EXPERIMENTAL MEFL1OI)S

'rhe Puiity of chemical is an impoi tdlrl 'I~PCLL 111 .tny I ~ X ~ ) ~ ~ I I ~ I I ~ I I ~ ~ I ~

wotlr on thermodynnm~cpropeillcs The errulh thol inlsc lrl cxpcr~mct~tiil

measurcmenl8 are clue lo impui~tlcssuch us wale1 W h U~~ S I I hcd
~ I iL I hy 111~
chemicals, dissoc~ationof chemicals on standing 01 cxposuic, nssoci~tt~on
c l ~
A continuous check on the pu~ityof the cl1cm1cnl8 11, nn rmport<,rtdntpomt in
any expeument on lhermodynamlcs apall from ~nltlulp u ~lical~on
~

All the chemicals used in lhc piesent stitdy weie pm~ficd hy ihc
standard mcthods described in h t c i a l u ~ c ~ ~ ~

Dimethyl Sulphoxide was dried over freshly Ignited quick hme and then
vacuum distilled the m~ddlefraction was collected and vncuuln distilled The

process was rcpeated unlill the electiic conduclivity of the sample wah
'
reduced to 107/Q Cmi or less The purified satuplo was degassed by
successive cycles of cooling pumping and melting and then stoled over
mercury out of contact w ~ t halr and in the dark I t was found thal buhhlo

formation occured on mixing unless tho component was cat efully degassed

Toluene (BDH) was washed with coneentraled sulphuric ac~dseve~altimca,

until the acid developed no more colour it was then treated with sodmm
liydroxide solution, and the alkali was removed by washlng wllh walor Thls
was kept over anhydrous calcium chloride overnlghl and Lhe driod saniple
was refluxed w t h metallic sodlum for 8 hours and finally dlslillcd over
sodium.
Blomobonzene (BDH) was d i ~ e dwith calc~ulnchlo~ldu~ n fd~ ~ i ~ l ~ o n , ~ l l y
distilled undel ~ e d u ~ p~essure
ed

d sshaklng wlth 6 ml po~tlonsof

E t h y l b c n z o ~ ~( eN d ~ l c h )was p u ~ ~ f i eby
concentiated sulphur~ca c ~ duntll the layer was colourless tlnd then wilh
sodlnm carbonate solut~on The sample was then shalten with wale1 and
finally dued wdh magnoslum sulphaf,e Aftel iwo dtst~lldl~o~is
oval sodium,

the ~niddlefsact~onof the second dlsllllate was takon

Nitrobcnxeno (BDH)was drlcd ovor anhydious calcluln chlorldc f o ~two

days and the dued sample was dlstilled in u fiact~onatmngcoh~rnnLIII~CI
i educed pressure

1,2.Dlehloroetha11e (BDH)was washed wilh d~lutebolulion of potasblum

hydroxide and then w t b water It was dr~edover pl~ospho~ouspontox~dc
and
dlstilled t,wce and the middle fiact~onwas collected

l , l , l - ~ c h l o r o e t h n n (SD's)
e was washed wrth concentvatod hycl~ochlo~tc
a c ~ dand 10 per cent potasslum caibonate solul~on The sample was dliod
over calc~umchiorlde for 6 houis and frncllonally dlstllled

1,1,2,2-Tetraahloroetham(BDH) was stii~edw t h concentratedsulpllur~c

acld a t 8oocfor 10 minutes The coloured acid was romoved and again 26 ml

73
ol t,he acid was dddcd Tho I~quidwns then w i ~ s l ~wllll
~ t l w,ltc~,rll ~ctlovel
poh~sslumcalbondle and distdled ovel vncuum DUIrng tile rlisbll,il~oi~
.11)(1ul
0 5 grams of phenol was added as a slahdl/ci

Tr~ohloroethene(BDHJ was slcam-d~ut~llcd

from I 0 pciccnl ~ ~ d c ~ u r n
hydloxide s l u r ~ y The 011 phase wab cooled to -30°Cto -50°C uod ~ c cwin
removed by filtralloll Tllc filtinte was fiacbonally dlbllllcd The ~niddlc
frachon was collected 1n a recslvei coveled wit11 a blaclc papel

Tetraohloroethene (BDHI was dncd ovct sodlu~nsulpli~leand r~uchonKilly

d~stilled

Ethyl methyl ketone (BDI-I) was tleated sovcral t ~ r n cw~l h satulated

potasslum carbonate solution The two layers were then ~ e p e ~ d l e dThe
ketone layer was distilled lo re~novewatcl I1 was then d ~ l e dfol one day
ova anhydious potassrum carbonate and fiactlondly dlst~lled

Diethyl ketone (Fluka) was drled over nnhyd~oussodlum sulphatc foi Lwo

days and fractionally dlstllled

Methyl propyl ketone (Aldrich) was dlied ove~potasslum ca~bonatcfoi three

days, boiled for two hours and fract~onallydislllled

Methyl isobutyl ketone (BDI-I)was dr~edover potasmu~ncarhonato for three

days, then boiled for two hours and fracl~anallydlslllled
Cyelohoxanone (Fluha ) was d ~ ~ clotd 24 li<tota ovrt dtit~ytl~ous
5odt111t1
sulphate and i~act~onally
dlsl~llcdLwlcc

M e r c u ~ y was first 1~111ln a fine s t ~ c ~ th~ough

m, a long Ionglh 111 5 p o LCIIL
nltr~cacid nnd the ploccss was lepealed u hc~nndtl~nc Pinally, mc~l:~ny
w:l\
passed through a column of wale) I1 was then d~iedby nlc,mh ol'lill,o~p~lpel
and then run through a haldened liltel paper w ~ l h pm-hole at, tho apex 01 tho
cone The dlied sample was finally d~stilledLwcc under retluccd p~cssl~ro
using
Gallenkamp mercury d~stlllatlonappal atus

Water : Delolllsed water (Permut~teplocess) was d~st~lled

tl~rlec To each lltte
of the d~strllatewas added 0 2 grams of potasslum pelmangannte m d 0 5 ggrms
of sodlum hyd~oxlde Thls alkaline solution wafi slowly distilled fiom a pyrex
vessel and the mmlddle fiact~onwas collected Tlle pur~tyof Lhe sample w ~ s

checked by measuring the conductt~ity,

The boiling polnts corrected to one atmospheric piessure and densit~es

determined at 303 16 K are presenled m Table 2 1 along wlth thc literature
values'74 @ Dissolved gases m organ~cl~quldsare often n soulce ol bubble
format~onwhch introduces an error m denslty and excess volume In ordc~to
overcome this dlfficult,y all the liqu~dsare degassed
Table 2 1. Bolllng points and densities at 303 15 K of pure
components.

Bolllng pmnt K Density pig cm

Compw~ent
Present L~teratwe '1'" Picsent L~te~atnrc '""
work wol k
diinethylsulphoxide 460 20 460 15 109564L 109680'

ethylbenzene 409 30 409 34 0 85820 0 85820

bl oinobenzene 429 20 429 19 148148 1 48160

nitlobenzene 483 90 483 95 119340 119841
etl~ylmethylketone 35270 35219 0 79450 0 79452

methylpiopyl ketone 373 50 373 56 0 79658 0 79656

cyclohexanone 428 76 428 80 0 93755 0 03761

tetrachloioethene 39426 394 22 1FOGS0 160640

 EXCESS ENTIIALI'Y

In plinciple the mola~excess cnlhelpy II", may he dcitvod fioin tho

lempcratule dependence of thc excess Gibbs fico cnct gy

In piactlce t h s is not sdtisfadoly method, ah mcaburcnlonl ol G"

