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Optimization of solubilizers combinations

on the transparent liquid soap with the


addition of peppermint (Mentha piperita L.)
and lavender (Lavandula L.) oil
Cite as: AIP Conference Proceedings 2120, 050020 (2019); https://doi.org/10.1063/1.5115696
Published Online: 03 July 2019

Susinggih Wijana, Tika Puspita and Nur Lailatul Rahmah

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AIP Conference Proceedings 2120, 050020 (2019); https://doi.org/10.1063/1.5115696 2120, 050020

© 2019 Author(s).
Optimization of Solubilizers Combinations on the
Transparent Liquid Soap with the Addition of Peppermint
(Mentha piperita L.) and Lavender (Lavandula L.) Oil
Susinggih Wijana1, a), Tika Puspita1, b) and Nur Lailatul Rahmah1, c)
1
Department of Agro-industrial Technology, Faculty of Agricultural Technology, Universitas Brawijaya
Jl. Veteran, Malang 65145, Indonesia
a)
Corresponding author: susinggihwijana@gmail.com
b)
tikatikb@gmail.com
c)
nur_laila@ub.ac.id

Abstract. Transparent soap usually produced using a synthetic substance. Therefore, the formula optimization of
transparent soap must be conducted with natural substances. The essential oils can be used as alternative natural substances
and a transparent agent such as peppermint and lavender oil. Furthermore, peppermint and lavender oil have an antibacterial
activity which is beneficial for skin health. Therefore, this study aimed to determine the optimum formula mainly the
solubilizer of essential oil to produce transparent soap using natural substances with antibacterial activity, especially S.
aureus growth. The solubilizers used included ethanol, glycerin, and liquid sugar. The studied responses included
transparency, viscosity, pH, and total fatty acids. A Simplex Lattice Design (SLD) method which consisted of 13 formulas
was carried out to determine the optimum soap characteristics namely organoleptic, free alkali, specific gravity, foam
power, and antibacterial activity. The results showed that the optimum solubilizer formula was 20% liquid sugar, 18%
ethanol, and 18% glycerin. The average of transparency, viscosity, pH, and total fatty acids responses were 98,3%, 553,33
cP, 10,04 and 19,85%, respectively. The characteristics of soap were free alkali 0,12±0.015%, specific gravity 1,161 g/ml,
foam power 1,05±0,050 cm, and growth inhibition zone of S. aureus 10,17± 2,753 mm.

INTRODUCTION
Soap products that are increasingly prevalent in the market are liquid consistency soaps because they are more
practical, easy to store, hygienic, and not easily damaged [1]. Liquid soap is produced by the reaction of saponification
between oil and fat with Potassium Hydroxide (KOH) [2]. One of the innovations in soap products based on their
appearance is transparent soap. Transparent soap has an attractive appearance, so the price is relatively higher than
other soaps [3] and even reach two times then translucent soap.
The level of transparency of soap can be obtained from a mixture of several transparent agents such as glycerin,
ethanol, and sugar. According to Mabrouk [4], transparent agents can maintain the transparency of soap by acting as
a solvent that can inhibit the crystallization of soap. Research on transparent soap making has been carried out by
Hambali [5] using transparent agent combinations, namely 13% glycerin, 15% ethanol, and 17% sucrose. Similar
research has also been carried out by Prapanta [6] with the addition of essential oils from Citrus nobilis Lour. var.
Microcarpa. The combination of transparent agents used is 11% glycerin, 15% ethanol, and 17% sugar.
The right proportion of transparent agent combinations can produce good characteristics of transparent soap, so
optimization of the soap formula needs to be done. There are many optimization models can be used, but the famous
one is the response surface method. Sameera and Raju [7] proposed a Simplex Lattice Design optimization with
relatively simple procedures, and analysis can be done with certain models. Therefore, the Simplex Lattice Design
was carried out to optimize the proportion of transparent agents to produce a transparent liquid soap.

