ANALYTICAL SCIENCES FEBRUARY 1988, VOL.

4 13

Effect of Interfering Ion Concentration and Method of Calculation

on Potentiometric Selectivity Coefficients of Crown Ether Based
Liquid Membrane Ion Selective Electrodes

Abdulrahman S. ATTIYAT* and Gary D. CHRISTIAN**

*Department of Chemistry , Yarmouk University, Irbid, Jordan
**Department of Chemistry , BG-10, University of Washington, Seattle, WA 98195, U.S.A.

The potentiometric selectivities of two 14-crown-4 ethers incorporated in PVC membrane electrodes were deter-
mined for lithium with respect to sodium and potassium in different solvents and in different carrier solutions
using flow injection analysis. Four methods for calculating selectivity coefficients were compared. A correlation is
made between the relative levels of the interfering ion and primary ion and the numerical values of the selec-
tivity coefficients calculated by the different methods. An increased level of sodium causes divergence among
the values of the selectivity obtained by different methods, increases the selectivity of lithium over sodium,
decreases the sensitivity and the slope of the calibration graph, and distorts the linearity of the curve.

Keywords Ion selective electrode, selectivity coefficients, crown ethers, liquid membrane electrode, lithium

The selectivity of an ion selective electrode for an

ion, i, with respect to another, j, is usually expressed by
the selectivity coefficient (K 9L). The numerical value
of this coefficient for certain electrodes depends on the
level of the interfering ion, the composition of the
solution to which the electrode is exposed, and the
method used in calculating the selectivity coefficient.'-3
The methods employed for calculating selectivity
coefficients, such as the matched potential, separate
solution or fixed interference methods'-4, may lead to
different numerical values for a selectivity coefficient
for the same electrode."2,5 In polymeric ion selective
electrodes incorporating neutral carriers, the potentio-
metric output and the selectivity of the electrode with a
given carrier depends also on the exact composition of Experimental
the electrode membrane3'6'7'8,including the nature and
amount of the ionophore, the plasticizer, and the Reagents and chemicals
additives. Therefore, the composition of the electrode, Chlorides of sodium, potassium, lithium and magne-
the conditions under which the measurements are taken sium were dried at 140°C for 48 h before their use in
and the methods used in calculation should be stated in preparing standard solutions. Distilled deionized water
reporting values of selectivity coefficients. was used to prepare the aqueous solutions. Ionophores
In this study, the selectivity coefficients of two 1 and 2 were supplied by R.A. Bartsch, Department of
neutral carrier-based electrodes incorporating two 14- Chemistry, Texas Tech University, Lubbock, TX.
crown-4 ethers (1 and 2) were calculated for lithium Poly(vinyl chloride) (PVC, high molecular weight) was
with respect to sodium and potassium, using different obtained from Fluka AG. o-Nitrophenyl octyl ether
methods, at different levels of the interfering ions, and (NPOE) and potassium tetrakis(p-chlorophenyl)bo-
in different solutions. Matched potential, separate rate (KTpC1PB) were obtained from Specialty Organics,
solution and fixed interference methods were used in Inc., Irwindale, California, and tetrahydrofuran (THF)
conjunction with flow injection analysis measurements from EM Science, Cherry Hill, New Jersey was used to
to calculate the selectivity coefficients. dissolve the electrode matrix.
M
14
Apparatus
A flow injection analysis (FIA) system with a flow
cell incorporating a series of silver wire electrodes
similar to that reported earlier2 was used for
measurements. The electrode membranes were pre-
pared by dissolving 1.5 mg ionophore, 65 mg NPOE, 1
mg KTpCIPB and 33 mg PVC in 350 µl tetrahydro-
furan. Each of the membrane matrices was applied on
