J Solid State Electrochem (2016) 20:28792893
DOI 10.1007/s10008-016-3295-3
ORIGINAL PAPER
Potentiometric determination of ascorbic acid
in wateracetonitrile solution using pyrite
and chalcopyrite electrodes
Zorka Stani 1 & Jelena Stepanovi 1
Received: 23 May 2016 / Revised: 12 June 2016 / Accepted: 15 June 2016 / Published online: 24 June 2016
# Springer-Verlag Berlin Heidelberg 2016
Abstract Performance characteristics of the solid-state poten-
tiometric sensors, based on natural sulfide minerals pyrite and
chalcopyrite, are assayed in aqueous and non-aqueous medi-
um. The electrodes are simply and quickly prepared using
inexpensive material that originate from natural environment.
The pyrite and chalcopyrite electrodes exhibit good sensitivity
and repeatability, stable potential with respect to time, short
response time (less than 15 s), the sub-Nernstian response,
with a slope of 48.0 mV per decade for pyrite and 41.6 mV
per decade for chalcopyrite over a wide concentration range of
copper(II) ion in acetonitrile, and a possibility of application
without a time limit in aqueous and non-aqueous solution, as
well. The practical applicability of these indicator electrodes is
their utilization in potentiometric determination of L-ascorbic
acid in water and water-acetonitrile, by using Cu(II) solution
as the titrant, in pure compound and pharmaceutical formula-
tions. The determination of 10.511.5 mg (0.50 mL) of L-
ascorbic acid shows average recoveries of 98.2101.9 %, with
relative standard deviations of 0.10.9 %. The results show
that the large potential break is obtained at the equivalence
point when the titration was carried out in the presence of
chelating bidentate ligand, neocuproine. This is a very simple,
precise, reliable and sensitive one-step method, suitable for
work in the laboratory and can be carried out directly, without
any prior treatment of the investigated samples.
* Zorka Stani
zorkas@kg.ac.rs
1
Department of Chemistry, Faculty of Science, University of
Kragujevac, R. Domanovi 12, P.O. Box 60, Kragujevac 34000,
Serbia
Keywords L-ascorbic acid . Pyrite . Chalcopyrite .
Potentiometry . Neocuproine . Acetonitrile
Introduction
L-Ascorbic acid (2-oxo-L-threo-hexono-1,4-lactone-2,3-
enediol; vitamin C) is very important and an essential vitamin
for human body. It belongs to the group of water-soluble vi-
tamins and non-enzymatic antioxidants [1]. Thanks to the sig-
nificant physiological function that L-ascorbic acid has, it is
part of the biosynthesis and metabolism of various biological-
ly important compounds [2, 3]. L-ascorbic acid acts as a pow-
erful antioxidant that collects and neutralizes free radicals,
such as reactive oxygen and nitrogen species. In that manner,
L-ascorbic acid prevents reaction of free radicals with
biomacromolecules of lipids, proteins, carbohydrates, and
DNA molecules, and thus, it also prevents the occurrence of
many biochemical and functional disorders at the cells level
that, further, lead to a variety of chronic degenerative diseases,
such as cancer, cardiovascular diseases, diabetes mellitus, and
multiple sclerosis [4]. Also, L-ascorbic acid is known as a
stimulator of the immune system, that stimulates the formation
of white blood cells and, in that manner, this acid participates
in the fight against viral, fungal, and bacterial infections [5].
As a natural antihistamine, L-ascorbic acid inhibits the opera-
tion of the histamine which belongs to the biogenic amines,
and thereby reduces the allergic effects [6].
The majority of plants and animals have the ability to syn-
thesize vitamin C. However, the human body depends on
exogenous sources of vitamin, due to lack of the enzyme L-
gulono--lactone oxidase which catalyzes the last step in its
biosynthesis [7]. Daily needs are provided through food and a
variety of pharmaceutical preparations, which include a wide
range of solid and liquid supplements. Both forms of L-
2880
ascorbic acid, natural and synthetic, are chemically identical
and there is no difference in their biological activity.
Therefore, determining L-ascorbic acid in a variety of natural
substances, food, medicine, physiological fluids, and pharma-
ceutical and cosmetic products is of great physiological and
medical importance. Due to a very significant role in the hu-
man body and large application of L-ascorbic acid, especially
in medicine, but also in various industries, such as food, phar-
maceutical, cosmetic, nowadays, special attention is paid to
find fast, reliable, inexpensive, and simple methods of its
analysis.
There are a number of methods for determining L-
ascorbic acid. These include a classical visual titrimetric
method with various oxidizing agents, such as 2,6-
dichlorophenolindophenol, tetrachlorobenzoquinone
(chloranll), N-bromosuccinimide, potassium iodate, ceri-
um (IV) sulfate, potassium hexacyanoferrate (III) [8 and
refs. therein]. These methods are very simple and easily
applicable, but they could only be applied on the pure
samples. They are non-specific, because, the presence of
many colored and reducing substances in various prepa-
rations, interfere the determination of L-ascorbic acid.
Nowadays, the separation methods, such as capillary elec-
trophoresis [9], liquid chromatography [10], especially
high-performance liquid chromatography with electro-
chemical detector linked [11], and gas chromatography
[12], are extremely efficient techniques for determining
L-ascorbic acid in different foodstuffs and biological
fluids. Above-mentioned methods are precise, accurate,
and selective, but require expensive instruments and can-
not be used for routine analysis that has a large number of
samples. In addition, fluorimetric and chemiluminescent
methods of analysis are applied, and they are usually au-
tomated which results in a significantly lower spending of
samples and applied reagents, and also in the higher speed
of operation, but, they are difficult to implement in col-
ored and bleared solutions [13]. In laboratory conditions,
both direct and indirect methods of spectrophotometry, in
the presence of iron(III)/iron(II) or copper(II)/copper(I)
redox systems, with different complexing reagents, are
often used [1416]. The main disadvantage of these
methods is the low selectivity of the determination in real
samples due to the presence of a number of organic and
reducing substances that absorb in the same UV/VIS field
as the measured products of the reaction.
