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Research ArticleThermoacoustic Volumetric and Viscometric Investigations inBinary Liquid System of Cyclohexanone with Benzyl Benzoate atT = 30815 31315 and 31815 K
Sk Md Nayeem1 M Kondaiah2 K Sreekanth3 and D Krishna Rao4
1Department of Physics KRK Govt Degree College Addanki 523 201 India2Department of Physics NM Govt Degree College Jogipet Medak District Telangana 502270 India3Department of Physics PBN College Guntur District Nidubrolu 522124 India4Department of Physics Acharya Nagarjuna University Nagarjuna Nagar 522 510 India
Correspondence should be addressed to D Krishna Rao krdhanekulayahoocoin
Received 5 September 2014 Accepted 26 November 2014 Published 29 December 2014
Academic Editor Ahmet Z Sahin
Copyright copy 2014 Sk Md Nayeem et alThis is an open access article distributed under the Creative CommonsAttribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited
Ultrasonic velocities (119906) densities (120588) and viscosities (120578) of binary liquid mixtures of cyclohexanone with benzyl benzoateincluding pure liquids over the entire composition range have been measured at 30815 K 31315 K and 31815 K Using theexperimental results parameters such as molar volume (119881
119898) isentropic compressibility (119896
119904) intermolecular free length (119871
119891)
acoustic impedance (119885) internal pressure (120587119894) enthalpy (119867) Gibbs free energy of activation of viscous flow (119866lowast119864) and
excessdeviation properties of these including partial molar volumes (1198811198981
1198982) partial molar volume of the components at infinite dilution (119881infin
1198981119881infin1198982
) and excess partial molar volume at infinite dilution(119881119864infin1198981
and119881119864infin1198982
) have been computedThe observed negative values of119881119864119898Δ119896119904 119871119864119891 and 120587119864
119894and positive values of 119911119864119867119864 Δ119866lowast119864Δ120578
and Δ119906 for all the liquid mixtures studied clearly indicate the presence of strong dipole-dipole-type interactions fitting of smallermolecules into bigger molecules Further theoretical values of sound velocity and viscosity in the mixtures have been evaluatedusing various theories and have been compared with experimental values to verify the applicability of such theories to the systemsstudied
1 Introduction
Volumetric viscometric and ultrasonic investigations ofliquid mixtures are of considerable importance in under-standing the intermolecular interactions occurring amongcomponent molecules and they find application in severalindustrial and technological processes [1 2] The work onmedicinally used chemical compounds requires the attentionof the society in all aspects including ultrasonic behaviourBenzyl benzoate is a carboxylate ester which is used in oilyinjections and as an insect repellent and as acaricide andpediculicide in veterinary hospitals It is an effective andinexpensive topical treatment for human scabies It is a polar(120583 = 206D) molecule (C+=Ominus) with the structure shownin Figure 12 Behaviour of benzyl benzoate in many liquids
such as aliphatic alkanes aromatic alkanes aliphatic alcoholssubstituted benzenes acetates ketones and DMSO (supersolvent) has been thoroughly studied ultrasonically [3ndash6]
Ketone is an organic compound that contains a carbonylgroup and two aliphatic or aromatic substituents containingthe chemical formula RCOR1 Here R and R1may be same ordifferent incorporated into a ring (alkyl aryl and heterocyclicradicals) Cyclohexanone is a ketone liquid The chemicalreactivity of the carbonyl group (C+=Ominus) plays important rolein chemical reactions and is influenced considerably by stericeffects The greater electronegativity of Ominus and high dipolemoment make ketones polar (120583 = 325D) The resonancestructure shown in Figure 12 illustrates this polarity Thusa study on thermophysical properties data of binary liquidmixtures has attracted considerable interest in the literature
Hindawi Publishing CorporationJournal of ermodynamicsVolume 2014 Article ID 487403 13 pageshttpdxdoiorg1011552014487403
2 Journal of Thermodynamics
[7ndash10] Cyclohexanone and its derivatives are used for thesynthesis of pharmaceuticals dyes herbicides pesticidesplasticizers and rubber chemicals
The liquids under investigation have been chosen onthe basis of their medicinal and industrial applicationsThese applications have greatly stirred the need for extensiveinformation on the thermodynamic acoustic and trans-port properties of these solvents and their mixtures [11ndash13] Ultrasonic and density data for binary mixtures ofbenzyl benzoate with Isomers of butanol have been stud-ied previously in our laboratory [14] The literature surveyreveals that Madhuri et al [15] have reported ultrasonicvolumetric and viscometric studies of benzyl benzoate withacetonitrile and benzonitrile Recently Sri et al [16] reportedultrasonic velocity and density in binary liquids of certainaldehydes and esters In the present investigation a detailedstudy of the binary mixture of benzyl benzoate (BB) withcyclohexanone (CH) at three temperatures 30815 K 31315 Kand 31815 K is aimed From the experimentally measureddata of ultrasonic velocity (119906) densities (120588) and viscosities(120578) thermodynamic and other related parameters like molarvolume isentropic compressibility acoustic impedance freelength relaxation time internal pressure enthalpy andGibbsfree energy of activation of viscous flow are computed andin terms of some of these excessdeviation parameters thenature of molecular interactions is predicted in the binarymixtures An evaluation of velocities and viscosities usingthree different empirical theories is also attempted at all thethree temperatures
2 Experimental Section
Benzyl benzoate (BB) and cyclohexanone (CH) used inthe present study were the AR grade products from LOBAChemicals India and were purified by standard methodsdescribed in the literature [17ndash19] The mass fraction purityof liquids obtained is gt0995 Before use the chemicals werestored over 04 nm molecular sieves approximately for 72 hto remove water content and degassed and latter kept in airtight bottles The mass measurements are performed witha METTLER TOLEDO (Switzerland make) AB135-SFACTdigital balance with an accuracy of plusmn001mgThe uncertaintyin the mole fraction is 10minus4 The ultrasonic velocity ofpure liquids and their binary mixtures has been measuredby using a multifrequency ultrasonic interferometer (M-82 model) supplied by Mittal Enterprises New Delhi ata fixed frequency of 2MHz with an accuracy of plusmn02The temperature of liquid sample in the interferometer cellis maintained constant by circulating water pumped fromconstant temperature water bath In the present study theconstant temperature water bath (digital electronic) suppliedby Concord Instruments Co Ltd Chennai (RAAGA type)has been used The instrument can maintain temperature toplusmn001 K as per its specifications
Densities and viscosities of pure liquids and liquid solu-tions are determined using 5 cm3 two stem double walledParker amp Parker-type pycnometer [20] andOstwald viscome-ter which is standardized as described by Naidu and Prasad
[21] using triply distilled water respectively The estimatedaccuracy in measuring the density is 3 in 105 parts Theuncertainty in the viscosity measurement is plusmn02 Thedetailed description of measurement of density and viscosityis discussed in our previous papers [22ndash25] The densitiesvelocities and viscosities of pure liquids in this investigationat temperature of 30815 K 31315 K and 31815 K are compiledin Table 1 together with the literature data [15 26] availableThese results are found to be in good agreementwith reporteddata
3 Results and Discussion
Themeasured values of density velocity and viscosity and thecalculated values ofmolar volume isentropic compressibilityfree length acoustic impedance internal pressure relaxationtime enthalpy and Gibbs free energy of activation of viscousflow are calculated using standard relations and are presentedin Table 2 with mole fraction of cyclohexanone in benzylbenzoate In the present investigation the values of 119906 and 119911increase and those of 119896
119904and 119871
119891decrease as the mole fraction
increases The variation of ultrasonic speed in a solutiondepends upon the increase or decrease of 119871
119891after mixing
the components This is due to the fact that ultrasonic speedincreases if the intermolecular free length decreases and viceversa The decrease in the values of 119896
119904and 119871
119891with mole
fraction in the present study indicates significant interactionsbetween CH and BB molecules
Study of deviationexcess properties plays vital role inthe study of molecular interactions The nonlinear variationof excessdeviation properties with mole fraction of BB isresponsible for nonideality in the systems of binary liquidmixture [15]The factors responsible for such departure fromideality may either be due to the presence of intermolecularforces between the constituents in the mixture or due tocompound formation between solute and solvent or as aresult of association of either to form complex molecules[27] These excess parameters throw light upon the strengthof interaction and their variation with mole fraction findsapplication in typifying the physicochemical behaviour ofliquid mixtures [28]
The deviationexcess properties have been calculatedusing the relation
119884119864
= 119884real minus 119884ideal (1)
where 119884119864 represent deviationexcess value of the parameter119884real is the experimental value of the parameter of liquidmixture and 119884ideal is the ideal value of the parametercomputed theoreticallyThe119884119864 = 119881119864
119898is excess molar volume
119885119864 is excess specific acoustic impedance Δ119896
Table 1 Comparison of experimental values of ultrasonic velocity (u) density (120588) and viscosity (120578) of pure liquids with the literature valuesconcerned at 30815 31315 and 31815 K
1199041 1198961199042are the volume fractions and isen-
tropic compressibilities of components 1 and 2 respectivelySince 119896
119904is not additive on mole fraction but is additive
on volume fraction hence such values are calculated usingvolume fractionB
119894
B119894=
119909119894119881119894
sum119909119894119881119894
(3)
The excessdeviation properties have been fitted to a Redlich-Kister-type polynomial equation [29]
119884119864
= 119909 (1 minus 119909)
119895
sum
119894=0
119860119894(1 minus 2119909)
119894
(4)
where 119909 is the mole fraction of CH and for evaluating Δ119896119904 119909
is replaced by volume fraction (B119894) and 119860
119894are the adjustable
parameters of the function and are determined using the leastsquare method In the present investigation ldquo119894rdquo values takenare from 0 to 4The corresponding standard deviations 120590(119884119864)were calculated using the expression
120590 (119884119864
) =[
[
sum(119884119864
exp minus 119884119864
cal)2
(119898 minus 119899)
]
]
12
(5)
where ldquo119898rdquo is the total number of experimental points and ldquo119899rdquois the number of coefficients in (4) The calculated values ofthe coefficients 119860
119894along with the standard deviations (120590) are
given in Table 3Figure 1 represents the variation of excess molar volume
(119881119864
119898)with mole fraction of CHThe sign of119881119864
119898depends upon
the contraction and expansion of volume of the liquids due tomixingThe excessmolar volume is the resultant contributionfrom several opposing effects namely chemical physical andstructural [30] The chemical or specific interactions resultin volume contractions leading to negative excess molarvolume and these include charge-transfer complexes dipole-dipole dipole-induced dipole interactions and formationof H-bonding between component molecules The physicalinteractions or nonspecific interactions are weak and theseinclude breaking of the structure of one or both of the com-ponents in a solution that is the loss of dipolar associationbetween the molecules (dispersion forces) steric hindranceof the molecules and H-bond rupture and stretching of self-associated molecules (like alcohols)The structural contribu-tions are mostly negative and arise from several effects such
minus0025
minus0020
minus0015
minus0010
minus0005
00000 02 04 06 08 1
x
VE m
(10
minus5
m3middotm
olminus
1)
Figure 1 Variation of excess molar volume 119881119864119898 with mole fraction
119909 of CH in BB at (X) 30815 K (◼) 31315 K and (998771) 31815 K
as interstitial accommodation and geometrical fitting of onecomponent into another due to the differences in the molarvolume and free volume between components In the presentinvestigation the sign of 119881119864
119898is found to be negative over the
entire composition rangeThe nature of existing interaction in a binary liquid
can also be analysed by knowing their individual chemicaland physical properties It is well known that BB and CHare polar and their dipole moment values follow 120583CH =325D gt 120583BB = 206D In the present study possibilityof Keesom dipole-dipole van der Waals forces which arisedue to the dipole moment of the components gives stronginteractions leading to negative values of 119881119864
119898[31] Moreover
the liquids BB and CH lack hydroxyl groups hence thepossibility for formation of intermolecular hydrogen bonds istrifling Further themolar volumes of CH and BB are 104459and 190428 (times10minus5m3sdotmolminus1) respectively at 30815 K Thisimplies that geometrical fitting of smaller molecules intothe voids created by the bigger molecules is most favorableThe 119881119864
119898values in binary mixture are thereby decreased with
increasing temperature Negative 119881119864119898values indicate strong
interactions following the order 31815K gt 31315K gt
30815KAccording toRastogi et al [32] such behaviourmayarise due to the fact that as temperature increases thermalenergy activates the molecule this would increase the rateof association of unlike molecules Similar type of trend wasobserved by Baragi et al [33] in methyl cyclohexane withalkanes
The strongmolecular interactions in the presented binarysystem are well reflected in the properties of partial molarvolumes The partial molar volumes 119881
1198981of component 1
(CH) and 1198811198982
of component 2 (BB) in the mixtures havebeen calculated by using the following equations
1198811198981
= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
1198811198982
= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(6)
where 119881lowast
1and 119881
lowast
2are the molar volumes of the pure
components of CH andBB respectively By differentiating (4)and then rearranging one can get the following equations for1198811198981
and 1198811198982
The derivates in the above equations are obtained bydifferentiating Redlich-Kister equation (8) which leads to thefollowing equations for 119881
1198981and 119881
1198982
1198811198981
= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(7)
1198811198982
= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(8)
The excess partial molar volumes are then given by
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(9)
The values of 1198811198981
and 1198811198982
are tabulated in Table 4 Thistable reproduces the values of 119881
1198981and 119881
1198982for both the
6 Journal of Thermodynamics
components in the mixtures are smaller than their individualmolar volumes in the pure state this indicates that shrinkageof volume takes place onmixing CHwith BB Figures 2 and 3represent the disparity of excess partialmolar volumes of119881119864
1198981
and 1198811198641198982
respectively in the binary mixture Examinationof these figures not only reveals the existence of strongforces between the unlike molecules but also supports thedeductions drawn from excess molar volume
The partial molar volumes and excess partial molarvolumes of the components at infinite dilution 119881infin
1198981 119881infin1198982
119881
119864infin
1198981 and119881119864infin
1198982 respectively were obtained by putting 119909 = 0
reported in Table 5 This table shows that these values arenegative from which we conclude that strong interactionsexist among the unlike molecules of the mixtures whichsupport the trends of 119881119864
119898values observed in these mixtures
Figures 4 and 5 represent the deviation in isentropiccompressibility (Δ119896
119904) and excess intermolecular free length
(119871119864
119891) respectively These values are found to be negative for
the system under investigation at all temperaturesThe natureof Δ119896119904 119871119864119891plays vivacious role in assessing the compactness
due to molecular rearrangement The extent of molecularinteractions in liquid mixtures may be due to charge transferdipole-induced-dipole dipole-dipole interactions and inter-stitial accommodation leading to more compact structuremaking Δ119896
119904and 119871119864
119891negative The values of the excess func-
tions Δ119896 119871119864119891depend upon several physical andor chemical
contributions [34ndash37] The physical contribution consists ofdispersion forces or weak dipole-dipole interaction that leadsto positive values of Δ119896
119904and 119871
119864
119891 Another factor which
involves a physical contribution is the geometrical effectallowing the fitting of molecules of two different sizes intoeach otherrsquos structure resulting in negativeΔ119896
119904119871119864119891valuesThe
strength of the interactions increases with temperatures asobserved frommore negative values of the excess parametersThey are negative throughout and become more negative atall concentrations as the temperature is increased In hetero-molecular interaction between the component molecules ofthe mixtures Fort and Moore [38] found that the negativevalue of excess compressibility indicates greater interactionbetween the components of themixtures due to the formationof hydrogen bond Thus the negative Δ119896
119904values for binary
mixtures indicate strong interactions between BB and CHAccording to Singh et al [39] negative values of excess
intermolecular free length119871119864119891indicate that soundwaves cover
longer distances due to decrease in intermolecular free lengthascribing the dominant nature of hydrogen bond interactionbetween unlike molecules Fort andMoore indicated that thepositive values of excess free length should be attributed to thedispersive forces and negative excess values should be due
1
05
0
minus05
minus15
minus25
0 02 04 06 08 1
xminus1
minus2
VE m
2(1
0minus
5m
3middotm
olminus
1)
Figure 2 Variation of excess partial molar volume1198811198641198982
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
5
4
3
2
1
0
minus1
minus2
0 02 04 06 08 1
xV
E m1
(10
minus5
m3middotm
olminus
1)
Figure 3 Variation of excess partial molar volume 1198811198641198981
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
minus01
minus02
minus03
minus04
minus05
minus06
minus07
0 02 04 06 08 1
x
Δk
s(1
0minus
10Pa
minus1)
Figure 4 Variation of deviation in isentropic compressibility Δ119896119904
with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and(998771) 31815 K
minus0030
minus0025
minus0020
minus0015
minus0010
minus0005
00000 02 04 06 108
LE f
(10
minus10
m)
x
Figure 5 Variation of excess free length 119871119864119891 with mole fraction 119909
of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
