Evaluation of interaction energies and thermodynamic

IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
__________________________________________________________________________________________
Volume: 02 Issue: 08 | Aug-2013, Available @ http://www.ijret.org 442
EVALUATION OF INTERACTION ENERGIES AND THERMODYNAMIC
PROPERTIES IN BINARY MIXTURE OF REACTIVE ORANGE 107 DYE
+ TRITON X-114 SURFACTANT AT 303.15, 313.15 & 323.15K: AB INITIO
METHOD AND EXPERIMENT
Appusamy Arunagiri1
, Komal Priya2
, Duraimurugan Alias Saravanan3
, Ponnusamy Kalaichelvi4
,
Ramalingam Anantharaj5
1, 2, 3, 4
Department of Chemical Engineering,National Institute of Technology Tiruchirappalli,
Tiruchirappalli, 620015Tamilnadu, India.
5
Department of Chemical Engineering, Faculty of Engineering, University of Malaya,
50603Kuala Lumpur, Malaysia, anantharaj@um.edu.my
Abstract
It is critically important to understand the interactions between surfactant triton X-114 and reactive orange 107/water due to
decolorization of waste water by surfactants. In this work, the structure of surfactant triton X-114, reactive orange 107 dyes, water,
surfactant triton X-114+ reactive orange 107, surfactant triton X-114 + water and reactive orange 107dyes+water were optimized
systematically at HF/6-31G level. It was found that reactive orange 107 is close to the surfactant triton X-114 structure. There exist
CH--π interaction, π--π interaction n--H interaction and n--π interactions between surfactant triton X-114 and reactive orange 107
dyes. The interaction energy between surfactant triton X-114 and reactive orange 107 dyes, water is -92073.8853, 4303.4720 kJ.mole-
1
, showing preferential adsorption of reactive orange 107 by surfactant triton X-114,in agreement with experimental results of
surfactant triton X-114 + reactive orange 107 dyes in binary mixture at 303.15, 313.15 and 323.15K.
Keywords:Ab initio method, interaction energy, cloud point extraction, reactive orange 107dyes, triton X-114surfactant,
thermodynamic properties
---------------------------------------------------------------------***------------------------------------------------------------------------
1. INTRODUCTION
Textile industries consume large amount of water and dyes for
the wet processing of textiles, especially for coloring cotton,
wool, silk and polyamide textiles. After wet processing, the
colored effluents discharged from these industries are not
found to be environmentally friendly and economically viable
due to very low concentration of dyes present in these
effluents. The presence of very low concentration of dyes in
effluent discharged from these industries is highly visible and
undesirable due to their chemical structure which causes
higher thermal stability, low reactivity. In addition, dyes are
highly resistant to fading when exposed to light, water,
organic and inorganic solvents. Dyes have a synthetic origin
and complex aromatic molecular structures and therefore it
possess more stable and difficult to biodegradation, but it’s
highly soluble in water. Dyes have also been considered to be
responsible for changing properties of waste water, and thus
the waste water has high COD, large amount of suspended
solids, largely fluctuating pH,high temperature,
unboundcolorants, dye impurities, auxiliaries and surfactants.
Thus, they affect dyeing process efficiency, decolorization and
degradedyeing waste water. Dyes in waste water have
carcinogenic, mutagenic and bactericide properties [1-5].
According to the directive of ecological and toxicological
association of dyes and organic pigments manufactures view,
the removal of dyes from colored effluent is not an easy task
but it is essential to protect the environment and minimize the
teratogenic human health effect. On the other hand, the
environmental protection agency proposed limit required less
than 5 ppm of dye content in waste water from 1500 p.m. by
2015 or near the future [6-8]. So far, various methods have
been employed in wastewater treatment plant but they are
inefficient for such depth removal of dyes. The various
methods are adsorption, oxidation, coagulation, flocculation,
chemical degradation, ozonation, enzymatic,catalyst,
surfactant, photo degradation and combination of
physiochemical and biological treatment. Therefore, the
development of new technologies is of particular interest in
providing environmentally friendly solution for dyes-free
clean water. But it is a very serious challenge to the textile
industry.

