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Research ArticleUltrasonic Investigations of Molecular Interaction inBinary Mixtures of Cyclohexanone with Isomers of Butanol
Sk Md Nayeem1 M Kondaiah2 K Sreekanth3 and D Krishna Rao4
1Department of Physics KRK Government Degree College Addanki 523 201 India2Department of Physics NM Government Degree College Jogipet Medak District Telangana India3Department of Physics PBN College Nidubrolu Guntur District India4Department of Physics Acharya Nagarjuna University Nagarjuna Nagar 522 510 India
Correspondence should be addressed to D Krishna Rao krdhanekulayahoocoin
Received 11 August 2014 Revised 21 October 2014 Accepted 3 November 2014 Published 18 December 2014
Academic Editor Parsotam H Parsania
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 speed 119906 and density 120588 have been measured in binary liquid mixtures of cyclohexanone with the isomers ofbutanol (119899-butanol sec-butanol and tert-butanol) at 30815 K over the entire range of composition Molar volume (119881
119898) adiabatic
compressibility (119896119904) intermolecular free length (119871
119891) acoustic impedance (119911) and their excessdeviation along with Δ119906 have been
calculated from the experimental dataThese values have been fitted to Redlich-Kister type polynomial equation Positive values of119881119864
119898Δ119896119904 119871119864119891and negative values of 119911119864Δ119906 have been observed for all the liquidmixtures indicating the existence of weak interactions
between components Rupture of H-bond or reduction in H-bond strength of isomers of butanol or breaking of the structure ofone or both of the components in a solution causes the existence of dispersions in the present investigated binary mixtures Thedata obtained from 119881
1198981 1198811198982
and excess partial molar volumes 1198811198641198981
1198811198641198982
reflects the inferences drawn from 119881119864119898 Furthermore
FTIR spectra support the conclusions drawn from excessdeviation properties The measured values of ultrasonic speed for all theinvestigated mixtures have been compared with the theoretically estimated values using empirical relations such as Nomoto VanDael and Vangeels Impedance and Rao specific sound speed
1 Introduction
Ultrasonic measurements are very useful in chemical andfood processing pharmaceuticals material testing andunderwater ranging and cleaning and are also commonlyemployed in mechanical machinery of materials [1] prepa-ration of colloids or emulsions the pregermination of seedsimaging of biological tissues [2] activation energy of meta-bolic process [3] formation and destruction of azeotropesin petrochemical industries [4] and nondestructive testing(NDT)
Alcohols are self-associated organic liquids used for thesynthesis of other organic compounds They are also widelyused as coupling and dispersing agents in the chemicalpharmaceutical and household industries and as carrier andextraction solvents for natural products Cyclohexanone andits derivatives are used for the synthesis of pharmaceuticals
dyes herbicides pesticides plasticizers and rubber chemi-cals Ketones are a class of an organic compound that containsa carbonyl group and two aliphatic or aromatic substituentscontaining the chemical formula RCOR1 (general chemicalformula of Ketones) The chemical reactivity of the carbonylgroup plays vital role in chemical reactions and is influencedconsiderably by steric effects The greater electronegativityof Ominus and high dipole moment value make Cyclohexanonepolar Scheme 1 illustrates this polarity Further the presenceof oxygen with its nonbonding electron pairs makes cyclo-hexanoneH-bond acceptorsThus a study on thermophysicalproperties data of binary liquid mixtures containing ketoneshas attracted considerable interest in the literature [5ndash9]
Literature survey reveals that Tsierkezos et al [10] studiedmolecular interactions in cyclohexanone with methanolethanol 1-propanol 1-butanol and 1-pentanol at 29315 Kand Sri Lakshmi et al [11] studied molecular interactions in
Hindawi Publishing CorporationJournal of Applied ChemistryVolume 2014 Article ID 741795 11 pageshttpdxdoiorg1011552014741795
2 Journal of Applied Chemistry
RR
RR
C CO O+ minus
Resonance structure
hArr∙∙
∙∙
∙∙
∙∙
∙∙
Scheme 1
cyclohexanone with 119899-heptanol 119899-octanol and isooctanolat temperatures 30315 30815 31315 and 31815 K overthe entire range of composition Keeping these importantaspects in mind the present study deals with ultrasonic andthermodynamic study of cyclohexanone (CH) with the iso-mers of butanol (119899-butanol sec-butanol and tert-butanol) at30815 K The liquids under investigation have been chosenon the basis of their multifold applications
2 Experimental Section
High purity analytical reagent (AR) grade compounds ofcyclohexanone (mass fraction purity gt 99) and 119899-butanolsec-butanol and tert-butanol (mass fraction purity gt 995)obtained from S D Fine Chemicals are used in the presentstudy The chemicals are further purified by standard meth-ods mentioned in [12 13]The weighing of solutions has beenmade usingMETTLER TOLEDO (Switzerlandmake) ABB5-SFACT digital balance with an accuracy of plusmn001mg Theuncertainty in themole fraction is 10minus4The ultrasonic speedsof pure liquids and liquid mixtures have been measuredusing an ultrasonic interferometer (Mittal type Model F-82)working at 2MHz fixed frequencywith an accuracy ofplusmn02The 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 of pure liquids and their mixtures have beendetermined by using a 5 cm3 two-stem double-walled Parkeramp Parker type pycnometer [15]This pycnometer is calibratedwith triply distilled water The pycnometer filled with airbubble free experimental liquids was kept in a transparentwalled constant temperature bath for 20 to 30min to attainthermal equilibrium The positions of the liquid levels in thetwo arms are recorded with the help of traveling microscopeAt least three to four measurements are performed fromwhich an average value of density of the experimental liquid isdetermined The estimated accuracy in the density measure-ment is 3 in 105 parts The ultrasonic speeds 119906 and densities120588 measured at 30815 K for the pure liquids used in this inves-tigation are compiled in Table 1 together with the literaturedata [11 14] available These results are in good agreementwith the reported data
3 Theory
Thermodynamic and acoustical parameters such as molarvolume (119881
119898) adiabatic compressibility (119896
119904) intermolecular
Table 1 Comparison of experimental values of density 120588 andultrasonic speed 119906 of pure liquids with the corresponding literaturevalues at 30815 K
Liquid 120588(kgmminus3) 119906(m sminus1)Presentwork Literature Present
work Literature
Cyclohexanone 93960 9396 [11] 136200 13620 [11]119899-Butanol 79650 7965 [14] 120930 12093 [14]119904119890119888-Butanol 79320 7932 [14] 117480 11748 [14]119905119890119903119905-Butanol 76840 7683 [14] 108600 10860 [14]
free length (119871119891) and acoustic impedance (119911) are evaluated
using the relations given below
119881119898=
119872eff120588
(1)
where119872eff is given by119872eff = (11990911198721 + 11990921198722) where1198721 and1198722are the molar masses of pure components and 120588 is the
density of the liquid mixtureThe speed of sound (119906) and the density of themedium (120588)
are related by using Newton and Laplace equation as
119896119904=
1
1205881199062
119871119891= 11987011989612
119904
(2)
Here119870 is the temperature dependent constant which is equalto119870 = (93875 + 0375119879) times 10minus8 where 119879 is absolute temper-ature Consider
119911 = 119906120588 (3)
In order to understand the nature of the molecular interac-tions between the components of the liquid mixtures it isof interest to discuss the same in terms of excess parametersrather than actual values Nonideal liquidmixtures show con-siderable deviation from linearity in their concentrations andthis has been interpreted to arise from the presence of strongorweak interactionsThedifference between the properties ofthe realmixtures (119884real) and those corresponding to idealmix-ture (119884ideal = sum119909119894119884119894) values namely excess properties (119884119864)such as excess molar volume (119881119864
119898) free length (119871119864
119891) acoustic
impedance (119911119864) and deviations in ultrasonic speed (Δ119906) iscomputed by the relation
119884119864
= 119884real minussum119909119894119884119894 (4)
where 119884119864 = 119881119864119898 119871119864
119891 119911119864 and Δ119906 119909
119894is the mole fraction and 119884
119894
is the value of the property of the 119894th component liquid ofmixture
The deviation in adiabatic compressibility (Δ119896119904) has been
calculated from the equation
Δ119896119904= 119896119904minus (Φ11198961199041+ Φ21198961199042) (5)
Journal of Applied Chemistry 3
where Φ1 Φ2 and 119896
1199041 1198961199042are the volume fractions and adi-
abatic compressibilities of components 1 and 2 respectivelySince 119896
119904is not additive on mole fraction but is additive on
volume fraction such values are calculated using volumefraction (Φ)
Φ119894=
119909119894119881119894
sum119909119894119881119894
(6)
The experimentally measured values of ultrasonic speed (119906)and density (120588) and calculated properties of molar vol-ume (119881
119898) adiabatic compressibility (119896
119904) intermolecular free
length (119871119891) and acoustic impedance (119911) and excessdeviation
thermodynamic properties 119881119864119898 119871119864119891 119911119864 Δ119906 and Δ119896
119904are
presented in Table 2 for all binary systems over the entirecomposition range of CH
The excessdeviation properties have been fitted to aRedlich-Kister type polynomial equation [16]
119884119864
= 11990911199092
119899
sum
119894=0
119860119894(1199092minus 1199091)119894
(7)
where119884119864 = 119881119864119898 119871119864
119891 119911119864
Δ119906 andΔ119896119904 1199091is the mole fraction of
the soluteThe values of Δ119896
119904have been fitted to Redlich-Kister type
polynomial with volume fraction instead of mole fraction inthe above polynomial and 119860
119894are the adjustable parameters
of the function and are determined using the least squaremethod In the present investigation ldquo119894rdquo values are taken from0 to 4 The corresponding standard deviation 120590(119884119864) wascalculated using the expression
120590 (119884119864
) =[
[
sum(119884119864
exp minus 119884119864
cal)2
(119898 minus 119899)
]
]
12
(8)
where ldquo119898rdquo is the total number of experimental points and ldquo119899rdquois the number of coefficients in (7) The calculated values ofthe coefficients119860
119894alongwith the standard deviations (120590) have
been presented in Table 3
4 Results and Discussion
Figure 1 represents the variation of excess molar volume (119881119864119898)
with mole fraction of CH The sign of 119881119864119898
depends uponthe contraction and expansion of volume of the liquids dueto mixing The factors that are mainly responsible for theexpansion of molar volume that is positive values of 119881119864
119898 are
the following (i) breaking of the structure of one or bothof the components in a solution that is the loss of dipolarassociation between themolecules (dispersion forces) (ii) H-bond rupture and stretching of self-associatedmolecules (likealcohols) (iii) the geometry of molecular structures whichdoes not favour the fitting of molecules of one componentinto void space of another molecule (iv) steric hindrance ofthe molecules The negative values of 119881119864
119898are due to the (i)
association of molecules through the formation of hydrogenbond that is strong specific interactions and (ii) accom-modation of molecules because of large differences in their
0
01
02
03
04
05
0 02 04 06 08 1
minus02
minus01
minus5
m3
mol
minus1)
VE m
(10
x1
Figure 1 Variation of excess molar volume 119881119864119898 with mole fraction
1199091 of cyclohexanone in (X) 119899-butanol(◼) sec-butanol(998771) and
tert-butanol at 30815 K and Tsierkezos et al [10] for cyclohex-anone + 1-butanol (dotted lines) at 29315 K
molar volumes In other words 119881119864119898arises due to the result
of physical chemical and structural contributions Physicalinteractions involving mainly nonspecific interactions suchas dispersion or weak forces (breaking of the liquid orderon mixing ie loss of dipolar association between themolecules) contribute to positive 119881119864
119898 The chemical or spe-
cific interactions such as complex formation and hydrogenbond formation between constituent molecules contributeto negative 119881119864
119898 The structural effects arise from interstitial
accommodation due to the difference in the molar volumesand free volumes between the liquid components on mixingcontributing to negative119881119864
119898[17]The variation of119881119864
119898is found
to be positive over the entire composition range in the presentinvestigation which indicates that weak forces exist Sri Lak-shmi et al [11] reported similar results in CHwith 119899-heptanol119899-octanol and iso-octanol at temperatures of 30315 3081531315 and 31815 KThe119881119864
119898data obtained by Tsierkezos et al
[10] for CH + 1-butanol binary system are negative at 29315 Kwhereas in our investigations they are found to be positivewhen performed at 30815 K Such behaviour may arise dueto the fact that as temperature increases the effective collisionbetween the component molecules increases Thus largernumber of free dipoles of component molecules may beavailable due to declusttering of molecules in the pure state
Thenature of interaction in binary liquids can be analysedby knowing their chemical and physical properties (physic-ochemical properties) Generally butanols are associatedthrough the hydrogen bonding as shown below and in thepure state they exhibit equilibrium between the monomerand multimer species Also they can be associated withany other groups having some degree of polar attractionsAs discussed earlier butanol exhibits strong intermolecularinteractions (H-bond) Alcohol size chain length and phys-ical properties (boiling point density hydrophobic propertyviscosity insolubility and refractive index) are importantparameters that must be taken into account to explain thebehaviour of the interactions (Scheme 2)
CH is a polar molecule because of the presence ofcarbonyl group (C=O) this is due to the fact that oxygenis more electronegative (Ominus) than carbon (C+) Thus they
4 Journal of Applied Chemistry
Table2Ex
perim
entalvalueso
fdensities120588ultrason
icspeeds119906m
olarvolume119881119898adiabaticcompressib
ility119896119904intermolecularfre
elength119871119891acoustic
impedance119911and
excessdeviatio
nprop
ertie
s119881119864 119898119871119864 119891119911119864
Δ119906andΔ119896119904fora
llbinary
syste
msw
ithmolefraction1199091ofcyclohexano
neat30815K
1199091
120588(kg
mminus3
)119906(msminus1
)119881119898(1
0minus5
m3molminus1
)119896119904(1
0minus10
Paminus1
)119871119891(1
0minus10
m)119911(1
06kg
mminus2
sminus1
)119881119864 119898(1
0minus5
m3molminus1
)Δ119896119904(1
0minus10
Paminus1
)119871119864 119891(1
0minus10
m)119911119864
(106
kgmminus2
sminus1
)Δ119906(msminus1
)CH
+119899-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09121
91391
133102
72125
89952
06281
12164
00977
03231
00107
minus00355
minus1755
08854
9072
0132296
72111
91843
06347
12002
01252
040
0800133
minus00432
minus2154
07211
87362
128396
71186
10204
806690
11217
02105
06763
00226
minus00697
minus3545
066
8786485
127447
70775
104903
06783
11022
02261
07151
00239
minus00726
minus3694
05232
84320
125214
69241
112327
07019
10558
02302
07516
00254
minus00730
minus3705
04752
83665
1246
98
68566
114565
07089
10433
02147
07367
00251
minus00703
minus3488
03231
81759
123068
66549
1215
5807302
10062
01776
06877
00232
minus00593
minus2795
02112
80599
122087
64872
126087
07437
09840
01311
05914
00197
minus004
60minus2068
01313
7999
1121519
63611
12861
07511
09720
00915
04550
00150
minus00328
minus1415
000
0079650
120930
61275
130345
07561
09632
000
00000
00000
00000
00000
CH+119904119890119888-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09212
91229
132922
7244
990
394
06297
12126
01060
03836
00126
minus00397
minus1802
08867
90208
131633
72474
93357
06399
11874
01397
05194
00171
minus00529
minus2446
07121
86217
126303
72207
106512
06835
10889
02705
09784
00316
minus00907
minus4507
06786
85620
125483
7204
2108709
06905
10744
02843
10245
00331
minus00935
minus4700
05123
8315
6122177
70717
118365
07205
10160
03018
10967
00354
minus00941
minus4893
046
8882613
121526
70273
120569
07272
1004
002967
10794
00349
minus00909
minus4729
03121
8092
6119
619
68217
1276
5107483
09680
02325
09202
00299
minus00724
minus3703
02797
80631
119309
67723
128921
07520
09620
02124
08684
00282
minus00672
minus3406
01112
79503
118057
65053
134011
07667
09386
00974
046
0400149
minus00320
minus1504
000
0079320
117480
63075
1352
9207703
09319
000
00000
00000
00000
00000
CH+119905119890119903119905-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09221
90829
131268
73361
92340
06364
11923
01562
04969
00150
minus00527
minus2781
08895
89642
129440
73779
96141
06494
11603
02106
06834
00207
minus00702
minus3710
07012
84030
121044
75179
117001
07164
10171
04235
15137
00457
minus01296
minus6909
06814
83551
120337
75205
119041
07226
10054
04337
15721
00475
minus01325
minus7069
05112
8017
9115277
74950
134939
07693
09243
04741
18707
00562
minus01378
minus7432
04777
79661
114465
74783
1376
6907771
09118
04703
18823
00566
minus01354
minus7319
03321
7791
2111524
73616
147714
08049
08689
040
9917
360
00519
minus01135
minus6241
02635
77360
110459
72878
1512
7508146
08545
03627
15506
004
63minus00973
minus5413
01323
7677
8109036
70894
155581
08261
08372
02150
09556
00285
minus00562
minus3215
000
0076840
108600
68232
155954
08271
08345
000
00000
00000
00000
00000
Journal of Applied Chemistry 5
Table 3 Coefficients 119860119894of Redlich-Kister type polynomial equation (7) and the corresponding standard deviations 120590 of all the systems at
30815 K
1198600
1198601
1198602
1198603
1198604
120590
CH + 119899-butanol119881119864
119898(10minus5m3 molminus1) 247625 minus57880 36945 minus31381 minus08351 00019
Δ119896119904(10minus10 Paminus1) 00183 minus00020 00075 00029 minus00004 00091
119871119864
119891(10minus10m) 08201 minus01460 02529 00638 01066 00009
119911119864(106 kgmminus2 sminus1) minus02875 00836 minus01081 00006 minus00202 00002Δ119906(msminus1) minus140 058 minus031 minus003 minus018 00024
CH + 119904119890119888-butanol119881119864
119898(10minus5m3 molminus1) 275896 minus9594 42809 minus22460 minus07780 00018
Δ119896119904(10minus10 Paminus1) 00267 minus0001 00001 00033 00034 00001
119871119864
119891(10minus10m) 11507 minus01810 00576 01082 00684 00011
119911119864(106 kgmminus2 sminus1) minus03733 01252 minus00791 00092 minus00110 00001Δ119906(msminus1) minus194 059 minus004 minus001 minus004 00006
CH + 119905119890119903119905-butanol119881119864
119898(10minus5m3 molminus1) 364535 minus123900 minus06780 01003 minus02750 00009
Δ119896119904(10minus10 Paminus1) 00428 00120 00024 00019 00011 00001
119871119864
119891(10minus10m) 18117 01253 01393 00862 minus00290 00006
119911119864(106 kgmminus2 sminus1) minus05484 01374 minus00850 00123 minus00032 00001Δ119906(msminus1) minus296 062 minus054 001 minus001 00001
R R R
Structure of alcoholOndashHmiddot middot middotOndashH middot middot middot middot middot middot OndashH
Scheme 2
Resonance structure
middot middot middot
R R
R
C OOminus H+
Scheme 3
cause strong dipole-dipole interactions in chemical reactionsMoreover CH lacks hydroxyl groups so it is incapable ofcreating intermolecular hydrogen bonds In CH + isomersof butanol binary systems the negatively charged oxygen(Ominus) in CH tries to drag the positively charged H+ whichwere bounded in very strong intermolecular interactions ofbutanol (Scheme 3) An equilibrium stage is reached whererupturing of hydrogen bond or reduction inH-bond strengthof butanol or breaking of the structure of one or both ofthe components in a solution that is the loss of dipolarassociation between the molecules (dispersion forces) [18]will be favourable leading to weak interactions This causesincrease in volume of binary liquid and explains the observedpositive values 119881119864
119898in the systems
Kiyohara and Benson [19] have suggested that Δ119896119904is
the resultant of several opposing effects Negative values ofΔ119896119904contribute to charge transfer dipole-induced dipole and
00
04
08
12
16
20
0 02 04 06 08 1
minus10
Paminus1)
x1
Δks
(10
Figure 2 Variation of deviation in adiabatic compressibility Δ119896119904
with mole fraction 1199091 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
dipole-dipole interactions interstitial accommodation andbreaking up of the alcohol structures leads to positive valuesof Δ119896119904 From Figure 2 the observed positive values of Δ119896
119904for
binary mixtures of CHwith 119899-butanol 119904119890119888-butanol and 119905119890119903119905-butanol are due to declustering of alcohols in the presence ofCH The positive deviation in Δ119896
119904for the binary systems fol-
lows the order CH+ 119905119890119903119905-butanolgt 119904119890119888-butanolgt 119899-butanolFigure 3 represents the variation of119871119864
119891withmole fraction (119909
1)
of CH The observed values of 119871119864119891are positive According
to Fort and Moore [20] positive 119871119864119891should be attributed to
the dispersive forces As mentioned earlier positive values ofΔ119896119904and 119871119864
119891are mainly attributed to weak forces between the
component molecules in the mixture [21]
6 Journal of Applied Chemistry
0
001
002
003
004
005
006
0 02 04 06 08 1
minus10
m)
x1
LE f(10
Figure 3 Variation of excess free length 119871119864119891 with mole fraction 119909
1
of cyclohexanone in (X) 119899-butanol(◼) sec-butanol(998771) and tert-butanol at 30815 K
00 02 04 06 08 1
minus004
minus008
minus012
minus016
6kg
mminus2
sminus1)
x1
ZE(10
Figure 4 Variation of excess acoustic impedance 119911119864 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
The variations of excess acoustic impedance (119911119864) anddeviation in ultrasonic speed (Δ119906) have been presented inFigures 4 and 5 respectively From Figure 4 it has beenobserved that the values of 119911119864 are negative over the entiremole fraction range indicating the decreasing strength ofinteractions between component molecules of the mixtureAccording to Gowrisankar et al [22] the negative valuesfor Δ119906 indicate the decrease in the strength of interactionbetween the molecules and the negative deviations in Δ119906from linear dependence suggest the presence of weak inter-action between the component molecules These deviationexcess properties further support the conclusions drawn from119881119864
119898 119871119864119891 and Δ119896
119904
The existing molecular interactions in the systems arewell reflected in the properties of partial molar volumes Thepartial molar volumes 119881
1198981of component 1 (CH) and 119881
1198982
of component 2 (isomers of butanol) in the mixtures overthe entire composition range have been calculated by usingthe following relations
1198811198981= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
00 02 04 06 08 1
minus20
minus40
minus60
minus80
x1
Δu
(msminus
1)
Figure 5 Variation of deviation in ultrasonic speed Δ119906 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
1198811198982= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(9)
where 119881lowast1and 119881lowast
2are the molar volumes of the pure com-
ponents of CH and butanols respectively The derivates inthe above equations are obtained by differentiating Redlich-Kister equation (7) which leads to the following equations for1198811198981
and 1198811198982
1198811198981= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(10)
1198811198982= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
+ 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(11)
using the above equations 1198811198641198981
1198811198641198982
have been calculatedusing
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(12)
The pertinent values of 1198811198981
and 1198811198982
are furnished inTable 4 From this table the values of 119881
1198981and 119881
1198982for
both the components in the mixtures are greater than theirrespective molar volumes in the pure state that is an expan-sion of volume takes place on mixing alcohols with ketoneThese results also support the observed positive values of119881119864
119898in all the binary systems Figures 6 and 7 represent the
variation of excess partial molar volumes of 1198811198641198981
(CH) 1198811198641198982
(isomers of butanol) in the binary mixtures Examinationof these figures reveals that dispersion forces exist betweenthe unlike molecules These figures support the conclusionsdrawn from119881119864
119898The partial molar volumes and excess partial
Journal of Applied Chemistry 7
Table 4 Partial molar volumes of CH (1198811198981
10minus5m3 molminus1) and butanols (1198811198982
10minus5m3 molminus1) of all the binary systems with mole fraction(1199091) of CH at 30815 K
CH + 119899-butanol CH + 119904119890119888-butanol CH + 119905119890119903119905-butanol1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
10000 7210 42676 10000 7210 49234 10000 7210 5461209121 7699 32512 09212 7681 38378 09221 7606 4459008854 7999 30035 08867 8130 34445 08895 7997 4078807211 10600 19303 07121 11586 20460 07012 12366 2341306687 11554 17041 06786 12354 18636 06814 12989 2202305232 14365 12385 05123 16219 12221 05112 19004 1308704752 15378 11198 04688 17234 11058 04777 20247 1189303231 19092 8232 03121 20995 8043 03321 25389 841602112 22264 6843 02797 21794 7619 02635 27459 756201313 24403 6314 01112 25586 6406 01323 30211 687400000 25905 6128 00000 26462 6307 00000 30421 6823
0
10
20
30
40
50
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m2
(10
Figure 6 Variation of excess partial molar volume 1198811198641198982
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
molar volumes ofCHand isomers of butanols in all the binaryliquid mixtures at infinite dilution 119881infin
1198981 119881infin1198982
119881119864infin1198981
and119881
119864infin
1198982 respectively were obtained by putting 119909 = 0 in (10)
and 119909 = 1 in (11) Consider
119881
119864infin
1198981= 1198600+ 1198601+ 1198602+ 1198603+ sdot sdot sdot = 119881
infin
1198981minus 119881lowast
1
119881
119864infin
1198982= 1198600minus 1198601+ 1198602minus 1198603+ sdot sdot sdot = 119881
infin
1198982minus 119881lowast
2
(13)
The pertinent values of 119881infin1198981
119881infin1198982
119881119864infin1198981
and 119881119864infin1198982