Journal of Thermodynamics 7
Table 4 Mole fraction (119909) and values of partial molar volume 1198811198982
(10minus5 m3sdotmolminus1) 119881
1198981(10minus5 m3
sdotmolminus1) of the binary system at 3081531315 and 31815 K
119909
119879 = 30815 K 119879 = 31315 K 119879 = 31815 K1198811198982
Figure 6 Variation of excess acoustic impedance 119885119864 with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
to hydrogen bond formation or dipole-dipole interactionsbetween solute and solvent In the present study the negativecontribution in all the systems prevails in the existenceof greater interactions Nain et al [40] also concluded asimilar observation From Figure 6 the excess values of 119885119864are found to be positive for the system at all temperaturesunder investigation According to Kondaiah andRao [41] thenature of the positive values of 119885119864 is attributed to specificinteraction between the heteromolecules This further sup-ports our earlier finding
The variations of excess internal pressure (120587119864119894) and excess
enthalpy (119867119864) are presented in Figures 7 and 8 for the present
minus35
minus30
minus25
minus20
minus15
minus10
minus5
000 02 04 06 08 10
x
120587E i
(kJmiddotm
olminus
1)
Figure 7 Variation of excess internal pressure 120587119864119894 with mole
fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
1000
2000
3000
4000
5000
6000
7000
8000
0 02 04 06 08 1
x
HE
(Jmiddotm
olminus
1)
Figure 8 Variation of excess enthalpy119867119864 with mole fraction 119909 ofCH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
system at all the three temperatures respectively From thesefigures it is observed that 120587119864
119894is negative and 119867119864 is positive
over the entire composition range of CH In accordance withKondaiah et al [42] the negative values of 120587119864
119894indicate the
existence of strong specific interactions and according toKumar and Rao [43] positive value of Δ119867 suggests strongbonding and exothermic reactionsThus it can be concludedthat strong specific interactions are operative in the systems
8 Journal of Thermodynamics
000
020
040
060
080
100
0 02 04 06 08 1
xΔ
Glowast
E(k
Jmiddotmol
minus1)
Figure 9 Variation of excess Gibbs free energy of activation of viscous flow Δ119866lowast119864 with mole fraction 119909 of CH in BB (X) 30815 K (◼)31315 K and (998771) 31815 K
000
005
010
015
020
025
0 02 04 06 08 1
x
Δ120578
(10
minus3
Nmiddotsmiddot
mminus
2)
Figure 10 Variation of deviation in viscosity Δ120578 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
investigated These conclusions support our earlier findingsof strong interactions The variation of excess Gibbs freeenergy of activation of viscous flow Δ119866lowast119864 with mole fractionof CH has been presented in Figure 9 at all temperaturesThese values are positive over the entire range of compositionof CH According to Iloukhani et al [44 45] negative valuesof Δ119866lowast119864 indicate the presence of weak physical forces such asdispersive forces in the system On the other hand positivevalues of it suggest strong specific interactions This alsosupports the conclusions drawn from our earlier findings
According to Fort and Moore [46] deviation in viscositytends to become more positive as the strength of the inter-action increases The deviation in viscosity variation gives aqualitative estimation of the strength of the intermolecularinteractions The deviation in viscosities may be generallyexplained by considering the following factors (i) The differ-ence in size and shape of the component molecules and theloss of dipolar association in pure componentmay contributeto a decrease in viscosity and (ii) specific interactions betweenunlike components such as hydrogen bond formation ordipole-dipole interactions or charge-transfer complexes maycause increase in viscosity in mixtures compared to in purecomponents [47]The former effect produces negative devia-tion in viscosity and latter effect produces positive deviationin viscosity A perusal of Figure 10 shows that the values ofΔ120578 are positive for the present system at three temperaturesThe positive Δ120578 values decrease with increasing temperatureThe positive Δ120578 values indicate specific interactions whilethe negative Δ120578 values indicate dispersion forces [48ndash50]
In the present investigation the positive values of all binarysystems may be attributed to the dipole-dipole interactionsThe sign and magnitude of Δ119906 play important roles indescribing molecular rearrangements as a result of molecularinteractions occurring among the component molecules inthe mixtures The excess ultrasonic speed with mole fractionof CH is shown in Figure 11 Here we observed that theΔ119906 values are positive for all binary systems over the entirerange of composition at all the studied temperatures Positivedeviations indicate the increasing strength of interactionbetween component molecules of binary liquid mixturesAccording to Reddy et al [51] strong interactions amongthe components of a mixture lead to the formation ofmolecular aggregates and more compact structures thensound will travel faster through the mixture by means oflongitudinal waves and hence the ultrasonic speed deviationswith respect to a linear behaviour will be positive while ifthe structure-breaking factor in the mixture predominatesresulting expansion then the speed of sound through themixture will be slower resulting in negative deviation in thespeed of sound According to Ali et al [52] more positivevalues mean much more strong interactions between themolecules Therefore based on the above references for thepresent scenario interactions are found to be in the order31815K gt 31315K gt 30815K this again emphasizes ourview regarding the interaction between CH and BB
In the present study theoretical sound velocities havebeen evaluated by considering CH as one component andBB as the other component in the binary mixture at all
Journal of Thermodynamics 9
0
5
10
15
20
25
30
35
40
45
0 02 04 06 08 1
xΔ
u(m
middotsminus1)
Figure 11 Variation of deviation in ultrasonic velocity Δ119906 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
C=O
R
R
C=O
R
R∙ ∙ ∙ ∙
∙ ∙ ∙∙
∙ ∙
+ minusO
O
Structure of benzyl benzoate Resonance structure of ketone
lt=gt
Figure 12
the three temperatures Such an evaluation of theoreticalsound velocity is useful to verify the applicability of variousassumes of the theories of liquid mixtures and to arriveat some useful implications regarding the (strength of)molecular interactions between component liquids in somecases The theoretical values of ultrasonic velocity obtainedusing various theories along with the experimental velocityand percentage deviation are summarized in Table 6 Nomoto[53] established the following relation for sound velocitybased on the supposition of the linearity of the molecularsound velocity and the additives of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(11)
Van Dael [54] obtained the ideal mixture relation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(12)
The impedance dependence relation used by Baluja andParsania [55] is given below
119880imp =sum119909119894119885119894
sum119909119894120588119894
(13)
where 119909119894is mole fractions119872
119894is molecular weight 119877 is the
molar sound speed and 119885119894is acoustic impedance of CH and
BB respectively at three temperaturesPercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906expt
] (14)
On observing Table 6 among all the empirical theoriesNomotorsquos relation gives the best estimate of experimental val-ues of sound velocity in the system followed by impedancersquosrelation In the present binary systems the difference betweenexperimental and theoretical velocities is greater where themole fraction of CH varies in the region 04 to 07 Hence itcan be qualitatively inferred that the strength of interactionin the binary mixtures is more in this range of compositionof binary mixtures
The dynamic viscosities of the liquid mixtures have beencalculated using the several empirical relations
Grunberg and Nissan [56] proposed the following equa-tion for the measurement of viscosity of liquid mixtures
where (119882visRT) is an interaction parameterThe theoretical viscosity values using (15) to (17) along
with the percentage error are compiled in Table 7 Theevaluated values of parameters 119866
12 11986712 and 119882visRT and
standard deviations 120590 (10minus3 kgminus1sdotsminus1) are presented in Table 8
10 Journal of Thermodynamics
Table 6 Experimental and theoretical velocities from various empirical relations and percentage deviation in velocities with molefraction119909 of CH with BB at 119879 = 30815 31315 and 31815 K
The estimated values of120590 are indicating that the viscosities arewell correlated by all the three viscosity models Prolongo etal [59] reported positive values of interaction parameters cor-responding to systems with negative excess molar volumesThis is consistent with our results Among all of thesemodelsthe viscosity representations obtained from the Hind modelare in best agreement with the experimental viscosity data
4 Conclusions
(i) Ultrasonic velocities densities and viscosities forbinary liquids of CH with BB are determined exper-
imentally at T = 30815 K 31315 K and 31815 K overthe entire composition range
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119885119864 120587119864
119894 119867119864 Δ119866lowast119864 and
Δ119906 are calculated from experimental results at allthree temperatures The excessdeviation propertiesare fitted to Redlich-Kister-type polynomial and cor-responding standard deviations are evaluated Theobserved negative values of 119881119864
119898 Δ119896119904 119871119864119891 and 120587119864
119894and
positive values of 119885119864 119867119864 Δ119866lowast119864 Δ120578 and Δ119906 for allthe liquid mixtures studied clearly indicate dipole-dipole-type interactions and the geometrical fitting
Journal of Thermodynamics 11
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
[7ndash10] Cyclohexanone and its derivatives are used for thesynthesis of pharmaceuticals dyes herbicides pesticidesplasticizers and rubber chemicals
The liquids under investigation have been chosen onthe basis of their medicinal and industrial applicationsThese applications have greatly stirred the need for extensiveinformation on the thermodynamic acoustic and trans-port properties of these solvents and their mixtures [11ndash13] Ultrasonic and density data for binary mixtures ofbenzyl benzoate with Isomers of butanol have been stud-ied previously in our laboratory [14] The literature surveyreveals that Madhuri et al [15] have reported ultrasonicvolumetric and viscometric studies of benzyl benzoate withacetonitrile and benzonitrile Recently Sri et al [16] reportedultrasonic velocity and density in binary liquids of certainaldehydes and esters In the present investigation a detailedstudy of the binary mixture of benzyl benzoate (BB) withcyclohexanone (CH) at three temperatures 30815 K 31315 Kand 31815 K is aimed From the experimentally measureddata of ultrasonic velocity (119906) densities (120588) and viscosities(120578) thermodynamic and other related parameters like molarvolume isentropic compressibility acoustic impedance freelength relaxation time internal pressure enthalpy andGibbsfree energy of activation of viscous flow are computed andin terms of some of these excessdeviation parameters thenature of molecular interactions is predicted in the binarymixtures An evaluation of velocities and viscosities usingthree different empirical theories is also attempted at all thethree temperatures
2 Experimental Section
Benzyl benzoate (BB) and cyclohexanone (CH) used inthe present study were the AR grade products from LOBAChemicals India and were purified by standard methodsdescribed in the literature [17ndash19] The mass fraction purityof liquids obtained is gt0995 Before use the chemicals werestored over 04 nm molecular sieves approximately for 72 hto remove water content and degassed and latter kept in airtight bottles The mass measurements are performed witha METTLER TOLEDO (Switzerland make) AB135-SFACTdigital balance with an accuracy of plusmn001mgThe uncertaintyin the mole fraction is 10minus4 The ultrasonic velocity ofpure liquids and their binary mixtures has been measuredby using a multifrequency ultrasonic interferometer (M-82 model) supplied by Mittal Enterprises New Delhi ata fixed frequency of 2MHz with an accuracy of plusmn02The temperature of liquid sample in the interferometer cellis maintained constant by circulating water pumped fromconstant temperature water bath In the present study theconstant temperature water bath (digital electronic) suppliedby Concord Instruments Co Ltd Chennai (RAAGA type)has been used The instrument can maintain temperature toplusmn001 K as per its specifications
Densities and viscosities of pure liquids and liquid solu-tions are determined using 5 cm3 two stem double walledParker amp Parker-type pycnometer [20] andOstwald viscome-ter which is standardized as described by Naidu and Prasad
[21] using triply distilled water respectively The estimatedaccuracy in measuring the density is 3 in 105 parts Theuncertainty in the viscosity measurement is plusmn02 Thedetailed description of measurement of density and viscosityis discussed in our previous papers [22ndash25] The densitiesvelocities and viscosities of pure liquids in this investigationat temperature of 30815 K 31315 K and 31815 K are compiledin Table 1 together with the literature data [15 26] availableThese results are found to be in good agreementwith reporteddata
3 Results and Discussion
Themeasured values of density velocity and viscosity and thecalculated values ofmolar volume isentropic compressibilityfree length acoustic impedance internal pressure relaxationtime enthalpy and Gibbs free energy of activation of viscousflow are calculated using standard relations and are presentedin Table 2 with mole fraction of cyclohexanone in benzylbenzoate In the present investigation the values of 119906 and 119911increase and those of 119896
119904and 119871
119891decrease as the mole fraction
increases The variation of ultrasonic speed in a solutiondepends upon the increase or decrease of 119871
119891after mixing
the components This is due to the fact that ultrasonic speedincreases if the intermolecular free length decreases and viceversa The decrease in the values of 119896
119904and 119871
119891with mole
fraction in the present study indicates significant interactionsbetween CH and BB molecules
Study of deviationexcess properties plays vital role inthe study of molecular interactions The nonlinear variationof excessdeviation properties with mole fraction of BB isresponsible for nonideality in the systems of binary liquidmixture [15]The factors responsible for such departure fromideality may either be due to the presence of intermolecularforces between the constituents in the mixture or due tocompound formation between solute and solvent or as aresult of association of either to form complex molecules[27] These excess parameters throw light upon the strengthof interaction and their variation with mole fraction findsapplication in typifying the physicochemical behaviour ofliquid mixtures [28]
The deviationexcess properties have been calculatedusing the relation
119884119864
= 119884real minus 119884ideal (1)
where 119884119864 represent deviationexcess value of the parameter119884real is the experimental value of the parameter of liquidmixture and 119884ideal is the ideal value of the parametercomputed theoreticallyThe119884119864 = 119881119864
119898is excess molar volume
119885119864 is excess specific acoustic impedance Δ119896
Table 1 Comparison of experimental values of ultrasonic velocity (u) density (120588) and viscosity (120578) of pure liquids with the literature valuesconcerned at 30815 31315 and 31815 K
1199041 1198961199042are the volume fractions and isen-
tropic compressibilities of components 1 and 2 respectivelySince 119896
119904is not additive on mole fraction but is additive
on volume fraction hence such values are calculated usingvolume fractionB
119894
B119894=
119909119894119881119894
sum119909119894119881119894
(3)
The excessdeviation properties have been fitted to a Redlich-Kister-type polynomial equation [29]
119884119864
= 119909 (1 minus 119909)
119895
sum
119894=0
119860119894(1 minus 2119909)
119894
(4)
where 119909 is the mole fraction of CH and for evaluating Δ119896119904 119909
is replaced by volume fraction (B119894) and 119860
119894are the adjustable
parameters of the function and are determined using the leastsquare method In the present investigation ldquo119894rdquo values takenare from 0 to 4The corresponding standard deviations 120590(119884119864)were calculated using the expression
120590 (119884119864
) =[
[
sum(119884119864
exp minus 119884119864
cal)2
(119898 minus 119899)
]
]
12
(5)
where ldquo119898rdquo is the total number of experimental points and ldquo119899rdquois the number of coefficients in (4) The calculated values ofthe coefficients 119860
119894along with the standard deviations (120590) are
given in Table 3Figure 1 represents the variation of excess molar volume
(119881119864
119898)with mole fraction of CHThe sign of119881119864
119898depends upon
the contraction and expansion of volume of the liquids due tomixingThe excessmolar volume is the resultant contributionfrom several opposing effects namely chemical physical andstructural [30] The chemical or specific interactions resultin volume contractions leading to negative excess molarvolume and these include charge-transfer complexes dipole-dipole dipole-induced dipole interactions and formationof H-bonding between component molecules The physicalinteractions or nonspecific interactions are weak and theseinclude breaking of the structure of one or both of the com-ponents in a solution that is the loss of dipolar associationbetween the molecules (dispersion forces) steric hindranceof the molecules and H-bond rupture and stretching of self-associated molecules (like alcohols)The structural contribu-tions are mostly negative and arise from several effects such
minus0025
minus0020
minus0015
minus0010
minus0005
00000 02 04 06 08 1
x
VE m
(10
minus5
m3middotm
olminus
1)
Figure 1 Variation of excess molar volume 119881119864119898 with mole fraction
119909 of CH in BB at (X) 30815 K (◼) 31315 K and (998771) 31815 K
as interstitial accommodation and geometrical fitting of onecomponent into another due to the differences in the molarvolume and free volume between components In the presentinvestigation the sign of 119881119864
119898is found to be negative over the
entire composition rangeThe nature of existing interaction in a binary liquid
can also be analysed by knowing their individual chemicaland physical properties It is well known that BB and CHare polar and their dipole moment values follow 120583CH =325D gt 120583BB = 206D In the present study possibilityof Keesom dipole-dipole van der Waals forces which arisedue to the dipole moment of the components gives stronginteractions leading to negative values of 119881119864
119898[31] Moreover
the liquids BB and CH lack hydroxyl groups hence thepossibility for formation of intermolecular hydrogen bonds istrifling Further themolar volumes of CH and BB are 104459and 190428 (times10minus5m3sdotmolminus1) respectively at 30815 K Thisimplies that geometrical fitting of smaller molecules intothe voids created by the bigger molecules is most favorableThe 119881119864
