Solids

Definition
Rigid, hard substances having definite shape, definite volume and cannot flow are called solids."
Important Points
1- Particles are closely packed 5- Well-ordered arrangement
2- Particles show only vibrational motion (Lowest K.E.) 6- Incompressible
3- Strong cohesive forces (I.M.F.) 7- Higher density than liquids and gases
4- No Diffusion in solids. 8- Slightly expand on heating
Difference between Crystalline and Amorphous Solids
Property Crystalline Solids (Ionic, Giant Amorphous Solids
Covalent, Molecular & Metallic Solids)
Shape Definite characteristic geometrical shape Irregular shape
Internal Structure Long-range three dimensional regular & Short-range, disordered, non-recurring,
repeating arrangement irregular arrangement
Nature True solids Pseudo solids or super cooled liquids or
highly viscous liquids
Cooling (Growth Formed by slow cooling Formed by rapid cooling
of crystal)
Melting Point Sharp and characteristic melting points Gradually soften over a range of
temperature
Heat of Fusion Definite and characteristic heat of fusion No definite heat of fusion
Anisotropy Anisotropic in nature (Different properties Isotropic in nature (Small regions of
along different directions) symmetry are called Crystallites)
Cleavage Break sharply along definite planes (Cleavage Irregular fracture with curved surfaces
Property itself anisotropic)
Rigidity Rigid under stress May deform under stress
Entropy Lower due to ordered structure Higher due to disordered structure
Examples NaCl, Sugar, Ice, Diamond, Cu, Zn Rubber, Plastic, Glue, Glass, Paper
Applications used where mechanical strength and rigidity used in manufacturing (e.g., plastics,
are needed (e.g., gemstones, construction) rubber, adhesives, optical fibers)

Properties of Crystalline Solids

(i) Geometrical Shape: Definite (Ordered arrangement)
(ii) Melting point: Definite (Ordered arrangement)
(iii) Cleavage planes: Breakdown from different directions (inclined at some angle). Cleavage itself
anisotropic behavior.
(iv) Anisotropy: Physical properties depending upon direction. e.g. electrical conductivity (Graphite
is conductor parallel to layers, but non-conductor perpendicularly), cleavage, refractive index,
thermal expansion.
(v) Symmetry: repetition of faces angles or edges by rotating the crystal. (Center of Symmetry,
plane of symmetry, axis of symmetry)
(vi) Habit (Growth) of crystal: Shape of crystal in which it usually grows (on cooling). e.g. NaCl
cubic, but 10% urea in NaCl makes it needle like.
(vii) Isomorphism: Two or more substances showing same crystalline forms. (1)-Different physical
and chemical properties. (2) Isomorphs have same atomic ratio and geometry (Radius Ratio).
 e.g. Cu, Ag, Au, Al, Ca, Sr, Ni, Pt (1:1) FCC
IA(Alkali metals), Ba, Fe, V, Cr (1:1) BCC
Zn, Cd, Graphite, Be, Mg, Sc, Ti, Co (1:1) Hexagonal
NaF, MgO, NaCl (1:1) Cubic
NaNO3, CaCO3 (1:1:3) Rhombohedral (nitrate and carbonate ions are triangular planar)
K2SO4, Na2CrO4 (2:1:4) Orthorhombic (sulfate and chromate ions are tetrahedral)
(viii) Polymorphism: Compound having more than one crystalline form (due to non directional nature
of ionic bonds).
Polymorphs have same chemical properties but different physical properties.
e.g. AgNO3 (Rhombohedral & Orthorhombic)
CaCO3 (Trigonal & Rhombic)
(ix) Allotropy: Element having more than one crystalline form.
Allotropes (Allotropic forms) have same chemical properties but different physical properties.
e.g. Carbon= Cubic (Diamond) & Hexagonal (Graphite)
Sulphur (S8) = rhombic and monoclinic
Tin (Sn)= Grey tin(cubic) & white tin(tetragonal)
(x) Transition Temperature: Temperature at which two crystalline forms of a compound
(polymorphs) or element (allotropes) coexist in dynamic equilibrium. Transition temperature is
always less than the melting point of that specie.
𝟏𝟐𝟖℃
e.g. 𝐾𝑁𝑂3 (𝑂𝑟𝑡ℎ𝑜𝑟ℎ𝑜𝑚𝑏𝑖𝑐) ⇔ 𝐾𝑁𝑂3 (𝑅ℎ𝑜𝑚𝑏𝑜ℎ𝑒𝑑𝑟𝑎𝑙)
𝟗𝟓.𝟓℃
Sulphur (S8) rhombic ⇔ Sulphur (S8) monoclinic
𝟏𝟑.𝟐℃
Grey Tin ⇔ White Tin

Crystal Lattice
 Crystal is made of particles (atoms, ions or molecules).
 A crystal lattice represents the array (repeating pattern) of particles in 3D space.
 Particles occupy fixed positions (called lattice points or lattice sites) in space.
 3D arrangement of points is called a crystal lattice or space lattice.

