5124 J. Chem. Eng.

Data 2010, 55, 51245127

Solubility of Benzoic Acid in Pure Solvents and Binary Mixtures

Jyothi Thati, Fredrik L. Nordstrom, and ke C. Rasmuson*,,

Department of Chemical Engineering and Technology, Royal Institute of Technology (KTH), SE-100 44 Stockholm, Sweden,
Abbott Laboratories, Process R&D, North Chicago, IL, United States, and Department of Chemical and Environmental Science,
Materials and Surface Science Institute, University of Limerick, Limerick, Ireland

The solubility of benzoic acid has been determined in ethanol, toluene, heptane, cyclohexane, pentane, and
chloroform and in binary mixtures of ethanol + heptane and ethanol + toluene, in the temperature range of
(278.15 to 323.15) K. The solubility is high in ethanol, reasonably high in chloroform, lower in toluene,
and quite low in the remaining three pure solvents. In the binary mixtures the solubility of benzoic acid
increases with increasing concentration of ethanol. The solubility of benzoic acid increases with increasing
temperature.

Introduction Experimental Work

In industry, solubility data in different solvents and temper- Materials. Benzoic acid (CAS No. 65-85-0) of 99.7 % purity
atures are routinely collected across many different scientific was purchased from Merck and was used without further
disciplines to enable efficient isolation of a product or an purification. Ethanol (CAS No. 64-17-5) of 99.7 % purity was
intermediate by crystallization. The solubility properties deter- purchased from Solveco Chemicals, heptane (CAS No. 142-
mine the method of supersaturation generation in crystallization 82-5 and purity 99 %), cyclohexane (CAS No. 110-82-7 and
and the yield and productivity of the process. The most common purity 99.5 %), and pentane (CAS No. 109-66-0 and purity g
crystallization operations are cooling crystallization, antisolvent 95 %) from VWR, and toluene (CAS No. 108-88-3 and purity
crystallization, or a combination of the two. A suitable solvent (99 to 99.4) %) and chloroform (CAS No. 67-66-3 and purity
system amenable for isolation by crystallization should at the (99 to 99.4) %) from Merck.
starting condition provide a sufficiently high solubility to Solubility Measurements. The solubility of benzoic acid was
completely dissolve the product without dramatically increasing determined by the gravimetric method4 in pure ethanol, heptane,
the solution volume but also allow for a significant reduction toluene, cyclohexane, pentane, and chloroform, in a temperature
in solubility at the end of the process to reduce product losses range of (278.15 to 323.15) K. The solubility was also
and increase process yield. To fulfill these requirements, it is determined in the binary mixtures of ethanol + heptane and
desired to use a solvent system where the effect of temperature ethanol + toluene, in the range of (0 to 50) % by mass of ethanol
on solubility is great (in cooling crystallizations) and/or where in the mixture. The solvent mixtures were prepared by weighing
the solubility difference between the co- and antisolvent is the desired amount of each solvent. Benzoic acid saturation was
significant (in antisolvent crystallizations). reached by dissolution from a surplus of solid benzoic acid
Benzoic acid and its salts are used mainly as food preserva- added to the solution. The bottles were placed at a certain
tives against yeast and mold. It is used to make a large number temperature, and the solution concentration was recorded over
of chemicals such as phenol, benzoate plasticizers, and so forth. time up to 1 week. The attaining of equilibrium was verified
Benzoic acid is also used as a bacteriostatic and bactericidal by continuous concentration measurements over time and when
agent and acts as an antiseptic stimulant and also an ingredient there was no change in concentration, that time was considered
in Whitfields ointment in the treatment of ringworm. It is also as the time to reach equilibrium (i.e., 2 h). The temperature
used in cosmetics, resin preparation, plasticizers, and so forth. was controlled by thermostat baths, and the true temperature
In this paper the solubility of benzoic acid in pure ethanol, was validated by using a calibration mercury thermometer
toluene, heptane, cyclohexane, pentane, and chloroform at (Thermo-Schneider, Wertheim, Germany, uncertainty of (
different temperatures, (278.15 to 323.15) K, has been inves- 0.01).
tigated. In addition, the solubility has also been determined in
binary mixtures of ethanol + toluene and ethanol + heptane. The solubility is determined in temperature steps starting at
Solubility data of benzoic acid in some pure and binary mixtures 278.15 K. The bottle with solvent or solvent mixture is initially
are available in the literature.1-3,6-8 However, there are no cooled to 278.15 K at which an amount of benzoic acid is added.
experimental data available in the literature for the solubility The solution is stirred by magnetic stirrer for 2 h and is then
in heptane, pentane, and chloroform and neither for the solubility turned off to allow the suspended solid phase to settle down
in the binary mixtures of ethanol + toluene and ethanol + for 30 min. Syringes (10 mL) with needles are used to sample
heptane. (2 to 5) mL of the clear solution from the bottles. Then a filter
(PTFE 0.2 m) is mounted on the syringe through which the
* To whom correspondence should be addressed. E-mail: [email protected]. solution is transferred into preweighed glass vials. The weight
Tel.: +46-8-7908227. Fax: +46-8-105228. of the glass vial with the saturated solution is recorded. The

