Salt Effect in VaporNLiquid Equilibrium,

Part 11'
A . I . JOHNSON' nnd W. F. FURTER,'
Previoub work in the field of salt effect in vapor-
liquid equilibrium and the theory involved are re-
viewed briefly. Vapor-liquid equilibrium data at
atmoupheric pressure are reported for the systems
methanol-water, ethanol-water, and n-propanol-water,
each saturated with a variety of common inorganic
salts. A simple equation is proposed for the repre-
sentation of salt effect. An attempt is made to ascertain
the theoretical fiignificance of this equation, and in
so doing, t o relate salt effect in vapor-liquid equili-
Iirium t o the properties of the system romponents.
PrQvioiiw Srilt E# wt Studies in Vnpor-liquid
Equilihrium
Liiiitc!, , qtdi c\ of wl t cfcct on ;ipor-liqiid c
cur\ ~5 \vcrc undcr;:il,cn I )? J ost"', Yaniaiiioto'",
anJ N;indi"l, I%og'irt aiiJ I %r.~i i i ~cs'~ ,3', l,'o\ ("!, (:raven'
( iuycr, and J ohnsen'"', I hirlcr"'~'oJ , (:osta Novella and
l ':i rrawl l l l , [ ;oogin and Siiiitlit'!'. and J ohnson. I'urtcr, arid
\\'art1 ll.il.
Other in\ cstig;itors cli5tillcd t)inar!, iiii\turc5, first alone,
and then in the prc:cncc of salts. incawring either tlic tlistillation
rate or dcgrcc of cnrichnicnt of the o\ crhcdd product. ' I hcsc
were ()iiartaroli llJ ,'z,ll;l, ligridcs ct al"", and C'irtancn 'Ix).
licfcrcnccs to salt effect arc found i n \\ork by Rlarillcr aiid
<: out ant "' ", I \;cyc~~~"), Sunicr'?'', and \\'alkcr ct aIfyii.
Still other investigators drew conclusions froin \ apor prcs-
sure iiicasiircniciits that arc related to t he subject, those I)cing
)\,I I$al I l I %(! \\' ri gilt I ?I, 2 :t, 2h > , Proszt and l i ol l ar(2i ,2x', and
Miller'29'. .!Iillcr. as early as 1x07, stated that the addition
of a dissolved salt iiiorc solihlc i n water than in ethanol to
aqueous ethanol u,ould result i n the depression of the partial
pressure of the Lvatcr and i n the elevation of that of the al c ohol .
Th e niagnitiirlc of salt effect woul d dcpcnd on the di fcrcnec 111
thc solut)ilitics of the \alt in pure water and i n pure al coh~l .
Flc ot)scrvcd that the total pressure of an cthanol-\\,arcr mistllrc
at constant tcmpcraturc \\' as increased by the addition of potas-
s i ui n chloride. Miller concluded that \\ hcthcr t he total vapor
pressure of a binary systcm was raised or lo\vcred l)y salt
addition dcpcndccl merely on whether thc partial pressure
one conipoiiciit u' as lo\vcrcti more or less than that of the othcr
\US r ai d, this i n turn depending on the properties of the
c( )Illpollelits.
...............................................................................
1 hlrrnirscript reccioed Octobcr 19, 1959; nccci i t r d Fc~linrnr!~ 17, 1980.
2Aasociatc Pr of csr or of Clwniicnl Engrnccrina. Unicrr.yity of Toronto,
:{Rc,senrch Centrc, Du Font of Conrrilo Li ni i t d, Kingston, Ont .
Contribution f r om the Dc8/~iirtmcnt of Choiiicrrl Knginwring, U ~ , i ~ ~ ~ ~ i f ~
of Toronto, Toronto, Ont .
Toronto. Ont.
Industrial application5 of salt effect in vapor-liquid cquitib-
riuni ivcrc reported by I bgart and 13runjcs"~z), (hrl i ai i '"',
I)ittiiiar[:"'. hlorrell and (;illilaiidi:r21, and l i el l y' ~~J! .
Smi c of the best prc\'lolls uorL in the field was carried
out 1)). C iaru iii'.{'I, Kcidcr mi d .l'lioiiii~soii[~z,J , Tursi and
.l'hoiiipson'""', and fs.ogg','ii, I hi\\ r, in only the l at t er two
iincstigations \\'ere even ciiipirical correlations attempted.
'l'hcsc arc rc\.ic\vcd else\\ here"".
In general, the previous work in the ticld of salt cffcct i i i
\,alw)r-Iiquid equilil)riuni has t)ccn rather unccrtrin in nature ant1
tending to lack in fiindaiiicntal approach. I)oiit)ts have been
voiced over the validity of man!' of thc data. 1,ittlc but qtial-
itativc ot)scrvations contirniing the carlv work of hlillcr have
hccn drau 11.
Previous Snlt E#ect Studies in Liquid-liquid
Equilibrium
"Salting nut" I S used gcncrall!, to denot e a decrcasc 111 thc
solubility the noiiclcctrolytc in the solution, or, niore rigor-
I I US~) : , dn increasc 111 i ts activity coctticicnt, caused by the salt
addition. "Salting-in" rcfcrs to the opposite case.
-1'Iic complete Iltcraturc on salting i n and out 111 liquid
solutions has hccn rcvic\vcd coniprchcnsi\dv h\, Imig and
,llcl)c\ it(4"'. 'l'hc!. indicate that thc standarci m&hod of cor-
relating salt effect is to rcprcscnt the logarithni of the activity
coctticicnt of tlic noncl cctrol ~w as a powr scrics in thc
concentrations of all solute spccics (salt and nonelectrolyte)
at constant teml xnturc and pressure, assuming thc solvent to
be a structureless dielectric continuuni and all deviations from
ideality being due to electrostatic interaction al one. Onl y thc
linear ter m arc retained, assumlng niodcrate solute concentra-
tions. The result I S the limiting relation
( 1 )
in which components I , 2 , and 3 represent water, nonelectrolytc,
and salt respectively.
Salt effect thcnrics are generally concerned with the CdkUla-
tion of k,?, thc ion-nonclcctroIytc interaction parameter, and
not with k?!, the nonelcctrolytc sclf-intcraction pararnctcr. Thc
usual units are either niolarity or mole fraetinn. The quantity
of k, , is hno\vn as the "salting out parameter" and is commonly
used to indicate magnitude of salt effect. Negative values of
k3.L indicate the occurrence of the opposite effect, salting in.
