Acid:Base Chemical Equilibrium

1
CHAPTER 15 (B&O)
NON ACID/BASE CHEMICAL EQUILIBRIUM

Problems to prepare students for hourly exam II.

Non acid-base equilibrium concepts

Non acid-base equilibrium calculations

Le Chateliers Principle

E. Tavss 2/12
2
NON ACID-BASE EQUILIBRIUM CONCEPTS

Chem 162-2011 Hourly Exam II Answers
Chapter 14 - Non Acid/Base Chemical Equilibrium
13. 2NO(g) Cl
2
(g)
2NOCl(g) K
p
1.40 x 10
5
at 298K

What is K
p
at 298 K Ior the reaction: NOCl(g)

NO(g) Cl
2
(g)

A. 7.14 x 10
-6

B. 3.57 x 10
-6

C. 1.34 x 10
-3

D. 5.34 x 10
-3

E. 2.67 x 10
-3

The equilibrium equation is reversed and halved. ThereIore, the new K is the square root oI the inverse oI the
original K. 1/((1.40x10
5
)
0.5
) 2.67 x 10
-3

10. Which oI the Iollowing statements concerning the reaction quotient Q and/or the equilibrium
constant K is false?

A. Q must be equal to K at equilibrium.
B. The larger the value oI K, the Iarther the Iorward reaction proceeds toward
completion.
C. As the temperature increases, the value oI K increases.
D. The concentrations oI pure solids and pure liquids are omitted Irom the
expression Ior Q, because they do not change during the course oI a chemical
reaction.
E. By comparing the value oI Q

with K one can predict the direction oI
change Ior a system not initially in equilibrium.

A. True. II Q K, then the system is at equilibrium.
3
B. True. The larger the value oI K, the Iurther the reaction goes to the right (which means, toward
completion).
C. False. As the temperature increases in an endothermic reaction, the value oI K increases; but as the
temperature increases in an exothermic reaction the value oI K decreases.
D. True. Whether the measurement is Q or K, the concentrations oI pure solids and pure liquids are
omitted Irom the equilibrium expression because only substances that change in concentration are
included, and pure solids and pure liquids don`t change in concentration.
E. True. II Q is smaller than K then the reaction will go to the right; iI Q is larger than K then the
reaction will go to the leIt.

CHEM 162-2010 EXAM II
25. SO
2
Cl
2
(g)
SO
2
(g) Cl
2
(g) K 0.070

Flask X: 0.50 mol SO
2
Cl
2
, 0.10 mol SO
2
, 0.20 mol Cl
2
in 0.50L
Flask Y: 0.50 mol SO
2
Cl
2
, 0.10 mol SO
2
, 0.20 mol Cl
2
in 1.00L
Flask Z: 0.50 mol SO
2
Cl
2
, 0.10 mol SO
2
, 0.20 mol Cl
2
in 2.00L

Which Ilask will result in a reaction Iorming more Cl
2
?

A. Flask X only
B. Flask Y only
C. Flask Z only
D. Flasks X and Y only
E. Flasks Y and Z only

Flask X:

SO
2
Cl
2
(g)

SO
2
(g) Cl
2
(g)
Initial 1.00 0.20 0.40
Change
Equilibrium
Q (|SO
2
||Cl
2
|)/|SO
2
Cl
2
|
Q (|0.20||0.40|)/|1.00| 0.080. Q ~ K. Reaction will go to the leIt; |Cl
2
| will be decreased.

Flask Y:

SO
2
Cl
2
(g)

SO
2
(g) Cl
2
(g)
Initial 0.50 0.10 0.20
Change
Equilibrium
4
Q (|SO
2
||Cl
2
|)/|SO
2
Cl
2
|
Q (|0.10||0.20|)/|0.50| 0.040. Q K. Reaction will go to the right; |Cl
2
| will be Iormed.

Flask Z:

SO
2
Cl
2
(g)

SO
2
(g) Cl
2
(g)
Initial 0.25 0.05 0.10
Change
Equilibrium
Q (|SO
2
||Cl
2
|)/|SO
2
Cl
2
|
Q (|0.05||0.10|)/|0.25| 0.020. Q K. Reaction will go to the right; |Cl
2
| will be Iormed.

Answer: Flasks Y and Z only

16. Given: C(s) CO
2
(g)
2CO K
p
1.3 x 10
14

COCl
2
(g)
CO(g) Cl
2
(g) K
p
167

Calculate K
p
Ior: C(s) CO
2
(g) 2Cl
2
(g)
2COCl
2

A. 2.2 x 10
16

B. 7.8 x 10
11

C. 1.3 x 10
12

D. 2.6 x 10
11

E. 4.7 x 10
9

Use Hess`s Law.
C(s) CO
2
(g)
2CO K
p
1.3 x 10
14

For the 2
nd
equation, reverse it and double it; correspondingly, invert and square the K
p
.
2CO(g) 2Cl
2
(g)
2COCl
2
(g) K
p
(1/167)
2

Add the equations and multiply the equilibrium constants.
C(s) CO
2
(g) 2Cl
2
(g)
2COCl
2
K 4.66 x 10
9

6. Which oI the Iollowing is true about a chemical reaction at equilibrium?
5

X. The rate oI the Iorward reaction equals the rate oI the reverse reaction.
Y. There is no observable change in any property oI the system.
Z. The molecules have less kinetic energy than beIore equilibrium was reached.

A. X and Y only
B. X only
C. Y only
D. X and Z only
E. X, Y, and Z

At equilibrium, the Iorward and reverse reactions proceed at equal rates, and the concentrations oI
reactants and products remain constant. Since there is no change in the concentrations oI reactants and
products, and change in properties (e.g., vapor pressure) will only result iI the concentrations oI reactants
and products change, then there is no change in any property oI the system. A. X and Y only.

CHEM 162-2009 FINAL EXAM
CHAPTER 14 - NON ACID/BASE CHEMICAL EQUILIBRIUM
44. Consider the equilibrium reaction: N
2
O
4
(g)
2NO
2
(g)
Which oI the Iollowing correctly describes the relationship between K
c
and K
p
Ior the reaction?

A. K
p
RT x K
c

B. K
p
K
c

C. K
p
(RT x K
c
)-1
D. K
p
K
c
/RT
E. K
p
RT/K
c

N
2
O(g)
2NO
2
(g)
n 2 1 1
K
p
K
c
(RT)
n

K
p
K
c
(RT)
1

K
p
K
c
(RT)
K
p
RT x K
c
A

CHEM 162-2009 HOURLY EXAM II ANSWERS
CHAPTER 14: NON ACID/BASE CHEMICAL EQUILIBRIUM
11. Which statement is correct about a system at equilibrium?

A. The concentrations oI reactants must equal the concentrations oI the products.
6
B. The Iorward and reverse reactions occur at identical rates.
C. The concentrations oI reactants and products can be changed by adding a catalyst.
D. The concentrations oI reactants and products are not aIIected by a change in temperature.
E. The reaction continuously oscillates between reactants and products.

The two rules regarding equilibrium are (1) the Iorward rate oI the reaction is equal to the reverse rate oI
the reaction, and (2) there is no change in the concentration oI the reactants or products
A. False. The concentrations oI reactants and products are rarely equal.
B. True. The Iorward and reverse reactions must occur at identical rates. This results in no change in the
concentration oI reactants or products.
C. False. A catalyst doesn`t change the Free Energy oI reactants and products (to be discussed in the
chapter on Thermodynamics). Since the equilibrium constant is directly related to the Iree energy, then
the equilibrium constant won`t change, and thereIore the concentrations oI reactants and products won`t
change.
D. False. The concentrations oI reactants and products are aIIected by a change in temperature. In Iact, a
change in temperature is the only thing that will aIIect the equilibrium constant, and correspondingly, the
concentrations oI reactants and products.
E. False. The system slowly and steadily comes to an equilibrium value, and then stays there. It doesn`t
oscillate back and Iorth like a pendulum.

