Electrochrmxa Acta 1964, Vol 9 pp 231 to 240 Pergamon Press Ltd Prrnted m Northern Ireland

INVESTIGATION OF ADSORPTION OF ORGANIC

SUBSTANCES BY DIFFERENTIAL CAPACITANCE
MEASUREMENTS*
B B DAMASKIN
Department of Electrochermstry, Moscow State Umverslty, Moscow, U S S R

Abstract-By usIng theFrumkmlsotherm and taklngmtoconslderatlonthedependenceoftheattractlon

constant on the electrode potential (v), It 1s possible to mterpret quantitatively the C/q curves (C IS
the dlfferentlal capacitance) of the mercury electrode m the presence of ahphatlc organic compounds
(t-C,H,,OH , n-C,H,,OH , z-C,H,,OH , n-C.,H,COOH) The constants necessary for the calculation
charactenze the adsorption state (the adsorption energy, the onentatlon of the molecules on the
surface, and the adsorption potential) and allow the calculation of the dependence of the coverage
on the potential and on the concentration of the orgamc substance In the case of adsorption of
pyrrdme and amlme on mercury, the C/v curves are also characterized by the presence of two peaks
But, as shown by the comparison of the calculated values with the experimental ones, the anodlc
peaks observed are due to a change m the orlentatlon of adsorbed molecules upon the transition to
positive mercury charge, rather than to their desorptlon

R&m&On a montre qu’ene mployant l’lsotherme de Froumkme et en tenant compte de la

dtpendance de la constante d’attractlon du potentlel de l’tlectrode (q) on peut mterprkter d’une
mamere quantitative les courbes C/p, (C-capacltb dlfferentlelie) de l’electrode de mercure en
prkence de composCs ahphatlques @z-C,H~~OH, I-C~H~~OH, I-C~H~~OH, n-CpHoCOOH) Les
constantes, qm sont n&cessalres pour le calcul, caractCrlsent l’Ctat d’adsorptlon (&nerge d’adsorptlon,
orlentatlon des mol&ules sur la surface, potentlel causC par l’adsorptlon) et permettent de calculer la
dkpendance de I’adsorptlon du potentlel et de la concentration du compost orgamque Dans le cas
de l’adsorptlon de la pyndme et de l’amlme sur le mercure, les courbes C/q pr&sentent aussl deux pies,
cependant la comparalson des courbes calcu&s theonquement avec les courbes expCrlmentales
montre que les p~cs anodlques ne sont pas dus & la d&sorptlon des mol&ules du compost orgamque,
mals dus au changement de leur onentatlon quand on passe aux charges posltlves du mercure

Zusammenfassun@% wurde gezelgt, dass die Anwendung der Isotherme Fnunkms unter Beruck-
slchtlgung der Abhanglgkelt der Aunehungskonstante vom Potential der Elektrode (q) es ermoghcht,
die C/wKurven (C-dlfferentrale Doppelschlcht kapautat) der Quecksllberelektrode m Anwesenhelt
von ahphatlschen orgamschen Verbmdungen (n-C,H1lOH, J-C,H~~OH, r-C,H,,OH , n-C,H,COOH)
quantltatlv zu mterpretleren Die zur Berechnung notlgen Konstanten charaktensleren den Adsorp-
tlonszustand (Adsorptlonsenergle, Orlentlerung der Molekule an der Obertlache, Potentialsprung
mfolge Adsorption) und gestatten es, die Abhanglgkelt des Bedeckungsgrades vom Potential und der
Konzentratlon des orgamschen Stoffes zu berechnen Im Falle der Adsorption von Pyndm und
Amlm zelgen die C/q-Kurven an Hg ebenfalls zwel Maxima, der Verghch der Versuchsergebmsse
rmt den berechneten Werten zelgt Jedoch, dass die anodlschen Maxima mcht durch Desorptlon der
orgamschen Molekule erklart werden konnen, sondem auf eme Veranderung der Onentlerung
derselben helm ubergang zu posltlveren Potentlalenhmwelsen

UNTIL recently, differential capacitance measurements were prmclpally used for the
qualitative mvestlgatlon on the dependence of adsorption of organic substances on
electrode potential, quantitative data were obtained only for the region of maximum
adsorption, where the dependence of the capacitance on the coverage of the surface
with organic substance of the differential capacitance curves obtained m the presence
of ahphatlc organic compounds has recently been considered 1-3 We shall not
discuss here the non-thermodynamlcal method of Devanathan since, as shown by
Frumkm and Damaskm,4 the equation used3 IS incorrect
* Presented at the 14th meeting of CITCE, Moscow, August 1963, manuscript received
9 September 1963
1 231
232 B. B DAMASKIN

