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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
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-
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
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
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
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
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
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].
(3)
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
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
mol1 )
(S cm2
(mol kg1 )
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
340
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.
341
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.
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
342
4. Conclusions