Appendix C

Arsenic Thermodynamic Data

C.1 Introduction
Italicized terms in the text of this appendix or words derived from the italicized terms are defined in the
glossary of Appendix B.
Table C.1 lists published thermodynamic data for arsenic, including: the more common elemental
forms, selected compounds, and some aqueous and gaseous species. The table contains Gibbs free energy
(Gf ), enthalpy (Hf ), entropy (S), and heat capacity (Cp) values at 1 bar pressure and mostly at
298.15 K (25 C). For thermodynamic data of chemical species not containing arsenic, extensive tables
occur in geochemistry textbooks and other references, including: (Barin, 1995; Robie, Hemingway and
Fisher, 1979; Wagman et al., 1982; Drever, 1997; Eby, 2004; Faure, 1998; Lide, 2007; Krauskopf and
Bird, 1995). Thermodynamic data are important in examining the behavior of arsenic in mineralwater
interactions, studying water quality issues, investigating the formation of ore deposits, developing and
interpreting Eh-pH diagrams, and designing environmental remediation projects (Nordstrom and Archer,
2003, 12).
Not all published and widely accepted thermodynamic values are reliable. Nordstrom and Archer (2003)
provide a detailed review of the controversies, uncertainties, and problems related to thermodynamic data
for arsenic and its compounds and aqueous species. Many of the data are contradictory and the methods
that produce the data are sometimes questionable or have not been thoroughly documented. Too often,
data in the literature have been passed from reference to reference without critical evaluations. Some
of the data have high measurement errors, were produced under undefined or poorly defined laboratory
conditions, and involved unrepresentative sampling (Matschullat 2000, 298; Nordstrom and Archer, 2003).
Furthermore, other questionable data originate from obscure documents or are written in languages that
many individuals cannot read and properly interpret. Therefore, thermodynamic results must be accepted
with a certain amount of caution. The table in this appendix includes thermodynamic data from various
sources, which provide users with some idea of their variability. Although sometimes unavoidable, users

Arsenic Edited by Kevin R. Henke

2009 John Wiley & Sons, Ltd. ISBN: 978-0-470-02758-5

476

Arsenic

are cautioned to avoid mixing data from different literature sources when performing calculations for a
reaction. Using data from multiple sources may introduce serious errors (Wagman et al., 1982; Eby, 2004,
474).

C.2 Modeling applications with thermodynamic data

Once high-quality laboratory data are available, they may be used in geochemical computer models, such
as MINTEQA2 (Allison, Brown and Novo-Gradac, 1991) and PHREEQC (Parkhurst and Appelo, 1999).
Langmuir (1997, 558561) provides a brief review of the different types of geochemical models and their
advantages and limitations. Geochemical models allow users to avoid tedious calculations. When properly
utilized, they may: (1) derive adsorption models, (2) identify probable aqueous species and estimate their
activities, (3) model the effects of pH, reduction/oxidation (redox conditions), temperature, ionic strength,
and other factors on arsenic chemistry, and/or (4) identify possible precipitates. However, as discussed in
Chapter 2, geochemical models are often incapable of accurately representing and predicting the complex
behavior of arsenic in natural environments. Specifically, the models typically fail to predict the presence
of metastable species, sluggish chemical reactions, and the effects of biological organisms.

C.3 Thermodynamic data

As(0) (elemental arsenic,

rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)

Elemental
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)

Chemical species

400
400
500
500
600
600
700
700

xls
xls
xls
xls
xls
xls
xls

298.15

xls

xls

298.15

xls

298.15

298.15

xls

xls

298.15

xls

Phase Temperature
(K)

Gibbs free
energy (Gi )
(kJ mol1 )

Enthalpy (Hi )
(kJ mol1 )

57.696

57.68

53.569

53.55

48.790

48.77

43.065

43.04

35.706

35.6

35.69

35.1

35.63

Entropy (Si ) (J
mol1 K1 )

27.054

27.05

26.501

26.51

25.945

25.96

25.388

25.38

24.652

24.65

24.43

Heat Capacity
(Cpi ) (J
mol1 K1 )

(continued overleaf )

Robie, Hemingway
and Fisher (1979)
Barin (1995)

Robie, Hemingway
and Fisher (1979)
Barin (1995)

Robie, Hemingway,
and Fisher (1979)
Barin (1995)

Robie, Hemingway
and Fisher (1979)
Barin (1995)

Robie, Hemingway
and Fisher (1979)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Barin (1995)

Nordstrom and
Archer (2003)
Wagman et al. (1982)

Reference

Table C.1 Thermodynamic data for arsenic, its compounds, and its aqueous and gaseous species at 1 bar pressure. Note that the units of Gi and
Hi are 1000 times larger than Si and Cpi . 1 kcal = 4.184 kJ. C = K 273.15. (See Appendix A for other unit conversions). Phases include:
amorphous (am), aqueous species (aq), gas, liquid (liq), and crystalline solids (xls).

