SCH 103 PHYSICAL CHEMISRY I

COURSE OUTLINE
- Gaseous state: Kinetic theory of gases, general
- Equation of state units of variable
- Properties of molecules and gas laws
- Velocities of molecules and kinetic energy
- Specific heat: Cp and Cv for mono atamic gases
- Behavior of real gases
- Determination of molar masses
- Gas liquid equilibrium
- Liquid and their solutions containing non volatile solutes
- Modes of expressing concentrations, colligation properties and Raoult’s law
- Solution of gases in Liquids Henry’s law solutions of two volatile (ideal) liquid
- Chemical equilibrium constant equilibria in gas phase, Ka and Kp interlationship
- Ionic equilibria and solubility product principle and their salts,
- dissociation constant, hydrogen ion concentration and PH scale.
- Ionic product of water, theory of acid /base indicators.

Ref.
1. General chemistry 2nd Ed.
David Becker
2. A. level chemistry
Ramasden
3. Any physical chemistry text book

Mode of Assessment
Exam 70%
Assignment and Cats 20%
Practical 10%
 WK TOPICS
1 Gas laws
2 Kinetic theory of gases, grahams law of diffusion
3 velocity of molecules behavior of real gases, determination of molar masses.
4 Gas- liquid-equilibrium, liquids and their solutions containing volatile solutes,
5 modes of expressing concentrations, colligative properties,
6 CAT I
7
8 colligative properties, and the raoults l, solutions of gases in liquids, henry law
9 Chemical equilibrium, equilibrium constant, equilibria in gas phase, Kc and Kp
interrelationship
10 ionic equilibria and solubility product principle, aqueous solutions of weak acids,
weak bases and their salts,
CAT II
12 dissociation constant and hydrogen ion concentration and the pH scale, ionic product
of water, theory of acid base indicators
Revision and Exams

WEEK 1
Gas laws
Experiments with a large number of gases reveal that form main variables are usually sufficient to
define the state or condition of a gas. These are temperature (T), pressure (P), volume (V) and the
quantity of the gas which is usually expressed as the number of moles (n). The equations that
express the relationship among P, T, V and n are known as gas laws or equations of state.

BOYLE’S LAW: pressure-volume relationship.

This was investigated by a British chemist Robert Boyle in 1662. It states that at constant
temperature, the volume of a definite mass of a gas in inversely proportional to its pressure.
They found out that when to the pressure of the gas was increased the volume decreased.
Mathematically it can be expressed as
 1
Vα
P
1
V  Constant X
P
PV  Constant (describes a hyperbola)

By potting P against V the obtain a hyperbola (curve)

P

P2
P1

V2 V1

The area P1V1 and P2 V2 are equal

Then P1 V1 = P2 V2
1
When P is plotted against 𝑉 we obtain a straight line passing through the origin

1
𝑉
When PV is plotted against P we obtain a horizontal straight line
PV

P
It has been shown that gases don’t obey Boyle’s law under all the conditions. All gases come closer
to obeying the law at low density.

Units of pressure
Torr are units of pressure and 1torr-101325 Pascal (pa)
1atm = 1.0132x105 nm-2 =1.0132x105 pa =760 mmHg
SI unit for pressure is nm-2

CHARLES LAW: temperature volume relationship

Two French scientists Gay lussac and J. Charles independently measured the expansion of gases
that occurs when the temperature is raised while the pressure was kept constant. They found out
the volume varied linearly with temperature. Thus doubling the temperature doubles the volume.
It states as follows the volume of a fixed mass of gas is directly proportional to absolute
temperature at constant pressure.
By plotting volume (V) against absolute temperature (T) we get

On extrapolation the cuts the temperature axis at -273.15 oC. At this point the gas would
theoretically have no volume however most gases highly on solidify before this point is reached.
The point is referred to as absolute zero and it is from this point that the absolute temperature
scale on Kelvin scale is derived i.e T= t + 273. To convert Celsius scale to Kelvin scale 273 is
added and vice versa.
For example
20 oC = 20 +273=293 K
Kelvin scale is converted to celsius scale by subtracting 273
373 K= 373-273=100 oC
Mathematically Charles law is expressed as
Vα T
V  Constant X T
V
 Constant
T
A gas which obeys Charles and Boyle’s law is ideal

EQUATION OF STATE FOR AN IDEAL GAS

The results of Boyle’s and Charles may be combined in an expression, which represents the
relationship between P, V and T of a given mass of gas; such an expression is called an equation
of state.
1
Boyle’s law Vα (at constant , n, T)
P
Charles law V αT (at constant , n, P)

Avogadro’s law V α n (at constant , P, T)

These relationship can be combined and we get

nT
Vα
P
If n = 1 mole then,

T
Vα
P
Therefore,
T
V  constant x
P
Thus,
PV
 constant
T
If a given mass of gas have volume V1 at temperature T1 and pressure P1 and volume V2 at
temperature T2 and pressure P2
The relationship becomes

P1V1 P2 V2

T1 T2

This equation is called the equation of state for ideal gas

N.B.
Temperature must always be in Kelvin in the ideal equation of state.
Example
If the volume of a gas collected at 60 oC and 1.05 x 105 Nm-2 is 60cm3, what would be the it’s
volume of gas at stp
Solution
P1 = 1.05 x 105 Nm-2
T1 = 273 x 60=333 K
V1 = 60cm3
Standard conditions (stp) are
P2 = 1.01 x 105 NM-2 (or 760 mmHg or 1 atm)
T2 = 1.01 x 105 NM-2
T2= 273K
V 2=?
𝑃1 𝑉1 𝑃2 𝑉2 𝑃1𝑇2 𝑉1
Since = then V2 =
𝑇1 𝑇2 𝑃2𝑇1

1.05 𝑥 105 𝑥 60 𝑥273

= 1.05 𝑥 105 𝑥 333

= 51 cm3
From the equation,
𝑃𝑉
= Constant
𝑇

the constant is called the gas constant (R)

We can therefore say,
𝑃𝑉
=R
𝑇

And when 1mole of gases is used and it R is referred to as molar gas constant
For n moles of the gas the equation becomes
𝑃𝑉
= 𝑛𝑅 , and it is called the ideal gas equation (which is obeyed by all the gases).
𝑇

The ideal gas equation can be used to determine other quantities involving gas such as
concentration.
Concentration (C) is defined as moles per volume
𝑛
C= 𝑉

We can rearrange the ideal equation as follows

n
Therefore P = V RT

Then P = CRT
Also n can be given as mass of gas as a fraction of the relative formula mass M
𝑚
n=𝑀 we can replace n in the equation
𝑛
p=𝑉 𝑅𝑇

we get,
𝑚
𝑅𝑇 𝑚𝑅𝑇
P = 𝑀𝑉 = 𝑀𝑉
𝑚
Since defines density ρ then
𝑉

We can rearrange and obtain

ρRT
M
P

GAS CONSTANT (R)

The gas constant R is a very important quantity and we need to work out its volume and units.
The value of R can be worked out using pressure in NM-2 or atm.
At stp the volume of 1mole of an ideal gas occupies 22.4l (22.4 x 10-3 M3), the pressure is 101325
NM-2 or 1 atm while the temperature is 273K
Hence in SI unit
𝑝𝑣 101325𝑁𝑚−2 𝑥 22.4𝑥10−3 𝑚3
R=𝑛𝑇 = 1𝑚𝑜𝑙 𝑥 273𝐾

= 8.314J mol-1k-1(J=Nm)
Alternatively we can use pressure in atm
We get
𝑝𝑣 1 𝑎𝑡𝑚 𝑥 22.41
R=𝑛𝑇 = 1𝑚𝑜𝑙 𝑥 273 𝑘

= 0.0821 atm mol-1k-1

Note: the value and the units for the gas constant, R, depends on the pressure units used.

