iGC SEA
Reproducibility of the Dispersive Component of
Surface Energy Measured by Inverse Gas
Chromatography.
Part I: Energetically Homogeneous Powders
Surface Measurement Systems Ltd.
The aim of this study is to demonstrate the unrivalled performance of the SMS iGC SEA instrument, as well
as the effect of column-to-column variability on the results obtained.
Introduction
In this technical note, the experiment-to-
experiment and column-to-column
reproducibilities for inverse gas chromatography
experiments performed with an SMS iGC SEA
have been investigated.
4-acetamidophenol, a readily available
pharmaceutical ingredient, has been used as a
representative material for the determination of
the dispersive component of the surface energy
by iGC SEA. This material, in common with many
pharmaceutical compounds, is expected to be
energetically homogeneous.
Method
4-Acetamidophenol, commonly known as
paracetamol, was purchased from Sigma Aldrich
with a purity of minimum 99.0%. For the
preparation of the columns, around 250 mg of
the powder was filled into a silanised standard
column (2 mm ID, 300 mm long) using the SMS
sample-packing device. All the columns have
Technical
Note 801
been prepared using the same batch of material
and using the same frequency and duration of
tapping during packing.
All analyses were carried out using the SMS-iGC
SEA instrument and the SMS-iGC v1.1 analysis
suite of macros.
All columns were initially conditioned at 30oC for
2h and 0% relative humidity (RH) and
experiments were carried out at 30°C and 0% RH
with injections of 0.03 P/P0 elutant vapour
concentrations for all elutants. A flame ionisation
detector was used to determine the
chromatograph and resulting retention times.
The analysis of the dispersive component of the
surface energy was performed by measuring the
net retention volume VN (measured retention
volume – dead volume) for a series of alkane
elutants (undecane, decane, nonane, octane and
heptane). The dead volume was determined by
injecting methane, a probe molecule that does
not interact significantly with low energy
materials.
By plotting RTln(VN) versus a(γLD)1/2 , where a is
the molecular area of the probe molecule and γLD
is the dispersive component of the surface energy
of the liquid elutant (surface tension), a straight
line is produced. Its slope equals to 2NA(γSD)1/2
P-SCI-317 v1.0 12NOV2013
from which γSD, the dispersive component of the
solid surface energy, can easily be deduced [1].
A total of twenty-two different columns (labelled
A, B, C, …U, V) of 4-acetamidophenol were
packed and analysed.
Columns A-D have been analysed 10 times in a
row (i.e. using the same column) while
performing another conditioning of 2h at 30oC
between each run.

Figure1.Experiment to experiment reproducibility

Results of dispersive component of surface energy.

-Column A –
The results are given in Tables 1 & 2. Table 1
displays the values of dispersive surface energy
obtained for the 10 successive runs carried out on
columns A-D whereas Table 2 displays the values
obtained for the first run of all 22 columns.
In Figures 1 & 2, the dispersive component of the
surface energy for all ten runs of sample A and
sample B respectively are plotted.
Figure 3 illustrates the dispersive component of
the surface energy of the first run of the 22
different columns.
Table 1: Experiment-to-experiment reproducibility Figure2.Experiment to experiment reproducibility
results (10 runs of columns A, B, C & D of 4- of dispersive component of surface energy. -
acetamidophenol) Column B –
-2
Column Dispersive component of surface energy (mJ.m )
Run1 Run2 Run3 Run4 Run5 Run6 Table 2: Column-to-column variability results (first
run for all 22 columns of 4-acetamidophenol)
A 40.36 42.17 42.50 43.52 43.55 44.17
Column A B C D E F G H I J K
B 41.80 41.79 43.60 43.16 43.06 44.33 Disp comp
of
40.36

