Physical Chemistry BUK

DEPARTMENT
OF
PURE AND INDUSTRIAL CHEMISTRY
BAYERO UNIVERSITY, KANO
CHM 1251 – PHYSICAL CHEMISTRY

LEVEL ONE LECTURE NOTES
2012/2013 SESSION
FOR STUDENTS FROM FACULTIES OF

SCIENCE
MEDICINE
ENGINEERING
AGRICULTURE
EDUCATION
By
MAGAJI LADAN
Dr. SAMINU MUHAMMAD DAGARI
AYUBA ABDULLAHI MUHAMMAD
Dr. UMAR IBRAHIM GAYA
Dr. ABDULLAHI NUHU
Dr. MUHAMMAD BASHIR IBRAHIM
SHEHU HABIBU
ABUBAKAR USMAN KATSINA
MUSTAPHA GARBA DANLAMI
DEAL GASES
I An Ideal Gas is any gas that obeys the equation of state PV = nRT.
Where P is the pressure of the gas, V is the volume, n is the number of moles, R
is the molar gas constant and T is the temperature.
DERIVATION OF IDEAL GAS EQUATION

The ideal gas equation is derived by combining Boyle’s and Charles’s laws and
Avogadro’s hypothesis.
From Boyle’s law
P1V1 = k1 and P2V2 = k2 ……………………………..1
From Charles’s law,
V1/T1 = k1 and V2/T2 = k2 …………………………….2
1|Page CHM 1251 -PHYSICAL CHEMISTRY (2012/13 SESSION)
Combining (1) and (2) gives;
= k1 and = k2 or = k …………...............3
For a fixed mass of gas, the constant is proportional to the number of moles, n.
= (constant) x n …………………………………..4
The new constant is called R, the molar gas constant.
So, = nR or PV = nRT ………………………………… 5
PV= nRT (5) is known as the IDEAL GAS EQUATION.
The ideal - gas equation is called an equation of state for a gas because it contains all
the variables (T,P,V and n) which describe completely the condition or state of any gas
sample. If we know the three of these variables, it is enough to specify the system
completely because the fourth variable can be calculated from the ideal-gas equation.
The Numerical value of R. From the ideal-gas equation, we can write
R=
We know that one mole of any gas at STP occupies a volume of 22.4litres. Substituting
the values in the above expression, we have
R= = 0.0821atmLmol-1K-1
R has various equivalent values depending on the units of P and V used in the ideal-
gas equation.
R can also be expressed in Jmol-1K-1 as follows.
1atm = 1.0132 105Nm-2 and 1dm3 = 10-3m3.
R= 0.0821 atmLmol-1K-1 = 0.0821 atmLmol-1K-1x 1.0132 105Nm-2x10-3m3xatm-1xdm-3 =
8.314J mol-1K-1 where 1J= 1Nm.
Therefore R= 8.314J mol-1K-1
CALCULATING THE NUMBER OF MOLES, n

Number of moles =
Example: Calculate the number of moles of the following gases;

1) 5.6g of Nitrogen gas, N2(g) 2) 1.32g of CO2(g)
Solution:
1) nN2(g) = (5.6/28)mol = 0.20mol
2) n CO2(g) = (1.32/44)mol = 0.03mol
The usefulness of the ideal gas equation is that it relates the four variables, P,V,n and
T, that describe a sample of gas at one set of conditions.
Example:
What pressure, in atmosphere is exerted by 54.0g of Xe in a litre flask at 293K?
Solution:
V= 1.0L, n= 0.411mol, T = 293K and P=?
Solving PV=nRT for P and substituting gives P= nRT/V
= (0.411mol)( 0.0821 atmLmol-1K-1)(293K)/1.0L; P = 9.89atm
EXPRESSING PV=nRT INTERMS OF DENSITY, ρ

Density is defined as mass per unit volume i.e ρ=m/v …….1
For an ideal gas PV=nRT
V = nRT/P ……………………………………..2
Put eqn 2 in 1, we have
ρ = Pm/nRT …………………………………..3
But n= mass/molar mass = m/M ………………4
Put eqn 4 in 3
ρ = PM/RT ……………………………………5
Example: Calculate the density of Ammonia (NH3) in gL-1 at 0.989atm and 55oc.
Solution: The molar mass of NH3, N is 17.03gmol-1
ρ = PM/RT = (0.989atm)( 17.03gmol-1)/ ( 0.0821 atmLmol-1K-1)(328K); ρ =0.625gL-
1
DALTON’S LAW OF PARTIAL PRESSURE

States that the pressure of a mixture of gases is equal to the sum of the pressures of
all of the constituent gases alone.
Mathematically; Total Pressure, PT = P1 + P2 + ……… Pn
Consider a mixture of 2 gases A and B. We are to show that Total Pressure, P T =
Partial Pressure of A, PA + Partial Pressure of B, PŶ
i.e PT = PA + PB
For a gaseous mixture, the volume of each component as well as the final volume is
the same.
By definition;
ntotal = n A + nB ………………………………………….1
from ideal gas equation PV=nRT
ntotal = PtotalV/RT ……………………………………….2
nA = PAV/RT ……………………………………………3
nB = PBV/RT……………………………………………..4
substitute 2, 3,and 4 in 1
PtotalV/RT = PAV/RT + PBV/RT
Ptotal = PA + PB …………………………………………..5
Equation 5 is the mathematical expression of Dalton’s law of partial pressure.
MOLE FRACTIONS
By definition nA + nB = ntotal ……………………………….1
Divide eqn.1 through by ntotal
nA/ ntotal + nB/ ntotal = ntotal/ ntotal = 1
XA + XB = 1, where XA = nA/ ntotal, the mole fraction of A and XB = nB/ ntotal, the mole
fraction of B.
The sum of the mole fractions of the components of a mixture is equal to 1.
RELATION BETWEEN PARTIAL PRESSURE, MOLE FRACTION AND TOTAL

PRESSURE.

Consider an ideal gas mixture (binary) of A and B. From the ideal gas equation
PV=nRT;
PA = nART/V ………………………………………………….i
Ptotal = ntotalRT/V ………………………………………………ii
Divide eqn (i) by eqn (ii)
PA/ Ptotal =nA/ntotal = XA …………………………………………iii
:. PA = XA Ptotal …………………………………………………..iv
The partial pressure of a particular component is equal to its mole fraction multiplied
by the total pressure.
Exercise: What pressure is exerted by a mixture of 2.0g of H2 and 8.0g of N2 at 273K
in a 10litre container?
KINETIC MOLECULAR THEORY OF GASES

Maxwell and Boltzmann (1859) developed a mathematical theory to explain the
behavior of gases and the gas laws. It is based on the fundamental concept that a gas
is made of a large number of molecules in perpetual motion. This theory is called the
Kinetic Molecular Theory or the Kinetic Theory of Gases.
Assumptions of the KMT
1) A gas consists of extremely small discrete particles called molecules dispersed
throughout the container. It means that the actual volume of the molecules is
negligible compared to the total volume of the gas. The molecules of a given gas
are identical and have the same mass (m).
2) Gas molecules are in constant random motion with high velocities. They move in
straight lines with uniform velocity and change direction on collision with other
molecules or the walls of the container.
3) The distance between the molecules is very large and it is assumed that van der
Waals attractive forces between them do not exist. Thus the gas molecules can
move freely, independent of each other.
4) All collisions are perfectly elastic. Hence, there is no loss of the kinetic energy of
a molecule during collision.
5) The pressure of a gas is caused by the hits recorded by molecules on the walls
of the container.
6) The average kinetic energy (1/2mv2) of the gas molecules is directly proportional
to absolute temperature. This implies that the average kinetic energy of
molecules is the same at a given temperature.
FUNDAMENTAL EQUATION FOR THE PRESSURE OF A GAS.

PV= mNu2
This is the fundamental equation of the kinetic molecular theory of gases. It is
called the Kinetic Gas Equation. This equation although derived for a cubical vessel,
is equally valid for a vessel of any shape. The available volume in the vessel could
well be considered as made up of a large number of infinitesimally small cubes for
each of which the equation holds.
u2 is the mean of the squares of the individual velocities of all the N molecules of
the gas.
KINETIC GAS EQUATION INTERMS OF KINETIC ENERGY
Let N be the number of molecules in a given mass of gas,
PV= mNu2 ……………………………………1
= mNu2 ……………………………………2
= N e…………………………………………..3
where e is the average kinetic energy of a single molecule.
Therefore, PV= Ne = E …………………………4
where E is the total kinetic energy of all the N molecules. The equation (4) is called
the kinetic gas equation in terms of kinetic energy.
We know that the general ideal gas equation is PV= nRT……………5
From (4) and (5) above
E = nRT………………………………………………6
For one mole of a gas, the kinetic energy of N molecules is,
E= ……………………………………………….7
Example: Calculate the kinetic energy of two moles of N2 at 27oC. Take R =
8.314JK-1mol-1
Solution: We know E = nRT, where n = 2.0mol, T = (27 + 273) K = 300K
and R = 8.314JK-1mol-1
on substitution we have E = X 2.0mol X 8.314JK-1mol-1 X 300K =7482.6J
Therefore the kinetic energy of two moles of N2 is 7482.6J.
DEDUCTION OF GAS LAWS FROM THE KINETIC GAS EQUATION

1) Boyle’s Law
According to the Kinetic Theory, there is a direct proportionality between absolute
temperature and average kinetic energy of the molecules i.e.,
mNu2 T or mNu2 = kT ………………………..1
mNu2 = kT or mNu2 = kT …………………2
Substituting the above value in the kinetic gas equation PV = mNu2, we have
PV = kT ……………………………………3
The product PV, therefore, will have a constant value at a constant temperature.
This is Boyle’s Law.
2) Charles’ Law: As derived above,
PV = kT ……………………………………………..i
Divide bothsides of equation (i) byV,
V = k/P.T ……………………………………………..(ii)
At constant Pressure, P.
V = k’T ……………………………………..(iii)
Where k’ = k/P,

Or V T …………………………………………(iv)
This implies that, at constant Pressure, volume of a gas is proportional to Kelvin
temperature and this is Charles Law.
3) Avogadro’s Law: Consider equal volume of 2 gases at the same pressure,
PV = m1N1u12 ………………………………..(i) kinetic eqn of 1st gas
PV = m2N2u22 ………………………………..(ii) kinetic eqn of 2nd gas
Therefore, m1N1u12 = m2N2u22 ………………(iii)
When the temperature (T) of both the gases is the same, their mean kinetic
energy per molecule will also be the same.
m1u12 = m2u22 ……………………………..(iv)
Dividing (iii) by (iv), we have
N1 = N2
Or, under the same conditions of Temperature and Pressure, equal volumes of
the 2 gases contain the same number of molecules. This is Avogadro’s Law.
4) Graham’s Law of Diffusion:

If m1 and m2 are the masses and u1 and u2 the velocities of the molecules of
gases 1 and 2, then at the same pressure and volume.
m1N1u12 = m2N2u22 ……………………….1
By Avogadro’s Law, N1 = N2 …………………………………….…2
m1u12 = m2u22 ………………………………......3
If M1 and M2 represent the molecular masses of gases 1 and 2, then,
( )2 = ………………………….……4
= ……………………………5
The rate of diffusion (r) is proportional to the velocity of molecules (u),
therefore,
= = ….6
This is Graham’s law of diffusion.
ROOT MEAN SQUARE VELOCITY

If V1, V2, V3 ……………….. Vn are the velocities of n molecules in a gas, U2, the mean of
the squares of all the velocities is:
Taking the square root, we have,
U is thus the Root Mean Square Velocity or RMS velocity. It is denoted by U.

The value of the RMS of velocity U, at a given temperature can be calculated from the
kinetic gas equation.

For one mole of gas, ………………………………………………………………………… (3)
Therefore,
And,
Where M = molar mass
By substituting the values of R, T and M, the value of U (RMS velocity) can be

determined.
RMS velocity is superior to the average velocity considered earlier. With the help of U,
the total kinetic energy of a gas sample can be calculated.
REAL GAS
Distinction between Ideal and Real gases
1. An ideal gas is infinitely compressible; a real gas will condense to a liquid at
some pressure.
2. The particles of an ideal gas lose no energy to its container. A real gas conducts
and radiates heat, thereby losing energy.
3. There is no attraction between the molecules of an ideal gas. A real gas has
particle attractions.
4. An ideal gas can follow the formula A real gas does not follow this
formula.
DEVIATIONS FROM IDEAL BEHAVIOUR
An ideal gas is one which obeys the gas laws or the gas equation at all
pressures and temperatures. However, no gas is ideal. Almost all gases show
significant deviations from the ideal behavior. Thus the gases H2, N2 and CO2 which fail
to obey the ideal gas equation are termed non ideal or real gases.
COMPRESSIBILITY FACTOR
This is a quantity that measures the deviation of a real gas from ideal behaviours. It is
defined by the equation;
Where Z = compression factor
P, R and T have their usual meanings.

=> Z = 1 at all conditions.
For a real gas, Z depends on the value of PVm relative to RT.
At high pressures PVm > RT so that Z > 1. The gas is said to deviate positively from
ideality and is less compressible than an ideal gas.
At low pressure, PVm < RT. Z is less than 1. The gas deviates negatively from ideality
and is more compressible than an ideal gas.
CONCLUSIONS
From the above discussions, it can be concluded that:
1. At low pressures and fairly high temperatures, real gases show nearly ideal
behavior and the ideal gas equation is obeyed.
2. At low temperatures and sufficiently high pressures, a real gas deviate
significantly from ideality and the ideal gas equation is no longer valid.
3. The closer the gas is to the liquefaction point, the larger will be the deviation
from the ideal behavior.
EXPLANATION OF DEVIATION – VANDER WAALS EQUATION

Van der Waals (1873) attributed the deviations of real gases from ideal behavior to
two erroneous postulates. These are:
i. The molecules in a gas are point masses and possess no volume.
ii. There are no intermolecular attractions in a gas.
Therefore, the ideal gas equation derived from kinetic theory could not hold
for real gases. Van der Waals pointed out that both the pressure (P) and volume (V)
factors in the ideal gas equation need to be corrected in order to make it applicable to
real gases.
Volume Correction
The volume of a gas is the free space in the container in which molecules move about.
Volume V of an ideal gas is the same as the volume of the container. The dot
molecules of ideal gas have zero-volume and the entire space in the container is
available for their movement. However, Vander Waals assumed that molecules of a
real gas are rigid spherical particles which possess a definite volume.
The volume of a real gas is, therefore, ideal volume minus the volume occupied by gas
molecules. If b is the effective volume of molecules per mole of the gas, the volume in
the ideal gas equation is corrected as: (V-b)
For n moles of the gas, the corrected volume is (V-nb)
Where, b is termed the excluded volume which is constant and characteristics for each
gas.
Excluded volume is four times the actual volume of molecules. Therefore, excluded
volume is not equal to the actual volume of the gas molecules.
Pressure Correction
A molecule in the interior of a gas is attracted by other molecules on all sides. The
attractive forces cancel out. But a molecule about to strike the wall of the vessel is
attracted by molecules on one side only. Hence it experiences an inward pull.
 A molecule about to strike the wall has a net inward pull;
 A molecule in the interior of gas has balanced attractions, therefore, it strikes the
wall with reduced velocity and the actual pressure of the gas, P, will be less than the
ideal pressure. if the actual pressure P, is less than Pideal by a quantity p, we have P =
Pideal – p or Pideal = P + p. P is determined by the force of attraction between
molecules (A) striking the wall of container and the molecule (B) pulling them inward.
The net force of attraction is, therefore, proportional to the concentration of (A) type
molecules and also of (B) type molecules. That is,
or or P =
Where n is the total number of gas molecules in volume, V and a is the proportionality
constant. Thus the pressure P in the ideal gas equation is corrected as
(P+ for n moles of gas.
VAN DER WAALS EQUATION

