Recent advances in the physical chemistry of the liquid state

doi:10.1016/0001-8716(76)80039-9

Advances in Molecular Relaxation Processes

Volume 8, Issue 3, July 1976, Pages 195-239

https://doi.org/10.1016/0001-8716(76)80039-9 Get rights and content

Abstract

A summary of recent progress in the physical chemistry connected with both equilibrium properties and molecular dynamics of pure liquids is presented. After a short survey of pair potentials and various aspects of the structure of monoatomic dense fluids, selected potential models for polyatomic molecules are discussed. In particular, some computational methods concerning evaluation of structural and thermodynamic properties in cases where the molecules interact via angle-dependent potentials are reviewed.

For the dynamics of translational motion of molecules in pure liquids, emphasis is placed on the long time behaviour of various correlation functions and their interpretation in terms of collective molecular motion. Some results of interaction induced light scattering are also included. The dynamics of vibrational motion is mainly discussed on the basis of the recently developed picosecond laser pulse technique. Rotational motion is treated from the viewpoint of orientational correlation functions and angular velocity correlation functions. This is followed by a discussion of some aspects of applying laser pulse methods for elucidating the rotational dynamics of molecules in solution. Finally, a few significant results concerning relaxation of flexible molecular groups are reported.

References (152)

F. Kohler
Advan. Mol. Relaxation Processes
(1972)
A.H. Narten
J. Chem. Phys.
(1972)
S.I. Sandler et al.
J. Chem. Phys.
(1974)
F. Kohler, J. W. Perram, Mol. Phys.,...
B. C. Freasier, D. Jolly and R. J. Bearman, in...
D. Levesque et al.
Phys. Rev., A
(1970)
F. Mezei
Z. Phys.
(1972)
T. Springer
R.C. Watson et al.
J. Chem. Phys.
(1974)
R.R. Alfano et al.
Phys. Rev. Lett.
(1972)
R.R. Alfano et al.
Sci. Amer.
(1973)
F. Kohler
(1972)

P. A. Egelstaff, C. G. Gray and K. E. Gubbins, in A. D. Buckingham (Ed.), M.T.P. Int. Rev. Science, Physical Chemistry,...

Y.S. Kim et al.

J. Chem. Phys.

(1974)

R.G. Gordon et al.

J. Chem. Phys.

(1972)

J.H. Dymond et al.

J. Chem. Phys.

(1969)

J.M. Parson et al.

J. Chem. Phys.

(1972)

J.M. Farrar et al.

J. Chem. Phys.

(1972)

V. Buck

J. Chem. Phys.

(1971)

U. Buck

Rev. Mod. Phys.

(1974)

Y. Tanaka et al.

J. Chem. Phys.

(1970)

G.C. Maitland et al.

Mol. Phys.

(1971)

G.C. Maitland et al.

Chem. Soc. Rev.

(1973)

K.K. Docken et al.

J. Mol. Spectrosc.

(1973)

J.A. Barker et al.

Mol. Phys.

(1971)

B.M. Axilrod et al.

J. Chem. Phys.

(1943)

B.M. Axilrod

J. Chem. Phys.

(1951)

J.A. Barker et al.

J. Chem. Phys.

(1974)

H.C. Longuet-Higgins et al.

Mol. Phys.

(1964)

H. Reiss

Advan. Chem. Phys.

(1965)

J.D. Weeks et al.

J. Chem. Phys.

(1971)

J.E. Enderby

C.A. Croxton

(1974)

E. Wilhelm

J. Chem. Phys.

(1974)

E. Wilhelm and F. Kohler, to be...

A. Barker et al.

J. Chem. Phys.

(1967)

W.R. Smith

(1973)

W. Malesinski, Proc. 1st Int. Conf. Calorimetry and Thermodynamics, Warsaw, August 31 – September 4, 1969, p....

J.R. Sweet et al.

J. Chem. Phys.

(1967)

a K. Singer, private...J. Barojas et al.

Phys. Rev., A

(1973)

P.S.Y. Chueng et al.

Mol. Phys.

