2354 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 41, No.

10

VAPOR-LIQUID EQUILIBRI.\

B I X A R YSY$rrrcifs. Several ciliyl

:~lcoliol-n.:tt.er i'uiis rvcre made to chccli
Figure 5 . S o l u b i l i t j I s o t h e r m s i n Weight 76 for Eth)I ~ I ~ ~ l i ~ l - IEicetate-
tti~ i , l i t S pc~ifurni:riicc: of the apparatus anti
Water ixlibmtioiis, I>erisit,ies,boiling points,
_ _ _ Present
~
:tiid y-x value.? checked the literatui'e
Bonner
--__ Berrh and Glasstone (20' C:.) tn rvithin analyt'ical accuracy.
The ethyl alcohol-ethyl acetate tlnt:i
:we given in Table VIA. Tho y-x v;rlues
are plotted in Figure 7 . These agrre
with the data of Furnas arid Leighton
except in the 50 to 75 mole % ethyl
alcohol region where the pre-ent, data
are slightly higher in ethyl alcohol.
The boiling points are plotted in Fig- ,
ure 8 arid the activity coefficic,nts in
1;iyurc 9. T h e act,ivity coefficient~sare
F i g u r e 6. Binodal C u r t e and Liquid-Phase Equilibria i n Mole % for E t h ? l eucellwt~lycorrelated b y the two-suffix
Alcohol-F,th>l 4 c e t a t e - F ater
Van 1,aar cquation ( 1 7 ) . [The ethyl
Temptmture, normal Imiling point: pressure, i 6 0 m m .

Figurc 5 were preparcd. The curves are in good agrccnieut witti

those of Bonncr (g), but do iiot agrce well with those of Bccch T.\RI.E Iv. TERK.4RY ( ' I n 1 . D I'oIST Ij.iT.L
and Glasstone ( 1 ) . S o t e that solubility of ethyl acetat,(, in the TI-eight Ratio,
water phase decreases with tcmperat,ure. \vt. c; E t h y l .Icetate: Clo,~; Point,
1Vati.r Ethyl hlcohol c. I<.
.5 7 1 21.7 19.0 2!l-". 1
6.33 21.7 30.2 103.3
C,73 21.7 3i.8 310.!)
i :3 "1 , $7 .!I 321,ll
8 1, 21.i !,O. i 332.8
TABLE 111. 13IK.Wl- T<THYL .\('ET.\TE - 1 v . I T E R
S (il < I . 87 13.3 "86.4
'(Vt. t;, Cloud Point,~-C. !I .(is 9 ,R i 2!l , 2
Ethyl Acetate E\-ix,rimcnt Litrratuw ' Ii 12,lI(i !i,Si m.2
1 1 I(i2 I? fi!) 14.8 286, !1
Watrr Phasc II.21 6; . ti!) 43 ,5 318.6

3.01 19.0 202.1 2.48 18.3 291.4

3.01 ,.. 20.h ' ( 8 ) 2'33,l 2.48 27.7 300, 8
3.4'1 ... 30.0 (8) 303.1 2.48
2 48
42.9
00,5
316.0
333.6
4.00 40.00 ( 8 ) 313.1
4.05 314 0 1 .3!1 s.L 281 . 3
5.00 330.4 I . .i9 li 7 '268.8
5.10 ... 60,bb'(8) 333.1 1..;<I 22.0 29.2.1
5.65 fi8.2 341.3 1 .i!l 44.2 31i.X
1 ,.in .ill, t j 323,:
1 ,3!l il,3 :% . 4
:i

\Yi,ii.!rt Ratio.
\\t.(? \Vatvr: (:loiirl I'oiiit,
I n the remaining figures, compositioiis are giveii iri mole pcr 1 :'wtatc' '':t'l) 1 - A h J h d 0 c. K
cent, converted from weight per cent analytical data. Thc 8 111 301.1
8 , (iB 1 312.7
tie line data are givvn in Table 1- and are plotted in Figure 6. < , I , Jti , 327.7
I ( 1 (ill 346.0
These were correlated by thc method of Ot,hmer and Tobias 11. 1:s 4 02 2 0 (i 293.7
(14), which permits estmpolation t o locate t,he plait point. The 1.1 O(i 1 ti.' 32 0 303.1
data all fell on a smooth curve on the Othnier plot, the fivc t#ic- 14.0: 1, li2 39 (1 312.1
14 31 4.n2 41 0 314.1
line points highest in ethyl alcohol forming a straight line. Tht' 1.5 !I(! 4 ,(il' .i1 , !I 325.0
other two points which include the et,hyl acet8ate-\vatcr binary 17.2,i 4 ti2 fi0,7 333.8
did not fall on the straight h e portion of the Othnier plot. I!, , 3!l 3 . 2!) 2:. 1 '298.5
21.8'1 3.2!1 24.3 307.6
The resulting conjugate curvc is shown in Figure ti wit,h the 25.10 R 20 18 (I 321.1
28 6 3 3 . ?!I 6 3 , :i 336.4
extrapolated portion dashed. A4smight have been anticipated, 32.00 3.29 i8.2 351.3
the plait point has the higheat boiling point of any composition I!). 87 3.12 20.6 293.9
on the boundary curve. This observation may soinetinie prove 23.24 3.12 :j2.0 305.1
2G. 9i ?,I2 46 , 4 319.5
useful for determination of plait point compositions. Another 81.33 3. I:! 66.4 33'3.5
noteworthy observation is that the tw+phase mixture con-
October 1949 INDUSTRIAL AND ENGINEERING CHEMISTRY 2355

