SCH 101 Notes

SCH 101: Introduction to Physical Chemistry
lecture notes
Kenyatta University
Chemistry Department
By
Isaac W Mwangi
TABLE OF CONTENTS
TABLE OF CONTENTS ...................................................................................................................................................... ii
INTRODUCTION TO FIRST YEAR (SCH 101) PHYSICAL CHEMISTRY COURSE OUTLINE ....................................................... v
Introduction to physical chemistry..................................................................................................................................... 1
The gaseous state ............................................................................................................................................................... 1
1.0 Introduction.............................................................................................................................................................. 1
1.1 The state of matter................................................................................................................................................... 1
1.1.1 Solids ..................................................................................................................................................................... 1
1.1.2 Liquids.................................................................................................................................................................... 1
1.1.3 Gases ..................................................................................................................................................................... 2
1.2 The gas laws ............................................................................................................................................................. 2
1.3.1 The Pressure-Volume Relationship: Boyle's Law .................................................................................................. 2
1.3.2 The Temperature-Volume Relationship: Charles's Law ........................................................................................ 5
1.3.3The Quantity-Volume Relationship: Avogadro's Law............................................................................................. 7
1.4 The equation of state and the ideal gas equation ................................................................................................... 8
1.4.1 The gas constant R............................................................................................................................................... 11
1.5 Mixture of gases: Dalton’s law of partial pressure................................................................................................. 12
1.6 The kinetic molecular theory of ideal gases ........................................................................................................... 14
Egg-in-the-Bottle Demonstration ................................................................................................................................... 0
2.0 Chemical equilibria ..................................................................................................................................................... 30
2.1 Introduction............................................................................................................................................................ 30
2.2 Learning goals ......................................................................................................................................................... 30
2.3 The concept of equilibrium .................................................................................................................................... 30
2.4 The magnitude of equilibrium constants ............................................................................................................... 32
2.4.1 The direction of chemical equation and K........................................................................................................... 34
2.6 Relationship between Kc and Kp ............................................................................................................................. 36
2.7 Approach to equilibrium ........................................................................................................................................ 38

ii
Introduction to physical chemistry-GASES
2.8 Heterogeneous equilibrium ................................................................................................................................... 40
2.9 Factors influencing equilibrium concentration ...................................................................................................... 41
Effect of change in Reactant or Product Concentrations ............................................................................................. 43
Effect of change in temperature .................................................................................................................................. 44
3.0 Acid-base equilibria ................................................................................................................................................ 46
3.1 Introduction ........................................................................................................................................................ 46
3.7.3 Neutralization indicators ................................................................................................................................. 60
4.1 Introduction ........................................................................................................................................................ 67
4.2 Liquid- vapour equilibria .................................................................................................................................... 68
4.2.1 Solutions .......................................................................................................................................................... 68
Colligative properties ............................................................................................................................................... 68
4.3. Raoult’s law .................................................................................................................................................. 69
Boiling point elevation (ebullioscopy) ...................................................................................................................... 72
Freezing point depression (cryoscopy)..................................................................................................................... 72
4.3 Positive deviation ............................................................................................................................................... 76
4.4 Immiscibility ....................................................................................................................................................... 77
4.5 Partition of solutes between two immiscible solvents ...................................................................................... 78
5.0 Electrochemistry..................................................................................................................................................... 82
5.1 Introduction ........................................................................................................................................................ 82
5.2 An electrochemical cell ...................................................................................................................................... 82
5.4 Reference electrodes and standard reduction potentials. ................................................................................ 84
5.5 The standard hydrogen electrode-SHE .............................................................................................................. 85
5.6 Standard reductive potentials ........................................................................................................................... 86
5.7 Preparation of cells............................................................................................................................................. 86
5.8 The Nernst equation........................................................................................................................................... 88
iii
Summary .................................................................................................................................................................. 88
5.9 Equilibrium constant .......................................................................................................................................... 91
REFERENCES ................................................................................................................................................................. 94
iv
INTRODUCTION TO FIRST YEAR (SCH 101) PHYSICAL CHEMISTRY COURSE OUTLINE
KENYATTA UNIVERSITY
CHEMISTRY DEPARTMENT
SCH 101 Introduction to physical Chemistry
Unit purpose
This is a first-year undergraduate course which presents an introduction to of physical chemistry, with view
to provide insights in fundamentals concept of gases (ideal gas and real gases; equilibria including solubility
product and electro chemistry. It will furnish the students with basic practical skills including safe working
practices in the laboratory and report writing of results factoring errors and accuracy. This will enable the
students to apply the general principles of physical chemistry on a broad range of topics.
Course Objectives
The course is intended to equip students with sufficient knowledge to enable them comprehend and relate to
other concepts encountered at a later stages, as they explore more in science. The fundamental concepts and
organizing principles of physical chemistry will provide the basis for all aspects of chemistry and related
fields. It is geared to give a detailed explanations of many chemical phenomena that can enable students
interpret various experiments results
1 and 2 Properties of gases: Describe how a given amount of gas responds to changes in pressure, volume, temperature and the quantity,
The ideal gas laws, kinetic molecular theory of gases, Use the ideal-gas equations to solve for one variable (P, V, n, or T) given the other three variables or information from which they can be determined. Use
Maxwell – Boltzmann distribution, deviation from the gas laws, including the combined gas law, to calculate how one variable of a gas (P, V, or T) responds to changes in one or more of the other variables.
ideality and Van – der Waal’s equation, Calculate the partial pressure of any gas in a mixture, given the composition of that mixture. Calculate the mole fraction of a gas in a mixture, given its
partial pressure and the total pressure of the system. Describe how the relative rates of effusion and diffusion of two gases depend on their molar masses
(Graham’s law). Explain the origin of deviation shown by real gases from the relationship PV/RT=1 for a mole of an ideal gas. Cite the general conditions of
P and T under which real gases most closely approximate ideal-gas behavior. Explain the origins of the correction terms to P and V that appear in the van
der Waals equation. Describe how molecular velocities are distributed in a sample of gas
3 and 4 Chemical equilibrium: Write the equilibrium expression for a balanced chemical equation, whether heterogeneous or homogeneous
Numerically evaluate Kc (or Kp) from knowledge of equilibrium concentrations (or pressures) of reactants or products, or from the initial
Reversible chemical reaction, equilibrium concentratrations and the equilibrium concentration of at least one substance.
constants and their dependence on concentration Interconvert Kc into Kp for a given chemical equation
Predict how a reaction at equilibrium would shift when temperature, pressure, and/or the concentrations of substances in the equilibrium is/are changed
and pressure, le Chateller’s principle
5 and 6 Ionic equilibria: Explain what is meant by the autoionisation of water, and write the ion product constants expressions for this process
Define pH, calculate pH on the knowledge of (H+) and as well perform reverse operation
Ionization of water, acids, bases and salts, pH and Identify the common strong acids and bases and calculate the pH of their aqueous solutions given their concentrations
buffer solutions; theory of acid/base indicators. Calculate the pH of weak acids and bases solutions in water given their concentrations and their respective Ka and K values and vice versa. Predict
whether a particular salt will be basic, acidic or neutral. Describe how a buffer solution of a particular pH is made and the reactions that allow it to control
pH. Calculate the change in pH of a sample of buffer solution of known composition caused by addition of a small amount of strong acid or base,
Calculate the concentration of each species present in a solution formed by mixing an acid and a base, Describe the form of the titration curves for
titration of a strong acid by a strong base, a weak acid by a strong base or a strong acid by a weak base. Set up the expression for the solubility-product
for a salt, Calculate Ksp from solubility data, and solubility from the value of Ksp , Calculate the effect of an added common ion on the solubility of a
slightly soluble salt.
7 and 8 Physical equilibria: Describe, with the aid of a phase diagram, the state in which a given substance will exist at any given temperature and pressure
Explain the causes of deviation from ideal behavior for solutions
Raoult’s law and its application to distillation, Describe the effect of solute concentration on the vapour pressure of a two component solution
solid – liquid equilibrium (SLE), Liquid – liquid Use Raoult’s Law to solve for one variable (P X P) given the other two variables or information from which they can be determined.
equilibia (LLE) between two immiscible liquids,
the distribution law and steam distillation.
9 and Electrochemistry: Define a galvanic cell, Represent a cell on a diagram, Write the anode, cathode and cell reaction for a given cell
10 Given appropriate electrode potentials, calculate the emf generated by galvanic cell, Describe the Hydrogen electrode, Define Standard electrode
Electrochemical processes, half reactions, standard potential, Given appropriate electrode potentials, calculate the emf generated by galvanic cells, Define electrolysis, Predict products of simple electrolytic
cell and electrode potential, EMF of a cell cells
Teaching methods
Teaching will be done through lectures and some selected laboratory exercises. The lectures are used for
developing a basic understanding of physical chemistry. A laboratory session will be included in the
teaching so that theoretical lectures will be translated into practice to improve the student’s knowledge.
By this, the students will gain a practical introduction to all the central parts of the syllabus and
confidence to approach unstable nuclides.
Assessment
A written examination (main University examination).of 2 hours duration will be taken at the end of the
semester which will be 70% of the total marks while 30% will be from continuous assessments which
may include CAT and any other (assignment) written reports.
References
1) Atkins, P.W., Physical Chemistry, and edition, OUP.
2) Any other physical chemistry textbook

Introduction to physical chemistry
What is chemistry?-Chemistry is the study of mater and energy and the interaction between them. What is
physical chemistry? Physical chemistry is a branch of chemistry that deals with the physical properties of
chemical substances (matter). This explains how specific chemical substances behave at differing conditions such
as pressure and temperature changes among many.
The gaseous state
1.0 Introduction
1.1 The state of matter
States of matter are the distinct forms that different phases of matter exist. In the physical sciences, a phase is a
region of space (a thermodynamic system), throughout which all physical properties of a material are essentially
uniform (Reichardt, 2007). Examples of physical properties include density, index of refraction, magnetization
and chemical composition. Matter exists in solid, liquid or gaseous phase usually referred to as the tree states of
matter. The three phases are clearly convertible as in ice, water and steam, which represent the same substance
in different phases.
But what makes them different?
1.1.1 Solids
In a solid the particles (ions, atoms or molecules) are closely packed together in the solid state, the particles are
fixed in a uniform manner, held in definite positions in a crystal lattice by strong forces operating between them.
As a result, solids are rigid, with definite shape and volume and can resist compression or distortion. Only
vibrational motion is allowed in solid particles. This vibrational motion is dependent on temperature, thus the
higher the temperature, the longer the vibrational distance making the forces between the particles weaker. At a
given temperature, these forces become so weak that the solid structure breaks down and the solid melts to
form a liquid.
1.1.2 Liquids
In the liquid state, the particles can move freely as they possess translation motion which has weak forces
operating between them as compared to the solids. However, these forces are not weak enough to allow a
complete separation of the particles from one another. A liquid is a nearly incompressible fluid that conforms to
the shape of its container but retains a (nearly) constant volume independent of pressure. Therefore a liquid
have definite volume with no definite shape but takes the shape of the container that hold it. The forces holding
the liquid particles together also depend on temperature. The higher the temperature, the faster the particles
become and therefore the weaker the forces holding them together. At a certain temperature, the forces
become so weak that the liquid particles breaks down and the liquid particles evaporate after boiling.
1
1.1.3 Gases
In the gaseous state, the restraining forces of attraction between the particles have been overcome completely.
The particles move in a complete random manner at high speeds. This because the molecules have enough
kinetic energy so that the effect of intermolecular forces is small and the distance between neighboring
molecules is much greater than the molecular size. As a consequence, gases have no definite shape or volume,
but occupies (or fills) the entire container in which it is confined and therefore highly compressible.
A solid can be converted to liquid by heating and a liquid can be converted to a gas by heating at constant
pressure to the boiling point, or else by reducing the pressure at constant temperature. The sensitivity to
changes in volume with changes in pressure and temperature is therefore:-
Solid<liquid << gas
The relation between volume, temperature and pressure is more on gaseous state hence will a subject in this
chapter.
1.2 Learning goals
By the end of this unit, students should be able to:-

 Describe how gases respond to changes in pressure, volume, temperature and the quality of gas.
 Use ideal-gas equation to solve for any one variable (P, V, n, or T) given the other three variables or
information from which they can be determined.
 Use the gas laws, including the combined gas law, to calculate how variable of gas (P, V, n, or T) responds
to changes in one or more of the variables.
 Calculate the partial pressure of any gas in a mixture, given the composition of that mixture.
 Calculate the mole fraction of a gas in a mixture, given its partial pressure and the total pressure of the
system.
 Describe how the relative rates of effusion and diffusion of two gases depend on molar masses
(Graham’s law).
 Explain the origin of deviation shown by real gases from the relationship PV/RT=1 for a mole of an ideal
gas.
 Cite the general conditions of P and T under which real gases most closely approximate ideal gas
behavoiur.
 Explain the origins of the correction terms to P and V that appear in the Van Der Waals equation.
 Describe how molecular velocities are distributed in a sample of gas.
1.2 The gas laws
Experiments with a large number of gases reveal that four variables are needed to define the physical condition,
or state, of a gas: temperature, T, pressure, P, volume, V, and the amount of gas, which is usually expressed as
the number of moles, n. The equations that express the relationships among T, P, V, and n are known as the gas
laws.
1.3.1 The Pressure-Volume Relationship: Boyle's Law
The first person to investigate the relationship between the pressure of a gas and its volume was a British chemist
Robert Boyle (1627-1691). He used a J-shaped tube like that shown in Figure 1.
2
Figure 1 An illustration of Boyle's experiment.
In diagram a, the volume of the gas trapped in the J-tube is 60 mL when the gas pressure is 760 torr. When
additional mercury is added, as shown in diagram b, the trapped gas is compressed. The volume is 30 mL
when its total pressure is 1520 torr, corresponding to atmospheric pressure plus the pressure exerted by the
760-mm column of mercury.
A quantity of gas is trapped in the tube behind a column of mercury. Boyle changed the pressure on the gas by
adding mercury to the tube. He found that the volume of the gas decreased as the pressure increased. He
observed that by doubling the pressure (by adding 760 ml of mercury) it caused the gas volume to decrease to
one-half its original value.
From that, he developed the Boyle’s law which stated that:-
The volume of a fixed quantity of gas maintained at constant temperature is inversely proportional to the pressure
1
i.e V 
P
Boyle's law can be expressed in mathematical terms as shown in equation1.
1
V  constantx or PV  constant (eq 1)
P
The value of the constant depends on the temperature and the amount of gas in the sample. A plot of P against V
at a constant temperature (isotherm) will give hyperbola as shown in figure 2 below.
3
Figure 2 Graphs based on Boyle's law of volume versus pressure
Plot another with different temperatures
The figure shows that as the volume increases, pressure decreases. Another plot of V against 1/P was done
and is presented in figure 3.
Figure 3 Graphs based on Boyle's law of volume versus 1/P.
The results obtained gave a linear relationship which has a constant gradient as shown. The results from
the isotherm in Figure 2 show that when the volume of gas V1 at pressure P1 is changed to a new volume
V2, the new pressure P2 can be evaluated using equation 2.
P1 V1  P2 V2 (eq 2)
This is because PV must remain constant.
Thus equation 2 can be applied to calculate the volume of a gas at any required pressure, if the volume and
the other pressure are known.
Sample exercise 1.1
The volume of a gas at 1 atm. pressure is 390 cm3. Calculate the volume the gas will occupy if the pressure
is increased to 1.5 atm at a constant temperature.
Solution
PV
From equation 2, P1 V1  P2 V2  V2  1 1 and place the respective values in the
P2
equation, thus
3
1 atm x 390 cm 3
V2   260 cm
1.5 atm
4
We see an application of Boyle's law every time we breathe. Between breaths, the gas pressure inside the
lungs equals atmospheric pressure. The volume of the lungs is governed by the rib cage, which can expand
and contract, and the diaphragm, a muscle beneath the lungs. Inhalation occurs when the rib cage expands
and the diaphragm moves downward. Both of these actions serve to increase the volume of the lungs, thus
decreasing the gas pressure inside the lungs. The atmospheric pressure then forces air into the lungs until
the pressure in the lungs once again equals atmospheric pressure. Exhalation involves the reverse process:
The rib cage contracts and the diaphragm moves up, both of which decrease the volume of the lungs. Air is
forced out of the lungs by the increase in pressure caused by this reduction in volume.
Practise exercise 1.1
Calculate the final volumes which would be occupied by a gas at constant temperature from the
information given in the data below.
Initial volume/ cm3 Initial pressure Final pressure Final volume/ cm3
152 750 mm Hg 760 mm Hg
180 760 mm Hg 720 mm Hg
5250 1 atm. 1.35 atm.
1540 1.01 x 105 Pa 7.35 x 105 Pa
1.3.2 The Temperature-Volume Relationship: Charles's Law
The relationship between gas volume and temperature was discovered in 1787 by the French scientist
Jacques Charles (1746-1823). He found out that the volume of a fixed quantity of gas at constant pressure
increases linearly with temperature. This implies that the change in volume is directly proportional to
temperature at a constant pressure. He came up with a law called the Charles’s law which states that:-
The volume of a fixed mass of any gas increases by the same fraction (δV) for ever degree rise in
temperature.
Therefore, if V0 is the volume of a given quantity of gas 0˚C (at a constant pressure) the volume V t at any
temperature t˚C is given by equation 3 given below.
Vt  V0  δV V0 t  Vo (1  δV t) (eq 3)
The fraction δV which is also called the co-efficient of expansion was found to be 1/273
Therefore equation 3 can be re-written to read as equation 4 below.
t
Vt  Vo (1  ) (eq 4)
273
5
If equation 4 expanded, it would read as Vt=V0+V0t/273. It can be considered as a general linear quadratic
equation, y=mx+c. When a plot of volume against temperature gives rise to a straight line with an intercept of V0
and a gradient V0/273. Figure 4 gives a plot of volume against temperature.
Figure 4 A plot of Volume of an enclosed gas as a function of temperature at constant pressure.
If the line is extrapolated it intercepts the temperature axis at -273˚C. Upon making that intercept our new
origin, we obtain a new temperature scale called the Kelvin scale referred to as absolute temperatures (T
Kelvin or T K). The relationship between the Kelvin scale and the Celsius scale is done by adding 273 to the
latter (T K=273+˚C).
It is assumed that gases have zero volume at this temperature. However, this condition is never fulfilled
because they liquefy or solidify before reaching that temperature.
Then two different volumes V1 and V2 at temperatures t1 and t2 respectively can be evaluated by placing the
respective values in equation 4 above.
Thus
t1
V1  Vo (1  ) (eq 5)
273
t2
V2  Vo (1  ) (eq 6)
273
Dividing equation 5 by equation 6 gives rise to equation 7 below
 t 
Vo  1  1 
V1  273  273  t1
  (eq 7)
V2  t 2  273  t 2
Vo  1  
 273 
Since 273+˚C =T Which is the conversion of Celsius to Kelvin scale, the equation 7 can be re-written as
equation 8 below
V1 T V V
 1 or 1  2 (eq 8)
V2 T2 T1 T2
From equation 8, it can concluded that

6
V
 cons tant (eq 9)
T
From equation 9 shows an alternative of stating the Charles Law stating that:-
The volume of a given mass of a gas at constant pressure is directly proportional to the absolute
temperature increases by the same fraction (δV) for every degree rise in temperature V  T .
In real life application, this is why hot-air balloons rise because air expands as it is heated. The warm air in
the balloon is less dense than the surrounding cool air at the same pressure. The difference in density
causes the balloon to ascend. Similarly, a balloon will shrink when it is cooled.
Sample exercise 1.2
At 0˚C, the volume of a given gas is 546 cm3. Calculate the volume the gas would occupy at 14˚C.
Solution
V1 T V V
From equation 8,  1 or 1  2 and place the respective values in the equation, thus
V2 T2 T1 T2
V1 T2 546 cm3 x 287 K

