Headspace-Gas Chromatography: The Influence of Sample
Volume on Analytical Results
L. S. Ettrel* / B. Kolb 2
1Department of Chemical Engineering, Yale University, EO. Box 2159, New Haven, CT 06520, USA
2Bodenseewerk Perkin-Elmer & Co. GmbH, 7770 Oberlingen/See, FR Germany
Key Words
Gas chromatography
Headspace sampling
GC theory
Influence of sample volume
Summary
The role of the volume of the sample and the sample vial in
equilibrium headspace-gas chromatography is discussed.
A new term, the sample phase fraction (~s) is introduced.
It is shown that if the value of ~s is kept constant, the vial's
volume h as no influence on the "sensitivity"of the he adspace
analysis (which is proportional to the concentration of the
analyte in the headspace), in a given headspace sampling
system, concentration of the compound of interest in the
headspace (c&) at equilibrium is related to the value of q~s:
a higher ~s will increase c&. However, the influence is
!mportant only in the case of low distribution coefficients:
in the case of higher distribution coefficients this influence
is negligible. This conclusion is also true for small changes
in the sample volume in duplicate analyses: exact
reproducibility of the sample volume is important only in
the case of low distribution coefficient values.
Introduction
Headspace.gas chromatography (HSGC) refers to a
!echnique where the liquid or solid sample is thcrmostated
in a Closed vessel until the volatile compounds present in
the Sample reach an equilibrium between the sample proper
and the gas volume above it, the so-called "headspace".
Next, an aliquot of the headspace is introduced into the gas
chromatographic (GC) column for analysis.
The advantages of HSGC are twofold. Because a clean,
homogeneous gas sample is introduced into the gas
chromatograph, the method permits the determination of
VOlatile compounds present in an essentially non-volatile
matrix which, as such, could not be introduced directly into
the instrument. The second advantage is that, by the proper
Chromatographia Vol. 32, No. 1/2, July 1991 Originals
0009-5893/91/7 0005-08 $ 03.00/0 9 1991 Friedr. Vieweg & Sohn Verlagsgesellschaft mbH
selection of the equilibrium conditions, mainly the
temperature, the concentration of the volatile compounds
can be enhanced in the headspace, facilitating in this way
the determination of trace concentrations in the sample.
In the description above the need for equilibrium was
stressed. For this reason the technique is sometimes called
equilibrium HSGC, in order to distinguish it from dynamic
HSGC, in which the total amount of volatile compounds
present in a sample is released from the sample. Since this
release is a relatively slow process, intermediate trapping
(adsorption or cryogenic trap), with subsequent very rapid
release (desorption) is needed to permit the introduction of
the volatiles as a single slug into the gas chromatograph.
Dynamic HSGC is also called as thepurge and trap method.
Our discussion here refers exclusively to equilibrium HSGC.
Modern HSGC is a widely utilized technique which generally
relies on highly automated instruments to provide the exact
control and reproducibility of the analytical conditions
needed for quantitative analysis. The most frequently used
systems employ a moving needle and the control of pressure,
time and temperature to transfer a certain volume of the
headspace of the thermostated sample vial directly into the
GC column. For detail of HSGC and the instrumental
systems refs. [1]-[9] should be consulted. Below, a brief
description is given for better understanding.
Principles of EquilibriumHeadspace Sampling
Figure 1 shows the principles of the system. The sample - a
liquid or solid - is contained in a thermostated glass vial
sealed with a serum cap. A movable needle is located
upstream of the column. In the system used by us (Models
HS-100/101/40 of Bodenseewerk Perkin-Elmer GmbH,
Oberlingen, FRG), thc lower part of this needle is hollow
and openings at the two ends of the hollow part permit gas
to enter or exit. The movable needle can have various
positions and the shaft of the needle has compartments
which can open or close these openings. Care is taken that
the carrier gas inlet pressure (Pi) is higher than the pressure
(Ph) reached in the headspace vial; because the vial is
thermostated at a temperature higher than atmospheric
(Tv > To), the headspace pressure in the vial will also be
higher than atmospheric pressure (Ph > Po)'
5
 | |
EQUILIBRATION ~l
CYL,'NDER
~.
r-
N 1 MOVABLE
3AhfPLIN6
NEEDLE
SAMPLE
VIAL
i--:------:-:J
ANALYSIS OF NEXT HEADSPACESAMPLE
Figure 1
The three basic steps of headspace sampling: (A) equilibration, (B) pressurization, and (C) transfer of an aliquot
of the headspace gas into the column.
During equilibration (Figure 1A) the needle is in a standby
position and its openings arc closed; the carrier gas flows
directly to the column. After equilibrium is reached,
sampling is commenced. In the first step (pressurization,
Figure ]B) the needle penetrates the serum cap of the vial
into the hcadspace; now the upper opening of the needle is
located so that part of the carrier gas can flow into the
sample vial and to build up its pressure until Ph = Pi- As the
next step (sample transfer: Figure 1C) the carrier gas flow is
temporary disconnected. Because the sample vial is now