arereported in Table 5 From this table it is seen that these valuesare positive from which we conclude that weak interactionsexist among the unlike molecules of the liquid mixtures
FT-IR spectra of pure CH butanols and binary mixturesof CH with butanols at equal concentrations are depicted inFigures 8 9 and 10 According to Karunakar and Srinivas[23] the intensity of an absorption in the IR spectrum isrelated to the change in dipole moment that occurs duringthe vibration Consequently vibrations that produce a largechange in dipole moment (eg C=O stretch) result in amore intense absorption than those that result in a relativelymodest change in dipole (eg C=C) Vibrations that do notresult in a change in dipole moment (eg a symmetrical
0
5
10
15
20
25
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m1
(10
Figure 7 Variation of excess partial molar volume 1198811198641198981
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
n-ButanolCH
Wave number (cmminus1)
CH + n-Butanol
Figure 8 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and 119899-butanol in the ratio 5 5 (green) andpure 119899-butanol (blue)
8 Journal of Applied Chemistry
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
sec-ButanolCH
Wave number (cmminus1)
CH + sec-Butanol
Figure 9 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and sec-butanol in the ratio 5 5 (green) andpure sec-butanol (blue)
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
tert-ButanolCH
Wave number (cmminus1)
CH + tert-Butanol
Figure 10 Fourier transform infrared spectra of pure cyclohex-anone (red) cyclohexanone and tert-butanol in the ratio 5 5(green) and pure tert-butanol (blue)
alkyne CequivC stretch) will show little or no absorption for thisvibration In the present FT-IR spectra liquid mixture showsvery small variations in the intensity of the respective bondsthat is dipole moment and hence it supports that weakinteractions take place between the components of liquidmolecules
Theoretical evaluation of ultrasonic speed in binary liquidmixtures and its correlation to study molecular interactionhas been successfully done in recent years Ultrasonic speedsin liquid mixtures have been calculated and compared with
Table 5 Partial molar volumes (119881infin1198981
119881infin1198982
) and excess partial molarvolumes (119881119864infin
1198981 119881119864infin1198982
) of the components at infinite dilution for allthe systems at 30815 K
System 119881
infin
1198981119881
infin
1198982119881
119864infin
1198981119881
119864infin
1198982
(10minus5m3 molminus1)CH + 119899-butanol 25519 43758 18696 36548CH + 119904119890119888-butanol 25561 509205 19253 42933CH + 119905119890119903119905-butanol 30034 55000 23211 47790
experimental values using various theories Such an evalua-tion offers a simple method to investigate molecular interac-tions besides verifying the applicability of various theories toliquid mixtures
Nomoto [24] established the following relation for soundspeed (119880
119873) based on the assumption of the linearity of the
molecular sound speed and the additivity of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(14)
where 119877119894is molar sound speed and 119881
119894is molar volume
van Dael and Vangeel [25] obtained the ideal mixturerelation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(15)
Baluja and Parsania [26] have given impedance relationon the basis of force of resistance for sound speed by theinteracting molecules
119880imp =sum119909119894119885119894
sum119909119894120588119894
(16)
Raorsquos (specific sound speed) [27] relation is given by
119880119877= (sum119909
119894119903119894120588)
3
(17)
where 119903119894= 11990613
119894120588119894is Raorsquos specific sound speed of 119894th com-
ponent of the mixturePercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906exp 119905
] (18)
Table 6 shows the values of ultrasonic speed computed byvarious theories along with their percentage error for all thesystems The variations between the evaluated and experi-mental values may be due to interactions occurring betweenthe hetero molecules of the binaries From the observedvalues of all three systems there is a good agreementbetween theoretical and experimental values through vanDeal andVangeel relation It can be seen fromTable 6 that thetheoretical values of ultrasonic speed calculated by using var-ious theories show deviation from experimental values Thelimitations and approximation incorporated in these theories
Journal of Applied Chemistry 9
Table 6Theoretical values of ultrasonic speed from various equations and percentage error withmole fraction1199091of CH for all binary systems
at 30815 K
1199091
119880119873
119880119881
119880Imp 119880119877
119880119873
119880119881
119880Imp 119880119877
CH + 119899-butanol10000 136200 136200 136200 136200 000 000 000 00009121 135001 134547 135043 129806 143 109 146 24808854 134632 134060 134687 128317 177 133 181 30107211 132309 131199 132427 122196 305 218 314 48306687 131549 130334 131681 120973 322 227 332 50805232 129386 128042 129542 118502 333 226 346 53604752 128656 127319 128814 117871 317 210 330 54803231 126283 125129 126429 116393 261 168 273 54202112 124478 123609 124594 116166 196 125 205 48501313 123158 122567 123239 116883 135 086 142 38200000 120930 120930 120930 120930 000 000 000 000
CH + 119904119890119888-butanol10000 136200 136200 136200 136200 000 000 000 00009212 134836 134412 134936 128464 144 112 152 33508867 134234 133650 134375 125830 198 153 208 44107121 131130 129973 131435 117255 382 291 406 71606786 130524 129300 130852 116263 402 304 428 73505123 127465 126097 127860 113158 433 321 465 73804688 126650 125296 127049 112705 422 310 455 72603121 123666 122524 124027 112004 338 243 369 63702797 123039 121972 123381 112051 313 223 341 60801112 119722 119210 119901 113885 141 098 156 35300000 117480 117480 117480 117480 000 000 000 000
CH + 119905119890119903119905-butanol10000 136200 136200 136200 136200 000 000 000 00009221 134013 133538 134413 126923 209 173 240 33108895 133099 132456 133651 123600 283 233 325 45107012 127840 126544 129065 109588 561 454 663 94606814 127289 125953 128564 108550 578 467 684 98005112 122570 121104 124087 102359 633 506 764 112104777 121645 120195 123170 101661 627 501 761 111903321 117638 116400 119036 100406 548 437 674 99702635 115760 114696 117000 100794 480 384 592 87501323 112183 111575 112939 103339 289 233 358 52300000 108600 108600 108600 108600 000 000 000 000
are responsible for the deviations of theoretical values fromexperimental values Nomotorsquos theory proposes that the vol-ume does not change upon mixingTherefore no interactionbetween the components of liquid mixtures has been takeninto account Similarly the assumption for the formation ofideal mixing relation is that the ratios of specific heats of idealmixtures and the volumes are also equal Again no molecularinteractions are taken into account But upon mixing inter-actions between the molecules occur because of the presenceof various types of forces such as dispersion forces chargetransfer and hydrogen bonding dipole-dipole and dipole-induced dipole interactions Thus the observed deviationof theoretical values of speed from the experimental values
shows that the molecular interactions are taking placebetween the CH and isomers of butanol molecules Thedeviations of experimental values and values calculated fromimpedance relation and Raorsquos relation imply nonadditivity ofacoustic impedance and Raorsquos speed in the liquid mixturesAmong all the empirical theories van Dael and Vangeelsrelation gives better estimate of experimental values of soundspeed in all the systems In the present binary systems thedifference between experimental and theoretical speeds isgreater where themole fraction of CH varies in the region 03to 06 Hence it can be qualitatively inferred that the strengthof interaction in the binary mixtures is more in this range ofcomposition of CH with isomers of butanol liquid system
10 Journal of Applied Chemistry
5 Conclusion
(i) Ultrasonic speeds 119906 and densities 120588 of mixtures ofcyclohexanone with 119899-butanol or sec-butanol or tert-butanol over the entire composition range have beenmeasured at 119879 = 30815K
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119911119864 and Δ119906 are calculated
from experimental data of density and ultrasonicspeed The excess and deviation properties have beenfitted to Redlich-Kister type polynomial and corre-sponding standard deviations have been evaluatedThe observed positive values of 119881119864
119898 Δ119896119904 and 119871119864
119891and
negative values of 119911119864 Δ119906 for all the liquid mixturesstudied clearly indicate the presence of weak inter-actions such as rupturing of hydrogen bond or reduc-tion in H-bond strength of butanol or breaking ofthe structure of one or both of the components in asolution
(iii) The deviationexcess properties have been fitted toRedlich-Kister type polynomial and the correspond-ing standard deviations have been calculated
(iv) The calculated values of partial molar volumes havealso been examined The observed higher partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate weak interactions present in the systems
(v) The strength of interaction in themixtures follows theorder CH + tert-butanol gt sec-butanol gt 119899-butanol
(vi) FT-IR spectra for the present binary mixture alsosupport the conclusions drawn from the 119881119864
119898 119871119864119891 Δ119896119904
Δ119906 and 119911119864(vii) Further theoretical values of sound speed in the mix-
tures have been evaluated using various theories andhave been compared with experimental sound speedsto verify the applicability of such theories to the sys-tems studied
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
One of the authors SkMdNayeem is thankful to UGC NewDelhi Government of India for the financial grants towardsMRP (MRP-467114C (SERO-UGC))
References
[1] T B Thoe D K Aspinwall and M L H Wise ldquoReview onultrasonic machiningrdquo International Journal of Machine Toolsand Manufacture vol 38 no 4 pp 239ndash255 1998
[2] G Thomas Chemistry for Pharmacy and the Life SciencesPrentice Hall London UK 1996
[3] A M Ababneh C C Large and S Georghiou ldquoSolvation ofnucleosides in aqueous mixtures of organic solvents relevanceto dna open basepairsrdquo Biophysical Journal vol 85 no 2 pp1111ndash1127 2003
[4] R E Treybal Mass Transfer Operations McGraw Hill Singa-pore 3rd edition 1981
[5] 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 atT = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[6] PGnanaKumari PVenkatesuMV PrabhakaraRaoM-J Leeand H-M Lin ldquoExcess molar volumes and ultrasonic studiesof 119873-methyl-2-pyrrolidone with ketones at 119879 = 30315 Krdquo TheJournal of ChemicalThermodynamics vol 41 no 5 pp 586ndash5902009
[7] M Sreenivasulu and P R Naidu ldquoExcess volumes and adiabaticcompressibility of binary mixtures of butyl amine and cyclicketonesrdquo Australian Journal of Chemistry vol 32 no 8 pp1649ndash1652 1979
[8] K Rajagopal and S Chenthilnath ldquoExcess thermodynamicstudies of binary liquid mixtures of 2-methyl-2-propanol withketonesrdquo Indian Journal of Pure amp Applied Physics vol 48 no5 pp 326ndash333 2010
[9] R K Bachu M K Patwari S Boodida and S Nallani ldquoVol-umetric and transport properties of binary liquid mixtures ofaliphatic ketones with phenylacetonitrile at T = 30815 Krdquo Jour-nal of Chemical amp Engineering Data vol 53 no 10 pp 2403ndash2407 2008
[10] N G Tsierkezos I E Molinou and A C Filippou ldquoThermo-dynamic properties of binary mixtures of cyclohexanone with119899-alkanols (C
1-C5) at 29315 Krdquo Journal of Solution Chemistry
vol 34 no 12 pp 1371ndash1386 2005[11] M Sri Lakshmi R R Raju C Rambabu G V R Rao and
K Narendra ldquoStudy of molecular interactions in binary liquidmixtures containing higher alcohols at different temperaturesrdquoResearchampReviews Journal of Chemistry vol 2 no 1 pp 12ndash242013
[12] A I Vogel Text Book of Practical Organic Chemistry LongmanLondon UK 5th edition 1989
[13] J A Riddick W Bunger and T K Sakano Techniques of Chem-istry Organic Solvents Physical Properties andMethods of Purifi-cation Wiley Interscience New York NY USA 4th edition1987
[14] R K Bachu andM K Patwari ldquoDensities viscosities and speedof sound of binary mixtures of phenylacetonitrile with somealiphatic alcohols at 30815 Krdquo Indian Journal of Chemistry Avol 47 no 7 pp 1026ndash1031 2008
[15] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Journal of Physical Chemistry vol 29 pp 130ndash1371925
[16] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification solutionsrdquoIndustrial and Engineering Chemistry vol 40 no 2 pp 345ndash348 1948
[17] R Vijaya Kumar S Viswanathan and M Anand Rao ldquoExcessvolumes speeds of sound and isentropic compressibilitiesof 2-propyn-1-ol + 12-dichloroethane +111-trichloroe thane+1122-tetrachloroethane and +trichloroethylene at 30315Krdquo
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Quantum Chemistry
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CatalystsJournal of
2 Journal of Applied Chemistry
RR
RR
C CO O+ minus
Resonance structure
hArr∙∙
∙∙
∙∙
∙∙
∙∙
Scheme 1
cyclohexanone with 119899-heptanol 119899-octanol and isooctanolat temperatures 30315 30815 31315 and 31815 K overthe entire range of composition Keeping these importantaspects in mind the present study deals with ultrasonic andthermodynamic study of cyclohexanone (CH) with the iso-mers of butanol (119899-butanol sec-butanol and tert-butanol) at30815 K The liquids under investigation have been chosenon the basis of their multifold applications
2 Experimental Section
High purity analytical reagent (AR) grade compounds ofcyclohexanone (mass fraction purity gt 99) and 119899-butanolsec-butanol and tert-butanol (mass fraction purity gt 995)obtained from S D Fine Chemicals are used in the presentstudy The chemicals are further purified by standard meth-ods mentioned in [12 13]The weighing of solutions has beenmade usingMETTLER TOLEDO (Switzerlandmake) ABB5-SFACT digital balance with an accuracy of plusmn001mg Theuncertainty in themole fraction is 10minus4The ultrasonic speedsof pure liquids and liquid mixtures have been measuredusing an ultrasonic interferometer (Mittal type Model F-82)working at 2MHz fixed frequencywith an accuracy ofplusmn02The 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 of pure liquids and their mixtures have beendetermined by using a 5 cm3 two-stem double-walled Parkeramp Parker type pycnometer [15]This pycnometer is calibratedwith triply distilled water The pycnometer filled with airbubble free experimental liquids was kept in a transparentwalled constant temperature bath for 20 to 30min to attainthermal equilibrium The positions of the liquid levels in thetwo arms are recorded with the help of traveling microscopeAt least three to four measurements are performed fromwhich an average value of density of the experimental liquid isdetermined The estimated accuracy in the density measure-ment is 3 in 105 parts The ultrasonic speeds 119906 and densities120588 measured at 30815 K for the pure liquids used in this inves-tigation are compiled in Table 1 together with the literaturedata [11 14] available These results are in good agreementwith the reported data
3 Theory
Thermodynamic and acoustical parameters such as molarvolume (119881
119898) adiabatic compressibility (119896
119904) intermolecular
Table 1 Comparison of experimental values of density 120588 andultrasonic speed 119906 of pure liquids with the corresponding literaturevalues at 30815 K
Liquid 120588(kgmminus3) 119906(m sminus1)Presentwork Literature Present
work Literature
Cyclohexanone 93960 9396 [11] 136200 13620 [11]119899-Butanol 79650 7965 [14] 120930 12093 [14]119904119890119888-Butanol 79320 7932 [14] 117480 11748 [14]119905119890119903119905-Butanol 76840 7683 [14] 108600 10860 [14]
free length (119871119891) and acoustic impedance (119911) are evaluated
using the relations given below
119881119898=
119872eff120588
(1)
where119872eff is given by119872eff = (11990911198721 + 11990921198722) where1198721 and1198722are the molar masses of pure components and 120588 is the
density of the liquid mixtureThe speed of sound (119906) and the density of themedium (120588)
are related by using Newton and Laplace equation as
119896119904=
1
1205881199062
119871119891= 11987011989612
119904
(2)
Here119870 is the temperature dependent constant which is equalto119870 = (93875 + 0375119879) times 10minus8 where 119879 is absolute temper-ature Consider
119911 = 119906120588 (3)
In order to understand the nature of the molecular interac-tions between the components of the liquid mixtures it isof interest to discuss the same in terms of excess parametersrather than actual values Nonideal liquidmixtures show con-siderable deviation from linearity in their concentrations andthis has been interpreted to arise from the presence of strongorweak interactionsThedifference between the properties ofthe realmixtures (119884real) and those corresponding to idealmix-ture (119884ideal = sum119909119894119884119894) values namely excess properties (119884119864)such as excess molar volume (119881119864
119898) free length (119871119864
119891) acoustic
impedance (119911119864) and deviations in ultrasonic speed (Δ119906) iscomputed by the relation
119884119864
= 119884real minussum119909119894119884119894 (4)
where 119884119864 = 119881119864119898 119871119864
119891 119911119864 and Δ119906 119909
119894is the mole fraction and 119884
119894
is the value of the property of the 119894th component liquid ofmixture
The deviation in adiabatic compressibility (Δ119896119904) has been
calculated from the equation
Δ119896119904= 119896119904minus (Φ11198961199041+ Φ21198961199042) (5)
Journal of Applied Chemistry 3
where Φ1 Φ2 and 119896
1199041 1198961199042are the volume fractions and adi-
abatic compressibilities of components 1 and 2 respectivelySince 119896
119904is not additive on mole fraction but is additive on
volume fraction such values are calculated using volumefraction (Φ)
Φ119894=
119909119894119881119894
sum119909119894119881119894
(6)
The experimentally measured values of ultrasonic speed (119906)and density (120588) and calculated properties of molar vol-ume (119881
119898) adiabatic compressibility (119896
119904) intermolecular free
length (119871119891) and acoustic impedance (119911) and excessdeviation
thermodynamic properties 119881119864119898 119871119864119891 119911119864 Δ119906 and Δ119896
119904are
presented in Table 2 for all binary systems over the entirecomposition range of CH
The excessdeviation properties have been fitted to aRedlich-Kister type polynomial equation [16]
119884119864
= 11990911199092
119899
sum
119894=0
119860119894(1199092minus 1199091)119894
(7)
where119884119864 = 119881119864119898 119871119864
119891 119911119864
Δ119906 andΔ119896119904 1199091is the mole fraction of
the soluteThe values of Δ119896
119904have been fitted to Redlich-Kister type
polynomial with volume fraction instead of mole fraction inthe above polynomial and 119860
119894are the adjustable parameters
of the function and are determined using the least squaremethod In the present investigation ldquo119894rdquo values are taken from0 to 4 The corresponding standard deviation 120590(119884119864) wascalculated using the expression
120590 (119884119864
) =[
[
sum(119884119864
exp minus 119884119864
cal)2
(119898 minus 119899)
]
]
12
(8)
where ldquo119898rdquo is the total number of experimental points and ldquo119899rdquois the number of coefficients in (7) The calculated values ofthe coefficients119860
119894alongwith the standard deviations (120590) have
been presented in Table 3
4 Results and Discussion
Figure 1 represents the variation of excess molar volume (119881119864119898)
with mole fraction of CH The sign of 119881119864119898
depends uponthe contraction and expansion of volume of the liquids dueto mixing The factors that are mainly responsible for theexpansion of molar volume that is positive values of 119881119864
119898 are
the following (i) breaking of the structure of one or bothof the components in a solution that is the loss of dipolarassociation between themolecules (dispersion forces) (ii) H-bond rupture and stretching of self-associatedmolecules (likealcohols) (iii) the geometry of molecular structures whichdoes not favour the fitting of molecules of one componentinto void space of another molecule (iv) steric hindrance ofthe molecules The negative values of 119881119864
119898are due to the (i)
association of molecules through the formation of hydrogenbond that is strong specific interactions and (ii) accom-modation of molecules because of large differences in their
0
01
02
03
04
05
0 02 04 06 08 1
minus02
minus01
minus5
m3
mol
minus1)
VE m
(10
x1
Figure 1 Variation of excess molar volume 119881119864119898 with mole fraction
1199091 of cyclohexanone in (X) 119899-butanol(◼) sec-butanol(998771) and
tert-butanol at 30815 K and Tsierkezos et al [10] for cyclohex-anone + 1-butanol (dotted lines) at 29315 K
molar volumes In other words 119881119864119898arises due to the result
of physical chemical and structural contributions Physicalinteractions involving mainly nonspecific interactions suchas dispersion or weak forces (breaking of the liquid orderon mixing ie loss of dipolar association between themolecules) contribute to positive 119881119864
119898 The chemical or spe-
cific interactions such as complex formation and hydrogenbond formation between constituent molecules contributeto negative 119881119864
119898 The structural effects arise from interstitial
accommodation due to the difference in the molar volumesand free volumes between the liquid components on mixingcontributing to negative119881119864
119898[17]The variation of119881119864
119898is found
to be positive over the entire composition range in the presentinvestigation which indicates that weak forces exist Sri Lak-shmi et al [11] reported similar results in CHwith 119899-heptanol119899-octanol and iso-octanol at temperatures of 30315 3081531315 and 31815 KThe119881119864
119898data obtained by Tsierkezos et al
[10] for CH + 1-butanol binary system are negative at 29315 Kwhereas in our investigations they are found to be positivewhen performed at 30815 K Such behaviour may arise dueto the fact that as temperature increases the effective collisionbetween the component molecules increases Thus largernumber of free dipoles of component molecules may beavailable due to declusttering of molecules in the pure state
Thenature of interaction in binary liquids can be analysedby knowing their chemical and physical properties (physic-ochemical properties) Generally butanols are associatedthrough the hydrogen bonding as shown below and in thepure state they exhibit equilibrium between the monomerand multimer species Also they can be associated withany other groups having some degree of polar attractionsAs discussed earlier butanol exhibits strong intermolecularinteractions (H-bond) Alcohol size chain length and phys-ical properties (boiling point density hydrophobic propertyviscosity insolubility and refractive index) are importantparameters that must be taken into account to explain thebehaviour of the interactions (Scheme 2)
CH is a polar molecule because of the presence ofcarbonyl group (C=O) this is due to the fact that oxygenis more electronegative (Ominus) than carbon (C+) Thus they
4 Journal of Applied Chemistry
Table2Ex
perim
entalvalueso
fdensities120588ultrason
icspeeds119906m
olarvolume119881119898adiabaticcompressib
ility119896119904intermolecularfre
elength119871119891acoustic
impedance119911and
excessdeviatio
nprop
ertie
s119881119864 119898119871119864 119891119911119864
Δ119906andΔ119896119904fora
llbinary
syste
msw
ithmolefraction1199091ofcyclohexano
neat30815K
1199091
120588(kg
mminus3
)119906(msminus1
)119881119898(1
0minus5
m3molminus1
)119896119904(1
0minus10
Paminus1
)119871119891(1
0minus10
m)119911(1
06kg
mminus2
sminus1
)119881119864 119898(1
0minus5
m3molminus1
)Δ119896119904(1
0minus10
Paminus1
)119871119864 119891(1
0minus10
m)119911119864
(106
kgmminus2
sminus1
)Δ119906(msminus1
)CH
+119899-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09121
91391
133102
72125
89952
06281
12164
00977
03231
00107
minus00355
minus1755
08854
9072
0132296
72111
91843
06347
12002
01252
040
0800133
minus00432
minus2154
07211
87362
128396
71186
10204
806690
11217
02105
06763
00226
minus00697
minus3545
066
8786485
127447
70775
104903
06783
11022
02261
07151
00239
minus00726
minus3694
05232
84320
125214
69241
112327
07019
10558
02302
07516
00254
minus00730
minus3705
04752
83665
1246
98
68566
114565
07089
10433
02147
07367
00251
minus00703
minus3488
03231
81759
123068
66549
1215
5807302
10062
01776
06877
00232
minus00593
minus2795
02112
80599
122087
64872
126087
07437
09840
01311
05914
00197
minus004
60minus2068
01313
7999
1121519
63611
12861
07511
09720
00915
04550
00150
minus00328
minus1415
000
0079650
120930
61275
130345
07561
09632
000
00000
00000
00000
00000
CH+119904119890119888-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09212
91229
132922
7244
990
394
06297
12126
01060
03836
00126
minus00397
minus1802
08867
90208
131633
72474
93357
06399
11874
01397
05194
00171
minus00529
minus2446
07121
86217
126303
72207
106512
06835
10889
02705
09784
00316
minus00907
minus4507
06786
85620
125483
7204
2108709
06905
10744
02843
10245
00331
minus00935
minus4700
05123
8315
6122177
70717
118365
07205
10160
03018
10967
00354
minus00941
minus4893
046
8882613
121526
70273
120569
07272
1004
002967
10794
00349
minus00909
minus4729
03121
8092
6119
619
68217
1276
5107483
09680
02325
09202
00299
minus00724
minus3703
02797
80631
119309
67723
128921
07520
09620
02124
08684
00282
minus00672
minus3406
01112
79503
118057
65053
134011
07667
09386
00974
046
0400149
minus00320
minus1504
000
0079320
117480
63075
1352
9207703
09319
000
00000
00000
00000
00000
CH+119905119890119903119905-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09221
90829
131268
73361
92340
06364
11923
01562
04969
00150
minus00527
minus2781
08895
89642
129440
73779
96141
06494
11603
02106
06834
00207
minus00702
minus3710
07012
84030
121044
75179
117001
07164
10171
04235
15137
00457
minus01296
minus6909
06814
83551
120337
75205
119041
07226
10054
04337
15721
00475
minus01325
minus7069
05112
8017
9115277
74950
134939
07693
09243
04741
18707
00562
minus01378
minus7432
04777
79661
114465
74783
1376
6907771
09118
04703
18823
00566
minus01354
minus7319
03321
7791
2111524
73616
147714
08049
08689
040
9917
360
00519
minus01135
minus6241
02635
77360
110459
72878
1512
7508146
08545
03627
15506
004
63minus00973
minus5413
01323
7677
8109036
70894
155581
08261
08372
02150
09556
00285
minus00562
minus3215
000
0076840
108600
68232
155954
08271
08345
000
00000
00000
00000
00000
Journal of Applied Chemistry 5
