J. Chem.

Thermodynamics1975,7, 839-846

A continuous-dilution
measurement
of static
binary liquid mixtures
R. S. MURRAY

device for the

vapour pressures

of

and M. L. MARTIN

Department of Physicaland Inorganic Chemistry,

University of Adelaide,Adelaide,South Australia
(Received10 March 2975)
A continuous-dilution
devicefor the rapid measurement
of static vaponr pressures
of

binary liquid mixturesas a function of compositionis described.Thesemeasurements

togetherwith computedexcessGibbsfree energies
are reportedfor benzene+ n-hexane
at 298.15K andcomparedwith the resultsof Dunlopet al.()

1. Introduction
In recent years continuous-dilution
dilatometry(*) and isothermal-dilution
calorimetry(3S4) have yielded highly accurate excess volumes and excess enthalpies of
binary liquid mixtures. This paper describes the construction and operation of a
continuous-dilution
device for making rapid and accurate determinations of static
vapour pressures and excess Gibbs free energies of binary liquid mixtures. The entire
composition range is covered in two experimental runs. The method has been used
to determine the excess Gibbs free energies for benzene + n-hexane at 298.15 K.
2. Experimental
A diagram of the vapour-pressure apparatus is shown in figure 1. A Pyrex-glass
vacuum line, interposed with Nupro bellows valves and Kovar glass-to-metal seals,
is mounted in a rigid brass framework to which is fitted an adjustable three-point
suspension for levelling purposes. A calibrated measuring burette MB of volume
about 18 cm3 consists of two sections of Veridia precision-bore (4 mm, 8 mm) glass
tubing with three fiducial marks along its length. A bulb B at the lower end of the
burette branches down to a mercury reservoir and out to valve 8 through which the
burette is filed with liquid from the degassing apparatus. The mercury reservoir is
connected via pulley-operated valve 6 either to a vacuum or to a nitrogen supply
so that the level of the mercury in the burette can be lowered or raised. A glass bowl
surrounding the bulb is fYled with ice or liquid nitrogen during distillation of liquid
into the burette. A 2 mm bore tube connects the upper part of the burette to pulleyoperated valve 4 through which additions of liquid are made to the vapour-pressure

840

R. S. MURRAY

AND

M. L. MARTIN

cell C. For very fine control and avoidance of side thrusts on the valve 4, a brass bar
of adjustable length is interposed between the valve spindle and the pulley shaft.
The cell contains a coiled platinum stirrer mounted below a small glass-enclosed
magnet which is activated by a solenoid, and is connected to the manometer constructed of Veridia precision-bore (20 mm) tubing and mounted over a mercury
reservoir. Mercury levels in the manometer are adjusted as described for the burette

FIGURE 1. Vapour-pressure apparatus. Manometer M constructed from 20 mm Veridia precisionbore tubing with fiducial marks F4, F5; cell C, capacity 50 cm3 containing liquid of known mass
introduced through valve 2; platinum coil stirrer PS connected to a sealed glass tube containing
soft iron and lifted upwards by solenoid S; 12.7 mm Nupro stainless-steel bellows valves, 0, 1 to 3;
and 6.35 mm Nupro stainless-steel bellows valves, 0,4 to 8, with connexions to the valves through
Kovar glass-to-metal seals using zytel or teflon ferrules and Swagelok fittings; pulleys Pl to P3
to operate valves 4 to 6; mercury reservoirs Rl and R2; Dewar D raised with rod R to surround
cell, ice water added through Dewar funnel DF; calibrated measuring burette MB constructed
of 4 mm and 8 mm Veridia precision-bore tubing with fiducial marks Fl to F3 ; bulb B surrounded
by glass bowl GB, liquid introduced from degassing apparatus through valve 8.

