JOURNAL OF COLLOID AND INTERFACE SCIENCE 9"3, 577--599 (1967)

Cross-sectional Areas of Molecules Adsorbed on Solid Surfaces

A. L. M c C L E L L A N AND I-t. F. H A R N S B E R G E R

Chevron Research Company, Richmond, California 94802

Received August 19, 1966

Livingston has published two articles
(111, 112) with the title used above. These
papers are now 15 or more years old, and
there is some value to re-examining the sub-
jeer. The most obvious fact is t h a t con-
siderably more data are now available. Some
of the factors responsibIe are (1) the natural
tendency to make more use of the gas
adsorption technique as it continues to
yield fruitful information; (2) efforts to use
the method of Brunauer, E m m e t t , and Teller
(40a) with adsorbates which do not require
liquid nitrogen; (3) the growing awareness of
the gas adsorption method in scientific fields
farther and farther removed from catalysis,
where it first started; and (4) the usual scien-
title curiosity to apply a proved technique
to new chemical systems.
During the past 25 years, it has become
fairly well agreed that the B E T theory has
some features that are probably oversim-
plifications of the true situation at the solid
interface. I n general, the alternate treat-
ments are more complicated to apply or
involve difficult experimental measurements.
Thus, a dichotomy exists. The B E T equa-
tions and method are used quite extensively
to determine surface area but with the
recognition t h a t errors of the order of 10 % -
20 % m a y exist. On the other hand, most
theoretical work now involves other equa-
tions, often applied to adsorption on rather
special solids chosen to be amenable to
calculations. Some of these methods (17,
73, 170) do not require assigning a molecular
area.
However, for the use of the B E T method
m a n y of the points of caution discussed b y
Livingston still apply. For example, the
cross-sectional area (usually symbolized a)
577
of nitrogen, the most frequently used stand-
ard gas, is still not completely agreed upon.
Most workers use 16.2 A 2, and we have
chosen this as our working standard.
T h e use of N2 as the p r i m a r y standard
has been questioned recently (3, 92, 136).
There are suggestions that the quadrupole
m o m e n t of N2 can interact with hydroxyl,
or other polar groups, leading to a change
in ~. Further testing is needed before the
use of N2 as the reference is abandoned
I t is also still quite common to use a cross-
sectional area calculated from liquid density.
I t is probably no longer reasonable to expect
to pick a single value of z for each molecule
and then expect that value to be applicable
on all absorbents. There are numerous papers
showing t h a t when applied to two or more
gases, such a procedure does not give the
same value of sample area for all samples
and all gases tested.
To help get an experimental answer to
the question " W h a t area does an adsorbed
molecule occupy?" we have collected all
the data we could find in which the adsorp-
tion of two or more gases was measured on
the same solid. These values for about 106
compounds are collected in Table I, which
also contains ~ values calculated b y three
m e t h o d s - - f r o m molecular models, critical
constants, and liquid density.
The three types of calculations were done
in the following ways. Molecular models were
built for each compound and a shadow-
graph was t a k e n with a point light source
6 feet away. The resulting shadowed areas
were measured with a planimeter. Both
m a x i m u m and minimum possible areas were
obtained. Such values are undoubtedly
smaller t h a n a molecule actually occupies,
578 McCLELLAN AND HARNSBERGER

even neglecting interaction with the surface.
This underestimation occurs because neigh-
boring molecules cannot fill in all the spaces
around such an outline. A single molecule
covers more space b y excluding other mole-
cules. Another way to estimate the area
from models is to make the shadowgraphs,
then draw a regular "area-filling" polygon
around the molecular shadow. Such a pro-
cedure tends to overestimate the area per
molecule.
The two-dimensional van der Waals' con-
stant b was derived from critical constants
of the bulk substance b y using Hill's for-
mula (82), b (in square Angstroms) = 6.354
(To/Pc) 2/3. Values for Tc and Pc were
taken from International Critical Tables
and Lange's Handbook of Chemistry, 10th
edition. However, critical constants are not
available for all adsorbates.
An estimate of area can be had from the
density of the adsorbed material if a shape
and packing of molecules are assumed (56).
If we make the usual approximation of
spherical shape and hexagonal close pack-
ing, the formula is:
o-= 1.091(M/Np) 2/3,
in which M is molecular weight, N Avo-
60
I I
PERFECT CORRELATION
N 50
=.<:
:
I--
0'3
Z ,40
LCJ
gadro's number, and p the density in grams
per cubic centimeter. Livingston gives other
formulas for different assumed packings
(112). Values for p were taken from the same
sources as critical constants. In this case,
p for the liquid or solid was calculated at or
near the temperature of adsorption.
Further, the table contains columns show-
ing the standard used by the original au-
thors and the corrected ~ value found for
the minority of cases that were not based
on zN~ = 16.2 A 2. The corrected values
were used in all averages, figures, and tables.
See the Notes on Use of the Table for details
INTERCOMPARISON OF METHODS
Since we have four methods for obtaining
~, there are six ways to pair them for com-
parison. A plot of the data in Table I
showed that the two-dimensional van der
WaMs contant derived from critical data is
closely related to ~ values calculated from
liquid density values. For most cases, t h e y
agree within 10%. Since liquid density is
more usually available or more easily meas-
urable, it will probably continue to be widely
used to estimate ~. However, critical con-
stants can be used too if they are readily
found.
Figure 1 shows z from adsorption data
I I I l I I I
085
53
0 o 086
082 S~ ~ 87
70
64 59 S =o61

72
O~
30
I
<E o o3e5
LLJ
)7
<E
~. DEN = 6 3 6 + 0 . 5 9 6 O'ADS. rDERIVED FROM]
~:: 2 0 • [SOLID POINTSJ
<E
.--I 89•
(,.9
LLI • MEASURED FIVE OR MORE T I M E S
J ~c o MEASURED LESS T H A N FIVE T I M E S

I I I I I 1 I I
20 30 4o 7050 60 80 90 I00

MOLECULAR AREA-ADSORPTION, R2
FIG, 1. C o r r e l a t i o n of m o l e c u l a r a r e a f r o m t w o m e t h o d s .
 CROSS-SECTIONAL AREAS OF MOLECULES 579

compared with that from liquid density.

