2486 J. Phys. Chem.

1982, 86, 2486-2490

Dlelectrlc Properties of Electrolyte Solutions. 1. Sodium Iodide in Seven Solvents at

Various Temperatures

Paul Winsor, I V , and Robert H. Cole’

Chemistry Department, Brown University, ProvMence, Rhode Island 029 12 (Received: September 23, 198 1;
I n Final Form: Januaty 7, 1982)

We report results from time domain reflection measurements for complex permittivities of sodium iodide solutions
in methanol, formamide, N-methylformamide, dimethylformamide, dimethylacetamide, propylene carbonate,
and dimethyl sulfoxide at concentrations in the range 0.02-1 M. Most of these are at 25 “C with results for
methanol and propylene carbonate at lower temperatures to -29 “C. The observed relaxation effects in the
range from 100 MHz to 8 GHz were all very nearly of Debye form with relaxation time decreasing slightly with
concentration for the hydrogen-bonding solvents, but significantly larger at the highest concentrations in the
two aprotic solvents. The decreases in static permitivity with concentration are in all cases larger than predicted
by the Hubbardansager theory of kinetic depolarizationand the differences correlate better with solvent molecule
dipole moments than with static solvent permittivity.

Introduction The purpose of the work reported here is to explore such

Until recently, decreases in static permittivity and
changes in relaxation properties of solutions with in-
creasing concentrations of ions have been interpreted in
terms of static effects of ion interactions with polar solvent
molecules. Models which have been proposed include
saturation of a solvent continuum near the ions, irrota-
tional binding of solvent molecules to ions, and polarizable
ion spheres in a polar continuum; these have been reviewed
by Hastedl and by Lestrade, Badiali, and Cachet.2
In 1977, Hubbard and Onsager3 pointed out another
effect as a result of changing electric fields of ions and
solvent dipoles moving in applied electric fields, with
counterpolarization of both from the finite dielectric re-
laxation time of the solvent molecules. The Hubbard-
Onsager4v5(HO) theory of this kinetic depolarization effect
for a continuum model predicts a decrease in solution
permittivity proportional to the product of solution con-
ductance and dielectric relaxation time 7D. The first ex-
perimental results to be compared with the HO theory, by
Van Beek and Mandel: showed that most of the observed
decrements for salts in methanol and an appreciable
fraction of decrements in water were accounted for by the
theory. A striking confirmation was found by Hall and
Cole6for sulfuric acid solutions with dipolar ions produced
by an excess of either H,O or SO3, as the very large de-
crements for given ion concentrations result in the kinetic
theory from the very long relaxation time ( T =~ 340 ps as
compared to 8 ps for water and 50 ps for methanol), while
the static models either predict negligible effects or require
ridiculuously large solvation numbers.
The solvent systems just mentioned are all hydrogen
bonded. The sulfuric acid system is the most highly
structured, yet most closely follows the HO theory pre-
dictions even though the theory is based on the treatment
of the solvent as a continuum fluid. Clearly further studies
are in order to define the circumtances under which the
HO theory is fully applicable or fails.
(1) Hasted, J. C. “Aqueous Dielectrics”; Chapman and Hall: London,
1973.
(2) Lestrade, J. C.; Badiali, J. P.; Cachet, H. “Dielectric and Related
Molecular Processes”; Chemical Society: London, 1975; Chapter 3.
(3) Hubbard, J.; Onssger, L.; Van Beck, W. M.; Mandel, M. Proc. Natl.
Acad. Sci. U.S.A. 94, 401 1977, 401.
(4) Hubbard, J.; Onsager, L. J. Chem. Phys. 67, 1977, 4850.
(5) Hubbard, J. J. Chem. Phys. 68, 1978, 1649.
(6) Hall, D. G.; Cole, R.H. J. Phys. Chem. 85, 1981, 1065.
questions by a systematic study of the dielectric behavior
of electrolyte solutions employing a single salt, NaI, in
several solvents with varying molecular weight, molecular
dipole moment, and macroscopic dielectric behavior. The
choice of NaI was made on the basis of solubility in a
variety of solvents and amount of other relevant data in
the literature for the solutions. The dielectric behavior
of the aprotic polar solvents selected, as modified by the
addition of conductive salts, had been studied only at
frequencies above 1.6 GHz and at excessively high incre-
ments of salt concentration (0.5-2 M).’ Because of recent
improvements in time domain reflectometry (TDR)8over
the methods described in ref 6, it has become possible to
study with reasonable precision systems with high static
permittivities and relaxation times greater than 30 ps.
The solvents used in this study are, in order of increasing
molecular weight, methanol (MeOH), formamide (F),
N-methylformamide (NMF), dimethyl sulfoxide (Me2SO),
dimethylacetamide (DMA),and propylene carbonate (PC).
Of these, only the first three are “associated” by hydrogen
bonding, while the amides differ only by the successive
addition of methyl groups and have nearly the same dipole
moments (3.7-3.8 D). In addition, measurements over the
range from 25 to -29 “C were made for the two solvents
with the most widely differing characteristics: PC, which
is the largest (mol wt = 102),most polar (p = 4.98 D), and
aprotic; and MeOH (mol wt = 32), the least polar GL = 1.70
D), and hydrogen bonded. In a companion paper we report
a study of several alkali halides in methanol to test the
molecular theory of kinetic depolarization developed by
Hubbard, Colonomos, and W ~ l y n e s . ~
Experimental Method
The arrangement employed here for TDR measurements
is open circuit sample termination, where the sample is
placed at the end of a 50-ohm coaxial line. The incident
pulse Vo(t)at the input of the empty cell is reflected un-
changed as V ( t )= Vo(t- 2d/c), where d is the effective
electrical length of the cell inner conductor (actual length
plus apparent length due to the inner conductor end ca-
(7) Barthel, J.; Behret, H.; Schmithals; F. Ber. Bunsenges. Phys.
Chem. 75, 1971, 305.
(8)Cole, R. H.; Winsor, P.; Mashimo, S. J.Phys. Chem. 84, 1980,786.
(9) Hubbard, J.; Colonomos, P.; Wolynes; P. G. J. Chem. Phys. 71,
1979, 2652.

