NITRATE-SELECTIVE LIQUID MEMBRANE-ELECTRODES

C. Liteanu*, E. Stefaniga** and E. HopTrtean**

* Department of Chemical Technology
University of Cluj-Napoca, Romania,
** Institute of Chemistry Cluj-Napoca, Romania

CONTENTS
Page
INTRODUCTION 160
NITRATE-SELECTIVE LIQUID MEMBRANE-ELECTRODES 160
Nitrate-Selective Liquid Membrane -Electrodes Based on
Quaternary A mmonium Salts 1*63
Nitrate-Selective Liquid Membrane-Electrodes Based on
Quarternary Phosphonium Salts 166
Nitrate-Selective Liquid Membrane-Electrodes Based on
Triphenyl Methane Dyes 167
Nitrate-Selective Liquid Membrane-Electrodes Based on
Complexes 168
Other Nitrate-Selective Membrane Liquid-Electrode Types 170
APPLICATION OF NITRATE-SELECTIVE UQUID MEMBRANE-
ELECTRODES 170
Determination of Nitrate in Soils and Rocks 170
Determination of Nitrate in Vegetable Extracts, Fruits
and Juices 173
Determination of Nitrate in Water 175
Determination of Oxides of Nitrogen in Gases and the
Atmosphere 177
Another Application of Nitrate-Selective Liquid
Membrane-Electrodes 179
REFERENCES 1on

159
 INTRODUCTION

Liquid membrane-electrodes (LME) are efficient both in direct deter-

mination and in industrial analysis due to their capacity to determine
ions in solutions selectively, continuously and quickly. Consequently
methods which use ion selective membrane-electrodes tend to replace
classical methods.
The nitrate-selective liquid membrane-electrode is of considerable
practical importance and in the present review, we discuss different
types o f NO3-selective liquid membrane-electrodes as well as their
practical applications.

NITRATE-SELECTIVE LIQUID MEMBRANE-ELECTRODES.

PERFORMANCES AND CLASSIFICATION DEPENDENT ON THE
ACTIVE ELECTRODE COMPONENT.

The nitrate-LMEs described in the technical literature are obtained

b y dissolving a long chain organic substance (e.g. quaternary ammonium,
phosphonium or arsonium salts, triphenylmethane dyes, Fe(II) or Ni
(II) o-phenanthroline complexes) which act as the electrode compound
and have ion exchange properties in different solvents.
In order t o obtain them as active electrode components a b u l k y ca-
tion (usually as nitrate) and an adequate solvent, are necessary.
The basis o f the electrode function may be written as

R X + NO3 = R N O j + X" (1)

where R denotes the active cation. The equilibrium must be displaced

towards the right. In this case the generated potential may be expressed

Ε = const. - 2 f 3 *T log(aA + K ^ A ^ a„) (2)

A

where K P ° ^ z a / z Β is the selectivity coefficient a; a . is the activity of

the primary ion; a f i the activity of the interfering ion B; and ζ the val-
ence o f the ion concerned.
From this expression it is apparent that the electrode would have an
ideal response, specific for i species (i = N O j ) if the selectivity coeffi-
cient were zero, but as an infinite selectivity is impossible the first term
in expression (2) is definite only i f K P o t R z A / z Β has a very low value or

160
when the interference is absent. Consequently in real cases, the contri-
bution of the second term always appears.
Among the parameters that influence the selectivity coefficient note
must be taken of the organic salt concentration /1 / in the solvent.
As a rule, the operating mechanism of a LME is based upon the for-
mation of a liquid extraction system, so that at the membrane-solution
interface an exchange takes place between the ions in the aqueous phase
and the same ions coupled to the organic group in the membrane phase.
A comparison of the values of the extraction constants ( E q B ) for
ion-pair formation of various anions with the tetrabutylammonium ion
/2/ and the selectivity constant K ^ - „ for the nitrate-selective elec-
trode based on tridodecylhexadecylammonium nitrate /3/, Table 1, illu-
strates this.

TABLE I
Ion pair extraction constants of the tetrabutyl-ammonium ion
compared with selectivity constants K ^ - of a nitrate
3>
ion-selective electrode with tridodecylhexadecylammonium nitrate /2/.

