A microcalorimeter for measuring heat effects of electrochemical reactions with submonolayer conversions.

We present a microcalorimeter for measuring heat effects during electrochemical reactions with conversions down to a few percent of a monolayer, referenced to the electrode's surface atoms. The design uses a thin pyroelectric polymer foil for temperature measurement at the backside of a thin electrode, similar to the concepts pioneered by the groups of D. A. King and Ch. T. Campbell for UHV adsorption microcalorimetry. To establish intimate thermal contact between electrode and sensor and utmost sensitivity, the free standing sensor and electrode foils are pressed together by air pressure, acting on the electrochemical cell. Pyroelectric temperature sensing is combined with pulsed electrochemistry, where the electrochemical heat is released on a time scale of about 10 ms, which is long enough for thermal equalization of the electrode-sensor assembly but short enough to avoid significant heat loss into electrolyte and cell compartment. As examples heat effects upon Ag deposition and dissolution as well as the electron transfer reaction of [Fe(CN)(6)](4-)/[Fe(CN)(6)](3-) are presented. The latter reaction was also employed for the calibration of the calorimeter.