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to calculate the viscosity. The densities of the different concentration were utilized for the
solutions were measured using a 15 mL double arm determination of inter-molecular interactions in the
pyknometer26 having accuracy ±0.00001g/mL and a solutions. The interaction parameters were obtained
single pan electronic balance (Citizen). with the help of Jones-Dole equation27:
(ƞ/ƞ0‒ 1) c‒ 0.5 = A + Bc0.5 … (1)
Results and discussion
The viscosity of the solution depends on the where A and B are the coefficient for the ion-ion
sulfuric acid concentration and the temperature of the and ion-solvent interaction respectively and c is the
solution. There is a deviation in linearity in the molar concentration. A representative plot between
concentration region 4.0 mol dm-3 to 7.0 mol dm-3 (η/ηo-1) c−0.5 and c0.5 is given in Fig. 2. The values of
with the major deviation at 1.0 mol dm-3 and the linearity coefficient show deviation from standard
9.0 mol dm-3 as shown in Fig. 1. These deviations value of 1.0, which shows the presence of three
indicate the formation of different ionic species. Such concentration regions due to different nature of
deviations are also observed in reported values of solute-solvent interactions.
viscosities10. The measured values of the viscosities The applicability of Jones-Dole equation in the
and densities are given in Table 1. The viscosities lower concentration of the sulfuric acid has been
measured in the study were used to calculate the value reported in literature17. The validity of Jones-Dole
of η/ηo at each concentration, where η and ηo are equation was checked graphically and the plot
viscosities of the solution and solvent respectively. At displays three straight lines between the concentration
each molar concentration ‘c’, the value of η/ηo is region of 1.0 mol dm-3 to 9.0 mol dm-3. For all three
collected in Table 1. The value of η/ηo obtained at concentration regions, 1.0 mol dm-3 to 4.0 mol dm-3,
Fig. 1 – Variation of viscosity (η) of aqueous sulfuric acid with Fig. 2 – Jones-Dole plot of aqueous sulfuric acid of varying
varying concentrations at 297.65 K. concentrations at 297.65 K.
Table 1 – Values of viscosity (η), density (ρ), η/ ηo and E* of aqueous sulfuric acid + water system at 297.65 K
a
c ƞ c 0.5 ρ η/ηo (η/ηo-1)c−0.5 E*
(mol dm−3) (cP) (mol dm−3/2)
1/2
(g cm-3) (mol−1/2 dm3/2) (kJ)
1.0 1.19 1.00 1.0379 1.20 0.20 0.43
2.0 1.44 1.41 1.0868 1.46 0.32 0.90
3.0 1.77 1.73 1.1431 1.79 0.45 1.41
4.0 2.08 2.00 1.1930 2.11 0.55 1.81
5.0 2.49 2.23 1.2326 2.52 0.68 2.25
6.0 3.03 2.44 1.3041 3.06 0.84 2.74
7.0 3.77 2.64 1.3563 3.81 1.06 3.28
8.0 4.44 2.82 1.3927 4.49 1.23 3.68
8.5 5.23 2.91 1.4212 5.30 1.48 4.09
9.0 5.84 3.00 1.4425 5.90 1.63 4.36
a
1.0–4.0 mol dm-3 (B = 0.353 dm-3/2mol-1, A = ‒ 0.162; R2 = 0.99); 4.0–7.0 mol dm-3 (B = 0.789 dm-3/2mol-1, A = ‒ 1.055; R2 = 0.97);
7.0–9.0 mol dm-3 (B =1.612 dm-3/2mol-1, A = ‒ 3.234; R2 = 0.95).
1082 INDIAN J CHEM, SEC A, SEPTEMBER 2016
4.0 mol dm-3 to 7.0 mol dm-3 and 7.0 mol dm-3 to H2SO4 ↔ H+ + HSO4−
9.0 mol dm-3, the values of A were calculated from H + H2O ↔ H3O+ (ion-solvent interaction)
+
the intercept and the values of B were calculated from H3O+ + HSO4− ↔ H4SO5
the slope. The data obtained are recorded in Table 1. H2SO4 + H2O ↔ H2SO4.H2O (solvent-solute interaction)
The values of linearities are also given for each Interaction in H2SO4-H2O
concentration region. The regression results for Scheme 1
Jones-Dole equation comprises a linear relationship The proposed interaction with water is in
for the obtained concentration regions of H2SO4 confirmation with the previous studies11, 13. In these
although the values of gradients are different. A reports, the hydrated sulfuric acid can exists at lower
comparison of the gradients clearly indicates that temperature and higher concentration region. In
there are three sulfuric acid-water systems between general, the value of stability constant increases with
concentration range of 1.0 mol dm-3 to 9.0 mol dm−3. the decrease in dielectric constant and dipole
Viscosity is a macroscopic property that represents moments of the solvent31. The dielectric constant of
the average behavior of a large number of water water has a large value and due to the presence of
molecule as reported in the literature28. The increase hydronium ion it acts as a strong donor solvent which
in viscosity of solution with the concentration of an results in the decrease of the stability constants of
acid can be explained from the rigid nature of sulfuric acid species.
solvation structure formed by the ion and its hydration In this study, we have obtained three specific
shell. The B-coefficient is a measure of order or regions of concentration which confirm the transition
disorder introduced in the solvent structure due to of species formed between the ions produced by
the ion or dipole formed by the solute29. The H2SO4 and water. The stability of the molecule
B-coefficients calculated with the help of Jones-Dole around the central atom is well known as O2S(OH)25.
equation are positive in all the three concentration The exchange of water molecule with H+ ion is
regions, which suggests that sulfuric acid acts as a responsible for the HSO53− species in presence of
structure maker in the concentration range under study. H2SO4 because H2SO5, peroxo-monosulfuric acid, is
The strength of solute-solvent interaction increases well known form of peroxy acid of sulphur32. The
with the increasing concentration of the acid. ionization of the proposed structure formed by
It is a general concept that molecules must have intermolecular interaction between HSO4− species and
sufficient energy to flow in the media. The flow hydronium ion may also maintain the transient
depends upon the viscosity and temperature. The equilibrium in the following manner13:
Boltzmann factor e−E/RT gives the relationship for H4SO5 ↔ 3H+ + HSO53−
increase in the number of molecules in viscous flow H2 + HSO53− ↔ H+ + SO42− + H2O +2e−
with the increase of temperature. Hence, the
Interaction between HSO4− species
resistance to flow is reciprocal to the above factor and and hydronium ion
viscosity can be given by equation30:
Scheme 2
η = Ae E*/RT … (2)
The species, HSO53−, has been reported in the
E* is the energy of activation of the molecule following equilibrium with standard potential –1.0933 V
taking part in a flow of liquid. The value of E* at (ref. 14). The interaction parameters obtained from
different concentration of aqueous sulfuric acid were Jones-Dole equation for concentration range under
obtained from viscosity data are tabulated in Table 1. study is in agreement with the proposed solution
The data analysis for rate change of the energy of structures along with interactions. The main
activation with concentration in the three different supporting evidences are as follows: The E* values
concentration regions of H2SO4 verifies the presence increases with increasing concentration of acid which
of the three concentration regions. In the calculation, indicates strong interactions between water and
the value of log A has been considered constant and sulfuric acid molecule. It can be supposed that there
negligible since the relation between the energy of are two association type structures in two distinct
activation and value of A follow the same trend. ranges in the higher concentration region whereas in
H+ always exists with HSO4− and hence the the lower concentration region, dissociation type
following interaction is proposed as given: structure is possible which is identified by the slow
NOTES 1083