Thermodynamics of Materials

1) What is a phase, constituent, component?

• Phase is homogeneous part of the system having the same properties and composition and
separated by interface from other part of the system.
• Constituent (Species) are particles which can exist in the system. They can be elements, molecules
or ions.
• Components are minimal numbers of constituents, which can describe composition of any phase of
the system and can be separated from the system and exist independently. Elements or compounds
can be selected as components.

2) Law of thermodynamics, condition for equilibrium, heat capacity, the Gibbs-Helmholtz equation;
First Law of the Thermodynamics:
• The first law is the principle of conservation of energy. In the closed system the heat transferred to
a system is spent to change of internal energy and work done by the system: Q= ΔU+A,
where Q is heat transferred to the system, ΔU is the change of internal energy and A is
the work done by the system.
• Work A is positive when the work is done by the system and negative when work is done on the
system (convention), but it can be accepted vice versa.
Second Law of the Thermodynamics:
• Second law of thermodynamics introduces entropy S as function of state dQ/T=dS
• The entropy is a measure of the amount of energy which is unavailable to do work. It is impossible
to construct a heat engine that operating in the cycle produce no effect other than absorption of
energy from one reservoir and performance of an equal amount of work.
• Entropy is a measure of disorder and a measure of multiplicity of the system.
Third Law of the Thermodynamics:
• Theorem of Nernst: When T → 0 K, heat capacity CP→0, thermal expansion coefficient αV →0 and
entropy S→0.
• The entropy of pure element or substance in a perfect crystalline form is zero at absolute zero
(Planck).
• At absolute zero, the system must be in a state with the minimum energy state and the perfect
crystal has only one minimum energy state.
Condition for the Equilibrium:
• dG=0 (minimum G) Equilibrium at constant T and P
(T and P are characteristic state variable)
dG<0 Spontaneous change at constant T and P

• dF=0 (minimum F) Equilibrium at constant T and V

(T and V are characteristic state variables)
dF<0 Spontaneous change at constant T and V

• dS=0 (maximum S) Equilibrium at constant U and V – isolated system

(U and V are characteristic state variables)
dS>0 Spontaneous change at constant U and V

Heat Capacity:
• Heat capacity is amount of heat need to transfer to a body to raise its temperature by 1K.
  H   S    2G   U   S 
CP =   = T   = −T  2  CV =   = T 
 T  P  T  P  T  P  T V  T V

Standard entropy at 298 K --- Kirchhoff’s Law

 2VT
C P − CV = β is compressibility, α is thermal expansion


1  V  1   2G  1  V  1   2G 
 =−   = −  2  =   =  
V  P T V  P T V  T  P V  PT  P

3) What is chemical potential, Gibbs-Duhem equation, Raoult’s law, activity, coefficient of activity?
Chemical Potential:

 G 
 i = G i =  

 i  T , P ,n
n µi – chemical potential
j

ni – number of moles of component or species

Gibbs – Duhem Equation: (describes the relationship between changes in chemical potential for
components in a thermodynamic system)
- The Gibbs energy change due to adding or removing material at
dG=idni+nid constant P and T

N
dG = − SdT + VdP +  i dni
i
-SdT+VdP=nidi
i

 n d
i
i i =0 in equilibrium at constant T and P
other forms of the Gibbs-Duhem equation
  ln  1    ln  2 
  ln  1    ln  2  x1   = x2  
x1   = x2    x1  P ,T  x2  P ,T
 x1  P ,T  x 2  P ,T
Raoult’s law:

• Partial pressure of solvent (component 1) is proportional to its mole fraction in the solution. The
law is valid for dilute solution of not volatile component in volatile solvent.

