Chapter 15

Practice Exercises

15.1 2N2O3 + O2
4NO2

15.2 (a)
[ H 2 O]2 = K (b)
[CO2 ][ H 2O]2 = Kc
c
[ H 2 ]2 [O2 ] [CH 4 ][ O2 ]2
15.3 Since the starting equation has been reversed and divided by two, we must invert the equilibrium constant,
and then take the square root: Kc = 1.2 × 10–13

15.4 If we divide both equations by 2 and reverse the second we get:

CO(g) + 1/2O2(g)
CO2(g) Kc = 5.7 × 1045

H2O(g)
H2(g) + 1/2O2(g) Kc = 3.3 × 10–41

Note that when we divide the equation by two, we need to take the square root of the rate constant. When
we reverse the reaction, we need to take the inverse.

Adding these equations we get the desired equation so we need simply multiply the values for Kc in order
to obtain the new value: Kc = 1.9 × 105

15.5 KP =
( PN O ) 2

2
( PN ) ( PO )
2 2

( PHI )2
15.6 KP =
( PH )( PI )
2 2

∆n g
15.7 Use the equation K p = K c ( RT ) . In this reaction, ∆ng = 3 – 2 = 1, so
1
K p = K c ( RT )
∆n g
(
= 7.3 × 1034 ) (( 0.0821 L atm
mol K ) ( 298 K ) ) = 1.8 × 1036

15.8 We would expect KP to be smaller than Kc since ∆ng is negative.

Use the equation:
∆n g
K p = K c ( RT )
Kp
Kc =
( RT )∆n g

In this case, ∆ng = (1 – 3) = –2, and we have:

Kp 3.8 × 10−2
Kc = = = 57
( RT )∆n g L atm
((
0.0821 mol K ( 473 K )
−2
) )
1
15.9 Kc =
 NH3 ( g )   HCl ( g ) 

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1
15.10 (a) Kc =
[Cl2 (g)]
(b) K c =  Na + (aq)   OH − (aq)  [ H 2 (g) ]
  
2
(c) K c =  Ag +   CrO 42 − 
   
2
Ca +2 (aq)   HCO − (aq) 
Kc =   
3
(d)
[ 2 ]
CO (aq)

15.11 To solve this problem, the first step is to find Q, the mass action expression, and then compare it to the
value for Kc. If Q is larger than Kc, then there are more products than the equilibrium concentration and the
reaction will move to reactants. If Q is smaller than Kc, then there are more reactants than the equilibrium
concentrations and the reaction will move to products.
For this reaction, the concentrations of H2, Br2 and HBr are all equal. If we set them to x, then we see that
they cancel to give Q = 1:

Q=
[ HBr ]2 = [ x ]2 = 1
[ H 2 ][ Br2 ] [ x ][ x ]
Q is larger than Kc, therefore the reaction will move to reactants.

15.12 Reaction (a) will proceed the least amount towards completion followed by reaction (c) and finally,
reaction (b) will proceed farthest to completion since it has the largest value for Kc.

15.13 Only the gases will be affected by the volume of the container. But the stoichiometric ratio of the reactants
to products is 5:5, so as the volume is changes, the number of moles of gas will not change, therefore the
reaction will not change, and there will be no change in the amount of H3PO4.

15.14 (a) The equilibrium will shift to the right, decreasing the concentration of Cl2 at equilibrium, and
consuming some of the added PCl3. The value of Kp will be unchanged.
(b) The equilibrium will shift to the left, consuming some of the added PCl5 and increasing the
amount of Cl2 at equilibrium. The value of Kp will be unchanged.
(c) For any exothermic equilibrium, an increase in temperature causes the equilibrium to shift to the
left, in order to remove energy in response to the stress. This equilibrium is shifted to the left,
making more Cl2 and more PCl3 at the new equilibrium. The value of Kp is given by the
following:
PPCl5
Kp =
PPCl3 × PCl 2
In this system, an increase in temperature (which causes an increase in the equilibrium
concentrations of both PCl3 and Cl2 and a decrease in the equilibrium concentration of PCl5)
causes an increase in the denominator of the above expression as well as a decrease in the
numerator of the above expression. Both of these changes serve to decrease the value of Kp.
(d) Decreasing the container volume for a gaseous system will produce an increase in partial pressures
for all gaseous reactants and products. In order to lower the increase in partial pressures, the
equilibrium will shift so as to favor the product side having the smaller number of gaseous
molecules, in this case to the right. This shift will decrease the amount of Cl2 and PCl3 at
equilibrium, and it will increase the amount of PCl5 at equilibrium. While the change in volume
will change the position of the equilibrium, it does not change the value for Kp.

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15.15 2CO(g) + O2(g)
2CO2(g)

Using the stoichiometry of the reaction we can see that for every mol of O2 that is used, twice as much CO
will react and twice as much CO2 will be produced. Consequently, if the [O2] decreases by 0.030 mol/L,
the [CO] decreases by 0.060 mol/L and [CO2] increases by 0.060 mol/L.

15.16 Kc =
[CO2 ][ H 2 ] =
(0.150)(0.200)
= 4.06
[CO][ H 2 O] (0.180)(0.0411)

15.17 (a) The initial concentrations were:

[PCl3] = 0.200 mol/1.00 L = 0.200 M
[Cl2] = 0.100 mol/1.00 L = 0.100 M
[PCl5] = 0.00 mol/1.00 L = 0.000 M
(b) The change in concentration of PCl3 was (0.200 – 0.120) M = 0.080 mol/L. The other materials
must have undergone changes in concentration that are dictated by the coefficients of the balanced
chemical equation, namely: PCl3 + Cl2
PCl5 so both PCl3 and Cl2 have decreased by 0.080 M
and PCl5 has increased by 0.080 M.
(c) As stated in the problem, the equilibrium concentration of PCl3 is 0.120 M. The equilibrium
concentration of PCl5 is 0.080 M since initially there was no PCl5. The equilibrium concentration
of Cl2 equals the initial concentration minus the amount that reacted, 0.100 M – 0.080 M = 0.020
M.
PCl5  (0.080)
(d) Kc = = = 33
PCl3 [ PCl2 ] (0.120)(0.020)

15.18 Kc =
[ NO2 ]2
[ N 2O4 ]
4.61 × 10 =–3 [ NO2 ]2
 0.0466 
 2 
 
[NO2] = 1.04 × 10–2 M

CH3CO 2 C2 H5 [ H 2 O ]
Kc = 
(0.910)(0.00850)
15.19 = = 4.10
CH3CO 2 H 
C2 H5 OH  (0.210) C 2 H5 OH 

[C2H5OH] = 8.98 × 10–3 M

15.20 Initially we have [H2] = [I2] = 0.200 M.

[H2] [I2] [HI]

I 0.200 0.200 –
C –x –x +2x
E 0.200–x 0.200–x +2x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ HI]2 =
(2x)2
= 49.5
[ H 2 ][ I2 ] ( 0.200 − x )( 0.200 − x )

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2x
Take the square root of both sides of this equation to get; = 7.04 . This equation is easily
( 0.200 − x )
solved giving x = 0.156. The substances then have the following concentrations at equilibrium: [H2] = [I2]
= 0.200 – 0.156 = 0.044 M, [HI] = 2(0.156) = 0.312 M.

