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Adsorption
and application in Surface Area and Porosity Analysis
References
1. 2. 3. 4. 5. 6. 7. Robert J. Silbey, Robert A. Alberty and Mougi G. Bawendi. 2005. Physical Chemistry, 4th ed., John Wiley & Sons. Atkins, P. W. and J. Paula, 2002. Physical Chemistry. 7th ed. London: Oxford University Press Laidler, K. J. and Meiser, J. H. 1999. Physical Chemsitry. 3rd ed. Boston: Houghton Mifflin Co. Levine, I. N., 2003, Physical Chemistry. 5th ed. Boston: McGraw Hill James E. House, 2007, Principles of Chemical Kinetics, 2nd ed. Amsterdam: Elsevier Paul A. Webb and Clyde Orr, Analytical Methods in Fine Particle Technology, Micromeritics, Norcross USA (1997) Terence Allen, Particle Size Measurement, 4th ed., Chapman and Hall, London (1990)

Introduction
Base on gas adsorption N2, Ar, Kr, CO2 Application Catalysts, activated carbons, carbons, pharmaceuticals, building materials, silicas and aluminas, metal powders, oxides and salts, adsorbents, ceramics, zeolites, pigments, glass, clay, LDH, nanocomposites etc Information Surface area, type of pore (non, micro, meso), pore size, pore volume, pore distribution, Principles Amount gas adsorbed depends on nature of the solids (adsorbent) and the pressure during adsorption. The amount adsorbed calculated by gravimetric or volumetric method. Isotherm - graph of amount adsorbed (V) vs P or P/Po (Po saturated pressure) the amount for complete monolayer coverage is determined, Vm

surface

area =

number of molecule cross sectional area of molecule (m 2 /g) weight of substance

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Quantitative analysis of adsorption process

Surface area of regular shape objects can be easily determined from their dimensions. However materials occur in nature are irregular in shape, complex and often contain pores and channels. If the internal structures of these materials are accessible by certain gas molecule it is possible to determine their total surface area by adsorption process. The extent of surface coverage is normally expressed as the fractional coverage, where:

number of adsorption sites occupied V = number of adsorption sites available Vm

Often expressed in terms of the volume of adsorbate adsorbed V, where Vm is the volume of adsorbate corresponding to complete monolayer coverage. The rate of adsorption, d/dt, is the rate of change of surface coverage, and can be determined by observing the change of fractional coverage with time.

adsorbate

Adsorption
adsorbent

d 2

4 Vm N A n= V molar A = n = s= A m 4 .35 V m where V m in cm 3 at STP m

d 2V m N A
4V molar

for N 2 s =

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What is ?

Schematic representation of absorption process of N2(g) on an adsorbent, eg. aerogel

>2

=2

=1

<1

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Thermodynamic
Factors affecting adsorption Chemical and physical properties of gas Chemical and physical properties of solid Temperature Pressure Spontaneous process G = -ve S = -ve (exothermic)

N2(g) N2(g) (adsorbed) H = G + TS = -ve Lenard-Jones potential

(r)
r

Molecule in contact with the surface for a certain time before desorbed into gaseous phase

Types of adsorption
There are two principal modes of adsorption of molecules on surfaces: Physisorption: the only bonding is by weak Van der Waals - type forces. There is no significant redistribution of electron density in either the molecule or at the substrate surface. Chemisorption: a chemical bond, involving substantial rearrangement of electron density, is formed between the adsorbate and substrate. The nature of this bond may lie anywhere between the extremes of virtually complete ionic or complete covalent character.

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Physisorption

Chemisorption

1. Caused by Van der Waals forces. No Electron tranfer/sharing occurs. electron transfer. Molecules adsorbed intact Caused by covalent/electrostatic forces. Dissociates into atoms, ions, or radicals 2. Heat of adsorption 2-6 kcal/mol. Heat of adsorption 10-200 kcal/mol. 3. A general phenomenon. i.e. condensation Specific and selective of a gas. 4. Physisorbed layer can be removed by Removed only by evacuation and heating evacuation at the temperature of adsorption. above adsorption temperature. 5. Multi-layer adsorption below the critical temperature of the gas 6. Appreciable only below the critical temperature. 7. Rate: May be fast or slow 8. Adsorption not strongly affected. Never exceeds a mono-layer. Appreciable at high temperatures also Rate: Instantaneous, A spontaneous process requires G<0 i.e G = H - TS <0. Highly affected. Surface compounds formation because of true chemical reaction.

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Langmuir Theory
The first adsorption theory proposed by Langmuir (J. Am. Chem. Soc. 40, 1361 (1918)). Adsorption limited to monolayer. Limited applicability to physical adsorption, more suitable for adsorption in solution such dye, ion exchange, etc Surface force is short range thus only molecules striking bare surface is adsorbed while other molecules reflected back into gas phase. Localised adsorption and enthalpy of adsorption is independent of the covered area. Uniform surface. Adsorbed molecule do not interact. At equilibrium the number of molecule evaporating is equal to the number condensing. Rate of adsorption Rate of collision gas -surface proportional to P = Rate of desorption Proportional to adsorbed surface

V rate 1 Vm

rate

V Vm

E ads Arrhenius factor exp RT

E Arrhenius factor exp des RT

Thus at equilibrium it can be written

V V E E P1 exp ads = k exp des V V RT RT m m

Where k is constant and since

H ads = Eads Edes the eq is becomes

H ads V / Vm P = k exp RT (1 V / Vm )
Since enthalpy of adsorption is independent of covered surface, thus

thus

H ads 1 k exp = RT b V / Vm bP = (1 V / Vm )

a constant

or

V=

bPVm 1 + bP

At low pressure bP<<1 thus V =VmbP At high pressure bP>>1 thus V=Vm

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The above equation can be written as isotherm Vm Vadsorbed

P 1 P = + V bV m V m
P V
1 Vm

slope =

Type 1 isotherm

intercept =

1 bVm
P

P/Po (Relative pressure) Po = saturated vapour pressure

Most of the Langmuir assumption are false. Surface of solids not uniform thus desorption depends on the location of adsorption. Interaction force between molecules is substantial. Adsorbed molecule can move from one site to another.

