Research Article Study of Transport Properties of Tris ... · Journalof Applied Chemistry...

Hindawi Publishing CorporationJournal of Applied ChemistryVolume 2013 Article ID 820153 4 pageshttpdxdoiorg1011552013820153

Research ArticleStudy of Transport Properties of Tris(hydroxymethyl)aminomethane Hydrochloride in 20 (vv)Acetone-Water System at 30315∘K

Ajita Dixit

Rungta College of Engineering and Technology Near Nandanvan Veer Savarkar Nagar Raipur (CG) 492010 India

Correspondence should be addressed to Ajita Dixit ajitadixitgmailcom

Received 23 April 2013 Accepted 18 July 2013

Academic Editor Stoyan Karakashev

Copyright copy 2013 Ajita Dixit This is an open access article distributed under the Creative Commons Attribution License whichpermits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Viscometric properties of Tris-(hydroxymethyl)amino methane hydrochloride are measured in 20 (vv) acetone-water system30315∘K The related parameters are the experimental values of viscosity (120578) allow to determine relative viscosity (120578

119903

) viscosity119861-coefficient of the Jones-Dole equation free energies of activation of viscous flow Δ1205830 =

1

and Δ1205830 =2

per mole solvent and soluterespectivelyThe excessmolar volume excess viscosity excess Gibbrsquos free energy and interaction parameter of Grunberg andNissanhave also been calculated These studies are of great help in characterizing the structure and properties of solutions The additionof an organic solvent to water brings about a sharp change in the solvation of ions

1 Introduction

The density is one of the key thermodynamic propertiesof electrolyte solutions and belongs with an equilibriumproperty while the viscosity is one of the key transportproperties of electrolyte solutions andbelongswith a dynamicstate property Both of them rein dispensable basic data toengineering design and process optimization Knowledge ofviscometric properties studied in binary solvent system isuseful for engineering design of new applications Viscositiesare important physico-chemical parameters widely studiedin aqueous aqueous-organic and others [1] The density andviscosity are important basic data used in chemical engineer-ing designs solution theory and molecular thermodynamics[2] Physicochemical processes of electrolyte solutions are ofconsiderable interest due to their importance in numerousindustrial processes Extensive experimental viscosity dataare available for mixed-solvent system In mixed-solventelectrolyte solutions viscosity is affected by the concentrationof electrolytes but also by the composition of the solventEven the viscosity of solvent mixtures may show a complexbehavior and change significantly with composition Theknowledge of physico-chemical properties of liquid mixturesof two or more components are of theoretical and industrial

importance due to their wide range of applicability as solventmedia in various physico-chemical processes In the presentinvestigation following parameters aremeasured by Viscositydata of tris (hydroxymethyl)aminomethane hydrochloride ismeasured in 20 (vv) acetone-water system 30315∘K is usedto determine B-coefficient (B) and constant characteristic ofion-ion interactions (119860) excess viscosity (119881119864) and excessmolar free energy of activation of flow (119866119864) The interactionparameters Gruenberg and Nissan (d) were also calculatedand reportedThe parameters are analyzed to be evaluated tounderstand solute-solvent interaction

2 Experiment

A stock solution of 0100M tris (hydroxymethyl)amino-methane hydrochloride is prepared in 20 (vv) acetone-water solvent by direct weighing Mass dilution techniqueused for preparation of other concentrations The concentra-tion of the solutions involved in the experiment was takenin range from 0010M to 0100M Mass dilution techniquewas applied to prepare the solution of different concentrationViscosities weremeasured by capillary viscometer of ostwald-Sprengel type (MaHaRaNa Instruments MFG-Company

2 Journal of Applied Chemistry

Table 1 Viscosities and densities of tris (hydroxymethyl)amino-methane hydrochloride in 20 (vv) acetone-water system at30315∘K

Concentration(mol dmminus3)

Density (120588)gm cmminus3

Viscosity (120578)mPa s

00100 09436 0930700200 09446 0967800300 09458 1014200400 09465 1034400500 09475 1119600600 09493 1167100700 09506 1233700800 09528 1301500900 09541 1368601000 09551 15004

