Application of DC and Mark-Space Bias Differential Electrolytic Potentiometry For Determination of Cyanide Using A Programmable Syringe Pump
Application of DC and Mark-Space Bias Differential Electrolytic Potentiometry For Determination of Cyanide Using A Programmable Syringe Pump
Application of DC and Mark-Space Bias Differential Electrolytic Potentiometry For Determination of Cyanide Using A Programmable Syringe Pump
DOI 10.1007/s13201-011-0010-5
ORIGINAL ARTICLE
Received: 1 March 2011 / Accepted: 28 July 2011 / Published online: 10 August 2011
The Author(s) 2011. This article is published with open access at Springerlink.com
Abstract This paper describes a rapid sequential injection titration method for the determination of cyanide in
aqueous solutions. Mercuric nitrate was used as a titrant
and a pair of gold-amalgam electrodes as an indicating
system. The technique of differential electrolytic potentiometry using both mark-space bias (m.s.b.) and dc current
for polarization was employed. The optimum values of
current and percentage bias were 5 lA and 13%, respectively. The effects of dispense time, volume of analyte,
supporting electrolyte, and the concentration of titrant were
investigated. The results obtained are in agreement with
those of the standard method (APHA), with a relative
standard deviation of 1.43%, t = 0.783, F = 1.713. A
sampling rate of about 20 samples per hour was achieved
with good reproducibility and lower consumption of
reagents.
Keywords
Introduction
Cyanide is used in many industrial applications such as
electroplating, precious metal refining, gold mining, metal
ore processing, and smelting, chemical and petrochemical
applications. Cyanide compounds used in industry include
hydrogen cyanide, cyanogen chloride, cyanide salts containing potassium or sodium, gold and silver cyanide. The
mining of gold depends on cyanidation (MacArthur et al.
1988). Cyanide leaching, which is one of the gold
T. A. Saleh (&) A. M. Abulkibash
Chemistry Department, King Fahd University of Petroleum
and Minerals, Box 6724, Dhahran 31261, Saudi Arabia
e-mail: tawfikas@hotmail.com; tawfik@kfupm.edu.sa
extraction technologies, has replaced the mercury amalgamation. It involves spraying sodium cyanide solution, of
a concentration of 200600 ppm, on piles of ground ore.
Gold reacts with cyanide to form a water-soluble compound. Gold then can be extracted by passing the solution
over an activated carbon. The remaining cyanide solution
is stored in covered ponds (Schnepp 2006).
Methods which are commonly used for the determination of cyanide include titrimetric, colorimetric and ion
selective electrodes. Titration of free cyanide with silver
nitrate is a traditional method (Clesceri et al. 1995).
However, halide species if present will be a source of
interference during titration. The colorimetric methods
suffer from interferences of the oxidizing agents used or
the buffers added. On applying ion selective electrodes
(ISE), cyanide is reduced during the addition of both, the
buffers and solutions that help in maintaining the ionic
strength. Moreover, the membrane itself could be easily
damaged or clogged in presence of silver ions. Halides,
sulfides, thiocyanate or any other complexing agents used
might interfere. ISE method suffers a drawback where it is
necessary to perform calibration every hour in order to
obtain a 2% reproducibility. This reproducibility is limited by factors such as temperature fluctuations, drift and
noise. The life of the ISE electrode is generally affected by
exposure to higher concentrations of cyanide ([10-3 M)
(Stankovic et al. 1993). Ion chromatography combined
with amperometry was applied for the determination of
cyanide (Themelis et al. 2009; Johnson and LaCours 1990).
Raman and IR spectroscopy, which are expensive techniques, have been used for the detection of cyanide (Lukey
et al. 1999; Stuart and Van der Heuvel 1992).
Based on the literature review, cheap, portable equipment and simple method are required to be used for in situ
analysis. Here, we reported a method consisting of syringe
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Experimental
Solution preparation
All chemicals used were of analytical grade and doubly
distilled water was used throughout. All reagents were
prepared and stored in polythene vessels.
1.
2.
3.
4.
5.
