ABSTRACT
I. SUMMARY 180
II. INTRODUCTION 181
III. THE STOCHASTIC APPROACH
OF CHROMATOGRAPHY 183
A. General Aspects 183
B. Basic Stochastic Model 185
IV. PEAK SHAPE FEATURES AND EXPERIMENTAL
ERRORS IN THE DETERMINATION OF THE
RETENTION FACTOR 189
A. Peak Splitting Effect 190
B. Peak Tailing Effect 191
C. Stochastic Bias Effect 192
D. Injection Effect 194
E. Unretained Tracer Selection Effect 195
V. EQUILIBRIUM CONDITIONS
IN CHROMATOGRAPHY 195
VI. DISCUSSION 197
A. Peak Splitting 198
B. Peak Tailing 199
C. Stochastic Bias 201
D. Injection 201
E. Number of Analyte Molecules 202
F. Selection of the Holdup Time Marker 206
VII. CONCLUSION 206
ACKNOWLEDGMENTS 208
GLOSSARY 208
REFERENCES 210
APPENDIX A 213
APPENDIX B 221
APPENDIX C 226
APPENDIX D 228
APPENDIX E 230
We report a detailed study concerning the correspondence between
separations by chromatography, dynamic quantities coming from
single-molecule measurements at the interfaces, and phase partition
equilibrium by using the unifying approach of the stochastic descrip-
tion. The fundamental hypotheses allowing establishing the proper
links between the three experimental techniques are discussed, and
the full correspondence between the different quantities is deter-
mined from basic principles. The expressions of the errors on the
retention factor which are intrinsically linked to the separation
process, and which arise from peak splitting, peak tailing, stochastic
bias, injection step, and number of the analyte molecules, are derived
under general conditions and discussed in detail. Reference is made
to the growing area of microsystems or nanosystems and chip tech-
nology, with numerical examples. How to determine the impact of
single-molecule dynamics observations on the chromatographic peak
shape of the experimentally observed sorption time distribution and,
in general, of the behavior of the species at the stationary phase
(surfaces, interfaces) is pointed out.
