52

Quantachrome Instruments

POWDER TECH NOTE

Adsorptives for Physisorption Experiments:
Selection and Their Physical Properties

Introduction
Characterization of porous materials is usually performed using gases at subcritical temperatures, such as
nitrogen at 77 K (T/Tc = 0.61), argon at 87 K (T/Tc = 0.58), CO2 at 273 K (T/Tc = 0.90) (a schematic phase
diagram for a pure fluid is shown in Fig. 1). Below the critical temperature, Tc, a clearly defined adsorptive
phase (adsorbate) is present as a liquid like film is formed on the walls of the pores. This allows one to
extract information about surface area, pore size and porosity from a proper analysis of physisorption
isotherms. At temperatures above the critical point, other adsorption applications (e.g. gas storage,
separation etc.) are the focus.

An important parameter for subcritical adsorption
experiments is saturation pressure, Po , which
depends on temperature. This is because the
thickness of an adsorbed (liquid-like) film, as well
as the pressure where pore filling and pore
condensation occur in a pore of given width, is
related to the difference in chemical potential of
the adsorbed phase (i.e. the adsorbate, µ a) and
the chemical potential of the bulk liquid (µ o) at the
same temperature at which the adsorption
experiment is performed. This chemical potential
difference can be related to the pressures P and P0
of the vapor in equilibrium with the adsorbed film
and the saturated liquid, respectively, by ∆µ o =
(µ a - µ o) = RTlnP/Po, where R is the universal gas
constant and T is the temperature. Hence, the
adsorbed amount is measured as a function of the
ratio P/Po and the accurate monitoring of the
saturation pressure is crucial in order to ensure
the highest accuracy and precision for pore size
and surface area analysis.
The saturation vapor pressure depends on
temperature. This is illustrated in the schematic
phase diagram in Fig. 1. The vapor pressure line,
which defines the temperatures and pressures
where vapor and liquid are in coexistence,
terminates in the critical point. The saturation
pressure increases exponentially with
temperature. For instance, an increase of ca. 0.2 K
results in a saturation pressure increase of ca. 20
torr for nitrogen at a temperature around 77 K.
Experimentally, there are many options for
determining the saturation pressure for a given
physisorption experiment. If the experiment is
performed at a temperature that is near the
boiling point of the adsorptive and with the right
equipment, it is possible to measure the saturation
pressure continuously throughout the experiment
(preferably, Po should be directly measured by
condensing nitrogen in a dedicated saturation
pressure cell contained in the coolant and
connected directly to a dedicated, high precision
pressure transducer).

When adsorption isotherms are measured at the

Figure 1. Schematic phase diagram of a fluid. The vapor
pressure line, which defines the temperatures and pressures
where gas and liquid are in coexistence, terminates at C, the
critical point. Tr is the triple point.
liquid nitrogen (77.35 K at 760 torr) or liquid
argon (87.27 K at 760 torr) temperature, the
coolant is usually held in a dewar flask. The
system is open to atmosphere and the
temperature of the liquid therefore depends on
both the ambient pressure and the presence of
impurities in the liquid, which tends to elevate the
boiling point. Depending upon the amount of
dissolved impurities, such as water vapor, oxygen
and other atmospheric gases, the pure liquid
nitrogen contained in the Po cell therefore exists at
a slightly elevated temperature (ca. 0.1 - 0.2 K),
which results in a saturation pressure increase of
ca. 10 - 20 torr. Hence, in order to perform an
accurate pore size analysis, Po should be

