Chemical Equilibrium

Chapter 14
1
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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
NO2
H2O (l) H2O (g)

Chemical equilibrium
N2O4 (g) 2NO2 (g)
2
 N2O4 (g) 2NO2 (g)

equilibrium equilibrium

equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4

3
constant

4
 N2O4 (g) 2NO2 (g)

[NO2]2
K= = 4.63 x 10-3
[N2O4]

aA + bB cC + dD

[C]c[D]d
K= Law of Mass Action
[A]a[B]b

5
 [C]c[D]d
K= aA + bB cC + dD
[A]a[B]b

Equilibrium Will
K >> 1 Lie to the right Favor products
K << 1 Lie to the left Favor reactants

6
Homogenous equilibrium applies to reactions in which all
reacting species are in the same phase.

N2O4 (g) 2NO2 (g)

[NO2]2 PNO2
Kc = Kp =
2

[N2O4] PN O
2 4

In most cases
Kc  Kp
aA (g) + bB (g) cC (g) + dD (g)

Kp = Kc(RT)n

n = moles of gaseous products – moles of gaseous reactants

= (c + d) – (a + b)
7
 Homogeneous Equilibrium

CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)

[CH3COO-][H3O+]
K′c = [H2O] = constant
[CH3COOH][H2O]

[CH3COO-][H3O+]
Kc = = K′c [H2O]
[CH3COOH]

General practice not to include units for the equilibrium

constant.

8
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)

(b) 2NO(g) + O2(g) 2NO2(g)

(c) CH3COOH(aq) + C2H5OH(aq ) CH3COOC2H5(aq) + H2O(l)

9
Example 14.1

Strategy

Keep in mind the following facts: (1) the KP expression applies

only to gaseous reactions and (2) the concentration of solvent
(usually water) does not appear in the equilibrium constant
expression.

10
Example 14.1
Solution

(a) Because there are no gases present, KP does not apply and
we have only Kc.
+ -
' [H 3O ][F ]
Kc =
[HF][H 2O]

HF is a weak acid, so that the amount of water consumed in

acid ionizations is negligible compared with the total amount
of water present as solvent. Thus, we can rewrite the
equilibrium constant as
[H 3O + ][F - ]
Kc =
[HF]
11
Example 14.1
2
(b) [NO 2 ] 2 PNO
Kc = Kp = 2

[NO]2 [O 2 ] 2
PNO PO2
'
(c) The equilibrium constant K c is given by

[CH3COOC 2 H 5 ][H 2 O]
K c' =
[CH 3COOH][C 2 H 5OH]

Because the water produced in the reaction is negligible

compared with the water solvent, the concentration of water
does not change. Thus, we can write the new equilibrium
constant as
[CH 3COOC2 H 5 ]
Kc =
[CH 3COOH][C2 H 5OH]
12
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.

13
Example 14.2
Strategy The concentrations given are equilibrium
concentrations. They have units of mol/L, so we can calculate
the equilibrium constant (Kc) using the law of mass action
[Equation (14.2)].

Solution The equilibrium constant is given by

2
[NO2 ]
Kc =
[NO]2 [O 2 ]

Substituting the concentrations, we find that

(15.5) 2 5
Kc = = 6.44 × 10
(0.0542) 2 (0.127)
14
Example 14.2

Check

Note that Kc is given without units. Also, the large magnitude of

Kc is consistent with the high product (NO2) concentration
relative to the concentrations of the reactants (NO and O2).

15
Example 14.3

The equilibrium constant KP for the decomposition of

phosphorus pentachloride to phosphorus trichloride and
molecular chlorine

PCl5(g) PCl3(g) + Cl2(g)

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?

16
Example 14.3

Strategy

The concentrations of the reacting gases are given in atm, so

we can express the equilibrium constant in KP. From the known
KP value and the equilibrium pressures of PCl3 and PCl5, we
can solve for PCl2.

17
Example 14.3
Solution
First, we write KP in terms of the partial pressures of the
reacting species
PPCl3 PCl2
Kp =
PPCl5

Knowing the partial pressures, we write

(0.463)(PCl2 )
1.05 =
(0.875)
or
(1.05)(0.875)
PCl2 = = 1.98 atm
(0.463)
18
Example 14.3

Check

Note that we have added atm as the unit for PCl2.

