David King and his group developed the first calorimeter that could measure heats of adsorption on the well-defined surfaces of single crystals with sufficient precision to reveal new understanding of surface chemistry. Since then, other groups including our own have adopted this technique and made substantial extensions, including: (1) detector improvements that allow routine measurements from 100 to 350 K with high precision (a standard deviation of 1.3 kJ/mol with gas pulses that contain only 1% of a monolayer), (2) metal adsorption and adhesion energies during thin film growth, (3) energetics of metal nanoparticles versus size, (4) measurements of electrochemical adsorption and reactions at liquid/solid interfaces, (5) measurements of protein adsorption, and (6) transient measurements of heat signal lineshapes during two-step reaction mechanisms (e.g., molecular adsorption followed by dissociation) that give the heats for both steps and the rate constant for the second step during every gas pulse. These extensions and their applications will be reviewed to assess the current state of adsorption calorimetry on well-defined surfaces, and its future prospects.Work supported by NSF grant #CHE-1010287.

David King's legacy of adsorption calorimetry on well-defined surfaces:  Where it has taken us

248th National Meeting (2014)

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