Journal of Scientific and Innovative Research 2016; 5(6): 208-214

Available online at: www.jsirjournal.com

Research Article
Effects of electrolytes on the surface and micellar
ISSN 2320-4818
JSIR 2016; 5(6): 208-214
characteristics of Sodium dodecyl sulphate surfactant
© 2016, All rights reserved
Received: 02-12-2016
solution
Accepted: 31-12-2016
Hailu Demissie*, Ramesh Duraisamy

Hailu Demissie Abstract

Department of Chemistry, College
of Natural Sciences, Arba Minch
University, Arba Minch, Goma- The effect of some electrolytes (namely sodium acetate and calcium acetate) on their critical micelle
Gofa Region, Ethiopia (East concentration (CMC), have been determined by spectrophotometric, conductometeric and surface tension
Africa) measurement method at 298K, 308K and 318K. From the surface tension data physico-chemical properties
Ramesh Duraisamy
such as surface excess concentration (Γ max) and minimum area per molecule (Amin) at surface have been
Department of Chemistry, College obtained. From the observed CMC data, free energy of micellization (∆Gmic), entropy change of micellization
of Natural Sciences, Arba Minch (∆Smic), and enthalpy change of micellizaton (∆Hmic) for the studied surfactant solutions with or without
University, Arba Minch, Goma- electrolyte have been obtained. The results have been interpreted in light of inter-molecular interaction.
Gofa Region, Ethiopia (East
Africa)
Keywords: Adsorption conductance, Critical micelle concentration, Micellization, Surfactant,
Thermodynamic parameters.

INTRODUCTION
Surface science is a fascinating scientific subject that defines the issue of amphiphiles, and more
specifically micellar and thermodynamic characteristics of surface active substances called surfactants.
Surfactant is coined word from surface active agent that is applied to molecules that migrate to interface
between two insoluble physical phases. Surfactants are amphiphilic, which was created by Paul Winsor
50 years ago [1] and comes from the Greek words; amphi, mean both and phillos expresses friendship,
and the term relates to the fact that all surfactant molecules consists of at least two parts. When the fluid
is water one usually talks about the hydrophilic and hydrophobic parts respectively. The hydrophilic part
is referred to us the head group and the hydrophobic is the tail.

When the surfactants are dispersed in aqueous solution it adsorbs at interface and self assemble in bulk
solution. Adsorption is the concentration of surfactants at interface, while self assembly is the
aggregation of surfactants into structure called micelle. Both these processes are driven by the
hydrophobic tails being expelled from solution. Surface active agents also aggregate in solution forming
micelles [2, 3]. The formation of micelles is generally understood in terms of hydrophobic effect which is
the main driving force. Besides, the hydrophobicity of surfactant molecules, the hydrophobicity of
solvent molecules is also important in understanding micellization process. Addition of small amount of
organic solvent has been known to produce marked change in the critical micelles concentration (CMC)
of ionic surfactants due to the tendency of the added solvent either to break or make the water structure
through solution of hydrophobic part of organic solvent [4]. Moreover, formation of micelles has been
observed in solvent having high degree of hydrogen bonding.

The driving force for surfactant adsorption is the lowering of free energy of the phase boundary [5].
Formation of dimmers, trimmers or other polymers in amphiophilic solutions reduces the contact area
Correspondence: between the hydrocarbon chain and the aqueous solvent and resulting to decrease in free energy. When
Dr. Ramesh Duraisamy
the hydrocarbon chain is long enough, hydrophobic driving force results in large scale association
Department of Chemistry, College
of Natural Sciences, Arba Minch structure (micelles). Adsorption of surfactant molecules at interface lowers surface tension (γ) and higher
University, Arba Minch, Goma- the surfactant adsorption makes the larger reduction of γ, where γ is interfacial tension and given in
Gofa Region, Ethiopia (East mJ/m2 or mN/m. Surfactant self-assembly in aqueous solutions has been investigated both
Africa) experimentally and theoretically. Experimental measurements of properties such as electrical
conductivity, surface tension, dye solubilization capacity, osmotic pressure, or light scattering intensity

