will do so. Thus in electrolysis of dilute solution of
copper(ii) sulphate the reaction at the copper anode is as following:
2Cu(s) ---> 2Cu+(aq)+ 4e-
rather than
4OH-(aq) --->2H2O(l) + O2(aq) + 4e-
6.8. The industrial importance of electrolytic methods.
(i) Electrolysis of fused halides for extraction of groups 1 and 2 metals of the Periodic
Table.
(ii) Electro-winning of gold in gold production.
(iii) Manufacture of Aluminium by electrolysis of purified Aluminium oxide, Al2O3,
dissolved in fused cryolite, Na3AlF6 .
(iv) Purification of copper by making it the anode in an electrolytic cell in which a pure
copper strip is used as the cathode.
(v) Production of chlorine gas and sodium hydroxide from brine(concentrated sodium
chloride).
(vi) Electroplating of articles using metals such as chromium, silver and nickel.
CHAPTER 7
7.0.PHASE EQUILIBRIA
Matter can exist in any one of the following three states, that is solid liquid and gas.
Solid ↔ liquid ↔ gas
In order to define the conditions of a system to exist in equilibrium a phase rule is used. This is a
generalization which seeks to explain, the equilibrium existing in heterogeneous system.
7.1. Phase (p)
PHYSICAL CHEMISTRY
Is the part of a system, which is homogeneous and capable of being mechanically separated from
other parts of the system.
7.2. Component(c)
Is a substance that make up the system, for example an equilibrium mixture of ice, water and
water vapour is expressed as a one component system, i.e. water. The components in a system
isdefined as the number of substances which must be chosen to express fully the composition of
every phase of the system.
7.3. Degrees of freedom (f)/variance
Is the number of intensive variables the can be changed independently without disturbing the
number of phases in equilibrium. In order to define completely a system at equilibrium, it is
necessary to state the values of certain variables, such as temp and pressure.
The phase rule: p + f = c + 2 p = no of phases, f = degrees of freedom and c = no of
components in the system. This equation tells us whether a system can reach equilibrium under
a given set of conditions. E.g.Liquid-vapour system of water at a fixed temp. p=2 f=1 and c=1.
i.e. 2+1=2+1. The phase rule is obeyed and a true equilibrium is feasible.
7.4. Phase equilibrium involving a single system
However strong the bonding that binds the individual particles, in a solid or a liquid, there are
always some particles, which possess, sufficient energy to escape into the gaseous phase.
evaporation / boiling
water
Fig 7.0 Water molecules leaving the bulk of the liquid.

If water is poured into an open vessel, it evaporates and the loss of energetic molecules would
result in reduction of temp. Energy is absorbed from the surroundings and a constant temp is
maintained. If the vessel is closed , and connected to a mercury manometer the pressure reaches
a maximum. A state of dynamic equilibrium would have been attained. The maximum pressure
developed by the water at a fixed temp is called its saturation vapour pressure. All solids and
liquids have their own characteristic saturation vapour pressure at a constant temp. At room temp
the vapour pressure of metals is too little to be detected, but for ethoxyethane (ordinary ether) is
quite appreciable.
Liquid↔vapour
Kp = Pliquid
A liquid boils when its saturation vapour pressure is equal to the external pressure. For a solid
the saturation vapour pressure is called the sublimation pressure.
7.5. Phase diagrams

PHYSICAL CHEMISTRY
The various equilibrium that can exist between phases is commonly presented on a phase
diagram. For a one component system, the behavior of various phases is shown by means of a
graph of temp versus pressure.
220 C A
Pressure Solid water

(atm) Liquid water
1.0
Pt O
D Water vapour
Tt 273.16K 373K 647K Temp/K
Fig 7.1. Phase diagram for a pure substance.(Ice / water/water vapour system)
In the diagram a line represents the conditions under which two phases exist in equilibrium. The
area bounded by the lines represents conditions under which only one phase exists. The degree of
freedom of water vapour f is equal to two (f=2).
Curve O-A relates to a 2 phase system and shows the pressure of vapour which is in equilibrium
with liquid water at different temps. The upper limit of OA corresponds to a temp of 647K is
called the critical temp of water. The lower limit of OB is at absolute zero temp. If a liquid is
cooled below its normal freezing temp, without solidifying, the liquid is said to be super cooled.
It posses vapour pressure which varies with temp shown by line OD. A super cooled liquid is
said to be in a metastable state.
Point O is called the triple point. It shows the conditions at which the three phases are in
equilibrium. At O f is equal to zero (f=0) and is known as an invariant system. For one phase
like ice f is equal to 2 (f=2) and is a bi-variant system.
Line OC (slops from right to left in an upward direction) shows the effect of pressure on the
melting of ice. When pressure is increased, the melting point of ice decreases.
Y Z
Pressure(atm)
PHYSICAL CHEMISTRY
Solid CO2 Liquid CO2
5.11 O
1.00 Gaseous CO2
216.6 Temp/K
Fig 7.2 Phase diagram for carbon dioxide.
The system for carbon dioxide is similar to the ice/water /water vapour system. There are,
however, two important differences: the triple point O is now above the atmospheric pressure(it
occurs at 5.11atm and a temp of 216.6K). This means that carbon dioxide will pass directly into
gas without becoming a liquid. It sublimes. Liquid carbon dioxide exists at pressures above
5.11atms. The second difference the line OY slopes from left to right in an upward direction.
This means that an increase in pressure raises the melting point of solid carbon dioxide.
7.6. Vapour pressure of ideal solutions
An ideal solution consisting of two components, A and B is one in which there is neither a
volume change on mixing (∆Vmix= 0) nor an enthalpy change in mixing (∆Hmix =0). The
tendency of particles in pure A to enter into the vapour phase is the same as in a mixture of A
and B. The relationship between partial vapour pressure, the vapour pressure and the mole
fraction of A is given in the Raoult’s law.
Raoult’s: The partial vapour pressure of any volatile component of an ideal solution is equal to
the vapour pressure of the pure component multiplied by the mole fraction of that component in
solution.
PA = PA0 XA
PA is the partial vapour pressure of component A

