METHOD FOR THE CALCULATION OF EFFECTIVE PORE SIZE

DISTRIBUTION IN MOLECULAR SIEVE CARBON

Geza HORVATHand Kunitaro KAWAZOE

Department of Chemical Engineering, University of Tokyo, Tokyo 113

Amethod for the calculation of effective pore size distribution from adsorption isotherms in molecular-sieve
carbon is described. This method is more exact theoretically as well as practically than previously described
methods. An average potential function has been determined inside the slit-like pores. With the help of this function
the doubtful use of the Kelvin equation can be avoided at the scale of molecular dimensions. The method gives poor
values for the larger pores but can be combined with the well-known Dollimore-Heal method at a pore size of
1.34 nm. Calculation is possible over a wide range of pore sizes. The calculation is shown through two examples
from N2 isotherms at 77.4K. The model can be extended to other pore shapes as well as to other
adsorbent-adsorbate pairs.

The calorimetric definition of qdlff is

Introduction
^diff = AHv*p_ RT_ (dhf/dna)T (3)
Molecular-sieve activated carbon usually contains
slit-like pores of the order of0.1 nm and the distances The molar integral change of entropy is
between the walls of slits are of the interest from the ASads=AStr+ASrot+ASyih (4)
standpoint of separation processes. Kawazoe et
^ i,i2-i4) repOrtec[
molecular-sieve
studies carbons.
activated
properties theseof
of severalHowever, Except for ASl\ the terms of this equation are nearly
constant, and we can write
authors found no reported theoretical works on pore ASads= AStr(w/wJ +AS0 (5)
size distribution at the scale of molecular dimensions.
Dollimore and Heal2) have given a review and The free energy change can be calculated from the
criticism of previous methods used for the calculation gas-phase pressure. Combining this with the previous
equation:
of pore size distribution. They pointed out that their
improved method also had some problems when AGad* = RTln {p/p0)
pores approach molecular dimensions, because the =AHads- T(ASu(w/wJ +AS0) (6)
Kelvin equation had been used. This problem has
been reported elsewhere also.9) If we consider the limit of zlGads as p approaches p0,
In the micropore domain the so-called "outer sur- lim AStT(w/wJ=0
face" of carbon atoms may be regarded as the
"effective radius of the carbon atom."4) Therefore,
lim p->Po
RT\n(p/po)=AHoads- TASo=0 (7)
the pore size itself must be called the "effective pore
size." This definition by Everett is in use in the case of then
micropores. For larger pores, the problem of the AHoads= TASo= -AHwap= - TASyaip (8)
uncertain size of the "outer surface" is negligible.
1. Theory Wecan also write
Consider the molar integral change of the free RTln (p/p0) = - qdá"- RT+K(Tp/e)(8n/dT)d
energy (Gibbs function for T=constant): - T(AS\w/wJ+AS0) (9)
AGads=AH*ds- TASads (1)
The molar integral change of enthalpy on adsorption Supposing that K(T/3/6)(dn/dT)d ^ RT, the expression
can be simplified to
AHads= -qdm-RT+K(Tp/9)(dn/dT)d (2)
RT\n(p/po)-AHvaP= -qdm-TASir{wlwJ (10)
is16) In the range of p/p0^pjpo>0, the above general
Received February 6, 1983. Correspondence concerning this article should be addressed equation is approximated into Eq. (12), since the
to K. Kawazoe, Dept. ofInd. Admin., Sci. Univ. ofTokyo, Noda 278. G. Horvath is now
at Dept. of Unit Operations, Univ. of Chem. Eng., Veszprem, Hungary.
adsorbed phase is considered similar to the liquid