International Conference on Biology and Applied Science (ICOBAS)


AIP Conf. Proc. 2120, 050020-1–050020-7; https://doi.org/10.1063/1.5115696
Published by AIP Publishing. 978-0-7354-1860-8/$30.00

050020-1
The use of soap as a cleaning product has been developed into antibacterial soap. Antibacterial soap can minimize
skin infections caused by bacteria. According to Orchard and Vuuren [8], the normal flora of the skin is
Staphylococcus aureus (S. aureus) which can cause infections and allergies to the skin, such as impetigo. Impetigo is
a skin infection caused by bacteria and is most often found in children. More than 62% of S. aureus is found in cases
of impetigo through scraping the nasal mucosa [9]. Therefore, the use of antibacterial soap needs to be done to prevent
the onset of the disease.
Many antibacterial soap products on the market use synthetic antibacterial active ingredients such as triclosan and
chloroxylenol [10]. The use of chemical soap continuously can cause antibiotic resistance [11]. Therefore, natural
antibacterial alternatives to soap need to be applied, one of which is by adding antimicrobial essential oils such as
peppermint oil and lavender oil.
The main component of peppermint oil is menthol (29 - 48%) [12]. According to Horváth and Koščová [13],
peppermint oil can inhibit the growth of S. aureus with a minimum concentration of 0.25%. Peppermint oil can cause
a very pungent aroma despite use in minimum concentrations. Therefore, peppermint oil needs to be combined with
other essential oils, such as lavender oil. The main components of lavender oil, linalool (53.5%), can have antibacterial
effects [14] and can be used as aromatherapy substances [15]. According to Djenane [16], lavender oil can inhibit the
growth of S. aureus with a minimum concentration of 0.025%. Therefore, the optimization study of a combination of
transparent liquid soap solvents with the addition of peppermint oil and lavender oil is expected to increase the added
value of soap products and be of interest to many consumers.

EXPERIMENTAL DETAILS

Experimental Design
Component level of solubilizer namely liquid sugar (A), ethanol (B), and glycerin (C) were determined prior to
optimization 56% of liquid soap as depicted in Table 1. A simplex lattice design was used to optimize the solubilizers
of liquid soap as depicted in Table 2, with the mathematical model within equation 1.
TABLE 1. Component Level of Solubilizers
Component Material Upper limit Lower limit Average Deviation
A Liquid sugar 20.00 22.00 20.67 0.7698
B Ethanol 18.00 20.00 18.67 0.7698
C Glycerin 16.00 18.00 16.67 0.7698
Total 56.00

Y =  1( A)   2( B )   3(C )   12( A)( B )   13( A)(C )   23( B )(C )   123( A)( B )(C )   12( A  B )   13( A  C )   23( B  C )
(1)
Where 20 ≤ (A) ≤ 22 (%); 18 ≤ (B) ≤ 20 (%); 16 ≤ (C) ≤ 18 (%) and (A) + (B) + (C) = 56%.

Preparation of Liquid Soap


Liquid soap was prepared using a hot process modified from Debnath et al. [17]. 28.22 ml of coconut oil, 18.8 ml
of palm olein, 5.23 ml of castor oil and 12.9 g of KOH were diluted in 27.56 ml distilled water. Gently agitated within
20000 rpm at 75 °C for 5 min until the soap paste was produced. The paste was then diluted with ethanol and glycerin
at 60 °C for 10 min before cooled. Liquid sugar was added to the cooled paste and stirred until homogeneous.
Peppermint and lavender oil were added to the transparent soap.

Research Parameters
The level of transparency was evaluated using UV-Vis spectrophotometer at a wavelength of 650 nm within 25
°C. Distilled water was used as a blank solution. The best formula is chosen based on the percent transmittance which
is close to 100% with a minimum value of 90% [18]. Another parameter namely viscosity and pH was determined
using viscometer LV and pH meter.

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TABLE 2. Experimental design
Component Response
NO A B C Liquid Ethanol Glycerin Transpar Viscosity pH Fatty
sugar ence Acid
1 1 0 0 22.00 18.00 16.00 β1 β1 β1 β1
2 0 1/3 2/3 20.00 20.00 16.00 β23 β23 β23 β23
3 0 1 0 20.00 20.00 18.00 β2 β2 β2 β2
4 2/3 1/3 0 21.33 18.00 16.00 β12 β12 β12 β12
5 1/3 0 2/3 21.33 18.67 16.67 β13 β13 β13 β13
6 0 0 1 20.67 18.00 16.00 β3 β3 β3 β3
7 2/3 1/3 2/3 20.67 19.33 16.67 β13 β13 β13 β13
8 0 2/3 1/3 20.67 18.67 17.33 β23 β23 β23 β23
9 1/3 1/3 1/3 20.00 19.33 16.67 β123 β123 β123 β123
10 1/3 2/3 0 20.00 18,67 17.33 β12 β12 β12 β12
11 1 0 0 22.00 18.00 16.00 β1 β1 β1 β1
12 0 1 0 20.00 20.00 16.0 β2 β2 β2 β2
13 0 0 1 20.00 18.00 18.00 β3 β3 β3 β3

