CHARACTERIZATION OF THE MIXING /
CHEMISTRY INTERACTION
IN THE TOROIDAL JET STIRRED COMBUSTOR
by
ROBERT BENEDICT BARAT
B.S., New Jersey Institute of Technology (1980)
M.S., New Jersey Institute of Technology (1983)
SUBMITTED TO THE DEPARTMENT OF CHEMICAL ENGINEERING
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
at the
MASSACHUSETTS INSTITUTE OF TECHNOLOGY
February 1990
Massachusetts Institute of Technology, 1990
Signature redacted
Signature of Author..................................... .........
Department of Chemical Engineering
Signature redactedJanuary 4,
. . . .....................
Certified by..
.
.
Professor John P. Longwell
Thesis Supervisor
Signature redacted
Certified by.............. .
3.
/...
. . . ..
Profess rAdel F. Sarofim
.:.
.
.. . . . .
1990
Thesis Supervisor
Signature redacted
Accepted by ......................................................
Professor William M. Deen
on Graduate Studies
Committee
Chairman, Departmental
MASSACHUSETS INSTITUTE
OF TECHNO LOGY
1
ARCHIVES
MAR 28 1990
UBRAREG
CHARACTERIZATION OF THE MIXING / CHEMISTRY INTERACTION
IN THE TOROIDAL JET STIRRED COMBUSTOR
by
ROBERT BENEDICT BARAT
Submitted to the Department of Chemical Engineering
on January 4, 1990 in partial fulfillment of
the requirments for the degree of
Doctor of Philosophy in Chemical Engineering
ABSTRACT
The
toroidal jet stirred combustor (TJSC) is nominally a
perfectly stirred reactor (PSR), and hence is useful for measuring
rates of reaction in the absence of transport
effects.
The
performance of the TJSC was observed over a wide range of operating conditions,
and any deviations from a PSR state were
assessed.
An appropriate reactor engineering model for the TJSC
was then developed to improve the quality of reaction kinetic data
interpretation.
In order to better understand the mixing / chemical
interaction in the TJSC,
chemical systems of current interest in which
the elementary chemistry
is fairly well understood were used.
These were equimolar CO/H2 and C2H4.
Probability density functions (PDF's) of the instantaneous
temperature
fluctuations characteristic of turbulent combusting
flows were measured with laser Rayleigh scattering locally induced
in the TJSC near the torus axis.
Under high temperature operating
conditions, the narrow, unimodal PDF's obtained suggested that the
TJSC is homogeneous.
Accompanying stable species
concentration
data confirmed that,
as a good first approximation,
the TJSC can
be taken as a PSR under these conditions.
At lower temperatures,
the combustion chemistry is sufficiently retarded such that the TJSC exhibits non-PSR behavior.
This
was manifested in broad,
bimodal PDF's indicating localized
combustion instabilities,
and in measured
unburned fuel in excess of PSR predictions.
concentrations
of
A
reactor engineering model was developed which adequately
describes TJSC performance under either PSR-like or non-PSR conditions.
The model combines a turbulent jet mixing zone with a
perfectly stirred zone.
The model uses full elementary reaction
mechanisms.
With the TJSC characterized, work was initiated on a chemical
system involving chlorine,
where the chemistry is not well understood.
In order to assess the impact of chlorine on the backmixed
2
combustion environment of an incinerator, CH3Cl was added to a
fuel lean C2H4/air system.
Enhanced instability and localized
blowout, as determined through Rayleigh PDF's, were observed in
the presence of chlorine.
Modeling analyses indicated that
chlorine destabilizes backmixed hydrocarbon combustion by inhibiting the burnout of CO through consumption of OH radical by HC1.
Thesis Supervisors:
Dr. John P. Longwell
Emeritus Professor of Chemical Engineering
Dr. Adel F. Sarofim
Professor of Chemical Engineering
3
ACKNOWLEDGEMENTS
I wish to acknowledge and thank the following people:
- Steve Smith and Farhad Zarinetchi of course VI,
who
invaluable technical assistance and became good friends.
provided
- Antony Beris,
now an assistant professor at U.
Delaware,
and
Phil Westmoreland,
now an assistant professor at U.
Mass.,
who
were sources of strength for me during my difficult first year.
- Prof.
Joe
Bozzelli of NJIT,
source for a rate constant.
my mentor and always
the
best
- Carl Wikstrom,
now an assistant professor at U.
Arkansas, who
was
a great help in the early stages of writing a TJSC hybrid
computer model,
and who shared with me the joys and miseries of
graduate study at MIT.
- Current
or past members of the combustion group:
Steve Lai,
C.S.
Chang, Tom Griffin, Joe Marr, Jack "Black Jack" Brouwer, and
Larry Monroe.
- Mario daSilva,
a first rate machinist and hell of a nice guy.
- Secretaries Gabrielle Joseph and Kathy Brownell,
whose company
I have enjoyed greatly and who always had coffee ready.
- The
"women behind the men" who so often shared in the comraderie: Karen Smith, Pam Wikstrom, Samira Marr, Kathy daSilva.
- My family,
whose steadfast support pulled me through some
the darkest hours.
of
- Miss Kathy Gasbarro,
my fiance, who truely made the difference
for me during my last six months here.
I wish
to acknowledge the following organizations which
provided financial support at separate times during the course of
this project: a) The Exxon Research & Engineering Co., b) The U.S.
Environmental Protection Administration.
4
--- -, -1-
-
-A
. . . . .
1.1. Importance of the chemistry / mixing interaction . .
1.2. Stirred reactor in combustion /
.
CHAPTER 1 -- MOTIVATION . . . . . . . . . . . .
. .12
.
TABLE OF CONTENTS
. .12
1.5. PSR and the approach to blowout
. . . . .
. . . . . .
. . . . . .
. . . .
.
1.4. Importance of flame stability
. . . . . . .
. .13
.
1.3. Toroidal jet stirred combustor (TJSC)
. .12
. .16
.
incineration research
. .17
1.6. Special interaction problem: chlorocarbon incineration . .17
CHAPTER 2 --
BACKGROUND . . . .
. . . . . .
. . . . . . . . . .20
2.1. Observed deviation from PSR behavior . . .
. . . . . . . .20
2.2. Previous modeling efforts
. . . . . . . .20
. . . . . . . .
2.3. Independent cold flow studies by LIF . . . .
. . . . . . .22
CHAPTER 3 --
. . . . . .
. . . . . . .26
. . . . . . . . . . . . .
. . . . . . .26
OBJECTIVES AND APPROACH
3.1. Thesis objectives
3.2. Study of TJSC using system of known kinetics . .
3.3. Desired data . .
. . .
. . . . .26
. . . . . . . . . . . . . .
3.4. TJSC characterization - model development
. . . .26
. . . . . .
. .28
3.5. Special application: CH3C1 oxidation in TJSC . . . . . . .28
CHAPTER 4 --
CHAPTER 5
5.1. Optics
--
EXPERIMENTAL SYSTEM
. . .
.
. . . . . .
/ laser / electronics / signal sampling .
5.2. TJSC with optical access . . . . . . . . . . . .
5.3. Gas sampling and analyses
. . . . . . .
C5
. . . .
.
4.2. Description of the physics . . . . . . . . . .
. . . .29
.
. .
. . . .30
.
.
. . . .36
.
4.1. Brief review of LRS for flame thermometry
. . . .29
. . . .36
.
LASER RAYLEIGH SCATTERING FOR TEMPERATURE
. . . .40
.
- --- --.
. . . .42
CHAPTER 6 --
OPTICAL SYSTEM PERFORMANCE / LIMITATIONS . . . . .46
6.1. Optical calibration
6.2.
. . . .
System noise . . . . . .
. . . . . .
.
. . .
.
.
.
. . . . . . . . .46
.
6.3. Theoretical description of system noise
.
.
.
.
.
.
.
.
.50
.
.
.
.
.
.
.
.
.52
.
.
.
.
.
.
.56
6.4. Observed fluctuations and PDF deconvolution
CHAPTER 7 --
DATA / OBSERVATIONS FOR TJSC CHARACTERIZATION
7.1. Introduction .
.
.
.
.
.
.
.
7.2. Mechanics of PSR modeling
CHAPTER 8 --
. .
.
.
. . . . .
.
.
.
.
.
.
. . . . . .
. . . . .
Important guiding observations .
.
.
.
.
.59
. .60
. . . . . . . . .82
.
.
.
.
.
.
.
. 117
.
. 117
. . . . . . . . . . 117
.
.
8.4. New PFR (jet mixing) / PSR hybrid model
8.5. Mechanics of PFR(JM)/PSR modeling
.
. . . . . . .59
ORIGINAL MODELING FOR TJSC CHARACTERIZATION
8.2. TJSC modeling approaches .
.
.
.
.
.
.
.
.
.
. 119
. .
. . . . . . 120
.
.
.
.
.
.
. 122
. .
. 125
SPECIAL CHEMISTRY \ MIXING INTERACTION PROBLEM
. 137
8.6. Results of new hybrid model
CHAPTER 9 --
.
. . . . . . . . . . . . . . .
8.1. Fluid mechanics or detailed chemistry?
8.3.
.
. . . . . . . . .
7.3. Oxidation of CO/H2 . . .
7.4. Oxidation of C2H4
.
. .59
9.1. Introduction .
.
.
.
.
.
.
. . . . . . . . . . .
.
.
.
. .
.
.
.
.
.
.
.
.
.
.
. 137
9.2. Fuel lean CH3C1 oxidation mchanism development .
.
.
.
. 137
9.3. C2H4/CH3Cl oxidation data and PSR modeling .
. . . . . . 140
9.4. Use of PSR code for chlorine chemistry study .
9.5. Use of new hybrid model
.
. . . . . 153
. . . . . . . . . . . .
. .
. 168
CHAPTER 10 - FINAL DISCUSSION, CONCLUSIONS, RECOMMENDATIONS . 171
REFERENCES
. . . . . . . . . . . . . . . . . . . . . . . . . 175
6
-j
APPENDICES
. . . . . . . . . . . . . . . . . . . . . . . . . 178
A.l. Experimental and computer procedures . . . . . .
. .
. . 179
A.2. Rayleigh data workup and PDF generation
. .
. . 185
. . . . . . . . . . . . .
. . 186
A.3. Applications of QRRK . . .
A.4. Jet mixing equations for CHEMKIN . . .
A.5. Elementary reaction mechanisms .
A.6. Computer programs
. . . .
. . . . . . . . . 224
. . . .
. . . . . . . . 228
. . . . . . . . . . . .
7
. . . . . . . 239
-J
LIST OF TABLES
1-1: Characteristics and range of operating conditions of
the toroidal jet stirred combustor . . . . . . . . . .
.
.15
4-1: Rayleigh scattering differential cross sections
.33
.
.
.
.
7-1: Feed and operating conditions for fuel lean CO/H2
runs with increasing dilution for laser data . . .
.
.
. .61
7-2: Feed and operating conditions; observed, PSR, and
PSR+PQ concentrations for selected CO/H2 cases . .
.
.
.
.79
.
.
.
.
.83
7-4: Feed and operating conditions for fuel lean C2H4
runs with increasing dilution for laser data . . .
.
.
.
.90
7-5: Feed and operating conditions; observed, PSR, and
PSR+PQ concentrations for fuel lean C2H4 cases
with increasing dilution . . . . . . . . . . . . .
.
.
. 102
7-3:
Feed and operating conditions for selected fuel
lean C2H4 runs for laser data
. . . . . . . . .
7-6: Feed and operating conditions for selected fuel
rich C2H4 runs for laser data
. . . . . . . .
. . . . . 108
7-7: Feed and operating conditions; observed, PSR, and
PSR+PQ concentrations for a fuel rich C2H4 case
.
.
.
. 116
8-1: Observed, PSR, PSR+PQ, PFR(JM)/PSR, and PFR(JM)/PSR+PQ
concentrations for selected CO/H2 cases
.
.
.
.
.
.
.
. 126
8-2: Observed, PSR, PSR+PQ, PFR(JM)/PSR, and PFR(JM)/PSR+PQ
concentrations for fuel lean C2H4 cases with
increasing dilution
. . . . . . . . . . .
. . . . . . . 128
8-3: Observed, PSR, PSR+PQ, PFR(JM)/PSR, and PFR(JM)/PSR+PQ
concentrations for a fuel rich C2H4 case
.
.
.
.
.
.
.
. 135
9-1: Feed and operating conditions for diluted fuel lean
C2H4 and C2H4/CH3Cl runs for laser data
9-2: Observed,
.
. . . . . . . 141
PSR, and PSR+PQ concentrations for diluted
fuel lean C2H4 and C2H4/CH3Cl cases
. . . . .
. . . . .152A
9-3: Parameters for PSR calculations of temperature vs. mass
throughput for diluted fuel lean C2H4 and
C2H4/CH3Cl runs
.. . . .
. . . . . . . . . . . . . .
. 155
9-4: PSR calculated concentrations for diluted fuel lean
C2H4 and C2H4/CH3C1 runs near blowout
8
. . .
. . . . . . 158
9-5: PSR calculated rates-of-production of OH for diluted
fuel lean C2H4 and C2H4/CH3C1 runs near blowout
. . . . 161
9-6: PSR calculated rates-of-production of 0 for diluted
fuel lean C2H4 and
C2H4/CH3Cl runs near blowout
.
.
.
. 163
9-7: PSR calculated rates-of-production of H02 for diluted
fuel lean C2H4 and C2H4/CH3C1 runs near blowout . . . . 164
9-8: PSR calculated rates-of-production of C1 for diluted
fuel lean C2H4/CH3C1 run near blowout . . . . . . . . .166
9-9: PSR calculated rates-of-production of H for diluted
fuel lean C2H4 and C2H4/CH3C1 runs near blowout
. . . . 167
9-10: Observed, PSR, PSR+PQ, PFR(JM)/PSR, and PFR(JM)/PSR+PQ
concentrations for diluted fuel lean C2H4 and
C2H4/CH3Cl cases . . . . . . . . . . . . . . . . . . . .169
A-1: Reactions for
Cl/C2 Hydrocarbon Oxidation
. . . . . . .228
A-2: Species thermodynamic properties for C1/C2 hydrocarbon
oxidation . . . . . . . . . . . . . . . . . . . . . . .232
A-3: Reactions for fuel lean CH3Cl oxidation
. . . .
. .
. .233
A-4: Thermodynamic properties for chlorine containing
species
. . . . . . . . . . . . . . . . . . . . . .
. .235
A-5: Sources and notes on non-QRRK reactions in CH3C1
mechanism . . . . . . . . . . . . . . . . . . . . . . .236
9
A4
LIST OF FIGURES
1-1: Cross section of toroidal jet stirred combustor .
.
.
.
. 14
1-2: Idealized performance curves for a PSR
.
.
.
. 18
.
.
.
.
.
2-1: TJSC water model with single jet air injection
. . . . . 21
2-2: Fuel rich C2H4 combustion thermocouple traces in TJSC . . 23
2-3: LIF data from cold flow studies in aluminum TJSC
4-1: Rayleigh scattering optical sample volume .
.
.
.
5-1: Experimental apparatus for Rayleigh scattering
5-2: Electronic signal traces and sampling gate
5-3: TJSC optical access . . . . . . . . . . .
5-4: Flow system for current TJSC
5-5: Gas sampling train
.
.
. 25
.
.
.
. 31
.....
.
.
.
.
37
.
. 39
. . . . . . 43
. . . . . . . . . . . . . . .
. . . . 44
. . . . . . . . . . 47
6-2: Optical calibration: Net mean signal vs. pressure
6-3: Optical calibration:
.
. . . . . . . . 41
. . . . . . . .
6-1: TJSC optical calibration scheme . . .
.
.
.
.
. 49
System noise vs. mean net signal
.
. 51
6-4: Optical calibration: Signal distribution about the mean . 53
7-1: Rayleigh PDF mean and thermocouple temperatures as a
function of feed dilution for fuel lean CO/H2 . . . .
.
. 62
7-2 (A-->K): Observed and deconvoluted Rayleigh PDF's for fuel
lean CO/H2 oxidation with increasing dilution . . 64
7-3: Rayleigh temperature rms fluctuation as a function of
feed dilution for fuel lean CO/H2 . . . . . . . .
. . . . 76
7-4: Spatial thermocouple traces for fuel lean CO/H2:
undiluted and diluted . . . . . . . . . . . . . . . . .
. 78
7-5: Spatial thermocouple traces for CO/H2: rich and lean
.
.
(A-->D): Observed and deconvoluted Rayleigh PDF's for
selected fuel lean C2H4 oxidation . . . . . .
.
. 84
7-7: Rayleigh PDF mean and thermocouple temperatures as a
function of feed dilution for fuel lean C2H4
. . . .
.
. 91
7-6
81
7-8 (A-->E): Observed and deconvoluted Rayleigh PDF's for fuel
lean C2H4 oxidation with increasing dilution
10
.
.
92
7-9: Rayleigh temperature rms fluctuation as a function of
feed dilution for fuel lean C2H4 . . . . . . . . . . . . 99
7-10: Spatial thermocouple traces for fuel lean C2H4:
undiluted and diluted . . . . . . . . . . . . . . .
. . 100
7-11: CO concentrations as a function of feed dilution for
fuel lean C2H4: observed and PSR+PQ . . . . . . . . . . 105
7-12: C1+C2 hydrocarbon concentrations as a function of
feed dilution for fuel lean C2H4: observed and PSR+PQ . 106
7-13 (A-->D): Observed and deconvoluted Rayleigh PDF's
for selected fuel rich C2H4 oxidation . . . . . 109
7-14: Spatial thermocouple traces for C2H4: rich and lean . . 115
8-1: Schematic for PFR(JM)/PSR hybrid model
. . . . .
. . . 121
8-2: CO concentrations as a function of feed dilution for
fuel lean C2H4: observed, PSR+PQ, PFR(JM)/PSR+PQ
. . . 131
8-3: C1+C2 hydrocarbon concentrations as a function of
feed dilution for fuel lean C2H4: observed, PSR+PQ,
and PFR(JM)/PSR+PQ . . . . . . . . . . . . . . . . . . 132
9-1 (A-->E): Observed and deconvoluted Rayleigh PDF's for
selected fuel lean C2H4 and C2H4/CH3C1 runs .
.
143
9-2: Spatial thermocouple traces for diluted C2H4 and
C2H4/CH3C1 runs . . . . . . . . . . . . . . . . . . . . 150
9-3: Calculated PSR temperature as a function of mass flow
rate for diluted C2H4 and C2H4/CH3C1 runs . . . . . . . 154
9-4: Mechanistic pathways for diluted C2H4 oxidation . . . . 159
9-5: Mechanistic pathways for diluted C2H4/CH3C1 oxidation
.
160
A-1: Control volume for PFR(JM) enthalpy and mass balances
.
225
I I
CHAPTER 1 --
MOTIVATION
Importance of the Chemistry / Mixing Interaction
interaction of mixing and chemical reaction is of funda-
The
especially as
mental importance in chemical engineering,
applied
On the most basic level, fuel and oxidant must be
in combustion.
brought into contact in the presence of sufficient energy in order
for
reaction to proceed.
affected
by
The performance of a combustor will be
this contacting,
both in terms
of
efficiency
and
product / byproduct formation.
Stirred Reactor in Combustion / Incineration Research
The
istry
usefulness
research
of the stirred reactor as a reaction
tool derives from its simulation of
stirred
reactor (PSR).
formity
of temperature and composition.
fresh
feed
a
chem-
perfectly
Such a reactor is characterized by
Ideally,
immediately mixes into the volume of
before reaction of this new fluid begins.
the
uni-
incoming
reacting
Homogeneity of
fluid
mixing
must occur on both micro and macro length scales.
In
such
particular
a reactor,
species
the net molar rate of reaction r.
i per unit volume is obtained from
a
of
a
simple
*
mass balance on that species between inlet and outlet
r. - m (y. - y.
1
1
where
weight
- mass flow rate,
m
of i,
L
) / (V W.)
1
V - reactor volume,
y. - mass fraction of i,
(1-1)
W.
-
molecular
and * represents the feed
condition.
A
series
of
elementary
reactions
account for each net reaction rate r..
12
are
written
The set of reaction
to
mass
balances are solved simultaneously for given feed conditions.
is determined from the corresponding enthalpy balance
temperature
or
can be measured.
then
The predicted outlet concentrations
compared to the observed concentrations y..
quality data,
the
The
y.
Assuming
are
good
a lack of agreement suggests errors or omissions in
elementary
reactions
reaction rates.
proposed to account for
the
observed
A review is then performed of assumed elementary
reaction kinetic rate constants and species thermodynamic
values.
In this way, reaction chemistry research is performed with a PSR.
Toroidal Jet Stirred Combustor
The "state of the art" PSR for gas phase combustion
research
is embodied in the toroidal jet stirred combustor (TJSC) developed
by Nenniger et.al.
key
(1984).
characteristics
The TJSC is shown in Figure 1-1, with
listed
in Table 1-1.
Premixed
fuel
oxidant is injected into the torus through a manifold of 32
sonic velocity jets.
pated
and
near-
The turbulent fluid mechanical energy dissi-
from the inlet jets provides the power to mix the
incoming
feed into the reacting bulk flow.
The
TJSC
is
used
for
studies, as described above.
rich
ethylene
(1985).
Vaughn
(C2 H 4 )
(1988)
fundamental
combustion
chemistry
The fixation of nitrogen during fuel
combustion was
recently
studied
by
studied the formation of soot and
cyclic aromatics during combustion of fuel rich C2H
Sun
poly-
and C2H4/ben-
zene (C6 H 6 ) blends. Each study treated the TJSC as a PSR.
While
above
scopic
the
studies,
PSR assumption proved
to be
certain non-PSR behavior was
reasonable
observed.
in
the
Macro-
temperature inhomogeneities were observed by Vaughn (1988)
13
14
MANIFOLD
:
0
e0
Ib~
000
EXITS
00.0
-
-.
.00
TORUS
0
*
FIGURE 1-1:
-'
.*....'.
a
;
0
.--..
.. so.0
.e.s
Cross section of toroidal jet stirred combustor
TABLE 1-1
Characteristics and Range of Operating Conditions
of the Toroidal Jet Stirred Combustor
(cm)
REACTOR VOLUME
(cm)
TORUS MINOR DIAMETER
MEAN AXIAL FLOW VELOCITY
250
3.2
(m/s)
100 -
MEAN RESIDENCE TIME (10 3 s)
3 -
12
MASS FLOW RATE (g/s)
5 -
15
NUMBER
OF FEED JETS
32
JET TUBE DIAMETER (cm)
TURBULENT MIXINGS PER
RESIDENCE TIME
0.1
40 -
m)
5
KOLMOGOROV SCALE (10-5 m)
2
TAYLOR SCALE (10-4
(K)
PRESSURE
atm)
15
(
TEMPERATURE
2'00
1200
-
1
60
1900
A
during
C2H
fuel rich C2H
and
02
conversions
combustion
operations.
concentrations.
greater
of
He
under-predicted
Darivakis
(1986)
observed
observed
fuel
than predicted by a PSR model for fuel
lean
equimolar mixtures of CO and
H2.
These
nagging
issues of non-PSR behavior must be addressed in order to have full
confidence in recommending the TJSC for use in bench scale combustion /
incineration research.
The
The
PSR has special implications for incineration
highly recirculated flame stabilization zone just
from
be
downstream
the nozzle of many large scale burners and incinerators
modeled as a PSR.
fuel and air,
free
research.
can
It is in this highly turbulent region where
usually non-premixed,
are contacted.
radicals and energy from the downstream
Recirculated
combustion
provide
the active environment for flame ignition and stabilization.
Importance of Flame Stability
The
issue
of
stability in backmixed
practical and research implications.
depends
combustion
has
both
Flame stability, in general,
on a sufficient flow of heat and radicals to
ignite
the
incoming feed. As discussed earlier, the first zone of many industrial combustors can be likened to a PSR.
ization
occurs
as
heat
and
active
In this region, stabil-
radicals
from
combustion
downstream are backmixed into the incoming feed.
Stability is the key issue in the Special Problem section
be
discussed
later.
Flame instability can lead to products
incomplete combustion (PIC).
to
of
These can be as simple as excess CO
to complex and highly toxic chlorinated dioxins.
16
PSR and the Approach to Blowout
A stable operating point occurs
using idealized operating curves.
on
stability
PSR
illustrates the basic concept of
1-2
Figure
the high temperature branch when the reaction rate matches the
heat balance.
As the mass flow rate is increased and the tempera-
ture drops, blow out is approached.
The
approach toward a blowout point for a PSR
homogeneity even up to and including the
reactor
plete
assumes
com-
blowout.
Whether the TJSC behaves in this manner is an important issue
First, by studying the TJSC as we push
research for two reasons.
it
we are
toward blowout,
istry
interaction.
under
these
emulates
a PSR.
actually examining the mixing / chem-
How well the TJSC can
strenuous
for
maintain
conditions is a test of
Second,
does exhibit inhomogeneity,
how
as blowout is approached,
homogeneity
closely
it
if the TJSC
such as partial or localized blowout,
this non-PSR condition can lead to PIC.
impli-
This has serious
cations for hazardous waste incineration.
Special Interaction Problem: Chlorocarbon Incineration
Incineration
is
the disposal of chlorinated hydrocarbon (ClHC)
wastes.
chlorine
has been shown to have a negative impact on
flames.
It
velocities
for
currently viewed as a practical option
However,
hydrocarbon
flame
has been experimentally observed that laminar
decrease as the Cl/H molar ratio in the fuel increases
(Valeiras et.al., 1984). Weiss et.al. (1958) observed that a bench
scale,
fuel
lower
spherical jet stirred combustor (nominally a PSR)
lean
mixtures
of isopropyl chloride and air blows
mass flow rates than comparable hydrocarbons for
17
feeding
out
the
at
same
18
FIGURE 1-2
Idealized performance curves for a PSR
Stable High
Temperature Branch
A Blow-out
limit
Unstable Branch
LU
LU
LU
Stable low temperature Branch
MASS FLOW RATE
--
Stable
operating point
t
xr. Unstable
point
Enthalpy
balance
ILU
Reaction Rate
Equation
TEMPERATURE
-
U
equivalence ratios.
The apparent
general slowing of the chemistry in ClHC flames
has important implications for incineration.
cal
tool
for
associated PIC.
istry
The TJSC is a logi-
research into ClHC flame stability and
We are motivated,
the
often
then to understand the
chem-
/ mixing interaction in the TJSC so as to better understand
and design ClHC incinerators.
19
CHAPTER 2
--
BACKGROUND
Observed Deviation from PSR Behavior
Deviations
from PSR performance were observed in the TJSC by
Darivakis (1986) and Kridiotis et.al.
(1989).
CO/H 2 (equimolar mixture) combustion,
the measured outlet concen-
During fuel
lean
trations of H2 and CO were lower than predicted by a PSR model. No
significant
macro-scale temperature inhomogeneities were seen for
these fuel lean burns.
Darivakis postulated a degree of plug flow
character in the TJSC in order to account for this behavior.
Some
insight has been gained from water models of the
TJSC.
Residence time distribution experiments by Thomas (1979) suggested
that the equivalent of about 10 % of the reactor volume behaves as
a plug flow reactor (PFR).
graph
Examination of the water model
in Figure 2-1 shows the jet penetration and breakup.
evident
that a significant degree of jet character is
well into the volume.
photoIt is
maintained
Longwell and Bar-Ziv (1989) concluded that
the jet mixing nature of the flow must be considered as the source
of the departure from ideal behavior.
Previous Modeling Efforts
A model consisting of two PSR units in series was
by Darivakis (1986).
considers
problem.
the
the
postulated
This model ignores micro-mixing effects and
non-PSR behavior of the TJSC to be a
macro-mixing
Measured concentrations of CO and H2 were compared
predicted
outlet
concentrations from the second
PSR
to
unit.
Reasonable fits to the data were obtained by assigning ten percent
of
the
cases.
total
TJSC volume to the first PSR unit
At higher equivalence ratios (ca.
20
for
fuel
lean
0.7), though, the model
FIGURE 2-1
Photograph of the toroidal reactor water model
(Photograph by J.E. Nenniger)
21
underpredicts CO.
A
zero
developed
dimensional
by
redispersion
stochastic
Pantelides (1985).
concept
micro-mixing and
model
for
It employed
of Curl (1963).
the
the
This model
TJSC
was
coalescenceonly
examined
could not predict greater-than-PSR conversions.
Kridiotis et. al. (1989) introduced macro-mixing effects with
a
spatially
dependent
redispersion mechanism.
able,
mixing
intensity,
stochastic model using
the model satisfactorily predicted
the
It was concluded that the TJSC
more from imperfect macro-mixing than
mixing.
coalescence-
With an arbitrary, yet physically reason-
observed CO and H2 concentrations.
suffers
a
imperfect
micro-
This is consistent with the above suggestion of a degree
of plug flow character.
During
(1988)
fuel rich C2 H4 / air combustion in the
TJSC,
underpredicted experimentally observed parent C2H
concentrations by assuming a PSR model.
Vaughn
and
02
Observed product concen-
trations were reasonably well predicted with the PSR assumption. A
significant
macro-scale
temperature inhomogeneity,
as shown
in
Figure 2-2,
was observed from a thermocouple trace.
In order
to
the
rationalize
suggested
concentration
use of the two PSR's
volume blown out.
fit to the C2H
and
data,
temperature
in series model,
Vaughn
with the
first
This approach did not sufficiently improve the
and 02 data.
Independent Cold Flow Studies by LIF
A series of room temperature studies in a full scale aluminum
mock-up
vessel
of the TJSC have been performed by
is
operated at reduced pressures to
22
Bar-Ziv
simulate
(1989).
The
combustion
FIGURE 2-2
REACTOR TEMPERATURE PROFILES
6mm TEMP=1628 K ETHYLENE COMBUSTION
1630
-
1650
*
i
*1
1610
0
1570
-
1550
-
l590 L
1530
G
*1
/0
F
]
0
1310 L
-
I
1190
*-
1470
0-o
0
=2.O
*
(=2.2
1450
-1.2
-0.8
-0.4
0.0
0.4
0.8
1.2
DISTANCE FROM REACTOR CENTER LINE
FROM: VAUGHN (1988)
23
1.6
-1
densities.
for
The
flows are
turbulent flow.
maintained at high Reynold's
numbers
Laser induced fluorescence (LIF) of NO2 as a
tracer in air is used as the flow diagnostic.
Figure 2-3 shows five LIF spatial profiles obtained along the
laser
beam
upstream
jet.
pressures
The
when
the NO2
The
(60-350
tracer is
introduced
into
Torr) and residence times
There
is
Notice
single
profiles were generated over a wide range
(7.5-50
superimposability of these profiles implies
turbulence.
a
of
millisec).
fully
developed
that the concentration field is not uniform.
a significant tracer concentration in the
axial
zone.
Notice
also the similarity in shape to the thermocouple trace
Figure
2-2.
These data suggest that a degree of
jet
of
character
persists into the volume.
Probability
density
functions
(PDF)
of
the
LIF
signal
obtained near the centerline of the torus are shown in Figure 2-3.
The
narrower
Therefore
it
PDF was obtained with tracer present in
represents
the inherent
noise) of the LIF measurements.
statistical
all
jets.
error
(shot
The root mean square (rms) fluc-
tuation here is about 4 % of the mean.
The wider PDF was obtained
from
This
single
jet
tracer
injection.
considers the jet mixing in the TJSC.
is
PDF.
experiment
However,
actually
the observed PDF
a convolution of the inherent shot noise and the
true
mixing
It is estimated that the true mixing PDF (i.e. deconvoluted)
has an rms concentration fluctuation of about 4 %.
24
FIGURE
25
2-3
LASER
BEAM
LENS
0.8
C.6
0.4
distance.m11
Five (superimposed) laser induced fluorescence
profiles of NO 2
in
the observation line in the
reactor for residence times of 7.5-50msec and
pressures of 60-350torr.
0.07
0.06-
0.05
0
0.044
0.03-
0.02
-
4
+3
4
0.01 500
D
540
.
++
ta
16+
50
C0
00
+
620
Sao
700
NUMBER OF PHOTONS
PDFs of the concentration of NO 2 a at point on the
center line of the reactor: NO 2 was flown from all
only
(crosses) and NO2 was flown from one jet
jets
(squares).
CHAPTER 3
--
OBJECTIVES AND APPROACH
Thesis Objectives
The
objective
of
this work is a
characterization
of
the
interaction of turbulent mixing and chemical reaction in the TJSC.
Specifically, the goal is an appropriate model, or modeling guidelines
for the TJSC which will improve the quality of kinetic data
interpretation.
This model must explain any departures from
PSR
behavior under stable operating conditions where the TJSC would be
used for reaction kinetic studies.
Of equal importance, the model
must
be able to incorporate large elementary reaction mechanisms,
such
as
those used in
hydrocarbon
combustion
modeling,
while
remaining computationally tractable.
Study of TJSC Using System of Known Kinetics
Of
the
mixing
/ chemistry interaction,
process which is least understood.
terize
the
TJSC,
it is
the
mixing
Therefore, in order to charac-
systems in which the elementary
fairly well understood will be used.
chemistry
is
A systematic "decoupling" of
the mixing and chemistry is then possible.
Elementary reaction mechanisms are well established for
CO/H 2
oxidation,
Mechanisms for C
the simplest system.
carbon oxidation are significantly more complex,
understood.
The
but fairly
recent mechanism compiled by Miller and
(1988) is appropriate for the fuels of interest,
laboratory:
and C2 hydro-
equimolar CO/H2 and C2H .
well
Bowman
to date, in this
Therefore, the chemistry
for these fuels will be taken as known.
Desired Data
Turbulent
combusting flows are characterized by
26
temperature
fluctuations. In the TJSC, the rapid breakdown of turbulent eddies
is
important for well stirred behavior
bility
density
instantaneous
breakup
function (PDF) measurements
temperature
would
and the mixing process.
temperature
(Chomiak,
PDF's
offer
of
1984).
the
insight
In other
fluctuating
into
words,
Proba-
the
eddy
experimental
would offer insight into the mixing
and
sub-
sequent degree of homogeneity of the TJSC.
The
fluid
method
used to measure the temperature of
able
The
Also, the measurement technique must
to spatially resolve an appropriate eddy
length
scale.
Taylor micro-scale represents an intermediate turbulent
size.
As shown in Table 1-1,
is approximately 5 x 10~
is
turbulent
eddy must do so on a time scale which effectively "freezes"
the eddy in space and time.
be
a
about 100
m/sec.
eddy
a typical Taylor scale for the TJSC
meters (m). The mean axial flow velocity
Assuming a 5 % tolerance,
the
sampling time must be 2.5 x 107 seconds or shorter.
temperature
In addition,
the sampling time must be shorter than typical elementary reaction
time scales so that reaction in the eddy is not appreciably advancing while the sample is being taken.
that
characteristic
destruction
Kridiotis (1986) calculated
chemical times for
species
production
during CO/H2 combustion in the TJSC are on the
and
order
of milliseconds.
We
will
examine the TJSC under both stable
conditions approaching blowout.
equimolar CO/H 2 .
lower
conditions
and
The fuels burned will be C2H
and
Blowout will be approached through successively
temperatures obtained by dilution of the premixed feed with
N2 . Rayleigh temperature PDF's and concentration data will be gen-
27
erated.
