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Impact of Electrolytic Clarification on Turbidity of Cane Juice

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JCBPS; Section A; May 2015 – July 2015, Vol. 5, No. 3; 2762-2772. E- ISSN: 2249 –1929

Journal of Chemical, Biological and Physical Sciences

An International Peer Review E-3 Journal of Sciences
Available online atwww.jcbsc.org
Section A: Chemical Sciences

CODEN (USA): JCBPAT Research Article

Impact of Electrolytic Clarification on Turbidity of

Cane Juice
Rajneesh Dwivedi1*and Zulfiqarali2

*1Department of Chemistry, Shri V.N. Karvariyamaha vidyalaya, majhgaon, Banda,( U.P.) Inia
2
Department of Chemistry, Integral University, Kursi Road, Lucknow-222660.(U.P.)India

Received: 20 June 2015; Revised: 6 July 2015; Accepted: 16 July 2015

Abstract: The clarification of raw cane juice to produce high quality sugar has been
brought by an electrical process without the use of hazardous chemicals or of heat. The
electrical process is performed with graphite electrodes modified with a protective layer
of polypyrrole (ppy). Various physico-chemical parameters such as color, pH, purity,
turbidity, pol, brix, reducing sugars of crushed cane (green and burned) juice, mixed juice
and clarified juice were studied. The results showed that pol, brix, reducing sugars and
turbidity are higher in crushed cane juice. Clarified cane juice had low, turbidity,
reducing sugars, pol, and brix ,but had significantly lower pH, purity and color when
compared to crushed cane juice.This simple procedure, of electrolytic clarification of
cane juice by using novel electrode, provide an energy efficient and environmentally
friendly protocol that could be industrially utilized to replace the conventional
clarification process in sugar productions.
Keywords: Electrical process, Graphite electrode, Polypyrrole (ppy), Sugarcane, Cane
juice, clarification.

INTRODUCTION

On the basis of color, the sugar crystals have the value and acceptability in the world market. Besides this,
cane juice contains a large no of natural coloring compounds and other constituents such as polyphenols,
chlorophyll and anthocyanin, amino acids etc.1. These coloring matters could not be eliminated by the

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Impact… Dwivedi & Zulfiqarali

clarification of cane juice and generate color during post clarification process up to the raw cane sugar 2.
These coloring matters are extracted along with the cane juice during milling of the process3. The
coloring matters constitute a portion of non-sugars matters that should be eliminated at the subsequent
processing of sugar4. Other coloring matters are also formed during juice processing operation as a result
of chemical reactions, such as caramalisation and the reactions between certain non-sugar materials5. The
type of cane, soil, growing environment, geographical area, milling operation and refining process
employed are also responsible for such reactions during processing6.
Mathur7 concluded that polyphenols formed brown-iron complexes whereas others generate color by
polymerization due to the effect of high temperature used in processing operations. The colored non-sugar
materials present in cane juice can be removed by various chemical or physical processes.
The one important physical process, to clarify the cane juice, is “Electrolytic clarification”. The use of
electricity for the clarification of cane juice has fascinated the attention of many researchers and scientists
as well as chemists of sugar industry in the past8. Lima got a patent for electrolytic clarification of cane
juice9. Weisseger Electrolyzed cane juice between aluminum electrodes10. The process of electrolysis
clarification involved passing the electric current through the system using aluminum electrode with the
salts and acid content of the juice. Later on, Ghosh employed Iron electrode for clarification of cane juice,
which was comparatively cheaper from the economical point of view and suggest the mechanism of the
process11, 12.
Doss has made certain modifications in the process of clarification and found that electrolysis of juice in
acidic condition is more advantageous and beneficial than at higher pH13. Further Tiwari and Srivastava
employed graphite electrodes for the clarification of cane juice to avoid the dissolution of electrodes and
inclusion of ionic impurities in the clarified juice14. The results obtained through graphite electrodes were
quite up to mark except some limitation at a higher potential.
To protect the electrode and to make the clarification efficiency, better it was decided to make coats of
any conducting material which must not affect the clarification efficiency, however if possible should
increase the clarification efficiency. For this reason the coating of conducting polymer was tried on the
electrode, which finally served the purpose efficiently.
Out of many conducting polymers viz. polyaniline, polythiophene, polyacetylene and polypyrrole (all are
conducting polymer) the most effective material to serve the purpose was polypyrrole. Regarding the
preparation and the functioning of the electrode other conducting polymers, i.e. polyethylene,
polythiophene, polyacetylene were also tried and have their own limitations, i.e. the starting material for
the preparation of polypyrrole by electrolysis was pyrrole (monomer).Pyrrole differ from other similar
monomers i.e. thiophene, aniline, acetylene etc. as it dissolved readily in water whereas others are either
insoluble or sparingly soluble in water. At the same time polypyrrole was comparatively more electron
rich with a consequence that at comparatively lower potential oxidation of water does not interfere with
the process, whereas in other cases viz. thiophene, aniline etc.15, this was a big problem. As such, at low
potential the chance of oxidation of water was eliminated in case of polypyrrole.

