CHEMICAL EQUILIBRIUM

(PhysicaI Chemistry I)

NELSON M. PANAJON
Department of Chemistry
CENTRAL LUZON STATE UNIVERSITY
 CHEMICAL EQUILIBRIUM

TO BE IN EQUILIBRIUM
is to be in a state of balance.
- can be static or dynamic

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 2

 CHEMICAL EQUILIBRIUM

- occurs when opposing reactions proceed

at equal rates
- holds true for reversible reactions
- concentrations of the reacting species no
longer change as dynamic equilibrium is
achieved

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 3

 CHEMICAL EQUILIBRIUM
Recalling kinetics:
for N2O4 (g) 2NO2 (g)
rateforward = -Kf [N2O4]
ratebackward = -Kb [NO2]2

at equilibrium:
rateforward = ratebackward
Kf [N2O4] = Kb [NO2]2

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 4

 CHEMICAL EQUILIBRIUM

for N2O4 (g) 2NO2 (g)

- Kf [N2O4] = - Kb [NO2]2
becomes
Kf [NO2]2
= = equilibrium constant (or Keq)
Kb [N2O4]
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 5
 CHEMICAL EQUILIBRIUM
The fate of the reacting species at equilibrium .
(Chemistry: The Central Science ©2012 by Brown etal)

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 6

 EQUILIBRIUM CONSTANTS

- generally expressed either as Kc (for

gases and aqueous solutions) or Kp (for
gases)
- KC depends on molar equilibrium
concentration while KP is based on
pressure

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 7

 EQUILIBRIUM CONSTANTS
- KC and KP are related to each other by the
equation:
Kp = Kc(RT)Δn
where Kp and Kc – equilibrium constants
R – universal gas constant
T – absolute temperature
Δn = molegaseous products – mole gaseous reactants

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 8

 WRITING EQUILIBRIUM EXPRESSIONS
CHARACTERISTICS:
01. The equilibrium constant of a reaction in
the reverse direction is the inverse (or
reciprocal) of the equilibrium constant of
the reaction in the forward direction.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 9

 WRITING EQUILIBRIUM EXPRESSIONS
CHARACTERISTICS:
02. The equilibrium constant of a reaction that
has been multiplied by a number is equal
to the original equilibrium constant raised
to a power equal to that number.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 10

 WRITING EQUILIBRIUM EXPRESSIONS
CHARACTERISTICS:
03. The equilibrium constant for a net reaction
made up of two or more reactions is the
product of the equilibrium constants for the
individual reactions:

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 11

 WRITING EQUILIBRIUM EXPRESSIONS
CHARACTERISTICS:
04. Pure liquids and pure solids are not
included in the equilibrium expression.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 12

 SIMPLIFYING EQUILIBRIUM
CONSTANT EXPRESSIONS
Neglect x (or change in concentration) if the
analytical concentration is > 0.01 Keq OR if the ratio
between analytical concentration and equilibrium
constant is greater than 100.
For example, if the analytical (initial) concentration
is known to be at the 10-2 place and the equilibrium
constant is at the magnitude of 10-8, x may easily be
neglected since the difference in magnitude is 106 .

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 13

 LE CHATELIER’S PRINCIPLE

When change (or stress) is

added to a system at equilibrium,
the equilibrium will shift in a
direction that tends to relieve or
counter the stress.
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 14
 LE CHATELIER’S PRINCIPLE
- affected by factors like
I. Specie concentration
II. Pressure
III. Temperature

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 15

 LE CHATELIER’S PRINCIPLE

I. Effect of Concentration on Equilibria

- changes in concentration do not affect
the equilibrium constant, they affect the
position of the equilibrium

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 16

 LE CHATELIER’S PRINCIPLE

I. Effect of Concentration on Equilibria

- addition of a specie will shift the
equilibrium in the direction of decreasing
the concentration of the added specie

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 17

 LE CHATELIER’S PRINCIPLE

I. Effect of Concentration on Equilibria

- removal of a specie will shift the
equilibrium in the direction of increasing
the concentration of the removed specie

