Jones-Dole

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].

The viscosities of the acetone-bromosuccinic acid mixed solvents were derived from the Jones-Dole (33) equation and data acquired by Muller, who used the special viscometer described by Tuan and Fuoss (34). The values used for the viscosities (in poise) of solvents I-V were 3.02 X 10 3, 3.05 X 10-3, 3.08 X 10-3, 3.13 X 10-3, and 3.02 X 10-3, respectively. The literature value for the dielectric constant of acetone, 20.7, was used as the dielectric constant for each solvent. This is justified because at the highest concentration of bromosuccinic acid its mole fraction is less than 0.004. 

Viscosity data for fairly dilute salt solutions are usually discussed in terms of the Jones-Dole equation (3)... 

Fitting the Jones-Dole equation to the data was not done in the usual manner in the linearized form (17/170 — 1 )/C1 2 = A + BC1/2, since this casts a heavy burden on the required precision of 170 and also inflates the errors at the lower-concentration end. Instead, we used the form ... 

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.

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 calculation of viscosities of electrolyte mixtures can be accomplished with the method of Andrade (see Ref. [40]) extended with the electrolyte correction by Jones-Dole [44]. First, the pure component viscosities of molecular species are determined by the three-parametric Andrade equation, which allows a mixing rule to be applied and the mixture viscosity of an electrolyte-free liquid phase to be obtained. The latter is transformed into the viscosity of the liquid phase using the electrolyte correction term of Jones and Dole [44], whereas the ionic mobility and conductivity are used as model parameters. 

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. 

As before, the Jones-Dole Equation (12) was fitted to the data by a least squares procedure, in the form... 

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... 

Jones-Dole viscosity equation, 124 Jones-Partington supersaturation equation, 372... 

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. 

Concentration dependence of the viscosity of electrolyte solution has been empirically expressed by the Jones-Dole equation (eq.(l)),where r/ and rjo are the viscosities of solution 77/rjo = 1+aVc+Be (1)... 

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. 

Generally, the additives change the structure of water and thus the free energy of the interaction between polymer and water. The additives influence the solution viscosity and are classified into structure making (cosmotropes) and structure breaking (chaotropes). The viscosity r] of an aqueous solution (up to about 0.1 M), relative to the viscosity rjo of water at the same temperature, varies with the additive concentration according to the Jones-Dole expression... 

Another transport property sensitive to solvent structural eflFects is the viscosity B coeflBcient obtained from the Jones-Dole equation (23),... 

The viscosity of aqueous solutions has been studied extensively some of the more pertinent data, including that for a few non-aqueous solutions, are discussed by Harned and Owen. In most cases the data can be adequately represented by the Jones-Dole equation ... 

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... 

The fluidity of a liquid, its rate of flow under a pressure gradient, is the reciprocal of its viscosity. The dynamic viscosity of water, jjw, although rather small compared with that of other liquids, is caused by the extensive network of hydrogen bonds existing in it that must be partly broken for the water to flow (Jenkins and Marcus 1995 Marcus 2009a). Ions affect the dynamic viscosity of the solution, n], some electrolytes enhancing it whereas others diminishing it. The effect is described up to fairly concentrated solutions by the Jones-Dole expression (Jones and Dole 1929) ... 

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