0022-3654182f2086-2486$01.25/0 0 1982 American Chemical Society

Dielectric Properties of Electrolyte Solutions The Journal of Physical Chemistry, Vol. 86, No. 13, 1982 2487

pacitance). Denoting the reflection from the cell fded with - 40 I

sample by R(t),the total permittivity tt* of the sample is
I
given by the simple relation6 0.10 M NaI in Methanol, I
25'C d
I
- 30 I
I
where uo and r are the Laplace transforms of Vo(t)and I
R(t),respectively. The effects of propagation and multiple
reflections in the finite sample length are given by the
factor f ( 2 ) N 1- az2,where 2 = (wd/c)tt*1/2, for the short
sample cell (d = 0.7 mm) used here. The V ( t )and R ( t )
records are obtained by sampling oscilloscope and sig-
nal-averaging techniques; these, as well as the numerical
methods used to evaluate the transforms uo + r and uo -
r are described in detail elsewhere.8J0
Since the total permittivity of a solution with dc con-

w -
ductance diverges as (iw)-l in the limit of low frequency,
0, it is useful to calculate a sample permittivity t* that
is the total permittivity minus the permittivity attributable 5 10 20 30
to dc conductance. Thus, we have
4TUo Flgure 1. Complex permittivities for 0.10 M NaI in metanoi at 25 "C.
e* = -- (2) Open and filled clrcles are values before and after subtracting dc
iw conductance contribution to t"(w). Solld curve is a "Debye semicircle".
where uo is the dc specific conductance in esu. The "static"

limit E*(W -
permittivity e8 for conducting solutions is then simply the
0). The specific conductance is proportional

