electrochemical reduction
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Electrochemistry is the branch of
physical chemistry Physical chemistry is the study of macroscopic scale, macroscopic and Microscopic scale, microscopic phenomena in chemistry, chemical systems in terms of the principles, practices, and concepts of physics such as Motion (physics), motion, energy ...
concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outcome of a particular chemical change, or vice versa. These reactions involve electrons moving via an electronically-conducting phase (typically an external electrical circuit, but not necessarily, as in
electroless plating Electroless plating, also known as chemical plating or autocatalytic plating, is a class of industrial chemical processes that create metal coatings on various materials by autocatalysis, autocatalytic redox reaction, chemical reduction of metal ca ...
) between electrodes separated by an ionically conducting and electronically insulating electrolyte (or ionic
species In biology, a species is the basic unit of Taxonomy (biology), classification and a taxonomic rank of an organism, as well as a unit of biodiversity. A species is often defined as the largest group of organisms in which any two individuals of ...
in a solution). When a chemical reaction is driven by an electrical potential difference, as in
electrolysis In chemistry Chemistry is the scientific study of the properties and behavior of matter. It is a natural science that covers the elements that make up matter to the compounds made of atoms, molecules and ions: their composition, str ...
, or if a potential difference results from a chemical reaction as in an
electric battery An electric battery is a source of electric power consisting of one or more electrochemical cells with external connections for powering Electricity, electrical devices. When a battery is supplying power, its positive terminal is the cathode a ...
or
fuel cell A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen fuel, hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most bat ...
, it is called an ''electrochemical'' reaction. Unlike in other chemical reactions, in electrochemical reactions electrons are not transferred directly between atoms, ions, or molecules, but via the aforementioned electronically-conducting circuit. This phenomenon is what distinguishes an electrochemical reaction from a conventional chemical reaction.


History


16th–18th century

Understanding of electrical matters began in the sixteenth century. During this century, the English scientist William Gilbert spent 17 years experimenting with
magnetism Magnetism is the class of physical attributes that are mediated by a magnetic field, which refers to the capacity to induce attractive and repulsive phenomena in other entities. Electric currents and the magnetic moments of elementary particles ...
and, to a lesser extent, electricity. For his work on magnets, Gilbert became known as the ''"Father of Magnetism."'' He discovered various methods for producing and strengthening magnets. In 1663, the German
physicist A physicist is a scientist who specializes in the field of physics, which encompasses the interactions of matter and energy at all length and time scales in the physical universe. Physicists generally are interested in the root or ultimate caus ...
Otto von Guericke Otto von Guericke ( , , ; spelled Gericke until 1666; November 20, 1602 – May 11, 1686 ; November 30, 1602 – May 21, 1686 ) was a German scientist, inventor, and politician. His pioneering scientific work, the development of experimental me ...
created the first electric generator, which produced static electricity by applying friction in the machine. The generator was made of a large
sulfur Sulfur (or sulphur in British English British English (BrE, en-GB, or BE) is, according to Oxford Dictionaries, " English as used in Great Britain, as distinct from that used elsewhere". More narrowly, it can refer specifically to the ...
ball cast inside a glass globe, mounted on a shaft. The ball was rotated by means of a crank and an
electric spark An electric spark is an abrupt electrical discharge that occurs when a sufficiently high electric field creates an Ionization, ionized, Electric current, electrically conductive channel through a normally-insulating medium, often air or other ga ...
was produced when a pad was rubbed against the ball as it rotated. The globe could be removed and used as source for experiments with electricity. By the mid-18th century the French
chemist A chemist (from Greek ''chēm(ía)'' alchemy; replacing ''chymist'' from Medieval Latin ''alchemist'') is a scientist trained in the study of chemistry. Chemists study the composition of matter and its properties. Chemists carefully describe th ...
Charles François de Cisternay du Fay had discovered two types of static electricity, and that like charges repel each other whilst unlike charges attract. Du Fay announced that electricity consisted of two fluids: ''"vitreous"'' (from the
Latin Latin (, or , ) is a classical language belonging to the Italic languages, Italic branch of the Indo-European languages. Latin was originally a dialect spoken in the lower Tiber area (then known as Latium) around present-day Rome, but through ...
for ''"glass"''), or positive, electricity; and ''"resinous,"'' or negative, electricity. This was the ''two-fluid theory'' of electricity, which was to be opposed by
Benjamin Franklin Benjamin Franklin ( April 17, 1790) was an American polymath who was active as a writer, scientist, Invention, inventor, Statesman (politician), statesman, diplomat, printer (publishing), printer, publisher, and Political philosophy, politi ...
's ''one-fluid theory'' later in the century. In 1785,
Charles-Augustin de Coulomb Charles-Augustin de Coulomb (; ; 14 June 1736 – 23 August 1806) was a French officer, engineer, and physicist. He is best known as the eponymous discoverer of what is now called Coulomb's law, the description of the electrostatics, electrostatic ...
developed the law of
electrostatic Electrostatics is a branch of physics that studies electric charges at rest ( static electricity). Since classical times, it has been known that some materials, such as amber, attract lightweight particles after rubbing. The Greek word f ...
attraction as an outgrowth of his attempt to investigate the law of electrical repulsions as stated by
Joseph Priestley Joseph Priestley (; 24 March 1733 – 6 February 1804) was an English chemist, Natural philosophy, natural philosopher, English Separatist, separatist theologian, Linguist, grammarian, multi-subject educator, and Liberalism, liberal Politi ...
in England. In the late 18th century the Italian
physician A physician (American English), medical practitioner (English in the Commonwealth of Nations, Commonwealth English), medical doctor, or simply doctor, is a health professional who practices medicine, which is concerned with promoting, mai ...
and
anatomist Anatomy () is the branch of biology concerned with the study of the structure of organisms and their parts. Anatomy is a branch of natural science that deals with the structural organization of living things. It is an old science, having its ...
Luigi Galvani Luigi Galvani (, also ; ; la, Aloysius Galvanus; 9 September 1737 – 4 December 1798) was an Italian physician, physicist, biologist and philosopher, who studied Galvanism, animal electricity. In 1780, he discovered that the muscles of dead fr ...
marked the birth of electrochemistry by establishing a bridge between chemical reactions and electricity on his essay ''"De Viribus Electricitatis in Motu Musculari Commentarius"'' (Latin for Commentary on the Effect of Electricity on Muscular Motion) in 1791 where he proposed a ''"nerveo-electrical substance"'' on biological life forms.John Robert Norris, Douglas W. Ribbons (1972
Methods in microbiology, Volume 6
Academic Press. p. 248
In his essay Galvani concluded that animal tissue contained a here-to-fore neglected innate, vital force, which he termed ''"animal electricity,"'' which activated
nerve A nerve is an enclosed, cable-like bundle of nerve fibers (called axons) in the peripheral nervous system. A nerve transmits electrical impulses. It is the basic unit of the peripheral nervous system. A nerve provides a common pathway for the E ...
s and
muscle Skeletal muscles (commonly referred to as muscles) are Organ (biology), organs of the vertebrate muscular system and typically are attached by tendons to bones of a skeleton. The muscle cells of skeletal muscles are much longer than in the other ...
s spanned by metal probes. He believed that this new force was a form of electricity in addition to the ''"natural"'' form produced by
lightning Lightning is a naturally occurring electrostatic discharge during which two electric charge, electrically charged regions, both in the atmosphere or with one on the land, ground, temporarily neutralize themselves, causing the instantaneous ...
or by the
electric eel The electric eels are a genus, ''Electrophorus'', of Neotropical realm, neotropical freshwater fish from South America in the family Gymnotidae. They are known for their electric fish, ability to stun their prey by generating electricity, deli ...
and torpedo ray as well as the ''"artificial"'' form produced by
friction Friction is the force resisting the relative motion of solid surfaces, fluid layers, and material elements sliding (motion), sliding against each other. There are several types of friction: *Dry friction is a force that opposes the relative la ...
(i.e., static electricity).Frederick Collier Bakewel
Electric science; its history, phenomena, and applications
Ingram, Cooke (1853) pp. 27–31
Galvani's scientific colleagues generally accepted his views, but
Alessandro Volta Alessandro Giuseppe Antonio Anastasio Volta (, ; 18 February 1745 – 5 March 1827) was an Italian physicist, chemist and lay List of lay Catholic scientists, Catholic who was a pioneer of electricity and Power (physics), power who is credite ...
rejected the idea of an ''"animal electric fluid,"'' replying that the frog's legs responded to differences in metal temper, composition, and bulk. Galvani refuted this by obtaining muscular action with two pieces of the same material. Nevertheless, Volta's experimentation led him to develop the first practical battery, which took advantage of the relatively high energy (weak bonding) of zinc and could deliver an electrical current for much longer than any other device known at the time.


