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# MTD Important questions and answers (Short answer questions) 1) State any three applications of thermodynamics in metallurgy Ans:

In the construction of phase diagrams To understand various chemical reactions To predict the correct reducing agent in Ferrous and non ferrous extractive metallurgy To understand phase transformations during heat treatment of an alloy To predict new phases in the development of newer materials ) State a) the first law of thermodynamics !) its mathematical equation and c) la!el the terms Ans: Statement: The total energy of an isolated system remains constant, though there are changes from one form of energy to another. Mathematical equation: !"#\$ \$here ! %hange in internal energy of the closed system " ! &eat transferred to or from the system \$ ! wor' done (y or on the system ") Define a) heat of reaction !) heat of reaction at constant pressure c) heat of reaction at constant #olume Ans: a) \$eat of %eaction: The amount of heat evolved or a(sor(ed in a chemical reaction when the reaction is performed according to a (alanced chemical equation at a given temperature and pressure is called heat of reaction !) \$eat of %eaction at constant &ressure: The heat of reaction at constant pressure at a certain temperature is defined as the amount of heat evolved or a(sor(ed at constant pressure when the reaction is performed according to a (alanced chemical equation. This is represented (y & c) \$eat of %eaction at constant #olume: The heat of reaction at constant volume at a certain temperature is defined as the amount of heat evolved or a(sor(ed at constant volume when the reaction is performed according to a (alanced chemical equation. This is represented (y or ) ') (rite any three statements of Second law of thermodynamics Ans: *tatement+,: - It is impossi(le to construct a machine, operating in cycles, which will produce wor' continuously (y a(sor(ing heat from a single heat reservoir. - ./elvin+0lanc' statement of the second law1 *tatement+2: - &eat does not flow spontaneously from a cold to a hot (ody .%lausius statement of the second law1 *tatement+3: - \$henever a spontaneous process ta'es place, it is accompanied (y an increase in the total entropy of the universe That is *univ 45

)) (hat information can !e drawn from a positi#e slope change of a line in the *llingham diagram+ Ans: The slope of the llingham diagram is given (y +6*5 7ut ,S- . S- products / S-reactants ,S- (ecomes negative when S-reactants 0 S- products then only the slope 8/,S-) (ecomes positive, This implies that the reactants are undergoing phase transformation which may (e either melting are (oiling depending upon the value of /,S- if +6*5 is low it is melting if +6*5 is high it is (oiling. 1) (hy the line of the reaction 2 3 4 . 24 is down wards in the *llingham diagram. Ans: For the reaction 234 ..0 24 \$e have a solid reacting with a gas to produce two moles of gas, and so there is a su(stantial increase in entropy so the line slopes sharply downward as shown (elow in the figure. ntropy change for the reaction is given as *5 ! .2*5 8%9: # .2*5;%4 < *5 892:1 &ere *5;%4 is assumed negligi(le since ;%4 is solid. *ince for every one mole of consumption of 92gas two moles of %9 gas is (eing produced Therefore 2*5 8%9: 4 *5 892: 7ut slope of the line is given as ! +*5 ; 5 &ence the line of the reaction 2% < 52 ! 2%9 is down wards in the llingham diagram.

5) Slate Trouton6s rule and its use Ans: Trouton7s rule: It states that the molar entropy of vapori=ation of various liquids at their normal (oiling point is almost same and is a(out >?+>> @ /+, mol+, 9r 2, cal. I.e. * ! &AT(.p ! 2, cal 8se: The rule is used to estimate the enthalpy of vapori=ation of liquids whose (oiling points are 'nown.

9) Define: a) fugacity !) acti#ity: Ans: a) ;ugacity: it is a measure of escaping tendency of a su(stance to prefer one phase 8liquid, solid, gas: over another. It is represented (y BfC Fugacity appers as pressure (ut not really the pressure it is also 'nown as pseudo pressure or fictitious pressure (ut at low pressures fugacity approaches pressure mathematically it is expressed as

!) Acti#ity: the activity of a su(stance is defined as the ratio of fugacity in the given state to the fugacity in the standard 8or pure: state. Mathematically it is expressed as shown (elow a . f<f- where Ba7 denotes the DactivityE =) An Aluminium > Magnesium alloy contains =1:) atom? aluminium: 2alculate the composition of the alloy in wt?: The atomic weights of Al and Mg are 1:=9 and ':" respecti#ely:
Solution:
Wt FofAl = atomF AlXatwtAl X ,55 atomF AlXatwtAl + atomF MgXatwtMg

Wt FofAl =

## I,.H X 2J.I> X ,55 I,.H X 2J.I> + 8,55 I,.H: X 2G.32

. = :" Therefore \$tF of Mg ! ,55+I2.3 !5:5 1-) Define rate of a reaction and e@press it mathematically

Kate of a reaction can (e defined as the decrease in concentration of reactants or increase in concentration of products with respect to time. Mathematically it can (e expressed as shown (elow: %hange in concentration of reactants or products Time Kate of a reaction !

If concentration is expressed (y BxC then the change in concentration is expressed (y BdxC, Then dx is positive for the products since the concentration of products increases with time, whereas for reactants dx is negative since the concentration of reactants decrease with time. Then the rate of reaction can also (e expressed as dx dT Kate ! \$here dx +++ the change in concentration of products dT+++ the change in time +dx dT Kate ! \$here dx +++ the change in concentration of reactants dT+++ the change in time Define a) System !) Surrounding c) !oundary with a neat sAetch 9r

11) Ans:

System: L *ystem is that part of the universe, which is under thermodynamic study Surroundings: verything external to the system is called surroundings Boundary: The real or imaginary surface separating the system from the surroundings is called the (oundary *@ample: L gas entrapped in a cylinder fitted with piston as illustrated (elow :

1 ) A System a!sor!s :) Acal of heat from the surroundings at constant pressure then it performs a worA of '19C calculate the change in internal energy of the system Solution: Lccording to First law of thermodynamics d8 . DE > D( &ere M" . 2.H ' cal ! 2H55 N G.,> @ ! ,5GH5 @ M\$ ! ?H5 @ ,Oow d) ! ,5GH5 # G,>5 . 1 5- C 1") Define a) *@othermic reaction !) *ndothermic reaction and c) state sign con#entions Ans: a) *@othermic reaction: The reactions, which are accompanied (y the evolution of heat, are 'nown as exothermic reactions. In exothermic reactions the enthalpy of products is less than that of the reactants. !) *ndothermic reaction: The reactions, which are accompanied (y the a(sorption of heat, are 'nown as endothermic reactions. In endothermic reactions, the enthalpy of products is more than that of the reactants. For these reactions & ! <ve. c) Sign con#ention: For xothermic reaction & ! +ve, for endothermic reaction & ! <ve.