119898values in binary mixture are thereby decreased with
increasing temperature Negative 119881119864119898values indicate strong
interactions following the order 31815K gt 31315K gt
30815KAccording toRastogi et al [32] such behaviourmayarise due to the fact that as temperature increases thermalenergy activates the molecule this would increase the rateof association of unlike molecules Similar type of trend wasobserved by Baragi et al [33] in methyl cyclohexane withalkanes
The strongmolecular interactions in the presented binarysystem are well reflected in the properties of partial molarvolumes The partial molar volumes 119881
1198981of component 1
(CH) and 1198811198982
of component 2 (BB) in the mixtures havebeen calculated by using the following equations
1198811198981
= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
1198811198982
= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(6)
where 119881lowast
1and 119881
lowast
2are the molar volumes of the pure
components of CH andBB respectively By differentiating (4)and then rearranging one can get the following equations for1198811198981
and 1198811198982
The derivates in the above equations are obtained bydifferentiating Redlich-Kister equation (8) which leads to thefollowing equations for 119881
1198981and 119881
1198982
1198811198981
= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(7)
1198811198982
= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(8)
The excess partial molar volumes are then given by
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(9)
The values of 1198811198981
and 1198811198982
are tabulated in Table 4 Thistable reproduces the values of 119881
1198981and 119881
1198982for both the
6 Journal of Thermodynamics
components in the mixtures are smaller than their individualmolar volumes in the pure state this indicates that shrinkageof volume takes place onmixing CHwith BB Figures 2 and 3represent the disparity of excess partialmolar volumes of119881119864
1198981
and 1198811198641198982
respectively in the binary mixture Examinationof these figures not only reveals the existence of strongforces between the unlike molecules but also supports thedeductions drawn from excess molar volume
The partial molar volumes and excess partial molarvolumes of the components at infinite dilution 119881infin
1198981 119881infin1198982
119881
119864infin
1198981 and119881119864infin
1198982 respectively were obtained by putting 119909 = 0
reported in Table 5 This table shows that these values arenegative from which we conclude that strong interactionsexist among the unlike molecules of the mixtures whichsupport the trends of 119881119864
119898values observed in these mixtures
Figures 4 and 5 represent the deviation in isentropiccompressibility (Δ119896
119904) and excess intermolecular free length
(119871119864
119891) respectively These values are found to be negative for
the system under investigation at all temperaturesThe natureof Δ119896119904 119871119864119891plays vivacious role in assessing the compactness
due to molecular rearrangement The extent of molecularinteractions in liquid mixtures may be due to charge transferdipole-induced-dipole dipole-dipole interactions and inter-stitial accommodation leading to more compact structuremaking Δ119896
119904and 119871119864
119891negative The values of the excess func-
tions Δ119896 119871119864119891depend upon several physical andor chemical
contributions [34ndash37] The physical contribution consists ofdispersion forces or weak dipole-dipole interaction that leadsto positive values of Δ119896
119904and 119871
119864
119891 Another factor which
involves a physical contribution is the geometrical effectallowing the fitting of molecules of two different sizes intoeach otherrsquos structure resulting in negativeΔ119896
119904119871119864119891valuesThe
strength of the interactions increases with temperatures asobserved frommore negative values of the excess parametersThey are negative throughout and become more negative atall concentrations as the temperature is increased In hetero-molecular interaction between the component molecules ofthe mixtures Fort and Moore [38] found that the negativevalue of excess compressibility indicates greater interactionbetween the components of themixtures due to the formationof hydrogen bond Thus the negative Δ119896
119904values for binary
mixtures indicate strong interactions between BB and CHAccording to Singh et al [39] negative values of excess
intermolecular free length119871119864119891indicate that soundwaves cover
longer distances due to decrease in intermolecular free lengthascribing the dominant nature of hydrogen bond interactionbetween unlike molecules Fort andMoore indicated that thepositive values of excess free length should be attributed to thedispersive forces and negative excess values should be due
1
05
0
minus05
minus15
minus25
0 02 04 06 08 1
xminus1
minus2
VE m
2(1
0minus
5m
3middotm
olminus
1)
Figure 2 Variation of excess partial molar volume1198811198641198982
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
5
4
3
2
1
0
minus1
minus2
0 02 04 06 08 1
xV
E m1
(10
minus5
m3middotm
olminus
1)
Figure 3 Variation of excess partial molar volume 1198811198641198981
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
minus01
minus02
minus03
minus04
minus05
minus06
minus07
0 02 04 06 08 1
x
Δk
s(1
0minus
10Pa
minus1)
Figure 4 Variation of deviation in isentropic compressibility Δ119896119904
with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and(998771) 31815 K
minus0030
minus0025
minus0020
minus0015
minus0010
minus0005
00000 02 04 06 108
LE f
(10
minus10
m)
x
Figure 5 Variation of excess free length 119871119864119891 with mole fraction 119909
of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
Journal of Thermodynamics 7
Table 4 Mole fraction (119909) and values of partial molar volume 1198811198982
(10minus5 m3sdotmolminus1) 119881
1198981(10minus5 m3
sdotmolminus1) of the binary system at 3081531315 and 31815 K
119909
119879 = 30815 K 119879 = 31315 K 119879 = 31815 K1198811198982
Figure 6 Variation of excess acoustic impedance 119885119864 with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
to hydrogen bond formation or dipole-dipole interactionsbetween solute and solvent In the present study the negativecontribution in all the systems prevails in the existenceof greater interactions Nain et al [40] also concluded asimilar observation From Figure 6 the excess values of 119885119864are found to be positive for the system at all temperaturesunder investigation According to Kondaiah andRao [41] thenature of the positive values of 119885119864 is attributed to specificinteraction between the heteromolecules This further sup-ports our earlier finding
The variations of excess internal pressure (120587119864119894) and excess
enthalpy (119867119864) are presented in Figures 7 and 8 for the present
minus35
minus30
minus25
minus20
minus15
minus10
minus5
000 02 04 06 08 10
x
120587E i
(kJmiddotm
olminus
1)
Figure 7 Variation of excess internal pressure 120587119864119894 with mole
fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
1000
2000
3000
4000
5000
6000
7000
8000
0 02 04 06 08 1
x
HE
(Jmiddotm
olminus
1)
Figure 8 Variation of excess enthalpy119867119864 with mole fraction 119909 ofCH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
system at all the three temperatures respectively From thesefigures it is observed that 120587119864
119894is negative and 119867119864 is positive
over the entire composition range of CH In accordance withKondaiah et al [42] the negative values of 120587119864
119894indicate the
existence of strong specific interactions and according toKumar and Rao [43] positive value of Δ119867 suggests strongbonding and exothermic reactionsThus it can be concludedthat strong specific interactions are operative in the systems
8 Journal of Thermodynamics
000
020
040
060
080
100
0 02 04 06 08 1
xΔ
Glowast
E(k
Jmiddotmol
minus1)
Figure 9 Variation of excess Gibbs free energy of activation of viscous flow Δ119866lowast119864 with mole fraction 119909 of CH in BB (X) 30815 K (◼)31315 K and (998771) 31815 K
000
005
010
015
020
025
0 02 04 06 08 1
x
Δ120578
(10
minus3
Nmiddotsmiddot
mminus
2)
Figure 10 Variation of deviation in viscosity Δ120578 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
investigated These conclusions support our earlier findingsof strong interactions The variation of excess Gibbs freeenergy of activation of viscous flow Δ119866lowast119864 with mole fractionof CH has been presented in Figure 9 at all temperaturesThese values are positive over the entire range of compositionof CH According to Iloukhani et al [44 45] negative valuesof Δ119866lowast119864 indicate the presence of weak physical forces such asdispersive forces in the system On the other hand positivevalues of it suggest strong specific interactions This alsosupports the conclusions drawn from our earlier findings
According to Fort and Moore [46] deviation in viscositytends to become more positive as the strength of the inter-action increases The deviation in viscosity variation gives aqualitative estimation of the strength of the intermolecularinteractions The deviation in viscosities may be generallyexplained by considering the following factors (i) The differ-ence in size and shape of the component molecules and theloss of dipolar association in pure componentmay contributeto a decrease in viscosity and (ii) specific interactions betweenunlike components such as hydrogen bond formation ordipole-dipole interactions or charge-transfer complexes maycause increase in viscosity in mixtures compared to in purecomponents [47]The former effect produces negative devia-tion in viscosity and latter effect produces positive deviationin viscosity A perusal of Figure 10 shows that the values ofΔ120578 are positive for the present system at three temperaturesThe positive Δ120578 values decrease with increasing temperatureThe positive Δ120578 values indicate specific interactions whilethe negative Δ120578 values indicate dispersion forces [48ndash50]
In the present investigation the positive values of all binarysystems may be attributed to the dipole-dipole interactionsThe sign and magnitude of Δ119906 play important roles indescribing molecular rearrangements as a result of molecularinteractions occurring among the component molecules inthe mixtures The excess ultrasonic speed with mole fractionof CH is shown in Figure 11 Here we observed that theΔ119906 values are positive for all binary systems over the entirerange of composition at all the studied temperatures Positivedeviations indicate the increasing strength of interactionbetween component molecules of binary liquid mixturesAccording to Reddy et al [51] strong interactions amongthe components of a mixture lead to the formation ofmolecular aggregates and more compact structures thensound will travel faster through the mixture by means oflongitudinal waves and hence the ultrasonic speed deviationswith respect to a linear behaviour will be positive while ifthe structure-breaking factor in the mixture predominatesresulting expansion then the speed of sound through themixture will be slower resulting in negative deviation in thespeed of sound According to Ali et al [52] more positivevalues mean much more strong interactions between themolecules Therefore based on the above references for thepresent scenario interactions are found to be in the order31815K gt 31315K gt 30815K this again emphasizes ourview regarding the interaction between CH and BB
In the present study theoretical sound velocities havebeen evaluated by considering CH as one component andBB as the other component in the binary mixture at all
Journal of Thermodynamics 9
0
5
10
15
20
25
30
35
40
45
0 02 04 06 08 1
xΔ
u(m
middotsminus1)
Figure 11 Variation of deviation in ultrasonic velocity Δ119906 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
C=O
R
R
C=O
R
R∙ ∙ ∙ ∙
∙ ∙ ∙∙
∙ ∙
+ minusO
O
Structure of benzyl benzoate Resonance structure of ketone
lt=gt
Figure 12
the three temperatures Such an evaluation of theoreticalsound velocity is useful to verify the applicability of variousassumes of the theories of liquid mixtures and to arriveat some useful implications regarding the (strength of)molecular interactions between component liquids in somecases The theoretical values of ultrasonic velocity obtainedusing various theories along with the experimental velocityand percentage deviation are summarized in Table 6 Nomoto[53] established the following relation for sound velocitybased on the supposition of the linearity of the molecularsound velocity and the additives of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(11)
Van Dael [54] obtained the ideal mixture relation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(12)
The impedance dependence relation used by Baluja andParsania [55] is given below
119880imp =sum119909119894119885119894
sum119909119894120588119894
(13)
where 119909119894is mole fractions119872
119894is molecular weight 119877 is the
molar sound speed and 119885119894is acoustic impedance of CH and
BB respectively at three temperaturesPercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906expt
] (14)
On observing Table 6 among all the empirical theoriesNomotorsquos relation gives the best estimate of experimental val-ues of sound velocity in the system followed by impedancersquosrelation In the present binary systems the difference betweenexperimental and theoretical velocities is greater where themole fraction of CH varies in the region 04 to 07 Hence itcan be qualitatively inferred that the strength of interactionin the binary mixtures is more in this range of compositionof binary mixtures
The dynamic viscosities of the liquid mixtures have beencalculated using the several empirical relations
Grunberg and Nissan [56] proposed the following equa-tion for the measurement of viscosity of liquid mixtures
where (119882visRT) is an interaction parameterThe theoretical viscosity values using (15) to (17) along
with the percentage error are compiled in Table 7 Theevaluated values of parameters 119866
12 11986712 and 119882visRT and
standard deviations 120590 (10minus3 kgminus1sdotsminus1) are presented in Table 8
10 Journal of Thermodynamics
Table 6 Experimental and theoretical velocities from various empirical relations and percentage deviation in velocities with molefraction119909 of CH with BB at 119879 = 30815 31315 and 31815 K
The estimated values of120590 are indicating that the viscosities arewell correlated by all the three viscosity models Prolongo etal [59] reported positive values of interaction parameters cor-responding to systems with negative excess molar volumesThis is consistent with our results Among all of thesemodelsthe viscosity representations obtained from the Hind modelare in best agreement with the experimental viscosity data
4 Conclusions
(i) Ultrasonic velocities densities and viscosities forbinary liquids of CH with BB are determined exper-
imentally at T = 30815 K 31315 K and 31815 K overthe entire composition range
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119885119864 120587119864
119894 119867119864 Δ119866lowast119864 and
Δ119906 are calculated from experimental results at allthree temperatures The excessdeviation propertiesare fitted to Redlich-Kister-type polynomial and cor-responding standard deviations are evaluated Theobserved negative values of 119881119864
119898 Δ119896119904 119871119864119891 and 120587119864
119894and
positive values of 119885119864 119867119864 Δ119866lowast119864 Δ120578 and Δ119906 for allthe liquid mixtures studied clearly indicate dipole-dipole-type interactions and the geometrical fitting
Journal of Thermodynamics 11
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
Table 1 Comparison of experimental values of ultrasonic velocity (u) density (120588) and viscosity (120578) of pure liquids with the literature valuesconcerned at 30815 31315 and 31815 K
1199041 1198961199042are the volume fractions and isen-
tropic compressibilities of components 1 and 2 respectivelySince 119896
119904is not additive on mole fraction but is additive
on volume fraction hence such values are calculated usingvolume fractionB
119894
B119894=
119909119894119881119894
sum119909119894119881119894
(3)
The excessdeviation properties have been fitted to a Redlich-Kister-type polynomial equation [29]
119884119864
= 119909 (1 minus 119909)
119895
sum
119894=0
119860119894(1 minus 2119909)
119894
(4)
where 119909 is the mole fraction of CH and for evaluating Δ119896119904 119909
is replaced by volume fraction (B119894) and 119860
119894are the adjustable
parameters of the function and are determined using the leastsquare method In the present investigation ldquo119894rdquo values takenare from 0 to 4The corresponding standard deviations 120590(119884119864)were calculated using the expression
120590 (119884119864
) =[
[
sum(119884119864
exp minus 119884119864
cal)2
(119898 minus 119899)
]
]
12
(5)
where ldquo119898rdquo is the total number of experimental points and ldquo119899rdquois the number of coefficients in (4) The calculated values ofthe coefficients 119860
119894along with the standard deviations (120590) are
given in Table 3Figure 1 represents the variation of excess molar volume
(119881119864
119898)with mole fraction of CHThe sign of119881119864
119898depends upon
the contraction and expansion of volume of the liquids due tomixingThe excessmolar volume is the resultant contributionfrom several opposing effects namely chemical physical andstructural [30] The chemical or specific interactions resultin volume contractions leading to negative excess molarvolume and these include charge-transfer complexes dipole-dipole dipole-induced dipole interactions and formationof H-bonding between component molecules The physicalinteractions or nonspecific interactions are weak and theseinclude breaking of the structure of one or both of the com-ponents in a solution that is the loss of dipolar associationbetween the molecules (dispersion forces) steric hindranceof the molecules and H-bond rupture and stretching of self-associated molecules (like alcohols)The structural contribu-tions are mostly negative and arise from several effects such
minus0025
minus0020
minus0015
minus0010
minus0005
00000 02 04 06 08 1
x
VE m
(10
minus5
m3middotm
olminus
1)
Figure 1 Variation of excess molar volume 119881119864119898 with mole fraction
119909 of CH in BB at (X) 30815 K (◼) 31315 K and (998771) 31815 K
as interstitial accommodation and geometrical fitting of onecomponent into another due to the differences in the molarvolume and free volume between components In the presentinvestigation the sign of 119881119864
119898is found to be negative over the
entire composition rangeThe nature of existing interaction in a binary liquid
can also be analysed by knowing their individual chemicaland physical properties It is well known that BB and CHare polar and their dipole moment values follow 120583CH =325D gt 120583BB = 206D In the present study possibilityof Keesom dipole-dipole van der Waals forces which arisedue to the dipole moment of the components gives stronginteractions leading to negative values of 119881119864
119898[31] Moreover
