J. Chem.

Thermodynamics 1998, 30, 709]712

Article No. ct970335

Isopiestic studies on ( methanol H sodium

bromide H ammonium bromide) at the
temperature 298.15 K: comparison with
the partial ideal solution model
Zhi-Chang Wang, a Xiu-Yan Li, and Yi-Hui Liu
Department of Chemistry, Northeastern Uni¨ ersity, Shenyang 110006,
Liaoning, P.R. China

Isopiestic measurements have been carried out for the ternary system Žmethanol q sodium
bromide q ammonium bromide. at the temperature 298.15 K. The results fit the partial ideal
solution model within experimental errors. Q 1998 Academic Press

KEYWORDS: isopiestic studies; Žmethanol q sodium bromide q ammonium bromide.;

partial ideal solution model

1. Introduction
By using the isopiestic technique, accurate activity data have been determined for
hundreds of binary and ternary aqueous solutions at the temperature T s
298.15 K.Ž1. Bonner Ž2. has recently extended this technique to binary methanol
solutions at T s 298.15 K. Until now, however, the same measurements have not
been carried out for any ternary systems involving organic solvents. On the other
hand, we have extended the isopiestic technique to binary and ternary alloys,Ž3 ] 5.
molten salt mixtures Ž6,7. and slags,Ž8. as well as quaternary aqueous solutions,Ž9 ] 11.
and compared the results with a partial ideal solution modelŽ12 ] 16. proposed
previously. In this study, we tried to extend this technique to ternary methanol
solutions, taking  methanolŽA. q sodium bromideŽB. q ammonium bromideŽC.4 as
an example, and to compare the experimental results with the partial ideal solution
model.

2. Experimental
Isopiestic measurements were made by the method described previously.Ž9 ] 11.
Analytical grade NaBr, NH 4 Br, and NaI . 2H 2 O were obtained from Shenyang
Chemical Co. and reagent grade methanol was supplied by Tianjin Chemical Co.
The reported total amount of solid impurities was mass fraction - 1 . 10y4 for each
of the salts. Both NaBr and NH 4 Br were recrystallized from doubly distilled water
a
To whom correspondence should be addressed.

0021]9614r98r060709 q 04 $30.00r0 Q 1998 Academic Press

710 Z.-C. Wang, X.-Y. Li, and Y.-H. Liu

and were then dried at low pressure over CaCl 2 , at T s 323 K for NH 4 Br and at
T s 423 K for NaBr. The NaI . 2H 2 O was recrystallized from Žwater q acetone.
and was dried at T s 333 K under reduced pressure. All the salts were then kept
over P2 O5 in a vacuum desiccator before use. Methanol was further purified by
repeated distillation, and the middle half of the starting material of each distillation
was used. Each sample was run in duplicate and  methanolŽA. q sodium iodide4
was used as the reference standard. Preliminary experiments showed that the
isopiestic equilibria might be achieved within Ž3 to 5. d. Therefore, the formal
equilibrium period was Ž5 to 8. d for each run. At the end of the run, after pressing
a lid on to all the cups, the isopiestic apparatus was placed in a dry container where
the temperature was kept near to T s 273 K. After opening the isopiestic apparatus,
individual caps were immediately placed on the cups before they were weighed.
The maxmium difference between duplicates was not larger than 0.5 per cent, and
in most cases the difference was not larger than 0.1 per cent. The osmotic
coefficient calculated according to Bonner Ž2. was uncertain by about 1 per cent.Ž2.

3. Results and conclusions

If m and f denote molality and osmotic coefficient, respectively, and the superscript
oo
denotes the behaviour for the binary subsystem  methanolŽA. q non-volatile
soluteŽB.4 , or  methanolŽA. q non-volatile soluteŽC.4 , isopiestic behaviour of a
ternary methanol solution  methanolŽA. q non-volatile soluteŽB. q non-volatile
soluteŽC.4 , which obeys the partial ideal solution modelŽ12 ] 16. due to zero
interchange energy between B and C, may be expressed as:

Ž m Brmoo
B . q Ž m C rm C . s 1,
oo
Ž 1.
at constant aA and within 0 F Ž m Crmoo C F 1. In other words, if a ternary system
.
which follows the partial ideal solution model, and two of its binary subsystems are
isotonic Žthe solvent activities of all three are equal., then this ternary system has
such a composition that it can be prepared by mixing these two binary subsystems.
The deviation of a real system from equation Ž1. can then be defined by:

B . q Ž m C rm C . 4 y 1,
D s  Ž m B rmoo oo
Ž 2.
at constant aA and within 0 F Ž m C rmoo
C F 1. Table 1 shows eight sets of isopiestic
.
results for the  methanolŽA. q sodium bromideŽB. q ammonium bromideŽC.4
ternary system. The first column gives the molality of the reference system
 methanolŽA. q sodium iodide4 . The second and third columns give the molalities
m B of NaBr and m C of NH 4 Br. The fourth column gives the osmotic coefficient of
the solutions investigated. The fifth column gives the values of the D function
defined by equation Ž2.; it can be seen that < D < F 0.003.
According to Rard and Platford,Ž1. an individual isopiestic molality at equilibrium
can be determined to "Ž0.0005 . m. to "Ž0.001 . m., and the molality ratio of the
reference standard to the test solution determined to Ž"0.001 to "0.002. at
T s 298.15 K for aqueous solutions under favorable conditions. However, the
precision of the isopiestic experiments for methanol solutions at T s 298.15 K is
 ŽMethanol q sodium bromide q ammonium bromide. at T s 298.15 K 711

