M-2380

J. Chem. Thermo&namics 1989, 21. 801-809

Excess enthalpies
of (acetone + water)
at 278.15, 288.15, 298.15, 308.15, 318.15,
and 323.15 K
H. T. FRENCH
Department of Physical and Inorganic Chemistry.
University of Adelaide, Adelaide, S.A. 5001, Australia
(Received 23 March 1989)
Excessmolar enthalpies of {xCH,COCH,+(l
-x)H,Oj have been measured at 278.15,288.15,
298.15, 308.15, 318.15,and 323.15K using a mixture-displacement calorimeter. Partial excess
molar enthalpies of each substance are also reported.

1. Introduction
As part of the study of transport properties,(i the variation of the excess molar
enthalpies of (acetone + water) with temperature have to be known accurately. In
the compilation by Christensen et ~1.~excessmolar enthalpies of (acetone + water)
measured by various researchers up to 1981 were reported. Comparisons of the
reported values including the more recent work by Villamanan and Van Nessf3
revealed a high degree of scatter. In the present work a systematic study of the excess
enthalpies of (acetone + water) as a function of temperature was undertaken, using a
mixture-displacement calorimeter described by Stokes.(4

2. Experimental
Deionized rain water was purified by the Milli-Q Reagent-Water System from
Millipore. The conductivity of the water was 1O--5S .rn- 1 before exposure to air.
Analytical-grade acetone, manufactured by M & B, was purified further by fractionally distilling it from dried molecular sieve 3A. The column was 1 m long and
distillation was carried out at a reflux ratio of 40. Prior to the distillation, all the
glassware was flushed and filled with high-purity nitrogen. The purity of each
fraction was checked with g.1.c.and i.r. spectroscopy. Only fractions with purity
>99.99 moles per cent were retained for the enthalpy measurements.The acetone
was stored under high-purity nitrogen.
Present address: Bld. 23 Labs Area, Defence Science and Technology Organisation, P.O. Box 1700.
Salisbury, S.A. 5108. Australia.
002IL9614/89/080801+09 SO2.OOjO

I! 1989 Academic Press Limited

802

H.T.FRENCH

Initially, to remove the last traces of water, the distilled acetone was stored over
Linde molecular sieve 3A. This proved to be disastrous; the liquid treated in this way
had a significantly higher density and produced different i.r. spectra. Evidently the
acetone had undergone a reaction, probably a dimerization to 4-hydroxy-4-methyl2-pentanone (diacetone alcohol) or its dehydration product 4-methyl-3-pentene-2one (mesityl oxide) in the presence of the molecular sieve. Thus acetone cannot be
dried by simply passing it through molecular sieve without further treatment.
The density of acetone was measured by pyknometry in a thermostatted bath
controlled to f0.002 K. Each determination was done in triplicate. with the usual
procedures for buoyancy correction.
The excessenthalpies were measured in a mixture-displacement calorimeter with a
semi-automatic control constructed by Professor R. H. Stokes in Armidale.4 Both
exothermic and endothermic mode of operations were used. The mixing-vessel
volume was about 29 cm3.
Prior to a run both substanceswere degassed.The liquid in the burette was then
injected into the mixing vessel in pulses of 0.002 cm3. In the initial stages readings
were taken at intervals of 0.25 cm3 increasing gradually to a maximum of 2.00 cm3
towards the end of the run. The total volume added from the burette to cover the
whole mole-fraction range with reasonable overlap was about 25 cm3 when water
was added, and 29 cm3 when acetone was in the burette.
The semi-automatic control of the rate of injection worked very well in the large
part of the run, manual operation being needed only in the cross-over between
endothermic and exothermic regions. The calorimeter was immersed in a water bath
controlled to F0.002 K. All temperature measurements were based on IPTS-68.

