By Donald Langmuir
Langmuir offers an intensive presentation of typical chemical concentrations, platforms and strategies to assist readers (1) comprehend controls at the chemical caliber of floor and subsurface waters, and (2) distinguish among the average and the anthropogenic. in contrast to so much authors, whose civil/sanitary engineering backgrounds advertise a extra aquatic chemistry point of view, Langmuir?s geology/geochemistry event focuses insurance at the chemical interactions among water and geological fabrics. The booklet presents precious education in utilizing within the geochemical computing device code MINTEQA2 as an quintessential problem-solving device.
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ZOKsp values are for the dissolution reaction written in the form: Si02 + 2H 20 ~ H4 SiO%. The Ksp function for chalcedony is from Nordstrom et al. (1990). The Ksp functions for quartz and amorphous silica are from Rimstidt and Barnes (1980). 21Nordstrom et al. (1990). The K value is Keq for the dissolution reaction written: Mg,Si z0 5(OH)4 + 6W =3Mg2+ + 2H4SiO~ + H20. 46 Thermochemical Principles Chap. 2 Equilibrium constants and enthalpies of selected reactions at 25°C and 1 bar pressure I Fluoride and Chloride Species Reaction H+ + P- = HFo W+2F-=HFi Na+ + F- = NaFo Ca2+ + F- = CaP Mg2+ + F- = MgP Mn 2++ P- == MnP Fe2++ F- = FeP Fe3+ + F- == FeF2+ Fe3++ 2F- = FeF!
Because it takes energy to break the bonds in most minerals (and in salts, generally) mineral dissolution is usually an endothermic process. In other words, most minerals (silicates, aluminosilicates, oxides, and sufides) increase in solubility (thus in their Ksp values) with increasing temperature (Fig. 7). This explains the relatively high concentrations of dissolved silica found in geothermal waters and why amorphous silica [Si0 2(am)] tends to precipitate, thus clogging heat exchangers when geothermal waters cool at the land surface.
4 cm 3/mol for Li+ and 36 cm3/mol for 1-, for example. Molar volumes of ions increase with increasing temperature. AV~ is negative for most ionization and dissolution reactions so that pressure generally increases the progress of ionization reactions and the solubility of minerals. Molar compressibilities for minerals range from 0 to -4 X 10-9 cm3lbar mol and can be assumed equal to zero up to about I kb pressure. Values for ions KO are generally in the range - 5 to -10 X 10-3 cm3lbar mol. AK~ for completely ionic reactions is small, but for dissolving minerals it may be large.