Substituting the values of corrected pressure and volume in the ideal gas equation,
, we have
(P+
This is known as Vander Waals equation for n moles of a gas. For 1 mole of a gas
(n=1), Vander Waals equation becomes ( P +
Constant a and b in Vander Waals equation are called Vander Waals constants. These
constants are characteristic of each gas.
DETERMINATION OF a AND b
From the expression P = , the value of a is given by the relation a = =
atmlitre2mol-2 if the pressure is expressed in atmosphere and volume in litres. Thus a is
expressed in atmlitre2mol-2 units. Since nb is excluded volume for n moles of gas, b =
= its volume is expressed in litres, b is in litre mol-1 units.
SI Units of a and b
=
= Nm4mol-2
b = Volume mol-1 = m3mol-1
Example: Calculate the pressure exerted by 1.00mole of methane (CH4) in a 250mL

container at 300K using Van der Waals equation. What pressure will be predicted by
ideal gas equation? Take a= 2.253atmL2mol-2, b= 0.0428Lmol-1 and R=
0.0821atmLmol-1K-1.
Solution
(P +
P = 82.8atm.
The ideal gas equation predicts that
P = nRT/V = 98.5atm.
LIMITATION OF VAN DER WAALS EQUATION

Van der Waals equation explains satisfactorily the general behavior of real gases. It is
valid over a wide range of pressures and temperatures. However it fails to give exact
agreement with experimental data at very high pressures and low temperatures.
EXERCISES
1) One mole of CO2(g) occupies 0.382x103m3 at 40oC. Calculate the pressure that
the gas would exert assuming ideal behavior. Take R = 8.314Jmol-1K-1.
2) Convert the following Physical quantities to the required units: 365cm to m,
22400cm3 to dm3 then to m3 and 760torr to Nm-2.
3) The hottest place on record in North America is Death Valley in California. It
reached a temperature of 134oF in 1913. What is this temperature reading in
degrees Celsius? In Kelvins?
4) The total pressure exerted by a mixture of 2 gases A & B is 76.2cmHg. The
number of moles of the 2 gases is 0.0075 and 0.0040 respectively. Calculate the
partial pressures of the 2 gases.
5) Nitric acid, a very important industrial chemical, is made by dissolving the gas
NO2(g) in water. Calculate the density of NO2 gas, in g/L, at 1.24atm and 50oC.
6) A sample of hydrogen gas (H2) has a volume of 8.56L at a temperature of OoC
and a pressure of 1.5atm. Calculate the moles of H2 molecules present in this
gas sample.
7) What is the volume of a gas balloon filled with 4.00moles of He when the
atmospheric pressure is 748torr and the temperature is 30oC?
8) Calculate the root mean square speed of O2 molecules in a cylinder at 21oC and
15.7atm.
9) The density of a gas was measured at 1.50atm and 27oC and found to be
1.95g/L. Calculate the molar mass of the gas.
10) Calculate the pressure exerted by 1.0mole of methane, in a
o
500mL vessel at 25 C assuming a) Ideal behavior and b) Non-Ideal behavior.
11) Define the compressibility factor of a gas. The compressibility
factors of 2 gases are ZA = 0.65 and ZB = 1.23 (i) state the nature of deviation
of each gas from ideality. (ii) How does the ease of compression of each gas
compare with that of an ideal gas?
HERMOCHEMISTRY
Thermochemistry is the study of energy changes, which occur during chemical

Treactions.
Definition of Some Terms

Enthalpy (H) is the quantity of heat, which flows into or out of a system at constant
pressure.
Enthalpy change (H) of a reaction is the difference between the sum of enthalpies of
products and the sum of enthalpies of reactants.
10 | P a g e C H M 1 2 5 1 - P H Y S I C A L C H E M I S T R Y (2012/13 SESSION)
 H =  H (products) –  H (reactants)
Unit of H
The unit of H used in thermochemical measurements is kilojoule (kJ). If the
amount of substance is 1mole, the unit of  H is kilojoule per mole (kJmol–1).
The old unit of H is kilocalorie (kcal) or kilocalorie per mole (kcal mol – 1).
The two units are related as follow:
Kcal mol–1 = 4.184kJmol–1
Exothermic reaction is a reaction in which heat is given out to the surroundings.
The energy diagram for this reaction is given below.
Reactants H = HP – HR, where HR, HP are

Energy
HR
the enthalpies of reactants and
H products. H is negative because
Products H is less than H .
P R
Reaction path
HP
Endothermic reaction: is a reaction in which heat is absorbed from the surrounding.

The energy diagram is given below:
Products
HP
 H = H P – HR
Energy
H  H is positive because
Reactants
HP is greater than HR
Reaction path
HR
THERMOCHEMICAL EQUATION
A thermochemical equation is a balanced chemical equation showing the physical
states of all reactants and products and the enthalpy change of the reaction.
Manipulating thermochemical equations
(i)If the balanced equation is reversed, the sign of  H is changed
(i.e. PLUS is changed to MINUS and vice-versa)
For example.
H2(g) + ½ O2(g)  H20(l).  H1= – 286kJ mol–1
Reversing the equation gives:
H2O(l)  H2(g) + ½ O2(g),  H2= –  H1 = + 286kJ mol–1
(ii) If the balanced equation is multiplied by a factor n,  H is also multiplied by the

same factor.
For example.
H2(g) + ½ O2(g)  H20(l).  H1= – 286kJmol–1
Multiplying the equation by 3 gives:
3(H2(g) + ½ O2(g)  H20(l),  H1= – 286kJ)
3H2(g) + 3 2 O2(g)  3H20(l), 3  H1= – 858kJ
NOTE: If H is multiplied by a number, “mol–1” is dropped in the unit.
(iii) The physical states of all reactants and products must be indicated in
thermochemical equations.
STANDARD ENTHALPY CHANGES

Standard enthalpy change of formation (  H of )
This is the heat change when one mole of a substance is formed from its constituent
elements at standard state.
To write a thermochemical formation equation, we need to know the physical states of
all reactants and products at standard state (i.e. a state at which P = 1atm and T =
25oC).
A thermochemical equation for the formation of water from its elements at standard
state. At standard state, hydrogen and oxygen are gases, water is a liquid. So, the
formation of water can be represented by the thermochemical equation;
H2(g) + ½ O2(g)  H2O(l), H of = – 286kJmol–1
Standard enthalpy change of combustion ( H oc )
This is the heat given out when one mole of a substance is completely burnt in
oxygen.
C s   O 2 g     CO 2 g  , H1
complete
Combustion
The enthalpy change of this reaction H1 is equal to H oc (C(s))

C s   12 O 2 g  Combustion
 CO g  , H 2
incomplete
The enthalpy change of the reaction H 2 is not equal to H oc (C(s))

The general equation for the combustion of a hydrocarbon CnHm is given by:
CnHm +  n   O2 ( g )  nCO2 ( g )  H 2 O(l )
m m
 4 2
Standard enthalpy change of sublimation H sub
o
 is the heat required to convert 1
mole of a solid substance to gas at standard state.
Na s  
 Na g  , H sub
o
Na s   = + 108kJmol–1
Standard enthalpy change of atomization H sub
o
 or dissociation H odiss  is the
heat required to convert a mole of gaseous molecules to atoms at standard state.
 2Cl g  H odiss Cl 2 g   = + 242kJmol
–1
Cl 2 g  
Ionization Potential (IP) is the energy required to remove an electron completely
from a gaseous metal atom.
Group IA elements (Li, Na, K etc) lose only one electron.
 N a g   e, IP Na g   = + 500kJmol
–1
Na g  
Group IIA elements (Be, Mg, Ca etc) and Group IIIA elements (e.g. Al) lose two
and three electrons respectively. The ionization occurs in steps.
 Alg  1st I P Al g   = + 578kJmol
–1
Alg  
 Al2g 2nd I P Al g   = + 1817kJmol
–1
Alg  
 Al3g 3rd I P Al g   = + 2745kJmol
–1
Al2g 
The I P (Al(g)) is the sum of the ionization potentials of the three steps above.
 Al3g  3e, I P Al g   = + 5140kJmol
–1
Alg  
NOTE: In numerical problems, where a metal ionizes in more than one step, you may
be given the overall I P, or the I P’s of the individual steps (from which the overall I P
can be determined)
Electron affinity (EA) is the energy absorbed or released when 1 mole of a gaseous
anion (negative ion) is formed from 1 mole of gaseous atoms.
Group VIIA elements (F, Cl, Br etc) gain only one electron.
 Cl g  , EA Cl  g   = – 364kJmol
–1
Cl  g   e  
Group VI (O, S etc) and group V (N, P etc) gain two and three electrons
respectively. The electron gain occurs in steps
Lattice energy H L  is the energy released when 1 mole of an ionic solid is formed
from gaseous ions.
 NaCl s  , H L NaCl s   = – 776kJmol
–1
Na g   Cl g  
 Al2 O 3 s  , H L Al 2 g O 3 s   = + 15301kJmol
–1
2Al3g  3O 2g 
Lattice dissociation energy H L D  is the energy absorbed when 1mole of an ionic
solid is dissociated into its gaseous ions.
H L D is equal and opposite in sign to H L for any substance.
Bond Energy (B E) is the energy released when 1 mole of a chemical bond is formed
from free gaseous atoms.
–1
 H  H, BE H  H = – 433kJmol
H g   H g  
–1
 C  H, BE C  H = – 413kJmol
C g   H g  
Bond Dissociation Energy (BDE) is the energy absorbed when 1 mole of a
chemical bond is dissociated into free gaseous atoms. BDE is equal and opposite in
sign to BE for any substance.
Standard enthalpy change of neutralization H neut  is the heat given out when
one mole of hydrogen ion from an acid is just neutralized by a base in dilute solution.
–1
 NaCl aq  H 2 Ol  , H neut = – 57.3kJmol
HClaq  NaOH aq 
When a strong acid is neutralized by a strong base, the heat of neutralization has
approximately a constant value of – 57kJmol–1. This is due to complete ionization of
the strong acid and the strong base.
However, when the acid or the base is weak, a further heat change is involved in
ionizing the weak acid or base. So, the enthalpy of neutralization is either greater or
less than – 57kJmol–1.
Standard enthalpy change of solution H solution
Integral heat of solution and heat of solution at infinite dilution
The integral heat of solution is the total heat change when one mole of a solute is
dissolved in a specified amount of solvent. For example, when 1mole of HCl is
dissolved in 50moles of water, 73kJ of heat are evolved. So, the integral heat of
solution is – 73kJmole–1.
 HCl50H 2 O, H = –73kJmol
–1
HCl q   50H 2 O l  
If a concentrated solution is diluted, the integral heat of solution changes further
depending on the amount of water added. For a very dilute solution, further dilution
would cause no additional heat change. The corresponding
H value is called the heat of solution at infinite dilution.
–1
HCl g   aq   HCl aq, H = –75kJmol
Heat of solution of ionic solids
The enthalpy change of solution of an ionic solid depends on the energy absorbed
in breaking up the crystal lattice H L D  and the energy released in hydrating the ions
H hydration .
H solution  H LD  H hydration
Depending on the relative values of H L D and H hydration , an ionic solid will dissolve
with absorption or evolution of heat.
Enthalpy Sign Enthalpy Sign

Change Change
Hf + or – EA + or –
HC – HL –
Hsub + HLD +
Hdiss + Hneut –
IP + Hsolution + or –
BE – BDE +
HESS’S LAW OF CONSTANT HEAT SUMMATION

When reactants are converted to products, the enthalpy change is the same
regardless of the path followed, provided the initial and final conditions are the same.
As a consequence of this law, thermochemical problems can be solved either
from
i) a thermochemical cycle or
ii) a combination of thermochemical equations
THERMOCHEMICAL (OR BORN – HABER) CYCLE

Consider the following reactions;
H1
A  B 
 P
A 
H2
C
B 

H3
D
P 

H4
C D
The reactions can be represented in a cycle as follows;
Path 1
A + B H 1
P
H 2 H 3
H 4
C + 2 D
Path
The conversion of P can be achieved either along path 1 or path 2. By Hess’s law, the
energy changes along the two paths are equal.
Energy change along path 1 = H1
Energy change along path 2 = H2 + H3 – H4
 H1 = H2 + H3 – H4
NOTE: The negative sign attached to H4 shows that path 2 is opposite to the
direction of the arrow.
Born – Haber cycle involving formation and combustion reactions

A general cycle involving formation and combustion reactions is given below;
Reactants at their Formation

equation Product
standard states
Combustion
equation
Combustion Combustion equation

products
If A and B react to give a product P, then will give the same combustion products
as P. This is the basis of the above cycle.
Example 16
The heats of combustion of H2(g) and C(s) are – 286 and – 393kJmol-1 respectively. The
heat of formation of benzene is +48.1kJmol-1
(a) Write thermochemical equations for the energy changes.
(b) Construct a Born-Haber cycle and use it to calculate the heat of combustion of
benzene.
Answer
(a) The thermochemical equations for the energy changes are:
combustion of H2(g)
1
H2(g) + O2(g)  H2O(l), H 1o = – 286kJmol–1 ……………..... (1)
2
Combustion of C(s)
C(s) + O2(g)  CO2(g), H 2o = – 393kJmol–1 …………………….. (2)
Formation of C6H6(l)
6C(s) + 3H2(g)  C6H6(l), H 3o = + 48kJmol–1………………………..(3)
Combustion of C6H6(l)
15
C6H6(l) + O2(g)  6CO2(g) + 3H2O(l), H 4o = ?……………… (4)
2
Next, use the thermochemical equations to construct a Born – Haber cycle
Steps
Write down the formation equation
6C(s) + 3H2(g)   C6 H6 (l)
Draw arrows to show the complete combustion of 6C(s) and 3H2 (g)
C6 H6 (l) will give the same combustion products as 6C(s) + 3H2(g) . So, draw an
arrow from C6 H6 (l) to 6CO2 (g) + 3H2 O(l)
The amount of O2(g) required to completely burn C6 H 6 l  is

3 15
6O 2 g   O 2 g   O 2 g 
2 2
6C(s) + 3H2 (g) C6 H6 (l)
6O2 (s) 3 15
2
O 2 g  2 O 2 g 
6CO2(s) + 3H2O(l)
Write the correct enthalpy change on each arrow H10 is the enthalpy change for the
combustion of 1H2 (g). So 3H 02 is the enthalpy change for combustion of 3H 2 g 
Similarly, 6H 02 is for 6C(s). H 30 and H 04 are the enthalpy changes for the formation
and combustion of C6H6 (l) respectively.
The complete thermochemical cycle is given below;
Path 1
H 3o
6C(s) + 3H2(g) C6H6(l)
6O2(g) 6 H 2o
3 H 4o
O2(g) 3 H 1o 15
O2(g)
2 2
6CO2(g) + 3H2O(l)
Path 2
The reactants 6C(s) + 3H2(g) can be converted to the product C6H6(l) either
along path 1 or path 2.
Enthalpy change along path 1 = H 3o