208
as a function of surfactant concentration shows a sharp transition in the behavior of surfactants by altering the solvent property and such studies
value of the measured property over a very narrow range of surfactant provide us information of both fundamental and applied importance.
concentration. This surfactant concentration is identified as the critical Solvent property can be varied in different ways, for example, (i) by
micelle concentration (CMC). At surfactant concentrations below the taking pure solvents of different polarity, (ii) by taking mixed solvents
CMC, mainly singly dispersed molecules and possibly some small containing either mixtures of water and non aqueous solvent or mixtures
aggregates such as dimers and trimers are present in the solution. In of two non aqueous solvents, and (iii) by adding electrolytes or non
contrast, at concentrations above the CMC, micelles containing a large electrolytes to water or any other solvent.
number of surfactant molecules are formed in the solution. At relatively
low or moderate surfactant concentrations, these aggregates can assume Surfactants
a variety of shapes such as spherical micelles, slightly asymmetrical
globular or ellipsoidal micelles, and large rod like micelles which may From the commercial point of view surfactants are classified according
be rigid or flexible and spherical bilayer vesicles. At larger to their use. The most accepted and scientifically sound classification of
concentrations of surfactants in solution, liquid crystalline aggregates surfactants is based on their dissociation in water.
can come into existence. Physico-chemical studies of surfactant
Anionic surfactant
solutions are important from theoretical as well as applied points of
view. Anionic surfactantis dissociated in water to form amphiphilic anion, and
a cation,which is in general, an alkaline metal (Na+, K+) or a quaternary
Polymers in aqueous and non-aqueous media and there interaction with
ammonium. They are the most commonly used surfactants. They
various surfactants micelles have widely been studied in the light of
include salts ofalkyl benzene sulfonic acid (detergents), fatty acids
aggregation, hydrogen bonding, geometry, correlation time,
(soaps), laurylsulfate (foaming agent), di-alkyl sulfosuccinate (wetting
conformation, hydrodynamic and thermodynamic studies. However,
agent), lignosulfonates(dispersants) etc. Anionic surfactants accounted
studies on the effect of electrolytes on the surface and micellar
50 % of the world production.
characteristics of surface active compounds is only limited. Therefore,
in this proposed research work was investigating the effects of some Cationic surfactants
salts on the surface and micellar characteristics of an anionic surfactant
such as sodium dodecyl sulphate (SDS). This current study specifically Cationic surfactants are dissociated in water into an amphiphiliccation
focused to examine the effect of sodium acetate and calcium acetate on and an anion, most often of the halogen type. A very large proportion of
the micellar characteristics of SDS on aqueous solution. Furthermore, this class corresponds to nitrogen compounds such as fatty amine salts
this research to explore the effect of these studied salts on surface and and quaternary ammoniums, with one or several long chain of the alkyl
thermodynamic properties of aqueous SDS solution. type, often coming from natural fatty acids. These surfactants are in
general more expensive than anionic, because of the high pressure
Review of Literature hydrogenation reaction required during their synthesis. As a
consequence, they are used only in cases where no cheaper substitute is
Surfactant and their Properties
available, i.e. (1) as bactericide, (2) as positively charged substance
An amphiphilic substances exhibit a double affinity, which can be which is able to absorb on negatively charged substrates to produce
defined from the physico-chemical point of view as a polar-apolar antistatic and hydrophobant effect, often of greater commercial
duality. A typical amphiphilic molecule consists of two parts: i.e., a importance like as corrosion inhibition.
polar group which contains heteroatoms, means atoms such as O, S, P,
Nonionic surfactants
or N included in functional groups called alcohol, thiol, ether, ester,
acid, sulfate, sulfonate, phosphate, amine, amide etc. On the other hand, Nonionic surfactantsareabout 45% of the overall industrial production.
an essentially apolar group which is, in general, a hydrocarbon chain of They do not ionize in aqueous solution, because their hydrophilic group
the alkyl or alkyl benzene type, sometimes with halogen atoms and even is of a non dissociable type, such as alcohol, phenol, ether, ester, or
a few non ionized oxygen atoms. Surfactants are amphiphilic molecules, amide. A large proportion of these nonionic surfactants are made
that dynamically associate in aqueous solution above as certain critical hydrophilic by the presence of a polyethylene glycol chain, obtained by
concentration termed as CMC to form large molecular aggregates of the poly condensation of ethylene oxide. They are called poly
colloidal dimensions termed as micelles and above the CMC, there ethoxylated non ionics. In the past decade glucoside (sugar based) head
exists a dynamic equilibrium between the monomers and micelles [2, 6, 7]. groups have been introduced in the market, because of their low
At surfactant concentrations near CMC, aggregation of surfactant toxicity. As far as the lipophilic group is concerned, it is often of the
monomers occurs to form roughly spherical or ellipsoidal shaped alkyl or alkyl benzene type, the former coming from fatty acids of
micelles. Each micelle is composed of a certain number of surfactant natural origin. The poly condensation of propylene oxide produces a
molecules that dictate the general size and geometry of the particular polyether which (in opposition to polyethylene oxide) is slightly
micellar system. hydrophobic. This polyether chain is used as the lipophilic group in the
so-called poly ethylene oxide-propylene oxide block copolymers, which
As hydrophobic interaction,the solute has either full or partial
are most often included in a different class, e.g. polymeric surfactants.
hydrophobicity on the type of solvent–solute interaction on colloids.
When the solutes are amphiphilic innature, hydrophobic interaction Amphoteric (ampholytic) surfactants
leads to two significant phenomena, viz. adsorption and aggregation [8].
This interaction is not water specific and therefore solvophobic When a single surfactant molecule exhibits both anionic and cationic
interaction is used as a general term. Thus, self-organization of charges it is called amphoteric andzwitterionic. This is the case of
amphiphiles takes place only in the presence of a solvent and result the synthetic products like betaines or sulfobetaines and natural substances
solvent properties can be greatly influence the adsorption and such as amino acids and phospholipids. Amphotric surfactants can be
aggregation phenomena. Therefore, studies are made on the aggregation anionic (negatively charged), cationic (positively charged) or non-ionic

