CHM152 Final Review #1 (Ch.

12, 13) KEY

1. 2HBr H2 + Br2
a. Express the rate of reaction with respect to each of the reactants and products

Rate of reaction =

1 HBr 1 H2 1 Br2
=
=
2 t
1 t 1 t

b. In the first 15.0s of this reaction the [HBr] dropped from 0.500M to 0.455M. Calculate the
average rate of reaction for this interval.

Rate of reaction =

1 0.455M - 0.500M
= 0.0015 Ms
2
15.0s

c. If the volume of the reaction vessel was 0.500L, what amount of Br2 (in moles) was formed
during the first 15.0s?

0.0015 Ms =

1 Br2
1 15.0s

Br2 = 0.0225M

0.0225 mol 0.500L

= 0.011mol Br2
L
1

2. What are the units for k in each of the following

a. First-order reaction: s-1 or 1/s
b. Second-order reaction: Ms-1 or M/s
c. Zero-order reaction: M-1s-1 or 1/Ms
3. The data below were collected for the following reaction:
2NO2 + F2 2NO2F
[NO2](M)
0.100
0.200
0.200
0.400

[F2](M)
0.100
0.100
0.200
0.400

Initial Rate (M/s)

0.026
0.051
0.103
0.411

Rate = k[A] [B]

x

[A]
Rate 1
= k 1
Rate 2
[A] 2

Write an expression for the reaction rate law and calculate the value of the rate constant, k. What is
the overall order of the reaction?
x

1.96 Ms = k(2 )x

x =1

2.01 Ms = k(2 )y

y =1

0.051 Ms
0.200M 0.100M
= k

M
0.026 s
0.100M 0.100M
0.103 Ms
0.200M 0.200M
=
k

0.051 Ms
0.200M 0.100M
0.026 Ms = k (0.100M )1 (0.100M )1

Rate = 2.6 Ms [NO 2 ][F2 ]

k = 2.6 M1s

2nd order overall

[B]1

[B] 2

4. The decomposition of SO2Cl2 is first order in SO2Cl2 and has area constant of 1.42x10-4 s-1 at a certain
temperature.
ln2
ln2
t1 =
= 4.88x10 3 s
a. What is the half-life for this reaction?
t1 =
4 1
2
2

1.42x10

b. How long will it take for the concentration of SO2Cl2 to decrease to 25% of its initial
()2 = or 25%. 9.76x103s

concentration? Two half-lives.

c. If the initial concentration of SO2Cl2 is 1.00M, how long will it take for the concentration to
decrease to 0.78M?

[A]
ln t
[A] 0

= kt

0.78M
-4
ln
= (1.42x10 1s ) t
1.00M

t = 1.75x10 3 s

d. If the initial concentration of SO2Cl2 is 0.150M, what is the concentration of SO2Cl2 after
2.00x102s? After 5.00x102s?

[A] t
-4
2
ln
= (1.42x10 1s ) (2.00x10 s)
0.150M

ln[A] t ln(0.150M) = (1.42x10 -4 1s ) (2.00x10 2 s)

ln[A] t ln(0.150M) = (1.42x10 -4 1s ) (2.00x10 2 s)

e ln[A] t = 1.922 5

ln[A] after 200.s = 0.146M

After 500s, 0.140M (work not shown)

5. A reaction has a rate constant of 0.0117/s at 400.K and 0.689/s at 450.K.
a. Determine the activation energy for the reaction

k
E
ln 1 = a
k2
R

1 1

T1 T2

ln

0.0117 1s
Ea
1
1
=

1
0.698 s
8.314J/mol K 400.K 450.K

E a = 1.22x10 5

J
mol

b. What is the value of the rate constant at 425K?

ln

J
0.0117 1s
1.22x10 5 mol
1
1
=

k2
8.314J/mol K 400.K 425K

ln(0.0117 1s ) lnk 2 = 2.158

6. Consider the following three-step mechanism for a reaction:

Fast
Cl2(g) 2Cl(g)
Cl(g) + CHCl3(g) HCl(g) + CCl3(g) Slow
Cl(g) + CCl3(g) CCl4(g)
Fast
a. What is the overall reaction?
Cl2(g) 2Cl(g)
Fast
Cl(g) + CHCl3(g) HCl(g) + CCl3(g) Slow
Cl(g) + CCl3(g) CCl4(g)
Fast
Cl2(g) +CHCl3 HCl(g) + CCl4(g)

e lnk 2 = e 2.290

k 2 = 0.101 1s

b. Identify the intermediates in the reaction.

