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A calorimetric study has been made of proton ionization in dilute aqueous solution from aliphatic carboxylic acids a t 10, 25, and 40" (13 acids) and at 25" (3 acids). Values of A S " are calculated by combining the resulting AH" values with AGO values obtained from the literature or determined from potentiometric o r calorimetric measurements. The trends in AGO, AH", and ASo are described by an electrostatic model, and deviations from this model are taken as a measure of nonelectrostatic substituent effects for carboxylic acids.his study was undertaken as part2 of a program

W(CO)a(NCCH3)3], Mr=391.02, orthorhombic, Pnma, a=9.019 (3), b= 10.6204(17), c =12.3625 (16) A, V=l184.18A 3, Z=4, Dx= 2.193 g cm -3, 2(Mo Ka) = 0.71069 A, g = 99.61 cm -~, F(000)=728, room temperature, final R--0.0207 for 959 independent observed reflections. The structure is octahedral (fac) with effective Car and space-group-imposed C s symmetry. There are no unusual bond distances or angles.

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