Fluid Phase Equrlzbria, 83 (1993) 253-260 253

Elsevier Science Publishers B.V., Amsterdam

SIMULTANEOUS SOLUBILITY OF AMMONIA AND SULFUR DIOXIDE IN

WATER AT TEMPERATURES FROM 313.15 K TO 373.15 K AND PRESSU-
RES UP TO 2.2 MPa
B. Rumpf, F. Weyrich and G. Maurer’
Lehrstuhl fiir Technische Thermodynamik, Universitat Kaiserslautern
D-6750 Kaiserslautern, Federal Republic of Germany

Keywords: gas solubility in liquids, weak electrolytes, sulfur dioxide, ammonia, water, experiments,
data, phase equilibria in complex mixtures

ABSTRACT
The simultaneous solubility of ammonia and sulfur dioxide in water was measured by a synthetic
method in the temperature range from 313.15 K to 373.15 K at two overall molalities of ammonia
(fiNIf, zz 3 mol/kg and IfiN& x 6 mol/kg) and pressures up to 2.2 MPa corresponding to a maximum
overall molality of SOs of about 10 mol/kg. Pitzer’s semiempirical approach is used to correlate the
new data. Results are reported and compared with literature data and correlations.

INTRODUCTION
In many chemical plants, for example in coal gasification processes or desulfurization equipment,
aqueous solutions of weak electrolyte gases have to be processed. The basic design of such equipment
requires information on phase equilibrium. Experimental data for the simultaneous solubility of the
weak base ammonia and acid gases like carbon dioxide, sulfur dioxide or hydrogen cyanide in most
cases are restricted to small ranges of temperature and composition. Therefore, physico-chemical
models for the involved complex equilibria cannot be tested or improved. As part of an ongoing
project dealing with experimental and theoretical work on the solubility of weak electrolyte gases in
aqueous phases, this contribution reports on experimental results for the simultaneous solubility of
ammonia and sulfur dioxide in water. From the new data, interaction parameters for an adapted
Pitzer model were determined.

EXPERIMENTAL
The apparatus for measuring the solubility of a gas in aqueous solutions is a modification of the
equipment presented in a recent publication on the solubility of hydrogen cyanide and sulfur dioxide
in water (Rumpf and Maurer, 1992).
In an experiment, a thermostated high pressure optical cell (material: Hastelloy C) is partially
filled with a known amount of the ammoniacal solution. At next, a known amount of sulfur dioxide
is added. More aqueous solvent is filled into the cell by a calibrated high pressure displacer until the
gas is completely dissolved. The pressure in the cell is reduced stepwise by withdrawing very small
amounts of the liquid mixture until the first stable bubble appears.
The mass of the gas (about 0.7 to 14 g) charged into the cell is determined by weighing with an
uncertainty of f 0.008 g. The volume of the ammoniacal solution filled into the cell was determined
by measuring the position of the high pressure displacer piston before and after each experiment.
The mass of the ammoniacal solution charged into the cell is determined with an relative uncertainty
of about 0.9 %.
‘Author to whom correspondence should be addressed

03783812/93/$06.00 01993 Elsevier Science Publishers B.V. All rights reserved

254

The temperature was determined with two calibrated platinum resistance thermometers placed in
the heating jacket of the cell with an uncertainty of about f 0.1 K.
Pressure transducers with ranges of 0.25, 0.6 and 2.5 MPa were used to determine the solubility
pressure. Before and after each series of measurements, the transducers were calibrated against a
pressure gauge. The maximum uncertainty in the pressure measurement as determined from the
calibration is 0.6 kPa at pressures up to 0.6 MPa and 11 kPa at higher pressures.
The ammoniacal solutions were prepared in a storage tank. The overall amounts of ammonia and
water f&led into the storage tank were determined by weighing. Corrections for the masses of ammo-
nia and water present in the gas phase have been applied, The combined uncert~nty in determining
the molality of ammonia (resulting from uncertainties in determining the mass of the components as
well as in determining the composition and the volume of the vapor phase) does not exceed 610-”
mol/kg (%H, % 3 mol/kg) and l.lO-’ mol/kg (h,v~~ x 6 mol/kg) (for details see Rumpf, 1992).

SUBSTANCES
High grade sulfur dioxide (2 99.98 mass per cent) and ammonia (2 99.999 moles per cent) were
purchased from Messer Griesheim, Ludwigshafen and used without further purification. Water was
deionized and further purified by vacuum distillation.

