Densities and viscosity measurement of
K3[Cr(C2O4)3]3H2O in water, methanolwater, isopropanol-water and DMSO-water
at 303.15K
Smrutiprava Das*
Monalisa Das†
Ajay Pattanaik‡
*
[Corresponding Author], [Ravenshaw University, Cuttack, India], [ dassmrutiprava@yahoo.com ],
[09437604667].
†
[Ravenshaw University, Cuttack, India]
‡
[Khalikote Autonomous College, Berhampur, India]
© 2012. Smrutiprava Das, Monalisa Das, & Ajay Pattanaik.. This is a research/review paper, distributed
under the terms of the Creative Commons Attribution-Noncommercial 3.0 Unported License
http://creativecommons.org/licenses/by-nc/3.0/, permitting all non-commercial use, distribution, and
reproduction in any medium, provided the original work is properly cited.
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Densities and viscosity measurement of
K3[Cr(C2O4)3]3H2O in water, methanol-water,
isopropanol-water and DMSO-water at 303.15K§
Smrutiprava Das, Monalisa Das, & Ajay Pattanaik
Abstract
Densities and viscosity of K3[Cr(C2O4)3]3H2O in water, methanol-water, isopropanol- water and
DMSO- water have been measured at 303.15 K. From the density data, the values of apparent
molar volume and limiting molar volume have been determined. The result of viscosity data have
been fitted to Jones-Dole equation to get the Falkenhagen coefficient and Jones-Dole coefficient.
The main thrust of the study is to correlate such physicochemical properties and relevant
interaction parameters with the nature of molecular interactions.
Keywords: density, viscosity, solute-solute interaction, solute-solvent interaction.
§
Acknowledgment
Nil
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I.
Introduction:
the formation of transition state is accompanied by
Studies on physicochemical properties on
solution provide a very useful tool in elucidating the
structural interactions among the components. Such
properties are dependent upon temperature and
composition of solutions. The addition of organic
solvent to an aqueous solution of electrolyte brings a
chance in ion salvation and reactivity of dissolved
electrolyte1-2. The method of studying the molecular
interactions
determined
from
the
variation
of
thermodynamic parameters and their excess values
with composition gives an insight into the molecular
process3-5. Density measurements can give interesting
information about ion-ion, ion-solvent and solventsolvent interactions. Parmer etal
6
have reported the
determination of partial molar volumes of different
acids in aqueous mixtures of ethanol at different
concentrations. Ram Gopal etal
7
studied the partial
molar volume of some halides in formamide and Nmethyl acetamide. Kurotaki and Kawamura
8
have
studied the partial molar volumes of trivalent Co(II)
and Cr(III) complex ions in water to examine the
structure making and structure breaking effects of
complex ions. Viscosity is the property of liquid that
depends on intermolecular forces, the structural
aspects of a liquid. Hence viscosity of solutions at
different solvent composition is very much important
to investigate ion-solvent interaction in electrolytic
solutions. The viscosity data were also analyzed on
the basis of transition state theory which indicates that
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the rupture and distortion of intermolecular forces in
solvents. The viscosity and density measurements of
glycine and DL-alanine in dioxane+water mixtures
were carried out by Wadi etal 9. Dey etal
determined
viscosity
‘B’
coefficient
10
were
potassium
halides in water+pyridine suggesting the large ‘B’
coefficients in terms of ion-solvent and solventsolvent interactions. Ziogas and Papanastasious
11
were determined the density, molar volume and
viscosity changes of liquid systems in DMSO+metal
nitrate
mixtures
indicated
that
cation-dipole
interactions are strong in DMSO than other aqueous
solutions. Thus physicochemical studies involving the
determination of density, partial molar volume,
viscosity have proven a considerable importance in
studying ion-ion and ion-solvent interactions in
aqueous and mixwd aqueous solvent media12-17. Arti
Goyal and Mukhtar Singh
18
have determined
densities and viscosities of ternary liquid mixture at
298.15 K. R. Palani etal
19
have determined the
physicochemical behaviour of monohydroxy alcohols
with DMSO. Ligia-Maria OMOTA etal
20
have
predicted the determination of densities and derived
properties of water, 1,4-Dioxane and DMSO at
different temperatures. This present paper aims at
determination of experimental data of densities(d) and
viscocities(nr) of K3[Cr(C2O4)3]3H2O with water,
methanol-water, isopropanol-water and DMSO-water
mixtures at 303.15 K.
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II.
Theory:
(E. Merck > 99.9% pure), DMSO (Ranbaxy) were
The apparent molar volume(Vф) have been
purified by recommended methods
determined employing the relation 21.
25
. The complex
K3[Cr(C2O4)3]3H2O were synthesized by the method
26
. The densities were determined by using specific
Vф= 1000(d0-d)(cd0)-1+M2d0-1 - - - - - (1)
gravity bottle by relative measurement method with
Where m2 is the molecular weight of solute concerned
accuracy ± 1 X 10-5 gm ml-1. For viscosity
d and d0 denote the densities of solution and
measurements Ostwald viscometer was used with
solvent respectively
c is the concentration of the solution.
accuracy nearly 0.3%. the viscometer was caliberated
frequently with distilled water. The flow time was
also measured by using digital clock (0.01 sec).
