APPENDIX

с
REFERENCE TABLES

TABLE C.I Selected Standard Electrode Potentials

in Aqueous Solutions at 25°C in V vs. NHE a

Reaction Potential, V
+
Ag + e «± Ag 0.7991
AgBr + e *± Ag + Br~ 0.0711
AgCl + e +± Ag + СГ 0.2223
Agl + e ?± Ag + I~ -0.1522
A g 2 O + H 2 O + 2e +± 2Ag + 2OH" 0.342
Al 3 + + 3 e ^ A l -1.676
Au + + e <=* Au 1.83
Au 3 + + 2e^±Au + 1.36
p-benzoquinone + 2H + + 2e *± hydroquinone 0.6992
Br2(aq) + 2e<± 2Br~ 1.0874
Ca 2 + + 2e ?± Ca -2.84
Cd 2 + + 2e ?± Cd -0.4025
Cd 2 + + 2e ?± Cd(Hg) -0.3515
Ce 4 + + ^ ^ ± C e 3 + 1.72
Cl2(g) + 2e<± 2СГ 1.3583
HC10 + H + + e ?± |C1 2 + H 2 O 1.630
C o 2 + + 2^ ?± Co -0.277
Со3+ + ^ ^ ± С о 2 + 1.92
C r 2 + + 2^ ^± Cr -0.90
Cr 3 + + ^ ^ ± C r 2 + -0.424
Cr 2 O^" + 14H+ + 6e <=> 2Cr 3 + + 7H2O 1.36
Cu + + e «± Cu 0.520
Cu 2 + + 2CN" + e ?± Cu(CN)^ 1.12
Cu 2 + + в ^ Cu + 0.159
Cu 2 + + 2^ «± Cu 0.340
Cu 2 + + 2^ «± Cu(Hg) 0.345
Eu 3 + + ^ ^ E u 2 + -0.35
1/2F2 + H + + e <± HF 3.053
F e 2 + + 2^ ?± Fe -0.44
Fe3++e^Fe2+ 0.771
Fe(CN)^" + e <=t Fe(CN)^" 0.3610

(continued)

808
TABLE C.I (continued)

Reaction Potential, V
+
2H + 2e «± H 2 0.0000
2H 2 O 4- 2e <± H 2 4- 2OH~ -0.828
+
H 2 O 2 4- 2H + 2e <± 2H 2 O 1.763
2+ 2+
2Hg + 2e +± Hg 2 0.9110
+
Hg^ + 2e<^2Hg 0.7960
Hg 2 Cl 2 + 2e <± 2Hg + 2СГ 0.26816
Hg 2 Cl 2 + 2<? «± 2Hg + 2СГ (sat'd. KCl) 0.2415
HgO + H 2 O+ 2e <± Hg 4- 2OH~ 0.0977
Hg 2 SO 4 + 2e <=* 2Hg + SO2;" 0.613
I 2 + 2e *± 21" 0.5355
I3- + 2*«±3I~ 0.536
K + 4- e *± К -2.925
Li + + <? ^± Li -3.045
Mg 2 + 4- 2e z± Mg -2.356
M n 2 + + 2e ?± Mn -1.18
M n 3 + 4- e <=* M n 2 + 1.5
MnO 2 + 4H + 4- 2e *± M n 2 + + 2H 2 O 1.23
МПО4 + 8H + 4- 5e +± M n 2 + + 4H 2 O 1.51
Na + 4- e <± Na -2.714
N i 2 + + 2e <± Ni -0.257
Ni(OH)2 + 2e «± Ni + 2OH" -0.72
O 2 4- 2H + + 2^ ?± H 2 O 2 0.695
O 2 + 4H + + 4^ ?± 2H 2 O 1.229
O 2 + 2H 2 O + 4^ ?± 4OH~ 0.401
O 3 + 2H + + 2^ <=^ O 2 4- H 2 O 2.075
P b 2 + + 2e ?± Pb -0.1251
P b 2 + + 2e ?± Pb(Hg) -0.1205
PbO 2 + 4H + + 2^ ^ P b 2 + + 2H 2 O 1.468
PbO 2 4- SOl~ 4- 4H + 4- 2e <± PbSO 4 + 2H 2 O 1.698
PbSO 4 4- 2e <± Pb + S O ^ -0.3505
P d 2 + + 2e «± Pd 0.915
Pt 2 + + 2e ?± Pt 1.188
PtCl|" + 2e ?=> Pt 4- 4СГ 0.758
PtClg" + 2^ i=± PtCl^" + 2СГ 0.726
Ru(NH 3 )^ + ^ ^ R u ( N H 3 ) i + 0.10
S + 2^ <± S2~ -0.447
Sn 2 + 4- 2^ <± Sn -0.1375
Sn 4 + 4- 2^ *± Sn 2 + 0.15
Tl + + г ^ TI -0.3363
Tl + + g +± Tl(Hg) -0.3338
T l 3 + + 2^ <^ Tl + 1.25
3+
u + з^^и -1.66
U4+ + ^ ^ U 3 + -0.52
UOj + 4H + 4- ^ ?± U 4 + 4- 2H 2 O 0.273
UO^ + 4- ^ ?± U O j 0.163