__________________________________________________________________________________________
Cloud point extraction (CPE) as an extraction method has
been extensively used in the separation and purification
process because of mild operating condition and very
straightforward processes [9]. CAE process can be easily
overcome the disadvantages of the above conventional method
for decolorization of degradation of wastewater plants. At a
certain temperature, aqueous solution of a nonionic surfactant
becomes turbid. With further increase of temperature, solution
separates into two phases such as surfactant rich phase and an
aqueous phase.Surfactant rich phase has small volume
compared to the solution and so- called coacervate phase,
whereas the aqueous rich phase containing surfactant
concentration slightly above the critical micelle concentration
(CMC) [10]. This temperature is known as cloud point
temperature (CPT) of the surfactant. The cloud point is strictly
defined as a particular surfactant concentration (e.g., 1wt %)
due to phase boundary between two phases which is fairly
independent of concentration.The cloud point is generally
quite close to the lower consulate solution temperature. At the
cloud point temperature, the solute present in aqueous solution
of nonionic surfactant is distributed between two phases [11].
This phenomenon is known as cloud pointextraction (CPE)
[12,13].
The process efficiency depends on the surfactant types and
chemical structure because there are several physical and
chemical interactions involved in the formation of a complex
between surfactant and dyes at a cloud point temperature [14-
16].On the other hand there is some possibility for structural
orientation between similar aromatic ring structure of
surfactant and dyes such as CH--π interaction,π--π interaction,
n--π interaction [17-20]. Apart from these interactions, the
charge -- charge interaction and hydrogen bond with neutral
molecule interaction can also play important role in the
separation of dyes from waste water [21]. In order to
understand the reactivityof dyes with surfactant, the molecular
identification of structure and hetero atom in the structure and
their interaction energy are strongly needed to be clarified. But
the molecular level analyses of dyes and surfactant have not
been reported on elsewhere. It is well known that the
thermodynamic properties could be explained very clearly
about the interaction between two compounds such as excess
molar volume [22] and deviation of refractive index, viscosity
and surface tension [23-25].
Recently, ab initio molecular orbital calculation has become a
powerful tool for studying intermolecular interactions and
structural orientation. The intermolecular interaction and
structural orientation can give detailed information about the
ability, feasibility and efficiency of the process, in order to
minimize the experimental cost and have chosen potential
candidate for the particular separation process. Since the
interactions energy control the structural assemblies and their
properties in the mixture. Further, the removal of trace amount
of reactive dyes from aqueous solution by current
conventional method is not effective because of its chemical
and physical resistant to the process. However the presence of
heteroatoms in the aromatic structure of reactive orange 107,
these species are involved in a great variety of chemical and
physical interactions in the decolourization and recovery
process using active absorbent, surfactant and catalyst. It is
believed that a deep knowledge of these interactions can be of
fundamental importance to understanding the intrinsic nature
of the microscopic forces that regulate the phase equilibrium
in waste water treatment.So far as we know, there are no
published quantum chemistry studies on the interaction
between complex formed between triton X-114 surfactant and
reactive orange 107 dye and /or water molecules using ab
initio methods with 6-31G* basis set.
The aim of the present work is to study the interaction energy
of the complex formed between surfactant triton X-114 +
water, surfactant triton X-114 + reactive orange 107dyes and
reactive orange 107 dyes + water system using ab initio
methods with 6-31G* basis set.To make the comparison and
understand the behavior of interaction parameters in the above
complex systems have been studied through cloud point
extraction (CPA) process.Density, viscosity and refractive
index of pure and mixture of surfactant triton X-114, reactive
orange 107 dyes and water were measured at 303.15, 313.15
and 323.15K. From the measureddata,the thermodynamic
properties of these binary systems were calculated.It is very
easy to understand the behavior of surfactant triton X-114 with
reactive orange 107 dyes andwater molecules at different
temperatures. In addition, the molecular aggregation in binary
mixture can also be analyzed.
2. COMPUTATIONAL DETAILS
MOLDEN visualization package [26] has been used to prepare
the chemical structure of triton X-114 surfactant (Figure 1),
reactive orange 107 dyes(Figure 2) and water. The complex
system of Triton X -114 surfactant with reactive orange
107dyes (Figure 3), Triton X -114 surfactant with water
molecules and reactive orange 107 with water molecules were
drawn using dummy atom initially. After geometry
optimization, the complex system does not have dummy atom
which is making a barrier between these two molecules at gas
phase studies. These similar concepts have been used earlier
by Meng et. al. [27] and Turnet et.all,[28] for ab initio
calculations.
Quantum chemical calculations were performed using Hartee
Fock (HF) theory with 6-31G* basis set. The geometry
optimizations were carried out using HF/6-31G* level of
theory. At the same level of theory, the fundamental
vibrational frequency calculations were carried out to ensure
the true minima. The total electronic energies for triton X-114
surfactant, reactive orange 107dyes, water and their complex
were corrected with the basis set superposition error using
Boys-Bernardi counterpoise techniques [29]. All theoretical

