=

o
z
ELECTROCHEMICAL
ut
o. DATA
o.

Table A.4 Standard Reduction Potentials at 25oC.

Main group elernents:

Half-Cell Reaction EON

2IJ+ + 2 e' -+ Hz(g) 0.0000

Li+ + e- -+ Li(s) -.3.045
Na+ + e- -+ Na(s) -2.714
K+ + e- -+ K(s) -2.9?5
Rb+ + e- -+ Rb(s) -2.9?5
Cs++ e- -+ Cs(s) -2.92,3
Be2++ 2 e- -+ Be(s) -r.97
Mg2+* 2 e- -+ Mg(s) -2.ffi6
Ca2++ 2 e- --+ Ca(s) -2.U
Ba2++ 2 e- -r Ba(s) -2.92
Al3+ + 3 e- -r Al(s) -L.67
COz(g)+ 2}l+ + 2 e' -+ CO(g)+ HzO -o.106
COzG)+2H+ +2e- '+ HCOOH -o.199
2COzG)+2H+ +2e' -+ HzCzOn 4.475
Pb2++ 2 e- -+ Pb(s) -o.12'1
PbOz(s)+ 4 H+ + 2 e' -+ Pb2++ 2H2O 1.468
NO3-+ 3 H+ + 2 e- -+ HNOz +H2O 0.9{
NO3-+4 H+ + 3 e- -+ NO(g)+ 2H2O 0.96
NO3-+ 10 H+ + 8 e- -+ NH4+ + 3 HzO 0.875
PO(OH)g+ 2 H+ + 2 e' --s HPO(OH)z+ H2O 4.276
HPO(OH)z+ 2 H+ + 2 e- --t H2PO(OH)+HzO 4.499

438
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8LV'I OzH 9 + (Dzrg F -a 0I + +H ZI + -eorg a
6!8'r OzH+-eorg e -aZ++HZ+ -torg
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9LT'T OzH+zon e -a++HZ+-eO13
I8I'I OzH + zotCtt <- .a Z+ +H8 + -8OI3
I(E'I OaH + -8OICe- -a Z + +HZ + -IOIC
w'z -JZ e -az+(a)zg
tr'0 (be;gzg <- -az+ +H z +(s)s
80'0 zegzsZ"- -aZ+-z9O?S
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0?'0 OaH +-zeozs e -a? + +1g1Z+(be)agg6
9Gv- O?HZ+ -r9gzg ? -aZ+ +Hi + -z7OSZ
?6'r -11;10
Z+ -z8OS<- -a Z,+ OaH + -z7OS
96'T zrOSZ ? -aZ+-z8OzS
69r'r O?HZ <- -aZ+ +HZ+zOzH
flL'0 OUH+.OH t- -a + +H +zOzH
9@'0 76z9 <- -aZ++H7+1312c
g?tO- zOH e -a++H+(3)zO
9ZZ't (t)8Hsv e -a I + +H I + (s)sv
0Fz;o OzH I +(s)sv e -a I + +HB + e(HO)sV
099'0 OaH + e(HO)sV e- -a Z,+ +HZ + e(HO)OsV
III'O_ 8Hd <- -og++Hg+(s)d
tfr'v OzH I + (s)d e -a I + +H I + z(HO)OdH
Nofl uorpEau llac-JIBH
68r B1BO lBJrruar{corlJalg
440 Appendix

Table A.4 Standard Reduction Potentials at 25oC (continued)

Main group elements:

Half-Cell Rpaction EON
2 HOI + 2 H+ + 2 e- --+I2(s)+ 2HzO 1.4
Iz(s)+ 2 e' -+ 2I' 05355
I g - + 2 e -- r 3 I ' 0.536
Idaq) + 2 e' -+ 2I' 0.@1

Tronsition and post-tronsition elcmcnt s:

Half-Cell Reaction EON
VOz++2H++e-+ VO2++HzO 1.m0
VO2+ + 2H+ + e- -+ V3+ + HZO 0.337
V3++e- + V2* 4.255
',12*+2e- + V(s) -1.13
Cr2O72-+ 14 H+ + 6 e- -r 2 Cr3++7 1;120 L38
Cr3+ + e- --r Cr2* 4.421
Cr2++ 2 e- -r Cds) -0.90
MnOa- + e- --) MnO42- 0.56
MnOa- + 8 H+ + 5 e- -+ Mn2+ + 4H2O 1.51
MnOz(s)+ 4 H+ + 2 e' -+ Mn2+ + 2HzO r.z3
Mn3+ + e- -r Mn2+ 1.5
Mn2++2e- + Mn(s) -1.18
Fe3++e- + Fd+ 0.nt
Fe(phen)3++ e- -+ Fe(phen)z+ 1.13
Fe(CN)o3-+ e' -r Fe(CN)oa 0.361
Fe(CN)oa- +2e- -+ Fe(s)+6CN- -1.16
Fe2++ 2e--+ Fe(s) 4.4
Co3*+ e- -+ Co2* L.y2
Co(NH3;63+ + e- -) Co(NH3)62+ 0.058
Co(Phen)g3+ + e- --) Co(phen)g2+ 0.327
Co(C2Oa;33- + e- -+ Co(C2Oa;3a- 0.57
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00'0- eHNI + (s)nC+ -aZ+ +zt(8IIII)nC
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r6r'0 - I C + ( s ) n ce - a + ( s ) p n c
69r'0 +nc e -a++znc
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Z
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442 . Appendix 3

