Physical Chemistry

The second stage

Free energy functions
1. Gibbs free energy (G)
Thermodynamic energy new discovered by Mr. Gibbs
describes the state of the system of constant pressure
and constant temperature, according to the following.

G = H - TS

Changes Gibbs free energy with pressure and

temperature
A = U – TS
A = U - TS
Gibbs free energy changes with volume and
temperature
The master equation of closed systems
They are systems that allow the exchange of energy
between them with the surrounding with constant mass
Derivation Maxwell's relationship in relation to
the Gibbs
Derivation Maxwell's relationship in relation to the
Helmholtz function
Chemical potential (2 phases) ‫الجهد الكيميائي‬
(Molar free energy of molecular):Studying multi component system
which include chemical reaction, it is necessary to add some limits to
the equations of the closed systems of the pure substance or a system
that has a chemical structure constant.

‫دراسة االنظمة المتعددة المكونات والتي تتضمن التفاعالت الكيميائية وعليه من الضروري‬
‫اضافة بعض الحدود الى المعادالت لالنظمة المغلقة للمادة النقية أو النظام الذي يمتلك‬
‫تركيب كيميائي ثابت‬

dG = vdp – sdT for closed system

For open system (2 phases)

N= Number of molecules
Chemical potential: The rate of change of the Gibbs
free energy of system with the number of mole (n1) and
can be considered the driving force for chemical
equilibrium system.
Chemical potential of pure materials

Relationship chemical potential with activity

The chemical potential of a given component in a liquid solution ()

 = o + RT lin (pi/pi o)
pi= vapour pressure of that component
pi o = pressure of the pure component at the same T and P
If ideal solution → Pi = x Pi o

 = o + RT lin (xi)
For non-ideal solution
 = o(ℓ) + RT [lin xi + α xi 2 + ß xi3 +…..)
pi= xi piº exp[α xi 2 + ß xi3 +…..]= ai piº
α and ß constants
ai= activity

Relationship chemical potential with activity

Go= (ℓoL+ m oM) – (a oA + b oB)

= Go
 a am 
 L M 
Gr= Go + RT lin  aa ab  eq.
 A B 
a L a m
M
K.= a a a b
A B

 G = Go + RT lin K
o=G
Go = - RT lin K
1=a
 Chemical Equilibrium
Heat is energy flowing from a high temperature object to a low temperature
object. When the two objects are at the same temperature, there is no net flow of
energy or heat. That is why a covered cup of coffee will not be colder than or
warmer than the room temperature after it has been in there for a few hours.
This phenomenon is known as equilibrium. In this example, we deal with the
flow of energy.

Equilibria happen in phase transitions. For example, if the temperature in a

system containing a mixture of ice and water is uniformly 273.15 K, the net
amount of ice formed and the melt will be zero. The amount of liquid water will
also remain constant, if no vapour escape from the system. In this case, three
phases, ice (solid) water (liquid), and vapour (gas) are in equilibrium with one
another. Similarly, equilibrium can also be established between the vapour
phase and the liquid at a particular temperature.

Equilibrium conditions also exist between solid phases and vapour phases.
These are phase equilibria.

In Stoichiometry calculations, chemical reactions may not be as complete as we

have assumed. For example, the following reactions are far short of completion.

2 NO2→ N2O4

3 H2 + N2→ 2 NH3

H2O + CO →H2 + CO2

Let us consider only the first reaction in this case. At room temperature, it is
impossible to have pure NO2 or N2O4. However, in a sealed tube (closed
system), the ratio

Is a constant. This phenomenon is known as chemical equilibrium.

Types of chemical equilibrium
1. Homogenous equilibria

One phase = gas or liquid or solid

2. Heterogeneous equilibria

More than phase = solid — gas or liquid — gas or solid —

liquid.

Homogeneous Reaction
1. There are no changes in the number of moles.

H, + I. 2HI
§& § §&
An
= 0

K, =K, (RT)™
- Ky = Ky
H,+L 2HI
Ny, Ny,
Cr = - Cp — Vv

Thay
Cy = “Vv

Cra
K.= Cc. FC

sem (2 (2 |
V V

H,+1L = 2HI
a b
a—-x b-x ZX
2x?
Ke= (a—x)(b—x)
 2. Homogeneous in the liquid phase.

CH;COOH + C,H;0H ==> CH;COOC;H; + H,0

a b oO oO
a—xX b-x x x

XX

VV
K.= a-x b-x
Vv V

K,#K, An#o

3. Homogeneous reaction change the number of

moles.
N,O, — 2NO,
8 8
An=2-1=1
K, = K, (RT)“ =K,RT
 Pp?
NO,
Ky=
N30,

Qn,o,

Px204 = N Py.

Protal = Pt
Dyno,
PxNo2— N Py.

