PSC 480/740

Problem Set 2
Questions Chapter 2, Levenspiel
1.

1
ANSWER KEY

If the reaction is not elementary, one cannot know the order. If the reaction is
elementary, the order is 2nd in either direction.
[ A ]
= k1[ A][B]
dt

d [A ]
= k 1[ R ]2
dt

2.

1 d [ NO 2 ]
d [O 2 ] d [ N 2 O5 ]
= 2
=
2
dt
dt
dt

3.

The same. ( rA =

4.

1760 (s-1)
6 (mol/m3)

5.

1
1
[A ]
1 d [ B] 1 d [ R ]
No, they are not. rA = rB = rR =
=
=
3
2
dt
3 dt
2 dt

6.

3.0 x10-4

7.

a)

atm-1 hr-1

b)

One mole of an ideal gas at 400K occupies 32.82 L atm .

PV
L atm
L atm
400 K = 32.82
= RT = 0.082053
n
K mol
mol

d [A ]
, regardless of how the stoichiometric equation is written.)
dt

L
mol hr

FG
IJ b g
FG IJ
H
K
H K
F 1 IJ 32.82 FG L atmIJ = 120
F L IJ
3.66 G
. 10 G
H atm hr K
H mol K
H mol hr K
2

8.

If 1 >> k2[N2O], then the reaction is second order in N2O, and second order
overall.
If 1 << k2[N2O], then the reaction is first order in N2O, and first order overall.
If 1 k2[N2O], then the order cannot be specified.

PSC 480/740
Problem Set 2
Questions Chapter 2, Levenspiel

ln

9.

FG
H

2
ANSWER KEY

IJ
K

FG
H

k1
= 197
. 103 times faster
k2

10.

2.74 x102 kJ mol-1

11.

E = 45.0 kJ mol-1
6.0

-1

5.8

ln(Running speed)

IJ
K

E 1 1
300 kJ mol 1
1
1
k1
=

K 1 = 7.586
=

3
1
1
R T1 T2
8.314 10 kJK mol 923 773
k2

ln(Running speed) = -5412K + 23.87

5.6

5.4

5.2

5.0

0.00332

0.00336

0.00340

0.00344

0.00348

-1

12.

1.5 times

13.

Growth rate = 1/Growing days.

28.2 kJ mol-1

14.

At 60F (288.6 K), k = 1.333 chirps s-1

At 80F (299.7 K), k = 2.667 chirps s-1
E = 44.9 kJ mol-1

15.

Reaction order = ln3/ln2 = 1.585

16.

Order in A = 1/2. Order in B = 2/3.

17.

Order in A = 1. Order in B = 2/3.

0.00352

PSC 480/740
Problem Set 2
Questions Chapter 2, Levenspiel
18.

3
ANSWER KEY

First, assume second step is rate limiting.

d [O 2 ]
= k 3[ NO *3 ]
dt
Apply steady-state approximation to NO3* and NO*:
d [ NO*3 ]
= 0 = k1[ N 2 O5 ] k 2 [ NO 2 ][NO*3 ] k3[ NO*3 ] k 4 [ NO* ][NO*3 ]
dt
k1[ N 2 O5 ]
[ NO*3 ] =
k 2 [ NO 2 ] + k 3 + k 4 [ NO* ]

d [ NO* ]
= 0 = k 3[ NO*3 ] k 4 [ NO* ][NO*3 ]
dt
k
[ NO* ] = 3
k4
Therefore, [ NO*3 ] =

k1 [ N 2 O 5 ]
k 2 [ NO 2 ] + 2 k 3

Inserting this into the rate equation yields:

d [O 2 ]
k k [N O ]
= 1 3 2 5
dt
k 2 [ NO 2 ] + 2 k 3
But, this yields first-order kinetics only if k2[NO2] << k3, which contradicts the
assumption that step 2 is rate-limiting.
Therefore, assume step 3 is rate-limiting:
d [O 2 ]
k k [N O ]
= k 4 [ NO * ][NO*3 ] = 1 3 2 5
dt
k 2 [ NO 2 ] + 2 k 3
If k2 << k3, then this analysis is consistent with first-order kinetics:
d [ O 2 ] k1[ N 2 O 5 ]
=
dt
2
19.

