Int. J. mech. 3ci. PergamonPress. 1971. Vol. 13, pp. 803-812.

Printedin GreatBritain

D I E S E L F U E L P R O P E R T I E S FOR COMBUSTION
CALCULATIONS

T. J. WILLIAMS
University of Wales Institute of Science and Technology

(Received 16 A p r i l 1971, and in revised f o r m 5 J u l y 1971)

Summary--The composition of diesel fuel in relation to its thermodynamic properties is

discussed. I t is indicated that there is less correlation between the fuel specification and
the properties than in the case of petrols.
Maxwell's correlation methods and hydrocarbon mixture data are employed to deter-
mine the properties of a light diesel off. Methods of approximation and reduction of this
data are presented which give rapid methods of estimation of specific enthalpy and volume
with allied properties without excessive computer storage requirements. The methods
cover the whole range of stabes required, including the neighbourhood of the critical point.
A computer program for evaluation of the properties is described.

NOTATION
P pressure
V volume
R M universal gas constant
T absolute temperature
i~ PV/RMT
T~ critical temperature
Pc critical pressure
Pa P/Pc
C~ molar concentration of component i of mixture of all components except fuel
CF molar concentration of fuel
H molar specific enthalpy
Cp molar specific heat at constant pressure
Cv molar specific heat at constant volume
VI molar specific volume

INTRODUCTION
CURRENT research into t h e c o m b u s t i o n processes in diesel engines requires a
knowledge o f t h e s t a t e a n d properties of t h e fuel droplets arising f r o m t h e
injection processes. These droplets n o r m a l l y occur initially a t near-critical
pressures a n d a t t e m p e r a t u r e s s o m e w h a t below t h e critical. E v a p o r a t i o n
h i s t o r y c o m p u t a t i o n s carried out b y W i e b e r 1 indicate t h a t t h e droplets o f t e n
r e a c h s t a t e s in t h e v i c i n i t y of t h e critical point, as indeed would be expected.
I n this region t h e specific volume, e n t h a l p y a n d allied p r o p e r t i e s c a n n o t be
o b t a i n e d b y t h e simple p r o c e d u r e s usually applied in regions well r e m o v e d
f r o m t h e critical point, i.e. t h e use of c o n s t a n t , p r e s s u r e - i n d e p e n d e n t specific
a n d l a t e n t h e a t s a n d c o n s t a n t specific volumes. I t is t h u s n e c e s s a r y t o o b t a i n
a n d store a m o r e detailed a n d c o m p r e h e n s i v e description of t h e fuel p r o p e r t i e s
a n d t o devise a m e a n s of c o m p u t i n g values a p p r o p r i a t e to p a r t i c u l a r states.
803
804 T.J. WILLIAMS

This requirement leads to two difficulties which might be named "thermo-

dynamic" and "descriptive". The thermodynamic difficulties arise from the
fact t h a t a mixture without a constant boiling point and hence saturation line
is dealt with and concern is with pressure/temperature regions where the fuel
cannot be treated as an ideal gas. Fig. ] illustrates the variation in the thermo-
140

130

120

IiO
% "Non ideal" gas region

50

40

o.. 30

20 Critical pressure Critical pressure

Ideal
gas region
I NOvapour data in
,0~this region ~"~-'~-------"t" /

200 400 600 800 1600

Temperature, K
Critical
temperature

FIG. l . Gas-phase variation over the relevant pressure-temperature field.

dynamic characteristics of the fuel over the field of pressures and temperatures
encountered in diesel combustion problems. The descriptive difficulties arise
because the usual specification characteristics, e.g. specific gravity, carbon:
hydrogen ratio, 90 per cent volume temperature, cetane number, etc. cannot
be correlated with the thermodynamic properties. This situation may be
contrasted with t h a t for the petrols and lighter distillation fractions where it is
possible to assume t h a t the fuel is a paraffin, calculate its average molecular
weight from the carbon:hydrogen ratio and use the properties of the nearest
pure paraffin (usually heptane or octane).
Diesel fuels however consist of mixtures of paraffins, cyclo paraffins and
aromatics in varying proportions as shown in Table 1 condensed from data
give by Sacharen7
The cetane number is not a reliable guide to the composition because of the
practice of using additives to natural or cracked fractions having a low cetane
 Diesel fuel properties for combustion calculations 805

number. We are thus not able to choose a representative pure substance but
shall adopt instead the technique initiated nearly 40 years ago by Watson and
Nelson3 and culminating in the comprehensive data book on the properties of
petroleum fractions by Maxwell.4 By these methods the thermodynamic data

