-

Resolution Column Efficiency

P. Sandra,

Laboratory of Organic Chemistry, University of Gent, Krijgslaan 281 (S4), 8-9000 Gent, Belgium

Equation (25) can be simplified to

In a previous contribution in this fundamentals Section of the Journal [l],the

contribution of the column efficiency N,
the separation factor u and the retention
factor ktopeak resolution was discussed
The key equation
optimization

for

H=:

+ CMUt CsU

(26)

and the malor sources of solute spreading

in capillary columns are:

separation

B longitudinal diffusional spreading

C, resistance to mass transfer in the
mobile phase

shows that peak resolution is proportional to the square root of the plate number
N Dividing the column length L by the
plate number N gives us the column
length of one plate.
L

H=-N

(24)

The plate height H is also called the

Height Equivalent to One Theoretical
Plate (HETP) This is a theoretical concept indicating that length of the column
in which there is perfect equilibrium of
the solutes between the mobile and the
stationary phase
For a given columnlength the shorter the
plate height H, the higher the plate
number N, and the better the separation
or resolution R, The H- value is a measure
for the zone spreading (band broadening) during the elution process and is a
function of the carrier gas velocity U The
relation H-U was derived for packed
column GC by Van Deemter, Zuiderweg,
and Klinkenberg [2]and adapted to capillary columns by Golay (31

DM diffusion coefficient in the mobile

phase (DGfor gas IS also used)
Ds diffusion coefficient in the stationary
phase (DLfor liquid is also used)
r, column radius
0 1989 Dr. Alfred Huethig Publishers

df average film thickness of the

stationary phase
k the retention factor

Cs resistance to mass transfer in the

stationary phase

The Golay equation is applicable to the

capillary columns nowadays used in
everday work. For very long columns
(>50 m) and/or columns with smallinternal diameter (< 0.2 mm), factors have to
be included to correct for the compressibility of the mobile phase. The reader is
referred to [4-61 for more details in this
respect. Moreover,eq. (25) is onlyvalid for
partition chromatography. For adsorption chromatography, 1.e. porous layer
open tubular (PLOT) columns-Porapak,
alumina, molecular sieves-consult ref.

'31.

H (m)

The graphical representation of the effect

of the mobile phase linear velocity U on
the plate height His shown in Figure 1
and

BtifDMt,
CMt if r, t and/or DMJ-,
CS t if dft and/or Ds J-,
the influence of k will be
discussed later.

The optimummobilephasevelocity (&)

that corresponds to the minimum plate
is indicated
height (Hmln)

Figure 1
Computer reconstructed H Z plot ( d f = 1 km).

B term: D M = 0.2 cmVs hydrogen.

C,term: k=IO,r,=O.O125cm.
CLterm: dt= 1 X 10-4 cm dimethyl silicone.
Ds=3.3 X 10-6 cm2Is (at 85%).
D, and Ds were calculated from experimental
curves.

fcmls)

Journal of High Resolution Chromatography

273

Fundamentals

Figure 2

Computer reconstructed H - i plot (df=0.25 pm).

Cs<< Cy.For parameters see Figure 1,df=0.25
X 10-4 cm dimethyl silicone.

In the practice of CGC different situations

may arise. The most important ones are:
1) The resistance to mass transfer in the
mobile phase ( CM)controls H
(Figure 2)
2) The resistance to mass transfer in the
stationary phase (Cs) controls H
(Figure 3)

ii (cm / s)

3) Both CM and Cs contribute to band

broadening, as is the case in Figure 1
Emphasis w11 be placed on situations 1
and 2

C, Controls H.
Cs can be neglected for columns with a
thin film or a large p value (> 100).The p
value or phase ratio is defined as:
Figure 3
Computer reconstructed H-G plot (df = 5 pm).
CS>> CM. For parameterssee Fig. 1, df :5 X 10-4
cm dimethyl silicone.