RESULTS
The experimental results for the simultaneous solubility of ammonia and sulfur dioxide in water at
temperatures between 313.15 and 373.15 K are given in table 1. Two overall modalities of ammonia
(%HJ 2: 3 mol/kg, mN& x 6 mol/kg) were investigated at total pressures up to 2.2 MPa corre-
sponding to a maximum overall molality of sulfur dioxide of about 10 mol/kg. The concentration
range was limited by the appearance of a second, sulfur dioxide rich phase at sulfur dioxide molalities
somewhat higher than those reported in table 1.
Some of the results are plotted in fig. 1. The addition of sulfur dioxide to an ammoniacal solution
at fixed temperature and overall molality of ammonia results in a decrease in total pressure as both
gases are dissolved chemically. When nearly all ammonia present in the liquid phase is converted
into ionic form, a rapid increase in the total pressure is observed. Increasing the overall amount of
ammonia in the liquid phase at mole ratios O< tiso,/rizN~~ SO.5 results in an increase in total pres-
sure. The opposite behaviour is observed for fisoz/Ifi~~a 21. Due to the strong chemical reactions,
a decrease in the total pressure below the vapor pressure of pure water at the same temperature is
observed at mole ratios 0.5< fi~o,/fi~~, <l.

MODELING
Fig. 2 shows a scheme of the model applied to correlate the new data. The model is a modification
of the thermodynamic framework developed by Edwards et al. (1978). Due to the chemical reactions,
the liquid phase contains ammonia and sulfur dioxide not only in molecular but also in ionic form.
To calculate the true molalities of the species present in the hquid phase, the condition for chemical
equilibrium yields the following expression for the thermodynamic equilibrium constant of reaction R:

(1)

The following balance equations for the overall amounts of ammonia and sulfur dioxide present in
the liquid phase were applied:
 Table 1: Exp. results for the simultaneous solubility of ammonia and sulfur dioxide in water

K
T

313.18
mNH,
mol/kg

3.192
%OL

0.000
T P
MPa

0.0182
T

353.10
G-Lmol/ kg

3.193 0.000
P
MPa

0.0944
T

373.06
LYTL
mol/kg

3.191 0.000
I
P
MPa

0.1838
313.20 3.192 3.306 0.0232 353.12 3.193 0.556 0.0809 372.98 3.190 0.000 0.1841
313.19 3.192 3.717 0.0799 353.10 3.193 1.183 0.0683 373.07 3.191 0.586 0.1603
313.18 3.192 4.601 0.1968 353.10 3.193 1.908 0.0459 373.01 3.191 1.199 0.1274
313.16 3.191 5.647 0.3269 353.11 3.193 2.ri.59 0.0467 373.09 3.191 1.741 0.1028
313.18 3.191 6.806 0.4534 353.11 3.192 3.4’13 0.1365 373.06 3.191 2.437 0.0954
313.10 6.085 0.000 0.0305 353.12 3.193 3.705 0.2400 373.09 3.191 2.720 0.0945
313.06 6.085 6.245 0.0341 353.11 3.192 4.974 0.689 373.09 3.191 3.184 0.1140
313.15 6.085 6.960 0.1318 353.09 3.193 4.990 0.695 373.08 3.191 4.019 0.5509
313.11 6.085 7.468 0.1860 353.11 3.193 5.506 0.865 373.08 3.191 4.620 0.859
313.11 6.085 7.643 0.2076 353.10 3.192 5.997 1.006 372.99 3.190 5.720 1.379
313.12 6.085 8.748 0.3408 353.10 3.192 7.693 1.443 373.19 3.190 7.450 2.045
333.09 3.194 0.000 0.0433 353.09 6.083 0.000 0.1405 372.88 6.086 0.000 0.2640
333.12 3.193 0.702 0.0373 353.15 6.082 0.434 0.1346 372.88 6.086 0.648 0.2489
333.12 3.193 1.407 0.0254 353.15 6.082 1.194 0.1183 372.86 6.086 0.713 0.2470
333.11 3.193 2.462 0.0214 353.15 6.082 2.116 0.0883 372.88 6.086 1.548 0.2077
333.12 3.193 3.030 0.0214 353.15 6.082 2.764 0.0601 372.90 6.086 2.028 0.1779
333.12 3.193 3.567 0.1133 353.14 6.081 3.583 0.0434 372.93 6.086 2.675 0.1331
333.11 3.193 3.580 0.1203 353.16 6.081 4.849 0.0412 372.94 6.086 3.297 0.1072
333.12 3.193 4.034 0.2236 353.15 6.081 5.718 0.0469 372.92 6.086 3.837 0.0931
333.11 3.193 5.379 0.5144 353.15 6.081 6.838 0.3380 372.87 6.086 5.125 0.0950
333.11 3.193 6.051 0.646 353.15 6.081 7.496 0.5785 372.99 6.086 5.814 0.0933
333.11 3.193 7.457 0.890 353.16 6.081 8.219 0.831 373.06 6.080 6.220 0.1978
333.13 3.193 7.797 0.945 353.09 6.082 8.734 1.005 373.03 6.081 6.757 0.4789
333.18 6.084 0.000 0.0682 353.09 6.082 9.550 1.254 372.94 6.086 6.770 0.4934
333.16 6.084 0.941 0.0602 353.10 6.082 10.522 1.542 373.05 6.079 7.734 1.020
333.17 6.084 1.953 0.0448 373.03 6.080 8.724
333.18 6.084 6.306 0.0752 373.13 6.079 10.182
333.18 6.083 6.587 0.1378
333.18 6.084 7.349 0.3220
333.19 6.084 7.861 0.4259
333.18 6.084 8.483 0.5631
333.17 6.083 9.537 0.771

