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

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12/30/2013 AMMASI A CSIR -NML India

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 ????

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Derived from Greek word & is the science of flow of heat
 Developed in 19th and early 20th century

(i) Invention of stream engine in 18th century and issue of the relation between heat and work . (ii) Count Rumford observed that qg ∞ work done (iii) In 1840 Joules experiment proved the count Rumford observation. This was led to First law of thermodynamics . (iv) In mid 19th Entropy as the thermo parameter (v) In 1904 W Nerst and Max Planck absolute entropy value - Third law of thermodynamics

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Entirely empirical ,observation and common sense Developed before people knew about atom and molecules so

science based on macroscopic properties of matter.

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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
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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 & ??

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Quasi equilibrium

Para equilibrium
Metastable equilibrium

Unstable equilibrium

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Thermodynamics terminology

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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

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Extensive properties
 Those properties of system that

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

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 : 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

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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. C&S

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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.

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Common sense law : Concept of temperature and heat flow A B TA=TC TB=TC

C Then TA=TB

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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.

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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 .

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Based on Boyles’s law – Empirical law

PV
PV=0= f(T)

-273.15

0 T(₀C)

100

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Boyle's &Charles' law

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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 Energy is conserved! NO THEORETICAL PROOFF
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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.

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

If a system does work on the external world, and no heat is added, its internal energy decreases.

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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

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

Specific heat ,
atomic heat and molar heat

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

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Amount of heat required to raise the temperature of 1 g of a substance by 1° C or 1 K
Substance
Water Ice Steam Al (s) Fe (s)

Specific heat (c) J/g °C
4.184 2.03 2.01 0.897 0.449

Amount of heat (J)
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Heat capacity at constant pressure (Cp) U = f ( T,P) dE= δq-P dV

Relation between Cv and Cp

For an ideal gas and isothermal process

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

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

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

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Heat of formation of compound 3 Fe2 O3 + CO =2Fe3O2 +CO2 Heat of reaction 2 Al +3/2 O2 = Al2O3 Heat of combustion C +O2= CO2 Heat of transformation Zn s  Zn l @ 963K Heat of solution

∆H r = -2.67 kJ/mole ∆H f =-1700kJ/mole

∆H = -393.5kJ/mole
Lf,Zn =+7.28 kJ/mole

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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

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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 .

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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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EntropyAMMASI A

CSIR -NML India

Ssurr

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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AMMASI A CSIR -NML India

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

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Classical thermodynamics .

A microstate specifies all molecular details about the system including the position and velocity of every molecule. In statistical mechanics, entropy is given as:
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"
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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-TS 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
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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

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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 Combined statement of first and second law 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
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Thermodynamic conditions for spontaneity and equilibrium for closed system. Spontaneous Equilibrium Non spontaneous

ΔGS < 0
ΔSU > 0
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ΔGS = 0
ΔSU = 0
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ΔGS > 0
ΔSU < 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 δw’ = 0 d G = V dP-S dT
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Apply relation to Eq (a) (δT/ δV)S = -(δP/ δS) V (δT/ δP)S = (δV/ δS )P Maxwell Relation (δP/ δT)V= (δS/ δV)T (δV/ δT)P= -(δS/ δP)T

These Equations are used to calculate thermodynamic parameter.

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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 ???

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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

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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
SAB –SA-SB = 0 the substance can not drop to 0 K by

The temperature of finite ways
.
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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-OThird 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 process ..

Transition from one state to another state

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Zero th law :Common sense Temperature 1st law of thermodynamics : you can break even Internal energy and Enthalpy 2nd law of thermodynamics : you can break even at Entropy and Free energy 3rd law of thermodynamics : you cant get to 0K Absolute value ..
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0K

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
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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.

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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. a = f /f ₀
Activity is a measure of free concentration. Concentration available for reaction.

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dG= RT d (lnf) = RT d (f₀ a) = RT(dln f₀)+ 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 = GI₀ +RT (ln a1 )
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Chemical reaction under isothermal isobaric condition

aA + bB +…. = dD +eE +….
∆G = ∆G₀ +RT ln( aDd.aEe / aAa .aBb ) ∆G = ∆G₀ + RT ln Q @ Equilibrium ∆G = 0 0 = ∆G₀ + RT ln K ∆G₀ = -RT ln K
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where K= (Q )eq

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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

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d ∆G₀ = ∆V₀ dP-∆S₀ dT At constant pressure d ∆G₀ = -∆S₀ dT

Gibbs –Helmholz Eq Integrating and divided by T 2

Von’t Hoff Equation

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

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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/ ∂n1) dn1
+

(∂ G/ ∂ n2)+……

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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

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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.

