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Ring-Disc Electrodes
Part 2.-Theoretical and Experimental Collection Efficiencies
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* AND S. BRUCKENSTEIN
BY W. J. ALBERY -1
Received 8th December, 1965
A fundamental parameter for a ring disc electrode is N, the collection efficiency. An exact
solution for N is derived by rigorously solving the convective diffusion equation with the proper
boundary conditions. Experimental results obtained on six different electrodes are in excellent
agreement with the predicted values of N. The new theory is compared with an earlier approximate
treatment which, depending on the electrode geometry, may lead to errors of up to 25 %.

Using the method described previously,l we calculate in this paper an exact

solution for N, the collection efficiency of a ring-disc electrode ; N is defined as the
proportion of material produced electrochemically on the disc electrode, which
reaches the ring electrode. If all the material reaching the ring electrode is electro-
or chemically converted back into its precursor, then
N = ring current/disc current = -i~/i~.
The negative sign is included since the flux of material and therefore the current must
be flowing in opposite directions at the disc and at the ring electrodes. To find N
we need to calculate the limiting ring current for a given disc current.
The equation obtained below yields values of N in excellent agreement with
experimental values in the literature 2 and with the thin-ring, thin-gap electrodes
studied experimentally in this paper. With these electrodes the approximate solution
of Ivanov and Levich 5 gives values for N which are up to 25 % too large,

DIFFERENTIAL EQUATION AND BOUNDARY CONDITIONS

In the absence of kinetic complications, the basic convective diffusion equation 6

is
a2C i ac
- +-+--
d2C
u,-++,- =
ar ax ax2 ar2 r ar
Since, in solution, convection is a much more efficient transport process than diffusion
we may write 6 for a rotating disc,
up = Crx and v, = -Cx2, (2.2)
where the convection constant C = 0.5 10w 3 b - 1 / 2 .Furthermore outside a layer of the

- - -
order of 10 A next to the disc the radial convection term is much larger than the radial
diffusion terms ; e.g., taking v 10-2 cm2 sec-l,0-2 x 102 radians sec-1, r-0-5 cm,
D 10-5 cm2 sec-1, we have D/rv, 3 x lO-g/x. Thus the amount of material
transported radially by diffusion is negligible compared to that transported by
* Physical Chemistry Laboratory, Oxford.
Department of Chemistry, University of Minnesota, Minneapolis 55455.
1920
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W. J . ALBERY, A N D S . BRUCKENSTEIN 1921
convection and the radial diffusion terms can be dropped from eqn. (2.1). The
equation then becomes :
r-ac -x- ac = D
--1 __
a2C
(2.3)
dr ax c x ax2’
Let the radius of the disc electrode = r1, the internal radius of the ring electrode
= r2 and the external radius of the ring electrode = r3. Then the boundary condi-
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tions 5 for the differential equation (2.3) are :

(1) all zones, x + m , c+O ;
(2) zone of the disc, r<r1, at x = 0, d c p x = iD/n+FD ;
(3) zone of the gap, r l < r < r2, at x = 0, &/ax = 0 ;
(4) zone of the ring electrode, r2 < r e r3, at x = 0, c = 0.
Also we may write

Now let
,i = nFD2n
s:: (ac/ax),=,rdr.

w = (C/D)+X,
and
nr:nFD*CC’
u=- .c,
iD
then eqn. (2.3) becomes
au ,au
rw-----w - = a-
2U
ar aw dw2
with boundary conditions :
(1) w+w, u - t o ; (2.8)
(2) r < q , w = 0, &/dw = - 1 ; (2.9)
(3) rl<r<r2, w = 0, dufaw = 0; (2.10)
(4) ~ 2 < r < r 3 , w = 0, u = 0. (2.11)
Also

(2.12)

ZONE OF THE D I S C E L E C T R O D E

In this zone the classical situation of uniform accessibility to the surface of the
disc prevails, i.e., terms in a / d r are zero and one merely has to solve the differential
equation
__
aZU - 2au
aw2--w- aw
with boundary conditions (2.8) and (2.9) to give 6
r 3-3,
u = 3T(i+)- 3+ exp ( -A3)dL.
J O
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1922 R I N G - D I S C E L E C T R O D E C O L L E C T I O N EFFICIENCIES