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Impact… Dwivedi & Zulfiqarali

MATERIALS AND METHODS

a) Preparation of novel electrode for clarification: The conducting polypyrrole coated graphite
electrode was prepared in a special type of self-designed electrolytic cell (Fig.1) which was fabricated
at Indian Institute of Technology (IIT), Kanpur.
b) Electrochemical polymerization of pyrrole on graphite electrode: The electrochemical
polymerization of pyrrole on graphite electrode produced a strongly adhered, durable film with
enhanced and good electrode properties (Diaz and Kanazawa 1979). Our interest to prepare of
durable, conducting organic graphite electrode surface led us to this approach.Chemicals used for the
deposition of polypyrrole on graphite electrode were pyrrole (Merk), sodium par toluene sulphonate,
calcium hydride obtained from Merk India Ltd. Electrolytic cell with graphite rod, conducting glass
electrode, saturated calomel electrode (SCE) is shown in Fig.1. A regulated constant D.C power
supply source, Elnova was used for a constant potential in the circuit during the electrolysis.

Fig.1: Polypyrrole coated graphite electrode.

A mixture of distilled pyrrole and sodium par toluene sulfonate solution was used as an electrolytic
solution for the deposition of polypyrrole on the graphite electrode. The graphite electrode was
attached to the positive terminal whereas both saturated calomel electrode and conducting glass
electrode were attached to the negative terminal of the source. A constant potential of +1.0 V was
applied to the graphite electrode with respect to saturated calomel electrode and Electrolyzed for

2764 J. Chem. Bio. Phy. Sci. Sec. A, May 2015 – July 2015; Vol.5, No.3; 2762-2772.
Impact… Dwivedi & Zulfiqarali

about one hour. A thick black film of polypyrrole was formed on graphite electrode. This result was
further confirmed by spectral technique.
c) Electrolysis of cane juice by polypyrrole coated graphite electrode: Green and burned samples of
sugarcane (variety CO 767) were collected from the fields of National Sugar Institute (Govt. of
India), Kanpur. The sugarcane was crushed in electrically driven crusher in the laboratory and the
juice samples; crushed (untreated), mixed (water imbibition), and clarified (by electrolysis) juice were
stored at 40C for subsequent analysis. The electrolysis of about two liter raw juice was carried out in a
circular electrolytic cell (diameter=11cm, height=14cm) using polypyrrole coated graphite electrode.
The Fig. 2 shows the circuit diagram for the electrolytic clarification of cane juice.

Multimeter
+
Electrons
A
Electrons
V Regulated D.C. Power Supply
D.C. Voltmeter

Polypyrrole +
Coated
Graphite
Electrodes

Cane Juice

Fig.2: Circuit diagram for electrolysis of cane juice.

