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AMMSI A CSIR National Metallurgical Laboratory Jamshedpure,India. masi@nmlindia.org & masi.mett@gmail.com

Thermodynamics is the science of flow of heat

Thermodynamics is the study of the effects of work, heat, and

energy on a system.

Thermodynamics is only concerned with macroscopic changes and observations. Not only

Heat transfers until thermal equilibrium is established.

Nothing happening.

Eventhough law ‘s thermodynamics are empirical and

observation ,No one are violating so for

Why is it so ????

Derived from Greek word & is the science of flow of heat

  • Developed in 19 th and early 20 th century (i) Invention of stream engine in 18 th century and issue of the relation between heat and work .

(ii) Count Rumford observed that q g ∞ work done (iii) In 1840 Joules experiment proved the count Rumford

observation. This was led to First law of thermodynamics . (iv) In mid 19 th Entropy as the thermo parameter (v) In 1904 W Nerst and Max Planck absolute entropy value - Third law of thermodynamics

Entirely empirical ,observation and common sense

Developed before people knew about atom and molecules so science based on macroscopic properties of matter.

A thermodynamic system is said to be at equilibrium when it is at mechanical, thermal and chemical equilibrium.

The word equilibrium means a state of balance.

In a state of thermodynamic equilibrium, there are no net

flows of matter or of energy, no phase changes, and no unbalanced potentials (or driving forces), within the system.

For a thermodynamic system thermal equilibrium is achieved when temperature is constant, mechanical equilibrium is attained when pressure or volume is constant and chemical

equilibrium is attained when the chemical potentials are constant.

Nothing is happening

Alternately, at equilibrium the total energy is minimum or

equilibrium corresponds to a minimum energy state. It was already mentioned that at complete equilibrium dG=0

and that a system is in mechanical, thermal and chemical

equilibrium. At mechanical and thermal equilibrium in a heterogeneous

system, the pressure and temperature is equal in all the

phases. The concept of chemical equilibrium can be understood in terms of the chemical potential.

Nothing is happening and Absence of driving potential & ??

Para equilibrium

Para equilibrium Quasi equilibrium Metastable equilibrium Unstable equilibrium 12/30/2013 AMMASI A CSIR -NML India

Quasi equilibrium

Metastable equilibrium

Unstable equilibrium

Thermodynamics terminology

Thermodynamics terminology 12/30/2013 AMMASI A CSIR -NML India
Describing systems requires : Variable or parameter which can quantitatively measurable ex: p, T, V, n,

Describing systems requires:

Variable or parameter which can quantitatively

measurable

ex: p, T, V, n, m, …

Intensive & Extensive properties

System is Homogeneous or Heterogeneous

System is in Equilibrium State

The number of components

Extensive properties

  • Those properties of system that vary with its size or mass

  • These properties of system are

additive Total volume of a system is sum of all the volume

of the component part V T = V2 +V2 +V3 +…

Intensive properties

  • Those properties of system that are independent of its size or mass

  • These properties of system are not additive. Hence a value may be assigned at each point in system.

Ex : M,V ,E ,H ,S and G etc of a substance

Ex : P,T ,ρ , η and molar energy etc of substance

Note : Ratio of any extensive properties is independent of the total mass All specific and molar properties are intensive properties

Classical thermodynamics concerns the relationships between bulk properties of matter. Nothing is examined at the atomic or molecular level.

Statistical thermodynamics seeks to explain those bulk properties in terms of constituent atoms. The statistical part

treats the aggregation of atoms, not the behavior of any

individual atom.

Thermal equilibrium: Two systems are said to be in thermal equilibrium if there is no net

Thermal equilibrium: Two systems are said to be in thermal equilibrium if there is no net flow of heat between them when they are brought into thermal contact.

Temperature is the indicator of thermal equilibrium in the sense

that there is no net flow of heat between two systems in thermal

contact that have the same temperature.

THE ZEROTH LAW OF THERMODYNAMICS

Two systems individually in thermal equilibrium with a third system are in thermal equilibrium with each other.

Common sense law : Concept of temperature and heat flow A B T A =T C
Common sense law : Concept of temperature and heat flow A B T A =T C
Common sense law : Concept of temperature and heat flow
A
B
T A =T C
T B =T C
C
Then T A =T B
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AMMASI A CSIR -NML India

Temperature is the indicator of thermal equilibrium in the sense that there is no net flow of heat between two systems in

thermal contact that have the same temperature.

THE ZEROTH LAW OF THERMODYNAMICS

Two systems individually in thermal equilibrium with a third system are in thermal equilibrium with each other.

Temperature is a measure of average kinetic energy of particle in a substance. Temperature really tells

Temperature is a measure of average kinetic energy of particle in a substance.