1;kctrolytc dissociation niust be considered when attcnipting to
placc salts i n order of cffccti\ciichs. I f niolccular values are
used for LV:t, the salt prani ctcr then includes consideration of
ionic charges and the nuint)er of ions per salt molecule. This
equation has t)ccn found successfill wen at quitc high salt
concentrations ( 4" ) .
I(IR Y : ~ =ki:! &V,i +k.2 .V.. . , .
The Canadi an Journal of Chemical Engineering, June, 1960
78
The causes and effects of the preferential attraction of a
dissolved salt for nnc coniponcnt of a water-noiiclectrolyte
solution over the other havc bccn explained in various salt
effect thcorics, sonic quant i t at i ve but most qualitative. These
attempts can he classified under one of the following. hydration,
electrostatic interaction. \ .in dcr \\'aal's forces, and internal
pressure. They arc discusmi at length I)!, I .ong and hl cl kvi t ( 40) .
The electrostatic thcorics of I)chye and , hk. \ul cy(~~)~
K i rkw~d( 4~) , and others. \\ hilc giving the only really quanti-
tative approach to salt effect, ),icld onl y limiting laws hccausc
of their restrictive assiiniptions. .l'hcy do indicate that the
logarithm of the activity cocficient of the nonclcctrolytc is
proportional to the ionic strength (and hcncc mole concciitra-
tion) of the salt i n the limiting casc of infinite dilution. . i t
finite electrolyte concentrations the clcctrostatic field of an ion
would be expected to he \vcakcncd by ion interaction. Furthcr-
more, the parameters in\.olvcd i n applying these equations arc
often dificiilt to evaluate. -\ltshuller and I':verson(4:g) state that
experimental iiicasurciiicnts of dielectric constants of electrolytic
solutions havc been confusing and coiitradictory. 'They also
state that ionic radii ol)taincd crystallograpliically do not apply
with cxactncss in solution. :\!can ionic radii and distances of
closest approach arc nehulous propcrtics, dltficult to evaluate.
The literature contains few data on the effect of noriclcctrolytc
concentration on dielectric dccrcriicnt. l 'hc electrostatic thcorics
fill generally 111 predicting thc salting out
<:ontinuing in the sinipli tied I)chavior pattern siiggcstcd by
Gross'"!'), salting i n \voulti indicate a preferential attraction of
ions for the nonclcctrolytc over the solvent,
nonelectrolytc is less polar. .l'hc larger the ion, the lesser its
electrostatic field. I n the prcsciicc of either undissociatcd salt
molecules or large ions. (the casc i n point I S mercuric chloride),
the highly polar \Yarer molcculcs would tend niorc towards
orienting into an associated state u i t h each other than with the
salt, forcing the salt particles i nt o the vicinity of the less polar
nonclcctrolytc molcculcs. 'l'hc large ion, attractcd to a non-
electrolyte molcculc, would result in the formation of an ion-
nonelectrolytc association.
Since 110 one theory has I)ccn able to represent satisfactorily
the data on salt effect i n the l i q u i d phase escept in rcstricted
and limiting cases, previous investigators in gcncral agreed that
salt effect is caused hy a complcsity of forces and interactions,
no one of which is suficicntly insignificant in relation to the
others that it may be neglected.
THEORETICAL PRI NClPLES
?'he cffect of a salt, when addcd to a solution of two liquid
components, is to altcr the coniposition of the equilibrium vapor
phase. r\ltcrations in propertics such as vapor composition and
total pressure or boiling tcinpcrature caused by the salt addition
are outward manifestations of the effect of the salt on the more
fundamcntal propertics of the two volatile componcnts, their
chemical potentials.
Salt Eflect o n Chemical Potential
Consider a two-coniponent, two-phase system in which both
components appear in t)oth liquid and gaseous phases. It will
be designated by lack of sul)script. To this systciii is addcd a
non-volatilc dissolved salt which appears only in the liquid
phase. Thi s latter system \viIl be designated by the subscript "so.
Assume the numbcr of molcculcs prcsent in the vapor phase
to be sufficiently small compared to the liquid that a change in
vapor composition will not alter the ratio of the two volatilc
components in the liquid. .4ssume equilibrium to exist in each
of the two systems described ;ihnvc.
Butl ~r( ~~"J ) pointed out that the preferential attraction of the
added ions for one volatile coniponcnt over the other rcniovcs
molecules of the formcr con~po~icnt from their solution role.
This decreases their activity i n the main body of the solution.
Moleculcs of the other coniponcnt are expelled from the ionic
regions into a greater activity in the solution. He indicated
that the nct result was a reduction i n the chemical potential of
the fornicr component and an incrcase in that of the latter.
I t would therefore he rational t o seek a corrclation for salt
effect in vapor-liquid equilibrium in the altering of the chcmical
potentials of the twn volatile coiiipoiicnts hy the salt.
Ilcfinc a measurc of salt ef f ect as:
effect =(pir - p i ) - ( p ; < - p ; ) ( 2)
Assuinc the vapor phase to he an ideal gaseous solution.
( 3 )
.issuniing at constant pressurc, that the salt addition has a
negligible effect on thc tcmpcrature of the boiling system.
substitution of Fkpation (1) into I:.quation ( 2 ) yields
1 iencc
p: =F," +HI' lop y , a
(1)
Since the values of n l and n2, and hence of x. havc not been
altcrcd by salt addition,
a,
a
eHec-t =HI' l op . ( 5 )
Siiicc the system variables arc pressure, temperature, and
the amounts of the components, and since pressure. teinpcratiii-c
and tlic amounts of thc two volatile components i n the liquid
phase are fiscd, the above quantity suggests itself for relating
salt effect on the vapor phase to salt concentration In the liquid.
Assume a llnear relationship as a first approximation.
a,
a
7' log =C Na . . ( 7 )
Reduction of Gilliland's Equation
C~ilIilaiid'~4), using ternary van 1 ,J ar equations, established
that thc ef f ect of the addition of a volatile, nonclcctrolytic,
liquid third component to the vapor-liquid cquilibriuni of a
binary system was
7?'/-y11
72/71
I'log =c#J va ( 8)
where c#J is a function of the ternary van I,aar coeHicicnts.
In the nomenclature of the present investigation, and making
the same assuinption that the temperature of the boiling system
has not bccn altered materially at constant pressure by thc third
component addition, the ahovc equation reduces to
a,
a
T log -- =f(Nn)
which IS similar to Fquation ( 6 ) , although derived for non-
clcctrolyte third components from van Laar cquations.
