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FARADAY AND HIS LAWS OF ELECTROLYSIS AN APPRECIATION

Article  in  Bulletin of Electrochemistry · November 1991

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Bulletin of Electrochemistry 7 (11) Nov 1991, pp 481-484 0256-1654191/$ 3-50
@1991 CECRI

FARADAY AND HIS LAWS OF ELECTROLYSIS AN APPRECIATION

FRANK C WALSH

Applied Electrochemistry Group, Chemistry Department, Portsmouth Polytechnic, White Swan Road, Portsmouth, POl 2DT, UK

[Received: 1991 October; Revised: 1991 November]

In connection with the birth bicentenary of Michael Faraday (1791-1867), an appreciation of bis life and career, his
laws of electrolysis and their applications are discussed as applicable to electrochemical technology. The factors which
cpntributed to Faraday's success as a 1>cientist and engineer are also indicated.

Key words: Michael Faraday, Faraday's laws of electrolysis, electrochemical technology

MICHAEL FARADAY
1791 Bicentenaiy Year 1991

lHE®
INSTITUTE
OF METAL
FINISHING
Ei<1crH-, 4t Holk>wa7 llad,
Courlesy or The Royal lnstitulion of Great Orltain lli...lacJl.o.,. IJINQ

Fig 1: A Commemorative Bicentenary Cover of a Postage Stamp Issued by the Institute of Metal Finishing.
The 22 pence stamp was issued by the British Post Office on 5th March 1991 as part of a set which also acknowledged the contributions to science from
Babbage (22 pence), Watson Watt (31 pence) and Whittle (37 pence).
Faraday's bicentenary is being celebrated in several other ways
in Britain, as illustrated by the following examples:
(i) An exhibition of his life and work is running until the end of
1991 at the Science Museum in London.
(ii) A memorial service was held on 2dth September, 1991 at
Westminster Abbey.
(iii) A television program entitled "Faraday's Dream" was shown
on 21st September on BBC 2 and provided a dramatisation of
his life and work.
(iv) Many articles have appeared in the popular scientific press and
in technical journals, e.g. [1-3].
(v) A book has been published by the Director of the Royal
. .-- - _..,_.u ·'- ~
Institution [4] which supplements earlier biographies, e.g. [5,6] .
1• ... . . . ' ... " ... .
Such recognition is rarely afforded to scientists and only
exceptionally to (electro)chemists. It is therefore interesting to
consider Faraday's contributions to electrochemistry within the
framework of his other achievements and against his general
Fig. 2: A Bank Note Marking the Bicentenary of Faraday's Birth. background.
The £20 note, which was issued in 1991 by the Bank of England,
illustrates the "Royal Institution Christmas Lectures Initiated in 1826-The FARADAY'S LIFE AND CAREER
Magneto-Electric Spark Apparatus".· The note contains some micro lettering
using a list of new words introduced by Faraday.
Michael Faraday was born on 22nd September 1791 in a slum
in the Newington area of South London as the third child of a
blacksmith. The family were of the Sandemanian faith ( a strict
INTRODUCTION religion of Scottish origin) and Faraday became a devout follower.
His early education was sparse and in 1805 he became
The bicentenary of Michael Faraday's birth has recently been apprenticed to a bookbinder. In the years to follow, Faraday
acknowledged in the UK by the issue of a postage stamp and a read many texts and learned essential communication skills via
bank note bearing his image. handwritten notes and illustrations. This period also kindled
 WALSH-Faraday and his laws of electrolysis: An appreciation

