p-block

p- block elements Key Points

Group 13: B, Al, Ga, In, Tl

General Properties of Group 13 Elements

•Have an valence electronic configuration of ns²np¹
•They primarily exhibit a +III oxidation state. The stability of the +I oxidation state increases
down the group for In and Tl due to the inert pair effect, This effect refers to the reluctance of
the heavier ns² electrons to participate in bonding.
•Metallic character, boron is a non-metal that primarily forms covalent compounds. The
metallic character increases as you descend the group, with aluminum, gallium, indium, and
thallium being metals.

•The heavier elements (Ga to Tl) also exhibit a lower (+I) oxidation state due to the inert pair
effect, where the ns² electrons become less available for bonding down the group. The stability
of the +I state increases down the group (Ga < In < Tl) .
They tend to form trivalent compounds that are electron deficient. This electron deficiency
makes these compounds Lewis acids, meaning they can accept a pair of electrons.
The heavier elements (Ga, In, Tl) tend to be more ionic and less covalent than those of boron
and aluminum [1]. Their compounds are also more basic [1].
These heavier Group 13 elements also form organometallic compounds containing
metal-carbon bonds. Examples include trimethylgallium (Ga(CH₃)₃), trimethylindium (In(CH₃)₃),
and trimethylthallium (Tl(CH₃)₃). These compounds are particularly important as precursors in
Metal-Organic Chemical Vapor Deposition (MOCVD) for the production of semiconductor
materials. The source also mentions the formation of other organoindium and organothallium
compounds in the context of various reactions.

Oxidation States and Types of Bonds

•Boron only shows a +III oxidation state in its stable compounds.
•Aluminum also primarily exhibits the +III oxidation state.
•Gallium mainly shows +III, but +I is also observed.
•Indium exhibits both +III and +I states, with +I becoming more stable.
•Thallium also shows +III and +I states, with +I being the more stable oxidation state
•The (+III) oxidation state is the most important for all Group 13 elements [1].
•Covalency is suggested for compounds with elements in the (+III) oxidation state because of
the small size and high charge of the M³⁺ ions, leading to a high polarizing power (Fajans' rules).
p-block

•The sum of the first three ionization energies is high for Group 13 elements, favoring covalent
bond formation .
•The electronegativity values are smaller than for Group 14, and the difference is not large
enough to suggest ionic bonding for Groups 1 and 2.
•Simple monomeric M³⁺ ions are unlikely to exist in solution due to high hydration energy .

•Electronegativity values vary, decreasing from B to Al, then slightly increasing down the
group.
•Atomic and ionic radii increase down the group, with some irregularities due to poor shielding
by d electrons. But for atomic radii, there is a smaller increase from Ga to Al due to the
lanthanide contraction, where the filling of the 3d orbitals in Ga results in a higher effective
nuclear charge.
•Melting and boiling points (Table 10.2): Boron has very high values due to its strong covalent
network. Gallium has an unusually low melting point (30 °C). Melting and boiling points
generally decrease from Al to Tl.
Electropositive Character
•Electropositive character increases from B to Tl, making them more reactive towards
non-metals and more likely to form positive ions [4]. Standard electrode potentials (E°) become
less negative from Al to Tl (except for Ga), indicating a decreasing tendency to lose electrons [3].
Ionization Energy
•The sum of ionization energies generally decreases down the group due to increasing atomic
size and shielding. However, there are some irregularities due to the filled d and f orbitals
affecting the effective nuclear charge.

Boron ( highly covalent due to its size and high electronegativity)

Preparation of Boron
•Boron can be prepared by the reduction of boron oxide (B₂O₃) with electropositive metals like
Na, K, or Mg at high temperatures, or by reducing boron halides with hydrogen [3].
Reactions of Boron
•Boron is unreactive in its crystalline form but reacts at high temperatures with oxygen to form
B₂O₃, with nitrogen to form boron nitride (BN), and with halogens to form boron halides (BX₃)
•It reacts with alkali metals to form metal borides.
•Boron reacts with hot concentrated nitric acid to form boric acid (H₃BO₃)

Compounds of Boron and Oxygen

•Boric acid (H₃BO₃) is a white crystalline solid soluble in water and acts as a weak monobasic
acid. It has a layered structure due to hydrogen bonding.
p-block

•Borates are salts of boric acid. They exist as orthoborates (BO₄³-), metaborates (BO₂-), and
polyborates.
•Borax (Na₂[B₄O₅(OH)₄]·8H₂O) is an important borate mineral containing both triangular and
tetrahedral boron units [9]. Its aqueous solution is alkaline [10].
•Sodium perborate (NaBO₃·xH₂O or Na₂[B₂(O₂)(OH)₄]·(6-8)H₂O) is used as a bleaching
agent [10]. It contains a peroxide linkage (O-O) .

Tetrahydroborates (Borohydrides)
•tetrahydroborates are compounds containing the [BH₄]⁻ ion, also known as the borohydride
ion. The tetrahydroborate ion, [BH₄]⁻, is a well-known stable complex ion that is isoelectronic
with methane.
Aluminum Tetrahydroborate (Al(BH₄)₃):
Aluminum tetrahydroborate is described as a volatile, covalent compound.
It can be prepared by the reaction of aluminum chloride (AlCl₃) with lithium borohydride
(LiBH₄)
Alkali Metal Tetrahydroborates: The alkali metal tetrahydroborates, such as sodium
borohydride (NaBH₄) and lithium borohydride (LiBH₄), are mentioned as valuable reducing
agents in both inorganic and organic chemistry. They are stable in alkaline aqueous solutions
and ketones but react readily with acids to liberate hydrogen. These tetrahydroborates are noted
for their ability to reduce aldehydes to primary alcohols and ketones to secondary alcohols.
Esters, carboxylic acids, and epoxides are generally not reduced by NaBH₄ but are reduced by the
more reactive LiBH₄. The tetrahydroborate ion is noted to be a reducing agent.

