benzene acetone
TRANSCRIPT
-
8/16/2019 Benzene Acetone
1/6
M-890
J.
Chem.
Tbww&a&cs 197&10,1101-1106
Isothermal liquid-vapour equilibria
2. The binary systems formed by benzene
+ acetone, + methyl ethyl ketone, + methyl
propyl ketone, and + methyl isobutyl ketone
M. DIAZ PERA, A. CRESPO COLIN, and A. COMPOSTIZO
Departamento de Quimica FL&a, Facultad de Ciencias Qufmicas,
Universkhd Complutense, Madrid-3, Spain
(Received 13 February 1978; in revised form 17 April 1978)
Vapour pmasures
at 323.15 K by a dynamic method and refractive indices at 303.15 K
have been m#lsursd for several bi i systems umsistin8 of benzene + acetone, + methyl
ethyl ketone (MEK), + methyl propyl ketone (UPK), and + methyl isobutyl ketone
(MIK). The vapour pressureshave been used to calculate excessGibbs free energies.
1. -
Continuing our study on the Gibbs free energy of binary mixtures of a hydrocarbon
+ a ketone, liquid-vapour equilibria were measured at constant temperature for
benzene + a ketone. In order to calculate the excess Gibbs free energy G’ for each of
the binary mixtures at 323.15 K, measurements were made of the total vapour pressure
p as a function of liquid-phase composition x, and also of the vapour-phase composi-
tion y, whose experimental values were checked against those calculated by EWker’s
method.(*)
2.
Experimental
MATERIALS
Benzene (Carlo Erba RS), and acetone (Riedel-de Habn) were purified by well
established methods.(3) The purity of the materials used was checked by measuring
their refractive indices nl, and densities p. Values for these materials were: benzene,
nD(303.15 K) = 1.49481 (lit., (4) 1.49478) and p(298.15 K) = 0.87370 g cmT3 (lit.,@)
0.87370 g cm-‘); acetone, n,(303.15 K) = 1.35335 (lit.,‘6’ 1.35407) and p(298.15 K)
= 0.78491 g cme3 (lit., c6)0.78501 g cm-‘). Our criterion of purity for all liquids was
the constancy of their vapour pressures. These are given in table 1 together with the
literature values calculated from Antoine equations. For methyl ethyl ketone, MEK,
methyl propyl ketone, MPK, and methyl isobutyl ketone, MIK, the samples were
similar to those used in part I. (l) Densities, refractive indices, and vapour pressures
are given there.
0021-%14/78/111101+06 $01.00/O Q 1978Academic Press Inc. (London) Ltd.
-
8/16/2019 Benzene Acetone
2/6
1102
M. DIAZ PERA, A. CRESPO COLI-N, AND A. COMPOSTIZO
TABLE 1. Vapour pressures of the pure compounds
TIK
PlkPa
Benzene Acetone
obs.
API”’
obs. API”’
308.15 19.776
313.15
24.399
318.15 29.791
323.15 36.162
328.15
43.600
333.15 52.204
338.15 62.076
343.15 73.431
348.15 86.372
19.773 46.518
46.538
24.369 56.525 56.549
29.799 68.229 68.244
36.169 81.835 81.819
43.592 - -
52.192 - -
62.096 - -
73.438 - -
86.362 - -
MEASUREMENTS
The apparatus used to measure vapour pressure was a dynamic ebulliometer.(8’
Pressures are accurate to within + 7 Pa, mole fractions to + 0.0005, and the tempera-
ture to +O.Ol K. The errors in GE arising from uncertainties in p alone are about
0.5 J mol-’ for the acetone and MEK mixtures and 0.8 J mol-’ for the MPK and
MIK mixtures.
Refractive indexes for benzene + acetone, + MEK, + MPK, and + MIK deter-
mined at 303.15 K are listed in table 2 together with the corresponding mole fraction.
They were used to draw calibration curves giving the compositions of the liquid and
vapour phases against the refractive index. These curves have been fitted by least
squares to an equation of the type nD = &A&-‘. Values of the coefficients Ai and
their standard deviations are given in table 3. The experimental values of p, X, and y
at 323.15 K are given in table 4. The chemical potentials and the corresponding values
for GE are given in table 4. The molar volumes V* and the second virial coefficients B
are given in table 5, together with the coefficients B12 estimated as {(Bi/;” + Bi$3)/2}3.
