98 INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS a —+— as - ht {| 408s Tw | om Lap — wis | | } | 10 S| | oT Ss % Figure 3.17 Generalized density correlation for liquids. (Based on A. L. Lydersen, R. A. Greenkorn, ‘and 0. A. Hougen, Generalized Thermodynamic Properties af Pure Fluids, Unie, Weconsin, Eng, Expt Sta. Rept. 4, 1955.) - (b) The reduced conditions are 100 128 T,=0.764 — P, 0.887 From Fig. 3.17, we have p, ~ 2.38. Substituting this value along with V, into Eq, (3.51) gives Vv. _2s = 23 _ 30.5 cm‘ mol! p 238 In comparison with the experimental value of 28.6.m" mol ', this result is in error by 66 percent If we start with the experimental value of 29.14 em” mol ' for saturated liquid at 310 K, Eq, (3.52) may be used. For the saturated liquid at T, ~ 0.764, we find from Fig. 3.17 that p,, = 2.34. Substitution of known values into Eq. (3.52) gives 2.34) Le 234) 28.65 cm’ mol! 2 con (34) 28.65 r ‘This result is in essential agreement with the experimental value. PROBLEMS 3.1 An incompressible fuid is contained in an insulated cylinder fitted with a frictionless piston. Can fenergy as work be transferred to the fluid? What is the change in internal energy of the Auld when the pressure is increased from P, to P:? Nobuo engausity 32 Express the volume expe its partiat derivatives. For w water be compressed at 50°C 3.3 Five kilograms of liquid fof state at 1 bar during whic land AU’. The following pro, independent of temperature: is 1,590kg m. 34 One mole of an idea! V, = 0.005 m? to P, = 1 bar (a) Constant volume. (b) Constant temperature (e) Adiabatically. ‘Assuming mechanical evers ‘on a single PV diagram 3S An ideal gas, Co=(S/ Py = 1Obar and V;=1m't (2) Isothermal compression (b) Adiabatic compression (e) Adiabatic compression (d) Heating at constant vol (e) Cooling at constant pre Cateutate Q. W. SU" and 8 a single PY diagram. ©1M6 A gid, nonconducting ‘membrane. On one side of other side is a perfect vacu: temperature of the gas? Ho process by which the gas can aan ideal gas for which Cy 3:7 An idea! gas, Cp = (7/: changes in a series of nonfl (a) From an initial state of to ¥7(psia) [600 kPa] (b) tis then cooled 10 104 (o) Finally, the gas is expa Caleulate Q, W, AU, and & Repeat these calcula aan efficiency foreach proce: process. [348 One cubic meter of an as follows (a) By & mechanically reve {b) Hy a mechanically reve (o) By an adiabatic, irre 100 kPa For each case calculate tt 21d mol" K | © 49 A perfectly insulated, piston of high thermal cone and 300K js on one seo (a) What ae the finalODYNAMICS Lrdersen, R.A. Greenkorn, Unie. Wisconsin, Eng. Expt long with V, into Eq. . this result is in error “for saturated liquid = 0.764, we find from (3.52) gives or! rctontess piston. Can nergy of the fluid when ps 99 32 Express the volume expansivty and the isothermal compressibility as functions of density p and its partial derivatives. For water at $O°C and Uae, «= 4418 x 10° bar. To what pressure must ‘be compressed at SO°C to change its density by I percent? Assume that « is independent of P. 33 Five kilograms of liquid carbon tetrachloride undergo a mechanically reversible, isobaric change of state at I bar during which the temperature changes from 0 to 20°C. Determine AV‘, W, Q. H', nd AU" The following properties For liquid casbon tetrachloride at 1 bar and O°C may be assumed independent of temperature: 6 = 1.210 "K ', Cy = 084K ke KY. The density at O"C and I bar is 1.590kEm * 34 One mole of an ideal gas, Cy = (7/2)R and Cy =(5/2)R, expands from Py = 10 bar and V, = 0005 m? to. P, = Lar by each of the Following paths (2) Constant volume {b)“Constant temperature (o) Adiabatically. ‘Assuming mechanical reversibility, calewlate W, Q, AU, and AH for each process. Sketch each path oon a single PV diagram, 35 An ideal gas, Cy ~(5/2)R and Cy ~(3/2)R, is changed from Py = Ubar and Vj = 10m" to P,~ 1Obar and Vi 1m’ by the following mechanically reversible processes: (a) Isothermal compression (b) Adiabatic compression followed by cooling at constant pressure. (c) Adiabatic compression followed by cooling at constant volume. (d) Heating at constant volume Followed by cooling at constant pressure (©) Cooling at constant pressure followed by heating at constant volume. Calculate Q, W, AU and SH for each of these processes, and sketch the paths of all processes on a single PV diagram. 