Fluid Phase Equilibria 352 (2013) 110–113

Contents lists available at SciVerse ScienceDirect

Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Short communication

Solubility of citric acid in water, ethanol, n-propanol and in mixtures

of ethanol + water
Mauro Lúcio N. Oliveira a , Ricardo A. Malagoni b , Moilton. R. Franco Jr. b,∗
a
Federal University of Mato Grosso, School of Chemical Engineering, Rodovia Rondonópolis-Guiratinga, km 06, Sagrada Familia, Rondonopolis, MT
78.735-901, Brazil
b
Federal University of Uberlândia, School of Chemical Engineering, João Naves de Ávila Avenue, 2121, Building: 1K, Campus Santa Mônica, Uberlândia, MG
38.408-144, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The solubility of citric acid or 3-carboxy-3-hydroxypentanedioic acid in water, ethanol, n-propanol and
Received 19 March 2013 ethanol + water mixtures at temperatures ranging from 293.7 to 333.1 K was investigated. The experi-
Received in revised form 10 May 2013 mental results obtained were correlated with the temperature for pure solvents by two equations based
Accepted 16 May 2013
on the literature. For ternary systems, data were correlated as function of alcohol concentration for each
Available online 29 May 2013
temperature. Regarding the pure solvents, both of the models demonstrated good agreement with the
experimental data. There are disagreements with the recent work published by Daneshfar et al. (2012)
Keywords:
[12]. It was observed that adding ethanol in the water increased citric acid solubility in all cases.
Citric acid
Fitting © 2013 Elsevier B.V. All rights reserved.
Mixtures of solvents
Solubility

1. Introduction was systematically measured by a static analytical method. The

results were correlated using different equations available in the
Citric acid or 2-hydroxypropane-1,2,3-tricarboxylic acid literature.
(C6 H8 O7 , CAS No. 77-92-9) is a weak organic acid and is often
used as a natural preservative. It also used to add an acidic or sour 2. Experimental
taste to food and beverages. Citric acid anhydrous is produced as
translucent crystals and as white crystalline powder. It is odorless 2.1. Materials
and has a strong acidic taste. Storage in tight containers away from
heat and humidity is recommended. Citric acid is widely used Chemicals. Laboratory deionized (E.J. Krieger & Cia, Ltd., model
in the food, beverage, and pharmaceutical industries to impart a Permution) and distilled (Quimis, model G.341.25) water was used
clean, refreshing tartness. Its prime use is as an acidulant, but it in the experiments. Organic solvents, ethanol and n-propanol, were
is also used as sequestrant of metal ions to give protection from acquired from Isofar Chem. Ind. and the mass fractions of purities
the development of off-flavors and off-odors in certain foodstuffs were 99.9% in mass fraction. 3-Carboxy-3-hydroxypentanedioic
[1,2]. A major industrial use of citric acid is in the manufacture acid (>99.5%, mass fraction) obtained from Vetec Chemical Reagent
of ecologically compatible detergents. It is also used in chemical was dried at 393 K. All chemicals used in the experimental part
cleaning, concrete admixtures, plasticizers, and a range of other were used without further purification. The sample was kept in a
applications. desiccator with dry silica gel.
The solubility of solids in liquids is one of the most important
research field [3–10] and is significant for the development of the
2.2. Experimental apparatus
solution theory. However, conflicting solubility data of citric acid
have been reported in the literature [11,12] and specifically for
The solubility of citric acid was measured using an equilibrium
the acid in pure ethanol and water. In this paper, the solubility
cell similar to that reported in the literature [9,10]. The experimen-
of citric acid in water, ethanol, n-propanol and ethanol + water
tal setup was comprised of cells connected in series using latex
hoses. Temperatures in the cells were kept constant by circulating
water in the jacket from a thermostatized bath (Tecnal, TE-184).
∗ Corresponding author. Tel.: +55 34 3239 4249; fax: +55 34 3239 4249. Silicone septum were put on the sampling points to seal the equi-
E-mail address: [email protected] (Moilton.R. Franco Jr.). librium cells and allow the sampling through glass syringes. At the

0378-3812/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fluid.2013.05.014
 M.L.N. Oliveira et al. / Fluid Phase Equilibria 352 (2013) 110–113 111

Table 1
Experimental and calculated (Eqs. (2) and (3)) solubility of citric acid in pure solvents at different temperatures.