The limiting apparent molar volume, Vф0 is obtained
Precautions regarding prevention of evaporation of
from the Vф data using 21,
solvent were also taken.
Vф = Vф0 + SVC1/2 - - - - - (2)
Where SV is the slope of the linear variation22 and is
considered to be the factor describing ion-of
solvent interactions in the system studied.
IV.
Result and Discussion:
The synthesized complex K3[Cr(C2O4)3]3H2O was
subjected to calculate the densities and viscosities in
water,
methanol-water,
isopropanol-water
and
DMSO-water mixtures at 303.15K. These solutions
The viscosity data have also interpreted in the
light of Jones-Dole equation 23.
were prepared by dissolving a known amount of
complex in aqueous solutions containing 20%, 30%,
and 40% u/v of methanol, isopropanol and DMSO to
nr = 1 + A C1/2 + BC - - - - - (3)
where nr is the relative viscosity. A is the
Falkenhagen
24
obtain the concentration of solutions ranging from
0075, 0.01, 0.02, 0.03 and 0.05 M of the Complex.
coefficient and B is the Jones-Dole
coefficient ant are obtained from the plot of nr-1/√C
verses √C.
The measured densities, apparent molar
volume (Vф), limiting molar volume (Vфo) and
experimental slope (Sv) of water, methanol-water,
III.
Experimental:
isopropanol-water, DMSO-water are presented in
All the chemicals used were of analytical
table-1 where the values of Vфo and Sv have been
grade. The chemicals like oxalic acid, potassium
evaluated by computerized least-square fitting to eq.
oxalate, potassium dichromate, methanol, isopropanol
(2). It was observed that the apparent molar volume
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(Vф) decreases with increase in concentration of the
seems to be sufficiently strong to prevent the solute-
solution in methanol-water and isopropanol-water
solvent interactions. This explains the lower values of
mixtures. The values of limiting apparent molar
Vф of the complex in methanol-water and DMSO-
(Vфo)
volume
was obtained by plotting a graph
between Vф and √ for DMSO-water and methanol-
water mixtures.
water as shown in figure-1 and 2 respectively. It was
The viscosities of the complex in water and in
solutions of varying volume percentage ( %) of
seen that the values of Vф for the complex in
methanol, isopropanol and DMSO increase with
methanol-water are positive. The positive values of
increase in concentration of solutions. The viscosity
Vф indicate the presence of strong solute-solvent
values, the values of A (Falkenhagen coefficient) and
interactions. But a sharp decrease in the values of Vф
B(Jones-Dole coefficient) are listed in table-2. The
in methanol-water and isopropanol-water occur which
increase in viscosity with increase in concentration
suggests that the strength of solute-solvent interaction
may be due to the increasing tendency of the solute
is reduced with increase in concentration of solution.
molecules to associate in the form of clustering entity
The values of Vф increases slightly in aqueous
in solute-solvent systems. The plots of nr-1/√ verses
medium (Table-1) from positive to negative value
√ for the complex in DMSO-water and isopropanol-
showing
interaction
water are linear as shown in figure-3 and 4
between substrate and water with increase in substrate
respectively. From such plots it is logical to evaluate
concentration. But in case of DMSO-water medium,
the coefficients A and B. The values of these
there is a rapid increase in Vф (almost 20 times
coefficients depend upon the composition of the
greater than aquous medium) indicating enhancement
solutions. The Falkenhagen coefficient ‘A’ measures
in
in
the ionic interaction and Jone-Dole coefficient B is a
concentration of DMSO which may be attributed to
measure of effective solvodynamic volumes of
increased solvation of the complex in DMSO-water
solvated ions and is governed by size and shape effect
medium than in aqueous medium..
of solute and structural effect induced by solute-
increase
solute-solvent
in
solute-solvent
interaction
with
increase
Table-1 shows that the values of SV in all
sovent interactions 27-28. From table-2 it was observed
cases are Iargely negative which indicate the weak
that the values of A are positive and increase in all the
existence of ion-ion or solute-solute interactions. But
solutions showing strong solute-solute interactions in
the values of SV become positive in water and
solute molecules. The values of B are negative in all
DMSO-water which suggest that the solute-solvent
cases which measure the solute-solvent interactions.
interactions in solutions become stronger. Thus
The magnitude of ‘B’ coefficients is smaller
solute-solvent interaction through hydrogen bonding
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compared to ‘A’ coefficients showing that ion-ion
more prominent in 2-propanol-water and methanol-
interactions dominate over ion-solvent interactions.
water. Cr(III) complex is more reactive in DMSOwater as compared to
2-propanol-water
and
V.
ConclusionIn the light of above observations, it may be
methanol-water because of strong solute-solvent
concluded that ion-solvent interactions exist resulting
interaction, DMSO is a suitable solvent for such type
in attractive forces which promote the structure
of particular ion as compared to 2-Propanol.
interaction in DMSO. Hence to study the ion-solvent
making tendency. The solvent –solvent interaction is
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OMOTA and Oana Clocirian, Ravue Roumaine
de Chimie, 54(1), 63-73 (2009).
