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The partial molar volume of the proton in water determined by laser-induced optoacoustic studies

✍ Scribed by Claudio D. Borsarelli; Silvia E. Braslavsky

Publisher
Elsevier Science
Year
1998
Tongue
English
Weight
675 KB
Volume
43
Category
Article
ISSN
1011-1344

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✦ Synopsis

The structural volume change associated with the formation and decay of the metal-to-ligand charge-transfer (MLCT) state of (2,2'bipyridine) tetracyanoruthenate(II) complex, Ru(bpy)(CN)42 , AVMLcr, has been studied as a function of pH in dilute aqueous solutions ( < 0.4 M) using time-resolved laser-induced optoacoustic spectroscopy. The values of AVMLcT for the MLCT formation of the complex strongly depend on pH, ranging from + 3.0 + 0.3 cm3/mol at pH = 0.35 to + 15.0 + 0.5 cm3/mol at pH = 6.63. The reduction of A VMLcT at low pH values is assigned to the fast excited-state proton ejection undergone by monoprotonated Ru (bpy) (CN)42-. With the A VMLC-r values and the Drude-Nemst equation for the electrostriction effect with an empirically determined constant, a value for the 'absolute' partial molar volume of the hydrated proton in water of V°,. = ( -5.5 + 0.8) cm3/mol is obtained, in good agreement with literature data.

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