Advanced Thermodynamics

Lecture 7

S.S.Mallick Department of Mechanical Engineering Thapar University, Patiala

MST marks distribution: 4 numerical x 4 marks each: 16 marks 4 theory questions - (3+3+3+5): 14 marks Total: 30 marks

(1) Refrigerant-134a is to be compressed from 0.14 MPa and 10C to 0.8 MPa and 50C steadily by a compressor. Taking the environment conditions to be 20C and 95 kPa, determine the exergy change of the refrigerant during this process/the minimum work input that needs to be supplied to the compressor per unit mass of the refrigerant. At inlet: h = 246.36 kJ/kg; s = 0.9724 kJ/kgK At exit: h = 286.69 kJ/kg; s = 0.9802 kJ/kgK

(2) Steam enters an adiabatic turbine steadily at

3 MPa and 400C and leaves at 50 kPa and 100C. Determine the exergy change in this process and compare that with that in an ideal expansion (isentropic)

Properties of Ideal and Real Gases and Mixtures

pV = nRuT (or pV = RT) is valid for ideal gas only Ideal gas: molecules are spaced are far apart so that behavior a molecule is not influenced by the presence of other molecules i.e there is no attractive or repulsive force acting between molecules also we assume that the molecules are point masses (i.e. they do not occupy any space) but these assumptions are not strictly valid for gases (day-to-day engineering) real gases Real gases pV = ZRT {Z: compressibility factor)

Under some conditions real gas can be considered behaving as ideal gas.... No intermolecular forces and gas molecules do not occupy any space Very low densityhigh temperature Molecules are too far apart K.E. effect>> intermolecular force effect Real gases: (p+a/V2)(v-b) = RTone of the earliest equation of state a attractive forces b finite volume of molecule

Daltons law of additive pressures: The pressure of a gas mixture is equal to the sum of the pressures each gas would exert if it existed alone at the mixture temperature and volume Pm = Pi (at Tm, Vm).Pi : partial pressure Amagats law of additive volumes: The volume of a gas mixture is equal to the sum of the volumes each gas would occupy if it existed alone at the mixture temperature and pressure Vm = Vi (at Tm, Pm) .Vi : partial volume Daltons and Amagats law hold exactly for ideal gas mixtures but only approximately for real gas mixtures effect of intermolecular forces for real gases (especially at high density)

Daltons and Amagats law hold exactly for ideal gas mixtures but only approximately for real gas mixtures effect of intermolecular forces for real gases (especially at high density) For an ideal-gas mixture, the mole fraction, the pressure fraction, and the volume fraction of a component are identical

Compressibility factor For ideal gas: PV/RT = 1 For real gas: PV/RT 1 For real gas: PV/RT = Z. Z: compressibility factor The more Z is away from 1 ideal to real Z varies with P and T

Ideal gas line: Z =1 For 35, 50, 60 K lines, Z first decreases & then increases with increase in pressure For 100, 200, 300 K lines Z increases continuously with increase in pressure Explain the shape of curves why U (or V) shapes for the lower temp curves??

Fig: Z for hydrogen

What happens with increase in p??

Compression decrease in volume results in increase in pressure 1) Molecules come closer to each other (increases mutual attraction) Molecules striking on the wall, are being somewhat pulled back by the attractive forces of other molecules Also molecules lose their individual energy by collision etc

Fig: Z for hydrogen

Result: pressure of real gas < ideal gas i.e. had it been ideal gas, its pressure would have been higher than that of real gas To accommodate this, a/V2 is added to P PV/RT = Z = 1(ideal gas) (P + a/V2)V/RT = Z1 Z1> Z. Z increases as p increases 2) Compression: larger no. of molecules per unit volume Hence molecular volumes can not be ignored anymore Net free volume: V b; i.e P (V-b)/RT = Z2 Z2< Z. Z decreases as p increases

Shape of the curve (Z value ) is a balance between Z1 and Z2 e.g. for the 35K line, up to 20 bar Z2 effect predominates over Z1 and then Z1 takes over .but WHY?? .and WHY the 100/200/300K lines do not have U shapes??.. i.e. the temperature effect

