988 J. Barthel et. al.: Dielectric Relaxation of Aqueous Electrolyte Solutions etc.

[6] B. Platzer and G. Maurer, Fluid Phase Equilibria 51, 223

(1989).
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u,.,,, = cc
1 . 1
XI, '.XI'UCh polarer Fluide und deren Gemische. Dissertation. Universitiit
Kaiserslautern 1990.
[8] F. Tsai and J. Shyu, J. Chin. 1. Ch. E. 16, 157 (1985).
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of gases and liquids, 4th cd., McGraw-Hill, New York 1987.
Y
[I21 K. H. Simmrock, R. Janowski, and A. Ohnsorge, Critical data
of pure substances, Dechema Chemistry Data Series Vol. 11,
Part 1, Frankfurt 1986.
[13] Kirk-Othmer, Enzyclopedia of chemical technology, 3rd ed.,
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[I41 G. Hommel, Handbuch der gefiihrlichen Cuter, Springcr-Ver-
[l] E. Bender, Die Berechnung von Phasengleichgewichten mit
lag, Berlin, Heidelberg 1988.
dcr thcrmischen Zustandsgleichung dargestellt an den reinen
[l5] D. Ambrose, J. E. Conett, J. H. S. Green, J. L. Hales, A. J.
Fluiden Argon, Stickstof& Sauerstoff und an ihren Gemischen. Head, and J. F. Martin, J. Chem. Thermodyn. 2, 1143 (1975).
Habilitationsschrift, Ruhr-Universitat Bochum 1971.
[16] J. Timmermanns, Physico-chemical constants of pure organic
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[17] N. B. Vargaftik, Tables of the thermophysical properties of
[3] D. Walther, Messung und Korrelation von Hochdruck-
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[18] D. R. Stull, Ind. Eng. Chem. 39, 517 (1947).
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Germany 1983. final version: May, 1Ist 1992)

Dielectric Relaxation of Aqueous Electrolyte Solutions.

I. Solvent Relaxation of 1:2, 2:1, and 2:2 Electrolyte Solutions
J. Barthel, H. Hetzenauer, and R. Buchner
lnstitut fur Physikalische und Theoretische Chemie, Universitat Regenburg, Germany

Dielectric Reluxution 1 Solutions 1 Spectroscopy, Microwuves

Complex permittivity measurements on aqueous solutions of CdCI?, CuCL, MgS04, CdS04, Na2S04,
Cd(CI04)2,and MgCI2 in the frequency range from 0.9 to 90 GHz are reported. The data analysis reveals
thc superposition of 2 Debye dispersion steps for thc solvent thus supporting multi-step relaxation mcch-
anisms discussed for water in the literature. An additional low frequency process is found for CdCI,. CuCh,
MgS04, CdS04, and Na2S04solutions due to solute relaxation, but not for Cd(CIO& and MgC12 solu-
tions. - The decrease of the static solvent permittivity at increasing clectrolytc conccntrations is intcr-
pretcd in terms of irrotational bonding and kinetic depolarization and is used to determine effective
solvation numbers. The dependence of the main (low frequency) relaxation time of water on electrolyte
conccntration is explained with the help of the reorientation and residence times of water in the hydration
spheres of ions and in the bulk. The high frequency relaxation time is approximately concentration
indcpendcnt, whereas the dispersion amplitude of the process increases with clectrolytc concentration.