The adsorption value for each substance is 51 BENZENE~ ~2LUENE:
the average of all tabulated results except
those marked "x" in column 8. The ad-
sorption method gives generally a larger
estimate of z than do liquid density cal-
culations. The same trend was found when
values from molecular models or van der
I ETHAN BUTANE
Waals' constants were compared with values 5

derived from adsorption data. Figure 1 also

contains a least squares line for the com-
pounds represented by the solid points. ~ "METHA~ ETHANOL
These compounds are those for which five
or more adsorption values are available in
Table I.
~ 5 NH3~ ~BUTANOL
The trend displayed in Fig. 1 suggests
that one way to estimate ~ is to calculate
it from liquid density, then to use a correla-
tion curve, such as Fig. 1, to get a value
tending toward the average adsorption value.
Such a procedure is at least a step toward
overcoming some of the known flaws in 15 A ~
using the liquid density calculation alone
These flaws are: (1) the assumptions of
10 Kr
spherical shape and close-packing mentioned 5
earlier, and (2) the different surrounding for
an adsorbed molecule compared to one in a r,

liquid. B y using a correlation curve such as

Fig. 1, some allowances are made for devia-
tions from these idealized conditions.
STANDARD VALUES OF
From Table I we can choose 16 substances
that are most often used as adsorbates.
These are compared in Fig. 2, were histo-
grams of the ~ values are presented. The
histograms show the expected general trend
of organic molecules toward larger size as
the number of carbon atoms increases. T h e y
also illustrate the somewhat more compact
grouping of values for the inorganic com-
pounds. The poor grouping of benzene values
is disturbing, especially as it is commonly
used by Russian workers as a standard ad-
sorbate. Note that six values in the table
are not in the figure. For the organic com-
pounds there is such poor "peaking" of
values that picking a best value is either a
purely averaging process or becomes a mat-
ter of considerable search and evaluation of
individual investigations.
We can, however, settle on some recom-
MOLECULA
AREA,
R ~a
Fm. 2. Histogramsofmoleeularareameasured
byadsorption.
mended z values based on the reported data
of Table I using 16.2 A ~ for N2 at - 1 9 5 ° C .
as the primary standard. These are collected
in Table II.
Simple averaging gives rather wide con-
fidence limits which include the liquid den-
sity value except for butane and benzene.
However, in all cases except argon, the liquid
density value is near the lower limit of the
range given. Therefore, the recommended
values are the larger, average values with
argon as the exception. Within the confidence
limits given, which are usually ± 1 0 % -
30 %, there is no significant difference be-
tween molecular area on porous and non-
porous samples.
SOME TRENDS
Table I affords data for showing trends
in homologous series or for other collec-
tions of molecules having a specific charac-
 TABLE 1
C I ¢ O s s - S E c T I O N A L A R E A OF A D S O R B E D M O L E C U L E S

NOTES ON USE OF THE TABLE

Column
1-3 C o l u m n heading self-explanatory. I n column 2, the s y m b o l s are:
VdW--a calculated from v a n der Waals' constants.
Mod.--a calculated fl'om model.
1.d.--a calculated from l i q u i d density a t b o i l i n g p o i n t or (temperature).
za--average a calmflated from a d s o r p t i o n values i n columns 6 a n d 7, those m a r k e d " x " excluded.
4 A comma between the formulas of adsorbents means t h a t substances were each tested. A dash means the sample was a mixture.
A notation such as 6 SiO2 means six different silicas were tested a n d gave the values f o u n d i n column 6.
5 Self-explanatory. The n o t a t i o n " n . s . " here a n d elsewhere means " n o t specified b y the original a u t h o r s . "
6 Values in parenthesis were ea]eulated as part of this work, usually from Vm.
7 Values corrected to a reference a as g i v e n in Table II.
8 The symbols used are: n p - - S a m p l e j u d g e d to be nonporous.
x--Value n o t included in average, qa, in column 2. c~
9 A b l a n k means aN2 = 16.2 A2 was used b y the original authors. A n u m b e r alone is the value, other t h a n 16.2 A~, used for aN2.
If some other substance was the s t a n d a r d one, i t is identified a n d z g i v e n .
10 Self-explanatory

Area per molecule (A2)

Formula Compound name ~. o. a Adsorbent T, (°C.) Refer-
Sta :us ence
Adsorption Adsorption corrected Reference for
for ~v adsorbed area

Ar Argon 1 AgI --195 (lO.O) ~v

nlJ 164
VdW 13.6, Mod. 11.4, I.d. 13.8 (--195) Graphite --195 (11.1) np 164
Za = 14.7 TiO2--anatase --195 (12.4) np 164
Diamond, graphite --195 12.8 np 115
Graphitized C --183 12.8 np ~v
102
Ni (OH), --195 12.9 13.6
c 15.4 172
106
NiO d --195 13.6 14.3 15.4 172
Mo --183, --195 13.6 14.3 np 15.4 79
Glass --195 t3.7 np 57
BN --210 to --197 13.7 14.3 15.6 140
Graphite --195 13.8 np 178
TiO2, rutile --196 13.8 np 85
CdO --183, --195 14.0 80
Coal --184 (14) 13.3 17 122
Poly (tetrafluoroethylene) --189 14.1 13.8 np 16.6 67
Poly (propylene) --190 14.1 13.8 np 16.6 66
TiO~, SiO2 --183 14.3 e A r = 13.8 at 107
--196°C.
KC1 --185 14.3 13.9 np 16.7 94
CsI --196 14.4 13.3 np 17.0 174
 Graphon --185 14.4 133
SiO2 n.s. (14.6) 163
SiO2 --195 14.7 55
5A12Oa --195 15.4 15l
C e m e n t paste --183 (16.0)/ 34
TiO~, SiO~, AI20;~, MgO, --195 16.6 50
Fe~O~
TiO~-HJ anatase --195 16.6 np 46
AI:O~ --1957 i6.6 49
TiO2-HJ anatase --i96 16.88 np 135
SiO~ --195 17.6 55
MgO --183, --195 17.67 ~ x Crystal struc- 179
Q
ture of MgO
AI foil --196 17.9 np 36 0
TiO~--HJ anatase --183 18.19 135
Zr --183, --196 i8.2 np 72
C e m e n t paste --195 (19.3) i 34 bl
AI foil --186 24.8 x 36 ©
AsH~ Arsine As --78.5 11 9O
0C12F2 Diehlorodifluoromethane (Freon-12) Coal --33 4O 17 at --184°C. 122
VdW 29 Mod. 16.7-18.1
CC13F Trichlorofluoromethane Graphitized C --78 to 13 (27.2) 27.6 Ar = 13.6 117 F~
CCh Carbon tetrachloride Graphitized C --40 to 50 (28.5) 28.9 np Ar = 13.6 117
VdW 34.4 Mod. 23.4 ].d. 32.3
aa = 39.2
MgO 25 30.5 42.1 C6H6 = 31.2 160
NiO 25 32.3 44.5 C~H~ = 31.2 160
12 ©
Graphitized C 20.2 37 np
Graphitized C 20 37 np 14
Graphite, charcoal 0 40.7 139
©
Graphltlzed C 20 44 np N2 n.s. 98
SiO2 26 63.6 x 176 N
CF4 Carbon tetrafluoride Fauj asite 193.1 (27.3) 22.7 Ar = 16.6 j 19 0
VdW 22.0 Mod. 13.9 Poly (tetrafluoroethylene) --123 22.2 21.7 16.6 67 F~
~a = 21.9 Poly (propylene) --131 21.9 21.4 16.6 66
N
CIICleF Dichlorofluoromethane Ag, W, ZnO 37.5 52 5~
VdW 27.2 Nod. 15.4-19.2 ].d. 25.7 glass, Monel
{o 7~ 40.1 52
CIiCI3 Chloroform Graphitized C --50 to 50 (27.5) 27.9 Ar = 13.6 117
VdW 29.5 Mod. 18.3-19.7 1.d. 28.5 SiO2 26 54.7 N2 n.s, 176

a I d e n t i f y i n g n u m b e r used in correlation charts.