As
a starting point for the modeling effort,
PSR
model
results will be compared to the observed species concentrations.
TJSC Characterization - Model Development
The
PDF's
and stable species data will together be used
to
characterize the TJSC. A performance model will be developed based
on this characterization.
In
order
whether
to develop an appropriate model,
we
must
decide
to emphasize fluid mechanics or detailed chemistry.
answer
The
to the above question is at the heart of the debate as
the best way to handle modeling of the TJSC.
to
Due to computational
load restrictions of available computers, simultaneous solution of
complete
turbulent
Navier-Stokes equations and
reaction sets is not feasible.
full
elementary
The desired emphasis of combustion
chemists is on detailed chemistry.
Therefore,
our approach will
be to simplify the fluid mechanical description while
maintaining
the full elementary chemistry.
Special Application: CH3C1 Oxidation in TJSC
With
where
the
chlorine,
the
TJSC characterized,
chemistry
is not
well
study will begin on a
understood.
The
system
impact
of
added as CH 3Cl, on the oxidation of C2H4 in a backmixed
combustion environment will be examined.
28
- -
CHAPTER 4
LASER RAYLEIGH SCATTERING FOR TEMPERATURE
Brief Review of LRS for Flame Thermometry
The temporal and spatial requirements discussed above suggest
use
of
temperature.
tant
focussed laser beam as
a pulsed,
for
1988).
This
avoids both the fluid mechanical and catalytic
which can accompany thermocouple use in flames.
species
in
flame
Laser Rayleigh Scattering (LRS) has become an impor-
tool in flame thermometry (Eckbreth,
method
diagnostic
the
flame contribute
to
the
optical
intrusions
With LRS,
total
all gas
elastic,
non-
resonant scattering.
An
ment
of
instantaneous
temperatures
obtained
by
is the measure-
(densities)
Bimodal probability density functions
flames.
ture,
important application of LRS thermometry
in
turbulent
(PDFs) of tempera-
Dibble and Hollenbach (1981) in
a
turbulent
premixed methane /
air flame,
show the fluctuating reaction zone,
or
Similarly,
root mean square
flame front.
(rms)
temperature
fluctuations
measured in turbulent jet diffusion flames
the
of shear mixing (and subsequent combustion) of
regions
and oxidant.
Rajan,
et.
al.
indicate
fuel
(1984) measured instantaneous IRS
line profiles in a premixed turbulent propane /
air
method eliminated the effects of flame front motion,
flame.
This
allowing for
accurate comparison of experimental and model rms density values.
these cases,
In
These
LRS was applied to non-distributed
flames.
systems exhibited some form of flame front and regions with
widely different densities.
These systems were not even nominally
well stirred.
The
current use of LRS to study temperature (density)
29
fluc-
-l
tuations in the TJSC is novel since the system examined should
in
a distribted combustion regime (Longwell and
There
should
be no flame front.
Bar-Ziv,
It is desired
to
be
1989).
distinguish
between relatively small differences in conversion of reactant, as
opposed
to
gases.
Our
simply
the difference between
application
of
burned
LRS inside an
and
enclosed
unburned
combustion
vessel is also novel.
Description of the Physics
Rayleigh
menom;
scattering
that is,
is an elastic light scattering
pheno-
the wavelength of the scattered radiation is the
same as the incident light.
There is no energy exchange, such as
in absorption.
The basic relation describing LRS from gases,
illustrated in
Figure 4-1, is given by
I
(Dibble
and
Io
fL
C
I
o
Hollenbach,
energy (Joules),
N
k
1981) where Ir -
incident laser energy,
=
(4-1)
m(41
collected
C -
system calibra-
constant accounting for optical collection and
efficiencies,
f)
scattering
transmission
- optical collection solid angle (steradian), L
-
tion
-
r
length of laser beam segment forming the optical sample volume and
determined by detector slits (cm), N - total number density of the
gas (1/cm 3),
and
2
(cm /steradian).
km - mean differential scattering cross section
This value
k
is a mole fraction weighted
m
mean
given by
k
-
mk
where
k.
-
scattering
1
E k. x.
i
(4-2a)
cross sections of species i and x.
1
30
-
mole
w
10
/ /
Laser Beam
/
I
jr
/
I
FIGURE 4-1
Rayleigh Scattering Optical Sampling Volume
fraction of i.
The dimension W, seen in Figure 4-1, is the laser
beam waist at the focal point.
As
will be discussed in the upcoming Experimental
section,
Apparatus
the incident laser beam used in this study is vertically
polarized.
Therefore,
the
appropriate differential
scattering
cross sections correspond to vertically polarized scattered light.
These are independent of the scattering angle and are given by
k. -
dG d0.2 4 TT
( L, - 1) 2
23
- - ------------------------------df)
2
4
(3 - 4 Pvi)
(4-2b)
NN.
(Rudder and Bach, 1968) where
- index of refraction of gas i at
-
standard temperature and pressure (STP: 273
K, 1 atmosphere), N
3
molecular number density at STP - 2.69 x 10 19 / cm3,
>
wavelength
gases
(cm),
and
= depolarization
=vi
Pvi
in this study have
ratio.
The
scattering
values which are essentially
zero.
The scattering cross sections used are listed in Table 4-1.
For
the current LRS thermometry application,
begin with the
ideal gas law, which is given by
where
P A
P - pressure (atm),
atm/mole-K),
absolute
A
/ (R T)
R
-
(4-3)
the ideal gas constant
- Avogadro's number (6.02 x 10
temperature (K).
23
(82.1
/mole),
Substitute for number density
cm3
and T
-
N -
N
from
equation (4-3) into equation (4-1) to yield
I - I C f) L P A k /
r
o
o m
The
observed
(R T)
signal S is assumed to be proportional to
collected scattered energy Ir according to
32
(4-4)
the
-4
TABLE 4-1
Rayleigh Scattering Differential Cross Sections
(10
Gas
-28
2
cm /steradian)
k.
(at 488 n)*
k.
(corrected'to 532 run)
N
8.780
6.216
02
7.309
5.175
CO
10.97
7.767
CO2
20.11
14.24
H20
6.280
4.446
C2 H
52.47
37.15
H
1.910
1.352
2
2
HCl
13.70@
CH3 Cl
40.57@
* Muller-Dethlefs and Weinberg (1978)
@ calculated from refractive indeces
33
I
S -
C' Ir
(4-5)
Substitute equation (4-5) into
S - C' I
Take
(4-4)
C f) L P A
to obtain
/
k
(R T)
the pressure P and incident energy I
(4-6)
to be constant.
Lump
all the constants together and rewrite equation (4-6) as
S - C" k
C f) L P A
In order to obtain C",
with
reference
a
(4-7)
overall proportionality constant C" is given by
C" - C' I
The
T
/ R
(4-8)
a reference experiment is
signal (S ) is obtained at room
known gas composition (k ).
performed.
temperature
(T
)
where the
/
Applying equation (4-7)
in
this case yields
C"- S
This
T
/ k
(4-9)
value C" will be used in the conversion of Rayleigh
signals
to temperatures.
Obtaining
flame temperatures from equations (4-7) and
(4-9)
requires the gas composition. Instead of assuming a constant k
in
m
the flame (Dibble and Hollenbach,
a
simple
released
raise
adiabatic flame
upon
temperature
relationship.
The
heat
incremental combustion of the feed is absorbed
the resulting mixture to the
example,
1981), the current work assumes
combustion
adiabatic
temperature.
to
For
of a fuel lean mixture of ethylene (C2 H4 ) in
air according to
34
A
+ 3 0
C2H
yields a simple,
relationship
2 CO2 + 2 H20
(4-10)
nearly linear (correlation coefficient >
between
mean cross section
k
0.999)
and adiabatic
flame
temperature T
-
k
A T + B
(4-11)
m
where A, B depend on the
As
and
composition and temperature of the feed.
feed is converted (combusted),
mean
cross
adiabatic temperature T
section km changes according
to
the
rises
resulting
mixture composition.
Substitution of equation (4-11) into (4-7) gives the
working
relation for obtaining flame temperatures from Rayleigh signals.
T - C" B /
The
value
C"
(S - A C")
is obtained from the
equation (4-9).
35
reference
(4-12)
experiment
using
--
CHAPTER 5
EXPERIMENTAL SYSTEM
Optics. Laser, Electronics, and Signal Sampling
The
experimental apparatus
is illustrated in Figure 5-1.
Quanta Ray frequency doubled Nd:YAG laser produces 6.5
A
nanosecond
(ns) pulses of plane polarized 532 nanometer (nm) light at a 10 Hz
repetition
rate.
Residual
fundamental radiation at 1064 nm
is
still present since the doubling efficiency is approximately 50 %.
beam is passed through an anti-reflection coated
meter
(mm)
from
milli-
focal length singlet lens which gradually narrows
an initial diameter of 6.4 mm to a focal point waist
intensity contour)
The
These
reflectance
(99
of 200 microns (Mm).
mirrors
residual
are fused silica flats
of 532 run light
at 450 incidence.
for
high
This allows for attenuation by transmission of
1064 nm light.
the beam,
coated
and low reflectance of 1064 run light
The beam passes through the
a pair of fused silica windows.
located
it
main beam is elevated and turned with a two mirror peri-
scope.
via
900
%
The
combustor
The focal point (waist)
forming the scattering sampling volume (Figure 4-1),
inside the combustor.
The incident beam
is
of
is
vertically
polarized (relative to the optical table).
Rayleigh
scattered
light is collected by a pair
convex
lenses [f -
passes
through a polarizing beamsplitter.
is
25 centimeter (cm),
d -
7.5 cm].
component.
bandwith
The
planolight
The transmitted light
horizontally polarized (relative to the table) and
as p-polarized.
of
designated
The reflected light is the s-polarized orthogonal
In each case, the light then passes through a 1.1 nm
interference filter centered at 532 nm.
36
Dual pairs
of
REACTOR
w
BEAM
W
Is
G
'AL
STOP
W'\ RAYL LIGHT
I
PERISCOPE
LENS
A ATT.
A7
,
LENSES
REAM
'..AM
______POLARIZING
.T
INF. FILTER
SLITS
ND:YAG
LASER
i
532nm
.
SUETACT
BOXCAR
BUS
COMPUTER FIGURE 5-1
PDF
:Experimental apparatus for Rayleigh scattering
37
>P IN
F )TODE
& F.A.
horizontal and vertical slits in front of each detector
the object size of the Rayleigh sample volume.
determine
All slits are set
at the laser beam waist diameter of 200 M1m. The s-component light
is
measured
volts DC.
side-on
by
a model C31034 RCA head-on PMT powered
The p-component
PMT
is measured by a model R928
typically powered at 550 volts DC.
supplies are both Pacific Instruments model 204.
the
two
by
1500
Hamamatsu
The
PMT
power
The signals from
PMTs are subtracted to yield a net signal.
A
detailed
explanation of the need for and operation of the two PMT system is
given in the upcoming Optical System Performance section.
A
representation of the net signal
is shown in Figure
5-2.
The 6.5 ns laser pulses create Rayleigh photon pulses of the
same
duration.
Short
PMT
response times (c.a.
result in pulses of charge,
time
constant
decay
25
ns)
effectively
which are allowed to decay with an RC
of 10 millisec (ms).
This allows the
signal
back to the baseline well before the next pulse.
voltage
is
measured
since it is proportional to the
The
to
peak
number
of
Rayleigh photons.
The
peak
Rayleigh voltage is measured by opening
a
narrow
electronic gate of 20 microseconds width just after the peak so as
to
The
avoid high frequency RF noise coincident with the laser pulse.
measurement
is performed by an EG&G/PAR
averager used as a sample-and-hold device.
also sampled before the peak.
is
performed by the boxcar,
4420
chronous
boxcar
The signal baseline is
Pulse-to-pulse baseline subtraction
thus accounting for PMT dark current
and any black body radiation from the TJSC walls.
levels
open
model
electronic pulse from the laser triggers the
the sampling gates at the appropriate times.
38
A
boxcar
synto
The boxcar is
RAYLEIGH
'1'I
I
I
I
I
I
II
11
BASELINE
SAMPLING
POINT
1,
TRIGGER
wD
qhLJ
GW
RAYLEIGH
SAMPLING
POINT
TIE
(Au)
---
'RC
>
FIGURE 5-2
Electronic Signal Traces and Sampling Gates
=
=
20JSEC
1.5
MSEC
I
interfaced,
via
an IEEE bus,
to a laboratory computer for
data
storage and analysis.
Accurate
requires
measurement
of
Rayleigh
scattering
fluctuations
that the pulse-to-pulse monitoring of laser beam
sity fluctuations,
which are about 3 %.
inten-
Setting the laser singlet
lens at a 50 angle of incidence to the laser beam reflects a small
fraction
bandwidth
of
the
laser beam through an
interference
diode detector.
filter
attenuator
and
1.1
nm
a
PIN
(centered at 532 nm) into
The resultant reference signal is sampled by the
boxcar in a manner similar to the above described approach for the
Rayleigh
signals.
Sufficient
signal-to-noise
is
available
precisely measure the laser intensity fluctuations.
nals
to
Rayleigh sig-
are then corrected on a pulse-to-pulse basis to
a
constant
average incident energy
I0.
TJSC With Optical Access
Only
differed
one TJSC was constructed and used in this project.
from TJSC's used in earlier studies in
this
It
laboratory
only by virtue of its optical access.
The
optical access added to the TJSC for this work is
in Figure 5-3.
The quartz windows for passage of the laser
are
placed about 38 cm from the beam focal point.
was
found
to ensure window integrity
energy fluxes.
incoming
sample
volume
This
beam
distance
at the highest laser
beam
An optical baffle is placed in the extension tube
holding the incident beam window in place.
the
shown
glare cocurrent with the laser
This removes some
beam.
for the collection of the Rayleigh
approximately along the axis of the torus.
40
The
of
optical
scattering
is
41'
SIDE VIEW
Toroidal Jet Stirred Combustor With Optical Access
TOP VIEW
WIWINDW
T/C
WINDOW
FIGURE
5-3
A
A
quartz viewing window is placed on the TJSC outer
for passage of the scattered light.
is
casing
The solid collection angle 0
determined by the approximately 0.5 cm hole in the TJSC
Similar
size
holes
in the TJSC walls allow for passage
wall.
of
the
laser beam.
The
laser beam passes at a 450 angle across the
meter (3.2 cm) of the torus.
minor
dia-
In the line of sight of the collec-
tion optics, the beam is passing only 1.6 cm in front of the white
refractory
wall
scattering
off
of the combustor.
the
Rayleigh scattering.
An
undesireable
background
wall at 532 nm is collected along
with
The compensation for this glare is the
the
pri-
mary subject of the Optical System Performance section.
In addition to Rayleigh scattering,
TJSC
were
typical
gas temperatures in
also measured with a type R thermocouple
inserted
position of the T/C bead is 6 mm
torus wall, about 20 % across the minor diameter.
the
(T/C).
in
The
from
the
The flow system
for the current TJSC is shown in Figure 5-4.
Gas Sampling and Analyses
The
gas sampling system is shown in Figure 5-5.
Stable
gas
species
are
probe.
Because the probe accesses the TJSC through the exit hole
collected
for the laser beam,
with a water
cooled,
stainless
steel
laser experiments and probe sampling are
performed simultaneously.
The probe tip is inserted about 6
not
mm in
from the torus wall.
The
metal
gas sample stream is drawn through the cooled probe by a
bellows pump.
Temperature profiles measured in the
probe
suggest that gas quench rates are comparable to those observed
42
by
C
99o9REG
9-I
C
V
H
c
WATER BAINI
60C
-C
REG
C2H4
FIGURE 5-4:
~A)
Gas Flow System for Current
Toroidal Jet Stirred Combustor
X
3-Wh11)OW
N2
x2
rIUSH
s
-
AIR
COM P
F-FLAStIOACK ARRESTOR
S-PRESS. SENSOR
1-hERMOCOUPLES
Fw-MAIN AIR
1-N? ADDITION
F20 Ii--F3V
5
RE
9
T1
TO__
L7TJ2
VENT
RUPTURE
DISK
LN2
REACTOR
FIGURE 5-5
GAS SAMPLING SYSTEM FOR STABLES
T:JSC
probe
7
knockout
to
grab
jar
PUMP
to
vent
to
vent
-P
-7
Vaughn (1988).
The
remove
gas
quenched gas stream passes through a knockout filter
entrained moisture.
A gas handling manifold directs
to
the
either to an online oxygen analyzer (not used in this study),
grab sample gas jars,
or vent. Grab samples are taken for offline
gas chromatographic (GC) analyses.
Separate CC analyses
examine
for the presence of light hydrocarbons and fixed gases.
The GC's used in this study are located in Room
fixed
gases are separated on a Porapak
Q
66-125.
The
column operated isother-
mally, with helium carrier, in a Perkin Elmer Sigma II GC equipped
with
a thermal conductivity detector.
vides separation of H2,
quantified
with
N2,
02,
Ar,
Operation at -850 C
and CO.
The signals
a Hewlett Packard 3390A integrator.
This
cedure is internally referred to as GC Method 8PQ with
Method
6.
proare
pro-
integrator
The column is operated at 250 C for separation of CO 2
using GC Method 7PQ and integrator Method 5.
In both cases,
the
typical injection volume is 0.1 cc.
The
light
hydrocarbons
are separated on a two
operated
with
argon
equipped
with
a flame ionization detector and
rator.
A
Porapak T column separates CH
carbons at 50
and C
carrier gas in a Hewlett
C.
column
Packard
5830
integ-
at 100 C and C2
hydro-
This analysis uses GC Method
with a typical injection volume of 1.0 cc.
45
GC
dedicated
A picric acid on Graphpak column separates
hydrocarbons at 500 C.
set
C3
1G-PT
--
CHAPTER 6
OPTICAL SYSTEM PERFORMANCE /
LIMITATIONS
Optical Calibration
The
the
passage of the laser beam through the narrow confines of
white
glare.
walled combustor creates
The
extraction
of the
an
Rayleigh scattering
background is based on polarization.
detail,
the
scheme.
scattering
undesireable
background
from
this
Figure 6-1 illustrates,
measurement and background
in
compensation
This glare is concurrent with the laser beam pulses,
and
is not related to thermal radiation from the hot TJSC walls.
The
Rayleigh
scattered
light from the
gas
vertical polarization of the incident laser beam.
was observed to be depolarized.
the polarizing beamsplitter,
maintains
The
the
background
The total scattered photons enter
which is coated for 532
nm.
Light
reflected from the splitter is a combination of the already verti-
cally polarized Rayleigh light (Ir) and the vertical,
nent, of the background
(Bs).
or s-compo-
The transmitted light is the ortho-
gonal p-component of the background.
and
signal
generating signal
B
S
S
photons pass into
The
S
factors a,
light enters
- a (I
S
The
B
the
head-on
PMT,
the
side-on
PMT,
b are linear
+ B
2
- b B
)
generating
Rayleigh
.
The
r
proportionality
(6-1)
constants.
These
signals enter a variable subtractor operational amplifier circuit.
This device is represented by
d
Y/2
46
~1
(6-2)
RAYLEIGH (R)
+ STRAY (B)
R + B
PMT iT2]
& BU F F ER
S2
=
POLARIZING
BEAMSPLITTER
S
a (R+BS)
B,
p
w
'7
VARIABLE
--
ISUBTRACTOR
S
4
b B
PMT I 1
& BUFFER
p
I
SD
TO
BOXCAR
S2
Fr
FIGURE
6-1
:
S1
(nfa)
)
fr
= -nsB
Y3. B S -b
B
p
Signal subtraction for extraneous glare removal
R +F
7
where
of
is a variable scaling factor (0 <
(6-1)
equations
constant
7
< 1).
into (6-2) shows that the
Substitution
is
background
offset to the linear relationship between net signal
a
Sd
and Rayleigh light Ir'
(7Ya) Ir +
Sd
(6-3)
r
The offset is given by
r
- b B
sp
a B
=
(6-4)
The purpose of the optical calibration is to vary
offset
7
such that the
r vanishes.
The calibration is performed with a variable pressure experiment at room temperature.
to a vacuum chamber.
The combustor is temporarily
The net signal
Sd is measured as a function
of nitrogen (or air) pressure P in the combustor.
and km,
substitute equation (4-4) into (6-3)
Sd -'T C
converted
P +
With constant T
to yield
r
(6-5)
where C# is an overall calibration constant given by
C
-a
I
C f) L A
k
/
(R T)
After a variable pressure run, any non-zero offset
(6-6)
r
prompts an
adjustment of the electronic subtractor via the scaling factor
This
rarily small.
6-2.
is repeated until the observed offset
procedure
The result of such a
After calibration,
is
7.
arbit-
calibration appears in Figure
the optical system is ready for combus-
tion experiments.
Another
source
of
undesireable light which can
enter
the
collection optics is blackbody radiation from the high temperature
48
-
700
{7
600
-
I
500
400
-
-
If
I'
LA'
I
-
300
z
I
200
I
100
-
EnTO
I
00
I
I
i
200
600
400
Pressure (Torr)
FIGURE 6-2: Optical Calibration -
- Final result, no offset
800
reactor
walls.
This radiation is broad-banded and
unpolarized.
The interference filters placed in front of each PMT are
at
nm with a 1 nm bandwidth,
532
this
component of the radiation.
centered
so will only allow passage
It has been observed that
of
any
contribution to each individual PMT signal from thermal
radiation
is small compared to the laser induced glare at 532 nm.
In addi-
tion,
in
the baseline subtraction used with the boxcar, as described
the Experimental Apparatus section,
will eliminate any radia-
tion component to the signal.
System Noise
A key experimental goal of the present work is to measure the
magnitude
of temperature fluctuations in the turbulent
the TJSC.
Each laser pulse yields a data point.
bustion
experiment,
are taken.
Pulse-to-pulse corrections
for
measured,
arate
due
points
laser intensity flucAny
fluctuation in
corrected net signal Sd is the result of Rayleigh
fluctuations,
of
In a given com-
a statistically large number of data
tuation are made in the raw data processing.
the
flame
scattering
to density (temperature) changes which must be
and random noise from the experimental system.
measurement of the magnitude of the system
absence of density fluctuations,
noise,
A sepin
the
is needed in order to accurately
interpret the observed signal fluctuations.
A
measurement
of the magnitude of the system noise is
formed simultaneously with the optical calibration.
of
The
data
one
such
The
calibration are presented in Figures 6-2
per-
results
and
6-3.
points on Figure 6-2 are each mean values based on over
1000
points
(laser pulses).
The error bars shown
50
are
+/- one
FIGURE 6-3
1.8
Observed and Predicted System Noise as a Function of Mean Net Signal
~1-i-
1.6
-
-
1.7
1.5
-
C4,
I
-
1.4
-
1.3
-
1.2
-
0.9
0.8
-
o
0.7
0.6
U.5
-I
1.7
0
I
I
1.9
Measured Noise
I
I
2.1
I
i
2.3
I
2.5
log(10) Mean Net Signal (mV)
+
Est. Shot Noise
.
2.7
I
,
0
1
-
w
1.1
-
L
E
0
0
2.9
Since corrections have already been made for
standard deviation.
pulse-to-pulse laser intensity fluctuations during raw signal data
and only inert gas occupies the combustor during
processing,
the
calibration,
error
bars
represent
magnitude
the
inherent system noise as a function of mean signal value.
the
of
the
The one
standard deviation magnitude, E, of this noise varies with
mean Sd
signal value, as shown in Figure 6-3, according to
E /S d - f S dg
d
(6-7)
The parameters f, g are specific for each optical calibration.
For
a given mean signal value S
a PDF or histogram of the
system noise is essentially a Gaussian distribution in
shown by the example signal PDF in Figure 6-4.
full-width-at-half-maximum
shape,
as
The PDF height and
correspond to values calculated for
a
Gaussian distribution with a given standard deviation.
as will be shown in
This system noise is optical shot noise,
the
next
(Yariv,
1985).
our
In
noise follows a
case,
the
Poisson
number
of
distribution
photoelectrons
by the Rayleigh pulses are sufficiently large that
generated
Poisson
Shot
section.
distribution
is
readily
approximated
by
a
the
Gaussian
distribution.
We must now examine the observed functional depen-
dence
noise magnitude with mean signal
of
the
ensure
to
that
system noise is limiting shot noise.
Theoretical Description of System Noise
The
photons
fundamental
impinging
efficiency
derives
shot
noise associated with a pulse
on a PMT photocathode
surface
of
n
p
77 quantum
from the uncertainty in the number of
52
of
photo-
FIGURE 6-4
40,. 1 r
23. 2
EXPERIMENTAL NOISE DISTRIBUTION
IS GAUSSIAN-SHAPED
exp = 31 mv
rexp
rGau = 74 mv
P max = 24
17. 4
Pmax = 26
Gau
%
0
N
0N
= 80 mv
exp
%
20. 3'
%jJ
-- 14. 5111. 3L
O 8.7
0.
5.8
2.9
0
0
200
400
600
800
1000
1200
NET SIGNAL (MV)
1400
1600
1800
2000
It can be described (Yariv, 1985) by
electrons emitted.
shot noise / pulse
---------------------photoelectons / pulse
Q
charge
The
( n 77)1/2
------------n 7
=
(6-8)
collected at the PMT anode from the photon pulse can
be written as
Q - V C - V (RC) / R - V
where V - peak voltage as the charge
the
R.
Q
T / R
(6-9)
is allowed to decay
across
associated RC circuit with total capacitance C and resistance
The peak voltage V and RC time constant
The
charge
Q
7 are observed.
can also be written in terms
of
the
photons
collected per pulse
Q - n
where G - PMT gain and e -
77 G e
(6-10)
1.6 x 10~19 coulombs / electron.
Setting equation (6-9) equal to equation (6-10) and substitution
for (n17) ) into equation (6-8) results in an expression for
the shot noise per pulse in terms of observable quantities.
1/2
(6-11)
expression
can be written for each PMT and
its
associated
Let S. - mean signal for PMT i.
signal V in the mean.
rms
shot
(G.eR./ T.)
noise from detector i.
For convenience,
define m.
full
1
1/2
Recall the subtraction described in equation (6-2).
noise
Let N.
-
This
-
[ G e R /7]1/2 /
shot noise / signal -
The shot
from PMT #2 is designated as N2 and is associated with
signal
S2,
not (Y
2).
The shot noises from each
independent; hence, their variances are additive.
54
PMT
the
are
The variance on
I
the net signal
Sd can be written as
(Nd 2 =
Substituting
tion
(6-12)
(N1)2 + (N2 2
(6-12)
equation (6-11) for each PMT signal into
/
yields an expression for the shot noise
equa-
mean
net
signal ratio.
Nd
m1 2 Sl + m 2
d
Using equation (6-2), write signal
During
the
background,
S1,
which
) /
7
(6-14)
is
based
solely
on
the
procedure,
depolarized
was observed to be constant (as it should be) as
pressure was varied.
to
(6-13)
the variable pressure optical calibration
signal
13)
d
1/2
S2 in terms of net signal Sd.
d + S1
2
2
the
Substitute equation (6-14) into equation (6-
obtain an expression for the shot noise as a function
of
the measured net signal
Sd'
N
-- --Sd
[m 2 S
2
d +
/ 7 ]1/2
-----------------------------------
-
Sd
A comparison of the observed noise,
cular
shot
6-3.
noise,
The
G
parameters mi:
ohms,
measured during a parti-
optical calibration and given by equation (6-7),
predicted
Figure
Tl
-
T2
=
as given by equation (6-15),
following values were used
to
- 1 x 10 5, G2 - 4.5 x 10 5, R1
1.5 ms.
with
is made
calculate
-
R2
=
the
in
the
4.2 x 10
The mean signal S1 was found to be a
constant 285 millivolt (mv) for this calibration.
5
(6-15)
d ranged from 50 to 700 mv.
55
The net signal
the functional dependence of the shot
As seen in Figure 6-3,
noise with mean signal is correctly predicted. The calculated shot
noise
levels exceed the measured system noise by approximately
a
only
a
A reduction in the gain factors G.
factor
of
2.2.
factor
of
5 would result in nearly perfect
factors
for
by
agreement.
The
sheets
are taken from manufacturer specification
listed
factory-new
PMT tubes and are not
actually
G.
here.
measured
these tubes have been in service for a number of years,
Since
is felt that actual G. values are somewhat lower.
it
Therefore, the
observed system noise is taken to be fundamental shot noise.
Observed Fluctuations and PDF Deconvolution
Rayleigh signal data
points from combustion are individually
converted to temperatures through the use of equation
statistically
large
(at least 2000 data points) set of
from a given run are arranged into a PDF
tures
size of 500 K.
Figure
7-2A
A
(4-12).
tempera-
with typical
bin
in
Such an observed temperature PDF is presented
fuel lean
for a stable,
This observed PDF is actually
shot noise blurring.
run.
CO/H 2 /air combustion
the true temperature PDF widened by
Therefore, it must be systematically decon-
voluted to reveal the best estimate of the true temperature PDF.
The deconvolution process utilizes the Constrained
Restoration
Algorithm (Schafer et.al.,
1981).
Iterative
This approach is
frequently used in digital image processing for noise removal
image
enhancement.
and
Assume the observed distribution is a super-
position sum of the true distribution and a blurring function
Y(n)
-
E
H(n,m) X(m)
m
56
(6-16)
where
Y(n)
is the observed probability of the
nth
temperature,
X(m) is the true probability of the mth temperature, H(n,m) is the
blurring
function relating the system response to a unit
at index m.
impulse
For the current work, H(n,m) is a matrix of Gaussians
with a varying standard deviation.
The algorithm consists of the recursion
Xk+1' - Xk
+
(6-17)
CL (Y - Xk H)
subject to the constraints
(6-18)
Xk+1 - C [Xk+l'I
where C[ ] signifies the constraint operator.
The steps are:
(a) Take a first guess at true distribution X1 (n).
(b) Apply the Gaussian blurring function H(n,m).
(c) Subtract the result from the observed Y(n).
(d) Multiply the residual by a scalar
(e) Add
this
product
(usually 2).
to the original guess
X1 (n)
to
form
X2 (n).
(f) Apply the constraints to X 2 '(n)
to generate the next guess
X 2 (n).
(g) Continue this process until Xk(n) converges.
For
the present work,
the constraints are:
1) no
and 2) no temperatures greater than the
probabilities,
flame temperature assuming complete feed conversion.
negative
adiabatic
Convergence
is obtained in 10 to 15 itterations.
An
example
discontinuous
deconvoluted PDF is shown in
Figure
7-2A.
nature of the deconvoluted PDF's is an artifact
57
The
of
the deconvolution procedure. The true PDF is most probably smooth.
We are primarily interested in the root mean square (rms) temperature
fluctuation (i.e.
is
which
unaffected
discontinuous PDF.
where
by a post-deconvolution
Real bimodal
smoothing
mean),
of
the
PDF behavior, such as in Figure
is similarly unaffected. A possible smoothing routine might
7-21,
use
one standard deviation of the PDF
a
simple
arithmetic averaging of adjacent bins of
there are discontinuities which are clearly not
of temperature inhomogeneities.
58
the
PDF
reflective
-9_
--
CHAPTER 7
DATA AND OBSERVATIONS FOR TJSC CHARACTERIZATION
Introduction
As
been
described earlier,
used
an equimolar mixture of CO and H2 has
in this laboratory in past studies
for
terization (Darivakis, 1986; Kridiotis, 1989).
TJSC
charac-
Much work has also
been done with C 2H . These later efforts (Sun, 1985; Vaughn, 1988;
Lam,
1988) treated the TJSC as a PSR.
In this project,
we will
take selected optical and species data from both these fuels.
a
starting point for the TJSC characterization,
we will
As
compare
its performance in this project to the PSR model.
Mechanics of PSR Modeling
Comparisons
TJSC
operation
of experimental concentration data
from
stable
will be made with predictions from a single
PSR
model. In the current project, the PSR model uses the PSR computer
code of Glarborg et.
rate,
al.
(1986).
The feed composition, mass flow
and observed T/C temperature are input,
volume (250 cm 3)
along with reactor
and pressure (1 atm).
The kinetic mechanism employed is taken from the C 1 /C 2 hydrooxidation
includes
set
of Miller and
Bowman
a subset for oxidation of CO and H
tion parameters are given in Appendix 5,
made
in
K,
one atmosphere).
Rice-Ramsberger-Kassel
et.al.,
this
Table A-1.
selected reactions in order to yield
1986)
This
Changes were
parameters
(ca.
Unimolecular and bimolecular
treatments
were employed.
(Dean,
1985;
appro900
Quantum
Westmoreland
(Discussion of the use of QRRK
project will be presented in the Special
59
set
The kinetic reac-
for the conditions of interest in this study
priate
1600
(1988).
-
carbon
Problem
in
Section).
The
QRRK input parameters and calculated rate constant parameters
for these modified reactions are included in Appendix 3.
Table A-
2 in Appendix 5 lists the thermodynamic properties for the species
used in this mechanism.
In all cases,
the reactor model output was further processed
in a probe quench (PQ) calculation.
effect
This simulates the quenching
of the water cooled probe actually used to collect the gas
samples from the TJSC.
temperature
profile.
It assumes a PFR behavior with an
The
imposed
probe quench calculation utilizes
CHEMKIN / LSODE package of Kee et.al.
(1980).
the
The FORTRAN driver
program appears in the Appendix.
In
the
current project,
an attempt to measure
temperature profile in the probe was not very
the
dimensions
of
the
actual
successful.
Since
the probe used are similar to those
used
by
Vaughn (1988), a similar temperature profile was assumed.
All
of
compositions are reported on a water free basis
because
the inability to accurately measure the water vapor content of
the sample.
Droplets of water were observed in the knockout
(see Figure 5-5).
trap
Therefore, it was assumed that the quenched gas
samples collected were saturated at room temperature and one
grab
atmosphere.
Oxidation of CO/H2
A
rates)
fuel lean (equivalence ratio - 0.52,
equimolar
temperatures
Table
tures.
7-1
by
fixed fuel
and
CO/H 2 mixture was burned at successively
addition
of diluent N2 to
the
lists the feed rates and thermocouple
premixed
(T/C)
lower
feed.
tempera-
Figure 7-1 shows how the T/C measurements decrease as
60
air
the
TABLE 7-1
TJSC Oxidation of CO/H 2 /Air Mixtures for Laser Data
Base Feed Gas Rates (scfm):#
Fuel --
->
2.06
(52.27 mole % CO, bal. H 2)
Air -- -> 9.5
Window N2 --- > 1.0
Equiv. Ratio --
->
0.516
PDF
Fig.No.
Dil.N2
(scfm)
Dil.N2
/total@
Total Mass
(g/s)
T/C Temp.
