Gas-Solid Chromatography of Hydrogen Bonding Compounds
Antonio Di Corcia and Fabrizio Bruner
Istituto di Chimica Analítica and Laboratorio Inquinamento Atmosférico del Consiglio Nazionale delle Ricerche,
Universita di Roma, 00185 Roma, Italy
The use of gas-solid chromatography is extended to
the elution of polar compounds by treating Graphon,
MT, and FT with hydrogen at 1000 °C. In comparing
the adsorption isotherms before and after treatment,
it appears that chemisorbed oxygen, always present in
these adsorbents, is removed. Peak tailing is elimi-
nated or strongly reduced and the elution of tiny
amounts of alcohols, aliphatic amines, and free car-
boxylic acids can be performed on these columns. The
results given by the adsorbents used are compared
with those obtained with GLC and untreated materials;
several analytical applications can be realized with this
chromatographic material.
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The interest of analytical chemists in gas-solid chroma-
tography has grown rapidly since a number of important
results have been achieved with this technique. The analysis
Downloaded via TUBITAK ULAKBIM on October 8, 2019 at 13:13:07 (UTC).
of permanent gases and low boiling liquids is possible at room
temperature only with gas-solid chromatography and certain
problems oP'igh selectivity can be solved with it (J).
This development is related to a number of achievements
concerning the possibility of better controlling the homono-
geneity, geometrical structure, and chemical nature of the
adsorbents.
Moreover, the fact that most of the adsorbents have a high
thermal and chemical stability and that the expansion of the
working range of the gas chromatographic columns can be
now raised up to 500 °C, makes adsorption gas chromatog-
raphy particularly valuable for use with analytical tempera-
ture-programmed columns.
Nevertheless, gas-liquid chromatography is more widely
used than GSC for the analysis of hydrogen bonding com-
pounds, even though gas-liquid partition presents some
serious problems; among these bleeding of the fixed liquids
at high temperatures is by far the most important.
The chief obstacle to the analysis of such compounds by
GSC is the fact that an otherwise uniform surface is always
contaminated to a greater or lesser extent by active functional
groups which yield specific interactions.
Such chemical inhomogeneity has a profound influence on
the adsorption of polar compounds, provoking an initial
pronounced “knee-bend” in the absorption isotherms, at
least yielding the peak asymmetric or, in many cases causing
an almost irreversible adsorption, responsible for the so
called “ghost peaks.”
Several methods have been described to linearize the ad-
sorption isotherms, the most important being the following:
Deposition of monomolecular layers of strongly adsorbed
substances (especially polymers) on the absorbing surface of a
nonporous or macroporous adsorbent (2); blocking of the
active centers of an inhomogeneous surface with a highly
polar liquid (3, 4); and use of a strongly adsorbed carrier
(1) M. Taramasso and A. Timidei, in reprints of the 8th Inter-
national Symposium on Gas-Chromatography, N. Stock, Ed.,
Institute of Petroleum, London, 1970, paper 3.
(2) C. Vidal-Madjar and G. Guiochon, Nature, 215, 1372 (1967).
(3) J. R. Lindsay-Smith and D. J. Waddington, Anal. Chem.,
40, 523 (1968).
(4) A. Di Corcia, D. Fritz, and F. Bruner, ibid., 42,1500 (1970).
1634 · ANALYTICAL CHEMISTRY, VOL. 43, NO. 12, OCTOBER 1971
gas or mixing of proper deactivating substances in a common
carrier gas (5, 6).
In some cases, the methods mentioned above attain the aim
of eliminating the active centers completely, but each of them
has some serious limitations. For example, as already re-
ported in our recent work (4), surface coating of Graphon,
a well known example of partially graphitized carbon black,
with small amounts of liquids, whose affinity for the active
sites is analogous to that of the compounds to be analyzed,
yielded good results for the linear elution of highly polar
compounds. But, because of the relatively high volatility
of the deactivating liquid ( or glycerol), its use is limited
to the range of temperature below 100 °C.
Our efforts have recently been devoted to the search for
adsorbents for gas-solid chromatography which are able to
