![Electrolysis Apparatus](https://upload.wikimedia.org/wikipedia/commons/d/d1/Electrolysis_Apparatus.png)
In
chemistry
Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions ...
and
manufacturing
Manufacturing is the creation or production of goods with the help of equipment, labor, machines, tools, and chemical or biological processing or formulation. It is the essence of secondary sector of the economy. The term may refer to a r ...
, electrolysis is a technique that uses
direct electric current (DC) to drive an otherwise non-spontaneous
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 ...
. Electrolysis is commercially important as a stage in the separation of
elements from naturally occurring sources such as
ores
Ore is natural Rock (geology), rock or sediment that contains one or more valuable minerals, typically containing metals, that can be mined, treated and sold at a profit.Encyclopædia Britannica. "Ore". Encyclopædia Britannica Online. Ret ...
using 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 electrod ...
. 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 static electric field, it corresponds to the work needed per unit of charge to m ...
that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity".
Etymology
The word "electrolysis" was introduced 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 inducti ...
in 1834, using the
Greek
Greek may refer to:
Greece
Anything of, from, or related to Greece, a country in Southern Europe:
*Greeks, an ethnic group.
*Greek language, a branch of the Indo-European language family.
**Proto-Greek language, the assumed last common ancestor ...
words "amber", which since the 17th century was associated with
electrical phenomena
This is a list of electrical phenomena. Electrical phenomena are a somewhat arbitrary division of electromagnetic phenomena.
Some examples are:
* Biefeld–Brown effect — Thought by the person who coined the name, Thomas Townsend Brown, to ...
, and ' meaning "dissolution". Nevertheless, electrolysis, as a tool to study chemical reactions and obtain pure
elements, precedes the coinage of the term and formal description by Faraday.
History
In the early nineteenth century,
William Nicholson and
Anthony Carlisle
Sir Anthony Carlisle FRCS, FRS (15 February 1768 in Stillington, County Durham, England – 2 November 1840 in London) was an English surgeon.
Life
He was born in Stillington, County Durham, the third son of Thomas Carlisle and his first wife, ...
sought to further
Volta's experiments. They attached two wires to either side of a
voltaic pile
upright=1.2, Schematic diagram of a copper–zinc voltaic pile. The copper and zinc discs were separated by cardboard or felt spacers soaked in salt water (the electrolyte). Volta's original piles contained an additional zinc disk at the bottom, ...
and placed the other ends in a tube filled with water. They noticed when the wires were brought together that each wire produced bubbles. One type was hydrogen, the other was oxygen.
In 1785 a Dutch scientist named
Martin van Marum
Martin(us) van Marum (20 March 1750, Delft – 26 December 1837, Haarlem) was a Dutch physician, inventor, scientist and teacher, who studied medicine and philosophy in Groningen. Van Marum introduced modern chemistry in the Netherlands after ...
created an electrostatic generator that he used to reduce tin, zinc and antimony from their salts using a process later known as electrolysis. Though he unknowingly produced electrolysis, it was not until 1800 when William Nicholson and Anthony Carlisle discovered how electrolysis works.
In 1791
Luigi Galvani
Luigi Galvani (, also ; ; la, Aloysius Galvanus; 9 September 1737 – 4 December 1798) was an Italian physician, physicist, biologist and philosopher, who studied animal electricity. In 1780, he discovered that the muscles of dead frogs' legs ...
experimented with frog legs. He claimed that placing animal muscle between two dissimilar metal sheets resulted in electricity. Responding to these claims,
Alessandro Volta
Alessandro Giuseppe Antonio Anastasio Volta (, ; 18 February 1745 – 5 March 1827) was an Italian physicist, chemist and lay Catholic who was a pioneer of electricity and power who is credited as the inventor of the electric battery and the ...
conducted his own tests.
This would give insight to
Humphry Davy
Sir Humphry Davy, 1st Baronet, (17 December 177829 May 1829) was a 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 elements for t ...
's ideas on electrolysis. During preliminary experiments, Humphry Davy hypothesized that when two elements combine together to form a compound, electrical energy is released. Humphry Davy would go on to create Decomposition Tables from his preliminary experiments on Electrolysis. The Decomposition Tables would give insight on the energies needed to break apart certain compounds.
In 1817
Johan August Arfwedson
Johan August Arfwedson (12 January 1792 – 28 October 1841) was a Swedish chemist who discovered the chemical element lithium in 1817 by isolating it as a salt.
Life and work
Arfwedson belonged to a wealthy bourgeois family, the son of th ...
determined there was another element, lithium, in some of his samples; however, he could not isolate the component. It was not until 1821 that
William Thomas Brande
William Thomas Brande FRS FRSE (11 January 178811 February 1866) was an English chemist.
Biography
Brande was born in Arlington Street, London, England, the youngest son of six children to Augustus Everard Brande an apothecary, originally fro ...
used electrolysis to single it out. Two years later, he streamlined the process using lithium chloride and potassium chloride with electrolysis to produce lithium and lithium hydroxide.
During the later years of Humphry Davy's research, Michael Faraday became his assistant. While studying the process of electrolysis under Humphry Davy, Michael Faraday discovered two
laws of electrolysis
Faraday's laws of electrolysis are quantitative relationships based on the electrochemical research published by Michael Faraday in 1833.
First law
Michael Faraday reported that the mass (m) of elements deposited at an electrode is directly prop ...
.
During the time of Maxwell and Faraday, concerns came about for
electropositive
Electronegativity, symbolized as , 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 atomic number and the d ...
and
electronegative
Electronegativity, symbolized as , 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 atomic number and the d ...
activities.
