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Ind. Eng. Chem. Res.

1998, 37, 1167-1172 1167

Solubility of Sulfur Dioxide in Sulfuric Acid of High Concentration


Qinglin Zhang, Hui Wang, Ivo G. Dalla Lana, and Karl T. Chuang*
Department of Chemical and Materials Engineering, University of Alberta,
Edmonton, Alberta T6G 2G6, Canada

The solubility of sulfur dioxide (SO2) in concentrated aqueous sulfuric acid (60-96 wt %) was
measured at different SO2 partial pressures and at temperatures of 298, 383, and 393 K. A
correlation is derived relating the SO2 solubility in aqueous sulfuric acid solution with different
SO2 partial pressures. Further simplifications for high concentrations of the sulfuric acid solution
allow the direct determination of a Henry’s law constant and its dependence on temperature
using the measured solubility data and the correlation. A comparison of the correlation with
limited literature data is also presented. The correlation well represents both the experimental
data of this work and the data reported in the literature. The overall heats of solution of SO2
in 79.01 and 95.91 wt % sulfuric acid solutions were also estimated using a van’t Hoff type
dependence of Henry’s law constant on temperature.

Introduction Equilibrium Equation of the SO2-H2SO4


Aqueous Solution System
Sulfur dioxide (SO2) is frequently encountered when
recovering metals from sulfide ores, in sulfuric acid Solution of SO2 in aqueous sulfuric acid solution can
production, in the combustion of sulfur-containing fossil be considered as a single solute gas-liquid equilibrium
fuels, and during sulfur recovery from hydrogen sulfide. system. The vapor phase dissociation of SO2 is ap-
It is possible to analyze SO2 recovery by gas-liquid preciable only at high temperatures (Edwards et al.,
absorption in an appropriate solvent providing solubility 1975) and may therefore be neglected in our work. The
properties are available. In our work, we needed to vapor pressure of H2SO4 is also extremely low under
establish material balances for sulfur in the two phases our experimental conditions and can be neglected (Perry
of the gas-liquid system, SO2-concentrated sulfuric and Green, 1984). In aqueous sulfuric acid solution, SO2
acid. However, a comprehensive survey of the literature exists in molecular and ionic forms. The chemical
indicated very limited information on solubility of SO2 equilibrium between these two forms may be described
in sulfuric acid of concentration from 60 to 96 wt % at by an ionization equilibrium constant, K. For the SO2
temperatures >373 K. and aqueous sulfuric acid system, the simpler pertinent
Of the available properties, the majority deal with equilibrium reactions possible in the liquid phase are
SO2 solubility at 101.3 kPa and 353 K or lower temper- listed below:
atures (Miles et al., 1920 and 1946; Lopatto et al., 1934;
Johnstone et al., 1934; Hayduk et al., 1988). Although SO2 + H2O S H2SO3 (1)
various studies have been carried out on SO2 solubility
in pure water (Edwards et al., 1975 and 1978; Rumpf
H2SO3 S HSO3- + H+ (2)
and Maurer, 1992) or in dilute sulfuric acid of concen-
trations of <22 wt % (Pitzer et al., 1977; Hunger et al.,
1990; Govindarao et al., 1993), no model is available to HSO3- S SO32- + H+ (3)
correlate the SO2 solubility in sulfuric acid of high
concentration. When the available data are examined,
many inconsistencies are evident, even in regions where H2O S H+ + OH- (4)
different sets of data overlap. As a result, the literature
does not provide reliable solubility values for calcula-
tions at different process conditions. Additional experi- H2SO4 S H+ + HSO4- (5)
mental data at high acid concentrations and tempera-
tures are needed. A correlation of such information The corresponding chemical equilibrium constants
based on sound thermodynamic principles would also can be written as follows:
be useful.
In this paper, we report experimental results for the mH2SO3 γH2SO3
solubility of SO2 in concentrated sulfuric acid solutions K1 ) (6)
at temperatures of 298, 383, and 393 K and at different mSO2mH2O γSO2γH2O
SO2 partial pressures. A simple correlation was estab-
lished to relate the partial pressure of SO2 to the mHSO3-mH+ γHSO3-γH+
solubility of SO2 in sulfuric acid of high concentrations K2 ) (7)
at temperatures up to 393 K. mH2SO3 γH2SO3

