OpenStax-CNX module: m62047 1

Equilibrium Constants *

OpenStax Chemistry: Atom First

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Abstract
By the end of this section, you will be able to:

• Derive reaction quotients from chemical equations representing homogeneous and heterogeneous
reactions
• Calculate values of reaction quotients and equilibrium constants, using concentrations and pressures
• Relate the magnitude of an equilibrium constant to properties of the chemical system

Now that we have a symbol (

) to designate reversible reactions, we will need a way to express mathe-
matically how the amounts of reactants and products aect the equilibrium of the system. A general equation
for a reversible reaction may be written as follows:

mA + nB+
xC + y D (1)

We can write the reaction quotient (Q ) for this equation. When evaluated using concentrations, it is

c
called Q . We use brackets to indicate molar concentrations of reactants and products.

x yn
[C] [D]
Qc = m (2)
[A] [B]
The reaction quotient is equal to the molar concentrations of the products of the chemical equation (multi-
plied together) over the reactants (also multiplied together), with each concentration raised to the power of
the coecient of that substance in the balanced chemical equation. For example, the reaction quotient for
the reversible reaction 2NO2 (g)
N2 O4 (g) is given by this expression:

[N2 O4 ]
Qc = 2 (3)
[NO2 ]

Example 1
Writing Reaction Quotient Expressions
Write the expression for the reaction quotient for each of the following reactions:

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(a) 3O2 (g)

2O3 (g)
(b) N2 (g) + 3H2 (g)
2NH3 (g)
(c) 4NH3 (g) + 7O2 (g)
4NO2 (g) + 6H2 O (g)
Solution
O3 ]2
[
(a)
O2 ]3
Qc = [
[NH3 ]2
[N2 ][H2 ]3
(b) Qc =

[NO2 ]4 [H2 O]6

7
[NH3 ] [O2 ]
(c) Qc = 4

Check Your Learning

Write the expression for the reaction quotient for each of the following reactions:
(a) 2SO2 (g) + O2 (g)
2SO3 (g)
(b) C4 H8 (g)
2C2 H4 (g)
(c) 2C4 H10 (g) + 13O2 (g)
8CO2 (g) + 10H2 O (g)

[SO3 ]2 ; (b) Q = [C2 H4 ]2 ; (c) Q = [CO2 ]8 [H2 O]10 13

note: (a) Qc = [SO2 ]2 [O2 ] c [C4 H8 ] c [C4 H10 ]2 [O2 ]

The numeric value of Q c for a given reaction varies; it depends on the concentrations of products and
reactants present at the time when Q c is determined. When pure reactants are mixed, Q c is initially zero
because there are no products present at that point. As the reaction proceeds, the value of Q c increases as
the concentrations of the products increase and the concentrations of the reactants simultaneously decrease
(Figure 3). When the reaction reaches equilibrium, the value of the reaction quotient no longer changes
because the concentrations no longer change.

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Figure 3: (a) The change in the concentrations of reactants and products is depicted as the 2SO2 (g) +
O2 (g)
2SO3 (g) reaction approaches equilibrium. (b) The change in concentrations of reactants and
products is depicted as the reaction 2SO3 (g)
2SO2 (g) + O2 (g) approaches equilibrium. (c) The graph
shows the change in the value of the reaction quotient as the reaction approaches equilibrium.

When a mixture of reactants and products of a reaction reaches equilibrium at a given temperature, its
reaction quotient always has the same value. This value is called the equilibrium constant (K ) of the
reaction at that temperature. As for the reaction quotient, when evaluated in terms of concentrations, it is
noted as K .c
That a reaction quotient always assumes the same value at equilibrium can be expressed as:

x y m
[C] [D] ... n
Qc at equilibrium = Kc = [B] ... (4)
[A]
This equation is a mathematical statement of the law of mass action: When a reaction has attained
equilibrium at a given temperature, the reaction quotient for the reaction always has the same value.

