Paper-IL Chapter- TS-equation, Maxwell's equation ‘Theorem: Condition of exact differential: Let 2=2(n,y) az az s= (2) a2) 0 dz = Mdx + Ndy Where M :) dr and N= (&) dy Now y y aM Pz Te Hence, Q. Derive Maxwell's equations (i) Helmholtz free energy: Helmboltz free energy or Helmholtz function is defined as F TS For a pure substance undergoing an infinitesimal reversible process dF = dU —Td8 — Sav 8 TdS = dU + PdV, So, we can write dF = —Pdv — As F is exact differentiable type z = Mdx + Ndy, so we get (a), --@r), 1oP\ _ (as aT), \WV), This is Maxwell's Ist equation. This relation can be written as as\ _ (aP wv), \aT), From this relation we see that for any thermodynamic system, the increase of entropy per unit increase of volume at constant temperature is equal to the increase of pressure per unit increase of temperature in an isochoric (V =constant) process, (ii) Maxwell’s 2nd relation: Gibbs’ free energy: Gibbs’ free energy is defined as G=U-TS+PV For an infinitesimal reversible process dG= U —TdS — SaT + PdV +VdP As TdS = U + Pav dG = —SdT + VaP As G is exact differentiable, so we get -Ge),- (er), ‘This is known as Maxwell’s 2nd relation. This relation can be written as (-m),-(=r), From this relation we see that the decrease of entropy per unit increase of pressure at isothermal process is equal to the inerease of volume per unit increase of temperature at isobaric (P = constant) process. (ii) Maxwell’s 3rd relation Internal energy: We have from first law of thermodynamics dQ= dU +dVv 2TdS = dU + PdV dU =TdS — PdV (s),--(=5), ‘This is Maxwell's 3rd relation. This relation says that the increase of temperature per As U is exact differentiable, unit increase in volume in a reversible adiabatic (isentropic, S' =constant) process is equal to the decrease of pressure per unit inecase in entropy in an isochoric(V=constant) process, (iv) Maxwell’s 4th relation: We have enthalpy H= 14 PV dH = dU + PdV + VaP dH =dQ+VdP dH =TdS + VdP (=), - (3s), ‘This is Maxwell's dth relation. This relation says that the increase of temperature per s H is an exact differentiable, unit increase of pressure in a reversible adiabatic process (isentropic, § = constant) is equal to the increase of volume per unit increase of entropy in an isobaric proce: ‘Theorem IL If f = f(.yz) (=), (a),),Proof: Let y=ulf,2) oy oy GB) Putting the value of y in eq(1), we get «-(5) «+ ),G «-(G),-),6 Comparing (3) and (4), we get coefficient of df is ae) _ ((ae) (ae) (ay (3). ((@),* &),@)) Oz\ _ (dx) (ay oe, : oy, f ae f az\ (ac\ (ay (2e), (5), (62), 4 and that of dz 2‘Theorem! If x = 2(y, z) and z = 2(y,z), then (=), (2),(),-> Proof: Let Putting the value of dz in eq(1), we get 8) @@)+-@) (3) @))G) (Ge (3) «-((5).-( From (3) we get coefficient of dr Coefficient of dyQ. Prove that. Proof: Let ,_ (av a2V a (35) e+ (F ) ar qa) Let T=T(P,V) (a) .,, (a) 5, ar (5) a + (7), (2) Putting the value of dT in eq(1), we get ar), (a) ,, (ae), 2” (ar), #”) w=), From (3) we get coefficient of dr (3), Jae + (=r), (ar 8)Coefficient of dP Q. Derive T-dS equations First Td equation Lot entropy S$ is a function of T and V. ic. S(L,V) a: 3 is = (2 as (28) ar+( w Multiplying both sides by T, we get Tas a)As specific heat at constant volume Cy = (3) Tds =€ wat; From Maxwell’s first equatin we get ‘as\ _ (aP WV), \aT), TdS = CyaT + (=) So, we get from (2) This is known as first TdS equation. nd TAS eqn Let entropy $i As specific heat at constant pressure Cp = () P a: TdS =CpaT +T P dS = CpdT + (4 8 @) @) ay () (2)From Maxwell’s second equation we get as av OP), \OT pat —1(2”) ap Spal (3), This is known as second TS equation. So, we get from (2) Tas ‘Third Ta (3) a) Q) (2)We have first TdS equation oP TdS = CydT +T| — | dV 1 ° (ir), o and second TdS equation av Tas = Cpat -T(<) ap 2) ‘dS = Crd ( ar), 2) From (1) and (2) we get (3) T=T(P,V) (0 i Comparing (3) and (4), we get coefficient of dP @ 7(% ar *(#), OP), (Cp—GvCoefficient of dV, we also get Again we have (6) From (5) and (6) w Case-1: Here (#) = =-Ve. Hence Pp Cp > Cy Case-2: When T = 0 i.e. at absolute temperature Cp—Cy =0 C= =0. eg, Water at 4°C, density maximum, Cy =0 ulCp = Cy Case-4: For perfect gas PV =RT PdV +VdP = Ral (Ov. , (FF, R a R or), P PdV +VdP =0 (B),--8 When P = constant So we get Cased: or Prove that Cp — Cy = “°V. We have volume expansion coefficient =i (& 'vV\ar],, av oT), 1 (av Ke~ (3), 12 wW and volume compressibilitySo we get av\* (oP. ~cv=-1(3) (3) oT) ,\oV), 1 Cp — Cy = -TYV? x = p — Cy xe Ty Cp- Cv = In terms of linear expansion coefficient a = 2, we get Tee C6 eV Q. Prove that (#) ~ aie (34) s P We have first Td equation wage ,(2P\ Tas = CydT (3) a eo) For isentropic process ($ = constant, dS = 0) aP\ vd + (sr) p(OP\ ny Cyal = -1 (FF), ov), “ Again we haveDividing (1) t Q. Prove that (#) s We have second T'S equation Tas cyar -1() dP a) P For isentropic process (= constant, dS = 0) ), a) 2) Again we have Dividing (1) by (2) we getQ. State and explain Joule’s law For an ideal gas, the internal energy does not change with volume and pressure when temperature remains constant. i.e. and Hence internal energy (U) does not change unless temperature (7) changes. So, U T) only for an ideal gas. This is known as Joule’s law. Explaination: The properties of a substance are related by TdS = dU + PdV ds = P IU + dV 1) rt T ( Let the internal energy (U) is a function of T and V. ice. Sub: z((#) an (),”) + fw Bye Again, we consider (4)Comparing (3) and (4), we get coefficient of aT ),- (er) © =(2 6 vy \T), coefficient of dV 1 i +p\= 6 i((rr),+")-( ® Now differentiating (5) wat. V when T 1 7) Tr (7) Differentiating (6) wt. T when V = constant, 1/ PU : oP’ 1 (8 T\aTov \aT),) T? 8) From (7) and (8) we get (9) For alll ideal gas Putting this value in (9) we getSo, internal energy U does not change when volume V changes at constant tempera- ture. Similarly, if we take U=U(T,P) then we get (10) For alll ideal gas Putting this value in (9) we get au (5),-° So the internal energy does not change when P changes at constant temperature. Hence, u=u(r) Phase transition: ‘There are three types of states of a substance. eg. (i) Solid 7