Enthalpy change along path 2 = 6 H 2o + 3 H 1o – H 4o
Note the negative sign attached to H 4o . It shows that the path taken is opposite to
the direction of the arrow.
By Hess’s law, the enthalpy changes along the two paths are equal.
H 3o = 6 H 2o + 3 H 1o – H 4o
48 = – 2358 – 858 – H 4o
H 4o = – 2358 – 858 – 48 = – 3264kJ
The heat of combustion of C6H6(l) is – 3264kJ.
Born-Haber cycle for polymerisation reaction

A general cycle for polymerisation reaction is given below;
Polymerisation
equation Polymer
n (monomer)
Combustion
equation
Combustion Combustion
products
equation
Example 17: Given that:

15
C6H6(l) + O2(g)  6CO2(g) + 3H2O(l), H 1o = – 3260kJ.
2
5
C2H2(g) + O2(g)  2CO2(g) + H2O(l), H 2o = –1300kJmol–1
2
Calculate the heat of polymerization of acetylene to benzene.
Answer
Let H 3o be the heat of polymerization of acetylene to benzene.
i.e. 3C2H2(g) C6H6(l), H 3o = ?
acetylene benzene
Born-Haber cycle
H 3 o
3C2H2(g)  C6H6(l)
15 NOTE:
H 1o O2(g)
15 2
3 H 2o O2(g) Convince yourself on how the
2 complete cycle is arrived at.
6CO2(g) + 3H2O(l)
By Hess’s law
–1
H 3o = 3 H 2o – H 1o = 3(– 1300) – (–3260) = – 640kJmol
Born – Baber cycle for formation of ionic solids

A general cycle is presented below;
H of
Ionic compound
Metal(solid) + Gaseous non-metal
18 | P a g e C H M 1 2 5 1 - P Hmolecules
Y S I C A L atomisation
CHEMISTRY (2012/13 SESSION)
sublimation
Gaseous
Metal(gas)
The above cycle shows the various processes involved in converting a metal, M, and a
non-metal gaseous molecule(s) to gaseous ions, and the formation of an ionic
compound from these ions.
Example 18
Calculate the lattice energy of sodium chloride from the following data;
–1
H of (NaCl(s)) = – 411kJmol
Heat of sublimation of Na(s) = +108kJmol–1
Dissociation energy of Cl2 (g) = 242kJmol–1 (endothermic)
 Na g  g  , I P = + 500kJmol–1
Na g  
EA (Cl(g)) = 364kJmol–1 (exothermic)
Solution
The thermochemical cycle for the formation of NaCl(s) is given below:
H of
Na(s) + 1 Cl2(g) NaCl(s)
2
H sub 1
H diss
2
Na(g) Cl(g)
H lattice
IP EA
Na+(g) + Cl – (g)
By Hess’s law.
H of = H sub
o
+ 1 H diss
o
+ IP + EA + H lattice
o
= H f – ( H sub +
o
H lattice
o o 1 H diss
o
+ IP + EA) …………………….. (1)
2
Given that, H of (NaCl(s)) = – 411kJmol, H sub Na ( g )  = +180kJmol–1
o
H odiss Cl 2 ( g )  =+242kJmol , IP Na ( g )  = +500kJmol , EA(Cl(g) = – 364kJmol .

–1 –1 –1
The lattice energy of NaCl(s) is calculated as follows

Substituting the above values in equation (1)
H lattice
o
= – 411– [108 + 1 (242) + 500 – 364] = – 411 – 365 = –776kJmol-1
2
Example 19: Study the following thermochemical cycle

H of Al2O3(s)
2Al(s) + 3 O2(g)
2
2 H 2 3
H 6
2
2Al(g)
3O(g)
2 H 3
3 H 7
H 9
2Al+(g)
2 H 4 3O(g)
2Al2+(g)
3 H 8
2 H 5
2Al3+(g) + 3O2– (g)
(a) Identify the enthalpy changes  H1,  H2……….  H9

(b) Calculate the lattice energy of Al2O3(s) given that
 H1 = –1676,  H2 = +324,  H3 = + 578,  H4 = + 1817,  H5 = + 2745,
-1
 H6 = +498,  H7 = –141,  H8 = +791kJmol ,  H9 =?
Answer
(a)  H1 = H f (A12O3(s),  H2 = H sub
o o
(Al(s)),  H3 = 1st IP of Al(g)
 H4 = 2nd IP of Al(g),  H5 = 3rd IP of Al(g),  H6 = H diss (O2(g))
o
 H7 = 1st EA of O(g),  H8 = 2ndEA of O(g),  H9 = Al2O3(g))

(b) By Hess’s Law,
3
 H1 = 2(  H2 +  H3 +  H4 +  H5) +  H6 + 3(  H7 +  H8) +  H9
2
3
 H9 =  H1 – 2(  H2 +  H3 +  H4 +  H5) –  H6 – 3(  H7 +  H8)
2
3
= –1676 – 2(324 + 578 + 1817 + 2745) – (498) – 3(–141 + 791)
2
= –1676 – 10928 – 747 – 1950 = – 15301
The lattice energy of Al2O3(s) is therefore –15301kJmol–1
Born – Haber cycle for bond energy calculations

This is a cycle for formation or combustion reactions into which dissociation,
sublimation and bond energy equations are included.
Examples 20: Calculate the average C – H bond energy from the following data;
C(s) + O2(g)  CO2(g), H 1o = – 393kJmol–1
1
H2(g) + O2(g)  H2O(l), H 2o = – 286 kJmol–1
2
–1
C(s)  C(g), H 3o = +716kJmol
H2(g)  2H(g), H 4o = +433kJmol–1
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l), H 5o = – 890kJmol–1
CH4 (g) has 4C – H bonds which are formed by the reaction
4BEC – H
C(g) + 4H(g) CH4 (g)
The gaseous atoms are formed by the reactions

H 3
o
C s   C g 
H 4
2H 2 g  2 4H g 
o
The other reactions required to complete the cycle are combustion reactions of
2H2 (g) , C (s) and CH4 (g)
Born-Haber cycle.
4BEC-H CH4 (g)
C(g) + 4H(g)
H 3o 2 H 4o H 5o
C(s) 2H2(g)
2O2(g)
O2(g) H o
1 O2(g) 2 H o
2
CO2(g) + 2H2O(l)
By Hess’s law.
4BEC-H = – H 3o – 2 H 4o + H 1o + 2 H 2o – H 5o
= – 716 – 2(433) – 393 + 2(–286) – (–890)

= –1657
 1657
BEC-H = = –414.25kJmol–1
4
The bond energy of C – H bond is – 414.25kJmol–1
Born-Haber cycle for bond dissociation energy calculations
The BDE cycle of a compound is a mirror image of its BE cycle. So, in this case the
first equation is the dissociation of the compound to the individual atoms
Example 21: Calculate the average bond dissociation energy of C-H from the following
data.
C(s) +O2(g)  CO2(g), H 1o = – 393kJmol–1
1
H2(g) + O2(g)  H2O(l), H 2o = – 286kJmol–1
2
C(s)  C(g), H 3o = +716kJmol–1
H2(g)  2H(g), H 4o = + 433kJmol–1
CH4(g) + 2O2(g)  CO2(g) +2H2O(l), H 5o = – 890kJmol–1
Answer
The Born-Haber cycle for BDE is a mirror image of that of BE. Compare the cycles
in examples 20 and 21.
CH4(g) 4BDEC-H Born-Haber Cycle

C(g) + 4H(g)
H 3o 2 H 4o
H o
5
C(s) 2H2(g)
O2(g) H 1o O2(g) 2 H 2o
2O2(g)
CO2(g) + 2H2O(l)
By Hess’s law.
4BDEC-H = H 5o – H 1o – 2 H 2o + H 3o + 2 H 4o
= – 890 – (–393) – 2(–286) + 716 + 2(433)

= – 890 + 393 + 572 + 716 + 866 = + 1657
 1657
BDEC-H = = + 414.25kJmol–1
4
The bond dissociation energy of C – H bond is +414.25kJmol–1
In calculating the BE and BDE of a liquid substance, an additional step for its
vaporization should be included in the cycle as the following example shows;
Example 22: Calculate the standard enthalpy of formation of ethanol (CH3CH2OH) from
the following data:
CH3CH2OH(l)  CH3CH2OH(g), H vap
o
= + 39kJmol–1
C(s)  C(g), H1o = +716kJmol–1
H2(g)  2H(g), H 2o = + 433kJmol–1
O2(g)  2O(g), H 3o = + 498kJmol–1
BEC-H = – 413kJmol–1, BEC-C = – 345kJmol–1
BEC-O = – 351kJmol–1, BEO-H = – 463kJmol–1
Answer
Born-Haber cycle
H rxn
2C(g) + 6H(g) + O(g) CH3CH2OH(g)
2 H 1o 3 H 2o ½ H 3o H vap
o
2C(s) + 3H2(g) + ½ O2(g) H of

CH3CH2OH(l)
H H
H C C O H
H H
has 5(C – H), 1(C – C), 1(C – O) and 1(O – H) bonds.
H orxn = 5BEC-H +BEC-C+BEC-0+BEO-H

= 5(– 413) – 345 – 351– 463 = – 3224kJ
1
H orxn = – 2 H 1o – 3 H 2o – H 3o + H of + H vap
o
1
– 3224 = –2 (716) – 3(433) – (498) + 39 + H of
2
= – 2941 + H of
H of = – 283kJmol–1
The standard enthalpy change of formation of ethanol is – 283kJmol–1
NOTE: Use the following values for examples 5.23 and 5.24
H – H = + 433kJ mol–1 , C – H = + 413kJ mol–1
C – C = + 345kJ mol–1 , C C = +594kJ mol–1
Hsub
o
Cs   = + 716kJ mol–1, H odiss H 2 g    = + 433kJ mol–1
Examples 23
Calculate the resonance energy of benzene if its actual heat of formation is +
83kJmol–1
Answer
The resonance energy is the difference between calculated and actual values of
H o
f
Born – Haber cycle
H rxn
6C (g) + 6H(g)   C6 H6 (g)
6H1 3H2
H of
6C (s) + 3H2 (g)
By Hess’s law
Hrxn = – 6H1 – 3H2 + H of …………. (1)
But, Hrxn = 6BEC – H + 3BEC – C + 3BEC = C ………….. (2)
Equating (1) and (2)
6BEC – H + 3BEC – C + 3BEC = C = – 6H1 – 3H2 + H of
– 2478 – 1035 – 1782 = –4296 – 1299 + H of
–1
H of = 300 kJ mol
Resonance energy = H of (calculated) – H of (actual) = 300 – 83
= + 217kJ mol–1
The resonance energy of benzene is +217kJmol–1
Example 24
Calculate the strain energy of cyclopropane if its heat of formation is 53kJ mol–1
Answer
The structure of cyclopropane is
H H
C
H H
C C
H H
Born – Haber cycle
H vap
o
3C(g) + 6H(g) C3 H6 (g)
H f
o
3H1 3H2
3C(s) + 3H2(g)
By Hess’s law,
Hrxn = – 3H1 – 3H2 + H of ………………….. (1)
But, Hrxn = 6BEC – H + 3BEC – C …………………… (2)
Equating (1) and (2),
6BEC – H + 3BEC – C = – 3H1 – 3H2 + H of
6(– 413) + 3(–345) = – 3(716) – 3(433) + H of
–1
H of = – 66kJmol
Strain energy = H of (actual) – H of (calculated)
= 53 – (– 66) = 169kJmol–1
The strain energy of cyclopropane is +169kJmol–1
Example 25: Calculate the average C-C bond energy from the following data;
4C(s) + 5H2(g)  C4H10(g), H 1o = – 126 kJ mol–1
C(s)  C(s), H 2o = +716 kJmol–1
H2(g)  2H(g), H 3o = + 435kJmol–1
C(g) + H(g)  C-H, BEC–H = – 413 kJmol–1
Answer
Born–Haber Cycle
H H H H
10BEC-H + 3BEC-C H (g)
4C(g) + 10H(g) H C C C C
H H H H
H lo
4 H 2o 5 H 3
o
4C(s) + 5H2(g)
By Hess’s law,
10BEC-H + 3BEC-C = – 4 H 2o – 5 H 3o + H 1o
10(-413) + 3BEC-C = – 4(716) – 5(435) – 126
– 4130 + 3BEC-C = – 2864 –2175 –126
3BEC-C = – 2864 – 2175 – 126 + 4130 = – 1035
1
:. BEC-C = (–1035) = – 345kJ mol–1
3
The average value of C – C bond energy is – 345kjmol–1
Example 26: Calculate the enthalpy change of the reaction

CH4(g) +2O2(g)  CO2(g) + 2H2O(g), from the following bond dissociation energy values:
C – H = +413, O = O = + 497, C = O = + 803, O – H = + 463kJmol–1
Answer
In the reaction CH4(g) +2O2(g)  CO2(g) + 2H2O(g),
4(C – H), 2(O = O) bonds are broken, 2(C = O) and 4(O – H) bonds are formed.
Hreaction = BDE (bonds broken) – BDE (bonds formed)

BDE (bonds broken) = 4BDEC – H + 2BDEO = O
= 4(413) + 2(497) = 2646kJ
BDE (bonds formed) = 2BDEC = O + 4BDEO – H

= 2(803) + 4(463) = 3458kJ
Hreaction = 2646 – 3458 = – 812kJmol–1
Uses of bond energies
Some important uses of bond energies include:
(i) Comparing the strengths of bonds
(ii) Understanding structure and bonding
(iii) Estimating enthalpy changes of reactions
(iv) Understanding the mechanisms of chemical reactions
COMBINATION OF THERMOCHEMICAL EQUATIONS

It is not always necessary to draw a Born – Haber cycle when solving a
thermochemical problem. An alternative method of solution is by combination of
thermochemical equations.
Examples 27
Calculate the enthalpy change of the reaction.
C2H2 (g) + 2H2 (g)   C2 H6(g) , by combination of the following thermochemical
equations;
2C2H2 (g) + 5O2 (g)  4CO2 (g) + 2H2O(l), H1 = – 2602kJ ……. (1)
2C2H6 (g) + 7O2 (g)  4CO2 (g) + 6H2O(l), H2 = – 3123kJ …….... (2)
H2 (g) + 12 O2 (g) 
 H2O(l), H3 = – 286kJ …….... (3)
Answer
H  ?
The target equation is C2H2(g) + 2H2(g)  C2H2 (g)
The following manipulations are performed using equations ((1), (2) and (3) until the
target equation is obtained.
The target equation has 1C2H2 on the left. So, equation (1) is divided by 2.
5 H 1
C2H2 (g) + O2 (g) 
 2CO2 (g) + H2O(l) , ………………. (4)
2 2
There are 2H2 on the left of the target equation. Therefore, equation (3) is multiplied
by 2.
2H2 (g) + O2 (g) 
 2H2O(l) , 2H3 ………………………..…….... (5)
The target equation does not contain O2, CO2 and H2O. So, we have to find a way to
remove them.
To remove 2CO2 on the right of equation (4), divide equation (2) by 2 and reverse.
7  H 2
2CO2 (g) + 3H2O(l) 
 C2H6 (g) + O2 (g) , ………………... (6)
2 2
Adding equations (4), (5) and (6)
7
C2H2 (g) + 2H2O(l) + O2 (g) + 2CO2 (g) + 3H2O(l)
2
7

