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CHAPTER 4 PROPERTIES OF WORKING FLUIDS 4.1 Introduction 4.2 Burned and Unburned Mixture Composition 4.3 Gas Property Relationships 4.4 A Simple Analytic Ideal Gas Model 4.5 Relation Between Unburned and Burned Mixture Charts 4.6 Exhaust Gas Composition 1 4.1 Introduction The study of engine operation through an analysis of processes inside engine requires models for compositions and working fluids inside the engine, as well as, models for individual processesinduction, compression, combustion, expansion, and exhaust. This chapter deals with models for working fluid composition, and thermodynamics and transport properties. 2 Table 4.1 Working fluid constituents Process Spark-ignition engine Air Fuel1 Recycle exhaust2 Residual gas Compression Air Fuel vapor Recycle exhaust Residual gas Expansion Combustion products (mixture of N2, H2O, CO2, CO, H2, O2, NO, OH, O, H, …) Intake Exhaust 1 Compression-ignition engine Air Recycle exhaust2 Residual gas Air Recycle exhaust Residual gas Combustion products (mixture of N2, H2O, CO2, CO, H2, O2, NO, OH, O, H) Combustion products (mainly Combustion products (mainly N2, CO2, H2O and O2) N2, CO2, H2O and either O2 if < 1 or CO, and H2, if > 1) 3 Liquid and vapor in the intake; mainly vapor within cylinder 2 Sometimes used to control NO emissions x EXHAUST GAS RECIRCULATION (EGR) SYSTEM 4 Table 4.2 Categories of models for thermodynamics properties Unburned mixture Burned mixture 1.Single ideal gas throughout operating cycle with cv and cp constant Ideal gas; cv,b constant 2.Ideal gas; cv,u constant 3.Frozen mixture of ideal gases cv,u(T) 4.Frozen mixture of ideal gases Approximations fitted to equilibrium thermodynamic properties cv,u(T) 5.Frozen mixture of ideal gases cv,u(T) Mixture of reacting ideal gases in thermodynamic equilibrium Note: Subscript i,u, and b denote species i in the gas mixture, the unburned mixture, 5 and burned mixture properties respectively. 4.2 Burned and unburned mixture composition The mass of charge trapped in the cylinder (mc) is the inducted mass per cycle (mi) plus the residual mass (mr) left over from the previous cycle. mc = mi + mr Residual fraction xr mr xr mc In some engines, a fraction of engine exhaust gases is recycled to the intake to dilute the fresh mixture for control of NOx 6 Percent of exhaust gas recycled (% EGR) mEGR EGR(%) mi mEGR mi 100 : the mass of Exhaust Gas Recycled : inducted mass per cylinder Burned gas fraction, xb mc = mi + mr mEGR mr xb mc ( EGR / 100)(1 xr ) xr 7 ► Burned mixture composition Combustion of CHy with air y = H/C ratio Stoichiometric Combustion Equation: y y y CH y (1 )(O2 3.773N 2 ) CO2 H 2 O 3.773(1 ) N 2 4 2 4 8 Combustion equation (with equivalence ratio, ) written per mole O2: c 2(1 )H 2 O2 N 2 where nCO2 CO 2 n H 2O H 2 O nCOCO (1) n H 2 H 2 nO2 O2 n N 2 N 2 : N/O molar ratio (= 3.773 for air) ni : 4/(4+y) : moles of species i per mole O2 reactant 9 The ni are determined using these assumptions 1) 1 CO and H2 can be neglected 2) 1 O2 can be neglected 3) 1 water gas reaction can be assumed to be in equilibrium CO2 H 2 CO H 2 O with the equilibrium constant K P (T ) n H 2O nCO nCO2 n H 2 10 or Kp can be determined from 1.761 10 1.611 10 0.2803 10 ln K P 2.743 2 T T T3 3 6 9 Kp of 3.5 is often assumed which corresponds to the value at temperature T = 1740 K The ni is obtained from element balance of equation (1), and ni is shown in table 4.3 11 Table 4.3 burned gas composition under 1700 K species CO2 H2O CO H2 O2 N2 Sum: (nb) ni, moles/moles O2 reactant 1 1 2(1 ) absent ! absent ! c 2(1 ) c 0 0 1 (1 ) 1 c 2( 1) c absent ! 