Early history

One of the earliest uses of fire was in pottery making. Early humans undoubtedly observed that when clay was heated its water was driven out and a hard rock substance remained. Our ancestors made clay implements and art fixtures by heating their work in open pit fires, and clay implements from 20,000 years ago have been found. 

Early human civilizations used stone, bone, and wood for objects. Approximately ten thousand years ago, metals first appeared. The first metals used were those found in their native form, or in a pure, uncombined state. Most metals today are acquired from an ore containing the metal in combination with other elements such as oxygen. The existence of native metals is rare, and only a few metals exist in native form. Iron and nickel were available in limited supply from meteorites. The first metals utilized widely by humans were copper, silver, and gold. Pure nuggets of these metals were pounded, in a process known as cold hammering, with stones into various shapes used for weapons, jewelry, art, and various domestic implements. Eventually, smiths discovered if a metal was heated it could be shaped more easily. The heating process is known as annealing. Because the supply of native metals was limited, metal items symbolized wealth and status for those who possessed them. 

by the mid-1930s the literature described the ion exchange, adsorption, molecular sieving and structural properties of zeolite minerals as well as a number of reported syntheses of zeolites. The early synthetic work remains unsubstantiated because of incomplete characterization and the difficulty of experimental reproducibility. 

In 1962 Mobil Oil introduced the use of synthetic zeolite X as a hydrocarbon cracking catalyst In 1969 Grace described the first modification chemistry based on steaming zeolite Y to form an ultrastable Y. In 1967-1969 Mobil Oil reported the synthesis of the high silica zeolites beta and ZSM-5. In 1974 Henkel introduced zeolite A in detergents as a replacement for the environmentally suspect phosphates. By 2008 industry-wide approximately 367 0001 of zeolite Y were in use in catalytic cracking [22]. In 1977 Union Carbide introduced zeolites for ion-exchange separations. 

The first observation of the diurnal fluctuation of organic acids in succulent plants is rather difficult to assess. Osmond (1978) believes that M.Grew in 1682 was the first to realize acid accumulation in a succulent plant (Aloe). As early as 1804, De Saussure noted that darkened Opuntia did not liberate CO2, but did take up CO2. Hence, De Saussure was in fact the first who observed dark CO2 fixation in a CAM plant (see Chap. 5.1.1). The causal connection between dark CO2 fixation and acid synthesis, however, was not realized until 1948 (Thurlow and Bonner, 1948 Thomas, 1949). In 1815, Heyne noted remarkable taste differences in diurnal alterations of the leaf acidity in Bryophyllum calcycinum. He wrote  

As quoted in Kraus (1884), shortly after Heyne also H. F. Link observed acid fluctuations in Bryophyllum. Then in 1865, J. Liebig recorded day-night reciprocal carbohydrate-acid fluctuations in succulents (see Kraus, 1884), and Mayer in 1887 noted that organic acids produced in the dark were converted to carbohydrates 

Extensive research by Richards (1915), Bennet-Clark (1933 a, b). Wolf (1937), and then by such investigators as Pucher, Vickery, Thomas, Beevers, and Ranson firmly established the relationship between dark COj fixation and organic acid synthesis in succulent plants. Furthermore, during this early period before 1950 it was clear that the organic acids which accumulated during the dark phase, termed acidification by the early workers, were nearly quantitatively converted to carbohydrates (viz., starch) during the subsequent light or deacidification period (see Bennet-Clark, 1933 for example). 

Diamond, as a material, has been recognized as having unique properties for several thousands of years and references of it being used as an industrial tool can be traced back to at least 300 BC. At this time, whole stones appeared to have been used for engraving and, by 150 BC, India, where the early diamond deposits were discovered, had established an export trade with China for such diamond-tipped engraving tools for use in cutting very hard jade stone (Fig. 1). 

Company in Bartlesville, Oklahoma, USA [21], is an extremely important document that summarizes the details on the historical events that took place during this early period (1952-1960). It is highly recommended for anyone interested in imderstanding the early history of LDPE and HOPE. 

The low-pressure process is primarily responsible for the manufacture of the majority of polyethylene produced globally. In 2010, 75% of the polyethylene produced (115 billion poimds) was manufactured with a low-pressure process and 25% (39 billion pounds) was manufactured with a high-pressure process. 