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?

20
Example 14.4

Strategy

The relationship between Kc and KP is given by Equation (14.5).

What is the change in the number of moles of gases from
reactants to product? Recall that

Δn = moles of gaseous products - moles of gaseous reactants

What unit of temperature should we use?

21
Example 14.4

Solution

The relationship between Kc and KP is

KP = Kc(0.0821T )Δn

Because T = 273 + 220 = 493 K and Δn = 1 - 3 = -2, we have

KP = (10.5) (0.0821 x 493)-2

= 6.41 x 10-3

22
Example 14.4

Check

Note that KP, like Kc, is a dimensionless quantity. This example

shows that we can get a quite different value for the equilibrium
constant for the same reaction, depending on whether we
express the concentrations in moles per liter or in atmospheres.

23
Heterogenous equilibrium applies to reactions in which
reactants and products are in different phases.

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

[CaO][CO2] [CaCO3] = constant

K′c =
[CaCO3]
[CaO] = constant

[CaCO3]
Kc = [CO2] = K′c x Kp = PCO2
[CaO]

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.

24
 CaCO3 (s) CaO (s) + CO2 (g)

PCO 2 = Kp

PCO 2 does not depend on the amount of CaCO3 or CaO

25
Example 14.5

Write the equilibrium constant expression Kc, and KP if

applicable, for each of the following heterogeneous systems:

(a) (NH4)2Se(s) 2NH3(g) + H2Se(g)

(b) AgCl(s) Ag+(aq) + Cl-(aq)

(c) P4(s) + 6Cl2(g) 4PCl3(l)

26
Example 14.5
Strategy We omit any pure solids or pure liquids in the
equilibrium constant expression because their activities are unity.

Solution
(a) Because (NH4)2Se is a solid, the equilibrium constant Kc is
given by
Kc = [NH3]2[H2Se]

Alternatively, we can express the equilibrium constant KP in

terms of the partial pressures of NH3 and H2Se:
2
K p = PNH 3
PH 2Se

27
Example 14.5

(b) Here AgCl is a solid so the equilibrium constant is given by

Kc = [Ag+][Cl-]

Because no gases are present, there is no KP expression.

(c) We note that P4 is a solid and PCl3 is a liquid, so they do not

appear in the equilibrium constant expression. Thus, Kc is
given by
1
Kc = 6
[Cl 2 ]
28
Example 14.5

Alternatively, we can express the equilibrium constant in terms

of the pressure of Cl2:

1
Kp = 6
PCl2

29
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.

30
Example 14.6
Strategy

Remember that pure solids do not appear in the equilibrium

constant expression. The relationship between KP and Kc is
given by Equation (14.5).

Solution

(a) Using Equation (14.8) we write

KP = PCO2
= 0.236

31
Example 14.6

(b) From Equation (14.5), we know

KP = Kc(0.0821T)Δn

In this case, T = 800 + 273 = 1073 K and Δn = 1, so we

substitute these values in the equation and obtain

0.236 = Kc(0.0821 x 1073)

Kc = 2.68 x 10-3

32
 [C][D] [E][F]
A+B C+D K′c K′c = Kc′′=
[A][B] [C][D]
C+D E+F K′′c
[E][F]
A+B E+F Kc Kc =
[A][B]

Kc = Kc′ x Kc′′

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.

33
N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)

[NO2]2 [N2O4] 1
K= = 4.63 x 10 -3
K′ = = = 216
[N2O4] [NO2] 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.

34
Example 14.7
The reaction for the production of ammonia can be written in a
number of ways:

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

1 3
(b) 2 N2(g) + 2 H2(g) NH3(g)
1 2
(c) 3 N2(g) + H2(g) 3 NH3(g)

Write the equilibrium constant expression for each formulation.

(Express the concentrations of the reacting species in mol/L.)

(d) How are the equilibrium constants related to one another?

35
Example 14.7

Strategy

We are given three different expressions for the same reacting

system. Remember that the equilibrium constant expression
depends on how the equation is balanced, that is, on the
stoichiometric coefficients used in the equation.