3. Results and discussion

The densities of acetone at various temperatures are given in table 1. Literature
values are included for comparisons. The densities of water were those of Ke11.8
It can be seen that some of the older literature values of the acetone densities are
significantly higher than those obtained in this work and by Stokes.@The higher
values are most likely due to the presence of water in the acetone.
The liquid compositions and excessenthalpies were calculated using the method
described in reference 9. Taking substance 1 to be the one injected into the vessel
initially filled with substance 2, the following equation permits the calculation of the
composition of the liquid in the calorimeter vessel:
ln(n,/n,,i) = -

(Vi/I: V,)da,
s0

(1)

where n, is the amount of substance 2 present in the vessel,n,,, is the initial amount
of substance 2, V, is the partial molar volume and FT is the molar volume of
substance 1, V, is the volume of the mixing cell, and u is the volume of substance 1
added since the start of a run. (The above equation was taken from equation (4) of
reference 9, in which V;Cwas erroneously printed instead of VT.)

H:{xCH,COCH,+(l

803

-x)H,O}

With the mixture-displacement calorimeter, the quantities obtained experimentally

were the partial excess enthalpies of the substance in the burette. The measured
enthalpies were first fitted by the least-squares technique to the equation:
HF/(J+mol-) = (l-x,)

,$(1-2x,),

(2)

i=O

where x1 is the mole fraction of substance 1 at the mid-point of each increment. By

means of the Gibbs-Duhem equation in a modified form:

= (H:-x,~H#Lx,}/~;,

@lx;

(3)

equation (2) can be integrated to

HE/(J.moll)

= -(x2/2) i

(k,/(i+ l)}(l -2x1)+.

(4)

i=O

Equation (4) permits the calculation of HL from HF, and HF is calculated from HE
and Hy.
For the whole mole-fraction range at a fixed temperature, two runs were made,
starting with one of the two pure substances in the calorimeter. Consequently two
sets of calculations were required starting from the ends of the mole-fraction range.
Once these were completed the excessmolar enthalpies were combined and re-fitted
to the equation:
H$/(J . mall ) = x( 1-x) i

ai( 1-2x),

(5)

i=O

using the least-squares technique.

The excess molar enthalpies, and the partial excess molar enthalpies of each
substance are given in table 2. In the above calculation the excessmolar volumes of
the mixtures were needed. They were taken from those reported by Dizechi and
Marschall.() The inclusion of the excess molar volumes made a difference of at
most 1 per cent to the excessmolar enthalpies.
For the sake of consistency, the partial molar excessenthalpies reported in table 2
are those derived from the final fitting equation (5), as the measured values cover
only half the composition range for each substance. The uncertainty in these partial
molar values may be estimated as + 1 per cent for large values to f 2 J. mol- l for
smaller values.

TABLE 1. Densities of acetone

278.15
288.15
298.I5

0.80677
0.79571
0.79574
0.78437
0.78432

Source

T/K

Present work
Present work
Reference5
Present work
Reference6

298.15
308.15
318.15
323.15

Source
0.78433
0.78502
0.77281
0.76104
0.75504

Reference7
Reference5
Reference6
Reference6
Reference6

H. T. FRENCH

804
TABLE

.-.sL

J.mol-

Excess molar enthalpies and partial excess molar enthalpies for

/xCH,COCH,
(A)+(1 -x)H,O
(B)}

HI

J.mol

HE

HE

J,mol-

J.molV

HB
FiGi=

T= 278.15 K
0.0019
0.0061
0.0104
00147
0.0190
0.0255
0.0342
0.043 1
0.0522
0.0613
0.0704
0.0797
0.0887
0.1024
0.1215
0.1414
0.1618
0.1820
0.2025
0.2233
0.2440
0.2597
0.2707

-24
-73
-122
-168
-213
-276
-353
-424
-487
-544
-592
-636
-672
-715
-762
-792
-810
-817
-815
- 805
-788
-771
-758

0.0020
0.0060
0.0103
0.0147
0.0190
0.0255
0.0343
0.0432
0.0524
0.0616
0.0708
0.0801
0.0890
0.0957
0.1057
0.1227
0.1425
0.1629
0.1817
0.1949
0.2059
0.2168
0.2264
0.2349
0.2475
0.2676

