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UNITED STATESDEPARTMENT OF THE INTERIOR
GEOLOGICAL SURVEY
PARTIAL COMPILATION AND REVISION OF BASIC DATA IN THE WATEQ PROGRAMS
By D. Kirk Nordstrom, Susan D. Valentine, James W. Ball, L. Neil
Plummer and Blair F. Jones
Water-Resources Investigation Report 84-4186
Menlo Park, California 1984
UNITED STATES DEPARTMENT OF THE INTERIOR
WILLIAM P. CLARK, Secretary
GEOLOGICAL SURVEY
Dallas L. Peck, Director
For additional information write to:
Office of the Regional Hydrologist Water Resources Division 345 Middlefield Road Menlo Park, CA 94025
Copies of this report can be purchased from;
Open-File Services Section Western Distribution Branch U.S. Geological Survey Box 25425, Federal Center Denver, Colorado 80225 (Telephone: (303) 234-5888)
CONTENTS
PageAbstract--- - - - - 1Introduction 2Evaluation of the Debye-Hiickel solvent parameters 3Compilation of data- - - - 6
Sources of data- - - - - -- -- 6The data base listing- - - - -- 8Refinement of the standard state thermodynamic properties of Fe2 *
and Fe 3 aqueous ions-- - - 10Thermodynamic data for aqueous Fe2 - - - 10Thermodynamic data for aqueous Fe3 - - - 12Internal consistency-- - - 14Reference source codes- 15
Acknowledgments 15References cited- -- - - - - -- - - - 16
ILLUSTRATION
PageFigure 1. Deviation of three evaluations for the temperature depen
dence of the dielectric constant relative to Malmberg and Maryott's data- - - 5
TABLES
Page Table 1. Debye-Hiickel "A" parameters as a function of temperature 6
2. List of compilations searched- 73. Heat of solution of FeCl 2 (solid) 114. Three sets of internally consistent, standard state (298.15 K)
thermodynamic data for Fe 2 (aq), Fe 3 (aq), Fe(OH) 2 (c), and goethite 13
5. Symbols used for "source" code- - -- 156. Partial compilation of thermodynamic data for the WATEQ
programs - 19
III
PARTIAL COMPILATION AND REVISION OF BASIC DATA
IN THE WATEQ PROGRAMS
By D. Kirk Nordstrom, Susan D. Valentine, James W. Ball, L. Niel Plummer, and Blair F. Jones
ABSTRACT
Several portions of the basic data in the WATEQ series of computer programs (WATEQ, WATEQF, WATEQ2, WATEQ3, and PHREEQE) are compiled. The density and dielectric constant of water and their temperature dependence are evaluated for the purpose of updating the Debye-Hiickel solvent parameters in the activity £o- efficient equations. The standard state thermodynamic properties of the Fe 2 and Fe 3 aqueous ions are refined. The main portion of this report is a com prehensive listing of aluminum hydrolysis constants, aluminum fluoride, aluminum sulfate, calcium chloride, magnesium chloride, potassium sulfate and sodium sulfate stability constants, solubility product constants for gibbsite and amorjphous aluminum hydroxide, and the standard electrode potentials for Fe°(s)/ Fe 2 (aq) and Fe2+ (aq)/Fe 3+ (aq).
INTRODUCTION
Several computer programs that calculate multicomponent chemical equilib rium for homogeneous or heterogeneous aqueous systems are presently available (Nordstrom, _et_al., 1979). One major difficulty in using these programs is the lack of critically evaluated thermodynamic data, specifically equilibrium constants and reaction enthalpies. Stockmayer (1978) has noted that the effort to evaluate fundamental physical and chemical data lags behind the efforts in other areas of research and technological development. Poor quality data can have dire consequences when applied to such important societal problems as energy supply, environmental quality and industrial productivity (Lide, 1981). The lack of reliable aqueous thermodynamic data makes it difficult to interpret water-quality processes and problems which have become increasingly important with the continued development of energy resources and urban and industrial construction.
Before there can be a meaningful evaluation of data, all the relevant literature must be compiled. The main purpose of this report is to provide an update of the basic data compiled from literature references for selected aqueous reactions relevant to water-mineral equilibria. These data are or ganized in a form that is convenient for anyone using chemical equilibrium computer programs.
This compilation was initially begun to provide a more reliable data base for the WATEQ series of computer programs. The first program, WATEQ, was de veloped by Truesdell and Jones (1974) and included a complete list of equili brium constants and reaction enthalpies with reference sources for the program data base. WATEQF (Plummer, et al., 1976), the FORTRAN version of WATEQ, includes equilibrium constants for manganese species as well as some revisions of the earlier compilation. WATEQ2 (Ball, e_t al., 1979; 1980) was developed from WATEQ and WATEQF but kept the original programing language (PL/1). Sev eral trace elements (Pb, Cu, Zn, Cd, Ni, Ag, As, I) were added to WATEQ2 and some further revisions of the two previous data bases were given. PHREEQE (Parkhurst, ^t_ al^., 1980) computes chemical equilibria, pH, and pE (or Eh) for heterogeneous systems including reaction progress calculations and mass transfer between solution phase and solid phases (precipitation-dissolution processes). The PHREEQE data base is similar to that of WATEQF, but revised to be compatible with WATEQ2. Finally, WATEQ3, (Ball, £t al., 1981) has incorporated uranium species along with a few more changes in the coding and the data base. The increasing number of changes in these programs makes it difficult to keep track of the data base and is further motivation for organi zing the data into a form that can be easily documented, updated and reviewed by WATEQ users. This report is not intended as a primary reference of thermo dynamic data. It is only intended as an aid to WATEQ users so that they can make more informed decisions regarding water-quality interpretations when employing WATEQ computations.
EVALUATION OF THE DEBYE-HUCKEL SOLVENT PARAMETERS
The original WATEQ program utilized activity coefficients for the major ions in natural waters which were calculated from the extended Debye-Huckel equation with a linear term:
log y. - - + bl
in which y. is the activity coefficient of the i ion, z, is the ion charge, I is the ionic strength, A and B are the Debye-Huckel solvent parameters, I is an empirical ion-size parameter, and b is a fitting parameter. This form of the Debye-Hiickel equation was first proposed by Huckel (1925) and is nearly identical to the original Bronsted (1922) equation in which the linear term (bl) accounts for specific short-range interactions between ions of opposite charge. The A and B parameters are functions of the solvent density, the dielectric constant and the temperature:
A =1000 ekTj
where e is the electronic charge, e is the dielectric constant of the solvent, k is the Boltzmann constant, T is the absolute temperature, p 0 is the density of pure water, and N is the Avogadro constant. The following physical con stants, evaluated and revised by Cohen and Taylor (1973), were used in the calculations:
N = 6.022045 x 10 e = 4.803242 x 10 k = 1.380662 x 10
Jln 10 = 2.302585.
1016
mol"
esu erg
These constants were substituted into the definition of A and B to obtain:"*1
A 1.824814xl0x p< mole (kgu= and
50.29012xl0 8x
CeT)
cm" 1 mole" 1 (kguH 2U
These formulae are more precise than those used in Truesdell and Jones (1974) although the difference is only in the fifth significant figure.
The density has a much smaller effect on A and B than the dielectric con stant and an extensive compilation and evaluation is not necessary. The investigation of Gildseth, et al. (1972) provides an accuracy of 3 ppm and a mean absolute deviation of 0.7xlO" 6 g/mL over the temperature range 0-80°C for the density of water. The function which best fits their data and addi tional measurements of comparably high precision is:
po = 1 - (t-3.9863) 2 (t + 288.9414) + 0.011445 exp (-374.3/t) 508929.2 (t + 68.12963)
where t is degrees C. Any inaccuracies in this representation will be far overshadowed by the uncertainties in the dielectric constant of water.
The dielectric constant is fundamental to any electrolyte theory of aque ous solutions; however, it is not known with the accuracy required for many types of applications, including Debye-Huckel calculations. Truesdell and Jones (1974) used the data of Malmberg and Maryott (1956) in WATEQ. Since then, there have been several additional measurements and three major evalua tions of the data. The earliest evaluation is that of Helgeson and Kirkham (1974) who fit a single equation to measurements for the pressure and tempera ture range of 1-5000 bars and 0-600°C. Bradley and Pitzer (1979) developed a single equation for the dielectric constant up to 350°C and 1000 bars. The most comprehensive evaluation in which the measurements were weighted according to precision and according to temperature range during fitting is that of Uematsu and Franck (1980). In Figure 1 the deviations of each of these three fitted equations are compared to the data of Malmberg and Maryott (1956). It is very clear from this comparison that these three evaluations agree very well with each other, but differ markedly from the data of Malmberg and Maryott (1956) for 0-100°C. The Uematsu and Franck (1980) evaluation has been chosed for the temperature dependence of the dielectric constant of water. Since the WATEQ series data base is only considered to be reliable for the temperature range 0-100°C, we have reduced the lengthy equation of Uematsu and Franck (1980) to:
e = 2727.586 + 0.6224107T - 466.9151 InT - 52000.87/T.
This equation fits to within 0.01 of the dielectric constant (about 0.013%) given by Uematsu and Franck's equation at any temperature in the range of 0- 100°C. In Table 1 the Debye-Hiickel A parameter is recalculated at 10° inter vals from 0-100°C and compared with the original WATEQ values, the values of Helgeson and Kirkham (1974) and those of Bradley and Pitzer (1979). The differences between our A values and those from the recent literature are negligible. The change in the temperature dependence of the A parameter re flects the change in the dielectric constant data. These changes will improve the temperature dependence of the activity coefficients.
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FIGURE 1. Deviation of three evaluations for the temperature dependence of the dielectric constant relative to Malmberg and Maryott's data.
TABLE 1. - Debye-Hiickel "A" parameters as a function of temperature
t, °C WATEQ Helgeson & Kirkham, 1974
Bradley & Pitzer, 1974
COMPILATION OF DATA
Sources of Data
This report
0102030405060708090
100
0.49170.49870.50620.51410.52250.53140.54080.55070.56130.57250.5845
0.49130.49760.50500.51350.52310.53360.54500.55740.57060.58480.5998
0.49120.49770.50550.51460.52380.53420.54590.55760.57070.58500.6006
0.49120.49760.50520.51390.52350.53420.54590.55840.57180.58590.6007
Primary references containing thermodynamic measurements were compiled from the list of references in Table 2. In addition to these references, several journals including "Geochimica et Cosmochimica Acta," "Marine Chemistry," "Journal of Solution Chemistry," and "Journal of Chemical Thermo dynamics" were searched for references cited in articles already known to the authors. A computer search in "Chemical Abstracts" for reactions involving aluminum hydrolysis was carried out for the years 1967-1980. The result (Table 6) is a comprehensive listing of equilibrium constants and reaction enthalpies. Data were checked against the original primary reference if possible or against the abstract in "Chemical Abstracts" to see that the ci tation and the values were accurately and fully recorded. To narrow the search, only values reported for 25°C (with a few exceptions) were selected. No analytical equations of equilibrium constants as a function of temperature were used in this report.
TABLE 2. - List of compilations searched
Author(s) Bibliographic information
Baes, C. F., Jr. and Mesmer, R. E.
Bond, A. M., and Hefter, G. T.
[periodical]
Christensen, J. J., Eatough, D. J., and Izatt, R. M.
Chariot, G., Collumeau, A., and Marchon, M. J. C.
Naumov, G. B., Ryzhenko, B. N. and Khodakovskii, I. L.
Perrin, D. D.
Robie, R. A., Hemingway, B. S., and Fisher, J. R,
Sadiq, M., and Lindsay, W. L.
1976, The Hydrolysis of Cations, John Wiley and Sons, New York, 489 p.
1980, Critical Survey of Stability Constants and Related Thermodynamic Data of Fluoride Complexes in Aqueous Solution, IUPAC Chem. Data Ser. No. 27, Permagon Press, Oxford, 71 p.
Bulletin of Chemical Thermodynamics, Thermochemistry, Inc., Stillwater, Oklahoma.
1975, Handbook of Metal Ligand Heats and Related Thermodynamic Quanti ties, Marcel Dekker, New York, 495 p.
1971, Selected Constants: Oxidation- Reduction Potentials of Inorganic Substances in Aqueous Solution, Butterworths, London, 73 p.
1971, Handbook of Thermodynamic Data, Atomizdat, Moscow, 240 p. (Eng. trans. by G. Soleimani, ed., I. Barnes and V. Speltz, N.T.I.S. PB-226-722).
1969, Dissociation constants of in organic acids and bases in aqueous solution, Pure Appl. Chem., 20, 133-326.
1977, Thermodynamic Properties of Minerals and Related Substances at 298.15K and One Atmosphere Pressure and a High Temperatures, U.S. Geol. Survey Bull. 1259, 456 p.
1979, Selection of Standard Free Ener gies of Formation for Use in Soil Chemistry, Colo. State Univ. Tech. Bull. 134, 1069 p.
TABLE 2. - List of compilations searched Continued
Authors Bibliographic information
Sillen, L. G., and Martell, 1964, Stability Constants of Metal-Ion A. E. Complexes, Spec. Publ. No. 17, The
Chemical Society, London (Metcalfe and Cooper) 754 p.
Sillen, L. G., and Martell, 1971, Stability Constants of Metal-Ion A. E. Complexes, Spec. Publ. No. 25, The
Chemical Society, London (Alen and Mowbray), 865 p.
Smith, R. M., and Martell, 1976, Critical Stability Constants. A. E. Vol. 4: Inorganic Complexes, Plenum
Press, New York, 257 p.