470 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

phase and then surfaces. The potential, originated from the interac-
I TAS^w/wJKlq^l (ll) tion of the adsorbate molecules in a pore, increases
the interaction energy. The potential function be-
-qdiff=RT\n(p/p0)-AHá"» (12)
tween the two carbon layers filled with adsorbates is
Having considered the definition of qdl{{ on the NnAn+NAA,
molecular level16):
-qdi({=U0+Pa-AEyib-AEtr-AErot (13)
2<r4
- (fHfr
l-r
we used the samelogic to obtain:
'<m «
RTln (p/po) = Uo +Pa (14) where NAis the numberof molecules per unit area of
where the adsorbate and
Uo is the expression of the adsorbent-adsorbate 6mc2ocn(x A (19)
Aa
interactions, and
Pa is an implicit function of the adsorbate- Xa Xa
adsorbate-adsorbent interactions. 3á"c2*aXa
AA (20)
Some authors4'18'19* have determined potential func-
tions over a carbon layer and inside a pore having
where m is the mass of an electron, c is the velocity of
either slit-like or cylindrical shape. They suggest that
the so-called (10 : 4) potential is likely more realistic light, oca is the polarizability and %a is the magnetic
than the (9:3) potential, but it is not possible to susceptibility of an adsorbent atom, <xAand %Aare the
choose between these models on the basis of the polarizability and magnetic susceptibility of an adsor-
bate molecule.
precision with which they represent the adsorption Equation (18) consists of two parts. One of them,
data. Our aim was to develop a suitable method for NaAa\2o^ multiplied by the expression inthe parentheses,
the calculation and not to decide which is the most corresponds to K~X'UO (Eq. (14)); other cor-
adequate model among those mentioned above. responds to K'1 Pa (Eq. (14)).
The micropores of molecular-sieve materials are Having taken into account Eq. (14), an average
usually considered to be slits between two graphitized potential value that depends on the absolute values of
carbon layer planes.1* Supposing that the potential
fields of these layers can be approximated by a distances between the two layers can be calculated:
potential of the graphite layer, simple mathematical NnA»+NAA, r}d/2 d/2
expressions can be used.
RT\n (p/Po)=K 2a\l-d) [-V
The potential function20* over a graphite surface G\10 / \4 / ^ \1(T
(interaction energy between a gas molecule and an
infinite graphite layer) is HtJ -l^J +^J J* (21)
<P= 3.06<P*[- (<j/r)* + ((j/r)10] (15) where ^ is Avogadro's number, and
<P* = (NaAa)/(1.06)(2a*) ( 1 6) d= da +dA (22)

where a is the distance between a gas atom and the da is the diameter of an adsorbent atom, and dA is the
surface at zero interaction energy, r is the distance diameter of the adsorbate molecule. Integration gives
the following result:
from the surface, Na is the number of atoms per unit
area of surface, Aa is a constant given by the NaAa + NAAA
Kirkwood-Muller, London, etc., equations. RTln (p/Po)= K a\l-d)
The potential function between two parallel layers r10
in the case of one adsorbate molecule is: ,.10