15.21 Initially we have [H2] = 0.200 M, [I2] = 0.100 M.

[H2] [I2] [HI]

I 0.200 0.100 –
C –x –x +2x
E 0.200–x 0.100–x +2x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ HI]2 =
(2x)2
= 49.5
[ H 2 ][ I2 ] ( 0.200 − x )( 0.100 − x )
4x2 = 49.5(0.0200 – 0.300x + x2)
45.5x2 –14.9x + 0.990 = 0
Solve the quadratic equation:

−b ± b2 − 4ac − ( −14.9 ) ± (14.9 )2 − 4 ( 45.5 )( 0.990 )

x= = = 0.0.0934
2a 2 ( 45.5 )
The substances then have the following concentrations at equilibrium:
[H2] = 0.200 – 0.0934 = 0.107 M
[I2] = 0.100 – 0.0934 = 0.0066 M
[HI] = 2(0.0.0934) = 0.1868 M.

15.22 2NH3(g)
N2(g) + 3H2(g)

[NH3] [N2] [H2]
I 0.041 – –
C –2x +x +3x
E 0.041–x x +3x

Substitute the values for the equilibrium concentrations into the mass action expression:

Kc =
[ N 2 ][ H 2 ]3 =
( x )( 3x )
3
= 2.3 × 10–9
2
NH3  ( 0.041 − x )2
We will assume that x is small compared to the concentration of NH3, so the equation will simplify to:
27x 4
Kc = = 1.4 × 10–13
2
( 0.041)
x = 1.4 × 10–13
4

x = 6.2 × 10–4
[N2] = 6.2 × 10–4
[H2] = 1.9 × 10–3

15.23 N2(g) + O2(g)
2NO(g)

[N2] [O2] [NO]

I 0.033 0.00810 –
C –x –x +2x
E 0.033–x 0.00810–x +2x

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Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ NO]2 =
(2x)2
= 4.8 × 10−31
[ N 2 ][ O2 ] ( 0.033 − x )( 0.00810 − x )
If we assume that x << 0.033 and x << 0.00810, we can simplify this equation. (Because the value of Kc is
so low, this assumption should be valid.) The equation simplifies as:
(2x)2
Kc = = 4.8 × 10−31
( 0.033)( 0.00810 )
This equation is easily solved to give x = 5.7 × 10–18 M. The equilibrium concentration of NO is 2x
according to the ICE table so, [NO] = 1.1 × 10–17 M.

Review Questions

15.1 See Figure 15.1.

15.2 The reactants are the substances to the left of the arrow in a chemical equation, and in terms of equilibrium,
the concentration of the reactants are in the denominator in the mass action expression. The products are
the substances to the right of the arrow in a chemical equation, and in terms of equilibrium, the
concentration of the reactants are in the numerator in the mass action expression.

15.3 An equilibrium law is the statement that the reaction quotient, i.e., the value of Kc must be equal to the
numerical value of the mass action expression once equilibrium is attained.
The reaction quotient is the numerical value of the mass action expression.

15.4 The reaction quotient becomes equal to the value of Kc once equilibrium has been attained.

15.5 If the value of Q is less than Kc, then the ratio of the numerator, or products, to the dominator, or reactants,
is less than the ratio for the equilibrium values. In order to restore equilibrium the reaction must move to
increase the ratio, or increase the amount of products. Therefore, the reaction will proceed in the forward
direction.

15.6 By convention, the products are always written into the numerator and the reactants are written into the
denominator of the mass action expression.

15.7 This equilibrium constant is small, and we do not expect the equilibrium to favor products.

15.8 The increasing tendency to go to completion is: (a) < (c) < (b), based on the relative magnitudes of Kc.

∆n g
15.9 K p = K c × ( RT )

where ∆ng is equal to the change in the number of moles of gaseous material on going from reactants to
products. The value to be used for the gas constant, R, is 0.0821 L atm K–1 mol–1.

15.10 For the ith component of a gas mixture, the partial pressure is given by the ideal gas law:

n i RT
Pi = = MiRT, since ni/Vi is equal to molarity, Mi.
Vi

The proportionality constant between Pi and the molarity of the ith gas, Mi, is the product RT.

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15.11 In a homogeneous equilibrium, all of the reactants and products are in the same phase. In heterogeneous
equilibria, at least two different phases are found among the reactants and products.

15.12 This is possible because their concentrations are constants that are incorporated into the numerical values of
equilibrium constants. The concentrations may be considered constant because as the solid or liquid loses
(or gains) mass, it loses (or gains) a volume proportional to the mass.

15.13 The value for ∆ng, is the difference between the number of moles of reactant gas and the number of moles
of product gas:
∆ng, = (moles of gaseous products) – (moles of gaseous reactants)
∆ng, = 2 mol – 0 mol = 2

15.14 When a system at equilibrium is disturbed so that the equilibrium is upset, the system changes in a way that
opposes the disturbance and returns the system to a state of equilibrium.

15.15 If a reactant is added to the reaction, then the value of the reaction quotient will decrease since the
concentrations of the reactants is in the denominator of the reaction quotient. In order to re–establish
equilibrium, the reaction will have to shift to the products.

15.16 Since the volume is decreased, initially, the pressure will be increased. This reaction will then adjust to
relieve the excess pressure. This is done by moving to the side with fewer moles of gaseous substance. In
the reaction: N2O4(g)
2NO2(g), this is on the left side of the equation.

15.17 (a) This is an exothermic reaction. By increasing the temperature, shifts the equilibrium to the left,
more reactants are formed, therefore the denominator becomes larger, and the KP decreases.
(b) This is an endothermic reaction. By increasing the temperature, the equilibrium is shifted to the
right and more products are formed, and the numerator increases and KP increases.
(c) This is the same as part (a): an exothermic reaction and the increase in temperature shifts the
reaction to the left and increases the amount of the reactants and KP decreases.

15.18 A catalyst affects the rate of the reaction, but does not affect the position of the equilibrium. The catalyst
affects both the forward and the reverse reaction to the same extent, so the ratios of the forward and the
reverse reactions for the catalyzed and uncatalyzed reactions do not change.

Review Problems

2
15.19 (a) Kc = POCl3  (d) Kc =
[ NO2 ]2 [ H 2 O]8
2
PCl3  [ O 2 ] [ N 2 H 4 ][ H 2 O2 ]6

(b) Kc =
[SO2 ]2 [ O2 ] (e) Kc =
[SO2 ][ HCl]2
SO3 
2 [SOCl2 ][ H 2 O]

(c) Kc =
[ NO]2 [ H 2 O]2
[ N 2 H 4 ][ O2 ]2

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 Chapter 15

3
15.20 (a)
NCl3 [ HCl]
Kc =  (d) Kc =
[ HOCl]2
[ Cl2 ]3 NH3  [ H 2 O][Cl2 O]

2
(b) Kc =
[ PCl2 Br ][ PClBr2 ] (e) Kc = BrF5 
PCl3 
PBr3  [ Br2 ][ F2 ]5

(c) Kc =
[ HNO2 ]2
[ NO][ NO2 ][ H 2 O]
2 2 8

15.21 (a) Kp =
( PPOCl ) 3
(d) Kp =
( PNO ) ( PH O )
2 2

2 6
( PPCl ) ( PO )
3 2
( PN H )( PH O )
2 4 2 2

2 2
(b) Kp =
( PSO ) ( PO )
2 2
(e) Kp =
( PSO ) ( PHCl )
2

( PSO )
2
3
( PSOCl )( PH O )
2 2

2
( PNO )2 ( PH O ) 2
(c) Kp =
2
( PN H )( PO )
2 4 2

3
15.22 (a) Kp =
( PNCl ) ( PHCl )
3
(d) Kp =
( PHOCl )2
2
3
( PCl ) ( PNH ) 3
( PH O )( PCl O )
2 2

