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DEGRADATION OF SYNTHETIC ORGANIC DYES IN SOLUTION BY FERRATE –

HYPOCHLORITE OR CALCIUM HYPOCHLORITE DEGRADACIÓN DE TINTES
SINTÉTICOS ORGÁNICOS EN SOLUCIÓN POR FERRATO-HIPOCLORITO O...

Article  in  INVESTIGACION & DESARROLLO · July 2017

DOI: 10.23881/idupbo.017.1-4i

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 INVESTIGACIÓN & DESARROLLO, No. 17, Vol. 1: 43 – 53 (2017)
ISSN 2518-4431

DEGRADATION OF SYNTHETIC ORGANIC DYES IN SOLUTION BY FERRATE – HYPOCHLORITE OR

CALCIUM HYPOCHLORITE

DEGRADACIÓN DE TINTES SINTÉTICOS ORGÁNICOS EN SOLUCIÓN POR FERRATO-HIPOCLORITO

O HIPOCLORITO DE CALCIO

Pablo Marcelo Pérez Garcíaa,b, Sandra L. Ibáñez-Calerob and Ramiro Escalera Vásqueza
a
Centro de Investigaciones en Procesos Industriales – CIPI
b
Centro de Investigaciones Fitoquímicas-CIF
Universidad Privada Boliviana
[email protected]
(Recibido el 18 mayo 2017, aceptado para publicación el 16 de junio 2017)

ABSTRACT
This study investigated the use of ferrate – hypochlorite solution or solid Ca(OCl)2 as treatment options to remove color
and COD from solutions of the synthetic organic dyes: Reactive blue 19, Allura red and Reactive black 5. It was found
that doses around 1000 ppm Ca(OCl)2 had color removal efficiencies around 90 % for all the dyes after 15 minutes
reaction time; this treatment had a COD removal efficiency of 97 % for azo dye Allura red. The ferrate – hypochlorite
(0.06 mM - <400 ppm) treatment resulted in a 50% color removal for Reactive blue 19 dye after 1 hour reaction time.
The COD removal of Reactive blue 19 dye was improved from 40% to 84% when the ferrate – hypochlorite solution was
used.
Keywords: Ferrate, Synthetic Organic Dyes, Hipochlorite, COD Removal.

RESUMEN
Este estudio investigó el uso de una solución de ferrato – hipoclorito o Ca(OCl)2 sólido como opciones de tratamiento
para la remoción del color y de la DQO de soluciones de los tintes orgánicos industriales: Reactive blue 19, Allura red y
Reactive black 5. Se encontró que dosis de alrededor 1000 ppm de Ca(OCl) 2 generaron eficiencias de remoción de color
de alrededor el 90 % para todos los tintes luego de 15 minutos de reacción; este tratamiento tuvo una eficiencia de
remoción de la DQO de 97 % para el tinte azo Allura Red. El tratamiento con ferrato – hipoclorito (0.06 mM - <400
ppm) resultó en una remoción de color de 50 % para el tinte Reactive blue 19 después de 1 hora de reacción. La
remoción de la DQO del tinte orgánico industrial Reactive blue 19 fue mejorado del 40% al 84% cuando la solución
ferrato – hipoclorito fue utilizada.
Palabras claves: Ferrato, Tintes Orgánicos Industriales, Hipoclorito, Remoción DQO.

1. INTRODUCTION

Synthetic organic dyes are among the major chemicals used as manufacture goods by the textile industry[1]. These dyes
are recalcitrant chemicals and represent a major concern for the treatment of industrial textile effluents because
conventional wastewater treatment systems have been inefficient eliminating them[2], [3]. During the last decades, the
treatment technologies based on Advanced Oxidation Process (AOP) have garnered the great interest of the scientific
community for the treatment of industrial effluents containing high concentration of recalcitrant chemicals [4], [5].
During these processes, very reactive chemical species are introduced or produced in situ to oxidize organic matter,
ideally only generating CO2, H2O and biodegradable organic products. For instance, the application of the Fenton
reagent (a mixture of H2O2/Fe2+) generates hydroxyl radicals under the action of UV light triggering a complex chain
reaction provoking the organic matter decomposition declining the chemical oxygen demand (COD)[6]. Our group
reported[7] that a treatment based on photo-Fenton process which results in high removal efficiencies of color (77 %)
and COD (92 %) from industrial effluents containing high content of synthetic organic dyes. The process was conceived
in a solar light concentrating photo-reactor system with an average reaction time of 2.5 hours.