N= ty204 + DNo?
Van't Hoff equation
The equilibrium constant change with temperature
AG® =-RT link, K, = equilibrium constant

AG =0 at equilibrium

AG = AG° + RT linK Jalal

AG° =-RT linK

dAG* . (sink)
dT _ 7 Rimk,-RI dT :
1 | = AG° Rr | ” )
dT ° ~ dl >

Silseala US Alales CI esas

dAG°
AG®° = AH° + T dT

dAG* 5 { dlink
T| gp) =AG® -RT? [gp | eee (1)
p
P

dAG* ; 3
T) gp) = AG®- ABE oon (2)
P

dlinK AH*
dT RT
 AH°dT

Ky AH® Ty

[ dlink = aT
K, R i,2

AH? 1 1
IinK=-"p yp 7 Lae ils doles
2 1

Jog (SP:— . Ate (2-2)

°8 (Kp), ~ 2.303R \T, T,
AH°® T,-T,

~ 2.303R | TT,
Ty 4gpu Gls] Cub = (Kp),
Ty dayu ols] Cub = (Kp).

Example :- equilibrium constant Kp of the reaction

N, + 3H; 2NH;
(g) (g) (g)

1.64 x 107 at 400C° and 0.144 x 10% at 500C° .

Calculate the average temperature of the formation
of ammonia gas.
Sol. T; = 400 + 273 = 673 K
T, = 500 +273 =773K

Kp,= 1.64 x 107* , Kp, = 0.144 x 10"

 Kp, AH® (7 =)
log Kp, —-2.303R | T,T,
0.144x107 AH° 773-673
log T6axi0* ~ 2.303x1.987 [ea
AH® = - 25140 Cal
AH® = AH, Byles
Je Laill

1 3 °
ZNo + 5 Ho —— = NH3 AHF 2S) ba Jes
g g g
AH? = —2.5140
AHF’ = ~5 = 735 =- 12570 Cal/ mol

Lowering of the vapor pressure

When dissolve material non-volatile in liquid less vapor
pressure, before solvent (state of pure) the quantitative
relationship that connects the amount of decrease vapor
pressure of the solution and concentration had
discovered by the Raoult.
Md las Jaane Jas glans (4 SyUbie yt Sale 441d) ric
ceil AyeSIl ASDLally (Adal! alla) ASV) SS atlas Aaylee iL
CEES) of Sy glad! Las bere 8 Gola) plage Lays
lsh) D8 Os
P’ = the vapor pressure for pure solvent.
P = the vapor pressure for solution.
P°— P = decrease in the vapor pressure of the solvent.
p°®—P
Pp Relative lowering of the vapor pressure.
» jal) eae (8 aul) Goole
Nn,
“X= n, +n,
p®’—Pp n, AP
pe ~ X= nt+n, p°

pP?-P on, W,/M, |

no WM. at diluted solution
Pn, 1 1

aleall
8 nz Sees

Example:- When dissolve 18.04 gm of sugar

alcohol known (mantole) in 100 gm of the

water at 20C°, decreased water vapor

pressure from 17.535 mm Hg to 17.226
mm Hg in the same _ temperature.
Calculate the molecular mass for alcohol.
Sol. W,— 100g W,=18.04
M)= 18.02

P® = 17.535 mm Hg Curdrall jlas doris

iil
P = 17.226 mm Hg olka brie
Jslaall
pp-p W, M,
pe MM, wW,
17.535-17.226 18.04x18.02
17.535 M,x100
M,= 181

Elevation of Boiling point

Vapor pressure

Temperature
AT=T~—T,
AT = The amount of increase in the boiling point
AB Area
Ky = 4c Area
p°-—P
Ac= po Relative lowering of the vapor pressure

Ag = elevation of boiling point

AT= KX
dinP1 dP AH
dT PdT RT
Clausius — Clapyeron equation

AH = Ly

1 PW
P dt RT’
TAP Ww
P AT RT?
1 AP OL, . ,
Pp AT RT? When diluted solution

RT? AP RT? { P°-P

Al Tp Vv
Ly Vv

AP . .
p> ~ Relative Lowering of the vapor pressure of

solution
Al= L, P° = Ko p?

- b —
1000K,
M,

— 1000K, AP
— M,~ P®

AP =P°-—P

1000K, {P°—P
T= M Pp?
1
Phase boundaries
Vapor pressure
from

At phase boundary:
Dynamic equilibrium
between two phases
G = 0
 Phase boundaries: Where are they?
Phase 1: dGm(1) = Vm(1)dp - Sm(1)dT
Phase 2: dGm(2) = Vm(2)dp - Sm(2)dT } in equilibrium
Along the phase boundary, the molar Gibbs energies stay equal
 the changes in their molar Gibbs energies must be equal

