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Fluid Phase Equilibria 260 (2007) 335342

Apparent molar volume, isentropic compressibility and conductivity of


di-sodium hydrogen phosphate in water and in
aqueous solutions of 1-propanol
Rahmat Sadeghi , Roushan Khoshnavazi, Hana Parhizkar
Department of Chemistry, University of Kurdistan, Sanandaj, Iran
Received 24 June 2007; received in revised form 23 July 2007; accepted 23 July 2007
Available online 27 July 2007

Abstract
Precise measurements on the density and sound velocity of solutions of di-sodium hydrogen phosphate in 1-propanol + water mixed-solvent
media with alcohol mass fractions of 0.00, 0.05, 0.10 and 0.15 are reported in the 283.15303.15 K temperature range at 5 K intervals. Electrical
conductivity and refractive index of the solutions are studied at 298.15 K. From the experimental density and sound velocity data, the apparent molar
volume and isentropic compressibility values of di-sodium hydrogen phosphate have been evaluated. The results show a positive transfer volume
of di-sodium hydrogen phosphate from an aqueous 1-propanol solution to a more concentrated 1-propanol solution. The apparent molar isentropic
compression of di-sodium hydrogen phosphate in aqueous 1-propanol solutions is negative and it increases with increasing the concentration of
1-propanol and temperature. The negative values of apparent molar isentropic compression imply that the water molecules around the di-sodium
hydrogen phosphate are less compressible than the water molecules in the bulk solutions. The effects of the electrolyte concentration and relative
permittivity of the medium on the molar conductivity were also investigated.
2007 Elsevier B.V. All rights reserved.
Keywords: Apparent molar volume; Isentropic compressibility; Conductivity; Refractive index; Di-sodium hydrogen phosphate; 1-Propanol

1. Introduction
The salt in mixed solvent plays an important role in scientific research and the chemical industry, such as recycling of
organic solvent in a mixed-solvent system, design of extractors,
separation of mixtures, biological process, etc. Thermodynamic
properties of mixed-solvent electrolyte systems are necessary
for a fundamental understanding of the phase-forming ability
and also for the development of theoretical models for design
and simulation of these processes. Studies on the volumetric
and conductometric studies of electrolytes in different mixedsolvent systems are of great importance to obtain information as
to the solvation and association behavior of ions in solutions.
In this paper, we present our results on density and sound
velocity measurements at various temperatures and conductometric and refractive index measurements, at 298.15 K, of

Corresponding author. Tel.: +98 871 6624133; fax: +98 871 6624133.
E-mail addresses: rahsadeghi@yahoo.com,
rsadeghi@uok.ac.ir (R. Sadeghi).
0378-3812/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2007.07.066

di-sodium hydrogen phosphate in 1-propanol + water mixedsolvent media containing 0.00, 0.05, 0.10 and 0.15 mass
fractions of 1-propanol. Although there are some very limited
reports on the density [13] and electrical conductivity [4,5]
of binary aqueous di-sodium hydrogen phosphate (Na2 HPO4 )
solutions, however there are no any experimental data on the
ultrasonic velocity of aqueous solutions of Na2 HPO4 in the literature. Furthermore, volumetric, isentropic compressibility and
conductometric behavior of Na2 HPO4 in aqueous 1-propanol
solutions is scarce.
2. Experimental
2.1. Materials
1-Propanol was obtained from Merck (GR, min 99.5%). Disodium hydrogen phosphate (Na2 HPO4 ) was obtained from
Merck (GR, min 99.5%). The alcohol and salt were used without further purification, and double distilled, deionized water
was used.

336

R. Sadeghi et al. / Fluid Phase Equilibria 260 (2007) 335342

2.2. Apparatus and procedures


All the solutions were prepared by mass on a Sartorius
CP124S balance precise to within 0.0001 g. The density and
sound velocity of the mixtures were measured at different temperatures with a digital vibrating-tube analyzer (Anton Paar
DSA 5000, Austria) with proportional temperature control that
kept the samples at working temperature within 103 K. The
apparatus was calibrated with double distilled deionized, and
degassed water, and dry air at atmospheric pressure according
to the instrument catalog. Densities and ultrasonic velocities can
be measured to 106 g cm3 and 102 m s1 , respectively,
under the most favorable conditions. The uncertainties of density
and ultrasonic velocity measurements were 3 106 g cm3
and 101 m s1 , respectively. The specific conductivities of
the solutions were measured using a digital conductivity meter,
inoLab Cond 720 WTW (Germany). The conductivity measurement accuracy is 0.1%. A dip-type immersion conductance cell,
with a cell constant k = 0.475 1.5% cm1 , was used.
3. Results and discussion
Experimental data of density (d) and sound velocity (u) for
various Na2 HPO4 solutions determined at T = (283.15, 288.15,
293.15, 298.15 and 303.15) K are given in Table 1 . Experimental data of molar conductivity () and refractive index (n) for
investigated systems at T = 298.15 K are given in Table 2. The
dependence of density and ultrasonic velocity on temperature
and concentration has been calculated by means of the following
equation:


