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Ion-Selective Sensors.

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The phototropic properties of the glasses must be modified
for this purpose [521.
A phototropic glass for use in holography [ 2 9 * 5 1 , 5 2 1 must
have a high resolution. All phototropic glasses are better in
this respect than the best photographic layer, which is tied
t o the photographic grain. A high writing rate (at least 106
bits/s) is required, and the hologram must exhibit good
stability over long periods [291; this requirement is linked with
the regeneration time and the activation energy for regeneration1261. Extinction must also be possible; lasers operating in
the near IR region or heat may be used for this purposec361.
Baldwin 1531 has published information o n the determination
of the storage capacity of phototropic glasses for holography.
The use of a conducting film for accelerated regeneration,
which is essential for holographic applications, has been
described by Justice and LeiboldI361. The specimens are
coated o n both sides with a transparent, electrically conducting film of stannic oxide. The applied voltage was
120 V, and the power was approximately 48 W. Specimens
[52] G. Gliemeroth, Umschau in Wissenschaft und Technik 7,
210 (1970).
[53] W . J . Baldwin, Appl. Optics 6 , 1428 (1967).
with a half life of 500 s were completely regenerated in less
than 10 s on application of the electric field.
The use of phototropic glasses in micrography has been
described by DeKing 1541.
Other applications are instrument panels that are controlled
by computers and which write the data in the phototropic
glass with UV beams 1221. Automobile windshields, window
glass, etc. have been considered as a potential application
of phototropic glass.
W e thank Dr. H. Bach, Jenaer Glaswerk Schott & Gen.,
Mainz, for preparing
and making all the electron
micrographs shown in this article.
Received: March 21, 1970
[A 758 IE]
German version: Angew. Chem. 82, 421 (1970)
Translated by Express Translation Service, London
[54] E. &King, Report of the National Cash Register Co.,
London 1969, 206.
[55] A . Krauth and H . Oel, Glastechn. Ber. 42, 139 (1969).
[56] H . Bach and H . Schroder, J. Non-Cryst. Solids 3 , 1 (1970).
Ion-Selective Sensors
By Wilhelm Simon, Hans-Rudolf Wuhrmann, Milan VaSBk, Lavinia A. R. Pioda, Rene Dohner [*I,
and Zlata Stefanac [**I
Numerous advances have recently been made in the development of ion-selective (glass,
solid, liquid) membrane electrode systems, The theoretical principles and practical requirements of such ccsensors” are outlined in this article, and an attempt is made to review
their possible applications.
1. Introduction
already been discussed in detail in several publications [2,15-18,220-2241.
A number of reviews have been published on the selective detection of ions in aqueous and nonaqueous solutions by electrode systems [1-14,220,221,2561. The
present position in this field is described below, with
special emphasis on the discussion of various sensor
systems. The associated membrane phenomena have
[*I Prof. Dr. W. Simon, Dip1.-Phys. H. R. Wuhrmann,
Dip1.-Chem. M. VaSak, Dr. L. A. R. Pioda, and
Dip1.-Fernmeldetechniker R. Dohner
Laboratorium fur Organische Chemie der ETH
CH 8006 Zurich, Universitatsstrasse 6-8 (Switzerland)
[**I Prof. Dr. Z . Stefanac
Institut za medicinska istraiivanja
MoSe Pijade ul. 158, Zagreb (Yugoslavia)
[ l ] G. A . Rechnitz, Chem. Engng. News 45, No. 25, 146 (1967).
[2] G. Eisenman: Glass Electrodes for Hydrogen and Other
Cations, Principles and Practice. M. Dekker, New York 1967.
[31 M . Lavallie, 0. F. Schanne, and N . C. Hibert: Glass Microelectrodes. Wiley, New York 1969.
[41 R . G. Bates: Determination of pH, Theory and Practice.
Wiley, New York 1964.
151 D . J . G. Ives and G. J . Janr: Reference Electrodes, Theory
and Practice. Academic Press, New York 1961.
I61 E . M . Weyer, M . Krauss, and A . G. La Mirande, Ann. New
York Acad. Sci. 148, 1 (1968).
[71 E. Pungor, J . Havas, and K . Tdth, Instruments Control Syst.
38, 105 (1965).
Angew. Chem. internat. Edit.
1 Vol. 9 (1970)/ No. 6
The sensors to be considered here can be divided into
three basic groups, according to the type of membrane:
1. glass membrane
2. solid-state membrane: a. homogeneous solid-state
membrane
b. heterogeneous solid-state
membrane
3. liquid membrane:
a. electrically charged
ligand groups (ion exchangers) as membrane
components
_
_
~
[8] E . Pungor, K . Tdth, and J . Havas, Microchim. Acta 4-5,
689 (1966).
[9] E . Pungor and K . Tdth, Hung. sci. Instruments 14,15 (1968).
[lo] F. Oehme, Chem. Rundschau 21, 891 (1968).
