Electrolytic Cells
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An electrolytic cell is an
electrochemical cell An electrochemical cell is a device that either generates electrical energy from chemical reactions in a so called galvanic cell, galvanic or voltaic cell, or induces chemical reactions (electrolysis) by applying external electrical energy in an ...
that utilizes an external source of
electrical energy Electrical energy is the energy transferred as electric charges move between points with different electric potential, that is, as they move across a voltage, potential difference. As electric potential is lost or gained, work is done changing the ...
to force a
chemical reaction A chemical reaction is a process that leads to the chemistry, chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an Gibbs free energy, ...
that would otherwise not occur. The external energy source is a
voltage Voltage, also known as (electrical) potential difference, electric pressure, or electric tension, is the difference in electric potential between two points. In a Electrostatics, static electric field, it corresponds to the Work (electrical), ...
applied between the cell's two
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 a gas). In electrochemical cells, electrodes are essential parts that can consist of a varie ...
s; an
anode An anode usually is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, which is usually an electrode of the device through which conventional current leaves the devic ...
(positively charged electrode) and a
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device such as a lead-acid battery. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. Conventional curren ...
(negatively charged electrode), which are immersed in an
electrolyte An electrolyte is a substance that conducts electricity through the movement of ions, but not through the movement of electrons. This includes most soluble Salt (chemistry), salts, acids, and Base (chemistry), bases, dissolved in a polar solven ...
solution. This is in contrast to a
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. An example of a ...
, which itself is a source of electrical energy and the foundation of a battery. The net reaction taking place in an electrolytic cell is a non-spontaneous reaction (reverse of a spontaneous reaction), i.e., the
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol is a thermodynamic potential that can be used to calculate the maximum amount of Work (thermodynamics), work, other than Work (thermodynamics)#Pressure–v ...
is +ve, while the net reaction taking place in a galvanic cell is a spontaneous reaction, i.e., the Gibbs free energy is - ve.


Principles

In an electrolytic cell, a
current Currents, Current or The Current may refer to: Science and technology * Current (fluid), the flow of a liquid or a gas ** Air current, a flow of air ** Ocean current, a current in the ocean *** Rip current, a kind of water current ** Current (hydr ...
passes through the cell by an external
voltage Voltage, also known as (electrical) potential difference, electric pressure, or electric tension, is the difference in electric potential between two points. In a Electrostatics, static electric field, it corresponds to the Work (electrical), ...
, causing a non-spontaneous chemical reaction to proceed. In a galvanic cell, the progress of a spontaneous chemical reaction causes an electric current to flow. An
equilibrium Equilibrium may refer to: Film and television * ''Equilibrium'' (film), a 2002 science fiction film * '' The Story of Three Loves'', also known as ''Equilibrium'', a 1953 romantic anthology film * "Equilibrium" (''seaQuest 2032'') * ''Equilibr ...
electrochemical cell exists in the state between an electrolytic cell and a galvanic cell. The tendency of a spontaneous reaction to push a current through the external circuit is exactly balanced by a
counter-electromotive force Counter-electromotive force (counter EMF, CEMF, back EMF),Graf, "counterelectromotive force", Dictionary of Electronics is the electromotive force (EMF) manifesting as a voltage that opposes the change in current which induced it. CEMF is the EM ...
so that no current flows. If this counter-electromotive force is increased, the cell becomes an electrolytic cell, and if it is decreased, the cell becomes a galvanic cell. An electrolytic cell has three components: an
electrolyte An electrolyte is a substance that conducts electricity through the movement of ions, but not through the movement of electrons. This includes most soluble Salt (chemistry), salts, acids, and Base (chemistry), bases, dissolved in a polar solven ...
and two electrodes (a
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device such as a lead-acid battery. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. Conventional curren ...
and an
anode An anode usually is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, which is usually an electrode of the device through which conventional current leaves the devic ...
). The
electrolyte An electrolyte is a substance that conducts electricity through the movement of ions, but not through the movement of electrons. This includes most soluble Salt (chemistry), salts, acids, and Base (chemistry), bases, dissolved in a polar solven ...
is usually a
solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Solu ...
of
water Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance. It is the main constituent of Earth's hydrosphere and the fluids of all known liv ...
or other
solvent A solvent (from the Latin language, Latin ''wikt:solvo#Latin, solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a Solution (chemistry), solution. A solvent is usually a liquid but can also be a solid, a gas ...
s in which
ion 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 are dissolved.
Molten salt Molten salt is salt which is solid at standard temperature and pressure but liquified due to elevated temperature. A salt that is liquid even at standard temperature and pressure is usually called a room-temperature ionic liquid, and molten salts ...
s such as
sodium chloride Sodium chloride , commonly known as Salt#Edible salt, edible salt, is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. It is transparent or translucent, brittle, hygroscopic, and occurs a ...
can also function as electrolytes. When driven by an external voltage applied to the electrodes, the ions in the electrolyte are attracted to an electrode with 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 Aqu ...
, where charge-transferring (also called faradaic or
redox Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is t ...
) reactions can take place. Only with an external
electrical potential Electric potential (also called the ''electric field potential'', potential drop, the electrostatic potential) is defined as electric potential energy per unit of electric charge. More precisely, electric potential is the amount of work neede ...
(i.e., voltage) of correct polarity and sufficient magnitude can an electrolytic cell decompose a normally stable, or inert chemical compound in the solution. The electrical energy provided can produce a chemical reaction that would otherwise not occur spontaneously.
Michael Faraday Michael Faraday (; 22 September 1791 – 25 August 1867) was an English chemist and physicist who contributed to the study of electrochemistry and electromagnetism. His main discoveries include the principles underlying electromagnetic inducti ...
defined the cathode of a cell as the electrode to which cations (positively charged ions, such as silver ions Ag) flow within the cell, to be reduced by reacting with electrons (negatively charged) from that electrode. Likewise, he defined the anode as the electrode to which anions (negatively charged ions, like chloride ions Cl) flow within the cell, to be
oxidized Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
by depositing electrons on the electrode. To an external wire connected to the electrodes of a galvanic cell (or battery), forming an electric circuit, the cathode is positive and the anode is negative. Thus positive electric current flows from the cathode to the anode through the external circuit in the case of a galvanic cell.