(K)
11
19
12
10
9
18
8
17
13
16
14
7-2A
B
C
D
E
F
G
H
I
J
K
0
0
0.8
1.6
2.4
3.2
4.3
4.9
5.6
5.6
6.2
0
0
0.06
0.11
0.16
0.20
0.26
0.28
0.31
0.31
0.33
6.66
6.66
7.11
7.55
8.00
8.45
9.06
9.39
9.79
9.79
10.12
1630
1580
1600
1510
1440
1370
1330
1290
1290
1240
1240
$
Run
No.
standard conditions ---> 60 0 F, 1 atm
corrected for conductive losses
ratio of volumetric flows
61
FIGURE 7-1:
Deconvoluted PDF mean and thermocouple temperatures as
a function of dilution for fuel lean CO/H2 (Ct>- 0.52)
1.7
3
1.6j
0
3
DD
1.4
1.3-
0
w
1..2 -~
0
++
1.1
1
0.9
,
0
3
,0
0.04
0 ,0
0 .1
0.08
0.12
I
I
I
0.2
0.16
DILUENT N2 FLOW /
THERMOCOUPLE
+
I
I
I
0.24
TOTAL FLOW
I
I
0.28
RAYLEIGH PDF MEAN
I ++ I
+
n0
0.32
all
Ns
4
premixed feed is increasingly diluted.
Rayleigh
temperature
corresponding
to
PDF's were also
obtained.
the conditions of Table 7-1,
is
A
series,
presented
in
Figure 7-2 (A-->K). Only selected PDF's will be highlighted here.
The
PDF
pair (observed and deconvoluted) for
an
undiluted
feed is given in Figure 7-2A. The deconvoluted PDF is unimodal and
narrow,
with
an rms fluctuation of only 5.4 % (85 K).
The
PDF
pair for run with a dilution ratio - 0.20 is shown in Figure 7-2F.
The
rms fluctuation for the deconvoluted PDF has risen to 130
K.
Traces of low temperature material ( < 800 K) are now evident.
The PDF pair for a highly diluted (ratio - 0.26) run is given
in Figure 7-2G.
The deconvoluted PDF has a large rms
(170
K) and shows a significant probability of low
This
suggests
i.e.,
localized flame instability,
fluctuation
temperatures.
or partial
occasional bursts of gas which have not ignited.
on the contrary,
blowout;
The T/C,
was stable under these conditions and in no
suggested instability unless total TJSC blowout occurred.
more
The
An even
diluted run (ratio - 0.31) is shown in Figure
highly
rms fluctuation is very large
(275 K) and there is
way
7-21.
an
even
greater probability of low temperature material.
Figure
7-1
shows that the means of the
also decrease with increasing N2 dilution.
of
about
0.2,
deconvoluted
PDF's
Above a dilution ratio
the PDF means decrease at a faster rate than
the
corresponding T/C readings.
The
rms
temperature fluctuation of the
increases with increasing dilution,
rms
magnitude
precisely
deconvoluted
PDF's
as shown in Figure 7-3.
The
increases sharply for a dilution ratio about
0.2,
where the PDF means decrease sharply.
63
This
is
where
FIGURE 7-2
THE FOLLOWING SERIES OF OBSERVED AND DECONVOLUTED PDF'S
CORRESPOND TO THE CONDITIONS DESCRIBED IN TABLE 7-1
64
65
NAMEs RUN 11
RUN DATEx 7/15/Be
0 OF DATA POINTS
OF MEAN
WK
DEV. C)
81
-
1984
1536. 03
16.6417
SIZE (W)- 50
-o
m.
C
4
(observed)
-
2
0
30
520
740
1180
960
1400
1620
1840
20r0
2280
2500
TEMPERATURE (K)
FIGURE 7-2A: Rayleigh PDF's for fuel lean CO/H2 (C- 0.52);
T/C
.
67
-
1630 K; diluent N2 flow/total flow
-
POF MEAN (K) 1553.1
ST.DEV. a) - 5.41073
BIN SIZE CK) - 50
60.3-
(deconvoluted)
53.5
rms fluc.
85 K
46.9-
-
40.2
33.50.
26.98
20.1-
13.4-
5. 7
30
520
740
950
1180
TEMPERATURE
1400
400
1620
1940
2060
2290
2500
0.0
106
NAMEs RUN 19
RUN DATEs 7/15/88
1987
N OF DATA POINTS
8
POF MEAN (K) ST.0EV.
BIN SIZE
(W)
-
(K) -
1581.56
15.759
50
(observed)
m
4-j
CL
4
2
0
300
520
740
960
1180
1400
1620
1840
2060
2280
2500
(K)
TEMPERATURE
FIGURE 7-2B: Rayleigh PDF's for fuel lean CQ/H2
(4>=0.52); T/C=1580 K; dil.N2/total=O
PDF MEAN (K) 1515.14
ST. DEV. (Z) 5. 57774
BIN SIZE (K) - 50
23.4-
rms fluc. = 85 K
20. 8-
(deconvoluted)
18. 2-
15. 6
13
10.4
0
7.8
5. 2
2.
0
6
300
520
740
960
1180
1400
TEMPERATURE
(K)
1620
1840
2060
2280
2500
10-
67
NAME:
RUN 12
RUN DATE:
7/15/88
# OF DATA POINTS:
8
PDF
MEAN (K)
ST. 0EV.
(%)
16. 8334
-
BIN SIZE (K)
1994
1544.4
-
-
50
6-
(observed)
02
0
0
4
2
"_j
0
300
520
740
960
1180
1400
TEMPERATURE
FIGURE 7-2C:
23
PDF MEAN (K) ST.0EV. (%) -
-
BIN SIZE (K)
rms fluc.
20.7-
-
=
1620
1840
2060
2280
2500
(K)
Rayleigh PDF's for fuel lean CO/H2
(4b=0.52); T/C=1600 K; dil.N2/total=.06
1487.46
8.23467
50
120 K
18. 4-
(deconvoluted)
16.1-
13.8
-D
11.5-
m
0
9.2
6.9
4.6
2.3
0
30
520
740
960
1180
1400
TEMPERATURE
(K)
1620
1840
2060
2280
2500
10-
68
10
NAMEt RUN
RUN DATEt 7/15/83
8
2025
OF DATA POINTS
.#
PDF MEAN (K) ST.
DEV.
BIN SIZE
(Z)
-
(K)
1464.54
16. 7727
-
50
6
(observed)
CL
4
2
,
0
300
520
740
960
1180
1400
TEMPERATURE
1620
1840
2060
2280
2500
(K)
FIGURE 7-2D: Rayleigh PDF's for fuel lean CO/H2
(t>=0.52); T/C=1510 K; dil.N2/total=.11
35
-
POF MEAN (K) 1392.69
ST. DEV. (Z) - 7. 39904
BIN SIZE (K) - 50
31.5-
rms fluc. = 105 K
28
24.5
~
(deconvoluted)
21
17.5
m
0
a.
14
10. 5-
7
0
-
3.5
300
520
740
960
1180
1400
TEMPERATURE
(K)
1620
1840
2060
2280
2500
1
2r
69
NAMEs RUN 9
RUN
10
0
0 1
30 0
DATE:
7/15/88
# OF DATA POINTSt 2040
PDF.MEAN (K) I338.81
ST.DEV. (Z) - 18 .2085
BIN SIZE (K) - 510
(observed)
'~
520
740
960
1400
1180
1620
-
1840
2060
2280
2500
(K)
TEMPERATURE
FIGURE 7-2E: Rayleigh PDF's for fuel lean CO/H2
.(c=0.52); T/C=1440 K; dil.N2/total=.16
37
POF MEAN (K) - 1309.5
ST. 0EV. (%) - 9. 7767
BIN SIZE (K) - 50
33.3
rms fluc. = 130 K
29. 5-
(deconvoluted)
25.9-
22.2-
H
C-
1.5-
0
14.2-
-Li
11.1
J-
7.4
3.7
0
300
520
740
960
1180
TEMPERATURE
1400
(K)
1620
1840
2080
2280
2500
70
12 r
NAMEs RUN 18
RUN DATEs 7/15/88
0 OF DATA POINTS
PDF MEAN (K)
ST.DEV.
-
mX) -
BIN SIZE (K) -
2024
1323.98
15.1229
50
S
(observed)
I-
-J
0
C
a.
01
30 0
520
740
960
1190
1400
TEMPERATURE
FIGURE 7-2F:
POF MEAN K) - 1291.06
ST.DEV. (Z)
10. 1378
50
BIN SIZE (W)
1840
2060
2280
2500
(K)
Rayleigh PDF's for fuel lean CD/H2
(4b=.0.52); T/C=1370 K;
dil.N2 flow/total flow = 0.20
-
21
1620
18.9
(deconvoluted)
rms fluc. = 130 K
18. 9
14.7
H
12. 5
I-J
0
10.5
0.4
8.3
4.2
2.1
0
r-300
520
740
9860
----
~
1180
TEMPERATURE
1400
(K)
1820
1840
2050
2290
2500
71
12
NAMEa RUN
RUN
DATE,
8
7/15/98
# OF DATA POINTS# 2021
1155.38
PDF MEAN (K) ST.DEV. (M) - 19.3551
BIN SIZE 00 - 50
10
.9
(observed)
-J
0
0
0
0.
4
2
FL-L
.
SI
3010
520
1400
1180
960
740
TEMPERATURE
36
-
-
POF MEAN (K)
ST. DEV. CX)
BIN SIZE (K)
-
40
1620
1940
2060
2280
2500
(K
FIGURE 7-2G: Rayleigh PDF's for fuel lean
CO/H2 (C> =0. 52) ; T/C=1330 K;
1111.99
dil .N2 fl ow/total flow = 0.26
15.2265
50
(deconvol uted)
rms fl uc. = 170 K
32
29
H
24
-J
0
20
a.
l
12
Li
9
4
a
300
F,11
520
r-1740
960
1190
n
m
1400
TEMPERATURE 00
1620
1940
2060
2290
2500
12
r
72
NAMEx RUN 17
RUN DATEt 7/15/88
101F
#
OF DATA POINTSs
POF MEAN (K) ST.DEV.
(Z) -
1974
1128.38
21.8928
LL
8
50
-
BIN SIZE (K) -
6-4
m
(observed)
4
2
a
0
300
520
960
740
ILLL
K
&___
1400
1180
1620
1840
2060
2280
2500
43
38.7
-
-
)
PDF MEAN
ST.
ZEV.()
BIN SIZE (K
-
TEMPERATURE (K)
1092. 47
21.2626
50
FIGURE 7-2H: Rayleigh PDF's for fuel lean
CO/H2 (4>=.52); T/C=1290 K;
dil.N2 flow/total flow = 0.28
rms fluc. = 230 K
34.4-
30.1-
25.8-
(deconvoluted)
m
21.50
17.2-
12.9-
8.8
4.3
FIL= m n
0
300
520
740
960
11 80
1400
TEMF ERATURE
(K)
1620
1840
2060
2280
2500
73
10
NAMEs
RUN 13
RUN DATEs
7/115/99
J OF DATA POIINTSo
POF MEAN (K)
ST.0EV.
C)
-
-
BIN SIZE 00
-
1867
954.123
33.5764
50
Hc
(observ ed)
4
2
L
0
300
520
740
960
1400
1180
TEMPERATURE
1620 -
1940
2060
2280
2500
(K)
FIGURE 7-21:
Rayleigh PDF's for fuel lean CO/H2 (C$)- 0.52);
T/C - 1290 K; diluent N2 flow/total flow - 0.31
POF MEAN (K) - 936.01
ST.DEV. (Z) - 29.4422
BIN SIZE (K) - 50
23
20. 7[
(deconvoluted
18. 4-
rms fluc.= 275 K
-
16. 1
H
13.8
-J
11.5[
mr
9.2
a. 9 p
4.8
2.3
0
300
520
740
960
1190
TEMPERATURE
1400
00
1620
1940
2060
2290
2500
W
8
74
NAMEs RUN 1B
RUN DATE
7/15/88
# OF DATA POINTS
6
PDF MEAN
ST. 0EV.
(K)
(W)
1005
-
34. 7755
-
BIN SIZE (K) -
4
1775
50
(observed)
0
0r
2
030
520
740
960
1400
1180
TEMPERATURE
32. 4
POF MEAN CK) - 972.935
ST. 0EV. (Z) - 31. 3921
BIN SIZE (K) - 50
28..
rms fluc. = 305 K
25.2-
(deconvoluted)
1620
1840
2060
2280
2500
(K)
FIGURE 7-2J: Rayleigh PDF's for fuel lean CO/H2
(C =.52); T/C=1240 K;
dil. N2 flow/total flow = 0.31
21. 5
1
-J
0
14.4
10.81
--
7.2
3.6
-e
0
300
520
740
960
1180
1400
TEMPERATURE
(K)
1620
1840
2060
2280
2500
-I
101
75
NAME: RUN 14
RUN I)ATEs 7/15/88
# OF DATA POINTSt
.POF P EAN
ST. DE V.
(K) -
950.318
29.7192
(%) -
BIN S IZE (K)
1916
-
50
m
6
ICL
(observed I)
4
2
0
300
520
740
960
1180
1400
1620
1840
2060
2280
2500
TEMPERATURE (K)
POF MEAN (K) - 923.201
ST.0EV. (Z) - 29.0003
BIN SIZE (K) - 50
-
21
18.9-
FIGURE 7-2K: Rayleigh PDF's for fuel lean
CO/H2 (<$>=.52); T/C=1240 K;
dil.N2/total = 0.33
rms fluc. = 270 K
16. 8-
(deconvol uted)
-
14. 7-
12.8
jF
--
10. 5
-J
0
8.4
-
8. 3
1
4.2
2.1
n
300
520
740
960
1180
1400
TEMPERATURE
(K)
1620
1840
2060
2280
2500
FIGURE
7-3:
Deconvoluted PDF rms temperature fluctuation as
a function of dilution for fuel lean CO/H2 (4 - 0.52)
320-
-
300
-
280
260"
240-
O
220200180160-
140120 -E
100 -3
80
I
0
I
0.04
0.08
0.12
0.16
0.2
I
0.24
DILUENT N2 FLOW / TOTAL FLOW
0.28
0.32
significant low temperature gas begins to appear.
As
expected,
increasing
the
dilution.
T/C values and PDF
position,
with
A probable explanation lay with the
of the optical sample volume relative to the
of a feed jet.
sampling
decrease
The unexpected result is the divergence of
the T/C and PDF mean values.
position
means
trajectory
Recall from Figure 5-3 that the Rayleigh
volume is located on or near the torus axis.
optical
The
exact
though, especially relative to a jet trajectory, is not
known.
The T/C is normally inserted 6 mm in from the wall,
20
%
across the torus diameter.
diameter
are
are
diluted case.
across
the
fuel
lean
given for typical undiluted and diluted
(equivalence ratio ca.
profiles
Spatial T/C traces
which is
0.5) cases in Figure 7-4.
essentially flat,
Notice that the
even at the centerline
for
the
(The dashed lines on the traces represent the esti-
mated profile.after correction for T/C conductive losses).
These observations sugguest that the optical sampling
is
volume
somewhat offset from the torus axis and in the path of a
The
T/C
apparently traces across a region where significant
structure no longer exists; e.g.,
of a jet.
jet.
jet
"behind" the bending trajectory
The T/C reading is only about 70 K higher than the
PDF
mean at no dilution (see Figure 7-1). This would suggest that, for
these runs, significant reaction has occurred in the jet before it
has fully broken up.
Some
system
Table
to
new
concentration
data were obtained
supplement the existing
7-2 lists the feed conditions,
and PSR modeling results.
database
for
the
(Darivakis,
experimental
CO/H 2
1986).
observations,
Also listed are the figure numbers and
77
FIGURE 7-4
THERMOCOUPLE TRACE
1.65
-
1.6
-
1.7
-
~---
---
--
-
0
0
D
1.55
-
00
LLJ
1.45
-
-
1.5
qL.c
1.41.35
-
F-
1.3-
+
-
1.25
1.2
I
I
0
0
+
+
+++
20
"HOT" LEAN CO/H2
I
40
I
i
60
80
DISTANCE ACROSS DIAMETER (%)
+
rCOO U' LEAN CO/H 2
100
TABLE 7-2
TJSC Oxidation of CO/H 2 /Air Mixtures
5
6
7
6.70
9.76
5.55
CO
0.0755
0.0528
0.1350
H2
0.0862
0.0602
0.1541
02
0.1596
0.1115
0.0892
N2
0.6787
0.7755
0.6217
Dil.N 2 flow/total flow:@
0.0
0.30
0.20
0.507
0.507
1.620
1640
1300
1760
7.9
6.7
8.3
Case Number:
Feed Rate (g/sec):
Feed Mole Fractions:
Equivalence Ratio:
T/C Temperature (K):$
*
Residence Time (msec):#
Product Concentrations:
Measured:
PSR:
PSR+PQ:
0.0
0.08
0.02
0.0
0.07
0.04
5.02
4.47
5.31
0.15
0.38
0.27
0.89
0.55
0.50
10.7
9.09
8.54
7-2A
7-21
-
H2 (mole %)
85
275
CO (mole %)
Measured:
PSR:
PSR+PQ:
Corresponding PDF
Figure Number:
Decon.PDF rms fluc.(K):
*
#
$
@
water free basis
based on molar feed rate, T/C reading, total volume
corrected for conductive losses
flows are volumetric
79
deconvoluted
rms
of
fluctuations
Rayleigh
taken
PDF's
under
approximately the same combustion conditions.
For
observed
#5,
the
concentrations of CO and H2 are at least 50 % less
than
the stable,
high temperature (undiluted) case
Similar results were
the corresponding PSR/PQ calculated values.
observed by Darivakis (1986), who postulated a degree of plug flow
character in the TJSC to account for this behavior.
A very interesting result is seen for case #6.
The measured
CO concentration for this heavily diluted run, in contrast to case
exceeds the PSR/PQ prediction by nearily 50 %.
#5,
Such fuel gas
concentrations in excess of PSR+PQ predictions will be referred to
as excess unburned fuel.
The PDF for essentially the same condi-
tions (Figure 7-21) shows a much larger rms fluctuation (275 K vs.
85 K) and significant low temperature bursts. These data suggest a
correlation
between
the appearance of excess unburned
and
fuel
localized instability in the TJSC.
A
(Case
fuel
rich run (equivalence ratio -
tions agree,
concentraSimilar
while measured CO exceeds the model value.
results were reported by Darivakis (1986).
Measurements of 02 are
for fuel rich runs as it is the limiting
though,
reliable 02 data were available,
No
reagant.
for case #7.
The fol-
PSR -- > 0.06 mole% ; PSR+PQ
-- >
.
lowing 02 values were calculated:
0.001 mole%
performed
was
The experimental and PSR/PQ predicted H2
#7).
preferred
1.62)
What is more exciting is the T/C trace for this run, which is
shown
notice
in
Figure 7-5.
that
(Figure 7-4).
the
After correcting for
profile is flat,
conductive
as for the lean
CO/H 2
losses,
cases
This result is consistent with profiles observed by
80
FIGURE 7-5
THERMOCOUPLE TRACE
1.75
1.74
-1
1.73
-
1.72
-e4
1.71
1.7
1.69
1.68
00
1.65
1.64
1.63
/
1.62
0
1.61
1.6
1.59
1.58
1.57
1.56
0
1.55
I
0
20
0
40
DISTANCE ACROSS DIAMETER
"HOT" LEAN CO/H2
60
i
80
100
(7)
+
M
1.67
1.66
RICH CO/H2
co
Kridiotis (1986).
rich C2H
suggests
,
This is contrary to what has been observed for
as shown in Figure 2-2 (Vaughn, 1988).
that
This difference
the jet mixing in the TJSC accentuates
the
real
differences in chemistry and heat release rates between
rich CO/H 2
and rich C2H
Oxidation of C2H4
As with CO/H
much work has been done with C2H
in the TJSC.
This work, however, has treated the TJSC as a PSR. A series of new
data has been generated with C2H
Consider
in this project.
first Rayleigh temperature PDF's obtained for
ected fuel lean (equivalence ratio ca.
7-3
lists the feed and operating conditions.
deconvoluted
PDF's
The
T/C readings.
PDF's are quite narrow at these high
to
These deconvoluted
temperature conditions.
prove that the non-premixed
addition
window N2 was not the cause of the deconvoluted PDF width,
was performed with the window N2 reduced by 92 %.
that
in
The deconvoluted PDF
temperature fluctuations are about 85 K.
order
series
and
The means of the deconvoluted PDF's are about
80 K less than the corrected
In
Table
observed
for these runs are presented as a
Figure 7-6 (A-->D).
rms
0.5) C2 H4 /air runs.
sel-
of
Run #3
Table 7-3 shows
the RMS fluctuation is essentially unchanged as compared
the normal Runs #1,2.
The PDF width,
the
to
in fact, reflects the chem-
istry / mixing interaction in the TJSC.
As with the high temperature (undiluted) CO/H 2 run (Figure 72A)
these narrow PDF's are consistent with the claim by
and
Bar-ziv
(1989)
that
stable
throughout the reactor volume (i.e.
82
TJSC
flames
are
Longwell
distributed
no discernable flame fronts).
TABLE 7-3
TJSC Oxidation of Selected C2 H4 /Air Mixtures for Laser Data
1,2
Run Number:
3
<---
Run Date:
8
11/2/88
7.41
6.90
6.58
0.0330
0.0356
0.0373
02
0.1868
0.2011
0.2007
N
0.7802
0.7633
0.7620
0.0
0.0
0.530
0.530
0.557
T/C Temperature (K):$
1625
1645
1720
Residence Time (msec):
7.3
7.7
7.7
Corresponding PDF
Figure Number:
7-6A,B
7-6C
7-6D
85
75
Feed Rate (g/sec):
Feed Mole Fractions:
2H
2
Dil.N 2 flow/total flow:
#
Equivalence Ratio:
Decon.PDF rms fluc.(K):
*
#
$
@
0.0
95
ratio of volumetric flows
based on molar feed rate, T/C reading, total volume
corrected for conductive losses
window N2 set at normal value (1 scfm, 60 0 F, 1 atm) for
runs #1,2;
flow reduced to 0.08 scfm for runs #3-->8.
63
FIGURE 7-6
THE FOLLOWING SERIES OF OBSERVED AND DECONVOLUTED PDF'S
CORRESPOND TO THE CONDITIONS DESCRIBED IN TABLE 7-3
84
-A
8
85
NAME:
DATE:
RUN
# OF
6
PO
RUN 1
OATA
POINTSt
MEAN (K)
ST OEV.
(Z)
0
-
1981
1530.59
15. 5085
-
SIZE (K)
11
4
11/2/88
50
-
(observed)
a.
2
01
30 0
520
740
960
1180
1400
1520
1840
2050
2280
2500
TEMPERATURE (K)
FIGURE 7-6A: Rayleigh PDF's for fuel lean C2H4
(4 =. 53) i T/C= 1625 K; dil.N2/total=0.0
-
54
POF MEAN (K) 1548.77
ST.0EV. (%) 5.8555
BIN SIZE (K) - 50
49. 8-
rms fluc.
43. 2-
= 85 K
(deconvoluted)
37.8
K
--H
32. 4
-J
27
21.5
15.21
10.8
U
-
5. 4
300
520
740
960
1180
1400
TEMPERATURE (K)
1620
1840
2050
2280
2500
86
1C r
NAME: RUN 2
RUN DATE: 11/2/88
# OF DATA POINTS:
8
PDF MEAN
ST.0EV.
K) -
CZ)
-
BIN SIZE (K) -
1990
1625.48
15.0967
50
I-rJ
(observed)
0
a4
. 2
'
0
30 0
520
740
960
1180
1400
1620
1840
2060
2280
2500
TEMPERATURE (K)
FIGURE 7-6B:
Rayleigh PDF's for fue 1 lean C2H4
41
36.9-
rms fluc.
32.
-
-
POF MEAN (K)
ST.DEV. (Z)
BIN SIZE (K)
-
((I)=0. 53) ; T/C= 1625 K; dil.N2/total = 0.0
1553.79
4.93248
50
= 85 K
8-
28.7-
(deconvoluted)
24.
6-
m
20.
5-
0
16. 4-
12.3-
8.2
4.1
0
300
520
740
960
1180
1400
TEMPERATURE (K)
1620
1840
2060
2280
2500
-i
10
87
NAME,
RUN 3
RUN DATEs
8
11/2/88
# OF DATA POINTSs
POF MEAN
ST. OEV.
WK
-
az) -
IN SIZE CK) -
1995
1651.24
14. 9322
50
S-J
(observed)
4
2
0
300
520
740
1180
980
1400
1120
1840
2060
2280
2500
TEMPERATURE (K)
FIGURE 7-6C: Rayleigh PDF's for fuel lean C2H4
T/C = 1645 K; dil.N2/total = 0.0
37
POF MEAN 00
1570.63
ST.0EV. (Z)
4. 63438
SIN SIZE (K) - 50
33.3-
rms fluc.
= 75 K
6
-
29.
-
(C4=0.53);
(deconvoluted)
9
22.2
-
25.
18.5-
14.8-
11.1
7.4
3.7
0
300
520
740
960
1180
TEMPERATURE
1400
(K)
1620
1840
2080
2280
2500
a
98
AME3
RUN
DATE:
11/2/88
#
DATA POINTSt
PDF
EAN CK) -
ST.D
V.
2010
-
8
8
BIN SI E
(observed)
HL
14.9168
WZ) W<
1713. 13
-
50
4
2
0
300
520
740
1180
960
TEMPERATURE
1400
1820
1840
2060
2280
(K)
FIGURE 7-6D: Rayleigh PDF's for fuel lean C2H4
T/C = 1720 K; dil.N2/total = 0.0
(c>=0.56);
POF MEAN (K) - 1625. 9
ST. DEV. Ca) - 5. 90538
BIN SIZE (K) - 50
-
41
2500
36.9-
rms fluc.
= 95 K
32.8
28.7-
(deconvoluted)
H
24.8-
I-J
20. 5-
0
0.
16. 4-
8.2
-
4.1
-
12.3
0
300
520
740
960
1180
TEMPERATURE
1400
00
1820
1840
2060
2280
2500
Such
narrow PDF's (rms fluctuations about 5.5 % of the mean)
also
consistent with the PDF of the LIF signal
about
4
(rms
are
fluctuation
%) obtained near the torus axis (Figure 2-3) by
Bar-Ziv
(1989) in room temperature TJSC mixing studies.
Fuel
lean
successively
premixed
(T/C)
(equivalence
ratio - 0.54) C2 H4
was
burned
at
lower temperatures by addition of dilution N2 to the
feed.
Table 7-4 lists the feed rates and
temperatures.
Figure 7-7 shows that the
thermocouple
T/C
measurements
decrease with increasing dilution.
Rayleigh
corresponding
temperature
to
PDF
obtained.
the conditions of Table 7-4,
Figure 7-8 (A-->E).
The
PDF's were also
in
7-8A.
with an rms fluctua-
This result is very similar
undiluted CO/H 2 run in Figure 7-2A.
tion
presented
pair for an undiluted run is given in Figure
of only 5.3 % (85 K).
dilution
series,
Only selected PDF's will be highlighted here.
The deconvoluted PDF is unimodal and narrow,
tion
is
A
to
the
The PDF pair for a run with a
ratio - 0.07 is shown in Figure 7-8B.
The rms fluctua-
for the deconvoluted PDF has risen to 115 K,
but there
are
essentially no traces of low temperature material ( < 800 K).
Figure 7-8E shows the PDF pair for a highly
diluted lean C2 H
run (dilution ratio - 0.22).
(Figure 7-21), this C2H
As with the highly diluted CO/H 2 run
deconvoluted PDF has a large rms fluctua-
tion of 195 K and shows a significant probability of low
tures ( < 800 K),
sidering
suggesting localized flame instability.
Recon-
Figure 7-2F (lean CO/H 2 with dilution ratio - 0.20,
fluctuation - 130 K),
rms
tempera-
fluctuation
notice that fuel lean C2H
and a greater probability of
rms
yields a greater
localized
blowout
than fuel lean CO/H2 for about the same equivalence ratio (equiva89
TABLE 7-4
TJSC Oxidation of C 2 H 4 /Air Mixtures for Laser Data
Base Feed Gas Rates (scfm):#
Fuel --- > 0.468
Air --- > 12.47
Window N
--- > 1.0
E2
Equivalence Ratio
Run
No.
1
2
3
4
6
PDF
Fig.No.
7-8A
B
C
D
E
Dil.N2
(scfm)
0
1.1
2.9
3.6
3.9
--- >
Dil.N2
/total@
0
0.07
0.17
0.21
0.22
0.536
Total Mass
(g/s)
7.99
8.60
9.61
10.00
10.17
# standard conditions --- > 60 0 F,
$ corrected for conductive losses
@ ratio of volumetric flows
90
1 atm
T/C Temp.$
(K)
1670
1610
1480
1410
1380
FIGURE 7-7:
Deconvoluted PDF mean and thermocouple temperatures as
a function of dilution for fuel lean C2H4 (C4- 0.54)
1.7
1.6 -tJ
1.5+
1.4c
1.3w 0
w.r-
1.21.1-
w+
0.9
0
D
0.04
0.08
DILENT N2 FLOW
THERMOCOUPLE
+
0.12
0.16
/ TOTAL FLOW
RAYLEIGH PDF MEAN
0.2
FIGURE 7-8
THE FOLLOWING SERIES OF OBSERVED AND DECONVOLUTED PDF'S
CORRESPOND TO THE CONDITIONS DESCRIBED IN TABLE 7-4
92
93
10r
NAMEs
RUN I
RUN DATES 5/10/89
0 OF DATA POINTSe
.
8
POF MEAN 00 -
ST.DEV.
9
1689. 39
14.915
CZ) -
SIZE 00
1982
-
-J
50
(obsez ved)
I
4
2
0
3o
520
740
980
1190
1400
TEMPERATLRE
FIGURE
7-8A:
95
1620
1840
2080
2290
2500
CK)
Rayleigh PDF's for fuel lean C2H4 (($>- 0.54);
T/C - 1670 K; diluent N2 flow/total flow - 0.0
1583. 38
PDF MEAN 00 ST. DEV. a) - 5.27323
BIN SIZE 00 - 50
76. 5
(deconvoluted)
s
rms fluc. = 85 K
59. 5
8
51
4
42.*1
34
25. 5
17
8.5
a
200
520
740
90
.
.11 so
1400
TEMP ERATURE 00
162
1840
200M
2280
2500
94
12
NAME:
RUN 2
RUN DATE:
101
#
5/10/89
OF DATA POINTS:
POF MEAN CK) ST.DEY.
14.7373
C%) -
BIN SIZE 00
2032
1489.9
-
50
6
(observed)
D I
so 0
520
740
1180
960
1400
TEMPERATURE
FIGURE
33
7-8B:
P1F MEAN CK) - 1425.44
ST.DEV. ()
9.21025
BIN SIZE CK) - 50
1620
1840
2060
2280
2500
(K)
Rayleigi h PDF's for fuel lean C2H4 (C - 0.54);
i610 K; diluent N2 flow/total flow - 0.07
T/C -
29.7-
(deconvoluted)
26.41
fl
rms fluc.= 115 K
23. 11
H
19. 8
-J
16.5
13.2
9.9
6.6
3. 3 1
'
o 3010
520
740
960
1190
1400
TEMPERATURE 00
1620
1840
2080
2280
2500
95
1
NAMEt RUN 3
RUN DATE. 5/10/89
# OF DATA POINTSs
1992
POF MEAN (K) 1097.29
ST.DEV. (M) - 15.9623
BIN SIZE (K) - 50
14
12
(observed)
-J
4
2
D'
30 0
520
740
1180
960
1400
-
2620
1840
2060
2280
2500
(K)
FIGURE 7-8C:
177. 62
15.2546
50
Rayleigh PDF's for fuel lean C2H4 (C:- 0.54);
T/C - 1480 K; diluent N2 flow/total flow - 0.17
-
POF MEAN (K
ST. DEV. CX)
BIN SIZE CK)
21
-
TEMPERATURE
::.:
(deconvoluted)
1-.8
rms fluc.=
165K
14.7
1-
-
12.
10. 51
9.4
-A
6.3
4.2
2. 1
I
0
300
520
740
960
1180
TEMPERATURE
1400
(K)
1620
1840
2060
2260
2500
A
96
151
NAMEe RUN 4
RUN DATEt 5/10/89
# OF DATA POINTS# 1910
PDF MEAN K) 1012. 16
ST.DEV. CW) - 21.1597
BIN SIZE K) - 50
14
12-
-
10(observed)
m
0
a.
4
2
0I
A -------------- J
3010
520
740
960
1180
TEMPERATURE
FIGURE 7-8D:
1620
1840
2060
2280
2500
(K)
Rayleigh PDF's for fuel lean C2H4
(<: =.54); T/C=1410 K;
dil.N2 flow/total flow = 0.21
-
23
1400
POF MEAN (K)
ST.DEV. (Z) -
-
BIN SIZE (K)
-
1016.71
17.0119
50
20.7-
18.
(deconvoluted)
4
rms fluc. = 175 K
16. 1
H
13.8-J
11.5-
w
1
C
9.2
-
a-
6.9
4.6
2.3
.___
0
0 300
520
740
960
1180
TEMPERATURE
1400
(K)
1620
1840
2060
2280
2500
97
NAME RUN 6
RUN DATE 5/10/99
9 OF DATA POINTS
1983
PDF MEAN WK - 98. 533
ST. DEV. C) - 18. 8eg
BIN SIZE 00 - 50
.JL
14
121
8
10
9.-J
0
0
(observed)
6
4
2
0-
520
740
950
1190
1400
TEMPERATLRE
FIGURE 7-8E:
17.1
-
-
POF MEAN 00
ST. DEV.
i)
BIN SIZE 0<)
1940
2080
2280
2500
Rayleigh PDF's for fuel lean C2H4 (4 - 0.54);
T/C - 1380 K; diluent N2 flow/total flow - 0.22
-
19
1620.
CK)
9m0 998
20. 1695
50
rms fluc.
= 195 K
15.2
13.3
'I.
11.
-j
0
(deconvoluted)
9.5
7.6
L7 i
H.F
3..
1.9
a
WO0
520
740
960
1190
TEMPERATLRE
1400
00
1520
1940
2060
2290
2500
lence ratio ca. 0.53) and N2 dilution ratio (ca. 0.21).
A complementary observation is made in comparing the approximate
minimum dilution ratios which are needed
for CO/H 2 and
to generate significant low temperature bursts.
7-2G for CO/H 2 with Figure 7-8C for C2H
low
temperature
about
170 K.
C2H
whereas
Comparing Figure
notice that significant
,
bursts first appear for an
However,
C2H
rms
fluctuation
CO/H 2 requires a dilution ratio
0.26,
=
only requires 0.17.
Returning to the fuel lean C 2H
figure 7-7 shows
runs,
that
the deconvoluted PDF means decrease with increasing dilution.
with
the
CO/H 2 runs,
readings
of
the divergence of PDF means from
increases with added dilution.
As
the
This is consistent
T/C
with
the explanation offered earlier that the Rayleigh sample volume is
within a jet trajectory.
Therefore, it sees a greater concentra-
tion of cooler jet fluid.
well
mixed
fluid.
The T/C,
Figure
however, likely sees hotter,
7-9 shows the
deconvoluted
PDF
rms
temperature fluctuations rising steadily with increasing dilution.
Notice that the divergence of the deconvoluted PDF means from
the
T/C
readings
for C2H 4is greater than
the
divergence
for
CO/H 2 . For example, at a dilution ratio of 0.2, the divergence for
C2H
is about 400 K with an rms fluctuation of 180 K.
gence
130
for
K.