If the concentratron of an organic substance m the solutron 1s not too small,

drfferentral capacitance curves obtamed at low a.c. frequency correspond to eqmhb-
rmm amounts of the substance adsorbed. In this case, the shape of the drfferentral
capacrtance curves 1s determined by the equatron of the adsorption isotherm. The
adsorptron of the organic substance on mercury surface has been assumed1p2 to obey
the equation of the Frumkm rsotherm,6

Bc = j$eexp (-2a@,
where c 1s the concentratron of the organic substance, 8 = r/l?, the ratio of the
adsorbed amount, I’, to its hrmtmg value I’m (at c -+ co), a the attractron constant
characterrzmg the interaction between the adsorbed molecules and B the constant of
adsorptron equlhbrmm By means of the equation of the isotherm and the thermo-
dynamical relatronshrp
8 In c 1 i3&
- =-- _ (2)
( av 1B RTI?, 0 a0 /

where v 1s the potential of the electrode and E its charge, rt 1s possible to obtain a
complete picture of the dependence of adsorptron on potentral For this purpose It
1s necessary, however, to make an assumptron about the dependence of E on 0
According to Frumkm,6 m the case of ahphatrc compounds the electrode charge
changes hnearly with 8,
E = ~~(1 - 0) + C(P, - vN)e, (3)
P
where a0 = C,dq, C,, and C’ are the capacitances of the double layer at 0 = 0 and
s0
0 = 1 respectively and pN is the adsorptron potential, 1 e the shaft m the pomt of
zero charge upon the transrtron from 8 = 0 to 0 = 1 The pl potentials m thus and
m all subsequent equations are referred to the pomt of zero charge at 0 = 0 It
follows from eq (l)-(3) that the dependence of the constant of adsorption eqmhbnum
B on the electrode potential m the case of ahphatrc compounds IS expressed by the
relatronshrp

B = B, exp -
s’
I

(4)

where A and B, are constants, A = RTr, and B, IS related to the standard free
energy of adsorption at q~= 0 and 0 = 0 by
AGO= -RTln (55 5 B,)
On the basis of eq. (I), (3) and (4), provided a = const, Hansen, Mmturn and
Hrcksonl obtamed the expressron for the drfferentral capacrtance of the double layer
m the presence of an orgamc substance,

C = C,(l _ 0) + cfe + [&O

+ “‘y - VII2 h,

e(l - e)
h= (6)
i - 2ae(i - e)
But when thus equatron was compared wrth the experrmental data for the solutrons
 Investlgatlon of adsorptIon of organic substances by dlfferentlal capacitance measurements 233

of n-valerrc acrd in 0 1 N HCIOI supportmg electrolyte, a great discrepancy was ob-

served l A srmrlar drscrepancy was observed by us also when using eq (5) at constant
a to descrrbe the C/q curves m the presence of tert. amyl alcohol 2 We attributed
this discrepancy to the fact that the attractron constant a changed wtth the electrode
potential To a first approxrmatron the dependence of a on p can be accounted for by
means of the quantrty h m eq (5) An accurate expressron for the drfferentral capac-
stance of the double layer m the presence of orgamc substance, the adsorption of
which obeys eq (1) and (4) for any arbitrary dependence of a on v, 1s given by the
relation6

1
2
E0+ C’(r&F - cp)- 2A8 $
c = C,(l - e) + C’B + h, (7)
A
where vNo = ply, provided that daldg, = 0
In order to find the dependence of a on p from the experrmental data we assumed6s7
that the posrtron of the peaks on the C/pi curves 1s determined, mainly, by the quantity
h In thus case, the coverage at the maximum 19”‘~N 0 5 and the values of a at the
potentials of the peaks on the drfferentral capacrtance curves can be found from the
wrdth of the capacitance peaks (AT) and the slope of the curve expressmg the de-
pendence of the peak potentials (v,“““) on the concentration of orgamc substance,
Arp algc l+r
--
2 a mar --logG-&r,
- (8)
I V I 9
where
2-a 2-a
r l/2 = (9)
J- 4-_n T r3/, =
J- 8-a