19th century

In 1800, William Nicholson and Johann Wilhelm Ritter succeeded in decomposing water into
hydrogen Hydrogen is the chemical element with the Symbol (chemistry), symbol H and atomic number 1. Hydrogen is the lightest element. At standard temperature and pressure, standard conditions hydrogen is a gas of diatomic molecules having the chemical ...
and
oxygen Oxygen is the chemical element with the chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen Group (periodic table), group in the periodic table, a highly Chemical reaction, reactive nonmetal, and an oxidizing a ...
by
electrolysis In chemistry Chemistry is the scientific study of the properties and behavior of matter. It is a natural science that covers the elements that make up matter to the compounds made of atoms, molecules and ions: their composition, str ...
using Volta's battery. Soon thereafter Ritter discovered the process of
electroplating Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the redox, reduction of cations of that metal by means of a direct current, direct electric cur ...
. He also observed that the amount of metal deposited and the amount of oxygen produced during an electrolytic process depended on the distance between the
electrode An electrode is an electrical conductor used to make contact with a nonmetallic part of a Electronic circuit, circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of Electric battery, batteries that can ...
s. By 1801, Ritter observed thermoelectric currents and anticipated the discovery of thermoelectricity by
Thomas Johann Seebeck Thomas Johann Seebeck (; 9 April 1770 – 10 December 1831) was a Baltic German Baltic Germans (german: Deutsch-Balten or , later ) were Germans, ethnic German inhabitants of the eastern shores of the Baltic Sea, in what today are Eston ...
. By the 1810s,
William Hyde Wollaston William Hyde Wollaston (; 6 August 1766 – 22 December 1828) was an English people, English chemist and physicist who is famous for discovering the chemical elements palladium and rhodium. He also developed a way to process platinum ore into ...
made improvements to the
galvanic cell A galvanic cell or voltaic cell, named after the scientists Luigi Galvani and Alessandro Volta, respectively, is an electrochemical cell in which an electric current is generated from Spontaneous reaction, spontaneous Oxidation-Reduction reactions. ...
. Sir
Humphry Davy Sir Humphry Davy, 1st Baronet, (17 December 177829 May 1829) was a British people, British chemist and inventor who invented the Davy lamp and a very early form of arc lamp. He is also remembered for isolating, by using electricity, several C ...
's work with electrolysis led to the conclusion that the production of electricity in simple
electrolytic cell An electrolytic cell is an electrochemical cell that utilizes an external source of electrical energy to force a chemical reaction that would not otherwise occur. The external energy source is a voltage applied between the cell′s two electrode ...
s resulted from chemical action and that chemical combination occurred between substances of opposite charge. This work led directly to the isolation of metallic
sodium Sodium is a chemical element with the Symbol (chemistry), symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the ...
and
potassium Potassium is the chemical element with the Symbol (chemistry), symbol K (from New Latin, Neo-Latin ''wikt:kalium#Latin, kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little fo ...
by electrolysis of their molten salts, and of the
alkaline earth metal The alkaline earth metals are six chemical element A chemical element is a species of atoms that have a given number of protons in their atomic nucleus, nuclei, including the pure Chemical substance, substance consisting only of that spec ...
s from theirs, in 1808. Hans Christian Ørsted's discovery of the magnetic effect of electric currents in 1820 was immediately recognized as an epoch-making advance, although he left further work on
electromagnetism In physics, electromagnetism is an interaction that occurs between particles with electric charge. It is the second-strongest of the four fundamental interactions, after the strong force, and it is the dominant force in the interactions of a ...
to others.
André-Marie Ampère André-Marie Ampère (, ; ; 20 January 177510 June 1836) was a French physicist A physicist is a scientist who specializes in the field of physics, which encompasses the interactions of matter and energy at all length and time scales in th ...
quickly repeated Ørsted's experiment, and formulated them mathematically. In 1821, Estonian-German
physicist A physicist is a scientist who specializes in the field of physics, which encompasses the interactions of matter and energy at all length and time scales in the physical universe. Physicists generally are interested in the root or ultimate caus ...
Thomas Johann Seebeck Thomas Johann Seebeck (; 9 April 1770 – 10 December 1831) was a Baltic German Baltic Germans (german: Deutsch-Balten or , later ) were Germans, ethnic German inhabitants of the eastern shores of the Baltic Sea, in what today are Eston ...
demonstrated the electrical potential between the juncture points of two dissimilar metals when there is a temperature difference between the joints.Brian Scott Baigri
Electricity and magnetism: a historical perspective
Greenwood Publishing Group (2007) p. 73
In 1827, the German scientist
Georg Ohm Georg Simon Ohm (, ; 16 March 1789 – 6 July 1854) was a German physicist A physicist is a scientist who specializes in the field of physics, which encompasses the interactions of matter and energy at all length and time scales in the phys ...
expressed his
law Law is a set of rules that are created and are law enforcement, enforceable by social or governmental institutions to regulate behavior,Robertson, ''Crimes against humanity'', 90. with its precise definition a matter of longstanding debate. ...
in this famous book ''"Die galvanische Kette, mathematisch bearbeitet"'' (The Galvanic Circuit Investigated Mathematically) in which he gave his complete theory of electricity. In 1832,
Michael Faraday Michael Faraday (; 22 September 1791 – 25 August 1867) was an English scientist who contributed to the study of electromagnetism and electrochemistry. His main discoveries include the principles underlying electromagnetic induction, ...
's experiments led him to state his two laws of electrochemistry. In 1836, John Daniell invented a primary cell which solved the problem of
polarization Polarization or polarisation may refer to: Mathematics *Polarization of an Abelian variety, in the mathematics of complex manifolds *Polarization of an algebraic form, a technique for expressing a homogeneous polynomial in a simpler fashion by ...
by introducing copper ions into the solution near the positive electrode and thus eliminating
hydrogen Hydrogen is the chemical element with the Symbol (chemistry), symbol H and atomic number 1. Hydrogen is the lightest element. At standard temperature and pressure, standard conditions hydrogen is a gas of diatomic molecules having the chemical ...
gas generation. Later results revealed that at the other electrode, amalgamated
zinc Zinc is a chemical element with the Symbol (chemistry), symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 eleme ...
(i.e., zinc alloyed with mercury) would produce a higher voltage. William Grove produced the first
fuel cell A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen fuel, hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most bat ...
in 1839. In 1846, Wilhelm Weber developed the electrodynamometer. In 1868, Georges Leclanché patented a new cell which eventually became the forerunner to the world's first widely used battery, the zinc–carbon cell.Keith James Laidle
The world of physical chemistry
Oxford University Press (1995) pp. 219–220
Svante Arrhenius Svante August Arrhenius ( , ; 19 February 1859 – 2 October 1927) was a Swedes, Swedish scientist. Originally a physicist, but often referred to as a chemist, Arrhenius was one of the founders of the science of physical chemistry. He received ...
published his thesis in 1884 on ''Recherches sur la conductibilité galvanique des électrolytes'' (Investigations on the galvanic conductivity of electrolytes). From his results the author concluded that
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electr ...
s, when dissolved in water, become to varying degrees split or dissociated into electrically opposite positive and negative ions. In 1886, Paul Héroult and Charles M. Hall developed an efficient method (the Hall–Héroult process) to obtain
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element A chemical element is a species of atoms that have a given number of protons in their atomic nucleus, nuclei, including the pure Chemical substance, substan ...
using electrolysis of molten alumina. In 1894, Friedrich Ostwald concluded important studies of the conductivity and electrolytic dissociation of
organic acid An organic acid is an organic compound with acidic properties. The most common organic acids are the carboxylic acids, whose acidity is associated with their carboxyl group –COOH. Sulfonic acids, containing the group –SO2OH, are rel ...
s. Walther Hermann Nernst developed the theory of the
electromotive force In electromagnetism and electronics, electromotive force (also electromotance, abbreviated emf, denoted \mathcal or ) is an energy transfer to an electric circuit per unit of electric charge, measured in volts. Devices called electrical ''Transd ...
of the voltaic cell in 1888. In 1889, he showed how the characteristics of the voltage produced could be used to calculate the free energy change in the chemical reaction producing the voltage. He constructed an equation, known as
Nernst equation In electrochemistry Electrochemistry is the branch of physical chemistry concerned with the relationship between Electric potential, electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, ...
, which related the voltage of a cell to its properties. In 1898,
Fritz Haber Fritz Haber (; 9 December 186829 January 1934) was a German chemist who received the Nobel Prize in Chemistry in 1918 for his invention of the Haber process, Haber–Bosch process, a method used in industry to synthesize ammonia from nitrogen g ...
showed that definite reduction products can result from electrolytic processes if the potential at the
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction in ...
is kept constant. In 1898, he explained the reduction of
nitrobenzene Nitrobenzene is an organic compound with the chemical formula Phenyl, C6H5Nitro compound, NO2. It is a water-insoluble pale yellow oil with an almond-like odor. It freezes to give greenish-yellow crystals. It is produced on a large scale from be ...
in stages at the cathode and this became the model for other similar reduction processes.


20th century

In 1902,
The Electrochemical Society The Electrochemical Society is a learned society A learned society (; also learned academy, scholarly society, or academic association) is an organization that exists to promote an academic discipline, profession, or a group of related dis ...
(ECS) was founded. In 1909,
Robert Andrews Millikan Robert Andrews Millikan (March 22, 1868 – December 19, 1953) was an American experimental physicist A physicist is a scientist who specializes in the field of physics, which encompasses the interactions of matter and energy at all length ...
began a series of experiments (see
oil drop experiment The oil drop experiment was performed by Robert Andrews Millikan, Robert A. Millikan and Harvey Fletcher in 1909 to measure the Elementary charge, elementary electric charge (the charge of the electron). The experiment took place in the Ryerson ...
) to determine the electric charge carried by a single
electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electric charge. Electrons belong to the first generation (particle physics), generation of the lepton particle family, and are generally thought t ...
. In 1911, Harvey Fletcher, working with Millikan, was successful in measuring the charge on the electron, by replacing the water droplets used by Millikan, which quickly evaporated, with oil droplets. Within one day Fletcher measured the charge of an electron within several decimal places In 1923, Johannes Nicolaus Brønsted and Martin Lowry published essentially the same theory about how acids and bases behave, using an electrochemical basis. In 1937,
Arne Tiselius Arne Wilhelm Kaurin Tiselius (10 August 1902 – 29 October 1971) was a Sweden, Swedish biochemist who won the Nobel Prize in Nobel Prize in Chemistry, Chemistry in 1948 "for his research on electrophoresis and adsorption analysis, especiall ...
developed the first sophisticated
electrophoretic Electrophoresis, from Ancient Greek ἤλεκτρον (ḗlektron, "amber") and φόρησις (phórēsis, "the act of bearing"), is the motion of dispersed particles relative to a fluid under the influence of a spatially uniform electric fi ...
apparatus. Some years later, he was awarded the 1948
Nobel Prize The Nobel Prizes ( ; sv, Nobelpriset ; no, Nobelprisen ) are five separate prizes that, according to Alfred Nobel#Nobel Prize, Alfred Nobel's will of 1895, are awarded to "those who, during the preceding year, have conferred the greatest ben ...
for his work in protein
electrophoresis Electrophoresis, from Ancient Greek ἤλεκτρον (ḗlektron, "amber") and φόρησις (phórēsis, "the act of bearing"), is the motion of Interface and colloid science, dispersed particles relative to a fluid under the influence of a ...
. A year later, in 1949, the International Society of Electrochemistry (ISE) was founded. By the 1960s–1970s quantum electrochemistry was developed by Revaz Dogonadze and his students.