In November 1875,
Paul Émile Lecoq de Boisbaudran
Paul may refer to:
*Paul (given name), a given name (includes a list of people with that name)
*Paul (surname), a list of people
People
Christianity
*Paul the Apostle (AD c.5–c.64/65), also known as Saul of Tarsus or Saint Paul, early Chris ...
discovered
gallium
Gallium is a chemical element with the symbol Ga and atomic number 31. Discovered by French chemist Paul-Émile Lecoq de Boisbaudran in 1875, Gallium is in group 13 of the periodic table and is similar to the other metals of the group (aluminiu ...
using electrolysis of gallium hydroxide, producing 3.4 mg of gallium. The following December, he presented his discovery of gallium to the
Académie des sciences
The French Academy of Sciences (French: ''Académie des sciences'') is a learned society, founded in 1666 by Louis XIV at the suggestion of Jean-Baptiste Colbert, to encourage and protect the spirit of French scientific research. It was at the ...
in Paris.
On June 26, 1886,
Ferdinand Frederick Henri Moissan
Ferdinand Frédéric Henri Moissan (28 September 1852 – 20 February 1907) was a French chemist and pharmacist who won the 1906 Nobel Prize in Chemistry for his work in isolating fluorine from its compounds. Moissan was one of the original mem ...
finally felt comfortable performing electrolysis on
anhydrous
A substance is anhydrous if it contains no water. Many processes in chemistry can be impeded by the presence of water; therefore, it is important that water-free reagents and techniques are used. In practice, however, it is very difficult to achie ...
hydrogen fluoride to create a gaseous fluorine pure element. Before he used hydrogen fluoride, Henri Moissan used fluoride salts with electrolysis. Thus on June 28, 1886, he performed his experiment in front of the Académie des sciences to show his discovery of the new element fluorine. While trying to find elemental fluorine through electrolysis of fluoride salts, many chemists perished including Paulin Louyet and Jérôme Nicklès.
In 1886
Charles Martin Hall
Charles Martin Hall (December 6, 1863 – December 27, 1914) was an American inventor, businessman, and chemist. He is best known for his invention in 1886 of an inexpensive method for producing aluminum, which became the first metal to atta ...
from America and
Paul Héroult
Paul (Louis-Toussaint) Héroult (10 April 1863 – 9 May 1914) was a French scientist. He was the inventor of the aluminium electrolysis and developed the first successful commercial electric arc furnace. He lived in Thury-Harcourt, Normandy.
...
from France both filed for American patents for the electrolysis of aluminum, with Héroult submitting his in May, and Hall, in July. Hall was able to get his patent by proving through letters to his brother and family evidence that his method was discovered before the French patent was submitted. This became known as the
Hall-Héroult process which benefited many industries because aluminum's price then dropped from four dollars to thirty cents per pound.
Timeline
* 1785 –
Martinus van Marum
Martin(us) van Marum (20 March 1750, Delft – 26 December 1837, Haarlem) was a Dutch physician, inventor, scientist and teacher, who studied medicine and philosophy in Groningen. Van Marum introduced modern chemistry in the Netherlands after ...
's electrostatic generator was used to reduce
tin
Tin is a chemical element with the symbol Sn (from la, stannum) and atomic number 50. Tin is a silvery-coloured metal.
Tin is soft enough to be cut with little force and a bar of tin can be bent by hand with little effort. When bent, t ...
,
zinc
Zinc is a chemical element with the 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 (IIB) of the periodi ...
, and
antimony
Antimony is a chemical element with the symbol Sb (from la, stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient time ...
from their salts using electrolysis.
* 1800 –
William Nicholson and
Anthony Carlisle
Sir Anthony Carlisle FRCS, FRS (15 February 1768 in Stillington, County Durham, England – 2 November 1840 in London) was an English surgeon.
Life
He was born in Stillington, County Durham, the third son of Thomas Carlisle and his first wife, ...
(and also
Johann Ritter
Johann Wilhelm Ritter (16 December 1776 – 23 January 1810). was a Germans, German chemist, physicist and philosopher. He was born in Zamienice, Samitz (Zamienice) near Chojnów, Haynau (Chojnów) in Silesia (then part of Kingdom of Prussia, Pr ...
), decomposed
water
Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
into
hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
and
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
.
* 1808 –
Potassium
Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosphe ...
(1807),
sodium
Sodium is a chemical element with the 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 of the periodic table. Its only stable iso ...
(1807),
barium
Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element.
Th ...
,
calcium
Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to ...
and
magnesium
Magnesium is a chemical element with the 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 2 of the periodic ta ...
were discovered by
Humphry Davy
Sir Humphry Davy, 1st Baronet, (17 December 177829 May 1829) was a 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 elements for t ...
using electrolysis.
* 1821 –
Lithium
Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid el ...
was discovered by the English chemist
William Thomas Brande
William Thomas Brande FRS FRSE (11 January 178811 February 1866) was an English chemist.
Biography
Brande was born in Arlington Street, London, England, the youngest son of six children to Augustus Everard Brande an apothecary, originally fro ...
, who obtained it by electrolysis of lithium oxide.
* 1834 –
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 inducti ...
published his
two laws of electrolysis, provided a mathematical explanation for them, and introduced terminology such as electrode, electrolyte, anode, cathode, anion, and cation.
* 1875 –
Paul Émile Lecoq de Boisbaudran
Paul may refer to:
*Paul (given name), a given name (includes a list of people with that name)
*Paul (surname), a list of people
People
Christianity
*Paul the Apostle (AD c.5–c.64/65), also known as Saul of Tarsus or Saint Paul, early Chris ...
discovered
gallium
Gallium is a chemical element with the symbol Ga and atomic number 31. Discovered by French chemist Paul-Émile Lecoq de Boisbaudran in 1875, Gallium is in group 13 of the periodic table and is similar to the other metals of the group (aluminiu ...
using electrolysis.