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Example 2
Evaluating a Reaction Quotient
Gaseous nitrogen dioxide forms dinitrogen tetroxide according to this equation:

2NO2 (g)
N2 O4 (g) (5)

When 0.10 mol NO 2 is added to a 1.0-L ask at 25

◦
C, the concentration changes so that at

2
equilibrium, [NO ] = 0.016 M and [N O ] = 0.042 M. 2 4
(a) What is the value of the reaction quotient before any reaction occurs?
(b) What is the value of the equilibrium constant for the reaction?
Solution
0.10 mol = 0.10 M, and [N2 O4 ] = 0 M. Thus,
(a) Before any product is formed, [NO2 ] = 1.0 L
[N2 O4 ] 0
Qc = 2 = =0 (6)
[NO2 ] 0.102
(b) At equilibrium, the value of the equilibrium constant is equal to the value of the reaction
[ N2 O4 ] = 0.042
= 1.6 × 102 .
quotient. At equilibrium, Kc = Qc = [ NO2 ]2 0.0162 The equilibrium constant is
2
1.6 × 10 .
Note that dimensional analysis would suggest the unit for this K value should be M c − 1. However,
it is common practice to omit units for K c values computed as described here, since it is the
magnitude of an equilibrium constant that relays useful information. As will be discussed later in
this module, the rigorous approach to computing equilibrium constants uses dimensionless quantities
derived from concentrations instead of actual concentrations, and so K c values are truly unitless.
Check Your Learning
For the reaction 2SO2 (g) + O2 (g)
2SO3 (g) , the concentrations at equilibrium are [SO2 ] = 0.90
2 3
M, [O ] = 0.35 M, and [SO ] = 1.1 M. What is the value of the equilibrium constant, K ? c
note: K c = 4.3

The magnitude of an equilibrium constant is a measure of the yield of a reaction when it reaches equilibrium.

c
A large value for K indicates that equilibrium is attained only after the reactants have been largely converted

c
into products. A small value of K much less than 1indicates that equilibrium is attained when only a
small proportion of the reactants have been converted into products.
Once a value of K c is known for a reaction, it can be used to predict directional shifts when compared to

c
the value of Q . A system that is not at equilibrium will proceed in the direction that establishes equilibrium.
◦
The data in Figure 7 illustrate this. When heated to a consistent temperature, 800 C, dierent starting

2
mixtures of CO, H O, CO , and H 2 2 react to reach compositions adhering to the same equilibrium constant
(the value of Q c c
changes until it equals the value of K ). This value is 0.640, the equilibrium constant for
the reaction under these conditions.

◦
CO (g) + H2 O (g)
CO2 (g) + H2 (g) Kc = 0.640 T = 800 C (7)

It is important to recognize that an equilibrium can be established starting either from reactants or from
products, or from a mixture of both. For example, equilibrium was established from Mixture 2 in Figure 7
when the products of the reaction were heated in a closed container. In fact, one technique used to determine
whether a reaction is truly at equilibrium is to approach equilibrium starting with reactants in one experiment
and starting with products in another. If the same value of the reaction quotient is observed when the
concentrations stop changing in both experiments, then we may be certain that the system has reached
equilibrium.

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Figure 7: Concentrations of three mixtures are shown before and after reaching equilibrium at 800
◦
C
for the so-called water gas shift reaction: CO (g) + H2 O (g)
CO2 (g) + H2 (g) .

Example 3
Predicting the Direction of Reaction
Given here are the starting concentrations of reactants and products for three experiments involving
this reaction:

CO (g) + H2 O (g)
CO2 (g) + H2 (g) (8)

Kc = 0.64 (9)

Determine in which direction the reaction proceeds as it goes to equilibrium in each of the three
experiments shown.

Reactants/Products Experiment 1 Experiment 2 Experiment 3

[CO]i 0.0203 M 0.011 M 0.0094 M

[H2 O]i 0.0203 M 0.0011 M 0.0025 M

[CO2 ]i 0.0040 M 0.037 M 0.0015 M

[H2 ]i 0.0040 M 0.046 M 0.0076 M

Table 1
Solution
Experiment 1:

[CO2 ] [H2 ] (0.0040) (0.0040)

Qc = = = 0.039. (10)
[CO] [H2 O] (0.0203) (0.0203)
Q c< c
K (0.039 < 0.64)

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The reaction will shift to the right.