A great attention is paid to the electrochemical analytical
techniques for determining L-ascorbic acid, which are based
on its reducing properties [17]. A different standard, unmod-
ified electrode materials, such as platinum [18], gold [19], and
glassy carbon [20] have been examined, and it has been no-
ticed that during the process of direct oxidation of L-ascorbic
acid, accumulation of the various reaction products has been
occurred on the surface of the electrodes and it leads to a
J Solid State Electrochem (2016) 20:28792893
decrease in reproduction, as well as a slowdown kinetic elec-
tron transfer process. In order to overcome the above-
mentioned drawbacks, a numerous chemically and function-
ally modified electrode materials, based on active redox me-
diators [21] and polymers [22], noble metal nanoparticles
[23], carbon nanotubes [24], and graphene [25], have been
investigated in a real biological samples.
Another extremely important electroanalytical technique
for determining L-ascorbic acid is a potentiometric method.
Potentiometric detection based on using ion-selective elec-
trodes has been proved as very effective in analyzing the con-
tent of vitamin C in various samples of foodstuffs, beverages,
pharmaceutical preparations, and biological fluids. Different
types of specific and non-specific ion-selective electrodes for
the both direct and indirect potentiometric determination of
ascorbic acid have been developed. The electrodes with liquid
membrane have been successfully applied for determination
of L-ascorbic acid in pharmaceutical dosage forms [26].
Different electrodes were used in potentiometric determina-
tions of L-ascorbic acid, such as electrodes with homogenous
crystal membrane [27], a tubular silver electrode [28], a tubu-
lar electrode based on poly(vinyl chloride) [29], a modified
platinum electrode [30], an electrode based on polyaniline
doped with D,L-camphor sulfonic acid [31], a number of car-
bon electrodes based on modified carbon fiber [32],
spectroscopic-grade graphite [33], carbon paste chemically
modified with iron(II) phthalocyanine [34], and diisooctyl
phthalate [35], screen-printed carbon electrodes with poly(vi-
nyl chloride) membrane modified with deferent ionophores
(triphenyltin(IV) chloride, triphenyltin(IV) hydroxide,
palmitoyl-L-ascorbic acid, dibutyltin(IV) diascorbate) [36].
In the recent years, for rapid and accurate potentiometric test-
ing of L-ascorbic acid, a very sensitive solid-contact ion-se-
lective electrodes, based on glassy carbon modified with co-
balt phthalocyanine nanoparticles [37], organic electroactive
polymer polyaniline and tetrasubstituted thiacalix [4]arene as
ionophore [38], and with a layer of molecularly imprinted
polypyrrole which is synthesized in the presence of ascorbate
[39] have also been constructed.
Frequently, potentiometric titration method is applied for
the detection of L-ascorbic acid using copper(II) as a titrating
agent. Application of copper(II) solution, as a strong redox
reagent, in acetonitrile as a solvent, has its advantages, be-
cause the copper(I) is very stable in this solvent owing to its
strong solvation; the process of Cu2+ Cu+ takes place at a
very positive value of potential [40]. The method for deter-
mining micro amounts (0.55 mg) of L-ascorbic acid in a
variety of pharmaceutical products in aqueous solution (effer-
vescent tablets, oral drops, and injections), by using direct
potentiometric titration and copper-selective electrode as an
indicator electrode, has also been elaborated [41].
Riyazuddin and Nazor made copper-based mercury film elec-
trode for detecting 115 mg ascorbic acid by using direct
J Solid State Electrochem (2016) 20:28792893
potentiometric titration and copper(II) sulfate [42]. It is shown
that the proposed method for analyzing the content of vitamin
C in various pharmaceutical dosage forms, gives the same
results as the official British Pharmacopoeia (BP) method.
Fernandes and co-workers have developed a new potentio-
metric sensor based on graphite/epoxy electrode with a poly
(ethylene-co-vinyl acetate) membrane, doped with copper(II)
ions [43]. At the same year, the same authors developed a
sensitive potentiometric biosensor for measuring the concen-
tration of L-ascorbic acid, which is based on using ascorbate
oxidase enzyme immobilized on the graphite/epoxy electrode
[44]. The potential, due to the presence of copper (II) ions in
the molecular structure of the enzyme, is occurred at the sur-
face of the electrode, and it can be detected.
In order to find a new way to determine L-ascorbic acid,
materials that originate from the natural environment, solid-
contact ion-selective electrodes have been applied and fea-
tures of these electrodes are tested in aqueous and non-
aqueous medium. Our previous studies have shown that the
sulfide indicator electrodes can be successfully used as elec-
trochemical sensors for the detection of the equivalence point
in potentiometric acid-based, precipitation, complexometric,
and redox titrations of different compounds in aqueous and
non-aqueous media [4552]. Accordingly, the main objective
of this study is to explain further analytical application of the
handmade pyrite and chalcopyrite electrodes, as well as to
develop an inexpensive, rapid, and easy method for the poten-
tiometric redox and acid-based determination of biologically
important compounds, L-ascorbic acid, in pure compound and
pharmaceutical samples in water and in the mixture of water/
dipolar aprotic solvent acetonitrile, which is especially impor-
tant in the pharmaceutical and food industry, medicine, and in
many other fields, as well.
Experimental
Reagents
All of the chemicals used were of analytical reagents grade
and were used without further purification. They were pur-
chased from AppliChem, Sigma-Aldrich, Fluka, or
J.T.Baker. Acetonitrile was puriss p.a. purity (99.5 %).
Freshly deionized water was used throughout all operations
of experiment.
Hydrated copper(II) perchlorate, Cu(ClO4)26H2O, was
prepared by dissolving copper(II) carbonate in a small amount
of 72 % perchloric acid. The solution was boiled to remove
carbon dioxide, then cooled, and crystals were separated out,
dried under vacuum at room temperature until acquiring con-
stant weight, and stored in desiccator. Fresh hydrated
copper(II) perchlorate solution, approximately 0.04 M, was
prepared by weighing an appropriate amount of substance
2881
and dissolving it in the applied solvents (water or pure aceto-
nitrile). The concentration of the resulting solution was deter-
mined by complexometric titration with disodium salt of
EDTA in aqueous medium using murexide, mixed 1:1000
with sodium chloride, as the indicator. To prevent the hydro-
lysis of the copper(II), about 1 mL of 70 % perchloric acid was
added per liter of hydrated copper(II) perchlorate solution.
The solution was stored in borosilicate glass bottle with
ground-glass stopper. Since the reagent is reasonably unstable,
it was restandardized every few days.
The laboratory reagent grade potassium hydroxide (0.1 M)
in methanol was standardized against benzoic acid using thy-
mol blue as the indicator. A solution of the researched L-
ascorbic acid for redox and acid-based determination was pre-
pared by weighing a definite amount of the compound and
dissolving in the preferred volume of water or mixture of
wateracetonitrile (1:9, v/v). The solution was prepared daily
and stored in an amber bottle to avoid oxidation by air oxygen
and light. L-ascorbic acid pharmaceutical preparations were
obtained from a local pharmaceutical factory, Galenika a.d.,
Belgrade, Serbia.
