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Intro To Chemical Adsorption PDF
Intro To Chemical Adsorption PDF
Abstract
The chemical adsorption isotherm reveals information about the active surface of a material and has been em-
ployed for many years as a standard analytical tool for the evaluation of catalysts. Temperature-programmed reac-
tion techniques have emerged from the 1950’s as an indispensable companion to chemisorption isotherm analyses
in many areas of industry and research. This paper provides an introduction to these analytical techniques.
Keywords: chemical adsorption, temperature programmed reactions, TPD, TPR, TPO, catalyst
constant temperature is called the adsorption iso- aluminum component. The end product is a highly
therm. porous active metal ‘sponge’, all other scaffolding
materials having been removed. Another unsup-
Physical adsorption and desorption isotherms are
ported metal catalyst is produced by fusing or sinter-
important in characterizing the overall surface. The
ing metal oxides with promoters, thus forming a net-
slightest change in the shape of the plotted isotherm
work of pores throughout the metal mass (van der
is indicative of a particular surface feature. Analyses
Laan). An example of this is a fused iron ammonia
of physical adsorption isotherm data reveal the total
synthesis catalyst.
surface area, mesopore and micropore volume and
area, total pore volume, the distribution of pore vol- Zeolitic catalysts form another group. Zeolites are
ume and area by pore size, and surface energy distri- hydrated aluminosilicates and are used widely in the
bution. Thus, physical adsorption is an important tool chemical industry and refining operations. Their ac-
in the study of catalysts, particularly in evaluating the tivity is influenced by the silica to alumina ratio.
support structure. Amorphous silica-alumina catalysts have a lower
activity than zeolitic catalysts and are applied in mild
The chemical adsorption isotherm also evaluates hydrocracking operations. An acidic surface is re-
the surface, but is selective in that it only probes the quired for cracking and the acidity is associated with
active areas—those capable of forming a chemical the oxygen atoms attached to aluminum atoms.
bond with the adsorptive gas or vapor. This selectiv-
ity involves both the probe molecule and the molecu- 5. Chemisorption and catalysis
lar or atomic composition of the active material, so The catalytic process can be generalized by a
the choice of probe molecules is much more impor- short sequence of steps as follows. Consider reactant
tant in chemisorption tests. Although isothermal molecules A and B in the gaseous bulk above a solid
chemisorption tests are important in characterizing surface that supports an ensemble of active metal
active surfaces, temperature-programmed tests are sites S. If molecule A is chemically adsorbed on one
even more so. The basic form of data produced by of the active sites, a surface complex A is formed.
these tests resembles a chromatogram of temperature Next, A reacts with B forming molecule A+B, which
versus quantity desorbed. escapes the site, thus regenerating site S.
4. Catalyst Basics Sorption of at least one of the reactant molecules
A catalyst affects the rate of a chemical reaction. is required for catalysis to occur. If the accelerated
‘Rate' is the most important word in this description rate of reaction simply was due to the concentration
because a catalyst cannot induce a reaction that is not of molecules at the surface, catalysis would result
permissible under the laws of thermodynamics. A from physical adsorption of the reactants. Chemi-
catalyst only can increase the rate at which the reac- sorption is a essential step, the adsorbed molecule
tion approaches equilibrium. forming an intermediate surface complex that is more
receptive to chemical reaction. The dependence of
Heterogeneous catalysts include metals, metal catalysis on chemisorption is one reason why chemi-
oxides and solid acids. Pure metals may be employed sorption is such an informative analytical technique
as solid catalysts, or may be dispersed as small grains in the study of catalysis—the chemistry occurring in
on the surface of a supporting material such as TiO2, the application of the catalyst is being observed di-
ZrO2, Al2O3, or SiO2. The preparation of a sup- rectly in the laboratory.