36
Example 14.7
Solution 2
(a) [NH3 ]
Ka =
[N 2 ][H 2 ]3

(b) [NH3 ]
Kb = 1 3
[N 2 ]2 [H 2 ]2

(c) 2
[NH 3 ]3
Kc = 1
[N 2 ]3 [H 2]
37
Example 14.7

(d)
K a =K b2
K a =K c3
3
K b2  K c3 or Kb  Kc2

38
 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.
39
Chemical Kinetics and Chemical Equilibrium

kf ratef = kf [A][B]2
A + 2B AB2
kr rater = kr [AB2]

Equilibrium
ratef = rater

kf [A][B]2 = kr [AB2]

kf [AB2]
= Kc =
kr [A][B]2

40
 The reaction quotient (Qc) is calculated by substituting the
initial concentrations of the reactants and products into the
equilibrium constant (Kc) expression.
IF
• Qc < Kc system proceeds from left to right to reach equilibrium
• Qc = Kc the system is at equilibrium
• Qc > Kc system proceeds from right to left to reach equilibrium

41
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

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

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.

42
Example 14.8

Strategy

We are given the initial amounts of the gases (in moles) in a

vessel of known volume (in liters), so we can calculate their
molar concentrations and hence the reaction quotient (Qc). How
does a comparison of Qc with Kc enable us to determine if the
system is at equilibrium or, if not, in which direction will the net
reaction proceed to reach equilibrium?

43
Example 14.8

Solution

The initial concentrations of the reacting species are

0.249 mol
[N 2 ]o = = 0.0711 M
3.50 L
3.21  10 2 mol
[H 2 ]o = = 9.17  10 3 M
3.50 L
6.42  104 mol
[NH3 ]o = = 1.83  10 4 M
3.50 L

44
Example 14.8

Next we write

[NH 3 ]o2 (1.83 × 10-4 ) 2

Qc = 3
 -3 3
= 0.611
[N 2 ]o [H 2 ]o (0.0711)(9.17 × 10 )

Because Qc is smaller than 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.

45
 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.

46
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 H2(g) + I2(g) 2HI(g) is 54.3 at this
temperature. Calculate the concentrations of H2, I2, and HI at
equilibrium.

47
Example 14.9

Strategy

We are given the initial amounts of the gases (in moles) in a

vessel of known volume (in liters), so we can calculate their
molar concentrations. Because initially no HI was present, the
system could not be at equilibrium. Therefore, some H2 would
react with the same amount of I2 (why?) to form HI until
equilibrium was established.

48
Example 14.9
Solution We follow the preceding procedure to calculate the
equilibrium concentrations.

Step 1: The stoichiometry of the reaction is 1 mol H2 reacting

with 1 mol I2 to yield 2 mol HI. Let x be the depletion in
concentration (mol/L) of H2 and I2 at equilibrium. It
follows that the equilibrium concentration of HI must be
2x. We summarize the changes in concentrations as
follows:
H2 + I2 2HI
Initial (M): 0.500 0.500 0.000
Change (M): -x -x + 2x
Equilibrium (M): (0.500 - x) (0.500 - x) 2x
49
Example 14.9
Step 2: The equilibrium constant is given by

[HI]2
Kc =
[H 2 ][I 2 ]

Substituting, we get
(2x ) 2
54.3 =
(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
50
Example 14.9

Step 3: At equilibrium, the concentrations are

[H2] = (0.500 - 0.393) M = 0.107 M

[I2] = (0.500 - 0.393) M = 0.107 M
[HI] = 2 x 0.393 M = 0.786 M

Check You can check your answers by calculating Kc using

the equilibrium concentrations. Remember that Kc is a
constant for a particular reaction at a given temperature.

51
Example 14.10

For the same reaction and temperature as in Example 14.9,

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

52
Example 14.10

Strategy

From the initial concentrations we can calculate the reaction

quotient (Qc) to see if the system is at equilibrium or, if not, in
which direction the net reaction will proceed to reach
equilibrium. A comparison of Qc with Kc also enables us to
determine if there will be a depletion in H2 and I2 or HI as
equilibrium is established.

53
Example 14.10
Solution

First we calculate Qc as follows:

[HI]02 (0.0224) 2
Qc = = = 19.5
[H 2 ]0 [I 2 ]0 (0.00623)(0.00414)

Because Qc (19.5) is smaller than Kc (54.3), we conclude that the

net reaction will proceed from left to right until equilibrium is
reached (see Figure 14.4); that is, there will be a depletion of H2
and I2 and a gain in HI.

