Main group elements, also known as representative elements, are found in Groups 1, 2,
and 13–18 of the periodic table. These elements include the alkali metals, alkaline earth metals,
boron group, carbon group, nitrogen group, chalcogens, halogens, and noble gases.
Group 1: Alkali Metals
Elements: Li, Na, K, Rb, Cs, Fr.
Properties: Highly reactive, soft, low melting points, form +1 ions.
Group 2: Alkaline Earth Metals
Elements: Be, Mg, Ca, Sr, Ba, Ra.
Properties: Less reactive than alkali metals, form +2 ions, harder and denser
Group 13: Boron Group
Elements: B, Al, Ga, In, Tl.
Properties: Boron is a metalloid; others are metals. Form +3 oxidation state
Group 14: Carbon Group
Elements: C, Si, Ge, Sn, Pb.
Properties: Carbon is a nonmetal; Si and Ge are metalloids; Sn and Pb are metals.
Group 15: Nitrogen Group (Pnictogens)
Elements: N, P, As, Sb, Bi.
Properties: Nitrogen is a diatomic gas; others are solids with varying reactivity.
Group 16: Chalcogens
Elements: O, S, Se, Te, Po.
Properties: Oxygen is a diatomic gas; others are solids with varying reactivity.
Group 17: Halogens
Elements: F, Cl, Br, I, At.
Properties: Highly reactive nonmetals, form -1 ions.
Acid-Base Behavior:
Oxides of metals are basic (e.g., Na₂O, CaO).
Oxides of nonmetals are acidic (e.g., CO₂, SO₂).
Allotropy refers to the existence of an element in two or more different physical forms in the
same state (solid, liquid, or gas). This phenomenon is particularly common among main group
elements due to variations in bonding and atomic arrangement. Below is a detailed overview of
the allotropy of main group elements, organized by group.
Summary of Allotropy in Main Group Elements
Element Allotropes Key Features
Carbon Diamond, Graphite, Diverse bonding, sp²/sp³
Graphene, etc. hybridization.
Phosphorus White, Red, Black, Violet Tetrahedral P₄, polymeric
chains, layered.
Sulfur Rhombic, Monoclinic, S₈ rings, amorphous
Plastic chains.
Boron α-Rhombohedral, Icosahedral B₁₂ units,
β-Rhombohedral complex structures.
Oxygen O₂, O₃ Diatomic vs. triatomic
molecules.
Nitrogen N₂, Solid Nitrogen Triple-bonded N₂,
high-pressure forms.
Silicon Crystalline, Amorphous Diamond-like structure,
disordered forms
Summary of Allotrope Structures
Element Allotrope Structure Atomic
Arrangement
Carbon Diamond sp³ hybridized, 3D network of
tetrahedral tetrahedra
Graphite sp² hybridized, Layers of hexagons
hexagonal
Graphene sp² hybridized, Single layer of
hexagonal hexagons
Fullerenes Closed cages (e.g., Spherical or
C₆₀) ellipsoidal
molecules
Carbon Nanotubes Cylindrical tubes of Hexagonal lattice
graphene rolled into a tube
Phosphorus White Phosphorus Tetrahedral P₄ Discrete P₄ units
molecules
Red Phosphorus Polymeric chains of Amorphous or
P₄ units semi-crystalline
network
Black Phosphorus Layered, puckered Covalently bonded
hexagonal lattice layers
Sulfur Rhombic Sulfur S₈ rings Crystalline
arrangement of S₈
rings
Monoclinic Sulfur S₈ rings Needle-like crystals
Plastic Sulfur Long chains of Amorphous,
sulfur atoms disordered chains
Oxygen Dioxygen (O₂) Diatomic molecules Linear O=O
molecules
Ozone (O₃) Bent triatomic O-O-O with ~117°
molecules bond angle
Boron α-Rhombohedral Icosahedral B₁₂ 3D network of B₁₂
Boron units icosahedra
β-Rhombohedral Complex More complex 3D
Boron arrangement of B₁₂ network
and B₈₄ units
Silicon Crystalline Silicon Diamond-like cubic sp³ hybridized,
structure tetrahedral
Amorphous Silicon Disordered network Lack of long-range
order
Synthesis of Main Group Elements and Compounds
Group 1: Alkali Metals
Synthesis of Elements: Alkali metals are typically extracted by electrolysis of their molten salts
(e.g., NaCl for sodium).
