PSC 480/740 1

Problem Set 2 ANSWER KEY

Questions Chapter 2, Levenspiel

1. 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

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

d [A ]
3. The same. ( rA = , regardless of how the stoichiometric equation is written.)
dt

4. 1760 (s-1)
6 (mol/m3)

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

L
6. 3.0 x10-4
mol ⋅ hr

7. a) atm-1 hr-1

b) One mole of an ideal gas at 400°K occupies 32.82 L ⋅ atm .

PV FG L ⋅ atm IJ b g FG IJ
L ⋅ atm
n
= RT = 0.082053
HK ⋅ mol K
× 400 K = 32.82
H K
mol

F 1 IJ × 32.82 FG L ⋅ atmIJ = 120

3.66 G
F L IJ
. × 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 2
Problem Set 2 ANSWER KEY
Questions Chapter 2, Levenspiel

k1 E 1 1FG IJ
300 kJ mol −1 1 1
K −1 = 7.586
FG IJ
9. ln
k2
=− −
H
R T1 T2
=−
K −3 −1 −1
−
8.314 × 10 kJK mol 923 773 H K
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) = -5412K + 23.87
ln(Running speed)

5.6

5.4

5.2

5.0

0.00332 0.00336 0.00340 0.00344 0.00348 0.00352

-1
K

12. 1.5 times

13. Growth rate = 1/Growing days.

28.2 kJ mol-1

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

At 80°F (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.

PSC 480/740 3
Problem Set 2 ANSWER KEY
Questions Chapter 2, Levenspiel

18. 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

k1 [ N 2 O 5 ]
Therefore, [ NO*3 ] =
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)
k1
A+A A* + A
k-1

k2
A* R+S

d[ R]
= k 2 [ A*]
dt
PSC 480/740 4
Problem Set 2 ANSWER KEY
Questions Chapter 2, Levenspiel

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

b) 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) Overall first order.

b)
k1
O3 O2 + O fast
k-1
k2
O + O3 2O2 slow

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

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

and demonstrate inhibition using common free radical scavengers.

21.
k1
H3PO2 + H H3PO2* + H
k-1
k2
H3PO2* + Ox H3PO3

d [ H 3 PO 3 ]
= k 2 [ H 3 PO*2 ][O x ]
dt
PSC 480/740 5
Problem Set 2 ANSWER KEY
Questions Chapter 2, Levenspiel

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

k2
A + AB A2B

k1 [X]
23. K= = and [ E o ] = [ E ] + [ X]
k 2 [A][E]

k1[ A][E o ]
a) Combining the two equations above yields, [ X] =
k 2 + k1[A ]

The rate expression is then given by,

k k [A][E o ] k 3[A][E o ]
− rA = k 3[ X] = 1 3 =
k 2 + k1 [ A ] k2
+ [A ]
k1
PSC 480/740 6
Problem Set 2 ANSWER KEY
Questions Chapter 2, Levenspiel

b) 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] =
b g
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] = =
b g
k 2 + k 3 + k1 [ A ]FG k2 + k3IJ+ [A ]
H k1 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.