Combustion, early theories

Birth of Dr. John Mayow in London. Author of an early theory of combustion. 

The early theory of methane oxidation assumed that carbon and water ware tile initial products of reaction or that hydrogen burned preferentially to carbon. However, in 1861 Kersten0 declared that carbon monoxide and hydrogen were the primary products, and that although some free carbon may form at times, the carbon is normally oxidized to carbon monoxide before the hydrogeu is reacted upon. This idea, later revived by Misterli,7 involves the preferential combustion of carbon and is thus directly opposed to the hydroxylation theory. Tins theory might possibly apply to the case of acetylene combustion, since this hydrocarbou is sufficiently unstable as to explode alone under certain conditions, but cannot hold for the more saturated hydrocarbons which do not explode alone. 

The chronology of the most remarkable contributions to combustion in the early stages of its development is as follows. In 1815, Sir Humphry Davy developed the miner s safety lamp. In 1826, Michael Faraday gave a series of lectures and wrote The Chemical History of Candle. In 1855, Robert Bunsen developed his premixed gas burner and measured flame temperatures and flame speed. Francois-Ernest Mallard and Emile Le Chatelier studied flame propagation and proposed the first flame structure theory in 1883. At the same time, the first evidence of detonation was discovered in 1879-1881 by Marcellin Berthelot and Paul Vieille this was immediately confirmed in 1881 by Mallard and Le Chatelier. In 1899-1905, David Chapman and Emile Jouguet developed the theory of deflagration and detonation and calculated the speed of detonation. In 1900, Paul Vieille provided the physical explanation of detonation... 

John Mayow, 1641-1679, English chemist and physician, who died quite young. Famous for his early researches on combustion and respiration His theory of combustion was described in his tract entitled "De Sale Nitro et Spirito Nitro-aereo in 1674 ( 48). 

The molecular composition of picric acid was established in the early ninteenth century when it was the only highly-nitrated aromatic compound then known. It was evident that its oxygen content was insufficient for complete combustion (to C02 and H20). This was considered to be an adequate foundation for the erroneous theory that, because of its insufficient oxygen content, the substance has no explosive properties. It was believed that explosive properties are achieved only by mixing picric acid with oxidizing agents such as chlorates, or sodium or potassium nitrates. 

Early experiments of Berl and coworkers (15, 16), together with the findings of Withrow and Rassweiler (136), support the metallic theory of antiknock action. In Berl s work colloidal lead exhibited antiknock action, while colloidal lead oxide had no effect. Spectra of engine knocking combustion obtained by Withrow and Rassweiler showed the presence of metallic lead but not lead oxide or other lead oxides. The metallic theory is also supported by other investigators (96, 101, ) ... 

The crystalline inorganic monopropellants decompose directly from the solid to the vapor phase and are approximately described by the above mentioned theoretical work, in spite of the fact that the gas phase processes are simplified. However, the double-base propellants and other organic materials liquefy before vaporizing. In their combustion, so-called foam and fizz zones occur before the vapor phase processes. Much work has been done attempting to apply the conservation equations to the series of processes. This work forms the basis for the summary by Geckler (G3). It is the viewpoint of this author that too many parameters are determined empirically in this application of the theory, so that useful extrapolations are not possible. One must admire the manipulative skill of the early workers in this field and also their determination to formulate a complete theory. When and if the rate parameters become available, a useful theory will be developed with the aid of this early work. 

Daniel Bernoulli proposed the kinetic molecular theory for gases in the early 1700s to explain the nature of heat and Boyle s Law. At that time, heat was thought to be related to the release of a substance called phlogiston from combustible material. 

For heterogeneous propellants, the current situation is much less satisfactory. The complexity of the combustion process was discussed in Section 7.7. To employ a result like equation (66) directly is questionable, although attempts have been made to evaluate parameters like A and B of equations (67) and (68) from complicated combustion models for use in response-function calculations [81], [82]. Relatively few theories have been addressed specifically to the acoustic response of heterogeneous propellants [82]. Applications of time-lag concepts to account for various aspects of heterogeneity have been made [60], [83], a simplified model—including transient variations in stoichiometry—has been developed [84], and the sideways sandwich model, described in Section 7,7, has been explored for calculating the acoustic response [85], There are reviews of the early studies [7] and of more recent work [82],... 

They were expressed in his early book, Theory of Combustion and Gas Detonation, Moscow Akad. Nauk SSSR, 1944. 

Assuming the canonical view that chemistry emerged as a theoretical science only with Lavoisier s theory of combustion, Gillispie looked for an influence of that theory on Leblanc and also found nothing. That he did not look for an application of a scientific discovery made fifty years earlier by a chemist in the Academy of Sciences reflects the scant attention that historians of science have paid to the investigative activity of early eighteenth century chemistry.26... 

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