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You are on page 1of 3

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

b) Steady-state approach. Please

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

rad.

4. 1.0

_

6.62 10

3

rad

_

= 6.62 mrem

1.0

_

6.62 10

5

Gy

_

= 6.62

10

5

Sv

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