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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 outcome of a particular chemical change, or vice versa. These reactions involve electrons moving via an electronically-conducting phase between electrodes separated by an ionically conducting and electronically insulating electrolyte.
An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit. Electrodes are essential parts of batteries that can consist of a variety of materials depending on the type of battery.
An electrochemical cell is a device capable of either generating electrical energy from chemical reactions or using electrical energy to cause chemical reactions. The electrochemical cells which generate an electric current are called voltaic or galvanic cells and those that generate chemical reactions, via electrolysis for example, are called electrolytic cells. A common example of a galvanic cell is a standard 1.5 volt cell meant for consumer use. A battery consists of one or more cells, connected in parallel, series or series-and-parallel pattern.
The voltaic pile was the first electrical battery that could continuously provide an electric current to a circuit. It was invented by Italian chemist Alessandro Volta, who published his experiments in 1799. Its invention can be traced back to an argument between Volta and Luigi Galvani, Volta’s fellow Italian scientist who had gained notoriety for his experiments on frog legs. The voltaic pile then enabled a rapid series of other discoveries including the electrical decomposition (electrolysis) of water into oxygen and hydrogen by William Nicholson and Anthony Carlisle (1800) and the discovery or isolation of the chemical elements sodium (1807), potassium (1807), calcium (1808), boron (1808), barium (1808), strontium (1808), and magnesium (1808) by Humphry Davy.
In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage 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".
In chemistry, a half reaction is either the oxidation or reduction reaction component of a redox reaction. A half reaction is obtained by considering the change in oxidation states of individual substances involved in the redox reaction. Often, the concept of half reactions is used to describe what occurs in an electrochemical cell, such as a Galvanic cell battery. Half reactions can be written to describe both the metal undergoing oxidation and the metal undergoing reduction.
Redox 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 decrease in the oxidation state.
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 generally consists of two different metals, each immersed in separate beakers containing their respective metal ions in solution that are connected by a salt bridge or separated by a porous membrane.
An electrolytic cell is an electrochemical cell that utilizes an external source of electrical energy to force a chemical reaction that would otherwise not occur. The external energy source is a voltage applied between the cell′s two electrodes; an anode and a cathode, which are immersed in an electrolyte solution. This is in contrast to a galvanic cell, which itself is a source of electrical energy and the foundation of a battery. The net reaction taking place in a galvanic cell is a spontaneous reaction, i.e, the Gibbs free energy remains -ve, while the net reaction taking place in an electrolytic cell is the reverse of this spontaneous reaction, i.e, the Gibbs free energy is +ve.
In electrochemistry, standard electrode potential, or , 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 of a cell in which molecular hydrogen under standard pressure is oxidized to solvated protons at the left-hand electrode".
In electrochemistry, a half-cell is a structure that contains a conductive electrode and a surrounding conductive electrolyte separated by a naturally occurring Helmholtz double layer. Chemical reactions within this layer momentarily pump electric charges between the electrode and the electrolyte, resulting in a potential difference between the electrode and the electrolyte. The typical anode reaction involves a metal atom in the electrode being dissolved and transported as a positive ion across the double layer, causing the electrolyte to acquire a net positive charge while the electrode acquires a net negative charge. The growing potential difference creates an intense electric field within the double layer, and the potential rises in value until the field halts the net charge-pumping reactions. This self-limiting action occurs almost instantly in an isolated half-cell; in applications two dissimilar half-cells are appropriately connected to constitute a Galvanic cell.
A silver chloride electrode is a type of reference electrode, commonly used in electrochemical measurements. For environmental reasons it has widely replaced the saturated calomel electrode. For example, it is usually the internal reference electrode in pH meters and it is often used as reference in reduction potential measurements. As an example of the latter, the silver chloride electrode is the most commonly used reference electrode for testing cathodic protection corrosion control systems in sea water environments.
The Daniell cell is a type of electrochemical cell invented in 1836 by John Frederic Daniell, a British chemist and meteorologist, and consists of a copper pot filled with a copper (II) sulfate solution, in which is immersed an unglazed earthenware container filled with sulfuric acid and a zinc electrode. He was searching for a way to eliminate the hydrogen bubble problem found in the voltaic pile, and his solution was to use a second electrolyte to consume the hydrogen produced by the first. Zinc sulfate may be substituted for the sulfuric acid. The Daniell cell was a great improvement over the existing technology used in the early days of battery development. A later variant of the Daniell cell called the gravity cell or crowfoot cell was invented in the 1860s by a Frenchman named Callaud and became a popular choice for electrical telegraphy.
Pitting corrosion, or pitting, is a form of extremely localized corrosion that leads to the random creation of small holes in metal. The driving power for pitting corrosion is the depassivation of a small area, which becomes anodic while an unknown but potentially vast area becomes cathodic, leading to very localized galvanic corrosion. The corrosion penetrates the mass of the metal, with a limited diffusion of ions.
A zinc–carbon battery (or carbon zinc battery in U.S. English) is a dry cell primary battery that provides direct electric current from the electrochemical reaction between zinc and manganese dioxide (MnO2) in the presence of an electrolyte. It produces a voltage of about 1.5 volts between the zinc anode, which is typically constructed as a cylindrical container for the battery cell, and a carbon rod surrounded by a compound with a higher Standard electrode potential (positive polarity), known as the cathode, that collects the current from the manganese dioxide electrode. The name "zinc-carbon" is slightly misleading as it implies that carbon is acting as the oxidizing agent rather than the manganese dioxide.
The saturated calomel electrode (SCE) is a reference electrode based on the reaction between elemental mercury and mercury(I) chloride. It has been widely replaced by the silver chloride electrode, however the calomel electrode has a reputation of being more robust. The aqueous phase in contact with the mercury and the mercury(I) chloride (Hg2Cl2, "calomel") is a saturated solution of potassium chloride in water. The electrode is normally linked via a porous frit to the solution in which the other electrode is immersed. This porous frit is a salt bridge.
In electrochemistry, electrosynthesis is the synthesis of chemical compounds in an electrochemical cell. Compared to ordinary redox reactions, electrosynthesis sometimes offers improved selectivity and yields. Electrosynthesis is actively studied as a science and also has industrial applications. Electrooxidation has potential for wastewater treatment as well.
The Leclanché cell is a battery invented and patented by the French scientist Georges Leclanché in 1866. The battery contained a conducting solution (electrolyte) of ammonium chloride, a cathode of carbon, a depolarizer of manganese dioxide (oxidizer), and an anode of zinc (reductant). The chemistry of this cell was later successfully adapted to manufacture a dry cell.
In chemistry, ion transport number, also called the transference number, is the fraction of the total electric current carried in an electrolyte by a given ionic species i:
Galvanic 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 similar galvanic reaction is exploited in primary cells to generate a useful electrical voltage to power portable devices. This phenomenon is named after Italian physician Luigi Galvani (1737-1798).
References
- ↑ Wiley Interscience [ dead link ]
- ↑ "Galvanic Cells: Galvanic Cells".
- ↑ Bard, A. J. and Faulkner, L. R. "Electrochemical methods. Fundamentals and applications", John Whiley & Sons, Inc, 2nd edition, USA, 2001
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