ZONE OF THE G A P
Let y = ( r / q ) w , then using the relations :

@w = (:)y+:(g)r ’

(E)r L(E)r (ky($),

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= rl a Y and ($)r = ,
eqn. (2.7) becomes
au -i a2u
a(r3/3r;> - yay”
Let 51 = +[(r/t3)3- 11, then we must solve
au
-=-
1 a2U
351 Y dY2
with boundary conditions from eqn. (2.8), (2.10) and (3.1) :
y+m, u+o,
y = 0, au/ay = 0
and at
3-3,
= 0, u o = 3*l?(1+)-3*/ exp ( -A3)dA.
0
Applying the method given above we obtain from eqn. (2.21) of the previous
paper 1 that

where ii is the Laplace transform of u with respect to 51, $1 is the transformed variable,
z1 = sty, and q = [3%r(+)]-1.
We now evaluate the sum in the square bracket.

but each term xm has to be operated on rn times before it has a non-zero value when
x = 0 and as shown each operation throws out a factor of - 3 s;I(j-2/3). Hence,

Z O N E OF T H E R I N G E L E C T R O D E
Following the same transformations as used at the beginning of 5 4 we obtain :
aii-- -1-
- a2E
a52 Y aY2
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W. J . A L B E R Y AND S. BRUCKENSTEIN 1923
where y = YW/Y~,

-[(->'-(3].
the same definition as before,
t-2 = l

3 rl
r

and ii is u transformed with respect to t ~ .

We work with ii rather than u since the boundary condition for ii given by eqn.
(4.3) cannot easily be, and indeed need not be, inverted for our purposes.
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From eqn. (2.8), (2.11) and (4.3) the boundary conditions for eqn. (5.1) are:
y+co; ii-to; y = o ; u = o ;
and at 5 2 = 0, iio is defined by eqn. (4.3).
From eqn. (2.12) we wish to find

where u" is ZL transformed with respect to both c1 and ( 2 . s2 is the transformed variable
of & and the constants
={(->'
1 -I]r2
3 rl
and 1 r3
3 rl
=-[(->'-(33].
From the general method eqn. (2.14),1 putting y and u' equal to zero, we obtain

or substituting from eqn. (4.3)

N
EQUATION FOR
The double inverse transform in eqn. (5.3) is evaluated in appendix 1. From
eqn. (9-11) we have the result
+ +
N = 1 -F(a/P) P'[I -F(a)] -(I a + P)'(l -f'[(a/P)(l+ a + P)]), (6.1)
where
a = 3(; = (r2/r1)3--I.
p = 3 l ; = (r3/ri)3-(r2/ri)3
and

The integral in the expression for F(0) can be solved4 to give

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1924 RING-DISC ELECTRODE COLLECTION EFFICIENCIES

When 8 = 0, F( 8) = 0, and when 8 +a, I;( 0) -> 1. Values for F( 0) for 8 from 0 to 1
were calculated and are given in table 1. For values of 8 greater than 1 the following
transformation can be made. Writing x = A-1,
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TABLE
I-VALUES OF F(e) [EQN. (6.2)]
e -00 .o 1 -02 *03 -04 -05 -06 *07 -08 -09
0 .oooo * 1777 ,2234 -2551 -2801 -3010 -3191 ,3351 -3495 -3627
-10 -3748 -3860 -3964 *4063 -4155 -4242 -4325 -4403 -4478 *4550
-20 -4619 -4685 -4748 -4809 -4867 -4924 ~4978 -5031 -5082 -5132
-30 -5180 *5227 -5272 -5316 -5359 ,5400 -5441 ~5480 -5519 ,5557
-40 05593 ,5629 a5664 -5698 -5732 -5765 -5797 -5528 -5859 ,5889
-50 -5918 ,5947 -5975 -6003 -6030 -6057 -6083 -6109 *6135 -6159
-60 -6184 -6208 -6231 -6255 -6278 *6300 -6322 6344 *6365 -6386
-70 -6407 -6427 ~64.47 -6467 -6487 -6506 -6525 a6544 ,6562 -6580
-80 -6598 -6616 -6633 -6650 -6667 -6684 ~6700 -6717 -6733 -6749
-90 *6764 *6780 -6795 -6810 a6825 -6840 ~6854 -6869 -6883 -6897