Temperature really tells us how fast atom /molecules moving in the system . 12/30/2013 AMMASI A
Temperature really tells us how fast atom /molecules moving in
the system .
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AMMASI A
CSIR -NML India
Based on Boyles’s law – Empirical law PV PV=0= f(T) 100 0 -273.15
Based on Boyles’s law – Empirical law
PV
PV=0= f(T)
100
0
-273.15

T(₀C)

Based on Boyles’s law – Empirical law PV PV=0= f(T) 100 0 -273.15 T( ₀C) 12/30/2013
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AMMASI A CSIR -NML India

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1.First law of thermodynamics that energy cannot be created nor destroyed although it can be converted

1.First law of thermodynamics that energy cannot be created nor destroyed although it can be converted from one

form to another or transferred from a system to the

surroundings or vice versa

2.The total energy of the universe is a constant.

3.The energy of a system which isolated from

surrounding is constant

Simply the law of conservation of energy
Simply the law of conservation of energy
Energy is conserved!
Energy is conserved!

NO THEORETICAL PROOFF

1. It is not possible to construct a perpetual machine which can do work without the
  • 1. It is not possible to construct a perpetual machine which can do work without the expenditure of energy .if the were not true ,it would have been possible to construct such a machine .

  • 2. James joule (1850) conducted large no of Experiments regarding the conversion of work into heat energy . He

concluded that for every 4.183 J of work done on system,

one calorie of heat produced .

  • 3. Energy is conserved in chemical reaction also

1. It is not possible to construct a perpetual machine which can do work without the
If a system’s volume is constant, and heat is added, its internal energy increases If a

If a system’s volume is constant, and heat is added, its

internal energy increases

If a system’s volume is constant, and heat is added, its internal energy increases If a

If a system does work on the external world, and no

heat is added, its internal energy decreases.

If a system’s volume is constant, and heat is added, its internal energy increases If a
If a system’s volume is constant, and heat is added, its internal energy increases If a
If a system’s volume is constant, and heat is added, its internal energy increases If a
The total energy which includes the energy of creation of the system or matter (U) and

The total energy which includes the energy of creation of the system or matter (U) and the energy to displace the systems surroundings in the absence of external force fields so that the system can be created is given by enthalpy

The total energy which includes the energy of creation of the system or matter (U) and

In thermodynamics, the internal energy is the total energy contained by a thermodynamic system. It is the energy needed

to create the system. It excludes the energy to displace the

system's surroundings, or any energy introduced due to external force fields.

Internal energy has two major components, (i) Kinetic energy and (ii) Potential energy.

The kinetic energy is due to the motion of the system's particles whether it be the motion of atoms, molecules, atomic nuclei, electrons, or other particles (translations, rotations, vibrations).

The potential energy includes all energies given by the mass of

particles, by the chemical composition, i.e. the chemical energy stored in chemical bonds, the nuclear energy stored by the configuration of protons, neutrons, and other elementary particles in atomic nuclei.

U is function of state

--Amount of heat required to raise its temperature by one degree

--Amount of heat required to raise its temperature by one degree atomic heat and molar heatS p e c i f i c h e a t , Heat capacity at Volume (C ) U = f(V,T) dE= δ q-P dV 12/30/2013 AMMASI A CSIR -NML India " id="pdf-obj-22-4" src="pdf-obj-22-4.jpg">

atomic heat and molar heat

Heat capacity at Volume (C v ) U = f(V,T) dE= δq-P dV

--Amount of heat required to raise its temperature by one degree atomic heat and molar heatS p e c i f i c h e a t , Heat capacity at Volume (C ) U = f(V,T) dE= δ q-P dV 12/30/2013 AMMASI A CSIR -NML India " id="pdf-obj-22-28" src="pdf-obj-22-28.jpg">
--Amount of heat required to raise its temperature by one degree atomic heat and molar heatS p e c i f i c h e a t , Heat capacity at Volume (C ) U = f(V,T) dE= δ q-P dV 12/30/2013 AMMASI A CSIR -NML India " id="pdf-obj-22-30" src="pdf-obj-22-30.jpg">
--Amount of heat required to raise its temperature by one degree atomic heat and molar heatS p e c i f i c h e a t , Heat capacity at Volume (C ) U = f(V,T) dE= δ q-P dV 12/30/2013 AMMASI A CSIR -NML India " id="pdf-obj-22-32" src="pdf-obj-22-32.jpg">

Amount of heat required to raise the temperature of 1 g of a substance by 1° C or 1 K

Substance

Specific heat (c) J/g °C

Water

4.184

Ice

2.03

Steam

2.01

Al (s)

0.897

Fe (s)

0.449

Amount of heat required to raise the temperature of 1 g of a substance by 1°

Amount of heat (J)

Amount of heat required to raise the temperature of 1 g of a substance by 1°

Heat capacity at constant pressure (Cp)