* 1886 –
Fluorine
Fluorine is a chemical element with the symbol F and atomic number 9. It is the lightest halogen and exists at standard conditions as a highly toxic, pale yellow diatomic gas. As the most electronegative reactive element, it is extremely reacti ...
was discovered by
Henri Moissan
Ferdinand Frédéric Henri Moissan (28 September 1852 – 20 February 1907) was a French chemist and pharmacist who won the 1906 Nobel Prize in Chemistry for his work in isolating fluorine from its compounds. Moissan was one of the original mem ...
using electrolysis.
* 1886 –
Hall–Héroult process
The Hall–Héroult process is the major industrial process for smelting aluminium. It involves dissolving aluminium oxide (alumina) (obtained most often from bauxite, aluminium's chief ore, through the Bayer process) in molten cryolite, and el ...
developed for making
aluminium
Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
.
* 1890 –
Castner–Kellner process
The Castner–Kellner process is a method of electrolysis on an aqueous alkali chloride solution (usually sodium chloride solution) to produce the corresponding alkali hydroxide, invented by American Hamilton Castner and Austrian Carl Kellner in t ...
developed for making
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 caustic base and alkali ...
.
Overview
Electrolysis is the passing of a
direct electric current through an
electrolyte
An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
producing chemical reactions at the
electrode
An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of batteries that can consist of a variety of materials de ...
s and
decomposition
Decomposition or rot is the process by which dead organic substances are broken down into simpler organic or inorganic matter such as carbon dioxide, water, simple sugars and mineral salts. The process is a part of the nutrient cycle and is e ...
of the materials.
The main components required to achieve electrolysis are an
electrolyte
An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
, electrodes, and an external power source. A partition (e.g. an
ion-exchange membrane An ion-exchange membrane is a semi-permeable membrane that transports certain dissolved ions, while blocking other ions or neutral molecules.
Ion-exchange membranes are therefore electrically conductive. They are often used in desalination and c ...
or a
salt bridge
In electrochemistry, a salt bridge or ion bridge is a laboratory device used to connect the oxidation and reduction half-cells of a galvanic cell (voltaic cell), a type of electrochemical cell. It maintains electrical neutrality within the int ...
) is optional to keep the products from diffusing to the vicinity of the opposite electrode.
The electrolyte is a
chemical substance
A chemical substance is a form of matter having constant chemical composition and characteristic properties. Some references add that chemical substance cannot be separated into its constituent elements by physical separation methods, i.e., wi ...
which contains
free ions and carries
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 pa ...
(e.g. an ion-conducting
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
, solution, or a
ionic liquid
An ionic liquid (IL) is a salt in the liquid state. In some contexts, the term has been restricted to salts whose melting point is below a specific temperature, such as . While ordinary liquids such as water and gasoline are predominantly made of ...
compound). If the ions are not mobile, as in most solid
salts
In chemistry, a salt is a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a compound with no net electric charge. A common example is table salt, with positively cha ...
, then electrolysis cannot occur. A liquid electrolyte is produced by:
*
Solvation
Solvation (or dissolution) describes the interaction of a solvent with dissolved molecules. Both ionized and uncharged molecules interact strongly with a solvent, and the strength and nature of this interaction influence many properties of the ...
or reaction of an
ionic compound
In chemistry, an ionic compound is a chemical compound composed of ions held together by electrostatic forces termed ionic bonding. The compound is neutral overall, but consists of positively charged ions called cations and negatively charged i ...
with a
solvent
A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
(such as water) to produce mobile ions
* An ionic compound melted by heating
The electrodes are immersed separated by a distance such that a current flows between them through the
electrolyte
An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
and are connected to the power source which completes the
electrical circuit
An electrical network is an interconnection of electrical components (e.g., batteries, resistors, inductors, capacitors, switches, transistors) or a model of such an interconnection, consisting of electrical elements (e.g., voltage sources, ...
. A
direct current
Direct current (DC) is one-directional flow of electric charge. An electrochemical cell is a prime example of DC power. Direct current may flow through a conductor such as a wire, but can also flow through semiconductors, insulators, or even ...
supplied by the power source drives the reaction causing ions in the electrolyte to be attracted toward the respective oppositely charged electrode.
Electrodes of
metal
A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
,
graphite
Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on large ...
and
semiconductor
A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...
material are widely used. Choice of suitable
electrode
An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of batteries that can consist of a variety of materials de ...
depends on chemical reactivity between the electrode and electrolyte and manufacturing cost. Historically, when non-reactive anodes were desired for electrolysis, graphite (called plumbago in Faraday's time) or platinum were chosen.
They were found to be some of the least reactive materials for anodes. Platinum erodes very slowly compared to other materials, and graphite crumbles and can produce carbon dioxide in aqueous solutions but otherwise does not participate in the reaction. Cathodes may be made of the same material, or they may be made from a more reactive one since anode wear is greater due to oxidation at the anode.
Process of electrolysis
The key process of electrolysis is the interchange of atoms and ions by the removal or addition of electrons due to the applied current. The desired products of electrolysis are often in a different physical state from the electrolyte and can be removed by mechanical processes (e.g. by collecting gas above an electrode or precipitating a product out of the electrolyte).
The quantity of the products is proportional to the current, and when two or more electrolytic cells are connected in series to the same power source, the products produced in the cells are proportional to their
equivalent weight
In chemistry, equivalent weight (also known as gram equivalent) is the mass of one equivalent, that is the mass of a given substance which will combine with or displace a fixed quantity of another substance. The equivalent weight of an element is ...
. These are known as
Faraday's laws of electrolysis
Faraday's laws of electrolysis are quantitative relationships based on the electrochemical research published by Michael Faraday in 1833.
