International Journal of Agricultural
Science and Research (IJASR)
ISSN (P): 2250-0057; ISSN (E): 2321-0087
Vol. 6, Issue 5, Oct 2016, 21-28
© TJPRC Pvt. Ltd
PHYSICO-CHEMICAL PROPERTIES OF MARKING NUT SHELL
LIQUID (SEMECARPUS ANACARDIUM)
PRITI P LAD, BHAGYASHREE N PATIL, SUCHITA V GUPTA & ASHWINI GAWANDE
Department of Agriculture Process Engineering, DR. PDKV, Akola, Maharashtra, India
ABSTRACT
The physical properties of Marking Nut Shell Liquid (CNSL) were studied using standard procedures.
The physicochemical properties of crude oil and filter oil of marking nut shell liquid after extraction of liquid were
analysed. The physical properties of the MNSL studied were moisture content, Specific gravity and Viscosity, pH,
Refractive index. The chemical properties of the MNSL studied were Acid value, Saponication value, free fatty acid,
Iodine value. The specific gravity, pH, refractive index and viscosity of the MNSL of crude oil and filter oil were (0.951),
(3.227), (1.5006) and (1040 cP) and (0.948), (3.743), (1.5006) and (860 cp) respectively. The acid value, saponification
value, iodine value and free fatty acid were (22.037 mgKOH/g), (119.407 mgKOH/g), (56.89 mgiodine/100g) and (11.018
mgKOH/g) (for crude oil) and (14.821 mgKOH/g), (137.682 mgKOH/g), (69.987 mg iodine/100g) and (7.41 mgKOH/g)
(for filter oil). This is an indication that the oil is non-drying and may not be used for soap making. The investigation
Original Article
showed that MNSL is non-drying oil and it is useful in industries for paints, varnishes and surface coatings.
KEYWORDS: MNSL, Physic-Chemical Properties, Extraction
Received: Jul 17, 2016; Accepted: Aug 18, 2016; Published: Aug 20, 2016; Paper Id.: IJASROCT20163
INTRODUCTION
The Scientific name of marking nut is Semecarpus anacardium L belonging to the family Anacardiaceae.
It is known as bhallatak or Bhilwa in India and also called "marking nut" by Europeans, because it was used by
washermen to mark cloth and clothing before washing, as it imparted a water insoluble mark to the cloth.
The nut is about 2.5 cm long, ovoid and smooth lustrous black. The pericarp abounds in a black, oily bitter and
highly vesicant juice known as Bhilawan shell Liquid (BSL). It is a rich source of phenols, biflavonoids, phenolic
compounds, bhilawanols, minerals, vitamins and amino acids, which show various medicinal properties.
Traditionally, marking nut used for marking lines, manufacture of varnishes lacquers, enamels and paints.
It is also used for water proofing textile fabrics, imparting lather finish to cloth, paper boards and card boards, in
production of insecticides, antiseptics. (Majumdar et al 2008). Phyto-chemical examination revealed 3.85% of total
ash, 0.33% of acid insoluble ash, 11.27%alcohol soluble extractive, 11.84% water soluble extractive and 12.71%
moisture content in S. anacardium nuts also the presence of iron, copper, sodium, calcium and aluminium in traces
( Gouthaman, et al 2008).
MATERIALS AND METHODS
The research work was carried out at the Department of Agricultural Process Engineering, College of
Agricultural Engineering & Technology, and Akola. The marking nut shell was the main material, which was used
for the study. The physical properties of the MNSL extracted were determined using standard procedures.
www.tjprc.org
[email protected]
22
Priti P Lad, Bhagyashree N Patil, Suchita V Gupta & Ashwini Gawande
The samples of MNSL from the shells extracted by heating the cashew nut shells at 90, 110,130 and150 0C for 2, 4, 6 and 8
hours. The physical properties of the Crude MNSL extracted by traditional method and the MNSL extracted by heating
were compared. The experiments to analyze the quality of oil for the parameters namely, moisture content, Specific
Gravity and Viscosity, refractive index, pH, oil extraction, acid value, iodine value, free fatty acid, saponification value
were carried out.