Boron Nitride: Boron nitride, (BN)ₓ, can be formed from the reaction of boranes with ammonia
at higher temperatures. Boron nitride exists in different forms, including one that has a structure
similar to graphite. In boron nitride, one B atom and one N atom have the same number of
valence electrons as two C atoms. Thus boron nitride nitride has almost the same structure as
graphite. The layers are stacked on top of each other, giving a slippery solid. Figure 10.9 shows
the similarity in structure between boron nitride and borazine and graphite.

Boron Hydrides (Boranes)

•Boron forms a series of electron-deficient compounds called boranes (boron hydrides) [16].
They are classified into nido-boranes (B<0xE2><0x82><0x9Bn+2Hn+6), arachno-boranes
(B<0xE2><0x82><0x9Bn+4Hn+6), etc., based on their structures [16].

Diborane (B₂H₆) is the simplest borane. It has a unique bridged structure with two three-center
two-electron (3c-2e) bonds [17]. It is prepared by the reaction of boron trifluoride with lithium
aluminum hydride or sodium hydride [16]. Diborane is highly reactive and undergoes reactions
p-block

like hydroboration of alkenes and alkynes [18]. It reacts with ammonia to form borazine
(B₃N₃H₆), also known as inorganic benzene [19].

Borazine (B₃N₃H₆) has a cyclic structure similar to benzene, with alternating boron and
nitrogen atoms. Prop sim to Benzene.

Boron Halides
•Boron halides (BX₃) are strong Lewis acids because the boron atom has an incomplete octet. The
Lewis acidity order is typically BI₃ > BBr₃ > BCl₃ > BF₃, (due to pπ-pπ back bonding). Boron
trihalides undergo hydrolysis to form boric acid and hydrogen halide.
Boron also forms dihalides of the type BX₂, which are unstable and contain an unpaired
electron.
Organo-metallic comp: B-C in Hydroboration (alkenes and alkynes)

Al
In Group 13 elements, particularly aluminum, form coordination complexes with various
ligands due to their empty p orbitals [15].

Aluminum forms organometallic compounds with the general formula AlR₃, where R is an
alkyl or aryl group.
These compounds are important sources of carbanions and are used in organic synthesis
Trimethylaluminum (Al(CH₃)₃) and triethylaluminum (Al(C₂H₅)₃) have dimeric structures in
which the alkyl groups bridge the aluminum atoms.
•
Reaction with Dioxygen: Aluminum burns readily in air or dioxygen, and the reaction is
strongly exothermic (ΔH = -1670 kJ mol⁻¹). This reaction forms aluminum oxide (Al₂O₃). The
thermite reaction, involving aluminum and metal oxides like Fe₂O₃ or Cr₂O₃, generates high
temperatures and is used for welding metals and in incendiary bombs.
•
Reaction with Halogens and Sulphur: Aluminum reacts with halogens (e.g., Cl₂) when heated
to form aluminum halides (AlX₃). Aluminum sulphide (Al₂S₃) is formed by heating aluminum
with sulphur

Aluminum oxide/ Alumina (Al₂O₃) and aluminum hydroxide (Al(OH)₃) are amphoteric,
meaning they can react with both acids and bases. Al(OH)₃ dissolves acids and in strong bases to
form [Al(OH)₄]⁻ ions. Alumina reacts with acids to form aluminum salts and with bases to form
aluminates. For example, it reacts with NaOH to form NaAlO₂ or Na[Al(OH)₄]
p-block

•Aluminum halides:
Aluminum chloride (AlCl₃) and aluminum bromide (AlBr₃) are largely covalent in the anhydrous
state. They exist as dimers (Al₂Cl₆ and Al₂Br₆) in the vapour phase and in non-polar solvents.
Anhyd AlCl₃ is a Lewis acid and is used as a catalyst in FC alkylation/ acylation Rxns.
Aluminum halides are readily hydrolyzed by water, forming acidic solutions due to the
formation of hydrated aluminum ions and the release of HX.
Aluminum halides act as Lewis acids and form adducts with Lewis bases, such as ethers, amines,
and phosphines.

Alums
•Alums are a specific type of double salt that are hydrated sulfates with the general chemical
formula:M⁺M³⁺(SO₄)₂·12H₂O
Where, M⁺ is a monovalent cation, such as (K⁺), (Na⁺), (NH₄⁺), or (Tl⁺). M³⁺ is a trivalent metal
cation, most commonly (Al³⁺), but can also be (Cr³⁺), (Fe³⁺), or other trivalent ions like Ga³⁺, In³⁺,
V³⁺, Ti³⁺, Mn³⁺, Co³⁺. Aluminum forms common alums
Potassium/Potash alum: KAl(SO₄)₂·12H₂O , Sodium alum: NaAl(SO₄)₂·12H₂O

Cement
•Cement is a complex mixture of calcium aluminates and silicates. . Portland cement is a
common type, and its manufacturing involves heating a mixture of limestone, clay, and gypsum
in a rotary kiln at 1400-1600 °C . The main constituents are dicalcium silicate (Ca₂SiO₄),
tricalcium silicate (Ca₃SiO₅), and tricalcium aluminate (Ca₃Al₂O₆) .

Gallium, Indium, and Thallium:

•They form trihalides (MX₃), which are also Lewis acids. GaCl₃ forms a dimer (Ga₂Cl₆).
•Gallium and indium also form dihalides (MX₂) which disproportionate to M+ and M³+ halides.
•The +I oxidation state becomes more stable down the group, leading to stable monohalides
like InX and TlX (e.g., TlCl).
They also form organometallic compounds such as trimethylgallium (Ga(CH₃)₃),
trimethylindium (In(CH₃)₃), and trimethylthallium (Tl(CH₃)₃), used in MOCVD.
 p-block

Group 14 - C, Si, Ge, Sn, Pb

Valence Electronic configuration ns² np²
Ox states: The most important oxidation state is +IV, although the +II state becomes more stable
down the group due to the inert pair effect for Ge, Sn, Pb which possess both +2 and +4 ox states.

Chemical Reactivity: The reactivity of Group 14 elements varies significantly. Carbon is relatively
unreactive at room temperature but reacts at higher temperatures. Silicon and germanium are also
relatively inert but can react under specific conditions, Tin and lead are more reactive metals.