[ l l ] E. Pungor and J . Havas, Acta chim. Acad. Sci. hung. 50,
77 (1966).
[I21 J . 2‘. Clerc and W. Simon, Pharmac. Acta Helvetiae 40,
513 (1965).
[13] A . K . Convington, Chem. in Britain 5 , 388 (1969).
[14] K . Cammann, Fortschr. chem. Forsch. 8, 222 (1967).
1151 G. Eisenman, Analytic. Chem. 40, 310 (1968).
[16] J . Sandblom, J. physic. Chem. 73, 249 (1969).
[17] J . Sandblom, G. Eisenman, and J . L . Walkerjr., J . physic.
Chem. 71, 3862 (1967).
L181 R . P. Buck, Analytic. Chem. 40, 1432, 1439 (1968).
445
b. electrically neutral ligand
groups as membrane
components.
Figure 1 shows a diagram of a cell assembly for the
detection of ions. The membrane, which responds
selectively to ions, is normally combined in a unit with
the internal filling solution and inner reference electrode (internal reference electrode). Such “sensors”
are illustrated in Figure 2 for the membrane types
mentioned.
B
1
I
m
ma
Fig. 1.
\2
Membrane electrode cell assembly (schematic).
1: EMF; 2: membrane; 3: internal filling solution; 4: inner reference
electrode; 5: reference electrode (external); 6: solution to be measured.
Both the inner solution and the inner reference electrode may in principle be replaced by a direct electrical
connection to the corresponding side of the membrane [19-211. Such systems may occasionally be advantageous for membrane electrodes of types 2 and 3,
but are not recommended for glass electrodes in view
of the choice of the electrical zero of the cell assembly
and the choice of the isopotential p H (intersection of
isotherms) [19,22,231.
In the glass electrode (Fig. 2A), the ion-selective membrane is usually fused to an inert glass stem, while in
solid-statemembraneelectrodes it is usuallycemented to
an inert membraneshaft (Fig.2 C,D).For heterogeneous
solid-state membranes, Pungor et al. [7,11 2211 use about
30 to 50 wt.-% of ion-selective membrane component
(e.g. silver halide) having a grain size of 5-10 km in
a silicone rubber matrix. Other matrix materials that
have been used are paraffin wax, acrylamides, and
polyethylene c24-271.
1191 R . G. Bates, cf. [3], p. 1.
1201 Coleman Instruments (Maywood, HI.), Bull. B 329, No.
1168.
[21] L . Kratz: Die Glaselektrode und ihre Anwendungen.
D. Steinkopff, Frankfurt/Main 1950.
[22] D . Wegmnnn and W. Simon, Helv. chim. Acta 47, 1181
(1 964).
[23] J . T . Clerc, Z . Stefanac, and W. Simon, Helv. chim. Acta
48, 54 (1965).
I241 A . Shatkay, Analytic. Chem. 39, 1056 (1967).
[25] E. B. Buchanan j r . and J . L . Seago, Analytic. Chem. 40,
517 (1968).
[26] G . G . Guilbault and P. J . Brignac j r . , Analytic. Chem. 41,
1136 (1969).
1271 H . J . C. Tendeloo and A . Krips, Recueil Trav. chim. PaysBas 76, 703, 946 (1957); 77, 406, 678 (1958); 78, 177 (1959).
446
c
D
Fig. 2. Membrane electrodes (schematic).
A: Gloss electrode: 1: glass membrane; 2: internal filling solution; 3: glass
stem; 4: inner reference electrode.
B: L i p i d membrane electrode: 1: filter paper impregnated with ionselective ligand; 2: internal filling solution; 3: electrode shaft; 4: inner
reference electrode; 5: ion-selective ligand; 6: tube to receive internal
filling solution.
C : Electrode with homogeneous solid-state membrane: 1 : homogeneous
solid-state membrane; 2: internal filling solution; 3: electrode shaft;
4: inner reference electrode.
D: Electrode with heterogeneous solid-state membrane: 1 : heterogeneous
solid-state membrane; 2: internal filling solution; 3: electrode shaft;
4: inner reference electrode.
In the liquid membrane electrode of Figure 2B, a filter
paper impregnated with ion selective ligand acts as the
membrane. Any ion-selective component contaminating the solution being measured is replaced from the
reservoir 5 (Fig. 2B); this should ensure a long electrode life of the membrane electrode system Q81.
For ease of handling of the cell assembly and for working with small samples, it is advisable to combine the
ion-selective membrane with the inner reference electrode, the internal filling solution, and the reference
electrode that dips into the solution to be measured to
form a single structural unit (single-rod cell assembly,
combination electrode) [4,*2,291.
2. Theoretical Considerations
Though liquid junction potentials that depend on the
electrolyte of the reference electrode, the sample, the
temperature, and other factors arise a t the phase
boundary between the reference electrode and the
sample, it will always be assumed here that the poten(281 J . W. Ross, US-Pat. 3429785 (1969) Corning Glas Works,
Corning, N. Y., USA; Brit. Pat. 1107108 (1968).