(b) Kc =
( PPCl Br )( PPClBr )
2 2
(e) Kc =
( PBrF ) 5

( PPCl )( PPBr )
3 3 ( PBr )( PF )
5
2 2

(c) Kc =
( PHNO ) 2

( PNO ) ( PNO )( PH O ) 2 2

 Ag(NH ) +   Cd(SCN) 2 − 
Kc = 
3 2   4 
15.23 (a) (b) Kc =
 Ag +   NH 2 Cd 2+  SCN − 
4
  3    

 H O +   ClO −   2− 
HCO3  SO 4 
Kc =   
3
15.24 (a) (b) Kc =
[ HClO]  CO 2  [ HSO ]
 3  4

15.25 The first equation has been reversed in making the second equation. We therefore take the inverse of the
value of the first equilibrium constant in order to determine a value for the second equilibrium constant:
K = 1 × 1085

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15.26 If we reverse the second reaction and double it, we can then add the first and second reactions together to
obtain the desired reaction. When we double the second reaction we square the rate constant. When we
reverse it, we invert the rate constant. Consequently, we get the following:

2CH4(g)
C2H6(g) + H2(g) Kc = 9.5 × 10–13

2CH3OH(g) + 2H2(g)
2CH4(g) + 2H2O(g) Kc = 1.3 × 1041

Adding these equations we get:

2CH3OH(g) + H2(g)
C2H6(g) + 2H2O(g) Kc = 1.2 × 1029

Where the Kc for the final reaction is the product of the Kc for the first reaction and the Kc for the
“modified” second reaction.

15.27 (a) Kc =
[ HCl]2 (b) Kc =
[ HCl]
[ H 2 ][Cl2 ] 1
[ H 2 ] [Cl2 ]
2
1
2

Kc for reaction (b) is the square root of Kc for reaction (a).

15.28 Kc =
[ H 2 ][Cl2 ]
[ HCl]2
This is equal to 1/Kc for Review Problem 15.27(a).

15.29 M = P/RT

( 755 torr ) 
1 atm 
 760 torr 
M= = 0.0381 M
( L atm 318 K
0.0821 mol K ( ))
15.30 P = M × RT = (0.0250 mol/L)(0.0821 L atm/K mol)(418 K)
P = 0.858 atm

15.31 b, since ∆ng = 0

15.32 a, since ∆ng = 0

15.33 Kp = Kc × (RT)∆ng
Kp = 11[(0.0821 L atm K–1 mol–1)(498 K)]–2 = (5.98 × 10–4) × Kc
Kp = 6.3 × 10−3

15.34 Kp = Kc × (RT)∆ng
Kp = 2.9 × 104[(0.0821 L atm K–1 mol–1)(673 K)]1
Kp = 1.6 × 106

15.35 Kp = Kc × (RT)∆ng
2.7 × 10−2= Kc[(0.0821 L atm K–1 mol–1)(773 K)]1
Kc = 4.2 × 10−4

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15.36 Kp = Kc × (RT)∆ng
4.7 × 1057 = Kc × [(0.0821 L atm K–1 mol–1)(573 K)]–1
Kc = 2.2 × 1059

15.37 Kp = Kc × (RT)∆ng
5.4 × 10−5 = Kc[(0.0821 L atm K–1 mol–1)(1046 K)]–2
Kc = 0.40

15.38 Kp = Kc × (RT)∆ng
1
K p = 8.4 × 10−4  0.0821 mol
( L atm 668 K 
)
K ( )

Kp = 4.6 × 10−2
15.39 In each case we get approximately 55.5 M:
(a)
 1 g   1 mol H 2 O 
mol H 2 O = ( 25.0 mL H 2 O )    = 1.39 mol H 2 O
 1 mL   18.02 g H 2 O 
 1.39 mol H 2 O   1000 mL 
M=   = 55.6 M
 25.0 mL H 2 O   1 L 

(b)
 1 g   1 mol H 2 O 
mol H 2 O = (150.0 mL H 2 O )    = 8.324 mol H 2 O
 1 mL   18.02 g H 2 O 
 8.324 mol H 2 O   1000 mL 
M=   = 55.49 M
 150.0 mL H 2 O   1 L 

(c)
 1000 mL  1 g   1 mol H 2 O 
mol H 2 O = (1.00 L H 2 O )     = 55.5 mol H 2 O
 1 L  1 mL   18.02 g H 2 O 
 55.5 mol H 2 O 
M=  = 55.5 M
 1.00 L H 2 O 

15.40 The density is 2.164 g/mL.

 2.164 g   1 mol NaCl 
(
mol NaCl = 12.0 cm3 NaCl  ) 
 1 cm3  58.44 g NaCl 
 = 0.4444 mol NaCl

 0.4444 mol NaCl 

M=   = 37.03 M
 0.0120 L NaCl 

 1 mol NaCl 
mol NaCl = ( 25.0 g NaCl )   = 0.4278 mol NaCl
 58.44 g NaCl 
 1 cm3 NaCl   1 L NaCl 
L NaCl = 25.0 g NaCl   = 1.155 × 10−2 L NaCl
 2.164 g NaCl   1000 cm3 NaCl 
 
 0.4278 mol NaCl 
M=   = 37.04 M
 1.155 × 10−2 L NaCl 

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15.41 (a) Kc =
[CO]2 (d) Kc =
[ H 2 O][ CO2 ]
[O2 ] [ HF]2
5
(b) K c = [ H 2 O ][SO 2 ] (e) K c = [ H 2O]

(c) Kc =
[CH 4 ][ CO2 ]
[ H 2 O]2

15.42 (a) Kc =
[CO2 ] (d) K c = [ H 2O]
[SO2 ]
 Cl− 
(b) Kc =   (e) Kc =
[ N 2 ][ H 2 O]3
 Br 
− 2
NH3 
 
2
(c) K c = Cu 2+  OH − 
  

15.43
[HCl] [HI] [Cl2]
I 0.150 – –
C –2x +2x +x
E 0.150–2x +2x +x

Note: Since the I2(s) has a constant concentration, it may be neglected.

[HI]2 [Cl2 ]
Kc = = 1.6 × 10−34
[HCl]2
( 2x )2 ( x )
Kc = = 1.6 × 10−34
(0.150 − 2x)2

Because the value of Kc is so small, we make the simplifying assumption that (0.100 – 2x) ≈ 0.100, and the
above equation becomes:
[HI]2 [Cl2 ]
Kc = = 1.6 × 10−34
2
[HCl]
( 2x )2 ( x )
Kc = = 1.6 × 10−34
2
(0.150)

4x3 = 3.6 × 10–36; ∴ x = 9.65 × 10–13, and the above assumption is seen to have been valid.

[HI] = 2x = 1.93 × 10–12 M

[Cl2] = x = 9.65 × 10–13 M
[HCl] = (0.100 – 2x) ≈ 0.150 M

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 Chapter 15

15.44 AgCl(s) + Br–(aq)
AgBr(s) + Cl–(aq)

[Br–] [Cl–]
I 0.12 –
C –x +x
E 0.12–x +x

Substituting the above values for equilibrium concentrations into the mass action expression gives:
 Cl− 
Kc =   = x
= 360
 Br −  0.12 − x
 
Solving for the value of x: x = [Cl–] = 0.117 M and [Br–] = 0.12 – 0.117 = 0.0032 M.
If we concern ourselves with significant figures, the [Br–] ≈ 0.00 M.

