A new Technique for Heart Cutting in Gas Chromatography [1]

Eine neue Technik des "heart cuttings" in der Gas-

Chromatographie

Une nouvelle technique de "Heart Cutting" dans la

chromatographie en phase gazeuse
D.R. Deans, Research Department, Imperial Chemical Industries Ltd.,
Heavy Organic Chemicals Division, Billingham, Co. Durham, England

Summary: Heart cutting is commonly used in on-line chromato- Introduction

graphs, but is much less frequently used in laboratory chromato-
graphs because of the difficulty of installing a remotely operated The transfer of one or more selected groups of compounds
flow switching valve in a chromatograph oven and because of eluted from a gas chromatographic column onto a second
temperature limitations associated with such valves and their con-
tribution to peak spreading.
column is usually referred to as "Heart cutting" or "Cutt-
A system is described which eliminates the use of mechanical valves
hag". The two major areas o f application are in the analysis
in the oven and can be added easily and cheaply to existing chro- of complex mixtures and in the determination of trace
matogzaphs. The system can be used with capillary columns with- components.
out loss of efficiency and is sufficiently easy to operate that it is
used in control laboratories by process workers. In the case of complex mixtures, groups o f compounds
which show poor resolution or which are not resolved at
Zusammenfassung: Verschiedene Griinde Ftihrten dazu, day die all on the first column are selectively transferred to a
bei der Prozei~-GC iibliche Technik des 'heart cuttings', d.h. der second column of different characteristics. A simple
direkten I)berleitung yon Peaks von einer in die andere Trennsiiule example is in the analysis of saturated hydrocarbons
durcli Gaswegumschaltung, in normalen Labor-Chromatographen where a separation by carbon number is obtained on a
nut sehr selten angewendet wird : wegen der Schwierigkeiten,
eine indirekt gesteuerte Gaswegumschaltung in den Ofenraum vor-
non-polar column followed by a separation of the peaks
handener Gas-Chromatographen einzubauen; wegen der begrenz- for each carbon number into naphthenes and paraffins on
ten Temperaturbestandigkeit zugeh6riger Umschaltventile; wegen a polar column.
tier auftretenden Peakverbreiterung.
In trace analysis the column usually has to be overloaded
Das im folgenden beschriebene System vermeidet den Gebrauch
with the major component in order to obtain sufficient
mechanischer Umschaltventile und kann sowohl leicht als auch
billig in vorhandene Gas-Chromatographen eingebaut werden. signal from the trace component, and this frequently
Das System bewirkt auch bei Anwendung auf Trennkapillaren causes difficulty when the trace peak comes out on the
keinen Verlust an Trennleistung und ist so leicht zu verwirklichen, tail of the major peak. A substantial improvement in
daft es im Routinelabor yon den dortigen Mitarbeitern eingesetzt separation can be made by including a cutting device half
werden kann. way down the column so that only a small amount of the
major component is transferred with the trace component
Sommake: La technique de pr~16vement d'une fraction inter- onto the second half of the column. Overloading and tail-
m~diaire de l'dluant que 1'on trouve bien souvent en chromato-
glaphie industrielle, est beaucoup moins r~pandue dans la chroma-
hag on the second half of the column is thus eliminated or
tographic de laboratoire, ~tcause de la difficult6 d'installation d'une greatly reduced.
vanne de commutation dans le four d'un chromatographe, et en The technique of cutting is commonly practised in process
raison de la limitation de la temp6rature resultant de remploi de
ces vannes, et de leur effet sur l'61argissement den pies. chromatographs but has been used much less frequently
in the laboratory. A flow diagram typical of existing
L'article d6crit une m&hode de commutation du eourant de gaz
vecteur qui supprime l'emploi de vannes mdcaniques dans le four, systems is shown in fig. 1.
et que ron peut incorporer facilement et h peu de frais dans les The sample is injected with the four-way tap X in the
chromatographes existants. La m~thode peut dtre employee avec
position shown. When the required compounds start to
les cotonnes capiUaires sans perte d'efficacit~, et son mode op~ra-
toire est suffisamment facile pour permettre son emploi par des emerge from the first column, tap X is turned through
ouvriers nonqualifi~s dans les laboratoires de contr61e. 90 ~ so that they can pass on to the second column. By

