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Migration Rates of Solutes

The effectiveness of a chromatographic column in separating two solutes depends in part on the relative rates at which the two species are eluted. These rates in turn are determined by the rations of the solute concentrations in each of the two phases. Distribution Constants All chromatographic separations are based on differences between the mobile phase and stationary phases. For the solute species A, the equilibrium involved is described by the equation A (mobile) A (stationary) The equilibrium constant as K C= where (a A) S = activity of solute A in the stationary phase (a A) M = activity of solute A in the mobile phase We often substitue c S , the molar analytical concentration of the solute in the stationary phase etc etc. Hence, we get: K C= cS cM ( a A )S ( a A )M K C for this reaction is called a distribution constant, which is defined

Retention times The time t M between sample injection and the appearance of the non-retained species peak is called the dead or void time. The dead time (void time) t M is the time it takes for an unretained species to pass through a chromatographic column. All components spend this amount of time in the mobile phase. Separations are based on the different times t S that components spend in the stationary phase. The dead time provides a measure of the average rate of migration of the mobile phase and is an important parameter in identifying analyte peaks. The time required for the analyte zone to reach the detector after sample injection is called the retention time and is represented by the symbol t R . The analyte has been retained because it spends a time t S in the stationary phase. The retention time is then tR = tM + tS

Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3

The Retention Factor, k The retention factor is an important experimental parameter that is widely used to compare the migration rates of solutes on columns. For solute A, the retention factor k A is defined as
kA =

(K A V S ) VM

The equation rearranges to k A= t R t M t S = tM tM

The retention factor k A for solute A is related to the rate at which A migrates through a column. It is the amount of time a solute spends in the stationary phase relative to the time it spends in the mobile phase. Ideally, separations are performed under conditions in which retention factors for the solutes in a mixture lie in the range 1 to 5. Retention factors in gas chromatography can be varied by changing the temperature and the column packing. The Selectivity Factor The selectivity factor of a column for the two solutes A and B is defined as a= KB KA
K A is the

where K B is the distribution constant for the more strongly retained species B and constant for the less strongly held or more rapidly eluted species A. a= kB kA (t R )B t M (t R )A t M


Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3