the liquids BB and CH lack hydroxyl groups hence thepossibility for formation of intermolecular hydrogen bonds istrifling Further themolar volumes of CH and BB are 104459and 190428 (times10minus5m3sdotmolminus1) respectively at 30815 K Thisimplies that geometrical fitting of smaller molecules intothe voids created by the bigger molecules is most favorableThe 119881119864
119898values in binary mixture are thereby decreased with
increasing temperature Negative 119881119864119898values indicate strong
interactions following the order 31815K gt 31315K gt
30815KAccording toRastogi et al [32] such behaviourmayarise due to the fact that as temperature increases thermalenergy activates the molecule this would increase the rateof association of unlike molecules Similar type of trend wasobserved by Baragi et al [33] in methyl cyclohexane withalkanes
The strongmolecular interactions in the presented binarysystem are well reflected in the properties of partial molarvolumes The partial molar volumes 119881
1198981of component 1
(CH) and 1198811198982
of component 2 (BB) in the mixtures havebeen calculated by using the following equations
1198811198981
= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
1198811198982
= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(6)
where 119881lowast
1and 119881
lowast
2are the molar volumes of the pure
components of CH andBB respectively By differentiating (4)and then rearranging one can get the following equations for1198811198981
and 1198811198982
The derivates in the above equations are obtained bydifferentiating Redlich-Kister equation (8) which leads to thefollowing equations for 119881
1198981and 119881
1198982
1198811198981
= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(7)
1198811198982
= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(8)
The excess partial molar volumes are then given by
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(9)
The values of 1198811198981
and 1198811198982
are tabulated in Table 4 Thistable reproduces the values of 119881
1198981and 119881
1198982for both the
6 Journal of Thermodynamics
components in the mixtures are smaller than their individualmolar volumes in the pure state this indicates that shrinkageof volume takes place onmixing CHwith BB Figures 2 and 3represent the disparity of excess partialmolar volumes of119881119864
1198981
and 1198811198641198982
respectively in the binary mixture Examinationof these figures not only reveals the existence of strongforces between the unlike molecules but also supports thedeductions drawn from excess molar volume
The partial molar volumes and excess partial molarvolumes of the components at infinite dilution 119881infin
1198981 119881infin1198982
119881
119864infin
1198981 and119881119864infin
1198982 respectively were obtained by putting 119909 = 0
reported in Table 5 This table shows that these values arenegative from which we conclude that strong interactionsexist among the unlike molecules of the mixtures whichsupport the trends of 119881119864
119898values observed in these mixtures
Figures 4 and 5 represent the deviation in isentropiccompressibility (Δ119896
119904) and excess intermolecular free length
(119871119864
119891) respectively These values are found to be negative for
the system under investigation at all temperaturesThe natureof Δ119896119904 119871119864119891plays vivacious role in assessing the compactness
due to molecular rearrangement The extent of molecularinteractions in liquid mixtures may be due to charge transferdipole-induced-dipole dipole-dipole interactions and inter-stitial accommodation leading to more compact structuremaking Δ119896
119904and 119871119864
119891negative The values of the excess func-
tions Δ119896 119871119864119891depend upon several physical andor chemical
contributions [34ndash37] The physical contribution consists ofdispersion forces or weak dipole-dipole interaction that leadsto positive values of Δ119896
119904and 119871
119864
119891 Another factor which
involves a physical contribution is the geometrical effectallowing the fitting of molecules of two different sizes intoeach otherrsquos structure resulting in negativeΔ119896
119904119871119864119891valuesThe
strength of the interactions increases with temperatures asobserved frommore negative values of the excess parametersThey are negative throughout and become more negative atall concentrations as the temperature is increased In hetero-molecular interaction between the component molecules ofthe mixtures Fort and Moore [38] found that the negativevalue of excess compressibility indicates greater interactionbetween the components of themixtures due to the formationof hydrogen bond Thus the negative Δ119896
119904values for binary
mixtures indicate strong interactions between BB and CHAccording to Singh et al [39] negative values of excess
intermolecular free length119871119864119891indicate that soundwaves cover
longer distances due to decrease in intermolecular free lengthascribing the dominant nature of hydrogen bond interactionbetween unlike molecules Fort andMoore indicated that thepositive values of excess free length should be attributed to thedispersive forces and negative excess values should be due
1
05
0
minus05
minus15
minus25
0 02 04 06 08 1
xminus1
minus2
VE m
2(1
0minus
5m
3middotm
olminus
1)
Figure 2 Variation of excess partial molar volume1198811198641198982
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
5
4
3
2
1
0
minus1
minus2
0 02 04 06 08 1
xV
E m1
(10
minus5
m3middotm
olminus
1)
Figure 3 Variation of excess partial molar volume 1198811198641198981
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
minus01
minus02
minus03
minus04
minus05
minus06
minus07
0 02 04 06 08 1
x
Δk
s(1
0minus
10Pa
minus1)
Figure 4 Variation of deviation in isentropic compressibility Δ119896119904
with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and(998771) 31815 K
minus0030
minus0025
minus0020
minus0015
minus0010
minus0005
00000 02 04 06 108
LE f
(10
minus10
m)
x
Figure 5 Variation of excess free length 119871119864119891 with mole fraction 119909
of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
Journal of Thermodynamics 7
Table 4 Mole fraction (119909) and values of partial molar volume 1198811198982
(10minus5 m3sdotmolminus1) 119881
1198981(10minus5 m3
sdotmolminus1) of the binary system at 3081531315 and 31815 K
119909
119879 = 30815 K 119879 = 31315 K 119879 = 31815 K1198811198982
Figure 6 Variation of excess acoustic impedance 119885119864 with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
to hydrogen bond formation or dipole-dipole interactionsbetween solute and solvent In the present study the negativecontribution in all the systems prevails in the existenceof greater interactions Nain et al [40] also concluded asimilar observation From Figure 6 the excess values of 119885119864are found to be positive for the system at all temperaturesunder investigation According to Kondaiah andRao [41] thenature of the positive values of 119885119864 is attributed to specificinteraction between the heteromolecules This further sup-ports our earlier finding
The variations of excess internal pressure (120587119864119894) and excess
enthalpy (119867119864) are presented in Figures 7 and 8 for the present
minus35
minus30
minus25
minus20
minus15
minus10
minus5
000 02 04 06 08 10
x
120587E i
(kJmiddotm
olminus
1)
Figure 7 Variation of excess internal pressure 120587119864119894 with mole
fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
1000
2000
3000
4000
5000
6000
7000
8000
0 02 04 06 08 1
x
HE
(Jmiddotm
olminus
1)
Figure 8 Variation of excess enthalpy119867119864 with mole fraction 119909 ofCH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
system at all the three temperatures respectively From thesefigures it is observed that 120587119864
119894is negative and 119867119864 is positive
over the entire composition range of CH In accordance withKondaiah et al [42] the negative values of 120587119864
119894indicate the
existence of strong specific interactions and according toKumar and Rao [43] positive value of Δ119867 suggests strongbonding and exothermic reactionsThus it can be concludedthat strong specific interactions are operative in the systems
8 Journal of Thermodynamics
000
020
040
060
080
100
0 02 04 06 08 1
xΔ
Glowast
E(k
Jmiddotmol
minus1)
Figure 9 Variation of excess Gibbs free energy of activation of viscous flow Δ119866lowast119864 with mole fraction 119909 of CH in BB (X) 30815 K (◼)31315 K and (998771) 31815 K
000
005
010
015
020
025
0 02 04 06 08 1
x
Δ120578
(10
minus3
Nmiddotsmiddot
mminus
2)
Figure 10 Variation of deviation in viscosity Δ120578 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
investigated These conclusions support our earlier findingsof strong interactions The variation of excess Gibbs freeenergy of activation of viscous flow Δ119866lowast119864 with mole fractionof CH has been presented in Figure 9 at all temperaturesThese values are positive over the entire range of compositionof CH According to Iloukhani et al [44 45] negative valuesof Δ119866lowast119864 indicate the presence of weak physical forces such asdispersive forces in the system On the other hand positivevalues of it suggest strong specific interactions This alsosupports the conclusions drawn from our earlier findings
According to Fort and Moore [46] deviation in viscositytends to become more positive as the strength of the inter-action increases The deviation in viscosity variation gives aqualitative estimation of the strength of the intermolecularinteractions The deviation in viscosities may be generallyexplained by considering the following factors (i) The differ-ence in size and shape of the component molecules and theloss of dipolar association in pure componentmay contributeto a decrease in viscosity and (ii) specific interactions betweenunlike components such as hydrogen bond formation ordipole-dipole interactions or charge-transfer complexes maycause increase in viscosity in mixtures compared to in purecomponents [47]The former effect produces negative devia-tion in viscosity and latter effect produces positive deviationin viscosity A perusal of Figure 10 shows that the values ofΔ120578 are positive for the present system at three temperaturesThe positive Δ120578 values decrease with increasing temperatureThe positive Δ120578 values indicate specific interactions whilethe negative Δ120578 values indicate dispersion forces [48ndash50]
In the present investigation the positive values of all binarysystems may be attributed to the dipole-dipole interactionsThe sign and magnitude of Δ119906 play important roles indescribing molecular rearrangements as a result of molecularinteractions occurring among the component molecules inthe mixtures The excess ultrasonic speed with mole fractionof CH is shown in Figure 11 Here we observed that theΔ119906 values are positive for all binary systems over the entirerange of composition at all the studied temperatures Positivedeviations indicate the increasing strength of interactionbetween component molecules of binary liquid mixturesAccording to Reddy et al [51] strong interactions amongthe components of a mixture lead to the formation ofmolecular aggregates and more compact structures thensound will travel faster through the mixture by means oflongitudinal waves and hence the ultrasonic speed deviationswith respect to a linear behaviour will be positive while ifthe structure-breaking factor in the mixture predominatesresulting expansion then the speed of sound through themixture will be slower resulting in negative deviation in thespeed of sound According to Ali et al [52] more positivevalues mean much more strong interactions between themolecules Therefore based on the above references for thepresent scenario interactions are found to be in the order31815K gt 31315K gt 30815K this again emphasizes ourview regarding the interaction between CH and BB
In the present study theoretical sound velocities havebeen evaluated by considering CH as one component andBB as the other component in the binary mixture at all
Journal of Thermodynamics 9
0
5
10
15
20
25
30
35
40
45
0 02 04 06 08 1
xΔ
u(m
middotsminus1)
Figure 11 Variation of deviation in ultrasonic velocity Δ119906 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
C=O
R
R
C=O
R
R∙ ∙ ∙ ∙
∙ ∙ ∙∙
∙ ∙
+ minusO
O
Structure of benzyl benzoate Resonance structure of ketone
lt=gt
Figure 12
the three temperatures Such an evaluation of theoreticalsound velocity is useful to verify the applicability of variousassumes of the theories of liquid mixtures and to arriveat some useful implications regarding the (strength of)molecular interactions between component liquids in somecases The theoretical values of ultrasonic velocity obtainedusing various theories along with the experimental velocityand percentage deviation are summarized in Table 6 Nomoto[53] established the following relation for sound velocitybased on the supposition of the linearity of the molecularsound velocity and the additives of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(11)
Van Dael [54] obtained the ideal mixture relation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(12)
The impedance dependence relation used by Baluja andParsania [55] is given below
119880imp =sum119909119894119885119894
sum119909119894120588119894
(13)
where 119909119894is mole fractions119872
119894is molecular weight 119877 is the
molar sound speed and 119885119894is acoustic impedance of CH and
BB respectively at three temperaturesPercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906expt
] (14)
On observing Table 6 among all the empirical theoriesNomotorsquos relation gives the best estimate of experimental val-ues of sound velocity in the system followed by impedancersquosrelation In the present binary systems the difference betweenexperimental and theoretical velocities is greater where themole fraction of CH varies in the region 04 to 07 Hence itcan be qualitatively inferred that the strength of interactionin the binary mixtures is more in this range of compositionof binary mixtures
The dynamic viscosities of the liquid mixtures have beencalculated using the several empirical relations
Grunberg and Nissan [56] proposed the following equa-tion for the measurement of viscosity of liquid mixtures
where (119882visRT) is an interaction parameterThe theoretical viscosity values using (15) to (17) along
with the percentage error are compiled in Table 7 Theevaluated values of parameters 119866
12 11986712 and 119882visRT and
standard deviations 120590 (10minus3 kgminus1sdotsminus1) are presented in Table 8
10 Journal of Thermodynamics
Table 6 Experimental and theoretical velocities from various empirical relations and percentage deviation in velocities with molefraction119909 of CH with BB at 119879 = 30815 31315 and 31815 K
The estimated values of120590 are indicating that the viscosities arewell correlated by all the three viscosity models Prolongo etal [59] reported positive values of interaction parameters cor-responding to systems with negative excess molar volumesThis is consistent with our results Among all of thesemodelsthe viscosity representations obtained from the Hind modelare in best agreement with the experimental viscosity data
4 Conclusions
(i) Ultrasonic velocities densities and viscosities forbinary liquids of CH with BB are determined exper-
imentally at T = 30815 K 31315 K and 31815 K overthe entire composition range
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119885119864 120587119864
119894 119867119864 Δ119866lowast119864 and
Δ119906 are calculated from experimental results at allthree temperatures The excessdeviation propertiesare fitted to Redlich-Kister-type polynomial and cor-responding standard deviations are evaluated Theobserved negative values of 119881119864
119898 Δ119896119904 119871119864119891 and 120587119864
119894and
positive values of 119885119864 119867119864 Δ119866lowast119864 Δ120578 and Δ119906 for allthe liquid mixtures studied clearly indicate dipole-dipole-type interactions and the geometrical fitting
Journal of Thermodynamics 11
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
The strongmolecular interactions in the presented binarysystem are well reflected in the properties of partial molarvolumes The partial molar volumes 119881
1198981of component 1
(CH) and 1198811198982
of component 2 (BB) in the mixtures havebeen calculated by using the following equations
1198811198981
= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
1198811198982
= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(6)
where 119881lowast
1and 119881
lowast
2are the molar volumes of the pure
components of CH andBB respectively By differentiating (4)and then rearranging one can get the following equations for1198811198981
and 1198811198982
The derivates in the above equations are obtained bydifferentiating Redlich-Kister equation (8) which leads to thefollowing equations for 119881
1198981and 119881
1198982
1198811198981
= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(7)
1198811198982
= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(8)
The excess partial molar volumes are then given by
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(9)
The values of 1198811198981
and 1198811198982
are tabulated in Table 4 Thistable reproduces the values of 119881
1198981and 119881
1198982for both the
6 Journal of Thermodynamics
components in the mixtures are smaller than their individualmolar volumes in the pure state this indicates that shrinkageof volume takes place onmixing CHwith BB Figures 2 and 3represent the disparity of excess partialmolar volumes of119881119864
1198981
and 1198811198641198982
respectively in the binary mixture Examinationof these figures not only reveals the existence of strongforces between the unlike molecules but also supports thedeductions drawn from excess molar volume
The partial molar volumes and excess partial molarvolumes of the components at infinite dilution 119881infin
1198981 119881infin1198982
119881
119864infin
1198981 and119881119864infin
1198982 respectively were obtained by putting 119909 = 0
reported in Table 5 This table shows that these values arenegative from which we conclude that strong interactionsexist among the unlike molecules of the mixtures whichsupport the trends of 119881119864
119898values observed in these mixtures
Figures 4 and 5 represent the deviation in isentropiccompressibility (Δ119896
119904) and excess intermolecular free length
(119871119864
119891) respectively These values are found to be negative for
the system under investigation at all temperaturesThe natureof Δ119896119904 119871119864119891plays vivacious role in assessing the compactness
due to molecular rearrangement The extent of molecularinteractions in liquid mixtures may be due to charge transferdipole-induced-dipole dipole-dipole interactions and inter-stitial accommodation leading to more compact structuremaking Δ119896
119904and 119871119864
119891negative The values of the excess func-
tions Δ119896 119871119864119891depend upon several physical andor chemical
contributions [34ndash37] The physical contribution consists ofdispersion forces or weak dipole-dipole interaction that leadsto positive values of Δ119896
119904and 119871
119864
119891 Another factor which
involves a physical contribution is the geometrical effectallowing the fitting of molecules of two different sizes intoeach otherrsquos structure resulting in negativeΔ119896
119904119871119864119891valuesThe
