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SOCIETY OF AUTOMOTIVE ENGINEERS, INC.

400 Commonwealth Drive, Warrendale, Pa. 15096

A Computer Program for

Calculating Properties of
Equilibrium Combustion
Products with Some
Applications to I.C. Engines
Cherian Olikara and Gary L. Borman
University of Wisconsin

Automotive Engineering Congress and Exposition

Detroit, Michigan 750468
February 24-28, 1975
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Copyright © Society of Automotive Engineers, Inc. 1975

All rights reserved.
 Downloaded from SAE International by Indian Institute of Technology - Chennai, Wednesday, January 23, 2019

750468

A Computer Program for

Calculating Properties of
Equilibrium Combustion
Products with Some
Applications to I.C. Engines
Cherian Olikara and Gary L. Borman
University of Wisconsin

MANY MODELS FOR ENGINE COMBUSTION PROBLEMS use are given by References 6-9. The NASA-Lewis
the First Law of Thermodynamics as applied to program (9) is very extensive and includes ther
either the entire cylinder contents or to sub modynamic data for hundreds of species.
systems. Examples include models for spark ig The purpose of the present program is very
nition engines (1)*, diesel engines (2) and narrow by comparison to the NASA program. Its
stratified charge engines (3). Typically the purpose is to specifically deal only with the
major species of the products of combustion may gas phase products of combustion of hydrocarbon
be assumed to follow a shifting equilibrium fuels (containing, C, H, O, N atoms) and air.
process for thermodynamic purposes. For pur The program is however extended to calculate the
poses of chemical kinetics calculations, many partial derivatives of internal energy and molec
of the major species may also be assumed to be ular weight which are helpful when numerically
at the equilibrium concentration (4). Because solving the first law as a differential equation
of this wide spread use it is important to have in time using the method of Reference 10. Most
a rapid means of calculating the equilibrium in importantly, the program is to provide a rapid
ternal energy, molecular weight and species mole means of calculation comparable to the use of
fractions of the products of hydrocarbon-air com the regression analysis equations given in Ref
bustion. erence 11.
Calculation of the equilibrium composition
and internal energy of combustion products for ENERGY EQUATION FORMULATION
engine cycles goes back to the early work of
Tizard and Pye (5) and has been the subject of In order to treat the cylinder gas system
numerous computer studies, a sampling of which thermodynamically the system may be divided into
cells such that the composition and temperature
*Numbers in parentheses designate References at of each cell is uniform. This implies that the
end of paper molar average temperature of the cell may be

ABSTRACT
A computer program which rapidly calculates
the equilibrium mole fractions and the partial
derivatives of the mole fractions with respect
to temperature, pressure and equivalence ratio
for the products of combustion of any hydrocar
bon fuel and air is described. A subroutine is
also given which calculates the gas constant,
enthalpy, internal energy and the partial deriv
atives of these with respect to temperature,
pressure and equivalence ratio. Some examples
of the uses of the programs are also given.
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used to obtain the internal energy of the cell.
As an example, some models used for the spark
ignition engine products divide the products in
to subsystems (1) but assume the same pressure
for each subsystem while others (11) assign one
temperature for the entire product mass. The
first law for each system of products is
necessarily be true for the reactants (12).
The specific gas constant, where M is
the mean molecular weight, is a function of p, T,
F. The derivatives dp/dt in Equation 2 may be
obtained by differentiation of the ideal gas law
and substitution of:

for the dR/dt term. This gives:

The ideal gas equation cannot be explicitly

solved for p in terms of density, temperature
and composition.
If p, T, F and ? are known
at state "n" then the pressure at state n+1 may
be obtained by a first order approximation to
In order to solve Equation 1 it is necessary R. This gives:
to supply an equation of state and the internal
energy as a function of the composition and two
state variables such as pressure and temperature.
The volume must be determined from the fact that
the sum of all system volumes is equal to the
known total volume. A mass balance plus appro
priate flow equations determine the mass in the
system. The heat transfer may be modeled by the
use of empirical convection and radiation equa
tions which generally will be functions of the Equation 4 may be solved numerically using
temperature, density and composition as well as Equation 5 to evaluate p and appropriate differ
some characteristic velocity. ential conservation equations for m and F. An
For a numerical solution of Equation 1 it example of this technique is given later, but
is convenient to introduce the internal energy first we shall consider the program to evaluate
as the sum of the chemical energy and sensible u and R and their derivatives.
energy. For equilibrium the energy then can be
expressed as a function of the variables p, T EQUILIBRIUM THERMODYNAMICS
and F. The variable, F, is the fuel/air equiva Let the fuel CnHmOlNk and air (13) at equiv
lence ratio. For products formed directly from alence ratio F react and the products subject to
the reactants (fuel plus air) the value of F is temperature T and pressure p attain equilibrium.
the equivalence ratio of the reactants. For The numbers n and m should be nonzero; l and k
products of such a reaction mixed with air or may or may not be zero.
additional products of the same fuel the value
of F may be computed for a hypothetical reactant
F which would give the same atomic properties as
the resulting mixture. The term du/dt may be
written

The partial derivative terms can be calculated

directly from the equilibrium thermodynamics as
functions of T, p and F.
Little error is made for normal engine con
ditions if the products are assumed to be an
ideal gas mixture although the same may not
where x1 through x12 are mole fractions of the
product species. The number, x13, represents
the moles of fuel that will give one mole of
products.
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The left side of the equation may be written
as

Atom balances for the various elements give REDUCTION IN NUMBER OF EQUATIONS
Equation (8-1) gives
Equation (8-5) gives
These are now used to eliminate X12 and
x13 in Equations 8 and 9.

The constraint that the mole fraction of all the

products add up to unity requires that

To solve for the 13 unknowns, we need 7 more Denote the ratios

equations which are provided by the criteria
of equilibrium among the products, expressed
by the following 7 non-redundant hypothetical
reactions.

Now Equations 11 can be used in Equations 12 to

eliminate all variables except x4, x6, x8 and
X11. The resulting four nonlinear equations
with four unknowns may be expressed symbolically
by

Assume we know a vector

Where p is the pressure in atmospheres.
The equilibrium constants are curve fitted from
data in JANAF Thermochemical Tables, Second Edi which is reasonably close to the true solution
tion (1971). Details of fitting are given in vector
Appendix A. The expressions for equilibrium
constants can be rearranged to express mole
fractions of all the products of combustion in
terms of x4, x6, x8 and X11 the mole-fractions
of H2, CO, O2 and N2 respectively. The functions on the left side of the equations
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can then be expanded around the known vector as
a Taylor's series.
Neglecting the partial derivatives of second or
der and higher we get a set of linear equations
where ?xi are the approximate corrections.
where functions fj and their partial derivatives
are evaluated at the known vector.
This set of linear equations can be solved
for ?x4, ?x6, ?x8 and ?x11 using a Gaussian
elimination method. The improved values are then
The improved vector can now be used to
evaluate the partial derivatives and functions.
Further corrections can then be calculated and
applied. The iterative procedure is to be con
tinued until the relative changes in all the com
ponents are less than a specified value.
of the computation of the elements of Eq. 14 are
given in Appendix B.
INITIAL ESTIMATION OF MOLE FRACTIONS
The Newton Raphson iteration is not self
starting. Unless an approximate solution is
known from a previous execution of the subroutine
at conditions close to those presently encoun
tered, it is necessary to make an initial esti
mation to get the iteration started. The follow
ing method of estimation developed through judi
cious simplifying assumptions is found to be re
markably good.
Assume that the products are only H2, CO,
O2, H2O, CO2, N2 and Ar. Equation 6 becomes
From the C balance and Eq. 11-7
From the H balance and Eq. 11-6
and from the N, Ar, and O balances
Substituting for x6, x9 and X10, rearranging
terms and dividing through by x13,
Thus The quantity X13 can be estimated with good ac
curacy from the condition that the mole fractions
should add up to unity.
For F = 1 a good estimate of X13
obtained
be
can
from
For F > 1 an estimate of x13 can be obtained
from
Substitution of the estimated value of x13
into Eq. 16-6 gives an equation in the single un
Details known x8. After solving Eq. 16-6 by Newton's
method, the other unknowns may be obtained di
rectly by substitution into Equations 16-1, 16-2,
and 16-3. These initial estimates can then be
used to start the solution of Equations 13 by
use of Equations 14 and 15.
PARTIAL DERIVATIVES OF THE MOLE FRACTIONS
Starting with Equations 13, the functions
and hence the mole fractions are dependent upon
temperature, pressure and equivalence ratio.
For example, taking the total derivatives of
each equation with respect to temperature we get
four linear simultaneous equations in four un
knowns.
It is seen that the coefficient matrix is
the Jacobian that appeared in Newton Raphson
iteration. Similarly, it is seen that the matrix
equations for solving for the partial derivatives
with respect to pressure and equivalence ratio
would also be identical except that T is replaced
by p or F. Equations for the computations of the
elements of the coefficient matrix and the con
stant vector are given in Appendix C. Solution
of the equations sets (Equations 18 and similar
ones for p and F) can be accomplished in a
straight forward manner using the Gaussian elim
ination method. As shown in Appendix C the re
maining partial derivatives of x1,x2, etc. are
easily obtained by use of Equations 11 and 8-5
and direct substitution.
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The computation of the equilibrium mole
fractions and partial derivatives ofthe mole
fractions with respect to T, p, F iscarried
out by a FORTRAN coded program EQMD.A guide
for users is given in Appendix D anda program
listing is given in Appendix E.
ENTHALPY
AND ENERGY
INTERNAL

