Experimental methods in chemical engineering:

specific surface area and pore size distribution

measurements—BET, BJH, DFT

Raoof Bardestania , Gregory S. Patienceb , Serge Kaliaguine∗a

Accepted Article

a Department of Chemical Engineering, Laval University, 1065 Avenue de la Médecine,

Québec, QC, G1V 0A6, Canada
b Department of Chemical Engineering, Polytechnique Montréal, C.P. 6079, Succ. CV

Montréal, H3C 3A7, Québec, Canada

Abstract
Gas physisorption is an experimental technique based on equilibrium Van der
Waals interactions between gas molecules and solid particles that quantifies
the specific surface area (SSA), pore size distribution (PSD), and pore volume
of solids and powders. The performance of catalysts, absorbents, chromatog-
raphy column materials, and polymer resins depends on these morphological
properties. Here we introduce the basic principles and procedures of physical
adsorption, especially nitrogen physisorption, as a guide to students and re-
searchers unfamiliar with the field. The Brunauer-Emmett-Teller theory (BET)
is a common approach to estimate SSA that extends the Langmuir monolayer
molecular adsorption model to multilayer layers. It relies on an equilibrium
adsorption isotherm, measured at the normal boiling point of the adsorbate, eg,
77 K or 87 K for N2 and Ar, respectively. Web of Science indexed 45 400 articles
in 2016 and 2017 that mentioned N2 adsorption porosimetry—BET and BJH
(Barrett-Joyner-Halenda) keywords. The VOSViewer bibliometric tool grouped
these articles into four research clusters: adsorption, activated carbon in aque-
ous solutions for removal of heavy metal ions; synthesis of nanoparticles and
composites; catalysts performance in oxidation and reduction processes; and
photocatalytic degradation with TiO2 . According to the literature, the accu-
racy of the density function theory (DFT) method is higher than with the BJH
theory and it is more reliable.
Keywords: BET surface area, BJH, DFT, pore size distribution, specific sur-
face area

∗ Corresponding author email: [email protected]

This article has been accepted for publication and undergone full peer review but has not been
through the copyediting, typesetting, pagination and proofreading process which may lead to
differences between this version and the Version of Record. Please cite this article as doi:
10.1002/cjce.23632
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 INTRODUCTION

This paper is part of a series entitled “Experimental Methods in Chemical

Engineering”. As discussed in the introductory paper,[1] the objective is to pro-
vide chemical engineering students and researchers unfamiliar with the method
an overview of the principles and experimental approaches. Often these individ-
uals need to master several disciplines in the course of their research and cannot
Accepted Article

afford a systematic in-depth review of the literature dealing with all of the an-
alytical methods involved in their work. It is in this spirit that the Canadian
Journal of Chemical Engineering published these articles that are distinct from
typical research papers and correspond to a tutorial review. Indeed this article,
like any other in the series, is not intended for established researchers in the
field of BET measurements. We first describe the physisorption instrument and
the laboratory procedures to measure SSA and PSD. We then present the basis
of the theories and briefly highlight recent applications. Finally, we mention
the uncertainties and caution researchers to report significant figures based on
multiple measurements rather than instrument precision.
Specific surface area, SSA, is undoubtedly the most meaningful morphologi-
cal characteristic of solid substances in applications related to porous structures,
such as industrial adsorbents, catalysts, pigments, cement, and polymers.[2, 3]
Pores for which dpore < 2 nm are classified as micropores, while mesopores lie
between 2 nm to 50 nm, and macropores exceed 50 nm in diameter.[4] Micropores
are further subdivided into ultra micropores (dpore < 0.7 nm), medium-sized mi-
cropores (0.7 nm < dpore < 0.9 nm), and super-micropores (dpore > 0.9 nm).[5, 6]
Gas physisorption equilibrium isotherms of nitrogen, argon, or carbon diox-
ide adsorbates are the basis of the most reliable methods to measure porous
material SSA and pore size distribution, as well as average pore diameter and
volume.[7] At temperatures below 100 K, Van der Waals’ forces govern the inter-
action between gas molecules and surfaces with heat of adsorption lower than
4 kJ · mol−1 . These forces lead to the reversible physisorption of gas molecules
on material surface in multiple layers. Chemisorption, on the other hand, is
a different process, occurring with higher heat of sorption in a monolayer,
irreversibly.[8, 9] Brunauer et al.[10] extended the Langmuir theory of mono-
layer adsorption to include multiple layers for which only adjacent layers of gas
molecules interact to calculate surface area, SBET .
Barrett et al.[11] introduced the Kelvin equation to calculate pore size dis-
tribution, the Barrett-Joyner-Halenda (BJH) method. Seaton et al.[12] were the
first to propose the density functional theory (DFT) coupled with Monte Carlo
molecular simulations to more precisely calculate pore size distribution from
adsorption isotherms. For materials with highly disordered slit-like micropores
and spheres, non-local density functional theory (NLDFT) apply best.[13] To de-
termine pore size distribution, the BJH and DFT methods are complemented by
porosimetry methods on the large size range. Low pressure mercury porosime-
try applies to macropores (14 µm-200 µm) while high pressure Hg porosimetry
measures pore diameters as low as 3 nm (mesopores).[14]
The two major components of the N2 physisorption analyzer are the de-

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 To vacuum To adsorption

Cell holder VAC CAL

ADS
V3
BET cell P

ADS V1 V2 V4 V6 V7
Accepted Article

V5
Clamp VENT

Heating Dewar
Sample

mantle N2(liq)

Degassing Adsorption

Figure 1: Gas physisorption apparatus to obtain adsorption-desorption isotherm (vacuum