Another highly oxidant reagent based on iron is ferrate (FeO 42-), where iron has an oxidation state of +6. In aqueous
solution the ferrate is readily oxidized to Fe3+ having standard half-reduction potentials of +2.2 V and +0.72 V in acidic
and basic medium respectively, these potential values are comparable to those from common oxidizers as ozone or

UPB - INVESTIGACIÓN & DESARROLLO, No. 17, Vol. 1: 43 – 53 (2017) 43

DIO: 10.23881/idupbo.017.1-4i
 PÉREZ, IBÁÑEZ-CALERO AND ESCALERA

chlorine[8]. The advantages of using ferrate as oxidizing agent in wastewater treatment are its low toxicity and its
flocculating activity which increases the removal percentage of COD[8], [9]. Moreover its synthesis is simple from
affordable chemical compounds[10], [11] and the oxidation of organic matter by ferrate only produces innocuous
organic byproducts[12]; this is not always the case when ozone or chlorine derivatives are applied[13].

The use of ferrate as oxidizing agent for the removal of synthetic organic dyes form industrial effluents was reported by
Li et al.[14]. The authors declared a 95 % decolorization of a 50 ppm azo dye Orange II solution by batch reacting with
0.17 mM ferrate – hypochlorite solution after 30 minutes; this result demonstrated an oxidizing synergy between the
ferrate and hypochlorite since the treatment with only ferrate (10 ppm) led to 67% decolorization. Similar removal
efficiencies were reported by Xu et al.[15] and GC-MS analysis demonstrated that the first step of the decomposition of
the azo dye was the cleavage of the azo bond. On the other hand, Massoudinejad et al.[16] studied the treatment of
effluents from polyacrylic textile industry by Ca(OCl)2 direct application. A dose treatment of 2000 ppm led to >95%
color – COD removal with a reaction time of only 10 minutes. The authors declared that the absence of oxygen and
humic materials in the effluents avoid the formation of any hazardous chlorinated products such trihalomethanes (THM).
This work aims to study the decomposition treatment of three synthetic industrial organic dyes used by the textile
industry in Cochabamba[7], using ferrate – hypochlorite solution or solid calcium hypochlorite as oxidizing agents.
This report also includes the complete description of the synthesis and characterization of pure ferrate and ferrate –
hypochlorite solutions made from cheap and readily available starting materials. To the best of our knowledge this is the
first work concerning the use of ferrate – hypochlorite solution or Ca(OCl)2 for the removal treatment of the synthetic
organic dyes: Reactive blue 19, Allura red and Reactive black 5.

2. MATERIALS AND METHODS

2.1 General

The UV-vis spectra analyses were carried out using a Shimadzu UV-1601 spectrometer using quartz cells with 1 cm
length. The COD analysis were carried out by the “Centro de Aguas y Saneamiento Ambiental – CASA - UMSS” using
the standard method 5220 D. The synthetic organic dyes were provided by the local industry[7]. The rest of the
chemicals, in UPB laboratories, had technical grade qualities and were purchased in local stores.

2.2 Characterization of organic dyes

The UV-vis spectra were registered for 100 ppm solutions of each dye: blue, red and black. The solutions were prepared
using distilled water as solvent.

2.3 Wet chemical synthesis of ferrate

The used experimental procedure was developed by Ibañez et al.[10] 6 g of NaOH pulverized were placed into a 100 mL
beaker containing 80 mL of distilled water and magnetic stirred until total dissolution. 4 g of Ca(OCl)2 were added to the
basic solution and magnetic stirred at 60°C until the formation of an homogeneous white suspension. 500 mg of
pulverized FeCl3 were added to the suspension and the heating temperature was increased to 80 °C. The resulting
suspension was stirred at 80°C until a homogenous violet color appeared. The suspension was then cooled slowly to
room temperature. The suspension was placed in centrifugal tubes and centrifuged at 2000 rpm during 2 minutes. The
supernatant was removed and placed in a beaker. The final clear violet solution was UV-vis analyzed.

