In 1913, the German chemist Max Bodenstein first put forth the idea of chemical chain reactions. If two molecules react, not only molecules of the final reaction products are formed, but also some unstable molecules which can further react with the parent molecules with a far larger probability than the initial reactants. (In the new reaction, further unstable molecules are formed besides the stable products, and so on.)
In 1918, Walther Nernst proposed that the photochemical reaction between hydrogen and chlorine is a chain reaction in order to explain what is known as the quantum yield phenomena. This means that one photon of light is responsible for the formation of as many as 106 molecules of the product HCl. Nernst suggested that the photon dissociates a Cl2 molecule into two Cl atoms which each initiate a long chain of reaction steps forming HCl.[1]
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In 1923, Danish and Dutch scientists Christian Christiansen and Hendrik Anthony Kramers, in an analysis of the formation of polymers, pointed out that such a chain reaction need not start with a molecule excited by light, but could also start with two molecules colliding violently due to thermal energy as previously proposed for initiation of chemical reactions by van' t Hoff.[2]
Christiansen and Kramers also noted that if, in one link of the reaction chain, two or more unstable molecules are produced, the reaction chain would branch and grow. The result is in fact an exponential growth, thus giving rise to explosive increases in reaction rates, and indeed to chemical explosions themselves. This was the first proposal for the mechanism of chemical explosions.
A quantitative chain chemical reaction theory was created later on by Soviet physicist Nikolay Semyonov in 1934.[3] Semyonov shared the Nobel Prize in 1956 with Sir Cyril Norman Hinshelwood, who independently developed many of the same quantitative concepts.[2]
As can be explained using the steady-state approximation, the thermal reaction has an initial rate of fractional order (3/2), and a complete rate equation with a two-term denominator (mixed-order kinetics).[4][5]
A nuclear chain reaction was proposed by Leo Szilard in 1933, shortly after the neutron was discovered, yet more than five years before nuclear fission was first discovered. Szilárd knew of chemical chain reactions, and he had been reading about an energy-producing nuclear reaction involving high-energy protons bombarding lithium, demonstrated by John Cockcroft and Ernest Walton, in 1932. Now, Szilárd proposed to use neutrons theoretically produced from certain nuclear reactions in lighter isotopes, to induce further reactions in light isotopes that produced more neutrons. This would in theory produce a chain reaction at the level of the nucleus. He did not envision fission as one of these neutron-producing reactions, since this reaction was not known at the time. Experiments he proposed using beryllium and indium failed.
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