The diver-
CO/H2 is about 130 K with an rms fluctuation of
Alternatively,
about
greater dilution is needed for CO/H 2
to
achieve the same divergence and rms fluctuation
level for C2H
Spatial
T/C
traces
were taken for
typical
undiluted
and
highly diluted fuel lean (equivlence ratio - 0.5) C2 H4 combustion.
These profiles are shown in Figure 7-10.
Notice that the profiles
are flat (after correcting for T/C conductive losses).
98
FIGURE
7-9
fluctuation as
Deconvoluted PDF rns temperature
a function of dilution for fuel lean C2H4 (40.54)
200-
180
-
190-
0
1700
160z
o
150140-
-J
130-
V)
1200
110100-
90
80
0
0.04
0.08
0.12
DILUENT N2 FLOW /
0.16
TOTAL FLOW
0.2
.1
FIGURE 7-10
THERMOCOUPLE TRACE
1.7
0
0
-~
~___
-
1.65
1.6
-
0D
70
...........
.....................
00
-
1.55
-c
1.5
-
- c
W~
JCL
1.45
-
1.3
0
+t
+
+
1.4-
+
I-
-
M
t
I
0
20
rHOT" LEAN C2H4
I
I
I
40
60
80
100
DISTANCE ACROSS DIAMETER (.)
+
r"DILUTEDr" LEAN C2H4
Q
A
large set of concentration data were obtained for
the C2H
system at equivalence ratio -
Table 7-5 lists the feed conditions,
tures.
PSR
0.54 at progressively lower tempera-
results.
modeling
fluctuations
rms
deconvoluted
Also listed are the
of
the same conditions.
approximately
observed data,
and
numbers
and
figure
Rayleigh
PDF's
taken
under
pre-
The observed and PSR/PQ
dicted concentrations for CO and C +C 2 hydrocarbons are plotted in
N2
dilution
7-11 and 7-12 respectively as a function of the
Figures
excellant agreement with
At zero dilution (case #8),
ratio.
the data is obtained with a PSR+PQ model.
Notice
that
at
predictions
of
levels
high dilutions.
concentration
These
observed.
T/C
the Rayleigh PDF mean and the
of
increasing
large
significant
diverand
the
dilutions.
As
readings,
temperature fluctuations at high
rms
with the CO/H 2 case discussed earlier,
excess
PSR/PQ
surprisingly
Similarly,
C 1 +C 2 hydrocarbons are
exceeds
from PSR behavior are coincident with both the
deviations
gence
the observed CO
it can be claimed that the
unburned fuel (hydrocarbons and CO)
emitted
these
under
conditions result from lack of perfect mixedness.
At
First,
this point,
large
certain summarizing observations can be made.
temperature fluctuations and localized blowout
are
coincident with increased emissions of unburned excess fuel. These
can occur in highly backmixed systems even though global
T/C) might indicate stable operation.
ance (i.e.
to
this
behavior,
predictions
jet
as well as the conversions in excess
will
be offered later.
101
the key
of
PSR
is the persistence of
for undiluted fuel lean CO/H
structures which do not break down
discussion
Second,
perform-
quickly
Third,
enough.
Further
there is a very
real
102
TABLE 7-5
TJSC Oxidation of Fuel Lean C2 H4 /Air Mixtures
Case Number:
8
9
7.99
8.63
9.11
C2H4
0.0337
0.0312
0.0295
02
0.1879
0.1736
0.1643
N2
0.7784
0.7952
0.8062
0.0
0.08
0.13
0.538
0.538
0.540
T/C Temperature (K):$
1670
1590
1530
Residence Time (msec):
6.6
6.4
6.3
Measured:
PSR:
PSR+PQ:
0.26
0.36
0.26
0.30
0.37
0.29
0.39
0.38
0.32
Measured:
PSR:
PSR+PQ:
1.1
0.4
0.
0.2
0.6
0.2
1.7
0.9
0.5
0.
0.
0.
0.1
0.
0.
0.
0.
0.
0.3
31.5
0.
0.1
37.5
0.
0.1
43.4
0.
Feed Rate (g/sec):
10
Feed Mole Fractions:
Dil.N 2 flow/total flow:
*
Equivalence Ratio:
Product Concentrations:
CO (mole %)
CH4 (ppm)
C2 H6 (ppm)
Measured:
PSR:
PSR+PQ:
C2 H4 (ppm)
Measured:
PSR:
PSR+PQ:
103
TABLE 7-5 continued
C 2 H 2 (ppm)
0.
1.0
0.
0.
1.0
0.
Corresponding PDF
Figure Number:
7-8A
7-8B
85
115
Decon.PDF rms fluc.(K):
0.1
0.9
0.
-
Measured:
PSR:
PSR+PQ:
13
11
12
9.47
9.80
10.10
C2H
0.0284
0.0273
0.0268
02
0.1579
0.1524
0.1478
N2
0.8137
0.8203
0.8254
0.16
0.19
0.21
Equivalence Ratio:
0.540
0.537
0.543
T/C Temperature (K):$
1480
1440
1400
Residence Time (msec):
6.2
6.1
6.2
0.56
0.41
0.36
0.72
0.44
0.38
0.80
0.48
0.43
4.6
1.3
1.1
16.7
1.8
1.8
20.0
2.5
3.1
7.0
0.
0.
1.0
0.
0.
1.3
0.
0.
Case Number:
Feed Rate (g/sec):
Feed Mole Fractions:
*
Dil.N 2 flow/total flow:
Product Concentrations:
CO (mole %)
Measured:
PSR:
PSR+PQ:
CH 4 (ppm)
Measured:
PSR:
PSR+PQ:
C2 H6 (ppm)
Measured:
PSR:
PSR+PQ:
TABLE 7-5 continued
C2 H4 (ppm)
8.5
49.8
0.
103.
55.9
0.2
101.
64.2
0.6
Measured:
PSR:
PSR+PQ:
6.1
0.8
0.
10.6
0.8
0.
14.8
0.8
0.
Corresponding PDF
Figure Number:
7-8C
7-8D
165
175
Measured:
PSR:
PSR+PQ:
C2 H2
(ppm)
Decon.PDF rms fluc.(K):
* water free basis
# based on molar feed rate, T/C reading, total volume
$ corrected for conductive losses
104
FIGU R E 7-11
CO concentrations
for fuel lean C 2H
(CI=
cases
0.54)
0.8-
-
0.7
0
E
0.6-
0
0.5-
w
U
0.4-
03
+
0
0
U
0.3E 3-
0.2
-
0
0.02
I
I
I
0.04
I
0.06
I
I
0.08
I
I
MEASURED
0.12
0.1
DILUENT N2 FLOW
U
I
I
/
I
I
I
0.14
I
0.16
I
I
,0.18
I
I
0.2
TOTAL FLOW
+
PSR+PQ
5
Ji
FIGUFRE
C1+C 2
hydrocarbons for
7-12
fuel lean C 2 H4
cases
(4>=0.54)
140
J
130
120
01
0
110
E
100
0
90
z
80
z
0
In
0
70
60
50
C)
40
+
(r
0
30
20
10
0
H
-+
I
.I
0
0.02
I
I
I
0.04
U
I
0.06
0.08
0.1
DILUENT N2 FLOW
MEASURED
0.12
/
0.14
0.16
p0.18
0.2
TOTAL FLOW
+
PSR+PQ
C5
difference between CO/H 2 and C2H
the TJSC.
For the same mixing energy (i.e.
inducing
C2H
in their respective behavior
mixing time scales),
instability in the CO/H2 fuel is more difficult than
due to the faster chemistry of H
flame
in
speed
in
as evidenced from laminar
data 364 cm/sec for H2 ;
78 cm/sec
for
C2H
from
Gunther, 1974).
can also be made concerning the optical and probe
Inferences
sampling.
The
hydrocarbons
large calculated PQ effect on the residual
for
the
cool fuel lean C2H
cases
C, C2
suggests
the
following: a) Accurate modeling of the PQ effect for these species
such cases might not be feasible due to uncertainties
probe
reaction
hydrocarbons
dynamics;
b) The actual concentration of
CC2
entering the probe during the diluted runs is
prob-
ably much greater than the measured amounts (e.g.
for cases #12,13).
a factor of
clearly show localized blowout,
confirming the existence of significant amounts of
and
material;
The consumption of hydrocarbons in
c)
the level of CO,
raises
the
on
based
blowout
10
The corresponding Rayleigh PDF's, obtained by
the non-intrusive optical method,
thus
the
in
but not greatly (e.g.
factor of 10 taken above).
conditions,
not a PSR under these conditions.
PSR.
the
probe
about 20 to 30
Under
the CO and hydrocarbon levels
cantly above levels predicted for a
unburned
the
are
%
in
localized
signifi-
Therefore, the TJSC is
In the next section,
this pic-
ture will be incorporated into a hybrid TJSC model.
Rayleigh
rich
PDF's
were obtained for a limited number
C2 H4 /air runs.
listed
in
Figure
7-13
Table
7-6.
(A-->D).
The conditions and the PDF
statistics
The PDF pairs are shown as a
Notice
that
107
the
of
deconvoluted
series
PDF
fuel
are
in
mean
TABLE 7-6
TJSC Oxidation of Selected C2 H4 /Air Mixtures for Laser Data
Run Number:
6
4,5
Run Date:
<---
Feed Rate (g/sec):
7
11/2/88
7.94
6.10
5.78
C2H
0.0673
0.0962
0.1095
02
0.1278
0.1451
0.1532
N
0.8049
0.7587
0.7373
1.580
1.988
2.143
T/C Temperature (K):$
1600
1600
1600
Residence Time (msec):
6.8
8.9
9.4
Rayleigh PDF Mean (K):
1500
1475
1460
75
90
80
Feed Mole Fractions:
2
Equivalence Ratio:
RMS Fluctuation (K):
# based on molar feed rate, T/C reading, total volume
$ corrected for conductive losses
@ window N2 set at normal value (1 scfm, 60 0 F, 1 atm) for
runs #1,2;
flow reduced to 0.08 scfm for runs #3-->8.
108
FIGURE 7-13
THE FOLLOWING SERIES OF OBSERVED AND DECONVOLUTED PDF'S
CORRESPOND TO THE CONDITIONS DESCRIBED IN TABLE 7-6
109
110
14
NAMEs RUN 4
RUN DATEx 11/2/88
# OF DATA POINTSt
2007
POF MEAN (K) 1543.42
ST.DEV. (Z) 11.8523
BIN SIZE (K) - 50
12
10
m
(observed)
8
0
0i
4
2
0 1
30 0
520
740
960
1180
1400
TEMPERATURE
FIGURE 7-13A:
-1620
1840
2060
2280
2500
(K)
Rayleigh PDF's for fuel rich C2H4
(()=l.58);
T/C = 1600 K
58. 5-
-
-
P3F MEAN (K)
ST. 0EV. (Z)
BIN SIZE (K)
-
65
rms fluc.
52
45.5-
1498.82
4. 8572
50
= 75 K
(deconvoluted)
39
32.5
-
26
H
19.5-
13
6.5
0
i
_
300
520
740
960
1180
T1
~~F
I 1._______
1400
TEMPERATURE (K
1620
1840
2060
2290
2500
12r
III
NAMEs
RUN 5
RUN DATE:
10.
11/2/
88
# OF DATA POINI TSo
CW)
BIN SIZE (K)
a
2000
-
1532. 59
11.9983
-
ST. BEV.
-
POF MEAN (K)
50
m
(observ ed)
I-
8
4
2
0
I
520
960
740
1180
1400
1840
Rayleigh PDF's for fuel rich
T/C =
2060
2280
2500
00
TEMPERATURE
FIGURE 7-13B:
1620
C2H4
($>=1. 58)
1600 K
34. 2t-
-
-
POF MEAN (K)
ST. BEV.
WZ)
BIN SIZE (K)
-
38
1498.26
5.57972
50
30.4-
rms fluc.
= 75 K
-
28. 8
(deconvoluted)
22.e
--
15.2-
7.8
-
3.8
-
11.4-
U
300
520
740
960
1180
TEMPERATURE
1400
GO
1620
1840
2060
2280
2500
14
r
112
NAME& RUN 8
RUN DATE 11/29 B
OF DATA POINTSeI 2040
POF MEAN 00
1487. 72
ST. DEV. a
-)
C. 7505
BIN SIZE 00
50
-
.
-
1OI
8
(observ ed)
0'
520
0
740
G80
1190
1400
1820
1940
2080
2290
2500
TEMPERATURE 00
FIGURE 7-13C:Rayleigh PDF's for fuel rich C2H4
31
POF MEAN 00 ST. EV. CM BIN SIZE 00 -
27.
(4S- 2.0); T/C-1600 K
1478. 52
. 0425
50
rms fluc.= 90 K
24.9t
(deconvolu ted)
21.7
8
19.8
15.5
12.4
5.2
301 0
520
740
990
1190
TEMPERATURE
1400
00
120
140
200
2290
2500
113
NAMEs RUN 7
RUN DATE& 11/2/ '9
# OF DATA POINT So 2033
POF MEAN (0
1477. e
ST. 0EV.
Z)
10.057e
BIN SIZE GO
50
-
-
14-
-
12H
10-
I-J
0
(observed)
0
0
a-
4
2
0
300
520
740
960
1180
1400
1620
1840
2060
2280
2500
TEMPERATURE (K)
FIGURE 7-13D:
Rayleigh PDF's for fuel rich
C2H4
29
-
-
POF MEAN 00
ST. DEV. (Z)
BIN SIZE (K)
-
T/C = 1600 K
(c4=2.14)
1458. 44
5. 31378
50
26. 1-
rms fluc.
= 80 K
23.2-
20.3-
17.4-
(deconvoluted)
m
C-J
14.5-
11. B
E.7
5.8
2.9
0
71.
300
520
740
960
1180
,
1400
TEMPERATURE 00
I1 1-1________
1620
1840
2060
2280
2500
27
temperatures
observed from T/C traces under these
tures
sented
temperaas
conditions,
pre-
for an equivalence ratio - 2.0 case in Figure 7-14.
importantly,
low
cases
lean
This is consistent with the cooler core
7-6).
(Figure
somewhat cooler than the undiluted
are
the fuel rich PDF's (Runs #4
temperature material.
-- > #7)
Most
do not show any
that
This eliminates any speculation
the central core of the torus is blown out.
Finally,
gas sample was taken under fuel rich C2H
a
tions (equivalence ratio - 2.01)
operating
conditions,
simulation results.
by
Vaughn (1988).
exceed
those
implications.
fuel rich C2H
exception
.
Table 7-7 lists the feed
measured concentrations,
and PSR,
and
PSR+PQ
These data are consistent with those observed
Notice that the measured C2H
predicted by PSR+PQ.
For the most part,
and
02
This has important
the PQ calculation has little effect
predicted composition for fuel rich C2H
114
levels
modeling
though, TJSC performance under
conditions can be approximated by a PSR.
of C2H6,
condi-
combustion.
With the
on
the
FIGURE 7-T4
THERMOCOUPLE TRACE
1
-
1.68
1.67
0
1.66
01
1.65
0
1.64
-1--~~.~~
+
1.63
03
1.61
Ld
1.6
1.59
03
1.58
1.57
1.56
1.55
0
1.54
1.53
1.52
/
r.J
Z)
7
+
1.62
1.51
1.5
1.49
-f
+
I
0
I
20
0
rHOT" LEAN
I
I
I
I
40
DISTANCE ACROSS DIAMETER
C2H4
I
80
(%)
+
RICH C2H4
100
'4
116
TABLE 7-7
TJSC Oxidation of Fuel Rich C2 H4 /Air Mixtures
Case Number:
16
6.24
Feed Rate (g/sec):
Feed Mole Fractions:
C2H 4
0.094 9
02
0.141
N2
0.763 3
2.01
T/C Temperature (K):$
1620
Residence Time (msec):
7.8
*
Equivalence Ratio:
CO (mole
%
H2 (mole
6.2
7.5
7.5
02 (mole
C2 H2
C 2 H4 (ppm)
2800
855
607
0.9
0.4
0.3
Measured:
PSR:
PSR+PQ:
C2 H 6 (ppm)
130
38
145
%
Measured:
PSR:
PSR+PQ:
CH4 (ppm)
4200
2104
2345
12.4
12.5
12.6
Measured:
PSR:
PSR+PQ:
(ppm)
17400
13300
13086
Measured:
PSR:
PSR+PQ:
Corresponding PDF Figure Number:
Decon.PDF rms fluc.
%
Product Concentrations:
(K):
7-13C
90
* water free basis
# based on molar feed rate, T/C reading, total volume
$ corrected for conductive losses
CHAPTER 8
ORIGINAL MODELING FOR TJSC CHARACTERIZATION
--
Fluid Mechanics -or Detailed Chemistry ?
The
debate
answer
to
the above question is at the
heart
of
as to the best way to handle modeling of the TJSC.
computational
load restrictions of
available
the
Due to
computers,
simul-
taneous solution of complete turbulent Navier-Stokes equations and
full elementary reaction sets is not feasible.
sis of
The desired empha-
combustion chemists is on detailed chemistry.
Therefore,
our approach has been to simplify the fluid mechanical description
while maintaining the full elementary chemistry.
TJSC Modeling Approaches
This guiding philosophy, to date, has resulted in three types
of
models to describe the TJSC.
perfectly
perfect
uses
stirred
The first assumes the TJSC is
reactor (PSR).
This is the ideal
homogeneity of temperature and composition.
case
The
with
second
the coalescence-dispersion (c-d) algorithm proposed by
(1963).
a
Curl
The third approach considers a multi-environment system.
A) Perfectly Stirred Reactor (PSR)
As described in the Introduction,
as
as
well
Backmixing
case,
TJSC.
simplest model we can consider
for
the
assumed to occur much faster than
any
reactions,
the
is
the PSR is an ideal
thereby ensuring homogeneity on all length scales.
The
selected
TJSC
has been shown to deviate from
experimental data.
conversions
of
Darivakis
PSR
behavior
(1986) found experimental
CO and H2 in excess of PSR predictions
lean equimolar CO/H 2 runs.
for some product species,
for
for
fuel
While the PSR prediction was adequate
Vaughn (1988) underpredicted
117
observed
parent
02 and C 2H
PSR model.
concentrations for fuel rich C2H4 cases with a
In the current work, we have shown that the PSR model
significantly
underpredicts observed fuel gas
cooled (diluted) fuel lean CO/H2 and C2H
concentrations
in
cases.
B) Coalescence-Dispersion
The
et.al.
the
first c-d model of the TJSC was developed by
(1985).
reaction
cells,
Pantelides
The model was zero dimensional as it divided
volume
which had
into an arbitrary number
no physical meaning.
cells
was solved with a stochastic
model
suffered
of
elements,
not
or
The population balance of
Monte-Carlo
technique.
from numerical oscillations and a large
This
computa-
tional load, even for the relatively small CO/H2 reaction set.
could
up
predict conversions in excess of PSR
predictions
It
for
.
fuel lean CO/H
2
The
(1989).
second TJSC c-d model was developed by Kridiotis
It
was a one-dimensional model which treated
et.al.
the
fresh
feed as if it were emanating out from the torus center line.
This
model
adequately predicted the conversions observed for fuel lean
CO/H 2
combustion.
fluctuations
This
model did not produce
Also,
and so no PDF's.
under fuel rich conditions.
any
the model became
unstable
As above, this c-d model also became
computationally ponderous for the simple CO/H 2 set.
ability
temperature
The
applic-
of these c-d models for the much larger hydrocarbon reac-
tion sets is currently doubtful.
C) Multi-Environment Approach
This
reaction engineering modeling approach treats the
118
TJSC
as
some
combination of perfectly stirred reactors
plug flow reactors (PFR).
to a simple,
(PSR)
and/or
These models reduce the fluid dynamics
phenomenological level.
Computationally,
they are
fairly simple and easily allow for full reaction sets.
The
first multi-environment model used to describe the
developed
by Darivakis (1986),
TJSC,
consisted of two PSR's in series.
This arrangement introduces a degree of plug flow character
enspiel,
1972). This model adequately predicted the measured exit
concentrations for fuel lean CO/H 2 combustion.
accounted
for
conditions,
computational
line.
macroscopic
The first reactor
about 10 % of the total volume.
stability
seemed to suggest TJSC instability,
center
(Lev-
However,
T/C
Under fuel
problems in the
rich
first
PSR
or even blowout, in the torus
this is inconsistent with
the
profile along the torus diameter for
observed
fuel
rich
CO/H 2 ,
which showed the highest temperature in the center (Figure
7-5).
This profile is contrasted with the centerline temperature
dip seen in the T/C profile for fuel rich C2 H
In
the
current
environment model.
jet
with
project,
(Figure 7-14).
we have developed
a
new
multi-
It uses a PFR / PSR combination with turbulent
mixing in the PFR.
The discussion of this model
will
begin
a review of the major experimental observations which guided
the model development.
Important Guiding Observations
A number of TJSC experimental observations from this
project
and others were found to be important in developing the new multienvironment model.
They are as follows:
1) Greater conversions of CO and H2 than predicted for a
119
PSR
-1
during
high temperature (undiluted) fuel lean combustion of equi-
.
molar mixtures of CO/H
2
2) Flat temperature profile (T/C trace) across the TJSC torus
(normal
to
the plane of the jets) for both fuel
lean
and
rich
equimolar CO/H 2 combustion.
3)
with
Effectively
PSR behavior for fuel rich
C 2H
combustion
the exception of higher concentrations of parent C 2H
than predicted
and 02
for a PSR.
4) Non-uniform temperature profile across the torus for
rich C2H
runs,
with a temperature dip
fuel
of as much as 100 K along
the centerline.
5) Rayleigh temperature PDF's
fuel
rich C2H
near the torus centerline
for
which do not indicate low temperature material
or
localized blowout.
6)
Effectively PSR behavior for hot (undiluted),
fuel
lean
C H combustion.
2 4
7) Flat temperature profile for fuel lean C2H
8)
combustion.
Non-uniform LIF profile across the torus in a
room
tem-
perature mixing study (Bar-Ziv, 1989).
9)
Rayleigh
near the
temperature PDF's
torus
centerline
indicating localized blowout for cool (diluted) TJSC combustion.
10)
Observed
concentrations
of CO
and
light
higher than PSR predictions for cooled, fuel lean C2H
hydrocarbons
combustion.
11) Observed concentrations of CO higher than PSR predictions
for cooled, fuel lean CO/H 2 combustion.
New PFR (Jet Mixing) / PSR Hybrid Model
A
schematic of the PFR(JM)/PSR model is shown in Figure 8-1.
120
PER
PFR
U ..
>EXIT
I\
FIGURE 8-1:
Schematic for PFR(JM)/PSR model; idealized flow sketch
,.,o'
K
\K.
I,
N%%00.
'I
'I
'I
121
'5
I'
II
/
FEED--
/7
/000 le
A rationalization for this model can be obtained by
The feed jet enters the torus
accompanying TJSC flow sketch.
entrains surrounding
examining the
fluid. This is
and
simulated by the PFR portion
with multiple injection of recycled material. Then the jet
breaks
up into eddies of various sizes, which decay rapidly into the bulk
reacting
flow.
The
PSR
simulates the subsequent
bulk
fluid
reactions.
The fluid entrained by the incoming jets is a combination
hot
PSR
fluid and PFR outlet fluid,
the latter
residual jet material entrained by the next jet.
tent
with a number of observations:
accounting
of
for
This is consis-
a) Figure 2-1,
showing
air
injection into the TJSC water model and b) the LIF profile of BarZiv
(1989),
seen in Figure 2-3.
Mechanics of PFR(JM)/PSR Modeling
The
new hybrid model uses an original overall driver program
combines the plug flow (or batch) CHEMKIN /
which
tion package of Kee et.
borg et.
al.
(1986).
al.
of
integra-
(1980) with the PSR package of Glar-
The plug flow equations have been modified
to account for classical turbulent jet mixing,
development
LSODE
Dibble et.al.
(1989).
based on a similar
A description
of
these
The FORTRAN code for the hybrid
equations appears in Appendix 4.
model driver program is available in Appendix 6.
The
same
as
mechanism
reaction mechanisms used with the hybrid model
that
for
used with the PSR and PSR/PQ
work
C1 /C2 hydrocarbon oxidation and
the
are
earlier.
the
The
accompanying
species thermodynamic properties are listed respectively in Tables
A-1 and A-2 in Appendix 5.
122
As with the PSR modeling, we further process the hybrid model
results in a probe quench (PQ) calculation to allow for comparison
with experimental probe sampling results.
The driver program
for
the PQ is available in Appendix 6.
The
input file for the hybrid program requires the following
data:
1) feed inlet temperature,
fixed at an assumed 400 K in this
study to account for preheating in the jets.
(No external preheat
was used in this work).
2) reactor pressure, fixed at 1 atmosphere.
3) feed mole fractions.
4)
LSODE print-out time increment for the
PFR(JM),
set
at
0.03 ms in this work.
5)
elapsed time in PFR(JM), which is discussed below.
6)
PSR temperature,
taken as the corrected experimental T/C
reading.
7)
parameter
controlling composition of recycle
(entrained
fluid), which is discussed below.
8) sampling parameter,
which is discussed below.
9) convergence criterion for PFR(JM) outlet temperature,
set
at 20 K;
10) convergence criterion for PSR concentrations, set at 0.1.
The
driver program generates an initial guess and
by simple itterative substitution.
converges
Computation time for the CO/H 2
mechanism is about 5 minutes on the Room 66-125 MicroVax.
considerably larger C2 H4 mechanism,
For the
the computation time rises to
about 1-2 hours.
There
are three important parameters which govern the
123
model
(inputs #5,7,8 above). They were fixed for all cases in this study
at constant values.
section.
This
The first is the elapsed time in the PFR(JM)
value (0.16 millisec) corresponds to the distance
traveled by the entraining jet gas along a curving trajectory from
a nozzle to the torus axis, about 1 inch, assuming a jet exit Mach
number of 0.7.
For all cases, by the end of the PFR(JM) section,
the ratio of the mass rate of entrained gas to the feed mass
was
about 5.4.
The volume of the PFR(JM) section is
rate
calculated
from the total mass (jet + entrained) and effective density.
PSR
volume
cases
is calculated by difference from 250
studied,
cm
3
The
For
.
all
of PFR(JM) volume ranged from 5.4 to 7.9 % of the
total volume.
The second and third fixed parameters were optimized for
entire
CO/H 2
and
second
governs
C 2H4 data set generated in
the
relative contributions of
this
PSR
the
study.
and
The
PFR(JM)
outlet gases to the composition of the surrounding fluid which
entrained
by the incoming jets.
The ratio of the masses of
is
the
PFR(JM) outlet and PSR contributions is taken as
mass ratio Rl - f * rhopfr * vpfr /
(vpsr * rhopsr)
where rhopfr - mass density of PFR(JM) outlet gas,
the
vpsr
-
PSR volume, rhopsr -
PSR gas mass density, and f
It has been found that f - 10.0
second arbitrary parameter.
provides
the necessary PFR(JM) behavior which will
shortly;
for
example,
for
vpfr - PFR(JM)
-
volume,
(8-1)
be
discussed
high temperature (undiluted)
cases,
ignition and significant conversion must occur in the PFR(JM); for
cool (diluted) cases,
the PFR(JM) does not ignite so as to
124
simu-
late localized blowout.
It was found that mass ratio Rl assumed a
value of approximately 1.0 for all cases.
to
the
This dual contribution
entrained gas reflects the proximity of a given
jet to its downstream neighboring jet.
incoming
If the TJSC had only
one
The third and final parameter governs the composition of
the
jet, then f would be equal to zero.
sample drawn into the probe.
gas
sampling
the
Best results were obtained
PSR gas and a small contribution from
the
gas to account for the large amounts of unburned
outlet
observed in diluted cases.
by
PFR(JM)
material
The ratio of the masses of the PFR(JM)
outlet and PSR contributions is taken as
mass ratio R2 - g * rhopfr * vpfr /
where g - the third parameter,
cases.
(vpsr * rhopsr)
(8-2)
which was set equal to 1.0 for all
The remaining terms are defined above.
The mass ratio R2
is typically about 0.1.
Results of New Hybrid Model
The
and
hybrid model results are presented for individual
cases
The
compared to the experimentally observed concentrations.
PFR(JM) volume (as % of total)
and outlet temperature are listed.
For comparison, the PSR and PSR+PQ values are repeated.
A) Oxidation of CO/H
2
Table
runs
8-1
made in this study.
PFR(JM)/PSR+PQ
the
only
presents the hybrid model results for
observed
50
For the hot (undiluted) case
results for H2 and CO are in good
concentrations.
K lower than the PSR
the
CO/H 2
the
#5,
agreement
with
The PFR(JM) outlet temperature
temperature.
125
Rapid
ignition
is
and
TABLE 8-1
TJSC Oxidation of Fuel Lean CO/H 2 /Air Mixtures
5
6
7
0.507
0.507
1.620
1640
1300
1760
Residence Time (msec):
7.9
6.7
8.3
Dil.N2 flow/total flow:
0.0
0.30
0.20
PFR(JM) Outlet Temp.(K):
1588
1169
1719
PFR(JM) Vol.(% of total):
7.0
7.9
6.8
0.0
0.08
0.02
0.03
0.01
0.0
0.07
0.04
0.04
0.03
5.02
4.47
5.31
4.63
5.10
0.15
0.38
0.27
0.20
0.16
0.89
0.55
0.50
0.74
0.68
10.7
9.09
8.54
9.08
8.79
7-2A
7-21
-
Case Number:
Equivalence Ratio:
*
T/C Temperature (K):$
Product Concentrations:
H2 (mole %)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
CO (mole %)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
Figure Number:
Decon. PDF rms fluc.
*
#
$
@
85
(K):
275
water free basis
based on molar feed rate, T/C reading, total volume
corrected for conductive losses
flows are volumetric
& from PFR(JM)/PSR hybrid model calculation
126
-
Corresponding PDF
almost
complete
conversion in the PFR(JM) section
provides
the
additional conversion above PSR levels. Significant combustion has
occurred in the jet before complete mixing.
rapid ignition in this case,
The
temperatures throughout,
Rayleigh
with the accompanying high
is consistent with the narrow,
unimodal
temperature PDF's of the undiluted runs shown in
Figure
7-2A,B respectively.
The
PFR(JM)/PSR+PQ
closely
model
PFR(JM)
outlet
results
for the diluted
case
the observed concentrations than the
temperature is 130 K below the
#6
PSR+PQ.
PSR
more
The
temperature.
While significant H2 conversion has occurred, little CO is converted in the PFR(JM) section.
For this level of dilution,
the com-
parable Rayleigh PDF's of Figure 7-2 (I,J,K) show significant
temperature
material,
suggesting localized blowout.
low
These data
are consistent with the low temperatures in the PFR(JM) and the CO
concentrations in excess of the PSR+PQ prediction.
Reliable experimental data for 0
not
available
for
PFR(JM)/PSR+PQ
the
the
model
rich
CO/H 2
run
#7.
However,
offers a slightly improved prediction
The PFR(JM) outlet temperature
CO and H2 concentrations.
This is consistent with the
only 40 K below the PSR value.
rected
the limiting reagent, was
T/C trace of Figure 7-5 does not show any temperature
the
for
is
cordip
in the center, as with rich C2
H4
B) Oxidation of C2
H
Consider
first the sequence of cases (#8 -- > #13)
for
fuel
lean
C2H4* Results with the hybrid model are presented in Table 8-
2.
Figures
8-2
and 8-3 summarize the trends for
127
observed
and
TABLE 8-2
TJSC Oxidation of Fuel Lean C2 H4 /Air Mixtures
8
9
10
0.538
0.538
0.540
1670
1590
1530
Residence Time (msec):#
6.6
6.4
6.3
Dil.N 2 flow/total flow:@
0.0
0.08
0.13
PFR(JM) Outlet Temp.(K):
1548
1432
1141
PFR(JM) Vol.(% of total):
7.7
7.8
7.1
0.26
0.36
0.26
0.35
0.26
0.30
0.37
0.29
0.52
0.40
0.39
0.38
0.32
0.48
0.58
1.1
0.4
0.
0.
0.
0.2
0.6
0.2
1.7
0.1
1.7
0.9
0.5
3.8
17.3
0.
0.
0.
0.
0.
0.1
0.
0.
0.
0.
0.
0.
0.
3.9
0.2
Case Number:
Equivalence Ratio:
*
T/C Temperature (K):$
Product Concentrations:
CO (mole %)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
CH4 (ppm)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
C2 H 6 (ppm)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
C2 H(ppm)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
0.3
31.5
0.
0.
0.
128
0.1
37.5
0.
0.
0.
0.1
43.4
0.
1015.
2.1
TABLE 8-2 continued
C2 H2
(ppm)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM) /PSR+PQ:
0.1
0.9
0.
1.0
0.
0.
1.0
0.
0.
0.
0.
1.0
0.
0.
0.
Corresponding PDF
Figure Number:
9A
9B
Decon. PDF rms fluc. (K):
85
115
Case Number:
11
12
Equivalence Ratio:
0.540
0.537
0.543
T/C Temperature (K):$
1480
1440
1400
Residence Time (msec):
6.2
6.1
6.2
Dil.N 2 flow/total flow:
0.16
0.19
0.21
13
1097
1067
1036
PFR(JM) Vol.(% of total):
7.2
7.3
7.4
0.56
0.41
0.36
0.50
0.63
0.72
0.44
0.38
0.53
0.66
0.80
0.48
0.43
0.58
0.69
4.6
1.3
1.1
3.8
32.0
16.7
1.8
1.8
4.1
43.3
20.0
2.5
3.1
4.8
49.1
*
PFR(JM) Outlet Temp (K):
Product Concentrations:
CO (mole %)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
CH 4 (ppm)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
129
TABLE 8-2 continued
C 2 H 6 (ppm)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
7.0
0.
0.
3.7
1.4
1.0
0.
0.
3.5
5.9
1.3
0.
0.
3.3
16.2
8.5
49.8
0.
1053.
23.2
103.
55.9
0.2
1053.
110.
101.
64.2
0.6
1074.
274.
6.1
0.8
0.
1.0
0.3
10.6
0.8
0.
1.0
1.5
14.8
0.8
0.
1.0
3.0
C2 H4 (ppm)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
C2 H2
(ppm)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
Corresponding PDF
Figure Number:
9C
-
9D
Decon. PDF rms fluc. (K):
165
-
195
*
#
$
@
&
water free basis
based on molar feed rate, T/C reading, total volume
corrected for conductive losses
flows are volumetric
from PFR(JM)/PSR hybrid model calculation
130
FIGURE 8-2:
CO concentrations as a function of dilution for fuel
lean C2H4 (<I> - 0.54): observed, PSR+PQ, PFR(JM)/PSR+PQ
0.8
I
ii
0
0.7-
.~~-~0
E
0.6U
z
0
F:
0.5-
z
0.4-
/
z
0
0
+
0
0
0.3-
I+
n 2
-I ~-~I
0
3
0.02
MEASURED
0.04
0.06
0.08
0.1
DILUENT N2 FLO W /
+
PSR+PQ
0.12
I
I
0.14
I
I
0.16
t
-
I
0.18
0.2
TOTAL FLOW
PFR(JM)/PSR+PQ
w~
FIGURE 8-3:
Cl+C2 hydrocarbon concentrations as
dilution for fuel lean C2H4 ( c
PSR+PQ, PFR(JM)/PSR+PQ
-
a function of
0.54): observed,
350
300-
a.
