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Head of Department: Beroun Stanislav Project: LN 00B073 SM 393/2001 Number of the page: 15 Number of the supplement: 3
Liberec, 2001
Summary One of the most important relationships for property determination of engine calculations is the specific heat (heat capacity) and the specific heat ratio. The description of substance properties of chosen types of combustible mixtures and their combustion products (with respect to complete combustion) is based on the reference data.
Introduction As it is known from experience that it takes different amounts of energy to raise the temperature of identical masses of different substances by one degree. Therefore, it is desirable to have a property that will enable us to compare the energy storage capabilities of various substances. This property is the specific heat. The specific heat is defined as the energy required to raise the temperature of a unit mass of a substance by one degree. In general, this energy will depend on how the process is executed. In thermodynamics, there are two kinds of specific heats: specific heat at constant volume C v and specific heat at constant pressure C p . Physically, the specific heat at constant volume C v can be viewed as the energy required raising the temperature of the unit mass of substances by one degree as the volume is maintained constant. The energy required to do the same, as the pressure is maintained constant is specific heat at constant pressure C p . The specific heat at constant pressure C p is always greater than C v because at constant pressure the system is allowed to expand and the energy for this expansion work must also be supplied to the system. Specific heats can be expressed in terms of other properties; thus they must be properties themselves. From the definition of C v , the energy must be equal to C v dT, where dT is the differential change in temperature.
Thus, or
C v dT = du
(1) (2)
u Cv = T v
Similarly, an expression for the specific heat at constant pressure C p can be obtained by considering a constant-pressure. It yields h Cp = . (3 ) T P
A few observations can be made from previous equations. First, these equations are property relations and such as are independent on the type of processes. They are valid for any substance undergoing any process. The only relevance C v has to a constant volume process is that C v happens to be the energy transferred to a system during a constant-volume process per unit mass per unit degree rise in temperature. This is how the values of C v are determined. This is also how the name specific heat at constant volume originated. Likewise, the energy transferred to a system per unit mass per unit temperature rise during a constant-pressure process happens to be equal to C p . This how the values of C p can be determined and also explains the origin of the name specific heat at constant pressure. Another observation that can be made is that C v is related to the changes in internal energy and C p to the changes in enthalpy. In fact, it would be more proper to define C v as the change in the specific internal energy of substances per unit change in temperature at constant volume. Likewise, C p can be defined as the change in the specific enthalpy of a substance per unit change in temperature at constant pressure. In other words, C v is a measure of the variation of internal energy of a substance with temperature, and C p is a measure of the variation of enthalpy of a substance with temperature. A common unit for specific heat is [kJ/kgC] or [kJ/kgK] ~ ~ The specific heats are sometimes given on a molar basis. They are denoted by C v and C p and have unit [kJ/kmolC] or [kJ/kmolK]. Specific heats of real gases
The specific heat of ideal gases depends, at most, on temperature only. At low pressure all gases approach ideal-gas behavior and therefore their specific heats depend on temperature only. The specific heats of real gases at low pressure are called ideal-gas specific heats, or zero-pressure specific heats. Accurate analytical expressions for real-gas specific heats, based on direct measurements or calculations from statistical behavior of molecules, are available and tabulated or given as polynomials or empirical equations. The use of real/gas specific heat data is limited to low pressure, but these data can be also used at moderately high pressures with reasonable accuracy as long as the gas does not deviate from ideal/gas behavior significantly. The specific heat values for some common gases are listed as a function of temperatures in tables in many literatures. Tables giving the composition and thermodynamic properties of combustion products have been compiled. They are useful sources of property and species concentration data in burned gas mixtures for a range of temperatures. When large numbers of computations are being made or high accuracy is required, engine process calculations are carried out on a computer. Relationships which model the composition
and/or thermodynamic properties of unburned and burned gas mixtures have been developed for computer use. These vary considerably in range of application and accuracy. The most complete models are based on polynomial curve fits to the thermodynamic data for each in the mixture. For each component (i) in its standard state at temperature T (K), the specific ~ heat C pi is approximated in [3] by the polynomial: ~ C pi , (4 ) = ai1 + ai 2 .T + ai 3.T 2 + ai 4 .T 3 + ai 5 .T 4 ~ R
