Theory of Square Wave Voltammetry

Louis Ramaley and Matthew S . Krause, Jr.1

Department of Chemistry, University of Arizona, Tucson, Ariz. 85721

When the sum of a synchronized square wave and staircase potential i s applied to a stationary electrode, the double layer charging current may be made negligible by measurement at a suitable time after the pulses occur. The staircase allows the electrode potential to be swept over the useful potential range. The theory for a reversible system predicts that the resulting current-time behavior should be symmetrical and bellshaped with a peak at El/*. The peak current is a linear function of concentration and the square root of the square wave frequency. The peak current is a more complicated function of square wave amplitude, measurement time, and staircase amplitude. The similarity between this technique and square wave polarography is discussed.

THEUSEFULNESS of square wave polarography as developed by Barker ( I ) is well established in trace analysis. The ability to present the current output in the form of a symmetrical peak, rather than the waveforms obtained in dc polarography or linear sweep voltammetry, and the ability to measure Faradaic current at a time when the double layer charging current is negligible, are primarily responsible for its success. The sensitivity is limited by capillary noise (2) and the necessary resolution is obtained only at sweep rates of 1 V in 10 to 60 minutes. The use of stationary electrodes should eliminate capillary noise and allow rapid scan rates while maintaining high resolution. Mann (3, 4 ) has applied a staircase potential waveform to stationary electrodes and significantly reduced the effect of double layer charging current. The current waveforms obtained were similar to those of linear sweep voltammetry. The superimposition of a square wave on the staircase potential should result in higher sensitivity than in the case of the staircase alone, and a derivative or peak current waveform similar to that of square wave polarography should be observed. The waveforms for this technique, which the authors propose be called square wave voltammetry (SWV), are shown, somewhat exaggerated, in Figure 1. Since the potential sweep is discontinuous rather than linear, the tops of the pulses remain flat, even at rapid sweep rates. Since the double layer charging current is proportional to e-IIRC,where t is time, R is the solution resistance, and C is the double layer capacitance, and the Faradaic current is approximately proportional to t - l / * , the charging current decays much more rapidly than the Faradaic current, allowing measurements to be made at a time when the charging current can be considered negligible. The final current waveform is the differential sum of the current flowing at an instant, selected to reduce the effect of the charging current, along the cathodic half cycle of the square wave and that flowing at the same instant along the preceeding or following anodic half cycle.
1 Present address, E. I. du Pont de Nemours & Co., Inc., Marshall Research Laboratory, 3500 Grays Ferry Ave., Philadelphia, Pa. 19146

MEASURED CURRENT

DIFFERENTIAL CURRENT

n
TOTAL DIFFERENTIAL CURRENT

El/*

E -

[-)

Figure 1. Waveforms employed and obtained in square wave voltammetry

THEORY

Barker et al. (9,Matsuda (6), and Kambara (7) have discussed the theory of square wave polarography. Christie and Lingane (8) have derived an equation for staircase voltammetry. The theory presented below for square wave voltammetry is approached in a manner similar to that of Barker et al. and Kambara. The current resulting from the application of the potential waveform of Figure 1 to an electrode at which the reversible reaction Ox

+ ne-

+ Red

can occur may be easily determined if semi-infinite linear diffusion to the electrode is assumed. It has been demonstrated (5, 7) that for a planar electrode and a reversible redox couple, the concentrations at the electrode surface are functions only of the electrode potential and the bulk concentrations and not of any previous potential established at the electrode. Barker, R. L. Faircloth, and A. W. Gardner, Atomic Energy Research Establ. (Gt. Brit.) C/R-1786. (6) H. Matsuda, 2.Elektrochem., 60,489 (1957). (7) T. Kambara, Bull. Chem. SOC. Japan, 27 527 (1954). (8) J. H. Christie and P. J. Lingane, J. Electroanal. Chem., 10,
( 5 ) G. C .