Chem 162-2008 Exam II Answers
Chapter 14 Non Acid/Base Chemical Equilibrium
Adding equilibrium equations and multiplying K`s
3. Consider the Iollowing two reactions and their equilibrium constants.

Reaction 1: NO
2
(g)
NO(g) O(g) K
1
6.8 x 10
-49

Reaction 2: NO
2
(g) O
2
(g)
O
3
(g) NO(g) K
2
1.7 x 10
33

Calculate K Ior the reaction: O
2
(g) O(g)
O
3
(g)

(a) 1.2 x 10
-15

(b) 4.0 x 10
-82

(c) 8.7 x 10
14

(d) 2.5 x 10
81

(e) 4.3 x 10
41

This is Hess` law.
Reaction 1 gets reversed; thereIore, K
1
gets inverted.
Reaction 2 doesn`t change.
The sum oI reversed reaction 1 and reaction 2 equals the product oI K
2
and inverted K
1
.
NO(g) O(g)

NO
2
(g) 1/K
1
1/(6.8 x 10
-49
)= 1.47 x 10
48

7
NO
2
(g) O
2
(g)

O
3
(g) NO(g) K
2
1.7 x 10
33

O
2
(g) O(g)
O
3
(g) (1/K
1
) x (K
2
) (1.47 x 10
48
) x (1.7 x 10
33
) 2.50 x 10
81

4 Chem 162-2007 Final exam answers
Chapter 14 Non Acid-Base Chemical Equilibrium
Non Acid-Base equilibrium concepts

For which oI the Iollowing reactions is K
c
~ K
p
?
A. H
2
O(s) H
2
O(g)
B. H
2
(g) O
2
(g) H
2
O(g)
C. H
2
(g) Cl
2
(g) 2HCl(g)
D. 2KClO
3
(s) KCl(s) 3O
2
(g)
E. 2O
3
(g) 3O
2
(g)

K
pinatm
K
cinM
(RT)
ngas

K
p
K
c
when n
gas
0
K
p
~ K
c
when n
gas
~0
K
c
~ K
p
when n
gas
0.
A. n 1 0 1
B. n 1 1.5 -0.5
C. n 2 2 0
D. n 3 0 3
E. n 3 2 1

Actually, the relative values oI K
c
and K
p
also depend on the temperature. At 298K the rules
I wrote apply.
B

8

H
2
(g) I
2
(g) 2HI(g) K 54.5
What is the equilibrium constant Ior the reaction:
HI(g) H
2
(g) I
2
(g)
A. 27.2
B. 0.0367
C. 7.38
D. 1.45
E. 0.135

Reversing the reaction corresponds to inverting K.
Taking halI the reaction corresponds to taking the square root oI K.
Hence, we want to take the square root oI the inverse oI K.
(1/54.5)
0.5
0.135

9

Consider the Iollowing plot Ior the reaction:
A(g) B(g) K 3.0
X
Y
Z
[A] M
[
B
]

M
Equilibrium line

Which oI the Iollowing statements is true?
A. Point Z represents Q K.
B. Point X represents Q~K.
C. Point Y represents QK
D. Point X represents QK
E. The system is at equilibrium when |B| 4.0M and |A| 2.0M

Visualize an example oI 6 on the B axis meeting 2 on the A axis at Z
A. False. Point Z represents a 3/1 ratio oI |B|/|A|, which is equal to K.
B. False. This would be approximately 6/5 1.2, which is K.
C. False. This would be approximately 15/3 5, which is ~ K.
D. True. This would be approximately 6/5 1.2, which is K.
E. False. 4.0/2.0 2.0, which is K.

CHEM 162-2007 EXAM II ANSWERS
CHAPTER 14 NON-ACID/BASE CHEMICAL EQUILIBRIUM
NON-ACID BASE EQUILIBRIUM CONCEPTS
10
15. When I
2
(s) is added to water, a saturated solution at equilibrium results. The dissolved iodine
imparts a gold color to the water. The equilibrium is represented as:
I
2
(s)
I
2
(aq)

AIter equilibrium is established, some radioactive solid iodine is added to the solution. AIter a
period oI time, the solution remains saturated, and the intensity oI the gold color in the solution remains
the same. When the solution is tested, it is Iound that some oI the radioactivity is now in the solution as
well as in the solid.

What does this experiment indicate about the equilibrium?

(a) The rate oI dissolving is greater than the rate oI crystallizing
(b) The rate oI crystallizing is greater than the rate oI dissolving
(c) AIter equilibrium is established, no Iurther solid iodine dissolves
(d) The rates oI dissolving and crystallizing both approach zero.
(e) The iodine continues to dissolve and crystallize at equal rates

(a) The rate oI dissolving is greater than the rate oI crystallizing
False. The rate oI dissolving is only greater than the rate oI crystallizing at the beginning oI the reaction
when the solid is Iirst added to the solvent. At equilibrium the rate oI dissolving is equal to the rate oI
crystallizing.
(b) The rate oI crystallizing is greater than the rate oI dissolving
False. The rate oI crystallizing would only be greater than the rate oI dissolving in a pre-equilibrium
situation, such as iI the solution was cooled and the solid began precipitating out oI solution. However, in
this case we are at equilibrium, where, by deIinition, the rate oI crystallizing is equal to the rate oI
dissolving.
(c) AIter equilibrium is established, no Iurther solid iodine dissolves
False. This is a dynamic equilibrium in which it can microscopically be determined that even at
equilibrium solid iodine is dissolving in the solvent, while dissolved iodine is crystallizing onto the solid.
(d) The rates oI dissolving and crystallizing both approach zero.
False. II the rates oI dissolving and crystallizing both approached zero, then there would be no dynamic
equilibrium. However, there is always dynamic equilibrium (except Ior some unusual circumstances,
such as at absolute zero temperature).
(e) The iodine continues to dissolve and crystallize at equal rates
True. The Iirst sentence says that the pre-radioactive solution is at equilibrium. The IiIth sentence
suggests that the radioactive system continues to be at equilibrium. In a dynamic equilibrium, the Iorward
rate (dissolving) and the reverse rate (crystallization/precipitation) are equal.

11

NON ACID-BASE EQUILIBRIUM CALCULATIONS

25 Chem 162-2011 Final exam
Chapter 14 - Non-Acid/Base Chemical Equilibrium

Solid ammonium chloride, NH
4
Cl, decomposes when heated according to the equation
NH
4
Cl(s) NH
3
(g) HCl(g)
A sample oI solid ammonium chloride is heated to 400 K in an evacuated container. When the
system comes to equilibrium, some NH
4
Cl(s) remains and the total pressure in the container is
Iound to be 1.5 x 10
-4
atm. Assuming that the total pressure is due only to NH
3
and HCl, Iind K
p

Ior this reaction at 400 K.

