International Journal of Thermophysics (2022) 43:123

https://doi.org/10.1007/s10765-022-03055-4

Ascorbic Acid Solubility and Thermodynamic

Characteristics in Several Neat Solvents with Temperatures
Ranging from 293 to 313 K

Leila Nemdili1 · Rym Guedjali1 · Samah Habchi1 · Fatima Mameri2 ·

Ouahiba Koutchoukali1 · Aissa Dehane1 · Slimane Merouani1

Received: 20 March 2022 / Accepted: 2 June 2022 / Published online: 22 June 2022
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature
2022

Abstract
In this study, the solubility of ascorbic acid (AA) in eight pure solvents, including
water, ethanol, methanol, 2-propanol, acetone, acetonitrile, ethyl acetate, and tet-
rahydrofuran, was measured over the temperature range from 293 K to 313 K. The
correlation of the measured solubility data of AA was performed using three non-
ideal solution models, namely the modified Apelblat equation, Buchowski–Ksiazc-
zak model (λh equation), and the Van’t Hoff model. To understand the dissolution
thermodynamic of ascorbic acid, the enthalpy of dissolution ΔHsol, the entropy of
dissolution ΔSsol, and the change in Gibbs free energy ΔGsol were determined by the
modified forms of the Apelblat equation. The predicted results were in good agree-
ment with the experimental solubility data. Compared to the other thermodynamic
models, the computational results reveal that the modified Apelblat equation can
give better correlation results for all the selected solvents. The solubility of ascor-
bic acid increases with rising temperature for all the adopted solvents. In general,
the solubility of ascorbic acid in the four polar protic solvents obeys the following
order: water > methanol > ethanol > propan-2-ol. On the other hand, the solubility of
ascorbic acid in polar aprotic solvents is as follows: tetrahydrofuran > acetone > ace-
tonitrile > ethyl acetate. For all neat solvents, the dissolution process of ascorbic acid
was found to be endothermic, entropy-driven, and not spontaneous.

Keywords Ascorbic acid · Dissolution thermodynamic properties · Non-ideal

solution models · Solubility

* Slimane Merouani
sliman.merouani@univ-constantine3.dz
1
Laboratory of Environmental Process Engineering, Department of Chemical Engineering,
Faculty of Process Engineering, University Constantine 3 - Salah Boubnider, P.O. Box 72,
25000 Constantine, Algeria
2
Pharmaceutical Science Research Center, Constantine, Algeria

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123 Page 2 of 19 International Journal of Thermophysics (2022) 43:123

1 Introduction

Since it was discovered in the late 1920s, no other chemical has been as famous
as ascorbic acid (AA). Its antioxidant properties are almost universally recog-
nized. Ascorbic acid is also one of the most important vitamins in the human
diet. It appears as white to light yellow crystals or powder [1–5]. In general, the
knowledge of the solubility behavior of molecules in different solvents is a cru-
cial issue in the pharmaceutical industry, especially for the dimensioning of a
crystallization process (for purification and preparation of solid medicine). This
is because the solid–liquid equilibrium data in the system are the base of crystal-
lization work and they determine the capacity of production. On the other hand,
experimental investigations for solubility data are extensive and costly work, par-
ticularly during the development stage of the new active ingredient, where the
amount of active molecule available is limited. To tackle this problem, theoretical
investigation (prediction techniques) is regarded as a potent tool for an efficient
and economic pathway for the determination of the solubility of solutes in the dif-
ferent solvents.
It is noteworthy to indicate that the description of the liquid–solid equilibria is
not an easy task, due to the obvious complexity of the thermodynamic description
of condensed phases and the type of molecules that are considered. Indeed, the
crystal structure of active pharmaceutical ingredients is very particular: the mol-
ecules are generally very long and flexible [6]. The application of thermodynamic
models for the prediction of equilibriums is regarded as a feasible approach [7–9].
On the other hand, solubility data are helpful in supplying further information
such as thermochemical properties and intermolecular interactions that can lead
to a deeper understanding of the crystal formation of active pharmaceutical ingre-
dients [10]. Previous studies on the measurement and correlation of the solubility
of ascorbic acid in different solvents by the gravimetric method were performed
in mono-solvents and binary mixed solvents [10–12].
The present study aimed to measure experimentally the solubility of ascorbic
acid by an analytical method in eight different commonly used polar solvents: water,
methanol, ethanol, propan-2-ol, tetrahydrofuran, ethyl acetate, acetone, and ace-
tonitrile. The experiments were conducted in the temperature range of 293–313 K.
On the other hand, the experimental data of ascorbic acid solubility were fitted
using three non-ideal solution models, namely the modified Apelblat equation,
Buchowski–Ksiazczak model (λh equation), and the Van’t Hoff model. The obtained
findings are compared to those found in the literature. Finally, the thermodynamic
properties of ascorbic acid dissolution, i.e., ΔHsol, ΔGsol, and ΔSsol, in the differ-
ent neat solvents were also evaluated and discussed. The results (measurement and
fitting of AA solubility and evaluation of thermodynamic properties of AA disso-
lution) of the present paper are of great importance, due to their direct utility in
the pharmaceutical field especially in the dimensioning of crystallization process.
Therefore, with a simple comparison to the required extensive and costly work for
an experimental investigation of solubility data, the usefulness of our study is evi-
denced by the reduced time and work especially in the industrial domain.

