Hoffmann Markus M, Gonzalez Anthony A, Huynh Mandy T, Miller Kashane K, Gutmann Torsten, Buntkowsky Gerd
Department of Chemistry and Biochemistry, State University of New York Brockport, Brockport, New York 14420, United States.
Institute of Physical Chemistry, Technical University Darmstadt, Peter-Grünberg-Straße 8, D-64287 Darmstadt, Germany.
J Chem Eng Data. 2024 Jul 3;69(8):2688-2699. doi: 10.1021/acs.jced.4c00195. eCollection 2024 Aug 8.
Density, viscosity, and self-diffusion coefficients are reported for octan-1-ol and the related ether-alcohols 2-pentoxy-ethan-1-ol, 3-butoxypropan-1-ol, 4-propoxybutan-1-ol, 5-ethoxypentan-1-ol, and 6-methoxyhexan-1-ol covering temperature ranges from 298.15 to 359.15 K. These new data reveal structure-property relationships affected by the presence and the position of the ether moiety in the molecular structure of the ether-alcohols. Compared to octan-1-ol, the presence of the ether moiety causes an increase in intermolecular hydrogen bonding interactions, resulting in higher densities. The increase in density is less pronounced for those ether-octanols that engage in intramolecular hydrogen bonding. As for the effects of the ether moiety on the dynamics, these are generally faster for the ether-alcohols compared to octan-1-ol, suggesting that hydrogen bonding between ether oxygen and hydroxy hydrogen is weaker compared to hydrogen bonding between two hydroxy groups. The activation energies obtained from an Arrhenius analysis are higher for translational motion than for momentum transfer for all alcohols. There are additional finer details across the ether alcohols for these activation barriers. These differences cancel out for the mathematical product of self-diffusion coefficient and viscosity (). The effect of water impurities on the studied properties was also investigated and found to lead to small increases in densities for all alcohols. Viscosities decrease for octan-1-ol and 2-pentoxyethan-1-ol but increase for the other ether-alcohols that can engage in intramolecular hydrogen bonding.
报告了正辛醇以及相关醚醇(2-戊氧基乙醇、3-丁氧基丙醇、4-丙氧基丁醇、5-乙氧基戊醇和6-甲氧基己醇)在298.15至359.15 K温度范围内的密度、粘度和自扩散系数。这些新数据揭示了醚醇分子结构中醚部分的存在和位置对结构-性质关系的影响。与正辛醇相比,醚部分的存在导致分子间氢键相互作用增加,从而使密度更高。对于那些参与分子内氢键的醚辛醇,密度的增加不太明显。至于醚部分对动力学的影响,与正辛醇相比,醚醇的动力学通常更快,这表明醚氧和羟基氢之间的氢键比两个羟基之间的氢键弱。通过阿仑尼乌斯分析得到的所有醇类平移运动的活化能高于动量传递的活化能。这些醚醇的活化能障碍还有其他更细微的细节。自扩散系数和粘度的数学乘积()的这些差异相互抵消。还研究了水杂质对所研究性质的影响,发现所有醇类的密度都会略有增加。正辛醇和2-戊氧基乙醇的粘度降低,但其他能够参与分子内氢键的醚醇的粘度增加。