Migration rate of solutes in a chromatographic separation:

 

 

Average linear velocity of the solute

          where tR is the retention time

 

Average linear velocity of the mobile phase

              where tm  is the dead volume

or retention time of unretained peak

 

 


Distribution constant and retention time

 

Solute velocity =

mobile phase velocity x

fraction of time spent in stationary phase

 

and

 

fraction of time spent in stationary phase

 

= u  x

 

moles of solute in mobile phase

total moles of solute

 

 

 

 

substitute into expression for K

 

    

 

but these parameters are hard to measure

 

 

 


The Capacity Factor, k'

 

defined as:

 

 

so now

 

substituting equations for v and u

 

 

and rearranging:

 

 

all of which can be measured experimentally.


Separation:  The Selectivity Factor, a

 

easier to measure:

 

 

 

substituting  

 

 

so the difference in retention time leads to separation, and it is related to the k' of each compound

Effect of Phase Thickness on a Column