Vm(1)dp - Sm(1)dT = Vm(2)dp - Sm(2)dT

 [Sm(2) - Sm(1)]dT = [Vm(2) - Vm(1)]dp
trsS trsV


 dT trsV



Clapeyron equation
ils Walter: Chem 260
 Special case: The liquid-vapor boundary
dp vap S  vap H vap H  vap H pvap H
    
dT vapV TvapV TVm (g) T (RT / p) RT 2
trs  vap vapS vapV perfect gas
= vapH/T  Vm(g); approximation


Vm(l) small

vap H
p' T'

d ln p vap H

 d ln p   2 dT
RT
dT p T
 ln p' vap H  1 1 
Clausius-Clapeyron    
R T T ' 
equation
p


 Characteristic points
Same as melting point;
“normal” = at 1 atm Highest T for liquid

Closed vessel:
Pressure increases
until critical point is
Lowest T for reached (Tc, pc);
liquid phase boundary is lost

Open vessel:
Only set of
Vapor pressure equals
conditions
external pressure
where all three
phases coexist  vapor drives back
atmosphere: Boiling
(water: 273.16 K,
611 Pa)
How many phases can coexist in equilibrium?
Four phases: Gm(1) = Gm(2); Gm(2) = Gm(3); Gm(3) = Gm(4)
BUT: Only two unknown parameters (p, T) in a phase diagram

 Four phases cannot coexist

in equilibrium!
line

point
Phase rule: F = C - P + 2
F = Number of degrees of freedom
C = number of components
P = number of phases

area
Nils Walter: Chem 260
Phase diagrams: Water
dp  trs S

dT trsV
Liquid water
has a higher
density than
water ice

ice skating!
frozen ponds
sustain fish!

On Mt. Everest “boiling” eggs

becomes easier
 Phase diagrams: CO2 and Helium
CO2: quite typical He: solid and gas are
never in equilibrium;
He-II is superfluid

Sublimes at
1 atm; exists
as a liquid
only under
pressure
 Physical chemistry- 2 nd stage

Lecture No. 6
Phase equilibrium
 Phase equilibrium
Phase: It is a part of system, uniform through in all chemical
compositions and physical properties which is separated from
other homogenous parts of the system by boundary surface.

Components:
The number of component is the minimum number of substance of
which the composition of each of the phase.

Degrees of freedom (F): The number of intensive parameters

that must be specified in order to completely determine the
system.
Intensive variables are pressure, temperature, and composition,
that can be changed independently without loss of a phase.
Rule Phase:
This rule was suggested by J.W. Gibbs in 1874, so called Gibb’s rule.

F = C- P + 2 …..(1)

Where:
C is the number of components, usually elements or
compounds, in the system.

F is the number of degrees of freedom, or number of Josiah Willard Gibbs

variables, such as temperature, pressure, or composition
Josiah Willard Gibbs (1839
that are allowed to change independently without - 1903) has been reckoned
changing the number of phases in equilibrium. as one of the greatest
American scientists of the
19th century. He was
P is the number of phases present. awarded the first Doctor of
Engineering in the U.S.,
and was appointed Prof-
essor of Mathematical
In the system may be described separately. Physics at Yale in 1871.
He provided a sound
thermo-dynamic
foundation to much of
Physical Chemistry.
 Reduced Phase Rule

This rule is used, if no vapor phase is found in a

system, so the pressure is independent .

F = C- P + 1
 -

We used a reduced phase rule

because no steam system found.
a) b) c)
F=C- …..(7)

P
PHASE DIAGRAMS

The graphical presentation giving the conditions of pressure and

temperature under which the various phases are existing and
transform from one phase to another is known as the phase diagram
of the system. A phase diagram consists of areas, curves or lines and
points.

Phase Diagram

Depending upon the

For one Component present in system For two
component system component system
[Water system]

Component which react to Components which are

form compounds completely miscible but do
not react (Eutectic mixture)
[Pb-Ag system]

System having congruent System having

melting point [Zn – Mg Incongruent melting
system] point [Na-K System]
4 PHASE RULE FOR ONE-COMPOUNT SYSTEMS

The least number of phases possible in any system is one. So,

according to the phase rule equation, a one-component system
should have a maximum of two degrees of freedom.

When C = 1, P = 1

So, F=C−P+2=1−1+2=2

Hence, a one-component system requires a maximum of two

variables to be fixed in order to define the system completely. The two
variables are temperature and pressure. So, phase diagrams for one
component system can be obtained by plotting P vs T.
In case of a one-component system, phase diagram consists of
areas, curves or lines and points which provide the following
information regarding the system:
Point on a phase diagram represents a non-variant system.
Area represents a bivariate system
Curve or a line represents a univariate system.
Water system and the Sulphur system are the example of one
component systems.