Yatsimirskii, K. B. and 1960, Instability Constants of Complex Vasil'ev, V. P. Compounds, Van Nostrand, Princeton
(Engl. transl.), 214 p.
The Data Base Listing
In Table 6 we have compiled the reported equilibrium constant and enthalpy measurements for (1) aluminum hydrolysis, (2) aqueous ion associations for alu minum fluorides, aluminum sulfates, calcium chloride, magnesium chloride, potassium sulfate and sodium sulfate, (3) the solubility product constants for gibbsite and amorphous aluminum hydroxide, (4) the oxidation-reduction poten tials for the Fe°/Fe2+ and Fe2+/Fe3+ couples, (5} the standard state thepnod^- namic values of the following aqueous ions: Al 3 , Ca2 , Mg 2 , Fe , Fe , K , and Na , and (6) the standard state thermodynamic properties of solid gibbsite. These substances are listed in alphabetical order by element, and for any one reaction the listing of measurements is in chronological order. The values which were given in the WATEQ, WATEQF, and WATEQ2 publications are also pro vided for comparison. The standard state for aqueous species is the hypothet ical ideal solution of unit activity at unit molality, 298.15 K and 1 bar. The standard state for gibbsite is the pure crystalline solid of composition A1(OH) 3 at 298.15 K and 1 bar. The calorie, rather than the joule, was used as the unit of energy because most of the published data are reported in calories, and the integrity of the original data is preserved by avoiding any additional conver sions. The most obvious reason for using the calorie is that the WATEQ data base has always been in calories and keeping the same energy unit would be more convenient for WATEQ users. Anyone else who wants to use this data base for other purposes can easily make the conversion to joules. Furthermore, Adamson (1978) presents valid criticisms for not using SI units.
All equilibrium constants involving hydrolysis have been written in terms of H and H2 0 rather than OH". This uniformity required conversion of some of the reported values. The notation for equilibrium constants follows the symbols used by Sillen and Kartell (1964): *K X is the first acid dissociation con stant, *K2 is the second dissociation constant, etc. KI represents the addi tion of hydroxide ion to a metal cation. A subscript "s" refers to the solubility product for a solid phase. For example *KS <» for gibbsite refers to the reaction:
Al(OH) 3 (solid) + H2 0 = A1(OH)I + H+
and the product KxK2 refers to:
Al3 + 20H~ = A1(OH)I .
There has been considerable discussion in the literature concerning the existence of polynuclear species (e.g. Aveston, 1965; Baes and Mesmer, 1976). We feel that these species occur under non-equilibrium conditions that do not merit evaluation of an equilibrium constant value. However we have included a compilation of the equilibrium constants for the dimer because of the consis tency of the values and the direct spectroscopic evidence for its existence (Akitt, e_t al^., 1969). Unfortunately, the dimer was not fitted with the other recommended values for the aluminum hydrolysis constants and the gibbsite solubility product constants (May, et_ al_., 1979). For this reason we do not recommend that the dimer be used in WATEQ computations until such time that its importance can be evaluated. Preliminary testing indicates that it has a negligible effect on the other equilibrium constants (Howard May, oral commun.).
Occasionally a reported value is clearly of higher quality than the others, based on the experimental approach and the reported precision. These values have been identified in the REMARKS column of Table 6 by the word RECOMMENDED. Several reactions have not been "recommended" because they can not be adequately evaluated at this time.
Uncertainties reported by the original authors are given in parentheses following the reported value. These numbers usually represent one standard deviation. The original articles should be consulted for further information regarding errors.
Please note that equilibrium constants which can be calculated from stan dard state free energies are not included. Free energies of substances and re actions are usually not measured directly. Free energies are commonly derived from measurements of enthalpies, heat capacities and equilibrium constants. An exception is the measurement of the Fe°/Fe2+ electrode potential which is di rectly proportional to the free energy of the aqueous ferrous ion if the experiment is carried out under carefully controlled conditions. If an attempt is made to rebuild equilibrium constants from tabulated free energies through the equation, AG° = - RTlnK, then large uncertainties can result unless exactly the same path is used as that from which the free energies were originally calculated. Because free energies are usually taken from different sources, a calculated equilibrium constant can be seriously in error and inconsistent
with other data. The solubility product constant for siderite provides a typical example of this problem. Although it is listed in many standard com pilations, there has been no direct measurement of the free energy of siderite, If we use the free energy data listed in N.B.S. Technical Note Series 270-3 and 270-4 for FeC03 (c), Fe2+ (aq) and CO*" (aq), then the log K = -10.94. The source for AG°(FeC03 ) is a solubility product measurement of siderite which is log K = -10.68 (Kelly and Anderson, 1935), noticeably different from the value back-calculated from free energies. The reason for this discrepancy is relatively simple. Different values for AGj (Fe 2 ) and AG^(C0 2 ") were used by Kelly and Anderson (1935) to calculate AG° (FeC0 3 ) than are listed in N.B.S_. Tech. Notes 270-3 and 270-4. The biggest change has been in the AG~(Fe2 ). Although this example is a fairly typical one, there are some equilibrium constants which are inconsistent by an order of magnitude or more because of the cumulative errors in adding free energies from different sources. For this reason, we have only listed equilibrium constant and re action enthalpy measurements. No equilibrium constant data are based on free energy calculations. Such calculations can be used to check consistency when enough data are available, but for listing equilibrium constants only primary data are used.
Refinement of the Standard State Thermodynamic Properties
of Fe 2 * and Fe 3 * Aqueous Ions
Free energies of formation from the elements for aqueous Fe 2 and Fe 3 ions are reported anywhere in the range of -18.85 to -22.1 kcal/mole and -1.1 to -4.27 kcal/mole, respectively. Enthalpies and entropies are discrepant by similar amounts. Recent measurements (1968-1980) of heats of solution, heats of oxidation and an electrode potential measurement can be used to narrow the range of uncertainty to a more acceptable set of values.
2Thermodynamic Data For Aqueous Fe
AG^(Fe2+ ) can be obtained by three independent pathways.^ The first pathway is by combining the values for AH°(Fe 2 ) with AS£(Fe 2 ) using the equation:
AGj = AH° - TAS° . it r
where AH* AS°, and AG° are the standard state enthalpies, entropies, and Gibbs free energy of formation from the elements. In the second pathway, AG~ is obtained from the standard electrode potential, E°, for the Fe°(s)/Fe 2 * reaox couple using the equation:
= -nFE° .
10
The third pathway involves calculating AG^(Fe2 ) from measurements of AG the solubility product constant, K, of Fe(OH) 2 (c) from the relationship:
and
AG£ = -RT£nK .
The value for AHj(Fe2 ) can be obtained from heat of solution measure ments of FeCl 2 (c) and the enthalpies of formation of FeCl 2 (c) and Cl~(aq),
AH°(Fe2+ , aq) = AH°(FeCl 2 ) - 2AH°(C1~, aq) + AH£(FeCl 2 )
where AH°(FeCl 2 ) is the standard heat of solution of FeCl 2 . The AH°(FeCl 2 ) has been measured by Li and Gregory (1952), Cerutti and Hepler (197?) and Gobble^(1978). All three measurements are in close agreement (Table 3). The AH£(C1~, aq) is known with a high degree of reliability (e.g. CODATA, 1977) and the only known value for AH~(FeCl 2 ) is that from Koehler and Coughlin (1959). Combining these data, the resultant AH°(Fe2+ , aq) = -21.61 kcal/mol. The AS£(Fe2 ) can be calculated from the third-law entropy, S°(Fe2+ ) reported by Larson, et al. (1968) and the entropies of the elements from Robie, et al. (1978). The resultant AG°(Fe2+) = -21.34 kcal/mol. This pathway is shown as set I in Table 4.
Electrode potential measurements for the Fe°(s)/Fe2 couple can be reli able if (1) the iron is pure and free from defects, (2) no oxygen is present in the system, (3) the potential is independent of pH and (4) no hydrogen evolution takes place. No investigation has shown beyond doubt that all of these conditions have been met; however, the most reliable attempt is Johnson and Bauman (1978). Using their value of E° = 0.415 V we calculate AG°(Fe2 ) = -19.15 kcal/mol. This pathway is the basis for set II in Table 4. Tne range of measured values is shown in Table 6. The difference between this number and the number derived from enthalpies and entropies is 2.2 kcal/mol, hardly an acceptable inconsistency.
TABLE 3. - Heat of solution of FeCl 2 (solid)
AH° (kcal/mol) Reference
-19.5(^0.2) Li and Gregory (1952)
-19.7(-0.2) Li and Gregory (1952) corrected byCerutti and Hepler (1977)
-19.815 Cobble (1978)
-19.82 Cerutti and Hepler (1977)
11
Careful measurements of the log Ksp (-15.1) for Fe(OH) 2 (c) have been made by Leussing and Kolthoff (1953). Two values have been calculated for AH£ of Fe(OH) 2 (c) based on heat measurements (see JANAF Tables, Stull and Prophet, 1971). The more commonly accepted value of AH° = -135.8 kcal/mol was not con sidered by JANAF to be as accurate as AHj = -137.2 kcal/mol. JANAF used the latter value and an estimate of S° = 21.0 cal/deg-mol to obtain AG~ for Fe(OH) 2 (c) = -117.6 kcal/mol. We prefer the former enthalpy value which has additional support from the electrochemical measurements of Dibrov, et al. (1980). If the S° value of 21 cal/deg«mol is considered to be the best avail able estimate then th| AG£ = -116.2 kcal/mol. Combining this value with the Ksp we obtain AG°(Fe 2 ) = -20.40 kcal/mol. These values form the basis for set III in Table 4.
Thermodynamic Data for Aqueous Fe3
The thermodynamic properties of Fe 3 are usually obtained indirectly from data on Fe2+ and the Fe /Fe 3 electrode potential. One direct value is available on AH~(Fe3 ) = -10.89 (-.17) kcal/mol from measurements on the heat of oxidation of solid iron to Fe3 by H 20 2 (Vasil'ev, et al_., 1976). Since this value is dependent on the AH° for H202 , we rechecked the calculation by using the peroxide enthalpy given in Wagman, et al. (1968). The difference is only 50 cal/mol, thus we have accepted the original value reported by Vasil'ey, et al. (1976). We now have an independent check on AH°(Fe 2 ) through the Fe 2 / Fea^enthalpy. Unfortunately, the Fe 2 /Fe3 enthalpy is not precisely known (see Table 6). Values range from 9.2 to 10.2 kcal/mol. In addition, two mea surements have been reported for the heat of reaction, based on hydrogen peroxide oxidation of Fe2+ . Sousa-Alonso, et_ a^. (1968) reported -69.8(-0.4) kcal/mol and Bemardelli and Tumanova (1971) reported -71.11 ^-0.03) kcal/mol for the heat of this reaction. From these data the Fe 2 /Fe 3 reaction enthalpy is 9.26 and 10.57 kcal/mol, respectively. Thus the reaction enthalpy must lie in the range of 9.2 to 10.6 kcal/mol and from the frequency of reported values and the average, a reasonable estimate would be 10.0 kcal/mol. Using this number and the AH£(Fe3+ ) from Vasil'ev, et ajL (1976) we obtain AH°(Fe2 ) = -20.89 kcal/mol. These enthalpies are used in both sets II and III of Table 4.
The standard electrode potential (-.7702 volts) and thus the AG° (17.76 kc^l/ mol) is known very precisely and very accurately (see Table 6) for trie Fe 2 /Fe3 couple. For this reason, the same recommended value is used in every set of Table 4. Since only one measurement for the enthalpy and entropy of goethite have been reported in the literature (Barany, 1965; King and Weller, 1970), these values are also the same in each set.
12
TABLE 4. - Three sets of internally consistent, standard state
nnodynamic data for Fe2 (<
Fe(QH) 2 (c), and goethite
(298.15 K) thermodynamic data for Fe2+ (aq), Fe3+ (aq),
Species*
AG£(Fe 2+)
AH|(Fe2+ ) S°(Fe2+ )
AG°(Fe3+ )
AH|(Fe3+ ) S°(Fe 3+ )
AG°(Fe2+/Fe3+ )
AH°(Fe2+/Fe3+ )
AS°(Fe2+/Fe 3+ )
AG°(Fe(OH) 2 )
AH|(Fe(OH) 2 )
S°(Fe(OH) 2 )
log Ksp
AG° (goethite)
AH| (goethite)
S° (goethite)
log Ksp
AH°(FeCl 2 , solid)
Set I
-21.34
-21.61
-25.6
-3.78
-11.04
-65.3
17.76
10.57
-24.1
-117.6
-137.2
21.0
-15.3
-116.8
-133.7
14.4
-41.7
-81.69
Set II
-19.15
-20.89
-30.4
-1.39
-10.89
-71.9
17.76
10.0
-26.0
-115.0
-135.0
19.3
-15.1
-116.8
-133.7
14.4
-43.5
-80.97
Set III
-20.40
-20.89
-26.3
-2.64
-10.89
-69.4
17.76
10.0
-26.0
-116.2
-135.8
21.0
-15.1
-116.8
-133.7
14.4
-42.7
-80.97
*Free energies and enthalpies have units of kcal/mol and entropies have units of cal/deg«mol.
13
Internal Consistency
Based on the previous discussion, it is possible to derive three sets of data relating to the thermodynamic properties of aqueous Fe 2 and Fe 3 + as shown in Table 4. Each set is internally consistent but not entirely consistent with each other set. Each set assumes certain selected data to be the most reliable, and the remaining data are calculated from these selected values by the standard thermodynamic relationships.