__________________________________________________________________________________________
calculations were performed using the Gaussian03 software
package [30].
3. EXPERIMENTAL
Triton X-114 surfactant, purchased from Sigma Life Sciences,
India, was used as nonionic surfactant. It is highly pure and
water-soluble liquid. Triton X-114 contains approximately 8 -
9 ethoxy units per molecule (density at 298.15K is 1.058 g.
ml-1, Mol. Wt.: 537, λmax: 223nm), and is abbreviated as
surfactant triton X-114 (Figure 1). The critical micelle
concentration (CMC) of surfactant triton X-114 is 2.1×10−4M
at 298.15K and cloud point temperature is 298.15K[31].
Reactive Orange 107dye (Mol.Wt:566.49, density: 1.7 g/ml,
λmax: 411 nm) purchased from Nuchem chemicals,
Ahmedabad, India was used as solute (Figure 2). JASCO UV-
Vis spectrophotometer was used for recording
absorptionspectra and absorbance measurements using 1 cm
glass cells and it was calibrated.The calibration curve for
reactive orange 107 dyes is shown in Figure 4.
50 ml aqueous micellar solutions were prepared with different
concentrations of solute and surfactant. The concentration of
reactive orange dye used was 25 ppm. Surfactant triton X-114
concentration was varied from 0.01 M to 0.1 M. In various
literatures lower concentrations of surfactant were used, here
we increased the concentration of surfactant up to 0.1 M for
more efficient results. Solutions were heated above
CPT(298.15K) at three different temperatures 303.15K,
313.15K, and 323.15K. The temperature above the cloud point
temperatureof surfactant triton X-114 was taken for efficient
cloud point extraction to take place. The solution separated
into two phases above cloud point temperature. The volume of
surfactant-rich phase and dilute phase were noted down. Then
the concentration of reactive orange 107 dyes in dilute phase
was determined by UV- Spectrophotometer.The viscosity of
the separated phases was measured through Brookfield
Viscometer LVDVII+PRO and the refractive index was
measured by Deep Vision Refractometer(Guru Nanak
Instruments, New Delhi). The refractometer was calibrated
using water.For the measurement of density, 5 ml specific
gravity bottles were used.
4 .RESULTS AND DISCUSSIONS
The quantum chemical calculation and experiments were
conducted using reactive orange 107 deys as a model anionic
dye components and non-ionic surfactant triton-X 114. There
are different kinds of interaction can exist between dye and
surfactant / water molecules.It should be discussed in order to
understand the physical, chemical and structural interaction.
Dye solubilization results from the following interactions [32]:
• Dye is included into the polyoxyethylene exterior of
micelles by hydrophilic interactions.
• Hydrophobic interactions result in absorption of dye
into the hydrophobic core of surfactant micelles.
In non-ionic surfactants with the same hydrophobic group, as
the ethylene oxide chain length decreases which cause
micellize size increases whereasthe dye hydrophobicity
decreases that cause solubilization tendency decreases.
The possible physical and chemical interaction between
surfactant triton X-114 and reactive orange 107 dyes in the
mixture such as van der Waals interactions between alkyl
chains, hydrogen bond interaction with neutral molecules,
charge-charge interaction, n(O,N,S)--H interaction, CH-π
interaction,π--π interaction, n(O,N,S)--π interactions [17-20].
There are certain interactions between water and surfactant
molecules which affect the micellization of surfactant
molecules and solubilizaton of dye [33].
(i) Steric and electrostatic interactions between
surfactant hydrophilic moieties and water,
(ii) Conformational effects associated with hydrocarbon-
chain packing in the micellar core,
(iii) Curvature-dependent interfacial effects at the
micellar core-water interface, and
(iv) Hydrophobic interactions between surfactant
hydrocarbon chains and water.
4.1 Structure and Interaction Energy
Reactive orange 107 dyes are having two aromatic rings and
several functional groups. The functional group in reactive
orange 107 dyes is classified into two categories such as
chromofore and auxochromoe. The chromofore configurations
are represented by the azo group (-N=N-), ethylene group
(=C=C=), methine group (-CH=), carbonyl group (=C=O),
carbon-nitrogen (=C=NH), carbon-sulfur (=C=S), Nitro (-
NO2;-NO-OH), nitrozo (-N=O; =N-OH). These groups are
having highly electron acceptor which is indicating that the
groups of molecule looking for a rich electron center of the
atom in the chemical structure whereas the color of individual
dye is strongly depends on the presence of chromogene-
chromophore groups in their structures. Therefore, the reactive
orange 107 has a golden yellow color. The auxochrome
groups are ionizable groups which are responsible for the
dyeing capacity in the textile material and other materials. The
usual auxochrome groups are amines (-NH2), carboxyl (-
COOH), sulphonate (-SO3H), and hydroxyl (-OH). These
groups of molecules are having electron deficiency of the
atom in their molecular structure. Thus, the group of
molecules is existing low reactivity and high thermal and
chemical stability to deep conventional process such as
adsorption, precipitation, chemical degradation, photo
degradation, etc. The optimized structure of surfactant triton
X-114, reactive orange 107dyes and surfactant triton X-114 +
reactive orange 107 is given in Figure 1 to Figure 3.
The surfactant triton X-114 is consisting of the aromatic ring,
carbon, and hydrogen and oxygen atom in their chemical
structure. The total hydrogen atom in the surfactant triton X-

__________________________________________________________________________________________
114 is 50 which is higher than reactive orange 107 dyes
whereas the electronegative atom and ions such as nitrogen,
oxygen, sulfuratom and sodium ions located in the reactive
orange is 19 (4 nitrogen, 3 sulfur, 10 oxygen and 2 sodium
ions) which cause the rate of decolourization, degradability
and recovery of dyes from aqueous solution. However, these
electronegative atom and ions are playing significant role in
the formation of a bond between active surfactant, namely,
triton X-114 and reactive orange 107 dyes. Further, there are
several possible electron donor sites as available in the
surfactant to have hydrogen interaction with the neighboring
molecules like reactive orange 107 dyes. Furthermore the
surfactant triton X-114 and reactive orange 107 dyesare
having similar aromatic ring structure at the center of their
structures.It can be influenced on the effective structural
orientation between those two similar molecules via π--π
stacking and CH--π interaction and no (N, S, O) --π interaction
[17-20].
The total electronic energy of surfactant triton X-114, reactive
orange 107 dyes, water and their complex structures have been
studied using ab initio method and the results are presented in
Table 1.The total electronic energy of reactive orange is -
8131907.327 kJ.mole-1 (Table 1) whereas the surfactant has -
2022439.464 kJ.mole-1 (Table 1) and -199505.7064 kJ.mole-1
(Table 1) for water molecules. The total electronic energy of
surfactant triton X-114 is less than reactive orange 107 dyes
whereas higher than that of water molecules. It can be
explained that the removal of reactive orange 107 dyes from
water molecules required higher degree of adsorbent or
catalyst than that of reactive orange 107 dyes. The reactive
orange 107 dyes have more electron deficiency of atom
located in their molecular structure as well as unsaturated
bond orderwhich cause reactivity and stability of the
molecules in the complex systems.
From the total electronic energy values of individual
molecules such as reactive orange 107 dyes, surfactant triton
X-114, water, surfactant triton X-114+reactive orange 107
dyes, surfactant triton X-114+ water and reactive orange 107
dyes + water have been calculated and it’s given in Table 1.
The interaction energy of the complex system can be defined
as the difference between the total electronic energy of
mixture and total electronic energy of individual molecules
which can give the information about the strength of hydrogen
bond formation between two or more compounds in the
mixture. The interaction energy can be calculated according to
the following equation 1, 2 and 3.
( )tan an tanSurfac t Dyes Surfact t Dyes Surfac t DyesIE TE TE TE− += − +
(1)
( )tan an tanSurfac t Water Surfact t Water Surfac t WaterIE TE TE TE− += − +
(2)
( )Dyes Water Dyes Water Dyes WaterIE TE TE TE− += − +
(3)
Where, IE and TE are the interaction energy and total
electronic energy of the molecules and their cluster. The
interaction energy of the complex formed between surfactant
triton X-114 and reactive orange 107 dyes have -
92073.8853kJ.mole-1 (Table 1) whereas 4303.4720 kJ.mole-1
(Table 1) for surfactant triton X-114 + water,
4203.10926kJ.mole-1 (Table 1) for reactive orange 107 dyes +
water systems. The interaction energy between surfactant
triton X-114 + reactive orange 107 dyes show smaller values
with negative sign than that of reactive orange 107 dyes
+water and surfactant triton X-114+water systems due to the
presence of appreciable level of physical, chemical and
structural interaction between surfactant and dyes. It is
observed that surfactant triton X-114 has high potential to
separate reactive orange 107 dyes from aqueous solution
because these two molecules have several possible physical,
chemical and structural interactions such asCH--π
interaction,π--π interaction, n (S,N,O)--π interaction , S--H
interaction, N--H interaction, O--H interaction, hydrogen bond
interaction with neutral molecules and charge--charge
interaction[17-20]. Further, the charge--charge interaction is
the dominant interaction in the attraction and that the
interaction of surfactant triton X-114 with reactive orange 107
dyescomplex have smallervalues than that of surfactant triton
X-114 + water complex and reactive orange 107 dyes + water.
The surfactant triton X-114 is not close to water molecules,
resulting in immiscible with each other. It can be easily
observed that the interaction energy is inversely proportional
to distance between two interacting molecules. However the
conventional hydrogen bonds have strong directionality and
therefore, hydrogen bonds play important roles in controlling
the structure of molecular assemblies and their properties.
4.2 Effect of Surfactant Concentration and
Temperature on Refractive Index
Refractive index is related to the polarizability of molecules in
binary mixture. They can provide clear information aboutthe
interactionbetween those two molecules.In order to study the
effect of interactions with increasing alkyl chain length, the
refractive index of pure and mixture were measured (Table 2).
It was noted that there is chemical resistance offered which
cause familiar physical and chemical interactions [34] due to
the deficiency of the hydrogen atom.Figure 5 shows the
variation of refractive index with surfactant concentration 0.01
M to 0.1 M intwo differentphases. For aqueous phase,
refractive index is constant with increasing surfactant
concentration at 25ppm of dye concentration. The aqueous
phase mainly consists of water, whereas dye and surfactant are
present in negligible amount. The aqueous phase has the same
refractive index of water at room temperature i.e. 1.332 with
increasing surfactant concentration. The constituents of