100 79 I i

BO
P
F 'C.
E 60
0
-I
z
U
x 40
I-
W

se
-I 20
W
0 20 40 60 BO 100
0 FURNL1S 8 LEIGH
I MOLE % ETHANOL
0
Figure 8. Sornial Boiling Point
MOLE% E T H A N O L IN LIQUID Diagram (760 Rlni.) for Ethyl
tlcohol-Ethj 1 Acetate
E'igure 7 . \ apor-I,irpirl Equilib-
rium (760 T l n i . ) for Ethyl .tlcohol-
EthJl i c e t a t e
4
V A N L A A R EQUATION

alcohol-water activity cocfIicients correlate better by the four- 3 I 1 -___ 4.0372 8~0384

suffix reduced M;trgulcs equation ( I S ) with -1 = 0.738 (ethyl

alcohol), B = 0.42, and 1) = 0.3053.

TABIJ:v. TIE LISS n.4T.L

0 20 40 60 80 I00
: i o o C.)
MOLE '6 ETHANOL
Tis
Line ';b Kater ( , Ethyl .\lrohol T; Ethyl Acetatc
No. wt. hlolh- n-r. 3l<,l(> u-t . 3Iolc Figure 9. E t h s l Ucohol-Eth>l t c e t a t e \ c t i \ i t >
1 5.8 23.2 (1 0 94.2 76.8 Coefficients
93.7 98.1; 0 0 6.3 1 .'L
llormal hoiling point = ihO mm.
2 6.6 25 2 1.o 1 5 92.5 73.8
91.0 97,ii 2.2 0.9 6.8 1.d

__
6S,!l 88.4
-
13.8 7.0 17.3 4.6 0 , __ - ~ _ ~ ~ _ ~ ~ _ _.J~~-
!

;,,--+--;-->-I
I i
----I
EXPERI-ENTIL
I - -
i

T h e ethyl acetate-n-ater data are given in Table VIB. T h e

W
2oL1p.
6o
,
~ ~ _ _
;zp::;;
'
~~
e

y-x data were extended to the two-phase concentrations by means w

J --.+.---
~1 -1-, r7-
~l ~

of the Van Laar equations ( 3 )and are plotted in Figure 10. T h e I o

0
~, 1 ,

I I

1 !4. 1 94.0 84.0 fj80 277 1.01 ii !I1

plot of the water corner is 2 ,4.6 05,s 86.9 692 285 0.998 8 :33
given as Figure 14. T h e boil- 3 7 3 . 8 9 7 . 6 9 2.2 722 '97 0.995 8,:{ll
irig points are plotted in Figure " .I = ethyl alroliol, E = ethyl acetate, IV = water.
1.5 with a n enlarged plot of
 ran
1-
c,,

I'
SL'
S::
s'4
S3

0 20 40 60 80 IW
MOLE % ETHYL ACETATE

Figure 13. Ethyl Acetate-Water

Activity Coefficients
\orninI Iioiling p < > i n t = 760 nim.

WATER
E T H Y L AGETATE-

IJigiire 11. \ apor Liquid Equilibria in \Zole for E t h > l Z l c + o l ~ c , l -