Experiment 2:

[CO2 ] [H2 ] (0.037) (0.046)

Qc = = = 1.4 × 102 (11)
[CO] [H2 O] (0.011) (0.0011)
Q c> c
K (140 > 0.64)
The reaction will shift to the left.
Experiment 3:

[CO2 ] [H2 ] (0.0015) (0.0076)

Qc = = = 0.48 (12)
[CO] [H2 O] (0.0094) (0.0025)
Q c< c
K (0.48 < 0.64)
The reaction will shift to the right.
Check Your Learning
Calculate the reaction quotient and determine the direction in which each of the following reactions
will proceed to reach equilibrium.
(a) A 1.00-L ask containing 0.0500 mol of NO(g), 0.0155 mol of Cl2(g), and 0.500 mol of NOCl:

2NO (g) + Cl2 (g)

2NOCl (g) Kc = 4.6 × 104 (13)

3
(b) A 5.0-L ask containing 17 g of NH , 14 g of N , and 12 g of H : 2 2
N2 (g) + 3H2 (g)
2NH3 (g) Kc = 0.060 (14)

(c) A 2.00-L ask containing 230 g of SO (g): 3

2SO3 (g)
2SO2 (g) + O2 (g) Kc = 0.230 (15)

note: (a) Q c = 6.45 × 3

10 , shifts right. (b) Q c = 0.23, shifts left. (c) Q c = 0, shifts right

In Example 2, it was mentioned that the common practice is to omit units when evaluating reaction quotients
and equilibrium constants. It should be pointed out that using concentrations in these computations is a
convenient but simplied approach that sometimes leads to results that seemingly conict with the law of
mass action. For example, equilibria involving aqueous ions often exhibit equilibrium constants that vary
quite signicantly (are not constant) at high solution concentrations. This may be avoided by computing
K c values using the activities of the reactants and products in the equilibrium system instead of their
concentrations. The activity of a substance is a measure of its eective concentration under specied
conditions. While a detailed discussion of this important quantity is beyond the scope of an introductory
text, it is necessary to be aware of a few important aspects:

ˆ Activities are dimensionless (unitless) quantities and are in essence adjusted concentrations.
ˆ For relatively dilute solutions, a substance's activity and its molar concentration are roughly equal.
ˆ Activities for pure condensed phases (solids and liquids) are equal to 1.

As a consequence of this last consideration, Q c and K c expressions do not contain terms for solids or liquids
(being numerically equal to 1, these terms have no eect on the expression's value). Several examples of
equilibria yielding such expressions will be encountered in this section.

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1 Homogeneous Equilibria
A homogeneous equilibrium is one in which all of the reactants and products are present in a single
solution (by denition, a homogeneous mixture). In this chapter, we will concentrate on the two most
common types of homogeneous equilibria: those occurring in liquid-phase solutions and those involving
exclusively gaseous species. Reactions between solutes in liquid solutions belong to one type of homogeneous
equilibria. The chemical species involved can be molecules, ions, or a mixture of both. Several examples are
provided here.

[C2 H2 Br4 ]
C2 H2 (aq) + 2Br2 (aq)
C2 H2 Br4 (aq) Kc = 2 (16)
[C2 H2 ] [Br2 ]
[I3 − ]
I2 (aq) + I− (aq)
I3 − (aq) Kc = (17)
[I2 ] I−
 

Hg2
2+
(aq) + NO3 − (aq) + 3H3 O+ (aq)
2Hg2+ (aq) + HNO2 (aq) + 4H2 O (l) (18)


Hg
2+ 2 [HNO2 ]
Kc =
[Hg2 2+ ] [NO3 − ]

H3 O
+ 3 (19)

+  F− 
+

− H3 O
HF (aq) + H2 O (l)
H3 O (aq) + F (aq) Kc = (20)
[HF]
[NH4 + ] OH−
 
NH3 (aq) + H2 O (l)
NH4 + (aq) + OH− (aq) Kc = (21)
[NH3 ]
In each of these examples, the equilibrium system is an aqueous solution, as denoted by the aq annotations

2
on the solute formulas. Since H O(l ) is the solvent for these solutions, its concentration does not appear as
a term in the K c expression, as discussed earlier, even though it may also appear as a reactant or product
in the chemical equation.
Reactions in which all reactants and products are gases represent a second class of homogeneous equilibria.
We use molar concentrations in the following examples, but we will see shortly that partial pressures of the
gases may be used as well.

