Non-Stoichiometric Compounds
Submitted by: Muhammad Tayyab (Bsf2201113)
Muhammad Mohsin (Bsf2201106)
Asad Ali (Bsf2205713)
Submitted to: Dr. Adnan Asghar
Course: Inorganic material Chemistry
Semester: (6th) morning
Session: 2022-2026
Department of Chemistry
DIVISION OF SCIENCE AND TECHNOLOGY
UNIVERISTY OF EDUCATION, LAHORE
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1. Introduction:
Stoichiometric compounds are those compounds in which elemental or ionic
composition can be represented by small simple whole number ratio (empirical
formula). For example, NaCl have same cationic and anionic ratio which is 1:1 can
be represented by simple whole number ratio. Similarly Iron (II) oxide have simple
whole number ratio which is 1:1.
While non-stoichiometric compounds are those compounds in which elemental or
ionic composition cannot be represented by small simple whole number ratio, most
often, in such materials, some small percentage of atoms are missing or too many
atoms are packed into an otherwise perfect lattice work.
These compounds are also called as “Berthollide” and “Daltonides”. These names
come from Claude Louise Bethollet and John Dalton respectively, who in 19 th
century advocated the rival theories of the composition of substances.
For example, at 1000oC Composition of ‘‘iron monoxide’’ which is sometimes
referred to as wusite, Fe1-x O, varies from Fe0.89O to Fe0.96O.
Charge neutrality may also be maintained by electronic defects (electrons or holes
trapped at the defects). It also requires at least one element to exist in more than
one oxidation state. Hence deviations from stoichiometry are common only for d-
and f-block elements, which commonly adopt two or more oxidation states and for
some heavy p-block metals that have two accessible oxidation states. These
compounds are substances that exhibit variable composition but retains the same
structure type.
1.1. Table
Representative composition ranges of non-stoichiometry binary hydrides, oxides
and sulfides
d block
Hydrides:
TiHx 1-2
ZrHx 1.5 - 1.6
HfHx 1.7 - 1.8
NbHx 0.64 - 1.0
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Oxides (Rock salt type) :
TiOx
0.7 – 2.5
VOx
0.9 – 1.20
Sulfides:
ZrSx
0.9 – 1.0
YSx
0.9 – 1.0
Examples of Non-Stoichiometric Structures:
Compound Structure Type Deviation
Fe₀.₉₅O NaCl-type Metal vacancies
Zn₁₊ₓO Wurtzite Excess Zn atoms
TiO₁.₉₅ Rutile Oxygen vacancies
Cu₂O₁₋ₓ Cuprite Anion vacancies
2. Non Stoichiometric defects:
Cation to anion ratio disturbed
C : A
100 100 (stoichiometric defect)
99 100 (non-stoichiometric defect)
100 99 (non-stoichiometric defect)
Electrical conductivity maintained
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2.1. Metal excess defect:
A metal excess defect is a type of point defect that occurs in crystals where there
are more metal ions than anion ions. This disrupts the ideal crystalline structure
and can affect the material's properties.
There are two main ways that metal excess defects can occur:
a) Anionic vacancies: This occurs when an anion is missing from its lattice site.
The missing anion leaves a hole, which can be occupied by an electron to
maintain electrical neutrality.
Example:
➢ When NaCl is heated in a sodium Na vapor environment, excess sodium Na
atoms deposit on the surface of the NaCl crystal, causing Cl – ions to diffuse
into the surface and interact with the Na + ions, resulting eventually in the loss
of an electron.
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b) Interstitial cations: In this type of defect, extra cations are present at
interstitial sites (the spaces between atoms in a crystal lattice). This can occur if
the crystal incorporates impurities during growth, or if it is subjected to high
temperatures or pressures.
Example:
➢ For example, if zinc oxide (ZnO) is grown in an oxygen-deficient environment,
some of the zinc ions will occupy interstitial sites rather than their normal
lattice sites.
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Metal excess defects can have a number of effects on the properties of a material.