Neocuproine solution (0.12 M) was prepared by dissolving
an accurate mass of the substance in titrated solvents. The
following commercially available compounds, such as sodi-
um chloride, sodium fluoride, sodium iodide, sodium sulfate,
sodium nitrate, sodium acetate, potassium sodium tartrate,
benzoic, salicylic, and oxalic acid were also used in their orig-
inal state. Their solutions examined in the selectivity experi-
ment, were prepared from substances of analytical grade pu-
rity. An ionic strength of all working solutions was controlled
with 0.05 M tetraethylammonium perchlorate in correspond-
ing solvents.
Apparatus
Potentiometry, as electrochemical method, was used to
determine the general analytical performance characteris-
tics of the employed electrodes (potential changes over
the time, the changes in the potential as a function of
the concentration of copper(II) ions, response time, re-
peatability, chemical and physical durability, selectivity)
and to detect the end point of the redox and acid-based
titration. All measurements were performed with a digital
sensION-meter, model MM340, HACH whose resolution
was 0.1 mV. The temperature control was achieved using
a liquid thermostat VEB MLW Prufgerade-Werk,
Medingen. All the experiments were carried out at tem-
perature (25 0.1 C) and the analyte solutions were
magnetically stirred during measurements to provide uni-
form mass transport. All solutions were de-oxygenated by
pure bubbling nitrogen gas 10 min prior to each experi-
ment. During the experiments, the nitrogen flow was
maintained at the solution surface. The preparation as well
2882
as the transfer of solutions was carried out with minimum
exposure to air.
Electrodes
The experiments were carried out with a sample of either a
natural pyrite or chalcopyrite mineral, from the Veliki Krivelj
copper mine (Bor, Serbia), without any further purification of
these natural minerals. Chemical and spectrographic analyses
of the samples showed that the pyrite contained 44.3 % Fe,
52.5 % S, and 0.6 % Cu and the chalcopyrite 27.1 % Fe,
34.2 % S, and 33.2 % Cu [46].
The proposed pyrite (FeS 2 ) and chalcopyrite
(CuFeS2) electrodes were used as indicator electrodes.
The pyrite and chalcopyrite electrodes, manufactured in
our laboratory, were prepared as described in previous
papers [45, 46]. The electrodes working area were
0.25 cm2. Prior to experiments and after each electro-
chemical operations, the working surface of electrodes
were polished using alumina powder (0.05 m) for 30 s
to obtain a shiny new surface, rinsed with deionized
water and dried. The electrodes were conditioned for
an hour in the examined solvent, before the everyday
usage. Thereafter, the electrodes were ready to use,
without any further mechanical, chemical, or electro-
chemical pretreatment.
The response of the indicator pyrite and chalcopyrite
electrodes was compared with a conventional platinum
indicator electrode, for redox determination, and with a
conventional glass indicator electrode, for acid-based de-
termination. The platinum electrode was made in the
form of a spiral wire sealed into a glass tube with a
ground stopper. The pH electrode was glass electrode
type G-202C (Radiometer, Copenhagen).
The reference electrode was a modified saturated cal-
omel electrode (SCE). The modification of the classic
SCE of type 401 (Radiometer, Copenhagen) was done
by replacing the saturated aqueous solution of potassium
chloride with a saturated potassium chloride solution in
anhydrous methanol. This modification is performed in
order to reduce the diffusion potential between the in-
ternal solution of the electrode and the test solution, and
to avoid the influence of water in the test solution.
Procedures
The stationary potential measurements of the pyrite and chal-
copyrite electrodes were carried out at temperature 25 0.1 C
in a series of copper(II) solutions (at a concentration range
1.0 101 1.0 103 M and 1.0 105 1.0 107 M termined according to IUPAC guidelines using the separate
for FeS2, and 1.0 102 1.0 104 M for CuFeS2 electrode). solution method (SSM) [53]. The potential of a cell compris-
The potential of each solution was recorded when stable
values had been obtained. The calibration graphs were drawn
J Solid State Electrochem (2016) 20:28792893
by plotting the potential, E, versus the negative logarithm of
copper(II) concentration. The potential values determined in
this way, also were used to calculate the response time. A
constant ionic strength of solution was maintained with
0.05 M solution of tetraethylammonium perchlorate.
The potential changing of the pyrite and chalcopyrite
electrodes with time in solutions of different concentra-
tions of L-ascorbic acid was followed in mixture of
wateracetonitrile (1:9, v/v). These indicator electrodes
were coupled with a modified saturated calomel elec-
trode as the reference electrode. The electromotive force
(EMF) was measured in the following electrochemical
cells:
SCE | analyte solution | pyrite electrode
SCE | analyte solution | chalcopyrite electrode
The titration experiment was performed by adding the
titrant to the solution of the L-ascorbic acid (containing
10.536.0 mg, i.e., 0.501.00 mL). Copper(II) solution
was used as a titrant for redox, while potassium hydrox-
ide was used as titrant for acid-based determination. The
solution in a measuring cell was stirred by a magnetic
stirrer. The titration process was monitored potentiomet-
rically using different electrode couples (FeS2 SCE,
CuFeS2SCE, PtSCE, glassSCE), where the potential
values were plotted against the volume of the titrant
added and the titration end points were determined from
the second derivative of the titration curve. The equiv-
alence point of the reaction corresponded to the inflec-
tion point of the curve.
For the determination of L-ascorbic acid in pharmaceu-
tical tablets and capsules, each tablet/capsule was accurate-
ly weighed, disintegrated to a homogeneous fine powder,
mixed in a mortar, and dissolved in the preferred volume
of mixture of wateracetonitrile (1:9, v/v). After mixing
completely, the resulting solution was diluted in order that
the concentration of L-ascorbic acid was inside the linear
range of the calibration graph. Then, an exactly defined
aliquot of the test solution was transferred into the poten-
tiometric cell for titration, containing 10.5010.80 mg
(0.50 mL) of L-ascorbic acid. Also, for determination of
L-ascorbic acid in injection solutions, the contents of the
vial were transferred quantitatively into a calibrated flask
and the solution is diluted to volume with mixture of
wateracetonitrile (1:9, v/v). In this case, the same titration
procedure was carried out with pure compound and com-
mercial pharmaceutical formulations of L-ascorbic acid.
