lecture 2

Contents
• Equilibrium and Equilibrium conditions
• Derivation of Phase rule
• Degrees of freedom
 Condition for equilibrium between phases

Thermal Mechanical Chemical

equilibrium equilibrium equilibrium

Thermal equilibrium
T must be the same for all the phases
Otherwise heat would flow from phase to another

• Consider system of 2 phases 1 T1

• The entropy for two phases S1 , S2 T2
2
• dq is the heat transferred from 1 to 2 at equilibrium
• The change of entropy dS = dS1 +dS2 = 0 at equilibrium
But dS1 = - dq/T1 dS2 = dq/T2
dq/T1 + (- dq/T2 ) = 0
hence T1 = T 2
 Mechanical equilibrium
Pressure must be the same for all the phases
Otherwise one phase would increase in volume

 Consider system of 2 phases

  phase expanded into  phase by dV .
 At constant T
the change of Helmholts free energy is
dA = dA +dA =0 at equ.
But dA = - P dV and dA  = P  dV
Hence
P =P
 Remember : Helmholts free energy is the free
energy at constant volume
 ‫‪Chemical equilibrium‬‬

‫‪The chemical potential (µ)of any component is the same in all phases.‬‬

‫ناتداواتاطروات اكامدعو هوك نكولمكيوكترةوعمادواتآمجكواترديو) ‪( G‬وككوعد ا‬

‫اتك نكوتكروللنيورداكواترداديوناتامآونعد ا واتك نكميوا كدلو‬
‫‪ G‬‬ ‫‪‬‬
‫‪‬‬ ‫‪i‬‬
‫‪‬‬ ‫‪ ‬‬ ‫‪i‬‬
‫‪ n‬‬ ‫‪i‬‬ ‫‪‬‬ ‫‪p ,T , J‬‬

‫ناك كواتعتلادوتكورمتكواتعنا كوات اكامدعولمتكتمرتكو‬

‫‪p‬‬
‫‪i  i  i ............. ‬‬
‫‪1‬‬ ‫‪11‬‬ ‫‪111‬‬
‫‪i‬‬

‫ناك كو عملكو ًاواتكتمرتكو لدوعملا هوت ةواتك نكميو) ‪( C‬ولمتآدا كوارعاكو‬

‫‪ 11   111   1111  .......... ......   1p‬‬
‫‪ 21   211   2111  .......... ......   2p‬‬
‫‪ c 1   c 11   c 111  .......... .   c p‬‬
 ‫ارع ماوجمتريواتآندو‬
‫‪Derivation of Phase rule‬‬

‫كمعدلو كوتراكموكعمكمهويادوكعامكلوحعورمتكوعنا كوارعنهوتن وترروككوا آناد ووووووو‪P‬‬

‫) ‪( 1,11,111,………, P‬‬

‫نكمي ووووووووووووووووووووووووووووووووووووووووووووووووووووووووووووووووو‪C‬‬ ‫نترروككواتك‬

‫(‪C‬وووووو‪ ……….,‬و‪ 1,2,3,‬و‬
‫رداميواتآ جكورواتترروات نعوتنتناكةواتكعماديوات ككوتنلاواتكعمعو–واتتناكةواتكعماديواتكعنااريوحعواتكعمعو‬

‫ترروكتمر يواتاطروات اكامدع‬ ‫اتترروات نعوتنتناكةواتكعماديوتنلاوا آنادواتككعنمك‬

‫لمتك لكوتنربوا نةو(اتترروات نعوتنتناكةواتكعماديوتنلاوا آنادواتككعنمك‬

‫• اتترروات نعوتنتناكةواتكعماديوات ككوتنلاوا آنادواتككعنمكوحعواتكعمعوتنعو‬

‫ملو كواتتناكةوعركةورداكواترداديوناتامآوناتعد ا و‬
‫• وت عوا نكواتكعمعوكعنا كو لرو كو ةوا آنادوعريوكملورداكواترداديونو‬
‫اتامآونتنايواك كوعكلاةو ًاكواتكعماداكولتررو‪ 2‬و‬
‫• ترروكعمادايواتعد ا وتنآندواتنارررو ‪ C-1‬عد ا و‬

