CHAPTER 2

CHEMICAL EQUILIBRIUM
 Chemical equilibrium applies to reactions that can occur in both
directions.
 Example:

N2O4(g) 2NO2(g)

 Chemical equilibrium is achieved when

1. the rates of the forward and reserve reactions are equal
2. the concentration of the reactants and products remain constant.

 Homogenous equilibrium applies to reactions in which all

reacting species are in the same phase.
H2(g) + I2(g) 2HI(g)
 Heterogeneous equilibrium applies to reactions in which
reactants and products are in different phases.

CaCO3 (s) CaO (s) + CO2 (g)

 Equilibrium Constant Expression

aA + bB cC + dD

Kc = [C]c [D]d  The subscript in Kc indicates that the

concentration of the reacting species
[A]a [B]b are in molar, M (mol/liter)

 Kc does not depend on the initial conc. of the reactants and

products
 Kc depends only on the concentration at equilibrium.
 Kc depends on temperature. Different value of Kc at different T.
 When the direction of an equation is reversed, the new Kc is the
reciprocal of the original

K”c = 1/Kc

PCl3(g) + Cl2(g) PCl5(g) Kc = [PCl5]

[PCl3] [Cl2]

PCl5(g) PCl3(g) + Cl2(g) K”c = [Cl2] [PCl3]

[PCl5]
 When the coefficients in an equation are multiplied by a factor (e.g.
2), the Kc is raised to a power equal to that factor.

K”c = Kc2

PCl3(g) + Cl2(g) PCl5(g) Kc = [PCl5]

[PCl3] [Cl2]

2PCl3(g) + 2Cl2(g) 2PCl5(g) K’’c = [PCl5]2

[PCl3]2 [Cl2]2
 If a reaction can be expressed as the sum of 2 or more reactions,
the equilibrium constant for the overall reaction is given by the
product of the equation constant of the individual reactions.

Kc = K’cK”C

A + B C + D K’c
C + D E + F K”c
Overall reaction: A + B E + F Kc

[C][D] [E][F] [A][B]

K’cK”c = x = = Kc
[A][B] [C][D] [E][F]
 N2O4(g) 2NO2(g) Kc = [NO2]2
[N2O4]

 At constant T, the pressure P of a gas is directly

related to the [ ] of the gas.
 P = (n/V) RT
 Thus, we can write
2  PNO2 and PN2O4 are the equilibrium
P NO2
Kp = partial pressures (in atm) of NO2
PN2O4 and N2O4 respectively
 The expression for the equilibrium constant includes only
solutes (aq) and gases
 pure solids and liquids do not appear in the expression.
 Example:

CaCO3(s) CaO(s) + CO2(g)

Kc = [CO2]
Kp = PCO2

 Kc and Kp do not depend on the amount of CaCO3 or CaO

 The relationship between Kc and Kp

Kp = Kc(RT)n

R = gas constant = 0.0821 L.atm/K.mol

T = temperature in Kelvin (0 oC = 273.15 K)

Kp = Kc(0.0821 T)n

 In general, Kc  Kp
 Except in the special case in which n = 0
 Exercise
For the following reversible reactions at equilibrium, write
expression for Kc, and Kp if applicable.

1. HF(aq) + H2O(l) H3O+(aq) + F-(aq)

2. NaHCO3(s) NaOH(s) + CO2(g)

3. N2(g) + 3H2(g) 2NH3(g)

 Equilibrium constant & unit
• It is general practise not to include units for equilibrium
constant. Why?
 In thermodynamics, the eq. constant is defined in terms of
activities rather than [ ].
 In ideal system, the activity of a substance is the ratio of its
[ ] ( or partial P) to a standard value (1 M or 1 atm)
 Consequently, K has no units
 Example 1
The equilibrium concentrations of NH3, N2 and H2 are 0.25 M, 0.11 M
and 1.91 M, respectively. Calculate Kc for the following reaction

a) N2(g) + 3H2(g) 2NH3(g)

b) 2NH3(g) N2(g) + 3H2(g)

Answer

a) Kc = [NH3]2 = (0.25)2
[N2] [H2]3 (0.11) (1.91)3
 Example 2

The equilibrium constant Kp for the below reaction is 158 at 1000 K.

Calculate the equilibrium partial pressure of O2 if PNO2 = 0.400 atm and
PNO = 0.270 atm
2NO2(g) 2NO(g) + O2(g)
Answer

Kp = P 2NO PO 2 PO 2 = Kp P2NO2
P2NO2 P 2NO

= 346.7 atm
 Example 3
The equilibrium constant, Kp for the below reaction at 2200°C is 0.051.
Calculate the equilibrium constant, Kc
N2(g) + O2(g) 2NO(g)
Answer

Given:
Kp = 0.051
T = 2200 + 273 = 2473 K
n = 2-2 = 0
 Exercise 1

Consider the following equilibrium process at 700 oC

2H2(g) + S2(g) 2H2S(g)

Analysis shows that there are 2.50 moles of H2, 1.35 x 10-5 mole of S2
and 8.70 moles of H2S present in a 12.0 L flask. Calculate the
equilibrium constant Kc for the reaction.