2.4 Electrochemical synthesis of ferrate

The used experimental procedure was developed by Ibañez et al.[10] 30 g of NaOH were dissolved in 200 mL of
distilled water. This solution was placed inside an U shaped glass tube vertically installed using an utility clamp held to
a ring stand. An iron coiled wire was installed inside each extremity of the U-tube and connected to a voltage generator
using jump wires. 12 V were applied to the system until inside the anode extremity a clear violet solution appeared. The
voltage source was then switched-off and the iron electrodes were carefully removed. The ferrate solution was recovered
and placed in a beaker to further UV-vis analysis.

2.5 Color removal tests by ferrate – hypochlorite solutions

 Preparation of 200 ppm dye solution: 50 mg of dye were dissolved in distilled water inside a 250 mL volumetric
flask filled to the calibration mark.

44 UPB - INVESTIGACIÓN & DESARROLLO, No. 17, Vol. 1: 43 – 53 (2017)

 DEGRADATION OF SYNTHETIC ORGANIC DYES IN SOLUTION…

 Preparation of basic hypochlorite solution: 6 g of NaOH pulverized were placed into a 100 mL beaker containing 80
mL of distilled water and magnetic stirred until total dissolution. 4 g of Ca(OCl)2 were added to the basic solution
and magnetic stirred at 60°C until the formation of an homogeneous white suspension. The suspension was then
cooled slowly to room temperature. The suspension was placed in centrifugal tubes and centrifuged at 2000 rpm
during 2 minutes. The supernatant was removed and placed in a beaker.
 Color removal test with ferrate hypochlorite solution: 20 mL of 200 ppm blue dye solution were placed into a 100
mL beaker and 20 mL ferrate hypochlorite solution (absorbance: 0.65) were added under magnetic stirring. The
resulting solution was stirred during 15 minutes and its UV-vis spectrum was recorded.
 Color removal test with basic hypochlorite solution: 20 mL of 200 ppm blue dye solution were placed into a 100 mL
beaker and 20 mL basic hypochlorite solution was added under magnetic stirring. The resulting solution was stirred
during 15 minutes and its UV-vis spectrum was recorded.
 Color removal test with Ca(OCl)2: 40 mL of 200 ppm dye solution were placed into a 100 mL and an specific
amount of Ca(OCl)2 was added until magnetic stirring. The resulting solution was stirred during 15 minutes and its
UV-vis spectrum was recorded. Three tests were carried out for each dye using increasing quantities of Ca(OCl) 2:
approximately 50, 100 and 200 mg.

2.6 COD removal tests

 COD removal with Ca(OCl)2: This test was carried out using separately blue and red dye. 50 mg of dye were
dissolved in water inside a 250 mL volumetric flask filled to the calibration mark. 100 mL of this 200 ppm solution
were separated for COD analysis as blank. 100 mL were treated with 100 mg Ca(OCl) 2 (1000 ppm dose) under
magnetic stirring during 15 min. A little portion of the final solution was UV-vis analyzed and the remainder was
sent to COD analysis.
 COD removal with ferrate – hypochlorite solution: 50 mg of blue dye were dissolved in water inside a 250 mL
volumetric flask filled to the calibration mark. 100 mL of this 200 ppm solution were separated for COD analysis as
blank. 100 mL were treated with 10 mL of ferrate – hypochlorite solution (A=0.758, c=0.66 mM) during 1 hour. A
little portion of the final solution was UV-vis analyzed and the remainder was sent to COD analysis.

3. RESULTS AND DISCUSSION

3.1 Characterization of industrial organic dyes

Three colors of synthetic organic dyes were analyzed: blue, red and black. The chemical nature of each one was
characterized by UV-vis spectrometry and identified by comparison of the absorption spectra to those reported in the
literature. The absorption spectra were recorded in a wavelength range of 190 – 900 nm.

Figure 1 shows the absorption spectrum for the blue dye showing a maximum absorption at 590 nm. A comparison to
reported spectra[17] let us to conclude that the commercial name of this dye is Reactive blue 19.

