The number of hands increases with the surface concentration of chemisorbed CO,

whiCh is attributed to the surface heterogeneity of the solid Pd; each band results from
a separate homotattic patch, identified with each of the major crystal faces of the
adsorbent. The infrared spectra can also distinguish two or more simultaneously
occurring but different types of chemisorbed bond between the adsorbate and various
parts of the surface. Both quantitative and qualitative differences in the nature of
chemisorbed bonds can therefore be traced to structural differences in the lattice of
the substrate.
Investigation of the catalytic activity of different faces of a crystal have been
cited as evidence for the influence of lattice geometry on heterogeneous catalys is.
Such interpretations must, however, be accepted with reservations. The rates of
reaction between ethylene and hydrogen on evaporated films of the transition metals,
as determined by Beeck and his associates (26), can be correlated with eith( I; the lattice
spacing of the surface planes or with the percent d-electron character or the metal
bond. Rhodium, with a spacing of 3.75 A, has the greatest activity and .1so has the
highest percent d-electron character. The question then arises if the by :.rogenati on
of ethylene proceeds most readily on a rhodium substrate because of ti -R, favorable
geometry provided by the 3.75 A spacing or because of the high heat of adsorption
resulting from the high d-electron character of the metal bond. To select the geo-
metrical factor only as determining the forces at the surface of a solid is an over -
simplification, although unquestionably large net differences exist between the action
of one crystal face and another (27).
Adsorption from Solution by Solids
The adsorption of a solute, from its solution, by a solid surface is a phenomenon
considerably more complex than that of the adsorption of a gas Or vapor by a solid
surface; the number of components in the adsorption system is now increased by one,
so that we have at least a three-component system, and our knowledge of the liquid
state is notoriously more limited than our knowledge of gases. As a first approxima -
tion, however, we can think of the phenomenon as a distribution of the f;olute, now
known as the adsorptive, between the liquid solvent and the solid surface, both of
which are competing for it. ,
Solid :adsorbents are roughly classed as polar or nonpolar. On polar st :aces ion-
dipole or dipole-dipole interactions with the adsorptive are more prom i :lent than
interactions due to dispersion forces; on nonpolar surfaces, the latter pr dominate.
Examples of polar adsorbents are alumina, barium sulfate, calcium carbonate, glass,
ion-exchange resins, quartz, silica gel, titanium dioxide and most metallic oxides, and
zeolites; examples, of nonpolar adsorbents are carbon blacks, charcoals, graphite,
organic resins and plastics, paraffin, stibnite and most metallic sulfides, and talc.
Both adsorptive and solvent molecules can also be classified in the same way. A
polar molecule has a dipole moment, or a group, or even a bond, that is electrically
dissymmetric; a nonpolar molecule lacks this feature. The competition for the ad-
sorptive can be made to depend on polar versus nonpolar interactions. It polar
adsorptive will tend to prefer the more polar phase; a nonpolar adsorptive prefers
the more nonpolar phase. Thus, for example, the order of increasing extent of
adsorption of a series >f different adsorptives on a silica surface is the reverse of
that for the same adsorptivei, on sugar charcoal: ie, the more polar the adsorptive
molecule the greater its adsorption potential for the polar silica surface, and the
less its adsorption potential for the non polar charcoal. In general, the order of the
extent of adsorption on silica will alsolaold for other polar adsorbents, and the
order found for charcoal will hold for other nonpolar adsorbents. Water is readily
adsorbed by and therefore "wets" polar surfaces, which for that reason are often
called hydrophilic; whereas nonpolar surfaces are not "wetted" by water and are
called hydrophobic. Molecules that combine both polar and nonpolar groups in
their constitution are most readily adsorbed out of solution since they can orient
themselves at the interface with their polar portion toward the polar phase and their
nonpolar portion toward the nonpolar phase. Among molecules of this type we find
all surface-active agents; this kind of adsorption by such molecules in aqueous
solution accounts for their wetting and deterg3nt action (qv). The nonpolar portion
of these molecules is usually an aliphatic hydrocarbon chain, whose nonpolar
characteristics increase regularly with increasing chain length. Traube investigated
the lowering of surface tension caused by an homologous seri es of fatty acid
alcohols and found that for compounds of in-creasing chain length the
concentrations required to produce the same lowering of the surface tension were
reduced to about one third of the previous value each time the chain was increased
by one CH2 group. The surface-tension lowering is an indirect measurement of
the concentration of adsorptive at the liquidair interface, and it has proved
possible to make similar experiments to those of Traube by substitut -ing a liquAl
solid interface and measuring directly the quantity of solute adsorbed. For many
,systems thus studied the same rule stated by Traube can be applied ; the quantity
of solute adsorbed from an aqueous solution by a nonpolar adsorbent in-creases
geometrically (ie, by a constant factor) each time the chain length is increased by
one H2- group. Nona.queous solutions show an inverse relation of the same sort; a
polar adsorbent in a nonpolar solvent takes out less solute, by a constant factor,
each time ,:he chain length is increased by one CH2 group. Adsorbents of less
pronounced nonpolar surface may adsorb solute molecules by other attraction
mecha-nisms thall dispersion forces, eg, by electrostatic forces acting on ionic or
polar groups; the simple generalizations expressed by Traube's rule would not then
be applicable. We find, for example with cationic surface-active agents, that the
positive ionic charge of he surface-active ion can be adsorbed by polar surfaces,
such as glass or quartz, wl cl.eby the nonpolar portion of the adsorptive makes the
solid surface hydro-phobic; higher concentrations of solute a second layer of
surface-active ion adsorbs with a reverse orientation, so that the surface becomes
hydrophilic and positively charged. the second layer of adsorptive would agree
with the mechanism of Traube's rule, but the first layer would not. The E,regoing
generalizations of adsorption behavior have been summarized by Cassidy (3) in the
following iules to guide the prediction of the relative extents of adsorption. Rule .
Greater adsorption to a surface will occur from that system which produces the
greater lowering of interfacial tension. This rule follows from the Gibbs relation.
The interfacial tension is a manifestation (in part) of the unlikeness of the two
phase The adsorptive, as a result of adsorption, tends to reduce this unlikeness and
to make the transition in properties at the interface less abrupt. A corollary of this
rule is that a liquid which is highly adsorbed by a solid will show a low inter -facial
tension against the solid. Rule 2. The extent of adsorption is usually greater from
solvents in which the adsorptive is less soluble. A corollary to this rule is that for a
given adsorptive the better solvent, will make the better eluent. This rule can be
expected to hold well, particularly in those cases in which the solvents being
compared show about the same interfacial tension toward the adsorbent being used.
Rule 3. The more polar the substance the more extensive its adsorption at a polar
surface, other things being equal. A corollary to this rule is that a polar sub -stance
will be better adsorbed from a nonpolar solvent than from a polar one. Rule .4. The
less polar a substance the more extensive its adsorption at a non-polar interface,
other things being equal. But the range of values observed is usually not so wide as
that found with polar solids. This may be one reason why polar solids are more
favored for adsorption separations (except special separations such as de -
colorization); they are availabl e with a greater range of activity. Rule 5. Extent of
adsorption changes in a regular manner along an homologous series. This rule is
implicit in the concept of homology. Taken with 3 and .4. above a corollary
follows: since relative polarity decreases up an homologous serie, extent of -
adsorption to nonpolar surfaces should increase up the series. This is a restatement
of the Traube rule. Another corollary might be stated : since relative polarity de -
creases up an homologous series, extent of adsorption to polar surfaces should
increase down the series. Rule 2 would warn, however, that, since solubility
usually decreases (with any solvent) with sufficiently great increase in molecular
weight, his second corollary must be applied with discrimination.
THE SOLUTION ADSORPTION ISOTHERM The Langmuir and Freundlich
isotherm equations have been widely applied to adsorption from dilute solution. For this
application these equations have -,he follow-ing forms, respectively,