c Electron microscope, 13.5 A2.
d Plus 0.16 tI20.
e Average value of adsorption data agrees with electron microscope.
J" Original author used 12.8 A2.
a B y "preferred position" calculation.
Original author used 14.4 A2.
Oo
1 Assumed b y compilers.
 FABLE 1--Continued 7~
~9

~.rea per molecule (A ~)

?ormula '.ompound name Adsorbent ", (°C.) ~efer-
enee
kdsorption kdsorption corrected Status [ ~eference a for
f c r ,av adsorbed area

~H~O~ VormicAcid ~iO~ ~8 3.38 N2 n.s. 175

Mod. 10,6-15.8 l.d. 19.9
~H~ ~ebhane INH~)~PO~' 12MoO~ -183 15.0 69
VdW 16.5 Mod. 10.6 l.d. 15.8 (--196); ;iOn, C, Linde 5A -203 to --191 16.4 .7.3 15.4 96
15.9 (--184); 16.1 (-164); 16.4 (--160 ]raphitized C 16.4 6,6 ~r = 13.6 129
to --130) ~TaBr -208 to --198 19.8 63
~a = 17.8 3arhon 1.$, 18 185
.~raphitized C -160 to --130 18.1 k 31
kctivated charcoal -145 19.4 127
?uller's earth -195 21.3 98 7)
~H~O ~ethanol SiO~ ~5 4.1, 18.6, 18.6, 19.6, 3.7, 18.0, 18.0, 19.0, ~r = 2 0 . 8 59
V d W 2 2 . 2 M o d . 12.2-14.0 I.d. 18 27.9, 28.4, 29.4, 31.9 27.1, 27.6, 28.5, 31.0
~a = 21.9 .~raphite ), 29 14.1 np 37, 137
)raphite ~0 16 np 9
]raphitized C ~0 16.0 np
k~tapulgite n ~5-65 (16.7) 16.4 18
~arbon 20 18.5 ~H2CICH2C1 = 126
AhOa 25 28.2 177
8.7, 19.4, 19.7, 21.6,
; AhO~-ZnO 25 22.4, 22.7, 22.9, 27.2 77
9.8, 23.7, 24.4, 25.7,
26.4
g/gO ) 22.08 p ~rysta] struc- 79
ture of )~IgO
khOa l.s. 24.1 t56
3harcoal ~5 q
145
~iO~--A120a 1.s. 25 .04
~iO~ ~6 26.5 [76
]H~N ~ethylamine ~raphitized C ) 16.0 [02
1.d. 19.1
]~ChF~ ,2-Dichloro-1,1,2,2-tetrafluoroethane ?auj asite 148 (45.4) 17.7 ~r = 16.6 19
VdW 35 Mod. 14.8-26.0 ?auiasite ~03 (48.~) L9.2 ~r = 16.6 19
],F~ )erfluoroethane ?aujasite ~23 (36.5) ;0.4 ~r= 16.6 19
Mod. 13,7-21.1 ?auj asite ~53 (39.7) ;3.0 ~r = 16.6 19
],H, kcetylene 3arbon -78 (19.7) 2
VdW 18.5 Mod. 6.2-14.7 1.d. 18.7 (--78) ketivated charcoal -75 19.8 ~7
aa = 22.0 ,~lass -78 22.2 57
@O -80 26.50 r ~rystal struc- 79
ture of MgO
~H~Ch ,2-Dichloroethylene ~Iomoionic ~8.4 ~2.2) B u t a n e = 44 1
Mod. 12.4-28.6 l.d. 27.8 (25 °) ~aolinite
C2I-I~CI Chloroethylcne IIomoionic 0 (36.8) Butane ~ 44 91
Mod. 11.7-20.3 I.d. 24.9 (0°) Kaolinite
C~II4 Ethylene s --175 184
Y d W 20.1 Mod. 9.2-17.0 I.d. 20.6 (--140 °)
A c t i v a t e d charcoal --90 23.1 127
C2HdCI: 1,2-Dichloroethane 6 A120a 25 31.2, 35.2, 35.4, 36.0, 177
VdW 30.6 Mod. 22.3-24.1 1.d. 28.1 (25 °) 38.3, 39.6
ca = 35.4 4 AI~O~-ZnO 2 31.9, 32.6, 36.3, 37.9 177
C, HdO~ Acetic acid SiO: 38 19.58 N2 n.s. 175
V d W 30.5 Mod. 15.5-20.7 l.d. 22.9 (25 °) Graphitized C 20 20 N2 n.s. 98
Graphitized C 20 30 13
C2H6C1 Chloroethane G r a p h i t e , charcoal -78 23.2 139 C~
V d W 27.2 Mod. 14.1-16.6 1.d. 26.0 (0 °) Graphite 0 26.1 166
era = 30.1 Graphitized C --78 (27.3) n.s. 126 ©
Graphite 0 29.7 138
G r a p h i t e , charcoal 0 80 139
Graphitized C --25 (31.6) n.s. 126
136 C~
Graphitized C --78 32.6
Graphitized C 0 (33.3) n.s. 126
Graphitized C 25 (37.2) n.s. 126
Al20s 35 63ss N2 n.s. 186
C2Hd Io doethane Porous glass 75 (20) 74
Mod. 17.0-17.3 i,d. 28.2 (75) Iron 75 (26.6) 74
Glass spheres 75 (29) 74 70
C2H~ Ethane Q u a r t z beads --18 20.5 Microscope d a t a 39
V d W 21.7 Mod. 10.4-15.3 I.d. 22.7 (--88 °) Glass beads --183.5 20.5 Microscope d a t a 109
o~
era = 23.0 U Oxides -183.5 20.5 t Microscope d a t a 109
©
Glass tubes --186 2O.5 G e o m . area 5
UO2 --186 20,5 21.3 K r = 19.4 5
Graphitized C --125 to --60 (22.7 u) 29
NaCI, KC1 v' w,z --183 23 n.s. 150 o
F o l y (propylene) --86 23.5 22.9 16.6 66
TiO2--HJ anatase --183 24 HJ treatment-- 150 ©
see footnote 17
in Ref.
,Dr2
k Original authors used 16.9 A~,
n Outgassed a t 20°C.
P B y "preferred position" calculation,
q B a n g h a m ' s m e t h o d for surface area f r o m surface energy, 24.8 A~.
r B y "preferred position" calculation.
s F r o m density of solid b y X - r a y diffraction, 17.55 A z .
ss Area " a v a i l a b l e " to molecule.
t Only g a v e fair fit to microscope data.
u Original author used 21.5 As,
v On N a C l b y X ray, C~Hs vertical, 15.8 A2,
W A s in N o t e v b u t K C l , 19.7 A~. ¢Jl
x X - r a y diffraction, 20.5 AL
 TABLE 1--Continued ¢;"
o0

Area per molecule (A 2)