 2CO2 (g) + 3H2O(l) + C2H6(g) + O2 (g) ………………………… (7)
2
Cancelling elements and compounds that are the same on both sides of (7) gives the
target equation
C2H2 (g) + 2H2 (g) 
 C2H6 (g) ………………………. (8)
H 1 H 2
H = + 2H3 –
2 2
 2602    3123 
=    2  286    = – 311.5kJ
 2   2 
The enthalpy change of the reaction is – 311.5kJ.
Example 28
Given that;
2Cl(g)  Cl2 (g) , H1 = – 58kcal ….……… (1)
1 1
H2 (g) + Cl2 (g) 
 HCl(g) ……….……… (2)
2 2
1
H2 (g)  H(g) , H3 = 52kcal ………….… (3)
2
Calculate the enthalpy change of the reaction
H(g) + Cl(g)   HCl(g)
(a) by using an energey cycle
(b) by combination of thermochemical equations
Answer
(a) Born – Haber cycle
H(g) + Cl(g) Hrx HCl(g)

n
H 1 H2
H 3
2
1H + 1 Cl
2 (g) 2 (g)
2 2
NOTE
The directions of all arrows in the cycle should be the same as given in the equation.
Don’t change them!
Only one Cl(g) is used in the cycle. So, H1 should be divided by 2.
By Hess’s law
H 1
Hrcn = – H3 + + H2
2
58
= – 52 – – 22
2
= – 103kcal
(b) Combination of thermochemical equations

H
The equation H(g) + Cl(g)   HCl(g) can be obtained by combining
r x n
equations (1), (2) and (3) as follows;

Reverse equation (3)
Divide equation (1) by 2
Add them to equation (2) as follows;
1
H (g) 
 H 2  g  ,  H 3
2
H 1
1
2

2Cl ( g )  
 Cl 2 ( g ) ,
2
1 1
H 2 g   Cl 2 ( g )   HCl ( g ) , H 2
2 2
H1
H g    Cl g  
 HCl g  , H rxn ,   H 3   H 2
2
H1 58
H rxn   H 3   H 2 =  52   22
2 2
= – 103kcal
HEMICAL EQUILIBRIA
Chemical reactions that occur in either direction are called reversible reactions.
CThese types of reactions can generally be represented as
When A and B react to form C and D at the same rate at which C and D react to form
A and B, the system is said to be at equilibrium. ie Rate of forward reaction (Rf)
= Rate of reverse reaction (Rr)
The Equilibrium Constant
Suppose a reversible reaction occurs by a single elementary reaction step
The rate of forward reaction is ratef = Kf[A]2[B]

The rate of reverse reaction is rater = Kr[A2B]
At equilibrium, ratef = rater then Kf[A]2[B] = Kr[A2B] also
At any specific temperature both Kf and Kr are constants so Kf/Kr is also a constant
called the equilibrium constant, Kc or simply K.
Generally, for a reaction
Numerical values of Kc can come only from experiments. Some equilibrium constant
expressions and their numerical values at 250C are
The magnitude of Kc is a measure of the extent to which reaction occurs. For any
balanced chemical equation, the value of Kc
i) is constant at a given temperature
ii) changes if the temperature changes
iii) does not depend on the initial concentrations but rather on equilibrium
concentrations.
Example
Some nitrogen and hydrogen are placed in an empty 5.0 litre container at 500 0C.
When equilibrium is established, 3.01mol of N2, 2.10mol of H2 and 0.565mol of NH3
are present. Evaluate Kc for the following reaction at 5000C
Solution
The equilibrium concentrations are : [N2] = 3.01mol/5.00L = 0.602M, [H2] =
2.10mol/5.00L = 0.420M
[NH3] = 0.565mol/5.00L = 0.113M
The equilibrium lies to the left (reactant favoured).
Variation of Kc With The Form of The Balanced Equation

The value of Kc depends on how we write the balanced equation for the reaction.
Example
Consider the following chemical equation and its equilibrium constant at a given
temperature
Write the expression for and calculate the numerical value of the equilibrium constant
for each of the following equations at the same temperature
a)
b)
Solution
a) the original equation has been multiplied by 2, so Kc must be squared

b) the original equation has been multiplied by ½ (divided by 2), so K c must be raised
to the ½ power. The value of Kc’’ is the square root of the original K c value
The Reaction Quotient

The reaction quotient Q for the general reaction is given as
(not necessarily equilibrium concentrations)

The reaction quotient, Q is a measure of the progress of a reaction
Q < Kc: forward reaction predominates until equilibrium is established
Q = Kc : system is at equilibrium
Q > Kc : reverse reaction predominates until equilibrium is established
Example
At a very high temperature, Kc = 65.0 for the reaction below
The following concentrations were detected in a mixture. Is the system at equilibrium?

If not, in which direction must the reaction proceed for equilibrium to be established?
[HI] = 0.500M [H2] = 2.80M [I2] = 3.40M
Solution
But Kc = 65.0, so Q < Kc the system is not at equilibrium. For equilibrium to be

established the value of Q must increase until it equals Kc. This can occur only if the
numerator increases and the denominator decrease. Thus the forward (left to right)
reaction must occur to a greater extent than the reverse reaction, that is, some HI
must react to form more H2 and I2 to reach equilibrium.
Uses of The Equilibrium Constant, Kc

Once the value of Kc has been calculated from the equilibrium concentrations, the
process can be turned around to calculate equilibrium concentrations from the
equilibrium constant.
Example
The equation for the following reaction and the value of Kc at a given temperature are
given. An equilibrium mixture in a 1.00 litre container contains 0.25 mol PCl5 and 0.16
mol PCl3. What equilibrium concentrations of Cl2 must be present?
Solution
The volume of the container is 1.00 litre, the molar concentration (mol/L) of each
substance is numerically equal to the number of moles.
Often we know the starting concentrations and want to know how much of each
reactant and each product would be present at equilibrium.
Example
10.0moles of N2O is introduced into a 2.00L container at some temperature, where it
decomposes according to
At equilibrium, 2.20mol of N2O remain. Calculate the value of Kc for the reaction.
Solution
The reaction summary includes the values or symbols for the values of
i) initial concentrations
ii) changes in concentrations
iii) concentrations at equilibrium
At equilibrium, 2.20mol N2O remain

mol N2O reacting = 10.0mol N2O initial – 2.20mol N2O remaining = 7.80mol N2O
reacting
Initial [N2O] = 10.00 mol/2.00L = 5.00M
The concentration of N2O ie [N2O] that reacted = 7.80mol /2.00L =3.90M
From the balanced chemical equation, each 2 mol N2O that reacted produced 2mol N2
and 1mol O2
ie N2O : N2 : O2
2 mol 2 mol 1 mol
1 mol 1 mol ½ mol
Initial concentration 5.00M 0M

0M +
Change in concentration due to reaction -3.90M +3.90M
+1/2(3.90)M
Concentration at equilibrium 1.10M 3.90M
1.95M
Example
For the following reaction, the equilibrium constant is 49.0 at a certain temperature. If
0.400 mol each of A and B are placed in a 2.00 litre container at that temperature,
what concentrations of all species are present at equilibrium?
Solution
The initial concentrations are
[A] = 0.400 mol / 2.00L = 0.200M, [B] = 0.400 mol / 2.00L = 0.200M,
[C] = [D] = 0M
We know that the reaction can only proceed to the right at the start of the reaction
because only reactants are present.
let x = moles per litre of A that reacted
x = moles per litre of B that reacted
x = moles per litre of C and D that are formed
Initial concentration 0.200M 0.200M 0M 0M

+
Change in concentration due to reaction -xM -xM +xM +xM
Concentration at equilibrium (0.200 – x)M (0.200- x)M xM xM
= (x)(x) = x2 = 49.0
2
(0.200 – x)(0.200- x) (0.200 – x)
This quadratic equation has a perfect square on both sides
x/(0.200 – x) = 7.00; x = 1.40 – 7.00x; 8.00x = 1.40; x = 1.40/8.00
= 0.175
[A] = (0.200 –x)M = 0.200 – 0.175 = 0.025M
[B] = (0.200 –x)M = 0.200 – 0.175 = 0.025M
[C] = [D] = xM = 0.175M
Example
Consider the same system as in the example above at the same temperature, if 0.600
mol of A and 0.200 mol of B are mixed in a 2.00L container and allowed to reach
equilibrium, what will be the equilibrium concentrations of all species.
Solution
Let x = mol/L of A or B that reacted
x = mol/L of C and D formed
Initial concentration 0.300M 0.100M 0M 0M

+
Change in concentration due to reaction -xM -xM +xM +xM
Concentration at equilibrium (0.300 – x)M (0.100- x)M xM xM
= (x)(x) = x2 = 49.0
2
(0.300 – x)(0.100- x) 0.03 – 0.40x + x
2
x = 1.47 – 19.6x + 49x; 48x2 – 19.6x + 1.47 = 0
Solving using quadratic equation
a = 48, b = -19.6, c = 1.47
x = 0.309 or 0.099 and therefore x = 0.099

[A] = (0.300 –x)M = (0.300 – 0.099)M = 0.201M
[B] = (0.100 –x)M = (0.100 – 0.099)M = 0.001M
[C] = [D] = xM = 0.099M
Partial Pressures and The Equilibrium Constant

It is often more convenient to measure pressures rather than concentration of gases.
In general for reaction involving gases
Example
In an equilibrium mixture at 5000C we find
0
, and . Evaluate Kp at 500 C for the following
reaction
Solution
Relationship Between Kp and Kc

If the ideal gas equation is rearranged, the molar concentration of a gas is n/V = P/RT
or M = P/RT. Substituting P/RT for n/V in the Kc expression for the N2-H2-NH3 in
ammonia production reaction, equilibrium gives the relationship between Kc and Kp for
the reaction.
Kc = Kp(RT)2 and Kp = Kc(RT)-2

In general, the relationship between Kc and Kp is Kp = Kc(RT)∆n or Kc = Kp(RT)- ∆n
Where ∆n = (ngas product(s)) – (ngas reactant(s))
For reactions in which equal numbers of moles of gases appear on both sides of the
equation, ∆n = 0 and Kp = Kc.
Example
If Kc for ammonia reaction at 5000C (or 773K) is 0.286, calculate the Kp for such
reaction
∆n = 2 - 4 = -2
∆n
Kp = Kc(RT)
= (0.286)[(0.0821)(773)]-2 = 7.10 x 10-5
Heterogeneous Equilibria
Heterogeneous equilibria involves species in more than one phase. Consider the
following reversible reaction at 250C
For any pure solid of pure liquid, the activity is taken as 1, so terms for pure liquids or
pure solids do not appear in the K expressions for heterogeneous equilibria, ie for
above reaction
Kc = [O2] or Kp = PO2
Example
Write both Kc and Kp for the following reactions
a)
b)
c)
Solution
a)
b)
c) Kp is undefined because no gases are
involved.
Example
The value of Kp is 27 for the thermal decomposition of potassium chlorate at a given
high temperature. What is the partial pressure of oxygen in a closed container in
which the following system is at equilibrium at the given temperature?
Solution
Kp = (PO2)3 = 27
Let x atmosphere = PO2 at equilibrium
Then (PO2)3 = 27 =x3; x = 3.0 atmospheres
Relationship Between ∆G0rxn and K
The relationship between the free energies both at standard and non standard
conditions is given as
∆Grxn = ∆G0rxn + RTlnQ
Where R is the universal gas constant, T is the absolute temperature and Q is the
reaction quotient
When a system is at equilibrium ∆G0rxn = 0 and Q = K
Upon substitution 0 = ∆G0rxn + RTlnK; ∆G0rxn = -RTlnK
When the relationship ∆G0rxn = -RTlnK is used with
i) all gaseous reactants and products, K represents Kp
ii) all solution reactants and products, K represents Kc
iii) a mixture of solution and gaseous reactants, K represents the thermodynamic
equilibrium constant and there is distinction between Kp and Kc.
The thermodynamic equilibrium constant is defined in terms of activities of the species
involved
Where a is the activity of the substances.

∆G0rxn K Product formation
∆G0rxn < 0 K > 1 Products favoured over reactants at equilibrium
∆G0rxn = 0 K = 1 At equilibrium where [C]c[D]d…….= [A]a[B]b
∆G0rxn > 0 K < 1 Reactants favoured over products at equilibrium
Example
Calculate Kp for the following reaction at 250C
Solution
For all gaseous reaction, K = Kp and ∆G0rxn = -RTlnKp
= [ 2(0) + 0 ] - [ 2(104.2)] = -208.4KJ/mol or -2.084 x 105J/mol

But ∆G0rxn = -RTlnKp
lnKp = ∆G0rxn/-RT = -2.084 x 105/-(8.314 x 298) = 84.1
Kp = e84.1 = 3.3 x 1036
Evaluation of Equilibrium Constants at Different Temperatures

This is achieved by the use of van’t Hoff equation
Where is the equilibrium constant at T1

is the equilibrium constant at T2
Thus knowing the value of ∆H0 for a reaction and R at a given temperature, van’t Hoff
equation can be used to calculate the value of K at any other temperature.
Example
If Kp for the above reaction is 4.4 x 10-31 at 250C(298K) and ∆H0 is 180.5KJ/mol.
Evaluate Kp at 2400K.
Solution
= 63.8
= e63.8 = 5.1 x 1027
= 5.1 x 1027 x 4.4 x 10-3 = 2.2 x 10-3
Displacement of Equilibrium: Factors Affecting Chemical Equilibrium

The establishment of a chemical equilibrium is the result of a balance between the
forward and reverse reactions of a reversible reaction. Therefore, the equilibrium
position is altered by the factors which affect the rates of the forward and reverse
reactions unequally, and their effects were summarized by H. leChatelier in 1885. Le
Chatelier principle states that if one of the external factors which affect a
system in equilibrium is altered, then the system tends to react in such
away as to minimize any changes resulting from the alteration of the
external factors.
1. Displacement caused by concentration changes

Consider the general reaction
Provided the total volume and other factors such as temperature are kept constant, an
increase in the concentration of (say) A will produce an increase in the concentrations
of C and D, since Kc must be kept constant.
Example
The equilibrium constant for the formation of ethyl ethanoate is 4.0 at 700C. What
concentration of ester would be produced at equilibrium starting from one mole of
ethanoic acid and
i) 2 moles of alcohol
ii) 10 moles of alcohol
Solution
Initial concentration 2mol 1mol
0M 0M
Change in concentration due to reaction -xmol -xmol
+xmol +xmol
Concentration at equilibrium (2 – x)mol (1 - x)mol
xmol xmol
a) Kc = [CH3COOC2H5][H2O] = 4
[C2H5OH][CH3COOH]
= x2 = 4
(2 – x)(2 – x)
2
3x – 12x + 8= 0; x = 0.84 mol
b) Kc = x2 = 4
(10 – x)(1 –x)
3x2 -44x + 40 = 0; x = 0.97 mol
Thus a greater yield of ester follows an increase in the initial concentration of alcohol
(or acid) and the equilibrium is displaced to the right, but if one of the products is
removed from the reaction medium as it is formed then the equilibrium is displaced so
far to that the reaction may go to completion.
2. Displacement caused by changes in pressure

