Some Observations on the History of Electrochemistry in Europe

D. Noel Buckley

University of Limerick, Ireland

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1

Early Observations of Electricity

• Atmospheric Electricity
• Animal Electricity
• Static (Frictional) Electricity

Atmospheric Electricity

Lightning over Oradea, Romania during 2005 thunderstorm (Mircea Madau)

https://en.wikipedia.org/wiki/File:Lightning_over_Oradea_Romania_3.jpg

Animal Electricity

Electric catfish (centre) in Mastaba of Ti bas-relief, Saqqara, ancient Egypt https://en.wikipedia.org/wiki/History_of_bioelectricity

4000 BC: Electric catfish in Egyptian murals

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400 BC: Greek philosopher Plato to Socrates: “... you seem both in your appearance and in your power over others to be like a torpedo fish, who torpifies those who come near him ...”

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- P. Kellaway, Bulletin of the History of Medicine, 20, 112-137 (1946)

Frictional Electricity

600 BC: The Greek philosopher Thales of Miletus discovered that amber, when rubbed with cat’s fur, attracted feathers and other light objects. This is static electricity. The word comes from the Greek elektron  meaning “amber” (https://www.britannica.com/summary/electricity)

https://taraenergy.com/blog/history-of-electricity/

https://iep.utm.edu/thales/

Thales

(620-546 BC)

Electrostatic Machines

• Otto van Guericke
• first electric generator, 1663
• sulfur ball inside a glass globe
• ball rotated by means of a crank
• electric spark when a pad was rubbed against the ball
• Electrostatic Machines improved throughout the 1700s

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https://www.corrosion-doctors.org/Biographies/GuerickeBio.htm#:~:text=In%201663%20Otto%20van%20Guericke,globe%2C%20mounted%20on%20a%20shaft.

Otto van

Guericke

(1602-86)

Benjamin Franklin’s Electrostatic Machine��

Exhibit from the Benjamin Franklin collection in the Franklin Institute, Philadelphia, Pennsylvania, USA. Photographed by Daderot

Benjamin Franklin (1705-90)

Artist Anon. (Photo by Heritage Art/Heritage Images via Getty Images).

Leyden Jar

https://commons.wikimedia.org/wiki/File:Early_Layden_jar.png#/media/File:Early_Layden_jar.png

• Ewald Georg von Kleist
• Attempt to store electricity in water in a bottle
• Pieter van Musschenbroek
• Developed more fully
• Letter to Reaumur, led to name Leyden Jar

Von Kleist (1700-48)

https://pantheon.world/profile/person/Ewald_Georg_von_Kleist/

van Musschenbroek (1692-1761)

https://commons.wikimedia.org/wiki/File:P_v_Musschenbroek_t-E.jpg#/media/File:P_v_Musschenbroek_t-E.jpg

Leyden Jar Battery

Science History Institute/Gregory Tobias

https://sciencehistory.org/stories/magazine/leyden-jar-battery/

Electrochemistry to the rescue ...

Early Observations of Electricity

• Atmospheric Electricity
• Animal Electricity
• Static (Frictional) Electricity

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Early Observations of Electricity

• Atmospheric Electricity
• Animal Electricity
• Static (Frictional) Electricity
• Galvanic Electricity

Luigi Galvani (1737 – 1798)

https://commons.wikimedia.org/wiki/File:Luigi_Galvani,_oil-painting.jpg#/media/File:Luigi_Galvani,_oil-painting.jpg

• Galvani was a surgeon and biologist
• 1780s: Began studies of role of electricity in neuromuscular function
• January 1781: Spark from electrical

machine caused frog leg to twitch

• 1780 – 83: Effect of artificial electricity
• 1783 – 86: Other physicochemical effects
• 1786: Effect of atmospheric electricity
• September 1786: Effect of metal connection alone on frog leg twitching
• 1786 onward: Effect of metal connection
• Explained results as Animal Electricity

M. Piccolino, C. R. Biologies 329, 303–318 (2006)

Electrical spark causes frog’s leg to twitch (Jan. 1781)

As described at the beginning of the De Viribus, this observation became the starting point of all further investigations, and its fortuitous character is emphasised: a frog preparation contracts when somebody (“my wife or other” he notes in the experimental protocols) extracts the spark from an electrical machine which is “not connected” to the frog by any type of conductor.

