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Semi-Quantitative "Spot-test" of Cyanide

Article in Analytical Sciences · September 2003

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ANALYTICAL SCIENCES AUGUST 2003, VOL. 19 1139
2003 © The Japan Society for Analytical Chemistry

Semi-Quantitative “Spot-test” of Cyanide

José Arnaldo Dibbern FÁVERO and Matthieu TUBINO†

Instituto de Química, Universidade Estadual de Campinas, CP 6154, 13084-971 Campinas, SP, Brazil

A selective, sensitive, rapid and simple-handling analytical method for the determination of cyanide at low detection
limits in surface and underground water, soil and industrial waste samples was developed. The method is based on a
reaction, proposed by Guilbault and Kramer, where free cyanide reacts with p-nitrobenzaldehyde to form an intermediate
cyanohydrin, which reacts with o-dinitrobenzene to give a highly colored purple compound. The original procedure was
modified for application in a small device containing a gas-permeable membrane. The cyanide is converted in the
volatile hydrogen cyanide, which permeates through a PTFE membrane, reaching colorimetric reagents. In order to
obtain semi-quantitative results, printed color scales were built. The method allows rapid, accurate, selective, low-cost
and simple-handling determinations of free cyanide, even in complex samples. About 150 real samples were analyzed.
Less than 10 ng of free cyanide per ml (10 µg l–1) can be easily detected. For more concentrated solutions, the results had
been compared to those obtained using differential pulse polarography. The standard addition method was used for more
diluted solutions.

(Received December 27, 2002; Accepted May 19, 2003)

problem involving the colorimetric methods, i.e., it is

Introduction endangered by deep-colored samples. In order to apply this
method to industrial waste, in the present work a simple-
The determination of low amounts of cyanide ions is important handling pretreatment device was developed based on the
due to their high toxicity to living matter. A dramatic example permeation of hydrogen cyanide (HCN) through a semi-
of the effect that cyanide can cause to the environment is a permeable PTFE membrane, followed by reactions with
disaster that occurred almost three years ago in the Szamos colorimetric reagents and by visual detection. The system, built
river, Rumania, which also affected the Danube river. The low in acrylic, comprises two separated parts: a lower one, where
detection levels established by environmental protection the sample and a sulfuric acid solution 2 mol l–1 are inserted for
agencies for surface and underground water, soil and industrial the liberation of HCN, and a screw-cap where the analytical
waste demand the development of accurate and selective reagents are introduced (Fig. 1).
analytical methods. Semi-quantitative results are obtained by visually comparing
Since the 19th Century, hundreds of procedures for the the intensity of the colors developed by the samples in the
determination of cyanide have been proposed,2,3 using a variety
of analytical methodology: titrimetry,4,5 amperometry,6
polarography,7–10 voltammetry,11 potentiometry,12,13
electrophoresis, piezoelectricity, ion chromatography,16,17
14 15

HPLC,18,19 gas chromatography,20 biosensor,21 atomic

absorption,22 fluorometry,23 spectrophotometry,24–30 flow-
injection31–33 and other.34–37 Although colorimetric methods are,
in general, selective and sensitive, they are highly affected by
deep-colored samples and oxidizing or reducing agents.
Guilbault and Kramer38 developed a colorimetric method
based on the reaction of p-nitrobenzaldehyde with cyanide to
give an active reducing agent capable to promoting the
reduction of various compounds to form highly colored
products. The intermediate cyanohydrin reacts with o-
dinitrobenzene to give a highly colored purple compound, the
dianion of o-nitrophenyl hydroxylamine. Because cyanide is
regenerated, a catalytic reaction occurs, increasing the
sensitivity.
Despite the fact that this method shows high sensitivity and
selectivity for cyanide determination, it presents a common Fig. 1 Device containing a gas-permeable PTFE membrane: A,
screw-cap; B, reservoir for reagents, which is covered with the semi-
†
To whom correspondence should be addressed. permeable PTFE membrane; C, hole for the visualization of the
E-mail: [email protected] color; D, lower part; E, central reservoir for sample introduction; F,
This paper was partially presented in the 8th FECS.1 side reservoir for the sulfuric acid solution.
1140 ANALYTICAL SCIENCES AUGUST 2003, VOL. 19

Table 1 Attribution parameters of the software Paint® in function of the concentration of cyanide

Parameter 0.5 mg l–1 1.0 mg l–1 2.0 mg l–1 5.0 mg l–1 10.0 mg l–1 20.0 mg l–1
Scale 1 Tone 172 173 174 173 173 172
Saturation 75 83 79 80 81 82
Brightness 225 194 177 130 98 44
Red 237 200 181 124 91 41
Green 234 189 166 99 69 31
Blue 244 223 210 177 139 63