~ a i c l yextend over a lungc of niole llian 15 peicenl of thc tempci ature

The methods that have beon used to measuie the heals of mlxlng can

be broadly dlwded into slatie and dynam~cmethods Nlhough majoi~lyof the

woikers m t h ~ sfield have used static methods lhele are quite a few

references to the so.called continuous flow calor~mele~sIn the e o n t ~ ~ ~ u o u v

flow calorimeters accuiate detcimiiiatlon of flow lutes and tempciatu~e

changes are d~fficultsmce the quanlities used ate vei y small and lhorough

rnlxlng of the liquids may not be poss~blein thts lype of culo~imeter

The recent liteiature md~catestllal most of Lhe me8suicrnenls liavc

been made mth nchabatic cnlorimeters In an ndiabahc expenmant, the two

liquids are mlxed in a vessel whlch is thcrmally Isolated from its

sunoundmgs 1f'H is pos~live(endothermic) then there wlll be loweling of

the temperature In pracllce, electr~calenergy is usually supplied to the

calortmeter partially to nullik the temperature drop If 1 1 ~is negative

77
(exothe~m~c)
then the tompe~at~no i ~ i c soil ln~xnig A
of Llic cillo~~lnctc~

second experiment 1s necessdry to detc~mlncLhc .~monnLof cnc~gy 1crlu11rd

to produce Lhe same Lempe~alurerlse Allel n~ilrlyLwo idcnLlc,~I~ , l l oimct.cl

~ i

can be used7 A known amount of elect~lcdlenclgy 1s adder1 to thc hccond

cdorimetcr in such a way that the Lemperatu~cd~ffcroncobot.wocn tho Lwo

calo~imeteis~srsnim~sed
The two ~nnin~equne~ncnts
ol'mlxmg cdlo~11nctc1s

are (a) the absence of a vapoui space and (b) some mcanb Lo dlow fur the

volume change which occuis on inlxing ~ c ~ l a s h nhas

n ~ ~cvicwcdthe

mixlng colonmclers of the adiabatic type IIe ~onclndcdthdt ~liuslor thcin

were deficient in leims of the above iequnemenls The anc wli~chhas been

widely used and meets thc above requienients is Lhe one descilbcd by Lnrlun

and ~ c G l a s l i a n ~

An so thermal apparatus based on the Bunsen calo~imetei was

described by Malcom and owli ins on'^'^^ The mixmg vessel 1s surrounded

completely by a vessel contalninga liqtud, pol t of wh~ch16 frozen to give n

manlie around the inner walls. Any energy thus releafid or ahsol bed d u ~ ~ n g

the muring process causes meltlng or freezing of Lhe mantle and the volume

change that accompanies the process IS ineasured by the movcment of the

liquid or mercury in a capillary tube Buusen calor~meterscan be used to

measure energy changes for slow processes. A inqor disadvanlage is Lhal

measurements can only be made a t the meltlng Lemperaturo of the

colonmeter fluld Recently Davies and P c ~ t c h a r dhave

~ ~ d~scusscdin dotall

the stablllty and accuracy of Bunsen type calorimeters.

78
 Anothei type olcalo~imelel1s lhc isuthc~m:~ltllluhon cnlo~imrtcxl FIII

an cndothc~micsyslem, one component 1s blowly I ~ I J C C ~ 111to

C ~ ihc ~CIYIII<~

component w1i.h the simultaneous nddllion of olo~ti~cule n m a s ~ ~ l l i ~ l10u n l

mslntsln the calor~meterat constant temperaluie Iul u1111~1alus

.iuit,~hl~~
1o1

endolhe~m~c
systems was first descr~bcdby Mra7eky' and Van Ness Seve~.II

other calol~metersbased on the ori@nill design have been iapoilcd In Lhe

htel ature14 An appslatus wluch is mole suitable fa1 meas(111ngexothei I ~ I I L

enllialpies has been descr~bedby Vnn Ness and Gibbszl Mulalsam~and

Benson17 have constlvcted a slrnllol appxalus except that ihc cooling module

IS located in a second plug at the base of the vessel Tmakn el dl1\ des~libcd

an apparatus whlch uses thc same injccllon iechliique as the Van Ness type

calorimeter wlth a vessel of fixed dimensions In whlch mercury 1s displaced

as in the Stoke and Marsh type calor~meter A numbci of olhel isoihermal

dilution calorimeters whch contrun a vnpour space'""'" have been descr~bed

In a flow cala~~meter
the two hquids are Injected ~ n i mixing
o chamber

a1 a steady and known rate For an endothermic system the powel m the

heater is adjusted so that the temperature of the mlxed hquld is rest,ored to

that of the unmixcd l ~ q u ~Few

d measurements have been made wlth flaw

calorimeters The most accurate results are lhose by MeGIashan and

S t o e k l ~ ~ ~ ~ a rand
s t e~ dh o m s e n 'delcmned
~ a cahbrat~onconstant for

then LKB calor~meterby usmg various results determined by Marsh and Co-

workersL6 They estimated lhat Lhoir modified flow calor~nlelerwas

~ccu~.ilc
to about 2 J moll Goodwin ur~dNcwsli,iinL"hzivc dcici~hcd,i flow

caloi~mcte~
for use w ~ t halcohol dnd walci hy,yslcnlb

Picker and D~snoye~

sZ7have dosci ihed an inlcicsling cflloitrnc?lci Uy

~ e d u c ~ nLhe
g time talcen to rcach a steddy state and by cont~nuouslyvarynlg

the flow rat,es of the two liquids they managed lo obla~n(hc con~pleleexcczs

cntlialpy culve in less than one hot11 Bcckci e l nlLA, llave dcserihcd a

continuous method which iequlres two iuns lo covoi the whole cornpositloll

iange Onc cornpollen1 1s added at a constant rate lo a contu~iicicrf lixed

volume ~nrliallycontanlng the second coniponent The mole fiact~onof

m~xluregtadually changes in a known way dependmg on lhe flow late and

the volume Their caloilmete~was deslgned to have a veiy rupid response lo

hme so that h e mole Craclion versus excess onthulpy culve could bc recorded

In a cont~nuousmanner Comparison w ~ t hthe lest system, benzene +

carbontet~achlo~ideand chlorobenzene + toluene ~ndicate lhat the

calorimeter 1s capable of a plec~aonof shghtly bethi lhan one percenl

Major advantage of flow calor~meters1s that they a e more readlly adaptable

for measurements over a wlde range of temperature and plcssure

Description of the n e w Parr 1451 solution enlorimetor and

experimental proaedure

The new Parr 1461 soluhon calorimeter (cf Fig 2 1)was ueed in the

present work to determine the heats of m i n g of l~quldmixtu~es Thla

calo~imeterconsisls of a glass Dewar chamber wlth a rotating sample cell, a

 A 9 1 ~ 1 sp u s h r o d open5 the lornpk
cell to tort the r c o r t l o n

s t u r d y wooden Inrtrvrnrn
w i t h (1 sratn r t r i s t a n t
+,n,$h p r o v l d r r good th@rrnal
~ r u l o t o nand o term s u p p a r t
lnrrrltd through thecovrr d t r r
-1 16 cioscd Flxvd
bushlngr rncuv
r ~ g e c t o b l rttp
p l o ~ ~ r n o~t n tlh e

The entire calorlnslir

15 h l d ~ l t h l no
thm- walltd ctomkr.
steel shell w t t h 0
o t l h q ~ l dr e a c t o n 1 w t h
low-conductlvlhi
m l n l m ~ ml l a r l l g r

A t a t o t l n g 910% lomule
cell holds up to lo mi et
II llquld r r o c t a n t vltn
t h e r o t a r y r n ~ t l o nd t t
cell srrvlng o s an
The Owor and c t t c r t ~ v to g t t a t o r
its spoeer rlng coo
be ikt.hd uut
s o l i d S O m p l r r c o n ha
the s t o l n l r Y l h r l l
~ I l p h r ed l r r c t l y into ti
i r t l a n d i s h which d o s e
t h c b o t t o m d t h q gloss
c r l l When p v r n d p u t or
t h e tdl, the d l r h r o t o h l
wtth tk p u s h rod,
111ngtn9 i t s c ~ n h n t r
1 n t 0 the r e l u t ~ ~ond n
l t T V l l > 9 QS 0 ~ t l r ? l n ~
lmpdlar

Fig.2 1 Cross-sec tion 1451 Solut~oncalorimeter

the~m~stor l ~ u c ing h~ ~dgc,,111
probc and a specially designed l ~ r n p e r ~ ~mwml

assembled in a compact cabinet Temperal.urechanges L:UI 11cplollcd tlncc~ly

in Celslus degrees using an accessoiy sli rp chart 1c~oidc1All opeirttruni alc

straight foiward and easy to handle

Rotating Cell
The two-piece cell which serves hot,h as a sample holdei and dgrtalar,

cons~stsof a glass bell wh~ch1s closed w t h a delachablc Leflon dish The dish

fits silugly In the bottom of the bell wthoul I equlimg a gasket oi scoliiig i ing

Lo secure a tight seal L~quldsample is weighed dnectly into llle hell The
R
glass rod w h ~ c hIS used to open the cell to stm t mixing is insei led from the

