Powder Technology 116 Ž2001.

103–108
www.elsevier.comrlocaterpowtec

Nitrogen adsorption isotherms on carbonaceous materials.

Comparison of BET and Langmuir surface areas
a,)
´
V. Gomez-Serrano ´ ´ a, M.L. Gonzalez-Martın
, C.M. Gonzalez-Garcıa ´ ´ b
a
´
Departamento de Quımica ´
Inorganica, UniÕersidad de Extremadura, 06071-Badajoz, Spain
b
´
Departamento de Fısica, UniÕersidad de Extremadura, 06071-Badajoz, Spain

Received 1 November 1999; received in revised form 1 August 2000; accepted 4 September 2000

Abstract

This study compares the Brunauer–Emmett–Teller ŽBET. and Langmuir equations when applied to N2 adsorption isotherms at 77 K
on various carbon blacks and activated carbons. Adsorbent samples varied greatly in the degree of development of their surface area and
porosity. The activated carbons were more microporous and less mesoporous than the carbon blacks. The equations were applied up to
prp 0 s 0.20, 0.30, and 0.40. The values of the lineal correlation coefficient as a rule were above 0.990. From the derived BET Ž SBET .
and Langmuir Ž SL . surface areas, the conversion factor Ž a . of SL to SBET was calculated. The a mean value Ž a . and the standard
deviation coefficient Ž s . were also obtained. The N2 isotherms fit better to the Langmuir equation for the activated carbons and to the
BET equation for the carbon blacks. The factor a was markedly higher than the unit for all carbons. It increased significantly with
increasing prp 0 range. The a values were closer for each series of carbons, and larger for the carbon blacks than for the activated
carbons; in spite of the fact that the carbon blacks were more mesoporous. As shown by the a increments, the dependence of a on the
prp 0 range was less strong for the activated carbons for the two narrowest prp 0 ranges. The s values indicated that the influence of the
type of carbon on a was greater for the carbon blacks when fitting up to prp 0 s 0.30 or 0.40. q 2001 Elsevier Science B.V. All rights
reserved.

Keywords: Carbon black, Activated carbon; Surface areas

1. Introduction both equations should lead to similar results. However, as

The theory of Langmuir w1,2x is based on a kinetic
model of the adsorption process in which it is considered
that adsorption is restricted to a single monolayer and that
a dynamic equilibrium is reached between the gas phase
and the adsorbed state when the rates of adsorption and
desorption are equal. By adopting the Langmuir mecha-
nism, but introducing a number of simplifying assump-
tions, the Brunauer–Emmett–Teller Žabbreviated BET. w3x
equation was derived subsequently for multilayer adsorp-
tion. The BET equation reduces to the Langmuir equation
by putting the finite number of molecular layers N s 1
w4,5x. In accordance with this fact, when applied to the
monolayer region of adsorption isotherms for N2 at 77 K,
)
Corresponding author. Tel.: q34-24-289-300r395; fax: q34-24-289-
395.
known from the literature w4,6x, there is no general agree-
ment between both equations concerning their application
and derived surface area values.
Although initially set up for an open surface Ži.e., for
nonporous solids., strikingly, the Langmuir equation has
been used to explain the shape of the Type I isotherm,
which arises when the adsorbent is a microporous solid. In
contrast, the isotherms of Type II and Type IV, which are
typical of nonporous and mesoporous solids, respectively,
are generally amenable to the BET analysis.
The degree of conformity of the Langmuir equation
depends strongly on each adsorption system. The corre-
sponding plot of the isotherm may define a single straight
line or a broken line consisting of several straight sections
w4x; the line may also be distinctly curved w5x. For the BET
equation, the range of linearity is usually restricted to the
prp 0 values between 0.05 and 0.30 w4,6x or 0.35 w5,7,8x.
For activated carbons, however, this prp 0 range is much
narrower, i.e., prp 0 s 0.04–0.14 w9x or 0.05–0.20 w10x.