For example, they can:
➢ Increase electrical conductivity: Because the extra electrons in the crystal
lattice can move freely, metal excess defects can increase the conductivity of a
material. This can be beneficial in some applications, such as in solid-state
electrolytes.
➢ Change the color of a material: The presence of metal excess defects can
sometimes alter the way that a material absorbs light. This can cause the
material to appear colored. For example, zinc oxide (ZnO) is normally white,
but it can turn yellow when it is heated in an oxygen-deficient environment.
This is because the loss of oxygen creates metal excess defects in the crystal
lattice.
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2.2. Metal deficiency defect:
A metal deficiency defect is a type of point defect in a crystal lattice where a cation
(positively charged ion) is missing from its regular lattice site. This creates a
vacancy in the lattice and disrupts the overall electrical neutrality of the crystal.
Since most ionic compounds rely on a balance of positive and negative charges, a
metal deficiency defect needs to be compensated for to maintain electrical
neutrality. This compensation can happen in two ways:
a) Formation of cation vacancies with a higher valence:
In some cases, the remaining cations in the crystal lattice can increase their valence
state.
For example:
➢ In a compound like FeO iron(II) oxide, some of the Fe 2+ ions might be missing
from the lattice. To compensate for the missing positive charge, one or two of
the remaining Fe2+ ions can be oxidized to Fe³⁺ ions. This keeps the overall
charge of the crystal balanced but changes the ideal ratio of Fe to O ions in the
crystal, making it non-stoichiometric.
b) Presence of excess anions:
Anions (negatively charged ions) can occupy interstitial sites (spaces between regular
lattice sites) in the crystal lattice. This effectively adds extra negative charge to
compensate for the missing positive charge from the missing cation.
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Metal deficiency defects are more commonly observed in crystals formed by
elements that can exhibit variable oxidation states, such as transition metals. These
defects can have a significant impact on the physical properties of a material, such
as its electrical conductivity, diffusivity, and mechanical strength.
3. Properties of Non-Stoichiometric Compounds
Non-stoichiometric compounds are a fascinating class of materials with unique
properties stemming from their imperfect crystal structures. Unlike stoichiometric
compounds where elements combine in a simple whole number ratio, non-
stoichiometric compounds have a composition that deviates slightly from this ideal
formula. This deviation arises due to the presence of crystallographic defects,
which can be missing atoms (vacancies) or extra atoms occupying interstitial
positions.
Here's a detailed breakdown of the key properties of non-stoichiometric
compounds:
3.1. Electrical Conductivity:
• The presence of defects creates mobile charged species within the crystal
lattice. For example, missing cations (positively charged ions) in a metal oxide
can be compensated by the presence of an extra electron, making the material
an n-type semiconductor.
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• Conversely, extra cations can introduce holes, leading to p-type conductivity.
• By controlling the degree of non-stoichiometry, the electrical conductivity of
the material can be tuned for specific applications.
3.2. Magnetism:
• Non-stoichiometry can influence the oxidation state of certain elements in the
compound. This, in turn, affects the magnetic properties.
• For instance, in iron(II) oxide (FeO), vacancies at the iron sites can lead to the
formation of Fe(III) ions, altering the overall magnetic behavior of the material
and making it .
3.3. Color:
• The distribution of electronic energy levels within the material can be affected
by non-stoichiometry. This can influence the absorption and emission of light,
leading to variations in color.
• Wustite (FeO with iron vacancies): compared to stoichiometric FeO (green),
wustite exhibits a non-stoichiometric black color. The presence of iron
vacancies creates new energy levels that allow for the absorption of a wider
range of visible light wavelengths, resulting in a darker appearance.
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• Titanium Dioxide (TiO2): Non-stoichiometric TiO2 with oxygen vacancies can
exhibit a slightly yellow or blue hue compared to the typical white color of
stoichiometric TiO2. The vacancies create energy levels that can absorb light in
the ultraviolet range, influencing the overall color perception.
3.4. Catalytic Activity:
• The defects in non-stoichiometric compounds can act as active sites for
chemical reactions.