Table A5 BiochemicalReduction Potentials

Half-Cell Reaction E',lV

Reduction of a carboryl gttup to an ald.ehydc:
1,3-diphosphoglycerate+ 2 e- -{.216
-+ 3-phosphoglyceraldehyde+ HPOa2-
acetyl-CoA + 2 H+ + 2 e- -+ acetaldehyde+ coenzymeA 4.4L2
oxalate+3H+ +2e- + glyoxalate 4.462
gluconate+3H+ +2e- -+ glucose 4.47
acetate+3H+ +2e- --+acetaldehyde -o.598
Reduction of acarbonyl group to an alcohol:
dehydroascorbicacid + H+ + 2 e- -+ ascorbate 0.077
glyoxylate+2}J+ +2e' -+ glycolate -o.090
hydroxlpymvate + 2H+ + 2 e- -+ glycerate -o.158
oxaloacetate+ 2 H+ + 2 e- -+ malate -o.166
pynrvate + 2 H+ + 2 e' -+ lactate -{.190
acetaldehyde+2H++2e' -+ ethanol -o.197
acetoacetate+2}J+ 2 e- --+ p-hydrorybutyrate -{.349
Carborylation:
pyrrrvate + COz(g)+ H+ + 2 e- -+ malate -o.330
cr-ketoglutarate+ COzG)+ H+ + 2 e- -+ iso-citrate -o.363
succinate+ COzk) + 2H+ + 2 e' -+ a-ketoglutarate+ H2O -o.673
acetate+ COz(g)+ 2H+ + 2 e' -+ pymvate + HzO -{.699
Rcd.uction of o carbonyl group with formation of an omino group:
oxaloacetate+ NH4+ + 2 H+ + 2 e- -+ aspartate + HzO -o.107
pynrvate + NH4+ + 2H+ + 2 e' -> alanine + H2O -{.132
a-ketoglutarate + NH4+ + 2H+ + 2 e' --+ glutamate + HzO -{.133
Red.uction of a earbon-earbon double bond:
crotonyl-CoA+ 2 H+ + 2 e- --+butyryl-CoA 0.187
fumarate+2Il+ +2e' -+ succinate 0.031
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444 Appendix 3

Table A.6 SomeFormal Reduction Potentials

E'lV
couple lMHCloa lMHcl lMHzsoa
Ae(I)/Ae(O) 0.792 0.n8 0.77
As(V)/As(III) 0.577 0.577
Ce(IV)/Ce(III) L.lO t28 L.4
Fe(III)/Fe(II) 0.732 0.700 0.68
Ae(I)/Ag(O) 0.792 0.nB 0.77
As(V)/As(III) 0.577 0.577
Ce(IV)/Ce(III) L.70 L.28 I.4
Fe(III)/Fe(II) 0.732 0.700 0.68
H(r)fi(O) -0.005 -0.005
Hg(II)/Hg(I) 0.907
Hg(I)lHg(0) 0.776 0.n4 0.674
Mn(IV)/Mn(II) 1.2+
Pb(rr)/Pb(0) {.14 4.n
Sn(IV)/Sn(II) 0.14
Sn(II)/Sn(0) -0.16

Data from E. H. Swift and E. A. Butler, Quantitatiue

Measurements and Chemical Equilibria, San Francisco:
Freeman.1972.

Table .d7 ReferenceElectrode Potentials

Electrode E"'/V (dEld?)/mV K-l

Calomel(0.1 M KCI) 0.336 -O.08
Calomel(1.0 M KCI) 0.213 4.29
Calomel (satd. KCI) 0.2M -0.67
Ag/AgCl (3.5 M KCI) 0.n5 -O.73
Ag/AgCl (satd. KCI) 0.199 -1.01
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446 Appendix 3

Table A.9 Solvent Properties

Liquid Vapor - Dielectric

Solvent Range/oC Pressureb Constant Viscosity
water 0 3.2 78.4 089
propylene carbonate (PC) 49to?/12 0.0 &.4 25
dimethylsulfoxide 19to 189 0.1 6.7 2.00
(DMSO)
N,N-dimethylformamide -60 to 153 0.5 36.7 0.80
(DMF)
acetonitrile -44tD82 11.8 37.5 0.34
nitromethane -29 to 101 4.9 35.9 0.61
methanol -98 to 65 L6.7 32.7 0.&
hexamethylphosphor- 7 to233 0.01 30.d 3.47d
amide (HMPA)
ethanol -ll4tn78 8.0 2/1.6 1.08
acetone -95 to 56 2+.2 n.7 0.30
dichloromethane -95 to 40 58.1 8.9 0.41
trifluoroacetic acid -L5tn72 14.4 8.6 0.86
tetrahydrofuran (TTIF) -108 to 66 26.3 7.6 0.46
1,2-dimethoxyethane -58 to 93 10.0 72 0.46
(glyme, DME)
acetic acid 17to 118 2.0 6.2d 1.13
p-dioxane 12to 101 4.9 22 L,2

a Data at 25"C from J. A. Riddick and W. B. Bunger, Organic Soluents,

3rd ed, New York: Wiley-Interscience,1970.
b Vapor pressurein units of kPa.
c Viscosity in units of 10-3kg m-15-1.
d 2ooc.
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