| OEE ENO p(T. ° AHS73K — AH ogy = ACp(373 ~ 298) AH33k =-33.68 KJ mot! SECOND LAW OF THERMODYNAMICS Statement: Entropy of the universe (system + Surrounding) increases for irreversible process whereas it remains constant for reversible process, Entropy: The disorder is the manifestation of another thermodynamic property called entropy and is represented by the symbol (S). Obviously. entropy, like any other thermodynamic property such as internal energy (U) and enthalpy (H) should be a state function. The entropy change, AS is given by the equation AS = Sev e . Here, q,,. is the heat absorbed when the process is carried ouf reversibly and isothermally|(i.e., at constant T). The AS defined independent of path, as it is a state function. ‘Thermodynamics & Thermochemistry | 93INT-JAM/ M.Sc. Entrance Physical Significance of Entropy: ys ig! disorder of the system : Spontancous process are Accomp, Hh as increase in the disorder of the system. ity (W): All spontaneous process lead 10 incregg It appears that there isa close relation hey. (i) Entropy as ameasure of the by increase in entropy as We! (ii) Entropy as a measure of probabil entropy and also to increase in disorder entropy and the probability This relationship was expressed by Boltzmann [S=k in W] where k is Boltzmann constant =k ln W = k In (arrangement) Ny = kN, In (arrangement) S=R In (arrangement) Carnot Cycle / Carnot reversible heat engine : ‘The carnot cycle is a hypothetical, ideal & reversible cyclic process, devised bya french engines: Sadi Carnot (1824), to demonstrate the maximum convertibility of heat into work, Aa dea machine to demonsirate this cycle is called carnot heat engine, is maximum because the various steps involved are reversible & ‘The work done in a camot cyc! the reversible work is the maximum possible work which a system can do. Carnot heat engine is imaginary & regarded as standard (ideal) by which the performance of = actual heat engine is compared Heat source (T,) a w CH Sink 3) Process (4): Isothermal reversible expansion: PHP t+dP Wines a) | | L : _} = 8 dour = % Sau ‘Adiabatis rreverite Siem (q=0) | hn =O dey 29) 48, ASuu Note: For free expansion Entropy change in a few typical cases: Case 1: Entropy change for any Bas a h “(5 vehv at +—|| 50 By Ist equation of state nv I oer wv T ‘Thermodynamics & Thermochemistry |»UT-JAM/ M.Sc. Entrance I -1(2) ary tert, ] av tlath (tT lath Le op, (& fds = ecars (2) av fi Ie ¥ a), Let Cy be independent of temperature. hb (e Cy In 2+ ] av| at Nar vy J ropy change for an ideal gas (PV = aRT): oP Entropy change for any gas.) ad Sub Case: From above equation Lz Vy b R — ny In + rR In 2 nC p In + oR In as omni Ror 4S ving hy “This is the expression when both the volume and temperature or pressure and temperature ot an ideal gas are changed. (a) For an isothermal process, the change is given by the relation h & = "Rin nk In AS Y, "P (b) For the change of temperature at constant volume ts = acy In AS V 7 (c) For the change of temperature at constant pressure qt = nCp In AS P 7, ‘Sub-case : Entropy change for a van der Waal gas sen, in (2 =nb) AS = nC, In +R wn| Sam (a) When it expands isothermally only.\DEMY (b) When V is constant : CHEM ACA (VY, =nb) = (V, ~ nb [ssa eens Case 2: Entropy change ina reversine phase transformation Since the reversible phase transformation takes place at constant equilibrium temperature then entropy. (where q,,. isthe heat involved in the phase transformation) iy Examples solid > liquid AS tHy My liquid —— sotia s- 1 Entropy change in an reversible phase transition, A> B& thes nCp In B + niin A Vy A acy tn so in M2 v A N Mv Forinstance: The phase transformation of one mole of quid ‘water at -10°C (T, )to solid water 10°C can be calculated following the paths given below : Tiquid Hid iad —> sl (i) tiguid —> liquid Cy =75.312JK™! mol we we (ip Niquid = solid AH,,, = 6088.2 J mot! we re * (iy solid —> solid Cy, = 36401 IK mol! vc nrc Then changes of entropy can be calculated (liquid —> tiquia WC.1a0 rein 2.309 IK mot! Thermodynainics & Thermochemistry | 101i MTIAM / M.Sc. Entrance =Alt, _ 6088.2 i solid = Ay. =608 21.996 JK mat! ©) tn om? | AE ary (ii) (ey ite a8 = ney tn 2 ~ 46,401 2.303 log 458K mot! ry SE then, the change of the entropy of the process H,0(0 atm, 263K) —+ HO (1 atm, 263.) seit sane AS = AS, + AS) + AS, = 2.709 21.996 ~ 1.358 = -26,063 JK! mot! Case 3: Entropy change when two solids at different temperatures are brought together Let one at higher temperature T,, and other ut fower temperature T.. When tWo bodies 4. brought together then Heat lost = heat gain i.e. Heat lost by hot body = Heat gained by cold body (by conservation law) T+, CAT, -D= C.-T) Or T= —* (irthe two bodies are similar) Entropy changes of two bodies are bodies are ro ,» r ~ | far=c, in AS, 4,7 th 5.0 gmice at 273 K is added to 30 gm of water at 323 K in a thermally insulated contains: Mlusteation: What is the final temperature ? M,,, of ce at 273 K = 334.72 J gm G, of water = 4.184 JK-! gm! Mig oF water at 373 K = 2.259 J gn! Solutio Heat require to convert 5 gm of ice at 273 K to $ gm water at 273 K = G 8) * (334.72 J gm!) = 1673.65 Final temperature after mixing Heat gained by ice = Heat lost by hot water 102 | Thermodynamics & Thermochemistry(5 gm) 334.72) em!) +5 8) (4.184 -l CHEM ACADEM | 1) 23 K-T) Perr tKct 7 YOT~ 273K) =(30 g) (4.184 1K! gr T 73.6) + 20.923 | —— = 1673.6.) +2092 it 2}=sszu[ss Solving for T, we get T= 304.43 K ase 4: Entropy of mixing Entropy of mixing is defined asthe difference hetwe , sum of the entropy of the separate gases, cach at a er of the mixture of gas and the For amole of an ideal gas, ad 5= Cy eR dS V T v . dt (dv = fe, Ss eX jo foto fet S-CylnTHRInV +S, From above defination Thus MS pq =D (Cy INT Rin P~ Rin. x4 Sy) Le, in P~ Rin P+ Sy) ninx= = Ry inj +m Inxy +. Ryn, Ing, where n, and n, are number of moles and mole fraction of each constituent of the mixture. Mustration: Calculate the entropy of mixing of one mole of nitrogen gas and three moles of hydrogen ‘gas, assuming that no chemical reaction occurs. i. mixing is ideal Li 33 Soluion ‘The mole fraction are ota 4&7 6 form equation AS. Ryn In x, = R(m [nx + my In 3) +B mol) In ! = -8314 JK"! mol! [v odin 18.70 JK" THIRD LAW OF THERMODYNAMICS Statement : At absolute zero, the entropy of a perfect crystal is ero, ie $<0aT=0K But H,, D,, CO, NO, N,O & H,O posses certain amount of entropy even at absolute zero. This ‘s called residual entropy. ‘The cause of residual entropy is the confinement ‘of molecules in the degenerate lowest energy. level at 0°K in case of certain substance, i. crystalls at O°K are not perfect in true sense in such. ‘substances. “Thermodynamics & Thermchenstry | 103