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Chromatographic Analysis of Adsorption: Chemisorption and/or Physisorption

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Abstract

Eight systems namely the C6H6 /Fe2O3, C6H6/NO2/Fe2O3, C6H5CH3/Fe2O3, C6H5CH3/NO2/Fe2O3, C6H6/ZnO, C6H6/NO2/ZnO, C6H5CH3/ZnO, C6H5CH3/NO2/ZnO are examined through a version of inverse gas chromatography and six physicochemical adsorption quantities are determined for each heterogeneous system. Thus, the reversed flow—(inverse) gas chromatography is used for the investigation and study of adsorption phenomena taking place on these heterogeneous solid surfaces. In the case of iron oxide the presence of nitrogen dioxide facilitates the chemisorption. This is not obvious in the case of zinc oxide. However, nitrogen dioxide facilitates the adsorption of benzene and toluene through van der Waals forces in both oxides. Through the experimental local quantities determined and the detailed time-resolved analysis, useful information for the nature and the strength of the adsorbate–adsorbent as well as the adsorbate–adsorbate interactions have been extracted giving an insight into the topography of the active sites and the nature of the surface bonds.

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Acknowledgments

The authors acknowledge the financial support under the research program PYTHAGORAS II 2005–2007. The project is co-funded by the European Social Fund (75%) and National Resources (25%).

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Authors and Affiliations

  1. School of Chemical Engineering, National Technical University of Athens, 15780, Zografou, Athens, Greece

    Triantafyllia Agelakopoulou & Fani Roubani-Kalantzopoulou

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  1. Triantafyllia Agelakopoulou
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  2. Fani Roubani-Kalantzopoulou
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Corresponding author

Correspondence to Fani Roubani-Kalantzopoulou.

Glossary

H

height of sample peaks resulting from the flow reversal (cm)

t

time (min)

M

response factor of the detector

G

calibration factor of the detector (cm/mol cm−3)

c(l′, t)

measured sampling concentration of the gas at x = l′ (mol cm−3)

c * S

equilibrium adsorbed concentration of the gas adsorbate at time t (mol g−1)

a S

amount of solid material per unit length of column bed (g cm−1)

y

length coordinate along section L 2 (cm)

a y

cross sectional area of the void space in region y (cm2)

k 1

local adsorption parameter (s−1)

k −1

desorption rate constant (s−1)

k 2

surface reaction rate constant (s−1)

c y

gaseous concentration of the adsorbate as a function of time t and coordinate y along the column (mol cm−3)

D 1

diffusion coefficient of this gas adsorbate into the nitrogen carrier gas (cm2 s−1)

D 2

diffusion coefficient of this gas adsorbate into the gas phase in section y (cm2 s−1)

ε

local adsorption energies (kJ mol−1)

θ t

local adsorption isotherm (dimensionless)

c *smax

local monolayer capacity (mol g−1)

φ(ε; t)

probability distribution function for adsorption energies (mol kJ−1 min−1)

β

parameter for lateral interactions (dimensionless)

ω

lateral interaction energy (dimensionless)

z

number of neighbors for each adsorption site

R

gas constant

k

Boltzmann’s constant

h

Planck’s constant

u s (T)

partition function of the adsorbed molecule

b g (T)

partition function for rotations-vibrations in the gas phase

L 1

length of the empty section z of diffusion column (cm)

L 2

length of the filled section y of diffusion column (cm)

u

linear flow velocity of carrier gas (cm s−1)

M

molar mass of the adsorbate (kg mol−1)

n s

amount of adsorbate injected (mol)

SSA

specific surface area (cm2 g−1)

Ε

external porosity (dimensionless)

T

temperature (K)

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Agelakopoulou, T., Roubani-Kalantzopoulou, F. Chromatographic Analysis of Adsorption: Chemisorption and/or Physisorption. Chroma 69, 243–255 (2009). https://doi.org/10.1365/s10337-008-0882-1

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  • DOI: https://doi.org/10.1365/s10337-008-0882-1

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