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Safety with Cryogenic Fluids pp 32–81Cite as

Chemical Hazards

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Part of the book series: The International Cryogenics Monograph Series ((INCMS))

Abstract

Perhaps the most common but least understood hazard is that associated with exothermic chemical reactions. Such reactions may occur with certain combinations of cryogenic fluids and with cryogenic fluids in contact with their surroundings (e.g., liquid hydrogen-solid oxygen; gaseous hydrogen-air; methane-fluorine; liquid oxygen-oil). Theoretically, these reactions can occur at any given temperature T, and pressure P, if

$$\Delta {F_{{T,P}}} = \Delta H - T\Delta S < 0$$
((4.1))

where ΔF, ΔH, and ΔS are the free energy, enthalpy, and entropy changes, respectively. This equation gives the condition for stability of a chemical system; however, it gives no information on the rate at which a reaction occurs. For many reactions this rate is determined in part by the temperature and the activation energy E. According to the Arrhenius theory,1–3 the rate of an elementary reaction is

$$w = k{e^{{ - E/RT}}}$$
((4.2))

where κ is a constant, E is the activation energy, and R is the molar gas constant. The exponential term is the fraction of active molecules with energy in excess of E.

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  1. Bureau of Mines, U.S. Department of the Interior, Pittsburgh, Pennsylvania, USA

    Michael G. Zabetakis Ph.D.

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  1. Michael G. Zabetakis Ph.D.
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© 1967 Springer Science+Business Media New York

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Zabetakis, M.G. (1967). Chemical Hazards. In: Safety with Cryogenic Fluids. The International Cryogenics Monograph Series. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-5684-2_4

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  • DOI: https://doi.org/10.1007/978-1-4899-5684-2_4

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