Principles


Oxidation and reduction

The term "
redox Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate (chemistry), substrate change. Oxidation is the loss of Electron, electrons or an increase in the oxidation state, while reduction ...
" stands for reduction-oxidation. It refers to electrochemical processes involving
electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electric charge. Electrons belong to the first generation (particle physics), generation of the lepton particle family, and are generally thought t ...
transfer to or from a
molecule A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioche ...
or ion, changing its
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical Electrical charge, charge of an atom if all of its Chemical bond, bonds to different atoms were fully Ionic bond, ionic. It describes the degree of oxidation (loss of elec ...
. This reaction can occur through the application of an external
voltage Voltage, also known as electric pressure, electric tension, or (electric) potential difference, is the difference in electric potential between two points. In a Electrostatics, static electric field, it corresponds to the Work (electrical), w ...
or through the release of chemical energy. Oxidation and reduction describe the change of oxidation state that takes place in the atoms, ions or molecules involved in an electrochemical reaction. Formally, oxidation state is the hypothetical charge that an atom would have if all bonds to atoms of different elements were 100% ionic. An atom or ion that gives up an electron to another atom or ion has its oxidation state increase, and the recipient of the negatively charged electron has its oxidation state decrease. For example, when atomic
sodium Sodium is a chemical element with the Symbol (chemistry), symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the ...
reacts with atomic
chlorine Chlorine is a chemical element with the Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate betwee ...
, sodium donates one electron and attains an oxidation state of +1. Chlorine accepts the electron and its oxidation state is reduced to −1. The sign of the oxidation state (positive/negative) actually corresponds to the value of each ion's electronic charge. The attraction of the differently charged sodium and chlorine ions is the reason they then form an
ionic bond Ionic bonding is a type of chemical bonding that involves the Coulomb's law, electrostatic attraction between oppositely charged ions, or between two atoms with sharply different electronegativities, and is the primary interaction occurring in ion ...
. The loss of electrons from an atom or molecule is called oxidation, and the gain of electrons is reduction. This can be easily remembered through the use of
mnemonic A mnemonic ( ) device, or memory device, is any learning technique that aids information retention or retrieval (remembering) in the human memory for better understanding. Mnemonics make use of elaborative encoding, retrieval cues, and imagery ...
devices. Two of the most popular are ''"OIL RIG"'' (Oxidation Is Loss, Reduction Is Gain) and ''"LEO"'' the lion says ''"GER"'' (Lose Electrons: Oxidation, Gain Electrons: Reduction). Oxidation and reduction always occur in a paired fashion such that one species is oxidized when another is reduced. For cases where electrons are shared (covalent bonds) between atoms with large differences in
electronegativity Electronegativity, symbolized as ''Chi (letter), χ'', is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its ato ...
, the electron is assigned to the atom with the largest electronegativity in determining the oxidation state. The atom or molecule which loses electrons is known as the ''
reducing agent In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are commonly reducing agents include the Earth meta ...
'', or ''reductant'', and the substance which accepts the electrons is called the ''
oxidizing agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or "Electron acceptor, accepts"/"receives" an electron from a (called the , , or ). In ot ...
'', or ''oxidant''. Thus, the oxidizing agent is always being reduced in a reaction; the reducing agent is always being oxidized. Oxygen is a common oxidizing agent, but not the only one. Despite the name, an oxidation reaction does not necessarily need to involve oxygen. In fact, a
fire Fire is the rapid oxidation of a material (the fuel) in the exothermic chemical process of combustion, releasing heat, light, and various reaction Product (chemistry), products. At a certain point in the combustion reaction, called the ignition ...
can be fed by an oxidant other than oxygen;
fluorine Fluorine is a chemical element A chemical element is a species of atoms that have a given number of protons in their atomic nucleus, nuclei, including the pure Chemical substance, substance consisting only of that species. Unlike chemical c ...
fires are often unquenchable, as fluorine is an even stronger oxidant (it has a weaker bond and higher
electronegativity Electronegativity, symbolized as ''Chi (letter), χ'', is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its ato ...
, and thus accepts electrons even better) than oxygen. For reactions involving oxygen, the gain of oxygen implies the oxidation of the atom or molecule to which the oxygen is added (and the oxygen is reduced). In organic compounds, such as
butane Butane () or ''n''-butane is an alkane with the formula C4H10. Butane is a gas at room temperature and atmospheric pressure. Butane is a highly flammable, colorless, easily liquefied gas that quickly vaporizes at room temperature. The name b ...
or
ethanol Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an Alcohol (chemistry), alcohol with the chemical formula . Its formula can be also written as or (an ethyl ...
, the loss of hydrogen implies oxidation of the molecule from which it is lost (and the hydrogen is reduced). This follows because the hydrogen donates its electron in covalent bonds with non-metals but it takes the electron along when it is lost. Conversely, loss of oxygen or gain of hydrogen implies reduction.


Balancing redox reactions

Electrochemical reactions in water are better analyzed by using the ion-electron method, where H+, OH ion, H2O and electrons (to compensate the oxidation changes) are added to the cell's
half-reaction A half reaction (or half-cell reaction) is either the oxidation or reduction reaction component of a redox reaction. A half reaction is obtained by considering the change in oxidation states of individual substances involved in the redox reaction. ...
s for oxidation and reduction.


Acidic medium

In acidic medium, H+ ions and water are added to balance each
half-reaction A half reaction (or half-cell reaction) is either the oxidation or reduction reaction component of a redox reaction. A half reaction is obtained by considering the change in oxidation states of individual substances involved in the redox reaction. ...
. For example, when
manganese Manganese is a chemical element with the Symbol (chemistry), symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of ...
reacts with sodium bismuthate. :''Unbalanced reaction'': Mn2+ + NaBiO3 → Bi3+ + :''Oxidation'': 4 H2O + Mn2+ → + 8 H+ + 5 e :''Reduction'': 2 e + 6 H+ + → Bi3+ + 3 H2O Finally, the reaction is balanced by multiplying the stoichiometric coefficients so the numbers of electrons in both half reactions match :8 H2O + 2 Mn2+ → 2 + 16 H+ + 10 e :10 e + 30 H+ + 5 → 5 Bi3+ + 15 H2O and adding the resulting half reactions to give the balanced reaction: :14 H+ + 2 Mn2+ + 5 NaBiO3 → 7 H2O + 2 + 5 Bi3+ + 5 Na+


Basic medium

In basic medium, OH ions and
water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...
are added to balance each half-reaction. For example, in a reaction between
potassium Potassium is the chemical element with the Symbol (chemistry), symbol K (from New Latin, Neo-Latin ''wikt:kalium#Latin, kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little fo ...
and
sodium sulfite Sodium sulfite (sodium sulphite) is the inorganic compound with the chemical formula sodium, Na2Sulfite, SO3. A white, water-soluble solid, it is used commercially as an antioxidant and preservative. A heptahydrate is also known but it is less use ...
: :''Unbalanced reaction'': KMnO4 + Na2SO3 + H2O → MnO2 + Na2SO4 + KOH :''Reduction'': 3 e + 2 H2O + → MnO2 + 4 OH :''Oxidation'': 2 OH + → + H2O + 2 e Here, 'spectator ions' (K+, Na+) were omitted from the half-reactions. By multiplying the stoichiometric coefficients so the numbers of electrons in both half reaction match: :6 e + 4 H2O + 2 → 2 MnO2 + 8 OH :6 OH + 3 → 3 + 3 H2O + 6 e the balanced overall reaction is obtained: :2 KMnO4 + 3 Na2SO3 + H2O → 2 MnO2 + 3 Na2SO4 + 2 KOH


Neutral medium

The same procedure as used in acidic medium can be applied, for example, to balance the complete combustion of
propane Propane () is a three-carbon alkane with the molecular formula . It is a gas at standard temperature and pressure, but compressible to a transportable liquid. A by-product of natural gas processing and petroleum refining, it is commonly used as ...
: :''Unbalanced reaction'': C3H8 + O2 → CO2 + H2O :''Reduction'': 4 H+ + O2 + 4 e → 2 H2O :''Oxidation'': 6 H2O + C3H8 → 3 CO2 + 20 e + 20 H+ By multiplying the stoichiometric coefficients so the numbers of electrons in both half reaction match: :20 H+ + 5 O2 + 20 e → 10 H2O :6 H2O + C3H8 → 3 CO2 + 20 e + 20 H+ the balanced equation is obtained: :C3H8 + 5 O2 → 3 CO2 + 4 H2O


