Historical aspects

Iron oxides in soils have in common that they are of extremely small crystal size and/or low crystal order. This, in combination with their low concentration (only tens g kg in most soils) explains why soil iron oxides have escaped identification for a long time in spite of their obvious existence as seen from the soil colour. In the past, therefore, Fe oxides in surface environments have been considered to be amorphous to X-rays and often called limonite , which mineralogically, is an obsolete term. Furthermore, in order to identify the clay minerals in soils properly, Fe oxides are usually removed before X-ray diffraction methods are applied (Alexander et al., 1939 Mehra Jackson, 1960). 

However, in the last two decades or so, instrumental techniques for studying nano particles have been developed to such an extent (see Chap. 7) that soil Fe oxides can be identified, quantified and characterized in appreciable detail. These results have especially helped in understanding soil formation (pedogenesis) and the behavior of soils towards amendments and pollutants. 

Human use of C. sativa goes back over 10 000 years and the medicinal use can be definitely found in ancient Chinese writings from 1000 BC [126]. Modern medicinal use was mainly introduced by William B. O Shaugnessy who 

Black powder revolutionized warfare and also played a significant role in the overall development in the pattern of living throughout the world. The Chinese first used black powder as a gun propellant as early as 1130, placing it in bamboo tubes that were reinforced with iron to propel stone projectiles and arrows. The Chinese records also indicate that they used black powder in bombs for military purposes. 

High Energy Materials Propellants, Explosives and Pyrotechnics. Jai Prakash Agrawal Copyright 2010 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim ISBN 978-3-527-32610-5 

Around the same time, nitration of cellulose to produce nitrocellulose (NC also known as guncotton) was undertaken by different groups and finally the invention of NC was reported by Schonbein (Basel) and Bottger (Frankfurt) independently in 1846. Further, dynamite was invented by Alfred B. Nobel in 1866. 

Since black powder is relatively low in energy, it leaves a large proportion of corrosive solids after explosion and absorbs moisture readily, it was succeeded in late 1800s by smokeless gunpowder and picric acid. The first smokeless powder, known as cordite, was invented by tbe English chemists Sir James Dewar and Sir Frederick Augustus Abel in 1889. It was made in two forms a gelatinized nitrocellulose and a mixture of NC and NG with a small quantity of petroleum jelly added to act as a stabilizer. Smokeless powder soon became tbe primary ammunition for use in pistols. 

As early as 1873, picric acid was detonated to produce explosion. Subsequently, it was found to be a suitable replacement for black powder. From 1888 into World War I, it was used as a basic explosive for military purposes. Because it required prolonged heating at high temperatures in order to melt and because it also caused shells to corrode in the presence of water, an active search for better explosives continued. 

The property of elastic recovery of rubbers allows them to be used for many products which are subjected to deformation, whether by tension or compression, and must not be destroyed by such forces. Abrasion and corrosion resistances are often the main properties in choosing an elastomer-based product over alternative products. In the mineral processing industry, abrasion often results from a 

The rubber compounder tries to achieve the best compromise by choosing the elastomer or blends of elastomers and then adding various fillers and chemicals of which there are an almost infinite number of combinations. The mineral and chemical processing engineers 

2 Elastomer Types According to American Society of Testing Materials-ASTM D2000 

Survey of the Reactions of Aromatio Nitro-Compounds with Bases. 212 

Gazzolo (1900) thought that the intense colours produced from alkyl picrates and alkoxides could be best described by the quinonoid structure 1 (R = R = alkyl). The first strong chemical evidence that this was indeed the case was provided by Meisenheimer (1902). He obtained identical compounds by the addition of potassium methoxide to 2,4,6-trinitrophenetole and potassium ethoxide to 2,4,6-trinitroanisole. Acidification produced in each case a mixture of methyl and ethyl picrates. This led Meisenheimer to the conclusion that these compounds 

In 1952, Dewar devoted one of the papers in his famous series on perturba-tional molecular orbital theory of organic chemistry to free radical chemistry (Dewar, 1952). In Theorem 65 he states  

A + E substituent R and a — E substituent T can conjugate mutually through an odd alternant hydrocarbon radical S if R, T are both attached to active atoms in S. 

