Analytica Chimica Acto, 131(1981) 111-116

Ekevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

A HYDROGEN IONSELECI’WE LIQUID-MEMBRANE ELECI’RODE

BASE33 ON TRI-n-DODECYLAMINE AS NEUTRAL CARRIER

P. SCHULTHESS,Y. SHIJO., H. V. PHAM, E. PHETSCH, D. AMMANN and W. SIMON*

Swiss Fedeml Institute of Technology, Department of Organic Chemistry. CH-8092
Ziirich (Switzerland)
(Received 20th July 1981)

SUMMARY

An etectricaIly neutral hydrogen ion+zeIective carrier, tri-n-dodecylamine, is used as the

active component for liquid-membrane electrodes. The observed ion selectivities are
superior to those of previously described pH_sensitive liquid-membrane electrodes. The
electrode characteristics permit the study of inkacellular as well as extmcellular hydrogen
ion activities.

Attempts have recently been made to replace, in critical applications, the

pH-sensitive glass electrode by polymer-membrane electrodes [l-4]. For
this purpose, classical electrically-charged ion-exchangers have been used [ 2,
31. Even though the selectivity characteristics of the respective electrodes
were not always fully specified [ 1, 21, claims were made that these were
sufficient for the envisioned work [l-4]. By comparing these electrodes to
the glass electrode, however, it becomes evident that the selectivity charac-
teristics of liquid-membrane electrodes still need improvement.
In a search for carriers for anions, it was found that certain ethanolamines
exhibit hydrogen-ion carrier properties when incorporated in solvent poly-
meric membranes [5]. An unpublished study of the protonation of such
lipophilic ethanolamines by “C-n.m.r. spectroscopy in organic solvents (e.g.,
CDCIB, o-nitrophenyl octyl ether) indicated that in equihbrium with aqueous
solutions of pH >3 they are present predominantly in the unprotonated
form_ Similar behaviour was observed for lipophilic tertiary amines. Such
compounds are therefore likely to behave as neutral carriers for hydrogen
ions.
In this paper, a pH-sensitive neutral-carrier electrode based on tri-n-
dodecylamine is reported. This new solvent polymeric-membrane electrode
has very high selectivities that are more than adequate both for intracellular
and extracellular hydrogen ion activity measurements.

?resent address: Department of Environmental Chemistry, Faculty of Engineering,

University of Utsunomiya, Ishii-machi, Utsunomiya 321, Japan.

0003-2670/81/000~000/$02.50 e, 1981 Elsevier Scientific Publishing Company

 112

EXPERIMENTAL

Electrodes and membmne system

The cells used for measurements were of the type Hg; Hg,CL. KC1 (sati.)/
3 M KCl/samplc solution//membrane//buffer solution pH 5.6 (1.00 M citric
acid, 2.73 M NaOH, 0.01 M NaCI), &Cl; Ag. The external reference elec-
trode was a double-junction calomel electrode Philips R44/2SD/l (N. V.
Philips Gloeilampenfabrieken, Eindhoven, Holland). The liquid membranes
were mounted in Philips IS-561 electrode bodies.
The composition of the liquid membrane was 1.0% (w/w) tri-n-dodecyl-
amine (TDDA; zur Synthese; Merck, Darmstadt, GFR), 65.6% (w/w) bis-
(2-ethylhexyl) sebacatc (DOS; technical grade; Fluka, Buchs, Switzerland),
0.6% (w/w) potassium tet_rakis(p~hlorophenyl)boratc (KTpClPB), and
32.8% (w/w) polyvinyl chloride (PVC; S704 hochmolekular; Lonza, Visp,
Switzerland).
TDDA was distilled twice before use (0.06 mm Hg, 240-246°C). Elemen-
tal analysis gave the following results: calculated for C&,HT5N (522.00)
82.83% C, 14.48% H, 2.68% N; found 82.83% C, 14.29% H, 2.83% N.
KTpClPB was prepared as described by Cassaretto et al. [6]. Elemental
analysis gave the following results: calculated for C24H16BCIK (496.11)
58.10% C, 3.25% H, 28.59% Cl; found 58.02% C, 3.37% H, 28.34% Cl.
The membrane was prepared as described earlier [ 7]_

E_m.f. measurements
The e.m.f. values were measured at 20 i 1°C using a high-impedance
amplifier (operational amplifier 1702-01, Teledyne Philbrick, MA 02026) in
combination with an integrating digital voltmeter (Solartron 7055 Micro-
processor Voltmeter, Solartron Electronic Group Ltd., Farnborough,
Hampshire, England). The standard deviation arising from this measuring
equipment was <O.l mV for a single determination.
Selectivity factors were determined by the f=ed interference method
[8, 31 using solutions that were 0.99 mol 1-l in chloride and10.01 mol 1-l in
the hydroxide of the respective inizrfering cation. In the case of Ca**, some
precipitate was removed by filtration prior to the measurements (see Fig. 2).
The pH of the solutions was adjusted by the addition of hydrochloric acid.
In all experiments, the pH of the sample solutions was determined with a
Philips GA1 10 glass electrode [lo]. Titrations were done with an automatic
titrator (Potentiograph E436, Metrohm AG, Herisau, Switzerland).

Reagents
For all experiments, doubly-distilled water and chemicals of puriss or p-a.
grade were used. Solutions with a pH between 7 and 8 were buffcrcd with
Z-amino-2-hydroxymetyl-1,3-propanediol (Tris, puriss. p-a., Fluka) and a
universal buffer solution [ 111 was used for solutions in the pH range 2-13.
 113

EMF EMF
[mvl bl
300

200

100

576:ol
0 i

- 100

- 200 :-

- 300
- .-_-- -_---
12 10 6 6 4 2 PI+ 11 10 3 6 I

Fig. 1. pH response for the H.-selective liquid-membrane electrode at 20°C to buffered

solutions. The pH was adjusted by addition of hydrochloric acid or sodium hydroxide to
a buffer containing 69.0 mM Na*, 11.4 mM BO:-, 10.0 mM PO:- and 6.7 mM citrate.

