APPENDIX A

THERMODYNAMIC DATA

A.l Introduction

The thermodynamic tables presented here for enthalpy and internal energy differ from those that are usually
available, since they incorporate the enthalpy of formation. This means that there is no need for separate
tabulations of calorific values, and it will be found that energy balances for combustion calculations are greatly
simplified. The enthalpy of formation (Hj) is perhaps more familiar to physical chemists than engineers.

The enthalpy of fonnation (Hj) of a substance is the standard reaction enthalpy for the
formation of the compound from its elements in their reference state.

The reference state of an element is its most stable state (eg carbon atoms , but oxygen
molecules) at a specified temperature and pressure, usually 298.15 Kanda pressure of 1 bar.
In the case of atoms that can exist in different forms, it is necessary to specify their form, for
example, carbon is as graphite, not diamond.

Combustion calculations are most readily undertaken by using absolute (sometimes known as sensible) internal
energies or enthalpy. In steady flow systems where there is displacement work then enthalpy should be used;
this has been illustrated by Figure 3.8. When there is no displacement work then internal energy should be used
(Figure 3.7). Consider now Figure 3.8 in more detail. With an adiabatic combustion process from reactants
(R) to products (P) the enthalpy is constant, but there is a substantial rise in temperature.

Fig 3. 7 Constant volume combustion Fig 3.8 Constant pressure combustion

A.2 Introduction to Internal Combustion Engines- SOLUTIONS

(A.l

In the case of the isothermal combustion process (IR -+ IP) the temperature <n is obviously constant, and the
difference in enthalpy corresponds to the isobaric calorific value (-!:Jl/').

(A.2

A.2 THERMODYNAMIC PRINCIPLES

In the following sections, it will be seen how the thermodynamic data for: internal energy, enthalpy, entropy
and Gibbs function, can all be determined from measurements of heat capacity, and phase change enthalpies
(or internal energies). Furthermore, when the energy change associated with a chemical reaction is measured,
then the enthalpy of formation can be deduced. This in tum leads to 'absolute' values of internal energy,
enthalpy, entropy and Gibbs function, from which it is possible to derive the equilibrium constant for any
reaction.

A.2.1 Detennination of: Internal Energy, Enthalpy, Entropy and Gibbs Function

Figure 3.8 shows that the enthalpies of both reactants and products are in general non-linear functions of
temperature. The Absolute. Molar Enthalpy tables presented here, use a datum of zero enthalpy for elements
when they are in their standard state at a temperature of 25°C. The enthalpy of any substance at 25°C will
thus correspond to its enthalpy of formation, !:Jl1o. The use of these tables will be illustrated, after a
description of how they have been developed.

Tables are not very convenient for computational use, so instead molar enthalpies and other thermodynamic data
are evaluated from analytical functions; a popular choice is a simple polynomial. For species i

H.(1) = A.I + B.T + C.T2 + D.T 3 + E.T4 + F.T 5 (A.3

I I I I I I

from which it can be deduced (since dH = CPdn that:

Cp,l.(T) = B.l + 2C.T + 3D.T 2 + 4E.T 3 + 5F.T4 (A.4

I I I I

As U=H-RT

U.(T) =A.I + (B.I - R0 )T + C.T 2 + D.T 3 + E.T4 + F.T 5 (A.5

I I I I I

CV,l.(T) = (B.I - R) + 2C.T + 3D.T 2 + 4E.T 3 + 5F.T4 (A.6

0 I I l I
 APPENDIX A- THERMODYNAMIC DATA A.3

and as dH = CPdT = Td.S

dS = (Cpf1)dT,
integrating gives equation A.4 gives:

S.I 0 ::::: B.~n(T)

I
+ 2C.T
I
+ 3/2D.T
I
2 + 4/3E.T3 + 5/4F.r +G. (A.7
I I I

where G; is an integration constant that is used to set the zero datum, e.g. 0 K by Rogers and Mayhew (1988)-
the same datum does not have to be used as for enthalpy.

A more common choice is to use a polynomial function to describe the specific heat capacity variation, and to
divide through by the Molar Gas Constant (R.,). Equation A.4 becomes

(A.8

where a; = B;IR
0 , b; = 2C;IR
0 , C; = 3D/R 0 etc.

Table A.l Coefficients in Equations A.8 A.9 and A.10, for the evaluation of thermodynamic data from
Gordon and McBride (1971), except Argon, from Reid et al (1987).

N1 co NO Ar OH 0 H

1000-5000 K

0.28963el 0.36220El 0.31002El 0.29841El 0.44608El 0.27168El 0.31890El 2.5016 0.29106El 0.25421El 2.5
0.15155e-2 0.73618E-3 0.51119E-3 0.14891E-2 0.30982E-2 0.29451E-2 0.13382E-2 0 0.95932E-3 -0.27551E-4 0
-0.57235e-6 -0.19652E-6 0.52644E-7 -0.57900E-6 -0.12393E-5 -0.80224E-6 -0.52899E-6 0 -0.19442E-6 -0.31028E-8 0
0.99807e-10 0.36202E-10 -0.34910E-10 0.10365E-9 0.22741E-9 0.10227E-9 0.95919E-10 0 0.13757E-10 0.45511E-11 0
-0.65224e-14 -0.28946E-14 0.36945E-14 -0.69354E-14 -0.15526E-13 -0.48472E-14 -0.64848E-14 0 0.14225E-15 -0.43681E-15 0
-0.90586e3 -0.12020E4 -0.87738E3 -0.14245E5 -0.48961E5 -0.29906E5 0.98283E4 -745.852 0.39354E4 0.29231E5 0.25472E5
0.61615el 0.36151El -0.19629El 0.63479El -0.98636EO 0.66306El 0.67458El 0.43529El 0.54423El 0.49203El -0.460120EO

300- 1000 K

0.36748El 0.36256El 0.30574El 0.37101El 0.24008El 0.40701El 2.5016

-0.12082E-2 -0.18782E-2 0.26765E-2 -0.16191E-2 0.87351E-2 -0.11084E-2 0
0.23240E-5 0. 70555E-5 -0.58099E-5 0.36924E-5 -0.66071E-5 0.41521E-5 0
-0.63218E-9 -0.67635E-8 0.~210E-8 -0.20320E-8 0.20022E-8 -0.29637E-8 0
-0.22577E-12 0.21556E-11 -0.18123E-11 0.23953E-12 0.63274E-15 0.80702E-12 0
-O.l0612E4 -0.10475E4 -0.98890E3 -0.14356E5 -0.48378E5 -0.30280E5 -745.852
0.23580El 0.43053El -0.22997El 0.29555El 0.96951El -0.32270EO 0.43529El

, polynomial fit will only be satisfactory over a small temperature range (300- 1000 K or 1000- 5000 K), and such polynomial
~uations ought never to be used outside their range. As the specific heat capacity variation with temperature has a 'knee'
etween 900 K and 2000 K, then a single polynomial is never likely to be satisfactory. Instead, two polynomials can be used
A.4 Introduction to Internal Combustion Engines- SOLUTIONS

which give identical values of c, at the transition between the low range and the high range (the transition temperature is usually
chosen between 1000 and 2000 K). Examples of such polynomials are presented by Gordon and McBride (1971), and were used
as the basis for constructing the tables used here. The coefficients for the evaluation of the thermodynamic tables are summarised
in Table A.l.

The tables at the end of this Appendix present: the enthalpy (H), internal energy (U), entropy (S) and Gibbs energy (G) for
gaseous species (Table A.4) and fuels (Table A.5). The tables have been extrapolated below 300 K, and these data should be
used with caution. The entropy datum of zero at 0 K cannot be illustrated by the evaluation of equation A.10, since there is a
singularity in this equation at 0 K, and in ny case there will be phase changes. Phase changes will lead to isothermal changes
in entropy, and each different phase will have a different temperature/entropy relationship. Instead, use is made of the values
of entropy for substances at 25°C in their standard state at a pressure of 1 bar (WARNING - Many sources use a datum pressure
of 1 atm).

The entropy can be evaluated at other pressures from:

(All

The Internal Energy ( U) and Gibbs Function (G) are by defmition:

H = u + pV = u + ROT and (A12

With the superscript o referring to the datum pressure (p 0 ) of 1 bar. The Gibbs function can be evaluated at other pressures in
a similar way to the entropy (Equation A.ll), and through the use of this equation:

(A.13

The changes inS and G between state 1 (p" T1) and state 2 (p2 , TJ, for a gas or vapour, are given by:

(A14

and

(A15

When the entropy and Gibbs Function of a mixture is being evaluated, then the properties of the individual constituents are
summed, but the pressures (p 1 and p 2) now refer to the partial pressures of each constituent.

The use of these tables in combustion calculations, is best illustrated by an example.

