Electrolytic cell
Encyclopedia
An electrolytic cell decomposes chemical compounds by means of electrical energy, in a process called electrolysis
; the Greek word lysis
means to break up. The result is that the chemical energy is increased. Important examples of electrolysis are the decomposition of water
into hydrogen
and oxygen
, and bauxite
into aluminium and other chemicals.
and two electrodes (a cathode
and an anode
). The electrolyte
is usually a solution
of water
or other solvent
s in which ions are dissolved. Molten salts such as sodium chloride are also electrolytes. When driven by an external voltage
applied to the electrodes, the electrolyte provides ions that flow to and from the electrodes, where charge-transferring, or faradaic, or redox
, reactions can take place. Only for an external electrical potential (i.e. voltage) of the correct polarity and large enough magnitude can an electrolytic cell decompose a normally stable, or inert
chemical compound in the solution. The electrical energy provided undoes the effect of spontaneous chemical reactions.
or Galvanic cell
, converts chemical energy into electrical energy, by using spontaneous chemical reactions that take place at the electrodes. Each galvanic cell has its own characteristic voltage (defined as the energy release per electron transfer from one electrode to the other). A simple galvanic cell will consist only of an electrolyte and two different electrodes. (Galvanic cells can also be made by connecting two half-cells, each with its own electrode and electrolyte, by an ion-transporting "bridge," usually a salt bridge
; these cells are more complex.) The electrodes typically are two metals, which naturally have different reaction potentials relative to the electrolyte. This causes electrons of one of the electrodes to preferentially enter the solution at one electrode, and other electrons to leave the solution at the other electrode. This generates an electric current across the electrolyte, which will drive electric current through a wire that makes an exterior connection to each of the electrodes. A galvanic cell uses electrodes of different metals (except for a concentration cell
), whereas an electrolytic cell may use the same metal for cathode and anode.
A rechargeable battery
, such as a AA NiMH
cell or a single cell of a lead-acid battery
, acts as a galvanic cell when discharging (converting chemical energy to electrical energy), and an electrolytic cell when being charged (converting electrical energy to chemical energy).
defined the cathode
as the electrode to which cations (positively charged ions, like silver ions Ag)flow, to be reduced
by reacting with electrons (negatively charged) on the cathode. Likewise he defined the anode
as the electrode to which anions (negatively charged ions, like chloride ions Cl) flow, to be oxidized
by depositing electrons on the anode. Thus positive electric current flows from the cathode to the anode. To an external wire connected to the electrodes of a battery
,forming an electric circuit, the cathode is positive and the anode is negative.
Consider two voltaic cells, A and B, with the voltage of A greater than the voltage of B. Mark the positive and negative electrodes as cathode and anode, respectively. Place them in a circuit with anode near anode and cathode near cathode, so the cells will tend to drive current in opposite directions. The cell with the larger voltage discharges, making it a voltaic cell. Likewise the cell with the smaller voltage charges, making it an electrolytic cell. For the electrolytic cell, the external markings of anode and cathode are opposite the chemical definition. That is, the electrode marked as anode for discharge acts as the cathode while charging and the electrode marked as cathode acts as the anode while charging.
In molten sodium chloride, when a current is passed through the salt the anode oxidizes chloride ions (Cl) to chlorine gas, releasing electrons to the anode. Likewise the cathode reduces sodium ions (Na), which accept electrons from the cathode and deposits on the cathode as sodium metal.
NaCl dissolved in water can also be electrolyzed. The anode oxidizes chloride ions (Cl), and Cl2 gas is still produced. 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
gas and aqueous sodium hydroxide (NaOH) solution.
Commercially, electrolytic cells are used in electrorefining and electrowinning
of several non-ferrous metals. Almost all high-purity aluminium
, copper
, zinc
and lead
is produced industrially in electrolytic cells.
Electrolysis
In chemistry and manufacturing, electrolysis is a method of using a direct electric current to drive an otherwise non-spontaneous chemical reaction...
; the Greek word lysis
Lysis
Lysis refers to the breaking down of a cell, often by viral, enzymic, or osmotic mechanisms that compromise its integrity. A fluid containing the contents of lysed cells is called a "lysate"....
means to break up. The result is that the chemical energy is increased. Important examples of electrolysis are the decomposition of water
Water
Water is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...
into hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
and oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...
, and bauxite
Bauxite
Bauxite is an aluminium ore and is the main source of aluminium. This form of rock consists mostly of the minerals gibbsite Al3, boehmite γ-AlO, and diaspore α-AlO, in a mixture with the two iron oxides goethite and hematite, the clay mineral kaolinite, and small amounts of anatase TiO2...
into aluminium and other chemicals.
