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Comprehensive Treatise of Electrochemistry pp 249–337Cite as

Polarography

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Abstract

Polarography, one of the most widespread electrochemical techniques both for the study of electrochemical processes and for analytical applications, was introduced in 1922 by Heyrovský.(1) The name polarography was coined originally from the “electrochemical polarization” of the polarizable dropping mercury electrode (DME) in connection with a reference electrode when increasing successively a d-c voltage applied externally to the given cell. In terms of the later classification of various electrochemical techniques [see, e.g., References (2) and (3)], polarography belongs to the potentiostatic techniques with linearly increasing potential using a dropping mercury electrode as a working electrode.

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Abbreviations

a:

constant of interaction between adsorbed molecules

A:

surface area

A:

mean surface area

c:

concentration in general or at the electrode

c:

time independent concentration

c°:

concentration in the bulk

C:

capacity

Cd :

differential capacity

Cs :

series capacitance component of faradaic impedance [Eq. (169a)]

Cw :

effective capacitance of the Warburg impedance [see Eq. (169a)]

d:

density

D :

diffusion coefficient

DME:

dropping mercury electrode

E :

potential

E* :

potential referred to pzc

E 0 :

standard potential

E 1/2 :

half-wave potential

Er 1/2 :

reversible half-wave potential

E r 1/2 :

irreversible half-wave potential

E :

pulse or sine voltage amplitude

h :

height of the mercury column

Ia :

anodic current

Ja,s :

current in presence of surfactant

I ads :

adsorption current

Ī :

mean current

Ī ads,I :

mean adsorption limiting current

Ic :

cathodic current

Id :

limiting diffusion current

Id :

mean limiting diffusion current

I DL :

charging current

I l :

limiting current

Ik :

current controlled by the rate of chemical reactions

I rev :

current of a reversible charge-transfer reaction

I s :

alternating current

I sw :

square-wave current

k :

rate constant of forward chemical reaction

keM :

effective charge-transfer rate constant

k j :

consecutive formation constant for the j-th complex

k ox :

charge-transfer rate constant for oxidation

K red :

charge-transfer rate constant for reduction

k s :

rate constant of the surface chemical reaction

k’ :

rate constant of reverse chemical reaction

k* e :

charge-transfer rate constant given by Eq. (73)

k° e :

charge-transfer rate constant at E = E0

k° e,cor :

charge-transfer rate constant at E = E0 corrected for double-layer effect

oke :

charge-transfer rate constant on uncovered surface

ike :

charge-transfer rate constant in covered surface

K :

integral capacity per unit area

K’ :

integral capacity

K j :

formation constant for j-th complex

l :

length of the mercury jet

m:

flowrate

n:

number of electrons involved in an electrode reaction

Ox:

oxidized form

pzc:

potential of zero charge

P eff :

effective hydrostatic pressure

Pb :

back pressure

q :

charge density

qi :

charge density due to specifically adsorbed ions

Q :

charge at the electrode

r :

number of solvent molecules replaced by one molecule of a surfactant

r :

radius of the drop

rc :

radius of the capillary

R :

gas constant

R :

resistance

R ct :

charge-transfer resistance

Red:

reduced form

Rs :

resistive component of faradaic impedance [see Eq. (169)]

R w :

resistive component of the Warburg impedance [Eq. (169)]

s :

specific mass

t :

time

t d :

drop time

t p :

time of voltage application

t s :

half-period of the square-wave voltage

t 1 :

time of drop growth prior to voltage application

t’ :

time elapsed from the beginning of the last halfcycle

T :

temperature

v :

velocity

V:

volume

x :

distance from the electrode

Y’ f :

real component of faradaic admittance

Y″ f :

imaginary component of the faradaic admittance

z :

charge of the electroactive species

Z f :

total faradaic impedance

Z’ f :

real faradaic impedance component

Z″f :

imaginary faradaic impedance component

α:

charge-transfer coefficient of cathodic reaction

ß:

adsorption coefficient

γ:

surface tension

r:

surface excess

rm :

maximum surface excess

η:

viscosity

η1/2 :

polarographic overvoltage E1/2 - E0

V :

time for the complete coverage of the electrode

Φ:

fractional coverage

Φ:

charge-transfer resistance [Eq. (169)]

ℋ:

specific conductivity

ℋ:

Ilkovic constant [Eq. (25)]

λ:

mean value of Ilkovic constant

λ’:

potential function, A = exp (nF/RT)(E — E 0 )

λ’:

potential function, λ’ = exp (nF/RT)(E – E 1/2 )

μ:

thickness of reaction layer

σ:

Warburg coefficient

φ:

potential in the double layer

φ2 :

potential at the outer Helmholtz plane

Ø:

phase angle

ℋ1 :

function argument (see Eqs. (62), (101), and (114a))

Ψ:

eigenfunction

ω:

angular frequency

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  1. The J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, Prague 1, 11840, Czechoslovakia

    Jaroslav Kuta

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  1. Texas A&M University, College Station, Texas, USA

    Ralph E. White  & J. O’M. Bockris  & 

  2. University of Ottawa, Ottawa, Ontario, Canada

    Brian E. Conway

  3. Case Western Reserve University, Cleveland, Ohio, USA

    Ernest Yeager

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Kuta, J. (1984). Polarography. In: White, R.E., Bockris, J.O., Conway, B.E., Yeager, E. (eds) Comprehensive Treatise of Electrochemistry. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-2679-3_4

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