Indian Journal of Chemical Technology

Vol. 11, September 2004, pp. 714-718

Evaluation of apparent and partial molar volume of potassium ferro- and

ferricyanides in aqueous alcohol solutions at different temperatures
U N Dasha, G S Royb* & S Mohantyc
a

Department of Chemistry, Utkal University, Bhubaneswar 751 004, India

b
Department of Physics, Rajadhani College, Bhubaneswar, India
c
Department of Physics, S V M College, Jagatsinghpur 754 103, India

Received 19 September 2003; revised received 20 May 2004; accepted 16 June 2004
Apparent and partial molar volume of potassium ferro- and ferricyanides in aqueous alcohol solutions have been
determined at four different temperatures 298.15, 303.15, 308.15 and 313.15K with the objective of studying ion-solvent
interaction in these systems. The transfer of volumes for the transfer of these salts from aqueous alcohol solution to water
has been evaluated. Negative transfer of volume was observed and the results have been explained on the basis of
electrostriction.
IPC Code: G01 N 9/00, C01 C 3/12
Keywords: Apparent molar volume, partial molar volume, potassium ferrocyanide, apparent molar expansibility, aqueous
alcohol.

Evaluation of partial molar quantities are of

importance as they give a lot of informations
regarding ion-solvent interaction in various complex
compounds. But since these quantities are not directly
experimentally determined it is difficult to throw light
on molecular interaction in ternary mixtures. Further,
these quantities are related to the corresponding
apparent molar quantities which are directly
experimentally determined and can be used for
studying ion-solvent interaction in solution.
The partial and apparent molar properties of
potassium ferro and ferricyanides in water and
water+acetone mixtures have been reported earlier1.
The same properties of these salts in water +
methanol, water + ethanol and water + n-propanol
mixtures (5, 10 and 20 wt% in each case) at four
different temperatures: 298.15, 303.15, 308.15 and
313.15 K are reported here. Further, the transfer of
volumes for the transfer of these salts from aqueous
alcohol solution to water have also been determined.
The contributions of change in temperature, change in
composition and increase of chain length have been
discussed in the light of electrostriction.
Theory

The apparent molar volume V and apparent molar

__________
*For correspondence.

expansibility E are computed by the following

relations2,

V= 1000 (d0 c-1) (d0- d ) + M2 d0-1

and = 0 V + ( 0) 1000 c-1

(1)
(2)

where c is the molar concentration, d0 and d are the

densities of solvent and solution respectively, M2 is
the molecular weight of the solute, 0 and are the
co-efficients of thermal expansion of solvent and
solution respectively.
The V and data are fitted to Masson equation2
by least squares method,

V = V 0+S V c1/2
and = 0 + S c1/2

(3)
(4)

to obtain V 0, the limiting apparent molar volume, SV

the experimental slope of Eq.(3), 0, the limiting
apparent molar expansibility and S, the experimental
slope of Eq.(4).
The partial molar volume and partial molar
expansibility have been calculated from the relations3,
V2 = V + (1000 - c V) (2000 + S V c3/2)-1 S V c1/2 (5)

and

E2 = + (1000 - c) (2000 + S c3/2)-1 S c1/2

(6)

DASH et al.: EVALUATION OF MOLAR VOLUME OF POTASSIUM FERRO AND FERRICYANIDES

715

The apparent molar volume at infinite dilution, also

called the limiting apparent molar volume is equal to
the partial molar volume at infinite dilution V2 0.
The partial molar volume of transfer of the above
mentioned salts from aqueous alcohol solution to
water are calculated from the relation,

V0(tr) = V0 (aqueous alcohol) - V0 (water) (7)

Experimental Procedure
Potassium ferrocyanide and potassium ferricyanide
(BDH, Anal Rs) were kept over anhydrous calcium
chloride in vacuum desiccator until required.
Methanol, ethanol and n-propanol (BDH, Anal Rs.)
were dried over 4A molecular sieve and distilled.
Conductivity water (sp.cand.~10-6S cm-1) was used
for preparing water + alcohol mixtures. The alcohol
content in the mixed solvents was accurate to within
0.01% . The solutions were prepared on molal basis
and conversion of molarity was done by using
standard expression4. The densities were measured
pychnometrically (uncertainty 110-2 kg m-3).
Temperature was maintained by a thermostat with a
precision of 0.05 K.
Results and Discussion
A perusal of Table 1 and Fig. 1 shows that, V0
values of ferrocyanide salt are positive in water and
increases with temperature in all the solvents. With
increase of alcohol concentration, the value decreases
and becomes negative at certain composition.
Negative value of V0 provides evidence of
electrostriction5. Again, since V0 is a measure of ionsolvent interaction, the negative value indicates
weaker ion-solvent interaction. The result indicates,
that, the ion-solvent interaction increases with
temperature, decreases with alcohol concentration and
number of -CH2- groups in alcohol (i.e. chain length).
The lowering of V0 values is probably due to the
increased steric hindrance of the bulkier solvent
molecules to the ion-solvent interaction. The presence
of ion-solvent interaction between the molecules
promotes the structure making effect of the salts in
water + alcohol mixtures. In case of ferricyanide salt
(Table 2, Fig. 2), V0 values are positive in all the
solvents and at all the four temperatures. Ion-solvent
interaction of ferricyanide salt is greater than that of
ferrocyanide salt which implies that ferrocyanide salt
shows more structure making effect than ferricyanide
salt.