-22
-65
-109
-152
-192
-249
-319
-383
-442
-493
-538
- 578
-611
-633
- 660
-696
-723
-737
-740
-738
-734
-727
-720
-713
-701
-677

-11110
- 10343
-9938
-9593
- 9085
- 8468
-7691
- 6900
-6129
-5384
-4780
-4167
-3593
- 3622
- 2828
-2184
- 1591
- 1086
- 707
-499
-357
-210
-99
-22
110
262

12354
11424
10896
10584
10106
-9541
- 8533
-7591
- 6700
- 5901
- 5280
-4675
-3774
-3328
-2521
- 1845
-1307
-893
-554
-282
-60
69
155

0
-2
-6
-13
-21
-38
-66
- 102
-144
-191
-241
- 294
-345
-423
-527
- 625
-714
-796
-876
-954
- 1027
- 1071
- 1091

0.2654
0.2817
0.2995
0.3192
0.3396
0.3620
0.3879
0.4167
0.4495
0.4868
0.5294
0.5715
0.6121
0.6504
0.6844
0.7212
0.7627
0.8087
0.8486
0.8857
0.9225
0.9532
0.9841

-753
-731
- 705
-673
-638
-596
-547
-489
-421
-342
-251
- 161
-77
-1
61
122
178
221
238
230
195
140
56

169
281
381
469
541
602
656
699
732
753
758
743
711
666
614
546
458
351
255
167
88
36
5

- 1076
-1117
-1153
- 1206
- 1212
- 1283
-1323
- 1352
- 1379
-1394
- 1390
-1359
- 1320
- 1223
-1121
-980
-727
-358
141
716
1501
2235
3249

0.1645
0.1728
0.1819
0.1916
0.2020
0.2132
0.2254
0.2383
0.2525
0.2679
0.2852
0.3039
0.3237
0.3458
0.3705
0.3983
0.4293
0.4639
0.5037
0.5433
0.5814
0.6171
0.6477
0.6810
0.7186
0.7596

-732
-734
-735
-734
-731
-725
-716
-704
-689
- 670
-646
-618
-585
- 546
-500
-446
-383
-311
-227
-144
-66
5
62
119
175
224

- 1084
-904
-727
-554
-392
-236
-89
47
174
289
397
491
571
642
701
751
788
813
820
809
780
739
694
635
559
468

-675
- 708
-741
- 776
-814
-848
-885
-931
-981
-1015
- 1062
-1102
-1144
-1174
-1218
- 1249
- 1278
-1264
- 1284
- 1269
- 1236
-1185
-1091
-999
-812
-559

T=288.15K
0

-2
-6
-12
-19
-34
-60
-91
-128
-170
-214
-261
- 308
-343
-396
-483
- 580
-671
-747
- 796
-834
-870
-900
-927
-964
- 1022

H:{xCH,COCH,+(l

-x)H,O)

805

TABLE 2-continued
x
0.7965
0.8194
0.8399
0.8660

HE

fG

J.mol-

H:

J,moi-

J.mol-

254
265
269
265

381
325
275
213

-253
61
204
583

x
0.8921
0.9214
0.9535
0.9849

Xl
I mol

Hf
J.mol-l

HBt-

J.molk

248
213
150
57

153
91
37
4

1060
1655
2430
3513

T=298.15 K
0.0019
0.0060
0.0103
0.0147
0.0191
0.0256
0.0344
0.0435
0.0525
0.0617
0.0711
0.0807
0.0902
0.1045
0.1241
0.1450
0.1653
0.1853
0.2058
0.2183
0.2294
0.2496
0.2715
0.1670
0.1759
0.1852
0.1950

-19
-59
-100
-139
-176
-226
-289
-346
- 397
-442
-482
-517
- 546
-582
-616
-637
- 645
- 643
-633
-624
-615
- 594
-567
-641
-642
-641
-638