Ion Β NO3- CR Br" cio; cio4 r

E
QB/EQ,NO 3 - 1 3.2xl0"2 7.9x10"' 1 1.2x 10 2 42
E E
QB/ Q,NO3- 1 1.8x10"' 8.9x10"' - 11.1 6.5
Kpot
NOJ.B 1.0 5 χ 10" 3 0.16 1.66 800 17

Generally the ion exchanger is dissolved in a suitable solvent. In this

respect the solvent used must fulfil the following requirements:
- be water-immiscible so that any mixing of the phases will be
minimal,
- have a viscosity high enough to prevent its rapid loss by flow across
the membrane,
- have a high dielectric constant,
- be chemically stable
- be pure and have a high exchange capacity.
From the point of view of LME performances there are two practical
possibilities namely either to use a porous carrier e.g. a glass frit, (Fig. 1)
impregnated with a water-immiscible mixture of ion-exchanger and sol-
vent or an "inert" carrier such as cellulose acetate, PVC membrane,

161
Fig. 1. S c h e m a t i c representation of liquid membrane-electrode. 1-membrane;
2-screw head; 3-liquid ion exchanger; 4-internal reference solution;
5 - s i l v e r - s i l v e r c h l o r i d e reference e l e c t r o d e .

natural rubber, silicone rubber or another organic film compatible with

the ion exchanger and immiscible with water, Fig. 2.
The first possibility is disadvantageous mechanically because the or-
ganic liquid may leak into the aqueous sample solution. These electrodes
may suffer from pronounced and erratic potential drifts and are charac-
terized by fairly poor sensitivity and gradual changes of sensitivity and
selectivity.
These drawbacks have been eliminated by introducing a non-porous
PVC polymer support /4,5/ in which the organic solution of the ion ex-
changer is immobilized.
Depending on the chemical composition of the electrctde-active com-
pound NOj-selective LMEs based on the following have been devised:
1. quaternary ammonium salts, R 4 N +
2. quaternary phosphonium salts, R 4 P +
3. triphenylmethane dyes
4. Fe(II) or Ni(II) phenanthroline complexes.

162
Fig· 2.Liquid membrane-electrode. 1-PVC ion exchanger membrane; 2 - P V C
tubing; 3-internal reference solution; 4-araldite seal; 5-silver-silver chloride
electrode, 6-solder j o i n t ; 7-ground glass j o i n t ; 8-silicone rubber adhesive;
9-screened cable.

Nitrate-Selective Liquid Membrane-Electrodes Based

on Quaternary Ammonium Salts

In the case of these electrodes, the active electro.de component ful-

fils the necessary conditions namely: high molecular weight, good
chemical stability and the presence of a mobile positive cation, R 4 N + .
The possibility of employing a wide variety of organic solvent extrac-
tion (ion association and chelation) systems for use in ion-selective elec-
trodes has been explored by Coetzee and Freiser /6,7/. Organic and in-
organic salts of the tricaprylmethylammonium ion (Aliquat 336 S)
dissolved in 1-decanol, function as an organic phase component of a

163
hexadecyl benzylammonium nitrate in decylalcohol, tetraethylammo-
nium nitrate in octyl alcohol or cetyltrimethylammonium nitrate in
octyl alcohol were studied by Gordievskii et al. / I I / . The liquid mem-
brane-electrodes thus obtained have a high sensitivity towards N0 3 ~
giving a linear response from 10"1 to 10" 4 M in the presence of the fol-
lowing anions Π, Br", C 1 N 0 2 S 0 4 2 A c C T , H 2 P 0 4 C 0 3 2 " and F".
Trialkylbenzylammonium chloride in benzylchloride was used /12/
in the construction of an electrode with a more extended concentration
range.
N0 3 ~-selective electrodes having a particularly simple design were
made from tetraoctylammonium nitrate and tetradecylammonium ni-
trate in phenyl chloride /13/. The experimental data show that in the
case of the tetraoctylammonium nitrate electrode, chloride and bromide
interfere more strongly than with the tetradecylammonium nitrate elec-
trode.
Materova et al. /14/ studied a nitrate electrode based on the liquid
exchanger tetradecylammonium (TDA) nitrate in phenylchloride in
strong acid media. The experimental data showed a different response
of the electrode in these conditions, due to H N 0 3 molecules being
bound by the amino groups. Thus in acid solutions the calibration
curve shows linear parts whose angular coefficient is a multiple of
58 mV, Fig. 3.
The behaviour of the N0 3 ~-selective LME in strong acid media was
governed by the number of moles of H N 0 3 attached to the TDA · N 0 3
adduct in the organic phase.
When comparing the results of e.m.f. measurements to those obtain-
ed by absorption it is seen that determinations up to 0,2 Μ give a single
signal, that for the N 0 3 " - i o n . At higher concentrations, associations of
the type [ N 0 3 ~ · H N 0 3 ] or [ N 0 3 " · 1 , 5 H N 0 3 ] are also present.Simi-
lar responses are given by the triethylamminonitrate electrode /15/ as well
as nitrate-selective membrane electrodes obtained with other classes of
compounds e.g. phosphonium salts, triphenylmethane dyes and phen-
anthroline complexes /16,17/. The different responses of these elec-
trodes in acid media may be explained on the basis of complex forma-
tion. A determination method for the composition of complex particles
in organic media was thus established according to the angular coef-
ficient of the calibration regression equation:
Ε = f(log a A )
used in case of reversibility of the electrode towards A".

