Professional Documents
Culture Documents
SYNOPSIS
Key words:
Palm stearin,
Soap,
Spent lye.
INTRODUCTION
Soap is considered the oldest hygienic substance and has been used since the
Egyptian era (Tsujii, 1998). Because of the advent in the detergent industry, the
soap is nowadays used mostly as toiletry soap bar. However, the third world
countries still use soap abundantly for the fabric cleansing. It is important to point
out that the soap is also a component in the detergent formulation as a foam control
agent (Fujimoto, 1985). A historical survey of the soap-making reveals that the
natures of the fat and the alkaline substance employed in the saponification played
basic roles in the final performance of the soaps. Yet, the cleansing properties of
soap are more tightly bound to the nature of the used fatty matter than to the type of
the alkaline substance. To meet the criteria of the soap detergency such as firm
texture and foaming, the soap-making industries commonly manufacture their
household soaps employing a mixture of 75-85% of hard fats such as the beef tallow
or the palm oil and 15-25% of lauric fats such as the coconut oil or the palm kernel
oil. The luxury toilet soaps require a relatively higher content of lauric fat, but a skin
irritation may be caused when exceeding a certain percentage of this matter (lauric
acid).
335
ANALYSES
E XPERIMENTAL
ESTIMATION OF
A CID V ALUE , AV
Acidity =
V xN
x
1000
336
M
w
x 100
[1]
Moulay et al.: P A L M S T E A R I N I N S O AP M A K I N G P R O C E S S
AV = 2 x Acidity
[2]
V x N x 56.1
w
AV =
[3]
SV =
(V 0 - V) x N x M
w
[4]
V 0 is the volume in ml of the H 2 SO 4 solution, for the blank test, 22 ml; V is the
volume in ml of the H 2 SO 4 solution, for the fat; N is the normality of the H 2 SO 4
solution, 0.5; M is the molecular weight of KOH, 56.1 g/mole; w is the sample
weight in grams, 2.0624g.
E XPERIMENTAL ESTIMATION OF I ODINE V ALUE , IV
Initially, the Wijs reagent was prepared by dissolving 12g of iodine
monobromide (IBr) in 1L of glacial acetic acid in an amber flask.
A 0.6g of fat was accurately weighed and charged into a 250ml flame-dried
amber flask. After addition of 10ml of chloroform, the system was cooled by
immersing it in an ice-bath in order to add 25ml of the Wijs reagent. The system was
allowed to stand for 3h at room temperature. A 25ml of a 100 g/L aqueous solution
of potassium iodide was then introduced and the mixture was stirred for 2h. Finally,
70ml of distilled water was added to the mixture. The titration of this mixture with 0.1
N solution of sodium thiosulfate, Na 2 S 2 O 3, in the presence of starch was performed
to estimate the excess of iodine. Equation 5 allowed the estimation of IV:
IV =
(V0 - V) x N x M
w
[5]
337
UM =
w x 100
w0
OF SOAP
338
Moulay et al.: P A L M S T E A R I N I N S O AP M A K I N G P R O C E S S
[7]
[8]
Parameters
Palm stearin
Coconut oil
Beef tallow
SV (mg/g)
200
259
185
M*
280.50
216.60
307.25
AV (mg/g)
0.24
8.30
6.72
EV (mg/g)
199.76
250.70
178.28
IV (mg/100g)
24
38
H 2 O (%)**
0.04
0.05
0.97
UM (%)
0.36
0.28
0.50
0.9087 (30 C)
0.919 (24 C)
0.892 (51 C)
1.447
1.448
1.471
T (C)
52
22
40
Aspect***
0.8R/3Y
2.5R/10Y
1.4R /10Y/0.6B
40
2. B OILING
A small amount of 35% NaOH solution was added to the soapy paste obtained
in the saponification step, and the system was vigorously agitated under nitrogen
atmosphere and heated at 65 C for an additional time of 4h.
3. W ASHING
Sequential washings of the boiling product with water allowed adjusting both
the percentages of NaOH and NaCl to their ranges.