P1 = x1 P10
• P1 is pressure of solvent over solution, x1 – mole fraction of solvent, P01 is pressure of saturated
vapour of solvent over pure solvent.
• Ideal solution is a solution for which each component i obeys Raoult‘s law and chemical potential
for each component i is expressed:

i = i0 + RT ln xi
In real solutions,

i = i0 + RT ln ai
a ᵢ = γ ᵢ x ᵢ, a ᵢ is activity, γ ᵢ is coefficient of activity
Activity and Coefficient of Activity:
Activity is “effective” concentration at which phase would behave as ideal Standard state can be selected
as pure component at given P and T or as state of infinite dilute solution
Definition of activity of component i is equal:
µi – chemical potential
  i −  i0 
ai = exp  

 RT 
 i0 - chemical potential in standard state

Coefficient of activity γi relates activity to measured concentration ai = γi . xi

Substituting mi in equation of Gibbs-Duhem by i = i0 + RT ln ai
different form of Gibbs-Duhem equation can be derived

  ln a1    ln a2    ln  1    ln  2 
x1   = x2   x1   = x2  
 x1  P ,T  x 2  P ,T  x 1  P ,T  x 2  P ,T

4) How to determine phase compositions for two phase equilibriums in binary system? Lever rule for
binary system, types of phase diagrams…
To Determine Phase Composition for Two Phase Equilibrium in Binary System:
 nα – amount of phase α

nβ – amount of phase β

XαB – mole fraction of component B in phase α

XβB – mole fraction of component B in phase β

XB – mole fraction of component B in alloy X

n xA + n  x A = x A
   n ( xB − xB ) + xB = xB
 
n x B + n x B = x B
x B − x B
n =
xA + xB = 1; x A + xB = 1; x A + xB = 1 n xB + (1 − n ) xB = xB xB − x B
n + n  = 1 xB − x B
n =
xB − x B

Types of Binary Diagram:

 5) The Gibbs triangle: how to determine composition? Lever rule for ternary system (two-phase
equilibrium, three-phase equilibrium)

X1=h1/(h1+h2+h3); X2=h2/(h1+h2+h3);
X3=h3/(h1+h2+h3)

Lever Rule for Ternary System (Two Phase and Three Phase Equilibrium)

Q is bulk composition of two-
phase mixture a+b;
According to lever rule:
m/m = (xC – xC)/(xC – xC) or
m/m = (xB – xB)/(xB – xB)
m and m are mole fractions of
phases α and β
6) What is liquidus surface, isothermal section, vertical (isoplethal) section?
Q is bulk composition of tree-phase mixture a+b+g;
Amount of phase α, β and γ (mα, mβ and mγ) are determined from
mass balance
xA = m xA + m xA + m xA
x,B = m xB + m xB + m xB
xC = m xC + m xC + m xC
m/(m + m + m) = |Qa|/|a| ternary lever rule
m/(m + m + m) = |Qb|/| β b|;
m/(m + m + m) = |Qc|/|γc|
7) Types of invariant reactions in ternary system. Show temperatures directions (decrease) of mono-
variant reactions around invariant point and phase compositions in invariant reactions. How three
phase equilibria look at temperature below and above invariant point?
Check Slide no. 20 also Ternary 3-Phase equilibrium(Solidification)
Types of invariant reactions in ternary systems are eutectic, peritectic and isomorphous
8) The Gibbs energy expression for elements and stoichiometric compounds (CP expressed by Maier-
Kelly equation);
9) Substitutional solution model (the Gibbs energy expression, excess Gibbs energy, Redlich-Kister
polynomial, lattice stability);
10) Sublattice model (for description of which phenomenon it is used, use example Laves phase C15
(Fe2Zr) in Fe-Zr system (Fe,Zr)2(Zr,Fe) to write the Gibbs energy of Laves phase and reciprocal
reaction);
11) Sublattice model for ionic crystal (use example of stoichiometric magnesioferrite (spinel structure)
with disordering between tetrahedral and octahedral sites (Mg+2,Fe+3)(Fe+3,Mg+2)2(Va)2(O-2)4 to
write Gibbs energy expression, electro-neutrality reaction for inverse spinel, to draw electro-
neutrality line, to write reciprocal reaction);
12) Methods of experimental measurements of thermodynamic functions;
13) Methods of phase equilibria investigations;