164
 As we have already seen, one of the major contributions to the de-
sign of LMEs was the introduction of non-porous PVC membranes by
Moody et al. /4,5/. PVC membranes were also successfully used by
Ruzicka et al. /18/. Fiedler and Ruzicka /19/ established several rules
for the preparation of this type of membrane.
On this base it was established that N0 3 ~-selective electrodes may
be obtained by incorporating the ion exchangers of commercial elec-
trodes in polymers. Thus, Davies et al. /3/ established that in the case of
the electrodes supplied by Orion and Corning, the inclusion of the active
electrode component in PVC prolonged the functioning time of the de-
vice. The LME stability depends on how readily the electroactive mater-
ial dissolves in the aqueous sample phase /4,18-20/. This solubility is
highly dependent on the distribution coefficient of the electroactive
material between the membrane and the aqueous phase: the electrode
stability will improve with an increase of the distribution coefficient.
This coefficient is dependent on the choice of the plasticizer and its ad-
mixture with the electroactive material as well as the enthalpy of dis-
solution /21/ associated with this process. In this respect, a detailed

165
study 122/ of the response of NOj-selective LMEs was performed by
establishing some criteria for selecting the membrane constituents to
obtain optimal electrode parameters. This was proved using as active
electrode components trioctylmethylammonium (TOMAN), tetraheptyl-
ammonium (THAN), tetraoctylammonium (TOAN),tetradodecylammo-
nium (TDDAN) and tetratetradecylammonium (TTDAN) nitrates.
Using three of these quaternary ammonium salts /22/ in different sol-
vents /23/ it was established that the tetradodecylammonium nitrate
(TDDAN) electrode may be used to determine NOj at very low concen-
tration levels ( 5 x l O " 7 M ) in the pH range 3-11. The determination of
NO3 activity has been achieved similarly by use of a liquid membrane-
electrode whose active component is tetradecylammonium nitrate /24,
25/. A liquid membrane-electrode was also prepared by use of Aliquat
336 S nitrate /26/ in a PVC matrix and used to determine NO 3 in the
concentration range 1-10" 3 ' 5 M. The use of dibutylphthalate as plasti-
cizer /27/ in PVC does not change the electrode response, the NO3 ion
determination being achieved in the presence of other anions. The static
and dynamic response times for electrodes with PVC matrices have been
studied /28/.
An ingenious technique for constructing membrane electrodes con-
sists /29/ of a thin layer of liquid adsorbed on a porous carrier on the
electrode surface. The organic phase used was Aliquat 336 S /30/ as
nitrate or the liquid ion exchanger Orion 9 2 - 0 7 - 0 2 mixed with graphite
powder and treated with ceresin wax /31 / to inhibit the influence of pH.

Nitrate-Selective Liquid Membrane-Electrodes Based

on Quaternary Phosphonium Salts.

Various compounds of quaternary phosphonium salts are suitable

for making NOj-selective LMEs. The liquid membranes formed by
tetraoctylphosphonium salts in decyl alcohol or tetraphenylphosphon-
ium salts in nitrobenzene /32/ are sensitive to NOj.Cl", Br" and Γ ions.
In the case of membranes with tetraoctylphosphonium salts linear rela-
tionships are obtained between the potential and the ionic activity i;
Ε = f(aj) but a Nernstian behaviour was given only by the iodide ion in
the 10"1 - 10" 4 M concentration range.
The same electrode may be used for the direct determination of dif-
ferent acids e.g. H 3 P 0 4 , H 2 S 0 4 , H C 1 , H N 0 3 /33/ the relative errors of
the determination being < 10%.

166
 Other liquid membrane electrodes of this class were obtained using
compounds of the A l c 4 P N 0 3 type, where A l e may be tetracetylphos-
phonium (TCFN), tetraoctylphosphonium (TOFN) or tetraamylphos-
phonium (TAFN) nitrate dissolved in ethyl bromide /34/. The differing
electrode responses are determined by the difference between the solu-
bility of the salts in ethyl bromide; this difference decreases in the order
TCFN > TOFN > TAFN. The selectivity of the electrodes decreases in
the same order.
A NO3-selective electrode was obtained similarly using the tetra-
phenylphosphonium bromide /35/ in solvents such as chloroform, dich-
lorethane, benzyl alcohol, nitrobenzene or carbon tetrachloride. While
studying responses of the electrode in the presence of a series of anions:
S 0 4 2 " , C 0 3 2 - , P 0 4 3 " , citrate, H S 0 4 ' and H C 0 3 " it was established
that the use of benzyl alcohol introduces increased sensitivity to anions
that undergo alkaline hydrolysis. The presence of SCN~,C10 4 ~, CI" and
I" diminishes the electrode's sensitivity for nitrate.
Tributyloctadecylphosphonium nitrate /36/ dissolved in o - or p -
nitrophenyl-n-hexyl ether included in a PVC matrix also produces a
NO3 responsive electrode.

