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QUESTIONS

1. Explain the meaning of the following concepts, by presenting some figures when required.
a. The degree of freedom (f) and Gibbs phase rule (5).
b. Intensive and extensive properties of thermodynamic functions(5).
c. Chemical potential (5).
d. Compressibility (5).
Answer 1.
a. Degree of freedom: the number of variables that can be changed independently without
disrupting the equilibrium of the system, i.e. the variables when changed a new face is not
introduced or an existing face is not dispelled.

Gibbs Phase rule:
Gibbs phase rule states that if a system containing C components and P phases is in equilibrium the number of
degrees of freedom F is given by P+F= C+2
A degree of freedom is an intensive variable such as T, P. X A, XB . . . that can be varied independently while
still maintaining equilibrium. If pressure is maintained constant one degree of freedom is lost and the phase
rule becomes
P+F= C+1
b. (i)The intensive properties are those which are independent of the size of the system such as T
and P,
(ii) The extensive properties are directly proportional to the quantity of material in the system,
e.g. P, E, H, S and G.
c. Chemical potential:
If a small quantity of element A, dnA, mol, is added to a large amount of a phase at constant
temperature and pressure, the size of the system will increase by dnA, and therefore the total free
energy of the system will also increase by a small amount dG'. If dnA is small enough dG' will be
proportional to the amount of A added. Thus we can write
dG ' =μ A dn A (T, P, nB constant) (1.28)
The proportionality constant μA, is called the partial molar free energy of A or alternatively the
chemical potential of A in the phase which depends on the composition of the phase. When
equation 1.28 is rewritten it can be seen that a definition of the chemical potential of A, μ A , is
μ A ¿( ∂G ' / ∂ n A )T ,P ,n B

where G' corresponds to the Gibbs free energy of the whole system.
d. Compressibility:

At constant T0C the free energy of a phase increases with pressure such that ( ∂G
∂P)
=V ,
T
which
shows that the slope of the free energy surface on isothermal planes equals the molal volume of the
corresponding phase. The curvature of the free energy surface on isothermal planes (T=const.),
which is the second derivation of the free energy, directly relates to the compressibility of the
corresponding phases according to the equation
∂2G
( ) ( )
2
=
∂V
∂P T ∂P T
=−βV

where β is called compressibility, the change in volume with pressure and expressed as

Sketch T-P phase diagram for pure iron and explain why the slope of a®g phase transformation line is negative while g®liquid transformation line is positive. Compare the positions of the transition temperature. The partial differentiation of the equation G=f ( P . Answer 2. b. T tr with melting temperature of a pure substance for the temperature dependent allotropy to occur. Change in enthalpy with increasing temperature causes an increase in enthalpy of the system. 3. Answer 3. Explain this question by driving Clausius – Clapeyron equation. T ) is dG= ( ) ( ) ∂G ∂P T dP+ ∂G ∂T P dT . Since the transformation from γ to liquid involves increase in both volume and enthalpy of the system. a. This equation can be compared with dG=V dP−SdT equation. Draw a schematic G-T-P diagram ( G=f ( P . The lines of phase transformation can be calculated according to the Clasius-Clapeyron equation as expressed. T ) ) of one component system and show that the slopes of the free energy surface surfaces in isobaric and isothermal planes are equal to the molal entropies. Therefore it can be easily seen that the following equation hold: ( ∂G ∂P ) T =V and ( ∂G ∂T )P =−S . dT TΔV = dP ΔH Transformation from α to γ with increasing temperature at a constant pressure results in a decrease in volume since γ has a close packed structure. of the respective phases. a. Therefore the slope dT /dP<0 is negative. ( ) ∂P T =V . ∂G ∂G ( ) ∂T P =−S . because each represents the change in molal free energy of the system. the slope of (γ to liquid) transformation will be positive.2. and volumes .

........ Molar Free energy (XA + XB = 1) of a solid solution consisting of element A and B is given in terms of the corresponding potential energies...........… ......... a.......... ln X A + X B .. Answer 4... 4.. For temperature dependent allotropy of a pure substance to occur melting temperature of the substance should be greater than the transition temperature.... Otherwise melting would occur before allotropic transformation takes place. ln X B b. This is indicated in part (a) of the following figure... a... G=μ A . Draw the molar free energy curve of this solid solution as a function of XB at two different temperatures T1 and T2 (T1< T2) and interpret the change in curvature of these free energy curves...… .....……… (2) By using equation (1) and (2) prove that chemical potential of elements A and B can be calculated as shown below: mA = G A + RT .... (1) and also given in terms of molar free energies of pure elements G A and GB as follows: G= X A G A +X B G B + RT ( X A . ln X B ) . mA and mB as follows: G = mAXA + mBXB J / mol ..... b....... ln X A mB = GB + RT . X A +μ B .........…..... (2) When rearranging equation (2) ... X B … … … … (1) G= X A G A + X B GB + RT ( X A ln X A + X B ln X B ) .