U = f ( T,P)

dE= δq-P dV

Heat capacity at constant pressure (Cp) U = f ( T,P) dE= δ q-P dV Relation
Heat capacity at constant pressure (Cp) U = f ( T,P) dE= δ q-P dV Relation

Relation between Cv and Cp

Heat capacity at constant pressure (Cp) U = f ( T,P) dE= δ q-P dV Relation
Heat capacity at constant pressure (Cp) U = f ( T,P) dE= δ q-P dV Relation
Heat capacity at constant pressure (Cp) U = f ( T,P) dE= δ q-P dV Relation

For an ideal gas and isothermal process

Heat capacity at constant pressure (Cp) U = f ( T,P) dE= δ q-P dV Relation
Heat capacity at constant pressure (Cp) U = f ( T,P) dE= δ q-P dV Relation
Heat capacity at constant pressure (Cp) U = f ( T,P) dE= δ q-P dV Relation
Heat capacity at constant pressure (Cp) U = f ( T,P) dE= δ q-P dV Relation

H change when substance is heated from T1 to T2 @ constant P (a) Without phase transformation

H change when substance is heated from T1 to T2 @ constant P (a) Without phase

(b) with phase transformation ( melting, vaporization or other phase transformation .

H change when substance is heated from T1 to T2 @ constant P (a) Without phase

H ° 298 for pure element is assumed to be zero at standard state

Heat of formation of compound 3 Fe O + CO =2Fe O +CO Heat of reaction

Heat of formation of compound 3 Fe 2 O 3 + CO =2Fe 3 O 2 +CO 2 Heat of reaction 2 Al +3/2 O 2 = Al 2 O 3 Heat of combustion C +O 2 = CO 2 Heat of transformation

∆H r = -2.67 kJ/mole

∆H f =-1700kJ/mole

∆H = -393.5kJ/mole

Zn s

Zn l @ 963K

Heat of solution

L f , Zn =+7.28 kJ/mole

 The first law of thermodynamics provides no information regarding the feasibility of such transformation 
  • The first law of thermodynamics provides no

information regarding the feasibility of such transformation

  • First law does not provide any information regarding

the direction a processes will take whether it is a spontaneous or a non spontaneous process

i) In electric machines efficiency of the conversion of electrical energy to mechanical and vice versa

i) In electric machines efficiency of the conversion of electrical

energy to mechanical and vice versa can occurs as high as 90%

ii ) While , in heat engine efficiency of the conversion of heat energy into work is quite low ,10 to 40 %

Note : Irreversible nature of flow of heat & heat cant be transferred from low to high temperature without aid of external energy .

Kelvin-Planck statement

Clausius statement

There exists a property called entropy which is a thermodynamic property of a system.

Naturally occurring processes

are directional & irreversible

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Kelvin-Planck statement Clausius statement There exists a property called entropy which is a thermodynamic property of

Entropy

AMMASI A CSIR -NML India

Kelvin-Planck statement Clausius statement There exists a property called entropy which is a thermodynamic property of
Kelvin-Planck statement Clausius statement There exists a property called entropy which is a thermodynamic property of

S surr

 

H sys

T

Melting of solid is a accompanied by moderate S increase while vaporization involves really large S increase

solidification and condensation ???

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surr   sys T Melting of solid is a accompanied by moderate S increase

Let us ask a question as to whether it would be possible to

convert all the energy supplied to a system into useful work?

Although the first law indicates that out of the total energy

input to the system, part of it is usefully converted to work and

some of it is stored in the system, the first law is unable to quantify the non-recoverable losses of energy such as friction and dissipation.

Entropy is a thermodynamic property that is a measure of the energy not available for work in a thermodynamic process, such as in energy conversion devices, engines, or machines.

an energy TS is not available to do useful work

Classical thermodynamics .

Classical thermodynamics . A microstate specifies all molecular details about the system including the position and

A microstate specifies all molecular details about the system

including the position and velocity of every molecule. In statistical mechanics, entropy is given as:

Classical thermodynamics . A microstate specifies all molecular details about the system including the position and

ω is the number of microstates. In statistical mechanics, entropy is a measure of the number of ways in which a system may be arranged, often taken to be a measure of "disorder"

Free energy is the energy available to do work It is the total energy available in

Free energy is the energy available to do work

It is the total energy available in the system minus the energy not available for useful conversion to work.

We already said enthalpy and TS.

