Mikrochimica Acta [Wien] 1979II, 411--420

9 by Springer-Verlag 1979

Department of Chemistry, University of Missouri-Kansas City,

Kansas City, MO 64110, U. S. A.

Effect of Organic Solvents and Their Dielectric Constants

on Ion Selective Electrode Potential
By
Sunetra N. Kar Chaudhari and K. L. Cheng
With 5 Figures
(Received May 2, 1979)

While the potentiometric method with ion selective electrodes

(ISE) has been demonstrated to be an important technique in elec-
trochemistry in the past two decades, its study was mainly restricted
to aqueous solution. Few investigators used organic solvents in their
studies.
The purpose of the present work was to investigate the influence
of mixed solvents on the electric potential of lead and silver ion
selective electrodes and the correlation between the membrane po-
tential and the dielectric constants of solvents.
Kazarjan and Pungor 1 used Ag/AgC1 membrane in methanol,
ethanol, n-propanol and isopropanol for the determination of solu-
bility product of silver halides and the selectivity constant of iodide
ion selective electrode. Selig and Salomon 2 studied the potential
behavior of lead ion selective electrode in p-dioxane. Pataki et al. a
determined the mean activity coefficients in absolute ethanol solu-
tions of sodium iodide using sodium ISE and iodide ISE. Covington
et al. 4 studied free energies transfer in isoelectric solvent mixtures
of NaF with LaFa ISE and sodium response glass electrode. Ficdler ~
studied the effect of dielectric constant of the membrane solvent on
the selectivities of neutral carrier ligands in electrode membranes.
In the present study solid membrane electrodes were used, liquid
membranes being unsuitable because they are soluble in organic sol-
vents. We used mixed solvents in the test solution to study their
influence on the membrane potential.

0026-3672/79/7902/0411/$ 02.00
412 Sunetra N. Kar Chaudhari and K. L. Cheng:

Experimental
Reagents
Water-miscible solvents such as methanol, ethanol, 1,4-dioxane, and
DMSO were used in this study. The solvents were of the highest purity
grade available. The experiments were carried out in mixtures of distilled
or &ionized water and the appropriate organic solvents. All other chemicals
were of analytical reagent grade.
ISA (Ionic Strength Adjustor) 5 M NaC104.
Buffer solution (pH 4.0). 0.05 M potassium biphthalate buffer from
Fisher Scientific Co.
Methanol-formaldehyde solution (2 x 10 -a M formaldehyde in metha-
nol) was prepared by diluting 20 ml of 0.37% formaldehyde solution to
one liter with methanol.

Apparatus
Lead ion selective electrode used was from Orion Research, Model
No. 94-82A.
Reference electrode used was double junction electrode from Orion
Research, Model No. 90-02.
Potentiometer used was from Corning Scientific Instrument Co., Model
No. 10. Differential D. C. Voltmeter used was from John Fluke Manu-
facturing Co., Model 801, H series.

Procedure
Both the electrodes (lead ISE and reference electrode) were
rinsed for 0.5 rain with deionized water jet. They were dipped in
deionized water for 5 to 10 rain before use.
T o a 50.00 ml of methanol-formaldehyde solution (2 x 10 -3 M
formaldehyde in methanol) add a suitable a m o u n t of Pb(C104)2
solution, 2 ml of ISA solution, a desired volume of non-aqueous
solvent, and mix, adjusting to p H 4.7 + 0.1 using a minimum a m o u n t
of solid methenamine or 0.1 M HCIO4.
Whenever t w o solvents are mixed, some air bubbles are formed
on the electrode surface. The bubbles were removed before the
potential measurement was made. During each measurement, a
magnet bar is placed in the solution to insure proper mixing. Pre-
cautions should be taken so that the m o t o r for the magnetic stirrer
does not get too hot affecting the solution temperature.
For the study of the effect of dielectric constant on potential,
solutions of 10% aqueous solution of Pb ~+ or Ag + and 90% organic
solvent were taken and adjusted to p H 4.7. N o ionic strength ad-
juster was added and the dielectric constant of the mixed solvent
 Effect of Organic Solvents and Their Dielectric Constants 4]3

w a s c o n s i d e r e d to be a p p r o x i m a t e l y e q u a l to t h a t of the p u r e solvent.
D u e to lack of ISA, the p o t e n t i a l r e a d i n g s w e r e r a t h e r u n s t a b l e .

