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Physical and Inorganic Chemistry pp 33–144Cite as

Non-aqueous electrolyte solutions in chemistry and modern technology

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Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 111))

Abstract

In this paper a brief survey is given of the properties of non-aqueous electrolyte solutions and their applications in chemistry and technology without going into the details of theory. Specific solvent-solute interactions and the role of the solvent beyond its function as a homogenous isotropic medium are stressed. Taking into account Parker's statement1) “Scientists nowadays are under increasing pressure to consider the relevance of their research, and rightly so” we have included examples showing the increasing industrial interest in non-aqueous electrolyte solutions.

The concepts and results are arranged in two parts. Part A concerns the fundamentals of thermodynamics, transport processes, spectroscopy and chemical kinetics of non-aqueous solutions and some applications in these fields. Part B describes their use in various technologies such as high-energy batteries, non-emissive electro-optic displays, photoelectrochemical cells, electrodeposition, electrolytic capacitors, electro-organic synthesis, metallurgic processes and others.

Four Appendices are added. Appendix A gives a survey on the most important non-aqueous solvents, their physical properties and correlation parameters, and the commonly used abbreviations. Appendices B and C show the mathematical background of the general chemical model. The Symbols and abbreviations of the text are listed and explained in Appendix D.

in connexion with symbol Δ, cf. Fig. 1

means a superscript or subscript, see Section D.2.

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Abbreviations

NA :

Avogadro constant (6.022045±0.000031)×1023 mol−1

F:

Faraday constant (9.648456±0.000027)×104 C mol−1

h:

Planck constant (6.626176±0.000036)×10−34 J s

k:

Boltzmann constant (1.380662±0.000044)×10−23 J K−1

e0 :

charge of proton (1.602189±0.000005)×10−19 C

ε0 :

permittivity of vacuum (8.854188±0.000000)×10−12 J−1 C2 m−1

*:

pure substance also: non-Coulombic part of a quantity

∞:

infinite dilution

0:

standard

(0):

reference solvent (Section VIII)

(s):

solvent S (Section VIII)

≠:

activated complex

el:

Coulombic part of a quantity free particles also: final state (Section V)

(c):

molar scale

(m):

molal scale

(i):

component i

A:

association

calc:

calculated quantity

exp:

experimental quantity

FI:

free ion

iorj:

ions i or j also: index for summation formulae \(\sum\limits_i\)

ij:

ion j in the victinity of an ion i

IP:

ion pair

max:

maximum value

obs:

observed quantity

S:

solvent

Y:

electrolyte Y

+:

cation

−:

anion

±:

mean quantity of electrolyte Y

∞:

infinite frequency

dil:

dilution

lat:

lattice

sol:

solution

solv:

solvation

vap:

vaporation

tr:

transfer from water to a non-aqueous solvent

a, a* :

ion size parameter

c, c*, c*:

molarity [mol dm−3]

E, E*:

property (general) of an electrolyte solution (Sect. V) also: e.m.f (Sect. V)

f, fS :

activity coefficient (mole fraction scale)

fij, fji :

two-particle distribution function

gij, gji :

pair-correlation function

ΔG*, ΔG*, Δ*G:

Gibbs energy

ΔH*, ΔH*, Δ*H:

enthalpy

K, K* :

equilibrium constant

k, k*, k*:

rate constant, exception see D.1

m, m*, m*:

molality [mol kg−1] also: mass of particle (Sect. IV)

M:

mol dm−3

nS, nY :

amount of substance (number of moles)

N* :

particle density [particles per cm−3], exception see D.1

p:

pressure

q:

Bjerrum parameter, see Eq. (19 b)

R, R* :

distance parameter, see Figs. 2 and 3

R:

also: gas constant

\(r,r_* ,\vec r,\vec r_* :\) :

distance variable

ΔS*, ΔS*, Δ*S:

entropy

t*, t*:

transference number

t:

also: time

T, T* :

temperature [K]

V, ΔV*, ΔV* :

volume

W*, W*:

mean-force potential

x, x*, x*:

mole fraction

y, y*, y*:

activity coefficient (molar scale)

z, z* :

valency

Z, Z*, Z*, ΔZ*, ΔZ*, Δ*Z:

thermodynamic property (general), see Fig. 1

α:

degree of dissociation

(1−α):

degree of association

\(\bar \alpha :\) :

cubic expansion coefficient (Section V)

γ*, γ*:

activity coefficient (molal scale)

mγ*:

transfer activity coefficient

Γ:

ional concentration, see Table II

δ, δ* :

chemical shift

ε, ε*, ε*:

relative permittivity, exception see D.1

η:

viscosity

θ, θ* :

temperature [°C]

χ:

Debye parameter, see Table II

χ, χ* :

also: electrolytic conductivity [Ω−1 mol−1 cm2]

Λ*, Λ*:

equivalent conductance [Ω−1 mol−1 cm2]

λ*, λ*:

single ion conductance [Ω−1 mol−1 cm2]

μ*, μ*:

chemical potential

νiν mi :

stoichiometric number

ϱ:

density [g cm−3]

ω:

circular frequency

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  1. Institut für Physikalische und Theoretische Chemie der Universität Regensburg, FRG

    Josef Barthel, Heiner-J. Gores, Georg Schmeer & Rudolf Wachter

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Barthel, J., Gores, HJ., Schmeer, G., Wachter, R. (1983). Non-aqueous electrolyte solutions in chemistry and modern technology. In: Physical and Inorganic Chemistry. Topics in Current Chemistry, vol 111. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-12065-3_2

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