- R ( t ) and QO(t)= Vo(t) R(t) as t -

to P,/Q- where P, and Q m are the limits of Po@)= Vo(t)
+ m. For a cell
constant d defined in terms of a sample cell with the same 2or
No I in Methanol, 25OC

4 6 GHz
2 2 GHz
inner to outer conductor diameter ratio m the 50-ohm line,
the specific conductance (esu) is simply
E" 'C

The cell constants d and a were found by calibration

with water (to = 78.6 at 25 "C) as the standard of known
permittivity; this gave d = 0.694 mm and a = 1.5. The f ( 2 )
correction fails when 121I0.4, which corresponds to 3.9
GHz for water and 8 GHz for methanol at 25 "C.
The sample cell arrangement was similar to that de-
scribed by Hall and Cole: the principal differences being
in the arrangements for temperature measurement and
control. The temperatures 25 and 1 "C were maintained
by water and water/crushed ice baths. Below 0 "C, tem-
perature was maintained by dry ice slushes in both the cell
bath and a cooling jacket surrounding the coaxial line
below the bath, using 1-octanol for -15 "C and 2 -octanol
for -29 "C. The temperature was monitored by a two-
thermister probe and resistor network combination which
gave a direct digital readout down to 0 "C, below which
calibration with the melting points of known standards wm
necessary. Temperature precision was within 0.3 "C over
the whole temperature range and within 0.1 "C at room
temperature.
Since the purpose of this work was to measure relative
changes in permittivity on addition of electrolytes to
solvents rather than exact values, no special effort was
made to purify the commerically obtained solvents.
However, the solvents were assayed for water by Karl
Fisher Titration. The solvents used in the preparation of
the NaI solutions were methanol, Fisher certified ACS
(<0.1% H,O); formamide, Aldrich (<0.1% HzO, ca. 0.15
M ammonium formate); N-methylformamide,Aldrich 99%
(0.1% H20);dimethylformamide, B & A "reagent" (0.8%
H20);dimethyl sulfoxide, Mallinckrodt Analytical reagent
(<0.1% HzO); dimethylacetamide, Aldrich 99% (0.25%
H,O); and propylene carbonate, Aldrich 99% (<O.1% HzO)
or Fisher 98% (<0.1% HzO). Also, a series of NaI solu-
0 10 20 30 40
E'
Flgure 2. Complex permittivities of methanol solutions at 25 "C as
a function of NaI concentration: pure solvent (0),0.2 M (+), 0.5 M
(O), 1.0 M (X).
tions were prepared by using DMA solvent with water
content increased to 0.8%. The sodium iodide used was
either "Baker analyzed" reagent grade or Fisher "certified"
reagent grade, both with <0.01% listed impurities. Two
solutions of 0.15 and 0.30 M ammonium formate (Fisher
97%) added to formamide were included to assess the
effect of this impurity.
Results
The behavior of the total permittivity et* and permit-
tivity e* after subtracting the dc conductance term are
shown in Figure 1for a representative solution, 0.1 M NaI
in MeOH at 25 "C. In this and the other systems studied,
the deviations from simple Debye behavior indicated by
the semicircle are too small and variable to be significant,
and the data have therefore been represented by the Debye
equation
The effect of added salt and increasing conductance for
NaI in MeOH is shown in the complex plane plots oftf'
vs. t f in Figure 2 for four other concentrations; these
demonstrate the expected decrease in static permittivity
tgwith little change in high-frequency permittivity t, and
relaxation time TD. Similar patterns of behavior were
2488 The Journal of Physical Chemistty, Vol. 86,No. 13, 7982 Winsor and Cole