Assumption of Constant Temperat ure
I f Fquation (7) I S to bc applied in evaluating the effect of
salt concentration on the vapor-liquid cquilibrium rclarionships
of a boiling system at various solvcnt-nonelcetrolytc ratios, the
existence of a rclativcly narrow boiling temperature range
would permit thc assumption of constant tcmpcrature. I n this
casc, I:quation (7) reduces to
79
The Canadian Journal of Chernieal Engineering, June, 1960
where k3 is an empirical quantity representing the over-all
specific cffcct of a gi i w s;iIt oi i rlic :ipor-liquicl cqu1il)riuiii
of a given t)inary system.
Relation of Snlting Oui Parnmptsr i o Viipor-liyr&l
Equilibrium
'l'hc cfl-cct of salt conccntration on the acti\'it\, cocficicnt of
the nonclcctrol! tc (alcohol) I S reprehenred gcncrallj, by the
approxini:ire I,iliiatioii ( 1 ).
.\pplylng the l)ollntl;lry corlllltlorls that .I t .v3 == 0, logy 2s =
log 72, t l l l S c\prcssloll I)ccolllcs
2 )
whcrc k 3? i h the ioii-iioiicIcctroIytc paraiiictcr used by previous
investigators to iiicasiirc salting i n and out and k:, I ivould siiii-
ilarly rcprcscnt ion-solvent interaction.
I 'iluations (9) and ( I 3 ) arc identical \\,hen
ki =k i r - k.ii . . (1.1)
Cancelling-out of Terms
I ~iliiatioii ( Y) , \vliicli has t)ccn arri\.cd ;it from thrcc difTcrcnt
directions, postulates a linear relationship I)ct\vcen the qiiantitics
involvcd only for a constant sc)lvcnt-nonclcctrol~~tc composition
ratio. It has t)ccri argued that salt cfTcct is a coniplcs function
of intcractions and self-ciitcractions I)ctwccn all thrcc ctirnpo-
ncnts. In addition, the dcgrcc of dissociation of salts i n aqueous
alcohol I S known to vat-)' \\.ith the \\~atcr-alcohol ratio. ~l'hcre-
fore, no tlicory cxlbts to indicate that the value of k, should 1)c
cxpcctcd to rciiiain constant for a givcn system as the 1)inary
I iquid coni p( isi ti on I s vari cd .
It is evident from I;+ations ( 10) and ( I I ) that in thc a1)scncc
of simplifying assumptions the!. should have additional terms.
?'his fact t)ccorncs iiiorc apparent \vhcn 1~'quarions (10) and ( I 1 )
arc dcrivcci froin definitions of tlic activity cocfhcicnt and the
"Gibbs characteristic" 'I"'.
However, it is conceivable that tlicsc interactions may either
not vary apprccial)ly, o r , iiiorc I~kcl ) ~. tend tn halance c.ach
other, as the solvcnt-nonclcctrol!.rc rati o is varied. Shorlltl this
prnvc to be the case, then the addi t i onal tcrnis of I*.quations( 10)
and ( I I ) uoul d tend toward cancelling each other. Since
I:,quation (c)) represents the difl-crcncc bet\\
and ( I I ) , such a cancelling tendency noul d permit Is:qiiation (9)
to rcprcscnt a \rapor-liquid ccliiilit)riuni curve, and to rcprcscnt
it even in cases when I ~iluations ( 10) and ( I I ) failed altogctI1er
for varying values of Y?.
Corrplntion and Prediction
I laving csta1)lishcd the value of k.i . ai d kilo\\ ino tlic v<ipor-
liquid cqui1iI)riuni data fi)r tlic liinar!, s!.atciii trcc of a,l l t,
I~kliiation (9) \voiild pcriiiit the calculation of salt cKcct on
vapor-licluid cquilibriiini, a h o u l t l i t lie fi)und to apply.
[.'or an)' value of .xi, the equation uoi i l d r chc sal t concciitra-
tion to vapor coinposition. It \wniId prcdicr thc \ ~: i p: ) r- l i qui d
cquili1)rium curve for any givcn salt co~iccntr~ition o r calculate
the aniount of salt ncccssar\ for .I deal red \'ap:)r cnricliniciit.
In addi ti on, i f salt solut)ilit!. .IS a firiictioii of t)iii,iry IicllIid
conipositioii i s kno\ \ , n or can I)c c\tini:itcd, thi\ cqu.itioii \\,oi i I ci
predict the cqiii1it)riuin curve tor satur.itcd salt concciitr;ition
from the salt so1ril)ilitics i n the t\vo pi re coinl~)iicnts. 'l'lils
latter curve \vould represent the iii;i\iiniiiii cfl.cct poasit)lc from
a givcn salt, this iii;iuiiiiuiii cff'cct hclng .I fiinctiori not onI\ of
rIic sdlt cKcct paranictcr \)tit also of tIic soIuI)iIit! of tIic kxit.
EXPERIMENTAL METHOD
?
.\ primary purpose for cstat)li\hing tlic 1)in:i
cquilibriuni data of the rhrcc alcohol-\vatcr s-
compare tlicsc data to those i n the literature ;is
accuracy of the appi ratus :ind c\:I~criiiicntal nictliod. 'l'hc data
for the cthanol-\varcr systcn atmospheric pressure \vcrc rc-
ported i n Part I of t h i s scr
I). 1 hose for mctli;inol-\v;ircr
and n-pr[)pdii(il-\~~itcr, along \\ i th a coniparison \\.it11 1itcr:iturc
data, arc included 111 this piper. l'hc nicthod I\ that t1cscriI)cd
in Part I . In addition, i n each run wi th thcsc thrcc ti nary systems,
the stcad\. state liquid coiiiposition, calculated l ) \ , niatcr1;iI t ~ .
ancc froi i the voIuiiics anti cicnsitics of the charge to tIic still
and the stcad)' statc coridcnscd vapor holdup 111 the condcnsatc
chamber, \\'as coinpared to the actually measured \ aluc at the
end of the ri m. Thi s \\'as a check on the material balancc
mcthotl uscci to ohai n the cquilil)rium liquid conip)\ition on a
salt-frcc basis i n the presence of saturated salt.
Thc data for thcsc two systcms arc rcp:)rtcd in 1'aI)lcs 1
anti 2. Figures I arid Z illustrate thcsc data. \\,cr;igcs of the
~i rcraturc &td ()I] Ii,etJ lall()l.\\.atcI-' 11. ~~, ~~. : ' ~~, 52, il. 54!
n-prnpanoI-\vatcr ('4,46,4x,4'1J arc she\\ 11 as solid line\ i n thcsc
figures, whilc tlic poi nts rcprcscnt the cspcrinicnt:il dat a reported
in the tables.