(1) G. C. Barker and I. L. Jenkins, Analyst, 77,685 (1952). ( 2 ) G. C. Barker, Anal. Chim. Acta, 18, 118 (1958). CHE. ~~, (3) C. K. M ~ ~ ~ , A N A L M . ,1484(1961). (4) C. K. Mann, ibid.,37, 326 (1965).
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ANALYTICAL CHEMISTRY

176 (1965).

where DO is the diffusion coefficient of the oxidized species. The current may be obtained in the usual manner by differentiating Equation 2 with respect to .r and setting x = 0 in the resulting expression. This produces

The Cs may be obtained from the following expressions

c, =
/ /

(1 - (E,( E exp
-

exp

) ~- El _ nFiRT _ _ . - El . nF RT )

C*Q,

(4)

In the above expressions, . is the electrode area, Dn the dif4 fusion coeffiiiznt of the rzduced species, and the other symbols have their usual meaning. If it is further specified that the current will only be measured at a certain time during each half period of the square wave, then
t = ( j - 1)r T 87 0</3il (6) where p is the fraction of the square wave half period at which the current is measured. Substituting Equations 6 and 4 into Equation 3 results in

AE

( m ~ )

Figure 2. Effect of LIE on measured current (1)

The initial and boundary conditions may be stated as follows: at t

=

0, Cox = C*, CII~~I 0, 0 5 x 5 =

for and for

r > 0, Cox

C*, CRcd

- 0, x

03

< 7 (C,,),,, = c 1 7 < r < 27 (Co,)z_o C? = ( j - 1 ) < t < j r ( C O ~ ) ,=~C, ~ - ~

0<

To obtain the differential sum of the currents flowing during the anodic and cathodic half cycles, the current flowing during an even value of j is subtracted from that flowing during the preceeding or following odd value ofj, or
i,,,, = i,
iclif =

where t is time? x is distance from the electrode surfacc, and Cj is the concentration of the oxidized species established by electrode potential E, during thejtb half period, T , of the square wave. Ficks second law of linear diffusion

- i,-.: i,-] - i,
QI

fori forJ

= =

1, 3, 5 , 7 . . , 2, 4, 6 , 8

The ditkrzntial current thus becomes

I,,,f

= nFADo/C*
?,I
2

( -l)J[Ti-1T-p
1

-I

?c% Do d?COx at

ax

(1)

Q, - 281 -~. $. , 1 ( j - 2 + p?)l2

$. ~. - 2Q Q 1---~-1-1-..
(!3)1
?

Qj-z

may be solved using the method of the Laplace transform (9, 10, 11) in conjunction with the superposition principle (Z2) to give the following expression for the concentration of oxidized species as a function of distance and time

or

-t
(C, - C, - J erfc _ _ 2D01[t - ( j
X

- ~)TI, 2

(9) P. Delahay, New Instrumental Methods in Electrochemistry, Interscience, New York, 1954, p 46. (10) R. V. Churchill, Operational Mathematics, 2nd ed., McGraw-Hill Book Co.. Inc., New York, 1958. (1 1) H. S . Carslaw and J. C . Jaeger, Conduction of Heat in Solids, 2nd ed., Oxford University Press, London, 1959, p 62. (12) J. Crank, The Mathematics of Diffusion, Oxford University Press, London, 1956, p 9.

where Qo and Q-I are both unity. The above equations are strictly valid only for planar electrodes and for liquid electrodes of large volume if the reduced species is soluble in the electrode. At the measurement times encountered in such work, the diffusion layer thickness a t a spherical electrode is usually small compared to the radius of curvature of the electrode and the above equations will be valid. However, for reactions in which the reduced species is soluble in the electrode, the semi-infinite diffusion assumption will be invalid and the above equations will only be approximations for electrodes of small volume. It can iinmediately be seen that the difTerentia1 current is a linear function of the bulk depolarizer concentration and is directly proportional to r - I t 2 or to , f 1 ! 2 where ,fis the square wave frequency. In order to determine the other characteristics of the differential current, the summation in Equation %-hereafter referred to simply as 2-must be carried out. Calculations
VOL. 41, NO. 11, SEPTEMBER 1969