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 18

 LE CHATELIER’S PRINCIPLE

II. Effect of Pressure on Equilibria

- negligible on aqueous systems
- pressure can be varied in gaseous
equilibria thru:
(a) addition or removal of a gaseous
reactant or product

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 19

 LE CHATELIER’S PRINCIPLE

II. Effect of Pressure on Equilibria

- negligible on aqueous systems
- pressure can be varied in gaseous
equilibria thru:
(b) addition of an inert gas
(c) altering the system’s volume

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 20

 LE CHATELIER’S PRINCIPLE

II. Effect of Pressure on Equilibria

(a) for gaseous reactions, addition/removal
of a gaseous reactant/product have the
same effect as increasing/decreasing the
concentration of the reactant/product

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 21

 LE CHATELIER’S PRINCIPLE

II. Effect of Pressure on Equilibria

(b) for gaseous reactions, addition of an inert
gas in a system already at equilibrium
has no effect on the partial pressure of
the reacting species; hence has no effect
on the direction of equilibrium

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 22

 LE CHATELIER’S PRINCIPLE

II. Effect of Pressure on Equilibria

(c) for gaseous reactions, an increase in
pressure of a system (by reducing the
volume) favors the formation of lesser
number of moles of the gas

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 23

 LE CHATELIER’S PRINCIPLE

Effect of Temperature on Equilibria

- increasing the temperature of the system
favors the endothermic reaction; while
decreasing the temperature of the
system results to favoring the
exothermic reaction

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 24

 LE CHATELIER’S PRINCIPLE

Effect of Catalyst on Equilibria

- does not have any effect on the
equilibrium constant nor the position of
equilibrium

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 25

 EXERCISE:
A reaction occurs according to the equation:
2A Y + 2Z
If in a volume of 5 dm3 we start with 4 mol of pure A and find
that 1 mol of A remains at equilibrium, what is the
equilibrium constant Kc?

Ans:
2.7 mole/liter
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 26
 EXERCISE:
Given the following reactions at 700K,
H2(g) + I2(g) 2HI(g) Kp = 54.0
N2(g) + 3H2(g) 2NH3(g) Kp = 1.04 x10-4
calculate the value of Kc for the following reaction also at
700K:
2NH3(g) + 3I2(g) 6HI(g) + N2(g) Kc = ???

Ans:
4.59 x105
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 27
 EXERCISE:
Carbon monoxide gas is introduced to a container
containing an excess sulfur as in the given equation below.
2CO(g) + S(s) 2C(s) + SO2(g)
The initial pressure of the CO is 2.00 atm. When the system
reached equilibrium, the total pressure inside the container
becomes 1.03 atm. Determine the Kp for the given reaction
assuming the equilibrium pressures equals the activities.

Ans:
269
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 28
 EXERCISE:
The Kp for the given reaction below is 0.36 at a certain
temperature.
2CrSO4(s) Cr2O3(s) + SO2(g) + SO3(g)
If some solid CrSO4 was introduced to a container at
elevated temperature and with an initial SO3 partial
pressure of 1.00 atm, what would be the equilibrium partial
pressures of each gas?

Ans:
PSO3 = 1.28 atm; PSO2 = 0.28 atm
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 29
 THE REACTION QUOTIENT, Q:
PREDICTING THE DIRECTION OF EQUILIBRIUM

- set up similarly with the equilibrium

constant, K, but uses only the initial
concentration of the reacting species
wA + xB yC + zD
y
product [C] [D] z
Q = = w x
reactant [A] [B]
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 30
 THE REACTION QUOTIENT, Q:
PREDICTING THE DIRECTION OF EQUILIBRIUM

- If K > Q, then a net change occurs from

left to right (favors the forward reaction)
- If K < Q, then a net change occurs from
right to left (favors the reverse reaction)
- If Q = K, then the system is at equilibrium

