Isotope effect on the translational and rotational motion in liquid water and ammonia

被引:85
作者
Hardy, EH
Zygar, A
Zeidler, MD
Holz, M
Sacher, FD
机构
[1] Rhein Westfal TH Aachen, Inst Phys Chem, D-52056 Aachen, Germany
[2] Univ Karlsruhe, Inst Phys Chem, D-76128 Karlsruhe, Germany
关键词
D O I
10.1063/1.1340584
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
The dynamic isotope effects (IE) on the translational and rotational motion in liquid ammonia and water are reassessed by NMR measurements. For H2O/D2O the translational and rotational IE are clearly distinct. At 298 K, 23% and 30% are obtained, respectively. Both effects as well as the slopes of the temperature dependencies increase with decreasing temperature. For NH3/ND3 a rotational IE of 37% was observed at 298 K. A small increase to 40% at 222 K could be ascertained. The translational IE is about 15% at room temperature and exhibits a stronger temperature dependence. It is suggested that the observed deviations of the IE's from the square root of mass and square root of moments of inertia laws are caused by translation-rotation coupling as well as quantum effects. The experimental data obtained in the present paper are also of importance for the correct interpretation of all kinds of experiments on water and ammonia, where isotopic substitutions are involved. (C) 2001 American Institute of Physics.
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收藏
页码:3174 / 3181
页数:8
相关论文
共 43 条
[1]   NUCLEAR MAGNETIC RELAXATION IN LIQUID AMMONIA AND CONDITIONAL INERTIAL ROTATION IN LIQUIDS [J].
ATKINS, PW ;
LOEWENST.A ;
MARGALIT, Y .
MOLECULAR PHYSICS, 1969, 17 (04) :329-+
[2]   IS LIQUID WATER REALLY ANOMALOUS [J].
BASSEZ, MP ;
LEE, J ;
ROBINSON, GW .
JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (22) :5818-5825
[3]   New generalized gradient approximation functionals [J].
Boese, AD ;
Doltsinis, NL ;
Handy, NC ;
Sprik, M .
JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (04) :1670-1678
[4]   Self-diffusion in CD4 and ND3:: With notes on the dynamic isotope effect in liquids [J].
Buchhauser, J ;
Gross, T ;
Karger, N ;
Lüdermann, HD .
JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (06) :3037-3042
[5]   ROUGH HARD-SPHERE THEORY OF SELF-DIFFUSION CONSTANT FOR MOLECULAR LIQUIDS [J].
CHANDLER, D .
JOURNAL OF CHEMICAL PHYSICS, 1975, 62 (04) :1358-1363
[6]   TRANSLATIONAL AND ROTATIONAL DIFFUSION IN LIQUIDS .1. TRANSLATIONAL SINGLE-PARTICLE CORRELATION-FUNCTIONS [J].
CHANDLER, D .
JOURNAL OF CHEMICAL PHYSICS, 1974, 60 (09) :3500-3507
[7]   TRANSLATIONAL AND ROTATIONAL DIFFUSION IN LIQUIDS .2. ORIENTATIONAL SINGLE-PARTICLE CORRELATION-FUNCTIONS [J].
CHANDLER, D .
JOURNAL OF CHEMICAL PHYSICS, 1974, 60 (09) :3508-3512
[8]  
FRIEDMAN HL, 1974, MOL MOTIONS LIQUIDS, P87
[9]   Analysis of recent measurements of the viscosity of glasses [J].
Fulcher, GS .
JOURNAL OF THE AMERICAN CERAMIC SOCIETY, 1925, 8 (06) :339-355
[10]  
Geet A. L. V., 1970, ANAL CHEM, V42, P679