1400-AP3 9/8/99 4:40 PM Page 731

Appendix
Appendix 3

Appendix 3A
Solubility Products
Bromide (Br –) pKsp Ksp Cyanide (CN–) pKsp Ksp

CuBr 8.3 5 × 10–9 AgCN 15.66 2.2 × 10–16

AgBr 12.30 5.0 × 10–13 Zn(CN)2 (µ = 3.0 M) 15.5 3 × 10–16
Hg2Br2 22.25 5.6 × 10–23 Hg2(CN)2 39.3 5 × 10–40
HgBr2(µ = 0.5 M) 18.9 1.3 × 10–19
Ferrocyanide ([Fe(CN)64–]) pKsp Ksp
PbBr2(µ = 4.0 M) 5.68 2.1 × 10–6
Zn2[Fe(CN)6] 15.68 2.1 × 10–16
Carbonate (CO32–) pKsp Ksp
Cd2[Fe(CN)6] 17.38 4.2 × 10–18
MgCO3 7.46 3.5 × 10–8 Pb2[Fe(CN)6] 18.02 9.5 × 10–19
CaCO3 (calcite) 8.35 4.5 × 10–9
Fluoride (F–) pKsp Ksp
CaCO3 (aragonite) 8.22 6.0 × 10–9
SrCO3 9.03 9.3 × 10–10 MgF2 8.18 6.6 × 10–9
BaCO3 8.30 5.0 × 10–9 CaF2 10.41 3.9 × 10–11
MnCO3 9.30 5.0 × 10–10 SrF2 8.54 2.9 × 10–9
FeCO3 10.68 2.1 × 10–11 BaF2 5.76 1.7 × 10–6
CoCO3 9.98 1.0 × 10–10 PbF2 7.44 3.6 × 10–8
NiCO3 6.87 1.3 × 10–7
Ag2CO3 11.09 8.1 × 10–12
Hydroxide (OH–) pKsp Ksp
Hg2CO3 16.05 8.9 × 10–17 Mg(OH)2 11.15 7.1 × 10–12
ZnCO3 10.00 1.0 × 10–10 Ca(OH)2 5.19 6.5 × 10–6
CdCO3 13.74 1.8 × 10–14 ⋅
Ba(OH)2 8H2O 3.6 3 × 10–4
PbCO3 13.13 7.4 × 10–14 La(OH)3 20.7 2 × 10–21
Mn(OH)2 12.8 1.6 × 10–13
Chloride (Cl–) pKsp Ksp
Fe(OH)2 15.1 8 × 10–16
CuCl 6.73 1.9 × 10–7 Co(OH)2 14.9 1.3 × 10–15
AgCl 9.74 1.8 × 10–10 Ni(OH)2 15.2 6 × 10–16
Hg2Cl2 17.91 1.2 × 10–18 Cu(OH)2 19.32 4.8 × 10–20
PbCl2 4.78 1.7 × 10–5 Fe(OH)3 38.8 1.6 × 10–39
Co(OH)3 (T = 19 °C) 44.5 3 × 10–45
Chromate (CrO42–) pKsp Ksp
Ag2O (+H2O t2Ag+ + 2OH–) 15.42 3.8 × 10–16
BaCrO4 9.67 2.1 × 10–10 Cu2O (+ H2O t2Cu+ + 2OH–) 29.4 4 × 10–30
CuCrO4 5.44 3.6 × 10–6 Zn(OH)2 (amorphous) 15.52 3.0 × 10–16
Ag2CrO4 11.92 1.2 × 10–12 Cd(OH)2 (β) 14.35 4.5 × 10–15
Hg2CrO4 8.70 2.0 × 10–9 continued

731
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732 Modern Analytical Chemistry

Solubility Products—continued
Hydroxide (OH–) pKsp Ksp Sulfate (SO42–) pKsp Ksp

HgO (red) (+ H2O t Hg2+ + 2OH–) 25.44 3.6 × 10–26 CaSO4 4.62 2.4 × 10–5
SnO (+ H2O t
Sn + 2OH–)
2+ 26.2 6 × 10–27 SrSO4 6.50 3.2 × 10–7
PbO (yellow) (+ H2Ot Pb2+ + 2OH–) 15.1 8 × 10–16 BaSO4 9.96 1.1 × 10–10
Al(OH)3 (α) 33.5 3 × 10–34 Ag2SO4 4.83 1.5 × 10–5
Iodate (IO3–) pKsp Ksp Hg2SO4 6.13 7.4 × 10–7
PbSO4 7.79 1.6 × 10–8
Ca(IO3)2 6.15 7.1 × 10–7
Ba(IO3)2 8.81 1.5 × 10–9
AgIO3 7.51 3.1 × 10–8
Hg2(IO3)2 17.89 1.3 × 10–18 Sulfide (S2–) pKsp Ksp
Zn(IO3)2 5.41 3.9 × 10–6 MnS (green) 13.5 3 × 10–14
Cd(IO3)2 7.64 2.3 × 10–8 FeS 18.1 8 × 10–19
Pb(IO3)2 12.61 2.5 × 10–13 CoS (β) 25.6 3 × 10–26
Iodide (I–) pKsp Ksp NiS (γ) 26.6 3 × 10–27
CuS 36.1 8 × 10–37
AgI 16.08 8.3 × 10–17
Cu2S 48.5 3 × 10–49
Hg2I2 28.33 4.7 × 10–29
Ag2S 50.1 8 × 10–51
HgI2 (µ = 0.5 M) 27.95 1.1 × 10–28
ZnS (α) 24.7 2 × 10–25
PbI2 8.10 7.9 × 10–9
CdS 27.0 1 × 10–27
Oxalate (C2O42–) pKsp Ksp Hg2S (red) 53.3 5 × 10–54
CaC2O4 (µ = 0.1 M, T = 20 °C) 7.9 1.3 × 10–8 PbS 27.5 3 × 10–28
BaC2O4 (µ = 0.1 M, T = 20 °C) 6.0 1 × 10–6
SrC2O4 (µ = 0.1 M, T = 20 °C) 6.4 4 × 10–7
Phosphate (PO43–) pKsp Ksp Thiocyanate (SCN–) pKsp Ksp

