UNIT=H ‘ THERMODYNAMIC POTENTIALS & MAXWELL'S EQUATIONS (V), temperature (T) and entropy (S) which are useq known as thermodynamic variables. 1) Quantities like pressure (P), volume ( ic variables used for the complete "a to represent a thermodyramic system are 2) Combinations or fimetions of she thermodynami ' description of a system are known as thermodynamic potentials or th fictions. 3) The fou thermodynamic potentils exe () internal energy (U), (i) Helmholtz function (F), {iti enthalpy (FI) and (iv) Gibb's function (G).. i ; a 4) Thermodyramic functions arc of practical importance in studying the conditions of equilibrium of a system, 5) Thermodynamic potentials arc homogeneaus ie, they all represent the same quantity (energy). As all represent energy, they aré also known as thermodynamic potentials, 6) Thermodynamic variables are heterogeneous ie, each variable represents a different quantity, 7) Helmholtz fisnetion (F)=U - 1S Enihalpy (H}=U + PV and Gibb’s function (G) =U ~ TS + PV 8) Thermodynamic potentials in terns of thermodynamic variables arc av A). ‘nal ene yells Fin According to first law of thermodynamics, dQ=dU +dW=dli +P dv According to second law of thermodynamics, dQ= Ts Therefore, from first and second laws of thermedynamies TdS=dU+P dV or dU=Td3~PdV a) Differentiating eq. (1) with respect to S when V = constant, we get a 7 ly Differentiating this eq. with respect 10 V when $ = constant, we get (a(3) -(F } avas J," lav), ie Differentiating eq, (1) with respect o V when $ = constant, we get c n © AV), Differentiating this eq, with respect to when V = constant, we get GSR (Thermodyui(sz we | (Hl (ml a) Eq, (4) is known as Maxwell's first thermodynamic relation, 8). Helmboltz Function (F) and Maxwell's Second Relation: From cq. (1), dU=Tds-Pay => dU=d(TS)-S dT-PdVv = dU-TS) =-S aT- Pav = dF=-SdT-Pdv (5) ‘where F = U-TS is known as Helmholtz funetion. Differentiating eq. (5) with respect to T when V = constant, we get Differentiating this eq. with respect to V when T = constant, we get (a(#))- (a, ~~ (6) Differentiating eq, (5) with respect to V when T = constant, we get oF =| =-P av), Differestiating this eq. with respect to T when V = constant, we get (a(),)- iar — From, eqs. (6).and [fs wr wi), \ar), (8) Eq. (8) isknown os Maxwell's second thermodynamic relation. C). Entbalpy (H) and Maxwedl’s Third Relation: From eq. (1), au ‘dS -PdV = dU=TdS-d(PV)+ Vv aP => d(U+PV)=Tds+VeP dH=TdS+ VP ald where H = U + PV is known as enthalpy, Differentiating eq. (9) with respect to S when P = constant, we get =T Differemiating this eq. with respect to P when S = constant, we get GSR (Thermodynamics) 13fee I" Differentiating this eq. with respect to $ when (a) -(3), From, eqs. (10) and (11 P-when § = constant, we get P= constant, we get Eq, (12)is known as Maxwel’s third thermodynamic relation. D). Gibb’ id Maxwell's Jn: From €q, (1), dU =TdS-PdV = dU=«(Ts)-SdT-d(PV)+ V dP => d(U-TS+PV)=-SdT+ VdP dG=-SdT+VdP Where G=U ~ TS + PV is known as Gibb’s energy. Differentiating eq, (13) with respect to T when P= constast, we get 3s) =-S Tsp ing this eq, with respect to P when T = constant, we get 2(2] = (3) o\at),), \erh ing eq, (13) with respect to P when T= constant, we get 2G) cy OP Js Differentiating this eq. with respect to T when P= constant, we pet Gals) -Cer From, eqs "ia 15 dnl Eq. (16) is known as Maxwelt's fourth thermodynamic relation Diffferenti Differenti: GSR (The (10) ae (11) (12) a= (13) (14) (4) ase (16)sane ELE eecrertina 78) 1) -Gr- tw), ("Tas =<4Q) 7 (5) (3) (1) But, the amount of heat energy (dQ) required to change the state of unit mass of a substance al constant temperature is known as latent heat (1.). If Vi and Ve are the initial and final volumes of the substance, then (8) fe 0) Applications: 1) Effect of change of pressure oa the boiling poiat: All the liquids expand on boiling. ie, V2> Vi = V2—Viis tve and 2 istve (or) dT +dP i.e,, with the inerease in pressure, the boi i of liquids increases 2) Effect of change of pressure om the melfing point; (a) For the solids which expand on melting like wax and sulphur Va> Vi = V2 - V4 is +0 and igre (od) Tsar i.e, with the increase in pressure, the melting point of solids which expand on melting increases. {b) For the solids which contract on melting like ice: V2< Vi => V2 ~ Vi is -ve and {P igeve (or) aT oe -P aT ie, with the increase in pressure, the melting point of solids which contract on melting, decreases, 3) Regelation of ice: ‘The melting of ice under pressure and its refreezing, when the pressure is re is known as cegelation of ice. If two blocks of ice ave pressed together, their contac a surfaces will melt (pressure lowers the-melting point of icc), When the pressure is remot” the melting point rises back to normal and the water between the wo blocks freezes two blocks form a single piece es)‘Skating on ice is possible due to regelation of ice. Ie melts under skates and forms film of water on which the skater slides. In extremely cold weather, when the weight of te skater is not enough to melt the ice, skating is impossible. RATIO OF SPECIFIC HEATS; 1) The amount of heat energy required to increasc the temperature of one mole of a gas JC at constant pressure is defined as the molar specific heat at constant pressure (Cy) yy 00) _ (Tes a «-(2) -(34), 0 2) The amount of heat energy required to increase the temperature of one mole of a jas by 1°C at constant volume is defined as the molar specific heat at constant volume (C.). ag Tas ae «.