[C2 H4 ] [H2 ]
C2 H6 (g)
C2 H4 (g) + H2 (g) Kc = (22)
[C2 H6 ]
2
[O3 ]
3O2 (g)
2O3 (g) Kc = 3 (23)
[O2 ]
2
[NH3 ]
N2 (g) + 3H2 (g)
2NH3 (g) Kc = 3 (24)
[N2 ] [H2 ]
3 4
[CO2 ] [H2 O]
C3 H8 (g) + 5O2 (g)
3CO2 (g) + 4H2 O (g) Kc = 5 (25)
[C3 H8 ] [O2 ]
2
Note that the concentration of H O(g ) has been included in the last example because water is not the
solvent in this gas-phase reaction and its concentration (and activity) changes.
Whenever gases are involved in a reaction, the partial pressure of each gas can be used instead of its
concentration in the equation for the reaction quotient because the partial pressure of a gas is directly
proportional to its concentration at constant temperature. This relationship can be derived from the ideal
n
gas equation, where M is the molar concentration of gas,
V .

P V = nRT (26)

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n
P = RT (27)
V

= M RT (28)

Thus, at constant temperature, the pressure of a gas is directly proportional to its concentration.
Using the partial pressures of the gases, we can write the reaction quotient for the system C2 H6 (g)

C2 H4 (g) + H2 (g) by following the same guidelines for deriving concentration-based expressions:

PC2 H4 PH2
QP = (29)
PC 2 H 6
In this equation we use Q P to indicate a reaction quotient written with partial pressures: PC2 H6 is the partial
pressure of C H ;2 6 PH2 , the partial pressure of H2 ; and PC2 H6 , the partial pressure of C2 H4 . At equilibrium:
PC2 H4 PH2
KP = QP = (30)
PC2 H6
The subscript P in the symbol KP designates an equilibrium constant derived using partial pressures instead

P
of concentrations. The equilibrium constant, K , is still a constant, but its numeric value may dier from
the equilibrium constant found for the same reaction by using concentrations.
Conversion between a value for Kc , an equilibrium constant expressed in terms of concentrations, and a

P
value for K , an equilibrium constant expressed in terms of pressures, is straightforward (a K or Q without
a subscript could be either concentration or pressure).
The equation relating K c and K P is derived as follows. For the gas-phase reaction mA + nB
xC + y D:
x y
(PC ) (PD )
KP = m n (31)
(PA ) (PB )
x y
([C] × RT ) ([D] × RT )
= m n
([A] × RT ) ([B] × RT ) (32)
x
[C] [D]
ym
(RT )
+x y
n
= [B] × m+n (33)
[A] (RT )

= Kc (RT )
+
(x y)−(m n) + (34)

∆n
= Kc (RT ) (35)

The relationship between K c and K P is

∆n
KP = Kc (RT ) (36)

In this equation, ∆n is the dierence between the sum of the coecients of the gaseous products and the
sum of the coecients of the gaseous reactants in the reaction (the change in moles of gas between the
reactants and the products). For the gas-phase reaction mA + nB
xC + y D, we have

∆n = (x+y) − (m+n) (37)

Example 4
Calculation of KP
Write the equations for the conversion of K c to K P for each of the following reactions:
(a) C2 H6 (g)
C2 H4 (g) + H2 (g)

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(b) CO (g) + H2 O (g)

CO2 (g) + H2 (g)
(c) N2 (g) + 3H2 (g)
2NH3 (g)
◦
(d) K c is equal to 0.28 for the following reaction at 900 C:

CS2 (g) + 4H2 (g)

CH4 (g) + 2H2 S (g) (38)

What is K P at this temperature?