__________________________________________________________________________________________
coacervate phase are same as aqueous phase but the presentof
water is in negligible. In Figure 5, the refractive index
increases with surfactant concentration. The increase in
surfactant concentration causes more solubilization of dye
which increases the dye concentration in the coacervate phase.
This shows the refractive index of the phase is dependent upon
the composition of the phase and the amount of constituent
present.
The refractive index of the aqueous phase is same as water
1.332, even at different temperatures (Table 2). It is noted that
the amount of water influences on the refractive index of the
aqueous phase as well as the concentration of the dye and
surfactant has negligible. The refractive index is increased
with the increase in temperature (Table 2). As temperature
increases, the CMC value of surfactant decreases and that
causes increased dye solubilization. Water molecules are
dehydrated with increase in temperature in the coacervate
phase. Polar interaction between water and surfactant
molecule decreases whereas the hydrophobic interaction of
surfactant with dye increases with increase in temperature.
Due to decrease in the amount of water and increase in the
amount of dye in coacervate phase the refractive index
increases (Table 2). Thus, the refractive index of binary
mixture depends on the amount of dye and water present in the
coacervate phase.
Temperature on Density
Reactive Orange is an anionic dye. The density of the mixtures
is very strongly affected by the nature of the anion. Density is
related to the compactness of the structure of molecules. The
density in dilute phase is almost constantly with the increase
in surfactant concentration (Table 3) whereas the coacervate
phase density increases with increase in surfactant
concentration due to the presence of physical and chemical
interaction. Reactive orange 107 dyesare present more in
coacervate phase than dilute phase. Therefore there is a big
difference in the values of the density of dilute and coacervate
phase and also to increase in surfactant concentration.Density
of dilute phase decreases with increase in temperature due to
the presence of water and thus reduces the strength of
hydrogen in the mixture (Table 3). At lower concentrations of
surfactant, there is not much effect of temperature but as
surfactant concentration increases the density decreases with
increase in temperature (Table 3). This can be explained that
thehydrogen bonding is more temperature dependent than
compositions. At lower temperature, there is more hydrogen
bonding interaction between water and surfactant molecules
but at higher temperatures there is a dissociation of water
molecules from the surfactant molecules. So, the amount of
water increases in dilute phase of higher surfactant
concentration therefore resulting in a decrease in
density.Density of coacervate phase increases with increase in
temperature. For temperature 303 and 323 K there is gradual
increase in density with increase in surfactant concentration
but for 313 K there is a rapid increase in density in surfactant
concentration (Table 3). The density of coacervate phase
increases with temperature because there is a dehydration of
water molecules from surfactant molecules present in
coacervate phase. The decrease in water content with
temperature causes the density to increase with temperature.
Temperature on Viscosity
Viscosity is an important parameter in molecular interaction
studies. It has a strong effect on the rate of mass transport
within the solution. The viscosity of water is 0.8903 CP at 298
K. The identities of the anion and the cation which composes
the mixture have a huge effect on the viscosity of the liquid
mixture. Viscosity is also affected by the Van der Waals force
interaction. The interaction increases with ions exhibiting long
alkyl chains or a higher degree of branching. With respect to
the anionic species, higher basicity, size and relative capacity
to form H-bonds leads to more viscous mixtures. The viscosity
is almost constant with an increase in surfactant concentration
for dilute phase (Table 4). There is much amount of water
present in dilute phase so the viscosity of dilute phase lies
around that of water.
The viscosity increases with increase in surfactant
concentration in coacervate phase (Table 4). This is due to the
anionic nature of more dye solubilized with increasing
surfactant concentration. With the increase in surfactant
concentration, micelle concentration also increases due to
which more dye is solubilized. As the more dye is solubilized
in surfactant, van der wall interaction between dye and
surfactant increases. As already mentioned viscosity is
affected by increased van der Waal interaction therefore
viscosity is increased.There is no significant variation with
temperature in coacertvate phase (Table 4). The viscosity of
dilute phase is almost in between 0.75 and 0.89 mPa.S-1 .
This shows that the viscosity of dilute phase is depended
strongly on water content and weakly on temperature. The
viscosity increases with increase in temperature and decreases
with water content. As temperature is increased the
dehydration of surfactant molecules results in decreased
content of water in coacervate phase. As content of water
decreases with temperature the viscosity of the coacervate
phase increases as it leads to more solubilization of dye with
increasing temperature. With increase in temperature
hydrophobicity of surfactant molecules increases which leads
to more interaction of dye with the hydrophobic part. Water
interacts with the hydrophilic part of TX-114 through dipole-
dipole interactions. As temperature increases hydrophilic
nature of surfactant is reduced which results in dehydration of
water molecules. A small quantity of water causes a great
viscosity decrease. Thus this figure shows the great variations
of viscosity depend on the water content at all the studied
temperature (Table 4).