Unit Cell
 Unit cell is the smallest repeating part of a crystal lattice.
 It has all properties of the entire crystal.
 The entire crystal can be built by repeating the unit cell in 3D space.
 Knowing the unit cell = knowing the whole crystal structure.
 A unit cell is described by 6 parameters:
 3 lengths: a, b, c along x, y, z axis respectively.
 3 angles: α (between b & c), β (between a & c), γ (between a & b).
 These 3 sides & 3 angles are called unit cell dimensions or crystallographic elements.
 Comparison of Types of Solids (Based on Nature of Bonding)
Sr Giant Covalent Metallic
Property Ionic Solids Molecular Solids
(Atomic) Solids Solids
1 Constituent Atoms (form Small Molecules
Metal cations &
Cations & Anions delocalized
Particles Macromolecules) (Polar or non-polar)
electrons
2 Ionic bonds (Show
Network of
H-bonds (Dip-Dip) Metallic bonds
Bonding Type isomorphism & or Van der Waal’s (Strength = no
Covalent bonds
Polymorphism) (LDF) of valence e-)
3 Physical State Solid only Solid only
Solid (I2), Liquid Solid only (at
(H2O) or Gas (CO2) room temp)
4 Electrical
(Solid poor) Conductor
Poor (except Poor (Except HCl
Best Conductors
in Molten or aqueous due to free e-
Conductivity state due to free ions
graphite) solution)
(solid & molten)
5 Melting/Boiling Low (non-polar) to
High Very high Generally high
Point moderate (polar)
6 Hardness Hard but brittle Very hard
Soft (Weakest Hard, malleable,
forces=IMF) ductile
7 Variable (diamond: Low density,
High (except
Density Moderate to high high, graphite: Sometimes
Alkali metals)
low) transparent to light
8 High (especially
Non-volatile
Volatility Non-volatile Non-volatile (except Hg
gases)
vapor)
9 (I2) Soluble in non-
Insoluble in
Solubility Soluble in water most solvents
Insoluble in water polar solvents (CCl4)
(Like dissolve like) (Ion-Dipole) (may react with
(due to LDF)
acids or water)
10 Reactions
Fast (in solutions),
Slow
Slow to Moderate Moderate to
yield high (yield low) fast
11 Giant (Diamond,
Silicon, SiC, AlN & Dry Ice (CO₂), I₂,
Examples NaCl, MgO, CaCO3 SiO₂), Layered Glucose, Ice (H2O), Fe, Cu, Al, Zn
(Graphite, BN, solid HCl
CdI2)
12 Shown by Compounds
Elements & Elements &
Elements
compounds compounds

Iodine Structure (FCC)

o Discrete molecules (I2) forming crystals
o Non-polar nature (LDF)
o I-I bond distance:
 Solid state: 271.5 pm (longer due to Van der Waal’s forces).
 Gas phase: 266.6 pm (shorter, no intermolecular forces).
o Poor conductor due to localized electrons.
o Softer than covalent solids & compressible (Weak Van der Waal forces)
o Volatile, low melting point solid (LDF)
o Soluble in non-polar solvent CCl4
 NaCl Structure (FCC)
Ion Arrangement
o Each Na⁺ is surrounded by 6 Cl⁻
o Each Cl⁻ is similarly surrounded by 6 Na⁺
o Octahedral void & Coordination number = 6
o Coordination number: “No of oppositely charged ions
surrounding an ion”. Greater the size of central ion,
greater the coordination No.
Size & Distance
o Cl⁻ is larger than Na⁺ (Cl⁻: 18 e⁻, Na⁺: 10 e⁻).
o Distance between two adjacent Cl⁻ ions = 5.63 Å.
o Na⁺Cl⁻ distance = 2.815 Å (half of 5.63 Å).
Unit Cell Composition
o Cl⁻ ions:
 8 at corners (shared by 8 unit cells → contributes 1 Cl⁻).
 6 at face centers (shared by 2 unit cells → contributes 3 Cl⁻).
 Total Cl⁻ per unit cell = 4.
o Na⁺ ions:
 12 at edge centers (shared by 4 cells → contributes 3 Na+)
 1 at body center (contributes 1 Na+)
 Total Na⁺ per unit cell = 4.
o Formula units per cell = 4 Na+Cl-
o Total Ions per unit cell = 4 + 4 = 8
Important Points
o No discrete NaCl molecules in solid state—only a 3D lattice of ions.
o Formula Unit (Empirical formula) & Formula Mass ( Empirical formula mass)
o NaCl exists as independent molecules only in vapor phase.
o FCC structure

