Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S.

Qin)

8. Thermodynamics of solidification 1

8.1 The first law of thermodynamics Thermodynamics is concerned with energy and the way energy is transferred. The first law of thermodynamics addresses the energy conservation. It says that the energy can neither be created nor destroyed in a system of constant mass, although it may be converted from one form to another. The system exchanges energy with external environment by either changing its own internal energy or doing work to the environment. Suppose that q energy is exchanged between the system and environment, we define q>0 if energy is absorbed from the environment and q<0 if energy is evolved to the external environment. The internal energy is defined as the total kinetic energies and the energies of interaction of the particles of the particle in the system. The energy conservation gives the relationship

U = q w

(8.1)

where U is the change of internal energy, w is the work done by the system. If qP energy are introduced to the confined gas with constant pressure p, on the one side the internal energy of gas increases and on another side the gas is expanded to maintain the constant pressure, as illustrated in figure 1.

U1, v1

U2, v2

qP Figure 1. Gas expansion due to energy absorption

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

During the volume expansion, gas has done work by pushing the piston and the work is given by

w = p v

(8.2)

where v is the change in the volume of gas. Substituting eq. (8.2) into eq. (8.1) gives

U = q P pv
or

(8.3) (8.4)

(U + pv ) = q P
The term U+pv is called enthalpy H = U + pv . It gives

H = q P
When v=0 there is no done, equation (8.1) has the format of

(8.6)

U = q v
where qv is the energy absorbed by the system with constant volume.

(8.7)

The heat capacity is defined as the quantity of heat necessary to raise the system by a temperature T.

C=

dq dT

(8.8)

At constant pressure case it has

Cp =
At constant volume case it has

dH dT

(8.9)

Cv =

dU dT

(8.10)

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

The heat capacity C is temperature dependent and is often described using an empirical formula such as

C = a + bT + cT 1 + dT 2

(8.11)

The enthalpy of formation is defined as the heat evolved or absorbed when an alloy is formed from its elements. The reaction is called exothermic (negative enthalpy of formation) if there is an evolution of heat, otherwise called endothermic (positive enthalpy of formation). The enthalpy of formation can be measured or calculated. Hesss law states that the overall change in the enthalpy of chemical reaction is the same whether it takes place in one step or in several steps, which means that the enthalpy of formation is a quantity of state that independent of path. For example, the following reaction aA + bB + H = cC + dD (8.12) H can be obtained from

aH A + bH B + H = cH C + dH D
Now we calculate enthalpy change in figure 2. D H2 x+y C T2

(8.13)

A x+y

H1

B z

T1

Figure 2. Path independent enthalpy

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

It is known that enthalpy change in AC equivalents to A BC or ADC. In the path of A BC it has

H 1 + C p ( z ) dT
T1

T2

(8.14)

In ADC route it has

T2

(C

p ( x)

+ C p ( y ) )dT + H 2

(8.15)

T1

Hesss law leads to

H 2 = H 1 + C p ( z ) dT
T1

T2

T2

(C

p( x)

+ C p ( y ) )dT

(8.16)

T1

or

H 2 = H 1 + C p dT
T1

T2

(8.16)

where C p = C p ( z ) (C p ( x ) C p ( y ) ) is the difference between heat capacity of product and reactants, which is called Kirchhoffs law. In CALPHAD database, people uses 298.15 K as the reference point. Therefore the enthalpy of formation at temperature T is represented as
T

H T = H 298.15 +

dT

(8.17)

298.15

8.2 The second law of thermodynamics The second law of thermodynamics addresses the direction of reaction. Whether a reaction can be proceeded in a given direction depends on the so-called free energy. Entropy is defined as

dS =

q
T

(8.18)

It was found that the entropy of a closed system can only increase (irreversible reaction) or stay constant (equilibrium).

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

The function which decides whether a process will occur is the free energy change, G, where

G = U + pv TS

(8.19)

if G<0 the reaction will proceed. At constant pressure equation (8.19) changes into

G = H TS

(8.20)

where G is know as the Gibbs energy change of the process. At constant volume equation (8.19) changes into

F = U TS
F is called the Holmholtz energy. In pressure constant condition, it has

(8.21)

dS =

q
T

C p dT T

(8.22)

Choose 298.15 K as the reference point one has

ST = S 298.15 +

Cp T dT 298.15

(8.23)

Substituting equations (8.17) and (8.23) into (8.20), it has

T Cp GT = H 298.15 + C p dT T S + dT 298 . 15 T 298.15 298.15 T

(8.24)

By the second law of the thermodynamics, one can judge which solidification is possible once free energy of all possible phases are known. Figure 3 illustrates a schematic free energy change for solidification. It can be see that liquid will change into solid a when the temperature is dropped below the melting point. The solid b can never form because its free energy is always the highest.

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

Solid b Free energy Tam Solid a liquid temperature Figure 3. Schematic diagram of free energy change

REFERENCES 1. M.C. Flemings, Solidification processing, 1974. 2. N. Saunders and A.P. Miodownik, CALPHAD, 1998.