V2    574 cm3
T1 273 K
Calculate the volumes, which would be, occupied at the given final temperatures by the gases whose initial
volumes and temperatures are given the experimental data below. The pressure was maintained constant.
Initial volume/ cm3 Initial temperature Final temperature Final volume/ cm3
864 15˚C 20˚C
580 17˚C 0˚C
1168 292 K 273 K
516 -15˚C 12˚C
1.3.3The Quantity-Volume Relationship: Avogadro's Law
As gas is added in a balloon, the balloon expands. The volume of a gas is affected not only by pressure and
temperature but by the amount of gas as well. The relationship between the quantity of a gas and its
volume follows from the work of Joseph Louis Gay-Lussac (1778-1823) and Amadeo Avogadro.
7
From that observation, Avogadro came up with a law stating that:-
The volume of a gas maintained at constant temperature and pressure is directly proportional to
the number of moles of the gas.
V  constant x n (eq 11)
Thus by doubling the number of moles of gas will cause its volume to double if temperature and pressure remain
constant. Experimentally, 1 mole of gas at the same temperature and pressure occupies the same volume as any
other gas at the same temperature and pressure. From that information, it was found that under standard
temperature and pressure (STP) which are 0˚C (273 K) and 1 atm., 1 mole of gas occupies 22.4 litres. Amadeo
Avogadro hypothesised that:-
Equal volumes of all gases at the same temperature and pressure contain the same number of moles. Hence
volume is proportional to the number of moles ( V  n ) at constant temperature and pressure.
For 1 mole, this number is 6.023 x 10-23 molecules. This is called the Avogadro number.
How can we combine the three laws so far to obtain an equation of state?
1.4 The equation of state and the ideal gas equation
The results of Boyle and Gay Lussac may be combined in an expression, which represents the relationship
between pressure P, and temperature T of a given mass of gas. Such an expression is called the equation of state.
The universe can be divided into two portions, according to the convenience of person concerned namely the
system and its surrounding. A system is the region separated from the remainder of the universe by real or
imaginary boundaries for the purpose of observing interchanges of energy and matter between this region and
the rest of the universe. The state of a system and its description is given by specifying its composition, its
pressure and temperature.
In the preceding section, we examined three historically important gas laws. Each was obtained by holding two
variables constant in order to see how the other variables affect each other. Using the symbol ∝ which is read “is
proportional to” we have
1
Boyle’s law V (constant n, T)
P
Charles law V  T (constant n, P)
Gay-Lussac and Avogadro’s V  n (constant T, P)
We can combine these relationships to make a more general law:
nT
V (eq 12)
P
Consider a gas initially at a state where Volume V1 pressure P1 and temperature T1. If the state changes, such that
the new variables are P2, V2 and T2 respectively, then how will the two states be related? If initially the
temperature T1 is kept constant and the pressure changes to P2, the volume V1 changes to V’1 according to Boyle’s
law. NOTE the temperature IS KEPT CONSTANT T1
8
According to Boyles law, the pressure change expression can be written as shown below.
'
P1 V1  P2 V1 (eq 13)
and therefore
' P V
V1  1 1 (eq 14)
P2
If the pressure is maintained at P2 and the temperature changes to T2, then the volume changes to V2 according to
Charles law.
'
V1 V2
 (eq 15)
T1 T2
Substituting V’2 from equation 13
P1 V1 V2

P2 T2 T2
This equation can be rearranged to appear as shown in equation 16 below
P1 V1 P2 V2
 (eq 15)
T2 T2
This confirms that
PV
 constant (eq 1.16)
T
Equation 1.16 is called the equation of state for gases that obey Boyle’s law and Gay-Lussac’s law. This implies
that, for a definite mass of gas, any change in temperature and pressure will be accompanied by an adustiment of
PV
volume so the remai nsunal tered.The Value of the constant depends upon the mass and nature of the
T
gas.
However according to Amadeo Avogadro that equal number of molecules of different gases will occupy the same
volume at a given temperature and pressure. Thus applying Avogadro’s law where for 1 mole of gas, if
temperature and pressure are kept constant, all gasses occupy the same volume, since V is proportional to the
number of molecules then
9
PV
R (eq 1.17)
T
Where R is the constant in equation 1.16, and is called the gas constant. This value is the same for 1 mole of all
gases.
According to Amadeo Avogadro, that 1 mole of gas will have a volume V then n moles will have a total volume of
nV
Then for n moles, Equation 1.17 becomes;-
PV
 nR (eq 1.18)
T
Equation 1.18 is called the ideal gas equation and is obeyed by all ideal gases. The concept of ideal gas will be
made clearer later. The ideal gas equation can be ultilised in determining several other quantities involving gases
eg concentration C. Concentration is defined as number of moles per given volume i.e n/V. Therefore equation
1.18 can be expressed in concentration form to appear as shown in equation 19 below.
n
P RT (eq 1.19)
V
An ideal gas is a theoretical gas composed of a set of randomly moving, non-interacting particles. The ideal gas
concept is useful because it obeys the ideal gas law, a simplified equation of state and is amenable to analysis
under statistical mechanics.
An ideal gas is defined as one in which all collisions between atoms or molecules are perfectly eleastic and
in which there are no intermolecular attractive forces. One can visualize it as a collection of perfectly hard
spheres which collide but which otherwise do not interact with each other. In such a gas, all the internal
energy is in the form of kinetic energy and any change in internal energy is accompanied by a change in
temperature.
An ideal gas can be characterized by three state variables: absolute pressure (P), volume (V), and absolute
temperature (T). The relationship between them may be deduced from kinetic theory and is called the
Ideal gas law PV  nRT
From equation 1.19, then equation 1.20 is derived as shown.
P  CRT (eq 1.20)
Since number of moles n is given as mass of a gas as a fraction of it relative formular mass, m/M, equation 19 can
also be written as
m
P M RT mRT (eq 21)
V MV
m m
Equation 22 can be rearranged to read P  RT RT
MV V(RFM)
10
Since mass divided by volume m/V is density ρ then equation 21 can be re-written as equation 22 below
RT
P (eq 22)
M
From equation 22, the relative formula mass (M) of a gas can be determined by rearranging equation 22
RT
M (eq 22)
P
1.4.1 The gas constant R
The gas constant is a very important quantity and we need to work out its value and units. At STP, the volume of 1
mole of an ideal gas is 22.4 l or 22.4 x 10-3 m3. The pressure is 101325 N m-2 or 1 atm while the temperature is 273
K. Hence in SI units
2 3 3
PV 101325 Nm x 22.4 x 10 m 1 1
R   8.314 Jmole K (J  Nm) (eq 23)
nT 1 mol x 273 K
While working with volume in litres and pressure in atm, equation 23 can be written as equation 24 below
PV 1 atm x 22.4 l 1 1
R   0.0821 l atm mole K (eq 23)
nT 1mol x 273 K
The value of R as can be seen depends on our units of volume and pressure
Numerical values of the gas constants R in various pressure values
Units Numerical Value

-1 -1
1-atm mol K 0.0821
-1 -1
Cap mol K 1.987
-1 -1
J mol K 8.314
3 -1 -1
m -Pa mol K 8.314
-1 -1
L-tor mol K 63.36
Point of emphasis
 But while working with gases, the most commonly used values of R are 0.82062 atm mol-1 K-1 and
8.314 J mol-1 K-1
 The standard condition for gas behaviours (0 ˚C) are not the same as the standard conditions (STP)
in thermodynamics and thermo chemistry (25˚C)
 Any gas law can be derived from the gas equation
11
Sample exercise 1.3
What is the volume of 1 mole of an ideal gas at STP?
n n
Solution From equation 19, P RT therefore V  RT
V P
At STP P= 101325 N m2, T=273, and R=8.314 J mol-1 K After the respective values are placed in the
V T -1
1 mol x 8.314 J mol x 273 K 2 1
equation, then V2  1 2  -2  0.0224 J m N
T1 101325 N m
But J=Nm Then 0.0224 J m 2 N1 = 0.0224 N m m 2 N1 = 0.0224 m3 or 0.0224 l
Sample exercise 1.3
The density of nitrogen gas is 1.68 g l-1. What volume will the gas occupy at 273 and 100 Kpa?
Repeat the sample exercise 1.3 using values R=1-1tm mol-1 K-1; 0.0821 l-atm mol-1 K-1 Solution
1.5 Mixture of gases: Dalton’s law of partial pressure
This law is concerned with pressure of a mixture of gases. Due to the nature of ideal gases, in a mixture of
one or more gases each gas exerts the same pressure as that which it would have exerted if it was occupied
alone in a container.
Dalton’s law of partial pressure states that the total pressure of a mixture of gases is equal to the sum of the
partial pressure of the constituent gases.
Thus if p1, p2……p3 are partial pressures of the individual gases in a mixture, then the total pressure P is
given by
PT  p 1  p 2  p 3 .........pn (eq 1.24)
Considering the ideal gas equation (see example equation 18) PV  nRT then;
P1 V  n1RT and P2V  n2RT ⇒ PnV  nnRT (eq 1. 25)
Hence (P1  P2  P3  .......Pn )V  (n1  n2  n3  ....nn )RT (eq 1.26)
Thus n1  n2  n3  ....nn  n t
12
This can be re-written as PV  n t RT (eq 1.27)
Where nt is the total number of moles i.e Sum of n1+n2+n3…….nn
Dividing equation 1.25 by equation 1.27, the partial pressure p1 can be given by
n1 n
p1  P  X 1P and p 2  2 P  X 2P (eq 1.28)
nt nt
n1 n
X1 an X2 given by and 2 respectively, are called the mole fraction of the respective gases.
nt nt
Teaching notes
When explaining Dalton’s law, emphasize that each component is at the same temperature and occupies
the same volume.
Point of emphasis
The sum of the mole fractions of a mixture of gases must be equal to 1 i.e X i 1
Sample exercise 1.4

100 ml of oxygen at 1.75 atm and 200 ml nitrogen at 0.6 atm are passed into a vessel whose capacity is 500 ml. Calculate the total
pressure of the mixture in the vessel at the same temperature.
Solution
NOTE From equation 1.24, Pt=P1+P2
From P1 V1  P2 V2 , We obtain the new partial pressures of each gas as volume changes to 500 ml using the gas equation . The
total volume is 500 ml
For oxygen which was 100 ml, the partial pressure will be 100 ml x 1.75 atm =500 x Po - P100ml V100ml  P500ml V500ml
For nitrogen which was 200 ml, the partial pressure will be 200 ml x 0.6 atm =500 x PN - P200ml V200ml  P500ml V500ml
Po = 0.35 atm and PN = 0.24 atm
Ptotal = Po + PN= 0.35+0.24=0.59 atm – Alternatively, (PoVo)+ (PNVN)= PtVt
Sample exercise 1.4
A mixture of gases at STP contains 65% nitrogen, 15% carbon dioxide and 20% oxygen by volume. What is
the partial pressure of each gas in the atmospheres?
13
Solution to sample exercise 1.4
From PT  p 1  p 2  p 3 .........pn Then Pt= Pnitrogen + P carbon dioxide +Poxygen

65 15 20
= PT  760  760  760  760 mm Hg
100 100 100
What is the partial pressure of each gas in the atmospheres?
The pressures are 494, 152 and 114 mm Hg respectively
1.6 The kinetic molecular theory of ideal gases
Why does a gas obey Boyle’s law or Charles law? To understand the nature of gases, we develop a physical
picture of the gaseous state capable of explaining the various laws of gaseous behaviour. We propose the
hypothesis about the nature of the gas. Such hypothesis is referred to as a “model” for a gas. The
properties of the gas deduced from this model are then compared to the experimental properties of the
gas.
Having looked at the gas laws generally, it is important to try and understand them from the molecular
point of view. To develop our theory, we need to firstly define precisely a gas in a container in the form of
postulates. Thus the following (postulates) will hold for any ideal gas for the moment at low pressure and
moderate temperature.
 Gases are made of independent particles (atoms or molecules) moving in rapid motion and in
straight line.
 When the particles collide with others or with the surface of the container, there is no loss of
velocity (momentum conserved) thus the collision is perfectly elastic.
 The particles are viewed as being relatively far apart and their volumes relatively small (negligible)
compared to the total volume of the container. Thus the gas only occupies about 0.03% of the total
volume say for 1 mole of gas at STP.
 The particles exert no attractive or repulsive forces between (themselves) one another.
 The pressure (force per unit area) is due to the impact of the particles on collision with the walls of
the container
It is with these postulates that we want to represent mathematically in the molecular theory of gases to
obtain an equation of state.
Consider a gas contained in a cube of dimension 1 meter. See Figure 5. Focus on a single molecule of mass
m confined in an otherwise empty container of volume V (l3).
14
Figure 5 Gas in a container showing the movements in three dimensions
Although the molecules move randomly, assume that an average 1/3 (direction) move in the paths parallel
to each pair of opposite faces of the container. Then if N is the total number of molecules, then N/3
molecules move along x, y or z directions. How do we calculate the pressure which will be the force exerted
per square meter.
Consider a molecule of mass m, moving back and forth, along x direction. If u is the velocity of the molecule
per second, then the rate of collision with the side of the container is given by
1 velocity u
Rateof collision   times per second (eq 29)
time distance 2l
This is because the molecule will have to travel 2l meters before collision. The momentum before collision
is mu and since the collisions are perfectly elastic, then the momentum after collision will be the same but
in the reverse direction i.e –mu.
The change in momentum = mu- (-mu)=2mu (eq 30)
This momentum is transferred to the wall of the container. The rate of change of momentum is called
force.
change in momentum 2mu mu2

Force    (eq 31)
time 2l l
u
The total force exerted by N molecules moving in the x direction will be:-
N mu2 mNu2
Total force exerted by N molecules moving in the x direction  x  (eq 32)
3 l 3l
The area of each face is l2. The pressure exerted on each face perpendicular to the x-direction will be:-
2 2
Force mNu mNu
Pressure  2
V (eq 33)
area 3lxl 3l3
15
Since l3 is the volume of the container, the pressure P and be given by equation 34 below
mNu2
P (eq 34)
3V
But we should note that the molecule will not possess the same velocity u but an average velocity ū. Hence
equation 34 will read
2
mNu 1 2
P  P  Nu (eq 35)
3V 3
Where ū2 is called the mean square velocity and is the average of u2 for all molecules. Since no direction of
velocity is preferred, then the same pressure is exerted on each of the other faces perpendicular to y and z-
directions. Hence equation 35 applies for all directions. This equation gives the relationship between P, V
and the velocity of the molecules.
The kinetic theory and temperature
We need also to know the relationship between kinetic energy of the molecules with temperature. The
kinetic energy k per molecule is given by:-
1
k mu2 (eq 36)
2
2
mNu
Inserting k in equation 34 or 35- PV 
3
And having in mind that mu2  2 k we can re-write equation 34 or 35 in terms of k and it will read:-
2 1 2
PV  x mu2 x N  Nk (eq 37)
3 2 3
For n moles of gas
Since N is equal to the Avogadro’s number, (No), multiplies by n moles i.e n No. This implies that equation
37 can be re-written as:-
2
PV   nN0k (eq 38)
3
N0k is the total kinetic energy per mole=Ea
Therefore equation 38 can be written as
2
PV   nEa (eq 39)
3
Equation 18 shoe that PV  nRT
16
2
Therefore PV  nEa = nRT
3
3
Thus Ea  RT (eq 40)
2
3
This implies that kinetic energy is the same as RT for I mole of gases at any given temperature.
2
Teaching notes
It also implies that kinetic energy of a gas depends on the temperature of that gas.
Graham’s law of diffusion
2
mNu 1 2 3PV 2
If we can use equation 35 P   P  Nu we get  u  to get the root mean square
3V 3 mN
2
velocity ( u ), then
2 3PV 3RT
u   (eq 41)
mN mN
When n=1, N0=N and mN is equivalent to the formular weight, hence
2 3RT
u  (eq 42)
M
Equation 42 is called Graham equation of diffusion and can be used to determine the formular mass M1
and M2 when the respective root mean square velocities are known.
2 3RT
u1 M1 M2
  (eq 43)
2 3RT M1
u2 M2
Since the rate at which a gas diffuses is inversely proportional to its density, which in turn is proportional to
its formular mass, then
2
u1 M2 d t
  2  2 (eq 44)
2 M1 d t1
u2 1
17
Where t1 and t2 are the time it takes for equal volumes of two gases to diffuse under similar conditions.
Teaching notes
For all gases at the same temperature, the average kinetic energies are identical.
At a fixed temperature, the average speed of a lighter gas is greater than that of a heavier gas.
Sample exercise 1.5
It takes 2 minutes for nitrogen gas to diffuse through an orifice. How long will methane gas take to diffuse
through the same orifice?
Solution
2
u1 M2 d t
From equation 44,   2  2 , we plug in the known values to determine the unknown.
2 M1 d1 t1
u2
MN t 2 M 4 16 x 4
 2  Then we get N  2  x 2   1.51 minutes
MCH4 t1 x MCH4 x 28
Sample exercise 1.4
It takes a gas A 2.3 times as long to diffuse through an oriface as the same ammount of oxygen. What is the
molarmas of A ?
Solution
2
MA 2.3t M  2.3t 
  A    MA  MO2 x 2.3x2.3  32 x 5.29  169.28
MO2 t MO2  t 
1.7 Distribution of molecular velocities
We have already noted that gas molecules in a container do not move at the same speed. The distribution
of velocities was worked out using a probability theory by Maxwell Boltzmann to yield what is referred to
as Boltzmann-Maxwell distribution law. This mathematical law is represented as:-
1 dN 3 mn
 4 π(m/2πkT) 2 e 2kTu (eq 45)
N du
18
Where k is the Boltzmann-Maxwell distribution constant. The physical interpretation of this equation is that
1 dN
represents the fraction of total number of molecules having a particular velocity u. Graphically the
N du
law can be represented as shown in Figure 6.
Figure 6 Distribution of molecular speeds at different temperatures
Note that the curves are not symmetrical and hence the average speed is higher than the most probable.
Solving the equation for 1 mole of a gas yields the following:
2kT 2RT
Most probable velocities ump   (eq 46)
m M
Where k=R/N0 and mN0=M- see eq 38
u1  u2 8kT 8RT
Mean velocity, u Un   (eq 47)
N πm M
3kT 8RT
Root mean square velocity, u  (eq 48)
m M
This is similar to equation 35.
1.7 Real gases
An ideal gas is one that obeys Boyle’s law. But few gases are ideal. In fact if PV is plotted against P, the
gases deviate from ideal behaviour as pressure increases as shown in Figure 7.
19
Figure 7 A plot of the product of the pressure and volume (PV) against P for samples of H2, N2, CO2
What causes the deviation? Since Boyle’s law agrees with molecular theory of gases, then the problem
must lie in the postulates. Firstly, the molecules are said to have no attractive or repulsive forces between
them. This is not true at moderate to high pressures since these forcers exist. Due to attractive forces, the
pressure exerted by gas will actually be less than that is predicted by theory. We need then a correction for
pressure. Since the attractive forces as well as the number of molecules striking the walls are directly
proportional to the number of molecules N, then a correction term must be proportional to N2. The number
of molecules hitting the walls will be inversely proportional to the volume, hence force will vary as 1/V2 .
The correction term was then found to be a/V2 for 1 mole. Where “a” is a constant. The pressure becomes:-
2
a an
P 2 or P 2 for n moles of gas
(eq 49)
V V
Secondly, for one mole of gas, the postulate that molecules occupy (no space) negligible volume ought to
be modified. Thus molecules should be considered to have some (space) volume. Therefore, the volume
should be corrected to take into consideration of the volume occupied by the molecules to give the
effective volume. The correction term “b” (the co-volume) was found to be four times the actual volume of
the molecules. The correction factor is introduced to give the actual volume as V-b for 1 mole or V-nb for n
moles of gas.
The final equation of state for real gas becomes:-
 an2 
 P  2  V - nb  RT for n moles of gas (eq 50)
 V 
Equation 50 is called the Van der Waals equation. It is found to give a better description of the state of gas
where a and b are constants determined experimentally.
Point of emphasis
Gases deviate from ideality at high pressure.
20
Sample exercise 1.6
Compare the pressure predicted for 0.8 l of 0.5 moles CO2 at 273 K using
(a) The ideal gas equation
(b) The Van der Waals equation
Solution
1
nRT 0.5 mol x 0.821l atm mol K x 273K
Using the ideal gas equation PV  nRT then P   14 atm
V 0.8 l
 an2 
Using the Van der Waals equation  P  2  V - bn  RT for n moles of gas
 V 
2 -2 -1 2 2
nRT an 0.5 mol x 0.821 atm mol K x 273K 6.58l atm mol
P     11.95 atm
2 2
V - nb V 0.8 l - (0.5 mol x 0.56l mol) (0.8l)
As expected, the pressure in a is higher than in b
Sample exercise 1.6
Use the Vander Waals equation to predict the pressure exerted by 100 mole of argon enclosed in 5 l flask at
100˚C. compare your results with pressure predicted by ideal gas law. A=2.351 l2 atm mol-2 and b=0.0398 l
mol-2.
Summary
To describe the state or condition of a gas, we must specify the variables: pressure, temperature, volume
and quantity of gas. Pressure is defined as force per unit area. It is expressed in SI units as Pascals,
Pa (1 Pa=101325 M m-2=1 kg m-1 s-2) or more commonly in torr or in atmosphere (atm). One atm. Equals
101325 KPa or 760 torr.
The ideal-gas equation, PV=nRT, is the equation of state for an ideal gas. Most gases at pressures about 1
atm. and temperatures of 300 K and above obey the ideal gas equation reasonably well. We can use the
ideal gas equation to calculate variations in one variable when one or more of the others are changed. For
example, for a constant quantity of gas at constant temperature, the volume of the gas at constant
pressure, the volume of a gas is directly proportional to temperature (Charles’s law). Avogadro’s law states
that at a constant temperature and pressure, the volume of a gas is directly proportional to the quantity of
gas, that is the number of molecules.
In gas mixtures, the total pressure is the sum of all the partial pressures that each gas would exert if it were
under the same conditions (Dalton’s laws of partial pressures).
21
The kinetic –molecular theory accounts for the properties of an ideal gas in terms of a set of assumptions
about the nature of gases.
The molecules of a gas do not have the same kinetic at a given instant. Their speeds are distributed over a
wide range; the distribution varies with molar mass of a gas and with temperature
Departure from ideal behaviour increases in magnitude as pressure increases and as temperature
decreases.
Van der Waals Equation
The behavior of real gases usually agrees with the predictions of the ideal gas equation to within
5% at normal temperatures and pressures. At low temperatures or high pressures, real gases deviate
significantly from ideal gas behavior. In 1873, while searching for a way to link the behavior of
liquids and gases, the Dutch physicist Johannes van der Waals developed an explanation for these
deviations and an equation that was able to fit the behavior of real gases over a much wider range of
pressures.
Van der Waals realized that two of the assumptions of the kinetic molecular theory were
questionable. The kinetic theory assumes that gas particles occupy a negligible fraction of the total
volume of the gas. It also assumes that the force of attraction between gas molecules is zero.
The first assumption works at pressures close to 1 atm. But something happens to the validity of
this assumption as the gas is compressed. Imagine for the moment that the atoms or molecules in a
gas were all clustered in one corner of a cylinder, as shown in the figure below. At normal
pressures, the volume occupied by these particles is a negligibly small fraction of the total volume
of the gas. But at high pressures, this is no longer true. As a result, real gases are not as
compressible at high pressures as an ideal gas. The volume of a real gas is therefore larger than
expected from the ideal gas equation at high pressures.
Van der Waals proposed that we correct for the fact that the volume of a real gas is too large at high
pressures by subtracting a term from the volume of the real gas before we substitute it into the ideal
gas equation. He therefore introduced a constant
constant (b) into the ideal gas equation that was equal to the volume actually occupied by a mole of
gas particles. Because the volume of the gas particles depends on the number of moles of gas in the
22
container, the term that is subtracted from the real volume of the gas is equal to the number of
moles of gas times b.
P(V - nb) = nRT
When the pressure is relatively small, and the volume is reasonably large, the nb term is too small
to make any difference in the calculation. But at high pressures, when the volume of the gas is
small, the nb term corrects for the fact that the volume of a real gas is larger than expected from the
ideal gas equation.
The assumption that there is no force of attraction between gas particles cannot be true. If it was,
gases would never condense to form liquids. In reality, there is a small force of attraction between
gas molecules that tends to hold the molecules together. This force of attraction has two
consequences: (1) gases condense to form liquids at low temperatures and (2) the pressure of a real
gas is sometimes smaller than expected for an ideal gas.
To correct for the fact that the pressure of a real gas is smaller than expected from the ideal gas
equation, van der Waals added a term to the pressure in this equation. This term contained a second
constant (a) and has the form: an2/V2. The complete van der Waals equation is therefore written as
follows.
This equation is something of a mixed blessing. It provides a much better fit with the behavior of a
real gas than the ideal gas equation. But it does this at the cost of a loss in generality. The ideal gas
equation is equally valid for any gas, whereas the van der Waals equation contains a pair of
constants (a and b) that change from gas to gas.
The ideal gas equation predicts that a plot of PV versus P for a gas would be a horizontal line
because PV should be a constant. Experimental data for PV versus P for H2 and N2 gas at 0�C and
CO2 at 40C are given in the figure below. Values of the van der Waals constants for these and other
gases are given in the table below.
van der Waals Constants for Various Gases
Compound a (L2-atm/mol2) b (L/mol)

