The cosolvent effect on the transport parameters of HCl in aqueous plus organic solvent mixtures

被引:5
作者
Falciola, L [1 ]
Greggio, P [1 ]
Mussini, PR [1 ]
Mussini, T [1 ]
机构
[1] Univ Milan, Dept Phys Chem & Electrochem, I-20133 Milan, Italy
关键词
D O I
10.1021/je034244l
中图分类号
O414.1 [热力学];
学科分类号
摘要
The electromotive forces EA of concentration cells with transference Ag\AgCl\HCl(m(2,var)), (S + H2O)\\HCl(M-1,M-fixed), (S + H2O)\AgCl\Ag, where m(1,fixed) and M-2,M-var denote electrolyte molalities (fixed and variable, respectively), have been measured at T = 298.15 K in a wide range of aqueous organic solvents (S + H2O) with both protic (methanol, ethanol, propanol, ethylene glycol, and glycerol) and aprotic cosolvents (propylene carbonate, acetonitrile, and 1,4-dioxane) of low to high permittivities, allowing the determination of infinite dilution ionic transference numbers for HCl in such solvents. Appropriate combination of the latter with limiting molar conductivity data, determined in the same media, yielded the limiting ionic mobilities. The results provide an insight on the effect of the organic cosolvents on relative and absolute transport properties of HCl. They are compared with results obtained by our group for "viscous-motion" alkali halides MeCl, discussed in terms of dielectric friction parameters. For the limiting case of pure water, the abundant transference cell data available up to very high HCl concentrations have now been reassessed along our recently improved interpretative scheme.
引用
收藏
页码:1565 / 1573
页数:9
相关论文
共 56 条
[1]   Ionic mobility and ultrafast solvation: Control of a slow phenomenon by fast dynamics [J].
Bagchi, B ;
Biswas, R .
ACCOUNTS OF CHEMICAL RESEARCH, 1998, 31 (04) :181-187
[3]   Transference numbers of alkali chlorides and characterization of salt bridges for use in methanol plus water mixed solvents [J].
Basili, A ;
Mussini, PR ;
Mussini, T ;
Rondinini, S ;
Sala, B ;
Vertova, A .
JOURNAL OF CHEMICAL AND ENGINEERING DATA, 1999, 44 (05) :1002-1008
[4]   Limiting ionic conductance of symmetrical, rigid ions in aqueous solutions: Temperature dependence and solvent isotope effects [J].
Biswas, R ;
Bagchi, B .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (25) :5946-5953
[5]   ANOMALOUS ION DIFFUSION IN DENSE DIPOLAR LIQUIDS [J].
BISWAS, R ;
ROY, S ;
BAGCHI, B .
PHYSICAL REVIEW LETTERS, 1995, 75 (06) :1098-1101
[6]   Ionic mobility in alcohols: From dielectric friction to the solvent-berg model [J].
Biswas, R ;
Bagchi, B .
JOURNAL OF CHEMICAL PHYSICS, 1997, 106 (13) :5587-5598
[7]   The mobility of electrolyte ions [J].
Born, M .
ZEITSCHRIFT FUR PHYSIK, 1920, 1 :221-249
[9]   Transference numbers of NaCl in aqueous mixtures with organic solvents of moderate to low permittivities [J].
Ceccattini, PD ;
Mussini, PR ;
Mussini, T .
JOURNAL OF SOLUTION CHEMISTRY, 1998, 27 (01) :1-16
[10]   STANDARD POTENTIALS OF SILVER-SILVER CHLORIDE ELECTRODES IN AQUEOUS NORMAL-PROPANOL MIXTURES AT 25-DEGREES-C [J].
CLAUSSEN, BH ;
FRENCH, CM .
TRANSACTIONS OF THE FARADAY SOCIETY, 1955, 51 (05) :708-712