0032-5910r01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 2 - 5 9 1 0 Ž 0 0 . 0 0 3 6 7 - 3
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V. Gomez-Serrano et al.r Powder Technology 116 (2001) 103–108
At present, the BET empirical method of calculating
specific surface areas enjoys widespread use in characteri-
zation studies of carbonaceous materials and catalysts. It is
the most popular procedure for the determination of the
surface area of carbon blacks w11,12x, being the accepted
method to be used with such an aim w13x. Nevertheless, the
degree of reliability of the calculated values of surface area
depends greatly on the source. Thus, it has been reported
previously that the BET nitrogen adsorption surface areas,
as compared to the true ones, are within 20% with a wide
range of adsorbents w6x. For high surface area-activated
carbon fibers, the BET surface is overestimated by 40–50%
w14x. Also, it is within 10% of those surface areas obtained
by other methods for activated carbons w15x. For microp-
ores containing solids, in general, not only the BET equa-
tion, but also the Langmuir equation, often yields very
high values of surface area w4x, as the analysis does not
take into account the adsorption process described as
micropore filling w16x.
The above facts encouraged us to further investigate the
application of the BET and Langmuir equations to adsorp-
tion isotherms for N2 at 77 K. The abundant literature
found on this subject reveals that in many instances it has
been effected either separately or with different purposes.
Furthermore, the same kinds of carbonaceous materials
Že.g., carbon blacks. w17–19x. were frequently used. In this
study, two relatively numerous series of carbon blacks and
activated carbons are used as adsorbents. We first report
the N2 isotherms, mainly for comparison purposes. Then,
the Langmuir and BET equations are applied to such
isotherms, the surface areas of the carbons being calcu-
lated. The primary objective of this work was to compare
the BET Ž SBET . and Langmuir Ž S L . surface areas. These
are estimated at various prp 0 ranges to investigate the
influence of the porous structure of the carbons in the
ranges of micropores and small size mesopores Ži.e., the
pores involved in the adsorption process, which contribute
in fact to the measured surface area. on the derived S BET
and SL values. It is possible since, as can be assumed,
only the pores that possess appropriate pore sizes are
involved in the adsorption process of N2 within each prp 0
range. Adsorbent samples range widely from the porous
structure, which is reflected in their adsorption behavior
toward N2 at 77 K.
2. Experimental
The series of carbon blacks used in this study was made
up of eight carbons Žnotations are indicated in parentheses.:
Sterling V ŽSV., Vulcan 3 ŽV3., Vulcan 6 ŽV6., Black
Pearls 800 ŽBP800., Black Pearls 880 ŽBP880., Black
Pearls 1000 ŽBP1000., Black Pearls 1300 ŽBP1300. and
Black Pearls 2000 ŽBP2000., provided kindly by Cabot in
Spain. These carbons were sized, the fraction of particles
with sizes smaller than 0.32 mm being chosen. The series
Table 1
Notations and granulometric characteristics ŽGC. for the activated car-
bons
Sample Notation GC
Darco D-1 4–12 mesh Ž5–1.8 mm.
Darco D-2 20–40 mesh Ž0.9–0.45 mm.
Norit A NA -100 mesh Ž0.16 mm.
Panreac P powder
Norit RX1 Extra NE cylindrical pellets
of activated carbons consisted of five carbons, which were
employed as-received from commercial sources. Notations
and granulometric characteristics for the activated carbons
are shown in Table 1.
The adsorption isotherms for N2 at 77 K were deter-
mined using a Micromeritics ASAP 2010 surface area
analyser. Samples of 1.3 g for the carbon blacks and of 0.5
g for the activated carbons were used on average in each
adsorption experiment. The adsorbents were outgassed at
1208C overnight prior to the adsorption measurements.
3. Results and discussion
3.1. Adsorption isotherms
Figs. 1–3 show the N2 adsorption isotherms measured
on the carbons. For most of the carbon blacks, the isotherms
were earlier classified w20x according to the system origi-
nally proposed by Brunauer, Deming, Deming, and Teller
Žabbreviated BDDT. w21x. Also, the desorption branch of
the isotherms was then reported w20x. It should be noted
that all isotherms exhibited the presence of a hysteresis
loop, which is a characteristic feature of the Type IV
isotherm w4x. For the activated carbon NE, the isotherm is
typical Type I of the aforesaid BDDT classification sys-
tem. For the rest of the activated carbons, the isotherms
first display an initial ascending branch up to prp 0 f 0.10.
Then, the isotherms show a rather straight portion, which
extend up to prp 0 s 0.60–0.70. Finally, there is an up-
ward sweep near saturation pressure. The increase in the
N2 adsorption at high prp 0 values is greater for D-2.
3.2. Pore Õolumes
From the adsorption isotherms, the micropore volume
X
Ž Vmi . and mesopore volumes Ž Vme , Vme . were obtained.
X
Also, the percentages of microporosity Ž Pmi , Pmi . and
X
mesoporosity, Pme , Pme were calculated. The resultant
Ž .
X X
values of Vmi , Vme , Vme , Pmi , and Pmi are listed in Table 2.
The mesopore volume and the mesoporosity percentage
have been estimated at two prp 0 values, i.e., 0.40 and
0.95. These prp 0 values are the upper prp 0 limit of
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V. Gomez-Serrano et al.r Powder Technology 116 (2001) 103–108 105