a)
A+A
A*

k1
k-1
k2

d[ R]
= k 2 [ A*]
dt

A* + A
R+S

PSC 480/740
Problem Set 2
Questions Chapter 2, Levenspiel
But, Keq =
b)

4
ANSWER KEY

d[ R]
k1 [A*]
; therefore
= k 2 Keq [A]
=
dt
k 1 [A]

One could attempt to prove the existence of A*, and better yet, measure its
steady-state concentration.
d [A*]
= 0 = k1[A ]2 k 1[A*][A ] k 2 [A*]
dt
k1[A ]2
[A*] =
Keq [A ]
k 1[A ] + k 2
Or, one could see the effect on rate of a scavenger or trapping agent for the
proposed intermediate, A*.

20.

a)
b)

Overall first order.

O3
O + O3

k1
k-1
k2

O2 + O

fast

2O2

slow

1 d [O 3 ] 1 d [O 2 ]
=
= k 2 [O][O 3 ]
2 dt
3 dt
[O ]
k [O ]
[O] = 1 3 = Keq 3
[O 2 ]
k 1 [ O 2 ]
1 d [O 2 ]
= k 2 Keq [O 3 ]2 [O 2 ]1
3 dt
Rate =

To test the mechanism, one would wish to prove the participation of O

and demonstrate inhibition using common free radical scavengers.
21.
H3PO2 + H
H3PO2* + Ox

k1
k-1
k2

d [ H 3 PO 3 ]
= k 2 [ H 3 PO*2 ][O x ]
dt

H3PO2* + H
H3PO3

PSC 480/740
Problem Set 2
Questions Chapter 2, Levenspiel

5
ANSWER KEY

Application of the steady-state approximation to the active intermediate yields,

k [ H PO ][H ]
[ H 3 PO*2 ] = 1 3 2
k 1 [ H ] + k 2 [ O x ]
and therefore,
d [ H 3 PO 3 ] k1k 2 [ H ][O x ][H 3 PO 2 ]
=
dt
k 1 [ H ] + k 2 [ O x ]
At low [Ox], the right term of the denominator is negligible, and,
d [ H 3 PO 3 ] k1k 2 [O x ][H 3 PO 2 ]
=
dt
k 1
At high [Ox], the left term is negligible, and,
d [ H 3 PO 3 ]
= k1[ H ][H 3 PO 2 ]
dt
22.

With the first step rate limiting, the following mechanism is consistent with the
experimental rate law:
k1
A+B
AB
A + AB

23.

K=

a)

k2

[X]
k1
=
k 2 [A][E]

A2B
and

[ E o ] = [ E ] + [ X]

Combining the two equations above yields, [ X] =

The rate expression is then given by,
k k [A][E o ] k 3[A][E o ]
rA = k 3[ X] = 1 3
=
k2
k 2 + k1 [ A ]
+ [A ]
k1

k1[ A][E o ]
k 2 + k1[A ]

PSC 480/740
Problem Set 2
Questions Chapter 2, Levenspiel
b)

6
ANSWER KEY

In this case, apply steady-state approximation.

d[ X ]
= k1[ A][ E ] k 2 [ X ] k 3[ X ] = 0
dt
Substituting [ E ]o = [ E ] + [ X ] and solving for [X] yields,
k1[A][E o ]
[ X] =
k 2 + k3 + k1[A]

The rate expression is then given by,

k1k 3[A][E o ]
k 3[A][E o ]
rA = k 3[ X] =
=
k 2 + k 3 + k1 [ A ]
k2 + k3
+ [A ]
k1

FG
H

IJ
K

Note that the only difference is that the fast equilibrium approach imposes the restriction
that k2 >> k3; whereas the steady-state approach does not.