Fluid Phase Equilibria 405 (2015) 150156

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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

Excess molar enthalpies of the ternary mixture n-propanol + acetic

acid + water at 313.15 K and atmospheric pressure
Irina Letyanina, Nikita Tsvetov, Alexander Toikka*
Department of Chemical Thermodynamics and Kinetics, St. Petersburg State University, Universitetskiy Prospect 26, Peterhof, Saint Petersburg 198504, Russia

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 12 June 2015
Received in revised form 28 July 2015
Accepted 28 July 2015
Available online 30 July 2015

Excess molar enthalpies, HEm, for the ternary mixture n-propanol (n-PrOH) + acetic acid (AcOH) + water
(H2O) were measured at 313.15 K and atmospheric pressure using the Setaram C80 calorimeter. The data
for initial binary sub-systems were taken from the literature and correlated with the [137_TD$IF]RedlichKister
equation. The experimental results on the ternary system were tted by means of different variable
degree polynomials. Smooth representations of the results were used to construct constant excess molar
enthalpy contours on Roozeboom diagram. The capability of the NRTL model to predict excess molar
enthalpies for the ternary systems based on the data for the binary sub-systems was considered.
2015 Elsevier B.V. All rights reserved.

Keywords:
Excess molar enthalpies
n-Propanol
Acetic acid
Water

1. Introduction
Coupled processes of simultaneous chemical synthesis, separation of substances and purication of the products are
considered as the basis of energy- and resource-saving ecologically
pure chemical technologies. Complex approach to a problem of
investigation of this kind of processes leads to establishment of
new basic physical-chemical singularities. The experimental part
of the investigation includes the study of the multicomponent
reactive systems, for example, the system with n-propyl acetate
(n-PrOAc) synthesis, where coupled processes (chemical reaction
with simultaneous separation of reacting products) take place.
The solubility, chemical, vaporliquid and liquidliquid equilibria, phase transitions and critical state for n-propanol + acetic
acid + n-propyl acetate + water system are widely studied [17] at
different temperatures, e.g., 293.15, 303.15, 313.15, 353.15
383.15 K, while the thermodynamic properties of the mentioned
above quaternary system and involved ternary sub-systems are
studied considerably less. The investigation of the thermodynamic
properties, especially excess molar enthalpies, is quite important
to understand the molecular interactions in solutions, since they
provide direct information about the energetic effects arising
between the molecules present in the mixtures, which is essential
in developing solution theories and models.
The excess molar enthalpies of binary sub-systems of the
quaternary system n-PrOH + AcOH + n-PrOAc + H2O are quite

* Corresponding author.
E-mail addresses: alexander.toikka@chem.spbu.ru, a.toikka@spbu.ru (A. Toikka).
http://dx.doi.org/10.1016/j.uid.2015.07.053
0378-3812/ 2015 Elsevier B.V. All rights reserved.

sufciently studied [810]. The excess molar enthalpies data for

n-PrOH + AcOH, n-PrOH + n-PrOAc, and AcOH + n-PrOAc were
obtained in our scientic group at 313.15 K [11]. The experimental
data of ternary sub-system remain quite scarce. The only ternary
system n-PrOH + n-PrOAc + H2O was studied at 300.15, 323.15, and
348.15 K [12].
The present work reports the experimental excess molar
enthalpies for the ternary system n-PrOH + AcOH + H2O at
313.15 K and atmospheric pressure. The HEm experimental data
for appropriate binary systems are given in the literature
[11,1315]. The excess molar enthalpy data were tted using
RedlichKister, [138_TD$IF]Cibulka, Singh et al., NagataTamura and Morris
et al. equations. The data for binary systems were correlated with
the NRTL model, and obtained binary interaction parameters were
used to predict the excess molar enthalpies for the ternary
solution.
2. Experimental
2.1. Materials
N-propanol and acetic acid were supplied by Vekton (Russia).
The species used in the experiments were additionally puried by
distillation (the details were described previously in, for instance,
[2]). Water was bidistilled. The purity of the samples for calorimetric
experiments was checked with the gas chromatographmass
spectrometer GCMS-QP2010Ultra (Shimadzu, Japan), and also
conrmed by comparison of the measured refractive indexes, nD,
with the literature data [16]. The refractive indexes were determined with the IRF-454B2[139_TD$IF]M refractometer (KOMZ, Russia). The

I. Letyanina et al. / Fluid Phase Equilibria 405 (2015) 150156

purity of the compounds under study was estimated to be not less

than 0.996 for all substances. The physicalchemical properties of
pure substances were in agreement with the NIST Standard
Reference Database [17]. The specication of chemical samples is
given in Table 1.

