Actinide complexation kinetics: rate and mechanism of dioxoneptunium (V) reaction with chlorophosphonazo III

PDF Version Also Available for Download.

Description

Rates of complex formation and dissociation in NpO{sub 2}{sup +}- Chlorophosphonazo III (2,7-bis(4-chloro-2-phosphonobenzeneazo)-1,8- dihydroxynapthalene-3,6-disulfonic acid)(CLIII) were investigated by stopped-flow spectrophotometry. Also, limited studies were made of the rates of reaction of La{sup 3+}, Eu{sup 3+}, Dy{sup 3+}, and Fe{sup 3+} with CLIII. Rate determining step in each system is an intramolecular process, the NpO{sub 2}{sup +}-CLIII reaction proceeding by a first order approach to equilibrium in the acid range from 0.1 to 1.0 M. Complex formation occurs independent of acidity, while both acid dependent and independent dissociation pathways are observed. Activation parameters for the complex formation reaction are {Delta}H=46.2{+-}0.3 kJ/m ... continued below

Physical Description

22 p.

Creation Information

Fugate, G.; Feil-Jenkins, J.F.; Sullivan, J.C. & Nash, K.L. December 1, 1996.

Context

This report is part of the collection entitled: Office of Scientific & Technical Information Technical Reports and was provided by UNT Libraries Government Documents Department to Digital Library, a digital repository hosted by the UNT Libraries. More information about this report can be viewed below.

Who

People and organizations associated with either the creation of this report or its content.

Sponsor

Publisher

Provided By

UNT Libraries Government Documents Department

Serving as both a federal and a state depository library, the UNT Libraries Government Documents Department maintains millions of items in a variety of formats. The department is a member of the FDLP Content Partnerships Program and an Affiliated Archive of the National Archives.

Contact Us

What

Descriptive information to help identify this report. Follow the links below to find similar items on the Digital Library.

Description

Rates of complex formation and dissociation in NpO{sub 2}{sup +}- Chlorophosphonazo III (2,7-bis(4-chloro-2-phosphonobenzeneazo)-1,8- dihydroxynapthalene-3,6-disulfonic acid)(CLIII) were investigated by stopped-flow spectrophotometry. Also, limited studies were made of the rates of reaction of La{sup 3+}, Eu{sup 3+}, Dy{sup 3+}, and Fe{sup 3+} with CLIII. Rate determining step in each system is an intramolecular process, the NpO{sub 2}{sup +}-CLIII reaction proceeding by a first order approach to equilibrium in the acid range from 0.1 to 1.0 M. Complex formation occurs independent of acidity, while both acid dependent and independent dissociation pathways are observed. Activation parameters for the complex formation reaction are {Delta}H=46.2{+-}0.3 kJ/m and {Delta}S=7{+-} J/mK (I=1.0 M); these for the acid dependent and independent dissociation pathways are {Delta}H=38.8{+-}0.6 kJ/m, {Delta}S=-96{+-}18 J/mK, {Delta}H=70.0{+-} kJ/m, and {Delta}S=17{+-}1 J/mK, respectively. An isokinetic relationship is observed between the activation parameters for CLIII complex formation with NpO{sub 2}{sup +}, UO{sub 2}{sup 2+}, Th{sup 4+}, and Zr{sup 4+}. Rates of CLIII complex formation reactions for Fe{sup 3+}, Zr{sup 4+}, NpO{sub 2}{sup +}, UO{sub 2}{sup 2+}, Th{sup 4+}, La{sup 3+}, Eu{sup 3+}, and Dy{sup 3+} correlate with cation radius rather than charge/radius ratio.

Physical Description

22 p.

Notes

INIS; OSTI as DE97002721

Source

  • Other Information: PBD: Dec 1996

Language

Item Type

Identifier

Unique identifying numbers for this report in the Digital Library or other systems.

  • Other: DE97002721
  • Report No.: ANL/CHM/PP--87026
  • Grant Number: W-31-109-ENG-38
  • DOI: 10.2172/436450 | External Link
  • Office of Scientific & Technical Information Report Number: 436450
  • Archival Resource Key: ark:/67531/metadc686158

Collections

This report is part of the following collection of related materials.

Office of Scientific & Technical Information Technical Reports

What responsibilities do I have when using this report?

When

Dates and time periods associated with this report.

Creation Date

  • December 1, 1996

Added to The UNT Digital Library

  • July 25, 2015, 2:20 a.m.

Description Last Updated

  • Dec. 16, 2015, 10:41 a.m.

Usage Statistics

When was this report last used?

Yesterday: 0
Past 30 days: 0
Total Uses: 2

Interact With This Report

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

Fugate, G.; Feil-Jenkins, J.F.; Sullivan, J.C. & Nash, K.L. Actinide complexation kinetics: rate and mechanism of dioxoneptunium (V) reaction with chlorophosphonazo III, report, December 1, 1996; Illinois. (digital.library.unt.edu/ark:/67531/metadc686158/: accessed September 26, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.