l. Introduction
Dielectric relaxation experiments inform about the dis-
placement current resulting from the polarization of a sam-
ple in an externally applied time-dependent electric field.
With harmonic fields of angular frequency w, w = 2 x v , the
response of the sample is given by the complex permittivity
i ( w ) = c'(w)-ii"'(w), where ~ ' ( wcharacterizes
) the disper-
sion and c"(w) the energy absorption accompanying the po-
larity changes of the external field.
Complex permittivity spectra of electrolyte solutions and
their solvents in the microwave region reveal a wealth of
information on the structure and dynamics; they probe the
orientational, diffusional and H-bonding modes of solvent
and solute [l -31. Recent investigations show, that wide
 J. Barthel et. al.: Dielectric Relaxation of Aqueous Electrolyte Solutions etc.
frequency coverage and precise data are needed for the ex-
traction of unambiguous information from the microwave
spectra [4].
Despite of extensive studies in the microwave (MW) and
far infrared (FIR) region the spectrum of water is still con-
troversially discussed and models with one discrete relaxa-
tion time or with a distribution or superposition of relaxa-
tion processes are proposed in the Refs. [S-71. The choice
of the relaxation model for water affects to some extent the
interpretation of the dielectric properties of aqueous elec-
trolyte solutions. In electrolyte solutions dynamics and
structure controlled by solvent-solvent, solute-solvent and
solute-solute interactions are evidenced by changes of the
relaxation parameters of the solvent and by the appearance
of modes produced by dipolar solute species. A systematic
investigation of these phenomena is the prerequisite for the
understanding of many fundamental problems of the phys-
ical chemistry of technically important and biological proc-
esses.
In this contribution we present the results of a study on
the complex permittivity of aqueous solutions of cadmium
chloride, perchlorate and sulfate, of magnesium chloride and
sulfate, and of copper chloride and sodium sulfate. The dis-
cussion will be restricted to the properties of the solvent and
the modifications due to the ion-solvent interactions. The
contributions of specific solute-solute interactions to the
complex permittivity spectrum leading to the formation of
ion pairs of CdS04. MgS04, CdC12,CuC12,and Na2S04will
be discussed in a subsequent publication.
2. Experimental
2.1. Complex Permittivity Measurements
In the actual investigation the complex permittivity of the solu-
tions was determined at 25 to 31 spot frequencies in the range
0.95 I v/GHz I 89 with the help of one coaxial (0.95 to 2.5 G H z )
and five waveguide apparatus (4 to 89 GHz) using the method of
travelling waves. This method known to give highly precise results,
interferometrically probes the wavelength AM and in an independent
experiment the attenuation coefficient a of the electromagnetic wave
of frequency v transmitted in the sample-filled cell. Details of the
equipment and the measurement procedure are given in Refs. [8,9].
The Maxwell equations of electrodynamics show that for elec-
trically conducting samples, such as electrolyte solutions, a “gcn-
eralized” permittivity is the only quantity directly accessible in a
dielectric experiment
R ((1))
rj(w) = C(w) - i-.
(OEg
In Eq. ( I ) R ( Q ) is the frequency dependent conductivity of the sam-
ple. The separation of E(w) and R(w) requires assumptions. We
follow the common procedure taking R as independent of frequency
with K ’ ( w ) = ti and ti’’(cr)) = 0. ti is the conductivity determined
with a precision of 0.2% at quasi-static frequcncies with standard
methods of our laboratory [lo, 111; data are summarized in column
3 of Table 2.
In all cxperiments the temperature was 25.00 0.01 ‘ T . Taking
into account all sources of error the precision is approximately
1.5% for q’ and 2.5% for v’’ at v < 40 GHz and about 3% for
both quantities at higher frequencies. A discussion of the accuracy
of the equipment and possible error sources is given in Ref. [S].
989
2.2. Materials
Water was purified with the help of a Millipore” line yielding
samples with a conductivity of less than 2 . l o - ’ S m-’. CdClz
(Merck, for synthesis) was recrystallized twice from conductivity
water and dried for two days at 150 ’C. Cd(C104)2was synthesized
from stoichiometric amounts of CdCO, (Merck, reinst) and per-
chloric acid (60%, Merck, p. a.) [l2]; the product was recrystallized
from conductivity water. The other salts, CuCI2 . 2 H 2 0 (Merck,
p.a.), Na2S04 (Merck, p.a.), MgS04 . 7 H 2 0 (Merck, p.a.), and
3 C d S 0 4 . 8 H z O (Merck, p. a,), were used without further purifi-
cation. The concentrations of the solutions of the dry salts CdCI2
and Na2S04 were determined by weight, those of the Cd(C104)2,
CdS04, MgS04, and MgC12 solutions were obtained by complex-
ometric titration with EDTA. The concentration of CuCI2 was de-
termined by potentiometric titration with standard 0.1 N AgNO,
solution.
3. Results and Data Analysis
For the interpretation of dielectric relaxation experiments a de-
scription of the complex permittivity spectrum with the help of an
appropriate semi-empirical relaxation model is necessary. Gencrally
data fits can be carried out with the help of superimposed Havriliak-
Negami equations
where it is assumed that a sequence of n distinct processes contrib-
utes to the total spectrum with individual relaxation times r, and
weight factors y,. The relaxation parameters are arranged in nu-
merical order, beginning at the slowest relaxation time. The para-
/?,
meters a, and characterize symmetrical (Cole-Cole equation, 0 <
a, < I , /?, = 1) or asymmetrical relaxation-time distributions (Cole-
Davidson equation, a, = 0,O < /?, < 1) of process j; m, = 0, /?,= 1
reproduces a series of Debye relaxation processes.
The data analysis was executed by the fit of m measured data
) various relaxation models (1 I n I 4) by min-
triples ( v , ” , ~ ”to
imization of the error function x*.
(3)
where I is the number of adjustable parameters and U ( E ~ are ) the
respective standard deviations. In the following discussion we adopt
a clear-cut distinction between the relaxation parameters of solvcnt
and solute. The numbering of the relaxation processes of Eq. (2)
from low to high frequencies is replaced by the index “s” for the
solvent and the solute process is marked by the index “IP”. Then
E, = E,’ is the “static” permittivity of the solvent, T , ~is the time
constant of the slowest solvent relaxation process with dispersion
amplitude ( E , - E , ~ ) etc.. E and E , keep their meaning as “static” and
“infinite frequency” permittivity of the solution. As a consequence
E = E, = 6,’ (j = 1 in Eq. (2)) is valid in the pure solvent spectrum
and in the spectra of electrolyte solutions without ion-pair forma-
tion. For associating electrolytes the slowest relaxation process
(j= 1 in Eq. (2) is that of ion-pair formation, zI = zip, followed by
the slowest solvent process (j = 2 in Eq. (2)) with relaxation time
52 = 5,’ etc., see Tables 1 and 2.
The a priori choice of the “true” relaxation model reflecting the
microscopic properties of the system is not obvious. Different mod-
els may yield fits of comparable quality. With no other information
available from independent methods it is advantageous to prefer
the fit which requires the minimum number of adjustable para-
meters. The parameters also must be constistent within a series of
experiments reaching from the pure solvent to the highest concen-
tration studied for a given electrolyte.
990 J. Barthel et. al.: Dielectric Relaxation of Aqueous Electrolyte Solutions etc.

