Electrochemistry is a branch of chemistry that studies chemical reactions which take place in a solution at the interface of an electron conductor (a metal or a semiconductor) and an ionic conductor (the electrolyte), and which involve electron transfer between the electrode and the electrolyte or species in solution.
If a chemical reaction is driven by an external applied voltage, as in electrolysis, or if a voltage is created by a chemical reaction as in a battery, it is an electrochemical reaction. Chemical reactions where electrons are transferred between molecules are called oxidation/reduction (redox) reactions. In general, electrochemistry deals with situations where oxidation and reduction reactions are separated in space or time, connected by an external electric circuit to understand each process.
The 16th century marked the beginning of electrical understanding. During that century the English scientist William Gilbert spent 17 years experimenting with magnetism and, to a lesser extent, electricity. For his work on magnets, Gilbert became known as the "Father of Magnetism." He discovered various methods for producing and strengthening magnets.
In 1663 the German physicist Otto von Guericke created the first electric generator, which produced static electricity by applying friction in the machine. The generator was made of a large sulfur ball cast inside a glass globe, mounted on a shaft. The ball was rotated by means of a crank and a static electric spark was produced when a pad was rubbed against the ball as it rotated. The globe could be removed and used as source for experiments with electricity.
By the mid—18th century the French chemist Charles François de Cisternay du Fay discovered two types of static electricity, and that like charges repel each other whilst unlike charges attract. Du Fay announced that electricity consisted of two fluids: "vitreous" (from the Latin for "glass"), or positive, electricity; and "resinous," or negative, electricity. This was the two-fluid theory of electricity, which was to be opposed by Benjamin Franklin's one-fluid theory later in the century.
Charles-Augustin de Coulomb developed the law of electrostatic attraction in 1781 as an outgrowth of his attempt to investigate the law of electrical repulsions as stated by Joseph Priestley in England.
In the late 18th century the Italian physician and anatomist Luigi Galvani marked the birth of electrochemistry by establishing a bridge between chemical reactions and electricity on his essay "De Viribus Electricitatis in Motu Musculari Commentarius" (Latin for Commentary on the Effect of Electricity on Muscular Motion) in 1791 where he proposed a "nerveo-electrical substance" on biological life forms.
In his essay Galvani concluded that animal tissue contained a here-to-fore neglected innate, vital force, which he termed "animal electricity," which activated nerves and muscles spanned by metal probes. He believed that this new force was a form of electricity in addition to the "natural" form produced by lightning or by the electric eel and torpedo ray as well as the "artificial" form produced by friction (i.e., static electricity).
Galvani's scientific colleagues generally accepted his views, but Alessandro Volta rejected the idea of an "animal electric fluid," replying that the frog's legs responded to differences in metal temper, composition, and bulk. Galvani refuted this by obtaining muscular action with two pieces of the same material.
By the 1810s William Hyde Wollaston made improvements to the galvanic pile. Sir Humphry Davy's work with electrolysis led to the conclusion that the production of electricity in simple electrolytic cells resulted from chemical action and that chemical combination occurred between substances of opposite charge. This work led directly to the isolation of sodium and potassium from their compounds and of the alkaline earth metals from theirs in 1808.
Hans Christian Ørsted's discovery of the magnetic effect of electrical currents in 1820 was immediately recognized as an epoch-making advance, although he left further work on electromagnetism to others. André-Marie Ampère quickly repeated Ørsted's experiment, and formulated them mathematically.
In 1827 the German scientist Georg Ohm expressed his law in this famous book "Die galvanische Kette, mathematisch bearbeitet" (The Galvanic Circuit Investigated Mathematically) in which he gave his complete theory of electricity.
In 1832 Michael Faraday's experiments led him to state his two laws of electrochemistry. In 1836 John Daniell invented a primary cell in which hydrogen was eliminated in the generation of the electricity. Daniell had solved the problem of polarization. In his laboratory he had learned that alloying the amalgamated zinc of Sturgeon with mercury would produce a better voltage.
William Grove produced the first fuel cell in 1839. In 1846, Wilhelm Weber developed the electrodynamometer. In 1866, Georges Leclanché patented a new cell which eventually became the forerunner to the world's first widely used battery, the zinc carbon cell.
Svante August Arrhenius published his thesis in 1884 on Recherches sur la conductibilité galvanique des électrolytes (Investigations on the galvanic conductivity of electrolytes). From his results the author concluded that electrolytes, when dissolved in water, become to varying degrees split or dissociated into electrically opposite positive and negative ions.