Arsenic Thermodynamic Data

477

298.15
298.15

298.15

gas
As4
Gases and aqueous species
of arsenic compounds

298.15

am

gas
gas

298.15

am

As4
As4

875

xls

298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15

800

xls

gas
gas
gas
gas
gas
gas
gas
gas

800

xls

As(0) (elemental arsenic,

rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
rhombohedral or gray)
As(0) (elemental arsenic,
amorphous or black)
As(0) (elemental arsenic,
amorphous or black)

As+
As2+
As3+
As4+
As5+
As6+
As2
As2

Phase Temperature
(K)

Chemical species

Table C.1 (continued)

98.261

92.4
87.9

171.9
143

Gibbs free
energy (Gi )
(kJ mol1 )

153.30

143.9
144

1255.6
3059.8
5801.1
10644
16694
29045
222.2
194

13.6

4.2

Enthalpy (Hi )
(kJ mol1 )

327.43

314
330

239.4
242.2

63.82

61.344

61.33

Entropy (Si ) (J
mol1 K1 )

77.208

35.003

28.03

27.580

27.60

Heat Capacity
(Cpi ) (J
mol1 K1 )

Naumov, Ryzhenko
and Khodakovsky
(1974)
Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Wagman et al. (1982)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Barin (1995)

Robie, Hemingway
and Fisher (1979)
Wagman et al. (1982)

Robie, Hemingway
and Fisher (1979)
Barin (1995)

Reference

478
Arsenic

634.29
116.3
116.32
1431.1

132.1
130
130.00
270.3
261.5
261.50
305.0
305.01
785.8
785.76
785.76
821.3
821.32
1236.7

545.39

115.20
1333.1
1280.8
1709
161.67
159
159.80
258.05
248.9
248.66
259.4
259.08
905.67
770.76
770.65
774.16
774.01
1172.5

298.15
298.15
298.15
298.15
298.15
298.15

gas 298.15
gas 298.15
gas 298.15
gas 298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15

xls
xls
xls
xls
xls
xls

gas
gas
liq
liq
gas
gas
gas
liq
liq
gas

Ag3 AsO4
AlAs
AlAs
AlAsO4
AlAsO4
AlAsO4 2H2 O
(mansfieldite)

AsBr3

AsBr3
AsBr3
AsCl3

AsCl3
AsCl3
AsCl3
AsCl3
AsF3

AsF3
AsF3
AsF3
AsF3
AsF5

298.10
289.22
181.21
181.21

327.17
327.30
216.3
216.31
289.0

363.87
363.99
328.8

363.8

275.83

60.25
145.60

65.61
64.684
126.57
126.55

75.73
75.395

133.47

79.16
78.992

173.86

45.80
118.34

(continued overleaf )

Barin (1995)
Wagman et al. (1982)
Barin (1995)
Barin (1995)
Ryu et al. (2002)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Pankratov and
Uchaeva (2000)
Wagman et al. (1982)
Barin (1995)
Pankratov and
Uchaeva (2000)
Wagman et al. (1982)
Barin (1995)
Wagman et al. (1982)
Barin (1995)
Pankratov and
Uchaeva (2000)
Wagman et al. (1982)
Barin (1995)
Wagman et al. (1982)
Barin (1995)
Pankratov and
Uchaeva (2000)

Arsenic Thermodynamic Data

479

298.15
298.15
298.15
298.15
298.15

gas
gas
gas
gas
gas

gas
xls
xls
gas
gas
gas
gas
xls
xls
xls

xls
xls
xls
xls
xls

AsF5
AsF5
AsH3 (arsine)

AsH3 (arsine)
AsH3 (arsine)

AsH3 (arsine)
AsI3
AsI3
AsI3
AsI3
AsN
AsO
As2 O3 (arsenolite, cubic)

As2 O3 (arsenolite, cubic)

As2 O3 (arsenolite, cubic)

As2 O3 (arsenolite, cubic)

As2 O3 (arsenolite, cubic)
As2 O3 (claudetite,
monoclinic)
As2 O3 (claudetite,
monoclinic)
As2 O3 (claudetite,
monoclinic)

298.15

298.15

298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15

298.15
298.15

298.15
298.15
298.15

Phase Temperature
(K)

Chemical species

Table C.1 (continued)

66.442
58.2
58.158

38.911
196.27
57.287
657.27
657
666.1

656.97
655.67
655
664.0

69.109
59.4
59.091

15.321
167.97
84.715
576.34
576
588.3
576.41
575.96
576.53
576
589.1

66.44
66.4

1234.2
1236.8
66.40

1169.0
1169.6
68.91
68.93
68.83

Enthalpy (Hi )
(kJ mol1 )

Gibbs free
energy (Gi )
(kJ mol1 )

