UPSC MainsGEOLOGY-PAPER-II201820 Marks
Q7.

Illustrate with neat sketches internal structure of calcite. How would you explain the differences in the internal structure of calcite and its polymorph aragonite?

How to Approach

This question requires a detailed understanding of crystal structures, specifically focusing on calcite and aragonite. The approach should involve first illustrating the internal structure of calcite with neat sketches, highlighting its rhombohedral unit cell and the arrangement of ions. Then, a comparison with aragonite, its polymorph, should be made, emphasizing the differences in their crystal structures (orthorhombic for aragonite) and how these differences arise due to variations in ion arrangement and temperature/pressure conditions. Diagrams are crucial for a good score.

Model Answer

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Introduction

Calcite and aragonite are both polymorphs of calcium carbonate (CaCO3), meaning they share the same chemical formula but differ in their crystal structure. Calcite is the more stable form at ambient temperatures and pressures, commonly found in sedimentary rocks like limestone and chalk. Aragonite, however, forms under higher pressure and lower temperature conditions, often found in marine organisms’ shells and in some metamorphic rocks. Understanding their internal structures is crucial for interpreting geological processes and material properties. This answer will illustrate the internal structure of calcite and explain the differences between it and aragonite.

Internal Structure of Calcite

Calcite crystallizes in the rhombohedral system, a variant of the hexagonal crystal system. Its structure is based on a framework of interconnected CaO6 octahedra and CO32- triangles. The key features of calcite’s internal structure are:

  • Unit Cell: The basic repeating unit of calcite is a rhombohedral unit cell.
  • Ion Arrangement: Calcium ions (Ca2+) occupy specific sites within the octahedra, while carbonate ions (CO32-) are arranged in a triangular fashion.
  • Layered Structure: Calcite exhibits a layered structure along the c-axis, with alternating layers of calcium and carbonate ions.
  • Spiral Growth: Calcite crystals often exhibit spiral growth patterns due to the arrangement of ions during crystallization.
Calcite Unit Cell

Figure: Calcite Unit Cell showing arrangement of ions. (Source: Wikimedia Commons)

Internal Structure of Aragonite

Aragonite, also CaCO3, crystallizes in the orthorhombic system. While it shares the same chemical composition as calcite, its internal structure is significantly different:

  • Unit Cell: Aragonite’s unit cell is orthorhombic, meaning it has three unequal axes at right angles to each other.
  • Ion Arrangement: The arrangement of calcium and carbonate ions differs from calcite. Aragonite features a more distorted arrangement of the CaO6 octahedra and CO32- triangles.
  • Stacking Sequence: The stacking sequence of layers in aragonite is different from calcite, leading to its distinct crystal morphology.
  • Needle-like Crystals: Aragonite often forms needle-like or prismatic crystals, unlike the more blocky or rhombohedral shapes of calcite.
Aragonite Unit Cell

Figure: Aragonite Unit Cell showing arrangement of ions. (Source: Wikimedia Commons)

Differences between Calcite and Aragonite

The differences in internal structure between calcite and aragonite are primarily due to the different ways the calcium and carbonate ions arrange themselves. This is influenced by factors like temperature, pressure, and the presence of impurities.

Feature Calcite Aragonite
Crystal System Rhombohedral (Hexagonal) Orthorhombic
Stability Stable at ambient conditions Metastable at ambient conditions; stable at higher pressures and lower temperatures
Ion Arrangement Less distorted CaO6 octahedra and CO32- triangles More distorted CaO6 octahedra and CO32- triangles
Typical Morphology Rhombohedral, blocky Needle-like, prismatic
Density 2.71 g/cm3 2.93 g/cm3

The higher density of aragonite is a direct consequence of its more compact crystal structure. The different stacking arrangements also affect their optical properties, such as birefringence. The transition from aragonite to calcite is a reconstructive phase transition, requiring significant energy input to rearrange the ions.

Conclusion

In conclusion, both calcite and aragonite are polymorphs of calcium carbonate, but their distinct internal structures – rhombohedral for calcite and orthorhombic for aragonite – lead to differences in their physical properties and stability. These structural variations are governed by the arrangement of ions and influenced by environmental conditions like temperature and pressure. Understanding these differences is crucial for interpreting the geological history of rocks and the formation of biogenic minerals.

Answer Length

This is a comprehensive model answer for learning purposes and may exceed the word limit. In the exam, always adhere to the prescribed word count.

Additional Resources

Key Definitions

Polymorphism
The ability of a solid chemical compound to exist in more than one crystal structure. Polymorphs have the same chemical formula but different arrangements of atoms in their crystal lattice.
Birefringence
A property of certain crystalline materials where light is split into two rays, each traveling at a different velocity. This results in a double image when viewed through the crystal, and is a characteristic property of calcite.

Key Statistics

Approximately 4% of the Earth’s crust is composed of calcium carbonate, primarily in the form of calcite and aragonite.

Source: Winkler, H. G. F. (1975). *Petrogenesis of metamorphic rocks*. Springer-Verlag.

The solubility of aragonite in pure water is approximately 0.013 g/L at 25°C, slightly lower than that of calcite (0.014 g/L).

Source: Langmuir, D. (1997). *Aquatic chemistry*. John Wiley & Sons.

Examples

Coral Reefs

Coral reefs are largely constructed from aragonite skeletons secreted by coral polyps. The aragonite is precipitated from seawater, and the reef structure provides habitat for a diverse range of marine life.

Frequently Asked Questions

Why does aragonite convert to calcite over time?

Aragonite is metastable at surface conditions. Over geological timescales, it tends to revert to the more stable calcite form through a process called inversion. This process is accelerated by increasing temperature and the presence of fluids.

Topics Covered

GeologyMineralogyCarbonate MineralsPolymorphismMineral Structure