Determination of Crude Oil in Marking Nut Shell by Soxhlet Method
The crude oil was determined using Soxhlet apparatus by adopting the method suggested by Thimmaiah, (1999).
•
Weight 2-3 g of dried marking nut shell sample in a thimble (prepared from what man No.1 filter paper) and place
it in a Soxhlet apparatus.
•
Connect a dry pre-weighted solvent flask (‘a’, g) beneath the apparatus and the required volume of solvent
(Petroleum ether, b. p. 60-80 0C or ethyl ether or hexane) and connect to condenser.
•
Adjust the heating rate to give a condensation rate of 2-3 drops and extract for 16 h.
•
Remove the thimble and retain ether from the apparatus.
•
Evaporate the excess ether from the solvent flask on a hot water bath and dry the flask at 105 0C for 30 min.
•
Cool the flask in desiccators and weigh (‘b’, g)
Crude oil ontent % =
× 100
(1)
Determination of Moisture Content of MNSO
AOAC method was used for determining the moisture content of marking-nut shells. Initially weight of sample
was recorded, kept this sample in hot air oven at 105±2 0C for 24 h. (AOAC, 2000)
After drying, the sample was kept in desicator for 1 h. then the final weight of sample was recorded. The mean of
three replications were reported throughout the experimentation. The moisture content of sample was calculated on dry
basis by using following formula.
M. C. d. b. % =
%& %'
%'
( 100
(2)
Where,
•
M.C. = Moisture content, % (d. b.)
•
W1 = Initial weight of sample, g.
•
W2 = Final weight of sample, g.
Determination of Specific Gravity
An empty density bottle (pycnometer) and lid was weighed, W1 and the weight recorded. Distilled water was filled
into the density bottle and it was reweighed, W2 after which the same procedure was repeated but this time using the BSL
and weight recorded, W3. The experiment was done at ambient temperature (Mwangi, 2013).
Impact Factor (JCC): 4.8136
NAAS Rating: 3.53
Physico-Chemical Properties of Marking Nut Shell Liquid (Semecarpus Anacardium)
Speci,ic gavity =
1
&
'
&
23
(3)
Where
•
W1= Weight of empty density bottle, g
•
W2= Weight of density bottle with distilled water, g
•
W3= Weight of density bottle with bhilwa shell liquid, g
Determination of pH Value
The pH of marking nut shell oil was measured by using digital pH analyser
Determination of Refractive Index Determination
Refractive index was determined by using hand refractometer, which gave the reading directly in 0Brix. Averge of
3 replications were recorded as TSS of marking nut shell oil and 0Brix was converted into refractive index.
A few drop of the oil were poured on the glass window of the hand refractometer and the refractive index was
noted. This value was measured 3 times for each sample and the window was wiped thoroughly after each test.
The final refractive index was average of three replication.
Determination of Viscosity
The viscosity of marking nut shell oil was determined by Brookfield engineering Labs. Inc. Middlebord
Viscometer having model RVT (Umaru and Aberuagba, 2012).
Method
•
Mount the guard leg, if used, on the viscometer.
•
Attach the spindle to the viscometer lower shaft by lifting the coupling screw slightly. Hold it firmly with one
hand while screwing the spindle on with the other. Avoid putting side thrust on the shaft.
•
Lower and center spindle in the test material (600 ml beaker) until the meniscus of the fluid is at the center of the
immersion groove on the spindle’s shaft.
•
To make viscosity measurement, turn the motor switch “ON”. The energizes the viscometer drive motor.
Allow time for the indicated reading to stabilize. The time required for stabilization will depend on the speed at
which the viscometer is running and the characteristics of the sample fluid.
•
After indicating the reading turn the viscometer motor switch “OFF”. The viscosity is measured by following
formula:
Dial reading × Factor = viscosity in cP mPa. s
(4)
Determination of Acid value
The acid value of marking nut shell oil was determined by using following method (Thimmaiah, 1999).
www.tjprc.org
[email protected]
24
Priti P Lad, Bhagyashree N Patil, Suchita V Gupta & Ashwini Gawande
Method
•
Dissolve 1-10 g of oil or melted fat in 50ml of the neutral solvent in a 250 ml conical flask.
•
Add a few drop of phenolphthalein.