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International Journal of Thermophysics (2022) 43:123 Page 3 of 19 123

Table 1  Suppliers and purities Substance Molecular formula Mass frac- supplier
of the chemicals tion purity

Ascorbic acid C6H8O6 99.0 % PROLABO

Water H2O 99.5 % Distilled
Methanol CH3OH 99.5 % Honeywell
Ethanol C2H5OH 99.5 % BIOCHEM
Tetrahydrofuran C4H8O 99.5 % PANREAC
Ethyl acetate C4H8O2 99.5 % PROLABO
Acetone C3H6O 99.5 % Honeywell
Acetonitrile C2H3N 99.5 % MERCK
Propan-2-ol C3H8O 99.5 % PROLABO

2 Experimental

2.1 Materials

All of the chemicals [ascorbic acid (AA, MW: 176.12 g·mol−1), methanol (MW:
32.042 g·mol−1), ethanol (MW: 46.07 g·mol−1), propan-2-ol (MW: 60.10 g·mol−1),
tetrahydrofuran (MW: 72.11 g·mol−1), ethyl acetate (MW: 88.11 g·mol−1), acetone
(MW: 58.08 g·mol−1), and acetonitrile (MW: 41.05 g·mol−1)] were reagent grade
and were used as received without any additional purification. In addition, distilled
water was used as a solvent (MW: 18.015 g·mol−1). The chemicals purity (% mass
fraction) and molecular formula and suppliers are indicated in Table 1. The molecu-
lar structure of ascorbic acid is given in Fig. 1.

2.2 Solubility Measurements

The experimental measurement of ascorbic acid’s solubility in several neat solvents

(water, ethanol, methanol, acetone, propan-2-ol, acetonitrile, ethyl acetate, and tet-
rahydrofuran) was carried out by an analytical method. This technique consists of
sampling the solution at equilibrium to determine its composition. The experimental
protocol is described in Fig. 2. Sufficient amounts of ascorbic acid were first added
to 25 mL of solvent to allow the equilibrium to take place at an appropriate tem-
perature (step 1). A stirring water bath (Memmert WNB/WNE/WPE) was employed
to maintain the temperature (293, 298, 303, 308, or 313 K) with an accuracy of
± 0.1 K (step 2). This solution was stirred at 160 rpm for 6 h to ensure the achieve-
ment of the solid–liquid equilibrium state at the set temperature. The stirring was
subsequently stopped for 30 min to let the undissolved solid sink completely to the
bottom. After that, the prepared solutions were introduced into an incubator (step 3)
equipped with thermoregulation for 24 h. The resulting saturated solutions (a precip-
itate is observed at the bottom of the flask) were then filtered through a membrane
(0.22 µm), Step 4. For an accurate determination of AA’s solubility, steps 3 and 4

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123 Page 4 of 19 International Journal of Thermophysics (2022) 43:123

Fig. 1  Chemical structure of ascorbic acid

Fig. 2  Experimental setup of solubility measurement

are repeated three times (step 5). Finally, (steps 6, 7), the solubility of ascorbic acid
was quantified by a UV–Vis spectrophotometer (KLAB OPTIZEN POP).
It should be noted that the calibration curve is established through the preparation
(in 25 mL volumetric flasks) of a set of known concentrations of ascorbic acid (AA)
in the adopted pure solvents (water, methanol, ethanol, propan-2-ol, tetrahydrofuran,
ethyl acetate, acetone, and acetonitrile). The absorption of these solutions (vs. AA
concentration) was measured by a UV–Vis spectrophotometer (OPTIZEN POP)
from KLAB. Analytical wavelengths were chosen at the point of maximum absorb-
ance. Three separated curves were prepared in this way and their results were aver-
aged to obtain the final curve (calibration curve) used for the determination of the
concentration of ascorbic acid in the different samples (via interpolation). It is worth
mentioning that throughout the present work, all runs were performed in triplicate
and each experimental data point represents the averaged value. Error bars, ported in
relevant data, represent the deviation of means.

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International Journal of Thermophysics (2022) 43:123 Page 5 of 19 123

3 Thermodynamic Models

As it is known, the correlation of experimental data of solute’s solubility with the

different models is an important task to find the suitable equation describing the sol-
ubility behavior in selected solvents and to further understand the thermodynamic
properties of our solution (solvent and solute) under the operating conditions. For
this purpose, different non-ideal solution models can be employed [13, 14]. In this
study, three non-ideal solution models were used to correlate the experimental solu-
bility data (in polar and non-polar systems), namely the modified Apelblat equation
[15, 16], the Buchowski–Ksiazczak model (λh equation) [17–19], and the Van ’t
Hoff model [20, 21]. Details of each model are given in the following sections.