P2 + P3 ws
F = P1 exp
(1)
P4 wa + P 5 T + P 6
where ws and wa are the mass fraction of the salt and alcohol, respectively, T the absolute temperature, and P1 , P2 , P3 ,
P4 , P5 and P6 the curve-fit coefficients. The curve-fit coefficients P1 , P2 , P3 , P4 , P5 and P6 for density are 0.73045,
326.94027, 996.41225, 437.91214, 0.99749 and 756.66332,
respectively, and for sound velocity are 1742.5276, 0.0608,
0.3202, 1.9203, 0.0046 and 0.9741, respectively. Also,
the overall absolute relative deviation (ARD) for density and
sound velocity of investigated systems are 5.88 104 and 0.21,
respectively. On the basis of the obtained ARD values, we conclude that Eq. (1) can be successfully used for the correlation
of the investigated physical properties at different temperature
and concentrations. In fact, for each property, one set of parameters successfully has been used to correlate all experimental data
measured at five temperatures and four alcohol mass fractions.
The apparent molar volumes of the Na2 HPO4 , V , in aqueous
1-propanol solutions were computed from the density of the
solution by using the following equation:
V =

1000(d0 d) Ms
+
ms dd0
d

(2)

where Ms is the molar mass of the salt, d and d0 are the densities
of the solution and solvent, respectively. For ternary systems,
the 1-propanol + water is considered as the solvent. In Fig. 1,

comparison of the apparent molar volume of Na2 HPO4 measured in this work with those taken from Refs. [2,3] have been
made at T = 298.15 K. That is to say, the precisions of the densimeters used in Refs. [2,3] were reported to be 1 104 and
1 105 g cm3 , respectively.
In Fig. 2 the values of V are plotted as a function of salt
concentration at various 1-propanol concentration at 298.15 K.
The similar behavior was obtained for other temperatures. From
Fig. 2, it can be seen that the apparent molar volumes of
Na2 HPO4 in pure water increased along with an increase in the
salt molality. For the low concentrations of Na2 HPO4 , the small
volume of the salt is attributed to the strong attractive interactions
due to the hydration of ions. By increasing the salt concentration,
the ionion interaction increases and the positive initial slope
of V against salt concentration is attributed to these interactions. In the electrolyte solutions, the solutesolute interactions
are characterized by positive slopes of V versus concentration
plots [1]. This is attributed to the phenomenon, described in
terms of destructive overlap of co-spheres [6,7], resulting in a
net decrease of solvation, thereby increasing the solute volume.
Fig. 2 shows a positive transfer volume of Na2 HPO4 from an
aqueous solution to an aqueous 1-propanol solution. This indicates that the Na2 HPO4 ions in aqueous 1-propanol solutions
are larger than those in aqueous solutions and the value of V
increases as the concentration of 1-propanol increases. In Fact,
ternary aqueous solution of alcohols and electrolytes separates
into an alcohol-rich phase and a salt-rich phase over part of the
composition space [8,9]. The formation of aqueous two-phase
systems clearly indicates the mutual exclusion of the ions and
the alcohol and their high affinity for the water. It is possible that
even in homogeneous systems (below the phase boundary) the
ions are excluded from the near surface region of the alcohol in
solution. With increase in the concentration of the alcohol or the
salt, the extent of exclusion will increase. Ultimately, the system
could reach a state where, for entropic reasons, phase formation
would become favorable.
The larger values of V for Na2 HPO4 in higher concentration of 1-propanol are attributed to the two factors: (1) The
strong attractive interactions due to the hydrogen-bond formations between 1-propanol and water molecule induce the
dehydration of ions and therefore increase the V . (2) A particular complication, which occurs in many non-aqueous solvents
whose relative permittivities are significantly lower than that of
water, is the effect of ion pairing. The relative permittivity of
water and 1-propanol at 298.15 K is 78.30 and 20.34, respectively. The ion-pairing effect arises because in general the sum
of the molar volume values of free (dissociated) ions is smaller
than that of their ion pair due to the greater electrostrictive effect
of the ions on the solvent molecules [10].
From Fig. 2, we note that at each temperature, the values
of V of Na2 HPO4 in aqueous 1-propanol solutions show a
minimum. This minimum becomes more distinct and shows a
tendency to shift to a higher salt concentration as the concentration of 1-propanol increases. In fact, for low concentration
of the salt, the apparent molar volume of Na2 HPO4 in aqueous 1-propanol solutions decreases with the increase in the salt
molality, which is completely opposite to that for high concen-