ported catalyst involves selecting precursors of the
active components and any necessary promoters and The performance of a catalyst depends on several
mixing them in a solvent. The mixture forms a pre- variables. First, adsorption sites must be both nu-
cipitant, or is used to coat an inert carrier, or is used merous and available to the reactant molecules. In
to impregnate a carrier. Ultimately, the active metal some cases, grains of active metal are at the surface,
or precursor is dispersed on the carrier. The product but there also are grains located below the surface
is dried, mixed with a binder or forming agent, then and unavailable to the reactants. Adsorption sites
ground, pelletized, extruded, or otherwise shaped. simply being located on the surface is insufficient to
Finally, the material is calcined and activated by oxi- assure optimum performance. For example, some
dation, reduction, or other means. potential adsorption sites may be located deep within
a micropore that is too narrow for the reactant mole-
One type of unsupported catalyst is composed of pure cule to enter or for the reaction product to exit; in this
metal. Raney metal catalysts, for example, are pre- case the surface site cannot be an active participant in
pared by dissolving an aluminum-nickel alloy in a chemisorption. A site could be located along a tortu-
solution of sodium hydroxide, which dissolves the
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INTRODUCTIONTOCHEMICALADSORPTIONANALYTICALTECHNIQUESANDTHEIRAPPLICATIONSTOCATALYSIS
ous path that impedes the efficient flow of reactants from the injected quantity yielding the quantity ad-
toward the active site and products away from the sorbed from each injection. These are summed to
site. Since many active metals are very expensive, an determine the capacity of the sample mass. Injections
important design criterion is to maximize the number may be made by syringe or by a manual or automated
of active sites per unit of metal. HPLC-type, loop injection valve. Since the end-
point (saturation) is the only point measured, the
Catalytic activity depends on how rapidly
number of injections may be only a few and there are
chemisorption occurs and the strength (energy) of the
no pressure changes. Thus, the flowing-gas tech-
chemisorption bond. If the bond is too weak, the
nique is often performed manually, although auto-
molecule may desorb prior to reacting; if too strong,
mated instruments also are available.
the release of the product and regeneration of the site
may be retarded. Isothermal chemisorption methods Over the past few decades, temperature-
as well as temperature-programmed chemisorpiton programmed chemisorption analyzers have become
methods can be used to study surface energy distribu- recognized as extremely valuable tools for character-
tion. izing catalysts. The method is sometimes simply re-
ferred to as temperature-programmed reactions, and
Chemisorption as described above pertains to the use
includes Temperature-Programmed Desorption
of catalysts in various applications. The same reac-
(TPD), Temperature Programmed Reduction (TPR)
tions, only on a smaller scale, also can occur in a
and Temperature Programmed Oxidation (TPO). The
sample tube under controlled conditions allowing the
dynamic chemisorption method is particularly suit-
process to be studied. This is chemisorption used as
able to performing temperature program analyses.
an analytical technique. Chemisorption analyses are
applied to physically characterize a catalyst material, 6.2 Chemisorption Analyses
to determine a catalyst’s relative efficiency in pro-
The versatility of the chemisorption technique is il-
moting a particular reaction, to study catalyst poison-
lustrated by the extent of information about a mate-
ing, and in monitoring the degradation of catalytic
rial that can be acquired. Some of its versatility has
activity over time of use. Among the various instru-
been revealed in the discussion above. In the follow-
ment techniques used in analyzing catalysts, chemi-
ing sections, additional capabilities are explored.
sorption techniques are the most universally em-
ployed. In the examples that follow, only catalysts composed
of a single active species are considered to simplify
5. Chemisorption instruments
the math. In the case of mixed metal catalysts, many
Isothermal chemisorption analyses are obtained of the equations below would require summing a
by two chemisorption techniques: a) static volumetric series of terms, one for each adsorbing species and
chemisorption, and b) dynamic (flowing gas) chemi- each term weighted by the fractional contribution of
sorption. the species to the whole.
The volumetric technique is convenient for ob- 6.2.1 The chemisorption isotherm
taining a high-resolution measurement of the chemi-
An isotherm is a set of quantity-adsorbed versus pres-
sorption isotherm from very low pressure to atmos-
sure data points that characterize the adsorption proc-
pheric pressure at essentially any temperature from
ess at a constant temperature. To understand this bet-
near ambient to 1000+ oC. Commercial embodi-
ter, consider a reactor of constant volume V that
ments of this technique are almost exclusively auto-
contains a sample and a quantity of gas molecules N.
mated. Obtaining a high-resolution isotherm requires
Chemisorption theory assumes that the active surface
many, precise dosing steps in pursuit of the equilib-
of a solid contains a fixed number Ns of adsorption
rium point, and many pressure steps which, without
sites and only one molecule at a time can occupy a
automation, would be a time-consuming and error
site. The molecules in the sample tube that are com-
prone procedure.