Fatty acid (F) was determined based on the Indonesian National Standards. 10 g of soap sample (W) was diluted
with 50 ml of distilled water and 25 ml of HCl, then added with methyl orange indicator. The solution then precipitated
in the separating funnel. The solvent is shaken and washed with 10 ml of distilled water each washing until it does not
react acidically (tested with blue litmus paper). The solvent was filtered with N2SO4 anhydrous and put into a fat flask
that had known its weight along with boiling stone (W1). The solvent is distilled and the fat flask is dried at 105 °C
until a fixed weight (W2) was obtained. The total value of fatty acids is calculated based on the formula presented in
equation 2.
W1  W2
F =  100%
W (2)

Evaluation of Liquid Soap


Sensory evaluation was determined using 10 untrained panellists in the texture, color and aroma of liquid soap.
The liquid soap was compared with commercial soap. The liquid soap was then evaluated the foam stability based on
the height of the formed foam. 1 mL of liquid soap was diluted with 9 ml of distilled water, then homogenized using
vortex for 20 sec. The homogenized soap was then precipitated for 10 min before the height of the formed foam was
measured.
100 mL of alcohol was boiled in 250 ml erlemenyer flask, added 0.5 mL of phenolphthalein indicator and cooled
until 70 °C, then neutralize with 0.1 N KOH. 5 gram of soap samples, boiling stones, pairs of upright coolers were
added into the neutral alcohol, and heated to quickly dissolve over a water bath, then simmered for 30 min. If wasn’t
alkaline formed (not colored red), cooled to 70 °C and titrated with 0.1 N KOH solution in alcohol to arise red color,
hold for 15 sec. The total free alkali was determined in equation 3. Another evaluation was specific gravity using
pycnometer.
V NM
A =  100%
W (3)
Where V= KOH 0.1 N used (ml); N= normality of KOH; M= weight of lauric acid and W= weight of the sample.

RESULTS AND DISCUSSIONS

The response of Simplex Lattice Design


All response passed the requirement for Indonesian National Standards (SNI) within the combination of liquid
sugar, ethanol, and glycerin 20.00, 18.00, and 18.00% respectively. A special cubic model produced a significant

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influence on the response. The model regression equation for each response namely transparency (Y1), viscosity (Y2),
pH (Y3), and fatty acids (Y4) which is influenced by liquid sugar (X1), ethanol (X2), and glycerin (X3) with a 95%
confidence level can be seen in the following equations:
Y1 = 451 .731 X 1 X 2 (4)
Y2 = 299.487 X 1 + 379.487 X 2 + 561.026 X 3 - 402.692 X 1 X 2 - 451.154 X 1 X 3 - 811.154 X 2 X 3 + 6795 X 1 X 2 X 3 (5)
Y3 = 10.39239 X 1 + 10.3114 X 2 + 10.0406 X 3  0.845192 X 1 X 2  1.22942 X 1 X 3  1.27788 X 2 X 3 - 10.8225 X 1 X 2 X 3 (6)

