Unit 3.

Chemical Equilibrium

Chemical equilibrium – a dynamic system in which two or more opposing reactions are going on at the same time and
the same rate

 rate of forward reaction = rate of reverse reaction

The Law of Mass Action

aA +bB ⇌ c C +dD
where

A and B are reactions

C and D are products

a, b, c and d are stoichiometric coefficients in a balanced equation

The mass action expression consists of the product of the products, each raised to the power given by the
coefficient in the balanced chemical equation, over the product of the reactants, each raised to the power given by the
coefficient in the balanced chemical equation. This mass action expression is set equal to the equilibrium constant, K eq
or simply K .
c d
[C] [D]
K eq = a b
[ A ] [ B]
where brackets [ ] indicate molar equilibrium concentrations.

Example:
2
[SO¿¿ 3]
2 S O 2(g) +O2 (g) ⇌ 2 SO3 (g) K= 2
¿
[SO¿¿ 2] [O¿¿ 2]¿ ¿
K is a number equal to a particular ratio of equilibrium concentrations of product and reactant at a particular
temperature. The magnitude of K is an indication of how far a reaction proceeds toward product at a given
temperature.

For any balanced chemical equation, the value of K

 is constant at a given temperature;

 changes if the temperature changes;
 does not depend on the initial concentrations;
 depends on rea
 ction stoichiometry;
 can come only from experiments.

K c denotes equilibrium constant using equilibrium values of concentrations and is dimensionless.

K p denotes equilibrium constant using equilibrium values of partial pressures of gases.

Different Magnitudes of K:
 1. Small K. If a reaction yields very little product before reaching equilibrium, it has a small K, and we may even say
there is “no reaction”. For example, the oxidation of nitrogen barely proceeds at 1000 Kelvin.
N 2 ( g ) +O2 ( g ) ⇌ 2 NO (g) K=1 x 10
−30

a very small Kc means that a

reaction is not likely to happen.

2. Large K. Conversely, if a reaction reaches equilibrium with very little reactant remaining, it has a large K, and we
say it “goes to completion”. The oxidation of carbon monoxide goes to completion at 1000 Kelvin.

2 CO ( g ) +O2 ( g ) ⇌ 2C O2 (g) K=2.2 x 10

22

a very large Kc means that a reaction

is feasible

3. Intermediate K. When significant amounts of both reactant and product are present at equilibrium, K has an
intermediate value, as when bromine monochloride breaks down to its elements at 1000 Kelvin.

2 BrCl ( g ) ⇌ Br 2 ( g ) +Cl 2(g) K=5

Variation Of K c with the Form of the Balanced Equation

 The equilibrium constant of a reaction in the reverse direction is the inverse of the equilibrium constant of the
reaction in the forward direction.
 The equilibrium constant of a reaction that has been multiplied by a number is the equilibrium constant raised
to a power equal to that number.
 The equilibrium constant for a net reaction made up of two or more steps is the product of the equilibrium
constants for the individual steps.

Example 1: Variation of the Form of Kc

You are given the following reaction and its equilibrium constant at a given temperature.
4
2 HBr (g) +Cl 2(g ) ⇌ 2 HCl(g) + Br 2 (g ) K c =4.0 x 10
Write the expression for, and calculate the numerical value of, the equilibrium constant for each of the following at the
same temperature.
'
a. 4 HBr ( g) +2 Cl2 ( g ) ⇌ 4 HCl( g )+2 Br 2( g ) K c =?
1 1 '
b. HBr (g) + Cl ⇌ HCl(g) + Br K c =?
2 2(g ) 2 2 ( g)
Solution:
4 2
' [ HCl] [Br 2 ] ' 2 4 2 9
a. K c = 4 2
K c =K c =(4.0 x 10 ) =1.6 x 10
[HBr ] [Cl2 ]
[ HCl ] [ Br 2]1/ 2
K c =√ K c =√ 4.0 x 10 =2.0 x 10
' ' 4 2
b. K c = 1 /2
[ HBr ] [Cl2 ]

