Characteristics of Chemical Equilibrium

CHAPTER 6
CHEMICAL EQUILIBRIUM
Characteristics of Chemical Equilibrium
10.
a. The rates of the forward and reverse reactions are equal.

b. There is no net change in the composition (as long as temperature is constant).
11.
2 NOCl(g)
2 NO(g) + Cl2(g)
K = 1.6 105 mol/L
The expression for K is the product concentrations divided by the reactant concentrations.
When K has a value much less than one, the product concentrations are relatively small, and
the reactant concentrations are relatively large.
2 NO(g) N2(g) + O2(g) K = 1 1031
When K has a value much greater than one, the product concentrations are relatively large,
and the reactant concentrations are relatively small. In both cases, however, the rate of the
forward reaction equals the rate of the reverse reaction at equilibrium (this is a definition of
equilibrium).
12.
No, equilibrium is a dynamic process. Both reactions:

H2O + CO H2 + CO2 and H2 + CO2 H2O + CO
are occurring at equal rates. Thus 14C atoms will be distributed between CO and CO2.
13.
No, it doesn't matter which direction the equilibrium position is reached. Both experiments
will give the same equilibrium position because both experiments started with stoichiometric
amounts of reactants or products.
14.
H2O(g) + CO(g)
H2(g) + CO2(g)
K=
[H 2 ][CO 2 ]
= 2.0
[H 2 O][CO]
K is a unitless number because there is an equal number of moles of product gases as moles
of reactant gases in the balanced equation. Therefore, we can use units of molecules per liter
instead of moles per liter to determine K.
149
150
CHAPTER 6
We need to start somewhere, so lets assume 3 molecules of CO react. If 3 molecules of CO

react, then 3 molecules of H2O must react, and 3 molecules each of H2 and CO2 are formed.
We would have 6 ! 3 = 3 molecules of CO, 8 ! 3 = 5 molecules of H2O, 0 + 3 = 3 molecules
of H2, and 0 + 3 = 3 molecules of CO2 present. This will be an equilibrium mixture if K = 2.0:
3 molecules H 2 3 molecules CO 2
L
L
= 3
K=
5
5 molecules H 2 O 3 molecules CO
L
L
Because this mixture does not give a value of K = 2.0, this is not an equilibrium mixture.
Lets try 4 molecules of CO reacting to reach equilibrium.
Molecules CO remaining = 6 ! 4 = 2 molecules of CO
Molecules H2O remaining = 8 ! 4 = 4 molecules of H2O
Molecules H2 present = 0 + 4 = 4 molecules of H2
Molecules CO2 present = 0 + 4 = 4 molecules of CO2
4 molecules H 2 4 molecules CO 2
L
L
= 2 .0
K=
4 molecules H 2 O 2 molecules CO
L
L
Because K = 2.0 for this reaction mixture, we are at equilibrium.

15.
When equilibrium is reached, there is no net change in the amount of reactants and products
present because the rates of the forward and reverse reactions are equal to each other. The
first diagram has 4 A2B molecules, 2 A2 molecules, and 1 B2 molecule present. The second
diagram has 2 A2B molecules, 4 A2 molecules, and 2 B2 molecules. Therefore, the first
diagram cannot represent equilibrium because there was a net change in reactants and
products. Is the second diagram the equilibrium mixture? That depends on whether there is a
net change between reactants and products when going from the second diagram to the third
diagram. The third diagram contains the same number and type of molecules as the second
diagram, so the second diagram is the first illustration that represents equilibrium.
The reaction container initially contained only A2B. From the first diagram, 2 A2 molecules
and 1 B2 molecule are present (along with 4 A2B molecules). From the balanced reaction,
these 2 A2 molecules and 1 B2 molecule were formed when 2 A2B molecules decomposed.
Therefore, the initial number of A2B molecules present equals 4 + 2 = 6 molecules A2B.
The Equilibrium Constant

16.
The equilibrium constant is a number that tells us the relative concentrations (pressures) of
reactants and products at equilibrium. An equilibrium position is a set of concentrations that
satisfies the equilibrium constant expression. More than one equilibrium position can satisfy
the same equilibrium constant expression.
CHAPTER 6
151
Table 6.1 of the text illustrates this nicely. Each of the three experiments in Table 6.1 has
different equilibrium positions; that is, each experiment has different equilibrium
concentrations. However, when these equilibrium concentrations are inserted into the
equilibrium constant expression, each experiment gives the same value for K. The
equilibrium position depends on the initial concentrations one starts with. Since there are an
infinite number of initial conditions, there are an infinite number of equilibrium positions.
However, each of these infinite equilibrium positions will always give the same value for the
equilibrium constant (assuming temperature is constant).
17.
K and Kp are equilibrium constants as determined by the law of mass action. For K,
concentration units of mol/L are used, and for Kp, partial pressures in units of atm are used
(generally). Q is called the reaction quotient. Q has the exact same form as K or Kp, but
instead of equilibrium concentrations, initial concentrations are used to calculate the Q value.
We use Q to determine if a reaction is at equilibrium. When Q = K (or when Qp = Kp), the
reaction is at equilibrium. When Q K, the reaction is not at equilibrium, and one can deduce
the net change that must occur for the system to get to equilibrium.
18.
When reactants and products are all in the same phase, these are homogeneous equilibria.
Heterogeneous equilibria involve more than one phase. In general, for a homogeneous gasphase equilibrium, all reactants and products are included in the K expression. In
heterogeneous equilibria, equilibrium does not depend on the amounts of pure solids or
liquids present. The amounts of solids and liquids present are not included in K expressions;
they just have to be present. On the other hand, gases and solutes are always included in K
expressions. Solutes have (aq) written after them.
19.
Solids and liquids do not appear in equilibrium expressions. Only gases and dissolved solutes
appear in equilibrium expressions.
a. K =
PH 2O
[ H 2 O]
; Kp = 2
2
[ NH 3 ] [CO 2 ]
PNH 3 PCO 2
c. K = [O2]3; Kp = PO3 2
3
b. K = [N2][Br2]3; Kp = PN 2 PBr
2
d. K =
PH 2O
[ H 2 O]
; Kp =
[H 2 ]
PH 2
20.
Kp = K(RT)n, where n equals the difference in the sum of the coefficients between gaseous
products and gaseous reactants (n = mol gaseous products ! mol gaseous reactants). When
n = 0, then Kp = K. In Exercise 19, only reaction d has n = 0, so only reaction d has Kp =
K.
21.
Kp = K(RT)n, where n = sum of gaseous product coefficients ! sum of gaseous reactant

coefficients. For this reaction, n = 3 ! 1 = 2.
K=
[CO][H 2 ]2
(0.24)(1.1) 2
=
= 1.9 mol2/L2
(0.15)
[CH 3OH]
Kp = K(RT)2 = 1.9(0.08206 L atm K1 mol1 600. K)2 = 4.6 103 atm2
152
22.
CHAPTER 6
H2(g) + Br2(g) 2 HBr(g)
Kp =
a. HBr 1/2 H2 + 1/2 Br2
K 'p
2
PHBr
= 3.5 104
( PH 2 ) ( PBr2 )
(PH 2 )1/ 2 (PBr2 )1/ 2

PHBr
1/ 2
=
Kp
1/ 2
=
4
3
.
5
10
= 5.3 103
b. 2 HBr H2 + Br2
K 'p' =
c. 1/2 H2 + 1/2 Br2 HBr
23.
[N2O] =
(PH 2 )(PBr2 )
2
PHBr
K 'p'' =
1
1
=
= 2.9 105
4
Kp
3.5 10
PHBr
1/ 2
(PH 2 )
(PBr2 )1/ 2
= (K p )1/ 2 = 190
2.00 10 2 mol
2.80 10 4 mol
2.50 10 5 mol
; [N2] =
; [O2] =
2.00 L
2.00 L
2.00 L
2
2.00 10 2
2.00
[ N 2 O ]2
(1.00 10 2 ) 2
K=
=
=
[ N 2 ]2 [O 2 ] 2.80 10 4 2 2.50 10 5
(1.40 10 4 ) 2 (1.25 10 5 )
2.00
2.00
= 4.08 108 L/mol

If the given concentrations represent equilibrium concentrations, then they should give a
value of K = 4.08 108.
(0.200) 2
= 4.08 108
(2.00 10 4 ) 2 (0.00245)
Because the given concentrations when plugged into the equilibrium constant expression give
a value equal to K (4.08 108), this set of concentrations is a system at equilibrium
24.
Kp =
2
PNH
3
PN 2 PH3 2
(3.1 10 2 ) 2
= 3.8 104 atm2
(0.85)(3.1 10 3 ) 3
(0.167) 2
= 1.21 103
3
(0.525) (0.00761)
When the given partial pressures in atmospheres are plugged into the Kp expression, the value
does not equal the Kp value of 3.8 104. Therefore, one can conclude that the given set of
partial pressures does not represent a system at equilibrium.
CHAPTER 6
25.
Kp =
PH4 2
PH4 2O
153
; Ptotal = PH 2O + PH 2 , 36.3 torr = 15.0 torr + PH 2 , PH 2 = 21.3 torr

4
1 atm
21.3 torr
760 torr
Because l atm = 760 torr: Kp =

= 4.07
4
1 atm
15.0 torr
760 torr
Note: Solids and pure liquids are not included in K expressions.
26.
N2(g) + 3 H2(g) 2 NH3(g); with only reactants present initially, the net change that must
occur to reach equilibrium is a conversion of reactants into products. At constant volume and
temperature, n P. Thus if x atm of N2 reacts to reach equilibrium, then 3x atm of H2 must
also react to form 2x atm of NH3 (from the balanced equation). Lets summarize the problem
in a table that lists what is present initially, what change in terms of x that occurs to reach
equilibrium, and what is present at equilibrium (initial + change). This table is typically
called an ICE table for initial, change, and equilibrium.
2
PNH
3
N2(g)
+ 3 H2(g) 2 NH3(g)
Kp =
PN 2 PH3 2
Initial
Change
Equil.
1.00 atm
2.00 atm
0
x atm of N2 reacts to reach equilibrium
!x
!3 x
+2x
2.00 ! 3x
2x
1.00 ! x
From the setup: Ptotal = 2.00 atm = PN 2 + PH 2 + PNH 3

2.00 atm = (1.00 x) + (2.00 3x) + 2x = 3.00 2x, x = 0.500 atm
PH 2 = 2.00 3x = 2.00 3(0.500) = 0.50 atm
Kp =
27.
(1.00) 2
(2 x) 2
[2(0.500)]2
= 16 atm2
=
=
(1.00 x)(2.00 3 x) 3
(1.00 0.500)[2.00 3(0.500)]3
(0.50)(0.50) 3
PCl5(g) PCl3(g) + Cl2(g)
Kp =
PPCl3 PCl 2
PPCl5
To determine Kp, we must determine the equilibrium partial pressures of each gas. Initially,
PPCl5 = 0.50 atm and PPCl3 = PCl 2 = 0 atm. To reach equilibrium, some of the PCl5 reacts to
produce some PCl3 and Cl2, all in a 1 : 1 mole ratio. We must determine the change in partial
pressures necessary to reach equilibrium. Because moles % P at constant V and T, if we let x
= atm of PCl5 that reacts to reach equilibrium, this will produce x atm of PCl3 and x atm of
Cl2 at equilibrium. The equilibrium partial pressures of each gas will be the initial partial
pressure of each gas plus the change necessary to reach equilibrium. The equilibrium partial
pressures are:
154
CHAPTER 6
PPCl5 = 0.50 atm x, PPCl3 = PCl 2 = x