Table 3 Coefficients 119860119894of Redlich-Kister type polynomial equation (7) and the corresponding standard deviations 120590 of all the systems at
30815 K
1198600
1198601
1198602
1198603
1198604
120590
CH + 119899-butanol119881119864
119898(10minus5m3 molminus1) 247625 minus57880 36945 minus31381 minus08351 00019
Δ119896119904(10minus10 Paminus1) 00183 minus00020 00075 00029 minus00004 00091
119871119864
119891(10minus10m) 08201 minus01460 02529 00638 01066 00009
119911119864(106 kgmminus2 sminus1) minus02875 00836 minus01081 00006 minus00202 00002Δ119906(msminus1) minus140 058 minus031 minus003 minus018 00024
CH + 119904119890119888-butanol119881119864
119898(10minus5m3 molminus1) 275896 minus9594 42809 minus22460 minus07780 00018
Δ119896119904(10minus10 Paminus1) 00267 minus0001 00001 00033 00034 00001
119871119864
119891(10minus10m) 11507 minus01810 00576 01082 00684 00011
119911119864(106 kgmminus2 sminus1) minus03733 01252 minus00791 00092 minus00110 00001Δ119906(msminus1) minus194 059 minus004 minus001 minus004 00006
CH + 119905119890119903119905-butanol119881119864
119898(10minus5m3 molminus1) 364535 minus123900 minus06780 01003 minus02750 00009
Δ119896119904(10minus10 Paminus1) 00428 00120 00024 00019 00011 00001
119871119864
119891(10minus10m) 18117 01253 01393 00862 minus00290 00006
119911119864(106 kgmminus2 sminus1) minus05484 01374 minus00850 00123 minus00032 00001Δ119906(msminus1) minus296 062 minus054 001 minus001 00001
R R R
Structure of alcoholOndashHmiddot middot middotOndashH middot middot middot middot middot middot OndashH
Scheme 2
Resonance structure
middot middot middot
R R
R
C OOminus H+
Scheme 3
cause strong dipole-dipole interactions in chemical reactionsMoreover CH lacks hydroxyl groups so it is incapable ofcreating intermolecular hydrogen bonds In CH + isomersof butanol binary systems the negatively charged oxygen(Ominus) in CH tries to drag the positively charged H+ whichwere bounded in very strong intermolecular interactions ofbutanol (Scheme 3) An equilibrium stage is reached whererupturing of hydrogen bond or reduction inH-bond strengthof butanol or breaking of the structure of one or both ofthe components in a solution that is the loss of dipolarassociation between the molecules (dispersion forces) [18]will be favourable leading to weak interactions This causesincrease in volume of binary liquid and explains the observedpositive values 119881119864
119898in the systems
Kiyohara and Benson [19] have suggested that Δ119896119904is
the resultant of several opposing effects Negative values ofΔ119896119904contribute to charge transfer dipole-induced dipole and
00
04
08
12
16
20
0 02 04 06 08 1
minus10
Paminus1)
x1
Δks
(10
Figure 2 Variation of deviation in adiabatic compressibility Δ119896119904
with mole fraction 1199091 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
dipole-dipole interactions interstitial accommodation andbreaking up of the alcohol structures leads to positive valuesof Δ119896119904 From Figure 2 the observed positive values of Δ119896
119904for
binary mixtures of CHwith 119899-butanol 119904119890119888-butanol and 119905119890119903119905-butanol are due to declustering of alcohols in the presence ofCH The positive deviation in Δ119896
119904for the binary systems fol-
lows the order CH+ 119905119890119903119905-butanolgt 119904119890119888-butanolgt 119899-butanolFigure 3 represents the variation of119871119864
119891withmole fraction (119909
1)
of CH The observed values of 119871119864119891are positive According
to Fort and Moore [20] positive 119871119864119891should be attributed to
the dispersive forces As mentioned earlier positive values ofΔ119896119904and 119871119864
119891are mainly attributed to weak forces between the
component molecules in the mixture [21]
6 Journal of Applied Chemistry
0
001
002
003
004
005
006
0 02 04 06 08 1
minus10
m)
x1
LE f(10
Figure 3 Variation of excess free length 119871119864119891 with mole fraction 119909
1
of cyclohexanone in (X) 119899-butanol(◼) sec-butanol(998771) and tert-butanol at 30815 K
00 02 04 06 08 1
minus004
minus008
minus012
minus016
6kg
mminus2
sminus1)
x1
ZE(10
Figure 4 Variation of excess acoustic impedance 119911119864 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
The variations of excess acoustic impedance (119911119864) anddeviation in ultrasonic speed (Δ119906) have been presented inFigures 4 and 5 respectively From Figure 4 it has beenobserved that the values of 119911119864 are negative over the entiremole fraction range indicating the decreasing strength ofinteractions between component molecules of the mixtureAccording to Gowrisankar et al [22] the negative valuesfor Δ119906 indicate the decrease in the strength of interactionbetween the molecules and the negative deviations in Δ119906from linear dependence suggest the presence of weak inter-action between the component molecules These deviationexcess properties further support the conclusions drawn from119881119864
119898 119871119864119891 and Δ119896
119904
The existing molecular interactions in the systems arewell reflected in the properties of partial molar volumes Thepartial molar volumes 119881
1198981of component 1 (CH) and 119881
1198982
of component 2 (isomers of butanol) in the mixtures overthe entire composition range have been calculated by usingthe following relations
1198811198981= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
00 02 04 06 08 1
minus20
minus40
minus60
minus80
x1
Δu
(msminus
1)
Figure 5 Variation of deviation in ultrasonic speed Δ119906 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
1198811198982= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(9)
where 119881lowast1and 119881lowast
2are the molar volumes of the pure com-
ponents of CH and butanols respectively The derivates inthe above equations are obtained by differentiating Redlich-Kister equation (7) which leads to the following equations for1198811198981
and 1198811198982
1198811198981= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(10)
1198811198982= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
+ 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(11)
using the above equations 1198811198641198981
1198811198641198982
have been calculatedusing
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(12)
The pertinent values of 1198811198981
and 1198811198982
are furnished inTable 4 From this table the values of 119881
1198981and 119881
1198982for
both the components in the mixtures are greater than theirrespective molar volumes in the pure state that is an expan-sion of volume takes place on mixing alcohols with ketoneThese results also support the observed positive values of119881119864
119898in all the binary systems Figures 6 and 7 represent the
variation of excess partial molar volumes of 1198811198641198981
(CH) 1198811198641198982
(isomers of butanol) in the binary mixtures Examinationof these figures reveals that dispersion forces exist betweenthe unlike molecules These figures support the conclusionsdrawn from119881119864
119898The partial molar volumes and excess partial
Journal of Applied Chemistry 7
Table 4 Partial molar volumes of CH (1198811198981
10minus5m3 molminus1) and butanols (1198811198982
10minus5m3 molminus1) of all the binary systems with mole fraction(1199091) of CH at 30815 K
CH + 119899-butanol CH + 119904119890119888-butanol CH + 119905119890119903119905-butanol1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
10000 7210 42676 10000 7210 49234 10000 7210 5461209121 7699 32512 09212 7681 38378 09221 7606 4459008854 7999 30035 08867 8130 34445 08895 7997 4078807211 10600 19303 07121 11586 20460 07012 12366 2341306687 11554 17041 06786 12354 18636 06814 12989 2202305232 14365 12385 05123 16219 12221 05112 19004 1308704752 15378 11198 04688 17234 11058 04777 20247 1189303231 19092 8232 03121 20995 8043 03321 25389 841602112 22264 6843 02797 21794 7619 02635 27459 756201313 24403 6314 01112 25586 6406 01323 30211 687400000 25905 6128 00000 26462 6307 00000 30421 6823
0
10
20
30
40
50
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m2
(10
Figure 6 Variation of excess partial molar volume 1198811198641198982
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
molar volumes ofCHand isomers of butanols in all the binaryliquid mixtures at infinite dilution 119881infin
1198981 119881infin1198982
119881119864infin1198981
and119881
119864infin
1198982 respectively were obtained by putting 119909 = 0 in (10)
and 119909 = 1 in (11) Consider
119881
119864infin
1198981= 1198600+ 1198601+ 1198602+ 1198603+ sdot sdot sdot = 119881
infin
1198981minus 119881lowast
1
119881
119864infin
1198982= 1198600minus 1198601+ 1198602minus 1198603+ sdot sdot sdot = 119881
infin
1198982minus 119881lowast
2
(13)
The pertinent values of 119881infin1198981
119881infin1198982
119881119864infin1198981
and 119881119864infin1198982
arereported in Table 5 From this table it is seen that these valuesare positive from which we conclude that weak interactionsexist among the unlike molecules of the liquid mixtures
FT-IR spectra of pure CH butanols and binary mixturesof CH with butanols at equal concentrations are depicted inFigures 8 9 and 10 According to Karunakar and Srinivas[23] the intensity of an absorption in the IR spectrum isrelated to the change in dipole moment that occurs duringthe vibration Consequently vibrations that produce a largechange in dipole moment (eg C=O stretch) result in amore intense absorption than those that result in a relativelymodest change in dipole (eg C=C) Vibrations that do notresult in a change in dipole moment (eg a symmetrical
0
5
10
15
20
25
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m1
(10
Figure 7 Variation of excess partial molar volume 1198811198641198981
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
n-ButanolCH
Wave number (cmminus1)
CH + n-Butanol
Figure 8 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and 119899-butanol in the ratio 5 5 (green) andpure 119899-butanol (blue)
8 Journal of Applied Chemistry
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
sec-ButanolCH
Wave number (cmminus1)
CH + sec-Butanol
Figure 9 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and sec-butanol in the ratio 5 5 (green) andpure sec-butanol (blue)
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
tert-ButanolCH
Wave number (cmminus1)
CH + tert-Butanol
Figure 10 Fourier transform infrared spectra of pure cyclohex-anone (red) cyclohexanone and tert-butanol in the ratio 5 5(green) and pure tert-butanol (blue)
alkyne CequivC stretch) will show little or no absorption for thisvibration In the present FT-IR spectra liquid mixture showsvery small variations in the intensity of the respective bondsthat is dipole moment and hence it supports that weakinteractions take place between the components of liquidmolecules
Theoretical evaluation of ultrasonic speed in binary liquidmixtures and its correlation to study molecular interactionhas been successfully done in recent years Ultrasonic speedsin liquid mixtures have been calculated and compared with
Table 5 Partial molar volumes (119881infin1198981
119881infin1198982
) and excess partial molarvolumes (119881119864infin
1198981 119881119864infin1198982
) of the components at infinite dilution for allthe systems at 30815 K
System 119881
infin
1198981119881
infin
1198982119881
119864infin
1198981119881
119864infin
1198982
(10minus5m3 molminus1)CH + 119899-butanol 25519 43758 18696 36548CH + 119904119890119888-butanol 25561 509205 19253 42933CH + 119905119890119903119905-butanol 30034 55000 23211 47790
experimental values using various theories Such an evalua-tion offers a simple method to investigate molecular interac-tions besides verifying the applicability of various theories toliquid mixtures
Nomoto [24] established the following relation for soundspeed (119880
119873) based on the assumption of the linearity of the
molecular sound speed and the additivity of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(14)
where 119877119894is molar sound speed and 119881
119894is molar volume
van Dael and Vangeel [25] obtained the ideal mixturerelation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(15)
Baluja and Parsania [26] have given impedance relationon the basis of force of resistance for sound speed by theinteracting molecules
119880imp =sum119909119894119885119894
sum119909119894120588119894
(16)
Raorsquos (specific sound speed) [27] relation is given by
119880119877= (sum119909
119894119903119894120588)
3
(17)
where 119903119894= 11990613
119894120588119894is Raorsquos specific sound speed of 119894th com-
ponent of the mixturePercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906exp 119905
] (18)
Table 6 shows the values of ultrasonic speed computed byvarious theories along with their percentage error for all thesystems The variations between the evaluated and experi-mental values may be due to interactions occurring betweenthe hetero molecules of the binaries From the observedvalues of all three systems there is a good agreementbetween theoretical and experimental values through vanDeal andVangeel relation It can be seen fromTable 6 that thetheoretical values of ultrasonic speed calculated by using var-ious theories show deviation from experimental values Thelimitations and approximation incorporated in these theories
Journal of Applied Chemistry 9
Table 6Theoretical values of ultrasonic speed from various equations and percentage error withmole fraction1199091of CH for all binary systems
at 30815 K
1199091
119880119873
119880119881
119880Imp 119880119877
119880119873
119880119881
119880Imp 119880119877
CH + 119899-butanol10000 136200 136200 136200 136200 000 000 000 00009121 135001 134547 135043 129806 143 109 146 24808854 134632 134060 134687 128317 177 133 181 30107211 132309 131199 132427 122196 305 218 314 48306687 131549 130334 131681 120973 322 227 332 50805232 129386 128042 129542 118502 333 226 346 53604752 128656 127319 128814 117871 317 210 330 54803231 126283 125129 126429 116393 261 168 273 54202112 124478 123609 124594 116166 196 125 205 48501313 123158 122567 123239 116883 135 086 142 38200000 120930 120930 120930 120930 000 000 000 000
CH + 119904119890119888-butanol10000 136200 136200 136200 136200 000 000 000 00009212 134836 134412 134936 128464 144 112 152 33508867 134234 133650 134375 125830 198 153 208 44107121 131130 129973 131435 117255 382 291 406 71606786 130524 129300 130852 116263 402 304 428 73505123 127465 126097 127860 113158 433 321 465 73804688 126650 125296 127049 112705 422 310 455 72603121 123666 122524 124027 112004 338 243 369 63702797 123039 121972 123381 112051 313 223 341 60801112 119722 119210 119901 113885 141 098 156 35300000 117480 117480 117480 117480 000 000 000 000
CH + 119905119890119903119905-butanol10000 136200 136200 136200 136200 000 000 000 00009221 134013 133538 134413 126923 209 173 240 33108895 133099 132456 133651 123600 283 233 325 45107012 127840 126544 129065 109588 561 454 663 94606814 127289 125953 128564 108550 578 467 684 98005112 122570 121104 124087 102359 633 506 764 112104777 121645 120195 123170 101661 627 501 761 111903321 117638 116400 119036 100406 548 437 674 99702635 115760 114696 117000 100794 480 384 592 87501323 112183 111575 112939 103339 289 233 358 52300000 108600 108600 108600 108600 000 000 000 000
are responsible for the deviations of theoretical values fromexperimental values Nomotorsquos theory proposes that the vol-ume does not change upon mixingTherefore no interactionbetween the components of liquid mixtures has been takeninto account Similarly the assumption for the formation ofideal mixing relation is that the ratios of specific heats of idealmixtures and the volumes are also equal Again no molecularinteractions are taken into account But upon mixing inter-actions between the molecules occur because of the presenceof various types of forces such as dispersion forces chargetransfer and hydrogen bonding dipole-dipole and dipole-induced dipole interactions Thus the observed deviationof theoretical values of speed from the experimental values
shows that the molecular interactions are taking placebetween the CH and isomers of butanol molecules Thedeviations of experimental values and values calculated fromimpedance relation and Raorsquos relation imply nonadditivity ofacoustic impedance and Raorsquos speed in the liquid mixturesAmong all the empirical theories van Dael and Vangeelsrelation gives better estimate of experimental values of soundspeed in all the systems In the present binary systems thedifference between experimental and theoretical speeds isgreater where themole fraction of CH varies in the region 03to 06 Hence it can be qualitatively inferred that the strengthof interaction in the binary mixtures is more in this range ofcomposition of CH with isomers of butanol liquid system
10 Journal of Applied Chemistry
5 Conclusion
(i) Ultrasonic speeds 119906 and densities 120588 of mixtures ofcyclohexanone with 119899-butanol or sec-butanol or tert-butanol over the entire composition range have beenmeasured at 119879 = 30815K
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119911119864 and Δ119906 are calculated
from experimental data of density and ultrasonicspeed The excess and deviation properties have beenfitted to Redlich-Kister type polynomial and corre-sponding standard deviations have been evaluatedThe observed positive values of 119881119864
119898 Δ119896119904 and 119871119864
119891and
negative values of 119911119864 Δ119906 for all the liquid mixturesstudied clearly indicate the presence of weak inter-actions such as rupturing of hydrogen bond or reduc-tion in H-bond strength of butanol or breaking ofthe structure of one or both of the components in asolution
(iii) The deviationexcess properties have been fitted toRedlich-Kister type polynomial and the correspond-ing standard deviations have been calculated
(iv) The calculated values of partial molar volumes havealso been examined The observed higher partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate weak interactions present in the systems
(v) The strength of interaction in themixtures follows theorder CH + tert-butanol gt sec-butanol gt 119899-butanol
(vi) FT-IR spectra for the present binary mixture alsosupport the conclusions drawn from the 119881119864
119898 119871119864119891 Δ119896119904
Δ119906 and 119911119864(vii) Further theoretical values of sound speed in the mix-
tures have been evaluated using various theories andhave been compared with experimental sound speedsto verify the applicability of such theories to the sys-tems studied
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
One of the authors SkMdNayeem is thankful to UGC NewDelhi Government of India for the financial grants towardsMRP (MRP-467114C (SERO-UGC))
References
[1] T B Thoe D K Aspinwall and M L H Wise ldquoReview onultrasonic machiningrdquo International Journal of Machine Toolsand Manufacture vol 38 no 4 pp 239ndash255 1998
[2] G Thomas Chemistry for Pharmacy and the Life SciencesPrentice Hall London UK 1996
[3] A M Ababneh C C Large and S Georghiou ldquoSolvation ofnucleosides in aqueous mixtures of organic solvents relevanceto dna open basepairsrdquo Biophysical Journal vol 85 no 2 pp1111ndash1127 2003
[4] R E Treybal Mass Transfer Operations McGraw Hill Singa-pore 3rd edition 1981
[5] 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 atT = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[6] PGnanaKumari PVenkatesuMV PrabhakaraRaoM-J Leeand H-M Lin ldquoExcess molar volumes and ultrasonic studiesof 119873-methyl-2-pyrrolidone with ketones at 119879 = 30315 Krdquo TheJournal of ChemicalThermodynamics vol 41 no 5 pp 586ndash5902009
[7] M Sreenivasulu and P R Naidu ldquoExcess volumes and adiabaticcompressibility of binary mixtures of butyl amine and cyclicketonesrdquo Australian Journal of Chemistry vol 32 no 8 pp1649ndash1652 1979
[8] K Rajagopal and S Chenthilnath ldquoExcess thermodynamicstudies of binary liquid mixtures of 2-methyl-2-propanol withketonesrdquo Indian Journal of Pure amp Applied Physics vol 48 no5 pp 326ndash333 2010
[9] R K Bachu M K Patwari S Boodida and S Nallani ldquoVol-umetric and transport properties of binary liquid mixtures ofaliphatic ketones with phenylacetonitrile at T = 30815 Krdquo Jour-nal of Chemical amp Engineering Data vol 53 no 10 pp 2403ndash2407 2008
[10] N G Tsierkezos I E Molinou and A C Filippou ldquoThermo-dynamic properties of binary mixtures of cyclohexanone with119899-alkanols (C
1-C5) at 29315 Krdquo Journal of Solution Chemistry
vol 34 no 12 pp 1371ndash1386 2005[11] M Sri Lakshmi R R Raju C Rambabu G V R Rao and
K Narendra ldquoStudy of molecular interactions in binary liquidmixtures containing higher alcohols at different temperaturesrdquoResearchampReviews Journal of Chemistry vol 2 no 1 pp 12ndash242013
[12] A I Vogel Text Book of Practical Organic Chemistry LongmanLondon UK 5th edition 1989
[13] J A Riddick W Bunger and T K Sakano Techniques of Chem-istry Organic Solvents Physical Properties andMethods of Purifi-cation Wiley Interscience New York NY USA 4th edition1987
[14] R K Bachu andM K Patwari ldquoDensities viscosities and speedof sound of binary mixtures of phenylacetonitrile with somealiphatic alcohols at 30815 Krdquo Indian Journal of Chemistry Avol 47 no 7 pp 1026ndash1031 2008
[15] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Journal of Physical Chemistry vol 29 pp 130ndash1371925
[16] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification solutionsrdquoIndustrial and Engineering Chemistry vol 40 no 2 pp 345ndash348 1948
[17] R Vijaya Kumar S Viswanathan and M Anand Rao ldquoExcessvolumes speeds of sound and isentropic compressibilitiesof 2-propyn-1-ol + 12-dichloroethane +111-trichloroe thane+1122-tetrachloroethane and +trichloroethylene at 30315Krdquo
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Applied Chemistry 3
where Φ1 Φ2 and 119896
1199041 1198961199042are the volume fractions and adi-
abatic compressibilities of components 1 and 2 respectivelySince 119896
119904is not additive on mole fraction but is additive on
volume fraction such values are calculated using volumefraction (Φ)
Φ119894=
119909119894119881119894
sum119909119894119881119894
(6)
The experimentally measured values of ultrasonic speed (119906)and density (120588) and calculated properties of molar vol-ume (119881
119898) adiabatic compressibility (119896
119904) intermolecular free
length (119871119891) and acoustic impedance (119911) and excessdeviation
thermodynamic properties 119881119864119898 119871119864119891 119911119864 Δ119906 and Δ119896
119904are
presented in Table 2 for all binary systems over the entirecomposition range of CH
The excessdeviation properties have been fitted to aRedlich-Kister type polynomial equation [16]
119884119864
= 11990911199092
119899
sum
119894=0
119860119894(1199092minus 1199091)119894
(7)
where119884119864 = 119881119864119898 119871119864
119891 119911119864
Δ119906 andΔ119896119904 1199091is the mole fraction of
the soluteThe values of Δ119896
119904have been fitted to Redlich-Kister type
polynomial with volume fraction instead of mole fraction inthe above polynomial and 119860
119894are the adjustable parameters
of the function and are determined using the least squaremethod In the present investigation ldquo119894rdquo values are taken from0 to 4 The corresponding standard deviation 120590(119884119864) wascalculated using the expression
120590 (119884119864
) =[
[
sum(119884119864
exp minus 119884119864
cal)2
(119898 minus 119899)
]
]
12
(8)
where ldquo119898rdquo is the total number of experimental points and ldquo119899rdquois the number of coefficients in (7) The calculated values ofthe coefficients119860
119894alongwith the standard deviations (120590) have
been presented in Table 3
4 Results and Discussion
Figure 1 represents the variation of excess molar volume (119881119864119898)
with mole fraction of CH The sign of 119881119864119898
depends uponthe contraction and expansion of volume of the liquids dueto mixing The factors that are mainly responsible for theexpansion of molar volume that is positive values of 119881119864
119898 are
the following (i) breaking of the structure of one or bothof the components in a solution that is the loss of dipolarassociation between themolecules (dispersion forces) (ii) H-bond rupture and stretching of self-associatedmolecules (likealcohols) (iii) the geometry of molecular structures whichdoes not favour the fitting of molecules of one componentinto void space of another molecule (iv) steric hindrance ofthe molecules The negative values of 119881119864
119898are due to the (i)
association of molecules through the formation of hydrogenbond that is strong specific interactions and (ii) accom-modation of molecules because of large differences in their
0
01
02
03
04
05
0 02 04 06 08 1
minus02
minus01
minus5
m3
mol
minus1)
VE m
(10
x1
Figure 1 Variation of excess molar volume 119881119864119898 with mole fraction
1199091 of cyclohexanone in (X) 119899-butanol(◼) sec-butanol(998771) and
tert-butanol at 30815 K and Tsierkezos et al [10] for cyclohex-anone + 1-butanol (dotted lines) at 29315 K
molar volumes In other words 119881119864119898arises due to the result
of physical chemical and structural contributions Physicalinteractions involving mainly nonspecific interactions suchas dispersion or weak forces (breaking of the liquid orderon mixing ie loss of dipolar association between themolecules) contribute to positive 119881119864
119898 The chemical or spe-
cific interactions such as complex formation and hydrogenbond formation between constituent molecules contributeto negative 119881119864
119898 The structural effects arise from interstitial
accommodation due to the difference in the molar volumesand free volumes between the liquid components on mixingcontributing to negative119881119864
119898[17]The variation of119881119864
119898is found
to be positive over the entire composition range in the presentinvestigation which indicates that weak forces exist Sri Lak-shmi et al [11] reported similar results in CHwith 119899-heptanol119899-octanol and iso-octanol at temperatures of 30315 3081531315 and 31815 KThe119881119864
119898data obtained by Tsierkezos et al
[10] for CH + 1-butanol binary system are negative at 29315 Kwhereas in our investigations they are found to be positivewhen performed at 30815 K Such behaviour may arise dueto the fact that as temperature increases the effective collisionbetween the component molecules increases Thus largernumber of free dipoles of component molecules may beavailable due to declusttering of molecules in the pure state
