Relative Contributions of Molecular Diffusion and

Anastomosis in Gas Chromatographic Columns

ANTHONY B. LITTLEWOOD
School of Chemistry, The University, Newcastle upon Tyne, 7 , England

b Dispersionof chromatographiczones
in packed columns caused by uneven
flow of eluent through the packing
is relaxed by lateral mass transfer,
which consists of flow-independent
molecular diffusion and flow-dependent
anastomosis resulting from lateral random walk of eluent gas through the
interstices of packing. The relative
magnitude of the two mass transfers
is discussed and the conclusion is
that anastomosis is appreciable at
flow rates faster than about 20 cm.
per second in hydrogen or 5 cm.
per second in nitrogen. By using
flow rates faster than these, the extra
mass transfer provided by anastomosis enables columns to be operated
at more plates per second and thus
enables separations to be achieved
more rapidly.

to proceed on its way, and its lateral

motion in so doing contributes to the
lateral mass transfer.
This mass
transfer resulting from the irregular
flow patterns of the eluent in the packed
bed is conveniently called anastomosis, following Golay (6). Turbulence may also occur as an additional
feature.
Any lateral mass-transfer process
which augments the relaxing effect of
lateral molecular diffusion reduces the
value of H and thus improves the
column performance (4). Below, therefore, we examine the regimens in which
anastomosis contributes appreciably to
mass transfer.
Very recently, experiments similar to
those reported here have been described by Harper and Hammond ( 8 ) .
THEORY

N CHROMATOQRAPHIC columns, the

eluent flows along the axis of the

column a t different speeds in different
parts of the cross section of the column.
The very large dispersion of chromatographic zones that would result from
this uneven flow is relaxed and reduced
by lateral mass transfer. It has been
shown (6, 14) that if the actual dispersion from this source is measured by
a contribution, H*, to the height equivalent to the theoretical plate, H, or by a
van Deemter coefficient (17), C,

where u is the linear speed of the eluent,

D is the effective lateral diffusiun coefficient, and K is a constant depending on
the geometry of the column and the
fluid flow pattern. Giddings (2) has
studied the values of K for the case that
the unevenness of flow is over distances
of the column cross section in packed
columns of the order of few particle
diameters. Littlewood (14) has studied
values of K for various models of uneven flow such that the unevenness
extends over the whole column cross
section.
I n a packed column, lateral mass
transfer can occur by molecular diffusion. Also, an element of flowing
eluent encountering a particle on its
route is forced to flow around it in order
2

rn

ANALYTICAL CHEMISTRY

Molecular diffusion and anastomosis as

described above both occur by a random
walk process in which the many separate
elements of the diffusing species undergo
collisions which deflect individual elements in a choice of directions. In
general, the diffusion coefficient for such
a process is the product of the speed a t
which elements move between collisions,
the distance they move between
collisions, and a constant. In the case
of molecular diffusion, the elements are
molecules, the speed is the molecular
speed suitably averaged, the distance is
the mean free path, and the constant is
approximately l / 3 (16).
Diffusion by anastomosis can be
described by a diffusion coefficient, D,,
if the elements are small volumes of gas
of volume comparable with that of the
interstices of packed columns, the speed
is the eluent speed, u, the distance
between collisions is the particle
diameter, d,, and

D, = aud,
(2)
where is a constant. The main point
of interest is the value of the constant.
We suggest below that a t fast flows
D, is a major contributor to radial diffusion in cylindrical columns of packed
beds, and experimental evidence (10)
shows that in these conditions the
coefficient of radial diffusion is altered
by small alterations in the packing
technique. It is apparent, therefore,
(Y