Set I is based on (1) Cerutti and Hepler's (1977) arguments and data for heat of solution measurements of FeCl 2 (c) which provides AH° for Fe 2+ , and an estimated S° for Fe 2 * from Larson, et al. (1968) from which AG° for Fe 2+ is calculated, (2) the recommended value for E° of Fe 2+ /Fe 3+ and Bernardelli and Tumanova's (1971) value for AH° of Fe 2+ /Fe 3+ from which AG° AH° and S° for Fe3 * and the log Ksp for goethite are calculated and (3) the JANAF values for Fe(OH) 2 from which the log Ksp of Fe(OH) 2 is calculated. This set then becomes incon sistent with the E° for Fe°(s)/Fe2+ of Johnson and Bauman (1978), the data on Fe(OH) 2 by Dibrov, .et al. (1980) and Leussing and Kolthoff (1953), and the best estimated enthalpy for Fe 2+ /Fe3+ . A further check on inconsistencies can be made by comparing the Ksp for goethite calculated from free energy data with the ion activity product (IAP) measured by Langmuir and Whittemore (1971). The AG° for goethite can be obtained from the AH° of Barany (1965) and the S° data oi King and Weller (1970). Combining these data with the AG° of Fe3+ from set I gives a log Ksp =--41.7 which does not compare favorably with the range of log IAP = -43.3 to -43.5 for laboratory solutions containing crystal line goethite and groundwaters from aquifers containing iron minerals.
Set II is based on (1) Johnson and Bauman (1978) for AG° of Fe2+ and the recommended value of AG° for Fe 2+ /Fe3+ from which AG° of Fe 3 is calculated, (2) Vasilev, ejt al. (1976) for AH° of Fe 3 + and the best estimated AH° of Fe 2 + / Fe 3 "*" from which AH° of Fe 2+ is calculated and (3) the log Ksp for Fe(OH) 2 from Leussing and Kolthoff (1953) and S° for Fe(OH) 2 from Dibrov, et al. (1980) from which AG° and AH° of Fe(OH) 2 is calculated. This set, of course, is inconsis tent with nearly all of the data in set I including primary data such as AH° and S° for Fe24" and AH° for Fe(OH) 2 .
Set III appears to be the best compromise in that it is most consistent with all the primary data. Set III is based on (1) the JANAF estimate for S° of Fe(OH) 2 and the AH° of Fe(OH) 2 from Dibrov, et al. (1980) from which AG° of Fe(OH) 2 is calculated, (2) the log Ksp of Fe(OH) 2 from Leussing and Kolthoff (1953) and AG° of Fe(OH) 2 from the previous calculation from xrfiich AG° of Fe 2+ is calculated, (3) the best estimated AH° of Fe 2+ /Fe 3+ and the AH° of Fe3+ from Vasil'ev, ejt al. (1976) from which AH° of Fe 2 "1" is calculated. Everything else is calculated from these values. Altnough set III shows greater consistency with more of the data than any other set, there really is no optimal choice because of the inherently large uncertainties in some of the data. More accurate and more precise measurements of AH° for Fe2+ /Fe3+ , AG° for Fe 2+ and Fe34" would help to resolve these inconsistencies. It would also be highly desirable to make additional measurements of AH° and S° for goethite in order to reduce the uncertainty and inconsistencies related to the log Ksp for goethite.
14
Reference Source Codes
The symbols for the source column in Table 5 are abbreviated reference citations coded in a similar manner to those in Sillen and Martell (1964). Each reference abbreviation contains the year of publication followed by the first letter of the first author's last name. When more than one article could have the same designation, they are distinguished by a lower case letter starting with "a", e.g. 77Ha, 77Hb.
Additional information is provided by a slash (/), an equality symbol (=), or a comma (,); the symbols are explained in Table 5.
TABLE 5. - Symbols used for "source" code
Symbols Interpretation
60F=62F=63F Data from 60F, 62F, and 63F are identical
68S/72P Data from 68S has been modified by 72P
43B, 53L Data from 43B and 53L have been combinedor averaged
ACKNOWLEDGMENTS
We are very grateful to Bill Sanders and the staff of the Menlo Park USGS Library for their efficient and courteous assistance in the pursuit of obscure references. Generous assistance was also provided by the library staff at the USGS national headquarters, the University of Virginia and Stanford University. Manuscript reviews by Bruce Hemingway, John Haas, Jr., Howard May, George Parks, Yousif Kharaka, Meeshka Borisov and John Hem were especially helpful.
15
REFERENCES CITED
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Aveston, John, 1965, Hydrolysis of the aluminum ion: Ultracentrifugationand acidity measurements: Journal of the Chemical Society (London),p. 4438-4443.
Baes, C. F. and Mesmer, R. E., 1976, The hydrolysis of cations: New York,Wiley-Inter-science, Chap. 6.2, p. 112-123.
Ball, J. W., Jenne, E. A., and Nordstrom, D. K., 1979, WATEQ2 - A computerizedchemical model for trace and major element speciation and mineralequilibrium of natural waters, iii Jenne, E. A., ed., Chemical modelingin aqueous systems: Washington, D. C., American Chemical SocietySymposium Series 93, p. 815-836.
Ball, J. W., Nordstrom D. K., and Jenne, E. A., 1980, Additional and revisedthermochemical data and computer code for WATEQ2 A computerized chemicalmodel for trace and major element speciation and mineral equilibria ofnatural waters: U.S. Geological Survey Water-Resources Investigations 78-116, 109 p.
Ball, J. W., Jenne, E. A., and Cantrell, M. W., 1981, WATEQ3 A geochemicalmodel with uranium added: U.S. Geological Survey Open-File Report SI- 1183, 81 p.
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Bernardelli, A. E. and Tumanova, T. A., 1971, Thermochemical study of theoxidation of Fe2 ion with hydrogen peroxide in aqueous solution at 25°C,Trudy Leningradskogo Tekhnologicheskogo Instituta Tsellyulozono-Bumazhnoi Promyshlennosti 25, 112-115.
Bradley, D. J. and Pitzer, K. S., 1979, Thermodynamics of electrolytes. 12.Dielectric properties of water and Debye-Hiickel parameters to 350°C and1 kbar: Journal of Physical Chemistry v. 83, p. 1599-1603.
Bronsted, J. N., 1922, Calculation of the osmotic and activity functions insolutions of uni-univalent salts: Journal of the American ChemicalSociety, v. 44, p. 938-948.
Cerutti, P. J. and Helper, L. G., 1977, The enthalpy of solution of ferrouschloride in water at 298 K: Thermochimica Acta, v. 20, p. 309-314.
Cobble, J. W., 1978, Chemical thermodynamic studies of aqueous tracecomponents in light water reactors at high temperature and pressures:EPRI Report 311-2.
CODATA, 1978, Recommended key values for thermodynamics 1977: CODATABulletin 28, 17 p.
Cohen, E. R. and Taylor, B. N., 1973, Least-squares adjustment of thefundamental constants: Journal of Physical and Chemical ReferenceData 2, p. 663-734.
Criss, C. M. and Cobble, J. W., 1964, The thermodynamic properties of hightemperature aqueous solutions. 4. Entropies of the ions up to 200°and the correspondence principle: Journal of the American ChemicalSociety, v. 86, p. 5385-5393.
16
Dibrov, I. A., Chervyak-Voronich, S. M., Grigor'eva, T. V., and Kozoliva,G. M., 1980, New values of thermodynamic constants of some iron oxides:Soviet Electrochemistry, v. 16, no. 6, p. 675-679.
Diehl, Harvey, 1979, High precision coulometry and the value of the Faraday:Analytical Chemistry, v. 51, p. 318A-329A.
Gildseth, Wayne, Habenschuss, Anton, and Spedding, F. H., 1972, Precisionmeasurements of densities and thermal dilation of water between 5° and80°C: Journal of Chemical and Engineering Data, v. 17, p. 402-409.
Helgeson, H. C. and Kirkham, D. H., 1974, Theoretical prediction of thethermodynamic behavior of aqueous electrolytes at high pressures andtemperatures. 1. Summary of the thermodynamic/electrostatic propertiesof the solvent: American Journal of Science, v. 274, p. 1089-1198.
Huckel E., 1925, The theory of concentrated aqueous solutions of strongelectrolytes: Physik. Z. 26, 93-147.
Johnson, G. K. and Bauman, J. E., Jr., 1978, Equilibrium constants for theaquated iron (II) cation: Inorganic Chemistry, v. 17, p. 2774-2779.
Kelly, K. K. and Anderson, C. T., 1935, Contributions to the data ontheoretical metallurgy. 4. Metal carbonates Correlation and applica tions of thermodynamic properties: U.S. Bureau of Mines Bulletin 384,73 p.
King, E. G. and Weller, W. W., 1970, Low-temperature heat capacities andentropies at 298.51°K of goethite and pyrophyllite: U.S. Bureau ofMines Report of Investigations 7369, 6 p.
Koehler, M. F. and Coughlin, J. P., 1959, Heats of formation of ferrouschloride, ferric chloride and manganous chloride: Journal of PhysicalChemistry, v. 63, p. 605-608.
Langmuir, Donald and Whittemore, D. 0., 1971, Variations in the stability ofprecipitated ferric oxyhydroxides, in Hem, J. D., ed., Nonequilibriumsystems in natural water chemistry: Washington, Advances in ChemistrySeries 106, p. 209-234.
Larson, J. W., Cerutti, Paul, Garber, H. K., and Hepler, L. G., 1968,Electrode potentials and thermodynamic data for aqueous ions: Copper,zinc, cadmium, iron, cobalt, and nickel: Journal of Physical Chemistry,v. 72, p. 2902-2907.
Leussing, D. L. and Kolthoff, I. M., 1953, The solubility product of ferroushydroxide and the ionization of the aquo-ferrous ion: Journal of theAmerican Chemical Society, v. 75, p. 2476-2479.
Li, J. C. M. and Gregory, N. W., 1952, Heats of solution and formation ofsome iron halides: Journal of the American Chemical Society, v. 74,p.4670-4672.
Lide, D. R., Jr., 1981, Critical data for critical needs: Science, v. 212,p. 1343-1349.
Malmberg, C. G. and Maryott, A. A., 1956, Dielectric constant of water from0° to 100°C: U. S. National Bureau of Standards Journal of Research,v. 56, p. 1-8.
May, H. M., Helmke, P. A., and Jackson, M. L., 1979, Gibbsite solubility andthermodynamic properties of hydroxy-aluminum ions in an aqueoussolution at 25°C: Geochimica et Cosmochimica Acta, 43, p. 861-868.
17
Nordstrom, D. K., Plummer, L. N., Wigley, T. M. L., Wolery, T. J., Ball, J. W., Jenne, E. A., Bassett, R. L., Crerar, D. A., Florence, T. M., Fritz, B., Hoffman, M., Holdren, G. R., Jr., Lafon, G. M., Mattigod, S. V., McDuff, R. E., Morel, F., Reddy, M. M., Sposito, G., and Thrailkill, J., 1979, A comparison of computerized chemical models for equilibrium calculations in aqueous systems, in Jenne, E. A., ed., Chemical modeling in aqueous systems: Washington, D.C., American Chemical Society Symposium Series 93, p. 857-892.
Parkhurst, D. L., Thorstenson, D. C., and Plummer, L. N., 1980, PHREEQE A computer program for geochemical calculations: U.S. Geological Survey Water-Resources Investigations 80-96, 210 p.
Plummer, L. N., Jones, B. F., and Truesdell, A. H., 1976, WATEQ - A Fortran IV version of WATEQ, A computer program for calculating chemical equilibrium of natural waters: U.S. Geological Survey Water-Resources Investigations 76-13, 61 p.
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Sillen, L. G. and Martell A. E., 1964, Stability constants of metal-ion complexes, Spec. Publ. No. 17, Metcalfe and Cooper, Ltd., 754 p. Supplement No. 1, Special Publication No. 25 (1971), 865 p.
Sousa-Alonsa, A., Chadwick, Isabel, and Irving, R. J., 1968, The heat of oxidation of ferrous ions with hydrogen peroxide: Journal of the Chemical Society (A), p. 2364-2366.
Stull, D. R., and Prophet, Harold, 1971, JANAF thermochemical tables, 2nd ed., National Standard Reference Data Series - National Bureau of Standards 37, 1141 p.
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18
TABLE 6
19
TABL
E 6.
Partial
compil
atio
n of
thermodynamic
data
for
the
WATEQ
programs
hi**
aqueous
ion
1115*
* H20 - A1
0H2*
log
K
-4.85
-4.9
6
-5.10
-4.9
8
-4.96
-4.3
-5.86
-5.03
-4.9
7(.0
2)
-5.0
2
-5.05
-4.9
-4.7
(.3)
-4.49
-5.1
6
-4.6
1
-4.8
9
-4.9
9
Gj--116.97(.33)
kcal/mol H° 126.9(1 )
kc
al/m
ol S° 73.
6(3.
6) ca
l/de
g.mo
l Re
fere
nce:
77
H
* H*
Source
H°
Source
REMA
RKS
07B
42H
531
54S
55Ka-55Kb
55T
561
56K
56K-76B
60F-62F-63P
63R
65H
67H
68H
68S
10"5
M
alum
inum
perchlorate, values at
10~* an
d 10~* al
so gi
ven
69G
11.0
69G
T -
30°C
69N
0.1
M sodium pe
rchl
orat
e
71V
-5.0
1(.
04)
72P
-5.5
5(.
09)
74H
I
- 0.1
5
-5.0
0
74T
15
.64
74T
W
ATEQ
-4.9
7
76P
14.7
75
76P
WAT
EQP
-5.3
5
78H
1
-0
.4
-4.9
87(.
