Concepts from Chemical Reaction Kinetics - Elements of Environmental Engineering: Thermodynamics and Kinetics - page 263

at pH 7 for different CO 2 (aq) concentration:

[CO 2 ] 0 (mol/dm 3 ) r 0 (mol/dm 3 s)

1.25 × 10 − 3 3 × 10 − 5

2.5 × 10 − 3 5 × 10 − 5

5 × 10 − 3 8 × 10 − 5

2 × 10 − 2 1.5 × 10 − 4

Obtain the Michaelis-Menten parameters for the above reaction.
5.40 3 The atmospheric reaction of chlorine monoxide (ClO) with NO 2 proceeds
as follows:

ClO + NO 2 + M k f k b ClONO 2 + M

with k b = 10 − 6.16 exp ( − 90.7 kJ/mol /RT) inunitsofcm 3 /molecule/s.The
high and low pressure limiting rate constant at 298 K were obtained from
experiments as follows:
k 0 = 1.8 × 10 − 31 cm 6 / molecule 2 / s

∞ = 1.5 × 10 − 11 cm 3 / molecule / s.
Obtain the effective bimolecular rate constant k f at 298 K and 1 atm.
5.41 2 A recent article (Li et al., 2008) showed that apart from the well-
known ozone dissociation that produces OH in the atmosphere, there also
exists another pathway for OH production. This involves the reaction of
electronically excited NO 2 with H 2 O as follows:

k

J 1
−− h ν NO 2 , NO 2

NO 2 + M k 2 −→ NO 2 + M,

NO 2 + H 2 O k 3

−→ OH + HONO,

HONO J 4

−− h ν

OH + NO.

Apply a steady-state approximation to NO 2 to obtain the following
equation:

2 J 1 k 3 [ NO 2 ][ H 2 O ]
k 3 [ H 2 O ]+ k 2 [ M ]

r OH = .

5.42 2 An autocatalysis reaction is one in which the reactant is re-formed as the
reaction proceeds:

k 1
−−→ B, A

k 2
−−→ C + A. B + A

(a) Using the pseudo-steady-state approximation, derive the rate equa-
tion for the formation of the product C.