Journal of Cleaner Production xxx (2015) 1e6

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Natural surfactant extracted from Sapindus mukurossi as an

eco-friendly alternate to synthetic surfactant e a dye surfactant
interaction study
Sidra-Tul Muntaha, M. Nasiruddin Khan*
Department of Chemistry, University of Karachi, Karachi 75270, Pakistan

a r t i c l e i n f o a b s t r a c t

Article history: The comparative study between synthetic and natural surfactants was carried out using spectropho-
Received 7 April 2014 tometry, conductometric and surface tension measurement. The value of critical micelle concentration
Received in revised form for the natural surfactant was determined. The influence of temperature on conductance was observed
29 December 2014
and the interaction is found favorable at low temperature. The comparative interaction behavior of the
Accepted 8 January 2015
surfactants was studied by reacting them individually with an oppositely charged dye. The concentration
Available online xxx
of both the surfactants was varied from pre to post micellar region to examine spectral changes. It was
detected that the variation in the concentration of surfactant leads to the changes in the spectra of dye.
Keywords:
Natural surfactant
The study showed that the initial increase in surfactant concentration leads to the formation of stable
Critical micelle concentration ion-pair, but increasing concentration beyond its critical micelle concentration caused the dissolution of
Sodium dodecyl sulfate dye surfactant aggregates. The surface tension measurement was also performed. The values for equi-
Conductance librium constant and Gibbs free energy were calculated based on the theoretical model. On the basis of
Spectrophotometry these values, it is stated that the interaction between natural surfactant and dye is thermodynamically
favorable and competitive. The use of natural surfactant in place of synthetic surfactant is suggested as an
inexpensive, environmental friendly and cleaner substitute.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction researchers to use alternates to synthetic surfactants. The alter-

Amphiphiles that possess surface active properties are known as
surfactants. These agents contain both lipophilic and hydrophilic
groups in them so they exhibit fascinating and exclusive behavior.
Due to the behavior of surfactant, they are widely applicable in
industries as a wetting, flocculating and foaming agents, adhesives,
penetrators and de-emulsifiers (Mulligan, 2005, 2009; Gharaei-
Fathabad, 2011). The widespread use of surfactants in different
areas led the foundation of surfactant science. Surfactant science
starts getting its recognition as a separate field and also experi-
encing advancement day by day. This advancement in the tech-
nology of surfactant results in the addition of the huge variety of
surfactants. The upgradation of this technology can also impose
some serious environmental issues (Chevalier, 2002). Environ-
mental concerns on the use of surfactants initiate the interest of the
* Corresponding author. Tel.: þ92 3142134934.
E-mail address: nasiruk@uok.edu.pk (M.N. Khan).
nates can be natural surfactants.
The surfactants that are obtained directly from the natural
source are considered as natural surfactants. These surfactants can
be obtained either from the source having plant origin or animal
origin. During the collection of surfactant from the source, no
organic synthesis should have been involved not even as after
treatment. Some sort of separation techniques like extraction,
filtration, precipitation or distillation should be adopted to acquire
the product. The term “natural surfactant” was used by many re-
searchers to consider the molecules that are coming indirectly from
natural raw materials under this term (Holmberg, 2001; Rybinski,
2001; Salati et al., 2011). In literature, many examples of natural
surfactants are reported. Molecule (saponin) derived from the
plants belonging to the genus Sapindaceae can be the possible
alternative for synthetic surfactants as identified by Roy et al.
(1997) and Kommalapati et al. (1997). The other natural surfac-
tants like fatty acid esters of sugars and fatty acid esters or amides
of amino acids have been suggested to be used as surfactant in the
place of synthetic surfactant (Holmberg, 2001; Salati et al., 2011;
Johansson and Svensson, 2001). As stated by Holmberg (2001),

http://dx.doi.org/10.1016/j.jclepro.2015.01.023
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Please cite this article in press as: Muntaha, S.-T., Khan, M.N., Natural surfactant extracted from Sapindus mukurossi as an eco-friendly alternate
to synthetic surfactant e a dye surfactant interaction study, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.01.023
2 S.-T. Muntaha, M.N. Khan / Journal of Cleaner Production xxx (2015) 1e6