Nitrate-Selective Liquid Membrane-Electrodes Based

on Triphenyl Methane Dyes.

Several basic triphenylmethane dyes have been used as active com-

ponents in liquid membrane-electrodes selective for univalent anions
and various other dyes: e.g. azine, oxazine,thiazine, xanthene, acridine,
polymethine and phthalocyanine have also been examined.
The membranes /37/ formed by ΙΟ"2 Μ nitrates of Crystal Violet,
Ethyl Violet, Aniline Blue, Victoria Blue R, 4R, Β or BO, Acridine
Red 3B, Rhodamine 3B and 5G, Nile Blue Cyanine and Astra Blue in
nitrobenzene give the theoretical electrode responses for pN0 3 ~ from 1
to 3.5, the potential being established with a ±.0.3 mV repeatability
in a few seconds. It was ascertained that an extension of the concentra-
tion range between pNOj 4.4 and 5.3 is possible if the concentration of
the active components are decreased to 1(Γ3 and ΙΟ -4 Μ respectively.
Liquid membranes were obtained from the same component class
using other dyes: e.g. Malachite Green, Methyl Violet, Fuchsine Alkali
Blue, Crystal Violet and Gentian Violet /38/, but the results obtained
with Malachite Green, Alkali Blue and Fuchsine were unsatisfactory.

167
 Gentian Violet /39/ or Crystal Violet /38/ in tetrachlorethane, nitro-
benzene, chloroform and chlorbenzene were found to be adequate elec-
trode components for N0 3 ~. The nitrate ion determination was made in
the presence of a series of ions and it was established that chloride ion
interferes strongly but C 0 3 2 ~ HC0 3 ~ and HPO 2 " are without effect.
Generally liquid membrane electrodes based on this type of dye per-
mit the determination of N0 3 ~ over a large concentration range.

Nitrate-Selective Liquid Membrane-Electrodes

Based on Complexes.

Amongst the first anion selective membrane-electrodes were chelate

compounds of metals such as Fe 2 + or Ni 2+ with the organic ligand o -
phenanthroline /40/. Salts of Fe or NiL(N0 3 ) 2 type where L has the
structure shown below, function as anion exchangers:

2+

Ross /41/used the complexes of Ni 2+ , Co 2 + or Fe 2 + with bathophen-

anthroline or 1,10-phenanthroline in p-nitrocymene. The electrodes
thus obtained are stable and reproducible to ± 1 % , but the one based
on Fe 2 + with bathophenanthroline shows a tendency to undergo oxida-
tion to the Fe 3 + complex. Using the Fe 2 + complex of o-phenanthroline or
bipyridine /42/ a particularly good nitrate-selective liquid membrane-
electrode was obtained.
Liquid membranes containing tris(l ,10-phenanthroline) iron (II)
[Fe(phen) 3 ] 2 + , tris(4,7-diphenyl-1,1 O-phenanthroline) iron(II) [Fe
(d-phen) 3 ] 2 + and tetraheptylammonium ion (tetrahep) in nitrobenzene,
chloroform or n-amyl alcohol have been constructed and evaluated
/43/. The selectivity constants of these electrodes are given in Table III.

168
 TABLE III
Selectivity constants KP" 1 of phenanthroline and quaternary ammonium
ion-based NO3-selective liquid membrane-electrodes /43/.

2+
Interfering [Fe(d-phen) 3 ] [Fe(phen) 3 ] 2 + Tetraheptyl
ion (j)
1 xl(T3M 2 χ 10 3
Μ 2xlO" 3 M 5 xlO" 4 Μ 1 χ 10"2 Μ

nitro- chloro- amyl nitro- nitro-

i benzene form alcohol benzene benzene

NO3" 1 1 1 1 1
c r 40 21.7 4.0 3.0 27.5
Br~ 5.3 1.5 1.6 1.6 4.2
I~ 8.1 χ 10"2 1.8x10' "2 0.4 6.6 xlO" 2 9.1 xlO" 2
BF; 4.2 χ 10" 2 1.3x10 1.2 2 . 1 x 1 0 " ' 2.6 χ 10"2
CIO; 1.5 xlO" 3 8.3x10' -3 2.1x10"' 5.2 χ 10" 3 1.4 χ 10" 3
1.5 χ 10 - 3 1.3x10' -3 8.3x10"' 6.3 xlO" 4 7.8 χ 10 s
-3
SCN" 2.9 χ 10"2 2.9x10' 1^9x10"' 4.6 xlO" 2 3.3 χ 10"2