Ecuacion
And
Ecuacion
where x is the amount of solute adsorbed by m grams of the adsorbent when present at
the concentration C in the solution; a, b, k, and n are constants. In equation 75, a is a
measure of the. surface area of the solid, so that x/m = 0,8, and b is the reciprocal of the
constant K of equation 17 discussed above, and so is related to the adsorption potential
Un by the equation

Ecuacion
In equation 76 the constants I and n are relative measures of the surface area of the solid
and its adsorption potential; the value of n is usual ly between 0.1 and 0.5. The Langmuir
equation is based on the model of a uniform surface, or at least assumes that the heat of
adsorption does not vary with surface concentration; the Freundlich equation can be
derived by assuming an exponential distribution of adsorption po-tential energies. In
effect, as we have seen, the special models by which these equations are derived cannot
be proved to be valid even when the resulting equation describes the experimental data.
These equations are therefore better regarded as empirical, unless additional information
besides adsorption data is available about the system.
At higher concentrations these equations do not apply; frequently the adsorption of the
solute appears to go through a maximum, then decreases and may become negative, as
illustrated by the adsorption isotherms shown in Figure 9. For each adsorbent, ethyl
alcohol is adsorbed from a benzene solution at low concentration; similarly, at ow
concentrations of benzene in ethyl alcohol, a preferential adsorpti on of benzene takes
place, which also passes through a maximum. The peculiarity of a negative ad orption
stems from the customary method of calculating the amount adsorbed, which is taken as
proportional to the change in the concentration of solute in the solution as measured
before and after adsorption has occurred. If the solution is found to =e more concentrated
after reaching equilibrium with the adsorbent, then the solvent : -ather than the solute has
been preferentially adsorbed. When the simul-taneous ads:,rption of the two components
of the solution is taken into account the apparent anomaly of negative adsorption
disappears.
Kipling and Tester have shown how the adsorption isotherm for the complete range of
cot. :entration, as shown in Figure 9, can be related to the vapor adsorption isotherms
(29). They used the Langmuir equation to describe simultaneous adsorption from solution
of the two components; they also assumed that the whole surface of the adsorvent was
covered by the two adsorbed components, ie, B, + 02 = 1. Under these conditions the
fractions of the surface covered by each component are
Ecuacion
And
Ecuacion
The constants bi and b2 in equations 78 and 79 can be derived from the vapor adsorption
isotherms of the two components, which were measured by placing the adsorbent in the
vapor phase of the solution; by analysis of the mixed adsorbate both (xi/m) and (x2/m)
were determined separately, even though mixed vapors were used. The vapor adsorption
measurements provide an independent means of obtaining b1 and b2 for use in the
mathematical description by means of equations 78 and 79 of adsorption from solution.

