Theory and Application Voltammetry Measurement of Electrode Reaction Kinetics
Theory and Application Voltammetry Measurement of Electrode Reaction Kinetics
concentration
isotherm (21)-correctly describes the
data obtained. However, it seems unlikely that so many compounds would
show maxima or minima in nitrogen but
none of them would do so in Ar or CO,,
while they do give positive and negative
responses in these gases.
One possible alternative explanation
is that a concentration gradient is
established in the cell as a result of
thermal diffusion between the cell wall
and the hotter filament. This could
result in a transfer cf thermal energy
across the gradient, the so-called Dufour
effect (7). If so, it should be possible
to eliminate this effect by increasing
the tu1 bulence in the cell. Preliminary
investigation with such a cell indicates
that this is so.
The lack of W peaks and the low cost
of CO, suggest that it would be a better
carrier gas than nitiogen for preparative
work (and possibly even some analytical
work). Some workers have reported
collecting samples in CO, by freezing it
to dry ice (9). Also, the wide variation
in response values (positive and
negative) might be useful for qualitative
analysis of pure compounds. Further
work with COz and other carrier gases of
low T C is planned.
ACKNOWLEDGMENT
LITERATURE CITED
~~
(24) Stuve,~K.,
in Gas Chromatography1958, p. 178, I). H. Desty, ed., Academic Press, X e w Ynrk. l Q 5 .
(25) lerzele, AI., J .
(1964).
(26) Williams, A. F., Murray, W. J.,
Talanta 10, 937 (1963).
RECEIVEDfor review April 7, 1965.
Accepted July 22, 1965. Pre-ented at
the Pittsburgh Conference on Analytical
Chemistry and Applied Spectroscopy,
March 3, 1965.
years a number of
methods have been developed
for the measurement of electrode reaction kinetics. I n one sense, some of
URING RECENT
Mich.
1351
0.4
-0
I
120 60
-60
-120
(E E , , h mv.
--- iC.
= 0.5;
CY
= 0.7
= 0.3
ANALYTICAL CHEMISTRY
O+ne*R
E, - ut
E,
+ ut - 2uX
aco
Do - = k,(Co*/C~*)-"[Sx(t)]-* x
ax
(CO, = 0
aco
_-
avo
at - D O T ax
(9)
kb
(8)
( C O * / ~ R * ) ~ A ( ~ o)) ~ R(10)
,
T h e function Sx(t) is defined as
t<X
&(t) =
2ax
t>
(11)
where
a = nFv/RT
(12)
!4
t2O,x=O
(Do/DR)"'
(14)
at
(15)
Do aco
a,/Co*l/?rao,
(16)
Y =
y =
x(y)
= y4s/l/*aDo
(17)
(E
E,,h,
CY
CY
80
1006
3 120-
140-
160I
rnv
60
= 0.5
= 0.5
AEP X
$"
20
7
6
63
64
65
66
68
84
3
2
72
0.75
0.5
0.35
0.25
0.1
7~,*
mv.
61
92
105
121
141
212
1353
OF
Apparatus. T h e circuit was essentially the same as described previously (10). All measurements were
made with a three-electrode potentiostatic circuit, using a single Philbrick
>lode1 SK2-V operational amplifier
(G. A. Philbrick Researches, Inc.
Boston, Mass.). To improve rise-time
1354
ANALYTICAL CHEMISTRY
v,
volt/sec.
48.0
60.0
90.0
120,o
n,
mv.
$5
94
98
108
115
0.70
0.61
0.48
0.41
a Determined
Equation 17.
from
ke ,
cm./sec.
0.25
0.25
0.24
0.23
Figure 3; see
sodium sulfate.
+ = l/(nF/RT)nFAX
( T ~ D O ) ~ C ~ *(18)
R,
Thus, the variation of peak potential
separation with scan rate is quite similar
for the two cases.
The effect of ohmic potential losses
can be minimized in three mays. First,
b The polarographic
behavior
of
HE DROPPING-NERCURY electrode of
Teflon (DuPont) has been described
(8),and its operation in noncorroding
media was investigated (9, 10). A
review was given (8) of the polarography
-done before the D.3I.E. of Teflon was
developed -of substances in liquid hydrofluoric acid and in aqueous acid
fluoride media.
The polarography of lead in acid
fluoride media has been studied to a
limited estent. West, Dean, and Breda
( 2 1 ) obtained a well-defined wave for
lead in 0.5X Na2F2 [qic]-O.Ol% gelatin
solutions of p H 1.1 to 2.75 that contained considerable amounts of nitric
acid added to dissolve the lead fluoride
precipitate; the solutions therefore contained lead nitrate and slightly dissociated hydrofluoric acid. The polarography of lead, as PbF2,in liquid hydrofluoric acid was investigated briefly by
Clifford (2). Mesaric and Hume ( 7 )
used polarography to study lead fluoride
complexes and their solubilities; the
solutions they studied were 1mJf in
Pb+*, u p t o 0.7M in F-, and of 2 M
ionic strength adjusted by adding
KaC104. With a D.M.E. of Teflon,
Headridge and associates studied the
1355