0 (2 ) 12 Summation of moles above The value of c is obtained by solving the quadratic ( K 1)c 2 cK 2( 1) 2(1 ) 2K ( 1) 0 nb ni is given in the bottom line of Table 4.3 i Hence the mole fractions are ni ~ xi nb 13 For alcohols, alcohol-hydrocarbon blends, the 1 y z CH y Oz (1 )(O2 N 2 ) 4 2 per mole O2: C 2 (1 ) H 2 O2 (1 where z 2 ) N 2 (2) 2 2 z (1 ) 14 If we write * z and * 1 2 The reactant expression (2) becomes: * C 2 (1 ) H 2 O2 * N2 which is same form as the reactant expression for hydrocarbon fuel (1) Table 4.3 can still be used to give the burned gas composition, except Replacing ,, with * ,, * 15 Example 4.1 Calculate the low-temperature burned gas composition resulting from the combustion of 7 g/s air with 0.48 g/s ethane (C2H6) Kp is assumed 3.5. Stoichiometric combustion: (again ) C2 H 6 3.5(O2 3.773N2 ) 2CO2 3H 2O 3.5 3.773N 2 You’re supposed to ( A / F ) s 16.1 know how to 1 find (A/F)s!! ( F / A) s 16.1 ( F / A) actual 0.48 g/s 7 g/s given 16 ( F / A) actual 0.48 (16.1) 1.1 1 ( F / A) s 7 We need c since 1 based on Table 4.3 We can find c by solving the following equation ( K P 1)c 2 cK P 2( 1) 2(1 ) 2K P ( 1) 0 4 Where Kp = 3.5 and 4 y y = 6/3 from C3H6 Remember ?? Thus c 2 1.46c 0.18 0 c 0.134 nCO2 ~ mole fraction: xCO2 nb (use smaller positive value) 17 From Table 4.3, nb (2 ) (2 0.57)1.1 3.773 5.345 nCO2 ~ xCO2 nb nCO2 ( c) 0.57(1.1) 0.134 0.495 0.495 ~ 0.093 xCO2 5.345 Ans n H 2O 2(1 ) c 2(1 0.57 1.1) 0.134 0.88 ~x H 2O 0.88 0.164 5.345 Ans 18 ► Unburned mixture composition Number of moles of fuel per mole O2 in mixture depends on the molecular weight of fuel, Mf Molecular formula of fuel (CH y ) M f (12 y) The fresh mixture per mole O2 (CH y ) O2 N 2 Substituting M f /(12 y) from (3), then the reactant expression becomes 4 (1 2 ) (CH y ) O2 N 2 Mf 19 The unburned mixture (fuel, air, and a burned gas fraction), per mole O2 can be written: 4 (1 xb ) (1 2 ) (CH y ) O2 N 2 M f unburned reactants xb (nCO2 nH 2O nCO nH 2 nO2 n N2 ) unburned residuals The number of moles of each species in the unburned mixture, per mole O2, is summarized in Table 4.4. 20 Table 4.4 Unburned mixture composition Species fuel O2 N2 CO2 H2O CO H2 Sum1 ni, moles/mole O2 reactant 1 1 4(1 xb )(1 2 ) / M f 4(1 xb )(1 2 ) / M f 1 x b 1 xb xb xb ( c) 2 xb (1 ) 0 0 nu xb 2(1 ) c xb c xb 2( 1) c nu 21 The total number of moles of unburned mixture nu, 4(1 2 ) nu (1 xb ) 1 xb nb , and nb is given in Table 4.3 M f Previous table for burned mixture !!! Molecular weight of (burned and unburned) mixture The mass of mixture (burned or unburned) per mole O2 mRP 32 4 (1 2 ) 28.16 Molecular weight - burned mixture, Mb M b mRP / nb - unburned mixture, Mu M u mRP / nu 22 Molecular weight Equivalence ratio Figure 4.1 Molecular weight of unburned and burned 23 isooctane-air mixtures as a function of fuel/air equivalence ratio and burned gas fraction