‫ترروكعمادايواتعد ا وةترر ‪ P‬وا آنادو= )‪P ( C-1‬‬

‫اتترروات نعوتنتناكةواتكعماديوات ككوتنلاوا آناد =و‪+2‬و)‪(C-1‬و‪P‬‬

 ‫ملميواتربواتلمكعون نوتررواتتناكةواتكعماديواتكعنااريوحعواتكعمعو‬ ‫تر‬
‫ركةواتتمتعوااللوكلر واتاطروات اكامدعو‪µ‬وت ةوككواتك نكميو‪C‬و‬ ‫•‬
‫ناتاطروات اكامدعوتنك نكوحعو هوآندواتعلدوراتكوتنرداديوناتامآوناتعد ا وتطًاو‬ ‫•‬
‫اتآندو و‬
‫ردآواتعنا كواتعمعولاكوا آنادواتككعنمكواعآن و كوا نكواتاطروات اكامدعوت ةوك نكو‬ ‫•‬
‫كع منهوحعو ةوا آنادواتكعنااريوحعواتكعمعون ًاواتكعو‬
‫‪11  111  1111  ................  1p‬‬
‫‪ 21   211   2111  ................   2p‬‬
‫‪c1  c11  c111  ...........  c p‬‬
‫• ت ةوك نكوككواتك نكمي‬
‫ووووووووووووووتررو(‪(P-1‬وككواتكتمر يواتككملنكوناتك ع نكوككوكتمر يواتاطروات اكامدع‬
‫• تددع يلو يوتحونماونااو‪C‬وماوددملتعيمو‬
‫ترروكتمر يواتاطرورو‪C(P-1)‬‬ ‫•‬
‫‪F=  P(C-1)+2  –  C(P-1)  = C-P+2‬‬
DERIVATION OF THE PHASE RULE
Consider a heterogeneous system in equilibrium of C components
in which P phases are present. We have to determine the degrees
of freedom of this system i.e., the number of variables which must
be arbitrarily fixed in order to define the system completely. Since
the state of the system will depend upon the temperature and the
pressure, these two variables are always there. The concentration
variables, however, depend upon the number of phases. In order to
define the composition of each phase it is necessary to specify the
concentration of (C – 1) constituents of each phase, the
concentration of the remaining component being determined by
difference.
For P phases, therefore, the total number of concentration
variables will be P (C – 1) and these along with the two variables
mentioned above viz., temperature and pressure, make the total
number of the variables of the system equal to [P (C – 1) + 2].
On thermodynamic consideration
when a system is in equilibrium, the partial molal free energy of each constituent
of a phase is equal to the partial molal free energy of the same constituent in
every other phase. Since the partial molal free energy of the constituents of a
phase is a function of the temperature, pressure and (C – 1) concentration
variables, it follows that if there is one component in two phases, it is possible to
write one equation amongst the variables and if there is one component
in three phases, this fact may be written with the help of two equations. In
general, therefore, when P phases are present, (P – 1) equations are available for
each component and for C components, the total number of equations or
variables are C (P – 1).
Since the number of equations is equal to the number of variables, the number
of unknown variables or degrees of freedom (F) will be :
F = No. of variables – Number of equations
= [P (C – 1) + 2] – [C (P – 1)]
= PC – P + 2 – PC + C
=C–P+2
F=C–P+2
Number of degree of freedom (F)
• 1- The minimum number of intensive variables that must be specified to
find the value of all remaining intensive variables.

Consider P = 1 and C = 1 F= C-P+2= 1-1+2= 2

it will have a number of intensive properties, e.g. density, refractive index,
surface tension, viscosity, etc. but T and pressure are given, then the
substance will have a fixed value of other intensive properties.
2- The minimum number of intensive variables that can be changed
independently without changing the number of phases in equilibrium.
 Called the variance of the system.
• Simplistically speaking, there are only 3 intensive variable which
can describe any phase of a chemical system.
• Temperature(T), pressure(P) and composition/concentration ()

3- Is the smallest number of independent variables (P, T and

concentration) must be specified to describe completely the state of the
system.
 Example of system of one phase
(water vapor or water liquid or solid ice)
P= 1
F=C-P+2= 1-1+2=2
This implies that two variables (P and T) can be changed independently
(i.e., pick any dP and dT) and a single phase remains in equilibrium.
This system is called Bivariant system

Example of system of two phases of water

(G  L or G  S or L  S )
P= 2
F=C-P+2= 1-2+2=1 It is called Univariant system
There is only one degree of freedom–for the two phases to remain in
equilibrium, one variable can be changed freely (for instance, dP) but then
the change in the other variable (i.e., dT) must depend on the change of the
free variables:
dP
dT = f(P, T)
 Example of system of three phases of water
(G  L  S )
P= 3
F=C-P+2= 1-3+2=0 invariant system
There can be no change any variable that maintains three phase equilibrium.

and 4.579 mmHg °C 0.01

It is called triple point of water

Note:
Number of degree of freedom (F) can not be negative value
i.e. the lowest number of F=0
Extensive property : property various with the quantity of matter
Intensive property : property doesn’t various with the quantity of matter

Examples of extensive and intensive property

Extensive Intensive
Symbol SI units Symbol SI units
property property**

Volume V m3 or L Specific volume v m3/kg or L/kg

Internal energy U J Specific internal energy u J/kg

Entropy S J/K Specific entropy s J/(kg·K)

Enthalpy H J Specific enthalpy h J/kg

Gibbs free energy G J Specific Gibbs free energy g J/kg

Heat capacity Specific heat capacity

CV J/K cv J/(kg·K)
at constant volume at constant volume

Heat capacity Specific heat capacity

CP J/K cP J/(kg·K)
at constant pressure at constant pressure

A specific property: is obtained by dividing an extensive property of a

 For example,
 heat capacity
 extensive property of a system.
 Dividing heat capacity, Cp, by the mass of the system gives the specific
heat capacity, Cp, which is an intensive property.
 When the extensive property is represented by an upper-case letter, the
symbol for the corresponding intensive property is usually represented by
a lower-case letter. Common examples are given in the table below.
 To describe the state of a pure gas (P=1)
It is necessarily to specify only 2 variables T and P or P and V
because the third variable can be calculated from the equation of state.
Thus a pure gas has 2 degree of freedom

For one component system F= 3-P

F P
i.e. two independent variables are to be specified to describe the system 2 1
only one variable to describe the system 1 2

EX: if the system consists of

H2O (v) H2O (l)
It is necessary to specify only one variable i.e. temperature or pressure
because for a given T, pressure is automatically fixed.
 F P
We need not fix any variable or 0 3
no variable can not be altered without losing one of the phases

Because the 3 phases of water can exist only at 0.0099 C and 4.579 mm.