A. 7.5x10
-5

B. 2.8x10
-9

C. 5.6 x 10
-9

D. 2.0x10
-8

E. 4.0x10
-8

NH
4
Cl(s)
NH
3
(g) HCl(g)
Initial Y 0 0
Change -X X X
Equilibrium Y-X X X

X X 1.5 x 10
-4

2X 1.5 x 10
-4

X 7.5 x 10
-5
atm

|NH
3
||HCl| K
p

|7.5 x 10
-5
|| 7.5 x 10
-5
| K
p

K
p
5.625 x 10
-9

C

12
50 Chem 162-2011 Final exam
Chapter 14 - Non-Acid/Base Chemical Equilibrium

A reaction vessel at 27C contains a mixture oI SO
2
(initial P3.00 atm) and O
2
(initial P 1.00
atm). A reaction proceeds according to the equation below :

2SO
2
(g) O
2
(g) 2SO
3
(g)

At equilibrium, the total pressure was Iound to be 3.75 atm. What is the equilibrium constant
K
p
?

A. 1.9 x 10
1

B. 3.0
C. 2.7 x 10
-1

D. 5.3 x 10
-2

E. 1.1 x 10
-1

2SO
2
(g)
O
2
(g)
2SO
3
(g)

Initial 3.00 1.00 0
Change -2X -X 2X
Equilibrium 3.00-2X 1.00-X 2X

(3.00-2X) (1.00-X) (2X) 3.75 atm
X 0.25 atm

2SO
2
(g)
O
2
(g)
2SO
3
(g)

Initial 3.00 1.00 0
Change -2X -X 2X
Equilibrium 2.50 0.75 0.50
P
2
so3
/(P
2
so2
x P
o2
) (0.50
2
)/((2.50
2
)

x 0.75) 0.0533 K
p

D

16. 2SO
3
(g)
2SO
2
(g) O
2
(g) K
p
1.2 x 10
-5

13
A sample oI SO
3
(g) is placed in a container, initially exerting a pressure oI 0.800 atm. What is the
pressure oI O
2
(g) at equilibrium?

A. 0.0035 atm
B. 0.0070 atm
C. 0.012 atm
D. 0.0024 atm
E. 0.0096 atm

2SO
3
(g)

2SO
2
(g) O
2
(g)
Initial 0.800 0 0
Change -2X 2X X
Equilibrium 0.800-2X 2X X
(P
so2
2
x P
o2
)/P
so3
2
1.2 x 10
-5

((2X)
2
x X)/(0.800-2X)
2
1.2 x 10
-5

Use the small K rule to get around a quadratic equation.
((2X)
2
x X)/(0.800)
2
1.2 x 10
-5

4X
3
/0.64 1.2 x 10
-5
X 1.24 x 10
-2
P
o2

17. Br
2
(g) 3F
2
(g)
2BrF
3
(g) K
p
5.4 x 10
8

Assume 0.30 atm Br
2
and 0.60 atm oI F
2
are placed in a container. They react according to the
equation above. What is the pressure oI Br
2
(g) at equilibrium?

A. 0.10 atm
B. 2.6 x 10
-4
atm
C. 0.40 atm
D. 4.8 x 10
-3
atm
E. 0.028 atm

Br
2
(g)
3F
2
(g)

2BrF
3
(g)
Initial 0.30 0.60 0
Change -X -3X 2X
Equilibrium 0.30-X 0.60-3X 2X

|BrF
3
|
2
/(|Br
2
| x |F
2
|
3
) 5.4 x 10
8

|2X|
2
/(|0.30-X| x |0.60-3X|
3
) 5.4 x 10
8

Use a computer or a good calculator to solve Ior X:
X 0.199523
0.30-X P
Br2
0.100477 atm
14
0.60-3X P
F2
0.00143 atm
2X P
BrF3
0.399046 atm

ProoI: |BrF
3
|
2
/(|Br
2
| x |F
2
|
3
) 5.4 x 10
8

|0.399046|
2
/(|0.100477| x |0.00143|
3
) 5.42 x 10
8

But since we don`t have a computer or a good calculator, we have to resort to mathematical trickery.
|BrF
3
|
2
/(|Br
2
| x |F
2
|
3
) 5.4 x 10
8

|2X|
2
/(|0.30-X| x |0.60-3X|
3
) 5.4 x 10
8

Quadratic equation, so use large K rule.

F
2
is the limiting reactant.
Br
2
(g)
3F
2
(g)

2BrF
3
(g)
Initial 0.30 0.60 0
Change -0.20 -0.60 0.40
Equilibrium 0.10 0 0.40

P
br2
at equilibrium 0.10 atm

New problem: Let`s say that the problem asked Ior the pressure oI F
2
at equilibrium, not the pressure
oI Br
2
at equilibrium. How would we do that? Here is where we would use the large K rule Iollowed by the
small K rule. We already used the large K rule to get to the ICE table above. Now let`s use the small K rule
to Iind the pressure oI F
2
at equilibrium.

We went all the way to completion (to the right) with the large K rule. But we were Iorced to go a bit too Iar,
because F
2
cannot have a '0 value. It must have some Iinite value, even iI the value is extremely small. So
let`s go back, a little to the leIt, to get an equilibrium value Ior F
2
. That is, let`s now call the BrF
3
the
reactant, and convert some oI this reactant into products.

Br
2
(g)
3F
2
(g)

2BrF
3
(g)
Initial 0.10 0 0.40
Change X 3X -2X
Equilibrium 0.10 X 3X 0.40 2X
|BrF
3
|
2
/(|Br
2
| x |F
2
|
3
) 5.4 x 10
8

|0.40-2X|
2
/(|0.10X| x |3X|
3
) 5.4 x 10
8

This gives us another quadratic equation. How do we get around the quadratic equation. Now it`s a little
conIusing because now the product is the reactant and the reactants are the products. The equilibrium
expression and the equilibrium constant are conIusing because they are based on product divided by reactant,
which is now totally reversed. So to get around this conIusion, let`s reverse the ICE table, and
correspondingly, reverse the equilibrium equation, so that we will have the reactant (BrF
3
) on the leIt side and
the products (Br
2
and F
2
) on the right side. Since we reversed the equilibrium equation, we must now
correspondingly invert the equilibrium expression and the equilibrium constant.

2BrF
3
(g)

Br
2
(g) 3F
2
(g)
Initial 0.40 0.10 0
Change -2X X 3X
Equilibrium 0.40 2X 0.10 X 3X
15
(|Br
2
| x |F
2
|
3
)/|BrF
3
|
2
1/(5.4 x 10
8
) K 1.85 x 10
-9

(|0.10X| x |3X|
3
)/|0.40-2X|
2
1.85 x 10
-9

I don`t know what we call this equation, but it is more complex than a quadratic equation.
Let`s use the small K rule to get around this complex equation.
Drop the '2X Irom 0.40-2X, and the 'X Irom 0.10X, as 2X and X must be extremely small.
(|0.10| x |3X|
3
)/|0.40|
2
1.85 x 10
-9

X 4.79 x 10
-4

3X 1.44 x 10
-3
atm F
2
pressure

11. Solid ammonium chloride, NH
4
Cl, decomposes when heated according to the equation:
NH
4
Cl(s)
NH
3
(g) HCl(g)

A sample oI solid ammonium chloride is heated to 400 K in an evacuated container. When the
system comes to equilibrium, some NH
4
Cl(s) remains and the total pressure in the container is Iound
to be 1.5 x 10
-4
atm. Calculate K
p
Ior this reaction at 400 K.