Carbon and silicon are unaffected by water. Germanium is unaffected by water and dilute acids. Tin
reacts with steam and strong acids or bases. Lead is unaffected by water but dissolves in nitric acid
and hot concentrated sulphuric acid
Silicon reacts with steam at high temperatures to form SiO₂ and H₂. It also reacts with hot aqueous
alkali to form silicates and hydrogen.

Bond energies (M-M) decrease down the group. This, decreasing ability to form long chains
(catenation), with carbon exhibiting the most pronounced catenation

Metallic character increases down the group, Carbon and silicon are non-metals, germanium is a
metalloid, and tin and lead are metals.

Melting and Boiling Points: Carbon has a very high melting point. Silicon and germanium also
have high melting points. The melting points decrease down the group, with tin and lead
having lower melting points. This trend is related to the decreasing strength of metallic
bonding in the solid state. Boiling points also generally decrease down the group.

•Covalent radii increase down the group, while ionization energies and electronegativity
generally decrease, though there are some irregularities due to the increasing number of inner
electrons and d/f orbitals.

Organometallic Derivatives: Group 14 elements form organometallic compounds with

metal-carbon bonds. Tetraethyl lead (TEL) was historically used as an antiknock agent in
gasoline.

Key Differences Between Carbon and Heavier Elements:

•Carbon's ability to form strong pπ-pπ bonds is more pronounced than in heavier elements.
•Carbon typically has a coordination number of four.
•C-C bonds are significantly stronger than M-M bonds for heavier elements, affecting
catenation.
p-block

C
Inert Pair Effect: The tendency of the heavier elements (Ge, Sn, Pb) to show a more stable +II
oxidation state compared to the +IV state is due to the inert pair effect, where the ns² electrons
become reluctant to participate in bonding due to poor shielding by intervening d and f
electrons. This effect is most prominent in lead.

Carbides-hard materials: Carbides are binary compounds of carbon with metals or less
electronegative elements. Three main types:
•Ionic or salt-like carbides: Formed with highly electropositive metals (alkali and alkaline earth
metals). CaC₂, which reacts with water to produce acetylene (ethyne). Be₂C and Al₄C₃
•Interstitial or metallic carbides: Formed with transition metals. Carbon atoms occupy the
interstitial sites in the metal lattice. These carbides are very hard and have high melting points
but retain metallic conductivity. Examples TiC and WC.
•Covalent carbides: Formed with elements having electronegativity close to carbon. Example
silicon carbide (SiC, carborundum), a very hard and thermally stable material, Boron carbide B₄C.

Carbonates: Carbonates contain the CO₃²⁻ ion. Most metal carbonates are insoluble in water
and decompose upon heating to give metal oxides and CO₂. Sodium and potassium carbonates
are soluble in water. Bicarbonates (containing HCO₃⁻) exist in solution and some can be isolated
as solids. Heating bicarbonates leads to the formation of carbonates, CO₂, and water.

Sulphides of Carbon: Carbon disulphide (CS₂) is the most common sulphide of carbon. It is a
colorless liquid with a pungent odor and is highly flammable. It reacts with chlorine to form CCl₄
and S₂Cl₂. CS₂ is used in the manufacture of rayon.

Oxides:
★ CO (poisonous, reducing agent) forms metal carbonyls with many transition metals, acting
as a ligand, produced by the reaction of steam with hot coke (water gas) or with air (producer
gas)
★CO₂ (acidic, forms carbonates) produced by the complete combustion of carbon-containing
fuels, reaction of carbonates with acids. Used as a refrigerant (dry ice).
★Carbon Suboxide (C₃O₂) is a foul-smelling gas produced by dehydrating malonic acid. It is
unstable at room temperature.
★ Silicon dioxide/ Silica SiO₂ (inert, acidic, network solid). Reacts w water and no other acids
except HF. very hard, has a high melting point. reacts with strong alkalis at high temperatures to
form silicates.
 p-block

★Germanium, tin, and lead form oxides (GeO₂,SnO, SnO₂, PbO, PbO₂, Pb₂O₃, Pb₃O₄ ) with
varying properties; SnO and SnO₂ are amphoteric, and PbO is amphoteric while PbO₂ is a strong
oxidizing agent, also amphoteric.

Allotropes and Structures:

•Carbon has allotropes like diamond (tetrahedral, very hard, insulator, high mp),
graphite (layered,planar hexagonal rings, lubricant, conductor)- Within each layer, each carbon
atom is bonded to three other carbon atoms by sigma bonds, and the remaining electron forms a
delocalized π-electron cloud. These layers are held together by weak van der Waals forces,
allowing them to slide over each other, which accounts for graphite's softness and lubricating
properties. The delocalized electrons make graphite a good conductor of electricity. Graphite is
thermodynamically more stable. fullerenes (e.g., C₆₀)- cage like structure
•Silicon and germanium have a diamond-like structure.
•Tin exists as grey (cubic) and white (tetragonal) tin.
•Lead has a metallic (face-centered cubic) structure.

Si
Silicates: Silicates are compounds containing silicon and oxygen, with the basic structural unit
being the tetrahedral SiO₄⁴⁻ ion. These tetrahedra can be linked in various ways to form different
structures:
•Orthosilicates (nesosilicates): Isolated SiO₄⁴⁻ units, e.g., olivine.
•Pyrosilicates (sorosilicates): Two SiO₄⁴⁻ tetrahedra sharing one oxygen atom
(Si₂O<0xE2><0x82><0x87>⁶⁻), e.g., thortveitite.
•Cyclic silicates: Three or more SiO₄⁴⁻ tetrahedra linked cyclically by sharing two oxygen atoms
per tetrahedron (Si₃O<0xE2><0x82><0x89>⁶⁻, Si₆O<0xE2><0x82><0x92>¹²⁻), e.g., beryl.
•Chain silicates (pyroxenes): SiO₄⁴⁻ tetrahedra linked in a linear chain by sharing two oxygen
atoms per tetrahedron (Si₂O₆⁴⁻)n, e.g., enstatite.
•Double chain silicates (amphiboles): Two single chains linked by sharing oxygen atoms
(Si₄O₁₁⁶⁻)n, e.g., asbestos.
•Sheet silicates (phyllosilicates): SiO₄⁴⁻ tetrahedra linked to form a two-dimensional sheet by
sharing three oxygen atoms per tetrahedron (Si₂O₅²⁻)n, e.g., clay, mica, talc.
•Three-dimensional silicates (tectosilicates): All four oxygen atoms of each SiO₄⁴⁻
tetrahedron are shared, forming a three-dimensional network (SiO₂)n, e.g., quartz, feldspars,
zeolites, ultramarines.

