Phase Rule

PHASE RULE Introduction Minerals are the monitors of the physical and chemical conditions under which they
formed. The occurrences of minerals, their parageneses (stable associations), types of reactions, and compositional variation (e.g. zoned minerals) all provide important information about geologic history and processes. Of particular importance to geologists are: Estimates of pressure and temperature (geothermobarometry) Estimates of other physico-chemical conditions such as acidity (pH) and oxidation state (eH) Partial pressures of gases (e.g. fugacities of H2O, CO2 , etc.) Partitioning of major and trace elements between phases (e.g. minerals, melts and/or fluids) to characterize and quantify petrogenetic processes; and Use of minerals in geochronology and thermochronology
Dr. E. Laxminarayana
Mail: elxnkits@yahoo.co.in
PHASE RULE
Gibbs' Phase Rule provides the theoretical foundation, based in thermodynamics, for characterizing the chemical state of a (geologic) system, and predicting the equilibrium relations of the phases (minerals, melts, liquids, vapors) present as a function of physical conditions such as pressure and temperature. Gibbs' Phase Rule also allows us to construct phase diagrams to represent and interpret phase equilibria in heterogeneous geologic systems. In the simplest understanding of phase diagrams, stable phase (mineral) assemblages are represented as "fields" (see colored areas on the figure to the right) in "P-T space", and the boundaries between stable phase assemblages are defined by lines (or curves) that represent reactions between the phase assemblages.
PHASE RULE
Why We Need Phase Diagrams!