A. 5.6 x 10
-9

B. 2.3 x 10
-8

C. 3.5 x 10
-6

D. 1.5 x 10
-4

E. 7.8 x 10
-5

NH
4
Cl(s)

NH
3
(g) HCl(g)
Initial Y 0 0
Change -X X X
Equilibrium Y-X X X
X X 1.5 x 10
-4
atm
X 0.75 x 10
-4
atm
P
nh3
x P
hcl
K
p

0.75 x 10
-4
x 0.75 x 10
-4
0.56 x 10
-8
5.6 x 10
-9

CHEM162-2010 HOURLY EXAM II ANSWERS
CHAPTER 14 - NON ACID-BASE CHEMICAL EQUILIBRIUM
NON-ACID-BASE EQUILIBRIUM CALCULATIONS
35. Solid ammonium chloride decomposes when heated according to the Iollowing reaction:

NH
4
Cl(s)
NH
3
(g) HCl(g)
A sample oI ammonium chloride is heated in an evacuated container. At equilibrium, the total pressure in
the container is 1.5x 10
-4
atm. Calculate K
p
Ior this reaction.
A. 7.8x10
-5

B. 2.3x10
-8

16
C. 3.5x10
-6

D. 1.5x10
-4

E. 5.6x10
-9

NH
4
Cl(s)
NH
3
(g) HCl(g)

NH
4
Cl(s)

NH
3
(g) HCl(g)
Initial Y 0 0
Change -X X X
Equilibrium Y-X X X
|NH
3
||HCl| K
p

|X||X| K
p

But what is the value oI X?

X X 0.00015
2X 0.00015
X 0.000075
K
p
X
2
|0.000075|
2
5.6 x 10
-9

17

CHEM-2010 FINAL EXAM ANSWERS
CHAPTER 14 - NON ACID AND BASE CHEMICAL EQUILIBRIUM
21. 2BrCl(g)
Br
2
(g) Cl
2
(g) K
c
32 at 500K
What would happen iI a 1.0L bulb were Iilled with 0.10mol BrCl(g), 0.50mol Br
2
(g), and 0.50mol Cl
2
(g)?

A. Some BrCl will react spontaneously to Iorm additional Br
2
and Cl
2
.
B. Some oI the Br
2
and Cl
2
will react spontaneously to Iorm additional BrCl.
C. Nothing will happen because the initial concentrations correspond to equilibrium concentrations.
D. All oI the BrCl will be consumed.
E. All oI the Br
2
will be consumed.

2 BrCl(g)
Br
2
(g) Cl
2
(g)
0.10 0.50 0.50

K
c
(|Br
2
||Cl
2
|)/(|BrCl|
2
)
(|0.50||0.50|)/(|0.10|
2
) 25 Q
When Q is less than K
c
, then the numerator is too small, so the reaction will go to the right to make the
numerator larger and to reach equilibrium.

A. True
B. False. The reaction will shiIt to the right, not to the leIt.
C. False. The initial concentrations do not correspond to equilibrium concentrations.
D. False. The reaction will shiIt to the right, but no component is ever totally consumed.
E. False. The concentration oI Br
2
will increase, not decrease.

46. Given:
C(s) 2H
2
(g)
CH
4
(g) K
p
0.262 at 1270K
What is K
c
Ior the above reaction?

A. 20.5
B. 19.6
C. 12.9
D. 27.3
E. 16.3

K
p
K
c
(RT)
ngas

0.262 K
c
(0.08214 x 1270)
-1

K
c
27.3

18
23. 2N
2
O
5
(g)
4NO
2
(g) O
2
(g)

1.00 atm oI N
2
O
5
is placed in a container, and reacts to reach equilibrium in the above reaction. The total
pressure at equilibrium is Iound to be 2.35 atm. Assume constant volume and temperature. Calculate K
p

Ior this reaction.

A. 66.0
B. 131
C. 262
D. 393
E. 472

2N
2
O
5
(g)
4NO
2
(g) O
2
(g)

2N
2
O
5
(g)

4NO
2
(g) O
2
(g)
Initial 1.00 0 0
Change
Equilibrium

2N
2
O
5
(g)

4NO
2
(g) O
2
(g)
Initial 1.00 0 0
Change -2X 4X X
Equilibrium 1.00 2X 4X X
K
p
(|NO
2
|
4
|O
2
|)/|N
2
O
5
|
2

(|4X|
4
|X|)/|1.00-2X|
2
K
p

Two unknowns in one equation.
However, (1.00-2X) 4X X 2.35 atm
X 0.45 atm

2N
2
O
5
(g)

4NO
2
(g) O
2
(g)
Initial
Change
Equilibrium 0.10 atm 1.80 atm 0.45 atm
K
p
(|NO
2
|
4
|O
2
|)/|N
2
O
5
|
2

(|1.80|
4
|0.45|)/(|0.10|
2
) 472 K
p

8. 2NOCl(g)
2NO(g) Cl
2
(g) K
p
7.14 x 10
-6

19

NOCl(g) is placed in a container, exerting a pressure oI 1.5 atm beIore any reaction. Calculate the
equilibrium pressure oI Cl
2
.

A. 0.0085 atm
B. 0.016 atm
C. 0.024 atm
D. 0.032 atm
E. 0.048 atm

2NOCl(g)

2NO(g) Cl
2
(g)
Initial 1.5 0 0
Change -2X 2X X
K
p
(|NO|
2
|Cl
2
|)/(|NOCl|
2
)
(|2X|
2
|X|)/(|1.5-2X|
2
) 7.14x10
-6

This is a quadratic equation. Use the small K rule to get around the quadratic equation.
(|2X|
2
|X|)/(|1.5|
2
) 7.14x10
-6

X 1.59 x 10
-2
atm

7. A container initially contains 0.500 atm oI NH
3
(g), which decomposes into N
2
(g) and H
2
(g).
2NH
3
(g)
N
2
(g) 3H
2
(g)
II 10.0 oI the NH
3
reacts to reach equilibrium calculate K
p
Ior this reaction.

A. 5.2 x 10
-5

B. 2.3 x 10
-4

C. 8.3 x 10
-4

D. 3.8 x 10
-3

E. 7.6 x 10
-3

2NH
3
(g)

N
2
(g) 3H
2
(g)
Initial 0.500 0 0
Change -0.050 0.025 0.075
Equilibrium 0.450 0.025 0.075
K
p
(|N
2
||H
2
|
3
)/(|NH
3
|
2
)
(|0.025||0.075|
3
)/(|0.450|
2
) 5.21 x 10
-5

20

10. Consider the reaction
C(s, graphite) CO
2
(g)
2CO(g)
II the initial pressure oI CO
2
(g) is 0.458 atm and the total pressure at equilibrium is 0.757 atm, what is K
p

oI the reaction?
A. 1.26
B. 3.42
C. 4.65
D. 2.25
E. 5.98

C(s)
CO
2
(g)

2CO(g)
Initial 0.458 atm 0
Change -X 2X
Equilibrium 0.458 X 2X

0.458 X 2X 0.757
X 0.299 atm

C(s)
CO
2
(g)

2CO(g)
Initial
Change
Equilibrium 0.159 atm 0.598 atm
|CO|
2
/|CO
2
| K
p

(|0.598|
2
)/0.159 2.25 K
p
D

49. 2CO
2
(g)
2CO(g) O
2
(g) K
c
2.0 x 10
-7

II 2.0 mol oI CO
2
is placed in a 5.0 L container, and decomposes according to the above equation,
calculate the concentration oI O
2
at equilibrium.