~ ~ where C pi is in [cal/gmolK], and R is universal gas constant in [cal/gmolK]. Values of the coefficients aij for (CO2, H2O, CO, H2, O2, N2, OH, NO, O, and H) from the NASA program are given in table T 1 in [3] - supplement 1. Two temperature ranges are given. The (300 to 1000)K range is appropriate for unburned mixtures property calculations. The (1000 to 5000)K range is appropriate for burned mixtures property calculations. Polynomial functions for various fuels (in the vapor phase) have been fitted to the functional form (5), Af 5 ~ , (5 ) C pf = Af 1 + Af 2 .t + A f 3 .t 2 + Af 4 .t 3 + 2 t where t= T(K)/1000. The values for the coefficient Af1 to Af5 for typical petroleum-based fuels are taken from [3], see ~ table T 2 - supplement 2. The units of the coefficients give C pf in [cal/gmol.K] with t=T(K)/1000. In other literature [2], the specific heats are given as third-degree polynomials for several gases as a function of temperature and they expressed as: ~ C p = a + b.T + c.T 2 + d .T 3
, (6 )
C1 pm (T ) = A + B1 T
(1 e
exp C1 / T
C1 / T 2
e C2 / T C + B2 2 T 1 eC 2 / T
(7 )
Coefficients (A, B1 ,B2 ,C1 ,C2 ) depend on substances and they are listed in the table T 4. Table T 4: Coefficients for substances CH4, C3H8, C4H8 - according to [1]. Substance A B1 B2 C1 CH4 33,823 54,22 37,37 2239,83 C3H8 55,852 115,27 76,70 1545,097 C4H10 75,739 94,10 148,80 3958,111 C2 5918,8 3970,728 1546,537
~ This an important relationship for ideal gases since it enables us to determine C v from ~ knowledge of C p and the gas constant R. When the specific heats are given on a molar basis, R in the above equation should be replaced by the universal gas constant Ru. That is, ~ ~ C p = Cv + Ru [KJ/kmol.K] (11)
At this point, it is introduced another ideal-gas property called the specific heat ratio , defined as
Cp Cv
[-]
(12)
The specific heat ratio also varies with temperature, but this variation is very mild. For monatomic gases, its value is essentially constant at 1,667. Many diatomic gases, including air, have a specific heat ratio of about 1,4 at room temperature, whereas the value of specific heat ratio for multi-atomic gases is about 1,33. The specific heat ratio also could be determined for diatomic gases using empirical equation Schlle [4] as: T (13) = 1,41 0,572 10000
From the previous equation, a specific heat at constant volume can be expressed as: Cv = R 287,1 = 1 1
. (14)
mm =
it yields
mi
i =1
and
Nm =
Ni
i =1
(15)
m fi =
mi mm
and
Yi =
Ni Nm
(16)
From the above equations, specific heats of gas mixture during a process depending on temperature can be expressed as,
C pm =
m fiC pi ,
i =1
Cvm =
~ C vm =
k i =1
m fiCvi [kJ/kgC] ,
i =1
(17)
~ C pm =
k i =1
~ YiC pi
and
~ Yi C vi [kJ/kmolC]
(18)
Notice that properties per unit mass involve mass fractions (mfi) and properties per unit mole involve mole fractions (Yi). The relations given above are generally valid and are applicable to both ideal-and real-gas mixtures. Similarly, the specific heats of combustion products can be expressed. The calculations of specific heats are divided into two categories according to the excess-air ratio , which is often used to describe mixture strength: 1- stoichiometric mixture (SM) with =1, 2- lean-burn mixture (LB) with various values of .
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According to various fuels using mass fractions of individual components of mixtures and their combustion products. That are: - hydrogen-air mixture, - natural gas (NG)-air mixture, - liquefied petroleum gas (LPG) -air mixture (60%propane/40%butane), - gasoline-air mixture, - diesel-air mixture, - empirical equation Schlle . Values of substances ( H2O, CO2, O2, N2 and H2) are taken from tables in [4] and [2], whereas the specific heats values of gas substances(methane CH4, propane C3H8 and butane C4H10) are calculated by the empirical equation (7), and the values for gasoline and diesel are calculated by empirical equation (5). The calculations are based on the mass fractions of components of mixtures and products according to the following combustion equation (19):
3n + 1 3n + 1 3n + 1 C n H (2 n + 2 ) + . .3,76.N 2 (O2 + 3,76 N 2 ) n.CO2 + (n + 1)H 2 O + ( 1) O2 + . 2 2 2
(19)
The previous equation is valid for gas fuel (type CnH2n+2), so it can be valid for CH4, C3H8, C4H10 and H2 mixtures with air. The mass of mixture is equal to the mass of combustion products and it is expressed in [kg] as
2 + 14.n + .(205,92.n + 68,64) = A The mass fractions of individual components of mixture are:
(20)
m fCnH 2 n + 2 =
14.n + 2 , A
m fO2 =
16..(3.n + 1) , A
(21)
m fN 2 =
52,64..(3.n + 1) A
The mass fractions of individual combustion products are: m fCO2 = 44.n , A m fH 2O = and m fN 2 = 18.(n + 1) , A
52,64.(3.n + 1) (22) A A The unit of mass fraction is in [%] and the sum of the individual mass fractions is equal to one. The combustion equation for (60%propane, 40%butane)-air mixture is expressed as (23) : m fO2 = 16
( 1)(3.n + 1)
Mass of mixture is equal to the mass of combustion products and it is expressed in [kg] as:
49,6 + 768,768. = B The mass fractions of individual components of mixture are: m f (0,6C3 H 8 +0, 4C4 H10 ) = 49,6 , B
(24)
m fO2 =
m fN 2 = 589,568. B .