1') (rite a) any one statement in which Second law of thermodynamics can !e e@pressed and !) the mathematical equation of Second law of thermodynamics Ans: *tatement+,: - It is impossi(le to construct a machine, operating in cycles, which will produce wor' continuously (y a(sor(ing heat from a single heat reservoir. - ./elvin+0lanc' statement of the second law1 *tatement+2: - &eat does not flow spontaneously from a cold to a hot (ody .%lausius statement of the second law1 *tatement+3: - \$henever a spontaneous process ta'es place, it is accompanied (y an increase in the total entropy of the universe

That is *univ 45 O.7: any one statement can (e sufficient (: M" ! Tds \$here M" ! amount of heat transferred T ! Temperature in /elvin ds ! %hange in entropy 1)) State any three limitations and three uses of *llingham diagrams Ans: The limitations of llingham diagram are: ,: It is applica(le only to su(stances in their pure states that is pure metals and pure oxides or sulphides, (ut pure su(stances are rare in metal extractions therefore the information derived from the diagram cannot (e directly applied to actual reactions 2: %ompounds are assumed to (e stoichiometric which often is not true 3: The diagram shows the direction in which equili(rium lies (ut it does not specify the conditions under which it would (e reached G: Oo information on the 'inetics of the reactions can (e o(tained from the diagrams O.7: any three limitations can (e sufficient The uses of the *llingham diagram: ,: To determine the reducing agent for reducing a given metallic oxide to metalP 2: To determine the partial pressure of oxygen that is in equili(rium with a metal oxide at a given temperature, this will help us to predict the temperatures at which a metal is sta(le and the temperatures over which it will spontaneously oxidi=e 3: Qetermine the ratio of car(on monoxide to car(on dioxide 8%9A%9 2 ratio: that will (e a(le to reduce the oxide to metal at a given temperature. G: To determine the relative sta(ilities of oxides and sulphides etc. O.7: any three uses can (e sufficient 11) a) Define *llingham diagram !) write its principle of construction and c) draw the line for the reaction 2 3 4 . 24 Ans:

a) The llingham diagram is a plot (etween the standard free energy change 8R 5: of a reaction as a function of the temperature 8T: !) The principle of construction is ,F- . ,\$- /T ,S\$here 6R5 ! *tandard free energy change 6&5 ! standard enthalpy change

## 6*5 ! standard entropy change c)

15) The #apour pressure pG (measured in mm \$g) of liquid arsenicG is gi#en !y log p . / '1-<T 3 1:1= and that of solid arsenic !y log p . / 1='5<T 3 1-:9 2alculate the temperature at which the two forms of arsenic will ha#e the same #apour pressure Solution: It is given that the vapour pressures are equal, Therefore equating vapour pressures, + 2GJ5AT < J.JI ! + JIG?AT < ,5.> GG>?AT ! ,5I # J.JI ! G.,, 9r T ! GG>?AG.,, ! ,5I,.? / ! ,5I,.?+2?3 . 919:5 -2 (Ans) 19) a) Define He 2hatelier6s principle !) state the use of He 2hatelier6s principle c) name the #aria!lesG which affect the equili!rium of a reaction: Ans:

a: Se %hatelierTs principle can (e defined as: If a chemical system at equili(rium experiences a change in concentration, temperature, volume, or total pressureP the equili(rium will shift in a direction to which opposes or nullifies the imposed change. (: The principle is used (y chemists in order to manipulate the outcomes of reversi(le reactions, often to increase the yield of reactions c: Uaria(les that affect the equili(rium of a reaction are ,: %oncentration 2: Temperature 3: 0ressure and catalyst
1=) a) Define solution !) (right the equation for calculating wt ? from atom ? and c) atom? from wt?

Ans:
a: L solution is a homogeneous mixture composed of two or more su(stances. In the study of solutions, it is

customary to designate the component present in larger proportion as the solvent and the one in smaller proportion as the solute. (: quation for calculating wt F from atomF
Wt FofA = *imilarly, Wt FofB = atomF BXatwtB X ,55 atomF AXatwtA + atomF BXatwtB wt F A A atwtA X ,55 wt F A A atwtA + wt F B A atwtB wt F B A atwtB X ,55 wt F A A atwtA + wt F B A atwtB atomF AXatwtA X ,55 atomF AXatwtA + atomF BXatwtB

## c: quation for calculating atom F from wtF

atomFofA = *imilarly, atomFofB =

-) State the effect of temperature on rate of reaction with Arrhenius rate equation Ans: *ffect of Temperature: The rate of a reaction is increased considera(ly (y a little increase in temperature. The effect of temperature on the rate of the reaction can (e explained (y considering the Lrrhenius rate equation, which is given (elow Kate ! L e+"AKT \$here L+++0re exponential constant "+++Lctivation energy K+++)niversal gas constant T+++Temperature in / From the a(ove equation, we can conclude that the rate of a reaction increases exponentially with temperature. 1) a) Define \$omogeneous systemG gi#e one e@ample !) Define heterogeneous systemG gi#e one e@ample Ans: a) \$omogeneous system: L system, which consists of *ingle 0hase and )niform composition throughout, is called a &omogeneous system *@ample: L pure *olid or Siquid, L mixture of gases, \$ater < salt O.7: any one example can (e sufficient !) \$eterogeneous system: L system, which consists of More than one 0hases and %omposition, is not uniform is called &eterogeneous system *@ample: L Mixture two or more immisci(le solids, L Mixture of two or more immisci(le liquids, Ice in contact with water Ll+,2F *i

Rrey cast Iron 0earlite Metal # *lag + Ras ) Define a) \$eat 2apacity !) \$eat capacity at 2onstant &ressure c) \$eat capacity at 2onstant Iolume Ans: a) \$eat 2apacity - The quantity of heat required to raise the temperature of a (ody (y , 5 - If the temperature of the (ody is raised from T , to T2 (y passing an amount of heat ", the heat capacity % of the (ody is given (y % ! " A 8T2+T,: 89r: Q C= dT !) \$eat capacity at 2onstant Iolume - It is the amount of heat required to raise the temperature of a (ody (y , 5 at constant volume - It is denoted (y %v - Lt constant volume heat capacity can (e given as -

qV dT

\$here qv is heat a(sor(ed at constant volume c) \$eat capacity at 2onstant Iolume - It is the amount of heat required to raise the temperature of a (ody (y , 5 at constant 0ressure - It is denoted (y %p - Lt constant 0ressure heat capacity can (e given as -

CP =

dT

- \$here "0 is heat a(sor(ed at constant pressure ") calculate the heat of formation of J&2l)0 at =9 K from the following data: J&0 3 "(2l ) . L&2l"M N\$- =9 . /1):9 AcalO L&2l"M 3 (2l ) . J&2l)0 N\$- =9 . /"":9 Acal Solution: The required reaction is: ;04 < HA2 %l2 ! ;0%lH4 Set 2;04 < 38%l2: ! 2V0%l3W &52I> ! +,H.> 'cal+++++++ 8,: V0%l3W < 8%l2: ! ;0%lH4 & 2I> ! +33.> 'cal++++++++ 82: Multiply eqn 82: with B2C (oth sides 2V0%l3W < 28%l2: ! 2;0%lH4 & 2I> ! +J?.J 'cal+++ 83: Oow add eqn 8,: and 83: 2;04 < H8%l2: ! 2;0%lH4&52I> ! +>3.G 'cal+++++++ 8G: Qivide eqn 8G: with B2C
5 5