Group 2: Alkaline Earth Metals
Synthesis of Elements: Extracted by electrolysis of molten salts (e.g., MgCl₂ for magnesium)
Group 13: Boron Group
Synthesis of Elements: Boron is obtained by reduction of boron oxide
Group 14: Carbon Group
Synthesis of Elements: Carbon is obtained from natural sources (e.g., graphite, diamond).
Group 15: Nitrogen Group
Synthesis of Elements: Nitrogen is obtained from the fractional distillation of liquid air.
Group 16: Chalcogens
Synthesis of Elements: Sulfur is obtained from natural deposits or the Claus process.
Group 17: Halogens
Synthesis of Elements: Chlorine is obtained by electrolysis of NaCl solution.
Group 18: Noble Gases
Synthesis of Elements: Noble gases are obtained from the fractional distillation of air.
Bonding in Main Group Elements and Compounds
Ionic Bonding
Occurs: Between metals (Groups 1 and 2) and nonmetals (Groups 16 and 17).
Covalent Bonding
Occurs: Between nonmetals and metalloids (Groups 13–17).
Metallic Bonding
Occurs: In pure metals and alloys (Groups 1, 2, and some in Groups 13–15).
Coordinate Bonding
Occurs: When a lone pair of electrons is donated to an electron-deficient species.
Hydrogen Bonding
Occurs: In compounds with hydrogen bonded to highly electronegative atoms (e.g., O, N, F).
Structural Arrangements in Main Group Compounds
Ionic Structures
NaCl (rock salt structure): Face-centered cubic lattice of Na⁺ and Cl⁻ ions.
CaF₂ (fluorite structure): Cubic lattice with Ca²⁺ ions surrounded by F⁻ ions.
Covalent Structures
Diamond (carbon): Tetrahedral network of sp³ hybridized carbon atoms.
Graphite (carbon): Layers of sp² hybridized carbon atoms in hexagonal rings.
Molecular Structures
P₄ (white phosphorus): Tetrahedral arrangement of phosphorus atoms.
S₈ (sulfur): Crown-shaped rings of sulfur atoms.
Polymeric Structures
Boron nitride (BN): Hexagonal lattice similar to graphite.
Silicates (SiO₄): Tetrahedral units linked in chains, sheets, or 3D networks.
Cluster Structures
Boranes (e.g., B₂H₆): Electron-deficient clusters with multi-center bonding.
Zintl ions (e.g., [Pb₅]²⁻): Polyanionic clusters formed by post-transition metals.
Summary of Synthesis, Bonding, and Structure
Group Synthesis Bonding Structure
1 Electrolysis of Ionic Cubic (e.g., NaCl)
molten salts
2 Electrolysis of Ionic Cubic (e.g., MgO)
molten salts
13 Reduction of oxides Covalent, metallic Tetrahedral (e.g.,
Al₂O₃)
14 Natural sources, Covalent Tetrahedral
reduction (diamond), layered
(graphite)
15 Fractional Covalent, ionic Tetrahedral (P₄),
distillation, direct layered (black
reaction phosphorus)
16 Claus process, Covalent, ionic Ring (S₈), layered
direct reaction (Te)
17 Electrolysis, direct Ionic, covalent Molecular (Cl₂),
reaction ionic (NaCl)
18 Fractional Weak van der Monatomic (e.g.,
distillation of air Waals Xe)
