Chapter 14

Chemical
Equilibrium
Chapter Goals/Outline
1. The Concept of Equilibrium and the
Equilibrium Constant
2. Writing Equilibrium Constant Expressions
3. The Relationship Between Chemical
Kinetics and Chemical Equilibrium
4. What Does the Equilibrium Constant Tell
Us?
5. Factors That Affect Chemical Equilibrium
 Chemical Equilibrium
Equilibrium is a state in which there are no observable
changes as time goes by.
Chemical equilibrium is achieved when:
• the rates of the forward and reverse reactions are equal
and
• the concentrations of the reactants and products remain
constant.
Physical equilibrium
H2O  l  H2O  g 

Chemical equilibrium
N2O 4 ©gMcGraw-Hill
 Education.
2NO2  g 14-3
 Chemical Equilibrium
 Chemical equilibrium is a reversible reaction that the forward
reaction rate is equal to the reverse reaction rate.
 Reversible reactions do not go to completion.
- They can occur in either direction
a A  g + b B  g c C g + d D  g
Molecules are continually reacting, even though the overall
composition of the reaction mixture does not change.

Equilibrium is not
static, but is a highly
dynamic situation.
The reaction of 2NO2(g)  N2O4(g) over time in a closed vessel. The numbers of
NO2 and N2O4 in the container become constant (c and d) after time has passed. 4
 Equilibrium of N2O4
N2O 4  g 2NO2  g

Start with NO2 Start withEducation.

© McGraw-Hill N2O4 Start with NO2 & N14-5
2O4
Equilibrium Constant Expressions
aA + bB cC + dD
Law of Mass Action

K=
 C  D 
c d

 A  B
a b

 A, B, C, and D = chemical species.

 [ ] = concentrations of species at equilibrium.
 a, b, c, and d = coefficients in the balanced equation.
 K = equilibrium constant (given
© McGraw-Hill without units).
Education. 14-6
6
Equilibrium Constant Expressions
N2O4  g 2NO2  g

[NO2 ]2
K= = 4.63×10-3
N2O4 

Table 14.1 The NO2–N2O4 System at 25°C

K=
only one
equilibrium
constant, K

© McGraw-Hill Education. 14-7

equilibrium positions 7
Equilibrium Constant Expressions
Conclusions About the Equilibrium Expression
• K always has the same value at a given temperature
regardless of the amounts of reactants or products
that are present initially.

• For a reaction, at a given temperature, there are

many equilibrium positions but only one equilibrium
constant, K.

– Equilibrium position is a set of equilibrium concentrations.

8
Relationship of Equilibrium and K
aA + bB cC + dD K=
 C  D 
c d

Equilibrium Will
 A  B
a b

K >> 1 Lie to the right Favor products

K << 1 Lie to the left Favor reactants

K>>1 Products Reactants

K<<1
Reactants Products

 a © McGraw-Hill Education. b  14-9

9
Equilibrium Constant Expressions
Write equilibrium constant expressions for the
following reactions at 500 oC. All reactants and
products are gases at 500 oC.
P C l 5  P C l 3  C l 2 K
PCl 3 Cl 2 
PCl5 
HI 
2

H 2 + I 2  2 H I K
H 2 I 2 
 K=
 NO  H 2 O 
4 6

4 N H 3 + 5 O 2  4 N O + 6 H 2O
NH 3  O 2 
4 5
10
 Equilibrium Expressions Involving
Pressures (Kp)
Equilibrium Expressions Involving Pressures
• Kc involves concentrations. PV  nRT
n
• Kp involves pressures. P    RT
V
n
Example Because   has the units mol/L,
V
N2(g) + 3H2(g) 2NH3(g) P = [ ]RT

 
2

Kp =
PNH
3
K =
NH3  2

P P  N2 H2 

3
3
N H
2 2
11
 Homogeneous Equilibrium
Homogeneous equilibrium applies to reactions in which all
reacting species are in the same phase.
NO 
2 P2
N O  g 2NO  g K =  2 K = 2
NO
2 4 2 c N O  p P
 2 4 N O
2 4
In most cases Kc ≠ 𝑲p
aA  g + bB  g cC  g  + dD  g
Δn
The Relationship Between Kc and Kp: K = K RT 
p c
 R = 0.0821 L·atm/mol·K
 T = temperature (in Kelvin) Δn = (c + d) − (a + b)
 Δn = moles of gaseous ©products − moles of gaseous reactants
McGraw-Hill Education. 14-12
 Heterogeneous Equilibrium
Heterogenous equilibrium applies to reactions in
which reactants and products are in different
phases.
CaCO3  s  CaO  s  + CO2  g

