Fluid Phase Equilibria 388 (2015) 5965

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Correlation of solubility and calculation of thermodynamic properties

of guanidine nitrate in different solvents
Xiangyang Zhang a,b , Gang Qian a, * , Rui Wang c, Xiaowu Yang d, Lin Hao c,
Hongyuan Wei c, Xinggui Zhou a
a
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, 200237 Shanghai, China
b
Department of Product Engineering, East China University of Science and Technology, 200237 Shanghai, China
c
School of Chemical Engineering, Tianjin University, 300072 Tianjin, China
d
China Huanqiu Constracting & Engineering Corp., 200032 Shanghai, China

A R T I C L E I N F O A B S T R A C T

Article history: To realize the rapid solvent screening and further crystallization process optimization, experimental
Received 17 September 2014 determination of accurate solubility data of target solute in potential solvents is necessary. Using a
Received in revised form 19 December 2014 gravimetric method, solubilities of guanidine nitrate in water, methanol, ethanol, n-propanol and acetone
Accepted 26 December 2014
at temperature ranging from 278.05 K to 332.85 K at pressure p = 0.1 MPa were experimentally measured.
Available online 27 December 2014
Melting temperature, Tm, and fusion enthalpy, DHf, of guanidine nitrate were determined using
differential scanning calorimetry. Subsequently, Apelblat equation, vant Hoff equation, lh equation, and
Keywords:
Wilson model were used to correlate the measured solubility data, respectively. Dissolution of guanidine
Guanidine nitrate
Solubility
nitrate in all examined solvents was found to be endothermic and entropically favorable. Moreover, the
Solvent measured solubility data were combined with calculated ideal solubility data to calculate activity
Thermodynamic modeling coefcients at innite dilution based on the assumption of DCp = 0, which were then tted to a vant Hoff
like regular solution equation.
2014 Elsevier B.V. All rights reserved.

1. Introduction Moreover, as one of the most fundamental physicochemical

Guanidine nitrate (GN, CH6N4O3, CAS Registry No. 506-93-4) is
well known as a high energy fuel used in some gas generator and
solid rocket propellant applications. Moreover, it is also an
important intermediate for synthesizing sulfa and pyrimidine
nitrate drugs such as sulfadiazine and 2-amino-4-chloro-6-
methoxypyrimidine. Especially, the latter drugs have broad
spectrum, high selectivity and low toxicity, and are often used
for the treatment of malignant lymphoma, lung cancer, etc. [1]. The
chemical structure of GN is shown in Fig. 1.
In industrial, GN is mainly produced by condensation reaction
of urea and ammonium nitrate or fusion reaction of dicyandiamide
and ammonium nitrate [1]. In any case, the raw product is rened
by solution crystallization. The experimental determination of its
accurate solubility in potential solvents is then crucial for rapid
solvent screening and further crystallization process optimization.
* Corresponding author. Tel.: +86 21 64250937; fax: +86 21 64253528.
E-mail address: carlqg@ecust.edu.cn (G. Qian).
properties, solubility of materials in given system also provided
valuable information for the preference crystallization of target
polymorphic forms and estimation of crystallization efciency
[2,3]. However, the few available solubility data of GN in different
pure solvents have been reported at the beginning of last century
and show no systematic [4,5]. The present papers concerning
about GN mainly focused on the investigation on synthetic process
and thermal stability [6,7].
In this work, gravimetric method was used to determine the
solubility of GN in water, methanol, ethanol, n-propanol and
acetone at temperature ranging from 278.05 K to 332.85 K at
pressure p = 0.1 MPa. Melting temperature and fusion enthalpy
were measured using differential scanning calorimetry (DSC).
With these thermodynamic properties, Apelblat equation, vant
Hoff equation, lh equation, and Wilson model were used to
correlate the measured solubility data, respectively. To obtain
sufcient information for the selection of crystallization apparatus
and optimization of crystallization process, detailed and system-
atic thermodynamic properties of GN such as dissolution enthalpy,
DHsol, and dissolution entropy, DSsol, were calculated. Moreover,

http://dx.doi.org/10.1016/j.uid.2014.12.037
0378-3812/ 2014 Elsevier B.V. All rights reserved.
60 X. Zhang et al. / Fluid Phase Equilibria 388 (2015) 5965