1 TABLE 11: Dielectric Parameters of NaI-Propylene

Carbonate Solutions
C N ~ , K , ohm''
t, "C M m-' fS Em Tn, PS
25 0" 65.8 12.5 45
0.05" 0.104 64.1 12.5 47
o.loO 0.186 63.7 12.5 48
0.20" 0.323 60.4 13.0 49
0.50" 0.577 57.3 13.0 59
1.O0 0.715 53.2 14.0 70
25 0 64.9 12.5 44
0.10 0.207 61.5 12.5 45
0.20 0.350 59.8 12.5 48
0.35 0.493 57.3 12.5 55
1 0 71.2 12.7 71
0.10 0.139 66.5 12.5 75
0.20 0.230 64.8 12.3 76
0.35 0.304 62.0 12.0 82
-15 0 75.5 12.0 105
0.10 0.097 70.0 11.5 100
0.21 0.157 66.3 11.7 102
0.36 0.220 63.2 11.3 115
-29 0 78.3 9.7 141
0.10 0.052 74.8 12.2 160
Flgure 3. Plots of t' vs. ut" (lO1os-l) for solutions of NaI in methand 0.21 0.096 70.5 9.7 161
and propylene carbonate at 25 OC. In the lower plots for methanol, 0.37 0.120 67.8 11.2 198
the open circles are obtained by numerical integration of the reflection
data to 860 ps with an extrapolated exponential decay thereafter, the a These solutions were prepared with Aldrich 99% sol-
X's by numerical integration to 2000 ps plus an exponential decay. In vent (<0.1% H,O by Karl Fischer titration), all others with
the upper plots for propylene carbonate: solvent (0),0.2 M (+), 0.5 Fisher 98% solvent.
M (0).
TABLE 111: Dielectric Parameters of Solutions in
TABLE I: Dielectric Parameters of Formamide and N-Methylformamide at 25 "C
NaI-Methanol Solutions
K,ohm-'
CNaI, K, ohm-' added salt c, M m-l f S e- 7D,Ps
t, "C M m-
Formamide
25 0 0.310 104.5 8" 36
0.02 0.180 31.7 7.4 54 NH,COOH 0.15 0.587 102 34
0.04 0.295 32.2 8.2 55 NH,COOH 0.30 0.823 99.5 38
0.10 0.659 29.7 7.9 56 0.322 103.5 36
0.20 1.16 27.7 8.7 61 NaI 0.20 0.653 98.5 37
0.50 2.30 22.2 8.3 55 Na I 0.40 0.945 95 36
1.00 3.63 16.9 8.3 48 NaI 0.70 1.21 88 33
25 0 33.1 7.2 52
0.02 0.164 32.4
N-Methylformamide
7.2 55
0.038 181 10 123
0.04 0.303 31.6 7.5 55
0.06 0.432 31.0 8.2 56
NaI 0.20 0.716 149 13 121
0.10 0.665 30.1 8.7 63
NaI 0.40 1.191 125 12 110
1 0 37.3 6.9 85
NaI 0.70 1.667 100 13 111
0.06 0.347 33.9 7.0 85 " Estimated from ref 7
0.16 0.746 30.8 7.6 88
0.33 1.26 26.8 8.0 84 TABLE IV: Dielectric Parameters of Solutions of NaI
-1 5 0 41.5 7.7 128 in DMF, DMA, and Me,SO at 25 "C
0.06 0.277 37.8 7.2 125
0.17 0.588 33.3 7.5 121 solvent K, ohm-'
0.34 0.975 28.7 7.7 116 (%H,O) c,M m- ' ES E, T D , PS
-29 0 44.0 7.2 159 DMF (0.8) 37.1 5.0" 13.5
0.06 0.237 39.1 7.3 152
0.04 0.24 7 37.5 11.5
0.17 0.487 35.2 7.4 160
0.34
0.10 0.528 37.5 12.5
0.844 29.2 7.6 147
0.20 0.940 36.3 13.5
found for the other solvents. In the case of PC, the range 0.40 0.155 35.1 18.5
of measurement (f < 4 GHz) defined only about half the DMA (0.25) 38.6 5.0" 15
0.20 0.0771 35.1 17
total dispersion at 25 " C , but measurements at lower 0.40 0.120 32.9 22.5
temperatures giving more complete coverage showed no 0.70 0.151 29.7 24
significant deviations from Debye behavior. DMA (0.80) 39.3 5.0a 15.5
For solvents in which most of the relaxation was mea- 0.04 0.208 37.9 16
sured, relaxation times 7 D were determined by plots of d 0.10 0.441 37.3 17
vs. ut", which give straight lines of slope -7D if eq 4 is 0.20 0.731 36.1 20
0.40 1.17 34.4 20
satisfied. For others (DMF, DMA, Me,SO, F), the slopes Me,SO (0.1) 47.1 5.7a 19.4
of plots of t"/(t' - em) vs. w gave better values of T D on 0.04 0.116 47.1 19.3
using literature values for t, or other sufficiently accurate 0.10 0.268 46.1 19.7
estimates for these systems in which t, << e,. Repre- 0.20 0.475 44.7 20.4
sentative plots of t' vs. ut" are shown in Figure 3. 0.50 0.890 40.7 23.0
Representative values of conductance and dielectric 1.00 1.049 35.4 29.0
parameters for all the solutions studied are given in Tables " Estimated from ref 7.
Dielectric Properties of Electrolyte Solutions The Journal of Physical Chemistry, Vol. 86, No. 13, 1982 2489