⋅
Fe3(PO4)2 8H2O 36.0 1 × 10–36 CuSCN (µ = 5.0 M) 13.40 4.0 × 10–14
⋅
Zn3(PO4)2 4H2O 35.3 5 × 10–36 AgSCN 11.97 1.1 × 10–12
Ag3PO4 17.55 2.8 × 10–18 Hg2(SCN)2 19.52 3.0 × 10–20
Pb3(PO4)2 (T = 38 °C) 43.53 3.0 × 10–44 Hg(SCN)2 (µ = 1.0 M) 19.56 2.8 × 10–20

Source: All values are from Martell, A. E.; Smith, R. M. Critical Stability Constants, Vol. 4. Plenum Press: New York, 1976. Unless otherwise stated, values
are for 25 °C and zero ionic strength.

Appendix 3B
Acid Dissociation Constants
Compound Conjugate Acid pKa Ka

acetic acid CH3COOH 4.757 1.75 × 10–5

adipic acid HOOC(CH2)4COOH 4.42 3.8 × 10–5
5.42 3.8 × 10–6
alanine COOH 2.348 (COOH) 4.49 × 10–3
9.867 (NH3) 1.36 × 10–10
CHCH3

NH3+
aminobenzene 4.601 2.51 × 10–5
NH3+
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Appendix 3 733

Compound Conjugate Acid pKa Ka

4-aminobenzene sulfonic acid 3.232 5.86 × 10–4

–O S NH3+
3

2-aminobenzoic acid COOH 2.08 (COOH) 8.3 × 10–3

4.96 (NH3) 1.1 × 10–5

NH3+

2-aminophenol OH 4.78 (NH3); (T = 20 °C) 1.7 × 10–5

9.97 (OH); (T = 20 °C) 1.05 × 10–10
NH3+

ammonia NH4+ 9.244 5.70 × 10–10

arginine COOH NH2+ 1.823 (COOH) 1.50 × 10–2

8.991 (NH3) 1.02 × 10–9
CHCH2CH2CH2NHC (12.48) (NH2) 3.3 × 10–13

NH3+ NH2

arsenic acid H3AsO4 2.24 5.8 × 10–3

6.96 1.1 × 10–7
11.50 3.2 × 10–12

asparagine COOH 2.14 (COOH); (µ = 0.1 M) 7.2 × 10–3

8.72 (NH3); (µ = 0.1 M) 1.9 × 10–9
CHCH2CNH2

NH3+ O

aspartic acid COOH 1.990 (α-COOH) 1.02 × 10–2

3.900 (β-COOH) 1.26 × 10–4
CHCH2COOH 10.002 (NH3) 9.95 × 10–11

NH3+

benzoic acid 4.202 6.28 × 10–5

COOH

benzylamine 9.35 4.5 × 10–10

CH2NH3+

boric acid H3BO3 9.236 5.81 × 10–10

(12.74); (T = 20 °C) 1.82 × 10–13
(13.80); (T = 20 °C) 1.58 × 10–14
carbonic acid H2CO3 6.352 4.45 × 10–7
10.329 4.69 × 10–11
catechol OH 9.40 4.0 × 10–10
12.8 1.6 × 10–13

OH

continued
1400-AP3 9/8/99 4:40 PM Page 734

734 Modern Analytical Chemistry

Acid Dissociation Constants—continued

Compound Conjugate Acid pKa Ka

chloroacetic acid ClCH2COOH 2.865 1.36 × 10–3

chromic acid H2CrO4 –0.2; (T = 20 °C) 1.6
6.51 3.1 × 10–7

citric acid COOH 3.128 (COOH) 7.45 × 10–4

4.761 (COOH) 1.73 × 10–5
HOOCH2C C CH2COOH 6.396 (COOH) 4.02 × 10–7

OH

cupferron NO 4.16; (µ = 0.1 M) 6.9 × 10–5

OH
cysteine COOH (1.71) (COOH) 1.9 × 10–2
8.36 (SH) 4.4 × 10–9
CHCH2SH 10.77 (NH3) 1.7 × 10–11

NH3+

dichloroacetic acid Cl2CHCOOH 1.30 5.0 × 10–2

diethylamine (CH3CH2)2NH2+ 10.933 1.17 × 10–11
dimethylamine (CH3)2NH2+ 10.774 1.68 × 10–11

dimethylgloxime HON NOH 10.66 2.2 × 10–11

12.0 1 × 10–12

H3C CH3

ethylamine CH3CH2NH3+ 10.636 2.31 × 10–11

ethylenediamine +H NCH CH NH +
3 2 2 3 6.848 1.42 × 10–7
9.928 1.18 × 10–10

ethylenediaminetetraacetic acid (EDTA) HOOCH2C CH2COOH 0.0 (COOH); (µ = 1.0 M) 1.0

