Author

Karel

Date of Award

12-1984

Degree Name

Master of Arts

Department

Chemistry

First Advisor

Dr. Ralph K. Steinhaus

Second Advisor

Dr. Dean W. Cooke

Third Advisor

Dr. H. Dale Warren

Access Setting

Masters Thesis-Open Access

Abstract

The kinetics of the reaction of aquonickel (II) ion with N'N'-dimethlethylenediaminediacetic acid has been studied at 25°C and 0.1M iconic strength over a pH range of 6.0 to 9.3 using stopped-flow techniques. Formation reactions in all cases were first-order in Ni (II) and in ligand. The formation rate constant for the protonated and unprotonated species were evaluated and compared to their theoretical value. The rate-determining step is shown to be ring closure. A comparison of this system with other studies involving complexation of nickel (II) confirm the magnitude of the internal conjugate base effect and also shows a correlation between and the internal conjugate base rate enhancement and the structural environment of the nitrogen donor atom.

The exchange reaction between copper (II) and N,N'- dimethylethylenediaminediacetatonickelate (II) was studied at 25°C over a four fold variation was shown to be first-order in NiMEDDA and zero-order in copper. This zero-order dependence shows the inability of DMEDDA to unwrap from nickel and twist into a conformation suitable for bonding to copper prior to the rate limiting step.

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