The potentiometric selectivity coefficients (K pot
i; j ) were de-
ing an examined electrode and a reference electrode was mea-
sured in two separate solutions, one containing L-ascorbic
J Solid State Electrochem (2016) 20:28792893
acid (i), but no interfering ion and the other containing the
interfering ion (j), at the same concentration as the analyte,
but without L-ascorbic acid.
Results and discussion
Pyrite (FeS2) and chalcopyrite (CuFeS2) are one of the most
widespread sulfide minerals in nature. Due to their excellent
characteristics, such as semiconductivity, non-toxicity, and
availability in natural environment, pyrite and chalcopyrite
minerals are used as materials for various electrochemical ap-
plications in the form of solid state sensor materials [46, 49,
54].
Pyrite is an Fe(II) polysulfide with a cubic NaCl-type crys-
talline structure and it is the most thermodynamically stable
iron sulfide from all the others found in the nature. Pyrite
exists as an n-type or a p-type semiconductor and has a suit-
able band gap of 0.9 eV [55]. The nature and degree of
doping elements as a cationic impurity and the manner in
which the pyrite was formed, determine the type of
semiconductivity and the electrical resistivity [56]. The elec-
trical properties of pyrite have been investigated using a vari-
ety of spectroscopic methods [57]. The electrochemical and
semiconducting properties of pyrite samples were extensively
investigated by using cyclic voltammetry, electrochemical im-
pedance spectroscopy and Mott-Schottky methods [58].
Eghbalnia and Dixon concluded that pyrite samples with low-
er charge transfer resistance were better catalysts for iron(III)
reduction. The octahedrally coordinated Fe2+ in pyrite is in a
low-spin state with an electronic configuration of (t2g)6 (eg)0.
Its t 2g level is fully occupied by the six Fe electrons.
Moreover, each molecular orbital of the S2
2 anion in the pyrite
structure have paired electrons. All of that makes pyrite a non-
reactive and diamagnetic compound with no magnetic mo-
ment [59]. According to these characteristics (primarily
semiconductivity and chemical inactivity), it is possible to
use pyrite for the measurement of the potential changes.
Chalcopyrite is the most abundant copper sulfide mineral
and it crystallizes in the tetragonal system. Chalcopyrite is
very unreactive mineral with semiconducting properties. It is
relatively insoluble in water and its solubility is increased in
the presence of strong oxidizing agents. Furthermore, the elec-
trochemical behavior of chalcopyrite is similar to the pyrite.
Our previous investigation conformed that although pyrite
is close to be stoichiometric, naturally occurring pyrite
contained a wide range of trace elements (except 0.6 % Cu,
the following elements are presented: 0.001 % Mn, 0.36 % Al,
0.002 % Pb, 0.001 % Sn, 0.01 % Ni, 0.001 % Ag, 0.1 % Zn,
0.05 % Ti, 0.001 % Mo, 1.86 % SiO2) [46]. These deviations
are present due to substitutions of the Fe2+ or the S ion with
atoms of similar radius and charge or net polarity. Distribution
of these impurity elements can cause significant variations in
2883
the properties of this mineral, which can directly affect on the
reactivity of the pyrite surfaces and therefore on electrode
potential of surface layers. Copper can be present as either
substitution in the pyrites crystal lattice or as inclusion in this
mineral and can directly affect on the reactivity of the pyrite
surfaces. High percentage of copper is already contained in the
structure of chalcopyrite. Based on this, the potential of the
pyrite and chalcopyrite indicator electrodes will depend on the
concentration of iron and copper ions and also on any other
ions that are able to react with the S2 2 anions. Under these
conditions, it can be expected to obtain analytically useful
information which permits the analytical utilization of this
type of ion-selective electrodes. The interest to the develop-
ment of these electrochemical sensors for potentiometric titra-
tions is currently stimulated by possibility to determinate a
biological active compound, L-ascorbic acid, in water and
non-aqueous solvent acetonitrile.
Electroanalytical performance characteristics of the pyrite
and chalcopyrite electrodes
Measurements realized by potentiometry were used to identi-
fy, monitor, and compare electrochemical behavior, activity,
and main analytical properties (calibration plot and slope of
the potential response, response time, repeatability, durability,
selectivity) of these ion-sensing electrodes.
Potential of the electrodes In order to investigate the possi-
bilities of implementation of the FeS2 and CuFeS2 as indicator
electrodes, each of them, individually, was coupled with an
SCE and change of the potential with time was followed in
considered solvents (water or mixture of wateracetonitrile).
The potential of these electrodes slightly changed over the
time (a figure is not shown). Stable potentials were attained
for approximately 5 min in both of the investigated solutions.
Also, the potential changing of the pyrite and chalcopyrite
electrodes in relation to time was followed in solutions of
different concentrations of L-ascorbic acid (Fig. 1) and in
the mixture of wateracetonitrile (1:9, v/v). Measurements
were carried out in solutions with constant ionic strength
(0.05 M tetraethylammonium perchlorate). From this figure,
it can be seen that in all solutions, either low or high concen-
trations of L-ascorbic acid, the potential initially increased,
while after 23 min it remained nearly constant.
Response time of the electrodes The response time is one of
the most important parameter in describing the electrode char-
acteristics. The practical response time of the sensors was
tested by measuring the average time required for the pyrite
or chalcopyrite electrodes to reach a cell potential of 90 % of
the final equilibrium potential value, after successive immer-
sion in a series of copper(II) ion solutions; each having a
2884 J Solid State Electrochem (2016) 20:28792893

Fig. 2 Potentialtime curves for dynamic response time of the proposed

Fig. 1 The change of the potential with time for a FeS2 and b CuFeS2
indicator electrodes in mixture of wateracetonitrile in the presence of
different concentrations of L-ascorbic acid: 1 1.0 10 1 M, 2
1.0 102 M, 3 1.0 101 M, 4 1.0 101 M, 5 1.0 101 M, 6
1.0 101 M, and 7 1.0 101 M
tenfold difference in concentration. In this study, the response
of the sensors was recorded by changing the Cu(II) ion con-
centration in solution, over a concentration range from
1.0 107 to 1.0 101 M. Sequence of the measurement
was from lower to higher concentration. As depicted in Figs. 2
and 3, over the entire concentration range, the electrodes
reached their equilibrium response in a short time (12 s for
pyrite and 13 s for chalcopyrite electrode, Table 1) and after
that, potentials stayed constant with only a very slow diver-
gence with time.
a FeS 2 and b CuFeS 2 indicator electrodes for step changes in
concentration of Cu(II) ions in mixture of wateracetonitrile
1.0 102 1.0 104 M for copper(II) ion in mixture of
wateracetonitrile, with the sub-Nernstian slope of the calibra-
tion curve 41.6 0.5 mV per decade (Fig. 4b). The plots clearly
showed that copper(II) ions are responsible for the development
of the potential on the electrode surfaces. Since the potential of
the pyrite and chalcopyrite electrodes was very stable with time
and satisfactory linearity between the electrode potential and
concentration was obtained (Fig. 4, Table 1), these sensors can
be applied to the determination of investigated L-ascorbic acid in
aqueous and non-aqueous media.