179,2. , B
(25)
The mass fractions of individual combustion products are: m fCO2 = m fO2 = 149,6 , B and m fH 2O = m fN 2 = 79,2 , B (26)
179,2.( 1) B
589.568. . B
and mass of mixture is equal to the mass of combustion products and it is expressed in [kg] as:
114,62 + 1665,8928. = C
(28)
m fgasoline =
114,62 , C
m fN 2 = 1277,5728. . C
m fO2 =
388,32. , C
(29)
The mass fractions of individual combustion products are: m fCO2 = m fO2 = 363,44 C and m fH 2O = m fN 2 = 139,5 , C . (30)
388,32.( 1) C
1277,5728. C
and mass of mixture is equal to the mass of combustion products and it is expressed in [kg] as: 148,3 + 2124,408. = D The mass fractions of individual components of mixture are: (32)
m fdiesel =
1629,208. D The mass fractions of individual combustion products are: m fN 2 = m fCO2 = m fO2 = 475,2 , D 495,2. D and m fH 2O = m fN 2 =
148,3 , D
m fO2 =
495,2. , D
(33)
168,3 , D (34)
1629,208. . D
A few observations can be made from the above equations: All the above compressed chemical equations are valid for excess-air ratio 1 . The general combustion equation for chemical reaction (19) is valid for any gas fuel (type CnH2n+2)-air mixture including hydrogen-air mixture. The mass of the mixture is equal to the mass of the combustion products in [kg]. The mass fractions of individual components of mixture and combustion products are valid for any varying values of atom numbers of carbon and hydrogen (depends on fuel type) and various values of excess air ratio ..
Calculation evaluation
Specific heat of real gases is a significant gas property of substances which is affected by temperature. A specific heat of few substances is almost similar, while it is for others different depending on temperature and it is also expressly distinguished. Otherwise as it is seen in Fig. 1 to Fig 4 for CP, the specific heat values of substances ( N2, O2, CO2, air and empirical equation Schlle) are expressly distinguished from the specific heat values of hydrocarbons (CH4, C3H8, C4H10, C8,26H15,5 and C10,8H18,7), H 2O and H2 and from Cv values as well. Also the specific heat values of hydrocarbons above mentioned and water are clear different from hydrogen specific heat values at both constant pressure and volume, while for other substances(CH4, C3H8, C4H10, C8,26H15,5 and C10,8H18,7), the specific heats are not so different, because their variation with temperature is smooth and may be approximated as linear over small temperature intervals (a few hundred degrees or less).
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Similarly, the specific heat ratio also depends on temperature, it decreases with temperature increasing as it is shown in Fig. 5 for individual substances (H2, H2O, CH4, C3H8, C4H10, N2, O2, CO2, C8,26H15,5 , C10,8H18,7), air and empirical equation Schlle). In Fig. 6 and Fig. 7, the specific heat curves CV and CP respectively are shown, for methane-air mixture and its combustion products and as it is seen from curves that the CP and CV are also vary with temperature and with mixture richness - - and the specific heat is higher for fuel-rich mixtures, while its ratio =has less values for fuel-rich mixtures as it is seen in Fig. 11 with various values of =. On the specific heat and on its ratio has a significant effect, mixture composition as it was mentioned; Fig. 8 to Fig. 10 show the variation of Cv with temperature and with various values of excess air ratio for various gas-air mixture.= From the calculating values of substance properties for real fuel-air mixtures and their combustion products (Fig. 8 to Fig. 10) compared to the calculating values for substitute diatomic gas expressed by Schlle equation, has been relatively demonstrated a large difference. The following example proves this result: = For stoichiometric mixture of hydrocarbon fuels and air with temperature T=700 K, the specific heat at constant volume (CV) for real mixture is higher by 20%, with temperature T=2000 K, the specific heat (CV) of combustion products is almost higher by 13% than diatomic gas (according to Schlle equation). = The reciprocal relation between the values of the adiabatic exponent of real mixtures (and their combustion products) and the substitute diatomic gas is very important: the real mixtures have lower value () than the substitute diatomic gas- Schlle (Fig. 11). This fact partially eliminates the effect of higher values of the specific heats of real mixtures.