Table 2 Excess molar volume and excess viscosity of tris (hydrox-ymethyl)aminomethane hydrochloride in 20 (vv) acetone-watersystem at 30315∘K


Excess molar volume(119881119864)

Excess viscosity(120578119864)

00100 12691 minus0025700200 02639 0011300300 02360 0057700400 02169 0078000500 01935 0163200600 01526 0210700700 01206 0277300800 00713 0345200900 00396 0412201000 00165 05441

(I am not related to MFG company commercially) AjmerIndia) with accuracy of 01 K The Viscometer was calibratedwith triple distilled water Viscosity values were determinedusing the relation

120578 = 120588 (119870119905 minus119871

119905) (1)

where 120578 is a viscosity 120588 is the density of the liquid 119905 is theflow time and 119870 and 119871 are constants for given viscometerThe flow time was measured with digital stop watch withaccuracy of plusmn 001 sec The 119870 and 119871 were obtained by mea-suring the flow time of triple distilled water at temperature30315∘K All measurements were carried out in triplicate

3 Result and Discussion

31 Viscosities and Densities The values of viscosities anddensities are reported in Table 1 Viscosities of the solutionare increasing with the increase in concentration

32 Excess Molar Volume and Excess Viscosity

321 Excess Molar Volume It is calculated from followingexpression

119881119864

= 119881 minus (11988311198811+ 11988321198812) (2)

where 119881 = Molar volume of Tris-(hydroxymethyl)aminomethane hydrochloride solution119881

1=Molar volumeofmixed

solvent 1198812= Molar volume of solute 119883

1= Mole fraction of

solvent and1198832= Mole fraction solute

The data are shown in Table 2

322 Excess Viscosity The mixing of different compoundsgives rise to solutions that generally do not behave ideallyThe deviation from ideality is expressed by many ther-modynamic properties particularly by excess or residualextensive properties Excess thermodynamic properties ofmixtures correspond with the difference among the actualproperty and the property if the system behaves ideally andthus are useful in the study of molecular interactions andarrangements In particular they reflect the interactions thattake place among solute-solute solute-solvent and solvent-solvent species The excess viscosity (120578119864) has been evaluatedfrom the observed viscosity of the solution and that of its purecomponents using the relation [3]

120578119864

= 120578 minus (11988311205781+ 11988321205782) (3)

where 1205782= viscosity of solute

The data presented in Table 2 show that the 120578119864 valuesare positive in the entire concentration range at both thetemperatures This shows the presence of specific solute-solvent interactions such as hydrogen bond formation inthese systems [4]

33 B-Coefficients The Jones-Dole equation was used toanalyze the viscosities following the equation [5]

120578119903=120578

1205781

= 1 + 11986011988812

+ 119861119888 (4)

where 119860 = constant characteristic of ion-ion interactions119861 = constant characteristic of ion-solvent interactions and 119888= molar concentrations

The values of relative viscosities are presented in Table 3The Falkenhagan coefficient 119860 is also given for electrolytesThe B-coefficients obtained as slope of straight line have beenrecorded in Table 3

Einstein [6] proposed an equation

120578 = 1205781(1 + 25]) (5)

where ] = aggregate volume of the particles in a unit volumeof solution

The previous equation describes the concentrationdependence of the relative viscosity of solution of electrolyteThe coefficient of ] is 25] The term 25] is taken to be validfor electrolyte and it is equivalent to the product in BC in theJone-Doles equation The data are presented in Table 3

Journal of Applied Chemistry 3

34 Activation Parameter The viscosity data have also beenanalyzed on the basis of a transition state theory of relativeviscosity as suggested by Rama Rao et al [7] The viscosityB-coefficient is expressed by equation

119861 =

(1198810

1

minus 1198810

2

)

1000+

[(1198810

1

1000)Δ1205830 =

2

minus Δ1205830 =

1

]

RT

(6)

where 11988101

= partial molar volume of solvent 11988102

= partialmolar volume of solute Δ1205830 =

1

= free energy of activation permole of solvent Δ1205830 =

2

= free energy of activation permole ofsolute B = viscosity B-coefficient R = universal Gas constant(8314 JKminus1molminus1) and T = temperature (30315∘K)