strength of the interactions increases with temperatures asobserved frommore negative values of the excess parametersThey are negative throughout and become more negative atall concentrations as the temperature is increased In hetero-molecular interaction between the component molecules ofthe mixtures Fort and Moore [38] found that the negativevalue of excess compressibility indicates greater interactionbetween the components of themixtures due to the formationof hydrogen bond Thus the negative Δ119896
119904values for binary
mixtures indicate strong interactions between BB and CHAccording to Singh et al [39] negative values of excess
intermolecular free length119871119864119891indicate that soundwaves cover
longer distances due to decrease in intermolecular free lengthascribing the dominant nature of hydrogen bond interactionbetween unlike molecules Fort andMoore indicated that thepositive values of excess free length should be attributed to thedispersive forces and negative excess values should be due
1
05
0
minus05
minus15
minus25
0 02 04 06 08 1
xminus1
minus2
VE m
2(1
0minus
5m
3middotm
olminus
1)
Figure 2 Variation of excess partial molar volume1198811198641198982
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
5
4
3
2
1
0
minus1
minus2
0 02 04 06 08 1
xV
E m1
(10
minus5
m3middotm
olminus
1)
Figure 3 Variation of excess partial molar volume 1198811198641198981
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
minus01
minus02
minus03
minus04
minus05
minus06
minus07
0 02 04 06 08 1
x
Δk
s(1
0minus
10Pa
minus1)
Figure 4 Variation of deviation in isentropic compressibility Δ119896119904
with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and(998771) 31815 K
minus0030
minus0025
minus0020
minus0015
minus0010
minus0005
00000 02 04 06 108
LE f
(10
minus10
m)
x
Figure 5 Variation of excess free length 119871119864119891 with mole fraction 119909
of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
Journal of Thermodynamics 7
Table 4 Mole fraction (119909) and values of partial molar volume 1198811198982
(10minus5 m3sdotmolminus1) 119881
1198981(10minus5 m3
sdotmolminus1) of the binary system at 3081531315 and 31815 K
119909
119879 = 30815 K 119879 = 31315 K 119879 = 31815 K1198811198982
Figure 6 Variation of excess acoustic impedance 119885119864 with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
to hydrogen bond formation or dipole-dipole interactionsbetween solute and solvent In the present study the negativecontribution in all the systems prevails in the existenceof greater interactions Nain et al [40] also concluded asimilar observation From Figure 6 the excess values of 119885119864are found to be positive for the system at all temperaturesunder investigation According to Kondaiah andRao [41] thenature of the positive values of 119885119864 is attributed to specificinteraction between the heteromolecules This further sup-ports our earlier finding
The variations of excess internal pressure (120587119864119894) and excess
enthalpy (119867119864) are presented in Figures 7 and 8 for the present
minus35
minus30
minus25
minus20
minus15
minus10
minus5
000 02 04 06 08 10
x
120587E i
(kJmiddotm
olminus
1)
Figure 7 Variation of excess internal pressure 120587119864119894 with mole
fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
1000
2000
3000
4000
5000
6000
7000
8000
0 02 04 06 08 1
x
HE
(Jmiddotm
olminus
1)
Figure 8 Variation of excess enthalpy119867119864 with mole fraction 119909 ofCH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
system at all the three temperatures respectively From thesefigures it is observed that 120587119864
119894is negative and 119867119864 is positive
over the entire composition range of CH In accordance withKondaiah et al [42] the negative values of 120587119864
119894indicate the
existence of strong specific interactions and according toKumar and Rao [43] positive value of Δ119867 suggests strongbonding and exothermic reactionsThus it can be concludedthat strong specific interactions are operative in the systems
8 Journal of Thermodynamics
000
020
040
060
080
100
0 02 04 06 08 1
xΔ
Glowast
E(k
Jmiddotmol
minus1)
Figure 9 Variation of excess Gibbs free energy of activation of viscous flow Δ119866lowast119864 with mole fraction 119909 of CH in BB (X) 30815 K (◼)31315 K and (998771) 31815 K
000
005
010
015
020
025
0 02 04 06 08 1
x
Δ120578
(10
minus3
Nmiddotsmiddot
mminus
2)
Figure 10 Variation of deviation in viscosity Δ120578 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
investigated These conclusions support our earlier findingsof strong interactions The variation of excess Gibbs freeenergy of activation of viscous flow Δ119866lowast119864 with mole fractionof CH has been presented in Figure 9 at all temperaturesThese values are positive over the entire range of compositionof CH According to Iloukhani et al [44 45] negative valuesof Δ119866lowast119864 indicate the presence of weak physical forces such asdispersive forces in the system On the other hand positivevalues of it suggest strong specific interactions This alsosupports the conclusions drawn from our earlier findings
According to Fort and Moore [46] deviation in viscositytends to become more positive as the strength of the inter-action increases The deviation in viscosity variation gives aqualitative estimation of the strength of the intermolecularinteractions The deviation in viscosities may be generallyexplained by considering the following factors (i) The differ-ence in size and shape of the component molecules and theloss of dipolar association in pure componentmay contributeto a decrease in viscosity and (ii) specific interactions betweenunlike components such as hydrogen bond formation ordipole-dipole interactions or charge-transfer complexes maycause increase in viscosity in mixtures compared to in purecomponents [47]The former effect produces negative devia-tion in viscosity and latter effect produces positive deviationin viscosity A perusal of Figure 10 shows that the values ofΔ120578 are positive for the present system at three temperaturesThe positive Δ120578 values decrease with increasing temperatureThe positive Δ120578 values indicate specific interactions whilethe negative Δ120578 values indicate dispersion forces [48ndash50]
In the present investigation the positive values of all binarysystems may be attributed to the dipole-dipole interactionsThe sign and magnitude of Δ119906 play important roles indescribing molecular rearrangements as a result of molecularinteractions occurring among the component molecules inthe mixtures The excess ultrasonic speed with mole fractionof CH is shown in Figure 11 Here we observed that theΔ119906 values are positive for all binary systems over the entirerange of composition at all the studied temperatures Positivedeviations indicate the increasing strength of interactionbetween component molecules of binary liquid mixturesAccording to Reddy et al [51] strong interactions amongthe components of a mixture lead to the formation ofmolecular aggregates and more compact structures thensound will travel faster through the mixture by means oflongitudinal waves and hence the ultrasonic speed deviationswith respect to a linear behaviour will be positive while ifthe structure-breaking factor in the mixture predominatesresulting expansion then the speed of sound through themixture will be slower resulting in negative deviation in thespeed of sound According to Ali et al [52] more positivevalues mean much more strong interactions between themolecules Therefore based on the above references for thepresent scenario interactions are found to be in the order31815K gt 31315K gt 30815K this again emphasizes ourview regarding the interaction between CH and BB
In the present study theoretical sound velocities havebeen evaluated by considering CH as one component andBB as the other component in the binary mixture at all
Journal of Thermodynamics 9
0
5
10
15
20
25
30
35
40
45
0 02 04 06 08 1
xΔ
u(m
middotsminus1)
Figure 11 Variation of deviation in ultrasonic velocity Δ119906 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
C=O
R
R
C=O
R
R∙ ∙ ∙ ∙
∙ ∙ ∙∙
∙ ∙
+ minusO
O
Structure of benzyl benzoate Resonance structure of ketone
lt=gt
Figure 12
the three temperatures Such an evaluation of theoreticalsound velocity is useful to verify the applicability of variousassumes of the theories of liquid mixtures and to arriveat some useful implications regarding the (strength of)molecular interactions between component liquids in somecases The theoretical values of ultrasonic velocity obtainedusing various theories along with the experimental velocityand percentage deviation are summarized in Table 6 Nomoto[53] established the following relation for sound velocitybased on the supposition of the linearity of the molecularsound velocity and the additives of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(11)
Van Dael [54] obtained the ideal mixture relation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(12)
The impedance dependence relation used by Baluja andParsania [55] is given below
119880imp =sum119909119894119885119894
sum119909119894120588119894
(13)
where 119909119894is mole fractions119872
119894is molecular weight 119877 is the
molar sound speed and 119885119894is acoustic impedance of CH and
BB respectively at three temperaturesPercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906expt
] (14)
On observing Table 6 among all the empirical theoriesNomotorsquos relation gives the best estimate of experimental val-ues of sound velocity in the system followed by impedancersquosrelation In the present binary systems the difference betweenexperimental and theoretical velocities is greater where themole fraction of CH varies in the region 04 to 07 Hence itcan be qualitatively inferred that the strength of interactionin the binary mixtures is more in this range of compositionof binary mixtures
The dynamic viscosities of the liquid mixtures have beencalculated using the several empirical relations
Grunberg and Nissan [56] proposed the following equa-tion for the measurement of viscosity of liquid mixtures
where (119882visRT) is an interaction parameterThe theoretical viscosity values using (15) to (17) along
with the percentage error are compiled in Table 7 Theevaluated values of parameters 119866
12 11986712 and 119882visRT and
standard deviations 120590 (10minus3 kgminus1sdotsminus1) are presented in Table 8
10 Journal of Thermodynamics
Table 6 Experimental and theoretical velocities from various empirical relations and percentage deviation in velocities with molefraction119909 of CH with BB at 119879 = 30815 31315 and 31815 K
The estimated values of120590 are indicating that the viscosities arewell correlated by all the three viscosity models Prolongo etal [59] reported positive values of interaction parameters cor-responding to systems with negative excess molar volumesThis is consistent with our results Among all of thesemodelsthe viscosity representations obtained from the Hind modelare in best agreement with the experimental viscosity data
4 Conclusions
(i) Ultrasonic velocities densities and viscosities forbinary liquids of CH with BB are determined exper-
imentally at T = 30815 K 31315 K and 31815 K overthe entire composition range
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119885119864 120587119864
119894 119867119864 Δ119866lowast119864 and
Δ119906 are calculated from experimental results at allthree temperatures The excessdeviation propertiesare fitted to Redlich-Kister-type polynomial and cor-responding standard deviations are evaluated Theobserved negative values of 119881119864
119898 Δ119896119904 119871119864119891 and 120587119864
119894and
positive values of 119885119864 119867119864 Δ119866lowast119864 Δ120578 and Δ119906 for allthe liquid mixtures studied clearly indicate dipole-dipole-type interactions and the geometrical fitting
Journal of Thermodynamics 11
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
The strongmolecular interactions in the presented binarysystem are well reflected in the properties of partial molarvolumes The partial molar volumes 119881
1198981of component 1
(CH) and 1198811198982
of component 2 (BB) in the mixtures havebeen calculated by using the following equations
1198811198981
= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
1198811198982
= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(6)
where 119881lowast
1and 119881
lowast
2are the molar volumes of the pure
components of CH andBB respectively By differentiating (4)and then rearranging one can get the following equations for1198811198981
and 1198811198982
The derivates in the above equations are obtained bydifferentiating Redlich-Kister equation (8) which leads to thefollowing equations for 119881
1198981and 119881
1198982
1198811198981
= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(7)
1198811198982
= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(8)
The excess partial molar volumes are then given by
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(9)
The values of 1198811198981
and 1198811198982
are tabulated in Table 4 Thistable reproduces the values of 119881
1198981and 119881
1198982for both the
6 Journal of Thermodynamics
components in the mixtures are smaller than their individualmolar volumes in the pure state this indicates that shrinkageof volume takes place onmixing CHwith BB Figures 2 and 3represent the disparity of excess partialmolar volumes of119881119864
1198981
and 1198811198641198982
respectively in the binary mixture Examinationof these figures not only reveals the existence of strongforces between the unlike molecules but also supports thedeductions drawn from excess molar volume
The partial molar volumes and excess partial molarvolumes of the components at infinite dilution 119881infin
1198981 119881infin1198982
119881
119864infin
1198981 and119881119864infin
1198982 respectively were obtained by putting 119909 = 0
reported in Table 5 This table shows that these values arenegative from which we conclude that strong interactionsexist among the unlike molecules of the mixtures whichsupport the trends of 119881119864
119898values observed in these mixtures
Figures 4 and 5 represent the deviation in isentropiccompressibility (Δ119896
119904) and excess intermolecular free length
(119871119864
119891) respectively These values are found to be negative for
the system under investigation at all temperaturesThe natureof Δ119896119904 119871119864119891plays vivacious role in assessing the compactness
due to molecular rearrangement The extent of molecularinteractions in liquid mixtures may be due to charge transferdipole-induced-dipole dipole-dipole interactions and inter-stitial accommodation leading to more compact structuremaking Δ119896
119904and 119871119864
119891negative The values of the excess func-
tions Δ119896 119871119864119891depend upon several physical andor chemical
contributions [34ndash37] The physical contribution consists ofdispersion forces or weak dipole-dipole interaction that leadsto positive values of Δ119896
119904and 119871
119864
119891 Another factor which
involves a physical contribution is the geometrical effectallowing the fitting of molecules of two different sizes intoeach otherrsquos structure resulting in negativeΔ119896
119904119871119864119891valuesThe
strength of the interactions increases with temperatures asobserved frommore negative values of the excess parametersThey are negative throughout and become more negative atall concentrations as the temperature is increased In hetero-molecular interaction between the component molecules ofthe mixtures Fort and Moore [38] found that the negativevalue of excess compressibility indicates greater interactionbetween the components of themixtures due to the formationof hydrogen bond Thus the negative Δ119896
119904values for binary
mixtures indicate strong interactions between BB and CHAccording to Singh et al [39] negative values of excess
intermolecular free length119871119864119891indicate that soundwaves cover
longer distances due to decrease in intermolecular free lengthascribing the dominant nature of hydrogen bond interactionbetween unlike molecules Fort andMoore indicated that thepositive values of excess free length should be attributed to thedispersive forces and negative excess values should be due
1
05
0
minus05
minus15
minus25
0 02 04 06 08 1
xminus1
minus2
VE m
2(1
0minus
5m
3middotm
olminus
1)
Figure 2 Variation of excess partial molar volume1198811198641198982
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
5
4
3
2
1
0
minus1
minus2
0 02 04 06 08 1
xV
E m1
(10
minus5
m3middotm
olminus
1)
Figure 3 Variation of excess partial molar volume 1198811198641198981
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
minus01
minus02
minus03
minus04
minus05
minus06
minus07
0 02 04 06 08 1
x
Δk
s(1
0minus
10Pa
minus1)
Figure 4 Variation of deviation in isentropic compressibility Δ119896119904
with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and(998771) 31815 K
minus0030
minus0025
minus0020
minus0015
minus0010
minus0005
00000 02 04 06 108
LE f
(10
minus10
m)
x
Figure 5 Variation of excess free length 119871119864119891 with mole fraction 119909
of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
Journal of Thermodynamics 7
Table 4 Mole fraction (119909) and values of partial molar volume 1198811198982
(10minus5 m3sdotmolminus1) 119881
1198981(10minus5 m3
sdotmolminus1) of the binary system at 3081531315 and 31815 K
119909
119879 = 30815 K 119879 = 31315 K 119879 = 31815 K1198811198982
Figure 6 Variation of excess acoustic impedance 119885119864 with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
to hydrogen bond formation or dipole-dipole interactionsbetween solute and solvent In the present study the negativecontribution in all the systems prevails in the existenceof greater interactions Nain et al [40] also concluded asimilar observation From Figure 6 the excess values of 119885119864are found to be positive for the system at all temperaturesunder investigation According to Kondaiah andRao [41] thenature of the positive values of 119885119864 is attributed to specificinteraction between the heteromolecules This further sup-ports our earlier finding
The variations of excess internal pressure (120587119864119894) and excess
enthalpy (119867119864) are presented in Figures 7 and 8 for the present
minus35
minus30
minus25
minus20
minus15
minus10
minus5
000 02 04 06 08 10
x
120587E i
(kJmiddotm
olminus
1)
Figure 7 Variation of excess internal pressure 120587119864119894 with mole
fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
1000
2000
3000
4000
5000
6000
7000
8000
0 02 04 06 08 1
x
HE
(Jmiddotm
olminus
1)
Figure 8 Variation of excess enthalpy119867119864 with mole fraction 119909 ofCH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
system at all the three temperatures respectively From thesefigures it is observed that 120587119864
119894is negative and 119867119864 is positive
over the entire composition range of CH In accordance withKondaiah et al [42] the negative values of 120587119864
119894indicate the
existence of strong specific interactions and according toKumar and Rao [43] positive value of Δ119867 suggests strongbonding and exothermic reactionsThus it can be concludedthat strong specific interactions are operative in the systems
8 Journal of Thermodynamics
000
020
040
060
080
100
0 02 04 06 08 1
xΔ
Glowast
E(k
Jmiddotmol
minus1)
Figure 9 Variation of excess Gibbs free energy of activation of viscous flow Δ119866lowast119864 with mole fraction 119909 of CH in BB (X) 30815 K (◼)31315 K and (998771) 31815 K