Y = 21.5164 X + 23.6877 X + 20.3689 X


4 1 2 3 (7)
An increase in the dissolved index of soap which is easily soluble can be done to produce transparent soap. A high
refractive index can maximize the transmission of light that passes through the soap. One approach to maximize light
transmission on the soap is by adding solubilizer (solvent) [19]. The use of ethanol can increase the solubility of soap
and prevent the crystalline phase from forming, while sugar can help increase the refractive index of soap which is
easily soluble. The main ingredient that helps make soap transparent is ethanol which acts as a hydrotrope. According
to Kumar [20], hydrotopes are compounds that can significantly increase the solubility of organic solutes in water,
especially in alkaline-containing environments. The use of glycerin can improve the transparent texture of soap due
to the clear texture of glycerin.
The liquid sugar used consists of a mixture of fructose and glucose. According to Soto [21], the solubility of
fructose in water is much higher than glucose. Lower glucose solubility is due to a greater interaction factor of particles
between molecules, thus increasing the viscosity of the solution, while the high solubility of fructose is associated
with increased interaction of solvent particles. Increased viscosity occurs because of the formation of hydrogen bonds
formed between hydroxyl groups in adjacent molecules, thus giving the effect of branching polymers that can increase
the resistance of liquid sugar. According to Zumdahl and Decoste [22], increasing the number of hydrogen bonds
between adjacent molecules produces stronger intermolecular attractions. Strong intermolecular attractions make
molecules more difficult to move against each other, increasing viscosity. The simultaneous use of ethanol and
glycerin can increase viscosity because the hydroxyl group is capable of producing hydrogen bonds.
The pH value of the soap produced has fulfilled the requirements, which are still in the range of 8 - 11. The highest
pH value is obtained in formula 6 which is 10.58 with the total components of liquid sugar, ethanol, and glycerin as
much as 21.33, 18.67, and 16.00%. The lowest pH value was obtained in formula 13, which is 10.00 with the total
components of liquid sugar, ethanol, and glycerin 20.00, 18.00, and 18.00% respectively.
The three transparent agent components significantly influence the total soap fatty acids produced. The total value
of fatty acids has a tendency to increase along with the addition of ethanol. According to Spitz [23], ethanol functions
as a solvent in the manufacture of soap because it is easily soluble in water and fat. The addition of ethanol can increase
the solubility of soap and prevent the unexpected crystalline phase from forming in liquid soap, so the amount of
dissolved soap is greater. The more amount of soap dissolved means the more the number of fatty acids in the soap.
According to Wijana [24], total fatty acid levels have an impact on the level of effectiveness of clean soap. The lower
total levels of fatty acids, which means the lower the active ingredient in soap, the lower the net power of soap. The
contour plot of all response can be seen in the Fig. 1.

Optimization and Validation Simplex Lattice Design


The purpose of this study was to optimize transparency response values, viscosity, pH, and total fatty acids by
maximizing the transparency value of soap. The optimal solution produced consisted of a composition of liquid sugar
of 20%, 18% ethanol, and 18% glycerin. Desirability value is obtained at 0.864 which means that the optimal solution
is likely to have an accuracy of 86.4% based on optimized target parameters.
The optimal solution obtained from the Design Expert 11.0 Trial program was verified by testing the parameters
that were made a response to the optimal soap formula 3 times. Verification aims to confirm that the resulting model
is correct with the condition of the chosen trust (95%). The results of the verification obtained is that the optimum
formula has the test results according to predictions obtained through the Design Expert 11.0 Trial program. The
average response value of transparency, viscosity, pH, and total fatty acids were 98.3%, 553.33 cP, 10.04 and 19.85%,
respectively.

050020-4
A: Liquid sugar (%) A: Liquid sugar (%)
22 22
2 2

300

97.5 98 16 400
18
16 18

500
300
98 98.5 2 2
2 2 20 20 18
20 20 18 B: Ethanol (%) C: Glycerin (%)
B: Ethanol (%) C: Glycerin (%) Viscosity (cP)
Transparency (%)
(a) (b)
A: Liquid sugar (%) A: Liquid sugar (%)
22 22
2 2
21

10.4 10.5

10.5

16 18 16 22 18
10.3
22

23

21
10.4 10.2

10.5 10.1 20
2 2 2 2
20 20 18 20 20 18
B: Ethanol (%) C: Glycerin (%) B: Ethanol (%) C: Glycerin (%)
pH Fatty acid (%)
(c) (d)
FIGURE 1. The contour plot with a special cubic model for each response transparency (a); viscosity (b); pH (c); and fatty acid
(d)

Liquid Soap Characterization


The samples tested were Dettol brand commercial soap and optimal peppermint and lavender oil transparent liquid
soap. The attributes of the hedonic test include texture, aroma, and color. The organoleptic test results are presented
in Table 3.

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TABLE 3. Organoleptic test
Component Transparent soap Commercial soap; Dettol
Texture 4.6 4.4
Aroma 4.5 4.8
Color 3.5 4.4