The actually best water data from our laboratory (yielding 4 = Inclusion of the far-infrared data in the analysis changes the
78.04, rEl = 8.32 ps, asI = 0, Bsl = 1, E , ~= 6.09, rS2= 1.0 ps, aS2 picture, cf. Table l(b) and Fig. 1. Clearly, a single Debye equation
= 0, /Is2 = 1, E, = 4.6) are given in Ref. [S]. Table 1 and Fig. 1 (broken line in Fig. 1) is no longer sufficient to describe the exper-
illustrate the influence of model choice and frequency coverage on imental spectrum between 1.7 GHz and 410 GHz, nor is a sym-
the relaxation parameters. metrical relaxation-time distribution of Cole-Cole type appropriate
(not shown in Fig. 1). Both models exhibit systematic deviations at
high frequencies and thus indicate a fast mode contributing to the
Table 1
Parameters of various relaxation models for pure water at 25°C
relaxation mechanism. A proper fit of the data can only be achieved
with the help of the asymmetric C D distribution or by the super-
position of two Debye equations (2D). Based alone on numerical
model c, rdps a,l AI ~ $ 2 r.dPS x2 arguments from the data analysis a decision in favour of the C D
or the 2D model is difficult. The 2D model yields lower x 2 but has
(a) Data from 1.7 to 89 GHz an additional parameter; also the relative amplitude of the high-
frequency process is only 2% of the total dispersion amplitude
D 78.01 8.26 - - - - 5.63 0.13
( E -Em 1.
CC 77.95 8.26 -0.002 - - - 5.71 0.14
CD
2D
78.05
78.02
8.37
8.31
-
-
0.985
-
-
5.95
-
0.4
5.29
2.6
0.13
0.12 I
40 I I --. a

-
/
\
- \
(b) Data from 1.7 to 410 GHz"
- - 5.21
20
D 77.89 8.18 - - 0.17
CC 78.15 8.19 0.007 - - - 5.05 0.15
CD 78.08 8.53 - 0.962 - - 4.67 0.12
2D 78.04 8.32 - - 6.09 1.0 4.57 0.10 0
~ ~~
40
Relaxation parameters E,, 7,. a,, /3, and xz for D: Debye equation, CC: Cole-
Cole equation, CD: Cole-Davidson equation, 2D: superposition of 2 Debye
I -1
I
equations; O' FIR data from Ref. [13].
20 ' % '\ I 1
80 40 \

0 I
60 30

40 20
C"

20 10

0 20 40 00 80
-1
n n

-
2 5 1 0 50 100 500
frequency
Fig. 1 GHz
Dielectric dispersion ( ~ ' ( v ) )and loss ( ~ " ( v ) )spectrum of water at
25°C. The solid line is calculated with a two Debye relaxation
model and the broken line with a single Debye model using the
parameters of Table 1 (b). x : data of this work, + : interpolated
data of Hasted et al. [13]
The data analysis underlying Table 1 and Fig. 1 is performed
with (a) only data of our laboratory in the range 1.7 5 v/GHz 5
89 and (b) with the inclusion of FIR data between 170 and 410
GHz, published by Hasted et al. [13]. For set (a) Debye (D), Cole-
Cole (CC), and Cole-Davidson (CD) equations yield almost equal
values of x2. The distribution parameter a obtained for the CC fit
is close to zero showing that the assumption of a symmetric relax-
ation time distribution can be ruled out. Similarly, the unsymmetric
Cole-Davidson distribution achieves no significant improvement of
the Debye fit. Above 70 GHz the experimental 8'' data slightly
deviate from the fitting curve, indicating an additional high-fre-
quency process. Indeed, a fit with two superimposed Debye equa-
tions (2D) yields a slightly better x 2 ; however, it requires two ad-
ditional parameters when compared to the single Debye model.
Also the relaxation frequency (2rr rS2)-'is outside the covered fre-
quency range. Therefore with the data of our laboratory alone it is
impossible to decide which relaxation model applies for water, but
obviously a single Debye process is sufficient up to 70 GHz.
Fig. 2
Argand diagrams of(a) CdCI2, 1.0729 mol dm-I, (b) MgS04, 1.1012
mol dm-', and (c) Cd(C104)2,1.0187 mol dm-I aqueous solutions
at 25°C with underlying individual processes (full lines). The broken
line shows the diagram of pure water
The analysis of the data of electrolyte solutions yields two types
of diagrams, see Fig. 2. Solutions of Cd(C104)2and MgCI2 must be
distinguished from those of CdC12, CdS04, MgS04, Na2S04,and
CuC12. The spectra of the first class exhibit only the relaxation
processes of the solvent. The second class shows an additional dis-
persion step at the low-frequency side, which unambiguously must
be attributed to the formation of a polar solute species. Detailed
information on the solute relaxation process will be given in a
subsequent paper. Although only data up to 89 GHz are available
for the solutions a satisfactory fit of the data is - like for pure
water - only possible with the 2D or the CD model for the solvent
dispersion, yielding comparable x for all solutions. Due to severe
corrosion problems with CuCI2 only three concentrations were in-
vestigated at lower frequencies (v,,, = 39 GHz); we therefore usc
a single Debye process to fit the water contribution of CuC12 so-
lutions.
At low concentrations insuffcient frequency coverage leads to a
large scatter of the relaxation parameters when all model para-
meters are adjusted. Nevertheless, the infinite frequency permittivity
is found to be independent of concentration and nature of the elec-
trolyte. This observation is corroborated by Bennouna et al. [14]
 J. Barthel et. al.: Dielectric Relaxation of Aqueous Electrolyte Solutions etc. 991