[1] Water System

Water is a one component system which is chemically a single
compound involved in the system. The three possible phases in this
system are: ice (solid phase), water (liquid phase) and vapour
(gaseous phase).
Hence, water constitutes a three-phase, one-component system.
 Since water is a three-phase system, it can have the following
equilibria:
The existence of these equilibria at a particular stage depends
upon the conditions of temperature and pressure, which are the
variables of the system. If the values of vapour pressures at different
temperatures are plotted against the corresponding temperatures,
the phase diagram of the system is obtained.
The phase diagram of the water system is shown in Fig. 2.1. The
explanation of the phase diagram of water system is as follows:
(a) Curves

The phase diagram of the water system consists of three stable

curves and one metastable curve, which are explained as follows:

(i) Curve OB: The curve OB is known as vapour pressure curve of

water and tells about the vapour pressure of water at different
temperatures. Along this curve, the two phases—water and vapor
exists together in equilibrium.
At point D, the vapour pressure of water become equal to the
atmospheric pressure (100°C), which represents the boiling point
of water. The curve OB finishes at point B (temp. 374°C and pressure
218 atm) where the liquid water and vapour are indistinguishable
and the system has only one phase. This point is called the critical
point.
Applying the phase rule on this curve,

C = 1 and P = 2
 F=C−P+2=1−2+2=1

Hence, the curve represents a univariant system. This explains

that only one factor (either temperature or pressure) is sufficient to
be fixed in order to define the system.

(ii) Curve OA: It is known as sublimation curve of ice and gives the
vapour pressure of solid ice at different temperatures. Along
sublimation curve, the two phase’s ice and vapour exist together in
equilibrium. The lower end of the curve OA extends to absolute
zero (−273°C) where no vapour exists.
 Area Phase exits Component
(i) Area AOC ice H2O
(ii) Area COB water H2O
(iii) Area below BOA vapour
H2O Thus, for every area contains

C = 1 and P =
1 Therefore, applying phase rule on
areas
F=C−P+2=1−1+2=2

Hence, each area is a bivariant system. So, it becomes necessary

to specify both the temperature and the pressure to define a one
phase-system.
Table 2.1: Some salient features of the water system

Curve/ Name of Phases in No. of Degree of the

area/ point the equilibriu phase (P) freedom (F)
system m

Curve OB Vapourisation Liquid & vapour 02 01(Univariate)

curve
Curve OA Sublimation curve Solid & vapour 02 01(Univariate)
Curve OC Fusion curve Solid & liquid 02 01(Univariate)
Curve OA’ Metastable Liquid & vapour 02 01(Univariate)
vaporization curve
Area AOC Ice 01 02(Bivariate)
Area BOC Water 01 02(Bivariate)
Area AOB Vapour 01 02(Bivariate)
Point O Ice & water 03 0(Invariant)
& vapour
 5 TWO-COMPOUNT SYSTEMS

When the two independent components are present in a heterogeneous

system, the system is referred to as a two-component system. Hence,
according to the phase rule, for a two-component system having
one phase,

F=C−P+2=2−1+2=3

Therefore, the two component system having one phase will have
three degrees of freedom or three variables would be required to define
the system. The three variables are pressure (P), temperature (T) and
concentration (C). This will require a three-dimensional phase
diagram for the study of a two-component system. However, in order
to simplify the study, a two-component system is usually studied in
the form of a condensed system. A condensed system can be studied
by reducing a comparatively less important variable. This reduces the
degree of freedom of the system by 1 and the system can easily be studied
with the help of a two-dimensional phase diagram.
It can have a maximum of following four phases:

Solid lead, solid silver, Solution of molten silver & lead and
Vapors

The boiling points of silver and lead are considerably high and
the vapour pressure of the system is very low. So, the vapour phase
can be ignored and the system can be studied as a condensed
system. This system thus can be easily studied with the help of a two
dimensional T − C diagram and the reduced phase rule equation, F’
= C − P + 1, can be used. This system is generally studied at
constant pressure (atmospheric). The phase diagram of Lead-Silver
system is shown in Fig. 2.2.
(a) Curves
The phase diagram of the lead-silver system consists of following
curves, which are explained as follows:

(i) Curve AC (Freezing point curve of lead): The AC curve shows

the variation of the melting point of lead on addition of silver. The
pure lead melts at 327°C (point A). Addition of silver lowers its
melting point along curve AC. The added silver dissolves in molten
lead to form Ag-Pb solution with the separation of some part of solid
lead. Therefore, the two phases, solid lead and Ag-Pb solution remain
together in equilibrium along the curve AC.

Hence, P = 2, (solid Pb and melt of Ag-Pb)

C = 2(Pb and Ag)

So, C = 2 and P = 2,

On applying the reduced phase rule

F’ = C − P + 1 = 2 − 2 + 1 = 1 the system is
univariate.

(iii) Area BCF: The area consists of two phases—solid Ag and a

solution of Pb and Ag. Hence it is also univariate.

(i) Area DCFH: This area also has the two phases which are
solid Ag crystals and solid eutectic crystals. Hence C = 2 and
P = 2, the system is univariate.