0.
.
z
0
2:
0
250
200-
0
In
150II
i::i
N
100-
50-
C
0
0
t
.I
I
I
0.02 0.04
MEASURED
.I
0.06
I
Ir
0.08
I
I
0.1
DILUENT N2 FLOW
+
PSR+PQ
I
I
0.12
/
I
I
0.14
1
I
I
0.16
0.18
TOTAL FLOW
o
PFR(JM)/PSR+PQ
0.2
CO and C +C2 hydrocarbons (HC).
predicted
the
tion,
breaking
The
PFR(JM)/PSR+PQ
as
CO and HC rise suddenly,
observed
out.
With sufficient dilu-
PSR+PQ model is quite
generates
if
but
inadequate,
reasonable results.
were
they
the
While the fit
is
only semi-quantitative, the correct trends are evident.
The high PFR(JM) outlet temperature (1548 K) for case #8
indicates that ignition has occurred in the
dilution)
the
(no
jet.
All
has been consumed and a portion of the resulting CO also
C2H
conversion of most of the CO occurs in the PSR
oxidized. However,
This is consistent with the observation by Hottel et.al.
portion.
(1965) that hydrocarbon oxidation in stirred combustors occurs via
a
conversion of the fuel to CO and H 20,
rapid
followed
by
the
essentially all
the
slower CO burnout.
For case #9 (N2 dilution ratio - 0.08),
C 2H
is consumed in the PFR(JM),
but CO burnout occurs in the PSR
For higher dilution ratios (case #10 -- > case #13),
portion.
to
fails
PFR(JM)
ignite.
the
CO
and
case
#10
This results in the elevated
hydrocarbon concentrations drawn into the sample.
(dilution
ratio - 0.13) is consistent with the comparable PDF
Figure 7-8C.
gases,
of ignition in the PFR(JM) occurring in
loss
The
Notice the broad Rayleigh PDF and appearance of cool
indicating localized blowout.
the elevated CO and HC levels observed,
by a PSR model.
#9
is
not
behavior.
parable
in
This instability results in
which cannot be explained
On the contrary, a dilution ratio - 0.08 in case
sufficient
to cause the TJSC
to
deviate
from
PSR
The
com-
PDF in Figure 7-8B (dilution ratio - 0.07) shows no
evi-
No excess CO or hydrocarbons were observed.
dence of localized blowout.
133
The choice the blending parameter which controls the composition
of
The
with
correlated
the
parameter
blending
than
but more
about 0.17 (perhaps less,
of
ratio
adjusted so as
data.
This
0.08).
The
HC.
prevent
effectively
to
the
dilution
and
appearance of significant CO
was
a
for
PDF's indicated localized blowout
Rayleigh
in
10)
was actually influenced by the Rayleigh
model
PFR(JM)/PSR
at
recycle (currently set
entrained
the
ignition in the PFR(JM) and cause unburned material to be taken in
para-
This blending
the model sample for these dilution ratios.
meter for the entrained recycle was then used for all other cases.
The
with
hybrid model was tested for fuel rich
better
predicts
PSR+PQ.
The
than
the parent C2 H
directionally consistent with the
with the heavily diluted fuel lean C2 H
various fuel rich C2 H
cases.
Therefore,
torus is likely seeing less exothermic,
levels
Observed
show
the central core of
no
the
perhaps more endothermic,
of
C2 H
and 02 in excess
of
PSR+PQ
the
are likely due to partial sampling from the PFR(JM)
C2 H
alternative
is
The Rayleigh PDF's
than for fuel lean conditions.
reactions
where
This outlet
shown in Figure 7-13,
runs,
of localized blowout.
results
low
though, is higher than the corresponding values seen
temperature,
sign
the
lower
significantly
temperature dip observed in T/C traces (Figure 7-14).
for
model
than
and 02 concentrations
PFR(JM) outlet temperature is
the PSR temperature,
combustion,
The PFR(JM)/PSR+PQ
results given in Table 8-3.
the
C2H4
and 02 levels are higher than in the
PSR
zone.
explanation is that the reaction mechanism used
incomplete in describing fuel rich C2H4
134
combustion.
zone
An
here
Specif-
135
TABLE 8-3
TJSC Oxidation of Fuel Rich C2 H 4/Air Mixture
Case Number:
2.01
Equivalence Ratio:
16
T/C Temperature (K):$
1620
7.8
Dil.N2 flow/total flow:@
0.14
PFR(JM) Out.Temp.(K):
1248
PFR(JM) Vol.(% of total):
5.4
*
Residence Time (msec):
Product Concentrations:
CO (mole %)
12.4
12.5
12.6
12.7
12.8
4200
2104
2345
2021
2391
H2 (mole %)
C2 H6 (ppm)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
6.2
7.5
7.5
7.6
7.7
130
38
145
42
192
02 (mole %)
C2 H4 (ppm)
0.9
0.4
0.3
0.7
0.6
2800
855
607
2988
1935
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
C2 H2
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
(ppm)
17400
13300
13086
12059
11847
Corresponding PDF Figure Number:
13
Decon. PDF rms fluc. (K):
90
*
#
$
@
&
CH 4 (ppm)
water free basis
based on molar feed rate, T/C reading, total volume
corrected for conductive losses
flows are volumetric
from PFR(JM)/PSR hybrid model calculation
ically,
cals
interactions between H atoms and higher hydrocarbon radi-
(i.e.
mechanism,
This
would,
> C2 ),
might
in
not included in the Miller and Bowman
be lowering the overall H
turn,
atom
raise both the 02 and C2 H
concentration.
levels
reaction with H atom is the principle destruction route
parent species under fuel rich conditions.
136
(1988)
since
for these
--
CHAPTER 9
SPECIAL CHEMISTRY \ MIXING INTERACTION PROBLEM
Introduction
Incineration
for
chlorinated hydrocarbons
known
are
however,
nominally
modeled as a stirred reactor,
Halogens,
laminar
stabilization
can
be
we will use the TJSC
to
chemistry interaction problem of
lead
fuel
We will try to uncover the pathways
lean chlorocarbon oxidation.
As
Since the flame
1984).
the special mixing /
which
wastes.
many industrial scale furnaces and incinerators
of
study
(CHC) and other
option
disposal
to inhibit hydrocarbon oxidation in
(Valeiras et.al.,
flames
zone
is growing in importance as a
to flame instability.
done with the TJSC characterization,
was
Rayleigh
both
scattering and concentration data were obtained, though the latter
were
limited.
We
the Rayleigh data first,
i.e.,
concentrations and PSR,
any
of
the
presentation
format;
followed by the observed
species
will maintain the same
In order to perform
PSR+PQ predictions.
predictive calculations,
we must
first
obtain
an
elementary reaction mechanism for CH3 Cl oxidation.
Fuel Lean CH3Cl Oxidation Mechanism Development
prior mechanism has been located in the literature
No
is designed expressly for fuel lean CH3 Cl oxidation.
dedicated
which
Therefore, a
elementary mechanism was developed in conjunction
with
J. W. Bozzelli at NJIT as part of the cooperative EPA program. The
mechanism
development
described
below
is the
result
of
the
simultaneous
of both thermodynamic properties and kinetic reaction
rate constants for chlorine containing species.
In this way,
kinetic parameters are thermodynamically consistent.
137
The
the
thermo-
dynamic property estimation are discussed first.
A) Thermodynamic Properties
of the species considered in the CH3 Cl mechanism devel-
Many
opment are chloro-oxy compounds (stable and radical) for which
thermodynamic
properties
(Hf
available in the literature.
applied.
S
at 300 K and
C
C(T))
are
Estimation techniques were therefore
These are based primarily on group additivity, pioneered
by Benson (1976).
program
,
no
which
An especially useful group additivity computer
was
used is the "THERM"
package
of
Ritter
and
Bozzelli (1989).
When
able,
required properties for various groups were not
avail-
estimates were based on reasonable modifications to proper-
ties
of
analogous
groups.
Special attention was paid
to
the
effects of the Cl atom on intra-molecular bond strengths. The
\Hf
values used for the chloro-oxy species are consistent with experimentally
et.al.
determined bond energies recently published
by
Russell
(1989).
A
listing
of the thermodynamic properties for the
chlorine
containing species used or considered in this work is provided
Table
A-4
in Appendix 5,
with an indication of those for
in
which
original estimates were made.
B) Reaction Kinetics
The CH 3 Cl mechanism developed for this study appears in Table
A-3
of
pressure
Appendix 5.
over
This mechanism is valid for one
a temperature range of about 700-1600
atmosphere
K.
In
all
cases, rate parameters are thermodynamically consistent.
Nearly
each reaction listed in Table A-3 can be
138
catagorized
as
atom
one of the following:
combinations,
kinetic
general,
2) termolecular atom-
dissociations,
3) unimolecular
combinations,
radical
1) abstractions,
and 5) radical-unsaturate
radical-
4)
In
additions.
parameters for types 1 and 2 were obtained dir-
ectly from the literature.
The sources are listed in Table A-5 of
Appendix 5, with any minor modifications noted.
Reactions of types 3,
4,
and 5 are treated with the Quantum
Rice-Ramsberger-Kassel (QRRK) formalism (Dean,
et.al.,
the
This
1986).
1985; Westmoreland
method provides an accurate description of
temperature and pressure dependencies of the
rate
constants
for various product channels, including those which are chemically
Unimolecular
activated.
"DISOC"
(Type 3) are handled with
systems
Bozzelli,
QRRK program (Ritter and
(Types
reactions
4,
5) are described with
1988).
the
the
Bimolecular
"CHEMACT"
QRRK
computer program (Ritter and Bozzelli, 1988).
The
include
input parameters required for the QRRK programs
the following:
a) high pressure limit A factors,
with reverse
A
factors calculated from thermodynamics (ALS), b) activation energy
c)
barriers,
the geo-
number of oscillators,
molecular weight,
metric mean vibrational frequency,
and Lennard-Jones parametes of
the activated complex, and d) the energy transferred per collision
between
the complex and the bath gas.
mentioned
consistency
between
kinetic
An example of the
parameters
and
dynamics is a high pressure limit activation energy barrier
aforethermowhich
is at least as great as /\Hr for an endothermic process.
For all QRRK evaluations performed in this study,
parameters,
the
input
corresponding energy level diagram, and the resulting
139
calculated
in
rate constants for all product channels are
Appendix 3.
The output rate constants are in the form
three parameter,
which
A-1
presented
non-Arrhenius
curve fit.
of
a
Those rate constants
are listed but do not appear in the final mechanism (Tables
and
A-3
of Appendix 5) were found to
be
insignificant
as
compared to parallel channels.
The
mechanism developed here for fuel lean CH Cl
3
(reactions
in Table A-3, thermodynamic properties in Table A-4 of Appendix 5)
was
combined with the Miller and Bowman (1989)
Cl/C 2
hydrocarbon
oxidation set (reactions in Table A-1, thermodynamic properties in
Table A-2 of Appendix 5). Selected reactions from this hydrocarbon
set
were
treated with QRRK in order to be
consistent
with
the
temperature and pressure range of interest here (700 - 1600 K, one
atmosphere),
calculated
as discussed earlier.
The QRRK input parameters and
rate constants for these reactions also appear in
the
Appendix 3.
C2H4 / CH3C1 Oxidation Data and PSR Modeling
As
a
base
case,
a fuel lean (equivalence
ratio
-
0.55)
C2H /air flame was cooled with N2 added to the premixed feed as
diluent.
Table 9-1 gives a description of the feed and operating
conditions.
The Rayleigh temperature PDF pairs for this case are
shown in Figures 9-lA,B (runs #10,11).
low
ally
The small contributions at
temperatures (350 - 800 K) suggests that the TJSC is
stable.
The
deconvoluted PDF mean temperature is
cantly less than the T/C reading,
tion
a
in the penetrating,
marginsignifi-
suggesting little if any
entraining jet.
Chlorine is likely
have a significant effect such a marginally stable condition.
140
reacto
4
141
TABLE 9-1
TJSC Oxidation of C 2 H 4 /CH 3 Cl/Air Mixtures for Laser Data
Run Number:
10
11
Run Date:
<-- 5/10/89
PDF Figure Number:
9-1A
9-1B
Feed Rate (g/sec):
10.19
10.19
C2H
0.0268
0.0268
CH 3Cl
0.
0.
02
0.1464
0.1464
N
0.8268
0.8268
Dil.N 2 flow/total flow:
0.22
0.22
Equivalence Ratio:
0.550
0.550
T/C Temperature (K):$
1400
1400
Residence Time (msec):
6.1
6.1
Feed Mole Fractions:
#
2
Run Number:
7
8
9
<-- 5/10/89
Run Date:
PDF Figure Number:
9-1C
9-lD
9-1E
Feed Rate (g/sec):
10.32
10.33
10.33
C2H
0.0238
0.0218
0.0232
CH3 Cl
0.0087
0.0105
0.0092
02
0.1455
0.1456
0.1455
N
0.8220
0.8221
0.8221
Mole % of feed carbon
as CH3 Cl:
15.5
19.4
16.5
Dil.N 2 flow/total flow:
0.22
0.22
0.22
Feed Mole Fractions:
2
TABLE 9-1 continued
Equivalence Ratio:
0.580
0.557
0.573
T/C Temperature (K):$
1400
1380
1390
Residence Time (msec):
6.0
6.2
6.1
$
based on molar feed rate, T/C reading, total
volume
corrected for conductive losses
142
FIGURE 9-1
THE FOLLOWING SERIES OF OBSERVED AND DECONVOLUTED PDF'S
CORRESPOND TO THE CONDITIONS DESCRIBED IN TABLE 9-1
143
14
144
NAME& RUN
RUN DATE#
# OF DATA
PDF MEAN
I0
5/10/89
POINTS#
1629
WK - 1085.9
ST.DEV. a) - 14.4293
BIN SIZE CIO - 50
14
C
20f
(observed)
4
-
U
in 0
-
2
520
740
980
1190
1400
1620
1940
2060
2260
2500
TEMPERATURE 00
FIGURE
9-lA:
Rayleigh PDF' s for fuel lean C2H4 (C$>- 0.55);
T/C - 1400 K; diluent N2 flow/total flow - 0.22
-
-
PDF MEAN CIO
ST. DEV. CZ)
BIN SIZE 00-
1.
1065. 4
12. 8009
501
rms fluc.
17.1
=
135 K
15.4
-
13.2
(deconvoluted)
-J
.9
8.6
4.4
2.2
0
200
520
740
960
1190
1400
TEMPERATURE 00
1620
1940
2060
2280
2500
4
19e-
145
181.
NAMEs RUN 11
RUN DATEs 5/10/89
# OF DATA POINTSe 2033
PDF MEAN (0 - 1069. 75
ST.DEV. CX) 12.8555
BIN SIZE (K) - 50
14
9
12
-J
1i1*
w
w
(obser ved)
6
4.
2
0
520
3010
740
960
1160
1400
1620
1840
2060
2280
2500
TEMPERATURE (K)
FIGURE 9-1B:
Rayleigh PDF's for
fuel lean C2H4
(4>=.55) ; T/C = 1400 K; dil.N2
29
flow/total flow = 0.22
PDF MEAN (K) 1088.52
ST.DEV. () 11.6343
BIN SIZE (K) - 50
28. 1
23.2
20.3-
9
(deconvoluted)
17.4-J
14.5-
rms fluc.
I
= 125 K
-
11.61
9.7
5.8
2.9
0
0 300
520
740
960
Th
1180
TEMPERATURE
1400
00
1620
1840
2060
2280
2500
-A
I 4,
146
NiAME& RUN 7
RUN DATEs 5/10/89
OF DATA POINTS.
1775
PC F MEAN 00 98. 027
ST .EV.
) - 24. 1948
BI N SIZE 00 - 50
121
la
4
(observed)
a
4
21
D30
0
520
FIGURE
960
1180
1400
TEMPERATURE 00
1620
1840
2060
2L:90
2500
9-1C: Rayleigh PDF's for fuel lean C2H4 / CH3C1 (CI- 0.58);
(CH3C1 15 mole % of feed carbon); T/C - 1400 K;
diluent N2 flow/total flow
0.22
14. 4-
a)
BIN SIZE 00
rms
12. 9
=
-
ST. DEV.
-
PDF MEAN 00
-
-
1a
740
949. 949
24. 2638
50
fluc.
230 K
11.2.
8
.
9.
J1
61
a
(deconvoluted)
6.4
4..
.2
1.8
a00
520
740
960
1180
1400
TEMPERATURE 00
1620
1940
2060
2280
2500
147
lOr
NAME @RUN 8
RUNI DATE, 5/10/89
* OF DATA POINTSs
PDF MEAN 00 ST. D EV.
CX) -
BIN SIZE CX) -
1459
1025.67
26. 0243
50
6
I-
4
(ob served)
-J
2
520
30i0
740
960
1180
1400
1620
1840
2060
2280
2500
TEMPERATURE- (K)
FIGURE 9-1D:
-
-
ST.DEV. (X)
BIN SIZE (K)
1030.1
-
POF MEAN 00
21
Rayleigh PDF's for fuel lean C2H4/CH3Cl
(<$=.56); (CH3Cl=19 mole% of feed carbon);
T/C=1380 K; dil.N2/total = 0.22
23.6914
50
18.9.
rms fluc.
16.8
=
245 K
14.7
H
12.6
-J
10.5
(deconvoluted)
I
8.4
6.3
4.2
2.1
3D
-
0
520
740
960
1180
KH
n
1400
TEMPERATURE (K)
1620
1940
2060
2280
2500
148
NAME
RUN 9
RUN DATE
5/10/89
# OF DATA POINTS
PDF MEAN (K)
WX)
-
BIN SIZE (K)
1037.31
-
28.2492
-
fT. DEV.
1829
50
9
I-
(observed)
'4
2
300
0o
520
740
960
1180
1400
FIGURE 9-lE:
-
POF MEAN (K)
ST. DEV., C%) BIN SIZE (K)
-
12.6
11.2
1023.21
2 3.8169
50
1820
1840
2080
2280
2500
K)
TEMPERATURE
Rayleigh P DF's for fuel lean C2H4/ CH3Cl
(CH3Cl=16 mole% of feed carbon);
(<=. 57)
T/C=1390 K; dil.N2/total=0.22
[1 J
9.9
8.4
rms fluc.
9
= 245 K
(deconvoluted)
7
5.8
I
4.2
2.8
1.4
0
3C 0
520
740
980
1180
1400
TEMPERATURE
(K)
1620
1940
2080
2280
2500
The
feed and operating conditions for the
cases are also listed in Table 9-1.
pairs
C2 H4 /CH 3 C1/air/N 2
The Rayleigh temperature PDF
are shown in Figures 9-lC,D,E (runs #7,8,9).
The same air
and diluent N2 rates were used as in runs #10,11.
amount
of
C2H
retain
nearly
A
incremental
was replaced with sufficient CH3 Cl in
the
same
observed
T/C
order
temperature.
to
CH3 Cl
The
accounted from 15.5 to 19.4 mole % of the total feed carbon.
This
resulted in slightly higher fuel equivalence ratios (0.56 to 0.58)
than
for runs #10,11.
observation
This is consistent with the
experimental
of TJSC blowout with equivalence ratios the
those in runs #10,11 in the presence of chlorine.
same
as
Slightly higher
values were needed to keep the TJSC from blowing out altogether.
In the presence of chlorine, the deconvoluted PDF means (runs
#7,8,9) are shifted to lower temperatures as compared to the means
from runs #10,11.
tuation (ca.
cool
Notice the greater deconvoluted PDF rms
240 K vs. 130 K) and the larger total probability of
gases (300-800 K).
blowout.
fluc-
This suggests localized extinction,
or
While the T/C reading indicates no change, the Rayleigh
PDF shows that a small amount of chlorine has changed a marginally
stable hydrocarbon flame to an unstable system.
Spatial
T/C traces were taken for a diluted C2H
run
and
a
chlorine containing run. Both profiles are flat (after corrections
for T/C conductive losses), as shown in Figure 9-2.
Some
obtain
limited
concentration data were
experience in gas sampling in the hostile
chlorinated
species.
No
primarily
to
environment
of
gas standards with chorinated
were available at GC analysis time.
cooled
taken,
probe method was used,
The standard stainless
species
steel
which precluded any measurement of
149
FIGURE 9-2
THERMOCOUPLE TRACE
1.45
i
4-
-I-
+
--1.44
-
14
-
1.43
-
1.42
0
-
1.41
0j0001
o:2
1.39
0
1.38
-
LLJ
-
-
1.4
1.36
*1-
/
1.37
-
I-
-
Lli
1.35-
1.34
H
I
S
1.33
n
0
0
I
20
rCOO L" C2H4
I
I
60
40
DISTANCE ACROSS DIAMETER
+
(.)
"'COO L" C2H4 + CH3CI
I
80
100
A
HCl
or Cl 2
Table 9-2 lists the feed and operating
observed
species
results.
Also
fluctuations
concentrations,
listed
and
are figure numbers
PSR,
and
conditions,
PSR+PQ
predicted
deconvoluted
rms
of the Rayleigh PDF's taken under approximately
the
same conditions.
For the high dilution C2H
CO
and
the observed levels
C1+C2 hydrocarbons (HC) in excess of PSR predictions
consistent
with those seen earlier (Table 7-5).
CH 3 C1 (case #19)
was
case #18,
a
are
case
with
has a higher equivalence ratio than case #18.
observed during the Rayleigh experiments,
chlorine,
The
somewhat
of
As
in the presence of
higher equivalence ratio was
order to keep the TJSC from blowing out altogeter.
required
For case
in
#19
as compared to case #18,
the observed level of CO is higher, while
the HC level is lower.
Notice that the PSR+PQ calculation is not
adequate for either case.
For calculation purposes only,
a test case
(#19T) was
gen-
erated with the same equivalence ratio, feed rate, dilution ratio,
and temperature as case #19,
used
The
as fuel.
with the exception that only C 2 H4 is
This is one way to guage the impact of
PSR calculation indicated that,
chlorine.
in the presence of chlorine,
the CO concentration rose from 0.49 mole% to 0.64 mole%, while the
CO2 concentration dropped from 5.70 mole% to 5.49 mole%.
is inhibiting CO burnout.
Chlorine
The impact of chlorine is more closely
examined below.
151
152 A
TABLE 9-2
TJSC Oxidation of Fuel Lean C2 H4 /CH 3 Cl/Air Mixtures
<---
Run Date:
Feed Rate (g/sec):
10.17
19T%
19
18
Case Number:
11/3/89 --
->
10.34
10.34
Feed Mole Fractions:
C2H
0.0265
0.0239
0.0294
CH3 Cl
0.
0.0106
0.
02
0.1452
0.1440
0.1449
N
0.8283
0.8215
0.8257
0.23
0.22
0.22
0.548
0.609
0.609
T/C Temperature (K):$
1415
1440
1440
Residence Time (msec):#
6.0
5.9
5.9
0.91
0.46
0.41
1.17
0.64
0.60
0.49
0.43
5.09
5.17
5.49
5.56
5.70
5.80
52
2.3
2.6
26
0.5
0.
2.2
2.3
7
0.
0.
0
0.
0.
0.
0.
2
Dil.N2 flow/total flow:
*
Equivalence Ratio:
Product Concentrations:
CO (mole %)
Measured:
PSR:
PSR+PQ:
CO 2 (mole %)
Measured:
PSR:
PSR+PQ:
CH4 (ppm)
Measured:
PSR:
PSR+PQ:
C 2 H 6 (ppm)
Measured:
PSR:
PSR+PQ:
152B
TABLE 9-2 continued
Measured:
PSR:
PSR+PQ:
202
25.4
0.
51
0.9
0.
99
3.0
0.2
59.2
0.1
(ppm)
Measured:
PSR:
PSR+PQ:
-
C 2 H2
591
60.1
0.3
-
C2 H4 (ppm)
1.3
0.
43
-
2.9
0.
-
-
-
Measured:@
PSR:
PSR+PQ:
-
CH3 C1 (ppm)
?
-
1.8
1.8
-
-
-
Measured:
PSR:
PSR+PQ:
-
C2 H5 C1 (ppm)
-
?
0.0
0.12
-
-
-
Measured:
PSR:
PSR+PQ:
-
Cl 2 (mole %)
9-lA,B
9-1C
230
130
-
Decon.PDF rms fluc.(K):
0.80
0.81
-
Corresponding PDF
Figure Number:
-
-
Measured:
PSR:
PSR+PQ:
-
HC1 (mole %)
*
#
$
@
water free basis
based on molar feed rate, T/C reading, total volume
corrected for conductive losses
GC/FID response factor assumed same as for CHG 4 ;
no standard available at analysis time
% Model calculation only; no experiment performed
NOTE:
Two peaks were detected on GC/FID with retention times of
9.15 and 14.45 minutes, which are believed to be chlorocarbons.
Use of PSR Code for Chlorine Chemistry Study
A) Results
While the TJSC operated under marginally stable conditions is
not
a PSR,
path
use of the PSR code and its sensitivity and
reaction
analyses can offer insight into the destabilizing effects of
chlorine in a highly backmixed combustion environment.
Figure
presents the results of use of the PSR
9-3
simulate approaches to blowout.
to
code
The starting point A represents a
PSR approximation of the C2 H4 /CH 3 Cl experimental run whose PDF
is
shown
an
in
C 2 H4 -only
Figure 9-1C (run #7).
case similar to the experimental run whose PDF is
in Figure 9-1A (run #10).
loss,
Starting point B represents
Point B uses the same mass flow,
and equivalence ratio as for point A.
input parameters for points A and B.
cases
seen
heat
Table 9-3 lists
With these conditions,
have the same chemical heat input rates,
the
both
assuming complete
conversion to CO2, H 20, and HCl.
The
tures
curves in Figure 9-3 represent PSR
calculated
corresponding to increasing mass throughput
tempera-
rates,
always
with the same feed composition. Blowout was assumed to occur
when
the numerical PSR calculation failed to converge, and is indicated
on
Figure
9-3
by BO.
Points A' and B' are
taken
just
before
numerical failure.
Calculated
blowout
occurred at a 44 % lower mass flow
This
for the C 2 H 4 /CH3 C1 system than for the C2 H 4 -only system.
rate
is
consistent with the Rayleigh temperature PDF's of Figures 9-lC,D,E
(runs
#7,8,9)
which showed localized blowout in the presence
of
chlorine.
It is also consistent with the experimental observation
that,
order to maintain the same T/C
in
153
temperature,
a
higher
FIGURE 9-3: Calculated PSR temperature as a function of mass throughput
I
-
.
1.41
B
-
1.4
-
1.39
-
1.38
1.36
-
-
1.37
-
1.35
-
1.34
-
1.33
1.31
-
-
1.32
-
1.3
1.29
-
A'
-
1.28
-
1.26
BO
-
1.27
t
I
I
0
BO
20
40
I
60
MASS FLOW RATE (g/sec)
a
C2Hq- AIR--N2
0 C2 1 4-AIR-N 2 -CH 3 CL
80
TABLE 9-3
Parameters for Selected PSR Cases
Case:
A
B
A'
B'
Inlet Temp (K):
400.
400.
400.
400.
Heat Loss (cal/sec):
120.
120.
120.
120.
10.32
10.32
42.0
75.0
C2 H4
0.0238
0.0282
0.0238
0.0282
CH 3Cl
0.0087
02
0.1455
0.1462
0.1455
0.1462
N2
0.8220
0.8256
0.8220
0.8256
1384
1407
1287
1283
Mass Rate (g/sec):
Calculated Temp (K):
-
155
0.0087
-
Feed Mole Fraction:
ratio
equivalence
was needed in the C 2 H4 /CH 3 Cl case compared
to
the C2H -only case (0.58 vs. 0.55).
that
Notice
nearly the same.
the
two calculated
Therefore,
blowout
are
temperatures
individual reactions common to both
cases have equal reaction rate constants. Since flame stability in
TJSC requires that sufficient heat and radicals be
the
to
B'
comparison of cases A' and
react with the incoming feed,
provide insight into how chlorine is changing
will
generated
the
chemical
pathways and hence stability.
Rates-of-production
(AROP) and
sensitivity (ASEN) analyses
of those reactions which contribute directly (production or
rates
to each species.
consumption)
order
The ASEN option calculates
temperature sensitivity coefficients
(TSC);
the rate constant of the reaction being considered.
change
in
Both features
to gather insight into the important chemical
used
are
first
specifically,
the system temperature varies with an incremental
how
the
The AROP option calculates
are available from the PSR code.
pathways
occurring in our system.
TSC
The
which
values are especially useful
reactions
have the most impact on the system
the PSR stability.
and hence,
since
they
indicate
temperature,
A endothermic reaction can have a
positive TSC if it produces radicals which later react with
species
to release large amounts of heat.
thermic
step
can
Conversely,
have a negative TSC if the reaction
an
is
other
exochain
terminating.
Rate
and concentration data calculated at points A' and
both just before calculated blowout,
values to PSR are listed in Table 9-3.
156
will be examined.
B',
The input
The PSR calculated concen-
Based on
trations for these points are shown in Table 9-4.
analysis,
the major reaction pathways for B' and A' are presented
in Figures 9-4 and 9-5 respectively.
bers
in
parentheses show the fraction of the
indicated
species
The values in brackets are
sensitivity coefficients (TSC)
temperature
the num-
In these figures,
consumed via that particular reaction.
the
AROP
reac-
for those
tions as calculated by ASEN.
B) Observations
The
role
major goal of the modeling effort here is to define
of chlorine in destabilizing flames.
The discussion
the
below
focusses on the major reaction pathways influenced by chlorine.
The
presence
primary
pathway
of chlorine.
(C2H /air/N2),
0
consumption, and
changes
Figure 9-4 indicates that,
in case A'
for
in
case
the
B',
accounting for 51 % of C2 H
resulting in a CH 3 pathway.
consumer (61 %) of C2H
By contrast, Figure
(C2 H4 /CH 3 Cl/air/N 2 ),
the
primary
is H abstraction by Cl to yield C2 H
Only
reacts via 0 atom addition.
21 % of the C2H
sumption.
consumption
atom adds to C2H ,
9-5 indicates that,
Chlorine
for C2H
also
changes
the major
In case B' (Figure 9-4),
pathways
for
CH 20
con-
CH 2 0 is primarily consumed by
OH abstraction (49 %) and H abstraction (38 %), producing HCO and
H 20 or H
the
major
But in the presence of chlorine, (case A', Figure 9-5),
(81 %) of CH 2 0 is abstraction of
consumer
H
by
Cl,
producing HCl and HCO.
Table
sumption.
consumer
shows the very important differences in
9-5
In
(42
case
%)
A',
where chlorine is present,
of OH is reaction with HCl to form
157
the
H20
OH
con-
primary
+
Cl.
TABLE 9-4
PSR Calculated Results for Case B'
RESIDENCE TIME
MASS DENSITY
TEMPERATURE
8.94E-04
2.68E-04
1283.16
sec
gm/cm3
K
EXIT MOLE FRACTIONS
H
OH
H02
CH
CH3
C2H2
C2H5
HCO
CH20H
HCCOH
CH2CO
C4H3
5.27E-04
7.71E-04
4.64E-05
1.50E-09
3.38E-05
8.05E-06
3.37E-06
8.29E-06
3.23E-07
1.61E-08
1.18E-05
2.78E-13
H2
H20
H202
CH2(1)
CH4
C2H3
C2H6
CH20
C3H2
HCCO
C02
1.36E-03
5.26E-02
6.43E-06
6.67E-09
6.09E-05
3.55E-06
3.59E-06
1.11E-04
2.41E-12
4.49E-07
3.31E-02
0
02
C
CH2
C2H
C2H4
CO
CH30
N2
C4H2
C3H3
7. 04E-04
7. 33E-02
7.89E-11
3. 73E-07
6.41E-10
3. 70E-04
2. 16E-02
5. 66E-08
8. 15E-01
2. 18E-11
2.62E-10
PSR Calculated Results for Case A'
1.60E-03
2.68E-04
1287.10
RESIDENCE TIME
MASS DENSITY
TEMPERATURE
sec
gm/cm3
K
EXIT MOLE FRACTIONS
H
OH
H02
CH
CH4
C2H2
C2H5
HCO
CH20H
HCCOH
CH2CO
C4H3
CL2
COCL
CH2CLO.
C2H4OCL
2.39E-04
4.47E-04
1.85E-05
3.79E-10
7.17E-06
8.02E-06
6.71E-07
5.05E-06
1.84E-07
2.08E-08
1.14E-05
2.95E-13
2.52E-06
3.25E-09
4.31E-10
1.22E-09
H2
H20
H202
CH2
CH2(1)
C2H3
C2H6
CH20
C3H2
HCCO
C02
CL
HOCL
CH3CL
C2H5CL
8.49E-04
5.46E-02
2.15E-06
1.78E-07
2.77E-09
3.55E-06
1.10E-06
2.45E-05
8.40E-13
3.39E-07
3.35E-02
1.64E-03
3.61E-06
1.34E-05
2.01E-05
19"8
0
02
C
CH3
C2H
C2H4
CO
CH30
N2
C4H2
C3H3
HCL
CLO
CH2CL
COCL2
3. 51E-04
7. 12E-02
9.39E-12
2.16E-05
3.93E-10
1.41E-04
2. 14E-02
4.01E-08
8.09E-01
2.35E-11
2.26E-10
6. 83E-03
2. 75E-05
1.70E-05
2. 61E-09
FIGURE 9-4: Mechanistic pathways for C H
2 4
02
H, M
------------- >
(0.19)
[-0.11]
H
---------------(0.52)
[+0.10]*
>
H
------------ >
(0.71)
[+0.023]
HO2
oxidation
OH + OH
OH + 0
0
C 2H 4 ----------------------------- >
(0.51)
[+0.035]
OH
(0.17)
[+0.013]
\Vl/
C2H3 + H20
C2H3
02
>
----(0.87)
[+0.006]
H
(0.23)
[+0.015]
CH3 + HCO
J
0
(0.80)
[+0.015]
\
CH 20 + H
C2H3 + H2
CH 20 + HCO
CH2 0
OH
-------- > HCO + H20
(0.49)
[negl]
(0.38)
[-0.005]
H
HCO + H
2
HCO
02
M
--------- >
(0.60)
(+0.10]
CO + H
CO
(0.19)
(-0.04]
OH
---------- >
(0.99)
[+0.34]
CO2 + H
HO2 + CO
* TSC calculated for reverse reaction. Note that for a reaction
entered into the mechanism as A + B - C + D with the forward rate
constant k , CHEMKIN calculates the reverse rate constant from k
- kf/K where K - equilibrium constant.