08)
79M"
60B
11.9
(0.5
) 76
B-60
B WATEQ2;
RECOMMENDED;
H° an
d S° (-17.2(1.7)
cal/deg.mol) values fr
om76B
are
consistent wi
th 7
9M
References:
07B
BJerrum, H.(1907) Z.
Phys.
Chem
. 59
, 33
6-38
3.42
H Ha
rtfo
rd,
W.H.(1942) In
d. En
g. Ch
em.
34,
920-924.
531
Ito,
T.
and
Yui,
N.
(l95
3) Sci. Re
port
s Tohoku Un
iv.,
I,
37,
185-190.
54S
Schofield.R.K. an
d Taylor,A.¥.(l954)
J. Ch
em.
Soc.
(L
ondo
n),
4445-4448.
55Ka Ke
ntta
maa,J.(l955) Suom.
Kemi
stil
. 28
B 172-174.
55Kb Ke
nt tamaa,J.( 195
5) Ann. Ac
ad.
Sci.
Fe
nnic
ae,
All, No
. 67,
39 p
p.55
T Th
omps
on,L
.C.(
1955
) Ph
.D.
Thes
is,
Vayne
State
Univ., Detroit, 69 pp.
561
Ivanov,A.N.
and
Aleshin,S.N.(l956) Do
kl.
Mosk
. Sel'kh.
Akad
. Nauchn.
Konf.
22,
286-
292.
56K
Kubo
ta,H
.(l9
56)
Ph.D.
Thesis,
Univ.
Wisc
onsi
n, Ma
diso
n, 13
7 pp.
60F
Frin
k,C.
R.(l
960)
Ph.D.
Thesis,
Cornell
Univ., Ithaca,
161
pp.
62F
Frink.C.R.
an
d Peech,M.(l962) So
il Sci. Soc. Amer.
Proc.
26,
346-
347.
63F
Frink.C.R.
an
d Peech,M.(l963) In
org.
Ch
em.
2, 47
3-47
8.63
R Raupach,M.(l963) A
ust. J. So
il Res. J
_, 35-45.
65N
Nish
ide,
T. an
d Tsuchiya,R.(l 965) Bull.
Chem.
Soc. Jpn. 3§,
1398-1400.
67H
Hem.J.D. an
d Ho
bers
on,C
.E.(
l962
) U.S.
Ge
ol.
Survey W
ater
-Sup
ply
Pape
r 1827-A,
55 pp.
68H
Holm
es,L
.P.,
Cole
,D.L
., an
d Ey
ring
,E.M
.(l9
68)
J. Ph
ys.
Chem
. 72
, 30
1-30
4.68
S Su
lliv
an,J
.H.
and
Singley,J.E.(l968) J.
Am
. Wa
ter
Works
Asso
c. 60
, 12
80-1
287.
69G
Grunwald,E.
and
Fong,D.W.(l969)
J. Phya.
Chem
. 73,
650-
653.
69N
Nazarenko.V.A. an
d Ne
vska
ya,E
.M.(
l969
) Ru
ss.
J. Inorg. Ch
em.
\A_, 16
96-1
699.
71V
Volo
khov
.Y.A.,Pavlov,L.N.,Eremin,N.I.,
an
d Mironov,V.E.(l971) Zh
. Prikl. Khim.
44,
246-
249.
72P
Park
s,G.
A.(1
972)
Am.
Mine
ral.
57,
1163
-118
9.74
H Ha
yden
,P.L
. an
d Ru
bin.
A.J.
(197
4~T
in Aqueous-Environmental
Chemistry
of M
etals, Ru
bin,
A.J.
, ed
., An
n Ar
bor,
31
7-38
1.74
T Truesdell.A.H. an
d Jo
nes,
B.F.
(197
4) J.
Re
s. U.S. Ge
ol.
Survey £,
233-248.
76B
Baes
,C.F.,Jr.
and
Mesmer,R.M.(l976)
The
Hydrolysis of Cations, Wiley-Interacience,
Chap
. 6.2, 112-123.
76P
Plummer,L.N.,Jones,B.F., an
d Truesdell,
A.H.
(197
6) U.S. Geol.
Survey W
.R.I
. 76-13, 61
pp.
77H
Hemi
ngwa
y.B.S. an
d Ro
bie,
R.A.
(l97
7) Ge
ochi
m. Co
smoc
him.
Ac
ta 4J
_, 14
02-1
404.
78H
De He
k,H.
,Sto
l,R.
J.,
and
De Br
uyn.
P.L.
(l97
8) J.
Co
lloi
d Interface
Sci.
6£,
72-89.
79M
May,H.M.,Helmke,P.A.,
and
Jack
son,
M.L.
(197
9) Geochim. Co
smoc
him.
Ac
ta 4
3_,
861-
868.
806
Ball,J.W.,Nordstrom,D.K.,
and
Jenne,E.A.(l980) U
.S.
Geol
. Survey W
.R.I
. 78-116,
109pp.
Al3*
+ 2H
20 - Al(OH)*
+ 2H
*
log
K So
urce
H°
Sour
ce
REMA
RKS
-8.5
6 55
T
-8.6
3(0.1)
58G
TABL
E 6.
P
art
ial
com
pil
atio
n of
ther
mod
ynam
ic
dat
a fo
r th
e VA
TBQ
pro
gra
ma(
conti
nued
):
-9.7
65
H
-10
.60
68
3
-10
.28
(.5
) 68S
/72P
-9.9
69
H
-9.3
69
N/7
6B
-8.6
9(0
.1)
72P-
78H
-9.7
61
74
T
-10
.5
76B
-9.3
0
76P
-10.1
3(.
08)
79M
-60B
0.0
0.0
22.0
76B
10"^
M
alum
inum
p
erc
hlo
rate
, v
alu
e at
10""
-* M
un
reli
ab
le
mea
n fo
r re
sult
s at
10"'
an
d 10
"* perc
hlo
rate
0.1
M
sodi
um perc
hlo
rate
corr
ecte
d
to
I
0
calc
ula
ted
fr
om K
^ u
sing
log K
W -
-13
.99
7
(76B
)
VA
TBQ
estimate ba
sed
on a
linear in
crea
se in
hydrolysia constants
VATBQF
VATB
Q2 fo
r log
K; RE
COMM
ENDE
D;
H° wa
s ob
tain
ed by a
co
rrel
atio
n.
Referencea:
55T
Thompson
, L.C.(1955) Ph
.D.
Thesis,
Vayn
e St
ate
Univ., Detroit, 69 pp
.58G
Gaye
r,K.
H.,T
homp
son,
L.C.
, an
d Zajicek.O.T.(l958) Ca
n. J.
Chem.
36,
1268
-127
1.63
H Raupach,M.(l963) Aust.
J. Soil Hes. J_,
35-45.
68S
Sullivan,J.H.
and
Sing
ley,
J.E.
(1 %8) J.
Am.
Vater
Work
s As
soc.
60,
1280
-128
7.69
N Na
zare
nko.V.A. and
Nevskaya,E.M.(l969)
Russ.
J. Inorg. Ch
em.
_14_,
1696
-169
9.72
P Pa
rka,
G.A.
(197
2) Am.
Mineral. 57,
1163
-118
7.74T
True
sdel
l.A.H. and
Jones,B.P.(1974) J. Res. U.S. Ce
ol.
Survey 2,
23
3-24
8.76B
Baea
.C.F
.,Jr
. an
d Me
aner
,R.H
.Q97
6) Th
e Hydrolysis of
Cations,
Viley-Interscience,
Chap
. 6.
2, 112-123.
76P
Plum
mer.
L.N.
,Jon
es,B
.P.,
an
d Truesdell.
A.H.
(197
6) U.
S. Ge
ol.
Surv
ey V
.H.I.
76-13, 61
pp.
78H
Hemingway,B.S..Robie.H.A., an
d Ki
ttri
ck,J
.A.(
1978
) Ge
ochi
m. Co
smoc
him.
Acta 43
, 15
33-1
543.
79M
May,
H.M.
,Hel
mke,
P.A.
, an
d Jackson,M.L.(l 979)
Geoc
him.
Cosmochim. Ac
ta 4JJ, 86
1-86
8.808
Ball,J.V.,Nordstrom,D.K.,
and
Jenn
e.E.
A.(l
980)
U.S.
Ge
ol.
Surv
ey V
.R.I.
78-116,
109
pp.
0 - A1
(OH)
°
log
K
-15.
03
-15.2
Sour
ce
59A
68S
Source
REMA
RKS
10-4
-5M
alum
inum
pe
rchl
orat
e, va
lue
at 10
unreliable
-15.
6
-15.0
-15.
1
-16.
5
69N
69N/
76B
72P
76B
0.1
M so
dium
perchlorate
corr
ecte
d to I
* 0
esti
mate
based on
li
near
inc
reas
e in
hyd
roly
sis
constsnts
RECO
MMEN
DED;
H
obta
ined
by a
ssum
ing
a li
near
increase
-16.76(.09)
79M
33.0
References:
59A
Aksel'rud.N.V. an
d Sp
ivak
ovsk
ii,V
.B.(
l959
) Uk
rain
. Kh
im.
Zhur
. 25 14
-17.
68S
Sullivan,J.H
. an
d Singley,J.E.(1968) J.
Am.
Wate
r Wo
rks
Assoc.,
60,
1280-1287.
69N
Naearenko.V.A. an
d Ne
vaka
ya,E
.M.(
1 %9) Russ.
J. Inorg. Ch
em.
J4.,
1696-1699.
72P
Parks,G.A.
(1972) A
m. Mineral. 57,
1163-1187.
76B
Baea
.C.F
.,Jr
. an
d Meamer.R.M.Q976) The
Hydrolysis of C
atio
ns,
Wile
y-In
tera
cien
ce,
Chap
. 6.2, 11
2-12
3.
79M
May,H.M.,Hel
mke,
P.A.
, and
Jackson,M.L.(1979) Ge
ochi
m. Co
smoc
him.
Acta 4
3, 86
1-86
8.
A15+ + 4H
.O - Al(OH)"
+ 4H
* '
4
log K
-22.
47
-21.
81
-23.
25
-27.
98
-22.
21
-23.
26
-24.
24
-23.
57
-27.
69
-21.
94
-24.19
-23.3(.05)
-23.
3(.1
)
-22.05
-23.29
Sour
ce
08W/11S
20H
20H
34M
380
55R/72P-78H
55T
58G
60A
60G
64P
66K-
72P
66K-78H
67H
6&S
Sour
ceRE
MARK
S
Footnote (1 )
Foot
note
(1)
Foot
note
(2)
calculated from reported lo
g»K.
- -1
1.22
and log'K^K- - -1
6.76
derived
from reported log*K
. - -1
1.92
and
repo
rted
log
K Q
- -31.7
Foot
note
(1)
derived
from reported log
K .
-0.68
and
repo
rted
log
K Q
- -3
2.43
derived
from reported log
K .
* -0
.53
and
reported log
K Q
- -3
2.96
Foot
note
(3)
-4
-5
10
M al
umin
um pe
rchl
orat
e, va
lue
at 10
un
reli
able
TABL
E 6.
P
art
ial
com
pil
atio
n
of
then
nody
naro
ic
dat
a fo
r th
e W
ATEO
pro
gra
me(
con
tin
ued
):
-23
.37
70
B
-22
.07
73
H
-22.
71
74H
-22.054
74T-
60B
44.0
6 74T-80B
WATEQ
-23.0(.3)
76B-80B
WATEQ2
-22.99
2 76
P 42
.22
76P
WATEQF
-22.
16(.
03)
79M
References:
08W
W
ood,J
.K.(
1908)
J.
Che
ra.
Soc
. 93
, 4
11
-42
3.
118
Sla
de,R
.E.(
l91l)
Z.
E
lektr
och
em.
JJ7,
26
1-26
5.20
H
Hey
rov
aky
,J.(
192
0) J.
C
hem
. S
oc.
117.
10
13-1
025.
34M
M
affe
i,A
.(l9
34)
Gaz
z.
Chi
ra.
Ital.
64,
149-
160.
380
Ok
a,Y
.(l9
38
) J.
C
hem
. S
oc.
Jpn.
59,
971-
1013
.55
R
RuB
Bel
l,A
.S.,E
dw
ards,
J.D
.,
and
Tay
lor,
C.S
.(l9
55)
Tra
ns.
A
m.
Inst
. M
in.
Met
all.
E
ng.
203.
11
23-1
128.
55T
T
hom
pson
,L.C
.(19
55)
Ph.
D.
Th
esis
, V
ayne
S
tate
U
niv
.,
Detr
oit
, 69
pp.
58G
G
ayer
,K.H
.,T
hom
pso
n,L
.C.,
and
Zaj
icek
,O.T
.(l
958)
Can
J.
C
hem
. 36,
1268
-127
1.60
A
Ak
sel'ru
d,N
.V.(
l960)
Dok
l.
Aka
d.
Nau
k.
SSSR
13
2,
1067
-107
0.60
G
Go
to,K
.(l9
60)
Nip
pon
Kag
aku
Zas
shi
81,
349-
350.
64P
Plu
mb,
R.C
. an
d S
vain
e,J
.W.,Jr
.(l
964l~
J.
Phy
s.
Che
ra.
68,
2057
-206
4.66
K
Kit
tric
k,J
.A.(
l966)
Soil
S
ci.
S
oc.
Am
. P
roc.
30
, 59
5-59
8.67
H
Her
a,J.
D.
and
Rober
son.C
.E.(
1967)
U.S
. G
eol.
S
urve
y W
ater
-Su
pp
ly
Pap
er
1827
-A,
55
pp
.68
S S
ull
ivan
,J.H
. an
d S
ingle
y,J
.E.(
l 96
8) J.
