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Perturbation chromatography in chemically reactive systems
Author(s) -
Deans H. A.,
Horn F. J. M.,
Klauser Gernot
Publication year - 1970
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690160320
Subject(s) - perturbation (astronomy) , chemistry , stoichiometry , kinetics , chemical equilibrium , chemical reaction , chemical kinetics , thermodynamics , chromatography , physics , classical mechanics , quantum mechanics , organic chemistry
A one‐dimensional column is considered in which a number of chemical reactions with arbitrary kinetics may take place among an arbitrary number of components. Initially, the column is in complete chemical and physical equilibrium. A localized small perturbation is introduced in the column at time t = 0. It is shown that, in general, this initial perturbation separates into a definite number of peaks which move with different velocities. Each peak broadens according to an asymptotic relation, depending on a characteristic dispersion coefficient. If n is the number of components, m the number of independent reactions, and σ the number of equations of state to be considered, there are n‐m‐σ peaks. These peaks do not correspond to single substances as in classical chromatography, but each peak has an eigencomposition. The velocities of the peaks are derived as functions of stoichiometry and equilibrium data. The dispersion coefficients depend, in addition, on the kinetics of the chemical reactions and on the rate of mass transfer. Thus, perturbation chromatography offers a means of determining both equilibrium and rate data. The theory is illustrated by means of two examples.