ISSN 00271314, Moscow University Chemistry Bulletin, 2014, Vol. 69, No. 1, pp. 12–19. © Allerton Press, Inc.

, 2014.
Original Russian Text © E.M. Basova, V.M. Ivanov, O.K. Apendeeva, 2014, published in Vestnik Moskovskogo Universiteta. Khimiya, 2014, No. 1, pp. 15–23.

Spectrophotometric Determination of Thiocyanate Ions

in Stratal Waters
E. M. Basovaa, V. M. Ivanovb, and O. K. Apendeevaa
a
Dubna International University for Nature, Society and Man, Universitetskaya ul. 19, Moscow oblast, Dubna, 141980 Russia
b
Department of Chemistry, Moscow State University, Moscow, 119991 Russia
email: mvonavi@mail.ru
Received 20 July, 2013

Abstract—The formation of [FeSCN]2+ complex in hydrochloric and sulfuric acid medium was studied by
spectrophotometry using iron(III) sulfate and ammonium iron(III) sulfate solutions as reactants. A method
for the determination of 10–200 μg SCN– in 25 mL water solutions containing ammonium iron(III) sulfate in
sulfuric acid medium was developed; its determination limit is 2.6 μg (P = 0.99, n = 9). The method was applied
for the analysis of model water samples with macro and microcomponent compositions similar to that of water
from the Arigol licensed area. Operational control of the accuracy rate was performed by the standard addition
method. The developed method can be applied to analyze water samples containing 1–90 mg/L thiocyanate
ions.

Keywords: thiocyanate ions, Fe(III) complex, spectrophotometry, stratal waters

DOI: 10.3103/S0027131414010039

Anthropogenic sources and biodegradation of sul
fur compounds and biomasses are responsible for thio
cyanate ions in the environment. Thiocyanates are
used for the production of thiourea (source raw mate
rial), acrylic fibers (dispersion medium for copoly
mers), and corrosioninhibiting paints. They are used
in fabric dyeing and printing, in photography, for agri
cultural weeding, and as an indicator in the studies of
oil deposit distribution and stratigraphic structure.
Thiocyanate ions are generally found in industrial
wastewater. Thiocyanate ions in surface water may
originate from the waste water of coking plants, min
eral processing plants, and metallurgical works; thio
cyanates can form during the fertilizer manufacturing
process.
The method for spectrophotometric determination
of thiocyanate ions in waste water of concentrating
mills [1] is based on the formation of the red complex
in hydrochloric acid medium upon addition of
iron(III) chloride. The method is simple, however col
ored complex is unstable, and several ions interfere
with the analysis [2]. The major interfering substances
of wastewater are cyanide and hexacyanoferrate ions
that form insoluble salts when samples are treated with
concentrated zinc chloride solution. Such treatment
also isolates the concomitant xanthates, thiosulfate
and sulfide ions. Stratal waters contain none of these
substance; therefore, such treatment is not required
for their analysis. The method of spectrophotometric
determination of the SCN– complex with Fe(III) is
adapted for sequential injection analysis, which makes
it highly efficient (24 samples per hour) [3]. This
method was applied for the analysis of human saliva
(mM); this analysis allowed the identification of
smokers among the students [4]. No literature data are
available on the effect of natural or stratal water com
ponents on the determination of thiocyanate ions
complexed with Fe(III).
The purpose of this study was to develop a method
for the photometric determination of thiocyanate ions
complexed with Fe(III) in stratal water.
EXPERIMENTAL
Equipment. The experiment was performed using a
KFK2MP photometer.
Reagents. We used Fe2(SO4)3 ⋅ 9H2O (analytical
grade), NaCl (analytical grade), (NH4)2SO4 (pure),
NaHCO3 (analytical grade) (all these reagents were
from Vekton, Russia); NH4Fe(SO4)2 ⋅ 12H2O (reagent
grade), CaCl2 (pure), MgSO4 ⋅ 7H2O (reagent grade),
KH2PO4 (reagent grade), CuSO4 ⋅ 5H2O (pure),
ZnSO4 ⋅ 7H2O (pure), CrCl3 ⋅ 6H2O (pure), Na2B4O7 ⋅
10H2O (analytical grade), KBr (analytical grade),
AlCl3 (analytical grade), Pb(CH3COO)2 ⋅ 3H2O (ana
lytical grade), NiCl2 ⋅ 6H2O (pure) (all these reagents
were from Reakhim, Russia); KSCN (analytical
grade) (Khimreaktivkomplekt, Russia); concentrated
H2SO4 (reagent grade) and concentrated HCl (special
purity grade) (Sigma Tek, Russia); NaF (pure)
(AO Mosreaktiv, Russia); MnCl2 ⋅ 4H2O (analytical