who observe a plateau of the FIR refractive index of water for
wavenumbers V I 80 cm-’ and find no difference in the refractive
indicies of water and an 8 molar NaC104 solution for 7 150
cm-’. Therefore we decided to fix E, at the value obtained for pure
water, E, = 4.6, thus avoiding repercussions on the other fitting
parameters. This is marked by the superscript “f” in Table 2. Under
this condition the 2D model for the solvent (relaxation times with
subscript “sl” and “s2”) plus D for the solute (subscript “IP”) yields
more consistent parameters at variable electrolyte concentration
than the (CD + D) model. For the (CD + D) model the relaxation
times show a larger scatter and x 2 slightly increases lending credit
to the assumption of a distinct high-frequency dispersion step.
Due to the small dispersion amplitude of the solute, ( E - E ~ ) , at
the lowest concentration it was also necessary to fix the static per-
mittivity E of MgS04 and Na2S04to get reasonable values of E, TIP
and E ~ .The corresponding values with superscript “f” given in
Table 2 were interpolated with the help of appropriate polynomials
fitted to E = f ( c ) .
Table 2
Relaxation p;ir;imelers ror aqueou\ solutions or \;trious eleclrolytes at 22 C
For the solvent only the parameters of the 2D model are given
in Table 2 @,,r,,, E , ~ , rs2,E ~ ) these
; parameters are the base for the
further discussion. The relaxation parameters of the solutes ob-
tained for CdC12, CdS04, MgS04, Na2S04,and CuC12 solutions,
namely E, TIP, E~~~ = E,, given in Table 2, will be discussed in the
subsequent publication.
4. Discussion
4.1. The Relaxation Model of Pure Water
Pure water is a recommended reference liquid for the cal-
ibration of experimental set-ups in the microwave region
[S], for which Kaatze and Uhlendorf [lS] give a compre-
hensive study of literature data. Their fitting curve, obtained
with a single Debye equation, reproduces our data at fre-

electrolyte 2 - K
&
moldm-’ Sm-’

- 0 - - - 78.04 8.32 6.09 1.o 4.57 0.1

CdC12 0.01998 0.2840 78.39 299 77.61 8.40 6.57 1.4 4.6‘ 0.1
0.04872 0.5535 78.52 170 76.86 8.35 6.77 1.5 4.6‘ 0.08
0.09902 0.9102 78.43 146 76.08 8.44 7.87 2.0 4.6‘ 0.05
0.29845 1.7988 80.36 114 72.78 8.31 7.35 1.5 4.6‘ 0.1
0.51 315 2.3238 81.67 93.1 69.72 8.22 7.72 1.5 4.6‘ 0.1
0.7867 2.7406 85.75 106.8 66.55 8.25 8.20 1.6 4.6‘ 0.2
1.0729 2.8722 88.67 101.2 63.88 8.13 8.61 1.5 4.6‘ 0.1
1.4549 2.9108 93.59 11 5.4 61.02 8.30 9.76 1.6 4.6‘ 0.1

CdS04 0.02502 0.2851 79.55 127 76.72 8.33 6.82 1.6 4.6‘ 0.2
0.05362 0.5097 82.67 193 76.05 8.33 6.91 1.5 4.6‘ 0.2
0.1 171 0.9310 83.90 151 74.51 8.32 7.01 1.5 4.6‘ 0.2
0.2502 1.6373 86.37 126.1 71.96 8.37 7.34 1.3 4.6‘ 0.2
0.4916 2.6883 87.78 119.7 67.85 8.51 7.89 1.2 4.6n 0.3
1.1455 4.368 85.14 128.5 59.60 9.23 9.37 1.4 4.6n 0.2

MgS04 0.02950 0.3817 79.63‘ 227 76.79 8.41 6.44 1.5 4.6n 0.2
0.07296 0.8096 82.30 172 75.62 8.50 6.93 1.7 4.6‘ 0.2
0.07744 0.8298 82.84 180 75.17 8.37 6.57 1.5 4.6‘ 0.3
0.3634 2.7163 84.64 129.1 69.02 8.52 7.56 1.5 4.6‘ 0.2
0.6472 3.9983 82.61 113.6 63.88 8.77 8.36 1.6 4.6‘ 0.3
0.8206 4.576 80.00 106.3 61.04 8.79 8.29 1.5 4.6‘ 0.2
1.1012 5.2397 75.73 111.8 57.44 9.03 8.19 1.4 4.6‘ 0.3

Na2S04 0.09943 1.6261 77.43‘ 115 74.86 8.27 7.14 1.7 4.6‘ 0.2
0.29087 3.930 76.16 93.3 70.49 8.21 7.98 1.8 4.6‘ 0.1
0.46440 5.621 73.35 68.8 66.64 8.07 8.16 1.7 4.6‘ 0.3
0.62489 6.955 71.34 67.6 64.06 8.16 8.48 1.4 4.6‘ 0.3
0.97440 9.273 65.12 43.6 57.52 7.94 8.45 1.3 4.6n 0.4

CUClz” 0.4002 5.456 70.89 119 67.03 7.86 - - 6.2 0.5

0.7021 8.073 64.47 34.0 60.50 7.71 - - 6.6 0.2
1.0974 10.233 62.23 48.0 54.97 7.59 - - 7.1 0.2

Cd(C104)2 0.09964 1.8309 - - 74.49 8.24 7.08 1.9 4.6‘ 0.1

0.2926 4.783 - - 68.26 7.89 7.11 1.1 4.6‘ 0.1
0.5773 8.416 - - 60.67 7.58 8.59 1.5 4.6‘ 0.1
1.0187 12.644 - - 50.54 6.88 8.63 1.3 4.6‘ 0.2

MgC12 0.09590 1.7498 ~ - 74.90 8.51 7.41 1.5 4.6‘ 0.4

0.2974 4.684 - - 69.07 8.46 8.14 1.6 4.6‘ 0.3
0.5878 8.081 - - 62.31 8.52 9.35 1.9 4.6‘ 0.3
0.9778 1 1.497 - - 53.75 8.09 8.20 1.4 4.6‘ 0.2

Relaxation model: superposition of 2 o r 3 Debye eqs.; ’:parameter not adjusted; c: molarity; K: specific conductivity; ”: no E-band data available, high
frequency process omitted.
992 J. Barthel ct. al.: Dielectric Relaxation of Aqueous Electrolyte Solutions etc.