[29] Orion Research Inc. (Cambridge, Mass.) CAT/961 (1969).
Angew. Chem. internat. Edit.
VoI. 9 (1970) 1 No. 6
tial of the reference electrode with respect to the
sample is constant and independent of the nature
of the sample solution (Fig. 1)[4,19,30-341.
2.1. Glass Membranes, Solid-state Membranes
(Solid Ion-Exchange Membranes)
Relations based on investigations by Nicolsky [351 have
been derived from experimental data for the E M F of a
cell assembly with a liquid or solid ion-exchange membrane 115-171. These relations can be formulated as
follows for glass and pure solid ion-exchange membranes:
and
i= 1
for a given inner reference electrode system.
The selectivity constant K P , which characterizes the
preference of the sensor for the ion j as compared with
the ion i, is given by
where Kij is the equilibrium constant of the exchange:
Jsoiution
+ Imembrane
+
Jmembrane
+ Isoiution
(6)
and ui and uj are the mobilities of the ions in the membrane. If the sensor responds to a bivalent ion ( a l ) and
a monovalent ion (uz), eq. (3) becomes eq. (7):
R = gas constant; T = absolute temperature; F = Faraday
constant; ai = ion activities in the sample solution (monovalent ions); uf = ion activities in the internal filling solution
(monovalent ions); n = constant depending o n the ions i and
= selectivity constant (preference of
the membrane; K:,"
sensor for ion 2 in relation to ion 1).
n.15
11.15
I n sensors having a given inner reference electrode
system (uf constant), we have
n.3
n.2
Figure 3 shows functions of this nature for a glass
electrode cell assembly with a high selectivity for
sodium ions, one ion being H30f and the other a n
alkali metal cation in 0.1 M solution [361. The selectivis about 0.18 [*I 1361, so that for
ity constant
this sensor
uH+)'jn is negligible in relation
t o aNa+t/n
in aqueous NaCl solutions of medium pH,
and a linear relation should accordingly exist between
the E M F of the cell assembly and the logarithm of the
sodium ion activity of the sample. It can be seen from
Figure 4 that this is largely so [361. The linear regression
of the experimental E M F values for the activity range
10-1 to 10-4 M gives a value of 59.8 mV/pNa+ for the
slope of the electrode function, in good agreement with
the theoretical value of 59.2 mV/pNa+.
From eq. (1) we obtain in general for a mixture of N
monovalent ions with n = 1:
KE+,+
(Kg+H+
~
1 0 0 y
I
0
m
2----'-e
1
J
2
Na
0-
1
,
,
,
,
6
4
PH
,
,
,
8
,
,
10
12
+
Fig. 3. EMF changes for a Na+ responsive glass electrode in 0.1 M
alkali metal ion solutions at various pH values [361.
/
/
/
/
-200-
/
/
N
' :K
:
EMF(T) = E," (T)
+
R
T
. ai
i=t
N
(3)
i=l
1301 I. Feldman, Analytic. Chem. 28, 1859 (1956).
[31] K. Schwabe: pH-Messtechnik, 3rd Edit. T h . Steinkopff,
Dresden und Leipzig 1963.
[32] J. A. R. Kater, J. E. Leonard, and G. Matsuyama, cf. [6],
p. 54.
[33] G. Milazzo: Elektrochemie. Springer-Verlag, Vienna 1952.
[34] W. Simon and D. Wegmann, Helv. chirn. Acta 41, 2308
(19 5 8 ) .
[35] B. P. Nicolsky, 2. fiz. Chim. 10,495 (1937).
[36] 2.Sfefanac and W.Simon, Analyt. Letters I, No. 2 , l (1967).
[*I If the indices are transposed in the logarithmic term of eq.
(1) for n = 1, we obtain: K y = l / K P
Angew. Chem. internat. Edit. J Vol. 9 (1970) 1 No. 6
I11%I ,
l6%1.
+loo'
1
=
1
2
3
- log a+
,-
4
5
n=l
6
Fig. 4. Electrode function of a sodium-selective glass electrode assembly [aqueous NaCl solutions; cell assembly consisting of a glass electrode
and a calomel reference electrode (KCI satd.) with electrolyte bridge
(0.1 M NH4NOa)l 1361.