elute polar compounds even at very low concentrations,
without the use of any deactivating agent. This would allow
working at high temperatures, eliminating bleeding from the
column, and this is particularly important for gas chroma-
tography-mass spectrometry coupling. Moreover, the high
selective power and versatility of GSC would possibly open
new methods for faster and more effective analysis of com-
plex mixtures.
On the point of view of the adsorption energy, an ideal
adsorbent should be gaussian, i.e., the heats of adsorption
on the adsorptive sites should be displayed symmetrically
around an average value. This can be accomplished only if
the surface is geometrically and chemically homogeneous.
This is never true even with carbon blacks, which are normally
considered homogeneous adsorbents.
About fifteen years ago, Millard et al. (7) reported that the
surface oxygen complex on Graphon could be removed by
heating the adsorbent in a stream of hydrogen at 1000 °C.
After the hydrogen treatment, adsorption of water no
longer showed the small “knee” at the low-pressure end of the
isotherm, thereby indicating the disappearence of the im-
purity.
In this work we repeated the hydrogen treatment on
Graphon and extended it to other types of carbon blacks,
such as FT and MT. Very satisfactory results have been
obtained for the gas chromatographic analysis of mixtures
of aliphatic and aromatic amines and mixtures of aliphatic
acids and alcohols with very low sample sizes. The shape
of the adsorption isotherms before and after the treatment
are compared and their effect on the chromatographic proper-
ties of the adsorbents is discussed.
EXPERIMENTAL
Hydrogen Treatment. The carbon black sample, pre-
viously sieved at the desired mesh range, is placed in a piece
of iron tubing, which is in turn placed in a cylindrical oven
(Bicasa, Milan). The oven is then heated, keeping the
(5) J. Janak, Collection Czech. Chem. Commun., 19, 684(1953).
(6) A. Liberti, G. Nota, and G. Goretti, J. Chromatogr., 38, 282
(1968).
(7) B. Millard, E. G. Caswell, E. E. Leger, and D. R. Mills, J.,
Phys. Chem., 59, 876 (1955).
Figure 1. (a) Isotherms for methanol at 78 °C on
Graphon and on hydrogen-treated Graphon
(b) Isosteric heats of adsorption of methanol on
Graphon and on hydrogen-treated Graphon
0 10
sample under a pure hydrogen stream up to 1000 °C. This
temperature is maintained for about 4 hours. The time is
not very critical. In the original paper the treatment was
carried on for 12 hours, but in our experience no significant
further improvement is observed by extending the treatment
beyond 4 hours. A treatment time less than 4 hours can
sometimes give some irreproducibility of results.
Gas Chromatography. A Carlo Erba model GI gas chro-
matograph, equipped with a flame ionization detector was
used. For the determination of adsorption isotherms,
Teflon (Du Pont) tubing (1 m X 3 mm i.d.) was used as
column material. The mesh range was 60-80. Methanol
of research grade, injected by a 10-µ1 syringe (S.G.E. Mel-
bourne, Australia), was properly split at the column inlet
to obtain the desired sample size (10~6 gram).
The mesh ranges used for analytical columns were 60-80
and 80-100 for FT and MT, respectively. Glass columns
(80 cm X 2.5 mm i.d.) were used.
Artificial mixtures were prepared from commercial
sources. Graphitized carbon blacks were kindly furnished by
Dr. W. R. Smith from Cabot Corp., Billerica, Mass.
Pure nitrogen was used as carrier gas.
Analytical tests were performed using synthetic mixtures
consisting of solutions 1/10,000, V/V of each compound,
usually in diethyl ether, or in distilled water when low-boiling
amines were examined.
Sample blends were injected with a 10-µ1 S.G.E. syringe,
ANALYTICAL CHEMISTRY, VOL. 43, NO. 12, OCTOBER 1971
20 30 40 -
50
a io6
(9/9)
conveniently split to obtain the desired amount. When
hydrogen-treated adsorbents were examined, no ghosting
phenomena were observed and reproducibility of peak areas
for the same amount of any polar compound was about
1-3%, the range difference being attributed to syringe tech-
nique.
RESULTS AND DISCUSSION
Isotherm Modification by Hydrogen Treatment. The
isotherms and the isosteric heats of adsorption vs. coverage
of methanol for both untreated and hydrogen-treated Gra-
phon are shown in Figure 1 a and lb. Absorption isotherms
have been obtained from the chromatograms, using a method
