Chem Ch14

CHAPTER 14 | Chemical Equilibrium: Equal but Opposite Reaction Rates
14.1. Collect and Organize

For two reversible reactions, we are given the reaction profiles (Figure P14.1). The profile for the conversion of
A to B shows that reactant A has a lower free energy than product B. The profile for the conversion of C to D
shows that C has a higher free energy than D. From the profiles, we are to determine which reaction has the
larger kf, the smaller kr, and the larger value of Kc.
Analyze
The magnitude of the rate constant is inversely related to the magnitude of the activation energy, Ea. The
reaction with the larger kf, smaller kr, and the larger Kc is that reaction with the lowest Ea for the forward
reaction and where kf > kr.
Solve
The reaction C D has the larger kf, the smaller kr, and the larger Kc (because it has the lowest activation
energy for the forward direction).
Think about It
Remember that a large k (rate constant) means that the reaction is fast and therefore the reaction has a low
activation energy.
From Figure P14.2, depicting the molar concentrations of A (red spheres) and B (blue spheres) over time, we
are to determine whether the reaction reaches equilibrium, in what direction that equilibrium is achieved
(A B or B A), and what is the value of the equilibrium constant.
Analyze
(a) At equilibrium, the relative concentrations of A and B do not change.
(b) From Figure P14.2, we see that more A is present at the beginning of the reaction, but more B is present at
later times.
(c) The equilibrium constant can be calculated from the concentrations of A and B at equilibrium:
[ product ]
Kc =
[ reactant ]
Solve
(a) No. Because the last two boxes in Figure P14.2 do not contain the same number of A and B, we cannot tell
whether this reaction reaches equilibrium.
(b) A B
(c) If we assume that the last box in Figure P14.2 represents equilibrium, then
[ B] = 24 M = 1.5
Kc =
[ A] 16 M
Think about It
Equilibrium could be approached in this system starting with B reacting to give A. If we write that reaction as
B A, Kc would be
[A ] = 16 M = 0.667
Kc =
[B] 24 M
From Figure P16.3, showing 26 blue spheres (product B) and 13 red spheres (reactant A), we are to write the
chemical equation of the equilibrium reaction and calculate the value of Kc.
112
Chemical Equilibrium | 113

Analyze
(a) In this reaction, A is transformed into B. We represent a system at equilibrium by using double-headed
reaction arrows between the reactants and products. We will assume that one molecule of A produces one
molecule of B in the reaction.
(b) The value of Kc is the ratio of the concentration of the products (number of B spheres) and the concentration
of the reactants (number of A spheres) raised to their respective stoichiometric coefficients from the balanced
chemical equation.
Solve
(a) A B
26
(b) K c =
= 2.0
13
Think about It
If the chemical equation were written as 2A B, then Kc would be
[B]
26
Kc =
=
= 0.15
[A]2 (13) 2
We are to determine whether the reaction mixture depicted in Figure P14.4 is at equilibrium by comparing the
reaction quotient to the given equilibrium constant. If the reaction mixture is not at equilibrium, we are to
predict the direction in which it shifts in order to achieve equilibrium.
Analyze
Figure P14.4 shows 18 red spheres (A), 24 blue spheres (B), and 10 blue-red pairs (AB). If the reaction quotient
[ AB]
Q=
[ A ][ B]
is equal to 3.0, then the reaction is at equilibrium. If Q is less than 3.0, the reaction shifts to the right. If Q is
greater than 3.0, the reaction shifts to the left.
Solve
Q=
10
= 0.023
18 24
This reaction is not at equilibrium, as Q K, and because Q < K, the reaction shifts to the right to attain
equilibrium.
Think about It
When equilibrium is attained, the number of A, B, and AB molecules remains constant even though, at the
molecular level, the conversions of A and B to AB and AB to A and B continue (but at equal rates).
By comparing the relative distributions of reactants A and B with product AB at two different temperatures, as
shown in Figure P14.5, we can determine whether the reaction is endothermic or exothermic.
Analyze
From the equation
G = RT ln K = H T S
we see that as temperature rises for an exothermic reaction, G becomes less negative and therefore K
decreases. If, however, the temperature is raised on an endothermic reaction, G becomes more negative and K
increases. Therefore, if products increase upon raising the temperature, the reaction is endothermic; if products
decrease, the reaction is exothermic.
114 | Chapter 14
Solve
At 300 K the equilibrium mixture is 6 A, 10 B, and 5 AB. This gives an equilibrium constant of
K300 K =
5
= 0.083
6 10
At 400 K, the equilibrium mixture is 3 A, 7 B, and 8 AB. This gives an equilibrium constant of
8
K 400 K =
= 0.38
3 7
As temperature increases for this reaction, K increases, indicating that more products form at higher
temperatures, so this reaction is endothermic.
Think about It
We assume in this problem that the difference in entropy for the two temperatures at which this reaction is run
is minimal, so only H contributes to the difference in G at the two temperatures.
From the Arrhenius plot of ln K c versus 1/T (Figure P14.6), we are to determine whether the reaction is
endothermic or exothermic.
Analyze
The Arrhenius equation is
ln K c =
H " 1 % S
$ '+
R #T & R
where y = ln Kc, x = 1/T, m = HU R, and b = SU R.

Solve
The slope (m) of the graph is positive, so HU R is negative. The reaction is exothermic.
Think about It
If the y-axis in Figure P14.6 showed values of ln Kc, we would be able to calculate the slope of the line and
therefore estimate the value of H for the reaction.
We are asked to determine from Figure P14.7 whether the reaction depicted reaches equilibrium.
Analyze
Equilibrium is a state where the composition of the reaction is not changing.
Solve
A reaction is at equilibrium when the rate of the forward reaction equals the rate of the reverse reaction. As a
result, the concentration of neither the products nor the reactants will change at equilibrium. In Figure P14.7, we
see that both the concentrations of the reactants and the products level off after 50 microseconds. This is the
point of equilibrium. At 20 microseconds the concentrations of the reactants and the products are still changing,
so at this point, the reaction is not at equilibrium.
Think about It
Chemical equilibrium is a dynamic process. At the molecular level the forward and reverse reactions are still
occurring. Because they occur at the same rate, however, we observe no macroscopic changes in the
concentrations of the reactants and products in the mixture.

For the reaction rates shown in Figure P14.7, we are asked how the forward and reverse rates at 30 s compare
for the forward and the reverse reactions.
Analyze
We see on the plot that the concentration of the product B is higher than the concentration of the reactant A at
30 s, so the reaction is well on its way to formation of product B from reactant A. The reaction, however, has
not yet come to equilibrium, where the rate of the forward reaction is equal to the rate of the reverse reaction.
Solve
Because the reaction is still making product B and losing reactant A, the rate of the forward reaction must still
be larger than the rate of the reverse reaction.
Think about It
When the reaction reaches equilibrium, the concentrations of the reactants and products are unchanging. For
this reaction, equilibrium occurs after 50 s.
We are to describe an everyday experience of dynamic equilibrium.
Analyze
In a dynamic equilibrium, the forward and reverse processes occur at the same rate so that we observe no
changes in the concentrations of reactants and products.
Solve
Any process in which something is removed and replaced immediately would be an example. A common
example is that of an unopened soda bottle in which the dissolved carbon dioxide is continuously entering the
gas phase at the same rate at which undissolved carbon dioxide enters the liquid phase in a dynamic equilibrium
process.
Think about It
Once the soda bottle is opened, however, the rate of CO2 escaping the liquid phase is faster than the rate of CO2
entering the liquid phase, and the soda eventually goes flat.
We consider whether the sum of the concentrations of reactants equals the sum of the concentrations of the
products at equilibrium.
Analyze
Equilibrium is defined by an unchanging composition of a reaction mixture brought about by the rate of the
forward reaction equaling the rate of the reverse reaction.
Solve
No. The reaction may heavily favor either products or reactants. The definition of equilibrium does not specify
the distribution of the reactants and products.
Think about It
At any given temperature for a reaction at equilibrium, the value of Kc does not change. The ratio
[products]x/[reactants]y (where x and y are stoichiometric coefficients from the balanced chemical equation)
does not change.
For a reaction where kf > kr, we are to determine whether K is greater than, less than, or equal to 1.
116 | Chapter 14
Analyze
The equilibrium constant defined in terms of the rate constants for a reaction is
K=
kf
kr
Solve
When kf > kr, K is greater than 1.
Think about It
When K > 1, more products are present at equilibrium than reactants.
Using the relationship between K and kf and kr, we are to explain why K may be large even though kf and kr are
small.
Analyze
The equilibrium constant defined in terms of the rate constants for a reaction is
K=
kf
kr
Solve
The ratio kf to kr determines the magnitude of K. For example, if kf = 1 102 and kr = 1 108, then
1 102
K=
= 1 106
1 108
Think about It
Likewise, if kf and kr are both large, the value of K might be small, as in the following example:
1 106
K=
= 1 103
1 109
For the decomposition of N2O to N2 and O2, we are to identify the species present after 1 day from the given
molar masses. The initial reaction mixture contains 15N2O, N2, and O2.
Analyze
The only isotope in the reaction for oxygen is 16O, but for nitrogen both 15N and 14N are present at the beginning
of the reaction. After 1 day, the 14N will be incorporated into N2O and 15N will be incorporated into N2.
Solve
Molar Mass
28
29
30
32
44
45
46
Compound
14
N2
N14N
15
N2
O2
14
N 2O
15 14
N NO
15
N 2O
15
How Present
Originally present
From decomposition of 15N14NO
From decomposition of 15N2O
Originally present
From combination of 14N2 and O2
From combination of 15N14N and O2
Originally present
Think about It
The redistribution of 15N from N2O to N2 and of 14N from N2 to N2O demonstrates that both forward and reverse
reactions occur in a dynamic equilibrium process.

From the equation
and starting the reaction with
explain their appearance.
13
CO,
12
2 CO(g) + O 2 (g) 2 CO 2 (g)

CO2, and O2 we are to identify the compounds present after 1 day and
Analyze
The masses of the atoms combine to give the molar masses of the compounds seen in the reaction mixture:
12
C = 12 g/mol
13
C = 13 g/mol
16
O = 16 g/mol (the most abundant O isotope)
Solve
The compounds matched with their molar masses are as follows:
28 g/mol = 12CO
29 g/mol = 13CO
32 g/mol = 16O2
44 g/mol = 12CO2
45 g/mol = 13CO2
The reaction mixture initially contains
through the reverse reaction
13
CO,
12
CO2, and
16
O2. The
12
CO is produced in the reaction mixture
2 12CO2 O2 + 2 12CO
and the 13CO2 is produced through the forward reaction
2 13CO + O2 2 13CO2
Think about It
A reaction, even at equilibrium, is dynamic and isotopically labeled elements will, to some extent, be scrambled
throughout the reactants and products.
From the rate laws and rate constants for the forward and reverse reactions for
AB
we are to calculate the value of the equilibrium constant.
Analyze
At equilibrium, the rate of the forward reaction equals the rate of the reverse reaction. The equilibrium constant
is the ratio of the concentrations of the products raised to their coefficients to the concentrations of the reactants
raised to their respective coefficients.
Solve
For the reaction A B we are given that the forward reaction is first order in A:
Ratef = k1[A], where k1 = 1.50 102 s1
and that the reverse reaction is first order in B:
Rater = k1[B], where k1 = 4.50 102 s1
At equilibrium, ratef = rater, so
k1[A] = k1[B]
Rearranging this to give the equilibrium constant expression allows us to solve for Kc:
[ B] = k1 = 1.50 102 s 1 = 0.333
Kc =
[ A] k1 4.50 102 s 1
118 | Chapter 14
Think about It
For the reverse equilibrium
BA
the equilibrium constant is 1/0.333, or 3.00.

Given the equilibrium constant (Kc = 8.7 106) and the rate constant for the reverse reaction (kr = 0.54
M1 s1) for
2 NO(g) + O2(g) 2 NO2(g)
we are to calculate the rate constant for the forward reaction.
Analyze
At equilibrium, the rate of the forward reaction is equal to the rate of the reverse reaction, or
kf[NO]2[O2] = kr[NO2]2
Rearranging gives the equilibrium constant expression:
[ NO ] = k
[ NO] [ O ] k
2
Kc =
Therefore, kf = Kc kr.
Solve
kf = 8.7 106 0.54 M1 s1 = 4.7 106 M1 s1
Think about It
Because the equilibrium constant is large, it is consistent that kf > kr.
From the equation relating Kc and Kp, we can determine under what conditions Kc = Kp.
Analyze
The equation relating Kc and Kp is
Kp = Kc (RT )n
Solve
Kp equals Kc when n = 0. This is true when the number of moles of gaseous products equals the number of
moles of gaseous reactants in the balanced chemical equation.
Think about It
The value of Kp may also be less than Kc (for n < 0) or greater than Kc (for n > 0).
We are asked to determine at which temperature the values of Kc and Kp are equal for the reaction of nitrogen
with oxygen to give gaseous NO.
Analyze
The equation relating Kc and Kp is
Kp = Kc (RT )n
Solve
n
For this reaction n = 0, so the value of (RT) = 1. This means that
K p = K c (RT ) n = K c (RT )0 = K c 1
K p = Kc
Therefore, Kc and Kp are equal at all temperatures.