Kc = 1.08 x 107
 Exercise 2

CO(g) + 2H2(g) CH3OH(g)

The equilibrium constants Kc for the reaction is 10.5 at 220 oC.

What is the value of Kp at this temp.. .

Kp = 6.41 x 10-3
 Exercise 3
The equilibrium concentrations for the reaction between carbon
monoxide gas and chlorine gas to form phosgene gas, COCl2 at 74 oC
are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M. Calculate
the equilibrium constants Kc and Kp. .

CO(g) + Cl2(g) COCl2(g)

Kc = 216
 Summary of Guidelines for Writing Equilibrium Constant

 The concentration of the reacting species in the condensed

phase are expressed in mol/L. In the gaseous phase, the
concentrations can be expressed in mol/L or in atm.
 Kc and Kp is related by a simple equation: Kp = Kc(RT)n
 The concentration of pure solid, pure liquid (in
heterogeneous equilibria), and solvents (in homogeneous
equilibria) do not appear in the equilibrium constant
expressions.
 Kc and Kp are a dimensionless quantity (no unit).
 In quoting a value for the equilibrium constant, we must specify
the balanced equation and the temperature.
The magnitude of Kc and Kp and the position of equilibrium

 When K is very large

 The reaction proceeds far toward completion. The
position of equilibrium lies far toward the products
 When K  1
 The concentration of reactants and products are nearly
the same at equilibrium. The position of equilibrium lies
approximately midway between reactants and products
 When K is very small
 Very small amounts of products are formed. The
position of equilibrium lies far toward the reactants
 Predicting the Direction of a Reaction

 For reactions that have not reached equilibrium, write the reaction
quotient (Qc) by substituting the initial concentrations into the
equilibrium constant expression.
 To determine the direction in which the net reaction will proceed to
achieved equilibrium, compare the values of Qc and Kc.

 Qc < K c
 The system proceeds from left to right (consuming
reactants, forming products) to reach equilibrium.
 Qc = K c
 The system is at equilibrium.
 Qc > K c
 The system proceeds from right to left to reach equilibrium.
Qc < Kc Qc = Kc Qc > Kc
Example

At 430 oC, Kc = 54.3 for the reaction:

H2(g) + I2(g) 2HI(g)
Suppose at the start of the reaction, there are 0.243 mol H2, 0.146
mol I2 and 1.98 mol HI in a 1.00 L container at 430 oC. Decide
whether the system is at equilibrium or not. If it is not, predict which
way the net reaction will proceed

Answer
Qc = [HI]0 2 = (1.98)2
= 111
[H2]0 [I2]0 (0.243) (0.146)

Qc > Kc
 The net reaction will proceed from right to left until
equilibrium is reached.
 Exercise
For the synthesis of ammonia, the Kc at 479 K is 0.105. Suppose at
the start of the reaction, there are 2.00 M of H2 gas, 1.00 M of N2 gas
and 2.00 M of NH3 gas at 479 K. Does this reaction at equilibrium? If
it is not, predict which way the net reaction will proceed.
 Calculating Equilibrium Concentration

Example

At 698K, Kc = 54.4 for the reaction:

H2(g) + I2(g) 2HI(g)
If a 10.0L container is filled with 0.100 mol of H2(g) and 0.100 of I2(g) at
698K, determine the concentration of H2(g), I2(g) and HI(g) at equilibrium.

Solution

Given:
2
Kc = [HI] = 54.4
[H2][I2]
Reaction table

H2(g) + I2(g) 2HI(g)

Initial (mol) 0.100 0.1000 0

Change (mol) -x -x +2x

mol at eq. (0.100 – x) (0.100 – x) 2x

Conc. in (0.100 –x) (0.100 –x) 2x

mol/L 10.0 10.0 10.0
 2 (2x/10.0)2
Kc = [HI] =
[H2][I2] [(0.100 –x)/10.0] [(0.100 –x)/10.0]
= 54.4
50.4x2 – 10.88x + 0.54 = 0

Solving for quadratic equation

x = 0.0787 mol

[H2] = (0.100 - 0.0787)/10

= 2.13 x 10-3M

[I2] = 2.13 x 10-3M

[Hl] =
 Exercise 1

In 1.00L container was added 10.4 g PCl5 and heated at 150 oC. The
equilibrium pressure of the reaction was 1.91 atm.
PCl5(g) PCl3(g) + Cl2(g)
(i) The concentration of each gases at eq.
(ii) Kc at 150 oC.
(iii) Kp at 150 oC.
(iv) The percentage of the decomposition of PCl5(g).