Royal Institute of Technology (KTH). E-mail: [email protected].

Abbott Laboratories. E-mail: [email protected]. samples are then dried in ventilated laboratory hoods at room

University of Limerick. temperature (293.15 K). The solid sample mass is recorded
10.1021/je100675r 2010 American Chemical Society
Published on Web 10/26/2010
 Journal of Chemical & Engineering Data, Vol. 55, No. 11, 2010 5125

Table 1. Mole Fraction Solubility of Benzoic Acid in Pure Solventsa

x
T/K ethanol chloroform toluene cyclohexane pentane heptane
278.15 0.128 (0.0014) 0.074 (0.0002) 0.035 (0.0001) 0.004 (0.0001) 0.005 (0.0001)
283.15 0.139 (0.0021) 0.086 (0.0002) 0.043 (0.0003) 0.006 (0.0001) 0.005 (0.0001) 0.006 (0.0001)
293.15 0.166 (0.0011) 0.114 (0.0001) 0.062 (0.0005) 0.009 (0.0001) 0.007 (0.0002) 0.010 (0.0001)
303.15 0.196 (0.0002) 0.151 (0.0005) 0.089 (0.0006) 0.015 (0.0001) 0.011 (0.0003) 0.015 (0.0002)
313.15 0.234 (0.0011) 0.196 (0.0013) 0.128 (0.0003) 0.025 (0.0001) 0.022 (0.0002)
323.15 0.276 (0.0021) 0.253 (0.0012) 0.178 (0.0002) 0.039 (0.0005) 0.033 (0.0002)
a
The average of four samples; the standard deviation is in parentheses.

Table 2. Mole Fraction Solubility of Benzoic Acid in Binary Solvent Mixtures of Ethanol (2) + Heptane (1)a
100 w1
T/K 0 10 20 30 40 50
x
278.15 0.128 (0.0014) 0.121 (0.0008) 0.112 (0.0005) 0.102 (0.0003) 0.092 (0.0002) 0.079 (0.0002)
283.15 0.139 (0.0021) 0.132 (0.0007) 0.123 (0.0005) 0.111 (0.0022) 0.101 (0.0003) 0.087 (0.0002)
293.15 0.166 (0.0011) 0.158 (0.0003) 0.147 (0.0011) 0.135 (0.0009) 0.124 (0.0006) 0.107 (0.0005)
303.15 0.196 (0.0002) 0.188 (0.0009) 0.178 (0.0007) 0.164 (0.0016) 0.145 (0.0007) 0.132 (0.0007)
313.15 0.234 (0.0011) 0.227 (0.0007) 0.216 (0.0002) 0.203 (0.0005) 0.187 (0.0021) 0.165 (0.0005)
323.15 0.276 (0.0021) 0.271 (0.0007) 0.261 (0.0005) 0.246 (0.0007) 0.224 (0.0012) 0.203 (0.0009)
a
The average of four samples; the standard deviation is in parentheses. w1 ) the mass fraction of heptane in ethanol on a solute-free basis.