Therefore, in common metallurgical systems that operate at constant pressure, the energy available from a system to convert to useful work is the Gibbs free energy that is defined as

G=H-TS

According to II law , To predict the spontaneity of a process entropy

of universe is considered. It is difficult to determine ΔS surroundings in

most of the physical & chemical processes. Therefore a thermodynamic function which reformulates the spontaneity criterion considering only the system under study is required

Most of chemical and metallurgical reaction are performed at constant T & P Gibbs Free Energy (G)

Interest at System under constant T & Volume

Helmholtz Free Energy (A)

or Isothermal work

content A = E - TS

dA =-S dT P dV System under these condition is called closed system

Our ultimate object to express first & second law explicitly in

terms of T and P which experimentally most easily controlled

G = E + PV TS

or G = H TS

Also called as thermodynamics Potential

d G = dE +P dV +V dP -T dS- S dT

= -P dV +T dS +P dV +V dP -T dS- S dT = V dP-S dT δw’ δw’ = non mechanical work ,

Generally we always interest in P V type work So

d G = V dP-S dT

Thermodynamic conditions for spontaneity and equilibrium for closed system. Spontaneous Δ G < 0 Δ S

Thermodynamic conditions for spontaneity and equilibrium for closed system.

Spontaneous

ΔG S < 0

ΔS U > 0

Equilibrium

ΔG S = 0

ΔS U = 0

Non spontaneous

ΔG S > 0

ΔS U < 0

We know If z= f (x,y)

;

dz= Mdx +Ndy

(δ M / δy ) x = (δ N / δx)

----- Eq (a)

Following forms of combined Eq of first & second law of thermodynamics all of which apply to a system of constant composition and mass at equilibrium.

  • d E = T dS PdV

dH

= T dS + V dP

dA = -S dT P dV

  • d G = V dP-S dT

δw’ = 0

Apply relation to Eq (a)

(δT/ δV) S = -(δP/ δS) V

(δT/ δP) S =

(δV/ δS ) P

(δP/ δT) V = (δS/ δV) T

(δV/ δT) P = -(δS/ δP) T

Maxwell Relation

These Equations are used to calculate thermodynamic parameter.

First and second law of thermodynamics state that the energy and entropy of system are function

First and second law of thermodynamics state that the energy

and entropy of system are function of its state . Since these law

deal only with changes in energy and entropy respectively. absolute value of energy and entropy ???

In 1902, T.W. Richard who found that for many reaction ∆S and ∆Cp approach zero at low temperature & also he researched that relationship of T with ∆G or ∆H, which were measured by some battery reaction. ∆G and H are almost the same size at low temperature.

T 0K

,

H  G

Nernst heat theorem state that for all reaction involving substances

in condensed state ∆S is zero at absolute zero .

Debye’ s law Cv = aT 3

Planck state that Entropy of any homogeneous substance which

is in complete internal equilibrium may be taken as zero at 0K

S = 0 at absolute zero

Assignment of zero value to entropy of crystalline elements is

zero purely a convention and that assignment of a zero value to

entropy of most compound is a consequence of convection as well as third law .

Chemical reaction

A + B = AB

The

temperature

of

the

S AB S A -S B = 0 substance can

not drop to

0 K

by

finite ways

 

.

In actual practice it may and frequently does , happen that a phase cooled to vicinity of absolute temperature , more random atomic

arrangement characteristic of higher temperature is frozen

Ex when solid CO is cooled to a near absolute zero ,there is very strong presumption that molecules do not arrange themselves in

most orderly fashion . instead of -C-O-C-O-C-C- people found that C-O-C-O-O-

Third law applicable to solution , pure crystalline which are in complete internal equilibrium .

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(i) Adiabatic process ,∆U= -w (ii) Isochoric process ,W = 0 (iii)Isobaric process W=P(V2-V1) (iv) Isothermal

(i) Adiabatic process ,∆U=-w (ii) Isochoric process ,W = 0

(iii)Isobaric process W=P(V2-V1)

(iv) Isothermal process ..

Transition from

one state to another state

(i) Adiabatic process ,∆U= -w (ii) Isochoric process ,W = 0 (iii)Isobaric process W=P(V2-V1) (iv) Isothermal
Zero th law :Common sense Temperature 1 law of thermodynamics : you can break even Internal

Zero th law :Common sense Temperature 1 st law of thermodynamics : you can break even Internal energy and Enthalpy

2 nd law of thermodynamics : you can break even at 0K Entropy and Free energy

3 rd law of thermodynamics : you cant get to 0K Absolute value ..

Fugacity indicates the escaping tendency of the matter or substance or component. High fugacity would indicate

Fugacity indicates the escaping tendency of the matter or substance or component.

High fugacity would indicate a greater tendency of a compound to escape out of system, dissolve , intermix or react.

dG =V dP-S dT At constant T and for one mole of ideal gas

dG = RT d(lnP)

f = P @ all pressure

Fugacity for real or non ideal gas

dG= RT d (lnf)

Real gases approach ideal behavior as pressure is decreased Hence, P→0, f →P

As consequence of lower /decrease in pressure of an real gas f=P

Only at very high level of pressure and for an real gas we use

FUGACITY instead of PRESSURE. i.e. P→f at very high pressure.

