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Pure &Appl. Chem., Vol. 63, No. 12, pp. 1759-1779,1991. Printed in Great Britain. 0 1991 IUPAC
INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY
ANALYTICAL CHEMISTRY DIVISION COMMISSION ON ELECTROCHEMISTRY"
KINETIC PARAMETERS OF' THE ELECTRODE REACTION: 2 C1- @ C12 + 2e-
(Technical Report)
Prepared for publication by KOICHI TOKUDA' and KATSUMI NIK12
'Department of Electronic Chemistry, Graduate School at Nagatsuta, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 227, Japan
'Department of Physical Chemistry, Faculty of Engineering, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240, Japan
*Membership of the Commission during the period the report was prepared (1989-1991) was as follows:
Chairman: G. Gritzner (Austria); Secretary: G. S. Wilson (USA); Titular Members: D. Landolt (Switzerland); V. M. M. Lob0 (Portugal); W. Plieth (FRG); Margaretha Sluyters-Rehbach (Netherlands); K. Tokuda (Japan); Associate Members: C. P. Andrieux (France); Yu. A. Chizmadzhev (USSR); B. E. Conway (Canada); J. Koryta (Czechoslovakia); G. Kreysa (FRG); 0. A. Petrii (USSR); D. Pletcher (UK); M. J. Weaver (USA); National Representatives: A. J. Arvia (Argentina); T. Biegler (Australia); H. D. Hurwitz (Belgium); D. Pavlov (Bulgaria); G . Hortinyi (Hungary); S. K. Rangarajan (India); E. Gileadi (Israel); S. Trasatti (Italy); T. Watanabe (Japan); G. A. Wright (New Zealand); W. Paik (Republic of Korea); C. Gutierrez (Spain): D. Simonsson (Sweden); M. L. Berkem (Turkey); A. K. Covington (UK); D. Drazic (Yugoslavia).
Republication of this report is permitted without the need for formal IUPAC permission on condition that an acknowledgement, with full reference together with IUPAC copyright symbol (0 1991 IUPAC), is printed. Publication of a translation into another language is subject to the additional condition of prior approval from the relevant IUPAC National Adhering Organization.
Kinetic parameters of the electrode reaction: 2 CI-zC12 + 2e-
Abstract - Kinetic parameters of the electrode reaction, 2 C1- Z Clz + 2 e- , at various electrodes and in various electrolytes are compiled and tabulated.
INTRODUCTION
A large amount of data concerning the kinetic parameters characterizing the charge transfer process of a variety of electrode reactions have been published in the literature. A compi- lation of such data on charge transfer processes of metallic species was made by Tanaka and Tamamushi (ref. 1, 2 ) . In this document the compilation of the kinetic parameters of the electrode reaction, 2 C1-
C12 + 2 e-, at various electrodes and in various electrolytes is presented, covering up to the year 1989. The chlorine evolution reaction is one of the most important and interest- ing reactions in electrochemistry, both from the practical viewpoint of electrochemical technology and from the fundamental viewpoint of electrocatalysis. Detailed discussions of the mechanisms of this reaction can be found in the comprehensive reviews by Mussini and Faita (ref. 3 ) , by Novak, Tilak and Conway (ref. 4 ) and by Trasatti (ref. 5 ) . The data were extracted from the data bank at Electrochemical Data Center, Yokohama National University. The data are tabulated as much as possible in the form they are reported in the literature. However, for detailed information on a particular system, the original paper should be consulted because, as i s well-known, electrochemical kinetic parameters often depend not only on the electrode material but on the conditions of electrode preparation. General definitions and explanations of electrochemical kinetic parameters are given in ref. 2 and refs. 6-8 .
GENERAL REMARKS CONCERNING THE TABLE
1. Gencral arrangement and presentation of the parmeters: The following table summarizes the kinetic parameters of the electrode reaction at electrodes of various materials in var- ious electrolytes. atomic symbols.
2. Electrode: The first column presents the material and composition of the working electrode and the second gives the preparation and/or electrode treatment. When the same procedure is used for different electrode materials, a symbol *Pn (n=1,2, . . . I is used in place of a full description of the procedure. The place where the full description is given is indicated in the last column.
Electrode materials are arranged in alphabetical order according to their
3. Medim: The third column gives the composition of the solution and, when available, the practical pressure of chlorine gas above the solution. are aqueous. Note that M is used as the unit of concentration instead of mol/dm3. Pressure is given in atm if it i s used in the original literature. (1 M = 1 mol/dm3 and 1 atm =
1.01325~ lo5 Pa).
Un,less otherwise noted, the solutions
4. Temperature: This column gives the temperature in "C . 1760
Kinetic parameters of the electrode reaction: 2 Cl- = Cl, + 2e- 1761
5. Transfer coefficient and/or Tafel slope: The anodic ( a and cathodic ( a transfer coefficients are given in the fifth and sixth columns respectively. The slopes of Tafel plots for an anodic and cathodic branches (b, and b,) are often quoted in place of the trans- fer coefficients.
6. Rate constant or exchange current density: The symbol ko represents the standard heteroge- neous rate constant (also named conditional electrode reaction rate constant). More fre- quently than ko the values of the exchange current density 1. are reported. Finally, where available, the potential dependent rate constant, Lox, at a specified poten- tial is also tabulated. Numerical values in this column are often given in the form aEb rather than a x l o b ; e.g., 2.OE-3 should be read as 2 . 0 ~
7. Energy of activation: The eighth column gives the energy of activation for the indicated condition.
8. Method: The method for measuring the electrochemical kinetic parameters is shown in this column using the abbreviation given in the LIST OF SYMBOLS AND ABBREVIATIONS.
9. Note: Numbers in this column indicate footnotes. The symbol *F indicates that the parame- ter(s) were taken or calculated from a figure in the original literature.
10. Stoichiometric nmbers and reaction orders: When these values are reported in the origi- nal literature, then are cited in the footnotes.
LIST OF SYMBOLS AND ABBREVIATIONS
Symbols 4 - b, anodic Tafel slope b- cathodic Tafel slope - E electrode potential - E,, equilibrium potential - F Faraday constant 1 current density 10 exchange current density - ko - k,, - n, - n,(Clz) anodic reaction order in Clz - n,(Cl-) anodic reaction order in C1- - nc(Clz) cathodic reaction order in Clz n,(Cl-) cathodic reaction order in C1- e(Clz) partial pressure of chlorine - R gas constant - T thermodynamic temperature a, anodic transfer coefficient e cathodic transfer coefficient 7 overpotential Y stoichiometric number
surface area of the electrode
conditional electrode reaction rate constant electrode reaction rate constant for oxidation number of charge transferred in the rate determining step
Abbreviations chp chronopotentiometry CP current-potential curve fi faradaic impedance method gs galvanostatic method gsdp galvanostatic double pulse method lsv linear sweep voltammetry pd potentiodynamic method PS potentiostatic method RDE rotating disk electrode SCE saturated calomel electrode SHE standard hydrogen electrode
Acknowledgement Compilation of kinetic parameters of electrode reactions, at present being continued at Electrochemical Data Center, Yokohama National University, is partly supported by Grant-in- Aid for Scientific Research from the Ministry of Education, Science and Culture, Japan.