First law
Michael Faraday reported that the mass (m) of elements deposited at an electrode is directly prop ...
.
Each electrode attracts ions that are of the opposite
charge
Charge or charged may refer to:
Arts, entertainment, and media Films
* ''Charge, Zero Emissions/Maximum Speed'', a 2011 documentary
Music
* ''Charge'' (David Ford album)
* ''Charge'' (Machel Montano album)
* ''Charge!!'', an album by The Aqua ...
. Positively charged ions (
cation
An ion () is an atom or molecule with a net 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 positive by convent ...
s) move towards the electron-providing (negative) cathode. Negatively charged ions (
anion
An ion () is an atom or molecule with a net 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 positive by convent ...
s) move towards the electron-extracting (positive) anode. In this process
electron
The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family,
and are generally thought to be elementary particles because they have no kn ...
s are effectively introduced at the cathode as a
reactant
In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
and removed at the anode as a
product
Product may refer to:
Business
* Product (business), an item that serves as a solution to a specific consumer problem.
* Product (project management), a deliverable or set of deliverables that contribute to a business solution
Mathematics
* Produ ...
. In chemistry, the loss of electrons is called
oxidation
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
, while electron gain is called
reduction.
When neutral atoms or molecules, such as those on the surface of an electrode, gain or lose electrons they become ions and may dissolve in the electrolyte and react with other ions.
When ions gain or lose electrons and become neutral, they will form compounds that separate from the electrolyte. Positive metal ions like Cu
2+ deposit onto the cathode in a layer. The terms for this are
electroplating
Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the reduction of cations of that metal by means of a direct electric current. The part to be ...
,
electrowinning
Electrowinning, also called electroextraction, is the electrodeposition of metals from their ores that have been put in solution via a process commonly referred to as leaching. Electrorefining uses a similar process to remove impurities from a ...
, and
electrorefining
Electrowinning, also called electroextraction, is the electrodeposition of metals from their ores that have been put in solution via a process commonly referred to as leaching. Electrorefining uses a similar process to remove impurities from a ...
.
When an ion gains or loses electrons without becoming neutral, its electronic charge is altered in the process.
For example, the
electrolysis of brine produces hydrogen and chlorine gases which bubble from the electrolyte and are collected. The initial overall reaction is thus:
:2 NaCl + 2 H
2O → 2 NaOH + H
2 + Cl
2
The reaction at the anode results in chlorine gas from chlorine ions:
:2 Cl
− → Cl
2 + 2 e
−
The reaction at the cathode results in hydrogen gas and hydroxide ions:
:2 H
2O + 2 e
− → H
2 + 2 OH
−
Without a partition between the electrodes, the OH
− ions produced at the cathode are free to diffuse throughout the electrolyte to the anode. As the electrolyte becomes more
basic
BASIC (Beginners' All-purpose Symbolic Instruction Code) is a family of general-purpose, high-level programming languages designed for ease of use. The original version was created by John G. Kemeny and Thomas E. Kurtz at Dartmouth College ...
due to the production of OH
−, less Cl
2 emerges from the solution as it begins to react with the hydroxide producing
hypochlorite
In chemistry, hypochlorite is an anion with the chemical formula ClO−. It combines with a number of cations to form hypochlorite salts. Common examples include sodium hypochlorite (household bleach) and calcium hypochlorite (a component of ble ...
(ClO
−) at the anode:
:Cl
2 + 2 NaOH → NaCl + NaClO + H
2O
The more opportunity the Cl
2 has to interact with NaOH in the solution, the less Cl
2 emerges at the surface of the solution and the faster the production of hypochlorite progresses. This depends on factors such as solution temperature, the amount of time the Cl
2 molecule is in contact with the solution, and concentration of NaOH.
Likewise, as hypochlorite increases in concentration, chlorates are produced from them:
: 3 NaClO → NaClO
3 + 2 NaCl
Other reactions occur, such as the
self-ionization of water
The self-ionization of water (also autoionization of water, and autodissociation of water) is an ionization reaction in pure water or in an aqueous solution, in which a water molecule, H2O, deprotonates (loses the nucleus of one of its hydrogen ...
and the decomposition of hypochlorite at the cathode, the rate of the latter depends on factors such as
diffusion
Diffusion is the net movement of anything (for example, atoms, ions, molecules, energy) generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical p ...
and the surface area of the cathode in contact with the electrolyte.
Decomposition potential
Decomposition potential or decomposition voltage refers to the minimum voltage (difference in
electrode potential
In electrochemistry, electrode potential is the electromotive force of a galvanic cell built from a standard reference electrode and another electrode to be characterized. By convention, the reference electrode is the standard hydrogen electrode (S ...
) between
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 ...
and
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 whi ...
of an electrolytic cell that is needed for electrolysis to occur.
The voltage at which electrolysis is thermodynamically preferred is the difference of the electrode potentials as calculated using the
Nernst equation
In electrochemistry, the Nernst equation is a Thermodynamics#Chemical thermodynamics, chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction (half-cell or electrochemical cell, full cell reacti ...
. Applying additional voltage, referred to as
overpotential
In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly relat ...
, can increase the rate of reaction and is often needed above the thermodynamic value. It is especially necessary for electrolysis reactions involving gases, such as
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
,
hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
or
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 ...
.
Oxidation and reduction at the electrodes
Oxidation
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
of ions or neutral molecules occurs at 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 ...
. For example, it is possible to oxidize ferrous ions to ferric ions at the anode:
: Fe(aq) → Fe(aq) + e
−
Reduction of ions or neutral molecules occurs 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 whi ...