The alcohols ;ind salts used i n the invchtigation \\ crc of
analytical reagent grade. 'l'hcir c\act spccific'itions :ire listed
wi t h the original data""'.
I 'hc vapor-liquid cqui l i l ~ri uni data for the alcohol-\\ 'itcr-halt
systems \vcrc obtained \\ ith the appiratiis and method dc-
scribed in Part I . I;or sonic of the systems, saturated sal t
concentrations were measured b\. Al ohr titration for chloi-idc
i on, while for others the concentration \\' : i s nicrcl!~reportel1 as
being saturated. 71'hc stcad\, state liquid composition \vas cal-
culated by material t)aIancc. from the volunics 'ind dcnsitich of
the licl~i~d charged to the still before the addition of s:ilt and of
the stcady statc condensed vapor IiolJup. conipositions bcing
oI)taincd I)), specific gravit\' nica~urciiiciit of s:iiiiplcs.
EXPERIMENTAL RESULTS
l 'hc cxpcririiciital data for the alcohol-water t):nLir! systciiis
chcckcii \vi th the a v e r a d Iiteratrirc data to al)out tu ci-tenths
of onc molc per cent. I'hc comparison t)ct\wcn stcad), stxtc
liquid coinpositions ;ictuall!, measured and those dctcriiiincd b\.
material balance shoivcd an average dc\ iation of lcs\ than 011,-
tenth of one mol c per cent, indicating the sj xci i i to t)c c1osc.i
and the niatcrial balancc nicthotl a suital)lc tcchniqt1c.
'l'alilcs 1 and 2 list the cupcrimcntal data for mctliaiiol-\v.iter
and for ~i-propanol-\\~atcr and l'ahlcs 3 to 26 list the v:ipor-liqud
cquili1)rium data at atmospheric prc;surc for 2t alcohol-\\ atcr
saturated systems, the compositions being reported on a halt-
frcc h i s . ~I 'aI )I cs 27 and 28 rcpxt addi ti onal d.ita for the
systems iiicthanc~I-\\,~tcr-animonluIii chloridc ;inti nicthanol-
water-calciuni chlorldc in \\ hich for each of several I i qqi i t i
coinpositions on a salt frcc l):i\is, salt conccntratioii \\'as varic,i
t
The Canudian Jotrrncil c at Cheniical Engi neeri ng, June, 1960
80
00 01 0 2 03 0.4 0 5 0.6 0 7 0 8 0 9 10
X
Figure 1.
00 01 0 2 03 0 4 0 5 0 6 01 0 8 09 1 0
X
Figurr 2.
Typiral liquid-vapor rquilibriutu curves for methanol-watrr with ~ a l t rffrrt (atmosphcrir prrwsure) I
10
I I I I I I I 1 I
09 -
011
-
0 7 -
SODIUM CHLORIDE
I SATURATED I
0 2
O f / 01
0.0 1 I I I I I I 1 I
0 0 01 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 10
0 0 0 1 o e 0 3 0 4 0 5 0 6 0 7 o n 0 9 10
Figure 3. Figure 4.
Typical liquid-vapor equilibrium curves for ethanol-water wi t h salt rffcv-t (atmospheric pressure).
and its effect on vapour composition noted. <:oiiiplcte tal)ulatcd
data arc obtainat)lc from the .Aincrican I)ocuiiicntatioii Iiistitiitc.*
I;igurcs I to x illustrate soiiic of the typical vapor-liquid
cquilibriuni curves. The curves arc for atiiiospheric pressure
and are rcprtcd on a salt free basis. lhc curve for the corrc-
spmdi ng alcohol-\vatcr systcni \vithout salt i s slionm oi i each
figurc as a dashed linc for coinparison pnrposcs, i n ordcr that
rhc inagnitudc of the salt effect may be seen rcadily. I.itcraturc
data arc includcd on thcsc graphs for the systciiis for \ h c h any
cxist. (kniplctc graphs may he seen in thc original thesis. (:In)
OTahles 1 to 28 of this paper havcs ,hwn drpmitcd n\ Ihcnment No. fi2rifi
with the AD1 Auxiliary Puhliriitiim Froicct, Iliiit,idiiplicatiiin Srrvicc.,
Lihrary of Congrcw, Wa\hington 2.5. 11.C. A copy mny he ol)t.iinrd h y
citing the Docirnwnt No. and hy remitting $ 1.2.5 for photoprints. or
$1.25 for 3.5 nim. inicrofilm. Advance pnynwnt k requlrcd. bf.tk<.
cheques or monry nrdcrs pa s ~l ~l c to: Chirf. I l ~~i t i ~dupl i cat i i ~~~ Srrvicr.
Lihrary of Congress.
DISCUSSION OF RESULTS
Although most salts salted out alcohol froin water i n the
three alcohol-watcr binary systems invcstigatcd, as I S evidcnccd
by the iiicreascd activity of alcohol in the vapor phase, sonic
had little effect because of low solubility. T wo salts, mercuric
chloride and iiicrcuric bromide, caused salting in as illustratcd
i n Figurc 8. The occurrence of this latter effect rcsults in
negative valucs of k, .
Sonic very slight shift of the ethanol-water azcotropc to a
composition richer in ethanol apparctitly is caused by thosc salts
iiiost effective at salting out ethanol. Thi s effect is indcfinitc
because the solul)ilit!~of thcsc salts in the azwtropic mixture is
s o low that salt effect is alniost noncxistciit. X s shown in
I:igurcs 5 and 0 thesc salts do cause marked azcmropc shifts
The Canadian Journal of Cheniical Enginrering, June, 1960
81
10
I 1 I I 1 I 1 1 I
0 9
0 0
0 1
0 6
Y
01 O 2 I/
i
( SATURATED)
i
1 I 1 I I I I I I
00
0.0 01 0 2 0 3 0 4 0 5 0 6 0 7 0 0 0s 10
X
Figure 7-Liquid-vapor rquilibrium data for n-propanol-
water wi t h ammonia chloride (atmospheric pressure).
in the n-propaiiol-\vat~r systciii becausc of the higher salt sol-
ubility in the iiiorc water-rich azcotropic coinposition. R4crciirtc
chloridc (Figurc X), being qiittc solublc i t 1 the azcotroprc rcgioii\;
of both systciiis. caiiscs a substantial shift i n the other direction
owing to its salting i n ef f ect .
