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OF SYSTEMS AND PROCESSES
Adipic acid (AA) is a large-capacity product used coupling rod and introduced into a thermostat. The
mainly in fiber production. The solubility of solids in flask contents were stirred by reciprocal motion of the
liquids is one of the most important process param- flask, provided by a synchronous electric motor (e.g.,
eters and is of scientific interest for the development SD-54 motor with 60 rpm rotation speed) equipped
of the solution theory. with a crank system. The temperature was kept con-
stant to within + 0.1oC.
EXPERIMENTAL To measure the solubility by the isothermal meth-
Analytically pure grade adipic acid was recrystal- od, solution samples should be taken for analysis in
lized twice from water and dried at 120oC. Its melting
point was 151.5 + 0.2oC, which agrees with the most
reliable published data [1]. Chemically pure and
analytically pure grade organic solvents were dried
by standard procedures [2]. Acetone and alcohols
were kept for a day over drierite and then distilled.
1,4-Dioxane was kept over KOH for two weeks, re-
fluxed over sodium metal for a day, and then distilled.
Acetic acid had mp 16.6oC after twofold freezing.
The water content in solvents was no higher than
(wt %): 0.04 in methanol, 0.08 in ethanol, 0.06 in
propanol, 0.06 in isopropanol, 0.08 in n-butanol, 0.08
in tert-butanol, 0.02 in acetone, 0.02 in 1,4-dioxane,
and 0.1 in acetic acid. The water content in acetic acid
was determined using the melting point depression
curve [3] and in the other solvents, by Fischer titra-
tion. Double-distilled water was used.
The AA solubility was determined by the isother-
mal method. The thermodynamic equilibrium between
excess solid phase at the solvent was attained by con-
tinuous agitation and a constant temperature with a
device consisting of a U-10 ultrathermostat and a
mechanical stirrer. The stirrer was mounted on the
thermostat lid.
To determine the solubility, adipic acid and a solv- Sampler: (1) tube, (2) glass frit. (3) temperature-controlled
ent were charged into 100 3200-ml flasks with pipet, (4) connecting tubes, (5) conical ground-glass joint,
ground-glass stoppers. The flasks were fixed on a and (6) stopcock.
Table 3. Activity coefficients of adipic acid in water The coefficients of Eq. (3) are listed in Table 4.
ÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÂÄÄÄÄÄÄÂÄÄÄÄÄ
Then, using the known thermodynamic equations,
T, oC
³AA content in water,³ a ³ I ³ g
³ mol per 1000 g ³ ³ ³ we calculated DS and DH of solution (see Table 5). In
ÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÅÄÄÄÄÄÄÅÄÄÄÄÄ all the cases, the enthalpies of solution are positive
0 ³ 0.0475 ³ 0.028 ³ 0.004 ³ 0.999 and hence the enthalpies of solvation do not exceed
20 ³ 0.1263 ³ 0.017 ³ 0.006 ³ 0.998 the enthalpies of the molecular crystal lattice. In the
40 ³ 0.351 ³ 0.010 ³ 0.010 ³ 0.997 series of normal alcohols, the AA solubility decreases
60 ³ 1.182 ³ 0.006 ³ 0.020 ³ 0.996 from methanol to butanol, and the enthalpy of solu-
ÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄÄÁÄÄÄÄÄ tion increases. In other words, in the series of normal
alcohols, the interaction of AA molecules with solvent
Table 4. Coefficients of Eq. (3) molecules becomes weaker. For the most part of
ÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄ solvents studied, this interaction becomes weaker with
Solvent ³ A ³ B ³ C increasing temperature. Thus, an interesting fact is
ÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄ observed: the enthalpy growth in one case is accom-
Methanol ³ 8.69 ³ 30.0474 ³ 30.00009
Ethanol ³ 9.37 ³ 30.0487 ³ 30.00012 panied by a decrease in the solubility and in the other
Propanol ³ 10.36 ³ 30.0574 ³ 30.00011 case, by its increase.
Isopropanol ³ 9.98 ³ 30.0674 ³ 0.00003 The enthalpy of solution characterizes only the
Butanol ³ 10.80 ³ 30.0566 ³ 30.00014 energetic aspects of the solute3solvent interaction.
tert-Butanol ³ 8.11 ³ 30.0419 ³ 0.00004 However, the interaction between solvent molecules,
Acetic acid ³ 10.99 ³ 30.0509 ³ 30.00019 determining the solvent structure, also changes upon
1,4-Dioxane ³ 9.31 ³ 30.0549 ³ 30.0005 dissolution; this factor also affects the dissolution.