Parameter 0.02 mg l–1 0.05 mg l–1 0.1 mg l–1 0.2 mg l–1 0.5 mg l–1 1.0 mg l–1

Scale 2 Tone 172 175 173 173 173 173

Saturation 75 80 83 80 80 81
Brightness 225 209 194 154 114 74
Red 237 219 200 153 107 69
Green 234 211 189 133 81 52
Blue 244 233 223 194 162 105

Parameter 0.01 mg l–1 0.02 mg l–1 0.05 mg l–1 0.1 mg l–1 0.2 mg l–1 0.5 mg l–1

Scale 3 Tone 173 173 173 173 173 173

Saturation 83 83 80 82 82 81
Brightness 217 194 168 137 106 74
Red 227 200 170 133 99 69
Green 222 189 153 108 74 52
Blue 239 223 204 193 151 105
Parameter 0.01 mg l–1 0.02 mg l–1 0.05 mg l–1 0.1 mg l–1 0.2 mg l–1 0.5 mg l–1

Scale 4 Tone 172 173 173 174 173 172

Saturation 78 80 80 81 80 82
Brightness 201 168 130 81 65 44
Red 208 170 124 77 61 41
Green 200 153 99 57 46 31
Blue 227 204 177 115 92 63

Scale 1 Reaction time, 1 min; Scale 2 reaction time, 5 min; Scale 3 reaction time, 10 min; Scale 4 reaction time, 20 min.

device to a printed color scale. A scale developed through was used when recommended. Water was distilled in glass
software was printed on glossy paper, producing visually exact equipment and deionized in a Milli Q Plus Ultra Pure Water
colors and the color intensities related to the cyanide standard System. Industrial waste, soil and surface and underground
solutions submitted to the method proposed in this work. water samples were gently provided by a Brazilian chemical
For more concentrated cyanide solutions, the results obtained industry.
from the visual method for industrial waste, soil and surface and The reagents used in colorimetric measurements were
underground water were compared with data obtained with prepared as follows: p-nitrobenzaldehyde (1.5 × 10–1 mol l–1 –
differential pulse polarography. For the more diluted ones, 0.1130 g) was dissolved in 5.0 ml of ethyleneglycol
where instrumental methods usually do not work, standard monomethyl ether (methyl cellosolve); o-dinitrobenzene (1.5 ×
addition was adopted. 10–1 mol l–1 – 0.1260 g) was dissolved in 5.0 ml of methyl
cellosolve; an aqueous 7.5 × 10–1 mol l–1 NaOH solution was
prepared by dissolving 30 g in 1000 ml of water.
Experimental
Cyanide standard solutions
Equipments and reagents All cyanide standard solutions were carefully prepared in
Polarographic measurements7,10 were made using a NaOH (1.0 × 10–1 mol l–1) and kept in plastic flasks below 10˚C.
Radiometer (POL-150) with a mercury cell assembly (MDE- A concentrated cyanide solution (1000 mg l–1): 0.2500 g of
150). All solutions were deoxygenated with purified nitrogen. analytical-grade potassium cyanide was dissolved in 100.0 ml
Differential pulse polarograms were recorded, in a 0.1 mol l–1 of NaOH 1.0 × 10–1 mol l–1. A cyanide stock-solution (100 mg
NaOH solution between –100 mV and –350 mV, using a KCl l–1): 10.0 ml of the 1000 mg l–1 solution was transferred to a
saturated silver/silver chloride reference electrode, at a rate of 5 100.0 ml volumetric flask and the volume completed with
mV s–1. The pulse amplitude was –25 mV and the drop time NaOH (1.0 × 10–1 mol l–1).
was 1 s. Cyanide standard solutions were added with Cyanide working standard solutions: working standard
micropipettes with disposable tips. The solution was solutions were obtained by appropriate dilutions of the stock
deoxygenated for 40 s after each addition. Then, 6.00 ml of 1.0 solution, diluting with the NaOH 1.0 × 10–1 mol l–1 solution.
× 10–1 mol l–1 sodium hydroxide solution was introduced into a The cyanide stock solution must be changed monthly while
polarographic cell. The sample volume was 2.00 ml and the diluted standard solutions are discharged weekly, despite
standard addition volume was 50.0 µl. preservation in an alkali solution. The concentrated cyanide
All reagents used were of analytical grade. Standardization solution must be re-standardized before reutilization.
ANALYTICAL SCIENCES AUGUST 2003, VOL. 19 1141