Values of V* for the ketones were determined from density measurements and for
benzene have been reported elsewhere. (‘) The values of B for benzene and acetone were
interpolated from those in the literature”” and for other ketones they were given in
part l.(l)
Several equations have been proposed to express the variation of GE with composi-
tion.(“) We have chosen
GE/J mol’ ’ = x(1-x) i A,(1-2xjr-i,
j-1
and our values of GE, fitted by least squares, and the coefficients A, thus obtained and
their standard deviations d are given in table 6. The experimental values of GE are
plotted in figure 1 with the fitted curves. The standard deviations of y,
p,
and GE from
those calculated byBarker’s method
(‘) follow. For benzene + acetone: o(u) = 0.0024,
o(p/kPa) = 0.048, and a(G*/J mol-‘) = 5.4; for benzene + MEK: ob) = 0.0016,
-
8/16/2019 Benzene Acetone
3/6
1103IQUID-VAPOWR EQUILIBRIA IN mW ZENE + KETONE
X
nD
X
kl
X
nr,
X
nD
0 1.494Xl
0.0294 1.49338
0.0822 1.48495
0.0866 l&M50
0x942 1.m
0.2394 1.46522
0 1.49481
o.ou7
1.49249
0.0762
1.4&W
0.1581 1.47526
0.1736 1.47336
0.2030 1.46973
0
OSU42
0.0820
O.WO
0.1777
0.2152
0
0.0523
0.0781
O.lld2
0.1440
0.2042
1.4WU
I .48882
1.48907
1A@576
1 .m94
1A6734
1.4kWU
1Am6
1.m
1.47&M
1.47W
1 w9
- x)csHs + xCH,COCHs
1.45561 0.6220 1.41248
a3630 1.44886 0.6552 l&738
O&79 1.44140 0.7265 1.39682
0.4l3S6
1.43534
0.76T6 1.39m
O;S4X6 f.42409 0.8220 1.38207
0.5705 1.41995 0.8502 1.37762
(1
- x)CsHs + xCH&OGHs
:fz k.45323.45906 0.6063.6451 1.4Kw.42076
0.4030 1.44536 0.6%7 1.40975
0.4621 1.43819 0.7370 1.4aSo4
0.5102 1.43235 0.7681 1.40130
0.5526 l&723 O.&ilb 1.39734
(1 - x)C&b + xCHdZOCsH7
0.26iZS 1.46&64 0.5535 1.42892
0.3M6 lk.4sS48 o.s%e 1.42451
0,3sl li.45m 0.6714 1.41672
oAa %? l&M68 0.7374 1.4uiB
0.469l u39o7 0.78oS lAmI
0.5222 I.43229 0.8488 1.39921
0 - xK3u + xCHsCOCIHWb)GH,
om55 r.46541 0.4983 1.43392
0.2W 1.43702 0.5708 1.42686
O.Z W E.4sm
0.629t 1.42M3
1A4781 0.6869 1.41633
lA4437 0.7277 1.41272
f.43396 0.7995 1.40672
0.9123
1.36763
09578
1 m2s
1
1.35335
0.86&l 1.3rm2
0.9368 1.388t18
1 1.37378
OHJO 1.3%39
0.9468 1.39818
1 1.38534
0.8Z48
1.4WbS
O.Psw 1.394a6
1 1.39130
TABLE 3. CIxfIk i& A$ and standad deviation a for ttD - X,R,X~-~ at 303.15 K
(1 - 4w-b
+-S
1.49488 -0.11903 -QB2043 -BiW ll 3
+ --%COCsHs I.49478 -412380
0.08275 3
+ -d=K=Xb
I.49484 -8L13389 O.OB66 -O&W9 2
+ ~s~V2EfbXsHs
1.49481 -0.15015 0.06986 -0.OOM4 O.WB43 2
-
8/16/2019 Benzene Acetone
4/6
1104
M. DIAZ PERA, A. CRESPO COLIN, AND A. COMPOSTEO
TABLE 4. Liquid-phase mole fraction x, vapour-phase mole fraction y,
vapolupfcamamp*alld~GIbba~~
x
Y plkpa
e/J mol - 1
x
Y
P/k-
G=/JmOl-’
0
0.1564
0.1787
0.1975
0.2218
0.2358
0.2536
0.2732
0.3553
0.4183
0.4552
0.4714
0.4924
0
0.0774
0.0903
0.1135
0.1328
0.1554
0.1769
0.2117
0.2458
