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Oxidation Oxidation and reduction reactions are essential to life.

Oxidation of nutrients provides plants and animals with the energy they need to survive. When an organism dies, oxidation reactions are responsible for the decay of the organic matter. Oxidation reactions are also used by chemists to synthesize pharmaceuticals, textiles, dyes, paints and a multitude of other important products. Oxygen is third on the list of bulk chemicals produced per year in the United States. One of the most challenging questions about the origin of life on Earth is how early organisms protected themselves from oxygen in the atmosphere. All organic matter exposed to oxygen tends to be converted into carbon dioxide and water, and most minerals are oxidized forms of elements. Avoiding oxidation of materials is of practical concern as well: metals are painted or lubricated to inhibit oxidative corrosion and wood products are coated to prevent the oxidative degradation known as decay. The original definition of oxidation centered on the class of reaction in which one or more oxygen atoms from oxygen itself to another species was added to an element or compound. It became apparent, however, that other substances besides oxygen could add oxygen atoms to molecules. Species that cause oxidation are called oxidants or oxidizing agents. It is important to note that oxidation and reduction always occur in tandem: if a species in a reaction is oxidized, then some thing else must be reduced. Most metals are readily oxidized when exposed to the atmosphere. Many metal oxides are powdery, non-malleable, non-ductile substances. Only as the free metal do they have significant tensile strength and can they be shaped and formed into

useful tools or other objects. Engineers and scientists continually strive to develop better methods to prevent corrosion of metals by atmospheric oxygen. The current approach to understanding oxidation reactions has been developed from the idea that electrons are crucial to chemical bonding. When a metal is oxidized, it is converted from an uncharged atom to a cation by losing electrons. The definition of oxidation of a chemical species, including a particular atom within a molecule as well as entire molecules or ions, has been broadened to include any process in which the species loses electrons. Most compounds are covalent, not ionic. Covalent compounds can undergo oxidation: for example, the conversion of carbon monoxide to carbon dioxide. To encompass all oxidation and reduction reactions, it is necessary to determine the gain and loss of electrons for covalent as well as ionic and elemental species. Electrons are assigned to atoms in covalent and ionic compounds and the oxidation number of each atom is determined.
To determine if a change in the number of electrons of an atom has occurred, we must have some way of assigning the starting and ending states of atoms in terms of number of electrons. This requires determining the oxidation states of the atoms. Oxidation states are specified by oxidation numbers. A species is oxidized in a reaction if it undergoes a increase in oxidation number. A few simple rules are used to assign oxidation numbers. These rules are the result of assigning all electrons in a covalent bond to the more electronegative atom in the bond. Since only valence electrons are shared or transferred, the maximum positive oxidation number of an atom is the number of valence electrons. The rules are given in order of preference: if two rules apply, the first one is used. 1. The oxidation number of an atom in an elemental substance is zero. 2. The oxidation number of a monatomic ion is the charge on the ion. 3. The oxidation number of fluorine in all of its compounds is -1, because fluorine is the most electronegative element.

4. Because the hydrogen atom has only one electron to share and can accommodate only one electron, the oxidation number of hydrogen is +1 except when it forms compounds with metals, in which it is -1. 5. Because oxygen is the second most electronegative element, its oxidation number is -2 except when it bonds to fluorine [OF2: O = +2] or to itself, as in O2 (zero), H2O2 (-1), or HO2 (-1/2). 6. The oxidation number of the halogens other than fluorine is -1, unless they are bonded to oxygen or a more electronegative halogen. 7. The sum of oxidation numbers for all atoms in a polyatomic ion equals the charge on the ion, and the sum of all oxidation numbers for atoms in a neutral molecule equals zero. Oxidation numbers are not ionic charges. They can be computed for atoms in any compound, ionic or covalent. When two elements may combine in several different ratios, the oxidation number of an atom is specified by a Roman numeral in parentheses within the name of the compound. For example, three oxides of nitrogen are N2O (nitrogen(I) oxide), NO (nitrogen(II) oxide) and NO2 (nitrogen(IV) oxide), and two chlorides of iron are FeCl2 (iron(II) chloride) and FeCl3 (iron(III) chloride). For some compounds specific names were used to indicate an oxidation state before the current Roman numeral method was adopted. It is still common to see the older nomenclature. For example, copper(I) chloride is also known as cuprous chloride; copper(II) chloride, cupric chloride.Copper has two oxidation states: +1 and +2. The -ous ending on the name of the metal specifies the lower of the two oxidation states. The -ic ending specifies the higher oxidation state. Iron also has two common oxidation states: +2 and +3. For the compounds of iron, then, ferrous designates iron(II) and ferric, iron(III). Some elements combine is several ratios with different oxidation states, leading to a complex series of names. For example, the older names for the oxoacids and the corresponding ions of chlorine are: perchloric acid (HClO4), perchlorate ion (ClO2-), chloric acid (HClO3), chlorate ion (ClO2-), chlorous acid (HClO2), chlorite ion (ClO2-), hypochlorous acid (HClO), and hypochlorite ion (ClO-). In such as extensive series of names, the prefix "per-" indicates an oxidation state higher than the one designated with the -ate or -ic suffix and an oxidation state lower than the one with the -ite or -ous suffix is designated by the prefix "hypo-." The naming system using Roman numerals is preferred, because the oxidation state of the element is specified clearly. In a chemical reaction involving oxidation of one or more atoms, other atoms must be reduced to the same extent: electrons are not gained or lost in an overall chemical reaction. Since changes in oxidation numbers indicate changes in the number of electrons assigned to atoms, the overall change in oxidation numbers of all the atoms involved in the reaction must also be zero. This fact is critical in balancing chemical equations for oxidation-reduction reactions. Oxidation-reduction reactions cover a wide range of chemical changes, including reactions of atoms of the same element in different oxidation states. Three categories that encompass all these different oxidation-reduction reactions are: atom transfer reactions, electron transfer reactions, and disproportionation reactions. In an atom transfer oxidation-reduction reaction, the atom