Walther Hermann Nernst developed the theory of the electromotive force of the voltaic cell in 1888. In 1889, he showed how the characteristics of the current produced could be used to calculate the free energy change in the chemical reaction producing the current. He constructed an equation, known as Nernst Equation, which related the voltage of a cell to its properties.
In 1898 Fritz Haber showed that definite reduction products can result from electrolytic processes if the potential at the cathode is kept constant. In 1898 he explained the reduction of nitrobenzene in stages at the cathode and this became the model for other similar reduction processes.
A year later, in 1949, the International Society of Electrochemistry (ISE) was founded.
For example when atomic sodium reacts with atomic chlorine, sodium donates one electron and attains an oxidation state of +1. Chlorine accepts the electron and its oxidation state is reduced to −1. The sign of the oxidation state (positive/negative) actually corresponds to the value of each ion's electronic charge. The attraction of the differently charged sodium and chlorine ions is the reason they then form an ionic bond.
The loss of electrons from an atom or molecule is called oxidation, and the gain of electrons is reduction. This can be easily remembered through the use of mnemonic devices. Two of the most popular are "OIL RIG" (Oxidation Is Loss, Reduction Is Gain) and "LEO" the lion says "GER" (Lose Electrons: Oxidization, Gain Electrons: Reduction). For cases where electrons are shared (covalent bonds) between atoms with large differences in electronegativity, the electron is assigned to the atom with the largest electronegativity in determining the oxidation state.
The atom or molecule which loses electrons is known as the reducing agent, or reductant, and the substance which accepts the electrons is called the oxidizing agent, or oxidant. The oxidizing agent is always being reduced in a reaction; the reducing agent is always being oxidized. Oxygen is a common oxidizing agent, but not the only one. Despite the name, an oxidation reaction does not necessarily need to involve oxygen. In fact, a fire can be fed by an oxidant other than oxygen; fluorine fires are often unquenchable, as fluorine is an even stronger oxidant (it has a higher electronegativity) than oxygen.
For reactions involving oxygen, the gain of oxygen implies the oxidation of the atom or molecule to which the oxygen is added (and the oxygen is reduced). For example, in the oxidation of octane by oxygen to form carbon dioxide and water, both the carbon in the octane and the oxygen begin with an oxidation state of 0. In forming CO2 the carbon loses four electrons to become C4+ and the oxygens each gain two electrons to be O2-. In organic compounds, such as butane or ethanol, the loss of hydrogen implies oxidation of the molecule from which it is lost (and the hydrogen is reduced). This follows because the hydrogen donates its electron in covalent bonds with non-metals but it takes the electron along when it is lost. Conversely, loss of oxygen or gain of hydrogen implies reduction.
An electrochemical cell is a device that produces an electric current from energy released by a spontaneous redox reaction. This kind of cell includes the Galvanic cell or Voltaic cell, named after Luigi Galvani and Alessandro Volta, both scientists who conducted several experiments on chemical reactions and electric current during the late 18th century.
Electrochemical cells have two conductive electrodes (the anode and the cathode). The anode is defined as the electrode where oxidation occurs and the cathode is the electrode where the reduction takes place. Electrodes can be made from any sufficiently conductive materials, such as metals, semiconductors, graphite, and even conductive polymers. In between these electrodes is the electrolyte, which contains ions that can freely move.
The Galvanic cell uses two different metal electrodes, each in an electrolyte where the positively charged ions are the oxidized form of the electrode metal. One electrode will undergo oxidation (the anode) and the other will undergo reduction (the cathode). The metal of the anode will oxidize, going from an oxidation state of 0 (in the solid form) to a positive oxidation state and become an ion. At the cathode, the metal ion in solution will accept one or more electrons from the cathode and the ion's oxidation state is reduced to 0. This forms a solid metal that electrodeposits on the cathode. The two electrodes must be electrically connected to each other, allowing for a flow of electrons that leave the metal of the anode and flow through this connection to the ions at the surface of the cathode. This flow of electrons is an electrical current that can be used to do work, such as turn a motor or power a light.
