Sylhet Engineering College, Sylhet.

(Department of Computer Science & Engineering)

Assignment
Course Code: Phy 0533-1103
Course Title: Physics
Assignment no: 03

Assignment on: Crystalline Structure of NaCl, CsCl

Submitted to:
Nusrat Jahan
Lecturer (Non-tech, Physics)
Sylhet Engineering College

Submitted By
Shrabony Ghosh Tithy
Registration No: 2023331509
Department of Computer
Science & Engineering
 “Structural Analysis of NaCl and CsCl Crystals”

Introduction:
Solids can be divided into two main types: crystalline and amorphous. Crystalline solids have a
well-organized, repeating three-dimensional structure known as a crystal lattice. The unit cell
defines this structure. It is the basic repeating unit that forms the whole crystal when it repeats in
all three directions. Atoms' arrangement in materials helps us grasp their chemical and physical
properties. In this assignment, we will look at two common ionic compounds: Sodium Chloride
(NaCl) and Cesium Chloride (CsCl). We'll look at their unique structures, coordination numbers,
and the factors that shape these arrangements.

Crystal Structure of NaCl:

Sodium Chloride (NaCl), also known as rock salt, is a common example of an iconic crystal. Its
structure is built on a face centered cubic (FCC) pattern.
• Lattice:
NaCl crystallizes in a face-centered cubic (FCC) lattice structure, also known as a rock-
salt structure. This lattice is formed by Cl⁻ ions occupying the face-centered cubic
positions, while Na⁺ ions fill the octahedral voids created by the arrangement of Cl⁻ ions.
The overall arrangement forms a repeating pattern where each Na⁺ is surrounded by Cl⁻
ions and vice versa.
• Basis:
Na⁺ at (0,0,0) Cl⁻ at (½,½,½) This means each primitive cell contains 4 Na⁺ and 4 Cl⁻
ions (total of 8 ions). The arrangement of these ions in the face-centered cubic lattice
ensures maximum packing efficiency, allowing for stable ionic interactions. This
structure is commonly observed in alkali halides and plays a crucial role in defining the
physical properties of NaCl, including its high melting point and brittle nature.

• Primitive Angle:
The NaCl crystal system is cubic, where the primitive angles are α = β = γ = 90°. This
symmetry contributes to the isotropic nature of the crystal, allowing uniform physical
properties in all directions.

• Coordination Number:
In the NaCl crystal structure, each sodium ion (Na⁺) is surrounded by six chloride ions
(Cl⁻), and each chloride ion is similarly surrounded by six sodium ions. This arrangement
results in a 6:6 coordination, meaning both types of ions have six nearest neighbors of the
opposite charge. This symmetrical configuration maximizes electrostatic attraction and
contributes to the overall stability and compactness of the crystal lattice.

• Ions Per Unit Cell:

 In the NaCl crystal lattice, ions occupy specific position with in the face-centered cubic
(FCC) unit cell.
1. Chloride Ions (Cl−):
8 corner ions, each shared among 8 unit cells:
1
8×8=1

6 face- centered ions, each shared between 2 unit cells:

1
6×2=3

Total Cl− ions per unit cell, 1 + 3 = 4.

2. Sodium Ions (Na+):
12 edge centered ions, each shared among 4 unit cells:
1
12× 4 = 3

1 body centered ion, fully inside the unit cell:

1 × 1 =1
Total Na+ ions per unit cell, 3 + 1 = 4.
• Stability:
The stability of ionic crystal structures can be explained using the radius ratio rule, which
compares the radius of the cation (r⁺) to that of the anion (r⁻).
1.02 Å
Radius ratio = rNa+ / rCl- = 1.81 Å  0.56

According to the radius ratio guidelines, a ratio between 0.414 and 0.732 is suitable for an
octahedral arrangement, which corresponds to a coordination number of 6. Since the ratio
for NaCl falls within this range, the compound naturally adopts a 6:6 coordination and
forms a face-centered cubic crystal structure.