Electrochemical cells

An electrochemical cell is a device that produces an electric current from energy released by a spontaneous redox reaction. This kind of cell includes the
Galvanic cell A galvanic cell or voltaic cell, named after the scientists Luigi Galvani and Alessandro Volta, respectively, is an electrochemical cell in which an electric current is generated from Spontaneous reaction, spontaneous Oxidation-Reduction reactions. ...
or Voltaic cell, named after
Luigi Galvani Luigi Galvani (, also ; ; la, Aloysius Galvanus; 9 September 1737 – 4 December 1798) was an Italian physician, physicist, biologist and philosopher, who studied Galvanism, animal electricity. In 1780, he discovered that the muscles of dead fr ...
and
Alessandro Volta Alessandro Giuseppe Antonio Anastasio Volta (, ; 18 February 1745 – 5 March 1827) was an Italian physicist, chemist and lay List of lay Catholic scientists, Catholic who was a pioneer of electricity and Power (physics), power who is credite ...
, both scientists who conducted experiments on chemical reactions and electric current during the late 18th century. Electrochemical cells have two conductive electrodes (the anode and the cathode). The
anode An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
is defined as the electrode where oxidation occurs and the
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction in ...
is the electrode where the reduction takes place. Electrodes can be made from any sufficiently conductive materials, such as metals, semiconductors, graphite, and even
conductive polymer Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic polymers that Electrical conductance, conduct electricity. Such compounds may have metallic conductivity or can be semiconductors. The biggest advantage ...
s. In between these electrodes is the
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electr ...
, which contains ions that can freely move. The galvanic cell uses two different metal electrodes, each in an electrolyte where the positively charged ions are the oxidized form of the electrode metal. One electrode will undergo oxidation (the anode) and the other will undergo reduction (the cathode). The metal of the anode will oxidize, going from an oxidation state of 0 (in the solid form) to a positive oxidation state and become an ion. At the cathode, the metal ion in solution will accept one or more electrons from the cathode and the ion's oxidation state is reduced to 0. This forms a solid metal that electrodeposits on the cathode. The two electrodes must be electrically connected to each other, allowing for a flow of electrons that leave the metal of the anode and flow through this connection to the ions at the surface of the cathode. This flow of electrons is an electric current that can be used to do work, such as turn a motor or power a light. A galvanic cell whose
electrode An electrode is an electrical conductor used to make contact with a nonmetallic part of a Electronic circuit, circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of Electric battery, batteries that can ...
s are
zinc Zinc is a chemical element with the Symbol (chemistry), symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 eleme ...
and
copper Copper is a chemical element with the Symbol (chemistry), symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductility, ductile metal with very high thermal conductivity, thermal and electrical conductivity. A fre ...
submerged in
zinc sulfate Zinc sulfate is an inorganic compound. It is used as a dietary supplement to treat zinc deficiency and to prevent the condition in those at high risk. Side effects of excess supplementation may include abdominal pain, vomiting, headache, a ...
and
copper sulfate Copper sulfate may refer to: * Copper(II) sulfate, CuSO4, a common compound used as a fungicide and herbicide * Copper(I) sulfate, Cu2SO4, which is uncommonly used * Copper(II) sulfate, CuSO4 is greenish blue Copper compounds {{Chem-stu ...
, respectively, is known as a
Daniell cell The Daniell cell is a type of electrochemical cell invented in 1836 by John Frederic Daniell, a British chemist and meteorologist, and consists of a copper pot filled with a copper (II) sulfate solution, in which is immersed an unglazed earthenwar ...
. The half reactions in a Daniell cell are as follows: :Zinc electrode (anode): Zn → Zn2+ + 2 e :Copper electrode (cathode): Cu2+ + 2 e → Cu In this example, the anode is the zinc metal which is oxidized (loses electrons) to form zinc ions in solution, and copper ions accept electrons from the copper metal electrode and the ions deposit at the copper cathode as an electrodeposit. This cell forms a simple battery as it will spontaneously generate a flow of electric current from the anode to the cathode through the external connection. This reaction can be driven in reverse by applying a voltage, resulting in the deposition of zinc metal at the anode and formation of copper ions at the cathode. To provide a complete electric circuit, there must also be an ionic conduction path between the anode and cathode electrolytes in addition to the electron conduction path. The simplest ionic conduction path is to provide a liquid junction. To avoid mixing between the two electrolytes, the liquid junction can be provided through a porous plug that allows ion flow while minimizing electrolyte mixing. To further minimize mixing of the electrolytes, a salt bridge can be used which consists of an electrolyte saturated gel in an inverted U-tube. As the negatively charged electrons flow in one direction around this circuit, the positively charged metal ions flow in the opposite direction in the electrolyte. A
voltmeter A voltmeter is an instrument used for measuring electric potential difference between two points in an electric circuit. It is connected in parallel. It usually has a high resistance so that it takes negligible current from the circuit. ...
is capable of measuring the change of
electrical potential The electric potential (also called the ''electric field potential'', potential drop, the electrostatic potential) is defined as the amount of work (physics), work energy needed to move a unit of electric charge from a reference point to the sp ...
between the anode and the cathode. The electrochemical cell voltage is also referred to as
electromotive force In electromagnetism and electronics, electromotive force (also electromotance, abbreviated emf, denoted \mathcal or ) is an energy transfer to an electric circuit per unit of electric charge, measured in volts. Devices called electrical ''Transd ...
or emf. A cell diagram can be used to trace the path of the electrons in the electrochemical cell. For example, here is a cell diagram of a Daniell cell: :Zn , Zn2+ (1 M) , , Cu2+ (1 M) , Cu First, the reduced form of the metal to be oxidized at the anode (Zn) is written. This is separated from its oxidized form by a vertical line, which represents the limit between the phases (oxidation changes). The double vertical lines represent the saline bridge on the cell. Finally, the oxidized form of the metal to be reduced at the cathode, is written, separated from its reduced form by the vertical line. The electrolyte concentration is given as it is an important variable in determining the exact cell potential.


Standard electrode potential

To allow prediction of the cell potential, tabulations of
standard electrode potential In electrochemistry, standard electrode potential E^\ominus, or E^\ominus_, is a measure of the reducing power of any element or compound. The IUPAC "Gold Book" defines it as: ''"the value of the standard Electromotive force, emf (electromotive fo ...
are available. Such tabulations are referenced to the standard hydrogen electrode (SHE). The
standard hydrogen electrode The standard hydrogen electrode (abbreviated SHE), is a redox electrode which forms the basis of the Table of standard electrode potentials, thermodynamic scale of oxidation-reduction potentials. Its absolute electrode potential is estimated to be ...
undergoes the reaction :2 H+ + 2 e → H2 which is shown as a reduction but, in fact, the SHE can act as either the anode or the cathode, depending on the relative oxidation/reduction potential of the other electrode/electrolyte combination. The term standard in SHE requires a supply of hydrogen gas bubbled through the electrolyte at a pressure of 1 atm and an acidic electrolyte with H+ activity equal to 1 (usually assumed to be += 1 mol/liter, i.e. pH = 0). The SHE electrode can be connected to any other electrode by a salt bridge and an external circuit to form a cell. If the second electrode is also at standard conditions, then the measured cell potential is called the standard electrode potential for the electrode. The standard electrode potential for the SHE is zero, by definition. The polarity of the standard electrode potential provides information about the relative reduction potential of the electrode compared to the SHE. If the electrode has a positive potential with respect to the SHE, then that means it is a strongly reducing electrode which forces the SHE to be the anode (an example is Cu in aqueous CuSO4 with a standard electrode potential of 0.337 V). Conversely, if the measured potential is negative, the electrode is more oxidizing than the SHE (such as Zn in ZnSO4 where the standard electrode potential is −0.76 V).Wiberg, pp. 215–216 Standard electrode potentials are usually tabulated as reduction potentials. However, the reactions are reversible and the role of a particular electrode in a cell depends on the relative oxidation/reduction potential of both electrodes. The oxidation potential for a particular electrode is just the negative of the reduction potential. A standard cell potential can be determined by looking up the standard electrode potentials for both electrodes (sometimes called half cell potentials). The one that is smaller will be the anode and will undergo oxidation. The cell potential is then calculated as the sum of the reduction potential for the cathode and the oxidation potential for the anode. :''E''°cell = ''E''°red (cathode) – ''E''°red (anode) = ''E''°red (cathode) + ''E''°oxi (anode) For example, the standard electrode potential for a copper electrode is: ''Cell diagram'' :Pt , H2 (1 atm) , H+ (1 M) , , Cu2+ (1 M) , Cu :''E''°cell = ''E''°red (cathode) – ''E''°red (anode) At standard temperature, pressure and concentration conditions, the cell's emf (measured by a
multimeter A multimeter is a measuring instrument that can measure multiple electrical properties. A typical multimeter can measure voltage, electrical resistance, resistance, and electric current, current, in which case it is also known as a volt-ohm-milli ...
) is 0.34 V. By definition, the electrode potential for the SHE is zero. Thus, the Cu is the cathode and the SHE is the anode giving :''E''cell = ''E''°(Cu2+/Cu) – ''E''°(H+/H2) Or, :''E''°(Cu2+/Cu) = 0.34 V Changes in the stoichiometric coefficients of a balanced cell equation will not change the ''E''°red value because the standard electrode potential is an
intensive property Physical properties of materials and systems can often be categorized as being either intensive or extensive, according to how the property changes when the size (or extent) of the system changes. According to International Union of Pure and Appl ...
.


