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Spectrophotometric determination of
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Article in Analytica Chimica Acta · December 2001

DOI: 10.1016/S0003-2670(01)01364-2

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 Analytica Chimica Acta 449 (2001) 189–197

Spectrophotometric determination of sulphur dioxide

and hydrogen sulphide in gas phase by sequential
injection analysis technique夽
M. Kass, A. Ivaska∗
Laboratory of Analytical Chemistry, Process Chemistry Group, Åbo Akademi University, FIN-20500 Turku-Åbo, Finland
Received 11 December 2000; received in revised form 24 August 2001; accepted 24 August 2001

Abstract
Methods for determination of H2 S and SO2 in gas phase have been developed. The methods are based on absorption of
the gases in scrubbing solutions and subsequent sequential injection analysis (SIA) determination of the absorbed gases. The
reagents used in the SIA measurements, pararosaniline for SO2 and nitroprusside for H2 S, are very specific for the analytes.
Absorbance of the reaction products is measured at 558 nm. The methods have been developed for determination of SO2 in
the range 1.6–8.0 g/m3 and H2 S in the range 5–15 g/m3 . The relative standard deviation of the determinations is less than
2.5% (n = 10). The methods developed are intended for on-line monitoring of H2 S and SO2 in gas generated when heating
coal at coke production. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Sequential injection analysis; Sulphur dioxide; Hydrogen sulphide; Spectrophotometric detection; Coke production

1. Introduction of H2 S is burnt to SO2 and elementary sulphur is

Iron ore concentrate and coke are the basic raw ma-
terials for manufacturing pig iron. Coke is produced
by heating coal in a closed oven. The gas generated in
the cooking process contains H2 S among other com-
ponents. H2 S and some other gaseous components are
absorbed in a scrubbing unit. The scrubbing solution
is then distilled and the vapour is cracked in a cracking
reactor, over a nickel catalyst at 1100◦ C. In this pro-
cess H2 S remains unchanged while the other gases are
cracked to their elements. An excess of air is added to
the reactor and the airflow is adjusted so that one-third
夽 This work was presented at the 3rd International Colloquium on
Process Related Environmental Analytical Chemistry (PREACH),
Leipzig, Germany (4–7 October, 2000).
∗ Corresponding author. Fax: +358-2-215-4479.
E-mail address: ari.ivaska@abo.fi (A. Ivaska).
obtained according to the Claus reactions.
2H2 S + 3O2
2H2 O + 2SO2 (1)
3
2H2 S + SO2
2H2 O + Sx (2)
x
The individual concentrations of H2 S and SO2
have to be known both before the gas mixture enters
the cracking reactor and when it leaves the reactor,
in order to add a right amount of air to the gas mix-
ture. This is done in order to maximise the yield of
elementary sulphur. The expected range of gas con-
centrations to be monitored are 1.6–8.0 g SO2 /m3 and
5.0–15.0 g H2 S/m3 . Determination of H2 S and SO2 in
the coking plant gas is currently done by performing
manual titrations of the scrubbing solutions in which
the gases have been absorbed. H2 S is determined