127

113.3

107.41
113.37

117

107.4

222.78
213.05
213.05
388.34
391.82
225.6
230.27
107.38

222.78
223

317.26
223.0

Entropy (Si ) (J
mol1 K1 )

96.878
96.98

38.072
105.77
105.77
80.63
80.960
30.42
32.342
96.88

38.07

87.84
97.541

Heat Capacity
(Cpi ) (J
mol1 K1 )

OHare (1993)
Barin (1995)
Pankratov and
Uchaeva (2000)
Wagman et al. (1982)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Barin (1995)
Wagman et al. (1982)
Barin (1995)
Wagman et al. (1982)
Barin (1995)
Wagman et al. (1982)
Barin (1995)
Nordstrom and
Archer (2003)
Robie, Hemingway
and Fisher (1979)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Davis et al. (1996)
Barin (1995)
Nordstrom and
Archer (2003)
Robie, Hemingway
and Fisher (1979)
Naumov, Ryzhenko
and Khodakovsky
(1974)

Reference

480
Arsenic

aq

As3 S4 (SH)
2
298.15

127.19

96.2

95.4

xls 298.15

As2 S3 (orpiment)

85.8

84.9

xls 298.15

As2 S3 (orpiment)

66.9

245.11
76.8

aq 298.15
am 298.15

AsS(OH)(SH)
As2 S3

31.0

30.9

xls 298.15

AsS ()

36

35

xls 298.15

924.87
924.87
924.59
922.93
2104.6

4248.4
1196.2
31.8

782.78
782.3
782.09
733.31
685.66

1720

1092.2
31.3

AsS (, realgar)

298.15
298.15
298.15
400
500
298.15
298.15
298.15
298.15
298.15

xls
xls
xls
xls
xls
xls
xls
xls
gas
xls

As2 O5
As2 O5
As2 O5
As2 O5
As2 O5
As2 O5 4H2 O
As2 O5 4H2 O
(As2 O5 )3 5H2 O
As4 O6
AsS (, realgar)

164

163.8

200

63.5

63.5

105.4
105.40
142.62
174.77

409.35
62.9

105

924.7

782.0

xls 298.15

As2 O5

105.44

1194.32
917.59

774.96

xls 298.15
xls 298.15

117.00

654.80

576.64

xls 298.15

As2 O3 (claudetite,
monoclinic)
As2 O3 SO3
As2 O5

163

47

116.52
116.54
136.54
151.78

173.60
47

115.9

96.979

(continued overleaf )

Wagman et al. (1982)

Nordstrom and
Archer (2003)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Davis et al. (1996)
Wagman et al. (1982)
Barin (1995)
Barin (1995)
Barin (1995)
Wagman et al. (1982)
Faure (1998)
Wagman et al. (1982)
Barin (1995)
Nordstrom and
Archer (2003)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Nordstrom and
Archer (2003)
Helz et al. (1995)
Nordstrom and
Archer (2003)
Nordstrom and
Archer (2003)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Helz et al. (1995)

Barin (1995)

Arsenic Thermodynamic Data

481

xls
xls
xls
am
xls
xls
xls
xls
xls
xls
xls
xls

gas
xls
xls
xls
xls
xls
xls
xls
xls
xls

xls

As2 Se3
As2 Se3
As2 Se3
As2 Se3
As2 Te3
Ba3 (AsO4 )2
Ba3 (AsO4 )2
BaHAsO4 H2 O
Be3 (AsO4 )2
BiAsO4
BiAsO4
BiAsO4 (rooseveltite)

(CH3 )3 As

Ca(H2 AsO4 )2
Ca2 AsO4 OH
Ca3 (AsO4 )2
Ca3 (AsO4 )2
Ca3 (AsO4 )2
Ca3 (AsO4 )2 2.25H2 O
Ca3 (AsO4 )2 3H2 O
Ca3 (AsO4 )2 3.67H2 O

Ca3 (AsO4 )2 4H2 O

Ca3 (AsO4 )2 4.25H2 O

296

298.15

298.15
298.15
298.15
298.15
298.15
298.15
298.15
296

298.15

298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15

Phase Temperature
(K)

Chemical species

Table C.1 (continued)

4085

3298.7
3298.7

2054
1988
3061
3063.1
3063.0
3611.50
3787.87
3945
4019

12

86.1
81.1
102.51
53.1
37.656

3421.7

2738.1

795.21

88.4

101.43

39.580
3113.40
3192.2
1544.47
2525.5
619
695.43
613.58

Enthalpy (Hi )
(kJ mol1 )

Gibbs free
energy (Gi )
(kJ mol1 )

226.00
226

7.8

194.56

226.35

309.62

207.28

168.07

Entropy (Si ) (J
mol1 K1 )

249.79

121.39

127.49

257.21

232.52

121.12

Heat Capacity
(Cpi ) (J
mol1 K1 )