000
005
010
015
020
025
0 02 04 06 08 1
x
Δ120578
(10
minus3
Nmiddotsmiddot
mminus
2)
Figure 10 Variation of deviation in viscosity Δ120578 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
investigated These conclusions support our earlier findingsof strong interactions The variation of excess Gibbs freeenergy of activation of viscous flow Δ119866lowast119864 with mole fractionof CH has been presented in Figure 9 at all temperaturesThese values are positive over the entire range of compositionof CH According to Iloukhani et al [44 45] negative valuesof Δ119866lowast119864 indicate the presence of weak physical forces such asdispersive forces in the system On the other hand positivevalues of it suggest strong specific interactions This alsosupports the conclusions drawn from our earlier findings
According to Fort and Moore [46] deviation in viscositytends to become more positive as the strength of the inter-action increases The deviation in viscosity variation gives aqualitative estimation of the strength of the intermolecularinteractions The deviation in viscosities may be generallyexplained by considering the following factors (i) The differ-ence in size and shape of the component molecules and theloss of dipolar association in pure componentmay contributeto a decrease in viscosity and (ii) specific interactions betweenunlike components such as hydrogen bond formation ordipole-dipole interactions or charge-transfer complexes maycause increase in viscosity in mixtures compared to in purecomponents [47]The former effect produces negative devia-tion in viscosity and latter effect produces positive deviationin viscosity A perusal of Figure 10 shows that the values ofΔ120578 are positive for the present system at three temperaturesThe positive Δ120578 values decrease with increasing temperatureThe positive Δ120578 values indicate specific interactions whilethe negative Δ120578 values indicate dispersion forces [48ndash50]
In the present investigation the positive values of all binarysystems may be attributed to the dipole-dipole interactionsThe sign and magnitude of Δ119906 play important roles indescribing molecular rearrangements as a result of molecularinteractions occurring among the component molecules inthe mixtures The excess ultrasonic speed with mole fractionof CH is shown in Figure 11 Here we observed that theΔ119906 values are positive for all binary systems over the entirerange of composition at all the studied temperatures Positivedeviations indicate the increasing strength of interactionbetween component molecules of binary liquid mixturesAccording to Reddy et al [51] strong interactions amongthe components of a mixture lead to the formation ofmolecular aggregates and more compact structures thensound will travel faster through the mixture by means oflongitudinal waves and hence the ultrasonic speed deviationswith respect to a linear behaviour will be positive while ifthe structure-breaking factor in the mixture predominatesresulting expansion then the speed of sound through themixture will be slower resulting in negative deviation in thespeed of sound According to Ali et al [52] more positivevalues mean much more strong interactions between themolecules Therefore based on the above references for thepresent scenario interactions are found to be in the order31815K gt 31315K gt 30815K this again emphasizes ourview regarding the interaction between CH and BB
In the present study theoretical sound velocities havebeen evaluated by considering CH as one component andBB as the other component in the binary mixture at all
Journal of Thermodynamics 9
0
5
10
15
20
25
30
35
40
45
0 02 04 06 08 1
xΔ
u(m
middotsminus1)
Figure 11 Variation of deviation in ultrasonic velocity Δ119906 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
C=O
R
R
C=O
R
R∙ ∙ ∙ ∙
∙ ∙ ∙∙
∙ ∙
+ minusO
O
Structure of benzyl benzoate Resonance structure of ketone
lt=gt
Figure 12
the three temperatures Such an evaluation of theoreticalsound velocity is useful to verify the applicability of variousassumes of the theories of liquid mixtures and to arriveat some useful implications regarding the (strength of)molecular interactions between component liquids in somecases The theoretical values of ultrasonic velocity obtainedusing various theories along with the experimental velocityand percentage deviation are summarized in Table 6 Nomoto[53] established the following relation for sound velocitybased on the supposition of the linearity of the molecularsound velocity and the additives of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(11)
Van Dael [54] obtained the ideal mixture relation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(12)
The impedance dependence relation used by Baluja andParsania [55] is given below
119880imp =sum119909119894119885119894
sum119909119894120588119894
(13)
where 119909119894is mole fractions119872
119894is molecular weight 119877 is the
molar sound speed and 119885119894is acoustic impedance of CH and
BB respectively at three temperaturesPercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906expt
] (14)
On observing Table 6 among all the empirical theoriesNomotorsquos relation gives the best estimate of experimental val-ues of sound velocity in the system followed by impedancersquosrelation In the present binary systems the difference betweenexperimental and theoretical velocities is greater where themole fraction of CH varies in the region 04 to 07 Hence itcan be qualitatively inferred that the strength of interactionin the binary mixtures is more in this range of compositionof binary mixtures
The dynamic viscosities of the liquid mixtures have beencalculated using the several empirical relations
Grunberg and Nissan [56] proposed the following equa-tion for the measurement of viscosity of liquid mixtures
where (119882visRT) is an interaction parameterThe theoretical viscosity values using (15) to (17) along
with the percentage error are compiled in Table 7 Theevaluated values of parameters 119866
12 11986712 and 119882visRT and
standard deviations 120590 (10minus3 kgminus1sdotsminus1) are presented in Table 8
10 Journal of Thermodynamics
Table 6 Experimental and theoretical velocities from various empirical relations and percentage deviation in velocities with molefraction119909 of CH with BB at 119879 = 30815 31315 and 31815 K
The estimated values of120590 are indicating that the viscosities arewell correlated by all the three viscosity models Prolongo etal [59] reported positive values of interaction parameters cor-responding to systems with negative excess molar volumesThis is consistent with our results Among all of thesemodelsthe viscosity representations obtained from the Hind modelare in best agreement with the experimental viscosity data
4 Conclusions
(i) Ultrasonic velocities densities and viscosities forbinary liquids of CH with BB are determined exper-
imentally at T = 30815 K 31315 K and 31815 K overthe entire composition range
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119885119864 120587119864
119894 119867119864 Δ119866lowast119864 and
Δ119906 are calculated from experimental results at allthree temperatures The excessdeviation propertiesare fitted to Redlich-Kister-type polynomial and cor-responding standard deviations are evaluated Theobserved negative values of 119881119864
119898 Δ119896119904 119871119864119891 and 120587119864
119894and
positive values of 119885119864 119867119864 Δ119866lowast119864 Δ120578 and Δ119906 for allthe liquid mixtures studied clearly indicate dipole-dipole-type interactions and the geometrical fitting
Journal of Thermodynamics 11
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
components in the mixtures are smaller than their individualmolar volumes in the pure state this indicates that shrinkageof volume takes place onmixing CHwith BB Figures 2 and 3represent the disparity of excess partialmolar volumes of119881119864
1198981
and 1198811198641198982
respectively in the binary mixture Examinationof these figures not only reveals the existence of strongforces between the unlike molecules but also supports thedeductions drawn from excess molar volume
The partial molar volumes and excess partial molarvolumes of the components at infinite dilution 119881infin
1198981 119881infin1198982
119881
119864infin
1198981 and119881119864infin
1198982 respectively were obtained by putting 119909 = 0
reported in Table 5 This table shows that these values arenegative from which we conclude that strong interactionsexist among the unlike molecules of the mixtures whichsupport the trends of 119881119864
119898values observed in these mixtures
Figures 4 and 5 represent the deviation in isentropiccompressibility (Δ119896
119904) and excess intermolecular free length
(119871119864
119891) respectively These values are found to be negative for
the system under investigation at all temperaturesThe natureof Δ119896119904 119871119864119891plays vivacious role in assessing the compactness
due to molecular rearrangement The extent of molecularinteractions in liquid mixtures may be due to charge transferdipole-induced-dipole dipole-dipole interactions and inter-stitial accommodation leading to more compact structuremaking Δ119896
119904and 119871119864
119891negative The values of the excess func-
tions Δ119896 119871119864119891depend upon several physical andor chemical
contributions [34ndash37] The physical contribution consists ofdispersion forces or weak dipole-dipole interaction that leadsto positive values of Δ119896
119904and 119871
119864
119891 Another factor which
involves a physical contribution is the geometrical effectallowing the fitting of molecules of two different sizes intoeach otherrsquos structure resulting in negativeΔ119896
119904119871119864119891valuesThe
strength of the interactions increases with temperatures asobserved frommore negative values of the excess parametersThey are negative throughout and become more negative atall concentrations as the temperature is increased In hetero-molecular interaction between the component molecules ofthe mixtures Fort and Moore [38] found that the negativevalue of excess compressibility indicates greater interactionbetween the components of themixtures due to the formationof hydrogen bond Thus the negative Δ119896
119904values for binary
mixtures indicate strong interactions between BB and CHAccording to Singh et al [39] negative values of excess
intermolecular free length119871119864119891indicate that soundwaves cover
longer distances due to decrease in intermolecular free lengthascribing the dominant nature of hydrogen bond interactionbetween unlike molecules Fort andMoore indicated that thepositive values of excess free length should be attributed to thedispersive forces and negative excess values should be due
1
05
0
minus05
minus15
minus25
0 02 04 06 08 1
xminus1
minus2
VE m
2(1
0minus
5m
3middotm
olminus
1)
Figure 2 Variation of excess partial molar volume1198811198641198982
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
5
4
3
2
1
0
minus1
minus2
0 02 04 06 08 1
xV
E m1
(10
minus5
m3middotm
olminus
1)
Figure 3 Variation of excess partial molar volume 1198811198641198981
with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
minus01
minus02
minus03
minus04
minus05
minus06
minus07
0 02 04 06 08 1
x
Δk
s(1
0minus
10Pa
minus1)
Figure 4 Variation of deviation in isentropic compressibility Δ119896119904
with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and(998771) 31815 K
minus0030
minus0025
minus0020
minus0015
minus0010
minus0005
00000 02 04 06 108
LE f
(10
minus10
m)
x
Figure 5 Variation of excess free length 119871119864119891 with mole fraction 119909
of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
Journal of Thermodynamics 7
Table 4 Mole fraction (119909) and values of partial molar volume 1198811198982
(10minus5 m3sdotmolminus1) 119881
1198981(10minus5 m3
sdotmolminus1) of the binary system at 3081531315 and 31815 K
119909
119879 = 30815 K 119879 = 31315 K 119879 = 31815 K1198811198982
Figure 6 Variation of excess acoustic impedance 119885119864 with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
to hydrogen bond formation or dipole-dipole interactionsbetween solute and solvent In the present study the negativecontribution in all the systems prevails in the existenceof greater interactions Nain et al [40] also concluded asimilar observation From Figure 6 the excess values of 119885119864are found to be positive for the system at all temperaturesunder investigation According to Kondaiah andRao [41] thenature of the positive values of 119885119864 is attributed to specificinteraction between the heteromolecules This further sup-ports our earlier finding
The variations of excess internal pressure (120587119864119894) and excess
enthalpy (119867119864) are presented in Figures 7 and 8 for the present
minus35
minus30
minus25
minus20
minus15
minus10
minus5
000 02 04 06 08 10
x
120587E i
(kJmiddotm
olminus
1)
Figure 7 Variation of excess internal pressure 120587119864119894 with mole
fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
1000
2000
3000
4000
5000
6000
7000
8000
0 02 04 06 08 1
x
HE
(Jmiddotm
olminus
1)
Figure 8 Variation of excess enthalpy119867119864 with mole fraction 119909 ofCH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
system at all the three temperatures respectively From thesefigures it is observed that 120587119864
119894is negative and 119867119864 is positive
over the entire composition range of CH In accordance withKondaiah et al [42] the negative values of 120587119864
119894indicate the
existence of strong specific interactions and according toKumar and Rao [43] positive value of Δ119867 suggests strongbonding and exothermic reactionsThus it can be concludedthat strong specific interactions are operative in the systems
8 Journal of Thermodynamics
000
020
040
060
080
100
0 02 04 06 08 1
xΔ
Glowast
E(k
Jmiddotmol
minus1)
Figure 9 Variation of excess Gibbs free energy of activation of viscous flow Δ119866lowast119864 with mole fraction 119909 of CH in BB (X) 30815 K (◼)31315 K and (998771) 31815 K
000
005
010
015
020
025
0 02 04 06 08 1
x
Δ120578
(10
minus3
Nmiddotsmiddot
mminus
2)
Figure 10 Variation of deviation in viscosity Δ120578 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
investigated These conclusions support our earlier findingsof strong interactions The variation of excess Gibbs freeenergy of activation of viscous flow Δ119866lowast119864 with mole fractionof CH has been presented in Figure 9 at all temperaturesThese values are positive over the entire range of compositionof CH According to Iloukhani et al [44 45] negative valuesof Δ119866lowast119864 indicate the presence of weak physical forces such asdispersive forces in the system On the other hand positivevalues of it suggest strong specific interactions This alsosupports the conclusions drawn from our earlier findings
According to Fort and Moore [46] deviation in viscositytends to become more positive as the strength of the inter-action increases The deviation in viscosity variation gives aqualitative estimation of the strength of the intermolecularinteractions The deviation in viscosities may be generallyexplained by considering the following factors (i) The differ-ence in size and shape of the component molecules and theloss of dipolar association in pure componentmay contributeto a decrease in viscosity and (ii) specific interactions betweenunlike components such as hydrogen bond formation ordipole-dipole interactions or charge-transfer complexes maycause increase in viscosity in mixtures compared to in purecomponents [47]The former effect produces negative devia-tion in viscosity and latter effect produces positive deviationin viscosity A perusal of Figure 10 shows that the values ofΔ120578 are positive for the present system at three temperaturesThe positive Δ120578 values decrease with increasing temperatureThe positive Δ120578 values indicate specific interactions whilethe negative Δ120578 values indicate dispersion forces [48ndash50]
In the present investigation the positive values of all binarysystems may be attributed to the dipole-dipole interactionsThe sign and magnitude of Δ119906 play important roles indescribing molecular rearrangements as a result of molecularinteractions occurring among the component molecules inthe mixtures The excess ultrasonic speed with mole fractionof CH is shown in Figure 11 Here we observed that theΔ119906 values are positive for all binary systems over the entirerange of composition at all the studied temperatures Positivedeviations indicate the increasing strength of interactionbetween component molecules of binary liquid mixturesAccording to Reddy et al [51] strong interactions amongthe components of a mixture lead to the formation ofmolecular aggregates and more compact structures thensound will travel faster through the mixture by means oflongitudinal waves and hence the ultrasonic speed deviationswith respect to a linear behaviour will be positive while ifthe structure-breaking factor in the mixture predominatesresulting expansion then the speed of sound through themixture will be slower resulting in negative deviation in thespeed of sound According to Ali et al [52] more positivevalues mean much more strong interactions between themolecules Therefore based on the above references for thepresent scenario interactions are found to be in the order31815K gt 31315K gt 30815K this again emphasizes ourview regarding the interaction between CH and BB
In the present study theoretical sound velocities havebeen evaluated by considering CH as one component andBB as the other component in the binary mixture at all
Journal of Thermodynamics 9
0
5
10
15
20
25
30
35
40
45
0 02 04 06 08 1
xΔ
u(m
middotsminus1)
Figure 11 Variation of deviation in ultrasonic velocity Δ119906 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
C=O
R
R
C=O
R
R∙ ∙ ∙ ∙
∙ ∙ ∙∙
∙ ∙
+ minusO
O
Structure of benzyl benzoate Resonance structure of ketone
lt=gt
Figure 12
the three temperatures Such an evaluation of theoreticalsound velocity is useful to verify the applicability of variousassumes of the theories of liquid mixtures and to arriveat some useful implications regarding the (strength of)molecular interactions between component liquids in somecases The theoretical values of ultrasonic velocity obtainedusing various theories along with the experimental velocityand percentage deviation are summarized in Table 6 Nomoto[53] established the following relation for sound velocitybased on the supposition of the linearity of the molecularsound velocity and the additives of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(11)
Van Dael [54] obtained the ideal mixture relation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(12)
The impedance dependence relation used by Baluja andParsania [55] is given below
119880imp =sum119909119894119885119894
sum119909119894120588119894
(13)
where 119909119894is mole fractions119872
119894is molecular weight 119877 is the
molar sound speed and 119885119894is acoustic impedance of CH and
BB respectively at three temperaturesPercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906expt
] (14)