Formula Compound name No. Adsorbent T (°C.) Refer-
Status 1 Reference ¢ for ence
Adsorption Adsorption corrected
for Av adsorbed area

C~H~ Ethane-Continued (NH4)aPO4.12MoO~ --I00 24.6 69

Soils --78 (25.5F 128
Carbon --78 25.9 127
FuIler's earth --86 26.8 i npx [ 68
NaCI, KC1 a, ~ 150
C2H00 Ethanol 24 Glass 0 20 c 161
V d W 2 5 . 7 M o d . 12.8-18.8 1.d. 23.1 (25 °) Graphite 20 22 9
¢~ = 28.3 7 SiO2 25 22.0, 22.0, 27.5, 30.7, 86
30.8, 31.6, 35.3
8 AhOa 25 23.2, 23.6, 24.3, 25.9, 177 (3
30.0, 32.9, 34.4, 36.9
Attapulgite d !10-70 23.4 24.6 15.4 18
5 AhOa 25 24.3, 25.6, 26.8, 28.2, 20.2, 21.3, 22.3, 23.4, A r = 16.6 121 >
29.0 24.2
5 AhO~-ZnO 25 28.6, 32.7, 33.5, 34.7, 177 >
34.9
SiO2 26 31.1 176
3 SiO.~ 25 32.7, 37.6, 37.8 16.2, N20 = 20.4 t19
C~HsN2 1,2-Diaminoethane 25 AhOa, A h O ~ - Z n O 25 25.5, 29.0 177
Mod. 15.6-21.9
C~F~ Perfluoropropane 26 Fau] asite 343 (56.0) 46.5 A r = 16.6 19
Mod. 20.2-28.1 Faujasite 303 (58.3) 48.5 A r = 16.6 19
C~H6 Propene 27 Graphitized C --55 to --35 3O 32
SiO~ --55 to --35 39 28
C~H00 Acetone 28 Carbon 20 (16.7) CH~CICIt2C1 = 125 Q
28.2
VdW 31.4 Mod. 20.2-23.5 1.d. 27.5 (20 °) Gruphi~zed C 26 34 13
CaH~O~ Propionie acid 29 SiO2 38 25.01 N~ n.s. 175
VdW 32.4 Mod. 15.8-26.7 I.d. 27.4 (38 °)
CaHrCI Chloropropane 30 NiO, MgO 25 30.8 42.5 C~H0 = 31.2 160
VdW 31.6 Mod. 17.3-25.2 1.d. 31
C3H8 Propane 31 Graphitized C --55 to --35 32 32
VdW 27 Mod. 15.7-20.8 hd. 27.3 (--42 °) (NH4)~PO4.12MoO3 --64 35.5 69
ca = 36.4 Fu|ler's earth --45 35.8 68
A c t i v a t e d charcoal --39 36.0 127
AhOa 0 39 157
Carbon n.s. 4O 185
C3H80 1 Propanol 32 TiO~, SiO2 2O (21.o/ 111
VdW 30.8 Mod. 19.4-25.3 I.d. 27.2 (25 °) 6 AhO~ 25 25.0, 26.8, 27.0, 27.6, 177
~a = 32.8 36.0, 40.2
 TiO,~, rutile 25 26.6 84
3 Ge g 25 27-36 188
Fe2Oa 25 31h ~ J Method 114
SiO= 26 34.0 !76
TiOz, Fezes 25 37h H J Method 114
5 AI2Oz--ZnO 25 37.2, 37.5, 37.8, 38.3, 177
44.3
2-Propanol 33 8 A120a 25 30.6, 30.8, 31.7, 32.6, 177
VdW 29.9 Mod. 20.1-24.2 hd. 27.7 (25°) 40.5, 41.8, 42.7, 43.2
~a = 38.8
5 AhO~--ZnO 25 36.7, 42.3, 42.8, 44.0, 177
©
44.2
CaF~0 Perfluorobutane 34 Fauj asite 343 (62.2) 51.8 Ar = 16,6 19 0
VdW 41.5 Mod. 20.4-32.1 Fauj asite 303 (66.5) 55.3 Ar = 16.6 19
C4H40 l~uran 35 3 AlcOa 23 37, 38, 42 35.2, 39.3, 40 17 61
Mod. 14.4-27.0 1.d. 26.6 (20 °) C 23 42 40 17 6I
aa = 40.3 3 SiO2 23 45, 46, 46 43, 43.8, 43.8 17 61
C4It4S Thiophene Ni 25 33 n.s. 116
VdW 29.8 Mod. 18.1-30.7 l.d. 28.2 (25 °)
C4H~ Butadiene Carbon 0 32.9 26
C4H8 1-Butene SiO~--AhOa --78 (31.5) 118
VdW 30.7 Mod. 15.4-25.1 I.d. 30.5 (--6.3 °) Graphitized C 0 37.8 26
>
~a = 38.5 5 Carbons 0 37.8, 38.6, 38.7, 40.1, 26
N
40.6
Al.~Oa 0 42.7 52
cis-2-Butene 39 Carbon 0 38.5 26
trans-2-Butene 40 Carbon 0 33.4 26 ©
VdW 30.5i Mod. 17.6-27.8 1.d. 31.3 (20°) I{aolinite 0 40.0 37.4 Butane -- 44 91
C4HsO2 B u t y r i c acid 41 SiO2 38 31.35 N2 n.s. 175 N
VdW 33.5 Mod. 20.0-32.7 ].d. 31.6 (38 °) 0
C~I/gCI I -C]~lorobutane 42 G r a p h i tized C 20 43 N2 n.s. 98
Mod. 19,7-22.6 TiO2--rutile 25 46.2 84 0
C4H,0 Butane 43 ZnO 0 27.0 37.2 C6H6 = 31.2 160
VdW 32.0 Mod. 24.5-30.3 l.d, 32.3 NiO 0 30.5 42.0 CGII6 = 31.2 160
(--11.7 °) N
Carbon 0 32 58
~a = 44.8

z Original authors used 24.5 Ae.

a On NaCI by X ray, C2H6 flat, 29.5 A'<
b As i~l Note a b u t KC1, 31.7 A2.
c Methylene blue, 1 mg = 10,000 cm.2.
d Outgassed at 20°C.
/ Also checked b y X-ray method.
g n-Type, probably w i t h oxide fihn on surface.
h B E T method gave negative value of C, so value ill doubt.
i For a mixture of eis-trans isomers, l%ef. 83.
GO
 (~

TABLE 1--Continued

Area per molecule (A 2)

No. Adsorbent T , (°C.) Refer-
Formula Cornoo'dnd n alT~e ence
Adsorption Adsorption corrected Reference ~ for
adsorbed area

