Classified abstracts 14---26
16 : 19 parameter, are compared with experimental measurements of the
13. The study of physical adsorption by infra-red spectroscopy.
(France)
As a result of physical adsorption, both adsorbant and adsorbed
molecules suffer perturbations which are revealed in their corres-
ponding infra-red spectra. The detailed study of these spectra gives
information on the nature of the binding forces and adsorption
centres. Full interpretation of the results is however limited at
present to a few special cases. Thus the spectra of adsorbants of the
SiO2 class show the presence of (OH) groups on their surfaces even
after most thorough heating. In this case, physical adsorption is
accompanied by the formation of hydrogen bonds between the
hydroxyl groups. (France)
A Savary and S Robin, JPhys, 25 (6), June 1964, 119-124.
16
14. Nuclear magnetic resonance studies of adsorption on thorium
oxide. (USA)
W S Brey Jr and K D Lawson, J Phys Chem, 68, June 1964, 1474-
1481.
16
15. Interaction of ethane and ethylene with clean iridium surfaces.
( USA )
R W Roberts, JPhys Chem, 68, Sept 1964, 2718-2722.
16
16. An approach to a theory of monolayer permeation by gases.
( USA )
M Blank, JPhys Chem, 68, Oct 1964, 2793-2800.
16
17. The critical surface tension of glass. (USA)
D A Olsen and A J Osteraas, J Phys Chem, 68, Sept 1964, 2730-
2732.
16
18. Molecule-wall collisions in porous media at low gas pressure.
(USA)
It is shown by applying the cosine law of molecular reflection
derived by Knudsen that the expected number of wall collisions
experienced by a gaseous molecule chemically produced within a
double open-ended pore at low pressure is given approximately for
a zero-order reaction by 1/6(L/r) 2, where L is the length of the pore
and r the radius. Corresponding results for partially utilized pores,
pores closed at one end, and for first-order surface reactions in
pores open at both ends are (f(3--f)/12)(L/r) 2, (2/3)(L/r) 2, and
(1/2) • (L/r)2(h cosh ( h ) - s i n h (h))/h 2 sinh (h), respectively, where f
is the fraction of the pore utilized, h is the dimensionless quantity
L~/k2/rd, k is the intrinsic first-order surface reaction rate con-
stant, and D is the gaseous diffusion constant within the pores.
(Author)
W S Horton, JPhys Chem, 68, Aug 1964, 2278-2281.
16
19. Areas of uniform graphic surfaces. (USA)
The previous suggestion that conventional nitrogen areas of uni-
form surface graphites are too low is confirmed. Area measure-
ments by benzene, n-hexane, and ethyl chloride agree with nitrogen
areas if the cross section is taken as 20/~ 2 instead of 16.2A ~. A
proposed explanation is that nitrogen molecules are localized at
graphite lattice sites, so that each one fills four of the unit hexagons,
an area of 21~k2. Isotherms of similar size molecules, oxygen and
carbon monoxide, are in agreement with this model. General limi-
tations of surface area measurements by gas adsorption are dis-
cussed. (Author)
C Pieree and B Ewing, JPhys Chem, 68, Sept I964, 2562-2568.
16
20. Electric monopole and dipole discreteness effects in adsorption.
(USA)
Various consequences of element discreteness upon the electrical
characteristics of adsorbed systems of monopoles and dipoles are
discussed and methods for determining exact local potentials and
fields in such systems are outlined in terms suitably general for
wide application. (Author)
J R MaeDonald and C A Barlow Jr, J Phys Chem, 68, Oct 1964,
2737-2740.
16
21. Rates of surface migration of physically adsorbed gases. (USA)
A molecular model of the surface transport rate process is used to
develop quantitative rate equations; these, containing one arbitrary
49
surface migration rates of propane, butane, propylene, perfluoro-
propane, and dibromodifluoromethane over a wide range of pres-
sures and a moderate range of temperatures on one solid surface, an
alumina catalyst support. The agreement between the experimental
results and the theoretical equations developed in this study shows
an order-of-magnitude improvement over the prior art. As such,
the results of this study support the theoretical model used. Further
work, directed toward an understanding of the remaining para-
meter, would clearly be desirable in order to move more closely
toward entirely a priori predictions of the transport rates or mobi-
lities of adsorbed molecules. (Authors)
R K Smith and A B Metzner, JPhys Chem, 68, Oct 1964, 2741-2747.
