MTK - Dilute Solution and Phase Rule

Dilute Solution
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
Henrys Law
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
The constant is equal to the slope of the curve at zero

0
concentration of A, designated by g A (activity
coefficient of the solute A at infinite dilution).
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.
Henrys Law
aA
0A Henrys law constant
xA
Henrys Law
In concentratrated solution the standard state has been

defined as unit atmospheric pressure and unit activity i.e.
pure substance at any temperature.
In dilute solutions relative standard states other than pure
substance being used. Henrys law offers two such standard
states, called alternative standard states.
(1) Infinitely dilute, atom/mole fraction standard state.
(2) Infinitely dilute, wt% (w/o or %) standard state.
Solubility of Gases
It is important to note that the validity of Henrys law

depend upon the proper choice of solute species. For
example, consider
(a) solution of nitrogen in water
(b) solution of nitrogen in liquid iron
In the first case nitrogen dissolves molecularly as N2
K=
N 2 (g ) N 2 ( dissolved in water)
aN2
pN2
As solubility of N2 in water is low according to Henrys law

we have
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
Solubility of Gases
Thus the solubility of nitrogen in water is proportional to the

partial pressure of nitrogen gas in equilibrium with water.
Solubility can be expressed as mole fraction, cc per 100 g of
water or any other unit.
In the second case under consideration nitrogen dissolves
atomically in solid or liquid metals:
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
pN2 = k ' pN2
Solubility of Gases
Sieverts law
Since all the common diatomic gases N2, O2, H2

etc. dissolve atomically in metals, the general
expression for solubility is given as:
S =k
pN2
This is known as Sieverts law and can be stated

as solubility of diatomic gases in metals is
directly proportional to the square root of partial
pressure of the gas in equilibrium with the metal.
Metallurgical Engineerin
Alternative Standard States
g
1. Infinitely dilute, atom fraction standard state

Henerian standard state is obtained from Henrys law which,
strictly being limiting law obeyed by the solute in the dilute
solution is expressed by
aA
g A0
xA
as x A 0
where a A is the activity of A w.r.t Roultian

s tan dard state and g A0 is the Henery' s law cons tan t
If the solute obeys Henrys law over a finite concentration
range, then
a A g A0 . x A
g
Henerian standard state is obtained by the extending the

Henrys law line to xA = 1.
This state represents pure solute in the hypothetical,

nonphysical state in which it would exist as a pure component
if it obeyed Henrys law over the entire composition range
(i.e., as it does for a dilute solution)
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
where f A is the henerian activity coefficient

g
In the range of composition in which the solute obeys Henrys

Law, fA =1 and solute exhibit the Henerian ideality
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
g
The free energy change accompanying the transfer of one

mole of solute A from pure substance standard state
(Raoultian standard state) to Henerian standard state, that
is:
A (in the Raoultian standard state) A( in the Henerian standard state)
is given by
0
0
0
DG A ( R H ) = G A ( H ) - G A ( R )
The partial molar free energy of the solute at constant

concentration is independent of standard state. The value of
GA0 remains unchanged if G A ( R )
is added and
G A(H )
is subtracted from the right hand side of the above equation
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 )
g
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
g
2. Infinitely dilute, wt% standard state.

The use of this standard state eliminates the necessity of
converting weight percentages, obtained via chemical analysis, to
mole fractions for the purpose of thermodynamic calculations.
This standard state is particularly convenient to use in
metallurgical systems containing dilute solutes. This standard
state can formally be defined as:
aA
1 as wt.% A 0
wt.% A
or a A = wt.% A( wt .% A 0 )
g
If the concentration up to 1 weight-percent of solute

A, then aA = 1 at wt%A =1 and this 1 weight-percent
solution is then the standard state
W.r. t 1 weight-percent standard state, the activity
of solute A is given by
h A (1 wt %) = f A (1 wt %) . wt .% A
Where fA(1wt%) is the 1 wt.% activity coefficient and in

the range of composition in which A obeys the
Henrys law fA(1wt%) = 1
hA (1wt %) = wt .% A
g
We can also write
aA
x A .g A
=
hA(1wt %) f A(1wt %) .wt % A
cons tan t composition
In the range of composition in which the solute obeys