I-IV. Tables I and I1 give values for NaI in MeOH and

PC at four temperatures from 25 to -29 "C. Table In gives
values for NaI in NMF and for NaI and NH4COOH in F.
The last were obtained to estimate the amounts of NH4-
COOH present as principal contaminant in unpurified
formamide;" the increases in specific conductance indicate
that the solvent used was 0.15 M in NH,COOH and ex- 70
trapolation to zero conductance gives es and 108 in rea- No1 in PC125C
sonable agreement with the literature value 109.5.' Table ,- - ----_ - - - - _ -
IV gives the results for the other solvents; the results for
-_
DMA show that change in water content from 0.25 to 0.8% 60
had no significant effect on rD or the decrements in e, with
increasing concentrations of NaI. 0

1 1 1 I
The uncertainties in measured static permittivities e, 50 1

result principally from relative timing errors in the TDR

method.8 These increase for high sample conductances as
can be deduced from Figure 1, but for specific conduc-
tances less than 3.8 X ( P J Q m< 1with d = 0.694 mm)
the uncertainties in e, are less than 1 or f0.3% and the
uncertainties in rD are less than 8%.
Discussion
The most common explanation of decreasing static
permittivity es of electrolytes with increasing ion concen- Figure 4. Plots of static permittivity vs. specific conductance for
trations has been in terms of models of solvation or solutions in formamide, propylene carbonate, and methanol at 25 O C .
"irrotational binding"' of neighboring solvent molecules The filled circles in the upper plot are for NaI in formamide, the open
by the ions. Hall and Cole6pointed out that only a small circles for ammonium fonnate in formamide. The dashed lines are the
predictions of the HO theory for p = 1.
fraction of the very large decrements they obtained for
sulfuric acid solutions could be accounted for by any TABLE V : Solvent Parameters and Ratios of Observed
reasonable number of solvated molecules per ion, and a Decrements to Decrements Predicted b y the
similar situation is found in the present results for MeOH. HO Theory at 25 "C
If the equation proposed by Lestrade, Badiali, and Cachet2 A E-
is used, for example, the mean solvation numbers per ion mol (expt)/
pair in methanol are from 25 to 30 in MeOH. For a 0.5 solvent wt I.1, D eS Ae(H0)
M solution of NaI in MeOH, such solvation numbers would CH,OH (MeOH) 32 1.70 33.2 1.5
indicate by Hasted et al's equation12that 50% of the so-