Think about It
As we saw in Problem 14.17, Kc equals Kp only when n = 0.
Given three reactions involving nitrogen oxides, we are to write Kc and Kp expressions for each reaction.
Analyze
The Kc expression uses concentration (molarity) units for the reactants and the products, whereas the Kp
expression uses partial pressure. The K expression for a balanced chemical reaction takes the general form
wA + xB yC + zD
[C] y [D]z
Kc =
[A]w [B]x
Solve
(a) K c =
(b) K c =
[N 2O 4 ]
[N 2 ][O 2 ]
and K p =
(P )
( P )( P )
and
y
z
PC ) ( PD )
(
Kp =
( PA )w ( PB ) x
N 2O 4
N2
O2
)(
PNO2 PN2 O
[NO 2 ][N 2 O]
and K p =
3
[NO]
( PNO )3
( )( )
( )
2
PN2 PO2
[N ]2 [O 2 ]
(c) K c = 2
and K p =
2
2
[N 2 O]
PN2 O
Think about It
Kc uses concentration units (usually in moles per liter), whereas Kp uses partial pressure units (usually in
atmospheres).
For three balanced reactions, we are to write the equilibrium constant expressions.
Analyze
The Kc expression uses concentration (molarity) units for the reactants and the products, whereas the Kp
expression uses partial pressure. The K expression for a balanced chemical reaction takes the general form
wA + xB yC + zD
Kc =
Solve
(a) K c =
(b) K c =
[ ClO] [ O2 ]
[ Cl] [ O3 ]
and K p =
[ Cl ][ O ]
[ ClO]
and K p =
2
2
[O ]
=
[O ]
(c) K c
( PClO ) ( PO )
( PCl ) ( PO )
2
[C] y [D]z
[A]w [B]x
and K p
( P )( P )
Cl2
(P )
=
(P )
( PClO )
O2
O3
O2
and
Kp =
( PC ) y ( PD ) z
( PA )w ( PB ) x
120 | Chapter 14
Think about It
Kc uses concentration units (usually moles per liter), whereas Kp uses partial pressure units (usually
atmospheres).
Given a plot of the concentration versus time for the decomposition of N2O to N2 and O2 (Figure P14.21), we
are to estimate the value of Kc.
Analyze
The amounts of N2O, N2, and O2 are given in concentration units and the form of the Kc expression is
[ N ][ O ]
=
[ N O]
1/ 2
Kc
The concentrations of each species at equilibrium can be read from the graph as those concentrations that are no
longer changing with time. This occurs after 5 s and gives [N2] = 0.00030 M, [O2] = 0.00014 M, and
[N2O] = 7.10 106 M.
Solve
[ N ][ O ]
[ N O]
1/ 2
Kc =
(0.00030 M )(0.00014 M )1/ 2

= 0.50
(7.10 106 M )
Think about It
Because this equilibrium constant is neither high nor low, at equilibrium the distribution of the reactants and
products is expected to be roughly equal. A general rule is that if K < 0.01, the reactants are favored in the
equilibrium, and if K > 100, the products are favored in the equilibrium.
From the concentrations of O2, NO, and NO2 at equilibrium shown in Figure P14.22, we are to estimate Kc for
2 NO(g) + O 2 (g) 2 NO 2 (g).
Analyze
Equilibrium is achieved when the concentrations of the reactants and products in the reaction mixture no longer
change. For this reaction this is at [O2] = 0.007 M, [NO2] = 0.006 M, and [NO] = 0.004 M.
The equilibrium constant expression for this reaction is
[ NO ]
=
[ NO] [ O ]
2
Kc
Solve
(0.006 M )
=
=
(0.004 M ) (0.007 M )
2
Kc
300
Think about It
Because Kc is greater than 1, the product is favored in this reaction.
Given the balanced chemical equation and the equilibrium partial pressures of all species in the decomposition
reaction of H2S to give H2 and S, we are to calculate the value of Kp for the reaction.
Analyze
The form of the Kp expression for this reaction is
Kp =
( P )( P )
(P )
H2
H 2S
Solve
Kp =
( P )( P ) = (0.045 atm)(0.030 atm) = 0.068

(0.020 atm)
(P )
H2
H 2S
Think about It
Remember that equilibrium constants, K, do not have any units.
Given the partial pressures for H2O, H2, and O2 for the equilibrium reaction
2 H 2O(g) 2 H 2 (g) + O 2 (g)
we are to calculate the value of Kp.
Analyze
The Kp expression for this reaction is
(P ) (P )
=
(P )
2
Kp
H2
O2
H2 O
122 | Chapter 14
Solve
( P ) ( P ) = (0.0045 atm) (0.0030 atm) = 3.8 10

=
(0.040 atm)
(P )
2
Kp
H2
O2
H2 O
Think about It
Even though the partial pressure for each gas is in atmospheres, the equilibrium constant itself has no units
because each pressure in the expression is actually a ratio (which gives the activity) in which the units cancel.
Given the equilibrium molar concentrations of N2, O2, and NO, we are to calculate Kc for
N 2 (g) + O 2 (g) 2 NO(g)
Analyze
Kc =
Solve
[ NO]2
[ N 2 ][ O2 ]
(3.1 10 M )
=
(3.3 10 M )(5.8 10
2
Kc
= 0.50
Think about It
Be careful to account for the coefficients in the mass action equation when calculating Kc. In this problem, we
must be sure to square the equilibrium concentration of NO.
Given the equilibrium molar concentrations of N2O4 and NO2, we are to calculate Kc for the reaction
2 NO 2 (g) N 2O 4 (g)
Analyze
Kc =
[N O ]
[ NO ]
2
Solve
Kc =
( 2.9 10
( 4.2 10
)
M)
M
= 160
Think about It
Be careful to account for the coefficients in the mass action equation when calculating Kc. In this problem, we
must be sure to square the equilibrium concentration of NO2.
Given the initial moles of H2O and CO and the moles of CO2 present at equilibrium, we are to determine Kc for
H 2O(g) + CO(g) H 2 (g) + CO 2 (g)

Analyze
Because the ratios of reactants and products are 1:1:1:1, we do not need the volume of the vessel because that
volume would cancel in the final Kc expression. We can therefore simply use the mole amounts. Furthermore,
we can calculate the amounts of reactants and products present at equilibrium from the initial amounts of the
reactants, the given moles of the product CO2 formed (8.3 103 mol), and the stoichiometry of the reaction.
Solve
Reaction
Initial (mol)
Change (mol)
Equilibrium (mol)
H2O(g) +
H 2O
0.0150
x
0.0150 x
CO(g) H2(g) + CO2(g)

CO
H2
CO2
0.0150
0
0
x
+x
+x
0.0150 x
x
x
At equilibrium, we know that [CO2] = x = 8.3 103 mol. This gives

H2O = CO = 0.0150 x = 0.0067 mol
H2 = CO2 = x = 8.3 103 mol
[ H ][ CO ] = (8.3 10 mol)(8.3 10 mol) = 1.5

[ H O][ CO] ( 0.0067 mol)(0.0067 mol)
3
Kc =
Think about It
We must have a balanced chemical reaction so that we can stoichiometrically relate the quantity of products to
the reactants and correctly calculate the value of the equilibrium constant.
Given the initial moles of NO and H2 contained in a 100 mL vessel along with the concentration of NO at
equilibrium, we are to calculate the value of Kc for
2 H 2 (g) + 2 NO(g) 2 H 2O(g) + N 2 (g)
Analyze
The initial concentrations of the reactants are
2.60 102 mol NO
= 0.260 M NO
0.100 L
1.30 102 mol H 2
= 0.130 M H 2
0.100 L
Because we are given the [NO] at equilibrium, we can calculate the amount of NO reacted. From that we can
calculate by stoichiometry the equilibrium concentrations of H2, H2O, and N2 and calculate the value of Kc for
the reaction.
Solve
Reaction
Initial
Change
Equilibrium
H2(g) + 2 NO(g) 2H2O(g) + N2(g)

[H2]
[NO]
[H2O]
[N2]
0.130
0.260
0
0
2x
2x
+2x
+x
0.130 2x
0.260 2x
2x
x
At equilibrium, we know that [NO] = 0.161 M, so

[NO] = 0.161 M = 0.260 2x
x = 0.0495
124 | Chapter 14
Therefore, the equilibrium amounts of all species are
[H2] = 0.130 2x = 0.031 M
[NO] = 0.161 M
[H2O] = 2x = 0.0990 M
[N2] = x = 0.0495 M
[ H O] [ N ] = ( 0.0990 M ) ( 0.0495 M ) = 19
[ H ] [ NO] ( 0.031 M ) ( 0.161 M )
2
Kc =
Think about It
We must have a balanced chemical reaction so that we can stoichiometrically relate the quantity of products to
the reactants and to correctly calculate the value of the equilibrium constant.
We are given Kp = 32 for the following reaction at 298 K:
A(g) + B(g) AB(g)
We are to calculate the value of Kc, which we can do using the relationship
K p = K c ( RT )
Analyze
The change in the number of moles of gas for this reaction (n) is
1 mol AB (1 mol A + 1 mol B) = 1
Solve
L atm
298 K
32 = K c 0.08206
mol K
K c = 780
Think about It
When n is positive, Kp is greater than Kc, but when n is negative, Kp is less than Kc. When n is zero, Kp
equals Kc.
We are given Kc = 6.0 104 for the following reaction at 500 K:
CD(g) C(g) + D(g)
We are to calculate the value of Kp, which we can do using the relationship
K p = K c ( RT )
Analyze
(1 mol C + 1 mol D) (1 mol CD) = 1
Solve
L atm
500 K
K p = 6.0 104 0.08206
mol K
K p = 2.5 106
Think about It
When n is positive, Kp is greater than Kc, but when n is negative, Kp is less than Kc. When n is zero, Kp
equals Kc.

We are given Kp = 1.45 105 8ADF:78A>>AI;@9D735F;A@3F
U
N 2 (g) + 3 H 2 (g) 2 NH 3 (g)
We are to calculate the value of Kc.
Analyze
Rearranging the equation relating Kp and Kc to solve for Kc gives
Kp
Kc =
(RT ) n
The change in the number of moles is
(2 mol NH3) (1 mol N2 + 3 mol H2) = 2
The temperature in kelvins is 500 + 273 = 773 K.
Solve
Kc =
1.45 105
L atm
773 K
0.08206
mol K
= 0.0583
Think about It
Here, Kp < Kc because n is negative. When n = 0, Kp = Kc.
Given Kc = 5 105 for the following reaction at 298 K,
2 CO(g) + O 2 (g) 2 CO 2 (g)
we are to calculate the value of Kp, which we can do using the relationship
K p = K c ( RT )
Analyze
(2 mol CO2) (2 mol CO + 1 mol O2) = 1
Solve
L atm
298 K
K p = 5 10 0.08206
mol K
K p = 2 104
Think about It
The lower value of Kp is consistent with n being negative.
We are asked to determine in which of the three reactions the values of Kc and Kp are equal.
Analyze
Kp and Kc are equal when n = 0 in the relationship
K p = K c ( RT )
where n is the change in the number of moles of gas in the reaction:

n = (moles of gaseous products) (moles of gaseous reactants)
126 | Chapter 14
Solve
(a) n = 2 3 = 1
(b) n = 1 1 = 0
(c) n = 2 2 = 0
Reactions (b) and (c) have Kp = Kc. Only reaction (a) has Kp Kc.
Think about It
Remember that n is the difference in the moles of gaseous products and gaseous reactants. In reaction (b),
Fe(s) and FeO(s) are not considered.
For three reactions we are to determine for which the values of Kc and Kp are different.
Analyze
Kp and Kc are different when n 0 in the relationship
K p = K c ( RT )
where n is the change in the number of moles of gas in the reaction:

n = (moles of gaseous products) (moles of gaseous reactants)
Solve
(a) n = 2 1 = 1
(b) n = 2 3 = 1
(c) n = 3 2 = 1
For all three reactions (a c), Kp Kc.
Think about It
For reactions (a) and (c), Kp > Kc, whereas for reaction (b), Kp < Kc.
Given Kc
8ADF:78A>>AI;@9D735F;A@3F U
#
Cl2 (g) + CO(g) COCl2 (g)
we are to calculate the value of Kp 3F U-753@GE7F:7D7>3F;A@E:;B
K p = K c ( RT )
Analyze
For this reaction
n = (1 mol COCl2) (1 mol Cl2 + 1 mol CO) = 1
Solve
L atm
K p = 5.0 0.08206
598 K
mol K
= 0.10
Think about It
Because n is negative, the value of Kp is less than that of Kc.
Given Kp = 3.45 for the following reaction at 298 K:
SO 2 (g) + NO 2 (g) NO(g) + SO3 (g)

we are to calculate the value of Kc for the reverse reaction. We can use the relationships
K p = K c ( RT )
K reverse =
Analyze
For this reaction
1
K forward
n = (1 mol NO + 1 mol SO3) (1 mol SO2 + 1 mol NO2) = 0
Solve
Because n = 0,
Kp = Kc(RT)0 = Kc 1
and the value of Kc = Kp, so Kc = 3.45 for the forward reaction. For the reverse reaction,
1
1
K reverse =
=
= 0.290
K forward 3.45
Think about It
Only when n 0 would Kc and Kp be different in value.
We consider how K changes when the coefficients of a balanced reaction are scaled up or down.
Analyze
To answer the question, lets consider the following reactions:
(1) 2 A + B C
(2) 4 A + 2 B 2 C
The equilibrium constant expressions for the reactions are
[C]
[C]2
K1 =
and
K
=
2
[A]2 [B]
[A]4 [B]2
These are related by
K2 = (K1)2
Solve
When we scale the coefficients of a reaction up or down, the new value of the equilibrium constant is the first K
raised to the power of the scaling constant.
Think about It
Scaling reaction 1 by 1/3 gives
2
1
1
A+ B C
3
3
3
[C]1 3
K=
, or (K1 )1/3
[A]2 3 [B]1 3
We are to explain why the temperature and a written form of the equilibrium equation are needed when
reporting the value of K.
Analyze
As we saw in Problem 14.37, scaling a chemical equation up or down changed the value of the equilibrium
constant. Temperature and the value of K are related through Gibbs free energy:
G
= ln K
RT
128 | Chapter 14
Solve
The temperature and form of the equilibrium reaction must be given with a value of K because both the
stoichiometric scaling of the reaction and the temperature change the value of K.
Think about It
From the Gibbs free energy equation, we see that the value of K increases with an increase in temperature for a
spontaneous reaction (negative G) and decreases with an increase in temperature for a nonspontaneous
reaction (positive G).
Given the equilibrium constant for the reaction of 1 mol I2(g) with 1 mol Br2(g) to give 2 mol IBr(g), we are to
calculate the value of the equilibrium constant for the reaction of mol of I2 and Br2 to give 1 mol of IBr.
Analyze
The Kc expressions for these reactions are
2
IBr
Kc =
1
I 2 Br2
Kc =
and
IBr
12
I 2 Br2
12
Kc2 for the second reaction is, therefore, related to that of the first by
( )
Kc = Kc
2
Solve
( )
Kc = Kc
2
12
12
= (120)1 2 = 11.0
Think about It
When we multiply a chemical reaction by a number, the new value of the equilibrium constant is the first
equilibrium constant raised to that number.
Given the equilibrium constant for the reaction of 1 mol N2(g) with 3 mol H2(g) to give 2 mol NH3(g), we are to
calculate the value of the equilibrium constant for the reaction of 1/2 mol of N2 with 3/2 mol of H2 to give
1 mol of NH3.
Analyze
2
Kc =
1
NH 3
3
N 2 H 2
Kc =
and
( )
Kc = Kc
2
Solve
( )
Kc = Kc
2
12
NH 3
12
32
N 2 H 2
12
= (4.3 103 )1 2 = 6.6 102
Think about It
equilibrium constant raised to that number.