being oxidized or reduced is bonded with a different species in the product than in the reactant; it has been chemically transferred to form a new species. Reactions of non-metallic elements to form covalent compounds are atom transfer reactions. Because we exist in an oxygen rich atmosphere, the most prevalent class of atom transfer oxidation-reduction reactions involves oxygen. Such reactions include combustion, oxidative corrosion of metals, and metabolic oxidation of foods. Metabolism is just a form of controlled combustion, as is the rusting of iron. The complete metabolism of cane sugar and its complete combustion yield the same products: carbon dioxide and water. Reactions in which oxidation states change without the transfer of either the reductant or oxidant atoms are defined as electron transfer reactions. Electron transfer reactions occur in the process of metabolism and photosynthesis and are also used in large scale industrial processes when appropriate oxidants and reductants are mixed together. Electrochemical processes are also electron transfer reactions. Unlike most other types of chemical reactions, the reactants in an electrochemical process can be spacially separated as long as there is a means for electrons to flow from the reductant to the oxidant. Electrochemical oxidation is used industrially to protect and beautify metal surfaces by anodizing them and to produce many other products and it is used in methods to analyze the metal contents of samples (anodic stripping) as well as in other electroanalytical techniques. Reactions in which atoms of the same element are both oxidized and reduced are disproportionation reactions. An example is the reaction of two molecules of hydrogen peroxide to form two molecules of water and one molecule of oxygen. The oxidation number for both oxygen atoms in hydrogen peroxide is -1. In the products, the oxidation number of the oxygen atom in water is -2, while that in molecular oxygen is 0. The Periodic Table can be used to predict ability of species to act as oxidizing agents. The reactivity of nonmetallic elements often parallels their electronegativity: the more electronegative the element, the more powerful an oxidant. Fluorine is the strongest oxidant of all the elements. Oxygen, the next most electronegative element, is also a powerful oxidant, as are chlorine and bromine. Elemental nitrogen, however, is only capable of oxidizing a few metals such as lithium and magnesium. Ozone, an unstable, allotropic form of oxygen, is a more powerful oxidizing agent than O2. In acidic solution, it is one of the most powerful oxidizing agents known. When ozone functions as an oxidizing agent, one of its oxygens is reduced; the other two form a molecule of O2, another example of a disproportionation reaction. The reactivities of polyatomic ions as oxidants often follows a sequence in which the most highly oxidized central atom is each series of oxoanions of a particular element is the strongest oxidant. Thus, perchlorate ion is a stronger oxidant than chlorate ion, followed by chlorite ion and hypochlorite ion. There is a direct relationship within each series of oxoanions between oxidizing ability and oxidation state of the central atom. From one series of oxoanions to another, the reactivity depends both on the oxidation state of the central atom and its electronegativity. The more electronegative the central atom and the higher its electronegativity, the stronger the oxidant. Thus, chlorate ion is a stronger oxidant than bromate ion and so forth.

Liquid bleach used in the laundry is an alkaline solution of hypochlorite ion. The hypochlorite ion is an oxidizing agent that sterilizes water by ridding it of microorganisms. A convenient way to prepare solutions of hypochlorite ion is an oxidation-reduction reaction. When bubbled through alkaline water, chlorine gas disproportionates to form chloride ion and hypochlorite ion. Oxidation and reduction reactions are essential to life, abound in geological systems, and are mainstays of the chemical manufacturing industry. They differ from other reactions in that electrons are transferred from one species to another, thereby changing the oxidation number of atoms involved in the chemical change. Oxidation and reduction always occur together, for as one species is oxidized and loses electrons, another must gain electrons and be reduced. Balancing oxidation-reduction reactions requires consideration of the numbers of electrons gained and lost by atoms in the process, as well as to the conservation of matter. Rust, corrosion, spoilage of food, and combustion are all oxidations. Metabolism is a biochemically important oxidation process. The range of organic oxidation reactions is vast. Carbon in its most reduced form (oxidation number -4) is found in alkanes, which are typically fuels like methane, propane, and octane. Next are compounds such as methanol CH3OH) or the alkenes--compounds with carbon-carbon double bonds (oxidation number -2).Aldehydes contain carbons at an oxidation state of 0 (carboxylic acids, +2; and finally carbon dioxide, at +4, used as a fire extinguisher).