209
(no charged) in a solution, depending on the acidity or pH of the water. slope of the dependence k =f(c). The value of CMC is the intercept of
In acidic pH solutions, the molecule acquires a positive charge and two linear plots with mutually different slopes [13].
behaves like a cationic surfactant, whereas in alkaline pH solutions they
become negatively charged and behave like an anionic one. Surfactants and Surface Tension

Amphoteric surfactants are compatible with all other classes of Surface tension is due to asymmetric cohesive force at a surface. The
surfactants and are soluble and effective in the presence of higher Surface tension of liquids causes the formation of drops and is related to
concentrations of electrolytes, acids and alkalis. These surfactants may the attractive force between the molecules. These attractive forces are
contain two charged groups of different signs linked by a spacer, which dipole-induce-dipole forces and hydrogen bonding. In the bulk liquid, a
may be rigid or flexible, hydrophilic or hydrophobic, typically 2-8 molecule senses the equal attractive force in all directions, while for the
bridging atoms [9, 10]. Whereas the positive charge is almost always molecule at the surface of this attraction is lacking in one direction. This
ammonium, the source of the negative charge may vary (carboxylate, asymmetry is the origin of the surface tension. The surface tension is
sulphate, and sulphonate). These are mild with high foaming properties, reflection of the cohesive force in liquid, and the surface tension is
like an example of amphoteric surfactant alkyl betaine [2]. equivalent to surface free energy. Therefore it can be represented in
energy units, erg/cm2 or mJ/m2. In turn, the cohesive energy is a
Effect of Temperature on CMC function of the strength of the dispersion force in a liquid. Surface
tension is a measure of the free energy of the surface per unit area. It
The effect of temperature on the CMC of ionic surfactants is not straight can be thought of as the work required expanding the surface by a unit
forward [4], for instance, reported that when the temperature is increased, area. The surface tension of a pure liquid is a constant value at the given
the CMC first decreases, then undergoes through a minimum, and liquid.
finally increases. Other researcher [11] has observed a similar pattern
with nonionic surfactant solutions. Effect of cosolute on surface tension