Lop of the calormeter through the stlrring shaft and Into a socket in the

s is pushed downwad, the dish slides out of the

sample d ~ s hWhen t h ~ rod

cell and lemains attached to the lod, held at ii fixed d~slanceahovc the

bottom of the Dewu vessel In t h ~position

s the rod and dish lolate with the

cell, slingmg the components into the solut~oriand selving as an addrtional

~mpellerm the st~rrlngsystem Heat leak from the cell Lo nan wetted parts

of the system is held to a mlnlmum by a low conductivity, thln walled glass

stem an the sample cell and a plastic coupl~rigwhlcli f8sLens the cells to the

st~rrlngshaft The cell IS easy to load, easy lo clean and ~nlerch&ngeableThe

dish Itself is made of teflon reinforced wllh glass check for excellent

resistance to most chemical reagents and for good d~mensionalstabil~ty

St11rer Drlve
Thc stiner mcchan~smconsistsof an cxlcinally mounlcd clert~lo rni~lor
wllh a drlved belt which tuins the stnrlng shdfl a t a conslonl spccd
(app~oxmmately460 rpm) w l h no slippage and veiy l~ltlebeallng f ~ ~ c l ~ o n
The hallow shaft terminates at the underside of (.he calormmetel cr>velwhcle
l t j o ~ n the
s plasl~ccoupl~nyon the end of Ghe sample cell

RRactlon vessel
Excellent thermal msulabon is provlded by a fully sllvei ed glass Dewal
w l ~ c hsexves as a mlxing chamber 90 to 120 in1 of solul~onshould be placed
in t h ~ vessel
s to pioperly cover the rotatlng sample cell The cell ~ t s e l f w l l
hold upto 20 mi of lmquld sample 01 upto 2 giams of most crystalline sol~cls
The Dewa IS supported w~lhma stunless sleel ar-can Pom wlnch 111s casmly
removed fol fill~ngor cleanlng

Thermometer
Temnperature measaiements in this calorlmeler are laken w l h a glass-

sheatted thermistor probe combmed wlth a special budge mn a systenl

des~gnedfor hnear response over the temperature range froin 20' to 30°C

Mrithm t h s range each 100 mmcro volt change in output from thc bridge

represents a temperature change of exactly 0 001~C Thus when fed lo a

recording potentlometer and plotted on 10,000 or 1,000 m~lllvollcharl,

temperature can be read directly from the chart w~thoulapplylng a

convertion factor At the start of a m n the recorder is adjusted to z o ~ oand

a base readlng from the bridge is recorded, Any mbsequenl doviat~onfrom

the starhng temperature 1s then recorded directly ~n Celsius degrees If a

iecorder is not available, Lempcintures can bo i c ~ dTiom thc hildgo hy

bnlnnclng with a null detect01

The operatlngpimclplesubed in thls calo~~mctel

ale cl~ssicallysllnplc

Two components ale combined In a Dewal vessel and Lhe rcsult~ng

temperatwe change 1s measuied w t h a lhermislor blidge At the start of the
expellment one of the components, 1s held m sedled glass ~olnllng~ c l in
l
thermal contact w t h the other llquld but not coml)med with 11 The bystem
comes to equllibnum qulckly wlth a shght temperature dl 111 fiom thc heal of
stirrmg and from any heat leait into 01 oul of the calorimeter After recording
the mltlal drift and wthout mterruptlng the rotation of the sample cell, the
mixing process can be effected by depressing a push ~ o wh~ch
d drops the
contents of the cell into the suriounding liquld The mlxing lhcn p ~ ~ ~ c e e d s
lapidly under effective stlrllng of Lhe cell whlch ensures complete and
un~formdistrihutlon of liquid samples The tcmpelatu~echange produced
when the two components are m~xedwlll be sensed lmmed~alelyby lhe
Lhcnstor and recorded 011 a stlip char1

Measurement of h e a t s of mixlng
In the moasurcment of excem enthalpies, known welght of 100 ml of
componenl A is taken lnto the Dewar vessel 20 ml of component B is welghed
ln a sealed glass rotatlng cell Both the colnpoilents ale kept in lherlnal
contact with each othor in the Dewar mlxlng chamber a t 298 16 K After
a t t m m g the thermal equlhhrium component B in the rotating cell 1s mixed
with component A m the Dewar vessel by pushing the glass rod The
temperature change accompanying the mvllng process is sensed by the
the~mlstoland recolded on the s t ~ l cp h a t ictcl~dc~In 111~\~uhscyuenl~uns
100 in1 of earller experimental solution was taken as iolvcnt ant1 to cach a
pule and fresh solute was added These oxper~mentswcic ~ o ~ ~ l l n t11l
u c dthc
concentratlon reaches 50-60 pelcent Tlns pioceduic was lepeated hy tdklng
solvent as solute and the salute as solvenl In thls metl~orla small ellot in
lhe earher runs leads to large error in latter cxpel~meni Becuuse of lllc
hmltat~onsof the calor~meter,we are folced to adopt t h ~ method
s to cove1
the entne concentratlon range of zelo lo 100 per ccnt

The performance of the soluhon calorimeter has been checked f o botli

~

endothermic and exothermc ract~onsw ~ t hknown systems (1) benzene +

carbontet~achlorideand (2) chlorobenlrene f tolucne Thc cxpellmental data
. ~ ~Fig 2 2,
is very well In agreement m t h the ~eporteddata In l ~ t e r a t u ~ e "(cf
2 3) The agreement between the nleasured values and hterature data IS

w~tkin5 per cent and satisfaclory

The excess cnihalpy, IIE is then calculated knowing the energy

equlvalent of the system uslng the relat~on

where W2and W2are the we~ghtsof the corresponding components, Cpnand

Cpg are the heat capaclt~esof respect~vecomponents, E 1s the energy
equlvalent of the calorimeter (76 76 J K'), t IS the lemperature change and
n 1s the number of moles of the mixture
Pig.2.2 Heats of mlxlng f o r benzene +
carbontetrachloride
 M o l e f r c ~ r t ~ n on t r h l o r o b e n 7 e n e

Fig 2.3 Heats of mlxlng tor chlorobenzene +

ToI~~cnc
 Actinty co-effic~enls
and excess G~hbslrcc enelgics have bcc11 o h t ~ ~ n c d
riom expeilmental vapom-llquid equll~hiiumdata assuming ,I su~tnblcmodel
to1 the hquid slate The methods for exper~melltaldcteiminaLioii oCvapou~-
liquid equihbrium (VTJE)ate classified in10 lhe l'ollowing gioups
1) Distillation method
11) Statlc method
111) Girm~latlonmethod
iv) DCWand bubble point method ancl
V) Flow method

i) Distillation method
own^' has densed d~stillatlonmethod in 1879 In this method a
small amount of liquid is dist~lledf i o ~ nthe lalge cha~geThis method has a
disadvantage of consuluing large quanlity of condensate f o ~analysis, snice
the composition of the liquid phase must remaln constant Lmge erlors can
also be caused by condensat~onof vapour on the cold walls of the dist~llation

fla8k aL the beannmng of the experiment

ii) S t a t i c method
In thls method the solution is charged into a closed and evncuuted

cylinder, wh~chis placed in a thennostat The cylinder with its contents 16

rotated or shaken until the equllibr~um1sestablished between the vapour and

11qcud Then the samples are removed from both h e phases Tor analyaia. The

method is apparently simple, since remomng of gas sample for analysis

causes great difficult~eAt low pressures the amount of vnpour required for

85
nnalysls is same as the total nmoullt of vapoul phaho 111 the c y n i l ~ h ~ ~homh
u~n

and the removal of sample thus causes a markod d~stuibnnccin llrc

equllihr~um For thls leason, the static method 1s not used a1 medium ,md

low pressures Th~fimethod is moslly apphcdble at lugh piessules,

d the pressureltempe~aluieis in the vicinity of thc ~ i ~ l i cpoinl

pa~t~cularly al

of one of the constltucnts

iii) Cii.culation method

Thls metbod 1s mostly convenlcnt and w~delyused ~n tlic legion of

medlum and low pleasures All types of equil~briumslllls wllh s~mplc

cnculat~onare based on a common pnnclple (cf Fig 2 4) tl~oughLhey dlffcl

s~gnificantlyfrom one another in thew conslruction details

Fig 2 4
The vapours evolved from the boiling mlxture in the d~slillallonflask
(A) pass through the vilpour condult (+I and after complete condensation
collect In recelver (B) After filhng the ~ece~vel,
Lhe condensale relulns to

the dlstillahon flask through Lle liquid coildu~t(C),

in wh~chtheie is usually
a welr or cock inserted to prevent the flow of the lrquid from Lhe d ~ s t ~ l l a l ~ o n
flask back Into the receiver When we start the stlll, the recelver (B)Is empty,
at the lnstant when it first fills, it8 contents are richer 111 Lhe mole volatlle
~onsbtuenlthan Ule vapoui phase ovel the boil~ngm~xturein thc dlsllll~ng
l l a ~ lW
~ ~ t hthe further operation of the sllll, the contents of tho dist.illa11on

flask become richer in Lhe more volatile cornpollelit a i ~ dthc 1ecclvcl bccomcb

pooic~ Thls process continues until the steady state 16 attained, in which

the compositions in both the vessels no longer changc wilh lirnc Bolh
compositions are determlncd a~lalyllcally