OHare et al. (1990)

OHare (1993)
Barin (1995)
OHare (1993)
Barin (1995)
Zhu et al. (2005)
Barin (1995)
Zhu et al. (2005)
Barin (1995)
Wagman et al. (1982)
Barin (1995)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Pankratov and
Uchaeva (2000)
Ryu et al. (2002)
Ryu et al. (2002)
Ryu et al. (2002)
Barin (1995)
Wagman et al. (1982)
Zhu et al. (2006)
Zhu et al. (2006)
Bothe and Brown
(1999)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Bothe and Brown
(1999)

Reference

482
Arsenic

301.71

206.83

59

100

1446.0

1934.3
41.8
41.840
17.6
40.6
51
61.5
83

aq
xls
xls
xls
xls
xls
xls
xls

xls 298.15
xls 298.15

CaHAsO04
Cd3 (AsO4 )2
Cd3 (AsO4 )2
Cd3 As2
Cd3 As2
CdAs2
CoAs
CoAs (modderite)

CoAs2
CoAs2 (safflorite)

97

1716.1
1712.0

35.885

49

1533

xls 296
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15

7803

xls 296

5096.47
5636.7
7808

xls 298.15
xls 298.15
xls 296

xls 298.15
xls 296

Ca4 (OH)2 (AsO4 )2 4H2 O

Ca5 (AsO4 )3 OH

4941

Ca5 (AsO4 )3 OH
Ca5 H2 (AsO4 )4
Ca5 H2 (AsO4 )4 9H2 O
(ferrarisite)
Ca5 H2 (AsO4 )4 9H2 O
(guerinite)
CaH(AsO4 )H2 O

xls 296

Ca4 (OH)2 (AsO4 )2 4H2 O

3530

xls 298.15

Ca3 (AsO4 )2 8H2 O

2732

4928.86
5087

xls 298.15

Ca3 (AsO4 )2 6H2 O

258.82

125.30

(continued overleaf )

Naumov, Ryzhenko
and Khodakovsky
(1974)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Bothe and Brown
(1999)
Zhu et al. (2006)
Bothe and Brown
(1999)
Zhu et al. (2006)
Ryu et al. (2002)
Bothe and Brown
(1999)
Bothe and Brown
(1999)
Bothe and Brown
(1999)
Wagman et al. (1982)
Wagman et al. (1982)
Barin (1995)
Wagman et al. (1982)
Barin (1995)
Wagman et al. (1982)
Wagman et al. (1982)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Wagman et al. (1982)
Naumov, Ryzhenko
and Khodakovsky
(1974)

Arsenic Thermodynamic Data

483

298.15
298.15
298.15
298.15
298.15
298.15

xls
xls
xls
xls
xls
xls
xls
xls
xls
xls
xls
xls
xls
xls
xls
xls
xls

xls
xls
xls
xls
xls
xls

Co2 As
Co2 As3
Co3 As2
Co5 As2
Co3 (AsO4 )2
Co3 (AsO4 )2
CrAsO4
Cr3 (AsO4 )2
Cs3 AsO4
Cu3 As
Cu3 As
Cu3 (AsO4 )

Cu3 (AsO4 )2
Cu3 (AsO4 )2
Cu3 (AsO4 )2 6H2 O
Cu3 AsS4 (enargite)

Cu3 AsS4 (enargite)

Cu3 AsS4 (enargite)
Fe3 (AsO4 )2
Fe3 (AsO4 )2 8H2 O
(symplesite)
FeAs (westerveldite)
FeAs2 (loellingite)

298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15

Phase Temperature
(K)

Chemical species

Table C.1 (continued)

43.51
43.5

43.36
52.09

62.5
127

257.6

337.02
155.35
321.42
283.59

137.24
255.98

298.61

356.4

39.7
97.5
81.2
79.5

1864.3
1062.1
2218.2
1668.5
11.7
11.715
710.36

1522.6

179.0

Entropy (Si ) (J
mol1 K1 )

Enthalpy (Hi )
(kJ mol1 )

437.26
1753.93
3687.26

1620.8
1671.9
968.36
2027.0
1543.9

12.322
624.04
1300.7
1301.32
1316.0
2733.04
206.74

Gibbs free
energy (Gi )
(kJ mol1 )

50.36

190.4

264.31
119.10
261.83
176.22

93.080
176.36

258.21

Perfetti et al. (2008)

Naumov, Ryzhenko
and Khodakovsky
(1974)

Wagman et al. (1982)

Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Barin (1995)
Barin (1995)
Barin (1995)
Barin (1995)
Wagman et al. (1982)
Barin (1995)
Barin (1995)
Wagman et al. (1982)
Davis et al. (1996)
Barin (1995)
Davis et al. (1996)
Castro and Baltierra
(2005) and Kantar
(2002)
Seal et al. (1996)
Davis et al. (1996)
Davis et al. (1996)
Davis et al. (1996)