Fig. 1V ~ c1/2 for potassium ferrocyanide in 5wt% methanol at

(1) 298.15 K, (2) 303.15 K, (3) 308.15 K, (4) 313.15 K and in (5)
10 wt% methanol and (6) 20 wt% methanol at 298.15 K.

Fig. 2E ~ c1/2 for potassium ferricyanide in (1) 5 wt%

methanol, (2) 10 wt% methanol, (3) 20 wt% methanol, (4) 20 wt%
ethanol and (5) 20 wt% n-propanol at 298.15 K.

As observed, SV values are high and positive at

every temperature and decrease with temperature for
both the salts. Since, SV is a measure of ion-ion
interaction, the result indicates the presence of ion-ion
interaction in the system at every temperature and
both the salts ionize to a greater extent with increase
in temperature. Ion-ion interaction increases with
increase of alcohol content in the solution. This
suggests that more and more solute molecules are
accommodated within the void spaces left in the
packing of the large associated solvent molecules and
as such enhance the structure of the solvent.

INDIAN J. CHEM. TECHNOL., SEPTEMBER 2004

716

Table 1Values of V0 (m3mol-1), SV (m9/2 mol-3/2), V0(tr) (m3mol-1), E0 (m3mol-1K-1) and SE (m9/2 mol-3/2K-1) for potassium
ferrocyanide in water and water+alcohol system at different temperatures
wt. % alcohol

Temp (K)

106

0
V

109 S

105 0(tr)
V

106

0
E

-109 S

0.0

298.15
303.15
308.15
313.15

43.6
101.8
133.8
158.9

380.59
205.36
150.84
119.38

7.72
7.75
7.79
7.81

18.52
18.59
18.69
18.71

5 (methanol)

298.15
303.15
308.15
313.15

56.6
67.3
73.4
80.3

87.33
48.90
31.85
14.96

1.30
-3.45
-6.04
-7.86

1.54
1.57
1.58
1.59

4.83
4.99
4.99
5.01

10 (methanol)

298.15
303.15
308.15
313.15

15.1
32.3
47.8
52.6

167.02
120.87
79.03
76.11

-2.85
-6.95
-8.60
-10.63

2.53
2.55
2.56
2.58

6.26
6.36
6.32
6.40

20 (methanol)

298.15
303.15
308.15
313.15

-14.3
-7.4
2.5
16.7

358.48
338.48
311.37
261.62

-5.79
-10.92
-13.13
-14.22

2.02
2.04
2.05
2.06

6.29
6.43
6.36
6.41

5 (ethanol)

298.15
303.15
308.15
313.15

47.5
54.4
60.8
67.0

111.85
87.91
64.42
38.49

0.39
-4.74
-7.30
-9.19

1.27
1.26
1.26
1.28

4.70
4.57
4.57
4.64

10 (ethanol)

298.15
303.15
308.15
313.15

31.9
39.2
46.3
55.2

150.20
126.10
97.50
60.30

-1.17
-6.26
-8.75
-10.37

1.50
1.52
1.54
1.56

5.79
5.85
5.94
6.01

20 (ethanol)

298.15
303.15
308.15
313.15

-39.6
-14.6
18.1
48.5

481.44
391.74
246.84
114.48

-8.32
-11.64
-11.57
-11.04

5.86
5.89
5.95
6.04

24.50
24.60
24.90
25.40

5 (n-propanol)

298.15
303.15
308.15
313.15

17.1
24.9
34.6
47.9

267.49
261.62
250.06
213.88

-2.65
-7.69
-9.92
-11.10

1.97
1.99
2.02
2.05

3.31
3.36
3.46
3.54

10 (n-propanol)

298.15
303.15
308.15
313.15

4.6
12.3
25.6
35.1

275.16
271.01
252.65
226.87

-3.90
-8.95
-10.82
-12.38

2.08
2.09
2.12
2.13

3.49
3.49
3.56
3.56

20 (n-propanol)