Then
1 -F(@ G(l/@).
=
Values of G ( 4 ) for 4 from 0 to 1 were also calculated and are given in table 2. By
using the appropriate table the functions in eqn. (6.1) can be evaluated, for any
values of a and /?.
TABLE2.-vALUES OF G (4) [EQN. (6.3)]
4 -00 41 -02 *03 so4 a05 a06 -07 SO8 *09
0 *oooo -0191 *0302 60395 -0476 a0550 -0619 -0683 a0744 ,0802
*lo ~0857 *0910 -0961 *lo10 a1057 -1103 -1148 -1191 -1233 01274
.20 -1313 ~1352 -1390 *1427 -1463 -1499 -1533 -1567 *1600 el633
a30 -1665 -1696 ,1727 -1757 * 1787 -1816 -1845 -1873 a1901 a1929
*40 -1955 a1982 -2008 -2034 -2059 -2084 *2109 a2133 -2157 92181
*so -2204 -2227 -2250 ,2272 -2294 a2316 -2338 -2359 -2380 -2401
60 -2421 -2442 -2462 a2482 -2501 *2521 -2540 a2559 a2578 -2596
-70 -2614 -2633 -2651 -2668 ~2686 ,2703 -2721 -2738 -2755 -2771
-80 ,2788 -2804 -2821 -2837 -2853 -2868 *2884 ~2900 -2915 -2930
-90 -2945 a2960 -2975 -2990 -3004 -3019 a3033 -3047 -3061 -3075

Table 3 contains values of N computed for typical values of r?/r1 and r3/r2. For
most electrodes used in practice, N should be able to be found directly from this table.
The approximate formula 5 calculated by Ivanov and Levich has been shown 8
to give an equation for N :

+
where, in our notation, 1c3 = 1 -$(a 1)-1 and X3 = /?(a+ 1)-1. By means of the sub-
stitution x = it may be shown that
+
NIL = 0.9674Cl- F(a 0*25)/p]. (6.4)
 View Article Online
W . J . ALBERY A N D S . B R U C K E N S T E I N 1925
In his original treatment, Levich 5 considered the case where the intermediate
formed on the disc electrode can undergo a further heterogeneous reaction ;in other
words, there is competition between the second heterogeneous reaction and the
transport of the intermediate to the ring electrode. Under these conditions the
boundary condition for c at the disc electrode becomes 5 :
ac i, k'
+
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-=- -C;,
ax nrfnFD D

3.-vALUES
TABLE OF N FOR COMMON RADIUS RATIOS
* 3 h r21r1

1*02 1-03 1.04 1.05 1.06 1-07 1.08 14 9 1.10

1.02 -1013 a0976 ,0947 -0922 -0902 ,0884 -0869 -0855 ,0843
1-03 - 1293 -1250 -1215 -1186 -1162 -1140 -1121 -1104 -1089
1-04 -1529 -1483 -1444 -1412 *1385 -1360 ~1339 -1320 -1302
1*05 ~1737 -1687 -1647 a1612 -1582 -1556 ~1533 -1512 -1493
1-06 -1923 -1872 -1829 -1793 -1761 el733 -1708 -1686 * 1665

1-07 -2092 -2039 -1996 el958 -1925 -1896 -1869 -1846 -1824
1-08 -2247 -2194 -2149 -2110 -2076 a2046 *2019 1994 * 1972