(VAC), calibration (CAL), adsorbate (ADS), pressure gauge (P), V1-V7 valves)

gassing and adsorption stations (Figure 1). The first step in the process is to
calibrate a quartz cell used for gas adsorption: this cell is evacuated under high
vacuum (< Pa) at 300 ◦C for 2 h (degassing), followed by a complete adsorption
cycle in the empty cell at 77 K. The cell is then loaded with 50 mg-150 mg of
sample, and connected to the degassing station. Degassing the sample is to re-
move physically adsorbed water and volatiles that accumulated during storage.
For thermally sensitive solids, mild degassing temperatures are used, and for me-
chanically fragile porous materials, a stream of inert gas is introduced instead
of vacuum, using the adsorbate path (ADS) connected to the degassing station
(Figure 1). After degassing, the cell is transferred to the adsorption station and
evacuated. The adsorption cycle is performed by incremental introduction of
adsorbate gas using the calibration volume (CAL) connected to the adsorption
station. The difference between the measured pressure and that of the empty
cell correlates with the number of moles of adsorbed nitrogen. Nitrogen is the
preferred gas adsorbate because it is inert, available in high purity, inexpensive,
and interacts with most solids. During measurements, the cell is maintained at
liquid nitrogen boiling point using a Dewar flask filled with liquid nitrogen.
Nitrogen physisorption isotherms are categorized into six types (Figure 2).[15]
Materials such as zeolites and some types of activated carbon with mainly nar-
row micropores, display type I or Langmuir isotherm, where the pores fill at very
low relative pressure with a steep uptake, because of considerable adsorbent-
adsorbate interactions.[16] The limited amount of adsorbed gas is governed by
the accessible micropores volume instead of the actual internal surfaces. Non-
porous materials and those with mainly macropores yield isotherms of type II
(reversible isotherms), where N2 molecules are absorbed in mono/multi-layers
without restriction. The transition point from monolayer coverage to multi-
layer begins at point B in Figure 2. Type IV isotherms arise from solids with
micro- and mesopores, where the interactions between gas molecules and ad-

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 sorbent mesopore surface lead to capillary condensation. Type VI corresponds
to stepwise multilayer adsorption on a uniform non-porous surface. Adsorption
of Ar or Kr on graphitized carbon black at liquid nitrogen temperature mostly
leads to this isotherm type. The initial zero slope of types III and V at low
relative pressure reflects weak adsorbate-adsorbent interactions, comparable to
the adsorbate-adsorbate interactions. Nitrogen adsorption on polyethylene is
Accepted Article

an example of this case. This type of isotherms does not allow the estimation
of the solids monolayer capacity and thus SSA.[15, 16]
In the case of capillary condensation occurring in mesopores, the desorption
path will be different from that of adsorption, resulting in the formation of a
hysteresis loop (Figure 3).[15] The type of loop is mostly associated with the
pore shape.[17] Materials with uniform distribution of spherical and cylindrical
narrow mesopores exhibit H1 type of hysteresis loop. Type H2 hysteresis is
common for inorganic oxides with a complex network of interconnected narrow
pores. An oversimplified theory attributes it to difference in condensation and
adsorption rates in narrow necks versus the wider bodies—ink bottle pores.[18]
Loops of type H3 are found in solids consisting of aggregated non-rigid plate-
like particles, eg, some clays.[19] Type H4, on the other hand, is characteristic
of microporous substances with type I isotherms, with narrow slit-like pores.
For some microporous materials, the desorption curve lies above the adsorption
curve at low relative pressure (dashed lines in Figure 3). This phenomena may
be due to swelling of non-rigid micropores, irreversible adsorption of adsorbate
molecules (as long as the pore aperture is unaffected), or chemical interactions.

THEORY
The BET theory assumes that the adsorption energy is independent of the
adsorption sites and gas molecules interact only in the vertical direction, lat-
eral interactions between adjacent adsorbed molecules being negligible:[15, 20, 21]
Physisorption of the first adsorbate layer is as follows:
x 1 C −1
= + x (1)
W (1 − x) C × Wml C × Wml

where W is the mass adsorbed at relative vapor pressure; x = P/P0 (P and

P0 are the actual and saturated vapor pressures of adsorbate); and Wml is the
required mass of adsorbate forming a complete monolayer adsorbed on a given
sample. C is a constant, expressing the differences in the heat of adsorption of
the first and second or higher layers and depends on temperature and on the
heat of adsorption of the first layer E1 . For higher layers EL equals the latent
heat of condensation[22] :  
E1 − EL
C = exp (2)
RT
For type III and V isotherms, C = 1. Sing[23] recommended the derivation of
BET monolayer capacity, Wml , from the best linear fit of the adsorption branch
including point B. The BET theory can be applied over a relative pressure

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 I II
Accepted Article

III IV
Amount adsorbed (cm3 g–1 )

V VI

Relative pressure (P/P0 )

Figure 2: Nitrogen adsorption-desorption isotherms.[15]

(P/P0 ) from 0.05–0.35 in the adsorption branch of isotherm, where monolayer

adsorption takes place. The linear region of the BET plot (Figure 4), depends
on the type of adsorbate and adsorbent, as well as the temperature of physisorp-
tion. Some researchers, however, suggest the upper limit P/P0 ratio at 0.1 for
materials like graphitized carbon.[23]
According to Equation (1), a plot of x/W (1 − x)—y versus x gives a straight
1
line with an intercept at β0 = C×W ml
and a slope of β1 = (C − 1)/(C × Wml ).[3]
For a mildly air oxidized biochar, for example, the slope equals 53 g−1 and the
intercept is 0.48 g−1 (Figure 4).[24] The mass of gas that forms a monolayer,
Wml , is obtained from the sum of the intercept and slope:
1
= β0 + β1 (3)
Wml