This ups and down variations always occurs when two opposite effects In an aqueous system, added component can affect the surface tension
are competing. On one hand, an increase in temperature can bring a in three different ways. Organic water soluble material such as ethanol
reduction in the hydration of the surfactant hydrophilic group; this is the normally decreases the surface tension monotonically with increasing
well-known desolvatation effect which is responsible for the cloud point concentration. This is due to the preferential adsorption of organic
phenomenon of nonionic surfactant solutions. This effect tends to drive molecules at the liquid air surface. Surfactants on the other hand show a
the surfactant out of the aqueous solution and thus it favors the very large reduction in surface tension at very low concentration up to
formation of micelles, i.e., it decreases the CMC. On the other hand, an the CMC, where after the surface tension is practically constant. At
increase in temperature results in an increasing disorder in the structure concentration higher than CMC all additional surfactant will form new
of water phase, in particular the molecules which are located next to the micelles thus keeping the surfactant concentration (unimer activities)
surfactant hydrophobe. The higher in disorder, the less defined the more or less constant. Electrolytes normally increase the surface
direction of the unfavorable polar/apolar contact, and as a consequence tension, due to the reason is that the electrolytes are depleted from the
it becomes the weaker. Thus, the hydrophobic effect which drives the surface i.e., there is a negative adsorption of the ion at the liquid-air
surfactant molecule "tail" out of the water phase is also reduced when surface [14].
temperature is increased.
Effect of salt concentration
Effect of Co-solute on CMC
Addition of salt in surfactant solution is another way of reducing CMC
The role of co-solute/solvent in the process of formation of micelles in of surfactant. In general, repulsive forces between the head groups of
surfactant solution is of considerable interest both from the fundamental ionic surfactants are fighting against the aggregation. In the presence of
and the applied view points since application of surfactants in many salt, the repulsive forces of head group of SDS monomer decreases due
physic-chemical and interfacial phenomena largely depend on it [2]. to the electrostatic shielding effect resulting in the formation of micelle
Solublizing capacity, surface and micellar characteristics and at lower cmc [15, 16]. They further explained that electrical double layer
detergency of amphiophilic compounds are sensitive to the nature of was compressed due to the increased electrolyte concentration resulting
added cosolute/solvent and temperature [12]. in the reduced electrostatic attraction between ions and the micelles. The
As(V) replaces Cl- ions in CPC and arsenic solution, the As(V) binds
Principles of Determination of CMC closely with CPC ions and decreases the electrical charge on the surface
and reducing CMC [17]. As a result, non-trapped metals pass through the
The determination of CMC is generally based on the localization of the membrane leading to the lower rejection [17, 18]. Xuet al. reported that
position of a breaking point in the concentration dependencies of the cadmium removal efficiency decreased from 95% to 75% at NaCl
selected physical or chemical properties of surfactant solutions. Because concentration of less than 20 mM [15]. It could be due to the competition
of the surface activity of these substances, measurements of the surface between Cd2+ and Na+ ions to get at the micelle surface, and due to the
tension of surfactant solutions represent the principal method of CMCs formation of complex of Cl- and metal. The decrease of chromate
determination. However, it is rather tedious and time-consuming (CrO42-) removal from 1 to 0.15 mM when NaCl concentration
procedure. In the case of ionic surfactants, the utilization of increased from 1 mM to 500 mM. Aoudia et al. [19] reported that Cr3+
electrochemical measurements is much more convenient, especially the removal was also reduced with the addition of NaCl. In contrary, the
measurements of the electrical conductivity of their solutions with addition of NaCl has negative effect on the reduction of metal removal
varying concentration. The conductivity of any solution are directly and the formation of metal chloride. Basar et al. [20] explained that with
proportional to the concentration of its ions. The point, where the the increase of NaCl from 2 mM to 100 mM, CTAB rejection increased
micelle formation starts, is indicated by the breaking point in from 68% to 98%. On the contrary, LABS rejection rate decreased
concentration dependence of specific conductivity (k). It is easy to find slightly from 38% to 34% at the salt concentration of 2 mM and 100
the breaking point, because it marks a significant change of the linear mM, respectively. Sampler et al. [21] also reported the similar result of