R. Sadeghi et al. / Fluid Phase Equilibria 260 (2007) 335342

337

Table 1
Experimental density d (g cm3 ) and ultrasonic velocity u (m s1 ) of Na2 HPO4 in aqueous 1-propanol solutions at different temperatures
ms (mol kg1 )

T = 283.15 K

T = 288.15 K

T = 293.15 K

T = 298.15 K

T = 303.15 K

0.999699
1.000712
1.001193
1.001724
1.004226
1.005137
1.005499
1.006698
1.008573
1.010028
1.014532
1.024575
1.033102
1.033676
1.039478
1.042770
1.049547
1.059187
1.080356
1.100260

1447.59
1449.31
1450.01
1450.78
1454.15
1455.54
1456.03
1457.71
1460.29
1462.27
1468.37
1481.83
1493.18
1493.84
1501.63
1506.00
1514.92
1527.68
1555.68
1582.33

0.999099
1.000095
1.000568
1.001093
1.003557
1.004456
1.004814
1.005997
1.007845
1.009283
1.013727
1.023644
1.032074
1.032641
1.038379
1.041636
1.048344
1.057888
1.078873
1.098617

1466.25
1467.58
1468.27
1469.00
1472.30
1473.60
1474.06
1475.69
1478.18
1480.11
1486.02
1499.10
1510.08
1510.75
1518.31
1522.56
1531.24
1543.61
1570.83
1596.72

0.998203
0.999185
0.999653
1.000170
1.002606
1.003494
1.003847
1.005015
1.006844
1.008263
1.012655
1.022468
1.030813
1.031373
1.037057
1.040282
1.046928
1.056392
1.077209
1.096813

1482.66
1483.79
1484.45
1485.15
1488.36
1489.63
1490.07
1491.67
1494.08
1495.93
1501.68
1514.31
1525.02
1525.69
1533.03
1537.11
1545.52
1557.60
1584.03
1609.14

0.997043
0.998012
0.998476
0.998988
1.001399
1.002280
1.002628
1.003785
1.005595
1.007000
1.011349
1.021069
1.029340
1.029896
1.035533
1.038731
1.045323
1.054714
1.075384
1.094864

1497.00
1498.03
1498.65
1499.33
1502.47
1503.67
1504.09
1505.64
1507.97
1509.77
1515.33
1527.66
1538.02
1538.64
1545.81
1549.78
1557.99
1569.69
1595.38
1619.77

0.995645
0.996606
0.997065
0.997573
0.999963
1.000835
1.001179
1.002327
1.004121
1.005515
1.009828
1.019469
1.027674
1.028225
1.033820
1.036994
1.043542
1.052868
1.073410
1.092776

1509.44
1510.37
1511.00
1511.65
1514.71
1515.90
1516.30
1517.80
1520.08
1521.84
1527.25
1539.18
1549.25
1549.90
1556.85
1560.73
1568.70
1580.06
1605.08
1628.76

In aqueous solutions with wa = 0.05


0.0000
0.992444
1501.22
0.0035
0.992926
1502.06
0.0104
0.993900
1503.41
0.0212
0.995393
1505.21
0.0248
0.995875
1505.92
0.0285
0.996385
1506.57
0.0391
0.997848
1508.44
0.0518
0.999598
1510.92
0.0640
1.001258
1512.90
0.0715
1.002273
1514.18
0.1060
1.006936
1520.16
0.1425
1.011796
1526.34
0.1691
1.015339
1530.83
0.2116
1.020953
1537.70
0.2556
1.026587
1544.49
0.2935
1.031508
1550.51
0.3657
1.040663
1561.39
0.4448
1.050461
1572.84