0003-2670/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 3 - 2 6 7 0 ( 0 1 ) 0 1 3 6 4 - 2
190 M. Kass, A. Ivaska / Analytica Chimica Acta 449 (2001) 189–197
by iodometric titration and SO2 by acid–base titra-
tion. Therefore, there is an obvious need to develop
automatic methods for monitoring of H2 S and SO2 at
several stages of the coking process.
Sequential injection analysis (SIA) and its predeces-
sor flow injection analysis (FIA) are fast and reliable
techniques for automated chemical analysis [1,2]. SIA
is more suitable than FIA for on-line applications due
to the minimal amount of reagent needed for each
measurement cycle. Furthermore, the SIA instrument
is totally computer-controlled and is therefore suit-
able for different analyses just by selecting a proper
pre-programmed measurement protocol. It can also be
quickly and easily modified, meaning that the same
physical configuration of the flow manifold can be
used in several methods. The SIA system is robust and
reliable enough and therefore well-suited for monitor-
ing industrial processes in severe conditions.
SIA technique makes it possible to automate
well-known wet chemical and spectrophotometric
methods. The Schiff reaction presented already in
1866 is perhaps the most commonly used method
in determination of SO2 [3,4] and it has also been
used in FIA applications [5–7]. Similarly, nitroprus-
side was used for determination of sulphide [8–10]
◦
already long before Hansen and Ruẑička introduced
the FIA technique in 1974. The methylene blue (MB)
method is perhaps more frequently used for deter-
mination of H2 S and it is reported even to be more
sensitive than the nitroprusside method by a factor of
∼30 [9].
In this work we will develop methods for deter-
mination of H2 S and SO2 in coke production gas by
purging the gas through a scrubbing solution. Sam-
ples of that solution are then analysed by SIA methods
developed in this work.
2. Experimental
2.1. Chemicals
All chemicals used in the experiments were of
p.a. grade. Distilled and deionised water without
degassing has been used when preparing and diluting
the reagents. It has also been used as the carrier solu-
tion in the SIA system throughout the experiments.
Both gases used have been obtained from AGA. The
purity of the gases was ≥98.2% for H2 S and ≥99.98%
for SO2 .
The composition of the reagent solution used
in the spectrophotometric determination of SO2
was 0.033 g/l pararosaniline chloride (Sigma) in
0.4 M HCl containing 0.37% formaldehyde (Tamro,
Helsinki). The nitroprusside reagent solution used
for the spectrophotometric determination of H2 S was
prepared by dissolving 2.5 g/l nitroprusside (sodium
nitrosyl-pentacyanoferrate(III) dihydrate, Aldrich) in
a buffer solution. The buffer solution consisted of
0.1 M Na2 HPO4 (Merck) and NaOH making the final
pH 10.6.
The sulphite standards used in the SO2 determina-
tions were prepared by dissolving Na2 SO3 (Merck)
in a water solution containing ethylenediamine-
tetraacetic acid (Fluka) 1 g/l as a stabilising agent.
The sulphide standards used in the H2 S determina-
tions were made of disodiumsulphide nonahydrate,
Na2 S·9H2 O (Sigma). These solutions were stabilised
with l(+)ascorbic acid (Merck).
In the experiments where the gas flow contained
only SO2 , distilled and deionised water served as the
scrubbing solution. When only H2 S or both gases were
present, the scrubbing solution consisted of 1.0 g/l
ascorbic acid dissolved in 25 mM NaOH.
2.2. Apparatus
A commercial SIA flow system SIAmateTM anal-
yser from Arctic Instruments Oy Ab (Turku, Finland)
was used in the experiments [11]. The software,
AnalySIA, was used to control all the experimental
parameters and the data acquisition. The SIAmateTM
instrument has a built-in zoomable LED-specII
LED based photometer with a 0.76 mm light path.
Before running the experiments the detector was
tuned against a standard solution with a concentra-
tion slightly higher than the solutions to be deter-
mined. The absorbance was measured with a 558 nm
LED.
A schematic diagram of the sequential injection
flow system used is shown in Fig. 1. The size of the sy-
ringe of the piston pump was 2.5 ml. All tubings used
in the system were of polytetrafluoroethylene (PTFE)
with an inner diameter of 0.76 mm. The length of the
holding coil was 2.0 m and the length of the reaction
coil was 1.0 m.
 M. Kass, A. Ivaska / Analytica Chimica Acta 449 (2001) 189–197 191

Fig. 1. A schematic diagram of the SIA set-up.

