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J. Chem. SOC.,Faraday Trans. 1, 1983, 79,2583-2596

Ring-Di sc Electrodes
Part 21 .-pH Measurement with the Ring

AND ERNESTO
BY W. JOHN ALBERY* J. CALVO
Published on 01 January 1983 on http://pubs.rsc.org | doi:10.1039/F19837902583

Department of Chemistry, Imperial College, London SW7 2AY

Received 5th November, 1982

The development of a new ring-disc electrode technique is described in which a bismuth ring
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electrode is used as a potentiometric detector of changes in pH produced by reactions taking

place on the disc electrode. The convective-diffusion equation for the system is solved and
theoretical results are presented for the 'detection efficiency', which compares the change in
pH at the ring electrode with that at the disc-electrode surface. The effects of buffers are
considered. Provided that CO, is excluded, experimental results are found that are in excellent
agreement with the theoretical predictions. Results are presented for the generation of H+ and
OH- on nickel, gold and thionine-modified electrodes. The technique is shown to be very
sensitive in that fluxes as low as lo-', mol cm-2 s-l and changes in coverage of fractions of a
monolayer can be measured.

In the normal use of a ring-disc electrode,l intermediates or products of an

electrochemical reaction on the disc are swept outwards and measured on the
downstream ring electrode. The ring electrode is used as an amperometric detector
and is set at a potential which destroys all the target species reaching it. In this paper
we report the development of a ring electrode made of bismuth which is used in the
potentiometric mode to measure changes in pH caused by reaction taking place on
the disc. Various metal/metal oxide systems such as palladium,2 iridium,2 antimony3
or bismuth314can be used as pH electrodes. We chose to work with antimony and
bismuth since these electrodes can be prepared by room-temperature electroplating.
We found that the bismuth electrode was more easily prepared and performed better
than the antimony electrode. This paper therefore concentrates on the bismuth
electrode. We have previously considered potentiometric detection on the ring when
the electrochemical system is reversible5 or when it is irreversible6 with both the
reduced and oxidised species being soluble in the aqueous phase. The bismuth pH
sensor responds only to the pH of the solution and we therefore have to consider only
the distribution of pH in the vicinity of the ring-disc electrode.

THEORY
The convective diffusion equation for the rotating ring-disc electrode is7

where C = 8.0 W b ; , W is the rotation speed in Hz, v is the kinematic viscosity, r

is the radial distance, x is the distance normal to the electrode, c is the concentration
of either H+ or OH- and D is the diffusion coefficient of either H+ or OH-. Eqn (1)
is transformed by writing'
Y = (r/r1) ( C / D Y X
r = $[(qq)3-
13 (2)
2583
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2584 RING-DISC ELECTRODES

and u = ( c - c,)/c, (3)

where Y, is the radius of the disc and c , is the bulk concentration to give

Next we split u into two components

u = uD-u* (5)
Published on 01 January 1983 on http://pubs.rsc.org | doi:10.1039/F19837902583

where uD describes the concentration profiles in the zone of the disc. In this zone
u* = 0. For r > rl beyond the disc u* describes the difference between c and the disc
profile. Both uD and u* obey eqn (4).
We assume that the potentiometric detector has a very low exchange current, so
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that the flux of c at the surface of the electrode for both the gap and the ring detector
can be taken to be zero. So from eqn (2)-(5) for r > rl we have the following
boundary conditions :
c = o u*=o (6)
y+oo u*=o (7)

The usual Levich solution* for the disc electrode states that

From eqn (2), (8) and (9) we then find that the boundary condition at y = 0 becomes

Solution of eqn (4) for u* with the boundary conditions (6), (7) and (10) is carried
out by the usual Laplace transformation of the radial variable9 to give

The inverse transform is evaluated in the Appendix, which shows that

where B is the incomplete beta functionlo

'z(i79.= lo
5 t-%
(1dt

By means of the substitution t = 3, (1 + L)-l one can show that

'A499 = (2n/d3)F"x/(l--43

where F(8) is our previously defined function'

3;
(-)
(1+@)3
F(8) = 4.n In i + e
3
+-
2n tan-1 (s:).:.
2@- 1
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W. J. ALBERY AND E. J. CALVO 2585

t -------B-
GAP
RING
Published on 01 January 1983 on http://pubs.rsc.org | doi:10.1039/F19837902583
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0.01 I I
0.00 0.10 0.20
r/rl -1
Fig. 1. Plot of eqn (14) describing the concentration of electrogenerated species as a function
of the radial distance in the zones of the gap and of the ring electrode. The geometry of the
two electrodes used in this work is also shown.