C4Hzo Butane--Continued A12Oa 0 (37.1)i 157

TiO~, SiP2 0 37.6 A r = 13.8 107
k ? 38 108
Carbon~ 0 38.6 A r = 13.8 106
Graphitized C 0 39.7 26
UO~ --117 (41) 42.5 K r = 19.4 5
Graphitized C 30, 42 (42) 149
4 Carbons 0 39.7, 41.4, 43.7, 45.1 26 Q
2 Zn 0 41, 52 58
Graphite 0 41.5 24
A c t i v a t e d charcoal 0 42.1 127
Metal, glass --78 43.4 52
(NH4)3PO4-12MoO~ --23 44.1 69
Carbon 0 45 24
Metal, glass 0 46.9 52
Fuller's earth 0 47.0 68
Carbon n.s. 47 185
4 AhO3 0 48, 50, 52, 52 45.8, 47.6, 49.4, 49.4 17 61
Porous glass 0 49 57
BaSO4 0 (51) 73 ~D
3 SiO~ 0 54, 55, 56 51.4, 52.4, 53.4 17 61
t~
Glass 0 (55.8)m 51 7:
TiP2 0 (57) 73
Charcoal 0 59 53.4 17 61
2-Methylpropane Charcoal --18 47.4 127
VdW 32.0 Mod. 24.5-30.3 I.d. 32.3 Charcoal 0 53 50.4 17 61
(-11.7 °) Carbon n.s. 51 185
~a = 50.7 4 Al~Oa 0 50, 51, 53, 57 47.6, 48.5, 49.4, 54.3 17 61
3 SiO~ 0 51, 56, 60 48.5, 53.3, 57 17 61
C4H100 1-Butanol 6 A12Oa 25 27.4, 27.5, 28.8, 29.2, 177
VdW 32.1 Mod. 17-33 I.d. 31.2 (25 °) 39.9, 41.2
aa = 35.4 Graphite 20 35.3 9
5 A12Oa--ZnO 25 36.5, 38.4, 39.3, 40.7, 177
41.0
2-Butanol 6 AI~O~ 25 31.7, 33.2, 35.8, 36.5, 177
VdW 20 Mod. 17.6-30 1.d. 31.3 (25 °) 42.2, 47.6
aa = 39.4 AhO~--ZnO 25 48.8 177
 2-Methyl-l-propanol 47 6 AI~O~ 25 30.6, 30.8, 31.7, 32.6, 177
V d W 31.9 Mod. 22.2-27.3 43.1, 46.8
Ca = 40.1 4 AhO~-ZnO 25 44.0, 44.5, 45.0, 51.8 177
2-Methyl-2-propanol 48 4 AllO3 25 36.2, 36.5, 36.7, 39.2 177
V d W 33.7 Mod. 22.6-30.2 AhO~-ZnO 25 48.8 177
Ca = 39.5
C4H~00 E t h y l ether 49 Carbon 20 42
¥ d W 35.8 Mod. 19-31.5 I.d. 33.8 (20 °)
C4HuN Diethylamine 50 SiO~ 25 (43.2) 20
V d W 36.1 Mod. 26.8-31 I.d. 34.2 (25 °)
n-Butylamine 51 SiO2 25 (32.5) 20
Mod. 20-32 1.d. 30.9 (25 °)
C~H~N Pyridine 52 Graphite 20 39 11
(5
Mod. 39 44 Gra!ohitized C 20 38.2 102 ~V
C~H~0 Graphitized C 20 38.5 8 ©
Cyelopentane 53
V d W 32.1 Mnd. 24.5-26.2 i.d. 49.5 (0 °) SiO2 20 42 C6H0 = 40 99 O3
3 Al~O~ 46-49 A r = 16.6 121 5~
Carbon 0 47 24
C~
1-Methyl-2-butene A120~-Cr20~ 20-150 57 152 ~q
VdW 36.5 Mod. 22-31
2-Methyl-2-butene Carbon 0 46.7 26
Cr20,--AI~O~-K~O 20 57 A r n.s. 152
1-Pentene TiO~--anatase 20 49.3 46
Mod. 18.4-34 I.d. 34.9 (20 °)
2-]Pentane n Carbon 0 47.8 26
C~H~002 M e t h y l isobutyrate Carbon 20 37.7 CH2CICH2C1 125
V d W 40 Mod. 28.6-34 i.d. 37.0 (20 °) = 28.2 o~
CsH~2 Pentane Al2Os n.s. 33.2 156
©
V d W 37 Mod. 22.5-34 1.d. 36.2 (20 °) Carbon 10 37,1 54
aa = 49.2 8 A1203 25 38.2, 41.5, 42.5, 46.5, 177
49.0, 54.5, 60.6, 63.6 ©
7-A1:O3 20 45 H e x a n e = 51.5 15
Graphitized C 2O 45. O np 7
Graphitized C 20 45 np 102 C~
Silver 2O 46, 54 np 74
Graphite n.s. 46 np 167
4 Al~O3 25 46, 46.6, 49, 54.2 38, 88.5, 40.5, 44.8 A r = 16.6 121
5 A120.w-ZnO 25 51.5, 52.1, 56.7, 57.1, 177
69.3
TiO~--anatase 20 52.3 46
Carbon 0 53 24
(NII4)3PO4 • 12MoOs 0 53.3 69
Porous glass 20 (56) 74
Glass spheres 20 (64) np 74

] Original a u t h o r gives 39AL

k MgO, ZnO, CdO, SiOe, Cr20~, Mg, a n d Zn.
m Original author used 32 A~. Go
n Mixed sis a n d trans isomers.
 OO
FABLE 1--Continued o~

krea per molecule (A2)

'ormula :ompound name ~o. kdsorbent ", (°C.) ~efer
~ce
kdsorption ~dsorption corrected Leference ~ for
ldsorbed area

