c


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Brunauer, Emmett and Teller's model of multilayer adsorption is a random distribution of molecules on the
material surface.
c
 is the process of attraction of atoms or molecules from an adjacent gas or liquid to an exposed solid
surface. Such attraction forces (adhesion or cohesion) align the molecules into layers ("films") onto the existent
surface.

not to be confused with absorption; also not to be confused with chemisorption which actually is a
chemical reaction that generates a new chemical species at the exposed surface (e.g. metallic oxidation, like
steel rusting - or any corrosion).
The deposition may be driven by
ÀV 6  weak forces among atomic or molecular electric multipoles ("van der Waals", among
induced and/or fluctuating dipoles or "London", dipole-quadrupole etc.) will   the initial attraction;
ÀV
  strong ionic or metallic forces may  6 the setting of new layers onto the solid surface
(without generating new chemical species) ² as salt deposits (crystalline growth) from super-saturated
solutions OR as metal vapor deposition onto metallic surfaces.

covalent forces at solid surfaces will always create new chemical species; the formation of covalent solids
involves energy transfers that penetrate deep into the bulk, far beyond the surfaces - these are valence electron
rearrangements (phase transitions) at the whole scale of the involved bulk.
p
 
cdsorption is usually described through isotherms, that is, the amount of adsorbate on the adsorbent as a
function of its pressure (if gas) or concentration (if liquid) at constant temperature. The quantity adsorbed is
nearly always normalized by the mass of the adsorbent to allow comparison of different materials.
ÀV -
 
The first mathematical fit to an isotherm was published by Freundlich and Küster (1894) and is a purely empirical
formula for gaseous adsorbates,

where x is the quantity adsorbed, m is the mass of the adsorbent, P is the pressure of adsorbate and k and n are
empirical constants for each adsorbent-adsorbate pair at a given temperature. The function has an asymptotic
maximum as pressure increases without bound. cs the temperature increases, the constants k and n change to
reflect the empirical observation that the quantity adsorbed rises more slowly and higher pressures are required
to saturate the surface.

ÀV Ñ 

pn 1916, prving Langmuir published a new model isotherm for gases adsorbed to solids, which retained his
name. pt is a semi-empirical isotherm derived from a proposed kinetic mechanism. pt is based on four
assumptions

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These four assumptions are seldom all true: there are always imperfections on the surface, adsorbed molecules
are not necessarily inert, and the mechanism is clearly not the same for the very first molecules to adsorb to a
surface as for the last. The fourth condition is the most troublesome, as frequently more molecules will adsorb to
the monolayer; this problem is addressed by the BET isotherm for relatively flat (non-microporous) surfaces. The
Langmuir isotherm is nonetheless the first choice for most models of adsorption, and has many applications in
surface kinetics (usually called Langmuir-Hinshelwood kinetics) and thermodynamics.

Langmuir suggested that adsorption takes place through this mechanism: , where c is a gas
molecule and S is an adsorption site. The direct and inverse rate constants are k and k-1. pf we define surface
coverage, ș, as the fraction of the adsorption sites occupied, in the equilibrium we have

or

Where P is the partial pressure of the gas or the molar concentration of the solution. For very low pressures
and for high pressures

ș is difficult to measure experimentally; usually, the adsorbate is a gas and the quantity adsorbed is given in
moles, grams, or gas volumes at standard temperature and pressure (STP) per gram of adsorbent. pf we call vmon
the STP volume of adsorbate required to form a monolayer on the adsorbent (per gram of adsorbent),

and we obtain an expression for a straight line:

Through its slope and y-intercept we can obtain vmon and K, which are constants for each adsorbent/adsorbate
pair at a given temperature. vmon is related to the number of adsorption sites through the ideal gas law. pf we
assume that the number of sites is just the whole area of the solid divided into the cross section of the adsorbate
molecules, we can easily calculate the surface area of the adsorbent. The surface area of an adsorbent depends
on its structure; the more pores it has, the greater the area, which has a big influence on reactions on surfaces.

pf more than one gas adsorbs on the surface, we define șE as the fraction of empty sites and we have

and

where i is each one of the gases that adsorb.

