UPSC MainsGEOLOGY-PAPER-II201910 Marks
Q9.

Define thermodynamic phase rule and state its mathematical expression. Determine the degree of freedom for a system under equilibrium with 8 components and 5 mineral phases. Briefly discuss the principle of ACF diagram.

How to Approach

This question requires a demonstration of understanding of fundamental principles in petrology and geochemistry. The approach should begin with a clear definition of the thermodynamic phase rule, followed by its mathematical expression. Then, apply the rule to the given system (8 components, 5 phases) to calculate the degree of freedom. Finally, explain the principle behind the ACF diagram, highlighting its utility in understanding ternary systems. A structured response with clear definitions and calculations is crucial for scoring well.

Model Answer

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Introduction

The thermodynamic phase rule, a cornerstone of physical chemistry and petrology, provides a powerful tool for understanding the conditions of equilibrium in geological systems. It relates the number of degrees of freedom (F), components (C), and phases (P) present in a system at equilibrium. This rule is particularly valuable in interpreting the stability of minerals and the evolution of rocks under varying pressure, temperature, and compositional conditions. Understanding phase diagrams, like the ACF diagram, is essential for interpreting the mineral assemblages observed in metamorphic rocks and magmatic systems.

Thermodynamic Phase Rule: Definition and Mathematical Expression

The Gibbs Phase Rule states the number of independent intensive variables (degrees of freedom, F) that can be changed without altering the number of phases in a system at equilibrium. It is mathematically expressed as:

F = C - P + 2

Where:

  • F = Degrees of freedom
  • C = Number of components
  • P = Number of phases
  • 2 represents the two intensive variables, typically temperature and pressure.

The rule assumes that the system is in chemical equilibrium and that only intensive variables (temperature, pressure, composition) are considered, excluding extensive variables (mass, volume).

Degree of Freedom Calculation for the Given System

For a system under equilibrium with 8 components (C = 8) and 5 mineral phases (P = 5), the degree of freedom can be calculated as follows:

F = C - P + 2

F = 8 - 5 + 2

F = 5

Therefore, the system has 5 degrees of freedom. This means that five independent variables (e.g., temperature, pressure, and the compositions of four components, as one is fixed by stoichiometry) can be changed without altering the number of phases present in the system.

Principle of the ACF Diagram

The ACF diagram (Alkali – Feldspar – Calcium diagram) is a triangular diagram used to represent the chemical composition of igneous and metamorphic rocks, particularly those containing alkali feldspar, plagioclase feldspar, and calcium-bearing minerals. It’s a specialized type of ternary diagram.

Key Principles:

  • Ternary System: The ACF diagram represents a three-component system where the total composition is normalized to 100%. The three components are Alkali (A), Feldspar (F), and Calcium (C).
  • Compositional Representation: Each point within the triangle represents a unique chemical composition of the rock. The position of the point is determined by the relative proportions of the three components.
  • Mineral Assemblages: Different areas within the diagram represent the stability fields of different mineral assemblages. For example, the co-existence of alkali feldspar, plagioclase, and quartz is represented by a specific region.
  • Phase Boundaries: Lines within the diagram represent phase boundaries, indicating the conditions under which different mineral phases are stable. These boundaries are determined by experimental petrology and thermodynamic modeling.
  • Applications: The ACF diagram is used to interpret the petrogenesis of igneous and metamorphic rocks, to determine the pressure-temperature conditions of formation, and to predict the mineral assemblages that will form under specific conditions.

The ACF diagram simplifies the representation of complex chemical systems, allowing geologists to visualize and interpret the relationships between composition, temperature, pressure, and mineral assemblages. It is particularly useful in understanding the evolution of granitic magmas and the metamorphic reactions that occur in the crust.

Conclusion

The thermodynamic phase rule is a fundamental principle governing the behavior of geological systems at equilibrium. Applying this rule, we determined that a system with 8 components and 5 phases possesses 5 degrees of freedom. The ACF diagram, a powerful tool in petrology, allows for the visual representation and interpretation of complex chemical compositions and mineral assemblages, aiding in understanding the formation and evolution of rocks. These concepts are crucial for deciphering the geological history of our planet.

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

Phase
A phase is a physically distinct, chemically homogeneous, and mechanically separable portion of a system. Examples include solid minerals, liquids, and gases.
Component
A component is a chemically independent species that is necessary to define the composition of all phases in the system. It is chosen to minimize the number of independent chemical species required.

Key Statistics

The Earth's crust is composed of approximately 8 minerals making up 98.5% of its mass. (Source: Mason, B. (1966). *Principles of Geochemistry*)

Source: Mason, B. (1966)

Approximately 3,800 minerals have been identified, but only a few dozen are common rock-forming minerals. (Source: Deer, W. A., Howie, R. A., & Zussman, J. (1992). *An Introduction to the Rock-Forming Minerals*)

Source: Deer, Howie, & Zussman (1992)

Examples

Water's Phase Diagram

Water exhibits three phases – solid (ice), liquid (water), and gas (steam) – and its phase diagram illustrates the conditions of temperature and pressure under which each phase is stable. The triple point, where all three phases coexist, is a classic example of applying the phase rule.

Frequently Asked Questions

What happens if the phase rule is violated?

Violation of the phase rule indicates that the system is not at equilibrium. This could be due to kinetic factors (slow reaction rates) or the presence of metastable phases.

Topics Covered

GeologyPetrologyGeochemistryPhase EquilibriaMineralogyThermodynamics