(continued)
810 • Appendix C. Reference Tables

TABLE C.I (continued)

Reaction Potential, V

V 2 + + 2e<±W -1.13
v 3+ + e±±V2+ -0.255
vo 2 + + 2H + + e ^±V 3 + + H2O 0.337
voj -t- 2H + + e <^ V O 2 + H- H 2 O 1.00
Zn 2+ H - 2e ^± Zn -0.7626
ZnO 2 - + 2H2O + 2^^±Zn + 4OH" -1.285
a
The data in this table are mainly taken from A. J. Bard, J. Jordan, and
R. Parsons, Eds., "Standard Potentials in Aqueous Solutions," Marcel
Dekker, New York, 1985 (prepared under the auspices of the
Electrochemistry and Electroanalytical Chemistry Commissions of
IUPAC). Other sources of standard potentials and thermodynamic data
include: (1) A. J. Bard and H. Lund, Eds., "The Encyclopedia of the
Electrochemistry of the Elements," Marcel Dekker, New York,
1973-1986. (2) G. Milazzo and S. Caroli, "Tables of Standard
Electrode Potentials," Wiley-Interscience, New York, 1977. The data
here are referred to the NHE based on a 1-atm standard state for H2.
See the footnote in Section 2.1.5 concerning the recent change in
standard state.

Table C.2 Selected Formal Potentials in

Aqueous Solution at 25°C in V vs. NHEa

Reaction Conditions Potential, V

Cu(II) + e *± Cu 1MNH 3 + 1 M N H^ 0.01

lMKBr 0.52
Ce(IV) + e ±± Ce(III) IMHNO3 1.61
1MHC1 1.28
IMHCIO4 1.70
1MH 2 SO 4 1.44
Fe(III) + e ±± Fe(II) 1MHC1 0.70
10MHC1 0.53
IMHCIO4 0.735
1MH 2 SO 4 0.68
2MH3PO4 0.46
Fe(CN)^" + e ±± Fe(CNf)^" 0.1MHC1 0.56
1MHC1 0.71
1MHC1O 4 0.72
Sn(IV) + 2e *± Sn(II) 1MHC1 0.14
a
The data in this table are taken mainly from G. Chariot, "Oxidation-
Reduction Potentials," Pergamon, London, 1958. Additional values are found
in J. J. Lingane, "Electroanalytical Chemistry," Interscience, New York,
1958, and L. Meites, Ed., "Handbook of Analytical Chemistry," McGraw-
Hill, New York, 1963.
 Reference Tables 811

a
TABLE C.3 Estimated Standard Potentials in Aprotic Solvents, in V vs. aq SCE ^

Substance Reaction Conditions6 Potential, V

Anthracene (An) An + e *± An
7
DMF,0.1MTBAI -1.92
7
An + e *± An "
2
DMF,0.1MTBAI -2.5
An • + e *± An MeCN,0.1MTBAP + 1.3

Azobenzene (AB) AB + e «± AB
7
DMF,0.1MTBAP -1.36
Ph—N=N—Ph
7
AB + e^± AB "
2
DMF,0.1MTBAP -2.0
7
AB + e <=± AB MeCN,0.1MTEAP -1.40
-1.40
7
AB + e ?± AB PC0.1MTBAP
7
Benzophenone (BP) BP + e «± BP MeCN,0.1MTBAP -1.88
0 BP + e <± BP 7 THF,0.1MTBAP -2.06
BP + e ?± BP 7
PhCPhII BP 7 + ^ ?± B P 2 "
NH 3 ,0.1MKI
NH 3 ,0.1MKI
-123d
-U6d
1,4 Benzoquinone (BQ) BQ + ^ ^± BQ 7 MeCN,0.1MTEAP -0.54
/=\ BQ 7 + e ?± BQ 2 " MeCN, 0.1MTEAP -1.4