Most of thc salts that caused salting nut of the alcohols
were much tiiorc solul)lc in watcr than in thc alcohols. Sincc,
at saturatcd salt coticcnrrations, salt cffcct is a function of its
solubility in thc syst em, thc large salt cffcct in the watcr-rich
regions, which tcntls to diiiiinish rapidly as liquid composition
movcs toward the alcohol-rich region, I S cxplaincd. l 'hc shapc
of the solut)tlity curve also explains Lvhy salts such as mercuric
chloride, which are quitc soluOlc in both components, cxcrt a
more uniform cfTcct throughout the binary composition range.
10
0 9
38
0 7
0 6
Y
0 5
3 4
3 3
0 2
01
0 0
MERCURIC CHLORIDE
( SATURATED)
I 1 I 1 I I I I
0 0 01 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 1 0
X
Figure 8-Liquid-vapor equilibrium data for n-propanol-
water with mercuric chloride (atmospherir pressure).
.l'hc former ef f ect is chardctcrizccl by a slnall fractiondl \ J I U C
of the cxponcnt in I':cluation ( I j ) , inti the latter I)y J value
closer to unity.
bkaiiiiiiatioti of thc ddta sho\vs rhc hoiltiig ranges of the
systcms iiivestigatcd to he quite narrow over tilost of thcir
liquid composition rangc7. \\.'hen this range width is compared
t o the approuimatc absolute tcmpcraturc, the fractional variation
would appear sufficiently small to justify the assumption of
constant tctiipcratiirc. I.\arnination of thc data also s h o w s that
boiling point el evat i ons ani depressions caused by the salts arc
quite siiiall, usually a degree or less.
I ~~xpcri mcntal l ~~. saturation u as assuiiicd to cxist whcri a
slight cxccss of solid salt pcrhistcd over a period of timc. .Ill
salts employed in the investigation dissolved qutrc rapidly.
The Canadian Jorrmal of Chemical Engineering, June, 1960
82
AMMONIUM CHLORIDE- ETHANOL- WATER
I-
t
1.0
0.9
0.8
0 7
0.6
0.5
3
2
1
I I
Figure 9 - Typical calculated data showing interaction
~~ararnet c~s and rorrelation constant.
l*.urtherniorc, tlic s)zstcni was saturated with salt under conditions
of zero vapor condensate holdup. The establishiiicnt of a holdup
after tirst approaching saturation further ensures Its attainment
by rcinoving sniiic salt-frcc liquid from the salution as vapor to
create this holdup.
Because of the material I dui ce technique of establishing
thc equilibriuni liquid coiiiposition, salts Itnown to possess hy-
dratcd fnriiis at the conditions of tciiipcraturc and pressure
i n\dvcd were a\widcd generally .
salt prcscnt to cnsurc saturatioii, hy 1)ccoiiiing hydrated or
alcoholatcd, \vould alter liquid coiiiposition.)
In soiiic systcins the salting out ctfcct was of such iiiagiiitiidc
as to causc a rctluction of iiiutual solubilit) to the point of
formation of two liquid phases as illustrated in t:igurcs 0 and
7. Thi s effect t)ccoiiics iiiorc prol~al)lc as the alcohol series IS
ndcd and the alcohol-water nititual solubility is less.
.-In advantage of analysis of cqiiililmuiii liquid composition
b!. niatcrial balance occurs in systcnis in which the salt causes
formation of a region of t wo liquid pha.
charge I S analyscd before the salt is added, this iiicthod perinits
the cllcularion of over-all liquid composition at stcady state, a
quantity very clifticult to iIicasiirc otherwise. I n the rcgion of
two liquid phases, the phase rule indicates that x r o ilcgrccs of
frccdoin c\ist. a fact coritirnicd by the horimntal slope of thc
cquilil)rium curve. 111 this region the compositioiis of the vapor
and t wo liquid phases arc tiucd and only the relative aiiiouiits
of the t wo liquid phascs can 1)c varied.
(The slight L'S
TREATMENT OF EXPERIMENTAL RESULTS
(a) I n 'l'ablcs 27 and 28 data are reported for t wo systcnis
in which x: , was held constant at cacli of several values while salt
concentration was varied. As shown in Figure 9(c) the data
for each value of x:! \\'ere plotted as per I quation (9) and the
values of k , cstahlishcd. From thcsc \ dues of kl, the kllown
salt-frce tinary cqiiilibrium d:ita, and the cuperimcntally Incas-
urcd valucs of .v? and A':{, I,:qumon ( 9) \\;IS employed to calculate
vapor enrichnicnts. 'l'hcsc calcdatccl \.alucs of y. \\'ere compared
tn the eupcrimcntall\, dctcrinincd valucs. ?l'hc over-all average
numcricaI cieviation for the 17 cupcriiiiciital poIrits of these two
s)'stciiis \vas 0.003 niolc fraction. I:or a given s\'stcn). rhc value
of kl was otiscrved to t)c almost indcpcndcnt of s?.
(b) I hta arc rcported for 2-t s?'stcnis colisisting of alcohol-
water-saturated salt. I n 9 of rhcsc s\wcnis, saturated salt
concentrations were actually riirjsurcd.. l:or each of thcsc 9
systems. the data were plotted as per I : , pt l on ( 9 ) and a
straight line dr aw to determine the best s~ngl c value of kn
for the s)xciii. is aI)ovc, I:,quatiori ( 0) \ v ~s then used to caI-
culatc vapor conipositions. which \vcrc thcii coinpared to the
cxpcrinieiital \values. l'hc over-all a\'cragc nuriicrical deviation
for the I 16 cspcrinicntai points of thcsc o .ivstenis \\as O.OW
inolc fraction.
In additioii, as illustrated by I:igurcs 9(a) anti 9(l)), activitj,
coefhcicnts were calculatcd from the data, a i d thcsc data were
plotted as per Is:quations ( 10) and ( 1 1 ) for the purpose ofcuainin-
ing any tendency toward the proposed cancelling-out effect.
'I'ablc 29 lists the values of thc parameters obtained from these
plots. Values of k , , and arc reported to only two tigurcs
1)ccause of the apparent non-lincarity of the data with Fyuarioiis
(10) and ( 1 I ) . l 'hc additivir!. cuprcssed i n 1':quatioii (14) is
tn benoted.
(c) Providing the relation 1)ctwccn salt solubility and binary
composition is known, I:,quation ( 0) is propscd to predict thc
vapor-liquid cqiiiIiI)riuni ciirvc of a . ten1 from a knowledge of
only the solubility of the salt in each of the t wo pure volatile
coniponcnts.
for which saturated salt concentration data had IJccn iii
the intercepts representing the salt solubility in the t wo pure
components. 'lhcsc curves indicated that a relatively large
ainmint of the coiiipoiiciit i n which the salt is iiiorc soluble is
required to change the salt solubility appreciably froiii its value
i n the coiiipoiicnt in nhi ch i t is less soluble. Thi s effect is great
with large solubility di ffcrenccs of the salt hctwccn the two
coiiiponcnts and sniall nhcn the difference is little. In other
\vords, the solubility ct~rvcs wcrc fcstooii-ltlic in shape.