0.2737
0.3056
0.3357
0.3538
0.3737
0.3928
0.4109
0.4318
0.4543
0
0.1031
0.1533
0.2195
0.2541
0.2655
0.2914
0.3194
0.3430
a3746
0.3994
0.4241
0.4462
0.3535
0.3847
0.4090
0.4391
0.4557
0.4785
0.4963
0.5725
0.6224
0.6512
0.6606
0.6765
0.09X3
0.1061
0.1306
0.1502
0.1733
0.1945
0.2275
0.2599
0.2847
0.3141
0.3410
0.3571
0.3753
0.3925
0.4084
0.4275
0.4482
0.0520
0.0769
0.1125
0.1315
0.1381
0.1530
0.1698
0.1847
0.2055
0.2227
0.2406
0.2570
(1
36.162
48.280
49.737
50.817
52205
53.061
54.124
55.086
59.116
61.887
63.476
64.012
64.889
(1
36.162
36.845
36.936
37.092
37.221
37.340
37.426
37.528
37.610
37.676
37.725
37.766
37.785
37.804
37.816
37.838
37.834
37.834
(1
36.162
34.286
33.361
32.096
31.437
31.219
30.712
30.157
29.680
29.038
28.526
28.003
27.536
- - 2&S + xcH8cocHa
0.5388 0.7084
168.5
0.5546
0.7197
190.5 0.5976
0.7467
2026 0.6635 0.7899
217.2 0.7174 0.8234
zx
0.7446 O.&m
248:2
0.7564 0.8483
0.7811 0.8621
279.3
0.7987
0.8727
291.9 0.8170 0.8841
293.2 0.8402 0.8990
293.4 1
291.7
- 4c6H 6 -I- KH6cocpH6
0.4767 0.4691
iti
0.5aIl
0.4909
0.5271 0.5157
iti
0.5514 0.5388
0.5737 0.5599
82.6 0.5892 0.5743
89.3 0.6068
0.5915
97.4
0.6255 0.6092
104.0 0.7247 0.7063
109.3 0.7572 0.7398
113.3 0.7749 0.7575
116.7 0.8191 0.8034
118.2 0.8676 0.8548
119.7 0.8887 0.8775
120.7
0.9262 0.9181
122.3
0.9652 0.9609
122.1 1
122.1
- x)CaHs + xCIUOC&
0.2749
30.8
ii%
37.9 0.5045
iEi i
45.0 0.5572
0:3494
46.9 0.6123
0.4021
47.8 0.6702 0.4636
47.9 0.7362
0.5425
47.7 0.8104 0.6446
47.4
0.8614 0.7249
2:
0.8992
0.7905
0.9663 0.9237
45.2 1
43.7
66.669
67.301
68.834
71.279
72.995
73.810
74.354
75.143
75.656
76.286
77.076
81.835
37.824
37.817
37.796
37.758
37.724
37.698
37.665
37.638
37.329
37.204
37.134
36.952
36.737
36.632
36.440
36.233
36.066
27.044
26.619
26.291
25.163
23.979
22.727
21.305
19.701
18.5%
17.780
16.324
15.584
285.2
282.0
271.7
249.1
219.1
201.2
197.7
184.4
171.3
159.9
143.8
121.4
121.0
119.4
116.8
114.3
112.5
110.2
108.2
86.4
77.8
72.9
ii:74
38.5
25.3
11.2
42.2
iti
35:8
31.5
it:
16.7
12.5
i::
-
8/16/2019 Benzene Acetone
5/6
LIQUID-VAFGUR EQUILIBRIA IN ,BENZBNE $ KETONB 1105
TABLI?4-coWnued
x
Y PW
P/J mol- l x Y
PFpa
P/J mol-1
0
0.0164
0.0369
0.0698
0.0859
0.1136
0.1354
0.1735
02008
0.2275
0.2719
0.3096
0.3186
0.3431
0.3738
0.4201
0.0051
0.0112
0.0212
0.0261
0.0350
0.0422
0.0553
0.0649
0.0745
0.0917
0.1074
0.1112
0.1221
0.1364
0.1598
(1 -
36.162
35.141
35.232
34.414
34.009
33.308
32.755
31.781
31.084
30.413
29.264
28.283
28.055
27.411
26.600
25.386
NC&s -I- ~~cocH(cHaK &
0.4706 0.1884
6.0 0.4923
0.2018
12.1 0.5115 0.2141
20.8 0.5430 0.2359
23.6 0.5954 0.2758
29.2 0.6378 0.3127
33.1 0.6784 0.3519
38.9 0.7326 0.4132
41.3
0.7738 0.4675
43.4
0.7985 0.5039
45.4 0.8425 0.5780
46.5 0.8805 0.6530
z-i
0.9033 0.7044
4512
0.9522 0.8355
1
44.7
24.038