(the subscript to r mdrcates the relatrve height of the peak at which its wrdth can be
determined, I e rt 1s equal to the ratio h/h”““) The left hand side of eq (8) IS found
by experiment, while the rrght hand srde is calculated for varrous values of a This
method of determmatron of a is based only on the use of the Isotherm (1) and 1s free
of any assumptrons about the dependence of the adsorptron energy (I e. the quantrty B)
on the electrode potential At the potential of maximum adsorptton, the addrtronal
capacitance due to adsorption-desorptron processes 1s equal to zero, and hence
c = c,(l - e) + c’e m
a IS readily determined from the shape of the adsorption isotherm *
It is evrdent that the posrtron of the peaks on the C/v curves corresponds to the
maximum of the value of h only at not too low values of a, where a strong dependence
of h on the electrode potential IS observed ’ In the general case, the posmon of the
maximum on the differential capacitance curves m the presence of orgamc substance
1s determmed by the condrtron dC/dg, = 0 In thus case, the calculatron 1s possrble
only by the assumptron that Co = const and a = const , and consequently cannot be
quantitatrvely compared with the experrment Nevertheless, this calculatron
estabhshes the hmrts of the apphcabrhty of the above method of determmatlon of a
from the wrdth of the peaks and slope of the lg c/qFaz curve As shown by the anal-
ysis by Damaskm and Tedoradze,s the error m the determmatron of a by this method
at a > 1-Odoes not exceed 6 per cent At lower values of a, however, the error sharply
mcreases and the method becomes mapphcable
234 B B DAMASKIN

In collaboration with N B Gngorjev, R Lerkh and V K Venkatesan, we have

studied, by means of dlfferentlal capacitance measurements, the adsorption on mer-
cury of the followmg ahphatlc compounds t-C,H,,OH m 0 9 N NaF supportmg
electrolyte, n-C,H,lOH and z-C!sH,,OH m 1 N Na,SO, supportmg electrolyte
n-C,H,COOH m 0 1 N Na,S04 and 0 1 N H,S04 supportmg electrolytes. The
condltlon a > 1 0 was observed with all the compounds studled In all cases,
an approximately linear dependence of the attraction constant on the potentlai
was observed (a increases with mcreasmg q), which, as shown by thermodynamlcal

+. v(N C E )

FIG 1 Dlfferentlal capacitance curves for mercury m 0 9 N NaF (dashed hne) and with
additions of r-C,HIIOH 1,O 3, 2,0 1, 3,0 03, 4,0 01 M Solid lines, calculated by
means of eq (5), different symbols, expenmental data for the correspondmg solutions,
frequency 400 c/s

transformations using eq (1)<4), may be caused by a hnear change the adsorptlon

potential P)Nwith an increase m the coverage of the surface by organic substance*
By takmg mto conslderatlon the linear dependence of a on v, good agreement
between the calculated and the experimental dlfferentlal capacitance curves can be
obtained for all the ahphatlc compounds investigated These results are shown m
Figs l-4
On account of the quantttatlve agreement between theory and experiment, It 1s
possible to use the data on the dlfferentlal capacitance m the presence of organic
substances to calculate the coverage and the adsorptlon Isotherm over the whole
potential range under mvestlgatlon, and not only at the potential of maxlmum ad-
sorption where to the first approxlmatlon the dependence of the capacitance on 8 =
r/r, 1s linear s On the other hand, the constants necessary for the calculation,
determined by us from the experimental log c/plmaxcurve by the methods previously
* In this case qXo m eq (7) corresponds to the value of P)~ at 0 = 0
lnvestrgatron of adsorptron of orgamc substances by drfferentral capacrtance measurements 235

A v(NCE)

FIG 2 1 Differential capacrtance curves for mercury m 0 1 N Na,SO, wtth drfferent

addmons of n-C4HoCOOH 1, 0, 2,0 01, 3,0 02, 4,0 05, 5,O 10 M Sohd hnes,
calculated by means of eq (51, symbols and dashed hnes, expertmental data, frequency
400 c/s

200

“E
-z? I50
z

0‘ 100

SO

0 -10 -15
0 -05
9, v(NCE )
FIG 3 Dlfferentlal capacnance curves for mercury m 1 N Na,SO, wrth different
addmons of n-C,H,,OH, 1, 0, 2,0 01, 3,0 02, 4,0 04 M Sohd hnes, calculated by
means of eq (7)) dashed hnes, expenmental data, frequency 450 c/s
236 B B DAMAWN