K'c =
CaOCO2  CaCO3  = constant
CaCO3  CaO = constant
 CaCO3 
K c = CO2  = K'c × K p = Pco2
CaO

The concentration of solids and pure liquids are not included

in the expression for th©e McGraw-Hill
equilibriEducation.
um constant. 14-13
13
 Heterogeneous Equilibrium
CaCO3  s  CaO  s  + CO2  g

Equilibrium pressure of CO2 is the same at the same temperature,

despite the presence of different amounts of CaCO3 and CaO

𝑷𝑪𝑶𝟐 does not depend© McGraw-Hill amount of 𝑪𝒂𝑪𝑶𝟑 or 𝐂𝐚𝐎

on theEducation. 14-14
 Heterogeneous Equilibrium
• The position of a heterogeneous equilibrium does not
depend on the amounts of pure solids or liquids present.
• The concentrations of pure liquids and solids are
constant.
CH3COOH  aq + H2O l CH3COO-  aq + H3O+ aq
CH COO-  H O+ 
K'c =  3  3  H2O = constant
CH3COOH H2O  
  
CH COO-  H O+ 
Kc =  3  3  = K'c H2O
CH3COOH
 
General practice not to include units for the equilibrium constant.
© McGraw-Hill Education. 14-15
15
 Example 14.1
Write expressions for Kc , and Kp if applicable, for the
following reversible reactions at equilibrium:
a HF  aq + H2O l  H3O+  aq + F-  aq
H3O   F-  There are no gases present, hence, Kp
Kc 
HF does not apply and we have only Kc.

b  2NO  g + O2  g 2NO2  g
2 2
NO2  PNO
Kc =   Kp = 2
2
NO O2  PN2O PO2
   
c CH3COOH  aq + C2H5OH  aq CH3COOC2H5  aq + H2O l 
CH3COOC2H 5 
Kc =
C©HMcGraw-Hill
3COOH  C2H5OH
Education. 14-16
16
 Example 14.2
The following equilibrium process has been studied at 230°C
2NO  g + O2  g 2NO2  g 
In one experiment, the concentrations of the reacting
species at equilibrium are found to be [NO] = 0.0542 M, [O2]
= 0.127 M, and [NO2] = 15.5 M. Calculate the equilibrium
constant (Kc) of the reaction at this temperature.
Solution The equilibrium constant is given by
2
NO2 
Kc = 2
NO O2 

15.5
2
Substituting the 5
Kc = = 6.4 4 × 10
 0.0542
© McGraw-Hill Education.
 0.127
concentrations 2
14-17
17
 Example 14.3
The equilibrium constant Kp for the decomposition
of phosphorus pentachloride (PCl5) to phosphorus
trichloride (PCl3) and molecular chlorine (Cl2) is
found to be 1.05 at 250 °C. If the equilibrium partial
pressures of PCl5 and PCl3 are 0.875 atm and 0.463
atm, respectively, what is the equilibrium partial
pressure of Cl2 at 250 °C?

PCl5  g PCl3  g + Cl2  g

© McGraw-Hill Education. 14-18

18
 Example 14.3
Solution
First, we write Kp in terms of the partial pressures of
the reacting species P P PCl3 Cl2
Kp =
PPCl5
Given: Kp = 1.05 PPCl5 = 0.875 atm PPCl3 = 0.463
 0.463  PCl2 
1.05 =
 0.875 
PCl2 =
1.05  0.875
= 1.98 atm
 0.463
Note that we have©added
McGraw-Hillatm as the unit for PCl2
Education. 14-19
19
 Example 14.4
Methanol (CH3OH) is manufactured industrially by the
reaction: CO  g + 2H2  g CH3OH  g
The equilibrium constant (Kc) for the reaction is 10.5 at 220
°C. What is the value of KP at this temperature?
Solution The relationship between Kc and Kp is