- 10435
-9280
-8964
- 8608
-8139
-7615
- 6824
-6083
- 5397
-4739
-4152
-3594
-3092
- 2496
-1790
-1169
-812
-419
-141
0
102
272
409
-819
-642
-471
- 308

0
-2
-6
-12
-20
-34
-59
-88
-122
-160
-200
-244
-289
-356
-449
-542
-625
-697
-761
- 795
- 824
-875
-937
-628
-659
-692
- 728

0.2058
0.2174
0.23OQ
0.2437
0.2585
0.2747
0.2921
0.3113
0.3324
0.3555
0.3816
0.4113
0.4446
0.4828
0.5237
0.5634
0.6046
0.6427
0.6759
0.7129
0.7519
0.7950
0.8458
0.8884
0.9184
0.9504
0.9833

-633
-625
-613
- 599
- 580
-558
-531
-499
-462
-419
-368
- 309
-242
-164
-80
-1
77
145
198
249
291
317
316
281
234
I62
6

-150
1
144
276
397
505
600
682
750
804
846
876
892
895
881
854
808
750
688
605
506
388
249
143
81
32
4

- 760
-795
-832
-872
-906
-947
-983
- 1015
- 1058
- 1093
-1131
-1148
-1163
-- 1167
- 1137
-1103
-1040
-944
- 799
-631
- 369
78
636
1327
2003
2712
3452

0.0019
0.0060
0.0104
0.0147
0.0191
0.0257
0.0345
0.0436
0.0528
0.0620
0.0713
0.0808
0.0906
0.1052
0.1248
0.1443
0.1594
0.1688

-16
-51
-86
-119
-151
-197
-251
-301
-345
-384
-417
-446
-471
-501
-527
-541
- 545
- 542

-8605
-8156
- 7908
-7535
- 7084
-6599
- 5896
- 5243
-4601
-4022
-3506
- 2965
-2605
-2037
- 1408
-917
-605
-486

T=308.15
0
-2
-5
-9
-15
-28
-49
-77
- 108
-144
-181
- 220
-261
-322
-401
-477
- 534
- 560

K
0.1776
0.1872
0.1976
0.2086
0.2205
0.2335
0.2475
0.2626
0.2793
0.2975
0.3175
0.3397
0.3639
0.3913
0.4224
0.4571
0.4967
0.5428

-541
-538
-532
- 524
-514
-501
-484
-464
-440
-411
-377
-338
-293
-241
-180
-111
-32
59

-333
-183
-38
99
228
350
462
562
655
735
804
861
906
941
964
974
968
939

-591
- 620
-656
-690
-724
-751
- 792
-823
-857
- 890
-925
-963
-988
-1006
-1019
- 1028
-1009
-991

H. T. FRENCH

806

TABLE

Hii
J.molV

0.5953
0.6407
0.6756
0.7450

156
233
285
359

0.0042
0.0105
0.0149
0.0193
0.0236
0.0303
0.0393
0.0484
0.0577
0.0671
0.0768
0.0867
0.0964
0.1113
0.1314
0.1516
0.1766
0.1977
0.2145
0.2366
0.2586
0.2803
0.1616
0.1705
0.1795
0.1892
0.1997

0.0020
0.0062
0.0105
0.0150
0.0197
0.0262
0.0348
0.0439
0.0532
0.0627
0.0722
0.0820
0.0920
0.1070
0.1266
0.1472
0.1646
0.1743
0.1884

Hi
J.mol-

Z-continued

HB
J.molk

878
801
727
549

-882
-782
-637
-222

-32
-77
-106
-133
-159
- 196
-241
-281
-315
-345
-371
-393
-410
-429
-443
-447
-440
-426
-411
-385
-354
-321
-439
-436
-432
-425
-417

-7311
-6839
- 6530
-6153
-5863
-5370
-4713
-3985
-3621
-3102
-2618
-2155
-1848
-1359
-819
-406
0
220
417
589
729
836
-237
-92
39
168
292

-1
-5
-9
-15
-22
-36
-58
-85
-115
-149
- 185
-223
-260
-316
-388
-454
-528
-587
-632
-689
-738
- 766
-485
-517
- 539
- 569
-598