peting for an adsorption site represent a concentration
The flowing gas (dynamic) technique operates at C that can be expressed in general by solving the gas
ambient pressure. After the sample has been cleaned, law , or
small injections (doses) of accurately known quanti-
N/V = P/RT (1)
ties of adsorptive are administered in pulses until the
sample is saturated, thus the name, ‘pulse chemisorp- where N and V have previously been defined, P is
tion’. A calibrated thermal conductivity detector pressure, T temperature, and R the gas constant
(TCD) monitors the quantity of adsorptive that is not
taken up by active metals. This quantity is subtracted
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INTRODUCTIONTOCHEMICALADSORPTIONANALYTICALTECHNIQUESANDTHEIRAPPLICATIONSTOCATALYSIS
For a specific gas-solid system at equilibrium under involving fragmenting (dissociation) of the adsorp-
specific conditions of temperature and pressure, a tive molecule. The isotherm is asymptotic to θ = 1,
certain fraction θ of the total number of available which is full coverage, or completion of the
sites Ns will be occupied by nads adsorbed molecules. monolayer.
This is described by
Several Langmuir isotherms are illustrated in Figure
θ = nads/Ns (2) 1, the only difference being the magnitude of b. The
b parameter is directly related to surface energy; in-
The rate at which equilibrium is achieved depends on
creasing surface energy increases the probability of
the concentration of molecules involved as well as
adsorption at a given pressure. The b parameter is
other considerations, the latter being grouped into a
inversely related to temperature, which, when in-
parameter referred to as the ‘rate constant’ k.
creased, increases molecular energy and decreases the
For the adsorption process, the concentration of un- probability of adsorption at a given pressure.
adsorbed molecules competing for the remaining sites
In the illustration, b1 is less than b2, which is less
is C-θC and the rate of adsorption is kads(C-θC) or than b3, and so on, b5 being 50 times greater than b1.
kadsC (1-θ). For desorption the fraction of molecules From this one it may be inferred that the same sample
desorbed is ? and the rate of desorption is kdesθ. being analyzed at five different temperatures would
When equilibrium is achieved, the rate of adsorption produce a similar set of isotherms, as would five dif-
and desorption are equal, that is, ferent samples of different surface energy measured
kadsC (1-θ) = kdesθ (3a) at the same analytical temperature.
0.8
b3 gassing prior to second
0.7 adsorption test.
0.6
0.5 b2
0.4
After second adsorption R R I I I I R R
0.3 b1
test.
0.2
0.1
0
0 200 400 600 800 1000 Figure 2. Four steps in determining the isotherm
Pressure
Pressure (arbitrary units) for only irreversible adsorption.
Figure 1. A family of calculated Langmuir iso- The reversible and irreversible contributions to a
therms, each with a different value of b. combined isotherm can be distinguished by running a
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INTRODUCTIONTOCHEMICALADSORPTIONANALYTICALTECHNIQUESANDTHEIRAPPLICATIONSTOCATALYSIS
3
Differ-
2
ence
1
Test 2
0
0 100 200 300 400 500 600 700
Pressure (arbitrary units)
Figure 3. The isotherm resulting from Test 1 is a Figure 4. A series of detector signals following injec-
combination of reversible and irreversible adsorp- tions of X µl of adsorptive; the integrated area of each
tion. The isotherm from Test 2 corresponds only to
peak is indicated. None of injections 5, 6, and 7 was
reversible adsorption. The difference is the iso-
therm from only irreversible adsorption. adsorbed.
second adsorption test. After the initial adsorption The partial pressure of the adsorptive momentarily
test and prior to the second test, the sample is sub- increases over the sample as the pulse passes and
jected to vacuum only, causing the weakly adsorbed some or all of the injected quantity of gas is ad-
molecules to desorb, leaving only those molecules sorbed. Any unadsorbed gas is swept through the
that have formed a strong chemisorption bond with detector where it is registered. Note that, unlike the
the active surface. static method (described above), the net adsorption is
only irreversible adsorption because, after the pulse
The second adsorption test is performed under the
of adsorptive passes, the partial pressure of the ad-
same conditions as the initial test, but this time the
sorptive in the bulk gas is essentially zero and escap-
active surface is already covered with a chemisorbed
ing weakly adsorbed molecules are swept to the de-
monolayer. The uptake of adsorbate will be only that
tector by the carrier stream.