Therefore, a positive
TSC calculated from k means a positive TSC calculated
from kr
159
4
FIGURE 9-5; Mechanistic pathways for C2 H /CH3Cl
H, M
------------ >
(0.13)
[-0.12]
02
HO2
I
I
H
---------- >
(0.26)
[+0.019]
OH + OH
Cl
HC1 + 02
--------------(0.53)
[+0.17]*
H
(0.30)
[-0.016]
|
Cl
------------- >
C10 + OH
(0.32)
[+0.001]
OH + 0
|
|
0
-------
>
C1 + 02
(0.93)
[-0.005]
0
C 2H 4 ------------ >
(0.21)
[-0.004]
CH3 + HCO
I
0
Cl
oxidation
(0.61)
[+0.025]
Cl
CH3 1 --------- > CH2Cl + HC1
(+0.96)
I
[+0.0004]
I
------------- I
(0.77)
[+0.009]
H
CH3 + Cl
(0.62)
[negl]
CH 20 + H
C2H3 + HC1
I
I02
-------- >
I------->
CH 20 + HCO
Cl
--------- >
(0.81)
[+0.004]
M
HC1 + HCO
HCO
CO + H
(0.66)
[+0.13]
---------- >
H20
CO
0
---------- >
(1.00)
[+0.02]*
OH
---------- >
(0.98)
[+0.39]
CH 20 + Cl
(0.18)
[+0.002]
(0.93)
[+0.007]
CH20
0
HO2 + CO
(0.20)
[-0.07]
2 OH
HC1
CO2 + H
OH
---------- >
(0.70)
[-0.056]
0
------------- >
(0.19)
[+0.017]
* Temp. sens. coeff. calculated.for reverse reaction.
H20 + C1
OH + Cl
160
TABLE 9-5
Disposition of OH in Case B'
-0.019
-0.151
0.039
-0.059
0.016
-0.338
-0.052
-0.202
0.446
0.046
-0.025
0.415
0.028
-0.123
(-1.84E-05)
(-1.47E-04)
( 3.79E-05)
(-5.76E-05)
( 1.58E-05)
(-3.28E-04)
(-5.02E-05)
(-1.96E-04)
( 4.35E-04)
( 4.45E-05)
(-2.42E-05)
( 4.05E-04)
( 2.71E-05)
(-1.19E-04)
CH20H+H-CH3+OH
CH20+OH-HCO+H20
CH20+0=HCO+OH
HCO+OH=H20+CO
HCO+0=CO+OH
CO+OH=CO2+H
C2H4+OH=C2H3+H20
OH+H2=H20+H
O+OH=02+H
O+H2=OH+H
OH+HO2=H20+02
H+H02=20H
O+HO2=02+OH
20H=O+H20
NET RATE-OF-PRODUCTION (mole/cc-sec)
NET RATE-OF-CONSUMPTION (mole/cc-sec)
-
10.
51.
54.
55.
58.
62.
71.
132.
133.
134.
136.
137.
138.
139.
Rate of
Production
(mole/cc-sec)
-
Rxn.#
Normalized
Fraction
9.77E-04
9. 69E-04
Disposition of OH in Case A'
Rxn.#
10.
51.
55.
62.
71.
132.
133.
134.
137.
139.
166.
169.
185.
203.
Normalized
Fraction
Rate of
Production
(mole/cc-sec)
-0.012
-0.033
-0.036
-0.333
-0.020
-0.106
0.493
0.027
0.128
0.127
0.111
-0.420
-0.012
0.080
(-6.96E-06)
(-1.88E-05)
(-2.02E-05)
(-1.89E-04)
(-1.11E-05)
(-6.01E-05)
( 2.80E-04)
( 1.55E-05)
( 7.28E-05)
( 7.24E-05)
( 6.30E-05)
(-2.38E-04)
(-6.59E-06)
( 4.53E-05)
CH20H+H-CH3+OH
CH20+OH-HCO+H20
HCO+OH-H20+CO
CO+OH=CO2+H
C2H4+OH-C2H3+H20
OH+H2=H20+H
O+OH-02+H
O+H2-OH+H
H+H02=20H
20H-O+H20
O+HCL-OH+CL
OH+HCL=H20+CL
CH2CL+OH-CH20+HCL
H02+CL-CLO+OH
NET RATE-OF-PRODUCTION (mole/cc-sec) NET RATE-OF-CONSUMPTION (mole/cc-sec) -
161
5.69E-04
5.66E-04
9-5 shows this reaction to have a negative TSC
Figure
though
even
it
Only 33 % of the
is exothermic.
by reaction with CO to form CO2 + H,
consumed
however,
In case B',
tive TSC of +0.39.
-0.056
of
OH
is
being
with a large posi-
the largest single
OH
consumer (34 %) is reaction with CO to form CO2 + H, with a TSC of
+0.34.
Table 9-5 shows that the OH mole fraction for case A' is 42
% lower than case B'.
reaction OH + CO
=
Notice,
CO2 + H,
in each case, that the CO burnout
has the single largest TSC of all the
major reactions as shown in Figures 9-4 and 9-5.
Consider
largest
the
balance of 0 atom shown
in
Table
9-6.
The
0 consumer (22 %) in case A' is reaction with HCl to form
OH + Cl with a TSC of +0.017.
absence
of chlorine,
On the contrary, in case B', in the
the largest 0 consumer (35 %)
is
reaction
H20
Interestingly, note that the reaction OH + OH -
with CH 3 .
produces 12 % of the 0 in case B',
with a TSC of -0.014.
+ 0
In case
A', however, where the OH concentration is 42 % lower than in case
B' (see Table 9-4), this reaction runs in reverse.
It consumes 13
% of the 0 in order to produce OH with a positive TSC of +0.02.
The
disposition
of HO
as shown in
Table
9-7,
further insight into the retarding effect of chlorine.
the
two largest consumers (62 %) of HO 2 in case A' are
with Cl.
seen
provides
Together,
reactions
The reaction Cl + HO2 - HCl + 02 has a TSC of -0.016, as
on Figure 9-5.
In case A',
reacts with H to yield 2 OH,
In case B',
only 26 % of the available HO 2
which has a positive TSC of
without chlorine present, the reaction H + HO2
+0.019.
-
2 OH
Table
9-4
shows
that the HO2 concentration in case A' is
lower than in case B'.
162
60
%
is the largest HO2 consumer (71 %), with a positive TSC of +0.023.
TABLE 9-6
Disposition of 0 in Case B'
9.
54.
58.
59.
70.
82.
133.
134.
138.
139.
Rate of
Production
(mole/cc-sec)
-0.350
-0.077
-0.032
-0.032
-0.306
-0.014
0.873
-0.091
-0.055
0.119
(-1.72E-04)
(-3.79E-05)
(-1.58E-05)
(-1.58E-05)
(-1.51E-04)
(-6.77E-06)
( 4.35E-04)
(-4.45E-05)
(-2.71E-05)
( 5.94E-05)
CH3+0-CH20+H
CH20+0-HCO+OH
HCO+O-CO+OH
HCO+O-CO2+H
C2H4+0-CH3+HCO
C2H3+0-CH2CO+H
0+OH-02+H
0+H2=OH+H
O+H02-02+OH
20H-O+H20
NET RATE-OF-PRODUCTION
(mole/cc-sec)
-
Rxn.#
Normalized
Fraction
NET RATE-OF-CONSUMPTION (mole/cc-sec) =
4.99E-04
4.91E-04
Disposition of 0 in Case A'
Normalized
Fraction
Rxn.
9.
54.
58.
59.
70.
82.
133.
134.
138.
139.
166.
168.
191.
CH3+0-CH20+H
CH20+0-HCO+OH
HCO+O-CO+OH
HCO+O-CO2+H
C2H4+0-CH3+HCO
C2H3+0=CH2CO+H
O+OH-02+H
0+H2-OH+H
O+HO2-02+OH
20H=0+H20
O+HCL-OH+CL
O+CLO-CL+02
CH2CL+O-CH20+CL
-0.194
-0.015
-0.017
-0.017
-0.102
-0.012
0.992
-0.055
-0.019
-0.129
-0.224
-0.152
-0.032
NET RATE-OF-PRODUCTION (mole/cc-sec) NET RATE-OF-CONSUMPTION (mole/cc-sec) -
163
Rate of
Production
(mole/cc-sec)
(-5.44E-05)
(-4.17E-06)
(-4.77E-06)
(-4.77E-06)
(-2.87E-05)
(-3.36E-06)
( 2.80E-04)
(-1.55E-05)
(-5.35E-06)
(-3.62E-05)
(-6.30E-05)
(-4.26E-05)
(-8.96E-06)
2.83E-04
2.80E-04
TABLE 9-7
Disposition of HO2 in Case B'
23.
60.
76.
135.
136.
137.
138.
147.
CH20H+02-CH20+HO2
HCO+02-HO2+CO
C2H5+02-C2H4+HO2
H+02+M-HO2+M
OH+HO2-H20+02
H+H02-20H
O+HO2-02+OH
H+H02-H2+02
Rate of
Production
(mole/cc-sec)
0.061
0.361
0.014
0.555
-0.085
-0.709
-0.095
-0.096
( 1.76E-05)
( 1.03E-04)
( 4.10E-06)
( 1.59E-04)
(-2.42E-05)
(-2.03E-04)
(-2.71E-05)
(-2.76E-05)
-
NET RATE-OF-PRODUCTION (mole/cc-sec)
NET RATE-OF-CONSUMPTION (mole/cc-sec)
-
Rxn.#
Normalized
Fraction
2.86E-04
2.86E-04
Disposition of HO2 in Case A'
Normalized
Fraction
Rxn.
23.
60.
135.
136.
137.
138.
147.
202.
203.
CH20H+02-CH20+HO2
HCO+02-HO2+CO
H+02+M-H02+M
OH+HO2=H20+02
H+H02-20H
O+HO2=02+OH
H+H02=H2+02
H02+CL-HCL+02
H02+CL-CLO+OH
0.068
0.427
0.494
-0.039
-0.256
-0.038
-0.035
-0.302
-0.320
NET RATE-OF-PRODUCTION (mole/cc-sec) NET RATE-OF-CONSUMPTION (mole/cc-sec) -
164
Rate of
Production
(mole/cc-sec)
( 9.65E-06)
( 6.07E-05)
( 7.02E-05)
(-5.55E-06)
(-3.64E-05)
(-5.35E-06)
(-4.94E-06)
(-4.29E-05)
(-4.53E-05)
1.42E-04
1.42E-04
Table 9-8 indicates that Cl is heavily involved in the system
chemistry
of case A'.
The major consuming reaction (35 %) of Cl
is abstraction of H from CH20.
the key reaction OH + HCl
Cl
atom
=
The major producer (55 %) of Cl is
H20 + Cl.
As shown in Table 9-4, the
concentration is high compared to
the
other
important
radicals H, OH, 0, and
HO2'
In
case A',
consider the H atom disposition shown in Table 9-9.
reactions of H + Cl +
the
M = HCl + M and H + HCl
-
Finally,
H2 + Cl together account for only 13 % of the H atom
and
so are not major H atom sinks.
consumption,
While Table 9-4 shows that
H
atom concentration in case A' is 55 % lower than in case B', these
two
reactions
This
are
not responsible for the low
radical
levels.
conclusion can be contrasted with studies on flat flames
which flame retardation is attributed to a cycle of the above
in
two
reactions, catalyzed by Cl, wherein H atoms are recombined
into H 2
(Westbrook, 1982; Chang et.al., 1987).
C) Interpretation
We
have seen that CH3 Cl can inhibit the stability of a
/ air flame in the TJSC. As discussed earlier, and shown
lean C2 H
in
Table 9-5,
much of the required OH in case A' is lost by
reaction OH + HCl - H 20 + Cl,
is
fuel
which has a negative TSC.
the
The HCl
inhibiting CO oxidation during the later stages of the combus-
tion,
and
results
thus
suppressing the
major
exothermic
step.
Our
show that the dominance of this retardation reaction is a
characteristic of a backmixed reactor.
Further evidence of the impact of chlorine on reducing OH
these cases comes from the disposition of HO2 radical.
165
in
The forma-
TABLE 9-8
Disposition of Cl in Case A'
Rxn.#
152.
154.
156.
157.
166.
168.
169.
176.
183.
191.
193.
201.
202.
203.
H+CL+M-HCL+M
CL+H2=HCL+H
2CL+M-CL2+M
CL+HCO-HCL+CO
0+HCL-OH+CL
0+CLO-CL+02
OH+HCL-H20+CL
CH3CL+CL-HCL+CH2CL
CH2CL+H-CH3+CL
CH2CL+0-CH20+CL
CH20+CL-HCO+HCL
C2H4+CL-HCL+C2H3
H02+CL=HCL+02
H02+CL-CLO+OH
(mole/cc-sec)
-0.079
0.090
-0.012
-0.017
0.146
0.099
0.553
-0.117
0.072
0.021
-0.353
-0.201
-0.102
-0.108
(-3.33E-05)
( 3.87E-05)
(-4.92E-06)
(-7.OOE-06)
( 6.30E-05)
( 4.26E-05)
( 2.38E-04)
(-4.92E-05)
( 3.10E-05)
( 8.96E-06)
(-1.48E-04)
(-8.46E-05)
(-4.29E-05)
(-4.53E-05)
NET RATE-OF-PRODUCTION (mole/cc-sec) NET RATE-OF-CONSUMPTION (mole/cc-sec) -
166
Rate of
Production
Normalized
Fraction
4.30E-04
4.20E-04
TABLE 9-9
Disposition of H in Case B'
#
Rxn.
2.
9.
10.
52.
56.
57.
59.
62.
69.
73.
74.
132.
133.
134.
135.
137.
147.
CH3+H-CH4
CH3+0-CH20+H
CH20H+H-CH3+OH
CH20+H-HCO+H2
HCO+M-H+CO+M
HCO+H-CO+H2
HCO+0-CO2+H
CO+OH-CO2+H
C2H4+H-C2H3+H2
H+C2H4-C2H5
C2H5+H-2CH3
OH+H2=H20+H
0+0H-02+H
O+H2-OH+H
H+02+M=HO2+M
H+H02=20H
H+H02-H2+02
Normalized
Fraction
Rate of
Production
(mole/cc-sec)
-0.012
0.152
0.016
-0.100
0.293
-0.025
0.014
0.290
-0.061
-0.024
-0.021
0.173
-0.387
0.039
-0.141
-0.180
-0.025
(-1.31E-05)
( 1.72E-04)
( 1.84E-05)
(-1.13E-04)
( 3.31E-04)
(-2.80E-05)
( 1.58E-05)
( 3.28E-04)
(-6.88E-05)
(-2.67E-05)
(-2.35E-05)
( 1.96E-04)
(-4.35E-04)
( 4.45E-05)
(-1.59E-04)
(-2.03E-04)
(-2.76E-05)
-
-
NET RATE-OF-PRODUCTION (MOLES/CC-SEC)
NET RATE-OF-CONSUMPTION (MOLES/CC-SEC)
1.13E-03
1.12E-03
Disposition of H in Case A'
#
Rxn.
CH3+0-CH20+H
CH20H+H-CH3+OH
CH20+H-HCO+H2
HCO+M-H+CO+M
HCO+H-CO+H2
CO+OH-CO2+H
C2H4+H-C2H3+H2
OH+H2-H20+H
0+OH-02+H
O+H2-OH+H
H+02+M-HO2+M
H+H02-20H
H+CL+M-HCL+M
CL+H2-HCL+H
CH2CL+H-CH3+CL
( 5.44E-05)
( 6.96E-06)
0.099
0.013
-0.021
0.377
-0.014
0.344
-0.022
0.110
-0.513
0.028
-0.128
-0.067
-0.061
-0.071
-0.057
(-1.14E-05)
( 2.06E-04)
(-7.71E-06)
( 1.89E-04)
(-1.20E-05)
( 6.01E-05)
(-2.80E-04)
( 1.55E-05)
(-7.02E-05)
(-3.64E-05)
(-3.33E-05)
(-3.87E-05)
(-3.10E-05)
-
NET RATE-OF-PRODUCTION (mole/cc-sec)
NET RATE-OF-CONSUMPTION (mole/cc-sec)
-
9.
10.
52.
56.
57.
62.
69.
132.
,133.
134.
135.
137.
152.
154.
183.
Rate of
Production
(mole/cc-sec)
Normalized
Fraction
167
5.48E-04
5.46E-04
HO2 is especially important during the
of
tion
low
temperature
"induction period" (Warnatz, 1984) in many flames. In case B', the
second
after H + 02 - OH + 0
largest source (42 %) of OH,
provides 45 %,
Figures
is H + HO2 - 2 OH.
which
The case A' temperature PDF of
9-lC,D,E (runs #7,8,9) clearly shows the existence of low
temperature
primarily
gases
(< 1000 K).
consumed
by Cl.
In
case
A',
HO2
is
The reaction Cl + HO2 - HCl + 02
is
hence the negative TSC.
chain terminating,
however,
By depleting HO 2 , Cl
is inhibiting the burnout of CO, which is necessary for TJSC flame
stability.
we conclude that chlorine inhibits combustion
At this point,
our backmixed system through direct and indirect depletion
the
OH radical which dominates the oxidation of CO to
of
CO 2
.
in
Use of New Hybrid Model
The
with
new PFR(JM)/PSR model was applied to cases #18
the
results presented in Table
temperatures
suggest
PDF's
localized
PFR(JM)
outlet
the elevated CO and HC levels for cases
#18,19
blowout,
(see Figures 9-1).
predicts
cases
not
and
The
which is confirmed by
the
with
case
#19.
Rayleigh
The PFR(JM)/PSR+PQ model more
the observed CO concentration than the PSR+PQ
#18 and #19.
consume
9-10.
-- > #19T,
closely
for
both
It does better with the HC in case #18,
but
The probe quench
calculation
HC species especially fast in the presence
appears
of
chlorine.
This suggests that the chlorine kinetics may need refinement.
also
shows
dynamics.
the
to
need for a more quantitative description
of
It
PQ
Further use of the hybrid model can be considered when
a larger and concentration data set becomes available.
168
TABLE 9-10
TJSC Oxidation of Fuel Lean C2 H4 /CH 3 Cl/Air Mixtures
18
19
19T
Dil.N2 flow/total flow:
0.23
0.22
0.22
Equivalence Ratio:
0.548
0.609
T/C Temperature (K):
1415
1440
1440
Residence Time (msec):
6.0
5.9
5.9
Case Number:
0.609
1046
1087
1058
PFR(JM) Vol.(% of total):
7.5
7.8
7.6
0.91
0.46
0.41
0.56
0.68
1.17
0.64
0.60
0.81
0.97
0.49
0.43
0.60
0.75
*
PFR(JM) Outlet Temp (K):
Product Concentrations:
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
-
CO (mole %)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
?
?
5.09
5.17
4.77
4.84
5.49
5.56
5.07
5.15
-
CO 2 (mole %)
5.70
5.80
5.34
5.42
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
52
2.3
2.6
4.5
50.4
26
0.5
0.
6.7
0.
7
0.
0.
3.5
12.4
0
0.
0.
1.1
5.3
-
CH 4 (ppm)
2.2
2.3
4.8
66.3
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
169
-
C2H6 (ppm)
0.
0.
3.9
11.4
170
TABLE 9-10 continued
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
60.1
0.3
1073.
204.
202
25.4
0.
883.
0.
59.2
0.1
1238.
141.
(ppm)
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
99
-
C2 H2
591
-
C2 H4 (ppm)
0.9
0.
1.0
2.7
3.0
0.2
3.0
7.1
1.3
0.
1.5
3.2
-
43
2.9
0.
222.
0.
51
-
-
Measured:@
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
-
CH 3Cl (ppm)
1.8
118.
121.
-
?
0.0
0.12
0.0
0.04
-
?
0.80
0.81
0.78
0.97
-
?
1.8
-
-
-
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
-
Measured:
-
C 2H 5Cl (ppm)
-
Measured:
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
-
Cl 2 (mole %)
-
PSR:
PSR+PQ:
PFR(JM)/PSR:
PFR(JM)/PSR+PQ:
-
Measured:
-
HC1 (mole %)
* water free basis
@ GC/FID response factor assumed same as for CH ;
no standard available at analysis time
.0
CHAPTER 10 --
A
FINAL DISCUSSION,
summary
learned
sented
discussion
CONCLUSIONS, AND RECOMMENDATIONS
is
now presented of
what
in this project about the nature of the TJSC.
are the preliminary conclusions on the effect of
on backmixed hydrocarbon combustion.
Finally,
a few
has
been
Also
pre-
chlorine
recommenda-
tions for future work are made.
Mixing
in the TJSC occurs by the fluid mechanical action
turbulent jet entrainment and wall generated turbulence.
this mixing is complete before reaction begins.
tial
exists
fast
the
the
very
jet
This is evident with the
reacting CO/H 2 under high temperature (undiluted) fuel
conditions.
the
The poten-
for ignition and significant conversion in
structure before complete mixing occurs.
Ideally,
In reality,
breakdown of the jet structure is not infinitely fast.
of
lean
The very rapid consumption of H2 begins early (recall
high
laminar flame speed
enhances the CO conversion.
for
H
364
cm/sec),
and
Conversions of CO and H 2 greater than
predicted by a PSR model result.
The
slower
situation for C 2H
is somewhat different because of
reactivity (laminar flame speed of 78 cm/sec).
temperature,
fuel
lean operation,
the C 2H
the
For a high
reacts to CO in
the
entraining jet, but the complete CO burnout occurs after mixing is
complete.
The result is a CO conversion which is well
predicted
by a PSR/PQ model.
This jet structure behavior is linked to the non-PSR behavior
observed in low temperature (diluted) operations,
C 2H .
especially with
There is a correlation between large Rayleigh
fluctuations,
the
appearance
of
171
bursts
of
low
temperature
temperature
material,
the experimental observation of levels of
and
then the potential
as it breaks up,
jet
entraining
in
the
exists
for
in the recycled gas to initiate reactions
available
not
and
If sufficient heat is
in excess of PSR predictions.
hydrocarbons
CO
localized blowout and excess levels of unburned fuel gas.
important conclusion of this project is
An
that,
for
high
temperature stable operations, the TJSC flame is distributed.
PDF's
narrow
generated
(deconvoluted)
suggest a lack of flame fronts.
sary for PSR performance.
high
temperature
under
these
The
conditions
This distributed nature is neces-
Such performance has been observed for
(undiluted) fuel lean C2H
combustion.
It
is
.
also true, to a good first approximation, for fuel
lean CO/H 2
The
TJSC
combustion.
central
affect
essentially
behaves as a PSR for fuel
rich
C2 H
There is no localized blowout in the axial core.
temperature
parent C2 H
dip observed in T/C traces appears
and 02 concentrations due to partial
The
to
only
sampling
from this zone.
One
of
of the probe quench (PQ) calculation
impact
the
the most striking observations made in this work
on
hydrocarbon
concentrations under fuel lean conditions where localized
is
occuring
especially
probe.
in the TJSC.
hydrocarbons,
Hot radicals consume
blowout
unburned
gases,
in the first 0.1 ms of plug flow in the
This situation seriously complicates fuel lean hydrocarbon
modeling in the TJSC operated with localized instabilities.
these
is
hydrocarbons are converted to CO,
concentrations,
but
to a lesser extent.
the PQ also
Since
effects
CO
The PQ appears to have
less of an impact on fuel rich modeling in the TJSC.
Chlorine
has a significant impact on
172
TJSC
stability.
The
destabilizing
effect
of
CH3 Cl
on
fuel
lean
stability became evident at lower temperatures.
C2H
Modeling has sug-
gested that Cl atom becomes the dominant radical.
of
combustion
Destabilization
the TJSC is primarily due to inhibition of CO burnout.
petition for OH between CO and HCl results in less heat
A com-
available
for TJSC flame stabilization through backmixing.
A few recommendations are now offered for future work.
involve
work
performance
which
should be done regardless of
is judged.
First,
because
probe
should
capacity.
Clearly,
The
designed
prevailing
with
permanent
be
temperature
probe
the flow
residence time) and pressure in the probe should also
use
of the water cooled probe for
under cool,
mended.
profile
the
In addition,
the
cooled
water
measured so as to assess the capacity for aerodynamic
Further
data
A
temperature profile along
should be known for any TJSC temperature.
rate (i.e.
TJSC
reactions occur in
radicals just do not disappear.
be
the
the probe quench must be further
investigated and standardized.
probe
how
These
fuel lean conditions,
accurate
however,
quench.
hydrocarbon
is not
recom-
Molecular beam sampling would be a preferred alternative
as it offers true quenching capabilities.
In
order
to
support
the
theoretical
discussion
of
how
chlorine destabilizes backmixed combustion, it is recommended that
accurate
CO2
Measurements
measurements
indicate
be
made
with
and
without
CH3 Cl.
higher CO concentrations when chlorine
present, while calculations indicate less CO 2 .
with the proposed key destabilization mechanism,
This is consistent
which is inhibi-
tion of CO burnout due to consumption of OH by HCl.
173
is
This
impor-
tant finding would be greatly supported by accurate CO2 data.
In
addition, the CH3 Cl mechanism should be refined and experimentally
verified
expanded to accomodate fuel rich chemistry.
performed
It should also be
in well defined kinetic experiments.
such
under
conditions
to
Experiments should be
the
determine
effect
of
chlorine here.
From
operated
the point of view of an experimental
kineticist,
when
in the absence of local instabilities,
as a good
first
approximation
the TJSC can be taken to be a PSR within
all
the
other uncertainties of the experimental work, especially the probe
for all the fuels studied in this project.
quench,
desired,
However,
if
the hybrid PFR(JM)/PSR model can be used. Its simulation
of the jet mixing character of the TJSC is useful for those conditions
under
which
operating regime.
the TJSC is pushed into a
marginally
stable
It is also useful for cases of very fast chem-
istry (i.e. H2-) when observed conversions incrementally exceed PSR
predictions.
174
REFERENCES
Benson,
S.W., Thermochemical Kinetics,
Sons, New York (1976).
2nd.
ed.,
John Wiley
&
Bar-Ziv, E., personal communication (1989).
Chang, W.D., Karra, S.B., and Senkan, S.M., Combustion and Flame,
Vol. 69, p.1 1 3 (1987).
Chomiak, J., Energy Laboratory Report, Massachusetts Institute of
Technology, Cambridge, MA (1984).
Curl, R.L., AIChE Journal, Vol. 9, p. 175 (1963).
Darivakis,
G.S., M.S. Thesis, Department of Chemical Engineering,
Massachusetts Institute of Technology, Cambridge, MA (1986).
Dean, A.M.,
(1985).
Journal of Physical
Chemistry,
Vol.
89,
p.
4600
Dibble, R.W.,
Broadwell, J.E., Lutz, A.E., and Kee, R.J., Sandia
Report SAND89-8220, Sandia National Laboratories, Albuquerque, NM
(1989).
Dibble, R.W. and Hollenbach, R.E., Eighteenth Symposium (Int.) on
Combustion, p.
1489, The Combustion Institute,
Pittsburgh,
PA
(1981).
Eckbreth, A.C.,
Laser Diagnostics for Combustion Temperature and
Species, Energy and Engineering Series, Abacus Press, Cambridge,
MA (1988).
Glarborg,
P., Kee, R.J., Grcar, J.F., and Miller, J.A., Sandia
Report SAND86-8209,
Sandia National Laboratories, Albuquerque, NM
(1986).
Gunther, R., Verbrennung und Feuerungen, Springer, Berlin (1974).
Hottel, H.C., Williams, G.C., Nerheim, N.M., and Schneider, G.R.,
Tenth Symposium (Int.) on Combustion, p.
111, The Combustion
Institute, Pittsburgh, PA (1965).
Sandia Report
Kee, R.J., Miller, J.A., and Jefferson, T.H.,
Albuquerque,
NM (1980).
Laboratories,
Sandia
National
SAND80-8003,
Kridiotis, A.C., Ph.D. Thesis, Department of Chemical Engineering,
Massachusetts Institute of Technology, Cambridge, MA (1986).
Kridiotis, A.C., Longwell, J.P., Sarofim, A.F., and Bar-Ziv, E.,
Chemical Engineering Science, Vol. 44, No. 5, p. 1039 (1989).
F.W., Ph.D. Thesis, Department of Chemical Engineering,
Lam,
Massachusetts Institute of Technology, Cambridge, MA (1988).
175
Levenspiel, 0., Chemical Reaction Engineering, 2nd ed., John Wiley
& Sons, New York (1972).
Longwell, J.P. and Bar-Ziv, E., Combustion and Flame, Vol. 78, p.
99 (1989).
Miller, J.A.
and Bowman, C.T., Progress in Energy and Combustion
Science (1989).
Muller-Dethlefs, K. and Weinberg,
(Int.) on Combustion,
p.
985,
Pittsburgh, PA (1978).
F.J., Seventeenth Symposium
The Combustion
Institute,
Nenniger,
J.E., Ph.D. Thesis, Department of Chemical Engineering,
Massachusetts Institute of Technology, Cambridge, MA (1984).
Nenniger,
J.E., Kridiotis, A., Chomiak, J., Longwell, J.P., and
Sarofim, A.F., Twentieth Symposium (Int.) on Combustion, p. 473,
The Combustion Institute, Pittsburgh, PA (1984).
Pantelides, C.C.,
Erickson, W.D., Longwell, J.P., and Sarofim,
A.F., Chemical Engineering Science, Vol. 40, No. 3, p. 375 (1985).
Rajan,
S., Smith, J.R., and Rambach, G.D., Combustion and Flame,
Vol. 57, p. 95 (1984).
Ritter, E. and Bozzelli, J.W., personal communication (1988).
Ritter,
E. and Bozzelli, J.W., Central States Meeting of
Combustion Institute, Dearborn, MI (1989).
Rudder, R.R. and Bach, D.R., Journal of the
America, Vol. 58, No. 9, p. 1260 (1968).
Optical Society
the
of
Russell, J.J., Seetula, J., Gutman, D., Senkan, S.M., and Melius,
C.F.,
Second International Conference on Chemical Kinetics,
Gaithersburg, MD (1989).
Schafer, R.W., Mersereau, R.M., and Richards, M.A., Proceedings of
the IEEE, Vol. 69, No. 4, p. 432 (1981).
Thesis, Department of Chemical Engineering,
Sun, W. S., Ph.D.
Massachusetts Institute of Technology, Cambridge, MA (1985).
Thomas, A.C., B.S. Thesis, Department of Chemical Engineering,
Massachusetts Institute of Technology, Cambridge, MA (1979).
Valeiras, H., Gupta, A.K., and Senkan, S.M., Combustion Science
and Technology, Vol. 36, p. 123 (1984).
Vaughn, C.B.,
Ph.D. Thesis, Department of Chemical Engineering,
Massachusetts Institute of Technology, Cambridge, MA (1988).
176
-4
Warnatz, J., Combustion Chemistry, W.C.Gardiner, Jr., ed., p. 197,
Springer-Verlag, New York (1984).
Industrial
Weiss, M.A., Lang, R.J., and Longwell, J.P.,
Engineering Chemistry, Vol. 50, No. 2, p. 257 (1958).
Westbrook, C.K., Nineteenth Symposium (Int.) on Combustion,
127, The Combustion Institute, Pittsburgh, PA (1982).
and
p.
Westmoreland,
P.R., Howard, J.B., Longwell, J.P., and Dean, A.M.,
AIChE Journal, Vol. 32, No. 12, p. 1971 (1986).
Yariv, A., Optical Electronics, 3rd. ed., p. 317, Holt, Rinehart,
and Winston, New York (1985).
177
APPENDICES
Below is a list of the various
immediately follow, in order:
* APPENDIX 1 -+
+
+
+
appendices
which
EXPERIMENTAL AND COMPUTER PROCEDURES
Operation of combustor
Optical calibration
Rayleigh scattering during combustion
Collection of stable gas grab sample
* APPENDIX 2
--
RAYLEIGH DATA WORKUP AND PDF GENERATION
* APPENDIX 3
--
APPLICATIONS OF QRRK
* APPENDIX 4
--
JET MIXING EQUATIONS FOR CHEMKIN
* APPENDIX 5
--
ELEMENTARY REACTION MECHANISMS
+ Table A-1: Reactions for Cl/C2 Hydrocarbon Oxidation
+ Table A-2: Species Thermodynamic Properties for
Cl/C2 Hydrocarbon Oxidation
+ Table A-3: Reactions for Fuel Lean CH3Cl Oxidation
+ Table A-4: Thermodynamic Properties for Chlorine
Containing Species
+ Table A-5: Sources and Notes on Non-QRRK Reactions
in CH3Cl Mechanism
+ References for CH3Cl Mechanism Development
* APPENDIX 6 --
COMPUTER PROGRAMS
178
APPENDIX 1 --
This
section
the combustor,
computer
contains detailed procedures for operation
laser, optics, and electronics.
programs
Elephant")
EXPERIMENTAL AND COMPUTER PROCEDURES
for
use
on the
IBM
9001
Various dedicated
computer
("White
during the experiments and subsequent data workup
also described.
Therefore,
of
are
this section is primarily intended for
those who choose to continue this pioneering work.
Operation of Combustor
Prior to any burning,
(1)
the following steps are recommended:
Set WINDOW N2 flow to 1 scfm (rotameter
silver
float
to 90 at 80 psig).
(2) Switch on AFTERBURNER blowers.
(3)
Turn on ETHYLENE GLYCOL pump.
Set flow for jet
ring
cooling at about 30 psig.
(4)
spray
at
40 psig.
Check
for
on main COOLING WATER pump.
Turn
about
20
psig.
Set
second
Set
first
quench
at
about
spray
If using gas sampling probe, set flow at about 35 psig.
adequate
flow through window flange
and
afterburner
external cooling coils.
(5)
Activate cooling flowswitch ALARMS.
(6) Activate the thermocouple,
feed pressure, and "select-
a-temp" DIGITAL READOUTS.
The combustor ignition and warmup steps are as follows:
(1) Set MAIN AIR rotameter to 10 at 80 psig.
(2)
Set
(3)
Turn
PILOT AIR rotameter (silver float) to
45
at
80
Set PILOT H2 rotameter to
15
psig.
on IGNITOR coil.
179
(silver float) at 50 psig.
(4) Turn off ignitor after about 3 seconds of H2 flow. Look
for jump in thermocouple reading.
(5)
Begin
flow
of MAIN FUEL.
Look for
reading accompanied by a loud "pop" from
thermocouple
jump
large
the
in
TJSC.
.
Turn off pilot H
2
(6) For C2 H4
For
CO/H
set FUEL ROTAMETER to 15 and MAIN AIR to 25.
set FUEL ROTAMETER to 70 and MAIN AIR
to
19.
Both
rotameters should be operated at 80 psig.
(7) Turn off pilot air and continue WARMUP at about 1300 0C
for at least 45 minutes.
Optical Calibration
The optical calibration serves two purposes:
spurious
error.
glare,
a) null out the
and b) provide a measure of the inherent
system
The importance of this procedure cannot be overemphasized.
It is recommended that the calibration be performed often.
The following preparatory steps are necessary:
(1) Disconnect exhaust duct and attach plexiglass
cover
with fittings.
(2) Hook up vacuum pump ("Mobile Marilyn") to convenient
fitting on the cover.
(3) Close main feed valve to the reactor.
(4)
Disconnect pilot gas line and replace with line
(5)
Flow window N2 at about 0.5 scfm at 1 atm
to
manometer.
pressure
in the reactor vessel.
(6)
Carefully remove collection optics
180
train,
marking
the resident positions on the table.
(7) Remove, gently clean, and replace (if necessary) the
main scattering window.
(8)
Peer through the window and observe passage of the
focused laser beam through the vessel.
(9) Carefully adjust the periscope with remote cables in
order to visually minimize the glare.