that, apart from the difficulty of the

problem, no realistic precise calculations
of can be made that will be of general
use in gas chromatography. We must
therefore estimate it. One estimate
would be to use the constant
which
applies to molecular diffusion; another
estimate is given below.
In any cross section of the column,
there are stationary solid particles of
packing and mobile particles of
flowing gas; each particle is a volume of
eluent occupying an interstice. By
considering the progress of the cross
section through the column a t the
average elution speed, it is apparent
that the lateral motion of the particles
of eluent in the cross section as they
weave in and out of the particles of
packing is closely analogous to the twodimensional diffusion of a mixture of a
very light and a very heavy gas. The
constant for this kind of diffusion is
easily found to be 4 / 3 ~ = 0.4, so that
on this model, D, = 0.4 ud,, where
uis the average lateral velocity of the
eluate. The relation of the lateral
to the longitudinal velocity,
velocity, u,
u,depends on the shape and nature of
the packing-e.g., for a packing of flat
disks a t right angles to the pressure
gradient, u > u,but for cigar-shaped
particles along the pressure gradient,
u f < u. We do not study this further
here, but we suppose that in ordinary
packed columns of Celite which approximate to random spheres not quite closepacked, u is of the same order as u,
though less than it. We therefore
expect that is of the order of but less
than 0.4.
If there are two independent processes leading to mass transfer by diffusion in a given volume, the total
mass transfer is described by a diffusion coefficient, D, equal to the sum
of the coefficients for the separate processes, so that here
(Y

D, f D ,

(3)

where D, is the coefficient of molecular

diffusion. The mass transfer in a
chromatographic column is described by
D if the uneven flow which causes the
mass transfer is on so large a scale in
relation to the particle packing that
there are enough steps in the random
walk producing D, to enable the trans-

fer to be described in terms of a stochastically derived diffusion coefficient.

Elsewhere (14) we show that most of the
gas-phase dispersion in ordinary packed
columns such as are used in gas
chromatography is due to large scale
unevenness extending over many particle diameters. The same is probably
true in liquid chromatography. I n this
paper we use our previous conclusion,
and thus we combine Equations 1, 2,
and 3 to give:

H
0.9
m m.

0.80.7*
0.6

0.5 .

0.40.3.

This is a form of the coupling equation

of Giddings (3).

0.2

'

20
Figure 1.

EXPERIMENTAL

Carrier gas, either nitrogen or hydrogen, passed through a pressure controller (V.P.C. 1, Edwards and Co.,
Ltd.) , and through a simple introducing
port consisting of a compressed silicone
rubber disk in the side arm of a brass
T-piece such as is used for plumbing
1/4-inch pipe to the column. The
inlet pressure was measured with a
mercury manometer. At the column
outlet, the gas passed first through a
T-piece, the side arm of which was
fitted with an adjustable tap, and then
to a flame detector (Gas Chromatography, Ltd.) . For most of the runs,
the carrier gas flow was too great for
the flame detector, and thus most of the
gas was vented to waste through the
tap. Recording was done on a 1-second
full scale travel recorder (KoneywellBrown). The time constant of the
recorder was much less than 1 second for
short pen travels. For rapid peaks,
therefore, the peak height was restricted by reducing the detector sensitivity so that the pen could always
keep pace.
KOflowmeter was incorporated. The
linear flow rate a t a few suitable slow
flows was measured from the column
length and the time of passage through
the column of a nonabsorbed gas.
Values of the flow speed a t faster flows
were calculated from the retention
times of solutes compared to those a t
the measured slow flows and the appropriate pressure correction factors, j
(see below).
Columns not longer than about 2 feet
were used, so that flows of up to 50 crn.

Ref.
No.
I

Internal
diameter,
4

Support
Celite

I1

Celite

I11

Celite

IV

Celite

mm.

40

80

uo

100 cm/s

Typical plot of H vs. uo (column I)

1.
2.
3.
4.

3-Methylhexane in nitrogen
n-Heptane in nitrogen
2-Methyihexane in hydrogen
n-Heptane in hydrogen

per second using nitrogen and 100 cm.

per second or more using hydrogen
could be obtained without using pressure drops of more than 100 cm. of Hg.
Other details of columns are given in
Table I.
RESULTS