associated with reversible adsorption. Subtracting the
quantity reversibly adsorbed from the combined iso- As the monolayer forms on the active surface, less
therm at each pressure value yields an isotherm of and less of the injected adsorptive is taken up by the
ireversible adsorption. The analytical results are illus- sample. Injections continue until the sample is satu-
trated in Figure 3. rated, as indicated when all subsequent detector
peaks remain the same size. The results of such a
6.2.2 Number of accessible active sites
test are shown in Figure 4, which illustrates the out-
Both static volumetric and dynamic chemisorption put of the detector. The area of each peak is propor-
techniques can be used to measure the quantity of gas tional to the quantity of the injection that was not
required to form a monolayer of chemisorbate on an adsorbed.
active surface. The dynamic method yields only a
In Figure 4, the integrated area of peaks associated
single data point, which corresponds to the quantity
with injections 5, 6, and 7 indicate that no adsorp-
of adsorptive required to saturate the active surface
tion occurred, so the active area is saturated. All of
with a monolayer. The monolayer capacity of the
the first injection was adsorbed, as was 88% of injec-
active surface is calculated from the derived irre-
tion 2, 20% of injection 4, and 2% of injection 3.
versible adsorption isotherm illustrated in Figure 3.
From the known quantity of each injection, the frac-
Since the irreversible adsorption isotherm is asymp-
tion of each injection that was adsorbed, and the mass
totic to the value of total coverage (of the active sur-
of sample material, the number of moles of adsorp-
face), the plateau of the isotherm is extrapolated back
tive gas taken up by each gram of sample is deter-
to the y-axis to yield the monolayer capacity value.
mined.
Extrapolating to the y-axis the linear section of the
combined reversible-irreversible isotherms also pro- The adsorption process can involve the separation of
vides a reasonable value for the monolayer coverage a molecular adsorptive into two or more molecular or
quantity. atomic entities (ions or radicals), each entity forming
a bond with individual active surface sites. This is
The dynamic chemisorption method requires
called dissociative or second-order adsorption in
(manually or automatically) injecting small, pre-
contrast to first-order or non-dissociative adsorption
cisely-known quantities of adsorptive into a stream of
in which the adsorptive molecule remains intact dur-
inert carrier gas that flows through the sample bed.
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INTRODUCTIONTOCHEMICALADSORPTIONANALYTICALTECHNIQUESANDTHEIRAPPLICATIONSTOCATALYSIS
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INTRODUCTIONTOCHEMICALADSORPTIONANALYTICALTECHNIQUESANDTHEIRAPPLICATIONSTOCATALYSIS
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INTRODUCTIONTOCHEMICALADSORPTIONANALYTICALTECHNIQUESANDTHEIRAPPLICATIONSTOCATALYSIS
oxygen consumed during the reaction is related to the physisorption as well as the net energy path taken by
quantity of a species on the surface. the chemisorbed molecule. It should be understood
while examining this diagram that it is a basic depic-
6.2.7 Surface energy and first order kinetics
tion of a single molecule approaching a surface and
Adsorption and desorption mechanisms are com- considers only energy as a function of distance from
posed of some combination of elementary kinetic the surface, neglecting other variables.
steps. For example, a diatomic molecule can be ad-
One situation that would greatly change the shape of
sorbed or, as it approaches the surface, it may frag-
the chemisorption curve in Figure 7 would be if the
ment into atoms that are adsorbed independently.
adsorption process were to be dissociative. Dissocia-
The former case is called non-dissociative chemisorp-
tive chemisorption requires an expenditure of energy
tion or first-order kinetics, the latter is dissociative
(dissociation energy) to fracture the adsorptive mole-
chemisorption or second-order kinetics. First-order
cule. This would result in the net energy path having
kinetics will be of primary focus in the following
a positive peak just before the negative-going poten-
discussions.
tial energy well. This is illustrated in Figure 8. As in
The interaction of a single, isolated molecule with a Figure 8, the physical adsorption path initially is
surface can be depicted in a plot of potential energy more favorable (lower energy) as the molecule ap-
versus distance from surface as in Figure 7. For proaches the surface, but to dissociate and chemisorb,
comparison, Figure 7 also includes an energy plot for a positive energy step is required to make the transi-
tion to the chemisorption path. This energy is in ex-
5
Potential Ene rgy vs Dista nce from Surface cess of the dissipated potential energy of the mole-
4 cule.