Attacks on commercial aviation were regarded as unthinkable until the 1960s although a few incidents had occurred in the United States and abroad. Indeed, a commercial aircraft had been bombed in 1955 by Jack Graham in a bizarre scheme 

Starch Chemistry and Technology, Third Edition ISBN 978-0-12-746275-2 

Wheat (see Chapter 10) is the number one food grain consumed by humans, and its production leads all crops, including rice and com. Wheat is a cool-season crop, but it flourishes in many different agroclimate zones. It is believed to have originated in the fertile crescent of the Middle East, where radiocarbon dating places samples at, or before, 6700 bce, with wheat grains existing in the Neolithic site of Jamo, Northern Iraq.3 

A procedure for starch production was given in some detail in a Roman treatise by Cato in 184 bce.5 Grain was steeped in water for ten days and then pressed. Fresh water was added. Mixing and filtration through linen cloth gave a slurry from which the starch was allowed to settle. It was washed with water and finally dried in the sun. 

In the eighteenth century, more economical sources of starch than wheat were being sought. In 1732, the Sieur de Guife recommended to the French government that potatoes be used to manufacture starch. The potato starch industry in Germany dates from 1765 (see Chapter 11). 

In 1820, the production of potato starch had begun in Hillsborough County, New Hampshire. Potato starch use grew rapidly until 1895, at which time 64 factories were operating. They manufactured 24 million pounds (11 million kg) of starch annually during the production season, which lasted about three months. Rice starch manufacture began in the United States in 1815. However, production did not expand significantly, and the little rice starch used was mainly imported. 

Direct evidence for the ability of mitochondria to take up Ca from the medium in a respiration-dependent process was provided in 1961-1962 by Vasington and Murphy [4]. De Luca and Engstrom [5] extended the finding by demonstrating that respiration was not an absolute requirement for the uptake reaction, provided that 

In the early studies mentioned in the preceding section, mitochondria were normally exposed to concentrations of Ca in excess of 1 mM, and the uptake process was allowed to continue until massive amounts of Ca (and phosphate) were accumulated and precipitated inside. Under these conditions, in spite of the frequent presence of ATP/ADP and as protecting agents, mitochondria became 

In a study pubUshed in 1964, Rossi and Lehninger [20] extended the observations made by Chance in 1956 on the stimulation of oxygen consumption by mitochondria, and established that approximately 2Ca were transported into mitochondria as a couple of electrons traversed each one of the respiratory chain segments which were called, in the terminology of the 1960 s, coupling sites . They thus concluded that the Ca /oxygen ratio for the full respiratory chain span was 6. In other words, mitochondria use the same amount of respiratory energy to phosphorylate one ADP molecule or to transport across the membrane 2Ca .  

The matter of the ejection of during Ca uptake was reinvestigated by a number of authors [21-24], who found ratios between H ejection and Ca uptake approaching 2. Concomitant with the ejeetion of H , increase in the titratable alkahnity of the mitochondria was measured [25-28]. 

Depending on whether the source of energy is the respiratory chain or added ATP, the uptake of Ca is inhibited by respiratory chain inhibitors or oligomycin, respectively. As expected, protonophoric uncouplers inhibit in both cases. The competitive inhibition by Mg [29], is of particular interest, since it may have physiological significance due to the presenee of Mg in the cytosol of cells. Mg, however, is not transported by mitochondria through the Ca -uptake system which, on the other hand, translocates Mn, Ba and Sr (see Refs. 13-15 for reviews). 

The use of carbon for purposes other than as a fuel or in metallurgy is ancient various carbons are mentioned for medicinal use in an Egyptian papyrus (1550 B.C.). In the time of Hippocrates and Pliny, 

During the nineteenth century a number of attempts were made to prepare decolorizing carbons from other source materials. In 1822, Bussy,6 heating blood with potash, produced a carbon that had from twenty to fifty times the decolorizing power of bone char. Blood char so prepared was extensively used in laboratory studies until the introduction of modem activated carbons. Bussy also enhanced the adsorptive power of other chars by various methods, some of which were rediscovered years later by others. 