A circumstance so accidental as the slight illness of Madam Galvani gave rise to this important event. Her physician had recommended her to a diet of frog-broth, and several of the animals, prepared for the cook, chanced to lie on a table near an electrical machine. One of Galvani's assistants drew sparks from the conductor, and Madam Galvani was surprised to observe that when he did so the muscles of the frogs were distorted and assumed the appearance of life. She called Galvani to notice the strange circumstance. The experiment was repeated with success, and the philosopher, who knew little of electricity, but was a careful anatomist, believe'd he was on the brink of discovering the principle of life.

- J. M. Bleyer, Galvanism, in International Text-Book of Medical Electro-Physics and Galvanism for the use of Medical Students and Practitioners (The F. A. Davis Company, Philadelphia, 1895), p. A203.

- M. Piccolino, C. R. Biologies 329, 303–318 (2006)

Experiment on Atmospheric Electricity

[1] L. Galvani, De viribus electricitatis in motu musculari commentarius, De Bononiensi Scientiarum et Artium Instituto atque Academia commentarii 7, 363–418 (1791)

September 1786:

“... contractions appeared when the metallic hooks were pushed toward the iron bars of the railing, with no relation whatsoever with atmospheric events.”

- M. Piccolino, C. R. Biologies 329, 303–318 (2006), paraphrasing from [1]

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Mary Shelley’s Novel Frankenstein

https://en.wikipedia.org/wiki/Frankenstein

https://en.wikipedia.org/wiki/Mary_Shelley

https://www.britannica.com/topic/Frankenstein-film-by-Whale

• Inspired partly by “Animal Electricity” Experiments

Alessandro Volta (1745–1827)

• Volta was an “electrician”
• Had made many earlier electrical discoveries
• Initially agreed with Galvani’s Theory of Animal Electricity
• 1792: Began to doubt the theory
• Showed electricity was produced by two metals in salt solution with no animal involvement
• Invented voltaic pile
• Established “Electrochemical Series”
• Contact tension theory

Voltaic Pile

https://en.wikipedia.org/wiki/History_of_the_battery

Voltaic Pile and “Crown of Cups”

From the Philosophical Transactions in which Volta's letter to Joseph Banks was published. The letter was dated 20 March 1800. https://wellcomecollection.org/works/z7jzdcb7

“Crown of Cups”

Artwork from 'Electricite' (1911) by Max de Nansouty, part of the 'Les merveilles de la science' series of 1867-1891 by Louis Figuier.

Voltaic Pile

• The voltaic pile was the first source of continuous electric current
• Enabled a rapid series of other discoveries
• electrolysis) of water by William Nicholson and Anthony Carlisle (1800)
• the discovery Na, K, Ca, B, Ba, Sr and Mg by electrolysis of molten salts (Humphry Davy, 1907-08)
• Virtually the entire 19th-century source of electricity electrochemical batteries until the advent of the electrical generator in the 1870s.

Electrolysis of Water (1800)

https://commons.wikimedia.org/wiki/File:Anthony_Carlisle_by_Henry_Bone.jpg#/media/File:Anthony_Carlisle_by_Henry_Bone.jpg

Anthony Carlisle

(1768 – 1840)

William Nicholson

(1753-1815)

https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/elsa.202160003

• Built Zn-Cu Voltaic pile
• Immersed poles in water to produce H₂ and O₂
• First demo of interaction of electricity and materials causing chemical transformation

Sir Humphry Davy (1778 – 1829)

• British chemist and inventor
• Discovered Na, K, Ca, B, Ba, Sr and Mg by electrolysis of molten salts (1807-08)
• Studied the forces involved in these separations
• beginning of electrochemistry.
• Large electric battery in Royal Institution
• charcoal electrodes produced the first electric light

Faraday developed early theory of electrochemistry

Michael Faraday

by Thomas Phillips (Wikipedia)

• Described species carrying current (called them anions and cations)
• Coined terms electrode, anode, cathode
• Laws of Electrolysis
• 1^st Law: Mass m of element deposited m ∝ Q
• 2^nd Law: For any Q , m ∝ E where E = chemical equivalent weight

Early Battery Development

William Cruickshank (c.1740 – c.1811)

(wikipedia)

• First electric battery for mass production (1802)
• Sheets of copper and zinc in a rectangular wooden box filled with an electrolyte of brine, or dilute acid.