open to the column through the needle, and because at that
instant the pressure in the vial is equal to the headpressure
of the column, there is a flow of the headspace gas
transferring an aliquot of the gas onto the column. In the
system used by us the exact volume of this aliquot is
controlled by 'controlling the time of transfer. It is also
possible to insert a sample loop between the sample vial and
the column, and some commercial systems use this
arrangement. After the preset transfer time the transferred
gas sample is analyzed in the gas chromatograph while the
system switches back to the initial position (Figure 1A),
ready for the next sample. The peak area (A) obtained for
a volatile c o m p o u n d present in the sample will be
proportional to the concentration of the analyte in the
headspace (c~';):
A = (const.) c G
The distribution of the analyte between the sample and the
headspace (the gas phase) of the vial is described by its
distribution (partition) coefficient, K:
6 Chromatographia Vol. 32, No. 1/2, July 1991
9
PRES~UI~IZATION FRANSFEI~
L L
~ M N V [-
q CARRIER
Cr
b
]
/
_ o _
o_
[AMPLE o _
; . - -
K = c /ca (2)
where c} and c*G are the equilibrium concentrations of the
analyte in the sample and in the headspace (the gas phase)
of the vial, respectively. At a given temperature and for a
given sample, K is constant, Through this proportionality,
the peak area obtained can be directly related to the
concentration of the analyte in the sample.
The relationships expressed by Eqs. (1) and (2) also make
clear that the aim should always be to obtain as large a peak
as possible. Since, under given conditions, the peak area
obtained is directly proportional to the concentration of the
analyte in the headspace, it is also evident that one should
try to have as high a concentration in the headspace as
possible. Since a higher headspace concentration and thus,
a larger peak area, facilitates the determination of a smaller
concentration in the sample, we sh all call this the "sensitivity"
of the headspace analysis. This is not a precise term: by it,
we simply want to indicate the importance of c~.
S a m p l e V o l u m e as a Variable
H S G C analysis is normally carried out with help of highly
automated instrumental systems in which thermostating
time and temperature, carrier gas pressure, and gas sample
transfer time and temperature are precisely controlled. For
(1)
a given system, the sample vials are also standardized. In
most cases the volume of the vial is about 22 mL; some
older, semi-automatic systems utilize vials with a volume of
about 10 mL.
Originals
There is one condition which the analyst may individually % 13
[~ = - - and ~G - (12a-b)
set: this is the volume (amount) of the sample placed in the
l-q5 G 1 +13
sample vial. Surprisingly, there is almost no information in
the literature dealing with the influence of the sample
volume on the analytical result. In this paper, we investigate At equilibrium the analyte is distributed between the two
this question in detail. phases, the gas phase (the headspace) and the sample
phase. We are using an asterisk to indicate equilibrium
conditions; thus, at equilibrium we have the following
Theory entities:
c~, m~ - concentration and amount of the analyte in the
Let us start with some fundamental definitions and
relationships. The original sample is defined by V s, m s and introduced sample, at equilibrium;
Cs, where c~, m~; - concentration and amount of the analyte in the
Vs is the volume of thc original sample introduced into gas phase (headspace) of thevial, at equilibrium.
the sample vial; Note the difference between m s vs. m~ and cs vs. c~. During
ms is the mass of the analyte in the original sample; equilibration part of the analyte originally present in the
introduced sample is transferred into the gas phase, so that:
es is the concentration of the analyte in the original
sample expressed as mass per volume: m~ < m s a n d c ~ < c s
and
Cs = ms/V s (3)
The volume of the sample vial is V v and the volume of the m s = m~ + m 6 (13)
headspace (the gas phase) in the vial, after the sample is
For the sake of simplicity we assume that the introduced
introduced, is Vo:
sample volume remained unchanged. This is not entirely
Vv = Vs + V G (4) true since it is now at an elevated tcmperature and under a
The volume of the sample in the vial, as a fraction of the higher pressure; however, we neglect these effects which
vial's volume, ca n be expressed by the samplephasefraction, are minor.
q~s: We have already defined K, the distribution coefficient, as
'gs = Vs/V v (5) K = c~/c~ (2)
An analogous term would be the gas phase (headspace) Defining the two concentrations as
fraction, ,.bG:
c~ ~- m~/V s (14)
(I}G ~ VG/V v (6)
Note that and
c~ = m~/V G (15)
% + 9G= 1 (7)
wc can express the distribution coefficient as
These two terms are similar to the mole or volume fractions
Used in many cases. One example is the term used in liquid c~ m? VG na~
chromatography relating the volume of a mobile phase K= - - 13 (16)
c~ raG* Vs m~
COmponent to the volume of the total mobile phase:
Going back to Eq. (12) we can carry out the following
X i- xi (8) modifications:
Xl + - . , + x i + . . . +X n (13)
m S = m~ + m *G
where xl ... xi ... xn arc the volume fractions of the individ-
mS lll~ ITI*
G
Ual COmponents of the mobile phase. - +