;04 < HA2 8%l2: ! ;0%lH4 &52I> ! +G,.? 'cal++++++ 8H: The a(ove reaction is same as that of the required reaction Therefore the heat of formation of ;0%l H4 at 2I> / is ! /'1:5 Acal (Ans) ') a) write the mathematical relation !etween entropy and heat !) define spontaneous process and gi#e one e@ample Ans:

a) Mathematical relation !etween entropy and heat: For a reversi(le change ta'ing place at a fixed temperature 8T:, the change in entropy 8*: is equal to heat energy a(sor(ed or evolved divided (y the temperature 8T: That is, T S !) Spontaneous process: L process, which proceeds on its own accord, without any outside assistance, is termed a spontaneous or natural process or irreversi(le process. *@amples ,: Kolling stone from high level to low level 2: &eat flow from high temperature to low temperature 3: Ras flow from high pressure to low pressure O.7: any one example can (e sufficient
)) a) Define *llingham diagram !) State any three uses of *llingham diagrams Ans:

a: The llingham diagram is a plot (etween the standard free energy change 8R 5: of a reaction as a function of the temperature 8T:
(: The uses of the llingham diagram: H: To determine the reducing agent for reducing a given metallic oxide to metalP J: To determine the partial pressure of oxygen that is in equili(rium with a metal oxide at a given temperature, this will help us to predict the temperatures at which a metal is sta(le and the temperatures over which it will spontaneously oxidi=e ?: Qetermine the ratio of car(on monoxide to car(on dioxide 8%9A%9 2 ratio: that will (e a(le to reduce the oxide to metal at a given temperature. >: To determine the relative sta(ilities of oxides and sulphides etc 1) a) write the principle of construction of *llingham diagram and !) draw the lines for the reactions 2 3 4 . 24O 2 3 4 . 24 Ans:

a) The principle of construction is ,F- . ,\$- /T ,S\$here 6R5 ! *tandard free energy change 6&5 ! standard enthalpy change 6*5 ! standard entropy change !)

5) a) write the !asic idea that the phase equili!ria pro#ides !) write the 2lapeyron equation for solid > liquid equili!rium of a single component system and la!el the sym!ols Ans:

a) 0hase equili(ria, a (ranch of chemical thermodynamics. The (asic idea the phase equili(ria provide is to understand how we predict what phases will (e sta(le in a system at a given temperature, pressure, and composition, and how those sta(ility relations will change as the temperature, pressure and compositions are varied. !) ;or solid P liquid, equili(rium the %lapeyron eqn is: d& N\$fusion &fusion XSatent heat of fusion dTXchange in melting point

## . dT T NI \$here d0Xchange in pressure TXmelting point

9) Define: a) fugacity !) acti#ity: Ans:

## U X change in volume of liquid and volume of solid 8 i.e., Ul # Us:

a) ;ugacity: it is a measure of escaping tendency of a su(stance to prefer one phase 8liquid, solid, gas: over another. It is represented (y BfC Fugacity appers as pressure (ut not really the pressure it is also 'nown as pseudo pressure or fictitious pressure (ut at low pressures fugacity approaches pressure mathematically it is expressed as

!) Acti#ity: the activity of a su(stance is defined as the ratio of fugacity in the given state to the fugacity in the standard 8or pure: state. Mathematically it is expressed as shown (elow a . f<f- where a denotes the DactivityE =) a) Define solution gi#e one e@ample of a metallurgical solution !) define concentration of a solution c) Qame any three methods to e@press the concentration of a solute

Ans:
a: L solution is a homogeneous mixture composed of two or more su(stances. In the study of solutions, it is

customary to designate the component present in larger proportion as the solvent and the one in smaller proportion as the solute. xample: ,: %opper # Oic'el alloy 2: %opper # Rold 3: Lustenite G: Ferrite etc (: The 2oncentration of a Solution refers to the amount of the solute present in a given amount of solvent or solution. c: There are several ways to quantify concentration of a solution. They are Ltom fraction, Mole fraction, Molality, Molarity and Oormality etc
"-) State the effect of temperature on rate of reaction with Arrhenius rate equation Ans: *ffect of Temperature: The rate of a reaction is increased considera(ly (y a little increase in temperature. The effect of temperature on the rate of the reaction can (e explained (y considering the Lrrhenius rate equation, which is given (elow Kate ! L e+"AKT \$here L+++0re exponential constant "+++Lctivation energy K+++)niversal gas constant T+++Temperature in / From the a(ove equation, we can conclude that the rate of a reaction increases exponentially with temperature. *ssay questions 1) a) state the ideal gas equation and la!el the sym!ols !) Deri#e ideal gas equation using Boyle7s and 2harles7 laws Ans: a: The statement: 0U!nKT \$here 0+++pressure U+++Uolume n++++ Oum(er of moles of ideal gas K+++ )niversal gas constant T+++ L(solute Temperature of ideal gas !) Deri#ation of Ideal gas equation: Lccording to 7oyleCs Saw + U Y ,A0 8Lt %onstant T and m:

Lccording to %harlesC Saw + U Y T 8Lt constant 0 and m: %om(ining the a(ove two laws we can write U Y TA0 9r 0UAT ! / \$here / is a constant / value can (e found as follows: ++++++++++++++ 8,: \$here

05 is , atm pressure U5 is 22.G lit T5 is 2?35/ If the a(ove values are su(stituted in the a(ove equation 8,: we get / !5 .5>2, lit+atm This value of B/C i.e. 5.5>2, lit+atm is constant and is same for every gas. &ence B/C is replaced (y a new constant called )niversal gas constant. This is represented (y BKC Oow the ideal gas equation ta'es the following form for ,+mole of gas &I<T . % For n+moles of gas the equation is &I<T . n% (or) &I . n%T ) Define *nthalpy and e@plain the concept of enthalpy Ans: *nthalpy: the energy content of the system at constant 0ressure is called enthalpy *@planation: For a process at constant pressure, The wor' of expansion \$ ! 06U where 6U is the increase in volume. If the heat a(sor(ed is D"E Oow the equation "!6 <\$ (ecomes "0 !6 p< 06U The increase 6 p in the energy content is 6 p ! 2+ ,, \$here , and 2 are values of internal energy for initial and final states The accompanying increase of volume 6U is 6U ! U 2+U, U2, U, are the values of volumes for initial and final states Oow "p! 8 2Z ,: < 0 8U2+U,: "p ! 8 2<0U2: # 8 ,<0U,: X..., *ince 0 and U are state properties, quantity 8 <0U: is dependent only on thermodynamic state &ence 8 <0U: is the state property and also the extensive property The extensive thermodynamic property 8 <0U: is called the &eat content or nthalpy and is represented (y D&E & ! <0U The equation B,C will (ecome "p ! &2+&, 89r: "p! 6&p &, and &2 are the heat contents of initial and final states of the system and 6& p is the increase in the &eat content at constant 0ressure *ince the &eat content is a state property , the &eat change at constant 0ressure i.e., " p is also a state property ") *@plain !riefly the #ariation of heat of reaction with temperature and deri#e the Kirchoff7s equation Ans: The heat of reaction changes with temperature (ecause heat capacity is a function of the temperature. The equation representing the variation of heat of reaction with temperature is 'nown as Kirchoff7s *quation: %onsider the following reaction in which BLC represents the products and B7C represents the reactants L ++++++++++ 7 The change in enthalpy is given as & ! &0+&K ++++++++++++++ 83: \$here &0 represents the sum of enthalpies of products

&K represents the sum of enthalpies of reactants Therefore & ! &7+&L Oow differentiating 83: on (oth sides (y T [& [T [&7 [T [&L [T

8 7ut %p ! [& [T

[& [T

8 There fore

%07

%0L

8 Oow

[& [T

6%0

The a(ove equation is called /irchoffCs equation ') Deri#e the free energy relationships Ans: Lccording to first law of thermodynamics DE . d8 3 D( Lccording to second law of thermodynamics dS . DE<T .0 DE . T dS %om(ining the a(ove equations TdS . d8 3 D( ///////// (1) The a(ove equation is called com(ined equation of first and second law of thermodynamics. quation 8,: can (e written as TdS . d8 3 &dI ///////// ( ) Oow according to the definition of free energy R ! &+T* Qifferentiating the a(ove equation dR ! d& + Td* + *dT 9r dR ! d8)<0U: +Td* +*dT 9r dR ! d)<0dU<Ud0+ Td* +*dT 7ut from equation 82: Td* ! d) < 0dU

*u(stituting in the a(ove equation dR ! Td* <Ud0+ Td* # *dT dR ! Ud0 +*dT Lt constant pressure d0 ! 5 Therefore dR ! +*dT

( 9r

RF RT

)&

/SdT

///////////(")

Lgain according to the definition of free energy R ! &+T* Qifferentiating the a(ove equation dR ! d& + Td* + *dT 9r 9r 7ut from equation 82: dR ! d 8)<0U: +Td* +*dT dR ! d)<0dU<Ud0+ Td* +*dT

Td* ! d) < 0dU *u(stituting in the a(ove equation dR ! Td* <Ud0+ Td* # *dT dR ! Ud0 +*dT Lt constant temperature dT! 5 Therefore dR ! Ud0

( 9r

RF R&

)T

///////////(')

The a(ove 83: and 8G: equations are the relations (etween a) free energy and entropy and !) free energy and #olume these are called free energy relations.