-
HCONH, ( F ) 45 3.73 109.5 6.9
lution volume is taken up by solvation spheres. For sul- HCONHCH, (NMF) 59 3.83 182.4 5.7
furic acid solutions, a nearly quantitative agreement with HCON(CH,), (DMD) 73 3.86 37.1 $1.5
the Hubbard-Onsager formula for the kinetic depolari- CH,CON(CH,), (DMA) 87 3.81 38.6 5.0
zation effect was found, and it is appropriate first to (CH3)2S0 78 3.96 47.1 5.0
compare the present results with this theory. OCHCH,CH,OCO (PC) 102 4.98 65.8 6.1
The Hubbard-Onsager prediction for the decrease in
dielectric constant, At, on addition of conducting electro-
TABLE VI: Ratios of Observed to HO Theory
lytes is given by the relation (as corrected by Wolynes et Decrements in Methanol and Propylene Carbonate
a1.9) Solutions as a Function of Temperature
8a ( e , - e,) t, "C 25 1 -15 -29
Ae = - 3 p - 7 ~ 0 0 (5)
€8 Ae(expt)/Ae(HO) in MeOH 1.50 1.65 1.70 1.80
Ae(expt)/Ae(HO) in PC 5.7 6.9 8.5 8.9
where E,, e,, and T D refer to the pure solvent dielectric
parameters, and the specificconductance 6 in electrostatic tional to the specific conductance as long as the solution
units is given by uo = 9 X 10l1 K , where K is the specific relaxation times were nearly the same as for pure solvent.
conductance in ohm-' cm-'. The parameter p is unity for This is shown in the plots of Figure 4 for solutions of NaI
slip and 312 for stick boundary conditions in the H-D in the very different solvents formamide, propylene car-
ion-solvent continuum model. We assume that the slip bonate, and methanol. This is qualitatively as predicted
condition is more appropriate for spherical ions, and set by the HO theory, but the observed decrements are greater
p = 1 for comparison of the results with eq 5. Another than predicted from eq 5 with p = 1 by factors ranging
prediction of the theory is the onset of faster relaxation from 1.5 to 5, as listed in Table V for all solvents at 25 "C.
processes; if these cannot be resolved from the slower It is seen from Table V that there is no correlation with
principal relaxation, the effect may be to produce an ap- solvent permittivity, but, with DMF excepted, the decre-
parent relaxation time shorter than that of the pure sol- ments are much larger for solvent molecules with large
vent. dipole moments regardless of extent of association in the
For all solutions measured in this work, the decreases liquid, as judged by relative values of e, for example.
in static permittivity E, were found to be linearly propor- The ratios Ae(expt)/Ae(HO) listed in Table VI for
~ ~~ ~ methanol and propylene carbonate solutions increase
(IO) Cole, R. H.; Winsor, P. "Fourier, Hadamard, and Hilbert Trans- significantly at lower temperatures, as would be expected
forms in Chemistry";Plenum: New York, 1981; pp 183-206. if the difference between At(expt) and At(H0) is the result
(11) Verhoek, F. H. J. Chem. SOC.58, 1936, 2577.
(12) Haggis, G. H.; Hasted, J. B.; Buchanan, t. J. J.Chem. Phys. 20, of increased irrotational binding by stronger ion-dipole
1952, 1452. forces relative to thermal energy kT. The larger decre-
2490 The Journal of Physical Chemistry, Vol. 86, No. 13, 1982
50
No1 in DMS0,25C
45
CS
10.5M
40
K(ohm-'m-')
b1.C
35; .2 .4 . 6 , 8 1'0
Flgure 5. Static permittivity of NaI in Me,SO at 25 "C plotted against
specific conductance. Dashed line is the prediction of HO theory for
p = 1.
ments for the more strongly polar solvent molecules are
also consistent with attributing the excess to solvation by
ion-dipole forces, but we have found no very convincing
explanation for the exceptional behavior of DMF solutions
in this respect. If the observed differences At(expt) -
Ae(H0) are attributed to solvation effects, these numbers
could be compared with predictions of various models
which have been proposed. Such calculations would ob-
viously give smaller and more reasonable solvation num-
bers,particularly for methanol solutions, but the legitimacy
of assuming additivity of static and kinetic effects is
doubtful and can only properly be decided by a unified
theoretical treatment, as pointed out by Hubbard, Colo-