EXAMPLE a mixture of carbon monoxide and 10% excess air at 25°C is burnt at constant pressure, and it is assumed that
no carbon monoxide is present in the products. Treat air as 19% nitrogen and 21% oxygen, and estimate the
adiabatic flame temperature.
Solution

The stoichiometric equation is: CO + x(02 + 79/21 N 2) ..... C02 + 79x/21 N2

Balancing of the oxygen atoms gives: 1 + 2x = 2

With 10% excess air the combustion equation is:
 APPENDIX A- THERMODYNAMIC DATA A.5

At 25°C, the enthalpy of the reactants (HR) is: HR = -110.525 + 0.55(0 + 0) = -110.525 MJ!kmol_CO
Since the flame is adiabatic, then Hp = HR = -110.525 MJ!kmol_CO

Thus a temperature has to be found, at which the enthalpy of the products will sum to -110.525 MJ!kmol.

1'1 Guess 2000 K

HP, 2rm =1 X -302.128 + 0.05 X 59.171 + 2.07 X 56.114 = -183.013

2nd Guess 3000 K

Hp;3CXYJ =1 X -240.621 + 0.05 X 98.116 + 2.07 X 92.754 = -43.714

The 3nt guess can be based on linear interpolation:

T3 = 2000 + 1000x(-110.525 + 183.013)/(-43.714 + 183.013) = 2520 K

More accurate interpolation of the tables would lead to a temperature of 2523 K, but this is of limited purpose, since dissociation
results in a temperature of about 2350 K.

A.2.2 Equilibrium Constants

Chemical reactions move towards an equilibrium in which both the reactants and products are present. If the concentration of
the products is much greater than that of the reactants, then the reaction is said to be 'complete'. However, at the elevated
temperatures associated with combustion there may be reactants, products, and partial products of combustion (eg CO) all present.
Chemical reactions proceed in such a way as to minimise the Gibbs energy of the system, since this is the requirement for any
system to be in equilibrium. This can be established by considering equation 2.11:

(2.11)

If a system has the capability for doing work, then the Gibbs energy will be reduced, thus when no more work can be done, the
system will be in equilibrium and the Gibbs energy will be a minimum. For reacting mixtures it is helpful to introduce a
parameter to define the extent of a reaction (0.

At a constant temperature and pressure, consider a reaction in which A is in equilibrium with B:

For an infinitesimal changed~ of A into B:

the change in amount of A present is dnA = -d~, and

the change in amount of B present is dn 8 = +d~. (A.16

The change in Gibbs energy at constant temperature and pressure, when the concentration of a species changes (with no other
changes in composition of the mixture) is known as its chemical potential (p.). Thus

p. = (oG!on)r.p.nj (A.l7

The subscript nj indicating that there is no change in the amounts of any of the other species that might be present.

For our simple system with only substances A and B, then the change in Gibbs energy is given by:
A.6 Introduction to Internal Combustion Engines- SOLUTIONS

dG = (()Gf()n)r,p,ldJdnA + (iJG/()n)r,p,nA.dnB = P.AdnA + p.8 dn8

= -p.Ad~ + P.sd~ (A.l8

The change in Gibbs energy with a change in the extent of the reaction is:

(A.l9

and at equilibrium (iJG/iJ~h.p = 0. (A.20

Since the Gibbs energy is now a minimum, there can be no scope for the system to do any work, and the system will be at
equilibrium.

This now needs to be extended to a multi-component reaction, in which a kmols of species A, b kmols of species B and so on
react to produce c kmols of species C, d kmols of species D:

aA + bB ... ce + dD or, aA + bB - cC - dD = 0

This can be generalised as: (A.21

where "; is the stoichiometric coefficient of species A;.

When the extent of the reaction changes by d~, the amounts of the reactants and products change by:

dnA = -adt dn 8 = -bdt dnc = +cd~, and dn 0 = +dd~, (A.22

and in general (A.23

So, at constant pressure and temperature, the change in Gibbs energy is:

(A.24

and in general: dG = (Ev;p.;)dt and (A.25

and at equilibrium (iJG/iJ~)r,p = 0, so Ev;p.; = 0. (A.26

For species i: P.; = (iJG/iJn;)r,p,nj (A.l7

For a pure substance, the chemical potential (p.;) is simply the molar Gibbs energy Gin;. For one mole of gas:

(A.l3

so (A.27

where the superscript o refers to the use of a pressure datum of 1 bar.

For gaseous species i with ideal gas behaviour (enthalpy is not a function of pressure):

(A.28

or (A.29

where p*; represents the numerical value of the partial pressure of component i, when the pressure is expressed in units
of bar.
 APPENDIX A- THERMODYNAMIC DATA A.7

For the mixture at equilibrium: Ev;p.; = 0 (A.26

Combining equations A.26 and A.29 gives:

or (A.30

where !:J.G 0 = Ev;G; 0 , the change in Gibbs (or free) energy for the reaction,

and (A.31

where KP is the equilibrium constant of the reaction.

This is more frequently expressed as KP = ITp*t, with II denoting the product of the terms that follow. The equilibrium constant
has a strong temperature dependency, so it is convenient to tabulate lnKP" Although it has no pressure dependency, it is essential
to use the appropriate pressure units for the partial pressures unless Ev; = 0.

For the multicomponent reaction aA + bB.,... cC + dD:

(3.6

Remembering that p*; is the numerical value of the partial pressure of component i, when the pressure is expressed in units of
bar.

The equilibrium constant can be determined from the change in Gibbs energy of the reaction at the relevant temperature:

(A.32

Thus the equilibrium constants can be calculated from the Gibbs energy values in Tables A.4 and A.5, and this is indeed how
Table A.6 has been produced.

Tabulations of the equilibrium constants can be found in many sources (e.g. Howatson et al (1991), Haywood (1982) and Rogers
and Mayhew (1988)). For calculations, an analytical expression is frequently more convenient, and an appropriate form can be
found by dividing the equation for the Gibbs energy by R0 T. Such an equation was used by Olikara and Borman (1975).

(A.33

Who evaluated these coefficients for a number of equilibria in the range 600 to 4000 K. Olikara and Borman used a temperature
unit of kK and pressure units of atmospheres; in Table A.2 the pressure units have been converted to bar.

Regardless of the source of the equilibrium constant data, it is essential to pay strict attention to:

a) the pressure units

b) the form of the equation
A.8 Introduction to Internal Combustion Engines- SOLUTIONS

Table A.2 Coefficients for the evaluation of Log 1~; pressure units- bar, temperature units- kK

Constants
A B c D E
Reaction

'hH2 +:t H 0.432168 -0.112464 E2 0.266983 E1 -0.745744 E-1 0.242484 E-2

1h02 +:t 0 0.310805 -0.129540 E2 0.3214932 E1 -0.738336 E-1 0.344645 E-2

'hN2 +:t N 0.389716 -0.245828 E2 0.3142192 E1 -0.963730 E-1 0.585643 E-2

'h02 + 'hH2 +:t -0.141784 -0.213308 E1 0.853461 0.355015 E-1 -0.310227 E-2
OH

1hN 2 + 'h02 +:t 0.150879 E-1 -0.470959 E1 0.646096 0.272805 E-2 -0.154444 E-2
NO

H2 + 'h02 +:t -0.752364 0.124210 E2 -0.262575 E1 0.259556 -0.162687 E-1

H20

co+ 11202 -0.415302 E-2 0.148627 E2 -0.475460 E1 0.124699 -900227 E-2

+:tC02

Consider now the equilibrium between H 20, Hand OH, which is not detailed in Table A.2.

(A.34

However, it will be shown..how this can be reformulated in terms of the following tabulated equilibria:
Equation 4.11 can be rewritten as:

Thus (A.35
Kp,Hp
 APPENDIX A- THERMODYNAMIC DATA A.9

112
Y2H2 ¢ H Kp,ll = PH/PH2

%02 + Y2H2 ¢ OH Kp,OH = PoHI (PH1122 *Po112)

l

H2 + %02 ¢ H 20 Kp,H2o = PH2oi(PH2 * Po112)

2

PH PoH
*

This result can be generalised, and applied to the values of the equilibrium constants of formation of species (K1) from the
elements in their standard state. Thf? JANAF Tables (1983) tabulate log1J(1 for numerous species. For elements in their standard
state (e.g. N2 , 0 2 , He etc) log1J(1 is zero.

(A.36

A.3 Thermodynamic Data

The following fuel properties have been obtained from the listings of 'Physical and Thermodynamic Properties of Pure Chemicals'
by Daubert & Danner (1989). This comprehensive compilation covers the properties of solids, liquids and gases, with analytical
expressions and coefficients that enable the temperature dependency of the following properties to be determined:

Solid density
Liquid density
Vapour pressure
Enthalpy of vaporisation
Solid spe~ific heat capacity
Liquid specific heat capacity
Ideal gas specific heat capacity
Second virial coefficient (polynomials used in the Equation of State)
Liquid viscosity
Vapour viscosity
Liquid thermal conductivity
Vapour thermal conductivity
Surface tension
A.lO Introduction to Internal Combustion Engines- SOLUTIONS

Table A.3 Boiling Points, Enthalpy of Vaporisation, Liquid Density and Specific Heat Capacity, Molar Masses,
Standard Enthalpy of Fonnation, Standard State Entropy, and Calorific Values for fuels derived from
Daubert & Danner (1989).

