486

Geochcinistry, groundwarer andpoll~ition

Table l a. Summary of revised thermodynamic data. I: Fluoride and chloride species.

Reaction

log K

AHO
(kcallrAol)

H'+F=HP

log K

(kcall&ol)

3.18

3.18

+ F = AIFY*

AI"

1.06

7.0

3.76

AI"

+ 2 F = AIF,'

1.98

12.7

NB*+ F = N a P

---.

-0.24

AI"

+ 3 F = AIF;

2.16

16.8

+ F= C S
Mg" + F = MgP

4.12

0.94

AI"

+ 4 F = AIF,'

2.20

19.4

3.2

1.82

AI"

+ 5~

= AIF,"

1.04

20.6

----

0.84

AP+ 6 F = AIF,"

-1.67

20.6

---

1.O

2.7

6.2

-16.26

30.18

H'

+ 2 F = HF,'

Table lb. Summary of revised thermodynamic data. 11: Oxide and hydroxide species.

AHO

Reaction

4.55

Ca"

Mn"
Fe"

+ F = MnF
+ F = FeF

Fe" t F = FeF2'
Fe"

+ 2 F = FeF,'

4.8

Si(OH),

+ 4H' + 6 F

= SiF,"

10.8

5.4

14.0

Fe" + CI' = FeCV

----

0.14

Mn"

+ CI' = MnCI'

----

0.61

Fe" + CI' = FeCI"

5.6

1.48

Mn"

+ 3CI' = MnCI,'

----

-0.3 1

+ 3CI' = FeCI;

----

1.13

FeL+3F=FeF;

Mineral

Fe"

AH o

Reaction

log K

o<cal/&ol)
Cryoliie

Na,AlF, = 3Na'

Fluoriie

CaF, = Ca1'

Rcdox Potentials

+ Al" + 6 F

t 2F

AH O
otcall&ol)

Fe" = Fe"

+ e'

Mn" = Mn" + eReaction

E"
(volis)

9.09

-33.84

4.69

-10.6

log K

9.68

-0.770

-13.02

25.8

-1.51

-25.51

+ 011+ H,O = LiOtP + H*

Na' + H,O = NaOW + H'
H,O = H'

13.362 -14.000
0.0

K'

+ H,O = K O P + H'

+ H,O = CaOH' + H'

Mg" + H,O = MgOH' + H'
Sr" + H,O = SrOH' + H'
Ba" + H,O = BaOH' + H'

Ca"

Ra" + H,O = RaOH' + H'

Analyiical Expression< for Temperaiure Dependence

+ H,O = FeOH' + H'

Mn" + H,O = MnOH'

logKmuairrs = 66.348 4298.2IT - 25.271 log T

H'

-13.64

Fe" + H,O = FeOH" + H'

Fr" + ZH,O = Fe(OHh' + 2H'

10.4

-2.19

17.1

-5.67

0.0

-14.18

-----

-14.46

---

-1 1.44

-----

-13.29
-13.47

+ 3H,O = Fe(OH),O + 3H' 24.8

+ 4H,O = Fe(0H); + 4H' 31.9
2Fe" + 2H,O = Fq(OH):' + 2H' 13.5
3Fe" + 4H,O = Fe,(OH):' + 4H' 14.3
AP + H,0 = AIOH" + H'
11.49
Al" + 2H10 = AI(OHg + 2H' 26.90

-12.78

Fe"

-12.56

Fe"

-21.6

-13.49

Alh

+ 3H10 = AI(OH)P + 3H'

39.89

-16.9

-9.5

Al"

+ 4H,O = AI(0H);

42.30

-22.7

14.4

-10.59

4H'

AH o
(lLcal/rAol)

Pnilandiie

Ca(OH),

B~cite

Mg(OH), + ZH' = Mg" + 2H20

-27.1

16.84

Pyrolusirc
Hausmaniie

MnO, + 4H' + 2e- = Mn" + 2H,O

Mn,O, + 8H' + 2e' = 3Mn" + 4H10

-65.11
-100.64

41.38
61.03

Manganite

MnOOH

Pyochroiie

Mn(OH)2 + 2H' = Mn" + 2H10

Gibbsiie (crysialline)

AI(OH),

Ferrihydriie(morphous io
minocrysLalline)

+ 2H' = Ca" + 2H,O

-31O
.