Solution

Total mol at equilibrium

Initial mole
pv = nRT
n = pv/RT = 10.4 g / 208.5 gmol-1
= 1.91 x 1.00/0.0821x 423 = 5.00 x 10-2 mol
= 5.50 x 10-2 mol
 PCl5(g) PCl3(g) + Cl2(g)

Initial (mol) 5.00 x 10-2 0 0

change (mol) -X X X

eq. (mol) (5.00 x 10-2 – X) X X

Total mol at equilibrium = (5.00 x 10-2 –X) + X + X

5.5 x 10-2 = (5.00 x 10-2 + X)
X = 5.0 x 10-3 mol

(i) The concentration of each gases at equilibrium,

[PCl5] = 5.00 x 10-2 – X =
[PCl3] = [Cl2] = X =
 (ii) Kc = [PCl3][Cl2]
[PCl5]

(iii) Kp = Kc(0.0821T)∆n
∆n = 2 – 1 = 1
Kp =

(iv) % decomposes
= mol of PCl5 decomposes x 100
Initial mol of PCl5
= 5.0 x 10-3 x 100
5.0 x 10-2
= 10%
 Exercise 2
The equilibrium concentrations Kc for the decomposition of phosgene,
COCl2 is 4.63 x 10-3 at 527 oC. Calculate the equilibrium partial
pressure of all the components, starting pure phosgene at 0.760 atm.

COCl2(g) CO(g) + Cl2(g)

 Exercise 3
2NO2(g) N2O4(g)

If the concentrations at equilibrium of [NO2] = 0.025 M and

[N2O4] = 0.0869 M,
a) Calculate Kc.
b) Determine the equilibrium concentration for NO2 if the
concentration of N2O4 is 0.12 M

a) Kc = 138
b) [NO2] = 0.029 M
 Factors That Affect Chemical Equilibrium

1. Concentration
2. Pressure
3. Volume
4. Temperature

LE CHÂTELIER’S PRINCIPLE
Le Châtelier's principle states that when a system in chemical
equilibrium is disturbed by a change of T, P, V or [ ], the
equilibrium position will shift in the direction which tends to
counteract the effect of the disturbance.
 Changes in concentration
(adding/removing a reactant or product)

 Adding or removing a reactant or product will change its

concentration.
 This changes the value of Qc  so that Qc  Kc
 The system restores equilibrium by changing the [ ],
 until Qc = Kc
 Changing the concentration of reactant/product will shift the
equilibrium to the side that would reduce that change in
concentration.
 E.g.: If the concentration of a solute reactant is increased,
the equilibrium position shifts to use up the added reactants
by producing more products.
Example:

Fe3+(aq) + SCN-(aq) FeSCN2+(aq)

(colourless) (red)

 Increasing the concentration of either Fe3+(aq) or SCN-(aq) will result in

the equilibrium position moving to the right, using up the some of the
additional reactants and producing more FeSCN2+(aq).
 The solution will become a darker red colour.
 Removing some of the Fe3+(aq) or SCN-(aq) will result in the equilibrium
position moving to the left to produce more Fe3+(aq) and SCN-(aq).
 The solution will become less red as FeSCN2+(aq) is consumed.
 Increasing the concentration of FeSCN2+(aq) will result in the
equilibrium position moving to the left to use up some of the additional
FeSCN2+(aq) and producing more Fe3+(aq) and SCN-(aq).
 The solution will become less red.
 Removing some of the FeSCN2+(aq) will result in the equilibrium
position moving to the right to produce more FeSCN2+(aq).
 The solution will become a darker red colour.
 Changes in Volume & Pressure

 Changes pressure ordinarily do not affect the concentrations of reacting

species in condensed phases (aqueous solution) because liquids and
solids are virtually incompressible.
 However, concentration of gases are greatly affected by changes in
pressure.

n 1
PV = nRT P   R T P
V V

n
  = [ ] of gas in mol/L
V
 Changes in Pressure of Gaseous Equilibrium Systems
 Gas pressure is related to the number of gas particles in the system
 more gas particles means more gas pressure.
 Example:
2NO2(g) N2O4(g)

 Increasing the pressure on this equilibrium system will result in the

equilibrium position shifting to reduce the pressure, that is, to the side
that has the least number of gas particles.
 There are 2 gas particles on the left hand side of the reaction and
1 gas particle on the right hand side of the reaction.
 Increasing the pressure on this system results in the equilibrium
position moving to the right, consuming NO2(g) and producing more
N2O4(g).
 Reducing the pressure on this equilibrium system will result in the
equilibrium position moving to the left, that is, to the side that has the
most gas particles, in order to increase the pressure.
 Changes in Volume of Gaseous Equilibrium Systems
 Gas volume is related to gas pressure, a gas at reduced volume has a higher
pressure, a gas at increased volume has a lower pressure.
 Example:
2NO2(g) N2O4(g)
 Increasing the volume of this equilibrium system is equivalent to reducing
the pressure, so the equilibrium position moves to the side of the reaction
that has the most gas particles in order to increase the pressure.
 The equilibrium position shifts to the left producing more NO2(g) by
consuming N2O4(g).