A
m.
Wat
er W
orks
A
ssoc
. 60
, 12
80-1
287.
70B
B
erec
z.E
. an
d S
zit
a,L
.(l9
70)
Ele
ctro
chim
. A
cta
^5
, 14
07-1
419.
72P
Par
ka,
G.A
.(1972)
Am
. M
iner
al.
57,
1163
-118
9.73
H
Her
a,J.
D.,
Rober
son,C
.E.,L
ind,C
.J.,
and
Pole
er.W
.L.(
1973)
U.S
. G
eol.
Surv
ey W
ater
-Su
pp
ly P
aper
18
27-E
, 57
p
p.
74H
H
ayde
n,P
.L.
and
Rubin
.A.J
.(l
974)
in
A
queo
us-E
nvir
onm
enta
l C
hem
istr
y of
Met
als,
R
ubin
.A.J
.,
ed.,
Ann
A
rbor,
31
7-38
174
T
Tru
esd
ell.
A.H
. an
d Jo
nes
,B.P
.(l9
74)
J.
Hes
. U
.S.
Geo
l.
Sur
vey
£,
233-
248.
76B
B
aee.C
.P.,
Jr.
and
Mes
raer
,R.H
.(l9
76
) T
he
Hydro
lysi
s o
f C
atio
ns,
W
iley
-Inte
raci
ence
, C
hap.
6
.2,
112-
123.
76P
Plu
mm
er.L
.N.,Jo
nes
,B.F
.,
and
Tru
esdel
l,A
.H.(
1 9
76}
U.S
. G
eol.
S
urve
y W
.H.I
. 7
6-1
3,
61
pp.
78H
H
emin
gw
ay,B
.S.,
Ro
bie
,R.A
.,
and
Kit
tric
k,J
.A.(
l978)
Geo
chir
a.
Cos
moc
him
. A
cta
43,
1533
-154
3.79
M
May
,H.M
.,Hel
rake
,P.A
., an
d Ja
ckso
n,M
.L.(
1979)
Geo
chir
a.
Coa
moc
hira
. A
cta
43,
861-
868.
80B
B
all,
J.W
.,N
ord
stro
m,D
.K.,
an
d Je
nne,
E.A
.(l9
80)
U.S
. G
eol.
S
urve
y W
.R.I
. 7
8-1
16
, 109pp.
2A13*
+
2H90 -
[A19(OH)J4*
'2'
log
K So
urce
H°
Source
REMA
RKS
-8.0
6 48
F-54
F 0.
12 M
barium nitrate
-8.2
4 48
F-54
F 0.6
N barium nitrate
-7.55
55Ka
-55K
b 1-0.03-0.048
-6.2
7
56K
0.
0001
-
0.0
3 s
odiu
m per
chlo
rate
-7.0
7(.
06
) 65
A-7
2P
2 N
sodi
um per
chlo
rate
-7.7
71
M-7
6B
1 N
pota
ssiu
m ch
lori
de
-6.9
5(.
05
) 75
T
-7.1
78
H
1-0
.4
References:
48P
Fau
cher
re,J
.(l9
48
) C
ompt
. R
end.
22
7,
1367
-136
9.54
F F
auch
erre
,J.(
l954)
Bull
. C
him
. S
oc.
Fr.
, 25
7-26
7.55
Ka
Ken
ttam
aa,J
.(1
95
5)
Suom
. K
emis
til.
28
B,
172-
174.
55K
b K
entt
amaa
,J.(
l955)
Ann
. A
cad.
S
ci.
Fen
n.
All
, 67
, 1-
39.
56K
K
ubo
ta,H
.(l9
56)
Ph.
D.
Th
esis
, U
niv.
W
isco
nsin
, M
adis
on,
137
pp.
65A
A
ves
ton,J
.(1965)
J.
Che
m.
Soc
.(L
ondo
n),
4438
-444
3.71
M
Mes
mer
,R.M
. an
d B
aes,
C.F
.,Jr
.(1971 )
In
org
. C
hem
. _U
>,
2290
-229
6.72
P P
arks
,G.A
.(19
72)
Am
. M
iner
al.
57,
1163
-118
7.75
T T
urn
er,R
.C.(
1975)
Can
. J.
C
hem
. 53
. 28
11-2
817.
76B
B
aes,
C.F
.,Jr
. an
d M
eam
er,R
.M.(
l976
) T
he
Hyd
roly
sis
of
Cat
ion
s,
Wil
ey-I
nte
rsci
ence
, C
hap.
6.2
, 11
2-12
3.78
H
De H
ek,H
.,S
tol,
R.J
.,
and
De
Bru
yn,P
.L.(
1978
) J.
C
oll
oid
In
terf
ace
Sci
. 64
, 72
-89.
Al5
* +
F"
- A
1F2*
log
K So
urce
H°
So
urce
RE
MARK
S
6.13
42B-
43B
0.53
M potassium
nitrate
-57C
7.00
42B/55P
corrected
to I
- 0
6.16
43B/59K
0.53
M
pota
ssiu
m nitrate
1.15
53L
I - 0.06 - 0.
2
1.17
53L/59S
,
6.61
59
K I
- 0.
06 - 0.02
7.01
59K/68H
corr
ecte
d to
I
= 0
TABL
E 6.
P
art
ial
com
pil
atio
n
of
ther
mod
ynam
ic
dat
a fo
r th
e V
ATE
Q p
rogra
ms(
conti
nued
):
6.0
6
64B
6.9
6(.
06)
69B
6.6
9(.
02
) 71
A
6.1
14(.
C6)
71V
1.0
643B.53L/
59K-69B
7.01
74T>
*76P
-8
0B
0,74
71
V
0.64
(.05
) 75
V
0.0
aaau
med
T
- 25
°C,
I -
vari
able
RECO
MM
ENDE
D;
enth
alpy v
alue
is
for
1-0
.07
1 M
sodi
um perc
hlo
rate
VA
TEQ
-
VA
TEQ
F -
VA
TEQ
2-SOB
Ref
eren
ces:
42B
B
rosa
et,C
.(l9
42
) P
h.D
. T
hes
is,
Uni
v.
Lun
d,
Lun
d,
123
pp
.43
B
Bro
sset
.C.
and
Orr
ing,J
.(l9
43)
Sven
. K
ern.
T
idsk
r.
55,
101-
106.
53L
L
atim
er.V
.M.
and
Joll
y,V
.L.(
l95
3)
J.
Am
. C
hem
. S
oc.
75,
1548
-155
0.55
P P
aul,
A.D
.(1
95
5)
Uni
v.
Cali
f.
Rad
. L
ab.
Rep
t.
No.
U
CRL
2926
.57
C
Connic
k.R
.E.
and
Pouls
on,R
.E.(
l957)
J.
Am
. C
hem
. S
oc.
79,
5153
-515
6.59
K
Kin
g.E
.L.
and
Gal
lag
her
,P.K
.(l9
59
) J.
P
hya.
C
hem
. 63
, 10
73-1
076.
59S
Sco
tt,P
.C.(
1959)
Ph.
D.
Th
esis
, U
niv.
M
inn
eso
ta,
Min
nea
poli
s,
101
pp.
64B
B
randel
,V.
and
Sw
inar
ski,
A.(
l964)
The
ory
and
Str
uctu
re of
Com
plex
C
ompo
unds
, P
erga
mon
, 49
7 p
p.
68H
H
em, J
.D.(
196
8)
U.S
. G
eol.
S
urve
y V
ater
-Supply
P
aper
18
27-B
, 33
pp.
69B
B
aum
an,E
.V.(
l969)
J.
Inorg
. N
ucl
. C
hem
. 31
_,
3155
-316
2.71
A
Agar
wal
.R.P
. an
d M
ore
no,E
.C.(
l 97
1 )
Tal
anta
_18
, 8
73
-88
0.
71V
V
alker
.J.B
.,T
win
e,C
.R.,
and
Choppin
g.H
.(1971 )
J.
In
org
. N
ucl
. C
hem
. 33
, 18
13-1
817.
74T
T
rues
del
l.A
.H.
and
Jones
,B.P
.(1974)
J.
Res
. U
.S.
Geo
l.
Sur
vey
£,
233-
248.
75V
V
asi
l'ev.V
.P.
and
Ko
zlo
vak
ii.E
.V.(
l 97
5)
Zh.
N
eorg
. K
him
. 20
, 11
96-1
199.
76P
Plu
mm
er,L
.N.,
Jones
,B.P
.,
and
Tru
esdel
l,A
.H.(
l 97
6)
U.S
. G
eol.
S
urve
y V
.R.I
. 76-1
3,
61
pp.
SOB
Bal
l,J.
V.,N
ord
stro
m,D
.K.,
and
Jenne,
E.A
.(l
980)
U
.S.
Geo
l.
Sur
vey
V.R
.I.
78
-11
6,
109pp.
A13+
2P-
A1P
,
log K
11
.15
11.2
1
Sou
rce
-57C
43B
/59K
Sou
rce
1.93
53L
REM
ARKS
0.53 M
po
tass
ium
nitrste
I - 0.06 - 0.2
1.97
53L
/59S
9.06
11
.97
12
.75
57T
59K
59K
/68H
11.1
0 64
B
12.6
0(.10)
69B
1.98
12.0
4
12
.75
71A
74T
*76P
6
0B20.0
43B.53L/
59K-69B
75V
74T
*76P
-S
OB
I *
var
iable
I -
0.07
corr
ecte
d
to
I *
0
assu
med
T
* 25
°C,
I *
var
iable
RECO
MM
ENDE
D;
enth
alpy v
alu
e is
fo
r I
- 0.0
7
WAT
EQ -
WAT
EQF
- W
ATEQ
2
Ref
eren
ces:
42B
B
ross
et,C
.(l9
42
) P
h.D
. T
hes
is.
Uni
v.
Lun
d,
Lun
d,
123
pp.
43B
B
ross
et.C
. an
d O
rrin
g, J
. (1
943)
Sve
n.
Ker
n.
Tid
skr.
55
, 10
1-10
6.53
L L
atim
er.W
.M.
and
Joll
y,W
.L.(
l95
3)
J.
Am.
Che
m.
Soc
. 75
, 15
48-1
550.
57C
Con
nick
.B.E
. an
d P
ouls
on.R
.E.(
1957
) J.
Am
. C
hem
. S
oc.
79,
5153
-515
6.57
T T
anan
aev.
I.V
. sn
d V
inog
rado
va,
A.D
.(l9
57
) Z
h.
Neo
rg.
Khi
m.
2_,
2455
-246
7.59
K
Kin
g.E
.L.
and
Gal
lag
her
,P.K
.(l9
59
) J.
P
hys.
C
hem
. 63
, 10
73-1
076.
59S
Sco
tt,P
.C.(
1959)
Ph.
D.
Thes
is,
Uni
v.
Min
neso
ta,
Min
neap
olis
, 10
1 pp
.64
B
Bra
ndel
,¥.
and
Sw
inar
ski,
A.(
l96
4)
The
ory
and
Str
uct
ure
of
Com
plex
C
ompo
unds
, Pe
rgam
on,
War
saw
, 49
7 pp
.68
H
Hem
,J.D
.(19
68)
U.S
. G
eol.
S
urve
y W
ater
-Sup
ply
Pap
er
1827
-B,
33
pp.
69B
B
aum
an,E
.W.(
l969
) J.
In
org
. N
ucl.
Che
m.
31,
3155
-316
2.71
A
Aga
rwal
.R.P
. an
d M
oren
o,E
.C.(
l971
) T
alan
ta J
8,
873-
880.
74T
Tru
eade
ll,A
.M.
and
Jones
,B.F
.(1974)
J.
Res
. U
.S.
Geo
l.
Sur
vey
£,
233-
248.
75V
V
asil
'ev.V
.P.
and
Kozl
ovsk
ii,E
.V.(
l975)
Zh.
N
eorg
. K
him
. 20
, 11
96-1
199.
76P
Plu
mm
er.L
.N.,
Jones
,B.F
.,
and
Tru
esd
ell,
A.H
.(l9
76)
U.S
. G
eol.
S
urve
y W
.R.I
. 76
-13,
61
pp
.SO
B B
all,
J.W
.,N
ord
stro
m,D
.K.,
and
Jen
ne.
E.A
.(l
980)
U.S
. G
eol.
S
urve
y W
.R.I
. 78
-116
, 1
09
pp
.
Al3
* +
3F~
- A
1F°
log
K
15
.00
15.1
2
Sou
rce
42B
-43B
-5
7C
43B
/59K
2.1
2
2.1
8
Sou
rce
53L
53L
/59S
REM
ARKS
0.53
M
pota
ssiu
m nit
rate
0.53
M p
otas
sium
nit
rate
I -
0.06
-
0.2
16.0
359
KI
- 0.
07
TABL
E 6.
P
art
ial
com
pil
atio
n
of
ther
mod
ynam
ic
dat
a fo
r th
e W
ATEQ
pro
gra
ms(
conti
nued
):
17.0
2 59
K/6
8H
16.6
5(.
15)
69B
15.7
2
17
.02
71A
74T
-76P
-8
0B
2.1
6
2.5
0
3.0
7(.
3)
43B
.53L
/ 59
K-6
9B
74T
-76P
-S
OB
75V
corr
ecte
d
to
I *
0
RECO
MM
ENDE
D;
enth
alp
y v
alue
is
for
1-0
.07
WAT
EQ -
WAT
EQP
- W
ATE
Q2
Ref
eren
ces:
42B
B
roas
et,C
.(l9
42
) P
h.D
. T
hes
is,
Uni
v.