He 0.03412 0.02370
Ne 0.2107 0.01709
H2 0.2444 0.02661
Ar 1.345 0.03219
O2 1.360 0.03803
N2 1.390 0.03913
23
CO 1.485 0.03985
CH4 2.253 0.04278
CO2 3.592 0.04267
NH3 4.170 0.03707
The magnitude of the deviations from ideal gas behavior can be illustrated by comparing the results
of calculations using the ideal gas equation and the van der Waals equation for 1.00 mole of CO2 at
0oC in containers of different volumes. Let's start with a 22.4 L container.
According to the ideal gas equation, the pressure of this gas should be 1.00 atm.
Substituting what we know about CO2 into the van der Waals equation gives a much more complex
equation.
This equation can be solved, however, for the pressure of the gas.
P = 0.995 atm
At normal temperatures and pressures, the ideal gas and van der Waals equations give essentially
the same results.
Let's now repeat this calculation, assuming that the gas is compressed so that it fills a container that
has a volume of only 0.200 liters. According to the ideal gas equation, the pressure would have to
be increased to 112 atm to compress 1.00 mol of CO2 at 0C to a volume of 0.200 L.
The van der Waals equation, however, predicts that the pressure will only have to increase to 52.6
atm to achieve the same results.
24
P = 52.6 atm
As the pressure of CO2 increases the van der Waals equation initially gives pressures that are
smaller than the ideal gas equation, as shown in the figure below, because of the strong force of
attraction between CO2 molecules.
A plot of the product of the pressure times the volume for samples of H2, N2,
CO2 gases versus the pressure of these gases.
Let's now compress the gas even further, raising the pressure until the volume of the gas is only
0.0500 liters. The ideal gas equation predicts that the pressure would have to increase to 448 atm to
condense 1.00 mole of CO2 at 0oC to a volume of 0.0500 L.
The van der Waals equation predicts that the pressure will have to reach 1620 atm to achieve the
same results.
25
P = 1620 atm
The van der Waals equation gives results that are larger than the ideal gas equation at very high
pressures, as shown in the figure above, because of the volume occupied by the CO2 molecules.
Analysis of the van der Waals Constants
The van der Waals equation contains two constants, a and b, that are characteristic properties of a
particular gas. The first of these constants corrects for the force of attraction between gas particles.
Compounds for which the force of attraction between particles is strong have large values for a. If
you think about what happens when a liquid boils, you might expect that compounds with large
values of a would have higher boiling points. (As the force of attraction between gas particles
becomes stronger, we have to go to higher temperatures before we can break the bonds between the
molecules in the liquid to form a gas.) It isn't surprising to find a correlation between the value of
the a constant in the van der Waals equation and the boiling points of a number of simple
compounds, as shown in the fugure below. Gases with very small values of a, such as H2 and He,
must be cooled to almost absolute zero before they condense to form a liquid.
The other van der Waals constant, b, is a rough measure of the size of a gas particle. According to
the table of van der Waals constants, the volume of a mole of argon atoms is 0.03219 liters. This
number can be used to estimate the volume of an individual argon atom.
The volume of an argon atom can then be converted into cubic centimeters using the appropriate
unit factors.
26
If we assume that argon atoms are spherical, we can estimate the radius of these atoms. We start by
noting that the volume of a sphere is related to its radius by the following formula.
V = 4/3 r3
We then assume that the volume of an argon atom is 5.345 x 10-23 cm and calculate the radius of the
atom.
r = 2.3 x 10-8 cm
According to this calculation, an argon atom has a radius of about 2 x 10-8 cm.
Exercise one
1. During the course of a reaction, 0.25 moles of gas phase reactant becomes 0.50 moles of gas phase
product. The initial volume of the gaseous reactant is 125 cm3. What is the volume of the gaseous
product?
2. 1 l of an ideal gas at 0.4775 atm and 12.2˚C undergoes a change in volume and pressure to 5.3 l and
1.22 atm. What is the new temperature of the gas?
3. A helium balloon has a volume of 2 l. How many moles of helium will the balloon hold if it is filled
to a pressure of 1.01 atm at a temperature of 24˚C? How many grams of helium does it hold?
4. What is the density of carbon tetrafluoride at 1.0 atm and 298 K?
5. What is the pressure exerted by 100 moles of CO2 in a 22.4 l vessel at 273 K, a calculated from Van
der Waals equation? Compare your results with the pressure predicted by the ideal gas equation
given a=3.59 l2 and b=0.043 l mol-1.
6. What is the volume at STP, of 1.0 l of carbon tetrachloride?
7. 0.50 g of neon gas and 0.50 g of argon gas are placed in a 3.0 l flask at 27˚C. What is the partial
pressure of each gas and the total pressure of the mixture of the gases in the atmosphere?
8. 150 g of neon and 100 g of oxygen are placed in a flask at a temperature such that the total
pressure is 1,22 atm. What is the mole fraction and partial pressure of each gas?
9. At a given temperature and pressure, a certain amount of argon requires 277 s to diffuse through
a porous plug. How long will it take an equivalent amount of nitrogen to diffuse under the same
conditions?
10. Calculate the pressure exerted by 40 g of oxygen enclosed in a 1 l flask at 25˚C. (RFM of O=16)
27
Egg-in-the-Bottle Demonstration
A demonstration should be carried out “The Egg-in-the-bottle” to introduce the concept of air
pressure in a chamber at different temperatures. This illustrates the way temperature affects
pressure for students in agreement with gas laws.
Chemical equilibria
2.0 Chemical equilibria
2.1 Introduction
The conditions in which the concentrations of all reactants and products cease to change with time is called
chemical equilibrium. Chemical equilibrium occurs when opposing reactions are proceeding at equal rates.
Thus the rate of forward reaction is equal to the rate of the reverse reaction. In other words, the rate at
which products are formed from the reactants equals the rate at which the reactants are formed from
products. For equilibrium to occur, neither reactants nor products can escape from the system. Chemical
equilibria are of importance in explaining a great many natural phenomenon and play important roles in
many industrial processes. We will learn how to express the equilibrium position of a reaction in
quantitative terms, and we will study the factors that determine the relative concentrations of reactants
and products at equilibrium.
2.2 Learning goals
By the end of this unit you should be able to:-

 Write equilibrium expression for a balanced chemical equation, wheather heterogeneous or
homogeneous.
 Numerically evaluate Kc (Kp) from knowledge of equilibrium concentrations (pressure) of reactants
or products, or from initial concentrations and the equilibrium concentrations of at least one
substance.
 Interconvert Kc Kp.
 Calculate the reaction quotient, Q, and by comparison with the values of Kc or Kp determine
whether a reaction is at equilibrium. If it is not at equilibrium, you should be able to predict in
which direction it will shift to react equilibrium.
 Use the equilibrium constant to calculate how quantities of reactants and products are shifted by
change in temperature, pressure or the concentrations of substances in the equilibrium reaction.
2.3 The concept of equilibrium
The state of equilibrium can be defined as a condition in which all substances involved in a chemical
reaction have reached a final value of concentration.
What does this mean?
Let us consider the reaction of acetic acid with ethanol
CH3COOH + C2H5OH ⇌ CH3COOC2H5 + H2O (eq 2.1)

Acid Alcohol Ester Water
We find that, if infinitely only the acid and alcohol are mixed, then the ester and water are formed.
However, if it is the ester and water that are mixed, the acid and alcohol are produced. It is therefore clear
that equation 2.1 can be achieved from either end. Let us concentrate on the acid/alcohol reaction. When
the two are mixed, they start forming ester/water, at a given rate r1, whose concentration start increasing.
The formed products also start reacting in a reverse reaction at a given rate r2. A certain point is reached
when the rate of forward reaction r1 becomes equal to the rate of reverse reaction r2 i.e. r1= r2. Here the
forward reaction takes place with the same rate as the reverse reaction. The concentrations of all the four
Chemical equilibria
reactants remain constant and a state equilibrium is achieved. We should note that both forward and
reverse reactions have not stopped but only that they have the same rates. Such an equilibrium, which is
not “stagnant” is called a dynamic equilibrium. The final constant concentrations will not necessarily be the
same for any reaction.
Suppose we have the general reaction
(eq 2.2)
Where A, B, Y and Z are chemical species involved, and a, b, y and z are their coefficients in the balanced
chemical equation. According to the law of mass action, the equilibrium condition is expressed by the
equation 2.3 given below.
[Y]y [Z]z
KC  (eq 2.3)
[A]a [B]b
The square brackets in this equation signify molar concentrations.
The relationship in equation 2.3 is called an equilibrium expression or the equilibrium constant (K c)
expression. The equilibrium constant (Kc), is the numerical value obtained when we substitute actual
equilibrium concentrations into the equilibrium expression. The subscript c indicates that the quantity of
reactants is in moralities.
Note that once we know the balance chemical equation for equilibrium, we can write the equilibrium
expression even if we do not know the reaction mechanism. The equilibrium expression depends only on
the stoichiometry of the reaction and not mechanism.
Point of emphasis
 The notation Kc is a reminder that the amounts of materials are in molar concentrations.
 For a particular reaction, the value of the equilibrium constant varies with temperature
Sample exercise 2.1
Write an equilibrium expression Kc for the following reactions

(a) 2O3⇌3O3
(b) 2NO(g) + Cl2⇌ 2NOCl(g)
Solution
The equilibrium expression has the form of a quotient. The numerator contains the concentrations of
substances on the product side of the chemical eqation, each raised to a power equal to its coefficient in
the balanced equation. The denominator is similarly obtained using the substances on the reactant side.
[O2 ]3 [NOCl]2
(a) K C  (b) K C 
[O3 ]2 [NO]2 [Cl2 ]
31
Sample exercise 2.1
Write the equilibrium constan expression for H2(g) + I2(g) ⇌ 2HI(g)
2.4 The magnitude of equilibrium constants

Equilibrium constant can be very large or very small. The magnitude of the constant provides us with
important information about the equilibrium mixture. In order for the equilibrium constant to be so large,
the numerator of the equilibrium expression must be larger than the denominator.
K>>1: Equilibrium lies to the right, products favoured
K<<1: Equilibrium lies to the left, reactants favoured
We often do not know the equilibrium concentrations of all chemical species in equilibrium. However, if we
know the equilibrium concentrations of at least one species, we can generally use the stochiometry of the
reaction to deduce the equilibrium concentrations of the other species in the chemical equation. We will
use the following procedure to do this:-
1. Tabulate the known initial and equilibrium concentrations of all the species in the equilibrium
2. For those species for which both the initial and equilibrium concentrations are known, calculate the
changes in concentration that occurs as the system reaches equilibrium
3. Use stoichiometry of the reaction to calculate the changes in concentration for all the other species
in the equilibrium
4. From the initial concentration and the changes in concentration, calculate the equilibrium
concentrations. These are used to evaluate the equilibrium concentration.
Example
A mixture of 5.00 x 10-3 mol of H2 and 1.00 x 10-2 mol of I2 are placed in a 5.00 l container at 448 ˚C and
allowed to come to equilibrium. Analysis of the equilibrium mixture shows that the concentration of HI is
1.87 x 10-3 M. Calculate Kc at 448 ˚C for the reaction.
H2(g) + I2(g) ⇌ 2HI(g)
Solution
[HI]2
KC 
[H2 ][I2 ]
First, we tabulate the initial and equilibrium concentrations of all the species in the equilibrium. In our table
we also provide space for listing the changes in concentration. As shown below, it is convenient to use the
chemical equation as the heading for the table.
In this exercise, the initial concentrations of H2(g) and I2(g) must be caculated:
-3
5.00 x 10 mol -3
[H2 ]initial   1.00 x 10 M
5.00 l
32
Chemical equilibria
-2
1.00 x 10 mol -3
[I2 ]initial   2.00 x 10 M
5.00 l
Thus, the first entries in the table are:-
H2(g) + I2(g) ⇌ 2HI(g)
H2(g I2(g HI(g)

-3 -3
Initial 1.00 x 10 2.00 x 10 0.0
Change
-3
Equilibrium 1.87 x 10
Secondly, we calculate the change in concentration of HI, using the initial and equilibrium value. The
change is the difference between the initial and equilibrium value, 1.87 x 10-3 M.
Third, we use the stoichiometry of the reaction to calculate the changes in the other species. The balanced
chemical equation indicates that, for each 2 moles of HI formed, 1 mole of H2(g) is consumed. Thus, the
amount of H2(g consumed is
-3  1 mol H2 
(1.87 x 10 M)
   0.9300 x 10-3 M H2(g)
 2 mol HI 
The same line of reasoning gives us the amount of I2(g) consumed, which is also 0.93 x 10-3 M.
Fourth, we calculate the equilibrium concentrations, using the initial concentration and the changes. The
equilibrium concentration of H2(g) is the initial concentration minus the consumed.
-3 -3 -3
[H2]= 1.00 x 10 M - 0.93 x 10 M= 0.065 x 10 M
-3 -3 -3
[I2]= 2.00 x 10 M - 0.93 x 10 M= 1.065 x 10 M
Finally, now that we know the equilibrium concentrations of each reactant and product, we can use the
equilibrium expression to calculate the equilibrium constant.
KC 
[HI]
2

1.87 x 103 2  50.5
3 3
[H2 ][I2 ] (0.065 x 10 )(1.065 x 10 )
Another worked example
A mixture of 2.00 mol of H2 and 1.00 mol of I2 were placed in a 1.00 l container at 448 ˚C. Given that Kc is
50, calculate the concentrations of each at at equilibrium.
Then we create a table
33
H2(g I2(g HI(g)
Initial 2.00 moles 1.00 moles 0.0
-3 -3 -3
Change -0.935 x 10 --0.935 x 10 +1.87 x 10
No of moles at equilibrium 2-x 1-x 2x
No of moles at equilibrium (2-x)/1 (1-x)/1 (2x)/1
2 2
(2x ) 4x
KC   50  50  2
 Then work out  The value of x will be 0.935
(1 - x)(2 - x) (2 - 3x  x )
Take the inverse as the values are too big to work with
2
(2 - 3x  x ) 2
0.02  2
 0.92 x  3 x  2  0  The value of x will be 0.935
4x
Sample exercise 2.2

Sulphur trioxide decomposes at high temperature in a sealed container:
2S03(g) ⇌ 2SO2(g)+ O2(g)
Initially the vessel is charged at 1000 K with S03(g) at a concentration of 6.09 x 10-3 M. At equilibrium, the
concentration of S03(g) was 2.44 x 10-3 M. Calculate the value of Kc
Answer Kc= 4.07 x 10-3
Sample exercise 2.3

The reaction of N2(g) and O2(g) to form NO might be considered as means of fixing nitrogen.
N2(g) + O2(g) ⇌ 2NO(g)
-30
The value for the equilibrium constant for this reaction at 25˚C is K c=1 x 10 . Describe the feasibility of this reaction for nitrogen
fixation.
Find the Solution

The equilibrium constant for the reaction H2(g) + I2(g) ⇌ 2HI(g) varies with temparature in the following way: Kc=50.3 at 721 K and
Kc=54 at 700 K. Is the formation of HI favoured by higher or lower temperatures?
2.4.1 The direction of chemical equation and K

Because equilibrium can be approached from either direction, the direction in which we write the chemical
equation for equilibrium is arbitrary. For example, we can represent the NO2/N2O4 equilibrium as-
N2O4(g) ⇌ 2NO(g)
For the equation, we can write
2
[NO2 ] o
KC   0.212 (at 100 C)
[N2O 4 ]
We could equally well consider this same equilibrium in terms of the reverse reaction:-
2NO(g) ⇌N2O4(g)
The equilibrium expression is given by:-
[N2O 4 ] o
KC  2  4.72 (at 100 C)
[NO2 ]
The equilibrium expression for the reaction written in one direction is reciprical of the one for the reaction
written in the reverse direction.
Point of emphasis
34
Chemical equilibria
For the value of equilibrium constant to be meaningful, we must specify how equilibrium reaction is written;
which species are written on the product side and which are written on the reactants side.
For the formation of NH3 from N2 and H2, N2(g) +3 H2(g) ⇌ 2NH3(g); Kp =4.34 x 10-3 at 300˚C. What is the value
of Kc for the reverse reaction?
Calculate the concentration equilibrium constant Kc at 298 K for the following reactions:-
(a) 1 mole of acetic acid are mixed with 0.18 moles of ethanol to give 0.171 moles of ester at
equilibrium
(b) 1 mole of acetic acid are mixed with 1 mole of ethanol to give 0.667 moles of water at equilibrium
Sample exercise 2.4
At 25˚C, when 3 moles of acetic acid are mixed with 3 moles of ethanol and allowed to attain equilibrium,
the concentrations at equilibrium are found to be:-
Acetic acid- 1 mole, ethanol- 1 mole, ester- 2 moles and water 2 moles. What is the equilibrium constant
for this reaction?
CH3COOH + C2H2OH ⇌CH3COOC2H5 + H2O
CH3COOH C2H2OH CH3COOC2H5) H2O