0.991727
0.992202
0.993163
0.994635
0.995111
0.995615
0.997059
0.998784
1.000426
1.001426
1.006031
1.010833
1.014332
1.019886
1.025456
1.030332
1.039400
1.049113

1514.54
1515.39
1516.71
1518.46
1519.14
1519.79
1521.61
1524.05
1525.95
1527.21
1533.00
1538.95
1543.38
1550.10
1556.70
1562.62
1573.23
1584.44

0.990715
0.991182
0.992130
0.993586
0.994054
0.994553
0.995982
0.997687
0.999308
1.000299
1.004854
1.009605
1.013072
1.018569
1.024089
1.028921
1.037910
1.047547

1526.24
1527.08
1528.34
1530.01
1530.69
1531.31
1533.08
1535.45
1537.28
1538.48
1544.12
1549.91
1554.25
1560.81
1567.21
1572.98
1583.35
1594.30

0.989431
0.989894
0.990833
0.992275
0.992739
0.993232
0.994647
0.996335
0.997941
0.998923
1.003433
1.008142
1.011577
1.017027
1.022502
1.027296
1.036218
1.045786

1536.25
1537.05
1538.29
1539.91
1540.54
1541.15
1542.86
1545.18
1546.94
1548.14
1553.62
1559.28
1563.47
1569.83
1576.05
1581.69
1591.79
1602.47

0.987905
0.988363
0.989293
0.990723
0.991183
0.991673
0.993077
0.994751
0.996342
0.997315
1.001792
1.006461
1.009869
1.015280
1.020714
1.025474
1.034336
1.043844

1544.70
1545.46
1546.66
1548.26
1548.84
1549.44
1551.11
1553.37
1555.08
1556.23
1561.56
1567.07
1571.14
1577.31
1583.37
1588.87
1598.71
1609.10

In aqueous solutions with wa = 0.10


0.0000
0.987274
1547.38
0.0070
0.988144
1549.52
0.0103
0.988600
1550.05
0.0140
0.989084
1550.75
0.0232
0.990392
1551.89
0.0352
0.992011
1554.01
0.0354
0.992036
1554.22
0.0498
0.993970
1556.63
0.0640
0.995867
1559.00
0.0639
0.995880
1558.83
0.0858
0.998808
1562.28
0.1141
1.002546
1566.67
0.1345
1.005144
1569.45
0.1432
1.006284
1570.84
0.1445
1.006378
1570.92
0.1695
1.009787
1574.90
0.2028
1.014025
1579.44
0.2336
1.017992
1583.87
0.2822
1.024137
1590.29
0.3347
1.030636
1597.07

0.986285
0.987136
0.987585
0.988062
0.989357
0.990952
0.990974
0.992887
0.994757
0.994772
0.997663
1.001357
1.003928
1.005051
1.005146
1.008516
1.012706
1.016635
1.022717
1.029158

1555.57
1557.69
1558.17
1558.87
1559.93
1562.01
1562.15
1564.59
1566.88
1566.74
1570.09
1574.36
1577.08
1578.42
1578.51
1582.37
1586.69
1591.11
1597.39
1603.97

0.985011
0.985841
0.986286
0.986760
0.988041
0.989616
0.989637
0.991528
0.993377
0.993394
0.996256
0.999907
1.002453
1.003567
1.003659
1.006993
1.011144
1.015038
1.021064
1.027450

1562.42
1564.47
1564.94
1565.61
1566.68
1568.67
1568.76
1571.16
1573.36
1573.25
1576.50
1580.64
1583.30
1584.58
1584.68
1588.39
1592.60
1596.88
1602.99
1609.36

0.983475
0.984288
0.984729
0.985198
0.986469
0.988030
0.988048
0.989920
0.991752
0.991769
0.994603
0.998222
1.000746
1.001848
1.001941
1.005246
1.009362
1.013220
1.019198
1.025535

1567.98
1569.86
1570.33
1570.98
1572.07
1573.99
1574.06
1576.36
1578.48
1578.39
1581.52
1585.52
1588.12
1589.36
1589.46
1593.04
1597.11
1601.24
1607.15
1613.30

0.981701
0.982501
0.982938
0.983403
0.984666
0.986213
0.986230
0.988086
0.989901
0.989920
0.992732
0.996320
0.998825
0.999918
1.000010
1.003287
1.007371
1.011200
1.017139
1.023432