1.5 (COOH); (µ = 0.1 M) 3.2 × 10–2
+HNCH +
2CH2NH 2.0 (COOH); (µ = 0.1 M) 1.0 × 10–2
2.68 (COOH); (µ = 0.1 M) 2.1 × 10–3
HOOCH2C CH2COOH
6.11 (NH); (µ = 0.1 M) 7.8 × 10–7
10.17 (NH); (µ = 0.1 M) 6.8 × 10–11

formic acid HCOOH 3.745 1.80 × 10–4

fumaric acid COOH 3.053 8.85 × 10–4

4.494 3.21 × 10–5

HOOC

glutamic acid COOH 2.23 (α-COOH) 5.9 × 10–3

4.42 (λ-COOH) 3.8 × 10–5
CHCH2CH2COOH 9.95 (NH3) 1.12 × 10–10

NH3+
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Appendix 3 735

Compound Conjugate Acid pKa Ka

glutamine COOH O 2.17 (COOH); (µ = 0.1 M) 6.8 × 10–3

9.01 (NH3); (µ = 0.1 M) 9.8 × 10–10
CHCH2CH2CNH2

NH3+

glycine +H NCH COOH

3 2 2.350 (COOH) 4.47 × 10–3
9.778 (NH3) 1.67 × 10–10
glycolic acid HOCH2COOH 3.831 (COOH) 1.48 × 10–4

histidine H 1.7 (COOH); (µ = 0.1 M) 2 × 10–2

COOH N 6.02 (NH); (µ = 0.1 M) 9.5 × 10–7
9.08 (NH3); (µ = 0.1 M) 8.3 × 10–10
CHCH2
N
NH3+ H+

hydrogen cyanide HCN 9.21 6.2 × 10–10

hydrogen fluoride HF 3.17 6.8 × 10–4
hydrogen peroxide H2O2 11.65 2.2 × 10–12
hydrogen sulfide H2S 7.02 9.5 × 10–8
13.9 1.3 × 10–14
hydrogen thiocyanate HSCN 0.9 1.3 × 10–1

8-hydroxyquinoline 4.91 (NH) 1.23 × 10–5

9.81 (OH) 1.55 × 10–10

N
H+
OH

hydroxylamine HONH3+ 5.96 1.1 × 10–6

hypobromous HOBr 8.63 2.3 × 10–9
hypochlorous HOCl 7.53 3.0 × 10–8
hypoiodous HOI 10.64 2.3 × 10–11
iodic acid HIO3 0.77 1.7 × 10–1

isoleucine COOH 2.319 (COOH) 4.80 × 10–3

9.754 (NH3) 1.76 × 10–10
CHCH(CH3)CH2CH3

NH3+

leucine COOH 2.329 (COOH) 4.69 × 10–3

9.747 (NH3) 1.79 × 10–10
CHCH2CH(CH3)2

NH3+

lysine COOH 2.04 (COOH); (µ = 0.1 M) 9.1 × 10–3

9.08 (α-NH3); (µ = 0.1 M) 8.3 × 10–10
CHCH2CH2CH2CH2NH3+ 10.69 (ε-NH3);(µ = 0.1 M) 2.0 × 10–11

NH3+
continued
1400-AP3 9/8/99 4:40 PM Page 736

736 Modern Analytical Chemistry

Acid Dissociation Constants—continued

Compound Conjugate Acid pKa Ka

maleic acid HOOC COOH 1.910 1.23 × 10–2

6.332 4.66 × 10–7

malic acid OH 3.459 (COOH) 3.48 × 10–4

5.097 (COOH) 8.00 × 10–6
HOOCH2C CHCOOH

malonic acid HOOCCH2COOH 2.847 1.42 × 10–3

5.696 2.01 × 10–6

methionine COOH 2.20 (COOH); (µ = 0.1 M) 6.3 × 10–3

9.05 (NH3); (µ = 0.1 M) 8.9 × 10–10
CHCH2CH2SCH3

NH3+

methylamine CH3NH3+ 10.64 2.3 × 10–11

2-methylaniline CH3 4.447 3.57 × 10–5

NH3+

4-methylaniline 5.084 8.24 × 10–6

H3C NH3+

2-methylphenol CH3 10.28 5.2 × 10–11

OH

4-methylphenol 10.26 5.5 × 10–11

H3C OH

nitrilotriacetic acid CH2COOH 1.1 (COOH); (T = 20 °C , µ = 1.0 M) 8 × 10–2

1.650 (COOH); (T = 20 °C) 2.24 × 10–2
+HN CH2COOH 2.940 (COOH); (T = 20 °C) 1.15 × 10–3
10.334 (NH3); (T = 20 °C) 4.63 × 10–11
CH2COOH

2-nitrobenzoic acid COOH 2.179 6.62 × 10–3

NO2

3-nitrobenzoic acid COOH 3.449 3.56 × 10–4

NO2
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Appendix 3 737

Compound Conjugate Acid pKa Ka

4-nitrobenzoic acid 3.442 3.61 × 10–4

O2N COOH

2-nitrophenol OH 7.21 6.2 × 10–8

NO2

3-nitrophenol OH 8.39 4.1 × 10–9

NO2

4-nitrophenol 7.15 7.1 × 10–8

O2N OH

nitrous acid HNO2 3.15 7.1 × 10–4

oxalic acid H2C2O4 1.252 5.60 × 10–2
4.266 5.42 × 10–5
1,10-phenanthroline 4.86 1.38 × 10–5