18
turning tap X through a further 90 ~ succeeding unwanted Metal columns, both capillary and packed, have been used
components are vented to atmosphere. The needle valve for all applications so far, but there is no obvious reason
Y is adjusted so that the flow through the first column why glass should not be used. The connection between
remains constant irrespective of the position of tap X. the two columns has to serve as a slight flow restriction;
Similarly needle valve Z is adjusted to maintain a constant its dimensions are not critical and a 2-inch length of
flow through the second column. 20 thou i.d. capillary tube has been used satisfactorily for
The fact that the tap, or slide valve in process chromato- many applications. Where capillary columns and other
graphs, must be situated in the sample path is the point high efficiency systems have been used, the connection
of greatest weakness in these designs. The tap must be at and Tee pieces have been coated with stationary phase to
the operating temperature of the columns, i.e. it must be obtain maximum efficiency. The volume of the Tee pieces
inside the oven, yet it must be operated from outside the has been kept small by constructing them of brass or stain-
oven. Not only is the design of the tap and its construction less steel approximately 3/4 inch long, with a 42 thou hole
complicated, but in its incorporation into the whole chro- to take capillary connections and an 1/8 inch i.d. hole to
matograph unit is mechanicaUy difficult and usually ex- take 1/8 inch o.d. connection to packed columns and to
pensive; these problems tend to be magnified as the the gas lines. The Tee gas connection in the Tee piece is
operating temperature increases. The dead volume intro- 42 thou in each branch.
duced by the tap gives rise to reduced separation efficiency
and this is often aggravated by absorption of compounds
in tap lubricants or low friction plastics. Consequently injection ~rt pressure
cutting systems of this type cannot normally be used to r--- I L____I controllerI
t~ar~
any advantage with high efficiency columns.

In the method described in this paper the multiport first o~n

columr bocoaary
tap and its associated difficulties have been removed
completely. top b needle valve
C ~< ~-
pre~u..re .
leamt~rj con[roller Z
tad c r ' l ~
I
I
I
injection port I second
I colurnn L.) pressure gouge
J F2~ J
I I
I pressure J
I controller 1
I I
first I oven I
column I
bot~Jory L . . . .
Fig. 2
detector

needle valve y

I needle volve z
I
I The gas lines from taps B and C have been made of
second I
column I 3/32 inch i.d. (minimum) copper tubing so that the
I
I Fig. 1 pressure drop down these lines between the pressure
I
I controller and the column and the column and the needle
I
. . . . . . I
valve is negligible.
det~t~

Operation for Cutting and Forward Flow

Construction of the new System Taps A and C are left open at all times during cutting
operations; they are used for setting up purposes only.
The flow system used is shown in figure 2. The design of On forward flow the two columns are used in series, tap
the on/off taps is not critical as they are located outside B being closed. Carrier gas enters the chromatograph
the oven; spring loaded glass taps have been used up to from the supply through pressure controller 1 and tap A,
30 p.s.i.g, and Simplefix, and other similar metal toggle it flows down the two columns to the detector in the
valves up to much higher pressures. The choice of pressure normal way. Tap C is normally open but a negligible flow
controllers is not particularly critical but they should have of carrier gas enters the chromatograph through this line
a fast response and control at exactly the same pressure as pressure controller 2 set to control at the same pressure
OVer a flow rate range of say 0 - 170 ml/min. Edwards as that produced at the Tee connection by gas flowing
V.P.C.I. pressure regulators have been found satisfactory. down the first column from the inlet. The slow purging of