(ii) Area CEGD: The area also has the solid Pb crystals
and solid eutectic crystals phases. The system is
univariate.
 Table 2.2: Some salient features of the Pb-Ag system.
Curve/ area/ Name of Phases in No. of Degree of
point the system equilibrium phase (P) freedom (F)

Curve AC Freezing curve of Pb Pb & Melt (Pb+ Ag 02 01(Univariate)

Solution Pb & Ag)
Curve BC Freezing curve of Ag Ag & Melt 02 01(Univariate)
Pb & Ag)
Area ACE ..... Pb & melt 02 01(Univariate)
Area BCF ..... Ag & melt 02 01(Univariate)
Area above ..... Liquid (melt) 01 02(Bivariate)
ACB
Area ECF ..... Pb & Ag both in 02 01(Univariate)
solid
Point O Eutectic point Pb, Ag & melt 03 0(invariant)

(B) Systems having Congruent Melting Point

A binary system is said to possess a congruent melting point when it melts at a

sharp temperature to give a liquid of the same composition as that of the solid.

The components of a binary mixture at a certain stage enter into

chemical combination and form one or more compounds (inter-
metallic compounds) in stochiometric proportions. These
compounds melt sharply at a constant temperature into a liquid
having the same composition as that of the solid. The temperature at
which such a compound melts is called the congruent melting point.
Some common examples of this type of system are zinc-
magnesium system, mercury-thallium system, gold-tin system and
ferric chloride-water system etc.
 1 Zn-Mg system
Zn-Mg System is a two-component system and possesses a
congruent melting point. The phase diagram of Zn-Mg system is
shown in Fig. 2.3. In this system, the two components are zinc and
magnesium, which melt at 419°C and 650°C respectively which
are represented as point B and A in the phase diagram of the system.
Both metals enter into chemical combination and form an
intermetallic compound MgZn2 and melts at 590°C to give a liquid
of the same composition.
Hence, 590°C is the congruent melting point of the system.
In the reduced form, the system has the following four phases:
Solid magnesium, solid zinc, solid MgZn2 and liquid solution of Zn and
Mg.
On applying the reduced phase rule

F’ = C − P + l = 1 − 2 + 1 = 0

Therefore, at point D constitutes a non-variant system.

(ii) Point E (Eutectic point): Point E represents the eutectic point of

the system at a temperature of 345°C which is the least melting point
of Mg-MgZn2 system. Here, also three phases existing together in
equilibrium at point E are solid Mg, solid MgZn2 and liquid MgZn2.

Hence, C = 2 and P = 3,

F’ = C − P + 1 = 2 − 3 + 1 = 0 the system is non-variant.

(iii) Point C (Eutectic point): This point also represents the
eutectic point (380°C) which is the least melting point of Zn-
MgZn2 system. At this point, the three phases—solid Zn, solid
MgZn2 and liquid MgZn2 exist together in equilibrium.
Therefore,

C = 2 and P = 3

F’ = C − P + l = 2 − 3 + 1 = 0

Hence, point C represents a non-variant

system.

(c) Areas
The phase diagram of zinc-magnesium system consists of many
areas. The area above the curve BCDEA constitutes a single phase
system. The phase present in this area is a liquid melt consisting of a
liquid solution of zinc and magnesium.

Hence C = 2 and P = 1,

F’ = C − P + 1 = 2 − 1 + 1 = 2 that the system is

bivariate.

Most of the other areas of the Zn-Mg system consist of two phases
and they are univariate systems as represented in the phase
diagram. These areas are explained in detail in table 2.3.
 Table 2.3: Some salient features of the Zn-Mg system

Curve/ area/ point Phases in equilibrium No. of Degree of the

phase(P) freedom (F)

Curve BC (Freezing Zn & Melt (Containing Zn 02 01(Univariant)

curve of Zn) & MgZn2)
Curve AE (Freezing Mg & Melt (Containing Zn 02 01(Univariant)
curve of Mg) & MgZn2)
Curve CD MgZn2 & melt (Containing 02 01(Univariant)
Mg & MgZn2)
Curve DE MgZn2 & melt (Containing 02 01(Univariant)
Zn & MgZn2)
Curve CDE MgZn2 & melt 02 01(Univariant)
Area above BCDEA Liquid (Melt of Zn, Mg & 01 02(Bivariant)
MgZn2)
 Area BCF Zn & Melt(Containing Zn 02 01(Univariant)
& MgZn2)
Area DCG MgZn2 & Melt(Containing 02 01(Univariant)
Zn & MgZn2)
Area DEH MgZn2 & Melt(Containing 02 01(Univariant)
Mg & MgZn2)
Area AEI Mg & melt (containing Mg + 02 01(Univariant)
MgZn2)
Area below line FCG Zn & MgZn2 (both solid) 02 01(Univariant)
Area below line HEI Mg & MgZn2 ( Both solid) 02 01(Univariant)
Point C (Eutectic) Zn, MgZn2 & Melt(Containing 03 0(invariant)
Zn & MgZn2)
Point E (Eutectic) Mg, MgZn2 & Melt(Containing 03 0(invariant)
Mg & MgZn2)

(C) Incongruent Melting Point System

There are several systems in which components combine together to

form one or more compounds which are unstable and do not possess
congruent melting points. A system (compound) is said to possess
incongruent melting point, if on heating it decomposes much below
its melting point and forms a new solid phase and a solution having
different composition from the corresponding solid state. It has no
sharp melting point. The decomposition at this temperature is known
as transition or meritectic or peritectic rection and the temperature (the
incongruent melting point) is known as transition or meritectic or
peritectic temperature.

