This paper describes the construction and testing of a high-pressure joule-heating temperaturejump apparatus for the study of fast reactions in solution at pressures up to 2 kbar. Important features are: a liquid pressurizing medium; a Teflon membrane pressure transmitting device; a constant, pressure independent, electrode distance. The Co(II)-PADA reaction was used to test the system, and the results are in good agreement with earlier reported data.

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The effect of pressure on the reaction between Fe(III) and NCS− ions was reinvestigated using a recently constructed high‐pressure Joule‐heating temperature‐jump instrument. The results differ significantly from those reported by Jost [1], and the volumes of activation for the reactions of Fe(OH2)63+ and Fe(OH2)5OH2+ with NCS− are 6.7 ± 0.4 and ∼0 cm3 mol−1, respectively, at 20°C. The pressure dependences of the Fe(OH2)33+/Fe(OH2)5OH2+ and Fe(OH2)63+, NCS−/Fe(OH2)5NCS2+ equilibria are in good agreement with earlier findings. The significance of the results are discussed in reference to recent data on the solvent exchange and substitution reactions of Fe(III).

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