1500 1400
Specific heat Cp [J/kgK]
1300 1200 1100 1000 900 800 0 500 1000 1500 2000 2500 300 Temperature [K] CO2 O2 Schlle Air N2
Fig.1: Specific heat at constant pressure Cp for substances (N2, O2, CO2, air and empirical equation Schlle) as a function of temperature.
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C C4H8 4H10 H2 H2
C C8,26H15,5 8,26H15,5
20000 7300 18000 16000 6300 5300 4300 3300 2300 1300 0 500 1000 1500 2000 2500 Temperature [K] 14000 12000 10000 8000 6000 4000 2000 0 3000
Fig. 2: Specific heat at constant pressure Cp for substances (H2, H2O, CH4, C3H8, C4H10, C8,26H15,5 and C10,8H18,7) as a function of temperature.
1200 1100
Specific heat Cv [J/kgK]
1000 900 800 700 600 0 500 1000 1500 2000 2500 3000 Temperature [K]
Fig. 3: Specific heat at constant pressure Cv for substances (N2, O2, CO2, air and empirical equation Schlle) as a function of temperature.
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CH CH4 4 H2O H 2O
CC4H8 4H10 H2 H2
C8,26H15,5 C8,26H15,5
16000 7100 14000 12000 10000 8000 4100 6000 3100 2100 1100 0 500 1000 1500 2000 2500 Temperature [K] 4000 2000 0 3000
6100 5100
Fig. 4: Specific heat at constant volume Cv for substances (H2, H2O, CH4, C3H8, C4H10, C8,26H15,5 and C10,8H18,7) as a function of temperature
H2 H2 CC8,26H15,5 8,26H15,5 1,45 1,4
Specific heat ratio k [-]
1,35 1,3 1,25 1,2 1,15 1,1 1,05 1 0 500 1000 1500 Temperature [K] 2000 2500 3000
Fig. 5: Specific heat ratio for substances (H2, H2O, CH4, C3H8, C4H10, C8,26H15,5, C10,8H18,7, and Schlle equation) as a function of temperature.
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1300 1200 =1
CV [J/kg.C]
1600 1500 1400 1300 1200 1100 1000 0 500 1000 1500 2000 2500 Teplota [K] =1 1,4 2
Cp[J/kgC]
1,4
2000
2500
3000
Fig. 6: Specific heat at constant volume Cv for NG-air mixture and combustion products as a function of temperature and excess-air ratio=.=
Fig. 7: Specific heat at constant pressure Cp for NG-air mixture and combustion products as a function of temperature and excess-air ratio=.=
1300 1200 1100 1000 900 800 700 0 500 1000 1500 2000 2500 3000 Tem perature [ K ]
Fig. 8: Specific heat at constant volume Cv for various fuel-air mixture and combustion products a a function of temperature and excess-air ratio==1=compared to the Schlle equation=
=1
Gasoline-air mixture NG-air mixture LPG-air mixture Schlle equation gasoline-air products NG-air products LPG-air products
13
= 1,45
900 800 700 0 500 1000 1500 2000 2500 3000
NG-air mixture LPG-air mixture Schlle equation H2-air mixture NG-air products LPG-air products H2-air products
Temperature T[K]
Fig. 9: Specific heat at constant volume Cv for various fuel-air mixture and combustion products as a function of temperature and excess-air ratio==1,45==compared to the Schlle equation=
1300 1200 1100 1000 = 1,8 900 800 700 0 500 1000 1500 2000 Tem perature T[K]
NG-air mixture Diesel-air mixture Schlle equation H2-air mixture NG-air products DIESEL-air products H2-air products
2500
3000
Fig. 10: Specific heat at constant volume Cv for various fuel-air mixture and combustion products as a function of temperature and excess-air ratio==1,8=compared to the Schlle equation=
14
1,45
[-]
1,4
1,35
1,3
1,25
Fig. 11: The specific heat ratio methane-air mixture and combustion products as a function of temperature and various excess-air ratio= The specific heat of real gases mixtures is a significant gas property of substance, which is affected by temperature. With high temperatures of cylinder charge, the variation of specific heats is appreciable, which results in lowering maximum temperatures and pressures, cycle efficiency and mean effective pressure.