quencies 1.7 I v/GHz I 40 within our error limits. Also

the data of Buckmaster et al. [16,17] obtained at about
9 GHz and of Steinhoff et al. [18] at about 3.6 GHz, both
groups claiming highest accessible precision, show devia-
tions from our fitting curve which are smaller than 0.2% in
E’ and 0.5% in d’ and 0.06% in E’ and 0.07% in E”, respec-
tively. Additional literature data between 9 and 135 GHz
[19] confirm the accuracy limits of our experimental set-up
given in section 2 for v < 40 GHz. I i must be noted that
for all fitting models summarized in Table 1 the static per-
mittivity values of water extrapolated from our data in the
microwave region are systematically lower (0.4% for the
2-Debye model) than the results obtained with conventional
techniques, E = 78.36 [15,20].
For higher frequencies (v > 40 GHz) literature data are
scarce and scatter markedly so that they cannot be used to
assess the precision of our data in the 60-90 GHz region.
A detailed discussion of this problem is given in Ref. [a].
Usually the &”-datafrom the literature are larger (up to 10%)
than what is expected from the parameters of our 2-Debye
model. Only Richards and Sheppard [21] recently presented
precise temperature dependent complex permittivities of wa-
ter at 90 GHz which deviate from our fitting curve by only
1.5% in E’ and 0.3% in E“.
One might argue that the assumption of a fast Debye-
type relaxation process suggested by our 70 to 90 GHz re-
sults and the FIR data in the 170 to 410 GHz region [13] 75
is questionable both because the experimental error is fairly
large and other modes, especially hindered translations, 70
commonly assigned to the intense band at 190 cm-’ [22],
might contribute to the water spectrum. Inertial effects can
65
be excluded from the discussion because the librational
modes are observed in the 700 cm-’ region.
On the other hand the 2D model is compatible with
microscopic relaxation mechanisms proposed for water.
Haggis, Hasted and Buchanan [23] assume that 5 types of
H 2 0molecules are present in the liquid phase with fractions
fo,. . . ,f4,forming 0, 1, ..., 4 hydrogen-bonds with their next
neighbours. Whereas molecules with no or one bond are
able to rotate without breaking a bond, the 4- and 3-bonded
molecules must break H-bonds before reorientation. Among
the molecules with two H-bonds the authors distinguish two
types. Those bound with two donor or acceptor sites are
unable to rotate, but the so-called asymmetrical 2-bonded
state with one donor and one acceptor site of the molecule
involved in H-bonds may reorient easily. Ab-initio calcu-
4.2. The Influence of Electrolytes on the Dielectric
lations by Dunning et al. [24] support this assumption. Ac-
Properties of Water
cording to the authors of Ref. [23] the formation of this
asymmetrical 2-bonded state determines the rate of the dom- The Static Permittivity of the Solvent
inating dispersion step, whereas the actual rotation of the The concentration dependence of the static permittivity
molecules in this state is much faster and might be respon- of water in the solution, E,(c), given in column 6 of Table 2,
sible for the fast relaxation process with a characteristic time is shown in Fig. 3. E,(c) decreases with increasing salt addi-
of 1 ps. According to Hasted [25] the 0- and 1-bonded mol- tion and can be fitted to a polynominal of the type
ecules cause an absorption at about 0.05 ps (100 cm-l)
which would be too fast for our second process. &,(C) = &,(O) - 6, . c + Pe * c3’2. (4)
A similar theory was developed by Bertolini et al. [26]
by applying the percolation model of Stanley and Teixeira The decrease results from the interplay of a volume effect
[27] to dielectric relaxation and diffusion in pure water. The (@), irrotational bonding (IB) of the solvent molecules in the
 J. Barthcl et. al.: Dielectric Relaxation of Aqueous Electrolyte Solutions ctc. 993
__ ~- ~

Table 3
Dielectric depression parametera 6, and /), of Eq. (4) and numbers of irrotationally bound solvent molecules Z of aqueous electrolyte solutions
~ ~~~ ~~ ~~~~ .- -

/ dm'
electrolyte 6, / - ( z p"),) Z;;
, mol

CdS04 28.5 12.0 20.6 17.0 15.2 13.7 11.3 10.1

MgSOJ 31.8 12.8 23.8 19.3 17.0 16.1 13.1 11.5
CdCll 22.4 x.9 15.0 11.8 10.2 9.6 1.5 6.4
MgCI? 34.4 10.1 24.3 15.6 11.2 16.0 10.1 7.2
Na:SO, 30.1 9.6 21.2 13.6 9.9 13.9 8.8 6.3
Cd(CIO,), 39.8 12.8 25.1 16.2 11.8 15.5 9.5 6.5
CUCll 38.9 17.0 27.8 19.2 14.9 18.4 12.6 9.8

L: Lestrade model, B: Bruggeman-Kaatre model, con: corrected for kinetic depolarization, with slip (sl) or stick (st) boundary conditions.

vicinity of the ions, and of kinetic depolarization (KD). The-
oretical models have been proposed for the individual ef-
fects, where the equilibrium contributions @ and IB com-
monly are treated together. Assuming additivity of the in-
dividual contributions the limiting slope 6,:, see column 2 in
Table 3, can be written as
ancy can be avoided by the application of the limiting con-
dition c+O to all concentration-dependent quantities of
Eq. (6a). The concentration of the solvent, c,, as a function
of the solution density d is given by the relation

6, = 6: + 6EB+ 6,"" = + 6:" .

