Lecture 8

Van Deemter Equation!

Resolution
Describes how well 2 compounds are separated

1 1/2
Rs =
N (-1)
4

( )

efficiency selectivity

k =

tR-tM
tM

1+k

retention

1 < k < 10

Resolution
Describes how well 2 compounds are separated

1 1/2
Rs =
N (-1)
4
L
N=
H

( )
k

1+k

Maximize N

L
H

Resolution
L - length of column
Cannot increase indefinitely
Limited by:
Long runs times
Back pressure (LC)

H - height equivalent of a theoretical plate

Measure of Efficiency
Always want to minimize H
Getting the best performance from system

H depends on:
column parameters
mobile phase
flow rate

Described by Van Deemter

Van Deemter Equation

B
H A+
+ C

is flow rate

Van Deemter Equation

H A+

+ C

H
H min

A
B

(flow rate)

Van Deemter Equation

A term
Multipath Effect

Van Deemter Equation

A term
Multipath Effect

A Ce d p

Ce = particle shape
dp = diameter of particle

A term
Entirely dependent on column
Only important in LC

Van Deemter Equation

A term
Multipath Effect

H A
H
A

(flow rate)

Van Deemter Equation

B term
Longitudinal diffusion

Van Deemter Equation

B term
Longitudinal diffusion

DMP

DMP = diffusivity of mobile phase

B term
Inversely proportional to flow rate (fast)
Only important in GC (DMP of a gas)
Typical LC flow rate 0.2-0.5 mL/min
Typical GC flow rate 1-2 mL/min

Van Deemter Equation

B term
Longitudinal diffusion

(flow rate)

Van Deemter Equation

C term
Mass transfer

dt2

DMP

GC

LC

dp2
C

DMP

dt = diameter of tube
DMP = diffusivity of MP

dp = diameter of particles
DMP = diffusivity of MP
= tortuosity

Van Deemter Equation

C term
Mass transfer

dt2

DMP

GC

LC

dp2
C

DMP

Van Deemter Equation

C term
Mass transfer

dt2

DMP

GC

LC

dp2
C

DMP

Van Deemter Equation

C term
Mass transfer

dt2

DMP

GC

LC

dp2
C

DMP

Van Deemter Equation

C term
Mass transfer

H C
C

(flow rate)

Van Deemter Equation

GC

A+
H X

+ C
C

H
H min

A
B

(flow rate)

Van Deemter Equation

GC

+ C
C

H
H min
B

(flow rate)

Van Deemter Equation

GC

DMP

dt2
+

DMP

H
H min
B

(flow rate)

Van Deemter Equation

GC
Ideal Column (open tubular):
Small internal diameter (dt)
Use length to increase N (N=L/H)

Ideal Mobile Phase:

High diffusivity to C term and
allow higher flow rates

Van Deemter Equation

LC

H A+

+ C
C

H
H min

A
B

(flow rate)

Van Deemter Equation

LC

H A + C
C

(flow rate)

Van Deemter Equation

LC

dp2
H Ce d p +

DMP

(flow rate)

Van Deemter Equation

LC
Ideal Column (packed):
Small particles (dp)
Uniform particles (Ce and )
Cannot use length to increase N

Ideal Mobile Phase:

High diffusivity (DMP) to C term and allow higher flow rates

Van Deemter Equation

LC

dp2
H Ce d p +

DMP

Dong, M. Todays Chemist

at Work. 2000, 9(2), 46-48.

Van Deemter Equation

LC

dp2
H Ce d p +

DMP

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