Example 2: Variation of the Form of Kc

Given the following information,
HF (g) ⇌ H +(aq)
¿
+ F−¿
(aq) K eq =6.8 x 10
−4
¿¿
+¿ 2−¿ −6
H 2 C2 O4 (aq ) ⇌ 2 H (aq) +C 2 O4(aq) K eq=3.8 x 10 ¿ ¿
determine the value of the equilibrium constant for the following reaction:
2−¿ −¿
2 HF (g) +C 2 O4(aq) ⇌ 2 F (aq)+ H 2 C 2 O4 (aq) ¿ ¿

Solution: If we multiply the first equation by 2 and take the corresponding change to its equilibrium constant (raising to
the power 2), we get
+¿ −¿ '
2 HF (g) ⇌2 H(aq )+2 F(aq) K eq =¿ ¿ ¿

Reversing the second equation and again making the corresponding change to its equilibrium constant (taking the
reciprocal) gives
+¿ 2−¿ '' 1 5
2 H(aq) +C 2 O 4(aq ) ⇌ H 2 C2 O4 (aq) K eq = −6
=2.6 x 10 ¿ ¿
3.8 x 10

Get the sum of the two equations to give the net equation, and multiply the individual Keq values to get the desired
equilibrium constant.
+¿ −¿
2 HF (g) ⇌2 H(aq )+2 F(aq) ¿ ¿
+¿
2 H(aq) +C 2 O 42−¿
(aq ) ⇌ H 2 C 2 O 4 (aq) ¿ ¿

K eq '' ' =( 4.6 x 10−7 ) ( 2.6 x 105 )=0.1

2−¿ −¿
2 HF (g) +C 2 O4(aq) ⇌ 2 F (aq)+ H 2 C 2 O4 (aq) ¿ ¿

Types of Equilibria:

1. homogeneous equilibria – systems in which all the components of the reaction are in the same phase such as a
system involving gases

CO(g )+ 3 H 2(g) ⇌ CH 4 (g ) + H 2 O(g)

[ CH 4 ] [ H 2 O]
Example: K c=
[ CO ] ¿ ¿
2. heterogeneous equilibria – involves reactants and products in more than one phase.
Liquids and solids are not included in the equilibrium expression.
4
[H ¿ ¿2]
Example: 3 Fe( s) +4 H 2 O(g) ⇌ Fe 3 O4 (s) + 4 H 2(g ) K c= 4
¿
[H ¿¿ 2 O] ¿
a) N 2 (g) +3 H 2(g ) ⇌ 2 NH 3 (g)

b) CaCO3 ( s) ⇌CaO (s) +CO2 (g)

c) CO(g )+ 2 H 2 (g) ⇌ CH 3 OH (g)

d) H Cl(aq) +CaCO 3 ( s) ⇌CaCl 2 (aq )+CO 2 (g)

e) 2 Pb(NO¿¿ 3)2 (s ) ⇌ 2 PbO (s) +4 NO2 ( g) +O2 (g) ¿

Calculating Kc
The value of Kc can be determined depending on what data you have:

A. Given the concentration of products and reactants at equilibrium

Some N2 and H2 are placed in an empty 5.0 L vessel at 500 0C. When equilibrium is established, 3.01 mole
of N2, 2.10 mole of H2 and 0.565 mole of NH3 are present. Calculate K c for this reaction at 500 0C.
N 2 ( g) +3 H 2(g ) ⇌ 2 NH 3 (g)

Equilibrium concentrations:
[N2] = 3.01 mol/5L = 0.602 M [NH3] = 0.565 mol/5L = 0.113 M
 [H2] = 2.10 mol/5L = 0.402 M

2
[NH 3 ] (0.113)2
K c= = =0.29
[ N 2 ] [ H 2 ]3 (0.602)(0.42)3

B. Given the initial concentration of one or more species and the equilibrium concentration of another.
CO and H2 react according to the equation:
CO(g )+ 3 H 2(g) ⇌ CH 4(g )+ H 2 O(g)
When 1.00 mole CO and 3.00 mole H2 are placed in a 10.0 L vessel at 97 oC and allowed to come to equilibrium,
the mixture is found to contain 0.387 mole H2O. Calculate K c .