Spontaneity of redox reaction

During operation of an
electrochemical cell An electrochemical cell is a device capable of either generating electrical energy from chemical reactions or using electrical energy to cause chemical reactions. The electrochemical cells which generate an electric current are called voltaic o ...
,
chemical energy Chemical energy is the energy of chemical substances that is released when they undergo a chemical reaction and transform into other substances. Some examples of storage media of chemical energy include batteries, Schmidt-Rohr, K. (2018). "How ...
is transformed into
electrical energy Electrical energy is energy related to forces on electrically charged particles and the movement of electrically charged particles (often electrons in wires, but not always). This energy is supplied by the combination of electric current and electr ...
. This can be expressed mathematically as the product of the cell's emf ''E''cell measured in volts (V) and the
electric charge Electric charge is the physical property of matter that causes charged matter to experience a force when placed in an electromagnetic field. Electric charge can be ''positive'' or ''negative'' (commonly carried by protons and electron ...
''Q''ele,trans transferred through the external circuit. :Electrical energy = ''E''cell''Q''ele,trans ''Q''ele,trans is the cell current integrated over time and measured in coulombs (C); it can also be determined by multiplying the total number ''n''e of electrons transferred (measured in moles) times Faraday's constant (''F''). The emf of the cell at zero current is the maximum possible emf. It can be used to calculate the maximum possible electrical energy that could be obtained from a
chemical reaction A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the pos ...
. This energy is referred to as
electrical work Electric field work is the work performed by an electric field An electric field (sometimes E-field) is the field (physics), physical field that surrounds electrically charged particles and exerts force on all other charged particles in the ...
and is expressed by the following equation: :W_\mathrm = W_\mathrm = -n_eFE_\mathrm , where work is defined as positive when it increases the energy of the system. Since the free energy is the maximum amount of work that can be extracted from a system, one can write:Swaddle, pp. 308–314 :\Delta G = -n_eFE_\mathrm A positive cell potential gives a negative change in Gibbs free energy. This is consistent with the cell production of an
electric current An electric current is a stream of charged particles, such as electrons or ions, moving through an electrical conductor or space. It is measured as the net rate of flow of electric charge through a surface or into a control volume. The moving par ...
from the cathode to the anode through the external circuit. If the current is driven in the opposite direction by imposing an external potential, then work is done on the cell to drive electrolysis. A spontaneous electrochemical reaction (change in Gibbs free energy less than zero) can be used to generate an electric current in electrochemical cells. This is the basis of all batteries and
fuel cell A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen fuel, hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most bat ...
s. For example, gaseous oxygen (O2) and hydrogen (H2) can be combined in a fuel cell to form water and energy, typically a combination of heat and electrical energy. Conversely, non-spontaneous electrochemical reactions can be driven forward by the application of a current at sufficient
voltage Voltage, also known as electric pressure, electric tension, or (electric) potential difference, is the difference in electric potential between two points. In a Electrostatics, static electric field, it corresponds to the Work (electrical), w ...
. The
electrolysis In chemistry Chemistry is the scientific study of the properties and behavior of matter. It is a natural science that covers the elements that make up matter to the compounds made of atoms, molecules and ions: their composition, str ...
of water into gaseous oxygen and hydrogen is a typical example. The relation between the
equilibrium constant The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency ...
, ''K'', and the Gibbs free energy for an electrochemical cell is expressed as follows: :\Delta G^\circ = -RT \ln K = -nFE^_\mathrm . Rearranging to express the relation between standard potential and equilibrium constant yields :E^_ = \frac\ln K. At ''T'' = 298 K, the previous equation can be rewritten using the Briggsian logarithm as follows: :E^_ = \frac \log K


Cell emf dependency on changes in concentration


Nernst equation

The standard potential of an electrochemical cell requires standard conditions (Δ''G''°) for all of the reactants. When reactant concentrations differ from standard conditions, the cell potential will deviate from the standard potential. In the 20th century German
chemist A chemist (from Greek ''chēm(ía)'' alchemy; replacing ''chymist'' from Medieval Latin ''alchemist'') is a scientist trained in the study of chemistry. Chemists study the composition of matter and its properties. Chemists carefully describe th ...
Walther Nernst Walther Hermann Nernst (; 25 June 1864 – 18 November 1941) was a German chemist known for his work in thermodynamics, physical chemistry, electrochemistry, and solid state physics. His formulation of the Nernst heat theorem helped pave the wa ...
proposed a mathematical model to determine the effect of reactant concentration on electrochemical cell potential. In the late 19th century,
Josiah Willard Gibbs Josiah Willard Gibbs (; February 11, 1839 – April 28, 1903) was an American scientist who made significant theoretical contributions to physics, chemistry, and mathematics. His work on the applications of thermodynamics was instrumental in t ...
had formulated a theory to predict whether a chemical reaction is spontaneous based on the free energy :\Delta G = \Delta G^\circ + RT \ln Q Here Δ''G'' is change in
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work (physics), work that may be performed by a closed system, thermodynamically closed system a ...
, Δ''G''° is the cell potential when ''Q'' is equal to 1, ''T'' is absolute
temperature Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measurement, measured with a thermometer. Thermometers are calibrated in various Conversion of units of temperature, temp ...
(Kelvin), ''R'' is the
gas constant The molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol or . It is the molar equivalent to the Boltzmann constant The Boltzmann constant ( or ) is the proportionality f ...
and ''Q'' is the
reaction quotient In chemical thermodynamics, the reaction quotient (''Q''r or just ''Q'') is a dimensionless quantity that provides a measurement of the relative amounts of products and reactants present in a reaction mixture for a reaction with well-defined overall ...
, which can be calculated by dividing concentrations of products by those of reactants, each raised to the power of its stoichiometric coefficient, using only those products and reactants that are aqueous or gaseous. Gibbs' key contribution was to formalize the understanding of the effect of reactant concentration on spontaneity. Based on Gibbs' work, Nernst extended the theory to include the contribution from electric potential on charged species. As shown in the previous section, the change in Gibbs free energy for an electrochemical cell can be related to the cell potential. Thus, Gibbs' theory becomes :n_eF\Delta E = n_e F\Delta E^\circ - RT \ln Q Here ''ne'' is the number of
electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electric charge. Electrons belong to the first generation (particle physics), generation of the lepton particle family, and are generally thought t ...
s (in moles), ''F'' is the
Faraday constant In physical chemistry, the Faraday constant, denoted by the symbol and sometimes stylized as ℱ, is the electric charge per mole (unit), mole of elementary charges. It is named after the English scientist Michael Faraday. Since the 2019 redefi ...
(in
coulomb The coulomb (symbol: C) is the unit of electric charge in the International System of Units (SI). In 2019 redefinition of the SI base units, the present version of the SI it is equal to the electric charge delivered by a 1 ampere constant curre ...
s/ mole), and Δ''E'' is the cell potential (in volts). Finally, Nernst divided through by the amount of charge transferred to arrive at a new equation which now bears his name: :\Delta E = \Delta E^\circ - \frac \ln Q Assuming standard conditions (''T'' = 298 K or 25 °C) and ''R'' = 8.3145 J/(K·mol), the equation above can be expressed on base—10 logarithm as shown below:Wiberg, pp. 210–212 :\Delta E = \Delta E^\circ- \frac \log Q Note that ' is also known as the thermal voltage ''V''T and is found in the study of plasmas and semiconductors as well. The value 0.05916 V in the above equation is just the thermal voltage at standard temperature multiplied by the natural logarithm of 10.


Concentration cells

A concentration cell is an electrochemical cell where the two electrodes are the same material, the electrolytes on the two half-cells involve the same ions, but the electrolyte concentration differs between the two half-cells. An example is an electrochemical cell, where two copper electrodes are submerged in two
copper(II) sulfate Copper(II) sulfate, also known as copper sulphate, is an inorganic compound with the chemical formula . It forms hydrates , where ''n'' can range from 1 to 7. The pentahydrate (''n'' = 5), a bright blue crystal, is the most commonly encountered hy ...
solutions, whose concentrations are 0.05 M and 2.0 M, connected through a salt bridge. This type of cell will generate a potential that can be predicted by the Nernst equation. Both can undergo the same chemistry (although the reaction proceeds in reverse at the anode) :Cu2+ + 2 e → Cu
Le Chatelier's principle Le Chatelier's principle (pronounced or ), also called Chatelier's principle (or the Equilibrium Law), is a principle of chemistry Chemistry is the scientific study of the properties and behavior of matter. It is a natural science that ...
indicates that the reaction is more favorable to reduction as the concentration of Cu2+ ions increases. Reduction will take place in the cell's compartment where the concentration is higher and oxidation will occur on the more dilute side. The following cell diagram describes the concentration cell mentioned above: :Cu , Cu2+ (0.05 M) , , Cu2+ (2.0 M) , Cu where the half cell reactions for oxidation and reduction are: :Oxidation: Cu → Cu2+ (0.05 M) + 2 e :Reduction: Cu2+ (2.0 M) + 2 e → Cu :Overall reaction: Cu2+ (2.0 M) → Cu2+ (0.05 M) The cell's emf is calculated through the
Nernst equation In electrochemistry Electrochemistry is the branch of physical chemistry concerned with the relationship between Electric potential, electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, ...
as follows: :E = E^\circ - \frac \log \frac The value of ''E''° in this kind of cell is zero, as electrodes and ions are the same in both half-cells. After replacing values from the case mentioned, it is possible to calculate cell's potential: :E = 0 - \frac \log \frac = 0.0474\,\mathrm or by: :E = 0 - \frac \ln \frac= 0.0474\,\mathrm However, this value is only approximate, as reaction quotient is defined in terms of ion activities which can be approximated with the concentrations as calculated here. The Nernst equation plays an important role in understanding electrical effects in cells and organelles. Such effects include nerve
synapses In the nervous system, a synapse is a structure that permits a neuron (or nerve cell) to pass an electrical or chemical signal to another neuron or to the target effector cell. Synapses are essential to the transmission of nervous impulses from ...
and cardiac beat as well as the resting potential of a somatic cell.


