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CHE 602 Assignment 1

This document contains 4 chemistry problems related to enzyme kinetics, oxidation reactions, hydration reactions, and transition state theory. Problem 1 involves deriving an expression for the rate of a product formation that accounts for competitive inhibition. Problem 2 involves deriving rate laws for the degradation of motor oil both with and without an antioxidant present. Problem 3 involves deriving rate laws for the hydration of isobutene to t-butyl alcohol under different potential rate-limiting steps. Problem 4 involves using transition state theory to estimate a pre-exponential factor and determine a steric factor.

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86 views

CHE 602 Assignment 1

This document contains 4 chemistry problems related to enzyme kinetics, oxidation reactions, hydration reactions, and transition state theory. Problem 1 involves deriving an expression for the rate of a product formation that accounts for competitive inhibition. Problem 2 involves deriving rate laws for the degradation of motor oil both with and without an antioxidant present. Problem 3 involves deriving rate laws for the hydration of isobutene to t-butyl alcohol under different potential rate-limiting steps. Problem 4 involves using transition state theory to estimate a pre-exponential factor and determine a steric factor.

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aliggulam16
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We take content rights seriously. If you suspect this is your content, claim it here.
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CHE 602 – Assignment 1

Due: Monday, January 29 @ 11:59pm


Problem 1:
The simple Michaelis-Menten model does not deal with all aspects of enzyme-catalyzed reactions. The
model must be modified to treat the phenomena of inhibition.

The inhibition process in general may be represented by the following six-step scheme, in which I is the
inhibitor, EI is a binary enzyme-inhibitor complex, and EIS is a ternary enzyme-inhibitor-substrate
complex.

E + S →
k1
ES
k -1

E + I → EI k2
k -2

ES + I →
k3
EIS
k -3

EI + S →
k4
EIS
k -4

ES → E + P
k r1

EIS →
k r2
EI + P

In steps (1) and (2), S and I compete for (sites on) E to form the binary complexes ES and EI. In steps (3)
and (4), the ternary complex EIS is formed from the binary complexes. In steps (5) and (6), ES and EIS
form the product P; if EIS is inactive, step (6) is ignored.

Treatment of the full six-step kinetic scheme above with the PSSH leads to very cumbersome expressions
for [E], [EI], etc., such that it would be better to use a numerical solution. However, these can be greatly
simplified if we assume (1) the first four steps are at equilibrium, and (2) kr1 = kr2. With these
assumptions, show that:

Vmax [S]
rP =
[S] + K M (1 + [I]/K 2 )/(1 + [I]/K 3 )

where K2 = k-2/k2 (dissociation constant for EI)


and K3 = k-3/k3 (dissociation constant for EIS)

Problem 2:
One of the major reasons for engine oil degradation is the oxidation of the motor oil. To retard the
degradation process, most oils contain an antioxidant [see Ind. Eng. Chem. 26, 902 (1987)]. Without an
inhibitor to oxidation present, the suggested mechanism at low temperatures is
𝑘𝑘0
I2 �⎯� 2 I ∙
𝑘𝑘𝑖𝑖
I ∙ +RH �⎯� R ∙ +HI
𝑘𝑘𝑝𝑝1
R ∙ +O2 �⎯⎯� RO2 ∙
𝑘𝑘𝑝𝑝2
RO2 ∙ +RH �⎯⎯� ROOH + R ∙
𝑘𝑘𝑡𝑡
2 RO2 ∙ �⎯� inactive
Where I2 is an initiator and RH is the hydrocarbon in the oil.
When an antioxidant is added to retard degradation at low temperatures, the following additional
termination steps occur:
𝑘𝑘𝐴𝐴1
RO2 ∙ +AH �⎯⎯� ROOH + A ∙
𝑘𝑘𝐴𝐴2
A ∙ + RO2 ∙ �⎯⎯� inactive
(a) Derive a rate law for the degradation of the motor oil in the absence of an antioxidant at low
temperatures
(b) Derive a rate law for the rate of degradation of the motor oil in the presence of an antioxidant for low
temperatures.
(c) How would your answer to part (a) change if the radicals I⋅ were produced at a constant rate in the
engine and then found their way into the oil?

Problem 3:
t-Butyl alcohol (TBA) is an important octane enhancer that is used to replace lead additive in gasoline. t-
Butyl alcohol was produced by the liquid-phase hydration (W) of isobutene (I) over an Amberlyst-15
catalyst. The system is normally a multiphase mixture of hydrocarbon, water and solid catalyst. However,
the use of cosolvents or excess TBA can achieve reasonable miscibility.

The reaction mechanism is believed to be

Adsorption: I + S = I.S
Adsorption: W + S = W.S
Surface reaction: W.S + I.S = TBA.S + S
Desorption: TBA.S = TBA + S

Derive a rate law assuming:


(a) The surface reaction is rate-limiting.
(b) The adsorption of isobutene is limiting
(c) The reaction follows Eley-Rideal kinetics
I.S + W ↔ TBA.S
and that the surface reaction is limiting
(d) Isobutene (I) and water (W) are adsorbed on different sites
I + S1 ↔ I.S1
W + S2 ↔ W.S2
TBA is not on the surface, and the surface reaction is rate-limiting
Problem 4: Determination of Pre-exponential Factor from Transition State Theory
Consider the reaction between the methyl radicals to form ethane at 298 K.

CH 3 + CH 3 
→
k
C2 H 6

The activated complex will be denoted C2H6#. You will assume high vibration frequency for both CH3
and C2H6# (hence, qV = 1). You will also assume no electronic degeneracy.

a) Determine the translational, rotational, vibrational and electronic contributions for both CH3 and
C2H6#. Deduct the molecular partition function.
b) Estimate the pre-exponential factor of the rate constant k from the transition state theory.
c) Comparing the values of the pre-exponential factors obtained from both the transition state theory and
the collision theory, determine the steric factor.

Additional data:

For CH3: A = 9.32 cm-1, B = C = 14 cm-1

σ(symmetry number) = 3

For C2H6#: A = 4.66 cm-1, B = C = 2.80 cm-1

σ(symmetry number) = 18

For the collision theory you will assume a collision cross section, σ = 0.46 nm2

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