Acetone ³ 11.44 ³ 30.0430 ³ 30.00022
Water ³ 16.00 ³ 30.0408 ³ 30.00077 The joint analysis of the thermodynamic character-
ÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄ istics of AA dissolution shows that both the enthalpy
and entropy components increase in the series of
For poorly soluble, weakly dissociating substances, normal alcohols. The enthalpy component changes to
the activity a can be replaced by its mole fraction x a greater extent than the entropy component. As a
[12], and then result, the interaction between AA and alcohol mole-
cules becomes weaker in this series. With increasing
DG = 3RT ln x. (2) temperature, the entropy component increases faster
than the enthalpy component, and DG decreases.
To check the validity of such substitution, we Hence, the temperature affects more strongly the
determined the degree of AA dissociation in water solution structure, whereas the alcohol molecule size
using the Ostwald dilution law. The AA dissociation affects more strongly the energy of intermolecular
constant in water was taken from Dobos handbook interactions.
[13]. The a values obtained assuming the dissociation
constant to be temperature-independent are given in For isopropyl and tert-butyl alcohols, the enthalpy
Table 3. The solution ionic strengths I produced by component decreases with increasing temperature,
the ionized fraction of AA are also listed in Table 3. while the entropy component increases, i.e., both
The dependence of the AA activity coefficient on the components of the free energy favor dissolution,
solution ionic strength was determined in [14] from which explains their anomalous position in the alcohol
the solubility in water in the presence of electrolytes. series.
The calculated activity coefficients g are listed in It should be noted that the entropy component in-
Table 3. As seen, they only slightly differ from unity, creases to the greatest extent in water and acetone.
and hence Eq. (2) can be used for calculating DG. The AA solubility in these solvents is the lowest as
Since the AA dissociation constants in the chosen compared to the solubility in the other solvents
organic solvents should be substantially lower than in studied. This means that the water and acetone struc-
water, Eq. (2) is also applicable to the other solvents. tures are fairly stable at the temperatures studied and
The temperature dependence of DG is approxi- that AA dissolution actively breaks these structures.
mated by a quadratic equation: The structure of liquid tert-butyl alcohol is weak,
and AA molecules weakly affect the level of its
DG = A + B(T 3 273.15) + C(T 3 273.15)2. (3) ordering.
pounds. Intercollegiate Collection), Gor’kii: Gor’k. 1953, vol. 49, no. 12, pp. 140531410.
Gos. Univ., 1979, no. 8, pp. 28333. 9. Spravochnik po rastvorimosti (Handbook on Solubil-
2. Weissberger, A. and Proskauer, E.S., Organic Solv- ity), Kafarov, V.V., Ed., Moscow: Akad. Nauk SSSR,
ents. Physical Properties and Methods of Purification, 1961, vol. 1, book 1.
Riddick, J.A. and Toops, E.E., Eds., New York: Inter- 10. Mullin, J.W., Crystallization, London: Butterworth,
science, 1955. 1961.
3. Gyenes, I., Titration in Non-Aqueous Media, Co- 11. Li, I.F., Semenov, L.V., Gaile, A.A., and Pul’-
hen, D., Ed., Budapest: Akademiai Kiado, 1967. tsin, M.N., Zh. Fiz. Khim., 1984, vol. 58, no. 10,
4. Polyanskaya N.L. and Polyanskii, N.G., Zh. Fiz. pp. 243532438.
Khim., 1982, vol. 56, no. 2, pp. 5033504. 12. Krestov, G.A. and Abrosimov, V.K., in Termodinami-
ka i stroenie rastvorov: Mezhvuzovskii sbornik (Ther-
5. Shvedov, V.P. and Zhurenkov, E.M., Zh. Neorg.
modynamics and Structure of Solutions: Intercolle-
Khim., 1956, vol. 11, no. 7, pp. 165931661.
giate Collection), Ivanovo: Ivanov. Khim.-Tekhnol.
6. Gorodetskii, E.T., Izv. Vyssh. Uchebn. Zaved., Khim. Inst., 1976, issue 3, pp. 13328.
Khim. Tekhnol., 1980, vol. 33, no. 3, pp. 2683272. 13. Dobos, D., Electrochemical Data, Budapest: Akade-
7. Kreshkov, A.P., Osnovy analiticheskoi khimii (Funda- miai Kiado, 1978.
mentals of Analytical Chemistry), Moscow: Khimiya, 14. Mel’nik, V.V., Komar’, N.P., Shcherban’, S.N., and
1976, vol. 2. Slyshova, L.D., Izv. Vyssh. Uchebn. Zaved., Khim.
8. Davies, M. and Griffithes, D.M., Trans. Farad. Soc., Khim. Tekhnol., 1973, vol. 26, no. 8, pp. 1186 31188.