T A B L E 1. C O ~ Y P O S I ~ O ~ OF QAS OIL FRACTIONS F R O ~ U . S . A . ]FIELDS

Range of paraiTms Range of cycle-paraffins Range of aromatics

% % %
0-48 80-40 13-40

are correlated against volume average, weight average, molal average and
m e a n a v e r a g e b o i l i n g p o i n t ( o b t a i n e d f r o m t h e c r u d e oil a s s a y c u r v e ) a s w e l l a s
specific g r a v i t y a n d " c h a r a c t e r i s a t i o n f a c t o r " . T h i s l a t t e r f a c t o r is d e f i n e d a s
( b o i l i n g p o i n t o f fraction) x specific g r a v i t y . T a b l e 2 c o n d e n s e d f r o m N e l s o n ' s 5
d a t a s h o w s t h e v a r i a t i o n o f t h i s f a c t o r f o r a r a n g e o f d i e s e l fuels o f m i d b o i l i n g
p o i n t 560 K w i t h o u t a d d i t i v e s .

TABLE 2. VARIATION OF CHARACTERIZATIONFACTOR

Characterization factor Cetane number Base

12.9-12.15 72-59 Paraffin

12.1-11.5 58-42 Intermediate
11.45-10.5 40-20 Naphthenic

EVALUATION OF THE PROPERTIES OF A LIGHT DIESEL FUEL

The following d a t a were taken as representative of a light diesel fuel:
Specific gravity 0.84, i.e. 37 A P I ,
Volume averaged boiling point 598 K,
Slope of assay curve 4.6C/~/o,
Carbon/hydrogen ratio 0.639.
Application of the empirical correlations of Maxwell to this d a t a gives the following
preliminary information:
Molal average boiling point 521 K,
Mean average boiling point 551 K,
Weight average boiling point 600 K,
Characterization factor 12.0,
Molecular weight 222.
Pseudo-critical temperature 700 K,
Pseudo-critical pressure 16.9 bar,
The latter two characteristics are used for correlations where critical temperature and
pressure would be used for pure substances. These pseudo values were found b y K a y e
to give better correlations for mixtures, where the true critical conditions are obviously
a function of the highest fraction of the mixture.
W i t h this preliminary information we m a y now continue to use Maxwell's d a t a to
determine specific volume and enthalpy.

SPECIFIC VOLUME
Available liquid volume d a t a a t the critical pressure stops short of the critical tempera-
ture b u t is here extrapolated linearly to the known specific volume a t the critical point.
Specific volumes above and below the critical pressure are obtained b y linear interpolation
55
806 T.J. ~'VILLIA,MS

for p r e s s u r e f o r m t h e critical p r e s s u r e curve. 8I~/8P is t a k e n as a l i n e a r f m l c t i o n of t e m -

p e r a t u r e h a v i n g o n e of t w o f o r m s d e p e n d i n g o n w h e t h e r t h e t e m p e r a t u r e is a b o v e or
b e l o w 500 K . A " s a t u r a t i o n l i n e " is a d d e d in a s o m e w h a t a r b i t r a r y f a s h i o n b y d r a w i n g
a s t r a i g h t line f r o m t h e l i m i t a v a i l a b l e v o l u m e d a t a a t one b a r p r e s s u r e t o t h e critical
p o i n t . P o i n t s t o t h e left of t h i s line will b e well a b o v e t h e boiling p o i n t of m o s t of t h e
m i x t u r e a n d it seems r e a s o n a b l e t o a s s u m e t h a t u n d e r m o s t c i r c u m s t a n c e s t h e v a p o u r
p h a s e will e x i s t here. Specific l i q u i d v o l u m e is o b t a i n e d b y l i n e a r i n t e r p o l a t i o n in a t a b l e
of v o l u m e vs. t e m p e r a t u r e a t t h e critical pressure. T h i s v a l u e is " c o r r e c t e d " tbr p r e s s u r e
b y m e a n s of a l i n e a r f u n c t i o n of pressure. T h i s f u n c t i o n h a s one of t w o slopes as a n
a p p r o x i m a t i o n t o a s m o o t h curve. T h e d i s c o n t i n u i t y occurs a t 500 K . T a b l e 3 c o n t a i n s