his interest in construction of scientific apparatus; material from Second law

the Encyclopaedia Brittanica allowed him to construct a simple Faraday wrote: "Electrochemical equivalents coincide and are the
electrostatic generator and detector (a Leyden jar). same with ordinary chemical equivalents" Currently, it is no longer
Faraday's entry to science was via access to Royal Institution fashionable to use the term 'chemical equivalent' and it is replaced
lectures and as an assistant to Davy in 1813. The young Faraday by the ratio of molar mass of the species divided by the m.1mber of
soon established a reputation for the excellence of his experimental electrons per molecule [11 ]:
work and he soon developed independent theories which were
subjected to critical experimental test. His studies spanned the w ex: M/z ... (2)
subject areas of electricity, magnetism, heat, light, gravity and Combined laws
chemistry. A particular theme, however, was the existence of
From proportionalities (1) and (2), it follows that
force fields and their interaction. The majority of studies related
electricity to one of the other forces. w ex Q(M/z) .. . (3)
Faraday married a fellow Sandemanian in 1821 who provided One of Faraday's outstanding contributions was to identify the
consistent support throughout his career. In 1824, Faraday universal nature of this expression and to determine the constant
was elected a member of the Royal Institution (despite of proportionality. Hence
Davy's opposition) and in 1826 he launched two series which
w = (1/F)Q(M/z) . . . (4)
popularised science-the Christmas Lectures and the Friday
Evening Discourses. Faraday remained active for most of his life. where the Faraday constant now has an accepted value
In 1861 he reluctantly resigned from the Royal Institution due F = 96485C.mo1- 1
to failing health (although he still continued to give occasional Rearrangement of equation (4) gives
lectures). His last discourse was given on 20th June 1862. H
is interesting to note the scientist's humility; he graciously turned F = QM/ wz . .. (5)
down both a knighthood from Queen Victoria and the presidency which provides the basis of a simple experimental method for
of the R.I. determining the Faraday constant. It also shows that it is the
In his own time, Faraday was admired for his experimental ability quantity of electricity associated with electrolysis of one 'gram
and the capacity to explain the significance of his findings to a wide equivalent' i.e. 1/z moles of a substance.
variety of listeners, including lay audiences and children. Critical Another rearrangement of equation (4) gives:
experiments were often targeted following extensive surveys of the
w/ M = Q/zF ... (6)
literature together with a broad and up to date knowledge of
available hardware. It is clear, for example, that devices such as The left and right hand sides of equation (6) represent the
the Voltaic pile (1800) and the Daniell cell (1836) were essential amounts of chemical. change and electrical energy involved in an
sources of electrical energy in some of Faraday's early studies. electrochemical reaction respectively. This equation is a concise
Equally, he benefitted from .the contemporary discovery of the and quantitative statement of the equivalence between chemical
deflection of a compass needle by a wire carrying an electric current energy and electrical energy. .BY definition, the electrical charge is
(by Oersted in 1820) which was quickly followed by Ampere's the integral of current with respect to time:
experiment on the movement of two parallel wires when current
passed. Faraday also acknowledged contributions from Wollaston
concerning electromagnetic rotation in addition to his experiences
Q= JI · dt . . . (7) :
Many practical electrochemical reactions take place under constant
as Davy's assistant. The result of Faraday's integration of skills
current conditions and the electrical charge is the product of
and his ability to cross subject boundaries was often an elegant current and the time for which it passes:
demonstration of a working device, the electric motor and the
transformer being classical examples. Q =It .. . (8)
It is, however, unfair to limit our appreciation of Faraday to Additionally, the possibility of side reactions can be allowed for
his experimental flair together with his ability to demonstrate and by definirig a current efficiency. This is the fraction of the
even popularise science. His accomplishments as a theoretician total electrical charge (Oror) which is associated with the desired
were also remarkable. This is particularly evident in the laws of reaction (Q).
electrolysis which are elegant, quantitative and general statements </J = Q/Oror = (It)/(Irort) .. . (9)
arising from careful empirical observation in relatively simple Equatioa (6) may then be written:
apparatus.
n = </Jlrort/zF . .. (10)
FARADAY'S LAWS OF ELECTROLYSIS where n is the amount of material undergoing electrochemical
change.
Despite their importance in electrochemical science and
The fundamental importance of the Faraday constant at the
technology [7], these laws appear to be poorly understood by many
atomic level is embodied in the following expression:
young scholars and are now missing from some modern physical
chemistry (and even electrochemistry) text books. These laws were F=NAe ... (11)
published in 1833 and 1834 [8-10]. Following an exceptionally where NA is the Avogadro Number and e is the charge on a single
productive period in Faraday's life from January 1832 to December electron [12] (the elementary charge i.e.,):
1834. 4
(9.648456(27) x 10 C.mo1- 1 = (6.022045(31) x 10i3 mol- 1)

First law x (1.6021892(46) x 10- 19 q ... (12)

In Faraday's words, "Chemical action or decomposing power is In other words, F is a universal constant which is the product of
exactly proportional to the quantity of electricity which passes". two other ones. It represents the electrical charge associated with
A modern statement is that the mass of a substance deposited one mole of electrons.
or liberated during electrolysis is proportional to the quantity of
electricity passed: APPLICATIONS OF FARADAY'S LAWS OF ELECTROLYSIS
Facile manipulation of equations (6) and (10) provides expressions
wcx:Q .. . ( 1) which are routinely used in both laboratory and industrial
482
 WALSH- Faraday and his laws of electrolysis: An appreciation