It can be proved that t h ~ ssteady state collesponds to phase

eqtulibnum The vapour condensing in ihe icccivei is cor~t~ni~ously
111

equ~libriumwith the bolllng hqmd m the distlll~ngflask, I e , supel healing

w d partial condensatioil do not occur If this assulnption is fulfillcd fol the

steady state, we can only prove the ldentlty of the compos~tlonof the liquid
in the eeceivel w t h the compos~tionof the evolved vapom

At the steady state condltlon, the composlt~onin these vevselv docs ilol

change with time

where x i and ;
T denote the compovit~onin the distlllat~onflaslr and in

the receiver, expressed as the mole fractlon of the move volnl~lecomponent

and 't' 1s the t ~ m eIf the dlstdlat~onoccurs \nth a fimte velocity, then cluring

the interval dt, dn* moles of mixlure pass from A to B and during the same

period dn* moles relurn to the reflux from B to A Slnce the hold-up in the
receiver is constant we obtain
 If the vapour which 1s evolved from the murture of colnpos~tlonT. has
the cornposit~ony $, then the amount of volatila canstltuel~thansfeiied from
A to B is equal to y h dn* and the amount of this constltuent transfeired

from B to A is x b dn*- If equation (2 3) 1s to be satisfied as the conditio~~

for constant hold-up, we find for a material balance on the volallle
constltuent

Y;A dn* = lib dn* 25

whrch m combination wlth equation (2 4) ~ v e s

Since, foi a finite velocity of distlllatlon dn 'Idt 6 0 Equation (2 6) can be

fulfilled only if
z;B = Y;B 27
T h s proves the assumplion of equil~briumbetween the hquid phasc and the
cvolved vapour rn the distlllatlon flask 1 e ,the composition in the rcccivcr at
steady state is idenbail w t h the composition of the vapouls evolved from the

bolllng mlxture m the distillation flask and hence the steady stale
corresponds to phase equ~libr~um,

iv) Dew and bubble point method

Thls method has been used for a long time for the study of the phase
behawour of hydrocarbons, particularly those of lower molecular weight,
which ale gases 01 low bo~l~ngl~qulds
at noilnnl e o ~ i d ~ t ~ r ,llic
ni I ~ d ~ i ~ i l ~ r ~ g ~
of this method IS that it allows thc c ~ ~ t ~condrlions
cal to bc d e l c ~mlncd and
glves data on specific volumesof m~xturesa t h ~ g hp ~ c s s u ~ css~, r ~llic
c c tolal
compos~tionof the mixtuie is accuralely delermrned glavnnct~i~dlly
upon
chargmg There ure of courbe, disadvantages too Howovcr, 101 ~ c r t a l n
cond~bonsthe dew and bubble points arc not s~mplydefined as the required
measuremenls are lo he made w t h highly precise instrumentb 'I'he simple1
u n ~ t susing merculy as a valuable volume confin~ngfluid cun 1101bc used
below the fieezmgpo~ntof mercury Further, a large amount olexpe~~menlal
walk must h e done m order to define the accmate phase equilibria ovm all
ranges of llquid and vapour composit~ons Dew and bubble points alone
cannot define the compos~t~on
of the two phases m e q u ~ l i iuni
b ~ becaube more
complex systems are not umque functions of temperuluie and pycssure
accordmg to phase rnle

V) Flow method
of VLE of one or more feed
In t h ~ smethod for the determ~nat~on

stieams, which may elther be vapour or l ~ q u ale

~ d metmed continuously Into
an equilibrium chamber, where the total feed rmxture 1s pallially flashed

The liqu~deffluent 1s w~thdrawncont~nuoslyby ovorflow and the vapour

effluent by pressure control Heat Input late 1s controlled to @ve a set of
temperatu~ein the reboiler This method has been wdely used f o ~llie

deterinmation of VLE The primary disadvantages are those, the apparatus

IS Inherently more complex and uses more r a p ~ dapproach to equ~librrum,
relatively easler change of feed compos~t~on,
and low res~duetime in the
rebo~ler
 I methods of measuring bolllng polnts of'llqu~dsand liquid

vessel contamlng the borllng hquld and a thcrnio~nclo

1 to errors that could be ehminaled In thls method Lhc

iays supc~lieated,since the su~facetensloll of thc l~qulrl

on of mall bubbles oCvapour FOI the liquid mixtuies

~llonchanges continuously with the loss of volatile

tj: m erroneous bo~lingpolutof the m~xture F u i t h e ~In

,
a ,..qpolnt by t h s method, theie wll be some supel heating

llqu~ddue to hydiostat~chead The compllatlon of I-Idla

1 , iew made by Stan~slaw~ a l a n o w s k~emarns
~ ~ ~ t.he mosi

' % nvallable expenmental methods

tf,ctei w t h a thermal l ~ fpump

t that 1s used to dehve~.the

llquld to a thermometer In the dete~rnlnatlonof Lhe

+ Jutlons was lntloduced by ~ o t t i e l f ~T' h ~ apparatus

s was

' :ry ~ a s h b u ~and

m then
~ ~ mod~fiedby Swletoslawsk~e l allfi

clL ) developed the first ehull~ometerwhich conslst of a

, a d In anarrow tube wlth its eonlcal end at the bottom of

.
' other end on a horizontal plate where a t h e ~ m o m e t ewas
~

,, our phase Dunng the beallngproccss vapoura carry slugs

,Lorn through narrow funnel-ended glass tube, known as
I , # , v, lo the hor~nontalplate and from it on to the thermometer
I r u ~ ,between
l the 11qud and vapour phase is eslabhshed on the

8 lor, ~ ~
~ , , l O ~
 The ebulliometei developed by Swmtoslawski lo^ LII. J ~onhislia

theimowell fitted wllh an exteln~lglass spnal, biakes the ~un-nllliquid hoin

Cott~ellpump The boiling liquid spurting on to Lhe thermowell is

superheated Equilibrium between the liquid and vdpour phase 1s f i s l
estabhslied on a therinowell, a small par1 of the fulling supeilieated liquid
vapourlses at the expense of its sensible heat As a result, the temperature
falls on to the equihbnum value Since there is no loss of mater~alfiom the
system, there w d be no change m the compos~lionLhioughout the pe~iodof
heating At constant pressure boilmg poiilt with an accuracy of * 0001'~
Lan be measuied with this ebulliometei

Geneially, the followmg conditions whlch are based on lhose

~ complemented hy Hala el al , (loc

formulated piemously by ~ o w l e ?and

cit 1 should be fdflled by a pioperly reurculatlng still

(1) concentration grad~entsmust not occur m the boihng liqu~d,
(11) the equ~libr~um
vapour must not paltially condense,
(111) the walls of the bnlling flask must not be superheated to avoid non-
equihbrlum and total evoparation of adheling droplets of hquid,
(n) the condensate ~eturnedto t h e distillation flask must be perfectly
mixed wlth the maln port~onof the llquid in order to avoid its non-
equll~bnurnvapounmt~onas a result of its lowenng boihng pomt,
(v) the vapour leavlng the bo~lingliquld must not contan droplets of
liqu~d
(vl) The inslrulnent should be useful for the accurate meosuremenl, of the
bo~lingpoint
(vii) muring of equilibrium liqu~dw t h part of the return~ngcondensate
should not occur when liquid samples are collected,
(~111) equillbrlum should be reached as qulrkly us possible,
(IX) The arnouiit uf subslance ~equnedin the sludy sllould bc as litllc as
possible, and
(x) Lhc ~ n s t ~ u m eshould
ut be as simple as posslble

The Smetoslawslu type ebulliomeler satisfies all the above cond~lions

except (IX)condihun which does not pose aprohlem, since the chemicals ale
available m sufficient quantities Hence, this type of ebull~ometer1s adopted
in the present invest~gation