Now we solve for x using the information in the problem:
Ptotal = PPCl5 + PPCl3 + PCl 2 , 0.84 atm = 0.50 x + x + x, 0.84 atm = 0.50 + x,
x = 0.34 atm
The equilibrium partial pressures are:
PPCl 5 = 0.50 0.34 = 0.16 atm, PPCl 3 = PCl 2 = 0.34 atm
Kp =
K=
28.
PPCl 3 PCl 2
PPCl 5
Kp
(RT )
(0.34)(0.34)
= 0.72 atm
(0.16)
, n = 2 1 = 1; K p =
S8(g) 4 S2(g)
Kp =
0.72
= 0.017 mol/L
(0.08206)(523)
PS42
PS8
Initially: PS8 = 1.00 atm and PS2 = 0 atm

Change: Because 0.25 atm of S8 remain at equilibrium, 1.00 atm 0.25 atm = 0.75 atm of S8
must have reacted in order to reach equilibrium. Because there is a 4 : 1 mole ratio between
S2 and S8 (from the balanced reaction), 4(0.75 atm) = 3.0 atm of S2 must have been produced
when the reaction went to equilibrium (moles and pressure are directly related at constant T
and V).
Equilibrium: PS8 = 0.25 atm, PS2 = 0 + 3.0 atm = 3.0 atm; Solving for Kp:
Kp =
29.
(3.0) 4
= 3.2 102 atm3
0.25
When solving equilibrium problems, a common method to summarize all the information in
the problem is to set up a table. We commonly call this table an ICE table because it
summarizes initial concentrations, changes that must occur to reach equilibrium, and
equilibrium concentrations (the sum of the initial and change columns). For the change
column, we will generally use the variable x, which will be defined as the amount of reactant
(or product) that must react to reach equilibrium. In this problem, the reaction must shift
right to reach equilibrium because there are no products present initially. Therefore, x is
defined as the amount of reactant SO3 that reacts to reach equilibrium, and we use the
coefficients in the balanced equation to relate the net change in SO3 to the net change in SO2
and O2. The general ICE table for this problem is:
CHAPTER 6
2 SO3(g)
Initial
Change
Equil.
2 SO2(g)
155
+
O2(g)
K=
[SO 2 ]2 [O 2 ]
[SO 3 ]2
12.0 mol/3.0 L
0
0
Let x mol/L of SO3 react to reach equilibrium.
x
+x
+x/2
4.0 x
x
x/2
From the problem, we are told that the equilibrium SO2 concentration is 3.0 mol/3.0 L =
1.0 M ([SO2]e = 1.0 M). From the ICE table setup, [SO2]e = x, so x = 1.0. Solving for the
other equilibrium concentrations: [SO3]e = 4.0 x = 4.0 1.0 = 3.0 M; [O2] = x/2 = 1.0/2 =
0.50 M.
K=
[SO 2 ]2 [O 2 ]
(1.0 M ) 2 (0.50 M )
= 0.056 mol/L
=
[SO 3 ]2
(3.0 M ) 2
Alternate method: Fractions in the change column can be avoided (if you want) be defining x
differently. If we were to let 2x mol/L of SO3 react to reach equilibrium, then the ICE table
setup is:
[SO 2 ]2 [O 2 ]
O2(g)
K=
2 SO3(g) 2 SO2(g) +
[SO 3 ]2
Initial
Change
Equil.
0
0
4.0 M
Let 2x mol/L of SO3 react to reach equilibrium.
2x
+2x
+x
4.0 2x
2x
x
Solving: 2x = [SO2]e = 1.0 M, x = 0.50 M; [SO3]e = 4.0 2(0.50) = 3.0 M; [O2]e = x

= 0.50 M
These are exactly the same equilibrium concentrations as solved for previously, thus K will
be the same (as it must be). The moral of the story is to define x in a manner that is most
comfortable for you. Your final answer is independent of how you define x initially.
Equilibrium Calculations
30.
2 NO(g) N2(g) + O2(g) K =
[ N 2 ][O 2 ]
= 2.4 103; Because n = 0, K = Kp.
[ NO]2
Use the reaction quotient Q to determine which way the reaction shifts to reach equilibrium.
For the reaction quotient, initial concentrations given in a problem are used to calculate the
value for Q. If Q < K, then the reaction shifts right to reach equilibrium. If Q > K, then the
reaction shifts left to reach equilibrium. If Q = K, then the reaction does not shift in either
direction because the reaction is at equilibrium.
156
CHAPTER 6
a. [N2] =
Q=
2.0 mol
2.6 mol
0.024 mol
= 2.0 M; [O2] =
= 2.6 M; [NO] =
= 0.024 M
1.0 L
1.0 L
1.0 L
[ N 2 ]0 [ O 2 ]0
(2.0 M ) (2.6 M )
=
= 9.0 103
2
[ NO]0
(0.024 M ) 2
Q > K, so the reaction shifts left to produce more reactants in order to reach equilibrium.
b. [N2] =
Q=
(0.31 M ) (2.0 M )
= 2.4 103 = K; at equilibrium
2
(0.016 M )
c. [N2] =
Q=
d. Q =
0.62 mol
4.0 mol
0.032 mol
= 0.31 M; [O2] =
= 2.0 M; [NO] =
= 0.016 M
2.0 L
2.0 L
2.0 L
2.4 mol
1.7 mol
0.060 mol
= 0.80 M; [O2] =
= 0.57 M; [NO] =
= 0.020 M
3 .0 L
3.0 L
3 .0 L
(0.80 M )(0.57 M )
= 1.1 103 < K; reaction shifts right to reach equilibrium.
(0.020 M ) 2
PN 2 PO 2
2
PNO
(0.11 atm)(2.0 atm)

= 2.2 103
(0.010 atm) 2
Q < Kp (2.4 103), so the reaction shifts right to reach equilibrium.
31.
e. Q =
(0.36 atm)(0.67 atm)

= 4.0 103 > Kp; reaction shifts left to reach equilibrium.
(0.0078 atm) 2
f.
(0.51 atm)(0.18 atm)

= 2.4 103 = Kp; at equilbrium
(0.0062 atm) 2
Q=
CaCO3(s) CaO(s) + CO2(g)
Kp = PCO 2 = 1.04 atm
We only need to calculate the initial partial pressure of CO2 and compare this value to 1.04
atm. At this temperature, all CO2 will be in the gas phase.
a. PV = nRT, Q = PCO 2 =
n CO 2 RT
V
58.4 g CO 2
0.08206 L atm
1173 K
44.01 g/mol
K mol
=
=
50.0 L
2.55 atm > Kp
Reaction will shift to the left because Q > Kp; the mass of CaO will decrease.
CHAPTER 6
b. Q = PCO 2 =
157
(23.76) (0.08206)(1173)
= 1.04 atm = Kp
(44.01)(50.0)
At equilibrium because Q = Kp; mass of CaO will not change.

c. Mass of CO2 is the same as in part b. P = 1.04 atm = KP. At equilibrium; mass of CaO
will not change.
d. Q = PCO 2 =
(4.82) (0.08206)(1173)
= 0.211 atm < Kp
(44.01)(50.0)
Reaction will shift to the right because Q < Kp; the mass of CaO will increase.
32.
Q = 1.00, which is less than K. The reaction shifts to the right to reach equilibrium.
Summarizing the equilibrium problem in a table:
SO2(g)
Initial
Change
Equil.
NO2(g)
SO3(g)
+ NO(g)
K = 3.75
0.800 M
0.800 M
0.800 M
0.800 M
x mol/L of SO2 reacts to reach equilibrium
!x
!x
+x
+x
0.800 ! x
0.800 + x 0.800 + x
0.800 ! x
Plug the equilibrium concentrations into the equilibrium constant expression:

K=
[SO 3 ][ NO]
(0.800 + x) 2
, 3.75 =
; take the square root of both sides and solve
[SO 2 ][ NO 2 ]
(0.800 x) 2 for x:
0.800 + x
= 1.94, 0.800 + x = 1.55 ! (1.94)x, (2.94)x = 0.75, x = 0.26 M
0.800 x
The equilibrium concentrations are:

[SO3] = [NO] = 0.800 + x = 0.800 + 0.26 = 1.06 M; [SO2] = [NO2] = 0.800 ! x = 0.54 M
33.
H2O(g) + Cl2O(g) 2 HOCl(g)
K = 0.090 =
[HOCl]2
[H 2 O][Cl 2 O]
a. The initial concentrations of H2O and Cl2O are:

1.0 g H 2 O 1 mol
= 5.6 102 mol/L;

1 .0 L
18.0 g
2.0 g Cl 2 O 1 mol
= 2.3 102 mol/L

1 .0 L
86.9 g
Because only reactants are present initially, the reaction must proceed to the right to
reach equilibrium. Summarizing the problem in a table:
158
CHAPTER 6
H2O(g)
Cl2O(g)
2 HOCl(g)
5.6 102 M
2.3 102 M
0
x mol/L of H2O reacts to reach equilibrium
x
x
+2x
2.3 102 x
2x
5.6 102 x
Initial
Change
Equil.
K = 0.090 =
(5.6 10 2
(2 x) 2
x)(2.3 10 2 x)
1.16 104 (7.11 103)x + (0.090)x2 = 4x2

(3.91)x2 + (7.11 103)x 1.16 104 = 0 (We carried extra significant figures.)
Solving using the quadratic formula (see Appendix 1 of the text):
x=
7.11 10 3 (5.06 10 5 + 1.81 10 3 )1/ 2

= 4.6 103 M or 6.4 103 M
7.82
A negative answer makes no physical sense; we can't have less than nothing. Thus x =
4.6 103 M.
[HOCl] = 2x = 9.2 103 M; [Cl2O] = 2.3 102 x = 0.023 0.0046 = 1.8 102 M
[H2O] = 5.6 102 x = 0.056 0.0046 = 5.1 102 M
b.
H2O(g)
Cl2O(g)
2 HOCl(g)
0
0
1.0 mol/2.0 L = 0.50 M
2x mol/L of HOCl reacts to reach equilibrium
+x
2x
+x
x
x
0.50 2x
Initial
Change
Equil.
K = 0.090 =
[HOCl]2
(0.50 2 x) 2
=
[H 2 O][Cl 2 O]
x2
The expression is a perfect square, so we can take the square root of each side:
0.30 =
0.50 2 x
, (0.30)x = 0.50 2x, (2.30)x = 0.50
x
x = 0.217 M (We carried extra significant figures.)