341 Solvent Activation Parameter Δ1205830 =1

Δ1205830 =1

is calcu-lated from equation proposed by Eying et al

Δ1205830 =

1

= RT In(12057811198810

1

119867119873) (7)

where N = Avogadrorsquos number (6023 times 1023 gmsdotatom) H =Planckrsquos constant (6626 times 10minus34 Jsdotsec) and 120578

1= viscosity of

solvent

342 Solvent Activation ParameterΔ1205830 =2

Solvent activationparameter Δ1205830 =

2

is derived from following expression

Δ1205830 =

2

= Δ1205830 =

1

+ (RT1198810

1

)[1000119861 minus 1198810

1

minus 1198810

2

) (8)

The values of solvent Δ1205830 =1

and solute Δ1205830 =2

and activa-tion free energies are given in Table 4

According to Feakins model the greater the value ofΔ1205830 =

2

is the greater the structure ability of the solute isThe values of Δ1205830 =

2

are very large as compared to those ofΔ1205830 =

1

which suggests that the formation of transition state isaccompanied with breaking and distortion of intermolecularbonds

35 Excess Free Energy of Activation for Viscous Flow 119866119864 andInteraction Parameter 119889

351 Excess Free Energy of Activation for Viscous Flow 119866119864The extra-thermodynamic property excess Gibbrsquos free energyof activation of flow (119866119864) for the solution has been computedfrom the Eyring equation [8]

119866119864

= RT [In 120578119881 minus (1198831In 12057811198811+ 1198832In 12057821198812)] (9)

The values are listed in Table 5 The value of 119866119864 increaseswith the increase in concentration of solute and also increaseswith the increase in temperature suggesting the interactionsbecame stronger

Table 3 B-coefficient 119860 119861 of tris (hydroxymethyl)amino methanehydrochloride in 20 (vv) acetone-water system at 30315∘K

Concentration(mol dmminus3) 119861119888 119860 119861

00100 minus00057

01031 minus65591

00200 minus0045800300 minus0095900400 minus0117800500 minus0209900600 minus0261200700 minus0333100800 minus0406500900 minus0478901000 minus06214

Table 4 Activation parameters of tris (hydroxymethyl)amino-methane hydrochloride in 20 (vv) acetone-water system at30315∘K


Δ1205830 =

1

(in kJmolminus1) 105Δ1205830 =

2

(in kJmolminus1) 105

00100 26244 minus6483600200 26283 minus6479800300 26329 minus6475200400 26348 minus6473200500 26426 minus6465400600 26467 minus6461300700 26522 minus6455800800 26575 minus6450500900 26624 minus6445601000 26714 minus64365

Table 5 Excess molar free energy of activation of flow (119866119864) andGrunberg andNissan constant tris (hydroxymethyl)aminomethanehydrochloride in 20 (vv) acetone-water system at 30315∘K


Excess molar free energyof activation of flow (119866119864)

Grunberg and Nissan(119889)

00100 169678 0000100200 561698 0000400300 1030463 minus0001200400 1228588 minus0000700500 2027112 minus0000300600 2435637 minus0000200700 2990243 minus0000200800 3516797 minus0000300900 4017946 minus0000101000 4946975 minus00001

352 Interaction Parameter 119889 The impact of solute onviscosity is understood in terms of parameter 119889 whichis regarded as a measure of the strength of interaction


between components of solution It has been estimated usingrelationship proposed by Gruenberg and Nissan [9]

In 120578 = 1198831In 1205781+ 1198832In 1205782+ 11988311198832119889 (10)

where 119889 = Grunberg and Nissan parameter

119863 prop119882

RT (11)

where119882 = interaction energyThe values of 119889 are reported in Table 5

4 Conclusion

Knowledge of transport properties is important in all theseapplications to understand the molecular interactions Vis-cosity increases as a function of concentration and decreasesin increase in temperatures The values of B-coefficient showsolute-solvent interactions in the present systemsThe valuesΔ1205830 =

2

are very large as compared to those of Δ1205830 =1

whichsuggests that the formation of transition state is accompaniedwith breaking and distortion of intermolecular bonds Vol-umetric data are used to test molecular theories or modelsof solution to extend our understanding about molecularinteractions among components