Heat
Reference
Capacity
(Cpi ) (J
mol1 K1 )

484
Arsenic

aq 298.15

HAsO2
3

689

aq 298.15
aq 298.15

H2 AsO
3
H2 AsO
3
524

740.82

639.78

aq 298.15

H3 AsO03

714.79
714.74

1002.2
737.3
742.36

901.85
639.8
640.03

xls 298.15
aq 298.15
aq 298.15

GaAsO4
H3 AsO03
H3 AsO03

587.13
587.66

85.77

71
74.057
71

127.25
80.23
52.116
67.8
70.374
67.8

865.34

298.15
298.15
298.15
298.15
298.15
298.15

xls
xls
xls
xls
xls
xls

FeAsS (arsenopyrite)
FeAsS2 (loellingite)
FeAsS2 (loellingite)
GaAs (gallium arsenide)
GaAs (gallium arsenide)
GaAs (gallium arsenide)

298.15
298.15
298
298

772.39
772.62
1280.1
1279.2

1955.0
144.36

xls
xls
xls
xls

FeAsO4 2H2 O (scorodite)

Fe3 (AsO4 )2
FeAsS (arsenopyrite)
FeAsS (arsenopyrite)

298.15
298.15
298.15
296
1267.69
1766.0
136.45
141.6

xls
xls
xls
xls

FeAsO4
FeAsO4
FeAsO4 2H2 O (scorodite)
FeAsO4 2H2 O (scorodite)

15

110.5
112.79

200

150.12
212.4
195.8

80.1

64.18
64.183
64.2

339.91
68.5

161.54

197

118.26
85.0

70.83

46.23
46.858

264.64
68.44

117.05

(continued overleaf )

Barin (1995)
Ryu et al. (2002)
Ryu et al. (2002)
Krause and Ettel
(1988)
Davis et al. (1996)
Barin (1995)
Perfetti et al. (2008)
Pokrovski, Kara and
Roux (2002)
Davis et al. (1996)
Perfetti et al. (2008)
Davis et al. (1996)
Wagman et al. (1982)
Barin (1995)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Barin (1995)
Perfetti et al. (2008)
Nordstrom and
Archer (2003)
Pokrovski et al.
(1996)
Wagman et al. (1982)
Nordstrom and
Archer (2003)
Dove and Rimstidt
(1985)

Arsenic Thermodynamic Data

485

298.15
298.15
298.15
298.15
298.15
298.15

298.15
298.15

aq

aq
aq

aq
aq
aq
aq
aq
aq
aq
aq
aq
xls
xls
xls
xls

xls
xls

HAsO2
3

AsO3
3

AsO3
3

H3 AsO04
H3 AsO04

H2 AsO
4
H2 AsO
4

HAsO2
4

HAsO2
4
AsO3
4

HAsO3 F
AsO3 F2
Hg3 (AsO4 )2
InAs (indium arsenide)
InAs (indium arsenide)
InAs (indium arsenide)

InAsO4
KAs

298.15
298.15

298.15

298.15
298.15

298.15
298.15

298.15

298.15

298.15

Phase Temperature
(K)

Chemical species

Table C.1 (continued)

1271.0
58.6
58.601
57.7
978.30
102.9

1060.96
1027.45
1033.6
53.6
53.286
52.7
874.26

906.34
890.21

714.60
646.36

898.6
903.45

766.3
766.75

908.41

447.7

713.73

664

448

909.56
911.42

524.3

753.17
753.65

Enthalpy (Hi )
(kJ mol1 )

Gibbs free
energy (Gi )
(kJ mol1 )

154.85

323.47
75.7
75.701
75.7

176.31

11.42

117
112.38

198.3
183.07

187

Entropy (Si ) (J
mol1 K1 )

119.32

261.72
47.78
47.780

105.0

Heat Capacity
(Cpi ) (J
mol1 K1 )

Naumov, Ryzhenko
and Khodakovsky
(1974)
Dove and Rimstidt
(1985)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Perfetti et al. (2008)
Nordstrom and
Archer (2003)
Wagman et al. (1982)
Nordstrom and
Archer (2003)
Nordstrom and
Archer (2003)
Wagman et al. (1982)
Nordstrom and
Archer (2003)
Wagman et al. (1982)
Wagman et al. (1982)
Barin (1995)
Wagman et al. (1982)
Barin (1995)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Barin (1995)
Wagman et al. (1982)