298.15
303.15
308.15
313.15

-46.5
-25.6
-0.2
27.3

434.54
386.28
304.79
228.51

-9.01
-12.74
-13.40
-13.16

4.85
4.87
4.92
4.98

1.37
1.38
1.40
1.41

It is observed that the partial molar volume V2

increases with concentration and temperature in all
the solvents whereas decreases with increase of
alcohol content in the mixed solvent. Increase of V2
with concentration is owing to the structure breaking
of the solvent molecules in concentrated solutions of
high charge density ions like potassium characterized
by very strong interaction forces with the solvent

molecules and this interaction increases with

temperature and decreases with alcohol concentration.
The values of V0 (tr) are negative for both the
salts. The measured partial molar volume can be
considered to be a sum of the geometric volume of the
solute and changes in the solvent due to its interaction
with solvent. This simple approach has been widely
used in many models6 to interpret partial molar

DASH et al.: EVALUATION OF MOLAR VOLUME OF POTASSIUM FERRO AND FERRICYANIDES

717

Table 2Values of V0 (m3mol-1), Sv(m9/2 mol-3/2), V0(tr) (m3mol-1), E0(m3mol-1K-1) and SE (m9/2 mol-3/2K-1) for potassium
ferricyanide in water and water+alcohol system at different temperatures.
Temp (K)

106 V0

109 SV

105 V0(tr)

106 E0

-109 SE

0.0

298.15
303.15
308.15
313.15

104.1
131.9
151.7
168.6

23.58
148.11
131.64
107.06

4.21
4.24
4.27
4.28

7.81
7.91
7.95
7.98

5 (methanol)

298.15
303.15
308.15
313.15

99.2
104.7
119.9
129.2

178.27
158.92
103.26
73.63

-0.49
-2.72
-3.18
-3.94

2.07
2.10
2.13
2.13

7.26
7.51
7.53
7.49

10 (methanol)

298.15
303.15
308.15
313.15

83.5
90.3
103.0
114.9

182.69
169.32
125.21
94.68

-2.06
-4.16
-4.87
-5.37

2.14
2.16
2.16
2.17

6.32
6.52
6.37
6.40

20 (methanol)

298.15
303.15
308.15
313.15

71.5
75.7
95.0
107.8

190.83
188.21
129.56
98.26

-3.26
-5.62
-5.67
-6.08

2.60
2.64
2.65
2.67

7.10
7.39
7.24
7.28

5 (ethanol)

298.15
303.15
308.15
313.15

80.3
110.8
125.1
133.9

252.67
134.01
77.81
51.37

-2.38
-2.11
-2.66
-3.47

3.45
3.48
3.52
3.54

12.94
13.05
13.23
13.31

10 (ethanol)

298.15
303.15
308.15
313.15

73.4
93.9
107.5
121.3

241.68
157.87
108.55
59.14

-3.07
-3.80
-4.42
-4.73

3.09
3.13
3.17
3.25

11.72
11.89
12.09
12.50

20 (ethanol)

298.15
303.15
308.15
313.15

51.9
71.9
85.4
94.9

292.23
209.08
151.55
121.07

-5.22
-6.00
-6.63
-7.37

2.79
2.81
2.83
2.87

11.20
11.33
11.40
11.59

5 (n-propanol)

298.15
303.15
308.15
313.15

89.7
95.7
107.7
116.5

88.22
88.10
59.53
46.20

-1.44
-3.62
-4.40
-5.21

1.81
1.83
1.83
1.86

2.89
2.94
2.88
2.97

10 (n-propanol)

298.15
303.15
308.15
313.15

78.1
92.4
104.6
114.1

128.29
94.69
62.69
50.97

-2.60
-3.95
-4.71
-5.45

2.40
2.41
2.45
2.49

5.33
5.34
5.47
5.45

20 (n-propanol)

298.15
303.15
308.15
313.15

32.6
49.7
69.9
87.9

353.16
318.98
270.41
227.95

-7.15
-8.22
-8.18
-8.07

3.68
3.69
3.73
3.77

8.54
8.53
8.64
8.76

wt. % alcohol

volume data for a broad range of solutes. When two

charged centres are not separated by the distance 3-4
A, then their hydration co-spheres overlap which
results in the decrease in the electrostriction. The
overlap of co-spheres of two ionic species shows an
increase in volume whereas overlap of hydrophobichydrophobic and ion-hydrophobic groups results in
decrease in volume. In the present case there is

increase of electrostrictive solvation as well as

hydrophobic solvation. Hydrophobic solvation
increases as the number of -CH2- group increases in
the alcohols.
As expected, the partial molar expansibility E2
decreases with concentration and increases with
temperature. The value of 0 increases with
temperature indicating the presence of caging or

INDIAN J. CHEM. TECHNOL., SEPTEMBER 2004

718

packing effect8. As is seen, the 0 values increase

with increase of alcohol content in the mixed solvent.
This suggests that the structure making effect of the
electrolytes studied is favoured in aqueous alcohol
medium as compared to aqueous medium.

3
4
5
6

References
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8

Dash U N & Nayak S K, Thermochim Acta, 32 (1979) 331;

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