natural surfactants can be classified into three groups: i) surfactants Table 1

produced by fermentation of natural raw materials, ii) surfactants Chemical formula and molecular weight of triterpenoid saponins from the pericarp
of S. mukorossi Gaerten.
having natural hydrophilic head groups and, iii) surfactants that
possess natural hydrophobic tail (Holmberg, 2001; Kommalapati Formula Molecular weight Molecular ion Mass to charge ratio (m/z)
et al., 1997). The surfactants produced by fermentation are known C41H66O12 750 [C41H66O12 þ Na]þ 773
as biosurfactants. These surfactants can be produced by microbes C46H74O15 866 [C46H74O15 þ Na]þ 889
such as bacteria or yeast from the substrates like sugars, oils, al- C48H76O17 924 [C48H76O17 þ Na]þ 947.498
þ
C50H78O18 966 [C50H78O18 þ Na] 989.509
kanes and wastes (Mulligan, 2005, 2009; Gharaei-Fathabad, 2011). þ
C53H86O22 1074 [C53H86O22 þ Na] 1097
Natural surfactants possess several advantages over chemically C58H94O26 1206 [C58H94O26 þ Na]þ
1223
synthesized surfactants. They have low environmental risk as these C59H92O25 1200 [C59H92O25 þ Na]þ 1229
are of natural origin (Song et al., 2008). Some of the advantages of
such compounds over synthetic compounds are biodegradability,
low toxicity, biocompatibility, low cost, specificity. They are avail- them dispersed in different compartments of environment (soil,
able in large quantities and are also very effective in extreme water, and sediment). Such compounds are persistent in the envi-
conditions like temperature, pH and salinity. Natural surfactants ronment. The synthetic surfactants also inhibit the auto-filtering
can be very effectively used in environmental control (Kosaric, activity of aquatic organisms (Vorozhun and Ostroumov, 2009;
2001; Rahman and Gakpe, 2008; Chhetri et al., 2009). Ostroumov, 2003). These compounds are not only harmful for the
Surfactants fall in the first category of natural surfactants are aquatic life but also cause health hazards like dermatitis, respira-
those which are obtained directly from natural sources. These tory irritation, eye irritation, etc. (Gupta et al., 2003). The re-
include products like saponins and humic compounds. Humic acid searchers are very much keen in finding out the environmental
obtained from biomass as natural surfactant can have various in- friendly alternatives for such compounds due to this reason.
dustrial applications (Salati et al., 2011). It can also be used for soil The present work focused on replacing synthetic surfactant with
remediation (Conte et al., 2005). Saponins are used for washing of natural surfactant. For this purpose, the mode of action and the
soil (Roy et al., 1997), the removal of heavy metals from soil (Song chemistry of the proposed surfactant were investigated to preserve
et al., 2008), soil remediation (Kommalapati et al., 1997; Kosaric, efficacy of purpose while reducing toxicity of the synthetic sur-
2001; Hong et al., 2002), and enhanced oil recovery (Chhetri factant. Conductometric, spectrophotometric and surface tension
et al., 2009). measurement was carried out for this purpose. In addition, the pH
In the recent study, specie from Sapindaceae genus is considered measurement for natural surfactant was also performed to inves-
to be used as natural surfactant as the plants of this genus contain tigate the nature of the natural surfactant.
surface active agent known as saponins. These are the compounds
that have the tendency of producing lather or foam in aqueous
2. Experimental
solution similar to soap. Saponins can be found in a number of plant
species as well as in some marine organisms. The saponin rich
2.1. Reagents
species of genus Sapindaceae reported in literature include soap-
wort (Saponaria officinalis), Sapindus trifoliatus, soapbark (Quillaja
Fruit pericarp, cationic dye neutral red (NR), and synthetic sur-
saponaria), Sapindus emarginatus, soap root (Chlorogalum pomer-
factant sodium dodecyl sulfate (SDS) were purchased from local
idianum), soapnut (Sapindus mukurossi) or soapberry (Sapindus
supplier. The dye and synthetic surfactant was of Analytical Grade
saponaria) (Dunford, 2012; Kjellin and Johansson, 2010). Saponins
(AR). The known amounts of NR dye and SDS surfactant were dis-
are the organic compounds which contain glycosides with non-
solved in doubly distilled deionized water for the preparation of the
sugar aglycone. They resemble to sterol (Chhetri et al., 2009;
stock aqueous solution. The concentration was expressed in molar
Oleszek and Bialy, 2006). The specie used in the recent study is S.
concentration. The concentration of natural surfactant extract was
mukurossi which is also known as soapnut tree. In Asia, it is present
given as weight percent (wt%). The concentration of dye was kept
in tropical and subtropical regions. The fruit of this tree is known as
constant (5  105 M) during the investigation. Doubly distilled
soapnut or reetha and is traditionally used as a shampoo for
deionized water was used to make the subsequent dilutions.
cleaning hairs and as a detergent for cleaning woolen fabrics.
Soapnut is round, saponaceous and fleshy nut. The fruit of soapnut
tree is yellowish brown in color and changes its color on drying. The 2.2. Apparatus
fruit consists of seed encapsulated in a black hard and shiny
endocarp or shell and pericarp. The pericarp constitutes about 56% UVeVisible (UV-1601) spectrophotometer (Shimadzu, Japan)
of the whole fruit and the rest is balanced by the seed (Yin et al., with 1 cm path length quartz cells was used for the measurement of
2011). As presented in literature, the saponins are of different the absorption intensity of the aqueous solution. For the mea-
types (Vincken et al., 2007). The major saponins present in the surement of specific conductivity of the solutions, Conductivity
pericarp of the soapnut fruit are triterpenoid-type (Li et al., 2013). meter, model 4310 (Jenway) was used. Magnetic stirrer was used to
The chemical formula for saponins obtained from the soapnut fruit stir the extract of the natural surfactant. The solution of natural
as reported in literature are shown in Table 1 (Chhetri et al., 2009; Li surfactant was separated from the solid using laboratory centrifuge
et al., 2013; Huang et al., 2003, 2008). The percent compositions of (model YJ03-043-4000, China). The pH of the solution was recor-
the elements present in saponins were 51% O, 44% C, and 6% H. As ded by pH meter (model pH 900) manufactured by Precisa
saponins are the surface active agents (Roy et al., 1997; (Switzerland). The surface tension measurement was consummate
Kommalapati et al., 1997; Song et al., 2008; Chhetri et al., 2009), using stalagmometer (075920, Kocour, Chicago) at temperature
so their concentration of critical micelle formation was found to be 25  C (±1  C).
0.1%. The nature of saponins was considered as weakly acidic in
nature. The hydrolysis of glycosides was supposed to be the reason 2.3. Preparation of the natural surfactant
of the weakly acidic nature of saponins (Hong et al., 2002).
The extensive use of synthetic surfactant in households and The natural surfactant solution was prepared by using the
industries imposes serious environmental issues as the most part of method developed by Kommalapati et al. (1997) and Roy et al.