L2-Dimethylpropane (neopentane) 6O ~3raphitized C -46 to 20 1 12

VdW 36.5 Mod. 28-29 3arbon 7 24
3~rbon us. 2 85
-Methylbutane ,1 khOa--Cr2Os--K~O 0-150 6 kr~ ? 52
VdW 37 Mod. 26-34 I.d. 35.1 (--12 °)
)~IInO -Pentanol 2 ' AhOa 5 :7.6, 30.8, 32.8, 33.2, 77
Mod. 19-36 40.0, 44.6, 46.0
~a = 38.8 i AhOa--ZnO 5 ~7.8, 40.8, 41.8, 44.0, 77
45.6 7~
~6H~ ~enzene 13 ~iO~ 5.6 (22.2) .-4
45
VdW 32.5 Mod. 16-34 I.d. 32 (80 °) ~iO2 38 29.13 75
o'a = 43.6 i AlzO8 ,~O 35 1.4 kr = 15.4 51 -4
~IgO a.s. 36 16.2 nn 88
3iO~ ,~0 36 55
M~O~-boehmite ]5 37 9.1 IeO = 10.6 34
31ass spheres 75 (38) 74
~raphitized C ,~0 4O 87
2waphitized C 40.3 6
~iO2 a.s. (411 63
3raphite 3.5 41 67
.~raphitized C ~0 44 ~ n.s. 98
Darbon ~0 44. O x~
6
~arboll, noIlporous a.s. 44.5 41
]old 18 45 ILS. 58
:ton 75 46 lp 74
]arbon 1? 46.5 93
3raphitized C ,~1 48.3 lp 30
2r~Os--AhO~-K20 ~0 50 Ar = ? 53
Carbon, porous a.s. ;9, 58, 59 ¢ 41
3i0~ ~6 51.8 76
~iO~ ,~0 52.7 55
?orous glass 75 (57) 74
3aS04 ~0 61p,69pp 27
~yelohexane ,4 _3raphite L5 38 67
V d W 3 6 . 7 M o d . 29.4-35 I.d. 36.3 ~5 °) AltOs 19, 44.5, 45, 54.5 ',1, 35.4, 35.8, 43.4 A r = 16.6 21
qa = 4 1 . 7 ~iO2 41 43.3 H~O = 10.6 34
~.hO~ 42.6 35.5 A r = 16.6 21
~iO= 44 46.5 I-I20 = 10.6 34
~iO~ ,~0 45 48.3. Cell6 = 40 99
 Carbon 20 48 N2 n , s . 98
Cr203--AhOa--K20 20 53 Ar = ? 155
SiO2 26 76.8 176
2 SiO2 20 115, 136 55
Methyleyc]opentane 6~ SiO2 20 45 48.3 C6II~ = 40 99
C~H:4 Grap}fitized C 20 46 8
n-Hexane 6C 5 A120~ 20 41, 4l, 42, 47, 48 35.2, 35.2, 36, 40.3, 41.2 Ar ~ I5.4 151
VdW 42 Mod. 19-38 i.d. 41.3 (25 °) 7 Si02 25 48.8, 49.8, 51.9, 64.8, 47.4, 48.4, 49.5, 53.2, Kr = 20.8 59
~a = 56.2 70.6, 71.4, 76.2 68.6, 69.1, 74.0
Graphitized C 2o 51 87
MgO n.s. 51 16.2 q 88 O
Carbon n.s. 51.5 151
Graphitized C 2O 51.5 7 ©
Carbon 0 57.7 136
Oxides, metals, sulfides O 58.9 H J method 113 5~
(NtI4),PO4.12MoO~ 25 60.6 69
C~
Quartz n.s. 72 151
BaSO~ 20 (72qq ) 27
SiO~ 26 80.6 176
BaSO4 2O (8V) 27 >-
2,2-Dimethylbutane 67 Graphitized C 20 46.0 8
T-AhO3 20 46rr IIexane = 51.5 15
2-Methylpentane T-AhO3 20 48.5 tIexane = 51.5 15
C6H140 Propyl ether MgO 25 45.3 62.4 C6tt~ = 31.2 160
Mod. 40.2 l.d. 40.2
C~H~sN Triethylamine SiO2 320 43 103
©
VdW 43.2 Mod. 33-43 ].d. 41.7 (25 °)
C7F14 Perfluoromethylcyclohexane Faujasite 343 (76.4) 63.6 Ar = 16.6 19
VdW 48 Mod. 37-48 Faujasite 303 (83.7) 69.5 Ar = 16.6 19 ©
CTH8 Toluene ZnO 25 34.4 47.4 C6H6 = 31.2 160
¥ d W 38.5 Mod. 18-39 1.d. 34.4 (25 °) NiO, MgO 25 35.3 48.6 C6It~ = 31.2 160
Ca = 55.2 SiO2 20 46 49.4 C,H~ = 40 1OO if5
Graphitized C 20 46 8
Glass spheres 75 (46) 74
MoS2 26 50.2 67.2 C6H6 = 32.3 16
Iron 75 (59. 62) 74
SiO~ 26 58.2 176
Porous glass 75 (6i, 62) 74

nn Suggests 17.7 A: better for N2 on ionic MgO.

P Nonradioactive.
PP Radioactive.
q Suggests 17.7 A 2 is better on ionic MgO.
q q Radioactive.
r Nonradioactive.
r r Area with this z is low; requires 76 A~ to equal area from hexane.
Oo
 TABLE 1--Continued w,

Area per molecule (A2)

Adsorbent T, (°C.) Refer-
Formula Compound name
Status Reference ~ for ence
Adsorption Adsorption corrected
for A v adsorbed area

n-Heptane 73 SiO~ 38 29.2 x 175

VdW 47 Mod. 21-44 1.d. 42.7 (25 °) MgO 25 39.0 53.6 C6H16 = 31.2 160
qa = 63.1 ZnO 25 43.5 59.8 C6H~ = 31.2 160
5 SiO:, AhOz 25 46, 48, 48, 48, 56 54, 57, 57, 57, 66 H 2 0 = 10.6 134
MoS~ 26 49.0 65.2 CGH6 = 32.3 16
NiO 25 50.1 69.0 C61-1~ = 31.2 160
TiOe, SiO2 24 55 57.8 15.4 111
Graphitized C 20 57.3 7
SiO2 25 (58) 73
Fe2Oz 16.5 63.2 47, 48
C~
TiO2 25 (64) 73
Fe203 16.5 63.2 47, 48
Oxides, sulfides 25 64 HJ method 113
Fe~O3 23.1 65.7 47, 48
(NH4)3PO4.12 MoO~ 25 67.8 69
Fe208 29.5 69.2 47, 48
BaSO4 25 (72) 73
SiO2 26 83.6 176
2,2-Dimethy]pentane SiO2 65.6 (36) 45
V d W 45.2 Mud. 33-44 I.d. 43.1 (25 °)
3-Methylhexane Graphitized C 20 54.0 8
C~F~ Perfluoro dimethylcyelohexane Faujaslte 343 (83.9) 70.0 Ar = 16.6 19
Mod. 36-54 Faujasite 303 (92.6) 67.6 Ar = 16.6 19
CsH~0 Ethylbenzene SiO2 20 51 54.7 C6]:/~ = 40 i00
m-Xylene SiO2 20 52 55.8 C6H6 = 40 100
©
p-Xylene SiO2 20 5O 53.8 C~H~ = 40 10O
n-Octane MgO n.$. 58 88
V d W 50.8 Mod. 14-51 i.d. 46.6 (25 °) SiO~ 20 6O 64.4 C~H~ = 40 99
~a = 64.6 Graphitized C 20 61.0 7
(NH4)~PO4.12~¢ioO~ 29 75.0 69
2,2,4-Trimethylpcntane SiO2 20 54 58.0 C6H~ = 40 1O0
Graphitized C 20 54.5 8
CsH~gN Di-n-butylamine SiO2 25 (54.4) 20
Mod. 30-53 1.d. 47.2 (25 °)
Propylbenzene SiO2 20 57 61.2 C6][I6 = 40 100
¥ d W 47.8 Mod. 19-51 1.d. 41 (20 °)
Isopropylbonzene SiO2 20 58 62.3 C6H6 = 40 100
VdW 47.8 Mod. 19-51 l.d. 41.2 (20 °)
1,3,5-Trimethylbenzene SiO2 20 57 61.2 C6H~ = 40 100
Graphitized C 20 78 N~ n.s. 98
C~H~o n-Nonane (NH4)zPO4-12!VioO3 26.3 84.4 69
V d W 50.9 ~¢Iod. 22-55 1.d. 48.8 (26 °)
C~0Hls 2,6-Dimethyl-2,6-oc~adiene Carbon 100 80-84 159
Mod. 34-56 1.d. 48.4 (21 °)
C1017[ 22 n-Decane Carbon ~ IO0 86 159
VdW 61.0 Mod. 17-61 I.d. 53.5 (80°) Carbon ~s IO0 96 159
CO Carbon monoxide Ge --196 (10) Geom. area 110
VdW 15.6 Mod. 7-10 1,d. 16.8 Ni0 --195 (11.9) 12.5 15.4 172
~a = 15.0 N i (0H)2 --195 (12.9) 13.6 15.4 172
TiO~-anatase --195 14.73 H J method 135
CdO --195 16.2 80
TiO2-anatase --183 16.23 I I J method 135 O
CsI --I80 to --194 16.8 16.0 17.0 174 ©
CdO --183 16.9 16.0 17.1 80
Graphite --78 (20/ 178 O2
CO2 Carbon dioxide 3 NaCI 35 11.7, 15.4, 17.o 14.4, 19, 20.9 np, C~H~ = 85 180
No. lx C~
VdW 16.4 Mod. 5-11 l.d. 17.0 Many solids --78 14.i x n,s. 44
era = 21.8 Graphitized C --80 14.2 npx 25
Cellulose, poly (vinyli- --78 (19) 123
done chloride)
Attapulgite tt n.s. 19.5 20.5 N2 = 15.4 18
Glass --78 20.1 np 57
TiO2, SiO: --78 20.4 21.6 Ar = 13.8 107
Carbon --78 20.5 n.s. 145
Carbon --78 20.8 22.0 Ar = 13.8 106
MgO --77 22.08 u Crystal strue- 179 ©
ture of MgO
TiO2--anatase --78 25.39 np H J method 135
Carbon --79 24.4 168 ©
A t t a p u l g i t euu n.s. (25.5) 26.8 Nu = 15.4 18
CS2 Carbon disulfide Zn 0 23 58
VdW 23.5 Mod. 7-17 l.d. 22.4 (0°) Glass spheres 20 (59) 74
Porous glass 20 (72) 74
CIF3 Chlorine trifluoride NiF~ 28.2 22 N~ n.s. 60
Mod. 13-19
H2 I~Iydrogen Graphitized C -183 to -- 135 12.1 12.3 Ar = 13.6 129
P t film 16.9 18.4 K r = 18.5 35