Battery

Many types of battery have been commercialized and represent an important practical application of electrochemistry. Early
wet cell An electric battery is a source of electric power Electric power is the rate at which electrical energy is transferred by an electric circuit. The SI unit of Power (physics), power is the watt, one joule per second. Standard prefixes appl ...
s powered the first
telegraph Telegraphy is the long-distance transmission of messages where the sender uses symbolic codes, known to the recipient, rather than a physical exchange of an object bearing the message. Thus flag semaphore is a method of telegraphy, whereas p ...
and
telephone A telephone is a telecommunications device that permits two or more users to conduct a conversation when they are too far apart to be easily heard directly. A telephone converts sound, typically and most efficiently the human voice, into ele ...
systems, and were the source of current for
electroplating Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the redox, reduction of cations of that metal by means of a direct current, direct electric cur ...
. The zinc-manganese dioxide
dry cell upLine art drawing of a dry cell: 1. brass cap, 2. plastic seal, 3. expansion space, 4. porous cardboard, 5. zinc can, 6. carbon rod, 7. chemical mixture A dry cell is a type of electric battery, commonly used for portable electrical devices. Un ...
was the first portable, non-spillable battery type that made
flashlight A flashlight (American English, US, Canadian English, Canada) or torch (British English, UK, Australian English, Australia) is a portable hand-held electric lamp. Formerly, the light source typically was a miniature incandescent light bulb, b ...
s and other portable devices practical. The
mercury battery A mercury battery (also called mercuric oxide battery, mercury cell, button cell, or Ruben-Mallory) is a non-rechargeable electrochemical battery, a primary cell. Mercury batteries use a reaction between mercuric oxide and zinc electrodes in an ...
using zinc and mercuric oxide provided higher levels of power and capacity than the original dry cell for early electronic devices, but has been phased out of common use due to the danger of mercury pollution from discarded cells. The
lead–acid battery The lead–acid battery is a type of rechargeable battery first invented in 1859 by French physicist Gaston Planté. It is the first type of rechargeable battery ever created. Compared to modern rechargeable batteries, lead–acid batteries have ...
was the first practical secondary (rechargeable) battery that could have its capacity replenished from an external source. The electrochemical reaction that produced current was (to a useful degree) reversible, allowing electrical energy and chemical energy to be interchanged as needed. Common lead acid batteries contain a mixture of sulfuric acid and water, as well as lead plates. The most common mixture used today is 30% acid. One problem, however, is if left uncharged acid will crystallize within the lead plates of the battery rendering it useless. These batteries last an average of 3 years with daily use but it is not unheard of for a lead acid battery to still be functional after 7–10 years. Lead-acid cells continue to be widely used in automobiles. All the preceding types have water-based electrolytes, which limits the maximum voltage per cell. The freezing of water limits low temperature performance. The
lithium metal battery Lithium metal batteries are primary batteries that have metallic lithium as an anode. These types of batteries are also referred to as lithium-metal batteries after lithium-ion batteries had been invented. Most lithium metal batteries are n ...
, which does not (and cannot) use water in the electrolyte, provides improved performance over other types; a rechargeable
lithium-ion battery A lithium-ion or Li-ion battery is a type of rechargeable battery which uses the reversible Redox, reduction of lithium ions to store energy. It is the predominant battery type used in portable consumer electronics and electric vehicles. It als ...
is an essential part of many mobile devices. The
flow battery A flow battery, or redox flow battery (after reduction–oxidation), is a type of electrochemical cell where chemical energy is provided by two chemical components dissolved in liquids that are pumped through the system on separate sides of ...
, an experimental type, offers the option of vastly larger energy capacity because its reactants can be replenished from external reservoirs. The
fuel cell A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen fuel, hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most bat ...
can turn the chemical energy bound in hydrocarbon gases or hydrogen and
oxygen Oxygen is the chemical element with the chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen Group (periodic table), group in the periodic table, a highly Chemical reaction, reactive nonmetal, and an oxidizing a ...
directly into electrical energy with a much higher efficiency than any combustion process; such devices have powered many spacecraft and are being applied to
grid energy storage Grid energy storage (also called large-scale energy storage) is a collection of methods used for energy storage on a large scale within an electrical power grid. Electrical energy is stored during times when electricity is plentiful and inex ...
for the public power system.


Corrosion

Corrosion is an electrochemical process, which reveals itself as
rust Rust is an iron oxide, a usually reddish-brown oxide formed by the reaction of iron and oxygen in the catalytic presence of water or air moisture. Rust consists of hydrous ferric oxides, hydrous iron(III) oxides (Fe2O3·nH2O) and iron(III) oxi ...
or tarnish on metals like
iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundance ...
or
copper Copper is a chemical element with the Symbol (chemistry), symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductility, ductile metal with very high thermal conductivity, thermal and electrical conductivity. A fre ...
and their respective alloys,
steel Steel is an alloy made up of iron with added carbon to improve its strength of materials, strength and fracture toughness, fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that ...
and
brass Brass is an alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical ...
.


Iron corrosion

For iron rust to occur the metal has to be in contact with
oxygen Oxygen is the chemical element with the chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen Group (periodic table), group in the periodic table, a highly Chemical reaction, reactive nonmetal, and an oxidizing a ...
and
water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...
. The
chemical reaction A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the pos ...
s for this process are relatively complex and not all of them are completely understood. It is believed the causes are the following: Electron transfer (reduction-oxidation) :One area on the surface of the metal acts as the anode, which is where the oxidation (corrosion) occurs. At the anode, the metal gives up electrons. ::Fe → Fe2+ + 2 e :
Electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electric charge. Electrons belong to the first generation (particle physics), generation of the lepton particle family, and are generally thought t ...
s are transferred from
iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundance ...
, reducing oxygen in the
atmosphere An atmosphere () is a layer of gas or layers of gases that envelop a planet, and is held in place by the gravity of the planetary body. A planet retains an atmosphere when the gravity is great and the temperature of the atmosphere is low. A s ...
into
water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...
on the cathode, which is placed in another region of the metal. ::O2 + 4 H+ + 4 e → 2 H2O :Global reaction for the process: ::2 Fe + O2 + 4 H+ → 2 Fe2+ + 2 H2O :Standard emf for iron rusting: ::''E''° = ''E''° (cathode) − ''E''° (anode) ::''E''° = 1.23V − (−0.44 V) = 1.67 V Iron corrosion takes place in an acid medium; H+ ions come from reaction between
carbon dioxide Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon Carbon () is a chemical element with the chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetraval ...
in the atmosphere and water, forming carbonic acid. Fe2+ ions oxidize further, following this equation: : 4 Fe2+ + O2 + (4+2) H2O → 2 Fe2O3·H2O + 8 H+
Iron(III) oxide Iron(III) oxide or ferric oxide is the inorganic compound with the formula Fe2O3. It is one of the three main oxides of iron, the other two being iron(II) oxide (FeO), which is rare; and iron(II,III) oxide (Fe3O4), which also occurs naturally a ...
hydrate In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
is known as rust. The concentration of water associated with iron oxide varies, thus the chemical formula is represented by Fe2O3·H2O. An
electric circuit An electrical network is an interconnection of electronic component, electrical components (e.g., battery (electricity), batteries, resistors, inductors, capacitors, switches, transistors) or a model of such an interconnection, consisting of e ...
is formed as passage of electrons and ions occurs; thus if an electrolyte is present it will facilitate
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate (chemistry), substrate change. Oxidation is the loss of Electron, electrons or an increase in the oxidation state, while reduction ...
, explaining why rusting is quicker in
salt water Saline water (more commonly known as salt water) is water that contains a high concentration of solvation, dissolved salts (mainly sodium chloride). On the United States Geological Survey (USGS) salinity scale, saline water is saltier than brack ...
.


Corrosion of common metals

Coinage metals, such as copper and silver, slowly corrode through use. A
patina Patina ( or ) is a thin layer that variously forms on the surface of copper, brass, bronze and similar metals and metal alloys (tarnish produced by oxidation or other chemical processes) or certain stones and wooden furniture (sheen produced b ...
of green-blue copper carbonate forms on the surface of
copper Copper is a chemical element with the Symbol (chemistry), symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductility, ductile metal with very high thermal conductivity, thermal and electrical conductivity. A fre ...
with exposure to the water and carbon dioxide in the air.
Silver Silver is a chemical element with the Symbol (chemistry), symbol Ag (from the Latin ', derived from the Proto-Indo-European wikt:Reconstruction:Proto-Indo-European/h₂erǵ-, ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, whi ...
coins or
cutlery Cutlery (also referred to as silverware, flatware, or tableware), includes any hand Tool, implement used in preparing, serving, and especially eating food in Western culture. A person who makes or sells cutlery is called a cutler. The city of Sh ...
that are exposed to high sulfur foods such as
egg An egg is an organic vessel grown by an animal to carry a possibly fertilized egg cell (a zygote) and to incubate from it an embryo An embryo is an initial stage of development of a multicellular organism. In organisms that Sexual repr ...
s or the low levels of sulfur species in the air develop a layer of black
silver sulfide Silver sulfide is an inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield o ...
.
Gold Gold is a chemical element with the Symbol (chemistry), symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a Brightness, bright, slightly orange-yellow, dense, s ...
and
platinum Platinum is a chemical element with the Symbol (chemistry), symbol Pt and atomic number 78. It is a density, dense, malleable, ductility, ductile, highly unreactive, precious metal, precious, silverish-white transition metal. Its name origina ...
are extremely difficult to oxidize under normal circumstances, and require exposure to a powerful chemical oxidizing agent such as aqua regia. Some common metals oxidize extremely rapidly in air.
Titanium Titanium is a chemical element with the Symbol (chemistry), symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resista ...
and aluminium oxidize instantaneously in contact with the oxygen in the air. These metals form an extremely thin layer of oxidized metal on the surface, which bonds with the underlying metal. This thin oxide layer protects the underlying bulk of the metal from the air preventing the entire metal from oxidizing. These metals are used in applications where corrosion resistance is important.
Iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundance ...
, in contrast, has an oxide that forms in air and water, called
rust Rust is an iron oxide, a usually reddish-brown oxide formed by the reaction of iron and oxygen in the catalytic presence of water or air moisture. Rust consists of hydrous ferric oxides, hydrous iron(III) oxides (Fe2O3·nH2O) and iron(III) oxi ...
, that does not bond with the iron and therefore does not stop the further oxidation of the iron. Thus iron left exposed to air and water will continue to rust until all of the iron is oxidized.


Prevention of corrosion

Attempts to save a metal from becoming anodic are of two general types. Anodic regions dissolve and destroy the structural integrity of the metal. While it is almost impossible to prevent anode/
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction in ...
formation, if a non-conducting material covers the metal, contact with the
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electr ...
is not possible and corrosion will not occur.


