Department of Mining and Materials Engineering

REVIEW OF
ENGINEERING
THERMODYNAMICS

Ferrous Applications – Engineering Thermodynamics 1

 Gibbs energy
G = H – TS; G: Gibbs Energy, H: Enthalpy, S: Entropy
1. For pure elements or pure compounds (Al, O2, Al2O3, etc.)

GT  H  TS
o o o
T T

T T
C p
: Cp = a + bT + cT-2
H T  H   S T  S 298  
o o o o
298 K
C p dT K
dT
298 K 298 K
T + dTlnT + · · ·
is known (measurable)
enthalpy of compound at 298 K with
reference to pure stable elemental species standard entropy at 298 K
At 298 K, 1 atm ( H 0o K  0 , unknown) ( S 0o K  0 )

 0
o
Standard state for H : ΔH 298K
for all stable elements at 1atm and 298K. * In FactSage compound databases,
o o
Fe(bcc), Fe(fcc), Fe(l), H2O(l), H2O(g), H2(g), ΔH 298K, S 298, K ,C p are stored
O2(g), O(g), CaO, FeO, C(s), CO2, CO,.  Absolute Gibbs Energy of compounds
relative to elemental species.

Ferrous Applications – Engineering Thermodynamics 2

 Gibbs energy
2. Chemical reaction between pure compounds (No solutions)

nA + mB = AnBm

 G rxn  G A  ( nG  mG
o o o
Bm A B
)
n

 H  T  S rxn
o o
rxn

In many thermodynamics books,  H rxn o o

, S rxn are given.
These values are not absolute values, but dependent on each chemical
reaction.
 In FactSage, therefore, absolute Gibbs energy of each species
(relative to elemental species) is stored. Then, the reaction Gibbs
energy for any reaction can be automatically calculated from the Gibbs
energy of each species.

Ferrous Applications – Engineering Thermodynamics 3

 Gibbs energy
3. Chemical reaction involving gas

nA + mO2(g) = AnO2m

o o
 G rx n  G A  (nG A  m GO )
nO2m 2

o
G i  G i  RT ln Pi
for ideal gas species i

 G  mRT ln PO
o
2

At Equilibrium  G rxn  0

 G   RT ln(
o 1
m
)
PO
2

Ferrous Applications – Engineering Thermodynamics 4

 Gibbs energy
3. Chemical reaction involving gas (continued)

In general, for aA + bB(g) = cC + dD(g)

At equilibrium
d
PD
G   RT ln(
o
b
)
PB

G   RT ln K
o
K: Equilibrium constant

FactSage Reaction module can give this kind of answer

quickly. Reaction module is only for stoichiometric species
(No solutions are involved in the Reaction module
calculation)
Ferrous Applications – Engineering Thermodynamics 5
 Gibbs energy
4. Chemical reaction involving solid or liquid solutions
o
G i ( in so ln)
 G i ( pure )  RT ln( a i ) a: activity

change of Gibbs energy of i in solution

by interacting with surrounding species
Definition of activity

Pure Gas A Gas Mixture

o
pA pA PA
aA  o
  AxA
PA
∴ aA is the activity of species A in solution:
Pure Liquid A A in solution higher activity means a higher chance of
evaporating.

Ferrous Applications – Engineering Thermodynamics 6

 Gibbs energy
4. Chemical reaction involving solid or liquid solutions
Activity
1
ai  ( pi / pi )   i xi
o

(+) deviation: repulsion between i and other species

(+) deviation  a  x : more active chemical reaction of i
i i

ai ideal
(-) deviation: attraction between i and other species
 a  x : less active chemical reaction of i
i i
(-) deviation

0 xi 1

In general, for aA + bB(g) = cC + dD(g)

 G rxn  G products  G reactants

At Equilibrium
c d * FactSage solution databases contain
a C PD
G   RT ln(
o
) model parameters to calculate
Gi  ai
a b
a A PB

Ferrous Applications – Engineering Thermodynamics 7

 Gibbs energy minimization
In most thermodynamics texts, one calculates equilibrium conditions
G   RT ln K eq
o
 G rxn  0
In real calculations, we want to know the direction of reaction and
the final products
mA + nB Inputs (initial condition)

many possible outputs Tfinal, Pfinal

A2B (m-2)A
(n-1)B A2B (m-3)A
(m-1)A AB2 (n-3)B
AB2
(n-2)B
(m-x)A
(n-y)B
(xA-yB)soln
Final equilibrium state?
Ferrous Applications – Engineering Thermodynamics 8
 Gibbs energy minimization
(continued)
 We have to find out which phase assemblage is most stable at given Tf
and Pf for a given mass balance (inputs).
 Gibbs energy minimization routine. (ChemSage, Solgas-mix, etc.)
The most stable phase assemblage is the one with the lowest Gibbs
energy.

