Topic: Van-deemter plots for different chromatographic techniques

Course Title: Advanced chromatographic techniques

Course code: (CHEM5111)

Semester: 2nd

Program: MS Chemistry

Submitted to: Dr. Nagina Naveed

Submitted by:

Tayyaba Yaseen,

Iqra Ali,

Zarnab Akash Haider,

Aqsa Tahir

University of Education (Vehari Campus)

Van-deemter plots for different chromatographic techniques

Van-deemter plot for GC

Explanation

 For a packed GC column, Van Deemter showed that the broadening of a peak is the
summation of interdependent effects from several sources.
 For GC & OTC the factor A becomes nearly zero, so, band broadening decreases &
resolution increases.
 The term B represents longitudinal or molecular diffusion of the sample components in
the carrier gas or mobile Phase.
  In a given analysis, the sample components are fixed, and B or B/u is varied by pressure,
or flow rate of the carrier gas.
 High flow rates reduce the contribution of molecular diffusion, as this is a time-
dependent contribution, and high flow rates reduce the total analysis time.
 The term u is the average linear velocity of the carrier gas in cm/s.
Van-deemter plots for HPLC

Explanation

 Theoretical plate height is plotted versus average mobile-phase velocity.

 Uniformly sized spherical particles result in a smaller A value in the Van Deemter
equation.
 More rapid mass transport between the phases—necessary for high flow rates.
 Molecular diffusion in liquids is small, the B term is small.
 The detrimental increase in H at slow flow rates is much less pronounced than what was
in GC.

H Versus U Plots of different Particle Size

Explanation

 As particle size decreases, there is very little increase in the plate height with
an increase in the linear velocity.

 At high flow rates fast separations can be performed with little or no loss in
efficiency on the small particle columns.
 As particles get smaller, the Van Deemter H vs. u plot becomes flat at high
flow rates because smaller particles are less resistant to mass transfer (the C
term in the Van Deemter equation decreases).

Cs Versus Cm Plot
Explanation

 Cs represents to the concentration of the component in the stationary phase while C m

represents to the concentration of the component in the mobile phase.

 When a plot is drawn between Cs and Cm three types of curves (A,B and C) are obtained
as shown in the plot.

 Curve B is obtained when an equilibrium exists between the concentration of the

component in the stationary phase and concentration of the component in the mobile
phase. Straight curve shows that value of Cs/Cm is a constant known as partition constant
and an ideal symmetric peak is obtained.

 More symmetric the peak, better is the efficiency of the column and more better will be
the separation.
 Curve A is obtained when value of Cs is greater than value of Cm which shows that value
of K starts to increase from its constant value and an un-symmetric peak is obtained on
the chromatogram and this phenomenon is known as peak fronting (peak with a broader
first half and a narrower second half).
 Poor solubility of the sample i.e. its uneven distribution in the solution for examination,
contaminated column, overloading and over-packing of the column are the main causes
of peak fronting.
 This problem can be solved by reducing volume of the sample or concentration of the
solute, using pre-packed columns and cleaning the column using recommended
procedures.
 Curve C is obtained when value of Cs is less than value of Cm which shows that value of
K starts to decrease from its constant value and an un-symmetric peak is obtained on the
chromatogram and this phenomenon is known as peak tailing(peak with a broader second
half and a narrower first half).
 Secondary silanol interactions, over loading and column bed deformation are main causes
of peak tailing.
 Problem of peak tailing can be solved by using guard column, new column, reducing
sample size, using end-capped columns or working at high pH when analyzing basic
compounds(Because basic compounds don’t ionize at high or alkaline pH).