)) a) *@plain a!out the internal energy of a thermodynamic system !) pro#e that for a re#ersi!le process ds . Ans: a) Internal energy: The total of all the possi(le 'inds of energy of a system is called its internal energy. Internal energy of a system is made up of (y Internal potential energy Internal 'inetic energy Internal potential energy : This consists of the energy Que to electrostatic force of attraction (etween nucleus and electrons of the atom Que to inter molecular attractions Que to chemical (onds Internal Ainetic energy: This consists of the energy

Que to translational, vi(rational and rotational motions of molecules, atoms and electrons etc of the system Internal energy is a state property and extensive in nature. !) &roof of ds . - for a re#ersi!le process Set s, and s2 denote the entropies of (loc' , and (loc' 2 respectively, and let T , and T2 denote the temperatures of the (loc's. Set a small quantity Dq of heat flows from (loc' , to (loc' 2, and then the entropy change is given as under: DE

T1

T2

ds =

Q
T2

Q
T,

ds = Q.

, , 1 T2 T,

ds = Q.

T, T2 1 T,T2

For a reversi(le process T, T2 that is the difference in T, and T2 is negligi(le such that for practical purposes we can ta'e T, !T2 Then the entropy change d*rev ! q 8T, +T2:A T, T2 ! 5 Therefore for reversi(le process entropy change dS . -

1) Deri#e the 2lapeyron equation for Hiquid > Iapour equili!rium of a single component system Ans: %onsider the phase transformation of Siquid to Uapour of a one+component system such as pure metal Siquid 8S: \ Uapour 8U: the transition given (y quation 8,: is =ero. That is, R ! 5. RU ] RS ! 5 RU ! R S distur(ing the equili(rium Then From 8G: 8RU < dRU: ! 8 RS< dRS : RU ! RS 8H: 82: 83: 8G: 8,: *ince the S and U, phases are in equili(rium with each other. Therefore, the change in the Ri((s free energy for

If the temperature and pressure are altered slightly such that the free energy changes slightly (y dR without

dRU ! dRS 7ut we 'now from dR ! ] *dT < Udp Therefore dRS ! ] *SdT < USdp 8>: From 8J: Therefore 9r 9r 7ut dRU ! ] *U dT < UU dp

## ] *U dT < UU d0 ! ] *SdT < USd0 8*U] *S: dT ! 8UU+ US : d0 * dT ! U d0 d0AdT ! *A U * ! &vapAT

\$here &vap is latent heat of Uaporisation T is the temperature where phase transformation ta'es place that is (oiling point There fore d& N\$ . SSS(1") dT T NI The a(ove equation is called 2lapeyron *quation 5) a) Define the equili!rium constant for the reaction aA 3 !B . c2 3 dD !) 2alculate the equili!rium constant for the reaction: JQi40 3 (\$ ) . JQi0 3 (\$ -) At 5)-T 2 from the following data: JQi0 3 U (- ) . JQi40O NF4 . / ''" 1 3 =9:'' T C (\$ ) 3 U (- ) . (\$ -)O NF4 . / '1 - 3 )':9T C Ans: a) aA + bB <--> cC + dD

The upper case letters L and 7 are the reactants and % and Q are the products. The lower case letters a, ( are the no. of moles of reactants and c, d are the no. of moles of products The equili(rium constant 8/c: is defined as given (elow

!) 2alculation of equili!rium constant: Set ;Oi4 < ^ 852: ! ;Oi94P R9 ! +2GG32, < I>.GG T @++++++++++++++++8,: 8&2: < ^ 852: ! 8&25:P R9 ! +2GJ252 < HG.>T @ 9n *u(tracting 8,: from 82: +++++++++++++++++++++82:

;Oi94 < 8&2: ! ;Oi4 < 8&25:P R9 ! +,>>,+G3.JGT @ @ ++++++++++++++++83: The a(ove equation is the required reaction R9 at T! ?H5<2?3 ! ,523 is R9 ! +,>>,+G3.JG_,523 @ ! +GJH2G.?2@ 7ut the relation (etween equili(rium constant and free energy change is given (y R9 ! +KTln/e \$here /e is the equili(rium constant Therefore /e ! xp 8+R9AKT: ! xp 8GJH2G.?2A>.3,G_,523: ! xp 8H.G?: ! "5:) 9) a) Define %aoult7s law !) *@plain the factors causing a real solution to de#iate from ideal !eha#iour Ans: a) Raoults law: The activity of a component of an ideal solution is equal to its mole fraction. That is in an ideal solution of solvent A and solute B,

Where Activity of A ole fraction of A !imilarly aB " #B Where aB Activity of B #B ole fraction of B (: The deviations of a real solution from ideal (ehaviour are of two types they are ,: 0ositive deviation and 2: Oegative deviation The factors, which cause the deviations, are the interactions (etween similar and dissimilar atoms of the components of the solution. %onsider a solution in which the solvent is BLC and solute is B7C and if the interactions (etween similar atoms are FL+L and F7+7 and the interactions (etween dissimilar atoms are F L+7 then ,: If FL+L ! F7+7 ! FL+7 Then the solution (ecomes ideal 2: If FL+L < FL+7 > F7+7 Then the solution under goes negative deviation 2: If FL+L > FL+7 < F7+7 Then the solution under goes positive deviation The deviations are shown (elow in the diagram

=: a) *@plain the terms: heat and worA with units: State sign con#entions of heat and worA !) *@plain a!out worA of e@pansion: Deri#e equation for worA of e@pansion Ans: a) \$eat and (orA: \$hen a change in the state of a system occurs, energy is transferred to or from the surroundings. This energy may (e transferred as heat or mechanical wor'. \$eat: &eat is defined as the energy in transit (orA: Mechanical wor' is defined as force N distance. 9r \$ ! 0 U \$here 0 # is pressure U # is the change in volume 8nits of \$eat: In *.I units heat is measured in `oules. 8nits of (orA: In *.I units \$or' is measured in `oules. Sign 2on#ention of \$eat: The sym(ol of &eat is ". If the heat flows from the surroundings into the system to raise the energy of the systemP it is ta'en to (e positive, <". If heat flows from the system into the surroundings, lowering the energy of the system, it is ta'en to (e negative, +". Sign 2on#ention of (orA: The sym(ol of \$or' is \$. If the \$or' is done (y the system then wor' is ta'en as positive <\$. 9n the other hand if wor' is done on the system it is ta'en as negative, +\$. !) (orA of e@pansion: In physics, mechanical wor' is defined as force multiplied (y the distance through which the force acts. In thermodynamics the only type of wor' generally considered is the wor' done in expansion 8or compression: of a gas. This is 'nown as 0ressure #Uolume \$or' or 0U wor' or xpansion wor'.