Results and Discussion

Peroxide in Organic Solvents
Selig a n d S a l o m o n 2 e x p e r i e n c e d p o o r results w i t h p r o d u c t s of
p - d i o x a n e w h i c h c o n t a i n e d h y d r o g e n p e r o x i d e t h a t o x i d i z e d lead

o~ IOO[

-106

- IZ6

-140f

-/80t
-/80 i I I I I I I I I
/0 ZO 30 40
Organ~,.co~vent,X (v/iv) ,-
Fig. 1. Effect of solvent volume on potential of lead electrode
Curve 1 - - 10.2 M Pb(CIO@2 with ethanol; Curve 2 - - 10 .2 M Pb(C104)~ with
acetone; Curve 3 - - 10 .8 M Pb(C104)2 with ethanol; Curve 4 - - 10 .3 M Pb(C10@2
with acetone; Curve 5 - - 10 .3 M Pb(NO3)z with acetone; Curve S - - 10 .4 M
Pb(NO3)2 with acetone; Curve 7 - - 10.5 M Pb(C104)2 with acetone; Curve 8 - -
10 .4 M Pb(C104)2 with acetone; Curve 9 - - 10 .5 M Pb(C10@~ with ethanol;
Curve 10 - - 10-4 M Pb(C10@~ with ethanol; Curve 11 - - 10.6 M Pb(C104)~
with acetone; Curve 12 - - 10-~ M Pb(C104)~ with methanol (the solutions were
turbid); Curve 13 - - 10-~ M Pb(C104)2 with dioxane (the potential scale is
different)

sulfide m e m b r a n e surface. T h e y r e c o m m e n d e d m e t h a n o l or e t h a n o l
i n the use of lead i o n selective e l e c t r o d e for the t i t r a t i o n of sulfate.
W e used f o r m a l d e h y d e t o r e d u c e a n y h y d r o g e n p e r o x i d e i n the
o r g a n i c solvent. It is a s s u m e d t h a t o t h e r m i l d r e d u c i n g agents w o u l d
27 Mikrochim. Acta 1979 I I / 5 - 6
414 Sunetra N. Kar Chaudhari and K. L. Cheng:

also be effective to prevent the oxidation of lead sulfide. We have

found the existence of lead sulfate on the membrane surface by the
X-ray photoelectron spectrum. It is presumably formed during the
preparation of PbS and Ag2S in the presence of excess of sulfide
which is easily oxidized. The slightly soluble PbSO4 is not easily
washed off. It was found that use of EDTA and of physical rub-
bing to regenerate the electrode surface showed some success.

Effect of Solvent on Potential

After obtaining the results described previously with acetone,
more experiments with other water miscible solvents were carried
out. The results are shown in Fig. 1, and 2. There exists a general
trend that the potentials increased with increasing the amount of
organic solvent added. With exception of curves 9, 11 and 13 (con-
vex) in Fig. 1, all curves are concave. Methanol, ethanol and acetone
show a similar trend, regardless of lead perchlorate or lead nitrate
used. A slightly irregular deviation in curves 7 and 9 may be due
to the lower lead concentrations (1 • 10 -5 M and 1 • 10 -6 M). It is
interesting to note, however, that for 1 • 10 -2 M lead perchlorate
in p-dioxane, the solvent effect is more pronounced at less than
20% (v/v) p-dioxane, in contrast with the effects by methanol,
ethanol, and acetone where the solvent effect is pronounced at more
than 20%. It should be pointed out that the solution tested was a
mixture of three solvents, namely, water, 50% methanol, and various
amounts of appropriate organic solvent added.

Effect of Methanol
Methanol shows its positive effect on potential with the lead
solution (Fig. 1). However, it was noted that it caused turbidity
when both lead perchlorate (1 • 10 -2 M) and ISA (NaC104) solu-
tions were present. Neither one alone caused the turbidity. It is
believed that NaC104 is slightly soluble in a methanolformaldehyde
medium when Pb(C104)2 is present. It is possible that the precipitate
is a double salt of NaC104 and Pb(C104)2. When ethanol, acetone,
DMSO or dioxane was present, the solution was clear. Kazarjan
and Pungor 1 used the iodide ISE to study the Ks~ of AgI in 90%
methanol, which is comparable to our system of 88% methanol.
But they did not add formaldehyde and ISA solution in their system
as we did. It was not successful to substitute formaldehyde with
dimethylformamide or to use less than 50% methanol for obtaining
steady potential readings.
 Effect of Organic Solvents and Their Dielectric Constants 415

Effect of Dimethylsulfoxide (DMSO)

With dimethylsulfoxide the trend is reversed; the potential is
decreased linearly with increasing the a m o u n t of D M S O added
(Fig. 2). This may be explained in that the lead forms a complex
with the sulfoxide group in a similar manner as with sulfate group,
decreasing the lead ion activity.