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 H1 H2

Amount adsorbed (cm3 g–1 )

Accepted Article

H3 H4

Relative pressure (P/P0 )

Figure 3: Types of hysteresis loops obtained by nitrogen physisorption.[15]

The specific surface area, SSA, is as follows:

Wml
SSA = ×N ×A (4)
M ×m
where M is nitrogen molar mass; m it the sample mass; A the nitrogen molecular
cross sectional area (0.162 nm2 ); and N is Avogadro’s number.[3]
For the oxidized biochar with SSA = 65 m2 · g−1 , the mass of the monolayer,Wml ,
equals 1.68 × 10−8 mg for a 46 mg sample.
The Barrett, Joyner, and Halenda method,BJH, and density functional the-
ory, DFT, estimate pore size distribution,PSD, based on the physisorption equi-
librium isotherms. The BJH theory implements two fundamental assumptions;
first the shape of pore is cylindrical, and second the adsorbed amount results
from both physical adsorption on the pore walls and capillary condensation in
mesopores.[11] BJH, thus, considers the radius of pore as the sum of the mul-
tilayer thickness (t) and the meniscus radius obtained from Kelvin equation
(Equation (5)):
P 2γVM
ln = (5)
P0 rRT
where P/P0 is the relative pressure in equilibrium with a meniscus; γ is the
surface tension of the adsorbate in the liquid form; VM is the molar volume of the
liquid; R is the universal gas constant; r is the radius of the meniscus formed in

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 the mesopore; and T is temperature. BJH calculates the change in the thickness
of adsorbed film from the decrease of relative pressure in the desorption branch.
Each decrement is considered to result from evacuation of the largest pores from
the capillary condensate, as well as a reduction in thickness of the physically
adsorbed layer. This theory yields a particular equation correlating pore volume
and radius, which is solved by numerical iteration.[11] Owing to the restrictive
Accepted Article

hypotheses of BJH, this method fails to describe neither micropore diameter,

nor narrow mesopores.[25] Groen et al.[26] , for instance, associated this failure
with different physical effects during practical adsorption, eg, tensile strength
and pore network effects, which lead to incorrect both micro and mesopores size
estimates from the desorption branch.
The International Standard Organization (ISO)[27] recommends DFT to cal-
culate pore size distribution. The theory relies on the experimental adsorption
isotherm Nexp (P/P0 ) Equation (6)[28] :
Z DM
Nexp (P/P0 ) = NDFT (P/P0 , D) × f (D)dD (6)
Dm

where f (D) is an unknown pore diameter distribution function ; and Dm and

DM are the minimum and maximum pore sizes in the kernel, respectively.
The non-local density functional theory (NLDFT) reliably predicts pore sizes
of ordered mesoporous molecular sieves (silicas) given suitable parameters for
adsorbate-adsorbent interactions.[29, 30, 31] Physisorption analysis software such
as Autosorb-1 solves the set of equations by non-negative least squares.[32] For
carbonaceous materials, NLDFT assumes slit-shaped pores without network

Figure 4: Example of BET plot to derive β0 and β1 (Equations (1) and (4)).[24]

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 connections yet with ideal graphitic walls.[33] Quenched solid density functional
theory, QSDFT, represents roughness and the pore wall surface heterogeneity
with a single parameter.[29, 30] DFT is considered a more realistic and adaptable
calculation approach of pore size distribution. This is, for instance, evidenced by
the results in Table 1, from the differences between average pore size diameter
determined by the BJH and DFT methods for mesoporous silica after template
Accepted Article

removal, either by air calcination or ozone treatment.[31] For samples OTMS,

BJH results are close to DFT ones, while for samples CTAC and SBA-15 pore
diameters estimated by DFT are almost 1 nm and 2 nm higher, respectively.

Table 1: Examples of mesostructured silica, freed of template either by ozone treatment (-oz)
or air calcination (-cal) (adapted from Joshi et al[31] )

Sample BET area BJH pore size DFT pore size Total pore volume
(m2 · g−1 ) (nm) (nm) (cm3 · g−1 )
ms-OTMSa-oz 945 2.8 3.0 0.73
ms-OTMS-cal 926 3.0 3.2 0.77
ms-CTACb-oz 955 2.9 3.9 0.91
ms-CTAC-cal 1136 2.9 3.7 1.08
SBA-15-oz 711 10.0 12.0 1.16
SBA-15-cal 749 8.6 11.0 1.15
a Mesoporous silica - octadecyltrimethoxysilane.
b Mesoporous silica - cetyltrimethylammonium chloride.

APPLICATIONS

In 2016 and 2017, 70 articles in Can. J. Chem. Eng. mentioned N2 adsorp-

tion, BET, and BJH-DFT, which ranks this topic 3rd among all experimental
techniques. It was 4th (45400 occurrences) over the same period in the WoS
behind X-ray diffraction, scanning electron microscopy, and transmission elec-
tron microscopy.[1] Of the top 10000 cited articles, RSC Advances published 481
of them, followed by Desalination and Water Treatment (219), Chemical En-
gineering Journal (185), Applied Surface Science (167), International Journal
of Hydrogen Energy (151), Applied Catalysis B-Environmental (125), Ceramics
International (123), and Journal of Environmental Chemical Engineering (122).
The most prolific science category was physical chemistry with 2015 occurrences.
Chemical engineering has the second largest number of articles with 1744, fol-
lowed by multidisciplinary chemistry (1493), then multidisciplinary materials
science (1493), environmental engineering (715), and energy and fuels (713).
VOSviewer generated a bibliometric map of keywords from the 10 000 most
cited articles in 2016 and 2017 (Figure 5). The size of the circles is associ-
ated with the frequency of keywords in the articles corresponding to SSA and
pore size distribution, while the colors classify the subjects with similar con-
cepts. VOSviewer identified four main domains associated with SSA includ-
ing water treatment and adsorption in blue, nanoparticles and composites in

