Figure 2-1. Illustration of the states of a system in terms of the gravitational energy of a ball.

-1 -1 Ta ble 2 -1 Henrys La w constants for g ases at 1 bar total pressure in mol L-1 bar-1

T( oC) 0 5 10 15 20 25 30 35 40 50

O2 2.18 x 10 -3 1.91 x 10 -3 1.70 x 10 -3 1.52 x 10 -3 1.38 x 10 -3 1.26 x 10 -3 1.16 x 10 -3 1.09 x 10 -3 1.03 x 10 -3 9.32 x 10 -4

N2 1.05 x 10 -3 9.31 x 10 -4 8.30 x 10 -4 7.52 x 10 -4 6.89 x 10 -4 6.40 x 10 -4 5.99 x 10 -4 5.60 x 10 -4 5.28 x 10 -4 4.85 x 10 -4

C O2 7.64 x 10 -2 6.35 x 10 -2 5.33 x 10 -2 4.55 x 10 -2 3.92 x 10 -2 3.39 x 10 -2 2.97 x 10 -2 2.64 x 10 -2 2.36 x 10 -2 1.95 x 10 -2

H 2S 2.08 x 10 -1 1.77 x 10 -1 1.52 x 10 -1 1.31 x 10 -1 1.15 x 10 -1 1.02 x 10 -1 9.09 x 10 -2 8.17 x 10 -2 7.41 x 10 -2 6.21 x 10 -2

SO 2 3.5 6 3.0 1 2.5 3 2.1 1 1.7 6 1.4 6 1.2 1 1.0 0 0.837

Ta ble 2-2. Density of water, dielectric constant an d Debye-Hckel an d Trues dellJones constants at 1 bar pressure Debye-Hckel constants Te mperature ( oC) 0 5 10 115 20 25 30 35 40 45 50 55 60 Density o f water (kg m-3) 0.99984 0.99977 0.99970 0.99896 0.99821 0.99693 0.99565 0.99394 0.99222 0.99013 0.98803 0.98562 0.98320 Dielectric constant 87.8 191 85.8 838 83.9 785 82.1 042 80.2 618 78.4 520 76.6 755 74.9 326 73.2 238 71.5 493 69.9 094 68.3 043 66.7 342 A 0.49 12 0.49 42 0.49 76 0.50 12 0.50 52 0.50 94 0.51 38 0.51 85 0.52 35 0.52 87 0.53 42 0.53 99 0.54 59 B 0.3 248 0.3 254 0.3 262 0.3 270 0.3 279 0.3 289 0.3 299 0.3 310 0.3 322 0.3 334 0.3 347 0.3 360 0.3 373

Ta ble 2-3. Para meters for the Debye-Hckel an d Truesdell-Jones equations at 1 At m Debye-Hckel Ion H+ Na+ K+ Mg
2+

Truesdell-Jones ai ( ) 4.78 4.32 3.71 5.46 4.86 5.48 4.55 7.04 5.08 6.17 5.51 4.87 5.80 4.80 6.65 1 0.6 5 3.46 3.71 5.4 5.4 5.31 b (L mol -1) 0.2 4 0.0 6 0.0 1 0.2 2 0.1 5 0.1 1 0.0 9 0.2 2 0.1 6 0.2 2 0.2 2 0.2 4 0.1 0 0.0 1 0.1 9 0.2 1 0.0 8 0.0 1 0 0 -0.07

a i () 9.0 4.0 3.0 8.0 6.0 5.0 5.0 6.0 6.0 6.0 6.0 6.0 5.0 4.5 9.0 3.5 3.5 3.0

Ca2 + Sr 2+ Ba2 + Mn 2 + Fe2 + Co 2+ Ni

2+

Zn 2+ Cd 2+ Pb 2+ Al3 + OH F
-

ClHC O 3 CO 3 SO 4
2 2

4.0 4.5 4.0

Ta ble 2-4. A ppro priate ranges of ionic strengths for activity coefficient mo dels. Mo del Deb ye-Hckel Davies Truesdell-Jones Specific Ion Interaction Pitzer Ionic strength (moles L-1) 0 to 0.1 0 to 0.6 0 to 2 0 to 4 0 to 6

Figure 2-2. Schematic representation of the variation in activity coefficients versus the ionic strength of solutions.

Figure 2-3. Graphical illustration of various reaction orders in terms of the variation in concentration of species A versus time and reaction rate versus concentration of species A. After Appelo and Postma (1996).

Figure 2-4. Dissolution rates (mol m-2 s-1) for common minerals, carbonates, and silicates, as a function of pH. After Lerman (1990). From Transport and kinetics in surficial processes by A. Lerman in AQUATIC CHEMICAL KINETICS edited by W. Stumm, pp. 505-534. Copyright 1990. This material used by permission of John Wiley & Sons, Inc.

Figure 2-5. Comparison of half-lives of various reactions and residence times of water in different reservoirs. From Langmuir (1997).

Figure 2-6. Variation of free energy of nucleation as a function of particle radius. The maximum free energy of formation corresponds to the maximum energy barrier. At greater particle radii the free energy of nucleation decreases and eventually becomes negative, and nucleation will proceed spontaneously. Modified from Drever (1997).

Figure 2-7. Schematic representation of a mineral reacting with a solution during dissolution. The rate-controlling step can be the diffusion of species through the solution, diffusion of species through the reaction zone, or the rate of the surface reaction. Given the slow rate of diffusion of species through the reaction zone, at some point the thickness of this zone will become sufficiently great that the diffusion of species through the reaction zone will become the ratecontrolling step. Modified from Drever (1997).