devised by Glueckauf (8) and largely used by Kiselev (9).
From the isotherms at various temperatures, the isosteric
heats of adsorption at any value of surface coverage have been
calculated graphically by plotting the adsorption isosteres as
In p vs. 1 ¡T and determining the slope, which equals —q,%\R.
In these cases, straight lines were obtained and reproducibility
of heats of adsorption was good to within 3-4%.
That hydrogen treatment has removed chemisorbed oxygen
(8) E. Glueckauf, Discussions Faraday Soc7, 199 (1949).
(9) A. V. Kiselev, “Advances in Chromatography,” vol. 4, J. C.
Giddings and R. A. Keller, Ed., Dekker, New York, N.Y., 1967.
· 1635
Figure 2. (a) Isotherms for methanol at 33 °C on
FT and hydrogen treated FT
(b) Isosteric heats of adsorption of methanol on FT
and on hydrogen-treated FT
from Graphon is well evidenced because at any value of
partial pressure of methanol in the gas phase, the surface
of Graphon treated shows much less affinity for the hydrogen
bonding adsorbate than the untreated material, since at every
pressure the amount of methanol adsorbed is lower; after
the treatment, the initial curvature of the adsorption isotherm
is appeased, showing a more gaussian distribution of the
adsorptive sites; as a consequence, the isosteric heat curve
for treated Graphon, Figure lb, lies quite markedly lower
than that of the untreated material.
However, because of a residual specific activity of the
surface, the heat curve is not completely flat at low surface
coverage. Better results are obtained when FT and MT, two
other well-known examples of the G.C.B. series with surface
areas of about 15 and 8 mJ/g, respectively, are purified by
hydrogen at 1000 °C. Adsorption isotherms and isosteric
heats, relative to the adsorption of methanol on FT, are shown
in Figures 2a and 2b. The behavior of methanol on MT is
quite similar.
In this case, the great influence which a small amount of
residual oxygen has on the adsorption of the hydrogen-
bonding molecules is emphasized by the fact that the con-
taminated surface yields a type II isotherm, whereas the clean
surface gives a type III isotherm. This demonstrates that,
owing to high surface homogeneity, adsorbate-adsorbate
interactions come into play during adsorption of methanol
on purified FT also at low surface coverage. This results in
an increase of the heat of adsorption with increasing surface
coverage (Figure 2b).
Analytical Applications. Analytical applications of gas
chromatography offer a striking confirmation of the very
important improvement which can be obtained in the analysis
1636 · ANALYTICAL CHEMISTRY, VOL. 43, NO. 12, OCTOBER 1971
of “polar” mixtures, by using graphitized carbon blacks
previously decontaminated by hydrogen at 1000 °C.
Before discussing the results of this work, it is useful to
make a survey on the present situation in gas-solid chroma-
tography of polar compounds.
To date, the best examples of adsorbents available for the
analysis of polar compounds are the Porapak series, the
Chromosorb “Century Series,” and the graphitized carbon
blacks. The first two types of adsorbents, which are porous
cross-linked polymers, allow the analysis of any polar com-
pound. Nevertheless, there are three serious limitations to
the extensive use of these adsorbents. First, these polymers
cannot be used at temperatures above 230-250 °C, because at
higher temperature thermal degradation occurs. Second,
because of the high surface development of these polymers,
the compounds injected exhibit a large retention. For this
reason, coupled with their thermal instability, analyses of
polar compounds must be confined to the first terms of each
homologous series.
Last, but not least, relatively large samples of strong hydro-
gen-bonding compounds must be injected, in order to avoid
tailing of the peaks. This is probably due to a certain re-
sidual specific activity of these adsorbents.
As far as graphitized carbon blacks are concerned, their
surface density of hydrophilic sites is somewhat larger than
the preceding adsorbents, but these supports have no prob-
lems of chemical or thermal stability and surface development
of FT or MT does not hinder the elution of high-boiling
compounds.
The forthcoming results show that the potentiality of GSC
can be greatly enhanced by the use of purified graphitized
carbon blacks.