__________________________________________________________________________________________
4.5 Effect of Temperature and Concentration on
Excess Molar Volume (VE)
The excess molar volume depends on the composition and
temperature and is of great importance in understanding the
nature of molecular aggregation that exists in the mixture. The
excess molar volume is calculated by the following formula:
E
3 3
i i i i
i 1 i 1mix i
x M x M
V
= =
= −
ρ ρ
∑ ∑
(4)
Where xi (i =1, 2,3) is the mole fractions of dye (Reactive
Orange), surfactant (TX-114) and water respectively. Mi, (i
=1, 2, 3) is the molecular weights of dye, surfactant and water
respectively. i (i =1, 2, 3) is the density of the mixture (dye +
surfactant +water).
VE is the result of contribution from several opposing effects
which is divided into three types – physical, chemical and
structural effect [29]. Physical effects are due to non-specific
physical interactions such as dispersion force due to breaking
of dipoles or weak dipole-dipole interaction and van der Waals
interaction between alkyl chains. Chemical effect includes
charge – charge interaction, H-bond interaction, and donor-
acceptor complex forming interactions,CH--π interaction, π--π
interaction n(O,S,N)--H interaction and n(S,O,N)--π
interaction [17-20].Structural effect isgeometrical fitting of the
component molecules into each other’s structure and due to
the difference in molar and three volumes.Physical effects
make a positive contribution to VE, chemical and structural
effects make a negative contribution. Negative VE values
indicate that the chemical contributions are dominant. The
chemical or specific intermolecular interactions result in a
volume decrease, and these include charge transfer type forces
and other complex forming interactions. The structural
contributions are mostly negative and arise especially from
interstitial accommodation and changes of free volume.
Values of VE nearly zero, implies that the interactions
between unlike molecules are very similar to the
intramolecular interactions.
Figure 6 implies that the negative values of excess molar
volume are due to the dominant chemical effects than the
other effects in cloud point extraction. VEdecreases with
increase in temperature and surfactant concentration. At
higher temperature the chemical effects decreases and the
interaction between the like and unlike molecules are almost
similar i.e VE approaches zero, so there is very less interaction
between dye and surfactant and extraction of dye is inefficient.
So up to a certain value of temperature there is an effective
extraction of dye by surfactant and above a certain
temperature solubilization of dye decreases. As surfactant
concentration is increasing there is increase in excess molar
volume which shows increasing chemical and structural effect
with increasing surfactant concentration. So, the more dye is
solubilized with increasing surfactant concentration (Table 5).
CONCLUSIONS
A systematic study on the relative surfactant triton X-114,
reactive orange 107 dyes, water and its cluster total electronic
energy and thereby interaction energy for complex formed
betweensurfactant triton X-114+reactive orange 107 dyes,
surfactant triton X-114+reactive orange 107 and reactive
orange 107+water were performed in this work using ab initio
methods with 6-31G* basis set. The results on the complex
systems relative interaction were interpreted in terms of
influence of structure of both surfactant triton X-114 and
reactive orange 107 dyes, deficiency of hydrogen atom in the
reactive orange 107 dyes, the presence of electronegative atom
in the aromatic structure of reactive orange 107 dyes and some
other phytochemical interactions such as charge – charge
interaction, H-bond interaction, and donor-acceptor complex
forming interactions, van der Waals interaction between alkyl
chain, CH--π interaction, π--π interaction n(O,S,N)--H
interaction and n(S,O,N)--π interaction. To identify the
possible molecular interaction in the mixture of the above
systems experiment was carried out at different temperature
and different concentration of surfactant.In order to measure
the density, refractive index and viscosity of pure and mixedat
303.15, 313.15 and 323.15K and calculated their excess molar
properties. There is no significant concentration effect in
dilute phase of mixture properties whereas in coacervate phase
shows reliable influenced by the concentration of surfactant. It
is noted that density is strongly depends on temperature as
well as concentration of surfactant and the viscosity is
dependent on water or moisture content than temperature. It is
also observed that the surfactant triton X-114 and reactive
orange 107 dyes have mutual molecular interaction and
therefore they exhibit negative deviations while increasing
temperature the deviation has been changed drastically due to
minimize the effect of hydrogen bonds in the mixture.
Moreover, itis concluded that there is a strong possibility
toremovetraces of dyes from aqueous solution without
additional equipment requirements. But the structure
assemblies and their propertyrelationships are essential factors
to enhance the process efficiency.
NOMENCLATURE
CPE Cloud point extraction
IE Interaction energy
TE Total electronic energy
xi Mole fraction of component i
Mi Molecular weight of component i
i Density of component i
mix Density of mixture
VE Excess molar volume