1572.23
1573.95
1574.41
1575.03
1576.14
1577.98
1578.05
1580.24
1582.29
1582.22
1585.25
1589.11
1591.63
1592.83
1592.93
1596.36
1600.31
1604.27
1609.98
1615.89

In water
0.0000
0.0070
0.0104
0.0141
0.0320
0.0386
0.0411
0.0496
0.0632
0.0737
0.1066
0.1810
0.2454
0.2498
0.2939
0.3192
0.3723
0.4483
0.6185
0.7841

338

R. Sadeghi et al. / Fluid Phase Equilibria 260 (2007) 335342

Table 1 ( Continued )
ms (mol kg1 )

T = 283.15 K

T = 288.15 K

T = 293.15 K

T = 298.15 K

T = 303.15 K

1.042009
1.050382

1608.35
1616.37

1.040430
1.048735

1614.97
1622.79

1.038634
1.046877

1620.02
1627.58

1.036640
1.044824

1623.57
1630.84

1.034462
1.042594

1625.78
1632.72

In aqueous solutions with wa = 0.15


0.0000
0.983045
1584.05
0.0070
0.983915
1585.84
0.0113
0.984473
1586.44
0.0141
0.984833
1586.81
0.0278
0.986697
1588.83
0.0351
0.987673
1589.71
0.0495
0.989584
1591.69
0.0642
0.991530
1593.66
0.0849
0.994210
1596.15
0.1139
0.998021
1599.82
0.1403
1.001384
1602.97
0.1722
1.005459
1606.48
0.2021
1.009220
1609.70
0.2471
1.014759
1614.08
0.2948
1.020564
1618.43
0.3319
1.025135
1621.46
0.3686
1.029478
1624.01

0.981663
0.982507
0.983059
0.983414
0.985252
0.986215
0.988103
0.990024
0.992670
0.996436
0.999757
1.003786
1.007505
1.012979
1.018723
1.023247
1.027550

1586.55
1588.27
1588.84
1589.20
1591.13
1591.89
1593.88
1595.75
1598.00
1601.62
1604.59
1607.87
1610.95
1615.01
1619.03
1621.79
1624.16

0.980011
0.980834
0.981380
0.981732
0.983546
0.984498
0.986368
0.988263
0.990881
0.994606
0.997891
1.001879
1.005559
1.010976
1.016664
1.021143
1.025411

1588.09
1589.63
1590.17
1590.51
1592.34
1593.09
1594.97
1596.74
1598.90
1602.29
1605.06
1608.17
1611.01
1614.75
1618.42
1620.91
1623.14

0.978117
0.978922
0.979461
0.979810
0.981606
0.982548
0.984400
0.986275
0.988867
0.992557
0.995808
0.999757
1.003403
1.008774
1.014408
1.018852
1.023088

1588.60
1589.92
1590.44
1590.78
1592.50
1593.24
1594.99
1596.67
1598.76
1601.89
1604.47
1607.41
1610.02
1613.45
1616.79
1619.05
1621.16

0.976004
0.976790
0.977324
0.977672
0.979450
0.980383
0.982222
0.984080
0.986648
0.990309
0.993530
0.997448
1.001065
1.006390
1.011981
1.016391
1.020601

1588.12
1589.26
1589.76
1590.07
1591.69
1592.44
1594.06
1595.63
1597.65
1600.56
1602.95
1605.75
1608.15
1611.29
1614.36
1616.42
1618.43

0.4278
0.4976

trations of Na2 HPO4 . The measured apparent molar volume can


be considered to be the sum of the geometric volume of the
solute and changes in the solvent due to its interaction with the
solute. When two charged centers are not separated by a dis then their hydration co-sphere overlaps which
tance of 34 A,
results in a decrease in electrostriction [11]. The overlap of the
co-sphere of the two ionic species shows an increase in volume
whereas the overlap of the ion-hydrophobic group results in a
decrease in volume. For low concentration of the salt, decrease in
the apparent molar volume of Na2 HPO4 in aqueous 1-propanol
solutions by increasing the salt molality, is attributed to the overlap of the ion-hydrophobic group of 1-propnaol. But, for high
concentration of the salt, increase in the apparent molar volume
of Na2 HPO4 in aqueous 1-propanol solutions by increasing the

Fig. 1. Plot of apparent molar volume of Na2 HPO4 , V , in water against molality
of the salt, ms , at 298.15 K: , this work; , Ref. [2]; , Ref. [3].