Daniell Cell, 1836

https://en.wikipedia.org/wiki/John_Frederic_Daniell

• Voltaic pile problem
• Hydrogen bubbles at copper electrode
• Daniell cell has a copper sulfate solution, separated from zinc by a porous pot
• Longer, more reliable current than Voltaic pile.
• Voltage of about 1.1 volts.
• Became industry standard for electricity generation
• First working standard for definition of the volt

John Frederic Daniell

(1790 – 1845)

Grove Cell, 1844

• Grove cell
• zinc in sulfuric acid
• platinum in nitric acid
• separated by porous earthenware.
• Provided high current and nearly twice the voltage of the Daniell cell
• Poisonous nitric oxide fumes and voltage drops sharply as it discharges

William Robert Grove

(1811 – 1896)

Lead-Acid Battery, 1859

• First re-chargeable battery
• Two lead electrodes in sulphuric acid
• 2 V, almost twice the voltage of Daniell Cell
• Became industrially important after 1871 (Gramme dynamo)
• Still an important battery

Gaston Planté

(1834 – 1889)

(Wikipedia)

Leclanche Cell, 1866

• zinc negative
• carbon/manganese dioxide positive
• ammonium chloride electrolyte
• In 1876, Leclanché jellified the electrolyte with starch
• First version of “dry cell”
• In 1887 Carl Gassner improved dry cell
• Plaster of Paris instead of starch

Georges Leclanché

(1839 – 1882)

https://en.wikipedia.org/wiki/Georges_Leclanch%C3%A9

Nickel-Cadmium 1899

• Rechargeable battery
• First alkaline battery
• Nickel positive
• Cadmium negative
• Sodium hydroxide electrolyte
• Better energy density than Lead-acid
• More expensive

Ernst Waldemar Jungner

(1869 – 1924)

Electrodeposition

Electroplating

• Discovered in 1805 by Italian Luigi V. Brugnatelli.
• Connected a metal object in solution to a Voltaic pile
• Not much more was done until 1840
• Copper plating was used for coating printing plates
• John Wright discovered cyanide plating bath for gold and silver
• Wright's associates, George and Henry Elkington founded the electroplating industry in Birmingham from where it spread around the world.
• Commercial electroplating of nickel, brass, tin, and zinc were developed by the 1850s.

Luigi Brugnatelli (1761 – 1818)

Luigi Valentino Brugnatelli

engraving by F. Bordiga, 1806 (Wikipedia)

"I have lately gilt in a complete manner two large silver medals, by bringing them into communication by means of a steel wire, with a negative pole of a voltaic pile, and keeping them one after the other immersed in ammoniuret of gold newly made and well saturated".

Belgian Journal of Physics and Chemistry, (https://www.thoughtco.com/history-of-electroplating-1991599)

Elkington Electroplating in Birmingham

George Richards Elkington

(1801–1865)

by Samuel West (Wikipedia)

Elkington Silver Electroplating Works, Birmingham (1874)

https://victorianweb.org/art/design/metalwork/elkington.html

Woolwich Generator 1844

• Woolwich generator was used for electroplating - first industrial use.
• More generally, practical generators from about 1860

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Transport of current and �properties of electrolytes

Johann Wilhelm Hittorf (1824 – 1914)

• Transport of electricity in liquids and gases
• Ion transport numbers and their measurement

Friedrich Wilhelm Georg Kohlrausch (1840 – 1910)

• Electrolyte conductivity
• Thermal conduction
• Precision electrical measurements.
• Electrical and magnetic measuring units

Friedrich Wilhelm Ostwald (1853 – 1932)

• Dilution Theory of Electrolytes
• Catalysis
• Chemical equilibria
• Reaction velocities
• Nobel Prize (Chemistry) 1909

Dissociation of Electrolytes

• Ionic Dissociation
• Conductivity of electrolytes
• Definition of acids and bases
• Arrhenius equation
• Greenhouse effect
• Nobel Prize (Chemistry) 1903

Svante August Arrhenius

(1859 – 1927)

Concept of Unit Charge (e)

Hermann von Helmholtz (1821 – 1894)

George J. Stoney

(1826-1911).

J. J. Thompson

(1826-1911).