Calibration (by nitrogen compression) of the volume of the cell between fiducial
mark F4 and valve 4, about 70 cm3, enables corrections to be made for vapour
space. When necessary a small Dewar can be raised with a rod to cool the cell and
its contents.
The method for degassing liquids has been described by Dunlop et ~1.c~) Using
the apparatus shown in figure 2, liquid is distilled from the storage flask SF into
flask .F which is cooled with liquid nitrogen, With continuous pumping, the frozen
liquid is slowly sublimed on to the liquid-nitrogen-cooled
cold finger. Although one
sublimation completely degasses most liquids the procedure is always repeated.
The measuring burette is filled with liquid as follows : with liquid in the flask below
closed valve 9 the degassing apparatus is connected to the vapour pressure apparatus
through valve 8 and both sections are pumped down overnight on the bench to a

CONTINUOUS-DILUTION

VAPOUR-PRESSURE

APPARATUS

841

pressure of less than 1O-3 Pa. After closing valve 8 about 25 cm3 of liquid 1 are
thoroughly degassed and then distilled through re-opened valve 8 into the bulb
under the burette with the mercury level slightly below the glass bowl which is filled
with suitable coolant. Valves 4 and 8 are closed and, after thawing, liquid 1 is forced
into the burette by raising the mercury level so that it is finally contained under
positive pressure between valve 4 and the mercury meniscus which, ideally, is just
to valve 8
=?l

high
vacuum

FIGURE 2. Degassing apparatus. Storage flask SF containing liquid and drying agent, sealed
with Nupro valve; 6.35 mm Nupro stainless-steel bellows valves, 0, $to 13; cold-fingerCFto
hold
liquid nitrogen; flask F to contain liquid distilled from SF: Pirani gauge head P: tran T to remove
vapour used in flushing the apparatus; glass T-tubing connects valves-10 and 11 to-valve 8 of the
vapour pressure apparatus, replaced by glass U-tubing when degassing the liquid to be distilled into
a weighed ampoule or flask; weighed break-seal ampoule A with 6.35 mm Kovar glass-to-metal
seal for attaching to valve 13. (For connexion to valve 2 of the vapour-pressure apparatus the 6.35 mm
glass-to-metal seal is removed from the reweighed filled ampoule and a 12.7 mm Kovar glass-tometal seal is joined at the break-seal end of the ampoule.)

below fiducial mark F2. Any excess liquid is bled off through valve 8 before the
degassing apparatus is detached. The vapour-pressure apparatus is then transferred
to a thermostatted bath to test the effectiveness of the degassing procedure. After
re-connecting the apparatus to the pumps with flexible stainless-steel tubing and
re-evacuating, the mercury is raised to suitable levels in the manometer arms and a
small volume of liquid 1 is admitted to the cell until the mercury meniscus in the
burette rises close to the fiducial mark F2. The vapour pressure of liquid 1 is measured
as described below. The apparatus is then removed from the bath.
The following procedure is used to admit pure liquid 2 of known mass to the vapour
pressure cell: with valves 10 and 11 connected with glass tubing, about 25 cm3 of
liquid 2 of known mass are degassed and then sublimed into, and finally sealed in,

842

R. S. MURRAY

AND

M.

L. MARTIN

either a small weighed flask with attached Nupro valve or a weighed break-seal
ampoule attached to valve 13. The mass of liquid 2 is determined from accurate
weighings, to +O.OOOl g, corrected to vacua. After attaching the ampoule or flask
to valve 2 of the vapour pressure apparatus and thoroughly evacuating, the liquid is
distilled into the cell cooled with liquid nitrogen. The frozen liquid is pumped on
briefly before raising the mercury level into the manometer arms and then allowing
thawing to proceed.
The loaded vapour-pressure apparatus is placed in a vibration-free thermostatted
bath, reconnected to the pumps, and levelled. After temperature equilibration the
positions of Fl and F4 and all mercury menisci are measured with a 1 m cathetometer
(Precision Tool & Instrument Co.). To make an addition of liquid 1 the cell is first
cooled by adding ice + water to the suitably positioned Dewar and then a small
quantity of liquid is admitted from the burette through valve 4. The ice water
remains in position in the Dewar due to its density and by cooling the cell contents
obviates large pressure changes if the added liquid has a vapour pressure very different
from that of the liquid in the cell. (This procedure is also used to bring back into the
cell any liquid which has condensed on the mercury surface in the manometer, a
problem which occurs with pure liquids and sometimes with mixtures.) After temperature equilibration the mercury level in the burette is recorded and the levels in
the manometer are read off until, with periodic stirring, the difference is constant.
These three readings together with the known mass of liquid in the cell give the
composition of the cell contents to a precision of better than +0.0002 in the mole
fraction and the vapour pressure to within 54 Pa. Further additions of liquid are
made to complete the remaining half of the mole-fraction range. At the conclusion
of the run the contents of the cell are distilled into a weighed flask with attached
Nupro valve to test for quantitative transfer of liquid 2 and accuracy of burette
additions. The second half of the mole-fraction range is covered by a second series of
measurements with the positions of the liquids reversed.
Bath-temperature control to better than + 0.002 K is achieved by use of a thermistor
bridge and the feedback from a sensitive chart recorder to activate a thyratron relay
and a 100 W blackened light globe. The absolute bath temperature is measured to
about f 0.003 K with a pressure-insensitive bomb-calorimeter thermometer calibrated
carefully and frequently against a Leeds and Northrup
platinum
resistance
thermometer.
3. Materials
Univar A.R. grade benzene and Merck Uvasol spectroscopic grade n-hexane
were purified by methods previously describedc5, @ and stored over clean sodium
wire. Impurities of not more than 0.002 and 0.02 mole per cent for the respective
liquids were revealed by gas-chromatographic analyses using 10 m columns packed
with 10 mass per cent of didecyl phthalate or squalane on AW-DMCS Chromosorb W
at 333 K in an Fl 1 Perkin-Elmer gas chromatograph with flame-ionization detection.
Samples were degassed and stored in flasks SF with attached Nupro valves (figure 2)
over B.D.H. type 4A molecular sieves which had been previously outgassed and dried