Apparatus
The manifold used in this method consists of a programmable syringe pump (PSP) and infinity controller (IC)
combined with mark-space bias current source and silver
electrodes, as depicted in Fig. 1. PSP and IC are produced
by J-KEM Scientific, Inc. This PSP has multi-port distribution valves. Each port can be used for the suction and
dispensing the required solution. The syringe handles volumes of 1050 mL.
Procedure
Figure 1 illustrates the schematic diagram of the setup
employed in this study. The titration was carried out as
described in the following steps. In the initial step, the cell
and valves were cleaned by aspirating a certain volume of
the deionized water, and then dispense. Then, a certain
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Step
Action description
Time (s)
Valve
position
Flow rate
(lL/s)
Volume
(lL)
100
120
80
120
12
140
500
12
140
500
100
140
90
30
140
Aspirate water
10
140
500
10
140
500
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Calibration curve
Solutions of cyanide having different concentrations were
titrated with mercuric nitrate. Figure 6 shows the titration
curves obtained. The calibration curve was established with
linearity between 0.20 and 25 ppm. Above 25 ppm, there
was no linear response of the electrodes to different concentrations. Therefore, the linearity was difficult to be
obtained in the range between 0.20 ppm and concentrations
higher than 25 ppm. Therefore, the linearity was selected
in the range between 0.20 and 25 ppm. Calibration curve
(or calibration equation) between end point and concentration of cyanide y = 0.0051x ? 0.3669 where y potential
(V) and x is concentration (ppm) with 95% confidence
level, p = 0.050. The correlation coefficient was 0.9951.
Method evaluation
The optimum sequential injection titration system was
investigated for the effect of interferences, precision, and
sample frequency.
71
Interfering
ions
Tolerated
concentration
(ppm)
Cl-
350
I-
300
PO43-
500
SO42-
150
Cu2?
400
200
Ag?
350
Au
Deviation of 5% was allowed
in the peak height
Standard method
Precision
The reproducibility and precision of the system was evaluated on five runs and repetitive determinations of representative samples under the selected optimum conditions
using fixed cyanide ion concentration (50 ppm :
0.0012375 M). The percentage relative standard deviation
(RSD) was found to be better than 1.43% (n = 100). This
indicates that the proposed system has good precision.
Shewhart and Cusum control charts
The optimum conditions of the previous mentioned optimized parameters were applied during the performance of
these analyses. A standard solution of cyanide 50 ppm was
analyzed in the laboratory for 25 consecutive days, the
sample size being four on each cycle. Variability of signal
generated in different days was drawn in a Shewhart
(Miller and Miller 2000) control chart, Fig. 7. The cumulative sum of -0.9 was also statistically obtained as shown
4.9
20
20.4
50
49.1
98.0
102
98.2
4.9
98.0
20.5
102.5
49.0
98.0
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References
Comparisons of results with the standard method
The comparison between the proposed method and the
standard method was performed by real sample analysis.
The results obtained using the proposed sequential titration
method was statically evaluated and compared with the
standard method, American public health association
(APHA) (Clesceri et al. 1995). The results show good
agreement, Table 3. The calculated t value was 0.783
which is less than the tabulated t, 2.78 (p = 0.05, 95%
confidence level). In addition, it was found that F value is
1.713 that is less than the tabulated value, 3.708. In addition the cumulative sum was -0.9.
Conclusion
The proposed SI titration method is simple, rapid, inexpensive in terms of instrumentation cost, reagent and
sample consumption, and manpower. It has a good reproducibility with about 20 samples per hour sampling rate.
The sensitivity of the proposed method is greatly enhanced
by the use of m.s.b. current source for polarizing goldamalgam electrodes. The statistical analysis indicates that
t value was 0.783, F value was 1.713, and relative recovery
was 98102%. We here based on our findings recommend
the equipments to be compact in one unit and used as a
portable method for in situ detection of cyanide. A simple
column for cyanide separation can be involved as well to
get rid of the interferences.
Acknowledgments The authors acknowledge the financial support
of King Abdulaziz city for Science and Technology (KACST) under
project APR -26-72.The support of Chemistry department at King
Fahd University of Petroleum and Minerals is also acknowledged.
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