Pressure affects only those equilibria which show a change in volume between the
reactants and products. The effect of pressure changes on reactions in which gases
are involved are particularly important for the following reasons
i) in any gaseous reaction, an increase in pressure brings the reaction molecules closer
together and the reaction speeds up, that affects both forward and reverse reactions.
ii) the composition of the equilibrium mixture (but not the Kc) is altered in those cases
where there is a volume change
Example
In the reaction
∆n = nproduct – nreactant = 2 – 3 = -1
Increase in pressure favours smaller volume ie more SO3 will be formed, while
decrease in pressure favours higher volume ie more SO2 and O2 will be formed.
3. Displacement caused by changes in temperature

In all reactions, an increase in temperature causes an increase in the rate at which a
reaction takes place. Ie approximately double for every 100C rise in temperature. This
means that, at higher temperatures, the equilibrium position is attained more rapidly.
Temperature also has an effect on the value of the equilibrium constant. It may be
shown that log K α -∆H/T
For an exothermic reaction in which ∆H is –ve, log K (and therefore K) will become
progressively smaller as the temperature increases since K = [Products]/[Reactants]
the product concentration will fall with increasing temperature.
For endothermic reactions, ∆H is positive and at any temperature, log K is negative,
thus log K α -∆H/T or log 1/K α ∆H/T.
Hence as the temperature increases, K increases and the product concentration will
rise.
Example
The forward reaction is favoured by a decrease in temperature been exothermic, while

the reverse reaction is favoured by an increase in temperature.
NOTE: Effect of catalyst

A catalyst speeds up the rate of a chemical reaction. In equilibrium reactions, both
forward and reverse reactions are equally affected so that the position of equilibrium is
not changed, although the equilibrium state is arrived at more rapidly.
Problems
1. Write the Kc expression and its unit for the following reaction
CaCO3(s)  CaO(s) + CO2(g)
2. write the Kp expression and its unit for the following reaction
2NO2(g) + 4H2(g)  N2(g) + 4H2O(g)
-2
3. Kp for the reaction below is 40.7 atm at 400K. Calculate the Kc at this
temperature.
2NO2(g) + 4H2(g)  N2(g) + 4H2O(g)
4. 2SO2(g) + O2(g)  2SO3(g) ΔH = -791.6KJmol-1
i) What conditions will cause the increase in the product yield in the above
reaction?
ii) State whether the reaction is endothermic or exothermic and draw its energy
profile diagram
5. The equilibrium constant (Kc) for the formation of nitrosyl chloride, an orange
yellow compound from nitric oxide and molecular chlorine is 6.5 x 104 at 350C.
2NO(g) + Cl2(g)  2NOCl(g)
In a certain experiment, 2.0 x 10-2 mole of NO, 8.2 x 10-3 mole of Cl2 and 6.8 mole of
NOCl are mixed in a 2.0 dm3 flask. In which direction will the system proceed to reach
equilibrium?
6. Write the equilibrium constant expression for each of the following
a) 2CO(g) + O2(g)  2CO2(g)
b) P4(g) + 3O2(g)  P4O6(s)
c) 2HBr(g)  H2(g) + Br2(l)
d) SrCO3(s)  SrO(s) + CO2(g)
e) CO2(g) + H2(g)  CO(g) + H2O(g)
f) 2H2O2(g)  2H2O(g) + O2(g)
7. On the basis of equilibrium values, choose the reactions in which the reactants are
favored
a) H2O(l)  H+(aq) + OH-(aq) K = 1.0 x 10-14
b) 2Fe2+(aq) + 3S2-(aq)  Fe2S3 K = 1.0 x 1088
c) Ca3(PO4)2(s)  3Ca2+(aq) + 2PO43-(aq) K = 1.0 x 10-25
d) [AlF6]3-(aq)  Al3+(aq) + 6F-(aq) K = 2.0 x 10-24
8. Predict whether the equilibrium for the photosynthesis reaction described by the
equation below
6CO2(g) + 6H2O(l)  C6H12O6(s) + 6O2(g) ΔH0 = 2801.69
KJ / mol
Would i) shift to the right ii) shift to the left iii) remain unchanged if
a) [CO2] was increased b) [PO2] was increased c) one half of the C6H12O6
were removed
d) the total pressure was decreased e) the temperature was increased f) a
catalyst was added
9. For the reaction Br2(g)  2Br(g) Kp = 2550 at 4000K. What is the
value of Kc
10. For the reaction H2(g) + Cl2(g)  2HCl(g) Kc = 193 at 2500K. What
is the value of Kp
11. The following equilibrium partial pressures were measured at 7500C: PH2 = 0.387
atm, PCO2 = 0.152 atm, PCO = 0.180 atm and PH2O = 0.252 atm. What is the value of
the equilibrium constant Kp for the reaction
H2 + CO2  CO + H2O
12. Under what conditions are Kc and Kp numerically equal for any reaction at
equilibrium
13. The equilibrium constant Kp for the reaction indicated by the following equation is
0.715 at 470C N2O4(g)  2NO2(g) Calculate the partial pressures of N2O4 and
NO2 in an experiment in which 2.5 moles of N2O4 is placed in a 5.0 liter flask and
allowed to establish equilibrium at 470C
14. Nitrogen reacts with hydrogen to form ammonia N2(g) + 3H2(g)  2NH3(g)
an equilibrium mixture at a given temperature is found to contain 0.31mol/L N2, 0.50
mol/L H2 and 0.14mol/L NH3. Calculate the value of Kc at the given temperature.
15. For the following equation, Kc = 7.9 x 1011 at 500K H2(g) + Br2(g) 
2HBr(g)
a) 1/2H2(g) + 1/2Br2(g)  HBr(g) Kc = ?
b) 2HBr(g)  H2(g) + Br2(g) Kc = ?
c) 4HBr(g)  2H2(g) + 2Br2(g) Kc = ?
16. a) Define the reaction quotient, Q and distinguish between Q and K
b) Why is it useful to compare Q with K? What is the situation when i) Q = K ii)
Q < K iii) Q > K?
c) Kc = 19.9 for the reaction Cl2(g) + F2(g)  2ClF(g)
What will happen in a reaction mixture originally containing [Cl2] = 0.5mol/L, [F2] =
0.2mol/L and [ClF] = 7.3mol/L?
17. The concentration equilibrium constant for the gas phase reaction H2CO 
H2 + CO has the numerical value 0.50 at a given temperature. A mixture of H 2CO,
H2 and CO is introduced into a flask at this temperature. After a short time, analysis of
a small sample of the reaction mixture shows the concentrations to be [H 2CO] = 0.50
M, [H2] = 0.80M and [CO] = 0.25M. Classify each of the following statements about
this reaction mixture as true or false
a) The reaction mixture is at equilibrium
b) The reaction mixture is not at equilibrium, but no further reaction will occur
c) The reaction mixture is not at equilibrium, but will move toward equilibrium by
using up more H2CO
d) The forward rate of this reaction is the same as the reverse rate
18. a) State Lechateliers principle
b) Which factors have an effect on a system at equilibrium?
c) How does the presence of a catalyst affect a system at chemical equilibrium?
Explain your answer.
19. What will be the effect of increasing the total pressure on the equilibrium
conditions for
a) a chemical equation that has more moles of gaseous products than gaseous
reactants
b) a chemical equation that has more moles of gaseous reactants than gaseous
products
c) a chemical equation that has the same number of moles of gaseous reactants to
gaseous products
d) a chemical equation in which all reactants and products are pure solids, pure liquids
or in aqueous solution.
20. Suppose the following exothermic reaction is allowed to reach equilibrium
A(g) + 3B(g)  2C(g) + 3D(g) then we make each of the following
changes and allow the reaction to establish equilibrium. Tell whether the amount of B
present at the new equilibrium will be
i) greater than ii) less than iii) the same as the amount of B before the
change was imposed when
a) the temperature is increased while the volume is kept constant
b) more A is added
c) more C is added
d) a small amount of D is removed
e) the pressure is increased by decreasing the volume
ONIC EQUILIBRIA
I Introduction
We have learnt about non-ionic equilibria whose name implies those that do not form
any ions. In this section we are going to deal with ionic equilibrium which is concerned
with dissociation of substances in solution into ions and the reverse process. Ionic
equilibria come in two forms:
1. Dissociation equilibria
2. Solubility equilibria
Therefore, the basic reaction of ionic equilibria is ionisation and the players in these
equilibria are the acids, bases and salts. While dissociation equilibria are concerned
with the ionisation of substances, the solubility equilibria are primarily concerned with
the solubility properties salts in solution. As we shall see, both types of equilibria are
going to be discussed strictly as chemical changes. An acid or a base can be defined
either in terms of dissociation or proton transfer. For example an acid can be defined
as
1. a substance which dissociates to give hydrogen ion (or hydroxonium ion) as
the
only positive ion (Arrehnius definition)
2. a proton donor (Brønsted definition)
A base may be defined therefore a proton acceptor (Brønsted definition) or as a
substance which dissociates to give hydroxyl ion as the only negative ion (Arrhenius
definition). We are going to use the Brønsted acid and Brønsted base in many of our
discussions of acid-base equilibria (also called Brønsted equilibria). Acid-base equilibria
occurs when at least one component (either the acid or base) is weak (i.e. partially
dissociates). Let’s start by taking good examples of Brønsted equilibria.
NH3 + HCl NH4+ + Cl-
(Base) (Acid) (Acid) (Base)
It would be seen from the chemical equations that an acid reacts with a base to form
the corresponding ‘conjugate’ acid and conjugate base.
Dissociation equilibria
Brønsted equilibrium in water
Generally, any weak acid HA will dissociate in water according to the following
equation:
HA + H2 O H3O+ + A-
e.g. CH3COOH + H2 O H3O+ + CH3COO-
strong acid very weak base strong acid stronger base
HCl + H2 O H3O+ + Cl-

strong acid very weak base strong acid extremely
weak base
The equilibrium constant for the dissociation of the acid can be given in terms of the
concentration of the reactants and products as follows:
[H3O+ ][A] [H3O+ ][A]
K So, K [H 2O] 
[HA][H 2 O] [HA]
The concentration of water in a solution containing 1 mol/dm3 solute is only 2% lower
than that of water (which is 55.5 mol/dm3 if 1000g of water is considered). Therefore
[H2O] = constant.
[H3O+ ][A]
Because K[H2O] = Ka , we can write the following equation: Ka 
[HA]
Where Ka is the acid dissociation constant (acidity constant or acid ionisation
constant).
The Brønsted equilibrium of a base in water is given by
B + H2 O HB+ + OH-
e.g. NH3 + H2 O NH4+ + OH-
By analogous approach as in the case of acid
[HB+ ][OH - ]
Kb 
[B]
Where Kb is the base dissociation constant (base ionisation constant).
It is important to note that the numerical values of Ka and Kb are characteristics of a
particular acid or base, and is a measure of their strength. Like all equilibrium
constants
Problem: If 0.1 mol of ethanoic acid is dissolved in 1 dm3 of water and the
concentration of hydroxonium ions is 6.64 x 10-7 mol/dm3, calculate Ka for the ethanoic
acid
Solution: Write the equation for the ionisation of CH3COOH

CH3COOH + H2O H3O + CH3COO-
[H3O+ ][CH3COO- ]
Ka 
[CH3COOH]
But, After dissolution partial ionisation of the acid occurs,
[H3O+] = [CH3COO-] = 6.64 x 10-7 mol/dm3 ,
The resulting concentration of CH3COOH after this ionization is given by
[CH3COOH] = (0.1 - 6.64 x 10-7 mol/dm3) ≈ 0.1 mol/dm3
[H3O+ ][CH3COO- ] (6.64 x 10-7 )2
 Ka  
[CH3COOH] 0.1
 Ka = 4.41 x 10-12 mol/dm3
Amphiprotic behaviour of water

Water is amphoteric, it can even react with itself by a process known as autoionisation
(or autoprotolysis of water). The equation for autoionisation of water is given below:
H2 O + H2 O H3O+ + OH-
(Acid) (Base) (Acid) (Base)
+ -
[H3O ][OH ]
K
[H 2O]2
 K[H2O]2  [H3O+ ][OH- ]
But K[H2O]2  Kw
 Kw = [H3O+][OH-]
At 25 oC pure water [H3O+] = 1 x 10-7 mol/dm3 = [OH-]
So Kw = 1 x 10-14 mol2/dm6
It also follows that Kw = Kb x Ka
Concept of pH
pH scale represents the widely different hydronium ion concentrations conveniently on
graph. By definition,
“pH is the negative log to base ten of the molar hydrogen ion concentration”
Mathematically, pH = -log[H+]
In analogous manner pOH = -log[OH-]
The above notation has been extended to equilibrium constant. For example,
pKa = -logKa
If pH = 7 (e.g. for pure water), pOH = 7.
Therefore, pH + pOH = 14
(In support, observation has shown that as pH = 0, pOH = 14. Similarly when pH = 5,
pOH = 9)
But Kw = [H3O+][OH-]
 pKw = -log[OH-] + -log[H3O+]
= pH + pOH
pH + pOH = 14 = pKw
Problem: What is the maximum pH of a solution 0.1 mol/dm3 in Mg2+ from which
Mg(OH)2 will not precipitate? (Ksp = 1.2 x 10-11 mol2/dm6)
Solution: Write the equation for the ionisation of Mg(OH)2

Mg(OH)2 Mg2+ + 2OH-
Since Mg(OH)2 is a base we need to use Ksp to find [OH-] which can lead us to pH.
But Ksp = 1.2 x 10-11 = [H3O+][OH-] = [OH-]2
 [OH-]2 = 1.2 x 10-11 mol2/dm6
[OH-] = 1.1 x 10-5 mol/dm3
But pOH = -log[OH-]
 pOH = -log 1.1 x 10-5 = 4.96
Therefore, pH = 14-pOH = 9.04
pH of strong acid and strong base

In strong acids dissociation is virtually complete and stable salts are formed. Hence,
the formulae to use for the calculation of pH and pOH do not require any modification.
pH = -log[H3O+]
pOH = -log[OH-]
pH = pOH = 7
pKa for strong acids is negative (for example pKa(HNO3) = -1 and pKa (HCl) = -3). This
implies that Ka > 1.
In contrast, pKb for strong bases is positive (for example pKb(NO3-) = 15 and pKb (Cl-) =
17). This implies that Kb < 1 or negative.
Problem: Calculate the pH of (a) 0.05 mol/dm3 KOH (b) 0.1 mol/dm3 HCl
Solution:
(a) Write the equation for the ionisation of KOH
KOH + H 2O K+(aq) + OH-(aq)
Since KOH ionises completely in water
[OH-] = [KOH] = 0.05 mol/dm3
For a strong base pOH = -log[OH-]
or pOH = -log 0.05 = 1.3
But pH + pOH = 14
 pH = 14-pOH = 14-1.3 = 12.7
(b) Write the equation for the ionisation of HCl
HCl + H2O H3O+(aq) + Cl-(aq)
Since HCl ionises completely in water
[Cl-] = [HCl] = 0.05 mol/dm3
For a strong base pH = -log[H3O+] or pH = -log 0.1 = 1.0
Degree of ionization of weak acid and bases