Fuel Formula Boiling Point Enthalpy of Vaporisation' Densi~ 1

at 1 atm ( 0 C} at 298.15K (MJ!kmol) (kg/m ) kJ ~olK
Methane CH4 -161.5 8.171 422.5 57"
Propane C3Hs -42.0 18.743 582.5 106.3b
Benzene CJI6 80.1 33.790 872.9 135.6
Toluene C7Hs 110.6 38.341 864.7 156.1
n-Heptane C1H16 98.4 36.630 681.5 224.7
!so-octane CsH,s 99.2 35.142 690.4 236.4
(2,2,4-trimethy~entane)
n-Hexadecane ( etane) C,JI34 286.9 79.641 769.7 501.7
aMethylnaphthalene C10H7CH3 244.7 59.387 1017.2 224.4c
Methanol CH30H 64.7 38.012 789.6 81.6
Ethanol C2H50H 78.3 42.512 785.9 113.0
Nitro methane CH3N02 101.2 38.365 1112.7 106.3

M H sn Catonftc Vatues4 at 298.15K

Fuel Formula kglkmol MJ!kmol kJ!kmolK MJ!kmol MJ/kg
Methane CH4 16.043 -74.52 186.27 802.64 50.031
Propane C3Hs 44.096 -104.68 270.2 2043.15 46.334
Benzene CJI6 78.114 82.93 269.20 3169.47 40.575
Toluene C1Hs 92.141 50.00 319.74 3771.88 40.936
n-Heptane C1H16 100.204 -187.65 427.98 4501.53 44.924
!so-octane CsH,s 114.231 -224.01 422.96 5100.50 44.651
(2,2,4-trimethylpentane)
n-Hexadecane (Cetane) C,JI34 226.446 -374.17 781.02 10033.03 44.307
aMethylnaphthalene C 10H7CH3 142.2 116.86 377.44 5654.61 39.765
Methanol CH 30H 32.042 -200.94 239.88 676.22 21.104
Ethanol C2H50H 46.069 -234.95 280.64 1277.55 27.731
Nitromethane CH 3N0 2 61.040 -74.73 275.01 681.52 11.165

note 1 Properties have been evaluated at 25°C, except when a substance is a gas at this temperature, in which case the
evaluation refers to the normal boiling point.
note 2 These data were obtained from the 'Handbook of Chemistry and Physics' (70th ed CRC Press, 1990), with the exception
of the following data:
a Y S Touloukian & T Makita 'Specific Heat, nonmetallic liquids and gases', (Plenum, 1970)
b International Critical Tables, vol V, (McGraw Hill 1929)
c Daubert & Danner (1989)
note 3 The entropy values tabulated here for the standard state (S0 ) refer to a pressure of 1 atm (1.01325 bar), whilst the
entropy values evaluated in Tables A.4 and A.5 use a pressure of 1 bar as the datum; this accounts for the slight
differences in the numerical values for entropy at 298.15K. The standard state values can refer to a hypothetical state,
and this is indeed the case for many of these fuels, which cannot exist as a vapour at a pressure of 1 atm and a
temperature of 298.15K.
note 4 The calorific value-s have been determined from the difference in the enthalpies of formation of the fuel and products,
with all reactants and products in the vapour phase, this is known as the Net or Lower Calorific Value (LCV). When
the water vapour in the products of combustion has been condensed to its liquid state, the calorific value of the fuel is
known as the Gross or Higher Calorific Value (HCV), thus:
HCV = LCV + (n XHrg)H2o
where the enthalpy of condensation of the water vapour, Hrg = 43.99 MJ/kmol_H20.
 APPENDIX A- THERMODYNAMIC DATA A.ll

Table A.4 Thennodynamic data for gaseous species

'A B S 0 LUTE' M 0 LA R E N T H A L P Y
(MJ/kmol)
T(K) Air N, o, H, co co, H20 NO Ar OH 0 H T(K)

0 -8.774 -8.823 -8.709 -8.222 -119.363 -402.239 -251.763 81.717 -6.201 32.721 243.041 211.787 0
100 -5.784 -5.812 -5.755 -5.584 -116.336 -399.897 -248.414 84.423 -4.121 35.180 245.154 213.866 100
200 -2.855 -2.864 -2.858 -2.804 -113.387 -396.934 -245.097 87.231 -2.041 37.716 247.264 215.944 200
298.15 0.0 0.0 0.0 0.0 -110.525 -393.512 -241.824 90.080 .000 40.277 249.333 217.984 298.15
300 0.053 0.053 0.054 0.056 -110.471 -393.443 -241.761 90.135 .038 40.326 249.372 218.023 300
400 2.973 2.969 3.028 2.959 -107.550 -389.509 -238.371 93.125 2.118 43.005 251.477 220.101 400
T(K) Air N, o, H, CO CO, H,O NO Ar OH 0 H T(K)

500 5.930 5.909 6.089 5.880 -104.594 -385.208 -234.899 96.195 4.198 45.752 253.580 222.180 500
600 8.942 8.893 9.247 8. 811 -101.584 -380.605 -231.326 99.337 6.278 48.564 255.681 224.259 600
700 12.018 11.934 12.500 11.750 -98.505 -375.753 -227.639 102.547 8.358 51.437 257.780 226.337 700
800 15.164 15.042 15.837 14.704 -95.353 -370.699 -223.831 105.817 10.438 54.369 259.876 228.416 800
900 18.379 18.219 19.244 17.681 -92.128 -365.477 -219.899 109.143 12.518 57.358 261.971 230.495 900
T(K) Air N, o, H, CO C0 2 H,O NO Ar OH 0 H T(K)

1000 21.655 21.459 22.708 20.686 -88.838 -360.112 -215.841 112.518 14.598 60.399 264.063 232.573 1000
1100 24.984 24.756 26.213 23.729 -85.496 -354.624 -211.652 115.939 16.678 63.492 266.154 234.652 1100
1200 28.357 28.100 29.754 26.814 -82.107 -349.051 -207.337 119.400 18.758 66.633 268.243 236.730 1200
1300 31.772 31.489 33.328 29.942 -78.676 -343.395 -202.904 122.897 20.838 69.820 270.330 238.809 1300
1400 35.224 34.917 36.934 33.112 -75.208 -337.664 -198.359 126.427 22.918 73.050 272.416 240.888 1400
T(K) Air N, o, H, CO CO, H,O NO Ar OH 0 H T(K)

1500 38.711 38.380 40.571 36.323 -71.707 -331.867 -193.711 129.986 24.998 76.322 274.501 242.966 1500
1600 42.228 41.876 44.237 39.574 -68.176 -326.012 -188.966 133.572 27.078 79.634 276.585 245.045 1600
1700 45.774 45.400 47.931 42.865 -64.618 -320.105 -184.131 137.180 29.158 82.982 278.668 247.124 1700
1800 49.345 48.949 51.652 46.194 -61.037 -314.151 -179.212 140.808 31.238 86.365 280.751 249.202 1800
1900 52.940 52.522 55.399 49.560 -57.435 -308.158 -174.215 144.454 33.318 89.781 282.833 251.281 1900
T(K) Air N, o, H, CO CO, H,O NO Ar OH 0 H T(K)

2000 56.556 56.114 59.171 52.962 -53.815 -302.128 -169.146 148.116 35.398 93.228 284.915 253.359 2000
2100 60.190 59.725 62.967 56.399 -50.178 -296.068 -164.009 151.792 37.478 96.705 286.997 255.438 2100
2200 63.842 63.351 66.787 59.870 -46.527 -289.981 -158.810 155.480 39.558 100.208 289.079 257.517 2200
2300 67.510 66.991 70.630 63.373 -42.863 -283.870 -153.553 159.179 41.638 103.738 291.162 259.595 2300
2400 71.192 70.644 74.495 66.908 -39.189 -277.737 -148.243 162.886 43.718 107.292 293.246 261.674 2400
T(K) Air N, o, H, CO C0 2 H,O NO Ar OH 0 H T(K)

2500 74.887 74.308 78.381' 70.474 -35.504 -271.587 -142.883 166.602 45.797 110.868 295.330 263.753 2500
2600 78.595 77.981 82.288 74.068 -31.811 -265.420 -137.478 170.326 47.877 114.465 297.416 265.831 2600
2700 82.313 81.664 86.216 77.691 -28.111 -259.239 -132.031 174.055 49.957 118.083 299.503 267.910 2700
2800 86.041 85.354 90.163 81.341 -24.403 -253.045 -126.545 177.790 52.037 121.718 301.592 269.988 2800
2900 89.779 89.051 94. 13 0 85.016 -20.689 -246.838 -121.022 181.531 54.117 125.371 303.684 272.067 2900
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

3000 93.527 92.754 98.116 88.716 -16.969 -240.621 -115.467 185.276 56.197 129.040 305.777 274.146 3000
3100 97.282 96.464 102.120 92.439 -13.244 -234.393 -109.881 189.026 58.277 132.724 307.872 276.224 3100
3200 101.046 100.179 106.142 96.185 -9.514 -228.155 -104.266 192.780 60.357 136.421 309.971 278.303 3200
3300 104.818 103.900 110.182 99.953 -5.778 -221.907 -98.625 196.538 62.437 140.132 312.072 280.382 3300
3400 108.597 107.625 114.238 103.741 -2.039 -215.650 -92.959 200.300 64.517 143.855 314.177 282.460 3400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