TA
BL
E
1.
Ki
ne
ti
c
pa
ra
me
te
rs
o
f
th
e
re
ac
ti
on
-
2C1
=
Cl
z+
2e
Tran
sfer
co
effi
cien
t or
Ta
fel
slop
e Ra
te c
onst
ant
or e
xcha
nge
curr
ent
dens
ity
etho
d ef
er-
nce
lote
empe
ra-
ture
/"C
nerg
y ac
tiva
El
ect ro
de
Med
i um
Ma te
r i a
I Pr
epar
atio
n and/or
trea
tmen
t me
thod
an
od i c
ca
thod
ic
~~
ko=l
. 268
-3 cm/s
P 9
Ag p
late
d on
Pt
(A
=O. 63cm')
1.05
M HC
I t
IM &
SO
4
25
r .=O
. 69
n,=l)
r .=O
. 28
n,=l)
grap
hite
ia
tura
ted
NaCI
. )H
ca.
0. 5.
)(ClZ) =
lat
n
50
.= 12
0mV
at h
igh
cd)
.=4OmV
at lo
w cd)
.=-12OmV
ja=l
. 2E
-3 A
/cmZ
p-RD
E 10
1)
IDE
(A=O
. 95cm2).
:nbedded
in Tef
lon
slee
ve,
pree
lect
roly
- sis
at 5
0 mA/cm2
for
lh
RDE
(A=O
. 713cm2).
poli
shed
wit
h wa
ter-
proof A1203
pape
r and
fine
paper
!I%
ZnCl
z.
pH 3
. 29.
[C121=l. 17
g/dm3
25
' .= 12
4mV
.=-12OmV
.=-39. I
mV at
low
cd
ja=l
. ll
E-3
A/cm2
11
grap
hite
p-
RDE
IS
0
2
17%
ZnC
l2.
pH 3. 29.
[C121=l. 23
g/dm3
25
k=1.
16E-
2 cm/s at
E=31
0mV
vs.
SCE
k=6.
76E-
3 cm/s at
E=41
0mV
vs.
SCE
LM H
zS04
t
0.05
M HC
1 25
k"
=l. 74
E-3
cn/s
12
grap
hite
I
,=o.
45
z .=o
. 44
1.=2.
3 X
2RT/3F
rn 5 4 cn <
*P1
:p-g
s 13
gr
aphi
te
powder(lO-lSwt%)
and
bind
er w
ere
mixe
d.
comp
ress
ed in
to a
disk.
heat
ed
in air
at 24
OOC
for
30-4
0 nin. so
aked
in
1%
poly
styl
ene
soln
. in
benz
ene,
hea
ted
at
ca.
100°
C
(*P
I)
jM N
aC1.
:12
bubb
led
j~=2.
52E-
4 A/cm2
:p-g
s 14
3)
grap
hite
new
grap
hite
IM
NaCl
+ 1M
HC
1,=12'7mV
z a=
O. 4
6 25
14. 5
1,
=151
mV
z a=
o. 38
jo=
2. 35
E-4
A/cm2
30
1,=1
23mV
z
,=o.
49
j,=2.
46
8-4
A/cm2
E 1 ec
t rod
e Me
d i u
rn ‘e
mp. /“C
Tran
sfer
co
effi
cien
t Ra
te c
onst
ant
<ner
gy o
f ac
tiva
tion
Re
f.
Note
new
grap
hite
4M
NaC
l +
1M H
C1
io=2
. IO
E-4
A/cm
’ 14
gr
aphi
te
io=
2. 66
E-4
A/cnZ
a *
=O. 63
vitr
eous
ca
rbon
5M
NaC1. pH
ca.
P(Cl2)
? 95
Ib
”=iR
:h
i0=3
. OE
-4 A/
cm2
15
4)
vitr
eous
ca
rbon
5M
NaC
1. pH
ca.
P(Cl.2)
? i0=5.
OE-4
A/
cmZ
15
~
16
(cd
> 2
grap
hite
sp
ectr
osco
pica
lly
pu
re.
poro
sity
25%
fu
sed
LiCl
p(Cla)=l
atm
io=
l. 3E-
1 A/
cn2
5)
a .=1.
97
a .=2.04
a .=
2. 10
grap
hite
p
oro
us,
po
rosi
ty 3
0%
fuse
d Li
Cl
p(ClZ)=l
atm
io=
1. 9E
-1 A
/cm2
29. I
kJ/
mol
fo
r j,
16
~
17
io=
2. 4E
-2 A
/cm2
165
io=
2.
8E-2
A/
cm2
b,=95mV
a .=
2. 16
lOln
V
ba=1
02-
11 4m
V
llOm
V
pyre I y
t i,
grap
hi
a-di
re,
basa
l pl
ane,
en
caps
u-
late
d in
bor
on n
i-
trid
e, c
ircu
lar
and
plan
ar
(A=O
. 3cm‘)
AgC1
-NaC
1 m
e1 t
150
io=(l. 5
. 3. 0
-4.
0)
E-2
A/cm’
io=
l. 1E
O A/cm‘
pyro
lyti
t gr
aphi
b-
dire1
basa
l pl
ane.
en
caps
u-
late
d in
qua
rtz,
ni
trid
e. ci
rcul
ar a
nd
plan
ar
(A=O
. 3cm’)
AgC1
-NaC
I m
e1 t
150
io=(1. 7
-2.
0)E-
2 A/cm’
17
perp
endi
cula
r to
bas
- sl
pla
ne.
enca
psul
at-
:d in b
oron
nit
ride
. Jl
anar
and
cir
cula
r (A
=O. 3
cm’)
AgCl
-NaC
I me
lt
150
i0=(5. 0-
6. 0)E-2
A/cmZ
11
pyro
I y t
i i gr
aphi
c-
dire
i io
=l. 9E
O A/cm’
SPK gr
aphi
:n
caps
ulat
ed in b
oron
ii
trid
e. p
lana
r an
d :ircular.
poli
shed
on
3 di
amon
d wh
eel
(A=O. 3cm’)
AgC1
-NaC
I m
e1 t
750
17
io=l. 4
0E-1
A/cm2
b,=100.
108m
V
SPK gr
aphi
te
enca
psul
ated
in
quar
tz,
hemi
- sp
heri
cal.
(A=
O. 6cm')
AGKS
P gr
aphi
te
AGKS
PK
grap
hite
enca
psul
ated
in
bor
on
nitr
ide,
pla
nar
and
circ
ular
, po
lish
ed o
n a
diam
ond
whee
l.