447
KY
For a completely reversible cell assembly,
can in
principle be determined approximately by carrying
out measurements in a solution of the ion i and in a
solution of the ion j. If these are e.g. 0.1 M solutions of
monovalent ions, it follows from eq. (4) (cf. also 1371)
that:
0.1 M, Ion i: E M F ~
=
R-T
I$' (T) + __
In (0.1 + KY. 0)
F
(8)
KY.0.1)
(9)
0.1 M, Ion j: EMF2 = E," (T)
EMF2 - EMF1
log KEot
=
=
R-T
__ In
F
+
R.T
__ In (o+
F
KY
EMF2 - EMF1
59.2 mV
(10)
(25 "C)
Disturbances of the electromotive behavior of the
sensor are to be expected when ions (interfering ions)
form soluble products with membrane components
(and so destroy the membrane) or give sparingly
soluble compounds. In the second case, it is possible
to calculate the maximum permissible activity al,max
of the interfering ion 1 from the solubility products
L2.3 (solubility product of the original membrane
material) and L2.1 (solubility product of the sparingly
soluble compound formed) and the activity a3 of the
ion to be determined:
a1,max =
L2,1
~
a3,max
L2,3
Similarly, Pungor and Tdth (91 express the selectivity
constant of heterogeneous solid-state membranes in
terms of the solubility products Lkj and Lki of the
sparingly soluble membrane components:
The arguments for ion-exchange membranes should
be applicable only in part to solid membrane electrodes [15J.
2.2. Liquid Membranes
2.2.1. E l e c t r i c a l l y C h a r g e d L i g a n d s
Sandblom, Eisenman, and Walker [15-171 have derived
a relation for the E M F of a cell assembly consisting of
a liquid ion-exchange membrane electrode (Type 3a)
and a n external reference electrode.
Eq. (16) is valid only under the following conditions:
1. the ligands are situated exclusiveIy in the membrane;
2. there are no coions in the membrane;
3. equilibrium exists between the ion i and the ligand
at all points in the membrane;
4. associates and ion aggregates of higher order do not
occur;
5. the activities can be equated to the concentrations
inside the membrane;
6. the system is at zero current.
For certain special cases, the integrals over the thickness of the membrane in eq. (16) can be neglected or
can be easily calculated 1171. Thus in the steady state,
J 2 is equal to zero, owing to the disappearance of the
entire ligand flow. If the concentration of the free
ligand is negligible, J1 will also be zero, and eq. (16)
reduces for a given internal electrode system of the
sensor to
in analogy with eq. (4). According to equation (18) the
selectivity of the membrane is given mainly by the
solvent used to dissolve the ligand. According to
Eisenman [ ~ 5 1similar circumstances should hold for
systems with completely dissociated ligands.
If on the other hand the ligand is mainly in the undissociated mobile form, eq. (16) can be replaced (cell
assembly with a given internal electrode system) in the
limiting case [*I by
where uIs and u2s are the mobilities of the complexes
of the ligand with ions 1 and 2 respectively. For this
limiting case, therefore, the equilibrium constant K12
is a measure of the selectivity constant (cf. c371).
In the ideal case, it is accordingly possible to produce
liquid membrane sensors having widely different
selectivities with components having suitable Kij
values 13x1. The selectivity of glass and solid membrane
electrodes, on the other hand, depends on the product
of the exchange equilibrium constant Kij and the
mobility ratio of the ions in the membrane [eq. (5)].
I n view of the low mobility of Caz+ in glasses, therefore, it will be difficult to find glass electrodes with an
extremely high preference for this ion over alkali metal
ions [2J.
2.2.2. E l e c t r i c a l l y N e u t r a l L i g a n d s
ki
zi
=
=
(
exp -
R.T
valency of the ion i; p:
=
standard chemical potential of
the ion i in solution; p: (m) = standard chemical potential of
the ion i in the membrane phase.
[37] K . Srinivasan and G . A . Rechnitz, Analyt. Chem. 41, 1203
(1 969).
448
Eisenman, Ciani, and Szabd [220,222-2241 derived the
following equation for the E M F of a liquid-membrane
electrode of the electrically neutral ligand type and a
given internal reference electrode system:
[*I In the limiting case in question, u i s = uzs.
[38] C. J . Coetzee and H . Freiser, Analytic. Chem. 41, 1128
(1969).
Angew. Chem. internat. Edit. 1 Vol. 9 (19701 1 No. 6
R-T
- _ _ In (1
+ K l s a1 + &sad
(20)
Mobilities of electrically charged complexes within
the membrane;
kis, k 2 ~ : Distribution coefficients of the complexes between
sample solution and membranes;
K l s , K2s: Equilibrium constant of the interaction of the
cations with ligand in the sample solution.
U I S , ups:
Equation (20) holds only under the following conditions:
1. Two monovalent cations with the activities a1 and
a2 are in the sample solution;
2. The concentrations of all the electrically charged
species within the membrane are so small as compared
t o the concentration of the complexed cations that
only the flux of the complexes has to be considered to
account for the electric current in the integration of
the flux equation;
3. The activities of the complexed cations within the
membrane as well as the complexed cations and the
ligands in the sample solution are equal to the corresponding concentrations;
4. The fluxes of the complexes d o not disturb the
equilibrium a t the membrane boundary;
5. The concentration of electrically neutral complexes
and higher associates within the sample solution may
be neglected;
6. The system is a t zero current.
In equation (20) the second logarithmic term may be
neglected relative to the first if the concentrations in
the sample solution are so small that the complex formation in it may be neglected. Furthermore, the
constants of the first logarithmic term in equation (20)
can be expressed as a ratio of two equilibrium constants of the following salt extraction:
KI
I+(aqueous)
+ X-(aqueous) + Sforganic) t
IS+(orgAnic)+ X-(orgtinic)
(21)
Equation (20) therefore gives in analogy to equation(1)
3 1 selectivity
Since in most cases uIs rn ~ ~ ~ 1 2 2the
constants of liquid-membrane sensors with electrically
neutral ligands are mainly given by the ratios of the
equilibrium constants K 1 and K2 which again depend
on the ligands and other possible components of the
membrane.