We can also express thephase ratio, ~, of the vial containing Vs Vs Vs

the Sample:
But V s = VG/[3 (cf. Eq. (9)); therefore,
: vs/v s : (v v - Vs)/V s (9)
The phase ratio can be interrelated with the phase fraction ms m* m*
_ s +_E. 13
expressions: Vs Vs VG
= OG/q, s (10)
Cs = c~ + c~,. (17)

1 - ~s 1 Also, since c~ = K.c~, (cf. Eq. (2)), therefore,

13- and q~s - (lla-b)
q5s 1 +13 c s = K . c h + c&.13 = c&[K + 13] 08)

Chromatographia Vol. 32, No. 1/2, July 1991 Originals 7

From this equation we can express c~,:
cS
c~ - (19)
K+t3
We can also describe Eq. (18) by substituting Eq. (10) or Eq.
(11 a) for [3:
cS
c6 - (20a)
K + (OG/cbs)
cS
c*G - (20b)
1- ~s
K+--
% saturation:pressure of the compound of interest which, in
Eqs. (20a-b) express the equilibrium concentration in the
vial's headspace as a function of the original sample
concentration, the distribution coefficient and phase
fractions. They indicate that it is really not the absolute
volumes of the vial and the sample which are important but
rather their relative values expressed by the phase fractions.
From thcse two terms wc shall use the sarnplephasefraction
because we are investigating the influence of the sample
volume. It is also clear that the distribution coefficient also
has a major role. Let us now investigate a number of
situations in order to see the influence of the sample
volume.
Practical Problems
We are going to investigate the influence of two volumes:
the sample volume (Vs) and the vial's volume (Vv), with
respect to the analytical reproducibility, the "sensitivity" of
the headspace analysis and the influence of the vial's volume.
A brief explanation of these questions is in order here.
In HSGC, the sample placed in a vial can be analyzed only
once* because the removal of an aliquot of the headspace
changes the conditions and a second aliquot would give
different results. Therefore, in HSGC, duplicate analysis
means the analysis of aliquots of the same sample contained
in separate vials. The question we are referring to is whether
a different sample volume would influence the analytical
reproducibility.
As stated in the Introduction, HSGC is usually carried out
in highly automated systems, assuring the reproducibility
of the analytical conditions, among others the volume of
gas sample introduced into the column. The question we
are referring to is whether the sample volume influences
the "sensitivity" of the headspace analysis: in other words,
whether, by manipulation of the sample volume, one could
influence the concentration of the compound of interest in
the headspace.
In the theoretical discussion we have shown that the prin-
cipal variable is a relative term, which we have called the
*Except in the case of the so-called multiple headspace extraction
(MHE), one of the methods used for the quantitative determination
of the amount of a volatile compound present in the sample [10-12].
8 Chromatographia Vol. 32, No. 1/2, July 1991
sample phase fraction. Still, one should investigate how an
absolute change in the vial's volume will influence the
analytical result.
The Influence o f the Sample Phase Fraction
The first question we shall investigate is the influence of the
sample volume in an otherwise fixed system, i.e., with a
fixed vial volume. In this case the question can be best
approached by expressing the sample volume relative to
the vial volume, i.e., as the sample phase fraction.
Eq. (20b) makes it clear that, in addition to the sample
phase fraction, the distribution coefficient also has a major
role. The distribution coefficient is primary related to the
turn, increases exponentially with temperature [6].
In practical HSGC, one tries to decrease the value of the
distribution coefficient, (i.e., increase the concentration of
the compound of interest in the headspace) by increasing
the thermostating temperature. However, the matrix
compound must also be considered if it is volatile: we do not
want to increase its concentration in the headspace above
a certain limit, particularly if its peak elutes from the
column close to and/or before the peak of the analyte,
because this would unfavorably influence the GC separation.
Many of the practical H S G C determinations analyze
compounds present in aqueous solutions and the above
mentioned consideration particularly applies for such cases.
For example, if ethanol is determined from aqueous solutio~
(which is the case when determining the concentration of
ethanol present in blood), thermostating is most ofte~
carried out at about 60 ~ where the distribution coefficient
of ethanol is still high (about 550). From the point of
ethanol one would like to use a s o m e w h a t higher
thermostating temperature, in order to decrease the
distribution coefficient: e.g., at 80 ~ it is about 250.
However, at this temperature the vapor pressure of water
