THERMODYNAMICS Lecture Notes for B.Tech 1% YearEntropy Entropy is a measure of degree of disorder or randomness in a system. Entropy is also considered as a measure of unavailable form of energy. When a system goes from a more orderly to less orderly state, randomness increases and hence entropy of the system increases. e.g. when a solid changes to liquid there is an increase in entropy and when solidifaction occurs, entropy decreases. In general Entropy of Universe Increases Mathematical expression for entropy The change in entropy of a system (AS) is equal to the ratio of heat change (q) to the temperature (T) of the reversible cyclic process.Concept of Entropy Two main concept of entropy are (i) entropy is a measure of disorder of the system (ii) entropy is a measure of probability In a cyclic process heat cannot be completely converted into work and the efficiency of work engine is never hundred percent. When heat is absorbed by a gas, the kinetic energy of the gas molecules get increased and they will move faster. During this process the gas molecules may (i) collide with each other (ii) collide with the walls of the container collide with the face of the piston and the piston is pushed Of these collisions, only (iii) will bring about the expansion of the gas. (i) and (ii) will not bring any effective expansion of the gas. Thus some fraction of heat is wasted for the random motion of the gas molecule. This randomness is correlated with unavailable work. The extent of randomness or the unavailable work is indicated by the entropy of the system.Derivation Of Entropy From Carnot Cycle or Mathematical Treatment Of Entropy Concept =0 1 Tz Thus when the isothermal and adiabatic processes in a Carnot cycle are carried out infinitesimally slowly (i.e. reversibly), the summation of Uy is zero. The efficiency of Carnot’s engine may be denoted a aye Consider a cyclic process in which the change from the state A to state B and back to the state A is carried out reversibly. The path ABA may comprise of a number of Carnot cycles (ie, a series of isothermal and adiabatic changes). Hy _ For each Carnot cycle 7, + Tt 0 Pressure —> di Volume ——> When the changes are infinitesimal, xt =0 For series of Carnot cycle, xf =0Carnot cycle is performed in two steps viz., from A to Band then back from B to A, JEL (pach 1) +f) 2 ath 1) = 0 pi T ea 24 (math [) = Summation of all the 24 terms when the system changes from A toB along the path | [4 (pach 11) =summation of all the a terms when the system changes from B to A along the path II Sf 2epath 1D = = f° path 11) or ff 2 path 1D = +f (path) Both these integrals are independent of the path but depends only upon the value of some function at A (initial state) and the same function at B (final state) of the system. This function is called entropy (S). 6 _¢. = B44 — Sais the entropy in the initial state A AS = Sp—-Sa= Sa T ‘Sy is the entropy in the final state B For infinitesimally small change i q For finite change at constant temperature AS = —2%ENTROPY CHANGE IN AN ISOTHERMAL EXPANSION OF AN IDEAL GAS According to first law of thermodynamics, AU = q-w In isothermal expansion of an ideal gas carried out reversibly, there is no change in internal energy ie. AU = 0. “Trev —W = 0 or Trev = W or Grev = PdV Work done in the expansion of n moles of a gas from volume V, to V, at constant temperature Tis given by = i nRT In= V4 “drop = NRT In2 YY or AS = 2.303n Rlog @ 1 V3 tev = nR InZ = 4ENTROPY CHANGE IN A REVERSIBLE PROCESS ISOTHERMAL REVERSIBLE PROCESS If the system absorbs q amount of heat from the surroundings atc =f temperature T, the increase in entropy of the system is given by system ~ Entropy of the surrounding decreases, because the surroundings lose the same amount of heat q AS surroundings > Net change in the entropy is given by AStgeqy = ASsystem + ASsurroundings = (Bee ina reversible isothermal process, there is no net change in entropy ASrotq, = 0 ADIABATIC REVERSIBLE PROCESS In an adiabatic process, the system does not take or transfer the heat from the surroundings, i.e. q =0 AStorai = 0ENTROPY CHANGE IN AN IRREVERSIBLE PROCESS Consider a system maintained at a higher temperature T, and its surrounding at lower temperature T,. If q amount of heat passes irreversibly from the system (7,) to the surroundings (T,), Decrease in entropy of the system ASsy stem = > 1 : +4 Increase in entropy of the surroundings AS,, surroundings = |, 2 Net change in the entropy is given by Seta = AS system + ASvurraunaings MSrorat = H+ = alee] = Se total Ty q TyTs Since, T, > T,, (T,-T,) is positive. ASon = positive AStotai > 0 In an irreversible process, the entropy of the system increases. Since all spontaneous process are natural and irreversible process, the entropy of the system always increases.ENTROPY CHANGE IN PHYSICAL TRANSFORMATIONS or ENTROPY OF PHASE TRANSITION Transition from solid phase to liquid phase Consider a case when a solid changes into liquid state at its fusion point. The process requires absorption of heat (heat of fusion). Consider melting of 1 mole of a substance reversibly at the fusion point 7; at constant pressure, The entropy change of the process, AS, will be given by AH AS, = —L where AH;is the molar heat of fusion. Ts Transition from liquid phase to vapour phase Suppose 1 mole of a substance changes from liquid to vapour state reversibly at its boiling point T,, under constant pressure. The entropy change of the process, AS, will be given by AH, AS, = coal where AH, is molar heat of vaporization b The process of fusion and vaporization are both accompanied by increase of entropy because AH, and AH, are positive In the case of change of phase from vapour to liquid or from liquid to solid, then both AH,, and AH, will be negative and hence the process of condensation of vapour or freezing of a liquid is accompanied by decrease of entropy.Introduction to WORK AND FREE ENERGY FUNCTION We learnt from the second law of thermodynamics that the following equation AStotat = ASsystem + ASsurrounaings serves asa criteria of spontaneity or feasibility of a process. ASrorai > 0 B (i.e. total entropy change is positive), then the process is feasible. AStotat =0 > The system remains in a state of equilibrium The difficulty in finding out the change in entropy of the surroundings every time, leads to the introduction of two new thermodynamic functions which can be determined more conveniently. 1. Work function (or) Helmholtz work function (or) Helmholtz free energy (A) 2. Free energy function (or) Gibbs free energy (G)WORK FUNCTION A part of internal energy of a system can be used at constant temperature to do some useful work. The part of internal energy (U), which is isothermally available is called work function (A) of the system. It is mathematically defined as A=U-TS GIBBS FREE ENERGY A part of total energy of a system is converted into work and the rest is unavailable. The part of energy which is converted into useful work is called available energy. The isothermally available energy present in a system is called free energy (G). It is mathematically defined as Available energy (6) = Total energy (H) - unavailable energy (TS) G=H-TSSIGNIFICANCE OF THE WORK FUNCTION (A) The work function is given by 4=U-TS For small change in a reversible system at constant temperature Ad = AU —TAS But change in Entropy AS = nee = TAS = drev & AA=AU~drey From the equation of first law of thermodynamics AU=q+w map “AU ~drev Wrev Work done by the system is negative ~ Wrev = AU ~drev DA = — Wren Since the process is carried out reversibly, the work done is maximum # MA = —Wnax or —AA = Winax The decrease of work function (—AA) of a process