A. 5.8 x 10
-3
M
B. 2.7 x 10
-3
M
C. 4.6 x 10
-3
M
D. 2.0 x 10
-3
M
E. 9.2 x 10
-3
M

2CO
2
(g)

2CO(g) O
2
(g)
Initial 0.40M 0 0
Change -2X 2X X
21

(|CO|
2
|O
2
|)/|CO
2
|
2
2.0 x 10
-7

Use small K rule to avoid a quadratic equation.
(|2X|
2
|X|)/|0.40|
2
2.0 x 10
-7

X 0.002M D

1. 2SO
3

2SO
2
O
2
K
p
1.21 x 10
-5

II 0.60 atm oI SO
3
and 0.30 atm oI SO
2
are placed in a container, what is the partial pressure oI O
2
at
equilibrium?
A. 4.8 x 10
-5
atm
B. 0.042 atm
C. 8.4 x 10
-3
atm
D. 1.8 x 10
-4
atm
E. 7.2 x 10
-4
atm

2SO
3

2SO
2
O
2

Initial 0.60 0.30 0
Change -2X 2X X
Equilibrium 0.60 - 2X 0.30 2X X
(|SO
2
|
2
|O
2
|)/|SO
3
|
2
K
p

(|0.302X|
2
|X|)/|0.60-2X|
2
K
p

Use small K rule to avoid a quadratic equation:

2SO
3

2SO
2
O
2

Initial 0.60 0.30 0
Change -2X X X
Equilibrium 0.60 0.30 X
(|SO
2
|
2
|O
2
|)/|SO
3
|
2
K
p

(|0.30|
2
|X|)/|0.60|
2
1.21 x 10
-5

X 4.84 x 10
-5

6. Consider the reaction: NH
4
CO
2
NH
2
(s)
2NH
3
(g) CO
2
(g)
22
When solid NH
4
CO
2
NH
2
is placed in a previously evacuated container and allowed to reach equilibrium
according to the reaction above, the total pressure in the container is measured to be 0.447 atm. Calculate
K
p
Ior this reaction.

A. 3.31 x 10
-3

B. 0.0444
C. 5.12 x 10
-4

D. 0.0132
E. 0.762

NH
4
CO
2
NH
2
(s)

2NH
3
(g) CO
2
(g)
Initial Y 0 0
Change
Equilibrium

NH
4
CO
2
NH
2
(s)

2NH
3
(g) CO
2
(g)
Initial Y 0 0
Change -X 2X X
Equilibrium Y-X 2X X

2X X 0.447 atm
X 0.149 atm

NH
4
CO
2
NH
2
(s)

2NH
3
(g) CO
2
(g)
Initial Y 0 0
Change -X 2X X
Equilibrium Y-X 0.298 0.149
|NH
3
|
2
|CO
2
| K
p

|0.298|
2
|0.149| 1.32 x 10
-2

24. 2N
2
O
5
(g)
4NO
2
(g) O
2
(g)

1.00 atm oI N
2
O
5
is placed in a container, and reacts to reach equilibrium in the above reaction. The
partial pressure oI NO
2
at equilibrium is Iound to be 1.60 atm. Calculate K
p
Ior this reaction.

A. 4.1
B. 26
C. 13
D. 84
23
E. 66

2N
2
O
5

4NO
2
O
2

Initial 1.00 0 0
Change
Equilibrium 1.60

2N
2
O
5

4NO
2
O
2

Initial 1.00 0 0
Change -2X 4X X
Equilibrium 1.00 2X 1.60 X

0 4X 1.60
X 0.40

2N
2
O
5

4NO
2
O
2

Initial 1.00 0 0
Change -0.80 1.60 0.40
(|NO
2
|
4
|O
2
|)/|N
2
O
5
|
2
K
p

(|1.60|
4
|0.40|)/|0.20|
2
65.5

24
36 Chem 162-2008 Final Exam Answers
Chapter 14 Chemical Equilibrium

At 830 C, K
p
0.50 Ior the reaction
CaCO
3
(s) CaO(s) CO
2
(g)
A 1.00L Ilask containing some CaCO
3
(s) is evacuated and heated to 830 C. What
mass oI CaO (molar mass 56.08 g/mol) is also produced when equilibrium is
established?
A. 0.310g
B. 0.500g
C. 0.00552g
D. 5.3g
E. 0.411g

CaCO
3
(s)
CaO(s) CO
2
(g)
Initial Y 0 0
Change -X X X
Equilibrium Y-X X X
|CO
2
| K
p
0.50
|CO
2
X 0.50atm
PV nRT
0.50atm x 1.00L n x 0.08205Latmdeg-1mol-1 x (830 273K)
n 5.525 x 10
-3
mol CO
2

ThereIore, moles oI CaO Iormed is also 5.525 x 10
-3
mol.
5.525 x 10
-3
mol x 56.08g/mol 0.310 g CaO.

A


The reaction 2NO(g) Br
2
(g) 2NOBr(g) has K
c
1.310
-2
at 1000K. What is K
p
at
this temperature?
A. 88
B. 108
C. 1.610
-6

D. 1.1
E. 1.610
-4

K
p
K
c
(RT)
ngas

K
p
0.013 x ((0.08206 x 1000)
-1
)
K
p
1.58 x 10
-4

E
25

Given initial and total pressure, Iind K
p

16. H
2
at an initial pressure oI 10.0 atm at 3000 K dissociates into H atoms. When equilibrium is
established, the Iinal total pressure is 14.0 atm. Calculate K
p
Ior the dissociation reaction:

H
2
(g)
2H(g)

(a) 1.33
(b) 10.7
(c) 2.75
(d) 5.50
(e) 3.80

H
2
(g)

2H(g)
Initial 10.0 0
Change -X 2X
Equilibrium 10.0 - X 2X

10.0 X 2X 14.0 atm
X 4.0 atm

H
2
(g)

2H(g)
Initial
Change
Equilibrium 6.0 atm 8.0 atm
|H|
2
/|H
2
| K
|8|
2
/|6| K
K 10.7

Given initial value and solubility, Iind K
8. 2NH
3
(g)
N
2
(g) 3H
2
(g)

When 1.0 mol oI NH
3
(g) is placed in a 5.0 L container, 10.0 oI the NH
3
(g) reacts to reach
equilibrium. Calculate K Ior this reaction.

(a) 1.4 x 10
-3

(b) 3.5 x 10
-5

(c) 7.0 x 10
-4

26
(d) 8.3 x 10
-6

(e) 1.9 x 10
-6

2NH
3
(g)

N
2
(g) 3H
2
(g)
Initial 0.2M 0 0
Change -0.02 0.01 0.03

K (|N
2
||H
2
|
3
)/|NH
3
|
2
(|0.01||0.03|
3
)/(|0.18|
2
) 8.3 x 10
-6

Given initial value and K, Iind equilibrium values
4. 2NOCl(g)
2NO(g) Cl
2
(g) K
p
7.2 x 10
-6

NOCl(g) is added to a container, exerting a pressure oI 0.80 atm beIore any reaction. AIter equilibrium is
established, what is the pressure oI Cl
2
in the container?