On observing Table 6 among all the empirical theoriesNomotorsquos relation gives the best estimate of experimental val-ues of sound velocity in the system followed by impedancersquosrelation In the present binary systems the difference betweenexperimental and theoretical velocities is greater where themole fraction of CH varies in the region 04 to 07 Hence itcan be qualitatively inferred that the strength of interactionin the binary mixtures is more in this range of compositionof binary mixtures
The dynamic viscosities of the liquid mixtures have beencalculated using the several empirical relations
Grunberg and Nissan [56] proposed the following equa-tion for the measurement of viscosity of liquid mixtures
where (119882visRT) is an interaction parameterThe theoretical viscosity values using (15) to (17) along
with the percentage error are compiled in Table 7 Theevaluated values of parameters 119866
12 11986712 and 119882visRT and
standard deviations 120590 (10minus3 kgminus1sdotsminus1) are presented in Table 8
10 Journal of Thermodynamics
Table 6 Experimental and theoretical velocities from various empirical relations and percentage deviation in velocities with molefraction119909 of CH with BB at 119879 = 30815 31315 and 31815 K
The estimated values of120590 are indicating that the viscosities arewell correlated by all the three viscosity models Prolongo etal [59] reported positive values of interaction parameters cor-responding to systems with negative excess molar volumesThis is consistent with our results Among all of thesemodelsthe viscosity representations obtained from the Hind modelare in best agreement with the experimental viscosity data
4 Conclusions
(i) Ultrasonic velocities densities and viscosities forbinary liquids of CH with BB are determined exper-
imentally at T = 30815 K 31315 K and 31815 K overthe entire composition range
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119885119864 120587119864
119894 119867119864 Δ119866lowast119864 and
Δ119906 are calculated from experimental results at allthree temperatures The excessdeviation propertiesare fitted to Redlich-Kister-type polynomial and cor-responding standard deviations are evaluated Theobserved negative values of 119881119864
119898 Δ119896119904 119871119864119891 and 120587119864
119894and
positive values of 119885119864 119867119864 Δ119866lowast119864 Δ120578 and Δ119906 for allthe liquid mixtures studied clearly indicate dipole-dipole-type interactions and the geometrical fitting
Journal of Thermodynamics 11
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
Figure 6 Variation of excess acoustic impedance 119885119864 with molefraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
to hydrogen bond formation or dipole-dipole interactionsbetween solute and solvent In the present study the negativecontribution in all the systems prevails in the existenceof greater interactions Nain et al [40] also concluded asimilar observation From Figure 6 the excess values of 119885119864are found to be positive for the system at all temperaturesunder investigation According to Kondaiah andRao [41] thenature of the positive values of 119885119864 is attributed to specificinteraction between the heteromolecules This further sup-ports our earlier finding
The variations of excess internal pressure (120587119864119894) and excess
enthalpy (119867119864) are presented in Figures 7 and 8 for the present
minus35
minus30
minus25
minus20
minus15
minus10
minus5
000 02 04 06 08 10
x
120587E i
(kJmiddotm
olminus
1)
Figure 7 Variation of excess internal pressure 120587119864119894 with mole
fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
0
1000
2000
3000
4000
5000
6000
7000
8000
0 02 04 06 08 1
x
HE
(Jmiddotm
olminus
1)
Figure 8 Variation of excess enthalpy119867119864 with mole fraction 119909 ofCH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
system at all the three temperatures respectively From thesefigures it is observed that 120587119864
119894is negative and 119867119864 is positive
over the entire composition range of CH In accordance withKondaiah et al [42] the negative values of 120587119864
119894indicate the
existence of strong specific interactions and according toKumar and Rao [43] positive value of Δ119867 suggests strongbonding and exothermic reactionsThus it can be concludedthat strong specific interactions are operative in the systems
8 Journal of Thermodynamics
000
020
040
060
080
100
0 02 04 06 08 1
xΔ
Glowast
E(k
Jmiddotmol
minus1)
Figure 9 Variation of excess Gibbs free energy of activation of viscous flow Δ119866lowast119864 with mole fraction 119909 of CH in BB (X) 30815 K (◼)31315 K and (998771) 31815 K
000
005
010
015
020
025
0 02 04 06 08 1
x
Δ120578
(10
minus3
Nmiddotsmiddot
mminus
2)
Figure 10 Variation of deviation in viscosity Δ120578 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
investigated These conclusions support our earlier findingsof strong interactions The variation of excess Gibbs freeenergy of activation of viscous flow Δ119866lowast119864 with mole fractionof CH has been presented in Figure 9 at all temperaturesThese values are positive over the entire range of compositionof CH According to Iloukhani et al [44 45] negative valuesof Δ119866lowast119864 indicate the presence of weak physical forces such asdispersive forces in the system On the other hand positivevalues of it suggest strong specific interactions This alsosupports the conclusions drawn from our earlier findings
According to Fort and Moore [46] deviation in viscositytends to become more positive as the strength of the inter-action increases The deviation in viscosity variation gives aqualitative estimation of the strength of the intermolecularinteractions The deviation in viscosities may be generallyexplained by considering the following factors (i) The differ-ence in size and shape of the component molecules and theloss of dipolar association in pure componentmay contributeto a decrease in viscosity and (ii) specific interactions betweenunlike components such as hydrogen bond formation ordipole-dipole interactions or charge-transfer complexes maycause increase in viscosity in mixtures compared to in purecomponents [47]The former effect produces negative devia-tion in viscosity and latter effect produces positive deviationin viscosity A perusal of Figure 10 shows that the values ofΔ120578 are positive for the present system at three temperaturesThe positive Δ120578 values decrease with increasing temperatureThe positive Δ120578 values indicate specific interactions whilethe negative Δ120578 values indicate dispersion forces [48ndash50]
In the present investigation the positive values of all binarysystems may be attributed to the dipole-dipole interactionsThe sign and magnitude of Δ119906 play important roles indescribing molecular rearrangements as a result of molecularinteractions occurring among the component molecules inthe mixtures The excess ultrasonic speed with mole fractionof CH is shown in Figure 11 Here we observed that theΔ119906 values are positive for all binary systems over the entirerange of composition at all the studied temperatures Positivedeviations indicate the increasing strength of interactionbetween component molecules of binary liquid mixturesAccording to Reddy et al [51] strong interactions amongthe components of a mixture lead to the formation ofmolecular aggregates and more compact structures thensound will travel faster through the mixture by means oflongitudinal waves and hence the ultrasonic speed deviationswith respect to a linear behaviour will be positive while ifthe structure-breaking factor in the mixture predominatesresulting expansion then the speed of sound through themixture will be slower resulting in negative deviation in thespeed of sound According to Ali et al [52] more positivevalues mean much more strong interactions between themolecules Therefore based on the above references for thepresent scenario interactions are found to be in the order31815K gt 31315K gt 30815K this again emphasizes ourview regarding the interaction between CH and BB
In the present study theoretical sound velocities havebeen evaluated by considering CH as one component andBB as the other component in the binary mixture at all
Journal of Thermodynamics 9
0
5
10
15
20
25
30
35
40
45
0 02 04 06 08 1
xΔ
u(m
middotsminus1)
Figure 11 Variation of deviation in ultrasonic velocity Δ119906 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
C=O
R
R
C=O
R
R∙ ∙ ∙ ∙
∙ ∙ ∙∙
∙ ∙
+ minusO
O
Structure of benzyl benzoate Resonance structure of ketone
lt=gt
Figure 12
the three temperatures Such an evaluation of theoreticalsound velocity is useful to verify the applicability of variousassumes of the theories of liquid mixtures and to arriveat some useful implications regarding the (strength of)molecular interactions between component liquids in somecases The theoretical values of ultrasonic velocity obtainedusing various theories along with the experimental velocityand percentage deviation are summarized in Table 6 Nomoto[53] established the following relation for sound velocitybased on the supposition of the linearity of the molecularsound velocity and the additives of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(11)
Van Dael [54] obtained the ideal mixture relation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(12)
The impedance dependence relation used by Baluja andParsania [55] is given below
119880imp =sum119909119894119885119894
sum119909119894120588119894
(13)
where 119909119894is mole fractions119872
119894is molecular weight 119877 is the
molar sound speed and 119885119894is acoustic impedance of CH and
BB respectively at three temperaturesPercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906expt
] (14)
On observing Table 6 among all the empirical theoriesNomotorsquos relation gives the best estimate of experimental val-ues of sound velocity in the system followed by impedancersquosrelation In the present binary systems the difference betweenexperimental and theoretical velocities is greater where themole fraction of CH varies in the region 04 to 07 Hence itcan be qualitatively inferred that the strength of interactionin the binary mixtures is more in this range of compositionof binary mixtures
The dynamic viscosities of the liquid mixtures have beencalculated using the several empirical relations
Grunberg and Nissan [56] proposed the following equa-tion for the measurement of viscosity of liquid mixtures
where (119882visRT) is an interaction parameterThe theoretical viscosity values using (15) to (17) along
with the percentage error are compiled in Table 7 Theevaluated values of parameters 119866
12 11986712 and 119882visRT and
standard deviations 120590 (10minus3 kgminus1sdotsminus1) are presented in Table 8
10 Journal of Thermodynamics
Table 6 Experimental and theoretical velocities from various empirical relations and percentage deviation in velocities with molefraction119909 of CH with BB at 119879 = 30815 31315 and 31815 K
The estimated values of120590 are indicating that the viscosities arewell correlated by all the three viscosity models Prolongo etal [59] reported positive values of interaction parameters cor-responding to systems with negative excess molar volumesThis is consistent with our results Among all of thesemodelsthe viscosity representations obtained from the Hind modelare in best agreement with the experimental viscosity data
4 Conclusions
(i) Ultrasonic velocities densities and viscosities forbinary liquids of CH with BB are determined exper-
imentally at T = 30815 K 31315 K and 31815 K overthe entire composition range
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119885119864 120587119864
119894 119867119864 Δ119866lowast119864 and
Δ119906 are calculated from experimental results at allthree temperatures The excessdeviation propertiesare fitted to Redlich-Kister-type polynomial and cor-responding standard deviations are evaluated Theobserved negative values of 119881119864
119898 Δ119896119904 119871119864119891 and 120587119864
119894and
positive values of 119885119864 119867119864 Δ119866lowast119864 Δ120578 and Δ119906 for allthe liquid mixtures studied clearly indicate dipole-dipole-type interactions and the geometrical fitting
Journal of Thermodynamics 11
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
Figure 9 Variation of excess Gibbs free energy of activation of viscous flow Δ119866lowast119864 with mole fraction 119909 of CH in BB (X) 30815 K (◼)31315 K and (998771) 31815 K
000
005
010
015
020
025
0 02 04 06 08 1
x
Δ120578
(10
minus3
Nmiddotsmiddot
mminus
2)
Figure 10 Variation of deviation in viscosity Δ120578 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
investigated These conclusions support our earlier findingsof strong interactions The variation of excess Gibbs freeenergy of activation of viscous flow Δ119866lowast119864 with mole fractionof CH has been presented in Figure 9 at all temperaturesThese values are positive over the entire range of compositionof CH According to Iloukhani et al [44 45] negative valuesof Δ119866lowast119864 indicate the presence of weak physical forces such asdispersive forces in the system On the other hand positivevalues of it suggest strong specific interactions This alsosupports the conclusions drawn from our earlier findings
According to Fort and Moore [46] deviation in viscositytends to become more positive as the strength of the inter-action increases The deviation in viscosity variation gives aqualitative estimation of the strength of the intermolecularinteractions The deviation in viscosities may be generallyexplained by considering the following factors (i) The differ-ence in size and shape of the component molecules and theloss of dipolar association in pure componentmay contributeto a decrease in viscosity and (ii) specific interactions betweenunlike components such as hydrogen bond formation ordipole-dipole interactions or charge-transfer complexes maycause increase in viscosity in mixtures compared to in purecomponents [47]The former effect produces negative devia-tion in viscosity and latter effect produces positive deviationin viscosity A perusal of Figure 10 shows that the values ofΔ120578 are positive for the present system at three temperaturesThe positive Δ120578 values decrease with increasing temperatureThe positive Δ120578 values indicate specific interactions whilethe negative Δ120578 values indicate dispersion forces [48ndash50]
In the present investigation the positive values of all binarysystems may be attributed to the dipole-dipole interactionsThe sign and magnitude of Δ119906 play important roles indescribing molecular rearrangements as a result of molecularinteractions occurring among the component molecules inthe mixtures The excess ultrasonic speed with mole fractionof CH is shown in Figure 11 Here we observed that theΔ119906 values are positive for all binary systems over the entirerange of composition at all the studied temperatures Positivedeviations indicate the increasing strength of interactionbetween component molecules of binary liquid mixturesAccording to Reddy et al [51] strong interactions amongthe components of a mixture lead to the formation ofmolecular aggregates and more compact structures thensound will travel faster through the mixture by means oflongitudinal waves and hence the ultrasonic speed deviationswith respect to a linear behaviour will be positive while ifthe structure-breaking factor in the mixture predominatesresulting expansion then the speed of sound through themixture will be slower resulting in negative deviation in thespeed of sound According to Ali et al [52] more positivevalues mean much more strong interactions between themolecules Therefore based on the above references for thepresent scenario interactions are found to be in the order31815K gt 31315K gt 30815K this again emphasizes ourview regarding the interaction between CH and BB
In the present study theoretical sound velocities havebeen evaluated by considering CH as one component andBB as the other component in the binary mixture at all
Journal of Thermodynamics 9
0
5
10
15
20
25
30
35
40
45
0 02 04 06 08 1
xΔ
u(m
middotsminus1)
Figure 11 Variation of deviation in ultrasonic velocity Δ119906 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
C=O
R
R
C=O
R
R∙ ∙ ∙ ∙
∙ ∙ ∙∙
∙ ∙
+ minusO
O
Structure of benzyl benzoate Resonance structure of ketone
lt=gt
Figure 12
the three temperatures Such an evaluation of theoreticalsound velocity is useful to verify the applicability of variousassumes of the theories of liquid mixtures and to arriveat some useful implications regarding the (strength of)molecular interactions between component liquids in somecases The theoretical values of ultrasonic velocity obtainedusing various theories along with the experimental velocityand percentage deviation are summarized in Table 6 Nomoto[53] established the following relation for sound velocitybased on the supposition of the linearity of the molecularsound velocity and the additives of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(11)
Van Dael [54] obtained the ideal mixture relation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(12)
The impedance dependence relation used by Baluja andParsania [55] is given below
119880imp =sum119909119894119885119894
sum119909119894120588119894
(13)
where 119909119894is mole fractions119872
119894is molecular weight 119877 is the
molar sound speed and 119885119894is acoustic impedance of CH and
BB respectively at three temperaturesPercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906expt
] (14)
On observing Table 6 among all the empirical theoriesNomotorsquos relation gives the best estimate of experimental val-ues of sound velocity in the system followed by impedancersquosrelation In the present binary systems the difference betweenexperimental and theoretical velocities is greater where themole fraction of CH varies in the region 04 to 07 Hence itcan be qualitatively inferred that the strength of interactionin the binary mixtures is more in this range of compositionof binary mixtures
The dynamic viscosities of the liquid mixtures have beencalculated using the several empirical relations
Grunberg and Nissan [56] proposed the following equa-tion for the measurement of viscosity of liquid mixtures
where (119882visRT) is an interaction parameterThe theoretical viscosity values using (15) to (17) along
with the percentage error are compiled in Table 7 Theevaluated values of parameters 119866
12 11986712 and 119882visRT and
standard deviations 120590 (10minus3 kgminus1sdotsminus1) are presented in Table 8
10 Journal of Thermodynamics
Table 6 Experimental and theoretical velocities from various empirical relations and percentage deviation in velocities with molefraction119909 of CH with BB at 119879 = 30815 31315 and 31815 K
The estimated values of120590 are indicating that the viscosities arewell correlated by all the three viscosity models Prolongo etal [59] reported positive values of interaction parameters cor-responding to systems with negative excess molar volumesThis is consistent with our results Among all of thesemodelsthe viscosity representations obtained from the Hind modelare in best agreement with the experimental viscosity data
4 Conclusions
(i) Ultrasonic velocities densities and viscosities forbinary liquids of CH with BB are determined exper-
imentally at T = 30815 K 31315 K and 31815 K overthe entire composition range
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119885119864 120587119864
119894 119867119864 Δ119866lowast119864 and
Δ119906 are calculated from experimental results at allthree temperatures The excessdeviation propertiesare fitted to Redlich-Kister-type polynomial and cor-responding standard deviations are evaluated Theobserved negative values of 119881119864