Thenature of interaction in binary liquids can be analysedby knowing their chemical and physical properties (physic-ochemical properties) Generally butanols are associatedthrough the hydrogen bonding as shown below and in thepure state they exhibit equilibrium between the monomerand multimer species Also they can be associated withany other groups having some degree of polar attractionsAs discussed earlier butanol exhibits strong intermolecularinteractions (H-bond) Alcohol size chain length and phys-ical properties (boiling point density hydrophobic propertyviscosity insolubility and refractive index) are importantparameters that must be taken into account to explain thebehaviour of the interactions (Scheme 2)
CH is a polar molecule because of the presence ofcarbonyl group (C=O) this is due to the fact that oxygenis more electronegative (Ominus) than carbon (C+) Thus they
4 Journal of Applied Chemistry
Table2Ex
perim
entalvalueso
fdensities120588ultrason
icspeeds119906m
olarvolume119881119898adiabaticcompressib
ility119896119904intermolecularfre
elength119871119891acoustic
impedance119911and
excessdeviatio
nprop
ertie
s119881119864 119898119871119864 119891119911119864
Δ119906andΔ119896119904fora
llbinary
syste
msw
ithmolefraction1199091ofcyclohexano
neat30815K
1199091
120588(kg
mminus3
)119906(msminus1
)119881119898(1
0minus5
m3molminus1
)119896119904(1
0minus10
Paminus1
)119871119891(1
0minus10
m)119911(1
06kg
mminus2
sminus1
)119881119864 119898(1
0minus5
m3molminus1
)Δ119896119904(1
0minus10
Paminus1
)119871119864 119891(1
0minus10
m)119911119864
(106
kgmminus2
sminus1
)Δ119906(msminus1
)CH
+119899-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09121
91391
133102
72125
89952
06281
12164
00977
03231
00107
minus00355
minus1755
08854
9072
0132296
72111
91843
06347
12002
01252
040
0800133
minus00432
minus2154
07211
87362
128396
71186
10204
806690
11217
02105
06763
00226
minus00697
minus3545
066
8786485
127447
70775
104903
06783
11022
02261
07151
00239
minus00726
minus3694
05232
84320
125214
69241
112327
07019
10558
02302
07516
00254
minus00730
minus3705
04752
83665
1246
98
68566
114565
07089
10433
02147
07367
00251
minus00703
minus3488
03231
81759
123068
66549
1215
5807302
10062
01776
06877
00232
minus00593
minus2795
02112
80599
122087
64872
126087
07437
09840
01311
05914
00197
minus004
60minus2068
01313
7999
1121519
63611
12861
07511
09720
00915
04550
00150
minus00328
minus1415
000
0079650
120930
61275
130345
07561
09632
000
00000
00000
00000
00000
CH+119904119890119888-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09212
91229
132922
7244
990
394
06297
12126
01060
03836
00126
minus00397
minus1802
08867
90208
131633
72474
93357
06399
11874
01397
05194
00171
minus00529
minus2446
07121
86217
126303
72207
106512
06835
10889
02705
09784
00316
minus00907
minus4507
06786
85620
125483
7204
2108709
06905
10744
02843
10245
00331
minus00935
minus4700
05123
8315
6122177
70717
118365
07205
10160
03018
10967
00354
minus00941
minus4893
046
8882613
121526
70273
120569
07272
1004
002967
10794
00349
minus00909
minus4729
03121
8092
6119
619
68217
1276
5107483
09680
02325
09202
00299
minus00724
minus3703
02797
80631
119309
67723
128921
07520
09620
02124
08684
00282
minus00672
minus3406
01112
79503
118057
65053
134011
07667
09386
00974
046
0400149
minus00320
minus1504
000
0079320
117480
63075
1352
9207703
09319
000
00000
00000
00000
00000
CH+119905119890119903119905-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09221
90829
131268
73361
92340
06364
11923
01562
04969
00150
minus00527
minus2781
08895
89642
129440
73779
96141
06494
11603
02106
06834
00207
minus00702
minus3710
07012
84030
121044
75179
117001
07164
10171
04235
15137
00457
minus01296
minus6909
06814
83551
120337
75205
119041
07226
10054
04337
15721
00475
minus01325
minus7069
05112
8017
9115277
74950
134939
07693
09243
04741
18707
00562
minus01378
minus7432
04777
79661
114465
74783
1376
6907771
09118
04703
18823
00566
minus01354
minus7319
03321
7791
2111524
73616
147714
08049
08689
040
9917
360
00519
minus01135
minus6241
02635
77360
110459
72878
1512
7508146
08545
03627
15506
004
63minus00973
minus5413
01323
7677
8109036
70894
155581
08261
08372
02150
09556
00285
minus00562
minus3215
000
0076840
108600
68232
155954
08271
08345
000
00000
00000
00000
00000
Journal of Applied Chemistry 5
Table 3 Coefficients 119860119894of Redlich-Kister type polynomial equation (7) and the corresponding standard deviations 120590 of all the systems at
30815 K
1198600
1198601
1198602
1198603
1198604
120590
CH + 119899-butanol119881119864
119898(10minus5m3 molminus1) 247625 minus57880 36945 minus31381 minus08351 00019
Δ119896119904(10minus10 Paminus1) 00183 minus00020 00075 00029 minus00004 00091
119871119864
119891(10minus10m) 08201 minus01460 02529 00638 01066 00009
119911119864(106 kgmminus2 sminus1) minus02875 00836 minus01081 00006 minus00202 00002Δ119906(msminus1) minus140 058 minus031 minus003 minus018 00024
CH + 119904119890119888-butanol119881119864
119898(10minus5m3 molminus1) 275896 minus9594 42809 minus22460 minus07780 00018
Δ119896119904(10minus10 Paminus1) 00267 minus0001 00001 00033 00034 00001
119871119864
119891(10minus10m) 11507 minus01810 00576 01082 00684 00011
119911119864(106 kgmminus2 sminus1) minus03733 01252 minus00791 00092 minus00110 00001Δ119906(msminus1) minus194 059 minus004 minus001 minus004 00006
CH + 119905119890119903119905-butanol119881119864
119898(10minus5m3 molminus1) 364535 minus123900 minus06780 01003 minus02750 00009
Δ119896119904(10minus10 Paminus1) 00428 00120 00024 00019 00011 00001
119871119864
119891(10minus10m) 18117 01253 01393 00862 minus00290 00006
119911119864(106 kgmminus2 sminus1) minus05484 01374 minus00850 00123 minus00032 00001Δ119906(msminus1) minus296 062 minus054 001 minus001 00001
R R R
Structure of alcoholOndashHmiddot middot middotOndashH middot middot middot middot middot middot OndashH
Scheme 2
Resonance structure
middot middot middot
R R
R
C OOminus H+
Scheme 3
cause strong dipole-dipole interactions in chemical reactionsMoreover CH lacks hydroxyl groups so it is incapable ofcreating intermolecular hydrogen bonds In CH + isomersof butanol binary systems the negatively charged oxygen(Ominus) in CH tries to drag the positively charged H+ whichwere bounded in very strong intermolecular interactions ofbutanol (Scheme 3) An equilibrium stage is reached whererupturing of hydrogen bond or reduction inH-bond strengthof butanol or breaking of the structure of one or both ofthe components in a solution that is the loss of dipolarassociation between the molecules (dispersion forces) [18]will be favourable leading to weak interactions This causesincrease in volume of binary liquid and explains the observedpositive values 119881119864
119898in the systems
Kiyohara and Benson [19] have suggested that Δ119896119904is
the resultant of several opposing effects Negative values ofΔ119896119904contribute to charge transfer dipole-induced dipole and
00
04
08
12
16
20
0 02 04 06 08 1
minus10
Paminus1)
x1
Δks
(10
Figure 2 Variation of deviation in adiabatic compressibility Δ119896119904
with mole fraction 1199091 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
dipole-dipole interactions interstitial accommodation andbreaking up of the alcohol structures leads to positive valuesof Δ119896119904 From Figure 2 the observed positive values of Δ119896
119904for
binary mixtures of CHwith 119899-butanol 119904119890119888-butanol and 119905119890119903119905-butanol are due to declustering of alcohols in the presence ofCH The positive deviation in Δ119896
119904for the binary systems fol-
lows the order CH+ 119905119890119903119905-butanolgt 119904119890119888-butanolgt 119899-butanolFigure 3 represents the variation of119871119864
119891withmole fraction (119909
1)
of CH The observed values of 119871119864119891are positive According
to Fort and Moore [20] positive 119871119864119891should be attributed to
the dispersive forces As mentioned earlier positive values ofΔ119896119904and 119871119864
119891are mainly attributed to weak forces between the
component molecules in the mixture [21]
6 Journal of Applied Chemistry
0
001
002
003
004
005
006
0 02 04 06 08 1
minus10
m)
x1
LE f(10
Figure 3 Variation of excess free length 119871119864119891 with mole fraction 119909
1
of cyclohexanone in (X) 119899-butanol(◼) sec-butanol(998771) and tert-butanol at 30815 K
00 02 04 06 08 1
minus004
minus008
minus012
minus016
6kg
mminus2
sminus1)
x1
ZE(10
Figure 4 Variation of excess acoustic impedance 119911119864 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
The variations of excess acoustic impedance (119911119864) anddeviation in ultrasonic speed (Δ119906) have been presented inFigures 4 and 5 respectively From Figure 4 it has beenobserved that the values of 119911119864 are negative over the entiremole fraction range indicating the decreasing strength ofinteractions between component molecules of the mixtureAccording to Gowrisankar et al [22] the negative valuesfor Δ119906 indicate the decrease in the strength of interactionbetween the molecules and the negative deviations in Δ119906from linear dependence suggest the presence of weak inter-action between the component molecules These deviationexcess properties further support the conclusions drawn from119881119864
119898 119871119864119891 and Δ119896
119904
The existing molecular interactions in the systems arewell reflected in the properties of partial molar volumes Thepartial molar volumes 119881
1198981of component 1 (CH) and 119881
1198982
of component 2 (isomers of butanol) in the mixtures overthe entire composition range have been calculated by usingthe following relations
1198811198981= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
00 02 04 06 08 1
minus20
minus40
minus60
minus80
x1
Δu
(msminus
1)
Figure 5 Variation of deviation in ultrasonic speed Δ119906 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
1198811198982= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(9)
where 119881lowast1and 119881lowast
2are the molar volumes of the pure com-
ponents of CH and butanols respectively The derivates inthe above equations are obtained by differentiating Redlich-Kister equation (7) which leads to the following equations for1198811198981
and 1198811198982
1198811198981= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(10)
1198811198982= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
+ 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(11)
using the above equations 1198811198641198981
1198811198641198982
have been calculatedusing
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(12)
The pertinent values of 1198811198981
and 1198811198982
are furnished inTable 4 From this table the values of 119881
1198981and 119881
1198982for
both the components in the mixtures are greater than theirrespective molar volumes in the pure state that is an expan-sion of volume takes place on mixing alcohols with ketoneThese results also support the observed positive values of119881119864
119898in all the binary systems Figures 6 and 7 represent the
variation of excess partial molar volumes of 1198811198641198981
(CH) 1198811198641198982
(isomers of butanol) in the binary mixtures Examinationof these figures reveals that dispersion forces exist betweenthe unlike molecules These figures support the conclusionsdrawn from119881119864
119898The partial molar volumes and excess partial
Journal of Applied Chemistry 7
Table 4 Partial molar volumes of CH (1198811198981
10minus5m3 molminus1) and butanols (1198811198982
10minus5m3 molminus1) of all the binary systems with mole fraction(1199091) of CH at 30815 K
CH + 119899-butanol CH + 119904119890119888-butanol CH + 119905119890119903119905-butanol1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
10000 7210 42676 10000 7210 49234 10000 7210 5461209121 7699 32512 09212 7681 38378 09221 7606 4459008854 7999 30035 08867 8130 34445 08895 7997 4078807211 10600 19303 07121 11586 20460 07012 12366 2341306687 11554 17041 06786 12354 18636 06814 12989 2202305232 14365 12385 05123 16219 12221 05112 19004 1308704752 15378 11198 04688 17234 11058 04777 20247 1189303231 19092 8232 03121 20995 8043 03321 25389 841602112 22264 6843 02797 21794 7619 02635 27459 756201313 24403 6314 01112 25586 6406 01323 30211 687400000 25905 6128 00000 26462 6307 00000 30421 6823
0
10
20
30
40
50
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m2
(10
Figure 6 Variation of excess partial molar volume 1198811198641198982
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
molar volumes ofCHand isomers of butanols in all the binaryliquid mixtures at infinite dilution 119881infin
1198981 119881infin1198982
119881119864infin1198981
and119881
119864infin
1198982 respectively were obtained by putting 119909 = 0 in (10)
and 119909 = 1 in (11) Consider
119881
119864infin
1198981= 1198600+ 1198601+ 1198602+ 1198603+ sdot sdot sdot = 119881
infin
1198981minus 119881lowast
1
119881
119864infin
1198982= 1198600minus 1198601+ 1198602minus 1198603+ sdot sdot sdot = 119881
infin
1198982minus 119881lowast
2
(13)
The pertinent values of 119881infin1198981
119881infin1198982
119881119864infin1198981
and 119881119864infin1198982
arereported in Table 5 From this table it is seen that these valuesare positive from which we conclude that weak interactionsexist among the unlike molecules of the liquid mixtures
FT-IR spectra of pure CH butanols and binary mixturesof CH with butanols at equal concentrations are depicted inFigures 8 9 and 10 According to Karunakar and Srinivas[23] the intensity of an absorption in the IR spectrum isrelated to the change in dipole moment that occurs duringthe vibration Consequently vibrations that produce a largechange in dipole moment (eg C=O stretch) result in amore intense absorption than those that result in a relativelymodest change in dipole (eg C=C) Vibrations that do notresult in a change in dipole moment (eg a symmetrical
0
5
10
15
20
25
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m1
(10
Figure 7 Variation of excess partial molar volume 1198811198641198981
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
n-ButanolCH
Wave number (cmminus1)
CH + n-Butanol
Figure 8 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and 119899-butanol in the ratio 5 5 (green) andpure 119899-butanol (blue)
8 Journal of Applied Chemistry
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
sec-ButanolCH
Wave number (cmminus1)
CH + sec-Butanol
Figure 9 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and sec-butanol in the ratio 5 5 (green) andpure sec-butanol (blue)
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
tert-ButanolCH
Wave number (cmminus1)
CH + tert-Butanol
Figure 10 Fourier transform infrared spectra of pure cyclohex-anone (red) cyclohexanone and tert-butanol in the ratio 5 5(green) and pure tert-butanol (blue)
alkyne CequivC stretch) will show little or no absorption for thisvibration In the present FT-IR spectra liquid mixture showsvery small variations in the intensity of the respective bondsthat is dipole moment and hence it supports that weakinteractions take place between the components of liquidmolecules
Theoretical evaluation of ultrasonic speed in binary liquidmixtures and its correlation to study molecular interactionhas been successfully done in recent years Ultrasonic speedsin liquid mixtures have been calculated and compared with
Table 5 Partial molar volumes (119881infin1198981
119881infin1198982
) and excess partial molarvolumes (119881119864infin
1198981 119881119864infin1198982
) of the components at infinite dilution for allthe systems at 30815 K
System 119881
infin
1198981119881
infin
1198982119881
119864infin
1198981119881
119864infin
1198982
(10minus5m3 molminus1)CH + 119899-butanol 25519 43758 18696 36548CH + 119904119890119888-butanol 25561 509205 19253 42933CH + 119905119890119903119905-butanol 30034 55000 23211 47790
experimental values using various theories Such an evalua-tion offers a simple method to investigate molecular interac-tions besides verifying the applicability of various theories toliquid mixtures
Nomoto [24] established the following relation for soundspeed (119880
119873) based on the assumption of the linearity of the
molecular sound speed and the additivity of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(14)
where 119877119894is molar sound speed and 119881
119894is molar volume
van Dael and Vangeel [25] obtained the ideal mixturerelation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(15)
Baluja and Parsania [26] have given impedance relationon the basis of force of resistance for sound speed by theinteracting molecules
119880imp =sum119909119894119885119894
sum119909119894120588119894
(16)
Raorsquos (specific sound speed) [27] relation is given by
119880119877= (sum119909
119894119903119894120588)
3
(17)
where 119903119894= 11990613
119894120588119894is Raorsquos specific sound speed of 119894th com-
ponent of the mixturePercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906exp 119905
] (18)
Table 6 shows the values of ultrasonic speed computed byvarious theories along with their percentage error for all thesystems The variations between the evaluated and experi-mental values may be due to interactions occurring betweenthe hetero molecules of the binaries From the observedvalues of all three systems there is a good agreementbetween theoretical and experimental values through vanDeal andVangeel relation It can be seen fromTable 6 that thetheoretical values of ultrasonic speed calculated by using var-ious theories show deviation from experimental values Thelimitations and approximation incorporated in these theories
Journal of Applied Chemistry 9
Table 6Theoretical values of ultrasonic speed from various equations and percentage error withmole fraction1199091of CH for all binary systems
at 30815 K
1199091
119880119873
119880119881
119880Imp 119880119877
119880119873
119880119881
119880Imp 119880119877
CH + 119899-butanol10000 136200 136200 136200 136200 000 000 000 00009121 135001 134547 135043 129806 143 109 146 24808854 134632 134060 134687 128317 177 133 181 30107211 132309 131199 132427 122196 305 218 314 48306687 131549 130334 131681 120973 322 227 332 50805232 129386 128042 129542 118502 333 226 346 53604752 128656 127319 128814 117871 317 210 330 54803231 126283 125129 126429 116393 261 168 273 54202112 124478 123609 124594 116166 196 125 205 48501313 123158 122567 123239 116883 135 086 142 38200000 120930 120930 120930 120930 000 000 000 000
CH + 119904119890119888-butanol10000 136200 136200 136200 136200 000 000 000 00009212 134836 134412 134936 128464 144 112 152 33508867 134234 133650 134375 125830 198 153 208 44107121 131130 129973 131435 117255 382 291 406 71606786 130524 129300 130852 116263 402 304 428 73505123 127465 126097 127860 113158 433 321 465 73804688 126650 125296 127049 112705 422 310 455 72603121 123666 122524 124027 112004 338 243 369 63702797 123039 121972 123381 112051 313 223 341 60801112 119722 119210 119901 113885 141 098 156 35300000 117480 117480 117480 117480 000 000 000 000
CH + 119905119890119903119905-butanol10000 136200 136200 136200 136200 000 000 000 00009221 134013 133538 134413 126923 209 173 240 33108895 133099 132456 133651 123600 283 233 325 45107012 127840 126544 129065 109588 561 454 663 94606814 127289 125953 128564 108550 578 467 684 98005112 122570 121104 124087 102359 633 506 764 112104777 121645 120195 123170 101661 627 501 761 111903321 117638 116400 119036 100406 548 437 674 99702635 115760 114696 117000 100794 480 384 592 87501323 112183 111575 112939 103339 289 233 358 52300000 108600 108600 108600 108600 000 000 000 000
are responsible for the deviations of theoretical values fromexperimental values Nomotorsquos theory proposes that the vol-ume does not change upon mixingTherefore no interactionbetween the components of liquid mixtures has been takeninto account Similarly the assumption for the formation ofideal mixing relation is that the ratios of specific heats of idealmixtures and the volumes are also equal Again no molecularinteractions are taken into account But upon mixing inter-actions between the molecules occur because of the presenceof various types of forces such as dispersion forces chargetransfer and hydrogen bonding dipole-dipole and dipole-induced dipole interactions Thus the observed deviationof theoretical values of speed from the experimental values
shows that the molecular interactions are taking placebetween the CH and isomers of butanol molecules Thedeviations of experimental values and values calculated fromimpedance relation and Raorsquos relation imply nonadditivity ofacoustic impedance and Raorsquos speed in the liquid mixturesAmong all the empirical theories van Dael and Vangeelsrelation gives better estimate of experimental values of soundspeed in all the systems In the present binary systems thedifference between experimental and theoretical speeds isgreater where themole fraction of CH varies in the region 03to 06 Hence it can be qualitatively inferred that the strengthof interaction in the binary mixtures is more in this range ofcomposition of CH with isomers of butanol liquid system
10 Journal of Applied Chemistry
5 Conclusion
(i) Ultrasonic speeds 119906 and densities 120588 of mixtures ofcyclohexanone with 119899-butanol or sec-butanol or tert-butanol over the entire composition range have beenmeasured at 119879 = 30815K
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119911119864 and Δ119906 are calculated
from experimental data of density and ultrasonicspeed The excess and deviation properties have beenfitted to Redlich-Kister type polynomial and corre-sponding standard deviations have been evaluatedThe observed positive values of 119881119864
119898 Δ119896119904 and 119871119864
119891and
negative values of 119911119864 Δ119906 for all the liquid mixturesstudied clearly indicate the presence of weak inter-actions such as rupturing of hydrogen bond or reduc-tion in H-bond strength of butanol or breaking ofthe structure of one or both of the components in asolution
(iii) The deviationexcess properties have been fitted toRedlich-Kister type polynomial and the correspond-ing standard deviations have been calculated
(iv) The calculated values of partial molar volumes havealso been examined The observed higher partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate weak interactions present in the systems
(v) The strength of interaction in themixtures follows theorder CH + tert-butanol gt sec-butanol gt 119899-butanol
(vi) FT-IR spectra for the present binary mixture alsosupport the conclusions drawn from the 119881119864
119898 119871119864119891 Δ119896119904
Δ119906 and 119911119864(vii) Further theoretical values of sound speed in the mix-
tures have been evaluated using various theories andhave been compared with experimental sound speedsto verify the applicability of such theories to the sys-tems studied
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
One of the authors SkMdNayeem is thankful to UGC NewDelhi Government of India for the financial grants towardsMRP (MRP-467114C (SERO-UGC))
References
[1] T B Thoe D K Aspinwall and M L H Wise ldquoReview onultrasonic machiningrdquo International Journal of Machine Toolsand Manufacture vol 38 no 4 pp 239ndash255 1998
[2] G Thomas Chemistry for Pharmacy and the Life SciencesPrentice Hall London UK 1996
[3] A M Ababneh C C Large and S Georghiou ldquoSolvation ofnucleosides in aqueous mixtures of organic solvents relevanceto dna open basepairsrdquo Biophysical Journal vol 85 no 2 pp1111ndash1127 2003
[4] R E Treybal Mass Transfer Operations McGraw Hill Singa-pore 3rd edition 1981
[5] 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 atT = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[6] PGnanaKumari PVenkatesuMV PrabhakaraRaoM-J Leeand H-M Lin ldquoExcess molar volumes and ultrasonic studiesof 119873-methyl-2-pyrrolidone with ketones at 119879 = 30315 Krdquo TheJournal of ChemicalThermodynamics vol 41 no 5 pp 586ndash5902009
[7] M Sreenivasulu and P R Naidu ldquoExcess volumes and adiabaticcompressibility of binary mixtures of butyl amine and cyclicketonesrdquo Australian Journal of Chemistry vol 32 no 8 pp1649ndash1652 1979
[8] K Rajagopal and S Chenthilnath ldquoExcess thermodynamicstudies of binary liquid mixtures of 2-methyl-2-propanol withketonesrdquo Indian Journal of Pure amp Applied Physics vol 48 no5 pp 326ndash333 2010
[9] R K Bachu M K Patwari S Boodida and S Nallani ldquoVol-umetric and transport properties of binary liquid mixtures ofaliphatic ketones with phenylacetonitrile at T = 30815 Krdquo Jour-nal of Chemical amp Engineering Data vol 53 no 10 pp 2403ndash2407 2008
[10] N G Tsierkezos I E Molinou and A C Filippou ldquoThermo-dynamic properties of binary mixtures of cyclohexanone with119899-alkanols (C
1-C5) at 29315 Krdquo Journal of Solution Chemistry
vol 34 no 12 pp 1371ndash1386 2005[11] M Sri Lakshmi R R Raju C Rambabu G V R Rao and
K Narendra ldquoStudy of molecular interactions in binary liquidmixtures containing higher alcohols at different temperaturesrdquoResearchampReviews Journal of Chemistry vol 2 no 1 pp 12ndash242013
[12] A I Vogel Text Book of Practical Organic Chemistry LongmanLondon UK 5th edition 1989
[13] J A Riddick W Bunger and T K Sakano Techniques of Chem-istry Organic Solvents Physical Properties andMethods of Purifi-cation Wiley Interscience New York NY USA 4th edition1987
[14] R K Bachu andM K Patwari ldquoDensities viscosities and speedof sound of binary mixtures of phenylacetonitrile with somealiphatic alcohols at 30815 Krdquo Indian Journal of Chemistry Avol 47 no 7 pp 1026ndash1031 2008
[15] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Journal of Physical Chemistry vol 29 pp 130ndash1371925
[16] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification solutionsrdquoIndustrial and Engineering Chemistry vol 40 no 2 pp 345ndash348 1948
[17] R Vijaya Kumar S Viswanathan and M Anand Rao ldquoExcessvolumes speeds of sound and isentropic compressibilitiesof 2-propyn-1-ol + 12-dichloroethane +111-trichloroe thane+1122-tetrachloroethane and +trichloroethylene at 30315Krdquo
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
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Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
4 Journal of Applied Chemistry
Table2Ex
perim
entalvalueso
fdensities120588ultrason
icspeeds119906m
olarvolume119881119898adiabaticcompressib
ility119896119904intermolecularfre
elength119871119891acoustic
impedance119911and
excessdeviatio
nprop
ertie
s119881119864 119898119871119864 119891119911119864
Δ119906andΔ119896119904fora
llbinary
syste
msw
ithmolefraction1199091ofcyclohexano
neat30815K
1199091
120588(kg
mminus3
)119906(msminus1
)119881119898(1
0minus5
m3molminus1
)119896119904(1
0minus10
Paminus1
)119871119891(1
0minus10
m)119911(1
06kg
mminus2
sminus1
)119881119864 119898(1
0minus5
m3molminus1
)Δ119896119904(1
0minus10
Paminus1
)119871119864 119891(1
0minus10
m)119911119864
(106
kgmminus2
sminus1
)Δ119906(msminus1
)CH
+119899-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09121
91391
133102
72125
89952
06281
12164
00977
03231
00107
minus00355
minus1755
08854
9072
0132296
72111
91843
06347
12002
01252
040
0800133
minus00432