NH+ N
phenol 9.98 1.05 × 10–10

OH

phenylalanine COOH 2.20 (COOH) 6.3 × 10–3

9.31 (NH3) 4.9 × 10–10
CHCH2C6H5

NH3+

phosphoric acid H3PO4 2.148 7.11 × 10–3

7.199 6.32 × 10–8
12.35 4.5 × 10–13
phthalic acid COOH 2.950 1.12 × 10–3
5.408 3.91 × 10–6

COOH

piperidine 11.123 7.53 × 10–12

NH2+

proline 1.952 (COOH) 1.12 × 10–2

COOH 10.640 (NH) 2.29 × 10–11

N
H2+
continued
1400-AP3 9/8/99 4:40 PM Page 738

738 Modern Analytical Chemistry

Acid Dissociation Constants—continued

Compound Conjugate Acid pKa Ka

propanoic acid CH3CH2COOH 4.874 1.34 × 10–5

propylamine CH3CH2CH2NH3+ 10.566 2.72 × 10–11

pyridine 5.229 5.90 × 10–6

NH+

resorcinol OH 9.30 5.0 × 10–10

11.06 8.7 × 10–12

OH

salicylic acid COOH 2.97 (COOH) 1.07 × 10–3

13.74 (OH) 1.8 × 10–14

OH

serine COOH 2.187 (COOH) 6.50 × 10–3

9.209 (NH3) 6.18 × 10–10
CHCH2OH

NH3+

succinic acid HOOCCH2CH2COOH 4.207 6.21 × 10–5

5.636 2.31 × 10–6
sulfuric acid H2SO4 strong strong
1.99 1.0 × 10–2
sulfurous acid H2SO3 1.91 1.2 × 10–2
7.18 6.6 × 10–8

D-tartaric acid OH 3.036 (COOH) 9.20 × 10–4

4.366 (COOH) 4.31 × 10–5
HOOC CH CH COOH

OH

threonine COOH 2.088 (COOH) 8.17 × 10–3

9.100 (NH3) 7.94 × 10–10
CHCHOHCH3

NH3+

thiosulfuric acid H2S2O3 0.6 3 × 10–1

1.6 3 × 10–2
trichloroacetic acid Cl3CCOOH 0.66; (µ = 0.1 M) 2.2 × 10–1
triethanolamine (HOCH2CH2)3NH+ 7.762 1.73 × 10–8
triethylamine (CH3CH2)3NH+ 10.715 1.93 × 10–11
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Appendix 3 739

Compound Conjugate Acid pKa Ka

trimethylamine (CH3)3NH+ 9.800 1.58 × 10–10

tris(hydroxymethyl)-
aminomethane
(TRIS or THAM) (HOCH2)3CNH3+ 8.075 8.41 × 10–9

tryptophan COOH 2.35 (COOH); (µ = 0.1 M) 4.5 × 10–3

9.33 (NH3); (µ = 0.1 M) 4.7 × 10–10
CHCH2

NH3+
N
H

tyrosine COOH 2.17 (COOH); (µ = 0.1 M) 6.8 × 10–3

9.19 (NH3) 6.5 × 10–10
CHCH2 OH 10.47 (OH) 3.4 × 10–11

NH3+

valine COOH 2.286 (COOH) 5.18 × 10–3

9.718 (OH) 1.91 × 10–10
CHCH(CH3)2

NH3+

Source: All values are from Martell, A. E.; Smith, R. M. Critical Stability Constants, Vol. 1–4. Plenum Press: New York, 1976. Unless otherwise stated, values
are for 25 °C and zero ionic strength. Values in parentheses are considered less reliable.

Appendix 3C
Metal–Ligand Formation Constants
Acetate
CH3COO– log K1 log K2 log K3 log K4 log K5 log K6

Mg2+ 1.27
Ca2+ 1.18
Ba2+ 1.07
Mn2+ 1.40
Fe2+ 1.40
Co2+ 1.46
Ni2+ 1.43
Cu2+ 2.22 1.41
Ag+ 0.73 –0.09
Zn2+ 1.57
Cd2+ 1.93 1.22 –0.89
Pb2+ 2.68 1.40

continued
1400-AP3 9/8/99 4:40 PM Page 740

740 Modern Analytical Chemistry

Metal–Ligand Formation Constants—continued

Ammonia
NH3 log K1 log K2 log K3 log K4 log K5 log K6

Ag+ 3.31 3.91

Co2+ (T = 20 °C) 1.99 1.51 0.93 0.64 0.06 –0.74
Ni2+ 2.72 2.17 1.66 1.12 0.67 –0.03
Cu2+ 4.04 3.43 2.80 1.48
Zn2+ 2.21 2.29 2.36 2.03
Cd2+ 2.55 2.01 1.34 0.84

Chloride
Cl– log K1 log K2 log K3 log K4 log K5 log K6

Cu2+ 0.40
Fe3+ 1.48 0.65
Ag+ (µ = 5.0 M) 3.70 1.92 0.78 –0.3
Zn2+ 0.43 0.18 –0.11 –0.3
Cd2+ 1.98 1.62 –0.2 –0.7
Pb2+ 1.59 0.21 –0.1 –0.3

Cyanide
CN– log K1 log K2 log K3 log K4 log K5 log K6

Fe2+ 35.4 (β6)

Fe3+ 43.6 (β6)
Ag+ 20.48 (β2) 0.92
Zn2+ 11.07 (β2) 4.98 3.57
Cd2+ 6.01 5.11 4.53 2.27
Hg2+ 17.00 15.75 3.56 2.66
Ni2+ 30.22 (β4)