24 A cigid, aonconducting tank with a volume of 4m” is divided into two equal parts by a thin ‘membrane. On ane side of the membrane the tank contains nitrogen gas at Shar and #0°C, and the other side is a perfect vacuum. The membrane ruptures and the gas fills the tank. What is the final temperature of the gis? How much work is done? Is the process reversible? Deserihe a reversible process by which the gas can be returned (ois initial state, How much work is done? Assume nitrogen an ideal gas for which Cy, = (7/2)R and Cy = (5/2)R. [37 Am ideal gas, Cp = (7/2)R and Cy = (5/2)R, undergoes the following mechani changes in a series of nonflow processes: (a) From an initial state of 104(°F) [40°C] andl 21.75(psia) [150 KPa], itis compressed adiabatic to 87(psia) (600 kPal, (B) Its then cooled to 104(F) [40°C] at a constant pressure of ¥7(psia) [600 KPa} {c) Finally the gas is expanded isothermally to its original state Cateulate Q, W, AU, and AH for each of the three processes and for the eyete. Repeat these calculations for exactly the same changes of slate accomplished irreversibly with aan efficiency for each process of 80 percent compared with the corresponding mechanically reversible process 38 One cubic meter of an ideal gas at S00 K and 2,000 kPa expands to ten times its as Follows: (a) By a mechanically reversible, isothermal process. (6) By a mechanically reversible, adiabatic process, (e) By an adiabatic, ireversible process in which expansion is against a restraining pressure of 1W0KP, For each case calculate the final temperature, pressure, and the work done by the gas. C= Smt K *39 A perfectly insulated, rigid cylinder of 0.5-m" volume is divided in half by a weightless, frictionless piston of high thermal conductivity that is initially held in place by latches. An ideal gas at 100 kPa ‘and 300 K is on one side of the piston and the same ideal gas at 900 kPa and 300 K is on the other. (a) What are the final equilibrium temperature and pressure after release of the piston? ly reversible ly100 INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS (b) Suppose a rod attached to the piston extends through an end of the cylinder and acts against 4 constant resisting force equivatent to 100 kPa. What are the final equilibrium T and P upon release of the piston if Cy = (5/2)? 3.40 One pound mole of air, initially at 248("F) [120°C] and &(atm) [8.11 bar], undergoes the following ‘mechanically reversible changes. It expands isothermally to a pressure such that when itis cooled at constant volume to 68(*F) [20°C] its final pressure is 3(atm) [3.04 bar). If ar is assumed an ideal 48 for which Cy = (7/2)R and Cy = (5/2)R, calculate W, Q, AU, and AH. 3.11, An ideal gas is lowing in steady state through a horizontal tube, No heat is added and no shaft work is done. The cross-sectional area of the tube changes with length, and this causes the velocity to change. Derive an equation relating the temperature tothe velocity ofthe gas. Irnitrogen at 140°C flows past one section of the tube at a velocity of 2 ms ', what is its temperature at another section where its velocity is 40.ms~!? Cy = (7/2)R. 3.12 One mole of an ideal gas, initially at 40°C and | bar, is changed to 120°C and 15 bar by three different mechanically reversible processes: (a) The gas is first heated at constant volume until its temperature is 120°C; then it is compressed isothermally unti its pressure is 15 bar. (b) The gas is first heated at constant pressure until its temper isothermally to 15 bar. (©) The gas is first compressed isothermally to 15 bar; then it is heated at constant pressure to 120°C. Calculate Q, W, AU, and AH in each case. Take C= (7/2)R and Cy = (5/2)R. Repeat, with Co = (S/R and Cy = 3/2)R. 3.13 One mole of an ideal gas, initially at 20°C and | bar, undergoes the following mechanically reversible changes. It is compressed isothermally to a point such that when itis heated at constant volume to 100°C its final pressure is 1Obar. Calculate Q, W, AU, and AH for the process. Take Gp = (PDR and Cy = (5/2)R. > 3.14 Figure P3.14 depicts two mechanically reversible processes undergone by | mol of an ideal ga. Curves T, and T,, are isotherms, paths 2-3 and 5.6 are isobars, and paths 3-1 and 6-4 are at constant Volume. Show that W and Q are the same for processes 1-2-3-1 and 45.64 ture is 120°C: then itis compressed Figure P3. oe rere 3.48 A particular quanti reversible steps that toge isothermal to 3 bar. Is sat constant volume t each step of the cycle and 