Solution
(a) ∆n = (2) − (1) = 1
K P = K c (RT )
∆n
= Kc (RT )
1 = K c (RT )
(b) ∆n = (2) − (2) = 0
K P = K c (RT )
∆n
= K c (RT )
0 = K c
(c) ∆n = (2) − (1 + 3) = −2
K P = K c (RT )
∆n
= K
K
c (RT )− = (RTc)2 2
(d) K P = K c (RT)
∆n
= (0.28)[(0.0821)(1173)]
− 2 = 3.0 × 10
− 5
Check Your Learning
Write the equations for the conversion of K c to K P for each of the following reactions, which occur
in the gas phase:
(a) 2SO2 (g) + O2 (g)
2SO3 (g)
(b) N2 O4 (g)
2NO2 (g)
(c) C3 H8 (g) + 5O2 (g)
3CO2 (g) + 4H2 O (g)
◦
(d) At 227 C, the following reaction has K c = 0.0952:

CH3 OH (g)
CO (g) + 2H2 (g) (39)

What would be the value of K P at this temperature?

note: (a) K P = K c (RT )

− 1 ; (b) KP = K c (RT ); (c) K P = K c (RT ); (d) 160 or 1.6 × 2
10

2 Heterogeneous Equilibria
A heterogeneous equilibrium is a system in which reactants and products are found in two or more phases.
The phases may be any combination of solid, liquid, or gas phases, and solutions. When dealing with these
equilibria, remember that solids and pure liquids do not appear in equilibrium constant expressions (the
activities of pure solids, pure liquids, and solvents are 1).
Some heterogeneous equilibria involve chemical changes; for example:

− 2
(s)
Pb2+ (aq) + 2Cl− (aq) 2+
  
PbCl2 Kc = Pb Cl (40)

1
CaO (s) + CO2 (g)
CaCO3 (s) Kc = (41)
[CO2

C (s) + 2S (g)
CS2 (g) Kc = [CS2

Other heterogeneous equilibria involve phase changes, for example, the evaporation of liquid bromine,
S
[ ]2 (2)
as shown in the following equation:

Br2 (l)
Br2 (g) Kc = [Br2 ] (43)

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We can write equations for reaction quotients of heterogeneous equilibria that involve gases, using partial
pressures instead of concentrations. Two examples are:

1
CaO (s) + CO2 (g)
CaCO3 (s) KP = (44)
PCO2
PCS2
C (s) + 2S (g)
CS2 (g) KP = (45)
(PS )
2

3 Key Concepts and Summary

For any reaction that is at equilibrium, the reaction quotient Q is equal to the equilibrium constant K for
the reaction. If a reactant or product is a pure solid, a pure liquid, or the solvent in a dilute solution,
the concentration of this component does not appear in the expression for the equilibrium constant. At
equilibrium, the values of the concentrations of the reactants and products are constant. Their particular
values may vary depending on conditions, but the value of the reaction quotient will always equal K (K c
when using concentrations or K P when using partial pressures).
A homogeneous equilibrium is an equilibrium in which all components are in the same phase. A het-
erogeneous equilibrium is an equilibrium in which components are in two or more phases. We can decide
whether a reaction is at equilibrium by comparing the reaction quotient with the equilibrium constant for
the reaction.

4 Key Equations
ˆ Q= C D
[ ]x [ ]y m n
[ ]A x
[B]
y
where mA + nB
xC + y D
(PC ) (PD )
ˆ QP = (P m
A ) (PB )
n where mA + nB
xC + y D
ˆ P = MRT
∆n
ˆ KP = Kc (RT )

5 Chemistry End of Chapter Exercises

Exercise 1
Explain why there may be an innite number of values for the reaction quotient of a reaction at a
given temperature but there can be only one value for the equilibrium constant at that temperature.

Exercise 2 (Solution on p. 14.)

2 2
Explain why an equilibrium between Br (l ) and Br (g ) would not be established if the container
were not a closed vessel shown in .

Exercise 3
If you observe the following reaction at equilibrium, is it possible to tell whether the reaction
started with pure NO 2 or with pure N O ? 2 4
2NO2 (g)
N2 O4 (g)
Exercise 4 (Solution on p. 14.)
Among the solubility rules previously discussed is the statement: All chlorides are soluble except

2 2 2
Hg Cl , AgCl, PbCl , and CuCl.
(a) Write the expression for the equilibrium constant for the reaction represented by the equation
AgCl (s)
Ag+ (aq) + Cl− (aq) . Is K c> 1, < 1, or ≈ 1? Explain your answer.
(b) Write the expression for the equilibrium constant for the reaction represented by the equation
Pb
2+
(aq) + 2Cl− (aq)
PbCl2 (s) . Is K c> 1, < 1, or ≈ 1? Explain your answer.