would be increased to an undesirably high level and its large
p e a k - which emerges fairly close to that of ethanol-would
interfer with the small ethanol peak. On the other hand,
halocarbons, for example, have a much higher vapor
pressure at lower temperatures. Thus, in their determination
from aqueous solutions - one of the most important
environmental applications of H S G C - we have a very
favorable situation, with the value of the distributio~
coefficient close to unity.
It should be noted that in some cases, the value of the
distribution coefficient might even be less than unity which
means that upon equilibrium the concentration of the
analyte in the headspace is higher than in the sample (cf.
Eq. (2)). An example is the determination of vinyl chloride
monomer (VCM) in PVC plant effluents, an important
practical application of HSGC. In the H S G C method used
for this routine determination the vial is thermostated at
70 ~ At this temperature the distribution coefficient of
VCM for aqueous solutions is about 0.20*.
*The distribution coefficients given here were determined by Kolb,
using HSGC [13].
Originals
 Because of this wide range of the distribution coefficients,
we must investigate separately the situation with low and
high values. We shall consider three examples, with K
values of 0.20, 1.0 and 250. We assume the concentration of
the analyte in the sample as 100 ppb (= 100 ng/mL). For
each case, we shall consider two sample phase fractions, F s
= 0.20 and 0,80. In other words, we assume that the sample
volume is equal to 20 % and 80 % of the vial volume,
respectively. The calculations refer to a HS system with a
22-mL vial. Table I give the calculated numerical values
while an example for the calculation (for Case la) is given
in the Appendix. Below we express the results by giving the
COncentration of the analvte in the headspace at equilibri-
um (c~) as a function of tiae original sample concentration
(es) (cf. Eq. (20b)):
, Cs
cG =~
K + 1 - ~ S = a'cs (21)
~S
a- 1 volume has very little influence on the analytical results: a
1 -q~s
K + ~
~s
.Since in all cases we assume the same analyte concentration
m the samples (Cs) ' this a term is a direct indication of the
changes in the analyte concentration in the headspace for
various distribution coefficient and sample phase fraction
values
K - 0.21). (cf. Table I, Cases 1a-b). The following results
were obtained:
#
At dos = 0.20: c c = 0.238 cs
At dos = 0.80: c G = 2.222 cs
In other words, with a distribution coefficient of K = 0.20,
When filling the vial to 80 % of its volume by the sample, the
Concentration of the analyte in the headspace will be almost
ten times (precisely: 9.34 times) of that when the sample
OCCUpies only 20 % of the vial's volume.
Table I Numerical data for cases corresponding to samples with a
Wide range of distribution coefficients.
K = 1.00. (cf. Table I, Cases 2-b). The following results were
obtained:
At ~s = 0.20: c~ = 0.200 cs
At eos = 0.80: c~ = 0.800 cs
In other words, with a distribution coefficient of K = 1.00,
when filling the vial to 80 % of its volume by the sample, the
concentration of the analyte in the headspace will be four
times of that when the sample occupies only 20 % of the
vial's vohnne.
K = 250. (cf. Table I, Cases 3a-b). The following results were
obtained:
A t , b s = 0.20: C*G = 0.00394 cs
A t a ) s =0.80: c~=0.00400c s
In other words, with a distribution coefficient of K = 250,
the concentration of the analyte in the headspace will
increase only about one percent over the range of eos
considered.
The conclusion from these examples is that in the case of
samples with large distribution coefficients, the sample
one percent change in the headspace concentration for a 1:4
change in the volume (at K = 250) can be considered as
negligible; with a higher distribution coefficient, the
difference would be even less*. However, for low distribution
coefficients, the influence of the sample volume on the
concentration in the headspace is significant. Of course,
this influences the "sensitivity" of the headspace analysis
and may also influence the quantitative analysis. Whether
there is any such influence depends on the way quantitation
is carried out. In the case of the use of an internal standard,
there will be no difference in quantitation; however, if the
external standard, or standard addition methods are used,
it is important that the individual samples have the same
volume.
Sample-to-Sample Reproducibility
Let us consider a case when the sample is analyzed in
triplicate. For the sake of simplicity we assume a vial
volume of V v = 22 mL and a mean sample volume of 11 mL
(i.e., q~s = 0,5), with a + I mL change in the first and third
samples, representing a + 9.1% variation. We have the
following three cases:

la lb 2a 2b 3a 3b (a) (b) (c)

Cs ng/mL 100 100 100 Vs 10 mL 11 mL 12 mL
K
0.20 1.00 250.00 VG 12 mL 11 mL 10 m L
Vv mL 22.0 22.0 22.0 q~s 0.455 0.500 0.546
Vs mL 4.4 17.6 4.4 17.6 4.4 17.6
Vt3 mL 17.6 4.4 17.6 4.4 17.6 4.4
%
0.20 0.80 0.20 0.80 0.20 0.80 Again, we must consider separately the situations with the
4.00 0.25 4.00 0.25 4.0O 0.25 different distribution coefficient values. Table II gives
Ilns ng ~40.00 1760.00 440.00 1760.00 440.00 1760.00 numerical data for comparison; here only a summary of the
c~ ng/mL 23.81 222.22 20.00 80.00 0.394 0.40 results is given.
tn~. ng 419.06 977.77 352.00 352.00 6.934 1.76
c~ ng/mL 4.76 44.44 20.00 80.00 98.43 99.89
20.94 782.23 88.00 1408.00 433.07 1758.24
*For example, at K = 550,it is only 0.66 % for the two cases of c~s = 0.20
0.238 2.222 0.200 0.800 0.00394 0.00400 vs. 4~s = 0.80.

