Effects of Temperature on the Thermodynamic and Dynamical Properties of Glycerol-Water Mixtures: A Computer Simulation Study of Three Different Force Fields

被引:29
作者
Akinkunmi, Frederick O. [1 ]
Jahn, David A. [1 ]
Giovambattista, Nicolas [1 ]
机构
[1] CUNY Brooklyn Coll, Dept Phys, Brooklyn, NY 11210 USA
基金
美国国家科学基金会;
关键词
MOLECULAR-DYNAMICS; ISOTHERMAL COMPRESSIBILITY; SUPERCOOLED WATER; CONDENSED PHASES; AQUEOUS GLYCEROL; ENERGY FUNCTIONS; ORGANIC LIQUIDS; HEAT-CAPACITY; NUCLEIC-ACIDS; PRESSURE;
D O I
10.1021/acs.jpcb.5b00439
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Glycerol water solutions are relevant in technological and scientific applications, such as in the preservation of biomolecules and tissues at low temperatures. We perform molecular dynamics Simulations of glycerol-water mixtures with glycerol molar fractions of chi(g) = 0-100% at P = 0.1 MPa and T = 210-460 K. We focus On the effects of temperature and concentration on the thermodynamic (density rho, thermal expansion coefficient alpha(p), isobaric specific heat c(p), compressibility K-T) and dynamical (glycerol and water diffusion coefficients, D-g and D-w) properties of the mixtures. In particular, we test the sensitivity of computer simulation results to the glycerol force field and water model (TIP3P and TIP4P/2005) employed. All mixture models underestimate rho at high T and tend to overestimate rho at low T-j only the mixture model based on TIP4P/2005 water exhibits a density maximum at low chi(g), as expected. All models overestimate alpha(p), c(p), and K-T; they are able to reproduce qualitatively the T dependence of alpha(p) and K-T but fail in the case of c(p). In all cases, D-g and D-w follow the Vogel Tamman Fulcher equation and decouple at low T, with D-w/D-g increasing upon cooling. Overall, the mixture based on TIP4P/2005 water provides better thermodynamic and dynamical properties than the mixtures based on TIP3P water, even chi(g) = 20%.
引用
收藏
页码:6250 / 6261
页数:12
相关论文
共 62 条
[1]   A general purpose model for the condensed phases of water: TIP4P/2005 [J].
Abascal, JLF ;
Vega, C .
JOURNAL OF CHEMICAL PHYSICS, 2005, 123 (23)
[2]   Widom line and the liquid-liquid critical point for the TIP4P/2005 water model [J].
Abascal, Jose L. F. ;
Vega, Carlos .
JOURNAL OF CHEMICAL PHYSICS, 2010, 133 (23)
[3]  
Adamenko II, 2007, UKR J PHYS, V52, P855
[4]  
Allen M.P., 1988, Computer Simulation of Liquids
[5]   ANOMALOUS PROPERTIES OF SUPERCOOLED WATER - HEAT-CAPACITY, EXPANSIVITY, AND PROTON MAGNETIC-RESONANCE CHEMICAL-SHIFT FROM 0 TO -38 DEGREES [J].
ANGELL, CA ;
SHUPPERT, J ;
TUCKER, JC .
JOURNAL OF PHYSICAL CHEMISTRY, 1973, 77 (26) :3092-3099
[6]  
[Anonymous], 1963, PHYS PROP GLYC ITS S
[7]  
[Anonymous], 1926, Z ANORG ALLG CHEM
[8]  
[Anonymous], 1949, NOTH TAK PLAC GLYC 1
[9]   Fast relaxation and elasticity-related properties of trehalose-glycerol mixtures [J].
Averett, Devin ;
Cicerone, Marcus T. ;
Douglas, Jack F. ;
de Pablo, Juan J. .
SOFT MATTER, 2012, 8 (18) :4936-4945
[10]   INTRA-MOLECULAR HYDROGEN BONDS IN ETHYLENE GLYCOL, GLYCEROL, AND ETHYLENE CHLOROHYDRIN [J].
BASTIANSEN, O .
ACTA CHEMICA SCANDINAVICA, 1949, 3 (04) :415-421