PA0 is the vapour pressure of component A
XA is the mole fraction of component A
Similarly for B PB =PB0XB

PHYSICAL CHEMISTRY
The total vapour pressure of the solution ( at fixed temp) Pt is the sum of the vapour pressures of
A and B
PA+ PB=PA0 XA+ PB0XB and XA + XB = 1
7.7. Variation of total pressure with mole fraction
Total vapour
pressure (Pt)
Vapour
Pressure Partial vapour
Pressure forA
at fixed
Temp
Partial vapour
Pressure for B
0 0.5 1.0
Mole fraction of A
1.0 0.5 0
Mole fraction of B
Fig7.3 Showing variation of total vapour pressure with mole fraction.
In the above diagram the vapour pressure of A is greater than that of B, hence the vapour is
richer in A than in B. That is the mole fraction of a should be greater in the vapour than in the
liquid.
Suppose at a fixed temp a pure component a has a vapour pressure of 1x104 Pa and B 3x103 Pa.
Consider a solution in which the mole fraction of A and B are equal i.e. XA = XB = 0.5.
The partial vapour pressure of A, PA= (1 x104)x 0.5 = 5.0 x103Pa
The partial vapour pressure of B, PB = (3x103)x0.5 = 1.5 x 103Pa
The total pressure PA + PB =Pt= 5.0 x 103 + 1.5 x 103 = 6.5 x103 Pa

PHYSICAL CHEMISTRY
P A 5.0 x 103
The mole fraction of A in the vapour phase XA’ = = = 0.77
P A+ P 6.5 x 103
B
Therefore mole fraction of B in the vapour phase is : 1- 0.77 = 0.23. (XA in solution 0.5, in
vapour 0.77)
Values of XA= 0 up to XA= 1.0 can be calculated and plotted in a graph
10.0
9.0 Liquid composition curve
8.0
Vapour pressure/Pax10
3
7.0 Y Z
at fixed temp
6.0

PHYSICAL CHEMISTRY
5.0 Vapour
4.0 composition
3.0 curve
2.0
1.0
0 0.5 1.0
Mole fraction of component A
1.0 0.5 0
Mole frction of component B
Fig 7.4 Boiling point composition for component A and B
7.8. Boiling point –composition diagram for ideal solutions
Fractional distillation is based on the fact that the more volatile component is richer in the vapour
of a more volatile component.
For example:
2-methylpropan-1-ol CH3CH(CH3)CH2-OH and propanol CH3CH2CH2-OH
110

PHYSICAL CHEMISTRY
Boiling 100
Point C D
At 1atm
90
E F
80 G
0 0.1 0.20.3 0.4 0.5 0. 0.7 0.8 0.9 1.0
Mole fraction of propanol
Mole fraction of 2-methylpropan-1-ol
Fig 7.5 Showing enrichment of the vapour of a more volatile component
Consider a mixture which is 0.21 in propanol. This mixture will boil at a temp of about 97.50C
(C above). This liquid will be in equilibrium with a vapour richer in propanol point D (above
0.59). If the vapour is removed and cooled it will produce a liquid of composition 0.58(E
above)9lo. This is in equilibrium with a vapour of composition F. Remove and cool to G.
Repeating this process would result in the separation of pure propanol
7.9.Steam distillation

PHYSICAL CHEMISTRY
Fig 7.6 Distillation unit.

Steam distillation is a special type of distillation (a separation process) for temperature sensitive
materials like natural aromatic compounds.
Many organic compounds tend to decompose at high sustained temperatures. Separation by

normal distillation would then not be an option, so water or steam is introduced into the
distillation apparatus. By adding water or steam, the boiling points of the compounds are
depressed, allowing them to evaporate at lower temperatures, preferably below the temperatures
at which the deterioration of the material becomes appreciable. If the substances to be distilled
are very sensitive to heat, steam distillation can also be combined with vacuum distillation. After
distillation the vapors are condensed as usual, usually yielding a two-phase system of water and
the organic compounds, allowing for simple separation.