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 green, photocatalysis reactions in chartreuse, and catalysts in red. The most
frequent keyword is adsorption with 1795 occurrences (blue cluster), followed
by nanoparticles (1248, green cluster), and aqueous solution (1077, blue clus-
ter). The smallest circles (selective oxidation and porosity) correspond to 107
occurrences.
Specific surface area plays a primary role in the adsorption of chemicals
Accepted Article

and ions from either aqueous, or gaseous solutions, as well as in nanoparticle

applications.[34] The blue cluster (Figure 5) groups keywords related to water re-
mediation, mostly including adsorption, activated carbon, removal, wastewater,
aqueous solutions, equilibrium, kinetics, RSM (response surface methodology),
heavy metal ions, and methylene blue.[35]
The nanoparticle cluster (green) is strongly connected to adsorption, which
implies that researchers are seeking simple methods to synthesize particles like
carbon nanofibers (CNFs). Wang et al.[36] compared different methods to pro-
duce CNFs and mentioned template etching with SSA = 970 m2 · g−1 . This was
reported as a more efficient approach in CNFs synthesis than the conventional
ones such as catalytic growth, electrospinning activation, and electrospinning
PAN/pitch.[37, 38, 39] When surface area is the only targeted characterization of
an adsorbent, researchers prefer carbonaceous materials such as biochar rather
than CNFs, because they are easier to synthesize and modify.[40] Biochars are
applied for water remediation to remove heavy metal cations and chemicals.
Given its production conditions, biochar must be modified using chemical or
physical activation, in order to increase its BET surface area. Chu et al.[41]
investigated chemical activation using H3 PO4 . They reported that mixing
biochar with H3 PO4 , followed by carbonization at 350 ◦C, increased SSA from
9 m2 · g−1 to 795 m2 · g−1 . They obtained a higher surface area by first mix-
ing raw pine sawdust with H3 PO4 , followed by pyrolysis at 350 ◦C, resulting
in SSA of 1150 m2 · g−1 . The purpose of modifying the surface was to ad-
sorb carbamazepine and bisphenol from industrial wastewater. Bardestani and
Kaliaguine[24] instead applied steam activation to the increase biochar surface
area, which could be easily implemented in line with the pyrolysis process (post-
pyrolysis treatment). They used a pyrolysis biochar obtained from a mixture of
spruce, fir, and pine shredded wood pyrolyzed at 475 ◦C, and increased SSA of
the sample from 50 m2 · g−1 to 1025 m2 · g−1 , by steam activation at 900 ◦C for
1 h. The same biochar materials were also submitted to mild air oxidation at
200 ◦C, yielding much higher surface density of oxygenated functional groups.
This made the biochar interesting for cation adsorption in spite of a modest
increase in SSA.[42] Qian et al.[43] reported that surface area and micropores
of biochar contribute significantly to the sorption of organic contaminants from
water. However, the size of these pores is also important for this removal, since
targeted chemicals are found in different molecular sizes.[44]
More keywords are associated with the red cluster than any other and it is
centered around catalysis. Patience and Bockrath[45] showed that in the cat-
alytic partial oxidation of n-butane to maleic anhydride, yield decrease with
time was directly proportional to the loss in surface area (whereas initial yield
was independent of initial surface area). As reviewed by Sun et al.[46] , narrow

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 micropores of zeolites may reduce catalyst activity in the conversion of heavy
oil-based bulky molecules in different reactions, due to the decrease in reactants
diffusivity. The suggested solution introduces mesopores into a solely micro-
porous matrix. For example, mesoporous ZSM-5 shows much higher activity
in alkylation of benzene with ethylene than conventional ZSM-5, owing to its
much wider diffusion paths in the mesoporous structure.[47] Wang and Xiao[48]
Accepted Article

reviewed recent applications of nanoporous catalysts, eg, resins, metal oxides,

carbons, mesoporous silicas, polydivinylbenzene, and zeolites, that exhibit in-
teresting catalytic activity, recyclability, and product selectivity in a variety of
biomass conversion reactions. For example, Nafion/silica nanocomposites, SAC-
13, are highly active and recyclable in the esterification of short-chain carboxylic
acids, eg., acetic acid, owing to their proper pore diameter, while they show low
activity for the long-chain ones like caprylic acid, owing to a considerable accu-
mulation of these acid molecules on the external surface of SAC-13. Each type
of nanoporous catalyst, however, has special advantages for a targeted appli-
cation. Zeolites are thermally stable though relatively low in activity because
of their microporous structure; carbons have high thermal stability and surface
area, yet low wettability. New catalysts could, however, be synthesized with
the aim of combining required features. For instance, as discussed above, the
introduction of mesopores into zeolites removes some of their diffusional limi-
tations in reactions with bulky molecules. Oxidation of carbonaceous materials
increases oxygenated surface functional groups, thereby improving the surface
wettability.
Song et al.[49] investigated the effect of thermal carbonization and chemical
activation on walnut shell in catalytic hydrolysis of CS2 and COS from tail gas to
sulfur. The samples with the highest SSA also had the highest sulfur retention
capacity SSA >1000 m2 · g−1 . In a similar vein, a Fe−Cu−KOH catalyst sup-
ported on walnut shell activated carbon prepared by a sol-gel method was more
active when the surface area was higher, regardless of acidic site density or ther-
mal stability.[50] Acetaminophen was oxidized by ozone over a high surface area
modified MgO at a higher rate compared to a non-modified MgO.[51] Xu et al.[52]
reported that plasma-engraved Co3 O4 had two times higher SSA than the
pristine form, resulting in 10 times higher activity in oxygen evolution reaction.
Afshar-Taromi and Kaliaguine[18] investigated the effect of calcination time and
temperature, along with that of the mass ratio of Pluronic123 /Al(O−i−Pr)3 , to
identify optimal conditions to synthesize mesostructured γ-alumina as a cata-
lyst support. They reported that a calcination temperature of 700 ◦C for 3 h
produced a mesoporous sample with SSA of 259 m2 · g−1 . Li et al.[53] tried
to build a three-dimensional porous nano-network to improve oxygen reduction
(OR) electrocatalyst using iron and nitrogen-doped carbon (Fe/N/C) by im-
plementing a special sample preparation procedure using sodium chloride as a
template. NaCl promoted the formation of a 3D-Fe/N/C with a much higher
SSA and, as a result, higher activity in the electrocatalytic process, owing to
the facilitated transfer of O2 molecules. Joshi et al.[31] used two approaches for
template removal including air calcination and ozone treatment, and reported
that except for octadecyltrimethoxysilane mesoporous silica (OTMS), the for-