The ideal solubility shown in Eq. (1) is dened by

Nomenclature


DH f DC p
lnxid
1  1 lnT m
RT m R
A, B, C Empirical constant in Eq. (4)
DCp
 
Difference in heat capacity of the solute between DC p T m DH f 1 DC p
solid and liquid  lnT (2)
R R T R
h, l Parameters in Eq. (9)
m1 Mass of the solute, g where T, Tm and R refer to the absolute solution temperature,
m2 Mass of the solvent, g melting temperature and gas constant, respectively. DHf is the
M1 Corresponding molar mass of the solute, g/mol molar fusion enthalpy of the pure solute at the melting point. DCp
M2 Corresponding molar mass of the solvent, g/mol refers to the difference between the molar heat capacity of the
MAPD Mean absolute percentage deviation crystalline form and the hypothetical supercooled liquid form at
N Number of experimental point their melting point.
R2 Coefcient of correlation As to the activity coefcient in Eq. (1), it is usually assumed to
R Gas constant, J/mol K follow a vant Hoff-like equation within a narrow temperature
T Absolute temperature, K range [8]:
Tm Melting temperature, K
DHf Enthalpy of fusion at melting point, kJ/mol H1
E;1
S
E;1
DHmix DSmix
lng 1  1  (3)
DHmix Enthalpy of mixing, kJ/mol RT R RT R
DHd Enthalpy of dissolution, kJ/mol
DH0app
d
Apparent standard dissolution enthalpy change,
E;1 E;1
where H1 and S1 represent the limiting partial excess enthalpy
E;1
kJ/mol and entropy, DHmix and DSmix are the mixing enthalpy and entropy.
H1 Limiting partial excess enthalpy, kJ/mol All these parameters are assumed to be temperature-independent.
DSf Entropy of fusion at melting point, J/mol K
DSmix Entropy of mixing, J/mol K 2.1. Apelblat equation
DSd Entropy of dissolution, J/mol K
DS0app
d
Apparent standard dissolution entropic change, J/ Substituting Eqs. (2) and (3) into Eq. (1) gives
mol K
E;1
S1 Limiting partial excess entropy, J/mol K lnx1 A B=T ClnT (4)
DG0app
d
Apparent standard dissolution Gibbs energy
where A, B and C are parameters. Referring to the equations
change, kJ/mol
mentioned previously, the above parameters can be written as
x1id Ideal solubility of the solute, mol/mol
x1 Experimental solubility of the solute, mol/mol DH f DC p DSmix
A  1 lnT m (5)
g1 Activity coefcient of the solute in solution RT m R R
l12  l11 Cross interaction energy parameter in Eq. (12)
l21  l22 Cross interaction energy parameter in Eq. (13)
n1 Molar volume of solute DC p T m DHf  DHmix
B  (6)
n2 Molar volume of solvent R R

the activity coefcients at innite dilution were estimated based
on the assumption of DCp = 0, which were then tted to a vant Hoff
like regular solution equation to calculate the mixing enthalpy,
DHm, and mixing entropy, DSm.
2. Theory
The following thermodynamic relationship was usually used to
describe the temperature dependence of mole fraction equilibrium
solubility of crystalline in liquid solvent [8]:
1  lng 1
lnx1 lnxid
id
where x1 and x1 denote the mole fraction solubility of the solute 1
and ideal mole fraction solubility of the solute, g1 represents
activity coefcient of the solute in solution.
O form:
NH
HO N DH d
O As shown in Eq. (8), the dissolution enthalpy, DHd, and dissolution
H 2N NH 2
Fig. 1. Molecular structure of guanidine nitrate.
DC p
C (7)
R
Eq. (4) is known as Apelblat equation, which was originally
proposed by Apelblat and Manzurola and is frequently used to
correlate solubility [9]. The parameters can be regressed from the
temperature dependence of solubility data. However, the activity
coefcient cannot be easily obtained due to the fact that the
differential heat capacity is difcult to be experimentally
measured or regressed from the values of C = DCp/R. The detailed
information concerning about Apelblat equation can be consulted
(1) from numbers of published papers [10,11].
2.2. Vant Hoff equation
In the case of non-ideal solution, vant Hoff equation was
usually applied to correlate the experimentally measured solubili-
ty data [12,13]. The vant Hoff equation can be expressed in the
DSd
lnx1  (8)
RT R
entropy, DSd, can be estimated by plotting the lnx1 versus
reciprocal of temperature (1/T).
 X. Zhang et al. / Fluid Phase Equilibria 388 (2015) 5965 61