CONTINUOUS-DILUTION

VAPOUR-PRESSURE

APPARATUS

a43

at high temperature in vacua. These sieves were chosen for their extreme affinity for
water coupled with their ability to be degassed, a property not possessed by sodium
wire. Both liquids were degassed, as described above, just prior to use.
The condition of a liquid to be used for vapour pressure measurements was evaluated by measuring the equilibrium vapour pressure in the cell, then sweeping away
the vapour into a cold trap and retesting the remaining liquid. (The manometer levels
were lowered with liquid in the cell by first ballasting the high side of the manometer
with vapour from the same liquid contained in a flask attached to valve 2.) This
procedure produced no observable changes in benzene but successively reduced the
vapour pressure of n-hexane to a constant value indicating the presence of traces of
either air or volatile impurity in the sample. Samples of these liquids of similar purity
have previously been used for related work in this laboratory at which time their
densities were determined accurately and are in accord with those in reference 1 to
within &2x low5 g cme3. The masses of benzene and n-hexane injected from the
burette during a run were computed from these densities.
The vapour pressures of benzene (12.683 kPa) and n-hexane (20.153 kPa) at
298.15 K are in good agreement with literature values corrected to IPTS-68.l
4. Results and discussion
Excess Gibbs free energies GE(~l) were calculated from measured vapour pressures
using the method of Barker. () A vapour phase correction was applied in order to
obtain the true composition of the liquid phase. A computer program was used
to calculate GE&) and yl, the vapour phase composition, from an initial estimate
of x1 which ignored the vapour phase entirely. This value of y1 was then used to
compute a new x1 and the iterative cycle continued until convergence was obtained
in both modes, i.e. until successive values of x1 showed negligible changes while the
sum of the squares of the pressure residuals was minimized to give a least-squared
function of the form:
GE(xl)/RT = ~1x2 I;i Ui(Xl -~z)i.
(1)
Addition of extra terms ai and the introduction
tion (2) due to Myers and Scott,(*)
GE(xl)/RT

~1 x2

Z, Ui(Xl

-~z)i/{

of a skewing parameter K in equa1 -K(X,

-x2)},

(2)

produced no further significant reduction in the sum of the squares of the pressure
residuals.
Table 1 lists the experimental vapour pressures for two series of experiments at
calculated mole fractions x1 and y1 of n-hexane for the liquid and the vapour phases,
as well as the activity coefficients of n-hexane and benzene in the liquid phase and
excess Gibbs free energies at each mole fraction. The second virial coefficients of the
vapours used in calculating GE are those contained in reference 1.
In table 2 a comparison of the values of GE computed from the values of ni for both
runs in this work is made both against the originally reported values of Harris and
Dunlop() and, more directly, against the values calculated from their data fitted to

844

R. S. MURRAY
TABLE

1. Experimental

results

AND

for n-hexane

Sp = p(expt)

Xl
Run

Yl

plkpa

L. MARTIN
(1) + benzene

(2) at 298.15

- p(calc.)