ÀV 9


Often molecules do form multilayers, that is, some are adsorbed on already adsorbed molecules and the
Langmuir isotherm is not valid. pn 1938 Stephen Brunauer, Paul Emmett, and Edward Teller developed a
model isotherm that takes that possibility into account. Their theory is called BET theoryÃ VV VV
V V VV  V !V
 V V" 
c(g) + S cS

c(g) + cS cS

c(g) + c S c3S and so on

Langmuir isotherm (red) and BET isotherm (green)

The derivation of the formula is more complicated than Langmuir's (see links for complete derivation). We obtain:

x is the pressure divided by the vapor pressure for the adsorbate at that temperature (usually denoted P / P0), v
is the STP volume of adsorbed adsorbate, vmon is the STP volume of the amount of adsorbate required to form a
monolayer and c is the equilibrium constant K we used in Langmuir isotherm multiplied by the vapor pressure of
the adsorbate. The key assumption used in deriving the BET equation that the successive heats of adsorption for
all layers except the first are equal to the heat of condensation of the adsorbate.

The Langmuir isotherm is usually better for chemisorption and the BET isotherm works better for physisorption
for non-microporous surfaces.

ÀV D 

Two adsorbate nitrogen molecules adsorbing onto a tungsten adsorbent from the precursor state around an
island of previously adsorbed adsobate (left) and via random adsorption (right)

pn other instances, molecular interactions between gas molecules previously adsorbed on a solid surface form
significant interactions with gas molecules in the gaseous phase. Hence, adsorption of gas molecules to the
surface is more likely to occur around gas molecules that are already present on the solid surface, rendering the
Langmuir adsorption isotherm ineffective for the purposes of modelling. This effect was studied in a system
where nitrogen was the adsorbate and tungsten was the adsorbent by Paul Kisliuk (b. 19 -d. 008) in 1957. To
compensate for the increased probability of adsorption occurring around molecules present on the substrate
surface, Kisliuk developed the precursor state theory, whereby molecules would enter a precursor state at the
interface between the solid adsorbent and adsorbate in the gaseous phase. From here, adsorbate molecules
would either adsorb to the adsorbent or desorb into the gaseous phase. The probability of adsorption occurring
from the precursor state is dependent on the adsorbate¶s proximity to other adsorbate molecules that have
already been adsorbed. pf the adsorbate molecule in the precursor state is in close proximity to an adsorbate
molecule which has already formed on the surface, it has a sticking probability reflected by the size of the SE
constant and will either be adsorbed from the precursor state at a rate of kEC or will desorb into the gaseous
phase at a rate of kES. pf an adsorbate molecule enters the precursor state at a location that is remote from any
other previously adsorbed adsorbate molecules, the sticking probability is reflected by the size of the SD
constantV

These factors were included as part of a single constant termed a "sticking coefficient," kE, described below:
cs SD is dictated by factors that are taken into account by the Langmuir model, SD can be assumed to be the
adsorption rate constant. However, the rate constant for the Kisliuk model (R¶) is different to that of the Langmuir
model, as R¶ is used to represent the impact of diffusion on monolayer formation and is proportional to the
square root of the system¶s diffusion coefficient. The Kisliuk adsorption isotherm is written as follows, where Ĭ(t)
is fractional coverage of the adsorbent with adsorbate, and t is immersion time:

Solving for Ĭ(t) yields:

ÀV ]

D 

The Henderson-Kisliuk adsorption equation prediction of normalised impedance as a function of adsorption time,
where the first peak corresponds to the formation of an adsorbent surface that is saturated with MPc in its "lying
down" structure. The curve then tends to an impedance value that is representative of an adsorbent saturated
with "standing up" structure.

This adsorption isotherm was developed for use with the new field of Self cssembling Monolayer (ScM)
adsorption. ScM molecules adsorb to the surface of an adsorbent until the surface becomes saturated with the
ScM molecules' hydrocarbon chains lying flat against the adsorbate. This is termed "lying down" structure (1st
structure). Further adsorption then occurs, causing the hydrocarbon chains to be displaced by thiol groups
present on the newly adsorbed ScM molecules. When this adsorption step takes place, electrostatic forces
between the newly adsorbed ScM molecules and the ones previously adsorbed, causes a new structure to form,
where all of the ScM molecules are occupying a "standing up" orientation ( nd structure). cs further adsorption
takes place, the entire adsorbent becomes saturated with ScM in a standing up orientation, and no further
adsorption takes place.

