J. Chem. Thermodynamics 2002, 34, 11271136 doi:10.1006/jcht.2002.0975 Available online at http://www.idealibrary.

com on

Solubilities of L-glutamic acid, 3-nitrobenzoic acid, p-toluic acid, calcium-L-lactate, calcium gluconate, magnesium-DL-aspartate, and magnesium-L-lactate in water
Emanuel Manzurola
Department of Chemical Engineering, Negev Academic College of Engineering, Beer Sheva, Israel

and Alexander Apelblata

Department of Chemical Engineering, Ben Gurion University of the Negev, Beer Sheva, Israel

Solubilities of L-glutamic acid, 3-nitrobenzoic acid, p-toluic acid, calcium-L-lactate, calcium gluconate, magnesium-DL-aspartate, and magnesium-L-lactate in water were determined in the temperature range 278 K to 343 K. The apparent molar enthalpies of solution at T = 298.15 K as derived from these solubilities are sol Hm (L-glutamic acid, m sat = 0.0565 mol kg1 ) = 30.2 kJ mol1 , sol Hm (3-nitrobenzoic acid, m = 0.0188 mol kg1 ) = 28.1 kJ mol1 , sol Hm ( p-toluic acid, m = 0.00267 mol kg1 ) = 23.9 kJ mol1 , sol Hm (calcium-L-lactate tetrahydrate, m = 0.2902 mol kg1 ) = 25.8 kJ mol1 , sol Hm (calcium gluconate, m = 0.0806 mol kg1 ) = 22.1 kJ mol1 , sol Hm (magnesium-DL-aspartate tetrahydrate, m = 0.1469 mol kg1 ) = 11.5 kJ mol1 , and sol Hm (magnesium-L-lactate trihydrate, m = 0.3462 mol kg1 ) = 3.81 kJ mol1 . c 2002 Elsevier Science Ltd. All rights reserved. KEYWORDS: solubilities; organic acids and salts; molar enthalpies of solution

1. Introduction
In this work we present the solubilities of a number of organic acids and salts as a function of temperature and the results of measurements compared, if possible, compared with the literature data. This is a continuation of our studies dealing with the solubility in water of many organic substances having biological or industrial importance. (18) Some systems
a To whom correspondence should be addressed (E-mail: apelblat@bgumail.bgu.ac.il).

00219614/02

c 2002 Elsevier Science Ltd. All rights reserved.

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E. Manzurola and A. Apelblat

considered here exist in the main tabulations of solubilities, (912) but the available data are limited or discordant and therefore more consistent results are desirable. The solubilities of optical isomers of glutamic acid have already been determined a few times. In the literature there is some conicting notation when optical isomers are considered. In investigations performed before the Second World War l and d were associated with the measured direction of specic rotation []25 . Nowadays, [R] and [S] D forms are associated with the absolute conguration of optical isomers but in the case of sugars, amino acids, and closely related substances the older system of capital letters L and D is also used. In the Dictionary of Organic Compounds (13) it is reported that L -glutamic acid in water is in the [S] form, but []25 = +17 and therefore in old investigations D this means D-glutamic acid. In contrast, D-glutamic acid in water is in the [R] form, but []25 = 12.9 and therefore this is L-glutamic acid. This happens rarely, but in the case D of optical isomers of glutamic acid the melting temperatures of the L and D forms are different. (13) Old solubility values of D-glutamic acid (i.e. L-glutamic acid) were reported by Bayliss (14) at T = 311.65 K, Pfeiffer and Wurgler (15) at T = 293.15 K, Pfeiffer and Augern (16) at T = 294.15 K, Pertzoff (17) at T = 298.15 K, Dunn et al. (18) at three temperatures, (273.15, 298.15, and 323.15) K, and systematic measurements in the 273.15 K to 373.15 K temperature range were performed by Dalton and Schmidt. (19) There are no solubility data for L-glutamic acid. In the case of DL-glutamic acid, besides results from the Dunn et al. (18) and Dalton and Schmidt (19) investigations, new solubilities were reported by Apelblat and Manzurola (6) in the 278.15 K to 348.15 K temperature range. Considering glutamic acid solubilities, Dalton and Schmidt pointed out that, in addition to well-controlled experimental conditions, working with optically active materials is difcult because of contamination during the process of isolation by neutral salts, other amino acids, and partial racemization which occurs during hydrolysis of the protein from which the amino acids are obtained. There are only old solubility values for 3-nitrobenzoic acid (usually at high temperatures because the acid is slightly soluble in water), which are compiled in the Seidell tabulation. (9) These investigations were performed by Flaschner and Rankin, (20) Knox and Richards, (21) Sidgwick and Ewbank, (22) and Yajnik et al. (23) Recently, Biswas and Lahiri (24) reported the solubility of 3-nitrobenzoic acid, but only at T = 298.15 K. Solubilities of p-toluic acid as a function of temperature were already determined by us (6) and compared with those of Wright and Carstensen, (25) Strong et al., (26) Sugunau and Benny, (27) and old solubilities from the Beilstein electronic database. (12) Initially, solubilities of toluic acid as well as those of calcium-L-lactate and magnesium-DLaspartate served to verify that our measuring system was working properly after a long pause in experiments. However, since the solubility of p-toluic acid in water is very low and that of the calcium and magnesium salts were considered only once (4) (the temperature range in the case of calcium-L-lactate is now extended up to 344.65 K), it is worthwhile presenting new values for a better documentation of solubility data. No solubilities exist in the literature for calcium gluconate and magnesium-L-lactate. From measured solubilities of these substances the apparent molar enthalpies of solution at T = 298.15 K were calculated.