Sp/kPa

fi

P/J

mol-1

0
0.0039
0.0107
0.0212
0.0312
0.0398
0.0629
0.1079
0.1402
0.1643
0.1953
0.2247
0.2599
0.2853
0.3101
0.3320
*0.407s
0.4324
0.4599
0.4947
0.5332
0.5667
0.6076
0.6502
0.7046
0.7593
0.8281
0.8978
0.9347
0.9591
0.9835
1

0.0132
0.0352
0.0663
0.0936
0.1152
0.1670
0.2473
0.2936
0.3238
0.3585
0.3883
0.4206
0.4422
0.4624
0.4790
0.5351
0.5522
0.5715
0.5949
0.6211
0.6441
0.6721
0.7018
0.7411
0.7824
0.8379
0.8983
0.9335
0.9577
0.9827
a, = 0.61990

12.683
12.807
13.018
13.311
13.584
13.807
14.348
15.244
15.780
16.137
16.559
16.904
17.288
17.537
17.761
17.963
18.509
18.678
18.834
19.046
19.244
19.400
19.576
19.737
19.906
20.041
20.156
20.224
20.120
20.194
20.173
20.153

0.003
0.008
0.002
0.004
0.006
0.001
-0.003
-0.007
-0.006
0.000
0.005
0.005
0.003
0.001
0.017
-0.003
0.004
-0.009
0.004
0.001
-0.003
-0.001
0.000
-0.003
-0.004
-0.005
0.013
0.002
-0.001
0.000
-

2.1681
2.1327
2.0809
2.0337
1.9952
1.8992
1.7407
1.6459
1.5838
1.5125
1.4534
1.3913
1.3518
1.3168
1.2885
1.2070
1.1851
1.1628
1.1376
1.1132
1.0946
1.0749
1.0575
1.0392
1.0249
1.0120
1.0040
1.0016
1.0006
1.0001
-

al = -0.11672,
E(SP,)~

Run

M.

az = 0.03304,
= 0.050

l.&
1.0001
1.0005
1.0012
1.0019
1 SW45
1.0127
1.0208
1.0278
1.0382
1.0493
1.0641
1.0756
1.0876
1.0988
1.1417
1.1570
1.1747
1.1985
1.2262
1.2517
1.2845
1.3206
1.3698
1.4226
1.4936
1.5699
1.6115
1.6393
1.6674
-

7.5
20.5
39.8
57.7
72.5
110.6
176.2
217.0
244.1
275.2
300.8
326.7
342.3
355.2
364.7
384.,
387.1
387.6
384.9
377.8
368.2
352.3
331.2
297.6
256.6
195.4
123.0
80.9
51.6
21.1
-

a3 = -0.01375

kPa2

0
0.0133
0.0287
0.0463
0.0872
0.1404
0.1966
0.2590
0.3243
0.3736
0.4094
0.4562
*0.4569
0.5271
0.6277

0.0430
0.0866
0.1304
0.2128
0.2940
0.3603
0.4201
0.4739
0.5106
0.5362
0.5688
0.5695
0.6172
0.6867

12.683
13.079
13.507
13.958
14.849
15.784
16.571
17.283
17.880
18.274
18.530
18.825
18.821
19.212
19.650

-0.003
0.000
0.003
0.001
- 0.002
-0.003
0.003
-0.003
0.003
0.006
0.002
-0.005
-0.003
-0.009

2.1051
2.0345
1.9593
1.8071
1.6459
1.5113
1.3942
1.2990
1.2414
1.2057
1.1659
1.1653
1.1173
1.0672

1.0002
1.0009
1.0024
1.0082
1.0203
1.0381
1.0630
1.0944
1.1212
1.1424
1.1721
1.1726
1.2213
1.2999

