Advanced

Kinetics and equilibria for complex formation between palladium(II) and chloroacetate

Lubal, Premysl and Elding, Lars Ivar LU (2006) In Journal of Solution Chemistry 35(5). p.769-783
Abstract
Kinetics and equilibria for the formation of a 1:1 complex between palladium(II) and chloroacetate were studied by spectrophotometric measurements in 1.00 mol . dm(-3) HClO4 at 298.2 K. The equilibrium constant, K, of the reaction Pd2+ + HL reversible arrow PdL+ + H+ was determined from multi-wavelength absorbance measurements of equilibrated solutions at variable temperatures as log(10)K (298.2K) = 0.492 +/- 0.006 with Delta H-o = - 15.6 +/- 1.9 kJ . mol(-1) and Delta S-o = -43.0 +/- 6.3 J . K-1, mol and spectra of individual species were calculated. Variable-temperature kinetic measurements gave rate constants for the forward and backward reactions at 298.2 K and ionic strength 1.00 mol . dm(-3) as k(1) = 6.46 +/- 0.08 dm(3) . mol(-1) .... (More)
Kinetics and equilibria for the formation of a 1:1 complex between palladium(II) and chloroacetate were studied by spectrophotometric measurements in 1.00 mol . dm(-3) HClO4 at 298.2 K. The equilibrium constant, K, of the reaction Pd2+ + HL reversible arrow PdL+ + H+ was determined from multi-wavelength absorbance measurements of equilibrated solutions at variable temperatures as log(10)K (298.2K) = 0.492 +/- 0.006 with Delta H-o = - 15.6 +/- 1.9 kJ . mol(-1) and Delta S-o = -43.0 +/- 6.3 J . K-1, mol and spectra of individual species were calculated. Variable-temperature kinetic measurements gave rate constants for the forward and backward reactions at 298.2 K and ionic strength 1.00 mol . dm(-3) as k(1) = 6.46 +/- 0.08 dm(3) . mol(-1) . s(-1) and k(-1) = 2.91 +/- 0.03 s(-1), with activation parameters Delta H-1(not equal) = 56.55 +/- 0.75 kJ . mol(-1), Delta S-1(not equal) = -40.0 +/- 2.5 J . K-1 mol(-1), Delta H--1(not equal) = 64.42 +/- 0.50 kJ . mol(-1) and Delta S--1(not equal) = -20.3 +/- 1.7 J . K-1 . mol-1, respectively. From the kinetics of the forward and reverse processes, log(10) K = 0.346 +/- 0.007, Delta H-o = -7.9 +/- 0.9 kJ . mol(-1) and Delta S-o = - 19.8 +/- 3.0 J . K-1 . mol(-1) were derived, and these values are in good agreement with the results of the equilibrium measurements. The Specific Ion Interaction Theory was employed for determination of thermodynamic equilibrium constants for the protonation of chloroacetate (log(10) K-p(o) = 2.857 +/- 0.016) and formation of the PdL+ complex (log(10) K-o = 1.002 +/- 0.046, log(10) beta(o) = 3.859 +/- 0.048). Specific ion interaction coefficients epsilon(L-, Na+) = 0.042 +/- 0.022 kg . mol(-1), epsilon(L-, K+) = 0.081 +/- 0.021 kg . mol(-1), epsilon(PdL+, ClO4-) = 0.92 +/- 0.21 kg . mol(-1) were derived. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
LFER, thermodynamics, kinetics, equilibrium, palladium(II), chloroacetic acid, activation parameters
in
Journal of Solution Chemistry
volume
35
issue
5
pages
769 - 783
publisher
Springer
external identifiers
  • wos:000239310700009
  • scopus:33746228386
ISSN
1572-8927
DOI
10.1007/s10953-006-9019-z
language
English
LU publication?
yes
id
6c6bc3e2-4be2-498c-bf9b-100fca0c0112 (old id 399439)
date added to LUP
2007-10-09 09:58:10
date last changed
2019-02-20 04:45:27
@article{6c6bc3e2-4be2-498c-bf9b-100fca0c0112,
  abstract     = {Kinetics and equilibria for the formation of a 1:1 complex between palladium(II) and chloroacetate were studied by spectrophotometric measurements in 1.00 mol . dm(-3) HClO4 at 298.2 K. The equilibrium constant, K, of the reaction Pd2+ + HL reversible arrow PdL+ + H+ was determined from multi-wavelength absorbance measurements of equilibrated solutions at variable temperatures as log(10)K (298.2K) = 0.492 +/- 0.006 with Delta H-o = - 15.6 +/- 1.9 kJ . mol(-1) and Delta S-o = -43.0 +/- 6.3 J . K-1, mol and spectra of individual species were calculated. Variable-temperature kinetic measurements gave rate constants for the forward and backward reactions at 298.2 K and ionic strength 1.00 mol . dm(-3) as k(1) = 6.46 +/- 0.08 dm(3) . mol(-1) . s(-1) and k(-1) = 2.91 +/- 0.03 s(-1), with activation parameters Delta H-1(not equal) = 56.55 +/- 0.75 kJ . mol(-1), Delta S-1(not equal) = -40.0 +/- 2.5 J . K-1 mol(-1), Delta H--1(not equal) = 64.42 +/- 0.50 kJ . mol(-1) and Delta S--1(not equal) = -20.3 +/- 1.7 J . K-1 . mol-1, respectively. From the kinetics of the forward and reverse processes, log(10) K = 0.346 +/- 0.007, Delta H-o = -7.9 +/- 0.9 kJ . mol(-1) and Delta S-o = - 19.8 +/- 3.0 J . K-1 . mol(-1) were derived, and these values are in good agreement with the results of the equilibrium measurements. The Specific Ion Interaction Theory was employed for determination of thermodynamic equilibrium constants for the protonation of chloroacetate (log(10) K-p(o) = 2.857 +/- 0.016) and formation of the PdL+ complex (log(10) K-o = 1.002 +/- 0.046, log(10) beta(o) = 3.859 +/- 0.048). Specific ion interaction coefficients epsilon(L-, Na+) = 0.042 +/- 0.022 kg . mol(-1), epsilon(L-, K+) = 0.081 +/- 0.021 kg . mol(-1), epsilon(PdL+, ClO4-) = 0.92 +/- 0.21 kg . mol(-1) were derived.},
  author       = {Lubal, Premysl and Elding, Lars Ivar},
  issn         = {1572-8927},
  keyword      = {LFER,thermodynamics,kinetics,equilibrium,palladium(II),chloroacetic acid,activation parameters},
  language     = {eng},
  number       = {5},
  pages        = {769--783},
  publisher    = {Springer},
  series       = {Journal of Solution Chemistry},
  title        = {Kinetics and equilibria for complex formation between palladium(II) and chloroacetate},
  url          = {http://dx.doi.org/10.1007/s10953-006-9019-z},
  volume       = {35},
  year         = {2006},
}