VM volume of mobile phase in the

column
Vs volume of stationary phase in the
column
and for capillary columns is equal to

Both the column radius and the film

thickness have to be considered
Ignoring the Cs term in eq. (25) and (27)
gives

=r
J,=

For k 00, H,,,

diameter d,.
+

Hmm = rc

=19145r

1 + 6 k + Ilk2

and for k

3(1+k)z

On the other hand, the corresponding Gpt

deducedfromeqs (25)and(28)becomes

=&

274

10

20

LO

30

50

(33)
1 + 6 k + Ilk2
VOL. 12, MAY 1989

m:

,,-40.JmK

1,

60

70

80

90

100

ii (cm I s)

approaches the column

(32)
For thin film columns, H,,, is indepen
dent of the diffusion coefficient in the gas
phase and thus Hmlnis equal for nitrogen,
helium, or hydrogen as carrier gas

Gpt

(31)

i+6ki- ilk2

2.1

DM
~

(34)

rC

kbpt
is proportional to the diffusitivity in
the gas phase and inversely proportional
to the column radius. The DM values for
nitrogen, helium, and hydrogen are in the
ratios 1:2.5:4.In practical CGC on thin film
columns, hydrogen is the best choice as

the analysis time is reduced by a factor of

4 compared to nitrogen while the sensitivity is increased by the same order.
When hydrogen is not allowed for safety
reasons helium must be used.
Some experimental H-U curves for
columns varying in internal diameter are
shown in Figure 4. All columns were
coated with the same coating solution
(0.33% w/v dimethyl silicone in n-pentane) and thus have the same p value
(297).
Journal of High Resolution Chromatography

Fundamentals
Hmin(experimenta1) and Uopt can be deduced.
Hmln(theoret:,-al) is calculated from eq. (31).

Figure 4

H (mm>

0.88 111111

Experimental H-G curves for columns with different i d ' s . H was calculated for n-dodecane at
100OC. Carrier gas was hydrogen.

k is the retention factor of n-dodecane

[es.(111.
The coating efficiency (CEo/o)

0.70 mm

CE% =

Hmin(theoretica1)

x 100%

(35)

Hmin(expenmenta1)

is a measure of how well a column has

been coated or how homogeneously the
stationary film has been deposited.
Values for CP/o can be as high a s 95 to
100% for thin apolar dimethyi silicone
coatings. Conclusions about the value of
a capillary column drawn from the
coating efficiency are meaningful only if
band broadening is controlled solely by
the chromatographic process, 1.e. a
(extra-column) = 0. Split injection is
preferred for measuring CE%.On the
other hand, if the CEO/, of a capillary
column has been calculated under
optimized conditions, i.e. split injection,
column outlet close to the flame in FID,
the impact of extra column bandbroadening can be evaluated under other
instrumental conditions, e g. on-column
injection and ECD detection.

0.512 mm

0.
0.6

0.4

7
0.18 mm

Table 1

From the data in Figure 4and Table 1,the

following conclusions can be drawn:

Data for columns in Figure 4.

1.d.
(mm)

L
(m)

Hmln

Hmin

CE

df

exp. (mm)

theor (mm)

(cm/s)

(To)

(Pm)

0 For thin film columns (large p values)

0.18
0.27
0.51
0.70
0.88

37
60
58
50
49

0.19
0.27
0.49
0.71
0.88

0.18
0.24
0.46
0.66
0.78

45
32
25
16
14

94
89
93
86
88

0.15
0.23
0.43
0.59
0.74

diameter [eq. (32)].For commercially

available FSOT columns, the Hmlnvalues,
maximum number of plates per meter
and minimum length needed for 100,000
plates can be calculated (Table 2).
The drop in efficiency with increasing
internal diameter can easily be compensated by increasing the column length by
the same factor.

Table 2
Characteristics for FSOTcolumns coated with thin films.
dc

(mm)

0.05
0.10
0.18
0.22
0.25
0.32
0.63

Hmin (mm)

N/m

L for 100,000plates

0.05
0.10
0.18
0.22
0.25
0.32
0.53

20.000
10.000
5.556
4.545
4.000
3.125
1.887

5m
10 m
18 m
22 m
25 m
32 m
53 m

The characteristics of the columns are

listed in Table 1
In the table, Hmln(expenumenta~)
is the value
deduced from Figure 4
The H-U curves were recorded by inlecting a solution of n-dodecane together
with methane at a n inlet pressure PIThe
plate number is calculated by e q (6)
Journal of High Resolution Chromatography

N=2$(

H,,, is indeed proportional to the column

=16 ($
__
=554

)
6
$
(

The H and U-values are then calculated

from eqs (24)and (18) t M is the retention
time of methane which is not retained at
100C. The pressure is varied between PI
and P, and the corresponding H and U
values are plotted From the curve,

Gpt decreases with increasing internal diameter [eq (34)]At Elmln, for the
same column length, the larger the
column diameter, the longer the analysis
H
time This is also obvious from e q (21),
increases and U decreases
0

