CHEMICAL PROPERTIES OF ADVANCE INORGANIC

MATERIALS:
Chemical properties of advanced inorganic materials include the following:

i. Reactivity of advanced inorganic materials

ii. Chemical durability and corrosion resistance of advanced inorganic materi-
als

Reactivity of Advanced Inorganic Materials

Advanced inorganic materials exhibit a wide range of reactivities that are crucial
for their applications in various fields such as catalysis, energy storage, electronic
devices, and environmental remediation. The reactivity of these materials is influ-
enced by their composition, structure, surface properties, and electronic character-
istics. This detailed note explores the different aspects of reactivity in advanced in-
organic materials.

Types of Reactivity:
1- Redox Reactivity
Redox reactions involve the transfer of electrons between species. Advanced inor-
ganic materials can act as oxidizing agents (accepting electrons) or reducing agents
(donating electrons).

Oxidizing Agents: Materials such as permanganates (KMnO₄) and dichromates

(K₂Cr₂O₇) are strong oxidizing agents used in various chemical reactions, includ -
ing organic synthesis and wastewater treatment.

Reducing Agents: Metal hydrides (LiAlH₄), metal powders (Zn, Fe), and certain
metal complexes can serve as reducing agents, facilitating reactions that require
electron donation.

2- Acid-Base Reactivity
Inorganic materials can exhibit acidic or basic properties, influencing their reactiv-
ity in acid-base reactions.

Acidic Materials: Transition metal oxides (e.g., V₂O₅, MoO₃) and sulfates
(H₂SO₄) act as acids, donating protons or accepting electron pairs. These materials
are often used in catalysis and chemical synthesis.

Basic Materials: Oxides (e.g., MgO, CaO) and hydroxides (NaOH, KOH) act as
bases, accepting protons or donating electron pairs. They are used in neutralization
reactions and as catalysts in various chemical processes.

3- Surface Reactivity:
The reactivity of inorganic materials is significantly influenced by their surface
properties, particularly for materials used in catalysis and adsorption.

Surface Area and Porosity:

High Surface Area: Materials like zeolites, mesoporous silicas, and metal-organic
frameworks (MOFs) have high surface areas, providing numerous active sites for
reactions. This property enhances their catalytic activity and adsorption capacity.

Porosity: The presence of pores in materials increases the accessibility of reactants

to active sites, improving the efficiency of catalytic and adsorption processes.

Surface Functionalization:

Functional Groups: The introduction of functional groups (e.g., hydroxyl, amine,

carboxyl) on the surface of inorganic materials can modify their reactivity, selec-
tivity, and interaction with other molecules.

Nano structuring: Creating nanostructured surfaces, such as nanoparticles,

nanowires, and nanotubes, can enhance the reactivity of inorganic materials due to
increased surface-to-volume ratios and unique electronic properties.

4- Catalytic Reactivity:
Advanced inorganic materials are widely used as catalysts due to their ability to fa-
cilitate chemical reactions without being consumed in the process.
Heterogeneous Catalysis:

Metal Oxides: Oxides of metals like TiO₂, CeO₂, and Al₂O₃ are commonly used
as catalysts or catalyst supports in heterogeneous catalysis. They facilitate reac-
tions such as hydrogenation, oxidation, and polymerization.

Zeolites: These microporous aluminosilicates are used in petrochemical refining,

isomerization, and cracking processes due to their high surface area, acidity, and
shape-selective properties.

Homogeneous Catalysis:

Transition Metal Complexes: Soluble complexes of metals like Pt, Pd, and Rh
are used in homogeneous catalysis. They are essential in processes such as hydro-
formylation, hydrogenation, and cross-coupling reactions.

Organometallic Compounds: Compounds containing metal-carbon bonds, such

as ferrocene and Grubbs' catalysts, are used in organic synthesis and polymeriza-
tion reactions.

5- Photo reactivity:
Photoreactive inorganic materials can absorb light and initiate chemical reactions,
making them useful in photocatalysis and photoelectrochemical applications.