•
Titrate the content against 0.1N potassium hydroxide.
•
Shake constantly until a pink colour which persists for fifteen seconds is obtained.
Acid value mgKOH/g =
< = > ×? <
@
ABC×DE.F
(5)
Determination of Free Fatty Acid
The FFA value of marking nut shell oil was determined by using following method (Umaru and Aberuagba,
2012).
The amount of free fatty acid (FFA) was calculated as being equivalent to half the value of acid value,
FFA mgKOH/g =
GH I = >
(6)
J
Determination of Saponifocation Value
The saponification value of marking nut shell oil was determined (Thimmaiah, 1999).
Method
•
Accurately weigh out 1-2 g of oil into a 250 ml conical flask, add 25 ml of alcoholic KOH and dissolve the oil
completely.
•
Connect air condenser to the flask and boil for about 30 min on a boiling water bath.
•
Cool to room temperature; add 2-3 drops of phenolphthalein indicator and mix.
•
Titrate against standard 0.5N HCl until the pink colour disappears.
•
Treat the blank similarly in the absence of oil.
saponi,ication value of an oil (mgKOH/g) =
(L MN O < )×JP.QE
( )
(7)
Determination of Iodine Value
The Iodine value of marking nut shell oil was determined (Thimmaiah, 1999).
Method
•
Weigh out 0.2-0.3g of oil into 500 ml conical flask.
•
Add 20 ml of chloroform and dissolve the oil completely. Add 25ml of Hanus iodine solution, mix well, stopper
the flask and keep in dark for 30 min.
•
Add 20ml KI solution and mix well.
•
Titrate against standard 0.1N Na2S2O3 solution using starch as an indicator with vigorous shaking to extract the
Impact Factor (JCC): 4.8136
NAAS Rating: 3.53
Physico-Chemical Properties of Marking Nut Shell Liquid (Semecarpus Anacardium)
25
iodine from the chloroform layer.
•
Conduct test in the absence of oil.
Iodine number ofoil =
G×?×Q.FJES×FQQ
gI2/100g oil
(8)
Where
A = ml of Na2S2O3 (Blank-Test)
N = Normality Na2S2O3 solution.
RESULTS AND DISCUSSIONS
Physico-Chemical Properties of Marking Nut Shell Oil
After optimization, the marking nut shell oil extracted in oil expeller at optimum process variables
(hating temperature 115 0C, moisture content 6.5% (d. b.) and heating time 8h were used for analysis of physic-chemical
properties. The important properties of the marking nut shell oil i.e. viscosity, specific gravity, pH, refractive index, acid
value, free fatty acid, saponification value and iodine value were determined and are shown in Table.
Table 1: Physicochemical Properties of Marking Nut Oil
Sr. No.
1
2
3
4
5
6
7
8
Parameter
Specific gravity
pH
Refractive index
Viscosity (cp)
Acid value (mg KOH/g)
Free fatty acid (mg KOH/g)
Saponification value (mg
KOH/g)
Iodine value (g I2/100g)
Filter
Oil
0.948
3.743
1.5006
860
14.821
7.410
Crude
Oil
0.951
3.227
1.5006
1040
22.037
11.018
137.682
119.401
69.987
56.890
The specific gravity of filter oil and crude oil was in the range of 0.939 to 0.959 and 0.945 to 0.963 respectively.
From table, the average specific gravity of filter and crude oil was found to be 0.949 and 0.952 respectively. Similar results
were observed for cashew nut shell liquid (chaudhari et al 2012), jatropha seed oil (Joshi et al 2011), date seed oil
(Boukouada and Yousfi 2009).
The pH of marking nut shell oil for filter and crude oil was found in the range of 3.25 to 4.33 and 2.99 to 3.66
respectively. The average of pH of marking nut shell oil for filter oil and crude oil was found to be 3.74 and 3.22
respectively. Similar results were observed for cashew nut shell liquid by Patrick MM and Bildad KM, (2013).
Viscosity increased with molecular weight but decreased with increasing unsaturated level and temperature
(Akbar et al 2009). The viscosity of marking nut shell oil for filter and crude oil was recorded as 860 cP and 1040 at 25 0C
respectively. It is observed that the viscosity of filter oil is less than crude oil. Similar results were observed for cashew nut
shell liquid (chaudhari et al 2012) and jatropha seed oil (Joshi et al 2011).
