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Effect of Ultrasound on the Production Reaction Kinetics

of Sodium Thiosulfate
By Tuba Ingeç* and Taner Tekin

It is known that the production reaction of sodium thiosulfate which consists of the reaction of Na2SO3 with sulfur is considerably
slow. Ultrasound energy was used to increase the conversion fraction of sulfur and to accelerate the production reaction of
Na2S2O3, and the effect of ultrasonic energy on the reaction kinetics was investigated. The particle size, reaction temperature,
concentration of Na2SO3 solution and amplitude of ultrasound power were chosen as parameters. The experiments were
performed in the absence and presence of ultrasound. Considering the results the reaction is chemically controlled first order and
the activation energy is equal to 42 kJ/mol in both cases. The results indicated that the ultrasound energy increased the reaction
speed but it did not vary the activation energy. The effect of ultrasound is on the pre-exponential factor A. Finally, an empirical
relation is given which relates the rate constant to ultrasound power.

1 Introduction investigated by Mills et al. [8]. The influence of ultrasound on

the kinetic parameters of electrochemical redox reactions was
It has been recognized for many years that ultrasound investigated by Jung et al. [9]. The kinetics of the acid-
power has a great potential for use in a wide variety of catalyzed hydrolysis of ethyl acetate in ethanol-water binary
processes in the chemical and allied industries. Ultrasonic solutions was investigated by Tuulmets and Salmar [10].
processing means blasting liquids, usually water, with very This paper deals with the investigation of the effect of
intense sound at high frequency, producing very good mixing, ultrasonic energy on the kinetics of the dissolution of
and powerful chemical and physical reactions. Ultrasound elemental sulfur in a Na2SO3 solution. The purpose is to
power produces its chemical effects through the phenomenon increase the conversion fraction of sulfur and to accelerate the
of cavitation [1]. Increasing the reaction speed by ultrasound production reaction of Na2S2O3 which occurs in a slow rate.
power is based on this phenomenon. The process results from
the creation and collapse of billions of microscopic bubbles in Na2SO3 + S ® Na2S2O3 (1)
the liquid. Shock waves obtained by using ultrasound power
cause the occurrence of cavitation, and the surrounding liquid
molecules rush in to fill the cavity. When they reach the center
2 Experimental
of the cavity, they collide with each other with great force. That
makes the molecules bounce back, creating even more
Fraction size ranges of elemental sulfur were used for the
cavities. This generates many micro splits and pits. It is known
experiment: ±10+20, ±20+30, ±30+40 and ±40+45 mesh.
that these micro splits and pits either cause a reaction or
Our experimental setup consists of an ultrasonic generator
increase the reaction speed by increasing the effective area of
(Type Cole Parmer, Ultrasonic Homogenizer, 400 W, 20 kHz)
reaction by providing a new surface [2].
together with a probe with a tip radius of 1 cm and a dissolution
Pochivalov et al. [3] investigated the effect of ultrasound on
vessel equipped with a thermocouple. 0.75, 1, 1.25 and 1.5 M
the kinetics of the extraction of the polymer component from a
concentrations of Na2SO3 solution were used in the experi-
porous composite material. The destruction of carbon
ments. In a typical experiment 400 mL of Na2SO3 solution
disulfide in aqueous solutions by sonochemical oxidation
were poured into a thermostatic vessel, between 0.5 and 1 g
was studied by Appaw and Adewuyi [4]. The change of
amount of elemental sulfur was added and stirred mechani-
ultrasonic velocity in aqueous solution was investigated as a
cally. Solution samples were taken at corresponding intervals
function of particle size and suspension density by Sayan and
of time, filtered immediately with a vacuum pump and
Ulrich [5]. The effect of ultrasound (f = 20 kHz) on the
analyzed for determining Na2S2O3 by the volumetric method
decomposition of hydrazinium nitrate was investigated in a
[11]. Then, conversion fractions of sulfur were calculated. All
nitric acid medium by Venault et al. [6]. The use of ultrasound
the dissolution experiments were repeated at the same
in the dissolution kinetics of phosphate ore in HCl solutions
conditions by using the ultrasound power.
was studied by Tekin [7]. The effect of ultrasound on the
kinetics of the reduction of hexacyanoferrate (III) by
thiosulfate ions mediated by ruthenium dioxide hydrate was
3 Results and Discussion
±
In this paper particle size, concentration of Na2SO3
[*] T. Ingeç (e-mail: tingec@engineer.com), T. Tekin, Department of
Chemical Engineering, Faculty of Engineering, Atatürk University,
solution, temperature, and ultrasound power level were
25240 Erzurum, Turkey. chosen as parameters to investigate their effects on the