The ScM adsorbate is usually present in a liquid phase and the adsorbent is normally a solid. Hence,
intermolecular interactions are significant and the Kisliuk adsorption isotherm applies. The sequential evolution of
"lying down" and "standing up" mercaptopropionic acid (MPc) ScM structures on a gold adsorbent, from a liquid
MPc-ethanol adsorbate phase, was studied by cndrew P. Henderson (b. 198 ) et al. in 009. Henderson et al.
used electrochemical impedance spectroscopy to quantify adsorption and witnessed that the 1st structure had
different impedance properties to the nd structure and that both structures evolved sequentially. This allowed
four rules to be expressed:

ÀV That the amount of adsorbate on the adsorbent surface was equal to the sum of the adsorbate
occupying 1st structure and nd structure.

ÀV The rate of 1st structure formation is dependent on the availability of potential adsorption sites and
intermolecular interactions.
 ÀV The amount of 1st structure is depleted as nd structure is formed.

ÀV The rate of second structure formation is dictated by the amount of adsorbate occupying 1st structure
and intermolecular interactions at immersion time, t.

From these statements, Henderson et al. used separate terms to describe rate of fractional adsorption for 1st
structure [Ĭ1(t)] and nd structure [Ĭ (t)] as a function of immersion time (t). Both of these terms were dictated by
the Kisliuk adsorption isotherm, where variables with a subscript of 1 relate to 1st structure formation and a
subscript of relates to nd structure formation.

These terms were combined in the Henderson adsorption isotherm, which determines the total normalised
impedance detection signal strength caused by the adsorbate monolayer (z(t)) as a function of Ĭ1(t), Ĭ (t), ij1 and
ij . Values of ij are weighting constants, which are normalized signal values that would result from an adsorbent
covered entirely with either 1st structure or nd structure. This isotherm equation is shown below:

clthough the Henderson-Kisliuk adsorption isotherm was originally applied to ScM adsorption, Henderson et al.
hypothesised that this adsorption isotherm is potentially applicable to many other cases of adsorption and that
Ĭ1(t) and Ĭ (t) can be calculated using other adsorption isotherms, in place of the Kisliuk model (such as the
Langmuir adsorption isotherm equation).

c

  


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cdsorbents are used usually in the form of spherical pellets, rods, moldings, or monoliths with hydrodynamic
diameters between 0.5 and 10 mm. They must have high abrasion resistance, high thermal stability and small
pore diameters, which results in higher exposed surface area and hence high surface capacity for adsorption.
The adsorbents must also have a distinct pore structure which enables fast transport of the gaseous vapors.

Most industrial adsorbents fall into one of three classes:V

ÀV Oxygen-containing compounds ± cre typically hydrophilic and polar, including materials such as silica
gel and zeolites.
ÀV Carbon-based compounds ± cre typically hydrophobic and non-polar, including materials such as
activated carbon and graphite.
ÀV Polymer-based compounds - cre polar or non-polar functional groups in a porous polymer matrix.
- 
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Physisorption is quite fast at 'low temperatures, whereas chemisorption occurs at high temperature. pn general
both types of adsorption decrease with increase ir\ temperature since the processes are exothermic.

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pn both physisorption and chemisorption,. the amount of gas adsorbed at a given temperature increases initially
with increase in pressure, it almost becomes constant at high pressure. pn chemisorption, at high pressure the
adsorbed layer is monolayer; in physisorption it is multilayer.

cc

cdsorption is present in many natural physical, biological, and chemical systems, and is widely used in industrial
applications such as activated charcoal, capturing and using waste heat to provide cold water for air conditioning
and other process requirements (adsorption refrigerators), synthetic resins, increase storage capacity of carbide-
derived carbons for tunable nanoporous carbon, and water purification. cdsorption, ion exchange, and
chromatography are sorption processes in which certain adsorbates are selectively transferred from the fluid
phase to the surface of insoluble, rigid particles suspended in a vessel or packed in a column