Figure 3. Chromatogram showing the elution of
C4-C8 «-alcohols.
Column, 0.8 in X 2.5 m; packing material, FT (hydrogen
treated); sample size, 3 X 10
"8
gram; temperature,
165 °C; flow rate, 30 ml/min
In Figure 3,elution of C4-C8 «-alcohols is shown. This
chromatogram is particularly interesting as far as sample
size, column efficiency, and elution time are concerned.
Sample size, referred to each component, is, in fact, only
about 3 nanograms. Nevertheless, all peaks are still per-
fectly symmetrical. Moreover, it is noteworthy that the
number of effective plates, referred to «-octanol, is 1800 per
meter of column.
That GSC yields, especially at high linear gas velocities, a
higher column efficiency than GLC, has been explained (10)
in terms of a mass-transfer coefficient that is more favorable in
the case of gas adsorption than gas-liquid partition. This
difference becomes more pronounced when polar mixtures
have to be eluted. In this case, in order to avoid negative
adsorption effects by the supports, the liquid phase film thick-
ness must be rather high, and this affects the mass-transfer
coefficient negatively and causes peak broadening. Finally,
another interesting feature shown by the chromatogram
reported above is the short retention time exhibited by the
compounds eluted. In this connection it is interesting to note
that at 75 °C the retention time of n-butanol on a Hz-treated
FT column is only 3.5 minutes. We have found that the
same compound eluted at the same temperature, flow rate,
and column length has a retention time of 8.5 minutes using
Chromosorb W coated with 20% Carbowax 600. Using
other stationary phases, such as FFAP or Trimer Acid, «-
butanol requires even higher times to be eluted.
(10) A. V. Kiselev and Y. I. Yashin, in “Gas-Adsorption Chroma-
tography,” Plenum Press, New York, N.Y., 1969, p 2.
ANALYTICAL CHEMISTRY, VOL. 43, NO. 12, OCTOBER 1971
Figure 4. Chromatogram showing the elution of
C4-C8 free fatty acids
Column, 0.8 m X 2.5 mm; packing material, FT
(hydrogen treated); sample size, 1 X 10"7 gram;
temperature, 190 °C; flow rate, 30 ml/min
That analysis of polar mixtures can be performed by GSC
within a shorter time than by GLC is further confirmed by
the chromatogram of Figure 4, where the elution of C4-C8
free fatty acids at 185 °C is reported.
To emphasize what is said above, a comparative test has
been made. At 150 °C, 0.1 µ% of «-butyric acid was eluted
within 50 sec, using Hz-treated FT. On the other hand, to
elute the same compound, at the same operating conditions,
using FFAP, Ethofat, and Trimer Acid as liquid phases (11),
elution time of 8 min, 6.4 min, and 5.3 min, respectively, was
needed.
Retention times are used instead of specific retention
volumes because the operating conditions of GLC and GSC
are so different and so critical that the only way to make a
comparison of the results obtained with the two techniques
is to look at the analysis time required to have the most effec-
tive separation of certain compounds in the two cases.
Furthermore, the differences in the physical dimensions to
be used for expressing specific retention volumes in GLC and
GSC make a numerical comparison on these completely
unsignificant.
As can be seen, at a level of about 0.1 µg, free fatty acids
give some tailing of peaks. These broadened trailing edges
can be due to different reasons: adsorption by the injection
system, self-dimerization of the acidic molecules (12), or
residual basic activity not eliminated by the hydrogen treat-
ment. In spite of this, from the point of view of the amount
(11) W. K. Lee and R. M. Bethea, J. Gas Chromatogr., 6, 582
(1968).
(12) A. T. James and A. P. S. Martin, Biochem. J., 50, 679 (1952).
# 1637
 2 4

