On-line chromatographic analysis

As early as 1903-1906 a Russian botanist Mikhail Tsvet (Lecturer in the Warsaw University)
performed experiments trying to separate pigments of plants. Using a solvent, petroleum
ether, he washed the pigments through a vertical glass tube filled with a powder-like
absorbent, calcium carbonate. As the result of this procedure, he obtained a series of coloured
absorption bands. He first used a term ‘chromatography’ to describe this method. Word
‘chromatography’ consists of two words ‘chromatos’ (in Greek language means ‘colour’) and
‘grapho’ (in Greek language means ‘writing’), and means ‘colour writing’. By coincidence,
the surname ‘Tsvet’ in Russian language means ‘colour’.

Chromatography methods are classified regarding to the types of moving and stationary
phases according to Figure 7.1. (from Considine D. M. Process Instruments and Controls
Handbook. McGraw-Hill Book Company, Sydney, 1985, p. 6.170).

Chromatography

Liquid Chromatography Gas Chromatography

Liquid moving phase Gas moving phase

Liquid-Liquid Gas-Liquid
Chromatography Chromatography

Liquid stationary Liquid stationary

phase phase

Liquid-Solid Gas-Solid
Chromatography Chromatography

Solid (adsorbent, Solid (adsorbent)

ion-exchange) stationary phase
stationary phase

Figure 7.1. Classification of chromatography methods.

Physical absorption principles for separating of various components from a mixture of

chemical substances form the basis of chromatography (see Fig. 7.2). A gas mixture 1 to be
analysed is carried through a tube or column 2 by an inert carrier gas (nitrogen, helium) 3.
The gas mixture and the carrier gas form the moving phase. The column is filled (packed)
with materials 4, the stationary phase, which will absorb gases. Different components of the
gas mixture are delayed for varying increments of time. After the column, the separated gases
5 pass through a gas detector (flame ionisation detector, or thermal conductivity detector) 6.
This detector develops a signal 7, which then is transformed to the chromatogram 8. Using

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School of Pharmacy and Medical Sciences
Process Instrumentation, IL6
Lecturer: Dr. Alexander Badalyan
this chromatogram we can determine the type of a component and its quantity. In order to
achieve better separation of components from various mixtures different types of packing
materials should be chosen. The absorption of components by the stationary phase is highly
dependent on the operational conditions. Therefore, temperature, flowrate and pressure of a
carrier gas, sample valve timing, and detector sensitivity should be carefully controlled.

Chromatographs are widely used for composition measurements of gaseous and liquid
mixtures. Usually they are complex laboratory equipment. Modern on-line chromatography
systems for continuous, repetitive and fully automatic gas analysis have been developed, and
in principle have all essential elements inherent to laboratory-type equipment. Fig. 7.3
schematically shows an operational principle of an on-line gas-chromatograph.

1
3 2 4 5 6 7 8

Figure 7.2. Schematic of a gas-chromatograph (gas-solid chromatography).

A sample of a gas mixture 1 is withdrawn continuously from a process unit 2 and through a
shutoff valve 3, filter 3a (for removing of particulate matter) and pressure regulator 4 (for
reducing pressure to a lower constant value) circulates through a sample conditioning unit 5.
After the sample conditioning unit the stream enters the process 6 through a shutoff valve 7 in
the point of a lower pressure compared with the sample withdrawal point. The sample
conditioning unit allows to calibrate the gas-chromatograph with the synthetic calibration
blend from a container 8, through a pressure regulator 9, and to control flowrate. A carrier gas
(nitrogen, helium) is supplied from a cylinder 10, and its pressure is controlled by a pressure
regulator 11 and a pneumatic control section 12. An analyser 13 contains separating columns,
flame ionisation and/or thermal conductivity detector(s) and a temperature control unit. A
metering pump, which is placed in the sample conditioning unit, injects a small sample of an
already conditioned gas mixture into the separating column, which is placed in the analyser.
An electronic module 14 stores analytical programs in RAM and controls functions of the
analyser. Analytical data are transferred from the electronic module to a data processor 15,
where they are converted to analog signals. These signals are transmitted to a bar graph
recorder16 and a number of trend recorders 17. A host computer 18 controls all actions of the
chromatograph, receives results, alarm messages, stores application programs. A real-time
chromatogram is printed on the printer 19. Here are several values of parameters of a
chromatograph:

temperature in the temperature control unit - 40 to 200 C;

accuracy of temperature control - 0.2 C;
total length of separating columns - 10 m;
diameter of separating columns - 3 mm;

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School of Pharmacy and Medical Sciences
Process Instrumentation, IL6
Lecturer: Dr. Alexander Badalyan
 flowrate of a carrier gas - 40 to 160 cm3/min;
volumes of samples of gas mixtures - 0.5, 1, 2, 4 cm3;
volumes of samples of liquid mixtures - 0.004, 0.008, 0.032 cm3;
pressure of a gas carrier - 400 kPa;
output signal - 4 to 20 mA.
An output signal from a gas-chromatograph is usually used as an input signal for a controller,
which changes either process temperature or pressure or flowrate, etc., to bring a product
composition to the desired value.

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School of Pharmacy and Medical Sciences
Process Instrumentation, IL6
Lecturer: Dr. Alexander Badalyan
 11 16
17

12

10
14
13
18
15
2

1 3 3a 4 5 9

19
6 7

Figure 7.3. On-line chromatographic system.

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School of Pharmacy and Medical Sciences
Process Instrumentation, IL6
Lecturer: Dr. Alexander Badalyan