1363

a0

65

'c
6.0

' 0

I 0.3 0.9
0.1

02

0.4

0.5

0.6 0.7

0.8

1.0

P
Figure 3. Effect of /3 on measured current (2) at constant 7

4.50

5'0
I 2

IO

(msec:

Figure 4. Combined effect of T and p (measure instant) on measured current ( T - '12 2 ) COMPARISON WITH SQUARE WAVE POLAROGRAPHY

demonstrate that 2 , and therefore i d i f , are maximum at EIl2 and that the peak is bell-shaped and symmetrical as shown in Figure 1. The half-width of the peak is a function of n and AE, the peak-to-peak square wave amplitude. As long as A E < O.SRT/nF, the half-width is 90.5 mV for n = 1, 45.3 mV for n = 2, and 30.2 mV for n = 3. The half-width increases slightly as A E becomes larger than RT/nF-for example, a one-electron reaction and a square wave amplitude of 50 mV produce a half-width of 98.8 mV. The dependence of Z: on A E is shown in Figure 2. The calculations for this figure were performed with p = 0.60 and E,,, = -0.20 mV. Again, as long as A E < O.SRT/nF, Z is linear in A E and also linear in n. This has the result that the differential current is proportional to n 2 a t small AE. The effect of p on Z: is demonstrated in Figure 3 , where A E = 10 mV, EjtOP = -0.20 mV, and n = 1. This figure indicates that the highest sensitivity should be obtained with the smallest 0 at which the double layer charging current is negligible. The usual practice in square wave polarography is to make T as small as possible and set /3 a t 1.0, thus making T - large and Z small. ~ ~ ~ A slight gain in sensitivity can be obtained by making T large and p as small as instrumental factors will allow. This is shown in Figure 4, where again A E = 10 mV, Est,, = -0.20 mV, and n = 1. The points in this figure were calculated for a constant measure instantthe time after the square wave polarity change at which the current i s measured-of 500 psec by suitable adjustment of p and T . Sweep rate may be altered in two ways, by changing T or by changing E.,,,, the amplitude of the staircase waveform. The effect of T on differential current has already been discussed. The effect of E,,, is shown in Figure 5 , where n = 1, (3 = 0.60, and Z0is the value of Z for E,,,, = 0.0. This effect may be looked upon as a distortion of the square wave by the staircase wave. For example, if A E is 2.5 mV and Estepis -0.5 mV, the cathodic pulse will be -2.5 mV while the anodic pulse will be only +2.0 mV, a difference of 2 0 x . The result may be looked upon as a square wave with a n average amplitude of 2.25 mV, a distortion of 10% as indicated in Figure 5 . If ELtep summed with the cathodic half cycle rather than was the anodic half cycle, the current would tend to increase as Est,, was made larger, rather than decrease.
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ANALYTICAL CHEMISTRY

The above results are similar to those predicted by the theory of square wave polarography as originally presented by Barker et al. (5) provided that A E < 0.5 RTlnF. The equation derived by Barker et al. is

where P = exp(E - E1i2)RT/nF the other symbols have the and same significance as above. Equation 9 was derived assuming

AE
50 mV

20 mV

5 mV

0.88 0 -0.05-0.1

-0.2

- 0.5

Figure 5. Effect of square wave distortion (Estep) measured on current (2)

that AE < RTjnF, and that the average electrode potential < remained constant. The summation in Equation 9 does not converge rapidly, indicating that a large number of cycles of the square wave potential should occur before the current predicted by Equation 9 approximates that actually measured. Normally, at least 200 cycles pass before the measurement is completed. In this light it may seem surprising that Equations 9 and 8 produce similar results. The agreement between Equations 9 and 8 may be explained by considering the result for square wave polarography after any finite number of cycles.