PHYSICAL CHEMISTRY
Fig 7.7 Fractional distillation

As an example, consider the distillation of a mixture of water and ethanol. Ethanol boils at 78.4
°C while water boils at 100 °C. So, by gently heating the mixture, the most volatile component
will concentrate to a greater degree in the vapor leaving the liquid. Some mixtures form
azeotropes, where the mixture boils at a lower temperature than either component. In this
example, a mixture of 96% ethanol and 4% water boils at 78.2 °C, being more volatile than pure
ethanol. For this reason, ethanol cannot be completely purified by direct fractional distillation of
ethanol-water mixtures.
The apparatus is assembled as in the diagram. (The diagram represents a batch apparatus, as
opposed to a continuous apparatus.) The mixture is put into the round bottomed flask along with
a few anti-bumping granules (or a Teflon coated magnetic stirrer bar if using magnetic stirring),
and the fractionating column is fitted into the top. As the mixture boils, vapor rises up the
column. The vapor condenses on the glass platforms, known as trays, inside the column, and
runs back down into the liquid below, refluxing distillate. The column is heated from the bottom.
The efficiency in terms of the amount of heating and time required to get fractionation can be
improved by insulating the outside of the column in an insulator such as wool, aluminium foil or
preferably a vacuum jacket. The hottest tray is at the bottom and the coolest is at the top. At
steady state conditions, the vapor and liquid on each tray are at equilibrium. Only the most
volatile of the vapors stays in gaseous form all the way to the top. The vapor at the top of the
column, then passes into the condenser, which cools it down until it liquefies. The separation is
more pure with the addition of more trays (to a practical limitation of heat, flow, etc.) The

PHYSICAL CHEMISTRY
condensate that was initially very close to the azeotrope composition becomes gradually richer in
water. The process continues until all the ethanol boils out of the mixture. This point can be
recognized by the sharp rise in temperature shown on the thermometer.
Typically the example above now only reflects the theoretical way fractionation works. Normal
laboratory fractionation columns will be simple glass tubes (often vacuum jacketed, and
sometimes internally silvered) filled with a packing, often small glass helices of 4 to 7 mm
diameter. Such a column can be calibrated by the distillation of a known mixture system to
quantify the column in terms of number of theoretical plates. To improve fractionation the
apparatus is set up to return condensate to the column by the use of some sort of reflux splitter
(reflux wire, gago, Magnetic swinging bucket, etc.) - a typical careful fractionation would
employ a reflux ratio of around 10:1 (10 parts returned condensate to 1 part condensate take off).
In laboratory distillation, several types of condensers are commonly found. The Liebig condenser
is simply a straight tube within a water jacket, and is the simplest (and relatively least expensive)
form of condenser. The Graham condenser is a spiral tube within a water jacket, and the Allihn
condenser has a series of large and small constrictions on the inside tube, each increasing the
surface area upon which the vapor constituents may condense.
Alternate set-ups may utilize a "cow" or "pig" which is connected to three or four receiving
flasks. By turning the "cow" or "pig", the distillates can be channeled into the appropriate
receiver. A Perkin triangle is versatile piece of apparatus that can also be used to collect
distillation fractions which does not require a "cow" or "pig" adapter. A Perkin triangle is most
often used where the distillates are air-sensitive or where the fractions distill and are collected
under reduced pressure, but can be used for a simple and fractional distillation.
Vacuum distillation systems operate at reduced pressure, thereby lowering the boiling points of
the materials. Note that the use of anti-bumping granules will not work at reduced pressures.
7.10 Industrial distillation

Image 2: Typical industrial fractional distillation columnsDistillation is the most common form
of separation technology used in petroleum refineries, petrochemical and chemical plants ,
natural gas processing and cryogenic air separation plants.[2][3] In most cases, the distillation is
operated at a continuous steady state. New feed is always being added to the distillation column
and products are always being removed. Unless the process is disturbed due to changes in feed,
heat, ambient temperature, or condensing, the amount of feed being added and the amount of
product being removed are normally equal. This is known as continuous, steady-state fractional
distillation.
Industrial distillation is typically performed in large, vertical cylindrical columns known as

"distillation or fractionation towers" or "distillation columns" with diameters ranging from about
PHYSICAL CHEMISTRY
65 centimetres to 6 metres and heights ranging from about 6 metres to 60 metres or more. The
distillation towers have liquid outlets at intervals up the column which allow for the withdrawal
of different fractions or products having different boiling points or boiling ranges. By increasing
the temperature of the product inside the columns, the different hydrocarbons are separated. The
"lightest" products (those with the lowest boiling point) exit from the top of the columns and the
"heaviest" products (those with the highest boiling point) exit from the bottom of the column.
For example, fractional distillation is used in oil refineries to separate crude oil into useful
substances (or fractions) having different hydrocarbons of different boiling points. The crude oil
fractions with higher boiling points:
■have more carbon atoms

■have higher molecular weights
■are more branched chain alkanes
■are darker in color
■are more viscous
■are more difficult to ignite and to burn

PHYSICAL CHEMISTRY
Fig 7.8 Distillation of crude oil.