Repeatability of the electrodes The electrodes repeatability
was assessed by investigating the variation of the electrodes
potential in successive determinations. In order to examine the

Calibration curve of the electrodes Using the suggested in-

dicator electrodes and conditions described earlier, the potentio-
metric response of the sensors was studied at temperature
25 0.1 C, in a series of copper(II) concentrations and in
nitrogen-saturated solutions. To ensure constant ionic strength
and, therefore, to avoid the correction for liquid junction poten-
tial, all solutions of copper(II) were prepared with 0.05 M
tetraethylammonium perchlorate. This is very important, since
the concentration during measurements is changed around ten
times. The calibration graph was plotted as potential of the elec-
trode versus the negative logarithm of copper(II) ion concentra-
tion. The calibration curves of the pyrite and chalcopyrite elec-
trodes are shown in Fig. 4. The pyrite sensor displayed a linear
response over two concentration ranges
1.0 101 1.0 103 M and 1.0 105 1.0 107 M for
copper(II) ion in mixture of wateracetonitrile, with the sub-
Nernstian slope of the calibration curve 48.0 0.3 mV per de- Fig. 3 Response time of the proposed a FeS2 and b CuFeS2 indicator
cade (Fig. 4a). Also, the chalcopyrite sensor extended an appli- electrodes after immersing in 1.0 103 M solution of copper(II) ions in
cable linear response over concentration range mixture of wateracetonitrile
J Solid State Electrochem (2016) 20:28792893
Table 1 Performance
characteristics of the pyrite and Parameter
chalcopyrite electrode
Slope (mV decade1)
Sensitivity (mV decade1 cm2)
Correlation coefficient
Linear range (mol L1)
Detection limita (mol L1)
Quantification limita (mol L1)
Response time (s)
Lifetime
a
Average of seven measurements
repeatability, i.e., efficiency of the proposed electrodes in po-
tentiometric titrations, determination of L-ascorbic acid was
monitored by using chalcopyrite electrode and copper(II) so-
lution in mixture of wateracetonitrile (1:9, v/v), as a model (a
figure is not shown). For seven replicated titrations of
11.20 mg (0.50 mL) L-ascorbic acid, the relative standard
deviation (RSD) was 0.1 %. The result of the calculations
showed that there was no significant difference between the
response signals of the sensor during measurements and con-
firmed the stability and repeatability of the electrode.
Lifetime of the electrodes One of the main analytical char-
acteristic in choosing the applicability of sensor is its
lifetime or durability. The electrode durability was ap-
praised by investigation of the variation of the slope in
successive calibrations. It is showed how long the sensor
can be used, depending on the time interval, for deter-
mination without significant error, after its construction
date. Day to day calibration was performed using the
same tested sensor to evaluate its useful lifetime. The
repeatability for the slopes of the calibration curves in
Fig. 4 Calibration plot of the a pyrite and b chalcopyrite electrode potential versus negative logarithm of copper(II) ion concentration in the mixture of
wateracetonitrile
2885
Value
FeS2 CuFeS2
48.0 0.3 41.6 0.5
192.0 166.4
0.9974 0.9991
1.0 105 1.0 107 1.0 102 1.0 104
9.7 108 8.9 105
3.2 107 3.0 104
12 13
> a year > a year
consecutive measurements was evaluated over a period
of 1 year by recording their potential values for the cal-
ibration solutions and plotting the replication graphs. For
the proposed electrodes, the linear dynamic range, slope
of the calibration graph, and response time were almost
constant during this period. The calibration slope did not
modify more than 1 mV per decade change of concen-
tration. This showed that the lifetime of the suggested
selective electrodes was more than 1 year (Table 1).
When the electrodes were not used for measurements,
they were conserved at dry condition (keeping the sensor
away from the measuring solution) in a place protected
from dust, at room temperature. Before the next use, the
electrodes were kept in the investigated solvent for an
hour. A new surface for measurement (when electrodes
were frequently used for a longtime and were reused
after a long no-usage period) can be achieved daily, sim-
ply by polishing the electrodes with aluminum oxide, till
a shiny surface is obtained, by washing the electrodes
and continuing with use. The proposed sensors were
proved to work quite well under laboratory conditions.
2886
Moreover, investigation showed that it can be used with-
out any time limit and without considerable divergence
in the relative standard deviation.
Selectivity of the electrodes The selectivity behavior is
one of the most essential characteristics of the electrode,
which defined the possibility of an authentic measure-
ment for analyte ion. To research the selectivity of the
electrodes, their potential responses for primary ion (i)
were monitored in the presence of different interfering
foreign organic or inorganic anions (j), such as Cl, I,
F , SO24 , NO3 , CH 3 COO , C4 H4 O2 6 , C 6 H 5 COO ,
2
C6H4(OH)COO , and C2 O4 . The non-ideal behavior of
ion-selective electrodes is quantitative described by po-
tentiometric selectivity coefficient (K pot
i; j ). The selectivity
coefficients were determined according to IUPAC recommen-
dations, by the separate solution method (SSM) [53] with
0.02 M concentration of both, L-ascorbic acid and interfering
anions, in mixture of wateracetonitrile (1:9, v/v). The Table 2
showed data for the potentiometric selectivity coefficients of
the pyrite and chalcopyrite electrodes for several tested
substances. As it is shown, the studied compounds had no
significant interference on the sensors response. The
proposed electrodes were chemically inert to the other
The copper(II) ions are reduced to copper(I) by the L-
ascorbic acid, which is oxidized to dehydroascorbic acid,
through two electron transfers. The potential change was
caused by formation of the charged layer, due to the ex-
istence of the redox couple Cu2+/Cu+ on the electrodes
surface. That induced the potential variation, which is
detected by the pyrite and chalcopyrite electrodes. The
results of potentiometric determination of L-ascorbic acid
with copper(II) and proposed electrodes, in the mixture of
wateracetonitrile, are summarized in Table 3. Also, the
potential changes at the titration end point are shown in
Table 4. The titration curves of L-ascorbic acid in mixture
of wateracetonitrile as a solvent, including copper(II) as
titrant are presented in Fig. 5a. When the process was
J Solid State Electrochem (2016) 20:28792893
substances and had small values of selectivity coefficient.