151

mixtures with selected values of x1/x3 equal to 1, 3, and 1/3 were

prepared by weight. The excess molar enthalpies of the ternary
system HEm,123 were obtained from the relation
HEm;123 HEm;132 1  x2 HEm;13 ;

(1)
E

2.2. Apparatus
Excess molar enthalpies were measured with the C80 calorimeter
(Setaram Instrumentation, France, 2010). The calorimeter design is
based on the principles of Tian and Calvet [18]. Detailed description
of the calorimeter and used in the experiments membrane mixing
cells is given in [19,20] and in [11]. During the calorimetric
experiments the usual corrections on a rod movement and on the
heat of evaporation of the liquids were done. The procedure of
corrections is given in [11]. The standard atomic masses recommended by the IUPAC Commission [21] were used in the calculation
of all molar quantities. The necessary physical magnitudes were
taken in the NIST Standard Reference Database [17].
The apparatus and procedure were veried by measuring the
excess molar enthalpies of reference binary system hexane +
cyclohexane at 318.15 K. The results were found to differ by less
than 3% from those of literature data [22].
Thus the experimental set-up based on modern equipment
ensures a high delity of obtained experimental data.
2.3. Experimental procedure
The investigated mixtures were prepared by mass using a
Sartorius MSU225S analytical balance (precision
0.01 mg). The
uncertainties in the mole fractions were less than 0.0001. The
temperature was maintained constant at T = (313.15
0.05) K. The
excess molar enthalpy HEm,13+2 was determined for several
pseudo-binary mixtures in which component 2 (AcOH) was added
to binary mixture of component 1 (n-PrOH) and component 3
(H2O), having a xed mole ratio x1/x3. For this purpose, binary

where x2 represents the mole fraction of AcOH and H m,13 is the

excess molar enthalpy of the particular binary mixture.
In principal, in the ternary system n-PrOH + AcOH + H2O the
chemical reaction of esterication can occur during the measurements falsifying the calorimetric results. But in [11] we showed
that in the course of the calorimetric experiment the inuence of
the reaction heat ow rate was negligible.
3. Results and discussion
3.1. Binary systems
The involved in the ternary system of the present interest
binary mixtures were studied earlier. The excess molar enthalpies
of n-PrOH + AcOH system were reported in our previous manuscript [11]. The data were correlated using the RedlichKister
equation [23]:
N

HEm;ij xi xj S Ak xi  xj k ;

(2)

k0

where xi is the mole fraction of component i (n-PrOH), xj is the mole

fraction of component j (AcOH), Ak are the adjustable parameters, N
is the number of the parameters. The parameters of Eq. (2) for the
system n-PrOH + AcOH were tted in [11] and are given in Table 2.
The excess molar enthalpies of the system n-PrOH + H2O at
T = 313.15 K and atmospheric pressure were reported in [13]. The
obtained data are presented as Supplementary material,
Table S1 and in Fig. 1. The results of the investigation of the
excess molar enthalpies of the system AcOH + H2O at T = 313.15 K
and atmospheric pressure obtained by two groups of authors
[14,15] are given in Supplementary material, Table S2 and plotted

Table 1
The purities of the chemicals.
Component

CAS registry
number

Source

n-PrOH
AcOH
H2O

71-23-8
64-19-7
7732-18-5

Vekton 0.98
Vekton 0.98

Initial purity, mole

fraction

Purication
method

Purity, mole
fractiona

Analysis
method

Distillation
Distillation
Bidistillation

0.998
0.996
0.999

Gas chromatography, mass spectrometry and

refractometry

The uncertainty is estimated to be
0.002 mole fraction.

Table 2
Fitting parameters Ak and Cn for Eqs. (2) and (10) for binary and ternary mixtures of n-PrOH, AcOH and H2O, with average relative deviations, ARD, and standard deviations,
s (HEm).
Binary systems

Ternary system

Coeff.

n-PrOH (i) + AcOH (j)a

n-PrOH (i) + H2O (j)

AcOH (i) + H2O (j)

Coeff.

n-PrOH (1) + AcOH (2) + H2O (3)

A0
A1
A2
A3
A4
A5

1570.6
482.5
609.6
137.7

1531
1421
351.4
3062
2620
5674

1389
943.6
248.9
105.7
311.8
1092

C0
C1
C2
C3
C4
C5
C6
C7
C8
C9

7.476
21.48
23.75
22.93
30.09
47.92
11.85
13.32
31.18
41.49

ARD
s (HEm)

0.5%
1.3

8.0%
16.6

22.5%
14.2

Data are taken from [11].