10

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 ƉŚŽƚŽĚĞŐƌĂĚĂƚŝŽŶ
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Accepted Article

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ŵĞƚĂůŽƌŐĂŶŝĐĨƌĂŵĞǁŽƌŬƐ
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Figure 5: Bibliometric map of keywords created with VOSviewer software based on the 10 000
most cited articles in 2016 and 2017[54, 55]

mer provides pore structures with higher BET surface area (Table 1).

UNCERTAINTIES

Sources of error and limitations

Errors in gas physisorption isotherms determination include instrumental

errors and those related to sample preparation. To minimize operational errors,
the vacuum pump operation must first be checked before degassing. Degasser
filters eliminate particles that are entrained during degassing. The filter mainte-
nance thus improves pores evacuation. O-rings to hold the cell and insulate the
cell connection port must be crack-free, and therefore they should be changed
frequently. We recommend to wearing gloves when manipulating the quartz and
other cells to avoid adding natural oils from the fingers to the sample cell. Cal-
ibrating the cell before each gas physisorption isotherm improves measurement
accuracy and reduces operational error, though at the expense of productiv-
ity. Exceedingly high degassing temperatures and degassing times can change
the morphology of a sample, with a corresponding effect on the sample sur-
face area. Too mild degassing conditions may, however, not effectively evacuate

11

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 the pores from physisorbed water and volatiles, with pores remaining inacces-
sible to nitrogen molecules. This would underestimate pore volume and SSA.
Thus, samples, especially those with micropores, need to be degassed under
more severe conditions, while avoiding altering the material properties. As long
as degassing conditions change the sample mass, as in the case of some car-
bonaceous materials, BET measurements are unreliable and porosity estimates
Accepted Article

change with degassing time and temperature. Sigmund et al.[56] studied the role
of degassing temperature in the BET analysis of four types of biochar, carbon
nanotubes, and Al2 O3 . They reported that this parameter strongly influenced
SSA, changing the elemental compositions of biochar samples, even at a low
temperature of 105 ◦C. They proposed that researchers in the biochar commu-
nity prepare standardized degassing protocols, which, however, might be difficult
to achieve due to the different biochar sources and pyrolysis conditions. For in-
stance, Bachmann et al.[57] proposed a degassing temperature range of 100 ◦C to
200 ◦C, while Bardestani and Kaliaguine[24] found that degassing under 300 ◦C
does not allow nitrogen physisorption, owing to the presence of a heavy fraction
of pyrolysis bio-oil filling biochar pores. In order to obtain more precise SSA,
the sample mass should be measured after degassing. For samples that readily
adsorb humidity, they should be weighed shortly after degassing. Another com-
mon experimental mistake is associated with insufficient time allowed to reach
a stable sample temperature after each incremental addition of the adsorbate.
The adsorption process is exothermic and the temperature increases during the
process and sufficient time must be allowed for the temperature to return to the
isotherm temperature.
Often articles report SSA with too many significant figures. The absolute
precision of SSA measurement by BET is not higher than 5 % and reproducibil-
ity is in the range of 1 %. Thus, reporting data with more than three significant
figures is unwarranted.
Despite the relative accuracy and simplicity of the BET theory, it has been
criticized mainly because of its two main assumptions: it neglects lateral interac-
tions between adsorbed molecules (circumvented by working at low monolayer
coverage); and it assumes all adsorption sites are energetically equivalent.[58]
Kruk et al.[59] reported that BET is inaccurate to measure SSA of MCM-41
silica, since they have strongly heterogeneous surfaces that do not satisfy the
BET assumptions. As a result, they reported that SSA obtained by BET anal-
ysis was 10 % to 15 % higher than what is obtained from BJH analysis or an
equation considering geometrical properties (some special considerations such as
pore shape were expressed as an equation by these authors). The difference was
attributed to BET overestimation due to overlapping the monolayer formation
with multilayer adsorption. Other criticisms are also related to the lack of mo-
bility of the adsorbed molecules, which may result in the preferential location of
the adsorbate molecules in the outermost surface, or a lack of consistency with
the heat of adsorption values determined using other methods.[9]