Assignment
1. Calculate the volumes which would be occupied by a given gas at the given final pressure
whose initial volumes and pressure are given
2. Initial volume /cm3 initial pressure final pressure
a. 152 750 mm/Hg ` 760 mm/Hg
b. 180 760 mm/Hg 720
c. 5250 1atm 1.35 atm
5
d. 1540 1.01 x 10 pa 7.35 x 104 pa
3. The volume of a 5.2 cm3 sample gas at 700 Torr is increased to 780 Torr. What is the new
volume, if temperature and,n, are held constant.
4. Calculate the volume of 1 mole of an idea gas at s.t.p
5. The density of Nitrogen gas is 1.68g-1, what volume will it occupy at 273 and at 100 kpa
(R=8.314J mol-1k-1)

WEEK 2

DALTONS LAW OF PARTIAL PRESSURES

This law is concerned with the pressure of a mixture of gases. Assuming the gases don’t react with
each other. In a mixture of one or more gases each gas exerts the same pressure as that which it
would have if were alone, occupied the container. This is referred to as partial pressure of the gas.
The law states that:
the total pressure of a mixture of gasses is equal to the sum of the partial pressure of the
constituent gases.
If P1, P2, P3…….. are partial pressure of the individual gases in a mixture then the total pressure P
is given by
P= P1 +P2+P3 …………………
Considering the ideal gas equation we see that
P1 V =n1RT P2V=n2RT ………………………..etc
hence
(P1 +P2+P3…………..) V = (n1 +n2+n3………) RT
or PV=nRT
where, n is the total number of moles
n1 +n2+n3……………………… =1
n1 n2
p1 = v pT = X1 pT, p2 = p = X2 p
V
n1 n2
X1 and X2 given, by and 𝑟𝑒𝑠𝑝𝑒𝑐𝑡𝑖𝑣𝑒𝑙𝑦 are called mole fraction of the respective gas [N.B
V V
each component is at the same temperature and occupies the same volume. The sum of the mole
fraction is equal to 1.
Example
100 ml of oxygen at 1.78 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
From Boyle’s law we can obtain the partial pressure of each gas as the volume changes to 500ml
P1V1 =P2V2
100 ml x 1.75 atm =500 ml x PO
PO = 0.35 atm
200 ml x 0.6 atm = PN x 500ml
PN = 0.24 atm
Ptotal = PO +PN =0.35atm +0.24 atm
= 0.59 atm

THE KINETIC MOLECULAR THEORY OF IDEAL GASES

The laws that we have discussed describes the behavior of gases and they call for explanation
The Kinetic theory is based on a number of assumptions.
1. The molecules of gases are always in constant motion in straight lines. When temperature
is increased and volume decreased the pressure increases. This is because
 As the molecules collide with the walls of the container they exerts pressure on the
container
 If the volume is decreased molecular collide more frequently with the container and
the pressure increases.
 If the temperature is increased the molecules gain Kinetic energy thus increasing
the pressure.
2. The collisions are perfectly elastic molecules bounce off the walls with no loss of kinetic
energy. If this were not the case and if molecules rebounded with loss energy, they would
be giving up energy to the container and the temperature of the container would rise
while that of the gas falls.
3. The volume of the molecules is negligible compared to the total volume of the container
e.g. the gas only occupies 0.03% of the total volume.
4. The molecules /atoms exert no attractive or repulsive forces between them. The distances
between the molecules is so great compared the sizes of the molecules and therefore they
exert no force upon one another except during collisions.
Kinetic theory equation.
Based on the kinetic theory assumptions R.J Clausius derived the kinetic theory equation.
𝟏
PV= 𝟑 𝐦𝐍𝐜̅̅̅𝟐

Where,
P=pressure
V=Volume
M=mass of one molecules
̅̅̅
𝑐 2 = mean square velocity

If there are n1 molecules with velocity c1, n2 with velocity c2 etc c̅2 is given by
n2 c12 + n2 c22 + n3 c32 + ⋯
c̅2 =
n1 + n2 + n3 + ⋯

The square root of ̅̅̅

𝑐 2 , √̅̅̅
𝑐 2 is called the root mean square velocity (RMS velocity)
Examples
Calculate the RMS velocity oxygen molecules at s.t.p (0=16)
Method 1
Molar mass of oxygen = 32 gmol-1
In the equation,
1
PV= 3 𝑚𝑁𝑐̅̅̅2 for 1mole of the gas we have

Since PV=RT (replace PV with RT) in the above equation

1
We get RT= 3 𝑚𝑁𝑐̅̅̅2

Then N=L, avogadros constant and mL= M (M = molar mass given in Kg/mol)
The molar mass of gas in Kgmol-1 which gives
1
RT= 3 Mc̅2
3RT
= c̅2
M
3RT
c̅2 = M
3RT
c̅2 = M

̅̅̅̅̅ 3 x 8.314 x 273

c2 = 32
1000

√̅̅̅
𝐜 𝟐 = 𝟒𝟔𝟏𝐦𝐬 −𝟏
Therefore RMS velocity of oxygen at s.t.p is 461ms-1

Kgm 2
Units for RMS we know that 1J 
s2
V=m/s
Method 2
From the density oxygen 1.428 x 10-3 cm-3 at s.t.p

3pV V mN
c̅2 = (PV=RT)=nN since = p (density of the gas)
mN V
3P 3xpressure (n/m)
Therefore c̅2 = =
⍴ density of the gas in Kg m−3

⍴= 1.428 x10g-3cm-3 = 1.428Kg m-3 at s.t.p

5
3 x 1.013 x 10 𝑁/𝑚2
c̅2 = 1.428 Kg Kg m−3 the units simplify to Nm = J
 √̅̅̅
𝐜 𝟐 = 𝟒𝟔𝟏𝐦𝐬 −𝟏 𝐚𝐬 𝐛𝐞𝐟𝐨𝐫𝐞

Kgm 2
Recall 1J 
s2
TRANSLATIONAL ENERGIES
1
The translational kinetic energy of a partial is given by 2 mc 2

The translation kinetic energy of a number of molecules of gas, Et, is given by

1 1 1 1
Et = 2 mc12 + mc22 + mc32 … … . . 2 mcn2
2 2

If N = number of molecules and c̅2 = mean square velocity

1
Then Et== 2 mNc̅2
1
Since PV= 3 mNc̅2 = RT
1
Then, mNc̅2 = RT
3

mNc̅2 = 3RT
𝟑
Therefore, Et= 𝟐RT

For example the transitional Kinetic energy of 1 mole of a gas at 273K is given by
3
Et = 2 x 8.314 x 273 = 3.405 kJmol−1

Distribution of Molecular energies

Maxwell and Boltzman plotted distribution curves to show how the spread in value of molecular
energy (translational kinetic energy) changes with temperature
Note
1. The area under the area under the curve at lower and higher temperatures is the same and
adds to unity (1)
2. As the temperature is increased the energy of molecules also increases proportionately

Assignment
1. A mixture of gases at s.t.p contains 65 % Nitrogen, 15 % Carbon dioxide and 20%
oxygen by volume. What is the partial pressure of each gas
2. A 1500 ml mixture of O2, N2 and CO2 has a pressure of O2 and CO2 are 3.5 torr
and 125 torr respectively. What is the mole fraction of N2 in the mixture?

WEEK 3

REAL GASES
Ideal gases obey the Boyle’s law when PV is plotted against P. Real gas deviate from the ideal
gases at high pressures and low temperatures.
Causes for Deviations
i) Many gases approach ideal gas behavior at about 1atm pressure. At high pressures most
gases liquefy.
ii) At low temperatures must gases approach their boiling point.
Two assumptions of the Kinetic theory have to be modified in gases at high pressure and low
temperature. When gas molecules are compressed, the molecules come close enough for van der
between forces of attraction to operate between them. These attractions make the gas move
compressible than it is at low pressures at for 1mole of gas Pv < RT.

More attraction wall of the container

less force
A molecule striking the wall of the container experiences a force of attraction towards other
molecules of the gas and lessens the impact on the wall. The pressure needs to be corrected by
𝑎
adding a term 𝑉 2 to compensate for the intermolecular attraction. The effective pressure becomes
𝑎 𝑎𝑛2
𝑝 + 𝑉 2 𝑜𝑟 [𝑝 + ] for n molecules. The postulate or assumption that molecules occupy
𝑉2
negligible volume needs modification Molecules however are considered to occupy a certain
volume. The volume V is corrected for the molecules to yield an effective volume. The correction
term for volume “b” called co-volume is found to be equal to 4 times the actual volume of the
molecules is introduced to give the actual volume as v-b for 1 mole or v-nb for n moles of the gas.
The final equation becomes
an2
(p + ) (v − nb) = nRT f`or n moles
v2

This is called the Van der waals equation in which a and b are constant that are determined
experimentally. Easily liquefiable gases here like CO2 have the highest values of a white largest
molecules have highest value of b.
Example
Predict the pressure of 0.8l of 0.5moles of CO2 at 273K.
a. ideal gas equation
b. Van der waals equation
R= 0.0821 atm mol-1 K-1 or 8.314 JK-1 Mol-1
𝑛𝑅𝑇
a) PV = nRT = P= 𝑉
0.5𝑚𝑜𝑙 𝑥 0.821𝑎𝑡𝑚.𝐿 𝑚𝑜𝑙−1 𝑘 −1
= 0.8 𝑙
= 14 atm

b) Van der waals equation

a = 6.851 atm mol-2 and b= 0.0561mol-1
𝑛𝑅𝑇 𝑎𝑛2
p = 𝑣−𝑛𝑏 − 𝑉2
0.5𝑚𝑜𝑙 𝑥 0.821.1𝑎𝑡𝑚 𝑚𝑜𝑙−2 𝑘 −1 𝑥 273𝑘 6.581 𝑎𝑡𝑚−2
p= −
0.8𝑙−(0.5𝑚𝑜𝑙 𝑥 0.561−1 ) (0.81)2

= 14.52 atm -2.57atm = 11.95atm

The pressure in b is less than that in a

GRAHAMS LAW OF DIFFUSION

All gases spontaneously diffuse into one another to form a homogenous mixture. The relative rates
at which they diffuse depend on their densities. Graham law states that under the same conditions
the relative rates of diffusion of gases are inversely proportional to the square-root of their
densities
Thus for gases A and B

𝑟𝐴 √𝑝𝐵
=
𝑟𝐵 √𝑝𝐴
Where r = rate of diffusion

ρ= density
rA √MB
= where m =molar mass
rB √MA
𝑀
Since ρ=𝑉
𝑚

Example 1
50 cm3 of gas A effuse through a tiny hole in 146s. The same volume of CO2 effuses under the
same conditions in 115s. Calculate the molar mass of gas A.