0.9%
4.8

152

I. Letyanina et al. / Fluid Phase Equilibria 405 (2015) 150156

[(Fig._1)TD$IG]

where n is the number of experimental points. The results of data

correlation are presented in Tables S1 and S2 of Supplementary
materials and plotted in Figs. 1 and 2 correspondingly.

500

400

3.2. Ternary systems

300
HEm(J mol-1)

The measured values of excess molar enthalpies of the pseudobinary system, HEm,13+2, along with HEm,13 calculated via Eq. (2)
and obtained values of excess molar enthalpies of the ternary
system under study, HEm,123, at T = 313.15 K and atmospheric
pressure are presented in Table 3 and plotted in Fig. 3.
The values of HEm,123 were correlated using the following
equation:

200

100

0
0

0.2

0.4

0.6

0.8

HEm;123 HEm;bin DHEm;123 ;

-100

(5)

where
-200

HEm;bin HEm;12 HEm;23 HEm;31 ;

xn-PrOH

Fig. 1. Excess molar enthalpies, HEm, for the binary system n-PrOH + H2O at 313.15 K:
(*): experimental results [13]; solid line: [132_TD$IF]the RedlichKister equation; dashed line:
NRTL1 (parameters from Table 5); dotted line: NRTL2 (parameters from Table 6).

[(Fig._2)TD$IG]

(6)

known as the binary contribution to the excess ternary properties,

and HEm,ij are calculated by Eq. (2).
The last term, DHEm,123, represents the ternary contribution to
HEm,123. Several expressions were tested to correlate DHEm,123.
They were the Cibulka equation [24]:

DHEm;123 x1 x2 x3 C0 C1 x1 C2 x2 ;

(7)

350

the equation proposed by Singh et al. [25]:

DHEm;123 x1 x2 x3 C0 C1 x1 x2  x3 C 2 x21 x2  x3 2 ;

HEm(J mol-1)

250

(8)

the expression proposed by Nagata and Tamura [26]:

150

DHEm;123 x1 x2 x3 S C n 1  2x3 n RT;

n0

(9)

50

and the suggested one by Morris at al. [27]:[140_TD$IF]

0

0.2

0.4

-50

0.6

0.8

DHEm;123 x1 x2 x3 C0  C1 x1  C 2 x2  C 3 x 21  C 4 x 22  C 5 x1 x2

 C 6 x 31  C 7 x 32  C 8 x 21 x2  C 9 x1 x 22 RT

xAcOH

Fig. 2. Excess molar enthalpies, HEm, for the binary system AcOH + H2O at 313.15 K:
(^): experimental results [14]; (~): experimental results [15]; solid line: [13_TD$IF]the
RedlichKister equation; dashed line: NRTL1 (parameters from Table 5); dotted
line: NRTL2 (parameters from Table 6).

in Fig. 2. There are no any correlations of the experimental data in

[1315], so for subsequent calculations the RedlichKister Eq. (2)
was used to correlate the excess molar enthalpies of the systems
n-PrOH + H2O and AcOH + H2O.
The parameters were determined by the unweighted
least-square method. The quality of the t was assessed via the
standard deviation, given as
s
n
1
E
(3)
s Hm
S HE
 HEm;exp;i 2 ;
n  N i1 m;calc;i
where n is the number of experimental points, N is a total number
of coefcients.
The tting coefcients for the systems n-PrOH + H2O and
AcOH + H2O are summarized in Table 2 along with the standard
deviations, s (HEm), and average relative deviations, ARD:
E

ARD

100 n jHm;calc;i  Hm;exp;i j

S
;
n i1
jHEm;exp;i j

(4)