Large-scale industrial towers use reflux to achieve a more complete separation of
products. Reflux refers to the portion of the condensed overhead liquid product from a
distillation or fractionation tower that is returned to the upper part of the tower as shown in the
schematic diagram of a typical, large-scale industrial distillation tower. Inside the tower, the
reflux liquid flowing downwards provides the cooling needed to condense the vapors flowing
upwards, thereby increasing the effectiveness of the distillation tower. The more reflux is
provided for a given number of theoretical plates, the better the tower's separation of lower
boiling materials from higher boiling materials. Alternatively, the more reflux provided for a
given desired separation, the fewer theoretical plates are required.
Figure 7.8. Crude oil is separated into fractions by fractional distillation. The fractions at the top
of the fractionating column have lower boiling points than the fractions at the bottom. The heavy
bottom fractions are often cracked into lighter, more useful products. All of the fractions are
processed further in other refining units.Fractional distillation is also used in air separation,
producing liquid oxygen, liquid nitrogen, and highly concentrated argon. Distillation of
chlorosilanes also enable the production of high-purity silicon for use as a semiconductor.
In industrial uses, sometimes a packing material is used in the column instead of trays, especially
when low pressure drops across the column are required, as when operating under vacuum. This
packing material can either be random dumped packing (1-3" wide) such as Raschig rings or
structured sheet metal. Typical manufacturers are Koch, Sulzer and other companies. Liquids
tend to wet the surface of the packing and the vapors pass across this wetted surface, where mass

PHYSICAL CHEMISTRY
transfer takes place. Unlike conventional tray distillation in which every tray represents a
separate point of vapor liquid equilibrium the vapor liquid equilibrium curve in a packed column
is continuous. However, when modeling packed columns it is useful to compute a number of
"theoretical plates" to denote the separation efficiency of the packed column with respect to more
traditional trays. Differently shaped packings have different surface areas and void space
between packings. Both of these factors affect packing performance.
7.11. Non- Ideal mixtures

Raoult's Law only works for ideal mixtures. In these, the forces between the particles in the
mixture are exactly the same as those in the pure liquids. The tendency for the particles to escape
is the same in the mixture and in the pure liquids.
That's not true in non-ideal mixtures.
7.11.1. Distillation of non-ideal mixtures
If two solvents can form a positive azeotrope, then distillation of any mixture of those
constituents will result in the distillate being closer in composition to the azeotrope than the
starting mixture. For example, if a 50/50 mixture of ethanol and water is distilled once, the
distillate will be 80% ethanol and 20% water (see ethanol data page), which is closer to the
azeotropic mixture than the original. Distilling the 80/20% mixture produces a distillate that is
87% ethanol and 13% water. Further repeated distillations will produce mixtures that are
progressively closer to the azeotropic ratio of 95.5/4.5%. No number of distillations, however,
will ever result in a distillate that exceeds the azeotropic ratio. Likewise when distilling a mixture
of ethanol and water that is richer in ethanol than the azeotrope, the distillate (contrary to
intuition) will be poorer in ethanol than the original but slightly richer than the azeotrope. This
means the solution left behind will be richer in ethanol.
If two solvents can form a negative azeotrope, then distillation of any mixture of those
constituents will result in the residue being closer in composition to the azeotrope than the
original mixture. For example, if a hydrochloric acid solution contains less than 20.2% hydrogen
chloride, boiling the mixture will leave behind a solution that is richer in hydrogen chloride than
the original. If the solution initially contains more than 20.2% hydrogen chloride, then boiling
will leave behind a solution that is poorer in hydrogen chloride than the original. Boiling of any
hydrochloric acid solution long enough will cause the solution left behind to approach the
azeotropic ratio.
An azeotrope is a mixture of two or more liquids in such a ratio that its composition cannot be
changed by simple distillation. This occurs because, when an azeotrope is boiled, the resulting
vapor has the same ratio of constituents as the original mixture.

PHYSICAL CHEMISTRY
Because their composition is unchanged by distillation, azeotropes are also called (especially in
older texts) constant boiling mixtures. The word azeotrope is derived from the Greek words
ζέειν (boil) and τρόπος (change) combined with
7.11.2. Positive deviation
When the cohesive forces between like molecules are greater than the adhesive forces, the
dissimilarities of polarity or internal pressure will lead both components to escape solution more
easily. Therefore, the vapor pressure will be greater than the expected from the Raoult's law,
showing positive deviation.
Fig 7.9 Showing positive deviation.
If the deviation is large, then the vapor pressure curve will show a maximum at a particular
composition, e.g. benzene and ethyl alcohol, carbon disulfide and acetone, chloroform and
ethanol.
7.11.3. Minimum boiling or positive azeotrope
The below shows a positive azeotrope of hypothetical constituents, X and Y. The bottom trace
illustrates the boiling temperature of various compositions. Below the bottom trace, only the
liquid phase is in equilibrium. The top trace illustrates the vapor composition above the liquid at
a given temperature. Above the top trace, only the vapor is in equilibrium. Between the two
traces, liquid and vapor phases exist simultaneously in equilibrium: for example, heating a 25%

PHYSICAL CHEMISTRY
X : 75% Y mixture to temperature AB would generate vapor of composition B over liquid of

composition A.
Fig 7.10 Minimum boiling point azeotrope.
The azeotrope is the point on the diagram where the two curves touch. The horizontal and
vertical steps show the path of repeated distillations. Point A is the boiling point of a
nonazeotropic mixture. The vapor that separates at that temperature has composition B. The
shape of the curves requires that the vapor at B be richer in constituent X than the liquid at point
A. The vapor is physically separated from the VLE (vapor-liquid equilibrium) system and is
cooled to point C, where it condenses. The resulting liquid (point C) is now richer in X than it
was at point A. If the collected liquid is boiled again, it progresses to point D, and so on. The
stepwise progression shows how repeated distillation can never produce a distillate that is richer
in constituent X than the azeotrope. Note that starting to the right of the azeotrope point results in
the same stepwise process closing in on the azeotrope point from the other direction.
7.11.4. Negative deviation
When adhesive forces between molecules of A and B are greater than the cohesive force between
A and A, or B and B, then the vapor pressure of the solution is less than the expected vapor
pressure from Raoult's law. This is called a negative deviation from Raoult's law. These cohesive
forces are lessened not only by dilution but also attraction between two molecules through
formation of hydrogen bonds. This will further reduce the tendency of A and B to escape.

