PRESENTATION

Course Title: Pakistan Studies

Course Title:Course
Inorganic
Code: Chemistry-I
PKS-101
Course Code: CHEM-201
Submitted To: Mam Gulshan Naseem
Submitted To: Mam Umme Habiba
Submitted By:Submitted By: 22011510-009
22011510-009
22011510-06722011510-067
22011510-039 22011510-039
22011510-029
22011510-01322011510-029
22011510-013
 INTRODUCTION TO
POLYHALIDES
 Defination:

Polyhalides:
It is a type of organic compound that contains multiple halogen
atoms (such as fluorine, chlorine, bromine, or iodine) bonded to
a central carbon atom.
The term "polyhalide" literally means "many halides" and refers
to the presence of multiple halogen substituents in the molecule.
Polyhalides are commonly found in organic chemistry and are
used in various applications, including
1. Pharmaceuticals
2. Agrochemicals
3. Materials science
4. Catalysis
Examples.
1. Chloroform (CHCl3)
2. 2. Carbon tetrachloride (CCl4)

3. 3. Freons (e.g., CCl2F2)

4. 4. Polyvinyl chloride (PVC)

Polyhalides are often used as solvents, refrigerants, or

intermediates in chemical synthesis. However, some
polyhalides have raised environmental and health concerns
due to their toxicity and potential impact on ozone
depletion.
GENERAL
CHARACTERISTICS OF
POLYHALIDES
 Here are some examples to illustrate the general
characteristics of polyhalides:-
1. High reactivity: Chlorine trifluoride (ClF3) is a highly
reactive polyhalide that can react with water to form
hydrofluoric acid and hydrochloric acid.
2. Volatility: Bromine pentafluoride (BrF5) is a volatile
polyhalide that can be used as a solvent or propellant.
3. Stability: Iodine pentoxide (I2O5) is a stable polyhalide
that can be stored for long periods without decomposing.
4. Toxicity: Chlorine trifluoride (ClF3) is highly toxic and
can cause severe burns and respiratory damage.
5. High density: Iodine heptafluoride (IF7) has a high density
of 2.6 g/cm3 due to the presence of heavy iodine and fluorine
atoms.
6. Low polarity: Carbon tetrafluoride (CF4) is a non-polar
polyhalide that can dissolve non-polar compounds.
7. Reactivity with water: Chlorine trifluoride (ClF3) reacts
with water to form hydrofluoric acid and hydrochloric acid:
ClF3 + H2O → HF + HCl + OF
8. UV sensitivity: Bromine chloride (BrCl) is sensitive to UV
light and can decompose to form bromine and chlorine radicals:
BrCl → Br• + Cl•
These examples illustrate the diverse characteristics of
polyhalides, which depend on the specific compound and its
properties.
 HISTORICAL BACK GROUND

 1826: The concept of polyhalides was first introduced by

the English chemist Henry Cavendish, who discovered
the formation of chlorine trifluoride (ClF3) by reacting
chlorine with fluorine.
 1900s: The synthesis and characterization of various
polyhalides, such as interhalogen compounds (e.g., ClF,
BrF3), were reported by several chemists, including
Henri Moissan and Paul Lebeau.
 1920s-1930s: The development of new synthesis
methods and characterization techniques, like infrared
spectroscopy, enabled the discovery of more polyhalides,
including the first polyiodides (e.g., ICl2, IBr2).
 1950s-1960s: The structure and bonding of polyhalides
were investigated using X-ray crystallography and other
methods, leading to a better understanding of their
molecular geometry and chemical properties.
PROPERTIES OF POLYHALIDES
 All polyhalides are colored compound. Intensity of
colour increased with the increase in no of halogen atom
present.
 Polyhalides are generally soluble in water, but some of
them can dissociate in water to form free halogen and
halide ions.
 For example:
 ICL3 + H2O ICL2 + HCL +CL-
 BrF3 + H2O BrF2 + HF + F-
 PROPERTIES:
 Some of poly halides from complexes with organic
donar molecule. Some examples are:
 LiI3
 LiC6H6CN
 MI3(C6H5CN)2
 Effect of Heat: (Thermal Decomposition)
 Heating solid polyhalides leads to dissociation
 Dissociation decreases with increasing cation size
 Monohalides are more stable due to high resonance
lattice energy
 PROPERTIES:
 Reaction with halogens:
When a polyhalides is allowed to react with halogen
molecule. Halogen present in polyhalides are substituted
by atom of reacting halogens.
1. KIBr2 +Cl2 KICl2 +Br2
2. CsBr3 +I2 CsIBr2 + IBr
3. KI3 +Cl2 KICl2 +I2
4. CsI3 +Br2 CsIBr2 + I2
TYPES OF POLYHALIDES
 Overview: Brief introduction to different types:

 Di-halides: Compounds containing two halogen atoms. Example includes:

Dicholorine mono-oxide (

 Tri-halides: Compounds containing three halogen atoms. Examples

include: Iodine trichloride (), Bromine trifluoride ().

 Tetra-halides: Compounds containing four halogen atoms. Examples

include: Sulfur hexafluoride ()
CONT…..
 Penta-halides: Compounds containing five halogen atoms. Examples
include: Phosphorus pentachloride (𝑃𝐶𝑙5), Antimony pentafluoride ( 𝑆𝑏𝐹5).

Hexa-halides: Compounds containing six halogen atoms. Examples include:

Molybdenum hexafluoride (𝑀𝑜𝐹6).
 Poly-halide ions: Polyatomic ions containing halogen atoms. Examples
include: Triiodide ion (𝐼3−), Tetrachloroiodide ( 𝐼𝐶𝑙4−).
DIHALIDES - STRUCTURE AND
BONDING

•Example: Dichlorine monoxide (

•Structure: Bent due to lone pairs on oxygen
•Bonding: Covalent bonds between Cl and O
•Image:
TRIHALIDES - STRUCTURE AND
BONDING
 Example: Iodine trichloride ()
 Structure: T-shaped due to lone pairs on iodine
 Bonding: Covalent bonds with partial ionic character due to
electronegativity differences.
 Image:

 Example: Bromine trifluoride ()

 Structure: T-shaped with lone pairs influencing geometry
 Image:
TETRAHALIDES - STRUCTURE AND
BONDING

 Example: Carbon tetrachloride

 Structure: Tetrahedral with sp3 hybridization
 Bonding: Pure covalent bonds
 Image:
PENTAHALIDES - STRUCTURE AND
BONDING
 Example: Phosphorus pentachloride ()
 Structure: Trigonal bipyramidal with sp3d hybridization
 Bonding: Covalent bonds with some ionic character
 Image:
HEXAHALIDES - STRUCTURE AND
BONDING
 Example: Sulfur hexafluoride ()
 Structure: Octahedral with sp3d2 hybridization
 Bonding: Covalent bonds with high symmetry
 Image:
POLYHALIDE IONS - STRUCTURE AND
BONDING
 Example: Triiodide ion (−)
 Structure: Linear with delocalized electrons
 Bonding: Covalent bonding with resonance structures
 Example: Tetrachloroiodide ion −)
 Structure: Square planar
 Bonding: Ionic-covalent character
 Image:
OVERVIEW OF SYNTHESIS METHODS
 Direct Combination of Elements
 Halogen Exchange Reactions
 Redox Reactions
 Solvent-mediated Reactions

 Direct Combination of Elements

 Process: Direct reaction between halogen elements.
 Example: Synthesis of Bromine trifluoride (BrF3).
 Reaction: Br2 +3F2→2BrF3
 Conditions: Requires careful control of temperature and pressure.
 Conducted in a sealed container to manage reactive gases.
CONT….
 Halogen Exchange Reactions
 Process: Exchange of halogen atoms between compounds.
 Example: Synthesis of Iodine monochloride (ICl)
 Reaction: I + Cl → 2ICl
2 2
 Conditions: Often carried out in solution.