__________________________________________________________________________________________
ACKNOWLEDGEMENTS
The work is partially supported by Tamil Nadu State Council
for Science and Technology (TNSCST/S&T
project/VR/ES/2009-2010). The authors wish to thank
Taminadu State Council Science and Technology for their
financial support.
REFERENCES
[1]. Won, S.W., Choi, S.B., Yun, Y.: Performance and
mechanism in binding of ReactiveOrange 16 to various
types of sludge. Bioch. Eng. Journal. 28,208–214
(2006)
[2]. Renganathan, S., Thilagaraj, W.R., Miranda,
L.M.,Gautam, P. , Velan, M.: Accumulation of Acid
Orange 7, Acid Red 18 and Reactive Black 5 by
growing Schizophyllum commune. Biore.Technology.
97,2189–2193(2006)
[3]. Greluk, M., Hubicki, Z.: Comparison of the gel anion
exchangers for removal of Acid Orange 7 from aqueous
solution, Chem. Engg. Journal 170,184–
193(2011)
[4]. Tizaoui, C., Grima, N.: Kinetics of the ozone oxidation
of Reactive Orange 16 azo-dye in aqueous solution.
Chem.Engg. Journal 173, 463– 473(2011)
[5]. Rio ,A., Molina, J., Bonastre, J., Cases, F.: Influence of
electrochemical reduction and oxidation processes on
the decolourisation and degradation of C.I.
Reactive Orange 4 solutions. Chemosphere. 75 1329–
1337 (2009)
[6]. Aksu, Z.C., Cagatay, S.S.: Investigation of biosorption
of Gemazol Turquoise Blue-G reactive dye by dried
Rhizopus arrhizus in batch and continuous systems.
Sepa.and Puri. Technology.48,24-35(2006)
[7]. Lata, H.,Garg, V.K., Gupta, R.K.: Removal of a Basic
Dye from Aqueous Solution by Adsorption Using
Parthenium Hysterophorus: An Agricultural Waste.
Dyes and pigments.74, 653-658(2007)
[8]. Purkait,M.K., Das Gupta,S., De,S.: Determination of
design parameters for the Cloud Point Extraction
of Congo red and eosin dyes using Triton X-100. Sepa.
Sci. and Technology.51,137-142(2006)
[9]. Gullickson, N.D., Scamehorn, J.F.,
Harwell,J.H.:Liquid-coacervate extraction. In
Scamehorn, J.F., Harwell,J.H. (Eds.), Surfactant Based
Separation Processes. MarcelDekker Inc., New
York, 139–152(1989)
[10]. Kimchuwanit,W., Osuwan, S., Scamehorn, J.F.,
Harwell, J.H.,Haller, K.J.: Use of a micellar-rich
coacervate phaseto extract trichloroethylene from
water. Sepa.Sci. and. Technology.35 , 1991–2002
(2000)
[11]. Wang, Z., Zhao, F., Li, D.: Determination of
solubilizationof phenol at coacervate phase of cloud
point extraction.Colloid. Surf. A: Physico. Eng.
Aspects.216,207–214(2003)
[12]. Purkait, M.K., Vijay, S.S., Dasgupta,S., De, S.:
Separation of Congo red by surfactant mediated cloud
point extraction. Dyes Pigments.63,151-159(2004)
[13]. Purkait, M. K., Banerjee, S., Dasgupta,S., De, S.:Cloud
point extraction of toxic eosin dye using Triton X-100
as nonionic surfactant. Water Res.39, 3885-3890(2005)
[14]. Dutta,R.K., Bhat,S.N.: Dye-Surfactant Interaction in
Submicellar Concentration Range, Bullet.Chem.Soc.
Japan.65,1089-1095(1992)
[15]. Simoncic, B., Span, J.: A Study of Dye-Surfactant
Interactions. Part 1. Effect of Chemical Structure of
Acid Dyes and Surfactants on the Complex
Formation.Dyes and Pigments.36, 1-14(1998)
[16]. Simoncic, B., Kovac, F.: A Study of Dye-Surfactant
Interactions. Part 2. The Effect of Purity of a
Commercial Cationic Azo Dye on Dye-Surfactant
Complex Formation.Dyes and Pigments.40,1-9(1991)
[17]. Fernandes, A.M., Rocha, M.A.A., Freire, M.G.,
Marrucho ,I.M., Coutinho ,J.A.P., Santos, M.N.B.F.:
Evaluation of Cation-Anion Interaction Strength in
Ionic Liquids. J.Phy. Chemistry B 2011; 115: 4033–
4041.
[18]. Lu, R., Lin, J., Qu, Z.:Theoretical study on interactions
between
thiophene/dibenzothiophene/cyclohexane/toluene and
1-methyl-3-octylimidazolium
tetrafluoroborate.Stru.Chemistr DOI 10.1007/s11224-
012-0106-z.
[19]. Castellano, O., Gimon, R., Soscun, H.: Theoretical
Study of the σ-π and π-π Interactions in
heteroaromaticmonocyclic Molecular Complexes of
Benzene, Pyridine, and Thiophene Dimers:
Implications on the Resin-Asphaltene Stability in
Crude Oil. Energy &Fuels. 25,2526–2541(2011)
[20]. Anantharaj, R., Banerjee, T.: Quantum chemical studies
on the simultaneous interaction of thiophene and
pyridine with ionic liquid. AIChE Journal .57,749-
764(2011)
[21]. Manian, A.P.: Dye-Surfactant Interactions in
Thermosol Dyeing, approved by University of Georgia,
Aug 2002.
[22]. Yadava, S.S., Yadav, A.P.: Ultrasonic behavior of
binary liquid mixtures of 1-bromopropane with
cyclohexane and benzene. Ind. J.Pure &
App.Physics.42,338-340 (2004)
[23]. Saravanakumar, K., Baskaran, R., Kubendran,
T.R.:Densities, Viscosities, Refractive Indices and
Sound Speeds of Acetophenone with Methylacetate at
Different Temperatures. J.Chemistry.9,1711-
1720(2012)
[24]. Doroschuk, V.O., Kulichenko, S.A.,Lelyushok, S.O.:
The influence of substrate charge and molecular
structure on interphase transfer in cloud point extraction
systems. J.Coll. and Inter. Science.291,251–255(2005)
[25]. Yanfang,G., Tengfang, W., Dahong, Y., Changjun, P.,
Honglai,L., Ying, H.: Densities and Viscosities of the