2.3. lh equation X-ray diffraction (PXRD, D/MAX 2500), respectively. The mass
fraction purity is higher than 99% with the standard uncertainty of
lh equation can be written in the form [14] 0.005 and the corresponding structure is GN2 referring to

   literatures [17]. Organic solvents used for experiments including
1 1 1 1
1 exp lh  1 (9) methanol, ethanol, n-propanol and acetone are of analytical
x1 l T Tm
reagent grade, all supplied by Shanghai Chemical Reagent Co.,
Here, l and h are the two parameters. Among them, l represents China and used without further purication. Double-distilled
the mean association number of solute molecules, which reveals water was used in all experiments. Indium (supplied by
the departure from the ideal behavior of diffusion in solution PerkinElmer Ltd., purity higher than 99.999%) was used without
system. To h, it is the fusion enthalpy at melting temperature. further purication. The information of all materials used in this
work is listed in Table 1.
2.4. Wilson model
3.2. Procedure
As shown in Eq. (1), in order to calculate the real solubility of
crystalline in solvent, it is essential to estimate the values of ideal 3.2.1. DSC measurement
solubility and activity coefcient, respectively. Referring to Eq. (2), A DSC25-27 (module 910, NETZSCH, German) equipped with a
value of the ideal mole fraction solubility, x1id, can be estimated data station (Thermal Analyst 204, NETZSCH, German) under
with the knowledge of DHf, Tm and DCp. However, different from pressure p = 0.1 MPa was used to measure the values of melting
the melting temperature and fusion enthalpy, the differential temperature and fusion enthalpy of GN. Indium was used as
molar heat capacity for large amounts of substances cannot be reference for the calibration of DSC. The detailed calibration
easily determined. Given this situation, the contribution of it to the procedure can be found in literature [18]. After calibration, sample
ideal molar fraction solubility was usually ignored, that is DCp = 0 (about 5 mg) of pure GN was weighed with METTER AB265-S
was assumed [11,15]. Thus, Eq. (1) can be simplied to be balance with an accuracy of 0.01 mg and then placed in sealed
  aluminum pans (Aluminum capsules, 00026763, PerkinElmer
DH f 1 1
lnx1   lng 1 (10) model). During the scanning operation, high purity nitrogen gas
R Tm T was ushed throughout the DSC furnace to avoid condensation.
The sample was heated from 303.15 K to 503.15 K at xed heating
In a binary system, the activity coefcient can be estimated rate of 5 K/min.
based on Wilson model [16], which is given by
  3.2.2. Solubility measurement
L12 L21 A 100 mL double jacket vessel coupled with a thermostated oil
lng 1 lnx1 L12 x2 x2  (11)
x1 L12 x2 x2 L21 x1 bath (FT 32, Julabo Labortechnik, Gmbh, Germany) and magnetic
With agitator was used to perform the solubility measurement. The
  standard uncertainty of temperature is 0.05 K. Besides, to ensure
n2 l  l11
L12 exp  12 (12) the measurement accuracy, a condenser was installed on the top
n1 RT of the vessel to prevent the evaporation of the solvents. During
the experiments, excess amount of guanidine nitrate and
  corresponding solvent were transferred into the vessel and the
n1 l21  l22
L21 exp  (13) solution was then heated to the set temperature and maintained
n2 RT for at least 12 h. Thereafter, the stirring was stopped, and the
where l12  l11 and l21  l22 denote the cross interaction energy solution was kept still for 2 h to allow complete decomposition of
parameters, which are independent with temperature and ne crystals. After nishing the experiments, three samples were
composition. n1 and n2 refer to the molar volume of solute and carefully extracted from the upper clear solution with a 10 mL
solvent, respectively. suction pipet (a lter was xed on top to avoid the involvement of
ne crystals) and transferred into a weighted watch glass. Further,
3. Experimental the watch glass was reweighted to record the mass of solution and
then dried under vacuum circumstance at ambient temperature
3.1. Materials for 24 h. Finally, the dried watch glass was weighted again to
estimate the mass of residue solid (m1) and the evaporated solvent
Guanidine nitrate (supplied by Ningxia Beilite Chemical (m2). The mean values obtained from the three independent
Industry Co., Ltd., China) was recrystallized one time in aqueous measurements were used to calculate the mole fraction solubility
solution. Its purity and structure were analyzed by a HPLC x1 of guanidine nitrate in different solvents through the following
equipped with a UV detector (HP 1100 America) and Powder equation:

Table 1
Sample table.a

Chemical name Source Mass purity Purication method Analysis method

Guanidine nitrate Ningxia beilite chemical 0.99 Recrystallized HPLC
Methanol Shanghai chemical 0.99 None HPLC
Ethanol Shanghai chemical 0.99 None HPLC
n-propanol Shanghai chemical 0.99 None HPLC
Acetone Shanghai chemical 0.99 None HPLC
Indium PerkinElmer 0.99999 None ICP-MS
a
Standard uncertainty for mass fraction u is u(c) = 0.00001.
62 X. Zhang et al. / Fluid Phase Equilibria 388 (2015) 5965

0 6
Water
-5 5 Methanol
Heat Flow/W/g

-10 Ethanol
25.27 kJ/mol 4
-15 n-propanol

102x1
-20 3 Acetone
Water in Ref.[4]
-25
2
-30 487.17 K
1
-35
303.15 353.15 403.15 453.15 503.15
0
Temperature/K
270.15 280.15 290.15 300.15 310.15 320.15 330.15 340.15
Fig. 2. DSC curve of guanidine nitrate. Temperature/K

Fig. 4. Molar fraction solubility of guanidine nitrate in different solvents.

m1 =M1
x1 (14)
m1 =M1 m2 =M2

 1 K and DHf = 25.27  0.16 kJ/mol, where the uncertainty

where M1 and M2 are the molar masses of GN and corresponding
corresponded to a 95% condence interval. These results
solvents, respectively. The relative uncertainty of the experimental
are coincident with values reported in literatures (487 K and
solubility values is within 0.2%. Moreover, the equilibrated solid
25.6 kJ/mol) [19]. Moreover, the fusion entropy can be calculated
was extracted and characterized using PXRD to verify the form of
solid present at equilibrium. based on Eq. (15) to be DSf = 51.9 J/(mol K).

DH f
DS f (15)
4. Results and discussions Tm

4.1. Calorimetric measurement

The DSC curve (Fig. 2) obtained in our work revealed a small
peak at around 305 K. Szafranski et al. suggested that such a small
peak may be caused by the phase transition [19]. To verify the solid
form present at equilibrium, the equilibrated solids of GN obtained
under and above 305 K were characterized using PXRD. As shown
in Fig. 3, the positions of the main peaks, which reect the
symmetry and size of unit cell, are barely changed, indicating the
negligible inuence of temperature on the cell parameters.
As shown in Fig. 2, one can clearly notice that the values of
melting temperature and fusion enthalpy of GN are Tm = 487.17
323.35 K in methanol
Intensity
4.2. Solubility of guanidine nitrate
To validate the measurement reliability in this work, solubility
of GN in aqueous solution reported by Blair and Braham [4] was
taken as reference (shown in Fig. 4). It can be noticed that the
measured solubility data are in good agreement with those
obtained in References.
Fig. 4 and Table 2 show the measured mole fraction solubility
of GN in different solvents. It can be clearly noticed that, for all
cases, the solubility of GN increases with an increase in
temperature, indicating that dissolution of GN in all examined
solvents followed an endothermic process. Moreover, it can
also be seen that, from 278.05 K to 332.85 K, solubility of GN
in the anterior four solvents was: water > methanol > ethanol >
n-propanol. Referring to the physicochemical properties of
different solvents, the polarity of solvents was regarded as the
key factor to determine the solubility (the solvents polarity is in
the order: water > methanol > ethanol > n-propanol). With respect
to the solubility of GN in acetone, it increased abruptly and
exceeded continually the solubility of GN in the previous four
solvents. It indicated that the dissolution of GN in acetone is also
inuenced by other factors such as dipole moment (the solvents

293.25 K in methanol dipole moment is in the order: acetone > water > methanol >
ethanol > n-propanol).

323.25 K in water 4.3. Correlation of solubility data

As mentioned above, the small associated enthalpy change at

around 305 K will have neglected impact on the solubility. In this
section, the change in the solubility versus temperature slope was
288.25 K in water then ignored. Table 2 presents the mole fraction solubility of GN in
different solvents obtained experimentally and calculated using
Apelblat equation, vant Hoff equation, lh equation, and Wilson
5 10 15 20 25 30 35 40 45 50
model, respectively. The accuracy of calculated values based on
2-Theta
different correlation models were assessed by mean absolute
Fig. 3. XRD spectra for crystalline GN obtained under different conditions. percentage deviation (MAPD), which is dened by
 X. Zhang et al. / Fluid Phase Equilibria 388 (2015) 5965 63