The absolute enthalpy used here is defined

as

The values of the specific heats and heats of

formation were taken from Ref. 14 and were used
with a table look up and linear interpolation
program.
Using the results of Program EQMD the en
thalpy of the mixture, h, is easily calculated
as is the average molecular weight, M, and gas
constant, R.

we consider the expansion of a closed system of

products.
For the adiabatic constant pressure reaction
we first calculate the reactant mixture enthalpy.
If the fuel heat of formation is not known it can
be estimated using the heating value and H/C ra
tio (15). For higher pressures the non-ideal ef
fects (12) should be included. Having computed
the reactant enthalpy, hr, we hold p and F con
stant and solve for T

The partial derivatives are also easily computed. Using Newton's method
For example,

where Tn is the first estimate and Tn+1 is the

improved estimate. The first estimate can be
The other expressions for the partiais of h, u any reasonable number but preferably larger than
and R with respect to T, p and F are given in the expected solution. For our example, we take
Appendix C. methane at 536.4°R, one atmosphere and F = 0.8,
The computation of u, h, R and their par 0.9, 1.0, 1.1, 1.2, Figure 1 shows a plot of the
tials is carried out by FORTRAN coded program PER. result and Table 1 shows the progressive esti
A users guide is given in Appendix D and a mates of T for the F = 1.1 case. A plot of
program listing is given in Appendix E. ?(h-hr)/?F at the calculated F and T of values
Figure 1 gives the dashed curve of Figure 1. The
EXAMPLE CALCULATIONS zero point determines the F at the maximum flame
temperature.
Two simple cases are given here as examples The following example of expansion of a
to show the use of the programs. First we con closed system of products of combustion is given
sider the classical problem of computing the con only to illustrate the application of the pro
stant pressure adiabatic flame temperature. Second, grams to such calculations. The kinematic and
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Total mass of gas inside the system is
0.001244 lbm and there is no flow in or out of
the system. The fuel is C8H16 and equivalence
ratio F is 1.2. Initial conditions are T =
5600°R and p = 533 psi at ? = 20°. The expan
sion is assumed to follow shifting equilibrium.
Improved Euler method is used for solving the
differential equations. The steps taken at each
interval are listed below.
Let the temperature Tn and pressure Pn be
known at time tn where the derivative, dT/dt,
is calculated using Eq. 4.