3.1 Modified Apelblat Equation

This correlative model was firstly introduced by Apelblat and Manzurola [16].
The modified Apelblat equation [15, 16] was widely used in a variety of exper-
imental works [15, 22–25], where the solubility of solute (in mole fraction) is
related to the medium temperature. This semi-empirical equation (modified Apel-
blat equation) is suitable for polar and non-polar systems [26, 27]. It is based on
the solid-solvent behavior in the equilibrium of the solid–liquid phase as illus-
trated in the following equation:
ln x = A + B∕T + C ln T (1)
where x and T are the mole fraction (experimental solubility) of ascorbic acid and
the absolute temperature (K), respectively. A, B, and C are the model parameters.
The values of A and B indicate the impact of the solution non-ideality (solution
imperfection) on solute solubility and activity coefficients. While the constant C
reflects the effect of temperature variations on the solute fusion enthalpy.

3.2 λh Equation

The solid–liquid equilibrium data may be described by the two-parameter λh

equation proposed by Buchowski et al. [17–19]. By employing the Buchowski-
Ksiazaczak model (λh equation), there are only two adjustable parameters, λ and
h, needed to fit the experimental data. The simplicity and wide applicability of
this model are demonstrated by several successful implementations [28–32]. This
equation (λh equation) represents the influence of temperature on the solubility
(x) of solute [26, 33, 34] as follows:
( )
λ(1 − x) 1 1
ln 1 + = 𝜆h( − ) (2)
x T Tm

where x and T are the mole fraction of ascorbic acid and the absolute temperature. λ
(indicate the non-ideality of the real solution) and h (enthalpic factor) are the model

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parameters, which can be obtained from experimental data regression [19, 35, 36].
­Tm (K) is the melting temperature of ascorbic acid.

3.3 Van’t Hoff Model

The Van’t Hoff equation [20, 21, 37] has been previously proposed as an alternative
model to describe the temperature dependence of solubility (x) in the selected sol-
vents. The equation is expressed as follows:
ln x = a + b∕T (3)
where x and T are the mole fraction of ascorbic acid and the absolute temperature. a
and b are the model parameters computed from experimental solubility data.

4 Estimation of Models’ Parameters and Deviations Calculation

In the present study, the estimation of model parameters (A, B, and C of the modified
Apelblat equation, λ and h of the λh equation, and a and b of the Van’t Hoff equa-
tion) was performed using a non-linear regression method (Tables 5, 6, 7). Since the
three selected models involve different parameters that require adjustment and predic-
tion, the root mean square deviation (RMSD, Eq. 4), and the root absolute deviation
(RAD, Eq. 5) were employed for the evaluation of the model’s performance [21, 38]:
N e c
1 ∑ || xi − xi ||
RAD = | | (4)
N i=1 || xie ||

�
∑N
(xic − xie )2
RMSD =
i=1 (5)
N
where N is the number of performed experiments, xie and xic are the experimental and
the computed solubility values, respectively. The low RAD and RMSD values indi-
cate the high capacity of the adopted model to predict the ascorbic acid solubility
(i.e., experimental and predicted solubilities of AA are close or equal).

5 Results and Discussion

5.1 Solubility Data

5.1.1 Validation of Experimental Solubility of Ascorbic Acid

Before discussion of the correlation findings, our experimental results of ascorbic

acid (AA) solubility (using UV–Vis spectrophotometer) were compared to those

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International Journal of Thermophysics (2022) 43:123 Page 7 of 19 123

obtained by Shalmashi and Eliassi [11] as it is presented in Fig. 3. With a simple

comparison of both investigations it can be observed that our work is relatively
extended compared to that of Shalmashi and Eliassi [11]. In the present paper, three
non-ideal solution models (modified Apelblat equation, λh equation and Van’t Hoff
model) were adopted to correlate the experimental data of AA solubility compared
to only one model (Van’t Hoff model) in Shalmashi and Eliassi’ study. Therefore,
more possibilities are allowed in our work to discover which thermodynamic model
is adequate to satisfactorily correlate the solubility of ascorbic acid in different sol-
vents compared to the case of Shalmashi and Eliassi’ study [11]. On the other hand,
an analytical method (using UV–Vis) was employed in our work for the determina-
tion of ascorbic acid solubility compared to the gravimetric technique in Shalmashi
and Eliassi’ study. In addition, the performance of our thermodynamic models was
performed using the root mean square deviation (RMSD) and the root absolute
deviation (RAD), whereas only the RMSD was employed in Shalmashi and Eliassi’
work [11]. Moreover, regarding the estimation of the thermodynamic properties, the
modified Apelblat equation parameters were used in our work for the evaluation of
the dissolution’s enthalpy and entropy in addition to Gibbs free energy. Neverthe-
less, only the enthalpy of dissolution has been estimated in Shalmashi and Eliassi’
study using Dallos’s correlation.
As it can be seen in Fig. 3, our measured values of AA mole fraction solubili-
ties were found to be in good agreement with the literature’s values [11] with an
averaged deviation of ~ 14.3 %. The deviations may result from the differences in
measurement techniques (the gravimetric method was used by Shalmashi and Eliassi
[11]) and equipment, sampling conditions, and experimental handling. Moreover,
our experimental results (of AA solubility) are in line with those obtained by Hassan
et al. [10] and Neto et al. [12]. In addition, it is observed that for both sets of data
(our experimental results and Shalmashi and Eliassi’ findings [11], Fig. 3), the solu-
bility of ascorbic acid decreases in the order of water, methanol, ethanol, propan-
2-ol, tetrahydrofuran, acetone, acetonitrile, ethyl acetate. This order indicates that
the solubility of ascorbic acid throughout the eight solvents is not only explained by
the polarity of these solvents (Table 2), but also it may be ascribed to the molecular
weight or even the size of each solvent. More details about the solubility behavior of
ascorbic acid will be given in the following sections.