Values of H for suitable hydrocarbon

solutes were determined a t different flow
rates in the range 2 to 150 cm. per
second on the columns described in
Table I. H was plotted against uo, the
outlet flow rate. Typical plots or
column I are shown in Figure 1. It is
the characteristic slight concave curve
a t fast flows that is under discussion in
this paper.
We assume that the principal dispersing factors contributing to H are
H*, longitudinal diffusion, slow mass
transfer in the stationary phase, and
slow mass transfer of solute in the
mobile phase during equilibration.
Thus, we assume that H is given by:

fB
=jH*+

60

G+

where the curly brackets indicate

functional dependence. D,C, and C Iare

Table 1. Description of Columns

Proportion
d,,
Column tube
Stationary of liquid,
liquid
% (w./w.) av., mm.
material
Hexadecane 10.64
0.13
Soft
copper
Squalane
10
0.13
Hard
copper
Hexadecane 10.64
0.21
Soft
copper
Hexadecane 10.64/
0.13
Glass
8.66

constants discussed below. f and j are

functions of the ratio of inlet and outlet
pressure. f varies between unity and
9/8, and since this range of variation is
small, it is neglected. j is the pressure
correction factor of James and Martin,
and it is not neglected.
To examine H*, it is necessary to calculate by methods beyond dispute the
values of the second, third, and fourth
terms in Equation 5, so that they may be
subtracted from H , leaving H *. I n our
experiments, vapors with fairly large
values of k , the retardation ratio, have
been used. Had we used a nonabsorbed
vapor-e.g., air-as have some workers
(11), the terms in C, and Cl would have
been absent, and the isolation of H*
from H would have required less
reliance on previously established
theory. The drawback to the use of
nonabsorbed solutes is, however, that
a t very fast flows peaks would occupy so
short a time that they could not be
measured by the detection apparatus
available. For example, the standard
deviation of an air peak for column I
run a t 1 meter per second would be
about 0.04 second. By using vapors
with large values of k , reliable measurements of H can be made. The study of

Column
length,
cm.
59.5

60.0
59.5

71

Solutes used
3-Methylhexane
+Heptane
2-Methylpentane
n-Hexane
3-Methylhexane
n-Heptane
2-Methylpentane
%-Hexane

VOL. 38, NO. 1, JANUARY 1966

62
86
18
26
62
86
14
19

llr2
c, = 240,
~

Figure 2.

Typical plot of H
1.
2.
3.
4.

- B/u, vs. uo (column 11)

2-Methylpentane in nitrogen
n-Hexane in nitrogen
2-Methylpentane in hydrogen
n-Hexane in hydrogen

H* from these values is unaffected,

since H * is independent of k (14).
In some cases, there are sufficient
results at slow flow rates that B can be
measured by well established methods
(13). I n this way, the term due to
longitudinal diffusion can be subtracted.
Values of B so determined are underlined in Table 11. In other cases B
was calculated from the product of
known diffusion coefficients of the
solutes in the carrier gas (9) and a
tortuosity factor of 0.65. Previous
experience has shown that the tortuosity factor is within 10% of this
figure, and a check using the independently determined values of B given
in Table I1 shows that our results are
consistent with this. A typical plot of
(H - B/u,) against uo is given in
Figure 2.
I n Equation 5, C, is the coefficient of
the term describing the dispersion produced by noninstantaneous mass transfer of solute across the mobile phase
during its equilibration between the
phases. I n many previous discussions
of column dynamics, including the
authors previous paper on this subject
( 1 4 , H * is regarded as proportional to
uo, and the constant of proportionality
is included in C,. For the obvious
reason that here we are studying the
regimens in which H* is not proportional
to uo, we exclude it from C,. It is well
established that if H is dominated by
Cc rather than C,, H decreases with
increase in k ; if, however, C, is dom-

inant, H increases with increase in IC.

I n our experiments, the first case is
invariably true, and we assume that in
all cases of interest C I >C,. Since it
appears that Ci is only a small though
not negligible part of H , C, provides an
even smaller part of H . Further estimates of the magnitude of the term in
C, can be made as follows. C, is a t its
greatest when k + a. In this case, the
exact equation for C, in a capillary
column of radius r is

Table 11.

2-Methylpentane
B
33
41
9
11

D,
H2
N2

ANALYTICAL CHEMISTRY

06
rnrn.