Reference

486
Arsenic

1556.9
1702.4
126
371.5
3092.8

1455.7
1595.0

2775

xls
xls
xls
xls
xls
xls

LaAsO4
Li3 (AsO4 )
MgAs4
Mg3 As2
Mg3 (AsO4 )2
Mg3 (AsO4 )2

1668.7

1548.8
2021.1

xls 298.15
xls 298.15

K3 (AsO4 )
KUO2 AsO4

127.2
186.2
452.7
1180.7
1186.2

298.15
298.15
298.15
298.15
298.15
298.15

298.15
298.15
298.15
298.15
298.15

1035.9
1041.6

xls
xls
xls
xls
xls

KAs2
K3 As
K5 As4
KH2 AsO4
KH2 AsO4

163.47
173.13

237.82

155.02
155

117.89
161.84

172.29

126.73

(continued overleaf )

Wagman et al. (1982)

Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Barin (1995)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Barin (1995)
Barin (1995)
Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Ryu et al. (2002)

Arsenic Thermodynamic Data

487

Phase Temperature
(K)
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15
298.15

298.15
298.15
298.15
298.15

298.15
298.15
298.15
298.15
298.15
298.15

xls
xls
xls
xls
xls
xls
xls
xls
xls
xls

xls
xls
xls
xls

xls
xls
xls
xls
xls
xls

Chemical species

Mg3 (AsO4 )2
Mg3 (AsO4 )2 10H2 O
MgHAsO4
MgHAsO4 7H2 O
(roesslerite)
MgNH4 AsO4 6H2 O
MnAs ()
MnAs ()
MnAs ( )
MnAs
MnAs (kaneite)

Mn3 (AsO4 )2
Mn3 (AsO4 )2
Mn3 (AsO4 )2
Mn3 (AsO4 )2 8H2 O

MnHAsO4
MoAsO4
NaAs
NaAs2
Na3 As
Na3 As

Table C.1 (continued)

107.00
91.442
77.069

60

319.62

163.01
62.8
100
130
130.00

3316.7
51.861
53.297
56.902
59
57.3

2145.6
2366.3

1102.5
910.69
96.2
106.7
205
205.02

61.636
59.865
59.691

55.2
2167.4

2167.0
4055

817.79
89.1
100.4
187.4
187.10

225.10

3059.8

2831.7
5147.2
1187
2848

Entropy (Si ) (J
mol1 K1 )

Enthalpy (Hi )
(kJ mol1 )

Gibbs free
energy (Gi )
(kJ mol1 )

120.06

97.769

261.79

71.116
70.340
70.164

236.31

Heat Capacity
(Cpi ) (J
mol1 K1 )

Wagman et al. (1982)

Barin (1995)
Barin (1995)
Barin (1995)
Wagman et al. (1982)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Ryu et al. (2002)
Wagman et al. (1982)
Barin (1995)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Wagman et al. (1982)
Barin (1995)
Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Barin (1995)

Barin (1995)
Ryu et al. (2002)
Ryu et al. (2002)
Ryu et al. (2002)

Reference

488
Arsenic

xls
xls
xls
xls

xls
xls
xls
xls

xls 298.15
xls 298.15
xls 298.15

Na3 AsO4
Na3 AsO4
Na3 AsO4 12H2 O
NiAs (nickeline, niccolite)

NiAs
Ni3 (AsO4 )2
Ni3 (AsO4 )2
Ni3 (AsO4 )2 8H2 O
(Annabergite)

Ni5 As2
Ni11 As8
NH4 H2 AsO4

298.15
298.15
298.15
298.15

298.15
298.15
298.15
298.15

xls 298.15
xls 298.15

NaAsO2
NaUO2 AsO4 4H2 O

217.94

61

1540
1540.0
5092

73.291

1849.2

251.10
774.04
1059.8

1426.0

67.268
1579.3
1659.4
3482
242.11
762.63
832.9

190.63
468.88
172.05

45.380

344.80

660.53

2944.6

215.98
552.00
151.17

56.001

265.41

170.13

(continued overleaf )

Wagman et al. (1982)

Naumov, Ryzhenko
and Khodakovsky
(1974)
Wagman et al. (1982)
Barin (1995)
Wagman et al. (1982)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Barin (1995)
Wagman et al. (1982)
Barin (1995)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Barin (1995)
Barin (1995)
Wagman et al. (1982)

Arsenic Thermodynamic Data

489

298.15
298.15
298.15

xls

xls
xls
xls
xls
xls
xls

xls
xls
xls
xls
xls
xls
xls
xls
xls

NH4 H2 AsO4

(NH4 )2 HAsO4
(NH4 )3 AsO4
(NH4 )3 AsO4 3H2 O
Pb3 (AsO4 )2
Pb3 (AsO4 )2
Pb3 (AsO4 )2

Pb5 (AsO4 )3 Cl (mimetite)

Pb5 (AsO4 )3 OH

PbHAsO4

Rb3 (AsO4 )
Re3 As7
ReAsO4
Sn3 (AsO4 )2
Sr3 (AsO4 )2
Ti3 (AsO4 )2

298.15
298.15
298.15
298.15
298.15
298.15

298.15
298.15
298.15
298.15
298.15
298.15

298.15

Phase Temperature
(K)