Table 4.5 Factors for relating properties on molar and mass basis Quantity, per mole O2 in the mixture Moles of burned mixture (nb) Moles of unburned mixture (nu) General equation1 nb (1 ) 1 , 1 nb (2 ) , 1 4(1 2 ) 1 (1 xb ) 1 xb nb M f 1 Mass of mixture2 mRP 32 4 (1 2 ) 28.16 Mass of air2 1For hydrocarbon fuel, kg/kmol nb 0.36 4.773 nb 1.36 3.773 nu 0.08 4.773 0.28 xb nu 0.08 4.773 xb (1.28 1) 138.2 9.12 138.2 32 28.16 for air = 3.773; for fuels containing oxygen, are replaced for and 2Unit: Equation for C8H18-air mixtures respectively * and * 24 4.3 Gas Property Relationships Individual species in Unburned and Burned gas mixtures can be modeled as ideal gases. The most important relationship for property determination for engine calculations are summarized below Internal Energy u(T,v) and Enthalpy h(T,p) Specific heat Constant volume u du cv dT cv T T v Constant pressure h dh c p dT c p T T p 25 Specific heat ratio cp cv The change from its value at the reference condition T0, v0, p0 to the value at T, v, p u u 0 T c dT v T0 h h 0 T c dT p T0 entropy dv c p dp cv s so ds dT R dT R T v v p 26 dv cv ds dT R T v Integrate s ds s0 s T T0 s0 cv dT T T T0 Similarly, s v R v0 dv v cv dT R ln v ln v 0 T s0 T T0 c T p dT R ln v ln v0 p p0 The integral terms in the above equation are functions of temperature only, we define 27 v c v s0 dT R ln vo T T0 T s define Ψ(T) then s s0 T T0 c T p dT R ln p p0 Ф(T) s v s 0 R ln v0 (T ) s p s 0 R ln p 0 (T ) T c v(T ) dT T c p (T ) dT T T0 T T0 Thus the entropy change between state 1 and 2 p2 R ln s 2 s1 2 1 p 1 28 Isentropic process: s2 s1 p2 R ln s 2 s1 2 1 p 1 p ln 2 2 1 R p1 Mixture properties are determined either on mass or molar basis Mass basis u xi u i h xi hi s xi s i u xiu i Molar basis h xi hi s xi s i and c x c c x c v p i i v ,i p ,i c xc c xc v p i i v ,i 29 p ,i 4.4 A SIMPLE ANALYTIC IDEAL GAS MODEL - heat capacity c ,c p v are constant but different for unburned & burned gas mixture u c T h u c T h u v ,u u f ,u b v ,b b f ,b unburned h c T h h c T h u p ,u u f ,u b p ,b b f ,b burned h f ,u & h f ,b : enthalpies of formation of unburned and burned gas mixture at 0 K 30 Combustion process • Constant volume adiabatic u u u b c T h v ,u u f ,u cv,b T b h f .b (1) We solve for Tb by using relations Rb Ru Mu (2) Mb Cv R /( 1) (3) 31 From (1) c T h v ,u u T b f ,u cv,b T b h f .b 1 c c T h h f ,b u v , u f , u v ,b 1 + h f c T u v,u c c = T c v,b v,u Cv R /( 1) + u v,b h f c v,b γ -1 R = T R γ -1 u b b u + u h f c v,b 32 Tb γ -1 R = T R γ -1 u b Rb Ru Mu Mb = Mb Mu b + u u h f c Cv R /( 1) v,b γ -1 + h γ -1 T -1 R M R γ R γ -1 + M h γ -1 T γ -1 M R f b b u b b u u = Mb Mu b b f Mb b u u u M b T u h f T b= γ b-1 M u γ -1 + Ru u u u 33 - Constant pressure adiabatic h h u b hf b 1 M b u Tb T 1 u M R u u b u 34 u du cv dT cv T T v unburned burned Figure 4.2 Internal energy versus temperature plot for stoichiometric unburned and burned gas mixtures: isooctane fuel; unburned residual fraction 0.1. 