(A=O
. 3cm2)
enca
psul
ated
in
qu
artz
, hem
isph
eric
al,
(A=O
. 6cm
2)
AUC gr
aphi
te
enca
psul
ated
in
bor
on
nitr
ide,
pla
nar
and
circ
ular
, po
lish
ed o
n a
diam
ond
whee
l (A
=O. 3cm2)
glas
sy c
arbo
n ro
d se
aled
in
a Py
rex
glas
s tu
be,
the
end
bein
g cu
t o
ff at
45'.
poli
shed
wit
h al
umin
a po
wder
sus
pens
ion
vitr
eous
ca
rbon
en
caps
ulat
ed in
bor
on
nitr
ide,
pla
nar
and
circ
ular
, po
lish
ed o
n a
diam
ond
whee
l (A
=O. 3cm2)
-
Ref. -
11
E 1 ec
t rod
e Me
d i u
rn 'emp. /"C
Tran
sfer
co
effi
cien
t Ra
te c
onst
ant
lner
gy o
f ac
tiva
tion
lethod
P-gs
Ag
Cl-N
aC1
melt
75
0 jO=(l.O-l.
2)E-1
A/cm2
sdp
jo=Z
. OE
O A/cm2
jo=
Z. 3E-1
A/cm2
jo=2
. 8E
-1 A
/cm2
Ag
Cl-N
aCl
melt
P-
gs
17
jo=
(5. 2-5. 6)EO
A/cm2
.sdp
P-gs
T
10
4mV
11
AgCl
-NaC
I me
lt
jo=(l. 0
-2.
0)E-1
A/cm2
I
AgC1
-NaC
I me
1 t
11
jn=l
. 80
E-1
A/cm2
j0=3. 85
EO A/cm'
P-gs
:sdp
NaCl
+ A
lC13
mel
t log [a (C 1
-)I =
-I. 1.
p(C12)=l
atm
jn=(8.
A/cm2 6
f0. 8)E-6
P-PS
18
AgC1
-NaC
l me
lt
jo=(l. 5
-2.
5)E-2
A/cm2
17
jo=(O. 7
6~0.
9)EO
A/cm
:sdp
NaCl
+ K
Cl m
elt
mass
rat
io)
(NaC
l:KC
l=3:
1 in
j0=6. 63
A/c
m2
j0=7. 15
A/cmZ
jo=1
. 92
A/cm
2
1 19
se
aled
in
quar
tz,
I Dolis
hed
end
vitr
eous
ca
rbon
I
NaCl
+ K
Cl +
AlC
13
melt
(N
aCl:
KCl=
3:1
in m
ass
rati
o)
(AlC
13 1
3 wt%)
j0=5. 37
A/c
m2
jo=5
. 87
A/cm
2 j0=6. 43
A/cmZ
j0=6
. 91
A/cm2
j0.4.
95 A/cmZ
j0=5. 38 A/cm'
j0=5. 98
A/c
nZ
j0=6. 40 A
/cm2
NaCl
+ K
C1 +
AlC
13
melt
(N
aCl:
KC1=
3:1
in m
ass
rati
o)
(AlC
13 1
9 wt%)
820
8 50
88
0
;eal
ed in
quar
tz,
lolished e
nd
.dia
mete
r 0.
15cm
)
NaCl
t KC
I t
AIC1
3 me
lt (N
aCl:
KC1=
3:1
in m
ass
rati
o)
(AlC
13 29
Wt%)
‘emp
. /“C
rr
ansf
er
coef
fici
ent
Rate
con
stan
t ne
rgy
of
acti
vati
on
Ref -
19
-
20
~
20
Note
I
Medi
um
Elec
trod
e lethod
..
vitr
eous
ca
rbon
82
0 85
0 88
0
i0=4. 3
9 A/
cm2
j0=4. 8
8 A/
cm2
j0=5
. 41 A
/cmZ
8 20
8 50
880
jo=4. 0
2 A/cm2
jo-4. 31 A
/cmZ
j0=4. 8
2 A/cm‘
NaCl
t KC
I t
A1C
I3
melt
(N
aCI:
KC1=
3:1
in m
ass
rati
o)
(AIC
13 3
6. 5 w
t%)
c030
4 on
Ti
25
a .=
O. 5
b.=40mV
j0=4. 8
E-3
A/cmZ
75+ 4)
kJ/n
ol
for
Cla
ev
olut
ion
at E
=l.l
V vs.
SCE
:p-p
s .h
erma
1 de
comp
osit
ion
if C
o(N
03)~
appl
ied
’ired at
260°C.
with
.o
Ti
plat
e (l
cm’)
.
IuO?
in
terl
ayer
between
Co3
04 a
nd T
i l~g(p(Clz)/atmt
=O.
0
log (p(Clz)/atmt
=-0.
6
25
a ,=O.
5 j0=4. 5E-3
A cm-’
25
a a
=O. 5
jO=l. 1E-3
A cm-’
25
a ,=
o. 5
j0=1.OE-3
A cm
-’
25
a a
=O. 5
j0=4
.8E-4
A cK2
1M N
aCl
t 0.
01M
H
CI
log (p(Cla)/atmt
=-1.
5
I1M
NaCl
t 0.
01M
HC1
25
a ,=
O. 5
tl n lu‘ +
6)
tF
tP2
2
25
a ,=O
. 5
jo=8. 9
E-4
A cm-’
:p-ps
Co3
04 o
n Ti
herm
al d
ecom
posi
tion
if
CO(N03)z
appl
ied
o Ti p
late
(1 cm‘).
‘ire
d at 4
OOOC.
with
lu
O2
inte
rlay
er
between
Co3
04 and
Ti
*PZ)
log
(p(ClZ)/atmt
IOK
(p (C
1 z)/atm)
=-1.
0
25
-
25
a a
=O. 5
j0=4
.1E-4
A cm-‘
=-3.
33
jo=2
.6E-4
A cm-’
a .=O.
5
a a
=O. 5
25
i0=1
.4E-4
A cm-’
1M NaC
l t
0.01
M HC
1 lo
g Ip(ClZ)/atml
=-1.
5
2
4
m
Note
0,
'emp. /
"C
rran
sfer
co
effi
cien
t Ra
te c
onst
ant
Ref.
-
20
Med
i urn
nerg
y of
ac
tiva
tion
lethod
P-PS
E 1 ec
t rod
e
c0304
on T
i se
e *P
2 1M
NaCl
t 0.
01M
HC1
log 1p (C
1 z)/atmt
=-2.
0
25
a .=O
. 5
io=9. 1
E-5
A
P-KS
13
7)
se
e *P
1 5M
NaC
l.Cl
2 bu
bble
d ,,=2.3
X 2RT/3F
[jn)=l. 9E
-5A
/1
00
~ F
5M N
aCl. pH c
a. 3.5
P(C12)
? 95
,,=
2. 3 x
0. 68RT/F
i0=5. 5E-1
1 A/cm'
15
~
21
:S P-gs
25
io=2. O
E-4
A/cm'
8)
*F
sire
of
O.5n
m in
ii
amet
er s
eale
d in
gl
ass
(A=O
. 13
cm
')
tath
odic
pol
ariz
atio
i fo
r ca
. 5
min
at c
a.