This equation will apply approximately

to a packed column if r is interpreted
as approximately half the particle diameter. In hydrogen, the smallest diffusion coefficient that we consider is
about 25 sq. mm. per second and in our
columns, r is about 0.05 mm. Thus, the
greatest possible value of C, is approximately 0.05 millisecond. At uo =
100 cm. per second, this gives a contribution to H of 0.05 mm., which is only of
the order of 5 to 10% of H . Also, the
distances between the plots of H us. uo
for different solutes are roughly the
same in nitrogen as in hydrogen, again
suggesting that the role of the carrier
gas in this respect is irrelevant. For all
these reasons, we consider that C,
provides only a small term in H , and in
this study we ignore it.
In our columns, Cl is not negligible,
being of the order of 1 millisecond.
Values of C1may be obtained as follows.
At slow flows, both C, (whether
negligible or not) and the coefficient of
uoin the expression for H* are inversely
proportional to D,, the coefficient of
molecular diffusion of the solute in the
carrier gas. Let the sum of C, and the
coefficient be represented by C,. [C,
is the quantity called simply C, in (14)
and other papers on column dynamics.]

1.

05

04

20

40

60

80
crnl s

Figure 3.

IO0
a
.

H* vs. uo for column I

Experimental points for 3-methylhexone and n-heptane

Higher. Nitrogen carrier gas
Lower. Hydrogen carrier gas
Points for different solutes do not occupy significantly different positions and hence are not
distinguished
Theoretical lines
1. Nitrogen, CY = 0.24
2. Hydrogen, a = 0.24

of D, and B for Columns I to IV

(Sq.mm. per second)
n-Hexane
3-Methylhexane
D,
B
D,
B
31
38
30
37
8.5
10
8.1
10
Values

D,
27

7.2

n-Heptane
B
34
9

rnm.
Hp8

Values of Cl for Solutes on

Columns 1 to IV

Table 111.

Column
I

Solute
3-Methylhexane
*Heptane
2-Methylpentane
n-Hexane
n-Methylheptane
+Heptane
2-Methylpentane
n-Hexane

I1
I11

IV

Figure 4.

H*

c = C,

0.68

0.50

1.33
0.83
0.7

0.2
1.3
0.8

the published diffusion coefficients as in

Table I1 and from the slopes of the
experimental plots of Figures 3 to 6 at
slow flows, which equal KID,. Values
of K are given in Table IV. The
quantity d, was as in Table I.
Lines for different solutes in the
experimental plots of H* us. uo are
virtually coincident or not significantly
separated. This provides further indication that H* is independent of k (14)
and a t the same time it indicates that

vs. uo for column I1

Experimental points
2-Methylpentane
n-Hexane
Higher. Nitrogen carrier gas
lower. Hydrogen carrier gas
Theoretical lines, a = 0.24
1 2-Methylpentane in nitrogen
2, n-Hexane in nitrogen
3. n-Hexane In hydrogen
4. 2-Methylpentane in hydrogen

Let us also define

Ci, msec.

HX4
c1

mm.

(7)

Diffusion coefficients in hydrogen are

about 3.7 times as great as those in
nitrogen ( l d ) , and therefore the equations :

apply to a given solute in each of the

two gases. Values of C in each gas may
be measured from the slope at the origin
of plots such as those of Figure 2.
[In ( l d ) , the above equations were
written incorrectly, though used correctly; we take this opportunity to
correct them.] Values of Ct calculated
from Equations 8 are given in Table 111.
The contribution to H due to slow
mass transfer in the stationary phase
may be subtracted from (H - B/u,) by
subtracting the factor jC1uo,thus leaving

H*.
The above procedure for isolating
H * from H was followed for solutes
given in Tables I1 and I11 on the
columns described in Table I. The results are presented as the points in the
plots of H * us. uoin Figures 3, 4, 5, and
6: one figure for each column. In all
cases, H* is a monotonically increasing
function of u,, but except a t the slowest
flows it increases less than linearly, as
predicted by Equation 4.
The full lines in the figures are calculated from Equation 4,. putting u =
uoand with CY as specified in the legends.
For these plots, K was obtained from

30
Figure 5.

60

H*

cm/s

I50

120
0

vs. uo for column 111

Experimental points for 3-methylhexane and n-heptane

Higher. Nitrogen carrier gas
lower. Hydrogen carrier gas
Theoretical lines
1. Nitrogen, a = 0.1 3
2. Nitrogen, (I = 0.24
3. Hydrogen, CY = 0.1 3
4. Hydrogen, (I = 0.24

Table IV.

