Buback, M.; Morick, J.
Equilibrium Constants and Activation Rate Coefficients for Atom Transfer Radical Polymerizations at Pressures up to 2 500 Bar
Macromolecular Chemistry and Physics 2010, 211, 2154-2161.
 

Equilibrium constants, KATRP, and activation rate coefficients, kact, have been measured up to 2 500 bar and used for estimating reaction volumes, ΔVR, and activation volumes, ΔVact, respectively. Quantitative analysis of binary copper-ligand-alkyl bromide initiator systems, without monomer being present, has been carried out in a solution of acetonitrile by high-pressure online-FT-NIR/VIS spectroscopic monitoring of the CuII ligand species. The numbers for ΔVR and ΔVact are close to each other and reflect the characteristics of ligand complexation. Whereas ΔVR is almost insensitive to the type of initiator, the absolute KATRP clearly depends on this alkyl bromide species.