DIY
Isotherm plot of CO (molecular radius 57 pm) on 0.1 g activated carbon at STP is as follows 12 11 P (torr / cm3 ) V 10 9 100 200 300 P (torr) Calculate the specific surface area for the activated carbon. 400

y = 0.0082 x + 7.783 R2 = 0.998

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DIY Below are data for the adsorption of CO on charcoal at 273 K. Confirm that they fit Langmuir. Find the value of equilibrium rate constant and the adsorption volume at complete coverage P (kPa) V (cm3) 13.3 10.3 26.7 19.3 40.0 27.3 53.3 34.1 80.0 45.5 93.3 48.0

DIY Following are data for the adsorption of H2 on Cu at 25 oC. Confirm that they fit Langmuir at low coverage. Find the value of equilibrium rate constant and the adsorption volume at complete coverage P (Pa) V (cm3) 25 0.042 129 0.163 253 0.221 540 0.321 1000 0.411 1593 0.471

BET Theory
Important step forward in adsorption theory Brunauer, Emment, Teller (J. Am. Chem. Soc., 60, 309 (1938)) Multilayer adsorption Assumption: Forces that produce condensation responsible for multimolecular adsorption. They proceeded further from Langmuir theory, where the formation of first monolayer serves a site for the second layer and so on. Thus the concept of localization prevails and mutual interaction neglected. The equation

P 1 C 1 P = + V ( Po P ) V m C V m C Po
C = constant exp E1 q L RT

and

Where E1 = heat of adsorption of the first layer qL = latent heat of condensation of the adsorbate

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isotherm Vadsorbed

P V ( Po P )

slope =

C 1 VmC

Vm

intercept =
P/Po

1 Vm C
P/Po

slope + intercept =

C 1 1 1 + = Vm C Vm C Vm

1 = Vm slope + intercept
What about C value? Value of P/Po for BET plot are taken between 0.05 to 0.3. The upper limit can be lower. The value of C frequently between 50 and 100 for N2.

DIY
The following result was obtained for N2 adsorption on 0.85 g of titania at STP

P V ( Po P )
(cm-3)

slope = 100 10 4

intercept = 1.5 10 4
P/Po

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Single Point BET

P 1 C 1 P = + V ( Po P ) VmC VmC Po
Usually the intercept is small compared to the slope and may be considered insignificant. Thus the line may be forced to pass through origin. This equivalent by assuming C is large, C>>1, thus

1 0 VmC

and C-1 C

P 1 P = V ( Po P) Vm Po
Usually done for P/Po around 0.3 and C > 100. If C < 80 large error.

DIY
The following is the adsorption data of N2 adsorption on 1 g of TiO2(rutile) at 75 K. P(torr) V (mm3) 1.20 601 14.0 720 45.8 822 87.5 935 127.7 1046

Po=570 torr and the volumes have been corrected to STP. a. Show that the data agree with BET b. Determine the BET surface area.

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Adsorption desorption isotherms

Nonporous
Completion of first layer and beginning of additional layers

Porous
Desorption branch, behaves, according to Kelvin equation

Interaction with most energetic region of the solid

Adsorbing beginning bulk condesation into liquid

Same but rise more rapid at intermediate and hysteresis loop occur on desorption. Typical meso (> 2 nm) and macroporous (50 nm). Adsorbate molecules within the pores experience enhanced attraction thus lead to early condensation.

Micropores: dpore< 2 nm (N2 diameter around 0.35 nm) Mesopores: 2 nm < dpore< 50 nm Macropores: dpore> 50 nm

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Type of adsorption isotherm (IUPAC)

Characteristic of microporous and the amount adsorbed is micropore volume Nonporous or large pores C>2

Low affinity adsorption. Valueless in surface and pore analysis C<2

Type 2 with hysteresis due to capillary condensation

Type 3 with hysteresis

Multisteps adsorption for noble gas. Rare

Aaron Nackos, Adsorption, surface area and porosity - web

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de Boers hysteresis Loops

Catalysis Rate
Reaction catalysed by solid surface. The rate is determined by the amount of gas adsorbed or fraction of active site covered. Rate = k

Rate = k = k

V bP =k Vm 1 + bP

If reactant gas strongly adsorbed or high pressure, bP>>1

Rate = k

Zero order reaction

If reactant gas weakly adsorbed or low pressure, bP<<1

Rate = kbP

First order reaction

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Reaction can be followed by the change of pressure of reacting gas. For first order

rate =
Where k=kb. Integration gives

dPA = k ' PA dt

ln

PA.0 = k't PA

Found to be correct model for many reactions on solid surface. For cases of strongly adsorbed, zero order

rate =
Integrated form

dPA =k dt

PA, 0 PA = kt

There are also intermediate cases

dPA bP =k dt 1 + bP

In can be shown to the integrated form is (DIY)

1 PA, 0 ln + ( PA,0 PA ) = kt b PA
intermediate

Zero order

1st order P

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