Figure 5. Chromatograms showing the elution of aliphatic and aromatic

amines at several temperatures on MT (hydrogen treated)
(a) Column, 0.8 m X 2.5 mm; sample size, 3 X 10gram; temperature, 94 °C;
flow rate, 25 ml/min; 1, methylamine; 2, ethylamine; 3, trimethylamine; 4, tert-
butylamine; 5, isobutylamine; 6, n-butylamine
(b) Column, 0.8 m X 2.5 mm; sample size, 1 X 10~7 gram; temperature, 133 °C;
flow rate, 20 ml/min; 1, dimethylamine; 2, «-propylamine; 3, pyrrolidine; 4, di-
ethylamine; 5, piperidine; 6, di-n-propylamine;
(c) Column, 0.8 m X 2.5 mm; sample size, 1 X 10~7 gram; temperature, 243 °C;
flow rate, 15 ml/min; 1, Aniline; 2, «-heptylamine; 3, di-n-butylamine; 4, /V-methyl-
aniline; 5, n-octylamine; 6, , -dimethy¡aniline; 7, «-nonylamine; 8, ’, '-diethyl-
aniline

injectable, our column is more than competitive with respect
to GLC columns. Besides, no “ghosting” phenomena were
observed during our experiments.
Finally, in Figure 5 chromatograms of amines at several
temperatures on hydrogen-treated MT are reported.
In the case of amines, adequate applications of gas chroma-
tography have not been completely achieved. This fact is
largely due to the ease of hydrogen-bond formation with
amines.
Only two recent papers (4, 13) deal with quantitative mea-
surements of amines at very low concentration by gas chroma-
tography.
However, they have a limitation in that, because of the
relative volatility of the stationary phases used, only the first
terms of the amines can be eluted. It has already been shown
(74) that amines can be eluted by gas-solid chromatography
using a nonspecific adsorbent, like MT. But if the sample
size is less than 10~3 gram, badly skewed peaks are obtained.
Moreover, we found that if the amount of very active amine,
e.g., «-propylamine, is about 10-5 gram, almost no signal
is observed on the recorder paper.
On the contrary, after hydrogen treatment at 1000 °C, the
minimum sample size injectable can be lowered to about 0.1
Mg. As can be seen from Figure 5c, peaks relative to less
active amines, like aromatic and long-chain aliphatic amines,
(13) G. R. Umbreit, R. E. Nygren and A. J. Testa, J. Chromatogr.,
43, 25 (1969).
(14) A. V. Kiselev and Y. I. Yashin, Zh. Fiz. Khim., 40, 603 (1966),
are perfectly symmetrical, thus indicating that, in this case,
the sample size can be further decreased.
Another interesting feature shown by the chromatograms
relative to amines, is that, using appropriate temperature
programming, a large number of amines at low concentration
can be analyzed.
Low boiling amines must, in fact, be eluted on very polar
liquid phases, which cannot usually be used at the high tem-
peratures needed for the analysis of the high boiling terms.
Different columns must also be employed.
In eluting amines, MT yielded more symmetrical peaks
than FT. The reasons for this behavior have not been clari-
fied, and it seems to depend on the fact that the impurities
of the starting materials relative to the two graphitized carbon
blacks are quite different. On the other hand, MT shows the
same degree of deactivation as FT with regard to alcohols
and fatty acids. But, because of the very low mechanical
resistance of MT, which causes difficulties in its handling
and strongly affects the performance of the GC columns, FT
was preferred. Furthermore also in the elution of amines,
no “ghost peaks” have been observed.
As has been pointed out in the Experimental Section,
consecutive elutions of the same amine gave reproducibility
of the peak areas of about 3 %.
Finally, in Table I a comparison between the treated and
untreated graphitized carbon blacks is reported.
The quantities listed refer to the minimum sample size for
which reproducible retention times are obtained.
The results described above show that GSC of hydrogen

1638 · ANALYTICAL CHEMISTRY, VOL. 43, NO. 12, OCTOBER 1971

 lowered, so that treated FT and MT give considerable scope
Table I. Data
for rapid analysis with columns of high performance.
Elution Minimum
However, the most interesting point arising from this work
time, T, sample
min °c is the possibility of eliminating bleeding of the stationary
Sample Adsorbent size, ga
phase, which causes serious trouble for gas chromatography-
n- Amyl-alcohol Sterling FT 0.7 160 1 X io-6
Sterling FT
mass spectrometry coupling.
(H2 treated) 0.7 160 3 X 10-» The use of our columns coupled with mass spectrometry
/z-Butyric acid Sterling FT 1.3 190 1 X 10~4 can lead to cleaner and more reliable mass spectra, and,
Sterling FT consequently, to easier identification of an extended range of
(H2-treated) 1.3 190 1 X 10~7
X to"4 compounds, including the very polar, high-boiling and multi-
N-Methylaniline Sterling MT 1.4 243 1