Column
No.
I

Solute

I1

n-Cl
MeH)
2 MeP
n-Ce

I11

Parameters of Equation 4 for Columns I to IV

Z-FH>

Value of D , used,
sq. mm/sec.
H2
Nz

K , sq. mm. X 108

From Hz
From Nz

19.6

22.8

30

8.1

35
33

30.3
25.5

33
31

30

8.1

140

142

8.5

IV

75
75
30
8.1
n-Cs
Except for column 11,plots given by different solutes are not significantly different.

VOL. 38,

NO. 1,

JANUARY 1966

Figure 6.

H* vs. uofor column IV

Experimental points for 2-methylpentane and n-hexane

Higher. Nitrogen carrier gas
lower. Hydrogen carrier gas
Theoretical lines
1. Nitrogen,a = 0.24
2. Hydrogen,a = 0.24

the procedure for isolating H * is adequate.

If K is due to geometrical factors only
and is independent of carrier gas, its
values as calculated from D, and the
slope near the origin of the lines in the
figures should be the same in hydrogen
and in nitrogen. Table IV shows that
this is true, and gives confidence to the
plots shown in the figures, a t least for
the slower flows.
DISCUSSION

I n calculating the theoretical lines of

Figures 3 to 6 using Equation 4, the
experimental data have been used to fix
the value of K . The fit of the experimental points on the calculated lines,
therefore, serves only to establish the
value of a. When hydrogen is the
carrier gas, Figures 3, 4, and 6 for
columns I, 11, and IV show that the
points fit accurately a calculated line
with a = 0.24. With column 111,
which uses larger particles, a good fit is
obtained if a = 0.13. These values are
consistent with the theory presented.
I n the figures, the values of a which fit
the hydrogen curves are used to calculate curves for H * in nitrogen; essentially the difference is a compression
of the abscissa by a factor of 3.7. The
fit is adequate a t nitrogen flows less
than 25 cm. per second, but at faster
flows H* is always larger than is predicted and does not show signs of approaching an asymptotic value. We
offer no explanation; there may be
other terms in H, and also the anomaly
may result from some unrecognized
instrumental fault caused by the unusually fast streams of gas.
The results for a obtained here may be
compared with related results from other
studies. I n experiments similar in type
to those reported here, Harper and
Hammond (8) also find evidence of
6

ANALYTICAL CHEMISTRY

curvature of plots of H* us. uo,and present their data in graphs which are
essentially similar to those of Figures 3
to 6. Calculations from measurements
from their graphs, and also calculations
made from the parameters used in their
discussion (which differ from those
used here) lead to the result
= 1.
For example, simple calculation shows
that l / a = 4h/p2, where a is as in this
paper, and h and p are as in Harper and
Hammonds; Harper and Hammond
propose p = 2 h and h = 1; whence
a = 1. This value is very much higher
than is found here, and implies appreciable curvature of plots of H* us.
uo a t flows as small as 1 or 2 cm. per
second. This is contrary to our
experience.
Bernard and Wilhelm (1,12) describe
experiments performed using much
larger particles in a much larger tube
than here, with very fast flows indeed,
so that flow is turbulent and molecular
diffusion is negligible. They have
measured the coefficient of radial diffusion, which in their circumstances