The polypyrrole coated graphite electrodes were fitted tightly in high density polythene (HDPE) lid in
order to maintain a constant separation. A rectifier that is regulated D.C power supply (ELNOVA)
was used as a source of potential for electrolysis. A volt meter (range 0 - 30 volt) was connected
across the electrodes to monitor the potential difference of the electrodes during the electrolysis.
d) Determination of pH: The pH of the juice solution was measured using a pH meter (Century CP
901).
e) Determination of the sucrose content (pol): Refractometer was used to determine the sucrose
content (pol) with the help of double polarization method16.
f) Determination of Brix (dissolved solid): Brix of cane juice was determined as the corrected
reading of the refractometer following ICUMSA method17.
g) Reducing sugar determination: Reducing sugars in cane juice was determination using Fehling
solution as an oxidizing agent18. Reducing sugars percentage was calculated by using Johnsons table.

2765 J. Chem. Bio. Phy. Sci. Sec. A, May 2015 – July 2015; Vol.5, No.3; 2762-2772.
 Impact… Dwivedi & Zulfiqarali

h) Color value determination: ICUMSA color was determined by GS2/3-10 Method (ICUMSA
Method 2005). 50 gm. of cane juice was diluted to according to the need of the experiment and
filtered using a membrane filter (pore size 0.45 mm). The pH of the filtrate was adjusted to pH 7.0.
The absorbance was determined at 420 nm in 50 mm cell length with double beam UV-VIS
Spectrophotometer. The calculations are shown below.

As T
as = = − log s
bc bc
Where Ts = transmittancy

As = Absorbance
b = cell length
c = concentration of total solids (gm/cm3).
It was calculated with the help of refractometer Brix and specific gravity table for pure sucrose
solutions. In ICUMSA, Absorbance is multiplied by 1000.
i) Determination of turbidity: The hot clarified juice sample was cooled under running tap water to
room temperature (300C) then the Nester Tube filled by the sample that to be determined and read,
the reading is in NTU units.

RESULT AND DISCUSSION

1. Impact of milling on physico-chemical properties of green and burned cane:

Various physico-chemical parameters such as brix, pol, reducing sugar (RS), purity and pH were found to
be nearly similar for green cane and burned cane and did not differ significantly (Table 1). Because of the
presence of chlorophyll in the green cane, the color value (52700 IU) of the juice was significantly high
compared to burned cane juice (2800 IU).The variety of sugarcane and amount of chlorophyll were
reported to be reasons that governed the color value of the cane juice3.

Table 1: physico-chemical properties of green and burned cane juice .

Sample treatment Pol% Brix% Purity Color (ICUMSA) Reducing sugar pH

Green cane juice 17.21 19.46 86.28 52700 0.80 5.42
Burned cane juice 17.20 20.01 85.60 2800 1.16 5.41

2. The effect of processing on physico-chemical properties of burned cane juice:

Various physico-chemical parameters of crushed, mixed and clarified cane juice are represented in table
2. Pol and brix for crushed cane juice were found to be significantly higher than those of mixed juice and
clarified juice are comparable. The above quality parameters of both mixed and clarified juice are

2766 J. Chem. Bio. Phy. Sci. Sec. A, May 2015 – July 2015; Vol.5, No.3; 2762-2772.
Impact… Dwivedi & Zulfiqarali

comparable and not different significant. The higher brix (17.18) reading in the crushed juice may be due
to the presence of high amount of colloidal matters19.