𝑅𝑎𝑡𝑒 (𝐶𝑂2 ) 50⁄

= 115 = √ 𝑀𝐴
𝑅𝑎𝑡𝑒 (𝐴) 50⁄ 𝑀𝐶𝑂2
140
2
𝑀𝐴
(1.27)2 = (√𝑀𝐶𝑂 )
2

𝑀𝐴
(1.27)2 =
𝑀𝐶𝑂2
𝑀𝐴
(1.27)2 =
44
MA= 71g mol-1
Example 2
At a given temperature and pressure, a certain amount of proper C3H8 require 235s to effuse
through a porous plug. How long will it take an equivalent number of moles of CO to diffuse under
the same conditions?

𝑡𝐴 𝑀𝐴
𝑡𝐵
= √𝑀𝐵 Since t α density
Molar mass of proper = 44.09 g/mol
Molar mass of CO = 28.01 g/mol
Substituting the equation we get,

tco 28.01 g/m

= √ = 0.797
tC3 H8 MB44.09 g/m

tco = (0.797)(235s) = 𝟏𝟖𝟕 𝐬

N.B. Lighter gases take less time to diffuse than heavier gas. CO is lighter than propane therefore
it takes less time.
Assignment
1. At a given temperature and pressure a certain amount of argon (Ar) requires
277s to diffuse through a porous plug. How long will it take an equivalent
number of moles of (N2) to diffuse under the same conditions?

WEEK 4
CHEMICAL EQUILIBRIA
The condition in which the concentrations of all the reactants and products cease to change with
time is called chemical equilibrium. Chemical equilibrium occurs when opposing reactions are
proceeding at equal rates. The rate at which the products are formed from the reactant equals the
rate at which the reactants are formed from products. Chemical equilibrium are important in many
industrial processes.
The concept of Equilibrium
The state of equilibrium can be defined as a condition in which are the substances involved have
reached a final value of the concentration.
Consider the reaction between acetic acid and Ethanol for form ester.
CH3COOH +CH3CH2O ⇌ CH3COOC2H5 +H2O
C2H5OH
Acid Alcohol Ester Water
Initially only acid and alcohol are present. When the two are mixed ester and water are formed.
The reaction will proceed in that direction until such a time when the products are more than the
reactants. H2O and ester react to form acid and alcohol. This process will proceed until the time
when the rate of forward reaction is equal to the rate of backward reaction. Such an equilibrium is
referred to as dynamic equilibrium.
N.B. In a dynamic equilibrium the reactions have not stopped but they are of equal rates. The
symbol ⇌ is used to indicate equilibrium. Consider a general reaction,
aA +bB ⇌ cC +dD
where A,B,C and D are the chemical species involved and a,b,c and d are their coefficients in a
balanced chemical equation. We can express the equilibrium condition as
[𝐶]𝑐 [𝐷]𝑑
Kc = [𝐴]𝑎[𝐵]𝑏

Kc is called the equilibrium constant. It measures the extent in which the reactants are converted
into products before the equilibrium is reached. The concentrations is given in mol dm-3 when Kc
is obtained. Generally we can say that,
𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛𝑠 𝑟𝑎𝑖𝑠𝑒𝑑 𝑡𝑜 𝑡ℎ𝑒 𝑎𝑝𝑝𝑟𝑜𝑝𝑟𝑖𝑎𝑡𝑒 𝑝𝑜𝑤𝑒𝑟 𝑜𝑓 𝑡ℎ𝑒𝑖𝑟 𝑚𝑜𝑙𝑒𝑠
Equilibrium constant = 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑖𝑠𝑒𝑑 𝑡𝑜 𝑡ℎ𝑒 𝑎𝑝𝑝𝑟𝑜𝑎𝑡𝑒 𝑝𝑜𝑤𝑒𝑟 𝑜𝑓 𝑡ℎ𝑒𝑖𝑟 𝑚𝑜𝑙𝑒𝑠

The square bracket signify molar concentration.

For example
Write the equilibrium expression Kc for the following reactions.
a. CH3CO3H + C2H5OH ⇌ CH3COOC2H5 +H2O

[𝐶𝐻 𝐶𝑂 𝐶 𝐻 ]1 [𝐻2 𝑂]1

Kc = [𝐶𝐻 3𝐶𝑂 2𝐻]21 [𝐶5 1
3 2 2 𝐻5 𝑂𝐻]

b. I2(aq) +2Fe2+(aq) ⇌2I-(aq) +2Fe3+(aq)

2
[I− ]2 [Fe3+ ]
Kc = [I2 ][Fe2+ ]2

c. 3H2 +5N2⇌ 2NH3

[𝑁𝐻3 ]2
Kc = [𝐻 3 [𝑁 ]
2] 2

For a reaction of an alcohol with acid at 50oC the concentration of each substance at equilibrium
is given as [Acid] = 2.2 M [Alcohol] = 3.6 M, [ester]= 5.2 M [H2O]=3.8 M.
CH3CO2H +C2H5OH ⇌ CH3COO2C2H5 +H2O
[𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻]1 [𝐻2 𝑂]1 5.2𝑀 𝑋 3.8𝑀
Kc = [𝐶𝐻2 𝐶𝑂2 ]1 [𝐶2 𝐻5 𝑂𝐻]1
= 2.2𝑀 𝑋 3.6𝑀
 = 2.5

Example 2
Calculate the Kc for the reaction
2SO2 (g) +O2(g) ⇌ 2SO3(g)
If [SO2] =0.68 M, [O2] = 0.88 M and [SO3] =2.3 M
[𝑆𝑂3 ]2 [2.3M]2
Kc = [𝑆𝑂 2 =
] [0.68M]2 [0.88M]
= 13 M −1
2 ] [𝑂2

Notes
1. An equilibrium when all reactants are in the same phase is referred to as homogeneous. If
the reactants are in different phases it is described as heterogeneous.
Example
a. CO2(g) +H2 (g) ⇌ CO(g) +H2O(g) Homogenous
b. 3Fe(s) +4H2O(g) ⇌ Fe3O4(s) +4H2(g) Heterogeneous
2. This size of Kc tells us whether an equilibrium feverous reactants or products.
i. A large Kc indicates the concentration of product is large than the concentration of
reactants at the equilibrium.
ii. A small Kc indicates the concentration of the reactants is larger than the
concentration of the products at the equilibrium.
iii. If Kc is close to one the concentration of products and reactants are similar at the
equilibrium.

Assignment
a. Calculate the Kc for the equilibriums
2NO2 (g) ⇌ O2 (g) +2NO (g)
If [NO2] =0.016 M, [O2] = 0.13 M, [NO] = 0.26 M

b. Calculate the Kc for the following equilibrium

CO2(g) +H2(g) ⇌ CO(g) +H2O(g)

WEEK 4
MAGNITUDE OF EQUILIBRIUM CONSTANTS.
The magnitude of the equilibrium provides us with important information about equilibrium
mixture. In order for the equilibrium to be so large the denominator of the equilibrium must be
much larger than the numerator and vice-versa.
Kc>>>>>>> I equilibrium lives to the right products favored
Kc <<<<<<< I equilibrium lives to the left, reacts favored.
For example
COCl2 (g) ⇌ Co (g) +Cl2 (g) Kc = 2.2 x 10-10 reactants favored
2NO2 (g) ⇌ N2O4 (g) Kc =2.15x102 product favored
An equilibrium is able to shift in either direction i.e towards the reactants or products when a stress
is introduced in the equilibrium. The direction in which the equilibrium shifts is predicted by Lee
– Chartelier’s principle. It states that in any equilibrium, when a charge is made to some
external factor (such as temperature or pressure) the change in the position of equilibrium
is such as to tend to change the external factor in the opposite direction that removes the
stress.
Factors that affect equilibrium
1. Changes in concentration
When the connection of the reactants or products is increased the equilibrium will shift in
the direction that allows reduction in the concentration.
Consider the reaction
BiCl3 (aq) +H2O (l) ⇌ BiOCl (g) +2HCl (aq)
If little HCl is added the position of the equilibrium will shift the direction that will absorb
the excess acid i.e backward reaction takes place. More BiCl3 and H2O are formed.
2. Change in pressure
This mainly affects the gaseous reactions
For example
N2 (g) +3H2 (g) ⇌ 2NH3 (g)
If the pressure of the equilibrium mixture is increased the equilibrium shift in direction that
tends to decrease the pressure. This favored the reaction in which the number of molecules
are reduced. In the above reaction the number of molecules reduce in the ratio 4:2 in the
forward reaction. Hence increase in pressure favors production of ammonia gas.
3. Change in temperature
Changes in temperature have a great effect on the equilibrium. If the temperature is
increased the system adjust in the direction that absorbs the excess heat.
 a) For an Exothermic reaction
N2 (g) +3H2 (g) ⇌ 2NH3 (aq) …….. = -92 KJ mol-
Increases is temperature favors that reaction that removes the excess heat. In this case the
backward reaction is favored; more N2 (g) and H2 (g) are produced. Decrease in temperature
favors the forward reaction since it produces more heat hence more NH3 is produced.
b) Endethemic reaction
N2 (g) +O2 (g) ⇌ 2NO (g) ……… +180 KJ MOl-
Increase in temperature favors the reaction which absorbs more heat in this case the forward
reaction is favored hence more NO is produced.
4 Catalyst
Catalyst do not alter the position of the equilibrium. They only change the rate at which
equilibrium is attained.
Note: when writing the expression for Kc only include the components that are in the same
phase and NOT solids
Example
CaCO3 (g) ⇌ CaO (g) +CO2 (g)
Kc = [CO2] or Kp =PCO2
2HCl(g) +CaCO3(g) ⇌ CaCl2 (aq) +CO2 (g)
[𝐶𝑎𝐶𝑙2 ]
Kc = [𝐻𝐶𝑙]2
or K(c) = [CO2] =PCO2

