III Kinetics & Equilibrium-Review

III.

Kinetics & Equilibrium-Review AP Chemistry

1) Write the expression for K
eq
for the following reactions. In each case indicate whether the reaction is homogeneous
or heterogeneous.

a) 3 NO (g) N
2
O (g) + NO (g) b) CH
4
(g) + 2 H
2
S (g) CS
2
(g) + 4 H
2
(g)
c) Ni(CO)
4
(g) Ni (s) + 4 CO (g) d) HF (aq) H
+
(aq) + F
-
(aq)
e) 2 Ag (s) + Zn
+2
(aq) 2 Ag
+
(aq) + Zn (s)

2) Write equilibrium constant expressions for the following homogeneous equilibria.
a) C
2
H
4
O (g) CH
4
(g) + CO (g) b) 3 O
2
(g) 2 O
3
(g)
c) 2 N
2
O (g) + O
2
(g) 4 NO (g) d) 4 NH
3
(g) + 3 O
2
(g) 2 N
2
(g) + 6 H
2
O (g)

3) When the following reaction comes to equilibrium, does the equilibrium mixture contain mostly reactants or mostly
products?
a) N
2
(g) + O
2
(g) 2 NO (g); K
eq
= 1.5 x 10
-10

b) 2 SO
2
(g) + O
2
(g) 2 SO
3
(g); K
eq
= 2.5 x 10
9

4) The following is the chemical equation for the decomposition of formamide.
HCONH
2
(g) NH
3
(g) + CO (g)
Calculate the K
eq
using the equilibrium data [HCONH
2
] = 0.0637 mol/L, [NH
3
] = 0.518 mol/L, and [CO] =
0.518 mol/L.

5) Hydrogen and carbon disulfide react to form methane and hydrogen sulfide according to this equation.
4 H
2
(g) + CS
2
(g) CH
4
(g) + 2 H
2
S (g)
Calculate K
eq
if the equilibrium concentrations are [H
2
] = 0.205 mol/L, [CS
2
] = 0.0664 mol/L, [CH
4
] = 0.0196
mol/L and [H
2
S] = 0.0392.

6) Gaseous hydrogen iodide is placed in a closed container at 425
0
C, where it partially decomposes to hydrogen and
iodine: 2 HI (g) H
2
(g) + I
2
(g). At equilibrium it is found that P
HI
= 0.202 atm, P
H2
= 0.0274 atm, and P
I2
=
0.0274 atm. What is the value of K
p
at this temperature? How does this value compare to K
eq
?

7) At 500 K the following equilibrium is established: 2 NO (g) + Cl
2
(g) 2 NOCl
2
(g). An equilibrium mixture of
the three gases has partial pressures of 0.095 atm, 0.171 atm, and 0.28 atm for NO, Cl
2
, and NOCl, respectively.
Calculate K
p
for this reaction at 500 K. Calculate K
eq
for this reaction.

8) When the reaction: PCl
5
(g) PCl
3
(g) + Cl
2
(g) reaches equilibrium at 250
0
C, the equilibrium partial pressures
of PCl
5
, PCl
3
and Cl
2
are 0.875 atm, 0.463 atm, and 1.98 atm, respectively. Calculate K
p
and K
eq
for this reaction.

9) Given the following reaction at equilibrium, if K
p
= 1.05 at 250
o
C, Calculate K
c.

PCl
5
(g) PCl
3
(g) + Cl
2
(g)

10) The reaction: H
2
(g) + I
2
(g) 2 HI (g) is carried out at 690 K with the following initial concentrations: [H
2
] =
1.00 x 10
-3
M; [I
2
] = 2.00 x 10
-3
M; [HI] = 0.00 M. When the reaction reaches equilibrium, [HI] = 1.88 x 10
-3
M.
Calculate the equilibrium constant for this reaction.

11) At a certain temperature, the reaction 2 N
2
(g) + O
2
(g) 2 N
2
O (g) has an equilibrium constant K
eq
= 2.0 x 10
-
13
. A 3.0 liter container at this temperature contains 0.150 mole of N
2
and 0.270 mole of O
2
initially. Calculate the
equilibrium concentrations of N
2
, O
2
and N
2
O.

12) A particular first order reaction has a rate constant of 1.35 x 10
2
s
-1
at 250
o
C. What is the magnitude of k at 95.0
o
C if E
a
= 55.5 kJ/mol?

13) A sealed 1.0 L flask is charged with 0.500 mol of I
2
and 0.500 mol of Br
2
. An equilibrium reaction ensues:
I
2
(g) + Br
2
(g) 2 IBr (g)
When the container contents achieve equilibrium, the flask contains 0.84 mol of IBr. What is the value of Keq?