210
reduction of heavy metals (Cd 2+ , Cu2+, Ni2+, Pb2+, Zn2+) when NaCl Methods
was added in the surfactant SDS and alkylbenzenesulfonate.
Determination of critical micelle concentration
Thermodynamics of micellization
UV-Visible absorption spectroscopic method
Thermodynamic free energy of micellization (∆Gomic) for ionic
surfactants with or without cosolutewas determined by using the Absorbance of sparingly water soluble dye, p-dimethylaminoazo
following equation reported earlier [22]. benzene, mixed with surfactantsolutions with or without the salt
(electrolyte) was measured using UV-Visible spectrophotometer.
∆Gomic= (2–β) RT lnXcmc Spectral measurements were performed using the blank solution as a
reference. The absorption vs. concentration of surfactant was plotted
Where β is counter ion dissociation constant, R(8.314 J k-1mol-1 )is the and the CMC is determined from the inflection point of the curve [23].
gas constant, T the temperature in Kelvin and XCMC stands for the CMC
in the mole fraction unit. For nonionic surfactant solution with or Conductivity measurement
without cosolute standard Gibbs free energy of micellization was
obtained as: ∆Gomic = RT lnXcmc Conductance of surfactant solution was measured using a digital
conductivity meter connected with a dip type conductivity cell. The cell
The standard entropy of micelle formation (∆Somic) was calculated from constant was determined by measuring the conductance of standard KCl
the temperature dependence of standard Gibbs free energy of solution using the relation:
micellization using the relation:
Specific conductance (k) = observed conductance x (ℓ/a)
∆Somic= -∂ (∆Gmic) /∂T
where ℓ/a =cell constant, ℓ is distance between the two electrodes in the
The Standard enthalpy of micelle formation (∆Homic) was derived from cell and a is surface area of each electrode. The value of cell constant
either Gibb’s Helmoltz equation: ∆Homic= was obtained from observed conductance and the specific conductivity
o o
∆G mic + T∆S mic of a standard solution of 0.1M of KCl. CMC value of the surfactants
were obtained from the break-point of the plot of specific conductance
Surface excess concentration as a function of surfactant concentration [23].