The Refractive index and specific gravity were studied at room temperature at 25 0C. The Refractive index of
filter and crude oil was found to be 1.5006 and 1.5006 respectively. Both found same refractive index as 1.5006. Similar
www.tjprc.org
[email protected]
26
Priti P Lad, Bhagyashree N Patil, Suchita V Gupta & Ashwini Gawande
results were observed for jatropha seed oil (Joshi et al 2011) and date seed oil (Boukouada and Yousfi 2009).
Acid value is the number of milligrams of potassium hydroxide necessary to neutralize the free acids in 1 g of
sample. This value can be used for a purity check of oil and may be already started decomposition reactions. An acid value
is indication of the age and quality of the oil or fat.
Acid value of oil for marking nut shell for filtered was found in the range of 14.025 to 14.029mg KOH/g and for
crude oil was found in the range of 10.890 to 11.23mg KOH/g. Acid values of oil from marking nut shell for filtered and
crude oil was between 14.822 and 22.037 mg KOH/g respectively. The acid value which implies high fatty acid content in
the oil. Similar results were observed for jatropha seed oil by Joshi et al 2011.
Acid value measures the presence of corrosive free fatty acid and oxidation products. This was actually an
important variable in considering the quality of oil because the lower the free fatty acid, the better the quality of oil because
the lower the FFA, the better the quality of oil. The acceptable limit for edible oils I ≤ 10. FFA concentrations of the oils
were all higher than the maximum limit of 2.0% reported for high grade codex alimentarius. The free fatty acid (FFA) and
moisture content have significant effect on the transesterification of glyceride with alcohol using catalyst. The FFA for
marking nut shell oil for filter oil was found in the range of 7.013 to 8.014mg KOH/g and for crude oil was found in the
range of 10.891 to 11.225 mg KOH/g respectively. The average value of FFA of filter oil of marking nut and crude oil was
found 7.411mg KOH/g and 11.018mg KOH/g respectively. Similar results were observed for jatropha seed oil
(Joshi et al 2011; Umaru and Aberuagba 2012.
Iodine value is a measure of the unsaturation of fats and oils and is expressed in terms of the number of gram of
iodine absorbed per 100 gram sample. An iodine value of marking nut shell oil for filtered oil was found in the range of
66.911 to 73.833 g Iodine /100g. An iodine value of marking nut shell oil for crude oil was found in the range of 53.933 to
60.691 g Iodine /100g. Iodine values of marking nut shell oil for filtered and crude oil are 69.987 and 56.89 g Iodine /100g
respectively.
It indicates the degree of unsaturation in the fatty acid of triacyglycerol. This value could be used to quantify the
amount of double bond present in the oil which reflects the susceptibility of oil to oxidation. The iodine value obtained is
low suggesting the presence of saturated fatty acid and this places the oil in the non-drying groups as drying oil have an
iodine value above100. The iodine values of (56.89 - 69.987 g Iodine /100g) indicate that this oil is non-drying, highly
unsaturated oil. Similar results were observed for jatropha seed oil (Joshi et al 2011), date seed oil (Boukouada and Yousfi
2009) and cashew nut oil (Bello et al 2013; Akbar et al 2009).
Oils are classified into drying, semi drying and non- drying according to their iodine values. Since the iodine
value of marking nut shell oil is lower than 100 it could only be classified as non-drying oil (Boukouada and Yousfi et al
2009 for date seed oil)
Saponification value is expressed as number of milligrams of potassium hydroxide required to saponify 1 g of the
sample. The saponification value is an indication of the average molecular mass of fatty acids present in oil. Saponification
values of the marking nut shell for filtered oil was found in the range of 135.198 to 138.938 mg KOH/g. Saponification
values of the marking nut shell for crude oil was found in the range of 111.743 to 131.882 mg KOH/g respectively.
The average of saponification values of the marking nut shell for filtered and crude oil are 137.682 and 119.401 mg KOH/g
respectively.