+ 3H' + es = Mn" + 2H20

+ 3H'

+ 3H20
AI(OH), + 3H' = Alh + 3H,O
= Al"

Fe(OH), + 3H' = Feb

+ 3H10

22.8

----

25.34

.-.-

15.2

-22.8

8.1 1

(-24.5)

9.35

--.-

+ OH.

3.0

10 5.0

logK, = -283.9710 + 13323.00fl- 0.05069842T + 102.24447 log T -1119669K1

+ 14.327 log T

IogK, = -38.253 - 656.27fl

AI"

+ H,O = AIOW + H'

+ ZH,O = AI(OHg + 2H'
+ 3H,O = AI(0H): + 3H'

Al"

+ 4H,O = AI(0H); + 4H'

log, = 51.578 - 11168.9fl- 14.865 log T

Al"

log K

Analyticd Expressions lor Temperalure Dependence

Rcaction

AI"

-5.00
-10.1

---

Reaction

Gibbsile(micronysial1ine)

-2.95
-6.3

13.2

Mineral

H P = H'
CS, = Caz' t 2 F

AH: log K
o<cal/mol)

Reaction

Li'

Fe"

+ 4H10

Ay0 log K
(kcdlmol)

Reaction

log& = 88.500 9391.6fl

log, = 226.374

- 27.121 log T

- 18247.8fl - 73.597 log T

488 Geochemistry, groundwater andpollution

Table Id. Summary of revised thennodynamic data. IV:Silicate species.

Table Ic. Summary of revised thermodynamic data. IiI: Carbonate species.

Reaction

Ca"

CO,(g) = CO,(aq)
CO,(aq) + t4,O = H'

+ HCO;'

Sr"

+ HCO,'

Ba"
Fe"

= MgHCO;

+ HCO,'
+

= hlnHC0;

Mineral

3.545

3.224

Si(0H)P = SiO(0H); + H'

2.713

2.98

Si(0H): = SiO,(OHhh

5.22

2.81

3.55

2.71
4.90

Kiolinile

AI,Si,O,(OH),

Na'

+ CO,"

= NaCO,'

8.91

1.27

Ctuysotile

Mg,Si,O,(OH),

Ni'

Sqiolite

Mg,Si,0,,(OH).3HlO

-0.25

1.07

CaCO, = Ca1'

Dolomite(0rdered)

CaMg(C0,h

+ CO,*
= Ci'' + Mg"

Dolomite(bisordered)

CaMg(C0,h = Ca"

Slrontianiie

S m , = Sr" + CO,"

Sideriie(crystalline)

FeCO, = Fe"

Sideriie(precipitaied)

FeC0, = Fe"

Wiiherile

aCO, = Ba1'

Rliodoaosife(crysia1Line)

MnCO,

Rhodonosiie(syntlietic)

MiiCO, = Mn"

Reaciion

log K

HCO; = H'
Mg"

+ CO,"

+ HCO;

+ Mg" + ZCO,"

+ CO,"
+ CO,"
+ CO,"

logK2 = -107.8871 - 0.03252849T + 5151.79fl

= SrHCO,'

logK'
lngK,'=

= 1209.120 + 0.31294T

+ 2537.455fl + 20.92298 log T

+ 0.014867T
= -3.0938 + 0.013669T
= -1228.732 - 0.299444T + 35512.75fl + 485.818 log T

+ HCO;
+ CO,"

= CaCO,'

logbm]

Mg"

+ CO,"

= MgCOP

1 0 g . K ~ ~=; 0.9910

= aHCO,'

logKhIm'

SI=' + CO," = srco;

logK-:

Ray' t CO," = RaCO,'

logK,P

CaCO, = Ca"

+ CO,"

log&

CaCO, = Ca"