__________________________________________________________________________________________
Ionic Liquid [C4mim][PF6]+
N,N-dimethylformamide
Binary Mixtures at 293.15 K to 318.15 K. Chin.
J. Chem.l Engineering.16,256-262 (2008)
[26]. Schaftenaar, G., Noordik, J.H.: Molden: a pre- and
post-processing program for molecular and electronic
structures. J.Comp. Aid. Mole. Design. 14,123–
134(2000)
[27]. Meng, J., Dolle, A., Carper, R.W.: Gas phase model of
an ionic liquid: Semi-empirical and ab-initio bonding
and molecular structrure.J. Mole.Structure
(Theo).585,119–128(2002)
[28]. Turner, E.A., Pye, C., Singer, R.D.: Use of ab-initio
calculations toward the rational design of room
temperature ionic liquids. J.Phys. Chemistry
A.107,2277–2288(2003)
[29]. Boys,S., Bernardi, F.: Mole. Physics. 19,553(1970)
[30]. Frisch, M. J., Trucks, G.W.,Schlegel, H.B., Scuseria, G.
E.,Robb, M.A., Cheeseman, J.R., Montgomery ,J. A.,
Vreven. T., Kudin,K.N., Burant, J.C., Millam, J.M.,
Iyengar, S.S., Tomasi,J.,Barone, V., Mennucci, B.,
Cossi, M., Scalmani,G., Rega,N., Petersson,G. A.,
Nakatsuji, H., Hada. M., Ehara, M., Toyota,
K.,Fukuda.R., Hasegawa. J., Ishida, M.,Nakajima,
T.,Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X.,
Knox, J.E., Hratchian, H.P., Cross, J.B., Bakken,
V.,Adamo, C., Jaramillo, J., Gomperts, R., Stratmann,
R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C.,
Ochterski, J. W., Ayala ,P.Y.,Morokuma. K., Voth,
G.A., Salvador, P., Dannenberg, J.J., Zakrzewski,V.G.,
Dapprich, S., Daniels, A.D., Strain, M.C,, Farkas, O.,
Malick,D.K., Rabuck, A.D., Raghavachari,K.,
Foresman, J.B,, Ortiz,J.V., Cui,Q., BaboulA.G.,
Clifford, S., Cioslowski, J.,Stefanov,B. B., Liu, G,
Liashenko, A., Piskorz,P., Komaromi, I., Martin, R.L.,
Fox, D.J., Keith,T., Al-Laham,M .A., Peng, C.Y.,
Nanayakkara, A., Challacombe, M., Gill,
P.M.W.,Johnson, B., Chen,W., Wong,M.W.,
Gonzalez,C., Pople, J.A.: Gaussian 03, Revision C.02;
Gaussian: Pittsburgh, PA, 2004.
[31]. Musnickas, J., Skulkina, O., Treigiene, R., Rageliene,
L.: Effect of the Interaction between Acid Dye and
Nonionic Surfactants on the Adsorption of Dye in Wool
Fibre, Fibres & Textiles in Eastern Europe.16,70(2008)
[32]. Puvvada.: Molecular thermodynamic approach to
predict micellization, phase behavior and phase
separation of micellar solutions.Mass.
Inst.Technology.1-15(1989)
[33]. Yadava, S. S., Yadav, A., Kushwaha,N,, Yadav, N.:
Refractometric studies on molecular interactions
between some bromoalkanes and nonpolar
hydrocarbons. Ind.J.chemistry .48,650-657(2009)
[34]. Gowrisankar, M., Sivarambabu, S., Venkateswarlu, P.,
Siva Kumar, K.: Excess Volumes, Speeds of Sound,
Isentropic Compressibilities and Viscosities of Binary
Mixtures of N-Ethyl Aniline with Some Aromatic
Ketones at 303.15 K. Bull. Korean Chem. Soc.5,33
(2012)
Table1: The total electronic energy and Interaction energies between triton X-114, reactive orange 107 and their complex using ab
initio method with 6-31G* basis set.
S.No Name Total energy
(kJ.mole-1
)
Interaction energy
(kJ.mole-1
)
1 Dyes:
Reactive orange 107 (RO107)
-8131907.327 -
2 Surfactant:
Triton X-114 (TX-114)
-2022439.464 -
3 Water -199505.7064 -
4 RO107+Water -8327209.924 4203.109259
5 TX-114+Water -2217641.698 4303.472023
6 TX-114+RO107 -10246420.68 -92073.88529