Zeolites: Zeolites are aluminosilicates with a three-dimensional network structure containing

water molecules trapped in cavities and channels. They have a porous structure and are used as
molecular sieves, ion exchangers, and catalysts.
 p-block

Glass: Glass is an amorphous solid obtained by melting a mixture of silica, sodium carbonate,
and calcium carbonate, followed by rapid cooling. It is transparent and has a supercooled liquid
structure.
Organosilicon Compounds:
The Si-C bond is strong and less polar than the Si-O bond.
Contain Si-C bonds, including silicones (polymers with Si-O-Si linkages, stable and versatile)
and silanes (silicon hydrides, more reactive than alkanes).
Organosilicon compounds can be prepared by various methods, including the reaction of silicon
tetrachloride with Grignard reagents (RMgCl).

Silicones: organosilicon polymers containing Si-O-Si linkages. They are prepared by the
hydrolysis of dialkyldichlorosilanes (R₂SiCl₂). Silicones have properties like high thermal
stability, water repellency, and electrical insulation. They are used as lubricants, sealants, and in
medical implants. Silicones can undergo halogenation reactions.
Silanes (hydrides of Si: )(Si<0xE2><0x82><0x9nH<0xE2><0x82><0x8Bp2n+2>), are less stable
than alkanes due to the weaker Si-Si bond and the polar Si-H bond. They are highly reactive and
spontaneously flammable in air. Monosilane (SiH₄) is the most common silane.

Complexes of Silicon: Silicon can form complexes, particularly with fluoride ions, such as the
[SiF₆]²⁻ ion, where silicon is hexacoordinated.

Internal π-Bonding in d Orbitals: In compounds like trisilylamine (SiH₃)₃N, the nitrogen atom
is planar, suggesting sp² hybridization. This planarity is attributed to the formation of pπ-dπ
bonds between the lone pair of electrons on nitrogen (p orbital) and the empty d orbitals on
silicon.

Halides: Group 14 elements form tetrahalides (MX₄), where M = C, Si, Ge, Sn, Pb and X = F, Cl,
Br, I.
Carbon tetrachloride (CCl₄) is inert to hydrolysis due to the absence of low-lying d orbitals on
carbon. Silicon tetrachloride (SiCl₄) is readily hydrolyzed by water due to the presence of empty d
orbitals on silicon, allowing coordination with water molecules and subsequent nucleophilic
attack. Lead tetrahalides (PbX₄) are generally unstable and act as strong oxidizing agents, readily
reducing to the more stable Pb(II) state due to the inert pair effect. Tin also forms tetrahalides
(SnX₄). Dihalides (MX₂) are more stable for the heavier elements (Ge, Sn, Pb) due to the inert
pair effect. For example, PbCl₂ is more stable than PbCl₄. Tin(II) halides (SnX₂) are also known
and act as reducing agents.
p-block

Soluble Silicates: The reaction of silica with molten alkali carbonates produces soluble sodium
or potassium silicates (water glass), which are used in various applications, including as
adhesives and in fireproofing.
Hydrides of Tin and Lead: Tin hydride- stannanes are unstable. PbH₄ (Plumbane) is extremely
unstable and decomposes easily.
Group 15 - N, P, As, Sb, Bi

General Properties of Group 15 Elements (Nitrogen Group)

electronic configuration of ns²np³.

•The tendency to exhibit metallic character increases as you move down the group [2, 9].
Nitrogen and phosphorus are non-metals, arsenic and antimony are classified as metalloids, and
bismuth is a metal [2, 9].
•These elements commonly exhibit oxidation states of -III, +III, and +V [1, 7]. Nitrogen is
unique in displaying a broader range of oxidation states, from -III to +V [1, 7, 24]. The stability
of the +V oxidation state decreases down the group, while the stability of the +III
oxidation state increases [1, 2, 7, 9].
•Group 15 elements generally form covalent compounds due to their tendency to share
electrons to achieve a stable octet configuration [1, 2, 9]. Notably, nitrogen and phosphorus
can form multiple bonds involving π-orbitals [2, 9].

Nitrogen
Elemental nitrogen exists as a diatomic molecule, N₂, which is a colorless, odorless, and
tasteless gas [1, 7]. The N₂ molecule is exceptionally stable due to the presence of a very strong
triple bond (N≡N), characterized by a short bond length (1.09 Å) and a high dissociation energy
(945 kJ mol⁻¹) [1, 7]. This strong bond makes nitrogen relatively unreactive under normal
conditions [1, 7]. However, active nitrogen, generated by passing an electric spark through
nitrogen gas at low pressure, is significantly more reactive [1].

Ammonia (NH₃): A colorless gas with a pungent odor and is highly soluble in water, forming
ammonium hydroxide (NH₄OH), a weak base. Industrially, ammonia is synthesized via the
Haber-Bosch process, which involves the reaction of nitrogen with hydrogen at elevated
temperatures and pressures in the presence of a catalyst. Ammonia is crucial for the production
of nitrogenous fertilizers such as ammonium salts and urea, and it is also used in the
manufacture of nitric acid. Ammonia burns in dioxygen to produce nitrogen and water.

Hydrazine (N₂H₄): A colorless liquid with an odor resembling ammonia, it is a strong

reducing agent and has a tendency to decompose explosively. Hydrazine can form salts with
p-block

acids and acts as an electron donor, forming complexes with metal ions. Its applications include
rocket fuel and the treatment of boiler water to prevent corrosion.
•Hydroxylamine (NH₂OH): This compound forms colorless crystals and is thermally
unstable, often exploding upon heating. It is a weaker base compared to ammonia or hydrazine
and functions as a reducing agent.