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 31

 EQUILIBRIUM AND THERMODYNAMICS

Chemical equilibrium
is controlled by the
thermodynamics of the reaction.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 32

 FREE ENERGY IN EQUILIBRIUM
- is a definite measure of the reaction’s
spontaneity
- negative for spontaneous, positive for
nonspontaneous, and zero for processes
at equilibrium

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 33

 FREE ENERGY IN EQUILIBRIUM

- related to reaction quotient, Q, by the

equation:
ΔG = ΔGo + RT ln Q

which converts at equilibrium to:

ΔGo = -RT ln K
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 34
 FREE ENERGY IN EQUILIBRIUM
ΔGo = -RT ln K

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 35

 EXERCISE:
The standard Gibbs free energy for the following
reaction is 2.6 KJ/mole.
H2(g) + I2(g) 2HI(g)
A mixture initially contains 2.0 bars of hydrogen gas, 2.0
bars of iodine vapor and 0.50 bar of gaseous hydrogen
iodide in a sealed container at 398 K. Will more hydrogen
iodide form?

Ans:
Since ΔG is -6.6 KJ/mole, more HI will form
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 36
 EXERCISE:
Dinitrogen trioxide is an unstable compound that exists
in equilibrium with nitrogen oxide and nitrogen dioxide.
N2O3(g) NO(g) + NO2(g)
The standard Gibbs free energy of formation (in KJ/mole) is
139.3, 86.7, and 51 for N2O3, NO and NO2 respectively.
Calculate the Kp for the reaction at 25oC.

Ans:
1.3
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 37
 EXERCISE:
At 25 °C, the equilibrium constant is 1.0 ×10–5, and ΔS°
is 41.8 J/K-mol for the reaction given below.
CO(g) + H2O(g) CO2(g) + H2(g)
a. Calculate ΔG° and ΔH° at 25.0 °C.
b. Suppose that 2 mol of CO and 2 mol of H2O are
introduced into a 10-L vessel at 25°C. What are the
amounts of CO, H2O, CO2, and H2 at equilibrium?
Ans:
(a) ΔG° = 2.85 KJ/mole; ΔH° = 41.0 KJ/mole
(b) nCO2 = nH2 = 0.0063 ; nCO = nH2O = 1.99
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 38
 FREE ENERGY IN REDOX REACTIONS

- related to cell potential, Ecell, by the

equation:
ΔG = -nFEcell
where ΔG – (Gibb’s) free energy
n – number of electrons involved in the redox reaction
F – Faraday’s constant (96,485 Coulombs/mole of e-
Ecell – cell potential

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 39

 FREE ENERGY IN REDOX REACTIONS

- at standard conditions,
ΔG = -nFEcell
becomes
ΔG = -nFE cell
o o

o o o
where E cell = E cathode - E anode

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 40

 FREE ENERGY IN REDOX REACTIONS

- at standard and equilibrium conditions,

ΔGo = -nFEocell
and ΔGo = -RT ln K

which combines to form

o
E cell = RT ln K
nF
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 41
 Effect of Concentration on Cell Potential:
The Nernst Equation

For the redox reaction:

wA + xB → yC + zD

the ΔG = ΔG +
o RT ln Q

The Nernst equations!

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 42

 Effect of Concentration on Cell Potential:
The Nernst Equation

The Nernst equations can be simplified further at

o
25 C into:

Ecell = Eocell - 0.0257 V ln Q

n

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 43

 Effect of Concentration on Cell Potential:
The Nernst Equation

The Nernst
equations implies that
a cell could be created
that has the same substance
at both electrodes.
✓ Therefore, as long as the concentrations are
different, Ecell will not be 0.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 44

 EXERCISE:
Determine the cell potential at 298K for the following
reaction:
Cu(s) + 2Fe3+(aq) 2Fe2+(aq) + Cu2+(aq)
given that the [Fe3+] is 0.225M, [Fe2+] is 0.150M and that
[Cu2+] is 0.100M.