250

200

NE

s
d_
150

100

50

0
0 -0 5 -I 0 -I 5

4. v(NC El

FIG 4 DdTerentlal capacitance curves for mercury m 1 N NalSOI with different

addltlons of r-C,HIIOH 1, 0, 2, 0 005, 3, 0 01, 4, 0 02, 5, 0 04 M Sohd hnes,
calculated by means of eq (7) dashed lmea, expenmental data, frequency 450 C/S

60

50

40
“E

s
a
30

20

IO

4. v(NC E3
FIG 5 DdTerential capacitance curves for mercury m 0 5 N KC1 with different addltlons
of pyrldme 1, 0, 2,0 06, 3.0 10, 4,0 20, 5,O 30 M, frequency 400 C/S
 Investlgatlon of adsorption of orgamc substances by differential capacitance measurements 237

described6 characterrze the adsorptron state of the organic substance being investr-
gated, its adsorption energy, the area per molecule and, consequently, the orrenta-
tron on the surface and the adsorptron potential.
Good agreement between calculatron and experiment is observed, however, only
m the case of ahphatrc compounds An attempt to apply the theory to the adsorptron
of heterocychc or aromatrc compounds mvolves drfficultres caused by the T-electronic
mteractron between the molecules bemg mvestrgated and the mercury electrode surface.

I I I I
0 -0 5 -10 -I 5

$9 viN C E)
FIG 6 Dlfferentlal capacitance curves for mercury m 1 N KC1 wth different addltlons
ofamlme l,O, 2,001, 3,002, 4,005, 5,010, 6,020Mfrequency4OOc/s

Frg. 5 shows the differential capacrtance curves measured m 0.5 N KC1 with varymg
pyrrdme addrtrons .l” As m the case of ahphatrc compounds m the presence of pyridine,
there are two maxima on the C/p, curves, whrle at large positive or negatrve surface
charges the curves obtained m the supporting electrolytes with and without pyridme
addrtrons approach each other - indicating, as rt were, a process of organic substance
desorption. The simrlarrty between the drfferentral capacitance curves m the presence
of ahphatrc compounds and the C/q curves m KC1 solutions containmg amhne
obtained by us together wrth I P. Mrshutushkma (Fig 6) IS even greater. But the
srmrlanty m this case 1s only apparent. Whrle m the presence of ahphatic compounds,
both maxima on the C/v curves are due to the adsorptron-desorptron processes, m
the case of pyrrdme and amhne only the cathodic maxima correspond to these pro-
cesses The anodrc maxrma are due to the re-onentatron processes of adsorbed mole-
cules of orgamc substance on the mercury surface. the vertical orientatron of pyrrdme
and amhne molecules character&c of a negatrvely charged surface rs substrtuted by
a honzontal one, where the n-electrons of the pyrrdme or benzene rmg begm to interact
wrth the posrtrve charges of the mercury surface. An approxrmate comcrdence between
238 B B DAMASKIN

the value of the double layer capacitance found m the plain supportmg electrolyte and
that found m the presence of organic substance observed m the region of large posltlve
surface charges can be explamed by the n-electrons of the benzene or pyrrdme rmg
penetrating mto the metal and neutralizing the posltlve charges of the mercury surface,
as a result, the monolayer of the horlzontally oriented molecules, characterized by

I 1 I I
0 -05 -IO -15
+. v(NCE)
FIG 7 Differential capacitance curves for mercury m 1 N KC1 (dashed hne) and with
a 0 1 M addltlon of amlme, 1, calculated by means of eq (5)) 2, expenmental data,
frequency 400 c/s

the presence of the electronic “holes”, begins to act as the posltlvely charged metal
surface, attracting chlorme anions In this case, the double layer capacitance 1s
determined by the Cl- ion and the molecules of the solvent alone
On account of the change m the character of adsorption of pyrldme or amhne
molecules with the potential, the calculated differential capacitance curves can corre-
spond only to the cathodic branch of the experlmental C/v curve In the region of
posltlve surface charges, the calculated and the experlmental C/p curves no longer
agree (Fig 7) Thus, the contents m eq (1) and (4), obtained from the comparison of
the calculated and the experimental values, characterize the adsorption of pyrldme and
amhne only at negative surface charges
In the case of pyrldme adsorption on mercury, a very strong dependence of a on
p 1s observed m the extreme cathodic region the value of the attraction constant 1s
as high as 1 95-1 97, which accounts for the high and narrow desorptlon peaks
(Fig 5), whereas at posltlve surface charges a < 0, I e the repulsive forces between
the adsorbed pyrldme molecules predominate Nevertheless, almost over the whole
potential range Investigated the adsorptlon of pyrldme obeys the equation of the
Frumkm isotherm,l as seen from Fig 8* The dependence of the coverage on the
* A sharp change m the shape of the adsorption isotherms of pyndme with the electrode potential
was first observed by Glerst I1
 Investlgatlon of adsorptlon of organic substances by drfferentlal capacitance measurements 239