The (small) decrease in the number of moles of water was calculated from a balance for the total
amount of oxygen present in the liquid phase:

1000
72, = - - nHSO; - ns@- - nOH- (4)
MW
The charge balance yields

nH+ $ n,H$ = nHso; + 2 ’ nsOg- + nOH- . (5)

The total pressure and the vapor phase composition were caiculated using the equations

W(P-P:)).xW.y,
P.Yw-ip’,: =P;.&.e-v( (f-3
R.T

(4 i=NHs, SO*.
P. Yz . cp:’ = 4,” CT, P3 . f=P( (7)
256

Figure I: Experimental results for the simultaneous sotubility of ammonia and sulfur dioxide in
water. oq l : experimental results, this work. - correlation.

The caiCulation requires the knowledge of the temperature dependent equilibrium constants Kr-K4,
the activity coefficients of all species present in the liquid phase, Henry’s constants H!‘J) for ammonia
and sulfur dioxide in pure water, the vapor pressure, molar volume and dielectric constant of water
as well as information on the vapor phase nonideality and the partial molar volumes of the dissolved
gases.
The equilibrium constant for reaction Kr was taken from Bieling et al. (1989), those for reactions 2
and 3 from Kawazuishi and Prausnitz ( 1988) wh ereas the equilibrium constant for the autoprotolysis
of water was obtained from Edwards et al. (1978). Henry’s constants for ammonia and sulfur
dioxide were obtained from Bieling et al. (1989) and Rumpf and Maurer (1992), respectively. The
dielectric constant of pure water was taken from Bradley and Pitzer (1979). The vapor pressure and
the molar volume of water were taken from Saul and Wagner (1987)., A truncated virial equation
of state was used to calculate the fugacity coefficients. Pure component second virial coefhcients
BNH~.NH~and EL,, were calculated from a correlation based on the data recommended by Dymond
and Smith (1980). The second virial coefficient B soz,so2 and the mixed virial coefficients were taken
from Hayden and O’Connell (1975). There exist few methods to calculate activity coefficients of
both ionic and molecular solutes in concentrated electrolyte solutions. A well established method is
 257

vapor ”

NHs sos Hz0

t t t

NHs
I I
YOs
I
Hz0
NHs + Hz0 = NH: + OH- (1)
SOz + Hz0 = HSO; + H+ (2)
HSO, = SO;- + H+ (3)
Hz0 * H+ + OH- (4)
liquid ’

Figure 2: VLE and chemical reactions in the ammonia-sulfur dioxide-water system

the Pitzer model (Pitzer, 1973) as adapted by Edwards et al. (1978):