A calibration system was designed in order to 2.3. Procedure

achieve a flow of gas where the concentration of
H2 S and SO2 could be varied. Two mass flow The gas scrubbing was carried out according to the
controllers were used in order to achieve an accu- following procedure. First the airflow was set on, then
rate and repeatable flow of the desired gases. The the scrubbing solution (20 ml) was added to the scrub-
mass flow controllers, model 5850S, were obtained ber, and the flow indicators were adjusted in order
from Brooks Instrument B.V., Veenendahl, Holland. to get the desired flow through the scrubbing solu-
One of them was calibrated for SO2 and the other tion. The setpoint values for the H2 S- and SO2 -flows
one for H2 S. Communication between the mass flow were then given to the mass flow controllers. The time
controllers and the computer was established with of scrubbing was usually kept at 1 min. During this
the Brooks smart control® software. The mass flow time a counter was measuring the total amount of
controllers allowed easy adjustment of the gas flows concentrated gas that passed through the mass flow
and other operational parameters. With the system controllers. When the desired amount of the gas had
designed the flow of the concentrated gas could be
adjusted in the range 2–100 ml/min. The flow of air
could be controlled in the range 800–7300 ml/min by
changing the pressure of the air.
Two flow indicators (Sho-Rate 1355 Series) with
different capacities were also obtained from Brooks
Instrument B.V. These were used to measure the flow
with an accuracy of 5%. A schematic diagram of the
system configuration is shown in Fig. 2. Tubings of
stainless steel with an inner diameter of 2 mm were
used to take the concentrated gases to the scrubber.
All the other tubings were of polyurethane. Air was
used to dilute the gases to the desired concentrations.
Spectrophotometric measurements with wavelength
scanning were done with a Hitachi UV–VIS spec- Fig. 2. System for dilution and scrubbing of H2 S and SO2 gas.
trophotometer, Model U-2001. The measurements MH2 S and MSO2 = mass flow controllers for H2 S and SO2 , R1
were performed using cuvettes with 10 mm light path. and R2 = gas-flow indicators, SC = scrubber.
192 M. Kass, A. Ivaska / Analytica Chimica Acta 449 (2001) 189–197
passed, the flow of the concentrated gases was stopped.
Finally the scrubbing solution was removed manually
from the scrubber to be analysed with SIA.
A measurement cycle with the sequential injection
technique included the following steps: (1) washing
of the sample line with a fresh sample solution; (2)
aspiration of the sample to the holding coil; (3) as-
piration of the reagent to the holding coil; (4) flow
reversion and pumping the aspirated zones through the
reaction coil to the detector and further to the waste.
The photometric measurement was done at 558 nm.
When the pararosaniline reagent was used prob-
lems due to carryover effects was found. The reaction
product showed some affinity to the inner walls of
the tubing. This resulted in a rise of the background
signal of the detector after each measurement cycle.
Introduction of a washing step improved the stability
of the background signal. In this step 500 ␮l of 5 M
NaOH was aspirated to the holding coil and then
flushed through the reaction coil and the detector
before aspirating a new sample.
In all experiments the measurement cycle was
repeated three times for each concentration. The
collected data was median filtered making the distur-
bances caused by possible air bubbles disappear in
the signal when used for analytical evaluation. Cali-
bration curves can be made either by measuring the
peak height or as in our case by measuring the peak
area. The calibration points are plotted automatically
and linear or polynomial regression analysis is ap-
plied. The standard deviation (n = 5) in obtaining the
calibration points was 1–2%. No signal was observed
when pure water was introduced as blank.
3. Results and discussion
3.1. Zone dispersion
In the spectrophotometric methods used in this
work, the product of the reaction between the sample
and the reagent is detected. Reagent-based chemistries
of this type require at least medium dispersion so that
the reagent and sample zones will mix properly. Most
of the experiments were performed using 175 ␮l of
reagent and 50 ␮l of sample and the flow rate was kept
at 50 ␮l/s. These parameters have been successfully
used in a previous study with a similar flow mani-
fold [12]. The physical dispersion and zone overlap
obtained with these parameters was studied in the fol-
lowing way. A dye solution (bromothymol blue) was
aspirated first in the colourless carrier stream as the
reagent and in the next measurement as the sample
according to the SIA protocol. The absorbance was
measured at 635 nm. The tracer curves obtained are
