Thermodynamic and transport properties of binary liquid ...

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Der Pharma Chemica, 2014, 6(4):135-139
(http://derpharmachemica.com/archive.html)

ISSN 0975-413X

CODEN (USA): PCHHAX

Thermodynamic and transport properties of binary liquid mixtures of 1,4-
Dioxane with nitrobenzene at various temperatures using Mcallister model

Golamari Siva Reddy, R. Srinivasa Reddy and Mallu Maheswara Reddy

Centre of Bioprocess Technology, Department of Biotechnology, K L University, Vaddeswaram, Guntur,
Andhrapradesh, India

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ABSTRACT

The reason for this study directed in this exploration was to measure thermo physical properties like Viscosities, η,
and Densities, ρ, of 1,4-dioxane with nitrobenzene at distinctive mole fractions and different temperatures in the
atmospheric weight condition. From the exploratory information Excess molar volumes, VE, and deviations in
viscosities, ∆η, of mixtures at boundless weakening have been gotten. The measured frameworks showed positive
estimations of VE and negative estimations of ∆η. The double mixture 1, 4 dioxane + nitrobenzene show positive VE
and negative ∆η with expanding temperatures. The conclusions unmistakably show that frail collaborations
introduce in mixture. It is fundamentally in light of number and position of methyl gatherings exist in these fragrant
hydrocarbons. These measured information customized to the McAllister model to infer the double coefficients.
Standard deviations acquired from the fitted conclusions and the computed information is useful purposeful
blending conduct of the binary mixtures. It can derive that for our circumstance, the data found with the qualities
related by the relating model is outstandingly well. The atomic collaborations existing between the segments and
correlation of fluid mixtures were additionally talke.

Keywords: Density, Excess molar volume, 1,4 Dioxane, Nitrobenzene, Viscosity and Viscosity deviation.
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INTRODUCTION

In manufactured design and practical mixture process headway, the nuclear interchanges existing in procedure fluids
and thermo physical properties like Densities and viscosities accepting key part. These two are indispensable for
planning arrangements including compound allotments, hotness trade, mass trade, and fluid stream. It is basic from
feasible and theoretical viewpoints for appreciation liquid theory [1]. 1, 4 Dioxane usually known as magnificent
aprotic dissolvable, has a dipole development is zero. In polymerization and other concoction responses it was
utilized industrially like cleaning of polymer surfaces and electronic materials. The sweet-smelling hydrocarbon
particles have an extensive fourfold minute, which causes an orientational request in these fluids. The orientational
request is considered an incomplete arrangement of neighboring sections or perhaps of entire particles. Additionally,
double mixtures holding sweet-smelling hydrocarbons are intriguing in light of the fact that they have provisions in
the investigation of polymer stage graphs and the particular collaboration of polymers in blended solvents. 1, 4
Dioxane is cyclic ether that has electron-benefactor capacity at the sweet-smelling rings that demonstration like frail
electron acceptors. In this way, the 1, 4 Dioxane + Nitrobenzene mixtures will be intriguing on the grounds that they
include charge-exchange communications that may be affected by the vicinity of alkyl gatherings on the ring.
Different employments of 1, 4 Dioxane incorporate production of cements and concretes, antiperspirant fumigants,
beatufiers, medications, cleaning arrangements, attractive tape, plastic, elastic, insect poisons, herbicides, and as a
substance middle.

As a polymerization impetus, in the cleansing of pills, and 1, 4 Dioxane has low danger to amphibian life forms and
lethality qualities are more noteworthy than 100 mg/L. 1, 4 Dioxane is not liable to be intensely lethal. The whole go

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of organization was mulled over at T = (303.15to313.15) K. With this information, the overabundance molar volume
and deviation in thickness have been registered. These results have been fitted to the McAllister’s three-body model
is utilized to relate the kinematic viscosities of these parallel mixtures [1]. This investigated method to determine the
twofold coefficients and to gauge the standard deviation (σ) in the middle of trial and figured information.