Coating

Metals can be coated with
paint Paint is any pigmented liquid, liquefiable, or solid mastic composition that, after application to a substrate in a thin layer, converts to a solid film. It is most commonly used to protect, color, or provide texture. Paint can be made in ma ...
or other less conductive metals ('' passivation''). This prevents the metal surface from being exposed to
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electr ...
s. Scratches exposing the metal substrate will result in corrosion. The region under the coating adjacent to the scratch acts as the
anode An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
of the reaction. See
Anodizing Anodizing is an electrolyte, electrolytic Passivation (chemistry), passivation process used to increase the thickness of the natural oxide layer on the surface of metal parts. The process is called ''anodizing'' because the part to be treated fo ...


Sacrificial anodes

A method commonly used to protect a structural metal is to attach a metal which is more anodic than the metal to be protected. This forces the structural metal to be cathodic, thus spared corrosion. It is called ''"sacrificial"'' because the anode dissolves and has to be replaced periodically.
Zinc Zinc is a chemical element with the Symbol (chemistry), symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 eleme ...
bars are attached to various locations on steel
ship A ship is a large watercraft that travels the world's oceans and other sufficiently deep Sea lane, waterways, carrying cargo or passengers, or in support of specialized missions, such as defense, research, and fishing. Ships are generally dist ...
hulls to render the ship hull cathodic. The zinc bars are replaced periodically. Other metals, such as
magnesium Magnesium is a chemical element with the Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group ...
, would work very well but zinc is the least expensive useful metal. To protect pipelines, an ingot of buried or exposed magnesium (or zinc) is buried beside the pipeline and is connected electrically to the pipe above ground. The pipeline is forced to be a cathode and is protected from being oxidized and rusting. The magnesium anode is sacrificed. At intervals new
ingot An ingot is a piece of relatively pure material, usually metal, that is Casting, cast into a shape suitable for further processing. In steelmaking, it is the first step among semi-finished casting products. Ingots usually require a second procedu ...
s are buried to replace those dissolved.


Electrolysis

The spontaneous redox reactions of a conventional battery produce electricity through the different reduction potentials of the cathode and anode in the electrolyte. However, electrolysis requires an external source of
electrical energy Electrical energy is energy related to forces on electrically charged particles and the movement of electrically charged particles (often electrons in wires, but not always). This energy is supplied by the combination of electric current and electr ...
to induce a chemical reaction, and this process takes place in a compartment called an
electrolytic cell An electrolytic cell is an electrochemical cell that utilizes an external source of electrical energy to force a chemical reaction that would not otherwise occur. The external energy source is a voltage applied between the cell′s two electrode ...
.


Electrolysis of molten sodium chloride

When molten, the salt
sodium chloride Sodium chloride , commonly known as salt (although sea salt also contains other chemical salt (chemistry), salts), is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. With molar masses of ...
can be electrolyzed to yield metallic
sodium Sodium is a chemical element with the Symbol (chemistry), symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the ...
and gaseous
chlorine Chlorine is a chemical element with the Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate betwee ...
. Industrially this process takes place in a special cell named Down's cell. The cell is connected to an electrical power supply, allowing
electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electric charge. Electrons belong to the first generation (particle physics), generation of the lepton particle family, and are generally thought t ...
s to migrate from the power supply to the electrolytic cell.Ebbing, pp. 800–801 Reactions that take place in a Down's cell are the following: :Anode (oxidation): 2 Cl → Cl2 + 2 e :Cathode (reduction): 2 Na+ + 2 e → 2 Na :Overall reaction: 2 Na+ + 2 Cl → 2 Na + Cl2 This process can yield large amounts of metallic sodium and gaseous chlorine, and is widely used in
mineral dressing In the field of extractive metallurgy, mineral processing, also known as ore dressing, is the process of separating commercially valuable minerals from their ores. History Before the advent of heavy machinery the raw ore was broken up using ...
and
metallurgy Metallurgy is a domain of Materials science, materials science and engineering that studies the physical and chemical behavior of metallic Chemical element, elements, their Inter-metallic alloy, inter-metallic compounds, and their mixtures, which ...
industries. The emf for this process is approximately −4  V indicating a (very) non-spontaneous process. In order for this reaction to occur the power supply should provide at least a potential difference of 4 V. However, larger voltages must be used for this reaction to occur at a high rate.


Electrolysis of water

Water can be converted to its component elemental gases, H2 and O2, through the application of an external voltage.
Water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...
does not decompose into
hydrogen Hydrogen is the chemical element with the Symbol (chemistry), symbol H and atomic number 1. Hydrogen is the lightest element. At standard temperature and pressure, standard conditions hydrogen is a gas of diatomic molecules having the chemical ...
and
oxygen Oxygen is the chemical element with the chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen Group (periodic table), group in the periodic table, a highly Chemical reaction, reactive nonmetal, and an oxidizing a ...
spontaneously as the
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work (physics), work that may be performed by a closed system, thermodynamically closed system a ...
change for the process at standard conditions is very positive, about 474.4 kJ. The decomposition of water into hydrogen and oxygen can be performed in an electrolytic cell. In it, a pair of inert
electrode An electrode is an electrical conductor used to make contact with a nonmetallic part of a Electronic circuit, circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of Electric battery, batteries that can ...
s usually made of
platinum Platinum is a chemical element with the Symbol (chemistry), symbol Pt and atomic number 78. It is a density, dense, malleable, ductility, ductile, highly unreactive, precious metal, precious, silverish-white transition metal. Its name origina ...
immersed in water act as anode and cathode in the electrolytic process. The electrolysis starts with the application of an external voltage between the electrodes. This process will not occur except at extremely high voltages without an electrolyte such as
sodium chloride Sodium chloride , commonly known as salt (although sea salt also contains other chemical salt (chemistry), salts), is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. With molar masses of ...
or
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen ...
(most used 0.1 M). Bubbles from the gases will be seen near both electrodes. The following half reactions describe the process mentioned above: :Anode (oxidation): 2 H2O → O2 + 4 H+ + 4 e :Cathode (reduction): 2 H2O + 2 e → H2 + 2 OH :Overall reaction: 2 H2O → 2 H2 + O2 Although strong acids may be used in the apparatus, the reaction will not net consume the acid. While this reaction will work at any conductive electrode at a sufficiently large potential, platinum catalyzes both hydrogen and oxygen formation, allowing for relatively low voltages (~2 V depending on the pH).Wiberg, pp. 235–239


Electrolysis of aqueous solutions

Electrolysis in an aqueous solution is a similar process as mentioned in electrolysis of water. However, it is considered to be a complex process because the contents in solution have to be analyzed in half reactions, whether reduced or oxidized.


Electrolysis of a solution of sodium chloride

The presence of water in a solution of
sodium chloride Sodium chloride , commonly known as salt (although sea salt also contains other chemical salt (chemistry), salts), is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. With molar masses of ...
must be examined in respect to its reduction and oxidation in both electrodes. Usually, water is electrolysed as mentioned above in electrolysis of water yielding ''gaseous
oxygen Oxygen is the chemical element with the chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen Group (periodic table), group in the periodic table, a highly Chemical reaction, reactive nonmetal, and an oxidizing a ...
in the anode'' and gaseous
hydrogen Hydrogen is the chemical element with the Symbol (chemistry), symbol H and atomic number 1. Hydrogen is the lightest element. At standard temperature and pressure, standard conditions hydrogen is a gas of diatomic molecules having the chemical ...
in the cathode. On the other hand, sodium chloride in water dissociates in Na+ and Cl ions. The
cation An ion () is an atom or molecule with a net electric charge, electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be po ...
, which is the positive ion, will be attracted to the cathode (−), thus reducing the
sodium Sodium is a chemical element with the Symbol (chemistry), symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the ...
ion. The
chloride The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the chemical element, element chlorine (a halogen) gains an electron or when a chemical compound, compound such as hydrogen chloride is dissolved in water or o ...
anion An ion () is an atom or molecule with a net electric charge, electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be po ...
will then be attracted to the anode (+), where it is oxidized to chlorine gas.Ebbing, pp. 837–839 The following half reactions should be considered in the process mentioned: # Cathode: Na+ + e → Na''E''°red = –2.71 V # Anode: 2 Cl → Cl2 + 2 e''E''°red = +1.36 V # Cathode: 2 H2O + 2 e → H2 + 2 OH''E''°red = –0.83 V # Anode: 2 H2O → O2 + 4 H+ + 4 e''E''°red = +1.23 V Reaction 1 is discarded as it has the most negative value on standard reduction potential thus making it less thermodynamically favorable in the process. When comparing the reduction potentials in reactions 2 and 4, the reduction of chloride ion is favored. Thus, if the Cl ion is favored for reduction, then the water reaction is favored for
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate (chemistry), substrate change. Oxidation is the loss of Electron, electrons or an increase in the oxidation state, while reduction ...
producing gaseous oxygen, however experiments show gaseous chlorine is produced and not oxygen. Although the initial analysis is correct, there is another effect, known as the overvoltage effect. Additional voltage is sometimes required, beyond the voltage predicted by the ''E''°cell. This may be due to kinetic rather than
thermodynamic Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed b ...
considerations. In fact, it has been proven that the
activation energy In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joule per mole, joules per mole (J/mol), ...
for the chloride ion is very low, hence favorable in kinetic terms. In other words, although the voltage applied is thermodynamically sufficient to drive electrolysis, the rate is so slow that to make the process proceed in a reasonable time frame, the
voltage Voltage, also known as electric pressure, electric tension, or (electric) potential difference, is the difference in electric potential between two points. In a Electrostatics, static electric field, it corresponds to the Work (electrical), w ...
of the external source has to be increased (hence, overvoltage). Finally, reaction 3 is favorable because it describes the proliferation of OH ions thus letting a probable reduction of H+ ions less favorable an option. The overall reaction for the process according to the analysis is the following: :Anode (oxidation): 2 Cl → Cl2 + 2 e :Cathode (reduction): 2 H2O + 2 e → H2 + 2 OH :Overall reaction: 2 H2O + 2 Cl → H2 + Cl2 + 2 OH As the overall reaction indicates, the
concentration In chemistry, concentration is the Abundance (chemistry), abundance of a constituent divided by the total volume of a mixture. Several types of mathematical description can be distinguished: ''mass concentration (chemistry), mass concentration'', ...
of chloride ions is reduced in comparison to OH ions (whose concentration increases). The reaction also shows the production of gaseous
hydrogen Hydrogen is the chemical element with the Symbol (chemistry), symbol H and atomic number 1. Hydrogen is the lightest element. At standard temperature and pressure, standard conditions hydrogen is a gas of diatomic molecules having the chemical ...
,
chlorine Chlorine is a chemical element with the Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate betwee ...
and aqueous
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive, caustic base (c ...
.