x = [H2O] = [Cl2O] = 0.217 = 0.22 M; [HOCl] = 0.50 2x = 0.50 0.434 = 0.07 M
CHAPTER 6
34.
K=
159
[ HF]2
(0.400 M ) 2
=
= 320.; 0.200 mol F2/5.00 L = 0.0400 M F2 added
[H 2 ][F2 ]
(0.0500 M )(0.0100 M )
After F2 has been added, the concentrations of species present are [HF] = 0.400 M, [H2] = [F2]
= 0.0500 M. Q = (0.400)2/(0.0500)2 = 64.0; because Q < K, the reaction will shift right to
reestablish equilibrium.
H2(g)
Initial
Change
Equil.
K = 320. =
17.9 =
F2(g)
2 HF(g)
0.0500 M
0.400 M
0.0500 M
x mol/L of F2 reacts to reach equilibrium
x
x
+2x
0.0500 x
0.0500 x
0.400 + 2x
(0.400 + 2 x) 2
; taking the square root of each side:
(0.0500 x) 2
0.400 + 2 x
, 0.895 (17.9)x = 0.400 + 2x, (19.9)x = 0.495, x = 0.0249 mol/L
0.0500 x
[HF] = 0.400 + 2(0.0249) = 0.450 M; [H2] = [F2] = 0.0500 0.0249 = 0.0251 M

35.
2 SO2(g)
Initial
Change
Equil.
Kp = 0.25 =
O2(g)
2 SO3(g)
Kp = 0.25
0.50 atm
0.50 atm
0
2x atm of SO2 reacts to reach equilibrium
2x
x
+2x
0.50 x
2x
0.50 2x
2
PSO
3
2
PSO
PO 2
2
(2 x) 2
(0.50 2 x) 2 (0.50 x)
This will give a cubic equation. Graphing calculators can be used to solve this expression.
If you dont have a graphing calculator, an alternative method for solving a cubic equation is
to use the method of successive approximations (see Appendix 1 of the text). The first step is
to guess a value for x. Because the value of K is small (K < 1), not much of the forward
reaction will occur to reach equilibrium. This tells us that x is small. Lets guess that x =
0.050 atm. Now we take this estimated value for x and substitute it into the equation
everywhere that x appears except for one. For equilibrium problems, we will substitute the
estimated value for x into the denominator, and then solve for the numerator value of x. We
continue this process until the estimated value of x and the calculated value of x converge on
the same number. This is the same answer we would get if we were to solve the cubic
equation exactly. Applying the method of successive approximations and carrying extra
significant figures:
4x2
4x2
=
= 0.25 , x = 0.067
[0.50 2(0.050)]2 [0.50 (0.050)] (0.40) 2 (0.45)
160
CHAPTER 6
4x2
4x2
=
= 0.25 , x = 0.060
[0.50 2(0.067)]2 [0.50 (0.067)]
(0.366) 2 (0.433)
4x2
4x2
=
0.25,
x
=
0.063;
= 0.25,
(0.38) 2 (0.44)
(0.374) 2 (0.437)
x = 0.062
The next trial gives the same value for x = 0.062 atm. We are done except for determining
the equilibrium concentrations. They are:
PSO 2 = 0.50 2x = 0.50 2(0.062) = 0.376 = 0.38 atm
PO 2 = 0.50 x = 0.438 = 0.44 atm; PSO 3 = 2x = 0.124 = 0.12 atm
36.
Because only reactants are present initially, the reaction must proceed to the right to reach
equilibrium. Summarizing the problem in a table:
N2(g)
Initial
Change
Equil.
Kp = 0.050 =
O2(g)
2 NO(g)
Kp = 0.050
0.80 atm
0.20 atm
0
x atm of N2 reacts to reach equilibrium
x
x
+2x
0.20 x
2x
0.80 x
2
PNO
(2 x) 2
=
, 0.050[0.16 (1.00)x + x2] = 4x2
(0.80 x)(0.20 x)
PN 2 PO 2
4x2 = 8.0 103 (0.050)x + (0.050)x2, (3.95)x2 + (0.050)x 8.0 103 = 0

Solving using the quadratic formula (see Appendix 1 of the text):
x=
b (b 2 4ac)1/ 2
0.050 [(0.050)]2 4(3.95)(8.0 10 3 )]1/ 2
=
2a
2(3.95)
x = 3.9 102 atm or x = 5.2 102 atm; only x = 3.9 102 atm makes sense (x cannot
be negative), so the equilibrium NO concentration is:
PNO = 2x = 2(3.9 102 atm) = 7.8 102 atm

37.
The assumption comes from the value of K being much less than 1. For these reactions, the
equilibrium mixture will not have a lot of products present; mostly reactants are present at
equilibrium. If we define the change that must occur in terms of x as the amount (molarity or
partial pressure) of a reactant that must react to reach equilibrium, then x must be a small
number because K is a very small number. We want to know the value of x in order to solve
the problem, so we dont assume x = 0. Instead, we concentrate on the equilibrium row in the
ICE table. Those reactants (or products) that have equilibrium concentrations in the form of
0.10 x or 0.25 + x or 3.5 3x, etc., is where an important assumption can be made. The
CHAPTER 6
161
assumption is that because K << 1, x will be small (x << 1), and when we add x or subtract x
from some initial concentration, it will make little or no difference. That is, we assume that
0.10 x 0.10 or 0.25 + x 0.25 or 3.5 3x 3.5, etc.; we assume that the initial
concentration of a substance is equal to the final concentration. This assumption makes the
math much easier and usually gives a value of x that is well within 5% of the true value of x
(we get about the same answer with a lot less work).
We check the assumptions for validity using the 5% rule. From doing a lot of these
calculations, it is found that when an assumption such as 0.20 x 0.20 is made, if x is less
than 5% of the number the assumption was made against, then our final answer is within
acceptable error limits of the true value of x (as determined when the equation is solved
exactly). For our example above (0.20 x 0.20), if (x/0.20) 100 5%, then our
assumption is valid by the 5% rule. If the error is greater than 5%, then we must solve the
equation exactly or use a math trick called the method of successive approximations. See
Appendix 1 for details regarding the method of successive approximations, as well as for a
review in solving quadratic equations exactly.
38.
a. The reaction must proceed to products to reach equilibrium because only reactants are
present initially. Summarizing the problem in a table:
2 NOCl(g)
Initial
Change
Equil.
2 NO(g) +
Cl2(g)
K = 1.6 105
2.0 mol
0
0
= 1.0 M
2.0 L
2x mol/L of NOCl reacts to reach equilibrium
2x
+2x
+x
1.0 2x
2x
x
5
K = 1.6 10 =
[ NO]2 [Cl 2 ]
[ NOCl]2
(2 x) 2 ( x)
(1.0 2 x) 2
If we assume that 1.0 2x 1.0 (from the small size of K, we know that the product
concentrations will be small, so x will be small), then:
1.6 105 =
4x 3
, x = 1.6 102 M; now we must check the assumption.
1 .0 2
1.0 2x = 1.0 2(0.016) = 0.97 = 1.0 (to proper significant figures)

Our error is about 3%, that is, 2x is 3.2% of 1.0 M. Generally, if the error we introduce
by making simplifying assumptions is less than 5%, we go no further, the assumption is
said to be valid. We call this the 5% rule. Solving for the equilibrium concentrations:
[NO] = 2x = 0.032 M; [Cl2] = x = 0.016 M; [NOCl] = 1.0 2x = 0.97 M 1.0 M
Note: If we were to solve this cubic equation exactly (a longer process), we get x =
0.016. This is the exact same answer we determined by making a simplifying
assumption. We saved time and energy. Whenever K is a very small value, always make
162
CHAPTER 6
the assumption that x is small. If the assumption introduces an error of less than 5%, then
the answer you calculated making the assumption will be considered the correct answer.
b. There is a little trick we can use to solve this problem in order to avoid solving a cubic
equation. Because K for this reaction is very small (K << 1), the reaction will contain
mostly reactants at equilibrium (the equilibrium position lies far to the left). We will let
the products react to completion by the reverse reaction, and then we will solve the
forward equilibrium problem to determine the equilibrium concentrations. Summarizing
these steps in a table:
2 NOCl(g)
Before
Change
After
Change
Equil.
2 NO(g) +
Cl2(g)
K = 1.6 105
1.0 M
0
2.0 M
(K is small, reactants dominate.)
Let 1.0 mol/L Cl2 react completely.
+2.0
2.0
1.0
React completely
2.0
0
0
New initial conditions
2x mol/L of NOCl reacts to reach equilibrium
2x
+2x
+x
2.0 2x
2x
x
K = 1.6 105 =
(2 x) 2 ( x)
4x3
( 2.0 2 x) 2 2.0 2
(assuming 2.0 2x 2.0)
x3 = 1.6 105, x = 2.5 102 M; assumption good by the 5% rule (2x is 2.5% of 2.0).
[NOCl] = 2.0 0.050 = 1.95 M = 2.0 M; [NO] = 0.050 M; [Cl2] = 0.025 M

Note: If we do not break this problem into two parts (a stoichiometric part and an
equilibrium part), then we are faced with solving a cubic equation. The setup would be:
Initial
Change
Equil.
1.6 105 =
2 NOCl
2 NO
0
+2y
2y
2.0 M
2y
2.0 2y
Cl2
1.0 M
y
1.0 y
(2.0 2 y ) 2 (1.0 y )
(2 y ) 2
If we say that y is small to simplify the problem, then:

1.6 105 =
2 .0 2
; We get y = 250. This is impossible!
4y2
To solve this equation, we cannot make any simplifying assumptions; we have to find a
way to solve a cubic equation. Or we can use some chemical common sense and solve
the problem the easier way.
CHAPTER 6
c.
2 NOCl(g)
Initial
Change
Equil.
1.6 105 =
2 NO(g)
163
+
Cl2(g)
1.0 M
0
1.0 M
2x mol/L NOCl reacts to reach equilibrium
2x
+2x
+x
1.0 + 2x
x
1.0 2x
(1.0 + 2 x) 2 ( x) (1.0) 2 (x)
(1.0 2 x) 2
(2.0) 2
(assuming 2x << 1.0)
x = 1.6 105 M; Assumptions are great (2x is 3.2 103% of 1.0).
[Cl2] = 1.6 105 M and [NOCl] = [NO] = 1.0 M

d.
2 NOCl(g)
Before
Change
After
Change
Equil.
1.6 105 =
2 NO(g)
Cl2(g)
1.0 M
0
3.0 M
+2.0
2.0
1.0 React completely
2.0
1.0
0
New initial
2x
+2x
+x
1.0 + 2x
x
2.0 2x
x
(1.0 + 2 x) 2 ( x)
; solving: x = 6.4 105 M

2
4.0
(2.0 2 x)
Assumptions are great (2x is 1.3 102% of 1.0).

[Cl2] = 6.4 105 M; [NOCl] = 2.0 M; [NO] = 1.0 M
e.
2 NOCl(g)
Before
Change
After
Change
Equil.
1.6 105 =
2 NO(g)
Cl2(g)
2.0 M
1.0 M
2.0 M
+2.0
2.0
1.0
React completely
4.0
0
0
New initial
2x
+2x
+x
2x
x
4.0 2x
(2 x) 2 ( x)
4 x3
, x = 4.0 102 M; assumption good (2% error).

16
( 4 .0 2 x ) 2
[Cl2] = 0.040 M; [NO] = 0.080 M; [NOCl] = 4.0 2(0.040) = 3.92 M 3.9 M
164
CHAPTER 6
f.
2 NOCl(g)
2 NO(g)
Cl2(g)
1.00 M
1.00 M
1.00 M
Let 1.00 mol/L NO react completely (the limiting reagent).
+1.00
1.00
0.500 React completely
2.00
0
0.50
New initial
+2x
+x
2x
2.00 2x
2x
0.50 + x
Before
Change
After
Change
Equil.
K=
(2 x) 2 (0.50 + x) 4 x 2 (0.50)
= 1.6 105, x = 5.7 103 M

2
2
(2.00 2 x)
(2.00)
Assumptions are good (x is 1.1% of 0.50).