Kccause of the coinplcsity of the various solution phcnoniena
governing the solubility of an clcctrol!ttc across the entire coni-
position raiigc of a hl i i i g binary solvent under coiistarit pressure
conditions, an cmpiricLil soliil)ilit!, relation \vas chosen. The
contiguration of the iiicasurcd solul)ilit!~curves suggested the
following relation:
(IS)
tvherc S s I arid .S3? arc the intercepts of the S:3 versus .I-:! curve
and represent the salt solubility i i i the piire coiiipnneiits. The
\.alucs, taken froni SeidcII(A", of salt solubilitics at .I-:! values of
0, 0.5 and 1 were used to c\raluatc the constant tl for each
system. *['he values of S, , anJ S,{? were taken at a single teni-
pcratnrc for cach system, this teiiipcraturc representing the
average boiling temperature of tl ystciii. 'l'hc valuc of ka
was calculated For each of the 24 ciiis froin a single cspcri-
mental point of each syst em. 'l'hc values wed arc contained in
'I'ahlc 3 0 . ('l'hc rcasoii for k.3 differing for a given systeiii
\)ct\vcen 'l'ablcs 29 atid 3 0 lies 111 this siiiglc tciiipcrature at
Ivhich values of S:$ I and S, , \vcrc taken froin the literature.)
From the known salt-free binary vap:)r-liquid equilibriuin
curve and the values of . \ 13 calailatcd froiii S, (i n turii calculated
froni I<quation 1 F), the saturated aalr vapor-liquid equilibrium
curve \vas predicted with I,;quation (9) for each of the 24 systcrris
at x:! values froin 0 to in 0.1 iiicrcincnts. l 'hc calculated vapor
coriip)sitions were coiiiparcd to those t aken from the cxperi-
<:urvcs of S, against .r2 \vcrc plotted for the nine
.S,{ =(.L - .%I ) .,J +.%I ,
The Cnrindian Joiirrinl n/ Chertiicnl Eiigiiieeririg, June, 1960
83
! kl l
- ~~
- 1 2
- 1 2
- 1 2
- 1 0
- I 0
- I n
- I n
- I 0
- I 0
k3
3 12
3 5 6
5 18
3 38
3 40
4 16
1 75
2 83
-. -
2 m
nicntally ilctcriiiincd curves. 'I'hc over-all average dcviatioii
for the 264 point of thcsc 24 s)xciiis was 0.Ooi mol e fraction.
'l'hc detailed calculations and coiiiprisons outlined aliovc
are prcscntcd iiiorc fully cIsc\vIicrc'~'x'.
DISCUSSION
Represent at i on of Dicta
I:,quation (9) \vas found to represent salt cffcct on vapor-
liquid cqiiilibriiiiii succcssfidly wtic'ii salt coiiccntration was
varicd at coiistaiit x.. (kryi ri g this out at various ti ved valncs
indcpciident of tmiary liquid coiiipnsition.
This observation was further confirnictl i n the ability of
Ilquatioii (9) to represent the data for the nine s\sstcnis in which
salt concentrations were measured, using a single value of k3
over the entire liquid coi i i posi t i on range of each systciii. I.'urthcr-
iiiorc, for thc 2 t systems tested, t)ccauac saturmd salt conccntra-
tion as a fiinction of liquid conilmsitioii and tciiipcraturc \vas
capable of ki ng approsiiiiatcd, the cqtiation allowcd prciiictioii
of thc effect oi i the \~apor-liquid cquililmuni curve of saturatiiig
the systciii wi th salt, from a knowlcdgc of ttic hasic so1ut)ility
propcrtics of tlic coiiipoiicnts. ' 1 he rcprcscntation (if thc data
by I,;quation (9) was accurate to a iicvi.1tion of the order of
onc mole per cciit or less, thcsc tl tioris including any cspcri-
nicntal inconsistencies i n thc unsnioothcd data.
tCI11, thc ~]Ucllltlty kj \VdS folllld t0 t)C rCl atl VCl !'
Cancelling-out Eflect
'l'hc o1)scrvc.d lack of change in the valuc of the fiinction of
k , across rhc Iiqiiid coniposition range of a systcni would indicate
thc csistencc' of a halancing tcndcnc!~, or cancelling-out of oppos-
ing effects, aiiiong the various ef f ect s comprising the action of a
salt on vapor-liquid cqui1it)riuiii.
. An cx;iiiiiiiatioii of the pl ots of activit!, coetficicnt anci
relative volatility ratios against salt coiicentrdtioii as per I4:qiia-
tioiis ( o ) , ( I O), and ( I I ) for the iiiiic systciiis indicates clearly
that I,:cluation ( 0 ) tends t o rcprercnt thcsc data liricarly while
I ~iluations (10) and ( 1 I ) do not . b'igurc Y is includcd as a
saiiiplc illustration of one of these systems. I t may hc sccii from
thcsc plot\ that, for each 1 alue of salt concentration, the activity
coctficicnt ratio of the water tends to deviate in the same d~rcc-
tion frorii a bcst straight line as docs the activity coctficicnt
ratio of thc alcohol Since I~:quation (9) rcprcscnts the di ffcrcncc
tions tend to cancel,
cr thc entire vapor-
liquid cquilitirium cur\c of a given system with a single value
of k, .
Predi ct i on of Salting Paramet ers
.~l tl i oi i gl i I'i1iiatioiis ( 10) and ( I I ) rcducc in the limiting casc
of infinite dilution of oiic of tlie volatile coiiipoiiciits to Raoult's
I .aw, attcmlm t o calculate k , I arid k:,? froin vapor prcssurc
depression data were iiiisii fill, since it was found that thc
liiiiiting valiics so ohtaiiied di d not approsimatc tlie values in
the prcscncc of the second volatile component. I.'or tlicsc
systems i t has t u n necessary to estat)lish the value of kp froin
a single cspcriiiicnt'il dctcriiiination per system.
l<aoult'\ I ,a\v predicts that the salt would lo\vcr the vapor
prcssiirc of each volatile coniponcnt in the atwncc of the other.