Cl(g), CCl3(g)

c. What is the predicted rate law? k1[Cl2]=k-1[Cl]2 and k2[Cl][CHCl3]

Solve for
intermediate

[Cl] =

k 1 [Cl2 ]
k 2 [Cl][CHCl3 ]
k 1 Substitute to cancel

k2

k 1 [Cl2 ]
[CHCl3 ]
k 1

If the slow step is first, them the rate

law is based only on the slow step.
However, if the slow step is not first, it
is based on the slow step and any fast
steps before it (remember, bottleneck).
1

k[Cl2 ] 2 [CHCl3 ]

intermediate

7. The reaction below has an equilibrium constant of Kp=2.26x104 at 298K.

CO(g) + 2H2(g) CH3OH(g)
Calculate Kp for each of the following reactions and predict whether reactants or products will be
favored.
a. CH3OH(g) CO(g) + 2H2(g) reverse reaction soKp2 = 1/Kp1 = 4.42x10-5, reactant favored
b. CO(g) + H2(g) CH3OH(g) coefficients so Kp2 = (2.26x104) = 1.13x104, products
favored
c. CH3OH(g) 2CO(g) + 4H2(g) reverse reaction and doubled coefficients, so Kp2 = (2)(1/Kp1 ) =
8.84x10-5, reactants favored

K p = K c (RT) n

8. Calculate Kc for each of the following reactions (assume 298K):

1
atm
6.26x10 22 = K c (0.08206 Lmol
a. I2(g) 2I(g)
Kp = 6.26x10-22
K 298K)
b. CH4(g) + H2O(g) CO + 3H2(g) Kp = 7.7x1024 7.7x10 24 = K c (0.08206 Latm 298K) 2
molK

K c = 2.56x10 23
K c = 1.3x10 22

7. For the following reaction, Kc = 0.513 at 500K.

N2O4(g) 2NO2(g)
If a reaction vessel initially contains a N2O4 concentration of 0.0500M at 500K, what are the
equilibrium concentrations of N2O4 and NO2 at 500K?

I
C
E

N2O4(g) 2NO2(g)
0.0500M
0
-x
+2x
0.0500-x
2x

K=

(2x) 2
= 0.513
(0.0500 x)

[N2O4]eq= 0.0500-0.03846 = 0.0115M

K=

[NO 2 ]2
= 0.513
[N 2 O 4 ]

[0.0769] 2
= 0.514 0.513
[0.0115]

4x 2 + 0.513x 0.02565 = 0
Use quadratic Formula

x = 0.038 46 and x = 0.1667

[NO2]eq= 2(0.03846) =0.0769M

8. Consider the following reaction:

NiO(s) + CO(g) Ni(s) + CO2(g)

Kc = 4.0x103 at 1000K

If a mixture of solid nickel(II) oxide and 0.10M carbon monoxide were allowed to come to
equilibrium at 1000K, what would be the equilibrium concentration of CO2?
NiO(s) + CO(g) Ni(s) + CO2(g)
I
0.10M
0
C
-x
+x
E
0.10M-x
x
[CO]eq = 0.10M-0.010M=0

K=

[CO 2 ]
= 4.0x10 3
[CO]

x
= 4.0x10 3
(0.10 x)

[CO2]= 0.10M

x = 4.0x10 2 4.0x10 3 x
4.0 01x10 3 x = 4.0x10 2
x = 0.099975M = 0.10M

K=

0.099975
= 3999 4000
0.000025

9. Consider the following reaction at equilibrium:

2KClO3(s) 2KCl(s) + 3O2(g)
Predict whether the reaction will shift left, shift right, or remain unchanged upon each of the
following disturbances
a. O2 is removed from the reaction mixture.
Shift to right, O2 and KCl , KClO3
b. KCl is added to the reaction mixture.
Nothing will happen, solids do not affect eq.
c. KClO3 is added to the reaction mixture.
Nothing will happen, solids do not affect eq.
Shift to left, O2 and KCl, KClO3
d. O2 is added to the reaction mixture.