Lun
d,
Lun
d,
123
pp
.43
B
Bro
aset
.C.
and
Orr
ing,J
.(1 9
43)
Sven
. K
ern.
T
idsk
r.
55,
101-
106.
53L
L
atim
er.W
.M.
and
Joll
y,W
.L.(
l 95
3) J.
A
m.
Che
m.
Soc
. 75
, 15
48-1
550.
57C
C
onnic
k.R
.E.
and
Pouls
on.R
.E.O
957
) J.
A
m.
Che
m.
Soc
. 79,
5153
-515
6.59
K
Kin
g.E
.L.
and
Gal
lag
her
,P.K
.(l9
59
) J.
P
hys.
C
hem
. 63
, 10
73-1
076.
59S
Sco
tt,P
.C.(
19
59
) P
h.D
. T
hes
is,
Uni
v.
Min
nes
ota
, M
innea
poli
a,
101
pp.
68H
H
em,J
.D.(
l968)
U.S
. G
eol.
S
urve
y W
ater
-Su
pp
ly
Pap
er
1827
-B,
33
pp.
69B
B
aunan
,E.W
.(l9
69
) J.
In
org
. N
ucl
. C
hem
. 31
_,
3155
-316
2.71
A
Agar
wal
.R.P
. an
d M
ore
no
,E.G
.(1
97
1)
Tal
anta
JJ3
, 87
3-88
0.74
T
Tru
esd
ell.
A.H
. an
d Jo
nes,
B.P
.(l
974)
J.
R
es.
U.S
. G
eol.
S
urve
y 2
, 23
3-24
8.75
V
Vasi
l'ev.V
.P.
and
Kozi
lovB
kii
,E.V
.(l
975)
Z
h.
Neo
rg.
Khi
m.
20,
1196
-119
9.76
P P
lum
mer
.L.N
.,Jo
nes
,B.P
.,
and
Tru
esdel
l,A
.M.(
1976)
U.S
. G
eol.
S
urve
yW.R
.I.
76-1
3,
61
pp.
SOB
Bal
l.J.
W..
Ho
rdst
rom
,O.K
.,
and
Jenne.
E.A
.(l9
80)
U.S
. G
eol.
S
urve
y W
.R.I
. 7
8-1
16
, 109pp.
Al-
log
K
17.7
4
17.8
3
18
.71
19
.72
Sou
rce
42B
-43B
-5
7C
43B
/59K
59K
59K
/68H
2.4
0
2.1
4
Sou
rce
53L
53L
/59S
REM
ARKS
0.5
3 M
pota
ssiu
m n
itra
te
0.5
3
M p
ota
ssiu
m n
itra
te
I -
0.0
6 -
0.2
1-0
.07
corr
ecte
d
to
I -
0
19
.03
(.1
5)
69B
18
.47
71
A
19
.72
2.2
0
0.0
43B
.53L
/ 59
K-6
9BRE
COM
MEN
DED;
en
thal
py
val
ue
is fo
r I
- 0.0
7
WATE
Q - WA
TEQF
- WA
TEQ2
-SOB
-BOB
References:
42B
B
ross
etfC
.(l9
42)
Ph.
D.
Th
esis
. U
niv.
L
und,
L
und,
12
3 pp
.43
B
Bro
sset
.C.
and
Orr
ing,J
.(1943)
Sve
n.
Ker
n.
Tid
skr.
55
., 10
1-10
6.53
L L
atim
er.W
.M.
and
Joll
y,W
.L.(
l95
3)
J.
Am.
Che
m.
Soc
. 75
, 15
48-1
550.
57C
C
onni
ck.R
.E.
and
Pouls
on,R
.E.(
l957)
J.
Am.
Che
m.
Soc
. 79
, 51
53-5
156.
59K
K
ing.
E.L
. an
d G
alla
gh
er,P
.K.(
l95
9)
J.
Phy
s.
Che
m.
63,
1073
-107
6.59
S S
cott
,P.O
.(1959)
Ph.
D.
Th
esis
, U
niv.
M
inne
aota
, M
inn
eap
oli
s,
101
pp.
68H
H
em,J
.D.(
1968
) U
.S.
Geo
l.
Sur
vey
Wat
er-S
uppl
y P
aper
18
27-B
, 33
pp
.69
B
Bau
man
,E.W
.(l9
69)
J.
Inorg
. N
ucl.
C
hem
. 31
_, 31
55-3
162.
71A
A
garw
al.R
.P.
and
Mor
eno,
B.C
.(19
71)
Tal
anta
J8,
873-
880.
74T
Tru
esdel
l.A
.H.
and
Jones
,B.P
.(1974)
J.
Res
. U
.S.
Geo
l.
Sur
vey
2,
233-
248.
76P
Plu
mm
er,L
.N.,
Jones
,B.F
.,
and
Tru
esdel
l.A
.H.(
1976)
U.S
. G
eol.
S
urve
y W
.R.I
. 76
-13,
61
pp
.BO
B B
all,
J.W
.,N
ord
atro
m,D
.K.,
an
d Je
nne,
E.A
.(l9
80)
U.S
. G
eol.
S
urve
y W
.R.I
. 78
-116
, 10
9 pp
.
Al-
5F~
-
log
K
19.3
7
19.2
9
20
.04
20.9
1
Sou
rce
42B
-43B
43B
/59K
59K
59K
/68H
1.6
5
2.2
7
1.8
4
Sou
rce
53L
53L
/59S
43B
,53L
/ 59
K
REM
ARKS
0.53
M
pota
ssiu
m nit
rate
0.53
M
pota
ssiu
m nit
rate
I -
0.06
-
0.2
I -
0.07
RECO
MM
ENDE
D;
enth
alp
y v
alue
is fo
r I
- 0.0
7
Ref
eren
ces:
42B
B
ross
et,C
.(l9
42)
Ph.D
. T
hes
is,
Uni
v.
Lun
d,
Lun
d,
123
pp.
43B
B
ross
et.C
. an
d O
rrin
g,J
.(1
94
3)
Sve
n.
Ker
n.
Tid
skr.
55
, 10
1-10
6.53
L L
atim
er.W
.M.
and
Joll
y,W
.L.(
1953)
J.
Am.
Che
m.
Soc
. 75
, 15
48-1
550.
59K
K
ing,
E.L
. an
d G
alla
gh
er,P
.K.(
l95
9)
J.
Phy
s.
Che
m.'6
3,
1073
-107
6.59
S S
cott
,P.C
.(1959)
Ph.D
. T
hes
is,
Uni
v.
Min
neso
ta,
Min
nea
po
lis,
10
1 pp
.68
H
Hem
,J.D
.(19
68)
U.S
. G
eol.
Sur
vey
Wat
er-S
uppl
y P
aper
18
27-B
, 33
pp
.
TABLE
6.
Partial
comp
ilat
ion
of th
ermo
dyna
mic
data for
the
VATE
Q programs(continued):
Al3
* +
6P-
- A
1P|-
log
K
Sou
rce
V°
Sou
rce
REM
ARKS
19.6
4 42
B-4
3B
0.5
3 H
pota
ssiu
m nit
rate
-1.2
4
53L
/59S
20.6
6
59K
/68H
0.1
0
53L
RE
COM
MEN
DED;
en
thal
py v
alue
is fo
r I
- 0.0
6 -
0.2
Ref
eren
ces:
42B
B
roas
et,C
.(l9
42
) P
h.D
. T
hes
is,
Uni
v.
Lun
d,
Lun
d,
123
pp..
43B
B
ross
et,C
. an
d O
rrin
g,J
.(l9
43)
Sven
. K
ern.
T
idsk
r.
55,
101-
106.
53L
L
atim
er,W
.M.
and
Joll
y,W
.L.(
l 95
3) J.
A
m.
Che
m.
Soc
. 75,
1548
-155
0.59
K
Kin
g,E
.L.
and
Gal
lagher
,P.K
.(l
959)
J.
P
hys.
C
hem
. 65
, 10
73-1
076.
59S
Sco
tt,P
.C.(
1959)
Ph.
D.
Th
esis
, U
niv.
M
innes
ota
, M
innea
poli
s,
101
pp.
68H
H
em,J
.D.(
19
68
) U
.S.
Geo
l.
Su
rvey
Wat
er-S
up
ply
Pap
er 1
827-
B,
33
pp.
Al3*
+ SO
?" - A1SO*
4 4
log
K Source
H°
Source
REMA
RKS
3.20
62B-74T
2.29(.08)
69I-
74T
WATE
Q - WA
TEQP
-7
6P
-76P
3.73
65
H
3.01
(.08
) 69I-77N
WATEQ2
"60B
3.57
69S
3.2
70R
2.1
5
77N
-60B
ba
sed
on
Fuo
ss eq
uati
on
(Sie
bert
an
d C
hri
st,
unpubli
shed
dat
a)
Ref
eren
ces:
62B
B
ehr.
B.
and
Ven
dt,
H.(
196
2)
Z.
Ele
ktr
och
em.
66_,
22
3-22
8.65
N
Nis
hid
e,T
. an
d T
such
iya,
R.(
l 96
5)
Bu
ll.
Che
m.
Soc
. Jp
n.
38,
1398
-140
0.69
1 Iz
att,
R.M
.,E
ato
ug
h,D
., C
hri
stense
n,J
.J.,
and
Bar
tholo
mew
,C.H
.(l
969)
J.
C
hem
. S
oc.
A,
47-5
3.
69S
Str
yker,
L.J
. sn
d M
ati
jev
ic,E
.(l9
69
) J.
P
hys.
C
hem
. 73,
1484
-148
7.70
R
Ric
hburg
,J.S
. an
d A
dam
s,P
.(l9
70)
Soil
S
ci.
Soc
. A
m.
Pro
c.
3i,
72
8-73
4.
74T
T
rues
del
l.A
.H.
and
Jones
,B.F
.(1974)
J.
Res
. U
.S.
Geo
l.
Sur
vey
2_,
233-
248.
76P
Plu
mm
er.L
.N..
Jones
,B.F
.,
and
Tru
esd
ell,
A.H
.(l9
76)
U.S
. G
eol.
S
urve
y W
.R.I
. 7
6-1
3,
61
pp.
77N
N
ord
stro
m,D
.K.(
19
77
) P
h.D
. T
hes
is,
Sta
nfo
rd
Un
ivers
ity
, S
tanfo
rd,
210
pp.
80B
B
all,
J.W
.,N
ord
stro
m,D
.K.,
and
Jenne,
E.A
.(l
980)
U
.S.
Geo
l.
Sur
vey
W.R
.I.
78
-11
6,
109
pp.
A13
+ +
2SO
J- ,
A1(
S04
)~
log K
S
ou
rce
5.1
0
4.9
0(.
1)
62B
-74T
69I-
77N
-6
0B
H 3.0
7(.
2)
2.8
4
Sou
rce
69I*
74T
-7
6P
77N
-80B
REM
ARKS
WAT
EQ -
WAT
EQF
WA
TEQ
2;
enth
alp
y b
ased
on
F
uoas
eq
uati
on
(Sie
bert
an
d C
hri
st,
un
pu
bli
shed
d
ata)
Ref
eren
ces
:62
B
Beh
r.B
. an
d W
end t,
H. (
1 96
2 )
Z.
Ele
ktr
och
em.
66,
223-
228.
691
Izatt
,R.M
.,E
ato
ugh,D
.,C
hri
stense
n,J
.J.,
and
Bar
thol
omew
, C.H
.(l
969)
J.
C
hem
. S
oc.
A,
47
-53
.74
T
Tru
esdel
l.A
.H.
and
Jones
, B.F
. (1
97
4)
J.
Res
. U
.S.
Geo
l.
Sur
vey
2,
233-
248.
76P
Plu
mm
er.L
.N. .J
on
es, B
.F.
, an
d T
rues
del
l,A
.H.(
l 97
6)
U.S
. G
eol.
S
urve
y W
.R.I
. 76-1
3,
61
pp.
77N
N
orde
trom
, D.K
. (1
97
7)
Ph.
D.
Th
esis
, S
tanfo
rd
Univ
ersi
ty,
Sta
nfo
rd,
210
pp.
BOB
Ball
, J.W
., N
ords
trom
, D.K
. ,
and
Jenne,
E.A
.(l
980)
U
.S.
Geo
l.
Sur
vey
W.R
.I.
78
-11
6,
109
pp
.
Al(
OH
)5
soli
d:G
ibb
site
G
°.--
276.0
3(.
30)
kca
l/m
ol
H°,
--309.0
6(.
30)
kca
l/m
ol
S°-
16.3
6(.
03)
cal/
deg
.mol
Cp-
21.9
2 ca
l/d
eg.m
ol
Ref
eren
ces:
77
Ha,
77H
b
A1(
OH
)5
+ 3H
* -
Al3
* +
log
K
9.02
10.3 9.57
8.55
9.04
Source
20H
380
55T
57M
58G
-28
.0
Sou
rce
20H
REM
ARKS
aged
fo
r se
ver
sl
wee
ks
TABL
E 6.
P
art
ial
com
pil
atio
n
of
ther
mod
ynam
ic
dat
a fo
r th
e W
ATEQ
pro
gra
ms(
conti
nued
):
8.4
9(.
1)
60F-
62F
-76
B
10.8
63
F
7.9
7(.
05)
66K
9.3
5(.
3)
67H
11.4
0 71
D
8.22
72
3
10.4
74
H
10.0
5 74
H
8.04
(.0
3)
743
9.23
74
T-7
6P
9.30
78
Hb
8.1
1(.
02)
79M
8.75
(.0
5)
79M
=-60
B
-21.0
4(.
2)
74S-
76S
-25.