Desciiption of the experimental set up

used In thls woilr 1s shown in Wg 2 5
The Sw~etoslawslueb~~lllomete~
The hqu~dm the boihng tube 'A' is heated up by canthol w i e wound on a

sil~ca~ o dThe late of heabng is controlled by i~smga vurinc When Lhc liquid
slarls boiling, the bubbles of liqu~dcarry w t h them the slugs of liquid
through Cottrell tube 'C' whlch spurts on to the themowell 'B' In whch a

platinum 100 themomeler is placed The instrument 1s entlrcly closed and

all kinds of stoppers avoided, thus eliininatmg contamrnation from grease

etc The thermowell 1s fitted w t h an external glass spiial which brakes the

run-off liquid Equilibi~umbetween vapour phase and liquld phase is

established Iirst on thermowell '3'Dunng the measurement oftemperaLuie,

glycerol 1s added to the thermowell to lmprove heat transfer The vapours of

the liquids are condensed m the condenser 'E' and condensate falls fiom the
condenser to the drop counter 'D'from whlch it is fedback to Lhc boihng tube
'A' Vacuum 1s applied at the top of the condenser %' The rate of heat~ng
1s adjusted in such a way that condensate from the condenser %' results in
30 to 35 drops per minute in the drop counter 'D'.The block dlagram of the
cxpel~mentalset up in this worlr 1s shown 111 F I2~lj Thc sy,yslcn~p~I!L~SIIIo w,ii

measuied using the open limb meicuv manomctm as sliowli in the l,lr!ck

d~agrnm

~ e s o r i p t i o nof the experimental procedwe

standardisation of ebulliomete~s
Two ebulliometers were standaidised by measuring the vapour

picssu~e data of pure water at different pressuyes rangng from46-

715mmHg The measured vapour pressules of watel In ebulbometers I and

11 are presented In Table 2 2 The measu~edvalues arc in good a ~ e e m e n t

wltb the lite~atuievalues3'

The Antoine constants A, B and C and physlcal properties of the pule

components vlz , accentrlc fact01 ( w ) , critlcal tempeiature (T,),cl~tledl

cnlical volume (VJ and compress~bllityfact01 (Z,) that are ufied

pressure (PC),

m VLE caiculatlons are presented in Tables 2 3 and 2 4 iespecl~vely The

values arc taken from iiteratu~e""3g

Isobaric boiling points of binary mixtures

The boiling polntfi of the binary systems have been dete~mlneduslng

the ebulhometer techmque over the enhre ~ a n g of

e composlt~orl The h o ~ l ~ n g

pomts for the known bmary composlhons were measured a t 715 mm Hg

Wxtures of different compostlons were prepared by mixlng known weighls

of the pure mater~als The pure componenls were weighed using a Mettler

balance havlng an accuracy of i 0.0001 gms

 EBM-1 EBM-2 \laeuum- puma

FIG 2 6 .LINE OIACRAM OF EXPERtMENTAL SET UP

Table.2.2 . Vnpour pressures of pure water

'%) of Error
Vapour pressure
toc in mm Hg pcul - prtmtAmd
Pmmurd
Ebulllometer - I
36 0 46 -0 35
52 0 102 0 25
62 0 164 0 17
68 5 219 0 30
72 5 260 0 37
77 3 318 0 31
81 0 371 -0 07
84 4 423 0 30
87 9 486 0 00
90 0 528 -0 29
92 3 574 -0 01
94 6 626 -0 17
97 1 686 -0 OF
98 3 116 -0 16
Ebulliomcter - I1
36 7 46 -0 02
51 9 102 0 02
61 8 164 0 26
72 4 269 0 97
76 8 318 -0 39
80 7 371 -0 40
84 3 423 0 69
87 7 486 0 28
89 9 528 -0 08
92 2 574 0 12
94 5 626 -0.14
97 0 686 -0 14
98 2 716 -0 29
Table. 2 3 : Antoine constants of pure cornponcnts

Compound A B C
-
d~methylsulphoxldc 7 58667 1962 06 225 892

tolucne 6 96059 1348 77 219 976

ethylhenzene 6 96790 1431 71 214 099

chlorobenzene 7 18743 1556 60 230 000

hrornobenzene 7 25422 1688 40 250 000

ethylmethyl ketone 7 05954 1259 22 221 758

rnelhyllsobutyl ketone 6 82450 1256 45 203 000

cyelohexnnone 6 97840 1495 51 209 660

tetrachlolocthene 7 01870 1415 23 221 000

Table-2 4 , Crltlcnl constanth of the pore eonlponenl5

Compound o T,. PC vr 2,

If bar CII~

cyclohexanone 0 4500 629 20 3850 311 0 0 2290

Calculation of aCtlV1t.y coefficle~ltsand Vapour coml>os~tions
The vapour phase at low pressures 1s ldenl whlch leads to the s~mpllfied

valucs fol 4, = = 1 and the Integral in the pomtlng c o ~ ~ e c t l ofactor

n

wlll bc very small Under these cond~t~ons,

the total pressure of a hmaiy

system IS given by

If the complele experimental data of T,P, x and Y ole available for any

b~narysystem, the value of y, and y2 can be computed fiom equatlon (160)

at each llquid compositionx The act~mtycoefficient data is then fitted to the

to o b h n the pararnete~sm Van Laar equat~on,Margvles

liquld compos~t~on

eqnatlon etc The same info~matlonmay be obtained by reducing the

experimental effort of measuring both the Iiqud and vupour phase

composlbons x and y, smce, the uncextalnty m measullng vapoul

compositions is more compared to 11quid colnpos~t~onsMcasurement of

isothermal p-x or lsobarlc t-x data axe expected to g v e good est~mateof

parameters m the activlty coefficient expressions Van Ness et aI4', had

slrown that the calculated and experlmentd vapour compositions agree well

In the present study, the b0111ng polnts (t) of the blnary systems of

known composltlon (x) have been measured usmg ebull~omelertechnique

over the entlre range of composltlon at 716 mm Hg The 2-1: measuremenis

are used to compute vapour phase composlt~on,activlty coefficients and

Cxcess G~bbsfree energies basmg on Wilson model41," The Wilson equat~on

97
was chosen to represent the composition and le~npexdlu~e
dcpendencc of

phabe achvity coefficients y, di~dya

29
-
G = -
x, ln kl + ""121 - xa ln k a A,,]
RT
+

I and ale W~lsonpalameters whlch a e ternpe~at,u.ule

dependen

temperature dependence of these parametels is Dven by

where and % are liqu~dmold volumes at temperatuie T of the pure

l~quldsA and B Molal volumes were calculated using mod~fiedRockett

equation43, Dven by

v = Vr Z, 0

98
 and C = 217 In equatlon (2 16)

( A - A ) and - ;122) ale lnl~enas constants ovel a 11m1tcd

tempelalure lange When Lhe tcmpelatu~elnnge 1s wlde these also depend

on temperature A's ale the energies of interaction bebween Lhe molecules

deagnated m the subscr~ptsThe opt~mumWil6on constdntfi (

R
and ( -
R
"9 ~ n gobjectwe funcl~on,r j ~
are obtmned by m m ~ m ~ z the

usmg Nelder Mead optimzahon t e c h n ~ ~ u e ~ ~

The 11alue of Pal 18 Dven by

p, = 2 X& Y,P?

The vapour compos~t~on

was calculated usmg the following equat~on
~ h excess
c s eneigies weze ~akuinteclCI om ihc a c ~ ~ v~ocllicien
G ~ b b flee ~ty k

using t,he equation

A ready made computer programme available at I n d ~ a nInst~luteof

Chem~calTechnology, Hyderabad, India 1s used for the detelmlnation of heal

of muting, excess enthalpy Anloine constants, vapoul-l~quidequil~biiumdatd

correlation using t-x data

 EXCESS VOLUME

Excess volurnos ol binaiy l~quidmixtuies are dctcrmmed by two

pr~nciplemethods (1) dilecily by obse~vlngthe changc in volumc upon

mlxlngihe components in a dilatometer, (11)mdnectly by mcasuirngclcns~tres

of pule liquids and liquid murtures wrth pycnomete~ The dilferent

techniques employed for the delermination of excess volumes were ciit~cally

iev~ewedby att ti no*^, Marsh4%nd Hancla and Benson4'

I. DIRECT METHOD
Ulrect methods are capable of gmng more accurate and rebable 1esults

than the rndirect methods Two basrc des~gnsare available for diiect

measurement of They a e (a) batch or smgle composlt~ondilatomelei and

(b) clrlut~ond~latometers

a) Batch or single composition d i a t o m e t e r s

Batch dllatometers wele designed by Keyes and ~ r l d e b r a n d ~ '