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 Detection limits

The SSA detection limits depend on sample preparation (degassing condi-

tions) and especially the type of adsorbate. N2 could be used for most of the
porous materials. Some researchers, however, question whether N2 physisorp-
tion can allow the SSA of undeveloped porous structure to be determined, which
mainly consists of ultra micropores. They suggest performing adsorption using
Accepted Article

gases with smaller molecular size like argon and carbon dioxide. Wang et al.[60]
reported a very low SSA of 0.7 m2 · g−1 for a biochar obtained by pyrolysis of
Lauan wood (Philippine mahogany) at 500 ◦C. Chemical activation using KOH
then developed pores, which led to a decrease in average pore diameter from
9.5 nm to 2.2 nm with a SSA of 1100 m2 · g−1 . Sedghkerdar et al.[61] also re-
ported a very low SSA of 0.5 m2 · g−1 for Cadomin limestone with an average
pore diameter of 3.5 nm, used as the base material for synthesizing new sor-
bents for CO2 capture. These reported values indicate that a very low SSA is
possible to measure using N2 . On the other hand, Suliman et al.[62] reported
that nitrogen physisorption did not allow the SSA of a biochar prepared from
wood hybrid poplar at a pyrolysis temperature below 500 ◦C to be determined;
however, it could for samples prepared at higher pyrolysis temperatures. They
reported that the values of SSA for a pyrolysis biochar produced at 600 ◦C were
estimated to be 200 m2 · g−1 and 400 m2 · g−1 , using N2 and CO2 as adsorbates,
respectively. These authors ascribe these differences to the higher accessibility
of CO2 to micropores. Garrido et al.[63] attributed the difference in the value
of SSA between N2 and CO2 to the temperature at which adsorption takes
place. They mentioned that for solely microporous solids, narrow pores kineti-
cally restrict the entry of N2 molecules at 77 K. The kinetic diameters of CO2
(0.33 nm) and N2 (0.364 nm) are actually similar. An increase in temperature
would lead to an increase in the diffusion rate of the molecules, only resulting in
a faster adsorption of gas. Therefore, adsorption at 273 K or even 298 K using
CO2 would only accelerate the entry of the adsorbate into ultra micropores, not
the adsorption equilibrium.
There are also some concerns about using CO2 adsorption for the SSA mea-
surement of pyrolysis biochars, which are often loaded with heavy bio-oil. CO2
may dissolve in these heavy liquids, thus yielding overestimated SSA.[64] Con-
trary to the results of Suliman et al.[62] , Bae et al.[5] systematically investigated
the SBET of ultra-micropores zeolites and MOFs and reported that N2 was
appropriate for both these materials to determine the ultra-micropore fraction
(D<0.7 nm). Comparing with other studies, they concluded that BET calcu-
lations underestimate the SBET of MOFs and zeolites, with the standard BET
relative pressure range (0.05< P/P0 <0.3). They proposed a lower P/P0 range
of 0.0001–0.01 for a better estimation of SBET since ultra-micropores are filled
with the adsorbate at much lower relative pressures than the standard condi-
tions. They mentioned that Ar at 87 K could also be a reasonable choice for
substances with ultra-micropores. The results with Ar adsorption agreed well
with those measured by N2 over a range of low relative pressure.[65] Kim et al.[6] ,
however, criticized the conclusions of Bae and Walton’s findings, arguing that

13

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 it is impossible to measure nitrogen (at 77 K) and argon (at 87 K) isotherms
for ultra-microporous zeolites and MOFs with pore diameters close to the ki-
netic diameters of the adsorbates. They suggested that these molecules cannot
overcome the activation energy corresponding to pores entrance at cryogenic
temperatures. They then proposed that the SBET over a relative pressure range
of up to 0.034 determined from CO2 isotherm may be the most meaningful value
Accepted Article

for the materials with only ultra-micropores. Thus this issue of measuring SSA
of ultra-microporous materials is still debated.

CONCLUSIONS

Specific surface area along with pores size distribution (PSD) are fundamen-
tal physico-chemical properties that chemical engineers measure and control
while synthesizing solids and monitoring changes on stream. These physico-
chemical properties are determining factors for catalyst and adsorbent perfor-
mance, and other applications requiring high porosity. Although the technique
was developed nearly a century ago, challenges remain with respect to instru-
ment operation and calibration; researchers often misrepresent the certainty in
the measurement and report more significant figures than the method warrants.
The theory is well documented, however, assuming that the N2 adsorption en-
ergy is independent of the adsorption sites and lateral interactions between
adjacent molecules is negligible introduces error. We identify surprising contra-
dictions in data reporting associated with the types of adsorbate for the SBET
and highlight work that successfully applies N2 . The technique is straightfor-
ward for ceramics and metals, however for fragile substrates, we recommend
that researchers complete a systematic literature review to identify operating
conditions that minimize mechanical and thermal stresses. These are some of
the difficulties that confront researchers, particularly students and those unfa-
miliar with the technique who are the target audience for this article. Advances
in the instrumentation include multiple stations to accelerate the process and
minimize downtime, controlling the jacket temperature more precisely, and im-
proving the signal to noise ratio of the pressure transducers. Older systems took
up to 18 h per sample whereas recent technology has reduced this to 30 min.

NOMENCLATURE

A - molecular cross-sectional area of gas (m2 )

C - BET constant (Equation (2))
d - diameter (m)
dpore - pore diameter (m)
Dm - minimum pore size in the kernel (m)
DM - maximum pore size in the kernel (m)
E1 - heat of condensation of the first monolayer (kJ · mol−1 )
EL - latent (L) heat of condensation of multilayer (kJ · mol−1 )

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 g - gravitational constant (m · s−2 )
m - sample mass charged to cell (g)
M - molecular weight (g · mol−1 )
N - Avogadro constant (mol−1 )
P - pressure (Pa)
Ps - saturated vapour pressure (Pa)
Accepted Article

r - radius of a meniscus (m)

R - gas constant (8.314 J · mol−1 · K−1 )
SSA - specific surface area (m2 · g−1 )
SBET - BET surface area (m2 )
t - time (s)
T - temperature (K)
V - volume (m3 )
VM - molar volume of gas covering a monolayer of solids (m3 )
vpore - specific pore volume (mL · g−1 )
W - adsorbate mass adsorbed on solid (g)
Wml - adsorbate mass adsorbed in monolayer on solid (g)
x - P/P0

x
y- W (1−x)

Greek Letters
β0 - constant in Equation (3)
β1 - constant in Equation (3)
γ - surface tension

ACKNOWLEDGEMENT
Brendan A. Patience collected the data from WoS and created the VoSViewer
bibliographic map.

