Industrial Health, 1996, 34, 167-176 167

ORIGINAL ARTICLES

Selection of Desorbing Solvents for Organic Compounds

from Active Carbon Tubes

Yoshimi MATSUMURA

National Institute of Industrial Health,

21-1, Nagao 6-chome, Tama-ku, Kawasaki 214, Japan

(Received March 26, 1996 and in revised form May 7, 1996)

Abstract: To ensure the effectiveperformance of active carbon tubes for working

environmentmeasurements,suitable desorbing solventswere selectedfor 46 kinds of
organiccompoundsby the phaseequilibriummethod. The criteria for suitabledesorbing
solventsin this study was desorptionof the objectivecompoundsfrom activecarbon at
efficienciesgreaterthan 90% and to givegoodseparationbetweenits own peak and that
of the objectivecompoundon a gas chromatogram.For most non-polaror hydrophobic
compounds,carbon disulfidewas a versatile and effectivesolvent. But for polar and
hydrophiliccompoundslike alcohol,N,N-dimethylformamide and dimethylsulfoxidewere
good desorbing solvents if their peaks did not overlap with those of the objective
compounds. Mixtures of lower molecular weight alcohols with carbon disulfide or
dichloromethanecould be alternative solventsfor hydrophiliccompoundsas well. A
thermodynamicparameter of the solute-solventsystem,i.e., the mixingenergy derived
from the solubilityparameter,gavea rough indicationof the effectiveness of solventsbut
it couldnot be used as a criticalindicatorfor the efficientdesorbingsolventsfor organic
vapors collectedon activecarbon.

Key words: Activecarbontube- Adsorption- Desorption- Solvent- GCanalysis-

Organiccompounds- Solubilityparameter- Phaseequilibriummethod

INTRODUCTION

Active carbon tubes are one of the most versatile tools to collect airborne organic
vapors for working environment measurements. Most kinds of vapors collected
by active carbon tubes are treated with organic solvents for desorption and then
analyzed by gas chromatography (GC). For this purpose, a solvent is required to
desorb the objective compound with high and reproducible efficiency, as well as
to give satisfactory separation of its own peak from the peak of the objective
compound in GC. Many combinations of organic compounds and solvents have
168 Y. MATSUMURA

been reported for working environment measurements'-3~, but some of them still
do not give satisfactory desorption or their GC peaks overlap with GC peaks of
solvents themselves or of impurities in commercial solvents. Many industries use
volatile organic compounds as solvents and materials in mixed states, and there-
fore active carbon tubes are required to collect multiple organic vapors simulta-
neously, but one kind of solvent often cannot desorb all of them from active
carbon. Thus, information on suitable and unsuitable desorbing solvents is nec-
essary for field workers. This study is designed to obtain general knowledge to
be used for selection of effective desorbing solvents that can be widely used for
active carbon tubes.
The objective 46 kinds of organic compounds underwent experimental measure-
ment of desorption efficiencies from active carbon with various solvents, using the
phase equilibrium method. Most of these organic compounds are used as organic
solvents in Japan, but the use of some compounds is restricted due to their speci-
fied toxicity. Benzene4~ is not permitted to be used as a solvent due to its car-
cinogenicity, and carbon tetrachloride5~, 1,4-dioxane5~ and 1,2-dichloroethane5~ are
under special government notification for their carcinogenicity demonstrated in
animal experiments. The use of carbon tetrachloride and 1,1,1-trichloroethane as
organic solvents is also prohibited, due to their ozone-destructive properties. Thus,
the kinds of industrial solvents that were popular in the past are being replaced
with new ones, and environmental measurements in the workplace need to cope
with such changes. The results of this study suggest suitable desorbing solvents
for those compounds not included in this study, according to analogous chemical
properties.

MATERIALSAND METHODS

Materials: Active carbon was steam-activated coconut shell carbon, Pittsburgh PCB
12 x 30 (12-30 mesh, Calgon Co., Pittsburgh) with a N2-BET specific surface area
of 812 m2/g, which was degassed in vacuo (10 5 Torr) for 3 h and stored in a sealed
plastic container before use. Organic chemicals of GC grade or spectroscopic grade
were purchased for the desorption measurements. The kinds of objective com-
pounds and solvents used in this study are shown in Tables 1 and 2. They were
tested for impurities by GC before use in these experiments.
Methods: GC was the HP 5840A with an FID and an auto-sampler HP 7672A
(Hewlett-Packard Co., Avondale). A column measuring 6 ft long and about 2 mm
in diameter was used with the packings shown below.
1. FFAP (1): FFAP 2% (w/w) coated on Chromosorb WAW (60/80 mesh)
2. FFAP (2): FFAP 10% (w/w) coated on Tenax XA (60/80 mesh)
3. FFAP (3): FFAP 10% (w/w) coated on Flusin T (60/80 mesh)
4. Silicone OV-101: Silicone OV-101 5% (w/w) on Chromosorb WAW (60/80
mesh)
 DESORPTIONOF ORGANIC VAPORS FROM ACTIVE CARBON TUBES 169