at constant temperature gives a maximum work obtained from the system.SIGNIFICANCE OF THE GIBBS FREE ENERGY (G) Gibbs free energy is the total available energy present in a reversible system at constant temperature and pressure as useful work. G=H-TS For small change in a reversible system at constant temperature AG = AH — TAS enthalpy change (MH) isgiven by AH = AU + PAV AG = AU + PAV —TAS But, AA=AU-TAS and: AG=AA+ PAV Since —AA = Wax, AG = —Wyax + PAV PAV is work done by expansion Ww, is maximum work obtained from the system ad ¥ The decrease of free energy of a Winax — PAV = network or useful work process at constant temperature and pressure gives a useful work Hence, —AG = Wusefui obtainable from the system.MAXWELL RELATIONS OR THERMODYNAMIC RELATIONS The various expressions connecting internal energy (U), enthalpy (H), Helmholtz free energy (A), and Gibbs free energy (G), with relevant parameters such as pressure, temperature, volume and entropy are (i) dU = Tds — PdV (ii) dH =Tds +VdP (iii) dA = —SdT — PdV (iv) dG = —SdT + VdP Derivation for equation (ii) Derivation for equation (iii) H=U+PV A=U-—TS dH = dU + PdV +VdP dA = dU —TdS — SaT dH = (q — PdV) + PdV + VdP dA = dU — dq —SdT dH =q+VdP dA = —PdV — SdT dH = TdS + VdP From these expressions, the Maxwell relations are obtainedIf Vis constant, dV = 0, then eqn. (i) becomes ‘dU (),=7 If S is constant, dS = 0, then eqn. (i) becomes avy __ (>), =-P Differentiating eqn. (1) w.r.to Vat constant S, scar = (57) asav \av)s Differentiating eqn. (2) w.r.to $ at constant V, ue -(¥) avas— \asJy from eqn. (3) and (4) Following the same mathematical procedure on eqn (ii), (iii) and (iv) other expressions are derivedConsider eqn. (ii), dH =Tds + VdP If Pis constant, dP = 0, then eqn. (ii) becomes (55), =? If S is constant, dS = 0, then eqn. (ii) becomes (B.=" Differentiating eqn. (6) w.r.to P at constant $ san = (Ss) asap \ap/s Differentiating eqn. (7) w.r-to S at constant P was = (Ss) apas \as/p from eqn. (8) and (9)Consider eqn. (iii), dA = —-SdT — PdV If Vis constant, dV =0, then eqn. (iii) becomes oa (2) =-3 st If Tis constant, dT = 0, then eqn. (ii) becomes aA =). =-P ..(12) Differentiating eqn. (11) w.r.to V at constant T aa 2) orav avs yp Differentiating eqn. (12) w.r.to T at constant V a (2) avar— \ar/y from eqn. (13) and (14) (15)Consider eqn. (iv), dG = —SaT +VdP If P is constant, dP = 0, then eqn. (iv) becomes aG @= 5 If S is constant, aT = 0, then eqn. (iV) becomes ‘aG (), =v Differentiating eqn. (16) w.r.to P at constant T aa as orep @), Differentiating eqn. (17) w.r.to T at constant P 6 av apor (F, from eqn. (18) and (1! ++e(18) The equations (5), (10), (15) and (20) are known as Maxwell relationGIBBS - HELMHOLTZ EQUATION (or) Relation Between AG and AH Consider the relation for Gibbs Free Energy, G =H —TS (1) ButEnthalpy, H =U+ PV Therefore, G=U+PV—TS For infinitesimal change dG = dU + PdV + VdaP — TdS — SaT (2) first law of thermodynamics dU = dq — PaV second law of thermodynamics dq = TdS Therefore, dU =TdS — PdV (3) Substituting eqn. (3) in(2) dG = = ys - poy +pdv +VdP -Tds — SaT Therefore, dG = VdP — SdT (4) At constant pressure, dP =0, and (4) becomes dG = —SdT (5)@,-5 Substituting (6) in (1) G =H +7 (22) 5 This is one form of Gibb’s — Helmholtz equation For any two state of system the equation may be written as dG, = —S,dT (Initial state) dG, = —S,dT (final state) The change in the system is given as dG, — dG, = —S,dT — (-S,dT ) (Gz — Gy) = —(S2 — Si)dT dAG = -ASdT (8) CIN At constant pressure, (8) becomes (HP), =-as (9)But AG=AH—TAS or —AS= =~ (10) Substituting (10) in (9) Ge, = sete or AG —AH = (ee). Therefore, jag =AH4T (%) P This is another form of Gibb's — Helmholtz equation. It is applicable to all process occurring at constant pressure. For a reaction at constant volume, the corresponding equation will be