The degree of ionization (α) of a weak acid or a weak base is the extent to which it
ionizes in aqueous solution. If C is the concentration of a weak acid HA then α=
- +
[A ]/C or [H ]/C
Similarly for a weak base B α = [BH+]/C or [OH-]/C
Percentage ionization = α x 100
Note: the Ka expression of a weak acid or Kb expression for a weak base usually
reduces to a quadratic equation. Solution of the equation is either by approximation or
by quadratic formular.
1. To predict the method of solution of the quadratic equation, calculate C/Ka of the
weak acid or C/Kb of the weak base. If this value is equal to or greater than
1000, solution of the equation by approximation MAY be valid.
2. Apply the approximation to determine the [H+] or [OH-]
3. Calculate [H+]/C or [OH-]/C if the value is less or equal to 5%, the solution of
the equation by approximation is VALID.
4. If [H+]/C or [OH-]/C is greater than 5%, the equation is solved by the quadratic
formular.
Problem: Calculate a) [H+] b) [CH3COO-] c) [CH3COOH] d) α e) pH of a

-5
0.049mol/L acetic acid solution (Ka = 1.8 x 10 mol/L)
Solution
CH3COOH(aq) + H2O(l) = CH3COO-(aq) + H+(aq)
Iniial conc 0.049mol/L 0 0
Let x be the concentration of acetic acid which dissociates at equilibrium
CH3COOH(aq) + H2O(l) = CH3COO-(aq) + H+(aq)
Equilibrium conc 0.049 – x 0+x 0+x
The equilibrium concentrations are [CH3COOH] = 0.049 – x, [CH3COO-] = x,
[H+] = x
Ka = [CH3COO-][H+]
[CH3COO-]
1.8 x 10-5 = (x)(x)
(0.049 – x)
We now predict the method of solution of the above equation
C/Ka = 0.049/1.8 x 10-5 = 2722
Since C/Ka is greater than 1000, we apply the approximation method
0.049 – x ≈ 0.049
1.8 x 10-5 = x2/0.049
x = √(0.049 x 1.8 x 10-5) = 9.4 x 10-4mol/L
[H+] = 9.4 x 10-4mol/L
We check the validity of the approximation
[H+]/C = 9.4 x 10-4/0.049 = 0.019 or 1.9%
Since [H+]/C is less than 5% the approximation is valid
Then proceed to determine the other parameters
a) [H+] = 9.4 x 10-4mol/L
b) [CH3COO-] = x = 9.4 x 10-4mol/L
c) [CH3COOH] = 0.049 – x = 0.049 – 9.4 x 10-4 = 0.048mol/L
d) α = [H+]/C = 9.4 x 10-4/0.049 = 0.019 or 1.9%
e) pH = -log[H+] = -log(9.4 x 10-4) = 3.03
Problem
Calculate the pH of a 0.036mol/L nitrous acid (HNO2) solution (Ka = 4.5 x 10-4)
Solution
let x be the concentration of HNO2 which dissociates at equilibrium
HNO2(aq) + H2O(l) = H+(aq) + NO2-(aq)
Equilibrium conc 0.036 – x x x
2 -4
Ka = x /(0.036 – x) = 4.5 x 10
Predicting the method of solution
C/Ka = 0.036/4.5 x 10-4 = 80
Since this value is less than 1000, the equation can not be solved by approximation,
the quadratic formular has to be used
X2/ (0.036 – x) = 4.5 x 10-4
The equation expands to x2 + 4.5 x 10-4x – (4.5 x 10-4)(0.036) = 0
This equation is comparable to x2 + Kax –KaC = 0 which has a solution of x = -Ka ±
√(Ka2 + 4KaC)/2
Therefore Ka = 4.5 x 10-4 and C = 0.036
The positive root is x = -4.5 x 10-4 + √(4.5 x 10-4)2 + 4(4.5 x 10-4)(0.036) = 3.8 x
10-3mol/L
2
+ -3 -3
[H ] = 3.8 x 10 mol/L and pH = -log(3.8 x 10 ) = 2.42
pH of weak acid and weak base
Relationship Between Ka, Kb and Kw

Weak acids dissociate partially. Their pKa is positive (eg. pKa (NH4+) = 9.3 and pKa
(HCO3-) = 10.3). We may generally write the equation for the ionisation weak acids as
follows:
HA + H 2O H3O+(aq) + A-(aq)
[H3O+ ][A - ]
Ka 
[HA]
Because [H3O+] = [A-]
[H3O+ ]2
Ka 
[HA]
 Ka [HA]
1
2
 [H3O+ ]
If we take the logarithm to base 10 of both sides of the above equation.
log[H3O+] = ½log Ka + ½log[HA]
We can multiply this equation to by -1 give the following:
-log[H3O+] = -½log Ka - ½log[HA]
So that pH = ½pKa - ½log[HA] (formula for pH of Weak acids)
Problem: Find the pH of 0.1 mol/dm3 ethanoic acid

(the Ka of ethanoic acid is 1.78 x 10-5)
Solution: Write the formula pH = ½pKa - ½log[HA]
 pH = ½ (-logKa) - ½log[HA]
= ½ (-log1.78 x 10-5) – ½ log 0.1
= ½ (4.75) – ½ log 0.1
= 2.88 (write pH to 2 decimal places)
Tutorial Problems: Try solving this problem using the expression for Ka
1. Use the quadratic formula to find the [H3O+] recalling that [H3O+] = [A-] or
2. Assume instead of using the almighty quadratic formula that for weak acids [HA]
>> [H3O+])
Weak bases undergo partial ionisation in water as well as acids. Unlike weak acids
however, their pKb is negative and Kb is positive. We may generally write the equation
for the ionisation weak acids as follows:
B + H2O BH+(aq) + OH-(aq)
[BH + ][OH - ]
Kb 
[B]
For example the ionisation of NH3 proceeds as follows;
NH3 + H 2O NH4+(aq) + OH-(aq)
[NH 4 + ][OH - ]
Kb 
[NH3 ]
Because [OH-] = [BH+]
we can rewrite the general formula for base dissociation constant as follows:
[OH - ]2
Kb  Or Kb x [B] = [OH-]2
[B]
If we multiply the above equation by -1 and take the logarithm to base 10 of both
sides we obtain
-logKb - log [B] = -2log[OH]
Which is equivalent to pKb –log [B] = 2 pOH Or pOH = ½pKb- ½log[B]
Since pH = pKw-pOH
pH = pKw- ½pKb+ ½log[B]
If we substitute in the above equation Kb = Kw/Ka
we obtain pH = pKw- ½log (Kw /Ka) + ½log[B]
which can be written in the following form
pH = pKw- ½logKw +½logKa + ½log[B]
 pH = ½pKw + ½logKa + ½log[B] (pH of weak bases)
Problem: Find the pH of 0.01 mol/dm3 aqueous ammonia given that and Ka (NH4+) = 5
x 10-10
Solution:
Data: Ka (NH4+) = 5 x 10-10
We know that pH = ½pKw + ½logKa + ½log[B] (for weak bases)
Tutorial problems:
Try deriving this formula your way, from the base ionisation constant formula. In
addition, solve the problem above using Kb (NH3) = 1.8 x 10-5
a) by a formula
b) using Kb expression and quadratic equation
c) using assumption that [B] >> [OH-]
Problem: If during an experiment 2cm3 of 0.1 mol/dm3 HCl is added at a time to a

20cm3 volume of 0.5 mol/dm3 NaOH in a conical flask. Calculate (a) the pH of the
NaOH solution before the addition of the acid, (b) the number of moles of NaOH left
unreacted and (c) the pH of the resulting solution.
Solution:
(a) [OH-] = 0.1M
We know that, pOH = -log10 [OH-]
 pOH = - Log10 0.1 = 1
and pH = 14 – pOH = 14 – 1 = 13
(b) Since NaOH is in excess, HCl is the limiting reagent.
Initial number of moles of NaOH = MNaOH x VNaOH = 0.5moldm-3 x 0.02dm3 = 0.01mole
number of moles NaOH reacted = MHCl x VHCl = 0.5moldm-3 x 0.002dm3 = 0.001mole
But, moles of unreacted HCl = initial moles of NaOH - moles of NaOH reacted
= 0.01 – 0.001 = 0.009 mol
(c) After the addition of 2cm3 of HCl the total volume of the solution becomes 22cm3
or 0.022dm3. The pH of the resulting solution will not be 7 since NaOH is in
excess.
[OH-] = moles of unreacted NaOH = 0.009 mol = 0.41moldm-3
volume of resulting solution 0.022 dm3
pOH = - log10[OH-] = = -log 0.4 = 0.4
 pH = 14 – pOH = 14 – 0.4 = 13.6
The calculation can be continued with further addition of HCl till NaOH is no longer in
excess.
Buffer Solutions
A solution containing a mixture of a weak acid and its salt (i.e. the conjugate base) or
a weak base and its salt (i.e. the conjugate acid) is called buffer solution. A good
example of a buffer solution is consists of a mixture of ethanoic acid (that is a weak
acid) and its ester ammonium ethanoate (that is a conjugate base).
CH3COOH + H2O H3 O + CH3COO-
Amount: Relatively large Huge Relatively Small Relatively large
Because the corresponding salt is present (e.g. CH3COONa), common ion effect is
observed owing to the low concentration of hydroxonium ions formed by the weak
ethanoic acid. (Refer to common ion effect under solubility equilibria).
CH3COONa CH3COO- + Na+
Buffer solutions resist changes in pH on addition of acid or base. For example, in the
above reaction any addition of strong acid will cause the added H3O+ to react with
excess acetate to form the unionised ethanoic acid. On addition of strong base the
added OH- reacts with H3O+ to form water.
In the preparation of buffers some factors need to be considered which include buffer
range and buffer capacity. Buffer range refers to the pH range over which the buffer is
effective while buffer capacity is the amount of strong base (or strong acid) required
to alter the pH by 1 unit. The buffer capacity determines the amount of strong acid or
strong base that may be added without producing a significant change in pH. The
empirical equation that computes the pH of buffer is the Henderson-Hasselbalch
equation. This equation can be derived as follows.
For the dissociation of weak acid HA to give conjugate base A-
[H3O+ ][A - ]
Ka 
[HA]
[HA]
 Ka -
= [H3O+ ]
[A ]
If we take the negative logarithm to base 10 of both sides of the above equation we
obtain:
[HA]
pKa  log = pH
[A - ]
Where [HA] is the concentration of the acid and [A-] is the conjugate base which in
disguise, stands for the concentration of the salt.
[Acid]
pH = pK a  log (Henderson-Hasselbalch equation)
[Salt]
Similarly, for weak base and its salt:

[B]
[OH] = x Kb
[BH + ]
[Base]
Therefore: pOH = pK b  log
[Salt]
For the ionisation of a weak base:
B + H2O BH+(aq) + OH-(aq)
In analogous manner to weak acids derive the following equations for weak base and
its conjugate:
[Acid]
pOH = pK b  log
[Salt]
Problem: Calculate the pH of an aqueous buffer solution which contains 0.1 mol/dm3
NH3 and 0.2 mol/dm3 NH4Cl. (pKa (NH4+) = 9.3)
Solution: NH4Cl NH4+ + Cl-

0.2 mol/dm3
NH3 + H2O NH4+ + OH-
0.1 mol/dm3
Step 2: Select a suitable Henderson-Hasselbalch equation:
[Acid]
pH = pK a  log
[Salt]
Step 3: Identify the acid HA and the conjugate base A-
(0.2)
pH = 9.3  log
(0.1)
pH = 9.3 – 0.3 = 9.0
Acid-base titration and indicators

Basically, acid-base titration is a neutralization reaction in which the titrant is either an
acid or a base and the solution being basic or acidic respectively. Usually pH indicator
is added in order to show the endpoint. An acid-base indicator is a weak acid or base
with conjugate forms having different colours. The following equations represent the
change that takes place in an indicator which is a weak acid
+ -
HInd + H 2O H3O + Ind
Weak acid Conjugate base
The indicator constant Kind is given by the following equation:
[Ind - ][H3O+ ]
Kind 
[HInd]
By taking the –log of both sides and rearrangement we obtain the following equation:
[HInd]
pKind  pH  log
[Ind - ]
pH = pKind at the endpoint
pH < pKind when the indicator and corresponding colour are predominantly in
acidic form
pH > pKind when the indicator and corresponding colour are predominantly in
basic form
Endpoint is indicated by sharp colour change resulting from the addition of only a
slight excess of the titrant. The choice of appropriate indicator becomes necessary in
acid-base titration so as to achieve rapid colour change as endpoint is reached. Table
3.1 gives a guide to the choice of indicator, depending on the titrant and titrand used.
Table 3.1 Acid-base titrations and the suitable indicators for use
Acid-Base Titration Rapid pH Suitable
change occurs Indicator
Strong acid against 3.5 – 9.5 Any indicator
strong base
Strong base against 7.0 – 9.5 Phenolphthalein
weak acid
Strong acid against 3.5 – 7.0 Methyl orange
weak base pH curve or
Weak acid against weak No sharp No suitable titration curve is
base change indicator graph of pH versus
volume of titrant
used. The pH curve displays the progress of titration. At this juncture, it is important
to distinguish between equivalence point (or stoichiometric point) and endpoint. The
equivalence point is a specific point on the graph at exact which neutralization is
deemed complete. The pH of the indicator must change at the equivalence point of
the reaction. In other words endpoint must coincide with equivalence point. The
equivalent point can be seen by inspection, but can also be calculated precisely via
integral calculus by computing the points of inflection on the pH curve.
Case I: In case of titration of strong acid (e.g. HCl) versus strong base (e.g. NaOH)
where the pH of the resulting solution is ultimately 7, the endpoint could be called the
neutral point (even though the use of endpoint has been preferred by analysts). The
pH curve begins at high pH typical of strong base and ends at low pH typical of strong
acid. There is a rapid change in pH near the equivalence point (pH =7) (Fig. 3.2a).
pH = pOH = 7
14
pH
7 Equivalence point
0
25ml ml of acid
Fig 3.2a Strong acid versus strong base pH curve
Hydrolysis: Acid and base react to form salt and water. The reverse process (in which
the salt forms the acid and base in presence of water) is called hydrolysis. The salt of
stong acid and strong base does not undergo hydrolysis.
Case II: For titration of weak acid (e.g. CH3COOH) against strong base (e.g. NaOH)
HA + BOH BA + H2 O
Where B can be metal ion such as Na or non-metal ion such as NH4+
+
e.g. CH3COOH + NaOH CH3COONa + H2 O