nomos, and Wolynes.
With one exception, the linear decrease in e, with in-
creasing conductivity persists to remarkably high ion
concentrations with decrements as large as half the static
solvent permittivity. The exceptional behavior of the
M e 8 0 solutions is shown in Figure 5. Another indication
of increasingly complex behavior in MezSO and the other
aprotic solvent PC is the systematic increase of solution
relaxation time 71) with ion concentration, by 40% for 1.0
M NaI in Me2S0 and 30% for 0.5 M NaI in PC, both at
25 "C. From Table IV, there are smaller increases in 7 D
for the most concentrated DMF and DMA solutions, but
for the hydrogen bonded solvents there are small decreases
(<12% at the highest concentrations). There are indica-
tions of maxima in 7 vs. K for MeOH and F, but the
changes are not much greater than estimated precision of
the data, and further refinements of the experimental
method would be required to establish such an effect.
We have found no indications of significant deviations
from Debye relaxation behavior or of more than one re-
laxation process in any of the systems studied. The sul-
furic acid data of Hall and Cole did show a relatively small
Winsor and Cole
faster relaxation, as indicated by the Hubbard-Onsager
theory* with no calculation of expected magnitude avail-
able, but it was concluded that this secondary process was
more reasonably attributed to solvent structure effects.
Another possible source of dielectric relaxation effects
in electrolytes is from ion-ion interactions. The classic
Debye-Falkenhagen theory13of dilute solutions predicts
an increase in permittivity proportional to the square root
of ion councentration which relaxes at or near the Maxwell
time 7 M = ts/4?ru0(esu). The maximum loss '',E from this
process is predicted to occur at frequency w, = 2 . 2 ~ ~ for
-'
1:l salts. For NaI in methanol, this frequency is low
enough compared to TD-' for concentrations below 0.1 M
that any appreciable contribution would be observable, in
plots of t' vs. ut'' for example. We have found no such
indications for any of our solutions in the range 0.02-0.1
M and estimate from a detailed analysis that the dielectric
increment must be less than 0.2 for 0.02 M NaI in MeOH,
which is less than one-quarter of Mandel and Van Beeks
e ~ t i m a t e .We
~ did find slight increases (-0.04) in e, for
the 0.04-0.10 M solutions of NaI in DMF with 0.8% water,
but they are too small to be considered significant.
In conclusion, we find that the dielectric decrements
produced by NaI in methanol are some 50% greater at 25
"C than predicted by the Hubbard-Onsager continuum
theory of the kinetic depolarization effect, in agreement
with Mandel and Van Beeks3 findings for other salts in
methanol and in water. For other solvents with much
larger dipole moments (-4 D rather than 1.8 D), the ob-
served decrements are much larger than the calculated
kinetic effect and increase at lower temperatures, sug-
gesting the importance of short-range ion-dipole interac-
tions in immobilizing solvent molecules near the ions.
Short-range forces of this kind are implicity neglected in
the Hubbard-Onsager theory, which is the only treatment
so far available for solvents other than water and methanol.
For these, Hubbard, Colonomos, and Wolynesghave made
numerical calculations for a molecular kinetic response
theory treatment of ion-solvent interactions in water and
methanol. Their treatment reduces to the Hubbard-On-
sager result in the limit of large ion sizes, but gives larger
decrements for small ions (<1.5 8, radius) in methanol. As
a test of the theoretical predictions and to determine the
degree of ion specificity, we have made measurements of
several alkali halides in methanol which are reported in
the companion paper which follows.
Acknowledgment. This work was supported by the
National Science Foundation, in part by Grant CHE
7822209-A02 and in part by the Materials Science Program
at Brown University.
(13) Falkenhagen, H. 'Theorie der Elektrolyte"; Hirzel: Leipzig, 1971.