Surfaces Chemistry

Molecular Adsorption
. Adsorbent
. Adsorpate

Fractional Coverage .

=



=

where V equal to volume of adsorbate adsorbed and, is the volume adsorbate of complete
one layer coverage.

1
Type of Adsorption

)Physical Adsorption (physisorption
)Chemical Adsorption (Chemisorption

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M. A. Ibraheem
Surfaces Chemistry

.1
.2
.3 .
.
.4
.5
.6
.7
~20 1 .8
.9
.10

:
.
.1
.2
= 200 400 1 .3
( ) .4
.5
.6
.7
.8

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M. A. Ibraheem
Surfaces Chemistry

2
Surface Area of Adsorption




= 6.023 1023 1
22.4 . 1
Vmono
V

= = ,

Where Vm is the total volume of the surface

=


=


3
= = 3
4

1
3 3
(= )
4

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M. A. Ibraheem
Surfaces Chemistry

2
3 3
( = = 2 )
4

.
2
3 3
= 1
( 6.023 1023 1 )
22.4 . 4

3
IUPAC

& Zeolite Microporous
Activated carbon4

Macrooporous

Mesoporous Al2O3
SiO2

IUPAC
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M. A. Ibraheem
Surfaces Chemistry

.
.Isotherm

.1
.2 .
.3
.
Kd , Ka


) = (1

() N


=

( )
Langmuir Isotherm

= =
1 +
Exp : The Data Given below are for the adsorption of CO on charcoal at 273 K. Confirm that
they fit the Langmuir isotherm and find the constant K and the volume corresponding to
)complete coverage. In each case V has corrected to 1.00 atm (101.325 k Pa
P kPa 13.3 26.7 40.0 53.3 66.7 80.0 93.3
V cm3 10.2 18.6 25.5 31.5 36.9 41.6 46.1

Sol
= +

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M. A. Ibraheem
Surfaces Chemistry

With = , where is the volume corresponding to complete coverage some

denoted as So
1
= +

Hence a plot of P/V against P should give a straight line of slope 1 and intercept 1

the slope according to the curve is 0.009, so = 111 3 , the intercept at

= 1.1986 ~1.2,
2.5
1
=
(111 ) (1.20 3 )
3 2

(P Kpa)/V cm3)
1.5

= 7.51 103 1 1 y = 0.009x + 1.1986

0.5

0
0 20 40 60 80 100
(P KPa)

( )

2
= {(1 )}



= ()2


1
()2
=
1 + ()1/2
Different Value of K will obtain accordingly
with different temp , the temperature
dependence of K can be used to obtain
the isosteric enthalpy of adsorption.
the standard enthalpy of adsorption
at a fixed value The Langmuir isotherm for
different values of K: (a) non-
dissociative adsorption; (b)
dissociative adsorption, X2(gas)Page
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M. A. Ibraheem
Surfaces Chemistry

ln
( = )
2
Isosteric enthalpy of adsorption from the equilibrium constant.
BET Isotherm of multi layers 5
.
.
6 .
Stephen Brunauer, Paul Emmet and Edward Teller

. BET Isotherm


1 )( 1
= + ) (
) (
= ,
1

( = )/

Vmon = volume of gas required to form monolayer

Va= volume of gas adsorbed at pressure p
) ( Po: Saturated presuure of the absorbate

P: pressure of the adsorptive in equilibrium with the adsorbate. , : relative pressure

Or it could re arrange it as7

= , =
}) (1 ){1 (1

In a plot P/(Va(P-Po) versus P/Po, the slope and interception of the drawn best line can be
determined and c and Vm can be estimated.

)P/(Va(P-Po

Slope= m

Intercept=b

Page 7 of 9
M. A. Ibraheem P/Po
Surfaces Chemistry

1 ( 1)
= , =

When the value of P/Po less than 0.05 and greater than 0.35, BET plot is not linear. Then
other techniques must be used to evaluate Vm.

Determination of Specific Surface Area

BET

=


N
16.2A2 Adsorbate cross surface area Acs
M


= =

W
General solved examples
1. Heat of Adsorption Calculation
Measurements of N2 adsorption onto charcoal were performed and N2 adsorption was low.
Use these measurement to calculate the heat of adsorption of N2 onto charcoal ?
The adsorb amount of N2 at different temperature and pressure are below
0.92 ml/g at 4.8 and 190k
0.92 ml/g at 32bar and 250k
4

3
At low pressure the isotherm will show a linear
2

Section
1

= 0
1 + 0 2 P4 6 8

values is not available , but we know how much is adsorbed. So

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M. A. Ibraheem
Surfaces Chemistry

how much is adsorbed divided by the amount of N2 to cover the whole surface at low
pressure is equal to the coverage fraction or . So is proportional to the amount of gas was
adsorbed. Let assume is the proportional constant then
(0.92) = 1 (4.8 ) 1 = 0.1917
And at 250 k
(0.92) = 2 (32) 2 = 0.0287
K is related to the heat of adsorption

1 1 1
( )
=
= 1 2
2

0.1917
(
1

1
)
= 190 250
0.02825

ln 6.667 = (1.263 103 )


1.897 = (1.263 103 ) = 1.5 103


So = 8.314 (1.5 103 ) = 12.5 /

1
https://www.emedicalprep.com/study-material/chemistry/surface-chemistry/adsorption/
2
http://www.chemistrylearning.com/adsorption/#prettyPhoto
3
Recommendations: Reporting Physisorption Data for GasrSolid Systems with Special Reference to
the Determination of Surface Area and Porosity, IUPAC Commission on Colloid and Surface
Chemistry Including Catalysis, Pure Appl. Chem., 57 _1985. 603; Recommendations for the
Characterization of Porous Solids, IUPAC Commission on Colloid and Surface Chemistry, Pure
Appl. Chem., 66 _1994. 1739.
4
http://www.microtrac-bel.com/en/tech/bel/seminar02.html
5
Brunauer, Stephen; Emmett, P. H.; Teller, Edward (1938). "Adsorption of Gases in Multimolecular
Layers". Journal of the American Chemical Society. 60 (2): 309319
6
https://www.tau.ac.il/~phchlab/experiments_new/adsorption/Theory.html
7
Physical Chemistry P.W Atkins 9th ed.page 892.

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M. A. Ibraheem