the tip of a preconditioned silver wire electrode.2 Three
layers of 2 sl each were applied by means of a capillary
pipet. After the electrodes were dry, the flow channel
was sealed by a plastic sheet using double-sided tape,
and the cell introduced into the flow system. The
electrodes were conditioned in contact with 14 mM
sodium chloride solution for several hours before use.
A downstream silver-silver chloride electrode served as
the reference electrode.
A Beckman 3500 digital pH meter was used to
monitor the potential of the electrodes. The pH meter
was connected to a Linear chart recorder to record the
FIA signals.
Air-pressurized reference and carrier reservoirs were
used in connection with flow meters and debubblers.
The flow rates were 1 ml/ min for the carrier stream
and 0.2 ml/ min for the reference electrode stream. The
sample volume used was 200 µl, which allows zero
dispersion in the middle of the sample plug.
Procedure
Table 1 lists the solutions employed in the studies.
Standard solutions of 10, 14, 20, 70 and 140 mM
sodium chloride and 2.4 mM magnesium chloride and
5.5 mM potassium chloride were pumped as carriers
through the carrier and the reference electrode
channels. Standard solutions (primary ion) of 0.2, 0.5,
2, 5, 10, 20, 50, 100 and 200 mM lithium chloride
prepared in the carrier solution were injected in each
carrier, except when 14 mM sodium chloride carrier
was used, in which case the solvent of the lithium
standards was distilled deionized water. The FIA
signals obtained from injecting lithium standards in
each carrier were used to construct the lithium
calibration curve for both electrodes for that carrier.
Standard solutions (secondary ion) of sodium chloride
and potassium chloride (at different concentrations
given) dissolved in the carrier solutions were injected
Table 1 Compositions of solutions studied
ANALYTICAL SCIENCES FEBRUARY 1988, VOL. 4
into each carrier and the FIA signal recorded. When
14 mM sodium chloride carrier was used, the solvent of
these standard solutions was again distilled deionized
water.
Calculations of potentiometric selectivitycoefficients
Four methods were used to calculate the selectivity
coefficients of lithium relative to sodium and potas-
sium:
Method 1 is the matched potential method''2, where
the concentration of the primary ion (CLi)equivalent to
the signal of a known concentration of the interfering
ion (CM), both in a constant reference solution, is
obtained from the calibration curve. The selectivity
coefficient is calculated according to the equation:
LitM= CLi
M Measurements in 14 mM NaCI carrier with LiCI
dissolved in water do not correspond strictly to the
matched potential method, but rather represent a
variation on the matched potential and separate
solution methods, given as Method 2 in reference 2.
Method 2 is the mixed solution method or fixed
interference method2'4, where the linear portion of the
lithium calibration curve (obtained in the presence of a
fixed concentration of the secondary ion) is extra-
polated to the potential of the background secondary
ion solution; this corresponds to the carrier potential
(arbitrarily taken as 0) when it serves as the
background. The concentration of lithium (CLi) at that
point is equivalent to the concentration of the carrier
(CM) which represents the interfering ion, and the
selectivity coefficient is calculated in the same way:
K pot CLi
LiM- ~+ .............................. (2)
Method 39 is another form of the mixed solution
method, in which the selectivity coefficient is obtained
using the same equation (2), where CU is the con-
centration of lithium ion at the point where the cali-
bration curve deviates from the extrapolated Nernstian
line by 18 mV (for monovalent ions). And CM is the
background concentration of the interfering metal
(sodium or potassium). This corresponds to the point
at which the apparent concentration is theoretically
ANALYTICAL SCIENCES FEBRUARY 1988, VOL. 4 15

