ORIENTED DIPOLES AT INTERFACES - CALCULATION OF SURFACE-POTENTIAL AND SURFACE-TENSION

被引:15
作者
DUNCANHEWITT, WC
机构
[1] University of Toronto, Toronto, Ontario M5S 1A1
关键词
D O I
10.1021/la00054a035
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A simple method is introduced that estimates the surface free energy of pure, polar liquids. For long-chain amphiphiles, the calculation is almost intuitive. In addition to the refractive index spectrum and dielectric permittivites used to calculate the van der Waals component from the Lifshitz theory, knowledge of the partial charge distribution in the dipolar molecule, the molecular conformation, and a model of the molecular packing at the liquid/vapor interface is required. For smaller, highly polar molecules, the molecular packing at the interface is not as easily predicted intuitively so that knowledge of the surface potential jump, chi, is also required. This parameter is not experimentally accessible and the models used presently to calculate it from the surface potential, psi, are inadequate. In response to this need, a new model has been developed which predicts the surface potential jump from experimental data. Finally, the surface free energies of water, methanol, and several other polar liquids are calculated as the sum of a van der Waals contribution arising from the interactions between randomly oriented molecules and an electrostatic, orientational term calculated from the partial charge distribution in the molecules.
引用
收藏
页码:1229 / 1234
页数:6
相关论文
共 29 条
[1]  
ADAMSON AW, 1967, PHYSICAL CHEM SURFAC
[2]   THE REAL STANDARD POTENTIAL ON THE AQUEOUS HYDROGEN SCALE OF THE SILVER SILVER-CHLORIDE ELECTRODE IN METHANOL - THE SURFACE-POTENTIAL OF METHANOL [J].
BARRACLOUGH, CG ;
BORAZIO, A ;
MCTIGUE, PT ;
VERITY, B .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1988, 243 (02) :353-365
[3]   CHARGE-DISTRIBUTION AT THE GAS WATER INTERFACE - THE SURFACE-POTENTIAL OF WATER [J].
BORAZIO, A ;
FARRELL, JR ;
MCTIGUE, P .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1985, 193 (1-2) :103-112
[4]   REAL SOLVATION ENERGIES OF HYDROCARBON IONS IN ACETONITRILE AND SURFACE POTENTIAL OF ACETONITRILE [J].
CASE, B ;
HUSH, NS ;
PARSONS, R ;
PEOVER, ME .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1965, 10 (5-6) :360-&
[5]  
CHRISTOU NI, 1985, MOL PHYS, V55, P39
[6]  
DAVIS HT, 1975, J CHEM PHYS, V62, P412
[7]   CONTRIBUTION OF LONG-RANGE POLARIZATION FLUCTUATIONS TO SURFACE-TENSION OF LIQUIDS [J].
FULTON, RL .
JOURNAL OF CHEMICAL PHYSICS, 1976, 64 (04) :1857-1858
[8]  
GABLER R, 1978, ELECTRICAL INTERACTI, P79
[9]   ABSOLUTE ORIENTATION OF WATER-MOLECULES AT THE NEAT WATER-SURFACE [J].
GOH, MC ;
HICKS, JM ;
KEMNITZ, K ;
PINTO, GR ;
BHATTACHARYYA, K ;
HEINZ, TF ;
EISENTHAL, KB .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (18) :5074-5075