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A STUDY OF CONSTANT VOLUME COMBUSTION IN

HYDROCARBON-AIR SYSTEMS
a

Soupayan Mitra Research Fellow & Prabir Kumar Base Reader

a

Mechanical Engg Dept , Jadavpur University , Calcutta, 700 032, India

Mechanical Engg Dept , Jadavpur University , Calcutta, 700 032, India

Published online: 27 Apr 2007.

To cite this article: Soupayan Mitra Research Fellow & Prabir Kumar Base Reader (1995) A STUDY OF CONSTANT
VOLUME COMBUSTION IN HYDROCARBON-AIR SYSTEMS, Fuel Science and Technology International, 13:1, 25-48, DOI:
10.1080/08843759508947662
To link to this article: http://dx.doi.org/10.1080/08843759508947662

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FUEL SCIENCE AND TECHNOLOGY [NT'L., 13(1), 25-48 (1995)

A STUDY OF CONSTANT VOLUME COMBUSTION IN

Downloaded by [Columbia University] at 10:08 24 March 2015

HYDROCARBON-AIR SYSTEMS

Saupayan Mitra

Prabir Kumar Bose

Research Fellow

Reader

Mechanical Engg Dept.

Jadavpur University
Calcutta - 700 032
India

Me~hanical Engg Dept.

Jadavpur University
Calcutta - 700 032
India

ABSTRACT
A computational study

",i th

a deve loped goner,,1 ccmpu t e r-

program for the determination of equilibrium t~m~erature

and presure for constal,t volume combustion for any

hydrocarbon-air

mixture

in

presence

of

diluent

is

with particular reference to

methane-air
mixture at prescribed initial
conditions.
Several
observations are
noted
and
e~plained
and
same
computational values are compared with e:cperimental
values.

pr~sented

INTRODUCTION
The

objective

of

this

paper

is

to

study

the

equilibrium temperature, pressure and composition of the

25
Copyright :l 1995 by Marcel Dekker. Inc.

26

MITRA AND BOSE

products resulting from

process

of

constant

volume

mixtur~

hydrocarbon-air

initial conditions. The effects

temperature, pressure, diluent

of

combustion

at

the

ratio,

prescribed

parameters
and

equivalence

.atio have also been studied. The analysis

Downloaded by [Columbia University] at 10:08 24 March 2015

out

num~.icaly ~sing

was

a general computer code.

ca ied
Although

a number of p ap e r s a"d book'" are avai l eb le deal ing

the

constant

volume

extensive studies
reliable

are

comparision

combustion
very

much

between

tile

need

wi th

further

process,

in

of

.In

fact,

eHperimentaIly

numerically obtained values a.e scarce in the

and

available

literature.

THE BASIC RELATIONSHIPS

Certain simple assumptions are made in

the equilibrium
mixture.

Without

cum~licated

composition
those

and virtually

of

the

calculating

products

of

assumptions

it

is

imposaibJe

to

arrive

the

extremely
at

s o l ut icrrs . The assu.mptions are --il The flow is steady

flame ax i s ,

and

one

dimensional

along

the

27

STUDY OF CONSTANT VOLUME COMBUSTION

ii) The

combustion

products

are

homogeneous

and

of

constant composition throughout the flame.

iii) The combustion products obey the ideal gas laws.
iv) The flow is adiabatic and isentropic.
If these conditions are

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pressure and equilibrium

obeyed,

the

composition

of

temperature,
the

products

resulting from a combustion process at

constant

can be determined by applying the laws

of

volume

conservation

of mass and energy, laws of chemicaL equilibrium and the

concentration condition (combination of
Dalton's laws and the equation

of

Avogadro's

state

for

the

and
gas

phase) .
Thus, suppose

there

is

carbon-hydrogen-o:<ygen

-nitrogen reaction system and the initial stage

reactants are specified by
(0.)
. 1

temperature

and the number of moles (n.)