TABLE 3. VOLITME DATA

Temperature Specific v o l u m e a t 16"9 b a r

T (K) I,} (m~/kg mole)

250 0.2551
300 0-2656
35O O.2788
400 0"2945
450 0.3051
500 0.3314
550 0.3524
600 0.3866
650 0.4445
700 0.8442

Liquid: Specific g r a v i t y t a k e n as 0.84 a t 60F

16.9 b a r .
Specific v o l u m e a t p r e s s u r e P = VF + 0.0165
(16.9-P)*Z w h e r e Z --- 0 . 0 0 0 1 6 ( T - 2 5 0 ) , T <
500; Z = 0 . 0 0 0 4 ( T - 4 0 0 ) , T > 500.

d a t a for t h e critical p r e s s u r e c u r v e s a n d p r e s s u r e c o r r e c t i o n f a c t o r s for liquid. T h e a b o v e

m e t h o d s are c o n s i d e r e d a~lequate for c o m b u s t i o n c a l c u l a t i o n s w h e r e t h e a m o u n t of liquid
v o l u m e is n o t v e r y i m p o r t a n t . O t h e r t y p e s o f c a l c u l a t i o n s m a y w a r r a n t a m o r e d e t a i l e d
specification of l i q u i d v o l u m e .
D e v i a t i o n of t h e specific v o l u m e of t h e v a p o u r f r o m t h a t of a n ideal gas is c h a r a c t e r i z e d
b y / ~ defined b y [ P V / R M T ] , w h e r e P is pressure, V v o l u m e , T t e m p e r a t u r e a n d R M the
u n i v e r s a l gas c o n s t a n t . M a x w e l l ' s d a t a f o r / ~ h a s b e e n r e p l o t t e d a g a i n s t t e m p e r a t u r e for
a series o f v a l u e s of PR w h e r e PR is t h e r a t i o of a c t u a l p r e s s u r e t o critical pressure. B e l o w
t h e critical p r e s s u r e it was f o u n d possible to utilize a single c u r v e o f / ~ b y p l o t t i n g i t
a g a i n s t t h e p a r a m e t e r T-700 (PR) -'25 (see Fig. 2). A b o v e t h e critical p r e s s u r e it h a s b e e n
n e c e s s a r y t o use a n u m b e r o f s t r a i g h t lines, t h e p o s i t i o n a n d slope o f w h i c h are d e p e n d e n t
o n t h e p r e s s u r e , a n d a s i n g l e / z - T c u r v e as s h o w n in Fig. 3. T h e d o t t e d lines a r e a n
e n v e l o p e s u r r o u n d i n g c u r v e s p l o t t e d f r o m M a x w e l l ' s d a t a . T h e e r r o r is l a r g e r t h a n t h a t
of t h e s u b - c r i t i c a l case b u t n o w h e r e g r e a t e r t h a n 5 p e r c e n t .
T h e m a n n e r i n w h i c h t h e g r a p h s a n d e x p r e s s i o n s for v o l u m e c o v e r t h e p r e s s u r e
t e m p e r a t u r e field is s h o w n in Fig. 4. M a x w e l l r e c o m m e n d s t h a t in m i x t u r e s of fuels a n d
ideal gases t h e p r e s s u r e t o b e u s e d in c a l c u l a t i o n of/~ is P ~]C, w h e r e C is m o l a r concen-
t r a t i o n a n d P t h e t o t a l pressure. T h e specific v o l u m e of t h e m i x t u r e is g i v e n b y

[RM T(( 1 -- ~Cf) - Z , C , ) / P ] ,

w h e r e C t is fuel c o n c e n t r a t i o n . I n c a l c u l a t i o n s i n v o l v i n g a h o m o g e n e o u s m i x t u r e of fuel
v a p o u r a n d a i r t h e m o l a r c o n c e n t r a t i o n w o u l d b e a b o u t 0.01. A t a t o t a l p r e s s u r e of
a b o u t 160 b a r a n d t e m p e r a t u r e o f 1000 K / ~ w o u l d b e i n t h e r e g i o n of 0.9; t h u s i n v i e w
 Diesel fuel properties for combustion calculations 807

1.0

O.E

0.6

>1.-
o_1c=
Ill 04

0.2

T- O0
t 100 200 3'0 4'00
Critical Reduced temperature, K
temp

FIG. 5. Ideal gas deviation for sub-critical pressures.