In FactSage
i) Input amounts
ii) Select all possible product phases (solid compounds, solid
solutions, liquid solutions, gases)
iii) Set Tfinal and Pfinal
iv) Calculation (Gibbs energy minimization routine)
v) Equilibrium phase assemblage calculated

Ferrous Applications – Engineering Thermodynamics 9

 Ellingham diagrams
(A)
- Collection of ΔGo values for oxidation reactions
mA + O2 = AmO2 (reference: 1 mol of O2)
ΔGo (kJ / mole of O2)

- Only consider pure compounds.

(No solutions are considered.)
(B)
A + O2 = AO2
( a AO )
G  G  RT ln
o 2
, (  G  0 : Equilibriu m)
(a A ) ( pO )
2

G  RT ln p O
o
2

G  ( R ln p O )  T
o
2

T (K)

Ferrous Applications – Engineering Thermodynamics 10

 Solution thermodynamics
A-B solution, (Solid or liquid solution)
G s o lu tio n ( m o la r )   xigi
o
g i  g i  R T ln a i gi: partial molar Gibbs energy of i in solution

o
g solution gB

o
g A Δ g mix
 g  RT ln a A gB  B
o
g A A

RT ln a A
g A
  A

XB
 i : Chemical potential of i

o o
 ( x A g A  x B g B )  R T ( x A ln a A  x B ln a B )

Ferrous Applications – Engineering Thermodynamics 11

 Solution thermodynamics
A-B solution, (Solid or liquid solution)
o o
G s o ln (m o la r)  ( x A g A  x B g B )  R T ( x A ln a A  x B ln a B )
ai  x i i

1. Ideal solution:  A
 1,  B
1
o o
G s o ln ( m o la r )  ( x A g A  x B g B )  R T ( x A ln x A  x B ln x B )

2. Regular solution: RT ln  A
  AB
2
xB Ω: Regular solution parameter
o o
G s o ln ( m o la r )  ( x A g A  x B g B )  R T ( x A ln x A  x B ln x B )   AB
xAxB

Ferrous Applications – Engineering Thermodynamics 12

 Solution thermodynamics
A-B solution, (Solid or liquid solution)
o o
G s o ln (m o la r)  ( x A g A  x B g B )  R T ( x A ln a A  x B ln a B )

3. General solution:  A
 f ( x,T ) aA   AxA

o o ex
G s o ln ( m o la r )  ( x A g A  x B g B )  R T ( x A ln x A  x B ln x B )  G

  A B x A x B  R T ( X A ln  A  X B ln  B )
ex ij i j
“Polynomial model”: G 
i , j 1

* FactSage supports many complex solution models.

Solution databases (FToxid, FTSalt, ....) contain optimized
model parameters reproducing Gibbs energies of solutions.

Ferrous Applications – Engineering Thermodynamics 13

Gibbs Energy and Phase Diagrams
 A phase diagram shows graphically the minimum Gibbs
energy assemblages of a system.

T1

Porter, D.A., and Easterling, K.E., Phase Transformation in Metals and Alloys, 2nd Ed. CHAMAN & HALL (1992)

Ferrous Applications – Engineering Thermodynamics 14

Gibbs Energy and Phase Diagram
 A phase diagram shows graphically the minimum Gibbs
energy assemblages of a system.

T2

Porter, D.A., and Easterling, K.E., Phase Transformation in Metals and Alloys, 2nd Ed. CHAMAN & HALL (1992)

Ferrous Applications – Engineering Thermodynamics 15

Gibbs Energy and Phase Diagram
 A phase diagram shows graphically the minimum Gibbs
energy assemblages of a system.

T3

Porter, D.A., and Easterling, K.E., Phase Transformation in Metals and Alloys, 2nd Ed. CHAMAN & HALL (1992)

Ferrous Applications – Engineering Thermodynamics 16

Gibbs Energy and Phase Diagram
 A phase diagram shows graphically the minimum Gibbs
energy assemblages of a system.

