Chemistry 122

Mines, Spring, 2012

Answer Key, Problem Set 3 (shorter version; few explanations and work)
1. NT1; 2. NT2; 3. 14.21 & 14.22; 4. 14.4 and 14.23; 5. 14.28; 6. 14.30; 7. 14.33; 8. 14.35; 9. 14.36; 10. 14.39; 11. 14.44; 12. 14.45;
13. 14.48*; 14. 14.50a&c only, but add d: keep initial [A] and [B] at 1 M, but make initial [C] 4 M, and make coefficients as follows: a
3; b 2; and c 5 (as in part (c), do not solve for x! Just set up equation!)

--------------------------------------------1. NT1.

Consider a reaction represented by: 3 A(g) + B(g)

2 C(g) Assume a particular trials initial
concentrations were [A]0 = 9 M; [B]0 = 9 M, and [C]0 = 0 M, and that the final value for [B], when the system reaches
equilibrium ([B]eq), is 8 M (see left trace below).

B
Rf
A

Concen
-tration
(M)

Rate

3
C

Time

Time

(a) Copy the left plot down on your paper and add the traces for [A] and [C], being careful to consider the
stoichiometry of the reaction. (SEE ABOVE)
(b) Copy the right plot down on your paper and add a trace for the reverse rate (Rr). (SEE ABOVE)
(c) What two things must always be equal when a chemical system is at equilibrium?

Answer: Rf and Rr must be equal at equilibrium. That is the definition of (dynamic)

equilibrium: Rate forward = Rate reverse.
(d) Do you think that the value of the equilibrium constant for the reaction equation in question is somewhat large or
somewhat small? Give your reasoning.

Answer: Somewhat small. One reactant only goes down in value by ~11% (B), and the other by
only ~33%. That means reactant favored and a K smaller than 1.
2. NT2.

(a) State the law of mass action.

At a given temperature, when a given reaction system reaches dynamic equilibrium, regardless
of what the initial concentrations of reactants and/or products were, the value of the reaction
quotient, Q, always has the same value, called K:
For: a A + b B

cC + dD
c
eq
a
eq

d
eq
b
eq

[C] [D]
[A] [B]

(A, B, C, and D are gases or solution species),

for a system at equilibrium

(b) True or false: K changes as a reaction occurs, but Q does not.

False. Q changes as a reaction occurs, but K does not.

If forward reaction occurs ([products] increase and [reactants] decrease and so), Q must increase.
If reverse reaction occurs ([products] decrease and [reactants] increase and so), Q must decrease.
(c)

True or false: The value of K depends on the initial concentrations of reactants and products.
reasoning.

Give

False. The value of K is constant for a given reaction system, as long as T is kept constant. It
matters not what position the system starts off in. (See part (a)).
(d) True or false: The equilibrium concentrations of reactants and products depend on their initial concentrations.
Give reasoning.

True. If you start with different initial concentrations, then you (nearly always) end up with
different final (equilibrium) concentrations because of stoichiometry (mass conservation).
(e)

True or false: Reactions with large K values are fast. Explain.

PS3-1

Answer Key, Problem Set 3

False. A large K indicates only that once equilibrium is established, there will be a large
amount of products relative to reactants. It does not indicate how fast the forward reaction
occurs.
(f)

True or false: There is only one value of K for a particular system at a particular T, but there are an infinite
number of equilibrium positions / states. Explain.

True. As noted above, it is the value of the reaction quotient that is constant for any given
reaction system at equilibrium. But there are an infinite number of combinations of values that
will satisfy the equation given in part (a) for any given chemical equation. For example, if K =
[C] 2 [D]
, the following equations are all true (given a bit of
36 for a system in which K
[A][B]
uncertainty in each concentration value) even though the values for [A], [B], [C], and [D] are
different in each case:
36

62 1
1 1

36

1 82
1 1.777

36

20 6 2
54

36

1.68 4 2
etc.
3 0.25

Hopefully you can see that mathematically there are an infinite number of combinations of
values that will satisfy a given law of mass action equation. Thus there are an infinite number
of equilibrium positions or states for a given reaction system even though they are all
characterized by the same value of K.
3. 14.21 & 14.22
14.21. Write an expression for the equilibrium constant of each chemical equation.
(a) SbCl5(g)

(b) 2 BrNO(g)

(c)

Kc

SbCl3(g) + Cl2(g)