-(3) -C), ° 3) The bulk modulus (K) of a substance is defined as ap ap = a Ke eae strain (aviv) av ‘Therefore, the adiabatic bulk modulus, Ks = ~V| aV/s P and the isothermal bulk modulus, Kre -v(), (P72), 5.) 2. tea) Ebel Le) Ber GL) 4) The adiabatic expansion coefficient (7) is defined as | GG) , _ \ar, lav, ‘Submitting Maxwell's relations, we get i (2) my (2) s S)_ \OT Hy 8 jp \AT J, al (* Td8 = dQ) mm), (a), Cand (2) =Cy, the molar specific heats of the gas. 1 eke Se + ai Ka 0 / ‘Thus, the ratio of specific heats of a substance is equal to the ratio adial bulk moduli, GSR| Myce sotent 9 estou reqtrd to focease the lenoperatre of Gs take of gas by aac (2 -(4) ‘The amount of heat energy required to increase the temperature of one mole of a acon whe we or pica one) oe ‘Tas (ee) -(ir, ~o Let us consider that the entropy S be a function of variables V and T, ie., S>fV,T) —(l) a)" (ir), a), Mul nen ‘the equation with T, we get 15) -*(5).-7(5), (i), ~8) From eqs. (1), (2) and (3) we get enerr( i) (3) “0 From Maxwell's second relation, ( av), Substituting in eq. (4), we pet oF av) c-¢, = (2 } Bh —() Fea) aires lee cifterence Gerricen tie specific heats of a gas Fora perfect gas For one mole of an ideal gas, PV = RT Differentiating eq. (6) w.rto T when V is constant, we get (2) aes (2) =k a). at), ¥ Differentiating eq, (6) w.rto T when P is constant, we get Blea A) ae = (oe OT jy Substituting in eq, (5), we get G-y GN — TRE . TER 2g cepy-RD + Cr-CveR for an ideal pasTOULE—KELVIN COEFFICIENT: experimental set up is as shown in the figure. PQ isa thermally insulated cylinder containing porous plug G Noor material such as cotton wool) and is fitted with two nae pistons A and B. The porous plug separates the cylinder in to two [os 208 iy compressed to a high pressure Pt on onc side, The gas then passes through pars Hi | to the other side of low constant pressure Py. When the compressed gas molecules come towards the lower pressure: side afler passing through porous plug, Cede eed hence, suffer a change in temperature. The change in temperature is called as ‘Thomson or Joule-Kelvin effect. iS ERIM! i = "The porovs plug experiment gives the concept of Joule Kelvin, fect 4 The change in the temperature of a gas when il is passed from a region of constant high pressure to a region of lower constant pressure through a porous plug is known ax Joule-Kelvin or Jaul Results of the experiment (1) All gases suffer a change in temperature after passing: through the porous plug. (2) At ordinary temperatures all gases except hydrogen and helium show cooling effect. (3) The change in temperature is direetly proportional to the difference in pressure on the thwo sides of the parous plug, (4) The fall in temperature decreases as the initial temperature of the gas is raised (It becomes zero at a particular temperature which is different for different gases. Above this temperature, instead of cooling, heating is observed. The temperature at which Joule-Kelvin effect changes the sign is called as lemperature of inversion Thus, every gas below its temperature of inversion will cool on passing through porous plug. The inversion temperature of nydrogen is -80 °C. So, if it is pre-cooled to a temperature less than -80 °C and then passed through the porous plug, it suffers cooling.) (5) During Joule Kelvin effect, the enthalpy of the gas is constant Note: (dT/AP) is known as Joule-Kelvin coefficient. Deriv: i of Joule-Kelvin Coefficient: (From Maxveell's Equations) ring Joule-Kelvin effect, the enthalpy of th iS Parte katn ef Ipy of the gas is constant ie., > dH=dU+Pvj=0 ie, dU+PdV+VdP-0 But, according to first law of thermodynamics, dU + P dV = 40 and from second law of thermodynamics, dQeTds Therefore, TdS+¥ dP =0 Let us consider that the entropy S be a function of variables P ai oe es Pand Tie GSR ¢«(8 as dS= (3) er (Fat Substituting in eq, (1), we get cs s = 1 (3) ror) or evar &) . {88 a But, (2) Cr and from Maxwelt's 4" relation, (2) (%) ‘Substituting in the above equation, we get av -1( 8) wes car +VdP=0 Dividing with dP, we get ay m =-=(2) Eq. (2) is the general equation of Joule-Kelvin coefficient, Case (i): For an ideal gas: For one mole of an ideal gas, PV = RT ~--() Differentiating eq, (3) wir.to T when P is constant, we get "G+ (5 Substituting in eq. (2), we get R RT pv wR) -v (Fl-y (B)-y (#) eee fr 4 aP J, on cy CG (Since PV = RT) Conclusi For an ideal gas, Joule: Kelvin coefficient is zero. Case (ii): For a real gas (Van der Waal’s pas): For one mole of a real gas, Van der Waal’s equation is given by (ry where a and b are Van det Waal’s constants. Differeatiating eq, (4) w.r.to T when P ts constant, we get irslalwela From 9, (4), (Ps +) . eS Substituting in the above equation, we gct RT av’ 2a) av} r (See GAG -* ‘Multiplying the above equation with (V-b), we get GSR (Thermodynamics)