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Ionization of five aqueous fluorobenzoic acids: Conductance and thermodynamics

 

作者: LaurenceE.Strong,   CarterVanWaes,   KennethH.DoolittleII,  

 

期刊: Journal of Solution Chemistry  (Springer Available online 2004)
卷期: Volume 11, issue 4  

页码: 237-258

 

ISSN:0095-9782

 

年代: 2004

 

DOI:10.1007/BF00657316

 

出版商: Springer_US-Boston

 

数据来源: Springer

 

摘要:

The three monofluorobenzoic acids together with 2,4-difluoro and 2,6-difluorobenzoic acids in aqueous solution are the subject of precision conductance measurements. The experimental data are analyzed to give ionization constants and limiting conductances at temperatures from 0 to 100°C. Walden products for the acid anions are derived from the limiting conductances while the ionization consatants are fitted by statistical methods to the function pKa(m)=A+B/T+ C logT+DT. Only the 2,6- acid requires the fourth term of the function to fit the data to a precision of better than 0.03%. Mathematical analysis of the pK function gives the standard changes in enthalpy, entropy, and heat capacity. All the acids studied are more acidic than the parent, benzoic acid, as well as more acidic than the isoelectronic methylbenzoic acids. In general the increased acidity is tied to decreases in enthalpy while entropy changes on ionization differn little from those found for the parent acid

 

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