Henrys Law, fA(1wt%) =1 and A = A0 , therefore,
aA
xA.
0
=g A
wt % A
hA(1wt %)
cons tan t composition
g
We know that
wt.% A
MA
xA =
wt.% A 100 - wt.% A
+
MA
MB
Where MA and MB are the molecular weight of A and B. the first

term in the denominator is small compared to the second and the
relation may be simplified as
wt.% A
MA
wt.% A . M B
xA
=
100
100. M A
MB
xA
MB
Therefore,
=
wt.% A 100. M A
g
The free energy change accompanying the transfer of one mole

of solute A from pure substance standard state (Raoultian
standard state) to 1 wt.% standard state, that is:
A (in the Raoultian standard state) A( in the 1 wt.% standard state)
is given by
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
g
The free energy change accompanying the transfer of

one mole of solute A from Henerian standard state to
1 wt.% standard state, that is:
A (in the Henerian standard state) A( in the 1 wt.%
standard state)
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
In terms of logarithm
On differentiation,
Inserting this into G-D equation, we get
Chemical Potential
The general equation for the free energy change of a system

with temperature and pressure dG = VdP SdT, does not take
into account any variation in free energy due to concentration
changes.
G = G (T , P, n1 , n2 , ....)
We know
From the fundamentals of partial differentiation we have
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
called the chemical potential
Chemical Potential
= 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
dU = TdS - PdV + m i dni
Physical Meaning of
Chemical potential
Consider the change in free energy (dG/) of a system produced

by the addition of dnA mole of component A at constant
pressure and temperature. The change in free energy of a
system is given by dG = m A dn A = G A dn A
is the partial molar
free energy of component A in solution
G A =
= m A for a large quantity of solution
n A P ,T , n B
G
G A =
n A
= m A for one mole of solution

P ,T , n B
Chemical potential of either 1 g mol or 1 g atom of a substance

dissolved in a solution of definite concentration is the partial
molar free energy. Thus
Equality of chemical potential

amongst phases at equilibrium
We know: dG = - S dT + V dP + m dn
At constant T and P:dG
= dn
g
Consider two phases(I and II) in the system. Then,
Consider moving an infinitesimal of quantity dn1 from

phase
I to phase II. Then,

g
Therefore, total free energy change of the system

is
For equilibrium at constant temp and pressure
Hence,
It can be generalized for all components at constant
T and
P when phase I and II are at equilibrium as

g
Where P is the total no. of phases in the system
Phase Rule
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.
Phase Rule
As an example let us consider decomposition of calcium

carbonate :
CaCO3 (s) = CaO(s) + CO2(g)
According to the above definition, at equilibrium this system
will consist of two components since the third one is fixed by
the equilibrium conditions.
Thus we have three phases two solids (CaCO3 and CaO) and
a gas (CO2) and the system has only two components.
If CaO and CO2 are taken, the composition of calcium
carbonate phase can be expressed as xCaO + xCO2 giving
xCaCO3 (by the chemical reaction).
The composition of the three phases could be expressed
equally by taking CaCO3 and CaO or CaCO3 and CO2 as the
components.
Phase Rule
The dissociation of any carbonate, oxide or similar compounds

involves two components; the same is true in the case of salt
hydrate equilibria, for example : CuSO4.5H2O(s) =
CuSO4.3H2O(s) + 2H2O(g) when the simplest components are
evidently CuSO4 and H2O.
In the slightly more complicated equilibrium : Fe(s) + H2O(g) =
FeO(s) + H2(g) it is necessary to choose three components in
order that the composition of each of the three phases can be
expressed.
The composition of the two solid phases could be given in terms
of Fe and O, but these alone are insufficient to define the
gaseous phase which is a mixture of hydrogen and water vapour,
a third component, viz., H2O is necessary.
Phase Rule
The water system for example consists of one component, viz.,

H2O each of the phases in equilibrium i.e. solid, liquid and vapour
may be regarded as being made of this component only.
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.
Derivation of the Phase