5.1.2 Experimental and Correlated Data of Ascorbic Acid Solubility

The measured (using UV–Vis) and correlated values (using modified Apelblat
equation, ʎh equation, and the Van ’t Hoff equation) of ascorbic acid solubility are
summarized in Table 3 for the eight neat solvents (water, methanol, ethanol, pro-
pan-2-ol, tetrahydrofuran, acetone, acetonitrile, ethyl acetate) at the temperature
range from 293 K to 313 K. The evaluated parameters of the different thermo-
dynamic models are listed in Table 4 (modified Apelblat equation), 5 (λh equa-
tion), and 6 (Van’t Hoff model). For more clarification of the tabulated results in
Table 3, the correlated and measured values of AA solubility are traced as a func-
tion of the solution temperature for each solvent, Fig. 4. As it is seen in Fig. 4,
the solubility of ascorbic acid in each solvent increases monotonically with the

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123 Page 8 of 19 International Journal of Thermophysics (2022) 43:123

The present work Shalmashi and Eliassi The present work Shalmashi and Eliassi
0.0014 0.007

Mole fraction of ascorbic acid

Mole fraction of ascorbic acid

0.0012 0.006

Propan-2-ol 0.005 Ethanol

0.001
0.004
0.0008
0.003
0.0006
0.002

0.0004 0.001

0.0002 0
290 295 300 305 310 315 290 295 300 305 310 315
T (K) T (K)

The present work Shalmashi and Eliassi The present work Shalmashi and Eliassi
0.0014 0.016
Mole fraction of ascorbic acid

Mole fraction of ascorbic acid

0.0012 0.015
Tetrahydrofuran 0.014 Methanol
0.001
0.013
0.0008
0.012
0.0006
0.011
0.0004
0.01
0.0002 0.009

0 0.008
290 295 300 305 310 315 290 295 300 305 310 315
T (K) T (K)

The present work Shalmashi and Eliassi The present work Shalmashi and Eliassi
0.00055 0.0005
Mole fraction of ascorbic acid

Mole fraction of ascorbic acid

0.0005 0.00045

0.00045 Acetone 0.0004 Acetonitrile

0.0004 0.00035

0.00035 0.0003

0.0003 0.00025

0.00025 0.0002

0.0002 0.00015
290 295 300 305 310 315 290 295 300 305 310 315
T (K) T (K)

The present work Shalmashi and Eliassi The present work Shalmashi and Eliassi
0.0006 0.06
Mole fraction of ascorbic acid

Mole fraction of ascorbic acid

0.055
0.0005 Ethyl acetate
0.05
Water
0.0004
0.045

0.0003 0.04

0.035
0.0002
0.03
0.0001
0.025

0 0.02
290 295 300 305 310 315 290 295 300 305 310 315
T (K) T (K)

Fig. 3  Comparison of our experimental results for ascorbic acid solubility in the different neat solvents
[ethanol, methanol, water, propan-2-ol, tetrahydrofuran, acetone, acetonitrile, and ethyl acetate] with
those of Shalmashi and Eliassi [11]. Medium temperature ranges from 293 K to 313 K

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International Journal of Thermophysics (2022) 43:123 Page 9 of 19 123

Table 2  Geometrical formula and relative polarity of solvents

Solvent Geometric formula Relative polarity

Water 1

Methanol 0.762

Ethanol 0.654

Tetrahydrofuran 0.207

Ethyl acetate 0.228

Acetone 0.355

Acetonitrile 0.460

Propan-2-ol 0.546

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123 Page 10 of 19 International Journal of Thermophysics (2022) 43:123

Table 3  Molar fraction of experimental and predicted solubilities of ascorbic acid in solvents (ethanol,
methanol, water, propan-2-ol, tetrahydrofuran, acetone, acetonitrile, and ethyl acetate) for temperatures
ranging from 293 K to 313 K
Solvent T(K)± 0.1 103 Xexp 103Apelblat 103ʎh 103 Van ‘t Hoff