(10) Replace optical train and power-up the detectors and
associated electronics.
(11) With oscilloscope,
tor
signal
using the various optical mount
collection optics train.
the
this
optimize ("tweek-up") each detec-
The
in
the
Make sure the "head-on" PMT is "seeing"
Rayleigh scattering by observing
signal.
adjustments
the pressure dependence
"side-on" PMT signal must be
independent
of
of
pressure.
As
involves
at
discussed
earlier
in the
main
text,
the
the variation of the net mean signal (Sd)
room temperature.
Any observed offset
adjustment of the subtraction factor
program NS3TBLS.BAS (Appendix 6).
7.
F
calibration
with
pressure
is answered with an
This procedure uses the
All "White Elephant"
computer
programs used in this project are highly interactive.
The following steps are employed in the calibration process:
(1)
Activate boxcar,
then
turn on "White
Elephant"
computer with AUTOEXEC file in drive 0 attaching IEEE driver.
(2) Load BASIC, then load and run NS3TBLS.BAS.
(3) Set "zeroes" on all boxcar channels; then, check for
proper baseline subtraction on channels 3 and 4.
181
(4)
The
laser
intensity monitor signal
with the Rayleigh signal
channel 2,
is
input
to
Sd input into both channels 3
and 4.
(5)
Turn
on vacuum pump,
and set pressure
in
vessel
using control valve.
(6)
signals
Turn
on laser and observe laser intensity
on oscilloscope.
and
Using GATE MONITOR OUTPUTS on
Sd
boxcar,
check for correct placement of electronic sampling gates.
offset
(7)
Obtain
(8)
Collect
Sd vs.
pressure.
Plot up and notice
any
F.
eously.
Record
laser intensity monitor
signal
mean monitor signal and PDF of
simultan-
Sd both with
without correction for laser intensity fluctuations.
A
and
slightly
narrower PDF should be generated when correction is made for laser
intensity fluctuations.
(9) Vary subtraction factor
(10)
Itterate
on
becomes arbitrarily small.
and
correlate mean Sd
coordinates.
Record
vs.
7
steps 7,
8,
and repeat steps 7 and 8.
and 9 until
offset
r
Record final Sd vs. pressure relation
standard deviation of PDF
on
log-log
system noise parameters f,g (Equation
6-7)
for use in combustion PDF deconvolution.
Rayleigh Scattering During Combustion
to
Prior
ignition,
the following steps
are
of Rayleigh scattering data during combustion.
collection
recommended
that this effort not be pursued until
for
required
an
It is
acceptable
optical calibration has been performed.
(1)
Set WINDOW N2 rotameter to base value of 1 scfm (90
182
on silver float at 80 psig), but no air flow.
(2) Repeat steps 3,4, and 6 of the Optical Calibration.
(3) Check that mean Sd and accompanying PDF match
If not,
obtained at 1 atm in the Calibration.
values
those
check for
proper optical alignment, laser power, boxcar operation, etc.
(4)
Load program NS3DBLS.BAS (Appendix 6),
ensuring no
change in boxcar parameter from desired values.
(5) Collect and store reference (N2 at room temperature,
1 atm) data on diskette as prompted by program.
(6) Turn off laser beam and begin combustion warmup.
After ignition and warmup, set desired reactor conditions and
It is recom-
wait for steady state (see thermocouple time trace).
that the Rayleigh data collection begin with a
mended
burn
(equivalence ratio about 0.5) as a base point.
lean
fuel
When
ready,
carefully turn on laser and bring to desired power level.
Observe
oscope.
reasonable
the
Sd.
viewing
mean Sd and check if
approximate
If the combustion
the probable cause is dust /
then
window.
If high,
oscill-
on
it
and
compared to the thermocouple temperature
as
reference mean
the
intensity monitor and Sd signals
laser
Observe
is
the
Sd is low (absolute value),
condensation on the
inside
then a likely cause is too
of
much
glare; i.e., the glare nulling obtained in the optical calibration
is
failing
somewhat.
changes in the
This could be due to
reactor wall reflectivity.
combustion
induced
In either case,
some
adjusment can be made at data workup time if the offset is not too
great.
If the signal is very large, either play with the collec-
tion optics (GOOD LUCK!) or shut down.
183
Another optical
calibra-
tion would then be needed.
If the mean Sd looks reasonable,
and collect data.
set desired flow conditions
It is preferable to keep the laser firing,
practical, during non-collection periods.
if
There is a slight drift
in mean laser intensity for about 15 minutes after initial firing.
Collection of Stable Gas Grab Sample
The following procedure is recommended for use in
collecting
a grab sample from the TJSC for stable gas species analysis:
1)
Prior
window
to combustion start-up,
replace TJSC
holder with gas sampling probe flange.
laser
exit
Insert probe
and
connect flange N 2 purge (same as window N ).
2
2)
Prior
to combustion start-up,
set
cooling
water
flow
through probe (35 psig inlet pressure at low-flow alarm).
3)
With
TJSC operating at
desired
combustion
conditions,
isolate gas sample jar, and then evacuate with vacuum pump.
4)
Activate metal bellows pump sampling
pump.
Begin
with-
drawal of gas through cooled probe, water knock-out, pump, and out
to vent.
5)
jar.
Isolate sample jar.
Then redirect gas flow from vent
In an alternating fashion,
fill jar to about 3 psig,
to
then
evacuate. Repeat this flushing operation about 4 times.
6) Fill jar to about 3 psig,
and then isolate.
flow to vent.
7) Remove sample jar for analyses.
184
Redirect gas
- -
APPENDIX 2
Prior
run,
to workup of the Rayleigh scattering data for a
the
Equation
RAYLEIGH DATA WORKUP AND PDF GENERATION
relationship
between composition and temperature
(4-11) in the main text] must be
appropriate
AFT*.BAS,
"White
*
where
Elephant"
estimate
reactor,
higher
these
program (Appendix 6)
represents the particular
addition to feed flow rates /
an
calculated.
composition,
[see
Use
the
the
set
burned.
In
in
fuel
given
these programs require
of the temperature of the feed gas as it enters
the
and an estimate of the overall heat loss (as a % of
the
heating value of the input fuel rate).
numbers
can
Decent values for
be obtained by running the PSR
code
on
MicroVax computer in Room 66-125 in an "adiabatic" mode with
temperature
and heat loss as inputs.
Try to match the
the
feed
computer
generated temperature with the thermocouple measurement (corrected
for
conductive losses) for that run,
if appropriate
(e.g.
fuel
lean, high temperature run).
For Rayleigh data workup and temperature PDF generation,
"White
program
Elephant"
converts
generates a PDF,
is
(a)
program GLOBAL.BAS.
the
Sd
signals
to
interactive
temperatures,
The signal data
The following information is
temperature parameters [equation
system (shot) noise calibration parameters
decent guess at the deconvoluted PDF;
or
highly
and performs the deconvolution.
recalled from disk.
composition /
Rayleigh
This
maximum likely temperature.
use
[equation
requested:
(4-11)];
(b)
(6-7)];
(c)
(d) minimum likely signal Sd
Check that the calculated decon-
voluted PDF can regenerate fairly well the observed PDF.
If not,
readjust the deconvolution parameters or restart the data workup.
185
APPENDIX 3
Listed
bimolecular
below
are the input parameters and sources
the
energy level diagram is also included for each
QRRK
reaction
system.
The QRRK derived rate parameters are valid
one atmosphere pressure,
for
N2 bath gas, and an approximate tempera-
range of 700 - 1600 K.
non-QRRK reactions.
ten).
for
this
An
form
APPLICATIONS OF QRRK
and unimolecular QRRK calculations performed in
project.
ture
- -
Also listed are the sources for
In all cases,
the rate constants are in the
k - A * Tn * exp(-E/RT) for the forward direction (as
3
Units are in moles, cm , sec, kcal, K.
writ-
All reactions used
in this study are written as reversible for CHEMKIN.
186
the
187
INPUT PARAMETERS FOR UNIMOLECULAR QRRK
[C 2H3 ]
-
products
-
**
*
C2 H3
A
E
1.2 E+12
41.6
k
1
source
a
a
<v> - 1561/cm
b
LJ PARAMETERS :
c
e/k - 228. K
sigma - 4.19 A0
(a) For reverse: A-5E12, Ea-2.4 (Dean, 1985);
for forward, use thermo and A,Ea for reverse.
(b) From "CPFIT" program and Cp data.
(c) Estimated from critical properties for C2H4
(Reid, Prausnitz, and Sherwood).
UNITS:
* bimolecular:
cm 3/mole-sec
1/sec
unimolecular:
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
P
Bath
Gas (torr)
N
2
Reaction
C2H3C2H2+H
760.
A (cm3/
mole-sec)
n
5.62E+31
-6.06
E (kcal
/mole)
51.72
H -..
110.
108.7
H+C 2 H 2
100
90-
-J
K1
CD
8070
60r
106.3
z
LIJ
67.1
C2 H 3
INPUT PARAMETERS FOR UNIMOLECULAR QRRK
-
[CH 2 CO]
CH2 C-
products
*
k
**
A
1
E
5.0 E+15
<v> -
source
a
78.3
a
1193/cm
b
LJ PARAMETERS :
sigma
=
c
4.23 A 0
e/k -
314. K
A=5E12, Ea=0 (estimate);
(a) For reverse:
for forward, use thermo and A,Ea for reverse.
(b) From "CPFIT" program and Cp data.
(c) Estimated from critical properties for C2H4
(Reid, Prausnitz, and Sherwood).
* bimolecular:
UNITS:
unimolecular:
cm 3/mole-sec
1/sec
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
Gas
N2
P
A (cm3/
(torr)
Reaction
760.
CH2 CO-CH 2+CO
mole-sec)
2.01E+35
188
E (kcal
n
-6.68
/mole)
82.99
-1
70
CH 2 + CO
60-
50F
6>j
zJ
Li
40F
20
10
OF
JOF
-12.4
CH 2 CO
-20
189
INPUT PARAMETERS FOR BIMOLECULAR QRRK
[C2 H6 ]
H + C2H5
- products
*
k
**
A
1
1.8 E+14
-1
E
source
a
0.
a
1.26 E+16
100.1
b
2
7.94 E+16
89.8
c
3
3.0 E+12
78.
d
<v> - 1509/cm
e
LJ PARAMETERS
f
sigma - 4.34 A0
e/k = 247. K
(a) Al from thermodynamics and A-1; Ea=O for barrierless radical/radical combination.
(b) A-1 from Dean (1985); Ea-/\Hr-RTm.
(c) Ea=/\Hr-RTm; A2 from Dean (1985).
-
*
*
(d) A3=3*(ekTm/h)*exp(/\S /R) with Tm=1000 K and /\S
-7.5 eu (transition state theory); Ea-/\Hr+45
(e) From "CPFIT" program and Cp data.
(f) Estimated from critical properties for C2H6,
which
were estimated by Lydersen method
Prausnitz, and Sherwood).
UNITS:
* bimolecular:
cm 3/mole-sec
unimolecular: 1/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas (torr)
N2
760.
Reaction
H+C 2 H 5-[C
2 H 610
H+C2H52 CH 3
H+C2H5
2 H +H2
E (kcal
/mole)
A (cm3/
mole-sec)
n
5.18E+35
-6.83
6.81
8.73E+14
-0.08
3.08
5.95E+25
-4.22
8.86
190
(Reid,
90
80F
80.1
80K!
H+C 2 H 5
2 H6
K
2
K
70F
2 CH3
H~
60[
50-
69.6
KS(M)
H-C=C-H
IH
H
40
Q
w
20
LU
12.5
C 2 H4+ H2
IOF
-10
-20
-20.0
C2 H 6
191
INPUT PARAMETERS FOR BIMOLECULAR QRRK
CH3 + CH3 -
6[C - products
*
k
**
A
E
source
1
2.6 E+13
0.
a
-1
7.94 E+16
89.8
b
2
1.26 E+16
100.1
c
3
3.0 E+12
78.
d
a
<v> - 1509/cm
e
LJ PARAMETERS :
f
sigma - 4.34 A0
e/k - 247. K
(a) Al from thermodynamics and A-1; Ea=O for barrierless radical/radical combination.
(b) A-1 from Dean (1985); Ea=/\Hr-RTm.
(d) A3-3*(ekTm/h)*exp(/\S /R) with Tm-1000 K and /\S
-7.5 eu (transition state theory); Ea-/\Hr+45
-
(c) Ea-/\Hr-RTm; A2 from Dean (1985).
(e) From "CPFIT" program and Cp data.
(f) Estimated from critical properties for C2H6,
which
were estimated by Lydersen method
Prausnitz, and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm 3/mole-sec
1/sec
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas (torr)
N2
760.
Reaction
A (cm3/
mole-sec)
n
CH 3 +CH 3 -[C 2 H 6]0
2.68E+29
-4.95
6.13
CH 3+CH -H+C2H5
8.89E+18
-1.70
16.85
3.20E+25
-4.17
13.19
CH 3+CH3
2 H +H2
192
E (kcal
/mole)
(Reid,
90
1
19-.
80.1
8OF
K'->
[c2 H 6 *
K
70
2 CH3
H+C 2 H5
K2
K
H-C=C-H
HH
(-N
Li
50F
K 3(M)
40h
30F
'
-Li
w
w
20F
12.5
C 2 H4+ H 2
'OF
0
-10
20k
-20.0
C2H 6
194
INPUT PARAMETERS FOR BIMOLECULAR QRRK
-
H + C2 H
k
[C 2H5
-
products
A
E
source
a
1
3.98 E+13
2.6
a
-1
3.63 E+13
38.9
b
<v> - 1526/cm
c
LJ PARAMETERS
d
sigma - 4.34 A 0
e/k - 247. K
(a) Al, Ea from Dean (1985).
(b) k-i from thermodynamics and kl.
(c) From "CPFIT" program and Cp data.
(d) Estimated from critical properties for C2H6,
which
were estimated by Lydersen method
Prausnitz, and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm3/mole-sec
1/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas (torr)
N2
760.
Reaction
A (cm3/
mole-sec)
n
E (kcal
/mole)
H+C 2 H4 -[C 2 H 5 10
5.41E+35
-6.78
11.70
70 -
Kfi
64.6
60
H +Ij
4[2
67.2
(M)
H+C 2 H 4
50.
40-
30:
128.0
C2 H 5
20-L
(Reid,
199
INPUT PARAMETERS FOR BIMOLECULAR QRRK
H +
- (3H
k
A
products
*
**
E
a
source
1
2.62 E+14
0.
a
-1
1.0 E+16
105.1
b
<v> - 1957/cm
c
LJ PARAMETERS
d
sigma - 1.46 A0
(a)
(b)
(c)
(d)
UNITS:
-
e/k - 151. K
k-1 from thermodynamics and kl.
A-1, Ea(rev) from Dean (1985).
From "CPFIT" program and Cp data.
Estimated from critical properties for CH4,
which
were estimated by Lydersen method
Prausnitz, and Sherwood).
* bimolecular:
**
cm 3/mole-sec
unimolecular:
kcal/mole
1/sec
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas (torr)
N2
760.
Reaction
H+CH3 -[CH 4 0
A (cm3/
mole-sec)
7.09E+31
100-
80
n
-5.77
K,
H +CH 3
C
200-
-20-
I7.9
CH1
E (kcal
/mole)
5.89
(Reid,
INPUT PARAMETERS FOR BIMOLECULAR QRRK
H + COCi -
k
A
[HC1CO]
-
products
*
**
E
source
a
1
1.0 E+14
0.
a
-1
3.4 E+15
86.8
b
2
5.6 E+13
38.
c
3
1.1 E+15
78.
d
<v> - 1089/cm
e
LJ PARAMETERS :
f
sigma - 4.34 A0
e/k - 361. K
(a) Al appr. Af for H+.CH2Cl; Ea=0 due to radical/radical
recombination with no barrier.
.
(b) Reverse reaction (k_ 1 ) from thermodynamics and A1
-
(c) Ea from Setser and Lee (1985); A2 - ekTm/h with Tm
1000 K (transition state theory).
(d) Ea=/\Hr-RTm;
and A(rev).
A(rev) from NJIT group;
Af from thermo
(e) From "CPFIT" program and Cp data.
(f) Estimated from critical properties for HClCO,
estimated using Lydersen's Method (Reid, Prausnitz,
and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm 3/mole-sec
1/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
N2
760.
E (kcal
/mole)
A (cm3/
mole-sec)
n
H+COCl-[HC1CO]
3.13E+19
-2.93
1.77
H+COCl-CO+HC1
3.54E+16
-0.79
1.06
H+COCl-HCO+C1
3.42E+09
1.15
-0.18
Bath
P
Gas (torr)
Reaction
196
---
48.1
5 0K
K
[HCLCo]
H +COCL
K3
9.3
K2
HC O+ CL
Ks(M)
10
OH
0
LUQ
-J
L
-J
-I .3
-201Ld
01*
-39.3
HCLCO
-
4 8 .5
CO+ HCL
197
INPUT PARAMETERS FOR BIMOLECULAR QRRK
C1 + HCO
[HClCO]
-
-
products
*
k
**
E
A
source
a
1
1.0 E+13
0.
a
-1
1.1 E+15
78.
b
2
5.6 E+13
38.
c
<v> -
1089/cm
d
LJ PARAMETERS
e
sigma -
4.34 A 0
e/k -
361. K
(a) Al from NJIT group; Ea=0 due to radical/radical
recombination with no barrier.
(c) Ea from Setser and Lee (1985);
1000 K
A2 - ekTm/h with Tm
-
.
(b) Reverse reaction (k_ ) from thermodynamics
1
and A1
(transition state theory).
(d) From "CPFIT" program and Cp data.
(e) Estimated from critical properties
for HClCO,
Prausnitz,
estimated using Lydersen's Method (Reid,
and Sherwood).
* bimolecular:
UNITS:
unimolecular:
cm 3/mole-sec
1/sec
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
(torr)
N2
760.
E (kcal
A (cm3/
P
Gas
mole-sec)
n
/mole)
Cl+HCO-[HClCO]
6.42E+17
-2.67
1.41
Cl+HCO-CO+HCl
1.41E+14
-0.35
0.51
Reaction
198
K1
39.3
HCO+ CL
30k
-
50k
[HCLCo]
T
KK
2
20k
K5 (M)
10k
0
LU
H---CL
OH
-I13
OF
-20
wl
OF
40-
-39.3
HELCO
-
OH-
48.5
CO+ HCL
199
-1
INPUT PARAMETERS FOR BIMOLECULAR QRRK
Cl + CO - [COCl]
products
*
**
A
E
1
1.0 E+13
7.
a
-1
1.8 E+13
13.5
b
k
<v> -
source
a
699/cm
c
LJ PARAMETERS
d
sigma - 4.34 A0
e/k - 361. K
(a) Al, Ea from NJIT group.
.
(b) Reverse reaction (k_1 ) from thermodynamics
and k
(c) From "CPFIT" program and Cp data.
,
COHCl
(d) Estimated from critical properties for
estimated with Lydersen's method (Reid, Prausnitz,
and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm 3/mole-sec
1/sec
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas (torr)
N
2
760.
Reaction
Cl+CO-[COCl1]0
A (cm3/
mole-sec)
n
1.95E+19
-3.01
200
E (kcal
/mole)
8.07
12F
COCL]'
10-
"
9.5
8Ks(M)
KI K
6'-"N
4-)
2.5
CO+CL
2
0-o
w
-2-4.0
COCL
-6-
201
INPUT PARAMETERS FOR BIMOLECULAR QRRK
Cl + COC1 - [COCl2 ]
- products
*
**
A
E
1
1.0 E+13
0.
a
-1
7.5 E+15
76.9
b
2
5.6 E+13
66.2
c
k
<v> -
source
a
624/cm
d
LJ PARAMETERS :
e
sigma - 4.70 A0
e/k - 376. K
(a) Al from NJIT group; Ea-0 due to radical/radical
recombination with no barrier.
.
(b) Reverse reaction (k_ 1 ) from thermodynamics and k
(c) Ea-/\Hr+40; Af=(ekTm/h) with Tm-1000 K (transition
state theory).
(d) From "CPFIT" program and Cp data.
(e) Estimated from critical properties for COCl2
(Reid, Prausnitz, and Sherwood).
UNITS:
* bimolecular:
cm 3/mole-sec
1/sec
unimolecular:
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas
(torr)
N2
760.
A (cm3/
mole-sec)
Reaction
Cl+COCl-[CoCl210
Cl+COCl-CO+C1
n
E (kcal
mole)
3.40E+28
-5.61
3.39
1.49E+19
-2.17
1.47
2
202
-A
203
50k
140
Ki
30
24.9
K
[COCL 21
CL+COCL
20k
~\
K24
0
,C.
CL--ICL
13.6
lCH
CD
K 5 (M)
0
-ioF
-20
LI
L -26.4
C O+ CL 2
-30
40k
-5 0
-60
-52.6
COCL 2
INPUT PARAMETERS FOR BIMOLECULAR QRRK
Cl + HO2
[HOOCi]* = products
=
*
k
**
A
E
source
1
3.0 E+13
0.
a
-1
1.0 E+15
44.7
b
2
3.0 E+15
46.
c
a
<v> - 646/cm
d
1J PARAMETERS :e
sigma - 4.63 A0
e/k - 660. K
(a) Al from NJIT group; Ea=O due to radical/radical
recombination with no barrier.
.
(b) Reverse reaction (k_ 1 ) from thermodynamics and A1
(c) Ea=/\Hr-Tm; A-2 appr. Af for CH3+ClO
from thermodynamics and A2.
(1.3E13);
A2
(d) From "CPFIT" program and Cp data.
(e) Estimated from critical properties for
HOOC,
estimated using Lydersen's Method (Reid, Prausnitz,
and Sherwood).
UNITS:
*
bimolecular: cm 3/mole-sec
unimolecular: 1/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
(torr)
Gas
N2
760.
E (kcal
/mole)
A (cm3/
mole-sec)
n
Cl+HO 2 -[HOOCl]0
6.21E+31
-6.48
3.92
Cl+HO =OH+ClO
3.35E+14
-0.32
1.47
Reaction
204
L0
K
[HOOCL]
32.4
30B
CLO+OH
CL+HO 2
20F
KS(M)
(OQ-
OH
-
I0 F
-20
12.9
LJ
33.7
HOOCL
30H
205
INPUT PARAMETERS FOR BIMOLECULAR QRRK
C10 +
- [
. CH3
C1]= products
**
E
1
1.3 E+13
0.
a
-1
1.6 E+15
89.7
b
2
2.3 E+13
38.
c
3
1.9 E+14
63.2
d
*
A
k
<V> -
source
a
1111/cm
e
Li PARAMETERS
f
sigma - 5.12 A 0
e/k - 537. K
(a) Al appr.
0.5*Af for CH3+OH (2.6E13, Dean and
Westmoreland, 1987); Ea-0 for barrier-less radical/
radical recombination.
*
.
(b) Reverse reaction (k_1 ) from thermodynamics
and k1
(c) A2=*(ekTm/h)*exp(/\S /R) with Tm=1000 K and
/\S --4eu (from transition state theory); Ea-26+12
(ring strain + abstraction, from NJIT group).
(d) A-3 from NJIT group; A3 from thermodyamics and A-3;
Ea-/\Hr-RTm with Tm-1000 K.
(e) From "CPFIT" program and Cp data.
(f) Estimated from critical properties for CH30C1,
which were estimated by Lydersen method (Reid,
Prausnitz, and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm 3/mole-sec
1/sec
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
P
Bath
Gas (torr)
N2
760.
Reaction
A (cm3/
mole-sec)
n
E (kcal
/mole)
CH3+ClO-[CH3 On]0
2.59E+22
-3.70
2.44
CH 3+ClO=CH2 O+HC1
5.50E+14
-0.51
0.71
CH 3+ClO=CH3 0 +Cl
2.28E+07
1.54
-0.82
206
K1
[CH 3 OCLJ
59C. 3
60
CLO+CH 3
207
-I
K2
50
K3
K,(M)
32.8
20k
w
H
HH
-J
7.0
0
OH
CL
CL
0
10K
CH
30
+
I
30
-J
10k
-20k
30k
w
w
-31
CH 3 0CL
-40
-50
-
49.8
HCL+ CH 2 0
---------
INPUT PARAMETERS FOR UNIMOLECULAR QRRK
CH 3Cl
[CH 3 Cl]
products
**
*
=
k
A
E
1
1.0 E+15
81.6
a
2
1.7 E+14
127.4
b
3
8.9 E+15
98.8
c
source
a
<v> - 1565/cm
UJ PARAMETERS
sigma
=
d
:e
e/k - 350. cal
4.18 A0
(a) Ea=/\Hr-RTm; Af from NJIT group
(b) Ea=/\Hr+37.5; Af=3*ekTm/h with Tm - 1000 K
(transition state theory)
(c) Ea=/\Hr-RTm; A3 from thermo and A(rev)-1E14
(d) From "CPFIT" program and Cp data.
(e) Estimated from critical properties for CH3Cl
(Reid, Prausnitz, and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm 3/mole-sec
1/sec
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas (torr)
N2
760.
A (cm3/
E (kcal
/mole)
mole-sec)
n
CH 3Cl-CH 3+Cl
3.51E+36
-7.00
91.88
CH3 Cl-H 2+HC1
4.63E+28
-5.66
134.6
CH3 1-. H2 Cl+H
2.23E+34
-6.44
108.8
Reaction
208
II 0
W
-10
7.8
10 OF
90F
80
CH2CL+ H
81.2
70F
H2+HCL 70.3
60F
CH3 - CL
.64.0
w
-I
50
K2
40k
30F
/K
w
20I0i
OF
-io -,
20
K3
CH 3 CL
- 19.6
209
1
INPUT PARAMETERS FOR BIMOLECULAR QRRK
HO2 +
CH2C1
-
-
[CH 2 ClOOH]
*
E
A
k
products
**
source
a
1.0 E+13
0.
a
-1
5.6 E+16
65.0
b
2
2.6 E+15
41.4
c
1
<v>
=
787/cm
d
e
IJ PARAMETERS
sigma - 4.90 A0
e/k - 598. cal
(a) Al from NJIT group; Ea - 0 from barrier-less radical
/ radical recombination.
.
(b) Reverse reaction (k_1 ) from thermodynamics
and k1
(c) A-2 appr. 1E13 from NJIT group;
Ea-2 - 0 for
barrier-less radical/radical recombination;
k2 from
thermodynamics and k-2.
(d) From "CPFIT" program and Cp data.
(e) Estimated from critical properties for CH2C100H,
which
were estimated by Lydersen method (Reid,
Prausnitz, and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm 3/mole-sec
1/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas (torr)
N2
A (cm3/
mole-sec)
Reaction
760. HO2+.CH 2 C1=[CH 2 C100H]0
HO2+.CH2 Cl-CH 2ClO.+OH
210
n
E (kcal
/mole)
9.88E+28
-5.97
3.56
5.19E+14
-0.51
0.84
LOF
32.6
30
'
[CH 2 CLooH]
.CH 2 CL -+ HO 2
K2
20V
KS (M)
9.0
CH 2CLO
+OH
[oH
-
0
-
0
-
I0 O
-20
w
w1
-3 0F-
-32.4
CH 2 CLOOH
211
INPUT PARAMETERS FOR BIMOLECULAR QRRK
02 +
-
[CH 2 ClOO.]
CH2 C*
k
A
products
**
E
source
a
1
1.5 E+12
1.0
a
-1
5.7 E+14
26.6
b
2
1.2 E+15
55.6
c
4
8.0 E+12
31.5
d
-4
1.1 E+l1
19.6
e
5
1.2 E+13
2.0
f
<v> = 800/cm
g
LJ PARAMETERS
h
sigma
=
4.90 A0
e/k
=
598. K
(a) Al appr. 0.5*Af for 02+.CC (Af=3E12) from Bozzelli
and Dean (1989); Ea appr. 0.5+Ea for 0 + CH2C1.
.
(b) Reverse reaction (k_1 ) from thermodynamics and k
(c) A-2 appr. 0.5*Af from O+CH30. (Af-5E13) from Dean and
Westmoreland (1987); A2 from A-2 and thermodynamics;
Ef-/\Hr-RTm.
*
*
(d) A4-l*(ekTm/h)*exp(/\S /R) with Tm=1000K and /\S --4eu
(transition state theory); Ea-18+7+6.5 (for ring
strain+abstraction+/\Hr).
4
) from thermodynamics and k
.
(e) Reverse reaction (k
Ea for .CH200H -- > CH20+OH from Dean and
Westmoreland (1987); A-5 appr. 0.5 * Af for OH+CH20.
(f) Ea
(g) From "CPFIT" program and Cp data.
(h) Estimated from critical properties for CH2ClOOH,
which
were estimated by Lydersen method (Reid,
Prausnitz, and Sherwood).
UNITS:
*
bimolecular: cm 3/mole-sec
unimolecular: 1/sec
212
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
P
Bath
Gas (torr)
A (cm3/
mole-sec)
Reaction
6.73
4.59E+36
-8.22
0 2+.CH2 C1-CH 2Cl+0
8.08E-10
6.07
14.87
0 2+.CH2 Cl-.CH 200C1
1.20E+16
-2.96
8.56
0 2+.CH2 Cl-CH 2O+C1O
8.46E+13
-1.03
8.18
760. 02+.CH 2 C1l-(CH 2 C100.]
N2
E (kcal
/mole)
n
CH 2 CLO-+-0
60 ~61.7
50-
2
.
*0
KC1O
40Kl-
-CHCL+0
2
30 -
29.1
20 -.
+2
H
[CH 2CLOO]
I
~H
-35.2
KH
0
L
2 00CL]
[M]K
KA
lo -
11.9
2.0
.3.7
0-
CLO +CH2
5 2
-
-10
-C
PE. DIA GRAM : -CH2CL + 02
213
INPUT PARAMETERS FOR BIMOLECULAR QRRK
CH3 + .CH2 Cl -
A
Ea
*
k
Products
**
source
1
1.6 E+13
0.
a
-1
1.3 E+17
90.4
b
2
6.4 E+12
52.8
c
3
2.2 E+15
83.5
d
<v>
1085/cm
e
J PARAMETERS
f
=
sigma - 4.84 A
e/k - 379. K
(a)
A (forward) from 0.5 * high pressure A for H +
from Allara and Shaw ( ).
(b)
Reverse reaction (k_) from thermodynamics
(forward).
(c)
A2=3*(ekTm/h)*exp(/\S*/R) with /\S*--6.6eu (transition state theory); Ea=/\H -RTm with Tm=1000K
Ea - /\ H -RTm; A (forwardY from thermo and A (reverse) - high pressure A factor for CH3 + 2-C3H7 from
Allara and Shaw (1980).
From "CPFIT" program and C data.
Calculated from criticalp properties for C2H5 Cl
(Reid, Prausnitz, and Sherwood).
(d)
(e)
(f)
UNITS:
-
[C 2 H 5 Cl]
* bimolecular:
unimolecular:
cm 3/mole-sec
1/sec
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas (torr)
N2
760.
Reaction
A (cm3/
mole-sec)
n
E (kcal
/mole)
CH3+.CH2 Cl[C 2 H 5Cl]
8.47E+34
-6.75
8.08
CH 3+. CH 2Cl-C 2H +HCl
4.80E+24
-3.44
7.69
CH3 + CH 2Cl-C2 H5+Cl
2.04E+19
-1.81
10.34
214
and
C H
A
K7
64.2
#
70F
[2 H CL
K
-CH 2 CL +CH 3 I1
60k
56.9
2
C2 H5 +CL
50
KS(M)
H---CL
H-d
30k
-H
26.0
20k
10i
LU
-J
0
0
-
-J
-9.5
I0F
C 2 H 4 +HCL
Ld
-26.8
30k
C 2 H5 CL
215
INPUT PARAMETERS FOR BIMOLECULAR QRRK
0 + .CH2 Cl
k
A
1
-1
2
<v> -
- products
[CH 2 1O.]
*
**
E
source
a
2.0 E+13
0.5
a
1.2 E+16
84.5
b
3.0 E+13
7.0
c
1247/cm
d
LJ PARAMETERS
e
sigma - 4.61 A 0
e/k - 535. K
(a) Al appr. 0.35*Af for 0+CH3; Ea from Ea for 0 +
(Dean and Westmoreland, IJCK, 1987).
CH3
.
(b) Reverse reaction (k_1 ) from thermodynamics
and A1
CCCC. --- > C2H5+C=C as analagous reaction
(Af-2E13, Ea-/\Hr+7) from Dean (JPC, 1985).
Take A2-1.5*Af; Ea appr. /\Hr+7.
(c) Use
(d) From "CPFIT" program and Cp data.
(e) Estimated from critical properties for CH2C1OH,
which
were estimated by Lydersen method (Reid,
Prausnitz, and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm3/mole-sec
1/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
P
Bath
Gas (torr)
N2
760.
Reaction
A (cm3/
mole-sec)
n
O+.CH 2 Cl-[CH 2 ClO.]
2.55E+15
-2.02
1.23
O+.CH2 Cl=CH2 O+Cl
8.31E+13
-0.18
0.80
216
E (kcal
/mole)
CH 2 CLO-]
90
88.7K-
E =0.5
.CH 2 CL-+ 0
80F
70
60F
w
K2
KsM
50S
-J
0
f
-j
40
30
uJ
z
w
20
CL
H-C O
H
10
OF
RE.
9 2
2.2
1.
CH 2 CLO-
CF 20+CL
DIAGRAM: -CH 2 CLi-0
217
INPUT PARAMETERS FOR BIMOLECULAR QRRK
OH +
.CH2Cl
- products
[CH2ClOH]
*
k
**
A
E
1
1.6 E+13
0.
a
-1
2.4 E+16
91.0
b
2
7.6 E+12
40.6
c
3
5.5 E+15
81.2
d
<v>
=
source
a
e
1200/cm
LJ PARAMETERS :
sigma - 4.61 A0
f
e/k - 535. K
*
(b) Reverse reaction (k_1 ) from thermodynamics
and k
.
(a) Al appr. same as Af for CH2Cl+CH3; Ea=O for barrierless radical/radical combination.
(c) A4=*(ekTm/h)*exp(/\S /R) with Tm-1000 K and
/\S --4eu (from transition state theory); Ea-/\Hr+38.
(d) A-3 from NJIT group; A3 from thermodyamics and
Ea-/\Hr-RTm with Tm-1000 K.
A-3;
(e) From "CPFIT" program and Cp data.
(f) Estimated from critical properties for CH2C1OH,
which
were estimated by Lydersen method (Reid,
Prausnitz, and Sherwood).