25.1
52.8
82.9
146+
216.3
275.7
325.6
361.3
377.9
384.9
387.6
387.6
379.3
343.3

CONTINUOUS-DILUTION

VAFOUR-PRESSURE

l-cuntinued

TABLE

Xl

Yl

0.6911
0.7440
0.8135
0.8644
0.9224
0.9705
0.9896
1

0.7314
0.7708
0.8260
0.8690
0.9217
0.9685
0.9888
a, = 0.61993,

TABLE

2. Comparison

Run

PI@

Gp/kPa

19.885
20.028
20.152
20.206
20.221
20.202
20.169
20.153

0.007
0.006
-0.003
-0.003
-0.003
0.009
O.OOG
-

a2 = 0.03563,
al = -0.11567,
Z&@
= 0.025 kFa2

A
1.0445
1.0297
1.0153
1.0080
1.0026
1.0004
1.oooo
-

GE/J mol-l

1.3552
1.4050
1.4763
1.5333
1.6038
1.6674
1.6941
-

307.3
269.8
210.*
160.1
96.7
38.3
13.8
-

(1) + benzene

(2)

a3 = -0.00392

Run2

Harris
observed

and Dunlop)
cake., equation

(1)

GE/J mol-1

Xl
0.09787
0.17675
0.29029
0.36452
0.37531
0.48754
0.59742
0.69838
0.79959
0.90882

A2

of excess Gibbs free energies GE for n-hexane

with the results of Harris and Dunlop(l)
1

845

APPARATUS

a Misprinted

162.5
257.1
345.1
375.7
378.5
385.7
356.7
301.8
222.0
110.7
in the original

161.5
256.3
344.7
375.5
378.4
385.7
357.0
302.6
223.5
112.4

162.2
257.6
346.6
377.a
380.3
387.0
356.8
300.8
220.6
109.8

162.0
257.9
347.2
377.8
380.6
386.5
355.9
300.6
221.6
111.7

paper.(l)

a four-parameter equation (1) at their mole fractions. The agreement is within experimental error which, from an analysis of the equations : ( )
GE = x&+x,&
P? = RTln(~~i/~ix,)+(Vi-Bii)(Pi-~)+~6ijYj,

(3)

(4)
is approximately +2 J mol-l taking into account the approximation 6,, = 0 which
is widely used and is discussed in reference 1. The external consistency is shown by
the measurements around the overlap region (marked by asterisks in table 1).
It is believed that this apparatus offers some advantages over continuous-dilution
methods previously described. ~,~r) The relative simplicity of the cell ensures speedy
equilibration after an addition is made and, because of its extremely small leak rate
(less than 2 x 10V4 Pa mm-l), the vapour pressure of an enclosed liquid remains
static within experimental error for long periods. The mercury piston type burette
allows the introduction of rigorously degassed liquids and their subsequent storage in
that condition for indefinite periods.

846

R. S. MURRAY

AND

M. L. MARTIN

As transfer and testing of degassed liquids in the apparatus require 1 to 2 d, while

measurements of vapour pressures for each half of the composition range take a
further day, a complete mixture can normally be studied in 5 to 6 d.
We are grateful to Mr J. Netting and Mr G. Duthie for the construction of the
apparatus and to Mr M. A. Yabsley for assistance with the computing program.
This work was supported by a grant from the Australian Research Grants Committee.
REFERENCES
1. Harris, K. R.; Dunlop, P. J. J. Chem. Thermodynamics 1970,2,805.
2. Stokes, R. H.; Levien, B. J.; Marsh, K. N. J. Chem. Thermodynamics 1970,2,43.
3. Stokes, R. H.; Marsh, K. N.; Tomlins, R. P. J. Chem. Thermodynamics 1969,1, 211.
4. Ewing, M. B.; Marsh, K. N.; Stokes, R. H.; Tuxford, C. W. J. Chem. Thermodynamics 1970,
2, 751.
5. Bell, T. N.; Cussler, E. L.; Harris, K. R.; Pepela, C. N.; Dunlop, P. J. J. Phys. Chem. 1968,
72,4693.
6. Shepard, A. F.; Henne, A. L.; Midgely, Jr., T. J. Amer. Chem. Sot. 1931,53, 1948.
7. Barker, J. A. Aust. J. Chem. 1953,6, 207.
8. Myers, D. B.; Scott, R. L. Ind. Eng. Chem. 1963,55,43.
9. Scatchard, G.; Raymond, C. L. J. Amer. Chem. Sot. 1938, 60, 1278.
10. Tomlins, R. P. Paper presented at the Fifth National Convention of the Royal Australian
Chemical Institute, Canberra, 1974.
11. Gibbs, R. E.; Van Ness, H. C. Ind. Eng. Chem. 1972,11, 410.