Please cite this article in press as: Muntaha, S.-T., Khan, M.N., Natural surfactant extracted from Sapindus mukurossi as an eco-friendly alternate
to synthetic surfactant e a dye surfactant interaction study, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.01.023
 S.-T. Muntaha, M.N. Khan / Journal of Cleaner Production xxx (2015) 1e6 3

(1997). The known exact amount of dry and powdered fruit peri-
carp (for 2 % stock solution; 2 g in 100 mL) was taken and dissolved
in doubly distilled deionized water. The mixture was then stirred
for 3 h using magnetic stirrer at high speed. After the stirring the
supernatant was centrifuged using centrifugation machine for
about 45 min. The liquid is then filtered and collected into the
volumetric flask and the solution was made up to the mark with
doubly distilled deionized water. The solution obtained is known as
natural surfactant extract (SNS).

2.4. Procedure

SNS solution was titrated against strong base sodium hydroxide

(NaOH) and the pH was recorded after each addition of NaOH. The
absorption spectrum of dye was measured spectrophotometrically
by taking an exact volume of dye solution and adding the known
volume of doubly distilled deionized water in it to obtain the
required concentration. The concentration of dye for the mea-
surement was fixed so as to keep the absorption intensity in the
range. The known exact volume of dye and varying volume of
surfactant was taken in the reaction cell which contains a known
volume of deionized water for the preparation of series of reaction
mixtures. The spectrophotometric measurement of the reaction
mixture was carried out by measuring the amount of light absorbed
by the solution in the wavelength range of 400e800 nm. The
similar procedure was followed for recording the conductivity of
the solutions. The measurement of surface tension was performed
using drop counting method.
3. Results and discussion
3.1. pH-metric measurement of SNS
The nature of SNS was determined by measuring the pH of SNS
solution and was found to be acidic. This interpretation is compa-
rable to the study of Kommalapati et al. (1997) and Roy et al. (1997).
The nature of SNS was further confirmed by the pH-metric titration
of SNS with NaOH. Fig. 1 shows the plot of pH versus volume of
NaOH and Fig. 2 represents the first derivative plot of the pH-metric
titration curve.
It is clear from both Figs. 1 and 2 that SNS has a tendency to
neutralize strong base NaOH provides further evidence for the
acidic nature of the surfactant. Fig. 1 possesses two end points
which refer to the condition of a diprotic acid reacting with a
monoprotic base. Two sharp peaks can be seen in Fig. 2, which
represents that SNS possess two replaceable hydrogen which can
Fig. 2. First derivative plot of the titration curve between DpH/DV (ratio of change in
pH and change in volume) and average volume (Vavg) of NaOH.
be released on reaction with NaOH. As already mentioned, the fruit
pericarps contain glycosides. The hydrolysis of glycosides can be
the possible reason for the acidic nature of the SNS solution (Hong
et al., 2002).
3.2. Critical micelle concentration
The distinctive and elementary property that every surfactant
must possess is the ability to form micelles. All those physical
properties that are dependent on the number or size of the particles
in solution like surface tension, conductivity, viscosity, etc. are
greatly influenced by the micelle formation property of surfactants.
The critical micelle concentration (cmc) is the concentration of the
surfactant at which the surfactant molecules exist in aggregate
form. In the region of cmc, all these properties like conductivity,
surface tension are likely to show a bent in the curve when plotted
against the surfactant concentration.
The change in the conductance of SNS with the concentration of
SNS in the range of 0.08e0.15% is presented in Fig. 3. It is visible
from Fig. 3 that there is a sharp bent in the conductance curve in the
concentration range 0.1e0.12%. On an increase of SNS concentration
from 0.08 to 0.11%, the conductance also increases. In SNS con-
centration range of 0.1e0.12%, slight bent is observed then beyond
0.12%, the conductance increases again. At low SNS concentration,
the molecules are less and exist in the monomeric form, and water

Fig. 1. pH-metric titration curve between pH and volume of NaOH (V) for the titration Fig. 3. Critical micelle concentration determination of SNS using conductance mea-