Chemical species

Table C.1 (continued)

324.60

1181.6
1286.2
2166.9
1780.2

1669.0
95.395
771.57
1785.8
3317.1
2617.3

1553.1
1580.01
1579.3
2616.25
2659
805.66
1547.0
88.624
678.39
1564.6
3094.4
2547.3

267.06
336.81
170.00
303.93
312.1
339.4

172

1064.1

837.34

Entropy (Si ) (J
mol1 K1 )

Enthalpy (Hi )
(kJ mol1 )

Gibbs free
energy (Gi )
(kJ mol1 )

175.28
248.64
121.37
259.1
257.6
264.5

258.00

Heat Capacity
(Cpi ) (J
mol1 K1 )

Naumov, Ryzhenko
and Khodakovsky
(1974)
Wagman et al. (1982)
Wagman et al. (1982)
Wagman et al. (1982)
Barin (1995)
Davis et al. (1996)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Davis et al. (1996)
Lee and Nriagu
(2007)
Lee and Nriagu
(2007)
Barin (1995)
Barin (1995)
Barin (1995)
Barin (1995)
Barin (1995)
Barin (1995)

Reference

490
Arsenic

xls 298.15
xls 298.15
xls 298.15

ZnAs2
Zn3 As2
Zn3 As2

298.15
298.15
298.15
298.15
298.15
298.15

xls
xls
xls
xls
xls
xls

TlAsO4
YAsO4
Zn3 (AsO4 )2
Zn3 (AsO4 )2
Zn3 (AsO4 )2
Zn3 (AsO4 )2 2.5H2 O
(legrandite)

125.46

885.81
1416.8
1895.91
1895
1915.6
2611
299.74
160.54

281.92

168.04

948.56
1515.1

2134.7

41.8
133.89
32.2

125.23

145.69
120.75

255.28

Barin (1995)
Barin (1995)
Davis et al. (1996)
Wagman et al. (1982)
Barin (1995)
Naumov, Ryzhenko
and Khodakovsky
(1974)
Wagman et al. (1982)
Barin (1995)
Wagman et al. (1982)

Arsenic Thermodynamic Data

491

492

Arsenic

References
Allison, J.D., Brown, D.S. and Novo-Gradac, K.J. (1991) MINTEQA2/PRODEFA2: A Geochemical Assessment Model
for Environmental Systems: Version 3.0 Users Manual, U.S. Environmental Protection Agency, Washington, DC.
Barin, I. (1995) Thermochemical Data of Pure Substances: Parts 1 and II , 3rd edn. Weinheim, VCH Verlagsgesellschaft,
1885 pp.
Bothe, J.V. Jr. and Brown, P.W. (1999) The stabilities of calcium arsenates at 23 1 C. Journal of Hazardous
Materials, 69(2), 197207.
Castro, S.H. and Baltierra, L. (2005) Study of the surface properties of enargite as a function of pH. International
Journal of Mineral Processing, 77(2), 10415.
Davis, A., Ruby, M.V., Bloom, M. et al. (1996) Mineralogic constraints on the bioavailability of arsenic in
smelter-impacted soils. Environmental Science and Technology, 30(2), 39299.
Dove, P.M. and Rimstidt, J.D. (1985) The solubility and stability of scorodite, FeAsO4 .2H2 O. American Mineralogist ,
70(78), 83844.
Drever, J.I. (1997) The Geochemistry of Natural Waters: Surface and Groundwater Environments, Upper Saddle River,
NJ, Prentice Hall, 436 pp.
Eby, G.N. (2004) Principles of Environmental Geochemistry, Brooks/Cole-Thomson Learning, Pacific Grove, CA,
514 pp.
Faure, G. (1998) Principles and Applications of Geochemistry, 2nd edn. Prentice Hall, Upper Saddle River, NJ,
600 pp.
Helz, G.R., Tossell, J.A., Charnock, J.M. et al. (1995) Oligomerization in As(III) sulfide solutions: theoretical constraints and spectroscopic evidence. Geochimica et Cosmochimica Acta, 59(22), 4591604.
Kantar, C. (2002) Solution and flotation chemistry of enargite. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 210(1), 2331.
Krause, E. and Ettel, V.A. (1988) Solubility and stability of scorodite, FeAsO4 .2H2 O: new data and further discussion.
American Mineralogist , 73(78), 85054.
Krauskopf, K.B. and Bird, D.K. (1995) Introduction to Geochemistry, 3rd edn. McGraw-Hill, Boston.
Langmuir, D. (1997) Aqueous Environmental Geochemistry, Upper Saddle River, NJ, Prentice Hall, 600 pp.
Lee, J.S. and Nriagu, J.O. (2007) Stability constants for metal arsenates. Environmental Chemistry, 4(2), 12333.
Lide, D.R. (ed) (2007) CRC Handbook of Chemistry and Physics, 88th edn. CRC Press, Boca Raton, FL.
Matschullat, J. (2000) Arsenic in the geosphere A review. Science of the Total Environment , 249(13), 297312.
Naumov, G.B., Ryzhenko, B.N. and Khodakovsky, I.L. (1974) Handbook of Thermodynamic Data, (English translation). PB 226 722, Report No. USGS-WRD-74-001, U.S. Geological Survey, Menlo Park California, National
Technical Information Service, Springfield, Virginia.
Nordstrom, D.K. and Archer, D.G. (2003) Arsenic thermodynamic data and environmental geochemistry, in Arsenic
in Ground Water, (eds A.H. Welch and K.G. Stollenwerk), Kluwer Academic Publishers, Boston, pp. 125.
OHare, P.A.G. (1993) Calorimetric measurements of the specific energies of reaction of arsenic and of selenium
with fluorine. Standard molar enthalpies of formation f H o m at the temperature 2.98.15 K of AsF5 , SeF6 , As2 Se3 ,
As4 S4 , and As2 S3 . Thermodynamic properties of AsF5 and SeF6 in the ideal-gas state. Critical assessment of f H o m
(AsF3 , l)), and the dissociation enthalpies of As-F bonds. Journal of Chemical Thermodynamics, 25, 391402.
OHare, P.A.G., Lewis, B.M., Susman, S. and Volin, K.J. (1990) Standard molar enthalpies of formation and transition at the temperature 298.15 K and other thermodynamic properties of the crystalline and vitreous forms of
arsenic sesquiselenide (As2 S3 ). Dissociation enthalpies of As-Se bonds. Journal of Chemical Thermodynamics, 22,
1191206.
Pankratov, A.N. and Uchaeva, I.M. (2000) A semiempirical quantum chemical testing of thermodynamic and molecular
properties of arsenic compounds. Journal of Molecular Structure (Theochem), 498, 24754.
Parkhurst, D.L. and Appelo, C.A.J. (1999) Users Guide to PHREEQC (Version 2): A Computer Program for Speciation, Batch-reaction, One-dimensional transport, and Inverse Geochemical Calculations. U.S. Geological Survey
Water-Resources Investigations Report 99-4259, 312 pp.

