Jones—Dole coefficient

Table II. Solvent Viscosity, Jones—Dole Coefficients, and Dependence of Density on Salt Concentration at the Various Solvent Compositions...

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. 

The terms structure making and structure breaking are attributed to Gurney (1953), but Cox and Wolfenden (1934) were the first to mention the notion of water structure in the connection of the viscosities. Furthermore, Frank and Evans (1945) have already used the term structure breaking (but not -making ) with regard to effects of the alkali metal and halide ions, except Li+ and F , on the partial molar entropies of dilute aqueous solutions. The Jones-Dole -coefficient, Eq. (2.35), is the quantitative measure of this effect, and this equation may be recast in the form ... 

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. ... 

These results were then correlated to the Jones-Dole coefficient to investigate the dependence of enzyme activation on the kosmotropicity of the salt in a solvent such as hexane. Specifically, plotting enzyme activity as a function of the difference in J DB coefficients of the cations and anions of the salts, resulted in a clear trend towards increased enzyme activity when the difference between the kosmotropicity of the anion and the chaotropicity of the cation was increased (Figure 3.10) [46]. These results were consistent with those of Ru et al. [33], in that enzyme activity in salt-activated preparations in hexane positively correlates with increased kosmotropicity on the anion. As a result of the elucidation of the influence of the kosmotropic/chaotropic properties of salts on enzyme function, the role of water... 

Figure 3.10 Correlation between the observed reactivity of penicillin amidase formulations and the difference in the Jones-Dole coefficients of the kosmotropic anion and the chaotropic cation for single salt and binary salt mixtures [46].

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.

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.)... 

Jones-Dole equation, coefficients (viscosity of electrolytes) 1.5.52, table 1.5.9, I.6.78ff... 

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,...

Zi is the charge on species i, coefficient A depends on various solute and solvent properties, and the coefficients are specific to the individual ions. Parameters for the Jones-Dole equation at room temperature are tabulated by Marcus [79]. A semiempirical extension of the Jones-Dole equation to higher concentrations, and also a method for extrapolating room-temperature parameters to higher temperatures, are described by Lencka et al. [80]. Jiang and Sandler [81] have developed a different method, based on liquid-state theory, that also appears promising for correlation and limited prediction of electrolyte solution viscosities. 

Vosburgh and co-workers have reported for LiCl in some aliphatic alcohols up to butanol and Sobkowski and Mine have reported the same quantity for HCl in alcohols up to w-propanol. For both electrolytes increases as the number of carbons increase in the alcohol. Venkatasetty and Brown have measured the viscosities of Lil, NH4I and BU4NI in butanol at 0, 25 and 50°C and attempted to fit the data to the Jones-Dole equation. " Although measurements were made in relatively dilute solutions, deviations from linearity were observed over the concentration range studied and viscosity coefficients were not evaluated. 

Feakins and Lawrence measured the relative viscosities of sodium and potassium chlorides and bromides in NMF from 25 to 45°C and expressed the data by an expanded Jones-Dole equation. The viscosity coefficients, A, and were evaluated. While both and have positive values for every electrolyte studied in NMF, they are much smaller than the corresponding quantities in other organic solvents. The difference between the theoretical and experimental values of may be either positive or negative. 

Schmidt and co-workers ° have also measured apparent molal volumes and viscosities of several electrolytes in anhydrous ethylenediamine at 25°C and extrapolated the data to obtain F . They observed that Masson s equation (eqn 2.3.66) was valid over the concentration range studied and their data indicate that S is negative in this solvent. A theoretical value for the limiting slope, is not available. The viscosity data are in agreement with the Jones-Dole equation over the concentration range studied, but the coefficients of this equation were not reported. 

Archer and Gasser have measured the viscosity of DMSO-CsI solutions up to about 0.7 molar and employed the extended Jones-Dole equation to fit the data. The viscosities were not sufficiently accurate to evaluate consequently, this term was calculated theoretically and the Bn and coefficients evaluated by plotting — AnC -lljC... 

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... 

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 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).

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... 

Empirical Coefficients for the Modified Jones-Dole Equation (Equation 10.5) for 2(504)3 Solutions at Different Acid Concentrations and Temperatures... 

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