ISSN 10619348, Journal of Analytical Chemistry, 2015, Vol. 70, No. 6, pp. 685–690. © Pleiades Publishing, Ltd., 2015.

Original Russian Text © G.R. Ramazanova, T.I. Tikhomirova, V.V. Apyari, 2015, published in Zhurnal Analiticheskoi Khimii, 2015, Vol. 70, No. 6, pp. 602–607.

ARTICLES

Adsorption of Sunset Yellow FCF Food Dye from Aqueous Solutions

and Its Determination by Diffuse Reflectance Spectroscopy
G. R. Ramazanova, T. I. Tikhomirova, and V. V. Apyari
Department of Chemistry, Moscow State University, Moscow, 119991 Russia
email: tikhomirovatatyana@yandex.ru
Received May 13, 2014; in final form, October 15, 2014

Abstract—The adsorption of Sunset Yellow FCF food dye (Orange Yellow S, E110) from aqueous solutions
on silica adsorbents modified by alkyl groups and on γAl2O3 is studied. The adsorption attains a maximum
in the range 1 M HCl–pH 1 on Diasorb130C16 (79–87%), 0.5 M HCl–pH 6.8 on Diasorb130C16 and
Diasorb100C8 in the presence of trimethylammonium bromide (92–98%), and pH 1–5.6 on γAl2O3 (72–
87%). Calibration graphs of the dependence of the Kubelka–Munk function F on the dye concentration in
aqueous solutions are built. The possibility of the preconcentration of trace amounts of the dye from large vol
umes of solutions is shown. A method of dye determination is proposed based on its separation by adsorption
followed by determination by diffuse reflectance spectroscopy directly in the adsorbent phase and used in the
analysis of the O! Orange drink. The accuracy of the determination is verified by comparison with the results
obtained by the GOST P 524702005 procedure.

Keywords: Sunset Yellow FCF (Orange Yellow S), alumina, Diasorb130C16, Diasorb100C8, adsorption,
diffuse reflectance spectroscopy
DOI: 10.1134/S1061934815060131

The appearance and color of products are features
by which users can judge about the quality of a prod
uct. Natural dyes are unstable and can easily decom
pose under the conditions of manufacture; therefore,
the use of synthetic organic dyes has been recognized
a reliable and economic method of solving problems of
the restoration or creation of a necessary color in the
treatment of foodstuffs. However, synthetic dyes can
cause allergic reactions and various diseases; there
fore, their concentrations in foodstuffs should be con
trolled. In addition, dyes enter the environment with
waste waters of enterprises of the food industry; there
fore, there is a need of their detection and determina
tion in various environmental samples.
In determining dyes, they are often preseparated
with adsorbents, such as wool [1], polyurethane foams
[2–4], activated charcoal [5–7], chitosan [8, 9], per
lite [10–13], silica [14, 15], bentonite clays, rice husk,
hair [16, 17], etc. The preconcentration stage is partic
ularly necessary in the analysis of the purified sewage
waters, in which dye concentrations are at the trace
level. However, in the adsorption of dyes has not been
studied systematically in the majority of works. Often
no data were present on the dependence of adsorption
on pH and ionic strength and no partition coefficients
of compounds were reported. The published data on
the adsorption behavior of dyes on the same adsor
bents are often contradictory.
Previously we have shown that some anionic sul
foazo dyes are adsorbed on alumina and etherbased
polyurethane foams [18]. Their recoveries on polyure
thane foams were low and comprised 20–30%. Alu
mina was more efficient (70–80%). The results
obtained indicate the predominance of electrostatic
interactions between anionic forms of the dyes and the
adsorbent surface. In this case, recovery can depend
on the ionic strength of the solution. In this connec
tion, the choice of an adsorption system in which
extraction is due to interactions of other types, for
example, hydrophobic, is of current importance. One
of possible solutions is the sorption of a dye in the
molecular form, or the synthesis of a hydrophobic
compound by an interaction with an ionpair reagent
and followed by the extraction of the ion pair with
a nonpolar adsorbent, for example, hydrophobized
silica.
The aim of this work consisted in a comparison of
the characteristics of adsorption of Sunset Yellow FCF
food dye (Orange Yellow S, E110, see scheme), a rep
resentative of sulfoazo dyes widely used in the food
industry of many countries, Russian Federation
among them, but prohibited in the Unites States, Nor
way, Finland, etc., on alumina and silica adsorbents
modified by alkyl groups. In addition, we studied the
possibility of combining adsorption preconcentration
with the subsequent determination of the dye on the
adsorbent surface by diffuse reflectance spectroscopy.