Half reactions for a Daniell cell are these:
In this example, the anode is zinc metal which oxidizes (loses electrons) to form zinc ions in solution, and copper ions accept electrons from the copper metal electrode and the ions deposit at the copper cathode as an electrodeposit. This cell forms a simple battery as it will spontaneously generate a flow of electrical current from the anode to the cathode through the external connection. This reaction can be driven in reverse by applying a voltage, resulting in the deposition of zinc metal at the anode and formation of copper ions at the cathode. To provide a complete electric circuit, there must also be an ionic conduction path between the anode and cathode electrolytes in addition to the electron conduction path. The simplest ionic conduction path is to provide a liquid junction. To avoid mixing between the two electrolytes, the liquid junction can be provided through a porous plug that allows ion flow while reducing electrolyte mixing. To further minimize mixing of the electrolytes, a salt bridge can be used which consists of an electrolyte saturated gel in an inverted U-tube. As the negatively charged electrons flow in one direction around this circuit, the positively charged metal ions flow in the opposite direction in the electrolyte.
A cell diagram can be used to trace the path of the electrons in the electrochemical cell. For example, here is a cell diagram of a Daniell cell:
To allow prediction of the cell potential, tabulations of standard electrode potential are available. Such tabulations are referenced to the standard hydrogen electrode (SHE). The standard hydrogen electrode undergoes the reaction
The SHE electrode can be connected to any other electrode by a salt bridge to form a cell. If the second electrode is also at standard conditions, then the measured cell potential is called the standard electrode potential for the electrode. The standard electrode potential for the SHE is zero, by definition. The polarity of the standard electrode potential provides information about the relative reduction potential of the electrode compared to the SHE. If the electrode has a positive potential with respect to the SHE, then that means it is a strongly reducing electrode which forces the SHE to be the anode (an example is Cu in aqueous CuSO4 with a standard electrode potential of 0.337 V). Conversely, if the measured potential is negative, the electrode is more oxidizing than the SHE (such as Zn in ZnSO4 where the standard electrode potential is -0.763 V).
Standard electrode potentials are usually tabulated as reduction potentials. However, the reactions are reversible and the role of a particular electrode in a cell depends on the relative oxidation/reduction potential of both electrodes. The oxidation potential for a particular electrode is just the negative of the reduction potential. A standard cell potential can be determined by looking up the standard electrode potentials for both electrodes (sometimes called half cell potentials). The one that is smaller will be the anode and will undergo oxidation. The cell potential is then calculated as the sum of the reduction potential for the cathode and the oxidation potential for the anode.
For example, the standard electrode potential for a copper electrode is:
During operation of electrochemical cells, chemical energy is transformed into electrical energy and is expressed mathematically as the product of the cell's emf and the electrical charge transferred through the external circuit.
The emf of the cell at zero current is the maximum possible emf. It is used to calculate the maximum possible electrical energy that could be obtained from a chemical reaction. This energy is referred to as electrical work and is expressed by the following equation:
Since the free energy is the maximum amount of work that can be extracted from a system, one can write:
A positive cell potential gives a negative change in Gibbs free energy. This is consistent with the cell production of an electric current flowing from the cathode to the anode through the external circuit. If the current is driven in the opposite direction by imposing an external potential, then work is done on the cell to drive electrolysis.
A spontaneous electrochemical reaction (change in Gibbs free energy less than zero) can be used to generate an electric current, in electrochemical cells. This is the basis of all batteries and fuel cells. For example, gaseous oxygen (O2) and hydrogen (H2) can be combined in a fuel cell to form water and energy, typically a combination of heat and electrical energy.
Conversely, non-spontaneous electrochemical reactions can be driven forward by the application of a current at sufficient voltage. The electrolysis of water into gaseous oxygen and hydrogen is a typical example.
The relation between the equilibrium constant, K, and the Gibbs free energy for an electrochemical cell is expressed as follows:
Rearranging to express the relation between standard potential and equilibrium constant yields
The standard potential of an electrochemical cell requires standard conditions for all of the reactants. When reactant concentrations differ from standard conditions, the cell potential will deviate from the standard potential. In the 20th century German chemist Walther Hermann Nernst proposed a mathematical model to determine the effect of reactant concentration on electrochemical cell potential.
In the late 19th century Josiah Willard Gibbs had formulated a theory to predict whether a chemical reaction is spontaneous based on the free energy
Gibbs' key contribution was to formalize the understanding of the effect of reactant concentration on spontaneity.