Ethylenediamine
H2NCH2CH2NH2 log K1 log K2 log K3 log K4 log K5 log K6

Ni2+ 7.38 6.18 4.11

Cu2+ 10.48 9.07
Ag+ (T = 20 °C , µ = 0.1 M) 4.70 3.00
Zn2+ 5.66 4.98 3.25
Cd2+ 5.41 4.50 2.78

EDTA
–OOCH
2C CH2COO–

NCH2CH2N

–OOCH
2C CH2COO– log K1 log K2 log K3 log K4 log K5 log K6

Mg2+ (T = 20 °C, µ = 0.1 M) 8.79

Ca2+ (T = 20 °C, µ = 0.1 M) 10.69
Ba2+ (T = 20 °C, µ = 0.1 M) 7.86
Bi3+ (T = 20 °C, µ = 0.1 M) 27.8
Co2+ (T = 20 °C, µ = 0.1 M) 16.31
Ni2+ (T = 20 °C, µ = 0.1 M) 18.62
Cu2+ (T = 20 °C, µ = 0.1 M) 18.80
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Appendix 3 741

EDTA
–OOCH
2C CH2COO–

NCH2CH2N

–
OOCH2C CH2COO– log K1 log K2 log K3 log K4 log K5 log K6

Cr3+ (T = 20 °C, µ = 0.1 M) (23.4)

Fe3+ (T = 20 °C, µ = 0.1 M) 25.1
Ag+ (T = 20 °C, µ = 0.1 M) 7.32
Zn2+ (T = 20 °C, µ = 0.1 M) 16.50
Cd2+ (T = 20 °C, µ = 0.1 M) 16.46
Hg2+ (T = 20 °C, µ = 0.1 M) 21.7
Pb2+ (T = 20 °C, µ = 0.1 M) 18.04
Al3+ (T = 20 °C, µ = 0.1 M) 16.3

Fluoride
F– log K1 log K2 log K3 log K4 log K5 log K6

Al3+ (µ = 0.5 M) 6.11 5.01 3.88 3.0 1.4 0.4

Hydroxide
OH– log K1 log K2 log K3 log K4 log K5 log K6

Al3+ 9.01 (9.69) (8.3) 6.0

Co2+ 4.3 4.1 1.3 0.5
Fe2+ 4.5 (2.9) 2.6 –0.4
Fe3+ 11.81 10.5 12.1
Ni2+ 4.1 3.9 3
Pb2+ 6.3 4.6 3.0
Zn2+ 5.0 (6.1) 2.5 (1.2)

Iodide
I– log K1 log K2 log K3 log K4 log K5 log K6

Ag+ (T = 18 °C) 6.58 (5.12) (1.4)

Cd2+ 2.28 1.64 1.08 1.0
Pb2+ 1.92 1.28 0.7 0.6

Nitriloacetate
CH2COO–

N CH2COO–

CH2COO– log K1 log K2 log K3 logK4 log K5 log K6

Mg2+ (T = 20 °C, µ = 0.1 M) 5.41

Ca2+ (T = 20 °C, µ = 0.1 M) 6.41
Ba2+ (T = 20 °C, µ = 0.1 M) 4.82
Mn2+ (T = 20 °C, µ = 0.1 M) 7.44
Fe2+ (T = 20 °C, µ = 0.1 M) 8.33
Co2+ (T = 20 °C, µ = 0.1 M) 10.38
Ni2+ (T = 20 °C, µ = 0.1 M) 11.53
Cu2+ (T = 20 °C, µ = 0.1 M) 12.96
Fe3+ (T = 20 °C, µ = 0.1 M) 15.9
Zn2+ (T = 20 °C, µ = 0.1 M) 10.67
Cd2+ (T = 20 °C, µ = 0.1 M) 9.83
Pb2+ (T = 20 °C, µ = 0.1 M) 11.39 continued
1400-AP3 9/8/99 4:40 PM Page 742

742 Modern Analytical Chemistry

Metal–Ligand Formation Constants—continued

Oxalate
C2O42– log K1 log K2 log K3 logK4 log K5 log K6

Ca2+ (µ = 1 M) 1.66 1.03

Fe2+ (µ = 1 M) 3.05 2.10
Co2+ 4.72 2.28
Ni2+ 5.16
Cu2+ 6.23 4.04
Fe3+ (µ = 0.5 M) 7.53 6.11 4.85
Zn2+ 4.87 2.78

1,10-Phenanthroline

NH+ N log K1 log K2 log K3 logK4 log K5 log K6

Fe2+ 20.7 (β3)

Mn2+ (µ = 0.1 M) 4.0 3.3 3.0
Co2+ (µ = 0.1 M) 7.08 6.64 6.08
Ni2+ (µ = 0.1 M) 8.6 8.1 7.6
Fe3+ 13.8 (β3)
Ag+ (µ = 0.1 M) 5.02 7.04
Zn2+ 6.2 (5.9) (5.2)

Thiosulfate
S2O32– log K1 log K2 log K3 logK4 log K5 log K6

Ag+ (T = 20 °C) 8.82 4.85 0.53

Thiocyanate
SCN– log K1 log K2 log K3 logK4 log K5 log K6

Mn2+ 1.23
Fe2+ 1.31
Co2+ 1.72
Ni2+ 1.76
Cu2+ 2.33
Fe3+ 3.02
Ag+ 4.8 3.43 1.27 0.2
Zn2+ 1.33 0.58 0.09 –0.4
Cd2+ 1.89 0.89 0.02 –0.5
Hg2+ 17.26 (β2) 2.71 1.83