PN 59000-52 Rev A 1 of 6
 measured with the highest resolution possible. In
fact an error in Po of ca. 5 torr at a relative
pressure of 0.95 will lead to an error of 10% in the
calculated pore size.
Below, important experimental parameters
necessary to begin a physisorption analysis are
discussed. This is followed by an overview of gases
used in characterization of adsorbents as well as a
discussion of gases often studied for storage
applications.
Experimental Considerations
Choice of adsorptive
The choice of adsorptive is dependent on both the
information you wish to obtain about the
adsorbent and the limitations of the instrument
(see Tables 1 and 2). The adsorptive choice will
dictate the necessary pressure range for the
experiment. For example: in the case of micropore
measurements using nitrogen at ~77 K or argon
at ~87 K, or for krypton at ~77 K, the instruments
must be equipped with a turbomolecular pump
and the proper pressure transducers (e.g. 1 torr)
in order to achieve and accurately measure low
pressures. For carbon dioxide at ~273 K no
turbomolecular pump is required (see
Quantachrome’s Powder TechNote 35 [1]).
Compatibility
Before an adsorptive is chosen, its compatibility
with the instrument must be assessed. O-rings are
used in many Quantachrome instruments as gas
and vacuum-tight seals. O-rings are available in a
variety of different elastomeric materials and
these differ in their compatibilities with different
gases and vapors. O-ring materials commonly
employed by Quantachrome and their ratings for
use with common gases is given at the following
website:
http://www.quantachrome.com/technical/o_rings.html
Temperature
At temperatures which are below the critical point
of the gas, it may be possible to determine surface
area and pore size distributions of the adsorbent.
Below the critical temperature, it is convenient to
measure the Po value continuously during the
experiment using a dedicated Po cell. At
temperatures above the critical point, a saturation
pressure, Po , is no longer defined. A classical
surface area (BET) and pore size analysis is not
possible.
PN 59000-52 Rev A 2 of 6
If the experiment is performed at supercritical
temperatures, the user cannot use the measure Po
option. Instead, the user must enter a pseudo- Po
value (which we recommend to be 760 torr) in the
software. With this entered value, the data
obtained reflects the adsorbed amount as a
function of absolute pressure (in atm).
If the experimental temperature chosen has a Po
greater than atmospheric pressure, the measure
Po option may not be used. Enter a pseudo-Po
value and re-scale with the true Po after the
experiment (as an example, see Quantachrome’s
Powder TechNote 35 for carbon dioxide [1]). For
Po options on various Quantachrome instruments,
see Table 1.
Experimental parameters
In order to start an adsorption experiment, the
following three parameters must be known:
Temperature
Po option (Table 1)
Non-ideality factor (Table 2)
These parameters are necessary in order to begin
the experiment. Other parameters (such as cross-
sectional area, etc) may be entered before the
experiment is started or after the run has finished,
as needed for the desired data reduction.
Gases for Characterization: Alternatives to
Nitrogen
Although nitrogen at ~77 K is the adsorptive
traditionally used for characterization of porous
materials, some of its limitations, particularly for
the characterization of microporous or very low
surface area materials, make it necessary to team
nitrogen up with other gases to obtain full
characterization of the adsorbent. As examples,
argon is commonly used to determine pore size
distributions in microporous materials and carbon
dioxide may be used in cases where
ultramicropores (pores < 0.7 nm) are present.
Additionally, krypton is a good choice as
adsorptive in samples of very low surface area.
 Table 1. Instrument configuration and Po type.

Quantachrome Transducers Lowest P/Po

instruments [torr]
Turbopump Po options
range

Stationa,
Autosorb-iQ 1000 1 × 10-3 No
User Entered
Stationa,
Autosorb-iQ MP 1000, 10, 1 1 × 10-7 Yes
User Entered
Stationa,
Autosorb-6B 1000 1 × 10-3 No
User Entered,
Open to ambient,
Calculated
Stationa,
Autosorb-6B MP 1000, 10 1 × 10-5 Yes
User Entered,
Open to ambient,
Calculated
Measure, Entered, Daily,
Nova 1000 1 × 10-3 No
Calculate,
Continuous
User Entered,
Quadrasorb SI 1000 1 × 10-3 No
Calculate,
Measure every
X points
Quadrasorb SI MP 1000, 10 4 × 10-5 Yes User Entered, Calculate,
Measure every
X points
a. Station = continuous measurement of Po with a dedicated Po cell, and pressure transducer

Table 2. Physical properties of adsorptives.

