INTERNATIONAL ISO

STANDARD 9277

Third edition
2022-11

Determination of the specific surface

area of solids by gas adsorption —
BET method
Détermination de l'aire massique (surface spécifique) des solides par
adsorption de gaz — Méthode BET

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Reference number
ISO 9277:2022(E)

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ISO 9277:2022(E)

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 ISO 9277:2022(E)

Contents Page

Foreword......................................................................................................................................................................................................................................... iv
Introduction..................................................................................................................................................................................................................................v
1 ​Scope.................................................................................................................................................................................................................................. 1
2 ​Normative references...................................................................................................................................................................................... 1
3 ​Terms and definitions..................................................................................................................................................................................... 1
4 ​Symbols........................................................................................................................................................................................................................... 3
5 ​Principle......................................................................................................................................................................................................................... 3
6 ​Procedure..................................................................................................................................................................................................................... 4
6.1 ​Sample preparation............................................................................................................................................................................. 4
6.2 ​Experimental conditions................................................................................................................................................................ 7
6.3 ​Measuring methods for the assessment of the amount of adsorbed gas............................................. 8
6.3.1 ​General......................................................................................................................................................................................... 8
6.3.2 ​Static manometric (volumetric) method........................................................................................................ 8
6.3.3 ​Flow manometric (volumetric) method.......................................................................................................... 8
6.3.4 ​Gravimetric method......................................................................................................................................................... 9
6.3.5 ​Carrier gas method......................................................................................................................................................... 10
6.3.6 ​Dynamic vapour sorption method................................................................................................................... 11

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7 ​Evaluation of adsorption data............................................................................................................................................................. 11
7.1 ​General......................................................................................................................................................................................................... 11
7.2 ​Multipoint determination........................................................................................................................................................... 12
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7.3 ​Single-point determination....................................................................................................................................................... 13
8 ​Test report................................................................................................................................................................................................................ 14
ISO 9277:2022
9 ​Use of reference materials....................................................................................................................................................................... 14
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Annex A (informative) Cross-sectional areas of some frequently used adsorptives..................................... 15
4e0a90829aed/iso-9277-2022
Annex B (informative) BET area of microporous materials..................................................................................................... 16
Bibliography.............................................................................................................................................................................................................................. 21

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ISO 9277:2022(E)

Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular, the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation of the voluntary nature of standards, the meaning of ISO specific terms and
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expressions related to conformity assessment, as well as information about ISO's adherence to
the World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT), see
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www.iso.org/iso/foreword.html.
This document was prepared by Technical Committee ISO/TC 24, Particle characterization including
sieving, Subcommittee SC 4, Particle characterization.
ISO 9277:2022
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This third edition cancels and replaces the second edition (ISO 9277:2010), which has been technically
revised. 4e0a90829aed/iso-9277-2022
The main changes compared to the previous edition are as follows:
— the IUPAC classification of adsorption isotherms has been updated according to Reference [3];
— the description of dynamic vapour sorption (DVS) method in 6.3.6 has been added;
— Annex A has been revised;
— Annex B has been removed;
— the former Annex C (now Annex B) has been revised.
Any feedback or questions on this document should be directed to the user’s national standards body. A
complete listing of these bodies can be found at www.iso.org/members.html.

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 ISO 9277:2022(E)

Introduction
Gas adsorption allows for assessing surface area of nonporous materials and porous materials with
accessible porosity (which depends on the chosen adsorptive) via the Brunauer, Emmett and Teller
(BET) theory[1],[2]. The BET theory is applicable only to adsorption isotherms of type II (disperse,
nonporous or macroporous solids) and type IV (mesoporous solids) (see Figure 1, Type II and Type IVa
isotherms). However, in the case of Type IVb isotherms, caution is required since pore condensation can
occur at quite low p/p0 (see IUPAC recommendations[3]). The BET method cannot reliably be applied to
solids which absorb the measuring gas. A strategy for BET area determination of microporous materials
(type I isotherms) is described in Annex B.

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Key
X relative pressure
Y amount adsorbed

SOURCE IUPAC Recommendations, 1994. Reproduced with the permission of the authors.[2]

Figure 1 — IUPAC (2015) classification of adsorption isotherms

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INTERNATIONAL STANDARD ISO 9277:2022(E)

Determination of the specific surface area of solids by gas

adsorption — BET method

1 ​Scope
This document specifies the determination of the overall specific external and internal surface area of
either disperse (e.g. nano-powders) or porous, solids by measuring the amount of physically adsorbed
gas according to the method of Brunauer, Emmett and Teller method,[1] based on the 2015 International
Union for Pure and Applied Chemistry (IUPAC) recommendations[3].
NOTE For solids exhibiting a chemically heterogeneous surface, for example, metal-carrying catalyst, the
BET method gives the overall surface area, whereas the metallic portion of the surface area can be measured by
chemisorption methods.