There are charts for other gases also and the charts are qualitatively similar By suitably modifying the co-ordinates, it is possible to coincide the different charts into one Transformation: Reduced pressure for pressure = p/pc Reduced temperature for temperature = T/Tc {pc and Tc are critical pressure and temperatures respectively}

Mixture of ideal gases Basic assumption is that the gases in the mixture do not interact with each other. Consider a mixture with components {i: 1,2,3}... with masses m1, m2, m3 ...mi and with N1, N2, N3 ...Ni number of moles. The total mixture occupies a volume V, has a total pressure P and temperature T (which is also the temperature of each of the components) Total mass: m = mi N = Ni

Mass fraction of i: i = mi/m.i = 1; Yi = 1 Mole fraction of i: Yi = Ni/N The mass and number of moles of species i are related by: mi = NiMi Molar mass of the mixture: M = m/N = Ni Mi/N or M = (Ni/N) Mi or M = YiMi

Dalton 's Law of partial pressure Total pressure of an ideal gas mixture is equal to the sum of the partial pressures of the constituent components P = Pi P is the total pressure of the mixture; Pi is the partial pressure of component i is pressure of the species if it existed alone in the given temperature T and volume V Pi = NiRuT/VRu: universal gas constant Pressure fraction: mole fraction

Amagat's Law: Volume of an ideal gas mixture is equal to the sum of the partial volumes V = total volume of the mixture Vi = partial volume of the species i = volume of the species if it existed alone in the given temperature T and pressure P Volume fraction = Mole fraction

Thermodynamic properties of mixtures Internal energy: U = miui Enthalpy: H = mihi Entropy: S = misi Specific internal energy of the mixture: u = U/M = miui/M

Gas mixture (i.e. having different comp) can be described: mass basis mole basis mm = mi; Nm = Ni.. m: mass, N: mole Mass fraction of ith gas mfi = mi/mm; hence mfi = 1 Mole fraction of ith gas yi = Ni/Nm; hence yi = 1 Molar mass of ith gas: Mi = mi/Ni Apparent (or average) molar mass: Mm = mm/Nm Mm = mm/Nm = mi/Nm = Nimi/Nm = yiMi mfi/yi = Mi/Mm

Daltons law of additive pressures: The pressure of a gas mixture is equal to the sum of the pressures each gas would exert if it existed alone at the mixture temperature and volume Pm = Pi (at Tm, Vm).Pi : partial pressure Amagats law of additive volumes: The volume of a gas mixture is equal to the sum of the volumes each gas would occupy if it existed alone at the mixture temperature and pressure Vm = Vi (at Tm, Pm) .Vi : partial volume Daltons and Amagats law hold exactly for ideal gas mixtures but only approximately for real gas mixtures effect of intermolecular forces for real gases (especially at high density)

Daltons and Amagats law hold exactly for ideal gas mixtures but only approximately for real gas mixtures effect of intermolecular forces for real gases (especially at high density) For an ideal-gas mixture, the mole fraction, the pressure fraction, and the volume fraction of a component are identical

Compressibility factor For ideal gas: PV/RT = 1 For real gas: PV/RT 1 For real gas: PV/RT = Z. Z: compressibility factor The more Z is away from 1 ideal to real Z varies with P and T

Ideal gas line: Z =1 For 35, 50, 60 K lines, Z first decreases & then increases with increase in pressure For 100, 200, 300 K lines Z increases continuously with increase in pressure Explain the shape of curves why U (or V) shapes for the lower temp curves??

Fig: Z for hydrogen

What happens with increase in p??