1

of

(1.),
1

each

the diluent ratio (DR) and equivalence

of

the

pressure

components',

ratio

()

also specified. The equilibrium products are assumed

are
to

cons i s t of ten chemical species as folo",s

2 '

0. OH, H,

!-tz' !-tz 0 '

CO, COz' NO

Therefore, 12 unknown quantities

Y,'
"-

are

N.z
to

be

knuwn

to

'specify the state of the equilibrium namely, equilibrium

28

MITRA AND BOSE

temperature IT ), pressure (P ) and the number of

e
e
n. of each of the above ten chemical

species.

moles

This

is

done by solving 12 equations as fallows

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Equation.of State (1 equation) :

r:

P.'.!

f'li

Hence,

T.

M~5S

............

Te

P.

= ----r-

n.

(11

n.

Cnnservation Equations (4 equations) :

The conservation of the total

number

uf

atoms

from

reactants to products can be expressed as --

Ln 1.. c.1 = L n J.. C.J

or,

+ :< + y +

3n

:!

co
z
12 )

+ no + 2'DH + 2"l-~ + 2"1-<0

The conservation of the number of atoms of each

element

frem reactants to

by

products

can

be

e~pressed

conservation of the atomic ratio a, nand

[2n

co

+ n

n
+
r:o
z

co

n
co

+ n

0+ 2n

.. n

nOH

the

as,

..
"

(3 ~

29

STUDY OF CONSTANT VOLUME COMBUSTION

(::

2n H 0
2

r [

2n

co

..

..
2

2n

.
2

co

..

+ n

n/1 0

] = r. co

QH

..

2n

..

+ r.
2

..

..............

cc

OH

(4)

"NO]

(5)

Chemical Equilibrium (6 equations) :

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The number of
of

number

the

these

chemical

l'quations
species

is

equal
the

in

to

the

equi librium

products minus the number of the elements. The followinq

dissociation reactions are considered
n
CO
2

~
~

CO++0

k1

"
n

H
H + -}- 02
20,.., 2

co

.n

H
Z

n
H
20

OH + -}- H
2

1
-2- 2

-2

.....

--'"

k-r =

n
n

H
2

-'"
..,-

OH

1/2

1/2

J./'Z

J " ( 6)

e
tn.

1/2

J ..

(7)

1/2
H

e
tn.

1/Z
)

(8)

e
tn.
J

e
tn.

1/2

.n

>-

:?:

(.0

.n

1/2

e
tn.

.
r~~ .
r~~

(9)

(10)

MITRA AND BOSE

30
n

NO
n
of

Conse~vation

of the

.n

( 11 )

1/2:
0

(1 equation) :

Ene~gy

For- adiabatic cons t an t volume

ene~gy

NO

1/2:

p~oducts

combustion,

is equal to

the

ene~gy

the

total
of

the

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~eactants.

Hence, E.

E.

(12)

~Ihere,

E.

= n

(h~ }f

+ n

(hO
T

= L n. .(hoT
J

E. = [ n
.1

ihen

co

= E.

E.

co~

(ho
T

+ n

+ n

i.

(ho
T

co

(ho
T

co

--

i.

L n.R T.
1

-- L n.R T.
J

.1

L n.R T.
J

T = T

The above 12 equations

tempe~atu~e, p~essu~e

a~e

to be solved to

dete~mine

and composition of the

the

equilib~ium

products.

METHOD OF SOLUTION

The above equations are solved computationally

the solution
given by

p~ocedu~e

Ag~a",al

et a l ,

is essentially
(1975) ",ith

simila~

to

modifications.

and
that
The

31

STUDY OF CONSTANT VOLUME COMBUSTION

complete computer program is not included

here

space limitations, but is available

the

f rom

due

to

authors.

This program is of general nature and can be applied

to

any hydrocarbon-air mixture provided the assumptions and

chemical species considered here are taken and the final
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t,=mpcl'ature

is b e l ovi 4000 :-I~.a

RESULTS

DISCUSSION

As an illustration of the above procedure

we

have

computed values o r aqu i l ib r iu.n temperature, pressure and

composition of equilibrium products of

constant

combustion of methane-air mixture for different

volume
initial

pressures and temperatures and for different equivalence

and diluent ratios.
The equilibrium temperature (T ) and pressure

(P)

of the products of combustion of

1.00) methane-air mixtures

are

stoichiometric
plotted

Fig.2 for diluent ratio (DR) 0.0 and

The

composition

of

the

in

= 800

Fig.1

=
and

0.1, respectively.

equilibrium

products

function of equivalence ratio (l is plotted

and Fig.4 for T.

in

as

Fig.3

OK and 600 OK respectively. Figs.

