The fundamental resolution equation or Purnell equation is used in chromatography to help relate adjustable chromatographic parameters to resolution.

Equation

where,

= Number of theoretical plates

= Selectivity Term =

The term is the column factor, the term is the thermodynamic factor, and the term is the retention factor. The 3 factors are not completely independent, but can be treated as such.

Intervention To increase resolution of two peaks on a chromatogram, one of the three terms of the equation need to be modified.

N can be increased by lengthening the column (least effective, as doubling the column will get a or 1.44x increase in resolution). Increasing also helps. This can be done by lowering the column temperature in G.C., or by choosing a weaker mobile phase in L.C. (moderately effective) Changing α is the most effective way of increasing resolution. This can be done by choosing a stationary phase that has a greater difference between and . It can also be done in L.C. by using pH to invoke secondary equilibria (if applicable).

Resolution The fundamental resolution equation is derived as follows:

For two closely spaced peaks, , and ,

so,

Where and are the retention times of two separate peaks.

Since , then

Using substitution, .

Now using the following equations and solving for and

Substituting again and you get:

And finally substituting once more and you get the Fundamental Resolution Equation:

References

Bibliography Spring 2009 Class Notes, CHM 5154, Chemical Separations taught by Dr. John Dorsey, Ph.D, Florida State University