The ions did not interfere owing to the differences in ionic
size, and their mobility and permeability, as compared with
properties of L-ascorbic acid.
Analytical application of the pyrite and chalcopyrite
electrodes for determination of L-ascorbic acid
The pyrite and chalcopyrite sensors, connected with an
SCE as the reference electrode, were successfully applied
as the indicator electrodes, in the potentiometric redox
and acid-based titration of L-ascorbic acid, in water and
the mixture of wateracetonitrile (1:9, v/v). Likewise, the
proposed electrodes were used for determination of L-
ascorbic acid in pharmaceutical formulations. The results
gained by using the pyrite and chalcopyrite electrodes
were compared with the results derived with a conven-
tional platinum indicator electrode, for redox, and with a
standard glass indicator electrode, for acid-based
determination.
L-Ascorbic acid oxidation by copper(II) The titrations of L-
ascorbic acid in the mixture of wateracetonitrile with
copper(II) perchlorate, can be formulated according to Eq. (1):
followed by using FeS2, CuFeS2, and Pt electrodes, large
potential breaks were found in the vicinity of the equiva-
lence point. Table 4 indicates that very similar potential
jumps were obtained when the pyrite or the chalcopyrite
electrode was used as the indicator electrode; a larger
potential jumps were obtained with the pyrite electrode
(321 mV/0.3 mL) than with the platinum electrode
(210 mV/0.3 mL) in the mixture of wateracetonitrile.
The influence of the chelating bidentate ligand,
neocuproine (2,9-dimethyl-1,10-phenanthroline; Nc), on
the potential of the Cu2+/Cu+ system, as well as a benefit
of its application are also introduced in the present paper.
It is well-known that a redox potential of the metal ion
system can be changed by the complexation of metal ions
J Solid State Electrochem (2016) 20:28792893 2887

with a suitable ligand during reaction. In this case, the acid with a copper(II)-neocuproine compound, can be rep-
proposed method, based on the oxidation of L-ascorbic resented in the following way:

The presence of neocuproine causes a change in the where, cCu(II) and c Cu(I) are the total concentrations of
oxidizing power of copper(II), due to formation of the copper(II) and copper(I), respectively; L is a conditional re-
copper(II)-neocuproine complex. Thus, the oxidation re- dox potential of the Cu2+/Cu+ system in the presence of
action of L-ascorbic acid with copper(II) was favored in neocuproine and can be expressed by:
the presence of neocuproine. Similarly, to the consider- CuINc
ation in the review about ligand effect on the redox reac- L0 L 0:059log 4
CuIINc
tions [60], it could be concluded that the product formed
during this reaction, the colored orange-yellow copper(I)- where, L is a constant which depends on the construction of
neocuproine complex, has higher value of constant stabil- the membrane, Cu(Nc) indicates the coefficient of side reac-
ity then copper(II)neocuproine complex. Additionally, it tion for the complex formation of the relevant metal with Nc:
should be mentioned that the presence of a complexing Cu(I)(Nc) = 1 + n(Cu(I)(Nc))[Nc]n with
agent, neocuproine, which forms more stable complex n(C u(I)(Nc)) = [Cu(I)(Nc) n ][Cu + ] 1 [Nc] n (n = 1, 2);
with copper(I) than with copper(II), shifts the equilibrium Cu(II)(Nc)is analogically defined.
(Eq. 2) to the right side and the equilibrium constant be-
comes larger.
The potential of the recommended solid-state membrane
electrodes can be presented by Eq. (3): Table 3 Potentiometric redox titration of L-ascorbic acid in the absence
and the presence of a neocuproine
cCuII
E L0 0:059log 3 Electrode na Taken Found Standard
cCuI couple (mg) (%) deviation
(%)
Table 2 Potentiometric selectivity coefficients (K pot
i; j ) for pyrite and
chalcopyrite electrodes estimated by SSM method Absence of neocuproine solvent
Water FeS2SCE 7 11.30
Interfering ion (j) CuFeS2 7 11.30
K pot
i; j
SCE
PtSCE 6 11.30
FeS2SCE CuFeS2SCE
Wateracetonitrile FeS2SCE 7 11.30 99.9 0.4
(1:9) CuFeS2
Cl 2.32 103 5.17 103 7 11.20 100.4 0.1
SCE
I 2.11 103 2.29 103
PtSCE 6 11.20 100.9 0.2
F 3.41 103 7.55 103
Presence of neocuproine solvent
1.40 103 1.48 103
SO2
4
Water FeS2SCE 7 11.30 100.0 0.3
2.68 103
3.73 10 3 CuFeS2 7 11.30 100.9 0.4
NO3 SCE
C6H5COO 3.75 103
3.07 104 PtSCE 6 11.30 100.3 0.2
CH3COO 5.77 103 1.94 103 Wateracetonitrile FeS2SCE 7 11.30 100.1 0.2
4.64 104 2.90 104 (1:9) CuFeS2 7 11.30 100.1 0.2
C2 O2
4 SCE
C6H4(OH)COO 5.77 104
2.42 10 3
PtSCE 6 11.30 99.8 0.2
Tartrate 2.87 104 3.66 104
a
Number of determinations
2888 J Solid State Electrochem (2016) 20:28792893

Table 4 Potential jumps (mV/0.3 mL) at the end point in the
potentiometric titration of L-ascorbic acid using copper(II) as titrant in
the absence and in the presence of a neocuproine
FeS2SCE CuFeS2SCE PtSCE
Absence of a neocuproine solvent
Water
Water/acetonitrile (1:9) 321 334
Presence of a neocuproine solvent
Water 385 249
Wateracetonitrile (1:9) 610 465
The representative potentiometric titration curves of L-
ascorbic acid with copper(II) in the mixture of wateracetoni-
trile, in the presence of neocuproine, by using the electrode
couples FeS2SCE, CuFeS2SCE, and PtSCE are shown in
Fig. 5a. It is shown that the potential increases progressively
with the successive addition of copper(II) in the solution
which contains L-ascorbic acid and neocuproine. A sharp
jump of the potential was registered at the equivalence point
and the addition of a ligand neocuproine increases the sharp-
ness of the titration end point. In the presence of neocuproine,
remarkable potential breaks were obtained at the equivalence
point, in amount of ca. 610 mV/0.3 mL , 465 mV/0.3 mL , and
493 mV/0.3 mL , for the pyrite, chalcopyrite, and platinum
electrode, respectively (Table 4). Briefly, L-ascorbic acid was
oxidized much more rapidly and efficiently with copper(II)-
neocuproine compound than with copper(II). The potential
jumps were sufficiently large in the presence of a neocuproine
210
in the mixture of wateracetonitrile, by applying any of the
suggested indicator electrodes. For example, the potential
299
jump was 610 mV/0.3 mL in the presence of neocuproine
493
and 321 mV/0.3 mL in its absence, when a pyrite electrode
was used as the sensor during titration of L-ascorbic acid. The
response of the electrodes was fast and the equilibrium poten-
tial during the titration and at the equivalence point was
established within 30 s, and that allowed the precise determi-
nation of this compound under the above-mentioned
conditions.