 Redox Reactions
 Process: Oxidation-reduction reactions to form polyhalides.
 Example: Synthesis of Iodine trichloride (ICl 3)
 Reaction: I2 + 3Cl2 → 2ICl3​
 Conditions: Typically requires an oxidizing agent.
CONT….
 Solvent-mediated Reactions
 Process: Reactions carried out in a solvent to facilitate polyhalide
formation.
 Example: Synthesis of Triiodide ion (I3−) in aqueous solution
 Reaction: I2 + I- → I3
 Conditions: Involves the use of a suitable solvent like water or
acetonitrile.

 Synthesis of Dihalides
 Example: Dichlorine monoxide (Cl2O)
 Reaction: 2Cl2 + O2 → 2Cl2O2
 Conditions: Requires controlled conditions to prevent over-oxidation.
CONT……
 Synthesis of Trihalides
 Example: Bromine trifluoride (BrF3)
 Reaction: Br + 3F → 2BrF
2 2 3
 Conditions: Conducted in a sealed container to manage reactive gases.

 Synthesis of Tetrahalides
 Example: Carbon tetrachloride (CCl4)
 Reaction: CH4 + 4Cl2 → CCl4 + 4HCl
 Conditions: Requires a catalyst and controlled temperature.
CONT….
 Synthesis of Pentahalides
 Example: Phosphorus pentachloride (PCl5)
 Reaction: PCl3 + Cl2 → PCl5
 Conditions: Often carried out in a chlorinated solvent.

 Synthesis of Hexahalides
 Example: Sulfur hexafluoride (SF6)
 Reaction: S + 3F2 → SF6
 Conditions: High-temperature reaction with careful handling
of fluorine.
CONT…..
 Synthesis of Polyhalide Ions
 Example: Triiodide ion (I3−)
 Reaction: I2 + I− → I3−
 Conditions: Conducted in aqueous or polar organic solvent.
 Example: Tetrachloroiodide ion (ICl4−)
 Reaction: ICl3 + Cl− → ICl4−
APPLICATIONS OF
POLYHALIDES
Polyhalides are compounds containing multiple halogen atoms. They
have various applications across different fields due to their unique
chemical properties. Some applications are:
 Chemical Synthesis:

Iodine monochloride (ICl) in halogenation reactions.

ICl + C₆H₆→ C₆H₅+ HCl
 Catalysis:

N-Bromosuccinimide (NBS) for bromination.

C₆H₅CH₃ + NBS →C₆H₅CH₂Br+ succinimide
 Flame Retardants:

Hexabromocyclododecane (HBCD)
HBCD + heat→ HBR
 CONT…

 Pharmaceuticals:
lodoform as an antiseptic.
CHI₃ + 3NaOH → CI₃Na + H2O
 Agriculture:

Methyl bromide as a soil fumigant.

CH₃Br→ CH₃Br(vapor).
 Industrial Processes:

Chlorine trifluoride in semiconductor manufacturing.

CIF₃ + Si→ SiF₄+ Cl₂
REACTIVITY AND REACTIONS OF
POLYHALIDES
Polyhalides can exhibit various reactions and reactivities depending on the specific
halogens involved and their arrangement within the molecule. Some common reactions
and reactivities of polyhalides include:
 Substitution Reactions:

Nucleophilic Substitution:
Reaction of bromine trifluoride (BrF3) with water.
BrF₃+ H₂O → HF + HOBr + HBг.
 Electrophilic Substitution:

Reaction of chlorobenzene (C6H5Cl) with chlorine gas in the presence of a Lewis acid
catalyst
C₆H₅Cl+ Cl₂→ C₆H₄Cl₂ +HCl
 Redox Reactions:

• Oxidation:
Polyhalides containing iodine can be oxidized to iodate ions in the presence of an
oxidizing agent such as hydrogen peroxide.
51+ 6H+ 3H₂O₂ → IO₃+ 9H₂O
 CONT….
• Reduction:
Polyhalides like bromine can be reduced to bromide ions using reducing
agents such as sodium thiosulfate:
Br₂ + 2S₂O₃₂ → 2BrS₄O₆₂
 Complex Formation:

• Polyhalides can form complexes with transition metals.

