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J. Chem. Thermodynamics 1999, 31, 8591

Article No. jcht.1998.0424 Available online at
http:www.idealibrary.com on

Solubilities of o-
acetylsalicylic, 4-aminosalicylic,
3,5-dinitrosalicylic, and p-toluic
acid, and magnesium-DL aspartate
water from
in T ( ) 278 to 348

Alexander Apelblat a and Emanuel Manzurola

Department of Chemical Engineering, Ben Gurion Unionsity of the Nege,
Beer Shea, Israel

Solubilities of o-acetylsalicylic, 4-aminosalicylic, 3,5-dinitrosalicylic, and p-toluic acid, and magnesium-

DL-aspartate in water were determined in the temperature range Ž278 to 345. K.
The apparent molar enthalpies of solution at T 298.15 K were derived from these solubilities, and the
. first

resulting values are sol HmŽo-C9H8O4 , 22.9 kJ mol C m 0.0226 mol kg .

. first

, sol m . first
. first

, H 3,5-
H7Ž4-CHON,
73 m 0.00758 mol kg . 26.1 kJ mol m 0.0633 mol kg . sol mm
. first
. first

,
7 H 4O7 N2 , 28.7 kJ mol 0.00258 mol kg . sol HmŽ p-C8 H 8O2 ,
. first
.
24.0 kJ mol 1
first

, kg . 11.7 sol
kJ HmŽDL-C8H12O3N2
mol . Mg, m 0.1485 and mol
. first
. 1999 Academic Press

KEYWORDS: solubilities; organic acids; molar enthalpies of solution

1. Introduction

The present work continues our previous studies of the solubilities of organic
compounds of biological and industrial importance.Ž1 5. Solubilities of organic acids
and of magnesium-DL-aspartate in water as a function of temperature are reported
and compared, when possible, with the literature data. No solubilities exist for
magnesium-DL-aspartate and for 3,5-dinitrosalicylic acid in the main compilations
of solubilities,Ž6 8. and in the Beilstein electronic database.Ž9. Only a few solubilities
are known in the case of o-acetylsalicylic acid and 4-aminosalicylic acid,Ž9. while
solubilities of p-toluic acid are better documented.Ž9 12.
The apparent molar enthalpies of solution at T 298.15 K were calculated for these
substances from measured solubilities.

2. Experimental

o-Acetylsalicylic acid Ž2-acetoxybenzoic acid., 2-ŽCHCO .CHCO3 2 6 4 2 H Žmass fraction

0.99. from Aldrich;ŽOH.CO
4-aminosalicylic
H Žmassacid 4-amino-2-hydroxybenzoic
fraction 0.97. from Fluka;
Ž acid., NH CH
3,5-dinitrosalicylic
263 2

a
To correspondence who should be addressed ŽE-mail: apelblat@bgumail.bgu.ac.il..

0021961499010085 07 $30,000 1999 Academic Press

Machine Translated by Google
eighty six

A. Apelblat and E. Manzurola

acid Ž3,5-dinitro-2-hydroxybenzoic acid., O2NC6H2NO2ŽOH.CO2H Žmass fraction 0.98.

from Merck; p-toluic acid Ž4-methylbenzoic acid., CH3C6H4CO2H Ž . mass fraction
0.99 from
further BDH; and magnesium-DL-aspartate
purification. CH2CO242Mg.4H2O Ž in tetrahydrate,
the solubility
HO2CCH
experiments
. NH2without
. mass fraction 0.98 from Fluka were used

The dissolved measurements were performed with double distilled water Žin both
directions, by increasing and decreasing temperature as described elsewhere. In each Ž1.
few system under consideration, the Ž solidinliquid
preliminary . . was ensured
equilibrium
experiments the time
by checking
of stirring
and appealing settling at a temperatures in the studied temperature interval. In actual
experiments

TABLE 1. Solubilities m of organic acids and magnesium-DL-aspartate in water as a function of

temperature T
TK mŽ mol kg ... first

. TK mŽ mol kg
first

. TK mŽmol kg .
first

o-acetylsalicylic acid
278.15 0.0111 303.65 0.0265 326.15 0.0470
284.15 0.0141 309.15 0.0319 331.15 0.0517
289.15 0.0166 313.65 0.0342 336.65 0.0571
293.65 0.0201 316.65 0.0377 341.15 0.0622
299.65 0.0232 321.15 0.0414 345.15 0.0672

4-aminosalicylic acid
278.65 0.00351 298.65 0.00784 311.65 0.02514
283.65 0.00446 302.15 0.01002 313.15 0.03509
288.65 0.00567 306.65 0.01296 316.15 0.01819