Impact Factor (JCC): 4.8136
NAAS Rating: 3.53
Physico-Chemical Properties of Marking Nut Shell Liquid (Semecarpus Anacardium)
27
Because there is an inverse relationship between saponification value and weight of fatty acids in the oils, it can
be assumed that the oils hold fatty acids with 16–18 carbon atoms with a significant amount of saturated fatty acids in the
case of the date seeds oil. Similar results were observed for cashew nut oil (Bello et al 2013), jatropha seed oil
(Joshi et al 2011 and Akbar et al 2009).
CONCLUSIONS
•
The extraction of marking-nut shell oil in terms of shell and kernel was found to be 21.40 to 21.88% and 30.22 to
34.15%, respectively by soxhlet apparatus. The average value of oil content of marking nut shell oil is 21.69%.
The average value of marking nut kernel oil was found as 32.30%.
•
Moisture content of the MNS was 2.484 % and for MN deoiled shell and traditionally deoiled shell was found to
be zero percent.
•
Quality parameters which includes physical properties including pH, RI, Specific gravity and viscosity for filter
oil was found as 3.743, 1.5006, 0.948 & 860 cP and respectively and for crude was found as 3.227, 1.5006, 0.951
and 1040 cP respectively.
•
Quality parameters which includes chemical properties including FFA, acid value, iodine value and
saponification value for filter oil was found as 7.410 mg KOH/g, 14.821 mg KOH/g, 69.987 g I2/100g and
137.682 mg KOH/g respectively and for crude oil was found as 11.018 mg KOH/g, 22.037 mg KOH/g, 56.890 g
I2/100g and 119.401 mg KOH/g respectively.
REFRECNCES
1.
A.O.A.C, (2000) Official Method of Analysis, Association of Official Analytical Chemists, Wishington, D C. U.S.A. 2000.
2.
Akbar E, Yaakob Z, Kamarudin SK, Ismail M, and Salimon J, (2009) Characteristic and composition of jatropha curcas oil
seed from malaysi and its potential as biodiesel feedstock, European Journal of Scientific Research, 29(3):396-403.
3.
Bello
EI,
Akinola
AO,
OutF,
and
Owoyemi
TJ,
(2013)
Fuel
and physiochemical properties of
cashew
(Anarcardium Occidentale) nut oil, its biodiesel and blends with diesel. British Journal of Applied Science & Technology,
3(4): 1055-1069.
4.
Boukouada, M, and M. Yousfi, (2009) Phytochemical study of date seeds lipids of three fruits (phoenix dactylifera l) produced
in ouarglaregion. Annales de la Faculté des Sciences et Sciences deI’ngenieur, vol.1(3).
5.
Chaudhari AP, Thakor NJ, Mahale DM, Haldankar PM and. Sonawane SP, (2012) Physical properties of cashew nut shell
liquid.InternationalJournal of Application or Innovation in Engineering & Management (IJAIEM), vol-1.
6.
Gouthaman T, Kavitha MS, Ahmed BA, SenthilKumar Tand Rao MV, (2008) A Review on Semecarpus anacardium L.: An
Anticancer Medicinal Plant, Recent progress in medicinal plant (RPMP). Phytopharmacology & Therapeutic Values I, Vol.
19.
7.
Joshi A, Singhal P, and Bachheti RK, (2011) Physicochemical characterization of seed oil of jatropha curcas collected from
dehradun (Uttarakhand) India. International Journal of Applied Biology and Pharmaceutical Technology, volume: 2.
8.
Patrick MM and Bildad KM, (2013) Novel Unsaturated Polyester (UPE) Resin Based on Cashew Nut Shell Liquid (CNSL).
International Journal of Cur. Tr. Res (2013) 2 (1): 285-292
9.
Thimmaiah SK (1999) Standard methods of biochemical analysis. Kalyani publication. 49-60, 278-279.
www.tjprc.org
[email protected]
28
Priti P Lad, Bhagyashree N Patil, Suchita V Gupta & Ashwini Gawande
10. Umaru M and Aberuagba F (2012) Characteristics of a Typical Nigerian Jatropha curcas oil seeds for biodiesel production.
Research Journal of Chemical Sciences, 2(10): 7-12.
Impact Factor (JCC): 4.8136
NAAS Rating: 3.53