# PSC 480/740 Problem Set 2 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

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 400°K 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.

00340 0. k = 2.0 5.4 5. Levenspiel 9.667 chirps s-1 E = 44.6 K).314 × 10 kJK mol 923 773 k2 FG H IJ K FG H IJ K k1 = 197 × 103 times faster . 1.00352 K -1 12. 2.333 chirps s-1 At 80°F (299.0 kJ mol-1 6.87 -1 ln(Running speed) 5.00348 0.585 Order in A = 1/2.00344 0.PSC 480/740 Problem Set 2 Questions Chapter 2. 14. Order in B = 2/3.7 K). 28. 17. Order in B = 2/3. 16. 13. 11.5 times Growth rate = 1/Growing days.6 5. k2 10.00336 0.2 kJ mol-1 At 60°F (288. 2 ANSWER KEY ln E 1 1 300 kJ mol −1 1 1 k1 =− − K −1 = 7. Order in A = 1.586 =− − −3 −1 −1 R T1 T2 8.9 kJ mol-1 Reaction order = ln3/ln2 = 1.8 ln(Running speed) = -5412K + 23.2 5. k = 1.74 x102 kJ mol-1 E = 45.00332 0. .0 0. 15.

assume second step is rate limiting. which contradicts the assumption that step 2 is rate-limiting. a) A+A A* k1 k-1 k2 A* + A R+S d[ R] = k 2 [ A*] dt . 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. 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. then this analysis is consistent with first-order kinetics: d [ O 2 ] k1[ N 2 O 5 ] = dt 2 19.PSC 480/740 Problem Set 2 Questions Chapter 2. 3 ANSWER KEY First. [ 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. Levenspiel 18.

and better yet. one would wish to prove the participation of O⋅ and demonstrate inhibition using common free radical scavengers. Levenspiel But.PSC 480/740 Problem Set 2 Questions Chapter 2. 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. 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 . measure its steady-state concentration. A*. a) b) Overall first order. therefore = k 2 Keq [A] = dt k −1 [A] One could attempt to prove the existence of A*. Keq = b) 4 ANSWER KEY d[ R] k1 [A*] . 20. 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 could see the effect on rate of a scavenger or trapping agent for the proposed intermediate. 21.

the left term is negligible. 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]. and. d [ H 3 PO 3 ] k1k 2 [O x ][H 3 PO 2 ] = dt k −1 At high [Ox]. Levenspiel 5 ANSWER KEY Application of the steady-state approximation to the active intermediate yields.PSC 480/740 Problem Set 2 Questions Chapter 2. the right term of the denominator is negligible. With the first step rate limiting. d [ H 3 PO 3 ] = k1[ H ⊕ ][H 3 PO 2 ] dt 22. [ X] = The rate expression is then given by. K= k2 A2B and [ E o ] = [ E ] + [ X] [X] k1 = k 2 [A][E] a) Combining the two equations above yields. the following mechanism is consistent with the experimental rate law: k1 A+B AB A + AB 23. and. 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 ] .

apply steady-state approximation.PSC 480/740 Problem Set 2 Questions Chapter 2. k1[A][E o ] [ X] = k 2 + k3 + k1[A] b g 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 b g 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. Levenspiel b) 6 ANSWER KEY In this case. d[ X ] = k1[ A][ E ] − k 2 [ X ] − k 3[ X ] = 0 dt Substituting [ E ]o = [ E ] + [ X ] and solving for [X] yields.