CH4(g) + 2 H2S(g)

(d) 2 CO(g) + O2(g)

CS2(g) + 4 H2(g)

2
[BrNO]eq

Kc

Kc

2 CO2(g)

[SbCl5 ]eq
2
[NO]eq
[Br2 ]eq

Kc

2 NO(g) + Br2(g)

[SbCl3 ]eq [Cl2 ]eq

4
[CS 2 ]eq [H2 ]eq
2
[CH4 ]eq [H2S]eq
2
[CO 2 ]eq
2
[CO]eq
[O 2 ]eq

14.22. Find and fix each mistake in the equilibrium constant expressions

eq

eq

S
[
]
2
H
[

2 H2S(g)

2 H2(g) + S2(g)

Kc

]
S
2
H
[

(a)

Kc

eq

]
l2
C
[
]
O
C
[

COCl2(g)

Kc

eq

]
l2
C
O
C
[

(b) CO(g) + Cl2(g)

eq

eq

Kc

2
[H2 ]eq
[S 2 ]eq
2
[H2S]eq

[COCl2 ]eq
[CO]eq [Cl2 ]eq

(the exponents were missing)

(the numerator and

denominator were flipped)

4. 14.4 and 14.23

14.4.

What is the significance of the equilibrium constant? What does a large equilibrium constant tell us about a
reaction? A small one?

Answers: The equilibrium constant reflects the tendency of a reaction to occur in the forward
direction (as written). A large K indicates that once equilibrium is established, there will be a
great amount of products relative to reactants, which means the reaction tends to favor products
at equilibrium and thus has a great tendency to occur in the forward direction. A small K
indicates that once equilibrium is established, there will be a small amount of products relative to
reactants, which means the reaction tends to favor reactants at equilibrium and thus has very
little tendency to occur in the forward direction.

PS3-2

Answer Key, Problem Set 3

14.23. When [a] reaction [represented by the following chemical equation] comes to equilibrium, will the concentrations
of the reactants or products be greater? Does the answer to this question depend on the initial concentrations of
the reactants and products?
-5
2 C(g) Kc = 1.4 x 10
A(g) + B(g)

Answers: Reactants (will be greater). The equilibrium constant is fairly small (<< 1), meaning
reactant favored (at equilibrium). The initial concentrations do not matter because Q = K once
equilibrium is established.
5. 14.28.

The reaction [equation!] below has an equilibrium constant of Kp = 2.2 x 10 at 298 K.

CO2(g) + CF4(g)

2 COF2(g)

Calculate Kp for each of the reactions [equations!] and predict whether reactants or products will be favored at
equilibrium:
CO2(g) + CF4(g)

(a) COF2(g)

Answer: K1 x = K11/2 = (2.2 x 106)1/2 = 1.48.. x 103 = 1.5 x 103 ; products favored at equilibrium
(b) 6 COF2(g)

3 CO2(g) + 3 CF4(g)

Answer: K1 x 3 = K13 = (2.2 x 106)3 = 1.06..x 1019 = 1.1 x 1019 ; products favored at equilibrium
(c) 2 CO2(g) + 2 CF4(g)

4 COF2(g)

Answer: K-1 x 2 (K1 ) [(2.2 x 106)-1]2 (4.55..x 10-7)2 2.066.. 2.1 x 10-13; reactants favored
-1 2

6. 14.30.

Use the reactions [equations!] below and their equilibrium constants to predict [calculate!] the equilibrium
constant for the reaction [equation!], 2 A(s)
3 D(g)
B(g) + C(g)

A(s)

B(g) + 2 C(g)

3 D(g)

Answer: 4.75 x 10
2 A(s)

7. 14.33.

K2 = 2.35

-4

K1 K1 x 2 K12 = 0.03342 ( 1.115..x 10-3)

B(g) + 2 C(g)

B(g) + 2 C(g)
2 A(s)

K1 = 0.0334

3 D(g)

K2 K-2 K2-1 2.35-1 ( 4.255..x 10-1)

K1+2 K1K2 0.03342 x 2.35-1 4.747..x 10-4 4.75 x 10-4

3 D(g)

Write an equilibrium expression for each chemical equation involving one or more solid or liquid reactants or

products.
-

(a)

2-

CO3 (aq) + H2O(l)

(b) 2 KClO3(s)

(c)

HF(aq) + H2O(l)

HCO3 (aq) + OH (aq)

Kc

2 KCl(s) + 3 O2(g)

Kc

H3O (aq) + F (aq)

Kc

[HCO3 ]eq [OH- ]eq

2-

[CO3 ]eq
[O 2 ]3eq
1

[O 2 ]3eq

[H3O ]eq [F - ]eq

[HF]eq

(d) NH3(aq) + H2O(l)

8. 14.35.