Molecular Critical
Temp Non-ideality factor P0a
Gas Weight Temperature
[K] [torr-1] [torr]
[g/mol] [K]
Acetone 298 1.208 × 10-4 184.62 58.08 508.1

Acetonitrile 298 3.456 × 10-4 72.825 41.05 548

-5 b
Acetylene 298 1.163 × 10 37946 26.04 308.1

Ammonia 298 1.461 × 10-5 7490.2 17.03 405.7

Argon 77.35 11.4 × 10-5 205 (s) 230 (l) 39.948 151
-5
87.45 3.94 × 10 771.94

Benzene 298 1.095 × 10-4 94.519 78.11 562

Butane 273 1.42 × 10-4 769.87 58.12 425

-5
298 3.95 × 10 1816.3

n-Butanol 298 1.497 × 10-4 4.79736 74.12 563.1

Carbon Dioxide 195 2.57 × 10-5 760.98b 44.01 304.2

-6
273 9.078 × 10 26037

298 6.842 × 10-6 48095

Carbon Monoxide 87.45 4.64 × 10-5 1404 28.01 133.9

Continued…

PN 59000-52 Rev A 3 of 6
 … continuation of Table 2

Cyclohexane 298 9.341 × 10-5 96.978 84.16 553.5

-6
Ethane 298 9.912 × 10 31329 30.07 305.3

Ethanol 298 2.716 × 10-4 44.604 46.07 513.9

Ethyl Acetate 298 1.327 × 10-4 74.38 88.105 530.6

-4
Hexane 298 1.137 × 10 121.41 86.17 507.4

n-Hexanol 298 6.63 × 10-5 0.6697b 102.18 611

Hydrogen 77.35 2.16 × 10-6 N/A 2.016 33.3

-6
87.45 1.18 × 10 N/A

97 5.35 × 10-7 N/A

107 9.85 × 10-8 N/A

-4
Isopropanol 298 1.885 × 10 33.105 60.09 508.3
1.6
Krypton 77.35 3.00 × 10-5 83.8 209
2.63c
-5
87.45 2.00 × 10 13

Methane 273 3.15 × 10-6 N/A 16.04 190.4

-6
298 2.31 × 10 N/A
-4
Methanol 293 1.004 × 10 96.958 32.04 512.6

298 9.441 × 10-5 126.38

-5
303 8.875 × 10 163.14
-5
313 7.835 × 10 264.55

Nitrogen 77.35 6.58 × 10-5 759.55 28.02 126.2

-7
298 2.168 × 10 N/A
-6
Nitrous Oxide 298 7.004 × 10 42251 44.02 309.7

Oxygen 77.35 6.799 × 10-5 155.61 31.999 154.6

87.45 4.65 × 10-5 565.32

-7
298 8.627 × 10 N/A

n-Pentanol 298 5.32 × 10-5 1.5464 88.15 588.2

n-Propanol 298 1.587 × 10-4 14.922 60.09 536.8

-5
Sulfur Dioxide 298 1.19 × 10 2928.4 64.06 430.6

Sulfur Hexafluoride 298 1.503 × 10-5 17678 146.05 318.7

Tetrahydrofuran 298 3.240 × 10-5 129.64 72.11 540.1

-4
Toluene 298 1.505 × 10 21.894 92.13 592.2

Water 293 6.852 × 10-5 17.384 18.02 647.1

298 6.246 × 10-5 23.565

-5
303 5.706 × 10 31.582

313 4.793 × 10-5 54.95

a. http://webbook.nist.gov/chemistry/fluid/
b. CRC Handbook of Chemistry and Physics, 83rd edition.
c. Refer to Quantachrome’s Powder TechNotes 39 and 51.
N/A = Experimental temperature is greater than the critical temperature and the saturation pressure does not apply.