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Exercise 5
Among the solubility rules previously discussed is the statement: Carbonates, phosphates, borates,
and arsenatesexcept those of the ammonium ion and the alkali metalsare insoluble.
(a) Write the expression for the equilibrium constant for the reaction represented by the equation
CaCO3 (s)
Ca2+ (aq) + CO3 2− (aq) . Is K c> 1, < 1, or ≈ 1? Explain your answer.
(b) Write the expression for the equilibrium constant for the reaction represented by the equation
3Ba2+ (aq) + 2PO4 3− (aq)
Ba3 (PO4 )2 (s) . Is K c> 1, < 1, or ≈ 1? Explain your answer.

Exercise 6 (Solution on p. 14.)

Benzene is one of the compounds used as octane enhancers in unleaded gasoline. It is manufactured
by the catalytic conversion of acetylene to benzene: 3C2 H2 (g) −→ C6 H6 (g) . Which value of Kc
would make this reaction most useful commercially? K c ≈ 0.01, Kc ≈ 1, or Kc ≈ 10. Explain your
answer.

Exercise 7
Show that the complete chemical equation, the total ionic equation, and the net ionic equation for
the reaction represented by the equation KI (aq) + I2 (aq)
KI3 (aq) give the same expression for
the reaction quotient. KI 3 is composed of the ions K
+ and I3 − .
Exercise 8 (Solution on p. 14.)
For a titration to be eective, the reaction must be rapid and the yield of the reaction must
essentially be 100%. Is K c> 1, < 1, or ≈ 1 for a titration reaction?

Exercise 9
For a precipitation reaction to be useful in a gravimetric analysis, the product of the reaction must
be insoluble. Is K c> 1, < 1, or ≈ 1 for a useful precipitation reaction?

Exercise 10 (Solution on p. 14.)

c
Write the mathematical expression for the reaction quotient, Q , for each of the following reactions:
(a) CH4 (g) + Cl2 (g)
CH3 Cl (g) + HCl (g)
(b) N2 (g) + O2 (g)
2NO (g)
(c) 2SO2 (g) + O2 (g)
2SO3 (g)
(d) BaSO3 (s)
BaO (s) + SO2 (g)
(e) P4 (g) + 5O2 (g)
P4 O10 (s)
(f ) Br2 (g)
2Br (g)
(g) CH4 (g) + 2O2 (g)
CO2 (g) + 2H2 O (l)
(h) CuSO4 ·5H2 O (s)
CuSO4 (s) + 5H2 O (g)

Exercise 11
c
Write the mathematical expression for the reaction quotient, Q , for each of the following reactions:
(a) N2 (g) + 3H2 (g)
2NH3 (g)
(b) 4NH3 (g) + 5O2 (g)
4NO (g) + 6H2 O (g)
(c) N2 O4 (g)
2NO2 (g)
(d) CO2 (g) + H2 (g)
CO (g) + H2 O (g)
(e) NH4 Cl (s)
NH3 (g) + HCl (g)
(f ) 2Pb(NO3 )2 (s)
2PbO (s) + 4NO2 (g) + O2 (g)
(g) 2H2 (g) + O2 (g)
2H2 O (l)
(h) S8 (g)
8S (g)

Exercise 12 (Solution on p. 14.)

The initial concentrations or pressures of reactants and products are given for each of the following
systems. Calculate the reaction quotient and determine the direction in which each system will
proceed to reach equilibrium.
(a) 2NH3 (g)
N2 (g) + 3H2 (g) Kc = 17; 3 2
[NH ] = 0.20 M, [N ] = 1.00 M, [H ] = 2
1.00 M

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(b) 2NH3 (g)