potentral calculated allowmg for the change m a wrth e, 1s also m good agreement
with the data of electrocaprllary measurements for the greater part of the potentral
range studied, whereas the condition a = 0 (correspondmg to the Langmmr rso-
therm) does not agree with the experiment at all (Fig 9) Only m the case of large

FIG 8 isotherms of pyndme adsorptlon on mercury of dnferent potentials 1, -0 15,

2, -0 45, 3, -1 05, 4, -1 45 V (NC E ) Solid hnes, calculated by means of
eq (l), making allowance for the dependence of a onv, different symbols, experlmental
data found from electrocaplllary measurements

0 -0 5 -I 0 -I 5

6 v(NCE)

FIG 9 Dependence of the coverage on the potential m the solutron of 0 1 N KC1 + @3

M pyrldme cucles, expenmental data obtamed from electrocapdlary measurements,
solid line, calculated by means of eq (1) and (4) with an allowance for the dependence
of D on the potenttal, dashed hne, calculated at n = 0

posrtrve polarrzatrons do the expenmental values of 8 deviate from the calculated

curve as the result of the re-orrentatron of pyrrdme molecules, the adsorption
of the latter proceeding owmg to the r-electronic interaction with posrtrve mercury
charges
2$0 B B DAMAXIN

In the case of amhne adsorption on mercury, a very small dependence of the

attractron constant on the potential is observed. This dependence, when extrapolated
to the regron m which the electrode surface 1s posrtrvely charged, gives a value a > 0
This means, that with the adsorptron of anihne molecules m the vertical posrtron,
when E > 0, as well as when E < 0, the attractron between the molecules is predomr-
nant. Thrs rmphes that at the posmvely charged surfaces it is possible to have a tran-
sition from planar orientation of the amhne molecules to vertical orlentatron only by

C, M/L
FIG 10 Isotherms of amhne adsorption on mercury at E > 0, obtained from eleotro-
capdlary measorements m solutions of 1 N KC1 wnh different addmons of amhne
1, -05, 2, -04, 3, -03, 4, -02, 5, -01 V(q,NCE)

sufficiently increasing the bulk concentratron of amhne This conclusron 1s supported

by experiment. Thus, accordmg to V M. Gerovrch, at posrtrve surface charges two
sections are observed on the isotherms of amlme adsorption obtained from the electro-
capillary curves (Fig lo), which can be attributed to the change m the character of
amhne adsorption occurring with an increase of its bulk concentration a horrzontal
onentatron at small c 1s substrtuted by the vertical one at large c The shape of the
adsorptron isotherm shown m Fig 10 can no longer be described by eq. (1) This
effect 1s not observed m the case of pyndme apparently owmg to the fact that the
vertical onentatlon of pyndme molecules at posrtlve charges of the mercury surface 1s
hindered by a much greater value of the positive adsorption potential.
REFERENCES
1 R S HANSEN,R E MINTURNand D A HICKSON,J Phys Chem 60, 1185 (1956)
2 B B DAMASKINand N B GRIGORJEV, Dokl Akad Nauk SSSR 147,135 (1962)
3 M A V DEVANA~AN, Proc Roy Sot A 267,256 (1962)
4 A N FRUMKINand B B DAMAWN, m Modern Aspects of Electrochemrstry, No 3, ed J O’M
BXKRIS Butterworths, London (1964)
5 A N FRUMKIN,Z Phys 35,792 (1926)
6. B B DAMASKIN,Zh FIZ Khrm 37, 2483 (1963)
7 B B DAMASKIN,Dokl Akad Nauk SSSR 144,1073 (1962)
8 B B DAMAXIN, S VA&I&A and N B GRIGORIEV, Zh Rz Khzm 36,253O (1962)
9 B B DAMASKIN and G A TEWRAIXZE,Dokf Akad Nauk SSSR 152, 1151 (1963)
10 L D K.LJUKINA and B B DAMASKIN,Izv Akad Naak Otdel Khlm Nauk No 6,1022 (1963)
11 L GIERST,Transactzons of Sympostum on Electrode Processes, p 294 New York (1959)