Substitution of eqn (12) and (13) in eqn (1 1) together with evaluation of the constants
gives
uo/uD, = 1 -F[(r/r1)3- 11.
This equation is plotted in fig. 1. It describes the drop in the concentration of H+ or
OH- generated on the disc as one moves outwards in a radial direction across the
electrode surface. The plot starts at the outside edge of the disc (r = r l ) and as r
increases uo declines to zero, where from eqn (3) the concentration will be same as
in the bulk.
We also show in fig. 1 the location of the ring electrode for our electrodes (see below).
The bismuth electrode will measure an average value of c. Although no net current
flows through the electrode there will be a small inward flux of c on the inside edge
of the ring electrode and an equal small outward flux on the outside edge of the ring
electrode. The potential of the electrode will be such that these two fluxes exactly
balance giving no net current. Because of the low exchange-current density of the
electrode we assume that these fluxes make a negligible perturbation to the concen-
tration profile depicted in fig. 1. At one particular radial distance, across the ring
electrode, the flux will be zero and the value of c, E, at this radial distance will be the
value measured by the electrode. We assume that the inward and outward fluxes are
proportional to the difference c- c". The condition for zero current then becomes

Substitution for u and rearrangement gives

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2586 RING-DISC ELECTRODES

In eqn (1 5) we have introduced the equivalent of the collection efficiency; we propose
to call this ratio the 'detection efficiency', ND.
Substitution of eqn (14) into eqn (15) gives an integral for which we cannot find
an analytical solution. However, we have shown that results which are accurate to
within 1 % may be obtained by first treating r as a constant equal to 4(r2+ r,) in the
integral in eqn (1 5). This approximation is justified since the usual electrode geometry
is for the ring to be thin compared with the disc radius. We can then use Simpson's
rulell to carry out the integration
+ +
Published on 01 January 1983 on http://pubs.rsc.org | doi:10.1039/F19837902583

ii: = 34,) 34[4(r2 r,)] +&4(r3).

Substitution into eqn (1 5) gives
ND = 1 -4F[(:),- l]-jF[(--)'-r 2 + r 3 l]-)F[(:Y- 11. (16)
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2%
Like the collection efficiency ND is just a function of the geometry of the electrode.
We now relate c" as measured on the ring electrode to the disc current generating
c. From the Levich equation8

where Z D , is the diffusion length for W = 1 Hz, ZD, = 0.64 v i a and n is the number
of electrons for H+ or OH-. From eqn (3)' (15) and (17)

The response of c" to liDl depends on rotation speed because at high rotation speeds
the products of the disc reaction are swept away and do not build-up to such a large
concentration in the diffusion layer. Hence the experiment is more sensitive the lower
the rotation speed.
SELF-BUFFERING ACTION OF WATER
For experiments where the pH is greater than 8 we consider c to refer to OH- and
do not have to worry about the insignificant concentration of H+. Similarly for pH < 6
we consider c to refer to H+ and we do not worry about OH-. However, for
experiments near pH 7 we have to consider both H+ and OH-. In particular we will
consider the most sensitive sort of experiment when the pH of the bulk solution is
7. We then write the equivalent of eqn (1) for both H+ and OH-. We assume that
the diffusion coefficients are equal and subtract the two equations to obtain
- a2(a- b) a(a - b) a(a -b)
D-=-Cx2- +Crx-
ax2 ax ar
where a = [H+] and b = [OH-]. Now at a bulk pH of 7 , a equals b in the bulk of the
solution. Hence (a- b) obeys the same differential equation and the same boundary
conditions as c in eqn (1). Hence from eqn (15)
(a -b)R = ND(a-b)D. (19)
Now on the disc surface as in eqn (17)
liDl = nFnr,2DV21(a- b),JZ,, (20)
We also have that ab = Kw. (21)
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W. J. ALBERY AND E. J. CALVO 2587

where c can be either a or 6 . In eqn (22) the term K,c-l plays the same role as c ,
in eqn (18). However, it will be < lo-’ mol dmP3and hence c is less because some
OH- has to titrate the H+ and vice versa.
EFFECTS OF OTHER BUFFERS
Published on 01 January 1983 on http://pubs.rsc.org | doi:10.1039/F19837902583