Photocatalysis:

Titanium Dioxide (TiO₂): TiO₂ is widely used as a photocatalyst for water split-
ting, pollutant degradation, and organic synthesis due to its strong oxidative power
under UV light.

Zinc Oxide (ZnO): ZnO is another photocatalyst used in environmental remedia-

tion and antibacterial applications. It can degrade organic pollutants and produce
reactive oxygen species under UV light.

Photoelectrochemical Cells

Semiconductors: Materials like silicon (Si) and gallium arsenide (GaAs) are used
in photoelectrochemical cells for solar energy conversion. They generate electron-
hole pairs upon light absorption, driving redox reactions.
 6- Thermal Reactivity:
The thermal reactivity of inorganic materials is crucial for applications that involve
high temperatures, such as ceramic processing and combustion reactions.

Thermal Decomposition:

Metal Carbonates and Hydroxides: These materials decompose upon heating to

produce metal oxides and gases like CO₂ or H₂O. This property is used in pro-
cesses like lime production (CaCO₃ → CaO + CO₂).

Metal Nitrides and Carbides: Advanced materials like silicon carbide (SiC) and
titanium nitride (TiN) exhibit high thermal stability and are used in high-tempera-
ture applications, including cutting tools and furnace linings.

7- Combustion Reactivity:
Metal Powders: Metals like aluminum (Al) and magnesium (Mg) react exothermi-
cally with oxygen to produce metal oxides. These reactions are harnessed in py-
rotechnics and propellants.

Perovskite Oxides: Complex oxides with perovskite structures (e.g., LaFeO₃) are
used as catalysts in combustion reactions and solid oxide fuel cells due to their
thermal stability and redox properties

8- Electrochemical Reactivity:
Inorganic materials exhibit significant electrochemical reactivity, making them es-
sential in energy storage and conversion devices.

Batteries:

Lithium-Ion Batteries: Materials like lithium cobalt oxide (LiCoO₂) and lithium
iron phosphate (LiFePO₄) are used as cathodes in lithium-ion batteries due to their
ability to undergo reversible redox reactions.

Solid-State Batteries: Solid electrolytes like lithium garnets (Li₇La₃Zr₂O₁₂) en-

able the development of solid-state batteries with enhanced safety and energy den-
sity.
Fuel Cells:

Proton Exchange Membrane Fuel Cells (PEMFCs): Platinum-based catalysts

are used in PEMFCs to facilitate the hydrogen oxidation and oxygen reduction re-
actions.

Solid Oxide Fuel Cells (SOFCs): Ceramics like yttria-stabilized zirconia (YSZ)
are used as electrolytes in SOFCs, providing high ionic conductivity at elevated
temperatures.

Chemical Durability and Corrosion Resistance of Advanced Inor-

ganic Materials
Chemical durability and corrosion resistance are critical properties of advanced in-
organic materials, ensuring their longevity and reliability in various harsh environ-
ments. These properties are essential for applications in construction, transporta-
tion, energy, electronics, and biomedical devices. This detailed note explores the
factors influencing chemical durability and corrosion resistance, common types of
corrosion, mechanisms of protection, and examples of advanced inorganic materi-
als with superior durability and resistance.

1. Factors Influencing Chemical Durability and Corrosion Resis-

tance
Material Composition

 Metallic Inclusions: The presence of certain metals (e.g., chromium in

stainless steel) enhances corrosion resistance by forming protective oxide
layers.
 Alloying Elements: Additives such as molybdenum, nickel, and vanadium
improve the chemical durability and corrosion resistance of alloys.

Microstructure

 Grain Size: Fine-grained materials generally have higher resistance to cor-

rosion due to more uniform passive film formation.
 Phase Distribution: Homogeneous distribution of phases within the mate-
rial can reduce localized corrosion.
Surface Properties

 Surface Finish: Polished surfaces are less prone to corrosion compared to

rough surfaces that can trap corrosive agents.
 Coatings and Treatments: Surface treatments like anodizing, galvanizing,
and applying protective coatings enhance corrosion resistance.