57
74T
-76P
-22.8
(1)
78H
a-80
B
cam
e to
eq
uil
ibri
um
in
1-
3 m
onth
s fr
om au
per
aatu
rati
on,
2-6
mic
ro
met
er part
icle
aiz
e
amor
phou
s
well
-cry
stal
lize
d gi
bbsi
te,
agin
g ti
me a
bout 4 yrs.,
no d
ifference
in pa
rtic
les
.05-
50 m
icro
mete
rs in
size
micr
ocry
stal
line
gib
bsit
e, aged 2-20 wka
aged 24
hrs at
20°C
aged fo
r about
2 yrs.
amor
phou
s, ag
ed fo
r 24 h
rs.
microcrystalline,
aged 3
mont
hs
aged 1.5-2.5 yrs.
WA
TEQ
-
WA
TEQ
P
WAT
EQ2;
h
eat
of
solu
tion m
easu
red
on
sam
e m
ater
ial
from
66K
synth
etic
cry
stall
ine gib
bsi
te,
2-5
mic
rom
eter
s in
si
ze,
equ
ilib
riu
m w
as
rever
sed
and
reac
hed
in
a m
onth
or
less
WAT
EQ2;
nat
ura
l gib
bsi
te
from
M
inas
G
erai
s,
sam
e ex
per
imen
tal
deta
ils
as 7
9M a
bove
RECO
MM
ENDA
TION
: 1.
F
or cry
stall
ine g
ibbsi
te
the
log
K re
sult
s of
66K
.72S
.76S
an
d 79
Mar
e all
in
ex
cell
ent
agre
emen
t.
The
valu
e re
port
ed
by 7
9M is
re
com
men
ded.
2.
The
uppe
r so
lubil
ity li
mit
is
no
t w
ell-
def
ined
, bu
t it
pr
obab
ly l
ies
in th
e ra
nge
of
log
K =
9.35
-1 0
.8 f
or
a m
icro
cryst
alli
ne
to
an a
mor
phou
s p
recip
itate
, re
spec
tivel
y.
Ref
eren
ces:
20H
H
eyro
vsk
y,J
.(l9
20)
J.
Che
ra.
Soc
. 11
7.
11-2
6.38
0 O
ka, Y
.( 1
938)
J.
C
hem
. S
oc.
Jpn.
59
, 97
1-10
13.
55T
Tho
mps
on, L
.C.(
195
5)
Ph.
D.
Th
esis
, W
ayne
S
tate
U
niv
.,
Det
roit
, 69
pp.
57M
M
iron
ov.N
.N.
and
Odnose
vts
ev,A
,I.(
l 95
7)
Zh.
N
eorg
. K
him
. £,
2202
-220
7.58
G
Gay
er,K
.H.,T
hom
pson
,L.C
., an
d Z
ajic
ek,O
.T.(
l 95
8) C
an.
J.
Che
m.
36,
1268
-127
1.60
F F
rink,C
.R.(
l960)
Ph.
D.
Thes
is,
Corn
ell
Uni
v.,
Ithac
a,
161
pp.
62F
Fri
nk,C
.R.
and
Pee
ch,M
.(l9
62)
Soil
S
ci.
Soc
. P
roc.
26
, 34
6-34
7.63
F F
eitk
nech
t,W
. an
d S
chin
dle
r,P
.(l
963)
Pur
e A
ppl.
Che
m.
*>,
130-
199.
66K
K
ittr
ick,J
.A.(
l966)
Soil
S
ci.
Soc
. A
n.
Pro
c.
30,
595-
598.
67H
H
em.J
.D.
and
Rob
erso
n,C
.E.(
l 96
7) U
.S.
Geo
l. S
urve
y V
ater
-Sup
ply
Pap
er
1827
-A,
55
pp.
71D
D
ezel
ic,H
.,B
ilin
ski,
H.,
and
Wol
f,R
.H.H
.(19
71)
J.
Inorg
. N
ucl.
C
hem
. 33
, 79
1-79
8.72
S S
mit
h,R
.W.
and
Hem
,J.D
.(19
72)
U.S
. G
eol.
S
urve
y W
ater
-Sup
ply
Pap
er
1827
-D,
51
pp.
74H
H
ayde
n.P
.L.
and
Rubin
,A.J
.(1974)
in
Aqu
eous
-Env
iron
men
tal
Che
mis
try
of
Met
als,
R
ubin
,A.J
.,ed
.74S
Singh,S.S.(l974) Soil Sc
i. So
c. Am
. Proc.
3§,
415-417.
74T
Truesdell.A.H. an
d Jones,B.F.(1974) J. Re
s. U.S. Ge
ol.
Survey £,
233-248.
76B
Baes
,C.F
.,Jr
. and
Mesmer,R.M.(l976)
The
Hydr
olys
is of
Cations, Wiley-Interscience,
Chap.
6.2,
76P
Plum
mer.
L.N.
,Jon
es,B
.F.,
an
d Truesdell,A.H.(1 976)
U.S. Ge
ol.
Survey W.R.I. 76-13, 10
9 pp.
763
Sin
gh
,S.S
.(l9
76
) S
oil
S
ci.
121,
33
2-33
6.77
Ha
Hem
ingw
ay,B
.S.
and
Rob
ie.R
.777
1977
) U
.S.
Geo
l. S
urve
y J.
R
es.
£,4
13-4
29.
77H
b H
emin
gw
ay,B
.S..R
obie
.R.A
.,F
isher
,J.R
. an
d W
ilso
n,W
.H.(
l977
) U
.S.
Geo
l.
Sur
vey
5,
797-
806.
78H
a H
emin
gway
,B.S
.,Rob
ie,R
.A.,
and
Kit
tric
k,J
.A.(
l978)
Geo
chim
. C
osm
ochi
m.
Act
a 4£
, 15
33-1
543.
78H
b De
H
ek,H
., S
tol,
R.J
.,
and
De
Bru
yn,P
.L.(
1978
) J.
C
ollo
id
Inte
rfac
e S
ci.
64,
72-8
9.79
M
May
,H.M
.,Hel
mke
,P.A
., an
d Ja
ckso
n,M
.L.(
1 97
9)
Geo
chim
. C
osm
ochi
m.
Act
a 43
^,
861-
868.
80B
B
all,
J.W
.,N
ord
stro
m,D
.K.,
and
Jenne,
E.A
.(l
980)
U
.S.
Geo
l.
Sur
vey
W.R
.I.
78-1
16,
10
9p
p.
Ann
A
rbor
, 31
7-38
1
11
2-1
23
.
.CA
LCIU
M.
2 +
Ca
aque
ous
ion
Gj--132.125(.20) kc
al/m
ol
H°,-
-129
.80(
.20)
kc
al/m
ol
Refe
renc
e: 77
COca
l/de
g.mo
l
Source
REMA
RKS
T -
18°C
.075
-
1.00 M
sodium ch
lori
de
I - 0.7
theo
reti
cal
calc
ula
tion
1 M
NaN
O_,
by
io
n-s
elec
tiv
e el
ectr
ode
TABL
E 6.
Partial
comp
ilat
ion
of th
ermo
dyna
mic
data
for
the
WATEQ
prog
rama
(con
tinu
ed):
-0.1
2 75
S 1 M
NaNO_, by sil
ver
chlo
ride
electrode
0.35
78
J 1-0.6
-0.3
0 79E
1-0.7
Ref
eren
ces:
30R
H
igh
ella
to.E
.C.
and
Dav
ies,
C.W
.(l9
30
) T
rans.
F
arad
ay
Soc
. 26
, 59
2-60
0.43
H
Har
ned
,H.S
. an
d O
wen
,B.B
.(19
43)
The
P
hy
sica
l C
hem
istr
y o
f E
lectr
oly
tic
Solu
tions,
R
einhold
, p.
422.
62C
C
ors
aro,G
.(l9
62)
J.
Che
m.
Edu
c.
39t
622-
626.
71H
Nakayama,F.S.(l97l)
Soil Sci. So
c. Am.
Proc.
35,
881-883.
75E
Elgquist.B.
and
Wedborg,M.(l975) Ma
r. Ch
em.
2t 21
5-22
5.75
K Ke
ster
.D.R
. an
d Py
tkow
icz,
H.M.
(l97
5) Mar. Chem.
_3t
365-
374.
753
Such
a.L.
.Cad
ek.J
., an
d Ve
sely
,J.(
1975
) Co
llec
t. Cz
ech.
Ch
em.
Commun.
40,
2020-2024.
77CO CO
DATA
Bu
ll.
28,
17 p
p.78
J Johnson,K.
S. an
d Pytkowicz.H.M.d978)
Am.
J. Sci. 278, 14
28-1
447.
79E
Elgquist.B.
and
Wedborg,M.(l 979)
Mar. Chem.
7.,
273-
280.
....
....
....
....
....
....
....
....
....
....
....
....
....
....
IRON
.
2 +
Fe
aqueous
ion
G£ 19.15(.08)
kcal
/mol
e H°
--20
.82(
.7)
kcal
/mol
e S°
»-30
.3(2
.5)
cal/
deg.
mole
Cp
--0.
5(7.
2) ca
l/de
g.mo
l Re
fere
nces
: 78
J,79
B and
calc
ulat
ions
in this re
port
Fe5* aq
ueou
s io
n G°
--1.
39(.
08)
kcal
/mol
H^»-
10.8
4(.2
) kc
al/m
ol
S°--
72.0
(.7)
ca
l/de
g.mo
l Re
fere
nces
: se
e calculations in this re
port
Fe » Fe
2* *
2e"
E°(volts
) G°
(kca
l/mo
l)
Source
REMARKS
0.4413
-20.
35
26H
0.4402
-20.
30
32R
0.4090 (.00075)
0.44
2
0.46
7
0.41
53 (.001 3)
-18.85
-20. 39
-21.54
-19.15
53P
58H
60H
78J
V -
20°C
RECO
MM
END
ED
References:
26H
H
amp
ton
,W.H
.(l9
26)
J.
Ph
ya.
C
hem
. 30,
98
0-9
91
.32
R
Ran
dal
l.M
. an
d F
ran
dae
n,M
.(l
932)
J.
Am
. C
hem
. S
oc.
54
_,
47-5
4.
53P
P
atri
ck,W
.A.
and
Thom
pso
n,W
.E.(
1953)
J.
Am
. C
hem
. S
oc.
7
5,
1184-1
187.
58H
H
oar
,T.P
. an
d H
url
en
,T.(
19
58
) P
roc.
Inte
rn.
Com
ra.
Ele
ctro
chem
. T
herm
odyn
am.
Kin
et.
, 8
th
Mtg
.,
445-4
47.
60H
H
url
en
,T.(
l96
0)
Act
a C
hem
. S
can
d.
^4
, 1533-1
554.
78
J Jo
hnso
n,O
.K.
and
Baum
an.J
.E.,
Jr.(
l978)
Ino
rg.
Che
m.
JJ7,
2
77
4-2
77
9.
79B
B
ern
ard
ucci.
E.E
. ,M
ors
s,L
.R.,
an
d M
iksz
tal,
A.R
.(l
979)
J.
Solu
tion
Che
m.
8,
71
7-7
27
.
E°(v
olts
)G°
(kca
l/mo
l)
Source
H°(k
cal/
mol)
Source
-0.7
47
7 (
.00
05
)
-0.7
72
(.0
01
)
-0.7
70
1 (
.00
02
)
-0.7
39
4
-0.7
37
5 (
.00
1)
-0.7
49
-0.7
46
-0.7
67
-0.
674
-0.7
32
-0.7
38
-0.7
71
(.0
04
)
-0.7
37
5 (
.00
01
)
-0.7
70
(.002)
17
.24
17
.80
17
.76
17.0
5
17
.00
17
.27
17
.20
17
.69
15
.54
16.8
8
17
.02
17.7
8
17.0
1
17
.76
29P
29P
/34B
37S
51C
53M
58S
58S
58S
58S
58S
58L
58L
/60M
62Z
72W
-9.
53 (
.04)
50F
-9.9
5(.
05)
51C
-9.7
(.2)
53M
-10.2
(.4)
72W
REM
ARK
S
uncorrected
for
complexing
corrected
for
comp
lexi
ng
0.5
M perchloric acid
0.5
M perchloric acid
I "
1, so
dium
pe
rchl
orat
e and
perchloric acid
0.25 M
nitric acid
1 M
nitric acid
1 M
perc
hlor
ic ac
id
0.5
M su
lfur
ic acid
1 M
hydrochloric acid
uncorrected
for
complexing
corrected
for
comp
lexi
ng
1-2, sodium pe
rchl
orat
e and
perc
hlor
ic acid
TAB
U!
6.
Part
ial
com
pil
atio
n
of
ther
mod
ynam
ic d
ata
for
the
WAT
EQ p
rog
ram
s(co
nti
nu
ed):
-0.7
695
(.0
00
8)
17
.75
72
W/7
9M
-9.1
8
72W
/79M
dat
a re
fit
to li
near
equat
ion
-0.7
702
(.0
00
1)
17.7
6
34B
.37S
-1
0.0
(.5)
RECO
MM
ENDE
D;
wei
gh
ted
av
erag
e fr
om
fou
r d
iffe
ren
t60
M,7
2W
inv
est
igati
on
s;
for
enth
alp
y val
ue
see
tex
t
Ref
eren
ces:
29P
Popoff
.S.
and
Ku
nz,
A.H
.(l
929)
J.
A
m.
Che
m.
Soc
. 51
., 382-3
94.
34B
B
ray.
W.C
. an
d H
ersh
ey,A
.V.(
l93
4)
J.
Am
. C
hem
. S
oc.