AA=AU+T S,Application of Gibb’s —- Helmholtz equation Calculation of enthalpy change for the cell reaction (galvanic cell) If a cell yields nF Columbus of electricity in a reversible manner, it must equal to the decrease in the free energy, then -AG = nFE? (a) Where n =no. of electrons involved in the process F = Faraday = 96,500 coulombs E’ = Energy in volts Gibb’s — Helmholtz equation Substituting, -AG = nFE? AG =AH+T (=), —nFE° = AH +T CC), —nFE? = AH —nFT &), AW = =nFE? +nFT (2) (2) AH = —nF [E° -T &),] (3)Application of Gibb’s — Helmholtz equation (cont..) Calculation of EMF of the cell Diving eqn. (2) by nF AH _ _ po ae® nF Eo +T ( ar ), 0 = AH ‘an? (4) era -t4T(Z), Calculation of entropy change AH and AS are related by eqn. AG = AH — TAS (5) But, AG = nFE® and AH can be calculated from eqn. (3). Using these values AS can be calculated from eqn. (5) Gibb's — Helmholtz equation is applicable to all process occurring at constant pressure. It is used to calculate AH from values of free energy change at two different temperature.Van’t Hoff Isotherm Van't Hoff isotherm gives a quantitative relation for the free energy change accompanying a chemical reaction. Derivation Consider a general reaction aA+bB = mM+nN We know that Gibbs Free Energy, G=H~TS (1) But Enthalpy, H =U +PV Therefore, G=U+PV—TS For infinitesimal change dG = dU + PdV +VdP —TdS — SdT (2) first law of thermodynamics dU = dq — PdV second law of thermodynamics dq = TdS Therefore, dU = TdS — PdV (3) Substituting eqn. (3)in (2) dG = =¥s — pay + Pav + vaP bs sat Therefore, dG =VdP — SdT (4)At constant temperature, (dG); = VdP For 1 mole of ideal gas, PV = RT free energy change for 1 mole of any gas at constant temperature is given by ap aG = RT (“) (5) Integrating (5) / dG = RT IF = P G=G°+RTInP (6) where G®is integration constant called standard free energy change Let the free energies of A, B, M and N at their respective pressure Pg, Pg, Py and Py are Gy, Gg, Gy and G,, respectively. Then the free energy change for the above reaction is given by AG = [MGy + NGy] -— [aG, + bGp] (7) Substituting values of Gy, Gg, Gy and Gy from eqn. (6) into eqn. (7} AG = [(MG?y + MRTINPy) + (NG? y + NRTINPy)] — [(AG%4 + ARTINP,) + (bG"y + DRTINPs)]Py |™yp,7 AG = [(mG°y + nG°y) — (aG°4 + DG’ s)] +rrint wu)" Pr) Pal" (Pal? Pal [Py]" AG = AG? + ern ee (8) At equilibrium AG = 0, and therefore 0 = AG? +RTIn ameel,, a. 0 = AG? + ATINK gg where Keq = Tera lg! AG? = -RTInK yg (9) Substituting (9) in (8) AG = -RTINKeg + arin Ea Or (Pvl™[Pn I" AG = RT InKeg — RTIN This expression is called Van’t Hoff isothermVan’t Hoff Isochore or Van’t Hoff equation or Variation of equilibrium constant with temperature The effect of temperature on equilibrium constant is quantitatively given by Van’t Hoff equation. It can be derived by combaining Van’t Hoff isotherm and Gibbs-Helmholtz equation Van’t Hoff isotherm AG? = -RT IN Keg (1) Differentiating (1) w.r.to temperature at constant pressure BAG?) _ pp @ankp) = Rink, — RT SP (2) Where Kis equilibrium constant at constant pressure a ance) _ 2 d(nKp) 3} Multiplying (2)byT 7 (242 ) = -RT Ink, — RT? S22) (3) Substituting (1) in (3) (2) = AG° — RT? Soaked (4) ar /p aTGibb’s — Helmholtz equation for substances in their standard state oe yo gn (006? (5) age = ane +7 (SE) Substituting (5) in (4) aaGey _ oO 20G°) _ pz alnKp) r(2e ), = ae +7 (Ze ), RT? oe 206°) _ (286°) _ nyo = _ pp dnXp) rTP), (), OS Rr — yo = _ pre alin kp) AH? = —RT? SCke) AH? = RT? SQ) (6) ar (7) or This equation (7) is known as Van’t Hoff’s equation.Enthalpy change does not vary appreciably with change in partial pressure of reactants or products, So the Van’t Hoff’s equation may be written as H ar (8) A d(InKp) =z (In kp) = Bre Integration (8) between 7, and T; at which equilibrium constant are K? and K? and AH is constant KB AH (TdT (9) d(InKp)=—] => I, POOR Jy T? AH Ink —InK3 =a 2 AHT1 1 Ink} — Inks =FlE-z K} 4H [T,; AH {T,-T, P 2 2 yo 2 log = | (10) logk? — log = sso3R| ay, | Ki 2.303R 7,7, Other derivation by integrating (7 o) AH? pat lerivation by integrating (7) J aan) = [e i i a AH? Where C is constant of integration InKp = RT +C AH? lok =— F037 * ©Significance of Van’t Hoff equation . Equilibrium constant (K) and 4H of a reaction can be calculated using Van’t Hoff equation. . A plot of log Kp versus : will give a straight line with slope = a and from the slope the value of AH® can be calculated. (AH° = —2.303 RX slope). . If T2>T1, then | is positive. Kj > Kp, if AH is a positive quantity. i.e. for an endothermic reaction the equilibrium constant increases with temperature. . The magnitude of equilibrium constant also depends on whether partial pressures, molar concentration or mole fraction are used. . Two or more equilibria can be combine in order to get a new equilibrium |. The magnitude cf the equilibrium constant depends on how the reaction is written.Clapeyron-Clausius Equation Clapeyron-Clausius Equation is an equation of fundamental importance which finds extensive application in one component, two-phase systems was derived by Clapeyron and independently by Clausius from the second law of thermodynamics. The two-phases in equilibrium may be (1) Solid and Liquid, i.e. Solid = Liquid, at the melting point of the solid (2) Liquid and Vapour, i.e. Liquid = Vapour, at the boiling point of the liquid (3) Solid and Vapour, i.e. Solid = Vapour, at the sublimation temperature of the solid (4) One crystalline form to another crystalline form, e.g. Rhombic sulphur = Monoclinic sulphur, at the transition temperature of the two allotropic forms Consider the change of a pure substance from phase A to phase B in equilibrium with it at a given temperature and pressure. G, = free energy per mole of substance in initial phase A G,= free energy per mole of substance in final phase B, at equilibrium , G, = Gy there is no free energy change AG = G,- G,=0If the temperature of the system is raised from Tto T+ dT, In order to maintain equilibrium, the pressure has to increase from P to P+ dP free energy per mole of substance in phase A at new temperature (T + dT), and pressure (P+ dP) free energy per mole of substance in phase B at new temperature (T+ dT), and pressure (P+ dP) Since the two phases are still in equilibrium We know that Gibbs Free Energy, But Enthalpy, Therefore, For infinitesimal change According to first and second thermodynamics Therefore, Substituting eqn. (3) in (2) Therefore, = GytdG, = G,+dGz Gy + dG, = Gz + dG, (1) G=H-TS H=U+PV G=U+PV-TS dG = dU + PdV + VdP —-TdS —SdT (2) law of dU =dq-PdV dq =Tds dU =TdsS — PdV (3) dG =Tds — Pav + Pav + VdP —Tds ~ SdT dG = VdP —SdT (4)Substituting eqn. (4) fordG, dG, = V4dP — S,dT (5) Substituting eqn. (4) fordG, dGg = VzdP — SpdT (6) Since Gy = Ge, dG, = dGp (7) Substituting eqn. (5) and (6) in (7) VadP —S,dT =V,dP —S,dT VadP —VgdP = S,dT — SgdT dP( Va — Vp) = aT (Sa — Sp) Where V, is molar volume of pure substance in phase A and V, is molar volume of pure substance in phase B dP _ Sa-Sp (8) a Va-VB dP _ =(Sp-Sa) aT -Wp-Va) dP _ Sp-Sa aT Va-Va (9)V3—V,= change in volume when one mole of the substance passes from the initial phase A to final phase B, represented as AV 5;—5,= change in entropy when one mole of the substance passes from the initial phase A to final phase B, represented as AS dP _ As (10) aT AV ap Since, AS =f a aw (11) a__ 4 (12) aT T(Vg—Va) This is Clapeyron-Clausius equationConsider water in two phases in equilibrium with each other at temperature T Water (Liquid) = Water(Vapour) Then, q= molar heat of vaporization, AHv Vuquia 'S volume of one mole of water in liquid state Vyepour is volume of one mole of water in Vapor state \epour ap Hy &) a