© Career Avenues Chapter-1 Introduction to Thermodynamics Metallurgical Thermodynamics Intensive and Extensive properties 1[MT-Metallurgical Thermodynamics en Intensive Properties are those which are Independent of mass of system. Property of small portion of the system defines the property of whole of the system, Intensive properties are expressed in lower case letters except Pressure (P), temperature (1). All the specific properties are intensive properties Example: Pressure (P), temperature (1), density(p) ete. Path function and Point function ‘They depend only upon the initial and final condition state) ofthe system but not on the path followed hy the system They have exact differential ie. their Integration can be carried out simply. Differential amount is represented by symbol “a” ic, small change in volume will be expressed as aV. Change in value can be expressed as the difference between initial and final value o ffav=v,-v, Thermodynamic properties are point functions since fora given state there i a definite value for each property and is Independent of the path the system follows during the change of state In a cycle, since initial and final states are identical, the eyclc integral of a property (point function) is always zero ie. § V = 0.§P=0§T=0 ee Extensive Properties are mass dependent. Hence their value depends upon the size of the system. "An extensive property when expressed as per unit mass becomes an intensive property (Specific property). Extensive properties are expressed in upper case letter except mass. Example: mass (m), energy (E), enthalpy (HD, entropy (S) ete ‘They depend upon the path Followed by the system. ‘They have inexact differentia. Differential amount is represented by symbol6 1. for small work done OW and small heat transfer 6@ Work and heat are the path functions, Change in the value can NOT be expressed as the difference between initial and final value, [oe we, eam (but not AW) Before integration, multiplication with, integrating factor is required. www.cavindia.com© Career Avenues 3. Teal gas law Ideal gas equation PV=RT ‘where R is a constant known as the ideal gas constant Vis the molar volume of the gas. Mathematically, we write the equation of state, as follows; [PV = nRT ‘Where nis the number of moles 2[MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues Chapter-2 Laws of Thermodynamics 1, Statement of First Law of thermodynamics The first law of therenodynamies is based on the law of conservation of energy Le., energy can neither be converted. ‘or he destroyed it can only be converted from one form to another. According to first aw, the change in the internal enéryy (AU) ofthe system is equal to the quantity (q— W) au=q-W Where AU = finite change in the internal energy (q= amount of heat absorbed by the system W = work done by the system upon the surroundings For an infinitesimal small amount of work the first law of thermodynamics can he expressed as, aU = 3q—3W and ow = Pav DaU = bq — Pav 2. Heat Capacity. “The heat capacity of a substance 1s defined as the aMount of neat required to atse its temperature by one degree, In other words, It isthe ratio of the amount of heat energy transferred to an object to the resulting increase in its temperature, og or Units of heat capacity = = Cal/C mole (CGS unity 1K mol {S1 unit) ) Heat capacity at constant volume (Cy b) 3, Relation between Cy and Cy R| ‘Where R = universal gas constant a) Forideal gas [C, —C, = 3[MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues Gi Cy Enthalpy Enthalpy is the function of state and its value depends only on the starting and final state of the system. Itis the sum of the internal energy ofthe system plus the product ofthe pressure of the gas inthe system and its volume whieh is given by, H=U+PV Enthalpy is an extensive property as it depends on the amount of the system. wey (or G (=) oT Jp 8) First aw of thermodynamics in terms of Enthalpy [dH =5q+VaP| b) —_Enthalpy change at constant pressure (dP a= 5q Change in Enthalpy. Note: 1. When heat is evolved from the system enthalpy change (AH ) is negative and the reaction is termed as exothermic resction AH = Henat~ Hint =-Ve (When the reaction is exotherre, HiniHisis) 11/-When heat Is absorbed by the system enthalpy change (AFF) is postive and the reaction is termed as endothermic reaction, AH= Hon Hlnisa= #8 (When the réaction is endothermic, HaHa) Change in enthalpy for a chemical reaction Change in enthalpy for a chemical reaction is given by, AH =D Hratee “EA pena ‘Change in enthalpy for standard sate (Ge, at 298K, 1 atm pressure) AH2,=¥ Hr “Hosa Note I. The enthalpy ofthe pure element a 298 K i taken tobe zero for example H 298 [Fe(s)] = 0 ‘H® 298 [C]= 0 A|MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues 1 The enfhapy of a compounds taken as the enthalpy of formation (AK?) ) ——_Enthalpy change for a substance when temperature varies , 11h =fepar i 2) Enthalpy change fora substance from; to Tsat constant pressure with change of tate H-m,=["coaret, + fc (odr +t, +f Color , hy by “Where Tr= fusion temperature (transformation from solid to liquid) 1, = Boling temperature (transformation from liquid gos) Ly = latent heat of fusion La = Latent heat of boiling (Here, T> TT TH) 4. _Enthalpy change due to chemical reactions a) Heatof areaction(¥!,) AH, = (sum of heat content ofthe product) ~ (sum of heat content ofthe reactant) EHp - Hp b) — Heatof formation AF) Heat of formation is the enthalpy change when 1 mole of the compound is formed from its constituent elements is their stable forms, at 298 K and 1 stm pressure all; = Sp Phan _ seactante 5. Kirehhoff’s Law “The heat of redton (AHL) ofa given substance usualy alters with temperature change since c,-( oT Jp AH Hence, for a feaction at constant pressure, AC, =| ——— en ( On rearranging, the above equation we get, (AH) - AC,aT Now integrating over a temperature range from T: to T:, we get: tee 5 J d(aH) = [Acar oraH,, - AH, by i Heat of reaction at T: can be found out from Kirehhoi's equation. Ifheat of reaction at T and value of “Cr over a temperature range fom Tto Ts are lnown ACy =(E Cp aur ~E Caeser) “We knaw that S[MT-Metallurgical Thermodynamics www.cavindia© Career Avenues “And ‘Therefore, the above equation becomes T “This is another forrn of Kizchhof?'s Law Cp=a+bT +c Abn, + [Cp pat -E Cr mecon T i 6. Entropy Entropy isa thermadynamic property that increases when heat is supplied and decreases when heats rejected and remains constant if there is no heat transfer. ‘When a substance absorbs infinitesimal amount of heat in a reversible manner, at an absolute temperature T, ‘the entropy of a substance increases by dS, such that Saree - ase Where dS = change of entropy J/K/mol 6. = heat absorbed by the substance in a reversible manner ‘T= temperature ofthe substance in K ‘NOTE: The entropy change for a reversible process involving system and surroundings is zero (Isolated system} ie, ASnon + \Screaunting 1, The entropy change for an irreversible process involving system and surrounding is always greater than fe, ASy + \Ssreaunsing 20 ‘The Entropy of a substance (4a) OT) cn = (Sear Ty} as Cpd In Entropy change for a chemical reaction AS [Sum of entropies of products] [Sum of entropies of reactants] = Sproduer ~ © Steacant 6|MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues b) % a) b) eo If the substances are in standard state then, (298K, 1 atm) ASP =ESP product ~ ESP neactant Entropy change for a substance when itis heated from temperature T, to T: without change in state ne, as = as,—as, = [ae Entropy change for a substance when itis heated from temperature T, do T, with change in state, (SL) ar (2) + (8 (S2) ar Where Tm.= melting point ofthe substance 1 inital temperature Final temperature Ce (3) = heat capacity ofa substance in solid state CoC) = heat capacity of a substance in liquid state Lr= latent heat of fusion Le= latent heat of evaporation ‘Third Law of Thermodynamics Gibbs Free energy ‘The function G known as Gibs free energy or simply’free energy is defined by the relation: G=H-TS By differentiating eq (G = H— T'S) at constant temperature and pressure: aG = dH -Tas Free energy of a rea “The free energy change fora reaction Is the difference between the sum of the free energies of the products and that of the reactants at constant temperature. “Thus, fora feetion at temperature T: AG EC produc ¥ Grancans LH, -TYS,]-(EH, TES, sine SH, -SH, |-T[Ss,-S5,] “Therefore, AG-AHt—Tas HTS] Gibbs free energy for a reaction involves heating from