Thermodynamic variable (H,S & G etc ) of the substance in pure state are different from

Thermodynamic variable (H,S & G etc ) of the substance in pure state are different from those in state of solution.

There fore H,S & G changes with change in composition besides T & P .

Index to measure these changes in H ,S & G when pure substance goes into a state of solution.

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a = f /f

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Activity is a measure of free concentration.

Concentration available for reaction.

dG= RT d (lnf) = RT d (f a) = RT(dln f ) + dln a)

Activity of a substance in its standard state is to be unity .

dG = RT d(ln a) ……

..

(a)

Integrating eqn (a) from standard to actual state at constant T G-G ₀ = (RT ln a- RT ln a₀ )

General form : partial free energy of I th species

G I = G I

+RT (ln a 1 )

Chemical reaction under isothermal isobaric condition

aA + bB +…. = dD +eE +….

∆G = ∆G +RT ln( a D d .a E e

/ a A a .a B b

)

∆G = ∆G + RT ln Q @ Equilibrium ∆G = 0 0 = ∆G + RT ln K

∆G

= -RT ln K

where K= (Q ) eq

1) When K is greater than Unity ,Equilibrium lies well to right Product predominate in Eq

1) When K is greater than Unity ,Equilibrium lies well to right Product predominate in Eq mixture.

2) When K is less than unity ,Equilibrium lies to left

Reactant predominate

Feasibility of Reaction : ∆G≤0 & K ≥1

d ∆G = ∆V dP-∆S dT

At constant pressure

d ∆G = -∆S dT

d ∆G = ∆V dP- ∆S dT At constant pressure d ∆G = - ∆S dT

Gibbs Helmholz Eq Integrating and divided by T 2

d ∆G = ∆V dP- ∆S dT At constant pressure d ∆G = - ∆S dT

Von’t Hoff Equation

d ∆G = ∆V dP- ∆S dT At constant pressure d ∆G = - ∆S dT

It is for the chemical reaction involving the gases species Partial pressure ,total pressure and vacuum

Free energy of single phase at internal phase at equilibrium as a

function of T,P and Composition .

We assumed that there is no electric ,magnetic, gravitational and surface fields ,etc effect on our system.

dG =(∂G/∂P)dP + (∂G/ ∂T)dT+ (∂G/ ∂n 1 ) dn 1

+ (∂ G/ ∂ n 2 )+……

i) Dealing with the behaviour of heterogeneous system ii) possible to predict the effect of change of Pressure , Temperature and Concentration iii) American physicist willared Gibbs

Yale university Father of chemical thermodynamics

Let us consider a system of C components and P phases at temperature T and pressure P. The number of independent variables required describing the system is called degrees of freedom F

In any system the number of intensive variables are:

pressure, temperature plus the mole fractions of each component of each phase. Only C-1 mole fractions are needed. Thus for P phase, the number of intensive variables = P(C-1) + 2.

At equilibrium the chemical potential of phase must be equal,

i.e. µ i I = µ i II = µ i III = µ i IV = µ i V ….{there are P-1 such equations}. Since there are C components, equilibrium requires that there are C(P-1)

Degree of Freedom F = total required variables total restraining conditions

F = P(C-1) + 2 - C(P-1)

= PC - P + 2 -CP = C- P + 2

+ C

i.e., P+F=C+2

-

A phase diagram is a schematic representation of heterogeneous equilibrium in a system A phase diagrams

A phase diagram is a schematic representation of heterogeneous equilibrium in a system A phase diagrams show what phases exist at equilibrium

and what phase transformations

we can expect when we change one of the parameters of the

system (T, P,X).

We can have a variety of phase diagrams such as

1.Temp - Pressure, 2.chemical potential - Temp, 3.chemical Potential - chemical potential diagram, 4.chemical potential - composition diagram, 5.pressure - composition, 6.temperature- composition diagram and so on

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The slopes of the lines is given by the Clausius-Clapeyron

equation:

dP/ dT = ∆H /T∆S = ∆S/∆V

For some materials (H 2 O, Ga, Ge, diamond), however, ΔV = V s V l > 0 and

The slopes of the lines is given by the Clausius-Clapeyron equation: dP/ dT = ∆H /T∆S
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Factors that alter the state of equilibrium. (a)Concentration, temperature and pressure. (b)The addition of a catalyst has no effect.

According to this principle, if a system at equilibrium is

subjected to a disturbance( T,P & X) then the equilibrium shifts

in the direction that tends to nullify the effect of the disturbance or stress.

C + CO2 =2CO

∆H = +ve

Consider the variation of the free energy in the two phases I and II along their

Consider the variation of the free energy in the two phases I and II along their coexistence line:

dG I = dG II .

