Chemical Engineering Thermodynamics -1 2.23 First Law of Thermodynamics ‘The work done in a reversible adiabatic process is v2 w= fey v2 w= cf Heel" av v2 Copy” = v Sol", _ apy = mI vv] = a solvit'-vi"'] [as-1+1 = -@-b) we pailev"-cve"] -» (2.85) pv'=c C= PV! and C= PV! Thus, substituting for C, Equation (2.85) becomes Uppy. ye! Voy wes —P.v¥- v3] PV. — we = (2.86) We have, PV, = = RT; ... foran ideal gas. ‘Therefore, Equation (2.86) becomes = (2. WwW ya h-T) +» (2.87) POLYTROPIC PROCESS This a general process without specific conditions other than mechanical reversibility. All other processes are special cases of this general process. The law of this proc PV® = Constant, PV" = C where C and n are constants, and n is called the polytropic index The process which follows the path described by Equation (2.88) is called the polytropic process.Chemical Engineering Thermodynamics - | 2.24 First Law of Thermodynamics Special cases of a polytropic process for an ideal gas by assigning different values to n : Ina polytropic process : (i) When n = 0, PV° = C,ie., P = constant, the process reduces to a constant pressure process (an isobaric process). (ii) When n = 1, PV! = C, PV = constant, i.e.,T = constant (since PV = RT and if T = constant, PV = constant since R is a constant), the process reduces to a constant temperature procs an isothermal process. ii) When n = ©, PV = constant or PV = constant, i.e.,V = constant, the process reduces to a constant volume process - an isochoric proce: (iv) When n = y, PV" =C, the process reduces to an adiabatic process (an isentropic process). illustrated on a P-V diagram in Fig. 2.10. Fig. 2.10 : P-V diagram of various polytropic processes State Ito State A; Constant pressure cooling (n = 0) State | to State A’; — Constant pressure heating (n = 0) State 1 to StateB : — Isothermal compression (n = 1) State 1 to State B' : Isothermal expansion (n = 1) State 1 to StateC : Adiabatic compression (n = ) State 1 to State’: Adiabatic expansion (n = y) State 1 to StateD =: Constant volume heating (n= ©) State 1 to State D' : — Constant volume cooling (n = ©)Chemical Engineering Thermodynamics -| 2.25 First Law of Thermodynamics which are applicable to an ideal ga Thus, for | mole of an ideal gas a non-flow process are undergoing a reversible The general equations applicable to a polytropie process. polytropic process, we have dU = dQ-dW or AU=Q-W Pav or W = fPdVv CdT or AU = f Cyd dw " dU dH =CpdT or AH = f CpdT “The work done during a reversible polytropic process by 1 mole of an ideal gas is given by PV, -P2V2 W="n-1 .- (2.89) The work done during a reversible process is given by w w+ (2.90) The law of polytropic proc pyn . Pp (2.91) Substituting P from Equation (2.91) into Equation (2.90) gives w-faav=c ie ‘i Integrating gives, We ‘ ~} [vi""'- * —n+1 Me sat Cc mel, y-nel Cc nel weet ]=a a] _ pn w= aeiiey" cv" ] (2.92) We have pyvn =C te C = PV) and C = With these C values, Equation e 92) becomes w= O[pvt- vit! pvt vi") We . (2.93) We have, PV, =Chemical Engineering Thermodynamics -| 226 First Law of Thermodynamics Replacing P,V, and PV, from Equation (2.93) gives R(,-T) = (2.94) Equation (2.93) or (2.94) gives the work done by 1 mole of an ideal gas in a reversible polytropic process. Let us eliminate V, from Equation (2.93), as it is usually not known. _.. Equation (2.93) Pya = C and P,V2 = C PW) = P, *! un = ®) Vv, eu (2.95) ting for V> from Equation (2.95) in Equation (2.93), we get P,V, =P, (P,/P3)!™ Vi n-1 we bw npn v, ~ n-1 _ PV, — pn t/a pi" v ~ n-1 _ ya Pe mn. pit (PvP) Vi ~ n-l ... second term is multiplied by P,/P, ‘Taking P,V, common from the terms of the numerator on the R.H.S. gives .- (2.96)Chemical Engineering Thermodynamics | 227 First Law of Thermodynamics. Equation (2.96) can be used to calculate the work done in a reversible, non-flow, polytropic process. We have, P,V, = RT,. Therefore, Equation (2.96) becomes RT, P,)\(n-n/n 5 w= 5-1|!-|p, wa (2.97) ‘The change in internal energy for 1 mole of an ideal gas during a reversible polytropic process is given by dU = CydT_... valid for an ideal gas for any process If Cy is taken as constant, integration of the above equation yields AU = Cy(T:-T) -.- (2.98) G We have, a = Wy- Gy = Substituting for C,, Equation (2.98) becomes R au = 527 - (2.99) HEAT TRANSFER DURING A REVERSIBLE POLYTROPIC PROCESS We have, AU = Q-W 5 Q=AU+W (2.100) Substituting the values of AU from Equation (2.99) and of W from Equation (2.94) into Equation (2.100), we get This can be rewritten as 1 Rt-T9| 47-77 Q-)-(m-1 nen-ty [Se1 First Law of odynamics in! R(T, -T2) or Q= (ea)xw. [since we Rot) we (2.101) o- (=) x[ Work done in a reversible ] en y= 1) * Lnon-flow polytropic process FIRST LAW OF THERMODYNAMICS FOR STEADY-STATE FLOW PROCESS (OPEN SYSTEM) In the chemical process industry, we come across a variety of process equipments such as columns, etc. as well as machines such as pumps, reactors, absorption towers, distillation Compressors, etc. through Which there is a continuous flow of material in and out, Such processes are called flow processes and such devices operate as open systems ‘A process in which material continuously flows in and out of is called as a flow process. Most of the devices we come across are operated unde! which are invariant with time. A steady-state flow process is one in which the constant with time, ie., invariant with time. A steady-state flow process must s system through its boundary 1 steady-state conditions - conditions conditions at all points in the apparatus are isfy the flow into the apparatus is always equal to the rate of mass flow out of stem), so that the quantity of material within the apparatus is constant, ial in the apparatus over the the apparatus (sy i.e. there is no accumulation or depletion of the materi period of the time considered. (ii) The conditions such as temperature, pressure and composition of streams flowing at any point within the apparatus are constant. (iii) The rates of heat transfer and work transfer across the boundary of the system are constant with time. Thus, a heat exchanger operates in steady-state flow if the flow rates, compositions, temperatures, etc. of all entering as well as leaving streams are constant. Consider a steady-state flow system as shown in Fig. 2.11. Section 2 Heat exchanger ' ' ' 1 ' ' ' ' Turbine 1 1 ' L T 1 Fig, 2.11 : Steady-state flow process