E t h > l icetate-Water
Hirh water conrcntratiuri.i; p r c * ~ u r r760
, mrn.
2358 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 41, No. 10
ETHANOL
I o m ) i o \ i t i 0 1 1 s(sp :tr L: tc.11 into t t i I )
Ili~UIll 1,LJ I S I b 111 the c ~ l l l ~ l ~ ~ 1~ l ~ l ~ r
I 1 i v I orrdc tr\:lt(~ \,tnlpll~5fton1 o t l l c . 1

nii\turcs M hose c 11 n i p o ,I t i o t i 1.i\

i r i t h i t i the 70.3” C. zone i r e i e ob-
t.iincd in single phase by electrically
1 i c ntiiig the condensate chamticr b’or
AI I such s:impl(~, t 1ir c I I I 11lmsi t t I ,
wJnipo\itinn 1,i\ o i i t Iir 70O-niiii
Ijoider curve aoniex ht re bvtn eeii
the two points tor 70.3” C. shonri
iii Figure 6. T h e location of s m i -
ples betu een these limits vnrietl
w n e a h a t n i t h t h e initial cliLLrg(h
composition. This requires vapor and
liquid in the column, t o reach an
imniiscible or border curve composi-
tion, with little or no change of com-
position occurring above that point of
thc column. This confilms exist-
(mc(3of a minimuni Iioiling ccntcr v c -
tion of the border curve. O L w tlic
entire low-boiling zone, the lioiling
temperature of an? compobition
ETHYL nithin t h e zone is not more than
WATrK fiGETATE
:I few hundiedths of a dcgiee higher
Figure 1.5. Wiling Point Dingrani for E t h j l tlcnhol-Eth~l tcetate-Water than the Ion est boiling composition
Ternpcriiturr, (:.; prr-sure, i 6 0 m m . ; ronccntrution, molc 7~ 011 the boundary curve. &!neralitie-
of fractionation behavior in ternary
mistures containing azeotropes have
l)wn escellcntly plcsrntcd l)y I~;n.c~ll
and R-elch (.$).

i(:KSOW-LEI)G\l k : R T

The University of Texas Research Instit,utc provided thv

funds for purchase of the Podbielniak IIeligrid column.
Brvcrly Pett,y assisted in t h e preparation of the manuscript ,

(1) Beerh and Glasstone, J . Chem. Soc., 1938, 67.

(2) Bonner, W.D., J . P h y s . Chem., 14, 738 (1910).
(3) Colburn and Schoenboln, Trans. Am. Inst. Chem. E n g r s . ,
41, 421 (1945).
(4) Ewell and Welch, IXD. EXG.CHEJI.,37, 1224 (1945).
( 5 ) Furnas and Leighton, Ibid., 29, 709 (1937).
(0) Griswold and Buford, I b i d . , 41, 2347 (1949).
(7) Griswold, Chew, and Klecka, I b i d . , in press.
(8) “International Critical Tables,” Vol. 3, p. 358, X c w
York, hIcGraw-Hill Book Co., 1928.
(9) Ibid., Vol. 3 , p. 33; Vol. 7 , pp. 12, 67, 83, 1930.
(10) Keyes, D. B., ISD.ENG.CHEM.,24, 1096 (1932).
(11) Kireev, Kinov, and Grigorovich, J . Chem. I n d . (.lloscotu),
ETHYL ACETATE- 12, 936 (1036).
(18) Lccat, M.,in “Intcrnational Critical Tables,” T’ol. 3,
1;igure 16. Normal Bniling Points (760 \ I m . ) f o r Ethjl pp. 318, 320, 323, Kew Tork, McGraw-Hill Biiok ( ‘ o . ,
i i l c o h o l - E t h ~1 .icetate-Water 19%.
(I:{) lIerrinian, I t . IT., J . C’he?
Jligli water conrentrations: concentration.. r n o l c 5% (141 OtIiiiipI aiid Tohias. ISII.
(15) Si.lilehgci i i i i d Iiubasol-:&. %. I’hysilc. Chem., A . , 142, 2 5 ,
19”.
13ut l\Ierrinian stated th:it Iiis ati:tI~~.sc~s
n ~ w not
’ :rc.c.ur’:itc, :irrd ( I ( $ ) S l ~ x wC:,. S,, ( ‘ a , , , (‘hcni. P,.ocessIuris.. 25, 200 (1941).
he made no attempt t o a n n l ~ mvxpor ~ fr:trtionatetl from liquid IVoIil, K u r t . ’I’mris. Am. I r & . (‘hcm. Engrs., 42, 218 (1940)
(17’
(IS)
of t h r azeotropic composition. (19)
On tho t r r n a n - diagrams. :I minimum boiling toniperuturc of
”

70.3” C. ~ : i found
s
-

to ocrur ovcxr a sizable zone RS shown in ‘*pxE1’LD 8‘ ’’“.

1,’iKures I 1 and 12. Sevc.r:il diffcw~nt mistures in this zone
including the ternary :izeot ropc were charged t o a Podbielniilk
Heligrid column and fractionated. T h e column \vas operated
both under very high reflux ratio, and under total reflux followed
Ijy iiistantttneous top sampling. The ternarJ- azeotropic com-
position is heterogeneous :tt temperatures below approximately
5 ” (!. and vapor condensate rebulting from fractionation of this u
-
-