Silicic acid
Sillicic acid is the acid that forms the esters and salts called silicates and is rapidly released from inorganic silicates by hydrochloric acid. Silicic acid, however, is inherently unstable and will rapidly condense with itself with the elimination of water forming ‘dimers’, ‘trimers’ and eventually high molecular weight polymers. These polymeric aggregates grow in size until (depending on the environmental conditions, temperature, salt concentration, pH etc.) at a particular size, the hydroxyl groups on the surface of the aggregates begin to condense; the aggregates adhere to one another and the liquid gels. A somewhat complicated treatment of the gel eventually produces the so called silica gel that is extensively used in chromatography. The aggregates, called ‘primary particles’, are a network of silicon dioxide groups (actually they are better considered as a network of silicic anhydride groups) with hydroxyl groups covering the external surface. Silicon is the second most common element on the earth’s surface and the aluminum silicates represent the clays and shale’s widely present in the earths crust.
Author: RPW Scott
Book:Liquid Chromatography
Section:HPLC Stationary-Phases Silica-Gel Irregular
bonded phases were also based on silica gel. More recently, polymeric
stationary phases were introduced to provide materials that were insoluble in water
and that were stable at extremes of pH.
Silica Gel
The Preparation of Irregular Silica Gel
Silica gel is
manufactured by releasing silicic acid from a strong solution of sodium
silicate by hydrochloric acid. (Sodium silicate is prepared by heating sand at
a high temperature in contact with caustic soda or sodium carbonate).
Initially,
silicic acid is released,
Na2SiO3 +H2O +
2HCl = Si(OH)4 + 2NaCl
and then the
free acid quickly starts to condense with itself with the elimination of water
to form dimers, trimers and eventually polymeric silicic acid. The polymer
grows, initially forming polymer aggregates and then polymer spheres, a few
Angstrom in diameter. These polymeric
spheres are called primary silica particles. These primary particles
continue to grow until, at a particular size, the surface
HPLC Stationary-Phases Silica-Gel Irregular
Author: RPW Scott
Book:The Mechanism of Chromatographic Retention
Section:Retention Exclusion Silica-Gel-Preparation
enantiomorphic and, thus, optically active.
Silica, (SiO2) can be considered to be the anhydride of silicic
acid, and in its naturally occurring crystalline form, does hydrate to silicic
acid and, as a consequence, is very slightly soluble in water. However, the
hydration is very slow and it is not practical to produce silica gel, for
example, by directly hydrating quartz.
The Preparation of Silica Gel
Silica gel is
manufactured by Patrick's process which consists essentially of releasing
silicic acid from a strong solution of sodium silicate by hydrochloric acid.
(The sodium silicate is usually manufactured by heating sand at a high
temperature in contact with caustic soda or sodium carbonate
Retention Exclusion Silica-Gel-Preparation
Author: RPW Scott
Book:The Mechanism of Chromatographic Retention
Section:Retention Exclusion Silica-Gel-Preparation
Initially,
silicic acid is released,
Na2SiO3
+H2O + 2HCl = Si(OH)4 + 2NaCl
However, the
free acid quickly starts to condense with itself with the elimination of water
to form dimers, trimers and eventually polymeric silicic acid.
The
Polymerization of Silicic Acid
The polymer
continues to grow, initially forming polymer aggregates and then polymer
spheres, a few Angstrom in diameter. These polymeric
spheres are called primary silica particles. The primary particles
continue to grow until, at a particular size, the surface silanol groups
(hydroxyl groups attached to the surface silicon atoms) on adjacent primary
polymer particles, start condense. This condensation causes the primary particles to adhere to one another and at this
stage the
Retention Exclusion Silica-Gel-Preparation
Author: RPW Scott
Book:Liquid Chromatography
Section:HPLC Stationary-Phases Silica-Gel Structure
The Structure of Silica Gel
The matrix of
the primary silica gel particle consists of a core of silicon atoms
joined together with oxygen atoms by siloxane bonds (silicon-oxygen-silicon
bonds). On the surface of each primary particle some residual, uncondensed
hydroxyl groups from the original polymeric silicic acid remain. These residual
hydroxyl groups confer upon silica gel its polar properties. These hydroxyl
groups react with the silane reagents to form bonded phases. The silica surface
is quite complex and contains more than one type of hydroxyl group, strongly
bound or 'chemically' adsorbed water and loosely bound or 'physically adsorbed'
water. There are three types of hydroxyl group. The first is a single hydroxyl
group attached to a silicon atom which has three siloxane bonds joining
HPLC Stationary-Phases Silica-Gel Structure