. It is possible to reduce
ferricyanide
Ferricyanide is the anion e(CN)6sup>3−. It is also called hexacyanoferrate(III) and in rare, but systematic nomenclature, hexacyanidoferrate(III). The most common salt of this anion is potassium ferricyanide, a red crystalline material that i ...
ions to
ferrocyanide
Ferrocyanide is the name of the anion CN)6">cyanide.html" ;"title="e(cyanide">CN)6sup>4−. Salts of this coordination complex give yellow solutions. It is usually available as the salt potassium ferrocyanide, which has the formula K4Fe(CN)6. e ...
ions at the cathode:
:Fe(CN) + e
− → Fe(CN)
Neutral molecules can also react at either of the electrodes. For example: ''p''-benzoquinone can be reduced to hydroquinone at the cathode:
: + 2 e
− + 2 H
+ →
In the last example, H
+ ions (hydrogen ions) also take part in the reaction and are provided by the acid in the solution, or by the solvent itself (water, methanol, etc.). Electrolysis reactions involving H
+ ions are fairly common in acidic solutions. In aqueous alkaline solutions, reactions involving OH
− (hydroxide ions) are common.
Sometimes the solvents themselves (usually water) are oxidized or reduced at the electrodes. It is even possible to have electrolysis involving gases, e.g. by using a
gas diffusion electrode
Gas diffusion electrodes (GDE) are electrodes with a conjunction of a solid, liquid and gaseous interface, and an electrical conducting catalyst supporting an electrochemical reaction between the liquid and the gaseous phase.
Principle
GDEs are us ...
.
Energy changes during electrolysis
The amount of electrical energy that must be added equals the 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 that may be performed by a thermodynamically closed system at constant temperature and pr ...
of the reaction plus the losses in the system. The losses can (in theory) be arbitrarily close to zero, so the maximum
thermodynamic
Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of ther ...
efficiency equals the
enthalpy
Enthalpy , a property of a thermodynamic system, is the sum of the system's internal energy and the product of its pressure and volume. It is a state function used in many measurements in chemical, biological, and physical systems at a constant ...
change divided by the free energy change of the reaction. In most cases, the electric input is larger than the enthalpy change of the reaction, so some energy is released in the form of heat. In some cases, for instance, in the electrolysis of
steam
Steam is a substance containing water in the gas phase, and sometimes also an aerosol of liquid water droplets, or air. This may occur due to evaporation or due to boiling, where heat is applied until water reaches the enthalpy of vaporization ...
into hydrogen and oxygen at high temperature, the opposite is true and heat energy is absorbed. This heat is absorbed from the surroundings, and the
heating value
The heating value (or energy value or calorific value) of a substance, usually a fuel or food (see food energy), is the amount of heat released during the combustion of a specified amount of it.
The ''calorific value'' is the total energy relea ...
of the produced hydrogen is higher than the electric input.
Variations
Pulsating current results in products different from DC. For example, pulsing increases the ratio of
ozone
Ozone (), or trioxygen, is an inorganic molecule with the chemical formula . It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope , breaking down in the lo ...
to oxygen produced at the anode in the electrolysis of an aqueous acidic solution such as dilute sulphuric acid.
Electrolysis of ethanol with pulsed current evolves an aldehyde instead of primarily an acid.
Related processes
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 Oxidation-Reduction reactions. A common apparatus ...
s and
batteries
Battery most often refers to:
* Electric battery, a device that provides electrical power
* Battery (crime), a crime involving unlawful physical contact
Battery may also refer to:
Energy source
*Automotive battery, a device to provide power t ...
use spontaneous, energy-releasing
redox reactions
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
to generate an electrical potential that provides useful power. When a
secondary battery
A rechargeable battery, storage battery, or secondary cell (formally a type of energy accumulator), is a type of electrical battery which can be charged, discharged into a load, and recharged many times, as opposed to a disposable or prima ...
is charged, its redox reaction is run in reverse and the system can be considered as 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 electrod ...
.
Industrial uses
*
Electrometallurgy
Electrometallurgy is a method in metallurgy that uses electrical energy to produce metals by electrolysis. It is usually the last stage in metal production and is therefore preceded by pyrometallurgical or hydrometallurgical operations. The electr ...
of
aluminium
Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
,
lithium
Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid el ...
,
sodium
Sodium is a chemical element with the 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 of the periodic table. Its only stable iso ...
,
potassium
Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosphe ...
,
magnesium
Magnesium is a chemical element with the 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 2 of the periodic ta ...
,
calcium
Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to ...
, and in some cases
copper
Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkis ...
.
*
Production of chlorine and
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 caustic base and alkali ...
, called the
Chloralkali process
The chloralkali process (also chlor-alkali and chlor alkali) is an industrial process for the electrolysis of sodium chloride (NaCl) solutions. It is the technology used to produce chlorine and sodium hydroxide (caustic soda), which are comm ...
.
* Production of
sodium chlorate
Sodium chlorate is an inorganic compound with the chemical formula Na ClO3. It is a white crystalline powder that is readily soluble in water. It is hygroscopic. It decomposes above 300 °C to release oxygen and leaves sodium chloride. Sever ...
and
potassium chlorate
Potassium chlorate is a compound containing potassium, chlorine and oxygen, with the molecular formula KClO3. In its pure form, it is a white crystalline substance. After sodium chlorate, it is the second most common chlorate in industrial use. It ...
.
* Production of perfluorinated organic compounds such as
trifluoroacetic acid
Trifluoroacetic acid (TFA) is an organofluorine compound with the chemical formula CF3CO2H. It is a structural analogue of acetic acid with all three of the acetyl group's hydrogen atoms replaced by fluorine atoms and is a colorless liquid with a ...
by the process of
electrofluorination Electrochemical fluorination (ECF), or electrofluorination, is a foundational organofluorine chemistry method for the preparation of fluorocarbon-based organofluorine compounds.G. Siegemund, W. Schwertfeger, A. Feiring, B. Smart, F. Behr, H. Vogel, ...