2 ​Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
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ISO 8213, Chemical products for industrial use — Sampling techniques — Solid chemical products in the
form of particles varying from powders to coarse lumps
(standards.iteh.ai)
ISO 14488, Particulate materials — Sampling and sample splitting for the determination of particulate
properties
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3 ​Terms and definitions 4e0a90829aed/iso-9277-2022
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminology databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https://​w ww​.iso​.org/​obp
— IEC Electropedia: available at https://​w ww​.electropedia​.org/​
3.1
adsorption
enrichment of the adsorptive gas at the external and accessible internal surfaces of a solid material
3.2
physisorption
weak bonding of the adsorbate (3.2), reversible by small changes in pressure or temperature
3.3
adsorbate
adsorbed gas
3.4
adsorptive
gas or vapour to be adsorbed
3.5
adsorbent
solid material on which adsorption (3.1) occurs

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ISO 9277:2022(E)

3.6
isotherm
relationship between the amount of gas adsorbed and the equilibrium pressure of the gas, at constant
temperature
3.7
volume adsorbed
volumetric equivalent of adsorbed amount (3.8) expressed as gas at standard conditions of temperature
and pressure (STP)
3.8
adsorbed amount
number of moles of gas adsorbed at a given pressure and temperature
3.9
monolayer capacity
volumetric equivalent of monolayer amount expressed as gas at standard conditions of temperature
and pressure
3.10
surface area
area of the external surface of a solid plus the internal surface of its accessible macro-, meso- and
micropores (3.16)
3.11
specific surface area iTeh STANDARD PREVIEW
absolute surface area (3.10) of the sample divided by sample mass
3.12 (standards.iteh.ai)
molecular cross-sectional area
molecular area of the adsorbate (3.2), i.e. the area occupied by an adsorbate molecule in the complete
monolayer ISO 9277:2022
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3.13 4e0a90829aed/iso-9277-2022
nanopore
pore with width of about 100 nm or less
3.14
macropore
pore with width greater than approximately 50 nm
3.15
mesopore
pore with width between approximately 2 nm and 50 nm
3.16
micropore
pore with width of approximately 2 nm or less
3.17
relative pressure
ratio of the equilibrium adsorption (3.1) pressure, p, to the saturation vapour pressure (3.18), p0, at
analysis temperature
3.18
saturation vapour pressure
vapour pressure of the bulk liquefied adsorptive gas at the temperature of adsorption (3.1)

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3.19
free space
head space
dead space
dead volume
volume of the sample holder not occupied by the sample

4 ​Symbols
Table 1 presents the symbols used in this document, together with their common units derived from
the SI. For comparison purposes, the lUPAC symbols are also given. All specific dimensions are related
to sample mass in grams.

Table 1 — Symbols
Symbol Quantity Unit
am molecular cross-sectional area nm2
as specific surface area m2 g−1
C BET parameter a 1
L Avogadro constant (L = 6,022 × 1023) mol−1
m mass of the solid sample g
ma
na
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specific mass adsorbed a
specific amount adsorbed
1
mol·g−1
nm
nm,mp
(standards.iteh.ai)
specific monolayer capacity of adsorbate
specific monolayer capacity derived from multipoint measurement
mol g−1
mol g−1
nm,sp specific monolayer capacity derived
ISOfrom single-point measurement
9277:2022 mol g−1
p https://standards.iteh.ai/catalog/standards/sist/e184eb4e-ac7a-4781-9824-
pressure of the adsorptive in equilibrium with the adsorbate Pa
p0 4e0a90829aed/iso-9277-2022
saturation vapour pressure of the adsorptive Pa
p/p0 relative pressure of the adsorptive a 1
R molar gas constant (= 8,314) J mol−1 K−1
rs radius of uniform nonporous spheres nm
t time min
T temperature K
Va specific volume adsorbed cm3 g−1
Vp,micro specific micropore volume cm3 g−1
ρ (mass) density g cm−3
uc combined standard uncertainty for the certified specific surface area of a BET refer- m2 g−1
ence material
k coverage factor for the combined standard uncertainty a 1
U expanded uncertainty (U = k uc) for the certified specific surface area of a BET refer- m2 g−1
ence material
a According to ISO 80000-1, the unit for any quantity of dimension one (at present commonly termed “dimensionless”) is
the unit one, symbol 1.

5 ​Principle
The method specified involves the determination of the amount of adsorbate or adsorptive gas required
to cover the external and the accessible internal pore surfaces of a solid (see Figure 2) with a complete
monolayer of adsorbate. This monolayer capacity can be calculated from the adsorption isotherm using
Formula (1) (see 7.1). Any gas may be used, provided it is physically adsorbed by weak bonds at the

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ISO 9277:2022(E)

surface of the solid (van der Waals forces) and can be desorbed by a decrease in pressure at the same
temperature.