5. Porapak Q (60180 mesh)

The carrier gas was nitrogen, supplied at a rate about 30 ml/min. The running
conditions for GC were selected for each sample so as to give a symmetrical peak
of the objective compound with a certain retention time which did not shift with
changes in the size or concentration of the injected sample.
A series of solutions containing an objective organic compound and a desorbing
solvent at different concentrations (2 x 1O, 6 x 1O, 2 x 1O, 2 x 10'3 in v/v) were
prepared in 10 ml volumetric flasks. One ml of each solution was distributed into
four 2 ml vials. Active carbon of 100 mg was added to two vials among the four.
One ml of blank solvent was placed into a separate vial. All the vials were then
sealed with Teflon-coated aluminum caps. After 1 h standing at room temperature
with occasional vibration, the vials were mounted on a GC auto-sampler.
Series of the blank and sample solutions were analyzed by GC in the follow-
ing order to avoid contamination from previously run samples; the blank solvent,
first, followed by the two vials containing solutions with carbon, then the two vi-
als containing solutions without carbon as a unit and those units for the solutions
with higher concentrations. Each solution was analyzed twice, and the reproduc-
ibility of peak area within 3% was confirmed among the two measurements of two
samples of the same concentration. The four measurements for the two vials of
the same sample were averaged. The ratio of the concentration equilibrated with
carbon and the corresponding concentration without carbon was taken as the de-
sorbing efficiency, assuming that the adsorption equilibrium attained by contact of
the solution with active carbon is the same as that attained by desorption of the
same compound which had been adsorbed on active carbon, i.e., the Phase Equi-
librium Method for the determination of desorption efficiency.

RESULTS
ANDDISCUSSION

GC conditions
The optimum GC conditions used for the combination of objective compound
-desorbing solvent are shown in Table 1. Table 2 includes inadequate GC con-
ditions which could not produce satisfactory peak separations. The column
packings used in this study are rather resistant to high column temperatures nec-
essary for the analyses of samples containing compounds with high boiling points.
However, porous polymer beads showed rapid deterioration during the analyses of
solutions containing strong solvents like carbon disulfide.

Desorbing efficiency
Table 1 shows the pairs of objective compounds and desorbing solvents which
gave desorbing efficiencies greater than about 90% within the concentration ranges
of the sample solutions, and that also showed separated peaks in GC chromato-
grams.
170 Y. MATSUMURA

Table 1. Desorbing efficiencies of organic compounds with solvents and GC

analytical conditions.
 DESORPTION OF ORGANIC VAPORS FROM ACTIVE CARBON TUBES 171

Table 2. Inadequate desorbing solvents and GC analytical conditions.

Table 2 shows inadequate pairs of objective compounds and solvents due to

lower desorption efficiency or failure in GC peak separation.
Figure 1 shows the relationships between the concentration of the objective com-
pound in solutions with and without active carbon. The points plotted on the
diagonal line indicate that the objective compound is not retained at all on active
carbon in the presence of solvent, i.e., that there is full desorption efficiency. On
the other hand, the points plotted below the diagonal line indicate the lowering
of the objective compound concentration in the liquid phase when equilibrated with
active carbon, i.e., a lower desorption efficiency.
For cases of low desorbing efficiency, we noted that the desorbing efficiency
decreases in accordance with lower sample concentrations. This means that the
desorbing efficiency cannot be represented by a constant. The pairs of objective
compounds and desorbing solvents shown in Table 1 have satisfied the 90% stan-
dard for desorbing efficiency proposed in this study within the examined concen-
tration ranges.
The examined concentration ranges of the sample solutions from 2 x 10 5 to
172 Y. MATSUMURA

Fig. 1. The phase equilibria of organic compounds with active carbon in carbon
disulfide.
Co: Concentrations of organic compounds in solutions without active carbon.
C: Supernatant concentrations of organic compounds in solutions with active carbon.
Active carbon: Pittsburgh PCB 12 x 30, 100 mg.