(10)

where C0, . . . ,Cn are the tting parameters, R is universal gas

constant, T is temperature. Table 4 shows the standard deviations
obtained, when the different correlation expressions were used. It
can be observed that just the equation of Morris et al. was capable
to correlate adequately the experimental results.
The tting parameters C0, . . . ,C9 were computed from the
unweighted least-squares method, they are presented in Table 2,
together with Ak parameters calculated for involved binary
mixtures and their corresponding standard deviations and the
average relative deviations.
The results of the correlation via the Morris et al. equation are
reported in Table 3.
The correlation was used to construct Figs. 35. Fig. 3 shows the
representation of the energetic effects of pseudo-binary system,
composed of the binary n-PrOH + H2O and AcOH, considering three
blocks of data at xed compositions for the specied binary
systems. Fig. 4 shows the isolines corresponding to the projections
of the variation in compositions on a triangular diagram for the
different constant values of excess molar enthalpies, isoenthalpic
lines.
The ternary excess molar enthalpy shows maximum value at
xn-PrOH = 0.214, xAcOH = 0.467,[14_TD$IF]xH2O = 0.319, HEm,123 = 505 J mol1,
and minimum value at xn-PrOH = 0.06, xH2O = [142_TD$IF]0.94, HEm,123 =
139 J mol1, corresponding to the binary system n-PrOH + H2O.

I. Letyanina et al. / Fluid Phase Equilibria 405 (2015) 150156

153

Table 3
Experimental excess molar enthalpies, HEm,13 + 2, at 313.15 K for the addition of AcOH (2) to (n-PrOH (1) + H2O (3)) to form (n-PrOH (1) + AcOH (2) + H2O (3)), and values of
HEm,123 calculated from Eq. (1), using the smooth representation of HEm,13 with the RedlichKister equation; correlated with the Morris et al. equation excess molar
enthalpies of the ternary system (n-PrOH (1) + AcOH (2) + H2O (3)), HEm,Morris; predicted, HEm,NRTL1, and correlated, HEm,NRTL2, with the NRTL model excess molar enthalpies
of the ternary system (n-PrOH (1) + AcOH (2) + H2O (3)).a
x1

x2

HEm,13+2
(J mol1)

HEm,13

HEm,123

HEm,Morris

HEm,NRTL1

HEm,NRTL2

x1/x3 = 1
0.5
0.2501
0.2503
0.2001
0.2397
0.2999
0.2000
0.2002
0.1508
0.1503
0.1001
0.1000
0.0517
0.0533
0.3500
0.3458
0.3983
0.399
0.452
0.0507
0.2995

0
0.5002
0.5002
0.5983
0.4813
0.4000
0.5997
0.6002
0.7017
0.7004
0.8027
0.7987
0.8969
0.8918
0.3009
0.2974
0.1995
0.1991
0.1000
0.8979
0.3994

0
312
309
338
317
262
330
331
337
335
299
302
192
216
227
231
186
180
116
197
269

383
383
383
382
354
383
383
383
387
384
388
381
384
377
383
377
381
381
384
380
382

383
503
500
491
501
491
483
484
452
450
376
379
232
256
495
496
491
485
461
236
499

383
497
497
485
502
499
485
484
447
448
370
375
241
250
497
497
487
487
458
240
499

395
396
396
392
395
391
392
392
369
370
310
313
203
211
386
386
385
385
388
202
391

396
493
493
475
496
498
474
474
431
432
351
355
224
233
493
493
477
477
447
223
498

[134_TD$IF]x1/x3 = 3
0.75
0.6722
0.6729
0.593
0.5979
0.5194
0.5202
0.4503
0.3752
0.2987
0.3017
0.2263
0.2249
0.1505
0.1487
0.075
0.0747
0.374
0.3725

0
0.0996
0.101
0.1978
0.1996
0.2983
0.2959
0.4013
0.4998
0.5969
0.6047
0.7066
0.7004
0.7996
0.7984
0.8975
0.8921
0.4978
0.4968

0
72
73
128
128
178
175
232
267
306
310
316
315
285
283
194
197
265
266

335
339
336
347
338
346
348
332
334
345
319
309
334
333
349
356
393
341
346

335
377
375
406
399
420
420
430
435
445
436
407
415
351
353
230
240
436
440

335
377
375
406
401
420
420
426
437
441
435
414
419
359
361
234
245
438
439

316
323
322
341
338
360
360
381
397
398
399
373
374
313
314
199
207
396
396

314
358
357
401
397
434
434
457
470
463
460
421
425
347
349
217
227
470
471

x1/x3 = 1/3
0.25
0.2244
0.2223
0.1994
0.1992
0.1719
0.1804
0.1512
0.1506
0.1247
0.1244
0.1065
0.0998
0.0735
0.0754
0.0487
0.0496
0.0261
0.0301

0
0.1
0.1015
0.1993
0.2006
0.2924
0.298
0.3997
0.402
0.4991
0.4993
0.5911
0.5973
0.7004
0.699
0.798
0.8031
0.9054
0.8982