Examples: Following are some examples of the binary systems which

possess incongruent melting point:
 (i) Gold-antimony system
(ii) Sodium-bismuth system
(iii) Sodium-potassium system
(iv) Sodium sulphate-water system
(v) Potassium chloride-copper chloride system
 Problems about Clausius Clapeyron equation
Problem
1
The vapor pressure of a substance is 21 torr at 200 K. Calculate the vapor
pressure at 310 K if the enthalpy of vaporization is 24 kJ.mol-1.

Hint: ∆H = 24 x 103 j.mol-1, P1 = 21 torr, T1 = 300 K and T2 = 310

K. Find P2?1
Solution
-∆Hvap/R(1/T2 - 1/T1)
P2 = P1 e
-1
/8.314 J.K-1. mol-1(1/310 K - 1/300 K)
P2 = 21 torr x e-24000 J.mol

P2 = 28.6 torr

Problem 2
The vapor pressure of a substance is 30 torr at 250 K. At what temperature
will the substance have a vapor pressure of 150 torr? The enthalpy of
vaporization is 45 kJ.mol-1?
Hint: ∆H = 45 x 103 j.mol-1, P1 = 30 torr, P2 = 150 torr T1 = 250 K
and Find T2?

Solution 2

T2 = [ 1/T1 – R ln (p2/p1)/∆Hvap]-1
T2 = [1/250 K – 8.314 J.mol_1.K-1 ln (150 torr/30 torr)/ 45 x 103
J/mol-1]-1 T2 = [4 x 10-3 – 2.9737 x 10-3]-1
T2 = [3.7026 x 10-3 K-
1 -1
] T2 = 270.1 K
Problem 3
A liquid has v. p. of 2.02 x 103 N.m-2 at 293 K and heat of vaporization 41 kJ.mol-1.
The boiling point of liquid (in kelvin) is?

Hint: ∆H = 41 x 103 j.mol-1, P2 = 2.02 x 103, T2 = 293 K and P1 =

1.01 x 105
Solution 2
log p2/p1 = ∆Hvap/R (1/T1 - 1/T2)

1
 Problems about Clausius Clapeyron
equation log (2.02 x 103)/(1.01 x 105) = 41 x 103/2.303 x 8.314
x (1/T1 - 1/293)

-1.699 = 2.143 x 103 (1/T1 - 1/293)

-1.699/2.143 x 103 = 1/T1 - 1/293

-7.93 x 10-4 = 1/T1 - 1/293

1/T1 = 2.62 x 10-3

T1 = 381.7 K

2
Example 1: For water at 0 °C, the standard volume of
transition of ice to liquid is (−1.6 cm3 mol−1), and the
corresponding standard entropy of transition is (+22 J K−1
mol−1). Calculate the slope of the solid–liquid phase
boundary at that temperature?
Example 2: What is the expected boiling point of water at
98.7 kPa (approximately 740 torr, a typical barometric
pressure at 275 m altitude)? The heat of vaporization is
2258 J g-1, the molar volume of liquid water is 18.87 cm 3
mol-1, and the molar volume of steam is 30.199 dm3.mole-1,
all values referring to 373.15 K and 101.325 kPa (1 atm).
Solution: ΔvapH = 2258 J g-1, Vm(l) = 18.87 cm3 mol-1, Vm(g)
= 30.199 dm3 mol-1, T = 373.15 K and p = 101.325 kPa (1
atm).

For a decrease of 101.325 kPa ̶ 98.7 kPa = 2.625 kPa, there is a

decrease in temperature of 2.77 x 10-4 K Pa-1 x 2625 Pa = 0.73
K.
Therefore, the new boiling point is 373.15 K ̶ 0.73 K = 372.42 K.

Example 3: What is the rate of change per pascal in the

boiling point of water at a 100 ᶹC in atmospheric pressure?
The enthalpy of vaporization is 40.69 kJ mol-1, the molar
volume of liquid water is 0.019 x 10-3 m3 mol-1, and the
molar volume of steam is 30.199 x 10_3 m3 mole-1. All
values are given at 100 ᶹC, and 1.01325 bar.
Solution: ΔvapH = 40.69 kJ mol-1, Vm(l) = 0.019 x 10-3 m3
mol-1, Vm(g) = 30.199 x 10-3 m3 mol-1, T = 373.15 K

Example 4: Water has ΔvapH = 41 kJ mol-1 vapour pressure

at 373 K is 101.325 kPa. What is the vapour pressure at 298
K?
Solution: ΔvapH = 41 kJ mol-1, Ti = 373.15 K, T2 = 298.15 K,

pi = 101.325 kPa and pf =?