K = K RT 
Δn
p c
Δn = moles of gaseous products − moles of gaseous reactants
Kc = 10.5; T = 273 + 220 = 493 K, and ∆n = 1 − 3 = − 2
Kp = 10.5  0.0821 × 493 
-2

-3
= 6.41 × 10
© McGraw-Hill Education. 14-20
20
 Example 14.5
Write the equilibrium constant expression Kc, and KP if
applicable, for each of the following heterogeneous systems:
 a  NH4 2 Se  s  2NH3  g  + H2Se  g 

K c = NH3  H2Se
2 2
Kp = P NH3 PH2Se

b  AgCl  s  Ag  aq + Cl  aq

+ -
K c =  Ag  Cl 
+ -

c P4  s  + 6Cl2  g 4PCl3 l 

1 1
Kc = Kp = 6
Cl 2 
6
PCl2
© McGraw-Hill Education. 14-21
21
 Kc and Kp Expressions
What are Kc and Kp for the reaction?
You do it!
SO2 g   H2O  H2 SO3 aq  (at25 oC)

Kc =
H2 SO3  Kp =
1
 SO2  PSO2
CaF2  s  Ca2+aq  + 2 F1-aq  (at25 oC)
2
Kc = Ca  F 
2+   - 
K p is undefined
3Fe s  + 4H2O g  Fe3O4 s  + 4H2  g  (at 500 oC)

 P 
4
 H2 
4
H2
Kc = K =
 H2O  P 
4 p 4
H2 O 22
 Example 14.6
Consider the following heterogeneous equilibrium:
CaCO3  s  CaO  s  + CO2  g 
At 800°C, the pressure of CO2 is 0.236 atm. Calculate (a) Kp
and (b) Kc for the reaction at this temperature.
Solution KP = P CO2 = 0.236

K = K RT 
Δn
p c
Here, T = 800 + 273 = 1073 K; Δn = 1 and R = 0.0821.
0.236 = K c  0.0821 × 1073 
-3
K c = 2.68 × 10
© McGraw-Hill Education. 14-23
23
 Exercise
Consider the following equation: You do it!
N2(g) + 3H2(g) 2NH3(g)
Using the value of Kp (3.9 × 104), calculate the
value of Kc at 35 ⁰C.
Solution

Kp = K  RT 
n

 2 4 
3.9  10 = K  0.08206 L  atm/mol  K  308K 
4

K = 2.5  107 24
 Equilibrium Constants
Multiple Equilibria
' K '
=
 C D 
K ''
=
EF
 A B CD
A+B C +D K c c c

''
C+ D E+F K
EF
c

Kc =
A+B E+F Kc
 A B
' ''
Kc = K × K c c

If a reaction can be expressed as the sum of two or more

reactions, the equilibrium constant for the overall reaction
is given by the product of the equilibrium constants of the
individual reactions. © McGraw-Hill Education. 14-25
25
 Equilibrium Constants
N2O 4  g  2NO2  g  2 NO 2  g  N2O 4  g 

NO2 
2
-3 K' =
N2O 4  1
= = 216
K= = 4.63 × 10
N2O4  NO 2 
2
K

When the equation for a reversible reaction is written in

the opposite direction, the equilibrium constant becomes
the reciprocal of the original equilibrium constant.

© McGraw-Hill Education. 14-26

26
 Example 14.7
The reaction for the production of ammonia can be written
in a number of ways: Write the equilibrium constant
expression for each formulation. (Express the concentrations
of the reacting species in mol/L.)
Solution 2
NH 3 
a N2  g + 3H2  g 2NH3  g K a =
3
N2  H2 