W
N

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3000
u ...vJ

'i/T; =0.002.5

0-0075

o.oz S

0.015

0-01

W-

I:::.
UJ
a:

I--

::J
I-

a:
w

0-

I-

::2

i--

L, Tl = 1100 a::

L.-

-I-

T'=1I001::
p;

j '"

O.OS

t-Ti=IOOOJ:;

I-- r

::2

0.03 0.04

T; = 9 0 0 l

+-

Ti=eOOl
Pi

T'=O.O';

;..-r;;700r
fi= 600.l

a:

t : 5001r.:

CD

:J

:5
o-

1;=400.:

T,=3001;

I
2300 1
1

( I

10

( !

50

EQUILIBRIUM PRESSURE {Pel, bar

100

200

I s::

>

Fig. 1.

Constant

volume

(=1.00, DR= 0.0)

combustion

of

Methane-Air

mixture

t:I
ttJ

2
ttl

Downloaded by [Columbia University] at 10:08 24 March 2015

300~
Pi IT; 00025

0.0040 0.0050 0.0015 0010

I
J

o"i

t:.

--

w
o.
::<
w
r

--

on

--l

c::
e
-<

o-n

!-f-n -'500'

l - l-,"""",

I-l - I--

0.020 O.02S 0.03

I-

t-e-~ l -

I--

- -

a:
:::J
!;
a:

0.015

Ti=IAQOJ:

on

I-J--r Ti" IlOO l:

0.Ol5

--rTo :1100K

--l

0.040

<

Tio 1100r:

To' 1000

o
l:

r-

c::

0.050

Ti=9QQl:

i;~800"

::<

[I1

0060

Ti- ]QOK

:::J

c::

on

1; "oDOr.

0:

:::tJ:l
--l

CD

(5

To 500 l:

;:;
:::J

li~OOl

oW

22001
1

Fig. 2.

Ti- JOOt

! ,

I ! !

10

50

EQUILIBRIUM PRESSURE (Pe), bar

Constant volume combus Lcn of Methane-Air mixture (=1. DO,

OR= 0.10)

w
w

Downloaded by [Columbia University] at 10:08 24 March 2015

34

MITRA AND BOSE

r
"it

UJ

g
Z

E
en
~

::;

20

2
..... 10

1.0

09
O.B
0.7

06
05
04

EQUIVALENCE RATIO

Fig. 3.

<+> - -

Equilibrium composition of combustion

products
of
Methane-Air
mixture
(pi=20bar, Ti=800K, DR=O.O)

Downloaded by [Columbia University] at 10:08 24 March 2015

STUDY OF CONSTANT VOLUME COMBUSTION

1...
UJ

Q
t:::

Ul

Fig. 4.

Equilibrium composition of combustion

products
of
Methane-Air
mixture
(pi=20bar, Ti=600K, DR=O.O)

3S

MITRA AND BOSE

_ - - - - - - - - - - - - Ti'\OOOK,DR'O.O

_-------------Ti'\OOOK,DR'O.\

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_ - - - - - - - - - - - - - Ti' 600K,DR,0.0

_ - - - - - - - - - - - - - - - Ti, .OOK,DR '0.0

INITIAL

PRESSURE I P i l , b o r -

Effect of initial pressure on equilibrium

temperature (=1.00)

Fig. 5.

5,6 and 7 show, respectively, T

p

vs. P. , T
1

vs. T.

vs. P. curves. Effects of equivalence ratio on T

1

at constant P. (5 bar) and T. 1500 I()

Fig.S

(T

v s , )

and Fig.9 (P

From the above

curves

vs ,

and

~ho\olf1

are

and

and
in

1.
results

some

general

observations ha"e been noted

i)

For

any

particular

T.