The results obtained were the color, and aroma attributes of Dettol soap were preferred by panelists as a whole
compared to transparent liquid peppermint and lavender oil. The aroma attribute is the lowest attribute of its
assessment in transparent peppermint and lavender oil liquid soap products. This is because the peppermint aroma is
more dominant than lavender. Meanwhile, the texture attributes of peppermint and lavender oil transparent liquid soap
are preferred over Dettol soap. This is because the thickness of Dettol soap is too high. According to Karsheva [25],
the viscosity is the two parameters of concern in liquid soap preparations. Viscosity aims to determine the consistency
of the preparation, which will later affect the application of preparations such as easily poured from the container but
not easily spilt flowing from the hands.
The free alkaline analysis aims to determine the amount of free alkaline present in the soap products produced.
Soap that has been made has free alkaline content of 0.12 ± 0.015%. The free alkali value obtained still meets the SNI
quality standard requirements for liquid bath soap, so transparent liquid peppermint oil and lavender soap are still safe
for use on the skin. According to Widyasanti [26], good soap is a soap that results from a perfect reaction between
fatty acids and alkalis which is expected to have no residue after the reaction. The excess alkali in soap should not
exceed 0.14% because alkali is hard and can cause irritation to the skin.
Specific gravity analysis aims to determine the weight ratio of liquid soap in the air at 25 °C to the weight of water
with the same volume and temperature. Soap that has been made has a specific weight of 1.161 g/mL. The value of
the specific gravity of the soap obtained did not meet the SNI standard for liquid bath soap i.e. 1.01-1.10 g/mL.
Increasing the value of the specific gravity of peppermint and lavender oil transparent liquid soap can be caused by
the high specific gravity of the solvent used, namely liquid sugar and glycerin, although it is dissolved with ethanol,
it is suspected that the substance mixed tends to have a high weight. According to Predianto [27], testing of specific
gravity is important because it can determine whether a solid can be mixed or not with other substances so that it will
be easier in the formulation of soap.
Foam power analysis is carried out by measuring foam height. The soap foam power test produced was done by
comparing the Dettol brand of commercial soap as a control. Transparent peppermint liquid soap and optimal lavender
oil have a foam height of 1.05 ± 0.050 cm. Commercial soap of the Dettol brand has a high foam value of 2.53 ± 0.076
cm. The test results showed that the power of peppermint and lavender oil transparent liquid soap was lower than the
Dettol brand of commercial soap. The low amount of soap foam produced when compared with the high Dettol brand
soap foam is caused by the absence of additional surfactant on the soap preparation. The composition of Dettol soap
is a surfactant, namely Sodium Lauryl Sulfate (SLS), which functions as a foam enhancer. According to Sari and
Ferdinan [28], SLS is a surfactant that is often used in making soap and in large doses can irritate the skin. Therefore,
soap making in this study did not use SLS.
Antibacterial activity characterized by the presence of a clear zone occurs around the paper disk in a petri dish
containing a suspension of the S. aureus bacteria. The test sample was divided into transparent liquid peppermint and
lavender oil (A), commercial Dettol (B) brand soap as a positive control, and transparent liquid soap without
peppermint oil and lavender (C) as negative controls. The test results showed that the samples tested could inhibit the
S. aureus bacteria. The inhibition zone of sample A was obtained at 10.17 ± 2.753 mm. The sample B inhibition zone
was obtained at 8.17 ± 1.755 mm. The inhibition zone of sample C was obtained at 3.00 ± 0.866 mm. The test results
show that transparent peppermint and lavender oil liquid soap has the greatest antibacterial activity compared to
similar commercial soaps that use chloroxylenol as an antibacterial agent.
Transparent peppermint oil and lavender liquid soap can inhibit bacterial growth due to both uses as an
antibacterial. According to Alankar [29] research, the antiplasmid activity of peppermint oil and its main constituent,
menthol, can remove plasmids in bacteria. According to Zengin and Baysal [30], linalool, a component of lavender
oil, is monoterpene alcohol which has a hydroxyl (-OH) group. The hydroxyl group is responsible as an antimicrobial
which results in interactions with intracellular components such as irregular and wrinkled cell structure, as well as
leakage of cell contents and lysis in S. aureus.
The test results also showed that transparent liquid soap without active substances also had antibacterial activity.
This activity is thought to arise from constituent components such as coconut oil. According to Thormar [31],
monolaurin, a monoglyceride compound contained in coconut oil, can damage bacterial cell walls and membranes,
resulting in cell leakage which ultimately leads to cell death.

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SUMMARY
Solvent combinations consisting of 20% liquid sugar, 18% ethanol, and 18% glycerin produced an optimal
transparent liquid soap in the appearance. However, the specific gravity has a slightly higher than Indonesian National
Standards by .061 g/mL. The transparent liquid soap formula with the addition of peppermint and lavender oil has a
greater antibacterial activity compared to the commercial soap that uses chloroxylenol as an antibacterial agent. This
study proved that the natural substance of peppermint and lavender oil have the antibacterial ability with potential
application to health benefit.

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