3. Sensor Systems
Glass 1391, solid [40,411, and liquid membrane electrode
systems 139,42,431 have been known for some time, but
apart from glass protodes, as can be seen from the
Angew. Chem. internat. Edit.
/ Vol. 9 (1970)1 No. 6
literature (Table 11, they have for obvious reasons only
recently come into wide use. Table 1 is the result of an
attempt to make a list (by no means complete) of
publications on the detection of individual ions by
means of ion-selective sensors. The reader is referred
in particular to some outstanding reviews in connection with glass electrodes [2-4,31,2201.
Manufacturers often designate electrodes according to
the ions for which they are supposed to be used. These
designations should not be taken too seriously, So called
“calcium electrodes” (liquid membrane electrodes)
prefer Zn2+ 1431 and “K+ glass electrodes” are usually
more sensitive to H+[21. The most selective sensor
available a t present is undoubtedly the glass protode,
which has KF&+ values of 10-13 (X+ = alkali metal
cation) 1441.
It can be seen fromTable 1 that the LaF3 homogeneous
solid-state membrane (single-crystal) sensor developed by Frant and Ross 1451 has proved to be generally
applicable for the detection of F-. Its main limitations
appear to be that OH- ions interfere in most cases at
high p H values ( > about S.5), owing to the selectivity
constant KF&- = 10-1, and uncertainties can arise
a t low p H values (< about 5 ) as a result of the formation of HF and HF,.
On the other hand, apart from the fundamental work
of Pungor et al. [7-9,11,2211, only relatively few publications on the use of heterogeneous solid-state membrane electrodes have appeared [46-481.
According to theoretical considerations, homogeneous
and heterogeneous silver iodide membrane electrodes
and Ag/AgI electrodes should respond similarly t o I-.
This is in fact so, as is shown in Figure 5 ; the observed
differences are due to the different histories of the electrodes and to differences in the liquid-junction potentials. The selectivities of adequately conditioned homogeneous and heterogeneous membrane electrodes and
electrodes of the second kind with the same ionselective components agree. Deviations are found only
with redox systems. The main advantage of the silver
halide solid-state membrane electrodes over the silver/
silver halide electrodes is that the former is less sensitive to redox systems; difficulties are to be expected if
strongly reducing components lead to the deposition
of silver on the membrane. Homogeneous solid-state
membrane electrodes appear t o have a longer life,
presumably because of the permeation in heterogeneous solid-state membrane electrodes (cf. 1461).
[391 M . Cremer, Z . Biol. 47, 562 (1906).
1401 H . J . C. Tendeloo, J. biol. Chemistry 113, 333 (1936).
[411 I . M . Kolthoff and H . L . Sanders, Proc. Amer. chem. Sac.
59, 416 (1937).
[42] R . Beutner, Amer. J. Physiol. 31, 343 (1912).
1431 F. W. Orme, cf. [3], p. 376.
[44] W. M . Baumann and W. Simon, Helv. chim. Acta, 52,
2054 (1969)
1451 M . S . Frant and J . W. Ross j r . , Science (Washington) 154,
1553 (1966).
1461 H . Malissa and G . Jellinek, Z. analyt. Chem. 245, 70
(1969).
1471 P. Hirsch-Ayalon, Electrochim. Acta 10, 173 (1965).
[481 G. A . Rechnitz, Z . F. Lin, and S . B. Zamochnick, Analyt.
Letters I , No. 1, 29 (1967).
449
Table 1.
Literature survey.