I.

and

Pi'

temperature (T ) and pressure (P ) are

e
e

the

equi 1 ibrium

highest

for

DR

37

STUDY OF CONSTANT VOLUME COMBUSTION

30001---~---------------,

Pi:50bof
Pi; 16 bar

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Pi: 400 bc r

'"
eo

::;
::>

2200 L-_---L_--.JL-_--L_--.J_ _---L_----I_ _...L....-.J

1300 1500
1100
700
900
500
300

Fig. 6.

Effect
of
initial
temperature
on
equilibrium temperature (=1.00) DR=O.l

=0.0 and the values of T

and P decrease monotonically

e
e
as DR increases from 0.0 to 0.2. This so happens since

presence of diluent mass helps lowering

do~

and

in combustion process.
iil For any particular DR and T i '

~rhen

P.

increases,

both T and P increases. But for constant DR and P.

e e l

38

MITRA AND BOSE

200r---------.,------;--_-;-_---,

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INITIAL PRESSURE (Pi). bar

Fig. 7.

--+-

Effect of initial pressure on equilibrium

pressure (=l.OO)

STUDY OF CONSTANT VOLUME COMBUSTION

39

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2600.---------------------------,

t
~
UJ

cr

UJ

a.
::;:
w

I-

::;:

:;)

cc

"'5

:::;

aw

EQUIVALENCE RATIO (~)

Fig. 8.

Effect
of
equilibrium
Ti=500K)

equivaIence
ratio
on
temperature
(pi=5.00 bar,

MITRA AND BOSE

40
27

1
.8

of
eo.
a:

UJ

::>
(/)

Downloaded by [Columbia University] at 10:08 24 March 2015

(/)

UJ

a:
Q.

:!
::>

Ii:
tll

::J

5
0

UJ

15.':----::-':----::'-::---7:---:-'::---;-';:--~--;_';;"-____:;_;

0.5

EQUIVALENCE RATIO ($) _ _

Fig. 9.

Effect
of
equilibrium
Ti=SOOK)

increases in T

equivalence
ratio
on
pressure
(pi=S.oo
bar,

and decreases in P

increases in T . Both pressure and

1

are

observed

temperature

with
appear

to dictate the degree of dissociation. According to

the

Law of Mass Action dissociation will be decreased as the

pressure

is

increased

because

the

volume

associated species is less than the volume

of

occupied

the
by

the dissociation products. On the other hand, the degree

STUDY OF CONSTANT VOLUME COMBUSTION

~Ii

of d i ssoc i at ion increases

Th~

effects

independent

of
of

pressure

combustion. Decrease
increase

in

in

and

are

temperature

Since

is

expected

Downloaded by [Columbia University] at 10:08 24 March 2015

in turn, tends

by

is

dissociation

endothermic process, a decrease in dissociation

in increase in T , \.llhich
e

not
volume

constant

fjlJring

dissociation

pressure.

temperature.

th increase in

ano t he r-

one

41

an

results

to

increase

dissociation. An increase in T. leads to an increase

in

to balance internal energy of reactants and

products

in canatsnt volume combustion. The ultimate result is an

equilibrium involving both temperature and pressure.

iii) For any particular
almost linearly

~ith

T.

P.

all

e:<cept

increase in the value of P

increase in T.

(for

for

with

small

P.

increases

The

P.

decelerates

with

for all DR.

I v ) The equivalence ratio (</II has

value of T

DRI

and P

Peak

impact

gr~at

values

of

on

and

the

Pare
e

observed near the stoichiometric mi:<ture. E:<cess fuel I

>

1) or excess air

( {

because a portion of

1)

heat

acts

released

utilised to raise these excess

fuel leads

to

incomplete

as

a
by

thermal
combustion

components.

combustion

sink

which

The

is

e:<cess

means

no

MITRA AND BOSE

42

release of all heat of

lead to low P
~)

and T

combustion.

and

temperature.

Downloaded by [Columbia University] at 10:08 24 March 2015

I:!

on

The

substances also act as a thermal

do",n P

these

factors

with excess fuel or excess air.