Oxides of Nitrogen: Nitrogen forms a series of oxides with varying oxidation states [2, 24]:
◦Nitrous oxide (N₂O) (+I): A neutral gas used as an anesthetic [2, 24].
◦Nitric oxide (NO) (+II): A neutral, paramagnetic gas that readily reacts with oxygen to form
nitrogen dioxide [2, 24, 25].
◦Dinitrogen trioxide (N₂O₃) (+III): An acidic blue liquid existing in equilibrium with NO and
NO₂ [2, 24, 25].
◦Nitrogen dioxide (NO₂) (+IV): An acidic, paramagnetic, brown gas that can dimerize to form
dinitrogen tetroxide (N₂O₄) [2, 24, 26].
◦Dinitrogen pentoxide (N₂O₅) (+V): An acidic solid that serves as the anhydride of nitric acid .

Oxoacids of Nitrogen:
◦Nitrous acid (HNO₂): An unstable acid formed in solution, it can act as both an oxidizing and
a reducing agent [2, 27, 28].
◦Nitric acid (HNO₃): A strong oxidizing agent that reacts with most metals, with the
reactivity depending on the concentration and the metal's activity [2, 28-31]. Concentrated nitric
acid can passivate some metals by forming a protective oxide layer [2, 13, 31]. Nitric acid is vital
in the production of fertilizers, explosives, and dyes [2, 29].

Salts: Nitrogen forms nitrates (salts of nitric acid, generally soluble in water) [2], nitrites (salts
of nitrous acid) [2], and hydrogen azide (HN₃), a highly poisonous and explosive liquid [2, 17].

Phosphorus

Phosphorus exists in several allotropic forms, the most common being white phosphorus,
red phosphorus, and black phosphorus [1, 3, 8, 9, 17]. White phosphorus is a soft, waxy,
highly reactive, and poisonous solid that spontaneously ignites in air [3, 8, 17]. Red phosphorus
is less reactive and non-poisonous [2, 3, 8, 9]. Black phosphorus is the thermodynamically most
stable allotrope and has a layer structure [3, 8].

Phosphine (PH₃): A colorless, extremely poisonous gas characterized by a rotten fish-like odor
[3, 11, 12]. It is less basic than ammonia and acts as a reducing agent [3, 4, 11, 12]. Phosphine
spontaneously catches fire in air due to the presence of diphosphine (P₂H₄) as an impurity
 p-block

Phosphorus Halides: Phosphorus forms trihalides (PX₃) and pentahalides (PX₅), with the
exception of PI₅ [3, 18, 21, 22]. Phosphorus trichloride (PCl₃) is a colorless, oily liquid that
hydrolyzes to form phosphorous acid (H₃PO₃) and HCl [3, 21]. Phosphorus pentachloride
(PCl₅) is a yellowish-white solid that readily sublimes and hydrolyzes to produce phosphoric acid
(H₃PO₄) and HCl [3, 21, 23]. Phosphorus halides are important chlorinating agents [3, 22, 23].

Oxides of Phosphorus:
◦
Phosphorus(III) oxide (P₄O₆): Formed when phosphorus is burned in a limited supply of air
◦
Phosphorus(V) oxide (P₄O₁₀): A white deliquescent solid produced by burning phosphorus in
excess air. It is a strong dehydrating agent and reacts with water to form phosphoric acid
(H₃PO₄) [3, 31, 32].

Oxoacids of Phosphorus: Phosphorus forms various oxoacids with phosphorus in oxidation

states of +1, +3, and +5 [3, 33]:
Orthophosphoric acid (H₃PO₄): Also known as phosphoric acid, it is a tribasic acid, forming
three series of salts (dihydrogen phosphates, hydrogen phosphates, and normal phosphates) [3,
33]. It is produced on a large scale for the manufacture of phosphate fertilizers [3, 34].
◦
Phosphorous acid (H₃PO₃): A dibasic acid with one non-ionizable hydrogen atom directly
bonded to phosphorus. It is a good reducing agent [3, 36, 37].
◦
Hypophosphorous acid (H₃PO₂): A monobasic acid with two hydrogen atoms directly
bonded to phosphorus. It is a strong reducing agent [3, 36, 37].
Other oxoacids include pyrophosphoric acid (H₄P₂O<0xE2><0x82><0x87>) and metaphosphoric
acids (HPO₃)n [3, 34-36].

Phosphates: Salts of phosphoric acid are widely used as fertilizers, including superphosphate
and triple superphosphate [3, 5, 20, 21]. Graham's salt is an example of a polymetaphosphate [3].
Arsenic, Antimony, and Bismuth
Moving down Group 15, these elements show a clear increase in metallic character [2, 9].
•
The stability of their hydrides (arsine - AsH₃, stibine - SbH₃, bismuthine - BiH₃) decreases
down the group, and they become increasingly strong reducing agents. Arsine is notably
highly toxic.
 p-block

•They form trihalides (e.g., AsCl₃, SbCl₃, BiCl₃) and can also form pentahalides with more
electronegative halogens (e.g., AsF₅, SbF₅, BiF₅) .

•They form oxides such as As₂O₃, Sb₂O₃, and Bi₂O₃. The acidic/basic nature of these oxides
changes down the group: As₂O₃ and Sb₂O₃ are amphoteric, while Bi₂O₃ is predominantly basic

Trends in Group 15 Hydrides

•The stability of the hydrides decreases in the order NH₃ > PH₃ > AsH₃ > SbH₃ > BiH₃
•Their reducing power increases down the group [3, 5, 10, 13].
•The basicity of the hydrides decreases down the group (NH₃ > PH₃ > AsH₃ ≈ SbH₃ < BiH₃) .
•The bond angles in the hydrides decrease down the group, which is attributed to the
decreasing electronegativity of the central atom and its increasing size [5, 10, 13].