plotted on the same time axis in Fig. 3. As can be
seen in the figure the zones overlap each other to such
an extent that necessary conditions for a reaction is
provided. Only the physical dispersion is illustrated in
this way. In real measurements, however, the chemi-
cal reaction will also make a further contribution to
the over-all dispersion.
3.2. Determination of H2 S
The nitroprusside reagent was first tested on stan-
dard solutions made of Na2 S·9H2 O. The AnalySIA
programme was programmed in such a way that
only one standard solution was needed to make a
calibration curve [11]. The procedure was such that
the standard solution was diluted on-line to differ-
ent calibration concentrations. First a measurement
was performed with the whole volume (50 ␮l) of the
standard solution. Then smaller and smaller volumes
were aspirated following aspiration of the ascorbic
acid solution (1.0 g/l) so that the volumes together
were always constant (50 ␮l/s). The last calibration
point was observed with a solution consisting only
to one-tenth (i.e. 5 ␮l) of the standard solution. This
procedure resulted in a linear calibration curve with
R 2 = 0.9941. The results were matched against man-
ually prepared standards (1.5–15 mM Na2 S), with
good agreement. The standard deviation (n = 5) of
the SIA method of these samples was ca. 1%.
It was found that addition of ascorbic acid to the
scrubbing solution increased the efficiency of the H2 S
absorption. However, if the ascorbic acid concentra-
tion was too high, formation of the coloured product
in the reaction between H2 S and nitroprusside in
the subsequent SIA determinations was depressed.
Optimisation of the ascorbic acid concentration in the
scrubbing solution was done by preparing solutions
with different ascorbic acid concentrations and by
purging a gas flow containing 10 g H2 S/m3 through
the solutions. A small sample from every scrubbing
solution was then analysed in the SIA system with
 M. Kass, A. Ivaska / Analytica Chimica Acta 449 (2001) 189–197
Fig. 3. Tracer curves obtained for the reagent (175 ␮l), and the sample (50 ␮l), when the flow rate was 50 ␮l/s.
nitroprusside as the reagent. An ascorbic acid con-
centration of 1.0 g/l was found to be suitable for the
scrubbing solutions in the future experiments.
[Fe(CN)5 NO]2− + S2− → [Fe(CN)5 NOS]4−
The reaction between nitroprusside and sulphide
proceeds according to reaction (3) and the product
formed has been reported to be unstable [9]. To study
the stability of the coloured product formed in reaction
(3) the absorbance spectrum was taken during 60 s
after mixing a Na2 S-standard (1 mM) and nitroprus-
side (2.8 mM) in a cuvette with 10 mm light path. An
absorbance spectrum was recorded for every 15 s and
the obtained absorbance spectra are shown in Fig. 4.
The spectrum recorded immediately after mixing
is obviously from an initial reaction product which
is then converted to the final product according to
reaction (3).
As can be seen in Fig. 4 a compound with an
absorbance maximum around 540 nm is formed
first. Then the absorbance maximum moves gradu-
ally towards higher wavelengths and finally settles
at 570 nm, whereafter the peak height decreases
gradually. In the SIA system used in this work the
absorbance is measured with a 558 nm LED. The
absorbance at this wavelength has its maximum value
at ca. 30 s. In the manifold used in this work it takes
193
ca. 20 s, with the flow rate of 50 ml/min, from the time
when the sample comes in contact with the reagent
in the holding coil and until the reaction product
reaches the flow cell. Therefore, introduction of a
(3)
stopped-flow period would not improve the response
considerably. Because the timing of all the operations
in a SIA system is done with a high accuracy by the
software, the time elapsed between the points when
the sample and the reagent come together and when
the absorbance measurement is done, is constant be-
tween different determinations and can be repeated
with high reproducibility. This allows reproducible
measurements even when the measurement is not
done at the maximum value of the absorbance.
Mixtures of air and H2 S in different concentrations
in the range 5–15 g/m3 were purged for 1 min through
the scrubbing solutions. A new solution was used for
every determination. A sample from each scrubbing
solution was then analysed in the SIA system (Fig. 5).
In this concentration range a linear response was
obtained (y = 7.16×105 x +1.43×106 , R 2 = 0.996),
when the area under the absorbance curves was plo-
tted versus the H2 S-concentration.
Since the gas flows are known, it is possible to
calculate the sulphide concentration that the scrubbing
solution would have if H2 S would be absorbed with
100% efficiency. By comparing the response of these
194 M. Kass, A. Ivaska / Analytica Chimica Acta 449 (2001) 189–197