In the case of surfactants the concentration of solute at the surface is Equivalent conductance at infinite dilution(Λo): The Equivalent
higher than that in the bulk solution. This difference of concentration of Conductance at infinite dilution was determined from the molar
solute in the bulk and at the surface is called surface excess conductance (measures the efficiency with which a given electrolyte
concentration (Γ). This surface excess concentration (Γ) at air liquid conducts electricity in solution) of the studied surfactant solution at 298
interface can be calculated using Gibbs adsorption equation: K, 308 K and 318 K. Equivalent conductance (Λ) of surfactant solutions
were calculated from:
𝑑𝑌
Γ = (2.303nRT)-1
𝑑𝑙𝑜𝑔𝑐
Λ = (1000 x k) / C
-1 -1 𝑑𝑌
where, R is gas constant(8.314JK mol ), is slop value of the pre
𝑑𝑙𝑜𝑔𝑐 where, k is specific conductance (Scm-1) and C is normality of solution
micelle plot between Y and log[surfactant], T is temperature in K and n in g.equ/dm3. Equivalent conductance at infinite dilution (Λo) was
is number of particle furnished by each molecule of the surfactant in obtained using Onsager equation:
solution (for SDS acting as bivalent, n=2).
Λ=ΛO–(AΛO+ B) C1/2
MATERIALS AND METHODS
Where, A and B are constants.
Materials and Apparatus
Surface tension measurement
Materials and apparatus which was used in the study are: Conductivity
meter for conductance measurement, conductivity electrode, Double Surface tension of surfactant solution in water was measured by drop
beam UV-visible spectrophotometer equipped with a pair of 10 mm weight method using a stalagmometer. The stalagmometer assembly
quartz tube, UV lamp, UV light cabinet, Stalagmo meter, Thermostat, consists of Pyrex glass bulb of spherical shape with an attached
magnetic stirrer, etc. capillary tube and the tip of the end is grounded. The surface tension of
the surfactant solutions under study was determined by multiplying the
Chemicals observed weight of one drop with the slope of the standard curve
between surface tension of liquid versus weight per drop. A plot of
Sodium dodecyl sulphate(BDH chemicals Ltd, England), potassium chl surface tension versus log of surfactant concentration was drawn. From
oride(99%, Blulux, Laboratory Ltd.), (p-dimethyl amino azo the break point of the plot, the CMC of surfactant was determined.
benzene(dye content: 85%, BDH chemicals Ltd, England),
Acetone(BDH chemicals Ltd, England), Sodium acetate (BDH RESULTS AND DISCUSSIONS
chemicals Ltd, England) and Calcium acetate (BDH chemicals Ltd,
England), Tolene (HPLC grade, Analytical reagent, CDH(P) LTD, Critical Micelle Concentration
India), ethanol(99% Hayman Ltd, England)and deionized water were
used for this study. Micellization occurs when surface active compounds form non-covalent
clusters in solution; this process is driven by the hydrophobic
effect(Rosen, M., 2004) each surface active agent can be characterized

211
by its critical micelle concentration (CMC). The formation of a micellar Further, addition of electrolyte causes a decrease in Amin. It is more
aggregates causea significant changes in physical properties, such as lower in the case of Ca(Ac)2. It is obvious since Ca2+ facilitate micelle
conductivity, molecular fluorescence and surface tension of surfactant formation than Na+, so that the surfactant monomers favor to
solutions. Therefore, for the determination of the concentration at which aggregation.
a surfactant forms a micelle, called CMC, it is possible to use
electrochemical or spectrtoscopic techniques and is detected as an Equivalent Conductance at infinite dilution (ΛO).
inflection point when physicochemical properties like surface tension
are plotted as a function of concentration. Equivalent Conductance at infinite dilution was obtained using Onsager
equation:
For the studied surfactant solutions, critical micelle concentration
(CMC) of SDS was determined by conductometric, surface tension and Λ=ΛO–(AΛO+ B) C1/2
UV-Visible absorbance spectroscopic techniques. Micelle formation is
where, A and B are constants.
indicated by the inflection point on the concentration dependent specific
conductivity (𝜘) plot and these are presented infigure1. Absorbance as A plot of Λ versus C1/2 is drown.The intercept of such plot gives ΛO
a function of SDS concentrations for SDS+Dye+H2O system is value and these values are also recorded and shown in table 2. It is
described in figure 2. The plot of surface tension versus log [SDS] is observed that an increase in temperature brings about an increase in the
presented in figure.3.The CMC values for aqueous surfactant solutions limiting conductance at infinite dilution (ΛO) for surfactant (SDS), due
of SDS using different methods were carried out and the data are to enhanced ionic mobility at higher temperature.
presented in Table 1.
Table 1: CMC values of surfactants from the literature
The break point in the concentration-conductivity curve can be
interpreted as sign of aggregation (shown in figure 4). The CMC values System / methods CMC (mM) at 298 K
for pure SDS solutions at 298 K, 308 K and 318 K are given intable.2 SDS by conductance 8.0
The CMC value of pure SDS aqueous solution obtained from SDS by surface tension 8.3
conductance (8.0 mM) and absorbance (7.8mM) methods are in fair SDS by absorbance 7.8
agreement. However, as usual CMC of SDS from surface tension
measurement (8.3 mM) is higher (figure.5). Average CMC value (8.1
mM) for SDS at 298 K was used in the subsequent calculation reported Table 2: Critical micelle concentration (CMC), surface excess
by Holmber et al. [2]. concentration (┌max) and minimum area per molecule (A min) for studied
surfactant systems with or without electrolytes
The CMC values were determined from the break point in plots of
absorbance as a function of [SDS] for SDS + dye + H2O solutions Γmax Amin
Temp. CMC ΛO x 10-1
containing sodium acetate or calcium acetate are presented in System (1x1010) (1x108)
(K) (mM) (µS m2 mol-1)
Table.2.CMC of the anionic surfactant (SDS) at 298K decreases with (molcm-2) m2
mixing 0.1M electrolytes(sodium acetate or calcium acetate). It may be
298 8.10 4.40 5.22 3.18
due to partial neutralization of anionic head group negative charge by
electrolyte cations [24]. Furthermore, CMC of SDS is markedly lower in SDS+H2O
308 8.17 6.00 - -
the cases of added sodium acetate and calcium acetate. (Figures 6 & 7).
Thus, further decrease in the CMC of SDS on adding Ca (Ac)2 is 318 8.25 8.70 - -
attributed to more effective head group charge neutralization by bivalent
Ca2+ than monovalent Na+. Surfactant head group charge neutralization SDS+0.1M
298 7.65 - 4.23 4.501
NaAc
by electrolytes cation facilitates micilization and hence lower CMC.
SDS+0.1M
298 6.01 - 3.32 3.92
Ca(Ac)2
Surface Physico-Chemical Properties