can be presumed to be produced entirely

by anastomosis, and from the results it
= 0.09 to CY = 0.12.
is found that
These figures are consistent with our
own figures for column 111.
Sternberg and Poulson ( I C ) , using
columns in which the particles of packing are not many times smaller than the
column tube, give data for H us, uo for
values of u. up to 140 cm. per second,
and draw attention to the fact that H
is smaller a t fast flows than would be
anticipated from the van Deemter
If their data [Figure
equation.
6 of (16)] are used to calculate
a , a very small value of about 0.03 is
obtained. This is reasonable, for in
these authors columns anastomosis is
impeded by the closeness of the walls.
Finally, Halasz and Horvath (7)
present curves of H us. ua for vapors in
packed capillary columns, in which the
significant observation is that there is
clearly no concave curvature even a t
flows greater than 100 cm. per second,
This is consistent with theory, since if
there are no multiple paths, there ought
to be no anastomosis.
The practical significance of these
studies is made evident in Figure 7,
which shows axes for plots of H us. u.
The slope of a line from any point on a
plot of H us. u to the origin is H / u .
Substituting H = 1/N and u = kl/t,
where 1 is the length of a column with AT
plates and t is the time of elution of a
solute with retardation ratio k , the slope
of the line is seen to be t/kN-Le.,
l/k multiplied by the time per plate.
In any plot of H us. u,the point which
connects to the origin by the straight
line of smallest slope gives the most
plates per second for a given value of
k. With an ordinary van Deemter
plot as indicated by line a, increase in
flow rate beyond the point where the
line has substantially reached its
asymptote, b, does not enable one to
obtain more plates per second. With
the plots as in c such as are discussed
here, however, the faster the flow, the
smaller the slope of lines drawn to the

origin from the point corresponding to

that flow. Hence, there can be a real
increase in analysis speed, resulting in
more plates per unit time. In gas
chromatography,
most
ordinary
columns employ particles for which
d, is between 0.1 and 0.2 mm. For most
vapors in hydrogen, D o is between 10
and 40 sq. mm. per second. Thus,
D, becomes comparable with D, when
u is between 20 and 50 cm. per second.
For vapors in nitrogen, D, is about fourfold less, and thus D, is comparable
with D owhen u is between 5 and 15 cm.
per second. These speeds are a little,
but not much, greater than are currently
used.
The quantity K forms a good parameter by which to judge the quality of
packing of a column. I n our previous
paper (14), this quantity was tabulated
under the heading C,D,. It describes
the extent to which unevenness of flow
contributes to the plate height. Values
for good ordinary packed columns are
and it is
about 20 to 30 sq. em. x
seen that two of the columns described
here have values in this region. Figure
1 shows that the minimum plate height
for heptane on column I is less than
0.35 mm. in nitrogen and only just
greater than 0.4 mm. in hydrogen;

these figures are characteristic of a good

column. Nevertheless, in this column,
reference to Figure 3 shows that 30%
of this plate height is caused by H*.
This indicates that the techniques by
which columns are packed do not produce an evenly permeable bed.
The extra relaxation provided by
anastomosis at fast flows merely reduces the term H*, which results almost
entirely from imperfect column packing.
It may well be argued that rather than
alleviate bad packing by the use of
fast flows, it would be better to improve
the packing. Nevertheless, the fact
remains that no one has yet found a way
of packing a powder into a tube in a
completely homogeneous manner, and
until this is done, operation of columns
a t fast flows may well prove desirable.
LITERATURE CITED

(1) Bernard, R. A., Wilhelm, R. H.,

Chem. Eng. Progr. 46, 233 (1950).
( 2 ) Giddings, J. C., ANAL. CHEM. 34,
1186 (1962).
(3) Ibid., 35, 439 (1963).
(4) Ibid., 36, 1170 (1964).
(5) Giddings, J. C., J. Chromatog. 5, 46
(1961).
(6) Golay, M. J. E., Nature 182, 1146
(1958).
( 7 ) Halasz, I., Horvath, C., ANAL.
CHEM.35, 499 (1963).

(8) Harper, J. M., Hammond, E. G.,

Ibid., 37, 486 (1965).
(9) Hirschfelder, G. O., Curtiss, C. F.,

Bird, R. B., hfolecular Theory of

Gases and Liquids, Wiley, New York,
19.54
---.