1-09 -2392 -2338 ,2292 -2252 *2217 -2186 -2158 -2133 -2110
1.10 a2526 -2472 -2426 a2385 -2350 -2318 -2289 -2263 -2240
1-12 -2772 -2717 -2670 -2629 ~2593 *2560 ~2530 -2503 -2479
1.14 ,2992 a2938 *2890 -2849 a2812 -2778 a2748 ,2720 *2695
1-16 -3192 -3138 -3090 -3048 -3011 -2977 -2947 -2919 -2893
1.18 -3375 -3321 ,3274 *3232 -3194 -3161 -3130 -3101 -3075
1*20 -3544 *3490 -3443 *3402 ~3364 -3330 -3290 ~3271 -3245
1-22 -3701 *3648 *3601 -3560 a3523 ~3489 a3458 -3429 -3403
1-24 -3848 *3795 -3749 ,3708 -3671 a3637 -3606 -3577 -3551
1-26 -3985 -3933 -3887 -3847 ,3810 -3776 -3745 -3717 -3691
1.28 -4115 *4063 *4018 a3977 -3941 -3907 -3877 03849 03822
1-30 -4237 -4186 -4141 a4101 ,4065 -4032 *4001 -3973 *3947
1-32 *4353 *4302 *4258 -4218 -4183 a4150 -4119 -4092 a4066
1-34 -4463 -4413 -4369 -4330 ,4294 -4262 -4232 04204 -4178
1.36 -4567 -4518 -4475 -4436 ,4401 -4369 *4339 *4311 -4286
1.38 -4667 ~4619 -4576 -4538 -4503 4-471 ,4441 a4414 *4389
1*40 -4762 *4715 -4673 *4635 ~4600 -4568 -4539 -4512 a4487

where k' is the heterogeneous rate constant in cm sec-1 and c; is the surface concentra-
tion of c on the disc electrode. We now define

then, as before, for the disc electrode at w = 0, du/dw = - 1 and from eqn. (3.1) we
obtain

Then, instead of eqn. (2.12), we have

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1926 R I N G - D I S C ELECTRODE COLLECTION EFFICIENCIES

where N' is the observed collection efficiency and N is the value obtained from
eqn. (6.1). The factor describing the effect of the heterogeneous reaction at the disc

is the same as the factor obtained in the treatment of Ivanov and Levich.5
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EXPERIMENTAL