3(1-d/2)3 9(1-d/2) 3(rf/2) 3

0 = [(NaAaW^)I ~ {°lrf + Mr)10
(23)
- W(/-r)}4+ W(/-r)}10] (17)
where / should be larger than d. When /=d, Eq. (21)
Where / is the distance between the nuclei of the two gives a finite value of p/p0, pc/p0. So the above
layers. The Frenkel-Halsey-Hill theory5 "8'15* uses equation is considered to be valid for p/po^Pc/Po>
the Kirkwood-Muller expressions for the calculation which satisfies the condition assumed for deriving Eq.
of adsorption potential. A similar expression is used (12).
for the present case of adsorption on two parallel Wenow have a function ofp with respect to /.
VOL. 16 NO. 6 1983 471
 Having used the data of a nitrogen isotherm at liquid (99.999%, Takachiho Kagakukogyo Ltd.) was used
nitrogen temperature, where W^=#(/?), the for adsorption.
expression A schematic diagram of the experimental apparatus
is shown in Fig. 2.
w/Woo =f(l- da) (24)
For measurement of the N2 isotherms at liquid N2
can be obtained. This function gives us the effective temperature a sample (~0.3g) was put into a sample
pore size distribution since w is considered as the mass holder and degassed at 200°C ,and 10"5 Torr
of the nitrogen adsorbed into pores smaller than (1.33x10~3Pa) pressure for at least 48 hours. A
(l-da), and w^ is the maximumamount of nitrogen Cahn electrobalance provided highly accurate mass
adsorbed into the pores. measurement. For the measurement of pressure
ULVAC ionization vacuum gauges and MKS
2. Model Parameters Baratron sensors were used (pressure ranges
The necessary physical data can be seen in Table 1. 1.33x l(T6-6.65x KT1Pa; 1.33x 10"1-105Pa).
Everett and Pawl4) give an equation for the calcu- The data obtained are shown in Table 4 and Fig. 3.
lation of a values:
<7=0.858d/2 (25) 4. Comparison of qdmValues from Different Sources
Using the N2 isotherm of HGS 638 at liquid N2
In our case, temperature the expression
g=0.275nm
qdm = RTln (po/p) + AHvap (27)
According to Walker20) the value ofNa=3.845 x 1015 can be calculated as a function of w/w^- If we
molec-cm"2 while NA=6.7 x 1014 molec-cm"2 calcu- compare the data of this calculation with the data of
lated from the liquid N2 density. From the numerical Kawai,n) good agreement can be seen (Fig. 4). Kawai
data substituted into Eq. (23) the following expression determined the qst values from isotherms at different
can be obtained, where / is in nm. temperatures. The empirical results confirm our sup-
w
. . 62.38
position that the TASXr{wlwao) term is really negligi-
ln (p//?o) = /3o64 ble in the circumstances mentioned above.
1.895xlO"3 2.7087x10 -7 5. Calculation of Pore Size Distribution Function
(/-0.32)3 (/-0.32)9 - 0.05014
Having determined w^, the maximumamount of
(26) N2 adsorbed into the pores at p/p0=0.9, the calcu-
lation of pore size distribution can be carried out.
From the theoretical part it follows that if we know Suitable (l-da) values between 0.35 and 1.4nm are
thep-l functions, we know the;?-(/- da) functions also chosen. Substituting these values of/ into Eq. (26), the
(Table 2). In the same table pore size calculated values of p are obtained. Using the data of the
according to Dollimore can be found. The two curves measured isotherms, the w values corresponding to
(Fig. 1) intersect at a pore size of 1.34nm and a the chosen (l-da) pore sizes can be found. Plotting
relative pressure of//=5 x lO~2. At this pressure the w/w^ against the (l-da), the pore size distribution is
slopes of the two curves are nearly equal. At the point obtained.
of intersection the two methods could be combined. The procedure itself is very simple. Table 5 shows
Beyond p' the Dollimore method can be used while the results of the calculation in the case of HGS638
belowpf the new method may be used. and HGM 366.
3. Experimental In Fig. 5 the molecular probe data3) ofHGS638 are
compared by the calculated pore size distribution. In
Table 3 gives the physical properties of the carbon Fig. 6 the effective pore size distribution curves of
samples used for this investigation. HGM366 and HGM 366 and HGS 638 can be seen. The main
HGS 638 respectively are molecular sieve carbons effective pore size of HGM366 is 0.42nm, obtained
provided by Takeda Ind. Co., Ltd. Research grade N2 from molecular probe data by Takeda Co.
Table 1. Physical properties for calculation of model parameters
C arbon Reference Nitr ogen Reference
0.3
Diameter [nm] 0. 34
0.808
Liquid density [g/cm3] 1.46x 10"24
Polarizability [cm3] 1.02 x 10 "24 2xl0~29
Susceptibility [cm3] 13.5 x 10 "29

472 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

 Table 2. The values of corresponding (plp0), (l-da) pairs Table 4. Data of isotherm
according to the new model and Dollimore
HGS 638 w0O=173.2mgN2/gC (p/Po=0.9)
Relative Effective pore size
pressure [nm] Adsorption
p/Po l-] New model (/-Ja) Dollimore model P w PlPo w/W oo
[Torr] [Pa] [mg N2/gC] [-] [-]
1.46x l(T7 0.4 -
6.47 x l(T7 0.43 - 2.3xl(T4 3.07xlO~2 3.34 3.03xlO~7 0.019
2.39x lO"6 0.46 - 3.8xlO~4 5.07xlO"2 6.7 5.00xlO~7 0.039
1.05x lO~5 0.5 - 8.1xl0~4 1.08X10'1 13.7 1.07xl0"6 0.079

1.54x l0~4 0.6 - 1.1xlO~3 1.47X10"1 18.7 1.45xlO~6 0.108

8.86x l0~4 0.7 - 2.1xlO~3 2.80X10"1 38.4 2.76xlO~6 0.222

2.95x lO""3 0.8 - 3.5xlO"3 4.67xlO"1 52.1 4.61x10~6 0.301

2.22x lO~2 1.1 1.16 1.01xlO~2 1.35 95.3 1.33xlO~5 0.550

4.61 x lO-2 1.3 1.32 4.3xlO~2 5.73x10 114.0 5.66xlO'4 0.658

7.59x l0~2 1.5 1.46 1.6 2.13xlO2 141.0 2.11xlO~3 0.814
3.15x lO"1 3.0 2.23 10.0 1.33xlO3 152.4 1.32xlO~2 0.880
7.24x lO"1 10.0 5.09 47.0 6.27xlO3 157.1 6.18x10~2 0.907
82.0 1.09xlO4 163.1 1.08xlO"1 0.942