Ethanol 293.15 2.308 ± 0.05 2.293 10.947 2.029

298.15 2.406 ± 0.01 3.013 12.147 2.691
303.15 4.107 ± 0.03 3.942 13.432 3.535
308.15 5.940 ± 0.01 5.134 14.804 4.604
313.15 6.210 ± 0.02 6.658 16.266 5.945
Methanol 293.15 10.85 ± 0.02 10.477 10.947 12.381
298.15 10.88 ± 0.04 11.665 12.147 13.785
303.15 13.07 ± 0.01 12.941 13.432 15.294
308.15 15.26 ± 0.03 14.310 14.804 16.911
313.15 15.33 ± 0.03 15.772 16.266 18.638
Water 293.15 28.000 ± 0.01 25.686 20.553 23.413
298.15 29.000 ± 0.03 31.655 24.652 31.577
303.15 38.700 ± 0.01 38.874 29.393 39.472
308.15 48.300 ± 0.02 47.581 34.845 47.111
313.15 58.000 ± 0.01 58.047 41.085 54.505
Propan-2-ol 293.15 0.45 ± 0.06 0.494 0.640 0.400
298.15 0.50 ± 0.04 0.648 0.816 0.529
303.15 0.95 ± 0.03 0.846 1.032 0.694
308.15 1.29 ± 0.04 1.100 1.295 0.902
313.15 1.29 ± 0.02 1.423 1.614 1.162
Acetone 293.15 0.260 ± 0.02 0.241 0.267 0.308
298.15 0.298 ± 0.05 0.284 0.314 0.327
303.15 0.310 ± 0.03 0.335 0.368 0.347
308.15 0.361 ± 0.03 0.393 0.430 0.367
313.15 0.490 ± 0.04 0.461 0.498 0.388
Acetonitrile 293.15 0.280 ± 0.07 0.252 0.252 0.302
298.15 0.290 ± 0.04 0.294 0.294 0.326
303.15 0.310 ± 0.02 0.341 0.342 0.351
308.15 0.390 ± 0.02 0.395 0.396 0.377
313.15 0.474 ± 0.02 0.457 0.456 0.403
Tetrahydrofuran 293.15 0.360 ± 0.03 0.338 0.404 0.378
298.15 0.410 ± 0.01 0.453 0.511 0.510
303.15 0.620 ± 0.03 0.604 0.643 0.681
308.15 0.820 ± 0.01 0.802 0.802 0.901
313.15 1.050 ± 0.02 1.060 0.993 1.181
Ethyl acetate 293.15 0.102 ± 0.05 0.035 0.097 0.168
298.15 0.106 ± 0.03 0.068 0.140 0.191
303.15 0.140 ± 0.04 0.132 0.199 0.216
308.15 0.170 ± 0.01 0. 250 0.279 0.243
313.15 0.500 ± 0.01 0.469 0.380 0.272

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International Journal of Thermophysics (2022) 43:123 Page 11 of 19 123

Table 4  Parameters of the modified Apelblat equation for the solubility of ascorbic acid in eight pure sol-
vents (i.e., ethanol, methanol, water, propan-2-ol, tetrahydrofuran, acetone, acetonitrile, and ethyl acetate)
Solvents A B C 105 RAD 105 RMSD R2

Water − 73.798 916 0.818 492 12.347 219 15.3 160.9 0.9 999
Methanol 1.399 998 − 1 855.691 0.0659 998 68.1 61.1 0.9 999
Ethanol − 97.770 889 0.042 329 16.142 646 67.9 49.9 0.9 999
Acetone − 64.128 434 − 1.968 960 9.824 517 2.46 209 2.47 867 0.9 999
Acetonitrile − 59.260 775 − 0.005 711 8.974 765 20.1 2.03 632 0.9 999
Ethyl Acetate − 232.2 258 − 6.258 182 39.083 717 1 217.08 5.15 616 0.9 999
Propan-2-ol − 98.566 174 0.064 519 16.012 592 111.3 13.1 0.9 999
Tetrahydrofuran − 106.33 121 2.778 530 17.311 120 5.0 647 2.45 001 0.9 999

rise of temperature (from 293 K to 313 K). A similar tendency was observed for
other drugs [13, 39, 40]. This behavior could be explained by the fact that high
temperatures lead to more effective collision and intermolecular interactions
between solute and solvents molecules thanks to their high kinetic energies. As
it is indicated in Table 3 and Figs. 3, 4 (either for the experimental or predicted
values of AA solubility), with the exception of methanol solvent, the AA solu-
bility in water is about one or even two orders of magnitude higher than those
obtained for the other solvents at the same temperature, whereas the AA solubil-
ity in water is about two times greater than that obtained for methanol solvent at
the same temperature. Therefore, water may be considered a better solvent for
acid ascorbic separation and purification from solutions. In the temperature range
from 293 K to 313 K, the order of solubility of ascorbic acid in the four polar
protic solvents (Figs. 3, 4, 5, 6, 7, Table 3) is as follows: water > methanol > etha-
nol > propan-2-ol. This order indicates that the solubility of ascorbic acid goes
down with decreasing relative polarity (Table 2) and increasing molecular size of
each solvent. As ascorbic acid is a polar organic molecule that has many hydroxyl
groups (Fig. 1), this affects its polarity as well as its hydrogen bonding capacity.
For that reason, molecules with lower molecular weight such as water compared
to other solvents used in this study reach equilibrium faster because the hydroxyl
groups existing on ascorbic acid can establish hydrogen bonds, enhancing its
solubility. The solubility of ascorbic acid in the polar aprotic solvents (Figs. 3,
4, 5, 6, 7, Table 3) obeys the following order: Tetrahydrofuran > acetone > ace-
tonitrile > ethyl acetate. It may be observed that the solubility of ascorbic acid in
this group of solvents (polar aprotic solvents) does not follow the relative polarity
order, but it is strongly related to the molecular weight (Table 2).
To verify the consistency between the measured and the correlated values (using
the three mathematical models) of acid ascorbic solubility, the root mean square
deviation (RMSD), and the root absolute deviation (RAD) were calculated accord-
ing to Eq-4 and 5 (see Tables 4, 5 and 6). It is found that for the three investigated
models (modified Apelblat equation, Van ’t Hoff equation, and ʎh equation), the
values of RAD and RMSD are close to zero, which supports the performance of
these thermodynamic models. According to Figs. 5, 6, 7 (and Tables 4, 5, 6), the