Table 2: The effect of processing on physico-chemical properties of burned cane juice:

Sample Pol% Brix% Purity Color Reducing pH Turbidity

treatment (ICUMSA) sugar (NTU)
Crushed 14.70 17.18 83.26 52700 1.02 5.36 13.00
juice
Mixed cane 11.14 20.01 93.16 3400 0.76 5.28 11.08
juice
Clarified 11.80 12.60 93.86 12008 0.82 6.20 8.41
cane juice

Among the three juice samples, the clarified juice attained highest color value (12008 IU). The high color
value of clarified juice may be due to the changes occurred in sugar and non-sugars matters due to factors
such as pH, heat, iron from equipment’s and the added chemicals such as lime20.
The application of heat or addition of chemicals during the clarification process brings about flocculation
or coagulation of the colloidal matters and reduced clarified brix reading21.
pH of the clarified cane juice (6.20) was significantly higher compared with those of the mixed (5.28) and
the crushed juice (5.36) samples. The reason for this may be due to the addition of lime lead to
neutralization of organic acids originally present in cane juice and hence resulted in high pH readings in
the clarified juice versus the mixed juice.
3. Effect of electrolysis on physico-chemical properties of the cane juice by using novel electrode:
Physico -chemical properties of the burned sugarcane juice affected by electrolysis using novel electrode
are represented in Fig. 3 to 7. The electrolysis was performed up to one hour at an interval of 10 minutes
at the constant temperature of 300C. The potential applied was 5, 10 and 15 volts during the course of
electrolysis of cane juice.
From the graphical presentation (Fig.3) it is obvious that the pol content decreased as a function of time
and applied potential. From the results of pol it was found that at lower potential of 5 volts, it decreased
from its initial value of 15% to 12% in 60 minutes of electrolysis. However, at higher potentials of 10
and 15 volts the pol content decreased to a greater rate and finally attained the values of 11.60 and
11.10% respectively, at the end of the experiment. Above 15 volts no significant decrease in pol content
was observed. The apparent loss of pol was found to be due to the removal of the invert sugar by the
oxidation on the novel electrode.

2767 J. Chem. Bio. Phy. Sci. Sec. A, May 2015 – July 2015; Vol.5, No.3; 2762-2772.
Impact… Dwivedi & Zulfiqarali

16

15

14
Pol Content (%)

13 5 volt
10 volt
12 15 volt

11

10
0 10 20 30 40 50 60
Time (min.)

Fig. 3: Variation of pol content with time and potential.

Further to this, during the course of electrolysis the brixcontent decreased with increase in time of
electrolysis and applied potential. At 5 volt, the results obtained are shown in Fig.4. The initial
brixcontent was 17.18 0brix which decreased during the course of electrolysis and finally attained a value
of 15.50 0brix. Whereas when the potential was increased to 10 and 15 volts at same temperature, the brix
was found to be 14.51 and 12.79 0brix respectively at the end of experiment. When experiment was
performed above 15 volt no significant change in brix data was observed. This greater decrease in brix
content with rise in applied potential may be due to the charge neutralization of the naturally occurring
inorganic ions such as Na+, K+, Ca+ etc. and also precipitation of colloidal impurities present in cane juice.

18.00
17.00
16.00
15.00
Brix content (%)

5volt
14.00
13.00 10volt
12.00 15volt
11.00
10.00
0 10 20 30 40 50 60
Time (min.)

Fig. 4: Variation of brix content with time and potential.

2768 J. Chem. Bio. Phy. Sci. Sec. A, May 2015 – July 2015; Vol.5, No.3; 2762-2772.
Impact… Dwivedi & Zulfiqarali

When the experiment was performed at the potential of 5 volt and temperature was maintained at 300C,
the purity rise of cane juice is shown in Fig.5. The initial purity of cane juice was 80.39 units. Up to first
30 minutes there was little change in purity and there after it started increasing up to maximum and
attained a constant value of 83.64 units after 60 minutes. There was an increase of about 3.0% in the
purity of cane juice. Whereas when the potential was increased from 5 to 10 and 15 volts the increase in
purity was 7.45% and 13.67% at constant temperature of 300C (Fig.5). Further increase in potential as
such did not make any significant change in the increase of purity.
The purity rise with potentials was due to the removal of organic and inorganic impurities viz. Colloidal
matters, coloring matter and amino acids. The neutralization of charges of colloidal matters allowed to
coalesce together, the smaller colloidal particles forms a bigger flock, resulting there by either settling or
coming on the surface of the cane juice in the form of froth, which in turn removed the protective colloids
by the process of surface adsorption. The high purity rise at higher potential, i.e. at 15 volts compared to
5 and 10 volts may be due to the greater extent of neutralization of charges at higher potentials. More
generation of hydrogen ions (H+) during electrolysis made the juice acidic.
In the clarification process the progressive increase in the reducing sugar content was observed with the
applied potential. At 5 volts the reducing sugar increased and attained a value of 0.55% at the end of
electrolysis.