1 3 NH3 
b  N2  g + H2  g NH3  g  K =
2 2 b 1 3
N2  H2 
2 2
© McGraw-Hill Education. 14-27
 Example 14.7
Solution 2
NH3 3
c
1
N2  g + H2  g
2
NH3  g  Kc = 1
3 3
N2  H2 
3

d) How are the equilibrium constants related to one

another?
2
K a = Kb
3
Ka = KC
3
2 3
Kb = ©KMcGraw-Hill
C or K b =
Education.
K 2
C 14-28
28
Writing Equilibrium Constant Expressions
1. The concentrations of the reacting species in the
condensed phase are expressed in M. In the gaseous
phase, the concentrations can be expressed in M or in atm.
2. The concentrations of pure solids, pure liquids and solvents
do not appear in the equilibrium constant expressions.
3. The equilibrium constant is a dimensionless quantity.
4. In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.
5. If a reaction can be expressed as a sum of two or more
reactions, the equilibrium constant for the overall reaction
is given by the product of the equilibrium constants of the
individual reactions. © McGraw-Hill Education. 14-29
29
Chemical Kinetics and Chemical
Equilibrium
kf
rate f = k f  A B
2

A + 2B AB 2
kr rater = kr  AB2 
Equilibrium
ratef = rater
2
k f  A  B = kr  AB2 

kf  AB2 
= KC = 2
kr  A  B
© McGraw-Hill Education. 14-30
30
 Reaction Quotient (Qc)
The reaction quotient (Qc) is calculated by substituting
the initial concentrations of the reactants and
products into the equilibrium constant (Kc) expression.

aA + bB cC + dD

C0 D0c d
 C  D 
c d

Qc = Kc =
 A 0 B0  A  B
a b
a b

Subscripts zero indicates initial concentrations

© McGraw-Hill Education. 14-31
31
 Reaction Quotient
Qc = Kc - the system is at equilibrium.
Qc < Kc - system proceeds from left to right to reach
equilibrium
Qc > Kc - system proceeds from right to left to reach
equilibrium more reactants
more products no net change

Qc < Kc
Qc = Kc Qc > Kc

32
 Example 14.8
At the start of a reaction, there are 0.249 mol N2, 3.21 x 10-2
mol H2, and 6.42 x 10-4 mol NH3 in a 3.50 − L reaction vessel
at 375 °C. If the equilibrium constant (Kc) for the reaction is
1.2 at this temperature, decide whether the system is at
equilibrium. If it is not, predict which way the net reaction
will proceed. N  g + 3H  g 2NH  g 
2 2 3
Solution
The initial concentrations of the reacting species are
N2  =
0.249 mol
 0 = 0.0711 M
3.50 L -2
H2  =
3.21 × 10 mol -3
 0 = 9.17 × 10 M
3.50 L -4
NH3  = 6.42 × 10 mol =1.83 × 10-4 M
 0 3.50 L
© McGraw-Hill Education. 14-33
33
 Example 14.8
Next we write

Qc =
NH3 0
2

=
 1.83 × 10  -4 2

N2 0 H2 0  0.0711   9.17 × 10 

3 -3 3

Q c = 0.611 Kc = 1.2
Because Qc < Kc (1.2), the system is not at equilibrium.

The net result will be an increase in the concentration of

NH3 and a decrease in the concentrations of N2 and H2. That
is, the net reaction will proceed from left to right until
equilibrium is reached.
© McGraw-Hill Education. 14-34
34
 Calculating Equilibrium
Concentrations
1.Express the equilibrium concentrations of all
species in terms of the initial concentrations and
a single unknown x, which represents the change
in concentration.

2.Write the equilibrium constant expression in

terms of the equilibrium concentrations. Knowing
the value of the equilibrium constant, solve for x.

3.Having solved for x, calculate the equilibrium

concentrations of all species.
© McGraw-Hill Education. 14-35
35
 Example 14.9
A mixture of 0.500 mol H2 and 0.500 mol I2 was placed in a
1.00 − L stainless-steel flask at 430 °C. The equilibrium
constant Kc for the reaction is 54.3 at this temperature.
Calculate the concentrations of H2, I2, and HI at equilibrium.
H2  g  + I2  g  2HI  g 

Solution
Step 1: ICE-Chart
H2 + I2 2HI
I - Initial M : 0.500 0.500 0.000
C - Change M : -x -x +2x
E - Equilibrium M  0.500 -x   0.500 -x
© McGraw-Hill Education.
 2x
14-36
36
 Example 14.9
Step 2: The equilibrium constant is given by