temperature T: to T, in a reversible manner ‘without change of state seer fat ofa] fas of 2 sit, 15, [jeri Sio| 7[MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues 10, The Maxwell's a= Tas + VaP dG ~ ~Sar + VaP 11, Statement of the Third Law of Thermodynamics “The figure given above shows a method of evaluating entropy éhange of reaction at absolute zero. “The starting point ofthe cycle isa system composed of only reactants atthe absolute zero, 1 step of the cycles: consist in heating only the feactants ta Some temperature T. From previous experience itis Inown that T is the temperature at whieh the resetants are in equilibrium with the products. 2° step of the cycles: the reaction isallowed to proceed completion at temperature T. ‘377 step of the eyeles: The products are cooled to the absolute zero, ‘a step of the cycles; It is the imaginary step, in which the reverse reaction is allowed to proceed ‘The total entropy change over the cycle is zero, ie, ASL #ASy + AS + AS =0 or Wy = a(S, +45, + 45,,) Since the entropy change during the first three steps ean be measured experimentally, the entrapy ehange at ‘the absolute zero can be determined by the equation ASy = (AS, +48, + 45 ,,) 12, ‘Thermodynamics Processes 8[MT-Metallurgical The modynamics www.cavindia.com© Career Avenues P=C Isobaric Process Pv Isothermal Process pve Polyiropic Process PV'=C Adiabatic Process BxeHo Isochoric Process ‘sobaric Process | —— W, = PIV, — Wa] 0, =me, (7, -T)] = a | | — ‘Adiabatic Process, |\. —ai “Approcess —.. ae ) (3) ee t-f) le sno heat ‘wansfer Isotherm Process 1 “A process ‘where ‘emperatur — -eremains i =merin Fv] ‘constant sc a Mesh) Gi. =me, (7-7) . ind -Py.n8] = Pune =P ni 9[MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues Chapter eI city, Activity, Es ium Constant and Solution od Fugacity Coefficient “The ratio of fugacity to pressure is referred to as fugacity coefficient and s denoted by ¢. It is dimensionless and depends on nature of the gos, the pressure and the temperature. Integrating the equation dG = RTd (Inf) between pressures fand f, Since f° =P" and = P we can write the above equation as G G4 RT Ings + RTIng Activity, Activity is defined as the ratio of fugacity of the substance in its actual State toils fugacity in the standard stat. £ F Gibbs free energy in terms of activity ‘The concept of activity denotes the change in free energy (AG) when a substance goes from standard state (Le, pure state) to a state of a solution (Le. actual state). Generalizing it for species, we have: G-G?=RT Ina: ‘Therefore G,=G? + RTIna, Where G, 0 arial free energy of ith spectes (in actual state of 1) free energy of ith species (in standard state of i) Chemical rium For the chemical reaction: JA+KB IC +mD ‘The equilibrium expression is 10|MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues au [As [AG =AH — TAS . ‘action wil go spontaneously : + Reaction needs input of energy to go The signof AG Depends onthe sign of AG > p> Depends onthe relative valuesof AW, A Sand 6. LeChatelier’s Principle 7. Gibbs-Helmholtz equation tis given by In other forms, 8. Name Hoff equation tis given by, JA[MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues ae << ; { p= i seepe AIR. 9. Clausius-Clapeyron equation 10. Ideal and Non-Ideal Solutions a) Raoult’s Law Raoult's Law states that the partial presse of the vapour of any component of an ideal solution is equal to ‘the product ofits mol fraction and the vapour pressure of the pure component at the same temperature as ‘that of Ideal solution Pra Xa Pe Where Pq patil pressure ofthe vapour of any component (A) Xi Mol froction _P? = vapout pressure ofthe pure component Consider the ease ifthe vapour behaves as an ideal gas In such case Py fr And we know thet Inother words, Raoult’ law can also be defined as,"The activity of a component is equal to the mol fraction ‘of the component” 412|MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues ») e ct a Henrys Law Henry's law states thatthe activity of the component is equal to its mole fraction ayaX, y= 7Xy ‘Where is the activity coefficient. For component i For an ideal solution 7=1 since a= X; For & non ideal solution i>] (ve deviation) <1 (ve deviation) ‘This implies that Non — ideal solution does not obey