Ferrocene (Cp2Fe) Cp 2 Fe + + ^ i=± Cp 2 Fe MeCN,0.2MLiClO4 +0.31

Nitrobenzene (NB) NB + e «± NB 7 MeCN, 0.1 MTEAP -1.15
Ph—NO 2 NB + e ?± NB 7 DMF,0.1MNaClO4 -1.01
NB + e ?± NB 7 NH 3 ,0.1MKI -0.42^
NB 7 + e ?± N B 2 " NH 3 ,0.1MKI -\2A\d
Oxygen O 2 + e ?± O 2 7 DMF,0.2MTBAP -0.87
O 2 + € ?± O 2
T
MeCN, 0.2 M ТВ АР -0.82
O2 + e<± O2T DMSO,0.1MTBAP -0.73
+
Ru(bpy)§ (RuLf) RuL^+ + ^ <=* RuL^+ MeCN,0.1MTBABF4 + 1.32
у—\ /—\ \ RuL^+ + e <^ RuL3+ MeCN, O.IMTBABF4 -1.30

bpv=<oWq)
\_N N-/ /
RuLj + g ?± RuL^
RuL^ + e ?± RuL^"
MeCN,0.1MTBABF4
MeCN,0.1MTBABF4
-1.49
-1.73
Tetracyanoquino- TCNQ + ^ ?± TCNQ7 MeCN, 0.1 MLiC10 4 +0.13
dimethane (TCNQ)
TCNQ 7 + e <± TCNQ 2 " MeCN, 0.1 M LiClO4 -0.29

N,N,N',N'- TMPD • + e <=± TMPD DMF, 0.1 M ТВ АР +0.21

Tetramethyl-p-
phenylenediamine
(TMPD)

•NMe9

Tetrathiafulvalene + e ^± TTF MeCN, 0.1 M TEAP +0.30

(TTF)
T T F 2 + + e ^± TTF^ MeCN, 0.1 M TEAP +0.66

{continued)
812 • Appendix C. Reference Tables

TABLE C.3 Estimated Standard Potentials in Aprotic Solvents, in V vs. aq SCEa'*

Substance Reaction Conditions6' Potential, V

1
Thianthrene (TH) TH ^ + e <^ T H MeCN, 0.1 M ТВABF 4 +1.23
T H 2 + + e ^±TH* MeCN,0.1MTBABF 4 +1.74

CoJL JjOJ TH* + e <:±TH

TH2+ + e
SO 2 ,0.1MTBAP
SO 2 ,0.1MTBAP
+0.30 e
+0.88 e

Tri-TV-p-tolylamine TPTA + + e ±± TPTA THF,0.2MTBAP +0.98

(TPTA)

fl
See footnote in Table C.I.
^Problems arise in reporting potentials in nonaqueous solvents. The practice of using an aqueous SCE as a
reference electrode introduces an unknown and sometimes irreproducible liquid junction potential. Sometimes
reference electrodes made up in the solvent of interest (e.g., Ag/AgClO4) or QREs are employed. Results here
are reported vs. an aqueous SCE unless noted otherwise. While there has not yet been an adopted convention for
reporting potentials in nonaqueous solvents, a frequent practice is to reference these to the potential of a
particular reversible couple in the same solvent. This couple (sometimes called the "reference redox system") is
usually chosen on the basis of the extrathermodynamic assumption that the redox potential of this system is
only slightly affected by the solvent system. Suggested reference redox systems include ferrocene/ferrocenium,
Rb/Rb+, Fe(bpy)3+/Fe(bpy)3+ (bpy = 2,2'-bipyridine), and aromatic hydrocarbon/radical cation. For further
information concerning these problems, the following references can be consulted: ( 1 ) 0 . Popovych, Crit. Rev.
Anal. Chem., 1, 73 (1970); (2) D. Bauer and M. Breant, Electroanal. Chem., 8, 282 (1975); (3) A. J. Parker,
Electrochim. Ada, 21, 671 (1976).
c
See Standard Abbreviations.
vs. Ag/Ag+ (0.01 M) in NH 3 at -50°C.
d

e
vs. Ag/AgNO3 (sat'd) in SO 2 at -40°C.