• These sites can provide suitable locations for reactant molecules to adsorb and
participate in reactions.
• When TiO2 has oxygen vacancies, it becomes a more effective photo catalyst
for water splitting. The vacancies create electron-trapping sites that participate
in the light-driven generation of reactive oxygen species, which are crucial for
breaking down water molecules.
3.5. Thermal expansion:
• In some cases, non-stoichiometry can lead to an increase in thermal expansion.
This can occur due to the presence of vacancies within the crystal lattice can
act as additional free space.
• Non-stoichiometry can also lead to a decrease in thermal expansion in certain
scenarios. If extra atoms (interstitials) occupy positions within the lattice, they
can create a more tightly packed structure resulting in a lower overall
expansion.
• Doping zirconia with certain elements can create vacancies, leading to a higher
thermal expansion coefficient compared to the pure stoichiometric form. This
property is utilized in materials like yttria-stabilized zirconia (YSZ).
• Non-stoichiometric Tungsten Bronzes (MxWO3) exhibit a fascinating
dependence of thermal expansion on their non-stoichiometry. At specific
compositions, they can show a very low thermal expansion coefficient.
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3.6. Other Properties:
Non-stoichiometry can also influence other properties, including:
• Mechanical strength
• Optical properties (refractive index)
4. Factors Affecting Properties:
• The type of defect (vacancy, interstitial)
• The extent of non-stoichiometry (deviation from ideal formula)
• The arrangement and distribution of defects within the crystal lattice
5. Variable Valency & Transition Metals
One major reason of non-stoichiometry is common in transition metals is due to their ability to
exist in multiple oxidation states:
Fe → Fe²⁺ and Fe³⁺
Mn → Mn²⁺, Mn³⁺, Mn⁴⁺
Ti → Ti³⁺ and Ti⁴⁺
This flexibility allows them to compensate for missing or excess atoms, maintaining charge
balance without disturbing the crystal too much.
6. Periodic Table Perspective
Groups involved: Primarily d-block (Groups 3 to 12)
Periods involved: Periods 4, 5, and 6
Also observed in some f-block elements (lanthanides & actinides)
Examples:
Element Group Compound Example
Fe (Iron) Group 8 Fe₀.₉₅O
Cu (Copper) Group 11 Cu₂O₁₋ₓ
Ti (Titanium) Group 4 TiO₁.₉₅
V (Vanadium) Group 5 VO₁.₈
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7. Detection Methods of non stoichiometric compounds:
There are large number of methods for detection of non-stoichiometric compounds:
• X-ray Analysis
• Density Measurements
• Magnetic Measurements
• UV visible spectra
• Neutron diffraction
7.1. X-ray analysis:
It is a method to detect non-stoichiometric compounds. By subjecting a sample to X-
ray radiation and analyzing the resulting diffraction pattern, we can determine the
arrangement of atoms in the crystal lattice. Any deviations from the expected
stoichiometry can be observed through changes in the diffraction pattern. It's a
really powerful technique that provides valuable insights into the composition and
structure of compounds.
7.2. Density method:
To detect non-stoichiometric compounds, one method is the density method. It
involves comparing the experimental density of a compound with the theoretical
density calculated from its stoichiometry. If the experimental density doesn't match
the theoretical density, it suggests the presence of non-stoichiometry.
7.3. Magnetic measurements:
It is used to detect non-stoichiometric compounds. By measuring the magnetic
properties of a compound, such as its magnetic susceptibility or magnetization, we
can gain insights into its stoichiometry. Non-stoichiometric compounds often
exhibit deviations in their magnetic behavior compared to their stoichiometric
counterparts. It is a method that helps us to understand the
composition of materials.
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7.4. Neutron diffraction:
It is a powerful method to detect non-stoichiometric compounds. By bombarding a
sample with neutrons and analyzing the resulting diffraction pattern, we can
determine the arrangement of atoms in the crystal lattice. Any deviations from the
expected stoichiometry can be observed through changes in the diffraction pattern.
It is a technique that provides valuable insights into the structure of compounds.
