Principles of chromatography

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Stronger attraction to the stationary phase means slower movement; stronger preference for the mobile phase means faster movement.

Two phases separate a mixture

Chromatography separates components because they interact differently with a stationary phase and a mobile phase. Adsorption to the stationary phase slows movement; solubility in the moving phase favors travel. Thin layer chromatography (TLC) separates spots on a plate; column chromatography separates bands that leave the column at different times.

The same components separate into spots on a plate or bands in a column.
Plate and column chromatography Khan Academy · CC BY-NC-SA 4.0 · Original image ↗
TermDefinition
Mobile phase or carriersolvent moving through the column
Stationary phase or adsorbentsubstance that stays fixed inside the column
Eluentfluid entering the column
Eluatefluid exiting the column (that is collected in flasks)
Elutionthe process of washing out a compound through a column using a suitable solvent
Analytemixture whose individual components have to be separated and analyzed
A column labeled with eluent, analyte, stationary phase, mobile phase, and collected eluate.
Parts of a chromatography column Khan Academy · CC BY-NC-SA 4.0 · Original image ↗

Follow the bands

Load the sample, pass eluent through the stationary phase, and collect successive fractions of eluate. Components that spend less time retained emerge first. Retention time measures how long a component takes to reach the detector or column outlet.

Successive stages of column chromatography with different colored components leaving at different times.
Collecting separated components Khan Academy · CC BY-NC-SA 4.0 · Original image ↗

Original comparison of methods

TechniqueStationary phaseMobile phaseBasis of separationNotes
*Paper chromatographysolid (cellulose)liquidpolarity of moleculescompound spotted directly on a cellulose paper
*Thin layer chromatography (TLC)solid (silica or alumina)liquidpolarity of moleculesglass is coated with thin layer of silica on which is spotted the compound
*Liquid column chromatographysolid (silica or alumina)liquidpolarity of moleculesglass column is packed with slurry of silica
Size exclusion chromatographysolid (microporous beads of silica)liquidsize of moleculessmall molecules get trapped in the pores of the stationary phase, while large molecules flow through the gaps between the beads and have very small retention times. So larger molecules come out first. In this type of chromatography there isn’t any interaction, physical or chemical, between the analyte and the stationary phase.
Ion-exchange chromatographysolid (cationic or anionic resin)liquidionic charge of the moleculesmolecules possessing the opposite charge as the resin will bind tightly to the resin, and molecules having the same charge as the resin will flow through the column and elute out first.
Affinity chromatographysolid (agarose or porous glass beads on to which are immobilized molecules like enzymes and antibodies)liquidbinding affinity of the analyte molecule to the molecule immobilized on the stationary phaseif the molecule is a substrate for the enzyme, it will bind tightly to the enzyme and the unbound analytes will pass through in the mobile phase, and elute out of the column, leaving the substrate bound to the enzyme, which can then be detached from the stationary phase and eluted out of the column with an appropriate solvent.
Gas chromatographyliquid or solid supportgas (inert gas like argon or helium)boiling point of the moleculessamples are volatilized and the molecule with lowest boiling point comes out of the column first. The molecule with the highest boiling point comes out of the column last.

*Fall under the category of ‘Liquid Chromatography’

In ideal size exclusion chromatography, separation depends on pore access rather than specific binding. In gas chromatography, volatility and stationary-phase interactions both influence retention; boiling point alone is not always enough to predict order.

Polarity and solvent choice

Paper chromatography and TLC make separated spots visible, as with leaf pigments. Keep the starting spot above the solvent level; mark the solvent front before it evaporates.

Leaf pigments separate into colored bands on chromatography paper.
Separating leaf pigments Khan Academy · CC BY-NC-SA 4.0 · Original image ↗

In normal-phase chromatography, a polar stationary phase retains polar molecules more strongly. A more polar mobile phase generally competes more effectively for those sites and moves retained compounds farther or elutes them sooner. Reversed-phase chromatography uses a nonpolar stationary phase and a polar mobile phase. Changing the mobile phase during a run is gradient elution.

Solvent polarity changes between hexane and acetonitrile, altering the movement of retained compounds.
Changing the mobile phase Khan Academy · CC BY-NC-SA 4.0 · Original image ↗

Calculate the retention factor

Rf = distance traveled by the component ÷ distance traveled by the solvent front. Measure both from the starting line. Rf is dimensionless and normally lies between 0 and 1. Compare values only under matching stationary-phase and solvent conditions.

TLC spots C, A, and B travel 1, 2, and 3 centimeters while the solvent front travels 5 centimeters.
Distances used to calculate Rf Khan Academy · CC BY-NC-SA 4.0 · Original image ↗
ComponentDistance travelled by the component (cm)Distance travelled by the solvent (cm)Retention factor (Rf) of the component
C15RfC = 1/5 = 0.2
A25RfA = 2/5 = 0.4
B35RfB = 3/5 = 0.6

In this example, B travels farthest and has the largest Rf; C is retained most strongly and has the smallest Rf. A larger TLC Rf usually corresponds to faster elution in a comparable column system.

22 terms, alphabetically ordered

Adsorption
Association of a molecule with a surface, such as the stationary phase in chromatography.
Affinity chromatography
Separation by specific binding between a target and an immobilized ligand, followed by selective release.
Analyteanalytes
A substance being measured or separated within a sample; the source table uses the term for the mixture under analysis.
Antibodyantibodies
An immune protein that specifically binds a molecular target called an antigen.
Centimetercm
A unit of length equal to one hundredth of a meter.
Chromatography
Separation of mixture components by their different interactions with a stationary phase and a moving mobile phase.
Eluate
The fluid that leaves a chromatography column, containing any eluted sample components.
Eluent
The fluid introduced into a chromatography column.
Elutionelute · eluted
Removal of a component from the stationary phase by the flowing mobile phase.
Enzymeenzymes
A biological catalyst that speeds a reaction without being consumed. Most enzymes are proteins.
Gas chromatographyGC
Separation of volatile, thermally stable compounds carried through a column by a gas. Retention depends on volatility and stationary-phase interactions.
Gradient elution
Changing mobile-phase composition during a separation, for example increasing salt or organic solvent concentration.
Ion exchange chromatographyIEX · ion-exchange chromatography
Separation by net charge through reversible binding to an oppositely charged resin.
Mobile phasecarrier
The moving fluid that carries a sample through a chromatographic system.
Normal-phase chromatographynormal phase chromatography
Chromatography with a polar stationary phase and a less polar mobile phase. More strongly adsorbed polar components are retained longer.
Retention factorRf · RfC · RfA · RfB
In TLC, the distance traveled by a sample spot divided by the distance traveled by the solvent front, both measured from the origin. RfC, RfA, and RfB denote the values for components C, A, and B.
Retention timeretention times
The elapsed time between sample injection and detection of a component leaving the column.
Reversed-phase chromatographyreverse-phase chromatography
Chromatography with a nonpolar stationary phase and a polar mobile phase. Hydrophobic components tend to be retained more strongly.
Size exclusion chromatographySEC · size-exclusion chromatography · gel filtration chromatography
Separation by hydrodynamic size using porous beads. Large molecules access fewer pores and usually elute before small molecules.
Solubility
The extent to which a substance can dissolve in a solvent.
Stationary phaseadsorbent
The material that remains fixed in a chromatographic system.
Thin layer chromatographyTLC · thin-layer chromatography
A method that separates sample spots as solvent moves along a thin stationary layer, often silica, on a plate.

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