1000. GE
R.T.n,.M,
= Jr(l) + C m, m, (P!,:’ + P!,:’h(J)) + C ma. mJ mk ’ T,J,k . (8)
W#W w.k#w

As seven dissolved species are considered in the liquid phase, that equation in principle requires 56
binary interaction parameters fi!,;‘, @,$) and 84 ternary param eters r,,+ where only four parameters
$0) ) may be obtained from the binary subsystems. But
(P(O)
NH3,NHJr S02,so2, rNH~.NH~.NHa, TSo~So,,So~
this large number of unknown parameters may be reduced drastically by the following approxima-
tions: In the concentration range investigated, it seems to be reasonable to neglect all interaction
parameters between two or more ionic species of the same sign of charge. As the concentrations of H+
and OH- are rather small in comparison to other species, all interaction parameters between those
and other solute species are set to zero. Furthermore, molecular ammonia and sulfur dioxide are not
simultaneously present in the liquid phase (cf. fig. 2), therefore, all parameters describing interacti-
ons between those species are neglected. The parameter &kZ,NH3 was obtained from a correlation
based on literature data for the solubility of ammonia in water whereas the parameter &~Z,so2 was
taken from Rumpf and Maurer (1992) (cf. table 2).
Further considerations (cf. Rumpf, 1992) s h owed that the following equations may be used to
describe the interactions between the dissolved gases and the salts NH4HS0s, (NHd)sSOs:

B,t$, = v+ /3,$,+ v- @, (9)

rG.MX,MX= vt TG,M,M + 2 u+ ’ V- ~G,M,,,’ + V’ TG,X,X (10)
r G,G,MX = u+ TG,G,M + u- rG,G,X (11)
where G is either SOz or NHs and M,X is either NH:,HSO, or NH:,SOi-. A sensitivity study
showed that including the parameters B$La,(NH,)lso,: B&,NH,HS~~~ ~NH~.NH~,(NH,)~so~,
r NH~,(NH,)~sO~,(NH,)~SO~ and FS02,NH,HS03,NH,WS03 is sufficrent to correlate the new data within
the experimental uncertainty. The temperature dependence of the binary interaction parameters
was taken into account whereas it was neglected for the ternary parameters. The binary and ternary
parameters were simultaneously fitted to the new results for the total pressure. The resulting numbers
are given in table 2. Furthermore, table 2 re orts numbers for the temperature dependence of the
ionic interaction parameters /3$+ HSO-, pcH+ P so2-, /$k+ HSO-, /$$+ soz-, rNH:,NH:,HSO; and
rNH+ NH+ soz- which were deter&ed3from data ;eportec! ‘by johnstoye (51935) for the total and
part% ,‘,kss:res above solutions containing ammonia and sulfur dioxide (0.51 %so,/~fi~~, 51).
258

Table 2: Interaction parameters for describing the simultaneous solubility of ammonia and sulfur
dioxide in water

T,‘,/Ii

273.15 473.15

293.15 393.15

313.15 373.15

308.15 368.15

‘NH;,NH;,SO:- -0.00477 - -

Again, the influence of temperature on the ternary parameters was neglected whereas it was taken
into account for the binary parameters.
The combined set of parameters correlates the new data with an average relative deviation of only
2.6 % (I & I:;“=14 %, 1G II”- -4.8 kPa at T=313.06 I< and p=34.1 kPa).
Table 3 reports relative and absolute deviations between the correlation of the present work and li-
terature data. All of these authors (most of the data were reported more than thirty years ago) report
partial pressures of sulfur dioxide in the order of about 10 kPa, therefore larger relative deviations

Table 3: Comparison of literature data with the correlation of the present work

Source of data

323 14 2.0 - 37.3 - - - 0.01 - Newall (1955)

303-323 24 14.7 - 51 - 0.8 Sedov (1957)

303-368 103 13.0 12.5 228 36.3 8.6 2.4 0.34 1.2 1.5 Szarawara (1961)
 259

are observed. But the absolute deviations are mostly less than 1 kPa. The numbers for psoz given by
Berdyanskaya are mostly larger than those calculated from the correlation of the present work. The
opposite behaviour is observed for the data given by Sedov (1957) and Szarawara (1961) whereas
the data given by Jackson (1955), Johnstone (1955) and Newall (1955) show no systematic deviations.

CONCLUSIONS
The simultaneous solubility of ammonia and sulfur dioxide in water was determined by a synthetic
method at temperatures 313.15<T/Ks373.15 and pressures up to 2.2 MPa. Interaction parameters
for an adapted Pitzer model were determined from the new measurements. Work on extending the
results to higher molalities of ammonia and other temperatures as well as further work on correlating
the data with various models is in progress.

ACKNOWLEDGEMENT
Financial support of this investigation by the government of the Federal Republic of Germany
(BMFT Grant No. 0326558 A), BASF AG, L u d wi‘g s h a f en and Lurgi AG, Frankfurt is gratefully
acknowledged.