In addition to the assumptions made in deriving Equation 9, Equation 10 has the additional restriction that the electrode is prebiased at some potential Eo before application of the square wave potential, and that on application of the square wave, the electrode potential oscillates between Eo and some more cathodic potential. Equation 10 reverts to 9 when j goes to infinity. The terms in the second brackets of Equation 10 very closely

approach the summation of Equation 9 (carried to infinity) after only a few terms. In the worst case (@= 1) Equations 9 and 10 agree within 1 after five cycles of the square wave have occurred. Thus, if the square wave polarograph is operated according to the restriction imposed in deriving Equation 10, Equation 9 is a very good approximation to the actual current after only a few cycles of the square wave have occurred. In square wave voltammetry, the current flowing a t any time could be considered the result of the application of four or five square wave cycles to an electrode prebiased at a given potential if Eatep were very small compared to A E so that the average electrode potential did not change appreciably during the four or five cycles. Equation IO could be applied to this case, and Equation 9 would be a good approxiniation. Thus, if the square wave distortion is small, square wave voltammetry and square wave polarography produce the same results. The experimental verification of the above theory is presented elsewhere (13).

RECEIVED review May 1, 1969. Accepted June 2, 1969. for

(13) M. S. Krause, Jr., and L. Ramaley, ANAL.CHEM., 1365 41, (1969).

Analytical Application of Square Wave Voltammetry

Matthew S.Krause, Jr.,l and Louis Ramaley
Department of Chemistry, University of Arizona, Tucson, Ariz. 85721

The previously proposed theory for square wave voltammetry (SWV) i s verified by results obtained using the iron (111/11) oxalate redox system. The method used to generate the potential-time waveform and the operation of the instrument are briefly described. The application of this technique to analysis i s examined and detection limits-e.g., 2.5 X 10-8M for n = S f o r representative redox couples are presented. The results indicate that SWV offers most of the advantages of square wave polarography and is accomplished in much shorter analysis times, inasmuch as sweep rates of 50 sec/V or less are employed as opposed to the 1060 min/V rates used in square wave polarography.

IN VOLTAMMETRIC electroanalytical methods, the minimum measurable Faradaic current is usually limited by the magnitude of the double layer charging current. The use of a discontinuous potential change, as in square wave polarography ( I , 2), has been very successful in reducing the effect of this charging current. Square wave polarography is one of the most sensitive, direct electroanalytical techniques. The current potential waveforms obtained, being related to the first derivative of a dc polarogram, offer excellent resolution of successive electroactive species in multi-component analyses. However, the method is restricted to slow sweep rates (1 V in 10 to 60
1 Present address, E. I. du Pont de Nemours and Co., Marshall Research Laboratory, 3500 Grays Ferry Ave., Philadelphia, Pa. 19146

minutes) and the minimum concentration of depolarizer detectable is limited by background currents resulting from capillary response (2). Attempts have been made to combine a square wave voltage with a rapidly changing dc ramp at a dme late in the drop !ife. The resultant technique of oscilloscopic square wave polarography (3, 4) has achieved only moderate success, and the detection limits obtained were only about those of dc polarography, because of interference from the double layer current resulting from the rapid dc ramp. Mann (5, 6) has demonstrated the utility of a staircase potential sweep function in the reduction of double layer current in linear sweep voltammetry. This discontinuous sweep function allowed rapid sweep rates while maintaining the current waveforms of linear sweep voltammetry. The combination of a square wave of half-period T with a staircase voltage function of period 2.r should allow rapid potential sweep without any interference from double layer currents, while still affording the advantages of square wave polarography. The use of a hanging mercury drop test electrode (hmde) should eliminate the effect of capillary response, and the result should be a rapid, sensitive analytical technique. The theory and potential-time waveforms for this technique have been previously presented (7). In this paper, the ex(3) Y . Saito and K. Okamoto, Rec. Polarog. (Kyoto), 10, 227 (1962). (4) K. Okamoto, Modern Aspects of Polarography, T. Kambara, Ed., Plenum Press, N. Y., 1965, p 225. ( 5 ) C. K. Mann, ANAL. CHEM., 1484(1961). 33, (6) C. K. Mann, ibid.,37,326 (1965). ( 7 ) L. Ramaley and M. S . Krause, Jr., ibid., 41,1362 (1969).
VOL. 41, NO. 11, SEPTEMBER 1969

(1) G. C. Barker and I. L. Jenkins, Analyst, 77 685 (1952). (2) G. C. Barker, Anal. Chim. Acta, 18, 118 (1958).

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