Reactivity in Solids

The reactivity of a substance depends on the elements and

geometric structures of the materials from which it is composed.
These structures depend not only on the properties of the specific elements
but also on how these elements interact with each other.
Factors affecting the reactivity
 the nature of the elements in the substrate
 the crystal faces which are exposed

The nature of the elements in the substrate

The reactivity of the substance refers to the catalytic activity which depends
on the d-band occupancy. It illustrates how the activity changes with
substrate across the periodic table. This can be explained better by volcano
curves typically known as ‘Balandin volcano plot’.

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Reactivity in Solids
The nature of the elements in the
substrate

 From the adjacent figure it is clear

that the catalytic activity is low for Sc on
the left-hand side of the periodic table.
 Activity increases to a maximum at Co
and then decreases again towards
copper on the right-hand side.
 From Sc to Mn the chemisorption of
CO is too strong to allow this reaction
proceed.
 Adsorption on Fe, Co and Ni gives a
sufficiently reactive CO adsorbate to
CO adsorption CO reactive CO
enable it to react once chemisorbed. too strong for once adsorption
 On Cu, the surface is insufficiently reaction chemisorbed too weak to
allow CO
reactive to crack the CO and so the bond
catalytic activity for hydrocarbon cleavage
synthesis is very low.
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Reactivity in Solids
The crystal faces which are exposed

 Studies of the reaction rate have been carried fcc (111) plan

out on a range of flat, stepped and kinked

surfaces.
 It is found that aromatization and cyclization
Terrace-flat
reactions proceed much faster on the (111) Surface
faces of fcc metals such as Pt compared to their fcc (111)
rates on (100) faces. terrace

 Aromatization on Pt has shown faster rates on

stepped and kinked surfaces. These two surface
morphology provide regions of considerable Stepped
reactivity. Surface

 The surface structure (both electronic and fcc (310)

step
fcc (111)
geometric) can be modified by adsorption of terrace
another species to alter the reactivity or to
improve efficiency of a given reaction.
Kinked
 The structure modifiers are also used to block Surface
the sites which are too reactive.
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Tarnishing Reactions
Definition[4]
Tarnishing is the term used for a process in which a solid reacts with a liquid or a
gas to form a solid compound which builds up a layer between the reactants. The
oxidation of metals constitutes the main group of such reactions.

Different Product Layers

Protective and Non-protective Layers
The course of the reaction will largely depend upon the compactness of the
product layer. If porous, it does not prevent the direct access of the gas to the
surface of the solid, so that the rate of the reaction will be independent of the
layer thickness and thus constant in time (linear growth).

The tarnishing reactivity depends on the morphology of the reaction products -

 If porous, it does not prevent the direct access of the gas to the surface of the
solid, so that the rate of the reaction will be independent of the layer thickness
 If a compact layer is formed, further reaction can only proceed by transport of
at least one of the reactants through the product, and therefore the rate will
decrease with increasing layer thickness and thus with time
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Tarnishing Reactions
Protective and Non-protective Layers
The porous non-protective layers can be formed if the ratio of the molar volume
of product to that of the reacting solid is smaller than unity. This happens in the
case of the oxidation of most metals of the groups IA and IIA.

Thick, Compact Product Layers

In this case the reaction where a relatively thick (> 10 - 5 cm) layer of compact
reaction products is formed, so that surface phenomena most often do not
control the rate or influence it by electrical effects, is considered.

The kinetics follow the parabolic rate law x  t1/2, corresponding to an expression
for the reaction rate of the form dx/dt = k/x (x = thickness of the layer at time k =
parabolic rate constant).

Kinetics of this form are characteristic for a reaction limited by transport

phenomena through a layer of increasing thickness.

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Tarnishing Reactions
Thick, Compact Product Layers[4]
This type of layer formation can be attributed to the following manners-
I) the metal/product interface and by
II) the product/gas interface.
The reaction mechanism must involve one of
the following ionic transport phenomena:
 Motion of interstitial cations or anion
vacancies from I to II, or
 Motion of cation vacancies or interstitial
anions from II to I.
 Simultaneously, an electronic transport
process must take place, i.e., either the flow of
electrons from I to II or of holes from II to I.
Fig. Schematic representation of
The tarnishing rate is controlled by the flow of transport phenomena which may be
the particles caused by the diffusion and involved in the tarnishing reaction M +
1/2X2 --> MX. All defects are assumed
migration.
to be singly ionized.
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Tarnishing Reactions
Thick, Compact Product Layers
Factor Influencing Tarnishing Rate
 The tarnishing rate can be altered by influencing the flow of the slower
diffusing reactant, i.e., of the electronic charge carriers and
 of the ionic defects if the product is mainly an electronic conductor.

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