T(Vpapour—Vtiquia) For Water (Ice, Solid) = Water(Liquid) aP AH (14) aT — T(Viiquid-V solid) Where, AH,is enthalpy or molar heat of fusion of iceIntegrated form of Clapeyron-Clausius equation for (Liquid) = (Gas) equilibrium For (Liquid) = (Gas) equilibrium, Clapeyron-Clausius equation (13) can be integrated ap Any T(Vgas—V tiquid) V, ar Jyas is considerably greater than the Viiquia Thus (Vyas — Viiquia) can be taken as Vyas dp AHy Therefore, the above equation reduces to aT TVgas For 1 mole of ideal gas, PV= RT, therefore, gas = RT/P aP _ Atty P_ Pty ar T RT RT? dP _ Aty | aT Po RT? d(nP) _ AHy aT RT?Integrated form of Clapeyron-Clausius equation for (Liquid) = (Gas) equilibrium Assuming that AHv remains constant over a small range of temperature, fdQnP) = sss = (16) InP =" (-2)+¢ inp =~“ (2) 4¢ (17) ber =e +e 0 Where Cand C’ are integration constants AH, From (18) a plot of log P against 1/T yield a straight line with a slope = — — and intercept =C’ 2.303 RIntegrated form of Clapeyron-Clausius equation for (Liquid) = (Gas) equilibrium Integrating (16) between certain limits of pressure P, and P, corresponding to temperature T, and T, fp dn P) =e nS (19) P, Inpe= = Hl. Ings Fle-a fe ohh) PB RIT tog = ate P, 2303Rl Te | (20)Thermodynamics of Open Systems: Concept Of Chemical Potential In a closed system, the composition remains constant. However, in open system, the composition of the system changes by adding or taking out substances or by chemical reaction. In such cases, the state of system involves P, Tand composition of the system. Let T and P be the temperature and pressure respectively of a system. Let ny, Mz, N3,......4n, be the respective number of moles of the constituents, 1,2,3.. Then, G must be a function of T, P, ny, My, MyyvemeM; Le. G=fUT, Py my My gy) where n,+ nj+ ny ‘n, = total number of moles = N For small change in temperature, pressure and number of moles of the components, the change in free energy dG will be given by dG = (2), aT + (@., dP + (#) dn, + (*) dn TP M2, TP my. M3 Rj dG dG + (=) dn; ... at (=) dn; A TP ny Mgenaty BY) 5b na tigis called partial molal free energy (G) dny or often called as chemical potential (j1,) of the component i. This term was first introduced by Gibbs an? WTP my Marly Substituting chemical potential terms, AP + yydny + pydrg ++ sydry TN Where jty, [1y,.--,44 are chemical potentials of the components 1, 2,....,j respectively If temperature and pressure remain constant, then (dG) rp = pdr + dng + + day If the system has definite composition having n,, ny, 3, 3....0.j. respectively then on integration n; moles of constituents 1, 2, @rpn = tym + Myre bet pny For total of one mole of pure substance G = 1 ie. free energy is identical with chemical potentialGibbs-Duhem equation We know that the free energy of a homogeneous system, at constant temperature and pressure is equal to the sum of the product of chemical potential and the number of mole of each component. G@)rpw = yma F blyng Hoe + yyy The free energy of the system can change either by the change of chemical potential of component or its number of moles in the system. In order to get a general express for the change in G at a given T and P, differentiating the above equation dG = wydny + mydyy, + phydmy + radu, ++ sydny + nyc, dG = (uid + uydng + syd) + (mydu + radu, ++ yd The first term on the right hand side is equal to dG at constant (dGdre = wad + Hydra +o + tydry temperature and pressure. i.e.Gibbs-Duhem equation Therefore, at constant temperature and pressure for a system of definite composition nydu, + radu, ++ njdyy = 0 nya, =0 Da This equation is known as Gibbs-Duhem equation. For system having only two components (e.g. binary solution) the above equation reduced to ndu, + modu, =0 ng 2a, mh du Thus, variation in chemical potential of one component affects the other component