-15
-43
-71
-98
-126
-161
-202
-240
-273
- 302
-326
-347
-363
-382
-396
-400
-396
-392
-384

- 7025
- 6688
-6362
-6049
-5566
- 5059
-4531
-4008
- 3428
-2878
- 2449
-2012
-1749
- 1294
-761
-363
-121
0
170

0.8389
0.9040
0.948 1
0.9820

fCl
J.molk

H:
J.mol-

HBE-J,mol-

372
295
190
75

281
117
38
5

874
1978
2949
3901

-406
-392
-376
-356
-332
-304
-273
-235
-192
- 143
-87
-21
52
133
212
283
340
384
417
443
450
422
362
294
196
72

409
520
622
716
801
876
940
995
1039
1072
1093
1100
1089
1056
1000
926
844
758
668
555
411
271
160
91
35
4

-626
-643
-676
- 707
-736
-767
- 802
- 829
-856
-875
-885
-889
-874
-839
-767
-675
-547
-385
- 183
130
582
1241
1943
2647
3388
4404

-370
- 362
-350
-336
-319
-299
-275
- 247
-216
-180
-136
-87
-31
34
106
186
262
328
382

268
381
495
605
703
792
872
945
1004
1055
1097
1126
1143
1145
1128
1088
1027
950
865

- 526
-552
-571
-604
-632
-657
-689
-709
-735
- 763
-779
-805
- 806
-815
- 806
- 763
-691
-581
-439

T= 318.15 K
0.2111
0.2235
0.2369
0.2513
0.2672
0.2845
0.3033
0.3243
0.3476
0.3733
0.4021
0.4349
0.4719
0.5139
0.5568
0.5985
0.6365
0.6712
0.7047
0.7447
0.7942
0.8437
0.8873
0.9191
0.9525
0.9846

T= 323.15 K
0
-2
-5
-9
-16
-27
-46
-70
-98
-128
-160
- 193
-227
-277
-340
-402
-452
-478
-511

0.1874
0.1975
0.2089
0.2216
0.2349
0.2491
0.2647
0.2821
0.3003
0.3206
0.3442
0.3701
0.3990
0.4322
0.4695
0.5116
0.5543
0.5948
0.6324

H$CH,COCH,+(lTABLE

Y
0.6667
0.6961
0.7360
0.7923
0.8447

f&t

Hi

J,mol-

J.mol-I

423
450
474
477
439

2-continued

HB"
J.mol

776
695
577
408
258

807

x)HzO;

-280
-110
189
720
1431

Xl
J,molF

0.8870
0.9 182
0.9504
0.9831

HF4

HB"

J.molF

J.rnol~

151
86
34
4

2115
2114
3466
4337

373
302
04
78

Errors in the measured Hf: values are mainly due to not quite restoring the vessel
to the baseline temperature at the end of a step. The effect,of such errors on Hz is
largely cancelled in the following step. The uncertainty in the mole fraction is
+O.OOOl.The parameters for equation (5) are given in table 3.
Figures 1 and 2 show the excessmolar enthalpies of (acetone + water) at 298.15
and 323.15 K respectively. The more recent literature values are included for
comparisons. In general the agreement between the results from the present work
and the literature values is poor, with the exception of those reported by Belousov
and Sokolova.) Quite good agreement was obtained with their results at both
308.15 and 323.15K.
It can be seenin figure 1 that the disagreement with Coomber and Wormalds12
results at 298.15 K occurred mainly in the exothermic region. This was probably
caused by the different methods in which the exothermic run was done. In the
present work isothermal conditions were maintained in both endothermic and
exothermic runs, in the latter by means of a Peltier diode. Coomber and Wormaldi2
allowed their mixtures to increase their temperatures, the excess enthalpies being
calculated from the deflection of the chart recorder attached to the calorimeter
thermocouple. It was possible that this procedure introduced a significant
uncertainty to their results.
The disagreement between the present results and those of Villamanan and Van
Nessf3)occurs mainly in the endothermic region; up to x z 0.2 the two sets of results
agree well. The cause for the discrepancy in this case was probably the presence of

