Professional Documents
Culture Documents
Henrys Law
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Henrys Law
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Metallurgical Thermodynamics
Henrys Law
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
p Aa x A
i.e. p A = kx A
(1)
dividing by p 0A we have
pA k
= 0 .x A i.e.a A = const x A or a A a x A
0
pA pA
a A = g A0 . x A
Like Raoults law, Henrys law is valid within a concentration
range where the extent varies from one system to another,
but it is valid only at low concentration.
Metallurgical Thermodynamics
Henrys Law
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
aA
xA
Metallurgical Thermodynamics
Henrys Law
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Metallurgical Thermodynamics
Solubility of Gases
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
K=
N 2 (g ) N 2 ( dissolved in water)
aN2
pN2
a N 2 = k xN 2
xN 2
or K =
kxN 2
pN2
K
( so lub ility ) = p N 2 = k p N 2
k
Metallurgical Thermodynamics
Solubility of Gases
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
N 2 ( g ) 2 N (in Fe)
K=
N ( inFe )
pN 2
( kx N ) 2
pN 2
K
or x N (inFe ) ( so lub ility ) =
k
Metallurgical Thermodynamics
Solubility of Gases
Sieverts law
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
S =k
pN2
Metallurgical Thermodynamics
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
aA
g A0
xA
as x A 0
a A g A0 . x A
Metallurgical Thermodynamics
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
h A = 1 = 0A at x A = 1 .
This is the henerian s tan dard state and
h A is the henerian activity
Having defined the Henrian standard state, the activity of A
in solution with respect to the Henrian standard state is
given by:
hA = f A . x A
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
hA = xA
a A x A .g A g A
=
=
hA x A . f A f A x A = cons tan t
In the range of composition in which the solute obeys Henrys
Law, fA =1 and A = A0
aA
0
=gA
hA
x A = cons tan t
Metallurgical Thermodynamics
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
DG A ( R H ) = G A ( H ) - G A ( R )
DG A0 ( R H ) = G 0A ( H ) - G 0A ( R ) + G A ( R ) - G A ( H )
) (
= G A ( R ) - G 0A ( R ) - G A ( H ) - G 0A ( H )
Metallurgical Thermodynamics
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
But
G A - G A0 = R T ln a A
a
Hence, DG A0 ( R H ) = RT ln A
hA x A =cons tan t
= RT ln g A0
Metallurgical Thermodynamics
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
aA
1 as wt.% A 0
wt.% A
or a A = wt.% A( wt .% A 0 )
Metallurgical Thermodynamics
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
h A (1 wt %) = f A (1 wt %) . wt .% A
hA (1wt %) = wt .% A
Metallurgical Thermodynamics
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
aA
x A .g A
=
aA
xA.
0
=g A
wt % A
hA(1wt %)
Metallurgical Thermodynamics
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
We know that
wt.% A
MA
xA =
wt.% A 100 - wt.% A
+
MA
MB
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
aA
DG ( R 1 wt. %) = RT ln
h
A (1Wt .%) x A = const
0
A
MB
= RT ln g + RT ln
100.M A
0
A
Metallurgical Thermodynamics
Metallurgical Engineerin
Alternative Standard States
D E P A R T M E NT O F
g
Indian Institute of Technology( Banaras Hindu University)
is given by
DG A0 ( H 1 wt. %) = DG A0 ( R 1 wt. %) - DG A0 ( R H )
MB
0
= RT ln g A0 + RT ln
- RT ln g A
100.M A
MB
= RT ln
100.M A
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
In terms of logarithm
On differentiation,
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Metallurgical Thermodynamics
Chemical Potential
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
G
G
G
G
dG =
dn1 +
dn2 + ......
dT +
dP +
, P , n2 ....
, P , n1 ....
T P ,ni
P T , ni
n1 Texcept
n2 Texcept
n1
n2
G'
= S'.dT + V' dP +
ni
G
n P,T,n .......
