I= ADSORPTION OF ALCOHOL VAPOURS ON YTTRIA STABILIZED ZIRCONIA CATALYSTS
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Title of Thesis
ADSORPTION OF ALCOHOL VAPOURS ON YTTRIA STABILIZED ZIRCONIA CATALYSTS

Author(s)
Faeza Imtiaz
Institute/University/Department Details
Department of Chemistry/ Quaid-i-Azam University
Session
2002
Subject
Physical Chemistry
Number of Pages
169
Keywords (Extracted from title, table of contents and abstract of thesis)
alcohol vapours, yttria stabilized zirconia catalysts, zirconia, yttria, 'ink bottle' pores

Abstract
Yttria stabilized zirconia powders were prepared with 3, 5, 8 and 10 mol% of added yttria. The structural analysis of these samples was carried out using X-Ray Diffraction, Particle Size Distribution, Nitrogen Adsorption, Mercury Porosimetric and Scanning Electron Microscopic techniques. The XRD studies indicated that the Z3 Y and Z5Y were tetragonal whereas Z8Y and ZIOY were found to be cubic in shape.

Surface area was calculated using Nitrogen Adsorption Isotherms. It was found that with an increase in mole percent of Y 20 j in zirconia, there was an increase in surface area up to 5 mol% but after that it started decreasing. Mieroporosity or the powders was calculated by applying Dubinin-Radushkevich equation to the data obtained from nitrogen adsorption. D-R plots were found to be linear in the low relative pressure region and then there was an upward deviation at higher relative pressure in all the five systems. This deviation from the linearity shows a heterogeneous system of micropores. The deviation may also be due to the capillary condensation in transitional pores or multilayer formation on the walls of macropores.

Pore size distribution in all the powders was studied using Mercury Porosimetric Technique. The irreversibility of hysteresis in Mercury Porograms indicated the presence of 'ink bottle' pores. The results obtained from SEM technique indicated that particles were round in shape. The particles were found to be of non-uniform size distribution.

Adsorption of MeOH EtOH, PrOH and BuOH on pure and yttria stabilized zirconia was carried out between 273 to 303K. The isotherms obtained were of Type II. The surface area was calculated using Langmuir and BET adsorption isotherm equations and was found maximum for Z5Y powder. The isosteric heat of adsorption was calculated. Heat of adsorption, in general, seemed to be consistent with the earlier proposed idea of two adsorption processes occurring simultaneously, one with a small activation energy and the other with a large activation energy.

Thermodynamic parameters such as change in free energy, entropy and enthalpy of adsorption were calculated using Virial isotherm. It was found that maximum adsorption had taken place on Z5Y sample. Most probably it was due to the strongest affinity of Z5Y for the alcohols among all the samples. IR spectroscopic studies were also carried out in the range 4000 to 400 cm -1 and the adsorption of alcohols was confirmed by the results obtained.

Water vapour adsorption on zirconia was also studied. The isotherm obtained was of Type V, a characteristic of weak gas-solid interactions. The value of surface area obtained from the water vapor adsorption was much lower than that obtained from the nitrogen adsorption.

Download Full Thesis
4796.97 KB
S. No. Chapter Title of the Chapters Page Size (KB)
1 0 Contents
413.57 KB
2 1 Introduction
512.51 KB
  1.1 Zirconia And Its Applications 1
  1.2 Importance Of Zirconia 3
  1.3 Motivation Of Work 3
  1.4 References 4
3 2 Adsorption
611.11 KB
  2.1 Adsorption Isotherm 12
  2.2 Theories Of Adsorption 15
  2.3 Reference 28
4 3 Experimental
180.71 KB
  3.1 Sample Preparation 30
  3.2 Representative Samples 31
  3.3 Adsorption Study 32
  3.4 Reference 36
5 4 Characterization Of The Samples Prepared Results And Discussion
1618.84 KB
  4.1 Scanning Electron Microscopy 37
  4.2 Particle Size Distribution 41
  4.3 Mercury Porosimetry 49
  4.4 X-Ray Diffraction 59
  4.5 Nitrogen Adsorption Measurements 70
  4.6 Water Vapor Adsorption 83
  4.7 References 88
6 5 Adsorption Of Alcohol Vapours Results And Discussion
1655.05 KB
  5.1 Types Of Isotherms 90
  5.2 Surface Area 103
  5.3 Isosteric Heat Of Adsorption 112
  5.4 Thermodynamic Parameters Determined From A Varial Isotherm Expression 134
  5.5 Infrared Spectroscopic Studies Of The Zirconia Powders After Alcohol Adsorption Conclusion 148
  5.6 References 151