52nd International Chemistry Olympiad, Istanbul, TURKEY Preparatory problems: THEORETICAL

Problem 23. Reaction Kinetics with Absorbance Measurement

It is often experimentally convenient to use an analytical method that provides an instrumental

signal that is proportional to concentration, rather than providing an absolute concentration.
Absorbance, fluorescence intensity, and conductance are examples of this type of instrument
response. The requirements are that the reactants and products both give a signal that is directly
proportional to their concentrations and there is an experimentally usable change in the observed
property as the reactants are transformed into the products. In this experiment, absorption
spectroscopy and Beer’s law can be used.

A is the reactant and B is the only product (A → B) and both give an absorbance at selected
wavelength that is directly proportional to their concentrations. In this experiment, ƐA≠ƐB, where
Ɛ is the molar absorptivity.

For the hydrolysis of A to B in aqueous solution, the absorbance-time data are given in the Table
below. The experimental conditions: pH of the medium is 7.0 and temperature is 25 °C. The
initial A concentration is 4.0 × 10–6 M and measurements are recorded at 400 nm in a 5-cm cell.

t/s At
0 0.0840
20 0.1090
60 0.1515
120 0.2010
160 0.2255
200 0.2440
∞ 0.3170

23.1. Calculate the molar absorptivities of A and B under these conditions.

23.2. Find the rate constant.

23.3. Find the half-life (t1/2).

23.4. After how many seconds [A] is equal to 1.0 × 10–6 M?

23.5. If k is equal to 0.01029 s–1 at 30 °C, calculate Ea.

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52nd International Chemistry Olympiad, Istanbul, TURKEY Preparatory problems: THEORETICAL

23.6. Assuming that the transition state rate constant is equal to one obtained from the
experimental data, calculate activation free energy.

𝑘𝐵 𝑇 −∆𝐺‡ /𝑅𝑇
𝑘𝑇𝑆𝑇 = 𝑒
ℎ

where is the Boltzmann constant, is Planck’s constant, and R is the universal gas constant.

The condensation reaction of acid catalyzed ethylene glycol and terephthalic acid is monitored
as a function of extent of the reaction (p: ratio of condensed [A] to [A]0) and the reaction obeys
second-order kinetics. The concentration of each monomer is equal to each other and it is
[A]0=4.8 mol dm–3.

Time (h) Extent of Reaction

0 0
0.5 0.636
1.5 0.839
2.5 0.897

23.7. Find the rate constant.

23.8. Find the half-life of the reaction.

23.9. What will the monomer concentration be after one hour?

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