19
this line by any slight leak of gas through the pressure noted pressure (or fractionally higher). At this stage, with
controller serves to prevent diffusion of small amounts of the detector operating at the maximum sensitivity required
major components into this branch of the Tee. for the analysis, opening and closing tap A should not give
any movement of base line due to pressure change at the
On 'cut flow" tap B is open. Carrier gas enters through
inlet to the second column. If movement is observed the
pressure controller 1 and flows down the first column
pressure from controller 2 should be increased until the
and out through tap B and the needle valve. At the same
movement on operating tap A just disappears. It should
time carrier gas enters through pressure controller 2 and
be noted that delayed base line shift on operating tap A
tap C. At the Tee piece the gas divides, a small part of it
can occasionally occur, at high sensitivities, due to change
flowing up to join the gas coming from the first column
in stationary phase bleed signal. If the first column contains
and go out through tap B and the needle valve. The major
a phase which decomposes slowly to give low boiling
part of the gas from controller 2 flows down the second
material which is eluted rapidly through the second column
column and out through the detector.
it is possible to confuse this shift with that due to pressure
To change from forward flow, where the compounds change. (Some polyethylene glycol stationary phases can
emerging from the first column go on to the second show this characteristic.)
column, to cut flow, where the compounds emerging
With taps A, B and C open the cut needle valve is ad-
from the first column are diverted to atmosphere, it is
justed until a flow roughly equal to that expected down
necessary only to open tap B. To revert to forward flow,
the first column is obtained at the exit from the needle
tap B is closed. The operation of this tap causes no base
valve. If the cut needle valve is correctly adjusted no peak
line movement on the chromatogram due to change in
should be obtained from the detector at the end of the
flow or pressure at the inlet to the second column, as this
second column when a compound (preferably a rapidly
is maintained constant by pressure controller 2.
eluted one, such as methane) is injected. Ifa peak is ob-
The timing of the operation of tap B has to be determined tained the cut needle valve is opened fractionally more
for each particular application. A number of injections are and the injection repeated. This adjustment and test is
made with successively increasing or decreasing times of repeated until the cut needle valve is open just sufficiently
operation of the tap until the desired effect is shown on to prevent compounds from the first column getting on
the chromatogram. Often the timing of the operation of to the second column when tap C is open. The system
tap B is not critical. Where accurate timing on a complex should then be ready for operation. It is not difficult, with
chromatogram is needed a monitor detector at the exit of a little experience, to set up a system without using taps A
the first column can be useful. or C or the pressure gauge. Consequently, after experience
Three forms of detection have been used successfully for has been gained, construction costs can be reduced by
monitoring. A thermal conductivity detector has been used omitting them.
with packed columns where the sensing cell of the detector
is placed immediately at the exit of the first column and
before the first Tee piece. This system is satisfactory
where thermal conductivity detector characteristics are
suitable. A flame ionisation detector has been used on a Other Modes of Operation
permanent bleed through a restricted capillary from the
exit of the first column. While this gives satisfactory 1. Hold
results, the control of the quantity of bleed to the detector By closing tap A (with tap C open and tap B either
is somewhat limited as this depends on the pressure at the open or shut) flow in the first column is arrested, while
end of the first column and the degree to which the flow down the second column continues. This technique
capillary is restricted. Much better control of the bleed has been used as an aid to separation of complex mixtures
rate to a flame ionisation detector is obtained by operating where two packed columns with different stationary pha-
the detector at controlled pressure 1). Where a capillary ses were used as the first and second columns. Hold up of
first column is used accurate control of a small bleed is flow in chromatographs is commonly used in process
necessary and this latter method is preferred. chromatographs to facilitate separation.
Initial setting up of the flows may be undertaken by first This technique has also been applied to the back-flushing
operating with tap A open and taps B and C closed. The system described by the author [2].
irdet pressure is adjusted on pressure controller 1 to give
the desired linear gas rate through both columns for the
2. Combination With Back-flushing
analysis to be carried out. The pressure indicated on the
pressure gauge is noted and tap A closed and tap C opened. The cutting system described has for many applications
Pressure controller 2 is adjusted until the gauge reads the been combined with the author's back-flushing system
[2]. A flow diagram is shown in figure 3. It will be seen
that the only addition is an effluent line which Tees into
1) Details of a technique for controlling the operating pressure of the carrier gas inlet line to the injection port. This Tee
a flame ionisation detector at above atmospheric pressure may pice must be at oven temperature to avoid condensation
be obtained from the author. of heavy materials when backflushing and consequent