Fertilizers
Nitrogen fertilizers, including ammonia, ammonium salts, urea, and nitrates, promote leaf
growth and overall plant productivity [5, 20]. Urea (NH₂CONH₂) is a widely used nitrogenous
fertilizer [5, 20].
Phosphorus fertilizers, often in the form of phosphates like superphosphate [Ca(H₂PO₄)₂], are
crucial for root development [5, 20].
p-block

Group 16: O, S, Se, Te, Po

•The Group 16 elements are non-metals or metalloids. Collectively they are called the
"chalcogens" or ore-forming elements because many metal ores are oxides or sulphides.
•Their importance in industrial chemicals.
•Moving down the group, metallic character increases, and non-metallic character decreases.
•
Oxygen and sulfur are non-metals, selenium and tellurium are metalloids, and polonium is a
radioactive metal.
•Elements exhibit allotropy.
•The general electronic configuration is s²p⁴, requiring two additional electrons to achieve a
stable noble gas configuration. This leads to a common oxidation state of (-II). However, they
also exhibit positive oxidation states (+IV and +VI), especially when bonded to more
electronegative elements like oxygen and fluorine.
•
The ability to show positive oxidation states increases down the group as the inert pair effect
becomes more significant, making the s electrons less available for bonding.
•
Oxygen is highly electronegative. Electronegativity decreases down the group.

•Atomic and ionic radii increase down the group.

•Ionization energy decreases down the group.
•
The elements form covalent bonds and can form two covalent bonds to achieve a stable gas
configuration, for example, in H₂O, H₂S, and Cl₂O.
•
Higher catenation ability (forming chains of identical atoms) is observed for sulfur compared to
oxygen due to stronger single bonds and weaker pi bonds.

Oxygen (O):
•Oxygen exists mainly as diatomic oxygen (O₂) and ozone (O₃).
•Dioxygen (O₂) is a colorless, odorless, and tasteless gas. It constitutes about 21% of the
atmosphere. Liquid oxygen is pale blue and paramagnetic.
•
Ozone (O₃) is an allotrope of oxygen, prepared by subjecting oxygen to a silent electric discharge.
Higher concentrations of O₃ can be obtained by liquefaction and fractional evaporation. Ozone is
a pale blue gas with a pungent odor, and in concentrated form, it is dangerously explosive.
 p-block

•
Dioxygen supports combustion and is essential for respiration.
•Ozone is a powerful oxidizing agent, stronger than dioxygen. It is used as a germicide,
disinfectant, and for bleaching oils, ivory, and starch. It also protects the earth from harmful UV
radiation.
•Oxygen exhibits an oxidation state of (-II) in most of its compounds, but also shows (-I) in
peroxides (e.g., H₂O₂ and Na₂O₂) and (-½) in superoxides (e.g., KO₂) and (+II) in OF₂.
•
Oxygen forms oxides which can be acidic (e.g., CO₂, SO₂), basic (e.g., Na₂O, MgO), amphoteric
(e.g., Al₂O₃, ZnO), or neutral (e.g., CO, N₂O).
•
Peroxides contain the O₂²⁻ ion and have oxygen in the -1 oxidation state. Superoxides contain
the O₂⁻ ion with oxygen in the -½ oxidation state.

Sulfur (S):
•Sulfur exists in several allotropic forms, the most important being rhombic (α-sulfur) and
monoclinic (β-sulfur). Rhombic sulfur is stable at room temperature and transforms to
monoclinic sulfur above 369 K. Both forms consist of puckered S<0xE2><0x82><0x88> rings.
•
Sulfur exhibits a greater tendency for catenation than oxygen, forming chains up to S₂₀.
•Common oxidation states of sulfur are -II, +2, +4, and +6.
•
Hydrogen sulfide (H₂S) is a colorless gas with a rotten egg smell. It is a weak acid.
•
Sulfur dioxide (SO₂) is a colorless gas with a pungent, suffocating odor. It is produced by burning
sulfur in air or roasting sulphide ores. SO₂ is an acidic oxide and acts as a reducing as well as an
oxidizing agent. It is used as a bleach, disinfectant, and preservative.
•
Sulfur trioxide (SO₃) exists in different polymeric forms. It is produced by the catalytic oxidation
of SO₂. SO₃ is a highly acidic oxide and readily absorbs moisture to form sulfuric acid (H₂SO₄).
•
Sulfuric acid (H₂SO₄) is a very important industrial chemical. It is prepared on a large scale by
the Contact Process. H₂SO₄ is a strong acid, a dehydrating agent, and an oxidizing agent. It
forms two series of salts: sulfates and hydrogen sulfates.
•
Thiosulfates contain the S₂O₃²⁻ ion. Sodium thiosulfate (Na₂S₂O₃) is used in photography as a
fixer.
•
 p-block

Oxoacids of sulfur include sulfurous acid (H₂SO₃), sulfuric acid (H₂SO₄), thiosulfuric acid
(H₂S₂O₃), polythionic acids (H₂S<0xE2><0x82><0x9B>O₆), peroxodisulfuric acid
(H₂S₂O<0xE2><0x82><0x88>), and others.
Selenium (Se), Tellurium (Te), and Polonium (Po):
•
Selenium exists in several allotropic forms, including red (non-metallic) and grey (metallic, most
stable). It is used in photoelectric cells.
•
Tellurium also exhibits allotropy and is less abundant than selenium.
•
Polonium is a radioactive element and has no stable isotopes.
•
These elements also form hydrides (H₂Se, H₂Te, H₂Po), dioxides (SeO₂, TeO₂, PoO₂), and
trioxides (SeO₃, TeO₃).
•The acidic character of their hydrides increases down the group (H₂S < H₂Se < H₂Te).
•Their oxides are generally acidic or amphoteric.

Hydrides of Group 16 Elements:

•The hydrides (H₂E, where E = O, S, Se, Te, Po) have angular structures.
•
Bond angle decreases down the group due to decreasing electronegativity and increasing lone
pair repulsion.
•Thermal stability decreases down the group (H₂O > H₂S > H₂Se > H₂Te).
•Reducing power increases down the group (H₂O < H₂S < H₂Se < H₂Te).
•Acidic character increases down the group (H₂O < H₂S < H₂Se < H₂Te). Water is neutral, while
the others are acidic.
•H₂O has unusually high boiling point due to extensive hydrogen bonding. The boiling points
generally increase down the group due to increasing molecular size and van der Waals forces, but
H₂O is an exception.