CO(g )+ 3 H 2(g) ⇌ CH 4(g )+ H 2 O(g)

Initial 1.00 mol/10.0 L 3.00 mol/10.0 L 0 0
Change −x −x +x +x
Equilibrium 0.1− x 0.3−3 x 0.387 mol/10.0 L x

Equilibrium concentrations:

[ CO ] =0.1−x=0.1−0.0387=0.0613 M
[ H 2 ]=0.3−3(0.0387 M )=0.1838 M
[ CH 4 ]=x =0.0387 M
[ H 2 O ]=x=0.0387 M

[ CH 4 ] [ H 2 O] (0.0387)(0.0387)
K c= = =3.93
[ CO ] [ H 2 ]
3
(0.0613)(0.1839)
3

A. Given the initial concentration of one species and how much of that species was used.
Consider the reaction,
H 2 ( g )+ I 2 ( g ) ⇌2 HI (g)
H 2(g) + I 2(g) ⇌ 2 HI (g )
Initial 0.200 M 0.100 M 0M
Change −0.096 −0.096 +2(0.096)
Equilibrium 0.104 M 0.004 M 0.192 M

2 2
[HI ] (0.192)
K c= = =88.6
[ H 2 ] [I 2 ] (0.104)(0.004)
The Relationship Between K c and K p
If reactants and products ae gases, a mass action expression can be expressed in terms of partial pressure
instead of molar concentrations because,

Molar concentration of a gas α partial pressure of gas

from the ideal gas equation PV = nRT

where P = pressure of the gas in atm
 V = volume of the gas in L
n = no. of moles of the gas
Latm
R = universal gas constant, 0.08206
molK
T = temperature in Kelvin
n n
P= RT since M =
V V

P=MRT

Example 1: Consider the reaction, N 2 ( g ) +3 H 2 ( g ) ⇌ 2 N H 3 (g)

2
[ NH 3 ] 2 PNH
K c= 3
K p= 3

3
[N 2 ][ H 2 ] P N PH
2 2

△ ngas
K p=K c x (0.0821 T )

where △ ngas =no . of moles of gaseous products−no . of moles of gaseou s reactants

Example 2: Determine K p for the reaction 2 S O 2(g) +O2 (g) ⇌2 SO 3 (g) if K c =56 at 900 K.

△ ngas =2 moles products−3 moles reactants=−1

−1
K p= ( 56 ) ( 0.0821 x 900 ) =0.76

Predicting the Direction of the Reaction: The Reaction Quotient, Q

 Expression is same as Kc except that in Q, concentrations are not at equilibrium.
a. if Q> K c
the denominator must become larger to reach equilibrium, therefore more reactants are
produced and the reaction proceeds ← ( to the left )
b. if Q< K c
at equilibrium the denominator must become smaller, hence the reactants are used up and
the reaction goes → ( to the right )

c. if Q=K c
the reaction is at equilibrium

Example: Given the equation N 2 (g) +O 2(g ) ⇌ 2 NO (g) Kc = 6.2 x 10 -14 at 2000 °C
If we start with 0.0520 mol of N2(g), 0.0124 mol O2(g) and 0.0020 mol NO(g) in a five-liter (5.0 L) flask which direction will be
favored?

Solution:
Step 1: Find the concentration in mol/liter

0.0020 mol
[ NO ]= =0.0004 M
5.0 L
 0.0124 mol
[ O2 ]= 5.0 L
=0.00248 M

0.0520 mol
[ N 2 ]= 5.0 L
=0.0104 M
Step 2: Substitute the concentrations into the Q expression
2 2
[NO ] (0.0004)
Q= = =0.0065
[ N 2 ] [O2 ] (0.0104)(0.00248)

Since the value of the Q is larger than the Kc, the reaction will go in the direction that will increase the denominator, therefore it
will go to the left ( ← ).
Le Chatelier’s Principle
Le Chatelier’s Principle states that whenever a system at equilibrium is subjected to a stress, the equilibrium will
shift in a direction so as to relieve that stress.