[NO] = 2x = 1.1 102 M; [Cl2] = 0.50 + 0.0057 = 0.51 M
[NOCl] = 2.00 2(0.0057) = 1.99 M
39.
2 CO2(g)
Initial
Change
Equil.
2 CO(g)
O2(g)
K=
[CO] 2 [O 2 ]
[CO 2 ] 2
= 2.0 106
2.0 mol/5.0 L
0
0
2x mol/L of CO2 reacts to reach equilibrium
2x
+2x
+x
2x
x
0.40 2x
K = 2.0 106 =
2.0 10-6
[CO] 2 [O 2 ]
[CO 2 ] 2
(2 x) 2 ( x)
; assuming 2x << 0.40 (K is small, so x is
(0.40 2 x) 2
small.)
4x3
4 x3
6
,
2
.0
10
=
, x = 4.3 103 M
2
0
.
16
(0.40)
Checking assumption:
2(4.3 10 3 )
100 = 2.2%; assumption is valid by the 5% rule.
0.40
[CO2] = 0.40 2x = 0.40 2(4.3 103) = 0.39 M

[CO] = 2x = 2(4.3 103) = 8.6 103 M; [O2] = x = 4.3 103 M
40.
a. The reaction must proceed to products to reach equilibrium because no product is present
initially. Summarizing the problem in a table where x atm of N2O4 reacts to reach
equilibrium:
Initial
Change
Equil.
N2O4(g)
4.5 atm
x
4.5 x
2 NO2(g)
0
+2x
2x
Kp = 0.25
CHAPTER 6
Kp =
2
PNO
2
PN 2O 4
165
(2 x) 2
= 0.25, 4x2 = 1.125 (0.25)x, 4x2 + (0.25)x 1.125 = 0
4 .5 x
We carried extra significant figures in this expression (as will be typical when we solve
an expression using the quadratic formula). Solving using the quadratic formula (see
Appendix 1 of text):
x=
0.25 [(0.25) 2 4(4)(1.125)]1/ 2

0.25 4.25
=
, x = 0.50
2( 4)
8
(Other value is negative.)

PNO 2 = 2x = 1.0 atm; PN 2O 4 = 4.5 x = 4.0 atm
b. The reaction must shift to reactants (shift left) to reach equilibrium.
N2O4(g)
Initial
Change
Equil.
Kp =
0
+x
x
2 NO2(g)
9.0 atm
2x
9.0 2x
(9.0 2 x) 2
= 0.25, 4x2 (36.25)x + 81 = 0 (carrying extra sig. figs.)
x
Solving: x =
(36.25) [(36.25) 2 4(4)(81)]1/ 2

, x = 4.0 atm
2( 4)
The other value, 5.1, is impossible. PN 2O 4 = x = 4.0 atm; PNO 2 = 9.0 2x = 1.0 atm
c. No, we get the same equilibrium position starting with either pure N2O4 or pure NO2 in
stoichiometric amounts.
d. From part a, the equilibrium partial pressures are PNO 2 = 1.0 atm and PN 2O 4 = 4.0 atm.
Halving the container volume will increase each of these partial pressures by a factor of
2. Q = (2.0)2/8.0 = 0.50. Because Q > Kp, the reaction will shift left to reestablish
equilibrium.
N2O4(g)
2 NO2(g)
Initial
New Initial
Change
Equil.
Kp =
4.0 atm
8.0
+x
8.0 + x
1.0 atm
2.0
2x
2.0 2x
( 2.0 2 x) 2
= 0.25, 4x2 (8.25)x + 2.0 = 0 (carrying extra sig. figs.)
8 .0 + x
166
CHAPTER 6
Solving using the quadratic formula: x = 0.28 atm

PN 2O 4 = 8.0 + x = 8.3 atm; PNO 2 = 2.0 2x = 1.4 atm
41.
CaCO3(s)
CaO(s) + CO2(g)
Kp = 1.16 = PCO 2
Some of the 20.0 g of CaCO3 will react to reach equilibrium. The amount that reacts is the
quantity of CaCO3 required to produce a CO2 pressure of 1.16 atm (from the Kp expression).
PCO 2 V
1.16 atm 10.0 L

= 0.132 mol CO2
0.08206 L atm
RT
1073 K
K mol
1 mol CaCO3
100.09 g
Mass CaCO3 reacted = 0.132 mol CO2
= 13.2 g CaCO3
mol CO 2
mol CaCO3
13.2 g
Mass % CaCO3 reacted =
100 = 66.0%
20.0 g
n CO 2 =
42.
This is a typical equilibrium problem except that the reaction contains a solid. Whenever
solids and liquids are present, we basically ignore them in the equilibrium problem.
NH4OCONH2(s)
2 NH3(g) + CO2(g)
Kp = 2.9 103
0
0
Some NH4OCONH2 decomposes to produce 2x atm of NH3 and x atm of CO2.
Change
+2x
+x
Equil.
2x
x
Initial
2
PCO 2 = (2x)2(x) = 4x3
Kp = 2.9 103 = PNH
3
2.9 10 3
x =
1/ 3
= 9.0 102 atm; PNH 3 = 2x = 0.18 atm; PCO 2 = x = 9.0 102 atm
Ptotal = PNH3 + PCO 2 = 0.18 atm + 0.090 atm = 0.27 atm

1
43.
4.5 109 L 0.08206 L atm
373 K , where n = 1 2 = 1
a. Kp = K(RT) =
mol
K mol
Kp = 1.5 108 atm1

b. Kp is so large that at equilibrium we will have almost all COCl2. Assume Ptotal
PCOCl 2 5.0 atm.
CHAPTER 6
CO(g) + Cl2(g)
Initial
167
COCl2(g)
Kp = 1.5 108
0
0
5.0 atm
x atm COCl2 reacts to reach equilibrium
+x
+x
x
x
x
5.0 x
Change
Equil.
Kp = 1.5 108 =
5.0 x 5.0
2
x2
x
(Assuming 5.0 x 5.0.)
Solving: x = 1.8 10-4 atm. Check assumptions: 5.0 x = 5.0 1.8 104 = 5.0 atm.
Assumptions are good (well within the 5% rule).
PCO = PCl2 = 1.8 104 atm and PCOCl2 = 5.0 atm
Fe3+(aq)
44.
Before
Change
After
Change
Equil.
SCN(aq)
FeSCN2+(aq)
K = 1.1 103
0.10 M
0
0.020 M
Let 0.020 mol/L Fe3+ react completely (K is large; products dominate).
0.020
0.020
+0.020
React completely
0
0.08
0.020
New initial
x mol/L FeSCN2+ reacts to reach equilibrium
+x
+x
x
x
0.08 + x
0.020 x
K = 1.1 103 =
[FeSCN 2 + ]
0.020 x
0.020
=
3+
( x)(0.08 + x) (0.08) x
[Fe ][SCN ]
x = 2 104 M; x is 1% of 0.020. Assumptions are good by the 5% rule.

x = [Fe3+] = 2 104 M; [SCN-] = 0.08 + 2 104 = 0.08 M
[FeSCN2+] = 0.020 2 104 = 0.020 M
Le Chatelier's Principle
45.
Only statement d is correct. Addition of a catalyst has no effect on the equilibrium position;
the reaction just reaches equilibrium more quickly. Statement a is false for reactants that are
either solids or liquids (adding more of these has no effect on the equilibrium). Statement b is
false always. If temperature remains constant, then the value of K is constant. Statement c is
false for exothermic reactions where an increase in temperature decreases the value of K.
46.
A change in volume will change the partial pressure of all reactants and products by the same
factor. The shift in equilibrium depends on the number of gaseous particles on each side. An
increase in volume will shift the equilibrium to the side with the greater number of particles
in the gas phase. A decrease in volume will favor the side with lesser gas-phase particles. If
there are the same number of gas-phase particles on each side of the reaction, a change in
volume will not shift the equilibrium.
168
CHAPTER 6
When we change the pressure by adding an unreactive gas, we do not change the partial
pressures (or concentrations) of any of the substances in equilibrium with each other since the
volume of the container did not change. If the partial pressures (and concentrations) are
unchanged, the reaction is still at equilibrium.
47.
a. No effect; adding more of a pure solid or pure liquid has no effect on the equilibrium
position.
b. Shifts left; HF(g) will be removed by reaction with the glass. As HF(g) is removed, the
reaction will shift left to produce more HF(g).
c. Shifts right; as H2O(g) is removed, the reaction will shift right to produce more H2O(g).
48.
a. Doubling the volume will decrease all concentrations by a factor of one-half.

1
[FeSCN 2 + ] eq
2
= 2 K, Q > K
Q=
1
1
3+
[Fe ] eq [SCN ] eq
2
2
The reaction will shift to the left to reestablish equilibrium.

b. Adding Ag+ will remove SCN- through the formation of AgSCN(s). The reaction will
shift to the left to produce more SCN-.
c. Removing Fe3+ as Fe(OH)3(s) will shift the reaction to the left to produce more Fe3+.
d. Reaction shifts to the right as Fe3+ is added.
49.
H+ + OH H2O; sodium hydroxide (NaOH) will react with the H+ on the product side of
the reaction. This effectively removes H+ from the equilibrium, which will shift the reaction
to the right to produce more H+ and CrO42-. Because more CrO42 is produced, the solution
turns yellow.
50.
a. The moles of SO3 will increase because the reaction will shift left to use up some of the
added O2(g).
b. Increase; because there are fewer reactant gas molecules than product gas molecules, the
reaction shifts left with a decrease in volume.
c. No effect; the partial pressures of sulfur trioxide, sulfur dioxide, and oxygen are
unchanged, so the reaction is still at equilibrium.
d. Increase; Heat + 2 SO3 2 SO2 + O2; decreasing T will remove heat, shifting this
endothermic reaction to the left.
e. Decrease
CHAPTER 6
51.
a. Right
b. Right
169
c. No effect; He(g) is neither a reactant nor a product.
d. Left; because the reaction is exothermic, heat is a product:

CO(g) + H2O(g) H2(g) + CO2(g) + heat
Increasing T will add heat. The equilibrium shifts to the left to use up the added heat.
e. No effect; because the moles of gaseous reactants equals the moles of gaseous products
(2 mol versus 2 mol), a change in volume will have no effect on the equilibrium.
52.
a. Shift to left
b. Shift to right; because the reaction is endothermic (heat is a reactant), an increase in
temperature will shift the equilibrium to the right.
c. No effect
d. Shift to right
e. Shift to right; because there are more gaseous product molecules than gaseous reactant
molecules, the equilibrium will shift right with an increase in volume.
53.
a. Left
b. Right
c. Left
d. No effect (reactant and product concentrations are unchanged)

e. No effect; because there are equal numbers of product and reactant gas molecules, a
change in volume has no effect on the equilibrium position.
f.
54.
Right; a decrease in temperature will shift the equilibrium to the right because heat is a
product in this reaction (as is true in all exothermic reactions).
When the volume of a reaction container is increased, the reaction itself will want to increase
its own volume by shifting to the side of the reaction that contains the most molecules of gas.
When the molecules of gas are equal on both sides of the reaction, then the reaction will
remain at equilibrium no matter what happens to the volume of the container.
a. Reaction shifts left (to reactants) because the reactants contain 4 molecules of gas
compared with 2 molecules of gas on the product side.
b. Reaction shifts right (to products) because there are more product molecules of gas (2)
than reactant molecules (1).
c. No change because there are equal reactant and product molecules of gas.
d. Reaction shifts right.
e. Reaction shifts right to produce more CO2(g). One can ignore the solids and only
concentrate on the gases because gases occupy a relatively huge volume compared with
solids. We make the same assumption when liquids are present (only worry about the gas
molecules).
170
CHAPTER 6
55.
An endothermic reaction, where heat is a reactant, will shift right to products with an increase
in temperature. The amount of NH3(g) will increase as the reaction shifts right, so the smell
of ammonia will increase.
56.
As temperature increases, the value of K decreases. This is consistent with an exothermic

reaction. In an exothermic reaction, heat is a product, and an increase in temperature shifts
the equilibrium to the reactant side (as well as lowering the value of K).
Additional Exercises
57.
a. N2(g) + O2(g) 2 NO(g)
Kp = 1 1031 =
2
2
PNO
PNO
=
(0.8)(0.2)
PN 2 PO 2
PNO = 1 1016 atm

In 1.0 cm3 of air: nNO =
PV
(1 10 16 atm)(1.0 10 3 L)
=
= 4 1021 mol NO
RT
0.08206 L atm
(298 K )
K mol
4 10 21 mol NO 6.02 10 23 molecules

2 103 molecules NO
=
mol NO
cm 3
cm 3
b. There is more NO in the atmosphere than we would expect from the value of K. The
answer must lie in the rates of the reaction. At 25C, the rates of both reactions:
N2 + O2 2 NO and 2 NO N2 + O2
are so slow that they are essentially zero. Very strong bonds must be broken; the
activation energy is very high. Therefore, the reaction essentially doesnt occur at low
temperatures. Nitric oxide, however, can be produced in high-energy or hightemperature environments because the production of NO is endothermic. In nature, some
NO is produced by lightning and the primary manmade source is automobiles. At these
high temperatures, K will increase, and the rates of the reaction will also increase,
resulting in a higher production of NO. Once the NO gets into a more normal
temperature environment, it doesnt go back to N2 and O2 because of the slow rate.
58.
a.
Na2O(s) 2 Na(l) + 1/2 O2(g)
K1
2 Na(l) + O2(g) Na2O2(s)

1/K3
___________________________________________________
Na2O(s) + 1/2 O2(g) Na2O2(s)

K=
2 10 25
= 4 103 L1/2/mol1/2
29
5 10
K = (K1)(1/K3)
CHAPTER 6
171
NaO(g) Na(l) + 1/2 O2(g)
b.
Na2O(s) 2 Na(l) + 1/2 O2(g)
K2
K1
1/K3
2 Na(l) + O2(g) Na2O2(s)
________________________________________________________________
K = K2(K1)(1/K3) = 8 102 L/mol
NaO(g) + Na2O(s) Na2O2(s) + Na(l)
2 NaO(g) 2 Na(l) + O2(g)
c.
K 22
1/K3
2 Na(l) + O2(g) Na2O2(s)
________________________________________________________________
K = K 22 (1/K 3 ) = 8 1018 L2/mol2
2 NaO(g) Na2O2(s)
59.
60.
O(g) + NO(g) NO2(g)
K = 1/6.8 1049 = 1.5 1048
O2(g) + O(g) O3(g)
K = (1.5 1048)(1.7 1033) = 2.6 1081 L/mol
NO2(g) + O2(g) NO(g) + O3(g)

K = 1/5.8 1034 = 1.7 1033
__________________________________________________________________________
2 A(g) + D(g)
K1 = (1/3.50)2 = 8.16 10 2
2 A(g) + 2 B(g)
2 C(g)
C(g)
K2 = 7.10
____________________________________________________________
C(g) + D(g) 2 B(g)
K = K1 K2 = 0.579
Kp = K(RT)n, n = 2 (1 + 1) = 0; because n = 0, Kp = K = 0.579.

C(g)
+ D(g)
Initial 1.50 atm

Equil. 1.50 x
0.579 = K =
1.50 atm
1.50 x
2 B(g)
0
2x
(2 x) 2
(2 x) 2
=
(1.50 x)(1.50 x) (1.50 x) 2
2x
= (0.579)1/2 = 0.761, x = 0.413 atm
1.50 x
PB (at equilibrium) = 2x = 2(0.413) = 0.826 atm
Ptotal = PC + PD + PB = 2(1.50 0.413) + 0.826 = 3.00 atm
PB = BPtotal, B =
PB
0.826 atm
=
= 0.275
Ptotal
3.00 atm
172
CHAPTER 6
61.
3 H2(g)
Initial
N2(g)
2 NH3(g)
[H2]0
[N2]0
0
x mol/L of N2 reacts to reach equilibrium
3x
x
+2x
[H2]0 3x
[N2]0 x
2x
Change
Equil.
From the problem:

[NH3]e = 4.0 M = 2x, x = 2.0 M; [H2]e = 5.0 M = [H2]0 3x; [N2]e = 8.0 M = [N2]0 x
5.0 M = [H2]0 3(2.0 M), [H2]0 = 11.0 M; 8.0 M = [N2]0 2.0 M, [N2]0 = 10.0 M
N2(g)
62.
3 H2(g)
Kp = 5.3 105
2 NH3(g)
P0 = initial pressure of NH3

0
0
P0
2x atm of NH3 reacts to reach equilibrium
+x
+3x
2x
x
3x
P0 2x
Initial
Change
Equil.
From problem, P0 2x =
Kp =
P0
, so P0 = (4.00)x
2.00
[(4.00) x 2 x]2
[(2.00) x]2
(4.00) x 2
4.00
=
=
=
= 5.3 105, x = 5.3 104 atm
3
3
4
( x)(3x)
( x)(3x)
27 x
27 x 2
P0 = (4.00)x = 4.00(5.3 104 atm) = 2.1 103 atm

63.
a.
Initial
Change
Equil.
PCl5(g)
PCl3(g)
P0
x
P0 x
0
+x
x
+ Cl2(g)
0
+x
x
Kp = (PPCl3 PCl 2 ) / PPCl5

P0 = initial PCl5 pressure
Ptotal = P0 x + x + x = P0 + x = 358.7 torr
P0 =
n PCl5 RT
V
2.4156 g
0.08206 L atm
523.2 K
208.22 g/mol
K mol
=
= 0.2490 atm (or 189.2 torr)
2.000 L
x = Ptotal P0 = 358.7 189.2 = 169.5 torr

PPCl 3
= PCl 2 = 169.5 torr
1 atm
= 0.2230 atm
760 torr
CHAPTER 6
PPCl5 = 189.2 169.5 = 19.7 torr

Kp =
b.
173
1 atm
= 0.0259 atm
760 torr
(0.2230) 2
= 1.92 atm
0.0259
PCl 2 =
n Cl 2 RT
V
0.250 0.08206 523.2

= 5.37 atm Cl2 added
2.000
PCl5(g)
PCl3(g)
Cl2(g)
Initial
0.0259 atm
0.2230 atm
0.2230 atm
Adding 0.250 mol Cl2 increases PCl 2 by 5.37 atm.
Initial'
Change
After
Change
Equil.
0.0259
+0.2230
0.2489
x
0.2489 x
0.2230
0.2230
0
+x
x
5.59
0.2230
5.37
+x
5.37 + x
(from a)
React completely
New initial
(5.37 + x)( x)
= 1.92, x2 + (7.29)x 0.478 = 0
(0.2489 x)

PPCl3 = 0.0650 atm; PPCl5 = 0.2489 0.0650 = 0.1839 atm; PCl 2 = 5.37 + 0.0650
= 5.44 atm
64.
Initial
Change
Equil.
SO2Cl2(g)
Cl2(g)
P0
x
P0 - x
0
+x
x
SO2(g)
0
+x
x
P0 = initial pressure of SO2Cl2
Ptotal = 0.900 atm = P0 x + x + x = P0 + x

x
100 = 12.5, P0 = (8.00)x
P0
Solving: 0.900 = P0 + x = (9.00)x, x = 0.100 atm

x = 0.100 atm = PCl 2 = PSO 2 ; P0 x = 0.800 0.100 = 0.700 atm = PSO 2Cl 2
Kp =
PCl 2 PSO 2
PSO 2Cl 2
(0.100) 2
= 1.43 102 atm
0.700
174
65.
CHAPTER 6
N2O4(g) 2 NO2(g)
Kp =
2
PNO
2
PN 2O 4
(1.20) 2
= 4.2 atm
0.34
Doubling the volume decreases each partial pressure by a factor of 2 (P = nRT/V).

PNO 2 = 0.600 atm and PN 2O 4 = 0.17 atm are the new partial pressures.
Q=
(0.600) 2
= 2.1, Q < K; equilibrium will shift to the right.
0.17
N2O4(g)
Initial 0.17 atm

Equil. 0.17 x
Kp = 4.2 =
2 NO2(g)
0.600 atm
0.600 + 2x
(0.600 + 2 x) 2
, 4x2 + (6.6)x 0.354 = 0 (carrying extra sig. figs.)
(0.17 x)

PNO 2 = 0.600 + 2(0.052) = 0.704 atm; PN 2O 4 = 0.17 - 0.052 = 0.12 atm
66.
a.
PPCl5 =
b.
n PCl5 RT
V
PCl5(g)
2.450 g PCl 5
0.08206 L atm
600. K
208.22 g/mol
K mol
=
= 1.16 atm
0.500 L
PCl3(g)
Cl2(g)
Kp =
Initial 1.16 atm

0
0
x atm of PCl5 reacts to reach equilibrium
Change x
+x
+x
Equil. 1.16 x
x
x
Kp =
x2
= 11.5, x2 + (11.5)x 13.3 = 0
1.16 x
Using the quadratic formula: x = 1.06 atm

PPCl5 = 1.16 1.06 = 0.10 atm
c.
PPCl3 = PCl 2 = 1.06 atm; PPCl5 = 0.10 atm

Ptotal = PPCl5 + PPCl3 + PCl 2 = 0.10 + 1.06 + 1.06 = 2.22 atm
d. Percent dissociation =
x
1.06
100 =
100 = 91.4%
1.16
1.16
PPCl3 PCl 2
PPCl5
= 11.5
CHAPTER 6
67.
a.
2 NaHCO3(s)
Na2CO3(s)
175
+
CO2(g) + H2O(g)
Kp = 0.25
0
0
NaHCO3(s) decomposes to form x atm each of CO2(g) and H2O(g) at
equilibrium.
+x
Change
+x
Equil.
x
x
Initial
Kp = 0.25 = PCO 2 PH 2O , 0.25 = x2, x = PCO 2 = PH 2O = 0.50 atm

b.
n CO 2 =
PCO 2 V
RT
(0.50 atm)(1.00 L)
= 1.5 102 mol CO2
(0.08206 L atm K 1 mol 1 )(398 K )
Mass of Na2CO3 produced:

1.5 102 mol CO2
1 mol Na 2 CO 3 106.0 g Na 2 CO 3
= 1.6 g Na2CO3
mol CO 2
mol Na 2 CO 3
Mass of NaHCO3 reacted:

1.5 102 mol CO2
2 mol NaHCO3 84.01 g NaHCO3
= 2.5 g NaHCO3
mol CO 2
mol
Mass of NaHCO3 remaining = 10.0 2.5 = 7.5 g

c. 10.0 g NaHCO3
1 mol NaHCO 3
1 mol CO 2
= 5.95 102 mol CO2

84.01 g NaHCO 3
2 mol NaHCO 3
When all the NaHCO3 has just been consumed, we will have 5.95 102 mol CO2 gas at
a pressure of 0.50 atm (from a).
V =
68.
nRT
(5.95 10 2 mol)(0.08206 L atm K 1 mol 1 )(398 K )
=
= 3.9 L
P
0.50 atm
a.
2 AsH3(g)
Initial
Equil.
392.0 torr
392.0 - 2x
2 As(s)
3 H2(g)
0
3x
Ptotal = 488.0 torr = 392.0 2x + 3x, x = 96.0 torr

PH 2 = 3x = 3(96.0) = 288 torr; PAsH3 = 392.0 2(96.0) = 200.0 torr
b. Kp =
(PH 2 ) 3
(PAsH3 ) 2
( 288) 3
1 atm
= 0.786 atm
= 597 torr
2
760 torr
(200.0)
176
CHAPTER 6
69.
NH3(g)
H2S(g)
NH4HS(s)
K = 400. =
1
[ NH 3 ][H 2S]
2.00 mol
2.00 mol
5.00 L
5.00 L
x mol/L of NH3 reacts to reach equilibrium
Change !x
!x
0.400 ! x
Equil.
0.400 ! x
Initial
1
1
K = 400. =
, 0.400 ! x =
(0.400 x)(0.400 x)
400.
Mol NH4HS(s) produced = 5.00 L
1/ 2
= 0.0500, x = 0.350 M
0.350 mol NH 3
1 mol NH 4 HS
= 1.75 mol
L
mol NH 3
Total mol NH4HS(s) = 2.00 mol initially + 1.75 mol produced = 3.75 mol total
3.75 mol NH4HS
51.12 g NH 4 HS
= 192 g NH4HS
mol NH 4 HS
[H2S]e = 0.400 M x = 0.400 M 0.350 M = 0.050 M H2S

PH 2S =
70.
n H 2S RT
V
n H 2S
V
RT =
0.050 mol 0.08206 L atm
308.2 K = 1.3 atm

L
K mol
Assuming 100.00 g naphthalene:

93.71 C
1 mol C
= 7.802 mol C
12.011 g
6.29 g H
1 mol H
= 6.24 mol H;
1.008 g
7.802
= 1.25
6.24
Empirical formula = (C1.25H) 4 = C5H4; molar mass =
32.8 g
= 128 g/mol
0.256 mol
Because the empirical mass (64.08 g/mol) is one-half of 128, the molecular formula is C10H8.
C10H8(s)
Initial
Equil.
C10H8(g)
0
x
K = 4.29 10 6 = [C10H8] = x
K = 4.29 10 6 = [C10H8]
CHAPTER 6
177
Mol C10H8 sublimed = 5.00 L 4.29 10 6 mol/L = 2.15 10 5 mol C10H8 sublimed
Mol C10H8 initially = 3.00 g
2.15 10 5 mol
100 = 0.0919%
2.34 10 2 mol
Percent C10H8 sublimed =
71.
5.63 g C5H6O3
1 mol C 5 H 6 O 3
= 0.0493 mol C5H6O3 initially
114.10 g
Total moles of gas = ntotal =

at equilibrium
C5H6O3(g)
Initial
1 mol C10 H 8
= 2.34 10 2 mol C10H8 initially
128.16 g
Ptotal V
1.63 atm 2.50 L
= 0.105 mol
=
0.08206 L atm
RT
473 K
K mol
C2H6(g) + 3 CO(g)
0.0493 mol
0
0
Let x mol C5H6O3 react to reach equilibrium.
!x
+x
+3x
x
3x
0.0493 ! x
Change
Equil.
0.105 mol total = 0.0493 x + x + 3x = 0.0493 + 3x, x = 0.0186 mol

3
0.0186 mol C 2 H 6 3(0.0186) mol CO
3
2.50 L
2.50 L
[C H ][CO]
= 6.74 10 6 mol3/L3
K= 2 6
=
[C 5 H 6 O 3 ]
(0.0493 0.0186) mol C 5 H 6 O 3
2.50 L
Challenge Problems
72.
N2O4(g)
a.
Initial
Change
Equil.
2 NO2(g)
0
+(0.32)x
(0.32)x
x
!(0.16)x
(0.84)x
(0.84)x + (0.32)x = 1.5 atm, x = 1.3 atm; Kp =
N2O4
b.
Equil.
2 NO2 ; x + y = 1.0 atm;

y
(0.42) 2
= 0.16 atm
1.1
y2
= 0.16
x
Solving: x = 0.67 atm (= PN 2O 4 ) and y = 0.33 atm (= PNO 2 )
178
CHAPTER 6
c.
N2O4
Initial
Change
Equil.
2 NO2
0
+2x
0.33 atm
P0
!x
0.67 atm
P0 = initial pressure of N2O4
2x = 0.33, x = 0.165 (using extra sig. figs.)

P0 ! x = 0.67, P0 = 0.67 + 0.165 = 0.84 atm;
73.
a.
2 NO(g)
Initial
Change
Equil.
Br2(g)
0.165
100 = 20.% dissociated
0.84
2 NOBr(g)
98.4 torr
41.3 torr
0
2x torr of NO reacts to reach equilibrium
2x
x
+2x
98.4 2x
41.3 x
2x
Ptotal = PNO + PBr2 + PNOBr = (98.4 - 2x) + (41.3 x) + 2x = 139.7 x

Ptotal = 110.5 = 139.7 x, x = 29.2 torr; PNO = 98.4 - 2(29.2) = 40.0 torr = 0.0526 atm
PBr2 = 41.3 29.2 = 12.1 torr = 0.0159 atm; PNOBr = 2(29.2) = 58.4 torr = 0.0768 atm
Kp =
2
PNOBr
(0.0768 atm) 2
=
= 134 atm1
2
2
PNO PBr2
(0.0526 atm) (0.0159 atm)
b.
2 NO(g)
Initial
Change
Equil.
Br2(g)
2 NOBr(g)
0.30 atm
0.30 atm
0
2x atm of NO reacts to reach equilibrium
2x
x
+2x
0.30 2x
0.30 x
2x
This would yield a cubic equation, which can be difficult to solve unless you have a
graphing calculator. Because Kp is pretty large, lets approach equilibrium in two steps:
Assume the reaction goes to completion, and then solve the back equilibrium problem.
2 NO
Before
Change
After
Change
Equil.
Br2
2 NOBr
0.30 atm
0.30 atm
0
Let 0.30 atm NO react completely.
0.30
0.15
+0.30
React completely
0
0.15
0.30
New initial
2y atm of NOBr reacts to reach equilibrium
+2y
+y
2y
0.15 + y
0.30 2y
2y
CHAPTER 6
179
K p = 134 =
(0.30 2 y ) 2
(0.30 2 y ) 2
= 134 4y2 = 536y2
,
2
(
0
.
15
+
y
)
( 2 y ) (0.15 + y )
If y << 0.15:
(0.30) 2
536y2 and y = 0.034; assumptions are poor (y is 23% of 0.15).
0.15
Use 0.034 as an approximation for y, and solve by successive approximations (see

Appendix 1):
(0.30 0.068) 2
= 536y2, y = 0.023;
0.15 + 0.034
(0.30 0.046) 2
= 536y2, y = 0.026
0.15 + 0.023
(0.30 0.052) 2
= 536y2, y = 0.026 atm (We have converged on the correct
0.15 + 0.026
answer.)
So: PNO = 2y = 0.052 atm; PBr2 = 0.15 + y = 0.18 atm; PNOBr = 0.30 2y = 0.25 atm
74.
a. If the volume is increased, equilibrium will shift to the right, so the mole percent of N2O5
decomposed will be greater than 0.50%.
4 NO2
1.000 atm
0.0050
0.995
0
+0.010
0.010
2 N2O5
b.
Initial
Change
Equil.
Kp =
O2
0
+0.0025
0.0025
(0.010) 4 (0.0025)
= 2.5 1011 atm3
2
(0.995)
The new volume is 10.0 times the old volume. Therefore, the initial partial pressure of
N2O5 will decrease by a factor of 10.0.
PN 2O5 = 1.00 atm
2 N2O5
Initial
Change
Equil.
1.00
= 0.100 atm
10.0
4 NO2 +
0.100 atm
0
2x
+4x
4x
0.100 2x
2.5 1011 =
O2
0
+x
x
(4 x) 4 ( x)
(4 x) 4 ( x)
, 2x = 2.0 103 atm = PN 2O5 decomposed

(0.100 2 x) 2
(0.100) 2
2.0 10 3
100 = 2.0% N2O5 decomposed (moles and P are directly related)
0.100
180
75.
CHAPTER 6
P4(g) 2 P2(g) Kp = 0.100 =
PP22
PP4
; PP4 + PP2 = Ptotal = 1.00 atm, PP4 = 1.00 PP2
Let y = PP2 at equilibrium, then Kp =
y2
= 0.100
1.00 y
Solving: y = 0.270 atm = PP2 ; PP4 = 1.00 0.270 = 0.73 atm

To solve for the fraction dissociated, we need the initial pressure of P4.
P4(g)
Initial
Change
Equil.
2 P2(g)
P0
0
P0 = initial pressure of P4
x atm of P4 reacts to reach equilibrium
x
+2x
P0 x
2x
Ptotal = P0 x + 2x = 1.00 atm = P0 + x

Solving: 0.270 atm = PP2 = 2x, x = 0.135 atm; P0 = 1.00 0.135 = 0.87 atm
Fraction dissociated =
76.
0.135
x
=
= 0.16, or 16% of P4 is dissociated to reach equilibrium.
P0
0.87
Equilibrium lies to the right (Kp values are very large). Let each reaction go to completion
initially, and then solve the back equilibrium problems.
CH4 + 2 O2
Before 1.50
15.00
After
0
12.00
2 C2H6 + 7 O2
Before 2.50
After
0
12.00
3.25
CO2
0
1.50
+ 2 H2O
0
3.00 atm
4 CO2 + 6 H2O
1.50
6.50
3.00
10.50 atm
Thus after we let the two reactions go to completion, we have 3.25 atm O2, 6.50 atm CO2, and
10.50 atm H2O. Lets solve the back equilibrium problems to determine the equilibrium concentrations.
CH4
Initial
Change
Equil.
0
+x
x
2 O2
3.25 atm
+2x
3.25 + 2x
K p = 1.0 10 =
4
PCO 2 PH2 2O
PCH 4 PO2 2
CO2
6.50 atm
x
6.50 x
2 H2O
10.50 atm
2x
10.50 2x
(6.50 x)(10.50 2 x) 2
6.50(10.50 ) 2
x(3.25 + 2 x) 2
x(3.25) 2
CHAPTER 6
181
x = PCH 4 = 6.8 103 atm; assumptions are good.
2 C2H6(g) +
7 O2(g)
4 CO2(g)
+ 6 H2O(g)
0
+2x
2x
3.25 atm
+7x
3.25 + 7x
6.50 atm
4x
6.50 4x
10.50 atm
6x
10.50 6x
Initial
Change
Equil.
Kp = 1.0 108 =
4
PCO
PH6 2O
2
PC22 H 6 PO7 2
(6.50 4 x) 4 (10.50 6 x) 6
(6.50) 4 (10.50 ) 6
( 2 x) 2 (3.25 + 7 x) 7
4 x 2 (3.25) 7
2x = PC 2 H 6 = 0.079 atm; assumptions are good.