[21]. H.S. harned and B.B. Owen, The physical
chemistry of electrolyte solutions, 3rd
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Text Book of quantitative chemical analysis, Vth
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[27]. R.H.
Stokes
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International
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(New York), 9, (1962).
JournalsBank.com (2011).
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Vф ml mol-1
-76.894
-14.001
171.234
187.256
199.520
206.124
5143.231
3885.369
2140.086
1463.294
997.885
3508.319
2658.262
1384.678
960.149
695.998
2752.602
1997.885
1195.998
928.703
667.131
30%
isopropanol
-water
0.0075
0.01
0.02
0.03
0.05
0.0075
0.01
0.02
0.03
0.05
0.97494
0.97870
0.97964
0.98152
0.98433
0.99185
0.99467
0.99654
0.99748
1.00031
3256.438
2187.2565
1291.031
960.841
715.558
992.287
583.482
441.973
426.252
394.803
40%
isopropanol
-water
0.0075
0.01
0.02
0.03
0.05
1.00688
1.00875
1.00969
1.01063
1.01345
-1020.291
-831.611
-218.403
-14.001
130.652
20%
DMSOwater
Concentration mol dm-3
0.005
0.0075
0.01
0.025
0.05
0.1
0.0075
0.01
0.02
0.03
0.05
0.0075
0.01
0.02
0.03
0.05
0.0075
0.01
0.02
0.03
0.05
0.0075
0.01
0.02
0.03
0.05
1.02566
1.02660
1.02848
1.02942
1.03411
-3536.013
-2624.755
-1162.491
-643.623
-285.133
0.0075
0.01
0.02
0.03
0.05
1.04163
1.04351
1.04539
1.04632
1.04914
-5675.071
-4322.869
-2011.548
-1209.661
-587.021
0.0075
0.01
0.02
0.03
0.05
1.05102
1.05290
1.05572
1.05854
1.06232
-6932.931
-5266.265
-2530.416
-1618.466
-870.038
20%
isopropano
l-water
K3[Cr(C2O4)3]3H2O
40%
methanol water
30%
methanolwater
20%
methanolwater
Water
d gm ml-1
0.99842
0.99936
1.00218
1.00312
1.01251
1.02378
0.96085
0.96179
0.96273
0.96649
0.97025
0.97306
0.97400
0.97494
0.97964
0.98246
0.97870
0.98058
0.98152
0.98246
0.98621
30%
DMSOwater
Complex
40%
DMSOwater
Table-1 Density (d), apparent molar volume (Vф), limiting apparent molar volume (Vф0) and
experimental slope (SV) in water, water-methanol, water-isopropanol, water-DMSO mixtures.
JournalsBank.com (2011).
Vф0 ml mol-1
SV ml3/2 mol-3/2
-1.7
-0.9656
6.5
-1.88
4.45
-1.279
2.35
-0.466
4.05
-1.1503
1.1
-0.2679
-1.24
-1.4281
-4.51
-1.428
-7.3
-2.144
-7.2
-2.05
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10.0415
10.1374
10.1766
10.2422
10.3873
10.7733
12.2924
12.3985
12.6219
12.6767
13.7531
30%
methanolwater
0.0075
0.01
0.02
0.03
0.05
14.65391
14.7846
14.7802
15.2872
15.4946
40%
methanolwater
0.0075
0.01
0.02
0.03
0.05
16.6071
16.8216
17.0467
17.1414
17.3381
20%
isopropanol
-water
0.0075
0.01
0.02
0.03
0.05
16.4331
16.5498
16.8316
16.9879
17.1873
30%
isopropanol
-water
0.0075
0.01
0.02
0.03
0.05
17.8858
18.0293
18.1561
18.2529
18.6484
40%
isopropanol
-water
0.0075
0.01
0.02
0.03
0.05
18.8266
19.0630
19.2285
19.4414
19.6439
20%
DMSOwater
0.0075
0.01
0.02
0.03
0.05
13.6517
13.7121
13.7644
13.9071
14.1845
1.45
-0.6
0.0075
0.01
0.02
0.03
0.05
16.9891
17.0961
17.2102
17.3231
17.4326
2.2
-1.11
0.0075
0.01
0.02
0.03
0.05
20.6378
20.9058
21.1345
21.2430
21.4433
40%
DMSOwater
K3[Cr(C2O4)3]3H2O
20%
methanolwater
Water
0.005
0.0075
0.01
0.025
0.05
0.1
0.0075
0.01
0.02
0.03
0.05
30%
DMSOwater
Table-2 Viscosities (nr) and viscosity parameters of K3[Cr(C2O4)3]3H2O in water, methanol-water,
isopropanol-water and DMSO-water mixtures.
Complex
Concentration
nr
A
B
mol dm-3
milipoise
dm-3/2 mol-1/2
dm3 mol-1
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1.19
-0.466
1.3
-0.509
1.54
-0.6
1.77
0.674
1.83
-0.839
2.35
-1.48
2.41
2.61
-1.37
-1.37
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