Table 2
Mole fraction solubility (x) of guanidine nitrate in different solvents at temperature T and pressure p = 0.1 MPa, where xlh, xvant, xApel, and xwilson refer to the mole fraction
solubility calculated based on different models.a

Solvent Temperature (K) x  102 xlh  102 xvant  102 xApel  102 xwilson  102
Water 278.25 0.90 0.91 0.93 0.91 0.99
283.35 1.12 1.11 1.12 1.11 1.17
288.25 1.36 1.33 1.33 1.34 1.38
292.95 1.57 1.57 1.57 1.58 1.59
298.25 1.90 1.88 1.88 1.90 1.89
303.15 2.22 2.22 2.20 2.23 2.21
308.35 2.62 2.62 2.59 2.62 2.60
313.05 3.02 3.03 2.99 3.02 2.97
318.25 3.49 3.55 3.49 3.50 3.45
323.25 4.01 4.10 4.02 4.01 3.97
328.35 4.63 4.74 4.63 4.59 4.61
332.85 5.11 5.37 5.22 5.13 5.30

Methanol 278.25 0.63 0.63 0.63 0.63 0.65

283.25 0.75 0.76 0.76 0.76 0.77
288.25 0.92 0.90 0.90 0.90 0.91
293.25 1.07 1.07 1.07 1.07 1.07
298.35 1.26 1.26 1.26 1.27 1.27
303.15 1.48 1.47 1.47 1.47 1.47
308.35 1.74 1.73 1.72 1.73 1.71
313.15 1.98 2.00 1.99 1.99 1.99
318.25 2.27 2.31 2.30 2.30 2.30
323.35 2.64 2.67 2.65 2.65 2.69
328.05 3.05 3.04 3.01 3.01 3.05

Ethanol 278.05 0.30 0.31 0.31 0.31 0.31

283.15 0.37 0.37 0.37 0.37 0.38
288.35 0.43 0.44 0.44 0.44 0.44
293.15 0.51 0.52 0.51 0.51 0.52
298.25 0.62 0.61 0.60 0.60 0.61
303.25 0.70 0.71 0.70 0.70 0.71
308.25 0.81 0.83 0.82 0.82 0.82
313.05 0.94 0.95 0.94 0.94 0.94
318.05 1.08 1.10 1.08 1.08 1.08
323.25 1.24 1.26 1.24 1.24 1.25
328.35 1.43 1.45 1.42 1.42 1.43

n-propanol 278.25 0.09 0.09 0.09 0.09 0.12

283.25 0.13 0.12 0.13 0.12 0.14
288.25 0.17 0.17 0.17 0.17 0.18
293.15 0.20 0.22 0.22 0.22 0.23
298.35 0.29 0.29 0.29 0.29 0.29
303.15 0.41 0.37 0.37 0.37 0.38
308.35 0.48 0.48 0.48 0.48 0.47
313.15 0.61 0.60 0.61 0.61 0.60
318.25 0.77 0.77 0.77 0.77 0.76
323.15 0.92 0.96 0.96 0.96 0.94
328.05 1.20 1.19 1.20 1.18 1.22

Acetone 278.15 0.03 0.03 0.03 0.03 0.03

283.15 0.05 0.05 0.05 0.05 0.05
288.15 0.09 0.09 0.09 0.09 0.08
293.15 0.16 0.16 0.17 0.16 0.15
298.15 0.29 0.28 0.31 0.29 0.27
303.15 0.52 0.47 0.55 0.52 0.50
308.15 0.92 0.78 0.95 0.91 0.94
313.15 1.58 1.27 1.61 1.61 1.67
323.15 5.03 3.17 4.44 5.00 5.00
a
Standard uncertainties u are u(x) = 0.0000005, u(T) = 0.05 K and u(p) = 0.0025 MPa

!
1X N x1;i  xcal
1;i vant Hoff equation was used to predict the thermodynamic
MAPD j j  100 (16)
N i1 x1;i properties based on the measured mole fraction solubility data.

