_I.Aemsol Sci. Vol.29,Suppl. I, pp.

S379-S380, 1998
0 1998 Published by Elsevier Science Ltd. All rights reserved
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Pergamon

THERMODYNAMICS
FOR HIGHLY CONCENTRATED
WATER - AMMONIUM
SULFATE
SOLUTIONS
P. Korhonen,
Finnish
*University

Meteorological

A. Laaksonen*,
Institute,

of Kuopio,Department

E. Batris and Y. Viisanen

Sahaajankatu

of Applied

20 E 00810 Helsinki,

Physics,P.O.Box

Finland.

1627, 70211 Kuopio, Finland.

KEYWORDS
Activity coefficient,
solution.

surface

tension,

ammonium

sulfale,

ammonium

bisulfate,

supersaturated

Ammonium sulfate ((NH&So&

which dissolves to ammonia (N&+) and sulfate (S042- ) ions
in aqueous solutions, is a common substance in the atmospheric aerosol particles. At lower
ambient relative humidities
aerosol particles may be highly concentrated.
Hysteresis effect
allows even the existence of the supersaturated aqueous salt particles in the atmosphere, which
according to Rood et al. (1989) can be common in the atmosphere. Thus, one needs various
thermodynamical
data also for the supersaturated aqueous salt solutions, for example, when the
nucleation of the aerosol particles is studied with numerical models. In order to determine the
vapor pressures of ammonia and sulfuric acid above the aqueous ammonium
sulfate solution
particle one needs the mean ionic activity coefficient of the solute (e.g. Bassett and Seinfeld,
1983). We present here an equation for the mean ionic activity coefficient
of aqueous
(NH&S04
valid up to 26.8 mol/kg (the saturated solution ca. 5.834 mol/kg). We also present
the mean ionic activity coefficient
of aqueous ammonium
bisulfate (NH4HS04). When the
particles are small one needs in addition the surface tension of the solution against air. The data
for the aqueous (NH4)2SO4 surface tension is presented only for moderate concentrations.
We
present here an estimation for the surface tension of highly concentrated
water - ammonium
sulfate solution. In the following the thermodynamic
properties are presented at 298.15 K.
The mean ionic activity coefficient
of aqueous ammonium
sulfate in the molality scale is
obtained by solving first the osmotic coefficient from the water activity presented by Tang and
Munkelwiz (1994). They have given a fitting for water activities of aqueous ammonium sulfate
at the concentrations
from 0 to 26.8 mol/kg (O-78 mass %). The osmotic coefficient was then
fitted to the expanded Bromleys osmotic coefficient model presented e.g. by Saxena and
Peterson (198 1) who included third order polynomial terms in the model. We have included
polynomial terms to model up to 9th order terms. The mean ionic activity coefficient is then
obtained by using Gibbs-Duhem
equation. The mean ionic activity coefficient (r&) as a function
of ionic strength (I) can be calculated from
-0.5108~2+2-Ifi
log,,(y,)

+ (0.06+0.6B,)(Z+Z-11
(i +aZ)

(I+&)

+ ;B,Ii.
I
i=l

(1)

Here z and Z refers to the charge of ions present in the solution. The fitting coefficients are
following: Bl=-3.50390944E-2,
B2= 3.73770098E-3,
B3=-2.10301983E-4,
B4=7.18178119E-6,
Bs = - 1.58509094E-7,
B6 = 2.275843 lOE-9, B7 = -2.05355438E-11,
Bs = 1.0576675 lE- 13 and
Bg= -2.37107320E-16.
Here E-X equals to 10..
s379

S380

Abstracts of the 5th International Aerosol Conference 1998

Figure 1.The activity coefficients of ammonium sulfate and ammonium bisulfate calculated
with equation 1 (lines) and calculated with the equation presented by Jacobson et al. (1996).
The same approach is used for the mean ionic activity coefficient of aqueous ammonium
bisulfate. Our fitting for aqueous Nl&HSOh is valid at the concentration range from 0 to 270.0
mol/kg (0 - 96.9 mass %). The obtained fitting coefficients are following: B1=1.953416731E2, B2 = -9.764358756E-4, Bs=-2.152588991E-5, Bq= -2.811506513E-7, B5= 2.298668607E-9,
Bg = -l.l84459425E-11,
B7 = 3.729677698E-14, Bs = -6.545729067E-17 and Bs =
4.09 14 13234E-20 In figure 1. the activity coefficients are compared with coefficients presented
by Jacobson et al. (1996).
The surface tension of aqueous (NH&S04 solution against air for the mass fractions 0 to c 1.0
of ammonium sulfate is estimated from Gibbs adsorption isotherm with numerical integration.
The isotherm is fitted by using the water activity and surface tension (from ICT, (1960)) data
for the concentrations from zero to the saturated solution. We have fitted the obtained surface
tension (cr) in the following polynomial form
CT= iAiX;
i=O

(2)

where X,,, is the mass fraction of salt. The fitting coefficients are AO = 0.07 19121335 1, Ai =
0.02238717151, A2 = -0.07996064682, A3 = 0.6985161142, & = -2.361475486, A5 =
4.291669494, A6 = -3.664358167 and A7 = 1.143836868.
REFERENCES

Bassett M. and Seinfeld J.H., 1983: Atmos.Env., Vol. 17, pp. 2237-2252.
ICT (International Critical Tables), 1960, Vol. 3, McGraw-Hill, New York.
Jacobson M.Z., Tabazadeh A., Turco R.P., 1996: J. Geophys. Res., Vol. 101, pp. 9097-9091.
Saxena P. and Petersson T.W., 198 1: J. Colloid. Interf. Sci., Vol. 79, pp. 496-5 10.
Rood M.J., Shaw M.A., Larson T.V. & Covert D.S., 1989: Nature, Vol. 337, pp. 537-538.
Tang I.N. and Munkelwiz H.R. , 1994: J. Geophys. Res., Vol. 99, pp. 18801-18808.