Initial 3 moles 3 moles 0 moles 0 moles
Change 2 moles 2 moles 2 moles 2 moles
Equilibrium 1 moles 1 moles 2 moles 2 moles
2 x2
[CH 3COOC2 H 5 ][H 2O]
KC   V V 4
[CH 3COOH][C2 H 2OH] 1 x 1
V V
Note that if Kc = 4 for this reaction, then whatever initial portions that we start off with, at equilibrium, the
concentration will be such that this value is maintained. Note also in this case Kc has no units
2.5 Gaseous equilibrium
For gases it is more reasonable to use pressure in place of concentration. i.e for a gaseous reaction such as
35
eE + fF ⇌gG +hH (eq 2.4)
The constant will be:-
Pg G x Ph H
Kp  (eq 2.5)
Pe E x P f F
Where P represents the partial pressure of each gas at equilibrium and Kp is the equilibrium constant in
terms of pressure.
Under equilibrium conditions, at 500K and 1 atm total pressure, nitrosyl chloride is 27% dissociated according to the reaction:-
2NOCl⇌ 2NO +Cl2 Determine Kp
Sample exercise 2.5

At 300 K and 1 atm pressure, dinitrogen tetraoxide is 20% dissociated into nitrogen dioxide. Calculate the equilibrium constant Kp
for the reaction:- N2O4⇌ 2NO2
N2O4 NO2
Initial 1 moles 0 moles
Change 2 moles 2 moles
Equilibrium 1-α moles 2α
Total number of moles at equilibrium will be:-
No of moles of N2O4 + No of moles of NO2
1-α + 2α=1+ α
 1 -α   2α 
Therefore the partial pressure of N2O4   P and the partial pressure of NO2   P
1 α  1 α 
Where P is the total pressure
2
2
 2α P 
2 2
P NO
2  1  α  4α P 4 x 0.2 x 1 atm
Kp 
PN O
2 4


P 1 -α
1 α
  
1  α 1 - α  1  0.21 - 0.2
 0.167 atm
2.6 Relationship between Kc and Kp
Pressure is another way of expressing concentration. See equation 1.20, P  CRT . Therefore Kc can be
expressed in terms of Kp. How can we obtain the relationship?
Let us consider the following equilibrium:-
N2(g) + 3H2(g)⇌ 2NH3(g) (eq 2.6)
The concentration equilibrium constant, Kc, is given by:-
36
Chemical equilibria
2 2
P NH [NH3 ]
3
KP  whereas K c  (eq 2.7)
3 3
PN P H [N2 ][H2 ]
2 2
n
From PV  nRT  P  RT
V
ni
The partial pressure, i, of each gas can be expressed as Pi  RT  C iRT
V
Since Kp is given by the following expression,
2
P NH
Kp  3
3 (eq 2.8)
PN x P H
2 2
Then
CNH RT  2
2
C NH3 1 Kc
  
C N RT x C H RT 
3
Kp x (eq 2.9)
3 CN x CH RT
2
RT
2
2 2 2 2
It can be seen that Kp is not equal to Kc but is proportional to Kc
- Δn
Kp  K c (RT) (eq 2.10)
Where Δn is the difference between the number of moles of the products and those of the reactants in the
stoichiometric equation
Δn   no of moles produced -  no of moles reacting
For our equilibrium, i.e formation of ammonia, 2 moles of ammonia are formed after reacting 4 moles of
reactants.
Therefore
Δn  2  4  2 If we place the value of Δn in equation 2.10, we get
- -2
Kp  Kc(RT) (eq 2.11)
37
Where there is no change in the number of moles, Kp=Kc. An example is in the reaction between hydrogen
and iodine vapour.
H2(g) + I2(g)⇌2HI(g) (eq 2.12)
Common misconception
Students frequently arrive at the wrong sign for Δn in the expression Kp  Kc(RT)- Δn . Note that Kp is
in the left and Δn=product moles of gas-reactant moles of gas
Sample exercise 2.6
For the equilibrium 2S03(g) ⇌ 2SO2(g)+ O2(g) at temperature 1000 K, Kc has the value 4.07 x 10-3. Calculate the
value of Kp.
Ans. Kp =0.334
From the the sample exercise 2.6, there are 3 moles of gaseous products (2S03(g) + I2(g) ⇌ (2SO2(g)+ O2(g)) and
two moles of reactants Therefore Δn=3-2=1
The temperature is 1000 K and R=0.821
Practice exercise 2.6
At 457 K and a total pressure of 1 atm, nitrogen dioxide is 5% dissociated according to the equation
2NO2⇌2NO + O2 Calculate the constants Kp and Kc for this reaction.
2.7 Approach to equilibrium

We have stated that no matter what amounts of material we start off with in a reaction, the equilibrium
constant after establishment of equilibrium can be approached from either reactants forming products or
the vice versa. Following are examples to illustrate this fact.
a) One mole of H2 and one mole of I2 are introduced into a 1-liter box at 490 ˚C. Calculate the final
concentrations of reactants and products when equilibrium is established. Kc=45.9
If n is the number of moles of H2 that react, then
H2 I2 HI
Initial 1 1 0
Change n n 2n
Equilibrium 1-n 1-n 2n
38
Chemical equilibria
[HI]
2 2n 
2
4n
2
[H2 ][I2 ] 1 - n 1 - n  1 - n

Kc   V  2  45.9 ,
V V
The result of this quadratic equation, which can be solved to yield two values of 0.772 and 1.42.
Point of emphasis
o For the equation 0=ax2+bx+c, the value of x is given by solving the quadratic equation given
below
b  b2  4ac
o x
2a
After solving the value of n in the previous equation, it cannot be greater than 1 and in this case
n=0.772. Therefore the concentrations at equilibrium are H2 =0.228 moles, I2= 0.228 mole and
HI=1.544
b) If initially it was 2 moles of HI that were introduced into the box an n moles reacted. Then the
respective concentrations could be tabulated as shown
H2 I2 HI
Initial 0 0 2
Change n/2 n/2 -n
Equilibrium n/2 n/2 2-n
[HI]
2
2  n2
Kc 
[H2 ][I2 ]

n 2 n 2   45.9
Solving for n , gives n=456. This means that the concentration of H2= I2=0.225 and HI=1.544.
c) All materials may be present in different amounts initially. Here the direction of the reaction is not
obvious and one may choose whatever direction, forward or reverse to workout equilibrium
concentrations. So if the following were initially present, and the forward reaction assumed, 1 mole
H2, 2 moles of I2 and 3 moles of HI. If n H2moles of reacted, then
H2 I2 HI
Initial 1 2 3
Change n n 2n
Equilibrium 1-n 2-n 3+2n
For every n moles of H2 that react, n moles of I2 react as well and 2n moles of HI are produced. Note
that since a forward reaction has been assumed, if it is indeed a reverse reaction that takes place,
then n can be a negative value. Now
39
Kc 
[HI]2

3  2n   45.9
2
[H2 ][I2 ] 1 - n 2 - n
From the equation, n is found to be equal to 0.684. Therefore concentrations at equilibrium are:-
H2= 0.316, I2=1.316 and HI=4.544 386 moles
(Assume a reverse reaction and confirm that the same results are obtained)
2.8 Heterogeneous equilibrium
When all reactants and products are in the same phase in a reaction at equilibrium, then we have a
homogeneous equilibrium. If however any of the reactants or products are in a different phase, then a
heterogeneous equilibrium exists. Consider the reaction:-
CaCO3(s) ⇌ CaO(s) + CO2(g) (eq 2.13)
Here both solid and gas are involved and therefore this is an example of a heterogeneous equilibrium. The
equilibrium constant for this equilibrium can be given in terms of activity, ɣ, which refers to ‘effective’
concentration or active mass of substance. Thus
 CaO CO
K 2
(eq 2.14)
 CaCO
3
The active mass of a solid remains constant and therefore activity of solids is conventionally 1 while that of
a gas is equivalent to pressure at low pressures. Hence
Kc  γCO2  [CO2 ] or Kp  PCO2 (eq 2.15)
Since activity is also equal to concentration at low concentrations, Kp will be proportional to pressure of CO2
only, at any given temperature. Kp is therefore determined solely by the equilibrium pressure of CO2 and
not the amounts of CaCO3 and CaO.
Point of emphasis
Pure solids and liquids have essentially constant concentrations. In effect, we ignore the
concentrations of pure liquids, even though they must be physically present in the equilibrium
mixture.
Sample exercise 2.7

40
Chemical equilibria
Write the equilibrium expression for Kc and Kp for each of the following reactions:
(a) CO2(g) + H2(g) ⇌ CO(g) + H2O(l)

(b) SnO2(s) + CO2(g) ⇌ Sn(s) + 2CO(g)
Solution
2 2
[CO2 ][H2 O] [CO2 ] P CO
2
(a) K c   and KP 
[CO] [CO] PCO
This is because water is a pure liquid hence its concentration does not appear in thr eqilubrium expression
2 2 2
[Sn][CO] [CO] P CO
(b) Kc   and KP 
[SnO2 ][CO2 ] [CO ] PCO2
2
This is because Sn02 and Sn are both pure solids, their concentrations does not appear in the equilibrium
expression
Write the equilibrium expression for expression for Kc and Kp for the reaction:- Fe(s) H2O (g) ⇌ Fe3O4(s) + H2(g
2.9 Factors influencing equilibrium concentration
A reversible reaction in a dynamic equilibrium will maintain the condition indefinitely unless disturbed by
external changes. These are changes that will accelerate or retard either the forward or the reverse
reaction, therefore causing a change in equilibrium concentrations. These include:-
1. Addition or removal of a reactant or product, i.e change in concentration

2. Change in pressure/volume
3. Change in temperature
The effects are summed up by the Le Chatelier’s Principal which states:-
If a change in any of the factors upon which equilibrium depends is made to a system in equilibrium, the
equilibrium shifts in the direction which tends to nullify the effects of the change. Get another version
41
Le Chatelier’s principle can be stated as follows: If a system at equilibrium is disturbed by a change in
temperature, pressure, or the concentration of one of the components, the system will shift its equilibrium
position so as to counteract the effect of the disturbance.
Teaching notes
Consider changing the concentration or pressure of a substance in a reaction at equilibrium as

creating stress. The removal of something creates a “deficit stress”, and adding something creates
“excess stress”. Reactions will always respond to stress by reducing the deficit (making more of
what was removed) or by reducing the excess (consuming some of what was added). This
description works regardless of which side of the reaction is changed.
Point of emphasis
If you add a substance to a reaction at equilibrium, the reaction will shift to consume some of the
added substance. If you remove a substance from a reaction at equilibrium, the reaction will shift to
produce more of the removed substance.
We can deduce the rules for the temperature dependence of the equilibrium constant by applying Le
Châtelier's principle. A simple way to do this is to treat heat as if it were a chemical reagent. In an
endothermic reaction we can consider heat as a reactant, whereas in an exothermic reaction we can
consider heat as a product:
Endorthermic : Reactants  heat  Products (eq 2.16)
Exorthermi c : Reactants  Products  heat (eq 2.17)
When the temperature is increased, the equilibrium shifts in the direction that absorbs heat. In an
endothermic reaction, such as Equation 2.16, heat is absorbed as reactants are converted to products;
thus, increasing the temperature causes the equilibrium to shift to the right, in the direction of products,
and Kc increases. In an exothermic reaction the opposite occurs. Heat is absorbed as products are
converted to reactants, and so the equilibrium shifts to the left and Kc (eq 2.17) decreases. We can
summarize these results as follows:
Cooling a reaction has the opposite effect of heating it. As we lower the temperature, the equilibrium shifts
to the side that produces heat. Thus, cooling an endothermic reaction shifts the equilibrium to the left,
decreasing Kc. Cooling an exothermic reaction shifts the equilibrium to the right, increasing Kc
42
Chemical equilibria
Effect of change in Reactant or Product Concentrations
A system at equilibrium is in a dynamic state; the forward and reverse processes are occurring at equal
rates, and the system is in a state of balance. An alteration in the conditions of the system may disturb the
state of balance. If this occurs, the equilibrium shifts until a new state of balance is attained. Le Châtelier's
principle states that the shift will be in the direction that minimizes or reduces the effect of the change.
Therefore, if a chemical system is at equilibrium and we add a substance (either a reactant or a product),
the reaction will shift so as to re-establish equilibrium by consuming part of the added substance.
Conversely, removal of a substance will result in the reaction moving in the direction that forms more of the
substance.
Consider the reaction
H2 + I2⇌2HI (eq 2.18)
At equilibrium, the rate of reaction between H2 and I2 is the same as that of their formation from the
decomposition of HI. If either the concentration of H2 or I2 is increased, the rate of reaction in the forward
reaction increases causing an increase in the concentration of HI. As a result, the rate of formation of H2
and I2 then increases until at equilibrium, new equilibrium concentrations are attained. The result is
therefore the consumption of the added H2 and I2 to maintain the equilibrium constant.
Thus if either H2 or I2 or both concentrations are increased, the equilibrium shifts to the right while if HI
concentration is increased, the equilibrium shifts to the left. Decreasing the above concentrations has the
opposite effects. Note that Kc remains constant.
Effect of change in pressure
Consider an equilibrium mixture of N2, H2, and NH3:
N2(g) + 3H2(g) ⇌ 2NH3(g) (eq 2.19)
4 moles 2 moles
According to Le Chatelier’s principal, an increase in pressure in such a way that the total pressure of the
gases decreases. Note that in moving the equilibrium from left to right, causes the number of moles to
change from 4 to 2. For gases, an increase in the number of moles leads to an increase in pressure.
Therefore if external pressure is increased, the equilibrium shifts towards decreases number of moles thus
shifts the equilibrium to the right. An addition of H2 would cause the system to shift, so as to reduce the
concentration of H2 toward its original value. This can occur only if the equilibrium shifts to form more NH3.
At the same time, the quantity of N2 would also be reduced slightly. Addition of more N2 to the equilibrium
would likewise cause a shift in the direction of forming more NH3. However, if we add NH3 to the system at
equilibrium, the concentrations will adjust to reduce the NH3 concentration toward its original value; that
is, some of the added ammonia will decompose to form N2 and H2.
43
X2NH 3 1
Kp  x (eq 2.20)
XN2 XH 2 P2
X2NH3
Since Kp must remain constant, If P is increased must increase. This quality increases if
XN2 XH 2
X2NH3 increases and the product of XN2 and XH 2 decreases. This can be achieved by shifting of the
equilibrium to the right. If the numbers of moles is the same on both sides of the equition, then pressure
has no effect on such a equilibrium. An example of such is the reaction of hydrogen and iodine vapour in
equation 2.16. In such cases, and increase or decrease in external pressure has no effect on the
equilibrium.
Effect of change in temperature
Equilibrium concentrations are always defined at a given temperature and change if the temperature is
changed. This implies that equilibrium constant is temperature dependent. This is because temperature
increases the rate of forward or reverse reaction even if not at the same extent. For a system at
equilibrium, if the forward reaction is exothermic, the reverse reaction is endothermic and at the same
extent otherwise a situation where energy could be created or destroyed.
N2(g) + 3H2(g) ⇌ 2NH3(g) ΔH=-5508 J (eq 2.21)
For the reverse reaction
2NH3(g) ⇌ N2(g) + 3H2(g) ΔH=5508 J (eq 2.22)
According to Le Châtelier’s principle, the reaction in equation 2.19 will shift to the left if the temperature is
increased. This will enable the system to adsorb heat. In that case more N2(g) and H2(g) are formed. This
contributes to a decrease in Kp. The opposite happens for a decrease in temperature.
Summary
If the reactants and products of a reaction are kept contact, a chemical reaction can achieve a state in
which the forward and reverse reactions are occurring at equal rates. This condition is known as chemical
equilibrium. A system at equilibrium does not change with time. For such a system, we can define an
equilibrium constant, K,. At equilibrium, the equilibrium constant equals the equilibrium expression, which
is given by the product of the concentrations of the products, each raised to the power of its coefficient in
the balanced chemical equation, divided by a like product of the reactants concentrations. The equilibrium
constant changes with temperature but it is not affected by changes in relative concentrations of any
reacting substance or pressure or the presence of catalyst. In heterogeneous equilibria, the concentrations
of pure liquids are absent from the equilibrium expression.
If concentrations are expressed in molarity, we label the equilibrium constant Kc; If concentrations are
expressed in atmosphere, we use Kp. The constant Kc and Kp are related by the following equation:
44
Chemical equilibria
Kp =Kc (RT)Δn. A large value for Kc or Kp indicates that the equilibrium mixture contains more products that
reactants. A small value for the equilibrium constants means that the equilibrium lies towards the reactants
side.
Exercise 2
1. For the reaction of alcohol with an acid at 50˚C, the concentrations of each substance at
equilibrium are:-
Acid = 1.1 M, alcohol = 1.8 M, ester 2.6 M and H2O= 1.9 M. What is the equilibrium constant?
2. Kc= 0.050 at 2200˚C for the following equilibrium; 0,50 M gas in the equilibrium is introduced into a
flask at 2200˚C. In which direction will the reaction take place for equilibrium to be attained?
N2(g) + O2(g) ⇌ 2NO(g)
3. At 250˚C, Kc=3.2 x 103 for the equilibrium:- PCl3(g) + Cl2(g) ⇌ PCl5(g) . What is Kp at this temperature?
4. Given the following reaction; 2ICl3(g) ⇌ Cl2(g) + I2(g); Kc = 0.10, Determine the equilibrium
concentration of each of the substances when ICl initially at 0.7 M is allowed to come to
equilibrium.
5. At another temperature, the reverse equilibrium in question 5 has Kc = 0.52. What will be the
equilibrium concentrations of all the substances in the equilibrium when Cl2(g) and I2(g) both
initially at 0.01 M concentrations are allowed to come to equilibrium?
6. For the reaction- I2(g) ⇌ 2I(g) Kc = 6.6 x 10-2. What are the equilibrium concentrations of I and I2 if I2
initially at 3.5 M is allowed to come to equilibrium?
7. Consider the equation below:-
2HI(g) ⇌ H2(g) + I2(g
At equilibrium, the following are the concentrations, 2HI(g) = 0.21 M. H2(g) = I2(g)= 0.017 M. If more
HI is added to make the concentration 0.46 M, What will be the new concentrations when
equilibrium is established and in what direction has the original equilibrium shifted?
8. For the equilibrium 2NO(g) + O2(g ⇌ 2NO2(g); Kp = 140 atm-1 at 327 ˚C. Calculate Kp at 527 K given
that ΔH=-116 KJ mol-1. Comment on the difference between the values.
9. Kc at 25 ˚C for the reaction in question 1is 4. Is the equilibrium exothermic or endothermic?
45
3.0 Acid-base equilibria
3.1 Introduction
Acids and bases are important in numerous chemical processes that occur around us, from industrial
process to biological ones from reactions in the laboratory to those in the environment. We will see how to
describe the aqueous equilibria quantitatively in this section.
Acids and bases may be taken as substances that increase the concentration of H+(aq) and OH-(aq)
respectively. If an aqueous solution contains more H+(aq) than OH-(aq), the solution is acidic. Likewise, if the
solution contain more OH-(aq) than H+(aq), the solution is basic.
Why are these two ions of major importance in our discussions of aqueous chemistry? Is there a
relationship between the concentrations of these two ions in aqueous solution? We shall also broaden our
discussion to include additional equilibria involving slightly soluble salts.
3.2 Learning goals
 Explain what is meant by the ionization of water, and write the ion-product constant expression for
the process.
 Define pH; calculate pH from [H+] or [OH-] and perform the reverse operation.
 Identify the common strong acids and bases; be able to calculate the ph of their aqueous solutions
from known concentrations.
 Calculate the ph for a weak acid solution in water given the acid concentration and Ka; calculate Ka
given the acid concentration and pH.
 Predict whether a particular salt solution will be acidic, basic or neutral.
 Describe how a buffer solution of particular pH is made and the reactions that allow it to control
pH.
 Calculate the change in pH of a simple buffer solution of known composition caused by adding a
small amount of strong acid or base.
 Calculate the concentration of each species present in solution formed by mixing an acid and a
base.
 Describe the form of titration curves for titration of a strong acid by a strong base, a weak acid and
a strong base or a strong acid by a weak base.
 Set up the expression for the solubility-product for a salt.
 Calculate Ksp fro solubility product data, and solubility of a slightly from value of Ksp.
 Calculate the effect of an added common ion on the solubility of slightly soluble salt.
46
Acid-base equilibria
3.3 Ion product of water
Pure water ionizes to a very small extent according to the following equilibria
H2O(l)⇌H+(aq) + OH-(aq) (aq 3.1)
We shall call this process the ionization of water. At room temperature, only about one out of every 108
molecules is ionized at a given instant. No individual molecule remains ionized for long; the equilibria are
extremely rapid.
The equilibrium expression for the auto ionization is:-
[H ][OH ]
K (eq 3.2)
[H2O]
But concentration of water remains effectively constant as K is very small hence K[H2O]=Kw=[H+][OH-]. The
product of the two constants, [H+] and [OH-], defines a new constant, Kw. this is important equilibrium is
called the ion-product constant for water and has a value of 1 x 10-14 mol2 l-2at 25 ˚C. Kw must remain
constant for solutions in water and addition H+ or OH- from any other source constitutes a stress causing a
shift in equilibrium according to Le Châtelier’s principle. Even bases will have associated with them as [H+]
dependent on [OH-] and Kw. Therefore, for a pure solution that neither yields H+(aq) nor OH-(aq)Ions.
Kw =[H+][OH-]=10-14 Hence [H+]=[OH-]=10-7
A solution for which [H+]=[OH-] is said to be neutral. In most solution, H+ and OH- concentrations are not
equal. As the concentration of one of these increases, the concentration of the other must decrease so that
the ion product equals to 1.0 x 10-14. In acidic solutions, [H+] exceeds [OH-]. In basic solutions, the reverse is
true: [OH-] exceeds [H+].
Teaching notes
Other liquid solvents, such as NH3 also undergo auto-ionization.
Point of emphasis
The ion-product constant, Kw is unaffected by whether a solution is acidic or basic. An acid solution has
[H+]>[OH-], whereas a basic solution has [OH-]> [H+]. At 25 ˚C the product of [H+] [OH-] is always 1.0 x 10-14.
+ -
Because Kw varies slightly with temperature, the concentration of [H ] and [OH ] in a neutral solution also vary slightly with
temperature.
47
Sample exercise 3.1
Calculate the values of [H+] and [OH-] in a neutral solution at 25 ˚C.
Solution
By definition, in a neutral solution, [H+] equals [OH-]. Let us call the concentration of each of these species
in neutral solution x.
[H+] [OH-]= (X)(X)=1.0 x 10-14 ⇒ X2= 1.0 x 10-14
⇒ X= 1.0 x 10-7=[H+] = [OH-].
In acid solution, [H+] is greater than 1.0 x 10-7 M; and in basic solution, [OH-] is greater than 1.0 x 10-7 M.
Calculate the concentration of [H+(aq)] in
(a) a solution in which [OH-] is 0.010 M
(b) a solution in which [OH-] is 2.0 x 10-9 M
Calculate the concentration of [OH- (aq) ] in a solution in which
(a) [H+(aq)]= 2.0 x 10-6 M
(b) [H+(aq)]= [OH-+(aq)]
(c) [H+(aq)]= 1.0 x 10-2 M
3.4 The pH scale
The concentration of H+(aq) in a aqueous solution is usually quite small. For convenience, we therefore
express [H+] in terms of pH, which is defined as the negative logarithm in base 10 of [H+].
1
pH  log10[H ] 
log10 [H ]
For a neutral solution at 25 ˚C, *H+] = 1.0 x 10-7 M
pH=-log(1.0 x 10-7)=-(-7.00)=7.00
This means that the pH of a neutral solution is 7.00
The relationship among [H+], [OH-] and ph is summarized in Table 1 below.
Point of emphasis
48
pH=-log10[H+] means that p=-log10 and is always the case. Therefofore, pOH==-log10 [OH-]. In any solution,
[H+] [OH-]= 1.0 x 10 -14 . This means that pOH+ pOH=14
Relationship among [H+], [OH-] and pH at 25˚C
Table 1 A table of pH values
Solution type [H+]/ M [OH-]/M pH value
Acid >1.0 x 10 -7 <1.0 x 10 -7 <7
Neutral =1.0 x 10 -7 =1.0 x 10 -7 =7
Basic <1.0 x 10 -7 >1.0 x 10 -7 >7
Table 2 The approximate pH values of some common solutions
Table 5-2. Acidity of Some Common Solutions