minus2154
07211
87362
128396
71186
10204
806690
11217
02105
06763
00226
minus00697
minus3545
066
8786485
127447
70775
104903
06783
11022
02261
07151
00239
minus00726
minus3694
05232
84320
125214
69241
112327
07019
10558
02302
07516
00254
minus00730
minus3705
04752
83665
1246
98
68566
114565
07089
10433
02147
07367
00251
minus00703
minus3488
03231
81759
123068
66549
1215
5807302
10062
01776
06877
00232
minus00593
minus2795
02112
80599
122087
64872
126087
07437
09840
01311
05914
00197
minus004
60minus2068
01313
7999
1121519
63611
12861
07511
09720
00915
04550
00150
minus00328
minus1415
000
0079650
120930
61275
130345
07561
09632
000
00000
00000
00000
00000
CH+119904119890119888-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09212
91229
132922
7244
990
394
06297
12126
01060
03836
00126
minus00397
minus1802
08867
90208
131633
72474
93357
06399
11874
01397
05194
00171
minus00529
minus2446
07121
86217
126303
72207
106512
06835
10889
02705
09784
00316
minus00907
minus4507
06786
85620
125483
7204
2108709
06905
10744
02843
10245
00331
minus00935
minus4700
05123
8315
6122177
70717
118365
07205
10160
03018
10967
00354
minus00941
minus4893
046
8882613
121526
70273
120569
07272
1004
002967
10794
00349
minus00909
minus4729
03121
8092
6119
619
68217
1276
5107483
09680
02325
09202
00299
minus00724
minus3703
02797
80631
119309
67723
128921
07520
09620
02124
08684
00282
minus00672
minus3406
01112
79503
118057
65053
134011
07667
09386
00974
046
0400149
minus00320
minus1504
000
0079320
117480
63075
1352
9207703
09319
000
00000
00000
00000
00000
CH+119905119890119903119905-butanol
1000
09396
0136200
72100
83164
060
4012
797
000
00000
00000
00000
00000
09221
90829
131268
73361
92340
06364
11923
01562
04969
00150
minus00527
minus2781
08895
89642
129440
73779
96141
06494
11603
02106
06834
00207
minus00702
minus3710
07012
84030
121044
75179
117001
07164
10171
04235
15137
00457
minus01296
minus6909
06814
83551
120337
75205
119041
07226
10054
04337
15721
00475
minus01325
minus7069
05112
8017
9115277
74950
134939
07693
09243
04741
18707
00562
minus01378
minus7432
04777
79661
114465
74783
1376
6907771
09118
04703
18823
00566
minus01354
minus7319
03321
7791
2111524
73616
147714
08049
08689
040
9917
360
00519
minus01135
minus6241
02635
77360
110459
72878
1512
7508146
08545
03627
15506
004
63minus00973
minus5413
01323
7677
8109036
70894
155581
08261
08372
02150
09556
00285
minus00562
minus3215
000
0076840
108600
68232
155954
08271
08345
000
00000
00000
00000
00000
Journal of Applied Chemistry 5
Table 3 Coefficients 119860119894of Redlich-Kister type polynomial equation (7) and the corresponding standard deviations 120590 of all the systems at
30815 K
1198600
1198601
1198602
1198603
1198604
120590
CH + 119899-butanol119881119864
119898(10minus5m3 molminus1) 247625 minus57880 36945 minus31381 minus08351 00019
Δ119896119904(10minus10 Paminus1) 00183 minus00020 00075 00029 minus00004 00091
119871119864
119891(10minus10m) 08201 minus01460 02529 00638 01066 00009
119911119864(106 kgmminus2 sminus1) minus02875 00836 minus01081 00006 minus00202 00002Δ119906(msminus1) minus140 058 minus031 minus003 minus018 00024
CH + 119904119890119888-butanol119881119864
119898(10minus5m3 molminus1) 275896 minus9594 42809 minus22460 minus07780 00018
Δ119896119904(10minus10 Paminus1) 00267 minus0001 00001 00033 00034 00001
119871119864
119891(10minus10m) 11507 minus01810 00576 01082 00684 00011
119911119864(106 kgmminus2 sminus1) minus03733 01252 minus00791 00092 minus00110 00001Δ119906(msminus1) minus194 059 minus004 minus001 minus004 00006
CH + 119905119890119903119905-butanol119881119864
119898(10minus5m3 molminus1) 364535 minus123900 minus06780 01003 minus02750 00009
Δ119896119904(10minus10 Paminus1) 00428 00120 00024 00019 00011 00001
119871119864
119891(10minus10m) 18117 01253 01393 00862 minus00290 00006
119911119864(106 kgmminus2 sminus1) minus05484 01374 minus00850 00123 minus00032 00001Δ119906(msminus1) minus296 062 minus054 001 minus001 00001
R R R
Structure of alcoholOndashHmiddot middot middotOndashH middot middot middot middot middot middot OndashH
Scheme 2
Resonance structure
middot middot middot
R R
R
C OOminus H+
Scheme 3
cause strong dipole-dipole interactions in chemical reactionsMoreover CH lacks hydroxyl groups so it is incapable ofcreating intermolecular hydrogen bonds In CH + isomersof butanol binary systems the negatively charged oxygen(Ominus) in CH tries to drag the positively charged H+ whichwere bounded in very strong intermolecular interactions ofbutanol (Scheme 3) An equilibrium stage is reached whererupturing of hydrogen bond or reduction inH-bond strengthof butanol or breaking of the structure of one or both ofthe components in a solution that is the loss of dipolarassociation between the molecules (dispersion forces) [18]will be favourable leading to weak interactions This causesincrease in volume of binary liquid and explains the observedpositive values 119881119864
119898in the systems
Kiyohara and Benson [19] have suggested that Δ119896119904is
the resultant of several opposing effects Negative values ofΔ119896119904contribute to charge transfer dipole-induced dipole and
00
04
08
12
16
20
0 02 04 06 08 1
minus10
Paminus1)
x1
Δks
(10
Figure 2 Variation of deviation in adiabatic compressibility Δ119896119904
with mole fraction 1199091 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
dipole-dipole interactions interstitial accommodation andbreaking up of the alcohol structures leads to positive valuesof Δ119896119904 From Figure 2 the observed positive values of Δ119896
119904for
binary mixtures of CHwith 119899-butanol 119904119890119888-butanol and 119905119890119903119905-butanol are due to declustering of alcohols in the presence ofCH The positive deviation in Δ119896
119904for the binary systems fol-
lows the order CH+ 119905119890119903119905-butanolgt 119904119890119888-butanolgt 119899-butanolFigure 3 represents the variation of119871119864
119891withmole fraction (119909
1)
of CH The observed values of 119871119864119891are positive According
to Fort and Moore [20] positive 119871119864119891should be attributed to
the dispersive forces As mentioned earlier positive values ofΔ119896119904and 119871119864
119891are mainly attributed to weak forces between the
component molecules in the mixture [21]
6 Journal of Applied Chemistry
0
001
002
003
004
005
006
0 02 04 06 08 1
minus10
m)
x1
LE f(10
Figure 3 Variation of excess free length 119871119864119891 with mole fraction 119909
1
of cyclohexanone in (X) 119899-butanol(◼) sec-butanol(998771) and tert-butanol at 30815 K
00 02 04 06 08 1
minus004
minus008
minus012
minus016
6kg
mminus2
sminus1)
x1
ZE(10
Figure 4 Variation of excess acoustic impedance 119911119864 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
The variations of excess acoustic impedance (119911119864) anddeviation in ultrasonic speed (Δ119906) have been presented inFigures 4 and 5 respectively From Figure 4 it has beenobserved that the values of 119911119864 are negative over the entiremole fraction range indicating the decreasing strength ofinteractions between component molecules of the mixtureAccording to Gowrisankar et al [22] the negative valuesfor Δ119906 indicate the decrease in the strength of interactionbetween the molecules and the negative deviations in Δ119906from linear dependence suggest the presence of weak inter-action between the component molecules These deviationexcess properties further support the conclusions drawn from119881119864
119898 119871119864119891 and Δ119896
119904
The existing molecular interactions in the systems arewell reflected in the properties of partial molar volumes Thepartial molar volumes 119881
1198981of component 1 (CH) and 119881
1198982
of component 2 (isomers of butanol) in the mixtures overthe entire composition range have been calculated by usingthe following relations
1198811198981= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
00 02 04 06 08 1
minus20
minus40
minus60
minus80
x1
Δu
(msminus
1)
Figure 5 Variation of deviation in ultrasonic speed Δ119906 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
1198811198982= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(9)
where 119881lowast1and 119881lowast
2are the molar volumes of the pure com-
ponents of CH and butanols respectively The derivates inthe above equations are obtained by differentiating Redlich-Kister equation (7) which leads to the following equations for1198811198981
and 1198811198982
1198811198981= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(10)
1198811198982= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
+ 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(11)
using the above equations 1198811198641198981
1198811198641198982
have been calculatedusing
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(12)
The pertinent values of 1198811198981
and 1198811198982
are furnished inTable 4 From this table the values of 119881
1198981and 119881
1198982for
both the components in the mixtures are greater than theirrespective molar volumes in the pure state that is an expan-sion of volume takes place on mixing alcohols with ketoneThese results also support the observed positive values of119881119864
119898in all the binary systems Figures 6 and 7 represent the
variation of excess partial molar volumes of 1198811198641198981
(CH) 1198811198641198982
(isomers of butanol) in the binary mixtures Examinationof these figures reveals that dispersion forces exist betweenthe unlike molecules These figures support the conclusionsdrawn from119881119864
119898The partial molar volumes and excess partial
Journal of Applied Chemistry 7
Table 4 Partial molar volumes of CH (1198811198981
10minus5m3 molminus1) and butanols (1198811198982
10minus5m3 molminus1) of all the binary systems with mole fraction(1199091) of CH at 30815 K
CH + 119899-butanol CH + 119904119890119888-butanol CH + 119905119890119903119905-butanol1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
10000 7210 42676 10000 7210 49234 10000 7210 5461209121 7699 32512 09212 7681 38378 09221 7606 4459008854 7999 30035 08867 8130 34445 08895 7997 4078807211 10600 19303 07121 11586 20460 07012 12366 2341306687 11554 17041 06786 12354 18636 06814 12989 2202305232 14365 12385 05123 16219 12221 05112 19004 1308704752 15378 11198 04688 17234 11058 04777 20247 1189303231 19092 8232 03121 20995 8043 03321 25389 841602112 22264 6843 02797 21794 7619 02635 27459 756201313 24403 6314 01112 25586 6406 01323 30211 687400000 25905 6128 00000 26462 6307 00000 30421 6823
0
10
20
30
40
50
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m2
(10
Figure 6 Variation of excess partial molar volume 1198811198641198982
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
molar volumes ofCHand isomers of butanols in all the binaryliquid mixtures at infinite dilution 119881infin
1198981 119881infin1198982
119881119864infin1198981
and119881
119864infin
1198982 respectively were obtained by putting 119909 = 0 in (10)
and 119909 = 1 in (11) Consider
119881
119864infin
1198981= 1198600+ 1198601+ 1198602+ 1198603+ sdot sdot sdot = 119881
infin
1198981minus 119881lowast
1
119881
119864infin
1198982= 1198600minus 1198601+ 1198602minus 1198603+ sdot sdot sdot = 119881
infin
1198982minus 119881lowast
2
(13)
The pertinent values of 119881infin1198981
119881infin1198982
119881119864infin1198981
and 119881119864infin1198982
arereported in Table 5 From this table it is seen that these valuesare positive from which we conclude that weak interactionsexist among the unlike molecules of the liquid mixtures
FT-IR spectra of pure CH butanols and binary mixturesof CH with butanols at equal concentrations are depicted inFigures 8 9 and 10 According to Karunakar and Srinivas[23] the intensity of an absorption in the IR spectrum isrelated to the change in dipole moment that occurs duringthe vibration Consequently vibrations that produce a largechange in dipole moment (eg C=O stretch) result in amore intense absorption than those that result in a relativelymodest change in dipole (eg C=C) Vibrations that do notresult in a change in dipole moment (eg a symmetrical
0
5
10
15
20
25
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m1
(10
Figure 7 Variation of excess partial molar volume 1198811198641198981
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
n-ButanolCH
Wave number (cmminus1)
CH + n-Butanol
Figure 8 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and 119899-butanol in the ratio 5 5 (green) andpure 119899-butanol (blue)
8 Journal of Applied Chemistry
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
sec-ButanolCH
Wave number (cmminus1)
CH + sec-Butanol
Figure 9 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and sec-butanol in the ratio 5 5 (green) andpure sec-butanol (blue)
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
tert-ButanolCH
Wave number (cmminus1)
CH + tert-Butanol
Figure 10 Fourier transform infrared spectra of pure cyclohex-anone (red) cyclohexanone and tert-butanol in the ratio 5 5(green) and pure tert-butanol (blue)
alkyne CequivC stretch) will show little or no absorption for thisvibration In the present FT-IR spectra liquid mixture showsvery small variations in the intensity of the respective bondsthat is dipole moment and hence it supports that weakinteractions take place between the components of liquidmolecules
Theoretical evaluation of ultrasonic speed in binary liquidmixtures and its correlation to study molecular interactionhas been successfully done in recent years Ultrasonic speedsin liquid mixtures have been calculated and compared with
Table 5 Partial molar volumes (119881infin1198981
119881infin1198982
) and excess partial molarvolumes (119881119864infin
1198981 119881119864infin1198982
) of the components at infinite dilution for allthe systems at 30815 K
System 119881
infin
1198981119881
infin
1198982119881
119864infin
1198981119881
119864infin
1198982
(10minus5m3 molminus1)CH + 119899-butanol 25519 43758 18696 36548CH + 119904119890119888-butanol 25561 509205 19253 42933CH + 119905119890119903119905-butanol 30034 55000 23211 47790
experimental values using various theories Such an evalua-tion offers a simple method to investigate molecular interac-tions besides verifying the applicability of various theories toliquid mixtures
Nomoto [24] established the following relation for soundspeed (119880
119873) based on the assumption of the linearity of the
molecular sound speed and the additivity of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(14)
where 119877119894is molar sound speed and 119881
119894is molar volume
van Dael and Vangeel [25] obtained the ideal mixturerelation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(15)
Baluja and Parsania [26] have given impedance relationon the basis of force of resistance for sound speed by theinteracting molecules
119880imp =sum119909119894119885119894
sum119909119894120588119894
(16)
Raorsquos (specific sound speed) [27] relation is given by
119880119877= (sum119909
119894119903119894120588)
3
(17)
where 119903119894= 11990613
119894120588119894is Raorsquos specific sound speed of 119894th com-
ponent of the mixturePercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906exp 119905
] (18)
Table 6 shows the values of ultrasonic speed computed byvarious theories along with their percentage error for all thesystems The variations between the evaluated and experi-mental values may be due to interactions occurring betweenthe hetero molecules of the binaries From the observedvalues of all three systems there is a good agreementbetween theoretical and experimental values through vanDeal andVangeel relation It can be seen fromTable 6 that thetheoretical values of ultrasonic speed calculated by using var-ious theories show deviation from experimental values Thelimitations and approximation incorporated in these theories
Journal of Applied Chemistry 9
Table 6Theoretical values of ultrasonic speed from various equations and percentage error withmole fraction1199091of CH for all binary systems
at 30815 K
1199091
119880119873
119880119881
119880Imp 119880119877
119880119873
119880119881
119880Imp 119880119877
CH + 119899-butanol10000 136200 136200 136200 136200 000 000 000 00009121 135001 134547 135043 129806 143 109 146 24808854 134632 134060 134687 128317 177 133 181 30107211 132309 131199 132427 122196 305 218 314 48306687 131549 130334 131681 120973 322 227 332 50805232 129386 128042 129542 118502 333 226 346 53604752 128656 127319 128814 117871 317 210 330 54803231 126283 125129 126429 116393 261 168 273 54202112 124478 123609 124594 116166 196 125 205 48501313 123158 122567 123239 116883 135 086 142 38200000 120930 120930 120930 120930 000 000 000 000
CH + 119904119890119888-butanol10000 136200 136200 136200 136200 000 000 000 00009212 134836 134412 134936 128464 144 112 152 33508867 134234 133650 134375 125830 198 153 208 44107121 131130 129973 131435 117255 382 291 406 71606786 130524 129300 130852 116263 402 304 428 73505123 127465 126097 127860 113158 433 321 465 73804688 126650 125296 127049 112705 422 310 455 72603121 123666 122524 124027 112004 338 243 369 63702797 123039 121972 123381 112051 313 223 341 60801112 119722 119210 119901 113885 141 098 156 35300000 117480 117480 117480 117480 000 000 000 000
CH + 119905119890119903119905-butanol10000 136200 136200 136200 136200 000 000 000 00009221 134013 133538 134413 126923 209 173 240 33108895 133099 132456 133651 123600 283 233 325 45107012 127840 126544 129065 109588 561 454 663 94606814 127289 125953 128564 108550 578 467 684 98005112 122570 121104 124087 102359 633 506 764 112104777 121645 120195 123170 101661 627 501 761 111903321 117638 116400 119036 100406 548 437 674 99702635 115760 114696 117000 100794 480 384 592 87501323 112183 111575 112939 103339 289 233 358 52300000 108600 108600 108600 108600 000 000 000 000
are responsible for the deviations of theoretical values fromexperimental values Nomotorsquos theory proposes that the vol-ume does not change upon mixingTherefore no interactionbetween the components of liquid mixtures has been takeninto account Similarly the assumption for the formation ofideal mixing relation is that the ratios of specific heats of idealmixtures and the volumes are also equal Again no molecularinteractions are taken into account But upon mixing inter-actions between the molecules occur because of the presenceof various types of forces such as dispersion forces chargetransfer and hydrogen bonding dipole-dipole and dipole-induced dipole interactions Thus the observed deviationof theoretical values of speed from the experimental values
shows that the molecular interactions are taking placebetween the CH and isomers of butanol molecules Thedeviations of experimental values and values calculated fromimpedance relation and Raorsquos relation imply nonadditivity ofacoustic impedance and Raorsquos speed in the liquid mixturesAmong all the empirical theories van Dael and Vangeelsrelation gives better estimate of experimental values of soundspeed in all the systems In the present binary systems thedifference between experimental and theoretical speeds isgreater where themole fraction of CH varies in the region 03to 06 Hence it can be qualitatively inferred that the strengthof interaction in the binary mixtures is more in this range ofcomposition of CH with isomers of butanol liquid system
10 Journal of Applied Chemistry
5 Conclusion
(i) Ultrasonic speeds 119906 and densities 120588 of mixtures ofcyclohexanone with 119899-butanol or sec-butanol or tert-butanol over the entire composition range have beenmeasured at 119879 = 30815K
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119911119864 and Δ119906 are calculated
from experimental data of density and ultrasonicspeed The excess and deviation properties have beenfitted to Redlich-Kister type polynomial and corre-sponding standard deviations have been evaluatedThe observed positive values of 119881119864
119898 Δ119896119904 and 119871119864
119891and
negative values of 119911119864 Δ119906 for all the liquid mixturesstudied clearly indicate the presence of weak inter-actions such as rupturing of hydrogen bond or reduc-tion in H-bond strength of butanol or breaking ofthe structure of one or both of the components in asolution
(iii) The deviationexcess properties have been fitted toRedlich-Kister type polynomial and the correspond-ing standard deviations have been calculated
(iv) The calculated values of partial molar volumes havealso been examined The observed higher partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate weak interactions present in the systems
(v) The strength of interaction in themixtures follows theorder CH + tert-butanol gt sec-butanol gt 119899-butanol
(vi) FT-IR spectra for the present binary mixture alsosupport the conclusions drawn from the 119881119864
119898 119871119864119891 Δ119896119904
Δ119906 and 119911119864(vii) Further theoretical values of sound speed in the mix-
tures have been evaluated using various theories andhave been compared with experimental sound speedsto verify the applicability of such theories to the sys-tems studied
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
One of the authors SkMdNayeem is thankful to UGC NewDelhi Government of India for the financial grants towardsMRP (MRP-467114C (SERO-UGC))
References
[1] T B Thoe D K Aspinwall and M L H Wise ldquoReview onultrasonic machiningrdquo International Journal of Machine Toolsand Manufacture vol 38 no 4 pp 239ndash255 1998
[2] G Thomas Chemistry for Pharmacy and the Life SciencesPrentice Hall London UK 1996
[3] A M Ababneh C C Large and S Georghiou ldquoSolvation ofnucleosides in aqueous mixtures of organic solvents relevanceto dna open basepairsrdquo Biophysical Journal vol 85 no 2 pp1111ndash1127 2003
[4] R E Treybal Mass Transfer Operations McGraw Hill Singa-pore 3rd edition 1981
[5] 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 atT = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[6] PGnanaKumari PVenkatesuMV PrabhakaraRaoM-J Leeand H-M Lin ldquoExcess molar volumes and ultrasonic studiesof 119873-methyl-2-pyrrolidone with ketones at 119879 = 30315 Krdquo TheJournal of ChemicalThermodynamics vol 41 no 5 pp 586ndash5902009
[7] M Sreenivasulu and P R Naidu ldquoExcess volumes and adiabaticcompressibility of binary mixtures of butyl amine and cyclicketonesrdquo Australian Journal of Chemistry vol 32 no 8 pp1649ndash1652 1979
[8] K Rajagopal and S Chenthilnath ldquoExcess thermodynamicstudies of binary liquid mixtures of 2-methyl-2-propanol withketonesrdquo Indian Journal of Pure amp Applied Physics vol 48 no5 pp 326ndash333 2010
[9] R K Bachu M K Patwari S Boodida and S Nallani ldquoVol-umetric and transport properties of binary liquid mixtures ofaliphatic ketones with phenylacetonitrile at T = 30815 Krdquo Jour-nal of Chemical amp Engineering Data vol 53 no 10 pp 2403ndash2407 2008
[10] N G Tsierkezos I E Molinou and A C Filippou ldquoThermo-dynamic properties of binary mixtures of cyclohexanone with119899-alkanols (C
1-C5) at 29315 Krdquo Journal of Solution Chemistry
vol 34 no 12 pp 1371ndash1386 2005[11] M Sri Lakshmi R R Raju C Rambabu G V R Rao and
K Narendra ldquoStudy of molecular interactions in binary liquidmixtures containing higher alcohols at different temperaturesrdquoResearchampReviews Journal of Chemistry vol 2 no 1 pp 12ndash242013
[12] A I Vogel Text Book of Practical Organic Chemistry LongmanLondon UK 5th edition 1989
[13] J A Riddick W Bunger and T K Sakano Techniques of Chem-istry Organic Solvents Physical Properties andMethods of Purifi-cation Wiley Interscience New York NY USA 4th edition1987
[14] R K Bachu andM K Patwari ldquoDensities viscosities and speedof sound of binary mixtures of phenylacetonitrile with somealiphatic alcohols at 30815 Krdquo Indian Journal of Chemistry Avol 47 no 7 pp 1026ndash1031 2008
[15] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Journal of Physical Chemistry vol 29 pp 130ndash1371925
[16] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification solutionsrdquoIndustrial and Engineering Chemistry vol 40 no 2 pp 345ndash348 1948
[17] R Vijaya Kumar S Viswanathan and M Anand Rao ldquoExcessvolumes speeds of sound and isentropic compressibilitiesof 2-propyn-1-ol + 12-dichloroethane +111-trichloroe thane+1122-tetrachloroethane and +trichloroethylene at 30315Krdquo
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
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CatalystsJournal of
Journal of Applied Chemistry 5
Table 3 Coefficients 119860119894of Redlich-Kister type polynomial equation (7) and the corresponding standard deviations 120590 of all the systems at
30815 K
1198600
1198601
1198602
1198603
1198604
120590
CH + 119899-butanol119881119864
119898(10minus5m3 molminus1) 247625 minus57880 36945 minus31381 minus08351 00019
Δ119896119904(10minus10 Paminus1) 00183 minus00020 00075 00029 minus00004 00091
119871119864
119891(10minus10m) 08201 minus01460 02529 00638 01066 00009
119911119864(106 kgmminus2 sminus1) minus02875 00836 minus01081 00006 minus00202 00002Δ119906(msminus1) minus140 058 minus031 minus003 minus018 00024
CH + 119904119890119888-butanol119881119864
119898(10minus5m3 molminus1) 275896 minus9594 42809 minus22460 minus07780 00018
Δ119896119904(10minus10 Paminus1) 00267 minus0001 00001 00033 00034 00001
119871119864
119891(10minus10m) 11507 minus01810 00576 01082 00684 00011
119911119864(106 kgmminus2 sminus1) minus03733 01252 minus00791 00092 minus00110 00001Δ119906(msminus1) minus194 059 minus004 minus001 minus004 00006
CH + 119905119890119903119905-butanol119881119864
119898(10minus5m3 molminus1) 364535 minus123900 minus06780 01003 minus02750 00009
Δ119896119904(10minus10 Paminus1) 00428 00120 00024 00019 00011 00001
119871119864
119891(10minus10m) 18117 01253 01393 00862 minus00290 00006
119911119864(106 kgmminus2 sminus1) minus05484 01374 minus00850 00123 minus00032 00001Δ119906(msminus1) minus296 062 minus054 001 minus001 00001
R R R
Structure of alcoholOndashHmiddot middot middotOndashH middot middot middot middot middot middot OndashH
Scheme 2
Resonance structure
middot middot middot
R R
R
C OOminus H+
Scheme 3
cause strong dipole-dipole interactions in chemical reactionsMoreover CH lacks hydroxyl groups so it is incapable ofcreating intermolecular hydrogen bonds In CH + isomersof butanol binary systems the negatively charged oxygen(Ominus) in CH tries to drag the positively charged H+ whichwere bounded in very strong intermolecular interactions ofbutanol (Scheme 3) An equilibrium stage is reached whererupturing of hydrogen bond or reduction inH-bond strengthof butanol or breaking of the structure of one or both ofthe components in a solution that is the loss of dipolarassociation between the molecules (dispersion forces) [18]will be favourable leading to weak interactions This causesincrease in volume of binary liquid and explains the observedpositive values 119881119864
119898in the systems