(1975)

A. Koide et al.

Chem. Phys.

(1974)

A. Ben-Naim et al.A. Ben-Naim

J. Chem. Phys.

(1970)

F.H. Stillinger et al.

J. Chem. Phys.

(1974)

J.S. Rowlinson

Trans. Faraday Soc.

(1951)

R.O. Watts

Mol. Phys.

(1974)

J.W. Perram et al.

Advan. Mol. Relaxation Processes

(1974)

A. Rahman et al.

J. Chem. Phys.

(1971)

A. Rahman et al.

J. Chem. Phys.

(1972)

J.A. Barker et al.

Chem. Phys. Lett.

(1969)

R. O. Watts, Third International Conference on Chemical Thermodynamics, 3–7 September, 1973, Baden (Austria), Vol. 2,...

H. Kistenmacher et al.

J. Chem. Phys.

(1974)

H.L. Lemberg et al.

J. Chem. Phys.

(1975)

J.W. Perram et al.

Mol. Phys.

(1972)

J.W. Perram et al.

Mol. Phys.

(1974)

S.I. Sandler

Mol. Phys.

(1974)

W.A. Steele et al.

J. Chem. Phys.

(1974)

L. Verlet et al.

Mol. Phys.

(1974)

F. Kohler et al.

Chem. Phys. Lett.

(1975)

E. Wilhelm et al.

J. Chem. Phys.

(1971)

J.S. Rowlinson

(1971)

H. Reiss et al.

J. Chem. Phys.

(1974)

R.M. Gibbons

Mol. Phys.

(1969)

J. Vieillard-Baron

Mol. Phys.

(1974)

Cited by (22)