Ion/Component
Solid-state membrane
Glass membrane
homogeneous
H+, OHLi+
F-
[ 2 , 14, 58-86, 1941
[2, 70, 2441
CI
Br-
I-
heterogeneous
Liquid membrane
-
18, 67-69, 1791
11391
145, 84-139, 186,
212, 234-237,
262-2651
I41, 168-171, 202,
268, 2691
141, 192, 202, 2141
141, 184, 202, 214,
241, 270, 2711
IS, 46, 173, 176-178,
137, 167, I721
246, 2671
[9, 46, 176, 179, 2461
18, 9,46, 174-1841
Na’
12, 36, 64,70-78, 82, 107, 167,
I141,2081
K+
169, 185, 2431
[2, 50, 64, 70, 78-80, 2451
121
153--56,21.5,216, 227-230, 2501
Rb+
cs+
PI
n+
L-2, 2441
Sr2+
01
Cdz+
Mg2+
Ca2+
1-21
12391
[2, 641
12, 641
[24,40. 166, 2171
BaZ+
Ni2+
cuz+
Ag+
12501
P501
182,99, 141,2081
6, 24, 38, 43, 49, 64, 82, 99,
140-165, 208, 252, 253, 257-2611
[2I
r2, 81, 2441
sz-
CNZn2f
PbZ+
SCNBF i
[213,2401
[190,202, 214, 2421
D89, 190, 191, 193,
202, 2741
US71
[188.2501
:2501
[9, 176, 2541
[9, 175, 185, 1871
!43,2501
[2011
[19Z,2141
(2461
37, 195-199, 247-249, 272, 2731
:201, 2171
2461
2461
.8,48, 68, 69, 177-1791
b, 26, 481
,2661
c10;
NO;
so:-
[2501
’206,2551
ZOO]
37, 205, 2071
HzP04, HPOi-,
Poi112, 2381
~ 1 3 +
SiFzMnO;
Cr20310;
ReO;
coz
NH:
NH; (Enzymes)
’203,2041
2051
2051
2051
205, 2551
t2, 2091
12, 210, 211, 2451
[83, 231-2331
[49] R . Huston and J. N . Butler, Analytic.Chem. 41, 200 (1969).
[SO] Z . Stefanac and W. Simon, Helv. chim. Acta 51, 74 (1968).
[51] E. W . Moore, cf. [61, p. 93.
[521 E . W. Moore and 1. W. Ross, Science (Washington) 148,
71 (1965).
[53] Z . Stefanac and W. Simon, Chimia (Aarau) 20,436 (1966).
1541 2. Stefanac and W. Simon, Microchem. J. 12, 125 (1967).
1551 L . A . R . Pioda and W. Simon, Chimia (Aarau) 23,72 (1969).
1563 W. Simon, 135th Nat. Meeting Electrochem. SOC., New
York, N.Y. 1969; NRP Work Session on “Carriers and Specificity in Membranes”, MIT, Brookline, Mass., 1969; 20. Mosbacher Colloquium, Mosbach 1969; Tagung Analytische Chemie und Automation, Vienna 1968.
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Angew. Chem. infernat. Edit.
I
Vol. 9 (1970)/ No. 6
The homogeneous solid-state membrane electrodes
with AgCI, AgBr, AgI, and AgzS membrane for the
determination of C1-, Br-, I-, S2- or Ag+ and CNfunction mainly by the transport of silver ions in the
membrane. By mixing these membrane components
withcomponents oflarger solubility and acommon ion,
electrodes for further ions may be obtained. A mixed
crystal electrode with CuS-Ag2S and CdS-Ag2S
membrane for example responds to Cu2+ and Cd2+
respectively [201 213,2261. The electrode response for
the divalent cation in these cases is coupled with the
Ag+ electrode function by the sulfide ion.
solution is similar to that of the sample solution (cf.
also 1491). Sensor designs should accordingly allow
easy adaptation of the electrode fillings to the measurement problem. Electrode systems with exchangeable
membranes are illustrated in Figure 6. The arrangement of the membrane in the liquid membrane electrode prevents the inclusion of air bubbles at the lower
end of the sensor (Fig. 6b). Sealing of the membrane
is effected by pressure.
2
3
/"
L
5
6
7
0
10
9
' /
0
THEOR. INERNST/
11
L
1
1175951
2
3
4
-log a;--
5
6
Fig. 5. Electrode function of iodide sensors [aqueous KI solutions;
cell assembly consisting of ion-selective sensor and calomel reference
electrode (KCI satd.)]. The membrane of the sensor AgI-ETH is a
compressed membrane of purified AgI.
Though the nature of the inner solution of the electrode, according to eq. (l),(2), (18), and (20), should
influence only the electrical zero point &(T) of the cell
assembly, it has been found that many sensors work
best when the composition of their internal filling
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Angew. Chem. internat. Edit. 1 Voi. 9 (1970) 1 No. 6
b)
Fig. 6a.)
'
L
l
S
Sensor with exchangeable solid-state membrane.
1: Plug for inner reference electrode system and electrical screening;
2: screening; 3: metal cap; 4: contact pin; 5: silver contact; 6: metal
spring; 7: platinum duct; 8: glass insert; 9: inner reference electrode;
10: electrode shaft (plastic); 11: internal filling solution; 12: 0 ring;
13: membrane support (plastic); 14: silicone rubber sealing ring; 15: homogeneous solid-state membrane. The membrane 15 is held by sealing
ring 14. This is done by screwing 3 firmly onto I0 by the screening 2 and
the glass insert 8 .
b) Liquid membrane sensor.
14: 0 ring; 15: hollow cylinder (plastic) pressing on membrane 16;
16: liquid membrane (filter paper impregnated with ion-selective ligand).
The membrane 16 is fixed by the hollow cylinder 15 and the 0 ring 14.
This is done by screwing 3 firmly onto 10 by the screening 2 and the
glass insert 8.
