7.13.2                     Chromatography

 

Simple experiments to illustrate the techniques of paper and thin layer chromatography (preparation of plates not required) leading to an understanding of Rf values; two way chromatography.

The usefulness of the above techniques and of GLC. (the theory of chromatography is not required.)

 

Chromatography

This is an analytical technique for the sepctration of a mixture of solutes.

 Separation is achieved by the differential movement of individual solutes through a porous medium, under the influence of a moving solvent.  The degree of separation depends on four forces which operate independently of each other.

·        Rate of flow of solvent.

·        Solubility of the substance in the solvent.

·        Partition effects.

·        Adsorption effects.

 

The first two of theses are responsible for pushing the substance along the support material while the last two are responsible for retarding the movement of the substance.

Chromatography may be achieved by either a partition or adsorption mechanism.

 

Partition chromatography

This involves the separation of a mixture of substances by the partition between the moving solvent (mobile phase) and a stationary liquid (stationary phase) held on a suitable solid support.

             

Paper chromatography

Paper has associated with it moisture (10%) bound to the cellulose fibres which act as the stationary phase.  The solvent is the mobile phase.  The more soluble the component in the solvent the faster it will be washed along.

 


                                             0       0         0

 

 

 

 

 

·        Mark a pencil line about 2cm from the end of the chromatography paper.

·        Place spots of coloured dyes about 2cm apart along the line, avoiding the edges.

·        Record the original colour of each spot, in pencil, below the spot itself.

·        Wrap the chromatography paper into a cylindrical shape and clip the ends together with a paper clip or staple ( alternatively the flat sheet con be placed into a chromatography developing tank).

·        Place a small amount of a suitable solvent in a large beaker (or chromatography tank).

·        Carefully place the cylinder of chromatography paper into the beaker ensuring that the coloured spots are above the level of the solvent and that there is no contact between the cylinder and sides of the beaker.

·        Leave undisturbed until the solvent has travelled nearly to the top of the paper.

 

 

 

                                                     beaker

 

 

 

 

 

                                                     Coloured spots

                                                     Solvent level

 

 

 

 

 

 

 

 

 

 

·        Remove the paper and allow to dry before opening out flat.

                                                                                Solvent line

                                                      0         0

 

 

 

                                              0       0         0

 

 

The separated components can be obtained by cutting the paper into  strips and dissolving out each compound.

 

 

Gas-Liquid Chromatography

Here the mobile phase is an inert gas (usually helium or nitrogen) and the stationary phase is a non-volatile liquid held on a finely divided solid support.  The stationary phase is chosen according to the nature of the sample to be separated.  The material under test (either gas or volatile liquid) is injected into the apparatus and is carried by the stream of carrier gas into a long heated column packed with a porous solid  impregnated with a non-volatile liquid or oil. Gas-liquid partitioning occurs, the retention time being characteristic of a particular substance.

Detection is usually achieved by measuring the changes in thermal conductivity of the effluent gases.

 

Adsorption Chromatography

              

Separation is achieved by differences in the adsorption behaviour of substances between a moving liquid solvent and a station" solid phase.

The substances experience varying interactions with the surface of the solid adsorbent due to weak electrostatic forces.  Thus for two solute molecules A and B, if A is more strongly adsorbed it will move in the solvent more slowly than B and separation can be achieved.

 

 

Thin Layer Chromatography

              

A thin coating of an adsorbent material (silica gel, alumina A1203, cellulose, chalk) is spread evenly on a glass plate.  A solution of the mixture to be separated is spotted onto the adsorbent surface at one

 end.  The plate is then placed in a closed vessel containing an appropriate solvent so that the spotted end comes in contact with the solvent, which then moves across the adsorbent material.  The mixture separates into its components depending on the relative affinities for the adsorbent material compared with the migrating solvent.

 

Rf values

           

The movement of any substance relative to the solvent front in a given system is constant and characteristic of that substance.

The Rf value is used to express the relative distance that a substance has travelled (Rf<l).

 

            Rf=   distance substance has travelled from origin

                    distance solvent front has travelled from origin

 

 

                                      solvent front

 

                      no                        Rf (A)=

                                                          X

                  X

                                                Rf (B)= b

                                                          X

                      AO        b

 

 

 

                                      base line

 

 

Components separated from a mixture con often be detected visually as they may be coloured, but if colourless and therefore invisible further treatment will be necessary.

Fluorescence - many organic compounds fluoresce in u.v. light.

Radioactivity - detected using Geiger counter.

Chemical - colourless compounds are converted to a coloured product by treatment with a locating agent such as H2S or ninhydrin.

 

 


Two way chromatography

This is an adoption of chromatography in order to achieve better separation of the components of a mixture.  Chromatography is carried out twice with the chromatography paper being turned through 90o between the two developments.

 

 

                                       1 st separation        0

 

                                             vent 1

 

 

 

 

 

                                                                        Turn 90o

                                                                  v

 

 

                                         nd

                                        2 -1 separation

 

                                          solvent 2

 

 

From the Rf values for solvents 1 and 2 components can be identified.

 

Chromatography is used for testing the purity of a sample (and for analysis) as well as for separation.

Partition chromatography can be used for the analysis of dyes, the identification of sugars and the separation of cations e.g. Cu2+, Hg2+, Bi3+.

Thin Layer Chromatography can be used for the separation of amino acids and cations and anions e.g. Co2+, Mn2+, Ni2+.

Gas-liquid chromatography (or vapour phase chromatography) is  particularly useful for the analysis of volatile substances and is very important in the petroleum industry e.g. a gas chromatograph is attached to the process and small samples fed in for rapid analysis and results.

Volatile mixtures in the food industry, such as head space gases in wines and spirits, can also be analysed.