Inorganic Methods

Inorganic Methods. Before the development of electrolytic processes, hydrogen peroxide was manufactured solely from metal peroxides. Eady methods based on barium peroxide, obtained by air-roasting barium oxide, used dilute sulfuric or phosphoric acid to form hydrogen peroxide in 3—8% concentration and the corresponding insoluble barium salt. Mote recent patents propose acidification with carbon dioxide and calcination of the by-product barium carbonate to the oxide for recycle. 

Pansu, M., J. Gautheyrou. 2006. Handbook of Soil Analysis - Mineralogical, Organic and Inorganic Methods. New York Springer. 

A further distinction is made between organic and inorganic methods. For many inorganic elements, behaviour is highly dependent upon organic substances, and the two topics cannot be treated in isolation. Rather, inorganic methods must include a basic evaluation of organic components. 

EPA Superfund website. Contract Laboratory Program Inorganic Methods Web page, http //www.epa.gov/superfund/programs/clp/ilm5.htm. 

Luminescence has been used in conjunction with flow cells to detect electro-generated intennediates downstream of the electrode. The teclmique lends itself especially to the investigation of photoelectrochemical processes, since it can yield mfonnation about excited states of reactive species and their lifetimes. It has become an attractive detection method for various organic and inorganic compounds, and highly sensitive assays for several clinically important analytes such as oxalate, NADH, amino acids and various aliphatic and cyclic amines have been developed. It has also found use in microelectrode fundamental studies in low-dielectric-constant organic solvents. 

A method of estimating small amounts of water in organic liquids (and also in some inorganic salts) is that of Karl Fischer. The substance is titrated with a mixture of iodine, sulphur dioxide and pyridine dissolved in methyl alcohol. The essential reaction is ... 

A challenging task in material science as well as in pharmaceutical research is to custom tailor a compound s properties. George S. Hammond stated that the most fundamental and lasting objective of synthesis is not production of new compounds, but production of properties (Norris Award Lecture, 1968). The molecular structure of an organic or inorganic compound determines its properties. Nevertheless, methods for the direct prediction of a compound s properties based on its molecular structure are usually not available (Figure 8-1). Therefore, the establishment of Quantitative Structure-Property Relationships (QSPRs) and Quantitative Structure-Activity Relationships (QSARs) uses an indirect approach in order to tackle this problem. In the first step, numerical descriptors encoding information about the molecular structure are calculated for a set of compounds. Secondly, statistical and artificial neural network models are used to predict the property or activity of interest based on these descriptors or a suitable subset. 

An account will be given in this and the two following Sections of a number of inorganic reagents which find application in organic chemistry. No attempt will be made to describe the preparation of those reagents which can be purchased at a reasonable cost. In some cases, where the purified reagents are somewhat expensive, the methods of purification from the technical products will be outlined. 

A method for determining the SO, content of oleum is described in the author s Text Book 0/ Quantitative Inorganic Analysis Theory and Practice, Second Edition, 1951, p. 263 (Longmans, Green and Co. Ltd.). 

N-Benzylamides are recommended when the corresponding acid is liquid and/or water-soluble so that it cannot itself serve as a derivative. Phe benzylamides derived from the simple fatty acids or their esters are not altogether satisfactory (see Table below) those derived from most hydroxy-acids and from poly basic acids or their esters are formed in good yield and are easily purified. The esters of aromatic acids yield satisfactory derivatives but the method must compete with the equally simple process of hydrolysis and precipitation of the free acid, an obvious derivative when the acid is a solid. The procedure fails with esters of keto, sul phonic, inorganic and some halogenated aliphatic esters. 

If an appreciable amount of residue remains, note its colour. Add a few drops of water and test the solution (or suspension) with htmus or with Universal indicator paper. Then add a httle dilute hydrochloric acid and observe whether efiervesceiice occurs and the residue dissolves. Apply a flame test with a platinum wire on the hydrochloric acid solution to determine the metal present. (In rare cases, it may be necessary to subject a solution of the residue to the methods of qualitative inorganic analysis to identify the metal or metals present.) If the flame test indicates sodium, repeat the ignition of the substance on platinum foil. 

Semiempirical calculations have been very successful in the description of organic chemistry, where there are only a few elements used extensively and the molecules are of moderate size. Some semiempirical methods have been devised specifically for the description of inorganic chemistry as well. The following are some of the most commonly used semiempirical methods. 

The primary reason for interest in extended Huckel today is because the method is general enough to use for all the elements in the periodic table. This is not an extremely accurate or sophisticated method however, it is still used for inorganic modeling due to the scarcity of full periodic table methods with reasonable CPU time requirements. Another current use is for computing band structures, which are extremely computation-intensive calculations. Because of this, extended Huckel is often the method of choice for band structure calculations. It is also a very convenient way to view orbital symmetry. It is known to be fairly poor at predicting molecular geometries. 

The PRDDO (partial retention of diatomic differential overlap) method is an attempt to get the optimal ratio of accuracy to CPU time. It has been parameterized for the periodic elements through Br, including the 3rd row transition metals. It was parameterized to reproduce ah initio results. PRDDO has been used primarily for inorganic compounds, organometallics, solid-state calculations, and polymer modeling. This method has seen less use than other methods of similar accuracy mostly due to the fact that it has not been incorporated into the most widely used semiempirical software. 

The Fenske-Hall method is a modification of crystal held theory. This is done by using a population analysis scheme, then replacing orbital interactions with point charge interactions. This has been designed for the description of inorganic metal-ligand systems. There are both parameterized and unparameterized forms of this method. 

Ah initio methods are accurate and can be reliably applied to unusual structures and inorganic compounds. In most cases, HF calculations are fairly good for organic molecules. Large basis sets should be used. 

Modeling the lighter main group inorganic compounds is similar to modeling organic compounds. Thus, the choice of method and basis set is nearly identical. The second-row compounds (i.e., sulfur) do have unfilled d orbitals, making it often necessary to use basis sets with d functions. 

If these elements are included in an organic molecule, the choice of computational method can be made based on the organic system with deference to the exceptions listed in this section. If completely inorganic calculations are being performed, use a method that tends to correctly model the property of interest in organic systems. 

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