STRUCTURE OF LIQUIDS
1. VOLUME CHANGES ON FUSION AND VAPORISATION
Fusion (solid → liquid)
When a solid melts into a liquid, the increase in volume is very small (≈ 1%).
Reason: In a solid, particles are arranged in a rigid, ordered lattice.
When it melts, the order is partly lost, but particles are still fairly close together.
So only a small volume change happens.
👉 Example: Ice → water, the volume increases just slightly (except water has a special case
where ice is less dense).
🔹 Vaporization (liquid → gas)
When a liquid changes to vapour, the volume increases enormously (≈ 100–1000
times).
Reason: In a liquid, particles are close but mobile.
In gases, particles are far apart with almost no intermolecular attraction.
So a huge increase in volume occurs.
🔹 Conclusion
Solid → liquid: small increase in volume → structure becomes a little disordered.
Liquid → gas: large increase in volume → structure becomes highly disordered.
Hence, the order of particle arrangement decreases in the sequence:
Solid (most ordered) → Liquid → Gas (most disordered).
✨ Simple student-friendly version:
Melting: volume change is small.
Boiling: volume change is very large.
This shows that liquids are less ordered than solids, but more ordered than gases.
Would you like me to also cover the Enthalpies of Fusion and Vaporization (the next part in
your text), in the same step-by-step way?
When a solid melts into a liquid, the increase in volume is very small (about 1%) because the
particles, though slightly disordered, still remain close together, whereas during
vaporization, the volume increases enormously (about 100–1000 times) since the particles
move far apart with negligible intermolecular attraction; thus, the change in volume on
fusion is small but on vaporization is very large, showing that liquids are less ordered than
solids but more ordered than gases.
2. Enthalpies of Fusion and Vaporization
The enthalpy of fusion (ΔHf) is the heat required to melt one mole of a solid at its melting
point, and it is much smaller than the enthalpy of vaporization (ΔHvap), which is the heat
needed to convert one mole of liquid into vapour at its boiling point; this is because melting
only partially disrupts the orderly arrangement of particles, while vaporization breaks almost
all intermolecular forces to separate the particles widely, so far more energy is required for
vaporization than for fusion.
Let’s add examples with values:
For ice (H₂O):
o ΔHf (fusion) ≈ 6.1 kJ mol⁻¹ → energy needed to melt 1 mole of ice at 0 °C.
o ΔHvap (vaporization) ≈ 40.7 kJ mol⁻¹ → energy needed to convert 1 mole of
water into vapour at 100 °C.
o Clearly, ΔHvap ≫ ΔHf.
For argon (Ar):
o ΔHf ≈ 1.2 kJ mol⁻¹
o ΔHvap ≈ 6.4 kJ mol⁻¹
o Again, vaporization requires far more energy.
👉 This big difference shows that melting only slightly disturbs intermolecular forces, while
vaporization almost completely breaks them, needing much more energy.
3. X-ray Diffraction (XRD)
Definition: XRD is an analytical technique used to determine the crystalline structure
of materials by studying how X-rays scatter when they strike the crystal lattice.
Principle: Based on Bragg’s Law
nλ=2dsinθn\lambda = 2d\sin\thetanλ=2dsinθ
where nnn = order of reflection, λ\lambdaλ = X-ray wavelength, ddd = distance
between crystal planes, and θ\thetaθ = diffraction angle.
How it works: When X-rays hit a crystal, they are diffracted by the regularly spaced
atomic planes. Constructive interference occurs at specific angles, producing a
diffraction pattern (peaks).
What it tells us:
o Crystal structure (cubic, tetragonal, hexagonal, etc.)
o Interplanar spacing (d-spacing)
o Crystallite size (via Scherrer equation)
o Degree of crystallinity
o Phase identification (which compounds are present).
Applications: Widely used in chemistry, physics, materials science, nanotechnology,
geology, and metallurgy for studying metals, ceramics, polymers, and nanomaterials.
🔹 XRD for Liquids
Liquids lack long-range order (no repeating lattice like in crystals), but they do have
short-range order — neighbouring molecules have preferred distances and
orientations.
When X-rays are passed through a liquid:
o Instead of sharp Bragg peaks (as in crystals), we get broad diffuse halos in the
diffraction pattern.
o The main broad peak corresponds to the average intermolecular distance
between molecules.
From these patterns, scientists calculate the radial distribution function (RDF), which
tells how particle density varies with distance from a reference particle.
The first peak in RDF shows the most probable nearest-neighbour distance, while
subsequent smaller peaks give information about second and third neighbour shells.
🔹 What XRD reveals about liquids
Average intermolecular separation (from the position of the main peak).
Degree of short-range ordering among molecules.
Structural information useful for understanding liquid structure models (like
“random close packing” or local molecular arrangements).
✨ In simple words:
XRD can’t give sharp crystal structures for liquids, but it can show how far apart the
molecules usually are and how they’re arranged locally, using diffuse diffraction halos and
radial distribution functions