Substance pH [OH-] [H+]
Commercial concentrated HCl (37% by weight) ~ -1.1

1 M;; HCl solution 0.0
Gastric Juice 1.4
Lemon Juice 2.1
Orange Juice 2.8
Wine 3.5
Tomato Juice 4.0
Black Coffee 5.0
Urine 6.0
Rainwater 6.5
Milk 6.9
Pure Wtaer at 24°C 7.0
Blood 7.4
Baking soda solution 8.5
Borax solution 9.2
Limewater 10.5
Household ammonia 11.9
1M NaOH solution 14.0
Saturated NaOH solution ~15.0
The pH scale extends from 0-14 because nearly all solutions commonly encountered have pH in this range.
In principal, however, the pH values for strongly acidic solutions can be less than 0, and for strongly basic
solutions can be greater than 14.
Practice 3.2
49
a) In a sample of lemon juice, [H+] is 3.8 x 10-4 M. What is the pH?
b) A commonly available window cleaning solution has a [H+] is 5.3 x 10-9 M. What is the pH?
c) A solution formed by dissolving an anti acid tablet has a pH of 9.18. Calculate the [H+]
d) Calculate the pH of the following solutions:-
 M H3PO4
 2.0 M NaOH
3.4.1 pH of strong acids and strong bases
The six most common strong acids are HCl, HBr, HI, HNO3, HClO4 and H2SO4. Thus aqueous solution of nitric
acid, HNO3, consists entirely of H+(aq) and NO3- (aq) ions.
HNO3 ⇌ H+(aq) and NO3- (aq) (complete ionization) (eq 3.3)
In an aqueous solution of a strong acid, the acid is normally the only significant source of H+ ions. As a
result, the calculation of the pH of a solution of a strong acid is quite simple because H+ equals to the
original concentration of the acid. For example, in a 0.20 M solution of HNO 3 (aq), [H+] = [NO3-]= 0.20 M, the
concentrations of undissociated HNO3 molecules is virtually zero.
Sample 3.2
(i) What is the pH of 0.040 M solution of HClO4?
Solution
[H+] = [ClO4-]= 0.040 M. This is a strong acid that is completely ionized. Then pH=-
log(0.040)=1.40
(ii) An aqueous solution of HNO3 has a pH of 2.26. What is the concentration of the acid?
pH=-log [H+]=2.66⇒
(iii) Strong bases such as NaOH, KOH, and Ca(OH)2 completely dissociate into ions when in aqueous
solution. Thus, a solution labeled 0.30 m NaOH consists of 0.30 Na+ (aq) ions and 0.30 OH- (aq);
There are no un dissociated NaOH molecules.
What is the pH of 0.011 M Ca(OH)2?
Solution
[OH-]=2 x (0.11 M)= 0.022 M
[H+]=1.0 x 10-4/ 0.022 Why?
pH=-log(4.6 x 10-13)=12.34 or alternatively, pOH=-log 0.022= 1.66 Then 14-1.66=12.34
(iv) What is the concentration of a KOH solution whose the pH is 11.89?
3.4.2 pH of weak acids and bases
Most acidic substances are weak acids that only partially ionize in solution. We can express the extent to
which a weak acid ionizes by using the equilibrium constant for the ionization reaction. We can represent a
general acid by the formular HA, where A- is the conjugate base of the acid. The ionization equilibrium for
HA is given by
HA⇌H+(aq) + A-(aq) (eq 3.4)
The corresponding equilibrium expression is

50
[H ][A - ]
Ka  (eq 3.5)
[HA]
Where Ka is called the acid-dissociation constant
Similarly, many substances behave as weak bases in water. Such substances react with water, removing a
proton from water, thereby forming the conjugate acid of the base OH- ions.
Weak base + H2O⇌ conjugate acid + OH- (eq 3.6)
The most commonly encountered weak base is ammonia
NH3 + H2O(l) ⇌ NH+4(aq) + OH- (eq 3.7)
The equilibrium expression is

[NH4 ][OH- ]
K (eq 3.8)
[ NH 3 ][H 2O]
Because the concentration of water is essentially constant, the [H2O] term is incorporated in the
equilibrium constant giving

[NH4 ][OH- ]
K[ H 2O]  Kb  (eq 3.9)
[ NH 3 ]
The constant Kb is called the base-dissociation constant, by analogy with the acid-dissociation Ka, for weak
acids. The constant Kb always refers to the equilibrium in which a base reacts with H2O to form conjugate
acid and OH-.
The [H+] or [OH- ] for weak acids and bases respectively can only be obtained from Ka and Kb values.
Calculating pH for solution of weak acids
To calculate the pH of 0.1 M CH3COOH, the following steps are followed: Ka for acetic acid is 1.8 x 10-5
Acetic acid ionizes in solution thus
CH3COOH ⇌ CH3COO- + H+ (eq 3.10)
From equation 3.10 the dissociation constant can be calculated as shown in equation 3.11
[H  ][CH 3COO- ]
Ka  (eq 3.11)
[CH 3COOH]
We first note three important points
51
(i) The concentration of [H+] ions from the dissociation of water is very small,<<<10-7 hence can be
neglected
(ii) Since ionization constant is small, the [CH3COOH] at equilibrium will be approximately equal to
the original concentration [CH3COOH]0 i.e. 0.1 M
(iii) At equilibrium [CH3COO-] = [H+]
Therefore from equation 3.11

[H  ]2
Ka 
[CH 3COOH]0
Hence
[H  ]2  Ka [CH 3COOH]0  [H  ]  Ka [CH 3COOH]0
Therefore
[H ]  1.85 x 10-5 x 0.1  1.36 x 10 3 M
pH   log10 (1.36 x 10 3 )  2.87

Alternatively
1 1 1 1
[H  ]  K 2
a [CH3COOH]0 2 K 2
a x 0.1 2
Upon taking logs

1 1
- log10[H ]  -log10K 2
a  - log10 (0.1) 2
 pH   1 log10 (1.85 x 10 5 )  1 log10 (101 )
2 2
pH  2.37  0.5  2.87

We should note that in general,
pH  1 pKa  1 p[acid]
2 2
What is the pH of 0.01 M and 1M acetic acid, given that Ka= 1.8 x 10-5 at 25˚C.
For bases, a similar procedure is used but Kb e.g. for dissolution of ammonia in water is Kb =1.79 x 10-5
NH3 + H2O ⇌ NH4OH
NH4OH ⇌ NH+4 + OH-

[NH4 ][OH- ]
Therefore for 0.1 M of NH4OH solution Kb   1.79 x 10 5
[NH4OH]0
Hence pOH = -log10 1.79 x 10 5 x 0.1  2.87
52
Then pH = 14 - pOH  14 - 2.87  11.12
In general, for a partially dissociated base, pH = 14 - 1 2 pKb - 1 2 p[base]
What is the pH of 0.1 M CH3NH2 given that Kb=5 x 10-4 M

A solution is made by adding sodium hypochlorite, NaClO, to enough water to make 2.00 l of solution. If the
solution has a pH of 10.50, how many moles of NaClO were added to the water?
3.5 Hydrolysis of salts
Salts are products of neutralization of acids and bases. When a salt is added to water, the solution may
remain neutral or it may become acidic or basic depending on the type of salt. This is because certain ions
interact with water hence disturbing the self ionization of water equilibrium. This interaction of ions of a
salt is called hydrolysis.
There are four types of salts
1. Salts of strong acids and strong bases; e .g.

HCl+ NaOH⇌NaCl + H2O (eq 3.14)
The salt fully dissociates in water
NaCl + H2O ⇌ Na++ Cl- + H2O (eq 3.15)

+ -
No interaction occurs between Na or Cl with
water hence there is no hydrolysis and the solution is neutral
2. Salts of weak acids and strong bases; e.g.
CH3COOH + NaOH ⇌ CH3COONa + H2O (eq 3.16)
CH3COONa + H2O ⇌CH3COO + Na + H2O
- +
(eq 3.17)
The salt formed is completely dissociated. The acetate ions interact with water as follows
CH3COO- + H2O ⇌CH3COOH + OH- (eq 3.18)
The hydrolysis occurs and the solution is basic due to excess OH- ions. What then is the pH of 1 M sodium
acetate solution? First, equilibrium constant Kb for the hydrolysis in equation 3.18 is written.
[CH 3COOH][OH - ] [CH 3COOH][OH - ]

Kh   (eq 3.19)
[CH 3COO- ][H 2O] [CH 3COO- ]
Since activity of pure liquids such as water is 1, ther acetate ions, Kh = 5.4 X 10-10 .
53
[H ][A - ]
From the expression of Ka of equation 3.5 K a  and
[HA]
The ionic product of water Kw =[H+][OH-]=10-14, we find that
Kw
Kh  (eq 3.20)
Ka
Considering equation 3.20 and noting the following:-
1) Contribution of OH- from water is very small hence can be neglected. Implies that
[CH3COOH]= [OH-] Consider equation 3.18
Since CH3COO- is a weak base, i.e. hydrolysis constant is low then,

CH3COO-= 1 M
From that information, equation 3.19 can be written as,
[CH 3COOH][OH - ] [OH - ][OH - ] [OH- ]2 [OH - ]2

Kh  -
 -
 -
  5.4 x 10 10
[CH 3COO ] [CH 3COO ] [CH 3COO ] 1
Therefore
[OH- ]  5.4 x 10 10  2.3x 10 5  pOH   log10 (2.3x 10 5 )  4.64
Therefore pH=14-4.64=9.36
And clearly this salt in water gives a basic solution as predicted by equation 3.18
Alternatively
K w [OH- ] K w [salt]
Since Kh    [OH- ] 
K a [salt] Ka
pOH  1 2 pKw  1 2 pKa  1 2 p[salt]

2) Salt of a strong acid and a weak base e.g
HCl + NH4OH⇌ NH4Cl + H2O
NH4Cl + H2O ⇌ NH4+Cl-+ H2O
The ammonium ion interacts with water as follows

NH4+ + H2O ⇌ NH4OH + H+
Thus hydrolysis occurs and the resulting solution is acidic. The hydrolysis constant can be
given as:-
[NH 4OH ][H + ] K w

Kh  +
  5.6 x 1010
[ NH 4 ][H 2O] K b
Making similar assumptions as in the case of sodium acetate above, we find that for a 1.0
M NH4Cl solution,
54
Since [NH4OH]=[H+] then
[H + ]2 K w
Kh    5.6 x 1010 Therefore
1 Kb
[H  ]  5.6 x 10 10  7.5 x 10 4  pH   log10 (7.5 x 10 4 )  5.12
Hence this salt in water gives an acidic solution. We can also see here that
pH  1 2 pKw  1 2 pKa  1 2 p[salt]
3) Salts of weak acid and weak base

CH3COOH + NH4OH⇌ CH3COO- + NH4+ + H2O
NH4+ + CH3COO- + H2O ⇌ CH3COOH + NH4OH
[NH 4OH ][CH 3COOH ] K w

Kh  +

[ NH 4 ][CH 3COO- ] KbK a
We can see that from the expression for Ka, Kb and Kw We can get
Kw
Kh  (eq 3.22)
KbK a
Since neither the [H+] nor the [OH] appears in our hydrolysis equilibrium equation 3.22, then pH is
independent on the magnitudes of Ka and Kb as illustrated below in calculating pH of CH3COO NH4 salt
solution.
Since the ions are not strongly hydrolysed, then
NH4+ = CH3COO- =C (Concentration of the salt)
And then [NH4OH] and [CH3COOH] are approximately equal hence
Kw [NH 4OH ][CH 3COOH ] [CH3COOH ]2

Kh   
KbK a +
[ NH 4 ][CH 3COO- ] C2
From the equation above, making [CH3COOH] the subject

Kw [CH3COOH ]2 Kw
  [CH3COOH ]  C (eq 3.47)
KbK a C2 KbK a
55
Since Ka must remain constant in solution, i.e.
See equation 3.11
[H  ][CH 3COO- ] K [CH 3COOH]

Ka  Make [H+] the subject [H  ]  a
[CH 3COOH] [CH 3COO- ]
Then plug the value of [CH3COOH] as it is in equation 3.47
Ka Kw Kw
[H  ]  C  [H  ]  K a
C KbK a KbK a
Therefore
pH  1 2 pKw  1 2 pKa  1 2 pKb

Clearly whether the salt is acidic or basic depends on which of the two Ka or Kb is higher. In our case, pH =
7+2.37 i.e. the solution is neutral.
Practice 3.4
The dissociation constants of HCN and NH4OH are 7.2 x 10-10 and 1.85 x 10-5. What is the pH of a 0.05 M
NH4CN solution?
3.6 Buffer solutions
A buffer is a solution of known pH that resists change in pH when either H+ or OH- ions are added into it.
Buffer solutions are made by mixing a weak acid with one of its salts with a strong base or a weak base with
one of its salts with a strong acid. Example is acetic acid and sodium acetate (salt with NaOH) or ammonium
hydroxide and ammonium chloride (salt HCl). Consider a solution prepared by mixing 0.70 M acetic acid
and 0.60 M sodium acetate where Ka=1.85 x 10-5 M.
How can we obtain the pH of the buffer solution and how does it resist pH changes?
The acetic acid is partially dissociated while the salt, sodium acetate is fully ionised. Therefore the following
equilibria will exist in solution
CH3COOH ⇌ CH3COO- + H+ (eq 3.53)
CH3COONa ⇌ CH3COO- + Na+ (eq 3.54)
[CH 3COO- ][H  ] [CH 3COOH]

Ka   [H  ]  Ka (eq 3.55)
[CH 3COOH] [CH 3COO- ]
Due to the high concentration of acetate ions from the salt, equation 3.53, is suppressed to the left
(common ion effect) and hence we can neglect the dissociation of the acid and therefore in solution.
[CH3COOH]=0.70 M- concentration of the acid

56
If the above is taken to be true, then all the acetate ions present in solution are from the fully dissociated
salt, therefore
[CH3COO-]=0.60 M- concentration of the salt

Then equation 3.55 becomes
[acid] 0.7
[H  ]  K a  1.85 x 105 x  2.15 x 105 M
[salt] 0.6
(eq 3.56)
Then the pH = -log10 (2.15 x 10-5)=4.66
[acid ]
In general, for this type of buffer, [H  ]  K a (eq 3.57)
[salt]
Upon taking logs

pH  -log10Ka  - log10[acid] -log10[salt] or pH  pKa  p[acid] p[salt]
If we consider equation 3.57 and take logs, we get
[salt]
pH  pKa  log10 (eq 3.58)
[acid]
So that now it is the ration salt: acid that controls the pH of our buffer solution since Ka is constant. It is
important to note that since this ratio would not change on dilution, then the pH does not change upon
dilution.
Our second question is how the buffer resists change in pH. Considering equation 3.53 and 3.54 occurring
in the buffer solution if H+ ions are added, they react with CH3COO- to form CH3COOH thus the
concentration of CH3COOH increases whereas that of CH3COO- decreases. The ration of salt: acid remains
approximately constant hence no change in pH. If hydroxide ions are added, they react with undissociated
acid to form the acetate ions. Thus concentration of CH3COOH decreases while that of CH3COO- increases.
Again the ration of salt: acid remains effectively constant and therefore pH remains constant.
Sample exercise 3.4
What is the change in H+ ion concentration hence pH when 1 ml of 1M HCl is added to a litre of:-
(a) Pure water
(b) Buffer solution (acetate buffer)
Solution
(a) In pure water [H+] = 10-7 M and pH =7
57
1
The number of moles of H+ ions contained in 1 ml of 1 M HCl is x 1  0.001 M (103 M) .
1000
Therefore [H+] changes from 10-7 (in pure water) to 10-3 M ( a 104 fold change) and pH changes from
7 to 3.
(b) Again the same amount of 10-3 moles of H+ ions is added to the buffer solution. These react with
CH3COO- to form 0.001 moles of acetic acid. Hence the new [CH3COOH]=0.7+0.001=0.701 M and
the new [CH3COO-] =0.60-0.001=0.599 M.
[acid] 0.701
From equation 3.57 [H ]  K a  1.85x10 5 x  2 x 10 5 M
salt] 0.599
or equation 3.58
[acid] 0.701
pH  pKa  log10  4.73  log10  4.66
[salt] 0.599
Clearly there is no change in [H+] or the pH of our buffer solution unlike in pure water.
Calculate the change in pH when 1 ml of NaOH is added to 500 ml of:-

