Association methanol-water mixtures

Using the average value for the equilibrium constant, the distribution concentration of the different components of a methanol water mixture were calculated for initial methanol concentrations ranging from zero to 100%v/v. The curves they obtained are shown in Figure 28. The molar refractivities of 11.88 is also in accordance with that expected since the molar refractivity s of water and methanol are 3.72 and 8.28 respectively. The refractive index of the associate of 1.3502 is, as would be expected, higher than that of either water or methanol. 

Considering the hexadecane/water-methanol system the same arguments and treatment can be afforded to the methanol/water mixture on the assumption that it is a ternary mixture containing methanol, water and methanol associated with water. Thus, the equation used for the system of Katz et al. reduces to... 

Atkinson, G. Kor, S. K. (1965). The kinetics of ion association in manganese sulphate solutions. I. Results in water, dioxane-water mixtures, and methanol-water mixtures at 25 °C. Journal of Physical Chemistry, 69, 128-33. 

K. Ando and S. Kato, Dielectric relaxation dynamics of water and methanol solutions associated with the ionization of /V,/V-dimcltiylanilinc theoretical analyses, J. Chem. Phys., 95 (1991) 5966-82 D. K. Phelps, M. J. Weaver and B. M. Ladanyi, Solvent dynamic effects in electron transfer molecular dynamics simulations of reactions in methanol, Chem. Phys., 176 (1993) 575-88 M. S. Skaf and B. M. Ladanyi, Molecular dynamics simulation of solvation dynamics in methanol-water mixtures, J. Phys. Chem., 100 (1996) 18258-68 D. Aheme, V. Tran and B. J. Schwartz, Nonlinear, nonpolar solvation dynamics in water the roles of elec-trostriction and solvent translation in the breakdown of linear response, J. Phys. Chem. B, 104 (2000) 5382-94. 

The work reported by Ralph etal. (2003) is a well-rounded, self-contained essay on the DMFC. (See DMFC flow sheet in Figure 6.6.) Moreover, because Ballard/Johnson Matthey did not contribute on fuel cells at the Palm Springs Fuel Cell Seminar in 2002 (see below), Ralph etal. (2003) is the current information source, additional to the patents in the list of references. Note that the methanol-water mixture presents to the fuel electrode its associated methanol vapour pressure. The DMFC does not have an incompressible fuel. The cell needs circulators. It is incomplete. 

It should be pointed out, that although the relationship between distribution coefficient and methanol concentration is not linear, neither is it logarithmic a graph of log (distribution coefficient) against methanol concentration gives a shallow curve. In order to obtain an explicit function for the retention of a solute in terms of the original methanol concentration, it is necessary to determine the equilibrium constant for the association of water and methanol. This was carried out by Katz et al [7] using refractive index and density data for different methanol/water mixtures and an expression for the retention of the solute was proposed. 

H. Tsubota and G. Atkinson, J. Phys. Chem., 71, 1131 (1967). The association of MnS04 in methanol-water mixtures of high methanol content. 

When the relationship between the distribution coefficient of a solute and solvent composition, or the corrected retention volume and solvent composition, was evaluated for aqueous solvent mixtures, it was found that the simple relationship identified by Purnell and Laub and Katz et al. no longer applied. The suspected cause for the failure was the strong association between the solvent and water. As a consequence, the mixture was not binary in nature but, in fact, a ternary system. An aqueous solution of methanol, for example, contained methanol, water and methanol associated with water. It follows that the prediction of the net distribution coefficient or net retention volume for a ternary system would require the use of three distribution coefficients one representing the distribution of the solute between the stationary phase and water, one representing that between the stationary phase and methanol and one between the stationary phase and the methanol/water associate. Unfortunately, as the relative amount of association varies with the initial... 

Katz, Lochmuller and Scott also examined acetonitrile/water, and tetrahydrofuran (THF)/water mixtures in the same way and showed that there was significant association between the water and both solvents but not nearly to the same extent as methanol/water. At the point of maximum association for methanol, the solvent mixture contained nearly 60% of the methanol/water associate. In contrast the maximum amount of THF associate that was formed amounted to only about 17%, and for acetonitrile the maximum amount of associate that was formed was as little as 8%. It follows that acetonitrile/water mixtures would be expected to behave more nearly as binary mixtures than methanol/water or THF/water mixtures. 

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