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At equilibrium the chemical potential of phase must be equal, i.e. µiI= µiII= µiIII= µiIV= µiV….{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 = C- P + 2 i.e., P+F=C+2
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-

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.temperaturecomposition 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 (H2O, Ga, Ge, diamond), however, ΔV = Vs – Vl > 0 and

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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 ∆H₀ = +ve

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Consider the variation of the free energy in the two phases I and II along their coexistence line: dGI = dGII . V Idp − SIdT = V IIdp − SIIdT. V Idp − V IIdp = SIdT − SIIdT dP/ dT = (SI-SII )/(VI-VII) = ∆S /∆V

Latent heat (change in enthalpy): ∆H = T∆S H2O, Ga, Ge, diamond ΔV = Vs – Vl > 0
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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
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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.

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(1) Percentage by weight (2) Gram atomic basis (3) Mole fraction (4) Atomic fraction

(5) Normality
(6) Molality (7) Molarity

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Empirical Statement - Limited number of binary solution PA =XA P₀A --- (1) if vapour behaves as an ideal gas PA = fA and P₀A = f₀A i.e aA = XA Activity of a component equal to mole fraction of that component. An ideal solution one which obeys raoults law over all temperature and pressure aA = XA .....(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. aA ∞ XA 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

Non –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 .

components are different from those in the pure components  There is enthalpy change on 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.

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+Ve deviation from ideal behaviour
 A-B forces are less than A-A & B-

-Ve deviation from ideal behaviour
 A-B forces are more than A-A &

 

B forces– clustering 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=+
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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 ∆V=-

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

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Ideal solution
∆H mix = 0 & ∆V mix =0 ∆S mix = -R(X1lnX1 +X2lnX2) ∆G mix=RT(X 1lnX1+X2lnX2)

Regular solution
∆H mix = Ω XAXB ∆S mix = -R(X1lnX1 +X2lnX2) ∆Gmix= Ω XAXB -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
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SM

S A

 SB

HM
H A H B

GM

 GB  GA

0

XB

1

0

XB

1

0

XB

1

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

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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

Since

for ideal gas

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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

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Thermodynamics says??
can’t say 1 .How to make them

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

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

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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

<Fe2O3 >+ 3{CO} = 2<Fe> + 3{CO2 }

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

Presence of catalyst

Surface area of reactants - increase probability of collision of atom and molecules .
12/30/2013 AMMASI A CSIR -NML India

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
12/30/2013 AMMASI A CSIR -NML India

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 ?? (PseudoAMMASI reaction ) 12/30/2013 A CSIR -NML India

Rate of reaction is

A=X+Y

At beginning of reaction ,t=0 ; [A] = CO mole.lit -1 After the reaction has proceeded for some time t= t ; Co = C mole.lit -1 Unreacted will (Co – C ) mole.lit -1
Unit of k ??

On integrating Eq (2) for mentioned limits

t 0.5 ??

The time required to reduce the concentration of reactant to one half of its initial value . 12/30/2013 AMMASI A CSIR -NML India

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

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

Ca & Cb 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 ???
?????

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AMMASI A CSIR -NML India

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 

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

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

Adsorption of reactant into interfacial layer Chemical reaction between adsorbed components Desorption of products into the products phase

12/30/2013

AMMASI A CSIR -NML India

12/30/2013

AMMASI A CSIR -NML India

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)

12/30/2013

AMMASI A CSIR -NML India

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

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AMMASI A CSIR -NML India

Let us consider aA g + bB s = Cs + Dg
Rate =

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nB = rate of consumption of B per unit time JA = mass flux of reactant A at the gas/solid interface AS = Surface area of the gas/solid interface
AMMASI A CSIR -NML India

Method 1 : Based on concentration profile

Method 2 : Based on concept of mass transfer coefficient

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AMMASI A CSIR -NML India

aA g + bB s = Cs + D

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

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AMMASI A CSIR -NML India

Gas – Solid Liquid –Solid Liquid –Liquid Solid-Solid Gas- Liquid
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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>topochemical reaction iii) Sharp interface iv) Fixed size

12/30/2013

AMMASI A CSIR -NML India

Kinetics steps
i)

Transport of reactant A through gas film to the ash layer interface Diffusion of the reactant A through ash layer to the reaction interface Adsorption and Chemical reaction at the un-reacted core surface Desorption of the product at the reaction interface Transport of the product through the ash layer Transport of the product through the gas film
AMMASI A CSIR -NML India

ii)

iii)

iv)

v)

vi)

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Gas – Solid reaction

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AMMASI A CSIR -NML India

Dissolution of solid in a liquid – Leaching

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AMMASI A CSIR -NML India

Liquid –Liquid Reaction Slag – Metal reaction DS,DP & DMn etc

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AMMASI A CSIR -NML India

12/30/2013

AMMASI A CSIR -NML India

12/30/2013

AMMASI A CSIR -NML India