-8O r [p~Yzo+JS (M) Cookn#

I I~ I0]~ Ha
-80 d Ix~O- ~3
9 -"...~, ~ i i x i o -s ~
-I00

I -I~0
&
" -lO0

-/80
-180

-20U I I I I I I I I
10 20 dO 4O
o~So,, y: Ce/v) --

Fig. 2. Effect of dimethylsulfoxide (DMSO) on potential of lead electrode

Curve I - - 10-2 M Pb(C1Oa)2 with DMSO (without cooling); Curve 2 - - 10 3 M
Pb(CIO4)2 with DMSO (after cooling); Curve3 - - 10-4M Pb(C104)2 with
DMSO (after cooling); Curve 4 - - 10-5 M Pb(C104)~ with DMSO (after cooling)

T h e curve 1 was obtained f r o m the w a r m mixtures of water

and D M S O as they are exothermal when the t w o solvents mix to-
gether. Other three curves were obtained from the mixtures after
cooling to r o o m temperature. T h e linear relationship between the
potential and the a m o u n t of D M S O added would provide a basis
of estimating D M S O . For 10 -5 to 10 -8 M lead solution, adding
approximately 2 5 - - 3 5 % D M S O leveled off the decrease of potential.
One might arrive at an erroneous estimation of molar ratio of
Pb : D M S O by plotting intercepts of the curves.

Effect of p-Dioxane
In the experiment with 1,4-dioxane, it t o o k longer time (10--
15 rain) to achieve equilibrium. Potentials for solutions of 10 -4 M,
27*
416 Sunetra N. Kar Chaudhari and K. L. Cheng:

10 -~ M, and 10 -6 M lead perchlorate in 30% or more dioxane were

never steady. Furthermore, the electrodes with epoxide coatings are
easily damaged by dioxane if it is dipped in the solvent for a long
time. Further experiments with dioxane were discontinued. In the
future studies with dioxane, the electrode must be prepared and
sealed with dioxane-resistant materials.

Potential Curve Slope

The calibration curves of lead in acetone and ethanol are s h o w n
in Fig. 3 and 4. It is noted that not only are there linear relationships

"I
between the logarithm lead concentration and potential, but such

-20

-~0

eab

~ -/O0

-/20

/
-/60

- d O 0 ~
Io -B lO -5 IO-~ IO -3 lO -z lO -i IOo
lead Eoacentratian, Male5 per Liter

Fig. 3. Calibration plots for lead electrode in acetone

Curve 1 - - 38 ml of acetone; Curve 2 - - 30 ml of acetone; Curve 3 - - 20 ml of
acetone; Curve 4 - - 5 ml of acetone; Curve 5 - - 10 ml of acetone; Curve 6 - -
0 ml of acetone

a linear relationship is extended to lower lead concentrations (less

than 1 x 10 -6 M lead). The slopes for acetone (Fig. 3, curve 2) and
ethanol (Fig. 4, curve 1) were found to be 28 and 29 mV for tenfold
 Effect of Organic Solvents and Their Dielectric Constants 417

change of concentration, respectively. T h e y are close to the ideal

slope of 29.5 mV. It should be noted that the curves in Fig. 3 and 4
were plotted with potential vs. concentration. If they were plotted

-do

3
;'S
-60
d

-80

- I00

-IZOI
~.."
..'~ g'urye i
Methanol,(ML)
0=8
- .""J" Z 30
- I~O< 3 dO
4 /a
5 5
-/66' 6 0
l
7
-/86 _# I I
iu
Lead /0 -5 ij-~ 101-3 iol-d 10-1
g'ancentrahbn,
Molesper L/let
1010

Fig. 4. Calibration plots for lead electrode in ethanol

Curve 1 - - 38 ml of ethanol; Curve 2 - - 30 ml of ethanol; Curve 3 - - 20 ml of .
ethanol; Curve 4 - - 10 ml of ethanol; Curve 5 - - 5 ml of ethanol; Curve 6 - -
0 ml of ethanol

as activity instead of concentration, the slopes would be very close

to the Nernst slope. T h e slope for the lead solution in a pure water
solution varied widely because difficulties in obtaining a steady
reading were encountered. According to the r e c o m m e n d a t i o n by
O r i o n Research, I n c : , steady potential readings were obtained in
a 50% methanol-formaldehyde solution with a slope of 2 2 - - 2 5 mV.