The diluent ratio has an impact

pressure

All

the

equilibrium

diluent
~ink

and

lead

to

noted

to

be

shifted

towards

and

= 0.0

~alues

as DR increases from 0.0 to 0.2, the peak

are

are highest in a slightly rich mi:<ture for DR

low

and T
e

For any particular P. and T. , the value of P

inert

or

the

and

of P

chemically

correct mixture.
vi) The nature of the curves of percentage mole fraction
composition

of

equilibrium

equivalence ratio (Fig. 3

species

riith

respect

4J are also corroborate

to
the

theory.
Comparision With

EKperimental

Values

volume bomb used fur

experimentation

high pressure vessel

consisting

of

The
was
tolO

spherical halves with recess to Hupport a

perspex ring for viewing the flame

growth.

holes were provided in the

to

vessel

constant
spherical

140
10

mount

mm
mm

SiK

Ld.
thick
radial

necessary

pressure transducer, spark electrodes, thermocouples and

43

STUDY OF CONSTANT VOLUME COMBUSTION

connecting pipe lines for charging

and

evacuating

the

vessel. The combustion chamber pressure was monitored by

a Piezo

electric

transducer

",hose output ",as fed

to

(\(ristler

t or-a

model

NIC-310 dual beam oscilloscope through a I(.ris tl e r

model

type

7055131,

Nicolet

5006 charge amplifier. The p-t record

Downloaded by [Columbia University] at 10:08 24 March 2015

model

can

obtain"d

stored on a floppy disk or it can be directly f"d

cumputer by RS-232 interface

data. THe fuel-ai" mixture was

three

cylinder

containers.

for

furth"r

The

an a t ys i s

of

stor"d

in

and

prepar~d

to

be

ignition

system

was

essentially the same as that uesd in an automoble with a

IZV

battery

description

as
of

the

energy

experimental

Source.

set

up

d"tail"d

Th"
and

followed in conducting the tests hav" be"n

proc"dures
r"port"d

in

Computationally obtained values for DR : 0.0 at

T.

the paper of Sharma et al. (19921.

520

01(

are compared with E',<.perimental values of Sharma

et al. (1992) and Bose (1992) in Table -1.

the

d i f f ar-anc e

between

experimentally

In

ob s e r-ved

computationally ob t ai ned vu l u es nf equi librium

for methane-air mixture for all cases are

general,
ami

pressure

within

percent. It is seen that the diff"rence betwe"n the

11
two

MITRA AND BOSE

44

TABLE
COMPAIHSON

BEnj~:Ell

05S,="VED PFlE.SSURE

(HJD

NUI1ERICALLY

CALCULATED PRESSURE. ALaNG WITH EQUILIBRIUM

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TEMPERATURE IDR=O.O, Ti=520"k )

'f'
(bar)

f rain

~xp~rirnen~ }

<).85
1 ..00
1. 15
1.30

0.85
1.00
1 15
1.30

2 .. (1)
2.00

2.0<)
2.1)1)

3. (1)
3.00
3.01)
3 ..00

9.44
9.80
9.75
9.67

\calcu'
lated)

(calculated)

7.12

3.5~

9.67

9.9'7

1 .. 3~
2.21

10.0':1

407

12.46
14.90
14.65

13.6'7
1 q. S.

14.22

15. 1:;

8.t;8
- 2.48
.,. 2.1!~
+. 6.01

14.97

0.85

4. <)1)

18.39

18.21

1 .. t)l)

1\.00

19.79

19.'17

1 15
I .30

4.00
4.00

19.85
18.41

19.97

0.85

5 ..

1.00
1.15
1 ..30

5. 1)0
5.0<)

22.95
24.64

Z2.86
2q.27

24 .. 33
23. I 1

25.27

1)1)

5.00

ZS.OO

:C.364.25
2489.59
2513.67
2478.50
2367.45
2497.37

2519.25

0./,0.

23:!J9.80

1.90
+ C'.60
-+ 8.86

2']1)3 ..('6

- 0.40
- I. '\4
+ 2.68
+ 8.55

2321.96

2485.92
2371.95

251)6.28

2524.49
2:lS1.40

0.85

6.1)('1

27.27

27.44

-+

0.62

.... ""l" .... ,

.!.....Jf -.J

1 .I)i)
1 . 15
1 .. 30

6. (1)

29.25

29 17
30.Ql
30.! .3

0.27

251~8. 61

+ 3 .. (H)
-.10.82

2487.84

6.(1)

29.11

6.0<)

26.87

..