14) C (s) + H
2
O (g) CO (g) + H
2
(g) H = +131 kJ
A rigid container holds a mixture of graphite pellets (C (s)), H
2
O (g), CO (g), and H
2
(g) at equilibrium. State whether
the number of moles of CO (g) in the container will increase, decrease or remain the same after each of the following
disturbances is applied to the original mixture. For each case, assume that all other variables remain constant except
for the given disturbance. Explain each answer with a short statement.
a) Additional H
2
(g) is added to the equilibrium mixture at constant volume, b) The temperature of the
equilibrium mixture is increased at constant volume, c) The volume of the container is decreased at
constant temperature, and d) The graphite pellets are pulverized. (AP Exam 1998 D)

15) Determine the rate law and rate constant for the reaction: S
2
O
8
-2
(aq) + 3 I
-
(aq) 2 SO
4
-2
+ I
3
-
(aq), given the
following data:
Trial [S
2
O
8
-2
]/M [I
-
]/M Initial Rate/(M/s)
1 0.018 0.036 2.6 x 10
-6

2 0.027 0.036 3.9 x 10
-6

3 0.036 0.054 7.8 x 10
-6

4 0.050 0.072 1.4 x 10
-5

16) Determine the rate law and rate constant for the reaction: 2 NO (g) + O
2
(g) 2 NO
2
(g), given the following
data:
Trial [NO]/moles L
-1
[O
2
]/ moles L
-1
Initial Rate/( moles L
-1
s
-1
)
1 0.0126 0.0125 7.05 x 10
-3

2 0.0252 0.0250 5.64 x 10
-2

3 0.0252 0.0125 2.82 x 10
-2

17) The data in the table below were obtained for the reaction: A + B P

Experiment [A] (M) [B] (M) Initial Rate (M/s)
1 0.273 0.763 2.83
2 0.273 1.526 2.83
3 0.819 0.763 25.47

a) The order of the raction in A is? b) The order of the reaction in B is? c) The overall order of
the reaction is? d) For a first order reaction, what plot is needed?

18) Given the following reaction: 2 HI (g) H
2
(g) + I
2
(g)
Below is the value of the rate constant at various temperatures for the gas phase reaction above. Calculate
the activation energy.
T (K) k (litre/mol sec)
647 8.58 x 10
-5
666 2.19 x 10
-4

683 5.11 x 10
-4

700 1.17 x 10
-3

716 2.50 x 10
-3

Answers

1) a) K
eq
=
2
3
[ ][ ]
[ ]
N O NO
NO
b) K
eq
=
4
2 2
2
4 2
[ ][ ]
[ ][ ]
CS H
CH H S
c) K
eq
=
4
4
[ ]
[ ( ) ]
CO
Ni CO

homogeneous homogeneous heterogeneous

d) K
eq
=
[ ][ ]
[ ]
H F
HF

e) K
eq
=
2
2
[ ]
[ ]
Ag
Zn

homogeneous heterogeneous

2) a) K
eq
=
4
2 4
[ ][ ]
[ ]
CH CO
C H O
b) K
eq
=
2
3
3
2
[ ]
[ ]
O
O
c) K
eq
=
2
2 2
[ ]
[ ] [ ]
NO
N O O
d) K
eq
=
2 6
2 2
4 3
3 2
[ ] [ ]
[ ] [ ]
N H O
NH O

homogeneous homogeneous homogeneous homogeneous

3) a) mostly reactants b) mostly products

4) K
eq
= 4.212 15) Rate = 3.88 x 10
-3
M/s [S
2
O
8
-2
] [I
-
]

5) K
eq
= 0.257 16) Rate = 3.55 x 10
3
M
-2
s
-1
[NO]
2
[O
2
]

6) K
p
= K
eq
= 0.0184 17) a) 2 b) 0 c) 2 d) ln [A] vs. t

7) K
p
= 50.80, K
eq
= 2085.3 18) 189 kJ/mol

8) K
p
= 1.048, K
eq
= 0.0244

9) K
eq
= 2.45 x 10
-2

10) K
eq
= 55.6

11) [N
2
] = 0.05 M, [O
2
] = 0.09 M, [N
2
O] = 6.0 x 10
-9
M

12) E
a
= 9.56 x 10
3

13) K
eq
= 110

14) a) CO will decrease. An increase of hydrogen gas molecule will increase the rate of the
reverse reaction which consumes CO. A LeChatelier Priniciple shift to the left. b) CO will
increase. Since the forward reaction is endothermic and increase in temperature will cause the
forward reaction to increase its rate and produce more CO. A LeChatelier Priniciple shift to the
right. C) CO will decrease. A decrease in volume will result in an increase in pressure, the
equilibrium will shift to the side with fewer gas molecules to decrease the pressure, therefore a
shift to the left. d) CO will remain the same. Once at equilibrium, the size of the solid will affect
neither the reaction rates nor the concentration of reactants or products.

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III.

Kinetics & Equilibrium-Review AP Chemistry

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