(a) Pure water
(b) Buffer solution (acetate buffer)
In the case of a weak acid and one of its salt with a strong acid e.g. NH4OH and NH4Cl, similar consideration
show that
Kb [bas e]
OH-  (eq 3.59)
[s alt]
thus
pOH  pKb  p[base] p[salt]
pOH  pKw - (pKb  p[base] p[salt])
The extent to which a buffer solution resists pH is referred to as its buffer capacity. Clearly when this ratio
salt: acid in equation 3.57 or 3.59 is 1, then we expect maximum buffer capacity.
Thus the concentration of the acid and the salt should be kept as close as possible in making the buffer
solution.
3.7 Acid- base titrations
During neutralization reaction of an acid by a base, the pH obviously changes as the H+ ions are removed
from solution. Therefore pH changes can be ultilised in determining the end point of such a reaction.
However, we must take into consideration the hydrolysis of ions at endpoint and therefore the pH at this
58
endpoint may be <7, =7 or >7 depending on the strength of the acid and base used. Therefore, four cases
are encountered and the changes in pH as the titration continous are represented as shown in Figure 8a-d.
Figure 8
3.7.1 Strong acid- Strong base titrations
Consider titration of 25 ml of 0.1 M HCl with 0.1 M NaOH. At the commencement of the titration, [H+]=0.1
M and therefore pH=1. After addition of 5 ml of NaOH and equivalent 20 ml of 0.1 M HCl contained in 30 ml
of solution is left.
59
20
20 ml of 0.1 ml HCl contain x 0.1 molesof H ions. This amount in now present in 30 ml of solution,
1000
20 1000
therefore the concentration per liter is x 0.1 x  0.667 molesof H ions
1000 30
Thus pH=1.186
Similar calculations will show that the pH will change as follows
Vol. of NaOH added 0 5 10 20 24 25 25.1 26
pH 1 1.118 1.37 1.95 2.69 7 10.68 11.29
We should note that since the acid is completely dissociated, initially any added base does not affect a big
change in [H+] thus pH changes gradually before the end point. However at the end point, there is a big
change as the completely dissociated base will cause the pH to rise rapidly. Also the pH at the endpoint is 7
as Na+ and Cl- ions produced are not hydrolysed. Figure 8a-d.
3.7.2 Weak acid- Strong base titrations
Consider the titration of 50 ml 0.1 M acetic acid with 0.1 M NaOH. Initially before any base is added, the pH
will be 2.87, see 3.5.3.
K a [CH 3COOH]
As the titration progress, the [H+] will be given by [H  ]  and therefore is dependent on
[CH 3COO- ]
the concentration. Calculation of pH changes here as the titration progresses, is rather difficult since the
acid is not fully ionised and the degree of ionization will change throughout the titration. However at the
endpoint the pH can be obtained as shown in section 3.5 which is equal to 10.57. Curve 8C shows how the
pH changes during titration. Note that initially there is a marked increase in pH which is due to the
hydrolysis of acetate ions. The endpoint >7 as expected and beyond the endpoint the change is similar to
that of a strong acid-strong base as pH now changes only due to the added strong base.
The other two cases represented in 8B and D can be explained in a similar manner.
3.7.3 Neutralization indicators

Indicators are weak organic acids or bases which change colour according to H+ ion concentration of the
solution or liquid to which they are added. Like any other weak acid or base, the indicator is partially
dissociated i.e. an equilibrium exists between the unionized and ionised forms. For indicators, the
unionized form has a different colour from the ionised forms i.e. representing an acidic indicator as HIn
then
HIn ⇌ H++ In-
Colour 1 Colour 2
60
Colour 1 and 2 are different. In an acid solution, this equilibria shifts due to common ion effect giving colour
1 due to excess HIn. However in basic solution, OH- ions react with H+ ions to force the equilibrium to the
right hence colour 2. Due to excess In- is observed. If the colour of the indicator depends on which of the
two HIn or In- is excess then, when a base is added gradually, we expect that the colour change will be
gradual i.e. starting the colour of HIn and as more H+ ions are removed and more In- ions formed.
3.8 Solubility equilibria
Solubility is the amount of a solute that dissolves in a specified volume of solvent to give a saturated
solution. According to this definition then, few substances are insoluble since even for salts like silver
chloride which we refer as insoluble, in a saturated solution there will be small amounts of Ag+(aq) and Cl-(aq).
It is only because these amounts are so small that we refer to the salt as insoluble otherwise this is not
strictly so. Such salts whose solubility is very low are said to be sparingly soluble.
AgCl(s) ⇌Ag+(aq) + Cl-(aq) (eq 3.8.1)
At equilibrium, only 1.67 x 10-5 moles of AgCl dissolve in 1 liter of water. We can write the equilibrium
expression for the equilibria as:-
γ Ag γCl_
K (eq 3.8.2)
γ AgCl
Where γ is the activity, since it is the activity of solids and has a value of one, we can write
K sp  K γAgCl  [Ag ][Cl ] (eq 3.8.3)
In this case γ will be the same as the concentration of dilute solutions, i.e. Ksp is the product of the
concentrations of ions in the saturated solutions.
Ksp refers to as the solubility product.
Other examples could be:-
CaF2(S) ⇌Ca2 + (aq) +2F-(aq) K sp  K γCaF2  [Ca2 ][F ]2 (eq 3.8.4)
La(OH)3(S)⇌La3 + (aq) +3OH-(aq) K sp  K γLa(OH) 3  [La3 ][OH ]3 (eq 3.8.5)
We should note that under no circumstance can the solubility product be exceeded in a saturated solution
and that for concentrations that yield a product of lower value than Ksp the salt is soluble i.e. the solution is
no saturated. Also since solubility is dependent on temperature, then Ksp changes with temperature.
Solubility product of solubilities
61
Given the solubility of a salt, we can be able to obtain the solubility product as the following examples
show.
Sample exercise
The solubility product of AgCl is 1.67 x 10-5 moles per liter at 25˚C. Calculate the solubility product of AgCl.
1 mole of AgCl(s) would yield on complete dissociation 1 mole of each Ag+(aq) and Cl-(aq) ions. Therefore in a
saturated solution,
[Ag ]  [Cl ]  1.67 x 10 -5 molel1  K sp  (1.67 x 10 -5 )2  2.8 x 10 10 molel1
Practice exercise
The solubility of Ca(IO3)2 is 2.18 g l-1. Calculate the solubility product of Ca(IO3)2
Solubility from Ksp values
If the solubility product is known, then the solubility of a salt can be calculated as follows.
Sample exercise 3.5
Given that Ksp for AgCl is 2.8 x 10-10 mol l-1 at 25 ˚C. What is the solubility of AgCl in 1 liter of water?
K sp  (1.67 x 10 -5 )2  2.8 x 10 10 molel1

[Ag ]  [Cl ]  hence [Ag ] x [Cl ]  [Ag ]2
[Ag ]2  2.8 x 10 10 molel1  [Ag ]  2.8 x 10 10 molel1  1.67x 10 5 molel1
This is the concentration of Ag+ ions present in solution at equilibrium. From stoichiometry of the reaction,
this is the amount of AgCl(s) that has dissolved. Therefore the solubility of AgCl(s) is 1.67x 10 5 molel1
Sample exercise 3.6
The Ksp of CaF2 is 1.7 x 10-10 mol l-1 at 25 ˚C. What is the solubility of CaF2 in 1 liter of water?
Solution
The equilibrium can be expressed as
CaF2(S)⇌Ca2 + (aq) +2F-(aq) K sp  K γCaF2  [Ca2 ][F ]2
Here we should note that I mole of would yield I mole of Ca2 + (aq) and 2 moles of +2F-(aq), then the solubility
product will be equal to the concentration of Ca2 + (aq) +ions or half the concentration of 2F-(aq) present in
solution. [F-(aq) ] = 2[Ca2 + (aq)]
62
Since K sp  K γCaF2  [Ca2 ][F ]2 Since for every Ca ion there are two F- ions, Then
K sp  [Ca2 ][2Ca2 ]2  [Ca2 ]3  1.70 x 10 10  [Ca2 ]  3.5 x 10 4
This is then the solubility of CaF2

Given that Ksp for BaSO4 is 1.08 x 10-10 mol l-1 at 25 ˚C. Calculate its solubility in 1 liter of water.
Since Ksp cannot be exceeded in a saturated solution, any attempt to excced it by increasing the
concentration of ions results in precipitation so as to maintain the Ksp. If any of these ions present in the
equilibrium is added from another source, this results in a attempt to increase Ksp and therefore the salt
occurs. This is in accordance to Le Châtelier’s principle. This is called the common ion effect. We can
demonstrate the common ion effect with the following examples.
Sample exercise 3.7
Given that Ksp for AgCl is 2.8 x 10-10 M2, determine the solubility of AgCl(s) in 0.1 M AgNO3. We can only be
able to obtain the solubility of AgCl from concentrations of chloride ions since there is another source of
silver ions. AgCl(S)⇌Ag + (aq) +Cl-(aq) K sp  K γAgCl  [Ag ][Cl ] =2.8 x 10-10 M2
Note that no matter what the source of Ag + ions, Ksp remains constant. The total [Ag +] is the sum of the
contribution from AgNO3 (complete dissociated), 0.1 M and AgCl whose contribution must be less than 2.8
x 10-10 M ( amount expected in pure water) hence negligible in comparison with the amount contributed by
AgNO3 and therefore
[Ag +]=0.1 M
[Ag +][Cl-]= (0.1) [Cl-]= 2.8 x 10-10 M2
2.8 x 10-10
[Cl ]   8 x 10-9 mol l -1
0.1
This is now the solubility, which is clearly much lower than the solubility of water, due to common ion
effect
For a salt that is not univalent we should be extra careful in deciding the relationship between
concentrations of ions in the saturated solution to solubility. The following examples illustrate this.
Sample exercise 3.8
63
Ksp for CaF2 is 1.7 x 10-10 M2 at 25 ˚C. What is the solubility of CaF2 in 0.1 M Ca(NO3)2. We obtain the
solubility from the concentration of F- ion in the saturated solution again due to the fact that there is
another source of Ca2+ ions other than CaF2. Solubility will be equal to half [F-].
K sp  K γCaF2  [Ca2 ][F ]2 Then
1.70 x 10 10
K sp  (0.1)[F- ]2  1.70 x 10 10  [F- ]2   1.70 x 10 9 [F- ]  1.70 x 10 9  4.10 x 10 5 mol l1
0.1
[F- ] 4.10 x 10 5 mol l1

Solubility =   2.05 x 10 9 mol l1
2 2

What will be the solubility of silver chromate in o.2 M sodium chromate. Ksp for silver chromate is
8.79 x 10-12 mol3 l-3
Application for Ksp values
We can utilize Ksp values to determine whether precipitation occurs in a solution and hence even be able to
separate ions by precipitation since is never exceeded in solution as shown in examples below
Sample exercise 3.9
Should precipitation occur when 50 ml of 5.00 x 10-4 M Ca(NO3)2 is mixed with 50 ml of 2.00 x 10-4 M NaF.
Ksp of CaF2 =1.7 x 10-10 M3
Here we need to assume that no precipitation occurs and determine the expected Ksp. Since the volume has
doubled, the concentrations are halved. Note the two different souces of Ca2+ and F-.
Since [Ca2 ]  2.5 x 10 -5 M and[F ]  1.0 x 10 -5 M Then

Ksp  [Ca2 ][F- ]2  (2.5 x 10-4 M)(1.0 x 10-4 M)2  2.5 x 10-12 M3
We can see that expected Ksp is lower than 1.7 x 10-10 mol2 l-1 and hence precipitation will not occur. In
qualitative analysis, say of a suspected Cu2+/Zn2+ mixture, we would need to separate the two ions in order
to proceed. We can do this by differential precipitation. Thus, suppose we have a solution containing 0.02
M of Zn2+, how can we separate the two? Ksp for ZnS = 1.1 x 10-10 mol2 l-1 and l-1 and? Ksp for CuS = 8.0 x 10-
37
mol2 l-1 and l-1. CuS is much more insoluble as compared to ZnS.
Given that
H2S ⇌ 2H+ + S2- Ksp=1.0 x 10-22 (eq 3.8.6)
Then due to the common ion effect, we can control the concentration of S2 by adjusting that of H+ ions.
Thus if we bubble H2S gas into a solution containing 1 M H+ ions, since [H+]2 [ S2-] =1.0 x 10-22 and [H+]=1M
64
then [ S2-]=1.0 x 10-22 M. If this saturated solution is used in the mixture of Zn2+ and Cu2+ ions what
happens?
For Zn2+ ions Ksp=[Zn2+][S2-]=(0.02)( 1.0 x 10-24)= 2.0 x 10-24
For Cu2+ ions Ksp=[Cu2+][S2-]=(0.02)( 1.0 x 10-24)= 2.0 x 10-24
We can see that Cus will precipitate as its Ksp is exceeded but ZnS will remain in solution hence the two are
separated. Such a procedure is ultilised in qualitative analysis where ions are grouped together in inorganic
analysis according to their solubilities.
Summary
We have seen that acidic solutions are those that contain H+(aq) than OH-(aq) ions. Basic solutions contain
more OH- (aq) than H+ (aq) ions. The H+ (aq) ion is strongly bound to water, for this reason the hydroxonium
ion, H3O+(aq), is often used to represent the predominant form of H+ in water.
Water spontaneously ionizes to a slight degree ( auto ionization), forming H+(aq) than OH-(aq) ions. The
extent of ionization is expected by the ion-product constant of water:
Kw=[H+][OH-]=1.0 x 10-24)= 1.0 x 10-14(25˚C)
The relationship describes not only pure water, but aqueous solution as well. Thus, as [H+] increases,
=[H+][OH-]=decreases.
Strong acids are strong electrolytes, ionizing completely in aqueous solutions. Basic solutions are produced
by ionic hydroxides such as NaOH and by substances that react with water to produce [OH-] ions. Weak
acids are weak electrolytes; only part of the molecule exists in solution in ionised form. The extent of
ionization is expressed by acid-dissociation constant (Ka) for the reaction
HA(aq) ⇌ H+ (aq) + A-(aq)
Weak bases include amines, NH3, and the ions of weak acids. The extent to which a weak base reacts with
water to generate OH- and conjugate acid of the base is measured by the base-dissociation constant, Kb.
This is the equilibrium constant for the reaction
B(aq) + H2O ⇌ HB+ (aq) + OH-(aq) Where B is the base
The reaction of ions with water with a resultant change in pH is called hydrolysis. The cations of strong
bases (alkali and alkali earth metal ions) and the anions of strong acids do not undergo hydrolysis.
The equilibrium between a solid salt and its ions in solution provides an example of heterogeneous
equilibrium. The solubility product, Ksp is an equilibrium constant that expresses quantitatively the extent to
which the salt dissolves. Addition to the solution of an ion common to a solubility equilibrium causes the
solubility of the salt to decrease. This phenomenon is called common ion effect.
Exercise 3
1. The solubility of PhBr2 is 8.4 g l-1 of water. Determine Ksp for PhBr2
2. Ksp for Cu2S is 2.0 x 10-47 m3. Calculate the solubility of Cu2S.
3. What is the solubility of BaF2 in 0.20 M NaF. Ksp BaF2= 1.7 x 10-6 m3
4. Does CaCO3 precipitate if 50 ml of 3.0 x 10-5 M Ca(NO3)2 is mixed with 50 ml 4.0 x 10-4 M
Na2CO3? Ksp of CaCO3=8.7 x 10-9 m2
5. What is the percentage decrease in H+ ion concentration corresponding to an increase of 0.1 in pH?
6. What is hydrogen ion concentration in a solution with pH of (a) 4 and (b) 2.3 M
65
7. 1 ml of a 0.21 M NaOH solution is titrated with 0.0911 M HCl. What is the pH (a) before addotion of
acid (b) after addition of 12 ml of the acid (c) at equivalent point (d) after addition of 30 ml of the
acid (e) determine the volume at the equivalent point.
8. A buffer solution is prepared by adding 0.02 M acetic acid to 500.ml of 0.02 M sodium acetate and
making to the mark (1 liter) with water. Calculate the volume of HCl required to prepare a buffer
solution of pH 5. Ka=1.75 x x 10-5 for acetic acid.
9. Calculate the pH of a mixture of 50 ml acetic acid with 20 ml of 1 M NaOH Ka=1.75 x x 10-5 for
acetic acid.
10. In question 9 above, what will be the ratio salt: acid if the pH of the solution is changed to 4.3.
66
Phase equilibria
4.0 Phase equilibrium
4.1 Introduction
A phase is defined as a state of aggregation of molecules of a homogeneous system. This means that it is
uniform in both chemical composition and physical state. Depending on temperature and pressure,
different phases of a pure substance can exist in equilibrium. Also, phases of different chemical
composition but same physical state can exist in equilibrium e.g liquid/liquid. It is these types of equilibria
that we will deal with in this section. For a pure substance, the various equilibria that can exist at a given
temperature and pressure can be represented in what is called a phase diagram. Figure 9 represents a
phase diagram for water.
Figure 9 A phase diagram for water
The solid lines represent the conditions under which any two phases exist in equilibrium.
Thus
AT-The sublimation curve represents Solid-gas equilibria

TC-The melting curve represents Solid-liquid equilibria
TTc -The boiling curve represents Liquid-vapour equilibria
At T, the triple point, all the three phases are in equilibrium. Point Tc, the critical point represents the point
beyond which the vapour cannot be converted into liquid by application of pressure alone, the
temperature must be lowered to below Tc for condensation to occur.
The regions where the different phase exists are indicated on the diagram. With the aid of a phase diagram
therefore we can be able to describe precisely the state in which a given substance will exist at a given
temperature and pressure.
4.2 Learning goals

67
Phase equilibria
1. Describe, with the aid of a phase diagram, the state in which a given substance will exist at any
given temperature and pressure.
2. Explain the causes of deviation from ideal behaviour for solutions.
3. Describe the effect of solute concentration on the vapour pressure of two component solution.
4. Use Raoult’s law to solve for one variable (Pi, XiPoi) given the other two variables or information
from which they can be determined.
4.2 Liquid- vapour equilibria

At any given temperature below the boiling point of a liquid (or liquid mixture) there exist a vapour, Which
exerts a (vapour) pressure over the liquid in equilibrium. This means that a liquid exists with its vapour
which exerts pressure on its surface. Indeed the liquid boils when this vapour pressure, which increases
with temperature, becomes equal to the external (prevailing) pressure. This liquid-vapour equilibria is not
very important for a pure substance but becomes interesting in liquid-liquid mixture. Some pairs of liquids
(We shall limit our discussion to pairs) completely mix, (are miscible) while others do not mix, (immiscible)
and others are partially miscible. Let us consider miscible liquids first. These may form an ideal solution in
which the cohesive forces are approximately the same as those existing in the separate components of the
solution i.e. forces existing in a solution of A and B are approximately the same as those existing in pure A
and pure B.
Most variable composition equilibria are represented either at constant T with P and composition as
variables or constant P with T and composition as the variables.
4.2.1 Solutions
A solution is any homogeneous phase that contains more than one component. The component that
constitutes the large proportion –Solvent and the lesser proportion-Solute
Is there an ideal solution? We look for what we may call an ideal solution with a hope that the concept may
lead us to a better understanding of solutions in general. Imagine a solution of molecules A and B. If
molecular sizes are the same and intermolecular attraction of A for B and B for A are the same as the
attraction of A for B. The solution is considered ideal when there is a complete uniformity of intermolecular
forces.
Colligative properties
Physical properties can be divided into two categories. Extensive and Intensive properties.
Extensive properties comprise the factors such as mass and volume i.e. depend on the size of the
sample as it occupies volume and space. Intensive properties are the properties such as density
and concentration of the of the substance. The latter do not depend on the size of the sample
being studied. However there is a third category which is a subset of the intensive properties of a
system known as the colligative properties. The colligative property depends only on the ratio of
the number of particles of solute and solvent in the solution and not the identity of the solute.
68
Phase equilibria
4.3. Raoult’s law
When a solute is added to the solvent, some of the solute molecules occupy the space near the
surface of the liquid, as shown in the figure below. When a solute is dissolved in a solvent, the
number of solvent molecules near the surface decreases, and the vapor pressure of the solvent
decreases.
The number of solute and solvent molecules near the surface
This has no effect on the rate at which solvent molecules in the gas phase condense to form a
liquid. But it decreases the rate at which the solvent molecules in the liquid can escape into the
gas phase. As a result, the vapor pressure of the solvent escaping from a solution should be
smaller than the vapor pressure of the pure solvent.
P < Po
vapor pressure vapor pressure

of the solvent of the pure solvent
above a solution
Between 1887 and 1888, Francois-Marie Raoult showed that the vapor pressure of a solution is
equal to the mole fraction of the solvent times the vapor pressure of the pure liquid.
P = solvent Po
vapor pressure vapor pressure of the

of the solvent pure solvent
above a solution
69
Phase equilibria
This equation, which is known as Raoult's law, is easy to understand. When the solvent is pure,
and the mole fraction of the solvent is equal to 1, P is equal to Po. As the mole fraction of the
solvent becomes smaller, the vapor pressure of the solvent escaping from the solution also
becomes smaller.
Let's assume, for the moment, that the solvent is the only component of the solution that is
volatile enough to have a measurable vapour pressure. If this is true, the vapour pressure of the
solution will be equal to the vapour pressure of the solvent escaping from the solution. Raoult's
law suggests that the difference between the vapour pressure of the pure solvent and the solution
increases as the mole fraction of the solvent decreases.
Thus the Partial vapour pressure measures the escaping tendency of a molecule from solution, which in
turn is a measure of the cohesive forces present in solution. This law, discovered experimentally, is
applicable to liquids miscible in all proportions.
Raoult’s law
states that at any given temperature, the partial vapour pressure of component “i” in a
liquid mixture is Pi=PiO.Xi where Xi is the mole fraction of that component in the liquid phase,
and POi is its saturated vapour pressure of that component. The total pressure of a mixture
of components is the sum of the partial pressures of the individual components. PTOTAL=P1+
P2 + P3+………. Pn
To illustrate the application of Raoult’s law, we consider the following example.
Given that a mixture of benzene and toluene boils at 97˚C and 1 atm pressure and vapour pressure of pure
benzene and toluene are 1.67 atm and 0.84 atm respectively. Calculate
1. The mole fraction of benzene in the mixture
2. The composition of the initial condensate formed on distilling the mixture
Solution
First we should note that if the liquid is boiling at 1 atm pressure, then this is also the total vapour pressure
above the mixture. Therefore if XB is the mole fraction of benzene in the mixture, then 1- XB is the mole
fraction of toluene.
Hence
(XB x 1.67)+( 1- XB)0.84=1 atm This gives XB =0.210
1 atm is the atmospheric pressure.
The initial condensate will have the composition of vapour and therefore:-
70
Phase equilibria
XBPB0 0.21 x 1.67