We now examine the effect on the response of the ring electrode of a buffer in the
solution where [HA] = a’, [A] = b’ and the dissociation constant of HA is K . We
consider the case where c is H+, and again we assume that all diffusion coefficients
are equal. In this case we form the equivalent of eqn (1) for b and add it to eqn (1)
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itself to obtain
+
a2(c a’)
= - cx2-
a(c a’) + +
Crx-.
t3C

a22 ax ar
We define u = (c +a’ - c , -a ; ) / ( c , + a;). (23)
Since on the disc (aa’/ax), = 0 we have that on the disc surface

and since a obeys the same differential equation and boundary conditions as before
we have from eqn (15)
uR = ND (%ID* (25)
Now throughout the solution
a‘+b‘= a;+b‘, (26)
and for the fast proton transfers
b’c = Ka‘.
From eqn (26) and (27) both at the disc surface and in the bulk
a’ = c (a; + b’,)/(K+ c). (28)
From eqn (23)-(25) and (28) we find

The effect of the buffer is described by the term

If this term is large then the ring response will be destroyed. We now consider three
~~

approximations for B :
(a&+b;) K
(1) c o > c , > K B w
co c,

(2) c, > K > c , B w (ado +bdo)

CO
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2588 RING-DISC ELECTRODES

Inspection shows that B is largest for condition (2). This conditioli corresponds to
the buffer being all in the form of HA on the electrode surface and all in the form
of A in the bulk of solution. The flux of H+ has to titrate the buffer. Assuming for
this case that c , < c, we then obtain from eqn (29)

The ring response is reduced by the total concentration of buffer species in the
Published on 01 January 1983 on http://pubs.rsc.org | doi:10.1039/F19837902583

solution. For conditions (1) and (3) the effect is less serious since throughout the
solution the buffer species are predominantly HA and A, respectively. However, eqn
+
(29) and (30) show that to measure small values of c, it is vital that (a’, b’,) should
be as small as possible.
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Table 1. Ringdisc electrodes

electrode disc/ring rl/cma r,/cmb r3/cmc N,[eqn (W1

A Ni/Au 0.324 0.375 0.401 0.357

B Au/Au 0.357 0.377 0.397 0.497

a Radius of disc electrode; inner radius of ring electrode; outer radius of ring electrode.

EXPERIMENTAL
APPARATUS
Ringdisc electrodes were made in the normal manner’ with gold rings. Details are given
in table 1. The bismuth was electroplated onto the ring electrode following the procedure of
Harborough and Mathers.’, Before each set of experiments the bismuth electrode was polished
with 0.3 pm alumina. To measure its potential, the ring electrode was connected to a voltage
follower. For each set of experiments the response of the bismuth electrode was calibrated
against a glass electrode, see fig. 2 below. All potentials were measured and are reported with
respect to the saturated calomel electrode.
CONTROL OF BULK pH AND ELIMINATION OF co,
The purpose of these experiments is to monitor changes in pH. This means that the solution
cannot contain a buffer. We have therefore controlled the pH of the bulk solution using a Radio-
meter pH stat. In order to keep the buffer capacity as low as possible it is important to exclude
CO,. The following precautions were therefore taken. First, a rotating water seal was fitted to
the shaft of the disc drive. Unfortunately too much CO, could still enter the cell and so this
whole drive assembly was fitted with a cylindricaljacket which was flushed with argon. (Argon,
being heavier than air, proved more effective than nitrogen.) Secondly, all solutions were freshly
made up in a glove-box flushed with N,. The best results could not be obtained with solutions
that were more than a day old. Thirdly, ‘carbonate free’ AnalaR NaOH was used. Fourthly,
water from the solutions was doubly distilled under N, from alkaline KMnO, and always
handled under N,.
All reagents were of AnalaR grade. The argon (B.O.C., HP) was purified by bubbling through
Dreschel bottles containing first alkaline KMnO, to remove SO, and NO, secondly NaOH and
then SrCl, to remove CO, and finally the working solution ; all pipework in the gas train was
made of copper rather than plastic. The experiments were carried out in 0.1 mol dm-3 NaC10,
solution. All experiments were carried out at 298 K.
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W. J. ALBERY AND E. J. CALVO 2589