applications of electrochemistry [7]. Examples include both communicator provided essential skills for the rapid development
electrolytic cells, which utilise electric power to provide chemical and evaluation of his theories for the interaction of forces.
change (as in electrosynthesis and electroplating) and galvanic cells Faraday's stamina and persistence are also noteworthy; indeed,
which create electrical power via spontaneous chemical change, (as many of his early attempts to show interactions between forces
in batteries and corrosion) [13]: failed. One example is the effect of electricity on light (which
(i) In kinetic studies, differentiation of equation (10) provides was later demonstrated by Kerr in 1875). Initial experiments on
an expression for the rate of reactant depletion (or product magnetism and light also proved unsuccessful but paid off later
buildup) with time: on in 1845 when the magneto-optical or Faraday effect (rotation
. . . (13) of the plane of polarised light by a magnetic field) was ably
dn/ dt = </JhoT/zF demonstrated. In 1849, he failed to show that the forces. of
Equation (13) is written in terms of an amount per unit time. It is electricity and gravity could be interconverted. His conviction about
often more convenient to write the expression as a rate of change the unity of natural forces remained unshaken, however, and were
of concentration (amount ba8is) in a constant electrolyte volume unmistakably illustrated by his previous work on electro-magnetic
(V) system: induction and electrolysis.
dc/ dt = </Jlror/zFV ... (14) Faraday's laws of electrolysis have formed a foundation for
(ii) Electroanalytical determinations may be carried out for the quantitative electrochemistry and the applications span many
mass concentration: sectors of laboratory and industrial endeavour. The scale of
electrochemical technology may be simply indexed by the cell
C= </JITOTtM/zFV (15) current and electrode area. Perhaps even Faraday would have
or the total mass been surprised by the breadth of scale. At the high end, large scale
w = </JITOTtM/zF (16) chloralkali processing can involve cell currents and electrode area
(iii) In electrosynthesis, the rate of production of a species may of 107 A and 104 m2 respectively. In contrast, increasing attention
be related to the electrolysis cutrent and the batch time via is now being focussed upon microelectrodes which can involve
equation (13). The performance of electrochemical reactors is values of 10- 10 A and 10- 12 m2 respectively. This microscopic
often expressed in terms ·of a 'space-tim.e yield', Ysr wh,ich is limit is rapidly being extended and it is becoming possible to
the amount of product per unit reactor volume (VR) per unit study controlled monolayer and even single atom/ molecule surface
time. This figure of merit is given from equation (13) as changes on electrodes. Such studies have become possible by
Ysr = (dn/dt)(l/VR) (17) improved techniques for the preparation of electrodes, more
sophisticated control, more rapid perturbation response techniques
and the integration of spectroscopic techniques (which are often
Ysr = ef>hOT/ZFVR (18) used in situ ). Our understanding of electrochemical reaction
(iv) When electroplating at constant current, the time necessary to rates now includes complexities such as adsorption, nucleation and
reach a certain uniform deposit thickness, x, may be estimated crystallisation, and their effect on current- potential behaviour.
via: The successful design and application of electrochemical reactors,
... (19) devices and sensors also require an appreciation of materials
science ·and chemical engineering [14]. In all of the fields
where p is the density of the deposit.
(v) The theoretical quantity of electrical charge obtainable from a of electrochemical technology, however, Faraday's Laws of
battery may be related to the quantity of electroactive materials Electrolysis provide a fundamental building block.
via the equation:
Q = WZF/ Mef> . .. (20)
CLOSURE
(vi) In the case of uniform corrosion of metals, two common
methods for expression of the corrosion rate include the Finally, it is interesting-to consider the factors which contributed
averaged rate of penetration to Faradays' success as a scientist and engineer:
dx/ dt = jM/ pzF ... (21) (i) His wife provided tremendous moral support, as did the
couple's devotion to the Sandemanian religion.
where j is the current density, and the mean weight loss per unit ii) Apprenticeships as a bookbinder, then as Davy's assistant,
area per unit time provided a very useful and stimulating training. The Royal
-(1/A)(dw/dt) = jM/ zF ... (22) Institution proved to be both a fitting home and an inspirational
working environment for much of his life.
iii) Faraday's ability to devise critical experiments then to
DISCUSSION demonstrate them in a convincing manner was remarkable.
Early attempts were often refined in order to produce better
In these days of increasing specialisation and sophistication, it data and his ability to cross the traditional. boundaries between
is perhaps educational to look back upon the elegance and disciplines was a powerful driving force.
timeliness of Faraday's work. His clear vision of the interaction of iv) Elegance and diligence were hallmarks of his lecture
apparently separate forces and hence the equivalence of different presentations and the documentation of his laboratory studies.
types of energy ·was built upon a broad based and largely self- Experiments were not only finished rapidly but were published
taught ~ientific training. His experimental work was so often in a timely fashion whenever possible. Apparently, one of
made possible by an extensive and transdisciplinary knowledge of his monos was "work, finish, publish". Indeed, much of his
existing literature and hardware. His unification of theory and electrochemical output appeared in print in the short period
experimental work was systematic. The essential results were often 1833-1836.
demonstrated to a wide audience and Faraday was one of the v) Faraday's work laid the foundations for several academic
greatest popularisers of science. disciplines and industrial sectors including electroplating,
It is difficult (and unnecessary) to label Faraday as a chemist, electrolytic processing, electrical machines and electronic
a physicist or an engineer; his approach unified all of these materials.
professions; additionally, his abilities as a technician, illustrator and vi) The impact of his work was recognised by several eminent