Examples
a. Consider the equation

CO (g) + 2H2 (g) ⇌ CH3OH at 500 K

Calculate the equilibrium constant Kc and state whether it favors the reactants or products.
If [CO] = 0.091 M, H2 = 0.0822 M, [CH3OH] = 0.00892 M
When dealing with gases Kc = Kp
3[𝐶𝐻 𝑂𝐻] [𝐶𝐻 𝑂𝐻]
3
Kc = [𝐶𝑂][𝐻 2 ≡ Kp = [𝐶𝑂][𝐻 2
2] 2]

[0.00982𝑚]
= [0.0911][0.0822]2 = 14.5 M-2

Since the value of Kc >1. The equilibrium favors the products.

b. Consider the following equilibrium
 CO (g) +H2O(g) ⇌ CO2 (g) +H2 (g) Kc = 23.2 at 600 K
If the initial amount of CO and H2O were both 0.1M what will be the amount of each at
equilibrium
CO (g) + H2O(g) ⇌ CO2 (g) + H2 (g)
Initial 0.1M 0.1M 0 0
Change -x -x x x
Equilibrium 0.1-x 0.1-x x x
[𝐶𝑂2 ][𝐻2 ]
Kc = [
𝐶𝑂 ]⌈𝐻2 𝑂⌉

(𝑥)(𝑥)
= (0.1−𝑥)(0.1−𝑥)
= 23.2

𝑥2
23.2 = (0.1−𝑥)2
= 23.2

𝑥2
√(0.1−𝑥)2 =√23.2

𝑥
=0.1−𝑥 = 4.85

x= 0.485-4.85x
x+4.85x = 0.485
5.85x =0.485
0.485
x = 5.85 = 0.0829 M

Therefore [CO2] = [H2] = 0.0829 M

When gaseous reactants and products are considered the partial pressure are used to obtain Kp
For example in the decomposition of HI is given as follows
2HI (aq)⇌ H2 (g) + I2 (g)
PH2 .PI2
Kp = (PHI)2

Example 1
When 1mole of HI is allowed to dissociate in a 1.0dm3 vessel at 440 oC only 0.78moles of HI are
present at the equilibrium. What is the equilibrium constant Kp for this reaction
2HI (g) ⇌ I2 (g) + H2 (g)
Initial 0.22
Equilibrium 0.78 0.11 0.11
𝑃𝐼2 .𝑃𝐻2
Kp = (𝑃𝐻𝐼)2

Since 0.22 moles of HI decomposed 0.11 moles of I2 and H2 are formed at equilibrium
(0.11)(0.11) 1
Kp = (0.78)2
= 50 = 0.02

Example 2
If 2 moles of Hydrogen and 1mole of iodine are mixed together in a 1dm3 vessel at 440oC. How
many moles of HI, H2 and I2 will be present at equilibrium?
2HI ⇌ H2 + I2
Initial 2 1
Moles at equilibrium 2x 2-x 1-x
Assume that x moles of H2 and x moles of I2 are used then 2x moles of HI will be formed
2𝑥 2−𝑥 1−𝑥
Concentration at equilibrium moles/dm3 =
1 1 1
(2−𝑥)(1−𝑥)
Kp = =0.02 [Kp=0.02]
2𝑥

2−3𝑥+𝑥 2
= = 0.02
4𝑥 2

0.92x2 -3x+1 =0
Solving using the quadratic formula
−𝑏±√𝑏 2 −4𝑎𝑐
x= 2𝑎

We get x = 0.935
Hence at equilibrium
Moles of HI =2x =2x0.935=1.870
Moles of H2=2-x = 2-0.935=1.065
Moles of I2 -1-x=1-0.935=0.065
Example 3

At 300k and 1atm pressure di-nitrogen tetra-oxide is 20% dissociated into Nitrogen
dioxide. Calculate the equilibrium constant Kp for the reaction
N2O4(g) ⇌ 2NO2(g)
The fraction dissociated ∝ = 0.2
N2O4(g) ⇌ 2NO2(g)
Initial 1 0
At equilibrium 1-∝ 2∝
Total no of moles at equilibrium = 1-x+2x=1+x
1−∝𝑝
Partial pressure of N2O4 = 1+∝

PN2O2 = xp P= total pressure

2∝𝑝
Partial pressure of NO2 =
1+2

PNO2=xP
2∝ 2
𝑃 2 𝑁𝑂2 [ ] 4∝2 𝑝
1+∝
Kp=𝑃𝑁 = 1−∝ = (1−∝)(1+∝)
2 𝑂4
1+∝

4𝑥0.22 𝑥1𝑎𝑡𝑚
= (1−0.2)(1+0.2) = 0.167atm

Assignment
1. The equilibrium constant for the reaction
2NO2 (g) ⇌ N2O4 (g) at 298K is 200 mol-1dm3
a) Write an expression for the equilibrium constant for the reaction
b) If the concentration of N2O (g) in the equilibrium mixture at 298K is 2x 10-2 mole dm-3.
What is the concentration of NO2 (g)
c) Calculate the equilibrium constant at 298K for the reaction
½ N2O4 (g) ⇌ NO2 (g)
2. The equilibrium constant (Kp) for the synthesis of HCl (g)
HBr(g) and HI(g) are given below
Kp
H2 (g) +Cl2 (g) ⇌ 2HCl (g) 1017
H2 (g) +Br2 (g) ⇌ 2HBr (g) 109
H2 (g) + I2 (g) ⇌ 2HI (g) 10
a. What due the values of Kp tell you about the extent of the reaction
b. Which of the reactions would you regard as virtually complete
WEEK 5
RELATIONSHIP BETWEEN Kc AND Kp
Consider the equilibrium
N2 (g) +3H2 (g) ⇌ 2NH3 (g)
The expression for the equilibrium constant is given by
[NH3 ]2
Kc = [N 3
2 ][N2 ]

The partial pressure of each gas, i, can be expressed as

ni
Pi=( v ) RT = C, RT

Since Kp is given by the expression

P2 NH
Kp= PN.P3H3
2

Then
(CNH3 RT)2 C2 NH3 1
Kp= CN = [CN ] x (RT)2
2 RT.(CH2 RT)3 2 CH2

Kc
Kc
=(RT)2 = Kc (RT)-2

It can be seen that in this case kp ≠ Kc, in general

Kp = Kc(𝑅𝑇)∆𝑛 for the above equation ∆𝒏 = 2-4= -2
Where,
∆𝑛 is the difference between the number of molecules of products and those of reactants.
For H2 (g) +I2 (g) ⇌ 2HI (g) ∆𝑛 = 0
Hence Kp = Kc
In the reaction N2O4 (g) ⇌ 2NO2 (g).
Example
For the equilibrium 2SO3 (g) ⇌ 2SO2 (g) +O2 (g) at 1000 K the Kc has the value 4.07 x10-3. Calculate
the value for Kp. (R=0.082 L atm K−1 mol−1)

Kp = Kc(RT)∆n
 ∆𝑛 = 3 − 2 = 1
Kp = 4.07x 10-3 x 0.0821 x 1000
= 0.334
NB:
1. Kp and Kc have …….no units are said to be dimension less
2. In calculating the Kp, partial pressures are always in atm
3. The value of Kp and Kc are not necessarily the same because of the differences in units
Kp = Kc only when ∆𝑛 = 0

IONIC EQUILIBRIA
The equilibria between ions in solution are of particular interest because of their importance in
industrial analysical and biological processes. The principles and characterics of there ionic
equilibria are of course very similar to those used in considering other systems in chemical
equilibrium.
The equilibrium law may be applied to the equilibrium that exists between an almost insoluble
solid and its ions in solution and this gives condition for parcipitation of that solid in water at
constant temperature until attained, the rate at which Ag+ and Cl- go into solution is the same as
the rate at which they came out of solution back into the crystal laltice
Thus AgCl(g) ⇌ Ag+(aq) +Cl-(aq)
[Ag+ −
aq ][Claq ]
Keq = [AgCls ]

But [AgCl] represent the concentration of a pure solid which is a constant.