These stresses and their effects are summarized below:

A. Adding or subtracting a product or reactant

1. if species added is a solid or liquid, there is no effect on a gaseous equilibrium.
2. if species added or subtracted is a gas then:
a. adding species shifts direction away from the species added.
b. subtracting a species shifts direction towards the species removed.
B. Change in volume
1. if volume is decreased, the reaction proceeds towards the side with lesser moles of gas.
2. if volume is increased, the reaction proceeds towards side with more moles of gas.
3. if in the balanced equation there are the same number of moles of gas on both sides, a volume change will not
affect the equilibrium.
C. Change in pressure
1. increase in pressure shifts equilibrium in direction of decrease in the number of moles of gas
2. decrease in pressure shifts equilibrium in direction of increase in number of moles of gas.
3. if in the balanced equation there are the same number of moles of gas on both sides, a pressure
change will not affect the equilibrium.
* Pressure change does not apply if the pressure of the system is raised by merely adding an inert gas.
D. Change in temperature
1. If forward reaction is endothermic:
a. increase in temperature causes Kc to become larger
b. decrease in temperature causes Kc to become smaller
2. If forward reaction is exothermic:
a. increase in temperature causes Kc to become smaller
b. decrease in temperature causes Kc to become larger
E. Adding a catalyst
A catalyst changes the rate of reaction; but cannot shift the equilibrium in favor of either
products or reactants.

Effect of Various Disturbances on a System at Equilibrium

Disturbance Net Direction of Reaction Effect on Value of K
Concentration

Increase [reactant] Toward formation of product None

Decrease [reactant] Toward formation of reactant None
Increase [product] Toward formation of reactant None
Decrease [product] Toward formation of product None
Pressure

Increase P (decrease V) Toward formation of fewer moles of gas None

Decrease P (increase V) Toward formation of more moles of gas None
Increase P (add inert gas, no change in V) None; concentrations unchanged None
Temperature
 Increase T Toward absorption of heat Increases if ΔH° > 0
rxn

Decreases if ΔH° < 0

rxn

Decrease T Toward release of heat Increases if ΔH° < 0

rxn

Decreases if ΔH° > 0

rxn

Catalyst added None; forward and reverse equilibrium None

attained sooner; rates increase equally

Example: Applying a Stress to a System at Equilibrium.

Given the following reaction at equilibrium in a closed container at 500 ℃ , predict the effect of each of the
following changes on the amount of NH 3:
N 2 (g) +3 H 2 (g ) ⇌2 NH 3 (g) +heat o
Δ H =−92 kJ /mol reaction
4 moles 2 moles

a) increasing the T,
b) lowering the T,
c) increasing the P by decreasing the volume,
d) introducing some platinum catalyst,
e) forcing more H 2 into the system, and
f) removing some NH 3 from the system.

Solution:

Apply Le Chatelier’s principle to each part of the question.

a) ∆ H =−¿ exothermic forward reaction

↑ T favors the endothermic reaction (reverse in this case).
∴ Some NH 3 is used up. ( NH 3 decreased)

b) ↓ T Favors the exothermic reaction (forward in this case).

∴ More NH 3 is formed. ( NH 3 increased)

c) Increasing (↑) the P favors the reaction that produces the smaller number of moles of gas (forward in this case).
∴ More NH 3 is formed. ( NH 3 increased)

d) A catalyst does not favor either reaction.

∴ It would have no effect on the amount of NH 3.

e) Adding a substance favors the reaction that uses up that substance (forward in this case).
∴ More NH 3 is formed.

f) Removing a substance favors the reaction that produces that substance (forward in this case)
∴ More NH 3 is formed.

Problems:
1. The first step in industrial production of nitric acid is the catalyzed oxidation of ammonia. Without a catalyst, a
different reaction predominates:
4NH (g) + 30 (g) ⇌ 2N (g) + 6H O(g) 3 2 2 2

When 0.0150 mol of NH (g) and 0.0150 mol of O (g) are placed in a 1.00-L container at a certain
3 2

temperature, the N concentration at equilibrium is 1.96 x 10 M. Calculate K .

