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Vapor pressures of water over saturated solutions with regard to two salts, in the NaCl + KCl + H2O, NaCl
+ NaNO3 + H2O, KCl + KBr + H2O, KCl + KI + H2O, KCl + KNO3 + H2O, and KCl + K2SO4 + H2O
systems, are reported in the (278 to 323) K temperature range. The determined vapor pressures served to
obtain the water activities, the osmotic coefficients, and the molar enthalpies of vaporization.
x1H1 + x2H2 + x3H3 salt 3. However, taking into account that the mole fractions of
dp
( )
dT i
)
T[x1V1 + x2V2 + x3V3]
salts x2 and x3 are small compared with that of water x1 and
that the molar volume of water in the gaseous phase (ideal gas)
is considerably larger than the molar volumes of all components
H1 ) HG1 - HL1 ; V1 ) VG1 - VL1 in the solid and liquid phases, one has
H2 ) HS2 - HL2 ; V2 ) VS2 - VL2 3
which generalizes the Modell and Reid58 result for binary xiVi x1V1 x1VG1 ) x1RT p (2)
i)1
systems. In eq 1, xi are mole fractions of components in the
solution, i ) 1,2,3, where 1 is water, 2 is salt 1, and 3 is salt 2. thus, it follows from eq 1 and eq 2 that the Clausius-Clapeyron
Vi and Hi represent changes in the molar volumes and the equation can be approximated by
molar enthalpies of components, and G, L, and S denote gaseous,
liquid, and solid phases, respectively. Thus, the pressure-
temperature change is related to the change in the volume and
( d dTln p )m2,m3
)
H
RT2
(3)
the enthalpy associated with evaporating x1 moles of water while where the apparent molar enthalpy change is associated with
simultaneously crystallizing x2 moles of salt 2 and x3 moles of evaporation of water and simultaneous crystallization of salts
Figure 1. Vapor pressures p of saturated aqueous solutions of sodium Figure 2. Vapor pressures p of saturated aqueous solutions as a function
chloride and potassium chloride as a function of temperature T. 0, ref 1; of temperature T. b, NaCl + KCl + H2O; 0, NaCl + NaNO3 + H2O.
, ref 2; 4, ref 4; O, ref 21; and b, this work.
H R ) CT - B (5)
The parameters A, B, and C for the investigated systems were
evaluated by an unweighted multivariate least-squares method
using p values from Table 1, and they are reported in Table 2.
As pointed out above, it is possible to compare our vapor
pressures in the sodium chloride-potassium chloride-water
system with those in the literature (Figure 1), and as can be
observed the agreement is very satisfactory. Figure 2 presents
systems with sodium chloride and Figure 3 those with potassium
chloride. As can be observed in Figures 2, 3, and 4, irrespective
of temperature p(NaCl + KCl + H2O) > p(NaCl + NaNO3 +
H2O) and p(KCl + K2SO4 + H2O) > p(KCl + KBr + H2O)
p(KCl + KNO3 + H2O) > p(KCl + NaCl + H2O) > p(KCl +
KI + H2O). The vapor pressure of water is always higher in
the systems with potassium salts than with sodium salts; i.e.,
water passes into the gaseous phase more easily in the case of Figure 4. Vapor pressures p of saturated aqueous solutions as a function
potassium salts. of temperature T. O, NaCl + NaNO3 + H2O; b, KCl + KNO3 + H2O.
Determined vapor pressures of water p can be also expressed
in terms of the water activity a1(T, m2, m3) ) p(T, m2, m3)/ the molar mass of water; i, i ) 2, 3, denote the sum of
p*(T) and by the value of the osmotic coefficient ) stoichiometric coefficients; i ) 2 for 1:1 electrolytes; and i
(T, m2, m3) ) 3 for 1:2 electrolytes. Thus, to calculate the osmotic
1000 coefficients, knowledge of the composition at the invariant
(T, m2, m3) ) - ln a1(T, m2, m3) (6) points, m2 and m3, is necessary, and these solubilities were taken
M1(2m2 + 3m3)
from the literature. Phase diagrams, especially in the NaCl +
where p*(T) are vapor pressures of pure water at given T and KCl + H2O system,21,22,26,28,31,39,40 were investigated a number
they are available from the Saul and Wagner equation.59 M1 is of times, and they are relatively well-known and accurate;
1622 Journal of Chemical & Engineering Data, Vol. 54, No. 5, 2009
Acknowledgment
The authors appreciate the technical assistance of Mrs. Mary
Mamana.
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