Therefore Keq = [Ag+][Cl-] ≡ Ks = [Ag + ][Cl− ]
Ks is known as solubility product given by the symbol Ksp
Example 1
A saturated solution of silver chloride contains 1.46 x 10-3 gm dm-3 at 18 oC. What is the solubility
product of silver chloride at this temperature?
([Ag] =108, Cl =35.5)
Solubility of AgCl = 1.46 x 10-3gm dm-3
1.46 𝑥 10−3
= mol dm-3
143.5

= 1 x10-5mol dm-3
At Equilibrium
 AgCl(g) ⇌ Ag+(aq) + Cl-(aq)
[Ag+] = 1 x 10-5mol dm-3
[Cl-(aq)] = 1 x 10-5mol dm-3
Ksp (AgCl) = [Ag+ (aq)] [Cl-(aq)]
= (1 x 10-5) Mol dm-3 x (1 x 10-5) mol dm-3
= 10-10 mol2 dm-6
Example 2
The solubility product of silver carbonate at 20 oC is 8 x 10-12 Mol3 dm-9. What is its solubility at
this temperature?
Let the solubility be S mole dm-2
At equilibrium

Ag2CO3(s) ⇌ 2Ag+ (aq)+ CO2−

3 (aq) = 8 x 10
−12
mole3 dm−9

= [2𝐒]2 (s) = 8 x 10−12 mole3 dm−9

4𝐬3 = 8 x 10−12 mole3 dm−9
𝐒 3 = 2 x 10−12 mole3 dm−9
S=𝟏. 𝟐𝟓𝟗 𝐱 𝟏𝟎−𝟒 𝐦𝐨𝐥𝐞 𝐝𝐦−𝟑
≈ 𝟏. 𝟐𝟔 𝐱 𝟏𝟎−𝟒 𝐦𝐨𝐥𝐞 𝐝𝐦−𝟑
i.e the solubility of silver carbonate at 20 oC is 1.26 x 10−4 mole dm−3
Example 3
Calculate in g/l the solubility of AgCl at 25 oC if its solubility product is 2 𝑥 10−10 mol2 litre−2 at
this temperature.
Ag = 108, Cl=35.5
Ksp= [Ag + ][Cl− ] = 2 x 10−10 mol2 litre−2

[Ag + ][Cl− ] = √2 x 10−10

= 𝟏. 𝟒𝟏𝟒 𝐱 𝟏𝟎−𝟓 𝐦𝐨𝐥 𝐋𝐢𝐭𝐫𝐞−𝟏

But, the silver chloride concentration will be the same as that of its ions.
Therefore AgCl= 1.414 x 10−5 mol Litre−1
Solubility g/L = mole Litre x molar mass of AgCl
 = 1.414 x 10−5 x 143.5s Litre−1
= 𝟐. 𝟎𝟐𝟗 𝐱 𝟏𝟎−𝟑 𝐠 𝐋𝐢𝐭𝐫𝐞−𝟏

Assignment
1. The equilibrium concentration are [N2O4] = 0.00452 M, [NO2] = 0.0310 M at 1000 oC.
Calculate the value of Kp.
2. For Haber process
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
Kc = 9.60 at 300 oC calculate Kp for this reaction at this temperature. Kp = 0.335
3. Determine Kp value given the following information
N2O4 ⇌ 2NO2 (g) Kc = 5.9 x 10-3 at 2980K

WEEK 6
ION PRODUCT OF WATER
Pure water ionizes to a very small extent according to the following equilibria
+ −
H2O (l) ⇌ H(aq) + OH(aq)

This process is referred to as auto ionization of water at room temperature only 1 out of about 100
molecules is ionized at any given instant. No individual molecules remains ionized for ions the
equilibria is extremely rapid. Equilibrium expression for auto ionization of water is
[H+ −
aq ][OHaq ]
Keq = [H2Ol ]

But the concentration of water remains effectively a constant and Keq is very small.
Hence [Keq][H2O] =Kw =[H+][OH-]
The products of the two constant [Keq][H2O] define a new constant Kw which is referred to as
ION-PRODUCT constant for water
Kw has a value 1 x10-14 mol2 l-2 at 25oC
 Kw = [H+][OH-] = 10-14
Hence [H+] = [OH-] =10-7
A solution is which [H+] =OH-] is said to be neutral
Note
Any changes on the [H+] or [OH-] cause stress in the system which causes a shift in the system
according to le-charteliers principle. For an acidic solution, [H+] > [OH-] whereas for basic
solution has [H+] < [OH-] and this ensures the products [H+][OH-] is always a constant 1 x10-14
Example
Calculate the values of [H+] and [OH-] in a neutral solution at 25 oC. If Kw =10-4
By definition in a neutral solution [H+] = [OH-]
Let the concentration of each of the species be x.
Then [H+][OH] = 1.0 x 10-14
x x = 1.0 x 10-14
𝑥2 = 1.0 x 10−14
𝑥 = 𝟏. 𝟎𝐱𝟏𝟎−𝟕
ℎ𝑒𝑛𝑐𝑒 [𝐻 + ] = [OH-] = 𝟏. 𝟎𝐱𝟏𝟎−𝟕
in acid solution [H+]is greater than 1.0x10−7 M
In basic solution [OH-] is more than 1.0𝑥10−7 M
WEEK 7
THE PH SCALE
The concentration of H+ (aq) in an aqueous solution is usually small. We therefore express [H+] in
terms of pH.
pH of a solution is the negative logarithm to base 10 of the molar hydrogen ion concentration

1
PH= -log10 [H+] = log +
10 [H]

The PH scale ranges from 1-14

For a neutral solution at 25 oC
[H + ] = 1.0 x 10−7 M
PH = −log[1.0 x10−7 ] = −(−7) = 7
−7
−[log 1 + log1010

−[log 1 − 7 log10
10 ]

=0 +7

Therefore a PH of a neutral solution is 7.00

Note
pH = log10 [H + ]
p(OH-) = -log10 [OH − ]
In any solution [H + ][OH − ] = 1 x 10−14 and therefore pH + p OH =14
Examples
1. Calculate the PH of a solution whose hydrogen ion concentration is 0.001M l-1
+
PH = −log[Haq ]
= -log (0.001)
= -log 10 10-3
= 3[log 10 10]
=3
2. Calculate the PH of a solution with hydrogen in concentration of 6.28 x10-6Ml-1
PH= -log [H+]
=-log (6.28 x 10-6)
= - [log 6.28 +log 10-6]
 = -[log6.28-6]
= -0.798 + 6
= 5.202
It is also possible to describe alkalinity by PH because
[H+][OH-] = 1 x 10-14
Taking negative logarithm given
PH +p[OH] = 14
PH = 14 –P[OH]
Examples
1. Calculate the PH of a 0.001M solution of sodium hydroxide
P(OH-) = -log[OH-] = -log 1x 10-3 =3
PH = 14-P(OH)
=14-3
=11
2. Calculate the hydrogen in concentration in a solution with a pH of 8.54
–log [H+] = 8.54
Log [H+] = -8.54
[H+] = 10-8.54
[H+] = 2.88 x 10-9 M

3. Calculate the pH of 0.011M solution of Ca(OH)2

Ca (OH)2 ⇌ Ca2+ + 2OH-
[OH-] = 2 x 0.011M = 0.022
[OH-][H+] = 1 x 10-14
1 𝑥 1014 1 𝑥 10−11
H+ = 2 𝑥 0.011 = = 0.045 𝑥 1011
22

=4.5 𝑥 10−13
PH= log H + = − log(4.5 𝑥10−13 )
=12.34
Alternatively
P OH= - log (0.022)
=1.66
But PH = 14-P OH
= 14-1.66
 = 12.34

Assignment
1. Calculate the concentration of H+(aq) in
a. A solution in which [OH] is 0.010 M
b. A solution is which [OH-] is 2x10−9 M
2. Calculate the concentration of OH- (aq) in which
a. [H+] = 2x10−6 M
b. [H+] = [OH-]
c. [H+] = 10-2 M
3. Calculate the PH of lemon juice whose [H+] = 3.8 x 10-4 M.
4. Calculate the PH of a solution whose [H+] =5.3 x 10-6 M
5. Calculate [H+] of an acid solution made by dissolving a tablet whose pH =9.18
6. What is the concentration of a KOH solution whose PH is 11.89