3500 112.383 111.356 118.312 107.549 1.706 -209.383 -87.271 204.066 66.597 147.589 316.284 284.539 3500
3600 116.177 115.091 122.402 111.377 5.455 -203.106 -81.561 207.836 68.677 151.334 318.396 286.617 3600
3700 119.978 118.832 126.507 115.223 9.209 -196.819 -75.832 211.610 70.757 155.089 320.511 288.696 3700
3800 123.786 122.577 130.627 119.086 12.968 -190.522 -70.083 215.389 72.837 158.853 322.630 290.775 3800
3900 127.600 126.326 134.762 122.968 16.731 -184.215 -64.317 219.171 74.917 162.627 324.754 292.853 3900
T(K) Air N, o, H, co co, H20 NO Ar OH 0 H T(K)

4000 131.421 130.081 138. 911 126.866 20.499 -177.898 -58.533 222.958 76.997 166.409 326.881 294.932 4000
4100 135.249 133.840 143.074 130.781 24.272 -171.570 -52.733 226.748 79.077 170.200 329.014 297.011 4100
4200 139.083 137.604 147.249 134.713 28.049 -165.232 -46.918 230.543 81.157 173.998 331.150 299.089 4200
4300 142.923 141.373 151.436 138.662 31.831 -158.884 -41.088 234.342 83.237 177.805 333.292 301.168 4300
4400 146.769 145.147 155.634 142.627 35.617 -152.526 -35.242 238.145 85.317 181.620 335.439 303.246 4400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

4500 150.621 148.925 159.842 146.610 39.408 -146.159 -29.383 241.951 87.397 185.443 337.590 305.325 4500
4600 154.478 152.707 164.060 150.610 43.202 -139.783 -23.509 245.761 89.477 189.273 339.747 307.404 4600
4700 158.340 156.493 168.286 154.628 47.000 -133.400 -17.621 249.574 91.557 193.112 341.909 309.482 4700
4800 162.206 160.282 172.519 158.665 50.801 -127.012 -11.719 253.390 93.636 196.960 344.076 311.561 4800
4900 166.075 164.074 176.758 162.722 54.604 -120.619 -5.803 257.207 95.716 200.816 346.249 313.640 4900
5000 169.947 167.868 -181.001 166.800 58.409 -114.224 .127 261.025 97.796 204.682 348.427 315.718 5000
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

Note
The term 'ABSOLUTE' Molar Enthalpy adopted here, uses a datum of zero enthalpy for elements when they are in their
standard state at a temperature of 25°C. The enthalpy of any molecule at 25°C will thus correspond to its enthalpy of formation,
!:lHt. The tables have been extrapolated below 300 K, and these data should be used with caution.

The enthalpies have been evaluated by the integration of a polynomial function that describes the molar specific heat capacity ( C )
variation with temperature. The difference in Enthalpy of Reactants and Products at 25°C will thus correspond to the Constarit
Pressure Calorific Value of the reaction.
A.12 Introduction to Internal Combustion Engines- SOLUTIONS

'A B S 0 L U T E' M 0 LA R INTERNAL E N E R G Y

(MJ/kmol)

T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

0 -8.774 -8.823 -8.709 -8.222 -119.363 -402.239 -251.763 81.717 -6.201 32.721 243.041 211.787 0
100 -6.615 -6.643 -6.586 -6.415 -117.167 -400.729 -249.246 83.592 -4.953 34.349 244.322 213.034 100
200 -4.518 -4.527 -4.521 -4.467 -115.050 -398.597 -246.759 85.569 -3.704 36.053 245.601 214.281 200
298.15 -2.480 -2.480 -2.479 -2.476 -113.004 -395.991 -244.303 87.601 -2.479 37.798 246.854 215.505 298.15
300 -2.441 -2.441 -2.440 -2.438 -112.966 -395.937 -244.256 87.640 -2.456 37.831 246.877 215.528 300
400 -.352 -.356 -.298 -.367 -110.876 -392.835 -241.697 89.799 -1.207 39.680 248.151 216.776 400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)
500 1. 773 1. 752 1.931 1.723 -108.751 -389.366 -239.057 92.037 .041 41.595 249.423 218.023 500
600 3.953 3.904 4.258 3.822 -106.572 -385.594 -236.314 94.349 1.290 43.575 250.692 219.270 600
700 6.198 6.114 6.680 5.930 -104.325 -381.574 -233.459 96.727 2.538 45.617 251.959 220.517 700
800 8.513 8.390 9.186 8.053 -102.004 -377.351 -230.483 99.166 3.787 47.718 253.225 221.764 800
900 10.896 10.735 11.761 10.198 -99.611 -372.960 -227.382 101.660 5.035 49.874 254.487 223.012 900
T(K) Air N, o, H, co co, H2 0 NO Ar OH 0 H T(K)
1000 13.341 13.145 14.393 12.371 -97.153 -368.427 -224.155 104.204 6.284 52.085 255.749 224.259 1000
1100 15.838 15.610 17.067 14.583 -94.642 -363.770 -220.798 106.793 7.532 54.346 257.008 225.506 1100
1200 18.380 18.123 19.777 16.837 -92.084 -359.028 -217.315 109.422 8.781 56.655 258.265 226.753 1200
1300 20.963 20.680 22.519 19.133 -89.485 -354.204 -213.713 112.088 10.029 59.011 259.521 228.000 1300
1400 23.584 23.276 25.294 21.472 -86.849 -349.304 -210.000 114.787 11.278 61.410 260.776 229.247 1400
T(K) Air N, o, H, co co, H2 0 NO Ar OH 0 H T(K)
1500 26.239 25.908 28.099 23.851 -84.179 -344.339 -206.183 117.515 12.526 63.851 262.029 230.495 1500
1600 28.925 28.572 30.934 26.271 -81.479 -339.315 -202.270 120.268 13.775 66.330 263.282 231.742 1600
1700 31.639 31.265 33.796 28.730 -78.753 -334.239 -198.266 123.045 15.023 68.847 264.534 232.989 1700
1800 34.379 33.983 36.686 31.228 -76.003 -329.117 -194.178 125.842 16.272 71.399 265.785 234.236 1800
1900 37.143 36.724 39.601 33.762 -73.233 -323.955 -190.013 128.657 17.520 73.983 267.035 235.483 1900
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

2000 39.927 39.485 42.542 36.333 -70.444 -318.757 -185.775 131.487 18.769 76.599 268.286 236.730 2000
2100 42.730 42.264 45.507 38.938 -67.638 -313.529 -181.469 134.332 20.017 79.244 269.536 237.978 2100
2200 45.551 45.059 48.495 41.578 -64.819 -308.273 -177.102 137.188 21.266 81.916 270.787 239.225 2200
2300 48.387 47.868 51.507 44.250 -61.987 -302.993 -172.676 140.055 22.514 84.615 272.039 240.4 72 2300
2400 51.237 50.689 54.540 46.954 -59.144 -297.692 -168.198 142.932 23.763 87.337 273.291 241.719 2400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)
2500 54.101 53.521 57.595 49.688 -56.291 -292.373 -163.670 145.816 25.011 90.082 274.544 242.966 2500
2600 56.97'7 56.364 60.670" 52.451 -53.429 -287.038 -159.096 148.708 26.260 92.848 275.798 244.213 2600
2700 59.864 59.214 63.767 55.242 -50.560 -281.688 -154.480 151.606 27.508 95.633 277.054 245.461 2700
2800 62.761 62.073 66.883 58.060 -47.683 -276.325 -149.825 154.510 28.757 98.438 278.312 246.708 2800
2900 65.667 64.939 70.018 60.904 -44.801 -270.950 -145.134 157.419 30.005 101.259 279.571 247.955 2900
T(K) Air N, o, H, co co, H2 0 NO Ar OH 0 H T(K)
3000 68.583 67.811 73.172 63.772 -41.913 -265.564 -140.410 160.333 31.254 104.096 280.833 249.202 3000
3100 71.507 70.689 76.345 66.664 -39.019 -260.168 -135.656 163.251 32.502 106.949 282.098 250.449 3100
3200 74.440 73.573 79.535 69.579 -36.120 -254.762 -130.872 166.173 33.751 109.815 283.364 251.697 3200
3300 77.380 76.462 82.744 72.515 -33.216 -249.345 -126.063 169.100 34.999 112.694 284.634 252.944 3300
3400 80.328 79.356 85.969 75.472 -30.308 -243.919 -121.229 172.031 36.248 115.585 285.907 254.191 3400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)
3500 83.283 82.255 89.211 78.448 -27.395 -238.484 -116.372 174.965 37.496 118.488 287.184 255.438 3500
3600 86.245 85.159 92.469 81.444 -24.477 -233.038 -111.494 177.904 38.745 121.402 288.464 256.685 3600
3700 89.214 88.068 95.743 84.459 -21.555 -227.583 -106.595 180.847 39.993 124.325 289.747 257.932 3700
3800 92.191 90.981 99.032 87.491 -18.627 -222 .117 -101.678 183.794 41.242 127.258 291.035 259.180 3800
3900 95.174 93.900 102.336 90.541 -15.696 -216.642 -96.743 186.744 42.490 130.200 292.327 260.427 3900
T(K) Air N, o, H, co co, H2 0 NO Ar OH 0 H T(K)
4000 98.163 96.823 105.653 93.608 -12.759 -211.156 -91.791 189.700 43.739 133.151 293.623 261.674 4000
4100 101.160 99.751 108.984 96.692 -9.818 -205.659 -86.823 192.659 44.987 136.110 294.924 262.921 4100
4200 104.162 102.684 112.328 99.792 -6.872 -200.153 -81.839 195.622 46.236 139.077 296.229 264.168 4200
4300 107.171 105.621 115.684 102.909 -3.922 -194.636 -76.840 198.590 47.484 142.053 297.540 265.415 4300
4400 110.186 108.563 119.050 106.043 -.967 -189.109 -71.826 201.561 48.733 145.036 298.855 266.663 4400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