For the reaction of NO with NO3, we are to explain how Kc for the reverse reaction relates to Kc of the forward
reaction by writing their equilibrium constant expressions.
Analyze
The form of the equilibrium constant expression for the forward reaction is the ratio of the product of the
concentration of the products raised to their stoichiometric coefficients to the product of the concentration of the
products raised to their stoichiometric coefficients:
[products] y
Kc =
[reactants]x
Solve
The form of the equilibrium constant expression for the forward reaction is
[NO 2 ]2
K c,forward =
[NO][NO3 ]
For the reverse reaction, the equilibrium constant expression is
[NO][NO3 ]
Kc,reverse =
[NO2 ]2
Examining these two expressions, we see that
K c,reverse =
1
K c,forward
Think about It
Another way to think about this relationship is
Kc,forward Kc,reverse = 1
Given Kp = 4.5 105 for the reaction
3F
UI73D7FA53>5G>3F7Kp for
N 2 (g) + 3 H 2 (g) 2 NH 3 (g)

2 NH 3 (g) N 2 (g) + 3 H 2 (g)
at the same temperature.

Analyze
The Kp expressions for these reactions are
( NH )
( N )( H )
2
Kp =
1
Kp2 is, therefore, related to Kp1 by
Kp =
and
( N )( H )
( NH )
2
2
Kp =
2
1
Kp
Solve
Kp =
2
1
= 2.2 104
4.5 10 5
Think about It
When we reverse a reaction, the new equilibrium constant is the inverse of K for the forward reaction.
130 | Chapter 14
For two reactions of different stoichiometry for the reaction of SO2 with O2 to produce SO3, we are to write the
equilibrium constant expressions and explain how they are related.
Analyze
Equilibrium constant expressions take the form
wA + xB yC + zD
Kc =
Solve
The equilibrium expressions for the reactions are
[SO3 ]
Kc =
[SO2 ][O2 ]1 2
These expressions are related by
[C]y [D]z
[A]w [B]x
K c =
and
K c = ( K c )
[SO3 ]2
[SO2 ]2 [O 2 ]
Think about It
If the second reaction were
1
2
then
SO 2 (g) + 14 O 2 (g) 12 SO3 (g)
K c!! =
Given Kc = 0.11 for the reaction
[SO3 ]1 2
[SO 2 ]1 2 [O 2 ]1 4
2 NO(g) + 2 H 2 (g) N 2 (g) + 2 H 2O(g)
at a given temperature, we are to calculate Kc for

NO(g) + H 2 (g)
N 2 (g) + H 2O(g)
1
2
at the same temperature.

Analyze
2
N H O
K c = 2 2 2 2
and
Kc =
1
2
NO H 2
( )
Kc = Kc
2
Solve
12
K c = ( 0.11)
12
12
N 2 H 2O
NO H 2
= 0.33
Think about It
equilibrium constant raised to the number.
Given the value of Kc for the reaction
3
2 SO 2 (g) + O 2 (g) 2 SO3 (g)
as 2.4 10 , we are to calculate Kc for three other forms of this reaction at the same temperature.

Analyze
When a reaction is multiplied by a factor x, the new equilibrium constant is (Kc)x. When a reaction is reversed,
the new equilibrium constant is 1/Kc.
Solve
(a) This reaction is the original equation multiplied by 12 . The new Kc is
( 2.4 10 )
3 1 2
= 4.9 102
(b) This reaction equation is the reverse of the original equation. The new Kc is
1 2.4 10 3 = 420
(c) This reaction equation is the reverse of the original equation multiplied by 12 . The new Kc is
1 ( 2.4 103 )
12
= 20
Think about It
Because we can relate the equilibrium constants for different forms of a reaction, we need to tabulate only one
of the equilibrium constants. All others can be calculated from that value.
Given the value of Kc for the reaction
12
2 NO(g) + O 2 (g) 2 NO 2 (g)
as 5 10 , we are to calculate Kc for three other forms of this reaction at the same temperature.
Analyze
When a reaction is multiplied by a factor x, the new equilibrium constant is (Kc)x. When a reaction is reversed,
the new equilibrium constant is 1/Kc.
Solve
(a) This reaction is the original equation multiplied by 1/2. The new Kc is
(5 10 )
12 1 2
= 2 106
(b) This reaction equation is the reverse of the original equation. The new Kc is
1 5 1012 = 2 10 13
(c) This reaction equation is the reverse of the original equation multiplied by 1/2. The new Kc is
1 (5 1012 )
12
= 4 10 7
Think about It
Because we can relate the equilibrium constants for different forms of a reaction, we need to tabulate only one
of the equilibrium constants. All others can be calculated from that value.
We are asked to calculate K for a reaction given Kc values for two other reactions. We can add the two
equations and reverse the resulting equation and then calculate the equilibrium constant for this new chemical
equation.
132 | Chapter 14
Analyze
The Kc expressions for the reactions and the overall reaction are
A+2 BC
K1 =
C
= 3.3
2
A B
2
C2D
D
K 2 = = 0.041
C
2
A+2 B2 D
D
K3 = 2
A B
where K3 = K1 K2. The equilibrium constant for the reaction

2 DA+2 B
is the inverse of K3.
Solve
K=
1
= 7.4
0.041 3.3
Think about It
When we add reactions, the new equilibrium constant is the product of the equilibrium constants of the
reactions that were combined.
We are asked to calculate K for a reaction given Kc values for two other reactions. We can add the two
equations and reverse the resulting equation and then calculate the equilibrium constant for this new chemical
equation.
Analyze
The Kc expressions for the reactions and the overall reaction are
2GH
H 2 E+2 F
2 G 2 E+2 F
H
K1 = 2 = 3.1 10 4
G
2
E F
K 2 = = 2.8 10 2
H
E F
K3 = 2
G
where K3 = K1 K2. The equilibrium constant for the reaction

E+FG
will be 1 ( K 3 ) .
12
Solve
K = 1 (3.1104 2.8 102 )
12
= 340
Think about It
Remember that when we reverse an equation, the equilibrium constant is the inverse of the forward reaction
equilibrium constant.

14.49. Collect and Organize / Analyze
We are to define the term reaction quotient.
Solve
The reaction quotient is the ratio of the concentrations of the products raised to their stoichiometric coefficients
to the concentrations of reactants raised to their stoichiometric coefficients. The reaction quotient has the same
form as the equilibrium constant expression, but the reaction concentrations (or partial pressures) are not
necessarily at their equilibrium values.
Think about It
If the reaction quotient, Q, is greater than K, the reaction mixture must reduce its concentration of products to
attain equilibrium. When Q is less than K, the reaction mixture must increase its concentration of products to
attain equilibrium.
We are asked how, in most cases, the equilibrium constant K and the reaction quotient Q differ for a given
equilibrium system.
Analyze
Both K and Q take the form of the ratio of the concentrations of products raised to their stoichiometric
coefficients to the concentrations of reactants raised to their stoichiometric coefficients.
Solve
The reaction quotient Q is for a reaction mixture not necessarily at equilibrium. Only if the system is at
equilibrium is Q = K.
Think about It
If the reaction quotient, Q, is greater than K, the reaction mixture must reduce its concentration of products to
attain equilibrium. When Q is less than K, the reaction mixture must increase its concentration of products to
attain equilibrium.
We are asked what it means when Q = K.
Analyze
Solve
When Q = K the system is at equilibrium.
Think about It
Whenever Q K, the reaction is not at equilibrium and it adjusts its relative concentrations of reactants and
products so that Q = K.
We are to explain how comparing numerical values of K and Q allows us to determine whether a reaction is at
equilibrium and which direction a reaction will shift to attain equilibrium.
Analyze
Solve
When Q < K, the reaction shifts to the right, forming more products. When Q > K, the reaction shifts to the left,
forming more reactants. When Q = K, the reaction is at equilibrium.
134 | Chapter 14
Think about It
When Q K, the reaction shifts until Q = K. At that point no more changes in the relative concentrations of the
reactants and products occur as long as reaction conditions remain constant.
We are asked whether the reaction
A(aq) B(aq)
where [A(aq)] = 0.10 M, [B(aq)] = 2.0 M, and K = 22 is at equilibrium. If the reaction is not at equilibrium, we
are to state in which direction the reaction will proceed to reach equilibrium.
Analyze
The reaction quotient (Q) is
[ B] = Q
[ A]
where [B] and [A] are the concentrations of A and B in the reaction mixture. If Q > K, the reaction will proceed
to the left to reach equilibrium. If Q < K, the reaction will proceed to the right. If Q = K, the reaction is at
equilibrium.
Solve
2.0 M
= 20
0.10 M
No, the reaction is not at equilibrium. Q < K, so this reaction proceeds to the right to reach equilibrium.
Q=
Think about It
In this reaction, more B forms as the reaction proceeds to equilibrium.
We can compare Q versus K to determine in which direction the reaction will shift to attain equilibrium. We are
given Kc = 3 103.
Analyze
The form of the reaction quotient for this reaction is
Q=
[ D][ E ]
[ C ]2
If Q > K, the reaction will proceed to the left to reach equilibrium. If Q < K, the reaction will proceed to the
right. If Q = K, the reaction is at equilibrium.
Solve
(5 104 M )(5 104 M )

=1
(5 104 M )2
Because, Q > K (3 103), this reaction proceeds to the left to reach equilibrium, forming more of reactant C.
Q=
Think about It
To calculate the amount of each reactant and product at equilibrium, we solve for x in the following equation:
(5 10 4 M x) 2
K c = 3 10 3 =
(5 10 4 M + x) 2
Given two sets of reactant and product concentrations for the reaction of A and B to form C (where Kp = 1.00),
we are to determine whether either reaction mixture is at equilibrium. The temperature is 300 K.
Analyze
These systems are at equilibrium when Q = Kp = 1.00. For the reaction where A, B, and C are expressed in
terms of molarity, we must convert Kp to Kc by using
K p = K c ( RT )
where for this reaction n = 1.

Solve
1.0 atm
= 1.0
(1.0 atm)(1.0 atm)
This reaction mixture is at equilibrium.
(b) Rearranging the equation to solve for Kc gives
Kp
1.00
=
= 24.6
Kc =
n
1
( RT )
L atm
0.08206 mol K 300 K
1.0 M
Qc =
= 1.0
(1.0 M )(1.0 M )
Because Qc < Kc, this reaction mixture is not at equilibrium and shifts to the right to attain equilibrium.
(a) Qp =
Think about It
Both Kp and Kc are close to 1, and so these reaction mixtures have roughly equal proportions of reactants and
products when they reach equilibrium.
136 | Chapter 14
For the reaction
A(g) + B(g) C(g)

for which Kp = 1.00 at 300 K, we are to calculate Q for different partial pressures or concentrations of A, B, and
C to determine in which direction each reaction mixture will proceed to reach equilibrium.
Analyze
If Q > K, the reaction will proceed to the left to reach equilibrium; if Q < K, the reaction will proceed to the
right; if Q = K, the reaction is at equilibrium. Because we are given Kp for the reaction, we have to calculate Kc
for the conditions of part b from the relationship
K p = K c ( RT )
Solve
( PC ) =
1.0 atm
= 2.0
P
P
1.0
atm
)( 0.50 atm)
( A )( B ) (
For this reaction mixture, Q > K, so the reaction proceeds to the left.
(b)
Kp
Kc =
( RT )n
(a) Qp =
where R = 0.8206 (L atm)/(mol K), T = 300 K, and n = 1 2 = 1.
1.00
Kc =
L atm
0.08206 mol K ( 300 K )
1.0 M
Qc =
= 1.0
1.0 M 1.0 M
For this reaction mixture, Q < K, so the reaction proceeds to the right.
= 24.6
Think about It
Because Kc and Kp are both greater than 1, the products are favored for this reaction.
By comparing Q versus K for the reaction of N2 with O2 to form NO, we can determine in which direction the
reaction will proceed to attain equilibrium.
Analyze
The form of the reaction quotient for this reaction is
( PNO )2
Qp =
( P )( P )
N2
O2
Because n = 0 for this reaction, Kp = Kc = 1.5 10 .

Solve
(1.00 10 )
=
= 1.00
(1.00 10 )(1.00 10 )
3 2
Qp
Because Q > K, the system is not at equilibrium and proceeds to the left.
Think about It
For this problem Kp = Kc. This is not always the case, so be careful to notice which value is provided for K and
in what units the amounts of the reactants and products are expressed.

Given Kp = 4.3 104 at 650 K for the reaction of N2 with H2 to produce NH3, we can use the amounts of the
reactants and products present to calculate Q and then compare that value to Kc to determine whether more
ammonia will form in the reaction (reaction shifts to the right).
Analyze
Because the amounts of N2, H2, and NH3 are expressed in terms of molarity, we need to find the value of Kc
from Kp by using the equation
K p = K c ( RT )
Solve
For this reaction, n = 2 and Kc is
Kc =
Kp
( RT )n
The reaction quotient is
4.3 104
L atm
650 K
0.08206
mol K
= 1.2
(0.00020 M )2
= 0.15
(0.010 M )(0.030 M )3
For this reaction mixture, Qc < Kc, so the reaction proceeds to the right. Yes, more ammonia will form.
Qc =
Think about It
If we had not converted Kp to Kc, we would have reached the opposite conclusion that less ammonia would be
present once the reaction attained equilibrium.
Given initial concentrations of the reactants X and Y and product Z and the value of the equilibrium constant
(Kc = 1.00 at 350 K), we can use the reaction quotient to determine in which direction the reaction will shift to
reach equilibrium.
Analyze
The reaction quotient for this reaction has the form
Qc =
[Z]
[X][Y]
Solve
[Z]
0.2 M
=
=5
[X][Y] 0.2 M 0.2 M
Because Qc > Kc, the reaction proceeds to the left (a), producing more X and Y.
Qc =
Think about It
To calculate the equilibrium concentration of each reactant and product, we solve for x in the equation
0.2 x
1.00 =
( 0.2 + x )2
From the result of Problem 14.59, we are to determine how the concentration of reactant X changes from the
initial conditions to equilibrium.
Analyze
We determined in Problem 14.59 that the equilibrium shifts to the left.
138 | Chapter 14
Solve
The concentration of X increases when the equilibrium shifts to the left.
Think about It
At equilibrium, this reaction has a decreased concentration of product Z.
For the dissolution of CuS to give Cu2+ and S2 in aqueous solution, we are asked to write the Kc expression.
Analyze
Because any pure solids or liquids do not change in concentration during a reaction, their concentrations do
not appear in the mass action (equilibrium constant) expression.
Solve
Kc = [Cu2+][S2]
Think about It
Because the reactant in the dissolution reaction is a pure solid, only the concentrations of the products influence
the position of the equilibrium.
For the heterogeneous equilibrium reaction
Al2O3 (s) + 3 H 2O() 2 Al3+ (aq) + 6 OH (aq)
we are to write the Kc expression.
Analyze
Because any pure solids or liquids do not change in concentration during a reaction, their concentrations do
not appear in the mass action (equilibrium constant) expression.
Solve
K c = [Al3+ ]2 [OH ]6
Think about It
Because both reactants are either pure solids or pure liquids for this reaction, only the concentrations of the
products influence the equilibrium.
For the decomposition reaction of CaCO3 to CO2 and CaO, we are to explain why [CaCO3] and [CaO] do not
appear in the Kc expression.
Analyze
The Kc expression includes the concentrations of the reactants and products that may change during the reaction
attaining equilibrium.
Solve
The concentrations (expressed as densities) of pure solids (CaCO3 and CaO) do not change during the reaction
to attain equilibrium, and so they do not appear in the equilibrium constant expression.
Think about It
The form of Kc for this reaction is simply Kc = [CO2].

