CML 522 Chemical Dynamics & Surface Chemistry II sem, 2020-21

Assignment 2
Due Date: 7 Mar 2021

1. The second order rate constant for the alkaline hydrolysis of ethyl formate in 85% ethanol (aqueous) at
29.86 °C is 4.53 L mol–1 s–1.
(a) If the reactants are both present at 0.001 mol L–1, what will be the half-life of the reaction?
(b) If the concentration of one of the reactants is doubled and of the other is cut in half, how long will it
take for half the reactant present at the lower concentration to react?
[𝐴] 𝑌 −𝑌
2. The extent of reaction is given by 𝐸 = 1 − [𝐴] 𝑡 = 𝑌 0−𝑌 𝑡 . showed a plot of 𝑡/𝐸 versus time based on the
0 0 ∞

𝑡 1 𝑛
expression ≈ + 𝑡 can be used to determine the reaction order 𝑛 in the equation 𝑣 = 𝑘[𝐴]𝑛 .
𝐸 𝑘[𝐴]𝑛−1
0 2

Show that the expression is exact for zeroth and second order reaction and derive that it is an
approximation for first order reactions.
3. Kinetic data (dilatometer reading) for the decomposition of diacetone alcohol
[(CH3 )2 C(OH)CH2 C(O)CH3 → 2(CH3 )2 CO] is given in the table
Time/s 0 1800 3900 9300 13500 15900 18900 25200 27000 29100 34500 38700
𝑉𝑡 /ml 83.46 79.66 75.60 66.42 60.38 57.25 53.58 46.94 45.26 43.42 39.25 36.50

Plot 𝑉𝑡 as a function of time and fit the data to determine the order of the reaction. Preferably use origin
to carry out the least-squared-error-fit. Do the same using the Guggenheim method and the Kezdy-
Swinbourne approach.
4. The reaction 2A + B → P + Q was studied with [A]0 = 2[B]0. A plot of [A]−1
t versus time was

linear. What rate equations does this result suggest? What experiments could be designed to distinguish
among them?
5. Opposing reactions: Consider the kinetics of the N02 – catalyzed isomerization of olefins. Derive the
expression shown for 𝑘𝑐𝑖𝑠 , where 𝐾𝑇𝐶 = 𝑘𝑡𝑟𝑎𝑛𝑠 /𝑘𝑐𝑖𝑠 , in experiments starting only with cis-olefin.
𝑘𝑡𝑟𝑎𝑛𝑠
𝑡𝑟𝑎𝑛𝑠 − olefin + NO2 ⇄ NO2 + 𝑐𝑖𝑠 − olefin
𝑘𝑐𝑖𝑠
1 [T]t
𝑘𝑐𝑖𝑠 𝑡 = − ln{1 − (1 + 𝐾𝑇𝐶 ) }
(1 + 𝐾𝑇𝐶 )[NO2 ] [C]0 + [T]0
6. Parallel reactions: Consider a substance A that forms a mixture of P1 and P2 in parallel reactions, with
𝑘1 = 1.40 × 10−3 s−1 and 𝑘2 = 8.7 × 10−3 s−1. In an experiment with [A]0 = 3.7 × 10−4 M,

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CML 522 Chemical Dynamics & Surface Chemistry II sem, 2020-21
calculate the three concentrations at 𝑡 = 80 𝑠; at the time at which [A] = [P1]; and at the time at which
half the final amount of P2 is formed. When do the latter two events occur?
7. Steady-state kinetics: Consider the interchange of O2 and CO coordinated to myoglobin, an iron
porphyrin represented as PFe:
𝑘1 𝑘2
PFe(O2 ) ⇄ PFe + O2 ; PFe + CO → PFe(CO)
𝑘−1
Making the steady—state approximation for [PFe], derive the rate law. Next, repeat the derivation
including the reverse step with 𝑘−2. If [CO] and [02] are >> [PFe(O2)]0, what is the expression for the
rate?
8. An autocatalytic reaction is one where one of the products catalyses the reaction. Derive an integrated
rate law for the autocatalytic reaction A → P given that – d[A]/ dt = 𝑘[A][P] and initial [A] = 𝑎, [P] =
𝑝.
9. Steady-state approximation: One pathway for the net reaction FeIII + VIII → FeII + VIV is believed to be
the autocatalytic scheme:
𝑘1
III
Fe + V ⇄ FeII + V V
IV

𝑘−1
𝑘2
V V + V III → 2V IV
Derive the steady—state rate law. To what form does this reduce if 𝑘−1 [FeII ] ≫ 𝑘2 [V III ]?
10. 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
𝑘1
CH3 COOC2 H5 + OH ⇄ CH3 CO− (OH)OC2 H5
−

𝑘−1
𝑘2
CH3 CO− (OH)OC2 H5 → CH3 COOH + CH3 CH2 O−
𝑘3
CH3 COOH + C2 H5 O− → CH3 COO− + C2 H5 OH
Write the rates of formation of all the intermediate species? Under what conditions does this mechanism
give the observed rate law? For these conditions, express 𝑘𝑜𝑏𝑠 in terms of the individual steps of the
reaction mechanism.

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CML 522 Chemical Dynamics & Surface Chemistry II sem, 2020-21

11. One suggested mechanism for the reaction

S2 O2− − 2− −
8 + 3I → 2SO4 + I3

is:
S2 O2− − − 2−
8 + I ⇌ SO4 I + SO4 (rapid)
I− + SO4 I − → I2 + SO2−
4 (slow)
I− + I2 → I3− (fast)
while another is;
S2 O2− −
8 + I → SO8 I
3−
(slow)
SO8 I3− → I + + 2SO2−
4 (fast)
I− + I + → I2 (fast)
I− + I2 → 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.

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