Qerivation of equation for wor' of expansion: %onsider a gas contained in a cylinder fitted with a friction less piston. The constant pressure acting is 0. If the gas expands at constant pressure, the piston moves through a distance let this distance is DdlE. Then \$or' ! force N distance \$ ! f N dl 7ut f ! 0 N L 8here L!area of cross section of the piston: Therefore \$ ! 0 N L N dl ! 0 N U 8here U ! change in volume: Ras at constant pressure dl

## Therefore Wor\$ " %ressure # chan&e in 'olume

1-) Deri#e the relation !etween & (&ressure) and I (Iolume) in an adia!atic re#ersi!le process for an ideal gas Ans:

Deri#ation of %elation !etween & > I in an Adia!atic %e#ersi!le &rocess for an Ideal gas In an adia(atic reversi(le process, the first law of thermodynamics ta'es the following form " ! d) < 0dU 5 ! d) < 0dU d) ! +0dU Llso we have d) ! %vdT %vdT ! +0dU dT KT . +0dU %v ++++++++++ 8a: The state equation of an ideal gas is 0U! according to first law since in an adia(atic process " ! 5

## 8for , mole of gas:

Qifferentiating, 0dU < Ud0 ! KdT ++++++++++ 8(: *u(stituting 8a: in 8(: 0dU < Ud0 ! K 8+0dUA%v: ++++++++++++++++++++++ 8c: 7ut we have for I mole of ideal gas %p # %v ! K +++++++++++++ 8d: *u(stituting 8d: in 8c: 0dU < Ud0 ! 8%p # %v: 8+0dUA%v:

0dU 3

Ud0

%p %v

, 8+0dU:

%p %v

7ut

0dU 3 9r

Ud0

,:

8+0dU:

## Ud0 ! +0dU d0 0 . +dU U

9r Integrating on (oth sides we get d0A0 ! +8dUAU: 9r 9r 9r 9r ln 0 ! + lnU ln0 ! lnU+ 0 U ! %onstant!/ 0, U, ! 02 U2 ! /

11) a) state \$ess7s law of constant heat summation !) The reduction of iron o@ide in the !last furnace process according to the following reactions ";e 4" 3 24 . ;e"4' 3 24 O N\$- =9. /)":1 KC ;e"4' 3 24 . ";e4 3 24 O N\$- =9. 3'1:- KC ;e4 3 24 . ;e324 O N\$- =9. /19:' KC 2alculate N\$- =9 for the reactionG ;e 4" 3 "24 . ;e 3 "24

Ans:

a) \$ess7s law of constant heat summation This law can (e stated as: If a chemical change can (e made to ta'e place in two or more different ways, whether in one or several steps, the amount of total heat change is same no matter (y which method the change is (rought a(out. The law also follows as a mere consequence of the first law of thermodynamics. Set us suppose that a su(stance BLC can (e changed to BaC directly L ! a < ", \$here ", is the heat evolved in the direct change. \$hen the same change is (rought a(out through intermediate stages L < 7 ! "2 7 < % ! "3 % < a! "G The total evolution of heat ! "2 <"3 <"G !"H Lccording to &essCs law ", !"H !) Solution: 3Fe293 < %9 ! 2Fe39G < %92P Fe9 < %9 ! Fe<%92P &52I>! +H3., /@++++++++ 8,: &52I>! +,>.G /@+++++++++ 83:

Fe39G < %9 ! 3Fe9 < %92P &52I>! <G,.5 /@+++++++++ 82: Multiply eqn 82: with B2C 2Fe39G < 2%9 ! JFe9 < 2%92P &52I>! <>2.5 /@+++++++++ 8G: Ldd eqn 8,: and eqn 8G: 3Fe293 < 3%9 ! JFe9 <3 %92P &52I>! 2>.I /@++++++++ 8H: Multiply eqn 83: with BJC JFe9 < J%9 ! JFe<J%92P &52I>! +,,5.G /@+++++++++ 8J: &52I>! +>,.H /@++++++++ 8?: Ldd eqn 8H: and eqn 8J: 3Fe293 < I%9 ! JFe <I %92P Qivide eqn 8?: with B3C

## qn 8>: is the required eqn therefore N\$- =9. / 5: KC (Ans)

1 ) 2alculate the standard enthalpy and entropy changes at )T2 for the reaction: J2u0 + (4 ) . J 2u 40 NFo . /11= =-/11:' T log T 3 1 ":" T C Ans: 2alculation of standard enthalpy change: The enthalpy change in terms of Ro is given as

Therefore RoAT ! +,JI2I5AT+,J.G log T < ,23.3 ! +,JI2I5AT+,J.G ln TA2.353<,23.3 ! +,JI2I5AT+?.,2 ln T < ,23.3

## ! ,JI2I5AT2 + ?.,2.,AT1 < 5

7ut

! +T2 .,JI2I5AT2 + ?.,2.,AT11 ! +,JI2I5 < ?.,2 T ! +,JI2I5 < ?.,2_2I> ! +,J?,J> @ ! +,J?.,J> '@ Therefore the standard enthalpy change ! /115:119 AC 2alculation of standard entropy change:

## ! +?.,2 .,< ln T1 < ,23.3 7ut

so . ?.,2., < ln T1+,23.3 ! ?.,2., < ln 2I>1 # ,23.3 ! ?.,2.,<H.?1 # ,23.3 ! ?.,2.J.?1 # ,23.3 ! G?.?5G+,23.3 ! +?H.J @Adeg Therefore the standard entropy change 8so: ! /5):1 C<deg 1") a) State Temperature > heat capacity relation !) (rite a short note on heat change at constant #olume c) Deri#e Fi!!s > \$elmholtV equation Ans: a: The heat capacity of gases varies with temperature. The form of the expression that represents this variation cannot (e predicted (y means of thermodynamics, and so purely empirical formulae are used. Two such relations, which are used most widely, are ,: 2p . 3 T 3 T

2: 2p . 3 T / T/

\$here G G are constants %p +++ &eat capacity at constant pressure T +++ Temperature in /elvin (: For a process at %onstant Uolume, there is no xpansion and %ontraction i.e. 8dU ! 5: *o \$ ! 5 *o the equation " ! < \$ will (ecome " U ! 6 U &eat a(sor(ed at constant Uolume i.e., " U is equal to the energy increase 6 U accompanying the 0rocess c: Deri#ation of Fi!!s > \$elmholtV equation The Ri((s free energy for a closed system R ! &+T* Qifferentiating the a(ove equation dR ! d& + Td* + *dT 9r dR ! d 8)<0U: +Td* +*dT 9r dR ! d)<0dU<Ud0+ Td* +*dT 7ut Td* ! d) < 0dU 8com(ined eqn of first and second laws: *u(stituting in the a(ove equation dR ! Td* <Ud0+ Td* # *dT dR ! Ud0 #*dT at constant pressure 8d0 ! 5: the a(ove eqn reduces to 9r

## Ls the Ri((s energy for a closed system is it follows that

The dependence of the RAT ratio on T is found with the aid of the quotient rule:

1') Deri#e the 2lausius / 2lapeyron equation for Hiquid > Iapour equili!rium of a single component system and write its form after integration !etween pressures & 1G & and temperatures T1G T assuming N\$ constant Ans: Deri#ation of the 2lausius/2lapeyron *quation Lccording to %lapeyron equation the relation (etween vapour pressure and temperature for Siquid # Uapour equili(rium of a single component system is given as under d0 ! &

++++ 8,: \$e can ma'e two approximations, which will give us the %lausius+%lapeyron equation. ,: The first approximation is that the volume of a given amount of gas is much larger that the volume of an equivalent amount of solid or liquid. There fore U ! Ugas ] Uliquid b Ugas 9r 2: The second approximation is that the vapour produced (ehaves as an ideal gas therefore we can use the state equation of the ideal gas and we can replace Ugas (y the following. 0U ! KT 8ideal gas equation if n!,: That is, we set Ugas ! KTAp. \$ith these two approximations quation 8,: (ecomes d0A0 ! 8 &A KT2 :dT d ln0 ! 8 &A KT2 :dT 9r

dT

T U

+++++++++

d ln P H = dT RT 2

The a(ove equation is called the 2lausius/2lapeyron equation The a(ove equation ta'es the following form if it is integrated (etween pressures 0 ,, 02 and temperatures (etween T ,, T2 assuming & is constant
P, T

P2

d ln P = 8

H , dT : R T T2 2

ln

P, H , , = . 2 21 P2 R T, T2

The a(ove equation is very useful for estimating vapor pressures at any temperature if the vapour pressure at another temperature and the heat of vaporisation over that temperature range are 'nown. 1)) Deri#e the Iant \$off7s *quation for Isotherm for the reaction of the type aA 3 !B . c2 3 dD Ans: %onsider the given reaction at a temperature 8T: and a pressure 80: aL < (7 ;++4 c% < dQ The upper case letters L and 7 are the reactants and % and Q are the products. The lower case letters a,( are the no. of moles of reactants and c,d are the no. of moles of products The free energy change for the a(ove reaction is written as 6R ! R products # R reactants ++++++++++++++++++ 8,: R products ! cR% < dRQ ++++++++++++++++++++++++++ 82: R reactants ! aRL < (R7 +++++++++++++++++++++++++++ 83:

## Lpplying the a(ove equation to 82: and 83:

dRQ ! dR5 < dKT lnaQ +++++++++++++++++++++++ 8G: aRL ! aR5 < aKT lnaL ++++++++++++++++++++++++ 8H: (R7 ! (R5 < (KT lna7 ++++++++++++++++++++++++ 8J: *u(stituting the a(ove 8G:, 8H: and 8J: in 8,: 6R ! 8cR% <dRQ: # 8aRL<(R7: ! V8cR5 < cKT lna%: < 8dR5 < dKT lnaQ:W+V8aR5 < aKT lna: < 8(R5 < (KT lna7:W ! V8cR5< dR5:+8aR5< (R5:W < V8cKT lnac< dKT lnaQ:+8aKT lnaL< (KT lna7:W ! V86R5: < V8KTlnac%< KTlnadQ: + V8KTlnaaL< KTlna(7:W ! V86R5: < V8KT lnac%adQ:W + V8KTlnaaLa(7:W ! 6R5 < V8KT lnV8ac%adQ:A8aaLa(7:W 7ut V8ac%adQ: A 8aaLa(7:W ! /! the equili(rium constant Therefore 6R ! 6R5 < KT ln / If the a(ove reaction is under equili(rium at BTC and B0C then 6R ! 5 Therefore 6R5 ! +KT ln/++++++++++ 8?: The a(ove equation is called Iant \$off7s equation for isotherm. 11) a) write a short note on acti#ity coefficient !) *@plain the factors causing a real solution to de#iate from ideal !eha#iour Ans: a) Acti#ity 2oefficient: The ratio (etween Lctivity to mole fraction of a component in a solution is called Lctivity coefficient and is represented (y c and is written as follows c!aAN \$e can quantify the deviation of a solution from ideality (y using the activity coefficient In an ideal solution of L and 7, the L+L, 7+7 and L+7 interactions are identical and &ence a L ! NL 8here c ! ,: \$hen, L+7 interactions are stronger than L+L or 7+7 interactionsP Then a
L

; NL 8here c is ; , 8negative deviation from ideality: system can then tend towards compound formation and

## mixing is exothermic. xample: Fe+Oi 8liquid alloy:P

\$hen L+7 interactions are wea'er than L+L or 7+7 interactionsP then c is 4 , 8positive deviation from ideality:, system can then tend towards phase separation and mixing is endothermic. xample: Fe+%u liquid alloy ;actors causing de#iations from ideal !eha#iour (: The deviations of a real solution from ideal (ehaviour are of two types they are ,: 0ositive deviation and 2: Oegative deviation The factors, which cause the deviations, are the interactions (etween similar and dissimilar atoms of the components of the solution. %onsider a solution in which the solvent is BLC and solute is B7C and if the interactions (etween similar atoms are FL+L and F7+7 and the interactions (etween dissimilar atoms are F L+7 then ,: If FL+L ! F7+7 ! FL+7 Then the solution (ecomes ideal 2: If FL+L ; FL+7 4 F7+7 Then the solution under goes negative deviation 2: If FL+L 4 FL+7 ; F7+7 Then the solution under goes positive deviation 15: a) (rite any fi#e differences !etween re#ersi!le and Irre#ersi!le processes !) Define Thermodynamic equili!rium c) e@plain the criteria for the esta!lishment of thermodynamic equili!rium Ans: Keversi(le process ,: It ta'es place with infinitesimally small change 2: These are ideali=ed and true in principle only 3: *ystem is at equili(rium at all stages of the process G: \$or' done is maximum H: fficiency of reversi(le process is maximum J: This process can (e retraced (ac' in the opposite direction ?: xample: Ice can (e formed (y withdrawing heat from water at 55% under normal pressure. Further if heat is supplied at the same rate to ice at 55% under normal pressure water is formed at the same rate.

Irreversi(le process ,: It ta'es place with a finite change 2: Lll actual processes which occur are Irreversi(le 3: *ystem is at equili(rium only at the initial and final stages of the process G: \$or' done is less than that of reversi(le process H: fficiency is less J: this process cannot (e retraced (ac' in the opposite direction ?: xample: when two gases are allowed to mix up into a given volume at a constant temperature, the pressure in the container increases. 7ut the two gases cannot (e separated (y `ust with drawing the pressure from the mixture.

(: L *ystem is said to (e under Thermodynamic equili(rium if the system under goes infinitesimal change so that we L(le to determine the values of its state properties such as 0ressure, Temperature and Uolume. c: For the esta(lishment of Thermodynamic equili(rium the system should (e in Thermal equili(rium Mechanical quili(rium and %hemical equili(rium

Thermal *quili!rium means the temperature of the system must (e uniform throughout the system I.e. dT ! 5 \$here BdTC represents change in temperature Mechanical *quili!rium means the 0ressure of the system must (e uniform throughout the system I.e. d0 ! 5 \$here Bd0C represents change in pressure. 2hemical *quili!rium the %hemical %omposition of the system must (e uniform throughout the system I.e. d% ! 5 \$here Bd%C represents change in temperature 19: a) Define heat capacity at constant pressure (2p) and heat capacity at constant #olume(2#) !) Deri#e the relation !etween 2p and 2# for an ideal gas from first principles: Ans: a) \$eat capacity: The heat capacity is the amount of heat required to raise the temperature of the system (y one degree %elsius. The relationship (etween heat and temperature change is usually expressed in the form shown (elow 2 . E ,T

## \$here % is the heat capacity \$eat capacity at constant pressure 82&:: 2p . Ep ,T

\$here "p ! &eat content of the system at constant 0ressure \$eat capacity at constant #olume 82#:: E# ,T

2p \$here

E# ! &eat content of the system at %onstant Uolume. !) Deri#ation of the relation !etween 2p and 2# from first principles: Lccording to the definition of heat capacity at constant 0ressure 8% p:, %p is given (y the following equation

DEp 2p
!