+ CO,"

logK,

srco, = Sr" + CO,"

+ CO,"

+ 38.92561 log T - 563713.9/10

- 34765.05K - 478.782 log T

-3.248

Ba"

RaCO, = Ba"

- 40.45154 log T + 669365fly

+ 126.8339 log T - 1684915f11

= -59.215

Ca1'

+ 0.00667T

+ 0.012826T
= 0.1 13 + 0.008721T

= -1.019

logKmomm

= -171.9065

- 0.077993T + 2839.319fl + 71.595 log T

= -171.9773 - 0.07'7993T

+ 2903.293fl + 71.595 log T

= 155.0305 - 7239.594fl 56.58638 log T

logKWlmm = 607.642

2Si(OH)P + H,O

+ 2Si(OH);

+ 4H' + 0.5

H,O = 2

+ 6H' t 3H,O

Kerolite

Mg,Si,O,(OHh.H,O

Quaru

SiO,

Chalcedony

SiO,

+ 2H,O = Si(Otl)?

-35.3
46.8

t H,O

+ ~3~i(0ll)P
"

7.435
32.20

-10.7

15.76

-..

25.79

5.99

-3.98

= 3Mg2' + 4Si(OH):

2H,O = Si(0H)P

+ CO,"
= Mn" + CO,"

logKarn'

= 3Mg"

ZCO,"

logKl = -356.3094 0.06091964T + 21834.37fl

+ HCO; = MgHCO;

Sr"

logKIi = 108.3865 + 0.01985076T 6919.53fl

Cay' + HCO; = CaHCO,'

= 2AI"

+ 6H'

log K

Amorplious Sica SiO, + 2H,O = Si(0H)P

Analyiical Expression5 for Temperature Dependence

CO,@) = CO&)
CO,(aq) + H,O =
H' + HCO;

+ 6H'

2.5

o<cal/Aol)
CaCO, = Ca2' + CO,"

AH:

(kcalhol)

4.38

---

-23.0

Reaction

..-

HCO,' = NaIlCO,'

-9.83

17.6

---

= MnCO;

AH

Aragonite

6.12

+ 2H'

= FeCO,'

+ CO,"

Reaction

Calcile

Mineral

log K

(kcailmol)

+ CO:

Ray' + CO," = RaCO;

tlCO; = FeHCO;

Ayo

Reaction

Fe"

Mn"

+ HCO; = SrHCO,'
+ HCO,' = aHCO;

Mn1'

= CaCO,'

+ CO: = MgC0,O
Sr" + CO,' = SKO,'
Ba2. + CO,&= BaCO;

+ CO,"

HCO; = H'

+ CO,'

Mg"

Caz' + HCO; = CaHCO;

Mg"

AH: log K
(kcal/mol)

Reaction

+ 0.121098T - 20011.25fl - 236.4948

log T

Reaction

Analyiical Expressiom for Tcmperaiure Dependence

s~(oH)? =.s~o(oH); + H'

logKl = -302,3724 - 0.050698T + 15669.69K + 108.18466 log T

1119669fl"

Si(OH)P = SiO,(OHh'. + 2H'

logl = -294,0184 - 0.072650T + 11204.49fl + 108.18466 log T

1119669f12

Mg,Si,O,(OH), + 6H' =
3Mg" + 2Si(Otl)P + H,O

logK,

SiO, t 2H,O = Si(0H)P

logKWARrz= 0.41

2H10 = Si(0ll)P

SiO,

SiO,

+ 2H,O = Si(0H)P

= 13.248 + 10217.1fl 6.1894 log T

13Wfl

= -0.09 /- 1032/T

logKa
g

~ = -0.26
~
~731fl
~

490 Geoclreniistry,gro~itid~~nter
andpollrrrion
Table 2a. Trace elements: Arsenic.

Table le. Summary of revised therrnodynamic data. V: Sulfate species.