* To whom all correspondence should be addressed. E- mSO32-mH+ γSO32-γH+


mail: Karlt.chuang@ualberta.ca. Telephone: (403) 492 4767. K3 ) (8)
Fax: (403) 492 2881.
mHSO3- γHSO3-

S0888-5885(97)00611-8 CCC: $15.00 © 1998 American Chemical Society


Published on Web 02/12/1998
1168 Ind. Eng. Chem. Res., Vol. 37, No. 3, 1998

mOH-mH+ γOH-γH+
K4 ) (9)
mH2O γH2O

mHSO42-mH+ γHSO42-γH+
K5 ) (10)
mH2SO4 γH2SO4

These equilibrium constants have been reported as a


function of temperature in the literature (Lowell et al.,
1970; Pitzer et al., 1977).
At equilibrium, the overall mass balance for SO2 in Figure 1. Schematic diagram of the solubility measurement ap-
paratus: (1) gas supply cylinder; (2) gas reservoir; (3) pressure
the liquid phase gives: gauge; (4) solubility cell; (5) heater and magnetic stirrer; (6) needle
valve; (7) 3-way valve; (8) on-off valve.
mSO2 ) mSO2 + mH2SO3 + mHSO3- + mSO32- (11)
concentrations >22 wt %. Because our sulfuric acid
The corresponding charge balance in the liquid be- concentration of interest is in the range 65-98 wt %,
comes: the concentration of molecular SO2 in sulfuric acid
solution, mSO2, may be approximated by its solubility
mH+ ) mHSO3- + 2mSO32- + mOH- + mHSO4- (12) in sulfuric acid, (mSO2); that is:

For SO2 as a molecular solute, equilibrium between mSO2 = mSO2 (17)


vapor phase and liquid phase is given by:
Based on this assumption (eq 17), the activities of
φSO2PSO2 ) mSO2γSO2H (13) ionized species in sulfuric acid are no longer needed for
the calculation of the concentration of the molecular
The fugacity coefficient, φSO2, can be calculated from solute, SO2. In this paper, the assumption (eq 17) was
a correlation by Hayden and O’Connell (1975): used in the interpretation of sulfuric acid concentrations
>65 wt %. The concentration of dissolved molecular
BP SO2 is taken equal to the solubility of SO2 in concen-
φSO2 ) exp (RT ) (14) trated sulfuric acid. The latter was measured experi-
mentally.
The values of B are available for different species, Combining eqs 13, 14, 15, and 17, we obtain:
such as SO2, at different temperatures from a compila-
BP
tion by Dymond and Smith (1969). ln PSO2 + ) ln H + ln mSO2 + 2βSO2-SO2mSO2
By adopting Edwards’ simplification of the Pitzer RT
model for activities (Edward et al., 1975), the activity (18)
of SO2 may be estimated as follows:
At relatively low SO2 pressures and high temperatures,
ln(γSO2) ) 2βSO2-SO2mSO2 (15) φSO2 approaches unity, enabling eq 18 to be further
simplified to:
Because βSO2-SO2 is a parameter characteristic of the ln PSO2 ) ln H + ln mSO2 + 2βSO2-SO2mSO2 (19)
molecular-molecular interaction (Edwards et al., 1975
and 1978; Rumpf and Maurer, 1992), it can be consid- The Henry’s law constant defined in eq 18 or 19, H, can
ered to be independent of the solute-solvent system. be estimated using the experimental solubility data of
Accordingly, the correlation given by Rumpf and Maurer SO2 at different sulfuric acid concentrations and tem-
(1992) based on solubility data for the SO2-H2O system peratures.
is used to obtain the following:

137.92 31270 Experimental Section


βSO2-SO2 ) 0.0934 - + (16)
T T2 Materials. The SO2 (>99.9%) was purchased from
Linde, N2 (prepurified) was purchased from Praxair
The total concentration of SO2 dissolved in the aque- Canada Inc., and sulfuric acid (>96 wt %) was supplied
ous sulfuric acid solution, [i.e., the solubility of SO2 by Anachemia Canada Inc.
(mSO2)] is determined experimentally. However, to Sulfuric acid of a specific concentration was prepared
correlate the solubility of SO2 at different SO2 partial by adding the concentrated acid solution to distilled
pressure using eq 13, the solubility of molecular form, water, and the concentration was determined by titra-
SO2 (mSO2), has to be determined based on the equilib- tion using a standard 0.1 N NaOH solution (Fisher
rium eqs 6-10 and mass and charge balance eqs 11 and Scientific Ltd.).
12 in the liquid phase. Additionally, activity coefficients SO2 Solubility Measurements. A diagram of the
for the different species in the liquid phase are also apparatus used for solubility measurements is shown
required for the determination of solubility of molecular in Figure 1. Two vessels were used: a stainless steel
form SO2 (mSO2). gas reservoir of 334 cm3, and a solubility cell made of
In high concentration sulfuric acid solutions, the Pyrex glass with an internal magnetic stirrer and a
dissolved SO2 was shown to be present mostly in its volume of 122 cm3. A Heiss pressure gauge ((0.5 kPa)
molecular rather than ionic form (Gold and Tye, 1950). was used to measure the pressures in both the reservoir
Govindarao and Gopalakrishna (1993) further showed and the solubility cell. The temperature in the solubility
that ionization of SO2 becomes negligible at sulfuric acid cell was controlled with an OMRON digital temperature
Ind. Eng. Chem. Res., Vol. 37, No. 3, 1998 1169

Table 1. Solubility of Pure SO2 in H2SO4 Solution


H2SO4 H2SO4
concentration, SO2 partial SO2 solubility, concentration, SO2 partial SO2 solubility,
wt % pressure, kPa mmol/kg H2SO4 wt % pressure, kPa mmol/kg H2SO4
at 298 K
79.01 95.72 325.6 95.91 110.4 476.4
79.01 128.4 441.6 95.91 117.5 511.7
79.01 152.8 535.5 95.91 128.7 563.6
79.01 167.0 598.8 95.91 138.8 621.9
79.01 179.1 658.1 95.91 153.0 700.5
at 383 K
79.01 142.8 72.02 95.91 147.1 100.7
79.01 173.8 84.56 95.91 177.4 124.0
79.01 190.6 95.50 95.91 205.0 144.6
79.01 199.9 108.5 95.91 240.5 171.3
at 393 K
65.71 64.34 42.81 75.19 142.9 79.70
65.71 86.84 61.25 75.19 155.0 86.88
65.71 113.5 75.47 75.19 166.2 95.16
65.71 115.4 88.13
84.37 68.60 32.81
79.01 131.0 51.72 84.37 109.4 50.16
79.01 206.0 87.06 84.37 129.7 61.56
79.01 231.3 99.25 84.37 151.0 73.91
79.01 254.6 113.4 84.37 168.2 86.41
87.72 157.9 100.8 95.91 184.3 99.53
87.72 202.5 131.1 95.91 202.6 110.6
87.72 228.8 139.3 95.91 228.9 130.5
87.72 258.2 160.9 95.91 248.2 140.6