3
2.5
Absorbance [ ]

2
1.5
1
0.5
0
190 290 390 490 590 690 790 890
Wavelength [nm]

Figure 1 - Absorption spectrum for the dye “Reactive blue 19”.

UPB - INVESTIGACIÓN & DESARROLLO, No. 17, Vol. 1: 43 – 53 (2017) 45

 PÉREZ, IBÁÑEZ-CALERO AND ESCALERA

The chemical structure of this dye is presented in Figure 2. The molecular formula of this compound is
C22H16N2Na2O11S3 with a molecular weight of 626.5 g/mol. The compound is an anthraquinone dye (quinoid
chromophore)[18] and has auxochromes such as amine, sulfone and sulfonate.

O NH2
SO3Na

O
O O
O HN S S
ONa
O O

Figure 2 - Chemical structure of the dye “Reactive blue 19”.

The absorption spectrum of the red dye was recorded (Figure 3) showing a maximum absorbance at 490 nm. Its
comparison with the literature[19] let us to conclude that the commercial name of this dye is Allura red.

4
3.5
3
Absorbance

2.5
2
1.5
1
0.5
0
190 290 390 490 590 690 790 890
Wavelength [nm]

Figure 3 - Absorption spectrum for the dye “Allura red”.

The dye Allura red has the molecular formula C18H14N2Na2O8S2 and a molecular weight of 496.4 g/mol. The chemical
structure is showed in Figure 4. The compound is an azo dye[18], the azo chromophore is formed by tautomerism from
the hidrazone group. The auxochromes are methoxy and sulfonate groups.

NaO 3S

O
N
HN
O

SO 3Na
Figure 4 - Chemical structure of the dye “Allura Red”.

46 UPB - INVESTIGACIÓN & DESARROLLO, No. 17, Vol. 1: 43 – 53 (2017)

 DEGRADATION OF SYNTHETIC ORGANIC DYES IN SOLUTION…

Figure 5 shows the absorption spectrum for the black dye with a maximum absorption at 600 nm, the shape of the
spectrum is very broad. We compared this spectrum with the literature[20] concluding that the commercial name of the
dye is Reactive black 5.

2.5
Absorbance [ ]

1.5

0.5

0
190 290 390 490 590 690 790 890
Wavelength [nm]

Figure 5 - Absorption spectrum for the dye “Reactive black 5”.

The dye Reactive Black 5 has a molecular formula C16H21N5Na4O19S6 with a molecular weight of 991.8 g/mol. Figure 6
shows the chemical structure. The compound is an azo dye[18] with two azo chromophores (one is the hidrazone
tautomer); the auxochromes are sulfone, amine and sulfonate groups.

NaO 3S SO3Na

N N
N NH2 O HN
O O
S S
O O
O O
NaO 3S SO3Na
Figure 6 - Chemical structure of the dye “Reactive Black 5.

3.2 Characterization of ferrate

Ferrate was synthesized in solution by chemical wet and electrochemical methods. Previous works reported[21] that
aqueous ferrate solutions generates a maximum absorbance at approximately 510 nm. We show in figure 7, the UV/vis
spectra of our ferrate solutions obtained by wet chemical and electrochemical method. As can be seen, the maximum
absorbance matches at 510 nm for both synthetic routes. The maximum absorbance values were converted in ferrate
solution concentrations using 1150 L∙mol-1∙cm-1 as extinction coefficient [21]. The ferrate concentration in the solution
made by wet chemical method (0.66 mM) is around seven times higher than the concentration obtained by
electrochemical method (0.09 mM). A plausible explanation is that the iron rods used as electrodes did not offer a
convenient active surface to ensure an optimum mass transfer during the electrochemical synthesis.

UPB - INVESTIGACIÓN & DESARROLLO, No. 17, Vol. 1: 43 – 53 (2017) 47

 PÉREZ, IBÁÑEZ-CALERO AND ESCALERA

0.1 0.8

Absorbance [ ] (Electrochemical M.)