NT 9r R\$ NT

//////////////(1)

2p

//////////////( )

\$here DEp or R\$ is heat content of the system at constant pressure : T is change in temperature Lccording to the definition of heat capacity at constant 0ressure 8% v:, %v is given (y the following equation 2# 4r 2#
! !

DE# NT R8 NT

///////////////(") ///////////////(')

\$here DE or R8 is heat content of the system at constant volume. T is change in temperature Lccording to first law of thermodynamics: That is Lt constant pressure: DE . d8 3 D( DE . d8 3 &dI DEp . d8 3 &dI

Qividing the a(ove equation with dT 8change in temperature ) DEp dT . d8 dT 3 &dI dT ////////////////())

## *u(stituting (1) and (') in ()) we get 2p . 2# 3 p dI dT ///////////////(1)

For one mole of an Ideal gas, the state equation is Qifferentiating on (oth sides: Lt constant pressure: Therefore That is

&I . %T &dI 3 Id& . %dT d& . &dI 3 - . %dT &dI . %dT dI dT . % &

## *u(stituting this in eqn (1) 2p . 2# 3 &: % &

Therefore 2p . 2# 3 %

9r 2p / 2# . %

(1=) ;e 4"G &!4 and 2u 4 present in a dead roasted tin ore react according to the following equationsG during leaching with 1:11 M \$2l at )-2 ;e 4" 3 1 \$2l ()- \$ 4) . ;e2l" (1)- \$ 4) 3 "\$ 4 &!4 3 \$2l ()- \$ 4) . &!2l (1-- \$ 4) 3 \$ 4 2u 4 3 \$2l ()- \$ 4) . 2u2l ()- \$ 4) 3 \$ 4 2alculate the heat of leaching process at )-2 per 1-- Kg of oreG assuming that the Si4 and Sn4 present in the ore are unaffected during leaching: Fi#en: (i) 2omposition of dead roasted tin ore is 1-? ;e 4"G )? &!4G )? 2u 4G 1)? Si4 and rest Sn4 (ii) Standard heats of formation of ;e 4"G 2u 4G &!4G ;e2l" (1)- \$ 4)G 2u2l ()- \$ 4)G &!2l (1-- \$ 4)G \$ 4G \$2l ()- \$ 4) at )-2 are /1=1:"G /'-:-G /) :'G /= :-G /"-:=G /9": G /19:" and /15:' Acal<mole respecti#ely: (iii) Atomic weight of ;eG &!G 2u and 4 are )):9'5G -5: G 1":)'1 and 11 g respecti#ely Solution: 2ompound Fe293 %u29 0(9 Fe%l3 8,H5 &29: %u%l 8H5 &29: 0(%l2 8,55 &29: &29 &%l 8H5 &29: \$eat of formation (A cal) +,IJ.3 +G5.5 +H2.G +I2.5 +35.I +>3.2 +J>.32 +,?.G

Fe293 < J &%l 8H5 &29: ! 2Fe%l3 8,H5 &29: < 3&29 +++++++++++ 8,: &eat of leaching due to , mole of Fe293 is ! .2&f Fe%l3 8,H5 &29: < 3&f &291+.&f Fe293 < J &f&%l 8H5 &29:1 ! .2_8+I2.5: < 38+J>.32:1 # .+,IJ.3<J8+,?.G:1 ! +>>.2J 'cal That is heat of leaching due to ,J5 g 8since , mole of Fe 293 ! ,J5 g: Fe293 ! +>>.2J ' cal

Lmount of Fe293 present in ,55 'g of ore ! ,5F of ,55 'g ! ,5 'g Therefore heat of leaching due to ,5 'g or ,5555 g of Fe 293 ! .8+>>.2J:A,J51_,5555 ! +HH,J.2H ' cal 0(9 < 2 &%l 8H5 &29: ! 0(%l2 8,55 &29: < &29+++++++++ 82: &eat of leaching due to , mole of 0(9 is ! .&f 0(%l2 8,55 &29: < &f &291+.&f 0(9 < 2 &f &%l 8H5 &29:1 ! .8+>3.2: < 8+J>.32:1 # .8+H2.G: < 28+,?.G:1 ! +JG.32 'cal That is heat of leaching due to 223.2 g 8since , mole of 0(9 ! 223.2 g: 0(9 ! +JG.32 ' cal Lmount of 0(9 present in ,55 'g of ore ! HF of ,55 'g ! H 'g Therefore heat of leaching due to H 'g or H555 g of 0(9 ! .8+JG.32:A223.21_H555 ! +,GG5.I ' cal %u29 < 2 &%l 8H5 &29: ! 2%u%l 8H5 &29: < &29+++++++++ 83: &eat of leaching due to , mole of %u29 is ! .2 &f %u%l 8H5 &29: < &f &291+.&f %u29 < 2 &f &%l 8H5 &29:1 ! .28+35.I: < 8+J>.32:1 # .8+G5.5 < 28+,?.G:1 ! +HH.32 'cal That is heat of leaching due to ,G3., g 8since , mole of %u 29 ! ,G3., g: %u29 ! +HH.32 ' cal Lmount of %u29 present in ,55 'g of ore ! HF of ,55 'g ! H 'g Therefore heat of leaching due to H 'g or H555 g of %u29 ! .8+HH.32:A,G3.,1_H555 ! +,I33 ' cal Therefore the heat of leaching process at 2H 5% per ,55 /g of ore ! +HH,J.2H ' cal < +,GG5.I ' cal < +,I33 ' cal ! /99=-:1) A cal (Ans) -) a) State the concept of ;ree energy and gi#e its mathematical equation !) 2hromium and 2ar!on present in stainless steel form 2hromium car!ide at 1---2: Show !y thermodynamic calculations which of the metals among SiG TiG and I should !e alloyed to stainless steelG so as to pre#ent the formation of 2hromium car!ide: Fi#en: " 2r 3 2 . 2r"2 O NF- . / -9--/':- T cal

Si 3 2 . Si2O NF- . /1 55- 3 1:11 T cal I 3 2 . I2O NF- . / ---- 3 1:1 T cal Ti 3 2 . Ti2O NF- . /')--- 3 :9 T cal Ans: a: The energy freely availa(le in the system for doing useful wor' is called free energy. It is represented (y BRC. This is also 'nown as thermodynamic potential or Ri((sCs free energy. The mathematical definition of free energy is given (y F . \$ > TS \$here &+enthalpy of the system

T+a(solute temperature *+entropy of the system The a(ove equation infers that the total energy availa(le in the system is B&C Lnd the energy which is not used for doing wor' is BT*C this is also called the (ound energy, the remaining energy that is BRC is only availa(le in the system for doing useful wor' which is the free energy.