339
4. F ITTING
A volume of water was carefully added to the soapy paste in sequential
portions to induce dissolution. A foaming was observed, and a small amount of ethyl
alcohol was added to suppress it. The system was allowed to stand for four days at
room temperature, the period within which the soap was formed at the top layer.
A NALYSES
[9]
[10]
[11]
340
Moulay et al.: P A L M S T E A R I N I N S O AP M A K I N G P R O C E S S
A NALYSES
FI
% TFM =
[12]
Where 100 is the percentage by weight of the soap and X is the percentage of
water. X was estimated as follows: An evaporating dish containing 10g of soap was
placed in the oven at the temperature of 105C until a constant weight. The
percentage of water present in the soap was calculated using Equation 13.
Water (%) =
W1 - W2
x 100
W1 - W0
[13]
W 0 is the weight of the evaporating dish; W 1 is the weight of the soap
sample/dish before drying; W 2 is the weight of the soap sample/dish after drying.
F REE CAUSTIC ALKALI
In a 250 ml round-bottomed flask equipped with a reflux condenser, 10g of
soap and 100 ml of neutralized ethanol (80% v:v) were charged. The system was
heated in a sand bath until a homogeneous phase was observed. The mixture was
cooled to room temperature and titrated with 0.1 N ethanolic solution of H 2 SO 4 in the
presence of phenolphthalein. The alkali was estimated as % of Na 2 O using Equation
14.
[14]
0.04 x V x N x 100 x 31
Na2O (%) =
w
40
40 and 0.040 are the molecular weight of NaOH in g and mg, respectively; V is
the volume of the solution of 0.1 N H 2 SO 4 in ml; w is the weight of sample in grams;
31 is the equivalent mass of Na 2 O.
F REE SODIUM CHLORIDE
An amount of 10 g of soap was dissolved in 50 ml of hot water. A few millilitres
of 20% H 2 SO 4 and few drops of the methyl orange solution were added to the soap
solution which was heated until the colour turned rose. After cooling to room
temperature, the solution was filtered off and transferred into a 250 ml flask; water
was then added to make 250 ml solution. An aliquot of 100 ml was withdrawn and
poured into a 250 ml Erlenmeyer flask, and the H 2 SO 4 excess was neutralized with
concentrated sodium hydroxide solution. The neutralized solution was titrated with
0.1 N silver nitrate solution in the presence of few drops of 10% potassium chromate
solution as indicator; at the endpoint, the colour changed to red brick. The
percentage of sodium chloride present in the soap was estimated by Equation 15.
NaCl (%) =
V x 5.85
w
341
[15]
[16]
Where x 1 , x 2 , and x 3 are the weight fractions of the palm stearin, the beef
tallow, and the coconut oil, respectively; T PS , T BT , and T CO are their respective titres.
I ODINE VALUE
The iodine values, IV, were computed form the additive Equation 17.
IVS = x1IVPS + x2IVBT + x3IVCO
[17]
IV PS , IV BT , and IV CO are the iodine values of the palm stearin, the beef tallow,
and the coconut oil, respectively.
P ARTITION COEFFICIENT , K G
K G was computed via Equation 18 using the data of Tables 2 and 3.
( [glycerol]
+ [water]) soap
( [glycerol]
+ [water])
KG =
[18]
lye
Where ([glycerol] + [water]) soap and ([glycerol] + [water]) lye are the sum of
glycerol and water contents (%) in soap and spent lye, respectively.
W IGNER S CONSTANT , K S
The constant K s was determined according to the empirical Wigners equation
(Equation 19).
[NaCl] soap
= 1 - KS
[NaCl] lye
TFM
[19]
100
Where [NaCl] soap and [NaCl] lye are the percentages of salt (as NaCl) in the
soap and the spent lye, respectively, and are drawn from Tables 2 and 3. TFM is the
total fatty matter (%) of the soap taken from Table 3.