12
 SPECTROPHOTOMETRIC DETERMINATION OF THIOCYANATE IONS
grade) (HATSKP, Russia); (NH4)6Mo7O24 ⋅ 4H2O
(analytical grade) and K2SO4 (analytical grade)
(Ekros, Russia); uranin (sodium salt of fluorescein)
C20H10Na2O5, eosin C20H6Br4Na2O5, rhodamine 6G
C28H31ClN2O3, rhodamine C C28H31ClN2O3, and
7amino1,3naphthalenedisulfonic acid (potassium
salt, hydrate) C10H10KNO7S2 (AG acid).
All solutions were prepared with distilled water.
Preparation of solutions. FeCl3 ⋅ 6H2O, which is the
main reagent in the method [1], is highly hydroscopic.
Therefore, the present study was focused on the inter
action of thiocyanate ions with Fe2(SO4)3 ⋅ 9H2O and
alum. The concentration of Fe(III) required by the
method [1] is impossible to reach in the solutions of
these salts, because their water solubility is much lower
than that of the iron(III) chloride. The maximum
amount of Fe2(SO4)3 ⋅ 9H2O that can dissolve in water
in a 200mL flask was found to be 41.5895 g; complete
dissolution took 24 hours. The concentration of
Fe2(SO4)3 in the resulting solution was 0.35 M, and the
concentration of Fe(III) was 0.7 M.
The water solubility of alum is even lower; more
over, it was not significantly increased by heating or
acidifying the solution by hydrochloric or sulfuric
acid. The addition of HCl or H2SO4 is recommended
in order to increase the hydrolytic stability of Fe(III)
solutions. The alum solution was prepared by dissolv
ing 35.6822 g alum in a 100mL flask, followed by the
addition of 20 mL of of concentrated HCl or 5 mL
concentrated H2SO4; the undissolved reagent was fil
tered the next day.
Dilute solutions of HCl (H2SO4) were prepared by
diluting 20 mL (5 mL) stock solutions with water in
100mL flasks.
A standard solution of thiocyanate ions (1 mg/mL)
was prepared by dissolving 0.1673 g KSCN in water in
a 100mL flask. A working solution (100 μg/mL) was
prepared by diluting the standard solution with water.
RESULTS AND DISCUSSION
The Selection of Optimum Conditions for the Formation
of the Colored Complex
In the Fe(III)–SCN– system, the following com
plexes can be formed: [Fe(SCN)n]3 – n, where n = 1–6 [5].
Because of the excess concentration of Fe(III) during
the determination of SCN–, only the [FeSCN]2+ com
plex is actually formed. The acid medium (0.05–
2.00 M) is optimal for the complex formation; the
acidity can be adjusted by sulfuric, hydrochloric,
nitric, and hypochlorous acids [5].
We studied the effect of H2SO4 and HCl concentra
tions on the formation of the [FeSCN]2+ complex.
The solutions containing thiocyanate ions and Fe(III)
are redbrown in a sulfuric acid medium and yellow
red in a hydrochloric acid medium. It should be
emphasized that the control solution is also colored;
MOSCOW UNIVERSITY CHEMISTRY BULLETIN Vol. 69
13
A
0.8
0.7 1
0.6
0.5
0.4 2
0.3
0.2
0.1
0 2 4 6 8 10
V, mL
Fig. 1. Correlation between the optical density of the com
plex solution and the volume of Fe(III) solution (from
ammonium iron(III) sulfate) in the following media:
1, HCl; 2, H2SO4 ( c – = 100 μg/25 mL, cHCl = 0.2 M;
SCN
cH = 0.21 M; λ = 490 nm; l =5 cm).
2 SO 4
for that reason, the optical density at 490 nm was mea
sured against the control solution. The optical density
of the solution is increased in the hydrochloric acid
medium. The optimal acidity of the hydrochloric acid
medium was 0.2–0.3 M, while that of the sulfuric acid
medium was 0.07–0.22 M.
The correlations between the optical density of the
solutions and the concentration of Fe(III) for various
iron(III) salts are shown in Figs. 1 and 2. Both of the
studied reagents can be applied for the SCN– determi
nation. When using iron(III) sulfate, the optimal con
centration of Fe(III) in the sulfuric acid medium was
0.06–0.12 M and 0.12 M in the hydrochloric acid
medium. If alum was used, it was sufficient to add
4 mL solution to the 25mL flask. Being the most
available reagent, ammonium iron(III) sulfate was
chosen for routine analysis.
We studied the rate of the color development. The
experiment was performed in a threeblade mixer;
Fe2(SO4)3 in sulfuric acid medium was used as a
reagent. The results are shown in Table 1. The optical
density of the control solution is seen to be indepen
dent of the incubation period. The optical density of
the test solution can also be considered constant
within the studied range of time, because there is no
clear tendency towards its increase or decrease. Fluc
tuations are possibly related to the insufficiently stable
operation of a device. Thus, the optical density of
solutions containing the Fe(III)–SCN– complex can
be measured immediately after their preparation.
No. 1 2014