Fig. 1. Adsorption isotherms for carbon blacks. Fig. 3. Adsorption isotherms for the activated carbons.

application of the BET and Langmuir equations in this The values of the pore volumes ŽTable 2. show that, in
study, as seen below, and the prp 0 at which the mesopore general, regardless of the prp 0 value at which the meso-
volume is usually derived from the adsorption isotherms, pore volume is obtained, the activated carbons are more
simply by reading the volume of gas adsorbed at prp 0 s microporous than the carbon blacks and that these carbons
0.95. Therefore, Vme represents the volume of mesopores are more mesoporous than the activated carbons. The
X
that take part in the adsorption process of N2 at prp 0 s highest Pmi Ž89.7. and Pmi Ž82.1. values correspond to NE
X X
0.40 and Vme is the mesopore volume actually present in and those of Pme Ž35.5. and Pme Ž87.0. to SV and V6 and
X
the adsorbents. Obviously, the values of Vmi , Vme and Vme to BP800, respectively. Allowing for the morphological
will be more or less close to the true values for the pore properties of carbon blacks, their mesoporosity may be
volumes depending on the degree of involvement of the originated in the voids being between primary particles
wider pores of the carbons in the adsorption of N2 at the within a secondary particle Ži.e., assemblage of particles
aforementioned prp 0 values. In this connection, it should termed aggregate. together with those between a secondary
be recalled here that the physical adsorption of gases, by particle and its neighbors w4x. The pore size will depend on
virtue of the enhanced interaction potential w4,22x, is as- the shape of the carbon black aggregates. These vary in
sumed to occur preferably in narrower pores. Also, the
external surface may contribute to the extent of N2 adsorp-
Table 2
tion. If so, the deviation of the estimated pore volumes
Pore volumes for the carbon blacks and activated carbonsa
should be greater for the less porous carbons. X X X
Carbon Vmi Vme Vme Pmi Pme Pmi Pme
Žcm3 gy1 .
SV 0.014 0.0077 0.05 64.5 35.5 21.9 78.1
V3 0.03 0.015 0.13 66.7 33.3 18.7 81.3
V6 0.04 0.022 0.21 64.5 35.5 16.0 84.0
BP800 0.09 0.037 0.56 70.9 29.1 13.8 86.2
BP880 0.09 0.040 0.60 69.2 30.8 13.0 87.0
BP1000 0.13 0.046 0.65 73.9 26.1 16.7 83.3
BP1300 0.21 0.073 0.64 74.2 25.8 24.7 75.3
BP2000 0.60 0.170 0.88 77.9 22.1 40.5 59.5

D-1 0.24 0.060 0.30 80.0 20.0 44.4 55.6

D-2 0.25 0.070 0.41 78.1 21.9 37.9 62.1
NA 0.28 0.050 0.21 84.9 15.1 57.1 42.9
P 0.36 0.062 0.22 85.3 14.7 62.1 37.9
NE 0.55 0.063 0.12 89.7 10.3 82.1 17.9
a
Vmi s Ž Vad . p r p 0s0.10 Ž Vad s volume adsorbed., Vme s Ž Vad . p r p 0s0.40
X
yŽ Vad . p r p 0s0.10 , Vme s Ž Vad . p r p 0s0.95 yŽ Vad . p r p 0s0.10 ; all pore vol-
umes are expressed as liquid volumes. Pmi sVmi r Vmi qVme =100, Pme
X X X X
sVme r Vmi qVme =100, Pmi sVmi r Vmi qVme =100, Pme sVme r Vmi
X
Fig. 2. Adsorption isotherms for carbon blacks. qVme =100.
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V. Gomez-Serrano et al.r Powder Technology 116 (2001) 103–108