Ans:
0.47
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 45
 EXERCISE:
The following cell reaction occurs at equilibrium under
standard conditions:
Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s)
The standard Gibbs free energies of formation for the ions
are 65.5 KJ/mole for Cu2+, and -147.0 KJ/mole for Zn2+.
What is the standard cell potential for the reaction?

Ans:
1.101 V
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 46
 EXERCISE:
Calculate the solubility product and the solubility of
AgBr at 25 °C on the basis of the following standard
electrode potentials:
AgBr(s) + e- → Ag(s) + Br-(aq) Eo = 0.0713 V
Ag+(aq) + e- → Ag(s) Eo = 0.7996 V

Ans:
Ksp = 4.9 x10-13; 7.0 x10-7
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 47
 SPONTANEOUS CHEMICAL REACTIONS
AND THE EXTENT OF REACTION
Spontaneous change at constant T,P is towards
lower values of the Gibbs Energy (G).
For a reaction of the type
A B
the change in amount of A and B equals:
dnA = - dξ ; dnB = dξ
where ξ = extent of reaction (reported in moles)

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 48

 SPONTANEOUS CHEMICAL REACTIONS
AND THE EXTENT OF REACTION
✓ The reaction Gibbs energy, ΔGr,
is defined as the slope of the
graph of the Gibbs energy plotted
against the extent of reaction:
✓ If n mol of substance J are present
in a mixture, the chemical potential
(μ) of J is defined as:

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 49

 SPONTANEOUS CHEMICAL REACTIONS
AND THE EXTENT OF REACTION

✓ For a mixture composed of A and B,

we can write:
dG = μAdnA + μBdnB
dG = -μAdξ + μBdξ
dG = (μB – μA)dξ

becomes

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 50

 SPONTANEOUS CHEMICAL REACTIONS
AND THE EXTENT OF REACTION
slope

ΔGr is spontaneous when μB < μA

ΔGr is non-spontaneous when μB > μA
ΔGr is equilibrium when μB = μA

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 51

 SPONTANEOUS CHEMICAL REACTIONS
AND THE EXTENT OF REACTION

ΔGr is spontaneous when μB < μA

Reactions of this type is also called exergonic
(from Greek words for work-producing)
ΔGr is non-spontaneous when μB > μA
Reactions of this type is also called endergonic
(from Greek words for work-consuming)

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 52

 SPONTANEOUS CHEMICAL REACTIONS
AND THE EXTENT OF DISSOCIATION, α

Extent of dissociation, α, is the fraction of reactant

that has decomposed in an equilibrium reaction
– if the initial amount of reactant is n and the amount
at equilibrium is neq, then
α = (n − neq)/n
– if the initial amount of reactant is n and the
change is x, then α can also be:
PHYSICAL CHEMISTRY I: Chemical Equilibrium
α = x/n NMPanajon page 53
 EXERCISE:
A reaction, 2A → B, at certain temperature and
pressure advances by 0.051 mole the Gibbs energy of the
reaction changes by −2.41 kJ/mole. What is the Gibbs
energy at this stage of the reaction?

Ans:
-0.123 KiloJoule
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 54
 EXERCISE:
Assuming you start with only N2O4 for the reaction
given below, the equilibrium constant for the reaction
is 0.120 atm at 298 K when total pressure of system
is 2 atm.
N2O4(g) 2NO2(g)
Calculate the extent of dissociation, α, for the
reaction.
Ans:
0.122
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 55
 TEMPERATURE DEPENDENCE OF
EQUILIBRIUM
Le Chatelier’s principle predicts that for a
system at equilibrium:
✓ exothermic reactions: increased temperature
favours the reactants
✓ endothermic reactions: increased temperature
favours the products.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 56

 TEMPERATURE DEPENDENCE OF
EQUILIBRIUM
the slope of a plot of the equilibrium constant
(specifically, ln K) as a function of temperature may
be expressed in either of two ways:
(a) d/dT (ln K) = ΔHorxn/RT2 (Van’t Hoff equations)
(b) d ln K
= – ΔH o
rxn
d(1/T) R