PHYSICAL CHEMISTRY
Fig 7.11 Showing negative deviation.
For example, chloroform and acetone show such an attraction by formation of a hydrogen bond.
7.11.5. Maximum boiling or negative azeotrope
The diagram on the right shows a negative azeotrope of hypothetical constituents, X and Y.
Again the bottom trace illustrates the boiling temperature at various compositions, and again,
below the bottom trace the mixture must be entirely liquid phase. The top trace again illustrates
the condensation temperature of various compositions, and again, above the top trace the mixture
must be entirely vapor phase. The point, A, shown here is a boiling point with a composition
chosen very near to the azeotrope. The vapor is collected at the same temperature at point B.
That vapor is cooled, condensed, and collected at point C. Because this example is a negative
azeotrope rather than a positive one, the distillate is farther from the azeotrope than the original
liquid mixture at point A was. So the distillate is poorer in constituent X and richer in constituent
Y than the original mixture. Because this process has removed a greater fraction of Y from the
liquid than it had originally, the residue must be poorer in Y and richer in X after distillation than
before.

PHYSICAL CHEMISTRY
Fig 12 Maximum boiling point azeotrope.
If the point, A, had been chosen to the right of the azeotrope rather than to the left, the distillate
at point C would be farther to the right than A, which is to say that the distillate would be richer
in X and poorer in Y than the original mixture. So in this case too, the distillate moves away
from the azeotrope and the residue moves toward it. This is characteristic of negative azeotropes.
No amount of distillation, however, can make either the distillate or the residue arrive on the
opposite side of the azeotrope from the original mixture. This is characteristic of all azeotropes.
7.12. SOLID-LIQUID PHASE DIAGRAMS: TIN AND LEAD
This section explains the relationship between the cooling curves for liquid mixtures of tin and
lead, and the resulting phase diagram. It also offers a simple introduction to the idea of a eutectic
mixture. Detailed study of such systems, when the components are metallic, are carried out by
metallurgists. Such work is important in research devoted to the development of alloys with
certain specific properties.
7.12.1. Cooling curves for pure substances
Suppose you have some pure molten lead and allow it to cool down until it has all solidified,
plotting the temperature of the lead against time as you go. You would end up with a typical
cooling curve for a pure substance.

PHYSICAL CHEMISTRY
Fig 13 Cooling curve for pure lead.
Throughout the whole experiment, heat is being lost to the surroundings - and yet the
temperature doesn't fall at all while the lead is freezing. This is because the freezing process
liberates heat at exactly the same rate that it is being lost to the surroundings.
Energy is released when new bonds form - in this case, the strong metallic bonds in the solid
lead.
If you repeated this process for pure liquid tin, the shape of the graph would be exactly the same,
except that the freezing point would now be at 232°C.
Fig 13 Cooling curve for pure tin.

PHYSICAL CHEMISTRY
7.12.2. Cooling curves for tin-lead mixtures
If you add some tin to the lead, the shape of the cooling curve changes. The next graph shows
what happens if you cool a liquid mixture containing about 67% lead and 33% tin by mass.
Fig .14 Cooling curve for tin-lead.
There are lots of things to look at:
Notice that nothing happens at all at the normal freezing point of the lead. Adding the tin to it
lowers its freezing point.
Freezing starts for this mixture at about 250°C. You would start to get some solid lead formed -
but no tin. At that point the rate of cooling slows down - the curve gets less steep.
However, the graph doesn't go horizontal yet. Although energy is being given off as the lead
turns to a solid, there isn't anything similar happening to the tin. That means that there isn't
enough energy released to keep the temperature constant.
The temperature does stop falling at 183°C. Now both tin and lead are freezing. Once everything
has solidified, the temperature continues to fall.
7.12.3. Changing the proportions of tin and lead

PHYSICAL CHEMISTRY
If you had less tin in the mixture, the overall shape of the curve stays much the same, but the
point at which the lead first starts to freeze changes.
The less tin there is, the smaller the drop in the freezing point of the lead.
For a mixture containing only 20% of tin, the freezing point of the lead is about 275°C. That's
where the graph would suddenly become less steep.
BUT . . . you will still get the graph going horizontal (showing the freezing of both the tin and
lead) at exactly the same temperature: 183°C.
As you increase the proportion of tin, the first signs of solid lead appear at lower and lower
temperatures, but the final freezing of the whole mixture still happens at 183°C.
That continues until you have added enough tin that the mixture contains 62% tin and 38% lead.
At that point, the graph changes.
Fig. 15 Cooling curve 62% tin.
This particular mixture of lead and tin has a cooling curve which looks exactly like that of a pure
substance rather than a mixture. There is just the single horizontal part of the graph where
everything is freezing.
However, it is still a mixture. If you use a microscope to look at the solid formed after freezing,
you can see the individual crystals of tin and lead.