__________________________________________________________________________________________
Table 2: Experimental Refractive index values for dilute and coacervate phase as a function of temperature and surfactant
concentration.
Surfactant
Concentration
(M)
Temperature (K)
303.15K 313.15K 323.15K
Dilute Coacervate Dilute Coacervate Dilute Coacervate
0.01 1.332 1.3580 1.332 1.3605 1.332 1.3530
0.02 1.332 1.3560 1.332 1.3630 1.332 1.3560
0.03 1.332 1.3585 1.332 1.3640 1.332 1.3588
0.04 1.332 1.3595 1.332 1.3660 1.332 1.3610
0.05 1.332 1.3610 1.332 1.3665 1.332 1.3625
0.06 1.332 1.3610 1.332 1.3690 1.332 1.3670
0.07 1.332 1.3680 1.332 1.3685 1.332 1.3695
0.08 1.332 1.3680 1.332 1.3695 1.332 1.3745
0.09 1.332 1.3610 1.332 1.3700 1.332 1.3750
0.1 1.332 1.3610 1.332 1.3710 1.332 1.3780
Table 3: Experimental Density values in g/cc for dilute and coacervate phase as a function of temperature and surfactant
concentration.
Surfactant
Concentration
(M)
Temperature (K)
303.15 313.15 323.15
0.01 1.000032 - 1.000030 - 1.000022 -
0.02 1.000073 - 1.000142 - 1.000037 -
0.03 1.000163 - 1.000196 - 1.000000 -
0.04 1.000254 - 1.000175 - 1.000251 -
0.05 1.000456 1.013099 1.000182 - 1.000222 -
0.06 1.000417 1.014066 1.000222 1.012756 1.000235 1.017372
0.07 1.000472 1.014194 1.000378 1.015736 1.000273 1.017889
0.08 1.000636 1.013592 1.000449 1.018362 1.000354 1.019479
0.09 1.000626 1.014833 1.000525 1.019535 1.000317 1.019904
0.1 1.000707 1.015070 1.000527 1.020131 1.000396 1.019183

__________________________________________________________________________________________
Table 4: Experimental Viscosity values in mPa/s for dilute and coacervate phase as a function of temperature and surfactant
concentration.
Surfactant
Concentration
(M)
Temperature (K)
303.15 313.15 323.15
0.01 0.74 - 0.820 - 0.840 -
0.02 0.74 - 0.820 - 0.860 -
0.03 0.7 - 0.820 - 0.860 -
0.04 0.74 - 0.840 - 0.860 -
0.05 0.8 - 0.840 - 0.880 -
0.06 0.78 122.7 0.840 - 0.880 155.700
0.07 0.82 123.9 0.860 135.900 0.880 173.600
0.08 0.84 126.9 0.860 148.800 0.900 181.800
0.09 0.84 127.9 0.860 161.100 0.900 174.600
0.1 0.84 129.8 0.880 161.100 0.900 171.900
Table 5: Experimental Excess molar values in mPa/s for dilute and coacervate phase as a function of temperature and surfactant
concentration.
Surfactant
Concentration(M)
Temperature (K)
303.15 313.15 323.15
0.01 -0.00057 -0.00054 -0.00038
0.02 -0.00129 -0.00254 -0.00066
0.03 -0.00292 -0.00351 0.00456
0.04 -0.00456 -0.00314 -0.00450
0.05 -0.00476 -0.00476 -0.00398
0.06 -0.00749 -0.00398 -0.00422
0.07 -0.00628 -0.00628 -0.00491
0.08 -0.01143 -0.00807 -0.00637
0.09 -0.01126 -0.00943 -0.00570
0.1 -0.01271 -0.00947 -0.00711

IJRET: International Journal of Research in Engineering and Technology
__________________________________________________________________________________________
Volume: 02 Issue: 08 | Aug-2013, Available @
Figure 1: Optimized structure of surfactant
298.15K; Density at 298.15K: 1.052 gmL
Figure2: Optimized structure of reactive orange 107 dyes; class: diazo; reactive
1
; max (visible): 411nm; molecular weight: 566.49gmol
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319
__________________________________________________________________________________________
2013, Available @ http://www.ijret.org
Optimized structure of surfactant triton X-114 structure; octyl phenol polyethylene glycol ether;Cloud Pointtemperature:
298.15K; Density at 298.15K: 1.052 gmL-1
; max (visible): 223nm; molecular weight: 537g.mol
eactive orange 107 dyes; class: diazo; reactive group: vinyl sulphone; Density at 298.15K: 1.7g.mL
; max (visible): 411nm; molecular weight: 566.49gmol-1
.
eISSN: 2319-1163 | pISSN: 2321-7308
__________________________________________________________________________________________
452
structure; octyl phenol polyethylene glycol ether;Cloud Pointtemperature:
weight: 537g.mol-1
.
group: vinyl sulphone; Density at 298.15K: 1.7g.mL-

__________________________________________________________________________________________
Figure 3: Optimized structure of complex formed between surfactant triton X-114+ reactive orange 104 dyes using HF/6-31G*
level.
Figure 4:Calibration curve for Reactive Orange 107 dye
y = 0.022x + 0.011
R² = 0.998
0
0.5
1
1.5
2
2.5
0 10 20 30 40 50 60 70 80 90 100
Absorbance
Concentration of Reactive Orange (ppm)

__________________________________________________________________________________________
Figure 5: Variation of refractive index with TX-114 concentration for dilute and coacervate phase at 25ppm Reactive Orange
concentration and at 313 K temperature
Figure 6: Variation of excess molar volume with temperature and surfactant concentration at 25ppm reactive orange concentration.
1.330
1.335
1.340
1.345
1.350
1.355
1.360
1.365
1.370
1.375
0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10
RefractiveIndex
Concentration of TX-114 (M)
dilute phase
coac. phase
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1
(-ve)Excessmolarvolume,VE,cm3mol-1
Concentration of TX-114 (M)
303 K
313 K
323 K

Evaluation of interaction energies and thermodynamic

More Related Content

What's hot (18)

Viewers also liked (20)

Similar to Evaluation of interaction energies and thermodynamic (20)

More from eSAT Publishing House (20)

Recently uploaded (20)

Evaluation of interaction energies and thermodynamic