41.80

37.16

41.97

42.84

41.45

41.10

43.56

43.19

41.75

42.55

Surface
C 37.16 39.08 40.62 41.50 41.26 41.62 energy
mJ.m-2
D 41.97 42.64 44.44 45.38 45.72 45.81 Column L M N O P Q R S T U V
Disp comp
Column Run7 Run8 Run9 Run10 Mean Std
of
Dev Surface
43.00

41.29

39.03

42.99

41.36

41.84

42.60

44.34

40.47

42.51

42.22

(Run 1- 10) energy

A 44.33 42.67 43.40 43.05 42.95 2.52% mJ.m-2

B 44.33 43.40 42.29 42.25 43.00 2.07%

C 41.78 41.13 41.31 41.38 40.68 2.4%

D 47.02 45.68 46.44 45.97 45.11 3.42%


Figure3.Coumn to column variability of dispersive
component of surface energy – Run1 for all 22
columns-
The standard deviation is defined as the square
root of the sample variance. It has been
calculated using the following equation:
and has then been expressed as a percentage of
the average value.
The standard deviation for the dispersive
component of the surface energy determined for
10 successive runs carried out on the same
column ranges between 2.07% and 3.42% for the
four columns tested (A-D). The experiment-to-
experiment reproducibility is therefore very good
and inferior to 4%.
The standard deviation for the dispersive
component of the surface energy determined for
the first run of 22 different columns is 3.66%. The
column-to-column variability is also very good
and inferior to 4%.
The results are in good agreement with our
experience on a wide range of proprietary
pharmaceutical materials and other energetically
homogeneous powders.
Conclusions
This study demonstrates the excellent
reproducibility of the SMS iGC SEA instrument
compared to home-built iGC. The standard
deviation for experiment-to-experiment
reproducibility of dispersive surface energy is less
than 4%.
This is made possible thanks to the very accurate
mass flow controllers, the fully automated
injection system, the accurate temperature
control of the column oven and the separate and
accurate control of the solute temperature
provided by the SMS iGC instrument.
Most home-built iGCs do not offer such features
and therefore usually do not attain such a high
injection concentration accuracy and therefore
reproducibility in the results.
In addition, this study demonstrates that for an
energetically homogeneous material, the
variability between columns packed in the same
manner is comparable to the instrumental
reproducibility i.e. less than 4%.
The SMS iGC SEA instrument with its very good
reproducibility allows small differences between
samples to be measured reliably and therefore is
a useful tool in the determination of batch-to-
batch variations [2], surface treatment studies
[3], polymorph studies [4], investigation of
relative humidity on the determination of glass
transitions [5] and many other applications.
Acknowledgement:
SMS thanks Simone B. Reutenauer for her
contributions to the Technical note.
 iGC SEA
Technical
Note 801

References
[1]Frank Thielmann, David Butler, Determination of the dispersive surface
energy of Paracetamol by iGC at infinite dilution, SMS Application Note
202
[2]Simone B. Reutenauer, John Booth, Poul Bertensel, Identification of
Batch-to-Batch variations in the dissolution rate of a pharmaceutical drug
by iGC, SMS Case Study 501
[3]Frank Thielmann, David Butler, Investigation of the influence of
bleaching conditions on surface properties of standard hair samples by
iGC, SMS Application Note 210
[4]Dave A. Butler, Lesley A. Mackin, Characterisation of drug polymorphs
by iGC, SMS Application Note 207
[5]Frank Thielmann, Daryl Williams, Determination of the glass transition
temperatures of maltose and its dependence on relative humidity by
infinite dilution iGC, SMS Application Note 204

Head Office: United States Office:

Surface Measurement Systems, Ltd Surface Measurement Systems, Ltd, NA
th
5 Wharfside, Rosemont Road 2125 28 Street SW, Suite I
London HA0 4PE, UK Allentown PA, 18103, USA
Tel: +44 (0)20 8795 9400 Tel: +1 610 798 8299
Fax: +44 (0)20 8795 9401 Fax: +1 610 798 0334
Email: science@smsuk.co.uk Email: science@smsna.com