10 mA/cm'
0 0
9)
z s 10)
Z
UJ cn 0 0
z
*P3
95
3a=2
. 3x
0. 63
RT/F
15
Ir
5M N
aC1. pH
ca.
3.5
P(C1')
? i0=6. 4
E-3
A/cm'
Ir (i
ridi
um
oxid
e) o
n Ti
ther
mal
trea
tmen
t.
35mg
Ir/dm'
elec
trod
i su
rfac
e, p
olar
iza t
ioi
betw
een
pote
ntia
ls
for
hydr
ogen
and
3x
ygen
evo
ltio
n in
3.5
M H'S04
(*Pa)
0.05
M K
CI
p(ClZ)=
0.1
at
m t 0. 5 M
H'S04
3.=60mV
a .=
I jo
=2. 8E
-5 A
/cm"
P-PS
22
3,=60mV
a .=
I i0=4. 1E-5
A/cm'
0.1
M KC
1
p(Cla)=O.
1 at
m
0. 5 M
KC1
p(Clz)=O.
1 at
m
t 0. 5 M
H'S04
t 0. 5 M
H'S04
>.=60mV
a .=
I i0=4. 2E-5
A/cm'
1.0
M KC
1
p(ClZ)=O.
1 at
m t 0. 5 M
H'S04
s,=60mV
a .=1
i0=3. 5E-5
A/c
m'
Ir (i
ridi
um
oxid
e)
on Ti
see
tP3
22
1,=-
220m
\ I
,=O.
26
:p-p
s
:p-g
s 13
lr
Oa
see
*PI
5M N
aCl.
Cl2
bubb
led
3.=2.3
X 2RT/3F
(j0)=3.
9E-4
A /l
OO,u
F
5M N
aCl.
Cl2
bubb
led
3.=2.3
X 2RT/ZF
(jn)
=l.
44E-
4A
/lo
op
F
P-KS
13
7)
La
NiO3
se
e *P
1
see
*PI
5M N
aC1.
Clz
bubb
led
3a=2
. 3
X RT/ZF
[j0)=4. 33
E-4A
/100~ F
P-KS
13
7)
Elec
t rod
e Me
d i u
rn 'emp. /"C
'ran
sfer
co
effi
cien
t Re
f.
-
13
lethod
P-gs
Note
7)
act iv
a t io
r
/lOO
.u
F Mn
Oz o
n Pt
5M
NaC
I.CI
Z bu
bble
d la
=2
. 3
< RT/2F
1,=5
7mV
Mn
OZ dop
ed
with
Ir
(2
atom
ic %
)
ther
mal
deco
mpos
itio
n of
so
luti
on of
Mn(N03)2.
metal
salt
s and
HC1
at 160-180OC.
resu
ltin
g ox
ide
being
ther
mall
y tr
eate
d at
450O
C fo
r 20 h.
poli
shed
with
emer
y paper
to a
tab
let
shap
e (tP4)
3 M
NaCl
p(Clz)=l
atm
t 0. 5
M H2SO.q
30
fi
23
iP4
MnOZ
dop
ed
with P
d (2
at
omic
%)
see
tP4
3 M
NaCl
p(C
lz)=
l at
m t 0.5
M Hz
S04
30
1.=3
3mV
fi
23
~
23
i0=6. 1
E-2
A/cn2
MnOz d
oped
with R
u (2
at
omic
%)
atom
ic %
)
see
iP4
3 M
NaCl
p(Clz)=l
atm
t 0.
5 M
HzS
04
30
i0=4. 1E
-2 A/cm2
1.=5
5mV
MnOz
dop
ed
with
Pt
2 at
omic
%)
see
tP4
3M Na
Cl
p(Clz)=l
atm
t 0.
5 M
HzS
04
30
1.=4
5mV
23
i0=6. 8E
-2 A
/cmZ
MnOz
(Pd
dope
d, 2
and
5 at
omic
%
) (Pd 0. 2%
) (Pd 0. 5
%)
(Pd
1%
) (Pd
2%)
(Pd
5%)
Aque
ous
solu
tion
of
Hn(N03)2
and
PdCl
a was
drie
d, t
herm
ally
3e
comp
osed
in a
ir a
t 160-180'Cand
at 4
5OOC
for
16h
3 M
NaCl
t
1 M
HClO
i 1.
=30m
V 24
~
25
for Cl
z ev
olut
ion
at c
onst
anl
pot e
n t ia
l
31. 9
kJ/nol
26.8
kJ/mol
29.
3 kJ/mol
57.
3 kJ/mol
66. 9
kJ/mol
io=8
E-6 A/cmZ
i0=4. O
E-7
A/cm2
i0=3
. 7E
-3 A/cm2
PbOz
on
Ta
prep
ared
by
anod
ic
sxid
atio
n of
aq
ueou
s P bZi
so 1 u
t ion (
A= 1 cm ')
0.5
M Na
Cl
I *=
O. 1
74
P-PS
2.0
M Na
Cl
Y .=O
. 27
Pt
sire
of
0.5m
m in
iiam
eter
sea
led
in
jlas
s (A
=O. 05cm2)
O.2M
HC
1 t
1M H
zS04
p(CIz)=l
atm
25
21
11
) tF
Elec
trod
e Me
d i urn
’emp. /
“C
Ref.
-
26
Rate
con
stan
t co
effi
cien
t
j0=5
. 5E
-4 A/cm’
Tran
sfer
ne
rgy
of
acti
vati
on Me
thod
cp-g
s
Note
*P5
Pt
poli
shed
wit
h em
ery
pape
r. im
mers
ed i
n co
nc.
NaOH
and
con
c.
HC1
solu
tion
s (A
=lcm
‘)
(tP5
)
1M Na
Cl t
2M
Na
C104
Cl
z sa
tura
ted
Pt
cath
odic
pol
ariz
atio
n fo
r ca.
5 mi
n at
ca.
10
mA/cm‘
5M N
aC1. pH c
a.
3.5
P(Cl2)
? 95
b.=
2. 3
X
0. 6ORT/F
15
j0=8
. 5E
-3 A/cm’
12)
13)
r .=O
. 69
jo
=5. 7
E-3
A/cm’ I
Pt
RDE
in a
gla
ss t
ube
(A=O
. 78
5mm’
) 0.
012
M HC
l t
2.2
M HC
104
25
CP-R
DE
27
Pt
RDE
in a
gla
ss t
ube
(A=O
. 78
5mm’
) 0.
021
M HC
1 2.
2 M
HC10
4 25
CP
-RDE
27
Pt
RDE
in a
gla
ss t
ube
(A=O
. 78
5mm’
) 0.
037
M HC
l t
2. 2
M HC
104
25
CP-R
DE
27
Pt
RDE
in a
gla
ss t
ube
(A=O
. 78
5mm’
) 0.
063
M HC
1 +
2. 2
M HC
104
25
27
CP-R
DE
PS
Pt
-
Pt
wire
1M
HzS
04 t HC
1 ([HCl]=O.