Solubilities of organic acids and salts in water

1129

2. Experimental
The compounds L-glutamic acid (2-aminopentanedioic acid) HO2 CCH(NH2 )CH2 CH2 CO2 H, (mass fraction > 0.99); calcium gluconate {CH2 OH(HCOH)4 CO2 }2 Ca (mass fraction > 0.995) from Sigma; calcium-L-lactate tetrahydrate {CH3 CH(OH)CO2 }2 Ca 4H2 O (mass fraction > 0.995); magnesium-L-lactate trihydrate {CH3 CH(OH)CO2 }2 Mg 3H2 O (mass fraction > 0.995); magnesium-DL-aspartate tetrahydrate {HO2 CCH(NH2 )CH2 CO2 }2 Mg.4H2 O (mass fraction > 0.98) from Fluka; p-toluic acid (4-methylbenzoic acid) CH3 C6 H4 CO2 H, (mass fraction > 0.99) from BDH; and 3-nitrobenzoic acid, O2 NC6 H4 CO2 H, (mass fraction > 0.98) from Aldrich were used in the solubility experiments without further purication. Suspended excess solids were dissolved in water by stirring in double-walled tubes thermostated by circulating water. Fluctuations of temperature were less than 0.01 K. The solubility measurements were performed with doubly distilled water (in both directions, by increasing and decreasing the temperature) as described elsewhere. (18) In each system under consideration, the (solid + liquid) equilibrium was ensured by checking in preliminary experiments the time of stirring and gravitational settling at a few temperatures in the studied temperature interval. In actual experiments, times which were needed to attain the equilibrium were almost doubled (about 1 h for stirring and 24 h for settling). Weighed samples of saturated solutions of organic acids were titrated with solutions of NaOH (Frutarom Laboratory Chemicals Ltd, Haifa), standardized with potassium hydrogen phthalate (Rieden de Haen). Phenolphthalein served as an indicator and calcium and magnesium salts was titrated complexometrically with solutions of EDTA (Merck) using Eriochrome black T as an indicator. At each temperature, reported solubilities are the average value of four determinations. Excellent reproducibility of results was observed (relative error in solubility values is less that 0.8 per cent for all substances with the exception of magnesium-DL-aspartate where the error was larger at about 1.5 to 2.0 per cent).