165.0 2.20xlO4 166.8 2.17xlO"1 0.963

390.0 5.20xlO4 170.8 5.13xlO"1 0.986
535.0 7.13xlO4 171.8 7.04xlO"1 0.992
640.0 8.53xlO4 173.1 8.42xlO"1 0.999
740.0 9.87x lO4 173.5 9.74x lO"1 -

Desorption
P w p/po wjw^
[Torr] [Pa] [mg N2 /gC] [-] [-]
665.0 8.87xlO4 173.1 8.75xlO"1 0.999
Fig. 1. Pore size vs. pressure. 530.0 7.07xlO4 173.1 6.97xlO"1 0.999
420.0 5.60xlO4 172.8 5.52xlO"1 0.998
228.0 3.04xl04 170.1 3.00X10"1 0.982
Table 3. Physical properties of carbon samples used in this 150.0 2.12xlO4 168.4 2.09xlO"1 0.972
investigation 110.0 1.47xlO4 167.0 1.45xlO"1 0.964
94.0 1.25x lO4 166.1 1.24xlO"1 0.959
HGS 638 HGM 366 48.0 6.40xlO3 163.1 6.32xlO"2 0.942
13.8 1.84xlO3 157.1 1.82xlO~2 0.907
Particle density [g/cm3] 0.90 1.09 7.0 9.33xlO2 152.4 9.21x10~3 0.880
True density [g/cm3] 1.8 1.80.084 2.2 2.93xlO2 146.4 2.89x1Q~3 0.845
Micropore volume* [cm3/g] 0.21 0.56 7.47x10 137.7 7.37x10~4 0.795
Main pore size** [nm] 0.5 0.42
HGM 366 woo=67.5mgN2/gC (p/po=0.9)
* At liq. N2 temperature.
** From molecular probe data of Takeda Co. Desorption
P w PlPo W^ oo
[Torr] [Pa] [mg N2 /gC] [-] [-]
700.0 9.33xlO4 67.5 9.21x10"1 1.00

400.0 5.33xlO4 67.4 5.26xlO"1 0.998

100.0 1.33xlO4 66.7 1.32xlO'1 0.988
10.0 1.33xlO3 66.1 1.32x10~2 0.970
1.0 1.33xlO2 65.3 1.32xlO"3 0.967
1.0xlO"1 1.33xlO1 64.5 1.32xlO"4 0.956
5.0xlO"2 6.67 64.4 6.58xlO"5 0.954
l.OxlO"2 1.33 62.6 1.32xlO"5 0.927
3.0xl0-3 4.00X10-1 61.5 3.95xlO"6 0.911
1.25xlO~3 1.67X10"1 48.1 1.64xlO~6 0.713
Fig. 2. Schematic picture of experimental apparatus. 5.0xlO"4 6.67xlO~2 37.0 6.58xlO~7 0.548
1, microbalance; 2, glass tube; 3, weight; 4, sample; 5, N2- 2.3xlO-4 3.07xlO-2 26.1 3.03x10~7 0.387
bath; 6, gas bomb; 7, vacuum pump; 8, N2 inlet; 9, control 1.2xlO-4 1.60X10"2 12.3 1.58xlO~7 0.182
unit; 10, recorder; 1 1, ionization vacuum gauge (ULVAC); l.OxlO"4 1.33xlO~2 10.6 1.32xlO~7 0.157
12, measuring unit (ULVAC); 13, 14, Baratron sensors; 15,
measuring unit (Baratron); 16, diffusion vacuum pump.

advantages over previous methods, both in theoreti-

6. Discussion
cal exactness and ease of use. Previous methods did
The method described has been shown to have not consider the material properties of the adsorbents.
VOL 16 NO. 6 1983 473
 Fig. 3. N2 isotherms ofHGS 638 and HGM366 at liq. N2
temperature.
Fig. 5. Calculated effective pore size distribution of HGS
638 compared to molecular probe data (#). , calculated
curve (1-w/vO %.
N2
CH2C12
CH3(CH2)2CH3
CH3(CH2)3CH3
CH3(CH2)5CH3
CH3(CH2)8CH3
CH3(CH2)CH(CH3)2
CHC13

CH2-CH2x
O
CH2-Cu{

CH,

CH,
Fig. 4. qAm vs. w/w^ diagram ofHGS 638.