The great capacity of coconut char for adsorbing gases was reported by Hunter7 in 1865. Certain outstanding properties of coconut char have never been fully duplicated in any other char— and for some purposes coconut char is superior to all others. 

Stenhouse,8 in 1856, prepared a decolorizing char by heating a mixture of flour, tar, and magnesium carbonate Lee,9 in 1863, prepared a deodorizing carbon by the action of superheated steam and air on peat and in 1868, Winser and Swindells10 heated wastes from paper mills with phosphates. Some of the disclosures are similar to processes that are in current industrial use, and it is natural to inquire why they were not then developed on a commercial scale. 

One answer can be found in the manufacturing problems that are involved. Although activated carbon can be prepared with relative ease on a laboratory scale, the industrial production is attended by enjineering difficulties. The corrosive action of many activation conditions requires special structural materials that were not then available. Moreover, the successful industrial production of activated carbon depends on the skill of the manufacturer in controlling the environment of activation within narrow limits, and suitable instrumentation for such control is a relatively recent development. 

Roussak and H.D. Gesser, Applied Chemistry A Textbook for Engineers and Technologists, DOI 10.1007/978-l-4614-4262-2 3, Springer Science+Business Media New York 2013 

The Chemical Industry Today Microscopic vs Macroscopic Approach 

The first to consider such ideas scientifically were the Greeks at about 600 BC. They assumed that all matter was derived from water, which could solidify to earth or evaporate to air. This theory was later expanded into the idea that the world was 

Chemical Reactor Analysis and Applicatitms far the Practicing Engineer. By Louis Theodore 2012 John Wiley Sons, Inc. Published 2012 by John Wiley Sons, Inc. 

Aristotle believed that the elements formed a continuum of mass. He became the most influential of the Greek philosophers, and his ideas dominated science for nearly ISOO years. He believed that four qualities were found in nature heat, cold, moisture, and dryness. He proposed that elements were made up of these with each element containing variable amounts of these qualities. These, in turn, combined to form materials that are visible. Because it was possible for each element to change, the elements could be combined because it was possible that material substances could be built up from the elements. 

At approximately the same time a similar alchemy arose in China. The aim was to make gold, since it was believed to be a medicine that could offer long life or even immortality on anyone who consumed it. Nevertheless, the Chinese gained much practical chemical knowledge from incorrect theories. 

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Long D A 1988 Early history of the Raman effect Int. Rev. Phys. Chem. 7 314-49... 

Both processes were practiced in secret for some time after thek revival, and Httie is known of thek early history. The cementation process flourished in the United Kingdom during the eighteenth and nineteenth centuries and continued to be used to a limited extent into the early part of the twentieth century. 

The penicillins are a class of compound having the general structure (1). Because of their unique effectiveness in the treatment of bacterial infections in humans, these compounds have been investigated intensively from the chemical, microbiological and clinical points of view since about 1940. The early history of these developments (see especially B-80MI51100, B-49MI51100) contains the following pivotal studies ... 

One of the reasons the tribes of early history were nomadic was to move periodically away from the stench of the animal, vegetable, and human wastes they generated. When the tribesmen learned to use fire, they used it for millennia in a way that filled the air inside their living quarters with the products of incomplete combustion. Examples of this can still be seen today in some of fhe more primitive parts of the world. After its invention, the chimney removed the combustion products and cooking smells from the living quarters, but for centuries the open fire in the fireplace caused its emission to be smoky. In ad 61 the Roman philosopher Seneca reported thus on conditions in Rome ... 

This book is primarily directed at professional materials scientists and engineers, and they have no urgent need to see themselves defined. Indeed, it would be perfectly reasonable to say about materials science what Aaron Katchalsky used to say about his new discipline, biophysics Biophysics is like my wife. I know her, but I cannot define her (Markl 1998). Nevertheless, in this preliminary canter through the early history of MSE, it is instructive to examine briefly how various eminent practitioners have perceived their changing domain. 

Many other parepistemes were stimulated by the new habits of precision in theory. Two important ones are the entropic theory of rubberlike elasticity in polymers, which again reached a degree of maturity in the middle of the century (Treloar 1951), and the calculation of phase diagrams (CALPHAD) on the basis of measurements of thermochemical quantities (heats of reaction, activity coefficients, etc.) here the first serious attempt, for the Ni-Cr Cu system, was done in the Netherlands by Meijering (1957). The early history of CALPHAD has recently been... 