Quantitative electrolysis and Faraday's laws

Quantitative aspects of electrolysis were originally developed by
Michael Faraday Michael Faraday (; 22 September 1791 – 25 August 1867) was an English scientist who contributed to the study of electromagnetism and electrochemistry. His main discoveries include the principles underlying electromagnetic induction, ...
in 1834. Faraday is also credited to have coined the terms ''
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electr ...
'', electrolysis, among many others while he studied quantitative analysis of electrochemical reactions. Also he was an advocate of the law of conservation of energy.


First law

Faraday concluded after several experiments on
electric current An electric current is a stream of charged particles, such as electrons or ions, moving through an electrical conductor or space. It is measured as the net rate of flow of electric charge through a surface or into a control volume. The moving par ...
in a non-spontaneous process that the
mass Mass is an Intrinsic and extrinsic properties, intrinsic property of a body. It was traditionally believed to be related to the physical quantity, quantity of matter in a Physical object, physical body, until the discovery of the atom and par ...
of the products yielded on the electrodes was proportional to the value of current supplied to the cell, the length of time the current existed, and the molar mass of the substance analyzed. In other words, the amount of a substance deposited on each electrode of an electrolytic cell is directly proportional to the quantity of electricity passed through the cell. Below is a simplified equation of Faraday's first law: :m = \frac \cdot \frac where :''m'' is the mass of the substance produced at the electrode (in
gram The gram (originally gramme; SI unit symbol g) is a unit of mass in the International System of Units (SI) equal to one one thousandth of a kilogram. Originally defined as of 1795 as "the absolute weight of a volume Volume is a measure ...
s), :''Q'' is the total electric charge that passed through the solution (in
coulomb The coulomb (symbol: C) is the unit of electric charge in the International System of Units (SI). In 2019 redefinition of the SI base units, the present version of the SI it is equal to the electric charge delivered by a 1 ampere constant curre ...
s), :''n'' is the valence number of the substance as an ion in solution (electrons per ion), :''M'' is the molar mass of the substance (in grams per mole).


Second law

Faraday devised the laws of chemical electrodeposition of metals from solutions in 1857. He formulated the second law of electrolysis stating ''"the amounts of bodies which are equivalent to each other in their ordinary chemical action have equal quantities of electricity naturally associated with them."'' In other words, the quantities of different elements deposited by a given amount of electricity are in the
ratio In mathematics, a ratio shows how many times one number contains another. For example, if there are eight oranges and six lemons in a bowl of fruit, then the ratio of oranges to lemons is eight to six (that is, 8:6, which is equivalent to the ...
of their chemical equivalent weights. An important aspect of the second law of electrolysis is
electroplating Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the redox, reduction of cations of that metal by means of a direct current, direct electric cur ...
, which together with the first law of electrolysis has a significant number of applications in industry, as when used to protectively coat
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
s to avoid
corrosion Corrosion is a Erosion, natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosio ...
.


Applications

There are various important electrochemical processes in both nature and industry, like the coating of objects with metals or metal oxides through electrodeposition, the addition (
electroplating Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the redox, reduction of cations of that metal by means of a direct current, direct electric cur ...
) or removal (
electropolishing Electropolishing, also known as electrochemical polishing, anodic polishing, or electrolytic polishing (especially in the metallography field), is an electrochemical process that removes material from a metallic workpiece, reducing the surface roug ...
) of thin layers of metal from an object's surface, and the detection of alcohol in drunk drivers through the redox reaction of ethanol. The generation of chemical energy through
photosynthesis Photosynthesis is a process used by plants and other organisms to Energy transformation, convert light energy into chemical energy that, through cellular respiration, can later be released to fuel the organism's activities. Some of this chemica ...
is inherently an electrochemical process, as is production of metals like aluminum and titanium from their ores. Certain diabetes blood sugar meters measure the amount of glucose in the blood through its redox potential. In addition to established electrochemical technologies (like deep cycle lead acid batteries) there is also a wide range of new emerging technologies such as fuel cells, large format lithium-ion batteries, electrochemical reactors and super-capacitors that are becoming increasingly commercial. Electrochemical or coulometric titrations were introduced for quantitative analysis of minute quantities in 1938 by the Hungarian chemists László Szebellédy and Zoltan Somogyi. Electrochemistry also has important applications in the food industry, like the assessment of food/package interactions, the analysis of milk composition, the characterization and the determination of the freezing end-point of ice-cream mixes, or the determination of free acidity in
olive oil Olive oil is a vegetable oil, liquid fat obtained from olives (the fruit of ''Olea europaea''; family Oleaceae), a traditional Tree fruit, tree crop of the Mediterranean Basin, produced by pressing whole olives and extracting the oil. It is co ...
.


See also

* Bioelectromagnetism *
Bioelectrochemistry Bioelectrochemistry is a branch of electrochemistry Electrochemistry is the branch of physical chemistry concerned with the relationship between Electric potential, electrical potential difference, as a measurable and quantitative phenomenon, an ...
* Bipolar electrochemistry * Contact tension – a historical forerunner to the theory of electrochemistry. *
Corrosion engineering Corrosion engineering is an engineering specialty that applies scientific, technical, engineering skills, and knowledge of natural laws and physical resources to design and implement materials, structures, devices, systems, and procedures to mana ...
*
Cyclic Voltammetry Cyclic voltammetry (CV) is a type of voltammetry, potentiodynamic electrochemistry, electrochemical measurement. In a cyclic voltammetry experiment, the working electrode potential is ramped linearly versus time. Unlike in linear sweep voltammetry, ...
* Electrochemical impedance spectroscopy *
Electroanalytical methods Electroanalytical methods are a class of techniques in analytical chemistry which study an analyte by measuring the Voltage, potential (volts) and/or Electric current, current (amperes) in an electrochemical cell containing the analyte. These meth ...
* Electrocatalyst *
Electrochemical potential In electrochemistry, the electrochemical potential (ECP), ', is a thermodynamic measure of chemical potential that does not omit the energy contribution of electrostatics. Electrochemical potential is expressed in the unit of Joule, J/Mole (unit), ...
*
Electrochemiluminescence Electrochemiluminescence or electrogenerated chemiluminescence (ECL) is a kind of luminescence produced during electrochemical reactions in solutions. In electrogenerated chemiluminescence, electrochemically generated intermediates undergo a highl ...
* Electrodeionization *
Electropolishing Electropolishing, also known as electrochemical polishing, anodic polishing, or electrolytic polishing (especially in the metallography field), is an electrochemical process that removes material from a metallic workpiece, reducing the surface roug ...
*
Electroplating Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the redox, reduction of cations of that metal by means of a direct current, direct electric cur ...
*
Electrochemical engineering Electrochemical engineering is the branch of chemical engineering dealing with the technological applications of electrochemical phenomena, such as electrosynthesis of chemicals, electrowinning and refining of metals, flow batteries and fuel cells, ...
* Electrochemical energy conversion * Electrosynthesis * Frost diagram *
Fuel cells A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen fuel, hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most bat ...
*
ITIES In electrochemistry Electrochemistry is the branch of physical chemistry concerned with the relationship between Electric potential, electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, w ...
* List of electrochemists * Important publications in electrochemistry * Magnetoelectrochemistry * Nanoelectrochemistry *
Photoelectrochemistry Photoelectrochemistry is a subfield of study within physical chemistry concerned with the interaction of light with electrochemistry, electrochemical systems. It is an active domain of investigation. One of the pioneers of this field of electroche ...
* Plasma electrochemistry * Pourbaix diagram * Protein film voltammetry *
Reactivity series In chemistry, a reactivity series (or activity series) is an empirical, calculated, and structurally analytical progression of a series of metals, arranged by their "reactivity" from highest to lowest. It is used to summarize information about th ...
*
Redox titration A redox titration is a type of titration Titration (also known as titrimetry and volumetric analysis) is a common laboratory method of Quantitative research, quantitative Analytical chemistry, chemical analysis to determine the concentration ...
*
Standard electrode potential (data page) The data values of standard electrode potentials (''E''°) are given in the table below, in volts relative to the standard hydrogen electrode, and are for the following conditions: * A temperature of . * An Activity (chemistry), effective concen ...
*
Voltammetry Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied. The analytical data ...


References


Bibliography

*Ebbing, Darrell D. and Gammon, Steven D
General Chemistry
(2007) ,
Nobel Lectures in Chemistry
Volume 1, World Scientific (1999) *Swaddle, Thomas Wilso
Inorganic chemistry: an industrial and environmental perspective
Academic Press (1997) *Brett CMA, Brett AMO, ELECTROCHEMISTRY, Principles, methods, and applications, Oxford University Press, (1993) *Wiberg, Egon; Wiberg, Nils and Holleman, Arnold Frederic
Inorganic chemistry
Academic Press (2001)


External links

* * {{Use dmy dates, date=March 2017 Physical chemistry