(10) Huyten, F. H., van Beersum, w.,

Rijnders, G. W. A., Gas Chromatography 1960, Proceedings of 3rd
International Symposium, Edinburgh,
R. P. W. Scott, ed., Butterworths,
T,nnrlon.
1960.
~~,
..~.
.1) Kieselbach, R., ANAL. CHEM. 35,

1342 (1963).

. 2 ) Lapidus, L., Separation Processes

in Practice, R. F. Chapman, ed.,

Reinhold, New York, 1961.

.3) Littleyod, A. B., Gas Chromatography, p. 169, Academic Press,
New York, 1962.
.4) Littlewood, A. B., Proceedings of
5th International Symposium on Gas
Chromatography, Brighton, September
1964, A. Goldup, ed., Institute of
Petroleum, London, 1965.
(15) Present, R. D., Kinetic Theory of
Gases, McGraw-Hill. New York. 1958.
(16) Sternberg, J. C., Poulson, R. E.,
ANAL.CHEM.36. 1494 (1964).
~~.--,.
(17) Van Deemter; J. J., Zuiderweg, F. J.,
Klinkenberg, A., Chem. Eng. Sci. 5,
271 (1956).
RECEIVEDfor review June 7, 1965.
Accepted September 27, 1965. Troisihme
Symposium de Chromatographie en Phase
Gazeuse, organis6 par le Groupement
pour lAyancement des MBthodes Spectrographiques, B 1Ecole Polytechnique,
Paris, May 19, 1965.

Effects of Temperature on Carrier-Gas Flow Rates in

Packed and Capillary Columns
GARY HORLICK and W. E. HARRIS
Department of Chemistry, University o f Alberta, Edmonton, Alberta, Canada

H. W. HABGOOD
Research Council o f Alberta, Edmonfon, Alberta, Canada
The temperature dependence of
carrier-gas flow rate under conditions of constant inlet and outlet
pressures was measured for packed
and capillary columns of metal and
of glass using helium, hydrogen, and
nitrogen as carrier gases. With all
three gases over the temperature
range 25 to 200 C. the flow rate
as measured at a constant temperature may be taken as proportional
to ( l / T ) 1 . 7 for packed metal columns
and for capillary columns of either
metal or glass, and as proportional
to ( 1 /T)1.8 for packed glass columns.
The flow rates expressed at column
temperature will be proportional to
(1 / T ) O . 7 and ( 1 /T)O.*, respectivey. The
temperature coefficients for packed
columns are about 0.1 higher than
would be predicted theoretically.

the temperature of a column

for gas chromatography is increased, the carrier-gas flow rate will
decrease unless the flow rate is mainHEN

tained by increasing the column inlet

pressure. The principal effects of increased temperature are to increase gas
viscosity, to increase gas volumn, and
to change slightly the premeability of
the column. The overall effect of
temperature on carrier-gas flow rates is
of interest to the theory of programmed
temperature
gas
chromatography
(PTGC) and of concern to those doing
experimental work both in PTGC and
in isothermal chromatography a t different temperatures. Although a few
observations have been reported (2, ?),
this aspect of gas chromatography
seems to have been largely neglected.
When a column is operated so that the
volumetric flow rate is constant a t the
column outlet as measured a t a constant
temperature, the changes in gas volume
and viscosity with increasing temperature require an increased pressure drop
across the column. As a result, the
pressure-gradient correction factor decreases with increasing temperature.
I n contrast, when a column is operated
under conditions of constant inlet and

outlet pressures,
the decreasing
volumetric flow rate as measured a t the
column outlet and a t a constant temperature results in increasing peak areas
(using a thermal conductivity detector).
In general, the time taken for analysis
and the efficiency of a separation can be
influenced by the changes in flow resulting from temperature changes. I n
this study the effect of temperature on
flow rate is investigated for several
gases of interest in chromatography.
THEORY

The flow of a gas through a packed

chromatographic column may be described by Darcys law (1, 5 ) ; for gas
flow in a porous bed

F_, -- - BdP
A
t dz

(1)

where F , is the volumetric flow rate a t

Present address, Department of Chemistry, University of Illinois, Urbana, Ill.
VOL. 38, NO. I, JANUARY 1966