Nov.

23, 2021 CML101 Tutorial #2

1. Consider the reaction mechanism

k1
−−
A+B )−*
− C −−→ P
k −1

Write the expression for d[P]/ dt, the rate of product formation. Assume equilib-
rium is established in the first reaction before any appreciable amount of product
is formed, and show that d[P]/ dt = k2 K [A][B], where K is the equilibrium
constant for the first step.

2. The decomposition of ozone 2 O3 −−→ 3 O2 (g) occurs by the reaction mechanism

k1
−−
M ( g ) + O3 ( g ) )−*− O2 ( g ) + O ( g ) + M ( g )
k −1

k
O(g) + O3 (g) −−2→ 2 O2 (g)
where M is a molecule that can exchange energy with the reacting ozone molecule
through a collision, but does not react. Use this mechanism to derive the
rate law for d[O3 ]/ dt assuming that O(g) can be treated by a steady state
approximation(SSA). (Ans: -1/2d[O3]/dt = k1 k2 [O3 ]2 [M]/(k−1 [O2 ][M] + k2 [O3 ])

3. Explain why in the previous problem either (a) v−1  v2 and v−1  v1 or (b)
v2  v−1 and v2  v1 must be true for the SSA to apply. The rate law for the
decomposition reaction is found to be d[O3 ]/ dt = −k [O3 ][M]. Is this rate law
consistent with the conditions given by either (a) or (b) or both? (Ans: (b))

4. The rate law for the hydrolysis of ethyl acetate by aqueous sodium hydroxide at
298 K is kobs [OH− ][CH3 COOC2 H5 ]. The mechanism for the reaction is

1 k
CH3 COOC2 H5 + OH− )
−−
−*− CH3 CO− (OH)OC2 H5
k −1

k
CH3 CO− (OH)OC2 H5 −−2→ CH3 COOH + CH3 CH2 O−
k_3
CH3COOH + C2H5O– CH3COO– + C2H5OH
Write the rates of formation of all the intermediate species? Under what con-
ditions does this mechanism give the observed rate law? For these conditions,
express kobs in terms of the individual steps of the reaction mechanism. (Ans:
fast equilibrium for step 1; kk2 k1 )
−1

5. For a reaction A P, can a single-step and two-step mechanism be distin-

guished when the second step of the two-step scheme is rate determining?

6. A proposed mechanism for the reaction of nitramide in water is

−−
O2 NNH2 )−− O2 NNH− + H+
*

O2 NNH− −−→ N2 O + OH−

H+ + OH− −−→ H2 O
Nov. 23, 2021 CML101 Tutorial #2

k [O NNH ]
The experimentally observed rate law for the reaction is obs [ H2 + ] 2 . (a) What is
the overall reaction? (b) What are the units of kobs ? (c) Under what conditions is
this mechanism consistent with the rate law? (d) Express kobs in terms of the rate
constants of the elementary reactions. (e) With this mechanism as an example
explain the concept of rate determining step.
7. The chlorination of an organic molecule (M) to give P may proceed by the
following mechanism: (i) Cl2 2 Cl (ii) Cl + M R (iii) R + Cl2 P + Cl
(iv) Cl + Cl Cl2. (a) Setup the rate expressions for intermediates. (b) Apply
the steady state approximation to the intermediate species and obtain the rate
law.
8. A reaction A + B + C D follows the mechanism (i) A + B AB (ii) AB +
C D, in which the first step remains essentially in equilibrium. (a) Derive the
expected rate law and express kobs in terms of the rate constant of the elementary
reactions. (b) If ∆H and Ea are the enthalpy change for the first step and the
activation energy of the second step respectively, show that the dependence of
kobs on temperature is given by kobs = Ae−(Ea +∆H )/RT .
9. The mechanism for the nitrogen pentoxide catalyzed decomposition of ozone
is given below. Derive a rate law for the reaction by using the steady state
approximation.
k
N2 O5 −−1→ NO2 + NO3
k
NO2 + NO3 −−2→ N2 O5
k3
NO2 + O3 −−→ NO3 + O2
k
NO3 + NO3 −−4→ 2 NO2 + O2
10. One suggested mechanism for the reaction
S2 O82− + 3 I− −−→ 2 SO42− + I3−
is:
S2 O82− + I− −
)−
−− SO4 I− + SO42−
* (rapid)
k
I− + SO4 I− −−1→ I2 + SO42− (slow)
k
I− + I2 −−2→ I3− (fast)
while another is:
k
S2 O82− + I− −−1→ S2 O8 I3− (slow)
k
S2 O8 I3− −−2→ I+ + 2 SO42− (fast)
k3
I− + I+ −−→ I2 (fast)
k
I− + I2 −−4→ I3− (fast)
The reaction is first order both with respect to the persulfate and iodide ions.
(i) Derive the rate laws for these two mechanisms (ii) Discuss whether one
can differentiate if the reaction proceeds according to either or both of these
mechanisms.
Nov. 23, 2021 CML101 Tutorial #2

11. The Monsanto Company acetic acid process employs a rhodium based homo-
geneous liquid-phase catalyst which promotes methanol carbonylation in high
selectivity and at low pressures. The carbonylation catalyst is comprised of two
components, a soluble rhodium complex and an iodide promoter, usually HI
or CH3I. The catalytic species is believed to consist of a coordination complex
of rhodium with carbon monoxide and halogen ligands. The overall stoichiom-
etry of the acetic acid synthesis is represented simply by CH3OH + CO
CH3COOH. What is the expected rate law if the proposed mechanism is:

CH3OH + HI CH3I + H2O fast

[Rh(CO)2I2]– + CH3I [Rh(CO)2(CH3)I3]– slow

[Rh(CO)2(CH3)I3]– [Rh(CO)(COCH3)I3]– fast
[Rh(CO)(COCH3)I3]– + CO [Rh(CO)2(COCH3)I3]– fast
[Rh(CO)(COCH3)I3]– [Rh(CO)2I2]– + CH3COI fast
CH3COI + H2O CHCOOH + HI fast