We know that Kw = [OH][H3O+]
[H3O+ ][A - ]
Because K a  we can have the following expression for Kw :
[HA]
K [HA]
 K w  [OH] x a -
[A ]
The majority of the [OH-] in the solution is due to Brønsted equilibrium above and the
levels have outnumbered that of autoionisation. (Students should think of the reason)
Hence [OH-] = [HA],
K a [OH]2
 Kw 
[A - ]
If we make [OH] the subject of the formula and take –log of both sides of the
resulting equation we obtain:
pOH = ½ (pKw – pKa –log[A-])
The titration curve begins at a higher acidic pH and ends at high basic pH (Fig 3.2b).
The pH change at the equivalence point (pH > 7) is not so great and after the
equivalence point a buffer solution is formed. Because pKw = pH – pOH, the pH at that
equivalence point is given by:
pH = ½ (pKw + pKa + log[A-])
where [A-] = [Salt]
14
pH
Equivalence point
0
25ml ml of acid
Fig 3.2b Weak acid versus strong base pH curve
Problem: Calculate the value of pH at stoichiometric point of titration of 20 cm3 of 0.1

mol/dm3 HClO(aq) with 0.1 mol/dm3 NaOH
pKa (NaClO) = 7.4
Solution:
The first thing to note is that the titration is between weak acid and strong base.
HClO + NaOH NaClO + H2O
Therefore, pH = ½pKa + ½pKw + ½log [A-]
At the stoichiometric point the volume is twice 20 cm3
We know that MV = constant
So, 0.1 mol/dm3 x 20 cm3 = 40 cm3 x [NaClO]
The concentration of the salt = [NaClO] = 0.05 mol/dm3
pH = ½(7.4) + ½(14) + ½log (0.05)
pH = 9.4
Hydrolysis: For the hydrolysis of the salt of weak acid and strong base in water (which
is the reverse reaction to case II, the same pH formula (above) holds. However, we
can include the hydrolytic constant Kh in the equation.
For the hydrolysis of salt BA (of weak acid and strong base)
A- + H2O HA + OH- (the spectator ion B is not shown)
the hydrolytic constant Kh can be expressed by
[HA][OH - ]
Kh 
[A - ]
[OH- ][HA] [H + ]
Kh  x
[A- ] [H + ]
K
 K h  w which means pKh = pKw - pKa
Ka
If use this relationship, the pH equation above turns to the following
pH = ½pKw- ½pKa+ ½log [A-]
where [A-] = [Salt BA]
The pH of the solution at equivalence point (and so is the p Kind) as well as on
hydrolysis is greater than 7.
Case III: For strong acid (e.g. HCl) against weak base (e.g. NH3) the curve begins at
low pH and ends at a less high alkaline pH (Fig 3.2c). The pH change at the
equivalence point (pH < 7) is not great.
HA + BOH BA + H2 O
e.g. CH3COOH + NaOH CH3COONa + H2 O
[H3O+ ][A - ] [H3O+ ]2
Because K a  
[HA] [A- ]
we can have the following expression for [H3O+]:
[H3O+ ]  [A- ] x Ka 
1
2
If we take the –log of both sides of the equation we arrive at

-log[H3O+] = -½logKa - ½log[A-]
 the pH at stoichiometric point of strong acid-weak base titration is given by:
pH = ½pKa- ½log [A-]
Where [A-] = [Salt]
Problem: If 10 ml of 0.3 mol/dm3 NH3(aq) is reacted with H2SO4 what will be the pH at
stoichiometric point? pKa (NH4+) = 9.3
Solution: The first thing to note is that the titration is between strong acid and weak
base.
Therefore, pH = ½pKa- ½log [A-]
Now, the concentration of salt ([A-]) will depend on the concentration of the weak
base. At the stoichiometric point the volume will double and the concentration of the
salt can be obtained from the relationship MV = constant:
0.3 mol/dm3 x 10 cm3 = 20 cm3 x [A-]
The concentration of the salt = [A-] = 0.15 mol/dm3
pH = ½(9.3)- ½log 0.15 = 4.65 - 0.41
pH = 4.24
Hydrolysis: For the hydrolysis of the salt of strong acid and weak base in water (which
is the reverse reaction of Case III), the same pH formula (above) holds. However, we
may need to include the hydrolytic constant Kh in the equation.
For the hydrolysis of salt BA (of strong acid and weak base)
BA + H 2O HA + BOH
[B][H3O+ ]
Kh 
[BA]
[B][H3O+ ] [OH- ]
Kh  x
[BA] [OH - ]
K
 K h  w which means pKh = pKw – pKb
Kb
If use this relationship, the pH equation above turns to the following
pH = ½pKw- ½pKb+ ½log [A-]
The pH of this salt solution is on hydrolysis is < 7. The pKind is also < 7.
Case IV: There is difficulty in performing titrations involving weak acid (e.g.
CH3COOH) against weak base (e.g. NH3) because the pH change at equivalence point
is negligible. Fig 3.2d shows that the curve begins at higher acidic pH and ends at low
alkaline pH.
At the stoichiometric point pH = ½ (pKw + pKa - pKb)
14 14
pH pH
7 7
Equivalence point Equivalence point
0 0
25ml ml of acid 25ml ml of alkali
Fig 3.2c Strong acid versus weak base pH curve Fig 3.2d Weak base versus weak acid pH curve
Hydrolysis:
There is both cation and anion in the hydrolysis of the salt of weak acid and weak
base. However, we may need to include the hydrolytic constant Kh in the equation.
For the hydrolysis of salt BA (weak acid-weak base salt)
B+ + A- + H2O BOH(aq) + HA(aq)
[BOH][HA]
Kh 
[B+ ][A - ]
If we multiply the above equation and divide by [H+][OH-] we obtain
 [BOH]   [HA] 
Kh   + - 
x + - 
x [H + ][OH - ]
 [B ][A ]   [H ][A ] 
 [H ][A ] 
+ -
 [B ][OH ] 
+ -
But Ka =   and Kb   ,
 [HA]   [BOH] 
Kw
 Kh 
Ka Kb
From this relationship we can conclude that pKh = pKw - pKa - pKb
If use these relationship, the pH equation above turns to the following
pH = ½pKw- ½pKb+ ½log [A-]
Accordingly, the pH of this salt solution is < 7.
Case V: The pH at equivalence
point or theoretical endpoint
corresponds to the pH of the
solution of the salt formed. For
diprotic and polyprotic acids
which contain more than one
acidic hydrogen and ionise in
more than one step (e.g. H3PO4)
there exist more than one salt
each at a different pH (Fig.
3.2e). When these acids are 14
titrated against strong bases,
two different pHs are observed-
pH
at first and second equivalence
point. The pH at the first and
2nd Equivalence point
second equivalence point is 7
given approximately by:
pH = ½ (pK1 +pK2) and 1st Equivalence point
pH = ½ (pK2 +pK3)
respectively. Where K1, K2 and
0
K3 are rate constants for the ml of base
elementary steps of ionization.
Fig 3.2e pH curve for strong diprotic acid versus base
The visibility of the endpoints of
the titrations decreases. In
other words, the first endpoint
is most obvious.
Solubility equilibria
On addition of water to a sparingly soluble ionic salt, a saturated solution is formed.
Eventually, the ions so formed will be in equilibrium with the excess undissolved
solute.
MxXy(s) xM+(aq) + yX-(aq)
e.g. BaSO4 Ba2+ + SO42-
[Ba 2+ ][SO4 2+ ]
K
[BaSO4 ]
 [Ba2+][SO42-] = K[BaSO4]
The product [Ba2+][SO42-] at any instant is known as the ion activity product (IAP).
The IAP at saturation is known as the solubility product (Ksp).
 Ksp = [Ba2+][SO42-]
The following points should be noted about IAP.
1. In undersaturated solution IAP < Ksp
2. In saturated solution there is a state of equilibrium between salt and the solution
and IAP = Ksp
3. In supersaturated solution IAP > Ksp
Solubility product must not be confused with solubility. Solubility of a salt refers to the
total, maximum concentration of salt dissolvable.
Problem: Find the solubility product of BaSO4, if the saturated solution of the salt
contains 2.29 x 10-3 g/dm3 at 20 oC
Solution: The solubility (total concentration) of BaSO4 = 2.29 x 10-3 g/dm3 at 20 oC
We need to convert this concentration to that in molar unit. Since the molar mass of
BaSO4 = 233.2 g/mol the concentration in mol/dm3 is given by:
(2.39 x 10-3 g/dm3 )
Concentration (mol/dm3 )  = 1 x 10-5
2.33 g/mol
BaSO4 Ba2+ + SO42-

Ksp = [Ba2+][SO42-] = 1 x 10-5 mol/dm3 x 1 x 10-5 mol/dm3
 Ksp = 1 x 10-10 mol2/dm6 Note: (dm3 = L2)
Problem: Find the solubility of Ca(OH)2 in water if Ksp = 1.32 x 10-11 mol3/dm9
Solution: Ca(OH)2 Ca2+ + 2OH-
Ksp = [Ca2+][OH-]2
Let [Ca2+] = x, then [OH-] = 2x
Ksp = 1.32 x 10-11 = x x (2x)2
 4x3 = 1.32 x 10-11 x = 2.36 x 10-4 mol/dm3
Application of solubility product
1. Prediction of precipitation
If IAP is greater than Ksp value, it means precipitation can occur.
Problem: Determine whether a precipitate will form when equal volumes of 0.2
mol/dm3 Pb2+ and 0.3 mol/dm3 SO42- solution, if Ksp(PbSO4) = 2 x 10-8
Solution: PbSO4 Pb2+ + SO42-
Ksp = [Pb2+][SO42-] = 2 x 10-8 mol2/dm6
Immediately after mixing, the concentration of Pb2+ and SO42- ions gets halved
and the ion activity product becomes:
IAP = [Pb2+][SO42-] = (0.1) x (0.15) = 1.5 x 10-2 mol2/dm6
Because IAP is >> Ksp precipitation will occur.
2. Common ion effect
The solubility of an ionic salt will reduce if mixed with the solution of another salt
containing the same ion.
Generally, the solubility of salt A+B- will be reduced in the presence of A+ or B- from a
second source.
Problem: Calculate the solubility of AgCl (a) in water (b) in 0.1 mol/dm3 NaCl
Ksp(AgCl) = 2 x 10-10 mol2/dm6
Solution: (a) In water
AgCl(s) Ag+(aq) + Cl-(aq)
Let the solubility of AgCl be x
Ksp (AgCl) = [Ag+][Cl-] = (x) x (x)
Or 2 x 10-10 mol2/dm6 = x2 x = 1.4 x 10-5 mol/dm3
(b) In 0.1 mol/dm3 NaCl
0.1 mol/dm3 0.1 mol/dm3 0.1 mol/dm3
[Ag+] = x mol/dm3
[Cl-] = (x + 0.1) mol/dm3
Ksp (AgCl) = [Ag+][Cl-] = (x) x (x + 0.1)
2 x 10-10 mol2/dm6 = (x) x (x + 0.1)
But x << 0.1  (x + 0.1) ≈ 0.1
-10 2 6
2 x 10 mol /dm = (x) x (0.1)
x = 2 x 10-9 mol/dm3
3. Prediction of concentration of ions in solution
If an excess solution of a given cation (e.g. Ag+) is mixed with a solution of a suitable
anion (e.g. Cl-), the concentration of the cation remaining in solution can be calculated
using the Ksp of AgCl.
XIDATION AND REDUCTION (REDOX) REACTIONS
O Definitions
1. a) Oxidation is the addition of oxygen to or the removal of hydrogen from a
substance
examples i) addition of oxygen
2Mg + O2 2MgO
ii) removal of hydrogen
Zn + 2HCl ZnCl2 + H2
b) Reduction is the addition of hydrogen to or the removal of oxygen from a substance
examples i) addition of hydrogen
H2 + Cl2 2HCl
ii) removal of oxygen
Fe2O3 + 3CO 2Fe + 3CO2
2. a) Oxidation is the apparent loss of electrons by an atom, ion or molecule ie
Zn(s) Zn(aq) + 2e-
b) Reduction is the apparent gain of electron(s) by an atom, ion or molecule. ie
Cu2+(aq) + 2e- Cu(s)
The electron(s) lost in an oxidation process must be gained in a reduction process,
thus the two processes occur simultaneously in equivalent amounts and the net
reaction is therefore referred to as redox (reduction-oxidation) reactions.
The individual process of loss (oxidation) and gain (reduction) of electrons are written
separately as half equations, and the two summed up in stoichiometric proportions to
obtain the overall (redox) equation
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
The electron donor that causes reduction by loosing electron(s) which becomes
oxidized in the process is known as the reducing agent (or reductant) and the
electron acceptor that causes oxidation and which becomes reduced by gaining
electrons is known as the oxidizing agent (or oxidant). In the above example,
therefore, Zn is the reducing agent (reductant) and Cu2+ is the oxidizing agent
(oxidant).
3. a) oxidation is the increase in the oxidation number of an atom, molecule or ion.
b) reduction is a decrease in the oxidation number of an atom, molecule or ion.
Oxidation number (ON)

Oxidation number is the number of electrons that need to be added to an ion to make
it a neutral atom, while the oxidation state is a number written in roman numerals that
indicates the extent of oxidation of an atom.
Rules for assigning oxidation number

1. the ON of an atom (or molecule) of an element is 0 ie the ON of N 2 and O2 is 0
2. the ON of a monoatomic ion is equal to its charge ie ON of potassium in K + is
+1, zinc in Zn2+ is +2, sulphur in S2- is -2.
3. the sum of the ON of all atoms in polyatomic ion is equal to the charge on the
ion. ie in SO42-, ON = -2; in NO3-, ON = -1
4. for a neutral compound the sum of oxidation numbers is 0
5. the ON of hydrogen is taken as +1, except in metal hydrides such as NaH, LiH
etc where it is -1
6. the ON of oxygen is usually -2 except in peroxides (such as H2O2) where it is -1
and in superoxides (such as KO2, CsO2 etc) where it is -1/2
Uses of oxidation number

1. in naming inorganic compounds
2. in balancing redox equations
Oxidation number forms the basis for naming compounds according to the IUPAC
convention
Compound IUPAC Name
HNO3 Trioxonitrate (V) acid
HClO4 Tetraoxochlorate (VII) acid
H2SO4 Tetraoxosulphate (VI) acid
NaMnO4 Sodium tetraoxomanganate (VII)
K2Cr2O7 Potassiumheptaoxodichromate (VI)
Tests for oxidizing agents
1. most oxidizing agents liberate iodine from acidified potassium iodide solution.
This will result in the formation of a red brown solution that turns dark blue
upon addition of starch.
2. if sulphur(IV)oxide, SO2 is bubbled through a solution of an oxidizing agent, the
SO2 will be oxidized to the SO42- ion. The presence of the SO42- can be
confirmed using dilute trioxonitrate (V) acid and barium trioxonitrate (V)
solution. A white precipitate shows that the substance is an oxidizing agent.
Tests for reducing agents
1. reducing agents decolorize the deep purple colour of acidified potassium
tetraoxomanganate (VII) solution.
2. reducing agents produce a green solution upon warming with an orange
solution of acidified potassium heptaoxodichromate (VI), K2Cr2O7 solution.
Balancing redox reaction equations