Source: All values are from Martell, A. E.; Smith, R. M. Critical Stability Constants, Vol. 1–4, Plenum Press: New York, 1976. Unless otherwise stated, values
are for 25 °C and zero ionic strength. Values in parentheses are considered less reliable.
1400-AP3 9/8/99 4:40 PM Page 743

Appendix 3 743

Appendix 3D
Standard Reduction Potentialsa
E° E°′ E° E°′
Aluminum (V) (V) Bromine (V) (V)

Al3+ + 3e– t
Al(s) –1.676 Br2 + 2e– t 2Br– 1.087
Al(OH)4– + 3e– t Al(s) + 4OH– –2.310 HOBr + H+ + 2e– t Br + H O –
2 1.341
AlF63– + 3e– t
Al(s) + 6F– –2.07 HOBr + H+ + e– t ⁄ Br (l) + H O
1
2 2 2 1.604
BrO– + H2O + 2e– t Br + 2OH – – 0.76 1 M NaOH
BrO3– + 6H+ + 5e– t ⁄ Br (l) + 3H O
1
2 2 2 1.5

Antimony
E°
(V)
E°′
(V)
BrO3– + 6H+ + 6e– t Br + 3H O –
2 1.478

E° E°′
Sb(s) + 3H+ + 3e– t
SbH3(g) –0.510
Cadmium (V) (V)
Sb2O5(s) + 6H+ + 4e– t
2SbO+ + 3H2O 0.605
SbO+ + 2H+ + 3e– t
Sb(s) + H2O 0.212 Cd2+ + 2e– tCd(s) –0.4030
Cd(CN)42– + 2e– tCd(s) + 4CN– –0.943
2+
Cd(NH3)4 + 2e – tCd(s) + 4NH3 –0.622
E° E°′
Arsenic (V) (V) E° E°′
Calcium (V) (V)
As(s) + 3H+ + 3e– t AsH (g) –0.225
H3AsO4 + 2H+ + 2e–
3
t HAsO + 2H O
2 2 0.560 Ca2+ + 2e– t Ca(s) –2.84
HAsO2 + 3H+ + 3e– t As(s) + 2H O 2 0.240 E° E°′
Carbon (V) (V)

E° E°′ CO2(g) + 2H+ + 2e– t CO(g) + H O 2 –0.106

Barium (V) (V) CO2(g) + 2H+ + 2e– t HCO H 2 –0.20

Ba2+ 2e– t 2CO2(g) + 2H+ + 2e– tHCO 2 2 4 –0.481

+ Ba(s)
BaO(s) + 2H+ + 2e– t Ba(s) + H O2
–2.92
2.365
HCHO + 2H+ + 2e– t CH OH 3 0.2323

E° E°′
Cerium (V) (V)
E° E°′
Beryllium (V) (V) Ce3+ + 3e– t Ce(s) –2.336

Be2+ + 2e– t Be(s) –1.99

Ce4+ + e– t Ce 3+ 1.72 1.70 1 M HClO4
1.44 1 M H2SO4
1.61 1 M HNO3
E° E°′ 1.28 1 M HCl
Bismuth (V) (V) E° E°′
Bi3++ 3e– t Bi(s) 0.317 Chlorine (V) (V)
BiCl4– + 3e– t Bi(s) + 4Cl – 0.199 Cl2(g) + 2e– t2Cl– 1.396
ClO– + H2O + e– t 1
⁄2Cl2(g) + 2OH– 0.421 1 M NaOH

E° E°′
ClO– + H2O + 2e– t Cl– + 2OH– 0.890 1 M NaOH
Boron (V) (V) HClO2 + 2H+ + 2e– t HOCl + H2O 1.64
ClO3– + 2H+ + e– t ClO2(g) + H2O 1.175
B(OH)3 + 3H+ + 3e– t
B(s) + 3H2O –0.890 ClO3– + 3H+ + 2e– t HClO2 + H2O 1.181
B(OH)4– + 3e– t
B(s) + 4OH– –1.811 ClO4– + 2H+ + 2e– t ClO3– + H2O 1.201

continued
1400-AP3 9/8/99 4:40 PM Page 744

744 Modern Analytical Chemistry

Standard Reduction Potentialsa—continued

E° E°′ E° E°′
Chromium (V) (V) Iron (V) (V)

Cr3+ + e– tCr2+ –0.424 Fe2+ + 2e– t Fe(s) –0.44

Cr2+ + 2e– tCr(s) –0.90 Fe3+ + 3e– t Fe(s) –0.037
Cr2O72– + 14H+ + 6e– t 2Cr3+ + 7H2O 1.36 Fe3+ + e– t Fe 2+ 0.771 0.70 1 M HCl
CrO42– + 4H2O + 3e– t Cr(OH)4– + 4OH– –0.13 1 M NaOH 0.767 1 M HClO4
0.746 1 M HNO3
E° E°′
Cobalt (V) (V) 0.68 1 M H2SO4
0.44 0.3 M H3PO4
Co2+ + 2e– t Co(s) –0.277 Fe(CN)63– + e– t
Fe(CN)64– 0.356 0.71 1 M HCl
Co3+ + e– tCo2+ 1.92 Fe(phen)33+ + e– t
Fe(phen)32+ 1.147
Co(NH3)63+ + e– t
Co(NH3)62+ 0.1 Fe(CN)63– + e– t
Fe(CN)64– 0.356
Co(OH)3(s) + e– t
Co(OH)2(s) + OH– 0.17
Co(OH)2(s) + 2e – t
Co(s) + 2OH– –0.746
Ianthanum
E°
(V)
E°′
(V)
E° E°′
Copper (V) (V) La3+ + 3e– t La(s) –2.38