.
*
Purifying copper from refined
copper
Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkis ...
.
* Production of fuels such as
hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
for
spacecraft
A spacecraft is a vehicle or machine designed to fly in outer space. A type of artificial satellite, spacecraft are used for a variety of purposes, including communications, Earth observation, meteorology, navigation, space colonization, p ...
,
nuclear submarines
A nuclear submarine is a submarine powered by a nuclear reactor, but not necessarily nuclear-armed. Nuclear submarines have considerable performance advantages over "conventional" (typically diesel-electric) submarines. Nuclear propulsion, ...
and
vehicles
A vehicle (from la, vehiculum) is a machine that transports people or cargo. Vehicles include wagons, bicycles, motor vehicles (motorcycles, cars, trucks, buses, mobility scooters for disabled people), railed vehicles (trains, trams), wate ...
.
*
Rust removal and cleaning of old coins and other metallic objects.
Manufacturing processes
In manufacturing, electrolysis can be used for:
*
Electroplating
Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the reduction of cations of that metal by means of a direct electric current. The part to be ...
, where a thin film of metal is deposited over a substrate material. Electroplating is used in many industries for either functional or decorative purposes, as in-vehicle bodies and nickel coins.
*
Electrochemical machining
Electrochemical machining (ECM) is a method of removing metal by an electrochemical process. It is normally used for mass production and is used for working extremely hard materials or materials that are difficult to machine using conventional met ...
(ECM), where an electrolytic cathode is used as a shaped tool for removing material by anodic oxidation from a workpiece. ECM is often used as a technique for
deburring
A burr is a raised edge or small piece of material that remains attached to a workpiece after a modification process.
It is usually an unwanted piece of material and is removed with a deburring tool in a process called 'deburring'. Burrs are mo ...
or for etching metal surfaces like tools or knives with a permanent mark or logo.
Competing half-reactions in solution electrolysis
Using a cell containing inert platinum electrodes, electrolysis of aqueous solutions of some salts leads to the reduction of the cations (such as metal deposition with, for example, zinc salts) and oxidation of the anions (such as the evolution of bromine with bromides). However, with salts of some metals (such as sodium) hydrogen is evolved at the cathode, and for salts containing some anions (such as sulfate ) oxygen is evolved at the anode. In both cases, this is due to water being reduced to form hydrogen or oxidized to form oxygen.
In principle, the voltage required to electrolyze a salt solution can be derived from the
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 emf (electromotive force) of a cell in wh ...
for the reactions at the anode and cathode. The standard electrode potential is directly related to 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 that may be performed by a thermodynamically closed system at constant temperature and pr ...
, Δ''G'', for the reactions at each electrode and refers to an electrode with no current flowing. An extract from the
table of standard electrode potentials
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 effective concentration of 1 mol ...
is shown below.
:
In terms of electrolysis, this table should be interpreted as follows:
* Moving ''down'' the table, ''E''° becomes more positive, and species on the ''left'' are more likely to be ''reduced'': for example, zinc ions are more likely to be reduced to zinc metal than sodium ions are to be reduced to sodium metal.
* Moving ''up'' the table, ''E''° becomes more negative, and species on the ''right'' are more likely to be ''oxidized'': for example, sodium metal is more likely to be oxidized to sodium ions than zinc metal is to be oxidized to zinc ions.
Using the
Nernst equation
In electrochemistry, the Nernst equation is a Thermodynamics#Chemical thermodynamics, chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction (half-cell or electrochemical cell, full cell reacti ...
the
electrode potential
In electrochemistry, electrode potential is the electromotive force of a galvanic cell built from a standard reference electrode and another electrode to be characterized. By convention, the reference electrode is the standard hydrogen electrode (S ...
can be calculated for a specific concentration of ions, temperature and the number of electrons involved. For pure water (
pH 7):
* the electrode potential for the reduction producing hydrogen is −0.41 V,
* the electrode potential for the oxidation producing oxygen is +0.82 V.
Comparable figures calculated in a similar way, for 1 M
zinc bromide
Zinc bromide ( Zn Br2) is an inorganic compound with the chemical formula Zn Br2. It is a colourless salt that shares many properties with zinc chloride (ZnCl2), namely a high solubility in water forming acidic solutions, and good solubility in o ...
, ZnBr
2, are −0.76 V for the reduction to Zn metal and +1.10 V for the oxidation producing bromine.
The conclusion from these figures is that hydrogen should be produced at the cathode and oxygen at the anode from the electrolysis of water—which is at variance with the experimental observation that zinc metal is deposited and bromine is produced.
The explanation is that these calculated potentials only indicate the thermodynamically preferred reaction. In practice, many other factors have to be taken into account such as the kinetics of some of the reaction steps involved. These factors together mean that a higher potential is required for the reduction and oxidation of water than predicted, and these are termed
overpotential
In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly relat ...
s. Experimentally it is known that overpotentials depend on the design of the cell and the nature of the electrodes.
For the electrolysis of a neutral (pH 7) sodium chloride solution, the reduction of sodium ion is thermodynamically very difficult and water is reduced evolving hydrogen leaving hydroxide ions in solution. At the anode the oxidation of chlorine is observed rather than the oxidation of water since the overpotential for the oxidation of
chloride
The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride salts ...
to
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 ...
is lower than the overpotential for the oxidation of
water
Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
to
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
. The
hydroxide ion
Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It ...
s and dissolved chlorine gas react further to form
hypochlorous acid
Hypochlorous acid (HClO, HOCl, or ClHO) is a weak acid that forms when chlorine dissolves in water, and itself partially dissociates, forming hypochlorite, ClO−. HClO and ClO− are oxidizers, and the primary disinfection agents of chlorine so ...