7'7
_.

2525.76

45

STUDY OF CONSTANT VOLUME COMBUSTION

is always comparatively more on the richer side

or

the

stoichiometric value. This may be due, in part, to

the

lower availability of oxygen in the fuel

rich

The carbon in the fuel emits radiant heat at

mixture.
t/le

ratio

of fourth power of temperature.In fact, the high

Downloaded by [Columbia University] at 10:08 24 March 2015

species in the elevated flame

postflame regions may

not

temperature

even

be

energy

and

in

equilibrated

the
with

respect to internal partitioning of energy between their

own

internal

vibrational,

rotatonal

energy levels. E:ccess energy in

the

and

e I e c t r oo ic

Rl~ctronic

energy

levels may be lost as electromagnetic radiation which is

responsible, at least in part,
luminosity

of

flame.

These

for

the

factors

pressure rise to some extent low during

hich has

not

been

taken

into

characteristic
cause

the

peak

experimentation

account

in

case

of

computationally calculated pressure.

CONCLUSION

A complete general computer code has been developed

to calculate the equilibrium composition of the products
for the constant volume

combustion

of

hydrocarhon-~;r

46

MITRA AND BOSE

'mi x tur-e s under prescribed conditions. With the

the above code, the

help

combustion of methane-air

mixtures

at constant volume has been studied. Effects of

t~mpe('ature

ratio

, pressure, diluent ratio,

have

Downloaded by [Columbia University] at 10:08 24 March 2015

equilibrium

beeen

studied.

pressure

have

experimentally observed

The

computed

also

values

and

been
and

initial

equivalence

values

compared
good

of

of
wi ttl

agreement

e:,ists between the two.

NOMENCLATURE

DR

E.

E .
J

O
T

diluent ratio
mass of di luent
mass of total charge
~

total internal energy of

including diluent
reacta~ts

total internal energy of products

=total enthalpy at T with reference state at 298.16K

= equilibrium constant

"f '

"0 '"N
2

nuber of moles

of

fuel,

oxygen

nitrogen respectively
n.

= number of moles of ith reactant

n.

= number of moles of jth combustion product

and

47

STUDY OF CONSTANT VOLUME COMBUSTION

equilibrium pressure

e
P.

total pressure of reactants

pj

partial

universal gas constant

temoerature

= equilibrium

T.
Downloaded by [Columbia University] at 10:08 24 March 2015

su r a of jtt: coml:Juo;tion product

temperature

temperature of reactants

'J

p r-e s

= volume

~1,:(,'f,Z

number of

atoms

of

carbon,hydrQgen.OKygen

and nitrogen respectively

a

= atomic

ratio of carbon to

o~ygen

atomic ratio of hydrogen to oxygen

atomic ratio of nitrogen to oxygen

~ctual

fuel-air

ratio

'P = equi val en c era t i o = -:::T==::-:-==r:::-Z-:::-"T.77T:=7"":~=-=TC,-"""

stoIchiometric fuel aIr ratIO

REFERENCES

1. Agrawal, D. D., and Sharma, S. P. 1975(June). Journal

of Institute of Fuel, p.104.

2. Bose, P. K. 1992. PhD Thesis. Mechanical

Engin.ering

Department, liT Bombay, india.

3. Lewis, B., and Van Elba, G.

1~87.

Academic Press, New

Yor\<:.
4. Miller, P.A., and Mcconnel, 5.6.
Institute of Fuel., 45: p.43.

1972.

Journal

of

48

MITRA AND BOSE

5. Sharma, S. P., B051' , P. t<:., Iy"r, K. and JOSI'ph, C.

J., 1992. Proceedings of XII National Conference on I.C.
Engines and Combustion, lIP, Del,ra-Dun, India, p.507.

Downloaded by [Columbia University] at 10:08 24 March 2015

RECEIVED: JANUARY 24, 1994.

REVISED MANUSCRIPT ACCEPTED: APRIL 28, 1994.