150  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ceat.200401905 Chem. Eng. Technol. 2004, 27, 1
 Full Paper

reaction kinetics. The excess amount of Na2SO3 solution was For a first chemical reaction with respect to A,
used for running out the sulfur in the experiments. Experi-
ments were conducted in both the presence (ultrasound Al + bBs ® productsl (2)
power: 26.15 W) and absence of ultrasound to ascertain the
the shringing core model is expressed as
effect of ultrasound. In all the experiments, a stirring rate of
r
600 rpm was applied with a magnetic stirrer to avoid particles Rc Rt
-rB drc ˆ bk CA dt (3)
settling in the reactor. Conversion time data obtained with R0 0
various concentrations of Na2SO3 solution, particle sizes and
temperatures are given in Tab. 1; it can be clearly seen that where,
ultrasound enhances the reaction rates. !
Diffusion-controlled and kinetically controlled ªshrinking rc bks CA
R0 1 ˆ t (4)
coreº models [12] have been applied to the rate data; R0 rB
regression analysis revealed that the kinetically controlled !
NB0 rc
1=3†
first-order rate model fits the rate data better than the other CA ˆ CA0 1 X and ˆ 1 XB (5)
models. VbCA0 B R0

Table 1. Percent dissolved S vs time at various Na2SO3 concentrations, particle sizes, temperatures.

Particle size (mesh)

% S dissolved without ultrasound % S dissolved with ultrasound

Time (min) ±10+20 ±20+30 ±30+40 ±40+45 ±10+20 ±20+30 ±30+40 ±40+45

30 1.600 0.880 4.110 10.78 3.440 5.160 14.64 15.80

60 2.300 3.850 8.640 13.50 7.400 11.67 29.40 36.22

90 3.500 5.420 10.75 16.51 10.33 16.73 35.70 50.21

120 4.810 6.770 11.82 18.50 15.26 26.08 37.04 63.50

150 6.330 8.860 13.77 20.73 24.27 35.32 44.07 73.69

180 7.730 10.81 14.36 26.25 37.50 45.17 62.14 82.01

Na2SO3 Concentration (M)

% S dissolved without ultrasound % S dissolved with ultrasound

Time (min) 0.75 1 1.25 1.5 0.75 1 1.25 1.5

30 0.430 0.880 1.460 2.880 4.490 5.160 6.340 11.75

60 1.910 3.850 4.030 4.800 10.25 11.67 15.50 24.89

90 2.610 5.420 5.950 7.360 12.49 16.73 18.26 37.43

120 2.760 6.770 8.900 9.600 21.01 26.08 29.98 39.88

150 5.640 8.860 10.99 11.71 26.81 35.32 41.80 44.46

180 6.830 10.81 11.61 13.76 36.37 45.17 52.23 63.45

Temperature (K)

% S dissolved without ultrasound % S dissolved with ultrasound

Time (min) 313 323 333 343 313 323 333 343

30 0.330 0.880 0.960 1.150 4.690 5.160 7.860 14.78

60 2.170 3.850 4.920 5.880 10.83 11.67 16.73 30.69

90 2.950 5.420 6.890 7.800 14.78 16.73 30.21 46.24

120 3.450 6.770 10.27 14.47 21.16 26.08 41.82 62.02

150 4.430 8.860 13.06 17.09 27.08 35.32 55.96 76.79

180 5.350 10.81 15.84 19.32 33.49 45.17 68.32 87.03

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 Full Paper

1=3 bks CA
1 1 XB ˆ t (6) 0
rB R0 ultrasound
-1 non-ultrasound

R0 rB 1=3 -2
tˆ 1 1 XB † † (7)
bks CA -3

-4

ln k
R0 rB
sˆ (8) -5
bkS CA
-6
s-values were estimated by means of linear regression -7
analysis (R2 = 0.969). s-values were calculated for particle size,
-8
concentration of Na2SO3 solution, and temperature1). 2.9 2.95 3 3.05 3.1 3.15 3.2 3.25
The s vs particle size plot is given in Fig. 1; a linear relation is (1/T) x 10- 3 (K)
obtained according to Eq. (8). The ln(s) vs ln(CA) plot in Fig. 2 Figure 3. Arrhenius plot.
has a slope of 0.94, approximately equal to 1. These results
confirm that the rate equation (6) describes the rate data
sufficiently well. factor; for example, the collision of SO3±2 ions with elemental
sulfur, S2O3±2 ions with elemental sulfur in the crystal lattice,
SO3±2 ions with S2O3±2 ions in the aqueous phase, and also the
steric factor.
6000
non-ultrasound
ultrasound Ea =RT
kˆ Ae (9)
τ (min.)

4000
To investigate the effect of ultrasound power on the reaction
kinetics, controlled setting of power input is required. The
2000 amplitude setting of the generator is used for this purpose. A
linear dependence is obtained between amplitude setting and
power input measured by the calorimetric method [13].
0 The dependence of the reaction kinetics on ultrasound
0 0.2 0.4 0.6 0.8 1 power is usually expressed by the following relation [14]:
R0 (mm)

Figure 1. Plot of s versus particle radius.