15.45 (a) The system shifts to the right to consume some of the added methane.
(b) The system shifts to the left to consume some of the added hydrogen.
(c) The system shifts to the right to make some more carbon disulfide.
(d) The system shifts to the left to decrease the amount of gaseous moles.
(e) The system shifts to the right to absorb some of the added heat.

15.46 (a) increase; we are adding a reactant

(b) decrease; we are removing a reactant
(c) increase; decreasing the volume favors the side with fewer gas molecules
(d) no change; a catalyst increases the rate but does not affect the concentration
(e) decrease; this is an exothermic reaction so heat may be considered a product

15.47 (a) right (b) left (c) left

(d) right (e) no effect (f) left

15.48 (a) increase (b) increase

(c) increase (d) decrease

15.49 The mass action expression for this equilibrium is:

[PCl5 ]
Kc = = 0.18
[PCl3 ][PCl2 ]

(a) The value for the reaction quotient for this system is:

Q=
( 0.00500 ) = 4.96
( 0.0420 )( 0.0240 )
This is not the value of the equilibrium constant, and we conclude that the system is not at
equilibrium.

(b) Since the value of the reaction quotient for this system is larger than that of the equilibrium
constant, the system must shift to the left to reach equilibrium.

15.50 The mass action expression for the system is:

Kc =
[ NO]SO3  = 85.0
[SO2 ][ NO2 ]

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and the reaction quotient for the system is:

Q=
[ NO]SO3  =
( 0.0250 )( 0.0400 ) = 114
[SO2 ][ NO2 ] ( 0.00250 )( 0.00350 )
(a) The system is not at equilibrium because Q ≠ Kc.

(b) Since the value of the reaction quotient is larger than the value of the equilibrium constant, the
system must shift to the left in order to reach equilibrium.

CH3OH  CH3OH 
15.51 Kc =  = = 0.500
[CO][ H 2 ] ( 0.175)( 0.225)2
2

[CH3OH] = 4.43 × 10–3 M.

15.52 The mass action expression is:

2
PNH
3
KP = = 0.018
PN 2 PH3
2

Solving for [H2] gives:

2
PNH ( 20.5)2
PH 2 =3 3
= 3 = 26.3 atm
PN 2 K P (1.28) (0.018)

CH3OH  ( 0.00261) = 0.398

15.53 Kc =  =
[CO][ H 2 ]2 ( 0.105)( 0.250 )2
PC2 H5OH ( 6.99 )
15.54 KP = = = 9.35
PC 2 H 4 PH 2O ( 0.575)(1.30 )
15.55
[HBr] [H2] [Br2]
I 0.075 – –
C –2x +x +x
E 0.075–2x +x +x

The problem tell us that [Br2] = 0.0955 M = x at equilibrium. Using the ICE table as a guide we see that
the equilibrium concentrations are; [H2] = [Br2] = 0.0955 M and [HBr] = 0.500–2(0.0955) = 0.309 M.

Kc =
[ H 2 ][ Br2 ] =
( 0.0955)( 0.0955) = 0.0955
[ HBr ]2 ( 0.075 )2

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15.56 CH2O(g)
H2(g) + CO(g) Kc =

[ H 2 ][CO]
[CH 2 O]
[CH2O] [H2] [CO]
I 0.100 – –
C –x +x +x
E 0.100–x +x +x

The problem states that the equilibrium concentration of CH2O is 0.066 M. Therefore,
x = 0.034 M = [H2] = [CO] at equilibrium. Substituting these values into the mass action expression we can
determine Kc:

Kc =
[ H 2 ][CO] =
(0.034)(0.034)
= 1.8 × 10−2
[CH 2 O] 0.066

15.57 According to the problem, the concentration of NO2 increases in the course of this reaction. This means
our ICE table will look like the following:

[NO2] [NO] [N2O] [O2]

I 0.0560 0.294 0.184 0.377
C +x +x –x –x
E 0.0560 + x 0.294 + x 0.184 – x 0.377 – x

The problem tell us that [NO2] = 0.118 M = 0.0560 + x at equilibrium. Solving we get; x = 0.062 M.
Using the ICE table as a guide we see that the equilibrium concentrations are; [NO] = 0.356 M, [N2O] =
0.122 M and [O2] = 0.315 M.

Kc =
[ N 2 O][ O2 ] =
( 0.122 )( 0.315) = 0.915
[ NO2 ][ NO] ( 0.118)( 0.356 )

15.58 Kc =
[ NO2 ]4
[ N 2 O]2 [ O2 ]3
[N2O] [O2] [NO2]
I 0.020 0.0560 –
C –2x –3x +4x
E 0.020 – 2x 0.0560 – 3x +4x

At equilibrium [NO2] = 4x = 0.020 M

x = 0.0050M
So, [N2O] = 0.020 – 2(0.0050) = 0.010 M
[O2] = 0.0560 – 3(0.0050) = 0.041M

Kc =
[0.020]4 = 23
[0.010]2 [ 0.041]3

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15.59 2BrCl
Br2 + Cl2

[BrCl] [Br2] [Cl2]

I 0.075 – –
C –2x +x +x
E 0.075–2x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ Br2 ][Cl2 ] = ( x )( x ) = 0.145
[ BrCl]2 ( 0.075 − 2x )2
Take the square root of both sides to get

x
Kc = = 0.381
0.075 − 2x

Solving for x gives: x = 0.016 M = [Br2] = [Cl2]

15.60 2BrCl
Br2 + Cl2

In this problem, the reaction will shift from right to left as written above. This is due to the presence of
products and the absence of reactants.

[BrCl] [Br2] [Cl2]

I – 0.0225 0.0225
C +2x –x –x
E +2x 0.0225–x 0.0225–x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ Br2 ][Cl2 ] =
( 0.0225 − x )( 0.0225 − x ) = 0.145
[ BrCl]2 ( 2x )2
Take the square root of both sides to get

0.0225 − x
Kc = = 0.381
2x

Solving for x gives: x = 0.0128 M. The individual concentrations are then: [Br2] = [Cl2] = 0.0225 –
0.0128 = 0.00973 M, [BrCl] = 2(0.0128) = 0.0256 M.

15.61 The initial concentrations are each 0.280 mol/2.00 L = 0.140 M.

[SO3] [NO] [NO2] [SO2]

I 0.140 0.140 – –
C –x –x +x +x
E 0.140–x 0.140–x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

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 Chapter 15

Kc =
[ NO2 ][SO2 ] =
( x )( x ) = 0.500
SO3 [ NO ] ( 0.140 − x )( 0.140 − x )
Taking the square root of both sides of this equation gives: 0.707 = x/(0.140 – x)
Solving for x we have: 1.707(x) = 0.09898,
x = 0.0580 mol/L = [NO2] = [SO2],
[NO] = [SO3] = 0.140 – x = 0.0820 mol/L

15.62 The initial concentrations are each 0.140 M.

[SO3] [NO] [NO2] [SO2]

I – – 0.140 0.140
C +x +x –x –x
E +x +x 0.140–x 0.140–x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ NO2 ][SO2 ] =
( 0.140 − x )( 0.140 − x ) = 0.500
SO3 [ NO ] ( x )( x )
Taking the square root of both sides of this equation gives: 0.707 = (0.140 – x)/x. Solving for x we have:
1.707(x) = 0.140
∴ x = 0.0820 mol/L = [NO] = [SO3],
[NO2] = [SO2] = 0.140 – x = 0.0580 mol/L

Although these two systems reach different equilibrium positions, the equilibrium concentrations of the
four substances in each experiment give the same value for the equilibrium constant when substituted into
the mass action expression.