92.00

90.00

88.00

86.00
Purity ( %)

5 volt
84.00 10 volt

82.00 15 volt

80.00

78.00
0 10 20 30 40 50 60
Time (min)

Fig. 5: Variation of purity with time and potential.

However, at the higher potentials of 10 and 15 volts, the reducing sugar content increased to a greater
extent and finally attained the values of 0.70% and 0.83% respectively at the end of the experiment
(Fig.6). The increase in the quantity of reducing sugars with an applied potential was due the inversion of

2769 J. Chem. Bio. Phy. Sci. Sec. A, May 2015 – July 2015; Vol.5, No.3; 2762-2772.
Impact… Dwivedi & Zulfiqarali

sucrose at low pH and higher potentials that is at 10 and 15 volts in comparison to the lower potential of 5
volts. Above 15 volts no significant change in reducing sugar was observed.
0.90
0.80
0.70
Reducing sugar content (%)

0.60
0.50 5volt
0.40 10volt
0.30 15volt
0.20
0.10
0.00
0 10 20 30 40 50 60
Time (min.)

Fig. 6: Variation of reducing sugar content with time and potential.

Another important physico-chemical parameter, i.e. turbidity was measured during clarification of cane
juice. The graphical representation (Fig.7) shows that the turbidity of cane juice decreased with the
function of applied potential and time. At the lower voltage of 5 volts, the percent loss of turbidity was
found to be 16.5% in 60 minutes of electrolysis. When the potential was enhanced from 5 to 10 and 15
volts the rate of decrease in turbidity was more marked and finally attained the value of 10.01 NTU ( loss
24%) and 9.21 NTU (loss 31.1%) respectively at the end of the experiment (Fig.7). However Further
increase in potential as such did not make any significant change in turbidity in cane juice.

14.00
13.00
12.00
Turbidity (NTU)

11.00
5volt
10.00
10volt
9.00
15volt
8.00
7.00
6.00
0 10 20 30 40 50 60
Time (min.)

Fig. 7: Variation of turbidity with time and potential.

2770 J. Chem. Bio. Phy. Sci. Sec. A, May 2015 – July 2015; Vol.5, No.3; 2762-2772.
Impact… Dwivedi & Zulfiqarali

The decrease in turbidity may be due to the removal of organic and inorganic impurities, coloring matters,
colloidal matters caused by the neutralization of the charges during electrolysis.

CONCLUSION

The present study demonstrated that the electrolytic clarification technique of the cane juice by using self-
developed novel electrode gives precise and accurate results. This technique leads itself to complete
removal of colloids, organic and inorganic particles which are primarily responsible for the turbidity of
cane juice. The low turbidity of examining model (clarified cane juice) is required to give better color of
sugar crystals during sugar manufacture. The use of novel electrodes for electrolytic clarification also has
several advantages such as save on the power, easy maintenance of electrode materials, etc., but the most
significant advantage is that, it does not corrode due to which there is no additional contamination in the
cane juice, which was the main limitation of earlier attempts made by different workers.

ACKNOWLEDGEMENT

Authors are thankful to Director, National Sugar Institute, Kanpur, for providing research facilities.

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Corresponding author: Dr. Rajneesh Dwivedi*

*Department of Chemistry, Shri V.N. Karvariya Mahavidyalaya, Majhgaon, Banda, U.P.

2772 J. Chem. Bio. Phy. Sci. Sec. A, May 2015 – July 2015; Vol.5, No.3; 2762-2772.

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