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(rate theory)
A. Introduction
1. Band-broadening is a general term used to describe
the overall dispersion or widening of a sample peak as
it passes through a separation system.
Chromatographic column
Packed-bed system
Open-tubular system
Packed-bed system
Packed-bed system
1
-(x2/4Dt)
Cx = C0 (
)e
2 Dt
2 = 2Dt = 2D(
HL = (2)L/L = 2Dm/u
Packed bed
HL = (2)L/L = 2Dm/[u(1+p/e)]
Larger the Dm, larger the HL!
Larger the u, smaller the HL !
L
)
u
p: intraparticle porosity
e: interparticle porosity
Dm: solute diffusion coefficient in
mobile phase.
u: linear velocity of flow
Eddy
Diffusion
Profile of flow
HE =
dp1+x
(Dm)x
ux
Hs = qs k
(1+k)2
df2
u
Ds
k:capacity factor
df: thickness of stationary phase
Ds:solute diffusion coefficient in
stationary phase.
qs:shape factor for the stationary
phase coating coating (2/3 for a
thin layer on the support).
u: linear velocity of flow
HM = f(k)
(3)
dp2
Dm
H R = HS + HM
Less effect on GC
Dm
(1+p/e) u
+ 2 dp1+x
Htot =
u
D
dp
df
k
HL
ux
k
+ qs
x
(1+k)2
(Dm)
HE
HS
df2
u + f(k)
Ds
+
HM
dp2
Dm
Dm
(1+p/e) u
+ 2 dp1+x
ux
k
+ qs
x
(1+k)2
(Dm)
df2
u + f(k)
Ds
dp2
Dm
= ? (inflexion?)
d2(Htot)
(minimum or maximum?)
=
?
d2(u)
Good news: there is a minimum for Htot.
Htot = A + 2*(BC)1/2
uopt = (B/C)1/2
tR = k tM tR = (k+1) tM
Rs =
tR2 tR1
(Wb2+Wb1)/2