Components
An electrolytic cell has three component parts: an electrolyteElectrolyte
In chemistry, an electrolyte is any substance containing free ions that make the substance electrically conductive. The most typical electrolyte is an ionic solution, but molten electrolytes and solid electrolytes are also possible....
and two electrodes (a cathode
Cathode
A cathode is an electrode through which electric current flows out of a polarized electrical device. Mnemonic: CCD .Cathode polarity is not always negative...
and an anode
Anode
An anode is an electrode through which electric current flows into a polarized electrical device. Mnemonic: ACID ....
). The electrolyte
Electrolyte
In chemistry, an electrolyte is any substance containing free ions that make the substance electrically conductive. The most typical electrolyte is an ionic solution, but molten electrolytes and solid electrolytes are also possible....
is usually a solution
Solution
In chemistry, a solution is a homogeneous mixture composed of only one phase. In such a mixture, a solute is dissolved in another substance, known as a solvent. The solvent does the dissolving.- Types of solutions :...
of water
Water
Water is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...
or other solvent
Solvent
A solvent is a liquid, solid, or gas that dissolves another solid, liquid, or gaseous solute, resulting in a solution that is soluble in a certain volume of solvent at a specified temperature...
s in which ions are dissolved. Molten salts such as sodium chloride are also electrolytes. When driven by an external voltage
Voltage
Voltage, otherwise known as electrical potential difference or electric tension is the difference in electric potential between two points — or the difference in electric potential energy per unit charge between two points...
applied to the electrodes, the electrolyte provides ions that flow to and from the electrodes, where charge-transferring, or faradaic, or redox
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....
, reactions can take place. Only for an external electrical potential (i.e. voltage) of the correct polarity and large enough magnitude can an electrolytic cell decompose a normally stable, or inert
Inert
-Chemistry:In chemistry, the term inert is used to describe a substance that is not chemically reactive.The noble gases were previously known as inert gases because of their perceived lack of participation in any chemical reactions...
chemical compound in the solution. The electrical energy provided undoes the effect of spontaneous chemical reactions.
Galvanic cells compared to electrolytic cells
In contrast, a batteryBattery (electricity)
An electrical battery is one or more electrochemical cells that convert stored chemical energy into electrical energy. Since the invention of the first battery in 1800 by Alessandro Volta and especially since the technically improved Daniell cell in 1836, batteries have become a common power...
or Galvanic cell
Galvanic cell
A Galvanic cell, or Voltaic cell, named after Luigi Galvani, or Alessandro Volta respectively, is an electrochemical cell that derives electrical energy from spontaneous redox reaction taking place within the cell...
, converts chemical energy into electrical energy, by using spontaneous chemical reactions that take place at the electrodes. Each galvanic cell has its own characteristic voltage (defined as the energy release per electron transfer from one electrode to the other). A simple galvanic cell will consist only of an electrolyte and two different electrodes. (Galvanic cells can also be made by connecting two half-cells, each with its own electrode and electrolyte, by an ion-transporting "bridge," usually a salt bridge
Salt bridge
A salt bridge, in chemistry, is a laboratory device used to connect the oxidation and reduction half-cells of a galvanic cell , a type of electrochemical cell...
; these cells are more complex.) The electrodes typically are two metals, which naturally have different reaction potentials relative to the electrolyte. This causes electrons of one of the electrodes to preferentially enter the solution at one electrode, and other electrons to leave the solution at the other electrode. This generates an electric current across the electrolyte, which will drive electric current through a wire that makes an exterior connection to each of the electrodes. A galvanic cell uses electrodes of different metals (except for a concentration cell
Concentration cell
A concentration cell is a limited form of a galvanic cell that has two equivalent half-cells of the same material differing only in concentrations. One can calculate the potential developed by such a cell using the Nernst Equation. A concentration cell produces a voltage as it attempts to reach...
), whereas an electrolytic cell may use the same metal for cathode and anode.
A rechargeable battery
Rechargeable battery
A rechargeable battery or storage battery is a group of one or more electrochemical cells. They are known as secondary cells because their electrochemical reactions are electrically reversible. Rechargeable batteries come in many different shapes and sizes, ranging anything from a button cell to...
, such as a AA NiMH
NIMH
NIMH or NiMH may refer to:*Nickel-metal hydride battery, a type of rechargeable battery*National Institute of Mental Health, a part of the United States National Institutes of Health...
cell or a single cell of a lead-acid battery
Lead-acid battery
Lead–acid batteries, invented in 1859 by French physicist Gaston Planté, are the oldest type of rechargeable battery. Despite having a very low energy-to-weight ratio and a low energy-to-volume ratio, their ability to supply high surge currents means that the cells maintain a relatively large...
, acts as a galvanic cell when discharging (converting chemical energy to electrical energy), and an electrolytic cell when being charged (converting electrical energy to chemical energy).