342
Moulay et al.: P A L M S T E A R I N I N S O AP M A K I N G P R O C E S S
ester value (EV), iodine value (IV), total fatty matter (TFM), free caustic alkali
content, density, colour, and titre (T) were experimentally determined. The results of
the different analyses are summarized in Table 1. The fact that the palm stearin is
composed of mainly palmitic acid (50-74%), therefore considered as hard oil, makes
it a suitable substitute to the beef tallow. Thus, the saponification reaction was
carried out using 10% of coconut oil and 90% of palm stearin/beef tallow; the
amount of sodium hydroxide required for the saponification was estimated as
reported (Moulay et al., 2005) using the SVs of the fats and their weight
percentages. The results are actually in the range of the known values (Woollatt,
1985; Davidsohn and Milwidsky, 1987). After the saponification process, the spent
soap lyes were analyzed and the results are gathered in Table 2. The contents in
NaCl, alkali (NaOH), glycerol, and water were found to vary with stearin
concentration but in a non systematic fashion. Yet, the estimated values are within
the range of the standard ones (Woollatt, 1985; Davidsohn and Milwidsky, 1987).
Table 2: Composition of the spent soap lyes.
Run
Stearin (%)*
NaCl (%)
Alkali (%)
(%Na 2 O)***
Glycerol (%)
Water (%)**
F1
10
0.32 (0.248)
10.02
79.66
F2
10
11.5
0.28 (0.217)
7.36
80.86
F3
20
11
0.23 (0.178)
11.38
77.39
F4
30
13
0.33 (0.255)
9.20
77.47
F5
35
08
0.40 (0.310)
11.80
79.80
F6
40
9.5
0.50 (0.387)
12.88
77.12
F7
50
10.20
0.11 (0.085)
10.58
89.11
F8
60
12.50
0.24 (0.186)
10.01
77.25
F9
70
10.50
0.35 (0.271)
9.84
79.31
F 10
80
09
0.31 (0.240)
8.46
82.23
F 11
90
12
0.36 (0.279)
12.50
75.14
Table 3 compiles the analyses results of the soap produced at different palm
stearin extents. It can be noticed that the titre of the soap, T S , increases with an
increasing palm stearin concentration. The best soap formulations with respect to
the recommended titre (38-42 C) are the runs 2-4 corresponding to 10-35% of palm
stearin. The experimentally estimated titres presented in Table 3 are closer to the
343
theoretical ones. As shown in Table 3, the iodine values IV of the soap would be
lowered as the palm stearin content increased in the fat blend.
The salt content was found to be lower than unity and this finding is in a fair
agreement with the recommended salt concentration (<1%). Moreover, the total fatty
matter, TFM, was found to be in the range of 64-70% which is an acceptable value.
The lower salt concentrations coupled with the TFM values would indicate that the
actual saponification product is a neat soap and that the liquidation process, a
critical saponification step, was successful. The free caustic alkali of the soap was
about 0.05-0.11% suggesting an efficient washing process during the manufacture,
and this caustic amount would not cause a hand irritation.
Another parameter of the soap-making process is the partition coefficient, K G ,
which is the glycerol repartition between the final soap (neat soap) and the spent
lye. For a successful process, this factor was reported to be 0.4 (Woollatt, 1985). As
can be seen in Table 4, the value for K G is within 0.326 and 0.385 which is closer to
the commonly found one.
Table 3: Physico-chemical characteristics of the soap.
Run
IV
T (C) NaCl (%)
(mg/100g) S
Alkali (%)
(% Na2O)
Glycerol*
(%)
F1
34.9
38.2
0.30
0.11 (0.085)
69.55
23.88
6.16
F2
33.5
39.4
0.33
0.09 (0.070)
67.49
27.11
4.98
F3
32.1
40.6
0.39
0.04 (0.030)
68.12
26.44
5.01
F4
30.7
41.8
0.48
0.09 (0.070)
67.03
27.60
4.80
F5
30.0
42.4
0.54
0.12 (0.093)
66.70
27.96
4.68
F6
29.3
43.0
0.45
0.06 (0.046)
64.71
30.11
4.58
F7
27.9
44.2
0.40
0.08 (0.062)
66.93
27.11
4.88
F8
26.5
45.4
0.47
0.10 (0.077)
68.06
26.49
4.88
F9
25.1
46.6
0.35
0.05 (0.038)
70.41
22.90
6.29
F10
23.7
47.8
0.59
0.07 (0.054)
69.37
25.08
4.89
F11
22.3
49.0
0.44
0.07 (0.054)
67.21
27.41
4.87
It is worth mentioning that the present experimental results were in line with
the Wigners rule, also called the 66% rule. Indeed, the constant K S in the
empirical equation of Wigner, Equation 19, was found in the range of 1.374-1.471 as
given in Table 4. These values are not far from the common one, 1.50-1.53.