Figure 2 — Schematic cross-section of a particle with surface detected

by the adsorption method shown by dotted line

Nitrogen at its boiling point (about 77 K) was for many decades the adsorptive generally used for
the determination of the specific surface area, mainly because liquid nitrogen was readily available
and relatively strong attractive adsorptive-adsorbent interactions for many systems. However, due
to nitrogen’s quadrupole moment the orientation of a nitrogen molecule is affected by the surface
chemistry of the adsorbent. This leads to uncertainties in the surface area determination by nitrogen
in the order of approximately 20 % for some surfaces. However, argon at 87 K is a great alternative
because argon does, contrary to the diatomic nitrogen molecule, not exhibit a quadrupole moment.
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Hence, argon adsorption is less sensitive to the surface chemistry leading to a much more reliable
surface area determination for many adsorbent surfaces. If the sensitivity of the instrument when
(standards.iteh.ai)
using argon or nitrogen is insufficient for low specific surface areas of about 1 m2 g−1 or lower, the
application of krypton adsorption at liquid nitrogen temperature for the specific surface area analysis
is recommended. As a consequence of the low p0 of about 0,35 kPa for krypton at 77 K, the 'free
space' correction (see 3.19) for unadsorbed gasISO is significantly
9277:2022 reduced (to 1/300th) compared to the
conditions of nitrogen adsorption at the same temperature and it becomes possible to manometrically
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measure low uptakes of adsorptive with acceptable accuracy.
4e0a90829aed/iso-9277-2022 Although at 77 K krypton is about
38,5 K below its triple point temperature, there is some evidence from microcalorimetry and neutron
diffraction studies that in the BET region, the adsorbate may well be in a liquid-like state and therefore
the value of the supercooled liquid is recommended as the effective p0 for the construction of the BET
plot.
The results of measurements with different adsorptives may deviate from each other because of
different molecular areas, different accessibilities to pores (classified into micro-, meso-, macro- and
nanopores) and different measuring temperatures. Moreover, it is well known from the concepts of
fractal analysis that experimental results for the quantities of length and area in the case of irregular
complex structures – such as those which are found in most porous and/or highly dispersed objects –
are not absolute but depend on the measurement scale i.e. the “yardstick” used. This means that less
area is available for larger adsorbate molecules.
The adsorptive gas is admitted to the sample container, which is held at a constant temperature.
The amounts adsorbed are measured in equilibrium with the adsorptive gas pressure p and plotted
against relative pressure, p/p0, to give an adsorption isotherm. Adsorption isotherms may be obtained
by manometric (volumetric), by gravimetric or by the carrier gas method using continuous or
discontinuous operation (see 6.3).

6 ​Procedure

6.1 ​Sample preparation

Sampling shall be carried out in accordance with ISO 8213 and ISO 14488. Prior to the determination
of an adsorption isotherm, remove physically adsorbed material from the sample surface by degassing,
while avoiding irreversible changes to the surface. Ascertain the maximum temperature at which

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 ISO 9277:2022(E)

the sample is not affected by thermogravimetric analysis (see Figure 3), by spectroscopic methods,
or by trial experiments using different degassing conditions of time and temperature. When vacuum
conditions are used, degassing to a residual pressure of approximately 1 Pa or better is usually
sufficient. Degassing of the sample can also be performed at elevated temperature by flushing with an
inert gas (e.g. helium, nitrogen, argon). Degassing is complete when a steady value of the residual gas
pressure, p, of its composition or of the sample mass is reached.

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Key
X degassing time 1 sample
Y sample mass 2 vacuum generating system
T1 temperature too low: long degassing time 3 balance
T2 optimum temperature 4 oven
T3 temperature too high: gas evolution due to
decomposition of the sample

Figure 3 — Thermogravimetric control of degassing

Using the vacuum technique, isolate the heated sample container from the pump and trap (at time ti in
Figure 4). If the pressure is nearly constant over a period of 15 min to 30 min, degassing is complete.
This procedure also establishes the absence of leaks. The specific surface area should be related to the
mass of the degassed sample.

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ISO 9277:2022(E)

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Key (standards.iteh.ai)
X time p3(t) leak
Y pressure ISO 19277:2022
sample
t1 time of sample isolation 2 vacuum generating system
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p1(t) degassing complete, apparatus tight 4e0a90829aed/iso-9277-2022
3 manometer
p2(t) incomplete degassing 4 oven

Figure 4 — Pressure control of degassing

After degassing, the sample container is cooled to the measuring temperature. It should be noted that,
at low gas pressures, the temperature of the sample needs some time to equilibrate due to the reduced
thermal conductivity within the sample cell.

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