I Icncc the limiting values of k : , l and k:ir in thc absence of the
ilatilc coniponcnt \voul d hc cspccted to he ncgativc.
r, \VI I CI I salt is acidcd to a miutiirc of the t wo volatile
coiiipoiicnts, thc salt, in salting out one coml~oiicnt, acttially
r t u w i t s partial prcssurc while lowering that of the othcr. l 'hc
difference tictwccn the cffcct of the salt on a coiiiponcnt alonc
and on that coiiiponcnt i i i the prcscncc of the other would then
t)c an indication of the relative importance of the ot hr r in
dctcriiiining the tot:il salt cffcct in the iiiixtrirc.
I1 I~:(~"atlolls (10) and ( I I ) , thcsc d
g I squation (9) t o hold adcqiiatcl
0 225
n 118
0 125
0 3 2 0
n no 1
0 021
0 0 0 2
0 007
0 019
0 022
0 129
0 010
0 242
0 134
0 350
0 020
n 120
o 078
~ - -
-
n s
i n
n 3
n 3
0 . 3
0 3
0 3
1 0
1 0
0 2
0 1
0 3
0 3
0 2
0 4
0 2
1 0
i n
n 3
0 2
2 0
-0 9
3 6
4 8
4 2
3 0
3 5
-0 6
-0 9
0 1
2 0
1 0
3 5
2 4
3 5
6.9
6 3
2 7
4 0
-0 9
The Carradian Journal oj Chemical Engineering, June, 19M)
Therefore the departure of the salt-water interaction para-
meter knI froni a negative valiic could he considered a measure
of the relative significance of salt-alcohol intcraction in dctcr-
mining salt effect, and the departure ofthe salt-alcohol interaction
parameter k n 2 from a negative value a nicasurc of salt-water
interaction signi ficancc.
The salts aiiinioiiiiini, sodium, and pDtassiiini chloride salted
out the rhrcc alcohols under study froni aqucoiis solution quite
strongly. ?l'hc values of k:il were ol)served to t)c negative, while
those of the salting out paranictcr k , , were changed to sutistantial
positive values. 'l'his would indicate that salt effect is strongly
governed in the al)ovc examples by ion-\vatcr iiitcractioiis and
only by ioii-alcohol interactions. .l'his fits \\ell with the picture
of the strong afinity of the ions of these rhrcc salts f or highly
polar water molecules, i n effect rcpclling the less polar alcohol
niolectllcs from the ionic regions of the solution and removing
them from close coiitxt with the i ons.
Relation of Salt Eflect in Vapor-liquid Equilibrium
to Salting In and Out in Liquid Solutions
Salting nut of a non-clcctrolytc i n liquid solution has bccn
explained ti), the fict that the ions cscrt a preferential attraction
for the iiioleculcs of one volatile conip:)ncnt over those of the
other. 'l'hc former arc drawn into associations with the ions,
reducing their activity i n solution. 'I'hc latter arc espellcd froni
thc ion regions into a greater activlt!~in the body of the solution
reniotc froni the ions.
Hccausc of the electrostatic field of the ions and its attraction
for these molcculcs, the volatility of the regions consisting of
ion-molecule coinplcscs I S at)nornially l ow. I Icncc tlie vapor
composition is dcterniincd niainly by the solution rcb' 3 rions reniote
froni the ion fields (rather than by the over-all liquid composition
as woul d be the case i n the al wncc of the salt). Since the
portion of the liquid from \vhich iiiost of the vapor arises has
been increased in the less-attracted coiiiponcnt, the net result is
an altering of the cqiii1it)rium vapor composition. 'l'he increased
activity of this latter coiiiponcnt in solution is reflected by its
increased partial pressure in the vapor while the partial prcssiirc
of the more-attracted component I S reduced by the salt addition.
Reduction of Mutual Solubility
.AS a general rule, the degrcc of solubility of onc siit)stancc
in another depends on the dcgrce of siinilarity bctwecn the
molecules of tlie two su1)stances. 1,ikc thinqs -_ tend to dissolve
in each other. \\'hen lolls arc added to a solutloli of t\t'O \rolatllc
nonclcctrolytcs and they cxcrt a prcfcrcntial attraction for one
cornponcnt over the other, they enter into associations with this
coniponcnt. By s o doing, they reduce the degree of similarity
betwccn the t'wo conipnncnts. l 'hi s I S offered as a simple
qualitati\re explanation of the reduced mutual solubility that is
Relation of Salt Solubility to Salt Eflect
(a) Previous investigators have noted qualitatively that a
salt more solul)lc i n the less volatile coniponcnt than in the more
raises the relative volatility of the systcni and v~cc versa.
*I'hc relation of salt soIut)iIity to its attraction for a component
is postulated as the explanation for this observation. Since like
things t end to dissolve liltc, ionic sul)stances such as potasslut11
chloride would he expected to t)c iiiorc solut)lc in polar water
than in less polar alcohols. I n other words, as a general rule, rhc
salt wo i i l c l be more soluble in the compwnt for wliich it
exerts a grcatcr attraction in solution.
?I he salt, having a lesser attraction for the component in
which i t is less soluble, salts out this coniponcnt, hence raising
its volatlllty 111 relation to that of the other. If the coiiip[)ncnt
in which the salt I S less solul~lc is the niorc volatile, thc relative
T()latility of the system is r ai d, and vice vcrsa.
Since salt cffcct is governed by the dcgrce of difference
bct\frccn the attraction of the salt for one coniponcnt over the
othcr, the above postdate also explains why the niagnitudc of
salting out.
salt effect has been observed o tic a function of the difference
betwccn the solubilities of thc salt in the two pure components.
(b) I:or cases in which salts exhibit festoon-like solubility
ciirves with liquid compxition, a d lopnicnt similar to that of
Gordon(c16) will yield a inore rigorous basis for the rclation of
salt solihilitics in the two pure coiiiponents to salt effect in
vapor-liquid equilibrium at saturation.
For the purpose of the fi)llowing argiimcnt only, asslillie
that <:omp:)nent 1 is the coiiiponcnt in which the salt is niorc
solut)lc, and that 'I., P, and I / I arc held constant. \\'lien the
saturated salt is in cquili\)rium \vith a slight excess of solid salt
(i .c. its chemical potential I S constant) expansion of thc derivative
of the chemical potential of the si l t in i ts variables reduces to
Rearranging the order of difl-crcntiatioii, this expression
bccon1cs
the intcrccpt, at I I ? =1, of a tangent drawn at any point to the
curve of salt solubility plotted against salt-frcc binary composi-
tion x ? .
For salts exhibiting festoon-like solubility curves i n a binary
solvent, this intcrccpt woiild I)c generally ncgativc in value.