PHYSICAL CHEMISTRY
This particular mixture is known as a eutectic mixture. The word "eutectic" comes from Greek
and means "easily melted".
The eutectic mixture has the lowest melting point (which is, of course, the same as the freezing
point) of any mixture of lead and tin. The temperature at which the eutectic mixture freezes or
melts is known as the eutectic temperature.
7.12.4. What happens if there is more than 62% of tin in the mixture?
You can trace it through in exactly the same way, by imagining starting with pure tin and then
adding lead to it.
The cooling curve for pure liquid tin looks like this:
Fig 16.Cooling curve for pure tin.
It's just like the pure lead cooling curve except that tin's freezing point is lower.
If you add small amounts of lead to the tin, so that you have perhaps 80% tin and 20% lead, you
will get a curve like this:

PHYSICAL CHEMISTRY
Fig 16. Cooling curve for 80% tin.
Notice the lowered freezing point of the tin. Notice also the final freezing of the whole mixture
again takes place at 183°C.
7.13.The phase diagram
7.13.1. Constructing the phase diagram
You start from data obtained from the cooling curves. You draw a graph of the temperature at
which freezing first starts against the proportion of tin and lead in the mixture. The only unusual
thing is that you draw the temperature scale at each end of the diagram instead of only at the left-
hand side.
Fig. 17 Phase diagram for tin-lead.

PHYSICAL CHEMISTRY
Notice that at the left-hand side and right-hand sides of the curves you have the freezing points
(melting points) of the pure lead and tin.
To finish off the phase diagram, all you have to do is draw a single horizontal line across at the
eutectic temperature. Then you label each area of the diagram with what you would find under
the various different conditions.
Fig. 18 Labeled phase diagram for tin –lead.
7.13.2. Using the phase diagram
Suppose you have a mixture of 67% lead and 33% tin. That's the mixture from the first cooling
curve plotted above. Suppose it is at a temperature of 300°C.
That corresponds to a set of conditions in the area of the phase diagram labeled as molten tin and
lead.

PHYSICAL CHEMISTRY
Fig. 19 Constructing a cooling curve from 3000C
Now consider what happens if you cool that mixture. Eventually the temperature will drop to a
point where it crosses the line into the next region of the diagram.
At that point, the mixture will start to produce some solid lead - in other words, the lead (but not
the tin) starts to freeze. That happens at a temperature of about 250°C.
Fig. 20 Lead starts to deposit at 250oC

PHYSICAL CHEMISTRY
Now, it is the next bit that needs careful thinking about, because there are two different ways you
can look at it. If you have been taught to do it one way, then stick with that - otherwise you risk
getting very confused!
7.13.3. Thinking about changes in the composition of the liquid
When the first of the lead freezes, the composition of the remaining liquid changes. It obviously
becomes proportionally richer in tin. That lowers the freezing point of the lead a bit more, and so
the next bit of lead freezes at a slightly lower temperature - leaving a liquid still richer in tin.
This process goes on. The liquid gets richer and richer in tin, and the temperature needed to
freeze the next lot of lead continues to fall. The set of conditions of temperature and composition
of the liquid essentially moves down the curve - until it reaches the eutectic point.
Fig. 21 Change in the cooling curve.
Once it has reached the eutectic point, if the temperature continues to fall, you obviously just
move into the region of a mixture of solid lead and solid tin - in other words, all the remaining
liquid freezes.
7.13.4. Thinking about the composition of the system as a whole
We've seen that as the liquid gradually freezes, its composition changes. But if you look at the
system as a whole, obviously the proportions of lead and tin remain constant - you aren't taking
anything away or adding anything. All that is happening is that things are changing from liquids
to solids.

PHYSICAL CHEMISTRY
So suppose we continue the cooling beyond the temperature that the first solid lead appears and
the temperature drops to the point shown in the next diagram - a point clearly in the "solid lead
and molten mixture" area.
Fig. 22 Cooling beyond the first deposition.
What would you see in the mixture? To find out, you draw a horizontal tie line through that
point, and then look at the ends of it

PHYSICAL CHEMISTRY
Fig.23 Showing tie line.
At the left-hand end, you have 100% lead. That represents the solid lead that has frozen from the
mixture. At the right-hand end, you have the composition of the liquid mixture. This is now
much richer in tin than the whole system is - because obviously a fair bit of solid lead has
separated out. As the temperature continues to fall, the composition of the liquid mixture (as
shown by the right-hand end of the tie line) will get closer and closer to the eutectic mixture.
Fig.24 Showing relationship between temp and composition.
It will finally reach the eutectic composition when the temperature drops to the eutectic
temperature - and the whole lot then freezes.
At a temperature lower than the eutectic temperature, you are obviously in the solid lead plus
solid tin region. That's fairly obvious!
If you cooled a liquid mixture on the right-hand side of the phase diagram (to the right of the
eutectic mixture), everything would work exactly the same except that solid tin would be formed
instead of solid lead. If you have understood what has gone before, it isn't at all difficult to work
out what happens.
Finally . . . what happens if you cool a liquid mixture which has exactly the eutectic
composition?