s Devolatized.
ss Not volatized.
t Original author used 17.0 Ae.
tt Outgassed at 20°C.
u B y "preferred position" calculation,
uu Outgassed a t 360°C.
 TABLE 1--Continued ¢~
to
Area per molecule (A2)
Formula Compound name ~o. Adsorbent T, (°C.) Refer-
Adsorption Adsorption corrected Status Reference ~ for ence
for A v adsorbed area

H20 Water 94 5 I1Htes 6.2, 7.9, 8.0, 8.0, 9.2 vv H J method 131
VdW 13 Mod. 6-8 l.d. 10.5 (25 °) va]ue
~a = 12.5 Charcoal 25 (7.9) v N2 n.s. 144
(NHd)sPOd.12MoO3 25 (3.6) 69
13 Kalinites 20 12.6 vv 95
5Montmorillonites 25 9.8, 11.3, 11.5, 12.6, HJ method 130
14.8vv value
AgI --20 10 16 33
A t t a p u l g i t ew 50 (10.3) 10.8 N~ = 15.4 18
Graphitized C 19 10.5 np 10 ¢5
Graphitized C 30 10.6 np 102
Fe2Oax 25 10.8 78
7 SiO2 25 10.8, 1t.0, 11.9, 12.2, 10.5, 10.7, 11.6, 11.8, np K r = 20.8 59
12.5, 16.8, 20.4 y 12.1, 16.3, 19.8
SiO2 25 (11.1)v N2 = n.s. 144
Annealed SiO2 I5, 25 11.73 11.4 Kr = 20.8 70
Ge 25 11.8 np Ar n.s. 169
10 SiO~ 12 13.0, 13.4, 13.5, 13.7, N2 n.s. 120
14.9, 15.1, 15.5, 15.8,
>
18.1, 18.7
U n a n n e a l e d SiO2 15.25 13.73 13.3 X r = 20.8 70
CaCOa 15, 25 14.3 13.9 K r = 20.8 70
TiO2--rutile 25 15.1 16.27 84
Au 18 17 np n.s. 158
Glass 26.5 19.5 np 57
2 SiO2 20 24, 31 x 55
SiO2 26 P~
24.6 x 176
H2S tIydrogen sulfide 95 GIass spheres --79 (21 ) 74
VdW 16.5 Mod. 8-10
Iodine 96 BaCI~ n~s. 22.1 np n.s. 53
M o d . 10-17 Graphitized C 20 23.7 np Ns n.s. 98
MgO 25 35.3 Crystal struc- 179
ture of MgO
Carbon 25? 40 N~ n.s. 124
Kr Krypton 97 Graphitized C --183 14.5 x 102
VdW 15.6 Mod. 11.2 NiO ( + 0.16 H20) --195 (15.3) 16.1 15.4 172
o- = 20.2 NaBr --207 to --190 17.1 np 63
SiO2 --196 (18.5) 163
N i (O t t ) --195 (19.1) 20.1 15.4 172
G e (oxidized) --195 19.4 ± 0.2 20.4 np 15.4 147
 Poly (ethylene) --196 19.5 81
Poly (ethylene), n y l o n --196 19.5 187
Quartz --196 19.5 163
Tridymite --196 19.5 17.0 (at --183 °) 181
19.5 :t: i z 65
TiC2 --anatase --195 19.5 :t: 0.4 22
SiO~ --195 19.5 89
a
--195 20.8 52
Carbon, charcoal --78 21.0 Ar = 13.8 97
UO2, UO2 partly fluori- --195 (21)b 173
ded
Zr --183, --196 21.5 72
Q
Glass --195 21.5 22
Glass --205 21.6 N2 n , s . 163 O
Ti02--anatase --183, --195 21.78 H.J m e t h o d 22
CaCO~ --184 22.4 21.4 17 76, 75 b~
SiC2 --195 22.5 101
SiO~ --196 23.6 75 ©
SIO~ --184 24.2 21.3 17.0 75
NH3 Ammonia 98 Graphitized C --78 11.4 102
VdW 15.0 Mod. 7-10 1.d. 12.9 5 SiC2cc --34 9.5, 13.6, 14.1, 15, 16.5 21
~a ~ 14.0 Attapulgite 100 12.6 13.2 15.4 18
Charcoal --78 14.8 v 145
Charcoal --38 14.9 c 145 ~v
Glass --32.5 15.4 57
Gruphitized C --78 16.0 25
N~ Nitrogen TIC.2, SiC2 --196 12.9 Ar = 13.8 107
VdW 15.3 Mod. 7-10 I.d. 16.2 (--196 °) 3 A1203 --195 ©
15~1 12.5 Ar = 16.6 121
See note ~ 4 AhO~ --195 15-17.2 12.5-13.3 Ar = 16.6 121
~N: = 16.2 taken as s t a n d a r d in this NaC1 --195 15.9 19.2 CsHs = 35 180
work TiO2--anatase --195 16.27 HJ method 135 0
TiC2 anatase --195 17.72 HJ method 135
NeO Nitrous oxide 100 SiC2 n.s. (19.3) 163 C~
YdW I6.9 Mod. 7-13 I.d. 16.8 SiC2 --78.5 20.4 162
N20~ Nitric oxide dimcr 101 Carbon --154 31.4 N2 n.s. 165
N204 Nitrogen tetroxide 102 TiC2 --15 to 50 23.7 N2 n.s. 146

v Original author gave 10.5 A2.

v v Area varies with cation present, value g i v e n is average of 18 determined.