TABLE 1. Isopiestic results for the methanolŽA. q sodium bromideŽB. q ammonium bromideŽC.4
ternary system at T s 298.15 K, where m ref denotes values for the reference system methanolŽA. q
sodium iodide4, mo s 1 mol . kgy1 , f denotes osmotic coefficient, and D denotes the experimental
deviation from equation Ž1.

m refrmo m B rmo mC rmo f D

1.0002 1.0171 0 0.972

0 1.1444 0.863
0.8336 0.2086 0.948 0.0019
0.6402 0.4264 0.926 0.0020
0.4373 0.6558 0.904 0.0030
0.2230 0.8919 0.886 y0.0014
0.8816 0.8935 0 0.948
0 1.0130 0.836
0.7342 0.1833 0.923 0.0027
0.5627 0.3751 0.903 0.0001
0.3849 0.5776 0.880 0.0010
0.1967 0.7873 0.861 y0.0027
0.7345 0.7481 0 0.912
0 0.8493 0.803
0.6125 0.1533 0.891 y0.0008
0.4702 0.3137 0.871 y0.0021
0.3218 0.4835 0.847 y0.0006
0.1659 0.6620 0.824 0.0012
0.5597 0.5724 0 0.873
0 0.6538 0.764
0.4650 0.1223 0.851 y0.0006
0.3610 0.2408 0.830 y0.0010
0.2470 0.3707 0.809 y0.0015
0.1269 0.5086 0.786 y0.0004
0.4905 0.5019 0 0.858
0 0.5751 0.749
0.4116 0.1029 0.837 y0.0010
0.3169 0.2113 0.815 y0.0012
0.2173 0.3260 0.793 y0.0002
0.1118 0.4472 0.770 0.0004
0.4697 0.4741 0 0.866
0 0.5360 0.766
0.3883 0.0970 0.846 0.0000
0.2979 0.1986 0.827 y0.0011
0.2035 0.3053 0.807 y0.0012
0.1045 0.4181 0.786 0.0005
0.4301 0.4231 0 0.880
0 0.4682 0.796
0.3455 0.0862 0.863 0.0007
0.2644 0.1762 0.845 0.0012
0.1798 0.2695 0.829 0.0006
0.0913 0.3670 0.813 y0.0004
0.3831 0.3661 0 0.896
0 0.3971 0.826
0.2970 0.0745 0.883 y0.0011
0.2269 0.1507 0.869 y0.0007
0.1536 0.2303 0.855 y0.0005
0.0782 0.3121 0.841 y0.0004
712 Z.-C. Wang, X.-Y. Li, and Y.-H. Liu

limited by the relatively high solvent losses, similar to the same measurements for
aqueous solutions at high temperature. Thus, the value of < D < F 0.003 would
indicate that the  methanolŽA. q sodium bromideŽB. q ammonium bromideŽC.4
ternary system follows the partial ideal solution model within our experimental
errors.
It has been shown that the partial ideal solution modelŽ12 ] 16. is valid for the
systems  solventŽA. q soluteŽB. q soluteŽC. q ??? 4 with zero solute]solute
interchange energy. This argument is supported both by the literature data and by
our own isopiestic measurements for alloys,Ž4. molten salt mixtures,Ž7. slags,Ž8.
non-electrolyte aqueous solutions,Ž9,11. and electrolyte aqueous solutions.Ž10. This
paper presents the first evidence for  organic solventŽA. q soluteŽB. q soluteŽC.
q ??? 4 . We will soon report the isopiestic measurements for Žwater q methanol q
sodium bromide q ammonium bromide., where activities of both water and
methanol are equal for the quaternary system and its two ternary subsystems
Žwater q methanol q sodium bromide. and Žwater q methanol q ammonium
bromide.. One of the referees suggested that equation Ž1. is indeed fulfiled quite
accurately in, perhaps, up to 3 mol . kgy1 aqueous mixtures with a common ion and,
for Žwater q NaCl q CaCl 2 ., it is still fulfiled reasonably well up to 6.7 mol . kgy1
NaCl reference, but a larger deviation is expected when no common ion is present,
probably due to the larger interchange energy between the solutes in the latter
case. Therefore, further experimental determinations will be very interesting for
such  organic solventŽA. q soluteŽB. q soluteŽC.4 systems without a common ion,
such as  methanolŽA. q sodium iodideŽB. q ammonium bromideŽC.4 , to see if a
larger deviation from equation Ž1. exists.

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(Recei¨ ed 16 September 1997; in final form 9 December 1997)

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