Kc =
HI 2
 2x 
2

54.3 =
H2 I2   0.500 - x  0.500 - x 
Taking the square root of both sides, we get
2x
7.37 =
0.500 - x
x = 0.393 M
Step 3: At equilibrium, the concentrations are
H2  =  0.500 - 0.393  M = 0.107M
I2  =  0.500 - 0.393  M = 0.107M
HI = 2 × 0.393M = 0.786M
© McGraw-Hill Education. 14-37
37
 Example
You do it!
The equilibrium constant, Kc, is 3.00 for the
following reaction at a given temperature. If 1.00
mole of SO2 and 1.00 mole of NO2 are put into an
evacuated 2.00 L container and allowed to reach
equilibrium, what will be the concentration of each
(or all) compound at equilibrium?

S O 2 (g )  N O 2 (g ) 
 S O 3 (g )  N O (g )

38
 Example
Solution SO2(g)  NO2(g) 
 SO3(g)  NO(g)
I Initial 0.500 M 0.500 M 0 0
C Change - xM - xM +xM +xM
E Equilibrium 0.500  x M 0.500  x M xM xM

K
SO3 NO  3.00   x  x 
SO2 NO2  0.500  x 0.500  x 
This equation is a perfect square.
We can take the of both sides.
x
1.73 =
0.500  x
0.865 - 1.73 x  x; 0.865  2.73 x ; x  0.865
2.73
x  0.316M  SO3   NO
0.500  x M  0.184M  SO2   NO2  39
 Example 14.10
For the same reaction and temperature as in Example 14.9,
suppose that the initial concentrations of H2, I2, and HI are
0.00623 M, 0.00414 M, and 0.0224 M, respectively.
Calculate the concentrations of these species at equilibrium.
H2  g  + I2  g  2HI  g 
Solution From the initial concentrations we can calculate
the reaction quotient (Qc)
HI0 2
 0.0224 
2

Qc = = = 19.5
H2 0 I2 0  0.00623  0.00414 
Qc = 19.5 but Kc = 54.3
Qc < Kc The system shifts to the right to establish equilibrium
© McGraw-Hill Education. 14-40
 Example 14.10
Step 1: find equilibrium concentration from ICE chart
H2 + I2 2HI
Initial M : 0.00623 0.00414 0.0224
Change M : -x -x + 2x
Equilibrium M  0.00623 - x   0.00414 - x  0.0224 + 2x 
Step 2: The equilibrium constant is

Kc =
HI
2
 0.0224 + 2x 
2

54.3 =
H2 I2   0.00623 - x   0.00414 - x 
It is not possible to solve this equation by the square root shortcut.
54.3  2.58 × 10 -5 - 0.0104x + x 2  = 5.02 × 10 -4 + 0.0896 x + 4 x 2
50.3x2 -©0.654
McGraw-Hill 8.98 × 10-4 = 0
x +Education. 14-41
41
 Example 14.10
This is a quadratic equation of the form a x2 + b x + c = 0.
The solution for a quadratic equation (see Appendix 4) is
- b ± b2 - 4ac
x=
2a
Here, a = 50.3, b = − 0.654, and c = 8.98 x 10-4
 - 0.654  - 4  50.3  8.98×10-4 
2
0.654 ±
x=
2 × 50.3
x = 0.0114 M or x = 0.00156 M
x = 0.0114 M is physically impossible because the amounts of H2 and
I2 reacted would be more than those originally present.
H2  =  0.00623 - 0.00156  M = 0.00467 M
I2  =  0.00414 - 0.00156  M = 0.00258 M
HI =  0.0224 + 2 × 0.0
© McGraw-Hill 0156  M = 0.0255 M
Education. 14-42
42
 Example
Disturbing a System at Equilibrium
• To help with the calculations, we must determine the direction
that the equilibrium will shift by comparing Q with Kc.
• Example An equilibrium mixture from the following
reaction was found to contain 0.20 mol/L of A, 0.30 mol/L
of B, and 0.30 mol/L of C. What is the value of Kc for this
reaction?
A(g) B(g) + C(g)
Equil. []'s 0.20M 0.30M 0.30M

Kc 
B C  0.30  0.30 
 = 0.45
 A  0.20 43
 Example
• If the volume of the reaction vessel were suddenly
doubled while the temperature remained constant, what
would be the new equilibrium concentrations?
1. Calculate Qc, after the volume has been doubled