 Reducing the volume of this equilibrium system is equivalent to increasing

the pressure, so the equilibrium position moves to the side of the reaction
that has the least gas particles in order to reduce the pressure.
 The equilibrium position shifts to the right producing more N2O4(g) by
consuming more NO2(g).
 Changes in Temperature

 The effect of changing the temperature in the equilibrium can

be easily viewed by incorporating heat as either a reactant or
product.
 In an endothermic reaction, energy can be considered as a
reactant of the reaction.
 In an exothermic reaction, energy can be considered as a
product of the reaction.
 Changing the temperature not only affect the equilibrium, but it
also change the value of equilibrium constant
 Endothermic Equilibrium Systems

 Consider the following reaction at equilibrium:

H2(g) + I2(g) 2HI(g) H = +52 kJ/mol

colourless purple colourless

 This reaction can also be written with the energy term

incorporated into the equation on the side with the
reactants:

H2(g) + I2(g) +52 kJ 2HI(g)

colourless purple colourless
 Increasing the temperature of the equilibrium system will shift
the equilibrium position to the side that does not include the
energy term in order to reduce the temperature, that is to the
right.
 The increased heat will be consumed to produce more HI(g)
product.
 Since H2(g) and I2(s) will be consumed there will be less purple
solid in the reaction vessel.
 Reducing the temperature of the equilibrium system will shift
the equilibrium to the left in order to produce more heat.
 HI(g) will be consumed in order to produce more H2(g) and I2(s).
The amount of purple solid will increase.
 Exothermic Equilibrium Systems

 Consider the following reaction at equilibrium:

Ag+(aq) + Cl-(aq) AgCl(s) H = -112 kJ/mol

colourless white

 This reaction can also be written with the energy term incorporated
into the equation on the side with the products:

Ag+(aq) + Cl-(aq) AgCl(s) + 112 kJ

colourless white
 Ag+(aq) + Cl-(aq) AgCl(s) + 112 kJ
colourless white

 Increasing the temperature of this equilibrium system shifts

the equilibrium position to the left,
 consuming some of the energy and products to produce
more reactants.
 There will be less white AgCl(s) in the reaction vessel.

 Reducing the temperature of this equilibrium system shifts the

equilibrium position to the right,
 producing more heat and more white AgCl(s).
 Effect of adding an inert gas

 A noble gas such as helium does not react with other elements or
compounds.
 Adding an inert gas into a gas-phase equilibrium at constant
volume does not effect the equilibrium.
 This is because the addition of a non-reactive gas does not
change the partial pressures of the other gases in the container.
 While it is true that the total pressure of the system increases, the
total pressure does not have any effect on the equilibrium constant;
rather, it is a change in partial pressures that will cause a shift in the
equilibrium.
 However, if the volume is increase in the process, the partial
pressures of all gases would be decreased resulting in a shift
towards the side with the greater number of moles of gas.
 The Effect of a Catalyst

 The presence of catalyst does not shift the position of an

equilibrium system and does not alter the equilibrium constant

 Catalyst lowers Ea for both forward and reverse reactions.

uncatalyzed catalyzed
 Le Châtelier’s Principle

Change Equilibrium
Change Shift Equilibrium Constant

Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no
1. The equilibrium position of the reaction can be shifted in
the forward direction by _____.

A) Removing SO2
B) Adding Cl2
C) Removing Cl2
D) Removing SO2 and Cl2
2. The equilibrium , can be shifted toward more product
formation by _____.

H = 92.5 kJ.

A) Increasing temperature
B) Increasing pressure
C) Decreasing temperature
D) Increasing the concentration PCl3
3. The equilibrium pressure of NO2 in the equilibrium is
1.56 atm. Its pressure on the addition of a catalyst will be
_____.

2NO2(g) N2O4(g)

A) 1.06 atm
B) 0.75 atm
C) 1.56 atm
D) 2.71 atm
4.The addition of He to the following equilibrium at constant
volume _____.

A) Shifts the equilibrium to the left

B) Increases Kc
C) Shifts the equilibrium to the right
D) Has no effect
5. The position of the following equilibrium can be shifted to the
left by the addition of _____ at constant pressure.

A) CO
B) He
C) O2
D) None of the above