0
193
194
287
288
359
355
392
393
412
410
415
421
402
400
347
344
214
223

145
144
142
144
144
136
155
148
148
144
143
159
142
139
146
133
148
179
201

145
323
321
402
403
455
464
481
481
484
481
480
478
444
444
374
373
231
243

145
321
321
409
410
447
456
477
478
488
488
485
482
445
446
370
365
225
238

143
255
254
315
316
347
353
376
376
392
392
396
396
378
378
324
319
196
207

145
321
321
407
408
444
453
469
469
473
473
467
464
431
432
362
357
216
228

0.90%

16.00%

3.70%

ARD
a

Standard uncertainties of temperature T and mole fraction x are as follows: u(T) = 0.05 K, u(x) = 0.0001, and the relative expanded standard uncertainty Ur for the excess
enthalpies is Ur(HEm) = 0.03 (95% level of condence).

154

I. Letyanina et al. / Fluid Phase Equilibria 405 (2015) 150156

[(Fig._3)TD$IG]

[(Fig._4)TD$IG]

600

HEm(J mol-1)

400

200

0
0

0.2

0.4

0.6

0.8

xAcOH
Fig. 3. Excess molar enthalpies, HEm, for the ternary mixtures n-PrOH + AcOH + H2O
at 313.15 K. (*) xn-PrOH/xH2O = 1; (~) xn-PrOH/xH2O = 3; (^) xn-PrOH/xH2O = 1/3. Solid
lines: calculated values using Morris et al. equation for ternary systems.

Fig. 5 represents the lines of the constant ternary contribution

DHEm,123 to the excess molar enthalpy. The maximum value

is 110 J mol1 at xn-PrOH = 0.172, xAcOH = 0.168, xH2O = 0.660, and

the minimum value of the ternary contribution is 76 J mol1 at
xn-PrOH = 0.496, xAcOH = 0.374, xH2O = 0.130.

Fig. 4. Contours for the constant values of HEm for the ternary mixtures
n-PrOH + AcOH + H2O at 313.15 K.
N

S t ji Gji xj

G
j1
Sx
RT i1 i N

(12)

S Gki xk

3.3. NRTL model

k1

The experimental HEm data were also used to test the suitability
of the NRTL (Non-Random Two Liquid) model to predict the excess
molar properties of the ternary mixture on basis of the parameters
obtained after the treatment of the data for involved binary
systems.
The excess enthalpy, which indicates the temperature dependence of the excess Gibbs free energy, can be got through the
GibbsHelmholz equation [28]:
!
@GE =T
HE
 2:
(11)
@T
T
p;xi

[ here N is the number of the components in the system, G[146_TD$IF]ji = exp

145_TD$IF]w
(ajit ji), t ji is the dimensionless interaction parameter, which is
related to the interaction energy parameters Dgji = gji  gii (gji = gij)
by [147_TD$IF]t ji = (gji  gii)/RT, the parameter aji is the non-randomness
parameter (aji = aij). Therefore, it is possible to obtain the
expression of the excess enthalpy for multicomponent mixtures:
!
N

HEm RT Si1 xi

Sj1 xj tji Gji S xk Gki aki tki aji tji 1

k1

!2

(13)

S Gki xk

i1

For binary mixtures Eq. (13) can be written as follows:

HEm RTx1 x2

The expression for the excess enthalpy can be derived by

substituting GE from the excess Gibbs free energy equation. The
NRTL equation of the excess Gibbs energy for multicomponent
solutions is following [29]:[143_TD$IF][

!
G21 t 21 x1 x2 G21  ax1 t 21 G12 t 12 x2 x1 G12  ax2 t 12


2

2
x1 x2 G2121
x2 x1 G1212

[148_TD$IF]The parameters for the system n-PrOH + AcOH were calculated

earlier [11] and are presented in Table 5. The parameters for the
systems n-PrOH + H2O and AcOH + H2O were optimally tted by
minimizing the objective function, OF, between the calculated and
the experimentally determined HEm:
n

HEm;calc;i  HEm;exp;i

i1

HEm;exp;i

OF S
Table 4
Comparison of the standard deviations, s (HEm), obtained
with correlation equations applied.
Equation

s (HEm)

Cibulka [24]
Singh et al. [25]
Nagata and Tamura [26]
Morris et al. [27]

9.2
30.0
14.6
4.8

(14)

!2
;

(15)

where the summation is over all ith data point.