Several phases crystallize sequentially over T and P range Minerals that are solid solutions change composition during crystallization sequence Melt (magma) composition clearly also changes during this time Minerals that form and their sequence of crystallization depend on composition of magma, T, P etc P and presence/nature of volatiles can affect the temperature range of crystallization All of the above applies in reverse for melting of a rock (and generation of magma) Remember that a rock can form by cooling (quenching) at any time during crystallization and we need to understand which crystals are present, in what proportions, and their compositions Clearly the above is complicatedhence PHASE DIAGRAMS!!!
PHASE RULE
Phase rule predicts quantitatively existing between different phase of a heterogeneous systems. Definitions: Phase an homogeneous physically distinct and mechanically separable portion of system. which is separated from other such parts of the system by definite boundary surfaces. i) at freezing point , water consists of three phases ii) a gaseous mixture, being thoroughly misible in all portions, will constitute one phase only. Thus, a mixture of N2 and H2 forms one phase only. iii) if two liquids are immiscible, they will form two separate phases.
PHASE RULE
If 2 solutions are miscible they will form one liquid phase only. A solution of a substance in a solvent consists of one phase only. eg: glucose solution Each solid makes up a separate phase. eg: S can exist together, but these are all separate phases. A heterogeneous mixture like CaCO3(s) CaO(s) + CO2 consists three phases Fe(s) + H2O(g) FeO + H2 Consists three phases. A homogenous solid solution of a salt constitutes a single phase. eg:FeSO4.(NH4)2SO4.6H2O solution constitutes a single phase although it consists of FeSO4.(NH4)2SO4 &H2O
PHASE RULE COMPONENT: The smallest number of independent variable constitutes, taking part in the state of equilibrium , by means of which the composition of each phase can be expressed in the form of chemical equation. i) in water system the chemical composition of all the three phases in H2O. Hence it is one component system. ii) the sulphur system consists of four phases, rhombic, monoclinic, liquid and vapour. the chemical composition of all phases is S. hence, it is one component system. iii) a system of saturated solution of NaCl consists of solid salt, salt solution and water vapour. the chemical composition of all the three phases can be expressed in terms of NaCl & H2O. Hence it is a 2 component system.
PHASE RULE
In the thermal decomposition of CaCO3 is 2 component system. In the dissociation reaction CuSO4.5H2O(s) CuSO4.3H2O(s) + 3H2O(g) Fe(s) + H2O ) FeO(s) + H2(g) it is a three component system.
PHASE RULE Degree of freedom:
The minimum number of independently variable factors, such as T,P & composition of the phases, which must be arbitrarily specified in order to represent prefectly the condition of a system. In case of water system. if all the 3 phases are present in equilibrium, then no condition need to be specified, as the 3 phases can be equilibrium only at particular T and P. the system is, therefore zero variant or non-variant or invariant or has no degree of freedom. if the condition is altered, three phases will not remain in equilibrium and one of the phase disappears.
PHASE RULE
water(l) ) vapour(g) we must state either the T or P to define it completely, hence degree of freedom is one or system is univariant. For a system consisting water vapour phase only. We must state the values of both T & P in order to describe the system completely. Hence, the system is bivariant. NaCl(s) ) NaCl-water(aq) ) water vapour(g) we must state either the Tor P. because the saturation solubility is fixed at a particular T or P.
PHASE RULE PHASE RULE
The phase rule is a generalisation given by willard gibbs (1874). It may be stated as Provided the equilibrium between any number of phases is not influenced by gravity or electrical or magnetic forces or by surface action and only by temperature, pressure and concentraton, then the number of degrees of freedom (f) of the system is related to the number of components (c) and of phases (p) BY THE PHASE RULE EQUATION P+F=C+2
PHASE RULE
Water system
The water system consists of three phases ice(s) water(l) water vapour(g) C=1 F=C-P+2 =1-P+2 F =3-P i.e.the degree of freedom depends on the number of phases present at equilibrium i) if P=1; F=2 (bivariant system) ii) if P=2; F=1 (uni variant system) iii) if P=3; F=0 (in variant system)
PHASE RULE
PHASE RULE
PHASE RULE
i)
Areas AOB vapour AOC liquid BOC ice Because to locate any point in an area, T aswell as P co-ordinates need to be known. P=1 F=2
ii)
Boundry lines OA, OB, OC P=2 F=1 in order to locate any point on a particular line, either T or P co-ordinate should be known. because for fixed value of one co-ordinate, the second is automatically fixed. Dr. E. Laxminarayana
PHASE RULE
iii) Triple point the three curves OA,OB,OC meet at O. at which solid, liquid and vapour are simultaneously at equilibrium. this point at 273.16k (0.0098oc) and 4.579mm is called a triple point. P=3 F=0 i.e.neither P nor T can be altered, even slightly, with act causing the disappearance of the of the phases. iv) Metastable curve: as water doesnot always freeze at0oc, soif the vessel containing water and vapour is perfectly clean and free from dust, it is possible to super cool water several degrees below its freezing point O. the dotted curve OA, a continuation of vaporization curve AO. Dr. E. Laxminarayana
PHASE RULE
Represents the vapour pressure curve of super cooled water. This curve represents a metastable system.on slight disturbance the super cooled water at once changes to solid ice. It may be noted that metastable vapour pressure of supercooled water is higher than the vapour pressure of ice.
PHASE RULE Phase rule for two component alloy systems In a two component system when P=1 F=2-1+2 F=3 since the maximum number of degrees of freedom in a 2 component system is 3. a solid-liquid equilibrium of an alloy has practically no gas phase and the effect of pressure is small on this type of equilibrium. Thus keeping the pressure constant of a system in which vapour is not considered is known condensed system. It will reduce the degrees of freedom of the system by one and for such a system. The phase rule becomes F=C-P+1 this is known as the reduced or condensed phase rule. Having 2 variables T &concentration ( composition) Dr. E. Laxminarayana Solid-liquid equilibria are represented on T & composition.
PHASE RULE LEAD-SILVER SYSTEM
It is 2 component system with 4 possible phase solid Ag, solid Pb, solution Ag+Pb and vapour. At constant atmospheric pressure as the gaseous phase is practically and one variable pressure is neglected. F=3-P is applicable.
PHASE RULE
i)
Curve AO: (freezing point curve of Ag) Shows the effect of freezing point of Ag on addition of lead in small quantities. The curve starts from A (961oc).the melting point of Ag, where pure Ag coexists as solid and iquid. The curve indicates that the melting point of Ag falls gradually on adding Pb, along AO, till the lowest point O (303oc) is reached. At O, no more lead can go in solution and consequently, melting point of Ag doesnot fall any further and if any lead is added, it separates as the solid phase. F=3-P, F=1,i.e.the system is univariant The point O (303oc) corresponds to a fixed composition of (2.6% Ag and 97.4% Pb) is known as eutectic composition. Dr. E. Laxminarayana
PHASE RULE
ii)Curve BO (freezing point curve of Pb) Represents the effect on freezing point of Pb on gradual addition of small amounts of Ag to it.point B is the meeting point of pure Pb(327oc) Along BO the melting point gradually falls on the addition of Ag, till lowest point O is reached. Where the solution gets saturated with respect to Ag and the melting point of Pb does not fall any more. iii) Point O (eutectic point) The 2 curves AO and BO meet at O The point O reprents (303oc) a fixed composition (Ag=2.6%,Pb=97.4%) and is called eutectic composition. No mixture of lead & silver has a melting point lower than the eutectic temperature.
PHASE RULE
Below the temperature line of eutectic temperature, we have two regions in the diagram The region marked eutectic + solid Ag, in which crystalline silver and solid eutectic are stable. The region marked eutectic + solid Pb, in which crystaline Pb and solid eutectic are stable. iv) Area AOB: Represents solution of Ag + Pb If a sample of solution Pb containing less than 2.6% Ag is taken, say P. On allowing the mass to cool, the T gradually falls without any change in composition, till point p is reached on the curve BO. On lowering the T, lead begins to separate out and the composition varies along po, till point O is reached. Dr. E. Laxminarayana

Phase Rule

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PHASE RULE Introduction Minerals are the monitors of the physical and chemical conditions under which they

Why We Need Phase Diagrams!

PHASE RULE Degree of freedom:

PHASE RULE PHASE RULE

PHASE RULE LEAD-SILVER SYSTEM

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