where Me, and M , are the molar masses of the electrolyte
The volume effect results from the dilution of the polar sol-
and the solvent. Fitting the solution density to a poly-
vent by the apolar ions ( E z 2). Irrotational bonding of the
nomial of c (d, is the density of the pure solvent)
solvent molecules is caused by the strong electric field at the
surface of the ions which exerts a directing force on the
= ds + tll +

surrounding solvent dipoles reducing thus their ability to

follow the applied external field. This orientation leads to a
yields the limiting solvation number ZE
reduction of the dipole density in comparison to the ana-
lytical concentration and permits the calculation of effective
a1 - Me1
solvation numbers Z . It must be stressed that Z is not di- Z[ = lim
-0
Z L ( c ) = 6:q.
c
CL+ (9)
rectly comparable with the number of solvent molecules in M,
the primary solvation shell of the ions as it is determined
from X-ray and neutron scattering experiments or from The results for 6, = are given in column 3 of Table 3.
computer simulations; Z should rather be compared with The approach of Kaatze [35] starts from Bruggeman's
the primary solvation numbers (PSO) [33] which take into empirical mixing formula [ 3 6 ] for the dilution of a polar
solvent with a non-polar spherical solute of volume fraction
account the dynamical effect of solvation and give the num-
ber of solvent molecules moving- with the ion in the solution. vB and permittivity E,
Two models have been proposed in the literature for the
discussion of the equilibrium contribution 6Eq.
Starting from the Kirkwood-Frohlich equation and as-
(Es(C) - Ee) ' (x) E,(O) 1'3
= (1 - VB) ' (&s(O) - &e) . (10)

suming 6, = h:¶ Lestrade et al. [34] obtained at low elec-

trolyte concentrations An effective solvation number Z e (c) can be calculated from
the difference between the volume fraction uB of hydrated
ZdC) =
C,(C) - C,(O) + CL . c
(6a) ions determined with the help of Eq. (10) and the volume
C fraction D of the unsolvated electrolyte which is obtained
from the molar volume of the pure solvent, @, and the
where
solution density d according to

c, and c denote the molar concentrations of solvent mole-

cules and solute particles in the solution, respectively. Eq. (6) yielding for Z B ( C the
) expression
requires vanishing electrolyte concentration c, but it is com-
monly used in the literature for the calculaton of concen- 0B-D
zB(C) = -.
tration-dependent solvation numbers Z L(c). This discrep- c ' @,
994 J. Barthel et. al.: Dielectric Relaxation of Aqueous Electrolyte Solutions etc.
According to Kaatze the choice of a special mixture formula
is not essential as long as the volume fraction of non-polar
spheres uB is small. Again concentration independent sol-
vation numbers comparable to ZE, Eq. (9), are obtained
under the condition c-0. A Taylor-series expansion of
Eq. (10) at c = 0 yields for the volume fraction of the sol-
vated ions
and the zero-concentration limit ZU, of the Bruggeman num-
ber
CB = - .
1 +
2 E,/E*(O)
3QS E * ( O ) - E , .
The numbers ZU, calculated with our experimental data for
6,: = 6:“ and with E, z 2, as suggested by Kaatze, are given
in column 6 of Table 3.
In comparison with the coordination numbers (CN) from
simulation or scattering experiments, but also with primary
solvation numbers (PSO) given in the literature, cf. columns
2 and 3 of Table 4, both Z ; and ZU, are unreasonably large
for almost all electrolytes. Therefore dielectric saturation
and volume effect alone, with their contribution Seq = 6:
+ 6:’, are not suited to explain the dielectric decrement 6,:.
The equilibrium approaches d o not take into account the
dielectric friction, caused by the moving ion in a dielectric,
which reduces the ionic conductivity and also leads to a
decrease of solvent permittivity, called kinetic depolarization
(KD). According to the continuum theory of Hubbard and
Onsager [37,38], which was confirmed by Hubbard, Co-
lonomos and Wolynes as the limiting case of their micro-
scopic model for large ionic radii [39], the contribution of
kinetic depolarization, d f”, to the decrease of solvent per-
mittivity, A,: = E , ( O ) - E ~ ( C )is, proportional to the conduc-
tivity of the electrolyte and to the relaxation time r,(O) of
the pure solvent
The friction factor p is determined by the hydrodynamic
boundary conditions with p = 1 for stick and p = 2/3 for
slip ionic movement. For water at 25 C (Ebk equals 0.866
Rm and t$h equals 0.577 Qm. Eq. (15a,b) is strictly valid
at the limit of vanishing electrolyte concentration for a sol-
vent with a single Debye-type relaxation. For a relaxation
behaviour governed by a superposition of Deby processes
a modified equation is proposed by lbuki and Nakahara
[40]. Due to the small amplitude and relaxation time of the
high frequency process the results for water can be discussed
with the help of Eq. (15) by inserting ( E , - E ~ ~ )as the solvent
dispersion amplitude and the relaxation time tblwithout
significant error. The assumption of large ionic radii is jus-
tified by the large effective radii, also deduced for small cat-
ions from ionic conductivities, attributed to the solvation
shell moving with the cation [33].
28
24
20
16
12
4 8
4
0 2 4 6 8 1 0 1 2
X
s ,-I
Fig. 4
Dielectric depression AE = ~ ; , ( O ) - E , ( C ) of aqueous electrolyte so-
lutions as a function of specific conductivity ti at 25 C. ( I ) CdCI?,
( 2 ) CdSO.,, (3) MgS04, (4) CuCI2, ( 5 ) Na2S04, (6) Cd(CIO&, (7)
MgCI2.The straight lines stick and slip are calculated according to
the continuum model of kinetic depolarization (Eq. (21)) with re-
spective boundary conditions
Indeed, a linear dependence on ti is observed for the de-
crease of the solvent permittivity, & , ( O ) - E ~ ( C ) , at low con-
centrations. However, the experimental slopes are signifi-
cantly larger than the theoretical value tHOand they are
specific for the electrolyte, in contrast to Eq. (15a,b), cf.
Fig. 4. The strongly associating electrolytes CdCI2, CdS04,
and M g S 0 4(association constant K A > 80 dm3 mol- ’) differ
from the weakly or non-associating electrolytes MgCL,
Cd(C104)2,Na2S04,and CuCI? ( K , < 10 dm3 mol-’) which
are closer to the theoretical prediction.
Obviously, neither irrotational bonding corrected for the
volume effect of the ions, nor kinetic depolarization alone
can predict the magnitude of the experimental dielectric de-
crement. Assuming that the static permittivity of the solvent,
corrected for kinetic depolarization, E? (c), is given by the
relation
for all electrolytes, a corrected dielectric decrement Syris
obtained from the limiting slope which contains the equilib-
rium effects
Table 3 summarizes the corrected ZF and ZE numbcrs
(Zc,Orrand (Z?“) obtained for slip (subscript “sl”) and stick
(subscript “st”) conditions. The corrected solvation numbers
are considerably lower than the uncorrected ones of columns
3 and 6. From the standard deviations of the dielectric dec-
 J. Barthel et. al.: Dielectric Relaxation of Aqueous Electrolyte Solutions etc. 995