16
22. Physical adsorption on low energy solids. II. Adsorption of
nitrogen, argon, carbon tetrafluoride, and ethane on polypropolyene.
( USA )
Nitrogen and argon are adsorbed on a solid hydrocarbon surface
(polypropylene) as two-dimensional gases, nitrogen failing to
show the supermobility previously observed on polytetrafluoro-
ethylene (teflon). Carbon tetrafluoride and ethane are adsorbed
with some restriction of mobility, possibly due to their greater
energies of self-interaction, the entropy changes in adsorption being
intermediate between those associated with localization and with
free mobility in two dimensions. Film pressures at a coverage repre-
senting one statistical monolayer are 12 to 14 rgse/cm 2 for nitrogen,
argon, and ethane, but only 9 ergs/cm ~ for carbon tetrafluoride,
reflecting its appreciably lower free energy of adsorption. (Author)
D Graham, JPhys Chem, 68, Oct 1964, 2788-2792.
16
23. Molecular orbitalview ofehemisorbed carbon monoxide. (USA)
Carbon monoxide chemisorbed on metals is considered in the light
of Htickel molecular orbitals for the metal-carbon-oxygen bonds.
The Hiickel molecular orbitals predict the existence of a partially
filled 7r-molecular orbital which increases the metal-carbon bond
strength but decreases the carbon-oxygen bond strength. In this
model only effects in the ~-bonding system are considered; i.e.,
the o-bonds are assumed constant. This model qualitatively ex-
plains: (1) the occurrence of several carbon-oxygen stretching fre-
quencies in the infrared spectra of CO adsorbed on metals; (2)
differences in spectra of CO adsorbed on evaporated and supported
metals; (3) infrared band positions as a function of coverage; (4)
the effect of adsorbing other gases in addition to previously chemi-
sorbed CO; and (5) band shifts in going from adsorption on pure
Ni to a Ni-Cu alloy. (Author)
G Blyholder, JPhys Chem, 68, Oct 1964, 2772-2778.
16
24. The reaction of hydrogen with cerium metal at 25 °. (USA)
The rate of absorption of hydrogen by plates of cerium metal was
studied at 25.0 ° and pressures from 100 to 600 ram. For a given
constant pressure, the plot of hydrogen absorbed as a function of
time was sigmoidal. Corresponding to the different segments of the
absorption curves were the four reaction stages: (1) induction stage,
(2) autoacceleration stage, (3) linear stage, and (4) deceleration
stage. The reaction rate was found to be sensitive to gaseous im-
purities and to the thermal pretreatment of the metal samples. For
the linear stage of the reaction, the pressure dependence of the rate
could be described with reasonably accuracy by the equation r --
kip + k2, where r is the rate in ml (STP)/cm 2 of original surface,
kl = 5.0 × 10 4 ml/cm 2 ram-l, and ks varies from sample to
sample. Some aspects of the reaction are discussed. (Authors)
K H Gayer and W G Bos, J Phys Chem, 68, Sept 1964, 2569-2574.
16
25. The adsorption of oxygen on silver. (USA)
The rate of adsorption and desorption of oxygen on silver powder
has been measured from 77 to 351 ° at an oxygen pressure of 10
torr employing a vacuum ultramicrobalance. The measurements
were made on a silver surface on which both the total uptake and
the rate of adsorption were reproducible at any temperature and
pressure. Nominal activation energies of 3, 8, and 22 kcal/mole
which were measured are believed to correspond to dissociative
adsorption, molecular adsorption, and surface mobility of oyxgen
adatoms, respectively. Data on thermodesorption, vacuum desorp-
tion, and activation energy are combined to propose relative surface
coverages of the various adsorption types. (Author)
A W Czanderna, JPhys Chem, 68, Oct 1964, 2765-2772.