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Thermodynamic Measurements

  • C. M. Criss
  • M. Salomon
  • R. Garnsey
  • J. E. Prue
  • C. M. Criss

Abstract

Thermodynamic properties of solutions are not only useful for estimating the feasibility of reactions in solution, but they also offer one of the better methods of investigating the theoretical aspects of solution structure. This is particularly true for the standard partial molal entropy, heat capacity, and volume of the solutes, values of which are sensitive to the arrangement of solvent molecules around a solute molecule. They have been examined extensively B1–4 in aqueous solution for the purpose of structure interpretation and more recently in non-aqueous solutions.B5–8 Enthalpies and free energies of solvation and transfer between solvents have also been valuable in the testing of theoretical relationships such as the Born equation B9 and modifications of the Born equation,Bl0 as well as predicting solvation effects in reaction kinetics.B11,B12

Keywords

Activity Coefficient Partial Molal Volume Infinite Dilution Propylene Carbonate Silver Halide 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notation

ai

Activity of component i

a±

Mean activity of an electrolyte

a

Ion-size parameter

A

Debye-Hückel limiting slope constant for activity coefficients (eqn. 2.3.11)

AH, AV

Theoretical limiting slope for heats and volumes respectively

Aη

Experimental limiting slope for viscosities

b

Empirical constant in eqn. 2.3.67

B

Constant in eqn. 2.3.50

Bη

Empirical constant in eqn. 2.3.74

c

Molar concentration

C

Empirical constant in eqn. 23.50

Cp

Heat capacity at constant pressure

\({{\bar{C}}_{pi}}\)

Partial molal heat capacity of component i

\(\bar{C}_{pi}^{o}\)

Standard partial molal heat capacity of component i

d

Density of solution

do

Density of solvent

D

Empirical constant in eqn. 2.3.50

Dη

Empirical constant in eqn. 2.3.75

e

Electronic charge

εr

Dielectric constant (relative permittivity)

\({{\bar{G}}_{i}}\)

Partial molal free energy of component i

\(\bar{G}_{i}^{o}\)

Standard partial molal free energy of component i

H

Total enthalpy

\({{\bar{H}}_{i}}\)

Partial molal enthalpy of component i

\(\bar{H}_{i}^{o}\)

Standard partial molal enthalpy of component i

I

Ionic strength, defined by eqn. 2.3.12

\({{\bar{J}}_{i}}\)

Relative partial molal heat capacity of component i

k

Boltzmann constant

K

Constant used in eqn. 2.3.68 and defined by eqn. 2.3.70

Ks0

Solubility product constant

KV

Empirical constant in eqn. 2.3.71

\({{\bar{L}}_{i}}\)

Relative partial molal enthalpy of component i

m

Molal concentration

mi

Molal concentration of component i

m±

f Mean molal concentration of an electrolyte

Mi

Molecular weight of component i

ni

Number of moles of component i

N

Avogadro number

p

Pressure

R

Molar gas constant

SV

Experimental limiting slope for volume (including valence factor)

\({{\bar{S}}_{i}}\)

Partial molal entropy of component i

\(\bar{S}_{t}^{o}\)

Standard partial molal entropy of component i

T

Temperature

Ts

Standard temperature

V

Volume

\({{\bar{V}}_{i}}\)

Partial molal volume of component i

\(\bar{V}_{i}^{o}\)

Standard partial molal volume of component i

w

Valence factor defined by eqn. 2.3.69

xi

Mole fraction of component i

z+, z

Charge on indicated ion

ω

Special function defined by eqn. 2.3.49

α(m)

Degree of dissociation at molality m

α

Temperature coefficient of expansion

ß

Coefficient of compressibility

γ±

Mean activity coefficient of an electrolyte

∆G

Change in free energy

∆G°

Standard change in free energy

∆GsoIno, ∆HsoIno, ∆SsoIno

Standard change of indicated quantity upon dissolution of solute

∆Hfo

Standard enthalpy of fusion

∆Ha

Enthalpy of association

η

Viscosity of solution

ηo

Viscosity of solvent

к

Function defined by eqn. 2.3.73

Λ

Equivalent conductance

Λo

Equivalent conductance at infinite dilution

ν

Total number of ions produced by one molecule of electrolyte

ν+, ν-

Number of cations and anions in one molecule of electrolyte

ρ

Special function defined by eqn. 2.3.48

σ(x)

Special function in eqn. 2.3.43

CP,⌽H, ⌽L,⌽V

Apparent molal quantity indicated

Ωv

Function defined by eqn. 2.3.72

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Copyright information

© Plenum Publishing Company Ltd 1973

Authors and Affiliations

  • C. M. Criss
    • 1
  • M. Salomon
    • 2
  • R. Garnsey
    • 3
  • J. E. Prue
    • 4
  • C. M. Criss
    • 5
  1. 1.Dept. of ChemistryUniversity of MiamiCoral GablesUSA
  2. 2.Electronics Research CenterNational Aeronautics and Space AdministrationCambridgeUSA
  3. 3.Research LaboratoriesCentral Electricity Generating BoardLeatherheadEngland
  4. 4.Department of ChemistryThe UniversityReadingEngland
  5. 5.Department of ChemistryUniversity of MiamiCoral GablesUSA

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