An alternative method for solving problems where the reaction proceeds from right to left, such as this
problem, is to reverse the reaction written and use this “new” reaction as the basis for the problem. In
doing this, the mass action expression and the equilibrium constant must change to reflect the “new”
reaction. As outlined in Section 15.2, “when the direction of an equation is reversed, the new equilibrium
constant is the reciprocal of the original” and the “new” mass action expression is also the reciprocal of the
original. Try solving this problem using this method. Your answer should, of course, remain the same as
stated above.

15.63 The initial concentrations are all 1.00 mol/100 L = 0.0100 M. Since the initial concentrations are all the
same, the reaction quotient is equal to 1.0, and we conclude that the system must shift to the left to reach
equilibrium since Q > Kc.

[CO] [H2O] [CO2] [H2]

I 0.0150 0.0150 0.0150 0.0150
C +x +x –x –x
E 0.0150+x 0.0150+x 0.0150–x 0.0150–x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[CO2 ][ H 2 ] =
( 0.0150 − x )( 0.0150 − x ) = 0.400
[CO][ H 2 O] ( 0.0150 + x )( 0.0150 + x )

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 Chapter 15

We take the square root of both sides of the above equation:

( 0.0150 − x ) = 0.632
( 0.0150 + x )
and (0.632)(0.0150 + x) = 0.0150 – x
(1.632)x = 5.52 × 10–3, or
x = 3.38 × 10–3 mol/L
The equilibrium concentrations are then:
[H2] = [CO2] = (0.0150 – 3.38 × 10–3) = 0.0116 M,
[CO] = [H2O] = (0.0150 + 3.38 × 10–3) = 0.0184 M.

15.64 If we substitute the initial concentrations of 0.0400 M for each component of this mixture into the reaction
quotient expression that results from the balanced equation in the text, we see that the reaction quotient
equals one. Since Q > Kc, the reaction will proceed from right to left as written, i.e., [Br2] and [Cl2] will
decrease and [BrCl] will increase.

[BrCl] [Br2] [Cl2]

I 0.0450 0.0450 0.0450
C + 2x –x –x
E 0.0450 + 2x 0.0450 – x 0.0450 – x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ Br2 ][Cl2 ] =
( 0.0450 − x )( 0.0450 − x ) = 0.145
[ BrCl]2 ( 0.0450 + 2x )2

Take the square root of both sides of this equation to get;

( 0.0450 − x ) = 0.381 .
( 0.0450 + 2x )
This equation is easily solved giving x = 0.0158 M.
The substances then have the following concentrations at equilibrium:
[Cl2] = [Br2] = 0.0450 – 0.0158 = 0.0292 M,
[BrCl] = 0.0450 + 2(0.0158) = 0.0766 M.

15.65
[HCl] [H2] [Cl2]
I 0.0450 – –
C –2x +x +x
E 0.0450–2x +x +x

Kc =
[ H 2 ][Cl2 ] =
( x )( x ) = 3.2 × 10−34
[ HCl]2 ( 0.0450 − 2x ) 2

Because Kc is so exceedingly small, we can make the simplifying assumption that x is also small enough to
make (0.0450 – 2x) ≈ 0.0450. Thus we have: 3.2 × 10–34 = (x)2/(0.0450)2

Taking the square root of both sides, and solving for the value of x gives:
x = 8.0 × 10–19 M = [H2] = [Cl2]
[HCl] = (0.0450 – x) ≈ 0.0450 mol/L

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 Chapter 15

15.66 The initial concentrations are :

0.250 mol/4.00 L = 0.0625 M N2O
0.350 mol/4.00 L = 0.0875 M NO2

[N2O] [NO2] [NO]

I 0.0625 0.0875 –
C –x –x +3x
E 0.0625–x 0.0875–x +3x

Kc =
[ NO]3 = 1.4 × 10−10
[ N 2 O][ NO2 ]
(3x)3
Kc =
(0.0625)(0.0875)
x = 2.84 × 10–14
3

x = 3.05 × 10–5

Where we have assumed that x << 0.0625. Solving we get x = 3.05 × 10−5.

Therefore, the molar concentration of NO would be 3x or 3(3.05 × 10−5) M = 9.15 × 10−5 M.

15.67 Kc =
[ CO]2 [O2 ] = 6.4 × 10−7
[ CO2 ]2
[CO2] [CO] [O2]
I 2.25 × 10–2 – –
C –2x +2x +x
E 2.25 × 10–2 – 2x +2x +x

Kc =
[ 2x ]2 [ x ] = 6.4 × 10−7
2
 2.25 × 10−2 – 2x 
 
Assume x << 2.25 × 10–2.
4x 3
= 6.4 × 10−7 x = 4.3 × 10−4
(2.25 × 10−2 ) 2
[CO] = 2x = 8.6 × 10−4 M

15.68 Kc =
[ H 2 ]2 [O2 ] = 6.0 × 10−28
[ H 2 O]2
[H2O] [H2] [O2]
I 0.025 mol/5.00L – –
C –2x +2x +x
E 5.0 × 10–3 – 2x +2x +x

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 Chapter 15

Kc =
[ 2x ]2 [ x ] = 6.0 × 10−28
2
5.0 × 10 – 2x −3
 
Assume 2x << 5.0 × 10–3.

4x 3
= 6.0 × 10−28 x = 1.6 × 10−11
−3 2
(5.0 × 10 )
[H 2 ] = 1.6 × 10−11 M, [O 2 ] = 1.6 × 10−11 M

15.69 We first approach the problem in the normal fashion with an initial concentration of
PCl5 = 0.013 M.

[PCl3] [Cl2] [PCl5]

I – – 0.0175
C +x +x –x
E +x +x 0.0175–x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

PCl5  ( 0.0175 − x )
Kc = = = 0.18
PCl3 [ Cl2 ] ( x )( x )
rearranging; 0.18x 2 + x − 0.0175 = 0

We next attempt to use the quadratic equation to solve for the value of x, setting a = 0.18; b = 1; c = –0.013.

However, we find that unless we carry one more significant figure than is allowed, the quadratic formula
for this problem gives us a concentration of zero for PCl5. A better solution is obtained by "allowing" the
initial equilibrium to shift completely to the left, giving us a new initial situation from which to work:

[PCl3] [Cl2] [PCl5]

I 0.0175 0.0175 –
C –x –x +x
E 0.0175–x 0.0175–x +x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

PCl5  (+x )
Kc = = = 0.18
PCl3 [ Cl2 ] ( 0.0175 − x )( 0.0175 − x )
Now, we may assume that x << 0.0175. The equation is simplified and we solve for x
x = [PCl5] = 5.5 × 10–5 M.

15.70 All concentrations are a factor of ten less than the stated value due to the container size. Since Q < Kc for
this reaction, the reaction proceeds as written, i.e., from left to right.

[SO2] [NO2] [NO] [SO3]

I 0.0100 0.00600 0.00800 0.0120
C –x –x +x +x
E 0.0100–x 0.00600–x 0.00800+x 0.0120+x

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 Chapter 15

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ NO]SO3  =
( 0.00800 + x )( 0.0120 + x ) = 85.0
[SO2 ][ NO2 ] ( 0.0100 − x )( 0.00600 − x )
0.00510 – 1.36(x) + 85.0(x)2 = 9.60 × 10–5 + 0.0200(x) + (x)2
84.0(x)2 – 1.38(x) + 0.00500 = 0

The quadratic equation is used, with the following values: a = 84.0; b = –1.38;
c = 0.00500. Upon solving for x, we find that only the negative root is sensible:
x = 0.00542 M.