A longer residence time in the column

corresponds to greater band broadening
The sensitivity thus also decreases a s a
function of the column diameter
0 The slope of the H-U curve is much

steeper for wide bore columns To obtain

good efficiency, one must work close to
the optimal gas velocity This is not the
case for narrow bore columns
VOL. 12,MAY 1989

275

Fundamentals

Experimental H-U and TZ-U plots are

given for various carrier gases in Figure
5

The experimental data fit the theory perfectly.

rbpt H2= 40 cm/s, GptHe = 27 cm/s, Gpt
N 2 = 1 2 cm/s

To record TZ-U curves, a solution of

n dodecane and n-tridecane was analyzed Equation (22)canthenbe applied The
column was 20 m X 0 27 mm 1 d coated
22 pm df&methyl
was
measured on n-tridecane at 100C

Noteworthy that the

for nitrogen
to %pt
much steeper Working
therefore a must It is, however, obvious
from the curves that helium and prefer-

TZ

Figure5
Experimental H-ii and T Z - i plots as
function of the carrier gas. Column:
20m X 0.27mmi.d.,df=0.22pmdimethy1 silicone.Temperature: 100C, k =
11 for n-tridecane.

ably hydrogen should be used. For hydrogen the velocity can be increased to
values for above Gptwithout loosing too
much resolution power (Figure 5B).

C,Controls H
For thick film (low p value) columns the
Cs term can no longer be ignored
and
Depending on the film thickness (df)
the diffusivity in the stationary phase
( D s ) ,CSbecomes more and more important (Figure 1) and finally completely
governs H,,, (Figure 3)

and thus Hilnn t if dft

H,,, t if DM t
H,,, 1 if DS t
H,,, 1 if k t (This will be discussed in depth in the next
article in this series )

0.2 1

- 1 . L

H (mm)

H (m>

20 LO 60 80 100 120
G (cm/ s)

0 20 10 60 80 100 1;

TZ

22

a*.H2

1.2
1.0

1.2-

This should mean that for very thick film

columns, H,,, is independent of the
column radius1 This is indeed the case
when Ds is very small (seefurther) On the
other hand, Gptis inversely proportional
the thicker the film, the lower Gpt
to df,

N2

0.8-

0.4 0.6

L-

a21

0 10 20 30 LO 50

0 10 20 30 LO 50

0 10 20 30 LO 50

ii (cm? s)

Figure 6

Experimental H-u and TZ-li curves for a thick film column. Column: 15 m X 0.32 mm i.d.,
df:5 pm dimethyl sili~one.Temperature:85~C,
k = l 1 forn-octane and k=21 for n-nonane.

Table 3

Experimental H-U and 72-Ucurves have

been recorded on a column 15 m X 0 32
mm i d coated with 5 pm dimethyl silicone [9] The curves are represented in
Figure 6A for nitrogen and hydrogen for
n-octane (k= 10 5) and in Figure 6B,for
n-nonane (k= 21) Temperature of the
column was 85OC The TZ-U plots are
shown in Figure 6C Table 3 lists the
and corresponding
measured H,,, , kpt,
TZvalues

Experimental data on a thick film column.

N2
k

H,,, (mm)
rbpt

(cm/s)

10.5
0.68
6

TZ

276

21
0 46

7
22

VOL. 12, MAY 1989

From these data, the following conclusions can be drawn:

H2

10.5
0.96
14

21
069
185
17 5

0 In both cases (Nzand H2) Hmlnismuch

higher than for thin film columns For thin

film columns, the efficiency is only
slightly affected by the capacity ratio
Journal of High Resolution Chromatography

Fundamentals

This is not the case for thick film columns,

H,,, decreases with increasing capacity
ratio [eq (36)] The chromatographic
performance of the 5 pm column compar
ed to a thin film column IS only 50% fork=
10 5 using nitrogen, 32% fork= 10 5 using
hydrogen, 65% for k = 21 using nitrogen.
and 43% fork= 21 using hydrogen These
data do not really reflect the value of a
thick film column for practical CGC The
TZ value per meter for a conventional
capillary column is 2 2 1 TZ/m, for the
thick film column at Gpt this value is
1 4 1 5 TZlm for nitrogen (70%) and
1 1-12 TZ/m for hydrogen (56%) Com
pared to nitrogen, use of hydrogen at Qpt
(15-20 cm/s for the K s consideredl)
reduces the TZ value to 80% but the
analysis time is still roughly 2 5 times
shorter Figure 6C also reveals that the
efficiency foi nitrogen at the Gpt for
hydrogen is approximately equal to the
efficiency for hydrogen (crossing point of
the two curves)

An important parameter for thick film

columns, is the diffusitivity in the liquid
phase [lo].Figure 8 shows computerreconstructed H-Cplots for 0.32 mm and
0.53 mm i.d. columns coated with 3 pm
dimethyl silicone and 3 pm diphenyl
(50%) dimethyl (50%) silicone.