35 4.5 THERMODYNAMIC CHARTS (แผนภูมิ) 4.5.1 unburned mixture charts 1. Chart that relates the mixture temperature, pressure and volume in “compression process” 2. Chart that presents internal energy and enthalpy as functions of temperature ASSUMPTIONS : •Compression process is reversible and adiabatic •Fuel is in vapor phase •Mixture composition is homogeneous and frozen •Each species can be modeled as an ideal gas •The burned gas fraction is zero 36 v (T 2) (T 1) n u R ln 2 v1 p2 (T 2) T 1 n u R ln p1 nu : Moles of unburned gas per kilogram of fuel 3 n R J T K m p Pa v kg .K u kg air air 37 hs us Figure 4.3 Sensible enthalpy and internal energy of unburned 38 isooctane-air mixtures as function of temperature. Units:kJ/kg air in mixture. Figure 4.4 Isentropic compression functions, and , as39 function of temperature for unburned isooctane-air mixtures. Units: J/kg airK. Table 4.6 Unburned mixture composition for charts v (T 2) (T 1) n u R ln 2 v1 p2 (T 2) T 1 n u R ln p 1 40 Example 4.2 The compression process in an internal combustion engine can be modeled approximately as adiabatic and reversible (i.e., as an isentropic process). A spark-ignition engine with a compression ratio of 8 operates with a stochiometric fuel vapor-air mixture which is at 350 K and 1 atm at the start if the compression stroke. Find the temperature, pressure, and volume per unit mass of air at the end of the compression stroke. Calculate the compression stroke work. Give = 350 K at the start of compression, find of compression using the isentropic chart, Fig. 4-4 For = 150 J/kg air K. From Eq. (4.25a), at the end = 350 K, 1 150 292ln 757 J / kg air K 8 From table 4.6 Figure 4-4 Figure 4-4 then gives T2 = 682 K The ideal gas law gives This is wrong in your handout. Please correct it !! T2 v1 682 and p2 p1 8 15.5 atm T1 v2 350 42 150 350 K Figure 4.4 Isentropic compression functions, and , as43 function of temperature for unburned isooctane-air mixtures. Units: J/kg airK. 757 150 350 K 682 K Figure 4.4 Isentropic compression functions, and , as44 function of temperature for unburned isooctane-air mixtures. Units: J/kg airK. Note that p2 can also be obtained from Fig. 4-4: p2 2 1 980 180 ln 2.74 nu R 292 p1 p2 15.5 atm The compression stroke work, assuming the process is adiabatic and using the data in Fig. 4-3, is 45 u2=350 u1=40 T1=350 K T2=682 K Figure 4.3 Sensible enthalpy and internal energy of unburned 46 isooctane-air mixtures as function of temperature. Units:kJ/kg air in mixture. Problem 2 (20 points) A 3-liter, six cylinder SI engine is running at 3600 rpm. The engine has an equal size of bore and stroke. Its compression ratio is 9.5. The connecting rod length is 16.6 cm. If combustion ends at 20o after top center (ATC), calculate •Bore •Mean piston speed •Clearance volume •Piston velocity as soon as the combustion ends • Distant between the crank axis and the piston pin axis as soon as the combustion ends 47 Problem 3 (22 points) In an analysis of combustion of propane (C3H8) with air, it is found that the exhaust gas composes of CO2, O2, H2O and N2 in which CO2 is found to be 9 % by mole. Compute the fuel/air equivalence ratio and the corresponding A/F. (Molecular weight of air: 28.96, atomic weight H: 1, O: 16, C: 12, N: 14) 48 Problem 4 (15 points) Gaseous mixture in a closed tank composes of CO2, CO and O2. These gases are in chemical equilibrium based on Kp 2CO 2 2CO O 2 Pressure of the mixturein the tank is 1.4 atm. If there are 6 moles of CO, calculate the equilibrium constant Kp of this reaction. 