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 57

 TEMPERATURE DEPENDENCE OF
EQUILIBRIUM

d/dT (ln K) = ΔHorxn/RT2

- shows that d ln K/dT < 0 for a reaction that is
o
exothermic (ΔH rxn < 0) under standard conditions
- a negative slope means that ln K, and therefore K
itself, decreases as the temperature rises
- the opposite occurs in the case of endothermic
reactions
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 58
 TEMPERATURE DEPENDENCE OF
EQUILIBRIUM
d ln K
= – ΔH o
rxn
d(1/T) R
- shows that when −ln K is
plotted against 1/T, a straight
line is expected with slope
equal to ΔHorxn/R

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 59

 TEMPERATURE DEPENDENCE OF
EQUILIBRIUM
To find the value of the equilibrium constant at T2 in
terms of its value K1 at T1:
d ln K
= – ΔH o
rxn
d(1/T) R
d ln K = – ΔH o
rxn d(1/T)
R
ln K2 - ln K1 = – ΔH o
rxn (1/T - 1/T )
2 1
R
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 60
 EXERCISE:
The data below show the temperature variation of
the equilibrium constant of the reaction
Ag2CO3(s) 5Ag2O(s) + CO2(g)
T (in K) 350 400 450 500
K 3.98 x10-4 1.41 x10-2 1.86 x10-1 1.48
Calculate the standard reaction enthalpy of the
decomposition.
Ans:
80 KJ/mole
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 61
 EXERCISE:
Given that the standard free energy of formation
for ammonia is -16.45 KJ/mole and its enthalpy of
formation is -46.11 KJ/mole, calculate the equilibrium
constant for the synthesis of ammonia synthesis
reaction at 500 K.
N2(g) + 3H2(g) 2NH3(g)

Ans:
0.18
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 62
 EQUILIBRIUM AND ACTIVITY

The exact form of the equilibrium expression:

aA + bB → cC + Dd
for the given reaction is :
c d
C D
K= a b
A B

where a - the activities of the reacting species

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 63

 EQUILIBRIUM AND ACTIVITY

Activity
- the effective concentration of a given
specie in solution and is equal to:

where X = activity
[X] = Molar concentration
γX = activity coefficient
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 64
 EQUILIBRIUM AND ACTIVITY

Activity
- known as fugacity in ideal gas and is equal
to:
= γX P

where = activity/fugacity
P = partial pressure
γX = activity coefficient
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 65
 EQUILIBRIUM AND ACTIVITY

Activity
- difficult to work with; thus, assumed to be
proportional to molar concentration

- the assumption is only valid for dilute

solutions and with low electrolyte
concentration

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 66

 EQUILIBRIUM AND ACTIVITY

Activity
- the effective concentration of ion is usually
less than the actual concentration
- dependent on ionic strength of the solution,
ion size, ion charge and ion mobility

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 67

 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ

- calculated by the Debye-Hϋckel equation:

where Z - charge of the ion

α - ionic size (in picometers)
μ - ionic strength

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 68

 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ
- can also be calculated using the vpor
pressure of the pure components
γ = PA/xAPAo
where γ - activity coefficient
PA - vapor pressure of A in solution
PAo - vapor pressure of pure A
XA - mole fraction of A
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 69
 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ
– has the following properties:
(a) In very dilute solutions, the ionic strength is
minimal; activity coefficient is equal to unity
hence activity and molar concentration
becomes identical

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 70

 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ
– has the following properties:
(b) At high ionic strength (μ > 0.10 M), activity
coefficients often increase and may even
become greater than unity.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 71

 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ
– has the following properties:
(c) In solutions that are not too concentrated, the
activity coefficient for a given species is
independent of the nature of the electrolyte
and dependent only on the ionic strength.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 72

 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ
– has the following properties:
(d) For a given ionic strength, Effect of ionic strength
on activity coefficients.
the activity coefficient of an
ion decreases dramatically
from unity as the charge on
the species increases.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 73

 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ
– has the following properties:
(e) The activity coefficient of an uncharged
molecule is approximately unity, no matter
what the level of ionic strength.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 74

 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ
– has the following properties:
(f) At any given ionic strength, the activity
coefficients of ions of the same charge are
approximately equal; small variations can be
correlated with the effective diameter of the
hydrated ions.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 75

 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ
– has the following properties:
(g) The activity coefficient of a given ion describes
its effective behavior in all equilibria in which it
participates.