Qhromatographia Vol. 32, No. 1/2, July 1991 Originals 9

 Table II Numerical data corresponding to the examples used in the investigation of sample-to-sample
reproducibility.

4a 4b 4c 5a 5b 5c 6a 6b 6c
CS ng/mL 100 100 100
K 0.20 1.00 250.00
Vv mL 22.0 22.0 22.0
Vs mL 10.0 11.0 12.0 10.0 11.0 12.0 10.0 11.0 12.0
VO mL 12.0 11.0 ] 0.0 12.0 11.0 10.0 12.0 11.0 10.0
~I~S 0.455 0.500 0.546 0.455 0.500 0.546 0.455 0.500 0.546
1.200 1.000 0.833 1.2(X) 1.(/00 0.833 1200 1.000 0.833
ms ng 1000.00 1100.(X1 1200.00 1000.00 1100.00 1200.00 1000.00 1100.(X/ 1200.00
c(; ng/mL 71.43 83.33 96.81 45.46 50.00 54.56 0.3981 0 . 3 9 8 4 0.3987
m~ ng 857.15 916.66 968.05 345.46 550.00 545.55 4.778 4.383 3.987
c~ ng/mL 14.29 16.67 19.33 45.45 50.00 54.54 99.52 99.60 99.67
ms ng 142.85 183.34 231.95 454.54 550.00 654.45 995.22 1095.62 1196.01
a 0.714 0.833 0.968 0.455 0.500 0.546 0.004970 0.004975 0.004979

K = 0.20. (cf. Table If, Cases 4a-c). T h e following results Table !11 Numerical data for the investigation of tile influence of
were obtained: tim vial's volume.

(a) c*G = 0.714 c s 7a 7b 8a 8b

(b) c~ --0.833 c s
(c) c~, = 0 . 9 6 8 c s cs ng/mL i00 100
K 5.0 5.0
This corresponds to a variation of about + 15 %.
Vv mL 22.0 10.0 22.0 10.0
K = 1.00. (cf. Table II, Cases 5a-c). T h e following results Vs mL 4.4 2.0 4.0
were obtained: VG mL 17.6 8.0 18.0 6.0
(a) c~ : 0 . 4 5 5 c s ~S 0.2 0.182 0.4
(b) c~ = 0 . 5 0 0 c s 4.0 4.5 1.5
(c) c*G =0.546 c s ms ng 440.00 200.00 400.00 400.00
@, ng/mL 11.11 11.11 10.53 15.39
This corresponds to a variation of + 9 . 1 % .
mG ng 195.55 88.89 189.47 92.31
K = 250. (cf. Table II, Cases 6a-c). T h e following results c~ ng/mL 55.56 55.56 52.63 76.92
were obtained:
ms ng 244.45 111.11 210.53 307.69
(a) c~ = 0.004970 c s
(b) c~ =0.004975 c s
(c) CG* = 0.004979 Cs (i) The sample phase fraction is kept constant (at ~ s "
This corresponds to a variation of only + 0 . 1 % . 0.20) but the vial's volume (Vv) and hence, also the
sample volume (Vs) is changed (Cases 7a-b);
O u r conclusion is thus similar to that discussed earlier: the
sample volume is critical only for low distribution coefficient (ii) The sample volume is kept constant (at V s = 4 mL)
values. In the case of high values its influence on the but the vial's volume (Vv) and hence, also the sample
reproducibility of the analytical results is negligible. phase fraction (~s) is changed (Cases 8a-b).
As seen, in the first case, the concentration of the analyte in
the headspace (c~,) remained unchanged, while in the second
case, it changed: it became higher with the smaller-volume
Influence of the Vial Volume vial. These data permit us to draw the following conclusions;
In the Introduction we have mentioned that the various (a) If the sample phase fraction (aOs) is kept constant, the
commercial H S G C instruments do not necessarily use the "sensitivity" of the hcadspace analysis (which is
same type (volume) of vial although it is standardized for a proportional to c ~'~,the concentration in the headspace
given instrumental model. As mentioned, the two most volume at equilibrium) is the same, regardless of the
widely used vials have volumes of about 22 and 10 mL. vial's volume;
Thus, one may ask the question: if the same sample is (b) however, if the sample volume is kept constant, then
analyzed in these two vials under otherwise identical con- the headspace "sensitivity" will be higher with a
ditions, will there be any difference in the results? smaller-volume vial. This is, of course, in agreement
Using one typical example (% = 100 ppb, K = 5.0), Table I I I with our earlier conclusion related to the change in
presents the respective data for two comparisons, consider- the sample phase fraction: the headspace "sensitivity"
ing vials of 22 and 10 mL: is higher with a higher value of eps.