3
Energy (arbit rary units)
-2
0 5 10 15 20 25 termines if the system is in equilibrium. At equilib-
Energy path of molecule AB if non-dissoc iative
rium, a molecule at any location in the system should
-4
adsorption experience the same energy potential; this applies to
-6 Dist ancefrom surface (Angstroms)
molecules in the bulk gas or vapor surrounding the
Figure 8. Potential energy wells associated with physi- solid and to the adsorbed molecules at the solid sur-
cal adsorption and dissociative chemical adsorption. face.
The net energy path for a molecule to chemically ad-
sorb has a positive excursion called the activation en- For a specific adsorbate-adsorbent system, adsorption
ergy. This input of energy is necessary for adsorption equilibrium is achieved by a delicate balance between
and any subsequent catalytic reaction. the pressure P of the bulk gas phase, analytical tem-
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INTRODUCTIONTOCHEMICALADSORPTIONANALYTICALTECHNIQUESANDTHEIRAPPLICATIONSTOCATALYSIS
perature T, and the degree of surface coverage θ. step-by-step derivation is presented here because it
Experimentally, one of these parameters is held con- may be of interest to some readers and a detailed
stant, the other is assigned a value, and the third is derivation is difficult to find in the literature. Por-
observed to determine its value at equilibrium. An tions of what follows were gleaned from works of
isotherm conveys the degree of surface coverage as a Schroeder and Gottfried, Houston, Nix, and Garrett.
function of pressure at constant temperature (θ = Desorption involves the time rate of change of the
f(P)T), an adsorption isobar expresses the degree of number of adsorbed molecules N, algebraically ex-
surface coverage as a function of temperature at con-
pressed as ∆N/∆t. This also may be viewed as the
stant pressure θ = f(T)P), and an isostere shows the time rate of change in the number of available ad-
relationship between pressure and the temperature for sorption sites Na.
a constant degree of coverage. (P = f(T)θ).
(Note: Time-dependent and temperature-dependent changes
The Clausius-Clapeyron equation expresses the heat are more conveniently dealt with mathematically by consider-
of adsorption at a specific degree of surface coverage ing each step change in time or temperature to be infinitesi-
mally small. Thereby, ∆N/∆t can be replaced by dN/dt and
θ in terms of pressure and temperature, thus it yields algebraic manipulation is replaced by differential calculus.
the isosteric heat of adsorption qst. The equation in For readers not familiar with calculus, any expression of the
partial differential form is form dX/dY can be considered to be the slope of a plot of X
versus Y at a given value of X.)
qst = R(δlnP /δ(1/T)) (10)
The kinetic expression for the rate of desorption Rd
where T is temperature, P pressure, and R the gas is
constant. -dN/dt = Rd = k Nx (12)
Obtaining related values of temperature and pressure where k is the rate constant, -N the instantaneous
for a given degree of coverage is achieved by obtain- surface concentration (number) of the adsorbed spe-
ing multiple isotherms of the same sample at different cies (negative indicating decreasing), and x the ki-
temperatures and scaling the quantity adsorbed axis netic order. Only the simplest case, first order (non-
in units of degrees of coverage. This provides a dissociative) kinetics, is considered here; therefore
means for extracting from the set of isotherms, a set x=1. Note that the rate of desorption constantly
of isobars plotted as degree of coverage versus tem- changes as the number of molecules remaining on the
perature over the range of temperature used in the surface diminishes.
analyses. From the set of isobars, a set of pressure
versus temperature values for various values of val- Figures 8 and 9 illustrate that activation energy may
ues of volume adsorbed can be extracted. These are or may not be required to cause adsorption to pro-
plotted as ln(P) vs. 1/T. ceed. However, these figures also illustrate that there
always is an activation barrier that must be overcome
The Clausius-Clapeyron equation, above, can be re- for the molecule to desorb, that is, for the chemisorp-
grouped in linear form, y = m(x), yielding tion surface reaction to reverse. The relationship
between the rate constant and energy in energy-
ln(P)V = qst (1/T)V (11)
dependent reactions such as desorption can be ex-
R being a scaling constant that does not affect the pressed in an Arrhenius form, specifically
slope. For value of quantity adsorbed, there is a dif-
ferent slope, qst. Plotting the set of slopes as a func- k=Ae-Ed/RT (13)
tion of quantity adsorbed provides the sought-after where Edes is the activation energy and the subscript
graph of surface energy versus quantity adsorbed, ‘d’ identifying the particular case as that of desorp-
which relates to surface coverage or loading. tion. The pre-exponential factor A can be considered
Heat of adsorption also can be calculated from data the number of attempts by the molecule per unit time
obtained by dynamic chemisorption by what is some- to escape from the potential well. T is temperature
times called the ‘heating rate variation’ method. (degrees Kelvin) and R the universal gas constant.