Crystal Structure of CsCl:

Cesium chloride (CsCl) has a different type of cubic structure than NaCl. Instead of a face-centered
cubic pattern, CsCl forms a simple cubic lattice, where each ion sits at the center or corner of the
cube.
• Unit Cell Description:
The CsCl unit cell is characterized by:
1. Chloride Ions (Cl−): Occupying the eight corner positions of a cube.
2. Cesium Ion (Cs+): Located at the exact center of the cube (body-centered position).
It’s important to understand that even though there is an ion at the center of the cube, the
overall structure is still considered a primitive cubic lattice. This arrangement can also be
 thought of as two simple cubic lattices overlapping—one made of Cs⁺ ions and the other
of Cl⁻ ions—fitting together to form the complete crystal structure.
• Basis:
Cs⁺ at (0,0,0), Cl⁻ at (½,½,½). This means each unit cell contains 1 Cs⁺ ion and 1 Cl⁻ ion
(a total of 2 ions). The arrangement of Cs⁺ at the center and Cl⁻ at the corners (or vice
versa) results in a simple and symmetric structure, often referred to as body-centered type.
This compact and regular configuration contributes to efficient packing and strong ionic
bonding in the crystal. The relatively large size of the Cs⁺ ion allows it to accommodate
more anions around it, enabling a higher coordination number compared to structures like
NaCl.
• Primitive Angle:
The crystal structure is cubic, with angles α = β = γ = 90°. This symmetry makes the crystal
isotropic, meaning it exhibits uniform physical properties in all directions.
• Coordination Number:
Each Cs⁺ ion in the crystal is surrounded by 8 Cl⁻ ions, and each Cl⁻ ion is also
surrounded by 8 Cs⁺ ions. This results in an 8:8 coordination, meaning both ions are in
contact with eight oppositely charged neighbors, forming a highly symmetrical and
tightly packed structure.
• Ions per unit Cell:
In the CsCl crystal lattice, ions are arranged in a simple cubic structure with one ion at each
corner and one ion at the center of the cube.
1. Chloride Ions (Cl−): There are 8 chloride ions at the corners of the cube. Since each
corner ion is shared by 8 neighboring unit cells, the contribution is:
1
8×8=1

Total Cl− ions per cell: 1.

2. Cesium Ions (Cs+): There is 1 cesium ion at the body center of the cube, fully
contained within the cell:
1×1=1
Total Cs+ ions per unit cell: 1.
• Stability:
The stability of ionic crystal structures can be explained using the radius ratio rule, which
compares the radius of the cation (r⁺) to that of the anion (r⁻).
1.67 Å
Radius Ratio = rCs+ / rCl- = 1.81 Å  0.92

According to the radius ratio guidelines, a ratio greater than 0.732 favors a cubic
arrangement, which corresponds to a coordination number of 8. Since the ratio for CsCl is
approximately 0.92, the compound adopts an 8:8 coordination and forms a simple cubic
crystal structure.
Comparison and Contrast of NaCl and CsCl Crystal Structures:

While both NaCl and CsCl are ionic compounds exhibiting cubic crystal systems, their specific
arrangements differ significantly, primarily influenced by the relative sizes of their constituent
ions.

Properties NaCl Structure (Rock Salt) CsCl Structure

Simple Cubic (SC) or Primitive
Lattice Type Face Centered Cubic (FCC)
Cubic with basis
Body Centered position of Cl− SC
Cation Position Octahedral Holes of Cl− FCC lattice
lattice
Anion Position FCC lattice points Corner positions of the cube
Coordination 6:6 (Each ion surrounded by 6 8:8 (Each ion surrounded by 8
Number opposite ions) opposite ions)
Geometry of
Octahedral Cubic
Ions
Formula Units/
4 1
Unit Cell
Ion Size Ratio Typically between 0.414 and 0.732 Typically greater than 0.732 (e.g.,
(r+ / r−) (e.g., Na+ / Cl−  0.54) Cs+ / Cl−  0.93)
Packing
~ 67% ~ 68%
Efficiency

Application of NaCl and CsCl Crystals:

• NaCl (Rock Salt):

1. Essential for human nutrition (table salt).
2. Essential for industrial uses such as, Chlorine production, water softening, and
chemical synthesis.
3. Optical material in infrared spectroscopy due to transparency in IR regions.
• CsCl:
1. Used in density gradient centrifugation for DNA / RNA separation.
2. Scintillation counters in radiation detection (e.g., medical imaging).
3. Research in crystallography and solid – state ionics.

Conclusion:
CsCl and NaCl's crystal structures show how ionic sizes and Coulombic forces affect lattice
shape. The Radius Ratio Rule shows that CsCl has an 8:8 coordination. This leads to a simple
cubic structure. In NaCl, the coordination is 6:6, forming a face-centered cubic (FCC) lattice.
These structures show the importance of crystallography in determining material properties.
They matter a lot for important uses, from high-level science to daily nutrition. Understanding
these ionic arrangements is crucial for advancing solid-state physics and materials science