685
686 RAMAZANOVA et al.
HO
N In the study in the dynamic mode, we used a col
N
NaO3S SO3Na
Structural formula of the dye Sunset Yellow FCF.
EXPERIMENTAL
Reagents and equipment. We used the dye Sunset
Yellow FCF (SY) (SigmaAldrich). The stock solution
of SY (1 g/L) was prepared by dissolving an exact por
tion of a compound in distilled water. Working solu
tions (0.1 g/L) were prepared by diluting the stock
solution with water. To obtain ion pairs, we used a cat
ionic surfactant, cetyl trimethylammonium bromide
(CTMAB, 9.2 mM). The necessary value of pH was
adjusted using 0.1, 1, and 2 M HCl; the required ionic
strength was created using 1 and 2 M NaCl solutions.
All reagents were of analytical and better grade.
The electronic absorption spectra of the dye were
recorded on an SF103 spectrophotometer (Akvilon,
Russia). The absorbance of solutions was measured on
an SF46 spectrophotometer (LOMO, St. Petersburg,
Russia). Test tubes were shaken on a mechanical
EKROS6500 vibromixer. The pH of solutions was
measured with an EkspertpH pH meter; spectra of
diffuse reflection were measured on an EyeOne Pro
minispectrophotometer (XRite), which was pro
posed as an efficient alternative to a diffuse reflection
spectrometer [19, 20]. Adsorption in the dynamic
mode was performed using a 2115 Multiperpex peri
staltic pump (LKB BROMMA).
The adsorbents were Diasorb130C16 (specific
surface area 250 m2/g, particle size 40–160 µm), Dia
sorb100C8 (specific surface area 250 m2/g, particle
size 63–200 µm), silica of KSKG brand (specific sur
face area 250 m2/g, particle size 40–160 µm), and also
γAl2O3 (specific surface area 138 m2/g, particle size
63–200 µm).
Experimental procedure. To study adsorption in the
batch mode, 1mL portions of a working solution of
the dye (0.1 g/L) and HCl for the creation of the nec
essary pH value were placed in graduated test tubes of
the volume 15 mL; in the study of adsorption of the ion
pair, a CTMAB solution was also added; then an
adsorbent portion (0.10 g) was introduced and the
mixture was diluted to 10 mL with water. Before the
introduction into the solution, a portion of modified
silica was treated with a small amount of ethanol. The
test tubes were shaken on a vibromixer for the time
necessary for the attainment of an adsorption equilib
rium; then the sorbent was separated from the solution
by filtering through a paper filter. The concentration of
the dye in the water phase was determined by spectro
photometry using its intrinsic absorption at 484 nm.
The adsorbent was separated from the solution and
JOURNAL OF ANALYTICAL CHEMISTRY
dried in air; then spectra of diffuse reflectance were
measured.
umn (diameter 0.5 cm) with 0.20 g of an sorbent and
passed a test solution through it at a rate of 4–
6 mL/min using peristaltic pump.
The detection limit in determining SY by diffuse
reflectance spectroscopy was calculated by the equa
tion сmin = 3so/s', where so is the standard deviation of
the Kubelka–Munk function, calculated from the
coefficients of diffuse reflectance by the equation F =
(1 – R)2/(2R), for the blank experiment (20 measure
ments); s' is the slope of the calibration dependence
ΔF vs. cSY; ΔF = F – Fo, where F is the Kubelka–Munk
function of the adsorbent with the dye and Fo is the
Kubelka–Munk function of the pure adsorbent.
RESULTS AND DISCUSSION
The pH dependence of the dye adsorption was stud
ied in the batch mode (Fig. 1). Preliminary experi
ments demonstrated that time of attainment of an
adsorption equilibrium was 15 min on silica adsor
bents and 30 min on γAl2O3. The recovery of the dye
on Diasorb130C16 attained a maximum in acid
media (1 M HCl–pH 1) and comprised 79–87%. The
further increase in pH led to a decrease in recovery,
which was due to the transition of the dye to a less
charged form (pKa = 0.3, the value was calculated
using the standard software package by ACD Labs).
The surfaces of silica adsorbents Diasorb130C16
and Diasorb100C8 are hydrophobic; therefore, we
can conclude that adsorption on their surfaces was due
to hydrophobic interactions.
On the addition of CTMAB, the recoveries of SY
on Diasorb130C16 and Diasorb100C8 were
almost equal in the range 0.5 M HCl–pH 6.8 and
comprised 92–98%. The spectra of SY in aqueous
solutions in the presence of CTMAB exhibited a hyp
sochromic shift of the absorption maximum by 10 nm;
according to the data [21, 22], this is indicative of the
formation of an ion pair. Therefore, the addition an
ionpair reagent extended the region of extraction of
SY on hydrophobized silicas, because this resulted in
the formation of a hydrophobic ion pair in a wide
range of pH. The lower recovery from 1 M HCl was,
evidently, due to the transition of the dye to the molec
ular form, which led to the decomposition of the ion
pair of SY with CTMAB, and also due to the compet
ing action of the chloride ion.
In the preparation of hydrophobized silicas, not all
silanol groups of silica react with the organosilicon
modifier; therefore, some of silanol groups remained
nonbound and could affect the adsorption. To assess
the effect of residual silanol groups on the recovery of
the dye, we studied its adsorption on unmodified sil
ica. It was found that the KSKG silica virtually did
not adsorb SY (1–3%) in the whole studied pH range.
Vol. 70 No. 6 2015