Solvent T (K) xexp ± ı xlit(1) xlit(2) xc1 xc2

Water 293.7 0.1224 ± 0.0010 – – 0.1288 0.1270

303.3 0.1510 ± 0.0010 0.1445 0.058 0.1466 0.1468
313.4 0.1712 ± 0.0010 0.1700 0.091 0.1665 0.1676
322.2 0.1864 ± 0.0012 0.1977 0.141 0.1868 0.1876
333.1 0.2061 ± 0.0013 0.2275 0.174 0.2086 0.2080

Ethanol 293.7 0.2482 ± 0.0015 – – 0.2503 0.2503

303.3 0.2700 ± 0.0015 0.3027 0.051 0.2660 0.2660
313.4 0.2806 ± 0.0012 0.3297 0.069 0.2825 0.2826

n-Propanol 293.7 0.2743 ± 0.0013 – – 0.2741 0.2741

303.3 0.2794 ± 0.0013 – – 0.2799 0.2798
313.4 0.2859 ± 0.0015 – – 0.2857 0.2857

(1), Yang and Wang [11]; (2), Daneshfar et al. [12].

top of the cells were inserted teflon stoppers to seal the system and Table 2
Experimental and calculated results for citric acid in ethanol–water systems.
to fix the thermocouples.
The experimental solubility of citric acid in pure solvents and x2 T (K) xexp ± ı xc3
mixtures of them in the temperature range from 293.7 to 333.1 K 0.0000 293.7 0.1224 ± 0.0010 0.1414
was measured by a static analytical method described in other 0.1989 0.1721 ± 0.0010 0.1587
literature [9] and explained briefly here. The experimental satu- 0.3997 0.1876 ± 0.0010 0.1783
rated solutions were prepared by weighing (Model 521/2 – Nova 1.0000 0.2482 ± 0.0015 0.2525
0.0000 303.3 0.1510 ± 0.0010 0.1418
Ética ± 0.0001 g) excess solute, citric acid, in glass beakers contain-
0.1997 0.1678 ± 0.0012 0.1600
ing the solvents. Solute and suitable amount of solvent were added 0.3997 0.1752 ± 0.0010 0.1805
in the cells that had inside a teflon-coated magnetic stirring bar. 0.6005 0.1825 ± 0.0010 0.2038
Magnetic stirrers (Tecnal, model TE 0852) were turned on to mix 1.0000 0.2700 ± 0.0015 0.2594
0.0000 313.4 0.1712 ± 0.0010 0.1798
up the compounds at around of 1300 rpm. The temperature in the
0.1997 0.2097 ± 0.0012 0.1956
glass vessel was monitored by a calibrated digital thermocouple 0.3997 0.2164 ± 0.0013 0.2128
(Gauge, Model FK 100A C3V001 CE) with an uncertainty of 0.1 K. 0.6005 0.2196 ± 0.0012 0.2317
After 3 h stirring, the stirrers were turned off and mixture stayed 1.0000 0.2806 ± 0.0012 0.2743
decanting for eight or more hours. Using glass syringes (10 mL), 0.0000 322.2 0.1864 ± 0.0012 0.2067
0.1997 0.2395 ± 0.0013 0.2271
three independent samples were taking from the mixture in the cell
0.3997 0.2661 ± 0.0013 0.2495
and transferred to the volumetric flasks which were put in the stove 0.7988 0.2919 ± 0.0014 0.3011
(Odontobrás) at constant temperature (0.93 × 105 Pa; 74 ◦ C) until
constant dry weigh. The relative uncertainties of the experimental
solubility values are less than 0.015.
The mean values representing the average of more than three
presents their solubility data for comparison. As can be seen in
independent determinations were used to calculate the mole frac-
Table 2, our data are more closed to Yang and Wang data than the
tion solubility. The mole fraction solubility of the solute in different
other authors. It can confirm the sentence written by Daneshfar
pure solvents can be calculated by the following equation:
et al. [12] that the difference observed between their results and
m1 /M1 the results reported in literature is mostly due to the difference in
xexp = (1)
m1 /M1 + m2 /M2 + m3 /M3 methods of analysis or experimental error (Fig. 1).