!) Solution: First find the numerical values of the R 5 at T ! J55 < 2?3 ! >?3 / of the given reactions 3 %r < 2% ! %r3%2P R5 ! +25>55+G.5 T cal

R5 of %r3%2 at >?3 / ! +25>55+G.5_>?3 ! +2G2I2 cal *i < % ! *i%P R5 ! +,2??5 < ,.JJ T cal R5 of *i% at >?3 / ! +,2??5 < ,.JJ_>?3 ! +,,325.> cal U < % ! U%P R5 ! +25555 < ,.J T cal R5 of U% at >?3 / ! +25555 < ,.J_>?3 ! +,>J53.2 cal Ti < % ! Ti%P R5 ! +GH555 < 2.> T cal R5 of Ti% at >?3 / ! +GH555 < 2.>_>?3 ! +G2HHH.J cal Oow %ompare the Ualues of R5 of the a(ove compounds I,e 2r"2 O Si2O I2O and Ti2O 9n comparison, it can (e concluded that R 5 of Ti% is more negativeP this means the compound Ti% is more sta(le than %r3%2 Therefore, to prevent the formation of %hromium car(ide Ti should (e added 1) a) *@plain a!out the internal energy of a thermodynamic system !) Deri#e Fi!!s > \$elmholtV equation Ans: a) Internal energy: The total of all the possi(le 'inds of energy of a system is called its internal energy. Internal energy of a system is made up of (y Internal potential energy Internal 'inetic energy

Internal potential energy : This consists of the energy Que to electrostatic force of attraction (etween nucleus and electrons of the atom Que to inter molecular attractions Que to chemical (onds

## Internal 'inetic energy: This consists of the energy

Que to translational, vi(rational and rotational motions of molecules, atoms and electrons etc of the system

Internal energy is a state property and extensive in nature. !) Deri#ation of Fi!!s > \$elmholtV equation The Ri((s free energy for a closed system R ! &+T* Qifferentiating the a(ove equation dR ! d& + Td* + *dT 9r 9r 7ut dR ! d 8)<0U: +Td* +*dT dR ! d)<0dU<Ud0+ Td* +*dT Td* ! d) < 0dU 8com(ined eqn of first and second laws:

*u(stituting in the a(ove equation dR ! Td* <Ud0+ Td* # *dT dR ! Ud0 #*dT at constant pressure 9r 8d0 ! 5: the a(ove eqn reduces to

## Ls the Ri((s energy for a closed system is it follows that

The dependence of the RAT ratio on T is found with the aid of the quotient rule:

) a) State the Iapour pressure > Temperature %elationship of Hiquid > #apour equili!rium of a single component system !) !) (rite the 2lapeyron *quation for solid P liquid equili!riumG liquid P #apour equili!riumG AQD solid P #apour equili!rium and la!el the sym!ols Ans:

a: The relationship (etween vapor pressure and the temperature can (e explained with the 2lausius/2lapeyron equation.

d ln P H V = dT RT 2

Lccording to this equation, the rate at which the natural logarithm of the vapor pressure of a liquid changes with temperature is determined (y the molar enthalpy of vapori=ation of the liquid, the ideal gas constant, and the temperature of the system. If we assume that Hv does not depend on the temperature of the system, the %lausius+%lapeyron equation can (e written in the following integrated form where C is a constant.
ln P = H V +C RT

## The plot of vapor pressure versus temperature is shown (elow

(: ,: For solid \ liquid, equili(rium d0 ! dT \$here d0Xchange in pressure TXmelting point 2: For liquid \ vapour, equili(rium d0 ! dT \$here d0Xchange in pressure TX(oiling point 3: For solid \ Uapour, equili(rium d0 ! dT \$here d0Xchange in pressure TXsu(limation point &su(limation T U &su(limationXSatent heat of su(limation dTXchange in su(limation point &vap T U &vap XSatent heat of vaporisation dTXchange in (oiling point &fusion T U &fusion XSatent heat of fusion dTXchange in melting point

## U X change in volume of Uapour and volume of liquid 8 i.e., U v # Ul:

U X change in volume of Uapour and volume of solid 8i.e., U v # Us: ") Deri#e the Iant \$off7s *quation for Isotherm for the reaction of the type aA 3 !B . c2 3 dD Ans: %onsider the given reaction at a temperature 8T: and a pressure 80: aL < (7 ;++4 c% < dQ The upper case letters L and 7 are the reactants and % and Q are the products. The lower case letters a,( are the no. of moles of reactants and c,d are the no. of moles of products The free energy change for the a(ove reaction is written as 6R ! R products # R reactants ++++++++++++++++++ 8,: R products ! cR% < dRQ ++++++++++++++++++++++++++ 82: R reactants ! aRL < (R7 +++++++++++++++++++++++++++ 83: 7ut R ! R5 < KT lna cR% ! cR5 < cKT lna% *imilarly dRQ ! dR5 < dKT lnaQ +++++++++++++++++++++++ 8G: aRL ! aR5 < aKT lnaL ++++++++++++++++++++++++ 8H: (R7 ! (R5 < (KT lna7 ++++++++++++++++++++++++ 8J: *u(stituting the a(ove 8G:, 8H: and 8J: in 8,: 6R ! 8cR% <dRQ: # 8aRL<(R7: ! V8cR5 < cKT lna%: < 8dR5 < dKT lnaQ:W+V8aR5 < aKT lna: < 8(R5 < (KT lna7:W ! V8cR5< dR5:+8aR5< (R5:W < V8cKT lnac< dKT lnaQ:+8aKT lnaL< (KT lna7:W ! V86R5: < V8KTlnac%< KTlnadQ: + V8KTlnaaL< KTlna(7:W ! V86R5: < V8KT lnac%adQ:W + V8KTlnaaLa(7:W ! 6R5 < V8KT lnV8ac%adQ:A8aaLa(7:W 7ut V8ac%adQ: A 8aaLa(7:W ! /! the equili(rium constant Therefore 6R ! 6R5 < KT ln / If the a(ove reaction is under equili(rium at BTC and B0C then 6R ! 5 Therefore 6R5 ! +KT ln/++++++++++ 8?: The a(ove equation is called Iant \$off7s equation for isotherm. ') a) Define solution and gi#e an e@ample !) 2lassify the solutions !asing on their !eha#iour Ans: a: A solution is a homogeneous mixture composed of two or more su(stances. In the study of solutions, it is customary to designate the component present in larger proportion as the solvent and the one in smaller proportion as the solute. L common example of solution is salt or sugar, dissolved in water. xamples of solid solutions are alloys. 8BaC is activity: 8 BacC is the activity of B%C: Lpplying the a(ove equation to 82: and 83:

(: Qepending on the (ehaviuor of solutions they are classified as ,: Ideal solutions 2: Keal solutions and 3: Kegular solutions 1) Ideal solutions: L *olution is called ideal solution if the interactions (etween similar and dissimilar atoms is the same that is in an ideal solution of L and 7, the L+L, 7+7 and L+7 interactions are identical 9r FL+L ! F7+7 ! F%+% xample: %u+Oi alloys For an ideal solution &mix,ideal ! 5 *mix,ideal d 5 Umix,ideal ! 5 ) %eal solution: L *olution is called real solution if the interactions (etween similar and dissimilar atoms is different that is in a real solution of L and 7, the L+L, 7+7 and L+7 interactions are different 9r FL+L d F7+7 d F%+% For a real solution \$here F indicates the interaction &mix,real d 5 *mix,real d 5 Umix,real d 5 xample: Fe+Oi, Fe+%u ") %egular solution: L special type of a non+ideal or real solution whose (ehaviour is in (etween the ideal and real solutions for which the enthalpy of mixing is non+=ero (ut the entropy of mixing is identical to that of ideal solutions For a regular solution &mix,reg d 5 *mix,reg ! *mix,ideal Umix,reg d 5 \$here F indicates the interaction