Table 3
Application of the BET and Langmuir equations to the N2 adsorption isotherms at 77 K for the carbons. Values for the lineal correlation coefficient Ž r .
Carbon Langmuir equation BET equation
prp 0 y 1 prp 0 y 2 prp 0 y 3 prp 0 y 1 prp 0 y 2 prp 0 y 3
SV 0.9966 0.9922 0.9858 0.9999 0.9999 0.9997
V3 0.9970 0.9923 0.9857 0.9999 0.9997 0.9997
V6 0.9980 0.9933 0.9880 0.9999 0.9999 0.9996
BP800 0.9982 0.9942 0.9895 0.9999 0.9998 0.9988
BP880 0.9981 0.9940 0.9889 0.9999 0.9999 0.9993
BP1000 0.9983 0.9954 0.9921 0.9999 0.9995 0.9981
BP1300 0.9990 0.9974 0.9935 0.9999 0.9996 0.9978
BP2000 0.9990 0.9976 0.9967 0.9999 0.9985 0.9947

D-1 0.9988 0.9981 0.9972 0.9998 0.9987 0.9965

D-2 0.9985 0.9975 0.9963 0.9999 0.9991 0.9973
NA 0.9994 0.9990 0.9986 0.9995 0.9980 0.9950
P 0.9995 0.9991 0.9986 0.9995 0.9980 0.9951
NE 0.9994 0.9996 0.9997 0.9984 0.9957 0.9915

shape from individual spheroidal particles that are found in
some carbons to the more clustered and fibrous types that
are common in other carbons w23x.
3.3. Surface areas
To estimate the surface area of the carbons, the BET
and Langmuir equations have been applied to three gradu-
ally wider prp 0 ranges of the N2 isotherms. The upper
prp 0 limits for such ranges are 0.20 Ž prp 0 y 1., 0.30
Ž prp 0 y 2., and 0.40 Ž prp 0 y 3.. Their choice was made
by bearing in mind that the usual prp 0 range of applica-
tion of the BET equation is up to prp 0 s 0.30–0.35 w4–8x
and that for activated carbons this prp 0 value is lower
w9,10x. From the calculated values of the lineal correlation
coefficient Ž r, Table 3., which are commonly larger than
0.990 for the Langmuir equation and larger than 0.999 for
the BET equation, it follows that the N2 isotherms fit very
well to both equations. Their r value depends on the kind
of carbonaceous materials and on the prp 0 range. Gener-
ally, it is noticeably larger either for the activated carbons
ŽLangmuir equation. or for the carbon blacks ŽBET equa-
tion.. Furthermore, r as a rule undergoes a progressive
decrease with increasing prp 0 range. For some carbons
ŽSV, V3 and V6, BET equation; NE, Langmuir equation.,
however, the variation of r is of little significance. Notice
that in the case of the Langmuir equation r increases
slightly for NE, which is a typical microporous activated
carbon.
With regard to the values of S L and SBET ŽTable 4., it
is interesting to note first that both S L and S BET vary
greatly for carbons. For BP2000 and NE, particularly, the
degree of surface development is much larger than for the
rest of carbons. Therefore, the carbons used in this study

Table 4
Calculated S BE T and S L values for three prp 0 ranges.a Values of the correlation parameter between S L and S BET
Carbon S L Žm2 gy1 .rSBET Žm2 gy1 . a p r p 0y1 a p r p 0y2 a p r p 0y3
0 0 0
prp y 1 prp y 2 prp y 3
SV 47r37 54r37 62r36 1.27 1.46 1.72
V3 103r80 120r80 134r79 1.29 1.50 1.70
V6 149r115 171r114 191r112 1.30 1.50 1.71
BP800 301r235 338r230 375r222 1.28 1.47 1.69
BP880 291r227 331r224 367r218 1.28 1.48 1.68
BP1000 423r331 470r320 514r306 1.28 1.47 1.68
BP1300 679r529 731r515 801r489 1.28 1.42 1.64
BP2000 1958r1543 2091r1465 2237r1335 1.27 1.43 1.68