< H-s

CH
CH,-CH-CH,
14

15

CH2^CH2CH9
16 -CH /
CH, CH3
Table 5. Calculated values of effective pore size distribution
>H, CH2-CH2
.CH

17

19
18

CH/ 21
20

^H2 ^ch;
NCHXCH2
/CH2

hi XCH2

^rt2^CH2-CH2/
/CH2CH2./H
CH3-C(CH3)2-CH2-CH(CH3)2
CH3C(CH3)2-OH
^NH2

CC14

potelze W/W"HGM366 W/W-HGS638

[n m ] [-] [-]
0.4 0. 163 0.0087
0.43 0.51 1 0.0473
0.46 0.726 0.0895
0.5 0.926 0.531
0.6 0.956 0.739
0.7 0.958 0.808
0.8 0.970 0.866
1.1 0.977 0.906
1.3 0.978 0.924
1.5 0.985 0.935
Fig. 6. Calculated effective pore size distributions.

Agreement with the data obtained from molecular across a wide range of pressures.
probes is surprisingly good. Acknowledgment
Dollimore and Heal state2) that about 1.5nm is the The authors are indebted to the Takeda Co. and personally to
lower limit of their method in the case of cylindrical Mr. Kyoshi Itoga for providing the adsorbents and the molecular
pores, and in the lower interval it gives undoubtedly probe data.
poor values. Our model gives poor values for larger N omenclature
pores. We can state that the two models together
cover the full range of pore sizes. Aa = constant in Lennard-Jones potential [J/molec]
AA = constant in Lennard-Jones potential [J/molec]
The near-equality of the slopes of the two pore size da = diameter of an adsorbent atom [nm]
vs. pressure curves at their intersection ensures the dA = diameter of an adsorbate molecule [nm]
possibility of a relatively continuous calculation Eyih = vibrational energy [J/mol]

474 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

 a
translational energy [J/mol] = distance between a gas atom and the nuclei of
Erot rotational energy [J/mol] the surface at zero interaction energy [nm]
[J/molec]
G
free energy [J/mol] interaction energy
H
0*
Hads
enthalpy [J/mol] characteristic interaction energy [J/molec ]
[J/mol] la magnetic susceptibility of an adsorbent
tt ads enthalpy of adsorption [cm3]
#0
limited enthalpy of adsorption [J/mol] atom
Hvap [J/mol] Xa magnetic susceptibility of an adsorbate
enthalpy of vaporization [cm3]
hf residual heat of immersion [J/g] molecule
K Avogadro's number [molec./mol]
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Na numberof atoms per unit area of (1978).
adsorbent [atom/cm2]
NA
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"a adsorbed amount [mol/g] 1, 72, 619 (1976).
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Pc pressure corresponding to l=d (=da+dA) Oxford (1946).
Po
qdm
saturation pressure of N2 7) Halsey, G. D.: /. Chem. Phys., 16, 931 (1948); /. Am. Chem.
differential heat of adsorption Soc, 74, 1082 (1952).
q«
isosteric heat of adsorption 8) Hill, T. L.: /. Chem. Phys., 17, 590, 668 (1949).
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r distance from the nuclei of adsorbent layer [nm] 79, 737 (1975).
S entropy [J/(mol - K)]
£ads [J/(mol - K)] 10) "Kagaku Binran," Chem. Soc. of Japan, Maruzen (1966).
srot
entropy of adsorption [J/(mol - K)] 1 1) Kawai, T.: "Kitai no Kyuchakubunri ni Kansuru Kenkyu,"
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5vib
[J/(mol - K)]
^0
entropy of vibration P/(mol - K)] 13) Kawazoe, K., V. A. Astakhav and T. Kawai: Seisan-Kenkyu,
T
limited entropy value of adsorption (Journal of Institute of Industrial Science, University of
temperature Tokyo), 22, 491 (1970).
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the pores tg//gl Science," Vol. 4, p. 242, Wiley-Interscience, New York (1971).
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17) Samsonov: "Handbook of the Phys. Chem. Prop.," Plenum,
*a
polarizability of adsorbent tcm3] New York (1968).
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fraction of surface occupied by molecules [-] 19) Stoeckli, F.: Helv. Chim. Acta, 57, 2195 (1974).
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density of z-th compound

VOL. 16 NO. 6 1983 475