119898 Δ119896119904 119871119864119891 and 120587119864
119894and
positive values of 119885119864 119867119864 Δ119866lowast119864 Δ120578 and Δ119906 for allthe liquid mixtures studied clearly indicate dipole-dipole-type interactions and the geometrical fitting
Journal of Thermodynamics 11
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
Figure 11 Variation of deviation in ultrasonic velocity Δ119906 with mole fraction 119909 of CH in BB (X) 30815 K (◼) 31315 K and (998771) 31815 K
C=O
R
R
C=O
R
R∙ ∙ ∙ ∙
∙ ∙ ∙∙
∙ ∙
+ minusO
O
Structure of benzyl benzoate Resonance structure of ketone
lt=gt
Figure 12
the three temperatures Such an evaluation of theoreticalsound velocity is useful to verify the applicability of variousassumes of the theories of liquid mixtures and to arriveat some useful implications regarding the (strength of)molecular interactions between component liquids in somecases The theoretical values of ultrasonic velocity obtainedusing various theories along with the experimental velocityand percentage deviation are summarized in Table 6 Nomoto[53] established the following relation for sound velocitybased on the supposition of the linearity of the molecularsound velocity and the additives of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(11)
Van Dael [54] obtained the ideal mixture relation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(12)
The impedance dependence relation used by Baluja andParsania [55] is given below
119880imp =sum119909119894119885119894
sum119909119894120588119894
(13)
where 119909119894is mole fractions119872
119894is molecular weight 119877 is the
molar sound speed and 119885119894is acoustic impedance of CH and
BB respectively at three temperaturesPercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906expt
] (14)
On observing Table 6 among all the empirical theoriesNomotorsquos relation gives the best estimate of experimental val-ues of sound velocity in the system followed by impedancersquosrelation In the present binary systems the difference betweenexperimental and theoretical velocities is greater where themole fraction of CH varies in the region 04 to 07 Hence itcan be qualitatively inferred that the strength of interactionin the binary mixtures is more in this range of compositionof binary mixtures
The dynamic viscosities of the liquid mixtures have beencalculated using the several empirical relations
Grunberg and Nissan [56] proposed the following equa-tion for the measurement of viscosity of liquid mixtures
where (119882visRT) is an interaction parameterThe theoretical viscosity values using (15) to (17) along
with the percentage error are compiled in Table 7 Theevaluated values of parameters 119866
12 11986712 and 119882visRT and
standard deviations 120590 (10minus3 kgminus1sdotsminus1) are presented in Table 8
10 Journal of Thermodynamics
Table 6 Experimental and theoretical velocities from various empirical relations and percentage deviation in velocities with molefraction119909 of CH with BB at 119879 = 30815 31315 and 31815 K
The estimated values of120590 are indicating that the viscosities arewell correlated by all the three viscosity models Prolongo etal [59] reported positive values of interaction parameters cor-responding to systems with negative excess molar volumesThis is consistent with our results Among all of thesemodelsthe viscosity representations obtained from the Hind modelare in best agreement with the experimental viscosity data
4 Conclusions
(i) Ultrasonic velocities densities and viscosities forbinary liquids of CH with BB are determined exper-
imentally at T = 30815 K 31315 K and 31815 K overthe entire composition range
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119885119864 120587119864
119894 119867119864 Δ119866lowast119864 and
Δ119906 are calculated from experimental results at allthree temperatures The excessdeviation propertiesare fitted to Redlich-Kister-type polynomial and cor-responding standard deviations are evaluated Theobserved negative values of 119881119864
119898 Δ119896119904 119871119864119891 and 120587119864
119894and
positive values of 119885119864 119867119864 Δ119866lowast119864 Δ120578 and Δ119906 for allthe liquid mixtures studied clearly indicate dipole-dipole-type interactions and the geometrical fitting
Journal of Thermodynamics 11
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
Table 6 Experimental and theoretical velocities from various empirical relations and percentage deviation in velocities with molefraction119909 of CH with BB at 119879 = 30815 31315 and 31815 K
The estimated values of120590 are indicating that the viscosities arewell correlated by all the three viscosity models Prolongo etal [59] reported positive values of interaction parameters cor-responding to systems with negative excess molar volumesThis is consistent with our results Among all of thesemodelsthe viscosity representations obtained from the Hind modelare in best agreement with the experimental viscosity data
4 Conclusions
(i) Ultrasonic velocities densities and viscosities forbinary liquids of CH with BB are determined exper-
imentally at T = 30815 K 31315 K and 31815 K overthe entire composition range
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119885119864 120587119864
119894 119867119864 Δ119866lowast119864 and
Δ119906 are calculated from experimental results at allthree temperatures The excessdeviation propertiesare fitted to Redlich-Kister-type polynomial and cor-responding standard deviations are evaluated Theobserved negative values of 119881119864
119898 Δ119896119904 119871119864119891 and 120587119864
119894and
positive values of 119885119864 119867119864 Δ119866lowast119864 Δ120578 and Δ119906 for allthe liquid mixtures studied clearly indicate dipole-dipole-type interactions and the geometrical fitting
Journal of Thermodynamics 11
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
Table 7 Experimental and theoretical values of viscosity from various empirical relations and percentage deviation in viscosity in CH + BBat 119879 = 30815 31315 and 31815 K
119879 (K) Exptl viscosity Gruenberg Hind Katti G H K
Table 8 Various interaction parameters calculated from variousempirical relations and the corresponding standard deviations(12059010minus3Nsdotssdotmminus2) of the present systemCH+ BB at119879 = 30815 31315and 31815 K
of molecules leading to strong molecular interac-tions between CH and BB These strong interactionsincrease with temperature
(iii) The values of1198811198981
1198811198982
and1198811198641198981
1198811198641198982
are calculatedfrom experimental data The observed lower partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate that strong interactions present in the systemsupport the trends of 119881119864
119898values very well
(iv) The ultrasonic velocitiesviscosities computed fromthree different velocityviscosity theories were cor-related with the experimentally measured ultra-sonic velocities and their percentage deviationswere evaluated Among all the empirical theoriesNomotorsquos velocityHind viscosity relation gives thebest estimate of experimental values of sound veloc-ityviscosity in the system at all temperatures
12 Journal of Thermodynamics
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
Sk Md Nayeem is highly thankful to UGC New Delhi andGovernment of India for sanction of financial grant under XIIPlan towards MRP (MRP-467114(SEROUGC))
References
[1] J Rajasekhar and P R Naidu ldquoSpeed of sound of 1 3-dichlorobenzene + methyl ethyl ketone + 1-alkanols at 30315 Krdquo Journalof Chemical Engineering Data vol 48 pp 373ndash375 1996
[2] S L Oswal P Oswal and R P Phalak ldquoSpeed of soundisentropic compressibilities and excessmolar volumes of binarymixtures containing p-dioxanerdquo Journal of Solution Chemistryvol 27 no 6 pp 507ndash520 1998
[3] M Geetalakshmi Molecular interaction in the binary liquidmixtures-an ultrasonic study [PhD thesis] Sri VenkateswaraUniveristy Tirupati India 2006
[4] M Geetalakshmi P S Naidu and K R Prasa ldquoMolecular inter-actions in binary mixtures of benzyl benzoate with alcoholsrdquoJournal of Pure amp Applied Ultrasonics vol 30 pp 18ndash23 2008
[5] J Sivasankar M Geetalakshmi P S Naidu and K R PrasadldquoExcess parameters of benzyl benzoate in dichloromethane iso-butanolrdquo Journal of PureampApplied Ultrasonics vol 29 no 2 pp82ndash88 2007
[6] P RameshUltrasonic study of the binary liquid mixtures (BenzylBenzoate + Substituted Benzenes) [MS thesis] Sri VenkateswaraUniveristy Tirupati India 2008
[7] B Gonzalez D Dominguez and J Tojo ldquoPhysical properties ofthe binary systems methyl cuclopentane with ketones (acetonebutone and 2-pentanone) at 119879 = (29315 29815 30315)KrdquoJournal of Chemical Thermodynics vol 38 no 6 pp 707ndash7162006
[8] PM Krishna B R Kumar B Sathyanarayana K S Kumar andN Satyanarayana ldquoDensities and speeds of sound for binaryliquid mixtures of thiolane-11-dioxide with butanone pentan-2-one pentan-3-one and 4-methyl-pentan-2-one at T = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[9] P G Kumari P Venkatesu M V P Rao M-J Lee and H-M Lin ldquoExcess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 30315 KrdquoThe Journalof Chemical Thermodynamics vol 41 no 5 pp 586ndash590 2009
[10] M Sreenivasulu and P R Naidu ldquoExcess volumes and isen-tropic compressibility of binary mixtures of butyl amine andcyclic ketonesrdquo Australian Journal of Chemistry vol 32 pp1649ndash1652 1979
[11] S L Oswal and H S Desai ldquoStudies of viscosity andexcess molar volume of binary mixtures 3 1-Alkanol+di-n-propylamine and+di-n-butylamine mixtures at 30315 and31315 Krdquo Fluid Phase Equilibria vol 186 no 1-2 pp 81ndash1022001
[12] S Thirumaran and N Karthikeyan ldquoThermo-acoustical andexcess thermodynamic studies of ternary liquid mixtures ofsubstituted benzenes in aqueous mixed solvent systems at
30315 30815 and 31315 Krdquo International Journal of ChemicalResearch vol 3 no 3 pp 83ndash98 2011
[13] M V Rathnam R T Sayed K R Bhanushali and M SS Kumar ldquoMolecular interaction study of binary mixtures ofmethyl benzoate viscometric and ultrasonic studyrdquo Journal ofMolecular Liquids vol 166 pp 9ndash16 2012
[14] S M Nayeem and D K Rao ldquoUltrasonic investigations ofmolecular interaction in binary mixtures of benzyl benzoatewith isomers of butanolrdquo International Journal of PharmaResearch amp Review vol 3 no 2 pp 65ndash78 2014
[15] N JMadhuri P S Naidu J Glory andK R Prasad ldquoUltrasonicinvestigations of molecular interaction in binary mixtures ofbenzyl benzoate with acetonitrile and benzonitrilerdquo E-Journalof Chemistry vol 8 no 1 pp 457ndash469 2011
[16] S Sri Z Begum and C Rambabu ldquoTheoretical evaluation ofultrasonic velocities in binary liquidmixtures of anisic aldehydewith some esters at different temperatures using differenttheories and modelsrdquo Journal of Thermodynamic Catalysis vol4 pp 3ndash8 2013
[17] A I Vogel Text Book of Organic Chemistry JohnWiley amp SonsNew York NY USA 5th edition 1989
[18] J A Riddick W B Burger and T K Sankano Techniques inChemistry vol 2 John Wiley amp Sons New York NY USA 4thedition 1986
[19] B S Furniss A J Hannaford V S Rogers P W G Smith andA R Tachell Vogelrsquos Textbook of Practical Organic ChemistryLongman 4th edition 1980
[20] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Physical Chemistry vol 29 pp 130ndash137 1925
[21] P S Naidu and K R Prasad ldquoUltrasonic velocity and alliedparameters in solutions of cypermethrin with xylene andethanolrdquo Indian Journal of Pure and Applied Physics vol 42 no7 pp 512ndash517 2004
[22] M Kondaiah K Sreekanth D Sravana Kumar and D KrishnaRao ldquoVolumetric and viscometric properties of propanoicacid in equimolar mixtures of NN-dimethyl formamide +alkanols at TK = 30315 31315 and 32315rdquo Journal of SolutionChemistry vol 42 no 3 pp 494ndash515 2013
[23] M Kondaiah D S Kumar K Sreekanth and D K RaoldquoDensities and viscosities of binary mixtures of propanoicacid with N N-dimethylaniline and N N-diethylaniline atT = (30315 31315 and 32315) Krdquo Journal of Chemical andEngineering Data vol 57 no 2 pp 352ndash357 2012
[24] K Sreekanth M Kondaiah D Sravana Kumar and D KRao ldquoInfluence of temperature on thermodynamic propertiesof acid-base liquid mixturesrdquo Journal of Thermal Analysis andCalorimetry vol 110 no 3 pp 1341ndash1352 2012
[25] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueouselectrolyte solutionsrdquo Journal of Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2402ndash2415 2014
[26] M Sri Lakshmi R Ramesh Raju C Rambabu G V RamaRao and K Narendra ldquoStudy of molecular interactions inbinary liquid mixtures containing higher alcohols at differenttemperaturesrdquo Research amp Review Journal of Chemistry vol 2no 1 pp 12ndash24 2013
[27] B Jacobson ldquoIntermolecular free lengths in the liquid stateI Isentropic and isothermal compressibilitiesrdquo Acta ChemicaScandinavia vol 6 pp 1485ndash1498 1952
[28] S Glasstone Text Book of Physical Chemistry Macmillan 2ndedition 1995
Journal of Thermodynamics 13
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984
[29] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification of solutionsrdquoIndustrial amp Engineering Chemistry vol 40 no 2 pp 345ndash3481948
[30] M G Sankar V Ponneri K S Kumar and S SakamurildquoMolecular interactions between amine and cyclic ketonesat different temperaturesrdquo Journal of Thermal Analysis andCalorimetry vol 115 no 2 pp 1821ndash1827 2014
[31] S Gadzuric A Nikolic M Vranes B Jovic M Damjanovicand S Dozic ldquoVolumetric properties of binary mixtures of N-ethylformamide with tetrahydrofuran 2-butanone and ethy-lacetate from T = (29315 to 31315) Krdquo Journal of ChemicalThermodynamics vol 51 pp 37ndash44 2012
[32] M Rastogi A Awasthi M Gupta and J P Shukla ldquoUltrasonicinvestigations of XHO bond complexesrdquo Indian Journal ofPure and Applied Physics vol 40 no 4 pp 256ndash263 2002
[33] J G Baragi V K Mutalik and S B Mekali ldquoMolecular inter-action studies in mixtures of methyl cyclohexane with alkanesa theoretical approachrdquo International Journal of Pharmacy andBiological Sciences vol 3 no 2 pp 185ndash197 2013
[34] R Mehra A Gupta and R Israni ldquoExcess volume excessisentropic compressibility partial molar volume and specificheat ratio of ternary mixtures of cyclohexane + decane +alkanols at 29815 and 30815 Krdquo Indian Journal of Chemistryvol 40 no 5 pp 505ndash508 2001
[35] K K Ohomuru and S J Murakami ldquoSpeeds of soundexcess molar volumes and isentropic compressibilitiesof ldquo119909CH
3COC2H5
+ (1 minus 119909)C6H6rdquo ldquo119909CH
3COC2H5
+(1 minus 119909)C
6H5CH3rdquo ldquo119909CH
3COC2H5+ (1 minus 119909)C
6H5Clrdquo and
ldquo119909C2H5COC2H5+ (1minus119909)C
6H6rdquo at 29815 KrdquoChemicalThermo-
dynamics vol 19 pp 171ndash176 1987[36] P Venkatesu and M V P Rao ldquoExcess volumes of ternary
mixtures of NN-dimethylformamide + methyl isobutyl ketone+ 1-alkanols at 30315 Krdquo Fluid Phase Equilibria vol 98 pp 173ndash178 1994
[37] M V Rathnam M S S Kumar R T Sayed and D RAmbavadekar ldquoStudy onThermo Physical properties of binarymixtures of Butyl Propionate and ketones at 30315 and 31315 KrdquoEuropean Chemical Bulletin vol 3 no 2 pp 166ndash172 2014
[38] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[39] S Singh I Vibhu M Gupta and J P Shukla ldquoExcess acousticaland volumetric properties and the theoretical estimation of theexcess thermodynamic functions of binary liquid mixturesrdquoChinese Journal of Physics vol 45 no 4 pp 412ndash424 2007
[40] A KNain R Sharma A Ali and S Gopal ldquoDensities and volu-metric properties of ethyl acrylate + 1-butanol or 2-butanol or2-methyl-1-propanol or 2-methyl-2-propanol binary mixturesat temperatures from 28815 to 31815 Krdquo Journal of MolecularLiquids vol 144 no 3 pp 138ndash144 2009
[41] M Kondaiah and D K Rao ldquoExperimental study of the excessproperties for (1 2-dichloroethane or dichloromethane withN N-dimethyl formamide or dimethyl sulfoxide)rdquo Journal ofMolecular Liquids vol 195 pp 110ndash115 2014
[42] M Kondaiah K Sreekanth S M Nayeem and D K RaoldquoUltrasonic volumetric and viscometric study of aqueous-electrolyte solutionsrdquo Journal Chemical Biological amp PhysicalSciences vol 4 no 3 pp 2401ndash2415 2014
[43] D S Kumar andDK Rao ldquoStudy ofmolecular interactions andultrasonic velocity in mixtures of some alkanols with aqueous
propylene glycolrdquo Indian Journal of Pure and Applied Physicsvol 45 no 3 pp 210ndash220 2007
[44] H Iloukhani H A Zarei and M Behroozi ldquoThermodynamicstudies of ternary mixtures of diethylcarbonate (1) + dimethyl-carbonate (2) +NN-dimethylacetamide (3) at 29815 Krdquo Journalof Molecular Liquids vol 135 no 1ndash3 pp 141ndash145 2007
[45] H Iloukhani and Z Rostami ldquoMeasurement of some thermo-dynamic and acoustic properties of binary solutions of NN-dimethylformamide with 1-alkanols at 30∘C and comparisontheoriesrdquo Journal of Solution Chemistry vol 32 no 5 pp 451ndash462 2003
[46] R J Fort and W R Moore ldquoViscosities of binary liquidmixturesrdquo Transactions of the Faraday Society vol 62 pp 1112ndash1119 1966
[47] L Pikkarainen ldquoDensities and viscosities of binary mixturesof NN-dimethylacetamide with aliphatic alcoholsrdquo Journal ofChemical amp Engineering Data vol 28 no 3 pp 344ndash347 1983
[48] R Palepu J Oliver and D Campbell ldquoThermodynamic andtransport properties of o-chlorophenol with aniline and N-alkylanilinesrdquo Journal of Chemical and Engineering Data vol30 no 3 pp 355ndash360 1985
[49] R Palepu J Oliver and B Mackinnon ldquoViscosities and den-sities of binary liquid mixtures of m-cresol with substitutedanilinrdquo Canadian Journal of Chemistry vol 63 pp 1024ndash10301985
[50] T M Reed and T E Taylor ldquoViscosities of liquid mixturesrdquoJournal of Physical Chemistry vol 63 no 1 pp 58ndash67 1959
[51] Y Reddy P S Naidu and K R Prasad ldquoUltrasonic study ofacetophenones in the binary-mixtures containing isopropanolas common componentrdquo Indian Journal of Pure amp AppliedPhysics vol 32 no 12 pp 958ndash963 1994
[52] A Ali F Nabi and M Tariq ldquoVolumetric viscometric ultra-sonic and refractive index properties of liquid mixtures ofbenzene with industrially important monomers at differenttemperaturesrdquo International Journal of Thermophysics vol 30no 2 pp 464ndash474 2009
[53] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[54] W van Dael Thermodynamic Properties and Velocity of Soundchapter 5 Butterworth London UK 1975
[55] S Baluja and P H Parsania ldquoAcoustical properties of 3-120572- furylacrylic acid in protic and aprotic solventsrdquo Asian Journal ofChemistry vol 7 pp 417ndash423 1995
[56] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949
[57] R K Hind E McLaughlin and A R Ubbelohde ldquoStructureand viscosity of liquids Camphor + pyrene mixturesrdquo Transac-tions of the Faraday Society vol 56 pp 328ndash330 1960
[58] P K Katti and M M Chaudhri ldquoViscosities of binary mixturesof benzyl acetate with dioxane aniline andm-cresolrdquo Journal ofChemical and Engineering Data vol 9 no 3 pp 442ndash443 1964
[59] M G Prolongo R M Masegosa I Hernandez-Fuentes andA Horta ldquoViscosities and excess volumes of binary mix-tures formed by the liquids acetonitrile pentyl acetate 1-chlorobutane and carbon tetrachloride at 25∘CrdquoThe Journal ofPhysical Chemistry vol 88 no 10 pp 2163ndash2167 1984