PHYSICAL CHEMISTRY
It simply stays as a liquid mixture until the temperature falls enough that it all solidifies. You
never get into the awkward areas of the phase diagram.
7.13.5 Tin-lead mixtures as solder
Traditionally, tin-lead mixtures have been used as solder, but these are being phased out because
of health concerns over the lead. This is especially the case where the solder is used to join water
pipes where the water is used for drinking. New non-lead solders have been developed as safer
replacements.
Typical old-fashioned solders include:
60% tin and 40% lead. This is close to the eutectic composition (62% tin and 38% lead), giving a
low melting point. It will also melt and freeze cleanly over a very limited temperature range.
This is useful for electrical work.
50% tin and 50% lead. This will melt and freeze over a wider range of temperatures. When it is
molten it will start to freeze at about 220°C and finally solidify at the eutectic temperature of
183°C. That means that it stays workable for a useful amount of time. That's helpful if it is being
used for plumbing joints.
7.14. Ice and Salt
Alloys are not the only binary systems for which phase diagrams are useful. A portion of the
water-salt phase diagram is shown at the right below. At the left is pure water, in this case ice
below 0°C. On the right, but not shown, is pure salt, NaCl above 0.15°C and NaCl·H2O below.
Below the horizontal line at -21°C is solid ice + salt. We presume that ice and salt are
immiscible, so that in the solid state neither includes any of the other, which is a good
approximation. Above the horizontal line, there are three regions, the middle of which represents
a homogeneous solution phase, the other two mixtures of solution with solid ice and solid salt.
The point E is a eutectic, where three phases are present, so that f = 0. The vertical line above
point B represents a saturated solution of salt in water. The solubility of salt does not depend
much on the temperature. More accurate figures from a handbook give a solubility of 35.7% at
0°C, 39.8% at 100°C. The heat of solution of salt is -1180 cal/mole or -20.2 cal/g. The minus
sign indicates that heat is absorbed when salt dissolves. Since this happens at constant pressure
here, it is an enthalpy change, ΔH.

PHYSICAL CHEMISTRY
Fig. 25 Phase diagram for water-salt.
The latent heat of fusion of ice, another enthalpy change, is 79.67 cal/g. This means that
when a gram of ice melts to water, the heat required could cool that water to -80°C. In
equilibrium, of course, the water cannot cool and the heat must come from outside, say from the
drink the ice cube floats in. This is the familiar property of ice in maintaining a low temperature,
which it does effectively by the large latent heat. The ice will get your drink down to 0°C or die
trying. Usually, it dies trying and melts continuously no matter how well you have insulated the
glass. A mixture of crushed ice and water can usually get down to 0°C and provide a fixed
reference temperature for a thermocouple. This has to be done properly, for water has maximum
density at 3.8°C, and the ice is usually floating on 3.8° water (the increase in density is very
slight, however, only about 1 part in 10,000). The reference junction must be kept surrounded by
ice. Incidentally, the equivalent of a reference junction can be supplied in a fairly accurate and
drier fashion with electronics.
So we see that ice is a powerful cooling engine because of its latent heat, but can only go to 0°C,
which is not enough to freeze things. Also, ice is not always welcome in the winter, and it would
be good to have some way to melt it so the water would flow off and not make things slippery.
Both demands can be met with the help of salt, NaCl. Suppose the temperature corresponds to
point c, and we sprinkle salt on the ice. The ice melts, by means of the heat supplied by the
environment, and some salt solution is formed in the puddle, because the ice is not in equilibrium
with all that salt. The salt solution becomes more concentrated as the salt lying around dissolves
in the water from the melting ice. The ice tries to dilute the solution, while the salt wants to
concentrate it, and when point a is reached, all the ice has melted and we have a salt solution
only. If more salt is present, the solution becomes more concentrated and may reach point b,

PHYSICAL CHEMISTRY
where the solution is saturated, and any more salt would just precipitate out. Therefore, the
system ends up beyond b, with saturated solution and some solid salt, waiting for more ice.
Now suppose we mix ice and salt on purpose, to get a freezing mixture. The environment is not a
heat reservoir now. In fact, we make insulate it so that it must supply all the latent heat if the ice
is to melt. Ice and solution are both present, so we must be in the corresponding region to the left
of line AE in the phase diagram. Suppose the solution has a concentration corresponding to point
a. If a little more salt dissolves, the concentration may correspond to point e, to the right of the
equilibrium concentration, so ice dissolves to dilute the solution. The provision of the latent heat
required cools the system to point f, again on the equilibrium curve, but at a lower temperature.
Therefore, with ice, salt and solution all present, there cannot be an equilibrium until point E is
reached, where equilibrium can be established and maintained while all three phases are present.
The concentration at this point is 23% (some sources say 29%), from which the amount of salt
required can be estimated. The temperature is -21°C or -5.8°F, which is sufficient to freeze ice
cream.
The melting of ice extracts most of the heat, but the dissolving of salt contributes its part as well.
Magnesium chloride forms a eutectic at -33.6°C (-28°F) and 21.6%, and calcium chloride at -
55°C (-67°F) and 29.8%. Calcium chloride can be used to freeze mercury at -38°C. The hydrated
salts should be used for making freezing mixtures, and everything should be kept cold, insulated,
and mixed.
Aqueous solutions of alcohol, and other substances, such as ethylene glycol, depress the freezing
points of the solutions, as is well-known from motor-vehicle antifreezes. These can make
freezing mixtures and melt ice as well. I made a skull-and-crossbones Martini from denatured
alcohol and ice cubes, and got it down to -6°C in a few minutes. A 30% ethyl alcohol solution,
with a gravity of 0.954, gets you down to -19°C (-2°F). Glycerine gives a minimum at -37.8°C,
in a 70% glycerine solution.
Carbon dioxide sublimates at -78.5°C. Carbon dioxide snow, compressed into blocks, is "dry
ice" which is drier than freezing mixtures. It is often mixed with liquids like alcohol, acetone,
chloroform or ether to make a cooling bath. The temperature, however is not lower than the
sublimation temperature of CO2, and no eutectic is formed. Liquid nitrogen boils at -196°C and
is convenient to use, leaving no clean-up. With all these means at one's disposal, temperatures
down to 77K are available without machinery.