56,
1889
-189
3.37
S S
chum
b.W
.C.,S
her
rill
,H.S
. an
d S
wee
tser
,S.B
.(l
937)
J.
A
m.
Che
m.
So
c.5
9,
2360
-236
5.50
P P
on
tan
a(B
.J.(
1950)
The
C
hem
istr
y a
nd
Met
allu
rgy
of
Mis
cell
aneo
us
Mate
rials
, V
ol.
19B
, p.
321.
51C
C
onni
ck.H
.E.
and
McV
ey,W
.H.(
1951
) J.
A
m.
Che
mT
Soc
. 73,
1798
-180
4.53
H
Mag
nuss
on.L
.B.
and
Huiz
enda,
J.R
.(1953
) J.
A
m.
Che
m.
So
c.
75_,
22
42-2
246.
58L
L
apte
va,
O.H
.(l9
58)
Zh.
P
rikl.
K
him
. 31
., 12
10-1
215.
58S
Str
om
att,
R.V
.,P
eekem
a,R
.M.,
and
Sco
tt,P
.A.
(1 9
58)
HV
-582
12
(Han
ford
W
orks
).60
M
Mat
too,B
.».(
I960)
Zh.
P
rikl.
K
him
. 33
, 20
15-2
020.
62Z
Z
iele
n.A
.J.
and
Sull
ivan,J
.C.(
l962)
J.
Phy
s.
Che
m.
66,
1065
-106
9.72
W
Whi
ttem
ore.
D.O
. an
d L
angm
uir
,D.(
l972)
J.
Che
m.
Eng
. D
ata
V^,
28
8-29
0.79
N
No
rdst
rom
,D.K
.(1
97
9)
unpubli
shed
calc
ula
tions
......................................................M
AG
NE
SIU
M..........................................
Mg2* aq
ueou
s io
n G°
--10
9 kcal/mol
H°--112
kcal/mol S° 33 ca
l/de
g.mo
l Re
fere
nces
: 71
W,77
CO,7
9C
Mg2*
* Cl"
- MgCl*
log
K Source
H°
Source
REMARKS
none
30R
T -
18°C,
cited
by 753
smal
l 43
H cited
by 753
none
45
S ci
ted
by 753
-0.9801
73H
-0.3
2
-0.0
8
-0.11
-0.1
8
-0.47
0.28
75E
75S
75S
77F
78E
78J
1-0
.7
1 N
NaN
O,,
by i
on-s
ele
cti
ve ele
ctr
od
e
1 N
NaN
O-,
by s
ilver
ch
lori
de e
lectr
ode
I -
0.7
I -
0.6
Refe
renc
es:
30R
R
igh
ella
to,E
.C.
and
Dav
ies,
C.W
.(l9
30)
Tra
ns.
F
arad
ay
Soc
. 26
_,
592-
600.
43H
H
arn
ed.H
.S.
and
Ow
en,B
.B.(
l 94
3)
The
P
hy
sica
l C
hem
istr
y o
f E
lectr
oly
tic S
olu
tio
ns,
R
einhold
, N
.Y.,
422
pp.
45S
Sto
kes
,R.H
.(1945)
Tra
ns.
F
arad
ay S
oc.
41_,
64
2-64
5.71
W
Yag
man
,D.D
.,E
van
s,¥.H
.,P
arker
,V.B
.,H
alow
,I.,B
aile
y,S
.M..S
chum
m,R
.H.,
and
Ch
urn
ey,K
.L.(
l97
1)
U.S
. N
at.
Bu
r.
Sta
nd
. T
ech.
N
ote
270-5
, 37
pp
73H
H
avel
,J.
and
Ho
gfe
ldt,
E.(
l97
3)
Act
a C
hem
. S
cand
. 27
, 33
23-3
334.
75E
E
lgquis
t,B
. an
d ¥ed
borg
,M.(
l 97
5)
Mar
. C
hem
. 2.
21
5-2
25
.75
S S
uch
a,L
.,C
adek
,J.,
an
d V
esel
y,J
.(1
97
5)
Coll
ect.
C
zech
. C
hem
. C
omm
un.
40,
2020
-202
4.77
CO
CO
DATA
B
ull
. 28,
17
pp.
77F
Fis
her
,F.H
. an
d F
ox,A
.P.(
1977)
J.
Solu
tion C
hem
. £,
64
1-6
50
.78
E
Elg
quis
t.B
and
W
edbo
rg.M
.(19
78)
Mar
. C
hem
. £,
24
3-2
52
.78
J Jo
hn
son
,K.S
. an
d P
ytk
ow
icB
,R.M
.(l9
78)
Am
. J.
S
ci.
27
8.
1428
-144
7.79
C
Coff
y.G
. an
d O
lofs
son,G
.(1979)
J.
Che
m.
The
rmod
yn.
11,
141-
144.
.PO
TASS
IUM
.
K*
aque
ous
ion
G°-
-67.5
2(.
03)
kca
l/m
ol
H°-
-60.2
7(.
03)
kca
l/m
ol
S°=
-24
.14
(.0
6)
cal/
deg
.mo
l C
p-5
.3 ca
l/deg
.mol
Ref
eren
ces:
77
G,7
7CO
,81W
K* +
SO2."
- KSOT
4 4
log
K
0.82
0.96
0.84
7
0.75
0.83
Source
H°
Source
REMARKS
30H
50J
68T-
74T-
76P
3.08
2 68T-74T-76P
WATE
Q - WA
TEQF
691
1.01
691
72T
TABU
S 6.
P
art
ial
com
pil
atio
n of
ther
mod
ynam
ic d
ata
for
the
WAT
BQ p
rogra
ma(
conti
nued
):
0.8
5(.
05)
77N
-80B
2
.25
(1.0
) 77
N-8
0B
WAT
EQ2
1.02
77
P
Ref
eren
ces:
30R
R
igh
ella
to.E
.C.
and
Dav
ies.
C.W
.O 9
50)
Tra
ns.
F
arad
ay
Soc
. 26
, 59
2-60
0.50
J Je
nkin
s.I.
L.
and
Mon
k,C
.B.O
950
) J.
A
m.
Che
m.
Soc
. 72,
2695
-269
8.68
T
Tru
esdel
l.A
.H.
and
Hoate
tler,
P.B
.(l
968)
G
eoch
im.
Cos
moc
him
. A
cta
52,
1010
-102
2.69
1 Iz
att,
R.M
.,E
atough,D
.fC
hri
stense
n,J
.J.,
and
Bar
thol
omew
,C.H
.(1
969T
~J.
C
hem
. S
oc.
(A),
47-5
5.
72T
T
rues
del
l,A
.H.
and
Jon
es,B
.P.(
19
72
) u
np
ub
lish
ed
dat
a74
T
Tru
esdel
l,A
.H.
and
Jones,
B.P
.(l9
74)
J.
Res
. U
.S.
Geo
l.
Sur
vey
£,
255-
248.
76P
Plu
mm
er.L
.H.,
Jones
,B.P
.,
and
Tru
esdel
l,A
.H.(
l 97
6) U
.S.
Geo
l.
Sur
vey
W.R
.I.
76-1
5,
61
pp.
77C
O C
ODAT
A B
ull
. 28
, 17
pp.
77F
Pis
her
.P.H
. an
d P
ox
,A.P
.(l9
77
) J.
S
olu
tio
n
Che
m.
£,
64
1-6
50
.77
G
Gio
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o,G
.M.,
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P.,
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ini,
T.,
an
d R
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i,S
.(l9
77)
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Che
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The
rmod
yn.
J9_,
997-
1004
.77
N
Nord
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m,D
.K.(
197
7)
Ph.
D.
Th
esis
, S
tan
ford
U
niv
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ity
, S
tanfo
rd,
210
pp
. ~~
SOB
Bal
l,J.
W.,
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rdst
rom
,D.K
.,
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E.A
.(1960)
U.S
. G
eol.
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urve
y W
.R.I
. 7
8-1
16
, 109pp.
81W
W
agm
an,D
.D.,E
vans
,W.H
.,Par
ker,
V.B
.,Sch
umm
,R.H
., an
d N
utt
all
.R.L
.(l
981
) N
at.
Bu
r.
Sta
nd
. T
ech.
N
ote
270-8
, 15
4 pp
.
.SO
DIU
M.
Na*
aq
ueou
s io
n
G°-
-62.6
0(.
02)
kca
l/m
ol
H°-
-57.4
3(.
016)
kca
l/m
ol
S°=
M3.
96
cal/
deg
.mo
l.1
ca
l/d
eg.m
ol
Ref
eren
ces:
77
CO
,81W
Na*
* SO?" - NaSOT
4 4
log
K Source
H°
Source
REMARKS
0.70
30
R
0.72
50J-76P
1.10
76P
WATEQP
0.90
66
M
0.65
691
-0.4
9 69
1
0.3
05 (
.00
7)
0.2
26
0.6
86
1.14
1.1
7
1.11
1.1
0
0.8
2(.
05)
0.7
3
1.03
0.7
0(.
05)
1.0
0
0.7
3(.
01)
0.6
0 (.0
2)
0.5
7 (.0
3)
69P
7U*7
4T
741!
53K
/75F
a
69P
/75F
a
50J/
75F
b
75Fb
75H
75S
77F
77N
-80B
78F
79E
79E
79E
2.22
97U-74T
1.12
(.80
) 62A-77N-80B
0 80J
I - 0.
687
WATB
Q
T - 20°C
reca
lcul
ated
sound
absorption m
easurements
corr
ecte
d to I
0
refitted conductance
meas
urem
ents
to new
equa
tion
VATEQ2
I - 0.75
I » 0.
12
I - 0.17
I - 0.
21
Ref
eren
ces:
30R
R
igh
ella
to.E
.C.
and
Dav
ies,
C.W
.(l9
30
) T
rans.
F
arad
ay
Soc
. 26
, 59
2.50
J Je
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s.I.
L.
and
Mon
k,C
.B.(
1 95
0) J.
A
m.
Che
ra.
Soc
. 72,
2695
-269
8.53
K
Kurt
ze.G
. an
d T
amm
.K.O
953
) A
cuat
ica
2.
33-4
8.
62A
A
ust
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Mai
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) J.
P
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.,E
ato
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.,C
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1 %
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47-5
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69
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26
7.
217-
220.
71L
L
afon
.G.M
. an
d T
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l.A
.H.
(197
1 )
Am
. G
eoph
ya.
Uni
on T
ran
s.(a
bst
ract)
5j
?,
362.
74M
M
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no
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O.I
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a,L
.G.,
an
d P
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S.A
.(1974)
Dok
l.
Aka
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Nau
k SS
SR
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10
80-1
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74T
T
rues
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l.A
.H.
and
Jon
es,B
.F.(
19
74
) J.
R
es.
U.S
. G
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S
urve
y j?
, 23
3-24
8.75
Fa
Fis
her
,F.H
.( 1
975)
J.
S
olu
tio
n
Che
m.
4_,
237-
240.
75Fb
F
ish
er,F
.H.
and
Fox
,A.P
. (1
97
5)
J.
So
luti
on
C
hem
. 4_
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5-23
6.75
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422-425.
75S
Sant
os,M
.M.,
de Ca
rval
ho, J.R.F.G.,
and
de Carvalho.R.A.G.O 975
) J.
Solution Ch
em.
4.,
25-29.
76P
Plum
mer.
L.N.
.Jon
es,B
.F.,
an
d Truesdell,A.H.(l976) U.S. Geol.
Survey W
.R.I
. 76
-13,
61
pp
.77CO CODATA Bu
ll.
28,
17 pp
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F Fi
sher
,F.H
. an
d Fox,A.P.(l977) J. So
luti
on Chem.
£, 64
1-65
0.77
N Kordstrom,O.K.(1977) Ph.D.
Thesis,
Stanford Un
iver
sity
, St
anfo
rd,
210
pp.
78F
Fish
er,F
.H.
and
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A.P.
(197
8) J. So
luti
on Chem.
7, 56
1-57
0.79E
Emara,M.M.,Farid,N.A., an
d Li
n,C.
T.(l
979)
J. Ch
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56,
620-621.
80B
B
all,
J.W
.,N
ord
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.K.,
and
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E.A
.(1980)
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. G
eol.
S
urve
y W
.R.I
. 7
8-1
16
, 109pp.
80J
Joh
an
sso
n.O
..P
ers
son
.I.,
an
d W
edbo
rg.M
.(19
80)
Mar
. C
hem
. 8,
191-
198.
y\
TABL
E 6.
P
art
ial
com
pil
atio
n o
f th
erm
odyn
amic
dat
a fo
r th
e W
ATEQ
pro
gra
ma(
con
tin
ued
):
81V
W
agm
an,D
.D.,E
vana
,W.H
.,Par
ker,
V.B
. ,S
chun
m,8
.H.,
and
Nutt
all,
R.L
.(1981)
Nat
. B
ur.
Sta
nd.
Tec
h.
Not
e 27
0-8,
13
4 pp
.
Foot
note
s:(1
) log KS
() «
-34.0 (66K.79M)
for well-crystallized
gibb
aite
and
log KW
.
-13.
997
(76B)
were
used
to calculate
*K1K
2K5K
4 fr
om K
a4 or *
Kfl4
.
(2)
log K
Q m -31.2
from 6
3F (i
n gi
bbsi
te se
ctio
n) for amorphous
log
K 0
» -31.2
from 6
3F (i
n gi
bbsi
te se
Al(01f)3
waa ua
ed to calculate *K
1K2K
3K4
.
(3)
log K
0 - -3
2.65
fr
om 6
7H fo
r microcryatalline g
ibbs
ite
was
used to
calculate 'K.KK.
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