For example, tetrachloroaurate ion forms a complex with
potassium ions.
AuCl₄+ K→ K[AuCl₄]
 Acid-Base Reactions:

• Polyhalides can react with bases to form salts.

An example is the reaction of phosphorus pentachloride with
ammonia to form ammonium chloride and ammonium chloride
hydrochloride:
PCl₅+ 5NH₃ → NH₄C1+ NH₄C1.HC1
 CONT…
 Halogen Exchange:
• Polyhalides can undergo halogen exchange reactions. For
example, the reaction of iodine pentachloride with chlorine gas
yields iodine trichloride and chlorine monochloride.
ICl₅+ Cl₂ → ICl₃+ Cl₂Cl
 Polymerization:
 • Polyhalides can undergo polymerization reactions to form
polymers. For instance, the polymerization of tetrafluoroethylene
yields polytetrafluoroethylene , commonly known as Teflon:
 nC₂F₄→ (CF₂)n
ENVIRONMENTAL AND
BIOLOGYCAL INTERACTION
Some notable polyhalides and their environmental and biological
interactions are:
 Dichloromethane (CH₂Cl₂):

Dichloromethane can be found naturally in oceanic sources,

volcanoes, and wetlands. It contributes to air pollution.
It is used as a solvent in food technology, aerosol
formulations, and electronics manufacturing. However,
exposure to dichloromethane can be harmful to humans and
aquatic life.
 Chloroform (CHCl₃):

Chloroform was historically used as an extraction solvent for

fats, greases, and oils. However, it can contribute to air
pollution and environmental contamination.
 Chloroform has been used as an anesthetic and in dentistry. It’s also
employed in scientific research.
However, prolonged exposure can be toxic to the liver and other organs.
 CONT…..
 Carbon Tetrachloride (CCl₄):
Carbon tetrachloride depletes the ozone layer when released
into the air, leading to increased UV radiation exposure and
related health risks.
It’s a potent hepatotoxin (toxic to the liver). Scientific research uses
it to evaluate hepatoprotective agents.
 Iodoform (CHI₃):

Iodoform is insoluble in water but soluble in solvents like ethanol

and chloroform. Its environmental impact is relatively low.
Used in medicine and as an antiseptic.
While these compounds have various applications, their environmental
impact and biological interactions should be carefully considered .
 CHALLENGES
Polyhalides, which are compounds containing multiple halogen atoms,
can present various challenges in chemical reactions.
 Reactivity and Stability:

Polyhalides can be highly reactive due to the presence of

multiple halogen atoms. Their reactivity can lead to unexpected side
reactions or difficulties in controlling the desired outcome.Balancing
reactivity with stability is crucial. Some polyhalides may decompose
easily, making handling and storage challenging.
 Selectivity:Achieving selectivity in reactions involving polyhalides
can be tricky. Different halogen atoms may react differently, leading
to mixtures of products.Designing reactions that selectively target
specific halogen atoms within a polyhalide is a challenge.
 CONT….
 Solubility and Precipitation:
Polyhalides often have varying solubilities in different
solvents.
Finding suitable reaction conditions can be
complex.Precipitation of
polyhalides during reactions can hinder progress and
affect yields.
 FUTURE DIRECTION
 Development of new polyhalide synthesis methods
 Design of polyhalide materials for specific applications (e.g.,
optoelectronics, catalysis)
 Integration of polyhalides with other materials (e.g., metals,
polymers) to enhance properties
 Exploration of polyhalides for energy storage and conversion
 Investigation of polyhalides' potential in biomedicine and
pharmaceuticals
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