NH4 (aq) + OH (aq)

Kc

[NH4 ]eq [OH- ]eq

[NH3 ]eq

Consider the reaction [equation!]:

CO(g) + 2 H2(g)

CH3OH(g)

An equilibrium mixture of this reaction at a certain temperature was found to have [CO] = 0.105 M, [H2] = 0.114 M, and
[CH3OH] = 0.185 M. What is the value of the equilibrium constant (Kc) at this temperature?

Answer: 136 or 1.36 x 102

PS3-3

Answer Key, Problem Set 3

9. 14.36.

[CH3 OH]eq
2
[CO]eq [H2 ]eq

0
1
x
6
3
.
1

Kc

0.185
135.57.. 136 or
(0.105)(0. 114) 2

Consider the reaction [equation!]:

NH4HS(s)

NH3(g) + H2S(g)

An equilibrium mixture of this reaction at a certain temperature was found to have [NH3] = 0.278 M and [H2S] = 0.355 M.
What is the value of the equilibrium constant (Kc) at this temperature?

Answer: 0.0987 or 9.87 x 10-2

(0.278)(0.355) 0.09869..

0
1
x
7
8
.
9

10. 14.39.

[NH3 ]eq [H2S]eq

7
8
9
0
.
0

Kc

or

Consider the reaction [equation!]:

2 NO(g) + Br2(g)

2 NOBr(g) ; Kp = 28.4 at 298 K

In a reaction mixture at equilibrium, the partial pressure of NO is 108 torr and that of Br2 is 126 torr. What is the partial
pressure of NOBr in this mixture?

Answer: 0.308 atm or 234 torr

PNO 108 torr x
Kp

1 atm
0.1421..atm
760 torr

PBr 126 torr x

2

1 atm
0.1657..atm
760 torr

2
2
PNOBr
PNOBr
2

28.4 PNOBr
(28.4)(0.1421)2 (0.1657) 0.09502..
2
PNO PBr
(0.1421)2 (0.1657)
2

PNOBr 0.09502.. 0.3082.. 0.308 atm

11. 14.44.

or (in torr) : 0.308 atm x 760 torr/atm 234 torr

Consider the reaction [equation!]:

CO(g) + 2 H2(g)

CH3OH(g)

A reaction mixture in a 5.19-L flask at a certain temperature contains 26.9 g CO and 2.34 g H2. At equilibrium, the flask
contains 8.65 g CH3OH. Calculate the equilibrium constant (Kc) for the reaction [equation!] at this temperature?

Answer: 27.3
26.9 g CO x
2.34 g H2 x

1 mol
5.19 L
0.9603..mol CO

0.1850.. M CO (initially)
(12.01 16.00) g CO

1 mol
5.19 L
1.160..mol H2

0.2236.. M H2 (initially)
(2 x 1.008) g H2

8.65 g CH3OH x

1 mol
(4 x 1.008 12.01 16.00) g CH3 OH

5.19 L
0.2699..mol CH3 OH

0.05201.. M CH3OH
(at equilibrium)

Fill in what is known into an ICE table and use stoichiometry to determine E values:
Initial
Change

[CO] (M)
0.1850
-0.05201

[H2] (M)
0.2236
-2(0.05201)

[CH3OH] (M)
0
+0.05201

Equilibrium

0.1850 0.05201 =
0.1330

0.2236 2(0.05201)
= 0.1196

0.05201

Substitute into K expression:

[CH3 OH]eq
2
2 eq

[CO]eq [H ]

0.05201
27.33..
(0.1330)(0.1196)2

PS3-4

3
.
7
2

Kc

Answer Key, Problem Set 3

12. 14.45.

Consider the reaction [equation!]:

NH4HS(s)

NH3(g) + H2S(g)

-3

At a certain temperature, Kc = 8.5 x 10 . A reaction mixture at this temperature containing solid NH4HS has [NH3] =
0.166 M and [H2S] = 0.166 M. Will more of the solid form or will some of the existing solid decompose as equilibrium is
reached?