. The aqueous solutions resulting from this process is called
electrolyzed water
Electrolysed water (electrolyzed water, EOW, ECA, electrolyzed oxidizing water, electro-activated water or electro-chemically activated water solution) is produced by the electrolysis of ordinary tap water containing dissolved sodium chloride. The ...
and is used as a disinfectant and cleaning agent.
Research trends
Electrolysis of carbon dioxide
The electrochemical reduction or electrocatalytic conversion of
CO2 can produce value-added chemicals such
methane
Methane ( , ) is a chemical compound with the chemical formula (one carbon atom bonded to four hydrogen atoms). It is a group-14 hydride, the simplest alkane, and the main constituent of natural gas. The relative abundance of methane on Eart ...
,
ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds).
Ethylene i ...
,
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 ...
, etc. The electrolysis of carbon dioxide gives formate or carbon monoxide, but sometimes more elaborate organic compounds such as
ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds).
Ethylene i ...
. This technology is under research as a carbon-neutral route to organic compounds.
Electrolysis of acidified water
Electrolysis of water produces
hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
and oxygen in a ratio of 2 to 1 respectively.
:2 H
2O → 2 H
2 + O
2 ''E''° = +1.229 V
The
energy efficiency
Energy efficiency may refer to:
* Energy efficiency (physics), the ratio between the useful output and input of an energy conversion process
** Electrical efficiency, useful power output per electrical power consumed
** Mechanical efficiency, a ra ...
of water electrolysis varies widely. The efficiency of an electrolyzer is a measure of the enthalpy contained in the hydrogen (to undergo combustion with oxygen or some other later reaction), compared with the input electrical energy. Heat/enthalpy values for hydrogen are well published in science and engineering texts, as 144 MJ/kg. Note that fuel cells (not electrolyzers) cannot use this full amount of heat/enthalpy, which has led to some confusion when calculating efficiency values for both types of technology. In the reaction, some energy is lost as heat. Some reports quote efficiencies between 50% and 70% for alkaline electrolyzers; however, much higher practical efficiencies are available with the use of
polymer electrolyte membrane electrolysis Polymer electrolyte membrane (PEM) electrolysis is the electrolysis of water in a cell equipped with a solid polymer electrolyte (SPE) that is responsible for the conduction of protons, separation of product gases, and electrical insulation of the e ...
and catalytic technology, such as 95% efficiency.
The
National Renewable Energy Laboratory
The National Renewable Energy Laboratory (NREL) in the US specializes in the research and development of renewable energy, energy efficiency, energy systems integration, and sustainable transportation. NREL is a federally funded research and d ...
estimated in 2006 that 1 kg of hydrogen (roughly equivalent to 3 kg, or 4 liters, of petroleum in energy terms) could be produced by wind powered electrolysis for between US$5.55 in the near term and US$2.27 in the longer term.
About 4% of hydrogen gas produced worldwide is generated by electrolysis, and normally used onsite. Hydrogen is used for the creation of ammonia for fertilizer via the
Haber process
The Haber process, also called the Haber–Bosch process, is an artificial nitrogen fixation process and is the main industrial procedure for the production of ammonia today. It is named after its inventors, the German chemists Fritz Haber and C ...
, and converting heavy petroleum sources to lighter fractions via
hydrocracking
In petrochemistry, petroleum geology and organic chemistry, cracking is the process whereby complex organic molecules such as kerogens or long-chain hydrocarbons are broken down into simpler molecules such as light hydrocarbons, by the breaking of ...
. Recently, onsite electrolysis has been utilized to capture hydrogen for hydrogen fuel-cells in
hydrogen vehicles
A hydrogen vehicle is a vehicle that uses hydrogen fuel for motive power. Hydrogen vehicles include hydrogen-fueled space rockets, as well as ships and aircraft. Power is generated by converting the chemical energy of hydrogen to mechanical energy ...
.
Carbon/hydrocarbon assisted water electrolysis
Recently, to reduce the energy input, the utilization of carbon (
coal
Coal is a combustible black or brownish-black sedimentary rock, formed as rock strata called coal seams. Coal is mostly carbon with variable amounts of other elements, chiefly hydrogen, sulfur, oxygen, and nitrogen.
Coal is formed when dea ...
),
alcohol
Alcohol most commonly refers to:
* Alcohol (chemistry), an organic compound in which a hydroxyl group is bound to a carbon atom
* Alcohol (drug), an intoxicant found in alcoholic drinks
Alcohol may also refer to:
Chemicals
* Ethanol, one of sev ...
s (hydrocarbon solution), and organic solution (
glycerol
Glycerol (), also called glycerine in British English and glycerin in American English, is a simple triol compound. It is a colorless, odorless, viscous liquid that is sweet-tasting and non-toxic. The glycerol backbone is found in lipids known ...
, formic acid,
ethylene glycol
Ethylene glycol (IUPAC name: ethane-1,2-diol) is an organic compound (a vicinal diol) with the formula . It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an odo ...
, etc.) with co-electrolysis of water has been proposed as a viable option. The carbon/hydrocarbon assisted water electrolysis (so-called CAWE) process for hydrogen generation would perform this operation in a single
electrochemical
Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outco ...
reactor. This system energy balance can be required only around 40% electric input with 60% coming from the chemical energy of carbon or hydrocarbon. This process utilizes solid coal/carbon particles or powder as fuels dispersed in acid/alkaline electrolyte in the form of slurry and the carbon contained source co-assist in the electrolysis process as following theoretical overall reactions:
:Carbon/Coal slurry (C + 2H
2O) → CO
2 + 2H
2 ''E''′ = 0.21 V (reversible voltage) / ''E''′ = 0.46 V (thermo-neutral voltage)
or
:Carbon/Coal slurry (C + H
2O) → CO + H
2 ''E''′ = 0.52 V (reversible voltage) / ''E''′ = 0.91 V (thermo-neutral voltage)
Thus, this CAWE approach is that the actual cell overpotential can be significantly reduced to below 1.0 V as compared to 1.5 V for conventional water electrolysis.