V I dp − S I dT = V II dp − S II dT.

V I dp − V II dp

= S I dT − S II dT

dP/ dT

= (S I -S II )/(V I -V II )

= ∆S /∆V

Consider the variation of the free energy in the two phases I and II along their
Consider the variation of the free energy in the two phases I and II along their

Latent heat (change in enthalpy): ∆H = T∆S

H 2 O, Ga, Ge, diamond

ΔV = V s V l > 0

A solution is a homogeneous mixture of two or more substance whose composition can be varied

A solution is a homogeneous mixture of two or more substance whose composition can be varied within certain

limits . The substances making up the solution are called

components of the solution . A solution phase is one where two or more elements are mixed and exist as a single phase .

Depending upon the total no . of components in the solution

  • 1. Binary solution

  • 2. ternary solution

  • 3. quaternary solution

Solution

A phase is a region of space (a thermodynamic system), throughout which all physical, chemical and structural

properties of a material are essentially uniform.

The thermodynamic properties of a solution phase are

expressed in terms of mixing functions i.e., enthalpy,

entropy & Gibbs energy of mixing which is given as the thermodynamic property of the solution minus that of the pure phases.

(1) Percentage by weight (2) Gram atomic basis (3) Mole fraction (4) Atomic fraction (5) Normality (6) Molality (7) Molarity

Empirical Statement - Limited number of binary solution

P A =X A P

A

--- (1)

if vapour behaves as an ideal gas

P A = f A

and P A = f

A

i.e

a A

= X A

Empirical Statement - Limited number of binary solution P =X P A --- (1) if vapour

Activity of a component equal to mole fraction of that component. An ideal solution one which obeys raoults law over all

temperature and pressure

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= X A a A
= X A
a A

.....

(2)

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The pressure exerted by the vapour at the equilibrium at given temperature is called vapour pressure

Henry’s states that the activity of a compound is proportional

to its mole fraction.

a A ∞ X A

aA =Ÿ XA

Where Ÿ activity coefficient

For ideal solution Ÿ =1

.. and For non ideal solution 1< Ÿ >1

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Ideal solution

  • The interaction between the components are similar to those in the pure components

  • There is no enthalpy change on mixing

  • There is no volume change on mixing

  • Each components obeys Raoults law at all temperature and composition .

Non ideal solution

  • The interaction between the components are different from those in the pure components

  • enthalpy change on

There is

mixing

  • There is volume change on mixing

  • Their components do not obeys Raoults law at all temperature and composition .They show positive and negative deviation from Raoults law.

+Ve deviation from ideal behaviour

behaviour

  • A-B forces are less than A-A & B- B forcesclustering of solution

  • ∆H mix =+ because energy is required to break A-A or B-B attractive force

  • Dissolution process are endothermic ∆H=+

  • Since endothermic , heating will increase the solubility of such solution

  • Because of decrease in the magnitude of intermolecular force in solution ,the molecules will be loosely held i.e ∆V=+

  • A-B forces are more than A-A & B-B forces -compound formation

  • ∆H mix =- because energy is required to break A-A or B-B attractive force

  • Dissolution process are endothermic ∆H=-

  • Since exothermic , heating will decrease the solubility of such solution

  • Because of increase in force of attraction in solution ,the molecules will be held tightly i.e

When two or more liquid metals are mixed together ,for complete mixing, change in free energy

When two or more liquid metals are mixed together ,for complete mixing, change in free energy must be ve

∆G = G of all product –G of all reactant =-ve

Otherwise the metals would be immiscible

Ideal solution

∆H mix = 0

& ∆V mix =0

∆S mix = -R(X1lnX1 +X2lnX2)

G mix =RT(X 1lnX1+X2lnX2)

Regular solution

∆H mix = X A X B ∆S mix = -R(X1lnX1 +X2lnX2)

∆G mix = X A X B -RT(X1lnX1

+X2lnX2)

Where Ω = Interaction parameter + for repulsion or endothermic - for attraction or exothermic Ex Cu Ag , Al-Zn , Fe-Mn etc

Regular solution has same ENTROPY as an ideal solution of the same

composition

-Hildebrand

SB S M S A 0 X B 1 H M H A H B 0
SB S M S A 0 X B 1
SB
S M
S A
0
X B
1
H M H A H B 0 X B 1
H M
H A
H B
0
X B
1
G M GB GA
G M
GB
GA
  • 0 X B

1

SB S M S A 0 X B 1 H M H A H B 0
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AMMASI A CSIR -NML India

12/30/2013 AMMASI A CSIR -NML India
AMMASI A CSIR -NML India 12/30/2013

AMMASI A CSIR -NML India

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Feasibility of a reaction ??? Chemical potential is identical with partial molar free energy The concept

