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Rina Herdianita

 Chemical analyses of water samples are reported

in mg/kg solution (ci), equal to:
 mg/L of solution
 part per million (ppm) by weight

 Chemical calculations are generally in molal unit

(mi):
 moles/kg of solvent

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1000 ci
mi = 
MWi (1.000.000 - ci)

MW: Molecular Weight

ci : sum of the concentrations of all dissolved constituents

For thermal fluids:

ci
mi = 
1000 MWi

molesi
Xi = 
 moles
 moles includes all substances in any volume or mass of a mixture

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 An ideal solution or ideal mixture is a solution in

which the enthalpy of solution or enthalpy of
mixing is zero.
 The closer to zero the enthalpy of solution
is, the more “ideal” the behavior of the solution
becomes.
 Ideal solution is non-electrolytes mixture, where
the interactions between solute particles are so
weak.
 Concentration units of an ideal solution is
molality.

 For non-ideal solution, e.g. electrolytes, the

interactions between ions is so strong.
 Concentration units of a non-ideal solution is:
 Activity: thermodynamic concentration unit for solutes
in aqueous solutions
 Fugacity: thermodynamic concentration unit for gas
components in either vapor of liquid phases

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 If the activity is a and the concentration is

m, the relation is:
a = g.m
where g is the activity coefficients (which
measure deviation from ideality)
 For an ideal mixture, the activity coefficients (g)
are equal to one.
 For a non-ideal solution, the activity coefficients
(g) depend on the ionic charge (z) and ionic
strength (I, a measure of the average electrical
field surrounding an ion in solution).

Simple rules:
 All simple solids and water may be assumed to have
activities equal to 1.
 At most hydrothermal pressure, gas activities (or
fugacities) may be assumed to be equal to partial
pressure.
 Activities of dissolved species (ions & molecular or
uncharged species) may be calculated from some version
of the extended Debye-Hückel equation (this equation
actually calculates the activity coefficient, gi).

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Which z is.the ionic charge, I the ionic strength, å the ion size parameter, and
A, B, and B are constants.

I = ½ mizi2
Where zi is the ionic charge.

Values of ionic charge (z) and ion size parameter (å), for the common ionic species in
geothermal fluids (Truesdell and Jones, 1974). å is given in units of 10-8

H+ Na+ HCO3- HS- H3SiO4- H2BO3- F- SO42- NH4+ HSO4-

1 1 1 1 1 1 1 2 1 1
9.0 4.0 4.5 4.0 4.0 4.0 3.5 4.0 2.5 4.0

OH- CO32- Cl- Li+ K+ Ca2+ Mg2+

1 2 1 1 1 2 2
4.0 4.5 3.5 6.0 3.0 6.0 8.0

Activity coefficients.doc

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Value of the Debye-Huckel Coefficients A and B along the vapor pressure curve of water
(Helgeson et al., 1981). Units for A are kg1/2mole-1/2 and for B are kg1/2mole-1cm-1 x 108
(the product å x B cancels the 108 factor).

t(oC) A B t(oC) A B t(oC) A B t(oC) A B

0 0.4913 0.3247 90 0.5848 0.3401 180 0.7575 0.3605 270 1.0699 0.3855

10 0.4976 0.3261 100 0.5990 0.3422 190 0.7829 0.3629 280 1.1238 0.3889

20 0.5050 0.3276 110 0.6158 0.3443 200 0.8099 0.3655 290 1.1850 0.3926

30 0.5135 0.3291 120 0.6328 0.3465 210 0.8387 0.3681 300 1.2555 0.3965

40 0.5231 0.3307 130 0.6507 0.3487 220 0.8697 0.3707 310 1.3381 0.4009

50 0.5336 0.3325 140 0.6697 0.3510 230 0.9030 0.3734 320 1.4369 0.4058

60 0.5450 0.3343 150 0.6898 0.3533 240 0.9391 0.3762 330 1.5584 0.4114

70 0.5573 0.3362 160 0.7111 0.3556 250 0.9785 0.3792 340 1.7138 0.4178

80 0.5706 0.3381 170 0.7336 0.3580 260 1.0218 0.3822 350 1.9252 0.4256

.
.
 B is the deviation function and is the principal
extension term in the Debye-Hückel equation.
.
 Up to 250oC, B has values in the range 0.03 to
0.05 when concentrations are up to 3 molal
(Helgeson, 1969)