Efficiency of TPGC: Golay, Giddings and Method Translation

Walter Spieksma, Envantage Inc.

Method translation pursues faster, smaller GC columns. Gas diffusion (1 atm, 35C) by Fuller and CE 4. Temperature Programmed GC Resolution gain on the new column depends on sgi:
Equations for efficiency and pneumatics are evaluated for wistd

100(DFuller-DCE)/DFuller
Giddings divided TPGC elution in isothermal moves:
application in Envantage Method Translator. 5
0.2 www.envantage.com
0.7 u ( z )t rg i
Li (zone move) sg i winew
1. Gas Pressure in Capillaries 0
ki 1
Gas velocity and gas pressure in leak tight capillaries at -5 -1.0 -1.7 Sensitivity loss depends on sample reduction sr:
one temperature are related by perfect gas law: Retention time ti=t is the total of time intervals t the wistd
-10 -7.7
Pin uin Pu P( z)u( z) Poutuout [W/m2]
CH4 component i needs to elute from inlet to outlet. Capacity sli
-15 nC6 factor ki depends on isothermal equilibrium and phase sr winew
Experimental data are average velocity ( =L/t0) and head -20 ratio ki=kiEQ [Spieksma 1999]. Local velocity depends on Sample reduction is
pressure (Pgage=Pin-Patm=P). Gas pressure gradient is H2 He-19.4 N2 pressure gradient:
defined with absolute pressures P =Pin/Pout: Fuller and CE agree on H2 and N2 but differ on He. uout d std
f dc
std
Split new Areaistd
u( z) (local velocity) sr
P( z ) Pout P 2 z P 2 1 3. Efficiency of Capillary GC P z ( P 2 1)
2 d new
f dc
new
Split std Areainew
Different Height Equivalent to 1 Theoretical Plate Peak width at half height wi follows from plate height Sample load is the same at the same injection band width.
4
equations exist. HETP of our capillary GC inventor: Ni=L/Hi=8Ln(2)(ti/wi) and retention time ti=t0(ki+1): Envantage Method Translator shows the trilemma of
2 DiG Ad c 2 Bd 2f k 1 chromatography by an arrow from triangle center (1,1,1)
3
Hi u G L (Golay) wi i 8Ln(2) Li H i ( z ) (TPGC width) to (sg, rgnC6, slnc6). Compare ASTM D 6730 and Fast
u D Di u
P(z) [atm]

i D6730 by the Trenn Zahl plot of the n-paraffins ().

2 TPGC elution is an accumulation of moves Li with local
Giddings outlet HETP: Conclusions
and isothermal plate heights Hi(z) [Snijders 1995]. TPGC
1 2D u Ad Go 2
u Bd 2
is evaluated with Trenn Zahl TZ=(tn+1-tn)/(wn+1+wn)-1 of Giddings is the outlet version, Blumberg is an inlet
H i j'' f
out Go c i
(Giddings)
n-paraffins at successive carbon numbers. version of Golay HETP. Giddings zone move, Golay
u out Di DiL
0 5.Method Translation efficiency, Chapman-Enskog gas diffusion and Hagen-
0 0.25 0.5 0.75 1 and the quadratic HETP equation [Blumberg 1997]: Poiseuille are applied in the Envantage Method Translator
2
Speed gain is the reason for method translation:
z = L/L 81d c2 DiGo Pout 32 AL G u 2 u Bd f (www.envantage.com/analytical-software/).
Hi L (Blumberg) tistd t 0std
Average pressure P is the integral over the column: sgi at equal : sg References
1 1 1024 L G u 2 DiGo Pout Di tinew t 0new R.C. Reid, J.M. Prausnitz, B.E. Poling (1987) Properties of
P P( z )z Pout P 2 z ( P 2 1)z Pout / j result in similar HETP curves: Temperature program translation maintains temperatures, Gases &Liquids ISBN 0-07-100284-7
0 0 n-Hexane HnC6 = 0.300mm @ =23.8cm/s reduces times (tnew=tstd/sg) and increases ramps H. Snijders, H.G. Janssen and C.A. Cramers (1995) J.o.Chro A
GolayOut
1.2
(rnew=rstdsg) by equal speed gain. Fast retention Vol.718, p.339-355.
3 P2 1
HnC6 [mm] He @ 35C,100mx250mx0.5m DMS

L. Blumberg (1997) J.o.Hi.Res.Chro, Vol.20, p.597604.

j (Pout > 0) (James & Martin) temperatures are maintained (compare T-axes ).
2 P3 1 W. Spieksma (1999) J.o.Hi.Res.Chro, Vol.22, p.565588.
Blumberg Giddings
Hence follows James and Martin uout = P = jPout. 0.9
Laminar flow Hagen-Poiseuille velocity relation is:
j'd c2 Pgage
u (HP)
32 L G 0.6
Golay-CE
The Halasz j' gradient correction is related to j:
3 ( P 2 1)( P 1)
j' (Halasz)
4 P3 1 0.3
Halasz dependence on j follows from linear gradient
PL=(Pin+Pout)/2)=Pout(P+1)/2 and perfect gas law.
2. Diffusion in Gases 0.0
Boltzmann gas diffusion was developed into a working 23.8
0 10 20 30 40 50 60 70 80
equation independently by Chapman and Enskog: = L/t0 [cm/s]
3
0.00266 T 2 Golay HETP at outlet conditions follows from Giddings
D 2
i
G
. 2
[cm /s] (CE) rule: DG/u is constant over column length L:
P iG iG M iG 2 2
2 DiGo uout Ad c u Bd f
Collision diameter and integral of i (CH4 to nC6) and Hi L (GolayOut)
gas G (H2, He, N2) can be derived [Reid 1987]. In uout DiGo Di
cooperation with Giddings, Fuller derived a gas diffusion Giddings j'' is not required to find optimum velocity.
equation using the atom groups k in molecule i : Combine Blumberg, HP and the outlet-inlet diffusion
7 relation DiGo=PDiGi at high pressure drop P:
0.00143 T 4
[cm2/s] (Fuller)
D
i
Go
2 81DiGi j'Ad 2 Bd 2

Pout 3 v k 3 V G M iG Hi u Gi c Lf (Blumberg-HP)
32 j' u D Di
k i
2
Boltzmann reduced mass MiG is a molecular average. Blumbergs disagreement disappears by HP...