CHEM-307
Nonstoichiometric compounds
1. Introduction
In solid-state chemistry, the study of compound has been expanded to the crystal structure
level. The law of definite proportions, the law of constant composition, and the law of
conservation of mass state that a chemical compound always contains exactly the same
proportion of elements by mass. All chemical compounds obeying these laws are called as
stoichiometric compounds.
While nonstoichiometric compounds are the chemical compounds deviated from stoichi-ometry,
namely their elemental composition cannot be represented by a ratio of well-defined natural
numbers, and therefore violate the law of definite proportion.
These nonstoichiometric compounds exhibit different properties such as conductivity,
magnetism, catalytic nature, color, and other unique solid-state properties, which have important
technological [Link] are significant structural changes that are seen in
nonstoichiometric compounds. The phase of matter changes as external conditions such as
pressure, temperature, or chemical composition are varied. Due to sudden change in these
external thermodynamical conditions, the crystalline structure also changes.
2 History
Non-stoichiometric compounds are also known as berthollides, as violators of the law of definite
proportions, as opposed to the stoichiometric [Link] daltonides. The names come from
Claude Louis Berthollet and John Dalton, respectively, who in the 19th century advocated rival
theories of the composition of substances. A thongh Dalton "won" for the most part, it was later
recognized that the law of definite proportions had important exceptionsnop Slokchiomet
3 Classification and point defect formation in nonstoichiometric compounds
Element composition is the main criteria to classify the nonstoichiometric compounds. These
compounds exist only in the condensed state.
•Transition metal oxides are generally nonstoichiometric
•Some nitrides and sulfides also comes undersuch category.
Most nonstoichiometric compounds have compositions that are close to those of stoichiometric
compounds and can be expressed by formulas such as WO3x, Co1xO, Zn1+xO, and Ni1xO, in
which x is a positive quantity much smaller than 1.
In the WO3x case, an oxygen vacancy would be formed, and in some cases, there is metallic
deficiency that is seen. Due to deviation from stoichiometric composition, it would result in the
formation of some lattice [Link], in some nonstoichiometric compounds, there are
anionic vacancies and in some, there are cationic vacancies. These vacancies are formed due
to defects in the lattice structures of crystalline substances, such as the absence of ions from
sites that would normally be occupied.
The crystallographic point defects are the main defects in which interstitial atoms and vacancies
resulting from excess or deficiency of a component element. Point defects are an important
cause of formation of the nonstoichiometric compounds
There are two main point defects in nonstoichiometric compounds namely:
a) Frenkel defect
b) Schottky defect
a) Frenkel defect
The Frenkel defect explains a defect in the molecule, where an atom or ion (normally, the
cation) leaves its own lattice site vacant and instead occupies a normally vacant site.
b) Schottky defect
The Schottky defect forms when vacancies are created when oppositely charged ions leave
their lattice sites. Formation of these vacancies in stoichiometric system helps in maintaining an
overall neutral charge in the ionic solid. These created vacancies are filled by the movement of
surrounding atoms, due to which new vacancies are formed. The formation of defects in the
crystal will lead to a
decrease in the density of the crystal or metal. This can be understood by Figure 1.
Occurrence:
Nonstoichiometry in nickel oxide:
Nickel oxide is an antiferromagnetic and [Link] oxide (NiO) has been among some of
the transition metal oxide, which is most thoroughly studied by the researchers. It can be easily
synthesized and is very low in preparation cost, the nature of this material is such that it has low
toxicity and it is environmental friendly. The condition of synthesis of the material plays very
[Link] the condition of sample preparation changes, then the oxygen content of the
sample also changes, and NiO of different stoichiometry (Ni1xO) can be obtained. In such
samples, the composition ratios between nickel and oxygen are not exactly 1:1. Because of
excess oxygen and vacancies on Ni site, nickel oxide thus becomes a p- type metal-deficit
[Link] findings of investigations done by authors suggest that Ni vacancy is the
most dominant point defect present in the system, rather than oxygen interstitial.
Reason:
The main reason for changes in properties could be the excess oxygen present in the samples.
This excess oxygen also changes the oxidation state of nickel, which produces a vacancy at the
metal side to produce cation vacant nickel oxide. As the temperature of sintering of precursor
increases, the excess of oxygen decreases. Due to increase in the excess of oxygen, densities
of nickel oxide and activation energy of electrical conductivity decrease, but the lattice
parameter of such samples is unaffected. The diffusion of vacancies to the crystal surface is the
main reason for the decrease in vacancies.
Iron Oxide
Nonstoichiometry is pervasive for metal oxides, especially when the metal is not in its highest
oxidation state. For example, although wüstite (ferrous oxide), has an ideal (stoichiometric)
formula FeO, the actual stoichiometry is closer to Fe(0.95)O. The non- stoichiometry reflect the
ease of oxidation of Fe+2 to Fe+3 effectively replacing a small portion of Fe+2 with two thirds
their number of Fe+3. Thus for every three "missing" Fe2+ ions, the crystal contains two Fe ions
to balance the charge. The composition of a non-stoichiometric compound usually varies in a
continuous manner over a narrow range. Thus, the formula for wüstite is written as Fe-O, where
x is-a-small number (0.05 in the previous example) representing the deviation from the "ideal"
formula.
Palladium hydrides
Palladium hydride is a nonstoichiometric material of the approximate composition PdH, (0.02<
x<0.58). This solid conducts hydrogen by virtue of the mobility of the hydrogen atoms within the
solid. It is sometimes difficult to determine if a material is non-stoichiometric or if the formula is
best represented by large numbers. The oxides of tungsten illustrate this situation. Starting from
the idealized material tungsten trioxide, one can generate a series of related materials that are
Tungsten oxides
slightly deficient in oxygen. These oxygen-deficient species can be described as WO3-x, but
infact they are stoichiometric species with large unit cells with the formulas WnO(3n-2), where n
=20, 24, 25, 40. Thus, the last species can be described with the stoichiometric formula W(40)
O(118). whereas the non-stoichiometric description WO(2.95)implies a more random distribution
of oxidevacancies,
Applications
Ion conduction
The migration of atoms within a solid is strongly influenced by the defects associated with non-
stoichiometry. These defect sites provide pathways for atoms and ions to migrate through the
otherwise dense ensemble of atoms that form the crystals. Oxygen sensors and solid state
batteries are two applications that rely on oxide vacancies.
Superconductivity Cuprate superconductor
Many superconductors are non-stoichiometric. For example, yttrium barium copper oxide,
arguably the most notable high-temperature superconductor, is a non-stoichiometric solid with
the formula YxBa2Cu3O7-x. The critical temperature of the superconductor depends on the
exact value of x. The stoichiometric species has x=0, but this value can be as great as 1 value
of x. The stoichiomeni spiros-at-this valorcan-been-graatol.