Table 4 summarizes the contributions of

B, C,, and Cs for various film thicknesses,
diffusion coefficients Ds, and carrier
gases for a compound with retention
factor 10.

References
[ I ] P Sandra, HRC 12 (1989) 82

[Zl J J. V a n Deemter, F J Zuiderberg, and

A. Klinkenberg, Chem. Eng Sci 5 (1956)
271
131 M. J. E Golay in "Gas Chromatography".
Ed D. Desty, Butterworths,London (1958)
p. 36

141 J C. Giddings, S L. Seager,L. R. Stuchl. and

G. H Stewart, Anal. Chem 32 (196O;i 58.

0.53 nun
diMe

(51 J. C Sternberg and R E.Poulsen, Anal

Chem 36 (1964) 58.

0.32 mm
diMe

161 C. A. Cramers, F A Wynheymer, and J. A

Rijks, HRC & CC 2 (1979) 329

[7] L S Ettre, in "Open Tubular Columns in

Gas Chromatography", Plenum Press,
NewYork (1965) p. 108.

Gptis roughly half the Qptof thin film

columns for both carrier gases

0 The slopes of the curves are of course

much steeper than for thin film columns
but, contrary to thin film columns, the
curves flatten with increasing k values
The slopes of the curves are completely
governed by the CScontribution

The efficiency drop a s function ofincreasing film thickness is further illustrated by

a comparison (Figure 7) of the TZ value
(n-dodecaneln-tridecane)determined at
a fixed flow rate of 2 ml/min hydrogen for
a series of 20 m X 05 mm columns coated
with different film thicknesses ( 0 1 0 2
0 4 , 0 8 , 1 2 2, and 3 pm)

Figure 7
TZ

TZvalue as function of film thickness.Columns:20m X 0.5 mm i.d.

TZ values between n-dodecane
and n-tridecane.

Figure 8
Computer reconstructed H-G plots for 0.32mm
i.d.and0.53mmi.d.columnscoatedwith3 pmof
dimethyl siliconeand diphenyldimethyl silicone.
Values see text.

181 R C M d e Nils and J d e Zeeuw, in "Proc.

5th Int Symp Cap. Chrom" Ed J Rqks,
Elsevier, Amsterdam (1983) p 11
191 p Sandra, I Temmerman, and
stappe, HRC & CC 6 (1983) 501

Ver-

1101
F David. M Proot a n d P Sandra.HRC &CC
>
8 (1985) 551
,

DS values were measured from experimental curves [9,10]and are respectively

cm2/s (diMe) and 3.8 X
3.3 X
cm2/s (diPh-diMe). In this series, the
B term is equal for the four columns, the
CMtermis equal for column one arid three
and for column two and four while the CS
term is equal for column one and two and
for column three and four. The diffusion in
diPh-diMe silicone is so slow that the
efficiency is very low and, moreover, that
the efficiencies of the 0.32 and0.53mmi.d.
column are nearly equal [eq. (36)l.

Table 4
VOContribition of B, CM,and Cs to H.
k= 10, H2=30 cm/s, N,= 15 cm/s.
r, = 0.16 mm, D, = 0.1 cm2/s for N,, 0.2 cm2/s for H,.
DL 3.3 X
cm2/s (diMe) and 3.8 X
cm2/s.

Stat Phase
In order to obtain the same kvalues on all
columns, the analysis temperature was
adjusted according to the principle of an
increase of 15' on doubling df The
separation power is halved on going from
0 1 t o 3 pm
Journal of High Resolution Chromatography

df (pm)

NZ

B%
diMesilicone

024

300
diPh-diMesil

024

300

463
26
45
6

HZ

CMoio

CS%

B%

cp,pio

C,"o

532

05
44
4
87

46

53
21
49
4

1
61
8
93

30
51

18
43
3

VOL. 12,MAY 1989

277