(cf Fig 2 7) for dlrect measulement of The design of the apparatus has

been modified by seve~alworkers4' The apparatus is has~callyan U-tubc

w ~ t hmeicury at the bottom to separate tllc two components and with

grnduated capillaries on the ends of the two bulbs to measure Lhe volurnes

before and after mrxing The muting lo brought about by locking the

apparatus The cornpositron of the rnlxture is determined by drrecl weighirig

However, the ch~efd~sadvantageassociated wrth ilese dilatometers is the toss

of liqu~dsdue to evaporation of volatile compuncnls Ahmcd cl al" , ilnd
Bicnnan et a163,have modlfied the d~latometeidescrihcd by Puwell and

swmtons4 The modrfied apparatus elrml~~ales

the error due lu evapoiiltlon

of volat~lecomponents during lnjectlon The limbs of dilatometer a1 e filled

with the wmpanents prior to filling wrth meicuiy Each componeril is

lnjectcd m such a way that the llquld dssplacesme1cury m the con~erncdlimb

and is thus held over mercury rn the limbs Sloolcey et a15< have descr~bed

the balch dilatometei technique for the delermmatron of excess volume In

this method sutteen cells wcre used in a balch to covci Lbe whole mole

fractron range The totnl error m vE measulemenl IS conlilbutcd by the

factols (1) punly of Lhe liquids, (11) lemperaluic fluctuat~ons,(111)

uncertanty rn culhntometcr reading, (iv) componenl wc~ghiiig, (v) cap~llary

temperature correction, (vl) compresslbllity and (vii) vapour in tho unfilled

pait of the captllary

b) Dilution dilatometers
Drlutlon d~latometers are also called as continuous drlution

dllaiometers As the dilatometers requlre at least two runs to make

measurements over the entue mole fraction range, lhey are really called as

semi-conlinuous dllatometers S~ncetho publication of the des~gnby

Geffcken et d6,dllution dllatomcters have undergone a number of

modificalions ~ i l a t o m e t e r s " ~employed

~ III the inltlal stages had large

mixlng cells In order to get good precislon m detect~ngthe volume changes

the capaclly 1s Val led tiom 250 to 600 em" Recent developments have heen

aimed at malung dllatonlcte~sw ~ t hsmalle~mixlng cells, fewel stopclocks oi

llonc at all and simple Lo operate wthout saclificii~gplec~sion

Dilution dilatometer for the lesl system, cyclohexane + henzene with

a standard deviation of 0 0008 em3 moll was publ~shedby Slokes e l ale'

Mart111 and ~ u l r a y ~have

' slightly modificd the deslgn to facllitatc the

cleanmg, filling and callbiation pioceduics and a simplc vcrslon has been

reported by Rcede~et alRa The ccrnmeiiccrne~~t

old~lutioncannol be defined

dearly In the latter dllatometer due to the p~e~nlxiilg

of the two components

The eiror from this soulee can he reduced with careful manipulation

Dickmson ct d6', have constructed a dllut~ondilatometer wlth whlch they

obtained a standad demabon of0 002 mSmoll for the test syslem Thls

design has the advantages m the method of filling, the ease of opeinlion and

the elnn~nationof premwng Dlaz Pena and ~elgado" have ~eporteda

d~lutiondilatometer similar to that of Pflug and ~enson~"n allnos1 all of

these dllatometers the mlxing cells have a capaclty of about 50 cm3, part of

which is occupied by mercury

Bottomley and Scott" constructed a dilutlon d~latomete~

w~thout

greased slopcocks in whlch no stopcock is turned or adjusted during dilutloil

runs They have used this dilatometer for measuring excess volumes of the

order of 0 005 cmS moll The d~latometeris easy to operate but IC suffers

fmm follomg draw-backs (I) ~t 1s difficult to calibrate, (ii) it 1s hmited to

103
mcasule small volume changes only and ( n ~filling,
) w l i ~ d16~donc undc~

vacuum, 1s qulte Lcdlous Kuma~anand M~Glashan"'have publlslrcd an

improved velslon of the 'pease-frce t~ltingdilut~orid~latrrmcter'whlch is

easiel to operate and can he filled under atmospheric pressure This

d~latometer1s easy to calibrate and can be used to measure vE of any

magnltnde

Almost all of the dilut~ondilatometels descl~bedahovc do not measure

volumc changes at c o n s b t pressure The dilalonletei due to Tannkca ct aim ,

whicil is a simpler version of the one described by C h a ~ e y ~ oand

n Clec1ietso

1s the one which can be opeiated at constant pressuie Thls dilalomete~1s

capable of hlgh preaslon though difficult to opelate The standmd domalion

ieported for the l.est system 1s 0 00043 cm3 moll Janssens and ~ u e l ~ '

descnhed a dilution d~iatometcrwhich can he opeiated at a constant

pressure No mercury is used, which 1s an advanlage, smce some o ~ g a n ~ c

hqu~dsare reported to react w t h mernuy Janssens and Rue1 have oblained

a remarkable standard devlat~onof 0 0003 em3mol

2. INDIRECT METHOD
Excessvolumes are rndi~edlydeterm~nedfrom densities d p u r e hqulds

and hqu~dmxtures Thore are several methods for the determination of

dens~tyand these were discussed in detail by Bauer and Lewm7l The

methods may be class~fiedInto the following calegones on the type of Lhe

apparatus used (a) pycnometers, (b) dilatometers and (c) other dlverse
methods

104
(a) Pycnometer
~ a y - ~ u s f i ahas
c ~deslgncd
~ a pycnomete~s~rnilaito a specific g~dv~ly

bottle lo deteim~nedensities whc11 are uccniate lo fnuilh dec~lnalplacti The

deslgn of the pcynometer has been modified by seveial wol kers7' ?' P,irker

and parkerI6 and W a d and Wooks7' designed a blcapiilaly pycnornetel for

measulmg densihes of a slngle sample a1 valious temperatu~esPycnometei

measureinents are subjected to a numbei of corrections, lhe more ~ m p o ~ l a n t

one being the correct~onfor buoywcy and amounl of l ~ q u ~01d llqu~d

mixtn~esin the vapour phase Brown and Lane7Rhave exhaustively discussed

the effects of various ractois such as lsolope composit~ori,d~ssolvedgases,

~mpurllies,prcssuIe m d tempeiature on dcnsily mcasu~emc~its

b) Dilatomcter
NcubackTg descr~bed a dilatornetel, whlch was used for the

determmal~onof density by the we~ghtof mercury expelled or added lo the

dllatometer when the lemperatule is riused Improved verslons oCt11e welght

ddatometers have been reported by ~ u i l e wWood

~ ~ , and B1usiea1and Wirth

and ~ o s o u r d oThe
~ ~ double-armed dilatometer described by Hlldcbrand and

Ca1terB3used for the measurement of excess volu~nesat 303 15 K

C) Diverse methods
(1) Balancing column method
It 1s based on the pnnclple that the hydroatat~cprcssure of a gven
we~ghtof a l~quidIS proportional to itn density and this melhod isuseful when
small quantities ofliquld are available It is capahlo 01 ollcling ,In , I L < . I I I C L L ~

of 2 In 10"arts

(2) Buoyancy method

This methods"" is hased on Archimedes pllnc~pleand useful fut

tempelature varlatlon studles However, ~tis less wldely used nh 11is d~fiicult

to mantain temperature and avoid surface tens~oneffects Under oplnnum

conditions the method is capable of yielding an acculacy of 2 111 10" pal is

(3) Magnetic float method

Thls is another foim of the buoyance method The denslbes cif'hquids

and l~quidnuxtures have been deternuned wlth an dccuracy of 1 part m lo5

p a t s T h ~ method
s makes use of a sub-meiged float conlnining an n a n core,

the buoyance of which is del~catelycounter halanced by the pull of a curlent

carrying solenold This technique has been used f o ~piecise denslty

meabulemcnts by BenJammB6,Franks and Smiths7, Masterton and ~ e i l e ~ ' ~

m d ~ 1 1 l e i oHydrostahc
~~ weighing methods (suspended sinltcr) have been

uscd by Wirth84, Redhch and Bigelelsen" and SchulJgl Though the

hydrostahc method 1srapid the lesults obtaned by the ~nelhodare subjecled

to uncertainty arlslngfiom surface tension effect between the liquid surface

and the wlre to wluch the slnker is attached Amagnetic float densimeter for

the measurement of the density of organ~chqu~dshas been descr~bedrecently

by Benson and weeksg2, which has a scnsltlnty of 1ppm and a precision of

20 ppm It has been used lo determ~netho excess volume of bonzene t

cyclohexane system at 298 15 K

106
(4) M e c h a n ~ c aoscillator
l densirnetel method

A denslmeter whlch works on the pllnciple of mcthanlcal osc~llal~on

wasused by sevcral worl~ers""~ The majol soultes of el101 in this mcthcrtl

ale tempelature fluctuations and vauations ~n mole f i a c t ~ o ldullng

~

opelabon These factois can easlly be controlled In the manner suggesled by

Gootes et al" , and Radojkovlc et alYY, Adams et have descxlbed un

automated apparatus f o ~measullng the densities of the pure liquids and

llqu~dmuttures of varymg compos~tion

The measured dens~tleswere employed to compuie excess volumes

(indirect method) hg uslng the equation, as follows

wheie M, x, and p, represent the molai mass, male fiactlon and denstty of

the component '1' respectively p, refels to density of the lnixlule

In the present study, the dens~tiesof pure liquids were oblalnad w ~ t h

the help of a double stem pycnometer, or~gmallydeslgned by Pniker and

Parker7' (cf Wg 2 8) The denatlas were reproduclbie to two parts m 10'