Conflict of Interests

The author declare that she has no commercial relations withMFG Company

References

[1] S S Yadava Y Singh and N Kushwaha ldquoDensities andviscosities of alkylethanoates +cyclohexane +benzene +14-dimethylbenzene and +135-trimethylbenzene at 30815 KrdquoActa Chimica Slovenica vol 57 no 3 pp 707ndash715 2010

[2] X Z Yang and J Wang ldquoDensities and viscosities of 111015840-(pentane-15-diyl)-bis(pyridinium) dibromide in ethanol +water from (29315 to 34415) Krdquo Journal of Chemical ampEngineering Data vol 55 no 6 pp 2322ndash2325 2010

[3] G Jones and M Dole ldquoThe viscosity of aqueous solutions ofstrong electrolytes with special reference to barium chloriderdquoJournal of the American Chemical Society vol 51 no 10 pp2950ndash2964 1929

[4] D Feakins D J Freemantle and K G Lawerence ldquoTransitionstate treatment of the relative viscosity of electrolytic solutionsApplications to aqueous non-aqueous and methanol + watersystemsrdquo Journal of the Chemical Society Faraday Transactions1 vol 70 pp 795ndash806 1974

[5] M I Aralaguppi T M Aminabhavi R H Balundgi and S SJoshi ldquoThermodynamic interactions in mixtures of bromoformwith hydrocarbonsrdquo Journal of Physical Chemistry vol 95 no13 pp 5299ndash5308 1991

[6] A Pal and A Kumar ldquoViscosity of 1-propanol + ethylene glycoldimethyl + diethylene glycol dimethyl + tri-ethylene glycoldimethyl and + tetraethylene glycol dimethyl ethers at 2881529815 and 30815 Krdquo Indian Journal of Chemistry A vol 42 no11 pp 2708ndash2716 2003

[7] G V Rama Rao A V Sarma and C Rambabu ldquoEvaluation ofexcess thermodynamic properties in some binary mixtures ofo-chlorophenolrdquo Indian Journal of Chemistry A vol 43 no 12pp 2518ndash2528 2004

[8] L Grunberg ldquoThe viscosity of regular solutions systems involv-ing carbon tetrachloride benzene and cyclohexanerdquo Transac-tions of the Faraday Society vol 50 pp 1293ndash1303 1954

[9] L Grunberg and A H Nissan ldquoMixture law for viscosityrdquoNature vol 164 no 4175 pp 799ndash800 1949

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Table 1 Viscosities and densities of tris (hydroxymethyl)amino-methane hydrochloride in 20 (vv) acetone-water system at30315∘K


Density (120588)gm cmminus3

Viscosity (120578)mPa s

00100 09436 0930700200 09446 0967800300 09458 1014200400 09465 1034400500 09475 1119600600 09493 1167100700 09506 1233700800 09528 1301500900 09541 1368601000 09551 15004

Table 2 Excess molar volume and excess viscosity of tris (hydrox-ymethyl)aminomethane hydrochloride in 20 (vv) acetone-watersystem at 30315∘K


Excess molar volume(119881119864)

Excess viscosity(120578119864)

00100 12691 minus0025700200 02639 0011300300 02360 0057700400 02169 0078000500 01935 0163200600 01526 0210700700 01206 0277300800 00713 0345200900 00396 0412201000 00165 05441

(I am not related to MFG company commercially) AjmerIndia) with accuracy of 01 K The Viscometer was calibratedwith triple distilled water Viscosity values were determinedusing the relation

120578 = 120588 (119870119905 minus119871

119905) (1)

where 120578 is a viscosity 120588 is the density of the liquid 119905 is theflow time and 119870 and 119871 are constants for given viscometerThe flow time was measured with digital stop watch withaccuracy of plusmn 001 sec The 119870 and 119871 were obtained by mea-suring the flow time of triple distilled water at temperature30315∘K All measurements were carried out in triplicate

3 Result and Discussion

31 Viscosities and Densities The values of viscosities anddensities are reported in Table 1 Viscosities of the solutionare increasing with the increase in concentration

