Azides
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Azides
In chemistry, azide is a linear, polyatomic anion with the formula and structure . It is the conjugate base of hydrazoic acid . Organic azides are organic compounds with the formula , containing the azide functional group. The dominant application of azides is as a propellant in air bags. Preparation Sodium azide is made industrially by the reaction of nitrous oxide, with sodium amide in liquid ammonia as solvent: : Many inorganic azides can be prepared directly or indirectly from sodium azide. For example, lead azide, used in detonators, may be prepared from the metathesis reaction between lead nitrate and sodium azide. An alternative route is direct reaction of the metal with silver azide dissolved in liquid ammonia. Some azides are produced by treating the carbonate salts with hydrazoic acid. Bonding Azide is isoelectronic with carbon dioxide , cyanate , nitrous oxide , nitronium ion and cyanogen fluoride NCF. Per valence bond theory, azide can be described by sever ...
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Organic Azide
An organic azide is an organic compound that contains an azide (–) functional group. Because of the hazards associated with their use, few azides are used commercially although they exhibit interesting reactivity for researchers. Low molecular weight azides are considered especially hazardous and are avoided. In the research laboratory, azides are precursors to amines. They are also popular for their participation in the " click reaction" and in Staudinger ligation. These two reactions are generally quite reliable, lending themselves to combinatorial chemistry. History Phenyl azide ("diazoamidobenzol"), was prepared in 1864 by Peter Griess by the reaction of ammonia and phenyldiazonium. In the 1890s, Theodor Curtius, who had discovered hydrazoic acid (), described the rearrangement of acyl azides to isocyanates subsequently named the Curtius rearrangement. Rolf Huisgen described the eponymous 1,3-dipolar cycloaddition. The interest in azides among organic chemists has been ...
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Lead Azide
Lead(II) azide is an inorganic compound. More so than other azides, is explosive. It is used in detonators to initiate secondary explosives. In a commercially usable form, it is a white to buff powder. Preparation and handling Lead(II) azide is prepared by the reaction of sodium azide and lead(II) nitrate in aqueous solution. Lead(II) acetate can also be used. Thickeners such as dextrin or polyvinyl alcohol are often added to the solution to stabilize the precipitated product. In fact, it is normally shipped in a dextrinated solution that lowers its sensitivity. Production history Lead azide in its pure form was first prepared by Theodor Curtius in 1891. Due to sensitivity and stability concerns, the dextrinated form of lead azide (MIL-L-3055) was developed in the 1920s and 1930s with large scale production by DuPont Co beginning in 1932. Detonator development during World War II resulted in the need for a form of lead azide with a more brisant output. RD-1333 lead azide (MIL ...
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Hydrazoic Acid
Hydrazoic acid, also known as hydrogen azide or azoimide, This also contains a detailed description of the contemporaneous production process. is a compound with the chemical formula . It is a colorless, volatile, and explosive liquid at room temperature and pressure. It is a compound of nitrogen and hydrogen, and is therefore a pnictogen hydride. It was first isolated in 1890 by Theodor Curtius. The acid has few applications, but its conjugate acid, conjugate base, the azide ion, is useful in specialized processes. Hydrazoic acid, like its fellow mineral acids, is soluble in water. Undiluted hydrazoic acid is dangerously explosive with a standard enthalpy of formation ΔfHo (l, 298K) = +264 kJ/mol. When dilute, the gas and aqueous solutions (<10%) can be safely prepared but should be used immediately; because of its low boiling point, hydrazoic acid is enriched upon evaporation and condensation such that dilute solutions incapable of explosion can form droplets in the headspace o ...
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Silver Azide
Silver azide is the chemical compound with the formula . It is a silver(I) salt of hydrazoic acid. It forms a colorless crystals. It is a well-known explosive. Structure and chemistry Silver azide can be prepared by treating an aqueous solution of silver nitrate with sodium azide. The silver azide precipitates as a white solid, leaving sodium nitrate in solution. : X-ray crystallography shows that is a coordination polymer with square planar coordinated by four azide ligands. Correspondingly, each end of each azide ligand is connected to a pair of centers. The structure consists of two-dimensional layers stacked one on top of the other, with weaker Ag–N bonds between layers. The coordination of can alternatively be described as highly distorted 4 + 2 octahedral, the two more distant nitrogen atoms being part of the layers above and below. In its most characteristic reaction, the solid decomposes explosively, releasing nitrogen gas: : The first step in this decomposi ...
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Transition Metal Azide Complex
Transition metal azide complexes are coordination complexes containing one or more azide (N3−) ligands. Structure and bonding Azide is a pseudohalide but more nucleophilic than chloride. As a monodentate ligand, azide binds through one of the two terminal nitrogen atoms, i.e. M-N=N=N. The N3 unit is linear or nearly so. The M-N-N angles are quite bent. Azide functions as a bridging ligand via two bonding modes. Commonly the metals share the same nitrogen ("N-diazonium" mode). Less common is the motif M-N=N=N-M, illustrated by u(N3)(PPh3)2sub>2. Homoleptic complexes Many homoleptic complexes (with only one kind of ligand) are known. Coordination numbers range from 2 (e.g., u(N3)2sup>−) to 7 (e.g., (N3)7sup>−). Many homoleptic complexes are octahedral anions of the type (N3)6sup>n-: *dianions for tetravalent metals V, Pt, Ti, Zr, Hf *trianions for trivalent metals Cr, Fe, Ru, Rh, Ir *tetraanions for the divalent Ni For some metals, homoleptic complexes exist in two oxi ...