Thermodynamics, Free Energy

Josiah Willard Gibbs (1839-1903)

Hermann von Helmholtz (1821 – 1894)

Walther Hermann Nernst (1864 – 1941)

• Thermodynamics
• Nernst Equation (1887)
• Nobel Prize (Chemistry) 1920

Julius Tafel (1862 – 1918)

Julius Tafel, around 1905. (Courtesy Chemical Institute, Wurzburg University) https://knowledge.electrochem.org/encycl/art-t01-tafel.htm

Tafel Equation (1905)

η = a + b log i

pH Scale (1909)

Søren Peter Lauritz Sørensen

(1868–1939)

(Wikipedia)

• Head of Carlsberg Laboratory (1901-1938)
• Invented pH scale 1909
• Measured by
• Voltage at hydrogen electrode
• Indicators

Polarography

Mercury, Electrocapillarity, Poloragraphy ...

Nobel Lectures, Physics 1901-1921, Elsevier (1967)

Bohumil Kučera

(1874 - 1921)

M. G. Lippmann (1845 - 1921)

Jaroslav Heyrovský (1890 - 1967)

Wikipedia

http://www.jh-inst.cas.cz

Lippmann Capillary Electrometer

Mercury, Electrocapillarity, Poloragraphy ...

• Lippmann, 1873: Mercury, surface tension of polarized electrodes.
• Kučera, 1902: Surface tension by weighing mercury drops
• Heyrovský: Anomaly in drop weight vs potential curves.
• Friday, 10^th February 1922 afternoon
• measured current
• Reproducible I – V behaviour
• Wave-shaped curves
• Heights depended on concentration

Michael Heyrovský, “Polarography—past, present, and future”

J. Solid State Electrochem. 15, 1799–1803 (2011)

Birth of Polarography

The Basic Polarographic Method, 1922

J A R O S L A V H E Y R O V S K Ý

Nobel Lecture, December 11, 1959

• Working electrode: dropping mercury electrode
• High overpotential for hydrogen
• Excellent for probing electrochemical reductions
• Clean surface
• Counter electrode: mercury pool
• Positively polarised in chloride 🡪 calomel
• Large area
• Maintains constant potential during current flow
• Combined counter and reference electrode
• Control potential with a simple potentiometer
• Measure current with galvanometer

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The First Polarograph, 1924

J. Heyrovský, M. Shikata, “Researches with the dropping mercury cathode: Part II. The Polarograph”, Recueil des Travaux Chimiques des Pays-Bas, 44, 496-498 (1925)

(Wikipedia)

• J. Heyrovský, M. Shikata,
• First automatic recording of I – V curves
• Wooden drum
• wound with resistance wire
• sheet of photographic paper
• Mirror galvanometer
• Rotation of drum 🡪 x-axis (voltage)
• Light beam from mirror 🡪 y-axis (current)

The Importance of Polarography

• Fundamental
• Mercury-solution interface was ideal for many fundamental studies
• Polarograph enabled precise quantitative studies
• Emphasis on voltage as independent variable
• Operational
• First “automatic instrument”
• First instrumental analysis in analytical chemistry
• Chemical analysis
• Qualitative and quantitative analysis

Invention of Potentiostat 1941

Wenking Potentiostat

Hans Wenking (1923 - 2007)

Early potentiostat designs:

Wenking, Bank, Jaissle, Taccusel

First commercial potentiostat: ~1954

First commercial transistor radio: 1954

Charging Curve

D. N. Buckley, PhD Thesis, National University of Ireland (1975)

From HP Memory Project Collection. https://www.hpmemoryproject.org/wb_pages/wall_b_page_13.htm

© Hewlett-Packard, reproduced by permission.

Data Acquisition and Processing

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• Analog meters and chart recorders
• Data was typically read off manually
• Written in lab notebook
• Slide rule → Desk calculator (about 1970)
• Papers/theses handwritten for typist
• Word processing arrived about 1980
• Literature search: books of abstracts in library (Chem. Abs. etc)

Slide Rules

Slide-Rule Owner

Desk-top calculator ~ 1968

IBM Card Punch Machine

Punched Card

Line-Printer Paper

CONCLUSION

These things ... are the episodes of that cyclic poem written by Time upon the memories of men. The Past, like an inspired rhapsodist, fills the theatre of everlasting generations with their harmony.

- Percy Bysshe Shelley: A Defence of Poetry