Table 3. Mole Fraction of Benzoic Acid in Binary Solvent Mixtures of Ethanol (1) + Toluene (2)a
100 w2
T/K 0 10 20 30 40 50
x
278.15 0.128 (0.0014) 0.127 (0.0004) 0.125 (0.0004) 0.123 (0.0002) 0.119 (0.0003) 0.112 (0.0002)
283.15 0.139 (0.0021) 0.138 (0.0005) 0.137 (0.0003) 0.133 (0.0006) 0.129 (0.0003) 0.122 (0.0002)
293.15 0.166 (0.0011) 0.163 (0.0008) 0.161 (0.0009) 0.157 (0.0005) 0.152 (0.001) 0.145 (0.0001)
303.15 0.196 (0.0002) 0.194 (0.0002) 0.191 (0.0009) 0.186 (0.0003) 0.181 (0.0003) 0.172 (0.0001)
313.15 0.234 (0.0011) 0.231 (0.0004) 0.227 (0.0011) 0.222 (0.0005) 0.214 (0.0013) 0.203 (0.0001)
323.15 0.276 (0.0021) 0.273 (0.0015) 0.266 (0.0012) 0.262 (0.0011) 0.254 (0.0004) 0.243 (0.0008)
a
The average of four samples; the standard deviation is in parentheses. w2 ) the mass fraction of toluene in ethanol on a solute-free basis.

repeatedly throughout the drying process to establish the point

where the mass remained constant. The mass of the final dry
sample is then used for the calculation of the solubility. The
balance used during the experimental work has a resolution of
( 0.0001 g. For each data point an average of four measure-
ments are reported, two samples each from two equal experi-
mental solutions. After taking the samples from the saturated
solution at 278.15 K, the solution is heated to 283.15 K, then
to 293.15 K, and so on up to 323.15 K for further measurements,
of course always assuring that solid benzoic acid is present at
equilibrium. To sample the solution at high temperatures of Figure 1. Solubility (moles of solute/moles total) of benzoic acid in pure
(293.15 to 323.15) K, preheated syringes are used to avoid solvents between (278.15 and 323.15) K (average of four samples): (,
ethanol; 9, chloroform; 2, toluene; 4, cyclohexane; b, heptane; O, pentane.
crystallization in the syringes. The uncertainty of the solubility Lines are calculated using eq 1.
values based on the repeated observations is within 1 % for all
of the solubilities in pure solvents and mixtures.
solvent. The solubility difference between the cosolvent (i.e.,
Results and Discussion ethanol) and the antisolvent (i.e., heptane and toluene) increases
The mole fraction solubility of benzoic acid in the pure as the temperature is reduced, and this leads to that the curves
solvents is shown in Table 1. The mole fraction solubility of in Figure 2 and 3 diverge somewhat at increasing antisolvent
benzoic acid in the binary solvent mixtures is reported in Tables concentration.
2 and 3. Since the melting temperature of cyclohexane is 279.15 In the current contribution, the solubility of benzoic acid has
K and the boiling temperature of pentane is 309.15 K, the data been determined as a function of temperature in a total of six
for these solvents do not cover the entire temperature range. pure solvents and 10 binary solvent mixtures. The solubility of
By converting the experimental solubility into mole fraction benzoic acid is low in all pure solvents besides ethanol and
solubility, x, a so-called vant Hoff plot can be established and chloroform. The molar solubility decreases in the order ethanol,
is shown in Figure 1 for the pure solvents. The mole fraction chloroform, toluene, heptane, cyclohexane, and pentane. The
solubility in each binary solvent system is given in Figure 2 solubility of benzoic acid is decreasing with the increasing
and 3. As expected, the solubility in heptane and toluene is much fraction of toluene or heptane, respectively, in the binary
lower than in ethanol, and in the binary mixtures the solubility mixtures. With increasing temperature the solubility of benzoic
decreases nonlinearly with the increasing fraction of the nonpolar acid increases for all solvents and solvent mixtures. The
5126 Journal of Chemical & Engineering Data, Vol. 55, No. 11, 2010