3. Results and discussion

The solubilities of investigated substances as a function of temperature are presented in table 1 and plotted in gures 1 to 5. At constant pressure, for nonelectrolytes 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 using the relation: (28) ln m/(1/T ) =
sol Hm /[R(1 hm sat /55.5084)(1 + {

ln / ln m}T )],

(1)

where sol Hm is the molar enthalpy of solution, R is the gas constant, and m sat and are the molality of the nonelectrolyte and its activity coefcient at saturation point. Since the values of the activity coefcients in the investigated systems are unknown, it is possible to determine only the apparent enthalpies of solution by neglecting the activity coefcient term in equation (1). The dissociation effect is also neglected, and acids and salts considered here are treated as nonelectrolytes. Over the studied temperature range and introducing m o = 1 mol kg1 , the determined solubilities and molar enthalpies of

1130

E. Manzurola and A. Apelblat TABLE 1. Solubilities m of organic acids and salts in water as a function of temperature T
T /K m/(mol kg1 ) T /K m/(mol kg1 ) acid 328.15 330.15 330.15 332.15 335.15 337.65 340.05 340.05 342.15 342.15 0.1690 0.1914 0.1855 0.2040 0.2316 0.2463 0.2617 0.2603 0.2881 0.2929 T /K m/(mol kg1 )

L -glutamic

278.65 281.15 283.15 286.15 288.15 291.15 293.15 296.05 298.15 300.95 303.15 278.15 280.65 283.15 285.35 288.15 290.15 293.15 295.15 298.15 278.15 284.15 290.15 294.65 298.15 298.65 303.15 303.15 278.15 283.15 288.15 288.15 293.15

0.0240 0.0261 0.0303 0.0344 0.0393 0.0417 0.0481 0.0517 0.0583 0.0628 0.0698 0.0096 0.0098 0.0118 0.0118 0.0138 0.0141 0.0161 0.0170 0.0191 0.00148 0.00183 0.00199 0.00227 0.00278 0.00234 0.00345 0.00359 0.1555 0.1865 0.2130 0.2126 0.2548

305.85 308.15 310.95 313.15 315.65 318.15 320.65 323.15 325.35 325.35 328.15 300.15 303.15 305.15 308.15 310.65 313.15 315.65 318.15 320.95 308.15 308.15 308.15 313.15 313.15 313.15 318.15 323.15 308.15 308.15 312.15 312.15 313.15

0.0745 0.0855 0.0925 0.1006 0.1112 0.1235 0.1386 0.1477 0.1588 0.1658 0.1886 0.0206 0.0227 0.0252 0.0285 0.0314 0.0352 0.0386 0.0429 0.0493 0.00367 0.00368 0.00369 0.00436 0.00437 0.00469 0.00530 0.00652 0.4358 0.4342 0.5018 0.5025 0.5190

3-Nitrobenzoic acid 323.15 326.05 328.15 333.15 335.65 338.15 341.15 343.15 0.0543 0.0636 0.0703 0.0888 0.1036 0.1165 0.1445 0.1609

p-Toluic acid 325.15 328.15 331.15 333.15 334.65 338.15 340.15 343.15 325.95 325.95 327.65 327.65 329.15 0.00670 0.00785 0.00870 0.00942 0.0102 0.0112 0.0125 0.0137 0.9304 0.9272 0.9895 0.9956 1.0859

Calcium-L-lactate

Solubilities of organic acids and salts in water TABLE 1continued

T /K 293.15 297.85 298.15 302.85 302.85 303.15 303.15 307.65 307.65 278.15 283.15 288.15 293.15 298.15 278.15 283.15 288.15 293.15 298.15 278.65 283.65 288.15 288.35 292.85 293.65 297.65 297.95 302.65 m/(mol kg1 ) 0.2510 0.2933 0.3032 0.3491 0.3478 0.3520 0.3531 0.4254 0.4245 0.0440 0.0538 0.0625 0.0692 0.0799 0.1104 0.1169 0.1212 0.1332 0.1471 0.3258 0.3321 0.3369 0.3364 0.3425 0.3426 0.3476 0.3549 0.3630 T /K 313.15 316.95 316.95 317.65 317.65 321.35 321.35 322.25 322.25 303.15 308.15 313.15 318.15 323.15 303.15 308.15 313.15 318.15 323.15 307.15 307.65 312.15 313.15 316.65 321.15 323.15 325.45 326.85 m/(mol kg1 ) 0.5187 0.6288 0.6314 0.6183 0.6141 0.7575 0.7543 0.7663 0.7713 0.0915 0.1140 0.1243 0.1477 0.1842 0.1629 0.1861 0.2148 0.2386 0.2651 0.3729 0.3740 0.3836 0.3922 0.3980 0.4117 0.4203 0.4313 0.4383 328.25 331.35 333.65 336.25 341.65 342.15 343.15 0.4540 0.4636 0.4926 0.5078 0.5594 0.5742 0.6150 328.15 333.15 338.15 343.15 0.2854 0.3143 0.3518 0.4023 T /K 329.15 331.95 331.95 335.15 337.65 338.15 341.65 343.65 344.65 328.15 333.15 338.15 343.15 m/(mol kg1 ) 1.0891 1.280 1.286 1.446 1.860 1.806 2.115 2.539 2.669 0.2128 0.2345 0.2842 0.3553