salt molality, is attributed to the overlap of the co-sphere of the


two ionic species and also ion-pairing effect.
Based on the sound velocity and density values, the isentropic compressibility, (kPa1 ) values were calculated for the
investigated mixtures from LaplaceNewtons equation:
= d 1 u2

(3)

where u (m s1 ) is sound velocity. The isentropic compressibility


of all the solutions decreases with increasing salt concentration.
In Figs. 36, the isentropic compressibilities are plotted versus
the molality of Na2 HPO4 at different temperatures and alcohol
concentrations. From these figures, we note that at each working

Fig. 2. Plot of apparent molar volume of Na2 HPO4 , V , against molality of the
salt, ms , at T = 298.15 K: , in water; , in aqueous 1-propanol solution with
wa = 0.05; , in aqueous 1-propanol solution with wa = 0.10; , in aqueous
1-propanol solution with wa = 0.15.

1.3447
1.3448
1.3450
1.3452
1.3458
1.3464
1.3481
122.88
114.31
108.72
104.28
94.40
85.46
72.53
0.0049
0.0107
0.0155
0.0213
0.0428
0.0704
0.1436
1.3409
1.3411
1.3413
1.3415
1.3420
1.3428
1.3445
1.3471
1.3484

m (S cm2 mol1 )
ms (mol kg1 )

0.0049
0.0106
0.0155
0.0212
0.0422
0.0712
0.1402
0.2476
0.3073
1.3371
1.3373
1.3375
1.3376
1.3381
1.3388
1.3407
1.3433
1.3447
1.3461
1.3478

m
ms
n

140.20
130.12
126.34
121.35
109.13
96.92
86.28
74.66
70.09

mol1 )
(S cm2
(mol kg1 )

165.01
149.32
145.66
141.66
126.62
116.29
101.90
88.88
84.08
79.69
73.77
0.0049
0.0104
0.0155
0.0211
0.0420
0.0706
0.1427
0.2497
0.3076
0.3707
0.4479

m
ms
n

temperature and alcohol concentration as the concentration of


Na2 HPO4 is increased, is decreased. If we assume that the size
of the ion is not pressure dependent and the electrostricted water
is already compressed to its maximum extend by the charge on
the ions [12], we can assume that the compressibility of a binary
aqueous solution is mainly due to the effect of pressure on the
bulk (unhydrated) water molecules. As the concentration of the
electrolyte increases and a large portion of the water molecule
are elctrostricted, the amount of bulk water decreases causing the
compressibility to decrease. Figs. 36 show that for alcohol mass
fractions 0.00, 0.05, 0.10, the values of decrease by increasing temperature and the temperature dependence of becomes
greater as concentration of alcohol decreases. Fig. 6 shows that
for the alcohol mass fraction 0.15 (and higher), the values of
increase by increasing temperature. The temperature depen-

1.3328
1.3329
1.3331
1.3333
1.3340
1.3348
1.3357
1.3367
1.3379
1.3392
1.3421
1.3438
1.3458
1.3476
1.3490
1.3505
1.3524
1.3551

In aqueous solutions with wa = 0.10

Fig. 3. Plot of isentropic compressibility, , of the solutions of Na2 HPO4 in


water against molality of the salt, ms , at different temperatures: , T = 283.15 K;
, T = 288.15 K; , T = 293.15 K; , T = 298.15 K; , T = 303.15 K.

mol1 )
(S cm2
(mol kg1 )

In aqueous solutions with wa = 0.05

339

0.0049
0.0104
0.0154
0.0211
0.0413
0.0712
0.1066
0.1437
0.1927
0.2475
0.3697
0.4438
0.5295
0.6125
0.6768
0.7479
0.8346
0.9695

m
ms

192.10
180.20
173.51
166.73
153.42
139.74
130.57
123.40
116.23
109.67
98.60
92.24
86.21
81.58
77.82
74.45
70.61
65.36

mol1 )
(S cm2
(mol kg1 )

In water

Table 2
Experimental molar conductivity m (S cm2 mol1 ) and refractive index n of Na2 HPO4 in aqueous 1-propanol solutions at 298.15 K

In aqueous solutions with wa = 0.15

R. Sadeghi et al. / Fluid Phase Equilibria 260 (2007) 335342

Fig. 4. Plot of isentropic compressibility, , of the solutions of Na2 HPO4 in


aqueous 1-propanol solution with wa = 0.05 against molality of the salt, ms , at
different temperatures: , T = 283.15 K; , T = 288.15 K; , T = 293.15 K; ,
T = 298.15 K; , T = 303.15 K.