Mutual conjugation of, as we describe it nowadays, + M and — M substituents is equivalent to an extra stabilization of the system. Thus, we can interpret this statement as the first formulation of the captodative effect even though the term was coined much later. The difficulty of organic chemists to comprehend the rather mathematically formulated theorem must have hindered its wider recognition and seems to be the reason that the phenomenon of interaction of + M and — M substituents has been reinvented several times since then. It is remarkable that these rediscoveries were always initiated by experimental studies in free radical chemistry. 

Balaban (1971 Balaban et al., 1977) investigated radicals of type [1] by esr spectroscopy and noted their long lifetime, which he attributed to the push-pull character of the substituents involved and their mutual conjugation. Katritzky (Baldock et al., 1973, 1974 Katritzky and Soti, 1974) recognized in an analysis of merocyanines that there should be a related class of free radicals [2] which, in accordance with the stability of merocyanines, 

The familiarity with qualitative valence bond descriptions of substituent effects in combination with the known substituent effects in carbocations and carbanions led Viehe and his group to the postulate of a captodative effect for free radicals (Stella et al., 1978 Viehe et al., 1979). They did not seem to be aware of the earlier work which was of a more physical organic character. The fact that carbocations [8] are stabilized by + M substituents, and carbanions [9] by -M substituents, raised the idea that free radicals, as 

In addition to membrane-bound PLAiS, mammals have cytosolic PLAjS. Cytosolic PLAi activities have been studied in various tissues including heart, brain and testis. PA-PLAi has been purified from brain [45] and testes [39, 46]. Like other lipolytic enzymes, PLAi is affected by the assay conditions. Using a mixed micelle system Glomset and his colleagues [46] found that a 110 kDa enzyme from testes preferentially hydrolyzed phosphatidic acid. They cloned the PA-PLAi from bovine [16]. This PLAi lacks sequence similarity to type I PLAi, lysophospholipase, LCAT, and triacylglycerol lipases. 

The history of differential thermal analysis and differential scanning calorimetry, as well as thermal analysis, has been described in great detail by Mackenzie (10,11). 

Numerous review articles, book chapters, and books have appeared on the techniques of DTA/DSC. Murphy has written biennial reviews on the subject from 1958 to 1982 (25, 26) when it was taken over by Wendlandt (12, 13). Book chapters and/or books includes those by Smothers and Chiang (27,28), Wendlandt (23. 24), Garn (29), Mackenzie (30), Gordon and Campbell (32, 33), Kissinger and Newman (31), Barrall and Johnson (34), David (35X Barrall (36), Schultze (37), Ramachandran (38), Wunderlich (39), Porter and Johnson (40, 41), Schwenker and Garn (42), Smykaiz-KIoss (4), Pope and Judd (5), Paulik and Paulik (6), Jespeisen (7), Sestak (8), and others. A bibliography of all rhe books written on DTA/DSC and other TA techniques since 1937 has been compiled by Lombardi (9). 

Reinforced elastomers are one of the oldest and most important classes of composite materials (Ruffell, 1952 Sellers and Toonder, 1965 Stern, 1968, p. 278). When the automobile first became popular, the need to toughen tire rubber, especially against abrasion, became obvious. Although zinc oxide had already attained widespread use as a rubber colorant, in 1905 Ditmar realized the true importance of this material as a reinforcing agent for rubber. Many industry veterans can still remember when tires had white treads. However, such tire treads usually lasted less than 5000 miles, and the need for further improvements was imperative. 

In 1904 Mote had already discovered the reinforcing value of very fine carbon blacks. Carbon black proved much superior to zinc oxide for rubber reinforcement, and replaced the latter in tires between 1910 and 1915. At first, only small amounts of carbon black were used. In 1915, for example, tire tread compounds contained only about 22 % carbon black. At the present time this has increased to 50 % or more, and tire treads lasting up to 40,000 miles are now common. 