3,5-dinitrosalicylic acid
278.15 0.0332 309.15 0.1039 336.15 0.5375
284.15 0.0405 313.65 0.1208 336.65 0.5414
290.15 0.0530 317.15 0.1472 340.15 0.6987
294.15 0.0594 321.65 0.2005 346.15 1.1973
299.15 0.0702 326.15 0.2633
304.15 0.0882 331.15 0.3749

p-toluic acid
278.15 0.00148 308.15 0.00367 325.15 0.00670
284.15 0.00183 308.15 0.00368 328.15 0.00785
290.15 0.00199 308.15 0.00369 331.15 0.00870
294.65 0.00227 313.15 0.00436 333.15 0.00942
298.15 0.00278 313.15 0.00437 334.65 0.0102
298.65 0.00234 313.15 0.00469 338.15 0.0112
303.15 0.00345 318.15 0.00530 340.15 0.0125
303.15 0.00359 323.15 0.00652 343.15 0.0137

magnesium-DL-aspartate
284.15 0.1216 309.15 0.1771 333.15 0.2901
289.15 0.1277 314.15 0.1953 338.15 0.3158
294.15 0.1374 319.15 0.2140 343.15 0.3492
298.15 0.1485 324.15 0.2325 348.15 0.4058
304.15 0.1603 328.15 0.2599
Machine Translated by Google

Solubilities of organic acids and magnesium-DL-aspartate in water

eighty seven

FIGURE 1. Solubility m of o-acetylsalicylic acid as a function of temperature T. reference 9. , this work;

,

FIGURE 2. Solubility m of 4-aminosalicylic acid as a function of temperature T. reference 9. , this work;

,
Machine Translated by Google

88 A. Apelblat and E. Manzurola

the times needed to attain equilibrium were almost doubled Žabout 1 h for stirring and 24 h
for settling..
Weighed samples of saturated solutions of organic acids were titrated with solutions of
NaOH Ž . Frutarom Laboratory Chemicals Ltd, Haifa standardized
, with potassium
hydrogen phthalate Ž . Rieden de Haen . Magnesium-DL-asparate was titrated
complexometrically with solutions of EDTA . Merck using Eriochrome
black T as an indicator. At each temperature, the reported solubilities are the average of two,
or sometimes three determinations.

3. Results and discussion

At constant pressure, for solutes forming a hydrate having h molecules of water, the solubility
of a solid in a liquid as a function of temperature T is expressed by the relation:Ž13.

lnŽ
mm
4 . Ž.1 account 1 ln RKŽ1
4 . ln mm
hmM
H

sol .4,
m Ž1. first

where H issolthe
m molar enthalpy of solution, R is the gas constant, M is the molar mass of HO, first

m and are the molality2 of the solute and its activity coefficient, respectively, and m 1 mol kg .
. first

Since the values of the activity coefficients in the evaluated systems are unknown, it is possible
to determine only the apparent enthalpies of solution by neglecting the activity coefficient term
in equation Ž . first
.

FIGURE 3. Solubility as a function of temperature T: DL- , 3,5-dinitrosalicylic acid; , magnesium

aspartate.
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Solubilities of organic acids and magnesium-DL-aspartate in water 89

FIGURE 4. Solubility m of p-toluic acid as a function of temperature T. 11; reference , this work; , reference
,
12; , reference 10; , reference 9.

The solubilities of organic acids as a function of temperature are presented in table 1 and
plotted in figures 1 to 4. Over the studied temperature range they can be expressed as:

first

lnŽ . mm , oC HO
9 8 44 121.384 7918.44ŽTK. 17,308 LnŽTK. , Ž2.
278.15 K T 345.15 K; 4 FOR

lnŽ . mm , N4 5.6570
7 7 3 3142.10ŽTK ,
. first

Ž3a.
278.65 K T 300.50 K;

lnŽ . mm , 4 FOR 7N4

7 3 28.9562 10143.9ŽTK , 300.50K T 316.15K;
. first

Ž3b.

first

lnŽ . mm , 3.5-C7H4O7N2 4 799,043 32508.4ŽAccount.

120,621 lnŽ . , Ž4.
Account 278.15 Account 346.15 Credit ;
first

lnŽ . mm , p-C8H8O2 4 264.605 9059.53ŽTK.

40,069 lnŽ . , Ž5.
Account 278.15 Account 343.15 Credit ;
first

lnŽ . mm , DL-C8H12O8N2Mg4 190,743 7217.37ŽTK.