Feasibility of a reaction ??? Chemical potential is identical with partial molar free energy

Feasibility of a reaction ??? Chemical potential is identical with partial molar free energy The concept
Feasibility of a reaction ??? Chemical potential is identical with partial molar free energy The concept
Feasibility of a reaction ??? Chemical potential is identical with partial molar free energy The concept
Feasibility of a reaction ??? Chemical potential is identical with partial molar free energy The concept
Feasibility of a reaction ??? Chemical potential is identical with partial molar free energy The concept
Feasibility of a reaction ??? Chemical potential is identical with partial molar free energy The concept

The concept of chemical equilibrium can be understood in terms of the chemical potential

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1.We can visualize a process better because of the similarity of concept with some of the common physical process . Just as heat transfer from higher temperature to

lower temperature

11.Its is not necessary to bother about the overall reaction but it is sufficient to find out the chemical potential of the species concerned only

1.We can visualize a process better because of the similarity of concept with some of the

Since

1.We can visualize a process better because of the similarity of concept with some of the

for ideal gas

1.We can visualize a process better because of the similarity of concept with some of the
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Objective

  • To study the scope of reaction kinetics as to know the mechanism of reaction for maximum yield and rate in industrial process .

  • How to express the rate equation .

  • what are all factors influencing the rate of chemical process.

  • Determine the rate controlling step .

  • Study of metallurgical reaction

Thermodynamics says??

can’t say

1 .How to make them happen

2.How fast they will take place

3.The reaction mechanism

Say only

Thermodynamics is concerned with initial and final equilibrium state.

Thermodynamics quantifies

phase composition at

equilibrium

What kinetics is ???

1.Most chemical reactions

occur by a series of steps

called the reaction mechanism.

2.Kinetics is concerned with mechanism, time of

reaction, productivity

3.Kinetics judges the practical feasibility of a process kinetics determines the speed at

which a reaction proceeds

towards equilibrium

4.Kinetics study is essential for design & process development

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Rate of chemical reaction

The rate of reaction tells us how fast the reaction occurs

Let consider

X +Y A

Rate : Change in Concentration of any reactant or product in reaction per unit time

Rate of chemical reaction The rate of reaction tells us how fast the reaction occurs Let

<Fe 2 O 3 >+ 3{CO} = 2<Fe> + 3{CO 2 }

Rate of chemical reaction The rate of reaction tells us how fast the reaction occurs Let

Unit ???

Mole lit / sec , kg / sec or Mole / sec or else ???

Nature of reactant & products i. A2O3 acts as barrier to further contact between atmosphere andT h e c o l l i s i o n are less frequent when the conctn are goes lower 12/30/2013 AMMASI A CSIR -NML India " id="pdf-obj-92-2" src="pdf-obj-92-2.jpg">

Nature of reactant & products

i. A2O3 acts as barrier to further contact between

atmosphere and metallic Al

ii. Reactions between covalently bonded molecules are

slow

iii. Reactions which involve bond breaking are slower

Concentration of the reacting species

i) Reached thermodynamics Equilibrium and

ii) The collision are less frequent when the conctn are goes lower

Temperature of the system

As the temperature of system increase the kinetics energy of

molecules increase which increase the number of collision between the molecules

Temperature of the system As the temperature of system increase the kinetics energy of molecules increase
Temperature of the system As the temperature of system increase the kinetics energy of molecules increase

Presence of catalyst

Temperature of the system As the temperature of system increase the kinetics energy of molecules increase

Surface area of reactants - increase probability of collision of atom and molecules .

Sum of the power to which the concentration of the reactants must be raised to determine

Sum of the power to which the concentration of

the reactants must be raised to determine the rate of reaction .

The order of reaction is the total power of

reactant

Rate = k [A] m [B] n Then , the overall order of reaction is (m+ n )

Reactions are designed as first ,second , third order etc., according to the sum of the power is equal to one , two ., etc

The order of reactions were determined by experiments only

The magnitude of the order of reaction may be zero , fractional or integral values The

The magnitude of the order of reaction may

be zero , fractional or integral values

The order of reaction should be determined by experiments only . It cannot be predicted in terms of stoichiometry of reactants and products

Higher order reaction may be experimentally converted into simpler order reaction by using

excess concentration of one or more reactants ..

Why ?? (Pseudo reaction )

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Rate of reaction is

A = X + Y

Rate of reaction is A = X + Y At beginning of reaction ,t=0 ; [A]

At beginning of reaction ,t=0 ; [A] = C O

mole.lit -1

After the reaction has proceeded for some time t= t ; C o = C mole.lit -1

Unreacted will (C o C ) mole.lit -1

Rate of reaction is A = X + Y At beginning of reaction ,t=0 ; [A]

On integrating Eq (2) for mentioned limits

Rate of reaction is A = X + Y At beginning of reaction ,t=0 ; [A]

Unit of k ??

t 0.5

??