A word should be added about the present use of zinc oxide in rubber manufacture. The discovery early in this century that many organic vulcanization accelerators are not effective without zinc oxide led to continued usage of this material for purposes other than reinforcement. By far the major use of zinc oxide in the rubber industry today is for activation of organic accelerators, and not for reinforcement. 

Coal carbonization is the earliest and most important method. Coal carbonization is mainly used to produce cokes for metallurgy and some secondary products like coal gas, benzene, and methylbenzene. Coal gasification takes up an important position in chemical industry. City gas and varieties of fuel gases can be produced by coal gasification. The common role of low-tanperature carbonization, direct coal liquefaction, and indirect coal Uqnefaction is to produce liquid fuels. 

The ways in which coal may be converted to chemicals include carbonization (Chapters 16 and 17), hydrogenation (Chapters 18 and 19), oxidation (Chapter 12), solvent extraction (Chapters 11, 18, and 19), hydrolysis (Chapter 12), halogenation (Chapter 12), and gasification (followed by conversion of the synthesis gas Chapters 20 and 21). In some cases, such processing does not produce chemicals in the sense that the products are relatively pure and can be marketed as even industrial grade chemicals. 

A complete description of the processes to produce all of the possible chemical products is beyond the scope of this text. In fact, the production of chemicals from coal has been reported in numerous texts therefore, it is not the purpose of this text to repeat these earlier works. It is, however, the goal of this chapter to present indications of the extent to which chemicals can be produced from coal as well as indications of the variety of chemical types that arise from coal (e.g., see Lowry, 1945 Donath, 1963). 

On the basis of the thermal chemistry of coal (Chapters 13 and 16), many primary products of coal reactions are high-molecular weight species, often aromatic in nature, that bear some relation to the carbon skeletal of coal. The secondary products (i.e., products formed by decomposition of the primary products) of the thermal decomposition of coal are lower molecular weight species but are less related to the carbon species in the original coal as the secondary reaction conditions become more severe (higher temperatures and/or longer reaction times) (Xu and Tomita, 1987). 

In very general terms, it is these primary and secondary decomposition reactions of coal that are the means to produce chemical from coal. There is some leeway in terms of choice of the reaction conditions, and there is also the option of the complete decomposition of coal (i.e., gasification) and the production of chemicals from the synthesis gas (a mixture of carbon monoxide, CO, and hydrogen, H2) produced by the gasification process (Chapters 20 and 21). 

Many methods for the preparation of colloidal metals have been developed over the years since Faraday s experiments. For a survey of activity in the preparation of metal sols in the first half of the century, the reader is referred to the 1951 paper by Turkevitch, Stevenson, and Hillier [8] for detailed synthetic conditions and early electron microscopic characterizations of gold sols as prepared by the methods of Faraday (see above), Bredig (electric arc between gold electrodes 

In the early 1960s, Wanzlick published the first investigations concerning the chemistry of NHCs [19]. In 1968, the synthesis of first stable crystalline transition metal-carbene complexes based on imidazolium salts with mercury(II) and chromium(O), respectively, were published [20, 21]. In the following years, NHCs 

In the early years of the nineteenth century the dietary emphasis shifted from discussions of what not to eat to discussions of what to eat (Drummond and Wilbraham, 1939). This was the result of increased activity in analytical chemistry. Once again in the history of science as suitable methods were developed it became possible to open up whole new realms of knowledge. 

A certain Dr. William Front is credited with the statement in 1834 that there are three great proximate principles in food, one saccharine, one oily, and one albuminous. This idea, with the addition of a few minerals and some slight consideration of water, was to dominate dietary thought for nearly a century. 

One thesis of the present review has already been advanced (Pett et al., 1945), that all dietary standards to date result from critical situations in which scientists were required to consider the rather inadequate data and to state how much food or its constituents must be ingested to achieve a desired result. Thus such statements tend to be colored by the problem itself and by the purpose of the standard which is really the manner chosen to deal with the problem. 

