Karchaudhari1979 - Effect of Organic Solvents and Their Dielectric Constants On Ion Selective Electrode Potential
Karchaudhari1979 - Effect of Organic Solvents and Their Dielectric Constants On Ion Selective Electrode Potential
Karchaudhari1979 - Effect of Organic Solvents and Their Dielectric Constants On Ion Selective Electrode Potential
9 by Springer-Verlag 1979
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 .
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:
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
I -I~0
&
" -lO0
-/80
-180
-20U I I I I I I I I
10 20 dO 4O
o~So,, y: Ce/v) --
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:
"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
-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
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 ~"
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