1131

Calcium gluconate

Magnesium-DL-aspartate

Magnesium-L-lactate

solution can be expressed as: ln(m/m o ) = A + B (T /K)1 + C ln(T /K), sol Hm /R K = D + E {(T /K) 298.15}, (2) (3)

where the coefcients in the above equations were evaluated by an unweighted multivariate least-squares method from the reported solubilities, and are presented in table 2.

1132

E. Manzurola and A. Apelblat TABLE 2. Coefcients of the solubility and molar enthalpy of solution given by equations (2) and (3)
Substance
L -glutamic

A acid 33.141 432.55 296.93 492.75 193.64 190.74 209.16

B 1741.88 16202.4 9305.6 19186.4 6244.5 7217.4 8866.4

C 6.388 65.683 40.858 74.973 29.869 28.893 31.307

D 3631 3381 2876 3064 2661 1382 457

E 6.338 65.683 40.858 59.174 29.869 27.811 30.408

3-Nitrobenzoic acid p-Toluic acid Calcium-L-lactate Calcium gluconate Magnesium-DL-aspartate Magnesium-L-lactate

0.40 0.35 0.30 m/(mol . kg 1) 0.25 0.20 0.15 0.10 0.05 0.00 270

280

290

300

310

320

330

340

350

T/K
FIGURE 1. Solubility m of L-glutamic acid as a function of temperature T : , reference 12; , reference 18; , reference 19.

this work;

With the exception of old solubilities, (12) there is very good agreement between the results presented here for L-glutamic acid (gure 1) and those reported by Dunn et al. (18) and Dalton and Schmidt. (19) However, the estimated apparent molar enthalpies of solution at T = 298.15 K are different: 40.2 kJ mol1 , (17) 26.2 kJ mol1 , (18) and 25.3 kJ mol1 (19) as compared with our result of 30.2 kJ mol1 . It is worthwhile noting that the solubility of optically active acid is, as is usually observed, lower than the DL-form. (6, 18, 19)

Solubilities of organic acids and salts in water

0.16 0.14 0.12 m/(mol . kg 1) 0.10 0.08 0.06 0.04 0.02 0.00 280 290 300 310 320 330 340

1133

T/K
FIGURE 2. Solubility m of 3-nitrobenzoic acid as a function of temperature T : , reference 12; , reference 23.

, this work;

0.014 0.012 0.010 m/(mol . kg 1) 0.008 0.006 0.004 0.002 0.000

280

290

300

320

340

360

380

T/K
FIGURE 3. Solubility m of p-toluic acid as a function of temperature T : , this work; , reference 12; , reference 25; , reference 26; , reference 27.

, reference 6;

1134
3.0

E. Manzurola and A. Apelblat

2.5

2.0 m/(mol . kg 1)

1.5

1.0

0.5

0.0

280

290

300

310

320

330

340

350

T/K
FIGURE 4. Solubility m as a function of temperature T . Calcium-L-lactate: reference 4. Magnesium-DL-aspartate: , this work; , reference 6.

, this work; ,

0.6

0.5

m/(mol . kg 1)

0.4 0.3

0.2 0.1 0.0

280

290

300

310

320

330

340

T/K
FIGURE 5. Solubility m of as a function of temperature T . L -lactate.