Based on Gibbs' work, Nernst extended the theory to include the contribution from electric potential on charged species. As shown in the previous section, the change in Gibbs free energy for an electrochemical cell can be related to the cell potential. Thus, Gibbs' theory becomes
Finally, Nernst divided through by the amount of charge transferred to arrive at a new equation which now bears his name:
For example an electrochemical cell, where two copper electrodes are submerged in two copper(II) sulfate solutions, whose concentrations are 0.05 M and 2.0 M, connected through a salt bridge. This type of cell will generate a potential that can be predicted by the Nernst equation. Both electrodes undergo the same chemistry (although the reaction proceeds in reverse at the cathode)
Le Chatelier's principle indicates that the reaction is more favourable to reduction as the concentration of ions increases. Reduction will take place in the cell's compartment where concentration is higher and oxidation will occur on the more dilute side.
The following cell diagram describes the cell mentioned above:
Where the cell's emf is calculated through Nernst equation as follows:
's value of this kind of cell is zero, as electrodes and ions are the same in both half-cells. After replacing values from the case mentioned, it is possible to calculate cell's potential:
However, this value is only approximate, as reaction quotient is defined in terms of ion activities which can be approximated with the concentrations as calculated here.
The Nernst equation plays an important role in understanding electrical effects in cells and organelles. Such effects include nerve synapses and cardiac beat as well as the resting potential of a somatic cell.
A battery is an electrochemical cell (sometimes several in series) used for chemical energy storage. Batteries are optimized to produce a constant electric current for as long as possible. Although the cells discussed previously are useful for theoretical purposes and some laboratory experiments, the large internal resistance of the salt bridge make them inappropriate battery technologies. Various alternative battery technologies have been commercialized as discussed next.
Dry cells do not have a fluid electrolyte. Instead, they use a moist electrolyte paste. Leclanché's cell is a good example of this, where the anode is a zinc container surrounded by a thin layer of manganese dioxide and a moist electrolyte paste of ammonium chloride and zinc chloride mixed with starch. The cell's cathode is represented by a carbon bar inserted on the cell's electrolyte, usually placed in the middle.
Leclanché's simplified half reactions are shown below:
The mercury battery has many applications in medicine and electronics. The battery consists of a steel—made container in the shape of a cylinder acting as the cathode, where an amalgamated anode of mercury and zinc is surrounded by a stronger alkaline electrolyte and a paste of zinc oxide and mercury(II) oxide.
Mercury battery half reactions are shown below:
The lead-acid battery used in automobiles, consists of a series of six identical cells assembled in series. Each cell has a lead anode and a cathode made from lead dioxide packed in a metal plaque. Cathode and anode are submerged in a solution of sulfuric acid acting as the electrolyte.
Lead-acid battery half cell reactions are shown below:
At standard conditions, each cell may produce a potential of 2 V, hence overall voltage produced is 12 V. Differing from mercury and zinc-carbon batteries, lead-acid batteries are rechargeable. If an external voltage is supplied to the battery it will produce an electrolysis of the products in the overall reaction (discharge), thus recovering initial components which made the battery work.
These types of batteries are typically used for large-scale energy storage (kWh - multi MWh). Of the several different types that have been developed, some are of current commercial interest, including the vanadium redox battery and zinc bromine battery.
Fossil fuels are used in power plants to supply electrical needs, however their conversion into electricity is an inefficient process. The most efficient electrical power plant may only convert about 40% of the original chemical energy into electricity when burned or processed.
To enhance electrical production, scientists have developed fuel cells where combustion is replaced by electrochemical methods, similar to a battery but requiring continuous replenishment of the reactants consumed.
The most popular is the oxygen-hydrogen fuel cell, where two inert electrodes (porous electrodes of nickel and nickel oxide) are placed in an electrolytic solution such as hot caustic potash, in both compartments (anode and cathode) gaseous hydrogen and oxygen are bubbled into solution.
Oxygen-hydrogen fuel cell reactions are shown bellow:
The overall reaction is identical to hydrogen combustion. Oxidation and reduction take place in the anode and cathode separately. This is similar to the electrode used in the cell for measuring standard reduction potential which has a double function acting as electrical conductors providing a surface required to decomposition of the molecules into atoms before electron transferring, thus named electrocatalysts. Platinum, nickel, and rhodium are good electrocatalysts.
