The correct study of diffusive time evolution of concentration boundaries i
n n-component systems requires the use of all the (n-1)(2) diffusion coeffi
cients defined by Fick's law. However, to simplify the analysis, the so-cal
led pseudo-binary approximation is very often used. This can lead to very m
isleading results. On the other hand, the possibility to predict the diffus
ional behaviour of rt-component systems from the properties of correspondin
g binaries and from the knowledge of the solute-solute cross-interactions s
hould be a very important goal. If no "chemical" solute-solute interactions
are present in solution, the diffusion coefficients depend only on the "hy
drodynamic" or volumetric solute-solute interactions. This contribution, wh
ich is mostly reflected in the cross-diffusion coefficient values, is alway
s present and assumes an important role in solutions containing macromolecu
lar solutes. It is then very important in modelling the diffusion phenomena
in systems where a protein can crystallise in the presence of polymeric so
lutes as precipitating agents. The present paper is devoted to the study of
the hydrodynamic effects on the diffusion coefficients of poly(ethylenegly
col) samples, which is one of the widely precipitating agents used in the p
rotein precipitation. A predictive model to evaluate the diffusion coeffici
ents in the presence of the only hydrodynamic effect was applied with good
success to the systems presented and to a literature system NaCl-lysozyme-w
ater. (C) 2000 Published by Elsevier Science S.A.