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# Problem set 1

## Gabriel Christian V. Alava

April 24, 2014
For multiple choice questions, X means there is
no applicable choice.
I. 1. A
2. D
3. C
4. C
5. A
II. 1. B
2. C
3. B
4. D
5. B
6. C
7. B
8. B
9. C
10. B
11. C
12. B
13. A
14. B
15. A
16. 1. A
2. B
3. C
4. C
17. 1. B
2. A
3. X
4. B
III. 1. A. k = rate = 0.030 M min
1

d [D]
dt
= k
d [D] = kdt
_
[D]
t
[D]
0
d [D] =
_
t
0
kdt = kt
_
[D]
0
[D]
t
d [D] = [D]
0
[D]
t
= kt
t 1
2
=
1
2
[D]
0
k
= 2.5 min
B. k =
rate
[D]
0
= 0.20 min
1

d [D]
dt
= k [D]

d [D]
[D]
= kdt
_
[D]
t
[D]
0

d [D]
[D]
=
_
t
0
kdt = kt
_
[D]
0
[D]
t
d [D]
[D]
= ln [D]
0
ln [D]
t
= kt
t 1
2
=
ln 2
k
= 3.5 min
C. k =
rate
[D]
2
0
= 1.3 M
1
min
1

d [D]
dt
= k [D]
2

d [D]
[D]
2
= kdt
_
[D]
t
[D]
0

d [D]
[D]
2
=
_
t
0
kdt = kt
_
[D]
0
[D]
t
d [D]
[D]
2
=
1
[D]
t

1
[D]
0
= kt
t 1
2
=
1
[D]
0
k
= 5.0 min
D. k =
rate
[D]
3
0
= 8.9 M
2
min
1

d [D]
dt
= k [D]
3

d [D]
[D]
3
= kdt
_
[D]
t
[D]
0

d [D]
[D]
3
=
_
t
0
kdt = kt
_
[D]
0
[D]
t

d [D]
[D]
3
=
1
2 [D]
2
t

1
2 [D]
2
0
= kt
t 1
2
=
3
2[D]
2
0
k
= 7.5 min
2. A. rate = k [A] [B]
B. k = 2.0 10
2
M
1
min
1
3. The following rate constants will be used
for each reaction.
HA
k1

k1
H
+
+ A

(1)
X + H
+
k2

k2
XH
+
(2)
XH
+
k3
P (3)
A. a) Equilibrium approach
k
1
[HA] = k
1
_
H
+
_
A

= k
1
_
H
+

2
_
H
+

=
k
1
2
1
[HA]
1
2
k
1
2
1
k
2
[X]
_
H
+

= k
2
_
XH
+

_
XH
+

=
k
2
[X] [H
+
]
k
2
=
k
1
2
1
k
2
[X] [HA]
1
2
k
1
2
1
k
2
1
rate = k
3
_
XH
+

=
k
1
2
1
k
2
k
3
[X] [HA]
1
2
k
1
2
1
k
2
= k [X] [HA]
1
2
see the right column of the last
page.
B.
4. Let us rst solve for k
50

C
.
k
50

C
= k
25

C
e
Ea
R
(
1
298 K

1
323 K
)
=
ln 2
t 1
2
(25

C)
e
Ea
R
(
1
298 K

1
323 K
)
= 1.06 min
1
As previously derived in III(1)B,
t 1
2
(50

C)
=
ln 2
k
50

C
= 0.652 min
5. Let us rst solve for k. As derived in
III(1)B,
t 1
2
=
ln 2
k
k =
ln 2
t 1
2
= 2.0 10
2
min
1
We can nd the relation between pres-
sure and concentration.
PV = nRT = [A] V RT
P = [A] RT
As derived in III(1)B,
kt = ln [A]
0
ln [A]
t
= ln
[A]
0
[A]
t
= ln
P
A(0)
RT
P
A(t)
RT
= ln
P
A(0)
P
A(t)
e
kt
=
P
A(0)
P
A(t)
P
A(t)
= P
A(0)
e
kt
= 45 mmHg
Using the stoichiometry of the reaction,
we can nd a relation between [A] and
[B], assuming [B]
0
= 0.
[B]
t
= 2 ([A]
0
[A]
t
)
[B]
t
RT = 2 ([A]
0
[A]
t
) RT
P
B(t)
= 2P
A(0)
2P
A(t)
= 2P
A(0)
_
1 e
kt
_
= 1359 mmHg
We can now solve for the total pres-
sure P
total(t)
at t = 140 min, assuming
725 mmHg = P
total(0)
= P
A(0)
.
P
total(t)
= P
A(t)
+P
B(t)
= 1405 mmHg
6. The rst step is the slow step.
NO
2
Cl NO
2
+ Cl (slow)
NO
2
Cl + Cl NO
2
+ Cl
2
(fast)
7. We can derive a linear relationship be-
tween ln k and
1
T
.
k = Ae

Ea
RT
ln k =
E
a
R
_
1
T
_
+ ln A
Applying linear regression using
y = ln k
A = ln A
B =
E
a
R
x =
1
T
We get
B =
E
a
R
= -7029
E
a
= BR = 58.4 kJ
2
8. CF
2
Cl
2
+uv CF
2
Cl +Cl is the chain
initiation step. The rest are chain prop-
agation steps.
9. As derived in III(1)C,
1
[C
2
H
4
]
t
=
kt [C
2
H
4
]
0
+ 1
[C
2
H
4
]
0
[C
2
H
4
]
t
=
[C
2
H
4
]
0
kt [C
2
H
4
]
0
+ 1
[C
2
H
4
]
t
[C
2
H
4
]
0
=
[C
2
H
4
]
0
kt[C
2
H
4
]
0
+1
[C
2
H
4
]
0
=
625
2164
10. As derived in III(1)B,
kt = ln
_
39
Cl

0
ln
_
39
Cl

t
= ln
_
39
Cl

0
[
39
Cl]
t
k =
ln
[
39
Cl]
0
[
39
Cl]
t
t
= 1.26 10
2
min
1
t 1
2
=
ln 2
k
= 55 min
11. 1.
_
28 10
3
Ci
_
_
3.7 10
10 dps
Ci
_
=
1.0 10
9
dps
2. 1.0 10
9
Bq
3.
_
1.0 10
9
dps
_
(95 s) = 9.8
10
10
d. Therefore, we have
9.8 10
10
particles.
1
2
_
8.75 10
14 J

_
_
9.8 10
10

_
65 kg
We solve the above expression to get
6.62 10
5
Gy or 6.62 10
3
4. 1.0
_
6.62 10
3