(a) 0.010 atm
(b) 0.040 atm
(c) 0.060 atm
(d) 0.025 atm
(e) 0.075 atm

2NOCl(g)

2NO(g) Cl
2
(g)
Initial 0.80 atm 0 0
Change -2X 2X X
Equilibrium 0.80 2X 2X X

|NO|
2
|Cl
2
|/|NOCl|
2
7.2 x 10
-6

|2X|
2
|X|/|0.80-2X|
2
7.2 x 10
-6

Avoid a quadratic equation by using the small K rule.
|2X|
2
|X|/|0.80|
2
7.2 x 10
-6

X 0.0105 atm

27
Non Acid-Base equilibrium calculations
Common ion eIIect

Calculate the molar solubility oI Ag
2
SO
4
in 1.00M Na
2
SO
4
(aq). K
sp
oI Ag
2
SO
4
is
1.410
-5
.
A. 1.910
-3
M
B. 2.310
-3
M
C. 3.510
-3
M
D. 4.710
-4
M
E. 6.210
-3
M

Ag
2
SO
4

2Ag
SO
4
2-

Ag
2
SO
4
(s)

2Ag
(aq) SO
4
2-
(aq)
Initial Y 0 1.00
Change -X 2X X
Equilibrium Y-X 2X 1.00 X
|Ag
|
2
x |SO
4
2-
| K
sp

|2X|
2
x |1.00 X| (1.4 x 10
-5
)
SimpliIy due to small K rule:
|2X|
2
x |1.00| (1.4 x 10
-5
)
X 1.88 x 10
-3
M Ag
2
SO
4
solubility

28
Non Acid-Base equilibrium calculations

Consider the Iollowing equilibrium:
PCl
5
(g) PCl
3
(g) Cl
2
(g)
A Ilask is Iilled with PCl
5
to a pressure oI 2.00 atm at 300C and allowed to come to
equilibrium. Analysis shows the total pressure in the Ilask at equilibrium is 3.96 atm.
Determine the value oI K
p
at this temperature.
A. 3.96
B. 49.0
C. 96.0
D. 0.886
E. 7.84

PCl
5
(g)

PCl
3
(g) Cl
2
(g)
Initial 2.00 0 0
Change -X X X
Equilibrium 2.00 - X X X

At equilibrium, P
PCl5
P
Cl3
P
Cl2
3.96 atm
(2.00 X) X X 3.96 atm
X 1.96 atm
K (P
PCl3
x P
Cl2
)/P
PCl5

K (X x X)/(2.00 X)
K (1.96 x 1.96)/(2.00 1.96)
K 96.04

29

The pH in a saturated solution oI Mg(OH)
2
is 10.56. The K
sp
oI Mg(OH)
2
is
A. 1.3 10
-7

B. 4.8 10
-11

C. 1.2 10
-11

D. 3.6 10
-4

E. 2.410
-11

Mg(OH)
2
(solid)
Mg
2
(aqueous) 2OH
-
(aqueous)
pH 10.56
pOH 14.00 10.56 3.44
|OH
-
| 10
-pOH
10
-3.44
3.63 x 10
-4

|Mg
2
| |OH
-
| 1.82 x 10
-4

Mg(OH)
2

Mg
2
2OH
-

Initial
Change
Equilibrium 1.82 x 10
-4
3.63 x 10
-4

|Mg
2
||OH
-
|
2
K
sp

|1.82 x 10
-4
| x (|3.63 x 10
-4
|
2
) K
sp
2.40 x 10
-11

30
Chapter 14 Non Acid-base Chemical Equilibria
Selective precipitation

The concentration oI both Ag
(aq) and Pb
2
(aq) is 0.10M in a particular solution. Solid
NaCl is added slowly. What is the concentration oI Ag
that remains in solution when

PbCl
2
just begins to precipitate?
K
sp
oI AgCl 1.610
-10
; K
sp
oI PbCl
2
2.410
-4

A. 3.310
-9
M
B. 4.9 10
-3
M
C. 6.710
-9
M
D. 2.010
-10
M
E. 7.8 10
-3
M

AgCl
Ag
Cl
-

AgCl

Ag
Cl
-

Initial
Change
Equilibrium 0.10 X
|Ag
||Cl
-
| K
sp

|0.10||X| 1.6 x 10
-10

X 1.6 x 10
-9
M Cl
-
to begin precipitation oI AgCl

PbCl
2

Pb
2
2Cl
-

PbCl
2

Pb
2
2Cl
-

Initial
Change
Equilibrium 0.10 X
|Pb
2
||Cl
-
|
2
K
sp

|0.10||X|
2
2.4 x 10
-4

X 4.899 x 10
-2
M Cl
-
to begin precipitation oI PbCl
2
.

When PbCl
2
just begins to precipitate, the |Cl
-
| 4.889 x 10
-2
M

At 4.889 x 10
-2
M, the Ag
remaining in the solution:

|Ag
|| 4.889 x 10
-2
| 1.6 x 10
-10

|Ag
| 3.27 x 10
-9
M

31

NON-ACID BASE EQUILIBRIUM CALCULATIONS
6. 2SO
3
(g)

2SO
2
(g) O
2
(g) K
p
4.00 at 1100 K

Some pure SO
3
(g) is placed in a container and reacts to reach equilibrium. At equilibrium, the pressure
oI O
2
0.10 atm. Calculate the pressure oI SO
3
remaining at equilibrium.

(a) 0.055 atm
(b) 0.015 atm
(c) 0.080 atm
(d) 0.032 atm
(e) 0.0050 atm

2SO
3
(g)

2SO
2
(g) O
2
(g)
Initial Y
Change
Equilibrium 0.10

2SO
3
(g)

2SO
2
(g) O
2
(g)
Initial Y 0 0
Change -2X 2X X
Equilibrium Y-2X 2X 0.10

0 X 0.10
X 0.10 atm

2SO
3
(g)

2SO
2
(g) O
2
(g)
Initial
Change
Equilibrium Y-0.20 0.20 0.10
|SO
2
|
2
|O
2
|/|SO
3
|
2
K
p

|0.20|
2
|0.10|/|Y-0.20|
2
4.00
(((((|0.20|
2
) x |0.10|)/(|Y-0.20|
2
)) (4.00)),X)
Y 0.2316
0.2316 0.20 0.0316 atm SO
3
remaining at equilibrium

ProoI: ((|0.20|
2
) x |0.10|)/(|0.0316|
2
) 4.006

32

9. Solid NH
4
CO
2
NH
2
is placed in a container and decomposes into NH
3
and CO
2
to reach equilibrium. The
reaction is:

NH
4
CO
2
NH
2
(s)
2NH
3
(g) CO
2
(g) K
p
0.45

At equilibrium , what is the partial pressure oI CO
2
in the container?

(a) 0.67 atm
(b) 0.74 atm
(c) 0.32 atm
(d) 0.48 atm
(e) 0.15 atm

NH
4
CO
2
NH
2
(s)

2NH
3
(g) CO
2
(g)
Initial Y 0 0
Change -X 2X X
Equilibrium Y-X 2X X

|NH
3
|
2
|CO
2
| K
p

|2X|
2
|X| 0.45
((((|2X|
2
) x |X|) (0.45)),X)
X 0.483 atm

12. 2NO(g) Cl
2
(g)
2NOCl(g) K
p
1.6 x 10
8

II 3.0

atm NO(g) and 2.0 atm Cl
2
(g) are placed in a container and allowed to react to reach equilibrium,
what is the pressure oI the Cl
2
(g) at equilibrium?