32 Excess Molar Volume and Excess Viscosity

321 Excess Molar Volume It is calculated from followingexpression

119881119864

= 119881 minus (11988311198811+ 11988321198812) (2)

where 119881 = Molar volume of Tris-(hydroxymethyl)aminomethane hydrochloride solution119881

1=Molar volumeofmixed

solvent 1198812= Molar volume of solute 119883

1= Mole fraction of

solvent and1198832= Mole fraction solute

The data are shown in Table 2

322 Excess Viscosity The mixing of different compoundsgives rise to solutions that generally do not behave ideallyThe deviation from ideality is expressed by many ther-modynamic properties particularly by excess or residualextensive properties Excess thermodynamic properties ofmixtures correspond with the difference among the actualproperty and the property if the system behaves ideally andthus are useful in the study of molecular interactions andarrangements In particular they reflect the interactions thattake place among solute-solute solute-solvent and solvent-solvent species The excess viscosity (120578119864) has been evaluatedfrom the observed viscosity of the solution and that of its purecomponents using the relation [3]

120578119864

= 120578 minus (11988311205781+ 11988321205782) (3)

where 1205782= viscosity of solute

The data presented in Table 2 show that the 120578119864 valuesare positive in the entire concentration range at both thetemperatures This shows the presence of specific solute-solvent interactions such as hydrogen bond formation inthese systems [4]

33 B-Coefficients The Jones-Dole equation was used toanalyze the viscosities following the equation [5]

120578119903=120578

1205781

= 1 + 11986011988812

+ 119861119888 (4)

where 119860 = constant characteristic of ion-ion interactions119861 = constant characteristic of ion-solvent interactions and 119888= molar concentrations

The values of relative viscosities are presented in Table 3The Falkenhagan coefficient 119860 is also given for electrolytesThe B-coefficients obtained as slope of straight line have beenrecorded in Table 3

Einstein [6] proposed an equation

120578 = 1205781(1 + 25]) (5)

where ] = aggregate volume of the particles in a unit volumeof solution

The previous equation describes the concentrationdependence of the relative viscosity of solution of electrolyteThe coefficient of ] is 25] The term 25] is taken to be validfor electrolyte and it is equivalent to the product in BC in theJone-Doles equation The data are presented in Table 3



119861 =

(1198810

1

minus 1198810

2

)

1000+

[(1198810

1

1000)Δ1205830 =

2

minus Δ1205830 =

1

]

RT

(6)

where 11988101



1


2



Δ1205830 =1


Δ1205830 =

1

= RT In(12057811198810

1

119867119873) (7)


1= viscosity of

solvent



2


Δ1205830 =

2

= Δ1205830 =

1

+ (RT1198810

1

)[1000119861 minus 1198810

1

minus 1198810

2

) (8)





2


2


1




119866119864

= RT [In 120578119881 minus (1198831In 12057811198811+ 1198832In 12057821198812)] (9)




00100 minus00057

01031 minus65591




Δ1205830 =

1


2











In 120578 = 1198831In 1205781+ 1198832In 1205782+ 11988311198832119889 (10)


119863 prop119882

RT (11)


4 Conclusion


2





References



















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



119861 =

(1198810

1

minus 1198810

2

)

1000+

[(1198810

1

1000)Δ1205830 =

2

minus Δ1205830 =

1

]

RT

(6)

where 11988101



1


2



Δ1205830 =1


Δ1205830 =

1

= RT In(12057811198810

1

119867119873) (7)


1= viscosity of

solvent



2


Δ1205830 =

2

= Δ1205830 =

1

+ (RT1198810

1

)[1000119861 minus 1198810

1

minus 1198810

2

) (8)





2


2


1




119866119864

= RT [In 120578119881 minus (1198831In 12057811198811+ 1198832In 12057821198812)] (9)




00100 minus00057

01031 minus65591




Δ1205830 =

1


2











In 120578 = 1198831In 1205781+ 1198832In 1205782+ 11988311198832119889 (10)


119863 prop119882

RT (11)


4 Conclusion


2





References



















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



In 120578 = 1198831In 1205781+ 1198832In 1205782+ 11988311198832119889 (10)


119863 prop119882

RT (11)


4 Conclusion


2





References



















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Research Article Study of Transport Properties of Tris ... · Journalof Applied Chemistry...

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