The coefficient i except1ni
and is denoted by m hence
T , P , n1 ....
except n i
dn i
Metallurgical Thermodynamics
Chemical Potential
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
= mi
T
,
P
,
n
.....
n
i Except1 ni
m is an intensive variable
This gives a new sets of fundamental equations for the open
systems.
dG = - S dT + V dP + m i dni
dA = - S dT - PdV + m i dni
dH = TdS + V dP + m i dni
Metallurgical Thermodynamics
Physical Meaning of
Chemical potential
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
G A =
= m A for a large quantity of solution
n A P ,T , n B
G
G A =
n A
Metallurgical Thermodynamics
g
Indian Institute of Technology( Banaras Hindu University)
Metallurgical Thermodynamics
g
Indian Institute of Technology( Banaras Hindu University)
Metallurgical Thermodynamics
g
Indian Institute of Technology( Banaras Hindu University)
Metallurgical Thermodynamics
Phase Rule
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Phase(P)
A phase is defined as any homogeneous and physically distinct
part of a system which is separated from other part of the
system by a bounding surface. For example, at 273.15K, three
phases ice, water and water vapour can exist in equilibrium.
When ice exists in more than one crystalline form, each form
will represent a separate phase because it is clearly
distinguishable from each other.
Components(C)
The number of components in a system at equilibrium is the
smallest number of independently variable constituents by
means of which the composition of each phase present can be
expressed directly or in the form of a chemical equation.
Metallurgical Thermodynamics
Phase Rule
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Phase Rule
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Phase Rule
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Degrees of freedom(F)
The number of degrees of freedom is the number of variable
factors, such as temperature, pressure and concentration that
need to be fixed in order that the condition of a system at
equilibrium may be completely defined when referring to its
equilibrium phase diagrams.
Metallurgical Thermodynamics
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Problem:
A system is composed of a solid phase CaCO3, a solid phase CaO,
and a gas phase CO2 . The following equilibrium occurs:
CaCO3(s) = CaO(s) + CO2(g)
How many components are there and what are the degrees of
freedom?
Solution:
Species: CaCO3(s) , CaO(s), CO2(g) : N =3, Phases : two solid and a gas phase
P = 3. No. of independent reaction equilibria r = 1. There is no
stoichiometric or special constraints.
So s = 0 and t = 0
C = N-r-s = 3-1-0= 2
F = C-P+2-t = 2-3+2-0 = 1
Either temperature or pressure must be specified.
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Problem:
A pure solid NH4Cl is introduced into an evacuated chamber. It is
then allowed to decompose and equilibrium has been established by
following reaction:
NH4Cl(s) = NH3(g) + HCl(g)
Calculate the number of components and degrees of freedom.
Solution:
N = 3 (NH4Cl(s) , NH3(g) , HCl(g))
P = 1 solid (NH4Cl(s) ) + 1 gases (NH3(g) + HCl(g ) = 2
r=1
s = 1 as P NH3(g) = P HCl(g)
t=0
C = N r s = 3 1 -1 = 1
F = C P + 2 t = 1 -2 + 2 0 = 1
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Problem:
Solution:
D E P A R T M E NT O F
Metallurgical Engineering
Indian Institute of Technology( Banaras Hindu University)
Problem:
Consider reduction of FeO with CO under standard
conditions i.e. P = 1 atm.
FeO(s) + CO(g) = Fe(s) + CO2(g).
Calculate the number of components and degrees of
freedom.
Solution:
In this system we have P = 3 (i.e. two solids FeO and Fe
and a gaseous phase CO+CO2) and N = 4, r = 1, s = 0 and
t = 1 (PCO + PCO2 =1 atm)
C = N r s = 4 -1 -0 = 3
F = C - P + 2-t = 3 3 + 2 -1 = 1
Thus the above system has only one degree of freedom,
either temperature or pressure.
Metallurgical Thermodynamics