Raoult's law Law Sieve ‘This law is used to predict the solubility of gases in metals. Ie states that he solubility of a gas in a Uguid is proportional to the squace root ofthe gas pressure and increases with increasing temperture Example Ng(g) 224 (dssobved atoms) For the above equation, equilibrium constant 2 x lu Py, Now if the solution of gases obey Raoul’ law then ay={N] (Activity equals concentration) B,, = partial pressure of nitrogen gas ‘Thermodynamics of mixing of solutions ‘Thermodynamics of mixing of Ideal and Non- Ideal solutions For mixing of two or more liquid metals to takes place, the Gibbs free energy must be negative, otherwise ‘the metals would be immiscible. 43|MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues “where peducr= ft energy of products i.e. mixed solution Greacanes = F88 energy of reactants Le, metals to he mixed Integral molar functions of mixing ‘The mixing process when one mole of alloy is formed can be represented by XAA *XaB = ABs Now the free energy of mixing AGna is given by, AGnnis = Gan ~ (XaG"a + XG") (XaGa + XaGe)~ (XAG + XeG"s) XAGa G's) + Xe(Ger Gx) AGni= XAG, + XeAGe Where AGma= integral molar free energy of mixing Ga= partial molar property of A Gu= pattal molar property af B G*a= molar free energy of A in their pure states G*q= molar free energy of B in their pure states ‘Thermodynamics of iguid immiscibi ‘The enthalpy of mixing determines whether two liquids A and B mix AG nis = AHnic — TAS For mixing to occur, the following conditions are necessary @as=o (i AH <0 (Stronger A-B attraction) ‘The liquids are miscible at al temperatures (i) IfAH>0 (Stronger A-A, B-B attraction) Possibly miscible if AH < TAS (High Temperature) Possibly immiscible if AH > TAS (Low Temperature) ‘Thermodynamics of iquid immiscibility for Ideal Solutions For an Ideal Solution, the entropy of mixing is given by ASMois = -MR(KalNX4 + XelnXe) Where Xq and Xp are the mole fractions of the mole fractions of the two components and the enthalpy of mixing of Ideal solution is zero, 1iis the total number of motes ABP ga, ‘The Gibbs free energy of mixing is therefore, AG pig= AHP nix —TASHac, = MRT (LalmMy + Non Xa) 14|MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues b) Thermodynamics of Liquid immiscibiity for Regular Solutions For a regular or real solution, the entropy of misting is same as for the Ideal solution but the enthalpy now depends on the composition. ‘The Enthalpy afa Regular or Real Solution is given by, ABlas= OX Xn Interaction Parameter Where “The Gibbs Free Energy of mixing is given by NGnic= AH nic ~ TASnic For Non-Ideal/Regular/Real Solutions, AGax an be obtained by replacing mole fraction by activity AGuic MRT (Xalnas * Xolnas) Nov Alla MGaut Sa ‘Mfg = ART * Naa) + Taal Nal) ‘lls = ART OKain® * Kal) Since activity, a =X ‘Therefore, for Regular Solutions, AHmi= MRT (Xalny,, + Xalnyy) 13, Excess Properties If Gis the value of the thermodynamic function ita given solution, the excess thermodynamic property G*S isgiven by, @s=G-Gi Where Gis the coresponding thermodynamic property in an ideal solution having the same composition as the given solution Now Gibbs Free Energy for a regular solution is given by, AG: “AHnix~ TAS nic-nRT (alan + Xalnas) ‘Where ms the total number of moles ‘And Gibbs Free Energy for a eal solution is given by, AGilyic = Alas, — TAS nic = DRT (KalnX * XalnX) ‘This implies thatthe Excess Gibbs Free Energy is, AG* = AG “AGH nic ART (Xalnay * Xalnas)] — [MRT (KalnXa + XslnXs)] BRT (Xalny, * Xalny,) XaKe Hoss This implies that AG™ snd yg 23 Haws + Xow ‘On approximation, 15|MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues 14. Non-ideal dilute solution ‘where Ee =a constant This relationship is known as Henry's Law andy! referred to as Henry's Law Constant isthe atvity 1 ‘And for equilirium Ce) = 4,08) Where 1, (andy, (B) are the chemical potential of species Fin phases « and respectively ‘Chemical potential is ideal with partial molar free energy. From elementary thermodynamics we have, ae) = PCa) + RTIna,(@) and 4 (8) = uP (B+ RTIna,(B) ‘where i isthe chemical potential of tat its standard stat, Br the standard state of is the samte in both the phases then H@ = BD So, a(e) > a,(f), for transfer from ct to And for equilibrium, (a) = a,(f) 17|MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues Chapter-4 Electrochemistry 1. Difference between Galvanic cell and Electrolytic Cell Galvanie Cell Electrolytic Cell ‘Changes chemical energy into Electrical energy. 