Apart from their use in p H measurement, glass electrodes (mainly having the composition NASII-I 8 or
NAS27-4) are also used for the determination of
sodium and potassium ion activities[2.31. The glass
electrodes for the measurement of Na+ activities have
453
KF&a+ values of up to lO4[2,361; on the other hand,
selectivities for K+ over Na+ of only about 10 can be
obtained in glass electrodes for routine use [2,3,5OJ.
Glass electrodes are therefore suitable for the determination of potassium ions e.g. in blood serum only
if the influence of the sodium ions present in the sample
on the E M F of the measuring cell is taken into account.
Corrections of this nature are doubtful, in view of the
dependence of the Kg+,, values on the ion concentration and on the pretreatment of the electrode rs1,521
(cf. 1461). However, liquid membrane electrodes of type
3b with considerably higher selectivities for K+ over
Na+ than can be obtained with glass electrodes can be
produced with the aid of certain antibiotics that
selectively complex K+153-561. Thus valinomycin dissolved in diphenyl ether on Millipore filter c*] gives liquid membrane sensors (Fig. 6b) having a theoretical
linear electrode function to potassium ions in the range
10-1 to 10-5 M (Fig. 7) with selectivities for K+ over
Na+ of m4000 (cf. Table 2), and electrode resistances
of about 1 MG[5s,56,2271. With activity changes of
one order of magnitude, the potentials generally
approach in less than 30 sec to within rtO.5 mV of a
steady value, and normally to within 10.2 mV in one
minute, this value being maintained to within an
average of &1.4 mV over 150 hours with routine use
of the electrode in solutions of various KCI concentrations (10-1-10-4 M).
Table 2. Selectivity constants K E : K + for the valinomycin membrane
~
~~
electrode (25 "C; diphenyl ether).
Mf
KPot
M+K+
1 1 1 1 1 I
1 1 I 1 1 1
~
Rb+
K+
Cs+
NH4+
Na+
Li+
H+
0.52
I
2.6
84
3800
4700
18000
4. Error Considerations
A trivial error calculation shows that small uncertainties in the EMF measurement must lead to appreciable
percentage errors in the determination of the ion
activity or concentration (Table 3). Though shortterm reproducibility to within 0.001 p H unit can in
Table 3. Errors Aai in the determination of the ion activity due to uncertainties A € in the EMF measurement (25 "C).
Aui
_=_.
AE(mV)
10
1
0.1
0.01
zF
RT
A€
in % for ions having valency I
=
1
2
38.92
3.89
0.39
77.85
7.79
0.78
116.77
11.68
1.17
0.04
0.08
0.12
I
3
principle be achieved with glass electrode cell assemblies 1571, much larger deviations are found in practice.
Uncertainties of 0.03 to 0.05 p H unit have been found
in p H measurements on blood samples, presumably
as a result of fluctuations of the liquid-junction potentials [321. This corresponds to errors of 6.9 to 11.5 % in
the determination of the hydrogen ion activity. Standard deviations of (1 % can be achieved in the determination of Na+ concentrations [511. Reproducibilities
of this order can also be obtained with some liquid
membrane electrodes (Fig. 7). At present the valinomycin liquid-membrane electrode makes determinations of K+ in undiluted blood serum possible which
are at least as reproducible as those performed by
flame photometry [228,2291.
Heterogeneous solid-state membrane electrodes a t
least occasionally exhibit permeation of the membrane
by components of the electrode filling solution or of
the test solutionI461, which is probably one cause of
long-term changes in the electrode potential. In permeation experiments with 3H and 1311, homogeneous
solid-state membrane electrodes (AgI-ETH) were
found to have membrane permeabilities of the same
order as that of a Teflon membrane with similar
dimensions (zero current). The permeability of the
membrane can thus. be ruled out as a cause of longterm changes in the potentials of the electrodes examined. Silver halide electrodes occasionally exhibit
large fluctuations of potential as a result of changes in
the intensity of the light [218,2191.
5. Present Situation, N e w Directions
'""L
THEOR
INERNSTI
VALINOMYCIN
3001
2
3
L
5
6
7
-log a x + &
Fig. 7. Electrode function of the valinomycin liquid membrane electrode (25 "C). [Aqueous KCI solutions; cell assembly consisting of membrane electrode in accordance with Fig. 6 b and calomel reference electrode (KCl satd.) with electrolyte bridge (0.1 M NH4NO3)I.
I*] Type MF; Millipore Filter Corp., Bedford/Mass.
454
Although by now a t least 37 ions and components
(Table 1) may be selectively detected by membrane
electrode systems, there are at present only few analytically valuable sensors commercially available.
These may be used either for the direct potentiometric
determination of the activity of a given ion in a mixture of ions or for the indirect determination by potentiometric titration.