2. Types of Corrosion

Uniform Corrosion

 Definition: Even material loss across the entire surface due to a uniform
chemical or electrochemical attack.
 Examples: Rusting of iron and steel in atmospheric environments.

Explanation: It is quite complex but it may be considered essentially as an

electrochemical phenomenon. During corrosion at a particular spot on the
surface of the object made of iron, oxidation takes place and that spot be-
have as anode. The electron released at this anodic spot move through the
metal and go to another spot on the metal and reduce oxygen to oxides at
that spot in presence of H+(which is believed to be available from H2CO3.
Hydrogen ion in water may also be available due to dissolution of other
acidic oxides from the atmosphere). This spot behave as cathode and here re-
duction takes place.

Localized Corrosion

 Pitting Corrosion: Localized attack that results in small pits or holes, often
caused by chlorides in stainless steels.
  Crevice Corrosion: Occurs in confined spaces (e.g., under gaskets or bolts)
where the local environment can become more aggressive.
 Galvanic Corrosion: Occurs when two different metals are electrically con-
nected in a corrosive environment, leading to accelerated corrosion of the
less noble metal.

Stress Corrosion Cracking (SCC)

 Definition: The combination of tensile stress and a corrosive environment

leading to cracking.
 Examples: SCC in high-strength alloys exposed to chlorides or hydrogen.

Intergranular Corrosion

 Definition: Corrosion along grain boundaries, often due to segregation of

impurities or depletion of protective elements.
 Examples: Sensitization of stainless steel due to chromium carbide precipi-
tation.

High-Temperature Corrosion

 Definition: Corrosion occurring at elevated temperatures, often involving

oxidation or sulfidation.
 Examples: Oxidation of turbine blades in gas turbines, sulfidation in petro-
chemical environments.

3. Mechanisms of Protection
Passivation

 Definition: Formation of a thin, protective oxide layer on the material sur-

face that prevents further oxidation.
 Examples: Stainless steel forms a chromium oxide layer, aluminum forms
an alumina layer.

Cathodic Protection

 Definition: Using a more reactive "sacrificial" anode to protect the main

metal structure from corrosion.
 Examples: Zinc coatings on steel (galvanization), magnesium anodes in wa-
ter heaters.
Inhibitors

 Definition: Chemicals added to the environment to decrease the corrosion

rate by forming a protective film or modifying the environment.
 Examples: Chromates, phosphates, and molybdates used in cooling systems
and pipelines.

Coatings

 Organic Coatings: Paints and polymers that provide a physical barrier

against corrosive agents.
 Inorganic Coatings: Ceramic and metallic coatings that offer thermal and
chemical protection.

4. Examples of Advanced Inorganic Materials with Superior Dura-

bility and Corrosion Resistance
Stainless Steel

 Composition: Iron-based alloys with at least 10.5% chromium, often with

additions of nickel, molybdenum, and nitrogen.
 Properties: Forms a passive chromium oxide layer, providing excellent re-
sistance to oxidation and various forms of corrosion.
 Applications: Construction, chemical processing, medical devices, and ma-
rine environments.

Titanium and Titanium Alloys

 Composition: Pure titanium or alloys with aluminum, vanadium, and other

elements.
 Properties: Forms a dense, stable oxide layer (TiO₂) that provides outstand-
ing resistance to corrosion in chloride environments and oxidizing media.
 Applications: Aerospace, marine, chemical processing, and biomedical im-
plants.

Aluminum and Aluminum Alloys

 Composition: Pure aluminum or alloys with elements such as copper, mag-

nesium, silicon, and zinc.
 Properties: Forms a protective alumina (Al₂O₃) layer, offering good resis-
tance to atmospheric and aqueous corrosion.
  Applications: Automotive, aerospace, packaging, and construction.

Nickel-Based Superalloys

 Composition: Alloys based on nickel with additions of chromium, cobalt,

molybdenum, and other elements.
 Properties: Excellent resistance to oxidation, sulfidation, and other forms of
high-temperature corrosion.
 Applications: Gas turbines, jet engines, nuclear reactors, and chemical pro-
cessing equipment.