(a) 3.0 atm
(b) 2.0 atm
(c) 1.0 atm
(d) 0.5 atm
(e) 0.1 atm

2NO(g)
Cl
2
(g)

2NOCl(g)
Initial 3.0 2.0 0
Change -2X -X 2X
Equilibrium 3.0 - 2X 2.0 - X 0 2X
33

|NOCl|
2
/|NO|
2
|Cl|
2
K
p

|2X|
2
/|3.0-2X|
2
|2.0-X|
2
1.6 x 10
8

This calculation will result in an equation more complicated than a quadratic equation (i.e., an equation with
Iour roots).
One way oI solving this is with an advanced calculator:
((((|2X|
2
)/(|3.0-2X|
2
) x (|2.0-X|
2
)) (1.6 x 10
8
)),X)
X 1.500
ThereIore, |Cl
2
| 2.0 1.5 0.5 atm

Another way to solve this is to take advantage oI the large K, i.e., bring the reaction to completion.
NO is the limiting reactant.
2NO(g)
Cl
2
(g)

2NOCl(g)
Initial 3.0 2.0 0
Change -3.0 -1.5 3.0
Equilibrium 0 0.5 3.0
|Cl
2
| 0.5 atm

17. Suppose 2.00 mol oI H
2
(g) and 1.00 mol oI I
2
(g) are placed in a 1.00 L container, and they react to
Iorm HI(g). At equilibrium, it is Iound that 1.80 moles oI HI(g) are present in the container. Calculate K
Ior the reaction:

H
2
(g) I
2
(g)
2HI(g)

(a) 57.5
(b) 29.5
(c) 82.2
(d) 40.1
(e) 17.8

H
2
(g)
I
2
(g)

2HI(g)
Initial 2.00 1.00
Change
Equilibrium 1.80

H
2
(g)
I
2
(g)

2HI(g)
Initial 2.00 1.00 0
Change -X -X 2X
Equilibrium 2.00-X 1.00-X 1.80
34

02X 1.80
X 0.90M

H
2
(g)
I
2
(g)

2HI(g)
Initial
Change

|HI|
2
/|H
2
||I
2
| K
c

|1.80|
2
/|1.10||0.10| K
c

(|1.80|
2
)/(|1.10||0.10|) 29.45

35
LE CHATELIERS PRINCIPLE

Le Chatelier`s Principle
8. N
2
(g) 3H
2
(g)
2NH
3
(g) H -92 kJ

Assume this system is at equilibrium in a 1.0 L container at 500 K. Which oI the Iollowing changes
will result in a new equilibrium system with a higher value oI the equilibrium constant K?

X. Compress the system to 0.50 L at constant temperature.
Y. Cool the system to 400 K.
Z. Add a catalyst.

A. Y only
B. X only
C. X and Y only
D. Y and Z only
E. X, Y, and Z

This is an exothermic reaction.
N
2
(g) 3H
2
(g)
2NH
3
(g) heat

X. False. Compression increases the concentration oI all oI the substances. According to LeChatelier, the
stress oI the increased concentration will be relieved iI the equilibrium is shiIted to the right (Iewer
molecules). However, this does nothing to change the equilibrium constant. The only thing that will
change the equilibrium constant is a change oI temperature.
Y. True. II the system is cooled to 400 K, then heat will be removed Irom the system. In an exothermic
reaction, iI heat is removed, then the equilibrium will shiIt to the right to provide more heat. This
provides a higher value oI the equilibrium constant.
Z. False. Addition oI a catalyst has no eIIect on changing the equilibrium reaction or the equilibrium
constant.

36
4. For a particular gas phase reaction, the value oI K
p
will decrease as temperature increases:

A. iI H 0
B. iI H ~ 0
C. iI more moles oI gas are on product side oI reaction
D. iI more moles oI gas are on reactant side oI reaction.
E. under no circumstances.

According to LeChatelier, the only way that the value oI K
p
will decrease as temperature increases would
be iI the reaction is exothermic.
A B
C D
Addition oI heat will drive the reaction to the leIt, thereby decreasing the equilibrium constant. An
exothermic reaction means that H 0, i.e., that H is negative.

10. 2NO(g) O
2
(g)
2NO
2
(g) H -114 kJ
Assume that this system has reached equilibrium in a 1.00 L container at 298 K. Which oI the Iollowing
changes will result in a greater amount oI NO
2
(g) at equilibrium?

X. Raise temperature to 398 K
Y. Lower volume to 0.50 L
Z. Add a catalyst

A. Y only
B. X only
C. X and Y only
D. Y and Z only
E. X, Y, and Z

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

X. Raising the temperature will Iorce the reaction to the leIt, according to LeChatelier. This decreases
the amount oI NO
2
.
Y. Lowering the volume is the same as raising the pressure. According to LeChatelier, the system resists
the increase oI pressure. II the reaction moves to the right, then three moles oI gas will become two moles
oI gas, resulting in a reduced pressure. Moving to the right results in an increase in NO
2
concentration.
Z. Adding a catalyst only speeds up the reaction. It has no eIIect on the concentration oI reactants or
products.

37
LE CHATELIER`S PRINCIPLE
28. A 1.0 liter container holds PCl
3
, Cl
2
and PCl
5
in equilibrium at 298 K

PCl
3
(g) Cl
2
(g)
PCl
5
(g) H -87.9 kJ K
p
3.3 x 10
6

Which oI the Iollowing changes will increase the numerical value oI K
p
?

W. Compress the entire system to 0.50 liter.
X. Expand the entire system to 2.0 liter.
Y. Raise the temperature to 323 K.
Z. Lower the temperature to 273 K.

A. W and Y
B. Z only
C. Y and Z
D. W and Z
E. Y only

The only thing that will change the equilibrium constant is a change in temperature. In this case, the
reaction is exothermic, so we can write:
PCl
3
(g) Cl
2
(g)
PCl
5
(g)
II we remove the heat, the reaction will shiIt to the right, thereby increasing the numerical value oI the
equilibrium constant.

Lower the temperature to 273K B

14. N
2
O
4
(g)
2NO
2
(g)
N
2
O
4
(g) and NO
2
(g) reach equilibrium in a 1.00 L container. The volume oI the container is halved at
constant temperature. When equilibrium is reestablished:

A. The partial pressures oI both N
2
O
4
and NO
2
double.
B. The partial pressure oI NO
2
more than doubles, and the partial pressure oI N
2
O
4
less than doubles.
C. The partial pressure oI N
2
O
4
more than doubles and the partial pressure oI NO
2
less than doubles.
D. The value oI K increases.
E. The value oI K decreases.

This problem might have been better written iI it would have said, 'Relative to the initial equilibrium,
when equilibrium is reestablished:

II the volume oI the container is halved, then the pressure is doubled. This means that Ior an instant in
time the NO
2
and the N
2
O
4
pressures are doubled. LeChatelier tries to bring the pressure back toward
38
where the pressure was beIore it was doubled. Since conversion oI two NO
2
molecules to one N
2
O
4

molecule decreases the number oI molecules and thereIore decreases the pressure, then the equilibrium
equation shiIts to the leIt. This results in an increase in the N
2
O
4
pressure, to be slightly more than
double, and a decrease in the NO
2
pressure to be signiIicantly less than double, resulting in the total
pressure being less than double the initial.

A. False. This means that there is no shiIt in the reaction Irom right to leIt, which would result in
decreasing the added pressure.
B. False. This means that there is a shiIt in the reaction Irom leIt to right, which would result in
increased pressure, not decreased pressure.
C. True. This shiIt Irom right to leIt decreases the total pressure, so that it is less than double the original
pressure.
D. False. The shiIt in the equilibrium equation results in a reestablishment oI the original K.
E. False. The shiIt in the equilibrium equation results in a reestablishment oI the original K.

39

For the reaction

NH
3
(g) HCl(g) NH
4
Cl(s) H
o
177 kJ

What conditions Iavor the production oI ammonium chloride (NH
4
Cl)?