The heterogeneity of the adsorbent remains the unknown factor in all investiga-tions of
adsorption from solution. The presence of this factor nullifies all efforts to treat either the
Langmuir or the Freundlich equations as anything more than empirical descriptions;
different combinations of the solute adsorption mechanism and the distribution of
adsorptive potential energies can lead to either of these equations, and to several other
shapes of the adsorption isotherm besides. Recently Giles and co-workers (30) have
attempted to classify solution adsorption isotherm:3 for use in diagnosing adsorption
mechanisms and measuring specific surface areas of solids. Their system of classification
is based on the shape of the adsorption isotherm, and includes some of the shapes shown
in Figure 6. These shapes are not peculiar to mobile adsorbed films: an almost identical
series can be obtained by combining the Gaussian distribution of surface heterogeneities
with an adsorption equation derived by Fowler and Guggenheim for a localized film with
horizontal interactions (4). The shape of the adsorption isotherm, in short, is determined
by an unknown combination of both horizontal interactions and surface heterogeneity,
and whatever the one lacks in describing the data can be supplied by the other. The
system of Giles et al. is, in effect, to equate the heterogeneity to zero and to interpret all
difference's as due to variations in the adsorption mechanism. The system will therefore
br. successful with near-homotattic surfaces but could be completely wrong for surfaces
with a wide distribution of adsorption potentials. The latter type of surface,
unfortunately, is by far the more common. The system of Giles et al. can, however, be
applied with more probability of obtaining valid answers to the class of adsorption
isotherms pertain-ing to the adsorption of dyes and other large molecules.

ADSORPTION OF DYES
The effect of surface heterogeneity can be suppressed by using adsorbates of large
molecular size. This circumstance is perhaps the basis of the vali,lity of dye adsorption as
a technique for determining specific surface areas of solid adsorbents. The adsorption
isotherm is always determined in the dilute range of concentrations where competitive
adsorption of the solvent is not significant; such isc6herms fre-quently show a saturation
plateau at high equilibrium concentrations of the free dye. Sheppard and his co-workers
(31), who investigated the adsorption of cyanine dyes by silver halides in connection with
the study of optically sensitized photographic emulsions, concluded that the saturation
plateaus observed in the adsorption isotherms of a number of cyanines adsorbed by silver
bromide microcrystals corresponded to the formation of a close-packed monolayer of
essentially planar cations, oriented with the planes of the molecules steeply inclined to
the substrate, ie, a configuration in which the edge of the molecule is presented to the
substrate (edge-on adsorption).
When the dye molecule is nonplanar or has a relatively high solubility in water, these
being two distinct factors that reduce adsorptivity from aqueous solution, the type of
isotherm shown in Figure 10, curve 2, frequently results (32). This isotherm shows the
poor adsorptivity of the tetramethyl dye (curve 2 in the diagram) compared with its
planar counterpart (curve 1), and curves 3 and 4 show the poor adsorptivity of 2,2'-
cyanines whose molecules have been forced from planarity by bulky substituents in the
methine bridge. The discontinuity exhibited in the adsorption i sotherm of the tetramethyl
dye is accompanied by a change in the absorption spectrum of the adsorbed dye. In the
low-concentration "foot" of the isotherm, the spectrum is that of the isolated molecule as
modified by its adsorption, and probably corresponds to unassociated molecules in flat
orientation with respect to the crystal surface; in the other region, the absorption
maximum undergoes a bathochromic shift to a wavelength (J-band) similar to that of the
oriented aggregates of planar dyes in solution (micelles). For the nonplanar dye, if the
adsorption plateau is identified with the completion of a monolayer, the area per
molecule is found to be consistent only with edge-on adsorption, although the average
intermolecular distance, 5.98 A, is greater than for the corresponding planar molecules,
as might be expected from the twisted configuration of the molecule..
For dyes such as 1,1 '-diethyl-2,2'- cyanine, whose adsorption isotherm is shown in
Figure 10, curve 1, the critical concentration at which lateral interactions become strong
enough to induce cooperative edge-on orientation occurs in such a dilute solution that the
isotherm appears to be continuous on the scale shown. Nevertheless a small foot.,
corresponding to noncooperative adsorption, can sometimes be found in the adsorption
isotherm of well-adsorbed dyes; the effect can be magnified by making the adsorption
con litions less favorable, eg, by introducing competing adsorbate or an unfavorable
silver ion concentration.
With systems such as these, the large size of the adsorbate molecule so masks the smaller
scale heterogeneity of the substrate that conclusions about adsorption mechanisms drawn
from the shapes of the isotherms have more validity.