PROCESSES AT SOLID SURFACES

Introduction
Processes at solid surfaces govern the viability of

industry both constructively, as in catalysis, and destructively, as in corrosion.

Chemical reactions at solid surfaces may differ

sharply from reactions in the bulk, for reaction pathways of much lower activation energy may be provided, and hence result in catalysis.
The concept of a solid surface has been extended in

recent years with the availability of micro porous materials as catalysts.

The Growth and Structure of Solid Surface

The attachment of particles to a surface is

called adsorption.

The substance that adsorbs is the adsorbate The underlying material that we are

concerned with in this section is the adsorbent or substrate.

The reverse of adsorption is desorption.

Perfect Crystal Surface

A simple picture of a perfect crystal surface is as a tray of oranges in a grocery store

Surfaces Defect

The Extent of Adsorption

The extent of surface coverage is normally expressed as the fractional coverage,

 The fractional coverage is often expressed in terms

of the volume of adsorbate adsorbed by V = V

where V~ 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.

Technique of adsorption
One commonly used technique is therefore to

monitor the rates of flow of gas into and out of the system: the difference is the rate of gas uptake by the sample. Integration of this rate then gives the fractional coverage at any stage.

Technique of Desorption
In flash desorption the sample is suddenly heated

(electrically) and the resulting rise of pressure is interpreted in terms of the amount of adsorbate originally on the sample.
Gravimetry involeves weighing of the sample

during the desorption

Physisorption and Chemisorption

Physisorption
Van der walls interaction
Enthalpy of adsorption less than about 40 kJ/mol No appreciable activation energy involved in adsorption process

Chemisorption
Covalent bond
Enthalpy of adsorption greater than about 80 kJ/mol Activation energy may be involved in adsorption process

Multilayer adsorption occurs Adsorption leads to a monolayer , at most Exothermic Exothermic

Enthalphy of adsorption

Adsorption Isotherms
The free gas and the adsorbed gas are in dynamic

equilibrium, and the fractional coverage of the surface depends on the pressure of the overlying gas. The variation of with pressure at a chosen temperature is called the adsorption isotherm.

Langmuir Isotherms
The simplest physically plausible isotherm is based

on three assumptions: 1 Adsorption cannot proceed beyond monolayer coverage.

2
3

All sites are equivalent and the surface is uniform

The ability of a molecule to adsorb at a given site is independent of the occupation of neighbouring sites (that is, there are no interactions between adsorbed molecules).

Example

Graph of example 25.1

Self Test