AH,' log K
O<cal/mol)

Reaction

+ SO,* = HSO;

H'

Mn"

Li' +SO," = LiSO;

+ SO," = NaSO,'

Na'

+ SO,"

K'

C P

= KSO;

+ SO,"
t

Fe1'

+ SO,"

Fe"

+ HSO;

Fey'

= MnSOf
= FeSOf

= FeHSO,'

SO," = FeSO,'

Fe"

Al"

= BaSOP

+ 2S0,"

= AI(SO,),'

Mineral

Reaciion

Arsenoliie

As406

AIL + HSO; = AIHSO,"

SO," = RaSOP

+ 3H10

Asl,

Mineral

Ruction

Gypsum

CaS0,.2H ,O = Ca1'

+ SO," + 2H,O

+ SO,%

-0.109

-4.58

Anhydriic

CaSO. = Ca"

Celestik

SrSO, = Sr"

Bariie

BaSO. = Ba" t SO,"

6.35

-9.97

Radium sulfau

RaSO, = Ra"

+ SO,"

9.40

-10.26

+ SO,"

+ SO,'. + 7H10

Melanierite

FeS0,.7H10 = Fe"

Aluniic

KAI,(SO,X(OH), t 6H' = K' t 3A1" t 2S0," t 6H,O

-1.71

-4.36

-1.037

-6.63

4.91

+ 6H10
+ 6H20
A s o 5 + 3H10

= HSO;

logK2 = -56.889

As,06

4H3As0,

2H3As03

logK

+ SO,"

BaSO, = Ba"

+ SO,"

logKl-

RaSO. = Ra"

+ SO,"

SrSO, = Sr"

FcSO,.7H,O = Fe" + SO," + 7H,O

logK
l0gK-

= 197.52 8669.8n

13.29

+ 3HS' + 3H*

82.89
-5.405

e 2H3As0,

+ 3H' ~1 H3As0, + Al3* + 2H10

Ca3(As0,),.6H20 + 6H+ 0 2H3As04 + 3Ca1+ + 6H20
Cti3(As0,),*6H20 + 6H+ E1 3Cu2* + 2H,AsO, + 6H20
FeAs0,-2H20 + 3Ht # H3As0, + Fe3+ + 2H20
M~,(AsO~)~*~H,O
+ 6H' s 2H3As04 + 3Mn2' + 8H,O N~,(ASO,)~.~H,O
+ 6Ht # 2H3As0, + 3Ni2+ + 8H20 Pb,(As04), + 6H+ ~t 3Pb2* + 2H3As0,
AIAs0,*2H10

-1.4

B~,(AsO,)~ 6H'

19.8858 log T

- 3221.51r - 25.0627 108 T

- 69.835 log T
g b = -14805.9622 - 2.4660924T + 756968.533n
- 40553604Kz + 5436.3588 log T
= 136.035 - 7680.41K - 48.595 log 'I'
= 137.98 - 8346.87F - 48.595 log T
= 1.447 - 0.004153T - 214949ff
= 68.2401

CaS0,.2H10 = Ca" + SO," + 2H,O

CaSO, = Ca" t SO,"

+ 0.006473T + 2307.9n +

1.875
14.33

A$S3

Zn,(As0,),*2.5H20

+ SO.*

+ 3P + 3HC

4H3As0,

Claudeiiie

-2.209

40.25

e H,AsO,

+ 61i20 rt

Orpiinent

Analytical Expressiom for Tempaaiure Dependence

Reaction
H'

log K

FeL

Sr" + SO," = SrSOP

Ra"

+ SO,"

AHP
(kcalliiiol)

+ 2S0,' = Fe(SO,),'
+ HSO; = FeHSO,"
AlL + SO," = AISO.'

+ SO,* = CaSOf

Mg" t SO( = MgSOf

Ba"

Reaciion

Reaction

Realgar
Redox Poieniial

ASS

+ 3H10

+ 6Ht
#

r~ 2H3As0,

3Ba2'

+ 2H3As0,

e H3As03 + HS'

+ 3zn2+ + 2.5H10 2.64

+ ZH* + e'

30.545
AH,'

(kcallmnl\

log K