Here, N, x1,i and x1,ical refer to the number of experiment point,
measured and calculated solubility of GN, respectively. As listed in
Table 2, the overall calculated MAPDs for Apelblat equation, vant
Hoff equation, lh equation, and Wilson model are 1.01%, 2.01%,
3.15% and 3.47%, respectively. Although Apelblat equation gives the
best t, however, due to the limitation of Apelblat equation
mentioned above, thermodynamic information such as activity
coefcient lng 1 cannot easily been extracted. Given this situation,
4.4. Dissolution enthalpy and dissolution entropy
As mentioned in Eq. (8), dissolution enthalpy and dissolution
entropy of guanidine nitrate in different solvents can be calculated
from the slope and intercept of the plots of the logarithm of mole
fraction solubility versus reciprocal absolute temperature (Fig. 5).
In industrial, as one of the important physicochemical
properties, the slope of the solubility curve was usually taken as
64 X. Zhang et al. / Fluid Phase Equilibria 388 (2015) 5965

0 -2.5
Water
-2 Methanol -3
Ethanol

-4 n-propanol -3.5

lnx1
Acetone
lnx1

-4
-6
y = -2935.7x - 3.766
-4.5
-8

-5
-10 -0.0004 -0.0002 0 0.0002 0.0004
0.0029 0.0031 0.0033 0.0035 0.0037 0.0039
1/T-1/Thm
1/T
Fig. 6. Modied vant Hoff plot for experimental solubility of guanidine nitrate in
Fig. 5. Vant Hoff plot for guanidine nitrate in different solvents. aqueous solution.

the reference to select the apparatus of crystallization and its where n is the number of temperatures considered. In the present
operation method [20]. Namely, cooling crystallization was case, value of Thm is 304.72 K.
suggested in case of steep solubility curves. To the at solubility For electrolytes type one-one, if inter ionic interactions are not
curves, anti-solvent or evaporative crystallization were necessary. considered, the modied expression can be expressed by [22]
As shown in Fig. 5, the order of increasing rate of solubility of
 
guanidine nitrate in different solvents was acetone > n-propanol > @lnx1 DH0app
 d
(18)
water > methanol > ethanol. @1=T  1=T hm p 2R
Table 3 lists the calculated dissolution enthalpy and entropy. It
can be noticed that the dissolution of guanidine nitrate in all where DH0app
d
refers to the apparent standard dissolution
examined solvents within the experimental temperature range are enthalpy change. Based on Eq. (18), the modied vant Hoff plot
endothermic (DHd > 0), which is coincident with the results of for guanidine nitrate in aqueous solution is shown in Fig. 6.
increasing solubility with an increase on temperature. The As shown, the calculated data are in good agreement with those
endothermic process can be attributed to the stronger interactions obtained experimentally. Moreover, the apparent standard Gibbs
between guanidine nitrate molecules and solvent molecules than energy change, DG0app
d
, and entropic change, DS0app
d
, for solution
those between solvent molecules. Moreover, the positive values of process of electrolytes type oneone can be calculated by
dissolution enthalpy and entropy of guanidine nitrate in all
examined solvents indicated that the spontaneous process (DGd = DG0app
d
RT hm  intercept (19)
DHd  TDSd < 0) can only be realized by improving the values of
DSd. Namely, the dissolution process of guanidine nitrate in all
examined solvents belonged to entropy-driving process. DHd  DGd
DS0app
d
(20)
In addition, as an electrolyte drug, guanidine nitrate can T hm
dissociate in aqueous solution to generate two species, a With the two equations and the intercept obtained from Fig. 6
monovalent cation and a monovalent anion, respectively [21]. mentioned above, the apparent standard Gibbs energy change,
Under such situation, vant Hoff analysis was usually used to enthalpy change and entropic change of guanidine nitrate in
calculate the apparent standard enthalpy change of solution. aqueous solution 19.01  0.09 kJ/mol, 48.14 kJ  0.21 kJ/mol and
Pacheco and Martinez suggested that, in several thermodynamic 95.6  0.56 J/mol K can then be obtained.
treatments, some adjustments have been introduced in the vant With respect to the calculated dissolution enthalpy change, in
Hoff equation to reduce the propagation of errors and, therefore, to the case of ideal solution of unhydrated compounds, the following
separate the chemical effects from those due only to statistical relationship can be obtained [23],
treatments used when enthalpyentropy compensation analyses
are carried out [22]. On the basis, in our work, the mean harmonic DH d DHf
3 (21)
temperature (Thm) is used in vant Hoff analysis. Thm can be RT m RT m
calculated as
n However, to the real solution, the dissolution enthalpy can be
T hm Pn (17)
i1 1=T i expressed by

Table 3
Calculated DH and DS of guanidine nitrate in different solvents using the simplied assumption DCp = 0, where DHd, DSd, DHmix and DSmix are the dissolution enthalpy,
dissolution entropy, mixing enthalpy and mixing entropy, respectively. R2 refers to the corresponding correlation coefcient.

