Talanta 56 (2002) 1163 1165

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Short communication

Fast and highly selective determination of cyanide with

2,2-dihydroxy-1,3-indanedione
G. Drochioiu *
Chemistry Faculty, Al. I. Cuza Uni6ersity of Iasi, 11 Carol I, Iasi 6600, Romania
Received 23 July 2001; received in revised form 23 October 2001; accepted 26 October 2001

Abstract

A very simple, accurate, fast, selective and sensitive assay of cyanide based on its reaction with 2,2-dihydroxy-l,3-in-
danedione at basic pH is proposed. As little as 0.01 mg ml 1 of cyanide can be determined. The molar absorptivity
may reach 5.18.0 104 l mol 1 cm 1 depending on the reaction conditions. Thus, 1 ml of sample solution is mixed
with 500 ml of 5 mg ml 1 solution of 2,2-dihydroxy-1,3-indanedione monohydrate in 2% sodium carbonate. The
absorbance of the purple color is measured at 510 nm in 1-cm glass cuvettes, 10 15 min after mixing the reagents.
The procedure could also be used to identify free CN in natural waters and hydrocyanic acid in the environment.
2002 Elsevier Science B.V. All rights reserved.

Keywords: Cyanide assay; Ninhydrin reagent; 2,2-Dihydroxy-1,3-indanedione

After recent cases of cyanide pollution on the
Siret river in Romania, we decided to look for a
very simple, sensitive and selective assay of free
cyanide ions. In a previous paper [1], we suggested
that a suitably modification of cyanide reaction
with picric acid could serve as a very specific assay
of hydrocyanic acid. This method was subse-
quently improved by adding resorcinol [2]. Never-
theless, although specific and sensitive enough,
these procedures proved to be rather complicated
and required a water bath to perform the color
reaction as well. Other methods such as those
based on the Konig reaction [3] are relatively
sophisticated because of the number of steps and
* Tel.: +40-32-711-377; fax: +40-32-201-201.
E-mail address: gabidr@uiac.ro (G. Drochioiu).
their requirement for many reagents, some of
them being carcinogenic compounds [4,5]. Under
these circumstances, we also rejected the fluoro-
metric procedures because of their requirement
for a spectrofluorometer [6,7].
In a routine screening, we discovered a very
specific color reaction between cyanide ions and
2,2-dihydroxy-1,3-indanedione, an easily available
compound, in the presence of sodium carbonate.
The reaction of cyanide with 2,2-dihydroxy-1,3-
indanedione is as simple as the reaction of alka-
line solutions with phenolphthalein. Although this
reaction was not yet thoroughly investigated, we
consider that it could serve as an indicator for
cyanide presence. Due to the experimented data,
it was supposed that the first cyanide ion acts as a
reducer to form hydrindantin. Therefore, we pro-

0039-9140/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
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1164 G. Drochioiu / Talanta 56 (2002) 11631165
Fig. 1. Cyanide reaction with 2,2-dihydroxy-1,3-indanedione.
posed a corresponding reaction, which was de-
picted in Fig. 1.
After examination of the various reaction con-
ditions such as 2,2-dihydroxy-1,3 indanedione
and sodium carbonate concentrations and the
pH, the following procedure is recommended.
To 1 ml of aqueous sample solution add 500 ml
of 28 mM solution of 2,2-dihydroxy-1,3-indane-
dione monohydrate (5 mg ml 1) in 2% sodium
carbonate (pH 10.0). Purple color that appears
immediately could be an indicator of free cya-
nide ions. Stir and measure the color intensity
at 510 nm in 1-cm glass cuvettes of a spec-
trophotometer or a colorimeter.
Absorption spectra of the blank with 2,2-di-
hydroxy-1,3-indanedione and that of the colored
compound formed with cyanide ions are shown
in Fig. 2. The coloration was stable for at least
1 h at room temperature.
The calibration graph for cyanide was linear
in the range from 10 ng to 1.0 mg ml 1. The
Fig. 2. Absorption spectra of a 0.25 mg ml 1 CN solution
() and of the blank ().
regression equation for the calibration graph
was calculated to be: A= 1.932C + 0.002, where
A is the absorbance value at 510 nm, and C is
the cyanide concentration, expressed as mg
ml 1. The relative standard deviations (n= 6)
were 2.1% for 10 ng ml 1 cyanide and 1.5% for
1 mg ml 1.
The method was found to be free from most
interferences. Amino acids and ammonia ions
did not react under these reaction conditions. A
1000-fold molar ratio (to cyanide) of common
anions and cations such as nitrate, sulfate,
sulfite, sulfide, thiols, calcium, magnesium and
zinc did not interfere in the determination of 0.5
mg ml 1 cyanide. Ferro- and ferricyanide did
not react with the color reagent. Thiocyanate
interferes stoichiometrically, yielding positive er-
rors only if its concentration is higher than 5 mg
ml 1 SCN. Nevertheless, its molar absorptiv-
ity was proved to be less than 5% as compared
with cyanide molar absorptivity. In addition, the
interference of Cu2 + , Ag+, Hg2 + , Ni2 + , Cd2 + ,
Fe2 + , and Fe3 + on the determination of cya-
nide was tested.
To test the utility of the method, cyanide
added to natural water collected from Siret
River was determined. For 0.1 and 1.0 mg of
cyanide added to 1 ml of water sample, 99
101% recoveries were obtained.
The sensitivity of the method is greater than
that of the other methods based on using picric
acid [1], pyridine [5], picric acid and resorcinol
[2], and the procedure is simpler. We found a
molar absorptivity of 5.1104 l mol 1 cm 1
for less than 0.2 mg ml 1 CN and 8.0 104 1
mol 1 cm 1 for 0.2 mg ml 1 CN. Determina-
tion of cyanide in biological fluids and other
materials is of interest and the application of
the method for this purpose is under study. In
addition, some rapid procedures for the identifi-
cation of free cyanide ions in the environment
can be developed.
References
[1] G. Drochioiu, I. Mangalagiu, V. Tataru, Analyst 125
(2000) 939 941.
 G. Drochioiu / Talanta 56 (2002) 11631165 1165

[2] G. Drochioiu, G. Petrache, R. Cojocaru, M. Murariu,
Actes de Colloque Franco-Roumain de Chimie Applique e,
Bacau, Roumanie, 2000, 106 109.
[3] W. Ko nig, J. Prakt. Chem. 69 (1904) 105 137.
[4] L.S. Bark, H.G. Higson, Talanta 11 (1964) 471
472.
[5] S. Amlathe, V.K. Gupta, Fresenius J. Anal. Chem. 338
(1990) 615 617.
[6] A. Sano, M. Takezawa, S. Takitani, Talanta 34 (1987)
743 744.
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363 366.