REFERENCES
[1] G. S. Patience, Can. J. Chem. Eng. 2018, 96, 2312.
[2] J.-B. Donnet, E. Custodero, J. E. Mark, B. Erman, C. M. Roland, eds.,
The Science and Technology of Rubber, fourth edition edition, Academic
Press, Boston 2013, pp. 383 – 416.
[3] K. S. Sing, F. Rouquerol, J. Rouquerol, K. Sing, P. Llewellyn, G. Maurin,
eds., Adsorption by Powders and Porous Solids, second edition edition,
Academic Press, Oxford 2014, pp. 237 – 268.
[4] J. Rouquerol, D. Avnir, D. Everett, C. Fairbridge, M. Haynes, N. Pernicone,
J. Ramsay, K. Sing, K. Unger, J. Rouquerol, F. Rodrguez-Reinoso, K. Sing,
K. Unger, eds., Characterization of Porous Solids III, volume 87 of Studies
in Surface Science and Catalysis, Elsevier 1994, pp. 1 – 9.

15

This article is protected by copyright. All rights reserved.

 [5] Y.-S. Bae, A. Özgür Yazaydın, R. Q. Snurr, Langmuir 2010, 26, 5475.
[6] K. C. Kim, T.-U. Yoon, Y.-S. Bae, Microporous Mesoporous Mater. 2016,
224, 294 .
[7] A. Peigney, C. Laurent, E. Flahaut, R. Bacsa, A. Rousset, Carbon 2001,
39, 507 .
Accepted Article

[8] A. H. Berger, A. S. Bhown, Energy Procedia 2011, 4, 562 .

[9] D. Dollimore, P. Spooner, A. Turner, Surf. Technol. 1976, 4, 121 .
[10] S. Brunauer, P. H. Emmett, E. Teller, J. Am. Chem. Soc. 1938, 60, 309 .
[11] E. P. Barrett, L. G. Joyner, P. P. Halenda, J. Am. Chem. Soc. 1951, 73,
373.
[12] N. Seaton, J. Walton, N. quirke, Carbon 1989, 27, 853 .
[13] G. Kupgan, T. P. Liyana-Arachchi, C. M. Colina, Langmuir 2017, 33,
11138.
[14] C. H. Bartholomew, R. J. Farrauto, Fundamentals of Industrial Catalytic
Processes, 2nd edition, John Wiley & Sons 2005.
[15] K. S. W. Sing, Pure Appl. Chem. 1985, 57, 603 619.
[16] P. Schneider, Appl. Catal. A: Gen. 1995, 129, 157 .
[17] K. Kaneko, J. Membr. Sci. 1994, 96, 59 .
[18] A. Afshar-Taromi, S. Kaliaguine, Microporous Mesoporous Mater. 2017,
248, 179 .
[19] M. M. Labani, R. Rezaee, A. Saeedi, A. A. Hinai, J. Petroleum Sci. Eng.
2013, 112, 7 .
[20] G. Fagerlund, Mater. structures 1973, 6, 239.
[21] S. Lowell, J. E. Shields, M. A. Thomas, M. Thommes, Surface Area Analy-
sis from the Langmuir and BET Theories, Springer Netherlands, Dordrecht
2004, pp. 58–81.
[22] G. S. Patience, Experimental Methods and Instrumentation for Chemical
Engineers, 2nd edition, Elsevier B.V., Amsterdam, Netherlands 2017.
[23] K. Sing, Colloids Surfaces A: Physicochem. Eng. Aspects 2001, 187-188, 3
.
[24] R. Bardestani, S. Kaliaguine, Biomass Bioenergy 2018, 108, 101 .
[25] M. Luisa Ojeda, J. Marcos Esparza, A. Campero, S. Cordero, I. Korn-
hauser, F. Rojas, Phys. Chem. Chem. Phys. 2003, 5, 1859.

16

This article is protected by copyright. All rights reserved.

 [26] J. C. Groen, L. A. Peffer, J. Pérez-Ramı́rez, Microporous Mesoporous
Mater. 2003, 60, 1 .
[27] ISO-15901-3, Pore size distribution and porosity of solid materials by mer-
cury porosimetry and gas adsorption: Part 3: Analysis of micropores by
gas adsorption 2019, https://www.iso.org/standard/40364.html.
Accepted Article

[28] J. Landers, G. Y. Gor, A. V. Neimark, Colloids Surfaces A: Physicochem.

Eng. Aspects 2013, 437, 3 .
[29] P. I. Ravikovitch, A. Vishnyakov, A. V. Neimark, Phys. Rev. E 2001, 64,
011602.