APPARATUS

Current-voltage curves were obtained using Sargent model VX and XXI polarographs.
Ring-disc electrodes were fabricated using epoxy or Teflon for the insulated portion of the
electrodes. The disc portion of the electrode was constructed by silver soldering 0.040 in.
platinum (or gold) to a 3% in. shaft, while the ring electrode was fabricated by drilling out a
slightly larger disc of the electrode metal previously silver soldered to the end of a metal tube.
The epoxy insulated electrodes were prepared by first coating the edge of the disc and its
shaft with liquid epoxy resin, curing the resin and turning the electrode end of the rod to the
internal diameter of the ring electrode tube. All cured epoxy resin was removed from the last
3in. of the disc electrode shaft to provide a wide space for the fresh epoxy applied in the next
stage. The ring electrode tube was positioned on the disc electrode shaft and the entire
assembly placed through a rubber stopper into the bottom of a long glass tube. Liquid
epoxy resin was poured over the electrode in the glass tube and vacuum applied. Air was
admitted and vacuum re-applied. This process was repeated several times to ensure that the
liquid epoxy resin was forced into all crevices. After curing, the electrode was turned to an
outside diameter of -3 in. and the electrode face polished to a mirror finish using convention-
al metallographic techniques. Electrical contact to the disc was made by means of a wire
which dipped into a pool of mercury placed in a hole drilled in the top end of the disc elec-
trode shaft. Electrical contact to the ring electrode was made using a carbon brush which
contacted a metal tube insulated from the disc electrode shaft by a layer of epoxy resin. This
slip-ring was electrically connected to the ring electrode.
The metal parts of the electrodes fabricated from Teflon were constructed as for the
epoxy electrode. Teflon rod was drilled out slightly smaller than the disc electrode diameter,
heated to 150°C, and press fitted about the disc. After cooling, the Teflon was turned
slightly oversize as compared to the inner diameter of the ring electrode, and the ring elec-
trode was press fitted over the Teflon. Finally, another piece of Teflon was press fitted
about the outside of the ring to complete the assembly of the electrode. A short piece of the
top end of the ring electrode supporting tube was not covered with Teflon and served as the
electrical contact to the ring electrode. The face of the assembled ring-disc electrode was
polished to a mirror finish. Electrodes in long use yielded distinctly low values of N .
Gentle polishing immediately raised the value of N to its original value.
The electrode rotation assembly consisted of a synchronous motor geared to a hollow-
spindle which held the shaft of the electrode. Individual set screws permitted exact centering
of the electrode.
All chemicals were of analytical reagent-grade quality and conductivity-grade redistilled
water was used in preparing solutions. Solutions were de-oxygenated with nitrogen which
had been purified by passage through a heated furnace containing finely divided copper
dispersed in diatomaceous earth.
The electrochemical systems were studied at 25~0°Cand were :
(I) Reduction of cupric to cuprous ion at the disc in 1-Ox 10-4 M CuC12 in 0-5M KCl
and oxidation of cuprous to cupric ion at the ring electrode. co = 39.5,62.9 and 79.0 radians
sec-1, and limiting currents at disc were used.
(11) Oxidation of Br- from a solution of 0.1 M potassium bromide in 1 M sulphuric acid
at the disc electrode and reduction of Br2 at the ring electrode. ci, = 11,22,44, 110 and 196
radians sec-1. The disc current was varied between 0 and 10-3 A using the automatic
current scanning technique described elsewhere.10
 View Article Online
W . J . ALBERY A N D S . BRUCKENSTEIN 1927
(111) Oxidation of a silver plated gold disc in 0.1 M perchloric acid and reduction of
Ag(1) at the ring electrode ; co = 62-9 radians sec-1 ; disc current = 7.8, 19.9, 29-9 and 46.0
PA.
R E S U L T S AND D I S C U S S I O N
Table 4 compares experimental results for N for six electrodes of varying geometry
wi h calculated values for N , Ncalc from eqn. (6.1) and NIL from the Ivanov-Levich
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eqn. (6.4). The new equation for N gives better agreement with experiment than
the earlier approximate treatment. Table 5 gives the percentage difference between
the two predicted values for N , 100(N1~-Ncalc)/Ncalc,for a wide range of a and p.
For large values of a and/or the percentage difference is small and approaches
experimental error ; however, for small a and p, i.e., an electrode with a thin gap and
a thin ring, the earlier formula overestimates the ring current by a substantial amount.
TABLE
4.-cOMPARISON OF CALCULATED AND EXPERIMENTAL VALUES FOR N
A B C D E F
0.3480 0.3888 0.3672 0.3723 0.250 0.2500
0-3860 0.3988 0.3763 0.3817 0.276 0.2738
0.4375 0.4445 0.4369 0.4920 0.359 0.3592
0,3647 0,0792 0,0762 0.0777 0.3456 0.3136
0.6223 0.4151 0,6082 1.230 1-616 1~6524
0.26 1 0-268 0.318 0.414 0.393 0.401
0.303 0.333 0.389 0.488 0.453 0.438
0.264 i 0,266 & 0.328 f 0.430 i 0.37 to 0.38 4
-003 I -0031 *004111 so02 I 0938 2
0.262 & 0.268 f 0.424 & 0-39 2
0002 IL -002 I1 -005 ‘I 0.415 3
average
Nobs 0.263 0.267 0.328 0.426 0.39 0-38
* calc from eqn. (6.1); 7 calc from eqn. (6.4)
Roman numerals refer to system used. Other numbers are references.
TABLE
S.-PERCENTAGE DIFFERENCE BETWEEN NILAND Ncalc