344
Moulay et al.: P A L M S T E A R I N I N S O AP M A K I N G P R O C E S S
Run
F1
KS
1.395
KG
0.335
F2
1.439
0.364
F3
1.416
F4
1.437
0.354
0.374
F5
F6
1.398
1.472
0.356
F7
1.436
0.385
0.326
F8
F9
1.414
1.373
0.360
0.327
F10
F11
1.347
1.434
0.330
0.368
The palm stearin-based soap was a white material with a pleasant smell;
usually, the neat soap is devoid of smell and the use of a fragrant is always
necessary for the toilet soap-making. Soap, made wholly of beef tallow as the hard
fat component, frequently tends to give off rancidity in the long run. Thus, a
substitution extent of the tallow by the palm stearin may screen this drawback.
The cleaning performance tests were assessed on a tomato paste-dirtied white
fabric according to a described process (Moulay et al., 2003; Moulay et al., 2005).
The results were acceptable as the degree of whiteness of the washed fabric
specimen was high. Besides, the water solutions of the different soap samples gave
copious foaming, indicating a high washing performance.
CONCLUSION
In conclusion, the palm stearin is, in addition to its cost effectiveness, a good
tallow substitute in the soap-making as revealed by the properties of the soap. Also,
the soap-making process using the palm stearin as a part of hard fat showed that
the different parameters of the process were within the norms.
ACKNOWLEDGEMENTS
The authors are indebted to the ENCG firm (Entreprise Nationale des Corps Gras, Algiers)
for their supply of fats. We greatly thank the ENCG technicians for their helpful discussion.
REFERENCES:
Davidsohn, A. S., Milwidsky, B.M., 1987: Synthetic Detergents, seventh ed., - John Wiley &
Sons, New York, 315 pp.
deMan, J. & deMan, L. 1995:
st
International Society for Fat Research (ISF). The Hague. - Publ. PJ Barnes &
Associates, Bridgewater, pp.561-563.
Fujimoto, T., 1985. New Introduction to Surface Active Agents. - Sanyo Chemical Ind.
Ltd., Kyoto, 605pp.
Moulay, S., Bentaleb, H., Abdessemed, M., 2003: Algerian montmorillonite as a builder in a
detergent powder. - Journal of Surfactants and Detergents, 6: 113-118.
345
Moulay, S., Zenimi, A., Dib, M., 2005: Rosin/Acid oil-Based Liquid Soap. - Journal of
Surfactants and Detergents, 8: 169-174.
Norlida, H. M., Md Ali, A. R., Muhadkir, I., 1996: Blending of Palm Oil, Palm Stearin and
Palm Kernel Oil in the Preparation of Table and Pastry Margarines. - International
Journal of Food Sciences & Nutrition, 47: 71-74.
Norris, F. A., 1965: Fats and Fatty Acids. In: Kirk-Othmer Encyclopedia of Chemical
Technology, second ed. - John Wiley & Sons, New York, Vol. 8, pp.770-811.
Petrauskaite, V., de Greyt, W., Kellens, M., Huyghbaent, A., 1998: Physical and Chemical
Properties of trans-Free Fats Produced by Chemical Interesterification of Vegetable
Oil Blends. - Journal of the American Oil Chemists' Society, 75: 489-493.
Tsujii, K., 1998: Surface Activity: Principles, Phenomena and Applications. - Academic
Press, San Diego, 245pp.
Woollatt, E., 1985: The Manufacture of Soaps, Other Detergents and Glycerol, first ed. John Wiley & Sons, New York, 474pp.
346