10 Chromatographia Vol. 32, No. 1/2, July 1991 Originals

General Considerations in the Selection of
lhe Sample Vial and the Sample Phase
Fraction
The second conclusion above would indicate preference
for a smaller-volume vial. A further argument against
larger vials (and we may add: also against too large sample
VOlumes) is related to the time needed for equilibration. B.
~sobvious that if the sample volume is increased then, due
to the increased diffusion path length in liquid or bulky
solid samples, the equilibration time will increase. Thus,
from this point only, a small-volume vial, containing a
Small-volume sample would seem to be more desirable.
We have seen earIier that the sample phase fraction, i.e., the
relative sample volume, has a major influence only in the
case of highly volatile analytes (i.e., when the distribution
coefficient is low), and in such cases a higher sample phase
fraction would result in a higher concentration of the
analyte in the headspace. This, in itself, would favor larger
q~s values.
There are, however, further points one must consider when
selecting the size of the sample vial and the sample phase
fraction. One of these is related to sample introduction into
the column: there must be enough headspace gas available
for transfer into the column. For example, in the case of
splitless injection into a conventional open-tubular column
(0.25-0.32 mm ID), typical volumes of the headspace gas
transferred into the column are 50-200 J.tL. In such a case a
vial with a total volume of 1 mL, and used with a sample
phase fraction of e.g., q~s = 0.5 would be satisfactory.
HOWever, for packed columns and larger-diameter open-
tubular columns, or for conventional open-tubular columns
Used in the split mode, typical gas volumes transferred into
the column are as high as 0.5-2.0 mL. Thus, for such a
sYStem, a 1-mL volume vial would be insufficient. This is
one of the reaso1~s why present-day H S G C systems are
standardized with larger-volume vials.
A further reason why, in general, larger vials are preferred
issample homogeneity. This is often a problem,particularly
With solid samples and, therefore, one would like to analyze
as large a sample as possible in order to get a representative
aliquot. For example, 5 grams of a soil sample are likely to
be more representative than a 500-rag aliquot. Another
example of this is the HSGC analysis of printed packaging
film for residual solvents - a very importanl application of
the technique - where the piece placed in the vial should
COvet- as much as possible of the various colors used for
~rinting the film: a 10 cm x 10 cm piece is certainly more
representative than a I c m x 1 cm aliquot. Thus, one needs
a vial into which such sizes of solid samples can be placed.
These considerations are the reasons why the commercial
bISGc systems utilize vials with a larger volume, typically
10-22 mL, where a large enough sample aliquot can be
inserted to be truly representative, whi~e the headspace
volume is enough for any type of columns.
COnsidering now specifically the sample phase fraction
q~S), the new term introduced in this paper, we have
emonstrated that this is the value und not the absolute
Sample volume which is of primary importance with respect
Chromatographia Vol. 32, No. 1/2, July 1991 Originals
to sample-to sample reproducibility, when comparing HiS
systems with different-volume vials and concerning the
"sensitivity" of the headspace analysis. Thus, this new term
is an important variable in HSGC.
Sample-to-sample reproducibility is influenced by the