Solvents DHd (kJ/mol) DSd (J/mol K) R2 DHmix (kJ/mol) DSmix (J/mol K) R2

Water 24.41 48.79 0.999 1.79 6.08 0.932
Methanol 23.80 43.42 0.999 1.70 9.23 0.966
Ethanol 23.23 35.38 0.996 2.15 16.88 0.991
n-propanol 38.91 81.83 0.998 10.22 18.98 0.949
Acetone 85.18 237.70 0.998 59.87 185.55 0.990
 X. Zhang et al. / Fluid Phase Equilibria 388 (2015) 5965
Fig. 7. Vant Hoff plot of activity coefcient for guanidine nitrate in different
solvents using simplied assumption (DCp = 0).
DHd DHf DHmix (22)
Here, the mixing enthalpy DHmix, which dened as the enthalpy
change upon mixing of two liquids (fused solute and liquid
solvent), represents a measure of deviation of the real solubility of
a solutesolvent system from its ideal behavior. Referring to the
measured melting temperature, the values of DHd/RTm of
guanidine nitrate in different solvents can be calculated to be
6.03, 5.88, 5.74, 9.61 and 21.03, respectively. The deviation from
its ideal state (DHd/RTm  3) reveals the existence of strong
solutesolvent interactions [20].
4.5. Activity coefcient of guanidine nitrate
As the mole fraction solubility of guanidine nitrate in all
examined solvents is quite low (of the order of 103, presented in
Table 2), it is assumed that the last term in Eq. (1) represents the
innite dilution activity coefcient lng 11, which can be calculated
with knowledge of measured x1, DHf, Tm and DCp as mentioned in
Eqs. (1) and (2). However, considering the difculty of the
measurement of DCp, an assumption of DCp = 0 was usually made.
On this basis, the values of lng 11 were calculated and presented in
Fig. 7 by dots. Subsequently, based on Eq. (3), the values of lng 11
were tted to a vant Hoff like regular solution equation and the
results are shown in Fig. 7 by dashed line. The well linear
dependence of lng 11 against 1/T shown in Fig. 7 suggests the
feasibility of Eq. (3). Further, the slope and intercept were used to
estimate the values of DHmix and DSmix, and the results are listed in
Table 3. It can be noticed that the estimated values of DHmix are in
good agreement with the results obtained from Eq. (22).
5. Conclusions
Using gravimetric method, solubilities of guanidine nitrate in
ve different solvents including water, methanol, ethanol,
n-propanol and acetone have been experimentally determined
at temperature ranging from 278.05 K to 332.85 K at pressure
p = 0.1 MPa. Melting temperature, Tm, and molar fusion enthalpy,
DHf, of guanidine nitrate were determined using differential
65
scanning calorimetry. On this basis, Apelblat equation, vant
Hoff equation, lh equation, and Wilson model were used to
correlate the measured solubility data, respectively. The
results show that the solubility of guanidine nitrate in all
examined solvents increases with an increase on temperature.
The increasing rate is in the order: acetone > n-propanol > water >
methanol > ethanol. Subsequently, vant Hoff equation was applied
to calculate the dissolution enthalpy and entropy of guanidine
nitrate in different solvents, and modied vant Hoff equation was
used to calculate the apparent standard Gibbs energy change,
enthalpy change and entropic change of guanidine nitrate in
aqueous solution. The results show that the dissolution of
guanidine nitrate in all examined solvents was endothermic
and entropically favorable. Moreover, combining the measured
solubility data with calculated ideal solubility, activity coefcients
at innite dilution were estimated based on the assumption of
DCp = 0, which were then tted to a vant Hoff like regular solution
equation to calculate the mixing enthalpy, DHmix, and entropy,
DSmix, respectively.
Acknowledgments
We thank the nancial support by the National Natural Science
Foundation of China (NSFC, No. 21406071), the 111 Project of
Ministry of Education of China (B08021) and Ningxia Beilite
Chemical Industry Co., Ltd.
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