"All flows, all changes". Heraclides"It's not difficult to know, it is difficult to get familiar". Skovoroda The theory of gas chromatography, presented by
equation of Van Deemter,
(1) shows that for each chromatographic separation there exists an optimal flow rate above and below which
column efficiency is reduced.
In practice,
linear speed of
sample zone moved by
carrier gas, is changed continuously and increases as it approaches
outlet, which results in a non-effective use of a part of
column.
In this case equation (1) characterizes
optimal separation process only in that section of
chromatographic column through which
sample passes at an optional speed.
In equation (1) are constant values and is
speed of
moving zone of
sample which changes continuously in time. Thus equation (1) gets
following form:
(2) where is
speed of
sample at a distance from
beginning of
column and changes - increases - toward
outlet. This shows that HETP is not always optimal in all sections of
chromatographic column. Let be
length of
chromatographic column,
pressure at
inlet of
column and
pressure at
outlet of
column,
distance of a point on
chromatographic column from its inlet. It is evident that pressure at point on
column can be determined from
correlation
The flow rate at any point on
chromatographic column depends on pressure at that point, as well as on
inlet pressure and
outlet pressure of
column. But
pressure at any point on
column depends on
inlet pressure and
outlet pressure of
chromatographic column and on
distance from
column inlet. Thus
flow rate at any point on
column in case of fixed physical parameters of
chromatographic column can be considered as a function of pressure at this point and at
ends and of
distance of this point from
column inlet;
Consequently
whole process in
chromatographic column is characterized by a multiple of equations (3).
When at
inlet and outlet of
column
pressure is kept constant, each section of
chromatographic column, through which
sample zone moves, is characterized by its equation from multiple (3).
However
linear speed of
sample zone moving with
carrier-gas can be kept constant by programming
pressure gradient movement along
column in time, realizing
function: pressure - location - time by keeping constant
pressure difference ∆ p at
ends of
chromatographic column during
whole cycle of
analysis (Russia Patent "Chromatograph of A. S. Hayrapetyan").
The sample travels through
chromatographic column in time
where is
length of
chromatographic column and
optimal speed of
sample zone.
The pressure at
inlet and outlet of
chromatographic column, undergoing a change at equal intervals of time, is expressed by
where - sample injection time, and - elution time.
We mark by
the sections of
chromatographic column travelled by
sample zone with an optimal velocity of
carrier-gas at
corresponding moments of time,