In a useful review of dietary standards, Leitch (1942) ascribes to a certain Dr. E. Smith in England the first statement of dietary requirements. The critical situation was a cotton famine and widespread unemployment among English cotton workers. The purpose of the resulting standard was to avert starvation diseases, and the figures were in terms of carbon and nitrogen. 

The next general statement of requirements (Lusk, 1918) concerned only energy values, and was a preliminary to estimation of the total food requirements of the United Kingdom, France, and Italy as a basis for American exports of food to these countries. In other words the critical situation was the depletion of European food supplies due to World War I. In accepting Lusk s statement the Royal Society made additional notes regarding the amount of protein and the percentage of fat. 

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E. N. Bamberger, Bearing Design—Historical Aspects, Present Technology and Future Problems, American Society of Mechanical Engineers, New York, 1980, pp. 1-45. 

The reader is referred to previous reviews for historical aspects and early work. For condensed quinazoline systems, The Chemistry of Heterocyclic Compoundsr—Six Membered Heterocyclic Nitrogen Compounds with Four Condensed Rings should be consulted. 

See also Electric Power, Generation of Environmental Problems and Energy Use Explosives and Propellants Meitner, Lise Military Energy Use, Historical Aspects of Molecular Energy Nuclear Energy Nuclear Energy, Historical Evolution of the Use of Nuclear Fission Fuel Nuclear Fusion Nuclear Waste. 

See also-. Aviation Fuel Batteries Engines Fuel Cells Fuel Cell Vehicles Military Energy Use, Historical Aspects of Rocket Propellants Storage Technology. 

Militai"y Energy Use, Historical Aspects of Shannon A. Brown... 

Historical aspects of immunology 4.5.3 Regulation of complement activity... 

Herein we briefly mention historical aspects on preparation of monometallic or bimetallic nanoparticles as science. In 1857, Faraday prepared dispersion solution of Au colloids by chemical reduction of aqueous solution of Au(III) ions with phosphorous [6]. One hundred and thirty-one years later, in 1988, Thomas confirmed that the colloids were composed of Au nanoparticles with 3-30 nm in particle size by means of electron microscope [7]. In 1941, Rampino and Nord prepared colloidal dispersion of Pd by reduction with hydrogen, protected the colloids by addition of synthetic pol5mer like polyvinylalcohol, applied to the catalysts for the first time [8-10]. In 1951, Turkevich et al. [11] reported an important paper on preparation method of Au nanoparticles. They prepared aqueous dispersions of Au nanoparticles by reducing Au(III) with phosphorous or carbon monoxide (CO), and characterized the nanoparticles by electron microscopy. They also prepared Au nanoparticles with quite narrow... 

Hudson, C. S., Historical Aspects of Emil Fischer s Fundamental Conventions for Writing Stereo-formulas in a Plane, III, 1-22... 

Miller JA, Miller EC (1983) Some historical aspects of N-aryl carcinogens and their metabolic activation. Env Health Persp 49 3-12... 

It is worth noting some historical aspects in relation to the instrumentation for observing phosphorescence. Harvey describes in his book that pinhole and the prism setup from Newton were used by Zanotti (1748) and Dessaignes (1811) to study inorganic phosphors, and by Priestley (1767) for the observation of electroluminescence [3], None of them were capable of obtaining a spectrum utilizing Newton s apparatus that is, improved instrumentation was required for further spectroscopic developments. Of practical use for the observation of luminescence were the spectroscopes from Willaston (1802) and Frauenhofer (1814) [13]. 

HINDERSINN Historical Aspects of Polymer Fire Retardance... 

Pepys, J. and Bernstein, I.L., Historical aspects of occupational asthma in Asthma in the Workplace, L. Bernstein, M. Chang-Yeung, J.-L. Malo, and D. I. Bernstein, Eds. Marcel Dekker, New York, 5, 1999. 

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