MATERIALS AND METHODS

Materials
1, 4 dioxane and Nitrobenzene this were all supplied by M/s Merck Ltd. With expressed purities of superior to 99 %
were put away over atomic sifters (0.3 nm Merck, India). Nitrobenzene with a virtue of 99 % was given by Sigma-
Aldrich Chemicals and was utilized without further decontamination. To minimize the contact of these reagents with
sodden air, the items were kept in fixed jugs in a desiccator. The virtue of the substances was controlled by GLC.
Densities and viscosities of immaculate substances and their examination with writing qualities are recorded in
Table 1.

APPARATUS AND PROCEDURE
Estimations of the thickness, ρ, and the kinematic consistency, γ, of unadulterated fluids and their answers were
completed utilizing an Oswald Sprengel Pycknometer and Oswald Viscometer and two incorporated Pt 100
thermometers. The temperature in the cell was controlled to 0.001K with a corresponding temperature controller.
The device was initially aligned with triple refined water. The instabilities in thickness estimations were assessed to
be 2•10-3 g•cm-3 and. Further data about the exploratory strategies has been the kinematic viscosities of the
unadulterated fluids and their mixtures were measured at (303.15, 308.15, and 313.15) K.

The viscometer was loaded with fluid or fluid mixtures, and its appendages were shut with Teflon tops taking due
safety measure to decrease vanishing misfortunes. An electronic computerized stopwatch with an intelligibility of
0.01 s was utilized for stream time estimations. Analyses were rehashed at least four times for all structures, and the
results were arrived at the midpoint of. The tops of the appendages were evacuated throughout the estimation of
stream times. The measured estimations of kinematic consistency, γ, were changed over to element viscosity, η,
after duplication by the thickness. The reproducibility of element thickness was discovered to be inside 0.003 m
pa.s. A thermostatically controlled decently blended water shower whose temperature was controlled to 0.01 K and
It was utilized for all the estimations. Conductivity estimations were completed in a coat holding a conductivity cell
of cell steady 1.0 cm-1. Water was flowed in the coat from indoor regulator, and the temperature was kept up inside
± 0.01 K was utilized for all the measurements. The kinematic viscosity of solution γ is given by

γ=at-b/t (1)

Where γ is the kinematic viscosity, t is the flow time, the two constants a, and b are the kinematic viscosities, γ, and
densities. The uncertainty for the dynamic viscosity determination is estimated to be ± 0.5 %.Excess molar volumes,
VE, and viscosity deviation, ∆η, progressions of blending at different temperatures and environmental weight are
accounted for in Table 2 for the Nitrobenzene +1, 4 Dioxane. In Table 2, interaction between Nitrobenzene + 1, 4
Dioxane mixture is powerless contrasted with previous system connection between ethyl benzene + methyl ethyl
ketone [2-3]. The test qualities indicates plainly ethyl assemble in ethyl benzene and it structures dipole-dipole bond
with 1, 4 Dioxane, due to dipole-dipole bond, thermo physical properties diminishing with expansion of 1, 4
Dioxane at all temperature reported in Table 2. The related values by McAllister model are demonstrated in tables 4.
The got thermo physical information indicates high level of exactness contrasted and the exploratory qualities.
Parameters of McAllister nonlinear model, constants and standard deviations (σ) of Binary fluid mixtures are
demonstrated in Table 4.The abundance molar volumes, VE, dynamic consistency, η, and molar refraction
progressions of blending were computed from exploratory qualities utilizing the accompanying interpretations.

VE = (x1m1 + x2m2) / ρ12 - x1m1/ ρ1 –x2 m2/ ρ2 (2)

Where VE excess molar volume of the mixture,x1 and x2 are the malefactions of the component 1 and component
2,m1 and m2 are the coefficients of component 1 and 2, ρ12 mixture density and ρ1, ρ2 are the densities of component
1 and component 2.

The variation of excess molar volumes with the mole fraction of Nitrobenzene with 1,4 Dioxane at various
temperatures (303 .15, 308.15 and 313.15) K are represented in “Fig. 2”.