PHYSICAL CHEMISTRY
REFERENCES:
1. Beattie, J. A. and Bridgeman, O. C., J. Amer. Chem. Soc., 49, 1665 (1927).
2. Taylor, H. S. and Glasstone, S. (eds.), "A Treatise on Physical Chemistry",
vol. II, 187 ff. van Nostrand, Princeton, N.J. (1951).
3. Hecht, C. E. and Zimmerman, G., J. Chem. Ed., 10 (1954), pp. 530-33.
4. Experiments in Physical Chemistry, Shoemaker, D. P., Garland, C. W.,
Steinfeld, J. I. and J.W. Nibler, (McGraw-Hill, 1981), p. 65 ff.
5. ibid, 582-584.
6. Atkins, P.W. "Physical Chemistry", 5th ed., (Freeman, 1994), pp 104-108.
7. Int. Crit. Tables (Thode Library, ref. Q 199.N27)
8. J.H. Noggle, "Physical Chemistry", 3rd ed., Harper Collins, 1996 pp 104ff.
9. R.G. Mortimer "Physical Chemistry", Benjamin/Cummings, Redwood City,
Calif., 1993, pp 70-73.

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PHYSICAL

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 2

2.8. Effects of Conditions………………………………………………………………………38

6.2. Mechanism of electrolysis…………………………………………………………….......88

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 4

1.0 INTRODUCTION TO THERMODYNAMICS

1.1 Importance of Thermodynamics

1.2 Limitations of Thermodynamics

1.3 THERMODYNAMIC TERMS

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 5

1.3.2. Types of Systems

There are two broad classes which depend on :

a) (i) Homogeneous System:

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 6

a) Extensive property of a system depends on the amount of substance present in the

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 7

pV= nRT P = pressure V = Volume n = number of moles R = Gas Constant

a) Isothermal process: this type of process is carried out at constant temperature.

d) Isochoric process: the volume of the system does not change

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 8

1.3.9 Internal energy (U)

(i) Translational energy – associated with the translational motion of a molecule.

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 9

1.4. ENTHALPY OR HEAT CONTENT (H)

But p∆V = ∆nRT.

1.5. WORK, HEAT AND ENERGY

1.6. HEAT CAPACITY

1.7. FIRST LAW OF THERMODYNAMICS

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 10

1.7.1 Mathematical expression:

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Heat capacity at constant volume CV =

Heat capacity at constant pressure Cp =

1.7.2 Relationship between Cp and Cv

Internal energy is a function of temperature and volume

dU = CvdT + dV TdV ( dU ) (v)

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 12

For ideal gases ( dU

Therefore Cp – Cv= P ( dVdT ) p (viii)

But pV= nRT and V= ( nRTp )

From equation (viii) and (ix)

Therefore Cp – Cv =nR for ideal gases

1.8. THE SECOND LAW OF THERMODYNAMICS

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 13

2) Heat cannot pass from a cooler body to a warmer body.

Entropy is a measure of the randomness or disorder of the molecule of the system. It is a

1.8.3. Chemical reactions as dispersers of energy

1) 4Fe(s) + 3O→2Fe2O3(s) ∆ H =-1648KJ mo1 -1

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 14

∆S0(298K) = 2(87.4)-[ 4 ( 27.3 )−3 ( 208 ) ]

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 15

For rusting of iron. 1648 KJ are dispersed to the surrounding.

For dinitrogentetraoxide 57,7KJ are taken from the surroundings.

Therefore: ∆S(surrounding) = - ( ∆TH ) = - 57.7 x 103

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 16

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 17

Al2O3(s) +6Na(s)→ 3Na2O(s) + 2Al(s)

/kjmol-1 -400 Si(s) + O2(g)  SiO2(S)

Fig.1.2 Variation of free energy change (ΔG )with temperature.

ZIMBABWE SCHOOL OF MINES-NATIONAL DIPLOMA Page 18

2Mg(s) + O2(g) 2MgO(s)

4Au + 3O2 2Au2O3

-200 2CO +O  2CO