The selectivity coefficients do not depend on the membrane compo-

sition except with amyl alcohol as the solvent. The selectivity order is
P F 6 " > C 1 0 ; > S C N - > Γ > BF" > N 0 3 " > Br""> C P .
This order approximates to that of the increase of the hydration
energy of the anions thus indicating that the aqueous solvation energies
may play a predominant role in determining electrode selectivities for
these ions /42/.
With regard to the selectivity coefficient of the electrode based on
[ F e ( p h e n ) 3 ] 2 + in P h N 0 2 good results were obtained for some ions by
comparing it with the free extraction energy corresponding to the [Fe
( p h e n ) 3 ] 2 + salt in nitrobenzene /44/. It was ascertained that the factors
that influence the selectivity are identical with those which influence
the extraction process /45/. In case of the electrode based on the Ni 2 +
complex of tris(bathophenanthroline) the effects of three solvents i.e.
2-nitro-phenyloctyl ether, 2-nitrophenyl ether and 2 - n i t r o - p - c y m e n e
were studied and established /46/.
The effect of irradiation by 6 0 Co upon the stability of membrane
electrodes based on complexes was also studied /47/. It was ascertained
that radiation doses of 5 x l 0 7 r a d . m i r f 1 cause non-linearity of the
electrode function and that the main effect is on the inner reference
solution.

169
Other Nitrate-Selective Membrane Liquid-Electrode Types.

A nitrate selective liquid membrane-electrode was obtained using

Nitron nitrate in various solvents: e.g. benzyl alcohol, aniline or chloro-
form 148/ as the electrode active component. In the case of benzyl alcohol
there was a linear response of the electrode between 1 and 10"3 Μ and a
slope of 53-54mV over a pH range between 1 -9. The electrode charac-
teristics were also studied with nitrobenzene as the solvent /49/.
The membrane obtained by compacting diethyldithiosilver carbamate
with a slight excess of AgN0 3 , is responsive to nitrate between pH4 and
11 /50/. The ion exchange properties of pyridine or dimethylphenyl-
amine groups were used to obtain a similar nitrate-selective liquid
membrane-electrode /51/.

APPLICATION OF NITRATE-SELECTIVE LIQUID

MEMBRANE-ELECTRODES.

Determination of Nitrate in Soils and Rocks.

In agriculture as in geology an exact knowledge of the mineral com-

position of the soil is essential. Owing to the simplicity of the Potentio-
metrie method, N0 3 ~-selective membrane-electrodes have been used
widely for the rapid determination of the nitrate content of soils or soil
extracts, since the usual nitrate determination methods are tedious.
The nitrate in soil is usually determined by extraction, distillation,
microdiffusion or colorimetry /52/. A nitrate selective liquid membrane
electrode may be used in several ways to determine this ion in the soil
/53-57/. The presence of N 0 2 " or Cl~ ions interfere. NO3 activities
measured by the nitrate specific ion electrode have been compared in
soil suspensions and filtrates /58/. The data in Table IV show that the
mean values of the extractions do not differ much from those obtained
in suspensions or filtrates /58/. This is important because the filtration
of samples from clay soils requires a long time. It was also established
that the soil samples may be extracted with water, requiring in this case
a prompt analysis in order to prevent biological losses /58/ and to avoid
the use of phenylmercurinitrate as an inhibitor /59/. The analysis must
be carried out within an hour of extraction.
The presence of chloride in the soil or the introduction of KCl dur-
ing the extraction /58/ presents interference problems for the electrode

170
 TABLE IV
Determination of NO 3 in soil /58/. a

Method
Soil type
Electrode Xylenol Autoanalyzer

C u S 0 4 (0.01 M) KCl (2 Μ)

High organic sand 21.0 21.6 21.0

Sandy peat 13.1 14.2 14.0
Peat 1.6 1.5 1.5
Peat 2.0 1.3 1.3
Peat 5.2 4.7 4.7
Peat 63.8 63.3 67.2
Gay-peat 23.4 C 23.0 C

a) On filtrates of extracted samples (mg/litre - 1 ) one day after extraction.

b) Using sulphanilamide and N-l-naphthylethylendiamine reagents.
c) Mean values for copper sulphate and potassium chloride extracts by all three
analytical methods.

