Level: introductory+ (exercises 1-2), advanced (exercise 3)
Reference: Max Bodenstein, "Gas reactions in chemical kinetics II. Effect of the temperature on the formation and decomposition of hydrogen iodide," Zeitschrift für physikalische Chemie 29, 295-314 (1899).
Notes: Max Bodenstein (1871-1942) was a pioneer in gas-phase kinetics. His experimentation on the hydrogen iodide system was a landmark investigation of careful kinetic and equilibrium measurements over an extended temperature range (more than 200°C). As part of his analysis of these data, Bodenstein expressed the rate constants of decomposition and formation as a function of temperature. (In this respect, exercises 1 and 2 are similar to what Bodenstein did.) He did not fit his data to the Arrhenius equation, however, but a multi-parameter equation
ln k = -a/T + b ln T + cT + constant ,where a, b, and c are constants. (See Keith J. Laidler, "The Development of the Arrhenius Equation," 61, 494-8 (1984) for more on Bodenstein's work and on the temperature dependence of reaction rates.)
Bodenstein also made equilibrium measurements on the HI system, but he did not relate them to kinetic measurements. (Classic calculations includes a set of exercises based on his equilibrium measurements as well.)
Agreement of the standard enthalpy and entropy of reaction from these kinetic data with values derived from NIST tables is not great but not bad. The data Bodenstein published on equilibrium measurements (as opposed to kinetic measurements) agrees much better with handbook data.
Solutions: To download solutions, go to:
http://web.lemoyne.edu/giunta/classicalcs/bodenkin.doc
To download worked spreadsheet, go to:
http://web.lemoyne.edu/giunta/classicalcs/bodenstein.xls
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