Lattice Energy (Ionic Bond)

Definition
o Energy released when 1 mole of ionic crystal forms from gaseous ions (Exothermic) OR
energy needed to break 1 mole of solid into isolated gaseous ions (Endothermic).
o Units: kJmol⁻¹.
Na+(g) + Cl−(g) → NaCl(s) ΔH = −787 Kj.mol−1
Trends in Lattice Energy
o Decreases as ion size increases (weaker attraction due to larger distance).
o Increases with higher ion charge (stronger electrostatic attraction).
 LiCl (-833) > NaCl (-787) > KCl (-690) (same Cl⁻, increasing cation size).
 NaF (-895) > NaCl (-787) > NaBr (-728) (same Na⁺, increasing anion size).
Factors Affecting Lattice Energy (charge density = charge/size)
o Ionic radius (smaller ions → higher energy).
o Charge on ions (e.g., MgO > NaCl due to Mg²⁺ and O²⁻).
o Crystal packing efficiency e.g., FCC (more efficient) vs. BCC
Important points
 o Lattice energy is helpful in discussing structure, bonding, properties, stability, melting
point, and solubility of ionic compound.
o Covalent bonds (Bond energy) & Ionic bonds (Lattice energy)

Factors Affecting Shape of Ionic Crystals

1- Radius Ratio
𝒓+
o ( ) Determines coordination number and structure stability
𝒓−
o Example:
 NaCl is Face centered cubic (CN=6)
 CsCl is body centered cubic (CN=8)
2- Electrostatic Force (Coulombic Attraction)
o Governs shape, ions packing efficiency and lattice energy.
3- Poor Conductivity
o Solid state: Ions are fixed → no conductivity.
o Definite shape.

Diamond Structure (FCC)

Atomic Structure
 Carbon hybridization: sp³ (one s-orbital & three p-orbitals).
 Tetrahedral geometry: Each C-atom forms 4 covalent bonds at 109.5° angles.
Crystal Lattice
 Giant covalent network: Each C-atom bonded to 4 others in 3D.
 Bond length: 154 pm (C-C bonding only by sp3-sp3 overlap) uniform throughout
 Unit cell: Face-centered cubic (FCC) arrangement.
Properties
 Hardest natural material (continuous C-C covalent bonds).
 High melting point due to strong bonds.
 Electrical insulator (no free electrons; all valence electrons bonded).
 Thermal conductor (vibrational energy transfer via covalent network).
Macro-Molecule Concept
 Entire diamond is a single giant molecule called macromolecule.
 Comparison of Diamond & Graphite
Property Diamond Graphite

Hybridization C-atom Tetrahedral, sp³ C-atom Trigonal planar, sp²

2D layers (within layer covalent bond)

Bonding 3D covalent network
(between layers Van der Waals forces)

Conductivity Insulator Conductor parallel to layers (delocalized e⁻ within a layer)

Extremely hard (Giant 3D

Hardness Soft (slippery layers)
structure)

Unit Cell Face centered Cubic Hexagonal

Types of Cubic structures

Face-Centered Cubic (FCC)
Body-Centered
Property Simple Cubic (SC) or Cubic Close Packing
Cubic (BCC)
(CCP)

Space Occupied 52% 74%

68%
(Packing Efficiency) (Least efficient) (Most efficient)

Coordination Number
6 (Weak packing) 8 12 (Close-packed)
(Surrounding atoms)

Atoms per Unit Cell 1 2 4

8 corners + 8 corners +
Location of Atoms Only at 8 corners
1 center 6 faces

Density Lowest Medium Highest

Least stable (rare Moderate (high- Most stable (ductile &

Stability
in nature) melting metals) dense)

Polonium (Po), Alkali metals, Iron Aluminum (Al), Copper (Cu),

Examples
Manganese (Mn) (α-Fe), Tungsten (W) Gold (Au), Platinum (Pt)