as well as for the xylenol method. Chloride can, however, be avoided by

using a special buffer /60/ and nitrite may be destroyed with sulphamic
acid. /61/.
Other researches on soils /59,61 -64/ confirm chloride ion interfer-
ence in the determination of nitrate. It has also been mentioned that in
case of soils that do not contain water-extractable nitrates or nitrites,
the analysis may be performed by adding known amounts of K N 0 3
/61/.
The results thus obtained may be compared with those by the stan-
dard Kjeldahl method, but are lower than the phenol disulphonic acid
technique /61/. It was shown that the use of CaS0 4 facilitates the NO3
extraction from claylike soils and rocks /62/. The presence of interfer-
ing ions may be removed by adding Ag 2 S0 4 or CuS0 4 solutions (0.02
- 0.1 M) /65/ or sodium citrate /66/. Some errors which occur during
the nitrate ion determination in aqueous soil extracts may be elimin-
ated by the removal of colloidal particles by aggregation or filtration
with Polyacrylamide /64/. The nitrate content of tropical soils /67/ has
been determined using a nitrate selective liquid membrane-electrode
with the addition of nitrate standards containing known amounts of
interfering anions (N0 2 ~ and Cl~) which are frequently present in tropi-
cal soils. Thus it was established that this electrode may be used for ni-
trate determinations in soils with high salt contents by paying due at-

171
tention to the presence of interfering anions. The determination was
made in the range pH 4 to 8 in the presence of a high content of organic
matter (1-13%). Nitrate present in soil between 4 and lOOppmN con-
centration can be accurately determined provided ionic strength varia-
tions are eliminated by adding a 1% solution of Κ [ A 1 ( S 0 4 ) 2 ] /68/ or
CaCl 2 /69/.

The accuracy and the precision of the Potentiometrie method was tes-
ted by adding a known amount of N O j to the soil sample /59/. The
Potentiometrie method was also compared with the extraction-distil-
lation determination /70/ and colorimetric methods /71,72/. Good
agreement was obtained between the different techniques.
Generally, in soil analysis the extract should be decanted and centri-
fuged before the analysis but reproducible results may be obtained with
good stirring and temperature control of the solutions. This was made
possible by using the constant stirring cell /73/ shown in Fig. 4.

Fig. 4.Flow-through electrode unit. 1 -nitrate electrode; 2-reference electrode;

3-high impedance expanded scale pH-meter; 4-funnel; 5-magnetic stirrer;
6-air by-pass vent; 7-overflow to water pump.

Such a cell may be included in an automatic analysis system, which

determines several ions simultaneously (NOj, K + , Na + ) in soil extracts
/74/. A . 0 3 μ ΐ sample was injected in a 0.01 Μ N a 2 B 4 0 7 , 0 . 0 1 Μ NaOH
and 0.2% glycine jet to a cell containing the N0 3 ~-selective liquid mem-
brane-electrode /75/, which is able to determine the NO3 content with
a ± 2% standard deviation. A similar automatic system allows the deter-
mination of NO3 ion in the presence of K + or PO^" in samples smaller
than 5 μΐ /76/ or of NO3 and the pH of the soil /77/.

172
Determination of Nitrate in Vegetable Extracts, Fruits and Juices.

The NOJ content of vegetables can be considered as a measure of the

need to use chemical fertilizers. The nitrogen content in plants shows
the assimilation and the degradation of nitrogen containing fertilizers.
A quick nitrogen determination maybe performed with the Potentio-
metrie method using an LME.
The working procedure in case of these vegetables, which are solids,
consists of previous treatment of the dry samples by grinding or ashing
and extracting the residue in cold or hot water,alkali or acids as required
and determining the N O j ion in the solution.
Paul and Carlson /78/ have used this mode of action with an Orion
92-07 N 0 3 selective liquid electode. The presence of other ions in the
solution raised the problem of electrode selectivity. For nitrate-selec-
tive liquid membrane-electrodes, the severity of anion interference de-
creases 131 in the order: C 1 0 4 > I" > C 1 0 3 ~ > Br" > N 0 2 " > C N ~ >
C I " > S 0 4 2 " > H P < V " > F*. Chloride is contained in plants (0.5-2%)
but iodide which causes no problems is usually below the electrode de-
tection limit. The S 0 4 2 ' ion being tolerated by the LME allows N 0 3 "
to be extracted with 0,025 Μ A 1 2 ( S 0 4 ) 3 from grass, cereal crops and
strawberries /79/.
In order to determine N 0 3 ~ precisely in plant extracts, Cl~ elimina-
tion is recommended if it exceeds > 2%. A Dowex type cation resin or
precipitation with Ag 2 S0 4 may be used /78/. It was established that an
ion exchanger may be used if it is removed by filtration. The A g 2 S 0 4
may precipitate in the presence of a calomel electrode. Bicarbonate
(HC0 3 ~) or organic acid interference may be eliminated using the same
Dowex resin in the A1 J + form. The halogen or sulphide anion effect
maybe excluded by adding 0 , 0 2 - 0 , 1 Μ Ag 2 S0 4 or CuS0 4 to the liquid
plant extract /65/. Inconsistent results due to variation of ionic strength
may be excluded by adding a 1% [KA1 (S0 4 ) 2 ] /68/ or sodium citrate
/66/ solution.
The N 0 3 ion Potentiometrie method has been used /60,80,81/ with
few changes for a variety of plants. N 0 3 determination in vegetable ex-
tracts is also possible with the N 0 3 " selective electrode since nitrates
are highly water-soluble. This quality allows determinations in vegetable
residues /69/ by extracting with demineralized water. The results ob-
tained are in good agreement with those from the classical distillation
method.