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123 Page 12 of 19 International Journal of Thermophysics (2022) 43:123

Experimental Apelblat Van't Hoff Experimental Apelblat Van‘t Hoff

0.0018 0.008
Mole fraction of ascorbic acid

Mole fraction of ascorbic acid

0.0016 0.007
0.0014 Propan-2-ol Ethanol
0.006
0.0012
0.005
0.001
0.004
0.0008
0.003
0.0006
0.002
0.0004
0.0002 0.001

0 0
290 295 300 305 310 315 290 295 300 305 310 315
T (K) T (K)

Experimental Apelblat Van't Hoff Experimental Apelblat Van't Hoff

0.0014 0.02

Mole fraction of ascorbic acid

Mole fraction of ascorbic acid

0.0012
Tetrahydrofuran 0.018 Methanol
0.001
0.016
0.0008
0.014
0.0006
0.012
0.0004

0.0002 0.01

0 0.008
290 295 300 305 310 315 290 295 300 305 310 315
T (K) T (K)

Experimental Apelblat Van't Hoff Experimental Apelblat Van‘t Hoff

0.00055 0.0005
Mole fraction of ascorbic acid
Mole fraction of ascorbic acid

0.0005 0.00045
Acetone Acetonitrile
0.00045
0.0004
0.0004
0.00035
0.00035
0.0003
0.0003

0.00025 0.00025

0.0002 0.0002
290 295 300 305 310 315 290 295 300 305 310 315
T (K) T (K)

Experimental Apelblat Van't Hoff Experimental Apelblat Van't Hoff

0.0006 0.07
Mole fraction of ascorbic acid
Mole fraction of ascorbic acid

0.0005 0.06
Ethyl acetate Water
0.0004 0.05

0.0003 0.04

0.0002 0.03

0.0001 0.02

0 0.01
290 295 300 305 310 315 290 295 300 305 310 315
T (K) T (K)

Fig. 4  Experimental and correlated values (using the three thermodynamic models) of ascorbic acid
solubility in the different neat solvents [ethanol, methanol, water, propan-2-ol, tetrahydrofuran, acetone,
acetonitrile, and ethyl acetate]. Medium temperature ranges from 293 K to 313 K

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International Journal of Thermophysics (2022) 43:123 Page 13 of 19 123

Ethanol Propan-2-ol Methanol

Tetrahydrofuran Acetonitrile Acetone
Water Ethyl acetate

Predicted (Apelblat) 0.06

0.05

0.04

0.03

0.02

0.01

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Experimental
0.0016
0.0014
Predicted (Apelblat)

0.0012
0.001
0.0008
0.0006
0.0004
0.0002
0
0 0.0002 0.0004 0.0006 0.0008 0.001 0.0012 0.0014 0.0016
Experimental

Fig. 5  Predicted values of the solubility of ascorbic acid calculated by the modified Apelblat equation
(for ethanol, methanol, water, propan-2-ol, tetrahydrofuran, acetone, acetonitrile, and ethyl acetate) com-
pared to the experimental data for the temperature range from 293 K to 313 K

provided results by the three models are in good accordance with the experimental
data. Furthermore, it may also be noticed that the estimated results by the modified
Apelblat equation are the most consistent with the experimental data which illustrate
the Apelblat equation may also be applied to correlate the solubility of ascorbic acid
satisfactorily.