A. High temperature and low pressure
B. Low temperature and high pressure
C. Low temperature and low pressure
D. High temperature and high pressure
E. Addition oI an inert gas (constant volume)

H
o
oI -177 kJ means that it is an exothermic reaction.
NH
3
(g) HCl(g) NH
4
Cl(s)
The production oI NH
4
Cl would be Iavored iI the equilibrium reaction would shiI
to the right.
According to LeChatelier, removing heat (i.e., lowering the temperature) will
Iorce the reaction to the right. Also, since there are more moles oI gas on the leIt
than on the right, increasing the pressure will result in Iorcing the reaction to the
right (thereby lowering the pressure since a solid is Iormed Irom the gases).
Hence, option 'B, lowering the temperature and increasing the pressure will
Iorce the reaction to Iorm more NH
4
Cl.

Addition oI an inert gas will have no eIIect on the equilibrium reaction because
the inert gas is not part oI the equilibrium expression.

B

Le Chatelier; eIIect oI temperature in shiIting equilibrium
12. CuO(s) H
2
(g)
Cu(s) H
2
O(g) H -2.0 kJ

When the substances in the equation above are at equilibrium at pressure P and temperature T, the
equilibrium can be shiIted to Iavor the products by:

(a) increasing the pressure by lowering the volume oI the system.
(b) decreasing the temperature.
(c) increasing the pressure by adding an inert gas such as nitrogen.
40
(d) allowing some gases to escape at constant P, T.
(e) adding a catalyst.

H is negative; thereIore it is an exothermic reaction, so put heat on the right hand side oI the equation.
CuO(s) H
2
(g)
Cu(s) H
2
O(g)
(a) False. Since there is one mole oI gas on the leIt side, and one mole oI gas on the right side, increasing
the pressure will have no eIIect.
(b) True. Decreasing the temperature in an exothermic reaction will Iorce the equilibrium to the right.
(c) False. Even iI changing the pressure would shiIt the equilibrium (which it won`t in this case), adding
an inert gas would have no eIIect on the equilibrium because the inert gas is not in the equilibrium
expression.
(d) False. II we assume that both gases have an equal diIIusion rate, then allowing both gases to
somewhat escape, at constant pressure, would keep the Iinal pressure oI each gas the same, and
thereIore wouldn`t put a stress on the system. Hence, the equilibrium wouldn`t shiIt. On the other
hand, iI we assume that H
2
has a greater rate oI diIIusion than H
2
O, which is true, then more H
2

would escape than H
2
O, and the equilibrium would shiIt to the leIt, not to the right.
(e) False. Adding a catalyst speeds up the Iorward and reverse reactions, but has no eIIect on shiIting the
equilibrium.


Which condition will increase oI the value oI the equilibrium constant?
A. Raising the temperature at which an exothermic reaction is conducted.
B. Adding a catalyst to an endothermic reaction.
C. Raising the temperature at which an endothermic reaction is conducted.
D. Removing the products Irom the reaction mixture.
E. Reducing the size oI the container in a gas phase reaction.

A. False. Raising the temperature oI an exothermic reaction will drive the reaction to
the leIt, decreasing the value oI the equilibrium constant.
B. False. Adding a catalyst to any reaction doesn`t aIIect the equilibrium constant.
C. True. Raising the temperature oI an endothermic reaction will drive the reaction to
the right, increasing the value oI the equilibrium constant.
D. False. Removing the products Irom the reaction mixture (i.e., Irom the reactants
and/or the products) will tend to drive the reaction one way or the other, but will not
aIIect the equilibrium constant.
E. False. Reducing the size oI the container will increase the pressure iI the reaction
mixture contains gases, which will probably shiIt the reaction to the leIt or to the right,
depending on the reaction, but will not aIIect the equilibrium constant.

41

3. N
2
O
4
(g)
2NO
2
(g) K
p
80 at 25
o
C

Assume the reaction is in a 1.0 L container at equilibrium at 25
o
C. The volume oI the container is
halved to 0.50 L with the temperature maintained at 25
o
C. Which oI the Iollowing would be
correct when equilibrium is reestablished?

(a) The partial pressures oI N
2
O
4
and NO
2
both double and K
p
~ 80
(b) The partial pressures oI N
2
O
4
and NO
2
both double and K
p
80
(c) The partial pressure oI N
2
O
4
more than doubles, the partial pressure oI
NO
2
less than doubles, and K
p
80
(d) The partial pressure oI NO
2
more than doubles, the partial pressure oI N
2
O
4

less than doubles and K
p
~ 80
(e) The partial pressure oI N
2
O
4
more than doubles, the partial pressure oI
NO
2
less than doubles, and K
p
80.

II the volume oI the container is halved (at constant temperature and moles), then the pressure is
momentarily doubled, according to the Combination Gas Law. Doubling the pressure would
momentarily make the pressure oI NO
2
double, and the pressure oI N
2
O
4
double, which would result
in a momentary increase in the equilibrium constant. According to LeChatelier, the reaction will
shiIt in a direction to reduce this new high pressure, and thereby bring the equilibrium constant back
to its original value. Since going to the leIt will convert two molecules (oI NO
2
) into one molecule
(oI N
2
O
4
), then going to the leIt will reduce the pressure and bring the equilibrium constant back to
its original value. Hence, the NO
2
pressure will be reduced Irom double its value, and concurrently
the N
2
O
4
pressure will be increased to above double the value, and the equilibrium constant would
go back to its original value.
|NO
2
|
2
/|N
2
O
4
| 80
As an example, let |N
2
O
4
| 1 atm, and |NO
2
| 8.94 atm.
|8.94|
2
/|1| 80
Let the pressure instantaneously double.
|17.88|
2
/|2| 160
Then the equilibrium reaction adjusts so that the K oI 80 is restored.
|15.71|
2
/3.085 80 Note that the |NO
2
| decreases to a little less than double, while the |N
2
O
4
| increases
to more than double.

(a) False, because K
p
80 must be re-established.
(b) False, because iI the partial pressures oI N
2
O
4
and NO
2
both double then K
p
would be ~ 80.
(c) False, because K
p
oI 80 must be re-established.
(d) False, because K
p
oI 80 must be re-established.
(e) True, as can be seen by the Iinal concentrations being: |15.71|
2
/3.085 80

42
7 . Consider the reaction N
2
(g) 3H
2
(g)
2NH
3
(g) H -92.6 kJ

Assume that the reaction is at equilibrium in a 1.0 L container. Which oI the Iollowing changes
would result in a greater amount oI NH
3
in the container at equilibrium?

X. Add argon gas to the container with no change oI volume or
temperature.
Y. Add a catalyst to the container.
Z. Lower the temperature.

(a) Z only
(b) X only
(c) Y only
(d) X and Z only
(e) X, Y, ands Z

N
2
(g) 3H
2
(g)
2NH
3
(g)
X. False. Adding argon doesn`t aIIect the equilibrium. Although it aIIects the total pressure, it doesn`t
aIIect the pressure oI any oI the components in the equilibrium expression.
Y. False. Adding a catalyst doesn`t aIIect the equilibrium. Although it speeds up the reaction, it has no
eIIect, whatsoever, on any oI the components in the equilibrium expression.
Z. True. Lowering the temperature will shiIt the equilibrium to the right in the direction oI greater
ammonia. This can be looked at according to LeChatelier, in which case we are removing a
component Irom the right side oI the equilibrium reaction, so the equilibrium reaction will shiIt to
the right in an attempt to regain some oI that lost heat. This can also be looked at as the reaction
products have higher enthalpy than the reactants. Hence, Iorming more product will give oII heat,
bringing the system back to where it was originally, Irom the point oI view oI temperature.

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that remains in solution when

remaining in the solution:

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