Lecture 2

Introduction
History of Electrochemistry
Electrolysis cells/Galvanic cells
Electrode/Electrochemical process
Anode/Cathode
Anions/Cations

Electrochemistry is a multidisciplinary science concerned with the study

of the interconversion of chemical and electrical energy. It uses concepts and
notions borrowed from chemistry as well as electricity, but it has developed over
the time its own laws, concepts and terms becoming an independent,
selfsustained science.
This definition, largely accepted, has rather a historical importance, as it
does not take into account more recent electrochemical phenomena. An
alternative definition states that the electrochemistry is the science concerned
with the study of reactions in which charged particles (ions or electrons) cross
the interface between two phases of matter, typically a metallic phase (the
electrode) and a conductive solution called electrolyte or shorter the study of
electrically charged metal/solution interfaces. This definition appears to
correspond much better with the evolution and dynamics of this branch of
chemistry over the time.

How old are the first electrochemical artefacts?

Riddle of Baghdad’s battery

In 1936, while excavating ruins of a 2000-year-old village near Baghdad,

workers discovered mysterious small vase of bright yellow clay dating back two
millennia contained a cylinder of sheet-copper 13 cm x 4 cm (see fig. 1a). The
edge of the copper cylinder was soldered with a roughly 60% - 40% lead-tin
alloy comparable to today's solder. The bottom of the cylinder was capped with
a copper disk and sealed with bitumen or asphalt. Another insulating layer of
asphalt sealed the top and also held in place an iron rod suspended into the
centre of the copper cylinder (see fig. 1b). The rod showed evidence of having
been corroded with an acidic agent, possible vinegar, citrus zest or even sea
water.
German archaeologist , Wilhelm Konig, examined the object and came to
a surprising conclusion that the clay pot was nothing less than an ancient electric
battery.

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 Fig. 1a. The actual components of Fig. 1b. Battery parts
Baghdad’s battery

The ancient battery is kept in the Baghdad Museum, as well as those

others which were unearthed in Iraq, are all dated from the Parthian occupation
between 248 BC and 226 AD.
It is certain the Baghdad batteries could conduct an electric current
because many replicas have been made, including by students of ancient history
under the direction of Dr Marjorie Senechal, professor of the history of science
and technology, Smith College, US (see fig. 1c).

Fig. 1c. Cross section of a functional replica

of Baghdad’s battery

Dr. Konig also found copper vases plated with silver in the Baghdad
Museum, from Sumerian sites, dating back to at least 2500 BC. When the vases
were lightly tapped, a blue patina film separated from the surface, which is
characteristic of silver electroplated onto copper base and this may explain a
possible use of Bghdad’s battery.
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 Some other researchers have suggested the batteries may have been used
for medicinally purposes; the ancient Greeks left written testimonies of the pain
killing effect of electric fish when applied to the soles of the feet.
Other possible uses might have been for religious goals. A cluster of
batteries, connected in series or parallel, may have been put hidden inside a
metal statue or idol. Anyone touching this statue may have received a tiny but
noticeable electric shock, something akin to the static discharge.
Electrochemistry as a Science
The actual date of birth of electrochemistry may be traced in 1791 when
Luigi Galvani (1737-1798) noticed that touching detached frog legs with a
scalpel, they moved, and attributes this movement to animal electricity (see fig.
2). However, Alessandro Volta (1745-1827) has shown that the frog legs
twitched because a small current was generated by bringing in contact a scalpel
made of different metals via a biological liquid.
Volta is one of the most prolific forefathers of electrochemistry. In fact
the first understanding of an electrochemical cell and its practical manufacture
(1800) belongs to Volta (see fig. 3).