RESULTS AND DISCUSSION

RESPONSE OF THE BISMUTH ELECTRODE
In fig. 2 we show a typical calibration plot of the bismuth ring electrode potential
against pH as measured by a glass electrode; the disc electrode was at open circuit
and in equilibrium with the solution and the rotation speed was 9 Hz. In general we
find the relation
E/mV = EpH - (50 f5 ) pH. (31)
Published on 01 January 1983 on http://pubs.rsc.org | doi:10.1039/F19837902583

This is in reasonable agreement with the results of Strafelda and Singer13 who also
used a rotating-disc electrode. Less reliable results seem to be obtained on stationary
electrode^.^
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>
E
-200

-400

Fig. 2. Response of bismuth ring electrode (B) to pH as given by eqn (31).

CONTROL OF co,
In the experimental section we describe the precautions which are necessary to
prevent CO, (and possibly other acidic gases) from providing too much buffer capacity
in the solution. In fig. 3 we show pH titration curves of the bulk of the solution
obtained on a Radiometer pH stat where the pH of the solution was measured (on
a conventional glass electrode) as NaOH was added. The full line shows the theoretical
curve for a solution of zero buffer capacity. The other two curves are experimental
results, one when no precautions have been taken and the other where the full
procedure described above has been followed. The latter curve is close to the
theoretical curve and under these conditions no correction has to be made for
interference from HCO; etc. We estimate that the concentration of unwanted buffer
species is ca. 1-10 pmol dm-3.
THEORETICAL RESULTS FOR ND
We now turn to the detection efficiency for the ring-disc electrode. First in table
2 we report results for N D calculated using eqn (1 6) for electrodes of common radius
ratios. In general, ND is some two to three times larger than No, the collection efficiency
for the amperometric ring-disc experiment. This is because in the amperometric mode
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2590 RING-DISC ELECTRODES

there is a considerable loss of material from the centre of the disc electrode. It is also
interesting that N,, decreases with increasing width of the ring electrode. This is the
opposite to the case of amperometric collection and arises because the electrode is
sampling regions of lower concentration as the width of the ring electrode increases
(see fig. 1).

1c
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%,

4
50 100
concentration/pmol dm-3

Fig. 3. Typical pH titration curves of the bulk solution. The solid line shows the expected
response for zero buffer capacity; the open circles show the experimental response when
insufficient precautions to remove CO, have been taken; the closed circles show the response
when all the precautions described in the text have been taken.

Table 2. Values of N , calculated from eqn (16) for typical electrode geometries

r3/r2 1.02 1.03 1.04 1.05 1.06 1.07 1.08 1.09 1.10

1.02 0.635 0.599 0.569 0.544 0.522 0.501 0.483 0.467 0.452
1.03 0.617 0.584 0.556 0.532 0.51 1 0.492 0.475 0.459 0.444
1.04 0.602 0.571 0.545 0.522 0.50 1 0.483 0.466 0.45 1 0.437
1.05 0.588 0.559 0.534 0.512 0.492 0.475 0.459 0.444 0.430
1.06 0.575 0.547 0.524 0.503 0.484 0.467 0.45 1 0.437 0.424
1.07 0.563 0.537 0.514 0.494 0.476 0.459 0.444 0.430 0.4 17
1.08 0.552 0.527 0.505 0.486 0.468 0.452 0.438 0.424 0.41 1
1.09 0.542 0.518 0.497 0.478 0.46 1 0.445 0.43 1 0.418 0.406
1.10 0.533 0.509 0.489 0.470 0.454 0.439 0.425 0.412 0.400
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W. J . ALBERY AND E. J. CALVO 259 1

EXPERIMENTAL RESULTS FOR THE DETECTION EFFICIENCY

Fig. 4 shows typical experimental results for the ring-electrode potential as the disc
current generating H+ (upper set of curves) or OH- (lower set of curves) is increased.
In this paper the pH of the bulk solution is 7. The H+ and OH- have been generated
by galvanostatting a Ni disc electrode (electrode A). In fig. 5 and 6 all of the results

1 1'
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0.0
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- 0.4 t