3.16 An existing process (a) One mote of ai at 7 (b) The aie is then heated It is proposed to replace i land 3bar to some final p process equal t0 that of 1 ideal gas with Cy = (7/2) [AT Derive an equation (ofa gas from an initial v where b isa positive cons Derive am equation (of a gas from an initial p ‘expansion (Fg. (3.10)] tr How do these two re {RAB A substance for whic From initia state (Py, Vi) (a) Starting with the where A depends on T ot (b) Determine an © ‘constant substance whe 3.19 An empirical eqatio V for any mechanically « show that the process i isotherms ‘equation, 3.20 For methyl chloride Caleulate the work of me from 1 bar to 60 bar at 12 )DYNAMICS e eylinder and acts against uum T and P upon release undergoes the following : then itis compressed stant pressure to 120°C: =(5/2)R. Repeat, with ‘llowing mechanically itis heated at constant forthe process, Take #1 mot ofan ideal gas. and 6-4 are at constant VOLUMETRIC PROPERTIES OF PURE FLUIDS 101 AS A particular quantity of an ideal gas [Cy = (5/2)R] undergoes the following mechanically reversible steps that together form a eycle, The gas, initially at Har and 300 K, is compressed isotheesally to 3 bar. tis then heated at constant P to a temperature of 990 K. Finally, iti cooled at constant volume to its initial state with the exteaction of 1,300 as heat, Determine Q and W for ‘each step of the cycle and for the complete cycle 3.16 An existing process consists of two steps: (a) One mole of air at T, = 900 K and P, ~ 3 bar is cooled at constant volume to T; ~ 300K. () The air is then heated at constant pressure until its temperature reaches 900 K. Wis proposed to replace this two-step process by a single isothermal expansion of the air From 900 K and 3bat to some final pressure P. What is the value of P that makes the work of the proposed pprovess equal to that of the existing process? Assume mechanical reversibility and treat air as an ideal gas with Cy = (7/2)R and Cy = (5/208 3.I7 Derive an equation for the work of mechanically reversible, isothermal compression of I mol ‘of a gas from an initial volume V, to a final volume V; when the equation of state is PLV~ b= RT where b is @ positive constant Derive an equation for the work of mechanically reversible, isothermal compression of | mol of a gas from an initial pressure P, to a final pressure P, when the equation of state is the virial ‘expansion [Eq. (3.10)] truncated to z-148P How do these two results compare with the corresponding equations for an ideal gs? 3.48 A substance for which « is a constant undergoes an isothermal, mechanically reversible process from initia state (P), V,) to Binal state (P, Vs), where V is molar volume. (a) Starting with the definition of «, show that the path of the process is deseribed by V = Aexp(-xP) where A depends on T only: (b) Determine an exact expression which gives the isotfermal work done on J mol of this constant substance when x aed the initial and final pressures and molar volumes are knows, 3.49 An empirical equation, PV* = const, where V for any mechanically reversible process. Ass show that fl is constant, is sometimes used 0 relate P and wing the validity of this equation for an ideal gas, anf, ey" ~a-alt Ae, 1 the process is isothermal, 8 = 1. Show that this equation reduces in this ease to the isothermal-work equation, we Rrinet oRTinp. “3.20 For methyl chloride at 125°C the virial coeficients are B © = 18,200 em* mot 207.5cm! mol! Calculate the work of mechanically reversible, isothermal compression of | mol of methyl chloride from | bar to 60 bar at 125°C, Base calculations on the Following forms of the virial equation: BG @ Zarb S + RPS oy z102 INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS, ee Why don’t both equations give exactly the same result? 321 Calculate Z and V for methanol vapor at 200°C and 10 bar by the following equations: (a) The truncated virial equation (3.33) with the following experimental values of virial coefficients: 7 B= -219¢m' mot! C= =17,3006m* mol? () The truncated virial equation (3.31), with a value of B from the generalized Pitzer correlation, (c) The Redtich/ Kwong equation, with estimates of a and b from Eqs. (340) and (3.41). 