For the decomposition of NaHCO3 to Na2CO3, CO2, and H2O we are to identify the number of partial pressure
terms that are part of the Kp expression.
Analyze
The decomposition of NaHCO3 is described by the stoichiometric equation
2 NaHCO3 (s) Na 2CO3 (s) + CO 2 (g) + H 2O(g)
In the equilibrium expression, pure liquids and solids do not appear, so the only species that will appear in the
Kp expression are CO2 and H2O.
The reaction involves the breaking of bonds to form CO2 from CO32, so we expect this reaction to be
endothermic. If we increase the temperature, more products will form in this reaction by Le Chteliers
principle.
Solve
The Kp expression for the decomposition reaction of sodium bicarbonate is
( ) ( )
K p = PCO PH O
2
Therefore, the Kp expression has two partial pressure terms.

Think about It
If the water formed in this reaction were in the liquid form, the Kp expression would simply be
( )
K p = PCO

We are asked whether the value of K increases when more reactants are added to a reaction already at
equilibrium.
Analyze
The general form of the equilibrium constant expression for a reaction is
wA + xB yC + zD
Kc =
[C] y [D]z
[A]w [B]x
Solve
No, the equilibrium constant is not changed when the concentration of the reactants is increased. The relative
concentrations of the reactants and products in that case adjust until they achieve the value of K. The value of
the equilibrium constant is affected only by temperature.
Think about It
The value of the reaction quotient Q decreases below the value of K when reactants are added to a system
previously at equilibrium, and the reaction shifts to the right.
Given that adding reactants shifts a reaction to the right, we are to determine how adding a reactant to a reaction
mixture affects the rates of the forward and reverse reactions.
Analyze
At equilibrium, the rate of the forward reaction is equal to the rate of the reverse reaction. For the reaction A
B, the forward and reverse rate expressions are
Ratef = kf[A]
Rater = kr[B]
140 | Chapter 14
Solve
When a reactant is first added to a reaction mixture at equilibrium, the forward rate will increase in relation to
the reverse rate because we have increased the concentration of A in the rate equation, thereby increasing ratef.
As more product B is formed, the rater increases as ratef decreases as A is used up in the reaction. Eventually,
ratef = rater and the reaction again reaches equilibrium.
Think about It
Be sure to remember that it is the overall ratef that is equal to rater at equilibrium. It is not true that the rate
constants, kf and kr, are equal.
Given that the K for the binding of CO to hemoglobin is larger than that for the binding of O2 to hemoglobin,
we are to explain how the treatment of CO poisoning by administering pure O2 to a patient works.
Analyze
By giving a patient pure O2 to breathe, we increase the partial pressure of O2 to which the hemoglobin in the
patients blood is exposed. This oxygen can displace the CO bound to the hemoglobin through application of Le
Chteliers principle.
Solve
Combining the two equations, we can write the expression for the displacement of CO bound to hemoglobin
by O2:
Hb(CO)4 Hb + 4 CO(g)
Hb + 4 O 2 (g) Hb(O 2 )4
Hb(CO)4 + 4 O 2 (g) Hb(O 2 )4 + 4 CO(g)
As the concentration of O2 increases, the reaction shifts to the right and the CO on the hemoglobin is displaced.
Think about It
If we were given the values of the equilibrium constants for the reactions, we could calculate the new
equilibrium constant for the overall reaction.
We consider the effect of atmospheric pressure on the value of Kp for the reaction
2 NO 2 (g) N 2O 4 (g)
Analyze
Even though Los Angeles and Denver have different atmospheric pressures, the reaction will not be affected,
because the concentrations or partial pressures of the reactions are assumed to be the same.
Solve
A lower pressure in Denver than in Los Angeles at the same temperature does not change the value of Kp. Only
temperature affects the value of the equilibrium constant.
Think about It
As we will see later in the chapter, the value of Kp is dependent on the value of the free energy, as shown by the
equation GURT ln K. The free energy is affected by temperature, as shown by GU = HUTSU, and so
truly the only parameter that affects K is the temperature.
We are to interpret Henrys law through Le Chteliers principle.

Analyze
The dissolution of a gas (lets use oxygen in this example) in a liquid (lets use water) can be written as a
chemical equation:
O 2 (g) O 2 (aq)
Solve
According to Le Chteliers principle, an increase in the partial pressure (or concentration) of O2 above the
water shifts the equilibrium to the right so that more oxygen becomes dissolved in the water. This is consistent
with Henrys law.
Think about It
The solubilities of different gases in a liquid are different from each other, but all gases are more soluble in a
liquid when present at higher partial pressures.
We are to explain why adding an inert gas to a reaction mixture does not change the position of equilibrium for
the following reaction:
2 CO(g) + O 2 (g) 2 CO 2 (g)
Analyze
The equilibrium concentrations of reactants and products are expressed by the equilibrium constant equation:
(P )
=
(P ) (P )
2
Kp
CO2
2
CO
O2
Solve
Adding an inert gas to a reaction at equilibrium does not change the relative partial pressures of the reactant
gases. The partial pressure of the inert gas does not appear in the equilibrium constant expression, and so the
position of the equilibrium is unaffected.
142 | Chapter 14
Think about It
In this equilibrium mixture, adding either CO or O2 shifts the equilibrium to the right, whereas adding CO2
shifts the equilibrium to the left.
Of four reactions, we are to determine which will shift its equilibrium to form more products when the mixture
is compressed to half its original volume.
Analyze
Decreasing the volume by half doubles the partial pressures of all the gaseous reactants and products in the
reactions. This would cause a shift in the position of the equilibrium toward the side of the reaction with the
fewer number of moles of gas.
Solve
(a) This equilibrium shifts to the left, forming more reactants.
(b) This equilibrium shifts to the right, forming more products.
(c) This equilibrium shifts neither to the left nor to the right, as the number of moles of gas is the same on both
sides of the equation.
(d) This equilibrium shifts to the right, forming more products.
Reactions (b) and (d) will form more products when the volume of the mixture is decreased by half.
Think about It
The opposite shifts occur in the position of the equilibrium when the volumes of the reaction mixtures are
increased.
Of four reactions, we are to determine which will shift its equilibrium to form more products when the volume
of the reaction mixture is doubled.
Analyze
Doubling the volume of a reaction will decrease the pressure, which causes the equilibrium to shift toward the
side of the reaction that has the greater number of moles of gas.
Solve
(a) This equilibrium will shift to the left, forming more reactants.
(b) This equilibrium will not change.
(c) This equilibrium will shift to the right, forming more products.
(d) This equilibrium will shift to the right, forming more products.
Reactions (c) and (d) will form more products when the volume of the reaction mixture at equilibrium is
increased.

Think about It
The opposite shifts in equilibrium occur if the volume is decreased to increase the pressure, which favors the
side of the reaction with the fewer numbers of moles of gas.
We are to predict the effect on the position of the equilibrium
2 O3 (g) 3 O 2 (g)
with various changes in concentration and volume.
Analyze
Increasing the concentration of a reactant shifts the equilibrium to the right, whereas increasing the
concentration of a product shifts the equilibrium to the left. An increase in volume decreases the pressure and
shifts the equilibrium toward the side of the reaction with the greater moles of gas.
Solve
(a) Increasing the concentration of the reactant, O3, shifts the equilibrium to the right, increasing the
concentration of the product, O2.
(b) Increasing the concentration of the product, O2, shifts the equilibrium to the left, increasing the
concentration of the reactant, O3.
(c) Decreasing the volume of the reaction to 1/10 its original volume shifts the equilibrium to the left, increasing
the concentration of the reactant, O3.
Think about It
Adding O2 and decreasing the volume cause the same shift in the position of the equilibrium.
We are to predict the effect on the position of the equilibrium
2 NO 2 (g) NO(g) + NO3 (g)
with various changes in concentration and volume.
Analyze
Increasing the concentration of a reactant shifts the equilibrium to the right, whereas increasing the
concentration of a product shifts the equilibrium to the left. An increase in volume decreases the pressure and
shifts the equilibrium toward the side of the reaction with the greater moles of gas.
Solve
(a) Increasing the concentration of the product, NO, shifts the equilibrium to the left.
(b) Increasing the concentration of the reactant, NO2, shifts the equilibrium to the right.
(c) Because the moles of gaseous products equal the moles of gaseous reactants, increasing the volume of the
reaction has no effect on the position of the equilibrium.
Think about It
Increasing the concentration of NO3 has the same effect on the equilibrium as increasing the concentration of
NO.
We are to determine how decreasing the partial pressure of O2 affects the equilibrium
2 SO 2 (g) + O 2 (g) 2 SO3 (g)
Analyze
According to Le Chteliers principle, increasing the partial pressure or concentration of a reactant shifts the
equilibrium to the right. Decreasing the partial pressure of a reactant, then, shifts the equilibrium to the left.
144 | Chapter 14
Solve
Decreasing the partial pressure of O2 in this reaction shifts the equilibrium to the left.
Think about It
At equilibrium, then, we have less SO3 product when we reduce the partial pressure of O2 in the reaction
mixture.
We are asked to predict how the concentrations of H2, Cl2, and HCl in the equilibrium
H 2(g) + Cl2(g) 2 HCl(g)
will be affected if the equilibrium constant for the reaction of ammonia with hydrochloric acid
NH 3 (g) + HCl(g) NH 4Cl(s)
is much higher than that of the first reaction.
Analyze
If the K for the reaction of NH3 with HCl is much larger than that of H2 with Cl2, then adding NH3 to a reaction
mixture of H2, Cl2, and HCl will substantially remove HCl from that equilibrium mixture.
Solve
When NH3 reacts with HCl to remove HCl from the equilibrium mixture, the reaction to form HCl will shift to
the right. Because 2 mol of HCl is produced in the reaction of H2 with Cl2, the relative concentrations of H2 and
Cl2 will decrease at half the rate at which HCl decreases.
Think about It
By removing a product of a reaction through using a large-K process, we can drive even a low-K process to
completion.
For three processes at equilibrium, we are to determine which shows an increased yield of product C at
increasing temperatures.
Analyze
Endothermic processes have heat as a reactant. When the temperature is raised for these reactions, the
equilibrium shifts to the right, increasing the amount of product C formed.
Solve
Reaction (a) is the only endothermic process (H > 0), so it is the only process for which the product yield
increases with increasing temperature.
Think about It
Temperature changes do not affect the amount of product formed for reaction (b), for which H = 0.
For three processes at equilibrium, we are to determine which shows a decreased yield of product Z at
increasing temperatures.
Analyze
Exothermic processes have heat as a product. When the temperature is raised for these reactions, the
equilibrium shifts to the left, decreasing the amount of products formed.
Solve
Reaction (c) is the only exothermic process (H < 0), so it is the only process for which the product yield
decreases as the temperature of the reaction is raised.
Think about It
Temperature changes do not affect the amount of product formed for reaction (b), for which H = 0.

We are to explain why equilibrium calculations are simpler when no product is present at the start of the
reaction and when the value of the equilibrium constant, K, is very small.
Analyze
When no product is present, the reaction can only proceed to products; no reverse reaction can occur. When K is
very small, the reaction does not proceed very far to the right. The concentrations of products formed once the
reaction achieves equilibrium are very small.
Solve
When no products are present at the beginning of a reaction, we know that, no matter what the value of the
equilibrium constant, the reaction will proceed to the right, so the equilibrium expression for the reaction is
X+Y Z
x
([X] x)([Y] x)
We do not have to determine the reaction quotient for this situation because Q = 0 < K.
K=
When K is very small, the amount of reactants transformed into products is small, and so at equilibrium the
concentration of the reactants is approximately equal to the initial concentrations. This means that the
approximation
x
x
K=
([X] x)([Y] x) ([X])([Y])

for the reaction
X+Y Z
is valid. This makes our calculations easier and avoids having to use the quadratic equation.
Think about It
The assumption is considered valid if x < 5% for the value of both A and B.
For the reaction of 2 mol NO with 1 mol O2 to give 2 mol NO2, we are to determine whether the quadratic
equation could be used to solve for [NO2]eq.
Analyze
[NO2 ]2
Kc =
[NO]2 [O 2 ]
If [NO2]i = A, [NO]i = B, and [O2]i = C, the RICE table for this equilibrium would be
Reaction
Initial
Change
Equilibrium
2 NO(g)
[NO]
B
2x
B 2x
O2(g)
[O2]
C
+x
C+x
NO2(g)
[NO2]
A
+2x
A + 2x
and the equilibrium constant expression would be
Kc =
[A + 2x]2
[B 2x]2 [C x]
Solve
No, this equilibrium constant expression would require us to use a cubic equation to solve for [NO2].
146 | Chapter 14
Think about It
If the equilibrium constant is very small, however, the following assumption might be possible, which would
allow us to use the quadratic equation to solve for [NO2].
[A + 2x]2
[A + 2x]2
Kc =
[B 2x]2 [C x] [B]2 [C]

For the decomposition of PCl5 to PCl3 and Cl2 (Kp = 23.6 at 500 K), we are to calculate the equilibrium partial
pressures given the initial partial pressures of PCl5 and PCl3. We are also to determine how the concentration of
PCl3 and PCl5 change when more Cl2 is added to the system already at equilibrium.
Analyze
(a) To calculate the partial pressures of all the species present, we set up a RICE table. Because the initial partial
pressure of Cl2 is 0.0 atm, we know that the reaction proceeds to the right to attain equilibrium.
(b) To determine how the equilibrium shifts when Cl2 is added, we apply Le Chteliers principle.
Solve
(a)
Reaction
PCl5(g)
PPC15
Initial
Change
Equilibrium
0.560 atm
x
0.560 x
PCl3(g)
PPC13
0.500 atm
+x
0.500 + x
Cl2(g)
PC12
0.00 atm
+x
x
After placing these values into the equilibrium constant expression, we can solve for x by using the quadratic
formula:
( 0.500 + x)( x)
23.6 =
(0.560 x)
x 2 + 24.1x 13.216 = 0
x = 0.536 or 24.6
Because 0.500 + x would be negative if x = 24.6, the actual root for this problem is x = 0.536. The equilibrium
partial pressures of PCl5, PCl3, and Cl2 are
PPCl = 0.560 0.536 = 0.024 atm
5
PPCl = 0.500 + 0.536 = 1.036 atm

3
PCl = 0.536 atm

2
(b) When the partial pressure of Cl2 is increased, the partial pressure (or concentration) of PCl3 decreases and
the partial pressure of PCl5 increases.
Think about It
Because K > 1, the products of this reaction are favored.
For an initial partial pressure of NO2 of 0.900 atm in the reaction
2 NO 2 (g) N 2O 4 (g)
for which Kp = 4 at 298 K, we are to calculate the partial pressures of NO2 and N2O4 at equilibrium.