N2 (g) + 3H2 (g) KP = 6.8 × 104 ; initial pressures: NH 3 = 3.0 atm,
N 2 = 2.0 atm, H 2 = 1.0 atm
(c) 2SO3 (g)
2SO2 (g) + O2 (g) Kc = 0.230; [SO3 ] = 0.00 M, [SO2 ] = 1.00 M, [O2 ]
= 1.00 M
(d) 2SO3 (g)
2SO2 (g) + O2 (g) KP = 16.5; initial pressures: SO 3 = 1.00 atm, SO2
= 1.00 atm, O 2 = 1.00 atm
(e) 2NO (g) + Cl2 (g)
2NOCl (g) Kc = 4.6 × 104 ; 2
[NO] = 1.00 M, [Cl ] = 1.00 M,
[NOCl] = 0 M
(f ) N2 (g) + O2 (g)
2NO (g) KP = 0.050; initial pressures: NO = 10.0 atm, N 2 =
O2 = 5 atm
Exercise 13
The initial concentrations or pressures of reactants and products are given for each of the following
systems. Calculate the reaction quotient and determine the direction in which each system will
proceed to reach equilibrium.
(a) 2NH3 (g)
N2 (g) + 3H2 (g) Kc = 17; 3 2
[NH ] = 0.50 M, [N ] = 0.15 M, [H ] = 2
0.12 M
(b) 2NH3 (g)
N2 (g) + 3H2 (g) KP = 6.8 × 104 ; initial pressures: NH 3 = 2.00 atm,
N 2 = 10.00 atm, H 2 = 10.00 atm
(c) 2SO3 (g)
2SO2 (g) + O2 (g) Kc = 0.230; 3 2
[SO ] = 2.00 M, [SO ] = 2.00 M, [O ] 2
= 2.00 M
(d) 2SO3 (g)
2SO2 (g) + O2 (g) KP = 6.5 atm; initial pressures: SO 2 = 1.00 atm,
O 2 = 1.130 atm, SO 3 = 0 atm
(e) 2NO (g) + Cl2 (g)
2NOCl (g) KP = 2.5 × 103 ; initial pressures: NO = 1.00
atm, Cl 2 = 1.00 atm, NOCl = 0 atm
(f ) N2 (g) + O2 (g)
2NO (g) Kc = 0.050; 2 2
[N ] = 0.100 M, [O ] = 0.200 M, [NO] =
1.00 M

Exercise 14 (Solution on p. 14.)

The following reaction has K P = 4.50 × 10
5
−
at 720 K.
N2 (g) + 3H2 (g)
2NH3 (g)
If a reaction vessel is lled with each gas to the partial pressures listed, in which direction will

3
it shift to reach equilibrium? P (NH ) = 93 atm, P (N ) = 48 atm, and P (H ) = 52 2 2
Exercise 15
Determine if the following system is at equilibrium. If not, in which direction will the system need
to shift to reach equilibrium?
SO2 Cl2 (g)
SO2 (g) + Cl2 (g)
2 2 2
[SO Cl ] = 0.12 M, [Cl ] = 0.16 M and [SO ] = 0.050 M. K 2 c for the reaction is 0.078.

Exercise 16 (Solution on p. 14.)

Which of the systems described in Exercise give homogeneous equilibria? Which give heterogeneous
equilibria?

Exercise 17
Which of the systems described in Exercise give homogeneous equilibria? Which give heterogeneous
equilibria?

Exercise 18 (Solution on p. 14.)

For which of the reactions in Exercise does K c (calculated using concentrations) equal K P (calcu-
lated using pressures)?

Exercise 19
For which of the reactions in Exercise does K c (calculated using concentrations) equal K P (calcu-
lated using pressures)?

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Exercise 20 (Solution on p. 14.)

Convert the values of K c to values of K P or the values of K P to values of K . c
(a) N2 (g) + 3H2 (g)
2NH3 (g) Kc = 0.50 at 400 ◦ C
(b) H2 (g) + I2 (g)
2HI (g) Kc = 50.2 at 448 ◦ C
(c) Na2 SO4 ·10H2 O (s)
Na2 SO4 (s) + 10H2 O (g) KP = 4.08 × 10−25 at 25 ◦
C
◦
(d) H2 O (l)
H2 O (g) KP = 0.122 at 50 C
Exercise 21
Convert the values of K c to values of K P or the values of K P to values of K . c
(a) Cl2(g) + Br2 (g)
2BrCl (g) Kc = 4.7 × 10−2 at 25 ◦ C
(b) 2SO2 (g) + O2 (g)
2SO3 (g) KP = 48.2 at 500 ◦ C
(c) CaCl2 ·6H2 O (s)
CaCl2 (s) + 6H2 O (g) KP = 5.09 × 10−44 at 25 ◦
C
◦
(d) H2 O (l)
H2 O (g) KP = 0.196 at 60 C
Exercise 22 (Solution on p. 14.)
What is the value of the equilibrium constant expression for the change H2 O (l)
H2 O (g) at 30
◦
C? (See Appendix E.)

