Kinetics of the Chromium (II) Reductions of Glycinato- and Related Amino Acidato-ethylenediamine and Amine Complexes of Cobalt (III) PDF Download
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Author: Robert D. Williams
Publisher:
ISBN:
Category : Chromium
Languages : en
Pages : 244
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Author: Robert D. Williams
Publisher:
ISBN:
Category : Chromium
Languages : en
Pages : 244
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Author:
Publisher:
ISBN:
Category : Dissertations, Academic
Languages : en
Pages : 818
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Vols. for 1973- include the following subject areas: Biological sciences, Agriculture, Chemistry, Environmental sciences, Health sciences, Engineering, Mathematics and statistics, Earth sciences, Physics, Education, Psychology, Sociology, Anthropology, History, Law & political science, Business & economics, Geography & regional planning, Language & literature, Fine arts, Library & information science, Mass communications, Music, Philosophy and Religion.
Author: University Microfilms International
Publisher: Ann Arbor, Mich. : University Microfilms International
ISBN:
Category : Reference
Languages : en
Pages : 712
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Author: Dennis A. Estep
Publisher:
ISBN:
Category : Chemical kinetics
Languages : en
Pages : 102
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Author:
Publisher:
ISBN:
Category : Dissertations, Academic
Languages : en
Pages : 844
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Author: American Chemical Society. Committee on Professional Training
Publisher:
ISBN:
Category : Chemical engineering
Languages : en
Pages : 1188
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Author: Robert J. Balahura
Publisher:
ISBN:
Category : Chormium
Languages : en
Pages : 0
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The chromium(II) reduction of a series of pentaammine- cobalt(III) complexes has been studied. A classification into inner- or outer-sphere paths has been made and the position of attack of the reductant on the ligand determined. The oxygen-bonded complexes of formamide, N,N-dimethylform- amide, dimethylsulfoxide, and urea as well as the nitrogen bonded N-cyanoguanidine complex are reduced by means of an outer-sphere mechanism. On the other hand ligand transfer was shown to occur in the reduction of (NH[subscript 3])[subscript 5]CoNHCHO[superscript 2+], (NH[subscript 3])[subscript 5]CoNCNH[superscript 2+], (NH[subscript 3])[subscript 5]CoO[subscript 2]CNH[subscript 2][superscript 2+], (NH[subscript 3])[subscript 5]CoO[subscript 2]CC[subscript 6]H[subscript 4]CN[superscript 2+], and (NH[subscript 3])[subscript 5]CoNCO[superscript 2+]. Both outer- and inner-sphere paths operate in the reduction of the nitrile bonded 4-cyanophenol complex, the inner-sphere path comprising 20% of the overall reaction. For the reduction of the terephthalonitrile complex a classification into an inner- or outer-sphere path cannot be made/ and an outer-sphere electron transfer to the ligand is postulated as the rate-determining step. A large part of the work has been concerned with the characterization of the complexes and Chapter III describes the spectroscopic measurements undertaken as well as the chemical reactions of some of the complexes. The acid dissociation constant of the N isomer of formamidopentaamine- cobalt(III), cyanamidopentaamminecobalt(III), and the nitrile bonded 4-cyanophenol have been determined. The protonation equilibrium constant for carbamatopentaammine- cobalt(III) was also obtained. A kinetic study of the acid hydrolysis of isocyanatopentaamminecobalt(III) to form hexaamminecobalt(III) and carbon dioxide was carried out. The acylation of the cyanamide and 4-cyanophenol complexes was also studied. The results of the kinetic studies of the chromium(II) reductions indicate a possible correlation between the reduction rate and the half-wave potential for the reduction of the free ligand. The studies have led to the following generalizations regarding electron transfer reactions: (1) attack of reductant at a coordinated atom does not occur, (2) the atom attached to chromium(II) in the transition state must have two lone pairs of electrons, and (3) the reducibility of the complexed ligand plays an important role in the detailed mechanism for the transfer of the electron.
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Author: Janet Louise Laird
Publisher: National Library of Canada
ISBN: 9780315195219
Category : Chromium ions
Languages : en
Pages : 0
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The aquation and chromium(II) reduction reactions of a variety of sulfonamidopentaamminecobalt(III) complexes have been studied in 1 M LiClO4/HClO4. The rate law for the aquation of (NH35CoNHSO2NH22+ has the form -dln[complex]/dt = k2h[H+]/(Ka+[H+]), and the aquation kinetics of (NH3)5CoNHSO2R2+, (R = C6H4CH3-p, C6H4NO2-p), are consistent with the same rate law if Ka ” [H+]. The unusually large rate constants obtained, (e.g., k2h = 1.41 x 10-2 s-1 at 25°C, for (NH3)5CoNHSO2NH22+), are attributed to N-protonation of (NH3)5CoNHSO2R2+ followed by facile release of the neutral ligand. The chromium(II) reduction of (NH3)3CoNH2SO32 produces (H2O)3CrOSO2NH22+. The nitrogen and oxygen bonded linkage isomers are reduced at indistinguishable rates. Reduction of (NH3)5CoNHSO2NH22+ is competitive with aquation, and (NH3)5(2oNH2SO2NH23+ is reduced much more rapidly than the deprotonated species. The chromium(III) product is too unstable to be fully characterized, but a kineticspectrophotometric analysis indicates that ligand transfer does occur. Similar kinetic results were found for (NH3)5CoNHSO2C6H4CH3-p2+, but the chromium(III) product could not be detected. The kinetic trends for the pentaamminecobalt(III) complexes with SO42-, NH2SO3- and SO2(NH2)2 are discussed, and a bridged outer sphere mechanism is suggested to be most consistent with the results. Chromium(II) reduction of (NH3)5CoNHSO2C6H4NO2-p2+ involves reduction of both the Cobalt(III) and the NO2 group. Detection of a p-nitro radical complex has been accomplished by stopped-flow spectrophotometry. A step-wise mechanism consistent with the complex absorbance changes has been proposed and many of the specific rate constants have been measured. Rapid reduction of the nitro group to hydroxylamine occurs concurrently with reduction of the Co(III), the major amount of Co2+ coming from reduction of the p-nitroso radical intermediate. Further reduction of the hydroxylamine derivative is much slower. Similar results were found for the chromium(II) reduction of the free ligand, minus those reactions involving reduction of the metal.
Author: John S. Cardwell
Publisher:
ISBN:
Category : Chromium
Languages : en
Pages : 142
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Author: Nihon Kagakkai
Publisher:
ISBN:
Category : Chemistry
Languages : en
Pages : 1470
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