Analyze
To solve this problem, we need to set up a RICE table. Because no initial partial pressure of N2O4 is given, we
assume that it is initially 0.000 atm. The equilibrium constant expression for this reaction is
PN2 O4
Kp =
2
PNO2
Solve
Reaction
2 NO2(g) N2O4(g)
PNO2
Initial
Change
Equilibrium
0.900 atm
2x
0.900 2x
PN2O4
0.000 atm
+x
x
formula:
x
4=
(0.900 2x) 2
x
4=
0.81 3.6x + 4x 2
16x 2 15.4x + 3.24 = 0
x = 0.652 or 0.311
Because 0.900 2x would be negative if x = 0.652, the actual root for this problem is x = 0.311. The
equilibrium partial pressures of NO2 and N2O4 are
PNO2 = 0.900 2 x = 0.278 atm
PN2O4 = x = 0.311 atm

Think about It
Checking our results should give the value of the equilibrium constant:
0.311
= 4.0
Kp =
2
0.278

For the initial concentrations of H2O and Cl2O as 0.00432 M in the equilibrium reaction
H 2O(g) + Cl2O(g) 2 HOCl(g)
where Kc

3FUI73D7FA53>5G>3F7F:77CG;>;4D;G?5A@57@FD3F;A@EA8
2O,
Cl2O, and HOCl.
Analyze
We first set up a RICE table to solve this problem. We assume here that the initial concentration of
HOCl = 0.00 M. The equilibrium constant expression for this reaction is
[HOCl]2
Kc =
[H 2 O][Cl2 O]
Solve
Reaction
Initial
Change
Equilibrium
H2O(g)
+
[H2O]
0.00432 M
x
0.00432 x
Cl2O(g) 2 HOCl(g)
[Cl2O]
HOCl
0.00432 M
0
x
+2x
0.00432 x
2x
148 | Chapter 14
After placing these values into the equilibrium constant expression, we can solve for x by taking the square root
of both sides:
( 2 x )2
0.0900 =
(0.00432 x) 2
2x
0.300 =
0.00432 x
1.296 10 3 0.30 x = 2 x
x = 5.63 10 4
The concentration of all the gases at equilibrium are
[H2O] = [Cl2O] = 0.00432 x = 3.76 103 M
[HOCl] = 2x = 1.13 103 M
Think about It
This reaction, with its equilibrium constant less than 1, favors reactants over product at equilibrium.
For an initial partial pressure of N2 of 0.900 atm and of H2 of 0.500 atm, we are to determine the equilibrium
partial pressure of NH3 given that Kp = 4.3 104 at 648 K for the reaction
3 H 2 (g) + N 2 (g) 2 NH 3 (g)
Analyze
To solve this problem, we first need to set up a RICE table. Because no initial partial pressure of NH3 is given,
we assume that it is initially 0.000 atm. The equilibrium constant expression for this reaction is
(P )
=
(P ) (P )
2
Kp
NH 3
3
H2
Solve
Reaction
Initial
Change
Equilibrium
3 H2(g)
N2
PH2
0.500 atm
3x
0.500 3x
N2(g)
2 NH3(g)
PNH3
PN2
0.900 atm
x
0.900 x
0.000 atm
+2x
2x
After placing these values into the equilibrium constant expression, we can make simplifying assumptions:
4.3 10 4 =
(2x)
(0.500 3 x)3 (0.900 x)
(2x)
(0.500) 3 (0.900)
x = 3.48 10 3
Checking the assumptions shows that they are both valid (less than 5%).
3 3.48 103
3.48 103
and
100 = 2.1%
100 = 0.4%
0.500
0.900
The partial pressure of ammonia at equilibrium in this reaction mixture is 2x = 6.96 103 M.
Think about It
We could expand the equilibrium constant expression to give a cubic equation and solve, but making the
simplifying assumptions here helps us to solve the problem more quickly. Remember to always check any
simplifying assumptions you make against the 5% rule.

Given Kp = 2 106 3FU8ADF:7D735F;A@A8?A>A8&'I;F: 1/2 mol of O2 to give 1 mol of NO2, we are to
calculate the equilibrium ratio of the partial pressure of NO2 to that of NO in air, where the partial pressure of
oxygen is 0.21 atm.
Analyze
The Kp expression for this reaction is
Kp =
PNO2
PNO ( PO2 )
12
Solve
When PO = 0.21 atm,
2
PNO2
Kp =
= 2 106
PNO ( 0.21)
Rearranging this equation to solve for the ratio of the partial pressure of NO2 to the partial pressure of NO gives
PNO2
12
= 2 106 ( 0.21) = 9 105
PNO
12
Think about It
The high value of K indicates that the product NO2 is highly favored. This is consistent with the high value we
calculated for the ratio of the partial pressures.
For the equilibrium describing the reaction of C with H2O to give CO and H2, we are to calculate the
equilibrium partial pressures when PH2O = 0.442 atm, PCO = 5.0 atm, and Kc = 3.0 102 3F
U-73D7F:7@
to recalculate these pressures when the partial pressures of CO and H2 are increased by 0.075 atm.
Analyze
Because we are working with partial pressures in the equilibrium constant expression, we must convert Kc into
Kp. In the reaction, n = 1.
1
L atm
K p = K c ( RT ) n = 3.0 10 2 0.08206
1273 K = 3.13
mol K
For each part of the problem we set up a RICE table. The equilibrium reaction is
C(s) + H 2O(g) CO(g) + H 2(g)
Carbon is a pure solid and does not show up in the equilibrium constant expression:
PCO PH2
Kp =
PH O
2
Solve
(a)
Reaction
Initial
Change
Equilibrium
H2O(g) + C(s) CO(g)
PH2 O
0.442 atm
x
0.442 x
PCO
5.0 atm
+x
5.0 + x
H2(g)
PH2
0
+x
x
formula:
150 | Chapter 14
3.13 =
x 5.0 + x
(0.442 x)
x 2 + 8.13x 1.383 = 0
x = 0.167 or 8.30
The value of x = 8.30 would give negative partial pressures for CO and H2, so x = 0.167. The partial pressures
of the gases at equilibrium are
PH2O = 0.442 x = 0.275 atm
PCO = 5.0 + x = 5.17 atm, or 5.2 atm

(b)
PH2 = x = 0.167 atm

Reaction
H2O(g) + C(s) CO(g)
Equilibrium Mixture
Increase
New Initial
Change
Equilibrium
PH 2 O
0.275 atm
0.275
+x
0.275 + x
+ H2(g)
PCO
5.17 atm
+0.075
5.245
x
5.245 x
PH2
0.167 atm
+0.075
0.242
x
0.242 x
The equilibrium shifts to the left as predicted by Le Chteliers principle and confirmed by comparing Q versus K.
0.242 5.245
Q=
= 4.62
0.275
Q>K
After placing these values into the equilibrium constant expression, we can make the simplifying assumption
that x is small with respect to 5.245:
(5.245 x )( 0.242 x ) (5.245)( 0.242 x )
3.13 =
(0.275 + x)
(0.275 + x)
8.375 x = 0.40854
x = 0.0488
Checking our simplifying assumption shows that it is valid:
0.0488
100 = 0.9%
5.245
The partial pressures of the gases at equilibrium are
PH2O = 0.275 + x = 0.324 atm
PCO = 5.245 x = 5.20 atm

PH = 0.242 x = 0.193 atm
2
Think about It
Checking our results should give a value close to 3.13, the equilibrium constant value.
5.17 0.167
For part a:
= 3.14
0.275
5.20 0.193
For part b:
= 3.10
0.324
Given that Kp 3F
UI73D7FA53>5G>3F7 PCO and PCO at equilibrium for the reaction

2
CO 2 (g) + C(s) 2 CO(g)

where the initial partial pressures of CO2 and CO are 5.0 atm and 0.0 atm, respectively.

Analyze
Because carbon is a pure solid, it does not appear in the equilibrium constant expression:
2
PCO )
(
=
Kp
Solve
PCO
Reaction
CO2(g) + C(s) 2 CO(g)
Initial
Change
Equilibrium
5.0 atm
x
5.0 x
PCO2
PCO
0.0 atm
+2x
2x
formula:
1.5 =
( 2x )
(5.0 x)
4x + 1.5x 7.5 = 0
x = 1.20 or 1.57
The value of x = 1.57 would give a negative partial pressure for CO, so x = 1.20. The partial pressures of the
gases at equilibrium are
PCO = 2x = 2.4 atm
PCO 2 = 5.0 x = 3.8 atm
Think about It
Checking our results should give a value close to 1.5, the equilibrium constant value:
( 2.4)2
3.8
= 1.5

Given an equilibrium partial pressure for H2S of 0.355 atm in the reaction
NH 4SH(g) NH 3 (g) + H 2S(g)
with Kp
3FUI73D7FA67F7D?;@7F:77CG;>;4D;G?B3DF;3>BD7EEGD7A8&
3.
Analyze
Because NH4SH is a solid, it does not appear in the equilibrium constant expression:
)( )
Kp = PNH3 PH2S
We are given the values of Kp and PH S to substitute into the equation to solve for PNH .
2
3
Solve
PNH3 =
Kp
PH2S
0.126
= 0.355 atm
0.355
Think about It
Because the equilibrium partial pressures of ammonia and hydrogen sulfide in the reaction mixture are equal,
we can deduce from their 1:1 stoichiometry in the balanced equation that the initial reaction mixture contained
only pure NH4SH, which was then allowed to decompose in the reaction vessel to give equal amounts of NH3
and H2S.
152 | Chapter 14
For the decomposition of NO2 to NO and O2 when PO2 = 0.136 atm at equilibrium, we are asked to calculate the
partial pressures of NO and NO2 at equilibrium at 1000 K, where Kp = 158, and to calculate the total pressure in
the flask at equilibrium.
Analyze
(a) To calculate the partial pressures of NO and NO2, we set up a RICE table, where we start with pure NO2 (A)
and end with PO = 0.136 atm = x at equilibrium.
2
(b) The total pressure is
Solve
(a)
PT = PNO2 + PNO + PO2
Reaction
2 NO2(g)
PNO 2
O2(g)
PO 2
PNO
0.00 atm
+2x
2x
A atm
2x
A 2x
Initial
Change
Equilibrium
2 NO(g)
0.00 atm
+x
x
We know that at equilibrium x = 0.136 atm, so
K p = 158 =
( P ) = ( 2 x ) ( x ) = ( 0.272) ( 0.136)
(P )
(P )
(P )
( PNO )
O2
NO2
( 0.272 ) ( 0.136 )
NO2
158
PNO2 = ( 6.37 10 5 )
12
At equilibrium,
NO2
( PNO2 ) =
= 6.37 10 5
= 7.98 10 3 atm
PNO = 2x = 0.272 atm

PO2 = x = 0.136 atm
PNO2= 7.98 103 atm
(b) PT = 7.98 103 atm + 0.272 atm + 0.136 atm = 0.416 atm
Think about It
The amount of NO2 initially present can also be calculated:
A 2 x = 7.98 10 3 atm
Because x = 0.136 atm,
A = 7.98 10 3 + 2 0.136 = 0.280 atm
Given that Kp 3F
U8ADF:7D735F;A@
2 SO3 (g) 2 SO 2 (g) + O 2 (g)
in which SO3 was initially the only compound present and given that the equilibrium partial pressure of SO3 is
0.100 atm, we are to calculate the partial pressure of oxygen at equilibrium.
Analyze
Because we know that the reaction vessel initially contained only SO3, we know that the initial partial pressures
of the products (SO2 and O2) were 0.000 atm. We set up a RICE table describing this experiment, keeping in
mind that at equilibrium the partial pressure of SO3 is measured at 0.100 atm.