5.2 Estimation of Thermodynamic Properties of the Saturated Solutions

of Ascorbic Acid

To evaluate the dissolution behavior of AA in eight different neat solvents, the

enthalpy of dissolution ∆Hsol, the entropy of dissolution ∆Ssol, and the change in
Gibbs free energy ∆Gsol can be calculated using the modified Apelblat equation
parameters (A, B, and C) [41]:
ΔHsol = R(−B + CT) (6)

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123 Page 14 of 19 International Journal of Thermophysics (2022) 43:123

Ethanol Propan-2-ol Methanol

Tetrahydrofuran Acetonitrile Acetone
Water Ethyl acetate

0.06
Predicted (Van't Hoff ) 0.05

0.04

0.03

0.02

0.01

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Experimental
0.0015
Predicted (Van't Hoff )

0.0012

0.0009

0.0006

0.0003

0
0 0.0003 0.0006 0.0009 0.0012 0.0015
Experimental

Fig. 6  Predicted values of the solubility of ascorbic acid evaluated by the Vant’ Hoff equation (for etha-
nol, methanol, water, propan-2-ol, tetrahydrofuran, acetone, acetonitrile, and ethyl acetate) compared to
the experimental data for temperature range from 293 K to 313 K

ΔSsol = R(A + C(1 + lnT)) (7)

ΔGsol = ΔHsol − TΔSsol (8)

where R is the gas constant. Table 7 regroups the thermodynamic properties of
ascorbic acid in the different examined solvents from K 293 to 313 K, calculated
by Eqs. 6, 7, and 8. According to this table, all values are positive, indicating that
the dissolution processes of ascorbic acid are endothermic, entropy-induced, and not
spontaneous. It was further found that the lower values of ΔGsol (in all different sol-
vents) show a higher solubility in all the investigated systems. Nevertheless, over
the temperature range from 293 K to 313 K, the highest values of ΔHsol and ΔGsol
were retrieved for ethyl acetate (Table 7), which indicates low solubility of ascorbic
acid (poor solute–solvent interactions). In contrast, the lowest values of ΔGsol were
obtained for water with a relatively higher ΔHsol compared to that of methanol. This
indicates the high solubility of ascorbic acid in water (corroborates the results of

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International Journal of Thermophysics (2022) 43:123 Page 15 of 19 123

Ethanol Propan-2-ol Methanol

Tetrahydrofuran Acetonitrile Acetone
Water Ethyl acetate

0.06
Predicted ( ʎh)
0.05

0.04

0.03

0.02

0.01

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Experimental
0.0018

0.0015
Predicted ( ʎh)

0.0012

0.0009

0.0006

0.0003

0
0 0.0003 0.0006 0.0009 0.0012 0.0015 0.0018

Experimental

Fig. 7  Predicted values of the solubility of ascorbic acid calculated by the ʎh equation (for ethanol, meth-
anol, water, propan-2-ol, tetrahydrofuran, acetone, acetonitrile, and ethyl acetate) compared to the experi-
mental findings for the temperature range from 293 K to 313 K

Table 5  Parameters of the ʎh equation for the solubility of ascorbic acid in eight solvents (ethanol, meth-
anol, water, propan-2-ol, tetrahydrofuran, acetone, acetonitrile, ethyl acetate)
Solvent ʎ h 105RAD 105RMSD R2

Water 1.09 9876 2 887.5 582 5 096.032 333.0213 0.9997

Methanol 0.1 06548 17 042.0415 675.883 75.2679 0.9999
Ethanol 1.049 4 577.1613 2 199.1784 67.6314 0.9998
Acetone 0.00 9651 296 552.183 1 873.637 3.79 941 0.9999
Acetonitrile 0.0 07624 356 787.4214 21.0 314 2.10 157 0.9999
Ethyl Acetate 0.26 2909 23 963.6372 1 666.858 7.6 609 0.9999
Propan-2-ol 0.13 32 614.57963 4 056.1625 22.0311 0.9 999
Tetrahydrofuran 0.0 71072 58 041.3402 589.120 7.36 554 0.9999

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Table 6  Parameters of the Van ’t Hoff equation for ascorbic acid solubility in eight neat solvents (etha-
nol, methanol, water, propan-2-ol, tetrahydrofuran, acetone, acetonitrile, ethyl acetate)
Solvents a b 105 RAD 104 RMSD R2

Water 0.51 − 142.5 698 586.081 289.4908 0.9997

Methanol 2.01 − 1875.6546 3 554.3917 242.5233 0.9995
Ethanol 10.62 3547 − 4929.3173 2 064.5652 68.395 0.9998
Acetone − 4.471 488 − 1058.8158 220.0 324 5.47 226 0.9999
Acetonitrile − 3.591 759 − 1321.7653 196.7 939 4.15 782 0.9999
Ethyl Acetate − 1.176 869 − 2200.2282 1 462.3409 12.2 047 0.9999
Propan-2-ol 8.865 984 − 4889.9278 3 560.2228 21.7 882 0.9999
Tetrahydrofuran 9.952 143 − 5224.8794 2 407.0804 10.1 219 0.9999

Figs. 3, 4 and Table 3) with more absorption of energy compared to the methanol,
acetone, and acetonitrile, Table 7.