Exercise 23
Write the expression of the reaction quotient for the ionization of HOCN in water.

Exercise 24 (Solution on p. 14.)

Write the reaction quotient expression for the ionization of NH 3 in water.

Exercise 25
What is the approximate value of the equilibrium constant K P for the change C2 H5 OC2 H5 (l)

◦
C2 H5 OC2 H5 (g) at 25 C. (Vapor pressure was described in the previous chapter on liquids and
solids; refer back to this chapter to nd the relevant information needed to solve this problem.)

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Solutions to Exercises in this Module

Solution to Exercise (p. 10)
Equilibrium cannot be established between the liquid and the gas phase if the top is removed from the
bottle because the system is not closed; one of the components of the equilibrium, the Br 2 vapor, would
escape from the bottle until all liquid disappeared. Thus, more liquid would evaporate than can condense
back from the gas phase to the liquid phase.
Solution to Exercise (p. 10)
+ −
(a) Kc = [Ag ][Cl ] < 1. AgCl is insoluble; thus, the concentrations of ions are much less than 1 M ; (b)
Kc = 1
> 1 because PbCl2 is insoluble and formation of the solid will reduce the concentration
[Pb ][Cl ]
2+ − 2

of ions to a low level (<1 M ).

Solution to Exercise (p. 11)
[C H ]
Since Kc =
[C H ]
, a value of Kc
2
6 6
2
3 ≈ 6 6
10 means that C H 2 2
predominates over C H . In such a case, the

reaction would be commercially feasible if the rate to equilibrium is suitable.

Solution to Exercise (p. 11)
K c> 1
Solution to Exercise (p. 11)
[CH Cl][HCl] [NO] [SO ] 2 2

[CH ][Cl ] ; (b) Qc = [N ] [O ] ; (c) Qc = [SO ] [O ] ; (d) Qc = [SO2 ]; (e) Qc = [P ][O ] ; (f )

3 3 1
(a) Qc = 2 5
4 2 2 2

Qc = [[Br [CO ]
2 2 4 2
2
5
Br ] ; (g) Qc = [CH ][O ] ; (h) Qc = [H2 O]
] 2
2
2 4 2
Solution to Exercise (p. 11)
(a) Q c 25 proceeds left; (b) QP 0.22 proceeds right; (c) Qc undened proceeds left; (d) QP 1.00 proceeds
right; (e) Q P 0 proceeds right; (f ) Q c 4 proceeds left
Solution to Exercise (p. 12)
The system will shift toward the reactants to reach equilibrium.
Solution to Exercise (p. 12)
(a) homogenous; (b) homogenous; (c) homogenous; (d) heterogeneous; (e) heterogeneous; (f ) homogenous;
(g) heterogeneous; (h) heterogeneous
Solution to Exercise (p. 12)
This situation occurs in (a) and (b).
Solution to Exercise (p. 13)
−4 −39 −3
(a) KP = 1.6 × 10 ; (b) KP = 50.2; (c) Kc = 5.31 × 10 ; (d) Kc = 4.60 × 10
Solution to Exercise (p. 13)
KP = PH O = 0.042.
2
Solution to Exercise (p. 13)
[NH + ][OH ]
4
−
Qc = [HN ] 3

Glossary
Denition 45: equilibrium constant (K )
value of the reaction quotient for a system at equilibrium

Denition 45: heterogeneous equilibria

equilibria between reactants and products in dierent phases

Denition 45: homogeneous equilibria

equilibria within a single phase

Denition 45: Kc
equilibrium constant for reactions based on concentrations of reactants and products

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Denition 45: KP
equilibrium constant for gas-phase reactions based on partial pressures of reactants and products

Denition 45: law of mass action

when a reversible reaction has attained equilibrium at a given temperature, the reaction quotient
remains constant

Denition 45: reaction quotient (Q )

ratio of the product of molar concentrations (or pressures) of the products to that of the reactants,
each concentration (or pressure) being raised to the power equal to the coecient in the equation

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