49 4.5.2 Burned mixture charts 1. For products of combustion at high temperature 2. During expansion process ASSUMPTIONS : •Expansion process is reversible and adiabatic. •Each species in mixture can be modeled as an ideal gas. •Mixture is in thermodynamic equilibrium at temperature above 1700 K. Mixture composition is frozen below 1700 K. •At the datum state of 298.15 K and 1 atm chemical elements in their naturally occurring form (N2, O2, H2 as diatomic gases and C as solid graphite) are assigned zero enthalpy and entropy. 50 Figure 4.5 Internal energy versus entropy chart 51 for equilibrium burned gas mixture, isooctane fuel, equivalence ratio 1.0 Example 4.3 the expansion process in an internal combustion engine, following completion of combustion, can be modeled approximately as an adiabatic and reversible process (i.e., isentropic). Under full-center immediately following combustion is 7100 kPa. Find the gas state at the end of the expansion stroke and the expansion stroke work. The compression ratio is 8, the mixture is stoichimetric, and the volume per unit mass of air at the start of expansion is 0.125 m3/kg air Locate 7100 kPa and 0.125 m3/kg air on the = 1.0 burned gass chart (Fig. 4-8). This gives 2825 K, and s1 = 9.33 kJ/kg airK. The gas expands at constant entropy to m3/kg air. Following a constant entropy process from state 1 on Fig. 4-8 gives 52 1 2 Figure 4.5 Internal energy versus entropy chart 53 for equilibrium burned gas mixture, isooctane fuel, equivalence ratio 1.0 Looked up from chart at point 2, = 1840 K, = 570 kPa, and = -1540 kJ/kg air The expansion stroke work, assuming the process is adiabatic, is kJ/kg air 54 4.5 Relation between unburned and burned mixture charts (ความสั มพันธ์ ระหว่ างแผนภูมสิ ารผสมเผาไหม้ และไม่ เผาไหม้ ) Given unburned mixture at T1 , p1 , v1 , the combustion could be considered as (1) constant-volume adiabatic combustion (2) constant-pressure adiabatic combustion Charts Unburned - Compression process - Enthalpy and internal energy of the mixture = 0 at T = 298 K Burned - Expansion process - Enthalpy and entropy of the chemical elements in their naturally occurring form form (O2 , N 2 and H and C (solid))55are 2 assigned zero GOING FROM UNBURNED TO BURNED Combustion End of compression (unburned) Start of expansion (burned) Adiabatic Constant volume ub = u u Constant pressure hb = hu Relations between unburned and burned 56 Constant pressure Constant volume ub = u u hb = h u uu u s ,u u f ,u hu hs ,u h f ,u Fig. 4-3 Fig. 4-3 0.4, hf ,u 51.9 1181xb ,u f ,u 47.3 1183xb 0.6 , hf ,u 77.8 1771xb , u f ,u 70.9 177 xb 0.8 , hf ,u 103.8 2361xb ,u f ,u 94.6 2365xb 1.0 ,h f ,u u 129.7 2951xb , f ,u 118.2 2956 xb 1.2 , hf ,u 155.6 2759 xb , u f ,u 141.9 2769 xb 57 The datum for internal energy and enthalpy for the unburned mixture in unburned chart is different from that used in the burned chart. In order to locate the state of the unburned mixture in the burned chart, the reference datum has to be changed. These data can be related through the enthalpies of formation. The unburned mixture enthalpy hu with the same datum as the burned mixture is hu hs ,u h f ,u where hs,u is the sensible enthalpy 58 ~ h f ,i is the enthalpy of formation of unburned