doubled due to the presence of the secondary ion. In sensitivity and the slope of the linear portion of the
cases where the slope of the curve deviates from curve decrease as the level of the interfering ion
Nernstian, the amount of deviation from the linear increases; the slope is 58 mV/decade at 10 mM sodium
portion is corrected proportionally. and 46 mV/ decade at 140 mM sodium. The FIA
Method 4 is the separate solution method.4 In this potentiometric response in the NaCI carrier decreases
method equal concentrations of pure solutions of the as the NaCI concentration is increased. For the
electrode containing ionophore 2, similar results were
primary ion and the secondary ion are injected. The
selectivity coefficient is calculated from the measured obtained.
potentials of each solution:
Selectivitycoefficients
log Kpot EM- ELI Table 2 shows the selectivity coefficients of the
LI,M= s ...................... (3)
electrode incorporating ionophore 1, for lithium with
S is the slope of the lithium calibration curve. It is respect to sodium and potassium in different carrier
clear that this method can be used in this study only for solutions. The selectivity coefficients are listed for the
the lithium standards in water and the interfering ion four methods and at different concentrations of the
standards in water, injected in the 14 mM sodium interfering ions. The values obtained by the various
chloride carrier. The relatively large sample volume methods are generally similar in magnitude at the low
prevents dispersion in the middle of the sample plug, concentrations of the interfering ions, where the
which can be considered pure solution. response is Nernstian and the curve is linear. It has
been noted that selectivity coefficients vary with the
concentration of the interfering ion in solution, as well
Results and Discussion as the method used in calculation.) In this table, it is
seen that these values converge as the response
Calibration graphs approaches Nernstian and the linearity of the curve
Calibration graphs for the electrode with ionophore improves. But they diverge with the deviation from
1 for lithium standards in water, 5.5 mM KCl and 2.4 Nernstian and decreased linearity span caused by the
mM MgCI, when using 14 mM NaCI, 5.5 mM KCl and level of the interfering ions. The value of K !a, for
2.4 mM MgCl2 carrier solutions, respectively, exhibited example, is 0.1 obtained by three methods when the
good linearity with nearly Nernstian response. The level of the secondary ion (sodium) is 10 mM, but it
order of FIA potentiometric response in the different ranges between 0.06 to 0.016 when the level becomes
carriers was MgCl2>KC1>NaCI. For lithium stand- 140 mM, the condition at which the response deviates
ards dissolved in 10, 20, 70 and 140 mM NaCI from Nernstian (slope=48 mV/ decade).
solutions, which also act as carriers, the linearity, the Another feature in the table is the increase of the

Table 2 Selectivity coefficients of the electrode incorporating ionophore 1 , for lithium with respect to sodium and potassium,
in different carrier solutions
16 ANALYTICAL SCIENCES FEBRUARY 1988, VOL. 4

Table 3 Selectivity coefficients of the electrode incorporating ionophore 2, for lithium with respect to sodium and potassium,
in different carrier solutons

selectivity towards lithium over sodium when the
concentration of sodium in the solution and the carrier
increases. The same trend appears in the selectivity of
lithium over potassium.
Table 3 shows the same information for the electrode
incorporating ionophore 2. The same general features
of Table 2 appear in this table regarding the carrier
ions and diversion of the selectivity coefficients
obtained by the different methods, as well as the
increase of selectivity for lithium with the increase of the
level of the interfering ion. The linearity of the curve
and its slope decrease with the increase of the
interfering ion.
In conclusion, a high background level of the
interfering ion causes the following: a) makes the
response of the ion selective electrode deviate from
Nernstian response by decreasing the slope and the
linear portion of the curve, b) decreases the signal of
the lithium standards due to the increased background,
c) causes divergence of selectivity coefficient values
obtained by the different methods, d) increases the
selectivity for the primary ion with respect to the
interfering ion, and e) causes divergence of selectivity
coefficients determined by a given method (the
matched potential method) when different concentra-
tions of the secondary ion are used for the selectivity
measurements.
The authors ' gratefully acknowledge the support from the
Council for International Exchange of Scholars (Fulbright
Scholarship) and from Yarmouk University, Irbid, Jordan, to
A.S. Attiyat, and the supply of the crown ethers from R.A.
Bartsch.
References
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Acta,164, 279 (1984).
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Acta, 184, 259 (1986).
3. V. P. Y. Gadzekpo, J. M. Hungerford, A. M. Kadry, Y.
A. Ibrahim, R. Y. Xie and G. D. Christian, Anal. Chem.,
58, 1948 (1986).
4. IUPAC, Pure Appl. Chem., 48,129 (1976).
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Bartsch, unpublished work (1987).
6. D. Ammann, W. E. Morf, P. Anker, P. C. Meier, E.
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(1986).
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(Received September 14, 1987)
(Accepted October 19, 1987)