Ceramics

 Composition: Oxides (e.g., Al₂O₃, ZrO₂), carbides (e.g., SiC, WC), ni-
trides (e.g., Si₃N₄, BN), and other non-metallic compounds.
 Properties: High chemical stability, resistance to oxidation and corrosion,
and superior thermal stability.
 Applications: Cutting tools, wear-resistant coatings, high-temperature com-
ponents, and electronic devices.

Glass and Glass-Ceramics

 Composition: Silica-based materials with various additives to modify prop-

erties.
 Properties: High resistance to chemical attack by acids, alkalis, and other
corrosive agents.
 Applications: Chemical laboratory equipment, windows, electronic dis-
plays, and cookware.

Theories of corrosion by sheama farheen savanur:

1- Acid theory of corrosion
2- Dry or chemical theory of corrosion
3- Wet or electrochemical theory of corrosion

 Acid theory of corrosion:

When a metal is exposed to an acidic environment, it undergoes a series of electrochemical reac-
tions leading to its degradation. The primary steps in this process include:

Anodic Reaction (Oxidation)

  At the anodic sites on the metal surface, the metal atoms lose electrons and become metal
ions, which dissolve into the surrounding medium.
 For example, the oxidation of iron in an acidic solution can be represented as:

Fe Fe+2 + 2e-

Cathodic Reaction (Reduction)

 At the cathodic sites, the electrons released during the anodic reaction are consumed by a
reduction reaction. In acidic solutions, hydrogen ions (H⁺) from the acid are typically re -
duced to hydrogen gas (H₂).
 The reduction reaction can be represented as:

2H+ + 2e− → H2 ↑

Overall Reaction

 The overall corrosion reaction, combining the anodic and cathodic reactions, involves the
dissolution of the metal and the evolution of hydrogen gas.
 For iron in hydrochloric acid (HCl), the overall reaction is:

Fe + 2HCl → FeCl2 + H2↑

 Dry or Chemical theory of Corrosion:

Corrosion on the surface of a metal is due to the direct reaction of atmospheric gases like oxy-
gen, halogens, oxides of sulphur, oxides of nitrogen, H2S and fumes of chemicals with corrosion
of metal. Oxygen is mainly responsible for the corrosion of most metals when compared to other
gases and chemical.

Types of dry corrosion:

1- Oxidation corrosion
2- Corrosion by other gases such as chlorine, SO2, H2S, NOx.
3- Liquid metal corrosion
1- Oxidation corrosion:

Some of the metals directly react with oxygen in the absence of moisture. Alkali and alkaline
earth metals react with O2 at room temperature and from corresponding oxides.

During oxidation of metal, metal oxide is formed as a thin film on the metallic surface which
products the metal from further corrosion. If diffusion of wither oxygen or metal is across this
layer, further corrosion is possible. Thus the layer of metal oxides play an important role in the
process of corrosion.
 2- Corrosion by other gases such as Cl2, SO2, H2S, NOx.

In dry atmosphere these gases react with metal and form corrosion products which may be pro-
tective or non protective. Dry Cl2 reacts with Ag to form Agcl which is a protective layer while
Sncl4 is volatile.

3- Liquid metal corrosion:

In several industries molten metal passes through metallic pipes and causes corrosion due to
dissolution are due to internal penetration. For example liquid metal Mercury dissolved most
metals by forming amalgams there by corroding them.

 Wet or electrochemical theory of corrosion:

This type of corrosion when the metal come in contact with a conducting liquid or when two dis-
similar metals are immersed or dipped partly in a solution. There is formation of a galvanic cell
on the surface of metals parts of metal surface act as anode and rest act as cathode the chemicals
in the environment and humanity acts as an electrolyte oxidation of anodic part takes and it result
in corrosion at a anode while reduction take place at cathode corrosion product is formed on the
surface of the metal between anode and cathode.
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