The parameters of the NRTL equation for the systems
n-PrOH + H2O and AcOH + H2O are listed in Table 5 together with
ARD (Eq. (4)). The calculated parameters were used to calculate
the excess molar enthalpies, HEm,NRTL1, they are given in
Tables S1 and S2 of Supplementary material and plotted in
Figs. 1 and 2 (dashed lines) correspondingly. Note that the

I. Letyanina et al. / Fluid Phase Equilibria 405 (2015) 150156

[(Fig._5)TD$IG]

155

S2 of Supplementary material (column HEm,NRTL2) and plotted in

Figs. 1 and 2 (dotted lines). The correlated through new set of
binary interaction parameters excess enthalpies for the ternary
system under study are given in Table 3 (column HEm,NRTL2). As
can be seen, the ARD between the experimental and correlated
values became slightly higher for the binary systems (Table 6), and
considerably lower for the ternary system (Table 3). Therefore, the
prediction of the excess molar properties of the ternary systems
based on the data of involved binary systems using the NRTL model
can lead to an estimated error 1020%.
4. Conclusions

Fig. 5. Lines of the constant ternary contribution DHEm,123 to the excess molar
enthalpy HEm for the ternary mixtures n-PrOH + AcOH + H2O at 313.15 K.

Table 5
Binary interaction parameters in the NRTL Model calculated from the binary
systems.
j

[135_TD$IF]aji

Dgji

Dgij

ARD/%

n-PrOHa
n-PrOH
AcOH

AcOHa
H2O
H2O

0.15a
0.592
0.0263

1141.02a
960.4
16761

3628.34a
6355
11264

7.9a
7.7
8.2

Data are taken from [11].

concentration dependence of excess molar enthalpy for the system

AcOH + H2O is difcult to t, and the values of |HEm| are less than
10 J mol1 over the AcOH concentration range xAcOH < 0.1, therefore
the experimental values of excess molar enthalpies lied at
xAcOH < 0.1 were not considered in the NRTL treatment of the
system AcOH + H2O.
The obtained binary interaction parameters (Table 5) and
Eq. (13) were used to predict excess molar enthalpies for the
ternary system n-PrOH + AcOH + H2O. The results of prediction are
listed in Table 3 (column HEm,NRTL1). The average relative
deviation is 16.0%. Principally, this result may be regarded as
satisfactory; thus the NRTL model can be used to predict excess
molar properties of ternary systems based on the data of involved
binary sub-systems.
The Eq. (13) was also used to correlate 4 sets of experimental
data (3 binary and 1 ternary systems) and to obtain new NRTL
parameters for pairs n-PrOH + AcOH, n-PrOH + H2O, and AcOH +
H2O. The parameters were optimally tted by minimizing the
objective function OF (Eq. (15)). New NRTL parameters are
presented in Table 6. The correlated through the Eq. (13) and
new set of binary interaction parameters excess enthalpies for the
systems n-PrOH + H2O and AcOH + H2O are listed in Tables S1 and

Table 6
Binary interaction parameters in the NRTL Model calculated from the binary and
ternary systems.
[136_TD$IF]j

aji

Dgji

Dgij

ARD/%

n-PrOH
n-PrOH
AcOH

AcOH
H2O
H2O

0.0979
0.588
0.0301

2076.6
877.85
16782

4873.9
6614.2
10816

8.1
8.2
10.1

The excess enthalpies of the ternary solution n-PrOH + AcOH +

H2O at T = 313.15 K were determined by using the C80 Calvet
calorimeter (Setaram Instrumentation). The system shows mostly
endothermic HEm behavior at the measured temperature. The
measured excess molar enthalpy data were correlated with the
Morris et al. equation for ternary systems. The ARD was 0.9%. The
obtained data were also predicted and correlated with the NRTL
model. The ARD between the experimental excess enthalpies and
the predicted ones is 16.0%. The ARD between the experimental
excess enthalpies and the correlated ones with the NRTL model is [149_TD$IF]
3.7%. This indicates that the NRTL model can predict excess
enthalpies of the ternary solutions with an error 1020%.
Acknowledgments
Irina Letyanina acknowledges St. Petersburg State University for
a Research Fellow grant (12.50.1564.2013). Authors are also
grateful to Russian Foundation for Basic Research (grant 15-0302131). The purity investigation of the samples under study was
performed at the Center for Chemical Analysis and Materials
Research of Research Park of St. Petersburg State University. The
calorimetric investigations were carried out using the equipment
of the Center of Thermal Analysis and Calorimetry of St. Petersburg
State University.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.uid.2015.07.053.
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