1. 0. 0
5.
0.02
M)
25
a an
a =O
. 72
28
=O
. 27
wire
1M
Hz
S04
t HCI
([HCl]=O.
01,
0. 005
M)
25
a an
n =o
. 4
PS
28
ko
=9. 5
E-4
cm/s
Pt
shie
lded
ele
ctro
de
0. 1M
HC
l t
1M H2S
O4
25
a an
a =O
. 41
29
__
_
29
__
_
25
~
23
k=l.
54E
-13
cm/s
at E
=O.O
V v
s. NH
E k=
1.73
E-1
cm/s at
E=
1.43
6V v
s. NH
E
Pt
shie
lded
ele
ctro
de
0. 2M
HC
1 t
1M H
2SO4
25
a
aria
=O.
41
k=O.
97E
-13
cm/s
at E
=O.O
V vs.
NHE
k=1.
73E
-l cm/s at
E=
1.46
5V v
s.
NHE
Pt
noun
ted
in a
gla
ss
hold
er
(A=4
. 4cm
’) 0.
5 M
NaC
l a
.=O.
205
ljo=
l. 8
5E-3
A/cmZ
a .=O
. 40
0 I j0=
4. 4
58-3
A/cm’
2. 0
M
NaCl
3M NaCl
p(Cln)=l
atm
t 0.
5 M
HzS
04
Pt
smoo
th
30
3.=3
3mV
j0=
6.
7E-3
A/cm‘
Kinetic parameters of the electrode reaction: 2 C l - z Cl, i 2e- 1769
W
* a 3 3 3 3 3 3 3 - 3 - 3 4
0 m N c.7
N m
N m
N m
3 m
N m
Y)
00
I a 0 -
-
v1 a I 3
n
Y)
P
I n - Y)
n 3
> Y) - I
0 n - 0 E
Y .- w e . o N C
3
'=,
v1 n - I a 0
v1 a I
0
3
n I
0 n
-
N E 0 \ a m I
w 3
II 0 .- -
- w E 0 0 m I1
n -
LD N
-
0
N
X n - V m 2
5
N N E E
U N 0 0 E E \ \ 0 0 U U > > + +
N N N N N N E E E E E E 0 0 0 0 0 0 \\\\\\ U U = 2 = 2 < *
N N N N N N E E E E E E 0 0 0 0 0 0 \\\\\\ aaaaee ..
m I * * - L O I W I I I I
W L D W W W W wLD0000 . . . . . .
L D N N 3 3 3 It It I1 I1 I1 I1 0 0 0 0 0 0 .- .- .- .- .- .-
. . . . . . N3LDNNO) I1 II I, It I1 I1 O D D 0 0 0
- w E 0 3
3 I1
n -
LD N
w w w w w > E E E E E E 000000 weLDCDLDL0 NNNNNN I1 It I t I1 I1 tI a ' s I I * * L I
n n n n n e
L n L D L D L D 4 . 4 . 4 . 4 . e o c o e o c o r i l l r i l l 411 *I1
e e e e II I1 I1 I1 I1 It . I l i l i ( l l j '
o n n e o n n n n n n n
0 0 0 0 m L 0 r - m
L D L D L D L D L D Y ) NNNNNN
Y ) L D u 7 Y ) L D L D w w w w w w
LDLDLDLDLDLD NNNNNN
0
N
e P
3
5 u m I m 0 c N
m >.- m E .-0- 0
K * 0 OLD
m m 0 0 0 . m .v . -o u m m v II m ¶ m c - m e m e Y) a m e
w m 0 0 m i n k .- e m u o
. - - x F : m
c .--
.- 0 K n-
- n e o a
B m n m N
- m m .- a h cc.- 3 E o o c n ~
W a *
W
* m m (0
a
h
W a * m m Y)
h
0 .o ca
C L m w bow c he, m X L O m N ->o
0 - c o a a
W a * m a Y)
h
0 - Y
*a
h
0 .+ *&
0 .* -a
F:a m u x m m 0 m ) N ->o 0 0 c u a a
m u F: x c
4 a
C G V m m x c x m h 0 >o - o r
0 L
a o
e a m w x m m x c o m N - > o
O * 4- 0% a
m v e
- e a m w M u K x m m x c o m N ->o o c c o b a
c a
c a
2
.l .J
Not
e 0
RDE
-
Ref
.
0.1M
KC
I
p(C
lZ)=
O. 0
52 a
tm
t 0.
05M
HzS
04
RDE
0.2M
KC
I
p (C
1 z
) =O.
09
3a tm
t
0.05
M H
zSO
s
Rat
e co
nsta
nt
nerg
y of
ac
t iva
t ior
'e
mp.
/"I
25
leth
od
rran
sfer
co
effi
cien
t E
lect
rod
e
0.1M
KC
1
p(C
la)=
O. 0
26 a
tm
t 0.
05M
HzS
04
1,=-
16O
m\
jo=2
. 8E
-4
A/c
m2
p-RD
E 33
15
) *F
P
t a
a=O.
37
a ,=O.
31
a ,=O.
31
a .=O
. 20
Pt
25
1,=-
16O
mU
j0
=5.
2E-4
A
/cm
Z :p
-RD
E 33
15
) *F
Pt
RDE
25
j0=6
. 4E
-4
A/c
mZ
:p-R
DE
33
15)
*F
1~=
-160
m\
1,=-
29O
m\
0. 1
M KC
1
p(C
lZ)=
O. 0
85 a
tm
t 0.
05M
HzS
04
:P-R
DE
33
Pt
RDE
25
jo=
l. 1
E-3
A/c
m2
15)
*F
15)
*F
0.1M
KC
1
p(C
ln)=
O. 1
6 at
m
+ 0.
05M
HzS
04
RDE
25
r ,=o
. 12
jo
=l.
1E-3
A
/cm
Z :p
-RD
E 33
P
t 0.
1M
KCI
p (C
1 t
0.05
M H
zS0.
j =O
. 09
3a t
m
0
2
Pt
25
r .=o
. 12
jo
=l.
23E-
3 A
/cm
Z :p
-RD
E 33
15
) *F
:P-R
DE
33
__
_
33
15)
*F
Pt
RDE
25
r G=
O. 7
2 jo
=l.
5E-
3 A
/cm
2 0.
5M
KCl
p (6
1 2) =O
. 09
3atm
t
0. 5
M H
zS04
25
j0=2
. OE
-3
A/c
m2
:p-R
DE
15)
*F
Pt
z .=O
. 72
-
1M K
C1
p(C
lz)=
O. 0
93at
m
t 0.
5M
HzS
04
Pt (unp
as s i
va
t edl
a
.=O.
53
a a=
O. 5
2 a
.=O.
55
a a=
O.
64
a .=O
. 62
a
.=O.
45
a a=
O. 5
9 a
a=O.