[SO2] = 0.0100 – 0.00542 = 0.0046 M

[NO2] = 0.00600 – 0.00542 = 0.00058 M
[NO] = 0.00800 + 0.00542 = 0.0134 M
[SO3] = 0.0120 + 0.00542 = 0.0174 M

15.71
[SO3] [NO] [NO2] [SO2]
I 0.0750 0.0875 – –
C –x –x +x +x
E 0.0750 0.0875 +x +x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ NO2 ][SO2 ] =
( x )( x ) = 0.500
SO3 [ NO ] ( 0.0750 − x )( 0.0875 − x )
Since the equilibrium constant is not much larger than either of the values 0.0750 or 0.0875, we cannot
neglect the size of x in the above expression. A simplifying assumption is not therefore possible, and we
must solve for the value of x using the quadratic equation. Multiplying out the above denominator,
collecting like terms, and putting the result into the standard quadratic form gives:
0.500x2 + (8.13 × 10–2)x – (3.28 × 10–3) = 0

x=
−8.13 × 10−2 ± (8.13 × 10 ) −2
− (
4(0.500) −3.28 × 10−3 ) = 0.0335 M
2(0.500)

using the (+) root. So, [NO2] = [SO2] = 0.0335 M

15.72 If we substitute the initial concentrations for each component of this mixture into the reaction quotient
expression that results from the balanced equation in the text, we see that the reaction quotient equals
0.375. Since Q > Kc for this situation, the reaction will proceed from right to left, i.e., [Br2] and [Cl2] will
decrease and [BrCl] will increase.

[BrCl] [Br2] [Cl2]

I 0.0400 0.0300 0.0200
C +2x –x –x
E 0.0400+2x 0.0300–x 0.0200–x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

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 Chapter 15

Kc =
[ Br2 ][Cl2 ] =
( 0.0300 − x )( 0.0200 − x ) = 0.145
[ BrCl]2 ( 0.0400 + 2x )2
Rearranging we get the following quadratic expression: 0 = 0.42x2 – 0.0732x + 0.000368. Solving and
using the negative root gives x = 0.0052 M. The individual concentrations are: [Cl2] = 0.0200 – 0.0052 =
0.0148 M, [Br2] = 0.0300 – 0.0052 = 0.0248 M, [BrCl] = 0.0400 + 2(0.0052) = 0.0504 M.

15.73 Kc =
[ CO][ H 2 O] = 4.3 × 105
[ HCHO2 ]
Since Kc is large, start by assuming all of the HCHO2 decomposes to give CO and H2O

[HCHO2] [CO] [H2O]

I – 0.200 0.200
C +x –x –x
E +x 0.200 –x 0.200 –x

Kc =
[ 0.200][ 0.200] = 4.3 × 105
[x]
x = 9.3 × 10–8
so, at equilibrium
[CO] = [H2O] = 0.200 – x = 0.200 M

15.74 Because of the very large value of Kc, we start by realizing that nearly all of the 0.100 moles of H2 will
react with 0.100 moles of Br2 to form 0.200 moles of HBr. This brings us to a new "initial" condition that
is more realistically close to the true equilibrium condition, i.e., [HBr] = (0.200 moles/10.0 L) = 0.0200 M,
[Br2] = (0.100 moles/10.0 L) = 0.0100 M, [H2] = 0 M. Next, we proceed in the normal fashion, allowing 2x
mol/L of HBr to disappear, and making x mol/L each of H2 and Br2 in order to reach equilibrium:

[H2] [Br2] [HBr]

I – 0.0100 0.0200
C +x +x –2x
E +x 0.0100+x 0.0200–2x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ HBr ]2 =
( 0.0200 − 2x )2 = 2.0 × 109
[ H 2 ][ Br2 ] ( + x )( 0.0100 + x )
We next make the assumptions that (0.0200 – 2x) ≈ 0.0200, and (0.0100 + x) ≈ 0.0100, giving:
2.0 × 109 = (0.0200)2/(0.0100)(x)
x = 2.0 × 10–11 M = [H2].
The small size of x demonstrates that the assumptions made above were justified.

[HBr] = 0.0200 – 2x = 0.0200 M

[Br2] = 0.0100 + x = 0.0100 M

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 Chapter 15

Additional Exercises

15.75 (a) The mass action expression is:

Kp =
( PNO ) 2
= 0.140 atm
( PN O ) 2 4

Solving the above expression for the partial pressure of NO2, we get:

PNO2 = PN 2O 4 × K p = ( 0.225 atm )( 0.140 atm ) = 0.177 atm

(b) Ptotal = PNO2 + PN2O4 = 0.177 + 0.225 = 0.402 atm

3
[ NO]3 = ( 4.7 ×10 ) = 1.88 ×10−20
−8
15.76 Kc =
[ N 2 O][ NO2 ] ( 0.023)( 0.24 )
∆n
K p = K c ( RT ) = (1.88 × 10–20)(0.0821 × 298)1 = 4.6 × 10–19
g

5
H5 IO6 
15.77 Kc = = 1 × 10–85
7 7
 IO −   H + 
 3   

H5IO6 is a weak acid and must be part of the equilibrium expression. As ions, both H+ and IO3– are part of
the expression. H2O is ignored since it is a pure liquid and I2 is ignored since it is a solid at 25°C.

15.78 The initial concentrations are:

[NO2] = (0.250 mol/4.00 L) = 0.0625 M
[NO] = (0.275 mol/4.00 L) = 0.0688 M
[N2O] = (0.175 mol/4.00 L) = 0.0438 M
[O2] = (0.225 mol/4.00 L) = 0.0563 M

Substituting these values into the mass action expression we determine:

Q=
[ N 2 O][ O2 ] = ( 0.0438)( 0.0563) = 0.573
[ NO2 ][ NO] ( 0.0625)( 0.0688)
Since Q<Kc, this reaction will proceed from left to right as written. The ICE table becomes:

[NO2] [NO] [N2O] [O2]

I 0.0625 0.0688 0.0438 0.0563
C –x –x +x +x
E 0.0625 – x 0.0688 – x 0.0438 + x 0.0563 + x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ N 2 O][ O2 ] =
( 0.0438 + x )( 0.0563 + x ) = 0.914
[ NO2 ][ NO] ( 0.0625 − x )( 0.0688 − x )
To solve we need to use the quadratic equation. Expanding the above calculation we get:

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 Chapter 15

0.086x2 + 0.220x – 0.00146 = 0

Solving we get x = 0.00581. So,
[NO2] = 0.0625 – x = 0.0567 M
[NO] = 0.0688 – x = 0.0630 M
[N2O] = 0.0438 + x = 0.0380 M
[O2] = 0.0563 + x = 0.0505 M
15.79 First, calculate a value for Kc using a rearranged form of equation 15.9 and setting the value for ∆n to –1:

Kp 1.5 × 1018
Kc = = = 3.7 × 1019
∆n g −1
( RT )  0.0821 L atm
( ) ( 300 K )
 mol K

The value for the equilibrium constant is very large, indicating that the equilibrium lies far to the right. We
therefore anticipate that the initial conditions are unrealistic. The system is "allowed" to come to a more
realistic new initial set of concentrations, by reaction of all of the starting amount of NO, to give a
stoichiometric amount of N2O and NO2. Only then can we solve for the equilibrium concentrations in the
usual manner:

[NO] [N2O] [NO2]

I – 0.015 0.015
C +3x –x –x
E +3x 0.015 – x 0.015 – x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ N 2 O][ NO2 ] =
(0.015 − x)(0.015 − x)
= 3.7 × 1019
[ NO]3 (3x) 3

The simplifying assumption can be made that the value for x is much smaller than the number 0.015. Upon
solving for x we get: 27x3 = 6.1 × 10–24 x = 6.1 × 10–9 M
–8
[NO] = 3x = 1.8 × 10 M,
[N2O] = [NO2] = 0.015 – x = 0.015 M.

