On Using Thermo-Calc

Sourav Das,
Researcher,
Product Research Group,
Research and Development Division,
Tata Steel
15/01/2011

What is thermodynamics???
Science of flow of heat.

1.

It is universal. We can find it in both organic (mitochondria,

ATP etc) and inorganic (black holes, mechanical systems,
chemical reactions) objects.

2. It is based on macroscopic properties of matter.

3. Entirely empirical.

15/01/2011

Zeroth law : Defines temperature, T.

If A and C are both in thermal equilibrium with a third body B, then they are also in thermal
equilibrium with each other.

1st law

: Defines energy, U

Energy can be transformed (changed from one form to another), but can not created or destroyed.

2nd law

: Defines entropy, S

The entropy of an isolated system which is not in equilibrium will tend to increase with time.

3rd law

: Gives a numerical value to the entropy

As a system approaches to absolute zero, all the processes cease and the entropy of the system
approaches a minimum value

15/01/2011

15/01/2011

Symbols

Full names

Internal energy

Quantity of heat

Work done by the system

Volume of the system

Pressure

Temperature in absolute scale

CP

Specific heat capacity at constant pressure

CV

Specific heat capacity at constant volume

Enthalpy

Gibbs free energy

Internal Energy, U
A

q
U = q w
or
dU = dq dw, where, dw = PdV if P =
constant
15/01/2011

Enthalpy, H

H = U + PV

15/01/2011

Specific heat capacities

Heat absorbed per unit change in temperature (dq/dT).
Since,

dq = dU + dw = dU + PdV (at constant pressure)

So, specific heat at constant volume, CV =

Specific heat at constant volume

H = U + PV

15/01/2011

dH = d(U + PV) = dU + d(PV) = dU + PdV + VdP

= (dq PdV) + (PdV + VdP)
= dq + VdP

Cp =

H,

at constant pressure
P

T2

H C P dT

assuming CP is constant

T1

When the reaction A + B = C will be possible?

H = Hfinal Hinitial
= -ve

But, why is it only possible? Why will it not necessarily happen?

15/01/2011

Entropy, S
For a reversible process,

dq rev
dS
T

T2

or

CP
S
dT
T
T1
P/2

Why the reaction will happen in the direction of the arrow?

Why not in the opposite direction?
So, even if H = 0, a reaction may spontaneously
happen if the S > 0

Entropy is a capacity property. Different entropies can be added together

S1 + S 2 + S 3 = S 4

15/01/2011

Entropy, S (again)

Possible arrangement, W = 1,

Possible arrangement, W = very very large

Probability of getting all the n mlecules at one side = 4 / [n(n-1)]

How does Entropy fit with the probability picture?

Through Boltzmans law: S = k ln(w)
15/01/2011

10

Gibbs Free Energy, G

G = H TS

or G = H - TS

Note: This is probably the most important parameter

in all thermodynamical calculations

15/01/2011

11

Equilibrium

15/01/2011

12

Allotropic Transition in Pure Iron

D. R. Gaskell,
Thermodynamics of Materials

15/01/2011

13

Mechanical Mixture

(1-x)

Gibbs free energy per mole

free energy of
mechanical mixture

GB0

G*

G A0

1-x

B
Concentration x of B

15/01/2011

14

atomic
solution

Gibbs free energy per mole

Solution

free energy of
mechanical
mixture

G*

G A0

G M
G{x}
free energy of solution

A
15/01/2011

GB0

x
Concentration x of B

B
15

Chemical potential

dG

dG

'

'

A . dnA (T , P, const.)

A . dnA B dnB

dG
15/01/2011

(T , P const.)

A . (1 x) B x
16

Gibbs free energy per mole

Chemical potential

15/01/2011

GB0
G A0

A (1 x)
G{x}

B (x)
A

x
Composition

17

G{x} (1 x) A x B

Conditions:
1.Under standard conditions (T = 298 K and P = 101.3 kPa)
2.Without intermolecular interactions
3.Natural isotope composition of elements

15/01/2011

18

Equilibrium between two solutions

15/01/2011

19

Equilibrium between two solutions

(contd..)
T = T1 (constant)

wt% C
15/01/2011

20

Equilibrium between two solutions

(contd..)

T = T2 (constant), T2 >T1

X
15/01/2011

wt% C

21

Equilibrium between two solutions

(contd..)
T = T3 (constant), T3 > T2

wt% C

15/01/2011

22

Phase diagram between two phases

T = T3

+
T = T2

T = T1

15/01/2011

23

Phase diagram among three phases

M2
M1

x 2

15/01/2011

x 2

x2 ( ) x 2 ( ) x 2 ( )

x 2 ( )

24

We have considered:
1. Ideal solution (random distribution of solute atoms) and
no change in binding energy when we mix the atoms
together
2. Binary solution
1. In regular solution, there will be excess free energy of
mixing and there may be liking or disliking among the atoms
(back up slide for enthalpy of mixing)
2. There can be 8-10 elements in a commercial alloy
15/01/2011

25

T2

H C P dT
T1

For a reversible process,

assuming CP is constant

dq rev
dS
T

T2

or

CP
S dT
T
T1

Heat capacity is a function of:

1. vibration of atoms
2. magnetic property of the atoms
3. Electronic heat capacity due to electronic configuration
4. Curling up of molecules etc etc.
15/01/2011

26

CP = b1 + b2T + b3T2 + b4/T2

15/01/2011

27

X
15/01/2011

wt% C

28

15/01/2011

29

References:

1. Introduction to the Thermodynamics of Materials, 3rd edition,

D. R. Gaskell
2. Online available course materials from Georgia State University, USA
3. http://en.wikipedia.org
4. Classroom video lectures on Thermodynamics from MIT, USA
5. Class room video lectures from University of Cambridge, UK
6. Online course material from University of Texas at Austin, USA
7. Thermodynamics in Materials Science, International Edition1993,
R. T. DeHoff
8. An Introduction to Metallurgy, 2nd edition, A. H. Cottrell
9. Chemical Thermodynamics of Materials, C. H. P. Lupis

12/07/2010

30

Thank you
for
kind attention

15/01/2011

31

Free energy of mixing

If we consider an ideal solution, the entropy of mixing will be:

If we consider a regular solution, there will be always a

change in bond energy and there will be excess free energy

15/01/2011

32

15/01/2011

33

15/01/2011

34