4500 113.206 111.509 122.427 109.195 1. 993 -183.574 -66.798 204.536 49.981 148.027 300.175 267.910 4500
4600 116.232 114.460 125.813 112.363 4.956 -178.030 -61.756 207.515 51.230 151.027 301.500 269.157 4600
4700 119.262 117.414 129.208 115.550 7.922 -172.479 -56.699 210.496 52.478 154.034 302.831 270.404 4700
4800 122.296 120.372 132.609 118.756 10.892 -166.921 -51.629 213.480 53.727 157.050 304.167 271.651 4800
4900 125.334 123.333 136.017 121.981 13.863 -161.360 -46.544 216.465 54.975 160.075 305.508 272.898 4900
5000 128.374 126.296 139.429 125.228 16.836 -155.797 -41.446 219.452 56.224 163.110 306.854 274.146 5000
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

Note
The term 'ABSOLUTE' Molar Internal Energy adopted here, uses the same datum as the enthalpy table, namely a datum
of zero enthalpy for elements when they are in their standard state at a temperature of 25°C. The tables have been
extrapolated below 300 K, and these data should be used with caution.
The difference in Internal Energy of Reactants and Products at 25 oc will thus correspond to the Constant Volume Calorific
Value of the reaction. When there is a difference in the number of kmols of gaseous reactants and products, the Constant
Pressure Calorific Value (the difference in Enthalpy of Reactants and Products at 25°C) will differ from the Constant
Volume Calorific Value .
 APPENDIX A- THERMODYNAMIC DATA A.13

'A B S 0 L U T E' M 0 LA R E N T R 0 P Y
(kJ/kmolK)
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
100 162.167 159.512 173.442 100.054 165.543 179.639 152.512 179.394 132.087 157.595 138.332 92.008 100
200 182.484 179.963 193.531 119.277 186.001 199.953 175.510 198.821 146.504 175.143 152.960 106.416 200
298.15 194.096 191.614 205.150 130.689 197.646 213.811 188.820 210.398 154.809 185.550 161.376 114.715 298.15
300 194.276 191.794 205.332 130.868 197.826 214.041 189.028 210.580 154.938 185.713 161.507 114.844 300
400 202.675 200.182 213.880 139.216 206.229 225.329 198.775 219.176 160.921 193.418 167.564 120.824 400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

500 209.272 206.741 220.707 145.734 212.823 234.913 206.519 226.023 165.563 199.545 172.257 125.462 500
600 214.760 212.179 226.463 151.077 218.310 243.299 213.032 231.751 169.355 204.669 176.087 129.252 600
700 219.502 216.866 231.476 155.608 223.054 250.773 218.713 236.698 172.561 209.097 179.322 132.456 700
800 223.701 221.015 235.931 159.553 227.262 257.519 223.795 241.064 175.339 213.012 182.122 135.232 BOO
900 227.487 224.756 239.943 163.058 231.060 263.668 228.425 244.980 177.788 216.531 184.589 137.680 900
T(K) Air N, o, H, co co, H2 0 NO Ar OH 0 H T(K)

1000 230.938 228.170 243.591 166.224 234.525 269.319 232.700 248.536 179.980 219.735 186.793 139.870 1000
1100 234.111 231.312 246.935 169.127 237.712 274.541 236.693 251.796 181.962 222.682 188.786 141.851 1100
1200 237.046 234.222 250.015 171.811 240.661 279.390 240.447 254.807 183.772 225.415 190.604 143.660 1200
1300 239.779 236.934 252.876 174.315 243.407 283.917 243.995 257.606 185.437 227.965 192.275 145. 324 1300
1400 242.337 239.474 255.548 176.664 245.976 288.163 247.362 260.222 186.978 230.359 193.821 146.864 1400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

1500 244.743 241.863 258.057 178.879 248.392 292.162 250.569 262.678 188.413 232.617 195.259 148.298 1500
1600 247.013 244.119 260.423 180.977 250.671 295.941 253.631 264.991 189.756 234.754 196.604 149.640 1600
1700 249.162 246.255 262.662 182.972 252.827 299.522 256.562 267.179 191.017 236.783 197.867 150.900 1700
1800 251.204 248.284 264.789 184.875 254.874 302.925 259.373 269.253 192.206 238.717 199.057 152.088 1800
1900 253.147 250.216 266.815 186.694 256.822 306.166 262.075 271.224 193.330 240.564 200.183 153.212 1900
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

2000 255.002 252.058 268.750 188.439 258.679 309.258 264.675 273.102 194.397 242.332 201.251 154.278 2000
2100 256.775 253.820 270.602 190.116 260.453 312.215 267.181 274.896 195.412 244.028 202.267 155.292 2100
2200 258.474 255.507 272.379 191.731 262.152 315.047 269.600 276.611 196.379 245.658 203.235 156.259 2200
2300 260.104 257.125 274.087 193.288 263.780 317.763 271.936 278.255 197.304 247.227 204.161 157.183 2300
2400 261.671 258.680 275.732 194.793 265.344 320.373 274.196 279.833 198.189 248.739 205.048 158.068 2400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

2500 263.180 260.175 277.318 196.248 266.848 322.884 276.384 281.350 199.038 250.199 205.899 158.916 2500
2600 264.634 261.616 278.851 197.658 268.296 325.302 278.504 282.810 199.854 251.610 206.717 159.732 2600
2700 266.037 263.006 280.333 199.025 269.693 327.635 280.560 284.218 200.639 252.975 207.505 160.516 2700
2800 267.393 264.348 281.768 200.352 271.041 329.888 282.555 285.576 201.395 254.297 208.264 161.272 2800
2900 268.705 265.645 283.160 201.642 272.345 332.066 284.493 286.889 202.125 255.579 208.998 162.001 2900
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

3000 269.975 266.901 284.512 202.896 273.606 334.173 286.376 288.159 202.830 256.823 209.708 162.706 3000
3100 271.206 268.117 285.825 204.117 274.827 336.216 288.208 289.388 203.513 258.031 210.395 163.388 3100
3200 272.401 269.296 287.102 205.306 276.012 338.196 289.990 290.580 204.173 259.205 211.061 164.048 3200
3300 273.562 270.441 288.345 206.466 277.161 340.118 291.726 291.736 204.813 260.347 211.708 164.687 3300
3400 274.690 271.554 289.556 207.597 278.277 341.987 293.417 292.860 205.434 261.458 212.336 165.308 3400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

3500 275.788 272.635 290.736 208.701 279.363 343.803 295.066 293.951 206.037 262.540 212.947 165.910 3500
3600 276.857 273.687 291.889 209.779 280.419 345.571 296.675 295.013 206.623 263.595 213.542 166.496 3600
3700 277.898 274.712 293.013 210.832 281.448 347.294 298.245 296.047 207.193 264.624 214.121 167.065 3700
3800 278.913 275.711 294.112 211.863 282.450 348.973 299.778 297.055 207.747 265.628 214.687 167.620 3800
3900 279.904 276.685 295.186 212.871 283.427 350.612 301.275 298.037 208.288 266.608 215.238 168.160 3900
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

4000 280.872 277.635 296.237 213.858 284.381 352.211 302.740 298.996 208.814 267.566 215.777 168.686 4000
4100 281.817 278.564 297.264 214.825 285.313 353.773 304.172 299.932 209.328 268.502 216.303 169.199 4100
4200 282.741 279.471 298.271 215.772 286.223 355.301 305.573 300.847 209.829 269.417 216.818 169.700 4200
4300 283.644 280.357 299.256 216.701 287.113 356.795 306.945 301.741 210.318 270.313 217.322 170.189 4300
4400 284.529 281.225 300.221 217.613 287.984 358.256 308.289 302.615 210.797 271.190 217.816 170.667 4400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