28,893 lnŽ . , Ž6.
Account 284.15 Account 348.15 Account .
Machine Translated by Google

90 A. Apelblat and E. Manzurola

The coefficients in the above equations were evaluated by using an unweighted

multivariate least-squares method using the solubilities presented in table 1.
, Ž9.
In the case of o-acetylsalicylic acid figureŽ 1 . the literature solubilities are known only
from T Ž 287 to 310 K. Theindicative
data are . widelyinscattered
values the comparison
and canwith
only
ourberesults.
considered to have

Solubilities of 4-aminosalicylic acidŽ9. cover the same temperature interval and

show no clear temperature dependence Žbehave . figure differently,
2regions,
. The solubilities
below
having
and presented
two
above T here
distinct
300.5 K. The assumption that over the studied temperature interval the molar
enthalpy of solution various linearly with temperature was found inapplicable in this
case the branches of the solubility curve are represented by two equations Ž . 3a
and Ž3b.4.
Since the analysis of the solid phase was not performed, it is difficult to attribute
the transition near T 300.5 K to the formation of 4-aminosalicylic acid hydrate.
No solubilities for 3,5-dinitrosalicylic acid and for magnesium-DL-aspartate exist in
the literature. Contrary to other evaluated organic acids, 3,5-dinitrosalicylic acid is soluble
in water, especially for T 320 K Ž . figure 3 . In the case of
magnesium-DL-asparate, the solubility depends weakly on temperature, and
the apparent molar enthalpy of solution is rather low.
There is a very satisfactory agreement between our solubilities and the literature Ž9
12. data forremarkable
p-toluic acid over
fact the entirethat
considering temperature rangeof
the solubilities Ž p-toluic
. figure 4acid
. This
low is0.0015
a mare mol
Žin. water
from so
kg to m 0.014 mol kg .
. first
. first

Only the apparent molar enthalpies of solution were calculated at T 298.15 K from
equations Ž . 1 to Ž6. Žh 0 for organic acids, and h 4 in the case of magnesium-DL-
aspartate. by neglecting the activity coefficients in the evaluated HmŽo-C9H8O4 ,
molar enthalpies of solution are: 0.0226 mol kg . Ž sol systems. The apparent
m
. kJ mol. 26.1 kJ
first

, mol H7H4-CHON,
first
.
m 0.00758 mol kg . 22.9 first

sol m 73
. , sol m 3,5-FOR
first

H m ,
0.0633 mol kg H Ž pC . . 28.7 kJ
. ,
first first

7472
.kg mol , mol and
HOCHON8 8Mg, m 0.00258
m, 0.1485 mol kg . mol
11.7 kg . kJ mol.
. 24.0 sol m H DL-
first first

sol m 2
. .first first

8 12 3 2

The authors appreciate the technical assistance of Ms Ana Maron.

REFERENCES

1. Apelblat, A.; Manzurola, E. J. Chem. Thermodynamics 1987, 19, 317320.

2. Apelblat, A.; Manzurola, E. J. Chem. Thermodynamics 1989, 21, 10051008.
3. Apelblat, A.; Manzurola, E. J. Chem. Thermodynamics 1990, 22, 289292.
4. Apelblat, A. J. Chem. Thermodynamics 1993, 25, 14431445.
5. Apelblat, A. J. Chem. Thermodynamics 1997, 25, 15271533.
6. Seidell, A. Solubilities of Organic Compounds: 3rd edition, Vol. II. Van Nostrand: New York. 1941.
7. Seidell, A.; Linke, WF Solubilities of Inorganic and Organic Compounds: Supplement to the 3rd
edition. Van Nostrand: New York. 1952.
8. Stephen, H.; Stephen, T. Solubilities of Inorganic and Organic Compounds, Vol. 1, Part 1. Pergamon
Press: Oxford. 1963.
Machine Translated by Google

Solubilities of organic acids and magnesium-DL-aspartate in water 91

9. Beilstein Data. Beilstein Chemiedaten und Software GmbH. Beilstein Institut fuer Organischen
Chemie. 1990.
10. Wright, JL; Carstensen, JT J. Pharm. Sci. 1986, 75, 546551.
11. Strong, LE; Neff, RM; Whitesel, I. J. Solution Chem. 1989, 18, 101114.
12. Sugunau, S.; Benny, T. J. Chem. Eng. Data 1993, 38, 520521.
13. Williamson, AT Trans. Faraday Soc. 1944, 40, 421436.

(Receied
) April 28, 1998; in final form 7 August 1998

WA98021