Kiyohara and Benson [19] have suggested that Δ119896119904is
the resultant of several opposing effects Negative values ofΔ119896119904contribute to charge transfer dipole-induced dipole and
00
04
08
12
16
20
0 02 04 06 08 1
minus10
Paminus1)
x1
Δks
(10
Figure 2 Variation of deviation in adiabatic compressibility Δ119896119904
with mole fraction 1199091 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
dipole-dipole interactions interstitial accommodation andbreaking up of the alcohol structures leads to positive valuesof Δ119896119904 From Figure 2 the observed positive values of Δ119896
119904for
binary mixtures of CHwith 119899-butanol 119904119890119888-butanol and 119905119890119903119905-butanol are due to declustering of alcohols in the presence ofCH The positive deviation in Δ119896
119904for the binary systems fol-
lows the order CH+ 119905119890119903119905-butanolgt 119904119890119888-butanolgt 119899-butanolFigure 3 represents the variation of119871119864
119891withmole fraction (119909
1)
of CH The observed values of 119871119864119891are positive According
to Fort and Moore [20] positive 119871119864119891should be attributed to
the dispersive forces As mentioned earlier positive values ofΔ119896119904and 119871119864
119891are mainly attributed to weak forces between the
component molecules in the mixture [21]
6 Journal of Applied Chemistry
0
001
002
003
004
005
006
0 02 04 06 08 1
minus10
m)
x1
LE f(10
Figure 3 Variation of excess free length 119871119864119891 with mole fraction 119909
1
of cyclohexanone in (X) 119899-butanol(◼) sec-butanol(998771) and tert-butanol at 30815 K
00 02 04 06 08 1
minus004
minus008
minus012
minus016
6kg
mminus2
sminus1)
x1
ZE(10
Figure 4 Variation of excess acoustic impedance 119911119864 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
The variations of excess acoustic impedance (119911119864) anddeviation in ultrasonic speed (Δ119906) have been presented inFigures 4 and 5 respectively From Figure 4 it has beenobserved that the values of 119911119864 are negative over the entiremole fraction range indicating the decreasing strength ofinteractions between component molecules of the mixtureAccording to Gowrisankar et al [22] the negative valuesfor Δ119906 indicate the decrease in the strength of interactionbetween the molecules and the negative deviations in Δ119906from linear dependence suggest the presence of weak inter-action between the component molecules These deviationexcess properties further support the conclusions drawn from119881119864
119898 119871119864119891 and Δ119896
119904
The existing molecular interactions in the systems arewell reflected in the properties of partial molar volumes Thepartial molar volumes 119881
1198981of component 1 (CH) and 119881
1198982
of component 2 (isomers of butanol) in the mixtures overthe entire composition range have been calculated by usingthe following relations
1198811198981= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
00 02 04 06 08 1
minus20
minus40
minus60
minus80
x1
Δu
(msminus
1)
Figure 5 Variation of deviation in ultrasonic speed Δ119906 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
1198811198982= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(9)
where 119881lowast1and 119881lowast
2are the molar volumes of the pure com-
ponents of CH and butanols respectively The derivates inthe above equations are obtained by differentiating Redlich-Kister equation (7) which leads to the following equations for1198811198981
and 1198811198982
1198811198981= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(10)
1198811198982= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
+ 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(11)
using the above equations 1198811198641198981
1198811198641198982
have been calculatedusing
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(12)
The pertinent values of 1198811198981
and 1198811198982
are furnished inTable 4 From this table the values of 119881
1198981and 119881
1198982for
both the components in the mixtures are greater than theirrespective molar volumes in the pure state that is an expan-sion of volume takes place on mixing alcohols with ketoneThese results also support the observed positive values of119881119864
119898in all the binary systems Figures 6 and 7 represent the
variation of excess partial molar volumes of 1198811198641198981
(CH) 1198811198641198982
(isomers of butanol) in the binary mixtures Examinationof these figures reveals that dispersion forces exist betweenthe unlike molecules These figures support the conclusionsdrawn from119881119864
119898The partial molar volumes and excess partial
Journal of Applied Chemistry 7
Table 4 Partial molar volumes of CH (1198811198981
10minus5m3 molminus1) and butanols (1198811198982
10minus5m3 molminus1) of all the binary systems with mole fraction(1199091) of CH at 30815 K
CH + 119899-butanol CH + 119904119890119888-butanol CH + 119905119890119903119905-butanol1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
10000 7210 42676 10000 7210 49234 10000 7210 5461209121 7699 32512 09212 7681 38378 09221 7606 4459008854 7999 30035 08867 8130 34445 08895 7997 4078807211 10600 19303 07121 11586 20460 07012 12366 2341306687 11554 17041 06786 12354 18636 06814 12989 2202305232 14365 12385 05123 16219 12221 05112 19004 1308704752 15378 11198 04688 17234 11058 04777 20247 1189303231 19092 8232 03121 20995 8043 03321 25389 841602112 22264 6843 02797 21794 7619 02635 27459 756201313 24403 6314 01112 25586 6406 01323 30211 687400000 25905 6128 00000 26462 6307 00000 30421 6823
0
10
20
30
40
50
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m2
(10
Figure 6 Variation of excess partial molar volume 1198811198641198982
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
molar volumes ofCHand isomers of butanols in all the binaryliquid mixtures at infinite dilution 119881infin
1198981 119881infin1198982
119881119864infin1198981
and119881
119864infin
1198982 respectively were obtained by putting 119909 = 0 in (10)
and 119909 = 1 in (11) Consider
119881
119864infin
1198981= 1198600+ 1198601+ 1198602+ 1198603+ sdot sdot sdot = 119881
infin
1198981minus 119881lowast
1
119881
119864infin
1198982= 1198600minus 1198601+ 1198602minus 1198603+ sdot sdot sdot = 119881
infin
1198982minus 119881lowast
2
(13)
The pertinent values of 119881infin1198981
119881infin1198982
119881119864infin1198981
and 119881119864infin1198982
arereported in Table 5 From this table it is seen that these valuesare positive from which we conclude that weak interactionsexist among the unlike molecules of the liquid mixtures
FT-IR spectra of pure CH butanols and binary mixturesof CH with butanols at equal concentrations are depicted inFigures 8 9 and 10 According to Karunakar and Srinivas[23] the intensity of an absorption in the IR spectrum isrelated to the change in dipole moment that occurs duringthe vibration Consequently vibrations that produce a largechange in dipole moment (eg C=O stretch) result in amore intense absorption than those that result in a relativelymodest change in dipole (eg C=C) Vibrations that do notresult in a change in dipole moment (eg a symmetrical
0
5
10
15
20
25
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m1
(10
Figure 7 Variation of excess partial molar volume 1198811198641198981
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
n-ButanolCH
Wave number (cmminus1)
CH + n-Butanol
Figure 8 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and 119899-butanol in the ratio 5 5 (green) andpure 119899-butanol (blue)
8 Journal of Applied Chemistry
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
sec-ButanolCH
Wave number (cmminus1)
CH + sec-Butanol
Figure 9 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and sec-butanol in the ratio 5 5 (green) andpure sec-butanol (blue)
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
tert-ButanolCH
Wave number (cmminus1)
CH + tert-Butanol
Figure 10 Fourier transform infrared spectra of pure cyclohex-anone (red) cyclohexanone and tert-butanol in the ratio 5 5(green) and pure tert-butanol (blue)
alkyne CequivC stretch) will show little or no absorption for thisvibration In the present FT-IR spectra liquid mixture showsvery small variations in the intensity of the respective bondsthat is dipole moment and hence it supports that weakinteractions take place between the components of liquidmolecules
Theoretical evaluation of ultrasonic speed in binary liquidmixtures and its correlation to study molecular interactionhas been successfully done in recent years Ultrasonic speedsin liquid mixtures have been calculated and compared with
Table 5 Partial molar volumes (119881infin1198981
119881infin1198982
) and excess partial molarvolumes (119881119864infin
1198981 119881119864infin1198982
) of the components at infinite dilution for allthe systems at 30815 K
System 119881
infin
1198981119881
infin
1198982119881
119864infin
1198981119881
119864infin
1198982
(10minus5m3 molminus1)CH + 119899-butanol 25519 43758 18696 36548CH + 119904119890119888-butanol 25561 509205 19253 42933CH + 119905119890119903119905-butanol 30034 55000 23211 47790
experimental values using various theories Such an evalua-tion offers a simple method to investigate molecular interac-tions besides verifying the applicability of various theories toliquid mixtures
Nomoto [24] established the following relation for soundspeed (119880
119873) based on the assumption of the linearity of the
molecular sound speed and the additivity of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(14)
where 119877119894is molar sound speed and 119881
119894is molar volume
van Dael and Vangeel [25] obtained the ideal mixturerelation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(15)
Baluja and Parsania [26] have given impedance relationon the basis of force of resistance for sound speed by theinteracting molecules
119880imp =sum119909119894119885119894
sum119909119894120588119894
(16)
Raorsquos (specific sound speed) [27] relation is given by
119880119877= (sum119909
119894119903119894120588)
3
(17)
where 119903119894= 11990613
119894120588119894is Raorsquos specific sound speed of 119894th com-
ponent of the mixturePercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906exp 119905
] (18)
Table 6 shows the values of ultrasonic speed computed byvarious theories along with their percentage error for all thesystems The variations between the evaluated and experi-mental values may be due to interactions occurring betweenthe hetero molecules of the binaries From the observedvalues of all three systems there is a good agreementbetween theoretical and experimental values through vanDeal andVangeel relation It can be seen fromTable 6 that thetheoretical values of ultrasonic speed calculated by using var-ious theories show deviation from experimental values Thelimitations and approximation incorporated in these theories
Journal of Applied Chemistry 9
Table 6Theoretical values of ultrasonic speed from various equations and percentage error withmole fraction1199091of CH for all binary systems
at 30815 K
1199091
119880119873
119880119881
119880Imp 119880119877
119880119873
119880119881
119880Imp 119880119877
CH + 119899-butanol10000 136200 136200 136200 136200 000 000 000 00009121 135001 134547 135043 129806 143 109 146 24808854 134632 134060 134687 128317 177 133 181 30107211 132309 131199 132427 122196 305 218 314 48306687 131549 130334 131681 120973 322 227 332 50805232 129386 128042 129542 118502 333 226 346 53604752 128656 127319 128814 117871 317 210 330 54803231 126283 125129 126429 116393 261 168 273 54202112 124478 123609 124594 116166 196 125 205 48501313 123158 122567 123239 116883 135 086 142 38200000 120930 120930 120930 120930 000 000 000 000
CH + 119904119890119888-butanol10000 136200 136200 136200 136200 000 000 000 00009212 134836 134412 134936 128464 144 112 152 33508867 134234 133650 134375 125830 198 153 208 44107121 131130 129973 131435 117255 382 291 406 71606786 130524 129300 130852 116263 402 304 428 73505123 127465 126097 127860 113158 433 321 465 73804688 126650 125296 127049 112705 422 310 455 72603121 123666 122524 124027 112004 338 243 369 63702797 123039 121972 123381 112051 313 223 341 60801112 119722 119210 119901 113885 141 098 156 35300000 117480 117480 117480 117480 000 000 000 000
CH + 119905119890119903119905-butanol10000 136200 136200 136200 136200 000 000 000 00009221 134013 133538 134413 126923 209 173 240 33108895 133099 132456 133651 123600 283 233 325 45107012 127840 126544 129065 109588 561 454 663 94606814 127289 125953 128564 108550 578 467 684 98005112 122570 121104 124087 102359 633 506 764 112104777 121645 120195 123170 101661 627 501 761 111903321 117638 116400 119036 100406 548 437 674 99702635 115760 114696 117000 100794 480 384 592 87501323 112183 111575 112939 103339 289 233 358 52300000 108600 108600 108600 108600 000 000 000 000
are responsible for the deviations of theoretical values fromexperimental values Nomotorsquos theory proposes that the vol-ume does not change upon mixingTherefore no interactionbetween the components of liquid mixtures has been takeninto account Similarly the assumption for the formation ofideal mixing relation is that the ratios of specific heats of idealmixtures and the volumes are also equal Again no molecularinteractions are taken into account But upon mixing inter-actions between the molecules occur because of the presenceof various types of forces such as dispersion forces chargetransfer and hydrogen bonding dipole-dipole and dipole-induced dipole interactions Thus the observed deviationof theoretical values of speed from the experimental values
shows that the molecular interactions are taking placebetween the CH and isomers of butanol molecules Thedeviations of experimental values and values calculated fromimpedance relation and Raorsquos relation imply nonadditivity ofacoustic impedance and Raorsquos speed in the liquid mixturesAmong all the empirical theories van Dael and Vangeelsrelation gives better estimate of experimental values of soundspeed in all the systems In the present binary systems thedifference between experimental and theoretical speeds isgreater where themole fraction of CH varies in the region 03to 06 Hence it can be qualitatively inferred that the strengthof interaction in the binary mixtures is more in this range ofcomposition of CH with isomers of butanol liquid system
10 Journal of Applied Chemistry
5 Conclusion
(i) Ultrasonic speeds 119906 and densities 120588 of mixtures ofcyclohexanone with 119899-butanol or sec-butanol or tert-butanol over the entire composition range have beenmeasured at 119879 = 30815K
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119911119864 and Δ119906 are calculated
from experimental data of density and ultrasonicspeed The excess and deviation properties have beenfitted to Redlich-Kister type polynomial and corre-sponding standard deviations have been evaluatedThe observed positive values of 119881119864
119898 Δ119896119904 and 119871119864
119891and
negative values of 119911119864 Δ119906 for all the liquid mixturesstudied clearly indicate the presence of weak inter-actions such as rupturing of hydrogen bond or reduc-tion in H-bond strength of butanol or breaking ofthe structure of one or both of the components in asolution
(iii) The deviationexcess properties have been fitted toRedlich-Kister type polynomial and the correspond-ing standard deviations have been calculated
(iv) The calculated values of partial molar volumes havealso been examined The observed higher partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate weak interactions present in the systems
(v) The strength of interaction in themixtures follows theorder CH + tert-butanol gt sec-butanol gt 119899-butanol
(vi) FT-IR spectra for the present binary mixture alsosupport the conclusions drawn from the 119881119864
119898 119871119864119891 Δ119896119904
Δ119906 and 119911119864(vii) Further theoretical values of sound speed in the mix-
tures have been evaluated using various theories andhave been compared with experimental sound speedsto verify the applicability of such theories to the sys-tems studied
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
One of the authors SkMdNayeem is thankful to UGC NewDelhi Government of India for the financial grants towardsMRP (MRP-467114C (SERO-UGC))
References
[1] T B Thoe D K Aspinwall and M L H Wise ldquoReview onultrasonic machiningrdquo International Journal of Machine Toolsand Manufacture vol 38 no 4 pp 239ndash255 1998
[2] G Thomas Chemistry for Pharmacy and the Life SciencesPrentice Hall London UK 1996
[3] A M Ababneh C C Large and S Georghiou ldquoSolvation ofnucleosides in aqueous mixtures of organic solvents relevanceto dna open basepairsrdquo Biophysical Journal vol 85 no 2 pp1111ndash1127 2003
[4] R E Treybal Mass Transfer Operations McGraw Hill Singa-pore 3rd edition 1981
[5] 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 atT = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[6] PGnanaKumari PVenkatesuMV PrabhakaraRaoM-J Leeand H-M Lin ldquoExcess molar volumes and ultrasonic studiesof 119873-methyl-2-pyrrolidone with ketones at 119879 = 30315 Krdquo TheJournal of ChemicalThermodynamics vol 41 no 5 pp 586ndash5902009
[7] M Sreenivasulu and P R Naidu ldquoExcess volumes and adiabaticcompressibility of binary mixtures of butyl amine and cyclicketonesrdquo Australian Journal of Chemistry vol 32 no 8 pp1649ndash1652 1979
[8] K Rajagopal and S Chenthilnath ldquoExcess thermodynamicstudies of binary liquid mixtures of 2-methyl-2-propanol withketonesrdquo Indian Journal of Pure amp Applied Physics vol 48 no5 pp 326ndash333 2010
[9] R K Bachu M K Patwari S Boodida and S Nallani ldquoVol-umetric and transport properties of binary liquid mixtures ofaliphatic ketones with phenylacetonitrile at T = 30815 Krdquo Jour-nal of Chemical amp Engineering Data vol 53 no 10 pp 2403ndash2407 2008
[10] N G Tsierkezos I E Molinou and A C Filippou ldquoThermo-dynamic properties of binary mixtures of cyclohexanone with119899-alkanols (C
1-C5) at 29315 Krdquo Journal of Solution Chemistry
vol 34 no 12 pp 1371ndash1386 2005[11] M Sri Lakshmi R R Raju C Rambabu G V R Rao and
K Narendra ldquoStudy of molecular interactions in binary liquidmixtures containing higher alcohols at different temperaturesrdquoResearchampReviews Journal of Chemistry vol 2 no 1 pp 12ndash242013
[12] A I Vogel Text Book of Practical Organic Chemistry LongmanLondon UK 5th edition 1989
[13] J A Riddick W Bunger and T K Sakano Techniques of Chem-istry Organic Solvents Physical Properties andMethods of Purifi-cation Wiley Interscience New York NY USA 4th edition1987
[14] R K Bachu andM K Patwari ldquoDensities viscosities and speedof sound of binary mixtures of phenylacetonitrile with somealiphatic alcohols at 30815 Krdquo Indian Journal of Chemistry Avol 47 no 7 pp 1026ndash1031 2008
[15] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Journal of Physical Chemistry vol 29 pp 130ndash1371925
[16] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification solutionsrdquoIndustrial and Engineering Chemistry vol 40 no 2 pp 345ndash348 1948
[17] R Vijaya Kumar S Viswanathan and M Anand Rao ldquoExcessvolumes speeds of sound and isentropic compressibilitiesof 2-propyn-1-ol + 12-dichloroethane +111-trichloroe thane+1122-tetrachloroethane and +trichloroethylene at 30315Krdquo
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
6 Journal of Applied Chemistry
0
001
002
003
004
005
006
0 02 04 06 08 1
minus10
m)
x1
LE f(10
Figure 3 Variation of excess free length 119871119864119891 with mole fraction 119909
1
of cyclohexanone in (X) 119899-butanol(◼) sec-butanol(998771) and tert-butanol at 30815 K
00 02 04 06 08 1
minus004
minus008
minus012
minus016
6kg
mminus2
sminus1)
x1
ZE(10
Figure 4 Variation of excess acoustic impedance 119911119864 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
The variations of excess acoustic impedance (119911119864) anddeviation in ultrasonic speed (Δ119906) have been presented inFigures 4 and 5 respectively From Figure 4 it has beenobserved that the values of 119911119864 are negative over the entiremole fraction range indicating the decreasing strength ofinteractions between component molecules of the mixtureAccording to Gowrisankar et al [22] the negative valuesfor Δ119906 indicate the decrease in the strength of interactionbetween the molecules and the negative deviations in Δ119906from linear dependence suggest the presence of weak inter-action between the component molecules These deviationexcess properties further support the conclusions drawn from119881119864
119898 119871119864119891 and Δ119896
119904
The existing molecular interactions in the systems arewell reflected in the properties of partial molar volumes Thepartial molar volumes 119881
1198981of component 1 (CH) and 119881
1198982
of component 2 (isomers of butanol) in the mixtures overthe entire composition range have been calculated by usingthe following relations
1198811198981= 119881119864
119898+ 119881lowast
1+ 1199092(
120597119881119864
119898
120597119909
)
119879119875
00 02 04 06 08 1
minus20
minus40
minus60
minus80
x1
Δu
(msminus
1)
Figure 5 Variation of deviation in ultrasonic speed Δ119906 withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
1198811198982= 119881119864
119898+ 119881lowast
2+ 1199091(
120597119881119864
119898
120597119909
)
119879119875
(9)
where 119881lowast1and 119881lowast
2are the molar volumes of the pure com-
ponents of CH and butanols respectively The derivates inthe above equations are obtained by differentiating Redlich-Kister equation (7) which leads to the following equations for1198811198981
and 1198811198982
1198811198981= 119881lowast
1+ 1199092
2
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
minus 211990911199092
2
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(10)
1198811198982= 119881lowast
2+ 1199092
1
119895
sum
119894=0
119860119894(1199092minus 1199091)119894
+ 211990921199092
1
119895
sum
119894=1
119860119894(1199092minus 1199091)119894minus1
(11)
using the above equations 1198811198641198981
1198811198641198982
have been calculatedusing
119881
119864
1198981= 1198811198981minus 119881lowast
1
119881
119864
1198982= 1198811198982minus 119881lowast
2
(12)
The pertinent values of 1198811198981
and 1198811198982
are furnished inTable 4 From this table the values of 119881
1198981and 119881
1198982for
both the components in the mixtures are greater than theirrespective molar volumes in the pure state that is an expan-sion of volume takes place on mixing alcohols with ketoneThese results also support the observed positive values of119881119864
119898in all the binary systems Figures 6 and 7 represent the
variation of excess partial molar volumes of 1198811198641198981
(CH) 1198811198641198982
(isomers of butanol) in the binary mixtures Examinationof these figures reveals that dispersion forces exist betweenthe unlike molecules These figures support the conclusionsdrawn from119881119864
119898The partial molar volumes and excess partial
Journal of Applied Chemistry 7
Table 4 Partial molar volumes of CH (1198811198981
10minus5m3 molminus1) and butanols (1198811198982
10minus5m3 molminus1) of all the binary systems with mole fraction(1199091) of CH at 30815 K
CH + 119899-butanol CH + 119904119890119888-butanol CH + 119905119890119903119905-butanol1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
10000 7210 42676 10000 7210 49234 10000 7210 5461209121 7699 32512 09212 7681 38378 09221 7606 4459008854 7999 30035 08867 8130 34445 08895 7997 4078807211 10600 19303 07121 11586 20460 07012 12366 2341306687 11554 17041 06786 12354 18636 06814 12989 2202305232 14365 12385 05123 16219 12221 05112 19004 1308704752 15378 11198 04688 17234 11058 04777 20247 1189303231 19092 8232 03121 20995 8043 03321 25389 841602112 22264 6843 02797 21794 7619 02635 27459 756201313 24403 6314 01112 25586 6406 01323 30211 687400000 25905 6128 00000 26462 6307 00000 30421 6823
0
10
20
30
40
50
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m2
(10
Figure 6 Variation of excess partial molar volume 1198811198641198982
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
molar volumes ofCHand isomers of butanols in all the binaryliquid mixtures at infinite dilution 119881infin
1198981 119881infin1198982
119881119864infin1198981
and119881
119864infin
1198982 respectively were obtained by putting 119909 = 0 in (10)
and 119909 = 1 in (11) Consider
119881
119864infin
1198981= 1198600+ 1198601+ 1198602+ 1198603+ sdot sdot sdot = 119881
infin
1198981minus 119881lowast
1
119881
119864infin
1198982= 1198600minus 1198601+ 1198602minus 1198603+ sdot sdot sdot = 119881
infin
1198982minus 119881lowast
2
(13)
The pertinent values of 119881infin1198981
119881infin1198982
119881119864infin1198981
and 119881119864infin1198982
arereported in Table 5 From this table it is seen that these valuesare positive from which we conclude that weak interactionsexist among the unlike molecules of the liquid mixtures
FT-IR spectra of pure CH butanols and binary mixturesof CH with butanols at equal concentrations are depicted inFigures 8 9 and 10 According to Karunakar and Srinivas[23] the intensity of an absorption in the IR spectrum isrelated to the change in dipole moment that occurs duringthe vibration Consequently vibrations that produce a largechange in dipole moment (eg C=O stretch) result in amore intense absorption than those that result in a relativelymodest change in dipole (eg C=C) Vibrations that do notresult in a change in dipole moment (eg a symmetrical
0
5
10
15
20
25
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m1
(10
Figure 7 Variation of excess partial molar volume 1198811198641198981
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
n-ButanolCH
Wave number (cmminus1)
CH + n-Butanol
Figure 8 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and 119899-butanol in the ratio 5 5 (green) andpure 119899-butanol (blue)
8 Journal of Applied Chemistry
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
sec-ButanolCH
Wave number (cmminus1)
CH + sec-Butanol
Figure 9 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and sec-butanol in the ratio 5 5 (green) andpure sec-butanol (blue)
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
tert-ButanolCH
Wave number (cmminus1)
CH + tert-Butanol
Figure 10 Fourier transform infrared spectra of pure cyclohex-anone (red) cyclohexanone and tert-butanol in the ratio 5 5(green) and pure tert-butanol (blue)
alkyne CequivC stretch) will show little or no absorption for thisvibration In the present FT-IR spectra liquid mixture showsvery small variations in the intensity of the respective bondsthat is dipole moment and hence it supports that weakinteractions take place between the components of liquidmolecules