controller. Stainless steel tubing of 1/8 in. o.d. was used column temperature kept at 333 K and the detector
for all connections. Compared with the volume of the temperature at 408 K. The GC was calibrated using
gas phase in the solubility cell, the volume of the tubing standard gas mixtures of SO2 and N2 supplied by
was negligible. Praxair Canada Inc. The pressure of SO2 was then
The measurement procedure involved accurately calculated based on the analysis and the total pressure
weighing the solubility cell and magnetic stirrer before in the cell. The mass of SO2 remaining in the gas phase
and after charging the cell with ∼70 g of acid. The was estimated with the equation of state for an ideal
accurate weight of sulfuric acid of the desired concen- gas. The amount of SO2 transferred from the reservoir
tration is obtained by subtracting the weight of the cell to the solubility cell was calculated from the pressure
and the stirrer from the total weight including the acid. decrease in the reservoir. The solubility of SO2 in
The total volume of the cell and the connecting tubes sulfuric acid could then be obtained by subtracting the
was predetermined by filling the sealed cell with water. SO2 remaining in the cell as gas phase from the total
The volume of acid charged was determined based on amount of SO2 gas transferred to the cell from the
the weight and density for a particular acid concentra- reservoir.
tion and temperature. The volume of gas phase at An isotherm of SO2 solubility in aqueous sulfuric acid
equilibrium was then obtained by subtracting the acid as a function of partial pressure of SO2 can be measured
volume from the total volume. The acid was deaerated by gradually increasing the cell pressure and recording
for a few minutes, with a nitrogen purge, under reduced the pressure changes in both the reservoir and the
pressure and with stirring. The amount of acid evapo- solubility cell at equilibrium. Although it was possible
rated was considered to be negligible because of the very to complete all of the measurements simply by succes-
low vapor pressure of concentrated sulfuric acid. Before sive increases in gas pressure over an initial acid charge,
the SO2 gas was transferred from the reservoir to the each measurement was repeated with fresh acid (pre-
solubility cell, the initial pressure and temperature in pared in a large batch) to avoid possible accumulation
both the reservoir and the cell were recorded. The of experimental errors when the pressure change in the
temperature of the cell was raised to a predetermined reservoir was very small.
level. The SO2 gas was then introduced from the
reservoir to the desired pressure in the cell by adjusting Results and Discussion
the needle valve. When the stirrer was turned on, the
rate of solution of SO2 gas into the concentrated acid in Experiments were conducted with pure SO2 at dif-
the cell was initially very high requiring that additional ferent partial pressures and at temperatures of 298, 383,
gas be introduced to reach/maintain the desired pres- and 393 K. The results obtained from different experi-
sure. When the pressure in the cell became constant, ments are shown in Table 1.
the final pressure readings in both the reservoir and Estimation of Henry’s Law Constant, H. The
the solubility cell were recorded after an elapsed time Henry’s law constant, H, can be determined with eq 18
of at least 1 h to ensure equilibrium conditions. or 19 combined with eqs 14 and 16. The mean values
At equilibrium, the gas-phase compositions were of H and their mean square of variance are shown in
analyzed with a GOW MAC gas chromatograph (GC) Table 2 for different sulfuric acid concentrations and
equipped with a 2-meter long 1/8 in. o.d. stainless steel different temperatures. For comparison, the solubility
column packed with Poropak Q (-100+120 mesh). A data for pure SO2 reported by Hayduk et al. (1988) were
thermal conductivity detector (TCD) was used, with the also used to calculate H for 97 wt % sulfuric acid at 298
1170 Ind. Eng. Chem. Res., Vol. 37, No. 3, 1998

Table 2. Estimated Henry’s Law Constant


H2SO4
temperature, concentration, H, mPa (kg H2SO4 solution)/mol
K wt % by eq 18 by eq 19
298 79.01 0.2882 ( 0.02a 0.2955 ( 0.01a
298 95.91 0.2310 ( 0.01 0.2360 ( 0.01
298 97.00 0.2032 ( 0.01 0.2102 ( 0.01b
383 79.01 1.988 ( 0.08 2.012 ( 0.08
383 95.91 1.456 ( 0.02 1.475 ( 0.01
398 65.71 1.469 ( 0.08 1.482 ( 0.09
398 75.19 1.795 ( 0.02 1.813 ( 0.02
398 79.01 2.290 ( 0.09 2.327 ( 0.09
398 84.37 2.088 ( 0.07 2.105 ( 0.07
398 87.72 1.605 ( 0.06 1.628 ( 0.06
398 95.91 1.836 ( 0.09 1.861 ( 0.09
a Mean square of variance. b Taken from Hayduk et al., 1988.