Solve
Reaction
2 SO3(g)
Initial
Change
Equilibrium
2 SO2(g)
O2(g)
PSO 3
PSO 2
PO
A atm
A 2x
0.100
0.000 atm
+2x
2x
0.000 atm
+x
x
where A is the partial pressure of SO3 originally present in the reaction vessel, so that A 2x = 0.100 atm. All
we need, however, are the equilibrium partial pressures for the equilibrium constant expression
7.69 =
( 2 x ) 2( x )
(0.100) 2
0.0769 = 4 x 3
x = 0.268
The equilibrium partial pressure of oxygen is x = 0.268 atm.
Think about It
The initial partial pressure of SO3 in the experiment is A = 0.100 + 2x = 0.636 atm.
For the equilibrium reaction
N 2 (g) + O 2 (g) 2 NO(g)

the value of Kp is 0.050 at
U-73D7FA53>5G>3F7F:7B3DF;3>BD7EEGD7EA8&2, O2, and NO at equilibrium

given initial partial pressures for these gases of 0.79 atm for N2, 0.21 atm for O2, and 0.00 atm for NO.
Analyze
We set up a RICE table to solve this problem. The equilibrium constant expression for this reaction is
Kp =
( PNO )2
( P )( P )
O2
Solve
Reaction
N2(g)
PN 2
N2
O2(g)
2 NO(g)
PNO
PO 2
Initial
0.79 atm
0.21 atm
0.00 atm
Change
x
x
+2x
Equilibrium
0.79 x
0.21 x
2x
formula:
0.050 =
0.050 =
(2x)
(0.79 x)(0.21 x)
4x 2
(0.1659 x + x )
2
3.95x 2 + 0.050x 0.008295 = 0

x = 0.03993 or 0.05260
154 | Chapter 14
The value of x = 0.05260 would give a negative partial pressure for NO, so x = 0.03993. The partial pressures
of the gases at equilibrium are
PO = 0.21 x = 0.17 atm
2
PN 2 = 0.79 x = 0.75 atm

PNO = 2x = 0.080 atm
Think about It
Using these equilibrium partial pressures, we can check our answers, which should give Kp = 0.050:
( 0.080)2 = 0.050
( 0.75)( 0.17)

For the following reaction
2 NO 2 (g) 2 NO(g) + O 2(g)
6
the value of Kp is 6.5 10 3F

U -7 3D7 FA 53>5G>3F7 F:7 B3DF;3> BD7EEGD7E A8 &'2, NO, and O2 at
equilibrium if the initial pressure of NO2 is 0.500 atm.
Analyze
We assume that the initial pressures of the other gases in the reaction are 0.000 atm in setting up the RICE table
to solve this problem. The equilibrium constant expression for this reaction is
(P ) (P
2
Kp =
NO
(P )
O2
NO2
Solve
Reaction
2 NO2(g)
2 NO(g)
PNO
PNO 2
O2(g)
PO 2
Initial
0.500 atm
0.000 atm
0.000 atm
Change
2x
+2x
+x
Equilibrium
0.500 2x
2x
x
Because the equilibrium constant is small, this reaction does not proceed very far to the right and we may be
able to make a simplifying assumption. After placing these values into the equilibrium constant expression, we
can solve for x:
(2x) ( x )
2
6.5 10 6 =
(0.500 2 x) 2
(2x) ( x)
2
(0.500) 2
x = 7.41 10 3
Checking this assumption shows that it is valid:

2 7.41 103
100 = 3%
0.500
The partial pressures of the gases at equilibrium are
PNO2 = 0.500 2x = 0.485 atm
PNO = 2x = 0.0148 atm
PO2 = x = 0.00741 atm
Think about It
Our results, which show only a very small amount of product gases being formed, are consistent with the small
equilibrium constant for this reaction.

For the following reaction
2 H 2S(g) 2 H 2(g) + S2(g)
the value of Kc is 2.2 10 at 1400 K. We are to calculate the equilibrium concentration of H2S, given that the
initial [H2S] is 6.00 M.
Analyze
We are told to assume that the initial concentrations of H2 and S2 are 0.00 M. Because the equilibrium constant
is small, we may be able to make a simplifying assumption. The equilibrium constant expression for this
reaction is
[H ]2 [S ]
K c = 2 22
[H 2S]
Solve
Reaction
2 H2S(g)
[H2S]
6.00 M
2x
6.00 2x
Initial
Change
Equilibrium
2 H2(g)
[H2]
0.00 M
+2x
2x
S2(g)
[S2]
0.00 M
+x
x
Because the equilibrium constant is small, this reaction does not proceed very far to the right and we may be
able to make a simplifying assumption. After placing these values into the equilibrium constant expression, we
can solve for x:
(2x ) ( x )
2
2.2 10
(6.00 2 x)2
x = 0.126
( 2x ) ( x )
2
(6.00) 2
Checking this assumption shows that it is valid:

2 0.126
100 = 4%
6.00
The equilibrium [H2S] is 6.00 2x = 5.75 M.
Think about It
Without the simplifying assumption, we would have to solve a cubic equation.
Given that Kc = 6.1 103 3FU8ADF:7D735F;A@
N 2O 4 (g) 2 NO 2 (g)
and that the equilibrium concentration of NO2 is 2.2 107 M, we are to calculate the concentration of N2O4 in
the air.
Analyze
[NO 2 ]2
[N 2 O 4 ]
Because we are given the values of [NO2] and Kc, we need only solve for [N2O4].
Kc =
Solve
[N 2 O 4 ] =
[NO 2 ] (2.2 10 7 ) 2
=
= 7.9 10 12 M
Kc
6.1 10 3
156 | Chapter 14
Think about It
The equilibrium constant for the reverse reaction would be
Kc,reverse =
[N2 O4 ] 1
=
= 160
[NO2 ]2 Kc

For the following reaction, Kc = 5.0 at 600 K:
CO(g) + Cl2 (g) COCl2(g)
We are asked to calculate the partial pressures of the gases at equilibrium given that the initial partial pressures
of CO and Cl2 are 0.265 atm and that of COCl2 is 0.000 atm.
Analyze
We have to first calculate Kp from Kc where n = 1:
5.0
= 0.102
atm
L
0.08206
600
K
mol K
We can set up a RICE table to solve for the equilibrium partial pressures of the gases.
K p = Kc ( RT ) n =
Solve
Reaction
CO(g)
PCO
Initial
Change
Equilibrium
0.265 atm
x
0.265 x
Cl2(g)
PCl 2
0.265 atm
x
0.265 x
COCl2(g)
PCOCl 2
0.000 atm
+x
x
After placing these values into the equilibrium constant expression, we can solve for x by using the quadratic formula:
x
0.102 =
(0.265 x) 2
x
0.0702 0.530 x + x 2
0.102 x 2 1.05406 x + 0.00716 = 0
x = 10.33 or 0.00680
The value of x = 10.33 would give negative partial pressures for CO and Cl2, so x = 0.00680. The partial
pressures of the gases at equilibrium are
PCO = PCl = 0.265 x = 0.258 atm
2
0.102 =
PCOCl 2 = x = 0.00680 atm

Think about It
Checking our result, we get the value of Kp:
0.00680
= 0.102
(0.258) 2

For the reaction
2 CO(g) + O 2(g) 2 CO 2(g)
Kc =
3F
U-73D7FA53>5G>3F7F:7H3>G7A81'2 1'2] when [O2] at equilibrium is 0.0045 M.

Analyze
The Kc expression for this reaction is
[CO 2 ]2
[CO]2 [O 2 ]
Rearranging this expression gives the desired ratio of concentrations:
[CO]2
1
=
[CO2 ]2 K c [O 2 ]
Kc =
[CO]
=
[CO2 ]
1
K c [O2 ]
Solve
[CO]
1
=
= 15
[CO 2 ]
1.0 0.0045
Think about It
The equilibrium constant for the reverse reaction would be 1/Kc = 1.0.
We are to calculate the concentrations of all the gases at equilibrium for the reaction
CO(g) + H 2O(g) CO 2 (g) + H 2 (g)
given that the initial concentrations of all the gases are 0.050 M and that Kc = 5.1 at 700 K.
Analyze
[CO2 ][H 2 ]
Kc =
[CO][H 2 O]
We have to use Q, the reaction quotient, to determine the direction in which the reaction goes to reach
equilibrium:
Q=
(0.050)(0.050)
= 1.0
(0.050)(0.050)
Q < K, so the reaction proceeds to the right.

Solve
Reaction
Initial
Change
Equilibrium
CO(g)
[CO]
H2O(g)
[H2O]
0.050 M
x
0.050 x
0.050 M
x
0.050 x
5.1 =
Taking the square root of both sides:
(0.050 + x) 2
(0.050 x) 2
(0.050 + x)
(0.050 x)
0.1129 2.258 x = 0.050 + x
0.0629 = 3.258 x
0.0193 = x
2.258 =
CO2(g)
[CO2]
0.050 M
+x
0.050 + x
H2(g)
[H2]
0.050 M
+x
0.050 + x
158 | Chapter 14
The concentrations of the gases at equilibrium are
[CO] = [H2O] = 0.050 x = 0.031 M
[CO2] = [H2] = 0.050 + x = 0.069 M
Think about It
We did not need to use the quadratic formula here because with the concentrations of the reactants equal to each
other and the concentrations of the products equal to each other, we could simplify the math by taking the
square root of both sides of the equation to solve for x.
SO 2 (g) + NO 2 (g) SO3 (g) + NO(g)
given that the initial concentrations of SO2 and NO2 are 0.50 M, the initial concentrations of SO3 and NO are
0.0050 M, and Kc = 2.50.
Analyze
[SO3 ][NO]
= 2.50
[SO2 ][NO2 ]
We have to use Q, the reaction quotient, to determine the direction in which the reaction goes to reach
equilibrium:
(0.0050)(0.0050)
Q=
= 1.0 10 4
(0.50)(0.50)
Q < K, so the reaction proceeds to the right.
Kc =
Solve
Reaction
Initial
Change
Equilibrium
SO2(g)
[SO2]
0.50 M
x
0.50 x
NO2(g)
[NO2]
0.50 M
x
0.50 x
SO3(g)
[SO3]
0.0050 M
+x
0.0050 + x
NO(g)
[NO]
0.0050 M
+x
0.0050 + x
(0.0050 + x) 2
(0.50 x) 2
(0.0050 + x)
1.581 =
(0.50 x)
0.7905 1.581x = 0.0050 + x
0.7855 = 2.581x
0.30 = x
[SO2] = [NO2] = 0.50 x = 0.20 M
[SO3] = [NO] = 0.0050 + x = 0.30 M
2.50 =
Think about It
We did not need to use the quadratic formula here because with the concentrations of the reactants equal to each
other and the concentrations of the products equal to each other, we could simplify the math by taking the
square root of both sides of the equation to solve for x.
NO(g) + NO 2 (g) N 2O3 (g)

given that the initial amounts of NO and NO2 are 15 g and 69 g, respectively, contained in a 4.0 L flask. For this
D735F;A@3FU, Kp = 0.535.
Analyze
[N 2O3 ]
[NO][NO 2 ]
We are given the mass of each reactant and can convert those masses to molar concentrations by using the
molar mass of the reactants and the volume of the flask to give the initial concentration of the reactants for the
RICE table. Because we are given the value of Kp, we will have to calculate the value of Kc from Kp by using
Kp
Kc =
n
RT
Kc =
( )
where n = 1, R = 0.08206 L atm/mol K, and T = 298 K.

Finally, the flask initially contains only reactants, so we know that the equilibrium will proceed from initial
conditions to the right to form products.
Solve
The initial concentrations of the reactants are
1 mol
1
= 0.125M NO
30.01 g 4.0 L
1 mol
1
= 0.375M NO 2
69 g NO 2
46.01 g 4.0 L
15 g NO
The value of Kc is
Kc =
Reaction
Initial
Change
Equilibrium
Kp
( RT )
0.535
L atm
0.08206 mol K 298K
NO(g)
[NO]
0.125 M
x
0.125 x
13.08 =
13.08 =
NO2(g)
[NO2]
0.375 M
x
0.375 x
= 13.08
N2O3(g)
[N2O3]
0.0 M
+x
x
x
(0.125 x)(0.375 x)
x
(0.046875 0.500x + x 2
0.613125 6.54x + 13.08x 2 = x

13.08x 2 7.54x + 0.613125 = 0
x = 0.09796
[NO] = 0.125 x = 0.027 M
[NO2] = 0.375 + x = 0.277 M
[N2O3] = = x = 0.098 M
Think about It
This problem is multilayered in that we must realize at the start that Kc must be calculated from Kp and that we
have to compute the concentrations in moles per liter of each reactant before using the RICE table.
160 | Chapter 14
For the decomposition reaction of HI into H2 and I2, we are to calculate the concentrations of all the gases at
equilibrium
2 HI(g) H 2 (g) + I 2 (g)
given that the initial amount of HI is

93@6;E5A@F3;@76;@3$5:3?47DADF:;ED735F;A@3F
U, Kc =
0.0183.
Analyze
[H ][I ]
K c = 2 22
[HI]
We are given the mass of the reactant and can convert that mass to the molar concentrations by using the molar
mass of HI and the volume of the chamber to give the initial concentration of HI for the RICE table. The flask
initially contains only HI as the reactant and no H2 or I2 as products, so we know that the equilibrium will
proceed from the initial conditions to the right to form products.
Solve
The initial concentration of HI is
80.0 g HI
Reaction
Initial
Change
Equilibrium
1 mol
1
= 0.250M HI
129.91 g 2.5 L
2 HI(g)
[HI]
0.250 M
2x
0.250 2x
0.0 M
+x
x
0.0183 =
13.08 =
H2(g)
[H2]
I2(g)
[I2]
0.0 M
+x
x
x2
(0.250 2x)2
x2
(0.0625 x + 4x 2 )
0.9268x 2 + 0.0183x 0.00114375 = 0

x = 0.02662
[HI] = 0.250 2x = 0.198 M
[H2] = [I2] = x = 0.0226 M
Think about It
We cannot make a simplifying assumption in solving this problem because the value of x that we get from the
assumption is 13% compared to the 0.250 M it is subtracted from. Therefore, we must use the quadratic
equation for this problem.
We are to relate the sign of GUFAF:7?39@;FG67A8K.
Analyze
The equation relating GUFAK is
G = RT ln K

Solve
Yes, the value of GU ;E BAE;F;H7 I:7@ K < 1. Because ln K is negative for K < 1 and because GU
RT ln K, the value of GU;EBAE;F;H7
Think about It
This means that reactions with K < 1 are not spontaneous.
We are to explain why Kp is used in the equation
G = RT ln K
for reactions occurring in the gas phase, not Kc.
Analyze
If all the reactants and products are in the gas phase, the equilibrium constant can be expressed as Kp.
Solve
Because GU is referenced to standard-state conditions and we can express gas pressures in their standard states,
the equilibrium constant K in gaseous reactions can be Kp.
Think about It
The equation relating Gibbs free energy and the equilibrium constant K is powerful. We can calculate the value
of K by measuring G, or we can determine G by measuring K.
If a reaction starts with 100% reactants, we are to determine in which direction the reaction shifts when it is
spontaneous (GU

Analyze
G = RT ln K
Solve
When GU
, the ln K of the reaction is positive, giving K > 1. The reaction favors the formation of products,
so the reaction will shift to the right.
Think about It
The reaction will proceed to the right until the mixture of reactants and products as expressed in the reaction
quotient Q matches the value of the equilibrium constant K.
If a reaction starts with 100% products, we are to determine in which direction the reaction shifts when it is
spontaneous (GU

162 | Chapter 14
Analyze
G = RT ln K
Solve
The GU for a reaction is expressed for the forward reaction, and because this reaction is spontaneous we know
that K > 1. This reaction favors product formation. However, K would have to be infinite for the reaction to
produce 100% products. Therefore, the reaction will shift slightly to the left to achieve equilibrium.
Think about It
For a reaction in which GU > 0, the equilibrium lies farther to the left than for a reaction for which GU