[30] M. Thommes, B. Smarsly, M. Groenewolt, P. I. Ravikovitch, A. V. Neimark,

Langmuir 2006, 22, 756.
[31] H. Joshi, D. Jalalpoor, C. Ochoa-Hernández, W. Schmidt, F. Schüth,
Chem. Mater. 2018, 30, 8905.
[32] C. L. Lawson, R. J. Hanson, Solving least squares problems, [rev. ed.]
edition, Philadelphia: SIAM 1995.
[33] A. V. Neimark, Y. Lin, P. I. Ravikovitch, M. Thommes, Carbon 2009, 47,
1617 .
[34] Y. Feng, Y. Li, L. Shi, M. Wu, J. Mi, Can. J. Chem. Eng. 2017, 95, 2087.
[35] S. Hemidouche, L. Boudriche, A. Boudjemaa, S. Hamoudi, Can. J. Chem.
Eng. 2017, 95, 508.
[36] J. Wang, Z. Zhang, Q. Zhang, J. Liu, J. Ma, J. Mater. Sci. 2018, 53,
16466.
[37] C. Ma, R. Wang, Z. Xie, H. Zhang, Z. Li, J. Shi, J. Porous Mater. 2017,
24, 1437.
[38] O. Duman, S. Tunç, T. G. Polat, B. K. Bozoğlan, Carbohydr. Polym. 2016,
147, 79 .
[39] N.-N. Bui, B.-H. Kim, K. S. Yang, M. E. D. Cruz, J. P. Ferraris, Carbon
2009, 47, 2538 .
[40] V. Krstić, T. Urošević, B. Pešovski, Chem. Eng. Sci. 2018, 192, 273 .
[41] G. Chu, J. Zhao, Y. Huang, D. Zhou, Y. Liu, M. Wu, H. Peng, Q. Zhao,
B. Pan, C. E. Steinberg, Environ. Pollut. 2018, 240, 1 .
[42] R. Bardestani, C. Roy, S. Kaliaguine, J. Environ. Manag. 2019, 240, 404.
[43] K. Qian, A. Kumar, H. Zhang, D. Bellmer, R. Huhnke, Renew. Sustain.
Energy Rev. 2015, 42, 1055 .

17

This article is protected by copyright. All rights reserved.

 [44] H. Li, X. Dong, E. B. da Silva, L. M. de Oliveira, Y. Chen, L. Q. Ma,
Chemosphere 2017, 178, 466 .
[45] G. S. Patience, R. E. Bockrath, Appl. Catal. A: Gen. 2010, 376, 4.
[46] Q. Sun, Z. Dai, X. Meng, F.-S. Xiao, Chem. Soc. Rev. 2015, 44, 6018.
Accepted Article

[47] B.-L. Su, C. Sanchez, X.-Y. Yang, Hierarchically Structured Porous Mate-
rials, Wiley-VCH 2011.
[48] L. Wang, F.-S. Xiao, Green Chem. 2015, 17, 24.
[49] X. Song, K. Li, P. Ning, C. Wang, X. Sun, L. Tang, H. Ruan, S. Han, Appl.
Surf. Sci. 2017, 425, 130 .
[50] X. Song, K. Li, C. Wang, X. Sun, P. Ning, L. Tang, Chem. Eng. J. 2017,
330, 727 .
[51] A. Mashayekh-Salehi, G. Moussavi, K. Yaghmaeian, Chem. Eng. J. 2017,
310, 157 .
[52] L. Xu, Q. Jiang, Z. Xiao, X. Li, J. Huo, S. Wang, L. Dai, Angewandte
Chemie Int. Ed. 2016, 55, 5277.
[53] Y. Li, W. Liao, Z. Li, T. Feng, L. Sun, C. Guo, J. Zhang, J. Li, Carbon
2017, 125, 640 .
[54] N. J. van Eck, L. Waltman, Sci. 2010, 84, 523.
[55] Clarivate Analytics, Web of Science Core Collection, accessed on 12 July
2018, http://apps.webofknowledge.com 2018.
[56] G. Sigmund, T. Hüffer, T. Hofmann, M. Kah, Sci. The Total. Environ.
2017, 580, 770 .
[57] H. J. Bachmann, T. D. Bucheli, A. Dieguez-Alonso, D. Fabbri, H. Knicker,
H.-P. Schmidt, A. Ulbricht, R. Becker, A. Buscaroli, D. Buerge, A. Cross,
D. Dickinson, A. Enders, V. I. Esteves, M. W. H. Evangelou, G. Fellet,
K. Friedrich, G. Gasco Guerrero, B. Glaser, U. M. Hanke, K. Hanley,
I. Hilber, D. Kalderis, J. Leifeld, O. Masek, J. Mumme, M. P. Carmona,
R. Calvelo Pereira, F. Rees, A. G. Rombolá, J. M. de la Rosa, R. Sakra-
bani, S. Sohi, G. Soja, M. Valagussa, F. Verheijen, F. Zehetner, J. Agric.
Food Chem. 2016, 64, 513.
[58] A. Seri-Levy, D. Avnir, Langmuir 1993, 9, 2523.
[59] M. Kruk, M. Jaroniec, A. Sayari, Langmuir 1997, 13, 6267.
[60] S. Wang, H. Wang, Q. Yin, L. Zhu, S. Yin, New J. Chem. 2014, 38, 4471.
[61] M. H. Sedghkerdar, N. Mahinpey, Z. Sun, S. Kaliaguine, Fuel 2014, 127,
101 .

18

This article is protected by copyright. All rights reserved.

 [62] W. Suliman, J. B. Harsh, N. I. Abu-Lail, A.-M. Fortuna, I. Dallmeyer,
M. Garcia-Perez, Biomass Bioenergy 2016, 84, 37 .
[63] J. Garrido, A. Linares-Solano, J. M. Martin-Martinez, M. Molina-Sabio,
F. Rodriguez-Reinoso, R. Torregrosa, Langmuir 1987, 3, 76.

[64] A. Samanta, A. Zhao, G. K. H. Shimizu, P. Sarkar, R. Gupta, Ind. & Eng.

Accepted Article

Chem. Res. 2012, 51, 1438.

[65] K. S. Walton, R. Q. Snurr, J. Am. Chem. Soc. 2007, 129, 8552.

19

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