JOURN&IJ OF COLLOID AND INTERFAC~ SCIENCE 21, 405-414 (1966)

THE t-CURVE OF MULTIMOLECULAR N2-ADSORPTION

J. H. de Boer, B. C. Lippens, B. G. Linsen, J. C. P. Broekhoff,

A. van den Heuvel, and Th. J. Osinga
(Technological University of Delft, The Netherlands)
Received April 7, 1965

During his many years of editorship of this Journal, Victor K. La Mer

has certainly had the opportunity to witness major and minor changes in
theoretical conceptions. In colloid science, as in all other branches of
science, theoretical conceptions lead often to equations which fit experi-
mental data satisfactorily. Even if later such theoretical conceptions may
be proved to be wrong, the equations may serve a practical purpose. In
this special issue of the Journal of Colloid Science, dedicated to the parting
Editor-in-Chief, he may be interested to learn how the study of multi-
molecular adsorption, though approached theoretically from various
angles, is still largely based on empirical or semiempirical equations, which,
however, enable us to derive many useful data concerning the texture of
microporous substances, such as adsorbents, catalysts, or catalyst carriers.

I . T H E t - C u R v E , A ~([ASTER CURVE FOR MULTIMOLECULAR

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.

determinations. Recent experimental work (1) enables us to recommend

for this purpose, up to a relative pressure of 0.75, the data which we
published early in 1964 (2). We hope to extend the curve by further careful
measurements.
The data are expressed in terms of an average thickness of the adsorbed
layer in Angstrom units (hence the name t-curve). In doing so we assume
the adsorbed layer to behave as a normal liquid nitrogen layer with its
proper density at the given temperature, and we also assume a hexagonal
dense packing (2). In Fig. 1 we show this master curve (curve A) together
with the BET-curve (curve B) fitted to give the same surface area. As the
thickness of one statistical layer is 3.54 A, a value of n X 3.54 A indicates
an adsorption of n = Va/V,~ layers, where Va is the adsorbed volume and
Vm the monolayer capacity, both in milliliters STP per gram of adsorbent.

II. PRACTICAL APPLICATIONS

A practical way to use this master curve (curve A in Fig. 1) is to plot
experimental adsorption curves as a function of the t-values;hence V = f ( t )
instead of V = f ( p / p o ) . In any normal case of multimolecular adsorption
the experimental points should then fall on a straight line through the
origin. The slope of this line gives the specific surface area, S t , in m.~/g.,
by means of the equation (3):
St = 15.47(Va)/t. [1]
In Fig. 2 curve A gives the t-plot of an alumina prepared by heating
well-crystallized boehmite at 750°C. ; the isotherm of this specimen is de-
scribed in No. II of our series on pore systems in catalysts (4). A pore-size
distribution analysis of this alumina (5) showed a set of wide (>25 A)
slit-shaped pores, open on all sides, giving no capillary condensation during
the adsorption process, until high relative pressures ( > 0.75) were reached;
the desorption branch shows a wide hysteresis loop, closing at p i p e = 0.48.
During adsorption, therefore, the multimolecular adsorption develops, un-
hindered by capillary condensation or by closing of pores.
Curve B shows the t-plot of an alumina made by heating bayerite on
580°C. At a t-value of 4.65 A (piPe) = 0.24) the experimental curve devi-
ates from the straight line, indicating that more nitrogen is taken up than
corresponding with multimolecular adsorption. Capillary condensation has
set in at this point. At an average t-value of about 9 A (p/po N 0.72) the
pores responsible for this phenomenon are filled, and a new straight line
shows the continuation of the multimolecular adsorption on the remaining
surface (outer surface and/or surface in wide pores); the slope indicates
this remaining surface area to be about 20 m.2/g., whereas the original slope
of the t-plot indicated a surface area of 243 m.2/g. (S•ET = 245 m.2/g.).
Curve C gives the t-plot of an aluminum oxide (hydroxide) prepared by
 B

17~-

o /
- J
7 2.0

;o/j
-4
>o

0 Q1 Q2 Q3 0.4 Q5 0.6 Q7 Q8 0.9 1~

.... ~ P/Po
FIG. 1. The experimental m a s t e r curve for t h e adsorption of nitrogen a t 78°K.
(curve A), compared w i t h the B E T q s o t h e r m fitted to give t h e same surface area
(curve B).
407
408 DE BOER ET AL.

~ 580

,s,s0 7 J

,o-loo ~ #~ ~

.,, .... ,,,., .... , .... , .... ,, .... , . , . I , . . . 1,, °

O
tA

FIO. 2. V~-t-plots of some aluminas as described in the text

heating the same bayerite, as above, at 250°C. From the slope of the first
part of the t-plot follows St = 483 m.2/g. (SBET ---- 489 m.2/g.). Between
the t-values of 4 A and 5 A all narrow slit-shaped pores, which are responsi-
ble for this high value of surface area, are apparently filled; the new slope
indicates a surface area of about 20 m.2/g, for the surface area of wider
pores and the outer surface.
These examples may suffice to show the significance of the deviations
from the straight t-plot. Other combinations may be found; in many cases
a downward deviation indicating a closing of capillaries which, because of
their size and shape, do not give capillary condensation in the adsorption
branch (slit-shaped pores with parallel walls) may later be followed by an
upward deviation indicating capillary condensation in wider pores (in the
same elementary particles or as "stacking pores" between those particles),
etc. Together with the shape and the position of a hysteresis loop, the
t-method may give a rather useful picture of the pore texture of micro-
porous substances.
In some cases one may find pores of such narrow dimensions that a
normal BET-plot gives erroneous results. A t-plot does not give a straight
line through the origin in such cases, but yields lines cutting the zero
relative pressure at positive values. The slope of the line drawn from the
origin to the first experimental point at the lowest relative pressure gives
then a lowest value of the surface area. This method yields extremely
useful results with regard to the study of the texture of carbon blacks (6)
 THE t-CURYE OF MULTIMOLECULAR N2-ADSORI:'TION 409