Figure 4. Comparison of the solubility of benzoic acid in toluene (b,

experimental; 9, literature) and cyclohexane (, experimental; 2, literature).
Figure 2. Mole fraction solubility of benzoic acid in mixtures of heptane
+ ethanol (xm is specified as the mole fraction of heptane in the solvent Table 4. Regression Coefficients of Equation 1 for the Solubility of
mixture on a solute-free basis) between (278.15 and 323.15) K (average of Benzoic Acid in Pure Solvents in the Temperature Range of (278.15
four samples). (, 278.15 K; 9, 283.15 K; 2, 293.15 K; +, 303.15 K; O, to 323.15) K
313.15 K; , 323.15 K. Lines are calculated using eq 2.
solvent 10-2 A B 102 C
ethanol -1.0231 -6.1372 1.599
chloroform -14.9275 -0.2008 1.066
toluene -19.2702 -0.4993 1.466
cyclohexane -16.8388 -7.9394 3.071
pentane 4.4493 -20.9245 4.932
heptane -38.0341 8.4537 -0.032

Table 5. Regression Coefficients of Equation 1 for the Solubility of

Benzoic Acid in Ethanol + Heptane Mixtures in the Temperature
Range of (278.15 to 323.15) K and Solvent Composition in Mass
Fraction of Heptane (1) + Ethanol (2) on a Solute-Free Basis
100 w1 10-2 A B 102 C
0 -1.0231 -6.1372 1.599
10 1.4762 -8.0981 1.961
20 4.6488 -10.5239 2.396
30 6.1357 -11.8822 2.657
40 -0.5766 -7.5864 1.942
Figure 3. Mole fraction solubility of benzoic acid in mixtures of toluene
50 3.6213 -10.8402 2.515
+ ethanol (xm is specified as the mole fraction of toluene in the solvent
mixture on a solute-free basis) between (278.15 and 323.15) K (average of Table 6. Regression Coefficients of Equation 1 for the Solubility of
four samples). (, 278.15 K; 9, 283.15 K; 2, 293.15 K; +, 303.15 K; O, Benzoic Acid in Ethanol + Toluene in the Temperature Range of
313.15 K; , 323.15 K. Lines are calculated using eq 2. (278.15 to 323.15) K and Solvent Mass Fraction of Toluene (2) +
Ethanol (1) on a Solute-Free Basis

relationship between solubility and temperature has been 100 w2 10-2 A B 102 C
explored in detail in previous contributions for a number of 0 -1.0231 -6.1372 1.599
organic compounds.1,4,5 The general rule is that the lower the 10 1.0134 -7.4855 1.818
20 -1.3948 -5.8245 1.527
mole fraction solubility the higher is the temperature depen- 30 1.6961 -7.9302 1.877
dence, that is, the higher is the vant Hoff enthalpy of solution. 40 1.8489 -8.0594 1.893
This relationship can be readily observed in Figure 2. At 298.15 50 1.4659 -7.9388 1.878
K the solubility of benzoic acid in ethanol and toluene (0.5839
and 0.1034) is in good agreement with the values given in the
literature (0.584 and 0.106).6 The solubility of the benzoic acid the correlation coefficient (R2) exceeds 0.9996. For pure solvents
in toluene and cyclohexane is shown in Figure 4.7,8 The the solubilities calculated with eq 1, with parameters in Table
values for the solubility of benzoic acid in toluene given in 4, are shown in Figure 1 and for binary mixtures in Tables 5
the literature7 are lower than the values given in this work. The and 6.
literature work was done almost 90 years ago, and the At a constant temperature, the dependence of the solubility
experimental procedure has ignored some errors. The solubility on solvent composition in the binary mixtures of ethanol +
of benzoic acid and cyclohexane is shown in Figure 4 and is in heptane and ethanol + toluene is well-described by a second-
good agreement with the literature values.8 order polynomial:
The temperature dependence of the solubility can be well-
correlated by the nonlinear equation
ln(x) ) Dxm2 + Exm + F (2)