Absorbance [ ] (Wet Chemical M.) 0.09 0.7
0.08
0.6
0.07
0.06 0.5

0.05 0.4
0.04 0.3
0.03
0.2
0.02
0.01 0.1

0 0
400 450 500 550 600 650 700 750 800
Wavelenght [nm]

Figure 7 - Absorption spectra for ferrate solutions.”Solid line”: Wet Chemical Method “Dashed line”:
Electrochemical Method.

We studied the stability of our ferrate solutions following the kinetics of decomposition at room temperature. A marked
visual color change characterizes the decomposition of ferrate form strong violet to yellow brown. In order to compare
our results to those described in the literature[21], we assumed a first order kinetics. Figure 8 shows the kinetic
decomposition profile for the ferrate produced by both applied synthetic methodologies and their respective exponential
regression; the decomposition rate constants are 3×10-5 s-1 (wet chemical method) and 8×10-4 s-1 (electrochemical
method). From these values, we calculated the decomposition halftime of ferrate ion in solution: 6.5 hours (wet chemical
method) and 17 minutes (electrochemical method). The kinetic values for the ferrate solution synthesized by
electrochemical method correlate perfectly with those previously reported[21]. The higher stability of ferrate solution
made by wet chemical method might be due to the presence of hypochlorite; both species have in basic environment
similar redox potentials (around +0.8 V) so hypochlorite helps to avoid a fast reduction from iron +6 to iron +3.

Time [s]
Electrochemical M.
0 50 100 150 200 250 300 350
6.40E-04 8.00E-05
Electrochemical M.
Ferrate Conc. [M]

Ferrate Conc. [M]

Wet Chemical M.

6.20E-04
6.00E-05
6.00E-04
y = 7E-05e-8E-04x 4.00E-05
5.80E-04 R² = 0.9927
y = 0.0006e-3E-05x 2.00E-05
5.60E-04 R² = 0.9953
5.40E-04 0.00E+00
0 500 1000 1500 2000 2500 3000 3500 4000
Time [s]
Wet Chemical M.

Figure 8 - Kinetic profiles of ferrate solutions.

“Dots”: Electrochemical Method and “Triangles”: Wet Chemical Method.

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 DEGRADATION OF SYNTHETIC ORGANIC DYES IN SOLUTION…

3.3 Color removal tests

The color removal efficiency was tested for the Reactive blue 19 dye using the ferrate – hypochlorite solution and a
basic saturated hypochlorite solution as blank test. The tests were carried out at room temperature over 20 mL of 200
ppm dye solution. The addition of 20 mL of ferrate – hypochlorite solution or 20 mL of basic saturated hypochlorite
solution produced a color removal of >95 % after 1 hour agitation. In figure 9, a total disappearance of the signals at
visible region was observed; this might mean that the quinoid chromophore is completely cleaved. On the hand, the
spectra after treatment show strong signals at the UV region, this might indicate that the aromatic rings could not be
decomposed during the process.

4.5
4
3.5
Absorbance [ ]

3
Sample without treatment
2.5
2 Sample treated by Ferrate
1.5 - Hypochlorite
1 Sample treated with
0.5 hypochlorite
0
190 290 390 490 590 690 790 890
Wavelength [nm]

Figure 9 - Color removal test for 200 ppm blue dye solution.

Considering that the ferrate – hypochlorite and basic saturated hypochlorite solutions have the same color removal
efficiency, we decided then to try a treatment directly applying solid calcium hypochlorite to the dye solution. We
applied Ca(OCl)2 concentrations similar to those previously reported[16]. Figure 10 shows the spectra comparison for
the treatment of 40 mL of 200 ppm solution of Reactive blue 19 dye. The color removal was around 50 % after
15 minutes reaction for all the Ca(OCl)2 doses: 1375 ppm, 2443 ppm and 5700 ppm; but more than 95 % after 60
minutes of treatment with the lower dose of 1375 ppm. These results could indicate that the kinetics of the color
removal process is only depending on the dye concentration. The increase of signals at UV region might also indicate
that stable aromatic compounds stays after the cleavage of the quinoid chromophore.