rements errors in the order of 1 to 2 units are estimated for
all Z-values given in Table 3.
The comparison of the corrected Z numbers of Table 3
with primary solvation numbers from the literature requires
the separation into ionic contributions
z(c:: A:,:) = v+ Z(C'+)+v-Z(A'-).
For the chloride ion it is known from NMR-relaxation stud-
ies that the residence time and the reorientation time of a
water molecule in its hydration sphere are close to the data
for the bulk solvent [41]. Therefore we may assume that the
C1- ions d o not contribute to irrotational bonding, i.e. take
Z(Cl-) = 0, and obtain the single-ion contributions given
in Table 4. With the exception of (Z',""(Na+)),, z
(Zy(SO:-))sl all corrected data show equal sequences of
the ions and decreasing values of the solvation numbers
( Z y ) s l> (Z',""),, > ( Z ~ " ) )>
, , (Z",""),,. It should be men-
tioned that the splitting into ionic contributions without
correction for kinetic depolarization yields unrealistic and
inconsistent results.
The results show that at the present state of knowledge
the Z y - n u m b e r s with account for kinetic depolarisation
under slip boundary conditions yield the most reasonable
results for aqueous solutions. This is also valid for electrolyte
solutions in methanol [4]. Z y-values exceeding the coor-
dination number suggest that for the ions C d 2 + ,Mg2+ and
(18) probably Cu2+, a second hydration sphere with reduced
water mobility exists, an information which is also inferred
from a detailed analysis of scattering data [48]. A self-con-
sistent approach based on HNC-theory given by Kusalik
and Patey [49] was also tested, but at the present stage no
satisfactory results can be obtained for multiple charged
ions.
9.5
A
9
8.5
8
7.5

7
Table 4
Single ion solvation numbers of this work ( Z )and primary solvation numbers 6.5
(PSO) and coordination numbers (CN) from the literature 0 0.25 0.5 0.75 1 1.25 1.5
C
mol dm-'
-
Fig. 5
CI- 6 [44]; 8.2 [43] 2 + 1 [33] 0*) Or) O*) 0') Relaxation time of the main solvent dispersion step of aqueous
SO:- 8 [45] 1.4, 2.8, 7.9 [42] 4.5 5 3.5 4 solutions as a function of electrolyte concentration at 25°C. (1)
CIO; - 0.3 [42] 2 1 1 0.2 CdS04,(2) MgS04, (3) MgCL (4) CdC12, (5) N a W 4 ,(6) Cd(C104)~
Cd2' 4.4 [46], 6 [47] 10-12.5 [33] 12 10 1.5 6
Mg" 6.0 [43] 14-16 [33] 15 11.5 10 7.5
Cu" 6 [48] 10.5-12.5[33] 19 15 12.5 10 Relaxation Time of the Slow Solvent Process
Na' 6.5 [43] 4 k 1 [33] 4.5 2.5 2.5 1 The dynamics of the main solvent relaxation process is
strongly influenced by electrolytes. Inorganic salts com-
*) Assumption: Z(CI-) = 0; L: Lestrade model, B: Bruggeman-Kaatze
model, con: corrected kinetic depolarization, sl: slip, st: stick boundary monly produce a decrease of the relaxation time tsl,in con-
conditions. trast to ionic solutes with non-polar groups, such as tetraal-
kylammonium salts which increase the relaxation time
[ S O - 541. Fig. 5 exhibits the concentration dependence of
The primary solvation numbers (PSO) of Table 4 are ob- the relaxation times t Sfor
, the systems studied in this paper.
tained from isothermal compressibilities or single-ion con- Decrease as expected is observed only for Cd(C104)2and
ductivities [33,42] and the coordination numbers (CN) stem Na2S04,whereas CdC12 has almost no influence on the wa-
from computer simulations and scattering experiments ter dynamics and for C d S 0 4 and M g S 0 4 the relaxation
[43 -481. The solvation numbers (Z","'),, agree well with the times even increase. Especially interesting is the behaviour
primary hydration numbers from the literature. The as- of the MgC12 solutions which exhibit a shallow maximum.
sumption of ( Z ~ ( C l - ) ) , ,= 2 as the reference value, as With the exception of the approach of Giese, Kaatze and
suggested by the PSO of this ion, yields Lestrade numbers Pottel [55, 561 for aqueous chloride solutions, which does
for the other ions which are smaller than the corresponding not reproduce the results for MgCI2, there is no theoretical
PSO numbers of Table 4, but which are still reasonable. This treatment for the concentration dependence of the cooper-
is not true with the assumption of an unsolvated C10; ion ative relaxation time of aqueous electrolyte solutions in the
as the reference. literature. We also will restrict the discussion to some qual-
A check of the internal consistency is possible for the itative aspects at the time being.
sulfate ion. The sequence C1- -+ CdC12 + C d S 0 4 yields The observed relaxation time 7s1may be understood as
(Zy(SO:-))rl = 5.2, whereas (Zc,""(SO~-)),I = 3.7 is ob- the superposition of the relaxation process of pure water
tained from the series C1- -+ MgClz -+ MgS04. Both values and the reorientation process of the water molecules in the
are acceptable within their error limits. For the copper ion solvation shells of the ions characterized by the reorientation
the results are not satisfactory, due to the insufficient data time of the water molecules in the hydrate spheres, 7::dr, and
at low concentrations. by the average residence time of water molecules in the
996 J. Barthel et. al.: Dielectric Relaxation of Auueous Electrolvte Solutions etc.