K. As Table 2 shows, H depends strongly on the Figure 2. Solubility of pure SO2 in sulfuric acid solution at 298
temperature. The Henry’s law constant, H, is also a K. Key: (9) 79.01 wt % H2SO4; (b) 95.91 wt % H2SO4; (2) 97.00
complicated function of acid concentration. At 393 K, wt % H2SO4 (Hayduk et al., 1988). Dashed line: calculated with
H increases with sulfuric acid concentration and reaches eq 19; dotted line: calculated with eq 18.
a maximum at an acid concentration of ∼79 wt %;
further increase in acid concentration results in a
decrease in H. This complicated dependence of SO2
solubility on acid concentration has been observed by
many researchers and was summarized by Hayduk et
al. (1988). The small mean square of variance indicates
that either eq 18 or 19 well represent the relationship
between SO2 partial pressure and its solubility in
concentrated sulfuric acid solution. For process design
purposes, H may be estimated from correlation (eq 18)
or based on a single experimental solubility measure-
ment at a particular acid concentration and temperature
(eq 19).
With H values determined, the dependence of SO2
solubility in a specific acid concentration on SO2 partial
pressure can be calculated using either eq 18 or 19. For
a given partial pressure of SO2, PSO2, the solubility of
SO2, mSO2, can be calculated directly using eq 19. To Figure 3. Solubility of pure SO2 in sulfuric acid solution at 383
calculate the dependence of the solubility of SO2, mSO2, K. Key: (b) 95.91 wt % H2SO4; (O) 79.01 wt % H2SO4. Dashed
on its partial pressure using eq 18, a numerical iteration line: calculated with eq 19; dotted line: calculated with eq 18.
procedure has to be used because the total pressure, P,
is the sum of SO2 partial pressure, PSO2, and the vapor
pressure of the sulfuric acid solution. Because eq 18
cannot be solved analytically for PSO2 versus mSO2, a
FORTRAN program was developed to solve eq 18
numerically. The computer program involves an itera-
tive procedure where eq 18 is changed into the general
form of F(PSO2, mSO2) ) 0, and the iteration is continued
until the value of F becomes < 10-5.
Comparisons of the calculated SO2 solubility using
either correlation 18 or 19 with the experimentally
measured solubility data are shown in Figures 2-4.
Evidently, both correlations represent the experimental
data well (Figures 2-4). As shown in Figure 4, the
solubility of SO2 decreases with increase in acid con-
centration and reaches a minimum at ∼79 wt % sulfuric
acid. The calculated solubility values using either eq
18 or 19 overlapped in the experimental range of Figure 4. Solubility of pure SO2 in sulfuric acid solution at 393
K. Key: (O) 95.91 wt % H2SO4; (b) 87.72 wt % H2SO4; (9) 84.37
interest, confirming the validities of these correlations.
wt % H2SO4; (0) 79.01 wt % H2SO4; (2) 75.19 wt % H2SO4; (1)
The results also indicate that the assumption of ideal 65.71 wt % H2SO4. Dashed line: calculated with eq 19; dotted
gas behavior for SO2 is valid at the low partial pressures line: calculated with eq 18.
and high temperatures used in the experiments.
An additional comparison of the reported data with
the calculated solubilities was also done using eq 19 to Estimation of the Overall Heat of Solution. As
avoid the unnecessary iteration procedures. Figure 5 reported previously by Govindarao and Gopalakrishna
shows that these calculated solubility values agree well (1993), Henry’s law constant, H, exhibits a van’t Hoff
with the experimental data. equation-type dependency on temperature; that is:
Ind. Eng. Chem. Res., Vol. 37, No. 3, 1998 1171