Oxides of Group 16 Elements:

•
Dioxides (EO₂) and trioxides (EO₃) are common types of oxides.
•
The acidic character of dioxides increases down the group (SO₂ < SeO₂ < TeO₂).
•
SO₂ is a reducing agent, while TeO₂ is an oxidizing agent.
This information covers the essential properties, occurrences, and some key reactions of Group
16 elements and their important compounds as described in the provided sources.
 p-block

G17 Halogens: F, CL, Br, I, At

General Properties of Halogens
•'salt former', these elements readily react with metals to form salts [1].
•EC (ns² np⁵), needing only one more electron to achieve a stable noble gas configuration. This
makes them very reactive non-metals and strong oxidizing agents, readily acquiring an electron
(forming an ionic bond, giving X⁻) or sharing an electron with another atom (forming a covalent
bond)
•Fluorine is the most reactive element [1-3].
•
The reactivity of the halogens decreases down the group (F > Cl > Br > I) [1, 3-5]. This is because
fluorine has low-lying d orbitals available for bonding, whereas the other halogens have higher
energy levels [1].
•Electronegativity decreases down the group [1, 6]. Fluorine is the most electronegative
element, which explains its strong oxidizing ability .
•The atomic and ionic radii of the halogens increase down the group [1, 7]. The size difference
is particularly small between chlorine and bromine [1].
•
The melting and boiling points of the halogens increase down the group because the strength
of London dispersion forces increases with increasing molecular size and number of electrons [1,
6]. Fluorine and chlorine are gases, bromine is a liquid, and iodine is a solid at room temperature
[1, 6]. Astatine is a radioactive solid [1].
•
The colors of the halogens deepen down the group: fluorine is pale yellow, chlorine is
yellow-green, bromine is reddish-brown, and iodine is violet [1]. This is due to the absorption of
light promoting an electron to a higher energy state; as the energy levels become closer down
the group, light of lower energy (longer wavelength) is absorbed [1].
•
Solid halogens form black flaky or metallic lustrous crystals. Their electrical conductivity
increases from fluorine to iodine, with iodine behaving as a semiconductor in its liquid state due
to the transfer of charge along a limited extent [1].

Extraction and Production

•
Fluorine: Difficult to obtain due to its extreme reactivity. It was first prepared by Moissan in
1886 by electrolyzing a mixture of anhydrous KF in liquid HF [2]. Fluorine is obtained by the
electrolysis of KHF₂ [2]. The hydrogen liberated at the cathode must be separated from the
 p-block

fluorine liberated at the anode to prevent explosion [2]. The containers used in fluorine
preparation are often made of copper or Monel metal (Cu/Ni alloy) as they develop a protective
fluoride film [2]. Graphite can be used as the anode, and steel as the cathode [2].
•
Chlorine: Prepared by heating HCl with MnO₂ [8]. Industrially, it's produced by the Deacon
process (oxidation of HCl by atmospheric oxygen at 723 K in the presence of CuCl₂) [8, 9] or by
the electrolysis of brine (aqueous NaCl) [9].
•
Bromine: Obtained mainly from seawater and brine lakes, which contain bromide ions [9]. It is
recovered by oxidizing bromide ions with chlorine gas [7, 9].
•
Iodine: There are two main commercial methods for obtaining iodine: from Chile saltpeter
(which contains sodium iodate, NaIO₃) and from seaweed [7]. In both methods, iodate or iodide
is reduced to iodine using a suitable reducing agent like sodium bisulfite (NaHSO₃) or sulfurous
acid (H₂SO₃) [7].

Chemical Reactivity and Compounds

•Halogens form compounds with metals (ionic halides) and non-metals (covalent halides) [1].
•All halogens react directly with most metals to form metal halides. The reactivity generally
decreases down the group [10].
•Halogens react with hydrogen to form hydrogen halides (HX) [1]. The vigor of the reaction
decreases from fluorine to iodine [10].
•Halogens react with water in different ways [1, 3, 11]. Fluorine reacts vigorously to produce
oxygen and hydrogen fluoride [3, 11]. Chlorine and bromine react to form hydrohalic acid (HCl,
HBr) and hypohalous acid (HOCl, HOBr) [3]. Iodine dissolves in water only slightly [3].
•A halogen can displace a less reactive halogen from its salt solution (e.g., Cl₂ + 2Br⁻ → 2Cl⁻ +
Br₂) [1, 7]. The order of displacement is F₂ > Cl₂ > Br₂ > I₂ [1].

Hydrogen Halides (HX):

•Hydrogen halides are colorless gases at room temperature, with the exception of HF, which has
a higher boiling point due to strong hydrogen bonding between HF molecules [15, 16].
•
They are highly soluble in water, forming hydrohalic acids (HF, HCl, HBr, HI) [13, 15-18]. With
the exception of HF, these are strong acids [13, 15-18]. The acid strength increases down the
group (HF < HCl < HBr < HI) [16, 18, 19]. This trend is primarily attributed to the decrease in
bond dissociation enthalpy of the H-X bond down the group, making it easier to release H⁺ ions
[5, 16, 18]. The high enthalpy of hydration of the smaller F⁻ ion also contributes to the weak
acidity of HF [16, 18, 20].
•Hydrogen halides react with metals to produce metal halides and hydrogen gas [13, 16].
p-block

•HF is notably used to etch glass because it reacts with silica (SiO₂): SiO₂ + 4HF → SiF₄ + 2H₂O

Halogen Oxides and Oxoacids:

•Halogens form various oxides and oxoacids in which the halogen exhibits positive oxidation
states [21-23].
•
Oxides of fluorine (OF₂, O₂F₂) are generally unstable due to the high electronegativity of fluorine
[21, 23]. OF₂ is a pale yellow gas and a potent oxidizing agent [21, 23].
•
Oxoacids of chlorine include hypochlorous acid (HOCl), chlorous acid (HClO₂), chloric acid
(HClO₃), and perchloric acid (HClO₄) [21, 23]. The stability of these acids increases with the
increasing oxidation state of chlorine, while their oxidizing power also generally increases [21,
23]. HOCl is commonly used as a bleaching agent and disinfectant [23, 24].
•
Oxoacids of bromine include hypobromous acid (HOBr), bromous acid (HBrO₂), bromic acid
(HBrO₃), and perbromic acid (HBrO₄) [22, 23, 25]. These are generally less stable than the
corresponding chlorine oxoacids [22, 23, 25].
•
Oxoacids of iodine include hypoiodous acid (HOI), iodous acid (HIO₂), iodic acid (HIO₃), and
periodic acid (H₅IO₆ or HIO₄) [8, 23, 26]. Iodic acid (HIO₃) is a strong oxidizing agent [8, 23, 26].

