benzene acetone

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.


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,


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


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::


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:


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.

benzene acetone

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