483
 WALSH-Faraday and his Jaws of electrolysis: An appreciation

scientists. For example, Maxwell and Einstein acknowledged w mass of species kg

his contributions and provided a rigorous mathematical
x thickness of metal m
treatment behind Faraday's "lines of force" and "unity of
fields" theories. The search for a quantitative unified field Ysr space time yield mol . m- 3 . s- 1
theory is, of course, a central goal in theoretical nuclear physics.
Laboratory and industrial electrochemists owe a great debt to
z charge number for the
Michael Faraday for his discovery of the fundamental laws electrode reaction
of electrochemical energy conversion. These universal and
</> current efficiency
quantitative relationships have been routinely used by generations
of electrochemists. Their beauty and simplicity shine through in p density of metal kg . m3
the ever increasing complexity of modem electrochemistry.
We also have Faraday to thank for many of the fundamental Acknowledgement: The author gratefully acknowledges consent of
terms which are still used in electrochemistry. Guided by the the Bank of England to produce £ 20 E Banknote.
scholar Whewell, he introduced the words: electrolyse, electrolyte
electrolysis, electrode, anode, cathode, ion, anion and cation.
REFERENCES
NOMENCLATURE
l. J Baggott, The Myth of Michael Faraday, New Scientist, 2lst
September, 1991 pp 43-46
Meaning SI units 2. L Lewis, Michael Faraday 1791-1867, Trans Inst Metal Finish, 69(3)
Symbol
(1991)13; see also DR Gabe, Michael Faraday and his Constant, ibid,
69(4) (1991), (in the press)
3. J M Thomas, In Praise of Michael Faraday, Chem Brit, 27 (1991)
A electrode area mz 765-766
c reactant concentration moJ. m- 3 4. J M Thomas, Michael Faraday and the Royal Institution: The genius
of man and place, Adam Hilger, Bristol, (1991)
e elemenlary charge c 5. J AgaS5i, Faraday as a Natural Philosopher, University of Chicago
Press, Chicago, (1971)
F Faraday constant C . mo1- 1 6. D Gooding and FA L James (Eds), Faraday Rediscovered, Stockton
Press, New York, (1985)
I current associated with
7. D Pletcher and F C Walsh, Industrial Electrochemistry, 2nd Edn,
desired reaction A Chapman and Hall, London, (1990)
8. M Faraday, Experimental Researches in chemistry, 5th and 7th series,
IroT total current A Phil Trans, (1833) pp 675- 710; (1834), 77- 122
9. M Faraday, "On Electrochemical Decomposition': Athenaeum, (1834)
current density (= I/ A) A · m- 2 p 209
M molar mass of species kg. mo1- 1 10. W Ostwald, Electrochemistry, History and Theory, Viet, Leipzig,
(18%); republished as an English translation for the Smithsonian
n amount of species mol Institution, Amerind Publishing, New Delhi (1980)
11. F C Walsh, "The overall rates of Electrode Reactions; Faradays Laws
Q electrical charge for of Electrolysis", Trans Inst Metal Finish, 69(4) (1991) (in the press.)
desired reaction c 12. H Ellis (Ed), Nuffield Advanced Science Book of Data, Longman,
OroT total electrical charge c Harl0W, (1991)
13. B D Barker and F C Walsh, "Applications of Faradays Laws of
time s Electrolysis in Metal Finishing'~ Trans Inst Metal Finish, 69(4) (1991)
v electrolyte volume m3 (in the press.)
14. F C Walsh, 'Trends in Electrochemical Engineering" Bull Electrochem,
VR electrochemical reactor volume m3 7 (1991) 201-206 /

484

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