A(g) B(g) + C(g)

Equil. []'s 0.10 M 0.15 M 0.15 M

Qc 
B C  0.15  0.15 
 = 0.22
 A  0.10
Since Q < Kc the reaction will shift to the right to re-establish
the equilibrium. 44
 Example
2. Use algebra to represent the new concentrations.
A (g) B (g) + C (g)
New initial []'s 0.10 M 0.15 M 0.15 M
Change -x M +x M +x M
New Equil. []'s 0.10 - x  M 0.15 + x  M 0.15 + x  M
Kc =
B C  = 0.45 =
 0.15 + x 0.15 + x 
 A 0.10 - x 
Solve this quadratic equation
0.045 - 0.45 x = 0.0225 + 0.30 x + x 2
x  0.75 x  0.0225  0
2
45
 Example
- b  b 2  4ac
x
2a

 0.75  0.75 2  41 0.0225 

x
21
 0.75  0.81
x   0.78 and 0.03 M
2
Since 0 < x < 0.10, we can discard - 0.78 as an answer.
The only posible value is x  0.03 M.
 A  (0.10  x ) M  0.07 M
B   C   0.15  x  M  0.18 M
These are the new concentrations after the equilibrium has been disturbed.
46
 Le Châtelier’s Principle
If an external stress is applied to a system at equilibrium,
the system adjusts in such a way that the stress is partially
offset as the system reaches a new equilibrium position.
Changes in Concentration:
The system will shift away from the added
component. If a component is removed, the
opposite effect occurs.
N2  g + 3H2  g 2NH3  g

Equilibrium shifts left  Add NH3
to offset stress
When more NH3 is added to the system, the concentration of NH3 immediately increases.
Equilibrium shifts toward the reactants (to the left). The concentration of NH3 decreases, and
© McGraw-Hill
the concentrations of H2 and N2 increase, until a Education.
new equilibrium is reached. 14-47
47
 Le Châtelier’s Principle
Changes in Concentration:
aA + bB cC + dD

Shifts the
Change
Equilibrium
Increase concentration of product(s) left
Decrease concentration of product(s) right

Increase concentration of reactant(s) right

Decrease concentration of reactant(s)

© McGraw-Hill Education.
left 14-48
 Le Châtelier’s Principle
Changes in Volume and Pressure:
N2  g + 3H2  g 2NH3  g

Change Shifts the Equilibrium

Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas

Increase volume Side with most moles of gas

Decrease volume Side with fewest moles of gas
© McGraw-Hill Education. 14-49
49
 Le Châtelier’s Principle
Changes in Temperature:
N2O 4  g 2NO2  g ΔH° = 58.0 kJ/mol
Temperature: K will change depending upon the temperature
(endothermic – energy is a reactant;
exothermic – energy is a product)
• Endothermic– The system shifts to the right at higher temperature
• Exothermic – The system shifts to the left at higher temperature

Change Exothermic Rx Endothermic Rx

Increase temperature K decreases K increases
Decrease temperature© McGraw-Hill
K increases
Education.
K decreases14-50
50
 Le Châtelier’s Principle
Adding a Catalyst:
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner
Catalyzed

Uncatalyzed

Catalyst lowers 𝑬𝒂 for both forward and reverse reactions.

Catalyst does not change ©equilibrium
McGraw-Hill Education. 14-51
constant or shift equilibrium.
 Example 14.11
At 720 °C, the equilibrium constant KC for the following
reaction is 2.37 x 10-3. In a certain experiment, the
equilibrium concentrations are [N2] = 0.683 M, [H2] = 8.80
M, and [NH3] = 1.05 M. suppose some NH3 is added to the
mixture so that its concentration is increased to 3.65 M.
N2  g + 3H2  g 2NH3  g
(a) Use Le Châtelier’s principle to predict the shift in
direction of the net reaction to reach a new equilibrium.