Since XB (V)    0.3507
PTOTAL 1
Sample exercise 4.1
At 88˚C the saturated vapour pressure of benzene and toluene are 953 and 378 mm Hg respectively.
Calculate the vapour pressure of a benzene-toluene mixture containing 2 moles of benzene per mole of
toluene, assuming Raoult’s law is obeyed.
Solution
2 1
The mole fraction of each:- benzene  0.67 toluene  0.33
3 3
PTOTAL=P0BENZENE+ P0TOLUENE= (953 x 0.67) + (378 x 0.33)=763 mm Hg
Very few of the physical properties of a solution are colligative properties. As an example of this limited set of physical
properties, let's consider what happens to the vapour pressure of the solvent when we add a solute to form a
o
solution. We'll define P as the vapour pressure of the pure liquid and P as the vapour pressure of the solvent after a
solute has been added.
o
P = vapour pressure of the pure liquid, or solvent
P = vapour pressure of the solvent in a solution
When a solute is added to the solvent, some of the solute molecules occupy the space near the surface of the liquid,
as shown in the figure below. When this happens, the number of solvent molecules near the surface decreases, and
the vapor pressure of the solvent decreases.
When the temperature of a liquid is below its boiling point, we can assume that the only molecules that can escape
from the liquid to form a gas are those that lie near the surface of the liquid.
71
Phase equilibria
This is because addition of solute to form a solution stabilizes the solvent in the liquid phase, and hence lowers the
solvent’s chemical potential. This implies that the solvent molecules have a less tendency to move to the gas or solid
phases. As a result, liquid solutions slightly above the solvent boiling point at a given pressure become stable, which
means that the boiling point increases. Similarly, liquid solutions slightly below the solvent freezing point become
stable meaning that the freezing point decreases. Both the boiling point and the freezing point depression are
proportional to the lowering of vapor pressure in a dilute solution.
These properties are colligative in systems where the solute is essentially confined to the liquid phase. Boiling point
elevation (like vapor pressure lowering) is colligative for non-volatile solutes where the solute presence in the gas
phase is negligible. Freezing point depression is colligative for most solutes since very few solutes dissolve appreciably
in solid solvent.
These properties are colligative in systems where the solute is essentially confined to the liquid phase. Boiling point
elevation (like vapor pressure lowering) is colligative for non-volatile solutes where the solute presence in the gas
phase is negligible. Freezing point depression is colligative for most solutes since very few solutes dissolve appreciably
in solid solvents.
Boiling point elevation (ebullioscopy)
The boiling point of a liquid is the temperature (Tb) at which its vapor pressure is equal to the external pressure. The
normal boiling point is the boiling point at a pressure equal to 1atmosphere.
The boiling point of a pure solvent is increased by the addition of a non-volatile solute, and the elevation can be
measured by ebullioscopy. It is found that
Tb  Tb ( solution )  Tb ( solvent)  i.Kb .m
Here i is the van’t Hoff factor as above, Kb is the ebullioscopic constant of the solvent (equal to 0.512 °C kg/mol for
water), and m is the molarity of the solution.
The boiling point is the temperature at which there is equilibrium between liquid and gas phases. At the boiling point,
the number of gas molecules condensing to liquid equals the number of liquid molecules evaporating to gas. Adding a
solute dilutes the concentration of the liquid molecules and reduces the rate of evaporation. To compensate for this
and re-attain equilibrium, the boiling point occurs at a higher temperature.
If the solution is assumed to be an ideal solution, Kb can be evaluated from the thermodynamic condition for liquid-
vapor equilibrium. At the boiling point the chemical potential μA of the solvent in the solution phase equals the
chemical potential in the pure vapor phase above the solution.
Tb  Tb ( solution )  Tb ( solvent)  i.Kb .m
RMTb2
where the asterisks indicate pure phases. This leads to the result K b  , where R is the gas constant, M is the
H vap
solvent molar mass and ΔHvap is the solvent molar enthalpy of vapourization.
Freezing point depression (cryoscopy)
The freezing point ( ) of a pure solvent is lowered by the addition of a solute which is insoluble in the solid solvent,
and the measurement of this difference is called cryoscopy. It is found that
72
Phase equilibria
T f  T f ( solution )  T f ( solvent)  i.K f .m
Here Kf is the cryoscopic constant, equal to 1.86 °C kg/mol for the freezing point of water. Again "i" is the van 't Hoff
factor and m the molality.
In the liquid solution, the solvent is diluted by the addition of a solute, so that fewer molecules are available to freeze.
Re-establishment of equilibrium is achieved at a lower temperature at which the rate of freezing becomes equal to
the rate of liquefying. At the lower freezing point, the vapor pressure of the liquid is equal to the vapor pressure of the
corresponding solid, and the chemical potentials of the two phases are equal as well. The equality of chemical
RMT f2
potentials permits the evaluation of the cryoscopic constant as K b  , where ΔHfus is the solvent molar
H fus
enthalpy of fusion.
4.3.1 Vapour pressure of (two component) binary solution
If each component of a liquid mixture obeys Raoult’s law, then PA=PAO.XA and PB=PBO.(1-XA). Therefore, at
constant T, the total vapour pressure is PT=PA+PB
Thus P O B + XA(P OA - P O B).
The changes in the total and partial pressures with composition at constant temperature are represented
as shown in Figure 9
Figure 10 The changes in total pressure and partial pressure with composition at constant temperature
73
Phase equilibria
A homogeneous liquid mixture boils when the sum total of the partial vapour pressure of its components
equals to the external pressure. In most cases, the composition of the vapour differs from that of the
boiling liquid.
If the solution is ideal i.e. obeys Raoult’s law, the composition of the liquid boiling at a particular
temperature is obtained from the general equation:-
P= P O 2 + X1(P O 1 - P O 2).
The corresponding vapour composition in terms of mole fraction of component 1 in the vapour phase, is
obtained as follows:-
0
P1 P X
Compositio n of vapour   1 1
P1  P2 P
The above equations relate the liquid and vapour composition at the temperature at which the total vapour
pressure is P. The results of such calculations for liquids of various compositions at constant P can be
plotted on a “boiling-point-composition” diagram
Figure 11 Boiling-point-composition diagram
It will be noticed that for systems of this type, the vapour is always richer than liquid in the more volatile
component.
Binary solutions giving boiling-point diagrams similar to the one above can be separated into their
components by successive distillation.
Let us suppose that the original solution has a composition represented by point ‘a’. The solution will boil at
a temperature corresponding to ‘b’, and give a vapour of composition ‘c’ which condenses to give a liquid
of the same composition ‘d’. Therefore a series of volatization and condensation along b-c-d-e-f etc, finally
produces the pure vapour of the more volatile constituent.
74
Phase equilibria
The volatization-condensation steps described above can be performed in one operation by using fraction
distillation column.
In it’s simplest form, the column consists of a tube loosely packed with suitable solid material (e.g. galss
beads) and vertically attached to the top of the distillation flask. When the mixture in the flask is boiled, the
vapour condenses at various levels in the fractionating column. The resultant liquid flows back down the
column and is re-volatized by the upcoming vapour, so that the a-b-c-d etc take place automatically. The
technique of fraction distillation is of immense importance both in the lab and in various industrial
processes like the refining of petroleum
4.3.4 Deviations from Raoult’s law
Deviation arise when the two components (1 and 2 or A and B) of a binary solution do not exhibit similar
molecular interactions. As a result of these deviations, the vapour pressure composition diagram is no
longer linear, and this in turn affects the shape of the boiling point-composition diagram. We distinguish
the two types of deviation.
4.3.5 Negative deviations from Raoult’s law
This occurs if the vapor pressure of a mixture is lower than expected from Raoult's law, there is said to be a
negative deviation. This is evidence that the adhesive forces between different components are stronger
than the average cohesive forces between like components. In consequence each component is retained in
the liquid phase by attractive forces which are stronger than in the pure liquid so that its partial vapor
pressure is lower.
This implies that the attraction between the two components (1 and 2) is greater than the attraction 1-1 or
2-2. This may be visualized as the holding back of molecules that would otherwise go into vapour state. .
The vapour pressure of the system is lower than expected implying that there is reduction in vapour
pressure of the system. If the deviation is sufficiently large, the vapour pressure diagram exhibits a
minimum, and the boiling point exhibits a maximum. (The forces of attraction between A-B are stronger
than A-A) See Figure 11.
75
Phase equilibria
Figure 12 Vapour pressure composition diagram (negative)
Consequently, it is no longer possible to completely separate the components of the system by fractional
distillation. Consider for example a mixture of initial composition ‘a’. Successive volatization and
condensation will proceed along a-b-c-d etc so that component a B will be preferentially volatized and the
residue in the flask will tend towards composition A. After further colatilizations and condensations, no
further change in composition will be produced,. See Figure 12.
Figure 13 Boiling point composition diagram
Similarly, if the original mixture of composition ‘a’, the process will occur along a-b-c-d-e and component B
will be lost while the residue will tend towards A. The liquid of composition Z has the highest boiling point
and is referred to as an azeotropic or constant boiling mixture. Such mixtures can easily be distinguished
from compounds because their compositions vary with pressure. Examples include chloroform/ acetone
mixture which is contributed by hydrogen bonding.
4.3 Positive deviation

This type of deviation occurs when the attractive forces between components 1-1 and 2-2 are similar in
magnitudes, but the attraction between components 1-2 is weaker. This makes each component to easily
vaporise in the presence of the other. The vapour pressure of the system is greater than expected. The
results of a positive deviation are shown in Figure 13
Figure 14 Vapour pressure composition diagram (positive)
76
Phase equilibria
The vapour pressure diagram shows the vapour pressures of the various component compositions which is
higher than the ideal vapour pressure.
Upon successive volatization and condensation the distillate composition tend to the lowest boiling point Z2
which is the minimum-boiling azeotrope. The residue is richer in either component C or D. See Figure 14
Figure 15 Boiling point composition diagram (positive)
Again, the point with the lowest boiling point is the azeotropic point. If X is distilled, the vapour produces
the azeotrope and the liquid pure B, whereas when Y is distilled, the vapour produces azeotrope and the
liquid pure A.
It is also possible to draw composition lines on the graphs for vapour pressure. These are on the other side
of the curve for those for boiling point, but otherwise are the same. The diagrams show the same products
from fractional distillation that would be shown on the boiling point graphs. This confirms the result given
above. 0729136768
4.4 Immiscibility
Provided a system composed of two immiscible liquids is adequately agitated, so that each liquid has a
chance to vapourised, the total vapour pressure of the system will be the sum of the saturated vapour
pressures of the two components separately.
P=P01 + P02
The system boil at a temperature lower than the boiling points of the two components. This phenomenon
is exploited in a technique called the steam distillation. In the technique, a substance immiscible in water
can be distilled at a temperature lower than 100˚C by blowing a current of steam through it. After
condensation, the substance and water form two layers which may be separated.
77
Phase equilibria
W1 and W2 are the masses of the two substance in the distillate, M1 and M2 being the molar masses and n1
and n2 being the number of moles co-existing in the vapour phase. Assuming an ideal behaviour then
W1 M1n1 M1P10 Weightof X M1P10

   
W2 M2n2 M2P20 Weightof water MH2OPH2O V
At any given pressure P, the boiling point of the steam may be predicted by plotting P 01 and P02 against T
and finding the temperature at which P01 + P02 = P.
Sample exercise 4.2
For n-octane (bpt=126˚C, M1=114 x 10-3 kg mol-1) the steam distillation temperature at 760 mm Hg is found
to be 90˚C. At that temperature, the saturated vapour pressure of water (P02) is 526 mm Hg. How much n-
octane will distill over per unit mass of water?
Solution
W1 M1P10 (114 x 10 -3 ) (760 - 526)

   2.8 Kg of Octane willdistillper Kg of water
W2 M2P20 18 x 10 -3 x 526
The hydrocarbon terpinene was found to distill freely in steam at a temperature of 95˚ C when the
atmospheric pressure was 744 mm Hg; the vapour pressure of water at this temperature is 634 mm Hg. The
distillate contained 55% by weight of the terpinene. Calculate its molecular weight.
Solution
W1 M1P10 (18 x 0.55) (744 - 634)

   confirmthe ans isit95.42586750788644
W2 M2P20 18 x 10 -3 x 634
4.5 Partition of solutes between two immiscible solvents

When a solute ‘i’ is able to dissolve in two immiscible solvents (A and B) in contact, it will distribute itself
between them so that at equilibrium the ration of the concentrations between the two will be a constant.
(Xi )A
 KD Where Xi is the molefraction
(Xi )B
For dilute solutions the mole fraction Xi is proportional to concentration Ci.
Thus
78
Phase equilibria
(Ci )A
 KD WhereCi is the concentration
(Ci )B
This is the basis of liquid-liquid extraction.
Example
A solute in water is removed by shaking with an immiscible solvent (ether) and then separating the two
layers. A fixed volume of second solvent will extract more solute if it is used in several small quantities
rather than all at once in a single extraction.
Sample exercise 4.3
At 292 K, the distribution coefficient (partition coefficient) of butanoic acid CH3CH2CH2COOH between ether
and water is 3.5.
a) Calculate the mass of butanoic acid extracted by shaking 100 ml of water containing 10 g of
butanoic acid
b) What should be the mass of butanoic acid removed in each of two further extractions using 100ml
of ether each time?
c) Compare the total mass of butanoic acid extracted in these three successive extractions with that
in a single extraction using 300 ml of ether.
Solution
[CH3CH 2CH 2COOH ether ]

a) KD 
[CH3CH 2CH 2COOH water ]
Let x g be the mass of acid extracted by 100 ml of ether.
The concentration of the acid in the water and ether layers respectively is
10  x 1 x 1
[CH3CH2CH2COOHwater ]  g ml and [CH3CH2CH2COOHether ]  g ml
100 100
x
[CH3CH2CH2COOHether ] x
From KD   3.5  100   x  7.78 g
[CH3CH2CH2COOHwater ] 10 - x 10  x
100
b) The fraction of acid extracted is 0.778 g remaining 2.22 g of acid in water.
A second extraction will extract 2.22 x 0.778 =1.73 g leaving (2.22-1.73)g= 0.49 g.
A third extraction will remove 0.49 x 0.778=0.38 g
Total mass= 7.78 + 1.73 + 0.38 =9.89 g
79
Phase equilibria
y
[CH3CH2CH2COOHether ] y
c) For a single extraction, KD   3.5  300   y  9.13 g
[CH3CH2CH2COOHwater ] 10 - y 3(10  y)
100
This confirms that stepwise extraction gives better results
Raoult also discovered the relationship between the vapor pressure of a solution and the vapour pressure of a pure
solvent, Jacobus Henricus van't Hoff found that the osmotic pressure of a dilute solution ( ) obeyed an equation
analogous to the ideal gas equation PV=nRT. He cthen came with the equation shown below.
nRT

V
This equation suggests that osmotic pressure is another example of a colligative property, because this pressure
depends on the ratio of the number of solute particles to the volume of the solution n/V not the identity of
the solute particles. It also reminds us of the magnitude of osmotic pressure. According to this equation, a 1.00 M
o
solution has an osmotic pressure of 22.4 atm at 0 C.
This means that a 1.00 M solution should be able to support a column of water 670 inches, or almost 56 feet, tall!
Exercise 4
1. State Raoult’s law
Positive and negative deviations from Raoult’s law do occur. Explain this with reference to molecule
1 and 2 in a solution
2. Benzene and toluene form nearly ideal solutions. If at 300 K P0(toluene)=3.573 Kpa, P0(benzene)=9.657
Kpa. Compute the vapour pressure of a solution containing 0.60 mole fraction of toluene,
3. The partition coefficient of a substance Y between ether and water is 3. Y being mole soluble in
ether. 1oo ml of an aqueous solution containing 10 g of Y is shaken in
(a) 100 ml of ether

80
Phase equilibria
(b) Four successive quantities of 25 ml ether
Calculate the weight of Y left in (a) and (b)
4. Mixtures of water and methanol obey Raoult’s vapour pressure law. If the vapour pressure of pure
water at 298 K is 24 mm Hg. Calculate the partial vapour pressure of the water in a mixture if 36 g
water and 32 g methanol at this temperature given that H=1 C=12 and O=16.
5. The following results were obtained in an experiment to determine the partition coefficient of
ammonia between water and trichloromethane
10.0 ml of aqueous layer required 43.2 ml of 0.25 M of HCl for neutralization
25.0 ml of trichloromethane layer required 21.6 ml of 0.05 M of HCl for neutralization
Calculate the partition coefficient at the laboratory temperature.
6. Ethyl acetate and ethyl propionate form nearly ideal solutions over the entire range of
compositions. At 20 ˚C, vapour pressure of ethyl acetate is 72.8 mm Hg and ethyl propionate is 27.7
mm Hg.
(i) Calculate the vapour pressure of liquid mixture 25 g ethyl acetate and 50 g of ethyl
propionate
(ii) Calculate the mole fraction of each of the vapour phase
(CH3COO CH2CH3- Ethyl acetate CH3 CH2COO CH2CH3 -ethyl propionate ethyl propionate)
81
Electrochemistry
5.0 Electrochemistry
5.1 Introduction
Electrochemistry is a branch of chemistry that deals with the relationship between electricity and chemical
reactions. The transfer of electrons during oxidation-reduction reactions (since it involves migration of
electrons) can be used to produce energy in the form of electricity. In other instances, we can use electrical
energy to make some non spontaneous reactions or chemical processes occur. We shall begin our study of
electrochemistry by learning the simple galvanic or voltaic cell, labeling the anode, the cathode and
direction of ion and electron movement as well as the sign of the electrodes. A galvanic or voltaic cell is an
electrochemical that derives electrical energy from spontaneous redox reactions taking place within the
cell. It generally consists of individual cell with two different metals immersed in a solution and then
connected externally or two half-cells separated by a porous membrane but then two different metals
connected externally.
5.2 Learning goals
By the end of this unit, you should be able to:-

 Define a galvanic cell
 Represent a cell on a diagram
 Write the anode, cathode and cell reaction for a given cell
 Given appropriate electrode potentials, calculate the emf generated by galvanic cell
 Describe the hydrogen electrode
 Define the standard electrode potential
 Use the Nernst equation to calculate standard electrode potentials and equilibrium constants
 5.2 Learning goals
5.2 An electrochemical cell

When a piece of zinc is placed in a solution containing Cu2+(aq) ions. Some of the zinc dissolves and copper is
plated onto the zinc bar. This is a spontaneous “tendency” for this electron transfer reaction to take place:
Zn(s) Zn2+(aq + 2e- (oxidation)

Cu2+(aq) + 2e- Cu(s) (reduction)
Zn(s) + Cu2+(aq) Cu(s) + Zn2+(aq (Overall reaction)
Kc for this reaction is very high. At equilibrium, the product Cu(s) and Zn2+(aq) predominate over the
reactants. There is a greater tendency for copper ions to be reduced (gain electrons) than zinc ions to be
reduced. This tendency has been tabulated as a series of reduction potentials.
If the tendency for zinc to give up electrons were ultilised so that electrons were made to flow through an
external circuit, useful electrochemical work would be done. This is known as the voltaic or galvanic cell.
82
Electrochemistry
Figure 16 An electrochemical voltaic or galvanic cell
An electrochemical cell consists of:-
 Two conductors (electrodes) immersed in electrolyte solutions- An electrode is a

conductor that passes an electrical current from one medium to another, usually from
a power source to a device or material. It can take a number of different forms,
including a wire, a plate, or a rod, and is most commonly made of metal, such as
copper, silver, lead, or zinc, but can also be made of a non-metallic substance that
conducts electricity, such as graphite. Anode-the electrode at which oxidation occurs
Zn(s) Zn2+(aq + 2e-
 Cathode-the electrode at which reduction occurs
Cu2+(aq) + 2e- Cu(s)
(1) A salt bridge (to avoid mixing)- in case KNO3. In order that a charge disparity produced by the
movement of electrons during the operation of the cell can be neutralized and the electro
neutrality maintained e.g. in the zinc-copper cell, Zn2+ ions are produced at the anode and Cu2+
ions consumed at the cathode. An overall positive charge in the solution at the anode and an
overall negative charge in the solution at the cathode would prevent further movement of
electrons and the cell would cease to function. The salt bridge allows migration of ions: anions
towards the anode and cations towards the cathode. Conduction of electricity from one
electrolyte solution to another- occurs via migration of K+ ions from the bridge in one direction
and NO3- in the other.
(2) Voltage measuring device-
 Potential difference is developed by this cell, this potential difference is a measure of

the driving force of the reaction.
83
Electrochemistry
 Potentiometer-two connectors are positive and negative- which indicate the direction
of current
 If the concentrations of the reactants and products in the cell are far from equilibrium
value, potential difference is very large. However if the concentrations are at
equilibrium, the potential difference is zero.
Electrode potential can be referred to as:-
The potential difference between electrode and solution i.e. the potential difference produced between an
electrode composed of a given chemical element and the solution in which it is immersed or
The electrode potential is the voltage between an electrode and the solution or electrolyte that it is
immersed in or even the difference between the charge on an electrode and the charge in the solution.
Point of emphasis
(1) If the concentrations are far from equilibrium, current flowing through the cell can be harvested as
in the case of a battery
The battery is an electrochemical cell
Galvanic or voltaic cell – This is a store for electricity where spontaneous chemical reactions take
place to generate electricity
(2) We can also put a battery or power supply across a cell and drive the electrochemical reaction.
An electrolytic cell requires an external source of electrical energy. This is required to force the
reaction to proceed in the opposite direction.
(3) In a galvanic cell, the anode has a negative charge and the cathode has a positive charge.
Teaching notes
An aid to remembering the signs of the electrodes in a galvanic cell is the “an” for the anode for “a”
negative electrode
5.4 Reference electrodes and standard reduction potentials.