B
V *05 -20 -50 1.00 2.00 3.00 10-00 100*00
-05 28.6 25.7 18.1 11.3 5-6 3.1 - 1.1 - 3.0
-20 27.2 23-2 16.6 10.5 5-3 2.9 - 1.1 - 3.0
*50 23.0 19.5 14.2 9.3 4.8 2.7 - 1.2 - 3.0
1.00 18.4 15.6 11.6 7.8 4.1 2.3 - 1.2 - 3.0
2.00 13.6 11.6 8.7 5.9 3.1 1.7 - 1.3 - 3.0
3.00 11.1 9.4 7.0 4.7 2.4 1.2 - 1.4 - 3.0
10.00 5.3 43 3.0 1.7 -4 - -3 - 1.8 - 3.1
100~00 a1 -*3 -.9 -1.4 - 1.9 - 2.1 - 2.7 - 3.1
Ivanov and Levich 5 claim that their solution holds when “ r2 - r1 4 rz, r3 - r2 4rz ”
or in our notation for small values of a and p. In fact, this is the region where maxi-
mum deviation occurs. They also estimated that the value of N calculated by their
equation is approximately 5 % too high, and as will be seen from table 5 this is a
reasonable estimate of the correction needed for the typical electrodes (E and F in
table 4) used by Frumkin’s school.2 However, this is not the case for electrodes of
other geometries.
The discrepancy of about 3 % on the right of table 5 arises from the numerical
factor of 0.9674 in eqn. (6.4), since for large values of a, eqn. (6.4) becomes 0.9674
[l - F(a/p)]and eqn. (6.1) becomes 1 --F(a//l). With regard to other limiting proper-
ties, both equations correctly predict that N 4 , firstly as a i m , which corresponds
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1928 R I N G - D I S C ELECTRODE COLLECTION EFFICIENCIES

to an infinitely large gap, and secondly when p+O which corresponds to no ring
electrode.
However, when /3 tends to infinity, the ring electrode is infinitely large, all the
intermediate should be recovered, and N should tend to 1. This limiting property is
obeyed by eqn, (6.1),
Ncalc-+ +
1 p + p - F(a)] -pf[l -F(a)] = 1,
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but eqn. (6.4) gives N1~-+0-9674.

When a+O, a hypothetical zero gap electrode, N1~+0-9674[1 -F(ip-l)] while
N,,l,-+l+fl' -(l+p)'. (8.1)
The application of eqn. (2.14) of the previous paper 1 to the no gap electrode gives a
simpler analogue of eqn. (5.3) :
z,Ai(z,)
E(E) =J a)

4 aY y = o 0 s2 UOdZ,, ~

where uo is defined by eqn. (3.1). By similar arguments to that used in the evaluation
of TI in the appendix it may be shown that eqn. (8.1) is the correct form for this hypo-
thetical case. For small values of p we can expand 1 -F(1/4/3) = G(4p) to give
N1~+3f(l-8#?/5. . .), and from eqn. (8.1), Ncalc+p*(l-@B . . .). But for low
values of p, $p, and this explains why NIL> Ncalc in the upper left-hand corner of
table 5.
The p* term is identical in each formula and for hypothetical electrodes with
extremely small values of a and p there would again be only small differences between
the predicted values of N . Such electrodes would, however, be extremely difficult to
construct. In conclusion, N as defined by eqn. (6.1) is in excellent agreement with
experiment and obeys correctly all the limiting properties of a and p.
We thank Messrs. Dennis Johnson and Duane Napp for carrying out the experi-
mental measurements reported in this paper. This work was supported by the
National Science Foundation.
APPENDIX I
This appendix contains the evaluation of the inverse transform in eqn. (5.3). Let
us write

+
where TI is the inverse transform of the first term and T2 T3 is the inverse transform
of the second term.
First, taking TI,by a similar argument to that used in the previous paper 1 eqn.
(2.1%
z2Ai(z2)fdz2 = q
Y-0 Y+O
or

v+o
 W . J . A L B E R Y A N D S. B R U C K E N S T E I N View Article
1929Online

Now from eqn. (3.1)

auo/ay = -exp ( -4y3) = - c (-3y3)"/n!
n=O
+
and uo = 3*l?(1&) a series in y 3 n + l .
Inspection shows that in the q series in eqn. (9.2), when y = 0, all the terms equal
zero except for the first term, and therefore the q series reduces to 34T(l+)q.
For thep series we pursue a similar argument to that used for eqn. (4.2). Replac-
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+
ing 4y3 by x, a term in the expansion of exp( - x) of order n m must be operated on
+
n m times to provide a non-zero value when x = 0. Hence

Taking the inverse transforms and putting t2 = and = 5; we have

However, the hypergeometric series,9

and
F(~1,l;1; -s) = (1 +s)-". (9.3)
Thus

= (3{;)'+(1 +35;)3-(1+35;+3t;)3. (9.4)

Now we return to the second term in eqn. (9.1). Since the Z expression contains
only $1, it may be taken outside the integral and the first step is to find an expression
for
[ y z 2Ai(zZ)Ai(z1)dz2.