23.443
22.926
22.065
20.638
19.466
18.358
16.867
15.728
15.047
13.824
12.774
12.147
10.784
9.447
43.6
41.9
40.8
39.2
35.8
32.0
28.5
25.2
21.7
19.6
15.4
11.8
10.9
6.3
TABLE 5. Second virial co&cknts
B
and molar volumes V* of liquid at 323.15 K
-B&m3 mol-1 -B2&ms mol-1 -B&ma mol-1
V*/cnP mol - 1
Bauale
1204 92.232
Aatone 1601
1393 76.848
SE
3250843
2Ml501
110.7893.150
MIK
2148
1631
129.488
TABLE 6. Cocf lkknts A, and standard deviation u for the relation between cxces Gibbs
energy and mole fraction at 323.15 K
(I- .3cd%
+ SJ-bCOCHs
1166.2 -201.9
-43.7 87.2 155.6
+xc)4cocnHs
483.3 -110.6 46.5 -92.4
ii-i
+~cocsH7
161.2 -137.9
61.6 -2.1 47.8 014
+ xcHscocH(cHa)cnH6
167.8 -113.0 26.0 1.6
69.6 0.5
a(p/kPa) = 0.025, and cr(P/J mol”) = 1.7; for benzene f MPK: cr((v) = 0.0003,
a(p/kPa) = 0.006, and a(P/J mol’l)-= 0.5; and fbr benzene + MIK: S(Y) - 0.0003,
cQ/kPa) = 0.010, and @P/J mol-‘) = 0.9. Although the differences appear to be
significant, the consistency is as good as could be expected.
In all the investigated mixtures of benzene + a ketone, positive deviations from
ideality were observed at all mole fractions. For these systems GE lies in the order:
-
8/16/2019 Benzene Acetone
6/6
1186 M.DIAzPBRi&A.CIRESP[a CC&IN, ANID A. CO-0
0.2 0.4 0.6 0.8
X
FXXJRE 1. Composition epndence f the excess ibbsenergyPet 323.15 . 0, (1 - x)C&
+ xCflaC]OCHs; A, (1 - &Ha + xCH&OC,Hs; 0, (1 - x)&I& + xCH&OCIH~; and
A, (1 -
&aHs + xCH,CO~(CH,)c,H,.
MIK x MPK < MEK
c acetone. The differences between GE values for benzene +
MPK and + MIK
are within
experimental error. Maximum GE values were observed
at mole fractions of kttm above x = 0.3, b&h in Ibbntze~ and h tohene. This is also
observed in Brown and Smith’s
data
uJ) for the benzene + acetone at
318.15 K.
REPISFUZNCES
1. Diaz Peila,M.; CrespoColin, A.; Compostizo, . J. Chem. l%ermadynamics W78, l@, 337.
2.
Barker,J. A. But.
J. Chem. 19 3, .6, 207.
3.
Riddick,J. A.; Bun=, W. B.
Orgawk Solvera’s: Physicai fiqperties and Metho& qdPk@tation,
3rd editican.Wiley-Interscience: ew York. .wIO.
4. Fortziati, A. F.; Norris, W. R. ; Rossini, . D. J.
Res. hbt. Bar. Stand. lH9,43.555.
5. Dreisbach,R, R.
Physical Properties of Chemical Conlpormrls.
Advances n ChemistrySeries.
AmericanChemistrySociety.1955.
6. Timmennans,.
Physico-Chemical Constants of Pare Organic Compormds.
Elsevier:New York,
ii%o.
7. Sukcted Y&es of Physical and IL%enw&namk Prqx&s of i &bcarbom and Related Corn-
poundi API Research roject44.X967.
B.~~,hI.;R~~~D.jln.~SPe.Fh.Q~.~, ,nl.
9. Egloff , G. Physical Constants of H~bcuw. Reinidd: New York. B&5.
10. Dymond, J. H. ; Smith, E. B. 2% Virial Cs vf Gases. clprmdon Press: Oxford. 196%
11.
Manh, X. N. 3. Chem. %?r~ynamlcs lI, 9, $19.
12. Brown, I. ; Smith, F. AIM?. J. Ckm. VW, IO, 429.