Fig. 4. Absorbance spectra of the product formed from the reaction between hydrogen sulphide and nitroprusside at different time intervals
(0–60 s). Pure nitroprusside reagent solution did not absorb light in this wavelength range.

calculated concentrations with the experimentally ob-
tained values, it was found that the efficiency of the
H2 S absorption was over 90%. The reproducibility of
the method was tested with the same gas concentration
and flow by repeating the experiment ten times. Every
scrubbing solution was also analysed three times. The
standard deviation obtained was 2.5%.
This SIA method for determination of H2 S was
compared with a manual iodometric titration method.
Five different scrubbing solutions containing absorbed
H2 S were analysed with both methods. The individual
differences of the methods were compared with
Student’s t-test (t = 1.314). The methods are not
systematically different at the 90% confidence level.

Fig. 5. Detector response for determination of 5–15 g H2 S/m3 at 558 nm with nitroprusside as reagent.
 M. Kass, A. Ivaska / Analytica Chimica Acta 449 (2001) 189–197
The MB method has been used in application of
the FIA technique in determination of H2 S [13].
Kubáň et al. have compared the MB method with
the nitroprusside method [9]. They found the later
method more suitable in practical assay work. In our
SIA set-up the assay work using the MB method was
found to be more complicated and therefore the nitro-
prusside method was considered more suitable in our
applications although the reagent showed some insta-
bility. The signal decreased by 10% during 10 days.
Therefore, the reagent has to be replaced weekly in
continuous use.
3.3. Determination of SO2
The reaction between pararosaniline, formaldehyde
and sulphite has been described by Dasgupta et al. [4].
In our work the pararosaniline reagent was first tested
on standard solutions made of Na2 SO3 . Four standard
solutions with Na2 SO3 -concentrations in the range
0.16–1.1 mM was prepared and assayed in the SIA sys-
tem. The reaction between pararosaniline and sulphite
is rather slow, so introduction of a 15 s stopped-flow
period, when the sample and reagent were in the hold-
ing coil, increased the detector response considerably.
When the area under the obtained absorbance curves
was plotted versus the logarithm of the standard con-
centrations, a linear calibration curve was obtained
(y = 1.69 × 107 x + 3.89 × 107 , R 2 = 0.990).
Fig. 6. Detector response for determination of 1.6–8.0 g SO2 /m3 at 558 nm with pararosaniline as reagent.
195
Mixtures of air and SO2 in different concentrations
in the range 1.6–8.0 g/m3 was purged through 12 ml
of water in the scrubber. Small samples from each
scrubbing solution were analysed in the SIA system
with pararosaniline as the reagent. The absorbance
was measured at 558 nm and the response from each
sample is shown in Fig. 6. The area under the ab-
sorbance curves was plotted versus the logarithm
of the SO2 -concentration. A linear relationship was
hereby obtained (y = 2.57 × 107 x–2.39 × 106 , R 2 =
0.998). The relative standard deviation of the area
under the absorbance peaks of four similar samples
was 1.3%. Three repetitive determinations were made
on each sample.
A somewhat improved linearity (R 2 = 0.999) was
obtained when a chloroacetic acid was added to the
scrubbing solution. The reaction between SO2 and
pararosaniline is pH-dependent, but chloroacetic acid
in the scrubbing solution fixed the pH resulting in a
better reproducibility. The collection efficiency of the
scrubbing unit was 70% when the gas contained 5.6 g
SO2 /m3 and the calculations were done as described
in Section 3.2.
In order to compare this SIA method with a man-
ual acid–base titration method SO2 was determined
in five different scrubbing solutions by both methods.
Student’s t-test was performed on the results (t =
2.290). The two methods are not significantly differ-
ent at the 95% confidence level.