Cu+ + e– t Cu(s) 0.520

Lead
E°
(V)
E°′
(V)
Cu2+ + e– t Cu+ 0.159
Cu2+ + 2e– t Cu(s) 0.3419 Pb2+ + 2e– t Pb(s) –0.126
Cu2+ + I– + e– t
CuI(s) 0.86 PbO2(s) + 4H+ + 2e– t
Pb2+ + 2H2O 1.46
Cu2+ + Cl– + e– t
CuCl(s) 0.559 PbO2(s) + SO42– + 4H+ + 2e– t
PbSO4(s) + 2H2O 1.690

E° E°′
PbSO4(s)+ 2e– t
Pb(s) + SO42– –0.356
Fluorine (V) (V) E° E°′
Lithium (V) (V)
F2(g) + 2H+ + 2e– t 2HF 3.053
F2(g) + 2e– t 2F– 2.87 Li+ + e– t Li(s) –3.040

E° E°′ E° E°′
Gallium (V) (V) Magnesium (V) (V)

Ga3+ + 3e– t Ga(s) –0.529 Mg2+ + 2e– t

Mg(s) –2.356

E° E°′
Mg(OH)2(s) + 2e– t
Mg(s) + 2OH– –2.687
Gold (V) (V) E° E°′
Manganese (V) (V)
Au+ + e– t Au(s) 1.83
Au3+ + 2e– t Au+ 1.36 Mn2+ + 2e– t
Mn(s) –1.17
Au3+ + 3e– t Au(s) 1.52 M3+ + e– t
Mn2+ 1.5
AuCl4– + 3e– t Au(s) + 4Cl– 1.002 MnO2(s) + 4H+ + 2e– t
Mn2+ + 2H2O 1.23

E° E°′
MnO4– + 4H+ + 3e– t
MnO2(s) + 2H2O 1.70
Hydrogen (V) (V) MnO4– + 8H+ + 5e– t
Mn2+ + 4H2O 1.51
MnO4– + 2H2O + 3e– t
MnO2(s) + 4OH– 0.60
2H+ + 2e– t H (g) 2 0.00000
H2O + e– t ⁄ H (g) + OH
1
2 2
– –0.828
Mercury
E°
(V)
E°′
(V)
E° E°′
Iodine (V) (V) Hg2+ + 2e– t Hg(l) 0.8535
2Hg2+ + 2e– t Hg22+ 0.911
I2(s) + 2e– t 2I– 0.5355 2+
Hg2 + 2e – t 2Hg(l) 0.7960
–
I3 + 2e – t 3I– 0.536 Hg2Cl2(s) + 2e– t
2Hg(l) + 2Cl– 0.2682
HIO + H + 2e–
+ t
I– + H2O 0.985 +
HgO(s) + 2H + 2e – tHg(l) + H2O 0.926
–
IO3 + 6H + 5e+ – 1
t
⁄2I2(s) + 3H2O 1.195 Hg2Br2(s) + 2e– t
2Hg(l) + 2Br – 0.1392
–
IO3 + 3H2O + 6e – tI– + 6OH– 0.257 Hg2I2(s) + 2e– t
2Hg(l) + 2I– –0.0405
1400-AP3 9/8/99 4:40 PM Page 745

Appendix 3 745

E° E°′ E° E°′
Molybdenum (V) (V) Selenium (V) (V)

Mo3+ + 3e– t
Mo(s) –0.2 Se(s) + 2e– tSe2– –0.670 1 M NaOH
MoO2(s) + 4H+ + 4e– t Mo(s) + 2H O 2 –0.152 Se(s) + 2H+ + 2e– t
H2Se(g) –0.115
MoO42– + 4H2O + 6e– t Mo(s) + 8OH – –0.913 H2SeO3 + 4H+ + 4e– t
Se(s) + 3H2O 0.74

E° E°′
SeO43– + 4H+ + e– t
H2SeO3 + H2O 1.151

Nickel (V) (V) E° E°′

Ni2+ + 2e– t
Ni(s) –0.257 Silicon (V) (V)
Ni(OH)2(s) + 2e– t
Ni(s) + 2OH– –0.72 SiF62– + 4e– t
Si(s) + 6F– –1.37
Ni(NH3)62+ + 2e– t
Ni(s) + 6NH3 –0.49 SiO2(s) + 4H + 4e–
+ tSi(s) + 2H2O –0.909

E° E°′
SiO2(s) + 8H+ + 8e– t
SiH4(g) + 2H2O –0.516
Nitrogen (V) (V)
E° E°′
N2(g) + 5H+ + 4e– t
N2H5+ –0.23 Silver (V) (V)
N2O(g) + 2H+ + 2e– t
N2(g) + H2O 1.77 Ag+ + e– t
Ag(s) 0.7996
2NO(g) + 2H+ + 2e– t
N2O(g) + H2O 1.59 AgBr(s) + e– tAg(s) + Br– 0.071
HNO2 + H+ + e– t
NO(g) + H2O 0.996
Ag2C2O4(s) + 2e– t 2Ag(s) + C2O42– 0.47
2HNO2 + 4H+ + 4e– t
N2O(g) + 3H2O 1.297 AgCl(s) + e– tAg(s) + Cl– 0.2223
NO3– + 3H+ + 2e– t
HNO2 + H2O 0.94
AgI(s) + e– tAg(s) + I– –0.152
E° E°′ Ag2S(s) + 2e– t2Ag(s) + S2– –0.71
Oxygen (V) (V) Ag(NH3)2+ + e– t Ag(s) + 2NH3 0.373