of SNS with NaOH. surements versus concentration at 30  C.

Please cite this article in press as: Muntaha, S.-T., Khan, M.N., Natural surfactant extracted from Sapindus mukurossi as an eco-friendly alternate
to synthetic surfactant e a dye surfactant interaction study, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.01.023
4 S.-T. Muntaha, M.N. Khan / Journal of Cleaner Production xxx (2015) 1e6

Table 2
Properties of natural surfactant.

pH 4.12
pKa1 (negative log of first acidic dissociation 4.825
constant)
pKa2 (negative log of second acidic dissociation 6.65
constant)
cmc 0.13% (at 20  C),
0.105% (at 30  C)

molecules surround the hydrophilic part of the surfactant resulting

in an initial low conductance. Further increase in SNS concentration
leads to increase the conductance of the solution. The concentra-
tion at which micelle formation occurs there is an abrupt change in
conductance so the preceding concentration can be regarded as the
critical micelle concentration (cmc). Beyond SNS cmc, the
conductance increased again when the SNS concentration in-
creases. This may occur due to the formation of more micelles,
Fig. 5. Spectrophotometric measurement of NR and SNS with respect to time.
interaction of micelles with other micelles, the formation of bigger
micelles or accumulative intermicellar interaction. The cmc value
for SNS at two different temperatures is presented in Table 2 along molecule can attach with a water rich stern layer of micelle in the
with other properties of SNS. The cmc of SNS by surface tension manner of forming a sandwich (Tunç et al., 2012). Such arrange-
method and viscosity method was reported as 0.1% (Roy et al., 1997; ment of dye and surfactant molecules thus hydrates the hydrophilic
Kommalapati et al., 1997). part of the dye and leads to the initiation of van der Waals
interaction.
As SNS causes change in the absorption intensity of NR, the
3.3. Spectrophotometric measurement
change in the absorption intensity of NR was also observed over a
period of time. Fig. 5 represents the absorption spectra for SNSeNR
SNS is subjected to interact with the oppositely charged dye
complex over the time of 40 min. The spectra show gradual
Neutral Red (NR). The interaction between SNS and NR is displayed
decrease in the absorbance with respect to time. The small hypo-
in Fig. 4. It is clear from the figure that the addition of SNS to NR
chromic shift (decolorization) was observed when the dye was left
affects the absorption intensity of NR. The initial addition of SNS in
with SNS in the reaction mixture for 40 min.
NR solution results in the decrease in absorbance of the solution
In order to emphasize the use of SNS in place of synthetic sur-
(curve II). The decrease in absorbance is due to the formation of the
factant, NR was made to interact with synthetic surfactant SDS. For
SNSeNR ion pair. The further addition of SNS tends to increase the
this purpose comparison was made between a mode of action of
absorption intensity of the solution because of the formation of
SDS and SNS on similar dye. SDS contains sodium ion as a counter
micelle or more absorbing specie in the reaction mixture (curve III).
ion and it is an anionic surfactant. On comparing SNS and SDS on
On increasing the concentration of SNS more the absorbance de-
the basis of their nature, it can be said that both behaves as anionic
creases as the ion pair aggregates dissociates thus decreasing the
surfactant when interacted with opposite charged dye and form
absorbance (curve IV).
dyeesurfactant ion pair. Fig. 6 shows the absorption spectra for the
SNS and NR interaction can be regarded as electrostatic inter-
interaction of NR and SDS for 40 min time. The absorbance of NR
action because of the involvement of the ions donated by both
gradually decreases when NR was kept with SDS for 40 min. Each
reacting specie as they possess the counter ions. Another possible
spectrum was taken after 10 min time interval. The absorption
interaction between SNS and NR can be of hydrophobic nature (van
spectra indicated hypochromic shift (a decrease in absorption in-
der Waals interaction). In van der Waals interaction there is no
tensity) on interacting with SDS. This pattern is similar to that of
interaction of hydrophilic part of dye with the oppositely charged
group of the surfactant molecule instead of this the surfactant