196 M. Kass, A. Ivaska / Analytica Chimica Acta 449 (2001) 189–197
When low concentrations of SO2 are determined
the sensitivity of the Schiff reaction should be in-
creased. This can be done by having separated reagent
components and a different reagent addition sequence.
Dasgupta et al. have discussed the enhancement of
the sensitivity of the reaction in detail [4].
3.4. Simultaneous determination of H2 S and SO2
The reactions between pararosaniline and SO2 and
between nitroprusside and H2 S are rather specific. A
sample containing only SO2 does not give any re-
sponse with nitroprusside and H2 S does not react with
pararosaniline. Consequently the reactions have no
significant interference from the other gas.
A mixture of H2 S and SO2 was made and diluted
with air to the following concentrations: 10 g H2 S/m3
and 5.6 g SO2 /m3 . This gas mixture was purged
through the scrubber for 3 min. The scrubbing solution
consisted of 1.8 g ascorbic acid/l dissolved in 25 mM
NaOH. Two more experiments were done by purging
each of the gases at the mentioned concentrations at
time through scrubbing solutions. Samples from all
three scrubbing solutions were analysed in the SIA
system for SO2 and H2 S. When pararosaniline was
used both samples containing SO2 gave the same re-
sponse, independent of whether H2 S was present in
the purging gas or not. The sample containing only
H2 S did not show any response at all with pararosani-
line. Therefore, we can make the conclusion that H2 S
does not interfere the determination of SO2 . However,
SO2 showed some interference in the determination
of H2 S. The area of the absorbance peak for the sam-
ple containing both gases was approximately 70% of
the response of the sample containing only H2 S of the
same concentration. The sample with only SO2 did
not show any response with nitroprusside. It seems
that the presence of SO2 will, to some extent, block
or suppress absorption of H2 S from the gas phase to
the scrubbing solution.
4. Conclusions
In this study a process analytical method for mon-
itoring of hydrogen sulphide and sulphur dioxide
in gas phase has been developed. The method is
semi-automatic and it can be developed further in
such a way that it can be connected on-line to an
industrial process. A totally computer-controlled SIA
system is used, which makes it possible to use directly
the obtained signals for process control. This would
considerably improve the yield of elementary sulphur
from effluent gas compared with the currently used
process where the analytical determinations are done
by manual off-line methods.
The approach described in this paper offers advan-
tages that are important when an analytical method is
used on-line in industrial processes. Only very small
amount of reagent and sample are needed for the mea-
surements. Although the measurements would be done
throughout a day, only moderate amounts of waste is
generated. In addition to this, experience proves that
the instrument used in this study offers satisfactory
long-term stability.
The system has also the capability to be connected
in the next development state on-line to the process
to do automatic analysis of process gases. In such
an application the solution to the scrubber would be
introduced through the multi-position valve. Samples
would then be taken automatically and at the end of
each cycle the scrubber solution would be changed.
Similar SIA instrument as used in this work has been
in on-line use in a chemical production plant already
for some years and has shown good stability and
robustness in that environment.
Acknowledgements
The financial support from the National Techno-
logy Agency (TEKES), Outokumpu Research, OMG
Kokkola Chemicals, Rautaruukki Steel and Jernkon-
toret is gratefully acknowledged. This work has also
been supported by the Academy of Finland as part
of the Åbo Akademi University, Process Chemistry
Group, the National Centre of Excellence programme
2000–2005, project 64332.
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