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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
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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.
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