Arsenic Thermodynamic Data

493

Perfetti, E., Pokrovski, G.S., Ballerat-Busserolles, K. et al. (2008) Densities and heat capacities of aqueous arsenious and arsenic acid solutions to 350 C and 300 bar, and revised thermodynamic properties of As(OH)3 o (aq),
AsO(OH)3 o (aq) and iron sulfarsenide minerals. Geochimica et Cosmochimica Acta, 72(3), 71331.
Pokrovski, G., Gout, R., Schott, J. et al. (1996) Thermodynamic properties and stoichiometry of As(III) hydroxide
complexes at hydrothermal conditions. Geochimica et Cosmochimica Acta, 60(5), 73749.
Pokrovski, G.S., Kara, S. and Roux, J. (2002) Stability and solubility of arsenopyrite, FeAsS, in crustal fluids. Geochimica et Cosmochimica Acta, 66(13), 236178.
Robie, R.A., Hemingway, B.S. and Fisher, J.R. (1979) Thermodynamic Properties of Minerals and Related Substances
at 298.15 K and 1 Bar (105 Pascals) Pressure and at Higher Temperatures, Reprinted with corrections. Geological
Survey Bulletin 1452, United States Printing Office, Washington, DC, 456 pp.
Ryu, J-H., Gao, S., Dahlgren, R.A. and Zierenberg, R.A. (2002) Arsenic distribution, speciation and solubility in
shallow groundwater of Owens Dry Lake, California. Geochimica et Cosmochimica Acta, 66(17), 298194.
Seal, R.R. II, Robie, R.A., Hemingway, B.S. and Evans, H.T. Jr (1996) Heat capacity and entropy at the temperatures
5 K to 720 K and thermal expansion from the temperatures 298 K to 573 K of synthetic enargite (Cu3 AsS4 ).
Journal of Chemical Thermodynamics, 28(4), 40512.
Wagman, D.D., Evans, W.H., Parker, V.B. et al. (1982) The NBS tables of chemical thermodynamic properties:
selected values for inorganic and C1 and C2 organic substances in SI units. Journal of Physical and Chemical
Reference Data, 11(2), 1392.
Zhu, Y., Zhang, X., Xie, Q. et al. (2005) Solubility and stability of barium arsenate and barium hydrogen arsenate at
25 C. Journal of Hazardous Materials, 120(1-3), 3744.
Zhu, Y.N., Zhang, X.H., Xie, Q.L. et al. (2006) Solubility and stability of calcium arsenates at 25 C. Water, Air, and
Soil Pollution, 169(14), 22138.