Applications

Electrolytic cells are often used to decompose chemical compounds, in a process called
electrolysis In chemistry and manufacturing, electrolysis is a technique that uses Direct current, direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of c ...
—with ''electro'' meaning ''electricity'' and the Greek word ''
lysis Lysis ( ; from Greek 'loosening') is the breaking down of the membrane of a cell, often by viral, enzymic, or osmotic (that is, "lytic" ) mechanisms that compromise its integrity. A fluid containing the contents of lysed cells is called a ...
'' means ''to break up''. Important examples of electrolysis are the decomposition of
water Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance. It is the main constituent of Earth's hydrosphere and the fluids of all known liv ...
into
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
and
oxygen Oxygen is a chemical element; it has 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 reactivity (chemistry), reactive nonmetal (chemistry), non ...
, and
bauxite Bauxite () is a sedimentary rock with a relatively high aluminium content. It is the world's main source of aluminium and gallium. Bauxite consists mostly of the aluminium minerals gibbsite (), boehmite (γ-AlO(OH)), and diaspore (α-AlO(OH) ...
into
aluminum Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
and other chemicals.
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 ...
(e.g., of copper, silver, nickel, or chromium) is done using an electrolytic cell. Electrolysis is a technique that uses a direct electric current (DC). Commercially, electrolytic cells are used in the electrorefining and
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 ...
of several non-ferrous metals. Most high-purity
aluminum Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
,
copper Copper is a chemical element; it has symbol Cu (from Latin ) 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 pinkish-orang ...
,
zinc Zinc is a chemical element; it has symbol Zn and atomic number 30. It 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 periodic tabl ...
, and
lead Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
are produced industrially in electrolytic cells. As already noted, water, particularly when ions are added (saltwater or acidic water), can be ''electrolyzed'' (subjected to electrolysis). When driven by an external source of voltage, hydrogen (H) ions flow to the cathode to combine with electrons to produce hydrogen gas in a reduction reaction. Likewise, hydroxide (OH) ions flow to the anode to release electrons and a hydrogen (H) ion to produce oxygen gas in an oxidation reaction. In molten sodium chloride (NaCl), when a current is passed through the salt the anode oxidizes chloride ions (Cl) to chlorine gas, it releases electrons to the anode. Likewise, the cathode reduces sodium ions (Na), which accepts electrons from the cathode and deposits them on the cathode as sodium metal. Sodium chloride that has been dissolved in water can also be electrolyzed. The anode oxidizes the chloride ions (Cl), and produces chlorine (Cl2) gas, and, depending on the pH of the solution, can produce
Hypochlorous acid Hypochlorous acid is an inorganic compound with the chemical formula , also written as HClO, HOCl, or ClHO. Its structure is . It is an acid that forms when chlorine dissolves in water, and itself partially dissociates, forming a hypochlorite an ...
. However, at the cathode, instead of sodium ions being reduced to sodium metal, water molecules are reduced to hydroxide ions (OH) and hydrogen gas (H2). The overall result of the electrolysis is the production of
chlorine Chlorine is a chemical element; it has 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 between ...
gas at the anode, aqueous hypochlorous acid as the anolyte, hydrogen gas at the cathode, and aqueous
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...
(NaOH) as the catholyte. Industrially, this is known as 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 commodi ...
.


See also

*
Electrolysis In chemistry and manufacturing, electrolysis is a technique that uses Direct current, direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of c ...
*
Electrochemical cell An electrochemical cell is a device that either generates electrical energy from chemical reactions in a so called galvanic cell, galvanic or voltaic cell, or induces chemical reactions (electrolysis) by applying external electrical energy in an ...
*
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. An example of a ...


References

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