This point is called the triple point

When F= 0 the system is invariant

F= 1 univariant
F= 2 bivariant
EXAMPLE
CaCO3(s)‫وووووووووووو‬CaO(s)‫وووو‬+‫ووو‬CO2(g)‫ ووو‬Calculate‫و‬the‫و‬degree‫و‬of‫و‬freedom‫(و‬F)

F‫وو=وو‬C‫و–و‬P‫و‬+2 Means:‫و‬only‫و‬one‫و‬ The‫و‬number‫و‬of‫و‬components‫و‬is‫و‬not‫و‬

‫و=وووو‬2‫و–و‬3‫و‬+‫و‬2 variable,‫و‬either‫و‬ always‫و‬easy‫و‬to‫و‬determine‫و‬at‫و‬first‫و‬
‫و=وووو‬1‫(و‬univariant) temperature‫و‬or‫و‬pressure‫و‬ glance,‫و‬and‫و‬it‫و‬may‫و‬require‫و‬careful‫و‬
can‫و‬be‫و‬changed‫و‬ examination‫و‬of‫و‬the‫و‬pyhsical‫و‬
independently conditions‫و‬of‫و‬the‫و‬system‫و‬at‫و‬
equilibrium
Conclusions
1- The greater the C, the greater of F for a fixed no of P.
2- The greater P the smaller the no of variables
such as T, pressure and concentration that must be specified to
describe the system completely
3- For a given no of component, the no of phases is a maximum
when the variance is zero P ≤C+2
Fmax P min P max Fmin Phase rule No of C
2 1 3 0 F+P =3 1

3 1 4 0 F+P=4 2

4 1 5 0 F+P=5 3

5 1 6 0 F+P=6 4
Calculate the number of degree of freedom (F) for the following
systems:

1. Saturated solution of NaCl

2. Saturated solution of sugar.
3. Aqueous solution of NaCl and KCl
4. Mixture of H2, O2,and N2 gases
5. Solution of phenol and water.
6. Carbon (diamond- graphite)
7- 2H2O(L)  O2(g) + 2H2 (g)
8- NH4Cl(S)  NH3(g) + HCL (g)
9- Fe(S) + H2O(g)  FeO(S) + H2 (g)
System‫و‬name P( C ‫ و‬F(
F‫ور‬C-p+2
Saturated soln of 2 2 2-2+2‫ورو‬2 bivariant
sugar

Saturated soln of 3 3 3‫و‬-3+2‫وورو‬2 bivariant

NaCl and sugar
Soln of phenol+ 1 2 3 trivariant
H2O 2 1
 ‫‪Equilibrium Phase Diagrams‬‬

‫‪graphics represents the‬‬

‫هم سنيلا ةاقت موا ينيغيم ل اي نوسحظنلي ينس حضو ينايب سر‬
‫‪pressure‬‬ ‫• لت وظطا بحركن تم مارأ تلمصقأ لصا‬
‫‪Pase diagram‬‬
‫‪T‬‬
‫‪ -‬ن رطخم ماري رأنرمص ا = تقتا‬
‫تملا دحأ يب تقتا رت ظ‬
‫كخيم ب وم رون رطخم ماري بكاري تملا دحأ يب ت نكم ط ماظن ‪.‬‬

‫ف وظطا بحرنأ تمم رحدحرأ‬ ‫ت ظأ وظطا رحزاخا رطخي ىا رطمت ب مح‬

‫رطق وا برطلظو ا لصا‬
‫كخيم ب وم يمخا رط ا بكاري تملا دحأ يب ت نكم تمم أكا‬
‫رط ارأو ببارمل رطماظن ‪.‬‬
‫لت رطخملا رطلحأ ح زاظن كيحأ ن أكظي رطلقيا طما تظت‬
‫بكم ما تم ما ن رحدحرأ رطخحكح و‪.‬‬
Phase diagram for one component system
The properties of the system may be represented by any of the
following diagrams:

• Composition –temperature diagram

• Composition –pressure diagram
• Pressure –temperature diagram
Various types of equilibrium in one component system

p F Represented by
1 2 bivariant area
2 1 univariant curve
3 0 invarient Point at the intersect of two or more curves
We will study the equilibrium phases depend on the no of
components in the system:

- One component system

- Two components
- Three components
 ‫و‬C = 1
F= C-P+2= 3-P
The lowest no of phases =1
The maximum number of degree of freedom is F= 3-1 = 2

F‫ور‬3-P