Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005, India.
Carbohydr Res. 2010 Oct 13;345(15):2262-71. doi: 10.1016/j.carres.2010.07.021. Epub 2010 Jul 18.
Infinite-dilution standard partial molar volumes, V(2)(0), for various mono-, di-, and trisaccharides, and their derivatives (methyl glycosides) at molalities ranging from 0.04 to 0.12 mol kg(-1) in aqueous solutions of magnesium chloride of 0.5, 1.0, 2.0, and 3.0 mol kg(-1), have been evaluated over a range of temperatures from 288.15 to 318.15 K by density measurements employing a vibrating-tube densimeter. These data have been utilized to determine the corresponding standard partial molar volumes of transfer, Δ(t)V(2)(0), of saccharides and methyl glycosides from water to aqueous magnesium chloride solutions. The Δ(t)V(2)(0) values have been found to be positive, and their magnitudes increase with an increasing concentration of magnesium chloride in all cases. Partial molar expansion coefficients, (∂V(2)(0)/∂T)(P) and second derivatives thereof, (∂(2)V(2)(0)/∂T(2))(P) have been estimated. The magnitude of V(2)(0) values increases with an increase in temperature, indicating that hydration effects in solutions are strongly sensitive to temperature. Pair and higher order volumetric interaction coefficients (V(AB), V(ABB)) have also been obtained from Δ(t)V(2)(0) values by using the McMillan-Mayer theory. The various parameters have been discussed in terms of the solute (saccharide or methyl glycoside)-co-solute (magnesium chloride) interactions and are thus used to understand the mixing effects due to these interactions. These results have been compared with those earlier reported in the presence of electrolytes. An attempt is made to interpret the volumetric properties data in terms of the stereochemistry of the solutes.
在 288.15 至 318.15 K 的温度范围内,通过密度测量使用振动管密度计评估了在 0.5、1.0、2.0 和 3.0 mol kg(-1) 的氯化镁水溶液中,各种单糖、二糖和三糖及其衍生物(甲基糖苷)在 0.04 至 0.12 mol kg(-1) 的摩尔浓度下的无限稀释标准偏摩尔体积 V(2)(0)。这些数据已用于确定糖和甲基糖苷从水到氯化镁水溶液的相应标准偏摩尔传递体积 Δ(t)V(2)(0)。发现 Δ(t)V(2)(0) 值为正,并且在所有情况下,随着氯化镁浓度的增加,其幅度增加。已估算出偏摩尔膨胀系数 (∂V(2)(0)/∂T)(P) 及其二阶导数 (∂(2)V(2)(0)/∂T(2))(P)。V(2)(0) 值随温度升高而增加,表明溶液中的水合作用对温度非常敏感。还通过使用 McMillan-Mayer 理论从 Δ(t)V(2)(0) 值获得了对和更高阶体积相互作用系数 (V(AB)、V(ABB))。已根据溶质(糖或甲基糖苷)-共溶质(氯化镁)相互作用讨论了各种参数,并因此用于理解这些相互作用引起的混合效应。将这些结果与以前在存在电解质的情况下报告的结果进行了比较。尝试根据溶质的立体化学解释体积性质数据。