solvation shells, T ~ These

~ ~ quantities
. partially are accessible found in the literature, but the fact that the effective solva-
from NMR relaxation experiments and molecular dynamics tion number of (Zc,Orr = 4.5 is significantly smaller
simulations, cf. Table 5. If we assume that the influence of than the C N of 8, determined by X-ray diffraction [45],
cations and anions is independent and neglect the effects of suggests water exchange between the hydration sphere and
ion-pair formation at low concentrations, it is possible to the bulk in the time scale of T ~ ~ .
check the observed shifts of tsl with the data quoted in In analogy, the marked decrease of the relaxation time at
Table 5. increasing Cd(CIO& concentration (curve 6 ) is due to the
CIO; anion. Here it is known from NMR results [58,59]
that the hydration water reorients considerably faster than
Tahle S
Reorientation times. T:!"', and residence times, T,~,, in the hydrate spheres of the bulk water; also the effective solvation number is low,
the ions and in bulk water suggesting rapid exchange.
The slight decrease of zSIfor the Na2S04solutions should
then indicate a distinct increase of the water mobility in the
N a + hydration sphere which counteracts the relaxation time
H?O I 4.5 (286 K) [41] increasing effect of SO:-. However, molecular dynamics
Na ' 2.2 [41] 9.9 (282 K ) [41] simulations yield a larger reorientation time for water in the
2.6 [59] first hydration shell of N a + ions and the residence time
2 10' [57]
5.2 [ S S ] exceeds qt(0) [41]. A possible explanation for this discrep-
0.79 [59] ancy would be a secondary hydration region where the wa-
0.9 [ S S ]
4.5 (287 K) [41]
ter structure is broken [SO] and faster relaxation is possible.
CI -
1.0 [41]
1.3 [SO]
ClOJ 0.03 [59] - -
High-frequency Solvent Relaxation Process
0.4 [ 5 8 ]
The columns 8 - 10 of Table 2 summarize the parameters,
SO: 1.9 [SS] - - cS2,zS2,E , of the high-frequency dispersion step for the elec-
trolyte solutions with the exception of CuC12, where tech-
nical problems prevented a thorough investigation.
According to the literature the reorientation time and the Like for pure water, (csz-c,) is small compared to the
residence time of a water molecule in the vicinity of C1- are dispersion amplitude of the main solvent relaxation process
equal to the relaxation time of bulk water. This observation and its critical frequency v, = ( 2 x t S 2 ) - ' is outside the ac-
was precedingly used to set Z",""(Cl-) = 0. Our measure- cessible frequency range (89 G H z corresponds to 1.8 ps).
ments show that the addition of CdCI2 to water does not Unlike to water, no FIR data are available for the aqueous
change the main relaxation time up to concentrations of electrolyte solutions so that only trends can be given. Within
about 1.4 mol dm-3, see curve 1 of Fig. 5, leading to the experimental accuracy 7,2 depends neither on concentration
conclusion that the Cd2+ ion also has no influence on the nor on the nature of the dissolved electrolyte and an average
water dynamics in the time scale of our experiment, although value of 7,2 = (1.5 k 0.5) ps may be given. The difference
it is strongly solvated. This suggests that 7rcsand ~ k in: the
~ ~ of TS2 = 1.0 ps in pure water to the solution value of 1.5 ps
hydration shell of Cd2+ are much larger than the relaxation is possibly due to the restricted frequency coverage. The
time of bulk water. Unfortunately no appropriate literature corresponding dispersion amplitude shows considerable
data are available to support this conclusion. However, for scatter but roughly doubles when going from pure water to
Mgz+ it is known that the exchange of water molecules in a 1 molar solution. The trends observed for 7,2 and (c,?- c )
the solvation shell is very slow, T~~~ = 2 . 10Whs[57]; Cd2+ are in accordance with the model proposed by Haggis et al.
should behave similarly. The NMR data of Table 5 suggest [23] but actually a detailed interpretation of the high fre-
an increase in the reorientation time of the bound water quency dispersion step is not possible. Precise information
molecules around the magnesium ion which might explain will be available when the frequency coverage of our equip-
the small initial increase of 7,1 for MgCI2, although NMR ment will be extended to higher frequencies and to temper-
and dielectric relaxation experiments probe the reorienta- ature dependent experiments yielding the activation para-
tion of different vectors and the rotation of the solvation- meters of the relaxation processes.
shell water is not isotropic. Nevertheless, the weak concen- Financial support by the "Deutsche Forschungsgemeinschaft" is
tration dependence of 7,( together with large values of gratefully acknowledged.
ZTrrsuggest that at low concentrations Cd2+ and Mg2+
form stable hydration shells which only weakly interact with
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