Surface excess concentration (max)

The surface excess is a useful measure of effectiveness of adsorption at

the interface. The effectiveness of adsorption is an important factor for
determining the properties of surfactants like wetting, contact angle,
foaming,etc. The calculated values for maxfor the studied systems at
298 K are presented in Table 2. As it can be seen, the max for SDS at
298K is lower in the case of Ca(Ac)2 than for NaAc. This may be
because of divalent Ca2+ promotes micelle formation by reducing
surfactant head group repulsion.The value of minimum area per
molecule(Amin) of surfactant(SDS) were obtained using,

𝟏𝟎
Amin= x1013
𝑵
Figure 1: Plot of absorbance (A) as a function of concentrations of [SDS]+water
where, N is Avogadro’s number and Amin is minimum area per molecule system at 298K [CMC] = 7.9mM
in nm2

212
 Log[SDS]

Figure 6: Plot of surface tension Vs log[SDS] for SDS + NaAc + H2O system
Figure 2: Plot of absorbance (A) as a function of concentrations of [SDS]+0.1M at 298K
NaAc+ Water system at 298 K

Log[SDS]

Figure 7: Plot of surface tension Vs log[SDS] for SDS + Ca(Ac)2 + H2O system
at 298K
Figure 3: Plot of absorbance (A) as a function of concentrations of [SDS]+0.1M
Ca(Ac)2+water system at 298 K
Thermodynamic parameters of micellization

The main reason for micelle formation is the attainment of a minimum

free energy state. The main driving force for the formation of micelles is
the increase of entropy that occurs when the hydrophobic regions of the
surfactant are removed from water and the ordered structure of the water
molecules around this region of the surfactant molecule is lost.