Dens~tywas used a s one of the crlteria for Lhe purlby of the 11qulds
 To dcterm~nethe density of any liquid, the liquid was intioduced into

the empty weighed pycnometei w ~ t hthe help of u hypodcrm~cs y inge

~ unlil

the levels of the llqwd in the both Lhe stcni very nearly c o ~responded wiLh Lhe

maiks on the stems The exact innss of the liqu~dpresent m the pycnometcr

was determined wlth refeyenee to a dummy pycnometer The pycnometei

mth the liquid was kept immersed In the thclmosht at 303 16 i 0 01K ovei

a lenglh of time until the levels of l~quidweie stat~onalyin both llle l ~ n ~ b s

The heights of thc liquid level above (01 helow) the refeience mailrs on the

stems were measuled by the havell~ngmicroscope The exact volume of Lhr:

pycnometer included between the maiks a t 303 15 K was detelmnlned as

descr~bedbelow A length of the capillary, used fox maklng the stems, was

filled wlth pure mercury thcacl, and Lhe lenglh of thc melcury was measuled

by a Lravelhng minoseope F ~ o mthe weighl of Lhe merculy thicad, the

Internal dlameter of the tube was ascertained The volume of watei (V,,)

contamed ~nthe pycnometer was obtalned uslng the fallnula Mlp,,, whet e M

was the mass of water and p, was the dei~sltyof watcr a t 303 15 K

Thc volume of water (dV)above (or bclow) the m a ~ k was

s calculated

using the formula n$h (wheie r 1s the radius of the capillary of whlch the

stems were made of and h the corrected d~fference~n height belween the

mark and menlscus m both the slcms) Thms volume (dV) was Lhe differcncc

between the volume of water actually present in the pycuometet a1 303 16 K

and the volume of water that would fill the pycnomete~upto the marks at

303 15 K The exact volurna (V) of the pycnometer included between the

marks was then calculated by substract~ng(or addmng) dVfrom (to) Vw For

108
example the density of a pule h ~ u i d( p , ) 1s conipulcd u s ~ n glht~~cldtlon

p, = MJV, where M,and V, denote the mass and volumc of ihc 11qu1d L

I espect~vely

In the presenl study, the f o blnary

~ mixlurcs wcle nlcdsurcd with
lhe help of a batch dllatometer s ~ m l l ato~ that oCBrow11 and S m ~ t h ' and
~

rnod~fiedby Raoiol (cf Fig 2 9) was used It Included a delachuble capillary

ar~angcment The dilatometer was haslcally an U-tube of pyiex glass wlth

rne1cLuy at the bottom to sepalate the lwo components Oilc alrn of Lhe

U-lube was termmated wlth B-10 slandaid jolnl (Socket) and the o t h e ~arm

wlth B-14jolnt (socket) B-10 sloppel (or B.14 stoppel) closed one uf the

sockets and the other socket. was fitted wlth a standard B-14 cone (01 B.10

cone) fused on to a su~tablecapillary tube (lnner dlarnele~1 0 mm or 2 0 nnn),

l~awnga teflon cap \nth a small or~iiceto ensure that the pressulc lnsidc thc

oapilla~ywas equal to the atmo8phehenc p ~ e s s u ~The

e cone and stoppel are

intelchaugeable enabllng the apparatus to be used to measulo excess volumes

at other mole fractions Five &latometer8 of the type descr~bedIn Fig 2 9

wh~chdlffered m the capac~tiesof the compartments A and B were used to

cover the e n t ~ r erange of composition Composit~onof etlcli m ~ x l u l ewas

determ~neddlrectly by waghmg T h ~ offered

s an accuracy in fourth declmal

place The d~latomoterand its contents were placed 111a watcr lhermostul

controlled to withln t 0 01 K The dllatometer was allowed to stand in the

thermostat hll it altolned the temperature of the bath, whlch was Indicated

hy the constancy of the llquid mrniscus in the capill~lyas seen through a

travelling microscope whlch could read lo 0 01 mm The posrt~onof the

109
F I G U R E 2.9 Dllatarneler
constant liquid level was then lead, ~eldlivet o I' ~ c f c r c n n1,11k
~ e on l11e

caplllaly tube BY tlltlng the appalatus lcpeatcdly Lhe contents ol Lhc

dllatometer wcre then thoroughly mixed In oldel lo dl dm the hquld 111 the

capillary lntn the compartment the d~latometelwas placcd 111 powde~ed ice,

whlch facilitates the complete mlxlng of the components The d~lalumetei

wns then placed in the thermostat When the dllatometer attamed the

thermal equ~l~brlum
the posit~onof the hquid level ielatlve lo the iefcicncc

m a ~ kwas I ead agaui The molai excess volume V' was calculated uslng the

equation

where r , Ah and (IL, + n,) ale the ladius of the caplllary, change in hquid
level on m m g and total numbcr of moles of the inlxture respect~vely The

pelfolmance of the dllatometer was checked by meusuling the excess volulnes

of the leference binary system, bcnzene + cyclohexane at 298 15 Ti and the

results were compaed w t h those reported m hteiatu~eand we presenled in

Table 2 5 The execss volumcs wcrc leproduclble to +O 003 cm3moll

A total ermrm Pmeasurement iscontributed by the followingfaelors

(1) purity of the llqulds, (2) temperature fluctuations, (3) uncerlainty In

microscope readmg, (4) component we~ghmg, (5) caplllary tempnatuie

and (6) cornpress~b~l~ly

Qol~ccl~on
Table 2.5 : Value of Vn for equimolar cyclohexane + benzene

mixture at 298.15 K

VE
Refel ence
Cm mol -'
Pi esent woik
RaoLO'
Watson et a1
Powell and Swintons4
Stoolcey et al ,95
 ISENTROPIC COMPRESSIBILITY

Isentropic compressibllilies of llqulds and liquid mixtures ,11c

deteimmed elther by direct piezomeli~cmelhod or rrom sound velocil~esand

dens~tlesin indirect method

(I) Direct piezometrlc method

The d~rectmeasurements ale usually made by complessmg the 11quld
in a glass tube OL m a mela1 tube to a presswe of about one b a ~above Lhc

almospheiic pressure When tbe excess prcssulc is suddcnly rcleased the

change in sen tropic volume can eas~lybe observed if the vessel has d

capillary neck The measuerd value of compxessibil~tyhas to be conectcd fol

ccomp~ess~b~blllty
of glass or metal vessel

or'^' f i ~ s tmade p~ezometr~c

measurements involving olganic
liquids Two hypes of piezometcrs worc used of which one was made of
copper The piezometer offered an accuracy of one per cent The coppel
pieeumeter was canvenlent to bndle and Lhe cor~ectlonlo be made fol

the comp~essibilityof copper was found to be negligble IZ, values of

a number of liquids and of binary liquid mixtures upto 343 15 K were
measuxed by Staveley et allo3, Harrisun and Moelwyn-HughesIo4made
sim~lai nleasurements using the copper plezomcters Shinoda and
HildehrmdloGused all glass p~ezometers

A slngle plezometer was deslgned by Diaz Pena and McGIashanxoGto

measure the comprcsslbility upto 30 atms and upto a temperature of

303 15.K Late1 nlaz Pena and McGla~han'~%useda driuhlc pici.omeler lo

measure the co~nplessibllltiesof mlxt.uies of corbonleliachlo~~de

and

~yclohexanein tllc temperatuie range 283 15 K lo 328 16 I< I-Ioldc~and

whalleyIu7measured the comp~essibditiesof pule hqutds and liqmd m ~ x l u ~ e s

using an all glass plezometcr in Lhe tempe~atuielange 298 15K to 318 15K

and a pressuie range 5 to 100 bais The measuremenls wele acculate to one

pelcent

Ewmg et alloa , measured isothe~mal compress~bility, tl~eimal

expansivlly and theimd ppressule coeffic~entof benzene + cycluhexanc a1

298 15 K using dilut~onplezometer The apparatus 1s capable of a precision

of ri 2 ~ a - '

(2) Indirect d e t e m n a t i o n of Isentropic compressibility

Isent~opiccompressibility Ira can. be calculalrd using sour~dvelocity

ui, and density p, as follows

K, = u2 p1 2 23

Uensity 1s computed from expeiimental excess voluines and

compositions uslng the relation

whcre x and M represent the mole fraclion and molecular wighl of the

Correspandlng component Vstands for Ideal molar volume and denotes

excess molar volume of the hquid nuxtures.