Figure 5. Comparison of the model with reported experimental


data by Lopatto et al. (1934). Key: (b) 66.71 wt % H2SO4 at 303
K; (9) 66.71 wt % H2SO4 at 313 K; (2) 70.74 wt % H2SO4 at 303
K; (1) 70.74 wt % H2SO4 at 323 K. Dashed lines: calculated with Figure 6. Estimation of SO2 heat of solution in sulfuric acid.
eq 19. Key: (b,O) 79.01 wt % H2SO4 with H obtained with eqs 18 and
19, respectively, and ∆Hs ) 20.87 kJ/mol ; (9,0) 95.91 wt %
∆Hs H2SO4 with H obtained with eq 18 and 19, respectively, and ∆Hs
ln H ) ln as - (20) ) 20.95 kJ/mol; (2) 66.71 wt % H2SO4, with H obtained with eq
RT
19, and ∆Hs ) 19.70 kJ/mol; (1) 70.74 wt % H2SO4, with H
obtained with eq 19, and ∆Hs ) 22.61 kJ/mol.
Then, the heat of solution, ∆Hs, can be determined by
plotting ln H versus 1/T. The values of H for particular Table 3. Estimated Overall Heat of Solution of SO2
sulfuric acid concentrations and different temperatures sulfuric acid, temperature, ∆Hs,
are used to estimate the least-squares value of the wt % K kJ/mol reference
parameters as and ∆Hs in eq 20. Figure 6 shows
22.0 303-353 -15.78 Govindarao and
excellent linearity (with squared regression coefficient Gopalakrishna (1993)
(r2) > 0.999) for the sulfuric acid concentrations of 79.01 66.71 303-313 -19.70 Lopatto et al. (1934)
and 95.91 wt %. The data reported by Lopatto et al. 70.74 303-323 -22.61 Lopatto et al. (1934)
(1934) were also used to estimate the heat of solution 79.01 298-393 -20.87 this work
at acid concentrations of 66.71 and 70.74 wt %. Table 95.91 298-393 -20.95 this work
3 shows the overall heat of solution of SO2 estimated lated solubility using our correlations with the experi-
with eq 20 for different acid concentrations and tem- mental data follows. The main attribute of our simplified
perature ranges. correlation (eq 19) is that it contains no adjustable
For the solution of SO2 in water, Johnstone and parameters, which enables the evaluation of the solubil-
Leppla (1934) reported an estimated heat of absorption ity of SO2 in sulfuric acid at different partial pressures
of 26.08 kJ/mol for the following reaction; of SO2 from one experimentally determined value of SO2
solubility at the desired sulfuric acid concentration and
SO2 (gas) S SO2 (aqueous) (21) temperature.

If we consider that the solution of SO2 in high concen- Conclusions


tration acid involves only the reaction in eq 20 (i.e., no
dissociation or hydrolysis occurs), then the heat of The SO2 solubility in concentrated aqueous sulfuric
solution in a concentrated sulfuric acid solution should acid solution was measured at temperatures of 298, 383,
approximate the heat of absorption estimated by and 393 K and at different SO2 partial pressures. A
Johnstone and Leppla (1934). Our values, 20.87 and relatively simple correlation is presented that describes
20.95 kJ/mol for 79.01 and 95.91 wt % acid solutions, the solubility of SO2 in sulfuric acid. The good agree-
respectively, are in the range of the value of 26.08 kJ/ ment between the calculated solubility value and the
mol reported by Johnstone and Leppla (1934). This experimental data reported in the present study and
agreement further supports the assumption of little or also in the literature further strengthens the validity
no dissociation of SO2 occurring in sulfuric acid of high of the correlation and its assumptions. The correlation
concentrations. should be useful for predictions of the equilibrium
It has been shown that the presence of sulfuric acid solubility of SO2 in high concentration sulfuric acid
in the solution increases the hydrogen ion concentration, under various process conditions.
which suppresses the hydrolysis of dissolved SO2. The
hydrolysis of SO2 may be neglected even at acid con- Acknowledgment
centration of 22 wt % (Govindarao and Gopalakrishna The authors acknowledge the financial support from
1993). This assumption of negligible hydrolysis or the Natural Sciences and Engineering Research Council
dissociation of SO2 led to the simpler correlations of Canada. The fruitful discussions with Prof. A. Mather
developed in our study. This assumption presumably of the University of Alberta are much appreciated.
is even more valid at the much higher acid concentra-
tions (65-96 wt %) used in this study, compared with
Nomenclature
its verification at 22 wt % by Govindarao and Go-
palakrishna (1993). The good agreement of the calcu- as ) constant, defined in eq 20
1172 Ind. Eng. Chem. Res., Vol. 37, No. 3, 1998