4.5
4
3.5
Absorbance [ ]

3
Sample without treatment
2.5
1375 ppm - 15 minutes
2
2443 ppm - 15 minutes
1.5
5700 ppm - 15 minutes
1
1375 ppm - 60 minutes
0.5
0
195 295 395 495 595 695 795 895
Wavelenght [nm]

Figure 10 - Color removal tests for 200 ppm Reactive blue 19 solution treated with several Ca(OCl)2 doses.

UPB - INVESTIGACIÓN & DESARROLLO, No. 17, Vol. 1: 43 – 53 (2017) 49

 PÉREZ, IBÁÑEZ-CALERO AND ESCALERA

Encouraged by these results, we decided to treat solutions of the other synthetic dyes by increasing doses of Ca(OCl) 2.
The treatment of 40 mL of 200 ppm Allura red dye solution during 15 minutes resulted in a 50 % color removal with a
dose of 1275 ppm and 65 % for a dose of 2443 ppm or 5165 ppm. After one hour treatment, the lower dose 1275 ppm
resulted in >95 % color removal. The spectra in Figure 11 shows that once the azo chromophore is cleaved stable
aromatic residuals might stay in solution.

4.5
4
3.5
Absorbance [ ]

3
Sample without treatment
2.5
1275 ppm - 15 minutes
2
2443 ppm - 15 minutes
1.5
5165 ppm - 15 minutes
1
1275 ppm - 60 minutes
0.5
0
195 295 395 495 595 695 795 895
Wavelength [nm]

Figure 11 - Color removal tests for 200 ppm Allura Red solution treated with several Ca(OCl)2 doses.

Similar results were obtained when a 200 ppm Reactive black 5 dye solution was treated with increasing doses of
Ca(OCl)2. The treatment of 40 mL of this solution by 1330 ppm, 2480 ppm or 5050 ppm resulted in 58 % color removal
using any mentioned dose after 15 minutes treatment. After one hour treatment, the lower dose resulted once again in a
color removal >95 %. It seems that the kinetic of the decomposition process is also independent of the concentration of
Ca(OCl)2 as for the case of Reactive blue 19 dye. The absorption spectra after treatment (Figure 12) also indicate that
aromatic compounds might stay in solution after the cleavage of the azo chromophores.

4.5
4
3.5 Sample without
treatment
Absorbance [ ]

3
1330 ppm - 15 min
2.5
2 2480 ppm - 15 min
1.5
1 5050 ppm - 15 min

0.5 1330 ppm - 60 min

0
195 295 395 495 595 695 795 895
Wavelenght [nm]

Figure 12 - Color removal tests for 200 ppm Reactive Black 5 solution treated with several Ca(OCl)2 doses.

50 UPB - INVESTIGACIÓN & DESARROLLO, No. 17, Vol. 1: 43 – 53 (2017)

 DEGRADATION OF SYNTHETIC ORGANIC DYES IN SOLUTION…

3.4 COD removal tests

We tested first the COD removal efficiency by Ca(OCl)2 treatment for a 200 ppm Allura Red solution. The volume
treated was 100 mL with a dose of 1000 ppm and 15 minutes reaction time. The decolorization degree was >90% as it is
showed in figure 13. The COD charges for the non-treated and the treated samples were 2602 mg O2/L and 76 mg O2/L
respectively, this represents a 97 % COD removal.

4.5
4
3.5
Absorbance [ ]

3
2.5
2 Sample without treatment
1.5 Treated sample
1
0.5
0
190 290 390 490 590 690 790 890
Wavelength [nm]

Figure 13 - Color removal tests for 200 ppm Allura Red solution with 1000 ppm Ca(OCl) 2 dose.

We decided also to test the treatment COD removal efficiency for the anthraquinone dye Reactive Blue 19.
Anthraquinone dyes are more resistant to biodegradation than azo dyes[22]; for this reason, we decided to compare the
treatments with Ca(OCl)2 and ferrate – hypochlorite solution. 100 mL of 200 ppm Reactive blue 19 dye solution were
treated with 1000 ppm dose of Ca(OCl) 2 during 15 minutes (Sample 1) and 100 mL of 200 ppm Reactive blue 19 dye
solution were treated with 10 mL ferrate – hypochlorite solution (A=0.758, c=0.66 mM) during 1 hour (Sample 2). As it
can be seen in Figure 14, the decolorization efficiency for the treatment of sample 1 was around 80 % and for the
treatment of sample 2 was around 50 %.
4.5
4
3.5
Absorbance [ ]

3
2.5 Sample 1 without treatment
2 Sample 2 without treatment
1.5 Treated sample 1
1 Treated sample 2
0.5
0
190 290 390 490 590 690 790 890
Wavelength [nm]

Figure 14 - Color removal tests for 200 ppm Reactive Blue 19. Sample 1: ferrate – hypochlorite treatment.
Sample 2: Ca(OCl)2 treatment.