Compression decrease in volume results in increase in pressure 1) Molecules come closer to each other (increases mutual attraction) Molecules striking on the wall, are being somewhat pulled back by the attractive forces of other molecules Also molecules lose their individual energy by collision etc

Fig: Z for hydrogen

Result: pressure of real gas < ideal gas i.e. had it been ideal gas, its pressure would have been higher than that of real gas To accommodate this, a/V2 is added to P PV/RT = Z = 1(ideal gas) (P + a/V2)V/RT = Z1 Z1> Z. Z increases as p increases 2) Compression: larger no. of molecules per unit volume Hence molecular volumes can not be ignored anymore Net free volume: V b; i.e P (V-b)/RT = Z2 Z2< Z. Z decreases as p increases

Shape of the curve (Z value ) is a balance between Z1 and Z2 e.g. for the 35K line, up to 20 bar Z2 effect predominates over Z1 and then Z1 takes over .but WHY?? .and WHY the 100/200/300K lines do not have U shapes??.. i.e. the temperature effect

There are charts for other gases also and the charts are qualitatively similar By suitably modifying the co-ordinates, it is possible to coincide the different charts into one Transformation: Reduced pressure for pressure = p/pc Reduced temperature for temperature = T/Tc {pc and Tc are critical pressure and temperatures respectively}

Some thermodynamic properties of ideal gas Ideal gas: specific heats are constants..whereas for real gases they vary appreciably with change in temperature (and little with pressure) Tds = du + pdv; or, ds = du/T + pdv/T (1) Assumption: internal energy (u) is a function of T and v, i.e. u = f (T, v) (2) hence, du = (u/T)v dT + (u/v)Tdv (3) From (1) and (3), ds = 1/T(u/T)v dT + 1/T{(u/v)T+p} dv (4) Another assumption: s = f (T, v) (5) hence, ds = (s/T)v dT + (s/v)Tdv (6) Comparing (4) and (6), (s/T)v = 1/T(u/T)v (7) and (s/v)T = 1/T{(u/v)T+p} (8)

Differentiating (7) w.r.t v when T is constant, 2s/Tv = 1/T 2u/Tv (9) Differentiating (8) w.r.t T when v is constant, 2s/vT = 1/T 2u/vT + 1/T(p/T)v - 1/T2(u/v)T - p/T2 (10) From equation (9) and (10)some terms cancel out: (u/v)T + p = T(p/T)v (11) For ideal gas, pv = RT, or (p/T)v = R/v = p/T (12) From (11) and (12), (u/v)T = 0 (13) i.e. u does not change with change in v at constant temp in isothermal process, u remains constant Similarly considering u = f (T,p), you would get (u/v)T=0 (14) i.e. u does not change with change in p at constant temp Corollary from (13) and (14) u = f(T) (15) only for ideal gas, for real gas Z terms comes into play (Z is a function of p)

u = f(T) Joules law (u does not change unless T changes) Considering u = f (T, v) (16) du = (u/T)v dT + (u/v)T dv (17) Since (u/v)T = 0 (Joules law) and (u/T)v = cv Hence, du/dT = cv (18) valid only for ideal gas Since cv is constant for an ideal gas (ideal gas consideration), u is a linear function of T (remember: ideal gas only) h = u + pv (19) (for any gasideal/real) h = u + RT (20) (for ideal only) u is already a function T, so h = f(T) (21) For ideal gas only, dh = du + RdT (22) or dh/dT = du/dT + R (23) By definition dh/dT = cp (ideal gas only) and du/dT = cv, so cp = cv + R; or, cp cv = R (24)

cp/cv = (25); cv = R(-1) (26); cp = R/(-1) (27) Units of specific heats??? kJ/kg K General property relations: Tds = du + pdv (28) Tds = dh vdp (29) ds = du/T + p/T dv (30) ds = cv dT/T + R dv/v (31) Integrating (31) between states 1 and 2, s2-s1 = cv ln(T2/T1) + R ln(v2/v1) (32) From (29), ds = dh/T v/Tdp (33) ds = cp dT/T - R dp/p (34) After integrating, s2-s1 = cp ln(T2/T1) - R ln(p2/p1) (35) From (32) and (35), s2-s1 = cp ln(v2/v1) + cv ln(p2/p1) (36)

Change in internal energy in adiabatic, reversible process: Tds = du + pdv; for reversible, adiabatic process ds = 0, hence du = - pdv (48); Integrating (48) between states 1 and 2 and using pv = RT u2-u1 = {RT1/(-1)} {(p2/p1)(-1)/ -1} (49) exercise: derive (49) Enthalpy change in adiabatic, reversible process: Tds = dh vdp; for reversible, adiabatic process ds = 0, hence dh = - vdp (50); Integrating (50) between states 1 and 2 and using pv = RT h2-h1 = {RT1/(-1)} {(p2/p1)(-1)/ -1} (51) Enthalpy change is manifested as work output = h1 h2 exercise: derive (51)

