Цепные реакции: самоподдерживающиеся процессы в химии и физике

Self amplifying chain of events
chain reactions in chemistry and physics
A chain reaction is a sequence of reactions where a reactive product or by product causes additional reactions to take place. In a chain reaction, positive feedback leads to a self amplifying chain of events. Chain reactions are one way that systems which are not in thermodynamic equilibrium can release energy or increase entropy in order to reach a state of higher entropy. For example, a system may not be able to reach a lower energy state by releasing energy into the environment, because it is hindered or prevented in some way from taking the path that will result in the energy release. If a reaction results in a small energy release making way for more energy releases in an expanding chain, then the system will typically collapse explosively until much or all of the stored energy has been released. A macroscopic metaphor for chain reactions is thus a snowball causing a larger snowball until finally an avalanche results ("snowball effect"). This is a result of stored gravitational potential energy seeking a path of release over friction. Chemically, the equivalent to a snow avalanche is a spark causing a forest fire. In nuclear physics, a single stray neutron can result in a prompt critical event, which may finally be energetic enough for a nuclear reactor meltdown or (in a bomb) a nuclear explosion. Numerous chain reactions can be represented by a mathematical model based on Markov chains.

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. In 1923, Danish and Dutch scientists J. A. 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. Semyonov shared the Nobel Prize in 1956 with Sir Cyril Norman Hinshelwood, who independently developed many of the same quantitative concepts.

An avalanche breakdown process can happen in semiconductors, which in some ways conduct electricity analogously to a mildly ionized gas. Semiconductors rely on free electrons knocked out of the crystal by thermal vibration for conduction. Thus, unlike metals, semiconductors become better conductors the higher the temperature. This sets up conditions for the same type of positive feedback—heat from current flow causes temperature to rise, which increases charge carriers, lowering resistance, and causing more current to flow. This can continue to the point of complete breakdown of normal resistance at a semiconductor junction, and failure of the device (this may be temporary or permanent depending on whether there is physical damage to the crystal). Certain devices, such as avalanche diodes, deliberately make use of the effect.

Examples of chain reactions in living organisms include excitation of neurons in epilepsy and lipid peroxidation. In peroxidation, a lipid radical reacts with oxygen to form a peroxyl radical (L• + O2 → LOO•). The peroxyl radical then oxidises another lipid, thus forming another lipid radical (LOO• + L–H → LOOH + L•). A chain reaction in glutamatergic synapses is the cause of synchronous discharge in some epileptic seizures.