340

R. Sadeghi et al. / Fluid Phase Equilibria 260 (2007) 335342

Fig. 5. Plot of isentropic compressibility, , of the solutions of Na2 HPO4 in


aqueous 1-propanol solution with wa = 0.10 against molality of the salt, ms , at
different temperatures: , T = 283.15 K; , T = 288.15 K; , T = 293.15 K; ,
T = 298.15 K; , T = 303.15 K.

Fig. 7. Plot of isentropic compressibility, , of water + 1-propanol solutions


against temperature, t, at different alcohol mass fractions: , wa = 0.00; ,
wa = 0.05; , wa = 0.10; , wa = 0.15; , wa = 0.20; , wa = 0.25.

dence of for binary 1-propanol + water solutions is shown


in Fig. 7. Fig. 7 shows that the temperature dependence of ,
/t, for the binary solutions with wa 0.10 and wa 0.15
are negative and positive, respectively. Therefore, the temperature dependence of for ternary water + 1-propanol + Na2 HPO4
solutions is similar to those for solvents (water + 1-peopanol)
and we may conclude that the compressibility of a ternary
water + alcohol + salt solution is mainly due to the effect of
pressure on the bulk solvent molecules.
Plots of 0 versus the molality of Na2 HPO4 at different temperatures are shown in Fig. 8 for alcohol mass fractions
0.00 and 0.15. As can be seen from this figure, at each temperature the salt concentration dependence of becomes greater
as concentration of 1-propanol decreases. Also, Fig. 8 shows

that at each alcohol concentration the salt concentration dependence of becomes greater as temperature decreases. It has
been shown that the concentration dependence of in aqueous
solutions follows the order Na2 SO4 > MgSO4 > MgCl2 > NaCl
which holds for the hydration numbers [12]. In fact, the concentration dependence of becomes greater as the number of water
molecules affected by the ions increase. At higher temperatures,
ionsolvent interactions are weakened and therefore the number
of water molecules affected by the ions decrease. On the other
hand, the strong attractive interactions due to the hydrogen-bond
formations between 1-propanol and water molecule induce the
dehydration of ions and therefore by increasing 1-propanol concentration the number of water molecules affected by the ions
decrease.

Fig. 6. Plot of isentropic compressibility, , of the solutions of Na2 HPO4 in


aqueous 1-propanol solution with wa = 0.15 against molality of the salt, ms , at
different temperatures: , T = 283.15 K; , T = 288.15 K; , T = 293.15 K; ,
T = 298.15 K; , T = 303.15 K.

Fig. 8. Plot of 0 of the solutions of Na2 HPO4 in aqueous 1-propanol


solution with wa = 0.00 and wa = 0.15 (upper series) against molality of
the salt, ms , at different temperatures: , T = 283.15 K; , T = 288.15 K; ,
T = 293.15 K; , T = 298.15 K; , T = 303.15 K.

R. Sadeghi et al. / Fluid Phase Equilibria 260 (2007) 335342

341

Fig. 9. Plot of apparent molar isentropic compression of Na2 HPO4 , K , in


aqueous 1-propanol solution with wa = 0.10 against molality of the salt, ms ,
at different temperatures: , T = 283.15 K; , T = 288.15 K; , T = 293.15 K;
, T = 298.15 K; , T = 303.15 K.

Fig. 10. Plot of apparent molar isentropic compression of Na2 HPO4 , K , against
molality of the salt, ms , at T = 283.15 K: , in water; , in aqueous 1-propanol
solution with wa = 0.05; , in aqueous 1-propanol solution with wa = 0.10;
, in aqueous 1-propanol solution with wa = 0.15.