TABLE

TK
00
UI
02
a3
04
05
s

3. Parameters of equation: Hk/(J

mol I) = u( 1 - u) i ai( 1 -2.x) and standard deviations ,T

I =o

278.15

288.15

298.15

308. I5

318.15

323.15

-1257
-4306
- 1016
- 2396
- 1997
- 1515
2.8

- 942.2
-4231
- 905.6
- 2032
- 1749
- 1472
2.0

- 520. I
-4137
- 665.2
- 1915
- 1859
- 1097
2.0

- 103.5
-3996
-419.5
- 1732
-1662
- 990.3
1.1

423.8
-3878
431.2
-1355
~ 1405
-1177
2.7

655.9
-3741
- 324.8
-1398
-1503
-914.
2.4

I
0

0.2

0.4

0.6

0.8

FIGURE 1. Excess molar enthalpies for {xCH,COCH,+(l

-x)H,O}
l , reference 12; A, reference 13; + , reference 14; x , reference 15.

at 298.15K. 0, This work;

FIGURE 2. Excess molar enthalpies for {xCH,COCH3+(l

x1 reference 3; 0. reference 11.

-x)H,O)

at 323.15K. 0, This work;

H:{xCH,COCH,+(l

-.x)H,O]

809

water impurity in Villamanan and Van Nesss acetone which had an assay of 99.5
moles per cent.
The presence of a small amount of water as impurity in the acetone has a large
effect on the molar excessenthalpies at the acetone-rich end due to two contributing
factors. Firstly, even though the level of impurity is low, the additional water from
the impurity changes its mole fraction to a significant extent. For example 0.5 mole
per cent of water in the acetone will increase (1 -x) from 0.020 to 0.025. Secondly, the
rate of change of the excessmolar enthalpies as more water is added is high at this
end of the mole-fraction range: about 3 to 4 kJ. mol- . A large change in Hi is
brought about by a small change in x; 0.5 mole per cent of water impurity increases
Hz by 15 to 20 J.mol- at x ~0.98.
At the water-rich end the contribution made by the water impurity to the overall
mole fraction of water is insignificant, and the partial molar excess enthalpies of
water are small. The effect of the impurity on HE is therefore negligible.
I thank Professor R. H. Stokes for the loan of the apparatus and for his invaluable
help.
REFERENCES
1. Woolf, L. A. to be published.
2. Christensen, J. J.; Hanks, R. W.; Izett. R. M. Handbook of Heats of Mixing. Wiley: New York. 1982,
pp. 1458.
3. Villamanan, M. A.; Van Ness, H. C. J. Chem. Eng. Data 1984, 29, 429.
4. Stokes, R. H. J. Chem. Thermodynamics 1988, 20, 1349.
5. Timmermanns, J. Physico-chemical Constants of Binary Systems. Interscience: New York. 1950,
p. 355.
6. Stokes, R. H. personal communications.
7. Evans, D. F.; McElroy, M. I. J. Solufion Chem. 1975, 4, 413.
8. Kell, G. S. J. Phys. Chem. Ref Data 1977, 6. 1109.
9. Stokes, R. H. J. Chem. Thermodynamics 1986, 18, 359.
IO. Dizechi, M.; Marschall, E. J. Chem. Eng. Data 1982, 27, 358.
Il. Belousov, V. P.; Sokolova, E. P. Vestn. Leningrad Univ., Fii. Khim. 1966, 2 1, 90.
12. Coomber, B. A.; Wormald, C. J. J. Chem. Thermodynamics 1976, 8, 793.
13. Drinkard, W.; Kivelson, D. J. Phys. Chem. 1!%8,62, 1494.
14. Kister, A. T.; Waldman, D. C. J. Phys. Chem. 1958, 62, 245.
15. Hanson, D. 0.; Van Winkle, M. J. Chem. Eng. Data 1960, 5. 30.