\\'lien (2) is negative, and siiicc is inherently
71 I
11froni the abavc relation that p2 is an increasing
fiinction of salt concentration. \\'hen p 2 I S an increasing fiinction
of salt concentration, the Cibt)s-l>uhcm cqtiation indicates that
I.( I is a decreasing fiinction of salt conccntratioii. I n other words,
(:omponcnt 2, the comp:)ncnt in which the salt I S less soluble,
is salted out. I ts increased chcniical potential is iiianifestcd in
its increased concentration in thc vapor phase.
Nonelectrolyte Order
l 'hc electrostatic theories of salting out predict that the
degree of salting out in aqueous solution increases with a
decreasing dielectric cnnstaiit of the nonclcctrolyte.
Fnr a given salt, it was observed that the value of the salting
out paranictcr k S 2 was grcatcr for alcohols of lower pdari ty.
As the alcohol series is ascended and this component t)econies
less p:)Iar, it IS observed to be iiinrc strongly salted out from
aqueous solution by salts which cause this effect.
Order of Eflectiveness of Salts
Salts have been ranked i n their order of effectiveness pre-
viousl!~by the value of the salting out parameter k, ?.
The values of salt paranieters reported i n the 'l'rcatnicnt of
Rcsiilts section arc based on niolc fraction salt concentrations.
I:or highly clcctrovalent salts, salt order should be established
by k valires corrected for dissociation (ix. by ionic strength).
Ilowcvcr, this would not appl)' f or such salts as the mercuric
halides. Thcrcfore, a tiasis of comparison is difficult.
for salting
out in solutions of two pdar conipieiits yields the following
diminishing average order.
cations . 1.i - ,YCT - I< - /hi ~ Sl l , - K b - C H
anions : SO4 - C'I -- Hr ~ S O, ~ I
I<xamination of the cxpcriniental valucs of k3, corrected for
ionic strength, for various cations wi th cach anion and for
:\n average of the L h t a listed in the
The Cnnadian Journnl of Cheinicnl Engi neeri ng, June, 1960
85
various anions \vith each cation, :n each binary systclii, yields
the following cliiiiinisliing average order:
cations : A' l i li ~ I% ~ Hr7 ~ StI., - ilg
anions . SOI (.'I ~~ Hr - A'O;, I
Thi s o\)scrvcd salt order is atmut ah similar to the average
order i n the literature as any one from the invcstigatioiis making
up the avcragc litcratiirc order. (I t is to be emphasized that
this latter order I S very rough and changcdblc for polar so1vents.)
(;lasstone'"" lists the folln\ving crystallographic ionic radii :
1.i 0.60 .j.
S'I 0.95
I l g 1.10
\'/J 1 . 24
li 1 . 3 1
I t? I , 3 5
,VIl4 I.+X
lth I ,4!4
(' 5 I .69
The electrostatic theories of salt effect predict that salr
effect diminishes with increasing i o n r j d i i i h , hince tfic clcctro-
St'dtlC ficld of the ions is greatest when inn radiiis is SI i l dl ~eSt ,
causing a maxiniuiii attraction for highly polar water molccuks
undcr this condition. f lowevcr, i t has ticcn dcrliolistrated
previously that salt cffcct is not governed by electrostatic
interaction alone but is rather a coinplcx function of all possil)lc
interactions. Thi s accounts for the 6dCt that, although saltirlg
out generally diminishcs in aqueous solution with incrcasing ion
size, the order is not mirrored exactly. (I 'he covalent nature
of the niercuric halides accounts for the low r f f cct of the
relatively small mercuric inn).
SUMMARY
It is interesting to note that, for the systems investigated,
this apparent balancing of various intcractions enables this slmplc
relation to represent not only the effect of the variation of salt
conccntration on the vapor-liquid equilibriuni of a systcin for a
single ratio of the two volatile coinp)ncrits i n the liquid phase,
but also for any ratio of these two conlpnnents, with a single
valuc of kn.
Salt cffcct in vapor-liquid cquilihriuiii is proportional to the
valuc of kn. but i h limited by salt solubility. The valuc of kn
was found greatest for salts exhibiting the greatest solnbility
differences between the two coiiiponcnts. [I owevcr, the salt
inust be sutiiciently soluble in the conip:)nent in which it is less
so~ul i k, t o dissolve t ( J the concentration required for the scpara-
tion. Both factors iiiiist be considered in the choice of a salt as
dn extractive agent.
Acknowledgment
The authors wish to acknowledge tlir National Research Coiincil of
Canada f or their support in this investigation.
Nomenclature
Coniponcnt 1 =\v;itcr
2 =;ilc.ohol
,, 3 = s a l t
=moles of ~ i i i p ( ~ i i c ~ i t i i n vapor phasc
=niolr fractioii cmnipoiient i i l l liquid ( 3 conipoiiciit I )<i +i ,)
n,'
n, = , I ,, ,, ,, liquid ,,
N,
Si = ) ) ,, ,, ,, (salt-free l)a*i*)
?'. = ,, , I , , I S
n I ' n ?'
y: =-
n1' +N.'
Yl = - - ~ ~ -
nl' +nl'
T =temperature, "A-
T =total pressure. :itnioq>here.:
P,"
l',
p,
F,"
C =cmpiricai coiistiiiil
7,
a =rc.l;itive volatilit!
=vapour prcssurc of piire compo~ii~tii I ;it tenipcrature i n
=volilnic fr;ic.tioii c.r~nipi~i~ent I i n l i cl i i i I ( 3 coniponciit basis)
=chemicyil potential of (omponcilt I
=frc.c cairerg? C J f ~ ~ o i n p o i i c i i t I i n i t5 st.iiid;ird statc
=activity rocffic.i~-iit of coiiiponcnt I
qucstion
K =gos collstant
Y, n- Y? XI
a =
?' =L _ ~
References
l',d n: Y l s1
(1) J ost, W., Clicni.-Ing.-'Iech. 23, 64 (1951).
(2) Y,anianioto, Y., et al, Chem. ICng. (J apan) 16, 166 (19.52).
( 1) Samaddar, S. P.. and Nandi, S. K., Trans. Indian Ch. 1:.
(4) Bogart, 11. J . P., and Urunjcs, A. S., <;hein. Fmg. Progress
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* * *
ERRATUM:
.
An Analysis of Ai r and Solid Flow in a Spouted Wheat
.
.
Bed by B. Thorley, J . K. Saunby, K. B. Marhur and G. I,.
Osberg, from the October 1959 issue.
On page 186, column 2 , Equation ( 3 ) should read:
:
.
. instead of:
.
:
.
.
.
c ....................................................................................................... :.
The Canadian Journal at Chemical Engineerinl, June, 1960
87