D-1 757r607 803r577 853r536 1.25 1.39 1.59

D-2 774r618 828r592 888r555 1.25 1.40 1.60
NA 863r691 901r648 941r590 1.25 1.39 1.59
P 1084r868 1130r814 1182r746 1.25 1.39 1.58
NE 1678r1369 1717r1244 1748r1085 1.23 1.38 1.61
a
Here, SL and SBET Žand also pore volumes in Table 2. have been recalculated from the N2 isotherms just up to prp 0 s 0.20, 0.30, or 0.40. The SL
and S BE T values reported previously w24,25x were obtained using the volumes of N2 adsorption measured experimentally up to prp 0 values that,
according to the carbon, were more or less close to each upper prp 0 limit.
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V. Gomez-Serrano et al.r Powder Technology 116 (2001) 103–108
not only may show marked differences in their porous
structure, as described above, but also in the extent of their
surface area. Second, S L increases, whereas S BET usually
decreases, significantly as the prp 0 range increases. Ac-
cordingly, the estimated values of S L and S BET are influ-
enced in opposite direction by the prp 0 range, which
must also be stressed here.
To facilitate the comparison of SL and S BET , the sur-
face area ratio a s S LrSBET is used. Thus, the value of
this conversion factor indicates the degree of deviation of
S L from SBET . From the above SBET and SL values, a has
been first calculated for the various carbons at the three
prp 0 ranges. Then, the a mean value a and the standard
deviation coefficient Ž s . have been obtained separately for
the carbon blacks and for the activated carbons. The s
value gives one idea of the influence of the type of carbon
on a . Table 4 lists the resultant values of a , whereas
those for a and s are set out in Table 5.
For the three prp 0 ranges, the values of a ŽTable 4.
are usually closer for the carbons belonging to each series
of carbonaceous materials. This fact is important as such
carbons may differ greatly from the degree of development
of their microporosity and mesoporosity. As the best illus-
trative example, notice the values of the pore volumes and
porosity percentages for the couple SV and BP2000 ŽTable
2.. A more marked influence of Vmi on a p r p 0y1 and of
Vme on a p r p 0y3 was expected. However, a correlation
between a and the pore volumes is not observed at all.
Neither is it found with respect to Pmi or Pme . Accord-
ingly, it is clear that the structural parameter of the carbons
that plays the essential role in connection with the magni-
tude of a is not their pore volumes in the ranges of
micropores and small size mesopores Ži.e., the pores that
participate in the adsorption process of N2 at prp 0 values
up to 0.10 and between 0.10 and 0.40, respectively.. Since
the shape of the N2 isotherms ŽFigs. 1–3. is more similar
for each series of carbons and as SL and S BET were
obtained from such isotherms by applying the BET and
Langmuir equations within a particular prp 0 range, it is
evident that the a value is determined by the pore size
distribution of the carbons in such a prp 0 range. That is
to say, the a value depends on the variation of the volume
of pores Ži.e., it is dealt with an accumulative pore volume.
with their size.
The pore size distribution of the carbons is also the
responsible factor for the degree of conformity of the BET
and Langmuir equations. Thus, the values of the ordinate
Table 5
Values of a and s
Carbons a p r p 0y1 a p r p 0y2 a p r p 0y3 sp r p 0y1 sp r p 0y2 sp r p 0y3
Carbon 1.28 1.47 1.69 "0.01 "0.03
blacks
Activated 1.25 1.39 1.59 "0.01 "0.01
carbons
107
axis, which are used in the graphical representations, for a
given prp 0 value are only a function of the volume
adsorbed of N2 Žstp. and therefore of the total volume of
pores present in the carbon that participate actually in the
absorption process of N2 at such a prp 0 value. Needless
to say, the degree of conformity influences the values of
slope and intercept for the straight lines of the BET and
Langmuir plots and, hence, the calculated values of SL and
S BET and as a last resort of a . Owing to these facts,
perhaps it would be interesting to further investigate the
extent to which a hypothetical variation of the pore size
distribution for a few selected carbons would affect a .
However, such a study falls outside the scope of the
present treatment.
As shown in Table 4, the a values are larger than unit,
in particular for the carbon blacks. This is so in spite of the
fact that for these carbons the adsorption mechanism of N2
Žin the mesopores, at least. should be monolayerrmulti-
layer and the Langmuir adsorption model should then be