PN 59000-52 Rev A 4 of 6
 For Micropore Analysis
Argon
The characterization of microporous materials with
nitrogen at ~77 K is difficult because filling of
pores with dimensions of 0.5-1 nm occurs at very
low relative pressures (P/P0 =10-7 – 10-5). In this
low pressure regime, the rates of diffusion and
equilibration are very slow.
• Argon at ~87 K fills micropores of dimensions
0.5-1 nm at higher relative pressures (10-5 to
10-3 torr) leading to faster equilibration and,
subsequently, a reduction in analysis time.
• Pore filling pressure regions of argon at ~87 K
in zeolites are correlated with the pore
size/structure which allows one to resolve small
differences in pore size (resolution of 0.1 nm).
In contrast, for nitrogen at ~77 K, the pressure
where pore filling occurs also depends strongly
on specific interactions with cations in the
adsorbent meaning that the pressure where
pore filling occurs is not correlated with the
pore size/structure. Hence, pore size analysis
with nitrogen is not straightforward and argon
has been shown to be a better choice.
• Advanced theoretical approaches based on
statistical mechanics (such as NLDFT or QSDFT)
have been developed to assess pore size
distributions from argon adsorption
experiments.
Experiments may also be performed using argon
at liquid nitrogen temperatures (~77 K). Because
of the low saturation pressure this can lead to
increased sensitivity for surface area analysis.
Beyond this, however, argon at ~77 K is not
recommended because:
• A complete micro- and mesopore size analysis
is not possible because at ~77 K argon is
~6.5 K below the triple point temperature of
bulk argon.
• Analysis is limited to pore diameters smaller
than 15 nm due to the fact that pore
condensation cannot be observed above this
pore size (for details see [2]).
• Although the argon adsorption isotherm at
~77 K (on zeolites for instance) is still shifted
appreciably to higher relative pressures as
compared to the appropriate nitrogen
adsorption, the shift towards higher absolute
pressure is less pronounced as compared to
argon adsorption at ~87 K. This is due to the
low saturation pressure of argon at ~77 K (205
torr for solid argon and 230 torr for supercooled
liquid argon). Hence, argon adsorption at
~77 K does not offer the same experimental
benefits as compared to argon adsorption at
~87 K [3].
• There is some evidence that the structure of
the argon monolayer is highly dependent on the
surface chemistry of the adsorbent [4].
PN 59000-52 Rev A 5 of 6
Carbon dioxide
In the case of porous carbons, instead of nitrogen
analysis at ~77 K or argon analysis at ~87 K,
carbon dioxide at ~273 K can be employed to
measure pore sizes, particularly in the
ultramicropore (pores smaller than 0.7 nm)
regime. (For experimental details, see
Quantachrome’s Powder TechNote 35 [1].)
• Carbon dioxide has a higher diffusion rate than
nitrogen which allows the carbon dioxide
molecules to more easily access the
ultramicropores than nitrogen at ~77 K, thus
speeding up the analysis.
• Pore size distributions can be obtained from
the isotherm using NLDFT or Grand Canonical
Monte Carlo (GCMC) methods.
Experiments with carbon dioxide at ~195 K may
also be performed using either a cryostat (see
Quantachrome’s Powder TechNote 43 [7]) or a dry
ice/acetone mixture. This allows one to obtain the
complete carbon dioxide isotherm as the
kinetics/equilibration times are still quite
reasonable (compared to nitrogen and argon
adsorption at cryogenic temperatures).
It is important to note that carbon dioxide is not
suitable for exploring the pore size distribution of
zeolites, metal-organic frameworks (MOFs), or
certain oxides because of its strong quadrupole
moment which can lead to large specific
interactions with ions located in the zeolite or MOF
framework. Hence, if carbon dioxide is used as the
adsorptive in these materials, there is no clear
correlation between pore size and pore filling
pressure. It may, however, still be possible to
obtain accurate pore volume information for these
materials using carbon dioxide.
For Micropore Volume Determination
Water
An alternative for the determination of the total
micropore volume is the use of water as
adsorptive.
• Water is a very small molecule (kinetic
diameter 0.27 nm), and can therefore
penetrate very small pores (e.g. the sodalite
cages in NaA zeolite) which are not accessible
for nitrogen and argon at cryogenic
temperatures.
• Because of its strong dipole and the resulting
specific interactions with surfaces, it is not a
good choice for pore size analysis. However,
the comparison between the saturation
capacities measured with water, carbon
dioxide, argon and nitrogen can provide
complimentary structural information [3].
 For Low Surface Area Determination
Krypton
For low surface area samples, krypton at ~77 K is
often used as an alternative to nitrogen. For
details on krypton measurements, see
Quantachrome’s Powder TechNote 51 [5].
• At ~77 K, krypton has a lower vapor pressure
than nitrogen meaning that a fewer number of
molecules are contained within the void
volume of the sample leading to less
uncertainty in the surface area measurement
for low surface area samples.
Carbon Dioxide
Not only can carbon dioxide be used to
characterize ultramicropores (because
experiments are performed below the carbon
dioxide critical temperature), but there is also a lot
of interest in the storage of carbon dioxide.
Storage capacities may be determined at different
temperatures from the isotherm. Additionally,
isosteric heats of adsorption can also be calculated
for carbon dioxide using the adsorption isotherms
measured at different temperatures.