Fig. 2. Response of the cell assembly with the recommended membrane to H.-activities
at constant concentrations of interfering ions. The electrolyte solutions were adjusted to
pH 11-12 by the addition of NaOH, KOH, and Ca(OH), to NaCI, KCI, and CaCi, aolu-
tions, respectiveiy. The solutions were then acidified stepwise with hydrochloric acid.

RESULTS AND DISCUSSION

The response of the cell assembly (see Experimental) to changes in the pH

of the sample solution is presented in Fig. 1. Even at the ionic background
indicated, the response is linear over the pH range 4.5-11-O with a slope of
57.8 f 0.1 mV/pH (theoretical 58.17, 20°C). At pH values below 3.5 there
is, as expected for neutral-carrier electrodes [ 12, 131, anion interference
leading to low e.m.f. values. The detection limit in alkaline solutions (pH
12) is established by the interference of sodium ions. The slightly over-
theoretical slope in the pH region 3.54.5 has not been satisfactorily
explained. It in no way hinders the use of the electrode for pH studies in
biological systems (cf. Fig. 4). For measurements in acidic solutions, a differ-
ent liquid-membrane electrode has recently been presented [4].
Selectivities in respect to Na’, K*, and Ca*’ were evaluated by the fixed
interference method [8, 91 (Fig. 2). The resulting values of log KzA are
-10.4 for M = Na’, 4.8 for M = K’, and less than -11.1 for M = Ca2*. These
114

EHF
[d]

-_ _ -- - - .-

20

-?O

---- --..- ‘.- -LO

y----

--__ -60
------_____

i
82 70 74 70 pn

Fig. 3. ‘I’itrations of 0.1 M NaOH with 0.5 M HCI. indicating electrode: (---) glass clec-
trade of low alkaline error [lo] ; (-) liquid-membrane electrode based on the neutral-
carrier TDDA; (.---.) liquid-membrane electrode based on a synthetic proton carrier [3].
(na: moles of acid added, no u: initial moles of base).

Fig. 4. pH rcsponscs for the H.-selective liquidmembrane electrode to Tris-buffered solu-

tions without interfering ions: (o) before contact with serum; (=) after contact with serum;
(0) to Tris-buffered solutions with 24 mM NaHCO, ; (u) to human blood serum. The pH
of the serum was varied by addition of hydrochloric acid. Linear regression yields a slope
of 56.2 z 0.2 mV/pH (theoretical 58.17, 20” C).

exceptionally high ion selectivities are nearly of the same order of magnitude
as those reported for pH-sensitive glass-membrane electrodes (G-13 for
monovalent interfering ions M [14] ). This is corroborated by the titration
curves given in Fig. 3. The expected equivalence point is identical for the
neutralcarrier electrode, a commercially available glass-membrane electrode
(see Experimental) and for a recently described liquid-membrane electrode
based on a synthetic H*carrier [3]. As a consequence of inferior selectivi-
ties, the latter electrode shows a change at the inflection region of only
about 5 pH units, whereas the neutralcarrier electrode yields a change of
about 9 pH units, which comes close to that of the glass electrode.
As is to be expected from the selectivity data given above, there is no
interference from electrolytes in human blood serum in the physiologically
relevant pH range (Fig. 4). The addition of a typical extracellular concentra-
tion of hydrogencarbonate ions (24 mM) to the Tris-buffered solutions does
not significantly influence the slope of the electrode response (Fig. 4). This
 115

result underlines the fact that the choice of a strongly buffered acidic
internal fiiing solution (see ,Experimental) eliminatesthe otherwise observed
em-f. effect of CO* diffusion across the membrane (see [ 1,5] ).
The 90% response time of the electrode obtained by injection. of hydro-
chloric acid into sodium hydroxide is about 0.4 s. A slightly larger value
(0.6-1.5 s) was obtained for a glass electrode. Mixing of the injected solu-
tion probably accounts for the 0.4-s figure; possibly the glass electrode used
is intrinsically slower than the liquid-membrane system.
The resistance of the membrane in a Philips IS-561 electrode body is
470 + 100 kJ2 (N = 5) with the membrane having an approximate area of
25 mm2 and a thickness of 0.1 mm. This corresponds to a specific membrane
rcs%.ance of 11.8 f 2.5 MS2 cm (N = 5).
The stability of the e.m.f. measurements (standard deviation, 20 + 0.5”C)
was found to be kO.05 mV (N = 48) over periods of 12 h in Tris-buffered
solutions of pH 7.47. For the glass electrode under the same conditions, the
standard deviation was kO.06 mV (ZV = 48). The reproducibility of e-m-f.
measurements with the cell assembly was checked by alternating measure-
ments (10 min each) on two T&buffered solutions of pH 7.2 and 7.6,
respectively (20 f 1°C). The standard deviation in the e.m.f. differences
determined was 20.1 mV (N = 10). The glass electrode under the same condi-
tions gave exactly the same result.
The solvent polymeric-membrane electrode continuously contacted Tris-
buffered solutions or, occasionally, blood serum for two months without
any loss of performance. According to the lipophilicity of the membrane
components, 2 lifetime of several years in continuous use can be expected
[I51 -
A detailed study on the applicability of this neutralcarrier membrane to
measurements in whole blood with a view to routine clinical work and con-
tinuous monitoring during surgery is in progress_

This work was partly supported by the Swiss National Science Foundation.
One of us (P_ S.) thanks Corning Ltd. for a grant.

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