Given three reactions with associated GU H3>G7E I7 3D7 3E=76 FA 67F7D?;@7 I:;5: D735F;A@ :3E F:7 >3D97EF
value of K 3FU
Analyze
The equilibrium constant of a reaction is related to the Gibbs free energy through the equation
GURT ln K
Rearranging this equation gives
G
ln K =
RT
From this we see that the more negative the value of G, the larger K will be.
Solve
Two of the reactions have negative values of GU 3@6 3D7 EBA@F3@7AGE 4 3@6 5 F:7K I;>> :3H7 K > 1. The
reaction with the more negative free energy (reaction c) has the largest equilibrium constant.
Think about It
The value of K for reaction (c) is
ln K =
G
27.9 kJ
=
= 11.26
3
RT
8.314 10 kJ/mol K 298 K
11.26
K =e
= 7.8 10
Given the GUH3>G7 for the reaction of N2O with O2 as 68.9 kJ at 298 K, we are to calculate the value of the
equilibrium constant.
Analyze
The equilibrium constant of a reaction is related to the Gibbs free energy through the equation
GURT ln K
Rearranging this equation gives
G
ln K =
RT

Solve
ln K =
68.9 103 J/mol N 2O

G
=
= 27.81
RT
(8.314 J/mol K) 298 K
K = e27.81 = 8.37 1013

Think about It
Because the free energy of this reaction is positive, the reaction is nonspontaneous and if starting from pure
N2O, the reaction proceeds only slightly to the right to give products, as evidenced by its very small equilibrium
constant.
For the balanced equilibrium reaction
2 SO2(g) + O2(g) 2 SO3(g)

for which Kp = 3.4 at 1000 K, we are asked to calculate the enthalpy change of the reaction under standard
conditions, to calculate the value of value of Kp at 298 K, and finally to calculate the free energy change for the
reaction under standard conditions at 298 K to compare it with the value obtain using Appendix 4.
Analyze
(a) The enthalpy of the reaction under standard conditions may be calculated using the values for the enthalpy
of formation for the reactants and products in Appendix 4.
H rxn
= nH f,products
n H f,reactants
(b) We can calculate the value of the equilibrium constant at 298 K from the value of K at 1000 K and the
enthalpy of the reaction through the equation
K
H 1 1
ln 2 =
R T2 T1
K1
(c) The value of the equilibrium constant at 298 from part b can be used to calculate the standard free energy of
the reaction through
GURT ln K
and the value of the free energy from values in Appendix 4 can be calculated through the following equation for
comparison
= nGf,products
nGf,reactants
Grxn
Solve
(a) The enthalpy of the reaction under standard conditions is
H rxn
= ( 2 mol SO 3 ) ( 395.7 kJ/mol ) ( 2 mol SO 2 ) ( 296.8 kJ/mol ) + (1 mol O 2 ) ( 0.0 kJ/mol )
H rxn
= 197.8 kJ
(b) The value of the equilibrium constant at 298 from the calculated value of the enthalpy in part a and from the
value of K at 1000 K is
K
1
(197.8 103J/mol) 1
ln 298 =
298 K 1000 K = 56.045
3.4
8.314
J/mol
K 298
56.045
= 2.188 1024
3.4 = e
K 298 = 7.4 1024

(c) From the value of K at 298 K, we calculate the free energy at standard conditions:
G = (8.314 J/mol K) (298 K) ln(7.4 10 24 ) = 141.9 kJ/mol
164 | Chapter 14
From the standard free energy values in Appendix 4, the free energy at 298 K is
Grxn
= ( 2 mol SO 3 ) ( 371.1 kJ/mol ) ( 2 mol SO 2 ) ( 300.1 kJ/mol ) + (1 mol O 2 ) ( 0.0 kJ/mol )
= 142.0 kJ
Grxn
These values are very close to each other.
Think about It
This reaction is exothermic, so it makes sense that the equilibrium constant is larger at 298 K than at 1000 K.
Given Kp = 0.534 for the reaction of H2 with CO2 to produce H2O 3@6 ' 3F
U I7 3D7 FA 53>5G>3F7 F:7

value of the equilibrium constant, Kp, at 298 K from the value of the enthalpy of the reaction under standard
conditions, then calculate the value of free energy at 298 K from the equilibrium constant at 298 K and compare
that answer to the calculated value of GUby using Gf values from Appendix 4.
Analyze
(a) The enthalpy of the reaction under standard conditions may be calculated using the values for the enthalpy
of formation for the reactants and products in Appendix 4.
H rxn
= nH f,products
n H f,reactants
We can then calculate the value of the equilibrium constant at 298 K from the value of K 3F
U 3@6 F:7

enthalpy of the reaction through the equation
K
H 1 1
ln 2 =
R T2 T1
K1
(b) The value of the equilibrium constant at 298 K from part a can be used to calculate the standard free energy
of the reaction through
GURT ln K
and the value of the free energy from values in Appendix 4 can be calculated through the following equation for
comparison:
= nGf,products
nGf,reactants
Grxn
Solve
(a) The enthalpy of the reaction under standard conditions is
= (1 mol H 2O ) ( 241.8 kJ/mol ) + (1 mol CO ) ( 110.5 kJ/mol )

H rxn
(1 mol H 2 ) ( 0.0 kJ/mol ) + (1 mol CO 2 ) ( 393.5 kJ/mol )

H = 41.2 kJ
The value of the equilibrium constant at 298 K from the calculated value of the enthalpy in part a and from the
value of K 3F #
U is
! K $
1 $
(41.2 103 J/mol) ! 1
ln ## 298 && =
#
& = 11.54
8.314 J/mol K " 298 K 973 K %
" 0.534 %
rxn
! K $
# 298 & = e 11.54 = 9.77 106
# 0.534 &
"
%
K 298 = 5.21106
(c) From the value of K at 298 K, we calculate the free energy at standard conditions:
G = (8.314 J/mol K) (298 K) ln(5.21 10 6 ) = 30.1 kJ/mol

From the standard free energy values in Appendix 4, the free energy at 298 K is
= (1 mol H 2O ) ( 137.2 kJ/mol ) + (1 mol CO ) ( 228.6 kJ/mol )

Grxn
(1 mol H 2 ) ( 0.0 kJ/mol ) + (1 mol CO 2 ) ( 394.4 kJ/mol )

G = 28.6 kJ
These values are very close to each other.
rxn
Think about It
For this reaction, we can also calculate the entropy change from values in Appendix 4. From these values we
see that SU " ?A> K. Thus, this reaction is endothermic but favored by entropy, so at high enough
temperature the reaction becomes spontaneous.
In this problem we can add two equations to calculate GU3@6Kp at 298 K for the reaction
N 2 (g) + 2 O 2 (g) 2 NO 2 (g)
Analyze
To obtain the overall reaction, we simply add the two reactions given and add their GU H3>G7E -7 53@
calculate the value of Kc by using
GURT ln K
and from Kc we can calculate Kp by using
K p = K c ( RT )
where n for this reaction is 1.

Solve
Adding the equations gives the overall equation and GU
N 2 (g) + O 2 (g) 2 NO(g)
Rearranging to calculate Kc,
G = 173.2 kJ
2 NO(g) + O 2 (g) 2 NO 2 (g)
G = 69.7 kJ
N 2 (g) + 2 O 2 (g) 2 NO 2 (g)
G = 103.5 kJ
ln K =
G
103.5 kJ/mol
=
= 41.77
RT
8.314 10 3 kJ/mol K 298 K
41.77
K=e
= 7.24 10
The value of Kp can now be calculated:
19
K p = 7.24 10 19 [ (0.08206 L atm/mol K) 298] = 2.96 10 20

1
Think about It
Because the free-energy change is large and positive, K is much less than 1 and the reactants are greatly favored
over the product at equilibrium.
We can add three equations to calculate GU3@6Kp 3F
U8ADF:7D735F;A@
3 NO(g) N 2O(g) + NO 2 (g)
Analyze
In adding the equations, we might have to reverse one of the reactions, in which case we have to reverse the
sign of GU3EEA5;3F76I;F:F:3FB3DF;5G>3DD735F;A@Combining equations gives us the overall GUI:;5:9;H7E
Kp through the equation
GURT ln Kp
166 | Chapter 14
Solve
Adding the equations gives the overall Grxn

:
2 NO(g) + O 2 (g) 2 NO 2 (g)
G = 69.7 kJ
2 NO(g) + N 2 (g) 2 N 2O(g)
G = 33.8 kJ
2 NO(g) N 2 (g) + O 2 (g)
G = 173.2 kJ
G = 209.1 kJ
6 NO(g) 2 N 2O(g) + 2 NO 2 (g)
Dividing by 2 gives the desired reaction:
3 NO(g) N 2O(g) + NO 2 (g)
G = 104.55 kJ
The Kp for this reaction is
ln K p =
G
(104.55 kJ/mol)
=
= 16.27
RT
kJ
3
8.314 10 mol K 773 K
K p = e16.27 = 1.16 107

Think about It
Because GU;E>3D973@6@793F;H78ADF:7AH7D3>>D735F;A@K is much greater than 1 and the products are greatly
favored over the reactants.
Using the relationship
K
H 1 1
ln 2 =
R T2 T1
K1
we can determine whether a reaction is endothermic or exothermic if the value of K decreases with increasing T.
Analyze
In the equation, K2 < K1, so ln(K2/K1) < 0 and T2 > T1, so (1/T2 1/T1) < 0.
Solve
For ln(K2/K1) to be negative when (1/T2 1/T1) is also negative, the value of H must be negative and the
reaction must be exothermic.
Think about It
An endothermic reaction, by contrast, shows an increased K with increasing T because H > 0 and thus
ln(K2/K1) > 0, so K2/K1 > 0.
Given that the reaction of CO with O2 to give CO2 is exothermic, we are to determine whether Kp increases or
decreases with increasing temperature. We can use the relationship
K
H 1 1
ln 2 =
R T2 T1
K1
Analyze
In this equation H and, for T2 > T1, the quantity 1/T2 1/T1 are negative.
Solve
When both H and (1/T2 1/T1) are negative, ln(K2/K1) is also negative. This gives K2 < K1. The equilibrium
constant decreases for exothermic reactions as the temperature is raised.

Think about It
For an endothermic reaction, however, the equilibrium constant increases as temperature increases.
Given that Kp for the reaction of CO with H2O increases as the temperature decreases, we can use the
relationship
K
H 1 1
ln 2 =
R T2 T1
K1
to determine whether the reaction is endothermic or exothermic.
Analyze
In the equation K2 > K1, so ln(K2/K1) > 0. Because T2 < T1, (1/T2 1/T1) > 0.
Solve
For ln(K2/K1) to be positive when (1/T2 1/T1) is also positive, H must be negative and the reaction must be
exothermic.
Think about It
An endothermic reaction, by contrast, shows a decreased K with a decrease in temperature.
Given the equation
CH 4 (g) + H 2O(g) 3H 2 (g) + CO(g)

and that it is endothermic (HU
="I73D7FABD76;5FI:7F:7DF:7H3>G7A8Kp will increase, decrease, or
stay the same as the temperature is raised.
Analyze
By Le Chteliers principle, when a reaction is endothermic, heat is a reactant in the chemical process. If we
increase the amount of a reactant, we shift the equilibrium to the right.
Solve
Increasing the temperature shifts the equilibrium to the right, and so the value of the equilibrium constant
increases.
Think about It
For an exothermic reaction, the opposite occurs: the value of the equilibrium constant decreases as the
temperature of the reaction is raised.
Given HU
=" 3@6 Kc = 4.10 104 for the conversion of N2 and O2 FA &' 3F
U I7 3D7 FA

calculate the value of Kc 3FU
Analyze
The relationship between equilibrium constants at two different temperatures is given by
K
H 1 1
ln 2 =
R T2 T1
K1
where HU ;E F:7 7@F:3>BK A8 F:7 D735F;A@ ;@ joules per mole), R is the gas constant (in joules per mole per
degree kelvin), and T1 and T2 are the temperatures (in kelvins).
168 | Chapter 14
Solve
4.1 10 4
ln
K2
1.806 105 J/mol 1

1
8.314
J/mol
K
2273
K
298
K
4.1 10 4
ln
= 63.337
K2
4
4.1 10
= e63.337 = 3.214 1027
K2
K 2 = 1.3 10 31
Think about It
As we would expect, the equilibrium constant for this endothermic reaction decreases as the reaction is cooled.
Given HU92.2 kJ and Kp = 41 for the reaction of N2 and H2 to give NH3 at 400 K, we are to calculate the
value of Kp at 700 K.
Analyze
K
H 1 1
ln 2 =
R T2 T1
K1
where HU ;E F:7 7@F:3>BK A8 F:7 D735F;A@ ;@ joules per mole), R is the gas constant (in joules per mole per
degree kelvin), and T1 and T2 are the temperatures (in kelvins).
Solve
41
9.22 104 J/mol 1
1
ln
8.314 J/mol K 400 K 700 K

K2
41
ln
= 11.88
K2
41
= e11.88 = 1.446 105
K2
K 2 = 2.8 10 4
Think about It
As we would expect, the equilibrium constant for this exothermic reaction decreases as the reaction is heated.
Given that K1 = 1.5 105 3F
U 3@6 K2 3F
U I7 3D7 FA 53>5G>3F7 F:7 EF3@63D6 7@F:3>BK A8 F:7
reaction between NO and O2 to produce NO2.
Analyze
We can use the following equation to solve this problem:
K
H 1 1
ln 2 =
R T2 T1
K1