2 x 10 3 (v/v) correspond to 4.9 x 10' to 4.9 x 10-5moles of methanol (molar vol-

ume is 40.7 mmole-', smallest among the examined objective compounds) in 1
ml of solution and to 1.3 x 10' to 1.3 x 10-5moles of isoamyl acetate (150.3
mlmol-', the largest molar volume among the objective compounds) in the same
amount of solution. These concentrations in solution correspond to 12.0 to 1200
ppm of methanol per liter of air at 25°C and 3.18 to 318 ppm of isoamyl alcohol
per liter of air at 25°C. These concentration ranges may be a little higher than
those usually found in workplaces, but they are close. When a larger volume of
air, up to 10 liters, is drawn through an active carbon tube, the concentration ranges
of the prepared sample solutions correspond to concentrations that are one tenth
as high as those discussed above, which are the levels often encountered in working
environments. Thus, desorption efficiencies determined in this study are applicable
to practical samples.
 DESORPTION OF ORGANIC VAPORS FROM ACTIVE CARBON TUBES 173

Properties of selected desorbing solvents

The results shown in Tables 1 and 2 indicate that carbon disulfide is a widely
applicable solvent for non-polar or weakly polar hydrophobic organic compound
vapors that have been collected by active carbon tubes. This solvent has a very
short retention time and low sensitivity to GC-FID; these properties are also
advantages because they avoid peak overlapping on chromatograms. However, for
hydrophilic compounds like alcohol and phenol, carbon disulfide showed lower
desorption efficiencies. For these compounds, polar and hydrophilic solvents like
N,N-dimethylformamide and dimethylsulfoxide were effective. These strongly
hydrophilic solvents have long retention times in GC, and this is beneficial be-
cause their own peaks are easily distinguished from the peaks of many objective
organic compounds on GC. Mixtures of dichloromethane or carbon disulfide with
one of the lower molecular weight alcohol were also effective for the hydrophilic
compounds, in terms of avoiding GC peak overlap. p-Xylene was applied to acry-
lonitrile, but it doesn't appear a widely applicable solvent because of peak over-
lapping with many other compounds.

Survey of chemical thermodynamic properties relating to desorption efficiency

High desorption efficiency from active carbon means that dissolution of the target
compound into a solvent overcomes adsorption of the same compound by active
carbon. From this standpoint, the relationship between the desorption efficiency
and the molecular forces between solute and solvent was examined. A thermo-
dynamic parameter relating to mutual solubility of two organic liquids is the
solubility parameter, b (cal05cm15), which is defined by equation (1)6'.

b = (AE~IV)° 5 (1)

where AEI is a value derived from AEI = zH~ - RT (AHD is the heat of vapor-
ization, and V is the molar volume of a liquid). This term is taken to represent
the cohesive energy density of a liquid, and when two liquids with solubility
parameters of bt and b2 are mixed, the heat of mixing, ES is given by the follow-
ing equation (2)

£s = V1`Y22(o1- o2)2 (2)

where eS is the mixing energy (cal.mole 1), V, (cm3) is the molar volume of ob-
jective compound, ~2 is the volume fraction of solvent, and o1 and b2 are the
solubility parameters of objective compound and solvent respectively. When ~S is
low, the two components are generally taken to mix well.
To examine the relation between cS and the desorption efficiency observed in
174 Y. MATSUMURA

Table 3. Solubility parameters and calculated mixing energies

 DESORPTION OF ORGANIC VAPORS FROM ACTIVE CARBON TUBES 175

Fig. 2. Relationship between desorption efficiency and mixing energy.

this study, ~Swas calculated for the pairs of objective compounds and desorbing
solvents shown in Tables 1 and 2. Table 3 gives the values of 8, for the ob-
jective compounds, b2 for the solvents', and ESderived from them. In this table,
only those combinations using single component solvents were included. The mole
fraction of the solvent was assumed to be 1.0, because the solute concentrations
were very low. The relationship between the observed desorbing efficiency and
e is plotted in Figure 2. The desorption efficiencies given by ranges in Table
2 were represented by the average of the upper and the lower limit values ob-
served. This figure showed a rough tendency for the desorption efficiency to lower
with the increase of mixing energy. For instance, water desorbed methanol and
acetone only to a small extent in both cases accompanied by large mixing ener-
gies. The combinations of carbon disulfide and alcohols resulted in low desorp-
tion efficiencies and gave mixing energies from 31 to 226 cal/mole. However,
many combinations of carbon disulfide and hydrocarbons with larger mixing
energies than the pairs of carbon disulfide and alcohols resulted in high desorp-
tion efficiencies. Thus, the expected inverse relationship between mixing energy
and desorption efficiency seemed valid only for a limited number of the targeted
compound-solvent combinations, but not generally applicable to combinations of
solvents and solutes with a wide variety of hydrophilicity and polarity. Testing
the desorbing efficiency of binary solvents may also require modification of the
mixing model, or use of other indicators of effective desorption.
176 Y. MATSUMURA

ACKNOWLEDGEMENTS

The author is grateful to Ms. Miyuki Koizumi for her skillful assistance in this
study. The special financial support by the Ministry of Labor for this study is
acknowledged.

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