A comparison of the “reduction tendency” of various substances can be made. It would be useful if the
potentials for different half-cells could be tabulated. However, the potential of the half-cell itself cannot be
measured: it is possible to measure only the potential difference between two half cells. We therefore
select arbitrarily a reference electrode relative to which all other half-cells are measured. The results are
tabulated for standard half-cells, that is, all reacting species are at a concentration of 1 M (strictly speaking,
at unit activity) if in solution or at constant pressure if 1 atmosphere of gas.
Reduction potential
Reduction potential (also known as redox potential, oxidation / reduction potential) is a measure of the
tendency of a chemical species to acquire electrons and thereby be reduced. Reduction potential is
84
Electrochemistry
measured in volts (V), or millivolts (mV). Each species has its own intrinsic reduction potential; the more
positive the potential, the greater the species' affinity for electrons and tendency to be reduced. ORP is a
common measurement for water quality (Suslow, 2004)[ It is a measure of the tendency of the solution to
either gain or lose electrons when it is subject to change by introduction of a new species. This implies that
a solution with a higher (more positive) reduction potential than the new species will have a tendency to
gain electrons from the new species (i.e. to be reduced by the new species) and a solution with a lower
(more negative) reduction potential will have a tendency to lose electrons to the new species (i.e. to be
oxidized by the new species).
Because the absolute potentials are difficult to accurately measure, reduction potentials are defined
relative to a reference electrode. Reduction potentials of aqueous solutions are determined by measuring
the potential difference between an inert sensing electrode in contact with the solution and a stable
reference electrode connected to the solution.
5.5 The standard hydrogen electrode-SHE

Reduction potentials of aqueous solutions are determined by measuring the potential difference between
an inert sensing electrode in contact with the solution and a stable reference electrode connected to the
solution via a salt bridge (Gary, and Duffy, 2011).
The standard half-cell chosen as the reference half-cell is the hydrogen half cell: It contains a platinised
platinum electrode (inert) dipped in a solution of HCl which gives 1 M of H+(aq) and having hydrogen gas (H2)
at 1 atm continuously bubbled over the electrode.
Figure 17 The standard hydrogen electrode-SHE (anode) attached to another another cell cathode
The reduction reaction is
H+(aq) + e- H2(g)
Just as the transfer of hydrogen ions between chemical species determines the pH of an aqueous solution,
the transfer of electrons between chemical species determines the reduction potential of an aqueous
solution. It is therefore possible to define pE (logarithm of electron concentration in a solution) as
proportional to the redox potential (Stumm and Morgan, 1981). Sometimes pE is used as a unit of
reduction potential instead of Eh, in environmental chemistry.
85
Electrochemistry
The transfer for the hydrogen cell (usually referred to as a standard hydrogen electrode, SHE) is
assigned an arbitrary value of 0.00 V i.e. E˚= 0.00 V at a selected temperature, usually 298 K. E˚ is the
standard reduction potential, (standard indicative) relative to the hydrogen half-cell described above.
5.6 Standard reductive potentials

The standard reductive potentials of Zn2+(aq) can be measured by setting up an electrochemical cell which
contained H2 /H+(aq) 1M in one half-cell and Zn/Zn2+(aq) 1M in the other half-cell.
Figure 18 A set up for determining the Standard Reduction Potential of zinc
The measure the emf of the cell while the temperature is maintained at 298 K can be obtained by using
the following equation below.
E˚cell= E˚ observed - E˚ reference
From this equation, then cell potential is -0.76 V-0.00 V= -0.76 V
It can also be E˚cell= E˚ cathode- E˚ anode
The emf of the cell is then the standard electrode potential for the reduction reaction
Zn(s) Zn2+(aq + 2e- E˚= -0.76 V
E˚ values for other half cells can be determined in a similar manner and the recorded. Notice that the
respective concentrations of the test solutions in each half-cell are 1 M in the determination of E˚ values. If
it is not 1 M, the value determined is not E˚ but some other value which depend on the concentration of
the solution.
The more positive the value of E˚, the greater the tendency for reduction, and the better an oxidising agent
the material is. The more negative the value if E˚, the lower the tendency for reduction and the better the
reducing agent is the reduction product.
5.7 Preparation of cells

Line diagram
86
Electrochemistry
(anode)Zn/ZnSO4(1.0 M)//CuSO4(1.0 M)/Cu (cathode)

Figure 19 Cell line diagram
(i) The half-cell of the anode, where oxidation occurs, i.e. the half-cell with the lower oxidation
potential, is written left: the concentration of the species present is shown in the bracket.
(ii) The double vertical lines represent the salt bridge when the half-cells are not in contact. The ions or
aquated species of the half-cell should be next to the salt bridge symbol.
(iii) The half cell of the cathode, in which reduction occurs, i.e. the half-cell with more positive E˚ (less
negative) is written on the right hand side of the cell.
Calculation of E˚values
The E˚ (emf) of the cell is calculated from the equation-
E˚cell= E˚ right - E˚ left
When the E˚values are both relative to E˚ H2/H +(1 M) being assigned a value of 0.00 V. NOTICE THAT TWO
STANDARD REDUCTION POTENTIALS ARE NOT INVOLVED.
Eg: for the above cell, E˚cell= E˚ right - E˚ left = 0.43- (-0.76)=1.10 V Thus
Eg: for the above cell, E˚cell= E˚ cathode - E˚ anode = 0.43- (-0.76)=1.10 V
If the cell is correctly written with the anode on the left and cathode on the right and E˚ for the cell
(concentrations 1 M) is calculated as above, then E˚>0 (positive) and the redox reaction proceeds in the
direction shown, that is, zinc displaces copper ions from solution. A cell so constructed will produce a
voltage of 1.10 V. If E˚<0 (negative), the spontaneous redox reaction proceeds in the manner opposite to
that written. The spontaneous reaction can be reversed if a voltage greater than the voltage is applied.
The standard cell potential is the potential difference between the cathode and anode.
When the concentration of the solution is not 1.00 M, there is a departure of the cell potential from the
standard electrode potential as shown below.
E  Erex
0
kC
Where C = concentration
k= proportional constant
87
Electrochemistry
5.8 The Nernst equation
The actual value of electron concentration is not measurable as it is of order of 10^-55 M, yet it is
thermodynamically a well defined quantity. What matters is the logarithm of the quotient of concentration
of electrons in one solute with respect to the other, and that is, via Nernst equation, proportional to the
redox potential. This point of view is useful for understanding redox potential, although the transfer of
electrons, rather than the absolute concentration of free electrons in thermal equilibrium. It should be
noted that both pH and redox potentials are properties of solutions, not of elements or chemical
compounds, thus they depend on parameters such as concentrations and temperature.
What factors determine the magnitude of the cell potential?
 Energy is the inherent driving force reactions. All reactions move to minimize their energy, so if a
lot of energy is released when redox occurs, the potential will be large. This is expressed as their
standard electrode potential, E˚.
 Concentration. If concentration is high, Le Châtelier’s principal would say the driving force is grater,
therefore the potential is greater.
These concentration and electrode potentials are taken into account using the Nernst equation:
Giving a hypothetical reaction:
Ox + ne- Red
Half cell potential associated with this half cell is given by:
RT Red
E  Erex
0
 ln
nF Ox
0
Where Erex is the thermodynamic driving force for the reaction when the other half cell of the reaction is
SHE (standard reduction potential).
Summary
The standard cell potentials refer to cells in which all dissolved substances are at unit activity, which
essentially means an "effective concentration" of 1M. Similarly, any gases that take part in an electrode
reaction are at an effective pressure (known as the fugacity) of 1 atm. If these concentrations or pressures
have other values, the cell potential will change in a manner that can be predicted from the principles you
already know.
Suppose, for example, that we reduce the concentration of Zn2+ in the Zn/Cu cell from its standard effective
value of 1M to an to a much smaller value:
Zn(s) | Zn2+(aq, .001M) || Cu2+(aq) | Cu(s)
This will reduce the value of Q for the cell reaction

88
Electrochemistry
Zn(s) + Cu2+ → Zn2+ + Cu(s)
thus making it more spontaneous, or "driving it to the right" as the Le Châtelier principle would predict, and
making its free energy change ΔG more negative than ΔG°, so that E would be more positive than E°.
The relation between the actual cell potential E and the standard potential E° is developed in the following
way. We begin with the equation derived previously which relates the standard free energy change (for the
complete conversion of products into reactants) to the standard potential
If ΔG° = –nFE° then By analogy we can write the more general equation ΔG = –nFE
which expresses the change in free energy for any extent of reaction— that is, for any value of the reaction
quotient Q. We now substitute these into the expression that relates ΔG and ΔG° which you will recall from
the chapter on chemical equilibrium:
ΔG = ΔG° + RT ln Q
NOTE
All these E0 values are based on writing the equation as a reduction (that is also known as the standard
reduction potential).
Cl2 + 2e- 2Cl- E0=1.36 V Strong tendency to occur as reduction (i.e as written)
Na+ + e- Na E0=-2.71 V Strong tendency to occur as reduction (i.e opposite direction written)
If we take the Nernst equation, convert it to base 10, put in the actual values for R and F assuming the
reaction take place at room temperature (298 K), we get
0.059 Red
E  Erex
0
 ln
n Ox
Sample 5.1
Calculate the half-cell potential for Zn electrode in 10-2 M Zn(NO3)2 half-cell reaction:
0.059 1 0.059 1
Zn2+(aq + 2e- Zn(s) E  Erex
0
 ln 2  E  -0.76  ln  0.822 V
n Zn n 0.01
What does this mean?
The reaction proceeds as an oxidation, therefore Zn is anode
This is the cell potential we could get if we assemble the cell:
Any half-cell potential calculated using the Nernst equation is an E for a hypothetical cell which has the half
cell of interest as the cathode and the SHE as the anode. However, the negative sign on our example
indicates that if the assembled, the Zn electrode would be the anode.
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Electrochemistry
Consider the half-cell consisting of the SHE, but P(H2) and [H+] are different.
[P(H2) = 0.5 atm and [H+]=0.01 M]
So reaction:
2 H+ + 2e- H2
0.059 H2 0.059 0.5

E  Erex
0
 ln   E  Erex
0
 ln  0.1093
n H 2 0.01
This is how you calculate the half-cell potential, but we would also like to do this for the whole cell (i.e.
when you actually have two half-cells connected to each other).
In order to calculated the Ecell
The standard cell potential is the potential difference between the cathode and anode
 Write both half-cell reactions as reductions
 Calculate Ecell= E right - E left using Nernst equation
 Calculate Ecell= E right - E left
Sample exercise 5.2
Calculate the Ecell for the following

Zn/ZnSO4(1.0 M)//CuSO4(1.0 M)/Cu
Anode on the left
Zn2+ + 2e- Zn(S) E ˚= -0.763 V
0.059 1 0.059 1
E  Erex
0
 ln 2  E  -0.763  ln 2  0.763 V
n Zn n Zn
Cathode on the right
Cu2+ + 2e- Cu(S) E ˚= 0.337 V
0.059 1 0.059 1
E  Erex
0
 ln 2  E  -0.337  ln  0.337 V
n Cu n 1.00
Ecell= E right - E left=0.337-(-0.763)=1.10 V
90
Electrochemistry
So, cell reaction is spontaneous as written, the anodes reaction is in fact the oxidation and the cathode
reaction is in fact reduction reaction.
So what if the cell drawn in this way:-
Cu/CuSO4(1.0 M)//ZnSO4(1.0 M)/Zn
In such a presentation, Cu will be the anode while Zn is the cathode. Upon calculation the Ecell is negative
Sample 5.3
Calculate the standard electrode potential for Cd electrode in a solution of 0.010 M Cd2+
Cd2+ + 2e- Cd(s) E0=-0.403 V
0.0591 ox 0.0591 Cd(s) 0.0591 1

E  Erex
0
 ln  E  -0.403  ln 2  0.403  ln  0.462
n red 2 Cd 2 0.010
Sample 5.4
Calculate the potential for the following cell:-in a solution of 0.010 M Cd2+
Zn/ZnSO4(5.0 x 10-4 M)//PbSO4(Sat)/Pb

Step 1
PbSO4(S) + 2e- Pb(s) + SO42-(aq) E˚= -0. 305 V
Zn2+(aq + 2e- Zn(s) E˚= -0.76 V
Step 2
0.0591 ox 0.0591
E  Erex
0
 ln  E  -0.350  ln(5 x 10 -4 )  0.252V
n red 2
Step3
0.0591 ox 0.0591 1
E  Erex
0
 ln  E  -0.763  ln  0.860V
n red 2 (5 x 10 -4 )
Step4
Ecell= E right - E left=-0.252-(-0.860)=+0.608 V
5.9 Equilibrium constant

The equilibrium constant for the reaction
91
Electrochemistry
γcC γDd
aA + bB ⇌cC + dD is written as K eq  a b where γ  activity(concentration)
γ A γB
Therefore the associated Nernst equation can be written as
RT RT
Ecell  E0  m,Ecell  0 hence E0  lnKeq
lnKeq andwhenthe cellis at equilibriu
nF nF
This implies that Keq can be calculated from E0 values
Sample 5.6
Calculate the equilibrium constant for the reaction
RT 0.0257
Pb/Pb2+(0.1M)//Ag+(0.01M)/Ag E0=0.93 V ⇒From E0  lnKeq then 0.93  lnKeq
nF 2
Therefore ln Keq=72.37 and Keq=2. 7 x 10-31
Sample exercise 5.7
A piece of copper is placed in a 0.050 M solution of AgNO3. What is the equilibrium constant of the
solution?
The reaction is Cu(s) + Ag+ ⇌Cu2++2Ag(s)
Half reactions Ag+ + 2e-⇌2Ag(s) E0= 0.799 V
Cu(s) + 2e- ⇌Cu2+ E0= 0.399 V
Ecell= E right - E left=0.799 - 0.337=0.460 V
RT nF
From E0  lnKeq then lnKeq  E0
nF RT
⇒ln Keq=72.37 and Keq=3. 55 x 10-15
Summary
Spontaneous oxidation – reduction reactions can be used to generate electricity in galvanic cells. The
electrode at which oxidation occurs is called anode while the cathode is the where reduction take place.
A galvanic cell may be thought to possess a “driving force” that moves the electrons through the external
circuit, from anode to cathode. The driving force is called the electromotive force (emf) and is measured in
92
Electrochemistry
volts. The emf of a cell can be regarded as being composed of two parts: that due to oxidation at the anode
and that due to reduction at the cathode. Ecell= E oxd - E red
Oxidation potentials E ox and reduction potentials E red can be assigned to half-reactions by defining the SHE
as a reference:
2H+(1M) + 2e- H2(1 atm) E0=0.00 V
Standard reduction potentials are referred to as standard electrode potentials and are recorded for a great
variety of reduction half reactions.
The Nernst equation relates emf under non-standard conditions of standard emf:
2.303RT
E  E0  lnQ
nF
2.303RT
At equilibrium, Q=K and Ecell=0 Therefore E0  lnK
nF
This relates the standard emf to the equilibrium constant K
93
Electrochemistry
REFERENCES
Reichardt, C. (2007). Solvents and Solvent Effects in Organic Chemistry, Organic Process Research & Development
11, 105 - 113
Suslow, T.V. (2004) Oxidation-Reduction Potential for Water Disinfection Monitoring, Control, and Documentation,
University of California Davis, http://anrcatalog.ucdavis.edu/pdf/8149.pdf
Gary, vanLoon,; Duffy, S (2011). Environmental Chemistry - a global perspective (3rd ed.). Oxford University Press.
pp. 235–248.
Stumm, W. and Morgan, J. J. (1981): Aquatic chemistry, 2nd Ed.; John Wiley & Sons, New York.
94

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SCH 101: Introduction to Physical Chemistry

Introduction to physical chemistry..................................................................................................................................... 1

The gaseous state ............................................................................................................................................................... 1

1.1 The state of matter................................................................................................................................................... 1

1.1.1 Solids ..................................................................................................................................................................... 1

1.1.3 Gases ..................................................................................................................................................................... 2

1.2 The gas laws ............................................................................................................................................................. 2

1.3.1 The Pressure-Volume Relationship: Boyle's Law .................................................................................................. 2

1.3.2 The Temperature-Volume Relationship: Charles's Law ........................................................................................ 5

1.3.3The Quantity-Volume Relationship: Avogadro's Law............................................................................................. 7

1.4.1 The gas constant R............................................................................................................................................... 11

1.5 Mixture of gases: Dalton’s law of partial pressure................................................................................................. 12

1.6 The kinetic molecular theory of ideal gases ........................................................................................................... 14

Egg-in-the-Bottle Demonstration ................................................................................................................................... 0

2.0 Chemical equilibria ..................................................................................................................................................... 30

2.2 Learning goals ......................................................................................................................................................... 30

2.3 The concept of equilibrium .................................................................................................................................... 30

2.4 The magnitude of equilibrium constants ............................................................................................................... 32

2.4.1 The direction of chemical equation and K........................................................................................................... 34

2.6 Relationship between Kc and Kp ............................................................................................................................. 36

2.7 Approach to equilibrium ........................................................................................................................................ 38

2.8 Heterogeneous equilibrium ................................................................................................................................... 40

2.9 Factors influencing equilibrium concentration ...................................................................................................... 41

Effect of change in Reactant or Product Concentrations ............................................................................................. 43

Effect of change in temperature .................................................................................................................................. 44

3.0 Acid-base equilibria ................................................................................................................................................ 46

3.1 Introduction ........................................................................................................................................................ 46

3.7.3 Neutralization indicators ................................................................................................................................. 60

4.1 Introduction ........................................................................................................................................................ 67

4.2 Liquid- vapour equilibria .................................................................................................................................... 68

4.2.1 Solutions .......................................................................................................................................................... 68

Colligative properties ............................................................................................................................................... 68

4.3. Raoult’s law .................................................................................................................................................. 69

Boiling point elevation (ebullioscopy) ...................................................................................................................... 72

Freezing point depression (cryoscopy)..................................................................................................................... 72

4.3 Positive deviation ............................................................................................................................................... 76

4.4 Immiscibility ....................................................................................................................................................... 77

4.5 Partition of solutes between two immiscible solvents ...................................................................................... 78

5.1 Introduction ........................................................................................................................................................ 82

5.2 An electrochemical cell ...................................................................................................................................... 82

5.4 Reference electrodes and standard reduction potentials. ................................................................................ 84

5.5 The standard hydrogen electrode-SHE .............................................................................................................. 85

5.6 Standard reductive potentials ........................................................................................................................... 86

5.7 Preparation of cells............................................................................................................................................. 86

5.8 The Nernst equation........................................................................................................................................... 88

5.9 Equilibrium constant .......................................................................................................................................... 91

1) Atkins, P.W., Physical Chemistry, and edition, OUP.

2) Any other physical chemistry textbook

Introduction to physical chemistry

The gaseous state

1.1 The state of matter

But what makes them different?

Solid<liquid << gas

1.2 Learning goals

By the end of this unit, students should be able to:-

1.2 The gas laws

1.3.1 The Pressure-Volume Relationship: Boyle's Law

Figure 1 An illustration of Boyle's experiment.

From that, he developed the Boyle’s law which stated that:-

Boyle's law can be expressed in mathematical terms as shown in equation1.

Plot another with different temperatures

Figure 3 Graphs based on Boyle's law of volume versus 1/P.

This is because PV must remain constant.

Sample exercise 1.1