09

0,7 i""- - - Approximation

r r ' ~ L i m i t s of actual data

05

0.3 Y I I I I I I
700 SO0 900 I000 II00 1200 1400

Temperature, K
FIG, 3. Ideal gas deviation for super-critical pressures.

of the small concentration of fuel the error in taking the mixture as an ideal gas would be
small and becomes smaller at higher temperatures. I n this case, the use of the volume
data presented here would not be warranted. I n droplet combustion, on the other hand,
calculated values of/z can be as low as 0.25.
I n Fig. I the "saturation" line is tabulated at intervals of 50 K whilst the compressed
liquid a n d superheated vapour regions are described b y a small number of straight lines.
The temperature-enthalpy diagram is divided into a n u m b e r of regions in each of which
the enth~lpy is obtained b y linear interpolation for temperature and pressure. The values
of OH/OTand ~H/~P required for interpolation in regions R I , R4 and R5 are quoted in
Table 5 as S1-$6. The data have been converted from a d a t u m of liquid fuel at 60F to
elements at 0 K b y taking the heat of combustion of liquid fuel at 60F as 10, 151,
873 kJ/kg mole and using enthalpy data for the elements of the J.A.N.A.F3 tables.
All relevant enthalpy values are given in Tables 4 and 5.
808 T. ,1. WILLIAMS

o) "--.. --.~ nCre ~ .

/ ~-'~-~ --
#/ '- # / / Z ~ '
Region R5 7 ~///~
T,650, P~50/ . .~'//~T>725,
"/ //T P~,
725
700 . . . . . . ----~ --21c--- ---/--/---- 650<T
(critical) t/W/D ,o>.,

5~ 650
Region R2 / /~ PNI

o
600
E -all p, T.< 65"-'-0- - / 7r'rRegio~-"n RWgo
t % '-''z-~/''z-'r
#- ~ liquid if P>I and -<600

Liquid / Vapour
/ ~oo
/ Values tabulated
~ at 50K intervals
--Constant press, lines

Enthalpy

FIe. 4. Diagrammatic representation of approximate temperature-enthalpy

diagram.

TABLE 4. "SATuI~ATION ~ LINES

tt s Hg
Temperature Liquid Vapour
K (kJ/kg mole) (kJ/kg mole)

250 337,469 415,637

300 358,010 430,302
350 381,246 450,957
400 404,483 469,030
450 431,335 492,267
500 461,284 518,602
550 492,783 544,420
600 528,413 572,304
650 567,140 600,705
700 608,450 608,450
 Diesel fuel properties for combustion calculations 809
T A B L E 5. ~~ S U P E R H E A T " DATA

S1 797.4 kJ/kg mole K

$2 738.0 kJ/kg mole K
$3 796.5 kJ/kg mole K
$4 635.7 kJ/kg mole K
$5 509.6 kJ/kg mole bar
$6 102.5 kJ/kg mole bar
E n t h a l p y at 16.9 bar,
725 K 643,167.3 kJ/kg mole
Molecular weight 222
Once specific volume and enthalpy have been obtained it is a simple matter to obtain
internal energy as H - P V and specific heat as enthalpy or internal energy difference over
an interval of 1 K.
Since the mathematical methods employed are of a n elementary nature the pro-
gramming of the arithmetic operations is a simple matter. Construction of the logic for
choice of region requires some care, however, and appropriate logic diagrams for the liquid
and vapour phase are given in Figs. 5 and 6 respectively. I t m a y be noted t h a t these
diagrams overlap in some cases and a choice of phase is made irrespective of that initially
specified. Fig. 7 shows a logic diagram for computation of specific volume.

True

:otse

Folse

True

FIG. 5. Logic for liquid-phase enthalpy.