B ) the second virial coefficient of SO2 at a specified Govindarao, V. M. H.; Gopalakrishna, K. V. Solubility of Sulfur
temperature Dioxide at Low Partial Pressures in Dilute Sulfuric Acid
H ) Henry’s law constant, (kPa) (kg-solvent) (mol)-1 Solutions. Ind. Eng. Chem. Res. 1993, 32, 2111-2117.
∆Hs ) heat of solution of SO2 in sulfuric acid, kJ/mol Hayden, J. G.; O’Conell, J. P. A Generalized Method for Predicting
Ki ) the dissociation equilibrium constant for dissociation Second Virial Coefficients. Ind. Eng. Chem. Proc. Des. Dev.
1975, 14, 209-216.
reaction i
mj ) the concentration of the species j (molecule, cation, Hayduk, W.; Asatani, H.; Lu, B. C.-Y. Solubility of Sulfuric Dioxide
in Aqueous Sulfuric Acid Solutions. J. Chem. Eng. Data 1988,
or anion) in sulfuric acid solution, mole/(kg-sulfuric acid 33, 506-509.
solution)
Hunger, T.; Lapicque, F.; Storck, A. Thermodynamic Equilibrium
mSO2 ) solubility of SO2 in sulfuric acid solution, mol/(kg- of Diluted SO2 Absorption into Na2SO4 or H2SO4 Electrolyte
sulfuric acid solution) Solutions. J. Chem. Eng. Data 1990, 35(4), 453-463.
P ) the total gas pressure in the solubility cell, kPa Johnstone, H. F.; Leppla, P. W. The Solubility of Sulfur Dioxide
PSO2 ) the partial pressure of SO2 over sulfuric acid of given at Low Partial Pressures. The Ionization Constant and Heat of
concentration, kPa Ionization of Sulfurous Acid. J. Am. Chem. Soc. 1934, 56, 2233-
T ) absolute temperature, K 2238.
R ) gas constant, 8.314 J/(mol K) Lopatto, E. K.; Savinaev, A. M. J. Appl. Chem. (USSR) 1934, 7,
881-886.
Greek
Lowell, P. S.; Ottmers, D. M.; Strange, D. M.; Schwitzgebel, K.;
βSO2-SO2 ) the specific interaction parameter for SO2 Debeery, D. W. A Theoretical Description of the Limestone
molecules Injection-Wet Scrubbing Process, National Air Pollution Control
γj ) the activity coefficient of the species j in sulfuric acid Administration Contract Number CPA 22-69-138, 1970; Vol.
solution 1, NTIS Number PB 193-029.
φSO2 ) the fugacity coefficient of SO2 Miles, F. D.; Fenton, J. The Solubility of Sulfur Dioxide in Sulfuric
Acid. J. Chem. Soc. 1920, 117, 59-61.
Subscripts Miles, F. D.; Carson, T. Solubility of Sulfur Dioxide In Fuming
i ) dissociation reaction as defined by eq i, i ) 1-5 Sulfuric Acid. J. Chem. Soc. 1946, 786-790.
j ) species, H2O, H2SO4, H2SO3, SO2,H+, OH-, HSO3-, Perry, R. H., Green, D., Eds. Chemical Engineer’s Handbook, 6th
ed.; McGraw-Hill: New York, 1984; pp 3-68.
HSO4-, SO32-
s ) solution Pitzer, K. S.; Roy, R. N.; Silvester, L. F. Thermodynamics of
Electrolytes. 7. Sulfuric Acid J. Am. Chem. Soc. 1977, 99, 4930-
4936.
Literature Cited Rumpf, B.; Maurer, G. Solubilities of Hydrogen Cyanide and Sulfur
Dioxide in Water at Temperatures from 193.15 to 413.15 K and
Dymond, J. H.; Simith, E. B. The Virial Coefficients of Gases: A
Pressures up to 2.5 mPa. Fluid Phase Equilibr. 1992, 81, 241-
Critical Compilation; Oxford: New York, 1969.
260.
Edwards, T. J.; Newman, J.; Prausnitz, J. M. Thermodynamics of
Aqueous Solutions Containing Volatile Weak Electrolytes.
AIChE J. 1975, 21(2), 248-259.
Edwards T. J.; Maurer G.; Newman J.; Prausnitz J. M. Vapor- Received for review September 2, 1997
Liquid Equilibrium in Multicomponent Aqueous Solutions of
Revised manuscript received November 26, 1997
Accepted December 1, 1997
Volatile Weak Electrolytes. AIChE J. 1978, 4(6), 966-976.
Gold, V.; Tye, F. L. The State of Sulfur Dioxide Dissolved in
Sulfuric Acid. J. Am. Chem. Soc. 1950, 73, 2932-2934. IE9706119