Sterling MT
functional ones, which are contained in very complex mixtures
(H2-treated) 1.4 243 1 X 10~7 of interest in the fields of biological and biomedical chemistry.
°
This is the minimum amount to obtain reproducible retention
times.
ACKNOWLEDGMENT
The authors are indebted to A. Liberti for helpful dis-
bonding compounds with hydrogen-treated graphitized carbon cussions and R. Samperi for technical assistance.
blacks is not only competitive with, but in many cases defi-
nitely more convenient than, GLC on porous polymers.
The range of linearity of GSC is extended so that small Received for review March 30, 1971. Accepted June 22,
amounts of any polar compound can be detected. Column 1971. This work is supported by the Consiglio Nazionale
efficiency is enhanced and retention times are considerably delle Ricerche.

Electrooxidation of Iodine on Smooth

Platinum in Acetic Acid Medium

Influence of Adsorption of Electrode Products

upon Voltammetric Limiting Currents
Rolando Guidelli and Giovanni Piccardi
Institute of Analytical Chemistry, University of Florence, Florence, Italy

Iodine in acetic acid gives a single anodic voltammetric
curve on smooth platinum. The mean limiting current
decreases progressively with the rest time of the elec-
trode at a given constant potential tending to an asymp-
totic value, owing to the adsorption of electrode prod-
ucts. The use of a normal pulse-polarographic tech-
nique applied to a solid platinum microelectrode per-
mitted us to eliminate the inconvenience due to ad-
sorption. It was thus possible to attribute the anodic
wave of iodine to its electrooxidation to lv. A plausible
rate-determining stage for the overall electrode pro-
cess l2 ->- !v is the following: l2 I1 + l«u„.b.d + e.
Some general considerations about the influence of
and coworkers (2). In the cell of the DLPRE a Teflon-
finned piston containing an iron nucleus is moved by a mag-
netic coil, activated by short current pulses, producing a
rapid laminar flow of the solution around a hemispherical
platinum microelectrode. This flow is interrupted abruptly
by a valve about 30 msec (washing period, u) from its start.
With technique I, the cell of the DLPRE is directly con-
nected to a conventional polarograph. In this case the piston
is moved at regular intervals of time Zi, of the order of 3 to 5
sec. The washing period, z„, is therefore followed by a much
longer period of time, (Zi —

/») ~ h, during which the solution

the adsorption of electrode products upon voltam-
metric limiting currents are presented.
In a preceding paper (/) the authors reported that in acetic
acid, iodine gives two cathodic waves on a smooth platinum
microelectrode, due to its reduction to Ir and I"", respectively.
Tne aim of the present work is to study the behavior of iodine
toward electrooxidation on platinum in acetic acid medium.
To this end two different polarographic techniques were
employed, herein referred to as techniques I and II, both
making use of a platinum microelectrode with periodical
renewal of the diffusion layer (DLPRE) described by Cozzi
is perfectly still. If the potential applied to the DLPRE
is such as to allow the occurrence of a charge-transfer process,
then, during the washing period r„ the depolarizer reaches the
electrode surface both by diffusion and convection. At the
end of period tw, the depolarizer moves only by diffusion,
so that the instantaneous current decreases with time. At
the end of period Zi, a new washing sweeps away to a large
extent the effect of prior electrolysis; hence, the instantaneous
current increases sharply, reaching a maximum value, z'max,
at the end of the new washing period. The geometry of the
cell and the energy of the washing are so adjusted that z'm»x

(2) D. Cozzi, G. Raspi, and L. Nucci, J. Electroanal. Chem., 12, 36

(1) R. Guidelli and G. Piccardi, Anal. Lett., 1, 779 (1968). (1966).

ANALYTICAL CHEMISTRY, VOL. 43, NO. 12, OCTOBER 1971 · 1639