heat transfer models used below are extremely

simplistic.

are used as starting condi

tions for the subsequent time interval.
The results of the program for expansion
from ? = 20° to 180° is plotted in Figure 2.
In addition, the integrated values of pdV and Q
were also accumulated during the calculation.
The change in internal energy was calculated
from initial and final conditions. For a step
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7
size of 1° crank angle: "Engine Simulation Studies Conducted at the Uni
versity of Wisconsin." Tech. Report No. 11398,
U.S. Army Tank Automotive Command, March 1972.
3.L.W. Evers, P.S. Myers, and O.A. Uyehara,
"A Search For a Low Nitric Oxide Engine." Cen
tral States Combustion Institute Meeting,
Madison, Wisconsin, Spring 1974.
4.H.K. Newhall, "Kinetics of Engine-Generated
ACKNOWLEDGMENT Nitric Oxides and Carbon Monoxide." Twelfth
Symposium (International) on Combustion, 1969.
This report was submitted in partial ful 5.Tizard and Pye, "Empire Motor Fuels Commit
fillment of Grant Number R-802589-01-0 by the tee Report." Proc. Inst. of Automotive Engrs.,
University of Wisconsin-Madison under the partial Vol. 18, No. 1, 1923.
sponsorship of the Environmental Protection 6.H.N. Powell, A. Schaffer and S.N. Suciu,
Agency. Work was completed as of July 1, 1974. "Thermodynamic Properties--Properties of Combus
tion Gases, System: CnH2n-Air." General Elec
NOMENCLATURE tric Co., Cincinnati, Ohio, 1955.
7.H.K. Newhall and E.S. Starkman, "Thermody
Aij afi/axj
-

dQ/dt - rate of heat transfer

namic Properties of Octane and Air for Engine
Performance Calculations." SAE Paper 633G, 1963.
fi - nonlinear function of mole fractions 8.R.J. Steffensen, "A FORTRAN IV Program of
F - fuel/air equivalence ratio Thermochemical Calculations Involving the Ele
h - enthalpy per unit mass ments Al, B, Be, C, F, H, Li, Mg, N and 0 and
hi - enthalpy per mole of species i except
where otherwise defined
Their Compounds," PhD Thesis, Purdue University,
1966.
hr - reactant enthalpy per unit mass 9.S. Gordon, "Complex Chemical Equilibrium
Ki - partial pressure equilibrium constant Calculations." NASA Sp-239, Kinetics and Thermo
m - mass or number of H atoms in fuel dynamics in High Temperature Gases, March 1970.
molecule 10.G.L. Borman, "Mathematical Simulation of
M - molecular weight of mixture Internal Combustion Engine Processes and Perform
n - number of carbon atoms in fuel mole ance Including Comparisons with Experiments."
cule PhD Thesis, University of Wisconsin, Madison,
? - pressure 1964.
r,r',r" - proportions of N2, O2, Ar in air 11.R.B. Krieger, and G.L. Borman, "The Compu
R - specific gas constant of mixture tation of Apparent Heat Release for Internal Com
Ro - universal gas constant bustion Engines." ASME Proc. Diesel Gas Power,
t - time ASME Paper 66-WA/DGP-4, 1966.
T - temperature 12.J. Maniotes, "Ideal and Non-ideal Theoreti
Tij - gas
?xi/?xj
-
cal Equilibrium Calculations for Mixtures of
Tw side wall surface temperature Methane and Air." PhD Thesis, Purdue University
u - internal energy per unit mass 1962.
V - volume 13."CRC Handbook of Chemistry and Physics."
xi - mole fraction 71st Edition, Sea level atmospheric composition
? - gas constant correction factor of dry atmosphere, pp. F-147, 1970-71.
overdot - indicates d/dt 14."JANAF Thermochemical Tables." Second Edi
tion, The Dow Chemical Co., Midland, Michigan,
REFERENCES 1971.
15.H.N. Powell, "Applications of an Enthalpy
1.P. Blumberg and J.T. Kummer, "Prediction of Fuel/Air Ratio Diagram to 'First Law' Combustion
NO Formation in Spark-Ignited Engines--An Analy Problems." Trans. ASME, pp. 1129-1138, July
sis of Methods of Control." C.S.T., Vol. 4, 1957.
pp. 73-95, 1971. 16.I. Klotz, "Introduction to Chemical Ther
2.G.L. Borman, P.S. Myers, and O.A. Uyehara, modynamics." W.A. Benjamin Co., New York, 1964.
 Downloaded from SAE International by Indian Institute of Technology - Chennai, Wednesday, January 23, 2019
8
APPENDIX A
CURVE FITTING OF EQUILIBRIUM CONSTANTS
The equilibrium constants data was taken
from JANAF Thermochemical Tables (14), where
lNew
og10Kp Text
(formation) for all species are tabulated
as functions of the absolute temperature (°K).
Equilibrium constants for the reactions consid
ered in the equilibrium thermodynamics were cal
culated using the relation
Theoretical studies (16) suggest a function
relationship of the type
where T is the absolute temperature and A, B, C,
D, E are constants.
This model was used to fit the tabulated
data by means of a least squares fitting program.
A trade-off between the conflicting interests of
obtaining either high accuracy in a narrow range
of temperature or lower accuracy in a wider range
led to choosing 600 to 4000°K (1080 to 7200°R) as
the range most relevant to the study of combus
tion phenomena in engines.
The log Kp predicted by the equations were
compared with the original data and the devia
tions were less than 0.0009. (The original data
is tabulated only to the third decimal place and
so there is an inherent uncertainty of 0.0005.
Hence the deviations were not considered signi
ficant.)
A transformed temperature TA defined as
0.005 T/9 where T is in °R was used for fitting.
The constants A, B, C, D and E are listed in
Table A-1.
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APPENDIX B
MOLE FRACTION COMPUTATION EQUATIONS
In the specific problem under consideration,
we define for convenience, the following partial
derivatives