Solve
" 23 %
" 1
H
1 %
=
ln $
'
$
'
5
8.314 J/mol K # 1273 K 703 K &
# 1.510 &
H = 1.15105 J/mol, or 115 kJ/mol
Think about It
The result that this reaction, where K decreases with increasing T, is exothermic is consistent with our answer to
Problem 14.112.
Given the Kc values for the reaction
AB
at two different temperatures, we are to calculate the enthalpy of the reaction. We have Kc
3F
U3@6
Kc
3F
U
Analyze
K
H 1 1
ln 2 =
R T2 T1
K1
where HU;EF:77@F:3>BKA8F:7D735F;A@;@joules per mole, R is the gas constant in joules per mole per degree
kelvin, and T1 and T2 are the temperatures in kelvins.
Solve
! 0.455 $
! 1
H
1 $
ln #
&=
#
&
8.314 J/mol K " 323 K 373 K %
" 0.655 %
0.3643 = H (4.992 10 5 )
H = 7.298 103 J/mol, or 7.30 kJ/mol
Think about It
Because the value of Kc increased with increasing temperature, we would expect the enthalpy of this reaction to
be positive (endothermic).
Given the percentage of decomposition of CO2 at three temperatures and that each equilibrium mixture begins
with 1 atm of CO2, we are to determine whether the reaction is endothermic and then calculate Kp at each
temperature. We are also to comment on the decomposition reaction as a remedy for global warming.
Analyze
The amount of CO2 decomposed increases with increasing temperature. This means that K2 > K1 in the equation
K
H 1 1
ln 2 =
R T2 T1
K1
where T2 > T1, so (1/T2 1/T1) < 0. To calculate Kp for each temperature, we set up a RICE table:
Reaction
Initial
Change
Equilibrium
2 CO2(g)
PCO 2
1 atm
2x
1 2x
2 CO(g)
PCO
0 atm
+2x
2x
O2(g)
PO 2
0 atm
+x
x
170 | Chapter 14
We know that 2x is equal to the percent decomposition divided by 100 and that the form of the equilibrium
expression is
Kp =
( PCO )2 ( PO
(P )
CO2
Because the percent decomposition increases with temperature, the value of Kp is expected to increase as T
increases.
Solve
Because the value of K increases with increasing temperature, ln(K2/K1) > 0. With (1/T2 1/T1) < 0, the value of
H must be positive, so this reaction is endothermic.
At 1500 K, 2x = 0.00048, x = 0.00024, and 1 2x = 0.99952:
(0.00048)2 (0.00024)
Kp =
= 5.5 1011
(0.99952)2
At 2500 K, 2x = 0.176, x = 0.088, and 1 2x = 0.824:
(0.176)2 (0.088)
Kp =
= 4.0 103
(0.824)2
At 3000 K, 2x = 0.548, x = 0.274, and 1 2x = 0.452:
(0.548)2 (0.274)
Kp =
= 0.40
(0.452)2
As predicted, the value of the equilibrium constant increases with increasing temperature. This reaction,
however, does not favor products even at very high temperature, so this is not a viable source of CO and is not a
remedy to decrease CO2 as a contributor to global warming. Also, the process produces poisonous CO gas.
Think about It
By using values in Appendix 4, we can confirm that the reaction is endothermic.
For the decomposition of ammonia at 800 K:
2 NH 3 (g) N 2 (g) + 3 H 2 (g)
we are given that the equilibrium concentration of NH3 is 0.0040 M when the 1 L reaction vessel initially
contained 2.00 mol NH3. From this information we are to calculate Kp and Kc at 800 K.
Analyze
We set up a RICE table to obtain the equilibrium amounts of N2 and H2 so we can compute the value of Kc:
[N ][H 2 ]3
Kc = 2
[NH 3 ]2
We can then use the relationship
Kp = Kc(RT)n
where n = 2 for this reaction to calculate Kp from Kc.
Solve
Reaction
2 NH3(g)
[NH3]
Initial
Change
Equilibrium
2.00
2x
2.00 2x
N2(g)
[N2]
0
+x
x
3 H2(g)
[H2]
0
+3x
3x

We know that 2.00 2x = 0.0040, so x = 0.998. Therefore, at equilibrium [N2] = x = 0.998 M and [H2] = 3x =
2.994 M.
(0.998M )(2.994 M )3
= 1.67 106
Kc =
(0.0040)2
2
L atm
800 K = 7.21 109
K p = 1.67 106 0.08206
mol K
Think about It
This equilibrium very heavily favors the formation of products, as evidenced by its large equilibrium constant.
By combining the two equations given, we can calculate the overall equilibrium constant, K, for the reaction
and then calculate the concentration of X2 in an equilibrium mixture where [H2X]eq = 0.1 M and [HCl]eq =
[H3O+]eq = 0.3 M.
Analyze
When we add equations, the overall equilibrium constant is the product of the individual equilibrium constants.
From the overall reaction we can write the equilibrium constant expression and from that solve for [X2] at
equilibrium.
Solve
H 2 X(aq) + H 2O() HX (aq) + H 3O + (aq)
K1 = 8.3 10 8
HX (aq) + H 2O() X 2 (aq) + H 3O + (aq)
K 2 = 1 10 14
H 2 X(aq) + 2 H 2O() X 2 (aq) + 2 H 3O + (aq)
X 2 H 3 O +
Kc =
[ H2X]
K 3 = K1 K 2 = 8.3 10 22
2
We know that Kc = 8.3 1022, [H3O+] = 0.3 M, and [H2X] = 0.1 M for the saturated solution. Rearranging the
equilibrium constant expression and solving for [X2] gives
K c [ H 2 X ] 8.3 1022 0.1
2
=
= 9 1022 M
2
X =
+ 2
(0.3)
H3O
Think about It
Our answer makes sense because with a very small overall equilibrium constant, we expect a very small
concentration of product, X2.
For the reaction
NO 2 (g) + SO 2 (g) NO(g) + SO3 (g)

we are given the equilibrium concentrations, from which we can calculate Kc. We are to calculate the
concentrations of all species in the reaction mixture at a new equilibrium after the concentration of SO3 is
increased.
Analyze
The Kc expression for this reaction is
[NO][SO3 ]
(2.00)(0.600)
=
= 40.0
[NO2 ][SO2 ] (0.100)(0.300)
We set up a RICE table where the concentration of SO2 is increased from the first equilibrium value of
0.300 M to 0.800 M.
Kc =
172 | Chapter 14
Solve
Reaction
Initial
Change
Equilibrium
NO2(g)
[NO2]
0.100 M
x
0.100 x
SO2(g)
[SO2]
0.800 M
x
0.800 x
NO(g)
[NO]
2.00 M
+x
2.00 + x
SO3(g)
[SO3]
0.600 M
+x
0.600 + x
The direction of change is predicted by Le Chteliers principle: we increase the concentration of a reactant and
the equilibrium shifts to the right. To solve for x we must expand and solve by the quadratic equation:
(2.00 + x)(0.600 + x)
(1.20 + 2.60 x + x 2 )
40.0 =
=
(0.100 x)(0.800 x) (0.0800 0.900 x + x 2 )
39.0 x 2 38.6 x + 2.00 = 0

x = 0.935 or 0.0549
When x = 0.935, the concentrations of NO2 and SO2 will be negative, so x = 0.0549. The concentrations at
equilibrium are
[NO2] = 0.100 x = 0.045 M
[SO2] = 0.800 x = 0.745 M
[NO] = 2.00 + x = 2.05 M
[SO3] = 0.600 + x = 0.655 M
Think about It
To check our answer, we can substitute these concentrations into the Kc expression:
(2.05)(0.655)
= 40
(0.745)(0.045)

For the reaction of CH4 with S8 to form CS2 and H2, we are to calculate the value of the equilibrium constant by
GE;@9F:7D?A6K@3?;563F38DA?BB7@6;J8ADF:7D735F;A@3F4AF:U3@6
U
Analyze
We have to calculate the value of Kp from G at 5
U+A6AEAI7?GEF8;DEF67F7D?;@7HU3@6SU8DA?
tabulated values in Appendix 4:
HU1 115.3) + (8 0.0)] [(4 74.8) (1 0.0)] = 760.4 kJ
SU1 237.8) + (8 130.6)] [(4 186.2) (1 32.1)] = 1219 J/K
We can then calculate the value of GU and G
U through
GU = HU TSU
=" (298 K 1.219 kJ/K) = 397.1 kJ
G
U = HU TSU
=" (773 K 1.219 kJ/K) = 181.9 kJ
The value of Kp for each temperature is calculated though the value of GU:
G
ln K p =
RT
Solve
FU#:
ln K p =
397.1 kJ/mol
= 160.3
8.314 103 kJ
298 K
mol K
K p = e 160.3 = 2.47 1070

F
U #:
ln K p =
181.9 kJ/mol
= 28.30
8.314 103 kJ
773
K
mol K
K p = e28.30 = 1.96 1012

Think about It
This reaction changed its spontaneity upon heating because it is an endothermic reaction with a favorable
entropy change.
Given that Kc is 1.0 105 3FU8ADF:7D735F;A@5A@H7DF;@9'3@6
the value of Grxn

and predict the sign of Hrxn .
2O
to CO2 and H2, we are to calculate
Analyze
We can calculate GU8DA?Kc by using
G = RT ln K c
To figure out the sign of HU, we can qualitatively examine first whether entropy is expected to increase or
decrease for this reaction. We then can guess the sign of the enthalpy change for the reaction.
Solve
8.314 J
298 K ln(1.0 105 ) = 29 kJ/mol
mol K
The entropy of the reaction changes very little since the number of moles of gaseous products equals the
number of moles of gaseous reactants. Therefore, SU 0, so the sign of HU;E7JB75F76FA47@793F;H7E;@57
G = H T S .
Grxn
=
Think about It
This reaction is spontaneous largely because it is exothermic. Because SU 0, Grxn

29 kJ/mol.
Given GU 418.6 kJ for the reaction in which CaO reacts with SO2 in the presence of O2 to form solid
CaSO4, we can calculate K and then determine the PSO2 in this reaction when the partial pressure of oxygen is
0.21 atm.
Analyze
To calculate K from GU, we use
ln K =
The equilibrium constant expression for the reaction is
Kp =
ln K =
( P )( P )
1/ 2
SO2
Solve
G
RT
O2
418.6 kJ/mol
= 168.956
8.314 103 kJ/mol K 298K
K = e168.956 = 2.38 1073
174 | Chapter 14
2.38 1073 =
1
PSO2 (0.21)1/ 2
PSO2 = 9.2 1074 atm

Think about It
Essentially, all the SO2 is scrubbed by the CaO in this reaction, making this an efficient method to remove
SO2 from exhaust gases.
For the reaction
2 SO 2 (g) + O 2 (g) 2 SO3 (g)

we are to calculate Kp 3F
U3@68;@6F:7D3F;AA8 PSO / PSO when PO at equilibrium is 0.21 atm.

2
3
2
Analyze
First we have to calculate the value of Kc from G 3F
U+A6AEAI7?GEF8;DEF67F7D?;@7HU3@6SU
from tabulated values in Appendix 4:
HU 395.7) [(2 296.8) + (1 0)] = 197.8 kJ
SU 256.8) [(2 248.2) + (1 205.0)] = 187.8 J/K
G
U = HU TSU197.8 kJ (973 K 0.1878 kJ/K) = 15.07 kJ

From G, we can calculate Kc:
G
U = RT ln Kc
or
ln Kc = G
U/(RT)
15.07 kJ/mol
ln Kc =
= 1.863
8.314 103 kJ
973 K
mol K
Kc = e1.863 = 6.443
We can calculate Kp from Kc by using
Kp = Kc(RT)n
where n = 1 for this reaction.
Solve
Kp =
6.443
= 0.0807
L atm
973
0.08206
mol K
At equilibrium
(P )
=
(P ) (P )
2
Kp
SO3
2
SO 2
Rearranging for the ratio PSO /PSO gives

2
3
PSO2
PSO3
1
K p PO2
O2
1
0.0807 0.21
= 7.7
Think about It
This equilibrium favors the reactants, and so the ratio of the partial pressure of the reactant SO2 to the partial
pressure of the product SO3 is greater than 1.

Chem Ch14

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Chem Ch14

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CHAPTER 14 | Chemical Equilibrium: Equal but Opposite Reaction Rates

14.1. Collect and Organize

Chemical Equilibrium | 113

where y = ln Kc, x = 1/T, m = HU R, and b = SU R.

Chemical Equilibrium | 115

Chemical Equilibrium | 117

2 CO(g) + O 2 (g) 2 CO 2 (g)

CO is produced in the reaction mixture

the equilibrium constant is 1/0.333, or 3.00.

kf = 8.7 106 0.54 M1 s1 = 4.7 106 M1 s1

Chemical Equilibrium | 119

(0.00030 M )(0.00014 M )1/ 2

Chemical Equilibrium | 121

The equilibrium constant expression for this reaction is

( P )( P ) = (0.045 atm)(0.030 atm) = 0.068

( P ) ( P ) = (0.0045 atm) (0.0030 atm) = 3.8 10

Chemical Equilibrium | 123

CO(g) H2(g) + CO2(g)

At equilibrium, we know that [CO2] = x = 8.3 103 mol. This gives

[ H ][ CO ] = (8.3 10 mol)(8.3 10 mol) = 1.5

H2(g) + 2 NO(g) 2H2O(g) + N2(g)

At equilibrium, we know that [NO] = 0.161 M, so

Chemical Equilibrium | 125

where n is the change in the number of moles of gas in the reaction:

where n is the change in the number of moles of gas in the reaction:

n = (1 mol COCl2) (1 mol Cl2 + 1 mol CO) = 1

Chemical Equilibrium | 127

n = (1 mol NO + 1 mol SO3) (1 mol SO2 + 1 mol NO2) = 0

= (4.3 103 )1 2 = 6.6 102

Chemical Equilibrium | 129

N 2 (g) + 3 H 2 (g) 2 NH 3 (g)

at the same temperature.

Kp2 is, therefore, related to Kp1 by

SO 2 (g) + 14 O 2 (g) 12 SO3 (g)

2 NO(g) + 2 H 2 (g) N 2 (g) + 2 H 2O(g)

at a given temperature, we are to calculate Kc for

at the same temperature.

2 SO 2 (g) + O 2 (g) 2 SO3 (g)

Chemical Equilibrium | 131

2 NO(g) + O 2 (g) 2 NO 2 (g)

where K3 = K1 K2. The equilibrium constant for the reaction

where K3 = K1 K2. The equilibrium constant for the reaction

K = 1 (3.1104 2.8 102 )

Chemical Equilibrium | 133

Chemical Equilibrium | 135

(5 104 M )(5 104 M )

where for this reaction n = 1.

0.08206 mol K 300 K

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

where R = 0.8206 (L atm)/(mol K), T = 300 K, and n = 1 2 = 1.

0.08206 mol K ( 300 K )

Because n = 0 for this reaction, Kp = Kc = 1.5 10 .

Chemical Equilibrium | 137

The reaction quotient is

Chemical Equilibrium | 139

Therefore, the Kp expression has two partial pressure terms.

14.65. Collect and Organize

Chemical Equilibrium | 141

Chemical Equilibrium | 143

Chemical Equilibrium | 145

([X] x)([Y] x) ([X])([Y])

and the equilibrium constant expression would be

[B 2x]2 [C x] [B]2 [C]

PPCl = 0.500 + 0.536 = 1.036 atm

UI73D7FA53>5G>3F7 PCO and PCO at equilibrium for the reaction

U-73D7FA53>5G>3F7F:7B3DF;3>BD7EEGD7EA8&2, O2, and NO at equilibrium

the value of Kp is 6.5 10 3F

U-73D7FA53>5G>3F7F:7H3>G7A81'2 1'2] when [O2] at equilibrium is 0.0045 M.

U I7 3D7 FA 53>5G>3F7 F:7

U 3@6 F:7