77.
PO ( molar mass O 2 ) + PO3 (molar mass O3 )

P (molar mass)
= 2
RT
RT
d = density =
0.168 g/L =
PO 2 (32.00 g / mol) + PO3 (48.00 g / mol)

, (32.00)PO 2 + (48.00)PO3 = 6.18
0.08206 L atm
448 K
K mol
Ptotal = PO 2 + PO3 = 128 torr
1 atm
= 0.168 atm
760 torr
We have two equations in two unknowns. Solving using simultaneous equations:

(32.00)PO 2 + (48.00)PO3 = 6.18
(32.00)PO 2 (32.00)PO3 = 5.38
____________________________
(16.00)PO3 = 0.80
PO3 =
Kp =
0.80
= 0.050 atm and PO 2 = 0.118 atm
16.00
PO2 3
PO3 2
(0.050) 2
= 1.5 atm1
(0.118) 3
O2(g)
78.
Initial
Change
Equil.
100
!83
17
Thus: O =
2 O(g)
Assume exactly 100 O2 molecules.
0
+166
166
166
= 0.9071 and O 2 = 0.0929
183
182
CHAPTER 6
PO 2 = O 2 Ptotal ; and PO = OPtotal

Because initially Ptotal = 1.000 atm, PO 2 = 0.0929 atm and PO = 0.9071 atm.
Kp =
PO2
(0.9071) 2
= 8.86 atm
=
0.0929
PO 2
O2
Initial
Change
Equil.
2O
0
+2y
2y
x
!y
x!y
(2 y) 2
y
100 = 95.0; we have two equations and two unknowns.
= 8.86;
x y
x
Solving: x = 0.123 atm and y = 0.117 atm; Ptotal = (x y) + 2y = 0.240 atm
79.
4.72 g CH3OH
1 mol
= 0.147 mol CH3OH initially
32.04 g
Rate1
=
Rate 2
Grahams law of effusion:

Rate H 2
Rate CH 3OH
M CH 3OH
M H2
M2
M1
32.04
= 3.987
2.016
The effused mixture has 33.0 times as much H2 as CH3OH. When the effusion rate ratio is
multiplied by the equilibrium mole ratio of H2 to CH3OH, the effused mixture will have 33.0
times as much H2 as CH3OH. Let n H 2 and n CH 3OH equal the equilibrium moles of H2 and
CH3OH, respectively.
33.0 = 3.987
n H2
n CH 3OH
CH3OH(g)
Initial
Change
Equil.
0.147 mol
x
0.147 x
n CH 3OH
= 8.28
CO(g)
0
+x
x
From the ICE table, 8.28 =

Solving: x = 0.118 mol
n H2
n H2
n CH 3OH
+ 2 H2(g)
0
+2x
2x
2x
0.147 x
CHAPTER 6
183
0.118 mol 2(0.118 mol)
2
1.00 L 1.00 L
[CO][H 2 ]
K=
=
(0.147 0.118) mol
[CH 3OH]
1.00 L
80.
a. 89.7 g SbCl5
= 0.23 mol2/L2
1 mol
= 0.300 mol SbCl5 initially
299.1 g
SbCl5(g)
Initial
Change
Equil.
0.300 mol
(0.292)(0.300)
0.212
SbCl3(g) +
0
+0.0876
0.0876
Cl2(g)
0
+0.0876
0.0876 mol
0.0876 mol 0.0876 mol
15.0 L 15.0 L
K=
= 2.41 103 mol/L
0.212 mol
15.0 L
b. Let x = moles Cl2 added; reaction shifts left after Cl2 is added.
Equilibrium moles SbCl3 =
0.0876
= 0.0438 mol
2
Therefore, 0.0438 mol SbCl3 was reacted.

Equilibrium moles Cl2 = x + 0.0876 0.0438 = x + 0.0438
Equilibrium moles SbCl5 = 0.212 + 0.0438 = 0.256 mol
2.41 103
81.
a.
PPCl5 =
x + 0.0438 0.0438
15.0
15.0
=
; solving: x = 0.168 mol Cl2 added
0.256
15.0
n PCl5 RT
V
PCl5(g)
Initial
Change
Equil.
0.100 mol
0.328 atm
x
0.328 x
0.08206 L atm
480. K
K mol
= 0.328 atm
12.0 L
PCl3(g)
0
+x
x
Cl2(g)
0
+x
x
Kp = 0.267 atm
184
CHAPTER 6
Kp =
x2
= 0.267, x2 + (0.267)x 0.08758 = 0 (carrying extra sig. figs.)
0.328 x

PPCl3 = PCl 2 = 0.191 atm; PPCl5 = 0.328 0.191 = 0.137 atm
b.
Initial
Change
Equil.
PCl5(g)
P0
x
P0 x
PCl3(g)
0
+x
x
Cl2(g)
0
+x
x
P0 = initial pressure of PCl5
Ptotal = 2.00 atm = (P0 x) + x + x = P0 + x, P0 = 2.00 x

Kp =
x2
x2
= 0.267;
= 0.267, x2 = 0.534 (0.534)x
P0 x
2.00 2 x
x2 + (0.534)x 0.534 = 0;
solving using the quadratic formula:
0.534 (0.534) 2 + 4(0.534)
= 0.511 atm
2
P0 = 2.00 x = 2.00 0.511 = 1.49 atm; the initial pressure of PCl5 was 1.49 atm.
x=
n PCl5 =
PPCl5 V
RT
(1.49 atm)(5.00 L)
= 0.189 mol PCl5
(0.08206 L atm K 1 mol 1 )(480. K )
0.189 mol PCl5 208.22 g PCl5/mol = 39.4 g PCl5 was initially introduced.
82.
P0 (for O2) = n O 2 RT / V = (6.400 g 0.08206 684 K)/(32.00 g/mol 2.50 L) = 4.49 atm
2 O2(g) CO2(g) + 2 H2O(g)
2x +x
+2x
Change
CH4(g) +
x
Change
CH4(g) + 3/2 O2(g) CO(g) + 2 H2O(g)

y
3/2 y
+y
+2y
Amount of O2 reacted = 4.49 atm 0.326 atm = 4.16 atm O2

2x + 3/2 y = 4.16 atm O2 and 2x + 2y = 4.45 atm H2O
Solving using simultaneous equations:
2x +
2y = 4.45
2x (3/2)y = 4.16
(0.50)y = 0.29, y = 0.58 atm = PCO
CHAPTER 6
2x + 2(0.58) = 4.45, x =
83.
N2(g)
Equil.
4.45 1.16
= 1.65 atm = PCO 2
2
+ O2(g)
(3.7)p
185
2 NO(g)
Let:
equilibrium PO 2 = p
equilibrium PN 2 = (78/21)PO 2 = (3.7)p

equilibrium PNO = x
equilibrium PNO 2 = y
Kp = 1.5 104 =
2
PNO
PO 2 PN 2
N2
Equil.
2 O2
(3.7)p
Kp = 1.0 105 =
2 NO2
y
2
PNO
2
PO2 2 PN 2
We want PNO 2 = PNO at equilibrium, so x = y.

Taking the ratio of the two Kp expressions:
2
PNO
PO 2 PN 2
2
PNO
2
1.5 10 4
1.5 10 4
=
P
:
P
=
;
because
P
= 15 atm
NO
NO 2
O2
1.0 10 5
1.0 10 5
PO2 2 PN 2
Air is 21 mol % O2, so:
PO 2 = (0.21)Ptotal, Ptotal =
15 atm
= 71 atm
0.21
To solve for the equilibrium concentrations of all gases (not required to answer the question),
solve one of the Kp expressions where p = PO 2 = 15 atm.
1.5 104 =
x2
, x = PNO = PNO 2 = 0.35 atm
15[3.7(15)]
Equilibrium pressures:
PO 2 = 15 atm; PN 2 = 3.7(15) = 55.5 = 56 atm; PNO = PNO 2 = 0.35 atm
186
CHAPTER 6
84.
Initial
Change
Equil.
CCl4(g)
C(s) +
2 Cl2(g) Kp = 0.76
P0
x
P0- x
0
+2x
2x
P0 = initial pressure of CCl4
Ptotal = P0 x + 2x = P0 + x = 1.20 atm

Kp =
(2 x) 2
4 x 2 + (0.76) x
= 0.76, 4x2 = (0.76)P0 (0.76)x, P0 =
; substituting into
P0 x
0.76
P0 + x = 1.20:
2
4x
+ x + x = 1.20 atm, (5.3)x2 + 2x 1.20 = 0; solving using the quadratic formula:
0.76
x=
85.
Initial
Change
Equil.
2 (4 + 25.4)1/ 2
= 0.32 atm; P0 + 0.32 = 1.20, P0 = 0.88 atm
2(5.3)
SO3(g)
P0
x
P0 x
SO2(g) + 1/2 O2(g)

0
+x
x
0
+x/2
x/2
P0 = initial pressure of SO3
Average molar mass of the mixture is:

average molar mass =
dRT
(1.60 g / L) (0.08206 L atm K 1 mol 1 ) (873 K )
=
P
1.80 atm
= 63.7 g/mol
The average molar mass is determined by:

average molar mass =
n SO3 (80.07 g/mol) + n SO 2 (64.07 g/mol) + n O 2 (32.00 g/mol)

n total
Because A = mol fraction of component A = nA/ntotal = PA/Ptotal:

63.7 g/mol = =
PSO 3 (80.07) + PSO 2 (64.07) + PO 2 (32.00)

Ptotal
Ptotal = P0 x + x + x/2 = P0 + x/2 = 1.80 atm, P0 = 1.80 - x/2
63.7 =
(P0 x) (80.07) + x (64.07) +

1.80
x
(32.00)
2
CHAPTER 6
187
(1.80 3/2 x) (80.07) + x (64.07) +
63.7 =
x
(32.00)
2
1.80
115 = 144 (120.1)x + (64.07)x + (16.00)x, (40.0)x = 29, x = 0.73 atm

PSO 3 = P0 x = 1.80 (3/2)x = 0.71 atm; PSO 2 = 0.73 atm; PO 2 = x/2 = 0.37 atm
Kp =
86.
PSO 2 PO1/22
PSO3
(0.73) (0.37)1/ 2
= 0.63 atm1/2
(0.71)
The first reaction produces equal amounts of SO3 and SO2. Using the second reaction,
calculate the SO3, SO2, and O2 partial pressures at equilibrium.
SO3(g)
Initial
P0
Change
Equil.
x
P0 x
SO2(g)
1/2 O2(g)
P0
+x
P0 + x
P0 = initial pressure of SO3 and