4500 285.394 282.074 301.167 218.508 288.836 359.687 309.606 303.470 211.264 272.049 218.299 171.134 4500
4600 286.242 282.905 302.094 219.387 289.669 361.088 310.897 304.308 211.721 272.891 218.773 171.591 4600
4700 287.072 283.719 303.002 220.251 290.486 362.461 312.163 305.128 212.168 273.717 219.238 172.038 4700
4800 287.886 284.517 303.894 221.101 291.286 363.806 313.406 305.931 212.606 274.527 219.695 172.476 4800
4900 288.684 285.299 304.768 221.938 292.071 365.124 314.625 306.718 213.035 275.322 220.142 172.904 4900
5000 289.466 286.066 305.625 222.762 292.839 366.416 315.823 307.489 213.455 276.103 220.582 173.324 5000
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

Note
The entropy is evaluated by the integration of dS = (CvfT)dT. When CP is described by a polynomial function there is
a singularity at 0 K. The datum is provided by the values of entropy for substances at 25°C in their standard state at a
pressure of 1 bar (WARNING - Many sources use a datum pressure of 1 atm). The entropy can be evaluated at other
pressures from:

With the superscript o referring to the datum pressure (p 0 ) of 1 bar. When the entropy of a mixture is being evaluated,
then the properties of the individual constituents are summed, but the pressure (p) now refers to the partial pressures of
each constituent.
A.14 Introduction to Internal Combustion Engines- SOLUTIONS

'A B S 0 L U T E' M 0 LA R G I B B S E N E R G Y
(MJ/kmol)

T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

0 -8.77 -8.82 -8.70 -8.22 -119.36 -402.23 -251.76 81.71 -6.20 32.72 243.04 211.78 0
100 -22.00 -21.76 -23.09 -15.58 -132.89 -417.86 -263.66 66.48 -17.33 19.42 231.32 204.66 100
200 -39.35 -38.85 -41.56 -26.66 -150.58 -436.92 -280.19 47.46 -31.34 2.68 216.67 194.66 200
298.15 -57.87 -57.13 -61.16 -38.96 -169.45 -457.25 -298.12 27.35 -46.15 -15.04 201.21 183.78 298.15
300 -58.23 -57.48 -61.54 -39.20 -169.81 -457.65 -298.47 26.96 -46.44 -15.38 200.92 183.57 300
400 -78.09 -77.10 -82.52 -52.72 -190.04 -479.64 -317.88 5.45 -62.25 -34.36 184.45 171.77 400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

500 -98.70 -97.46 -104.26 -66.98 -211.00 -502.66 -338.15 -16.81 -78.58 -54.02 167.45 159.44 500
600 -119.91 -118.41 -126.63 -81.83 -232.57 -526.58 -359.14 -39.71 -95.33 -74.23 150.02 146.70 600
700 -141.63 -139.87 -149.53 -97.17 -254.64 -551.29 -380.73 -63.14 -112.43 -94.93 132.25 133.61 700
800 -163.79 -161.77 -172.90 -112.93 -277.16 -576.71 -402.86 -87.03 -129.83 -116.04 114.17 120.23 800
900 -186.35 -184.06 -196.70 -129.07 -300.08 -602.77 -425.48 -111.33 -147.49 -137.52 95.84 106.58 900
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

1000 -209.28 -206.71 -220.88 -145.53 -323.36 -629.43 -448.54 -136.01 -165.38 -159.33 77.27 92.70 1000
1100 -232.53 -229.68 -245.41 -162.31 -346.97 -656.61 -472.01 -161.03 -183.48 -181.45 58.48 78.61 1100
1200 -256.09 -252.96 -270.26 -179.35 -370.90 -684.31 -495.87 -186.36 -201.76 -203.86 39.51 64.33 1200
1300 -279.94 -276.52 -295.41 -196.66 -395.10 -712.48 -520.09 -211.99 -220.23 -226.53 20.37 49.88 1300
1400 -304.04 -300.34 -320.83 -214.21 -419.57 -741.09 -544.66 -237.88 -238.85 -249.45 1. 06 35.27 1400
T(K) Air N, o, H, co co, H2 0 NO Ar OH 0 H T(K)

1500 -328.40 -324.41 -346.51 -231.99 -444.29 -770.11 -569.56 -264. 03 -257.62 -272.60 -18.38 20.51 1500
1600 -352.99 -348.71 -372.44 -249.98 -469.24 -799.51 -594.77 -290.41 -276.53 -295.97 -37.98 5.62 1600
1700 -377.80 -373.23 -398.59 -268.18 -494.42 -829.29 -620.28 -317.02 -295.57 -319.55 -57.70 -9.40 1700
1800 -402.82 -397.96 -424.96 -286.58 -519.81 -859.41 -646.08 -343.84 -314.73 -343.32 -77.55 -24.55 1800
1900 -428. 03 -422.88 -451.54 -305.16 -545.39 -889.87 -672.15 -370.87 -334.00 -367.29 -97.51 -39.82 1900
T(K) Air N, o, H, co co, H2 0 NO Ar OH 0 H T(K)

2000 -453.44 -448.00 -478.32 -323.91 -571.17 -920.64 -698.49 -398.08 -353.39 -391.43 -117.58 -55.19 2000
2100 -479.03 -473.29 -505.29 -342.84 -597.13 -951.71 -725.08 -425.48 -372.88 -415.75 -137.76 -70.67 2100
2200 -504.80 -498.76 -532.44 -361.93 -623.26 -983.08 -751.92 -453.06 -392.47 -440.23 -158.03 -86.25 2200
2300 -530.73 -524.39 -559.77 -381.18 -649.55 -1014.72 -779.00 -480.80 -412.16 -464.88 -178.40 -101.92 2300
2400 -556.81 -550.18 -587.26 -400.59 -676.01 -1046.63 -806.31 -508.71 -431.93 -489.68 -198.86 -117.68 2400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

2500 -583.06 -576.13 -614.91 -420.14 -702.62 -1078.79 -833.84 -536.77 -451.79 -514.63 -219.41 -133.53 2500
2600 -609.45 -602.22 -642.72" -439.84 -729.38 -1111.20 -861.58 -564.98 -4 71.74 -539.72 -240.04 -149.47 2600
2700 -635.98 -628.45 -670.68 -459.67 -756.28 -1143.85 -889.54 -593.33 -491.76 -564.95 -260.75 -165.48 2700
2800 -662.65 -654.82 -698.78 -479.64 -783.31 -1176.73 -917.69 -621.82 -511.87 -590.31 -281.54 -181.57 2800
2900 -689.46 -681.32 -727.03 -499.74 -810.48 -1209.82 -946.05 -650.44 -532.04 -615.80 -302.41 -197.73 2900
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

3000 -716.39 -707.94 -755.41 -519.97 -837.78 -1243.14 -974.59 -679.20 -552.29 -641.42 -323.34 -213.97 3000
3100 -743.45 -734.69 -783.93 -540.32 -865.20 -1276.66 -1003.32 -708.07 -572.61 -667.17 -344.35 -230.27 3100
3200 -770.63 -761.56 -812.58 -560.79 -892.75 -1310.38 -1032.23 -737.07 -592.99 -693.03 -365.42 -246.65 3200
3300 -797.93 -788.55 -841.35 -581.38 -920.41 -1344.29 -1061.32 -766.19 -613.44 -719.01 -386.56 -263.08 3300
3400 -825.35 -815.65 -870.25 -602.08 -948.18 -1378.40 -1090.57 -795.42 -633.95 -745.10 -407.76 -279.58 3400
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

3500 -852.87 -842.86 -899.26 -622.90 -976.06 -1412.69 -1120.00 -824.76 -654.53 -771.30 -429.03 -296.14 3500
3600 -880.50 -870.18 -928.39 -643.82 -1004.05 -1447.16 -1149.59 -854.21 -675.16 -797.60 -450.35 -312.76 3600
3700 -908.24 -897.60 -957.64 -664.85 -1032.14 -1481.80 -1179.33 -883.76 -695.85 -824.02 -471.73 -329.44 3700
3800 -936.08 -925.12 -986.99 -685.99 -1060.34 -1516.62 -1209.23 -913.42 -716.60 -850.53 -493.17 -346.18 3800
3900 -964.02 -952.74 -1016.46 -707.22 -1088.63 -1551.60 -1239.29 -943.17 -737.40 -877.14 -514.67 -362.97 3900
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

4000 -992.06 -980.46 -1046.03 -728.56 -1117.02 -1586.74 -1269.49 -973.02 -758.26 -903.85 -536.22 -379.81 4000
4100 -1020.20 -1008.27 -1075.71 -750.00 -1145.51 -1622.04 -1299.83 -1002.97 -779.16 -930.65 -557.83 -396.70 4100
4200 -1048.42 -1036.17 -1105.48 -771.53 -1174.08 -1657.49 -1330.32 -1033.01 -800.12 -957.55 -579.48 -413.65 4200
4300 -1076.74 -1064.16 -1135.36 -793.15 -1202.75 -1693.10 -1360.95 -1063.14 -821.13 -984.54 -601.19 -430.64 4300
4400 -1105.15 -1092.24 -1165.33 -814.87 -1231.51 -1728.85 -1391.71 -1093.36 -842.18 -1011.61 -622.95 -447.68 4400
T(K) Air N, o, H, co co, H2 0 NO Ar OH 0 H T(K)