Any process that leads to free energy decrease will occur spontaneously
because it leads to the formation of a more stable system. Micelle
formation is, therefore, a spontaneous process. The standard free energy
change of micellization(∆G0mic) values for studied surfactants with or
without electrolyte(sodium acetate and calcium acetate) are all
negative(∆Gºm< 0) suggesting the feasibility of the micellization
(shown in table.3). The free energy change of micellization becomes
Figure 4: Specific conductance Vs[SDS] at 298K, 308K and
more negative on mixing the electrolytes (especially calcium acetate)
318K.(CMC=8.0mM)
and also with rise in temperature from 298K to 308K and to 318K.
Therefore, addition of electrolytes in a surfactant solution irrespective of
the nature of added electrolyte as well as higher temperature both
enhances the feasibility of micellization process. Though the
micellization process is generally opposed by endothermic enthalpy
change, yet the driving force in micellization process is the entropy gain
[25, 26]
. On mixing of electrolytes, ∆G0mic further decreases (become
more negative) it shows that ionic salts in aqueous surfactant solution
facilitates micellization.

The positive ∆Sºmic values are attributed to the disruption of water

structure around the hydrocarbon part of surfactant molecule as it
transfers from the aqueous bulk phase to non aqueousmicellar interior,
Log[SDS] when the electrolytes (0.1M sodium acetate or calcium acetate) were
Figure 5: Plot of surface tension Vs log[SDS] at 298K(CMC=8.3mM) added, the entropy of micellization increases. It is because in the
presence of electrolytes in the aqueous solution undergo enhanced water
structure due to ion hydration and entropy gain by transfer of surfactant

213
hydrophobic chain from bulk to micelle involves enhanced water 5. Bahadur, P., Parikh, J., Varade, D. (2003) “Adsorption characteristics and
structure disruption [25, 26]. micelle formation of two cationic surfactants and their mixtures in aqueous
solution”, Tenside Surf. Det., 40(4):215-219
Table 3: Thermodynamic parameters of Micellizationfor studied 6. Atkins P.W, (2001), Elements of physical chemistry, Oxford University
Press, 3rd edition, New York, pp.405-407
surfactant systems at 298k
7. Rusdi, M., Moroi Y.,Hlaing T . and Matsuoka K., (2005) “Micelle
formation and surface adsorption of octa ethylene glycol mono alkyl ether”,
Temp. ∆Gmic(kJmol -
∆Smic(kJmol -1
∆Hmic(kJmol -

System Bulletin of Chemical Society of Japan, Vol. 78(4) pp.604-610.

1 -1 -1 1
(K) K ) K ) K-1) 8. Tharwat, F., F. Th, (2009) “Colloids in Agrochemicals”, Journal of
Colloids and Interface Science, Vol.5,p/14.
SDS+H2O 298 -43.40 0.122 -7.044 9. Menger, F.M. and C.A. Littau, (1991) “Germini surfactants”, Journal of
Synthesis and Properties of Surfactants, New York, Vol.412, pp.75-83
10. Menger, F.M. and Littau, C.A.(1993) “Germini surfactants”, Journal of
SDS+0.1MNaAc 298 -46.69 0.133 -7.01 New class of Self Assembling Molecules., p.21
11. Crook, (1963) “Temperature dependence of surface phase behavior and
micelle formation of some nonionic surfactants”, Journal of Phys.Chem.,
SDS+0.1MCa(Ac)2 298 -49.97 0.140 -7.28
Vol.107, p.965
12. Dubey N., (2008) “Conductometricstudy of interaction between Sodium
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Conductometery, UV-visible spectrophotometeric and surface tension 13. Jahirul Islam, M., Choudhuri, M. M.R., Shahed, S.M.F. and Subhan,
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increasing the valence of cation of the electrolyte. Surface
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excess concentration for the studied systems is in the order of, using micellar enhanced ultrafiltraion with hollow fiber membrane”,
Colloids and Surfaces A: Physico-chemicaland Engineering Aspects,
(SDS + Ca(Ac)2 + H2O) < (SDS + NaAc + H2O) < (SDS H2O)
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 Standard Gibbs free energy change of micellization (∆G0mic)
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furtherdecreases showing that the presence of these 17. Geocol, H., Ergican, E., Fuchs, A. (2004) “Molecular level separation of
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studied surfactant. The decrease of CMC on mixing metal ions from dilute solutions using micellar enhanced ultrafiltration”,
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