40
j0=4
. 8E
-3
A/c
m2
jo=9
. 6E
-3
A/c
m2
j0=
5. 3
E-3
A/c
m2
j0=
3. 1
E-3
A/c
m2
jo=
l. 4E
-2
A/cm
' j0
=3. 8E
-2
A/c
m2
jo=2
. 6E
-2
A/c
m2
jo=2
. 4E
-2
A/cm
'
:p-g
s 34
*P
I 1M
HCI
3M H
CI
form
ed b
y m
elti
ng i
n
mou
nted
in
a
Pyre
x tu
be,
cath
od
ical
ly
A/c
m2
for
5 m
in
(tP
7)
sph
eric
al
butt
on
oxyg
en
flam
e an
d
po
lari
zed
at
0.5
6M HC
1
1M
NaC
l 2M
NaC
l 3M
NaC
l 4M
N
aCl
5M N
aCl
a a=
O.
49
a ,=
O.
65
a -=
O. 5
8 a
a=O.
66
a a=
O. 6
6
j0=6
. 'IE
-4
A/c
mZ
jo=l
. 66
E-3
A/c
m2
j0=3
. 9E
-4
A/c
m2
jo=
6. 4
E-4
A/c
m2
jo=l
. 4E
-4
A/c
m2
-
Ref.
't w
as e
lect
roch
emi-
:a
lly
plat
ed o
n Ti,
It l
ayer
thi
ckne
ss 3
0
'emp. /
"C
0.02
M Na
Cl +
IM
Na
CI04
. 1.00% Cl
p
rran
sfer
co
effi
cien
t
't w
as e
lect
roch
emi-
:a
lly
plat
ed o
n Ti,
't la
yer
thic
knes
s 30
ur
n
Rate
con
stan
t
0.02
M Na
Cl
+ 1M
Na
C104
. 1.
00% Cl
z
nerg
y of
ac
tiva
tion
I
Medi
um
Elec
trod
e Me
thod
No
te
~ ~~
;ee tP
7 2M
HC1
+ 3
M Na
Cl
a .=
O. 74
i0=5. 6
3E-3
A/cm
' 34
Pt
(u
npas
s i va
ted:
Pt
(pas
siva
ted)
a .=
O. 07
a &
=O. 07
a
.=O.
07
a a
=O. 07
4 a .=
O. 05
a a
=O. 06
a .=
O. 06
a .=
'O. 04
34
jo=l
. 7E
-3 A
/cmZ
jo=1. 7
E-3
A/cm
2 jo
=l. 8E
-3 A
/cm2
jo=l. 5
E-3
A/cn
2 jo
=Z. 2E
-2 A
/cm2
j0=4. 9E
-2 A
/cnz
j0=8. 6E
-2 A
/cm2
jo
=2
. 7E-1
A/
cmZ
io=8
. OE
-6 A/
cm2
j0=3. 2E
-6 A
/cmZ
jo=2
. OE
-5 A/
cm2
i0=1. 6E
-5 A
/cmZ
jo
=7. 1E-6
A/
cm2
1M H
CI
2M H
C1
3M H
CI
4M H
CI
5M H
CI
6M H
CI
7M H
CI
1M N
aCl
2M Na
Cl
3M N
aCl
4M N
aCl
5M N
aCl
;ee tP
7
iee
tP7
34
Pt
(pas
si va
t ed)
a .=
O. 15
a a
=O. 13
a .=
O. 12
a a
=O. 12
a a
=O. 14
a .=
O. 03
1 0,
3
(I)
i0=6
. 3E
-2 A
/cm2
34
Pt
(p
assi
va t e
d)
m 2 a 7)
Q
(I)
PtO2
on Ti
ISM NaCI
. Cl
a bu
bble
d (j0)=5.
50E-
4A
/100
u F
13
b.=2
. 3
X RT/2F
~-
30
jo=4. 6
E-4
A/cm
2 35
Pt
on Ti
1 =-
0.2v
0. 2V)
1,=-0.4-
-0.5
v :I
t] I>
0. 25
V)
:lo I<
Pt o
n Ti
30
b.=O
. 12
V (o
<o. Z
V)
jo=O. 6E
-3 A
/cm2
35
b,=O
. 6V
(
7l
>o. 4
V)
Pt p
late
d on
Ti
25
a .=
O. 74
k"=l. 28
8-3
cm/s
CP-P
S 1
2
z .=O
. 27
z ==
o. 2'
1 CP
-PS
12
Pt p
late
d on
Ta
1M
HzS
O4
+ 0.
05M
HCI
25
a .=
O. 73
k'
=l.
10E-
3 cm
/s
Pt
0 b,=(106
i 20)mV
jo=(
l.2F
O. 3
)E-4
A/cm2
cp-R
DE
36
18)
[C1-
1=4.
ImM
. [C
1~1=
14. 4m
M.
0.4M
LiC
IOa
in A
N
-
Ref
. E
lect
rod
e R
ate
cons
tant
E
nerg
y of
ac
tiv
atio
n M
et ho
d M
ed i
urn
[C1-
1=6.
2mM
. [C
121=
16. O
mM.
0.4M
L
iC10
4 in
AN
Not
e co
effi
cien
t
36
Pt
jo=
(l. 3
6f0
. 3)
E-4
A/c
m2
CP-R
DE
cp-R
DE
[C1-
]=8.
4mM
. [C
l;.l=
lO.
Id
. 0.
4M
LiC
104
in A
N
jo=
(l.0
7+0.
3)E
-4
A/cm
2 36
20
) P
t
[C1-
]=8.
5n
M.
[C12
1=23
. 9m
M.
0.4M
L
iC10
4 in
AN
36
jo=
(l. 5
3rt 0
.3)E
-4
A/cm
' cp
-RDE
CP-R
DE
36
2 1)
[Cl-
I =9
. 3mM
. [C
121=
26.
8mM
. 0.
4M
LiC
104
in A
N
[C1-
]=9.
3mM
. [C
1~1=
7. Om
M.
0.4M
L
iC10
4 in
AN
j0=
(1.8
0fo
.3)~
-4
A/c
m2
cp-R
DE
36
22)
j0=
(1.0
8+0.
3)E
-4
A/cm
2
[Cl-
l=9.
8mM
. [C
lzI=
lO. 4
mM.
0.4M
L
iC10
4 in
AN
36
jo=
(l. 7
7f
0.3)
E-4
A
/cm
2 23
) CP
-RDE
cp-R
DE
[Cl-
]=lO
. 6m
M.
[C1;
.1=1
5.
9mM
. 0.
4M
LiC
104
in A
N
jo=
(l.
33rt
O.
3)E-
4 A
/cm
2 36
0
[Cl-
I=ll
. 3m
M.
[C12
1=11
. 4m
M.
0.4M
L
iC10
4 in
AN
36
~
36
jo=
(l. 7
$f
0. 3
)E-4
A/
cm
jo=
(2. 2
0f0.
3)E-
4 A/
cm'
jo=
(l. 0
5f 0.
3)E
-4
A/c
m2
cp-R
DE
cp-R
DE
[Cl-
]=ll
. 4m
M.