322 Calculate Z and V for ethane at 50°C and 12 bar by the following equations: (a) The truncated virial equation (3.33) with the following experimental values of virial coeficients: B= 156.7 em! mol! C = 9,650.em* mol? (6) The truncated viria! equation (3.31), with a value of # from the generalized Pitzer correlation, (©) The Redlich/ Kwong equation, with estimates of a and b from Eqs. (340) and (3.41), +323 Calculate Z and V for sulfur hexafluoride at 100°C and 15 bar by the following equations: (a) The truncated virial equation (3.33) with the following experimental values of virial coefficients: B=-1634em' mol —C 120 em mol: (0) The truncated virial equation (3.31), with a value of B from the generalized Pitzer correlation. (e) The Rediich/Kwong equation, with estimates of « and from Eqs. (3.40) and (3-48) For sulfur hexafluoride, T= 318K, P, = 37.6bar, V. = 19% cm? mol "and w 0.286 324 Determine Z and V for steam at 250°C and 2,000 kPa by the following (a) The truncated virial equation (3.33) with the fol wing experimental values of virial coefficients: B= -152Sem! mol! C= —5,8000.m* mol? () The truncated virial equation (3.31), with a value of B from the generalized Pitzer correlation (6) The steam tables, 325 Caleulate the molar volume of saturated liquid and the molar volume of saturated vapor by the Redlich/ Kwong equation for one of the following and compare results with values found by suitable generalized correlations (a) Propane at 40°C where P* ~ 13.71 bar (b) Propane at 50°C where P= = 17.16 bar (e) Propane at 60°C where P™ = 21.22 bar (a) Propane at 70°C where Po = 28.94 bar (e) m-Butane at 100°C where P™ ~ 15.41 bar (A) mButane at 110°C where P= 18.66 bar. (@) m-Butane at 120°C where P™* = 22.38 bar (h) m-Butane at 130°C where P™ ~ 26.59 bar i) Isobutane at 90°C where P™ = 16.54 bar G) Isobutane at 100°C where P* = 20.03 bar {(K) Isobutane at 110°C where P™ = 24: bas. (0) tsobutane at 120°C where P* = 28.53 bar. (m) Chlorine at 60°C where P= = 18.21 bar (2) Chlorine at 70°C where P= = 22.49 hae (0) Chlorine at 80°C where P™ = 27.43 bar. (P) Chlorine at 90°C where P™ = 33.08 bar (q) Sulfur dioxide at 80°C where P™ = 18.6 bar. (2) Sulfur dioxide at 90°C where P™ = 23.31 bar. (6) Sutfar dioxide at 100°C where P™ = 28.74 bar. (1) Sulfur dioxide at 110°C where P*" = 35.01 bar. 3.26 Calculate the fllowi (a) The volume occupied (6) The mass of ethane ca 3.27 To a good approxima 900(psia) [6,206 kPa}? Ho 3.28 A04-m" vessel is use that at a temperature of: fof the vessel. For these cor ‘AL 320K the vapor press 3.29 A 1,000-()?[2832-m its vapor at 77(°F) (25°C) “The vapor pressure of w-b 3.30 Calculate the mass o 2,000(psia) [13,790 kPa} TE 10(Tb,) (4.58 kg] of does it exert pressure of 331 To what pressure doc 3.32 10 1 kg of water in a 3.33 A0.3-m' vessel holds is developed? 3.34 What is the pressure 3.35 A sigid vessel, fed (195.8°C), is allowed to nitrogen at its normal boil 3.36 The specific volume o volume at 400 K and 60 ba 337 The density of liquid ‘and 100 bar. 3.38 Estimate the density 3.39 Estimate the volume pressure of ammonia is 85 340 PVT data may be ish 1M is introduced into ath equilibrate, and the tempe (a) Approximately w sand P) ifthe maximus al (b) Approximately » maximum allowable erori that Z ~ 0.9 and that valu SAI For a gas described b than T., develop expressc “The expressions should co Note that in the limit as F 342 One mole of an idea reversible process. how tMODYNAMICS, ve following equations: al values of virial coefficients: o ‘eneralized Pitzer correlation, 540) and (40). 2 equations: 1 alues of virial coeficients Pp -neralzed Pitzer correlation. = 8.40) and (3.41) the following equations: | values of viral coefficients: eralized Pitzer correlation, (3.40) and G41). and w = 0286, wing values of viral eoeficients: reralzed Pitzer correlation. ve of saturated vapor by the ith values found by suitable VOLUMETRIC PROPERTIES OF PURE FLUIDS 103 326 Calculate the following: (a) The volume occupied by 20 kg of ethane at SOC and 30 bar () The mass of ethane contained in & 0.3-m" cylinder at 60°C and 130 ar 327 To.a good approximation, what is the molar volume of ethanol vapor at 900(°F) [482.22°C] and '900{ sia} [6,206 kPa}? How does this result compare with the ideal-gas value? 328 A.0-4-u1" vessel is used (0 store liquid propane at its vapor pressure. Safety considerations dictate that at a temperature of 320 K the liquid must occupy no more than 75 percent of the total volume fof the vessel, For these conditions, determine the mass of vapor and the mass of liquid in the vessel ‘AL 320K the vapor pressure of propane is 16.0 bar. 3.29 A 1,000-(f)'[28.32-m"] tank contains 500(ft)? [14.16 m’] of liquid n-butane in equilibsium with its vapor at 77(°F) [25°C]. Determine a good estimate of the mass of n-butane vapor in the tank, ‘The vapor pressure of n-butaae at the given temperature is 2.40(atm) {2.49 bar} 3.30 Caiculate the mass of ethane contained in a 0.5.