Angew. Chem. internat. Edit. J Vol. 9 (1970) J No. 6
Because of t h e restricted ion mobility in t h e membrane
phase, glass as well as solid-state membrane electrodes
have strict limitations in respect t o selectivity (see
Section 2). These limitations d o n o t hold for liquidmembrane electrodes. This advantage, however, has
its price in a relatively short life-time of t h e sensor a n d
a sometimes disturbing contamination of t h e sample
solution by membrane components. At present liquidmembrane electrodes f o r NO;, Ca2+, K+ as well as
[Ca2+ + Mg2+] (water hardness) seem t o b e finding
acceptance in a wide range of analytical applications.
Especially high selectivities are t o be expected f o r
liquid-membrane sensors with certain biologically
active materials (antibiotics) as membrane components. Unfortunately o u r knowledge i n connection
with t h e correlation of t h e structure of organic compounds with their ion specificity is still relatively
poor [56,225].
Extremely high selectivities a r e obtained if an enzymatic degradation of t h e components t o be determined
c a n be used. The enzyme-carrying matrix is sandwiched
between t h e sample solution a n d a sensor which
detects one of t h e degradation products 1 8 3 3 - 2 3 3 1 .
There is no d o u b t t h a t by now only a few possibilities
f o r t h e production of i o n selective sensors have been
pointed out. There is therefore a real h o p e t h a t research in this area will drastically influence analytical
chemistry in t h e widest sense.
This work was supported by the Schweizerischer Nationalfonds zur Forderung der wissenschaftIichen Forschung
(Project No. S188.2).
Received: September 2, 1969
[A 759 IE]
German version: Angew. Chem. 82. 433 (1970)
Translated by Express Translation Service, London
COMMUNICATIONS
New Methods for Preparation of
Glycosides 111 [**I
By Gunter Wulff, Gerhard Rohle, and Wolfgang Kruger [*I
Dedicated to Professor R. Tschesche on the occasion of his
65th birthday
Reaction of 2,3,4,6-tetra-O-acety1-a-~-g1ucopyranosy1
bromide with the silver salt of 4-hydroxyvaleric acid in benzene
gives the glucosyloxy-acid (2) and the I-0-(glycosyloxyacy1)glucose ( 3 ) as well as the very unstable I-0-acylglucose
(1).
H
Q
H
OAc
oH
=
-0-C-CHz-CHz-CH-CH3
(2), R
=
-0-CH-CHz-CHz-COOH
The new method is extremely simple and mild: one merely
stirs the readily available silver salt and, e.g., 2,3,4,6-tetra-Oacetyl-a-D-glucopyranosyl bromide in dry diethyl ether for 30
min at room temperature or for 4 h at -10 OC; and since no
water is produced there is none to remove. 4-Cholestenol, for
example, gives almost wholly 3,5-cholestadiene by the usual
methods, whereas we obtained the glucoside in 36 % yield.
The reaction is clearly applicable also to alcohols of various
types [51; and other cis-halogenoses, e.g., 2,3,4,6-tetra-Oacetyl-u-D-galactopyranosylbromide and 2,3,4-tri-O-acetylP-D-arabinopyranosyl bromide, react analogously.
The reaction is highly solvent-specific; it occurs best in
diethyl ether. Studies of anion-dependence, of the products,
and of the kinetics are in accord with a trimolecular synchronous mechanism.
AcO
(I), R
this reaction. Thus, for instance, we obtained cholesterol
P-D-glucoside in 58 % yield (only 33 % 121 or 43 % [31 by the
Konigs-Knorr method and 45 % by Kochetkov’s methodl41)
and a 65 % yield of tigogenin P-D-glucoside (45-50 % by
the Konigs-Knorr method).
II
0
c H3
H
OAc
AcO
CH-CH3
(3), R =
H
Silver salts of other 4- and of 5-hydroxyalkanoic acids give
analogous products. Moreover, silver salts of 2-, 3-, and
6-hydroxyalkanoic acids afford corresponding products, but
here the 1-0-acyiglucoses are appreciably more stable.
Thus glucosylation of the alcoholic hydroxyl group of the
hydroxyalkanoic acids occurs to a considerable extent in this
reaction. We have therefore investigated the possibility of
glucosylating added alcohols similarly. We found that, in the
presence of silver salts of 2-, 3-, or 4-hydroxyalkanoic acids,
or of 1,3- or 1,4-dicarboxylic acids, alcohols react with 2,3,4,6tetra-0-acetyl-a-D-glucopyranosyl
bromide in ether to give
good yields of 2,3,4,6-tetra-O-acetyl-~-~-glucosides.
Silver
4-hydroxyvalerate proved particularly favorable for use in
Angew. Chem. internat. Edit. / Vol. 9 (1970)1 No. 6
+ AgBr
This reaction occurs to any considerable extent only on the
surface of solid bifunctional anions of specific structure.
Such anions include those of 2-, 3-, and 4-hydroxyalkanoic
acids and of certain dicarboxylic acids in which neighboring
group effects limit the formation of 1-0-acylglycoses in favor
of glycoside formation by way of a trimolecular transition
455
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