2
−3
c

Answer: K = 5.90 x 10
c
−6

2. Calculate : K p for the following reaction:

PCI (g) + Cl (g) ⇌ PCl (g)
3 2 K = 1.67 (at 500 K) 5 c

−2
Answer: K p=4.07 x 10
3. The atmospheric oxidation of nitrogen monoxide,
2NO(g) + 0 (g) ⇌ 2N0 (g) 2 2

was studied at 184°C with initial pressures of 1.000 atm of NO and 1.000 atm of O . At equilibrium, 2

PO = 0.506 atm. Calculate K p .

2
4
Answer: K p=1.3 x 10

4. Chloromethane forms by the reaction

CH 4 (g) +Cl 2(g ) ⇌ CH 3 Cl(g )+ HCl(g )
At 1 500 K, K p=1.6 x 10 . In the reaction mixture, PCH =0.13 atm, PCl =0.035 atm,
4
4 2

PCH Cl =0.24 atm , and P HCl=0.47 atm. Is CH Cl or CH forming?

3
3 4

Answer: Q p < K p , so CH Cl is forming. 3

5. Nitrogen monoxide, oxygen, and nitrogen react by the following equation:

2NO(g) ⇌ N (g) + 0 (g); K = 2.3 x 10 at 298 K. 2 2 c
30

In the atmosphere, PO2 = 0.209 atm and PN2= 0.71 atm. What is the equilibrium partial pressure of NO in the air we
breathe? [Hint: You need K to find the partial pressure.] p

Answer: PNO = 2.7 x 10 atm −16

6. An inorganic chemist studying the reactions of phosphorus halides mixes 0. 1050 mol of PCI with 0.0450 mol of Cl 5 2

and 0.0450 mol of PCl in a 0.5000-L flask at 250°C: 3

PCI (g) ⇌ PCI (g) + CI (g) K = 4.2 x 10 . 5 3 2 c

−2

(a) In which direction will the reaction proceed?

(b) If [PCl ] = 0.2065 M at equilibrium, what are the equilibrium concentrations of the other
5

components?
Answers: (a) Q = 3.8 X 10 ; Q < K , so reaction proceeds to the right.
c
−2
c c

(b) [CI ] = [PCI ] = 0.0900 M + x = 0.0935 M.

2 3

7. In a study of the chemistry of glass etching, an inorganic chemist examines the reaction between sand (Si0 ) and 2

hydrogen fluoride at a temperature above the boiling point of water:

Si0 (s) + 4HF(g) ⇌ SiF (g) + 2H 0(g) 2 4 2

Predict the effect on [SiF ] when (a) H 0(g) is removed; (b) some liquid water is added; (c) HF is
4 2

removed; (d) some sand is removed.

Answers: (a) [SiF ] increases; (b) decreases; (c) decreases; (d) no effect.
4

8. Would you increase or decrease the pressure (via a volume change) of each of the following reaction mixtures to
decrease the yield of products?
(a) 2S0 (g) + 0 (g) ⇌ 2S0 (g)
2 2 3

(b) 4NH (g) + 50 (g) ⇌ 4NO(g) + 6H 0(g)

3 2 2

(c) CaC 0 (s) ⇌ CaC0 (s) + CO(g)

2 4 3

Answers: (a) Decrease P; (b) increase P; (c) increase P

9. How does a decrease in temperature affect the partial pressure of the underlined substance and the value of K for p

each of the following reactions?

 (a) C(graphite) + 2H (g) ⇌ CH (g);
2 4 ΔH° = −75 kJ
(b) N (g) + 0 (g) ⇌ 2NO(g);
2 2 ΔH° = 181 kJ
(c) P (s) + 10Cl Cg) ⇌ 4PCI (g);
4 2 5 ΔH° = − 1528 kJ
Answers: (a) PH2 will decrease; K will increase; (b) PN2 will increase;
p