Reversible isothermal process Integrating dw = pdv between states 1 and 2, W = v1v2pdv = v1v2RT dv/v = RT lnV2/V1 (52) Polytropic process pvn = c (c: constant) Not an adiabatic process (both work transfer and heat transfer are happening together) .but the process can be reversible in adiabatic process is a property of the gas, but n is not Exponent n defines the process; n: from experimental data T2/T1 = (p2/p1)(n-1)/n (53)

Change in internal energy in a polytropic process: u2 u1 = {p1v1/(-1)} {(p2/p1)(n-1)/n -1)} (54) exercise: derive (54) Change in entropy in a polytropic process: s2 s1 = (n )/{n(-1)} R ln(p2/p1) (55) exercise: derive (55) 12pdv = p1v1/(n-1)[1-(p2/p1){(n-1)/n}] (56) exercise: derive (56) -12vdp = np1v1/(n-1)[1-(p2/p1){(n-1)/n}] (57) exercise: derive (57)

Tds = du + pdv Reversible heat transfer between 1 and 2: 12 Tds = 12 du + 12 pdv = [( - n)/{(n-1)(-1)}] R (T1 T2) (57) = cv {( - n)/{(1 - n)} T (58) T = (T1 T2) = cn T (59) cn = ( - n)/(1 - n) is called polytropic specific heat exercise: derive (58 and 59) cn = (-1+1-n)/(1 - n) = {( - 1)/(1 - n)} + 1 Therefore, higher n higher polytropic specific heat

Generalised compressibility chart is applicable for both ideal and real gases Generalised compressibility chart shows: 1) At very low pressures (PR <<1), gases behave as ideal gas regardless of temperature. 2) At high temperatures (TR >2), ideal-gas behavior can be assumed with good accuracy regardless of pressure (except when PR >> 1). 3) The deviation of a gas from ideal-gas behavior is greatest in the vicinity of the critical point.

The deviation of a gas from ideal-gas behavior is greatest in the vicinity of the critical point.

Equations of state Attempt to define the real gas behavior Many modelsof which three are: 1. Van der Wasls equation (one of the earliestbut perception is it is not very accurate) 2. Beattie-Bridgeman equation (better accuracy than Van der Waals) 3. Benedict-Webb-Rubin equation (more recent and very accurate)

Van der Wasls equation (1873): (P + a/v2)(v b) = RT; v: specific volume: V/m a/v2: accounts for the intermolecular forces b: total volume occupied (consumed) by the gas molecules Intended to improve ideal gas equation Include in model: i) Intermolecular attraction forces ii) Volume occupied by the molecules themselves

Boundary conditions at critical point: (p/v)T=Tcr= 0 (2p/v2)T=Tcr= 0 Using these conditions, the values of a and b are found as: a = 27R2Tcr2/(64Pcr) b = RTcr/(8Pcr)

It is reported that Van der Walls model is not very accurate

Beattie-Bridgeman equation of state (1928) P = (RuT/vmolar2){1 c/(vmolarT3)}(vmolar + B) A/vmolar2 vmolar = V/N .N: number of moles A = A0 (1 a/vmolar) B = B0 (1 b/vmolar) The model is based on experimental determination of A0, B0, a, b, c

Benedict-Web-Rubin equation of state (1940) P = (RuT/vmolar) + (B0RuT A0 C0/T2)/vmolar2 + (bRuT a)/ vmolar3 + a/vmolar6 + {c/ (vmolar3 T2)}(1+/vmolar2) e-/vmolar2 Known to be reasonably accurate for densities up to 2.5cr

Comparison of the three models

Virial equation of state Equation of state of a substance can be expressed in series: P = RT/v + a(T)/v2 + b(T)/v3 + c(T)/v4 + d(T)/v5.. This and similar equations are called virial equations of state Coefficients a(T), b(T), c(T)that are functions of T (only) are called virial coefficients The coefficients can be determined experimentally or theoretically from statistical mechanics