ln x ) A(T/K)-1 + B + C(T/K) (1)

where x is the mole fraction solubility and xm is the mole fraction
on solute-free basis of the nonpolar solvent in the solvent binary
where x is the mole fraction solubility, T is the absolute mixture. D, E, and F are regression coefficients at each
temperature, and A, B, and C are regression coefficients that temperature and are listed in Tables 7 and 8. Overall, for all of
are listed in Tables 4, 5, and 6. Overall, for all of the correlations the correlations, the correlation coefficient (R2) exceeds 0.9992.
 Journal of Chemical & Engineering Data, Vol. 55, No. 11, 2010 5127

Table 7. Regression Coefficients of Equation 2 for the Solubility of form, toluene, heptane, cyclohexane and pentane. In binary
Benzoic Acid in Ethanol (2) + Heptane (1) Binary Mixtures on a solvent mixtures with ethanol, the solubility of benzoic acid
Solute-Free Basis at Different Temperatures
decreases with increasing concentration of heptane and toluene,
T/K D E F respectively. The solubility increases with increasing temperature
278.15 -2.4718 -0.7744 -2.0703 for all of the solvents and solvent mixtures of the work.
283.15 -2.2985 -0.7855 -1.9833
293.15 -2.0535 -0.7433 -1.8068 Literature Cited
303.15 -1.8902 -0.6747 -1.6343
313.15 -1.8166 -0.5303 -1.4552 (1) Apelblat, A.; Manzurola, E.; Balal, N. The solubilities of benzene
323.15 -1.649 -0.4861 -1.2814 polycarboxylic acids in water. J. Chem. Thermodyn. 2006, 38, 565
571.
Table 8. Regression Coefficients of Equation 2 for the Solubility of (2) Oliviera, A.; Coelho, C.; Pires, R.; Moilton, F. Solubility of benzoic
Benzoic Acid in Ethanol (1) + Toluene (2) Binary Mixtures on a acid in mixed solvents. J. Chem. Eng. Data 2007, 52, 298300.
Solute-Free Basis at Different Temperatures (3) Ricardo, P.; Moilton, F. Solubility of benzoic acid in aqueous solutions
containing ethanol or N-propanol. J. Chem. Eng. Data 2008, 53 (11),
T/K D E F 27042706.
278.15 -1.3395 0.0536 -2.062 (4) Nordstrom, F.; Rasmuson, . Solubility and melting properties of
salicylamide. J. Chem. Eng. Data 2006, 51, 17751777.
283.15 -1.1829 0.0055 -1.9739
(5) Nordstrom, F.; Rasmuson, . Polymorphism and thermodynamics of
293.15 -0.8723 - 0.104 -1.8023 m-hydroxybenzoic acid. Eur. J. Pharm. Sci. 2006, 28, 377384.
303.15 -0.5929 -0.1891 -1.628 (6) Chipman, J. The solubility of benzoic acid in benzene and in toluene;
313.15 -0.2943 -0.3157 -1.4475 Contribution from the Department of Chemistry, Illinois Wesleyan
323.15 -0.1092 -0.3344 -1.2831 University: Bloomington, IL, 1924; Vol. 46.
(7) Kirk, E.; Othmer, F. Kirk-Othmer Encyclopedia of Chemical Technol-
ogy, 4th ed.; Wiley: New York, 1993; Vol. 4, p 105.
The solubilities calculated with eq 2, with parameters in Tables (8) Long, B.; Li, J.; Zhang, R.; Wan, L. Solubility of benzoic acid in
7 and 8 are shown in Figures 2 and 3. acetone, 2-propanol, acetic acid and cyclohexane: Experimental mea-
surement and thermodynamic modeling. Fluid Phase Equilib. 2010,
297, 113120.
Conclusions
The solubility of benzoic acid in the pure solvents of the
present work is low with exception for chloroform and ethanol. Received for review June 21, 2010. Accepted October 13, 2010.
The molar solubility decreases in the order of ethanol, chloro- JE100675R