Dilute solutions of gases in liquids
1986, Fluid Phase Equilibria
The thermodynamic basis of high-precision methods for the determination of the solubility of gases in liquids is reviewed briefly. Various aspects of data reduction, including a survey of current estimation techniques for auxiliary quantities, such as virial coefficients and partial molar volumes, are presented. The final sections are devoted to data correlation and prediction of gas solubilities as function of temperature and pressure.
Molecular thermodynamics of flexible-molecule fluids
1985, Thermochimica Acta
Some of the most important problems encountered -in the statistical-mechanical treatment of dense, complex molecular fluids are indicated. Particular attention is given to the application of the generalized van der Waals concept to flexible-molecule fluids. Perturbed-hard-chain theory and chain-of-rotators theory are reviewed. This is followed by a brief summary of recent experimental work on thermodynamic excess properties of liquid mixtures of type (Y + an n-alkane). Several novel effects connected with local correlation of molecular orientation in the n-alkanes, with medium-induced conformational changes and with preferential orientation of strongly polar molecules are discussed (order/disorder phenomena).
Equilibrium properties of suspensions
1984, Advances in Colloid and Interface Science
This review gives a critical assessment of the various theoretical methods used to calculate, interpret and predict the equilibrium properties of stable particulate suspensions. The emphasis is on methods mainly used over the past decade to study osmotic pressure, static structure factor, radial distribution function, elastic constants and phase equilibria of suspensions of monodisperse spherical particles. The effects of polydispersity and non-sphericity of the particles are also briefly reviewed.
Although most applications to data have used a pair-wise additive interparticle potential energy function of the DLVO type, a general discussion of the nature of this interparticle potential is given.
An overview of the various statistical mechanical methods used is presented; this includes exact computer simulation methods and approximations such as perturbation theories an integral equation methods. Where possible direct comparisons are drawn between the results of accurate computer simulations and these approximate methods in order to indicate their relative merits, accuracy and range of validity. For situations where accurate experimental data exist, comparisons between theory and experimental results are made to assess the validity of models for the interparticle potentials.
Calorimetry: Its contributions to molecular thermodynamics of fluids
1983, Thermochimica Acta
This article reviews recent contributions of fluid phase calorimetry to the theory of pure fluids and fluid mixtures. Selected examples serve to illustrate the use of experimental results for the development of rational prediction techniques for thermodynamic quantities, which are of importance for the chemical engineer. For instance, the following topics are dealt with in some detail:
- •
  Low density fluids: virial coefficients;
- •
  Pure liquids: isothermal compressibility, heat capacity at constant volume;
- •
  Liquid mixtures: data correlation, group contribution methods;
- •
  Dilute solutions: enthalpy of solution.
Excess volumes and excess heat capacities of tetrachloroethene + cyclohexane, + methylcyclohexane, + benzene, and + toluene at 298.15 K
1982, The Journal of Chemical Thermodynamics
Molar excess volumes V_m^E at 298.15 K were obtained, as a function of mole fraction x, for the four liquid mixtures tetrachloroethene + cyclohexane, + methylcyclohexane, + benzene, and + toluene from measurements of the density with a vibrating-tube densimeter. The excess volumes are positive in all cases, the largest value of V_m^E being found for {xC₂Cl₄ + (1 − x)c-C₆H₁₂}: V_m^E(max) = 0.529 cm³·mol⁻¹ at x = 0.4540. The maximum values V_m^E(max)/(cm³·mol⁻¹) for the other mixtures, in the sequence given above, are: 0.180 at x = 0.4330, 0.405 at x = 0.4538, and 0.131 at x = 0.4532. A Picker flow calorimeter was used to determine molar excess heat capacities at 298.15 K for each of these binaries: C_{p, m}^E is negative for all four. In the same sequence, C_{p, m}^E(min)/(J·K⁻¹·mol⁻¹) is, respectively, −1.41 at x = 0.5323, −0.92 at x = 0.4899, −2.25 at x = 0.4196, and −0.54 at x = 0.4056.
Molar heat capacity of binary liquid mixtures: 1,2-dichloroethane + cyclohexane and 1,2-dichloroethane + methylcyclohexane
1979, Thermochimica Acta
The molar heat capacity at constant pressure, C_P, of the two binary liquid mixtures 1,2-dichloroethane + cyclohexane and 1,2-dichloroethane + methylcyclohexane were determined at 298.15 K from measurements of the volumetric heat capacity, C_P/V, in a Picker flow microcalorimeter (V is the molar volume). For the molar excess heat capacity, C_P^E, the imprecision of the adopted stepwise procedure is characterized by a standard deviation of about ± 0.05 J K⁻¹ mole⁻¹, which amounts to ca. 3% of C_P^E. Literature data on ultrasonic velocities, on molar volumes, and on coefficients of thermal expansion were used to calculate the molar heat capacity at constant volume, C_v, and the isothermal compressibility, β_T, of the pure substances, as well as the corresponding excess quantities C_V^E and (Vβ_T)^E of the binary mixture 1,2-dichloroethane + cyclohexane. A preliminary discussion of our results in terms of external and internal rotational behavior (trans-gauche equilibrium of 1,2-dichloroethane) is presented.

View all citing articles on Scopus

¹: Present address: Institut für Thermo- and Fluiddynamik, Ruhr-Universität Bochum, 463 Bochum (W. Germany)

View full text

Recent advances in the physical chemistry of the liquid state

Abstract

Advan. Mol. Relaxation Processes

J. Chem. Phys.

J. Chem. Phys.

Phys. Rev., A

Z. Phys.

J. Chem. Phys.

Phys. Rev. Lett.

Sci. Amer.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

Rev. Mod. Phys.

J. Chem. Phys.

Mol. Phys.

Chem. Soc. Rev.

J. Mol. Spectrosc.

Mol. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

Mol. Phys.

Advan. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

Phys. Rev., A

Mol. Phys.

Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

Trans. Faraday Soc.

Mol. Phys.

Advan. Mol. Relaxation Processes

J. Chem. Phys.

J. Chem. Phys.

Chem. Phys. Lett.

J. Chem. Phys.

J. Chem. Phys.

Mol. Phys.

Mol. Phys.

Mol. Phys.

J. Chem. Phys.

Mol. Phys.

Chem. Phys. Lett.

J. Chem. Phys.

J. Chem. Phys.

Mol. Phys.

Mol. Phys.