Corrosion is the term applied to metal rust caused by an electrochemical process. Most people are likely familiar with the corrosion of iron, in the form of reddish rust. Other examples include the black tarnish on silver, and red or green corrosion that may appear on copper and its alloys, such as brass. The cost of replacing metals lost to corrosion is in the multi-billions of dollars per year.
Some common metals oxidize extremely rapidly in air. Titanium and aluminium oxidize instantaneouly in contact with the oxygen in the air. These metals form an extremely thin layer of oxidized metal on the surface. This thin layer of oxide protects the underlying layers of the metal from the air preventing the entire metal from oxidizing. These metals are used in applications where corrosion resistance is important. Iron, in contrast, has an oxide that forms in air and water, called rust, that does not stop the further oxidation of the iron. Thus iron left exposed to air and water will continue to rust until all of the iron is oxidized.
Other prevention is called passivation where a metal is coated with another metal such as a tin can. Tin is a metal that rapidly corrodes to form a mono-molecular oxide coating that prevents further corrosion of the tin. The tin prevents the electrolyte from reaching the base metal, usually steel (iron). However, if the tin coating is scratched the iron becomes anodic and can corrodes rapidly.
Zinc bars are attached at various locations on steel ship hulls to render the ship hull cathodic. The zinc bars are replaced periodically. Other metals, such as magnesium, would work very well but zinc is the least expensive useful metal.
To protect pipelines, an ingot of buried or exposed magnesium (or zinc) is buried beside the pipeline and is connected electrically to the pipe above ground. The pipeline is forced to be a cathode and is protected from being oxidized and rusting. The magnesium anode is sacrificed. At intervals new ingots are buried to replace those lost.
The spontaneous redox reactions of a conventional battery produce electricity through the different chemical potentials of the cathode and anode in the electrolyte. However, electrolysis requires an external source of electrical energy to induce a chemical reaction, and this process takes place in a compartment called electrolytic cell.
When molten, the salt sodium chloride can be electrolyzed to yield metallic sodium and gaseous chlorine. Industrially this process takes place in a special cell named Down's cell. The cell is connected to an electrical power supply, allowing electrons to migrate from the power supply to the electrolytic cell.
Reactions that take place at Down's cell are the following:
The emf for this process is approximately -4 V indicating a (very) non-spontaneous process. In order for this reaction to occur the power supply should provide at least a potential of 4 V. However, larger voltages must be used for this reaction to occur at a high rate.
Bubbles from the gases will be seen near both electrodes. The following half reactions describe the process mentioned above:
Although strong acids may be used in the apparatus, the reaction will not net consume the acid. While this reaction will work at any conductive electrode at a sufficiently large potential, platinum catalyzes both hydrogen and oxygen formation, allowing for relatively mild voltages (~2V depending on the pH).
The following half reactions describes the process mentioned:
Reaction 1 is discarded as it has the most negative value on standard reduction potential thus making it less thermodynamically favorable in the process.
When comparing the reduction potentials in reactions 2 & 4, the reduction of chloride ion is favored. Thus, if the Cl- ion is favored for reduction, then the water reaction is favored for oxidation producing gaseous oxygen, however experiments shown gaseous chlorine is produced and not oxygen.
Although the initial analysis is correct, there is another effect that can happen, known as the overvoltage effect. Additional voltage is sometimes required, beyond the voltage predicted by the . This may be due to kinetic rather than thermodynamic considerations. In fact, it has been proven that the activation energy for the chloride ion is very low, hence favorable in kinetic terms. In other words, although the voltage applied is thermodynamically sufficient to drive electrolysis, the rate is so slow that to make the process proceed in a reasonable time frame, the voltage of the external source has to be increased (hence, overvoltage).
The overall reaction for the process according to the analysis would be the following:
As the overall reaction indicates, the concentration of chloride ions is reduced in comparison to OH- ions (whose concentration increases). The reaction also shows the production of gaseous hydrogen, chlorine and aqueous sodium hydroxide.
In other words, the amount of a substance deposited on each electrode of an electrolytic cell is directly proportional to the quantity of electricity passed through the cell.
Below a simplified equation of Faraday's first law:
An important aspect of the second law of electrolysis is electroplating which together with the first law of electrolysis, has a significant number of applications in the industry, as when used to protect metals to avoid corrosion.
The nervous impulses in neurons are based on electric current generated by the movement of sodium and potassium ions into and out of cells, and certain animals like eels can generate a powerful voltage from certain cells that can disable much larger animals.
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