where m1 , m2 and m3 represent the mass of the solute (citric acid),

solvent (water, ethanol or n-propanol) and ethanol only, respec-
tively. M1 , M2 and M3 are the respective molecular masses. The 0.40
experimental solubility data were fitted to the exponential equa-
tion and the parameters of the model were calculated. 0.35

3. Results 0.30
Solubility (mole fraction)

3.1. Experimental data and adjustments of solubility 0.25

0.20
Literature [7,8,13–18] has been recommending equations or
models to correlate solubility data. We can cite the useful corre-
0.15
lations proposed by Heidman et al. [16], Yaws et al. [17,18] and
Wang et al. [5,6]. Similarly and following these authors, solubility 0.10
of citric acid in pure solvents was correlated by Eqs. (2) and (3).
 B
 0.05
xc1 = exp A + (2)
T
0.00
290 295 300 305 310 315 320 325 330 335
 
xc2 = A exp(B T ) (3) Temperature (K)

The most recent data for citric acid in ethanol and water was Fig. 1. Mole fraction solubility of citric acid: (), water; (), ethanol; (), n-
presented by Daneshfar et al. [12] and Yang and Wang [11]. Table 1 propanol; ( ), correlated data with Eq. (2); (- -), correlated data with Eq. (3).
112 M.L.N. Oliveira et al. / Fluid Phase Equilibria 352 (2013) 110–113

Table 3
Parameters for Eqs. (2)–(4) for citric acid in pure solvents and mixtures at temperatures 293.7–333.1 K.

Solvent Parameter

A B rmsd × 103

Eq. Water 2.053 −1204.744 4.756

(2) Ethanol 0.334 −501.855 7.797
n-Propanol −0.882 −119.447 5.543

Solvent Parameter

B
A rmsd × 103

Eq. Water 3.712 × 10−3 1.212×10−2 5.858

(3) Ethanol 0.052 5.390×10−3 8.062
n-Propanol 0.186 1.335×10−3 5.458

T (K) Parameter

A B rmsd × 102

Eq. 293.7 0.153 0.517 2.389

(4) 303.3 0.141 0.628 1.689
313.4 0.179 0.419 1.298
322.2 0.209 0.460 1.894

3.2. Correlating the citric acid solubility in water-ethanol given in Table 3. In general, rmsd is found to be about 0.013 for
mixtures all concentrations and, therefore, the equation predicts the experi-
mental data reasonably well. The accuracy of the estimation of the
Eq. (4) was used to correlate the solubility data as a function of equation parameters is satisfactory, as also presented in Oliveira
ethanol concentration (x2 ) for each temperature. [10].
 The parameters and the root-mean-square deviations (rmsd) for
xc3 = A exp(B x2 ) (4) Eqs. (2)–(4) are shown in Table 3. The root-mean-square deviation
Results for solubility of citric acid in mixtures of ethanol–water is defined by Eq. (5).
can be found in Table 2 including the ones for pure solvents. As  1/2
1  cal
n
can be seen, the standard deviation (ı) presented low values in

exp 2
rmsd = xi − xi (5)
all cases. Differently from the butanedioic acid in ethanol–water n−1
i=1
mixtures [19], citric acid has not shown maximum solubility value
in any mixture. It was noted that solubility always increased for where n is the number of experimental points. Experimental (xexp )
the studied temperature range. In addition, citric acid presented and calculated (xc1 or xc2 ) data for pure solvents are listed in Table 1.
similar solubility in both alcohols and was more soluble in alcohol Also, Table 1 shows data from other researchers (xlit ) as well. It can
than in water contradicting the results of Daneshfar et al. [12]. be seen that the experimental data is reasonable correlated by both
In order to correlate the acid solubility in the ethanol–water equations (Fig. 2).
mixtures, it was used the Eq. (5). For this equation, the fitted param-
eters are listed in Table 3. This table shows the experimental and 4. Conclusion
calculated results of solubility for citric acid in ethanol–water. The
root-mean-square deviations results for the fitted curve are also The solubilities of 3-carboxy-3-hydroxypentanedioic acid in
ethanol, n-propanol, water, and ethanol–water mixtures have
been measured, respectively, at temperatures ranging from 293.7
to 333.1 K by a static analytical method. The solubilities of 3-
carboxy-3-hydroxypentanedioic acid in pure solvents increase as
the temperature rises. According to the findings presented, both
exponential equations correlated the experimental data with good
agreement.
In general for aqueous mixtures, adding alcohol to the sys-
tem caused increasing in the acid solubility. Also, the solubilities
of 3-carboxy-3-hydroxypentanedioic acid in mixtures of solvents
increase as the temperature increases.