Construction of the visual color scales Table 2 Cyanide analysis in waste from an acrylic polymer
An attempt was made to look for colors in ready-to-use color producing plant
palettes easily found in drawing software. Paint®, software Proposed methoda/mg l–1 Differential pulse
available in all computers equipped with Windows®, yields the Sample polarographyb/
Estimated
best results. With this procedure was found, and printed, the Range
mean value mg l–1
color which visually matched with that developed by the
analytical reaction. By varying the color brightness a complete 1 10 – 20 15 18.2 ± 0.5
color scale was constructed ranging from nearly white to deep 2 10 – 20 15 17.9 ± 0.5
purple. Moreover, for each defined color, Paint® attributes six 3 10 – 20 15 18.0 ± 0.5
parameters, which allow reconstruction of the color and its a. According to color scale 1. Reaction time 1 min.
intensities in any computer. The scale was compared with the b. Standard addition method. Three determinations were performed
color intensities developed in the permeation system for cyanide per sample. References 7, 10.
standards in concentrations ranging from 0.01 to 20 mg l–1. The
scale was printed on glossy paper using a HP Deskjet 820 Cxi
color printer.
enters the process carried by acrylonitrile. Three samples of
Analytical procedure this kind were analyzed, and the results were compared with
The standard color scale. All instructions refer to Fig. 1. Into those obtained by polarography (Table 2).
reservoir (B) of screw-cap (A) were added the following As can be seen from Table 2, the polarographic results were
reagents (in this order): 2 drops (0.05 ml) of a 1.5 × 10–1 mol l–1 within the range obtained using the proposed visual colorimetric
solution of p-nitrobenzaldehyde, 2 drops (0.05 ml) of a 1.5 × method.
10–1 mol l–1 solution of o-dinitrobenzene and 2 drops (0.05 ml) A kind of industrial waste, very likely to contain free cyanide
of a 7.5 × 10–1 mol l–1 solution of NaOH. A PTFE band, contamination, can be generated by nitrocellulose producing
commonly used for thread sealing was carefully stretched over plants. The proposed method was applied to two samples; in
reservoir (B), while always avoiding covering the screw-cap both cases a reddish-yellow coloration was obtained. During
thread. The lower part (D) contains two separated reservoirs. the nitrocellulose production process, there is a step where
Into the central one (E) was added 0.5 ml of a cyanide standard crude cellulose is blanched with sodium or calcium
solution and, into the side reservoir (F) was added 1 ml of a 2 hypochlorite. The residual hypochlorite contained in the
mol l–1 solution of sulfuric acid. After that, the cap was sample, reacts with sulfuric acid inside the permeation system,
carefully screwed to the lower part and the whole system was producing gaseous chlorine. This volatile compound permeates
turned upside down for few seconds to allow acidulation of the through the PTFE membrane, leading to a reaction observed
cyanide standard solution, promoting the liberation of gaseous through the reddish-yellow coloration. Hypochorite converts
HCN. Once the system was returned to its original position, a free cyanide to cyanate, which is easily converted to N2 and CO2
chronometer was started; the color developed for each standard (or CO32–) by excess hypoclorite. Therefore, if an excess
was compared with the color scale, constructed using Paint®, amount of this reagent is used for bleaching crude cellulose, the
within four different reaction times (1, 5, 10 and 20 min). cyanide will be totally destroyed.
Using this procedure, each cyanide standard was associated to a The method has also been successfully applied to free cyanide
specific color in a specific reaction time, resulting in four scales, analysis in surface and underground water samples which, in
one for each reaction time, composed of six colored circles some cases, demands periodical monitoring. Three surface
(diameter = 15 mm). The scales were built using the following water samples were collected in a river according to standard
reaction times and cyanide solutions: Scale 1 (reaction time = 1 procedures, and analyzed directly with the proposed method,
min): 0.5, 1.0, 2.0, 5.0, 10 and 20 mg l–1; scale 2 (reaction time with negative results in the three cases. To one sample was
= 5 min): 0.02, 0.05, 0.1, 0.2, 0.5 and 1.0 mg l–1; scale 3 added 0.01 mg l–1 of cyanide. It was analyzed again, showing a
(reaction time = 10 min): 0.01, 0.02, 0.05, 0.1, 0.2 and 0.5 mg result within the range of 0.01 to 0.02 mg l–1, using color scale 4
l–1 and scale 4 (reaction time = 20 min): 0.01, 0.02, 0.05, 0.1, (reaction time, 20 min).
0.2 and 0.5 mg l–1. The last scale, despite having the same A total of eighty two underground water samples were
attributions as scale 3, showed deeper colors, allowing more analyzed. They were collected from three different sources: a
sensitive semi-quantitative determinations. All of the scales phenol producing plant, a storage area for packed chemicals and
were established at the temperature of the environment, i.e., a methionine producing plant.
about 25˚C. The six Paint® parameters for constructing each For the phenol plant, twenty samples were collected from
colored circle of the four scales are given in Table 1. monitoring wells, and analyzed directly with the proposed
Sample analysis. Sample analyses were carried out using the method. Considering the detection limit of the method (0.01 mg
same procedure as described above, but introducing 0.5 ml of l–1), it was not found to be free cyanide contamination in any
the sample into the central reservoir in the lower part instead of sample. However, for some samples, the formation of a pale-
standards. yellow coloration was observed in the reaction cell, instead of
purple, indicating changes in the analytical conditions due to
some interference. It is well known that some underground
Results and Discussion samples present high concentrations of sulfide ions, and other
sulfur-containing ions. Reacting such samples with strong
The proposed method has been successfully applied to more acids, results in the liberation of H2S, which can permeate
than one hundred and fifty samples comprising several through a PTFE membrane, producing changes in the analytical
categories, such as underground, surface and potable water, medium. Unfortunately, the chemistry of sulfite ions is very
industrial waste and soil samples. similar to that of cyanide, and the elimination of such ions is not
Industrial waste from plants producing acrylic polymers is trivial without the loss of cyanide. If sulfide, polysulfides or
very often contaminated with free cyanide because this anion other sulfur ions like, S2O32–, are present, free cyanide can be
1142 ANALYTICAL SCIENCES AUGUST 2003, VOL. 19