Guidelines
1. identify the reducing and oxidizing agents with their products
2. write the balance half equations with regards to oxidation and reduction. If the
redox reaction takes place in an acidic medium then for every excess oxygen
atom, O, add two H+ to the same side and balance with one water, H2O on the
other side. If the reaction takes place in a basic medium, then for every excess
oxygen, O, atom, add one water, H2O to the same side and balance with two
OH- on the other side. If both oxygen and hydrogen are in excess on the same
side of the equation, an OH- can be written on the other side for each pair of
excess H and O.
3. Multiply the half equations where necessary to balance the electron transfer and
sum up the half equations to obtain the overall equation.
Examples
Balance the following equations
1. MnO4- + Sn2+ Mn2+ + Sn4+ (acidic medium)
2- 2+ 3+ 3+
2. Cr2O7 + Fe 2Cr + Fe (acidic medium)
- 2- 2-
3. MnO4 + SO3 MnO2 + SO4 (basic medium)
Solution
1. MnO4- + Sn2+ Mn2+ + Sn4+ (acidic medium)
Reduction half equation
MnO4- Mn2+
+7 +2
Manganese is reduced from +7 to +2 ON by accepting 5e-
MnO4- + 5e- Mn2+
Since the reaction takes place in acidic medium
MnO4- + 8H+ + 5e- Mn2+ + 4H2O---------1
Oxidation half equation
Sn2+ Sn4+
+2 +4
2+ 4+
Sn Sn + 2e- -------------2
Tin(II) has lost 2 e-
To balance the electrons we multiply equation 1 by 2 and equation 2 by 5 and add the
two equations to obtain the overall redox equation
2MnO4- + 16H+ + 10e- 2Mn2+ + 8H2O
2+ 4+ -
5Sn 5Sn + 10e
-
Overall reaction is 2MnO4 + 5Sn2+ + 16H+ 2Mn2+ +
5Sn4+ + 8H2O
2. Cr2O72- + Fe2+ Cr3+ + Fe3+ (acidic medium)
Reduction half reaction
Cr2O72- 2Cr3+
+6 +3
2- -
Cr2O7 + 6e 2Cr3+
Since the reaction takes place in acidic medium
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O--------1
Oxidation half reaction
Fe2+ Fe3+
+2 +3
2+
Fe Fe3+ + e-------------------------2
We multiply equation 1 by 1 and equation 2 by 6 to balance the electron transfer
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O
6Fe2+ 6Fe3+ + 6e-
Overall reaction Cr2O72- + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+
+ 7H2O
3. MnO4- + SO32- MnO2 + SO42- (basic

medium)
Reduction half equation
MnO4- MnO2
+7 +4
- -
MnO4 + 3e MnO2
The reaction takes place in a basic medium so we balance the oxygen thus
MnO4- + 2H2O + 3e- MnO2 + 4OH- --
------1
Oxidation half equation
SO32- SO42-
+4 +6
2-
SO3 SO42- + 2e-
We balance the O under alkaline conditions thus
SO32- + 2OH- SO42- + H2O + 2e- ------2
We multiply equation 1 by 2 and equation 2 by 3 to balance the electron transfer
2MnO4- + 4H2O + 6e- 2MnO2 + 8OH-
3SO32- + 6OH- 3SO42- + 3H2O + 6e-
Overall equation 2MnO4- + 3SO32- + H 2O 2MnO2 +
2- -
3SO4 + 2OH
Problems
1. give two definitions of reduction with examples
2. determine the oxidation number of manganese in MnO4- and that of chromium
in Cr2O72-
3. Consider the following reaction
Cu(s) + Ag+ (aq) Cu2+(aq) + Ag(s)
i) state the specie that is reduced
ii) which specie is oxidized
iii) write half cell equation for each of the reacting species
4. balance the following redox equations in both acidic and alkaline medium
i) Cr2O72- + SO2 2Cr3+ + SO42-
ii) MnO4- + C2O42- Mn2+ + 2CO2
-
iii) NO3 + H 2S NO + S
- 2+
iv) MnO4 + Fe Mn2+ + Fe3+
5. a) define oxidation and reduction in terms of electron transfer
b) what is the relationship between the number of electrons gained and lost in a
redox reaction
c) do all electrochemical cells involve redox reactions?
6. define and illustrate oxidizing and reducing agents
7. for each of the following unbalanced equations,
i) write the half reactions for oxidation and reduction,
ii) balance the overall equation in acidic solution using the half reaction method
a) Hg2+ + Pb Hg + Pb2+
b) MnO2 + Cl- Mn2+ + Cl2
2+ 4+
c) Sn + O2 Sn + H2O
8. for each of the following unbalanced equations,
ii) balance the overall equation in basic solution using the half reaction method
a) FeS + NO3- NO + SO42- + Fe2+
b) Cr2O72- + Fe2+ Cr3+ + Fe3+
c) S2- + Cl2 + OH- SO42- + Cl- + H2O
9. For each of the following unbalanced equations
ii) identify the species that lost and the species that gained electrons,
iii) write the balanced net ionic equation for the overall reaction
a) Ni + Sn2+ Ni2+ + Sn
- 2+
b) MnO4 + Cu Cu + Mn2+ (acidic solution)
- - 2-
c) Cr(OH)3 + IO3 I + CrO4 (basic solution)
- - -
d) N2O4 + Br NO2 + Br3 (basic solution)
- 2- - 3+
e) NO2 + Cr2O7 NO3 + Cr
10. Provide the IUPAC nomenclature for the following radicals
a) Cr2O72- b) ClO4- c) PO43- d) MnO4- e) NO3- f) C2O42-
LECTROCHEMISTRY
Branch of physical chemistry concerned with the behavior of ions in solutions, their
Einteraction with one another and with a metallic conductor (Electrode) and the
subsequent relation between chemical energy and electrical energy.
Uses of Electrochemistry
1. Power source
a. Batteries
b. Fuel cells (Space craft)
2. Corrosion prevention
3. Pollution analysis
4. Biomedical research
ELECTROLYTIC AND ELECTROCHEMICAL CELLS
Electrolytic Cell
Any device in which electrical energy is converted into chemical energy, e.g. any
set-up used in electrolysis; which comprises of:
1. An electrolyte
2. An electrodes
a. Anode which is the positive electrode
b. Cathode which is the negative electrode
3. Both the electrolyte and the electrode are existing in the same container; with
the two electrodes connected externally by an electric circuit serving as a source
of direct current (DC).
Electrochemical Cell
This is a device that converts chemical energy into electrical energy e.g.
batteries. In this type of cell Anode is the negative electrode while Cathode is the
positive electrode. Each electrode is dipped separately into its electrolyte or a paste
containing ions. The two separate electrolytes are connected (joined) by a salt bridge;
which is a paste of KNO3 or KCl.
CELL POTENTIAL
When a metal is in contact with water or ionic solution it dissociates to give ions
in the solution leaving behind electrons on the remaining surface of the metal; e.g.
The force with which these electrons are transported from the negative electrode to
the positive electrode is called electromotive force (EMF) or cell potential having a
unit of volts;
Reduction Potential
Generally when a metal electrode is dipped in its aqueous solution, the ions in
the solution try to withdraw electrons from the metal electrode in order to get
reduced. The extent with which this process takes place is referred to as reduction
potential.
STANDARD HYDROGEN ELECTRODE (SHE)

The SHE consists of hydrogen gas (H2(g)) at 1atm bubbling over a platinised
platinum plate (electrode) immersed in a solution of 1M HCl at 25°C. The platinised
platinum electrode has the following uses in the SHE:
1. It acts as an inert metal connection to the H2/H+ system.
2. It allows H2(g) to be adsorbed on its surface.
3. Being platinsed, it has increased surface area so that it can establish an
equilibrium between H2(g) and H+(aq) as rapidly as possible.
The SHE is assumed to have a standard electrode potential E°, of zero (0.00V); i.e. for
the reaction ½H2(g) → H+(aq) + e-; E° = 0.00V.
Standard Electrode (Half – Cell) Reduction Potential

To measure the standard reduction potential of a given half-cell;
1. All the ionic species must have a concentration of 1M.
2. All gases should be at 1atm pressure.
3. Working temperature should be 25°C, and
4. Platinum should be used as the electrode when the half-cell does not include a
metal.
Generally, the standard reduction potential (E°) of any half – cell is obtained by
reference to that of the SHE. For instance the standard reduction potential of a
Zn(s)/Zn2+(aq) half – cell, is the potential difference between SHE and the zinc half –
cell.
Generally,
E°cell = E°RHS - E°LHS
= E°Zn/Zn2+ - E°H2/H+
= E°Zn/Zn2+ - 0
E°Zn/Zn2+ = -0.76V
VOLTAIC CELL
This is formed by combining two types of half – cells, e.g. a Daniel cell is formed by
combining zinc and copper half cells.
In this cell the reaction taking place is Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s). The
standard reduction potential of this type of cell is defined as “the reduction potential
for the substance that actually undergoes reduction minus the reduction potential
for the substance that is forced to undergo oxidation”. Thus;
CELL DIAGRAM
A cell diagram is any representation that shows the nature of the electrode
material, nature of the solution in contact with the electrode, which half – cell is anode
or cathode and the reactants or products in each half cell.
To draw a cell diagram one needs to:
1. Identify the anode half – cell (Oxidation half – cell) i.e. the half – cell with
smaller or more negative E° value. Also to identify the cathode (reduction half
– cell) i.e. the half – cell with larger E° value.
2. The salt bridge is represented by a pair of vertical lines or single broken line
which separates the two half – cells.
3. A single vertical line is used to represent a phase boundary with the
concentration of the Mn+(aq) shown in brackets ( ).
4. If inert electrodes are used, the least oxidized specie is written next to it.
Thus, the cell diagram for Daniel cell is;
Similarly, the cell diagram for standard Zn electrode is;
While example of a least oxidized specie with inert electrode is;
ELECTROCHEMICAL SERIES
This is a series showing the arrangement of electrodes half – cell reactions and
their corresponding standard reduction potential, E°(V) in their decreasing or
increasing order.
Uses of Reduction Potential

1. Oxidising Agent/Oxidising Power
A positive value of E° implies that the corresponding electrode has tendency to
gain electrons; and the more the positive the E°, the greater the tendency of the
electrode to gain electron. Thus, any half – cell with positive E° value is an oxidizing
agent, and the oxidizing power increases with increase in the E° value.
2. Spontaneous Redox Reaction

A reaction is spontaneous if and only if E°cell is positive.
EXAMPLE
Assuming the reaction Fe2+(aq) + Ni(s) → Fe(s) + Ni2+(aq). The two half – cells
are:
Reduction half – cell; Fe2+(aq) + 2e- → Fe(s) having E° = -0.44V.
Oxidation half – cell; Ni(s) → Ni2+(aq) + 2e- having E° = +0.25V [NOTE: E° for
oxidation = - E° for reduction i.e. ]
from = -0.44 – (- 0.25) = - 0.19V; and therefore
the reaction is non-spontaneous.
EXERCISE
A mixture contains Cr3+(aq) and Zn2+(aq). Deduce the overall cell reaction and
calculate E°cell.
3. Determination of the Direction of a given Reaction

Recalling that for the reaction;
Fe2+(aq) + Ni(s) → Fe(s) + Ni2+(aq)
the cell potential (E°cell) is -0.19V which implies that the reaction is non –
spontaneous. However, for the reaction;
Fe(s) + Ni2+(aq) → Fe2+(aq) + Ni(s)
The half – reactions are:
Oxidation half – reaction: Fe(s) → Fe2+(aq) + 2e-
Reduction half – reaction: Ni2+ + 2e- → Ni
E°cell =
Thus, changing the direction of the reaction made it to become spontaneous.
4. Possible Half – Reaction Combination
 If the electrochemical series is arranged in an increasing order, then any
specie on the LHS of a given half – reaction will react spontaneously with
another specie on the RHS of a given half – reaction located above it. E.g.
Ca2+/Ca: Ca2+ + 2e- → Ca: E° = -2.87V
Na+/Na: Na+ + e- → Na: E° = -2.71V
This shows that Na+ can combine with Ca.
 If the electrochemical series is in decreasing order, then a specie on the LHS
combines with any specie on the RHS of a half reaction below it.
5. Preferential Discharge of Ions in Electrolysis
The more positive the E° of an ion in the electrochemical series, the more
preferentially it is discharged during electrolysis. E.g. in electrolysis of aqueous Cu2+
(i.e. Cu2+ & H2O) Cu(s) is deposited but not H2O, this is because Cu2+/Cu electrode
has E° = +0.34V, while H2O/H2 electrode has E° = -0.83V. However, in electrolysis
of aqueous Al3+, water is discharged but not Al(s) which has E° = -1.66V.
Reduction Potential in Non – Standard State (E)

For any given reaction of the type:
aA + bB → cC + dD
; where n is number of electrons transferred while Q is reaction
quotient defined by ; and if T = 25°C, ; thus

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DEPARTMENT

CHM 1251 – PHYSICAL CHEMISTRY

FOR STUDENTS FROM FACULTIES OF

DERIVATION OF IDEAL GAS EQUATION

CALCULATING THE NUMBER OF MOLES, n

Example: Calculate the number of moles of the following gases;

EXPRESSING PV=nRT INTERMS OF DENSITY, ρ

DALTON’S LAW OF PARTIAL PRESSURE

RELATION BETWEEN PARTIAL PRESSURE, MOLE FRACTION AND TOTAL

3|Page CHM 1251 -PHYSICAL CHEMISTRY (2012/13 SESSION)

KINETIC MOLECULAR THEORY OF GASES

FUNDAMENTAL EQUATION FOR THE PRESSURE OF A GAS.

DEDUCTION OF GAS LAWS FROM THE KINETIC GAS EQUATION

5|Page CHM 1251 -PHYSICAL CHEMISTRY (2012/13 SESSION)

4) Graham’s Law of Diffusion:

ROOT MEAN SQUARE VELOCITY

Taking the square root, we have,

U is thus the Root Mean Square Velocity or RMS velocity. It is denoted by U.

6|Page CHM 1251 -PHYSICAL CHEMISTRY (2012/13 SESSION)

Where M = molar mass

By substituting the values of R, T and M, the value of U (RMS velocity) can be

Where Z = compression factor

P, R and T have their usual meanings.

EXPLANATION OF DEVIATION – VANDER WAALS EQUATION

VAN DER WAALS EQUATION

Example: Calculate the pressure exerted by 1.00mole of methane (CH4) in a 250mL

LIMITATION OF VAN DER WAALS EQUATION

Thermochemistry is the study of energy changes, which occur during chemical

Definition of Some Terms

Reactants H = HP – HR, where HR, HP are

Endothermic reaction: is a reaction in which heat is absorbed from the surrounding.

(ii) If the balanced equation is multiplied by a factor n,  H is also multiplied by the

STANDARD ENTHALPY CHANGES

The enthalpy change of this reaction H1 is equal to H oc (C(s))

The enthalpy change of the reaction H 2 is not equal to H oc (C(s))

Enthalpy Sign Enthalpy Sign

HESS’S LAW OF CONSTANT HEAT SUMMATION

THERMOCHEMICAL (OR BORN – HABER) CYCLE

Born – Haber cycle involving formation and combustion reactions

Reactants at their Formation

Combustion Combustion equation

The amount of O2(g) required to completely burn C6 H 6 l  is

The complete thermochemical cycle is given below;

Enthalpy change along path 1 = H 3o

Born-Haber cycle for polymerisation reaction

Example 17: Given that:

Born – Baber cycle for formation of ionic solids

H odiss Cl 2 ( g )  =+242kJmol , IP Na ( g )  = +500kJmol , EA(Cl(g) = – 364kJmol .

The lattice energy of NaCl(s) is calculated as follows

Example 19: Study the following thermochemical cycle

(a) Identify the enthalpy changes  H1,  H2……….  H9

 H7 = 1st EA of O(g),  H8 = 2ndEA of O(g),  H9 = Al2O3(g))

Born – Haber cycle for bond energy calculations

The gaseous atoms are formed by the reactions

= – 716 – 2(433) – 393 + 2(–286) – (–890)

CH4(g) 4BDEC-H Born-Haber Cycle

= – 890 – (–393) – 2(–286) + 716 + 2(433)

2C(s) + 3H2(g) + ½ O2(g) H of