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 76

 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ

becomes

when α - ionic size is expressed in Angstrom units;

(1 A = 100 pm)
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 77
 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ

for single-charged ions, α = 3 Angstroms (or 300 pm)

simplifies into

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 78

 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ

becomes

μ - ionic strength equals values to 0.5 M

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 79
 EQUILIBRIUM AND ACTIVITY
Activity Coefficient, γ

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 80

 EQUILIBRIUM AND ACTIVITY

Ionic strength, μ
- results in electrostatic interactions with other
ions and the solvent and is given by:

where the square bracketed terms represent

molar concentrations of the individual ions
A,B, C and ZA, ZB, ZC, are their charges.
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 81
 EQUILIBRIUM AND ACTIVITY

Ionic strength, μ

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 82

 EQUILIBRIUM AND ACTIVITY

Ionic strength, μ

“The ionic strength of a solution of

a strong electrolyte consisting solely of
singly charged ions is identical to its
total molar salt concentration.”

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 83

 EQUILIBRIUM AND ACTIVITY

Ionic strength, μ

“For solutions with ionic strengths

of 0.1 M or less, the electrolyte effect is
independent of the kind of ions and
dependent only on the ionic strength.”

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 84

 EXERCISE:

Find the ionic strength of:

(a) 0.10 M NaNO3;
(b) 0.010 M Na2SO4 and
(c) 0.02 M KBr dissolved in 0.010 M Na2SO4.
Ans:
(a) 0.10 M
(b) 0.03 M
(c) 0.050 M

PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 85

 EXERCISE:

Find the activity coefficient of Ca2+ in a

solution of 3.3 mM CaCl2 given that Ca2+ has an
ionic size equal to 600 picometers.

Ans. 0.675
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 86
 EXERCISE:
Calculate the Ksp value for the 0.020 M solution
of potassium sulfate:
(a) disregarding activity; and
(b) considering activity given that ionic size for
potassium and sulfate ions are 3.0
Angstroms and 4.0 Angstroms respectively.
Answers:
(a) 3.2 x10-5
(b) 8.45 x10-6
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 87
 EXERCISE:
Calculate the Ksp value for the 0.020 M solution
of potassium sulfate:
(a) disregarding activity; and
(b) considering activity given that ionic size for
potassium and sulfate ions are 3.0
Angstroms and 4.0 Angstroms respectively.
Answers:
(a) 3.2 x10-5
(b) 8.45 x10-6
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 88
 EXERCISE:
The mole fraction of bromine is 0.06 in a solution of
bromine in carbon tetrachloride at 273 K. At this
temperature, the vapor pressures of pure bromine and
carbon tetrachloride is 125 torr and 33.9 tor respectively.
The partial pressure of CCl4 above the solution is 33.3 torr
while that of bromine is 7.90 torr. What are their
corresponding activities? Answers:
Br2 = 0.0630; CCl4 = 0.978
PHYSICAL CHEMISTRY I: Chemical Equilibrium NMPanajon page 89
REFERENCES
Atkins, P., & de Paula, J. (2015). Physical
Chemistry (9th edition). W.H. Freeman and Company:
New York, USA.
Ball, David W. (2015). Physical Chemistry
(2nd edition). Wadsworth Cengage Learning:
Stanford, USA.
REFERENCES
Levine, Ira N. (2009). Physical Chemistry
(6th edition). McGraw-Hill: New York, USA.

Mortimer, Robert G. (2008). Physical

Chemistry (3rd edition). Elsevier Academic
Press: Massachusetts, USA.