15.80 (a) Equilibrium is unaffected by the addition of a solid.

(b) Equilibrium is unaffected by the removal of a solid (provided it is not completely removed.)
(c) The equilibrium will shift to the left.
(d) The equilibrium will shift to the right.

15.81 The initial concentrations are: [NO2] = (0.250 mol/5.00 L) = 0.0500 M,

[NO] = (0.250 mol/5.00 L) = 0.0500 M, [N2O] = (0.250 mol/5.00 L) = 0.0500 M,
[O2] = (0.250 mol/5.00 L) = 0.0500 M.

Substituting these values into the mass action expression we determine:

Q=
[ N 2 O][O2 ] =
( 0.0500 )( 0.0500 ) = 1.00
[ NO2 ][ NO] ( 0.0500 )( 0.0500 )
Since Q > Kc, this reaction will proceed from right to left as written. The ICE table becomes:

[NO2] [NO] [N2O] [O2]

I 0.0500 0.0500 0.0500 0.0500
C +x +x –x –x
E 0.0500 + x 0.0500 + x 0.0500 – x 0.0500 – x

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 Chapter 15

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[ N 2 O][ O2 ] =
( 0.0500 − x )( 0.0500 − x ) = 0.914
[ NO2 ][ NO] ( 0.0500 + x )( 0.0500 + x )
Taking the square root of both sides we get K c =
( 0.0500 − x ) = 0.956
( 0.0500 + x )
Solving for x we get: x = 1.1 × 10–3. Thus, at equilibrium we have:
[N2O] = [O2] = 0.0489 M, [NO2] = [NO] = 0.0511 M.

If 0.050 moles of NO2 are added (note: 0.050 mol/5.00 L = 0.01 M NO2 added), the ICE table becomes:

[NO2] [NO] [N2O] [O2]

I 0.0511 + 0.01 0.0511 0.0489 0.0489
C –x –x +x +x
E 0.0611 – x 0.0511 – x 0.0489 + x 0.0489 + x

Substituting these values into the mass action expression gives:

Kc =
[ N 2 O][ O2 ] =
( 0.0489 + x )( 0.0489 + x ) = 0.914
[ NO2 ][ NO] ( 0.0611 − x )( 0.0511 − x )
Solving the quadratic expression, 0.086x2 + 0.200 x – 4.6 × 10–4 = 0, we get x = 0.00581. Thus, at
equilibrium, we now have:
[N2O] = 0.0547 M
[O2] = 0.0547 M
[NO2] = 0.0553 M
[NO] = 0.0453 M

15.82 Kc =
[ N 2 O][O2 ] = 0.914
[ NO2 ][ NO]
Let z = the initial concentration.

[NO2] [NO] [N2O] [O2]

I z z – –
C –x –x +x +x
E z–x z –x +x +x

Kc =
[x] [x] = 0.914
[ z -x ] [ z - x ]
Take the square roots of both sides to get
x
= 0.956 x = 0.0600 from the data in the problem so
z − x
0.0600
= 0.956 solving for z we get z = 0.12 M
z − 0.0600
 0.12 mol 
moles NO = moles NO 2 =   ( 5.00 L ) = 0.60 moles
 L 

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 Chapter 15

15.83 (a)

(b) F2(g) + PF3(g)
PF5(g)

PF5(g)
F2(g) + PF3(g)
(c)

Because the volume is smaller, LeChateliers Principle states that the equilibrium will favor the
products. Consequently, equilibrium will be shifted to the right in a smaller volume. As can be
seen here, a higher proportion of the reactants have reacted to form more PF5 as compared to the
case in (a).

15.84 We start by determining the initial concentration of NO2: [NO2] = 0.25 mol/4.00 L = 0.0625 M.

Next, this value is used in an equilibrium law type calculation using the equation:

3NO2
N2O5 + NO

[NO2] [N2O5] [NO]

I 0.0625 – –
C –3x +x +x
E 0.0625–3x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

N 2 O5 [ NO ] x2
Kc =  = = 1.0 × 10−11
3 3
[ NO2 ] ( 0.0625 − 3x )
Assume 3x << 0.0625
x2
= 1.0 × 10−11
3
( 0.0625)

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 Chapter 15

x = 4.9 × 10–8
[N2O5] = 4.9 × 10–8 M
mol N2O5 = (4.9 × 10–8 M)(4.00 L) = 2.0 × 10–7 mol N2O5

15.85 The concentration of the water needs to be calculated:

 1 atm 
17.5 torr  
M=
P
=  760 torr  = 9.57 × 10–4 M
RT
( −1 −1
0.0821 L atm mol K ( 293 K ) )
[NO] [NO2] [H2O] [HNO2]
I 2.59 × 10–3 2.59 × 10–3 9.57 × 10–4 –
C –x –x –x +2x
E 2.59 × 10–3 – x 2.59 × 10–3 – x 9.57 × 10–4 – x 4.0 × 10–4

4.0 × 10–4 = 2x
x = 2.0 × 10–4 M
[NO] = [NO2] = 2.59 × 10–3 – 2.0 × 10–4 = 2.39 × 10–3 M
[H2O] = 9.57 × 10–4 – 2.0 × 10–4 = 7.57 × 10–4 M

Kc =
[ HNO2 ]2 =
( 4.0 ×10 ) −4
= 37
[ NO][ NO2 ][ H 2 O] ( 2.39 ×10−3 )( 2.39 ×10−3 )( 7.57 ×10−4 )

2
15.86 Kc = NH3 
[ H 2 ]3 [ N 2 ]
0.135 =
( 0.030 )2
[ H 2 ]3 ( 0.50 )
[ H 2 ]3 =0.0133
[H2] = 0.237 M

Partial Pressures:
PNH3 = (0.030 M)(0.08214 L atm mol–1 K–1)(373 K) = 0.92 atm
PH 2 = (0.237 M)(0.08214 L atm mol–1 K–1)(373 K) = 7.26 atm
PN 2 = (0.50 M)(0.08214 L atm mol–1 K–1)(373 K) = 15.3 atm

Kp =
( PNH ) 3
=
( 0.92 )2 = 1.44 × 10–4
3
( PH ) ( PN )
2 2
( 7.26 )3 (15.3)

KP using Equation 15.9:

∆n g
K P = K C ( RT )
∆ng = 2 – 4 = –2 mol
KP = 0.135[(0.08214 L atm mol–1 K–1)(373)]–2 = 1.44 × 10–4

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 Chapter 15

Multi-Concept Problems

15.87 First, calculate the number of moles of CO used in the experiment, using the ideal gas law:

PV ( 0.177 atm )( 2.00 L )

n= = = 0.0145 mol
RT ( L atm 298 K
0.0821 mol K ( ) )

Next, calculate the partial pressure of CO at 400 °C:

P=
nRT
=
(
L atm
( 0.0145 mol ) 0.0821 mol K ) ( 673 K ) = 0.401 atm
V ( 2.00 L )
Next, we calculate the number of moles of water that are supplied to the reaction, and convert to partial
pressure for water, using the ideal gas equation:

 1 mol H 2 O 
mol H 2 O = ( 0.391 g H 2 O )   = 0.0217 mol H2O
 18.02 g H 2 O 

P=
nRT
=
(
L atm
( 0.0217 mol ) 0.0821 mol K ) ( 673 K ) = 0.600 atm
V ( 2.00 L )
Finally, we solve for the equilibrium partial pressure in the usual manner:

PHCHO2 PCO P H 2O
I – 0.401 0.600
C +x –x –x
E +x 0.401–x 0.600–x

Substituting the above values for equilibrium partial pressures into the mass action expression gives:

( PCO ) ( PH O ) (0.401 − x)(0.600 − x)

= 1.6 × 106
2
Kp = =
( PHCHO )2
x

Because Kp is so large, we assume x << 0.401 and x << 0.600. We then solve for
PHCHO2 = x = 1.5 × 10–7 atm.