(b) Confirm your prediction by calculating the reaction

quotient Qc and comparing its value with Kc.
© McGraw-Hill Education. 14-52
52
 Example 14.11
Solution (a) Answer: shifts from right to left
(a) The stress applied to the system is the addition of NH3. To
offset this stress, some NH3 reacts to produce N2 and H2 until a
new equilibrium is established. The net reaction therefore shifts
from right to left; that is, N2  g + 3H2  g 2NH3  g

(b) When some of the NH3 is added, the system is no

longer at equilibrium. The reaction quotient is given by
NH3 02
 3.65 
2

Qc = =
N2 0 H2 0
3
 0.683  8.80 
3

Q c = 2.86 × 10-2 but Kc = 2.37 x 10-3

Qc > Kc
The system shifts from right to left
© McGraw-Hill to establish equilibrium. 14-53
Education. 53
 Example 14.11
Figure 14.8 (shown below) shows qualitatively the changes
in concentrations of the reacting species.

When more NH3 is added to the

system, the concentration of NH3
immediately increases. Equilibrium
shifts toward the reactants (to the
left). The concentration of NH3
decreases, and the concentrations of
H2 and N2 increase, until a new
equilibrium is reached.

© McGraw-Hill Education. 14-54

54
 Example 14.12
Solution
Consider the following equilibrium systems: Shifts the
Equilibrium
a 2PbS  s  + 3O  g 2PbO  s  + 2SO  g
2 2 Left to right
b  PCl  g
5
PCl  g + Cl  g
3 2 Right to left
1 2
c H  g + CO  g
2 2
H O  g + CO  g
2 No effect
2 2
Predict the direction of the net reaction in each case as a
result of increasing the pressure (decreasing the volume)
on the system at constant temperature.
© McGraw-Hill Education. 14-55
55
Le Châtelier’s Principle - Summary

Shift Change Equilibrium

Change
Equilibrium Constant
Concentration yes no
Pressure yes* no
Volume yes* no
Temperature yes yes
Catalyst no no

* Dependent on relative moles of gaseous reactants and

products.
© McGraw-Hill Education. 14-56
56
 Example 14.12
Consider the following equilibrium process between
dinitrogen tetrafluoride (N2F4) and nitrogen difluoride (NF2):
N2F4  g 2NF2  g ΔH° = 38. 5 kJ/mol Solution

Equilibrium
Predict the changes in the equilibrium if Shifts
a) the reacting mixture is heated at constant
volume; Left to right
b) some N2F4 gas is removed from the
reacting mixture at constant temperature Right to left
and volume;
c) the pressure on the reacting mixture is Left to right
decreased at constant temperature; and
d) a catalyst is added to©the reacting
McGraw-Hill Education.mixture. No effect14-57
Le Châtelier’s Principle

58
 Chemistry In Action
Life at High Altitudes and Hemoglobin Production

Hb  aq + O2  aq HbO2  aq

Kc =
HbO2 
HbO2 

Because there is less oxygen, the equilibrium shifts toward

hemoglobin and away from oxyhemoglobin, required for normal
functioning.
Over time, the bodies of people residing at high altitudes begin
to form more hemoglobin to shift the equilibrium, increasing
the formation of oxyhemoglobin.
© McGraw-Hill Education. 14-59
59
 Chemistry In Action: The Haber Process
N2  g + 3H2  g 2NH3  g ΔH° = - 92.6kJ/mol

Because four moles of reactant gases Because the reaction is exothermic in

produce two moles of product gas, the the forward direction, the equilibrium
equilibrium can be pushed to the right at can be pushed to the right at low
high pressures. As pressure increases, pressures. As temperature decreases,
the mole percent of NH3 in the reaction the mole fraction of NH3 in the reaction
mixture increases. © McGraw-Hillmixture
Education. increases. 14-60
 Chemistry In Action: The Haber Process
N2  g + 3H2  g 2NH3  g ΔH° = - 92.6kJ/mol

The reaction mixture, which now contains N2, H2, and

NH3, is placed into an ammonia condenser to change
the temperature of the mixture and drive the
equilibrium toward NH3. The liquid NH3 is moved to
storage tanks, and the unreacted H2 and N2 are
recycled back to the compressor in the first step.
© McGraw-Hill Education. 14-61
61
 Thank you!

© McGraw-Hill Education. All rights reserved. Authorized only for instructor use in the
classroom. No reproduction or further distribution permitted without the prior written consent
14-62
of McGraw-Hill Education.