Anode and cathode definitions depend on charge and discharge
Michael FaradayMichael Faraday
Michael Faraday, FRS was an English chemist and physicist who contributed to the fields of electromagnetism and electrochemistry....
defined the cathode
Cathode
A cathode is an electrode through which electric current flows out of a polarized electrical device. Mnemonic: CCD .Cathode polarity is not always negative...
as the electrode to which cations (positively charged ions, like silver ions Ag)flow, to be reduced
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....
by reacting with electrons (negatively charged) on the cathode. Likewise he defined the anode
Anode
An anode is an electrode through which electric current flows into a polarized electrical device. Mnemonic: ACID ....
as the electrode to which anions (negatively charged ions, like chloride ions Cl) flow, to be oxidized
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....
by depositing electrons on the anode. Thus positive electric current flows from the cathode to the anode. To an external wire connected to the electrodes of a battery
Battery (electricity)
An electrical battery is one or more electrochemical cells that convert stored chemical energy into electrical energy. Since the invention of the first battery in 1800 by Alessandro Volta and especially since the technically improved Daniell cell in 1836, batteries have become a common power...
,forming an electric circuit, the cathode is positive and the anode is negative.
Consider two voltaic cells, A and B, with the voltage of A greater than the voltage of B. Mark the positive and negative electrodes as cathode and anode, respectively. Place them in a circuit with anode near anode and cathode near cathode, so the cells will tend to drive current in opposite directions. The cell with the larger voltage discharges, making it a voltaic cell. Likewise the cell with the smaller voltage charges, making it an electrolytic cell. For the electrolytic cell, the external markings of anode and cathode are opposite the chemical definition. That is, the electrode marked as anode for discharge acts as the cathode while charging and the electrode marked as cathode acts as the anode while charging.
Uses
As already noted, water, particularly when ions are added (salt water or acidic water) can be electrolyzed (subject to electrolysis). When driven by an external source of voltage, H ions flow to the cathode to combine with electrons to produce hydrogen gas in a reduction reaction. Likewise, OH ions flow to the anode to release electrons and an H ion to produce oxygen gas in an oxidation reaction.In molten sodium chloride, when a current is passed through the salt the anode oxidizes chloride ions (Cl) to chlorine gas, releasing electrons to the anode. Likewise the cathode reduces sodium ions (Na), which accept electrons from the cathode and deposits on the cathode as sodium metal.
NaCl dissolved in water can also be electrolyzed. The anode oxidizes chloride ions (Cl), and Cl2 gas is still produced. 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
Chlorine is the chemical element with atomic number 17 and symbol Cl. It is the second lightest halogen, found in the periodic table in group 17. The element forms diatomic molecules under standard conditions, called dichlorine...
gas and aqueous sodium hydroxide (NaOH) solution.
Commercially, electrolytic cells are used in electrorefining and electrowinning
Electrowinning
Electrowinning, also called electroextraction, is the electrodeposition of metals from their ores that have been put in solution or liquefied. Electrorefining uses a similar process to remove impurities from a metal. Both processes use electroplating on a large scale and are important techniques...
of several non-ferrous metals. Almost all high-purity aluminium
Aluminium
Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances....
, copper
Copper
Copper is a chemical element with the symbol Cu and atomic number 29. It is a ductile metal with very high thermal and electrical conductivity. Pure copper is soft and malleable; an exposed surface has a reddish-orange tarnish...
, zinc
Zinc
Zinc , or spelter , is a metallic chemical element; it has the symbol Zn and atomic number 30. It is the first element in group 12 of the periodic table. Zinc is, in some respects, chemically similar to magnesium, because its ion is of similar size and its only common oxidation state is +2...
and lead
Lead
Lead is a main-group element in the carbon group with the symbol Pb and atomic number 82. Lead is a soft, malleable poor metal. It is also counted as one of the heavy metals. Metallic lead has a bluish-white color after being freshly cut, but it soon tarnishes to a dull grayish color when exposed...
is produced industrially in electrolytic cells.
Cell types
- Concentration cellConcentration cellA concentration cell is a limited form of a galvanic cell that has two equivalent half-cells of the same material differing only in concentrations. One can calculate the potential developed by such a cell using the Nernst Equation. A concentration cell produces a voltage as it attempts to reach...
- Electrochemical cellElectrochemical cellAn electrochemical cell is a device capable of either deriving electrical energy from chemical reactions, or facilitating chemical reactions through the introduction of electrical energy. A common example of an electrochemical cell is a standard 1.5-volt "battery"...
- Galvanic cellGalvanic cellA Galvanic cell, or Voltaic cell, named after Luigi Galvani, or Alessandro Volta respectively, is an electrochemical cell that derives electrical energy from spontaneous redox reaction taking place within the cell...