The determination of L-ascorbic acid by potentiometric
titrimetric method with copper(II) perchlorate in water was
also studied. The copper(I) ions were highly instable in aque-
ous solution and analysis were carried out in nitrogen atmo-
sphere in order to avoid aerial oxidation of L-ascorbic acid.
The results showed that determination of L-ascorbic acid with

Fig 5 Potentiometric titration curves of L-ascorbic acid in 1 mixture of wateracetonitrile (1:9, v/v) and 2 water, obtained by using a pyrite, b
chalcopyrite, c platinum, and d glass indicator electrode; Presence of a neocuproine
J Solid State Electrochem (2016) 20:28792893 2889

Table 5 Potentiometric acid-based titration of L-ascorbic acid in the
mixture of wateracetonitrile
Electrode couple na Taken Found Standard Potential jumps
(mg) (%) deviation (%) (mV/0.3 mL)
FeS2SCE 7 36.00 99.9 0.4 135
CuFeS2SCE 7 36.00 99.9 0.5 137
GlassSCE 6 36.00 100.1 0.2 65
a
Number of determinations
copper(II) cannot be performed in the absence of complexing
agent, but on the other hand, the oxidation reactions easily
took place in the presence of neocuproine and, consequently,
L-ascorbic acid could be titrated with high accuracy and pre-
cision. Thus, a large potential break was observed at the equiv-
alence point when the titration of L-ascorbic acid with
copper(II) was carried out in the presence of 0.12 M
neocuproine, while the potentiometric determination of L-
ascorbic acid with copper(II), as it has already been men-
tioned, was impossible in the absence of this ligand. The re-
sults of potentiometric determination of L-ascorbic acid with
copper(II) and proposed electrodes, in water solution, are giv-
en in Table 3 and potential jumps at the titration end point are
presented in Table 4. Figure 5a showed titration curves of L-
ascorbic acid oxidation, with copper(II) solution as the titrat-
ing agent, in the presence of a neocuproine. As it is inferred,
the potential jumps of L-ascorbic acid at the equivalence point
were 385 mV/0.3 mL, 249 mV/0.3 mL, and 299 mV/0.3 mL
for the pyrite, chalcopyrite, and platinum electrode, respec-
tively. The effect of the concentration of neocuproine on the
titration curves of L-ascorbic acid was examined and suffi-
cient potential breaks at the equivalence point was observed
in the presence of neocuproine at concentration of 0.12 M. For
concentration of 0.07, 0.01, and 0.12 M neocuproine,
potential breaks were 233 mV/0.3 mL, 257 mV/0.3 mL, and
385 mV/0.3 mL, respectively. The concentration of 0.12 M
neocuproine proved to be the optimum condition. Increasing
of neocuproine concentration to a certain limit, caused an
increase of the potential jump on titration curve.
Finally, in the presence of neocuproine, sufficiently larger
potential breaks at the equivalence point were obtained in the
mixture of wateracetonitrile, than those obtained in water
solution (Table 4). When pyrite electrode was used as the
sensor, the potential jump at the titration end point was about
610 mV/0.3 mL in the mixture of wateracetonitrile and
385 mV/0.3 mL in water as a solvent. It might be attributed
to the slow establishing of equilibrium of the electrode poten-
tial after addition of the titrant copper(II) in the solution of L-
ascorbic acid.
The obtained results confirm that there is no statistically
significant difference between the theoretical and the found
values. The determination of 11.211.3 mg (0.50 mL) of the
L-ascorbic acid showed average recoveries of 99.8100.9 %,
with relative standard deviations of 0.10.4 % (Table 3). For
instance, the seven-time repeated titration of 11.30 mg
(0.50 mL) of L-ascorbic acid by using chalcopyrite electrode,
wateracetonitrile mixture, and in the presence of a
neocuproine, gives a standard deviation of 0.2 %, while the
same concentration of L-ascorbic acid in water solution has a
standard deviation of 0.4 %.