For Thin Film Analysis Methane

Krypton The use of porous materials for methane storage
Krypton can also be utilized at ~87 K for the pore is also of interest. As for hydrogen, in these
size analysis of thin films. For more detailed storage experiments, methane is supercritical and
information, see Quantachrome’s Powder can therefore not be used to characterize a
TechNote 39 [6]. material, but only to investigate its potential for
methane storage.

Gases for Storage Applications

Hydrogen
Hydrogen is supercritical at room temperature;
therefore, significant amounts of hydrogen can
only be stored at elevated pressures. However,
hydrogen adsorption experiments can still be
performed at subatmospheric pressures in order to
obtain information about the hydrogen storage
potential of an adsorbent. Cryogenic temperatures
can also be studied to increase hydrogen uptake.
Hydrogen isotherms measured at different
temperatures can be used to calculate the isosteric
heat of adsorption for the adsorbent. A
temperature range between 77 and 200 K is
available by coupling the instrument with a
cryostat (Quantachrome’s Powder TechNote 43
[7]). For more information on hydrogen
adsorption, see Quantachrome’s Powder TechNote
37 [8].
Conclusions
Gases other than nitrogen play an important role
in the characterization of porous materials and
offer better alternatives for determining properties
such as pore size, particularly for microporous
materials. An important consideration in the
physisorption of gases is the temperature at which
the experiment is being performed. If a
temperature below the critical point of the gas is
selected, information about the surface area, pore
size distribution, and porosity of the adsorbent can
be obtained. Advice has been given on setting up
physisorption experiments, including discussion of
some of the important experimental parameters
relative to the adsorptive of choice.

References

[1] Quantachrome Instruments, Powder TechNote 35, Micropore Size Analysis of Porous Carbons using CO2 Adsorption at 273.15 K.
[2] S. Lowell, J. Shields, M. A. Thomas, and M. Thommes, Characterization of Porous Solids and Powders: Surface Area, Porosity, and
Density, Springer, 2004.
[3] M. Thommes, Textural Characterization of Zeolites and Ordered Mesoporous Materials by Physical Adsorption in Introduction to
Zeolite Science and Practice (3rd revised edition), J. Cejka, H. van Bekkum, A. Corma, F. Schüth (eds.), Stud. Surf. Sci. Catal. 168,
Chapter 15, Elsevier, 207, 495-525.
[4] F. Rouquerol, J. Rouquerol, and K. Sing, Adsorption by Powders and Porous Solids, Academic Press, London, 1999.
[5] Quantachrome Instruments, Powder TechNote 51, Low Surface Area Analysis by Krypton Adsorption at 77.4K.
[6] Quantachrome Instruments, Powder TechNote 39, Aspects of a Novel Method for the Pore Size Analysis of Thin Films Based on
Krypton Adsorption at Liquid Argon Temperature.
[7] Quantachrome Instruments, Powder TechNote 43, Application of Customized Optistat DN Cryostat for Advanced Adsorption and
Structural Characterization Studies.
[8] Quantachrome Instruments, Powder TechNote 37, Hydrogen Adsorption: Experiment and Application.

This Powder Tech Note ©Quantachrome Instruments, 2011.

PN 59000-52 Rev A 6 of 6