Answer: more solid will form (because reverse reaction will occur; Q > K)
Qc [NH3 ][H2S] (0.166)(0. 166) 0.02755.. which is greater than Kc (= 0.0085) [Given]

If Q > K, then there are too many products to be at equilibrium and so reverse reaction will occur
more solid will form.

13. 14.48.

Nitrogen dioxide dimerizes according to the reaction [equation!]:

2 NO2(g)

N2O4(g) ;

Kp = 6.7 at 298 K

A 2.25-L container contains 0.055 mol of NO2 and 0.082 mol of N2O4 at 298 K. Is the reaction [system] at equilibrium?
If not, in what direction will the reaction proceed?

Answer: No, not at equilibrium. Forward reaction occurs (b/c Q < K)

n
RT Thus:
V

PV nRT P

PNO

nNO

PN O

nN O

Qp

PN O
2

2
PNO

RT

V
2

0.055 mol
0.08206
2.25 L

RT

0.8912

0.5977 2

L atm
mol K

298 K 0.5977..atm

0.082 mol
L atm
0.08206 mol
298 K 0.8912..atm
K
2.25 L

2.49.. which is less than Kp (= 6.7) [so not at equilibrium]

Q is too small system makes more products to reach equil. forward reaction occurs
14. 14.50a&c(+d).

Consider the reaction [equation!] and associated equilibrium constant:

a A(g) + b B(g)

c C(g)

Kc = 5.0

Find the equilibrium concentrations of A, B, and C for each value of a, b, and c. [For parts (a) and (c)] assume that the
initial concentrations of A and B are each 1.0 M and that no product is present at the beginning of the reaction. For
part (d), assume that the initial concentrations of A and B are each 1.0 M and that the initial concentration of C is 4.0 M.
(a) a = 1; b = 1; c = 2
(c) a = 2; b = 1; c = 1 (set up equation for x; dont solve)
(d) a = 3; b = 2; c = 5 (set up equation for x; dont solve)

* As noted below, there are many correct answers

for parts (c) and (d) because the answer here is an
algebraic expression whose form will depend on how
you define x. However, if you were to actually
solve for the final concentrations at equilibrium in all
cases, those answers would be the same in all cases.

Execution of Strategy (part (a)):

A(g) + B(g)

2 C(g)

Let x = [A] that is lost as equilibrium is established

PS3-5

2
[C]eq

[A]eq [B]eq

5.0

Answer Key, Problem Set 3

[A] (M)
1.0
-x
1.0 x

Initial
Change
Equilibrium
K

2
[C]eq

[A]eq [B]eq

2x 2

1.0 x 2

2x

1.0 x

[B] (M)
1.0
-x
1.0 x

5.0

[C] (M)
0
+ 2x
0 + 2x = 2x

2x 2

1.0 x 2

5.0

2.236.. 4.236x 2.236 x

2.236
0.527.. 0.53
4.236

[A]eq = [B]eq = 1.0 0.53 = 0.47 M

[C]eq = 2(0.53) = 1.06 = 1.1 M

Check:

2
[C]eq

[A]eq [B]eq

1.062
5.02 5.0
0.4730.473

Execution of Strategy (part (c)):

2 A(g) + B(g)

Initial
Change
Equilibrium

C(g)

[A] (M)
1.0
- 2x
1.0 2x

[C]eq
2
[A]eq
[B]eq

[B] (M)
1.0
-x
1.0 x

5.0

[C] (M)
0
+x
0+x=x

Substituting in (be very careful to really substitute innote the changes in the position of the square!):
K

[C]eq
2
eq

[A] [B]eq

1.0 2x 2 1.0 x

5.0

Execution of Strategy (part (d)):

3 A(g) + 2 B(g)
Q

[C]5
[A]3 [B] 2

5 C(g)

5
[C]eq
2
[A]3eq [B]eq

5.0

45
1024 , which means Q > K and reverse reaction occurs to reach equilibrium.
1312

Let 2x = [B] that is formed as equilibrium is established.

Initial
Change
Equilibrium

[A] (M)
1.0
+ 3x
1.0 + 3x

[B] (M)
1.0
+ 2x
1.0 + 2x

[C] (M)
4
- 5x
4 5x

NOTE: There are many correct answers to this problem as written, because there are many
ways to define x, and each one will have a different form. See complete key for
examples of this.

PS3-6