This research has been subsidized by the project of the Czech Ministry of Education, LN 00B073
References 1. Bure, M., Holub, R., Lietner, J., Vonka, P.: Termodynamick veliiny organickch slouenin, svazek 2. VCHT Praha, 1992. 2. Cengel, A. Y., Boles, M.A.: Thermodynamics. An Engineering Approach. 2th Edition. McGraw-Hill Inc. USA, 1994. 3. Heywood, J., B.: Internal Combustion Engine Fundamentals. McGraw-Hill Inc. USA, 1989. 4. Jastrembskij, A.S.: Technick termodynamika, I. dl, SNTL Praha, 1954
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Supplement1 - T 1: Coefficient for species thermodynamic properties (specific heats) - according to [3].
T range [K]
1000-5000 300-1000 1000-5000 300-1000 1000-5000 300-1000 1000-5000 300-1000 1000-5000 300-1000 1000-5000 300-1000 1000-5000 1000-5000 1000-5000 1000-5000
ai1
0,44608 (+1) 0,24008 (+1) 0,27168 (+1) 0,40701 (+1) 0,29841 (+1) 0,37101 (+1) 0,31002 (+1) 0,30574 (+1) 0,36220 (+1) 0,36256 (+1) 0,28963 (+1) 0,36748 (+1) 0,29106 (+1) 0,31890 (+1) 0,25421 (+1) 0,25 (+1)
ai2
0,30982 (-2) 0,87351 (-2) 0,29451 (-2) -0,11084 (-2) 0,14891 (-2) -0,16191 (-2) 0,51119 (-3) 0,26765 (-2) 0,73618 (-3) -0,18782 (-2) 0,15155 (-2) -0,12082 (-2) 0,95932 (-3) 0,13382 (-2) -0,27551 (-4) 0,0
ai3
-0,12393 (-5) -0,66071 (-5) -0,80224 (-6) 0,41521 (-5) -0,57900 (-6) 0,36724 (-5) 0,52644 (-7) -0,58099 (-5) -0,19652 (-6) 0,71555 (-5) -0,57235 (-6) 0,23240 (-5) -0,19442 (-6) -0,52899 (-6) -0,31028 (-8) 0,0
ai4
0,22741 (-9) 0,20022 (-8) 0,10227 (-9) -0,29637 (-8) 0,10365 (-9) -0,20320 (-8) -0,34310 (-10) 0,55210 (-8) 0,36202 (-10) -0,67635 (-8) 0,99807 (-10) -0,63218 (-9) 0,13757 (-10) 0,95919 (-10) 0,45511 (-11) 0,0
ai5
-0,15526 (-13) 0,63274 (-15) -0,48472 (-14) 0,80702 (-12) -0,69354 (-14) 0,23953 (-12) 0,36945 (-14) -0,18123 (-11) -0,28946 (-14) 0,21556 (-11) - 0,65224 (-14) -0,22577 (-12) 0,14225 (-15) -0,64848 (-14) -0,43681 (-15) 0,0
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Af1
-0,29149 -1,4867 -20,777 -0,55313 -20,7059 6,990 -240,078 -220,501 -90,1063
Af2
26,327 74,339 21,48 181,62 44,68 39,741 256,63 227,99 246,97
Af3
-10,610 -39.065 -164,125 -97,787 -27,501 -11,926 -201,68 -177,26 -143,74
Af4
1,5656 8,0543 52,832 20,402 7,2193 0,0 64,750 56,048 32,329
Af5
0,16573 0,01219 0,56635
Af6
-18,331 -27,313 -39,836
Af8
4,300 8,852 15,611 20,232 5,3375 7,6135 17,792 15,235 23,514
Isooctane C8H18 Methanol CH3OH Ethanol Gasoline Diesel C2H5OH C8.26H15.5 C7.76H13.1 C10,8H18.7
-0,03095 -60,751 0,20299 0,0 0,5808 0,4845 0,0518 -48,288 -60,214 -27.562 -17,578 -50,128
Cp ,f is in cal/gmol.K with
t=
T (K ) . 1000
Af6 gives enthalpy data at 298,15 K; (Af6 + Af8 ) gives enthalpy data at 0 K.
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