(f2) [0.0142-m?] vessel at 140(*F) [60°C] and 2,000(psia) [13,790 kPa} IF 10{1b,) [4.54 kg] of ethane is contained in a 0.5-(F1)"[0.0142-m'] vessel, at what temperature does it exert a pressure of 3,000(psia 331 To what pressure docs one fill 0.1-m’ vessel at 25°C in order to store 25 ke of ethylene init? 3.22 IF 1 kg of water in a 0.03-m1° container is heated to 451°C what pressure is developed? 333 A.G.3-m* vessel holds ethane vapor at 18°C and 2,500 kPa. If it is heated to 200°C, what pressure is developed? 3.44 What isthe pressure in 4 0.45-m’ vessel when itis charged with 8 kg of earbon dioxide at 40°C? 35 A rigid vessel, filled to one-half its volume with liquid nitrogen at its normal boiling point (195°C), is allowed to warm to 25°C. What pressure is developed? The molar volume of liquid nitrogen at its normal boiling point is 34.7 em’ mol . 336 The specific volume of isobutane liquid 4 300 K and 4 bar is 1.824 em" g'. Estimate the specific volume at 400 K and 60 bar 3.37 The density of liquid »-pentane is 0.630 g.cm™* at 18°C and | bar. Estimate its density at 150°C ‘and 100 bar, 3.38 Estimate the density of liquid ethanol at 190°C and 190 bar. 3.39 Estimate the volume change of vaporization for ammonia at 20°C. At this temperature the vapor pressure of ammonia is 857 kPa. 340 PVT data may be taken by the following procedure. A mass m of a substance of molar mass M is introduced into a thermostated vessel of known total volume V". The system is allowed to equilibrate, and the temperature T and pressure P are measured (a) Approximately what percentage errors are allowable in the measured variables (m, M, V', T, and P) if the maximum allowable error in the calculated compressibility factor Z is +1 percent? (b) Approximately what percentage errors are allowable in the measured variables if the ‘maximum allowable error in caleulated values of the second virial coeficient Bis +I percent? Assume that Z~ 09 and that values of # are calculated by Eq. (3.32) 341 For a gas described by the Redlich/ Kwong equation (Eq, (3.35)] and for a temperature greater than T,, develop expressions for the two limiting slopes, ‘The expressions should contain the temperature T and the Redlich/ Kwong parameters « and/or b [Note that in the limit as P > 0, V= cn, and that in the limit as P= 0, V= & 3.42 One mole of an ideal gas with constant heat capacities undergoes an arbitrary mechanically reversible process. Show that104 INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS 343 The PVT behavior of a certain gas is described by the eat Pv») where b is a constant. If in addition Cy is constant, show that (a) Uis a function of T only. (b) y= const (c) For a mechanically reversible adiabatic process, P(V~ b)” = const, ion of state T 344 A certain pas is described by the equation of state wonre(of)p m Here, b is a constant and 0 is a function of T only. For this gas, determine expressions for the isothermal compressibility « and the thermal pressure coefficient (@P/aT )y. These expressions should contain only T, P, 6, d8/dT, and constants 3.45 Methane gas is stored in a O.1-m! tank at 1,500 kPa and 25°C. Gas is allowed to flow from the tank through a partially opened valve into a gas holder where the pressure is constant at 115 kPa When the pressure in the tank has dropped to 750 kPa, calculate (a) ‘The mass of methane in the gas holderif the process takes place slowly enough that the temperature (b) The mass of methane in the gas holder and its temperature Ifthe process occurs so rapidly that heat transfer is negligible, ie. there is no heat transfer either between parts of the system oF between the system and the surroundings Ce) Woutd the answers to part (b) be di ‘Assume that methane is an ideal gas for which y= 1.3 ent if the pressure in the gas holder were 3004Pa? Heat transfer Consider, for by the oxidat alycol. The « temperatures and air, are t of the preheat with oxygen temperature. does not rise of CO,, anv amount of he associated w to glycol by result of the | between the from the wa resulting int All of tl chemical ma characterize: transition, 2 experimenta apply therm