📘 ❞ Groundwater Geochemistry ❝ كتاب ــ Broder J. Merkel اصدار 2005

عن كتاب Groundwater Geochemistry:
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Theoretical Background.........................................................................1
1.1 Equilibrium reactions....................................................................................1
1.1.1 Introduction...........................................................................................1
1.1.2 Thermodynamic fundamentals..............................................................4
1.1.2.1 Mass action law.............................................................................4
1.1.2.2 Gibbs free energy ..........................................................................6
1.1.2.3 Gibbs phase rule............................................................................7
1.1.2.4 Activity..........................................................................................8
1.1.2.5 Ionic strength.................................................................................8
1.1.2.6 Calculation of activity coefficient ...............................................10
1.1.2.6.1. Theory of ion dissociation.................................................10
1.1.2.6.2. Theory of ion interaction...................................................12
1.1.2.7 Theories of ion dissociation and ion interaction..........................14
1.1.3 Interactions at the liquid-gaseous phase boundary..............................17
1.1.3.1 Henry-Law ..................................................................................17
1.1.4 Interactions at the liquid-solid phase boundary...................................18
1.1.4.1 Dissolution and precipitation.......................................................18
1.1.4.1.1. Solubility product..............................................................18
1.1.4.1.2. Saturation index.................................................................20
1.1.4.1.3. Limiting mineral phases ....................................................22
1.1.4.2 Sorption.......................................................................................24
1.1.4.2.1. Hydrophobic /hydrophilic substances ...............................24
1.1.4.2.2. Ion exchange......................................................................24
1.1.4.2.3. Mathematical description of the sorption ..........................30
1.1.5 Interactions in the liquid phase ...........................................................34
1.1.5.1 Complexation ..............................................................................34
1.1.5.2 Redox processes..........................................................................36
1.1.5.2.1. Measurement of the redox potential ..................................36
1.1.5.2.2. Calculation of the redox potential .....................................37
1.1.5.2.3. Presentation in predominance diagrams ............................41
1.1.5.2.4. Redox buffer......................................................................45
1.1.5.2.5. Significance of redox reactions .........................................46
1.2 Kinetics.......................................................................................................49
1.2.1 Kinetics of various chemical processes...............................................49
1.2.1.1 Half-life.......................................................................................49
1.2.1.2 Kinetics of mineral dissolution....................................................50
1.2.2 Calculation of the reaction rate ...........................................................51
1.2.2.1 Subsequent reactions...................................................................52
VIII Table of contents
1.2.2.2 Parallel reactions .........................................................................53
1.2.3 Controlling factors on the reaction rate...............................................53
1.2.4 Empiric approaches for kinetically controlled reactions.....................55
1.3 Reactive mass transport ..............................................................................57
1.3.1 Introduction.........................................................................................57
1.3.2 Flow models........................................................................................57
1.3.3 Transport models ................................................................................57
1.3.3.1 Definition ....................................................................................57
1.3.3.2 Idealized transport conditions .....................................................58
1.3.3.3 Real transport conditions.............................................................60
1.3.3.3.1. Exchange within double-porosity aquifers ........................61
1.3.3.4 Numerical methods of transport modeling ..................................63
1.3.3.4.1. Finite-difference / finite-element method..........................63
1.3.3.4.2. Coupled methods...............................................................65
2 Hydrogeochemical Modeling Programs .............................................67
2.1 General........................................................................................................67
2.1.1 Geochemical algorithms .....................................................................67
2.1.2 Programs based on minimizing free energy........................................69
2.1.3 Programs based on equilibrium constants...........................................70
2.1.3.1 PHREEQC...................................................................................70
2.1.3.2 EQ 3/6 .........................................................................................72
2.1.3.3 Comparison PHREEQC – EQ 3/6...............................................73
2.1.4 Thermodynamic data sets....................................................................76
2.1.4.1 General ........................................................................................76
2.1.4.2 Structure of thermodynamic data sets .........................................78
2.1.5 Problems and sources of error in geochemical modeling....................80
2.2 Use of PHREEQC.......................................................................................84
2.2.1 Structure of PHREEQC under the Windows surface..........................84
2.2.1.1 Input ............................................................................................85
2.2.1.2 Thermodynamic data...................................................................93
2.2.1.3 Output..........................................................................................94
2.2.1.4 Grid .............................................................................................95
2.2.1.5 Chart............................................................................................95
2.2.2 Introductory Examples for PHREEQC Modeling...............................95
2.2.2.1 Equilibrium reactions ..................................................................95
2.2.2.1.1. Example 1: Standard output – seawater analysis...............96
2.2.2.1.2. Example 2 equilibrium – solution of gypsum....................98
2.2.2.2 Introductory examples for kinetics..............................................99
2.2.2.2.1. Defining reaction rates ....................................................100
2.2.2.2.2. BASIC within PHREEQC...............................................103
2.2.2.3 Introductory example for reactive mass transport .....................106