O2(g) + 2H+ + 2e– tHO 2 2 0.695 E° E°′

O2(g) + 4H+ + 4e– t 2H O 2 1.229 Sodium (V) (V)
H2O2 + 2H+ + 2e– t 2H O2 1.763
Na+ + e– t Na(s)
O2(g) + 2H2O + 4e– t 4OH – 0.401
–2.713

O3(g) + 2H+ + 2e– t O (g) + H O

2 2 2.07 E° E°′
Strontium (V) (V)
E° E°′
Phosphorus (V) (V) Sr2+ + 2e– t Sr(s) –2.89

P(s, white) +3H+

+ 3e–t PH (g) 3 –0.063
E° E°′
H3PO3 + 2H+ + 2e– t H PO + H O
3 2 2 –0.499 Sulfur (V) (V)
H3PO4 + 2H+ + 2e– t H PO + H O
3 3 2 –0.276
S(s) + 2e– tS2– –0.407
E° E°′ S(s) + 2H+ + 2e– t
H2S 0.144
Platinum (V) (V) S2O62– + 4H+ + 2e– t
2H2SO3 0.569
Pt2++ 2e– t
Pt(s) 1.188 S2O82– + 2e– t2SO42– 1.96
PtCl42– + 2e– t
Pt(s) + 4Cl– 0.758 S4O62– + 2e– t2S2O32– 0.080
2SO32– + 2H2O + 2e– t
S2O42– + 4OH– –1.13
E° E°′ 2SO32– + 3H2O + 4e– t
S2O32– + 6OH– –0.576 1 M NaOH
Potassium (V) (V)
2SO42– + 4H+ + 2e– t
S2O62– + 2H2O –0.25
K+ + e– t K(s) –2.924 SO42– + H2O + 2e– t
SO32– + 2OH– –0.936
SO42– + 4H+ + 2e– t
H2SO3 + H2O +0.172
E° E°′
Ruthenium (V) (V) E° E°′
Ru3++ e– t Ru2+ 0.249
Thallium (V) (V)

RuO2(s) + 4H+ + 4e– t

Ru(s) + 2H2O 0.68 Tl3+ + 2e– t Tl + 1.25 1 M HClO4
Ru(NH3)63+ + e– t
Ru(NH3)62+ 0.10 0.77 1 M HCL
Ru(CN)63– + e– t
Ru(CN)64– 0.86 Tl3 + 3e– t Tl(s) 0.742

continued
1400-AP3 9/8/99 4:40 PM Page 746

746 Modern Analytical Chemistry

Standard Reduction Potentialsa—continued

E° E°′ E° E°′
Tin (V) (V) Uranium (V) (V)

Sn2+ + 2e– t Sn(s) –0.19 1 M HCl U3+ + 3e– t

U(s) –1.66
Sn4+ + 2e– t Sn 2+ 0.154 0.139 1 M HCl U4+ +e– U3+ t –0.52
UO2+ + 4H+ + e– t
U4+ + 2H2O 0.27
UO22+ + e– t
UO2+ 0.16
UO22+ + 4H+ + 2e– tU4+ + 2H2O 0.327

E° E°′ E° E°′
Titanium (V) (V) Vanadium (V) (V)

Ti2+ + 2e– t Ti(s) –1.63 V2+ + 2e– t

V(s) –1.13
Ti3+ + e– t Ti 2+ –0.37 V3+ + e– V2+ t –0.255
VO2+ + 2H+ + e– t V +H O
3+
2 0.337
VO2+ + 2H+ + e– t VO + H O
2+
2 1.000

E° E°′ E° E°′
Tungsten (V) (V) Zinc (V) (V)

WO2(s) + 4H+ + 4e– t W(s) + 2H O

2 –0.119 Zn2+ + 2e– t
Zn(s) –0.7618
WO3(s) + 6H+ + 6e– t W(s) + 3H O
2 –0.090 Zn(OH)42– + 2e– t
Zn(s) + 4OH– –1.285
Zn(NH3)42+ + 2e– t
Zn(s) + 4NH3 –1.04
Zn(CN)42– + 2e– t
Zn(s) + 4CN– –1.34

Source: Values are compiled from the following sources: Bard, A. J.; Parsons, R.; Jordon, J., eds. Standard Potentials in Aqueous Solutions. Dekker: New
York, 1985; Milazzo, G.; Caroli, S.; Sharma, V. K. Tables of Standard Electrode Potentials. Wiley: London, 1978; Swift, E. H.; Butler, E. A. Quantitative
Measurements and Chemical Equilibria. Freeman: New York, 1972.
aSolids, gases, and liquids are identified; all other species are aqueous. Reduction reactions in acidic solution are written using H+ instead of H O+.
3
Reactions may be rewritten by replacing H+ with H3O+ and adding one molecule of H2O to the opposite side of the reaction for each H+; thus

H3AsO4 + 2H+ + 2e– t HAsO 2 + 2H2O

becomes
H3AsO4 + 2H3O++ 2e– t HAsO 2 + 4H2O
Conditions for formal potentials (E°′) are listed next to the potential.