b. As the temperature increases GA and GA decrease and the free energy curves assume a greater curvature. and e. ( ) ∂G ∂T P =−S 5. Apply the phase rule at temperature T2 between composition points b and c . The decrease in GA and GB is due to the thermal entropy of both components and is given by the following equation. b. 3a. a. d. G= X A (G A +RT ln X A )+X B (G B RT ln X B ) And comparing this with Equation (1) yields the followings: μ A =G A + RT ln X A μB =G B +RT ln X b. The free energy of the solution G will depend on G A and GB. free energy curves of liquid and solid phases in the system at different temperatures are given in Fig. Draw the binary phase diagram in Fig 3f and indicate the face domains on the diagram. Components A and B in a binary system are fully soluble in each other in liquid and solid states at all composition range. By making use of these free energy curves. Assuming that the free energy of liquid is lower than that of solid solution. c.

An ideal solid solution formed by elements A and B has molar free energy as expressed. Cite the difference between the intensive and extensive properties of thermodynamic functions and give examples for each property. H and G have dependencies on the size of the system.8 The rate of decrease in G with increasing T corresponds to – S. A. Use Clausius. this free energy curve must end asymptotically at the vertical axes of the pure components. Draw temperature – pressure diagram for pure iron and explain why the slope of the curve separating a phase from g phase is negative. 8. G curves of liquid decreases more rapidly due to its higher increase in entropy with increasing temperature. whereas extensive properties like V. However There will be a volume decrease when a is transformed to phase because molar volume . therefore at all temperature GLGS since entropy for liquid being always higher than that of solid.f=c-p+1 ® f=2-2+1=1 6. i. E.7 Intensive properties such as T and P are independent of the size of the system. Show that if the schematic curve given below is properly plotted.e. 7. A. The change in ΔH is always positive with increasing temperature. A. G= X A G A + X B G B + RT ( X A ln X A + X B ln X B) .Clapeyron equation to explain it. Enthalpy of the liquid is higher than that of the solid at all temperature. 9.Clapeyron equation: dP ΔH ( ) = dT eq T eq ΔV Which gives the change in dT required to maintain equilibrium between the two different phases (a g) if pressure is increased by dP. The relative position of G curves of solid and liquid is given in Figure on the right (G=H-TS). tangential to the vertical axes of the diagrams. Draw the relative position of the free energy curves for both liquid and solid phases as a function of temperature and explain why the rate of change in the free energy of liquid is faster than that of solids.9 Clausius.

A. d. dP of g is smaller than that of a V = V m−V m< 0 ¿ . 11. Components A and B in a binary system are fully soluble in each other in liquid and solid states at all composition range. the molar free energy of the components of the solution. The molar free energy-composition diagram for an ideal solution is given below. And explain shortly why the molar free energy curve at higher temperature assumes a greater curvature. 10. Therefore the molar free energy-composition diagram assumes a greater curvature. must end asymptotically at the vertical axes of the pure component. hypothetical and simple binary phase diagram is as follows: . A. draw the binary phase diagram in Fig 5f and indicate the face domains on the diagram. b. c.10 The molar free energy of an ideal solution is G1 ΔG mix ⏞ G=G 2 =X ⏞ A G A + X B G B + RT ( X A ln X A + X B ln X B ) GA and GB. Therefore the sign of ¿ ) which is the γ α ¿ ¿ ¿ slope of (a g) transformation is negative. A typical. Assuming that the free energy of liquid is lower than that of solid solution. decrease with increasing temperature. free energy curves of liquid and solid phases in the system at different temperatures are given in Fig.11 12. when properly drawn. By making use of these free energy curves. 5a. and e. Show that the free energy curve.

T(Eutectic) and T2] as indicated on the phase diagram above. a. A. T1. and A and B are the two components and α and  are two solid phases rich in A and B respectively. b. solidus and solvus lines on the diagram depicting by the corresponding letters .b Liquidus: Tm(A)ypzk Tm(B) Solidus: Tm(A)xapqtlTm(B) Solvus: Amo and Bnq . Indicate liquidus.Where L stands for liquid.12.a A. Tm(B). Draw the free energy curves of the existing phases at the given temperatures [T m(A).12.