ELSEVIER Journal of Chromatography A, 736 (1996) 21-30
JOURNAL OF
CHROMATOGRAPHY A
Study of the physico-chemical properties of some packing materials
II. General properties of the particles
a b c
Hong Guan " , Georges Guiochon a'b'*, Dorothy Coffey , Evelyn Davis d,
Kim Gulakowski d, David W. Smith a
"Department of Chemistry, The University of Tennessee, Knoxville, TN 37996-1600, USA
"Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6120, USA
CMetals and Ceramics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6064, USA
~Micromeritics, Norcross, GA 30093-1877, USA
Received 9 October 1995; revised 12 December 1995; accepted 13 December 1995
Abstract
Scanning electron microscopy reveals the shape and illustrates the particle size distribution of four different brands of
spherical silica particles used in preparative chromatography (C ~8-bonded Kromasil, Vydac, YMC, and Zorbax). Pycnometry
provides a direct estimate of the unaccessible volume fraction in a column. The retention volumes of benzene in
dichloromethane and of uracil in methanol provide two independent estimates of the total column porosity which are in
excellent agreement. Within 2 to 3%, the sum of these two fractional volumes is equal to unity, as expected, in spite of a
possible disagreement between the two sets of measurements due to the fact that the C,s bonded chains are collapsed during
the pycnometric measurements and are dissolved in the mobile phase during the chromatographic measurements. Finally,
estimates of the volume fractions of the column occupied by the bonded layer and the silica skeleton for two of the packing
materials suggest that the closed pore porosity is negligible (1 to 2% at most).
Keywords: Stationary phases, LC; Scanning electron microscopy; Preparative chromatography
I. Introduction
The reproducibility of packed columns for chro-
matography has always been a problem of serious
concern for practitioners [1]. So far, the reproducibil-
ity of the thermodynamic properties has attracted
most of the attention. Progress made over the years
in the manufacturing processes used to prepare silica
particles and to derivatize them when needed has
*Corresponding author. Address for correspondence: Department
of Chemistry, University of Tennessee, Knoxville, TN 37996-
1600, USA.
resulted in the present situation. Batch-to-batch
repeatability of chromatographic separations per-
formed with a given brand of packing is quite
reasonable for neat silica and alkyl-bonded silica
materials. There are still some significant fluctuations
of the retention factors, much smaller variations for
the separation factors. The results are generally less
satisfactory for some nonconventional bonded
phases, in which case there may be considerable
batch-to-batch variations in the yield of the bonding
reactions. Hence, the repeatability of some otherwise
difficult separations is not assured [2].
Until recently, the repeatability of the other col-
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