mixture per kilogram of air, defined as ~ ~ n h h f ,u i f ,i , i where ni = number of kilomoles of species i per kilogram of air Similarly, the internal energy uu is given by uu u s ,u u f ,u where u f ,u ni u~ f ,i i u Alternatively, f ,u can be obtained from ~ u f ,u h f ,u (nP nR ) RT 59 Expressions of h f ,uand u f ,u (kJ/kgair) at several : 0.4, hf ,u 51.9 1181xb ,u f ,u 47.3 1183xb 0.6 , hf ,u 77.8 1771xb , u f ,u 70.9 177 xb 0.8 , hf ,u 103.8 2361xb ,u f ,u 94.6 2365xb 1.0 ,hf ,u 129.7 2951xb ,u f ,u 118.2 2956 xb 1.2 , hf ,u 155.6 2759 xb , u f ,u 141.9 2769 xb 60 Example 4.4 Calculate the temperature and pressure after constant pressure adiabatic combustion of unburned mixture (with = 1.0 and x b= 0.08) at the state corresponding to the end of compression process: Tu = 682 K, u s ,u = 350 kJ/kgair, pu = 1.57 MPa and vu = 0.125 m3/kgair Analysis hb hu hb hs ,u hf ,u For (1) = 1.0 h f ,u 129.7 2951xb 129.7 236 366 kJ/kgair (2) 61 From figure 4.3 at T = 682 K, = 1.0, we obtain hs ,u 465 kJ/kgair (3) Replacing (2) and (3) into (1), resulting in hb hs ,u hf ,u hb = 465 - 366 = 99 kJ/kgair For constant pressure combustion, Pb = Pu = 1.57 MPa ub hb pbvb 99 1.57 103 vb kJ/kgair Using a trial and error procedure to find v b and u b at p 1570 kPa , from the burned chart (figure 4.5) for = 1.0 , we finally get ub 665 kJ/kgair , Tb 2440K, vb 0.485 m3/kg air 62ANS 1570 Figure 4.5 Internal energy versus entropy chart 63 for equilibrium burned gas mixture, isooctane fuel, equivalence ratio 1.0 TRIAL AND ERROR PROCEDURE 1. Make a reasonable guess of vb 2. Compute ub 3. For ub and pb = 1570 kPa locate point on the burned chart 4. Find vb from the chart and check if this vb is equal to vb in (1.) 5. Use vb in (4.) for computing ub as steps (2.) to (4.) repeat. 64 4.6 Intro. to Exhaust Gas Composition While the formulas for the products of combustion used in chapter 3 are useful for determining unburned mixture stoichiometry, they do not correspond closely to the actual burned gas composition. In the actual case, not all the fuel which enters the engine is fully burned inside the chamber; the combustion inefficiency even when excess air is present in a few percent. Also, the contents of each cylinder are not necessarily uniform in composition, and the amounts of fuel and air fed to each cylinder of a multi-cylinder engine are not exactly the same. For all these reasons, the composition of the engine exhaust gases cannot be easily calculated. 65 It is now routine to measure the composition of engine exhaust gases (e.g., CO2, NOx and unburned hydrocarbons and particulates). This is done to determine engine emissions. It is also done to determine the relative proportions of fuel and air which enter the engine so that its operating equivalence ratio can be computed. 66 Mole fractions of Fuel-air equivalence ratio Figure 4.6 Spark-ignition engine exhaust gas composition data in mole fraction as a function of fuel/air equivalence ratio. 67 Figure 4.7 Hydrogen concentration in spark-ignition engine 68 exhaust as a function of carbon monoxide concentration. Units: percent by volume. Figure 4.8 Exhaust gas composition from several diesel engines 69 in mole fractions on a dry basis as a function of fuel/air equivalence ratio.