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. 4.

The same. ( rA = 1760 (s-1) 6 (mol/m3)

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

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. 7.

3.0 x10-4 a) b)

L mol hr

atm-1 hr-1 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

FG IJ b g FG IJ H K H K F 1 IJ 32.82 FG L atmIJ = 120 10 FG L IJ 3.66 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 9.

2 ANSWER KEY

ln

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

FG H

IJ K

FG H

IJ K

k1 = 197 103 times faster . k2

10. 11.

2.74 x102 kJ mol-1 E = 45.0 kJ mol-1

6.0

5.8

ln(Running speed) = -5412K + 23.87

-1

ln(Running speed)

5.6

5.4

5.2

5.0

0.00332

0.00336

0.00340

0.00344

0.00348

0.00352

-1

12. 13. 14.

1.5 times Growth rate = 1/Growing days. 28.2 kJ mol-1 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 Reaction order = ln3/ln2 = 1.585 Order in A = 1/2. Order in B = 2/3. Order in A = 1. Order in B = 2/3.

15. 16. 17.

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* ] k3[ NO* ] k 4 [ NO* ][NO* ] 3 3 3 dt k1[ N 2 O5 ] [ NO* ] = 3 k 2 [ NO 2 ] + k 3 + k 4 [ NO* ]

d [ NO* ] = 0 = k 3[ NO* ] k 4 [ NO* ][NO* ] 3 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* ] = 1 3 2 5 3 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 A* + A R+S

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

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 2O2 fast 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 H3PO2* + H H3PO3

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

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* ] = 1 3 2 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=

k2

A2B and
[ E o ] = [ E ] + [ X]

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

a)

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.