followed more closely than for the activated carbons. The
worse fitting of the adsorption data to the Langmuir equa-
tion for the carbon blacks must contribute to the existing
discrepancy between the a values for both kinds of car-
bonaceous materials. It is corroborated with the results
obtained for BP1300 and BP2000. For this couple of
X
carbons, both Pmi and Pmi ŽTable 2. are higher than for
the remaining carbon blacks, the r values in the case of
the Langmuir equation ŽTable 3. are comparable to those
for the activated carbons, and the a values Žfor two prp 0
ranges, at least; Table 4. are lower than for the other
carbon blacks.
From the a values ŽTable 5., by comparing the a
increments Ž D a s a p r p 0yn y a p r p 0yny1 , with n s 2 and
3., it can be deduced that a depends on the kind of
carbonaceous materials and on the prp 0 range. Thus, the
D a values are rather close Ž0.19 and 0.22. for the carbon
blacks and significantly different Ž0.14 and 0.20. for the
activated carbons. For these carbons, also, the variation of
D a with the prp 0 range is less marked Ž D a s 0.14. in
the case of the two narrowest prp 0 ranges. Accordingly,
the a dependence on the prp 0 range is less strong when
the upper prp 0 limit is F 0.30. On the other hand, the
higher s values ŽTable 5. that arise for the carbon blacks
for prp 0 y 2 and prp 0 y 3 denote a greater influence of
the type of carbon on the a value. For the activated
carbons, s presents the same value irrespective of the
prp 0 range, and therefore the influence of the type of
carbon on a is similar for the three prp 0 ranges.
The above findings are really remarkable. This is so
mainly allowing for the widespread use of the BET and
Langmuir equations, together with the Dubinin–
Radushkevich equation w26x, in studies of the adsorption
"0.02 process and in the structural characterization of solids. In
"0.01
particular, the relative magnitude of a for the two series
of carbons is worth noting. It has been reported previously
w4x that a number of arguments suggest that for microp-
108 ´
V. Gomez-Serrano et al.r Powder Technology 116 (2001) 103–108
orous solids S L does not represent a true specific surface
and also that the calculated S L values are often improbably
high. Evidence is afforded by the Gurvitsch w27x rule,
which is often obeyed by systems showing Type I
isotherms. More recently, it has been stated by the IUPAC
Commission on Colloid and Surface Chemistry w28x that
for micropores containing adsorbents the values of the
surface area as derived by either the BET or the Langmuir
analysis are incorrect. The results obtained in this study
make it clear that the deviation of S L from S BET is less
important just for the activated carbons, which are more
microporous than the carbon blacks. Furthermore, the de-
gree of incorrectness of S L from SBET will be smaller with
decreasing and increasing prp 0 range, respectively, as
commonly in these directions SL and S BET are signifi-
cantly lower ŽTable 2.. Finally, it should be noted that an
indiscriminate use of either the Langmuir equation of the
BET equation to estimate the surface area of carbons will
be more feasible by narrowing the prp 0 range since the
S BET and SL values would be closer with each other.
4. Conclusions
The comparative analysis of the application of the BET
and Langmuir equations at three prp 0 ranges of the N2
isotherms at 77 K on two series of carbonaceous materials
show that such isotherms fit better to the Langmuir equa-
tion for the activated carbons and to the BET equation for
the carbon blacks. S L is invariably higher than S BET ,
irrespective of the carbon and of the prp 0 range. For both
series of carbons, the quotient a s S LrSBET increases
significantly with increasing prp 0 range. The a values
are larger for the carbon blacks than for the activated
carbons. The fact that the a values as a rule are closer for
each kind of carbonaceous material has been connected
with the more similar porosity distribution of the carbons
in the porosity fraction made up by the pores that take part
in the adsorption process of N2 within a particular prp 0
range. The dependence of a on the prp 0 range is less
strong for the activated carbons for the two narrowest
prp 0 ranges. The influence of the type of carbon on a is
more important for the carbon blacks in the case of the two
widest prp 0 ranges.
Acknowledgements
CMGG wishes to thank the Junta of Extremadura for a
postgraduate scholarship.
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