L-ascorbic acid neutralization by potassium hydroxide
The mechanism of pyrite and chalcopyrite dissolution is a
multiple electron transfer process and can oxidatively [59],
reductively [61], or chemically [62] occurr. The oxidative dis-
solution route has the main focus because the strongest influ-
ence on the state of the surface of these sulfide minerals has
concentration of oxygen from air or water. Also, potential of
suggested sensors depends on many other parameters, such as

Table 6 Results obtained in the analysis of L-ascorbic acid in pharmaceuticals samples in the absence and the presence of a neocuproine

Sample Proposed method Reference methodb (found RSD, %) Potential jumps

(found RSD, %) (mV/0.3 mL)

FeS2SCE CuFeS2SCE FeS2SCE CuFeS2SCE PtSCE

Absence of a neocuproine
Vitamin C tablets 98.6 0.4 98.4 0.6 101.1 0.1 340 324 217
Vc injection 98.7 0.9 98.4 0.1 101.1 0.1 383 359 280
Multivitamin capsulesa 98.5 0.6 101.6 0.2 98.7 0.3 336 342 301
Presence of a neocuproine
Vitamin C tablets 98.6 0.4 98.2 0.6 101.1 0.2 594 437 364
Vc injection 98.9 0.9 98.8 0.8 98.3 0.1 546 512 391
Multivitamin capsulesa 98.5 0.1 101.8 0.2 101.9 0.6 459 543 434
a
Other components: vitamin E, vitamin A, sodium selenite
b
Potenciometric method by using Pt electrode
2890
the nature and concentration of the present cations (especially
ferric ion), anions, and other chemical species, as well as the
pH value, ambient temperature, pressure, and the presence of
bacteria. It is generally accepted that the oxidation of pyrite
can be described by the following overall reactions:
FeS2 Fe2 2S0 2e in acidic solution 5 nk
FeS2 8H2 O Fe3 2SO2
4 16H
15e at higher potentials 6 layer acts as a sensor for the corresponding H3O+ ions in an
As it is reported in the literature, the main products
of oxidative dissolution of pyrite are Fe2+ and SO2
4
ions (and smaller amounts of intermediate oxidation
products such as sulfur, sulfite, thiosulfate) [59], and
under oxidizing conditions, chalcopyrite dissolves with
the release of different composition (Cu2+, Cu+, Fe3+,
Fe2+, S0, SO4 ) [54]. The hydrolysis of iron cations
Table 5 summarized the results of potentiometric acid-
based determination of L-ascorbic acid and potential jump
at the titration end point with potassium hydroxide, by using
proposed electrodes and wateracetonitrile mixture. There
was satisfactory agreement between the results obtained by
the pyrite and chalcopyrite electrodes on one side, and glass
indicator electrode on the other side. The potential jumps for
L ascorbic acid were large enough to allow the precise de-
termination under the employed conditions, applying the
indicator electrodes FeS2 (135 mV/0.3 mL) and CuFeS2
(137 mV/0.3 mL). A very similar jump was obtained when
the pyrite or the chalcopyrite electrode was used as the in-
dicator electrode (Table 5 and Fig. 5b). Moreover, larger
potential jump was obtained with the pyrite electrode than
with the glass electrode for the determination of L-ascorbic
acid in the mixture of wateracetonitrile. Also, the results
summarized in Table 5, indicate that the determination of
36.00 mg (1.00 mL) of the L-ascorbic acid has average
recoveries of 99.9100.1 %, with relative standard devia-
tions of 0.20.5 %.
J Solid State Electrochem (2016) 20:28792893
(reactions 5 and 6) can be described by the following
equation:
nk
Fen 2kH2 O FeOHk kH3 O 7
These ions form a hydroxysulfide/metal layer
nk
(ox = FeHk =FeS2 for pyrite and ox = FeHk
=CuFeS2 for chalcopyrite) on the surface of the minerals. This
aqueous and non-aqueous environment, as it is conformed in
our previous work [45, 46]. The potential is defined by
Eq. (8):
E E 0ox 0:059logakH3 O 8
The stoichiometry of the reaction of L-ascorbic acid with
potassium hydroxide, can be formulated in the following way:
Potentiometric redox determination of L-ascorbic acid in
pharmaceutical preparations The samples, analyzed by
the proposed method, were obtained from the local phar-
maceutical factory. The analyzed pharmaceutical formula-
tions were vitamin C tablets, Vc injections, and multivi-
tamin capsules. The tablets of ascorbic acid with labeled
content of 500 mg of active substance, were grounded,
dissolved in the mixture of wateracetonitrile, and titrated
with copper(II) solution. When a pyrite electrode was
used as the sensor for determination of L-ascorbic acid,
the potential jump was 594 mV/0.3 mL in the presence of
neocuproine, and 340 mV/0.3 mL in the absence of
neocuproine. Also, the potential jump of the applied chal-
copyrite electrode was about 437 mV/0.3 mL in the pres-
ence and 324 mV/0.3 mL in the absence of a neocuproine
(Fig. 5c). The determination of 10.57 mg (0.50 mL) L-
ascorbic acid showed average recoveries of about 98.2 %,
with relative standard deviations less than 0.6 %. The
sensors were utilized with success for L-ascorbic acid de-
termination in real samples of drugs as can be verified for
J Solid State Electrochem (2016) 20:28792893
the values listed in Table 6. The vitamin levels obtained
for all samples studied were compared with the results
obtained by a reference method based on a conventional
platinum indicator electrode. The results demonstrate ex-
cellent agreement and illustrates that the proposed poten-
tiometric method is reliable for the determination of
ascorbic acid in the vitamin preparations as those de-
scribed. Accordingly, the satisfactory recoveries and the
good agreements between the obtained values for L-
ascorbic acid in pure compound and pharmaceutical prep-
arations, indicate that the suggested electrodes have a
great potential in the practical sample analysis.
Conclusions
The results obtained from this study revealed that the poten-
tiometric sensors, based on natural sulfide minerals pyrite
and chalcopyrite, functioned as excellent solid-contact ion-
selective electrodes without an internal solution. The elec-
trodes could be used in the both direct potentiometric anal-
ysis (at a concentration range 1.0 101 1.0 103 M and
1.0 105 1.0 107 M for FeS2 and
1.0 102 1.0 104 M for CuFeS2 electrode) and in
potentiometric redox and acid-based titrations in aqueous
and non-aqueous media with high accuracy and precision.
The essential, biological and physiological significant com-
pound for the human organism, L-ascorbic acid, was suc-
cessfully determined by the proposed sensors. Therefore, the
propounded electrodes, compared with a platinum electrode
for redox determination and with a glass electrode for acid-
based determination, in the investigated solvents, offered
preponderantly attractive advantageous. High repeatability,
sensitivity and selectivity, low response time, long durability,
and wide linear concentration range, made the proposed
electrodes very useful sensors for accurate determination of
L-ascorbic acid. The sensors, made from inexpensive and
nontoxic material, were easily prepared. Also, the surface
of the electrodes can quickly be repaired. The sensors
showed satisfactory results when they were used for the
determination of L-ascorbic acid in pure compound and in
real samples. Finally, the presented method in this study is
simple, precise, accurate, and rapid, involving no prior treat-
ment of the sample and there are relatively no interferences
from excipients, commonly present along with L-ascorbic
acid, in drug formulations.
Further practical implementation of the pyrite and
chalcopyrite electrodes as sensitive potentiometric sen-
sors in aqueous and non-aqueous solutions, includes de-
termination of some compounds, isolated from natural
products and biological materials, and compounds
2891
important for the pharmaceutical and medical aspects,
as well.
Acknowledgments This research was financially supported by the
Ministry of Education, Science and Technological Development of
Republic of Serbia (Project No. 172036).
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