0.00 0.0 5 0.10

iD /mA
Fig. 4. Response of the ring electrode (A) to the generation of H+ (upper set of curves) and
of OH- (lower set of curves); the bulk pH was 7.0. The rotation speeds (in Hz) were as follows:
(a) 2, (b) 4 ( c ) 9, (4, 16 and (e) 25.

in fig. 4 are plotted according to eqn (18). For these experiments c, is negligible. Good
straight lines are obtained for data obtained at five different rotation speeds and five
different currents. Using eqn (30) for the effects of unwanted buffers the small
intercepts correspond to concentrations of the order of mol dm-3 and this value
is typical of the residual buffering action seen in fig. 3. In table 3 we compare the
gradients of fig. 5 and 6 with those calculated from eqn (18). Very good agreement
is found confirming the theory of the electrode and the response of the bismuth pH
sensor. It is interesting that the differences in the gradients and in the two sets of
curves in fig. 4 arise from the difference between D,+ and DOH-.To emphasise the
importance of the removal of CO, in fig. 6 we also show some early results obtained
with the same electrode when insufficient precautions had been developed.
TRANSIENT RESPONSE
Fig. 7 shows the response of the ring electrode [fig. 7(b)Jto a galvanostatic pulse
of disc current lasting 90 s [fig. 7(a)].It is gratifying that when the current is switched
on, the ring electrode responds within 5 s. On switching off the disc current, which
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2592 RING-DISC ELECTRODES

Published on 01 January 1983 on http://pubs.rsc.org | doi:10.1039/F19837902583
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( i D /E.tA)WIHz)-~

Fig. 5. Plot of c" from H+ data in fig. 4 according to eqn (18). Rotation speeds (in Hz) were
as follows: 0 , 2; 0,4; x , 9; +, 16 and 0 , 2 5 .

(iD /PA)( W I H ~ ) - +
Fig. 6. Plot of c" from OH- data in fig. 4 according to eqn (18). Rotation speeds are indicated
as in fig. 4. The curve shown by A is a typical result when insufficient precautions are taken
to remove CO,.

was done by disconnecting the disc electrode, much slower responses are seen on the
ring electrode. These slower responses must be caused by the slow release of OH- from
the nickel surface. In fig. 7(c) we convert these responses, using eqn (18), to a flux
of HO-,joH-, where in eqn (18) we replace liDl/nFzrf withjOH-.It is satisfactory that
the calculated fluxes of OH- from the nickel surface at the three different rotation
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W. J. ALBERY AND E. J. CALVO 2593

Table 3. Comparison of theoretical and experimental gradientsa

theoreticalb experimentalC

anodic (H+) 1.66 x 10-3 (1.7k0.2) x

cathodic (HO-) 2.46 x 10-3 (2.7 f0.3) x
Published on 01 January 1983 on http://pubs.rsc.org | doi:10.1039/F19837902583

a The units are mol cm-3 A-l Hz-t; calculated from eqn (18); from fig. 5 and 6.
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1 !

I
I
I I
I
I
I
1P

I ;I
I;,
I I "\
I I \.
II I %%
3-C- . rl I
0 0 100 200
tls
Fig. 7.Typical transient behaviour of a nickel disc electrode (A). (a) Rectangular pulse of current
on the disc electrode. (b) Response of the ring electrode at three different rotation speeds: upper
curve 1 Hz (a),middle curve 2 Hz (O), lower curve 4 Hz (0). (c) Flux of OH- at the disc
surface calculated using eqn (1 8) from the results in (b).
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2594 RING-DISC ELECTRODES

speeds are in excellent agreement. This shows first that the slow transient is not an
artefact of the bismuth electrode. Secondly it shows that the slow release of OH- from
the nickel surface is an irreversible reaction which is insensitive to the concentration
of OH- in the solution; identical kinetic behaviour is observed even though the ring
electrode has different pH time transients at the different rotation speeds. Thirdly it
is a measure of the sensitivity of this new technique that fluxes as low as ca.
10-l2 mol cm-2 s-l can be measured. Integration shows that the total amount of OH-
released was 6.9 x mol cm-2, which corresponds to a monolayer for a roughness
factor of 2.4.
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- 0.1 6.0

.
>
-02
4* 7.0 5

- 0.2 3.0
- 0.5 0 0.5
E,IV
Fig. 8. (a) Cyclic voltammogram of a modified thionine electrode (electrode B). (b) Resulting
pH-ogram seen on the ring electrode (-); the broken line (- - -) is the calculated response
using the data in fig. 7 ( a )and eqn (22).