LIST OF SYMBOLS
a, b, c coefficients for temperature dependence of interaction parameters
B(o) “observable” combination of binary interaction parameters
activity of component i
Cfs functions of ionic strength in Pitzers equation
GE excess Gibbs energy
H(“) Henry’s constant of component i in water (on molality scale)
1.w
I ionic strength (=f . C, m, zf)
KR equilibrium constant for chemical reaction R
M molar mass
m, overall molality of component i
m, true molality of component i
n, overall number of moles of component i
n, true number of moles of component i
N number of data points
P total pressure
PZ partial pressure of component i
R universal gas constant
T temperature
V partial molar volume
X mole fraction
z, number of charges of component i
Greek letters
/$O), /j(i) binary interaction parameters
V fugacity coefficient
I- “observable” combination of ternary interaction parameters
Y activity coefficient
iJ+, v- number of cations and anions in salt MX
rf,,R stoichiometric coefficient of component i in reaction R
7 ternary interaction parameter
260

Subscripts Superscripts
abs absolute max maximum
cal calculated min minimum
exp experimental S saturation
G gas tot total
i,j, k component i, j, k * normalized to infinite dilution
MX Salt MX
R reaction R
rel relative
w water

Definition of average absolute deviation: 1& laba=k . ~~=, 1pk,eol- pk,erp1

Definition of average relative deviation: ) G Ire,= k Cr=‘=,1pktc~:~~~1

REFERENCES
Berdyanskaya, R. A., Golyand, S. M. and Chertkov, B. A. , 1959. On the partial pressure of SOz
over ammonium sulfite-bisulfite solutions. Zh. Prikl. Khim., 37: 1930-1936.
Bieling, V., Rumpf, B., Strepp, F. and Maurer, G. , 1989. An evolutionary optimization method
for modeling the solubility of ammonia and carbon dioxide in aqueous solutions. Fluid Phase
Equilibria, 53: 251-259.
Bradley, D. J. and Pitzer, K. S. , 1979. Dielectric properties of water and Debye-Hiickel parameters
to 350% and 1 kbar. J. Phys. Chem., 83: 1599-1603.
Brelvi, S. W. and O’Connell, J. P. , 1972. Corresponding states correlations for liquid compressibi-
lity and partial molal volumes of gases at infinite dilution in liquids. AIChE-J., 18: 1239-1243.
Dymond, J. H. and Smith, E. B. , 1980. The virial coefficients of pure gases and mixtures. Oxford
University Press.
Edwards, T. J., Maurer, G., Newman, J. and Prausnitz, J. M. , 1978. Vapor-liquid equilibria in mul-
ticomponent aqueous solutions of volatile weak electrolytes. AIChE-J., 24: 966-976.
Hayden, J. G. and O’Connell, J. P. , 1975. A generalized method for predicting second virial coeffi-
cients. Ind. Eng. Chem. Proc. Dev., 14: 209-216.
Jackson, A. and Solbett, J. M. , 1955. As cited by: Berdyanskaya et al., 1959.
Johnstone, H. F. , 1935. Recovery of sulfur dioxide from waste gases. Ind. Eng. Chem., 27: 587-593.
Kawazuishi, K. and Prausnitz, J. M. , 1988. Correlation of vapor liquid equilibria for the system
ammonia-carbon dioxide-water. Ind. Eng. Chem. Res., 26: 1482-1485.
Newall, H. E. , 1955. As cited by: Berdyanskaya et al., 1959.
Pitzer, K. S. , 1973. Thermodynamics of electrolytes. I. Theoretical basis and general equations. J.
Phys. Chem., 77: 268-277.
Rumpf, B. and Maurer, G. , 1992. Solubility of hydrogen cyanide and sulfur dioxide in water at
temperatures from 293.15 K to 413.15 K and pressures up to 2.5 MPa. Submitted to Fluid
Phase Equilibria.
Rumpf, B. , 1992. Untersuchungen zur Lijslichkeit reagierender Gase in Wasser und salzhaltigen
wiilrigen Liisungen. Dissertation, Universitit Kaiserslautern.
Saul, A. and Wagner, W. , 1987. International equations for the saturation properties of ordinary
water substance. J. Phys. Chem. Ref. Data, 16: 893-901.
Sedov, N. V. , 1957. As cited by: Berdyanskaya et al., 1959.
Szarawara, J. , 1961. Studies on statics of the system: HsO-NHs-SO,. II. Diphase equilibrium
“solution-gas phase”. Chem. Stosowana, 3: 395-425.