T4

Porter, D.A., and Easterling, K.E., Phase Transformation in Metals and Alloys, 2nd Ed. CHAMAN & HALL (1992)

Ferrous Applications – Engineering Thermodynamics 17

 Thermodynamic Database
Development: FactSage
Pure compounds

GT  H  TS
o o o
T T
T
 Calorimetry
 emf
H T  H  C
o o
dT
298 K p
 Knudsen cell
298 K
T 298 K  Vapor pressure
C p
C p
S T  S 298    
o o o
K
dT S 298 K
dT
298 K
T 0K
T

Solution
 emf (activity)
   AB x A x B 
ex ij i j Knudsen cell (activity)
G
 Vapor pressure (activity)
i , j 1
 Solution calorimetry (enthalpy)
 Phase diagrams

Ferrous Applications – Engineering Thermodynamics 18

 Dilute Solutions
1

(+) deviation

aA ideal

o
(-) deviation
aA  
o
x A : Henry’s law
A
A
slope
  
o
A A
0 xA 1
Constant slope
Henrian activity coefficient
* In FactSage, you cannot see the Henrian activity coefficient (in general,
activity coefficient) value directly, but if you calculate the activity in the
Equilib module in the very dilute composition region, you can calculate the
Henrian activity coefficient using this relationship.
Ferrous Applications – Engineering Thermodynamics 19
 Dilute Solution
Most refining processes involve impurity elements (dilute solutes)
 Henrian activity is important

For example, Al-deoxidation process in steelmaking,

2 Al  3 O  Al 2 O 3 ( s )

( a Al ) ( a Al )
2O3 2O3
G   RT ln   RT ln
o

( ) ( O X
2 3 o 2 o 3
( a Al ) ( a O ) Al
X Al O
)


o
Al is the Henrian activity coefficient of Al in pure liquid Fe

Now, if we have other elements in Fe such as O, Mn, C, etc.

there is interaction between Al and these elements.
 Change of  from 
o
Al Al : interaction coefficients
ln   ln   x Al   xO  
o Al O C
Al Al Al Al Al
x C  ...

* FactSage FTmisc-FeLQ database contains these Henrian activity

coefficients and interaction parameters for liquid steel.
Ferrous Applications – Engineering Thermodynamics 20
 Change of Standard State
Gibbs Energy
o Change of standard state is like
g i ( wt .%)
temperature scales, K, oC (that is, just
o
g i(H ) the zero point of lnai is changed).

o
g i(R ) RT ln a i ( H ) RT ln a i ( wt %) G i  G i ( R )  RT ln a i ( R )  G i ( H )  RT ln a i ( H )
o o

RT ln a i ( R )
 G i ( wt .%)  RT ln a i ( wt .%)
o

gi(gi)

 Raoultian standard state  Henrian standard state

 G i ( R  H )  RT ln  i
o o a i(H )
 fi xi

ln f i   i x i   i x j   i x k  ...
i j k

 Raoultian standard state  1 wt.% standard state

  i M Bulk 
o
a i(w t.% ) = f i [ w t% i]
 G i ( R  wt %)  RT ln  
o
 
 100 M i  i j k
log f i  e i [ wt % i ]  e i [ wt % j ]  e i [ wt % k ]  ...

FactSage doesn’t provide standard state conversions. Users

must do the conversions
Ferroususing the formulae above.
Applications – Engineering Thermodynamics 21
 Gibbs energy of reaction
 G reaction  (  n i g i ) products  (  n i g i ) reactants
o
gi  g i
 RT ln a i
Activity of i
Standard state should be checked carefully

When the reactants or products are

- Pure species (not in a solution): activity = 1
- Species in solution: requires an activity value (can be calculated from FactSage)
No direct way to do this type of calculation in FactSage.
o
In FactSage,  G reaction (between pure species) can be calculated
from the Reaction module, and the activity of each solution species in
the reactants or products can be calculated using the Equilib module.
Then, using the above formula, we can calculate  G reaction
Ferrous Applications – Engineering Thermodynamics 22
 Heat evolution calculation
H = H final - H initial =
A(L)
H final

CP(l)
Heat (enthalpy)

Hm (melting)

A(s)
CP(s)

H initial
process
Ferrous Applications – Engineering Thermodynamics 23
 Heat evolution calculation
Hf = heat of formation (or reaction)
from A(s) + B(s) to AB(s)
(typically negative value)
A(s)
Heat (enthalpy)

B(s)
Hf

Negative H means AB(s)

“generation of heat”

process
Ferrous Applications – Engineering Thermodynamics 24
 Heat evolution calculation
A(L)

B(L)
Heat (enthalpy)

A-B solution
(liquid)
A(s)

B(s)
AB(s)
process
In FactSage, the H initial and H final are directly calculated because the H of each phase is
calculated from the thermodynamic equations (database) of each solid or liquid phase.
It is important to select proper initial and final materials states and temperatures
Ferrous Applications – Engineering Thermodynamics 25
 Heat evolution calculation
• Many industrial processes require mass and heat balance
calculations. FactSage can provide a very easy way to do such
calculations. For example, the following calculation would take
several hours or days (or more) manually, but it takes less than
1 minute with the FactSage Equilib module.

Fe-C ingot Heat

CaCO3 (500oC) loss
(25oC)
Final products
temperature
pressure
Fe-Mn-Si melt
(1600oC)

Ferrous Applications – Engineering Thermodynamics 26