Theoretical evaluation of ultrasonic speed in binary liquidmixtures and its correlation to study molecular interactionhas been successfully done in recent years Ultrasonic speedsin liquid mixtures have been calculated and compared with
Table 5 Partial molar volumes (119881infin1198981
119881infin1198982
) and excess partial molarvolumes (119881119864infin
1198981 119881119864infin1198982
) of the components at infinite dilution for allthe systems at 30815 K
System 119881
infin
1198981119881
infin
1198982119881
119864infin
1198981119881
119864infin
1198982
(10minus5m3 molminus1)CH + 119899-butanol 25519 43758 18696 36548CH + 119904119890119888-butanol 25561 509205 19253 42933CH + 119905119890119903119905-butanol 30034 55000 23211 47790
experimental values using various theories Such an evalua-tion offers a simple method to investigate molecular interac-tions besides verifying the applicability of various theories toliquid mixtures
Nomoto [24] established the following relation for soundspeed (119880
119873) based on the assumption of the linearity of the
molecular sound speed and the additivity of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(14)
where 119877119894is molar sound speed and 119881
119894is molar volume
van Dael and Vangeel [25] obtained the ideal mixturerelation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(15)
Baluja and Parsania [26] have given impedance relationon the basis of force of resistance for sound speed by theinteracting molecules
119880imp =sum119909119894119885119894
sum119909119894120588119894
(16)
Raorsquos (specific sound speed) [27] relation is given by
119880119877= (sum119909
119894119903119894120588)
3
(17)
where 119903119894= 11990613
119894120588119894is Raorsquos specific sound speed of 119894th com-
ponent of the mixturePercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906exp 119905
] (18)
Table 6 shows the values of ultrasonic speed computed byvarious theories along with their percentage error for all thesystems The variations between the evaluated and experi-mental values may be due to interactions occurring betweenthe hetero molecules of the binaries From the observedvalues of all three systems there is a good agreementbetween theoretical and experimental values through vanDeal andVangeel relation It can be seen fromTable 6 that thetheoretical values of ultrasonic speed calculated by using var-ious theories show deviation from experimental values Thelimitations and approximation incorporated in these theories
Journal of Applied Chemistry 9
Table 6Theoretical values of ultrasonic speed from various equations and percentage error withmole fraction1199091of CH for all binary systems
at 30815 K
1199091
119880119873
119880119881
119880Imp 119880119877
119880119873
119880119881
119880Imp 119880119877
CH + 119899-butanol10000 136200 136200 136200 136200 000 000 000 00009121 135001 134547 135043 129806 143 109 146 24808854 134632 134060 134687 128317 177 133 181 30107211 132309 131199 132427 122196 305 218 314 48306687 131549 130334 131681 120973 322 227 332 50805232 129386 128042 129542 118502 333 226 346 53604752 128656 127319 128814 117871 317 210 330 54803231 126283 125129 126429 116393 261 168 273 54202112 124478 123609 124594 116166 196 125 205 48501313 123158 122567 123239 116883 135 086 142 38200000 120930 120930 120930 120930 000 000 000 000
CH + 119904119890119888-butanol10000 136200 136200 136200 136200 000 000 000 00009212 134836 134412 134936 128464 144 112 152 33508867 134234 133650 134375 125830 198 153 208 44107121 131130 129973 131435 117255 382 291 406 71606786 130524 129300 130852 116263 402 304 428 73505123 127465 126097 127860 113158 433 321 465 73804688 126650 125296 127049 112705 422 310 455 72603121 123666 122524 124027 112004 338 243 369 63702797 123039 121972 123381 112051 313 223 341 60801112 119722 119210 119901 113885 141 098 156 35300000 117480 117480 117480 117480 000 000 000 000
CH + 119905119890119903119905-butanol10000 136200 136200 136200 136200 000 000 000 00009221 134013 133538 134413 126923 209 173 240 33108895 133099 132456 133651 123600 283 233 325 45107012 127840 126544 129065 109588 561 454 663 94606814 127289 125953 128564 108550 578 467 684 98005112 122570 121104 124087 102359 633 506 764 112104777 121645 120195 123170 101661 627 501 761 111903321 117638 116400 119036 100406 548 437 674 99702635 115760 114696 117000 100794 480 384 592 87501323 112183 111575 112939 103339 289 233 358 52300000 108600 108600 108600 108600 000 000 000 000
are responsible for the deviations of theoretical values fromexperimental values Nomotorsquos theory proposes that the vol-ume does not change upon mixingTherefore no interactionbetween the components of liquid mixtures has been takeninto account Similarly the assumption for the formation ofideal mixing relation is that the ratios of specific heats of idealmixtures and the volumes are also equal Again no molecularinteractions are taken into account But upon mixing inter-actions between the molecules occur because of the presenceof various types of forces such as dispersion forces chargetransfer and hydrogen bonding dipole-dipole and dipole-induced dipole interactions Thus the observed deviationof theoretical values of speed from the experimental values
shows that the molecular interactions are taking placebetween the CH and isomers of butanol molecules Thedeviations of experimental values and values calculated fromimpedance relation and Raorsquos relation imply nonadditivity ofacoustic impedance and Raorsquos speed in the liquid mixturesAmong all the empirical theories van Dael and Vangeelsrelation gives better estimate of experimental values of soundspeed in all the systems In the present binary systems thedifference between experimental and theoretical speeds isgreater where themole fraction of CH varies in the region 03to 06 Hence it can be qualitatively inferred that the strengthof interaction in the binary mixtures is more in this range ofcomposition of CH with isomers of butanol liquid system
10 Journal of Applied Chemistry
5 Conclusion
(i) Ultrasonic speeds 119906 and densities 120588 of mixtures ofcyclohexanone with 119899-butanol or sec-butanol or tert-butanol over the entire composition range have beenmeasured at 119879 = 30815K
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119911119864 and Δ119906 are calculated
from experimental data of density and ultrasonicspeed The excess and deviation properties have beenfitted to Redlich-Kister type polynomial and corre-sponding standard deviations have been evaluatedThe observed positive values of 119881119864
119898 Δ119896119904 and 119871119864
119891and
negative values of 119911119864 Δ119906 for all the liquid mixturesstudied clearly indicate the presence of weak inter-actions such as rupturing of hydrogen bond or reduc-tion in H-bond strength of butanol or breaking ofthe structure of one or both of the components in asolution
(iii) The deviationexcess properties have been fitted toRedlich-Kister type polynomial and the correspond-ing standard deviations have been calculated
(iv) The calculated values of partial molar volumes havealso been examined The observed higher partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate weak interactions present in the systems
(v) The strength of interaction in themixtures follows theorder CH + tert-butanol gt sec-butanol gt 119899-butanol
(vi) FT-IR spectra for the present binary mixture alsosupport the conclusions drawn from the 119881119864
119898 119871119864119891 Δ119896119904
Δ119906 and 119911119864(vii) Further theoretical values of sound speed in the mix-
tures have been evaluated using various theories andhave been compared with experimental sound speedsto verify the applicability of such theories to the sys-tems studied
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
One of the authors SkMdNayeem is thankful to UGC NewDelhi Government of India for the financial grants towardsMRP (MRP-467114C (SERO-UGC))
References
[1] T B Thoe D K Aspinwall and M L H Wise ldquoReview onultrasonic machiningrdquo International Journal of Machine Toolsand Manufacture vol 38 no 4 pp 239ndash255 1998
[2] G Thomas Chemistry for Pharmacy and the Life SciencesPrentice Hall London UK 1996
[3] A M Ababneh C C Large and S Georghiou ldquoSolvation ofnucleosides in aqueous mixtures of organic solvents relevanceto dna open basepairsrdquo Biophysical Journal vol 85 no 2 pp1111ndash1127 2003
[4] R E Treybal Mass Transfer Operations McGraw Hill Singa-pore 3rd edition 1981
[5] 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 atT = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[6] PGnanaKumari PVenkatesuMV PrabhakaraRaoM-J Leeand H-M Lin ldquoExcess molar volumes and ultrasonic studiesof 119873-methyl-2-pyrrolidone with ketones at 119879 = 30315 Krdquo TheJournal of ChemicalThermodynamics vol 41 no 5 pp 586ndash5902009
[7] M Sreenivasulu and P R Naidu ldquoExcess volumes and adiabaticcompressibility of binary mixtures of butyl amine and cyclicketonesrdquo Australian Journal of Chemistry vol 32 no 8 pp1649ndash1652 1979
[8] K Rajagopal and S Chenthilnath ldquoExcess thermodynamicstudies of binary liquid mixtures of 2-methyl-2-propanol withketonesrdquo Indian Journal of Pure amp Applied Physics vol 48 no5 pp 326ndash333 2010
[9] R K Bachu M K Patwari S Boodida and S Nallani ldquoVol-umetric and transport properties of binary liquid mixtures ofaliphatic ketones with phenylacetonitrile at T = 30815 Krdquo Jour-nal of Chemical amp Engineering Data vol 53 no 10 pp 2403ndash2407 2008
[10] N G Tsierkezos I E Molinou and A C Filippou ldquoThermo-dynamic properties of binary mixtures of cyclohexanone with119899-alkanols (C
1-C5) at 29315 Krdquo Journal of Solution Chemistry
vol 34 no 12 pp 1371ndash1386 2005[11] M Sri Lakshmi R R Raju C Rambabu G V R Rao and
K Narendra ldquoStudy of molecular interactions in binary liquidmixtures containing higher alcohols at different temperaturesrdquoResearchampReviews Journal of Chemistry vol 2 no 1 pp 12ndash242013
[12] A I Vogel Text Book of Practical Organic Chemistry LongmanLondon UK 5th edition 1989
[13] J A Riddick W Bunger and T K Sakano Techniques of Chem-istry Organic Solvents Physical Properties andMethods of Purifi-cation Wiley Interscience New York NY USA 4th edition1987
[14] R K Bachu andM K Patwari ldquoDensities viscosities and speedof sound of binary mixtures of phenylacetonitrile with somealiphatic alcohols at 30815 Krdquo Indian Journal of Chemistry Avol 47 no 7 pp 1026ndash1031 2008
[15] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Journal of Physical Chemistry vol 29 pp 130ndash1371925
[16] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification solutionsrdquoIndustrial and Engineering Chemistry vol 40 no 2 pp 345ndash348 1948
[17] R Vijaya Kumar S Viswanathan and M Anand Rao ldquoExcessvolumes speeds of sound and isentropic compressibilitiesof 2-propyn-1-ol + 12-dichloroethane +111-trichloroe thane+1122-tetrachloroethane and +trichloroethylene at 30315Krdquo
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Applied Chemistry 7
Table 4 Partial molar volumes of CH (1198811198981
10minus5m3 molminus1) and butanols (1198811198982
10minus5m3 molminus1) of all the binary systems with mole fraction(1199091) of CH at 30815 K
CH + 119899-butanol CH + 119904119890119888-butanol CH + 119905119890119903119905-butanol1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
1199091
1198811198981
1198811198982
10000 7210 42676 10000 7210 49234 10000 7210 5461209121 7699 32512 09212 7681 38378 09221 7606 4459008854 7999 30035 08867 8130 34445 08895 7997 4078807211 10600 19303 07121 11586 20460 07012 12366 2341306687 11554 17041 06786 12354 18636 06814 12989 2202305232 14365 12385 05123 16219 12221 05112 19004 1308704752 15378 11198 04688 17234 11058 04777 20247 1189303231 19092 8232 03121 20995 8043 03321 25389 841602112 22264 6843 02797 21794 7619 02635 27459 756201313 24403 6314 01112 25586 6406 01323 30211 687400000 25905 6128 00000 26462 6307 00000 30421 6823
0
10
20
30
40
50
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m2
(10
Figure 6 Variation of excess partial molar volume 1198811198641198982
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
molar volumes ofCHand isomers of butanols in all the binaryliquid mixtures at infinite dilution 119881infin
1198981 119881infin1198982
119881119864infin1198981
and119881
119864infin
1198982 respectively were obtained by putting 119909 = 0 in (10)
and 119909 = 1 in (11) Consider
119881
119864infin
1198981= 1198600+ 1198601+ 1198602+ 1198603+ sdot sdot sdot = 119881
infin
1198981minus 119881lowast
1
119881
119864infin
1198982= 1198600minus 1198601+ 1198602minus 1198603+ sdot sdot sdot = 119881
infin
1198982minus 119881lowast
2
(13)
The pertinent values of 119881infin1198981
119881infin1198982
119881119864infin1198981
and 119881119864infin1198982
arereported in Table 5 From this table it is seen that these valuesare positive from which we conclude that weak interactionsexist among the unlike molecules of the liquid mixtures
FT-IR spectra of pure CH butanols and binary mixturesof CH with butanols at equal concentrations are depicted inFigures 8 9 and 10 According to Karunakar and Srinivas[23] the intensity of an absorption in the IR spectrum isrelated to the change in dipole moment that occurs duringthe vibration Consequently vibrations that produce a largechange in dipole moment (eg C=O stretch) result in amore intense absorption than those that result in a relativelymodest change in dipole (eg C=C) Vibrations that do notresult in a change in dipole moment (eg a symmetrical
0
5
10
15
20
25
0 02 04 06 08 1
minus5
m3
mol
minus1)
x1
VE m1
(10
Figure 7 Variation of excess partial molar volume 1198811198641198981
withmole fraction 119909
1 of cyclohexanone in (X) 119899-butanol(◼) sec-
butanol(998771) and tert-butanol at 30815 K
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
n-ButanolCH
Wave number (cmminus1)
CH + n-Butanol
Figure 8 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and 119899-butanol in the ratio 5 5 (green) andpure 119899-butanol (blue)
8 Journal of Applied Chemistry
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
sec-ButanolCH
Wave number (cmminus1)
CH + sec-Butanol
Figure 9 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and sec-butanol in the ratio 5 5 (green) andpure sec-butanol (blue)
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
tert-ButanolCH
Wave number (cmminus1)
CH + tert-Butanol
Figure 10 Fourier transform infrared spectra of pure cyclohex-anone (red) cyclohexanone and tert-butanol in the ratio 5 5(green) and pure tert-butanol (blue)
alkyne CequivC stretch) will show little or no absorption for thisvibration In the present FT-IR spectra liquid mixture showsvery small variations in the intensity of the respective bondsthat is dipole moment and hence it supports that weakinteractions take place between the components of liquidmolecules
Theoretical evaluation of ultrasonic speed in binary liquidmixtures and its correlation to study molecular interactionhas been successfully done in recent years Ultrasonic speedsin liquid mixtures have been calculated and compared with
Table 5 Partial molar volumes (119881infin1198981
119881infin1198982
) and excess partial molarvolumes (119881119864infin
1198981 119881119864infin1198982
) of the components at infinite dilution for allthe systems at 30815 K
System 119881
infin
1198981119881
infin
1198982119881
119864infin
1198981119881
119864infin
1198982
(10minus5m3 molminus1)CH + 119899-butanol 25519 43758 18696 36548CH + 119904119890119888-butanol 25561 509205 19253 42933CH + 119905119890119903119905-butanol 30034 55000 23211 47790
experimental values using various theories Such an evalua-tion offers a simple method to investigate molecular interac-tions besides verifying the applicability of various theories toliquid mixtures
Nomoto [24] established the following relation for soundspeed (119880
119873) based on the assumption of the linearity of the
molecular sound speed and the additivity of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(14)
where 119877119894is molar sound speed and 119881
119894is molar volume
van Dael and Vangeel [25] obtained the ideal mixturerelation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(15)
Baluja and Parsania [26] have given impedance relationon the basis of force of resistance for sound speed by theinteracting molecules
119880imp =sum119909119894119885119894
sum119909119894120588119894
(16)
Raorsquos (specific sound speed) [27] relation is given by
119880119877= (sum119909
119894119903119894120588)
3
(17)
where 119903119894= 11990613
119894120588119894is Raorsquos specific sound speed of 119894th com-
ponent of the mixturePercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906exp 119905
] (18)
Table 6 shows the values of ultrasonic speed computed byvarious theories along with their percentage error for all thesystems The variations between the evaluated and experi-mental values may be due to interactions occurring betweenthe hetero molecules of the binaries From the observedvalues of all three systems there is a good agreementbetween theoretical and experimental values through vanDeal andVangeel relation It can be seen fromTable 6 that thetheoretical values of ultrasonic speed calculated by using var-ious theories show deviation from experimental values Thelimitations and approximation incorporated in these theories
Journal of Applied Chemistry 9
Table 6Theoretical values of ultrasonic speed from various equations and percentage error withmole fraction1199091of CH for all binary systems
at 30815 K
1199091
119880119873
119880119881
119880Imp 119880119877
119880119873
119880119881
119880Imp 119880119877
CH + 119899-butanol10000 136200 136200 136200 136200 000 000 000 00009121 135001 134547 135043 129806 143 109 146 24808854 134632 134060 134687 128317 177 133 181 30107211 132309 131199 132427 122196 305 218 314 48306687 131549 130334 131681 120973 322 227 332 50805232 129386 128042 129542 118502 333 226 346 53604752 128656 127319 128814 117871 317 210 330 54803231 126283 125129 126429 116393 261 168 273 54202112 124478 123609 124594 116166 196 125 205 48501313 123158 122567 123239 116883 135 086 142 38200000 120930 120930 120930 120930 000 000 000 000
CH + 119904119890119888-butanol10000 136200 136200 136200 136200 000 000 000 00009212 134836 134412 134936 128464 144 112 152 33508867 134234 133650 134375 125830 198 153 208 44107121 131130 129973 131435 117255 382 291 406 71606786 130524 129300 130852 116263 402 304 428 73505123 127465 126097 127860 113158 433 321 465 73804688 126650 125296 127049 112705 422 310 455 72603121 123666 122524 124027 112004 338 243 369 63702797 123039 121972 123381 112051 313 223 341 60801112 119722 119210 119901 113885 141 098 156 35300000 117480 117480 117480 117480 000 000 000 000
CH + 119905119890119903119905-butanol10000 136200 136200 136200 136200 000 000 000 00009221 134013 133538 134413 126923 209 173 240 33108895 133099 132456 133651 123600 283 233 325 45107012 127840 126544 129065 109588 561 454 663 94606814 127289 125953 128564 108550 578 467 684 98005112 122570 121104 124087 102359 633 506 764 112104777 121645 120195 123170 101661 627 501 761 111903321 117638 116400 119036 100406 548 437 674 99702635 115760 114696 117000 100794 480 384 592 87501323 112183 111575 112939 103339 289 233 358 52300000 108600 108600 108600 108600 000 000 000 000
are responsible for the deviations of theoretical values fromexperimental values Nomotorsquos theory proposes that the vol-ume does not change upon mixingTherefore no interactionbetween the components of liquid mixtures has been takeninto account Similarly the assumption for the formation ofideal mixing relation is that the ratios of specific heats of idealmixtures and the volumes are also equal Again no molecularinteractions are taken into account But upon mixing inter-actions between the molecules occur because of the presenceof various types of forces such as dispersion forces chargetransfer and hydrogen bonding dipole-dipole and dipole-induced dipole interactions Thus the observed deviationof theoretical values of speed from the experimental values
shows that the molecular interactions are taking placebetween the CH and isomers of butanol molecules Thedeviations of experimental values and values calculated fromimpedance relation and Raorsquos relation imply nonadditivity ofacoustic impedance and Raorsquos speed in the liquid mixturesAmong all the empirical theories van Dael and Vangeelsrelation gives better estimate of experimental values of soundspeed in all the systems In the present binary systems thedifference between experimental and theoretical speeds isgreater where themole fraction of CH varies in the region 03to 06 Hence it can be qualitatively inferred that the strengthof interaction in the binary mixtures is more in this range ofcomposition of CH with isomers of butanol liquid system
10 Journal of Applied Chemistry
5 Conclusion
(i) Ultrasonic speeds 119906 and densities 120588 of mixtures ofcyclohexanone with 119899-butanol or sec-butanol or tert-butanol over the entire composition range have beenmeasured at 119879 = 30815K
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119911119864 and Δ119906 are calculated
from experimental data of density and ultrasonicspeed The excess and deviation properties have beenfitted to Redlich-Kister type polynomial and corre-sponding standard deviations have been evaluatedThe observed positive values of 119881119864
119898 Δ119896119904 and 119871119864
119891and
negative values of 119911119864 Δ119906 for all the liquid mixturesstudied clearly indicate the presence of weak inter-actions such as rupturing of hydrogen bond or reduc-tion in H-bond strength of butanol or breaking ofthe structure of one or both of the components in asolution
(iii) The deviationexcess properties have been fitted toRedlich-Kister type polynomial and the correspond-ing standard deviations have been calculated
(iv) The calculated values of partial molar volumes havealso been examined The observed higher partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate weak interactions present in the systems
(v) The strength of interaction in themixtures follows theorder CH + tert-butanol gt sec-butanol gt 119899-butanol
(vi) FT-IR spectra for the present binary mixture alsosupport the conclusions drawn from the 119881119864
119898 119871119864119891 Δ119896119904
Δ119906 and 119911119864(vii) Further theoretical values of sound speed in the mix-
tures have been evaluated using various theories andhave been compared with experimental sound speedsto verify the applicability of such theories to the sys-tems studied
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
One of the authors SkMdNayeem is thankful to UGC NewDelhi Government of India for the financial grants towardsMRP (MRP-467114C (SERO-UGC))
References
[1] T B Thoe D K Aspinwall and M L H Wise ldquoReview onultrasonic machiningrdquo International Journal of Machine Toolsand Manufacture vol 38 no 4 pp 239ndash255 1998
[2] G Thomas Chemistry for Pharmacy and the Life SciencesPrentice Hall London UK 1996
[3] A M Ababneh C C Large and S Georghiou ldquoSolvation ofnucleosides in aqueous mixtures of organic solvents relevanceto dna open basepairsrdquo Biophysical Journal vol 85 no 2 pp1111ndash1127 2003
[4] R E Treybal Mass Transfer Operations McGraw Hill Singa-pore 3rd edition 1981
[5] 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 atT = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[6] PGnanaKumari PVenkatesuMV PrabhakaraRaoM-J Leeand H-M Lin ldquoExcess molar volumes and ultrasonic studiesof 119873-methyl-2-pyrrolidone with ketones at 119879 = 30315 Krdquo TheJournal of ChemicalThermodynamics vol 41 no 5 pp 586ndash5902009
[7] M Sreenivasulu and P R Naidu ldquoExcess volumes and adiabaticcompressibility of binary mixtures of butyl amine and cyclicketonesrdquo Australian Journal of Chemistry vol 32 no 8 pp1649ndash1652 1979
[8] K Rajagopal and S Chenthilnath ldquoExcess thermodynamicstudies of binary liquid mixtures of 2-methyl-2-propanol withketonesrdquo Indian Journal of Pure amp Applied Physics vol 48 no5 pp 326ndash333 2010
[9] R K Bachu M K Patwari S Boodida and S Nallani ldquoVol-umetric and transport properties of binary liquid mixtures ofaliphatic ketones with phenylacetonitrile at T = 30815 Krdquo Jour-nal of Chemical amp Engineering Data vol 53 no 10 pp 2403ndash2407 2008
[10] N G Tsierkezos I E Molinou and A C Filippou ldquoThermo-dynamic properties of binary mixtures of cyclohexanone with119899-alkanols (C
1-C5) at 29315 Krdquo Journal of Solution Chemistry
vol 34 no 12 pp 1371ndash1386 2005[11] M Sri Lakshmi R R Raju C Rambabu G V R Rao and
K Narendra ldquoStudy of molecular interactions in binary liquidmixtures containing higher alcohols at different temperaturesrdquoResearchampReviews Journal of Chemistry vol 2 no 1 pp 12ndash242013
[12] A I Vogel Text Book of Practical Organic Chemistry LongmanLondon UK 5th edition 1989
[13] J A Riddick W Bunger and T K Sakano Techniques of Chem-istry Organic Solvents Physical Properties andMethods of Purifi-cation Wiley Interscience New York NY USA 4th edition1987
[14] R K Bachu andM K Patwari ldquoDensities viscosities and speedof sound of binary mixtures of phenylacetonitrile with somealiphatic alcohols at 30815 Krdquo Indian Journal of Chemistry Avol 47 no 7 pp 1026ndash1031 2008
[15] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Journal of Physical Chemistry vol 29 pp 130ndash1371925
[16] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification solutionsrdquoIndustrial and Engineering Chemistry vol 40 no 2 pp 345ndash348 1948
[17] R Vijaya Kumar S Viswanathan and M Anand Rao ldquoExcessvolumes speeds of sound and isentropic compressibilitiesof 2-propyn-1-ol + 12-dichloroethane +111-trichloroe thane+1122-tetrachloroethane and +trichloroethylene at 30315Krdquo
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
8 Journal of Applied Chemistry
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
sec-ButanolCH
Wave number (cmminus1)
CH + sec-Butanol
Figure 9 Fourier transform infrared spectra of pure cyclohexanone(red) cyclohexanone and sec-butanol in the ratio 5 5 (green) andpure sec-butanol (blue)
020
040
060
080
100
500 1375 2250 3125 4000
Tran
smitt
ance
()
tert-ButanolCH
Wave number (cmminus1)
CH + tert-Butanol
Figure 10 Fourier transform infrared spectra of pure cyclohex-anone (red) cyclohexanone and tert-butanol in the ratio 5 5(green) and pure tert-butanol (blue)
alkyne CequivC stretch) will show little or no absorption for thisvibration In the present FT-IR spectra liquid mixture showsvery small variations in the intensity of the respective bondsthat is dipole moment and hence it supports that weakinteractions take place between the components of liquidmolecules
Theoretical evaluation of ultrasonic speed in binary liquidmixtures and its correlation to study molecular interactionhas been successfully done in recent years Ultrasonic speedsin liquid mixtures have been calculated and compared with