Rule Equation

Rule Equation

Rule Equation
Phase rule in Reactive

Components
Consider a system consisting of N chemical species and there

are P number of phases.
In this case the number of components differ from number of
species.
Let us consider there are three out of N species are chemically
active and participate in the following reaction:
AB(s) = A(g) + B(g).
The number of total variables = P(N-1) + 2
Total number of constraints due to phase equilibrium= N(P-1).
There is another additional constraints: AB(s) = A(g) + B(g).
Phase rule in Reactive

Components
Additional, in the absence of A(g) and B(g) in the starting

reactant mixtures, stoichiometric consideration requires that
PA= PB.
Some times, special constraints are placed on the system. For

example, the system under consideration, the partial pressure
of A has been fixed at 2 atm.
So this way total no. of constraints are = N(P-1)+1+1+1.
F = [P(N-1)+2] [N(P-1)+1+1+1] = (N-2) P +1 = C P +1
Generalizing, for a system in which there are r independent
chemical equilibria, s stoichiometric relation and t special
constraints we have
F = (N r s - t) P +2 = C- P + 2 t
where C = N - r - s
Application of Phase rule

in Reactive Components
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.

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

Problem:
Show that the system in which the reaction

Mn(s) + 2/3 AlCl3(g, 1atm) = MnCl2(l) + 2/3 Al (l)
is at equilibrium is invariant.
Solution:
N = 4 (Mn(s), AlCl3(g), MnCl2(l), Al (l))

P = 1 solid (Mn) + 2 liquids(MnCl2(l)and Al (l)) + 1 gas (AlCl3(g)) = 4
r=1
s=0
t = 1 (1 atm of AlCl3(g))
C = N r s = 4 1 0 = 3
F=CP+2t=34+21=0
This is an invariant system

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.

MTK - Dilute Solution and Phase Rule

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Dilute Solution

The constant is equal to the slope of the curve at zero

0A Henrys law constant

In concentratrated solution the standard state has been

It is important to note that the validity of Henrys law

In the first case nitrogen dissolves molecularly as N2

As solubility of N2 in water is low according to Henrys law

Thus the solubility of nitrogen in water is proportional to the

pN2 = k ' pN2

Since all the common diatomic gases N2, O2, H2

This is known as Sieverts law and can be stated

1. Infinitely dilute, atom fraction standard state

where a A is the activity of A w.r.t Roultian

Henerian standard state is obtained by the extending the

This state represents pure solute in the hypothetical,

where f A is the henerian activity coefficient

In the range of composition in which the solute obeys Henrys

The free energy change accompanying the transfer of one

The partial molar free energy of the solute at constant

2. Infinitely dilute, wt% standard state.

If the concentration up to 1 weight-percent of solute

Where fA(1wt%) is the 1 wt.% activity coefficient and in

We can also write

hA(1wt %) f A(1wt %) .wt % A

cons tan t composition

In the range of composition in which the solute obeys

cons tan t composition

Where MA and MB are the molecular weight of A and B. the first

The free energy change accompanying the transfer of one mole

The free energy change accompanying the transfer of

Inserting this into G-D equation, we get

The general equation for the free energy change of a system

called the chemical potential

dU = TdS - PdV + m i dni

Consider the change in free energy (dG/) of a system produced

= m A for one mole of solution

Chemical potential of either 1 g mol or 1 g atom of a substance

Equality of chemical potential

Consider two phases(I and II) in the system. Then,

Consider moving an infinitesimal of quantity dn1 from

Equality of chemical potential

Therefore, total free energy change of the system

Equality of chemical potential

Where P is the total no. of phases in the system

As an example let us consider decomposition of calcium

The dissociation of any carbonate, oxide or similar compounds

The water system for example consists of one component, viz.,

Derivation of the Phase

Derivation of the Phase

Derivation of the Phase

Phase rule in Reactive

Consider a system consisting of N chemical species and there

Phase rule in Reactive

Additional, in the absence of A(g) and B(g) in the starting

Some times, special constraints are placed on the system. For

Application of Phase rule

Application of Phase rule

Application of Phase rule

Show that the system in which the reaction

N = 4 (Mn(s), AlCl3(g), MnCl2(l), Al (l))

Application of Phase rule

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