The apparent molar isentropic compression K is defined as




V
(4)
K =
P T

283.15 K. Fig. 10 shows that at each temperature at a constant


salt concentration, the value of K of Na2 HPO4 increases as
the concentration of 1-propanol increases. The hydrogen-bond
interactions between 1-propanol and water molecule induce the
dehydration of ions and therefore at high alcohol concentrations
the water molecules around the ions become more compressible than those at lower alcohol concentrations. Furthermore as
mentioned above, at higher alcohol concentrations because of
ion-pairing effect, the number of water molecules affected by
the ions decrease.
Fig. 11 shows the variation of experimental molar conductivity of the investigated solutions of the Na2 HPO4 as a

The apparent molar isentropic compression of the Na2 HPO4 ,


K , in water and in aqueous 1-propanol solutions was computed
from the density and sound velocity experimental data according
to the following equation:
K =

1000( 0 )
+ V
m s d0

(5)

where and 0 are the isentropic compressibility of the solution and solvent, respectively. For systems containing both
Na2 HPO4 and alcohol, the alcohol + water is considered as the
solvent.
In Fig. 9, the temperature and concentration dependence
of K have been given for Na2 HPO4 in aqueous solution of
1-propanol with wa = 0.10. The similar behavior has been
obtained for the other systems investigated in this work. From
Fig. 9, it can be seen that the value of apparent molar isentropic
compression of di-sodium hydrogen phosphate in aqueous 1propanol solutions (and also in pure water) is negative and it
increases with increasing the concentration of Na2 HPO4 and
temperature. The negative values of apparent molar isentropic
compression imply that the water molecules around the disodium hydrogen phosphate are less compressible than the water
molecules in the bulk solutions. In fact, the negative values of K
of di-sodium hydrogen phosphate in aqueous 1-propanol solutions is attributed to the strong attractive interactions due to the
hydration of ions at low temperatures. By increasing temperature, ionwater interactions are weakened and therefore at high
temperatures the water molecules around the di-sodium hydrogen phosphate become more compressible than those at lower
temperatures. In Fig. 10 the values of K are plotted as a function of salt concentration at various 1-propanol concentration at

Fig. 11. Plot of molar conductivity, m , of the aqueous 1-propanol solutions


of Na2 HPO4 against the square root of the salt molaity, m0.5
s , at T = 298.15 K:
, in water; , in aqueous 1-propanol solution with wa = 0.05; , in aqueous
1-propanol solution with wa = 0.10; , in aqueous 1-propanol solution with
wa = 0.15.

342

R. Sadeghi et al. / Fluid Phase Equilibria 260 (2007) 335342

4. Conclusions

Fig. 12. Plot of refractive index, n, of the aqueous 1-propanol solutions of


Na2 HPO4 against the salt molaity, ms , at T = 298.15 K: , in water; , in aqueous 1-propanol solution with wa = 0.05; , in aqueous 1-propanol solution with
wa = 0.10; , in aqueous 1-propanol solution with wa = 0.15.

function of the square root of the salt molality at 298.15 K.


From this figure, it can be seen that the molar conductivities exhibit a slight increase in conductivity with decreasing
salt concentration, bending up at low concentrations. This
behavior is similar to those of polyelectrolytes. The effects
of 1-propanol concentration on the molar conductivity values
are directly evident from Fig. 11. The m values are found
to decrease with decreasing relative permittivity in going from
0.00 to 0.15 mass fraction 1-propanol + water mixtures over
the entire concentration range investigated. This is expected
because, as the relative permittivity of the medium decreases,
cationanion interactions increase and therefore ion-association
increases, which results in a lower mobility of the conducting
species.
Fig. 12 shows the variation of experimental refractive index
of the investigated solutions of the Na2 HPO4 as a function of
the salt molality at 298.15 K. From this figure, it can be seen
that the refractive index of solutions increases with increasing
the concentration of Na2 HPO4 and 1-propanol.

Experimental data at T = (283.15303.15) K of density and


sound velocity of di-sodium hydrogen phosphate in water + 1propanol mixed-solvent media containing 0.00, 0.05, 0.10 and
0.15 mass fractions of 1-propanol have been reported. The
values of apparent molar volumes and isentropic compressibilities of solutions were calculated from the measured data.
The results show a positive transfer volume of di-sodium
hydrogen phosphate from an aqueous solution to an aqueous 1propanol solution and at each temperature the apparent molar
volume of Na2 HPO4 increases by increasing the 1-propanol
concentration. The apparent molar isentropic compression of
di-sodium hydrogen phosphate in both binary and ternary solutions has negative values and it increases with increasing the
concentration of Na2 HPO4 , concentration of 1-propanol and
temperature. Finally, the electrical conductivity and refractive
index of the solutions of di-sodium hydrogen phosphate in
water + 1-propanol mixed-solvent media containing 0.00, 0.05,
0.10 and 0.15 mass fractions of 1-propanol have been reported
at 298.15 K. The molar conductivities are found to decrease as
the relative permittivity of the medium decreases.
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