173
 In the same manner, the N O j content of nutrient solutions /69,82/
may be determined, thus allowing the determination of nitrate absorp-
tion dynamics in plants. NOj has been determined by LMEs in sugar
beet leaves /81/. The values obtained in roots were higher than those in
leaves obtained using the phenoldisulphonic acid technique (387 ppm
as compared with 253 ppm) owing to the oxidation of amines especially
in the roots during the maceration in the phenolsulphonic method thus
increasing the nitrate contents. The N O j content of spinach /83,84/ was
also determined with a nitrate selective membrane-electrode. Ionic
strength variations were eliminated by extracting the spinach with a 1 %
N a 2 S 0 4 solution; the determination error was ca 3%. The Potentio-
metrie method was in this case compared with the xylenol colorimetric
method.
Chloride or oxalate present in spinach did not adversely influence
the results. The NO3-selective electrode was used also to determine 10
ppm quantities of NO3 in grass and clover /85/.
The standard addition method was studied in the case of the N 0 3
LME in the presence of interfering ions and a correction equation was
established /86/. A similar equation and the operating conditions for 8
different plants /87/ were established as follows:

ΔΕ
"Αν+ j h X
( V V
NO -(%)
B
weighed sample
v"TiT ^ v - V
10 -c

where
ΔΕ = potential difference (mV) resulting from the potential
measured before and after the addition of standard
Av and A n are the ordinates of the calibrations regression before
and after the addition
Bv and B n are the slopes of the calibration regressions before
and after the addition
η = the number of measurements
F = the stoichiometric factor
C = the final concentration after the standard addition in
100 ml solution.

174
 Milham et al. /60/ used a special buffer at pH = 3 containing sul-
phamic acid in order to destroy nitrites from plant samples. Close agree-
ment was obtained both by the Potentiometrie and by the Devarda alloy
reduction method, the correlation coefficient being ± 0,99 as may be
seen in Table 5.

TABLE V
Comparative determination of NO 3 in plants.

NO 3 - N/ppm
Plant
Devarda Direct potentiometry

Cotton petiole 24.100 24.100

17.100 17.100
18.720 18.710
2.560 2.530
11.670 1.640
Oat leaves 470 450
480 475
1.410 1.380
Maize leaves 2.980 2.950
120 100
Wheat leaves 1.460 1.460
Tomato leaves 641 638

The errors due to N0 2 may be eliminated by complexing with sulpha-

nilamide in 0.005 Μ H2 S0 4 allowing NO3 to be determined in the range
between 10 and 500 ppm /88/. Rapid NO3 analysis in plant extracts
may be done in a continuous flow cell /73/, the main variation coeffi-
cient of the results obtained on seven plant samples being ± 0.63% as
compared to ± 1.55% when each measurement was performed separ-
ately /60/.

Determination of Nitrate in Water.

A knowledge of the NO3 content of water is important in pollution

control because a high NO3 content has a harmful effect. Classical me-
thods rely on colorimetry (using brucine, 2,4-xylenol or phenoldisul-
phonic acid)but potentiometry with a NO3-selective liquid membrane-
electrode may also be applied.

175
 The nitrate content of drinking water containing high concentrations
of Ca and Mg soils /89/ has been effected in this way and the results
compared with those obtained with the spectrophotometric method
using phenoldisulphonic acid. In this case, the working conditions were
established and the influence of the ionic strength upon the potential
stability was studied.Similarly the NO3 ion content between 0.5-5 ppm
has been determined by potentiometry with a floride ion-selective elec-
trode and by spectrophotometry in mineral water /90/.
Langmuir and Jacobson /91 / have calculated the approximate amounts
of different anions which when present together with 10 mg NO3/I pro-
duce a 1% error by the LME method. The most interfering anion was
found to be N 0 2 with as little as 1.2 mg/1 sufficient to cause an error
+ 1%, C I " at 2 m g / l produced a similar error. Sulphate causes little in-
terference ; there must be > 5000 mg/1 S 0 4 2 " t o cause an error of l % i n
the determination.
The N0 3 -selective membrane electrode has been used to determine
N 0 3 " in various water samples and the problem of interferences and
their removal is frequently met. The elimination of nitrite may also be
performed with sulphamic acid according to the reaction:

2 N 0 2 " + (NH 2 OH) 2 H 2 S 0 4 —• 2N 2 Ο + S 0 4 2 " + 4H 2 Ο

or by quantitative reduction /92/ to NH 3 .