UPB - INVESTIGACIÓN & DESARROLLO, No. 17, Vol. 1: 43 – 53 (2017) 51

 PÉREZ, IBÁÑEZ-CALERO AND ESCALERA

It might seem that the treatment with only Ca(OCl)2 is more efficient than the treatment with ferrate – hypochlorite
solution at the concentrations accessible in our experimental conditions. It is important to mention that the effective
concentrations of the treating ferrate – hypochlorite solution are 0.06 mM - <400 ppm, which are much lower than those
previously reported[14], [16]. Before treatment, the experimental analysis of sample 1 and sample 2 indicated different
COD values (100 and 375 mg O2/L respectively) and the COD value after treatment was 60 mg O 2/L for both samples.
The difference between the initial COD’s, despite the same initial dye concentrations (UV-vis spectra totally superpose
in figure 14), might be due to the partial anthraquinone dye oxidation by dichromate during COD analysis[23]. Another
plausible explanation is the samples were analyzed at different times by the CASA laboratory which could lead to a
partial oxidation of the dye by the atmospheric oxygen. Nevertheless, the reference and treated sample were always
analyzed at the same time; therefore the COD removal percentages are valid. The above described results are very
encouraging since the efficient decolorization of Reactive Blue 19 dye by the two treatment methods, implies the
cleavage of the quinoid chromophore; which represents the key step for the total decomposition of this kind of
molecules[15].

4. CONCLUSION

In summary, we have presented a preliminary study for the removal treatment of three common used dyes (Reactive
Blue 19, Allura red and Reactive black 5) by Ca(OCl)2 or ferrate – hypochlorite solution. Both treatments efficiently
removed the color of 200 ppm dye solution in short time reaction (15 min). The COD removal efficiency for azo dye
Allura Red by reaction with Ca(OCl)2 (1000 ppm) was 97 %, this is very promising for the treatment of effluents having
high charges of dyes from this chemical family. For anthraquinone dyes, variability was observed for the COD values
before treatment (despite same dye concentrations), making inconsistent the evaluation of the treatment COD removal
efficiencies for this kind of dyes. This COD value erraticism might be eliminated measuring the organic content
concentration with the Standard Method 5520 B, open reflux method, as used in other reported studies[24]. To our
knowledge, this work is the first one studying the decomposition of the three above mentioned industrial synthetic dyes
by treating them with Ca(OCl)2 and ferrate – hypochlorite solution. We are preparing further detailed studies to
understand the chemical treatment mechanisms and to optimize COD analysis for anthraquinone dyes, building solid
scientific bases for a future technology transfer to local textile industries.

5. BIBLIOGRAPHY

[1] C. O’Neill, F. R. Hawkes, D. L. Hawkes, N. D. Lourenço, H. M. Pinheiro, and W. Delée, “Colour in textile
effluents – sources, measurement, discharge consents and simulation: a review,” J. Chem. Technol. Biotechnol.,
vol. 74, no. 11, pp. 1009–1018, 1999.
[2] S. Arslan, M. Eyvaz, E. Gürbulak, and E. Yüksel, “A Review of State-of-the-Art Technologies in Dye-Containing
Wastewater Treatment – The Textile Industry Case,” in Textile Wastewater Treatment, E. P. A. Kumbasar and A.
E. Körlü, Eds. Rijeka: InTech, 2016.
[3] S. Barışçı, O. Turkay, and A. Dimoglo, “Review on Greywater Treatment and Dye Removal from Aqueous
Solution by Ferrate (VI),” in Ferrites and Ferrates: Chemistry and Applications in Sustainable Energy and
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