Fig. 2. A depiction of Galvani’s

Fig. 3. Volta’s first battery
experiment on “animal” electricity

The name of electrochemistry is established in 1807 by Sir Humphry

Davy (1778 – 1829), one of the best electrochemists; he discovered with the
help of electrolysis a large number of elements such as sodium, potassium,
aluminium etc.
In 1834, Michael Faraday (1791 – 1867), Sir Humphry Davy’s former
assistant, postulates, on the basis of repeated replicated practical experiments
that the amount of chemical change is proportional to the quantity of electricity
passed, and that for the same quantity of electricity the amounts of different
substances deposited or dissolved are proportional to their chemical equivalent
weights. He introduced the terms cathode, anode, electrode, ion, cation, anion,
and electrolyte.
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 Fig. 4. Michael Faraday.
Gravure after a portrait of Charles Turner
Another important step in the development of electrochemistry is marked
in 1836 when John Daniell (1790-1845) invent an electrochemical cell
(Daniell’s cell) that would deliver a constant current over a long period of time.
Most of the people would not believe their ears when told that the so
common barely changed lead acid battery used largely in the automotive
industry dates from 1859, when Gaston Plante (1834-1889) has developed this
dominant cornerstone in rechargeable battery technology.
In 1866 Georges Leclanche (1839-1882) developed the zinc-manganese
dioxide battery, a battery still in use today. The end of the 19th Century brings
along important changes, especially in the field of theoretical and practical
electrochemistry:
- In 1888 Wilhelm Ostwald (1853-1932; Nobel Prize 1909) published its
research finding concerning the dilution law, defining the degree of ionisation of
an electrolyte to its concentration and establishing the basis of conductivity
theory;
- In 1889 Walther Nernst (1864-1941; Nobel Prize 1920) presented an
equation for the electromotive force developed by a given electrochemical
system, an important equation for the electrochemical theoretical calculus and
experimental research.
- In 1890s a lot of practical industrial electrochemical processes for the
production of chemicals are developed (the production of caustic soda and
chlorine from brine).
The beginning of the 20th Century (1901) is marked by Thomas A. Edison
(1847-1931) and Waldemar Jungner (1869-1924) who invent the first alkaline
rechargeable batteries, still in used today.
The first important discovery in the field of electrochemical
measurements belongs to Jaroslav Heyrovsky (1890-1967; Nobel Prize 1959)
who has used in 1922, for the first time, a dropping mercury electrode to analyse
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ions in solution by electrolysis. The technique has been named latter
polarography.
1935 marks the first commercially successful electronic pH meter,
constructed by Arnold O. Beckman (1900-2002). In 1960 Wilson Greatbatch
(1919-) develops the heart pacemaker powered by a battery designed by Samuel
Ruben (1900-1988) for Duracell. This type of battery will be further developed
to become an important brand name on the market.
1990s mark the point of extending the electric vehicles projects from the
laboratory phase to road testing phase. This phase was helped by important
discoveries in the field of rechargeable batteries and fuel cells.
2000s bring on the market large scale fuel cell plants (well over 100
MW) for renewable, clean electricity generation.
If one takes into consideration that electrochemical conversion of
chemical energy into electricity has one of the highest efficiencies and that more
and more practical electrochemical applications are put on the market the future
of electrochemistry looks very appealing (see fig 5).

Fig. 5. Practical applications of electrochemistry

Source: EPRI Report TR-107022/12.1997, Electrolytic Processes,
Present and Future Prospects

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 Electrolysis cells/Galvanic cells

The electrochemical reactions (excepting the natural occurring ones) take

place in well confined spaces, named electrochemical cells. Depending on the
particular nature of these reactions, the electrochemical cells may be divided in:
a) electrolysis cells
b) galvanic/voltaic cells
In an electrolysis cell one uses of an external electrical energy source,
either from a battery or a rectifier to drive a nonspontaneous redox reaction,
transforming the electrical energy into chemical energy, contained within the
reaction products.
Any electrolysis cell consists of a d.c. power supply, two identical or
distinct pieces of metal, semiconductors or graphite (electrodes) and an
electrolyte solution and may or may not be separated by a porous barrier that
prevents the reaction products from mixing (Fig. 6).

Fig. 6. Electrolysis cell

In a galvanic or voltaic cell a spontaneous redox reaction takes place,
resulting in an electromotive force (a voltage); should the circuit be completed
with an external resistor, then a direct current (the rate of flow of charge) is
generated, so the chemical energy is converted into an electric energy.

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 A typical galvanic cell consists of two pieces of metal, e.g. one zinc and
the other copper, each immersed in a solution containing a dissolved salt of the
corresponding metal. The two solutions are separated by a porous barrier or a
salt bridge that prevents them from rapidly mixing, but allows ions to diffuse
through (Fig. 7).

Fig. 7. Galvanic cell

A particular case of electrochemical cell is represented by a rechargeable

battery that acts as a galvanic cell during the discharge phase supplying
electrical energy and as an electrolysis cell during the recharge period when the
electric energy is stored under the form of chemical energy.
The process taking place in the above said cells can be represented as a
couple of chemical reaction and electron transfer generally known as
electrochemical processes, and the process taking place at any metal/electrolyte
interface is known as electrode process, where the electrode is the generic term
designated by an electronic conductor in contact with an ionic conductor (e.g.
metal in contact with an electrolyte).
Depending on the nature of the electrode process, the electrodes may by
called anode (electrode at which oxidation takes place):

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 R e d1 → Ox1 + z1e− (1a)

and cathode (electrode at which reduction takes place):

Ox2 + z2 e − → R e d 2 (1b)

regardless on the nature of the electrochemical cell (galvanic cell or electrolysis

cell). The above two reactions may be combined in an overall reaction:

z2 R e d1 + z1Ox2 → z2Ox1 + z1 R e d 2 (2)

In an electrolysis cell, the charged species from the electrolyte solution

shall migrate towards the opposite corresponding electrode: cations are the
positive species that move to the cathode and anions are the negative species
that move to the anode. As one may often confuse the polarity of electrodes, one
may emphasise the general rule that cathodes and anodes have opposite signed
in electrolysis cells with respect to the galvanic cells, namely: Electrolysis cell,
anode is (+) and cathode is (-); Galvanic cell, anode is (-) and cathode is (+).