15.88 Kc =
[CO]2 [O2 ] = 6.4 x 10−7
[CO2 ]2

[CO2] [CO] [O2]

I 0.0100 0 0
C –2x +2x +x
E 0.0100–2x +2x +x

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 Chapter 15

(2x)2 (x)
Kc = = 6.4 x 10−7
(0.0100 − 2x)2

x = 2.437 x 10-4 M round answer to 2.44 x 10−4

nRT −4 −1 −1
PCO = = [CO]RT = 2 x 2.44 x 10 M x 0.0821 L atm K mol x 2273 K
V

PCO = 9.11 x 10−2 atm

Molecules of O2 = 2.44 x 10-4 mol L-1 x 1.00 L x 6.02 x 1023 molecules O2 mol-1 = 1.47 x 1020

Density is defined as the mass of substance per volume. During the reaction the volume of the container
does not change and since we must conserve mass during a chemical reaction, the total number of grams of
substances does not change. Therefore, the density of the mixture does not change during the reaction.

We can use bond energies to determine the enthalpy of reaction.

4 C=O bonds are broken: 4 mol x 799 kJ/mol = 3196 kJ

1 O=O bond is formed: 1 mol x (− 494 kJ/mol) = − 494 kJ
2 C≡ O bonds are formed: 2 mol x (− 1072 kJ/mol) = − 2144 kJ

The total enthalpy change for the reaction, as written, is + 558 kJ. This is the amount of heat that would
have been required to form a mole of O2.

At equilibrium we have formed 2.44 x 10−4 moles of O2.

Therefore, the heat required is: (+558 kJ/mol O2) x 2.44 x 10−4 mol O2 = +0.136 kJ or +136 J

15.89 Kc =
[ NO][SO3 ] = 85.0
[SO2 ][ NO2 ]
The initial concentrations are: [SO2] = (0.0255 mol/10.00 L) = 0.00255 M,
[NO2] = (0.0600 mol/10.00 L) = 0.00600 M, [NO] = (0.0800 mol/10.00 L) = 0.00800 M,
[SO3] = (0.0446 mol/10.00 L) = 0.00446 M.

Calculate Q to determine the direction of the reaction.

(0.00800)(0.00446)
Q= = 2.3
(0.00255)(0.00600)

Therefore, the products are favored and the reaction will proceed to the right.

[SO2] [NO2] [NO] [SO3]

I 0.00255 0.00600 0.00800 0.00446
C –x –x +x +x
E 0.00255 – x 0.00600 – x 0.00800+ x 0.00446+x

(0.00800 + x)(0.00446 + x)
= 85.0
(0.00255 − x)(0.00600 − x)

x = 0.002324

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 Chapter 15

[SO2] = 0.000226 M [NO2] = 0.00368 M [NO] = 0.0103 M [SO3] = 0.00678 M

Grams of each gas:

SO2 0.000226 mol L-1 x 10.0 L x 64.06 g mol-1 = 0.146 g

NO2 0.00368 mol L-1 x 10.0 L x 46.00 g mol-1 = 1.69 g
NO 0.0103 mol L-1 x 10.0 L x 30.01 g mol-1 = 3.09 g
SO3 0.00678 mol L-1 z 10.0 L x 80.06 g mol-1 = 5.46 g

Total pressure of the mixture at equilibrium:

P = (n/V) RT = [Xi]RT where Xi is the molar concentration of the ith species.

PT = P(SO2) + P(NO2) + P(NO) + P(SO3)

PT = (0.000226 + 0.00368 + 0.0103 + 0.00678) mol L-1 x 0.0821 L atm K mol-1 x (460 + 273) K

PT = 1.26 atm

15.90 Kc =
[ NO]3 = 1.4 x 10−10
[ N 2 O][ NO2 ]
The molar concentration of the 300 mL sample of gas is given by:
800 torr
n
=
P
= 760 torr atm −1
V RT 0.0821 L atm K −1 mol−1 x (25 + 273)K

n
= 4.30 x 10−2 M
V

The concentration of the gas when placed in the 4.00 L container is given by:

4.30 x 10-2 M x (0.300L/4.00L) = 3.23 x 10-3 M

[N2O] [NO2] [NO]

I 0 0 3.23 x 10-3
C +x +x -3x
E +x +x 3.23 x 10-3 -3x

(3.23 x 10−3 -3x)3

= 1.4 x 10−10
(x)(x)
Be very careful about rounding your coefficients in the cubic equation. You should carry several decimal
places. The equilibrium constant is very small so most of the NO is converted to N2O and NO2. Thus, if
you are not careful you will end up with an answer for x that is larger than 3.23 x 10-3 M.

x = 1.075 x 10-3 M

At equilibrium:

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 Chapter 15

[N2O] = 1.075 x 10-3 M [NO] = 5.00 x 10-6 M

PT = (2 x 1.075 x 10-3 + 5.00 x 10-6) M x 0.0821 L atm K-1 mol-1 x 473 K = 8.37 x 10-2 atm

15.91 HCHO2(g)
CO(g) + H2O(g)

Since there is no HCHO2(g) present initially, we know this reaction will move from right to left as written.

[HCHO2] [CO] [H2O]

I – 0.20 0.30
C +x –x –x
E +x 0.20–x 0.30–x

Substituting the above values for equilibrium concentrations into the mass action expression gives:

Kc =
[CO][ H 2 O] =
( 0.20 − x )( 0.30 − x ) = 2.9 × 104
[ HCHO2 ] (x)
Since Kc is so large for the forward direction, we do not anticipate that the reverse reaction will proceed to
any appreciable extent. Therefore, we may assume x << 0.20 and x << 0.30. This simplifies the problem
immensely and we may solve for x.
x = [HCHO2] = 2.1 × 10–6 M.

At equilibrium we have:

0.2 moles of CO or 0.2 x 46 g/mol = 5.6 g

0.3 moesl of H2O or 0.3 x 18.0 g/mol = 5.4 g
2.1 x 10-6 moles of HCHO2 or 0 g

The density is: (5.6 + 5.6)g/1 L = 11.0 g/L

15.92 (a) The density of the gas before equilibrium:

92.01 g
Grams of N2O4 = 0.0245 mol N 2 O 4 x = 2.25 g
mol

46.00 g
Grams of NO2 = 0.0116 mol x = 0.534 g
mol

Density = (2.25 + 0.534)g/4.50 L = 0.620 g L-1

(b) Matter is not destroyed during a chemical reaction. Therefore, the density of the mixture cannot change
since the total mass of the system does not change and the volume remains constant.
Density = 0.620 g L-1

347