Since quantity adsorbed as a function of pressure is The product RT is thermal energy, so the exponent
not monitored by the dynamic method, an expression E/RT is the ratio of activation energy to thermal en-
of energy other than those of Eqs. 10 and 11 must be ergy. While E is larger than RT, there is little prob-
sought. As an exercise, such an expression is derived ability of desorption.
in the following paragraphs. The result (Equation Substituting the Arrhenius expression into Eq. 8
21) can be taken and used on faith and the drudgery gives
of wading through the math avoided. However, the
Rd = NAe -Ed / RT (14)
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INTRODUCTIONTOCHEMICALADSORPTIONANALYTICALTECHNIQUESANDTHEIRAPPLICATIONSTOCATALYSIS
This is the Polanyi-Wigner equation for rate of first- During a temperature-programmed analysis test, the
order desorption. One can experiment with this sample is heated linearly so that the temperature T at
equation to better understand what it describes in any time t can be calculated by
regard to desorption How desorption rate (Rd), cov- T(t) = To + βt (15a)
erage (N) and the energy ratio (Ed/RT) change as a
or
function of temperature are plotted in Figure 10, the
values being normalized on the vertical axis for con- dT(t)/dt = β (15b)
venience. During an actual experiment the detector
output would correspond to the rate of desorption. where β ?is the heating rate or ramp rate dT/dt in units
The temperature Tm at which the rate of desorption is of degrees K per unit time. As temperature is in-
maximum is easily observed in Figure 10 as it would creased, there is a change in the number of molecules
be on a plot of detector signal (quantity of evolved being desorbed per unit time, expressed by dN/dT.
molecular species) versus temperature. Multiplying the time-dependent heating rate (dT/dt)
in degrees/min by the temperature dependent rate of
desorption (-dN/dT) in molecules/degree) gives time-
Coverage, Rate of Desorption, and Energy Ratio vs. Tempera-
ture dependent rate of desorption, Rd. Mathematically,
% Max. Value of -Rd (equivalent to absolute
(16)
Value value of slope of coverage plot)
100
-dN/dT * dT/dt = dN/dt = Rd
Coverage (N)
80 Heating rate β was defined in Eq. 15a as dT/dt, there-
60
fore, substitution into the left side of Eq. 12 gives
Ed/RT
-dN/dT * β = Rd (17)
(energy ratio)
40
Figure 10. Parameters of Eq. 14 are plotted against and rearrangement yields the temperature-dependent
temperature. The amplitude of each parameter is di- rate of desorption,
vided by its maximum value x 100% as a means of nor-
-dN/dT = (NA/β) e-Ed/RT (19)
malizing the data.
which describes the rate of desorption plot in Figure
Note: Figure 10 was produced by Microsoft Excel® using 10. As temperature increases, the rate of desorption
Eq. 14 and arbitrary values for the parameters. This allows maximizes at Tm and at that temperature the slope
experimentation with the parameters and comparison of (first derivative) of Eq. 15 equals zero, that is,
various plots predicted by the Polanyi-Wigner model. It can
be observed that peaks are somewhat asymmetric around d[ (NA/β) e-Ed/RTm]/dT = 0 (20)
Tm, increasing the initial coverage value causes the peak to
increase in amplitude but with Tm remaining constant. For clarity and continuity, the reader is reminded that
Increasing the value of A causes the peak to move towards
lower temperatures. Increasing Ed causes the peak to
Equation 20 has the form d(uv)/dT, where u =
broaden and the maximum value occur at higher tempera- (A/b)N, v = e-Ed/RT, and N is a function of temperature
tures. (T).