Interhalogen Compounds:
Halogens can combine with each other to form interhalogen compounds with the general
formula XX'n, where X is the larger, less electronegative halogen, X' is the smaller, more
electronegative halogen, and n is an odd integer (1, 3, 5, or 7) [27, 28]. Examples include ClF,
BrF₃, IF₅, and IF<0xE2><0x82><0x87> [
These compounds are generally more reactive than the individual halogens (except for F₂)
because the X-X' bond in interhalogens is weaker than the X-X bond in elemental halogens .
•Their properties are intermediate between those of the constituent halogens [27, 28].
•Interhalogen compounds are covalent, and their structures can often be predicted using VSEPR
theory [6, 28].

Pseudohalogens and Pseudohalides:

•Pseudohalogens are diatomic or polyatomic species that exhibit chemical behavior analogous to
that of the halogens [29, 30]. Common examples include cyanogen (CN)₂, thiocyanogen (SCN)₂,
and azidogen (N₃)₂ [29, 30].
•Their anions are called pseudohalides (CN⁻, SCN⁻, N₃⁻) [29, 30]. These anions can form salts with
metals and show similar reactivity to halide ions [29, 30]. They can also form 'hydrogen halides'
 p-block

such as hydrogen cyanide (HCN), hydrogen thiocyanate (HSCN), and hydrazoic acid (HN₃), as
well as many other compounds analogous to those formed by halogens [29, 30].

Group 18 -He, Ne, Ar, Kr, Xe, Rn

Occurrence and methods of obtaining these elements:

Helium is found in significant quantities in natural gas deposits [1].
Neon, Argon, Krypton, and Xenon are present in the Earth's atmosphere and are commercially
obtained through the fractional distillation of liquid air [1].
Radon is a radioactive element produced by the radioactive decay of radium [1].
•
The noble gases have a range of important uses based on their unique properties [1]:
◦
Helium's exceptionally low boiling point makes it crucial in cryogenic research and for cooling
superconducting magnets [1]. Its low density and non-flammability make it ideal for filling
balloons and airships [1]. It is also used in breathing mixtures for deep-sea divers to prevent
nitrogen narcosis [1]. Notably, liquid helium exhibits superfluidity (Helium II) below a certain
temperature, a state with zero viscosity and unique thermal properties [2].
◦
Neon is primarily used in discharge tubes to produce a characteristic reddish-orange light,
widely used in advertising signs [1].
◦
Argon's inert nature makes it valuable as a protective atmosphere in metallurgical processes,
welding, and the production of titanium and other reactive metals [1].
◦
Krypton and Xenon are used in specialised discharge tubes and photographic flash lamps [1].
◦
Radon finds limited use in medical discharge tubes for radiotherapy [1].
•
The physical properties of noble gases are closely related to their monatomic nature and weak
intermolecular forces [2]. They exhibit very weak van der Waals (London dispersion) forces
between their atoms due to their non-polar nature [2]. This results in extremely low melting and
boiling points [2]. These melting and boiling points generally increase as you go down Group 18
(from Helium to Radon) due to the increasing atomic size and the resulting stronger London
dispersion forces [2]. Table 10.41 in the source provides specific values for these properties [2].
•
A pivotal discovery in chemistry was the realisation that Xenon, and to a lesser extent Krypton
and Radon, are not entirely inert and can form chemical compounds, primarily with highly
 p-block

electronegative elements like fluorine and oxygen [1, 3]. This contradicted the long-held belief
based on their stable electron configurations [3].
•
The first noble gas compound synthesized was Xenon difluoride (XeF₂) in 1962 [3]. The source
details the preparation of various xenon fluorides (XeF₂, XeF₄, XeF₆) by the direct reaction of
xenon with fluorine under varying conditions of temperature and pressure, often with a catalyst
[3, 4]. These fluorides are generally colourless crystalline solids that are susceptible to hydrolysis
[4, 5].
•
The source also describes the synthesis and properties of xenon oxides (XeO₃, XeO₄), which are
typically obtained by the hydrolysis of xenon fluorides [4, 5]. Xenon trioxide (XeO₃) is a
dangerous explosive in its dry state [4]. Xenon tetroxide (XeO₄) is also unstable [4].
•
Furthermore, xenon oxyfluorides (XeOF₂, XeOF₄) are discussed, formed through partial
hydrolysis of xenon fluorides or by the reaction of xenon oxides with xenon fluorides [4, 5].
These compounds exhibit interesting structural and bonding characteristics [4, 5].
•
The structures of xenon compounds can be effectively predicted using the Valence Shell Electron
Pair Repulsion (VSEPR) theory [6, 7]. The central Xenon atom can accommodate more than eight
electrons in its valence shell by utilising its available d-orbitals, leading to the expansion of its
octet [7].
•
The source provides tables (10.43 and 10.44) and figures (10.61 to 10.65) illustrating the
molecular geometries of various xenon compounds:
◦
XeF₂ is linear [6, 7].
XeF₄ is square planar [6, 8].
XeF₆ has a distorted octahedral geometry due to the lone pair of electrons [6, 8, 9].
XeO₃ is pyramidal [7, 9].
XeOF₂ is T-shaped [7, 9].
XeO₂F₂ has a see-saw shape [7, 9].
XeOF₄ is square pyramidal [7, 9].
XeO₄ is tetrahedral [7, 9].
[XeO₄]²⁻ (xenate ion) is also tetrahedral [7, 9].
XeO₃F₂ is trigonal bipyramidal [7, 9].
Ba[XeF<0xE2><0x82><0x88>] is octahedral [4, 7].
•
p-block

The bonding in xenon fluorides involves covalent bonds between Xenon and Fluorine atoms [6].
The ability of Xenon to form these bonds demonstrates that the concept of "inert gases" was an
oversimplification, particularly for the heavier members of the group [3].