Complex formation between iodine and the triphenyl compounds of the group VA elements.
Item
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Title
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Complex formation between iodine and the triphenyl compounds of the group VA elements.
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Identifier
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AAI9130395
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identifier
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9130395
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Creator
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Zhang, Yingru.
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Contributor
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Adviser: Seymour Aronson
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Date
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1991
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Physical | Chemistry, Analytical | Chemistry, Organic
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Abstract
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The iodine complexes of triphenylamine, triphenylphosphine, triphenylarsine and triphenylstibine were studied in the solid state and in organic solution.;In the solid state, the iodine complexes are stable over wide ranges of iodine concentration and are prepared by mixing the powder components. Triphenylstibine forms a liquid complex. By means of a solid state electrochemical technique, we have determined the Gibbs free energy of complex formation. The EMF data were obtained using solid electrochemical cells with an AgI electrolyte of the type:{dollar}{dollar}\rm \sp{lcub}(-){rcub} \ Pt\mid Ag \mid AgI \mid I\sb2(c) \mid Pt\ \sp{lcub}(+){rcub}{dollar}{dollar}where I{dollar}\sb2{dollar}(c) represents either pure or complexed iodine. The results indicate that the bond strengths between iodine and triphenyl compounds are in the order of P {dollar}>{dollar} As {dollar}>{dollar} Sb {dollar}>{dollar} N.;The electrical conductivities were also measured using the Van der Pauw four-probe technique for solid complexes and a two-probe method for liquid complexes. Activation energies were calculated from the temperature dependence of the conductivity of the complexes.;Electrochemical experiments were performed which demonstrate that conduction in these complexes is primarily electronic.;In organic solution, an electrochemical technique was employed to study the ionization of the iodine complexes of Ph{dollar}\sb3{dollar}N, Ph{dollar}\sb3{dollar}P, Ph{dollar}\sb3{dollar}As, Ph{dollar}\sb3{dollar}Sb and pyridine.;EMF measurements were made in 1, 2-dichloroethane on concentration cells of the type: Pt {dollar}\mid{dollar} I{dollar}\sb{lcub}2{rcub}{dollar}, R, TEAI(c) in 1,2-DCE {dollar}\parallel{dollar} I{dollar}\sb2{dollar}, R in 1, 2-DCE {dollar}\mid{dollar} Pt where TEAI represents tetraethylammonium iodide, R is a symbol for organic compounds. In conjunction with electrical conductivity measurements and UV-VIS spectrophotometric analysis, several different ionization mechanisms were proposed depending on the chemical nature and concentration ratio of the reactants. Equilibrium constants were calculated from the EMF data for the various ionization steps.;A {dollar}\sp{lcub}31{rcub}{dollar}P-NMR study was also performed to investigate the triphenylphosphine-iodine charge-transfer complex formation and ionization reactions.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