Remembering that z1 = (s~/s#z~,and using the relationship given in eqn. (2.17) of

the previous paper 1 we integrate twice by parts to obtain
a, co
z2Ai(z2)Ai(z,)dz2= pq - (sl/s2)*s Ait(z2)Ait(zl)dz2=
0 0

Hence
Pqr1 --(SllS2))1+ SllS2
s:z2Ai(z2)Ai(zl)dz2 = P 4 P -(~11s2)+11(1- S l l S 2 > *

We now invert with respect to s2. Leaving the second Z expression for the moment,
we may write :
1 sn 1 ( & s ~ ) ~ + ' - exp (t;sl)-1
2;
1 - C -L=-n+2
S1 n = O S2
s2
1n=O
c
12+1! sl"
(9.6)

61
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1930 R I N G - D I S C ELECTRODE COLLECTION EFFICIENCIES

and

where the sum

Published on 01 January 1966. Downloaded by University of Virginia on 02/10/2013 16:45:04.

is given by the differential equation

dS r+
- =s+-
di2 W)’
with the boundary condition S = 0 when A = 0.
Then

Substituting from eqn. (9.6), (9.7) and (9.8) in eqn. (9.5), the exponential terms
cancel out to give

We write

d<,
= -2s = 1-(1+3&)3, (9.9)
0 (1+ 3 5 3
where the same argument involving the hypergeometric function (eqn. (9.3)) has been
used.
To evaluate T3,the double Z term, we have to make use of the convolution theorem
and our result for T2 to give

where i2 = ti/&.Now

and we define

By means of the substitution 1 = (1 +3t;)x

3 t N + x)
 W. J. ALBERY A N D S . BRUCKENSTEIN View Article
1931 Online

the first bracket in the integral can be broken down into parts and
T , = (1 +35; +35;)3F[(5;/5;)(1 + +
3ti 3t;)J -(35;)fF(3t;)-F(51’/5,’), (9.10)
or writing a = 35; and p = 35i, we get from eqn. (9.4), (9.9) and (9.10),
N = T,-tTZ+T3 = l-F(alB)+fl’[l-F(a)l-
(1 +&+P)$(l-F[a/P>(l + ~ + p ) ] ) . (9.11)
Published on 01 January 1966. Downloaded by University of Virginia on 02/10/2013 16:45:04.

1 Albery, Trans. Faraday SOC.,1966, 62,1915.

2 Frumkin, Nekrasov, Levich and Ivanov, J. Electroanal. Chem., 1959/60, 1, 84.
3 Nekrasov and Berizina, Doklady Akad. Nauk. U.S.S.R., 1962,142,855.
4 Bruckenstein, Elektrochemiya, in press.
5 Ivanov and Levich, Doklady Akad. Nauk U.S.S.R., 1959, 126, 1029 ; Levich, Physicochemical
Hydrodynamics (Prentice Hall, New York, 1962), p. 329.
6 Levich, Physicochemical Hydrodynamics (Prentice Hall, New York, 1962), pp. 63-69.
7 Handbook of Chemistry and Physics, (Chemical Rubber Publishing Co., Cleveland, 1958),
p. 252.
8 Bruckenstein and Feldman, J. Electroanal. Chem., 1965, 9, 395.
9 Magnus and Oberhettinger, Formulas and Theorems for the Functions of Mathematical Physics
(Chelsea Publishing Co., New York, 1954), p. 7.
10 Albery, Bruckenstein and Johnson, Trans. Faraday SOC., 1966,62, 1938.