Fig. 4. Spectrophotometric measurement of NR and SNS interaction. Fig. 6. Spectrophotometric measurement of NR and SDS with respect to time.

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to synthetic surfactant e a dye surfactant interaction study, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.01.023
 S.-T. Muntaha, M.N. Khan / Journal of Cleaner Production xxx (2015) 1e6 5

SNS. Kommalapati et al. (1997) also made comparison between SNS

and SDS. The comparison was on the basis of their solubility
behavior and it was established that the performance of SNS so-
lutions is comparable to SDS (Kommalapati et al., 1997).

3.4. Conductance measurement

Conductance depends on many factors among these tempera-

ture is an important one. The conductance of a specie exists in
aqueous solution can be affected by bringing about the change in
temperature. In order to examine the influence of temperature on
the conductance of the aqueous dye and surfactant solution, the
conductance of the examined solutions was measured in the
temperature range of 2e50  C. The aqueous solutions were made
by taking a fixed known amount of dye and varying the amount of
SNS. The conductance of NReSNS as a function of concentration of
SNS at eleven temperatures is presented in Fig. 7. The plot in Fig. 7
shows that the conductance changes with the change in tempera-
ture thus confirming the temperature dependent nature of
Fig. 8. Plot of surface tension (mN m1) as a function of concentration of SNS at 298 K
conductance. The formation of dyeesurfactant complex relies on from pre micellar to post micellar region.
the required minimum concentration of surfactant (CRM). CRM is
shown with the vertical dotted line in Fig. 7. As the temperature
in water from pre micellar to post micellar concentration range. The
increased from 2 to 45  C, the value of CRM starts to increase. The
reduction in surface tension in the presence of varying amount of
conductance measured at 50  C seems to be very much linear
SNS from pre micellar to post micellar region is observed in Fig. 8.
corresponding to the condition of no interaction between dye and
The value of surface tension reduced as expected, when the con-
surfactant. From the plot, it is also inferred that the dyeesurfactant
centration of SNS was varied from 0.08% to 0.1%. At 0.1% SNS con-
interaction is favorable at low temperature. The similar behavior is
centration, the sharp change was observed. At that point SNS
also observed in the case of interaction of NR with SDS (Muntaha
showed bent in the value of surface tension which indicated that
and Khan, 2014).
cmc for SNS has been attained. It was also observed from the
conductance plot of SNS, that the cmc concentration for SNS is 0.1%.
3.5. Surface tension measurement After cmc, the surface tension was increased initially but the further
increase in SNS concentration (beyond cmc) reduced the surface
Surface tension is a property which emerged due to unbalancing tension more steadily. The bent in surface tension and conductance
in intermolecular forces encountered at a liquid/vapour and/or at 0.1% for SNS confirms the conclusion, presented also in the
liquid/solid interface. Surface active agent (surfactant) exhibits a literature sources (Mulligan, 2005a; Salati et al., 2011; Roy et al.,
characteristic feature to reduce surface tension of a solution. Sur- 1997); that the concentrations at which SNS exhibited changes in
factant in aqueous solution reduces the surface tension by mini- their behavior, are those specific to cmc points.
mizing the forces acting on the surface of a solution. It prevents the The plot of surface tension as a function of SDS concentration is
strong binding among water molecules; in response reduce the presented in Fig. 9. The surface tension was reduced when varying
intramolecular forces, stabilize the forces acting on the surface by amount of SDS was added into the aqueous solution. The concen-
linking with non-polar vapor phase via hydrophobic part and result tration of SDS was varied from pre micellar to post micellar region.
in lowering the surface tension of a solution. To find out the extent The first highest decrease in the value of surface tension corre-
of surfactant property in SNS and to compare it with synthetic sponds to the cmc of SDS. Then the subsequent increase in the SDS
surfactant, the successive addition of SDS and SNS solution is made concentration beyond cmc showed further reduction in surface
tension. When the pattern of surface tension reduction of SDS and
SNS was observed, they found to be similar. Both SNS and SDS had