The time required to reduce the concentration of reactant to one half of its initial

value .

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A + B = X + Y If Ca and Cb are concentration of A and B respectively at time t , the rate of reaction can be expressed as

A + B = X + Y If Ca and Cb are concentration of A and

If amount of each A & B reached after time t is x

A + B = X + Y If Ca and Cb are concentration of A and

C a & C b are the initial concentration of A & B respectively

On integrating within limits x=0 at t=0 and x=x at t=t

t 0.5

Unit of k ???

?????

A + B = X + Y If Ca and Cb are concentration of A and

Type of reaction

Homogenous reaction

  • Those which take place within one phase

i.e., single phase

  • Rate of reaction is proportional to that of volume of phase

  • No adsorption and desorption in homogeneous

e.g ., Reaction between gas molecules to produce gaseous products

burning of fuel gas in presence of oxygen, or reaction between aqueous

solution of acid and base

Heterogeneous reaction

  • Its involves more than one phase & reaction occurs not in bulk but at the interface .

  • Rate of chemical reaction is proposal to interfacial area between the two or more phase

    • Involving following steps

      • Adsorption of reactant into interfacial layer

      • Chemical reaction between adsorbed components

      • Desorption of products into the products phase

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Metallurgical systems are mostly heterogeneous Kinetic steps involved in heterogeneous reactions are:

i) Transport of heat/reactant species from bulk of phase A/B to the interface ii) Chemical reaction at the interface of phase A & B iii) Transport of the heat/product species from the interface to the bulk of phase A/B.

Rate Controlling step:

If step ii) is slowest step> Chemical reaction controlled (likely mechanism at comparatively low temperature)

If step i) or iii) is slowest step > heat /mass transfer controlled (most likely at comparatively high temperature)

Rate = k C Where k-Chemical rate constant C- concentration n – Order of reaction 12/30/2013

Rate = k C n

Where k-Chemical rate constant C- concentration n Order of reaction

Rate = k C Where k-Chemical rate constant C- concentration n – Order of reaction 12/30/2013
Let us consider aA + bB = C + D Rate = n = rate of

Let us consider aA g + bB s = C s + D g

Rate =

Let us consider aA + bB = C + D Rate = n = rate of
Let us consider aA + bB = C + D Rate = n = rate of

n B = rate of consumption of B per unit time J A = mass flux of reactant A at the gas/solid interface A S = Surface area of the gas/solid interface

Method 1 : Based on concentration profile Method 2 : Based on concept of mass transfer

Method 1 : Based on concentration profile

Method 1 : Based on concentration profile Method 2 : Based on concept of mass transfer

Method 2 : Based on concept of mass transfer coefficient

Method 1 : Based on concentration profile Method 2 : Based on concept of mass transfer
aA + bB = C + D ∆H =heat of reaction per mole of B consumed

aA g + bB s = C s + D

aA + bB = C + D ∆H =heat of reaction per mole of B consumed

∆H r =heat of reaction per mole of B consumed Q =Heat flux at the gas/solid interface

Gas – Solid Liquid – Solid Liquid – Liquid Solid-Solid Gas- Liquid 12/30/2013 AMMASI A CSIR

Gas Solid Liquid Solid Liquid Liquid Solid-Solid

Gas- Liquid

Model for rate equation:

i) Progressive reaction model,

ii) Shrinking core model

Assumption for shrinking core model:

i) Spherical particle

ii) Diffusion slower than chemical reaction>topo- chemical reaction

iii) Sharp interface iv) Fixed size

Kinetics steps

i)

Transport of reactant A through gas film to the ash layer interface

ii)

Diffusion of the reactant A

through ash layer to the

reaction interface

iii)

Adsorption and Chemical reaction at the un-reacted core surface

iv)

Desorption of the product at the reaction interface

v)

Transport of the product through the ash layer

vi)

Transport of the product through the gas film

Kinetics steps i) Transport of reactant A through gas film to the ash layer interface ii)
Kinetics steps i) Transport of reactant A through gas film to the ash layer interface ii)
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Dissolution of solid in a liquid Leaching

Dissolution of solid in a liquid – Leaching 12/30/2013 AMMASI A CSIR -NML India
Dissolution of solid in a liquid – Leaching 12/30/2013 AMMASI A CSIR -NML India
Dissolution of solid in a liquid – Leaching 12/30/2013 AMMASI A CSIR -NML India

Liquid Liquid Reaction Slag Metal reaction D S ,D P & D Mn etc

Liquid – Liquid Reaction Slag – Metal reaction D ,D & D etc 12/30/2013 AMMASI A
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