[Cl2
]=17
. 6m
M.
0.4M
L
iC10
4 in
AN
26)
[Cl-
l=12
. 1m
M.
[C1;
.]=9.
5m
M.
0.4M
L
iC10
4 in
AN
36
27)
tp-R
DE
:p-RD
E [C
1-]=
13.
8mM
. [C
121=
13. 7
mM.
0.4M
L
iC10
4 in
AN
36
jo=
(l. 5
4+0.
3)E
-4
A/cm
2
Kinetic parameters of the electrode reaction: 2 C l - t Cl, + 2e- 1773
h 3
m -
CD m
- w n m n I
0
h
y3 m
~
CD m
~
w
I
0
n m n
h m N
CD m
w a I
0
n
n
h
0 m
CD m
W
a I
n
n
-
CD m
- w n m n I
0
-
CD m
- w a I
n
n
CD N
_.
a I P 0
Do
-
d I
w h m
0
+I O N m e . o N\ - 4 I1 0 .-
d I
w h
m
0
i N m E . O
N\ - 4 I1 0 .-
-r I
w h m
0
i N * E . O -\ -< I1 0 .- -
- w N E 3-
-0 I N
' l o t 1 n -
w O E O h
30 -N
'b ti n
* I
w m
0
h
2 N W E . O
N\ -4 I1 0 .-
LD
I w
CD
0
h
+IN O E . o *\ -< II 0 .-
* I w
CD
0
h
t I N ' E .0 -I\ - 4 II 0 .-
y3
I w - CD
0
tl N O E .0 -\ - 4 I1 0 .- -
d I
w h en
0
+I O N N E . 0 N\ - 4 II 0 .- -
m w O E 4-
-0 I N
I!" ti n -
e I
w h CD
0
ON O E
- 4
+I
4< II 0
..7 - o w m e 3-
-0 I N
In" +I n -
I a
E 0
N I
W 0
3
I1 0
s -
N E 0 \ 4
* I
w y3
Ln I1 0 .- -
m w 3 E -0 I N
3-
+I n -
w * E 4-
30 VN
'b ti n
w d E m - -0 I N
I1u tl n
w y 3 E O h
30 VN
'b +I n
O > O E -0 I N
4-
ti n
w d E N h
30 -N
'b +I n
w m E y 3 h
30 -N
".ti n
w y3E C D h
' 0 VN
'I, +I n
w W E y 3 h
30 -N
'I, tl n -
0
w O E y 3 h
30 -N
'6 ti n
N y3
0 I1 4
e
y3 N 0 0 0 0 0 0 0 0 0
z 4
C
E I -4 CO E O
y3 .o 3 m .- I1 I1 A m n I N Z --* u o . - Y O
i :- .--
-
z 4
c .d
z: E - 4 N O
m o
I1 A
I I - d v . -0
. - r3 .- 7
-
z 4
e z: E - 4 m o
m o
.- .-
3 .- II A
I = -d u . Y O
n
-
+ 0 -Lo
O I
Z e d .- m .a
- 4
x n
t E CD
- 4
00
-I . . -
h
U E 0 P-
N N
0 I1 4 -
-4 0
0 m r
U Za, N C
m + 4 a 3- o m m v l z
N Z - -u
-
-
Y)
a * m m rn
-4 0
0 m z
U Z m
m + 4
o m m a z N I- 4 o
- - 4 - 2
a -c)
-
Lo
* m ar
a
vl
z 4
e ss- & A Z E E -4 3-0
3 N .- nn II II A
I N Z ---r o u . u-0
2 4
e is- W A Z E E -4 m - o
N 4.3
I1 I1 A -n I N Z --* v u . U U O
h
3
0 4 - h c o \- 4 - m a
w
--
h
N
y3 3
w
- h c o
\- + - m a
-- c)
a c)
a c)
a c)
a +- a
+- a
4 a
+- a
c)
a c)
a c)
a +- a
' 0.
02M Na
Cl t
1M
NaClO,,.
1.00
% C
ln
ther
mall
y fo
rmed
. ca
thod
ic p
olar
izat
ion
for
ca.
5min
at
ca.
10 mA/cmZ
5M N
aC1. pH c
a. 3.5
p(Clz)
?
smoo
th s
urface.
ca-
thod
ic p
olar
izat
ion
for
ca.
Smin
at
ca.
10 m
A/cmZ
5M N
aC1. pH
ca.
3.5
p(Cl2)
?
wire
of
0.5mm
in
diam
eter
se
aled
in
glas
s (A
=O. 06cm")
0. 2M
HCI
t 1M
lI2
SOa
p(ClZ)=I
atm
cath
odic
pol
ariz
atio
n fo
r ca.
Smin
at
ca.
10 mA/cm2
5M NaC1. pH ca.
3.5
p(Cl2)
?
iisk (A
=1.0
0 cm2)
4M N
aCl
t 1M
HCI
Cl
z sa
tura
ted
'emp. /"C
'ran
sfer
co
effi
cien
t Ra
te c
onst
ant
Ref.
-
38
E I ec t
rode
I
Medi
um
4
4
n
Note
ne
rgy
of
act i
vat i
or Me
thod
gs-p
s-
RDE
Pt/lr
on T
i (I
r 0. 0. 5.
2.
4 an
d 10
0%)
30
30
30
1.=30mV
1,=30mV
1,=30mV
and
-0.4V
for
10
satu
rate
d Na
Cl
time
s an
d he
ld a
t -0.4V
for
3s
Pt/lr
(30% I
r)
allo
y on
Ti
Pain
ted
with
mix
ture
of
PtCls. lr
C14
etc..
dried
and
heat
ed a
t 500°C
for
lh.
cool
ed
in w
ater.
I mg/cm2
of
PttI
r as
chl
orid
e
30
I =-0. 18
Ll
I<
0. 2V)
0=2.
OE-3
A/cm2
CP-P
S 35
37
)
-
38)
0.02
M Na
Cl t
1M
Na
C104
. 1.
00%
CI2
30
1.=0
. 15-
0. 2v
ia=
O. 6V
: g
<o. 2
V)
: g >o
. 4V)
0=2.
5E-3
A/cm2
CP-P
S 35
Pt/lr
(70:30)
95
la=2
. 3
x (0.27
-0.3
4)
x (RT/F)
0=3. 15E-3
A/cm2
15
~
15
39)
40)
0
2
Pt/lr
(70:30)
95
0=8.
5E-4
A/cmZ
Pt/Pd(l?. 0%)
allo
y se
e tP5
1M NaC
l t
2M N
aC10
4 C
l2 sat
urat
ed
o=4.
OE-4
A/cm2
26
Pt/Pd(24.0%)
allo
y se
e tP
5 1M
NaC
l t 2M
NaC
104
Clz
sat
urat
ed
0=4.
05-4
A/cm'
26
Pt/Rh(32.
4%)
allo
y se
e tP
5 1M
NaC
l t
ZM N
aC10
4 C
l2 sat
urat
ed
0=4.