The interference of Cl~ and HCO~ ions was removed with Ag 2 S0 4
in the presence of phosphate buffer /93/ which maintains a constant
ionic strength. The accuracy of the determination was > 2%. By adding
AgOH /94/ concentrations of NO3 down to 0.6mg/1 were determined.
If HCO3 or Cl~ exceed 40mg/l they may be eliminated with ion ex-
change resin in R-Ag form /95,96/.Ionic strength variations were elimi-
nated by adding K 2 S 0 4 /97/ or MgS0 4 /98/.
Bunton and Crosby /99/ have determined N 0 3 and obtained good
agreement in ten water samples both by colorimetric and Potentiometrie
methods. No significant differences were obtained from 400 water sam-
ples analyzed with the two methods by other workers /100/, but the
N O j - L M E Potentiometrie method was faster and easier to perform.
The same conclusion was reached by yet another group analyzing efflu-
ent water containing 2 - 2 0 m g NO3/I with the NO3-LME and the bru-
cine colorimetric method /101/. NO~ in water /102/ has been determined
with good results using LMEs base on triphenyl methane dyes.

176
Determination of Oxides of Nitrogen in Gases
and the Atmosphere.

The nitrate selective LME has been used recently for the rapid deter-
mination of nitrogen oxides in cigarette smoke and other gaseous mix-
tures.
Since combined nitrogen is present in gases mainly as oxides or NH3
or in various organic compounds, these must be converted to NOj be-
fore measurement /103-108/.
Di Martini /103/ has determined nitric oxide with a NO3-LME fol-
lowing ozonization and absorption in water. The reactions are:
NO + 0 3 —* N0 2 + 0 2
2N0 2 + 0 3 —> N 2 O s + 0 2
N 2 O s + H 2 0 —*• 2HNO3
3N0 2 + H 2 0 —> N 2 0 5 + 2H+ + NO
In this case the lower determination limit was 1.4 χ 10"8 mole. The N0 2
content in air was determined similarly /106/. The nitrogen oxides were
converted to N 0 3 " with 2% H 2 0 2 , the nitrate was then determined by
potentiometry. The method may be used if 40 times more S0 2 or S0 3
are present.
The nitrogen oxide content of cigarette smoke /108/ has been deter-
mined after dissolution in 0.1 Μ NaOH:
NO + NOj +20H- —• H 2 0 + N0 2 " + N0 3 "
I—Mn0 4 "-f
In this case the potential of the solution containing N0 2 ~ and N 0 3 "
was measured before and after the nitrite oxidation to nitrate. The N0 3 ~
content was also determined /109/ by the Gries method to enable a
comparison with a standard procedure; the results are given in Table 6.
Forney and McCoy /110/ have used a flow cell in which the NO3 LME
was connected to a F" reference electrode.The arrangement used is given
in Fig. 5.
This set-up was used for the first time by Mahahan /111/ to avoid a
liquid junction potential. Cl~and C10 4 "do not interfere and Br", Land
S 0 3 2 " ions, are masked with a 10~2 Μ silver fluoride solution which
simultaneously furnishes the necessary fluoride concentration. The val-
ues obtained agree well with those found by other techniques but the
LME method is quicker.

177
 TABLE VI
The comparative determination of N O j ' a n d NOj in cigarette smoke by the
Potentiometrie and Gries colorimetric methods.

NO3- found Difference NO; found Difference

Sample ppm ppm
Electrode Gries Electrode Gries

1. 3.4 2.5 6.9 4.9 6.6 1.7

2 3.8 2.8 1.0 5.5 6.8 1.8
3 2.8 5.0 2.2 1.4 1.6 0.2
4 3.3 4.2 0.9 7.7 6.0 1.7
5 3.6 3.0 0.6 7.3 6.2 1.1
6 3.8 2.9 0.9 5.0 6.0 1.0
7 3.3 3.0 0.3 6.0 5.2 0.8

Ail-

Fig. 5. S c h e m a t i c diagram of f l o w - t h r o u g h electrode unit and associated nitrate

monitor instrumentation.

178
Another Application of Nitrate-Selective Liquid
Membrane-Electrodes.

The NOj LME has been used in the study of the complex formation
of lanthanum ions with nitrate ions /112/. Two complexes with sto-
fcheiometrics of 1:1 and 1:3 (La 3 + :N03) are considered to exist in sol-
ution. It has been used as an indicator electrode in the titration of ni-
trate with diphenylthallium(III) sulphate /113/. In practical analysis, the
electrode has been used for the determination of nitrate in plutonium soils
/114/, nitrites / I I 5 , 1 1 6 / , oleum /117/ in pickling b a t h s / I I 8 / , in micro-
bial media /119/ and as a detector in ion exchange liquid chromato-
graphy/120/.

179
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