6 Conclusions

In the present paper, the solubility of ascorbic acid in eight pure solvents, includ-
ing water, ethanol, methanol, propan-2-ol, acetone, acetonitrile, ethyl acetate, and
tetrahydrofuran, was measured at temperatures ranging from 293 K to 313 K. A
good concordance was observed between our findings and those available in the
literature. The accuracy of the investigated models was clearly evidenced by the
low values (close to zero) of RMSD and RAD. The best fitting of the experi-
mental results of AA solubility was obtained via the modified Apelblat equation.
On the other hand, it was found that the solubility of ascorbic acid in water is
almost one or even two orders of magnitude higher than that in the remaining
solvents with the exception of methanol, in which the solubility of AA is approxi-
mately two-time lower than that in water at the same temperature. The solubility
of ascorbic acid in the four polar protic solvents is in the order: water > metha-
nol > ethanol > propan-2-ol, whereas, for the aprotic polar solvents, the solubility
of AA is in the order: tetrahydrofuran > acetone > acetonitrile > ethyl acetate.
Through the deep analysis conducted in the present work, it can be retrieved that
the efficacy of the modified Apelblat equation (compared to the other models) is
clearly evidenced for the prediction of ascorbic acid solubility (in the eight solvents)
over the temperature range from 293 K to 313 K. On the other hand, either using
others thermodynamic models or others solvents (e.g., a binary mixture), our find-
ings are possibly used for future comparisons in order to enhance our understanding
toward the behavior of ascorbic acid in the different operational conditions.
Finally, it should be noted that other experimental (e.g., laser monitoring obser-
vation technique, gravimetric method, and so on) and theoretical techniques (e.g.,
local composition model, Wilson model, non-random two liquid (NRTL Model),
and so on) are possibly used for the measurement and predication of AA solubility.
However, the spectrophotometric method and the theoretical models adopted in the

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International Journal of Thermophysics (2022) 43:123 Page 17 of 19 123

Table 7  Thermodynamic properties of ascorbic acid dissolution in different solvents (from 293 K to
313 K) using the parameters of the modified Apelblat equation
Solvent T (K) Xcal ΔHsol ΔSsol ΔGsol
KJ·mol−1 KJ·mol−1 ­K−1 KJ·mol−1

Ethanol 293 0.002 293 39.323 166 0.083 678 14.805 359
298 0.003 013 39.994 215 0.085 949 14.381 273
303 0.003 942 40.665 265 0.088 182 13.945 928
308 0.005 134 41.336 315 0.090 379 13.499 508
313 0.006 658 42.007 365 0.092 540 13.042 194
Methanol 293 0.010 477 15.588 992 0.0153 051 11.104 583
298 0.011 665 15.591 735 0.0 153 144 11.028 034
303 0.012 941 15.594 479 0.0 153 235 10.951 438
308 0.014 310 15.597 223 0.0 153 325 10.874 798
313 0.015 772 15.599 966 0.0153 413 10.798 113
Water 293 0.025 686 30.071 047 0.072 187 8.920 111
298 0.031 655 30.584 321 0.073 924 8.554 818
303 0.038 874 31.097 594 0.075 632 8.180 914
308 0.047 581 31.610 868 0.077 312 7.798 539
313 0.058 047 32.124 142 0.078 965 7.407 831
Propan-2-ol 293 0.000 494 39.006 171 0.0 698 435 18.542 025
298 0.000 648 39.671 815 0.0 720 961 18.187 160
303 0.000 846 40.337 458 0.0 743 113 17.821 126
308 0.001 100 41.003 102 0.0 764 902 17.444 107
313 0.001 423 41.668 745 0.0 786 340 17.056 282
Acetone 293 0.000 241 23.948 914 0.012 479 20.292 382
298 0.000 286 24.357 319 0.013 861 20.226 519
303 0.000 335 24.765 724 0.015 220 20.153 803
308 0.000 393 25.174 129 0.016 557 20.074 347
313 0.000 461 25.582 535 0.017 873 19.988 261
Acetonitrile 293 0.000 252 21.862 594 0.005 755 20.176 373
298 0.000 294 22.235 675 0.007 017 20.144 433
303 0.000 341 22.608 756 0.008 259 20.106 232
308 0.000 395 22.981 837 0.009 480 20.061 875
313 0.000 457 23.354 918 0.010 681 20.011 461
Tetrahydrofuran 293 0.000 338 42.146 823 0.0 774 038 19.467 510
298 0.000 453 42.866 447 0.0 798 391 19.074 385
303 0.000 604 43.586 070 0.0 822 339 18.669 186
308 0.000 802 44.305 693 0.0 845 895 18.252 111
313 0.001 060 45.025 317 0.0 869 072 17.823 354
Ethyl acetate 293 0.000 035 95.260 043 0.2 399 435 24.956 596
298 0.000 068 96.884 753 0.2 454 418 23.743 094
303 0.000 132 98.509 463 0.2 508 486 22.502 330
308 0.000 250 100.13 417 0.2 561 669 21.234 755
313 0.000 469 101.75 888 0.2 613 996 19.940 804

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present paper (Sects. 2.2 and 3) are mainly characterized by their simplicity and effi-
cacy for the evaluation and prediction of the solubility of the different solutes.

Acknowledgements This study was supported by The Ministry of Higher Education and Scientific
Research of Algeria (project No. A16N01UN250320220002) and the General Directorate of Scientific
Research and Technological Development (GD-SRTD).

Declarations

Conflict of interest All authors of this manuscript declare that they have no conflict of interest.

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