‫ كالبيرون نفترض ان المعادلة خطية من الدرجة األولى‬-‫ولغرض رسم معادلة كالوسيوس‬
:‫وكما هو موضح في المعادلة والشكل االتي‬

A. Objective types questions:

1. The degree of freedom at a triple point unary diagram for water
___________
(a) 0 (b) 1 (c) 2 (c) 3
2. Following is wrong about the phase diagram
(a) It gives information on transformation rate.
(b) Relative amount of different phases can be found under given
equilibrium conditions.
(c) It indicates the temperature at which the different phases start to
melt.
(d) Solid solubility limits are depicted by it.
3. Pick the odd one of the following:
(a) Isomorphous alloy (b) Terminal Solid Solution
(c) Intermediate Solid Solution (d) Compound
4. The boundary line between (Liquid + Solid) and (Solid) regions
must be part of _____
(a) Solvus (b) Solidus (c) Liquidus (d) Tie- Line
5. An invariant reaction that produces a solid up on cooling two
liquids:
(a) Eutectic (b) Peritectic (c) Monotechtic (d) Syntectic
6. A Liquid Phase produces two solid phases during _________
reaction up on cooling.
(a) Eutectic (b) Eutectoid (c) Peritectic (d) Peritectoid
7. On heating one solid phase results in another solid phase plus one
liquid phase during
----------- Reaction.
(a)Eutectic (b) Peritectic (c) Monotechtic (d) Syntectic

8. In a one component system the maximum number of phases that

can co-exists in
Equilibrium is:
(a) 1 (b) 2 (c) 3 (d) 4
9. In terms of number of phases (P), components (C) and degrees of
Freedom (F), the
Phase rule is expressed as:
(a) P + C = F + 2 (b) F= P + C – 2
(c) P + F = C + 2 (d) P- F = C + 2
10. In the phase diagram of the benzene- naphthalene system, the
point C is called the:
(a) Eutectic Point (b) Congruent Point (c) Triple Point (d) Critical
Point.
11. Lowest temperature is reached by using:
(a) CaCl22H2O (b) Acetone with dry ice (c) NH4Cl (d) Ether + Dry Ice
12. A compound with an incongruent melting point decomposes on
heating into:
(a) A liquid of the same composition as the solid.
(b) A new solid phase and a solution with a composition different
from that of the solid Phase.
(c) A new and a solution with the same composition as that of the
solid Phase.
(d) A solution of fixed composition.
B. Short Answer Questions:
1. Define the terms :- Phase, Components and degree of freedom
INTRODUCTION
Surface chemistry is the branch of Physical Chemistry that occurs at the surfaces or
interfaces. The interface or surface is represented by separating the bulk phases by a hyphen
or a slash. For example, the interface between a solid and a gas may be represented by solid-
gas or solid/gas. Due to complete miscibility, there is no interface between the gases. The
bulk phases that we come across in surface chemistry may be pure compounds or solutions.
The interface is normally a few molecules thick but its area depends on the size of the
particles of bulk phases. Many important phenomena, noticeable amongst these being
corrosion, electrode processes, heterogeneous catalysis, dissolution and crystallization occur
at interfaces. The subject of surface chemistry finds many applications in industry, analytical
work and daily life situations.
 SOME COMMON TERMS USED IN SURFACE
CHEMISTRY
1. Adsorption: As like to the liquid surface, there occur certain unbalance residual forces at the surface
molecules of the solid substances. Thus the tendency of the surface molecules of the solid substances
to attract the molecules of the other substances at the surface to minimize the unbalanced residual
forces is known as adsorption phenomena. Example : When the gases like NH3, Cl2, SO2 etc. comes
in the contact of charcoal then there occurs the adsorption of the gases at the charcoal surface.

2. Absorption: The process of attracting the molecules of the other substance in the inner bulk is
known as absorption phenomena. Example: When the NH3ngas comes in the contact of H2O
then the NH3 is absorbed by the H2O to form the NH4OH.
3. Sorption: When both the adsorption and absorption phenomena
take simultaneously, than such type of the process is known as sorption. Representation of
the adsorption, absorption and sorption process can be given as:
Adsorption and Absorption
Differences between adsorption and absorption
 In the adsorption phenomena two types of
the species are involved:
A. Adsorbent: That substance which attracts the molecules of the
other substance at its own surface will be called as adsorbent.
Generally solid substance can be used as a adsorbent in the
adsorption phenomena.
B. Adsorbate: That substances of which molecule are adsorbed at
the surface of the adsorbent will be called as adsorbate.
Mostly gaseous molecule can behave as an adsorbate in the
adsorption phenomena.
TYPES OF ADSORPTION
Depending on the force of attraction between the adsorbate and adsorbent surface the adsorption can be
divided in to two different types, which are given below:
1. Physical adsorption: Such type of the adsorption phenomena in which there occur a weak Van der
Waal attraction force between adsorbate and adsorbent surface is known as physical adsorption.
2. Chemical adsorption: Such type of the adsorption phenomena in which there occur a
strong chemical bonding between the adsorbate and adsorbent surface is known as chemical
adsorption.