The indication of excess molar volume of a framework relies on upon the relative greatness of
development/constriction on blending of two fluids. On the off chance that the components bringing about

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development overwhelm the withdrawal variables, the VE gets positive. Then again if the compression components
overwhelm the development variables, then VE get negative. The elements that are in charge of development in

volume are as takes after, Loss of dipolar affiliation and geometry of sub-atomic structure, which does not permit

fitting of one part into other segment. The Steric obstacle contradicts vicinity of the constituent atoms [4-6]. The
negative VE qualities emerge because of predominance of the accompanying components Chemical association

between constituent chemicals and convenience of particles of one segment into the interstitials of the atoms of the

other part. The Geometry of atomic structure that supports fitting of the segment atoms with one another. The
negative VE values in the mixtures under study demonstrate that collaborations between atoms of the mixtures are

stronger than communications between particles in the unadulterated fluids and that affiliated power rule the conduct

of the result.

∆η=η12-(x1η1+ x2 η 2) (3)

Where ∆η is the viscosity deviation and η is the dynamic viscosity.

The results of variation in viscosity deviations of binary systems consisting of Nitrobenzene with 1, 4 Dioxane at
temperatures of 303.15K, 308.15K, and 313.15K are represented in “Fig. 1”.This result shows negative deviations
over the whole go of mole portion. The thickness of the mixture firmly relies on upon the entropy of mixture, which
is connected with fluid's structure and enthalpy. It will hence with sub-atomic cooperations between the parts of the
mixtures. Thusly the thickness deviation relies on upon atomic associations and on the size and state of the atoms.

STANDARD DEVIATION

SD=(Σ(νexp - νcalc)2/(N-m)1/2 (4)

Where, N-Number of data points, m – Number of coefficients, the calculated values of coefficients along with the
standard deviation are given in table 4. Interaction parameters and Predicted kinematic viscosities and Excess molar
volume of Nitrobenzene and 1, 4-dioxane mixture at (303.15, 308.15 and 313.15) K are presented in table 3.

NON LINEAR MODEL
The binary mixture calculated data of VE, ∆η were correlated with the composition data by the McAllister Model.

The size ratio of the 2 molecules should be less than 1.5.

ln υ = x1 3 lnυ 1 + 3 x12 x2 lnυ 12 +3x1x22lnυ 21 + x2 3 lnυ 2 – (5)
ln( x1+ x2 M2/M1)+ 3x1 2x2 ln(( 2+ M2/M1 )/3 ) +
3x1x22ln( 1+ 2 M2/M1)/3) + x2 3 ln(M2/M1)

This McAllister equation is based on three body model. It contains 2 constants namely υ12 and υ21. The constants can
be evaluated using least square method.

Table-1: Experimental Densities and viscosities of Pure Liquids with Literature Values at 303.15K

Component T/K ρ/g.cm-3 Exptl η/(mpa.s) Exptl
1,4 Dioxane 303.15 Lit 1.0221 Lit 1.0985
Nitrobenzene 303.15 1.1909 1.6879
1.0222 1.0985
1.1999 1.6880

Table-2: Experimental Densities and viscosities of 1,4 Dioxane + Nitro Benzene at 303.15, 308.15 and 313.15K

X1 ρ 303.15K VE ρ 308.15K VE ρ 313.15K VE
0.0000 1.1909 η 0 1.2054 η 0 1.2998 η 0
0.1017 1.1886 0.6344 1.1987 0.7059 1.2082 0.4088
0.2101 1.0920 1.6879 1.2237 1.0214 1.6919 0.9749 1.1690 1.7896 0.7774
0.3431 1.0839 1.6549 1.6842 0.9874 1.5987 1.1458 1.0934 1.7523 0.9914
0.4899 1.0765 1.6020 2.1678 0.9658 1.4856 1.4670 0.9842 1.7413 1.1730
0.5063 1.0684 1.5963 2.1617 0.9412 1.4520 1.6085 0.9742 1.7354 1.2423
0.6173 1.0574 1.4988 2.2482 0.9357 1.3287 1.4808 0.9631 1.6987 0.9372
0.7459 1.0469 1.3850 1.8470 0.8756 1.3025 1.1035 0.8956 1.5360 0.7735
0.8583 1.0455 1.3210 1.5113 0.8654 1.2950 0.7168 0.8714 1.4851 0.4905
0.9101 1.0356 1.2972 0.9967 0.8653 1.2869 0.4820 0.8649 1.3985 0.2992
1.0000 1.0221 1.2531 0 0.8612 1.2063 0 0.8547 1.3560 0
1.0996 1.1968 1.2682
1.0958 1.1680 1.2847