WEEK 8

BUFFER SOLUTIONS
Buffer solutions resist charges in PH on addition of acid or alkali. Buffer are important in many
industrial processes where the PH must not deviate very much from the optimum value. In national
processes a change in only 0.5 pH of blood or body fluid can be fatal.
Buffer solutions usually consist of either
i. A solutions of weak acid in presence of ore of its salts eg ethanoic acid/sodium
Ethanoate, carbonic acid and NaHCO3 , propanoic acid/sodium propanoate
[H2CO3 ⇌ 𝐻𝐶𝑂3− + H3O+
Weak acid conjugate base

ii. Weak base in the presence of ore of its salts e.g ammonia solution /ammonium chloride
In order to understand how a buffer works we consider a hypothetical weak acid, H A in a solution
of its salt MA. In this solution HA will be slightly dissociated with MA is fully dissociated into its
ions
MA ⇌ H+ +A-
MA → M+ +A-
Hence the mixture contains a relatively high concentration of un–ionized HA (acid) and a relatively
high concentration of A- (a base). If the acid is suddenly added into this system H+ ions in the acid
will combine with A- to form un-ionized HA. Provided there is a large reservoir of A- ions in the
buffer nearly all the added H+ ions are removed.
Thus [H+] charges very little and the pH is only slightly altered. Alternatively if NaOH is suddenly
added to the system OH- combine with H+ to form water. This reduces the concentration of H+ in
the buffer solution. More HA dissociate to restore the equilibrium and the concentration of H+ rises
to almost its original value provided there is a large reservoir of HA in the buffer. The
concentration of H+ changes very little and again the pH is slightly altered.
A stable pH is due to
i) A high [A-] which traps added H+ ions
ii) A high [HA] which can supply H+ to trap OH-
Example
Weak acid HA dissociates according to the equation
HA ⇌ H+ (aq) +A- (aq)

INDICATORS
An acid /base indicator is either a weak acid or weak base that exhibits color change as the core of
H+ or OH- changes in aqueous solution eg. Litmus, methyl orange, phenolphthalein, bromothymol
blue. The indicators used in acid –base titrations are weak acids or weak bases the ions are of a
different color from un-dissociated molecules.

In solution
HL + H2O ⇌ H3O+ + L-
Red Conjugate base blue
The molecules HL are red and the anion L- are blue. The dissociation constant of the indicator is
[𝐻3 𝑂 + ][𝐿− ]
Ka = 𝐻𝐿
In acid solution [H3 O+ ] is high
H3O+ combine with L ions to form HL molecules which are red. In alkaline solution H3O+ are
removed to form L ions which are blue.
HL + OH- ⇌ L- +H2O
If [HL] = [L-] the indicator appears purple
Methyl orange is a weak base which can be represented by B
B+ H3O+ ⇌ BH+ + H2O
B molecules are yellow (base)
BH+ cations are red (Acid)
Examples
1. A buffer consist of 0.03M propanoic acid (Ka=1.4 x 10-5) and 0.30 M sodium propanoate.
What is pH of the buffer.
[𝐴− ]
PH = PKa + log [𝐻𝐴]

PKa = -log [Ka]

PKa= -log (1.4 x 10-5)
PKa=4.85
0.30
PH =PKa +log 0.30

PH =4.85 + 0
= 4.85

2. Calculate the PH of a buffer prepared by adding 20gms of NH4Cl to enough 0.75M NH3 to
produce 500 ml of solution (0.750 M NH3/ 0.748 M NH4+ buffer) PH = 9.247.
What is the pH of 3.00 ml of 0.100m KOH added to 100.0 ml of the buffer?
What is the pH of buffer solution that is 0.24 M NH3 and 0.20 M of NH4Cl
Ka = 5.6x10-10
A−
PH = PKa +log [HA]

PKa = −log(5.6 x 10−10 ) = 9.25

0.24
PH = 9.25 + log 0.20

pH = 12.5 +0.08 = 9.33

 a) If 0.005mol of NaOH is added to 0.50L of the buffer solution (0.24M NH3 and 0.20m
NH4Cl) what is the resulting pH?
0.005
= 0.01M [conc. of OH − ]
0.50
Buffer reaction NH4+ + OH − ⇌ H2 O + NH3
I 0.20 0.01 0.24
C - 0.01 0.01 0.01
E 0.19M 0 0.25M
I –initial
C- Change
E-Equilibrium

0.25M
PH = 9.25 + log
0.19
= 9.25 +0.12
= 9.37

b) If 0.03 mol of HCl is added to 0.50L of the buffer solution (0.24M NH3 and 0.20 M NH4Cl)
what is the resulting pH
mol 0.03
[HCl] = = = 0.06M
L 0.50L

NH3 + H + in solution Acid ⇌ H + + H2 O ⇌ H3 O +

NH3 + H3 O+ ⇌ NH4+ + H2 O
I 0.24 0.06M 0.20
C 0.06 -0.06M +0.06
E 0.18 0 0.26

𝐴− 0.18
PH = PKa +log [𝐻𝐴] = 9.25 + 0.26
= 9.25 -0.16
pH = 9.09
3. Calculate the final PH of a buffer solution containing 0.1M Sodium acetate and 0.2M acetic
acid (PKa = 4.76 following addition of 0.05M NaOH
CH3COOH ⇌ CH3COO- + H+
CH3COONa ⇌ CH3COO + Na+
I +0.05 +0.05
C 0.2-0.05 +0.05
E 0.15 0.15

pH = 4.76 +log 0.1 +0.05

0.2 -0.05
0.15
PH = 4.76 +Log 0.15
= 4.76
4. Suppose that 0.0200m NaOH is dissolved in 300ml of the following buffer solution.
0.40 M NaCH3CO2(aq) and 0.080 M CH3COOH(g).
What is the final PH of the solution?

PH of the solution in absence of added NaOH Pka =4.75

𝐴− 0.04
PH = Pka + log 𝑁𝐴 PH = 4.75 Log 0.08 = 4.45
After adding NaOH
NaOH + CH3COOH ⇌ NaCH3COO- + H2O
Moles = conc x V
CH3COOH = 0.08 x 3l = 0.0024

CH3COO- 0.04 x3l = 0.012 M

For the equation

CH3COOH + NaOH ⇌ NaCH3COO- + H2O

I 0.024 0.02M 0.012M
C -0.02 -0.02 +0.02
E 0.004 0 0.032

[CH3COOH] = 0.004/0.3l =0.013M

[ CH3COO-] = 0.032/0.3L = 0.107M
 𝐴− 0.107
P= PKa + log 𝑁𝐴 = 4.75 + Log 0.013

= 4.75+0.915
= 5.65

5. What is the PH after 1.0ml of 0.10M HCl is added to 10ml of Buffer

1ML =0.00L 10ML =0.01L
Total vol = 0.001L + 0.01L = 0.011L
Change in concentration 0.001L - 10ml
0.001 𝑥 0.1
0.011 0.011

= 9.1 x 10-3 HCl

Propanoic acid = 0.30M + 9.1 x 10-3 = 0.31M HA
Propanoate = 0.30M-9.1 x 10-3 = 0.29 MA-
0.29
PH =4.15 + log 0.31 = 𝟒. 𝟖𝟐

6. Calculate the PH of a buffer solution that is 0.250M in HCN and 0.170M in KCN for HCN
Ka=4.9 x 10-10 (PKa = 9.31)
base
PH = PKa + log acid
0.170
= 9.31 + log 0.250 = 𝟗. 𝟏𝟒

Assignment
1 Calculate the PH of a buffer solution that is 0.050 benzoic acid HC7H5O2 and 0.150 M in sodium
benzoate. NaC7H5O2). ka for benzoic acid = 6.5 x 10-5

WEEK 9

Henry’s law
Henry’s law is concerned with solubility of gases in liquids. It states the mass of gas dissolved
at Constant temperature per unit volume of solvent is directly proportional to the partial
pressure of the gas. This law may be expressed as
Ms =Kp
Where Ms is the mass of gas dissolved p is its partial pressure and K is a constant. The solubility
of a gas is the volume which will dissolve in unit volume of the solvent under stated conditions of
temperature and pressure. Eg the solubility of CO2 at 30oC and 1atm is 30cm3 in 1.0dm3 of water.
The absorption coefficient is the volume of gas (at s.t.p) that will dissolve at partial pressure of
1atm and a stated temperature in unit volume of the liquid
e.g the absorption coefficient of Nitrogen in water at 20oC is 0.010.
henry law dos not apply to gases which combine chemically with the solvent e.gHCl in solution in
water
example
if the composition of volume of air is 80% Nitrogen and 20% oxygen. Calculate the volume
composition of dissolved air in water at 20oC the absorption coefficients at 20oC are Nitrogen,
0.016 Oxygen 0.031 (ssume the volume of water was 100cm3)
ans
mole fraction Nitrogen =0.80
oxygen =0.20
the partial pressure of each ga is proportional to its mole fraction.
The absorption coefficient must be multiplied is the mole fraction to give the absorption th gas at
its partial pressure.
Vol of Nitrogen at s.t.p dissolving in 100cm3 water
= 100 x 0.016 x 0.80 = 1.28cm3
Vol of oxygen at stp dissolving in 100cm3 water
= 100 x 0.031 x 0.20 = 0.62cm3
Nitrogen =67%
Oxygen =33%
LIQUIDS
In liquids the molecules are closer together than in a gas.
The formation liquid from a gas due to attractive between molecules
The amount of heat required to convert 1 mole of liquid to vapor at 1am is called standard enthalpy
of vaporization
……..
Amount of heat is released when 1mole of solid into liquid at 1atm and is called standard Enthalpy
of melting…..
Molecules of liquid are in constant motion some of them have enough energy to excape from the
liquid into vapour state.
Molecules that remain in the liquid are of lower energy than those that escape.
The fraction of molecules with high energy increases as the temperature rises and therefore the
rate of evaporation increases with temperature. If the liquid is in closed container snd dome sre
directed back into the liquid (condense)
An equilibrium is reached when the rate at which molecules of liquid evaporate is equal to the rate
at which molecules of liquid evaporates is equal to the rate at which molecules of vapour condense.

