Kinetics and Mechanisms of Rapid Reactions in Solution
{'Code': '03090005', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'Raymond Mackay', 'PO_EMAI': None, 'PO_PHON': None}
This project is in the Inorganic, Bioinorganic and                              Organometallic Chemistry Program. The project is concerned with                 the development of a new technique called pulsed-accelerated-                   flow spectroscopy for the measurement of the rates of very fast                 irreversible chemical reactions in solutions. A key feature of                  the method is the variation of flow velocity to resolve mixing                  processes from chemical rate processes. The present capability                  of the technique allows the study of reactions with half-lives                  as short as 4 microseconds, or about 1000-fold faster than can                  be studied by stopped-flow techniques. The new technique allows                 the study of a large number of important reactions which were                   previously too fast to measure.                                                                                                                                 The design of the pulsed-accelerated-flow spectrometer will be                  modified in an effort to reduce the volume of solution required                 for a rate measurement and to allow the measurement of                          half-lives even shorter than 1 microsecond. The effects of flow                 velocity on mixing and on light scattering due to differences                   in refractive index of reactants and solvents will be                           determined. A major effort will be the study of rapid non-metal                 reactions, with emphasis on the mechanisms of halogen cation                    (X+) transfer from nitrogen, oxygen and other halogens to a                     variety of nucleophiles. Acid or base catalysis of these                        reactions will be investigated. The effect of initial halogen                   bond strength, the basicity of the oxidant, and the                             nucleophilicity of the reductant on relative rates will be                      determined. The mechanisms of breakpoint clorination will be                    investigated. Additional studies of Ni(III) complexes, of the                   kinetic advantage of inner-sphere bridging, and of other fast                   electron-transfer and metal ion substitution reactions will be                  pursued also.
{'FirstName': 'Dale', 'LastName': 'Margerum', 'PI_MID_INIT': 'W', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Dale W Margerum', 'EmailAddress': 'margerum@purdue.edu', 'NSF_ID': '000399949', 'StartDate': '01/01/1988', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
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{'Code': '1966', 'Text': 'SYNTHETIC INORGANIC'}
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