EW = (1 + dW)f (10)

10
9 where EW is the ultrasonic enhancement factor, calculated as
8
Kultrasound
7 EW = (11)
knon ultrasound
6
5
ln

4 By combining Eqs. (10) and (11) the following is obtained:

3
2 k = g ´ (1 + dW)f e±Ea/RT (12)
ultrasound
1 non-ultrasound

0 The data given in Tab. 2 are used in nonlinear regression

-0,29 0 0,22 0,41 analysis (error function @ 5´10±4) and unknown parameters are
ln CA estimated as g = 4785, d = 0.125 and f = 1.4. Thus, the Eq. (13) is
Figure 2. Plot of ln s versus ln CA.
given:

1:4 5050=T
The activation energy of the reaction is estimated from the k ˆ 4785 1 ‡ 0:125 W† e (13)
Arrhenius plot (Fig. 3) as 42 kJ/mol from ultrasound
experiments and 42 kJ/mol from non-ultrasound experiments. Finally, the rate expression can be summarized as follows:
Thus, the ultrasound does not influence the activation energy
of the reaction; its effect is solely focused on the pre- R0
rB
t=  
1=4
exponential factor A in Eq. (9), which embraces the collision b
CA
4785
1‡0:125W† e 5050=T

 
1=3
±
1 1 XS † (14)
1) List of symbols at the end of the paper.

152  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.de Chem. Eng. Technol. 2004, 27, 2
 Full Paper

Table 2. Rate constant k and ultrasound enhancement factor EW at various Ultrasound affects the pre-exponential factor A by enhancing
temperatures and ultrasound power.
primarily the collision of SO3±2 ions with elemental sulfur. Our
T (K ) Ultrasound k ” 10±4 EW opinion is that ultrasound enhances the attack of SO3±2 ions on
power (W) (cm/min) the elemental sulfur, this facilitates the formation of S2O3±2
313 0 4.940 1 ions.
323 0 9.980 1 Received: July 7, 2003 [CET 1905]

333 0 15.30 1

343 0 20.10 1
Symbols used
313 26.15 33.10 6.70

323 26.15 48.20 4.83 A [±] pre-exponential factor of Arrhenius

333 26.15 85.60 5.59
equation
CA [mol/dm3] molar concentration of Na2SO3
343 26.15 132.9 6.61
CA0 [mol/dm3] initial molar concentration of Na2SO3
323 22.95 31.84 3.19 E [kJ/mol] activation energy
323 29.35 135.1 13.54 k [cm/min] first-order reaction rate constant based
on unit surface area
NB0 [±] initial number of moles of solid reactant
Values calculated according to Eq. (14) are plotted against R [J/molK] ideal gas constant
experimental values in Fig. 4. The fitness is sufficiently good rc [mm] radius of unreacted core
to confirm Eq. (14). R0 [mm] initial particle radius
t [min] time
1 T [K] temperature
0,9 XB [±] fractional conversion of solid reactant
0,8
V [dm3] reaction volume
0,7
XS (Theoretical)

0,6
W [W] ultrasound power
0,5 rB [mol/dm3] molar density of solid reactant
0,4 s [min] time for complete conversion of solid
0,3 particle
0,2
0,1
0
0 0,2 0,4 0,6 0,8 1 References
XS (Experimental)

Figure 4. Theoretical versus experimental xs values. [1] T. J. Mason, J. P. Lorimer, Theory, Applications and Uses of Ultrasound
in Chemistry, Sonochemistry, Ellis, Horwood 1989.
[2] V. S. Moholkar, S. P. Sable, A. B. Pandit, AIChE J. 2000, 46 (4), 684.
[3] K. V. Pochivalov, A. M. Pronin, L. N. Mizerovskii, S. N. Kozlov, Fibre
Chem. 2000, 32 (4), 298.
4 Conclusion [4] C. Appaw, Y. G. Adewuyi, J. Hazardous Mat. 2001, 90 (3), 237.
[5] P. Sayan, J. Ulrich, Chem. Eng. Proc. 2001, 41 (3), 281.
The production reaction of sodium thiosulfate with running [6] L. Venault, P. Moisy, P. Blanc, C. Madic, Ultrason. Sonochem. 2001, 8
(4), 359.
Na2SO3 and elemental sulfur has been investigated in both the [7] T. Tekin, Hydrometallurgy 2002, 64, 187.
presence and absence of ultrasound. The particle size, reaction [8] A. Mills, L. Xiaojing, G. Meadows, Ultrason. Sonochem. 2000, 2 (1), 39.
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117.
tude of ultrasound power were chosen as parameters. [10] A. Tuulmets, S. Salmar, Ultrason. Sonochem. 2001, 8 (3), 209.
According to the results of the study, it was observed that [11] F. D. Snell, F. M: Biffen, Commercial Methods of Analysis, Mc Graw-
Hill, New York 1944.
with decreasing particle size and increasing concentration of [12] O. Levenspiel, Chemical Reaction Engineering, 2nd ed., Wiley, NewYork
Na2SO3 solution, the reaction temperature and amplitude of 1972.
ultrasound power increased the conversion fraction. [13] T. Kimura, T. Sakamoto, J. Leveque, H. Sohmiya, M. Fujita, S. Ikeda,
T. Ando, Ultrason. Sonochem. 1996, 3 (3), 157.
The reaction is chemically controlled and found to be first [14] C. Horst, Y. S. Chen, U. Kunz, U. Hoffmann, Chem. Eng. Sci. 1996, 51,
order and the activation energy is 42 kJ/mol in both situations. 1837.

______________________

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