Table 5 Partial molar volumes (119881infin1198981
119881infin1198982
) and excess partial molarvolumes (119881119864infin
1198981 119881119864infin1198982
) of the components at infinite dilution for allthe systems at 30815 K
System 119881
infin
1198981119881
infin
1198982119881
119864infin
1198981119881
119864infin
1198982
(10minus5m3 molminus1)CH + 119899-butanol 25519 43758 18696 36548CH + 119904119890119888-butanol 25561 509205 19253 42933CH + 119905119890119903119905-butanol 30034 55000 23211 47790
experimental values using various theories Such an evalua-tion offers a simple method to investigate molecular interac-tions besides verifying the applicability of various theories toliquid mixtures
Nomoto [24] established the following relation for soundspeed (119880
119873) based on the assumption of the linearity of the
molecular sound speed and the additivity of molar volume
119880119873=
(sum119909119894119877119894)
(sum119909119894119881119894)
3
(14)
where 119877119894is molar sound speed and 119881
119894is molar volume
van Dael and Vangeel [25] obtained the ideal mixturerelation
sum(
119909119894119872119894
1199062
119894
) =
1
sum119909119894119872119894
1
119880119881
2
(15)
Baluja and Parsania [26] have given impedance relationon the basis of force of resistance for sound speed by theinteracting molecules
119880imp =sum119909119894119885119894
sum119909119894120588119894
(16)
Raorsquos (specific sound speed) [27] relation is given by
119880119877= (sum119909
119894119903119894120588)
3
(17)
where 119903119894= 11990613
119894120588119894is Raorsquos specific sound speed of 119894th com-
ponent of the mixturePercentage deviation in ultrasonic speed is given by
Δ119906 = 100 lowast [1 minus119880cal119906exp 119905
] (18)
Table 6 shows the values of ultrasonic speed computed byvarious theories along with their percentage error for all thesystems The variations between the evaluated and experi-mental values may be due to interactions occurring betweenthe hetero molecules of the binaries From the observedvalues of all three systems there is a good agreementbetween theoretical and experimental values through vanDeal andVangeel relation It can be seen fromTable 6 that thetheoretical values of ultrasonic speed calculated by using var-ious theories show deviation from experimental values Thelimitations and approximation incorporated in these theories
Journal of Applied Chemistry 9
Table 6Theoretical values of ultrasonic speed from various equations and percentage error withmole fraction1199091of CH for all binary systems
at 30815 K
1199091
119880119873
119880119881
119880Imp 119880119877
119880119873
119880119881
119880Imp 119880119877
CH + 119899-butanol10000 136200 136200 136200 136200 000 000 000 00009121 135001 134547 135043 129806 143 109 146 24808854 134632 134060 134687 128317 177 133 181 30107211 132309 131199 132427 122196 305 218 314 48306687 131549 130334 131681 120973 322 227 332 50805232 129386 128042 129542 118502 333 226 346 53604752 128656 127319 128814 117871 317 210 330 54803231 126283 125129 126429 116393 261 168 273 54202112 124478 123609 124594 116166 196 125 205 48501313 123158 122567 123239 116883 135 086 142 38200000 120930 120930 120930 120930 000 000 000 000
CH + 119904119890119888-butanol10000 136200 136200 136200 136200 000 000 000 00009212 134836 134412 134936 128464 144 112 152 33508867 134234 133650 134375 125830 198 153 208 44107121 131130 129973 131435 117255 382 291 406 71606786 130524 129300 130852 116263 402 304 428 73505123 127465 126097 127860 113158 433 321 465 73804688 126650 125296 127049 112705 422 310 455 72603121 123666 122524 124027 112004 338 243 369 63702797 123039 121972 123381 112051 313 223 341 60801112 119722 119210 119901 113885 141 098 156 35300000 117480 117480 117480 117480 000 000 000 000
CH + 119905119890119903119905-butanol10000 136200 136200 136200 136200 000 000 000 00009221 134013 133538 134413 126923 209 173 240 33108895 133099 132456 133651 123600 283 233 325 45107012 127840 126544 129065 109588 561 454 663 94606814 127289 125953 128564 108550 578 467 684 98005112 122570 121104 124087 102359 633 506 764 112104777 121645 120195 123170 101661 627 501 761 111903321 117638 116400 119036 100406 548 437 674 99702635 115760 114696 117000 100794 480 384 592 87501323 112183 111575 112939 103339 289 233 358 52300000 108600 108600 108600 108600 000 000 000 000
are responsible for the deviations of theoretical values fromexperimental values Nomotorsquos theory proposes that the vol-ume does not change upon mixingTherefore no interactionbetween the components of liquid mixtures has been takeninto account Similarly the assumption for the formation ofideal mixing relation is that the ratios of specific heats of idealmixtures and the volumes are also equal Again no molecularinteractions are taken into account But upon mixing inter-actions between the molecules occur because of the presenceof various types of forces such as dispersion forces chargetransfer and hydrogen bonding dipole-dipole and dipole-induced dipole interactions Thus the observed deviationof theoretical values of speed from the experimental values
shows that the molecular interactions are taking placebetween the CH and isomers of butanol molecules Thedeviations of experimental values and values calculated fromimpedance relation and Raorsquos relation imply nonadditivity ofacoustic impedance and Raorsquos speed in the liquid mixturesAmong all the empirical theories van Dael and Vangeelsrelation gives better estimate of experimental values of soundspeed in all the systems In the present binary systems thedifference between experimental and theoretical speeds isgreater where themole fraction of CH varies in the region 03to 06 Hence it can be qualitatively inferred that the strengthof interaction in the binary mixtures is more in this range ofcomposition of CH with isomers of butanol liquid system
10 Journal of Applied Chemistry
5 Conclusion
(i) Ultrasonic speeds 119906 and densities 120588 of mixtures ofcyclohexanone with 119899-butanol or sec-butanol or tert-butanol over the entire composition range have beenmeasured at 119879 = 30815K
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119911119864 and Δ119906 are calculated
from experimental data of density and ultrasonicspeed The excess and deviation properties have beenfitted to Redlich-Kister type polynomial and corre-sponding standard deviations have been evaluatedThe observed positive values of 119881119864
119898 Δ119896119904 and 119871119864
119891and
negative values of 119911119864 Δ119906 for all the liquid mixturesstudied clearly indicate the presence of weak inter-actions such as rupturing of hydrogen bond or reduc-tion in H-bond strength of butanol or breaking ofthe structure of one or both of the components in asolution
(iii) The deviationexcess properties have been fitted toRedlich-Kister type polynomial and the correspond-ing standard deviations have been calculated
(iv) The calculated values of partial molar volumes havealso been examined The observed higher partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate weak interactions present in the systems
(v) The strength of interaction in themixtures follows theorder CH + tert-butanol gt sec-butanol gt 119899-butanol
(vi) FT-IR spectra for the present binary mixture alsosupport the conclusions drawn from the 119881119864
119898 119871119864119891 Δ119896119904
Δ119906 and 119911119864(vii) Further theoretical values of sound speed in the mix-
tures have been evaluated using various theories andhave been compared with experimental sound speedsto verify the applicability of such theories to the sys-tems studied
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
One of the authors SkMdNayeem is thankful to UGC NewDelhi Government of India for the financial grants towardsMRP (MRP-467114C (SERO-UGC))
References
[1] T B Thoe D K Aspinwall and M L H Wise ldquoReview onultrasonic machiningrdquo International Journal of Machine Toolsand Manufacture vol 38 no 4 pp 239ndash255 1998
[2] G Thomas Chemistry for Pharmacy and the Life SciencesPrentice Hall London UK 1996
[3] A M Ababneh C C Large and S Georghiou ldquoSolvation ofnucleosides in aqueous mixtures of organic solvents relevanceto dna open basepairsrdquo Biophysical Journal vol 85 no 2 pp1111ndash1127 2003
[4] R E Treybal Mass Transfer Operations McGraw Hill Singa-pore 3rd edition 1981
[5] 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 atT = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[6] PGnanaKumari PVenkatesuMV PrabhakaraRaoM-J Leeand H-M Lin ldquoExcess molar volumes and ultrasonic studiesof 119873-methyl-2-pyrrolidone with ketones at 119879 = 30315 Krdquo TheJournal of ChemicalThermodynamics vol 41 no 5 pp 586ndash5902009
[7] M Sreenivasulu and P R Naidu ldquoExcess volumes and adiabaticcompressibility of binary mixtures of butyl amine and cyclicketonesrdquo Australian Journal of Chemistry vol 32 no 8 pp1649ndash1652 1979
[8] K Rajagopal and S Chenthilnath ldquoExcess thermodynamicstudies of binary liquid mixtures of 2-methyl-2-propanol withketonesrdquo Indian Journal of Pure amp Applied Physics vol 48 no5 pp 326ndash333 2010
[9] R K Bachu M K Patwari S Boodida and S Nallani ldquoVol-umetric and transport properties of binary liquid mixtures ofaliphatic ketones with phenylacetonitrile at T = 30815 Krdquo Jour-nal of Chemical amp Engineering Data vol 53 no 10 pp 2403ndash2407 2008
[10] N G Tsierkezos I E Molinou and A C Filippou ldquoThermo-dynamic properties of binary mixtures of cyclohexanone with119899-alkanols (C
1-C5) at 29315 Krdquo Journal of Solution Chemistry
vol 34 no 12 pp 1371ndash1386 2005[11] M Sri Lakshmi R R Raju C Rambabu G V R Rao and
K Narendra ldquoStudy of molecular interactions in binary liquidmixtures containing higher alcohols at different temperaturesrdquoResearchampReviews Journal of Chemistry vol 2 no 1 pp 12ndash242013
[12] A I Vogel Text Book of Practical Organic Chemistry LongmanLondon UK 5th edition 1989
[13] J A Riddick W Bunger and T K Sakano Techniques of Chem-istry Organic Solvents Physical Properties andMethods of Purifi-cation Wiley Interscience New York NY USA 4th edition1987
[14] R K Bachu andM K Patwari ldquoDensities viscosities and speedof sound of binary mixtures of phenylacetonitrile with somealiphatic alcohols at 30815 Krdquo Indian Journal of Chemistry Avol 47 no 7 pp 1026ndash1031 2008
[15] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Journal of Physical Chemistry vol 29 pp 130ndash1371925
[16] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification solutionsrdquoIndustrial and Engineering Chemistry vol 40 no 2 pp 345ndash348 1948
[17] R Vijaya Kumar S Viswanathan and M Anand Rao ldquoExcessvolumes speeds of sound and isentropic compressibilitiesof 2-propyn-1-ol + 12-dichloroethane +111-trichloroe thane+1122-tetrachloroethane and +trichloroethylene at 30315Krdquo
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Applied Chemistry 9
Table 6Theoretical values of ultrasonic speed from various equations and percentage error withmole fraction1199091of CH for all binary systems
at 30815 K
1199091
119880119873
119880119881
119880Imp 119880119877
119880119873
119880119881
119880Imp 119880119877
CH + 119899-butanol10000 136200 136200 136200 136200 000 000 000 00009121 135001 134547 135043 129806 143 109 146 24808854 134632 134060 134687 128317 177 133 181 30107211 132309 131199 132427 122196 305 218 314 48306687 131549 130334 131681 120973 322 227 332 50805232 129386 128042 129542 118502 333 226 346 53604752 128656 127319 128814 117871 317 210 330 54803231 126283 125129 126429 116393 261 168 273 54202112 124478 123609 124594 116166 196 125 205 48501313 123158 122567 123239 116883 135 086 142 38200000 120930 120930 120930 120930 000 000 000 000
CH + 119904119890119888-butanol10000 136200 136200 136200 136200 000 000 000 00009212 134836 134412 134936 128464 144 112 152 33508867 134234 133650 134375 125830 198 153 208 44107121 131130 129973 131435 117255 382 291 406 71606786 130524 129300 130852 116263 402 304 428 73505123 127465 126097 127860 113158 433 321 465 73804688 126650 125296 127049 112705 422 310 455 72603121 123666 122524 124027 112004 338 243 369 63702797 123039 121972 123381 112051 313 223 341 60801112 119722 119210 119901 113885 141 098 156 35300000 117480 117480 117480 117480 000 000 000 000
CH + 119905119890119903119905-butanol10000 136200 136200 136200 136200 000 000 000 00009221 134013 133538 134413 126923 209 173 240 33108895 133099 132456 133651 123600 283 233 325 45107012 127840 126544 129065 109588 561 454 663 94606814 127289 125953 128564 108550 578 467 684 98005112 122570 121104 124087 102359 633 506 764 112104777 121645 120195 123170 101661 627 501 761 111903321 117638 116400 119036 100406 548 437 674 99702635 115760 114696 117000 100794 480 384 592 87501323 112183 111575 112939 103339 289 233 358 52300000 108600 108600 108600 108600 000 000 000 000
are responsible for the deviations of theoretical values fromexperimental values Nomotorsquos theory proposes that the vol-ume does not change upon mixingTherefore no interactionbetween the components of liquid mixtures has been takeninto account Similarly the assumption for the formation ofideal mixing relation is that the ratios of specific heats of idealmixtures and the volumes are also equal Again no molecularinteractions are taken into account But upon mixing inter-actions between the molecules occur because of the presenceof various types of forces such as dispersion forces chargetransfer and hydrogen bonding dipole-dipole and dipole-induced dipole interactions Thus the observed deviationof theoretical values of speed from the experimental values
shows that the molecular interactions are taking placebetween the CH and isomers of butanol molecules Thedeviations of experimental values and values calculated fromimpedance relation and Raorsquos relation imply nonadditivity ofacoustic impedance and Raorsquos speed in the liquid mixturesAmong all the empirical theories van Dael and Vangeelsrelation gives better estimate of experimental values of soundspeed in all the systems In the present binary systems thedifference between experimental and theoretical speeds isgreater where themole fraction of CH varies in the region 03to 06 Hence it can be qualitatively inferred that the strengthof interaction in the binary mixtures is more in this range ofcomposition of CH with isomers of butanol liquid system
10 Journal of Applied Chemistry
5 Conclusion
(i) Ultrasonic speeds 119906 and densities 120588 of mixtures ofcyclohexanone with 119899-butanol or sec-butanol or tert-butanol over the entire composition range have beenmeasured at 119879 = 30815K
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119911119864 and Δ119906 are calculated
from experimental data of density and ultrasonicspeed The excess and deviation properties have beenfitted to Redlich-Kister type polynomial and corre-sponding standard deviations have been evaluatedThe observed positive values of 119881119864
119898 Δ119896119904 and 119871119864
119891and
negative values of 119911119864 Δ119906 for all the liquid mixturesstudied clearly indicate the presence of weak inter-actions such as rupturing of hydrogen bond or reduc-tion in H-bond strength of butanol or breaking ofthe structure of one or both of the components in asolution
(iii) The deviationexcess properties have been fitted toRedlich-Kister type polynomial and the correspond-ing standard deviations have been calculated
(iv) The calculated values of partial molar volumes havealso been examined The observed higher partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate weak interactions present in the systems
(v) The strength of interaction in themixtures follows theorder CH + tert-butanol gt sec-butanol gt 119899-butanol
(vi) FT-IR spectra for the present binary mixture alsosupport the conclusions drawn from the 119881119864
119898 119871119864119891 Δ119896119904
Δ119906 and 119911119864(vii) Further theoretical values of sound speed in the mix-
tures have been evaluated using various theories andhave been compared with experimental sound speedsto verify the applicability of such theories to the sys-tems studied
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
One of the authors SkMdNayeem is thankful to UGC NewDelhi Government of India for the financial grants towardsMRP (MRP-467114C (SERO-UGC))
References
[1] T B Thoe D K Aspinwall and M L H Wise ldquoReview onultrasonic machiningrdquo International Journal of Machine Toolsand Manufacture vol 38 no 4 pp 239ndash255 1998
[2] G Thomas Chemistry for Pharmacy and the Life SciencesPrentice Hall London UK 1996
[3] A M Ababneh C C Large and S Georghiou ldquoSolvation ofnucleosides in aqueous mixtures of organic solvents relevanceto dna open basepairsrdquo Biophysical Journal vol 85 no 2 pp1111ndash1127 2003
[4] R E Treybal Mass Transfer Operations McGraw Hill Singa-pore 3rd edition 1981
[5] 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 atT = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[6] PGnanaKumari PVenkatesuMV PrabhakaraRaoM-J Leeand H-M Lin ldquoExcess molar volumes and ultrasonic studiesof 119873-methyl-2-pyrrolidone with ketones at 119879 = 30315 Krdquo TheJournal of ChemicalThermodynamics vol 41 no 5 pp 586ndash5902009
[7] M Sreenivasulu and P R Naidu ldquoExcess volumes and adiabaticcompressibility of binary mixtures of butyl amine and cyclicketonesrdquo Australian Journal of Chemistry vol 32 no 8 pp1649ndash1652 1979
[8] K Rajagopal and S Chenthilnath ldquoExcess thermodynamicstudies of binary liquid mixtures of 2-methyl-2-propanol withketonesrdquo Indian Journal of Pure amp Applied Physics vol 48 no5 pp 326ndash333 2010
[9] R K Bachu M K Patwari S Boodida and S Nallani ldquoVol-umetric and transport properties of binary liquid mixtures ofaliphatic ketones with phenylacetonitrile at T = 30815 Krdquo Jour-nal of Chemical amp Engineering Data vol 53 no 10 pp 2403ndash2407 2008
[10] N G Tsierkezos I E Molinou and A C Filippou ldquoThermo-dynamic properties of binary mixtures of cyclohexanone with119899-alkanols (C
1-C5) at 29315 Krdquo Journal of Solution Chemistry
vol 34 no 12 pp 1371ndash1386 2005[11] M Sri Lakshmi R R Raju C Rambabu G V R Rao and
K Narendra ldquoStudy of molecular interactions in binary liquidmixtures containing higher alcohols at different temperaturesrdquoResearchampReviews Journal of Chemistry vol 2 no 1 pp 12ndash242013
[12] A I Vogel Text Book of Practical Organic Chemistry LongmanLondon UK 5th edition 1989
[13] J A Riddick W Bunger and T K Sakano Techniques of Chem-istry Organic Solvents Physical Properties andMethods of Purifi-cation Wiley Interscience New York NY USA 4th edition1987
[14] R K Bachu andM K Patwari ldquoDensities viscosities and speedof sound of binary mixtures of phenylacetonitrile with somealiphatic alcohols at 30815 Krdquo Indian Journal of Chemistry Avol 47 no 7 pp 1026ndash1031 2008
[15] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Journal of Physical Chemistry vol 29 pp 130ndash1371925
[16] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification solutionsrdquoIndustrial and Engineering Chemistry vol 40 no 2 pp 345ndash348 1948
[17] R Vijaya Kumar S Viswanathan and M Anand Rao ldquoExcessvolumes speeds of sound and isentropic compressibilitiesof 2-propyn-1-ol + 12-dichloroethane +111-trichloroe thane+1122-tetrachloroethane and +trichloroethylene at 30315Krdquo
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
10 Journal of Applied Chemistry
5 Conclusion
(i) Ultrasonic speeds 119906 and densities 120588 of mixtures ofcyclohexanone with 119899-butanol or sec-butanol or tert-butanol over the entire composition range have beenmeasured at 119879 = 30815K
(ii) The values of 119881119864119898 Δ119896119904 119871119864119891 119911119864 and Δ119906 are calculated
from experimental data of density and ultrasonicspeed The excess and deviation properties have beenfitted to Redlich-Kister type polynomial and corre-sponding standard deviations have been evaluatedThe observed positive values of 119881119864
119898 Δ119896119904 and 119871119864
119891and
negative values of 119911119864 Δ119906 for all the liquid mixturesstudied clearly indicate the presence of weak inter-actions such as rupturing of hydrogen bond or reduc-tion in H-bond strength of butanol or breaking ofthe structure of one or both of the components in asolution
(iii) The deviationexcess properties have been fitted toRedlich-Kister type polynomial and the correspond-ing standard deviations have been calculated
(iv) The calculated values of partial molar volumes havealso been examined The observed higher partialmolar volumes in the liquid mixture when comparedto the respective molar volumes of pure componentsindicate weak interactions present in the systems
(v) The strength of interaction in themixtures follows theorder CH + tert-butanol gt sec-butanol gt 119899-butanol
(vi) FT-IR spectra for the present binary mixture alsosupport the conclusions drawn from the 119881119864
119898 119871119864119891 Δ119896119904
Δ119906 and 119911119864(vii) Further theoretical values of sound speed in the mix-
tures have been evaluated using various theories andhave been compared with experimental sound speedsto verify the applicability of such theories to the sys-tems studied
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
One of the authors SkMdNayeem is thankful to UGC NewDelhi Government of India for the financial grants towardsMRP (MRP-467114C (SERO-UGC))
References
[1] T B Thoe D K Aspinwall and M L H Wise ldquoReview onultrasonic machiningrdquo International Journal of Machine Toolsand Manufacture vol 38 no 4 pp 239ndash255 1998
[2] G Thomas Chemistry for Pharmacy and the Life SciencesPrentice Hall London UK 1996
[3] A M Ababneh C C Large and S Georghiou ldquoSolvation ofnucleosides in aqueous mixtures of organic solvents relevanceto dna open basepairsrdquo Biophysical Journal vol 85 no 2 pp1111ndash1127 2003
[4] R E Treybal Mass Transfer Operations McGraw Hill Singa-pore 3rd edition 1981
[5] 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 atT = (30315or 30815 or 31315) Krdquo Journal of Chemical and EngineeringData vol 54 no 6 pp 1947ndash1950 2009
[6] PGnanaKumari PVenkatesuMV PrabhakaraRaoM-J Leeand H-M Lin ldquoExcess molar volumes and ultrasonic studiesof 119873-methyl-2-pyrrolidone with ketones at 119879 = 30315 Krdquo TheJournal of ChemicalThermodynamics vol 41 no 5 pp 586ndash5902009
[7] M Sreenivasulu and P R Naidu ldquoExcess volumes and adiabaticcompressibility of binary mixtures of butyl amine and cyclicketonesrdquo Australian Journal of Chemistry vol 32 no 8 pp1649ndash1652 1979
[8] K Rajagopal and S Chenthilnath ldquoExcess thermodynamicstudies of binary liquid mixtures of 2-methyl-2-propanol withketonesrdquo Indian Journal of Pure amp Applied Physics vol 48 no5 pp 326ndash333 2010
[9] R K Bachu M K Patwari S Boodida and S Nallani ldquoVol-umetric and transport properties of binary liquid mixtures ofaliphatic ketones with phenylacetonitrile at T = 30815 Krdquo Jour-nal of Chemical amp Engineering Data vol 53 no 10 pp 2403ndash2407 2008
[10] N G Tsierkezos I E Molinou and A C Filippou ldquoThermo-dynamic properties of binary mixtures of cyclohexanone with119899-alkanols (C
1-C5) at 29315 Krdquo Journal of Solution Chemistry
vol 34 no 12 pp 1371ndash1386 2005[11] M Sri Lakshmi R R Raju C Rambabu G V R Rao and
K Narendra ldquoStudy of molecular interactions in binary liquidmixtures containing higher alcohols at different temperaturesrdquoResearchampReviews Journal of Chemistry vol 2 no 1 pp 12ndash242013
[12] A I Vogel Text Book of Practical Organic Chemistry LongmanLondon UK 5th edition 1989
[13] J A Riddick W Bunger and T K Sakano Techniques of Chem-istry Organic Solvents Physical Properties andMethods of Purifi-cation Wiley Interscience New York NY USA 4th edition1987
[14] R K Bachu andM K Patwari ldquoDensities viscosities and speedof sound of binary mixtures of phenylacetonitrile with somealiphatic alcohols at 30815 Krdquo Indian Journal of Chemistry Avol 47 no 7 pp 1026ndash1031 2008
[15] H C Parker and E W Parker ldquoDensities of certain aque-ous potassium chloride solutions as determined with a newpyknometerrdquo Journal of Physical Chemistry vol 29 pp 130ndash1371925
[16] O Redlich and A T Kister ldquoAlgebraic representation ofthermodynamic properties and the classification solutionsrdquoIndustrial and Engineering Chemistry vol 40 no 2 pp 345ndash348 1948
[17] R Vijaya Kumar S Viswanathan and M Anand Rao ldquoExcessvolumes speeds of sound and isentropic compressibilitiesof 2-propyn-1-ol + 12-dichloroethane +111-trichloroe thane+1122-tetrachloroethane and +trichloroethylene at 30315Krdquo
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Applied Chemistry 11
Journal of Chemical and EngineeringData vol 41 no 4 pp 755ndash757 1996
[18] J S Matos and J L Trenzado ldquoVolumetric properties and vis-cosities of the methyl butanoate+n-heptane+n-octane ternarysystem and its binary constitutions in the temperature rangefrom 28315K to 31315Krdquo Fluid Phase Equilibria vol 186 pp207ndash234 2001
[19] O Kiyohara and G C Benson ldquoUltrasonic speeds and isen-tropic compressibilities of n-alkanol + n-heptane mixtures at29815 KrdquoThe Journal of Chemical Thermodynamics vol 11 no9 pp 861ndash873 1979
[20] R J Fort and W R Moore ldquoAdiabatic compressibilities ofbinary liquidmixturesrdquo Transactions of the Faraday Society vol61 pp 2102ndash2111 1965
[21] A Ali A K Nain V K Sharma and S Ahmed ldquoUltrasonicstudies in binary liquid mixturesrdquo Indian Journal of Physics Bvol 75 no 6 pp 519ndash525 2001
[22] M Gowrisankar S Sivarambabu P Venkateswarlu and K SKumar ldquoExcess volumes speeds of sound isentropic compress-ibilities and viscosities of binary mixtures of 119873-ethyl anilinewith some aromatic ketones at 30315 Krdquo Bulletin of the KoreanChemical Society vol 33 no 5 pp 1686ndash1692 2012
[23] T Karunakar andCH Srinivas ldquoThermo acoustic and infraredstudy of molecular interactions in binary mixture aniline+1-butanolrdquo Research amp Reviews Journal of Pure and AppliedPhysics vol 1 no 1 pp 5ndash10 2013
[24] O Nomoto ldquoEmpirical formula for sound velocity in liquidmixturesrdquo Journal of the Physical Society of Japan vol 13 no12 pp 1528ndash1532 1958
[25] W van Dael Thermodynamic Properties and Velocity of SoundButterworth London UK 1975
[26] 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
[27] K Sreekanth D S Kumar M Kondaiah and D Krishna RaoldquoStudy of molecular interactions in the mixtures of secondaryalcohols with equimolar mixture of ethanol + formamide fromacoustic and thermodynamic parametersrdquo Journal of Chemicaland Pharmaceutical Research vol 3 no 4 pp 29ndash41 2011
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
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