Electrode Potential and Dielectric Constant of Solvent

Ordinarily, a salt is more dissociated with increasing the dielec-
tric constant of a solvent, and ion pairing is p r o m o t e d in organic
solvents. As the potential depends on the activity of lead ion, we
might expect that the potential should increase with increasing di-
electric constant of a solvent. Acetone and ethanol have lower dielec-
418 Sunetra N. Kar Chaudhari and K. L. Cheng:

tric constant than water; thus we might expect that with increase
of percentage of acetone or ethanol, the potential should decrease.
But the results shown in Figs. i and 2 indicate the opposite trend.
This trend was not affected by substituting ethanol for acetone,
by substituting lead perchlorate for lead nitrate, or by omitting the
methanol formaldehyde solution.
An increase in potential usually means an increase in activity of
the ion being measured and we know that the concentration is equal
to the activity divided by the activity coefficient. Since the concen-
tration is constant, the activity coefficient must increase in order to
increase the activity. Because of the present results, one may be
forced to interpret the ISE potential from a different mechanism.

1
0 /0 2a 30 I~0 30 ~0 70 80
ffle/eclrlr ffonJl,qnl; 8 ~"

Fig. 5. Effect of dielectric constant of non-aqueous solvents on electrode potential

reading

Fig. 5 shows clearly some definite correlation between a dielec-

tric constant of solvent and an electrode potential. The potentials
decrease approximately linearly as the dielectric constant of a sol-
vent increases; i. e., they are in reverse relation to each other. The
exception in this trend is water, so far as the lead ion electrode and
the silver arsenite electrode 7 are concerned. The high potential ex-
hibited by water having a high dielectric constant requires a dif-
ferent explanation. It should be kept in mind that factors other
than dielectric constant of a solvent can influence the lead ion activ-
ity and the electrode potential. Water exhibited about the same
potential effect as the methanol. More data are required to have
better understanding of the solvent effect on potential.
 Effect of Organic Solvents and Their Dielectric Constants 419

In the study of the behavior of silver and halide ion electrodes

in mixed solvents, the beneficial effect of solvents miscible with
water increases with decreasing dielectric constant to a limit beyond
which, as with dioxane, the potentials become erratic 8. In the same
study, methanol and acetone proved most suitable, and a volume
ratio of 8 0 : 2 0 s o l v e n t : w a t e r was advantageous. The electrode
behavior in a mixed solvent system seems to indicate a drastic
change in solvation of metal ions and electrode surface, adsorption
of ions would be favored as a result of change in free energy
solvation.

Summary
Effect of Organic Solvents and Their Dielectric Constants on Ion
Selective Electrode Potential
The effects of mixtures of water with methanol, ethanol, ace-
tone, dimethylsulfoxide (DMSO), and p-dioxane on the lead ion
selective electrode potential have been studied. With the exception
of DMSO which decreases the potential, other organic solvents
stated above show an increased potential effect. Both the lead ion
electrode and the silver arsenite electrode show an approximately
linear decreasing relationship between the potential and the dielec-
tric constant of organic solvents studied.

Zusammenfassnng
Uber die Wirkung organischer L6sungsrnittel und ihrer Dielektrizitdts-
konstante auf das Potential ionenspezifischer Elektroden
Die Wirkung yon w~iflrigern Methanol, ~thanol, Aceton, Dimethyl-
sulfoxid (DMSO) oder p-Dioxane auf das Potential einer bleispezifischen
Elektrode wurde untersucht. Mit Ausnahme von DMSO, das dieses Poten-
tial vermindert, haben die angefiihrten organischen L6sungsmittel die ent-
gegengesetzte Wirkung. Die bleispezifische Elektrode und die Silberarsenit-
elektrode zeigen ein etwa linear abnehmendes Verh~iltnis zwischen dem
Potential und der Dielektrizitiitskonstante der angefiihrten organischen
L6sungsmittel.

References
1 N. A. Kazarjan and E. Pungor, Analyt. Chim. Acta 51, 213 (1970);
60, 193 (1972).
2 W. Selig and A. Salomon, Mikrochim. Acta [Wien] 1975, 663.
3 L. Pataki, K. Harka, J. Havas, and G. Keomleg, Radiochem. Radio-
anal. Lett. 26, 75 (1976).
420 Sunetra N. Kar Chaudhari et al.: Effect of Organic Solvents

4 A.K. Covington, K. E. Newman, and M. Wood, J. C. S. Chem.

Comm., 1234 (1972).
5 U. Fiedler, Analyt. Chim. Acta 89, 111 (1977).
Orion Research, Inc., Analytical Methods, 2nd ed., January 1972, p. 13.
7 E. E. K. Chao, P h . D . Dissertation, University of Missouri-Kansas
City, 1976.
8 E. Bishop and R. G. Dhaneshwar, Analyst 88, 433 (1963).

Correspondence and reprints: Prof. K. L. Cheng, Dept. of Chemistry,

University of Missouri, Kansas City, MO 64110, U. S. A.