More interesting, as regards future developments, are the eiforts now being made to dispense with opium as an intermediate in the production of morphine. The early history of experiments in the direct extraction of the alkaloid from poppy capsules and poppy straw has been recounted by Goris and by Wiiest and Frey. ... 

Whittle, Sir Frank. (1945), The early history of the Whittle jet propulsion engine, Proc. Inst. Mech. Engrs. 152,419-435. 

The literature in this area is extensive and some of the concepts and symbolism may be transitory. This chapter reviews the field at a level and with a coverage adequate for the experimentalist to use the standard relationships and to follow their use in the mechanistic literature. Research on the meaning of the extrathermody-namic relationships themselves is beyond our needs the interested reader can explore these ideas further in the references cited. Grunwald has reviewed the early history of LFERs. 

Lipoic acid (6,8-dithiooctanoic acid) was isolated and characterized in 1951 in studies that showed that it was required for the growth of certain bacteria and protozoa. This accomplishment was one of the most impressive feats of isolation in the early history of biochemistry. Eli Lilly and Co., in cooperation with Lester J. Reed at the University of Texas and I. C. Gunsalus at the... 

Table 17.1 Early history of the halogens and their compounds...

The ability of a nltro group in the substrate to bring about electron-transfer free radical chain nucleophilic subsdnidon fSpj li at a saniratedcarbon atom is well documented. Such electron transfer reacdons are one of the characterisdc feanires of nltro compounds. Komblum and Russell have established ihe Spj l reaction independently the details of the early history have been well reviewed by them. The reacdon of -nitrobenzyl chloride v/ith a salt of nitro ilkane is in sharp contrast to the general behavior of the ilkyladon of the carbanions derived from nitro ilkanes here, carbon ilkyladon is predominant. The carbon ilkyladon process proceeds via a chain reacdon involving anion radicals and free radicals, as shovmin Eq. 5.24 and Scheme 5.4 fSpj l reacdoni. 

The early history of ionic liquid research was dominated by their application as electrochemical solvents. One of the first recognized uses of ionic liquids was as a solvent system for the room-temperature electrodeposition of aluminium [1]. In addition, much of the initial development of ionic liquids was focused on their use as electrolytes for battery and capacitor applications. Electrochemical studies in the ionic liquids have until recently been dominated by work in the room-temperature haloaluminate molten salts. This work has been extensively reviewed [2-9]. Development of non-haloaluminate ionic liquids over the past ten years has resulted in an explosion of research in these systems. However, recent reviews have provided only a cursory look at the application of these new ionic liquids as electrochemical solvents [10, 11]. 

The early history of redox initiation has been described by Bacon.23 The subject has also been reviewed by Misra and Bajpai,207 Bamford298 and Sarac.2,0 The mechanism of redox initiation is usually bimolecular and involves a single electron transfer as the essential feature of the mechanism that distinguishes it from other initiation processes. Redox initiation systems are in common use when initiation is required at or below ambient temperature and drey are frequently used for initiation of emulsion polymerization. 

Indeed it can be stated that the history of modern expls begins with the discoveries of nitroglycerin (NG) and nitrocellulose (or more correctly cellulose nitrate or NC) nearly 125 years ago, and their application to military and commercial usage. An excellent review of the early history of NC is given by. T.L. Davis (Ref 29, pp 244—56). The early histories of NG and EGDN (discovered in 1870) are summarized, respectively, in Vol 6, G99-R to G100-R and E259-R, and in the Naoum reference cited above... 

The expl nature of N trichloride has been known since the end of the 18th century when Sir H. Davy reported, The fulminating oil which you mentioned roused my curiosity and nearly deprived me of an eye. After some months confinement I am again well. (Ref 12). The early history of this compd is reviewed in this Ref. It is readily prepd by the action of Cl on ammonia or Amm salts (Refs 2,6 13) or by the electrolysis of an unstirred coned soln of Amm chloride at 35—40° (Ref 4). A procedure for the prepn of a soln of N trichloride in chlf is described In Ref 1, and prepn on an industrial scale in Ref 7... 

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