Extracting the log of both sides of Equation 10 pro- Equation 20 yields
duces
NA/β Ed/RTm2 e-Ed/RTm + A/β e-Ed/RTm dN/dT = 0
ln Rd = ln N + ln A - Ed / RT
(21)
Grouping this equation in linear form, y = (m)x +(b)
yields Now, substitute the right side of Equation 19 for
dN/dT (a negative value; see Equation 12) in Equa-
ln Rd = (-Ed / R)1/T + (ln N + ln A) tion 13 and factor. This gives
Plotting ln Rd versus 1/T produces a straight line NA/β Ed/RTm2 e-Ed/RTm - A/β e-Ed/RTm (NA/β) e-Ed/RTm = 0
having slope -Ed/R and intercept (ln N + ln A). The
problem, here, is that numerical values for Rd are not (22a)
available, so the derivation must be expanded. or
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INTRODUCTIONTOCHEMICALADSORPTIONANALYTICALTECHNIQUESANDTHEIRAPPLICATIONSTOCATALYSIS
NA/β Ed/RTm2 e-Ed/RTm = A/β e-Ed/RTm (NA/β) e- Ed/RTm = ln Tm2/β − ln Ed/AR (30a)
Ed/RTm
(22b)
Ed= RTm(ln Tm2/β − ln Ed/AR) (30b)
Eliminate common terms on left and right sides, and
there is left Ed= RTm(ln ATm/β − ln Ed/RTm) (30c)
Tm2/β = Ed/AR eEd/RTm (24) Much like the single point method of determining
BET surface area, this method introduces some error,
Taking the log of each side yields but it allows Ed to be estimated from a single desorp-
tion chromatogram. (Schroeder and Gottfried).
ln Tm2/β = Ed/RTm + ln Ed/AR (25a)
Rather than estimating the value of A, a series of
a linear equation in which y = ln Tm2/β,
x = 1/Tm , m chromatograms could be obtained for different values
= Ed/R, and b = ln Ed/AR. Plotting y versus x for a of β and the values of Ed and A determined from the
series of β values allows the determination of Ed. linear plot.
Another form of Equation 25a sometimes found in
In using the Redhead method, it must be remembered
the literature follows from expanding the logarithmic
that it applies only to first order kinetics. In regard to
terms to obtain
higher order reactions, Stoltz admonishes (Stoltze),
2lnTm – lnβ = Ed/RT + ln Ed/AR (25b) “To describe E obtained in this fashion as an ap-
proximation is an understatement, completely wrong
is a better description.”
Another way to arrive at Equation 25 from Equation SUMMARY
22a is to factor and rearrange the latter equation, giv-
ing Solid catalysts play a ‘behind the scenes role’ in mak-
-Ed/RTm ing affordable and even making possible many of the
NA/β e [Ed/RTm2 -Ed/RTm
- A/β e ] = 0 (26) benefits enjoyed in everyday life. Chemisorption is a
Dividing both sides of this equation by the expres- fundamental step in catalytic reactions, so being able
sion in the brackets gives to study the chemisorption process on a small scale in
the laboratory is of great benefit. Modern analytical
Ed/RTm2 = A/β e-Ed/RTm (27) instruments capable of characterizing these reactions
which is the same as Equation 23. are powerful tools for monitoring and controlling the
manufacture and application of catalysts and predict-
There also is the case ing performance characteristics of newly developed
[Ed/RTm2 - A/β e-Ed/RTm] = 0 (28a) catalyst materials.
or
Ed/RTm2 = A/β e-Ed/RTm (28b)
established by dividing both sides of Equation 26 by
the factors outside of the brackets or by logically de-
ducing that since neither factor NA/β nor e-Ed/RT has
a value of zero during the desorption process, the
expression in the brackets of Equation 26 must equal
zero. Rearranging yields
Tm2/β = Ed/AR eEd/RTm (29)
which is the same as Equation 24
Following the method of Redhead, Equation 25 is
rearranged as follows:
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INTRODUCTIONTOCHEMICALADSORPTIONANALYTICALTECHNIQUESANDTHEIRAPPLICATIONSTOCATALYSIS
John H. Sinfelt, Structure of Metal Catalysts, Review Gerard P. van der Laan, Kinetics, Selectivity and
of Modern Physics, Vol. 51, No. 3 (1979) Scale Up of the Fischer-Tropsch Synthesis, Doctoral
Thesis, University of Groningen, The Netherlands,
1999
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