Fig. 7. Effect of variation of SNS concentration on the conductance of NReSNS complex Fig. 9. Plot of surface tension (mN m1) as a function of concentration of SDS at 298 K
in the range of 2e50  C. from pre micellar to post micellar region.

Please cite this article in press as: Muntaha, S.-T., Khan, M.N., Natural surfactant extracted from Sapindus mukurossi as an eco-friendly alternate
to synthetic surfactant e a dye surfactant interaction study, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.01.023
6 S.-T. Muntaha, M.N. Khan / Journal of Cleaner Production xxx (2015) 1e6
Table 3
Values of thermodynamic parameters for dyeesurfactant ion pair formation.
Temperature Dyeesurfactant Equilibrium constant, Gibbs free energy,
( C) K (102 dm3 mol1) DG0 (kJ mol1)
20 NReSDS 380.91 25.70
NReSNS 8.61 16.46
25 NReSDS 385.95 26.16
NReSNS 8.61 16.74
30 NReSDS 344.85 26.32
NReSNS 8.64 17.03
lessened the surface tension. At the cmc concentration, the surface
tension value was greatly reduced in the presence of SDS and SNS
surfactant.
3.6. Thermodynamic parameters
The average of the reported molecular weights (Table 1) was
used to evaluate the thermodynamic parameters for NReSNS ion
pair formation. The theoretical model (Bracko and Span, 2000,
2001; Khan and Sarwar, 2006; Muntaha and Khan, 2014) was
implied for the determination of thermodynamic parameters for
NReSNS and NReSDS ion pair formation; the parameters are
expressed in Table 3.
Table 3 represents the values of equilibrium constant “K” and
Gibbs free energy “DG0” for both NReSDS and NReSNS ion pair
formation. For NReSDS and NReSNS, DG0 shows the similar trend.
The decrease in DG0 was observed when the temperature increased
from 20  C to 30  C in both the cases. The negative values of DG0 for
the NReSNS ion pair formation indicate the feasibility of the
interaction. It also expresses that the interaction is thermody-
namically favorable as the interaction is spontaneous. The values of
thermodynamic parameters for NReSDS ion pair formation are
slightly more than that of NReSNS. SNS contains bulky groups
which may hinder the interaction of NR with SNS resulting in
slightly less values of thermodynamic parameters for NReSNS ion
pair. This also suggests the use of SNS in place of SDS.
4. Conclusions
The natural surfactant solution was prepared. The pH-metric
titration was performed to determine the nature of surfactant
and found that SNS consists of two replaceable hydrogens which
can release on reacting with a base. The conductivity measurement
was carried out to determine the critical micelle concentration of
natural surfactant. The comparative interaction behavior between
cationic dye, natural surfactant and synthetic surfactant was
investigated using spectrophotometric, conductometric and sur-
face tension methods. The effect of temperature on the formation
dyeesurfactant complex was studied and it is concluded that the
formation of dyeesurfactant ion pair is favored by low temperature.
The spectrophotometric measurement of surfactant from pre to
post micellar region showed that the concentration of surfactant is
a very important factor because the interaction between dye and
surfactant and the dissolution both rely on surfactant concentra-
tion. The course of interaction of SNS and SDS with similar dye was
found to be comparable to each other. The surface tension mea-
surement for SNS and SDS was compared and it is found that both
SNS and SDS tend to have similar pattern. The values for equilib-
rium constant and DG0 were evaluated and it was found that the
interaction of NR with SNS is thermodynamically favorable. It is
suggested that SNS can be used as a natural alternative of the
synthetic surfactant.
Please cite this article in press as: Muntaha, S.-T., Khan, M.N., Natural surfactant extracted from Sapindus mukurossi as an eco-friendly alternate
to synthetic surfactant e a dye surfactant interaction study, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.01.023
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