CYCLIC pH-OGRAMS
Fig. 8 and 9 show the response of the ring electrode as cyclic voltammetry is carried
out on the disc electrode. In the first case the disc electrode was a modified thionine
electrodel* (electrode B) with some fifteen layers of thionine. At pH 7 the redox
reaction is
H

In fig. 8 we can see that the response of the ring electrode matches the change in
charge in the modified electrode. Using eqn (22), which allows for water buffer action,
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W. J. ALBERY AND E. J. CALVO 2595

and with n = 2, we can calculate from the cyclic voltammogram the expected change
in ER for the ring electrode. This is also shown in fig. 8. Reasonable agreement is found
between the theoretical and experimental curves.
Fig. 9 shows a similar experiment on the gold electrode (electrode B) at pH 7.
Again there is good agreement between the shapes of the voltammogram and the
pH-ogram. In this case if we calculate the expected ring response, using eqn (20), and
assuming a direct one-to-one correspondence between the flux of electrons and the
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I I

-0.15- 6.O

.
>
LLP %
- 0.20 - 7.0

- 0.25 - a0

ED/V
Fig. 9. (a) Cyclic voltammogram at a sweep rate of 2 m V s-l of a gold disc electrode (electrode
B). (b) Resulting pH-ogram on the ring electrode (-) and the calculated response from eqn
(22) (- - - -).

flux of H+ or OH-, the results in fig. 9 show that the experimental response is less
than the expected response. This may be because some OH- is adsorbed on the gold
surface or it may be caused by the residual buffering action of the solution. In any
case the experiment again demonstrates the sensitivity of the new technique. The
monitoring of local pH changes on complicated electrode systems such as modified
electrodes, oxide electrodes such as perovskites or enzyme electrodes should provide
us with valuable information on the kinetics and mechanism of these complicated
electrode systems. Far from being consigned to the museum,15the ring-disc technique
is proving as powerful as ever.

We thank the S.E.R.C. for financial support and are more than usually grateful to
Mr M. Pritchard who constructed the ring-disc electrodes. This is a contribution from
the Oxford Imperial Energy Group.
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2596 RING-DISC ELECTRODES

APPENDIX
In this appendix we evaluate the inverse transform in eqn (12). We use the convolution
+
theorem and the substitution t = 3R/( 1 3 5 ) to write

where B is the incomplete beta function.I0

Published on 01 January 1983 on http://pubs.rsc.org | doi:10.1039/F19837902583

W. J. Albery and M. L. Hitchman, Ring-Disc Electrodes (Oxford Science Research Papers, Clarendon
Press, Oxford, 1971).
W. T. Grubb and L. H. King, Anal. Chem., 1980,52, 270.
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D. J. G. Ives and G. T. Janz, Reference Electrodes, Theory and Practise (Academic Press, New York,
1961), chap. 7.
H. M. Sammour and A. A. Moussa, J. Chem. SOC.,1952, 1762.
W. J. Albery, S. Bruckenstein and D. T. Napp, Trans. Faraday SOC.,1966,452, 1932.
W. J. Albery and S. Bruckenstein, Trans. Faraday SOC.,1966, 62, 2596.
' W. J. Albery and S. Bruckenstein, Trans. Faraday SOC.,1966, 62, 1920.
* V. G. Levich, Physicochemical Hydrodynamics (Prentice Hall, Englewood Cliffs, N.J., 1962), p. 69.
W. J. Albery, Trans. Faraday Soc., 1966, 62, 1915.
l o M. Abramowitz and I. A. Stegun, Handbook of Muthematical Functions (Dover, New York, 1965),
p. 263.
l 1 M. Abramowitz and I. A. Stegun, Handbook of Mathematical Functions (Dover, New York, 1965),
p. 886.
** M. Harborough and F. C. Mathers, Trans. Electrochem. Soc., 1933, 64, 293.
l 3 F. Strafelda and E. Singer, Collect. Czech. Chem. Commun., 1966, 31, 3042.
l4 W. J. Albery, M. G. Boutelle, P. J. Colby and A. R. Hillman, J. Electronanal. Chem., 1982, 133, 135.
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(PAPER 2/ 1860)