7.5. UV-visible spectroscopy:
It is another method to detect non-stoichiometric compounds. It involves analyzing
the absorption or transmission of light in the UV-visible range by the compound.
Different stoichiometries can exhibit distinct absorption patterns, so by comparing
the spectra of the compound with the expected stoichiometric ratios, we can
identify any deviations.
8. Applications of Non-Stoichiometric Compounds
Non stoichiometric compounds find their applications in various fields:
8.4. Electrical Applications:
Non-stoichiometric metal oxides play a crucial role in various electronic devices
due to their ability to conduct electricity. This conductivity arises from defects in
their crystal structure created by the non-stoichiometry.
Vacancies or extra ions: When a metal oxide is non-stoichiometric, it may have
vacancies where an atom should be (e.g., missing oxygen atoms in titanium
dioxide, TiO₂). Alternatively, it might have extra ions occupying interstitial
spaces.
These defects create mobile charged species (electrons or holes) that can carry
current.
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Examples:
• Solid Oxide Fuel Cells (SOFCs): These electrochemical devices convert
chemical energy into electrical energy. A key component is the electrolyte,
which allows oxygen ions (O²⁻) to pass through but not electrons. Yttria-
stabilized zirconia (YSZ) is a common non-stoichiometric ceramic used as the
electrolyte in SOFCs. The presence of oxygen vacancies in YSZ allows for
high oxygen ion conductivity at high temperatures.
• Thermistors: These are temperature-sensitive resistors whose resistance
changes with temperature. Non-stoichiometric materials can be used as
thermistors because the number of mobile charges and, consequently, the
conductivity, is often temperature dependent. As the temperature increases,
more defects are created or become mobile, leading to higher conductivity.
8.5. Catalytic Applications:
Non-stoichiometry can create imperfections on the surface of a material, providing
active sites for catalytic reactions. These active sites can weaken bonds in reactant
molecules, facilitating their reaction.
Examples:
• DeNOx catalysts: Nitrogen oxides (NOx) are pollutants emitted from vehicle
exhaust. DeNOx catalysts reduce these emissions by converting them into less
harmful nitrogen (N₂) and oxygen (O₂). Non-stoichiometric oxides like cerium
dioxide (CeO₂) are effective DeNOx catalysts. The presence of cerium ions in
different oxidation states (Ce³⁺ and Ce⁴⁺) on the non-stoichiometric CeO₂
surface facilitates the reduction of NOx molecules.
• Water-gas shift reaction catalysts: This reaction (CO + H₂O → CO₂ + H₂)
is important for syngas production (a mixture of CO and H₂) and hydrogen
purification. Non-stoichiometric metal oxides like iron(II) oxide (FeO) can be
used as catalysts for this reaction. The missing iron atoms in non-
stoichiometric FeO create active sites for the reaction between CO and H₂O
molecules.
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8.6. Magnetic Applications:
The magnetic properties of materials can be influenced by non-stoichiometry. The
presence of vacancies or extra electrons can alter the electronic configuration of
atoms and their magnetic behavior.
Example:
• Mn-Zn ferrites: These are ceramic materials with various industrial
applications due to their magnetic properties. By carefully controlling the
oxygen content in Mn-Zn ferrites, manufacturers can tailor their magnetic
properties. This allows them to be used in transformers (where high
permeability is desired) or inductor cores (where high electrical resistivity is
needed).
8.7. Superconductors:
Superconductors are materials that exhibit zero electrical resistance at very low
temperatures. Non-stoichiometry plays a crucial role in the development of high-
temperature superconductors. These materials become superconducting at
temperatures much higher than traditional superconductors, making them more
practical for various applications.
Example:
• Yttrium Barium Copper Oxide (YBCO) with the formula YBa 2Cu₃O₇₋x
(where x can vary between 0 and 1) is a well-known high-temperature
superconductor. The oxygen vacancy (represented by x) significantly affects its
superconducting properties. As the value of x increases (more oxygen
vacancies), the transition temperature to the superconducting state decreases.
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