DIFFERENCE BETWEEN THE PHYSICAL AND

CHEMICAL ADSORPTION
Properties Physical adsorption Chemical adsorption
Specificity Physical adsorption does not having the Chemical adsorption has
specificity specificity
Force of attraction In the physical adsorption there occur In the chemical adsorption there
weak Vander waal force of attraction occur strong chemical bonding
between the adsorbate and adsorbent between the adsorbate and
adsorbent.
Enthalpy of adsorption In the physical adsorption there occur In the chemical adsorption there
very low enthalpy of adsorption(4- occurs very high enthalpy of
40KJ/mol) adsorption (40-400KJ/mol).
Activation energy Physical adsorption required negligible Chemical adsorption requires
activation energy value. certain activation energy value.
Reversibility Due to the weak Van der waal force of Due to the stronger chemical
attraction between the adsorbate and bonding between the adsorbate
adsorbent, the physical adsorption and adsorbent the chemical
having reversible nature adsorption having irreversible
nature.
Effect of temperature With the increase in the temperature, the With the increase in the
extent of physical adsorption is decreases temperature, the extent of
chemical adsorption is initially
 ADSORPTION ISOBAR
At a constant pressure the graph plotted between the x/m (extent of adsorption) and temperature T
or (the amount of the gas adsorbed per gram of the adsorbent (x/m)) is known as adsorption isobar. For
the physical and chemical adsorption, the adsorption isobar can be represented as:

Where χ = Amount of the adsorbate at the adsorbent or m = Surface mass of the adsorbent.
 ADSORPTION ISOTHERM
At the constant temperature the graph plotted between the extents of adsorption (x/m) and pressure (P) is known as
adsorption isotherm.
There are some different types of the adsorption isotherm which can be defined as:
 Type I: This type of behaviour is shown by gases in which, the extent of adsorption initially increases with the increase
in pressure, and thereafter approaches a saturation limit, much before the saturation pressure is reached.
 Type II: This type of behaviour is similar to type I adsorption isotherm, where the extent of adsorption increases with
the increase in pressure till the monolayer formation is complete. After the monolayer formation, multilayer adsorption
starts which increases with increase in the pressure. This type of behaviour can be explained by van der waals forces
operating between the consecutive layers
 Type III: This type of behaviour occurs when multilayer adsorption starts even before the monolayer
formation is complete
 Type IV: This is the duplication of type II adsorption isotherm. First the monolayer formation starts, then it
completes, and then the multilayer formation starts and thereafter it gets completed
 Type V: This behaviour is erratic and does not fall in any category, and therefore is separately classified as
type V adsorption isotherm.
Five main categories
of adsorption
isotherms showing the
amount of gas (x)
adsorbed on a
definite mass of
adsorbent (m); p0 is
the saturation
pressure
 Criteria of Adsorption

 We all know that adsorption is a spontaneous process. Thus, the free energy change of the system (ΔG) is
negative. When the adsorbate is adsorbed onto a surface, the translational freedom of the latter gets reduced,
making entropy change for the adsorption process a negative quantity. This makes the enthalpy change
negative for adsorption, with the condition that |𝚫H| > |T𝚫S|.
 Thus, the adsorption process is exothermic in nature. This can also be explained by the fact that adsorption
process involves attraction between the adsorbate and adsorbent molecules and there occurs a decrease in the
residual forces acting along the surface of the adsorbent. Consequently, there occurs a decrease in the surface
energy, which appears as heat. The amount of heat evolved when one mole of gas or vapour is adsorbed on a
solid is called as molar enthalpy of adsorption. As adsorption proceeds, this molar enthalpy of adsorption of
the adsorbate goes on decreasing, becoming less and less negative, and ultimately becoming equal to TΔS,
when 𝜟𝐺 becomes equal to zero. At this state, the system attains equilibrium.
 There are certain exceptions to the fact that enthalpy change for the adsorption process is always negative.
This occurs when dissociation of the adsorbate takes place and the latter has high translational mobility on the
surface. Example includes endothermic adsorption of hydrogen gas on the glass surface. Hydrogen molecules
dissociate into atoms on the glass surface, where they move freely. This is accompanied by a large increase in
the translational entropy, which is sufficient to overcome the small positive enthalpy change.