SO2 after first reaction occurs.
+x/2
x/2
Ptotal = P0 x + P0 + x + x/2 = 2P0 + x/2 = 0.836 atm

PO 2 = x/2 = 0.0275 atm, x = 0.0550 atm
2P0 + x/2 = 0.836 atm; 2P0 = 0.836 0.0275 = 0.809 atm, P0 = 0.405 atm
PSO 3 = P0 x = 0.405 0.0550 = 0.350 atm; PSO 2 = P0 + x = 0.405 + 0.0550 = 0.460 atm
For 2 FeSO4(s) Fe2O3(s) + SO3(g) + SO2(g):
Kp = PSO 2 PSO 3 = (0.460)(0.350) = 0.161 atm2
For SO3(g) SO2(g) + 1/2 O2(g):
Kp =
87.
PSO 2 PO1/22
PSO3
N2(g) + 3 H2 (g)
(0.460) (0.0275)1/ 2
= 0.218 atm1/2
(0.350)
2 NH3(g)
1.0 atm
N2(g)
Initial
Equil.
0.25 atm
0.25 x
Kp =
3 H2(g)
0.75 atm
0.75 3x
2
PNH
3
PN 2
PH3 2
2 NH3(g)
0
2x
= 6.5 103
188
CHAPTER 6
(2 x) 2
= 6.5 103; using successive approximations:
3
(0.75 3x) (0.25 x)
x = 1.2 102 atm; PNH 3 = 2x = 0.024 atm
10 atm
N2(g)
Initial
Equil.
2.5 atm
2.5 x
3 H2(g)
2 NH3(g)
7.5 atm
7.5 3x
0
2x
(2 x) 2
= 6.5 103; using successive approximations:
3
(7.5 3 x) (2.5 x)
x = 0.69 atm; PNH 3 = 1.4 atm
100 atm
Using the same setup as above:
4x2
= 6.5 103
3
(75 3x) (25 x)
Solving by successive approximations: x = 16 atm; PNH 3 = 32 atm

1000 atm
N2(g)
Initial
New initial
Equil.
3 H2(g)
2 NH3(g)
250 atm
750 atm
0
Let 250 atm N2 react completely.
0
0
5.0 102
x
3x
5.0 102 2x
(5.0 10 2 2 x) 2
= 6.5 103; Using successive approximations:
3
(3x) x
x = 32 atm; PNH 3 = 5.0 102 2x = 440 atm
CHAPTER 6
189
The results are plotted as log PNH 3 versus

log Ptotal. Notice that as Ptotal increases, a
larger fraction of N2 and H2 is converted
to NH3, that is, as Ptotal increases (V
decreases), the reaction shifts further to
the right, as predicted by LeChateliers
principle.
88.
a. Because density (mass/volume) decreases while the mass remains constant (mass is conserved in a chemical reaction), volume must increase. The volume increases because the
number of moles of gas increases (V n at constant T and P).
V
n
Density (initial)
4.495 g/L
=
= 1.100 = equil. = equil.
Density (equil.)
4.086 g/L
Vinitial
n initial
Assuming an initial volume of 1.000 L:
4.495 g NOBr
Initial
Change
Equil.
n equil.
n initial
1 mol NOBr
= 0.04090 mol NOBr initially
109.91 g
2 NOBr(g)
0.04090 mol
2x
0.04090 2x
2 NO(g) + Br2(g)
0
+2x
2x
0
+x
x
0.04090 2 x + 2 x + x
= 1.100; solving: x = 0.00409 mol
0.04090
If the initial volume is 1.000 L, then the equilibrium volume will be 1.110(1.000 L) =
1.110 L. Solving for the equilibrium concentrations:
[NOBr] =
0.03272 mol
0.00818 mol
= 0.02975 M ; [NO] =
= 0.00744 M
1.100 L
1.100 L
190
CHAPTER 6
[Br2] =
K=
0.00409 mol
= 0.00372 M
1.100 L
(0.00744) 2 (0.00372)
= 2.33 104 mol/L
2
(0.02975)
b. The argon gas will increase the volume of the container. This is because the container is a
constant-pressure system, and if the number of moles increases at constant T and P, the
volume must increase. An increase in volume will dilute the concentrations of all
gaseous reactants and gaseous products. Because there are more moles of product gases
versus reactant gases (3 mol versus 2 mol), the dilution will decrease the numerator of K
more than the denominator will decrease. This causes Q < K and the reaction shifts right
to get back to equilibrium.
Because temperature was unchanged, the value of K will not change. K is a constant as
long as temperature is constant.
89.
2.00 g
= 0.0121 mol XY (initially)
165 g/mol
(0.350)(0.0121 mol) = 4.24 103 mol XY dissociated
XY
Initial
Change
Equil.
0.0121 mol
0.00424
0.0079 mol
0
0
+0.00424
+0.00424
0.00424 mol 0.00424 mol
Total moles of gas = 0.0079 + 0.00424 + 0.00424 = 0.0164 mol

V n, so:
Vinitial =
Vfinal
n
0.0164 mol
= final =
= 1.36
Vinitial
n initial
0.0121 mol
(0.0121 mol)(0.008206 L atm K 1 mol 1 )(298 K )

nRT
=
= 0.306 L
0.967 atm
P
Vfinal = 0.306 L(1.36) = 0.416 L; Because mass is conserved in a chemical reaction:

density (final) =
mass
2.00 g
=
= 4.81 g/L
volume 0.416 L
2
0.00424 mol
[X ][Y] 0.416 L
K=
=
= 5.5 10 3 mol/L
[XY]
0.0079 mol
0.416 L
CHAPTER 6
191
Marathon Problem
90.
Concentration units involve both moles and volume and since both quantities are changing at
the same time, we have a complicated system. Lets simplify the setup of the problem
initially by only worrying about the changes that occur to the moles of each gas.
A(g)
Initial
Change
Equil.
B(g)
C(g)
K = 130.
0
0
0.406 mol
Let x mol of C(g) react to reach equilibrium
+x
+x
x
x
x
0.406 x
Let Veq = the equilibrium volume of the container, so:

[A]eq = [B]eq =
x
0.406 x
; [C]eq =
Veq
Veq
0.046 x
Veq
(0.406 x) Veq
[ C]
K =
=
=
x
x
[A ][B]
x2
Veq
Veq
From the ideal gas equation: V = nRT/P. To calculate the equilibrium volume from the ideal
gas law, we need the total moles of gas present at equilibrium.
At equilibrium: ntotal = mol A(g) + mol B(g) + mol C(g) = x + x + 0.406 - x = 0.406 + x
Therefore: Veq =
n total RT
(0.406 + x)(0.08206 L atm K 1 mol 1 )(300.0 K )
=
P
1.00 atm
Veq = (0.406 + x)24.6 L/mol

Substituting into the equilibrium expression for Veq:
K = 130. =
(0.406 x)(0.406 + x)24.6

x2
Solving for x (we will carry one extra significant figure):

(130.)x2 = (0.1648 x2)24.6, (154.6)x2 = 4.054, x = 0.162 mol
Solving for the volume of the container at equilibrium:
Veq =
(0.406 + 0.162 mol)(0.08206)(300.0 K )

= 14.0 L
1.00 atm

Characteristics of Chemical Equilibrium

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Characteristics of Chemical Equilibrium

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CHAPTER 6

a. The rates of the forward and reverse reactions are equal.

K = 1.6 105 mol/L

No, equilibrium is a dynamic process. Both reactions:

We need to start somewhere, so lets assume 3 molecules of CO react. If 3 molecules of CO

Because K = 2.0 for this reaction mixture, we are at equilibrium.

The Equilibrium Constant

Kp = K(RT)n, where n = sum of gaseous product coefficients ! sum of gaseous reactant

Kp = K(RT)2 = 1.9(0.08206 L atm K1 mol1 600. K)2 = 4.6 103 atm2

H2(g) + Br2(g) 2 HBr(g)

a. HBr 1/2 H2 + 1/2 Br2

(PH 2 )1/ 2 (PBr2 )1/ 2

c. 1/2 H2 + 1/2 Br2 HBr

= 4.08 108 L/mol

; Ptotal = PH 2O + PH 2 , 36.3 torr = 15.0 torr + PH 2 , PH 2 = 21.3 torr

Because l atm = 760 torr: Kp =

Note: Solids and pure liquids are not included in K expressions.

From the setup: Ptotal = 2.00 atm = PN 2 + PH 2 + PNH 3

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

PPCl5 = 0.50 atm x, PPCl3 = PCl 2 = x

Initially: PS8 = 1.00 atm and PS2 = 0 atm

Solving: 2x = [SO2]e = 1.0 M, x = 0.50 M; [SO3]e = 4.0 2(0.50) = 3.0 M; [O2]e = x

2 NO(g) N2(g) + O2(g) K =

(0.11 atm)(2.0 atm)

Q < Kp (2.4 103), so the reaction shifts right to reach equilibrium.

(0.36 atm)(0.67 atm)

(0.51 atm)(0.18 atm)

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

Kp = PCO 2 = 1.04 atm

At equilibrium because Q = Kp; mass of CaO will not change.

Plug the equilibrium concentrations into the equilibrium constant expression:

The equilibrium concentrations are:

H2O(g) + Cl2O(g) 2 HOCl(g)

a. The initial concentrations of H2O and Cl2O are:

= 5.6 102 mol/L;

= 2.3 102 mol/L

1.16 104 (7.11 103)x + (0.090)x2 = 4x2

7.11 10 3 (5.06 10 5 + 1.81 10 3 )1/ 2

x = 0.217 M (We carried extra significant figures.)

[HF] = 0.400 + 2(0.0249) = 0.450 M; [H2] = [F2] = 0.0500 0.0249 = 0.0251 M

4x2 = 8.0 103 (0.050)x + (0.050)x2, (3.95)x2 + (0.050)x 8.0 103 = 0

PNO = 2x = 2(3.9 102 atm) = 7.8 102 atm

1.0 2x = 1.0 2(0.016) = 0.97 = 1.0 (to proper significant figures)

(assuming 2.0 2x 2.0)

[NOCl] = 2.0 0.050 = 1.95 M = 2.0 M; [NO] = 0.050 M; [Cl2] = 0.025 M

If we say that y is small to simplify the problem, then:

(assuming 2x << 1.0)

x = 1.6 105 M; Assumptions are great (2x is 3.2 103% of 1.0).

[Cl2] = 1.6 105 M and [NOCl] = [NO] = 1.0 M

; solving: x = 6.4 105 M

Assumptions are great (2x is 1.3 102% of 1.0).

, x = 4.0 102 M; assumption good (2% error).

[Cl2] = 0.040 M; [NO] = 0.080 M; [NOCl] = 4.0 2(0.040) = 3.92 M 3.9 M

= 1.6 105, x = 5.7 103 M

Assumptions are good (x is 1.1% of 0.50).

[CO2] = 0.40 2x = 0.40 2(4.3 103) = 0.39 M

0.25 [(0.25) 2 4(4)(1.125)]1/ 2

(Other value is negative.)

(36.25) [(36.25) 2 4(4)(81)]1/ 2