, Calcium gluconate;

, magnesium-

Solubilities of organic acids and salts in water

1135

In the case of 3-nitrobenzoic acid (gure 2), whose solubility in water is rather low, (12, 2024) the agreement is satisfactory but only for T < 310 K; at higher temperatures, our results are always lower than those in the literature. (12) The compound p-toluic acid has the lowest solubility (6, 12, 2527) among the investigated substances (gure 3). Over the entire temperature range, very satisfactory agreement between available solubility data is observed. Also, the apparent molar enthalpies of solution for p-toluic acid are similar: 26.9 kJ mol1 , (26) 24.0 kJ mol1 , (6) and 23.9 kJ mol1 . (19) In gure 4, we present solubilities of calcium-L-lactate and magnesium-DL-aspartate; both solubilities were already determined by us. (4, 6) The repeated sets of data are very consistent (22.0 kJ mol1 (4) and 25.8 kJ mol1 for calcium-L-lactate tetrahydrate and 11.7 kJ mol1 (6) and 11.5 kJ mol1 for magnesium-DL-aspartate tetrahydrate), but for magnesium-DL-aspartate the old solubilities are somewhat lower above T = 305 K. No solubilities of calcium gluconate and magnesium-L-lactate are reported in the literature. Both salts are moderately soluble in water (gure 5), but the solubility of magnesium-L-lactate depends weakly on temperature and the apparent molar enthalpy of solution is rather low. The authors appreciate the technical assistance of Genadi Agronov, Zohar BenKoel, Amir Orieli, Alon Sade and Amos Toito.
REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. Apelblat, A.; Manzurola, E. J. Chem. Thermodynamics 1987, 19, 317320. Apelblat, A.; Manzurola, E. J. Chem. Thermodynamics 1989, 21, 10051008. Apelblat, A.; Manzurola, E. J. Chem. Thermodynamics 1990, 22, 289292. Apelblat, A. J. Chem. Thermodynamics 1993, 25, 14431445. Apelblat, A.; Manzurola, E. J. Chem. Thermodynamics 1997, 29, 15271533. Apelblat, A.; Manzurola, E. J. Chem. Thermodynamics 1999, 31, 8591. Apelblat, A.; Manzurola, E. J. Chem. Thermodynamics 1999, 31, 13471357. Apelblat, A.; Manzurola, E. J. Chem. Thermodynamics 2001, 33, 147153. Seidell, A. Solubilities of Organic Compounds: 3rd edition. Vol. 2. Van Nostrand: New York. 1941. Seidell, A.; Linke, W. F. Solubilities of Inorganic and Organic Compounds: 3rd edition. (suppl.). Van Nostrand: New York. 1952. Stephen, H.; Stephen, T. Solubilities of Inorganic and Organic Compounds. Vol. 1 (part 1). Pergamon Press: Oxford. 1963. Beilstein Data. Beilstein Chemiedaten und Software GmbH. Beilstein Institut fuer Organischen Chemie, 1990. Buckingham, J.: editor. Dictionary of Organic Compounds: 5th edition. Vol. 3. Chapman and Hall: New York. 1982, 27642765. Bayliss, W. M. J. Physiol. 1907, 36, 221252. Pfeiffer, P.; Wurgler, J. Z. Physiol. Chem. 1916, 97, 128147. Pfeiffer, P.; Augern, O. Z. Physiol. Chem. 1924, 133, 180192. Pertzoff, V. A. J. Biol. Chem. 1933, 100, 97104. Dunn, M. S.; Ross, F. J.; Read, L. S. J. Biol. Chem. 1933, 103, 579595. Dalton, J. B.; Schmidt, C. L. A. J. Biol. Chem. 1933, 103, 549578. Flaschner, O.; Rankin, I. G. Monatsh. Chem. 1910, 31, 2350. Knox, J.; Richards, M. B. J. Chem. Soc. (London) 1919, 115, 508531.

1136 22. 23. 24. 25. 26. 27. 28.

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Sidgwick, N. V.; Ewbank, E. K. J. Chem. Soc. (London) 1921, 119, 9791001. Yajnik, N. A.; Jain, M. P.; Nath, D. J. Indian Chem. Soc. 1925, 2, 115128. Biswas, P. K.; Lahiri, S. C. J. Indian Chem. Soc. 1994, 71, 551555. Wright, J. L.; Carstensen, J. T. J. Pharm. Sci. 1986, 75, 546551. Strong, L. E.; Neff, R. M.; Whitesel, I. J. Solution Chem. 1989, 18, 101114. Sugunau, S.; Benny, T. J. Chem. Eng. Data 1993, 38, 520521. Williamson, A. T. Trans. Faraday Soc. 1944, 40, 421436. (Received 22 November 2001; revised 6 February 2002; accepted 15 February 2002)

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