III. EQUATIONS DESCRIBING THE t-CuRvE

Figure 1 shows clearly that the B E T equation cannot describe the
experimental master curve of multimolecular nitrogen adsorption. 1V[any
modifications and alterations have been suggested to improve the B E T
equation or to adapt it to special cases. One of these suggested modifica-
tions, the equation given by R. B. Anderson (7), can be made to fit our
experimental curve A of Fig. 1. As shown in Fig. 3 the Anderson equation
Va __ CkX [2]
Y~ (1 -- k x ) ( 1 + (c -- 1)kx)

where x = p/po gives, when c = 53 and k = 0.76, a good fit with the ex-
perimental 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 con-
ception 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 multi-
molecular 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
A
log x = B - (Va)----~, [3]

where again x = p/po, Va is the adsorbed volume, and A and B are con-
stants. 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]

As t -~ 3.54Va/Vm (see Section I), the equation may also be written:

13.99(V~) 2 1.116(Vm) 2
log x -- 0.034 (3.54 Va) 2 - 0.034 (Va) 2 [3b]
410 DE BOER ET AL.

3£

/
2.C

I.C-

E
>u
c-

I ~ I i I I I I ~
0 0,1 0,2 0,3 0,4 0,5 0,6 Q7 0,8 0,9 1,0
~.m~.,..--- P/Po

FiG. 3. The theoretical isotherm of Anderson, fitted to the experimental points of

the universal t-curve.

According to ttarkins and Jura, the specific surface area can be derived
with the equation
S = ~/A. [4]
With N2 as an adsorbent at liquid ni£rogen temperature, and expressing
 THE t-CURVE OF MULTIMOLECULAR N2-ADSORPTION 411

1C
-3,0
I

d
S
8-

=2.0

6-
~z

I
4-

-1.0 ×

.c
¢

I I l I J l I [ I
0 0.1 Q2 Q3 Q4 Q5 0.6 Q7 Q8 Q9 1.0

~-I~,-,,,- 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 experi-
mental 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)
C
In x = -- - - [5]
(Va) r'
where C is a constant and x and V~ have the same meaning as above, as-
sumes 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, how-
ever, 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 ex-
plain the normal magnitude of the van der Waals' forces; they may, how-
ever, 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 inter-
section 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
 THE t-CURVE OF MULTIMOLECULAR N2-ADSORPTION 413

saturation pressure. The extrapolation of Eq. [3] gives Va/V,~ = 5.73

(t = 20.3 A) at p/po = 1. The Frenkel-Halsey-Hill equation, of course,
leads to infinite adsorption at saturation pressure. As already stated in
section I we hope to extend the experimental work and to avoid the con-
tributions from capillary condensation.

V. THE CURVE AT THE LOWER END OF RELATIVE PRESSURES

Our experimental curve starts at p/po = 0.08, where Va/V,~ = 0.99;
this means that the statistical monolayer of nitrogen is practically com-
plete. If the adsorbing surface were entirely homogeneous, a two-dimen-
sional gas (the adsorbed layer) would be in a two-dimensional condensed
state if the temperature of the experiment were lower than the two-dimen-
sional critical temperature. If the nitrogen molecules are still rotating in the
adsorbed state, or if they adsorbed in random positions or in flat positions,
their two-dimensional critical temperature would be well below 77°K.,
which is the experimentally used temperature. There would, therefore, not
be a two-dimensional condensation, unless the nitrogen molecules were
adsorbed in an upright position (15). Experimentally no two-dimensional
condensation was found in the monolayer region at 77°K. with nitrogen on
homogeneous surfaces (16).
It is quite possible that in multimolecular adsorption condensation to an
adsorbed liquid layer may occur. On a heterogeneous surface (all experi-
mental evidence and all equations in this article refer to heterogeneous
surfaces) adsorption on top of a monolayer, hence multimolecular adsorp-
tion, sets in at various relative pressures, depending on the strength of the
adsorption forces. These relative pressures may be, partially, far lower than
p/po ~ 0.1. In our experiments, therefore, we may expect a large number
of liquid patches in the adsorption layer, at p/po N 0.1 when the statistical
monolayer is nearly complete. This is the only reason for using the liquid
density for the adsorbed layer at such low relative pressure. From the prac-
tical point of view one may, of course, add, as further evidence, the facts
that the surface area per nitrogen molecule derived from the liquid density
(viz. 16.27 A 2) agrees well with the estimation of surface areas by the
"absolute method" of Harkins and Jura (17) and with the surface area
estimations by means of lauric acid (18). It may be remarked here that
this agreement does not hold when the Anderson equation is used instead
of the BET equation.
SUMMARY
ExperimentMly an identical multimoleeular adsorption curve of nitrogen
at liquid nitrogen temperature is found for a wide variety of adsorbents,
provided no capillary condensation occurs and no narrow pores are put out
of action in the course of progressing adsorption. This curve, at present
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 in-
formation 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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