constancy of the sample phase fraction only in the case of
low distribution coefficient values, i.e., in the case of highly
volatile analytes. In the case of analytes with high distribution
coefficient values at equilibrium conditions, the influence
of eps on sample-to-sample reproducibility is negligible.
With respect to the "sensitivity" of headspace analysis, if
the sample phase fraction (and not the absolute sample
volume) is kept constant, then the concentration of the
analyte in the headspaee (which is the variable primarily
influencing the "sensitivity") is independent on the actual
volume of the vial.
In general, if a high "sensitivity" of the headspace analysis
is desired, a relatively high sample phase fraction (ads) is
favorable. However, as indicated above, one must consider
the fact that a larger sample volume - particularly in the
case of liquid or bulky solid samples- increases the diffusion
path and hence, the time needed for equilibrium. Therefore,
for analytes having relatively high diffusion coefficients at
equilibrium conditions, sample phase fraction values of oPs
= 0.3-0.5 are recommended. On the other hand, for samples
containing analytes with higher volatility, sample phase
fraction values of 'I~s = 0.5-0.8 may be desirable.
Appendix
Example for the Calculation o f the Data Given in
Tables I - l I l
The example given here concerns Case la of Table I; all the
other calculations are carried out in a similar way.
The following values are set:
V v = 22 mL eos = 0.20 K = 0.20
c s = 100 ppb (wt/v) = 100 ng/mL
The calculated values:
Vs = q~s .Vv -- 4.4 mL t3 = (1- COs)leos : 4.00
V G = V v - V s = 17.6 mL
m s :: cs.V s = 440 ng
At equilibrium the amount and concentration of the ana-
lyte in the two phases will be:
c~-- Cs = I00 - 23.81ng/mL
1-OPs 0 . 2 0 + 4
K + ~
q~s
= c G .V c = 23.81 u 17.6 = 419.06 ng
ms = m s - m*G = 440 - 419,06 = 20.94 ng
cs = m*s/Vs = 20.9414.4 = 4.76 ng/mL
Finally, the value of a, used in the comparisons, is:
1 1
a= 1 - o0s 0.20 + 4 - 0.238
K + ~
~s
11
List of Symbols and Abbreviations
a A term expressed in Eq. (21).
A Peak area.
e*o Concentration of the analyte in the headspace volume
of the vial (the gas phase), at equilibrium.
cs Concentration of the analyte in the original sample.
cs Concentration of the analyte in the sample placed in
the vial, at equilibrium.
GC Gas chromatography.
HS Headspace;headspace sampling.
H S G C Headspace gas chromatography.
K Distribution (partition) coefficient of the compound
of interest at equilibrium, at the thermostating
temperature (= Cs/C~).
m o Amount of the analyte in th e headspace volume of the
vial (the gas phase), at equilibrium.
m s Amount of the analyte in the sample placed in the
vial, under the original conditions.
m*s Amount of the analyte in the sample placed in the
vial, at equilibrium.
Pi Carrier gas pressure at column inlet (headpressurc).
Po Atmospheric pressure.
Ph Pressure in the headspace of the sample vial, at
equilibrium.
T O Atmospheric temperature.
T v Temperature in thevial (thermostatingtemperature).
V G Volume of the headspace (the gas phase) in the vial.
V s Volume of sample in the vial.
V v Total volume of the vial.
[3 Phase ratio of the vial (= VUVs).
~G Gasphase (headspace) fraction in the vial (= V d V v ) .
~s Sample phase fraction in the vial (= Vs/Vv).
* Asterisk refers to equilibrium conditions.
12 Chromatographia Vol. 32, No. 1/2, July 1991
References
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[13] B. Kolb, unpublished data.
Received: Feb. 4, 1991
Revised manuscript
received:April 27,1991
Accepted: May 2, 1991
A,E
Originals