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Ligand
In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs, often through Lewis bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands". Metals and metalloids are bound to ligands in almost all circumstances, although gaseous "naked" metal ions can be generated in a high vacuum. Ligands in a complex dictate the reactivity of the central atom, including ligand substitution rates, the reactivity of the ligands themselves, and redox. Ligand selection requires critical consideration in many practical areas, including bioinorganic and medicinal chemistry, homogeneous catalysis, and environmental chemi ...
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Resonance Structure
In chemistry, resonance, also called mesomerism, is a way of describing Chemical bond, bonding in certain molecules or polyatomic ions by the combination of several contributing structures (or ''forms'', also variously known as ''resonance structures'' or ''canonical structures'') into a resonance hybrid (or ''hybrid structure'') in valence bond theory. It has particular value for analyzing delocalized electrons where the bonding cannot be expressed by one single Lewis structure. Overview Under the framework of valence bond theory, resonance is an extension of the idea that the bonding in a chemical species can be described by a Lewis structure. For many chemical species, a single Lewis structure, consisting of atoms obeying the octet rule, possibly bearing formal charges, and connected by bonds of positive integer order, is sufficient for describing the chemical bonding and rationalizing experimentally determined molecular properties like Bond length, bond lengths, Bond angl ...
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Valence Bond Theory
In chemistry, valence bond (VB) theory is one of the two basic theories, along with molecular orbital (MO) theory, that were developed to use the methods of quantum mechanics to explain chemical bonding. It focuses on how the atomic orbitals of the dissociated atoms combine to give individual chemical bonds when a molecule is formed. In contrast, molecular orbital theory has orbitals that cover the whole molecule. History Lothar Meyer in his 1864 book, ''Die modernen Theorien der Chemie'', contained an early version of the periodic table containing 28 elements, classified elements into six families by their valence—for the first time, elements had been grouped according to their valence. Works on organizing the elements by atomic weight, until then had been stymied by the widespread use of equivalent weights for the elements, rather than atomic weights. In 1916, G. N. Lewis proposed that a chemical bond forms by the interaction of two shared bonding electrons, with the repr ...
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Cyanogen Fluoride
Cyanogen fluoride (molecular formula: FCN; IUPAC name: carbononitridic fluoride) is an inorganic linear compound which consists of a fluorine in a single bond with carbon, and a nitrogen in a triple bond with carbon. It is a toxic and explosive gas at room temperature. It is used in organic synthesis and can be produced by pyrolysis of cyanuric fluoride or by fluorination of cyanogen Cyanogen is the chemical compound with the formula ( C N)2. It is a colorless and highly toxic gas with a pungent odor. The molecule is a pseudohalogen. Cyanogen molecules consist of two CN groups – analogous to diatomic halogen molecu .... Synthesis Cyanogen fluoride (FCN), is synthesized by the pyrolysis of cyanuric fluoride (C3N3F3) at 1300 °C and 50mm pressure; this process gives a maximum of 50% yield. Other products observed were cyanogen and CF3CN. For pyrolysis, an induction heated carbon tube with an internal diameter of 0.75 inches is packed with 4 to 8 mesh carbon gra ...
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Nitronium Ion
The nitronium ion, , is a cation. It is an onium ion because its nitrogen atom has +1 charge, similar to ammonium ion . It is created by the removal of an electron from the paramagnetic nitrogen dioxide molecule , or the protonation of nitric acid (with removal of ). It is stable enough to exist in normal conditions, but it is generally reactive and used extensively as an electrophile in the nitration of other substances. The ion is generated ''in situ'' for this purpose by mixing concentrated sulfuric acid and concentrated nitric acid according to the equilibrium: : Structure The nitronium ion is isoelectronic with carbon dioxide and nitrous oxide, and has the same linear structure and bond angle of 180°. For this reason it has a similar vibrational spectrum to carbon dioxide. Historically, the nitronium ion was detected by Raman spectroscopy, because its symmetric stretch is Raman-active but infrared-inactive. The Raman-active symmetrical stretch was first used to identif ...
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Cyanate
Cyanate is an anion with the structural formula , usually written . It also refers to any salt containing it, such as ammonium cyanate. It is an isomer of the much less stable fulminate anion .William R. Martin and David W. Ball (2019): "Small organic fulminates as high energy materials. Fulminates of acetylene, ethylene, and allene". ''Journal of Energetic Materials'', volume 31, issue 7, pages 70-79. A cyanate ester is an organic compound containing the cyanate group. The cyanate ion is an ambidentate ligand, forming complexes with a metal ion in which either the nitrogen or oxygen atom may be the electron-pair donor. It can also act as a bridging ligand. Cyanate ion The three atoms in a cyanate ion lie on a straight line, giving the ion a linear structure. The electronic structure is described most simply as : :Ö̤−C≡N: with a single C−O bond and a triple C≡N bond. The infrared spectrum of a cyanate salt has a band at ca. 2096 cm−1; such a high frequen ...
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Carbon Dioxide
Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is transparent to visible light but absorbs infrared radiation, acting as a greenhouse gas. It is a trace gas in Earth's atmosphere at 421 parts per million (ppm), or about 0.04% by volume (as of May 2022), having risen from pre-industrial levels of 280 ppm. Burning fossil fuels is the primary cause of these increased CO2 concentrations and also the primary cause of climate change.IPCC (2022Summary for policy makersiClimate Change 2022: Mitigation of Climate Change. Contribution of Working Group III to the Sixth Assessment Report of the Intergovernmental Panel on Climate Change Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA Carbon dioxide is soluble in water and is found in groundwater, lakes, ice caps, ...
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