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ADSORPTION OF N2
Ever since the Brunauer, Emmett, and Teller method for the estimation
of surface areas was introduced, a vast literature about the BET equation
has been published. The originators of the BET method knew that their
equation did not fit the experimental data for all relative pressures, and
they recommended rightly, for practical purposes, restricting its use to the
range of relative pressures between 0.05 and 0.35.
For other estimations, such as the sizes, the shapes, and the distribution
of capillaries, however, the multimolecular adsorption curve over its whole
range of pressures is required. If we restrict ourselves to one adsorbate
(nitrogen) and to one temperature (liquid nitrogen temperature) it is a
fortunate fact that, for a wide variety of adsorbents, the multimolecular
adsorption curve proves to be identical, provided no capillary condensation
occurs and no narrow pores are put out of action in the course of progressing
adsorption. These two restrictions, just mentioned, demand a careful choice
of the adsorbents for the determination of the universal multimolecular
adsorption curve which is to be used as a reference curve for texture
4O5
406
DE BOER ET AL.
[1]
17~-
7 2.0
6
5
;o/j
-4
>o
0 Q1 Q2 Q3
....
~
P/Po
0.4
Q5
0.6
Q7
Q8
0.9
1~
408
DE BOER ET AL.
,s,s0
580
,o-loo
#~
.,,
.... ,,,.,
....
, ....
J
~
, ....
,, ....
, . , .
1,,
tA
409
Y~
__
[2]
CkX
(1 -- k x ) ( 1 +
(c -- 1)kx)
where x = p/po gives, when c = 53 and k = 0.76, a good fit with the experimental curve. (The value of V,~ derived from an Anderson plot is always
higher than the corresponding figure from a BET-plot; in our case it is a
factor 1.16.)
This result, however, has no physical significance. In Anderson's conception k < 1 means that the heat of adsorption of the second and higher
layers is less than the heat of liquefaction--a condition which is even less
favorable for multimolecular adsorption than the B E T conception itself,
according to which the heat of adsorption of the second and higher layer
equals the heat of liquefaction. In the B E T theory a picture is chosen
which gives a high figure of combinatorial entropy because attraction forces
between neighbor molecules in the various layers are excluded. As 5/IcMillan
and Teller (8) have shown this means that the surface tension of the liquid
is neglected; when the real surface tension is introduced hardly any multimolecular adsorption occurs when the heat of adsorption of the second and
higher layers is not higher than the heat of liquefaction (9).
Starting from the conception of the condensed (liquid) character of the
mu]timolecular adsorbed film and from an empirical equation of state for
condensed films, Harkins and Jura (10) derived in 1944 a simple equation
log x = B -
A
(Va)----~,
[3]
where again x = p/po, Va is the adsorbed volume, and A and B are constants. Our experimental curve A of Fig. 1 can excellently be described by
this equation for all values of x between 0.1 and 0.75, as is shown in Fig. 4,
where we compare the experimental values of t with those calculated with
the equation:
13.99
log x = 0.034 -- t--V-
[3a]
13.99(V~) 2
(3.54 Va) 2 - 0.034
1.116(Vm) 2
(Va) 2
[3b]
410
DE BOER ET AL.
/
2.C
I.C-
>u
c-
0,1
~.m~.,..---
0,2
0,3
0,4
0,5
0,6
Q7
0,8
0,9
1,0
P/Po
[4]
411
-3,0
I
1C
8-
=2.0
6-
~z
I
4-
-1.0
.c
0.1
~-I~,-,,,-
Q2
Q3
Q4
Q5
0.6
Q7
Q8
Q9
1.0
P/Po
FIG. 4. The isotherm equation of Harkins and Jura, fitted to the experimental
points of the universal t-curve.
412
DE BOE~ ET AL.
Va in milliliters STP per gram and S in square meters per gram, they found
k = 4.06.
When we combine Eqs. [3b] and [4] with [1], we obtain:
k = 4.14.
In a study about the relationship between the B E T equation and the
equation of ttarkins and Jura, Livingston (11) concluded that, in a range
of relative pressures between 0.07 and 0.72, both equations may fit experimental data equally well, if the value of c in the B E T equation is chosen
between c = 50 and c = 100. Later in his paper, however, it is clearly
stated that Emmett's (12) calculations, showing that both equations may
cover an experimental plot between p/po = 0.11 and p/Po = 0.40 (for
c-values between 25 and 250), are correct. In the present section of this
article we come to the conclusion that the Anderson equation (one more
constant than the B E T equation) and the Harkins and Jura equation cover
our experimental master curve equally well for a long range of relative
pressures.
IV. THE HIGH ~ELATIVE PRESSURE END OF THE CURVE
The Frenkel-Halsey-Hill equation (13)
In x = -- - -
(Va) r'
[5]
where C is a constant and x and V~ have the same meaning as above, assumes an adsorbed multilayer of liquid character with the same density
and packing as the normal liquid, the heat of evaporation being higher
than the normal one due to the extra van der Waals' forces exercised b y
the adsorbent on the adsorbed liquid layer. If only London-dispersion
forces are present r - 3.
In many cases of adsorption on surfaces of oxides, salts, or metals, however, polar contributions are also present, and these contributions to the
van der Waals' forces tend to lower the value of r. In the old conception of
de Boer and Zwikker (14) (1928) such polar contributions were introduced
as an addition to the normal heat of evaporation. Since London introduced
the dispersion forces (1930) we know that polar contributions cannot explain the normal magnitude of the van der Waals' forces; they may, however, lower the value of r from 3 to values in the neighborhood of 2, as is
often found.
In the old conception of 1928, however, it was also suggested that a small
deviation of the liquid density (liquid packing) might lead to an intersection of the adsorption curve with the vertical axis at p/po = 1, instead
of gNing an asymptotic approach. Our experimental curve (curve A in
Fig. 1) shows the tendency to lead to a finite amount of adsorption at
413
414
DE ~OER ET AL.
known for relative pressures between 0.10 and 0.75, can be expressed in
terms of an average thickness of the adsorbed layer (the t-curve).
When experimental adsorption data on microporous adsorbents are
plotted as a function of this t-curve, the t-plot obtained gives direct information about the specific area, the capillary condensation, the width
of pores, etc.
Two equations m a y describe the t-curve more or less adequately; the
theoretical nonsignificance or significance of this is discussed.
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