4500 -1133.65 -1120.40 -1195.40 -836.67 -1260.35 -1764.75 -1422.60 -1123.66 -863.29 -1038.77 -644.75 -464.77 4500
4600 -1162.23 -1148.65 -1225.57 -858.57 -1289.27 -1800.78 -1453.63 -1154. OS -884.44 -1066.02 -666.61 -481.91 4600
4700 -1190.90 -1176.98 -1255.82 -880.55 -1318.28 -1836.96 -1484.78 -1184.52 -905.63 -1093.35 -688.51 -499.09 4700
4800 -1219.64 -1205.40 -1286.17 -902.62 -1347.37 -1873.28 -1516.06 -1215.07 -926.87 -1120.76 -710.45 -516.32 4800
4900 -1248.47 -1233.89 -1316.60 -924.77 -1376.54 -1909.72 -1547.46 -1245.71 -948.15 -1148.26 -732.44 -533.59 4900
5000 -1277.38 -1262.46 -1347.12 -947.00 -1405.78 -1946.30 -1578.99 -1276.42 -969.48 -1175.83 -754.48 -550.90 5000
T(K) Air N, o, H, co co, H,O NO Ar OH 0 H T(K)

Note
The Gibbs Function (G) is by definition: Go = H - TS 0

With the superscript o referring to the datum pressure (p 0 ) of 1 bar. The Gibbs function can be evaluated at other pressures in
a similar way to the entropy through the use of:

When the Gibbs Function of a mixture is being evaluated, then the properties of the individual constituents are summed, but the
pressure (p) now refers to the partial pressure of each constituent.
 APPENDIX A- THERMODYNAMIC DATA A.15

Table A.5 Thermodynamic data for fuels

ABSOLUTE MOLAR ENTHALPY

(MJ/kmol)

T(K) CH, C,H, C,H, CH,OH C,H,OH CH3 NO, T(K)

0 -B2.660 -115.697 74.264 36.B27 -213.096 -1B3.604 -431.071 100.199 -210.113 -246.415 -B4.B21 0
100 -80.470 -114.640 73.170 36.863 -210.350 -188.380 -425.008 98.184 -207.653 -244.471 -83.125 100
200 -77.740 -110.B26 76.290 41.489 -201.545 -201.761 -405.297 104.238 -204.545 -240.553 -79.660 200

298.15 -74.520 -104.680 82.930 50.000 -187.650 -224.010 -374.170 116.860 -200.940 -234.950 -74.730 298

300 -74.454 -104.543 B3.0B6 50.195 -187.342 -224.521 -373.480 117.155 -200.867 -234.829 -74.624 300
400 -70.606 -96.060 93.061 62.502 -168.357 -257.379 -330.987 135.847 -196.714 -227.463 -68.200 400

500 -66.197 -B5.627 105.760 77.961 -145.160 -301.001 -279.136 159.351 -192.197 -218.620 -60.563 500
600 -61.231 -73.475 120.774 96.150 -118.274 -355.997 -219.135 186.822 -187.444 -208.465 -51.871 600
700 -55.724 -59.814 137.734 116.679 -88.176 -422.921 -152.081 217.537 -182.602 -197.161 -42.272 700
BOO -49.694 -44.836 156.315 139.186 -55.298 -502.273 -78.961 250.894 -177.834 -184.870 -31.901 800
900 -43.170 -2B.713 176.235 163.340 -20.025 -594.497 -0.648 286.411 -173.320 -171.754 -20.880 900

1000 -36.185 -11.600 197.253 18B.838 17.303 -699.9B3 82.093 323.729 -169.256 -157.974 -9.319 1000
1100 -28.779 6.370 219.172 215.406 56.392 -819.065 168.609 362.607 -165.85B -143.690 2.685 1100
1200 -21.000 25.083 241.B39 242.801 96.994 -952.024 258.358 402.929 -163.357 -129.061 15.046 1200
1300 -12.902 44.443 265.142 270.810 138.908-1099.083 350.910 444.696 -162.000 -114.245 27.692 1300
1400 -4.546 64.374 289.012 299.247 181.97B-1260.412 445.945 488.032 -162.055 -99.399 40.564 1400
1500 4.001 84.819 313.424 327.957 226.094-1436.125 543.253 533.181 -163.803 -84.681 53.614 1500

ABSOLUTE MOLAR INTERNAL ENERGY

(MJ/kmol)

T(K) CH, C,H, C,H, CH,OH C,H,OH CH,NO, T(K)

0 -82.660 -115.697 74.264 36.827 -213.096 -183.604 -431.071 100.199 -210.113 -246.415 -B4.B21 0
100 -81.302 -115.471 72.339 36.032 -211.181 -189.212 -425.839 97.352 -20B.484 -245.303 -83.957 100
200 -79.403 -112.4B9 74.628 39.826 -203.207 -203.424 -406.960 102.575 -206.20B -242.216 -Bl. 323 200

298.15 -76.999 -107.159 80.451 47.521 -190.129 -226.489 -376.649 114.381 -203.419 -237.429 -77.209 298.15

300 -76.94B -107.037 80.592 47.701 -189.836 -227.015 -375.975 114.660 -203.362 -237.323 -77.11B 300
400 -73.932 -99.386 89.735 59.177 -171.683 -260.705 -334.313 132.521 -200.040 -230.7BB -71.526 400

500 -70.354 -89.785 101.603 73.B04 -149.318 -305.159 -2B3.293 155.194 -196.354 -222.777 -64.720 500
600 -66.220 -78.464 115.785 91.161 -123.263 -360.986 -224.124 1B1.B33 -192.433 -213.454 -56.B59 600
700 -61.544 -65.634 131.914 110.859 -93.996 -428.741 -157.901 211.717 -1BB.423 -202.9B1 -4B.092 700
BOO -56.346 -51.4B7 149.664 132.535 -61.949 -508.924 -85.612 244.242 -1B4.486 -191.522 -38.552 800
900 -50.653 -36.197 16B.752 155.B57 -27.508 -601.980 -8.131 278.92B -1BO.B03 -179.237 -28.363 900

1000 -44.499 -19.915 18B.938 1B0.523 B.9BB -70B.297 73.778 315.414 -177.571 -166.2B9 -17.633 1000
1100 -37.925 -2.776 210.026 206.260 47.246 -82B.211 159.463 353.461 -175.004 -152.836 -6.461 1100
1200 -30.977 15.106 231.862 232.B24 B7.016 -962.001 24B.3B1 392.951 -173.334 -139.038 5.068 1200
1300 -23.711 33.634 254.333 260.001 12B.099-1109.B92 340.101 433.8B7 -172.B09 -125.054 16.BB3 1300
1400 -16.186 52.734 277.372 2B7.606 170.33B-1272.052 434.304 476.391 -173.695 -111.040 2B.924 1400
1500 -8.4 71 72.34B 300.952 315.4B5 213.622-144B.597 530.7B1 520.709 -176.274 -97.153 41.143 1500
A.16 Introduction to Internal Combustion Engines- SOLUTIONS

ABSOLUTE MOLAR ENTROPY

(kJ!kmol)

T(K) CH,NO, T(K)

0 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0
100 154.754 220.323 222.796 255.497 313.582 601.601 524.594 288.137 204.204 231.886 232.013 100
200 173.463 245.721 242.855 285.836 372.338 512.423 656.095 327.134 225.502 258.289 255.365 200

298.15 186.270 270.200 269.200 319.740 427.980 422.960 781.020 377.440 239.880 280.640 275.010 298.15

300 186.709 270.877 269.941 320.612 429.229 421.472 783.545 378.644 240.342 281.265 275.584 300
400 197.739 295.137 298.432 355.785 483.534 327.662 905.102 432.056 252.261 302.348 293.974 400

500 207.556 318.341 326.667 390.157 535.134 230.781 1020.442 484.322 262.329 322.022 310.969 500
600 216.594 340.454 353.982 423.250 584.058 130.834 1129.626 534.308 270.989 340.503 326.790 600
700 225.073 361.484 380.091 454.853 630.395 27.912 1232.860 581.597 278.452 357.907 341.570 700
800 233.117 381.467 404.880 484.880 674.259 -77.859 1330.416 626.103 284.821 374.305 355.408 800
900 240.796 400.444 428.328 513.312 715.779 -186.332 1422.599 667.914 290.143 389.745 368.382 900

1000 248.152 418.466 450.463 540.165 755.090 -297.349 1509.738 707.217 294.429 404.258 380.558 1000
1100 255.207 435.587 471.349 565.480 792.333 -410.742 1592.170 744.261 297.674 417.869 391.996 1100
1200 261.974 451.865 491.067 589.313 827.653 -526.343 1670.243 779.336 299.857 430.597 402.749 1200
1300 268.454 467.358 509.716 611.729 861.196 -643.977 1744.310 812.760 300.949 442.455 412.870 1300
1400 274.646 482.126 527.403 632.801 893.109 -763.469 1814.728 844.868 300.916 453.457 422.409 1400
1500 280.541 496.230 544.243 652.608 923.542 -884.642 1881.854 876.010 299.718 463 612
0 431.412 1500

