Jones-Dole B coefficient

Viscosity of aqueous cesium chloride (CsCl) solution was measured in the range of 0.1-5.0 mol kg-i and 0.1-375 MPa at 25 °C. The Jones-Dole B coefficient of CsCl was obtained from the concentration dependence of the viscosity. It is negative not only at atmospheric pressure but also at high pressure, having a maximum against pressure at about 160 MPa. Similar maximum of the B was observed for aqueous sodium chloride (NaCl) solution. The similarity is discussed in terms of the water structure and dielectric friction theory. 

Figure 2. Pressure dependence of Jones-Dole B coefficients of cesium chloride and sodium chloride in water at 25 °C,...

Feakins D, Waghome WE, Lawrence KG (1986) The viscosity and structure of solutions. Part 1. a new theory of the Jones-Dole B-coefficient and the related activation parameters application to aqueous solutions. J Chem Soc Faraday Trans 82 563-568 Frank HS, Evans MW (1945) Free volume and entropy in condensed systems. III. entropy in binary liquid mixtures partial molal entropy in dilute solutions structure and thermodynamics in aqueous electrolytes. J Chem Phys 13 507-532... 

Table 30.3 Jones-Dole B coefficients at T = 2.3° C (see Equation (30.11)). Source RW Gurney, Ionic Processes in Solution, Dover Publications, New York, 1 962. Data are from C Jones and SK Talley, J Am Chem Soc, 55, 624 (1 933) C Jones and RE Stauffer, J Am Chem Soc, 62, 336 (1 940) and VD Laurence and JH Wolfenden, J Chem Soc, 1144 (1934).

Subsequently the same authors have reported [57] on their experiments with more details, in the same experimental conditions. A correlation was found between (lA7/dC and the Jones-Dole viscosity coefficient B defined by the relation... 

Table I contains the viscosities obtained for the solvent mixtures and the salt solutions. Table II summarizes the results for the solutions and contains the viscosity of each solvent mixture without added salt, the constants A and B of the Jones-Dole equation, the value of the density-concentration coefficient dp/dC, and the density of the solvent mixture.

Here r/0 is the viscosity in salt-free medium and A and B are constants at high salt concentrations, the second term becomes irrelevant. The constant B, which is the second virial coefficient signifying ion-solvent interactions, is termed the Jones-Dole coefficient after the inventors (Jones, 1929). Chaotropes have a coefficient B which is less than zero, whereas kosmotropes are characterized by 1 > 0. 

Gopal and Rastogi84) have determined the temperature and concentration dependence of the viscosities of solutions of a number of salts (mainly tetraalkyl-ammonium iodides) in NMA. They interpreted their results in terms of the Jones-Dole equation203) r = tj0(1 + A [C + BC). The value of B was calculated to be positive for all of the salts examined in NMA. For LiCl and KI the value of B was found to decrease with increasing temperature. A similar trend can be calculated for the temperature dependence of B for KBr and Nal204). On the other hand, the B coefficients for the tetraalkylammonium iodides increased with increasing temperature. 

The viscosity data are shown in Table I. Table II is a summary of results, showing the solvent properties (density and viscosity) and the solution parameters the density-concentration coefficients and the constants A and B of the Jones-Dole Equation. The values of B for the four salts, for which new data are reported, are shown as functions of x2 in Figure 1. (Some data from the literature are included as noted.)... 

However, it should be mentioned that specific ion effects were found even several decades before Hofineister. In 1847, Poiseuille was probably the first who noted that some salts increase the viscosity of water, whereas others decrease it. Jones and Dole in 1929, Cox and Wolfenden in 1934, and several other groups further refined the specific ion effect on water viscosity. From these viscosity smdies and in particular the Jones-Dole viscosity B coefficients, the expressions for water-structure maker and water-structure breaker were finally derived. They were first introduced in 1945 by Frank and Evans, who showed the relationship between viscosity and entropy of dilution. There is a third concept introduced by A. Voet [see also Eckfeldt ] the ordering ofions according to their lyotropic numbers. It nicely correlates with ion effects on the swelling... 

In the review paper by Jenkins and Marcus, a comprehensive collection of viscosity data and B coefficients can be found. Table 1 shows a few of these Jones-Dole coefficients. ... 

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