Electrocrystallization
A specialized application of electrolysis involves the growth of conductive crystals on one of the electrodes from oxidized or reduced species that are generated in situ. The technique has been used to obtain single crystals of low-dimensional electrical conductors, such as
charge-transfer salt
In chemistry, a charge-transfer (CT) complex or electron-donor-acceptor complex describes a type of supramolecular assembly of two or more molecules or ions. The assembly consists of two molecules that self-attract through electrostatic forces, ...
s and
linear chain compounds
Electrolysis of Iron Ore
The current method of producing steel from
iron ore
Iron ores are rocks and minerals from which metallic iron can be economically extracted. The ores are usually rich in iron oxides and vary in color from dark grey, bright yellow, or deep purple to rusty red. The iron is usually found in the fo ...
is very carbon intensive, in part to the direct release of CO
2 in the blast furnace. A study of steel making in Germany found that producing 1 ton of steel emitted 2.1 tons of
CO2e with 22% of that being direct emissions from the blast furnace. As of 2022, steel production contributes from 7 to 9% of global emissions. Electrolysis of iron can eliminate direct emissions and further reduce emissions if the electricity is created from green energy.
The small-scale electrolysis of iron has been successfully reported by dissolving it in molten
oxide
An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
salts and using a platinum anode. Oxygen anions form oxygen gas and electrons at the anode. Iron cations consume electrons and form iron metal at the cathode. This method was performed a temperature of 1550 °C which presents a significant challenge to maintaining the reaction. Particularly, anode
corrosion
Corrosion is a 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. Corrosion engine ...
is a concern at these temperatures.
Additionally, the low temperature reduction of iron oxide by dissolving it in alkaline water has been reported.
The temperature is much lower than traditional iron production at 114 °C. The low temperatures also tend to correlate with higher current efficiencies, with an efficiency of 95% being reported. While these methods are promising, they struggle to be cost competitive because of the large economies of scale keeping the price of blast furnace iron low.
See also
*
Alkaline water electrolysis
Alkaline water electrolysis has a long history in the chemical industry. It is a type of electrolyzer that is characterized by having two electrodes operating in a liquid alkaline electrolyte solution of potassium hydroxide (KOH) or sodium hydrox ...
*
Castner–Kellner process
The Castner–Kellner process is a method of electrolysis on an aqueous alkali chloride solution (usually sodium chloride solution) to produce the corresponding alkali hydroxide, invented by American Hamilton Castner and Austrian Carl Kellner in t ...
*
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 electrod ...
*
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 cell ...
*
Faraday's law of electrolysis
Faraday's laws of electrolysis are quantitative relationships based on the electrochemical research published by Michael Faraday in 1833.
First law
Michael Faraday reported that the mass (m) of elements deposited at an electrode is directly prop ...
*
Faraday constant
In physical chemistry, the Faraday constant, denoted by the symbol and sometimes stylized as ℱ, is the electric charge per mole of elementary charges. It is named after the English scientist Michael Faraday. Since the 2019 redefinition of S ...
*
Faraday efficiency Faraday efficiency (also called ''faradaic efficiency'', ''faradaic yield'', ''coulombic efficiency'' or ''current efficiency'') describes the efficiency with which charge (electrons) is transferred in a system facilitating an electrochemical reacti ...
*
Galvanic corrosion
Galvanic corrosion (also called bimetallic corrosion or dissimilar metal corrosion) is an electrochemical process in which one metal corrodes preferentially when it is in electrical contact with another, in the presence of an electrolyte. A sim ...
*
Galvanoluminescence
Galvanoluminescence Is the emission of light produced by the passage of an electric current through an appropriate electrolyte in which an electrode, made of certain metals such as aluminium or tantalum, has been immersed. An example being the el ...
*
Gas cracker A gas cracker is any device that splits the molecules in a gas or liquid, usually by electrolysis, into atoms. The end product is usually a gas. A hydrocracker is an example of a gas cracker. In nature, molecules are split often, such as in food d ...
*
Hall–Héroult process
The Hall–Héroult process is the major industrial process for smelting aluminium. It involves dissolving aluminium oxide (alumina) (obtained most often from bauxite, aluminium's chief ore, through the Bayer process) in molten cryolite, and el ...
*
High-pressure electrolysis
High-pressure electrolysis (HPE) is the electrolysis of water by decomposition of water (H2O) into oxygen (O2) and hydrogen gas (H2) due to the passing of an electric current through the water. The difference with a standard proton exchange mem ...
*
Overpotential
In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly relat ...
*
Patterson Power Cell
*
Thermochemical cycle Thermochemical cycles combine solely heat sources (''thermo'') with ''chemical'' reactions to split water into its hydrogen and oxygen components. The term ''cycle'' is used because aside of water, hydrogen and oxygen, the chemical compounds used in ...
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Timeline of hydrogen technologies
This is a timeline of the history of hydrogen technology.
Timeline
16th century
* c. 1520 – First recorded observation of hydrogen by Paracelsus through dissolution of metals (iron, zinc, and tin) in sulfuric acid.
17th century
* 1625 – Fi ...
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PEM electrolysis Polymer electrolyte membrane (PEM) electrolysis is the electrolysis of water in a cell equipped with a solid polymer electrolyte (SPE) that is responsible for the conduction of protons, separation of product gases, and electrical insulation of the e ...
References
{{Authority control
Chemical processes
Electrochemistry
Hydrogen production
Industrial processes
Industrial gases