54
Example 14.10

Step 1: Let x be the depletion in concentration (mol/L) of H2

and I2 at equilibrium. From the stoichiometry of the
reaction it follows that the increase in concentration for
HI must be 2x. Next we write

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)

55
Example 14.10
Step 2: The equilibrium constant is

[HI]2
Kc =
[H 2 ][I 2 ]

Substituting, we get
(0.0224 + 2x) 2
54.3 =
(0.00623 - x)(0.00414 - x)

It is not possible to solve this equation by the square root

shortcut, as the starting concentrations [H2] and [I2] are unequal.
Instead, we must first carry out the multiplications

54.3(2.58 x 10-5 - 0.0104x + x2) = 5.02 x 10-4 + 0.0896x + 4x2 56

Example 14.10
Collecting terms, we get

50.3x2 - 0.654x + 8.98 x 10-4 = 0

This is a quadratic equation of the form ax2 + bx + c = 0. The

solution for a quadratic equation (see Appendix 4) is
-b ± b 2 - 4ac
x=
2a

Here we have a = 50.3, b = -0.654, and c = 8.98 x 10-4, so that

0.654 ± (-0.654) 2 - 4(50.3)(8.98 × 10-4 )

x=
2 × 50.3
x = 0.0114 M or x = 0.00156 M
57
Example 14.10

The first solution is physically impossible because the amounts

of H2 and I2 reacted would be more than those originally
present. The second solution gives the correct answer. Note
that in solving quadratic equations of this type, one answer is
always physically impossible, so choosing a value for x is easy.

Step 3: At equilibrium, the concentrations are

[H2] = (0.00623 - 0.00156) M = 0.00467 M

[I2] = (0.00414 - 0.00156) M - 0.00258 M
[HI] = (0.0224 + 2 x 0.00156) M = 0.0255 M

58
Example 14.10

Check

You can check the answers by calculating Kc using the

equilibrium concentrations. Remember that Kc is a constant for
a particular reaction at a given temperature.

59
 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

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

Equilibrium
Add
shifts left to
NH3
offset stress

60
 Le Châtelier’s Principle

• Changes in Concentration continued

Remove
Add Remove
Add

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left
61
Example 14.11

At 720°C, the equilibrium constant Kc for the reaction

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

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. (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.
62
Example 14.11

Strategy

(a) What is the stress applied to the system? How does the
system adjust to offset the stress?

(b) At the instant when some NH3 is added, the system is no

longer at equilibrium. How do we calculate the Qc for the
reaction at this point? How does a comparison of Qc with Kc
tell us the direction of the net reaction to reach equilibrium.

63
Example 14.11

Solution

(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)

64
 Example 14.11

b) At the instant when some of the NH3 is added, the system

is no longer at equilibrium. The reaction quotient is given by

[NH3 ]02
Qc =
[N 2 ]0 [H 2 ]30
(3.65) 2

(0.683)(8.80)3
= 2.86  102

Because this value is greater than 2.37 x 10-3, the net

reaction shifts from right to left until Qc equals Kc.

65
Example 14.11

Figure 14.8 shows qualitatively the changes in concentrations

of the reacting species.

66
 Le Châtelier’s Principle

• Changes in Volume and Pressure

A (g) + B (g) C (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

67
Example 14.12

Consider the following equilibrium systems:

(a) 2PbS(s) + 3O2(g) 2PbO(s) + 2SO2(g)

(b) PCl5(g) PCl3(g) + Cl2(g)

(c) H2(g) + CO2(g) H2O(g) + CO(g)

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.

68
Example 14.12

Strategy

A change in pressure can affect only the volume of a gas, but

not that of a solid because solids (and liquids) are much less
compressible. The stress applied is an increase in pressure.
According to Le Châtelier’s principle, the system will adjust to
partially offset this stress. In other words, the system will adjust
to decrease the pressure. This can be achieved by shifting to
the side of the equation that has fewer moles of gas. Recall that
pressure is directly proportional to moles of gas: PV = nRT
so P  n.

69
Example 14.12
Solution
(a) Consider only the gaseous molecules. In the balanced
equation, there are 3 moles of gaseous reactants and 2
moles of gaseous products. Therefore, the net reaction will
shift toward the products (to the right) when the pressure is
increased.