As the molecules of vapour collide with the walls of the container the exert a pressure .the
maximum vapour pressure that can be developed is called saturated vapour pressureand itincreases
with temperature.
It depends on the liquid and the temparaturebut not the amount of liquid present.
Saturated vapour pressure is measured with a mercury barometer .

The liquid is introduced into the barometer and floats at the top of the mercury .the vapour formed
exerts pressure and the levels of mercury drops .the saturated vapour pressure is obtained by the
difference (h1-h2)mm for this temperature.
If a liquid is heated in an open container its saturated vapour pressure increases until it becomes
equal to the atmospheric pressure .at the point bubbles of vapour form in the interior of the liquid
and escapes into the atmosphere ,because the vapour pressure is high enough to push the air
asideand the liquid boils.the boiling temperature(point)is the temperature at which its vapour
pressure svp is equal to the external pressure normally 1atm pressure [its possible for a liquid to
boil below its boiling point]
Distillation under reduced pressure (vacuum distillation) is used in the purification of substances
which decompose at their boiling temperatures.
A pure liquid can be identified by its boiling point. When a boiling point is measured the
thermometer must measure the temperature of the vapour in equilibrium with the boiling liquid. It
should not be immersed in the liquid because of superheating.
The saturated vapour pressure of a liquid can be used to calculate the mass of the liquid that s
present in the vapour states in a given volume at a stated temperatures.
Example
A 1dm3 vessel contains air at 1.01 x 105NM-2 and 0oc. After 1.0gm of water introduced into the
vessel, the temperature was raised to 90oc. Calculate the mass of water that will vaporize. The
saturated vapour pressure of water at 90oc is 6.99 x 104 NM-2
Ans
Use the ideal gas equation
PV-nRT
Substitute P=6.99 x 104 NM-2 R= 8.314Jk-1Mol-1 T=363K
V=1.0dm3 =1 x 10-3 M3
𝑁 𝑀3
𝑃𝑉 6.99 𝑥 104 𝑥 0.001 𝑥
𝑀3
n= 𝑅𝑇 = = 3
𝑘
= 2.32 𝑥 10−2 𝑚𝑜𝑙
8.314 𝑥 363 .𝑘
𝐾𝑀

Mass = 2.32 𝑥 10−2 𝑥 18 = 0.417𝑔

Ideal solution- a mixture in whcu the molecules of different species are distinguishable and excut
the same and independent forces
Enthalpy o solution is zero volume mixing it zero

WEEK 10
SOLUTIONS OF LIQUID IN LIQUIDS
SOLUTION
A solution is a homogenous mixture of two substances. The saturated vapourpressue of the mixture
of liquids depends on the svp of the component and the composition of the mixture,
The composition of the mixture of each liquid is expressed as a mole fraction of each constituent.
For a mixture of liquid A and B
Mole fraction X for mole fraction
 𝑛𝐴
XA= 𝑛𝐴+𝑛𝐵

IdeaL SOLUTION
RAUNLTS LAW
It states that the saturated vapour of each component in the mixture is equal to the product of the
mole fraction of that component and the saturated vapour pressure of that component when pure.
This can be expressed as
PA =
Reanults law is obeyed by mixtures of similar compounds and they for Ideal solutions
An ideal solution has equal intermolecular forces no change in enthalpy (heat) and volume when
mixing.
The vapour above a mixture does not have the same composition as the liquid
If A is more volatile than B

The vapour is richer in the more volatile component

If

Example
A 80oC the vapour pressure of benzene is 10.0 x 104 NM-2 and that of methylbenzene is 4.0 x
104NM-2. Estimate the mole fraction of methylbernzene in the vapour in equilibrium with a liquid
mixture of benzene and methylbenzene at 80oC in which the mole fraction of methylbenzene is
0.60
Method
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑚𝑒𝑡ℎ𝑦𝑙𝑏𝑒𝑛𝑧𝑒𝑛𝑒 𝑖𝑛 𝑣𝑎𝑝𝑜𝑢𝑟 0.60 4.0 𝑥 104
= 𝑥 = 0.60
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐵𝑒𝑛𝑧𝑒𝑛𝑒 𝑖𝑛 𝑣𝑎𝑝𝑜𝑢𝑟 0.40 10 𝑥 104
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑚𝑒𝑡ℎ𝑦𝑙𝑏𝑒𝑛𝑧𝑒𝑛𝑒
Mole fraction of methylbenzene = 𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠

Amt of methylbenzene vapour = 0.6 𝑥 4𝑥 104

= 2.4 𝑥 104
Amount of Benzene =0.4 𝑥 10 𝑥 104 = 4 𝑥 104
….𝑥 2.4 𝑥 104
Mole fraction = = 0.375
6.4 𝑥 104

Vapour pressure composition curve for an ideal mixture of liquids

In a mixture where liquid A is more volatile than liquid B. the composition of the vapour in
equilibrium with the liquid mixture of different compositions is as shown.
The total saturaturatedvapour pressure is the sum of the partial vapour measured PA+PB when
the total vapour pressure is v, the composition of the vapour by the point v the live v …….. L is
called a tie time. The vapour is richer than the liquid in the more votilecomponent A.
Non ideal solutions
Non ideal solutions have vapour pressure greater or less than those predicted from Raounltlaw
.they exhibit positive and negative deviations from the Raounlt law.
Solutions which have v. pressure greater than predicted from Raoults law show positive deviations
from the law while those with vapour pressure lower than predicted are said to show negative

deviation
Boiling – temperature composition curve for systems which show deviations from Raounlts law
If the liquid with composition M is boiled the vapour has the same composition as the Tb don’t
change as distillation is continue
It is called Azeotropic o contact boiling mixture e.g Nitric acid / water Tb is maximu Benzene
/EthanolTb is minimum)
Azeotropic mixture is a mixture of two or more liquid whose proportions cannot be altend o
changed by simple distillation. This is because same popotions o constituents as the unboiled
mixture
A saturated solation is a chemical solution containing the maximum concentration of a solute
dissolved in a solvent. Additional solute will no dissolve in a saturated solution.

SOLUTION
A solution contains much solute as can be dissolved solute as can be dissolved at that temperature.
In presence of undissolved solute.
In a saturated solution a state of dynamic equilibrium exists with particles of solid. Constantly
dissolving and solute constantly being deposited.
The quantity of solid that dissolves in a certain quantity of liquid to form a saturated solution is
called the solubility of the solid.
Solubility is expressed as a solute dm-3 solution mol dm3 solute kg-1 solvent mol kg-1, mol
fraction mol dm-3
The solubility of a soluite can be found by
i. Titrimetric analysis
ii. Evaporation aknown mass of solution to dryness and weighning the solute that remains
iii. Conductometric analysis
M2
Area above the curve shows
Solubility concentration and temperature
g solute c/m-3 at which saturated solution
Are formed curve below shows the cohension,the
concentration
M1 And temperature at which unsaturated solution
exist
M3 T1 T2
Colligative [properties are properties of saolutions that depend on the ratio of the number of solute
particles to the number of solvent molecules in a solution on not on the nature of the chemical
species present
A solution at point X contains M2g of solute in 1 kg of solvent at temperature t3.
It is an unsaturated solution and when it is cooled it does not deposit solute until it reaches a
temperature t2. A t2 solute is deposited ans the concentration of the solution decreases. On further
cooling more solute is deposited and the concentration of the solution decreases. As the
temperature falls the concentration follows the curve YZ. At temperatures ti the mass of solute that
can remain in solution is M.g. the mass of solute that has crystallised between t2 and t1 is (M2-
M1)
A solution w containing M3g of solute in 1kg of solvent at t3 can be cooled from t3 to t1 without
depositing any solute as the solubility is never excellent
Recrystallization
Solids are purified by recrystallization from a suitable solvent e.g water ethanol propononeetc the
impure material is dissolved in the minimum quantity of hot solvent. The hot solution is filtered
to remove insoluble impurities. The filtered solution is allow to cool so that thesolutecrystalling
out. The impurities are present in smaller quantities and remain in solution at lower temperature.
The purity of solid is assed by finding its melting temperature. Colligative properties of solutions
are properties that depend upon thw concentration of solute molecules but not the identity of the
solute. They include lowering … pressure boiling point elevation freezing point depression and
….. pressure
Lowering of the vapour pressure of a
1. solvent by a solute
For solution of two liquids A and B , the Raounlt law states that the saturated vapour pressure of
each component. In the mixture is equal to the product of the mole fraction of that component and
the saturated vapour pressure of that component when pure
P= XAPAo + XBPBO
Where XA = mole fraction and of A
PAo = saturated vapour pressure of pure A
XB mole fraction of B
In a solution of solid B in liquid a is solid is involatile𝑃𝐵𝑜 IS neglible
Then P= 𝑋𝐴 𝑃 𝐴𝑜
Since XA is a fraction
P< 𝑃𝐴𝑜
The presence of a solute has lowered the saturated vapour pressure of the solvent.
It follow that the lowering of the vapour pressure 𝑃𝐴𝑜 – P is equal to the mole fraction of the solvate
𝑝𝑜 −𝑝 𝑛1
=𝑛
𝑝𝑜 1 𝑛2