Table 3 Cyanide concentrations in solid refuse from a from 0.5 to 1.0 mg l–1, while another sample presented
methionine producing plant contamination within the range from 0.02 to 0.05 mg l–1. The
cyanide concentration Cyanide concentration remaining samples did not present any detectable free cyanide
Sample (proposed method)e/ (D.P. polarography)f,g/ contamination. To validate the application of the visual method
mg kg–1 mg kg–1 in this specific kind of sample, the standard addition method
was used. A total recover of the added cyanide was observed.
01 0.05 – 0.1a 0.2 Working with samples of methionine refuse, nineteen solid
02 <0.01a <0.05 waste samples, collected over producing and storage areas were
03 <0.01a <0.05
analyzed. However, it was not possible to directly apply the
04 0.2 – 0.5b 1.4
05 0.01 – 0.02a <0.05
visual method because these samples presented an oily or waxy
06 <0.01a <0.05 aspect, making impossible to withdraw a representative small
07 0.5 – 1.0c 0.7 sample to carry out the analysis. To ensure more representative
08 0.1 – 0.2b <0.05 results, the material was homogenized and treated according to
09 0.2 – 0.5b 0.3 a standard procedure.41 The samples were acidified with
10 <0.01a <0.05 hydrochloric acid, and the generated hydrogen cyanide was
11 <0.01a <0.05 distilled and trapped in a sodium hydroxide solution. Over this
12 2.0 – 5.0d 3.4 alkaline solution, a colorimetric analysis was carried out with
13 0.02 – 0.05b <0.05 the proposed method, and the results were compared with those
14 >20d 18.3
obtained by differential pulse polarography (Table 3).
diluted 25 times 0.5 – 1.0c
12.5 – 25 in the sample
It can be easily observed that the analytical results obtained
15 >20d 20.8 with differential pulse polarography are within the ranges
diluted 10 times 1.0 – 2.0d obtained with the visual method, and expressed on original
10 – 20 in the sample samples.
16 1.0 – 2.0d 2.5
17 <0.01a <0.05
18 >20d 252 Conclusion
diluted 100 times 2.0 – 5.0d
200 – 500 in the sample The visual semi-quantitative colorimetric method developed in
19 5.0 – 10d 6.0
this work showed adequate sensitivity for free cyanide
a. According to color scale 4 (reaction time 20 min). determination in industrial waste and others samples resulting
b. According to color scale 3 (reaction time 10 min). from environmental controls. Due to its simple-handling
c. According to color scale 2 (reaction time 5 min). characteristics, low cost, reliability, and rapidity, the method is
d. According to color scale 1 (reaction time 1 min). suitable for use in field determinations, and also in the
e. minimum of two determinations per sample. laboratory, allowing quick responses when dealing with
f. References 7, 10. industrial waste and environmental systems. The visual limit of
g. Average of two determinations. The mean relative deviations of detection is about 0.01 mg ml–1 (10 ppb).
the cyanide concentrations obtained through differential pulse
The results obtained with the proposed method are in good
polarography are about 3 to 5% for the highest values. For the
smaller, a minimum deviation of about 0.05 mg kg–1 must be agreement with those determined by differential pulse
considered. polarography, which is a worldwide classic method for cyanide
determination.

readily and completely converted to thiocyanate. Nevertheless, Acknowledgements

in some cases, sulfide can be precipitated by the addition of lead
ions and removed by filtration.39,40 The standard addition The authors thank Fundação de Amparo à Pesquisa do Estado
method was applied to four samples. Total recovering was de São Paulo, FAPESP, and Conselho Nacional de
observed. In this case, standard addition was applied because Desenvolvimento Científico e Tecnológico, CNPq, for financial
the polarographic method does not have the required sensitivity. support.
From the underground water of a storage area for chemicals,
twenty water samples were also collected. The direct
application of the proposed method showed that cyanide was References
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