ABSOLUTE MOLAR GIBBS ENERGY

(MJ/kmol)
T(K) C 3 H0 C10 H7 CH, CH,OH C,H,OH CH,NO, T(K)

0 -82.660 -115.697 74.264 36.827 -213.096 -183.604 -431.071 100.199 -210.113 -246.415 -84.821 0
100 -95.946 -136.672 50.891 11.314 -241.708 -248.541 -477.467 69.370 -228.073 -267.660 -106.326 100
200 -112.432 -159.970 27.719 -15.678 -276.012 -304.246 -536.516 38.811 -249.645 -292.211 -130.733 200

298.15 -130.056 -185.240 2.668 -45.330 -315.252 -350.116 -607.031 4.326 -272.460 -318.623 -156.724 298.15

300 -130.467 -185.806 2.104 -45.988 -316.111 -350.962 -608.544 3.561 -272.970 -319.208 -157.299 300
400 -149.702 -214.115 -26.312 -79.811 -361.771 -388.444 -693.028 -36.975 -297.618 -348.402 -185.790 400

500 -169.975 -244.798 -57.573 -117.118 -412.727 -416.392 -789.357 -82.810 -323.361 -379.631 -216.047 500
600 -191.188 -277.747 -91.615 -157.800 -468.709 -434.498 -896.911 -133.763 -350.037 -412.767 -247.945 600
700 -213.275 -312.853 -128.329 -201.718 -529.452 -442.460-1015.083 -189.581 -377.519 -447.696 -281.371 700
800 -236.188 -350.009 -167.589 -248.718 -594.705 -439.985-1143.293 -249.989 -405.691 -484.314 -316.227 800
900 -259.886 -389.113 -209.260 -298.641 -664.226 -426.798-1280.988 -314.712 -434.448 -522.525 -352.424 900

1000 -284.336 -430.066 -253.211 -351.328 -737.787 -402.634-1427.645 -383.488 -463.686 -562.232 -389.877 1000
1100 -309.507 -472.776 -299.311 -406.623 -815.175 -367.249-1582.778 -456.080 -493.299 -603.346 -428.511 1100
1200 -335.368 -517.155 -347.441 -464.374 -896.190 -320.412-1745.934 -532.275 -523.185 -645.777 -468.253 1200
1300 -361.892 -563.123 -397.489 -524.438 -980.647 -261.912-1916.693 -611.892 -553.234 -689.437 -509.039 1300
1400 -389.049 -610.603 -449.353 -586.675-1068.375 -191.555-2094.674 -694.783 -583.337 -734.239 -550.808 1400
1500 -416.811 -659.526 -502.941 -650.956-1159.219 -109.162-2279.529 -780.833 -613.379 -780.100 -593.503 1500
 APPENDIX A- THERMODYNAMIC DATA A.l7

Table A.6 EQUILIBRIUM CONSTANTS

At a given temperature, the standard (referring here to a pressure of 1 bar) free enthalpy of reaction or Gibbs Energy change
(.6.G 0 ) , is related to the equilibrium constant (Kp) by:

and the following values of the equilibrium constants have been calculated from the Gibbs Energy tabulations in Tables A.4 and
A.5.

The chemical reactions considered here are presented in the form:

Ev;A; = 0, where: v; is the stoichiometric coefficient of the substance A;.

The partial pressures of the species in equilibrium are found from:

lnKP = Ev;lnp;·. where: the dimensionless quantity P;• is numerically equal to the partial pressure of substance A;, in
units of bar.

Reaction Number Valid Range: 300- 5000 K

1 - 2H + H2 = 0
2 -20 + 02 = 0
3 - 2NO + N2 + 0 2 = 0
4 - H 2 - 1h 0 2 + H20 = 0
5 - VzH 2 - OH + H20 = 0
6 - CO - 1/z 0 2 + C02 = 0
7 - CO -H 20 + C02 + H 2 =0

In KP- bar

Reaction Number

T (K) 1 2 3 4 5 6 7 T (K)

100 511.058 584.208 213.879 284.475 331.098 328.849 44.375 100

200 250.154 285.590 105.451 139.970 162.100 159.694 19.723 200

298.15 163.990 187.014 69.785 92.206 106.332 103.762 11.556 298.15

300 162.906 185.774 69.337 91. 604 105.630 103.058 11.454 300
400 119.151 135.735 51.277 67.320 77.322 74.670 7.350 400
500 92.824 105.639 40.433 52.689 60.291 57.617 4.928 500
600 75.220 85.531 33.199 42.896 48.908 46.244 3.349 600
700 62.612 71.139 28.027 35.875 40.758 38.124 2.249 700
800 53.130 60.326 24.146 30.591 34.632 32.037 1.447 800
900 45.735 51.902 21.126 26.468 29.858 27.308 .840 900

T (K) 1 2 3 4 5 6 7 T (K)
A.18 Introduction to Internal Combustion Engines- SOLUTIONS

T (K) 1 2 3 4 5 6 7 T (K)

J_OOO 39.803 45.153 18.709 23.160 26.031 23.528 .369 1000

1100 34.938 39.623 16.732 20.446 22.895 20.439 -.007 1100
1200 30.873 35.009 15.083 18.179 20.279 17.869 -.310 1200
1300 27.426 31.100 13.688 16.258 18.062 15.698 -.560 1300
1400 24.464 27.746 12.492 14.607 16.160 13.840 -.767 1400
1500 21.892 24.835 11.455 13.175 14.510 12.232 -.942 1500
1600 19.637 22.286 10.548 11.919 13.065 10.828 -1.091 1600
1700 17.643 20.035 9.748 10.810 11.790 9.591 -1.219 1700
1800 15.867 18.032 9.036 9.823 10.655 8.494 -1.330 1800
1900 14.275 16.238 8.400 8.940 9.640 7.514 -1.426 1900

T (K) 1 2 3 4 5 6 7
T (K)

2000 12.840 14.622 7.827 8.143 8.726 6.633 -1.510 2000

2100 11.540 13.160 7.309 7.422 7.899 5.838 -1.584 2100
2200 10.356 11.829 6.838 6.766 7.146 5.117 -1.649 2200
2300 9.273 10.613 6.408 6.167 6.460 4.460 -1.707 2300
2400 8.280 9.498 6.015 5.617 5.830 3.858 -1.759 2400
2500 7.364 8.471 5.653 5.111 5.251 3.306 -1.805 2500
2600 6.518 7.523 5.319 4.644 4.716 2.797 -1.847 2600
2700 5.733 6.645 5.010 4.211 4.221 2.327 -1.884 2700
2800 5.004 5.829 4.723 3.808 3.761 1. 891 -1.918 2800
2900 4.324 5.069 4.457 3.433 3.333 1.486 -1.948 2900

T (K) 1 2 3 4 5 6 7 T (K)

3000 3.689 4.359 4.208 3.083 2.934 1.108 -1.975 3000

3100 3.095 3.695 3.976 2.756 2.560 .756 -2.000 3100
3200 2.537 3.072 3.758 2.449 2.210 .426 -2.022 3200
3300 2.012 2.487 3.554 2.160 1. 881 .117 -2.043 3300
3400 1. 518 1.936 3.363 1. 888 1. 572 -.173 -2.061 3400
3500 1.052 1.416 3.182 1.631 1.280 -.447 -2.078 3500
3600 .611 .925 3.012 1.389 1.005 -.705 -2.093 3600
3700 .194 .460 2.851 1.159 .744 -.948 -2.107 3700
3800 -.202 .020 2.699 .941 .497 -1.178 -2.120 3800
3900 -.577 -.397 2.555 .735 .263 -1.396 -2.131 3900

T (K) 1 2 3 4 5 6 7 T (K)

4000 -.934 -.794 2.419 .538 .041 -1.603 -2.141 4000

4100 -1.273 -1.172 2.289 .351 -.171 -1.799 -2.150 4100
4200 -1.597 -1. 532 2.166 .173 -.372 -1.986 -2.159 4200
4300 -1.906 -1.875 2.049 .003 -.564 -2.163 -2.166 4300
4400 -2.201 -2.202 1. 937 -.159 -.747 -2.332 -2.173 4400
4500 -2.482 -2.515 1. 830 -.315 -.922 -2.494 -2.179 4500
4600 -2.752 -2.815 1.729 -.463 -1. 090 -2.648 -2.185 4600
4700 -3.010 -3.101 1. 632 -.606 -1.250 -2.795 -2.189 4700
4800 -3.258 -3.376 1.539 -.743 -1.403 -2.936 -2.193 4800
4900 -3.496 -3.640 1.450 -.874 -1.551 -3.071 -2.197 4900

T (K) 1 2 3 4 5 6 7 T (K)

5000 -3.724 -3.893 1.365 -1.000 -1.692 -3.200 -2.200 5000

5500 -4.740 -5.022 .988 -1. 564 -2.322 -3.773 -2.209 5500
6000 -5.586 -5.964 .678 -2.037 -2.847 -4.247 -2.210 6000

T (K) 1 2 3 4 5 6 7 T (K)