𝑝𝑜 = 𝑣𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡

P= vapour pressure of folution
𝑛1 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑒
𝑛2 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
The molar mass of state can be found from lowering of the vapour pressure that it produces
𝑝𝑜 −𝑝 𝑛
= 𝑛1 in dilute solutions 𝑛2 ≫≫ 𝑛1
𝑝𝑜 2

Notice that the lowering of the saturated vapourpressure depends on the molar concentration of
the solute Not on its identity. Substituting
𝑚
n=𝑀 𝑤ℎ𝑒𝑟𝑒 𝑚 = 𝑚𝑎𝑠𝑠
𝑚1
𝑝𝑜 −𝑝 𝑀1 𝑚1𝑀1
m= molar mass gives = =
𝑝𝑜 𝑚2/𝑀2 𝑚2𝑀1

if the masses of solute and solvent are known and the malor mass of the solvent is known, this
expression can be used to give M1 molar mass of the solute.
e.g A solution of 100g of solute in 1.0dm3 of water has a vapourpressure of 2.27 x 103 Nm-2 at
20oC. The saturated vapour pressure of water at 20oC is 2.34 x 10Nm-2
Calculate the molar mass of the solute
𝑝𝑜 −𝑝 𝑛 𝑀 𝑀
= 𝑛1 𝑀1 𝑀2
𝑝𝑜 2 2 1

2.34 − 2.27 100 18

= 𝑥
2.34 1000 𝑀1
18 𝑥 2.34
𝑀1 = = 60𝑔𝑚𝑜𝑙 −1
0.07 𝑥 10
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
Molarity = = (𝑚)
1𝑘𝑔 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
Molarity = 1 𝑙𝑖𝑡𝑟𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑀

2. elevation of Boiling temperatures

A solvent raises the temperature at which the solvent boils
This is because the presence of the vapour pressure of a solvent
The graph below shows the relationship between the lowering of the vapour pressure and the
elevation of the boiling point.

1.0Atm External pressure

Vapour Pure solvent

Pressure Solution ∆𝑇𝑏
4Tb = mKb
Boiling point of T1 T2 boiling point
of solution
solvent
∆𝑇𝑏 = 𝑇2 − 𝑇1
∆𝑇𝑏Is propotional to the molar concentration of solution.
WEEK 11

The boiling temperature of Ebullioscopic constant

The boiling temperature elevation is proportional to the concentration of solute. The elevation
produced.
∆𝑇𝑏 = 𝑇𝑏 ∝ 𝑚 And∆𝑇𝑏 = 𝑇𝑏𝑚 where m is the molarity of solution and represents moles of
solutes in 1 kg of solvent Kb is called molar boiling point elevation constant or molar boiling point
constant or ebullioscopic constant.
By 1 mole of solute in 1kg of water is 0.52kg. This value is called the ebulliscopic constant or
(boiling temperature constant) for water
For the other solutions, the boiling temperature elevation depends on the concentration of solute
and the magnitude of the ebullioscopic constant for the solvent.

Boiling temp elevation = boiling temperature constant X amount of solute/mol =K X M/W X

1/W
Mass of solvent/kg
Where k = ebullioscopic constant for the solvent (boiling point constant)
M = mass of the solvent
M = molar mass of the solute
W = mass of solvent (kg)
If w is expressed in kg, then
Boiling temperature elevation = K x m/g X 1
M/gmol-1 w/kg
Example
Calculate the molar mass of X if 5.00gm of X in 100.0g of water boiled at 100.420c
Boiling temperature = k x m/m x 1/w
0.42k = 0.52k x 50/m x 1/0.1
M = 62g/mol-1
The depression in freezing point temperature is directly proportional to the molar concentration of
the solute (number of molecule).
3. Depression of the freezing temperature of the solvent by a solute.
A solution has a lower freezing temperature (or freezing point) than the pure solvent freezing
temperature depends on concentration of particles in solution and not their nature.
1 mole of solute in 1 kg of water lower the freezing temperature by 1.86k.
The molar depression of the freezing temperature is called the cryoscopic constant (or freezing
temperature constant) of the solvent.
Freezing freezing
Temperature = temperature X amount of solute/mol = k x m/m x1/w
Depression constant mass of solvent/kg

Where m- mass of solute

M- The molar mass of the solute W-The mass of solvent in kg
K- Cryoscopic constant (Freezing units are K kgmol-1)
The graph below shows the vapour pressure curve for a solvent a solid solvent and a solution

vapour P1 Pure solvent

pressure Solid solvent solution
P2
∆𝑇𝑓 = 𝑚𝑘𝑓 T2 T1 Temperature

T1 is the freezing temperature of the solvent i.e the temperature at which its vapour pressure-
temperature curve intersects that of pure solvent, T2 is lower than T1. The solute has depressed
the freezing temperature of the solvent.
Example
A solution of 5.12g of Y in 100g of water froze at -0.28oc. if the cryiscopic constant for water is
1.86K kgmol-1, what is the molar mass of Y?

𝑚 1
Freezing temperature =𝐾 𝑥 𝑥
𝑀 𝑊
depression
5.12𝑚 1
0.280= 1.86 𝑥 𝑀
𝑥 0.1
The molar mass M = 340gMol-1
Heat capacity for momo-atomic gases
Mono.atomic is a combination of two words “mono” and atomic and means a single atom. A
mono.atomic gas is one in which atoms are not bound to each other for example all noble gases
are mono-atomic, agron, neon reryron etc.
The motion of a mono.atomic gas is translation. Thus in an adiabatic process mono.atomic gases
have an idealized Y-factor i.e heat capacity ratio or adiabatic index or ratio of specific heats or
poison constant. Is given by ratio of heat capacity at constant volume Cr
It is denoted by Y gamma
𝑐𝑝 𝑐𝑝
𝛾= =
𝑐𝑟 𝑐𝑟
Where c is he heat capacity and c the specific heat capacity (heat capacity per unit mass) of a gas
The suffixes p and v refer to constant pressure and constant volume.
An adiabaitic process takes place without transfer of heat or mass of substances between a
thermodynamic system and its surrounding. In an adiabatic process energy is transferred to the
surrounding only as work.
𝑐𝑝 5
𝛾= =
𝑐𝑟 3
5
Because molar heat capacity at constant Cp = 2 𝑅
35
Molar heat capacity at constant V Cr= 𝑅
2

Where R is the gas constant

 5
𝑐𝑝 𝑅 5
𝛾= = 33 = 3 = 1.67
𝑐𝑟 𝑅
2

This also applies to the ideal gas

Therefore the theoretical values of Cr, Cp and 𝛾 𝑎𝑟𝑒 𝑖𝑛 𝑎𝑔𝑟𝑒𝑒𝑚𝑒𝑛𝑡 𝑓𝑜𝑟 𝑚𝑜𝑛𝑜 −
𝑎𝑡𝑜𝑚𝑖𝑐 𝑜𝑟 𝑎𝑛𝑦 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠

WEEK 12

COLLIGATIVE PROPERTIES
These are properties of the solution which depend only on the number of solution particles but not
on the nature of solution.
They include:
i. Relative lowering in vapour pressure.
ii. Elevation in boiling point.
iii. Depression in freezing point.
iv. Osmotic pressure.
Relative lowering in vapour pressure.
When a non- volatile solute is added to a solvent, the vapor pressure of the solution decreases.
Let Xa be the mole fraction of the solvent
Let Xbo be the mole fraction of the solute and Pa be the vapour pressure of the pure solvent of
p be the vapour pressure of the solution.
Since the solute is non volatile, there will be no contribution of solute to the vapour pressure
and the vapour pressure of the solution will be only due to the solvent. Therefore, the vapour
pressure of solution (p) will be equal to the vapour pressure of the solvent (PA) over the
solution.
P= PA
PA = X A P A
PB = XB PB0
Since Xa is always less than one the vapour pressure of the solution is always less than poA i.e.
the vapour pressure of pure solvent
P < poA.
 The presence of a solute has lowered the saturated vapour pressure of the solvent.
Pure solution solute + solvent

Solute interferes with solvent

molecule for evaporating
vapour pressure existence.
Mole solute = lower pressure
P solution = x solvent x po solvent.