810 T.d. WILLIAMS

True
25~ True

False
I0~ True
m_
True
False
~Folse P,

---olse

True True
/

:olse
L False

True
m-

False

FIG. 6. Logic for vapour-phase enthalpy.

 Diesel fuel properties for combustion calculations 811

~
False

True False _
r

00~ True :

False

:alse

True ~

:olse

True ~

FIG. 7. Logic for specific volume computation.

COMPUTATIONAL METHODS
The methods described in the previous pages have been embodied in a n Algol pro-
cedure. I n systems where volume is an independent variable it m a y be necessary to
employ the procedure iteratively {which would not be the case for a n ideal gas); it is
thus important that computation should be rapid and it is for this reason that linear
interpolation has been extensively employed. The procedure is a compromise between
speed and storage requirements and could have been made faster b y storing m o r e / ~ - P - T
data and replacing the expression [700 ((PR)-'2s- 1)] by linear interpolation. However,
in its present form, since the amount of data is small and nearly all stored externally to
the procedure, modification to suit fuels of different characteristics should be a fairly
simple matter. I t should be noted, however, that for fuels of different characteristics,
e.g. residual otis, it will be necessary to generate new correlations b y the methods outlined
here. I t will also be necessary to insert new numerical values for the Pc, To and inter-
polation limits.

APPLICATION
Substitution of numerical values for the formal parameters: phase, pressure, tempera-
turc and concentration sets the variable F U E L P R O P to the numerical value of the
desired property. This property is specified b y the formal parameter P R O P which takes
812 T . J . WILLIAMS
the value of 1-6 to indicate internal energy, enthalpy, specific heat at constant pressure,
specific heat at constant vohtme, specific heat ratio C P / C V and specific volume respec-
tively. Thus fi)r the following conditions: vapour phase, 100 K, 100 kN/m s and 0.5 molar
concentration; the specific volume would be obtained by writing FUEL PROP (2, 1000,
100, 0.05, 6). The formal parameters may be treated as variables if it is necessary t~,
determine their values by iterative application of tile procedure.
A listing of the program can be obtained by application to the author.

CONCLUSIONS
The r e p o r t has d e m o n s t r a t e d a simple m e t h o d of describing the t h e r m o -
d y n a m i c properties of a h y d r o - c a r b o n m i x t u r e fuel for the whole of the pressure-
t e m p e r a t u r e - p h a s e range likely to be e n c o u n t e r e d during diesel c o m b u s t i o n
calculations.
The a c c u r a c y of r e p r e s e n t a t i o n of the d a t a is perhaps s o m e w h a t less t h a n
t h a t justified b y the correlation techniques for a particular, correctly specified,
fuel, The technique can, however, be m a d e more sophisticated b y increasing
the stored d a t a w i t h o u t g r e a t l y increasing the c o m p u t a t i o n a l time. I n most
practical cases where the fuel specification is k n o w n b u t vaguely, t h e repre-
sentation m a y be considered too detailed a n d some increase in d a t a storage
intervals is justified. Care m u s t be t a k e n in this case, to ensure t h a t the
" c o a r s e n i n g " of the d a t a does n o t obscure the qualitative aspects of the fuel
properties, p a r t i c u l a r l y in the region of the critical point.

Acknowledgements--This work was executed whilst the writer was seconded to the Depart-
ment of Mechanical Engineering at U.M.I.S.T., Manchester. The author is grateful to
Professor W. Johnson for the facilities made available there and to Professor R. S. Benson
for help and guidance in preparation of the manuscript.
REFERENCES
1. P. R. WIEBER, z t I A A Jour~zal l, 2764 (1963).
2. A. N. SACHAREN,Chemistry of Petroleum Hydrocarbons. Reinhold, New York (1954).
3. K. M. WATSONand E. F. NET,SO~~, Ind. Chem. Eng. 25, 880 (1933).
4. J. B. MAXWELL, Data Book on Hydrocarbons. Van Nostrand, New York (1950).
5. W. L. N~SLSON,Petroleum Refinery Engineering. McGraw-Hill, New York (1958).
6. W. B. KAY, Ind. Eng. Chem. 28, 1014 (1936).
7. J.A.N.A.F. Thermochemical Data Tables. Dew Chemical Corporation (1960).