113
 SOUND VELOCIlY

The lcchnlques employed for measuring sound velnclty cdn he b10.1dly

divided into two categolies

(a) Cont~nuouswave technique and
(b) Pulse technique

(a) Continuous wave technique

This technique includes optical methods based on the of

Lhe accoustlc g2atlng and lnterferometilc methodsi1' lhat excilc a liqu~cl

column into resonailce Varlable path intelfe~omete~s

have been widely uscd

and lecent advances permit accmacies of a few paits per mlll~onm sound

velocity measurements A double c~ystalinterferomete~was einployed ta

measure sound velocity at 600 MHz by Huntel and DardyU7

Sound volocity measurements have also becn c a n e d out wlth other

type of mterfe~ometersin which the resonance of the hquid filling a cavlty

was studied Earlurn titanate cylinder filled wth the exper~mentalhquid,

plated in such a way that one half acts as a source and other half acts as a

leeelver was used by Dobbs and meg gold"' Sound veloclty values fol

fourteen b ~ n a yliquld mixtures using a angle crystdl ~ntelfe~ornetet

at

400 KHz was measured by Fort and ~oore"' The interferometer was

sim~larto that of Hubbard and ~ o o r n ~ sbut a barlurn htnnak

' ~ incorpo~ated
~,

crystal rn the place of a quartz crystal Thls replacement became necessary

to avoid the need for hgh voltage and consequent insulal~ondifficulties The
uncertainty in the sound velocity nlcasuien~cillswas csl~matedit, bc 0 16

pelcent

(b) Pillse Techn~que

In thls technique, measurement of trans~tt ~ m ie b ~a Bven path length

enables one to evaluate sound veloc~hesin I ~ ~ u ~ d s ' " Techniques

'"~~ capable

of @mng an accuracy of 1 in 30,000 weie developed by Gieenspan and

~ s c l i i e ~ gM
' ~c~S,l ~ r n i n ~and
~ ' Bulow and ~ a z ~ a n ' ~ ~ h a s c ' ~ ~ e va o l o ~ c d

double cryslal lnterfcrometer (pulsed) w ~ t hwhlch veloc~tychanges can be

detezmmed w t h an accuracy of 0 005 per cent The veloclty measuiements

weie made by Xlyohara and co-wo~kers'~'~'~~

with leference to pulses, u s ~ i ~ g

the pulse - echo-overlap method in mult~pleecho mode i n this metliod the

velocity is determined by measuring the time interval between a pair of

echoes of an ultrasonic wave trvell~ngbetween a i~ansducerand ieflector

The ultrasonic mterferometer has some advantages over the pulse

techniqueis"he use of differential path length, instead of total path lenglh

and them accurate measurements w ~ t han optrcal interfeiometei, has an

advantage over other mterferomete~s'~~

In addllion, the interferomcter

requlres a s~mplemeasurement of frequency as opposed to a more d~fficult

measurement of llme interval in tlic pulse toch~iiq~ieInterferometer is the

refore found to he more sultable for the determlnat~onof temperature and

pressure coefficients of sound veloc~tyThe interferometnc method is llm~ted

due the narrowness of the band of appl~cablefrequenmes Pulse methods

cover a vvlder range and were particularly useful at higher frcquencies, 10 to

116
100 MF17 The supello1ity of the ull~~lsonlc
mtel lc~omctoiwda dis~uiictlin
det&l]by Del ~ r o s s o ' ~ ~

In the present work sound velocity in pule liquids and in blnaiy

m~xtuiesw a e measused uslng a single crystal valisble path liltel feiomett~i

A sketch of the mtelferometer cell is shown m Pig 2 10 The mlcrfe~osnete~

cell of capacity 12 cm' is made of a slainless steel lube of inner diamelel

0 9 cm is cesnenlcd at the botloln of the cell The ultiasonlc waves move fiam

lhis crystal till they are reflected back by the movable leflectol A fused

qualz rod 1s used as a leflector Thc reflecling surlacc 1s 1 4 cm 111 diarnctcl

Thls 1s coupled to a micrometer screw assembly reading upto 0 001 mm using

a teflon coupler ma the steel rod The micrometel sciew actuates the steel rod

whmh is spiing loaded to take cale of any bdck-lash The mlcronletei

assembly nlong with the reflector IS fiied to Lhe liquid cell with the hclp of a

tlueaded cup and teflon ring A heavy pedestal gves the measuling cell the

required stability Provision has been made for c~rculatmgwater at any

deslred tempeiature from a thermostatically controlled balh lnlo a jackel

around the measuring space to m a n t a n the exper~mentalhqmd a1 a constant

Lempc~atureduring the course olexpcriment

To exclte the transducer (crystal) at a fixed frequency of 4 MHz a

crystal controlled r-f oscillator (cf Plg 2 11)was used The H-T current to

the output tube n fed through a brldge network including a micro-ammeter

in such a way that the change in plate current can easlly be observed on the

mlcro-ammeter Two controls to regulate sensltlvlty and to adjust mitial

 MICROMETER

FIG 2.10
-~
INTERFEROM
-
E T E-~R C F L L
 10 pF
cl
C1
= 0 W7 &r
( 4 0 01 )IF

L,, - 001 PI

L1 and L2 Suitable C Q L ~

G = 1 It 011111 (Gd11) control)

c,lr~cnlof the mete1 me also ~ o v l d c d 1110
1nk1telomolu~thus L O ~ I S I S L111
~

an electrically driven quarte lldnsduccl couplad to llic I~~lnicI

colunln The

lenglh of liquld column can be varied by moving thc clu111tr ~ c i l c ~ ~B0cp111g

to~,

rts plane palallel lo the quartz clystal Whcncvcr t l ~ cd ~ s l ~ ~ 1~elwi.t.11

~ncc
quatz transduce~and the reflect01 co~lespondbto an 1nlcg1'11rnull~plcof hiill

wave lcngths, the llquld column vlh~atesin reasonance TI115 Icdds lo uo

Inclease in the motional lmpede~lceof lhc ltansduccl whrch cauhcs slin~p

d ~ pIn
s the r-f voltage across the transdueel Tile cuiicnt \.in rat~onsate nolcri

in lhe mcro-ammetex The distance eove~cdby loneclo~hclwccn ,my iwu

consecut~vedlps corresponds to one half wave lenglh, A12

Measurement of sound velocity

The lnterferomeler cell was tilled wlth expcirrnen1.1l liilu~cland was

connected lo lhe output tc~m~llals

of tile h ~ g hfrcqucncy gunelalor Lhlough

a shielded cable Tlic cell temperatuic was maintamed at 303 16 I< by

cnculallng watel fiom a the~mostatwhich was contlolled withm i O 01K

'Tho m~croineterscrew was slowly moved till the anude ciuient meler
showed a maximum and the readlng of the m~crometerwas noted whan thc

liqu~d attamed the temperature The d~slancebctwocn Lhc qonilz

llansducel and the reflector plnle was d~spluccdby movliig t.hc sc~ow

downwards To Improve the ucculacy of the mensurcmcnt, several nlaxlmu

were passed and the11 numbel- n (in l,h~scase 20) was co~lnled Tho nnodc

Current was finally adjusted to the moximuln and ihe reading of the
micrometer was agmn recorded The total d~stunce'd' moved by the

reflector was gwen by d = n A12

117
 The frcqumcy of Ilic quailz c~ybttllT bang , ~ L L U I J ~k110w11
C ~ Y I1

MHz), the sound velocity (u)was calculaled uslng llle ~ c ~ l n t ~rr o=n Thc

vnluc of u was obta~nedby movlng the rnl~~orncter

s ~ ~ 11pw:ittls
cw l'hc

average of the Lwo valucs was taken as sound veloc~ly Tlic v,ilucs ai t l ~ c

bound velonty are accurate to 0 15 pelcent The p c r f o i m ~ n ~olc lllc

~ntcifeioineterwas checked by compnnng Lhe sound vclocil~csrccoitlcd in

the piesent study wilh Lhose iepolted in Ll~eIlte~alule(cf T h l c 2 (5)

A leady made colnpute~progtainrne avnilnblc 111 Dcl)n~hnonlol

Chemistry S V Umve~sity,Tiiupat~1s used f o ~the deteimmul~unof exccss

volume Isent~oplccornpress~b~hty,
dewahon In Isent~oplcc o n i p l c a ~ ~ h ~ l ~ l y ,

piedictcd sound veloc~tles(CFT, FLT and Nomoto)

Table-2 6: Sound velocit~esof some pure l~quidsat 303.15 I(

U
Component Souncl veloc~ty-
m see-'

Present work Lite~at~~ie"~

carbontetrachloride 903 904

m-xylene 1304 1302

benzene 1279 1278

cyclohexane 1226 1229

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