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The interaction of small particles and thin films of metals with gases. I - A brief review of the early stages of oxide formation

Existing work on gas-solid reactions making use of thin film technologies is reviewed. The discussion concentrates on two major areas of gas-metal interactions: chemisorption and the early stages of oxidation of metals (characterized by a non-volatile reaction product) and catalytic surface reactions (featuring volatile reaction products). A brief survey of oxide formation on metals is presented. Here it is of importance to distinguish between reactions on continuous thin film substrates and reactions on particulate deposits. Small particle-gas interactions also affect the nucleation, growth and sintering processes of thin films. It is shown that various combinations of UHV and high resolution electron microscopy techniques, which include in situ experimentation, can provide the appropriate tools for studying angstrom particle chemistry.

Poppa, H.

Effect of the Electrostatic Field due to the Surface Monolayer Metal Atoms on the Dissociation of Homonuclear Diatomic Gases in Gas-Metal Surface Reactions

The present paper examines the role of an electrostatic field generated by the outermost monolayer of metal ions prior to gas adsorption in aiding the dissociation of homonuclear diatomic gas molecules. The interaction of five homonuclear diatomic gases, Cl 2 , F 2 , H 2 , N 2 and O 2 , with several pure metals are examined using Coulomb’s law to calculate the attractive and repulsive forces between the electrons or ions in the gas molecule and the free surface metallic electrons or ions assuming a Bohr model. These calculations demonstrate that the total energy of the electrostatic fields from the metals can exceed the molecular binding energies of Cl 2 , F 2 , and O 2 at some distance from the metallic surface thereby suggesting that these gases interact primarily with the metallic surface in their atomic states after molecular bond dissociation prior to reaction. In contrast, H 2 and N 2 gases do not dissociate prior to reaching the metal surface due to the fact that the effective charge of the gas ions is less than the total electron charge at the outermost electronic shell. The present results correlate linearly with the electrochemical series standard reduction potential as well as with the Pauling electronegativity for several metals.

Gas-metal reactions