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Table-3: Predicted kinematic viscosities by McAllister nonlinear model for 1,4Dioxane + Nitro Benzene at 303.15, 308.15 and 313.15 K

X1 γexpt(CS) γpred (CS) γexpt(CS) γpred (CS) γexpt(CS) γpred (CS)
303.15K (McAllister-303.15K) 308.15K (McAllister-308.15K) 313.15K (McAllister-313.15K)
0.0000 0.8053 0.7866 0.7701
0.1017 0.8204 0.8052 0.7162 0.7866 0.7923 0.7712
0.2101 0.8409 0.8204 0.7297 0.7163 0.8021 0.7956
0.3431 0.8633 0.8519 0.7421 0.7297 0.8377 0.8121
0.4899 0.8790 0.8666 0.7544 0.7532 0.8522 0.8399
0.5063 0.8795 0.8791 0.7608 0.7554 0.8718 0.8566
0.6173 0.8798 0.8796 0.7968 0.7709 0.8996 0.8719
0.7459 0.9347 0.8799 0.9311 0.7965 0.9101 0.8996
0.8583 1.0833 0.9348 1.0736 0.9422 1.6566 0.9121
0.9101 1.5305 1.0835 1.3980 1.0763 1.5988 1.6654
1.0000 1.6879 1.5315 1.6989 1.3979 1.9898 1.5684
1.6880 1.6998 1.9899

0 0.2 0.4 0.6 0.8 1
0

-0.02

Viscosity deviation -0.04

-0.06

-0.08 303.15K
-0.1 308.15K
313.15K
-0.12

Molefraction

.

Excess molar volume Figure 1: Deviation in viscosity (∆η) for 1, 4 Dioxane + Nitro benzene at 303.15, 308.15 and 313.15 K

2.5

303.15K
2 308.15K

313.15K
1.5

1

0.5

0 .
0 0.2 0.4 0.6 0.8 1
Molefraction 138

Figure 2: Excess molar volume (VE) for 1, 4 Dioxane + Nitro benzene at 303.15, 308.15 and 313.15 K

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Golamari Siva Reddy et al Der Pharma Chemica, 2014, 6 (4):135-139

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Table- 4: Parameters of McAllister nonlinear model, constants and standard deviations (σ) of Binary liquid mixtures

Temperature(K) υ12 υ21 Σ
303.15 0.8970 0.8529 0.0077
308.15 0.8564 0.8380 0.0058
313.15 0.8466 0.8125 0.0049

CONCLUSION

From the study, Inductive impact of nitrobenzene gathering in nitrobenzene is giving electron, because of this
Nitrobenzene gathering gets to be marginally positive and in the meantime phenyl gathering gets negative, this
makes the compound to weakly dipolar. For this situation, the power between not at all like atoms is lesser than the
energy between like particles in mixtures. It might be inferred that the positive Excess molar volumes and negative
deviations thickness because of frail sub-atomic associations existing between the binary mixtures of 1, 4 Dioxane +
Nitrobenzene. Thickness of the double mixture and the McAllister three-body model is extremely appropriate for
associating Kinematic consistency of the parallel mixture with least standard deviation in present study.

Acknowledgement
The authors are grateful to the Management of K L University for providing laboratory facilities and thankful to the
Editor and reviewers for their constructive comments.

REFERENCES

[1] Mc-Allister. R.A. 1960. The Viscosity of liquid mixtures, AICHE Journal.l6: 427-431.
[2] Martin Contreras S. 2001 J. Chem. Eng. Data, 46, 1149 - 1152.
[3] Golamari Siva Reddy and Mallu Maheswara Reddy, Journal of Chemical and Pharmaceutical Research, 2013,
5(11):644-648
[4] Changsheng, Y.; Wali, Yu; Peisheng, M. J. Chem. Eng. Data 2005, 50, 1197–1203.
[5] S. Senthil Raja and T. R Kubendran, 2004. J. Chem. Eng. Data, 49, 421-425.
[6] Baskaran.R. and Kubendran.T.R, 2007. Chemical Physics Research Journal, 2: 1-14.
[7] Fabio Comelli, Romolo Francesconi, Adriana Bigi, and Katia Rubini, 2006. J. Chem. Eng. Data , 51, 665-670

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