(b) The number of moles of products is 2 and that of reactants

is 1; therefore, the net reaction will shift to the left, toward
the reactant.

(c) The number of moles of products is equal to the number of

moles of reactants, so a change in pressure has no effect
on the equilibrium.
70
Example 14.12

Check

In each case, the prediction is consistent with Le Châtelier’s

principle.

71
 Le Châtelier’s Principle
• Changes in Temperature
Change Exothermic Rx Endothermic Rx
Increase temperature K decreases K increases
Decrease temperature K increases K decreases

N2O4 (g) 2NO2 (g)

colder hotter 72
 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

Catalyst lowers Ea for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift 73
equilibrium.
 Le Châtelier’s Principle - Summary

Change Equilibrium
Change Shift 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

74
Example 14.13
Consider the following equilibrium process between dinitrogen
tetrafluoride (N2F4) and nitrogen difluoride (NF2):

N2F4(g) 2NF2(g) ΔH° = 38.5 kJ/mol

Predict the changes in the equilibrium if

(a) the reacting mixture is heated at constant volume;
(b) some N2F4 gas is removed from the reacting mixture at
constant temperature and volume;
(c) the pressure on the reacting mixture is decreased at
constant temperature; and
(d) a catalyst is added to the reacting mixture.
75
Example 14.13
Strategy

(a) What does the sign of ΔH° indicate about the heat change
(endothermic or exothermic) for the forward reaction?

(b) Would the removal of some N2F4 increase or decrease the

Qc of the reaction?

(c) How would the decrease in pressure change the volume of

the system?

(d) What is the function of a catalyst? How does it affect a

reacting system not at equilibrium? at equilibrium?
76
Example 14.13

Solution

(a) The stress applied is the heat added to the system. Note
that the N2F4 → 2NF2 reaction is an endothermic process
(ΔH° > 0), which absorbs heat from the surroundings.
Therefore, we can think of heat as a reactant

heat + N2F4(g) 2NF2(g)

The system will adjust to remove some of the added heat

by undergoing a decomposition reaction (from left to right).

77
 Example 14.13
The equilibrium constant

[NF2 ]2
Kc =
[N 2 F4 ]
will therefore increase with increasing temperature because the
concentration of NF2 has increased and that of N2F4 has
decreased. Recall that the equilibrium constant is a constant
only at a particular temperature. If the temperature is changed,
then the equilibrium constant will also change.
The stress here is the removal of N2F4 gas. The system will
shift to replace some of the N2F4 removed. Therefore, the
system shifts from right to left until equilibrium is reestablished.
As a result, some NF2 combines to form N2F4.
78
Example 14.13
Comment

The equilibrium constant remains unchanged in this case

because temperature is held constant. It might seem that Kc
should change because NF2 combines to produce N2F4.
Remember, however, that initially some N2F4 was removed. The
system adjusts to replace only some of the N2F4 that was
removed, so that overall the amount of N2F4 has decreased. In
fact, by the time the equilibrium is reestablished, the amounts of
both NF2 and N2F4 have decreased. Looking at the equilibrium
constant expression, we see that dividing a smaller numerator
by a smaller denominator gives the same value of Kc.

79
Example 14.13

(c) The stress applied is a decrease in pressure (which is

accompanied by an increase in gas volume). The system
will adjust to remove the stress by increasing the pressure.
Recall that pressure is directly proportional to the number
of moles of a gas. In the balanced equation we see that
the formation of NF2 from N2F4 will increase the total
number of moles of gases and hence the pressure.
Therefore, the system will shift from left to right to
reestablish equilibrium. The equilibrium constant will
remain unchanged because temperature is held constant.

80
Example 14.13

(d) The function of a catalyst is to increase the rate of a

reaction. If a catalyst is added to a reacting system not at
equilibrium, the system will reach equilibrium faster than
if left undisturbed. If a system is already at equilibrium, as
in this case, the addition of a catalyst will not affect either
the concentrations of NF2 and N2F4 or the equilibrium
constant.

81
 Chemistry In Action
Life at High Altitudes and Hemoglobin Production

Hb (aq) + O2 (aq) HbO2 (aq)

[HbO2]
Kc =
[Hb][O2]

82
Chemistry In Action: The Haber Process
N2 (g) + 3H2 (g) 2NH3 (g) H0 = -92.6 kJ/mol

83