From Eqs. 11, we get

With the above notations, the elements of

Eq. 14 written as a matrix equation [A][?x] = [B]
can be expressed as
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APPENDIX C
PARTIAL DERIVATIVE COMPUTATIONEQUATIONS
Define

From Equations 11, Yi are seen to be functions

of x4, X6, x8 and x11 only.
Substituting for xi from Equation Cl in
Equation 12 and differentiating with respect to
T, we derive

Define

The model used for fitting equilibrium constants

KP is
Partial derivatives with respect to p are similar
to above except that ?/?T is replaced by ?/?p.
Note that C5 and C7 are not functions of p and
hence terms involving ?C5/?p and ?C7/?p drop out.
The parameters d2, d3 and d4 are functions
of F, but none of the Ci are. Hence From which we derive

CALCULATION OF PARTIAL DERIVATIVES OF REMAINING

MOLE FRACTIONS

From Equations 11

From the expression for Ci and di

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CALCULATION OF PARTIAL DERIVATIVES of R, h and u
From Equations 19 to 22

For partial derivatives with respect to p,

substitute ?/?p where ?/?T appears above.
Example:

For partial derivatives with respect to F, Note that the specific heats of the
species at constant pressure.
substitute zero where ?Ci/?T appears and ?/?F For partial derivatives with respect to p
elsewhere.
Example:
and F, replace ?/T with ?/?p and ?/?F respec
tively. The exceptions are

Exception:

APPENDIX D
GUIPE TO USING SUBROUTINES EQMD AND PER (where AN, AM, AL are the number of C, H and O
atoms in fuel molecules) free carbon will defi
PURPOSE OF THE SUBROUTINES - Subroutine EQMD nitely be formed. For C8H16, this maximum F is
can calculate the mole fractions xi of the prod 3.
ucts of combustion of any hydrocarbon fuel and The products of combustion are assumed to
air, at equilibrium under specified conditions of be ideal gases. This assumption is not valid at
temperature T, pressure p and equivalence ratio extremely high pressures (12).
F. It can also optionally calculate the partial HOW TO ACCESS THE SUBROUTINES - Transfer of
derivatives of the xi with respect to T, p and F. information between the calling program and the
Subroutine PER can calculate the average subroutines are through labelled COMMON areas
molecular weight M, gas constant R, enthalphy h and hence every program that calls the subrou
and internal energy u of the equilibrium products tines must contain
of combustion. It can also optionally calculate
the partial derivatives of R, h and u with re
spect to t, p and F.
In addition to carbon and hydrogen, the fuel
may or may not contain oxygen and nitrogen atoms.
The product species considered are H, O, N, H2,
OH, CO, NO, O2, H2O, CO2, N2 and Ar in gas phase.
LIMITATIONS OF THE SUBROUTINE - The equilib
rium constants used in the subroutines were
fitted as a function of temperature in the range
1080°R to 7200°R. The subroutines cannot be used
outside this range.
The subroutine cannot handle the formation
of free carbon. It can be shown that for equiva
lence ratio,
The above variables are input to the subroutine
and should be defined at the time of calling.
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The following are output variables. tered during calculation of
IERR - Error code with meaning as specified partial derivatives of mole
later. fractions.
XEQ(12) - Mole fractions of the product species. Immediately after every call to the subrou
XPA - The numbering code is given later. tine, the value of TERR must be checked. It
A parameter used in the subroutine. should be zero. If it is not, the numbers
It represents the modes of fuel that stored in the other output variable locations
will give one mole of products. are meaningless and should not be used. Prefer
rably print out the value of IERR and also the
condition (AN,AM,AL,AK,F,T,P,KLO)at which the
failure occurred.
AVM - Average molecular weight of products
of combustion
R - Gas constant BTU °R-1
H - Enthalpy BTU
U - Internal energy BTU

The partial derivatives defined earlier

have units of the variable per °R, per psi , per
unit fuel air equivalence ratio (dimensionless)
respectively. For example,
DXT(1) has units of °R-1
DRP has units of BTU
DHF has units of BTU
psi-1
°R-1
REFERENCE STATES - For computation of en HOW TO CALL SUBROUTINE PER - Both the
thalpies and internal energies, the following $INCLUDE cards and all three of the COMMON state
states were assigned zero value of enthalpies. ments are required. The subroutine PER will be
H2 (ideal gas) at 0°R executed every time the following statement is
O2 (ideal gas) at 0°R encountered.
N2 (ideal gas) at 0°R
C (Graphite) at 0°R
Ar (ideal gas) at 0°R
CONTROL VARIABLE -]KLO -
KLO = 0 The subroutine will make a fresh
estimate before iterating
KLO = 1 Closeness criteria built into the
subroutine will decide whether or
not to make a fresh estimate. THIS
IS RECOMMENDED.
The subroutine PER internally calls EQMD
KLO = 2 The subroutine will use input values with the same value of JDR and all the relevant
of H2, CO, O2 and N2 mole fractions outputs of EQMD are also available after a call
as initial estimates to PER. It is not necessary to call EQMD again.
However if only the mole fractions and/or their
ERROR CODE -]IERR - partial derivatives are needed and not the prop
IERR
= 0 No error. erties, some computation time could be saved by
= 1 Specified temperature out directly calling EQMD as explained below.
side 1080 to 7200°R range. HOW TO CALL SUBROUTINE EQMD ALONE - In this
= 2 Specified equivalence ratio case # INCLUDE CO*PER and COMMON/PROP/ cards are
too high as to cause forma not needed. The subroutine EQMD will be executed
tion of free carbon. each time the following statement is encountered.
= 3 Attempted to calculate an
estimate; but none found within
reasonable limits.
= 4 A singular matrix was encoun
tered during calculation of
mole fractions
= 5 Few mole fractions were cal
culated as negative during
iteration.
= 6 Newton Raphson iteration did SAMPLE PROGRAM - Listing of a sample program
not converge in 25 attempts. which calls subroutine PER is given on the fol
=7 A singular matrix was encoun lowing page.
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