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SHORTCOMINGS OF THE PLATE

THEORY

•H=

• PLATE THEORY DISREGARDS THE KINETICS OF MASS

TRANSFER;
• ASSUMES KD IS NOT AFFECTED BY PRESENCE OF OTHER
COMPOUNDS
• NEGLECTS THE DIFFUSION OF SOLUTE IN THE MOBILE PHASE
FROM ONE PLATE ANOTHER
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The plate theory successfully
accounts for the Gaussian
shape and rate of movement
down a column,
but fails to account for peak
broadening in a mechanistic
way.

It does not account for analyte

interaction with the stationary
phase

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 Observation from the
chromatogram

 1. Peak width increases

with retention time/
(volume)
 2. The peak width is
increases with residence
time
 3. and inversely related
to the mobile phase
velocity

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Van Deemter equation- rate theory

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The curves
illustrates that
there is an
‘optimal linear
velocity’ that
provides the
highest efficiency
(lowest HETP)…..

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 The Multipath Term (A)

The paths of individual analyte molecules will

differ as they take different routes thru the
spaces between particles (non-uniform column
packing) ≡ eddy diffusion
• A term depends on particle size distribution,
The smaller the particle size, the smaller the A term

Smaller particle sizes yield higher overall column

efficiencies and a much wider range of usable flow rates.
 -Longitudinal Diffusion (B)

H = A + B/u + Cu
Accounts for the spreading of molecules in both
directions of the band-center along the length of
the column (back and sideways diffusion of the
solute in the mobile phase) driven by the
concentration gradient.
Molecular diffusion (B)

􀀹 affected by temperature and pressure

􀀹 not important in LC – low diffusion

Coefficient

􀀹 inversely affected by mobile phase

Mass Transfer (C)

H = A + B/u +(Cs + Cm)u

Resistance to mass transfer in both the stationary

phase and the mobile phase prevents the existence
of instantaneous equilibrium.
 Stationary phase mass transfer …
different analyte molecules spend
different lengths of time in the
stationary phase, giving rise to
band-broadening.

mobile phase mass transfer..band-broadening due to

differences in the rate of diffusion of the solute
molecules between the mobile phase outside the
pores of the support(flowing mobile phase) to the
mobile phase within the pores of the support
(stagnant mobile phase).
Resistance to mass transfer (C):

Directly related to mobile phase flow rate

􀀹 Affected inversely by the diameter of

particles or inner diameter of capillary
Column

􀀹 Lower at higher temperatures (viscosity)

Conclusions:

Minimum value for H is achieved

when:
􀂾 stationary phase thickness is minimal

􀂾 column packed with the smallest particles

􀂾 capillary columns have the smallest

internal diameter

􀂾 mobile and stationary phases have low

viscosity and high diffusion coefficient
Zone Broadening and Column Efficiency
van Deemter Equation - Summary
H = A + B/u +(Cs + Cm)u
Zone Broadening and Column Efficiency
Relationship Between Plate Height and Column
Variables - van Deemter Equation
H = A + B/u + Cu H = A + B/u +(Cs + Cm)u
Important Chromatographic Terms