" Outgassed at 20°C.

x Sample m u s t be heated above 450°C.
Y Depends on surface-free energy.
z Value t h a t gives reasonable agreement for area of m a n y widely different substances.
Glass, W, ZnO, and A120~.
b Original author used 19.4 A t
c B a n g h a m ' s method of surface energy.
cc Calcined at 400°C.; other values at 200°C, and 800°C. ¢.5(
d Harkins and Jura (73) plotted isotherms for N~ on 86 solids. The histogram for ~ peaked at 14.05, 15.25, a n d 16.05 A2
 TABLE 1--Continued

Area per molecule (AS)

Formula Compound name Adsorbent T, (°C.) Refer-

ence
Adsorption Adsorption corrected Status Reference ¢r for
for Av. adsorbed aiea

Ne Neon Carbon --256 10.0 133

O2 Oxygen TiO~, SiOs, C --183 13.5 Ar = 13.8 106, 107
VdW13.5Mod. 6-9 I.d. 14.1 Attapu]gite e --194 (13.6) 14.3 15.4 18
~a = 13.6 CdO --195 13.7 80
TiO~--rutile --t95 13.8 85
KCI --185 14.0 16.3-17.1 94
CsI --200 14.1 13.4 17.0 174
CdO --183 14.1 13.4 17.1 80 C5
Me --183, --195 14.6 15.3 15.4 79
Charcoal --185 15.9 / 145
TiO~--anatase --195 17.5 4
C e m e n t paste --183 (17.6) c 34
>
A1 foil --196 20.3 36
SF~ Sulfur hexafluoride Graphitized C --76 to 82 23 25
¥ d W 26.7 Mod. 20.8 Fauiaaite 223 (32.8) 27.3 A r = 16.6 19
Faujasite 253 (34.8) 29.0 Ar = 16.6 19
SO2 Sulfur dioxide Graphitized C 0 13.8 102
VdW 20.0 Mod. 13-16 Graphitized C 0 19.4 23
Charcoal 0 27.1 g 145
7:
Xe Xenon AgI --124.6 18.1 np 164
VdW 18.5 Mod. 13.7 l.d. 18.6 (--109 °) N i film --195 19.3 18.6 np K r = 21 142
a = 23.2 N i film --183 19.5 np h 1
Graptfi tized C --124.6 19.9 np 164 ~V
N i film --183 21.8 21.0 np K r = 21 142
W film --183 23.0 np h 1
Ni, glass --195 23.6, 25.9 24.4, 26.8 np K r = 19.5 43 7:
Cu --183 24 25 np K r = 19-20 143
I n a c t i v e glass --195 24 24.9 np K r = 19.5 148
Zr --183, --195 24.1 np 72
TiOs --124.6 27.3 164
Charcoal 0 (28.2/ x A r = 13.8 97
Active glass --195 28.5 29.5 np K r = 19.5 148
Carbon 0 (32.4) I x Ar = 13.8 97

e Outgassed at 20°C.
] Bangham's surface energy method.
c Original author used 14.1 Ae.
g Bangham's surface energy method.
h From lattice dimensions of metal.
i Original author used 24.9 A2 and said low area was due to sieving.
 CROSS-SECTIONAL AREAS OF MOLECULES 595

TABLE II
RECOMMENDED MOLECULAR AREAS
[4- Values are 95% confidence interval (twice standard deviation)]
Area per molecule (A2)
Adsorbent Temp. (°C.) Comment
All exptl, values a Nonporous only Liquid density Recom-b
mended

Ar -195, -183 14.7 4- 4.1 14.1 ± 4.4 13.8 13.8 14.1 :t= 3.0 for
-183°C. values
Kr -196 20.3 4- 3.3 20.2 4. 2.6 -- 20.2
Xe -184 23.2 -4- 6.7 23.2 -4- 6.7 18.6 --
( - 109oc.)
I:I20 25 12.5 i 6.5 - - 10.5 12.5
Methanol 20-25 21.9 4- 9.0 -- 18 --
Ethanol 25 28.3 4- 11.2 -- 23.1 --
n-Butane 0 44.8 4. 9.8 44.4 4. 8.1 32.3 44.4
Benzene 20 43.6 4- 9.8 43.0 4. 6.0 32 43.0
~ Except those marked "x" in column 8.
b Used in compilation.

teristie. Figure 3 displays two such trends. CONCLUSIONS

Line I shows the direct relation between
liquid density and adsorption values of
¢ for 12 more or less spherical molecules.
As indicated on the figure, these include
inert gases, halogenated methane, acetone,
methanol, several hydrocarbons, and NHa.
Such a figure gives fairly direct evidence t h a t
the assumption of close-packing is not met in
the adsorption layer. If it were, we would
expect better agreement with the perfect
correlation line shown.
Line I I in Fig. 3 presents a similar plot
for paraffinic hydrocarbons and shows ¢ to
v a r y in a fairly regular manner, although
the cross-section value in the adsorbed layer
is larger t h a n t h a t calculated from the
density.
70 I t I l
~ < 60
-
1) The "size" of the adsorbed molecule
is not constant but varies with the adsor-
bent, temperature of adsorption, and choice
of reference substance.
2) Recommended values for molecular
cross-sections as reported are: N2 ( - 1 9 5 ° C . )
16.2 A 2, Ar ( - 1 9 5 ° C . , - 1 8 3 ° C . ) 13.8 A ~,
K r ( - 1 9 5 ° C . ) 20.2 A ~, benzene (20°C.)
43.0 A 2, and n-butane (0°C.) 44.4 A 2.
3) Of the four ways of estimating mole-
cular area discussed, two (based on liquid
density and v a n der Waals' constants) gen-
erally correlate well. Both these calculations
and t h a t based on molecular models tend
to give lower values t h a n the absorption
method.
4) A correlation line (Fig. 1) of molecular
1 1 I l I
area from liquid density with t h a t from ad-
SPHERICAL
sorption provides a w a y to allow partially
MOLECULES
~LINE I C~o for the variations resulting from the choice

z~$0 PERFECT COR RELATIO of standard substance as well as errors in the

assumptions made about molecular shape
and packing in liquids.
5) Within a homologous series (paraffins),
ACETONE° i
~ 2 H c4 C l z CaH4Clz good correlation is shown up to 8 carbon
,~20
co
~ oxe
°~CH o
atoms.
---JlO Ar CH4 4

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