20
contamination of the inlet gas on reverting to forward kyection port
flow. The effluent line carries a tap, tap D. When back- back flush
F.... r_ ~_~_, top a needle valve
flushing, tap A is dosed, tap C is open, tap D is open
and tap B is normally closed bat may be left open. To I t~c d pressure controller 1
revert to forward flow it is only necessary to open tap A '
I
I first
I
and close tap D. Tap A is opened fractionally before tap Icolumn
I needle valve 9
D is closed in order to flush out any compounds that could I
have diffused into the gas inlet line during back-flushing, 'I
I
I b

when the gas in this line is stationary. pressure

tap C controller
jr < 2
Back-flushed compounds may be detected as a combined I i
I >
peak with a detector on the effluent line. This detector '
can in some instances be the same one as the detector at I
I
the end of the second column. I ovqn
boundary

detector Fig. 4
injection port
r___[ 1 ---3 pre$.~.tl'~
~ . controller I

[ to~ d t>~ ~.
first bockflush
column needle valve
injection port
_m~ ~.
F .... controller 1
lx'essum I . .
Icapillarj c~176176 2
tap c --r I 1
f
I 0 '~ < first
I
I oven
I
I icolumn I boundary
i second k)pressure gauge I
column !
i
top b needle volve
I f 0 ~ >
I I pressure
I
!
L-__ i ....
l oven
I boundary
_I
E mic~oreoaor ~,~c controller
r~ <2

detector Fig. 3
i second
IIcolum n
I
I

detector Fig. 5

3. Combination of Different Column Diameters

Where a packed first column and a capillary second

column have been used the required linear gas rate down
both columns has been achieved by an additional gas line
and needle valve to act as a splitter before the capillary
column. This is shown in figure 4 in combination with or groups, selected by operation of tap B, go through the
back-flushing. The needle valve E is adjusted during the reactor and on to the second column. Two main modes
initial setting up, with tap A open and all others closed, of operation have been used. Firstly as an aid to identi-
to give the required split rate at the end of the first column. fication; an example of this is where hydrogenation, in
The remainder of the setting up and operation is exactly tile microreactor, of unknown unsaturated compounds
the same as for the normal system. The permanent gas eluted from the lust column has made it possible to
flow from this line has been used to feed a monitor deteo- attribute a carbon skeleton to the unknown by identifying
tor in some applications. the saturates produced by their retention times on the
second column. Secondly, as a method of investigating
kinetics of reactions, an example of this is where the
4. Inclusion of a Microreactor
microreactor has been used as a pyrolysis furnace to in-
The capillary connection between the two colunms has vestigate the breakdown products of individual compoundS
been replaced by a microreactor for a number of app- cut from a feedstock for comparison with the breakdown
lications as shown in figure 5. Only the chosen compounds products of the feedstock as a whole.

21
Discussion for some time by technicians in process laboratories with
only minimal training. A standard gas control unit is used
The advantages of the new system may be summarised as and can be attached to any chromatograph. Its operation
follows : is the same for all chromatographs. The ease with which
1. The dead volume associated with the use of taps in the the new system can be added to on existing chromatograph
sample path is eliminated. Consequently the cutting is one of its great advantages. The only requirement of an
technique may be applied to capillary and other high existing chromatograph is that it should be possible to run
efficiency columns. two 1/8 inch o.d. pipes from the gas control unit into the
2. The absence of flow switching valves or taps in the oven.

sample path eliminates the possibility of absorption of

sample components in tap lubricants or low friction
plastics.
L iteratu re C ited
3. The taps used are outside the oven, at ambient tempe-
rature, consequently no special design of tap or oven is [1] Part of this work was described by the author at a Gas Chromato o
required and the system is inexpensive and easy to add graphy Discussion Group Meeting at Leeds on 4th September 196!
(see J. Gas Chromatography 4, 34 1966).
to an existing chromatograph.
[2] D.R. Deans, J. Chromatog. 18, 477 - 481 (1965).
While the description of the flows and principles involved
may appear complicated the actual operation and setting Received Nov. 29, 1967
up of the system is simple. This technique has been in use Accepted Nov. 30, 1967

22