1. Anode is negative 2, Cathode is pesitive 3, Spontaneous reaction occurs 4, Does not require external voltage source 1. Anode is posit. 2. Cathode is negative 3. Non-spontaneous reaction occurs 4, Require external voltage source ‘Changes electrical energy into chemical reaction. 2. Electrolytes Strong Electrolytes ‘Weak Electrolytes ‘Allows a large amount of electricity to flow through them. “Allows a/small amount of electricity to ‘low through them. ‘Are completely dissociated Are partly dissociated Solutions contain only fee mobile ions Parlly ionized and parlly unionized molecules are present Examples Acids HCI, HNO: Bases - NaOH, KOH solution Salts - CuCl, PbBrz Examples, Acids ~ Acetic, Oxalic Bases - NHLOH Salts - NasCOs, Nal#COs ‘Anoile Cathode ‘connected to the positive terminal of the battery ‘connected to the negative terminal of tie battery ‘Acquires posilive charge during electrolysis, ‘Acquires negative charge during electrolysis ‘Migration point for anions “Migration point for cations Electrode Potential Electrode Potential is denoted as EMF (electro motive force). EMF of any electrolytic cell isthe sum of the EME produced at two electrodes. 18|MT-Metallurgical Thermodynamics www.cavindia© Career Avenues Blectose Oxidation reaction | Standard yoentel | Nature (vols) LilLit ub +3040 K IK K #2924 calc Co tee #2870 Nal met Na Netter 42710 ALLAP® al +1660 a tn | Za? in +0762 a Fe | Fet* Fe +0441 emg cal ca ca — -+0.403 wily? a +0236 suse? sn +0140 Pe lr rm +0126 Pingu | Hy — 000 cul cu co “0337 Ag lAgt Ag(s) — -0799 oxidising 4 gente Hg | He: Hg) — Hi -0920 aay |or cr — 11359 5. Earaday’s Law of Electrotvsis a) Faraday's First Law of Electrolysis, It states that the amount of any substance (W) that is deposited on an electrode is directly proportional to the quantity of electricity passed through the electrolyte wag where W = Weight of deposit () Q = quantity of elecrety (C) Now, we Bw that, Q-t Welt Where I= current (A) time (3) 2 = electrochemical equivalent b) —_Faraday’s Second Law of Electrolysis ‘The weight of the material (W) deposited at an electrode is directly proportional to the equivalent weight (B) of the material. Wor 19|MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues In other words, the same quantity of electricity id required to liberate 1-gram equivalent ofits own ‘compound, This quantity of electricity is known as Faraday's constant (F), ESFW Atomic weight(At) And equivalent weight (E)= —Trreneyi) at aw © Combination of Faraday’s First and Second Law of Electrolysis WXQE ‘Where F = 96500 Clmal In terms of Current density, iat “Mass flow rate, W 20[MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues Current Efficiency Current efficiency can be calculated in two ways: ‘Theoreticalamount of electricity ‘Actualamount of elecirielty consumed Current Efficiency: Actualamountof metal deposited ‘Theoreticalamountof metaldeposited (Curent Efficiency (Current efficiency is always less than 100%) Nernst equation Nernst sowed that forthe electrode reaction MY (aq.) + a MOS) ‘The electrode potential at any concentration measured with respect to SHE ean be represented by © orn) = Et) tn [But concentration of solid M is taken as unity. > Eye /m=Et,. fm oo ow sy nF ‘Where R is a gas constant (R) = 8.3.14]K" mol For any gener.al electrochemical reaction Ae BB se dD Nernst equation can be weitten as Eat ‘At equilibrium Ezat = 0 RT = yan, apne (Q=te) “Where Ke = equiibrum constant Sy Fink, WF 0.059 Ifthe reaction is taking place at room temperature E &y= 22 tog K 2A[MT-Metallurgical Thermodynamics www.cavindia.com© Career Avenues 9. Free energy of cell reaction ‘The reversible work done by galvanic cell is equal to decrease in its Gibbs energy and therefore, ifthe emt ofthe cells E and nF is the amount of charge passes and AG,,, isthe Gibbs energy of reaction then, © AG. = FE Ifthe concentration of al the reaction species is unity, then Ent = Ea © AGPan = -RFE%t on -1(nxe) nF AG}, =-RTINK, AG Sy 22[MT-Metallurgical Thermodynamics www.cavindia