3E-4
A/cm2
Pt/Ru(l7.0%)
allo
y se
e tP
5 1M
NaC
l t ZM
NaC
104
Cla
sat
urat
ed
0=4. 5E-4
A/cm2
,,=4.
OE-5
A/cm2
Rh
25
Rh
95
0=5.
9E-3
A/cmZ
Ru
25
1,=40mV
o=
l. 3E-4 A/cm'
-
e t hoc
95
25
40
80
-
Ref.
b,=2. 3
X
(0. 27
-0
.38)
x
(RT/F)
ba=4
0mV
a a
=O. 5
5 ?
0.
05
ba=3
4 f 0. 5mV
b.=34 f 0. 5mV
Elec
trod
e
30
30
20
20
Med
i urn
ba=4
0mV
ba=4
0mV
b.=95mV
b,=(108
f 12
)mV
emp. /"
C Tr
ansf
er
coef
fici
ent
Rate
con
stan
t :n
ergy
of
ac ti
vat
i( No
te
Ru
~ ~
~~
cath
odic
pol
ariz
atio
r fo
r ca.
Smin
at
ca.
10 mA/cm'
5M NaCl. pH ca
P(Cl*)
? jo
=2E-
4 A/cmz
S 15
43
)
RuOZ
(30mol%) /
Ti02(70mol%)
on Ti
Pain
ted
with
aq.
soln.
of T
iC13.
RuC1:
etc..
drie
d an
d firec
at 5
OO0C
for
lh
4M NaC
l +
1M HC1
Cl
z sa
tura
ted
!I. 2
kJ
/mc
'or cd
at
v =6
0mV
ai !-70°C
39
Ru02(10%)/TiOz
(90%)
on Ti
Pain
ted
with
mix
ture
of
RuC13.
butyl
tita
- na
te a
nd b
utyl al
co-
hol.
drie
d by h
eati
ng
up t
o 130°C
and
de-
comp
osed
the
rmal
ly
1M HCl
+ 1
M HzSO
13.3-44.
I ;J
/mol
fo
i :d a
t rl
:TO-
OO
mV
40
jo=6
. 7E-5
A/cm2
(a=-
142m
V)
j0=5. 1E
-4 A/cm'
(a=-
112m
V)
jo=2
. 8E-
4 A/cm'
j0=4. 5E
-4 A
/cmZ
j0=
7. 4E
-4 A
/cm2
j 1.
8E-3
A/cm'
60
80
RuOJ
Ti02
on
Ti (RuOz
1-
100%
)
ther
mal
deco
mpos
itio
r of
Ti
and
Ru s
alts
de
posi
ted
on Ti
base
300g
/dm3
Na
Cl
41
~
42
a s. ? *F
b
?
*F
RUOZ
(100%)
1. 5M
HCl
+ 2.
5M
NaC1.
p(Clz)=l
a ),-=120ml
j,,=l. 4E
-3 A
/cmZ
RUOZ
(100%)
1. 5
M HC
l +
2. 5M
NaCl.
p(Clz)=O.
0568
atm
),=-12Om1
jo=l. 6E
-4 A
/cm2
42
RUOZ
on Ti
coat
ed w
ith
6 co
ats
of 0
.4M
RuC1
3 in p
ro-
pano
l an
d fi
red
at
4OOO
C fo
r 1-50
h
5M N
aCl.
Cl
z sa
tura
ted
j0=6. 3E
-3 A
cm-'
43
RuOz
on Ti
coat
ed w
ith
2.4.6.8
coat
s of
0.4M
RuC1
3 in p
ropa
nol
and
firec
at 4
00°C fo
r 1-50h
5M N
aC1.
ClZ
satu
rate
d j0=3. 9E
-2 A
cm-'
43
RuOz/Ti02
on
Ti
(Ru02
Imol
%)
coat
ed w
ith
solu
tion
of
RuC
13 in p
ropa
nol
and
anhy
drou
s TiC14.
Ti(OEts)
in p
ropa
nol
and
fire
d in a
ir a
t 400°C
for
5min
and
then f
or 6
h (t
P8
)
5M NaCI.
C12
satu
rate
d jo
=4.0
E-5
A cK2
43
*P8
tF
~ jo=2
.0E-
4 A
cm-*
Elec
trod
e Me
d i u
n em
p. /“
C ra
nsfe
r co
effi
cien
t Ra
te c
onst
ant
Ref
see
tP8
5M NaCl.
Clz
sat
urat
ed
20
jo=8
. 9E-
5 A
cm-’
43
SF
RuOz/TiOn
on
Ti
(RuO
z 5IIIOl%)
RuOz/TiOz
on
Ti
(RuO
z 1011101%)
RuOJ
TiOz
on
(RuO
z ZO
nol%
) Ti
60
j0=2
.OE-
4 A
cm-‘
see
*PB
5M NaCl.
612
satu
rate
d 20
jo
=l.
OE-
3-2.
5E
-4
A CM-‘
43
*F
60
jo=
l. OE
-Z/A
cm
-’
5M NaCl.
612
satu
rate
d 20
jo
=1.
OE-
3-2.
5E
-4
A cf2
43
~
43
*F
see
*P8
RuOz/Ti02
on
(RuOz
25m
ol%
) Ti
see
SPB
5M
NaC1.
C12 sa
tura
ted
20
j0=4
. 5E-
3 A
cm-‘
0 0
s v) v, 0
SF
z 0
z
rn
I- rn
0
-I
33 0
0 I
*F
rn
v) <
*F
3
*F
5 2
60
j0=4
.OE-
3 A
cm-’
RuOJ
TiOz
on
(RuO
n 30
1~01
%)
Ti
see
*P8
5M NaC1.
Clz
satu
rate
d 20
j0
=4. 5
E-3
A CI
II-’
43
RuOJ
TiOz
on
Ti
(RuOZ
4011
101%
)
see
tPB
5M
NaCl.
Clz
satu
rate
d 20
j0
=7.
98-
3-6.
3E
-3
A cK2
43
RuOJ
TiOZ
on
Ti
(RuO~ 50
1110
1%)
5M NaC1.
C12
satu
rate
d j,
=7.
9-3E
-5.
OE-3
A
cm-‘
43
-
43
see
SPB
20
j0=5
. 6E-
3 A
CR-’
j0=
6.
38-3
-5.
6E-3
A
cK2
60
20
RuOz
/TiO
z on
(RuOz
6011101%)
Ti
see
SP8
5M N
aC1.
Cl
z sa
tura
ted
IF
RuOJ
TiOz
on
(RuOz
7Omo
l%)
Ti
see
*P8
5M N
aCl.
Clz
satu
rate
d 20
j,
=7.
1E-3
-5.
6E-3
A
cm-2
43
*F
RuOz/TiOz
on
Ti
(RuO
z 80
1110
1%)
see
tP
8 5M N
aCI.
Cln
satu
rate
d 20
j,=
7.
1E-3
A
cm-’
43
*F