List of symbols

A parameter of Eq. (1)

A parameter of Eq. (2)
A parameter of Eq. (3)
B parameter of Eq. (1)
Fig. 2. Mole fraction solubility of citric acid: (), ethanol–water at 293.7 K; (), B parameter of Eq. (2)
ethanol–water at 303.3 K; (), ethanol–water at 313.4 K; (), ethanol–water at
B parameter of Eq. (3)
322.2 K; (-), correlated data with Eq. (4) at 293.7 K; (–), correlated data with Eq.
(4) at 303.3 K; (••), correlated data with Eq. (4) at 313.4 K; (— - —), correlated data mi mass
with Eq. (4) at 322.2 K. Mi molecular mass
 M.L.N. Oliveira et al. / Fluid Phase Equilibria 352 (2013) 110–113 113

rmsd root-mean-square deviations [3] L. Dian-Qing, L. Jiang-Chu, L. Da-Zhuang, W. Fu-An, Fluid Phase Equilib. 200
T temperature (K) (2002) 69–74.
[4] C. Marche, C. Ferronato, J. Jose, J. Chem. Eng. Data 49 (2004) 937–940.
x1 molar fraction of acid [5] Q. Wang, H. Xu, X. Li, J. Chem. Eng. Data 54 (11) (2009) 3130–3132.
x2 molar fraction of solvent [6] Q. Wang, H. Xu, X. Li, J. Chem. Eng. Data 50 (2) (2005) 719–721.
exp
xi experimental acid solubility [7] B.Z. Ren, C.H. Hou, H.G. Chong, W.R. Li, H.J. Song, J. Chem. Eng. Data 51 (6) (2006)
2022–2025.
xical calculated acid solubility [8] A. Apelblat, E. Manzurola, N.A. Balal, J. Chem. Thermodyn. 38 (5) (2006)
xc1 calculated solubility using Eq. (1) 565–571.
xc2 calculated solubility using Eq. (2) [9] M.L.N. Oliveira, R.A. Malagoni, M. Fehr, M.R. Franco Júnior, Chem. Eng. Comm.
195 (2008) 1076–1084.
xc3 calculated solubility using Eq. (3) [10] M.L.N. Oliveira, Experimental study of solubilities of some acids in hydro-
ı standard deviation alcoholics mixtures, School of Chemical Engineering, Federal University of
Uberlândia, Uberlândia, Brazil, 2009 (Doctoral thesis), 340 pp. (in portuguese).
http://www.bdtd.ufu.br/tde busca/arquivo.php?codArquivo=2969
Acknowledgments [11] H. Yang, J-H. Wang, J. Chem. Eng. Data 56 (2011) 1449–1451.
[12] A. Daneshfar, M. Baghlani, R.S. Sarabi, R. Sahraei, S. Abassi, H. Kaviyan, T. Khezeli,
Fluid Phase Equilib. 313 (2012) 11–15.
This work was financially supported by FAPEMIG (Fundação de
[13] A. Apelblat, E. Manzurola, J. Chem. Thermodyn. 19 (1987) 317–320.
Amparo à Pesquisa do Estado de Minas Gerais). [14] A. Apelblat, M. Dov, J. Wisniak, J. Zabicky, J. Chem. Thermodyn. 27 (1995)
35–41.
[15] H. Buchowski, A. Ksia źczak, S. Pietrzyk, J. Phys. Chem. 84 (1980) 975–979.
References [16] J.L. Heidman, C. Tsonopoulos, C.J. Brady, G.M. Wilson, AIChE. J. 31 3 (1985)
376–384.
[1] S. Prasad, Anal. Chim. Acta 540 (2005) 173–180. [17] C.L. Yaws, X. Lin, L. Bu, Chem. Eng. 101 (1994) 119–128.
[2] J. Larsen, C. Cornett, J.W. Jaroszewski, S.H. Hansen, J. Pharm. Biomed. Anal. 49 [18] C.L. Yaws, X. Pan, X. Lin, Chem. Eng. 100 (1993) 108–111.
(2009) 11–17. [19] M.L. Oliveira, M.R. Franco Jr., Fluid Phase Equilib. 326 (2012) 50–53.