UNITS:
*
bimolecular: cm 3/mole-sec
unimolecular: 1/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
N2
E (kcal
/mole)
A (cm3/
mole-sec)
n
3.15E+28
-5.35
4.92
OH+.CH2 Cl-CH 2O+HC1
4.10E+21
-2.57
3.74
OH+.CH2 Cl=.CH2 OH+Cl
9.24E+ll
0.38
2.97
P
Bath
Gas
(torr)
Reaction
760. OH+.CH2 Cl-[CH 2ClOH]0
218
38.6
40
[CH 2 CLOH]
2
-CH 2 CL + OH
K2
30V
K
29.4
-CH 2 0H +CL
20H
10
KS(M)
LU
0
Oh
c-
PH,
H' H
-I 0b
Li)
-20
-3 0F
401-
50H
-52.4
CH 2 CLOH
'-60
219
-49.8
HCL+CH 2O
INPUT PARAMETERS FOR BIMOLECULAR QRRK
[.CH2CH2OC1
Clo + C2H 4
k
A
-
*
products
**
E
a
source
1
2.0 E+12
2.
a
-1
2.2 E+13
29.4
b
4
1.3 E+12
23.
c
-4
3.6 E+13
41.
d
5
2.4 E+14
18.4
e
<v> - 731/cm
f
LJ PARAMETERS
g
sigma - 5.64 A0
e/k - 592. K
(a) Al appr. 0.5*Af for OH+C2H4 (Af=4E12,Ea2
Benson, 1976); Ea appr. Ea for OH+C2H4.
from
.
(b) Reverse reaction (k_1 ) from thermodynamics and k1
*
*
(c) A4-1*(ekTm/h)*exp(/\S /R) with Tm-1000 K and /\S
7.5 eu (transition state theory);
Ea-16+7 (for ring
strain+abstraction).
.
(d) Reverse reaction (k 4 ) from thermodynamics and k
(e) Ea5 appr. Ea, A-5 appr. Af for CH3+C2H4-->1-.C3H7H
(Af-1.2Ell, Ea-7.7 from Allara and Shaw 1980); k5
from thermodynamics and k-5.
(f) From "CPFIT" program and Cp data.
(g) Estimated from critical properties for C2H5OC1,
which
were estimated by Lydersen method (Reid,
Prausnitz, and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm 3/mole-sec
1/sec
220
**
kcal/mole
2
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas
(torr)
N2
A (cm3/
mole-sec)
Reaction
760. C1O+C 2 H4 -[.CH2CH2Cl]
C10+C 2 H4 -[CH
C10+C 2H
K1
40
36.7
-
2 ClCH20.
CH 2Cl+CH2 0
n
E (kcal
/mole)
1.75E+32
-6.32
7.90
5.40E+24
-4.99
8.87
9.26E+18
-1.98
8.43
C CH2 -I
KL22CH2CH20CL]1H
[CH 2 CLCH[201
K4
H-C IK
-H
33.7
5
C2 H 4 +CLO
30
Li
KAS(M)
KBS(M)
20
CL 0
H-C----H
1 1
H H
--
8.3
10F
-CH CHOCL
OF
Lu
2HC2H1.4
84
-CH2CL +CH2
-10.
-10-
CH2CLCH20-
221
222
INPUT PARAMETERS FOR UNIMOLECULAR QRRK
CH2C10. -
- products
**
*
k
[CH 2 ClO.]
1
A
E
3.0 E+13
7.
source
a
a
<v> - 1247/cm
b
LJ PARAMETERS
c
sigma - 4.61 A0
e/k - 535. K
(a) See note c for O+.CH2Cl bimolecular QRRK input
(b) From "CPFIT" program and Cp data.
(c) Estimated from critical properties for C2H4
(Reid, Prausnitz, and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm 3/mole-sec
1/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas (torr)
2
760.
A (cm3/
mole-sec)
n
CH2 CO.-CH2 O+Cl
2.51E+24
-4.78
E (kcal
/mole)
10.07
C*L
Lr
H-c~Q
-
N
Reaction
I0
5
0.
H
-IJ
zw
u-I
2.2
CH 2 CLO-
2
-i
CH20 +CL
I
INPUT PARAMETERS FOR BIMOLECULAR QRRK
H +
CH2C1 -
k
- products
[CH 3 Cl]
**
E
1.0 E+14
0.
a
-1
8.9 E+15
98.8
b
2
1.0 E+15
81.6
c
*
A
1
source
a
<v> - 1565/cm
d
LJ PARAMETERS
e
sigma - 4.18 A0
e/k - 350. K
/
(a) Al from NJIT group;
Ea-0 for barrierless radical
radical combination.
(b) A-1 from thermodynamics and Al; Ea-/\Hr-RTm.
(c) Ea-/\Hr-RTm with Tm-1000 K;
A2 from NJIT group.
(d) From "CPFIT" program and Cp data.
(e) Estimated from critical properties for CH3C1
(Reid, Prausnitz, and Sherwood).
UNITS:
* bimolecular:
unimolecular:
cm 3/mole-sec
** kcal/mole
1/sec
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
Bath
P
Gas (torr)
N
2
760.
A (cm3/
mole-sec)
n
E (kcal
/mole)
H+.CH2Cl-[CH 3Cl]
1.06E+28
-5.01
4.35
H+.CH 2 Cl-CH 3+C1
1.68E+16
-0.68
1.02
Reaction
223
A
90
K1
CH2GL + H
81.2
80
(CH 3 CL]
IK
2N
70-
CH3
60
50
KS(M)
-J
-- J
40F
30
w
20F
IOF
OF
- 10
CH 3 CL
20F
19.6
223 B
+
CL
64.0
APPENDIX 4 - - JET MIXING EQUATIONS FOR CHEMKIN
usual plug flow (or batch) reactor species and
The
balance
equations used in CHEMKIN are as follows:
enthalpy
For species i,
the differential equation is
i-l,...,k
dY./dt - w. W. / p
1
1
1
of
t -
mass fraction of i,
where Y.
i,
W.
=
time, w.
molar reaction rate
=
and p - mass
molecular weight of i,
The
density.
enthalpy balance is given by
k
)
dT/dt - -1/(p C
where
- temperature,
T
h.
=
(h. w. W.)
specific enthalpy of i,
and
C
p
1
average
specific heat.
The species specific and mean
These
are calculated by various CHEMKIN subroutines.
=
quantities
equations
are integrated with the LSODE package.
The
above equations can be modified to describe a plug
with turbulent jet mixing (entrainment) of
reactor
Consider
et.al.
with
the
control
taken
surroundings.
from
Dibble
For the same application of turbulent jet mixing
(1989).
Dibble et.al.
reaction,
function
volume in Figure A-1,
flow
wrote the balance equations
as
a
The species balances
of distance x along the jet axis.
are
dY./dx - (Y
where
Ysi
-
C
entrained,
velocity,
d
.-Y.) + C..xw.W./(pu d
s,1
1
3)
C xw
1
(pO
mass fraction of i in the surrounding fluid
-
jet mixing parameter - 0.32, u
- equivalent nozzle diameter -
- nozzle diameter,
p
-
jet exit density,
224
-
d
ps
to
be
jet nozzle exit
s(pp)2 where d0
-
surrounding fluid
FIGURE A-1
entrainment
dmh
A
dx
are a, A
.~
h Yk
reaction
+
M hYk
kWk AAx
I
I
Ax
control volume.
BY DIBBLE ET.AL.
(1989)
225
AMhYk
density. The enthalpy balance is given by
C (dT/dx) p
k*k
Y
(1/x)
.(h
.-h.)
-
i.
s~
s,1
C x/(pu 0d )(h
d
w.W.)
. - specific enthalpy of i in the surrounding fluid.
where h
we will convert the
the purposes of the PFR(JM)/PSR model,
For
inde-
pendent variable from x to t.
A velocity relationship is needed
fully
developed
to do this conversion. The
velocity of a turbulent free jet
axial
be
can
*
estimated from
(1/x) - a/x
u - (u d /b)
u
=
velocity at a axial point x,
b -
an empirical
0.16
-
*
where
(Beer and Chigier,
We can
1983). For convenience here, a-u d /b.
further write
u -
dx/dt
=
a/x
Integrating with the assumed boundary condition of x-O at t-0,
we
obtain a relation between x and t.
For
the
we
conversion,
(df/dt)/(dx/dt).
use
the
relation
df/dx
Substituting, we have for our species balances
dY./dt 1
will
(Y
.-Y.)/(2t)
+ 2w.W./p
12.
1
S,1
The enthalpy balance becomes
C
k
(dT/dt) - 1/(2t) EY
p
k
i(hs
h)
,i
,~~~isl
226
-
( 2 /p)
1
(hw.Wi)
-
(2 a)1/ 2 t1 / 2
x
These
two balance equations are those integrated by LSODE in
new hybrid model.
is
Due to the singularity at t-0,
begun at a small t>0.
the
the integration
This issue might be investigated by
a
future intrepid graduate student.
An
overall
mass balance is also needed for the
model.
The
total mass (nozzle and entrained fluid) mixed on a molecular level
*
passing an axial point x is given by
m - m C x/d
o 2
where
C2
(Dibble
-
tially
C20.11.
empirical constant,
et.al.,
a
1989).
stagnant
m
For free turbulent jet flow into
surrounding
gas,
earlier derived relation,
get
m -
An
Dibble
et.al.
rate
essen-
recommend
Since the TJSC uses jets in a turbulent cross flow, the
mixing is probably much better.
the
mozzle fluid mass flow
-
We will take C2 -C1 -0.32.
Using
substitute for x in terms of t
to
**
1/2 1/2
(m C2 /d ) (2u d /b)
t
estimate must be made for u .
From Nenniger
et.al.
(1984),
typical jet exit Mach numbers are about 0.7 for 17 guage (0.041 in
ID) jet tubes.
For the current modeling, we are assuming the exit
gas temperature to be about 400 K.
to be about 920 ft/sec.
The velocity u0 is calculated
Substituting these values gives the total
mass at time t in the PFR(JM) section of the model.
m - m0 (587.) (ps
227
0
)1/4 t1/ 2
APPENDIX 5
Table A-1: Reactions for Cl/C2 Hydrocarbon Oxidation
REACTION
CH3 + CH3 - C2H6
CH3 + H
- CH4
CH4 + 02 - CH3 + H02
CH4 + H -
CH3 + H2
OH - CH3 + H20
H02 - CH3 + H202
H02 - CH30 + OH
02 - CH30 + 0
CH3 + 0 - CH20 + H
CH20H + H - CH3 + OH
CH30 + H = CH3 + OH
CH3 + OH - CH2 + H20
CH3 + H - CH2 + H2
CH30 + M - CH20 + H + M
CH20H + M - CH20 + H + M
CH30 + H - CH20 + H2
CH20H + H - CH20 + H2
CH30 + OH - CH20 + H20
CH20H + OH - CH20 + H20
CH30 + 0 - CH20 + OH
CH20H + 0 - CH20 + OH
CH30 + 02 - CH20 + H02
CH20H + 02 - CH20 + H02
CH2 + H - CH + H2
CH2 + OH - CH + H20
CH2 + OH - CH20 + H
CH + 02 - HCO + 0
CH + 0 - CO + H
CH + OH - HCO + H
CH + C02 - HCO + CO
CH + H - C + H2
CH + H20 - CH20 + H
CH + CH20 - CH2CO + H
CH + C2H2 - C3H2 + H
CH + CH2 - C2H2 + H
CH + CH3 - C2H3 + H
CH + CH4 - C2H4 + H
C +,02 - CO + 0
CH4
CH4
CH3
CH3
+
+
+
+
C +
OH - CO + H
C +
C +
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH3 CH2 + C02
+ 0 + 0 + 02 + 02 + 02 + 02 -
C2H2 + H
C2H + H
- CH20 + CO
CO + 2H
CO + H2
C02 + 2H
CH20 + 0
C02 + H2
CO + H20
SOURCE@
A
n
(Bi)
(B2)
(M3)
(M4)
(M5)
(M6)
(M7)
(M8)
(M9)
(M10)
(Ml)
(M12)
(M13)
(M14)
(M15)
(M16)
(M17)
(M18)
(M19)
(M20)
(M21)
(M22)
(M23)
(M24)
(M25)
(M26)
(M27)
(M28)
(M29)
(M30)
(M31)
(M32)
(M33)
(M34)
(M35)
(M36)
(M37)
(M38)
(M39)
(M40)
(M41)
(M42)
(M43)
(M44)
(M45)
(M46)
(M47)
(M48)
2. 68E+29
7.09E+31
7.90E+13
2.20E+04
1.60E+06
1.80E+11
2.OOE+13
2.05E+19
8.OOE+13
1.OOE+14
1.OOE+14
7.50E+06
9.OOE+13
1.OOE+14
1.OOE+14
2.OOE+13
2.OOE+13
1.OOE+13
1.OOE+13
1.OOE+13
1.OOE+13
6.30E+10
1.48E+13
1.OOE+18
1.13E+07
2.50E+13
3.30E+13
5.70E+13
3.OOE+13
3.40E+12
1.50E+14
1.17E+15
9.46E+13
1.OOE+14
4.OOE+13
3.OOE+13
6.OOE+13
2.OOE+13
5.OOE+13
5.OOE+13
5.OOE+13
1.10E+11
5.OOE+13
3.OOE+13
1.60E+12
5.OOE+13
6.90E+11
1.90E+10
-4.95
-5.77
0.000
3.000
2.100
0.000
0.000
-1.570
0.000
0.000
0.000
2.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
-1.560
2.000
0.000
0.000
0.000
0.000
0.000
0.000
-. 750
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
228
E
6130.
5890.
56000.
8750.
2460.
18700.
0.
29229.
0.
0.
0.
5000.
15100.
25000.
25000.
0.
0.
0.
0.
0.
0.
2600.
1500.
0.
3000.
0.
0.
0.
0.
690.
0.
0.
-515.
0.
0.
0.
0.
0.
0.
0.
0.
1000.
0.
0.
1000.
9000:
500.
-1000.
TABLE A-1 continued
CH2 + 02 - CO + OH + H
CH2 + 02 - HCO + OH
CH20 + OH - HCO + H20
CH20 + H - HCO + H2
CH20 + M - HCO + H + M
CH20 + 0 - HCO + OH
HCO + OH - H20 + CO
HCO +
M - H + CO + M
H2/1.9/
CO/1.9/
HCO + H - CO + H2
HCO + 0 - CO + OH
HCO + 0 - C02 + H
HCO + 02 - H02 + CO
CO + 0 + M - C02 + M
CO +
OH - C02 + H
CO + 02 - C02 + 0
H02 + CO - C02 + OH
C2H6 + CH3 - C2H5 + CH4
C2H6 + H - C2H5 + H2
C2H6 + 0 - C2HS + OH
C2H6 + OH - C2H5 + H20
C2H4 + H - C2H3 + H2
C2H4 + 0 - CH3 + HCO
C2H4 + OH - C2H3 + H20
CH2 + CH3 - C2H4 + H
H + C2H4 - C2H5
C2H5 + H - 2CH3
C2H5 + H - C2H6
C2H5 + 02 - C2H4 + H02
C2H2 + 0 - CH2 + CO
C2H2 + 0 - HCCO + H
H2 + C2H - C2H2 + H
C2H3 - C2H2 + H
C2H3 + H - C2H2 + H2
C2H3 + 0 - CH2CO + H
C2H3 + 02 - CH20 + HCO
C2H3 + OH - C2H2 + H20
C2H3 + CH2 - C2H2 + CH3
C2H3 + C2H - 2C2H2
C2H3 + CH - CH2 + C2H2
OH + C2H2 - C2H + H20
OH + C2H2 - HCCOH + H
OH,+ C2H2 - CH2CO + H
OH + C2H2 - CH3 + CO
HCCOH + H - CH2CO + H
C2H2 + 0 - C2H + OH
CH2CO + 0 - C02 + CH2
CH2CO + H - CH3 + CO
CH2CO + H - HCCO + H2
CH2CO + 0 - HCCO + OH
CH2CO + OH - HCCO + H20
CH2CO - CH2 + CO
C2H + 02 - 2CO + H
CH4/2.8/
(M49)
(M50)
(M51)
(M52)
(M53)
(M54)
(M55)
(M56)
C02/3.0/
(M57)
(M58)
(M59)
(M60)
(M61)
(M62)
(M63)
(M64)
(M65)
(M66)
(M67)
(M68)
(M69)
(M70)
(M71)
(M72)
(B3)
(B4)
(B5)
(M75)
(M76)
(M77)
(M78)
(B6)
(M80)
(M81)
(M82)
(M83)
(M84)
(M85)
(M86)
(M87)
(M88)
(M89)
(M90)
(M91)
(M92)
(M93)
(M94)
(M95)
(M96)
(M97)
(B7)
(M99)
229
8.60E+10
4.30E+10
3.43E+09
2. 19E+08
3.31E+16
1.80E+13
1.OOE+14
2.50E+14
H20/5.0/
1. 19E+13
3.OOE+13
3.OOE+13
3.30E+13
6.17E+14
1.5 1E+07
1.60E+13
5.80E+13
5.50E-01
5.40E+02
3.OOE+07
8.70E+09
1.10E+14
1.60E+09
2.02E+13
3.OOE+13
5.41E+35
8.73E+14
5.18E+35
8.43E+11
1.02E+07
1. 02E+07
4.09E+05
5.62E+31
4.OOE+13
3.OOE+13
4.OOE+12
5.OOE+12
3.OOE+13
3.OOE+13
5.OOE+13
3.37E+07
5.04E+05
2. 18E-04
4.83E-04
1.OOE+13
3.16E+15
1.75E+12
1.13E+13
5.OOE+13
1.OOE+13
7.50E+12
2.01E+35
5.OOE+13
0.000
0.000
1.180
1.770
0.000
0.000
0.000
0.000
-500.
-500.
-447.
3000.
81000.
3080.
0.
16802.
.250
0.000
0.000
-. 400
0.000
1.300
0.000
0.000
4.000
3.500
2.000
1.050
0.000
1.200
0.000
0.000
-6.78
-0.08
-6.83
0.000
2.000
2.000
2.390
-6.06
0.000
0.000
0.000
0.000
0.000
0.000
0.000
2.000
2.300
4.500
4.000
0.000
-. 600
0.000
0.000
0.000
0.000
0.000
-6.68
0.000
0.
0.
0.
0.
3000.
-758.
41000.
22934.
8300.
5210.
5115.
1810.
8500.
746.
5955.
0.
11700.
3080.
6810.
3875.
1900.
1900.
864.
51720.
0.
0.
-250.
0.
0.
0.
0.
14000.
13500.
-1000.
-2000.
0.
15000.
1350.
3428.
8000.
8000.
2000.
82990.
1500.
TABLE A-1 continued
C2H + C2H2 - C4H2 + H
H + HCCO - CH2(1) + CO
0 + HCCO - H + 2CO
HCCO + 02 - 2CO + OH
CH + HCCO - C2H2 + CO
2HCCO - C2H2 + 2CO
CH2(1) + M - CH2 + M
H/0.0/
CH2(1) + CH4 - 2CH3
CH2(1) + C2H6 - CH3 + C2H5
CH2(1) + 02 - CO + OH + H
CH2(1) + H2 - CH3 + H
CH2(1) + H - CH2 + H
C2H +
0
-
CH + CO
C2H + OH - HCCO + H
2CH2 - C2H2 + H2
CH2 + HCCO - C2H3 + CO
CH2 + C2H2 - C3H3 + H
C4H2 + OH - C3H2 + HCO
C3H2 + 02 - HCO + HCCO
C3H3 + 02 - CH2CO + HCO
C3H3 + 0 - CH20 + C2H
C3H3 + OH - C3H2 + H20
2C2H2 - C4H3 + H
C4H3 + M - C4H2 + H + M
CH2(1) + C2H2 - C3H3 + H
C4H2 + 0 - C3H2 + CO
C2H2 + 02 - HCCO + OH
C2H2 + M - C2H + H + M
C2H4 + M - C2H2 + H2 + M
C2H4 + M - C2H3 + H + M
H2 + 02 - 20H
OH + H2 - H20 + H
O + OH - 02 + H
O + H2 - OH + H
H + 02 + M - H02 + M
H20/18.6/
C02/4.2/
H2/2.9/
OH + H02 - H20 + 02
H + H02 - 20H
0 + H02 - 02 + OH
20H - 0 + H20
2H + M - H2 + M
11-2/0.0/
C02/0.0/
H20/0.0/
2H + H2 - 2H2
2H + H20 - H2 + H20
2H + C02 - H2 + C02
H + OH + M - H20 + M
H20/5.0/
H + 0 + M - OH + M
H20/5.0/
20 + M - 02 + M
H + H02 - H2 + 02
2HO2 - H202 + 02
3.OOE+13
1.OOE+14
1.OOE+14
1.60E+12
5.OOE+13
1.OOE+13
1. OOE+13
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.
0.
0.
854.
0.
0.
0.
4.OOE+13
1.20E+14
3.OOE+13
7.OOE+13
2.OOE+14
5.OOE+13
2.OOE+13
4.OOE+13
3.OOE+13
1.20E+13
6.66E+12
1.OOE+13
3.OOE+10
2.OOE+13
2.OOE+13
2.OOE+12
1.OOE+16
3.OOE+13
1.20E+12
2.OOE+08
4.20E+16
1.50E+15
1.40E+15
1.70E+13
1.17E+09
4.OOE+14
5.06E+04
3.61E+17
N2/1.3/
7.50E+12
1.40E+14
1.40E+13
6.OOE+08
1.OOE+18
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
1.500
0.000
0.000
0.000
0.000
1.300
-. 500
2.670
-. 720
0.
0.
0.
0.
0.
0.
0.
0.
0.
6600.
-410.
0.
2868.
0.
0.
45900.
59700.
0.
0.
30100.
107000.
55800.
82360.
47780.
3626.
0.
6290.
0.
0.00
0.000
0.000
1.300
-1.000
0.
1073.
1073.
0.
0.
(M140)
(M141)
(M142)
(M143)
9.20E+16
6.OOE+19
5.49E+20
1.60E+22
-. 600
-1.250
-2.000
-2.000
0.
0.
0.
0.
(M144)
6.20E+16
-. 600
0.
(M145)
(M146)
(M147)
1.89E+13
1.25E+13
2.OOE+12
0.000
0.000
0.000
-1788.
0.
0.
(M100)
(m101)
(M102)
(M103)
(M104)
(M105)
(M106)
(M107)
(M108)
(M109)
(M110)
(Mll)
(M112)
(M113)
(M114)
(M115)
(M116)
(M117)
(M118)
(M119)
(M120)
(M121)
(M122)
(M123)
(M124)
(M125)
(M126)
(M127)
(M128)
(M129)
(M130)
(M131)
(M132)
(M133)
(M134)
CO/2.1/
(M135)
(M136)
(M137)
(M138)
(M139)
230
TABLE A-1 continued
H202 + M - 20H + M
H202 + H - H02 + H2
H202 + OH - H20 + H102
(M148)
(M149)
(M150)
1.30E+17
1.60E+12
1.OOE+13
0.000
0.000
0.000
45500.
3800.
1800.
$
Rate constants are in the form A * Tn * exp(-E/RT) for forward direction.
All reactions are considered reversible. Units are in moles, cc, sec, K,
cal.
@
Reactions M# are from Miller and Bowman, 1988. Parameters for reactions
B# were developed as original work in this project.
231
APPENDIX 5
Table A-2: Species Thermodynamic Properties for Cl/C2 Hydrocarbon Mechanism
SPECIES
C
C2H
C2H2
C2H3
C2H4
C2H5
C2H6
C3H2
C3H3
C4H2
C4H3
CH
CH2
CH2(1)
CH20
*CH20H
CH3
CH30
CH30H
CH4
C2H50H
CO
C02
H
H2
H20
H202
HCCOH
HCO
H02
N2
0
02
OH
CH2CO
*HCCO
HF(298)
S(298)
CP300
CP500
CP600
CP800
CP1000
CP1500
171.31
134.01
54.20
67.10
12.54
28.02
-20.04
106.53
76.50
111.71
101.98
142.01
92.49
101.51
-27.70
-6.10
34.82
3.90
-48.00
-17.90
-56.20
-26.42
-94.0-6
52.10
.00
-57.80
-32.53
20.43
10.40
2.50
.00
59.56
.00
9.32
-12.40
42.40
37.76
49.57
48.02
56.20
52.38
60.14
54.73
56.22
59.90
59.79
65.27
43.72
46. 72
45.10
52.25
59.61
46.38
54.61
57.31
44.47
67.51
47.21
51.08
27.39
31.21
45.10
55.66
58.71
53.66
54.73
45.77
38.47
49.01
43.88
57.81
58.91
4.98
8.92
10.62
10.89
10.23
11.32
12.58
13.21
14.01
17.74
17.38
6.95
8.25
8.07
8.40
9.73
9.23
9.08
10.50
8.43
15.69
6.95
8.91
4.97
6.90
8.00
10.41
13.22
8.24
8.34
6.95
5.23
7.01
7.15
12.43
12.20
4.97
10.21
13.08
13.87
14.94
15.95
18.62
16.95
18.33
21.85
22.37
7.05
8.88
8.60
10.50
12.64
10.83
12.43
14.24
11.14
22.81
7.14
10.65
4.97
7.00
8.44
12.34
16.16
9.28
9.49
7.08
5.08
7.44
7.07
15.67
14.44
4.97
10.72
13.95
15.11
16.83
18.29
21.30
18.32
19.95
23.24
24.25
7.11
9.23
8.98
11.47
13.88
11.52
13.98
15.95
12.41
25.68
7.27
11.31
4.97
7.02
8.67
13.11
17.35
9.77
9.97
7.19
5.05
7.65
7.06
16.91
15.20
4.97
11.56
15.27
17.15
20.05
22.58
25.82
20.25
22.36
25.10
27.06
7.37
9.93
9.85
13.36
16.00
12.87
16.63
18.98
15.00
30.31
7.61
12.32
4.97
7.07
9.22
14.29
19.15
10.74
10.78
7.50
5.02
8.07
7.13
18.85
16.25
4.97
12.18
16.31
18.73
22.51
25.50
29.30
21.63
24.23
26.61
29.24
7.78
10.57
10.61
14.88
17.69
14.12
18.60
21.48
17.25
33.81
7.95
12.99
4.97
7.21
9.87
15.21
20.30
11.52
11.39
7.83
5.00
8.35
7.33
20.29
16.99
4.97
13.29
18.27
21.34
26.22
29.56
34.61
24.12
27.26
28.96
32.55
8.75
11.74
11.83
16.97
20.56
16.27
21.51
25.54
20.63
39.49
8.41
13.93
4.97
7.73
11.26
16.85
22.29
12.56
12.45
8.32
4.98
8.72
7.87
22.65
18.44
All species are taken in their standard states (gas) at one atmosphere.
Temperatures are in Kelvins.
*
Properties for this species estimated expressly for use in this study.
Properties for remaining species obtained from various sources.
232
APPENDIX 5
Table A-3: Reactions for Fuel Lean CH3C1 Oxidation
REACTION$
H + CL + M - HCL + M
H + CL2 - HCL + CL
CL + H2 - HCL + H
CL + CO - COCL
CL + CL + M - CL2 + M
CL + HCO - HCL + CO
CLO + H2 - HOCL + H
CLO + CO - C02 + CL
COCL + CL - COCL2
COCL + CL = CO + CL2
COCL + H - CO + HCL
COCL + H - HCO + CL
COCL + 02 - C02 + CLO
COCL + 0 - C02 + CL
0 + HCL - OH + CL
0 + CL2 - CLO + CL
0 + CLO - CL + 02
OH + HCL - H20 + CL
CH3CL + OH - CH2CL + H20
CH3CL + 0 - OH + CH2CL
CH3CL + H - H2 + CH2CL
CH3CL + 02 - H02 + CH2CL
CH3CL + H02 - H202 + CH2CL
CH3CL + CLO - HOCL + CH2CL
CH3CL + CL - HCL + CH2CL
CH3CL + CH3 - CH4 + CH2CL
CH3CL + H - HCL + CH3
CH3CL - CH3 + CL
CH3CL - CH2 + HCL
CH3CL - CH2CL + H
CH2CL + 02 - CLO + CH20
CH2CL + H - CH3 + CL
CH2CL + H02 - CH2CLO. + OH
CH2CL + OH - CH20 + HCL
CH2CL + OH - CH20H + CL
CH2CL + CH3 - C2H5CL
CH2CL + CH3 - C2H4 + HCL
CH2CL + CH3 - C2H5 + CL
CH2CL + 0 - CH2CLO.
CH2CL + 0 - CH20 + CL
CH2CLO. - CH20 + CL
CH20 + CL - HCO + HCL
CH20 + CLO - HOCL + HCO
CH3 + CLO - CH30 + CL
CH3 + CLO - HCL + CH20
CH4 + CLO - CH3 + HOCL
CH4 + CL - HCL + CH3
C2H4 + CLO - CH2CL + CH20
SOURCE@
A
(B8)
(B9)
(B10)
(Bl)
(B12)
(B13)
(B14)
(B15)
(B16)
(B17)
(B18)
(B19)
(B20)
(B21)
(B22)
(B23)
(B24)
(B25)
(B26)
(B27)
(B28)
(B29)
(B30)
(B31)
(B32)
(B33)
(B34)
(B35)
(B36)
(B37)
(B38)
(B39)
(B40)
(B41)
(B42)
(B43)
(B44)
(B45)
(B46)
(B47)
(B48)
(B49)
(B50)
(B51)
(B52)
(B53)
(B54)
(B55)
1.OOE+17
7.94E+13
4.80E+13
1.95E+19
5.75E+14
1.41E+14
1.OOE+13
6.02E+ll
3.40E+28
1.49E+19
3.54E+16
3.42E+09
7.94E+10
1.OOE+13
5.25E+12
1.26E+13
5.75E+13
2.20E+12
1.32E+12
1.70E+13
6.66E+13
4.OOE+13
1.OOE+13
5.OOE+12
5.OOE+13
3.31E+11
5.40E+13
5.53E+31
1.82E+25
1.31E+30
8.46E+13
1.68E+16
5.19E+14
4.10E+21
9.24E+11
8.47E+34
4.80E+24
2.04E+19
2.55E+15
8.31E+13
2.51E+24
5.OOE+13
1.20E+13
2.28E+07
5.50E+14
1.40E+13
2.57E+13
9.26E+18
233
n
0.0
0.0
0.0
-3.01
0.0
-0.35
0.0
0.0
-5.61
-2.17
-0.79
1.15
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
0.0
0.0
-5.63
-4.69
-5.23
-1.03
-0.68
-0.51
-2.57
0.38
-6.75
-3.44
-1.81
-2.02
-0.18
-4.78
0.0
0.0
1.54
-0.51
0.0
0.0
-1.98
E
0.
1200.
5000.
8070.
-1600.
510.
13500.
7400.
3390.
1470.
1060.
-180.
3300.
0.0
6400.
2800.
400.
1000.
2300.
7300.
10600.
52200.
16700.
8700.
1700.
9400.
6500.
88810.
132460.
106100.
8180.
1020.
840.
3740.
2970.
8080.
7690.
10340.
1230.
800.
10070.
500.
2000.
-820.
710.
15000.
3850.
8430.
TABLE A-3 continued
C2H4 + CLO - C2H40CL
C2H4 + CL - HCL + C2H3
H02 + CL - HCL + 02
H02 + CL - CLO + OH
H202 + CL - HCL + H02
H202 + CLO - HOCL + H02
(B56)
(B57)
(B58)
(B59)
(B60)
(B61)
1.75E+32
3.OOE+13
1.58E+13
3.35E+14
1.02E+12
5.OOE+12
-6.32
0.0
0.0
-0.32
0.0
0.0
7900.
5100.
0.
1470.
800.
2000.
$
Rate constants are in the form A * Tn * exp(-E/RT) for forward direction.
All reactions are considered reversible. Units are in moles, cc, sec, K,
cal.
@
Reactions M# are from Miller and Bowman,
developed as original work in this project.
234
1988.
Reactions
B#
were
APPENDIX 5
Table A-4: Thermodynamic Properties for Chlorine Containing Species
SPECIES
CL
HCL
CL2
CLO
CL20
OCLO
HOCL
COCL2
CHCLO
CH2CL
CH3CL
C2H5CL
*CH2CLOH
*CH2CLO.
*CH2CLOOH
*CH2CLOO.
*C.H200CL
CLOO.
*CH300CL
*CH30CL
*C2H50CL
*C2H40CL
COCL
*HOOCL
*CLC2H40H
*CLC2H40.
HF(298)
S(298)
CP300
CP500
CP600
CP800
CP1000
CP1500
28.90
-22.06
.00
24.20
21.00
25.00
-17.80
-52.60
-39.30
29.10
-19.59
-26.83
-52.40
-.50
-32.40
3.50
11.90
23.00
-30.00
-31.00
-39.20
8.30
-4.00
-12.90
-61.91
-10.00
39.50
44.64
53.30
54.10
64.00
61.50
56.50
67.80
61.80
59.60
56.01
66.03
66.91
64.31
75.11
73.11
81.61
63.01
77.11
68.91
79.11
81.41
63.51
65.11
77.41
74.81
5.20
6.96
8.10
7.50
11.41
9.99
8.91
13.81
11.12
9.32
9.77
15.06
12.98
11.60
17.76
16.21
16.56
11.92
17.82
12.86
17.87
17.10
10.81
13.46
17.89
16.54
5.40
6.99
8.59
8.21
12.76
11.72
10.08
16.26
13.55
11.14
13.20
21.67
16.93
14.82
22.91
20.09
20.05
13.04
22.97
17.68
26.06
24.49
11.68
15.75
25.20
23.10
5.41
7.07
8.74
8.43
13.12
12.27
10.50
17.03
14.42
12.14
14.63
24.28
18.55
16.17
24.84
21.69
21.50
13.34
24.89
19.70
29.04
27.00
12.00
16.53
28.00
25.63
5.35
7.29
8.91
8.69
13.46
12.97
11.13
17.97
15.70
14.10
17.02
28.43
21.19
18.43
27.75
24.28
23.84
13.61
27.77
22.97
33.46
30.47
12.51
17.58
32.32
29.56
5.30
7.56
8.99
8.81
13.55
13.32
11.58
18.45
16.58
15.83
18.87
31.47
23.16
20.14
29.75
26.11
25.52
13.68
29.79
25.27
36.50
32.71
12.90
18.21
35.41
32.39
5.20
8.10
9.10
9.00
13.81
13.80
12.40
19.21
18.11
18.31
21.80
36.27
26.16
22.66
32.56
28.38
27.74
13.81
32.83
27.98
41.09
36.24
13.64
19.03
40.20
36.73
All species are taken in their standard states (gas) at one atmosphere.
Temperatures are in Kelvins.
*
Properties for this species estimated expressly for use in this study.
Properties-for remaining species obtained from various sources.
235
APPENDIX 5
Table A-5: Sources and Notes on Non-ORRK Reactions in CH3C1 Mechanism
CH3C1 + OH -
.CH2C1
+ HC1
SOURCE: Kerr, Vol.1, p. 385.
CH3C1 + 0 - OH + .CH2Cl
SOURCE: Kerr, Vol.1, p. 69.
CH3Cl + H - H2 + .CH2C1
SOURCE: Ar-1.6E12,Er-14.
(NJIT group);
Af,Ea(for) from thermo
and Ar,Ea(rev)
CH3Cl + H - HCl + CH3
SOURCE: NJIT group
CH3C1 + Cl - HCl + .CH2Cl
SOURCE: NJIT group
CH3C1 + CH3 - CH4 + .CH2C1
SOURCE: Kerr, Vol.1, p. 1 9 4
CH3Cl + 02 - H02 + .CH2Cl
SOURCE: Af=0.5*Af for CH4+02
Ea-/\Hr
CH3C1 + H02 - H202 + .CH2Cl
SOURCE: Af-0.5*Af for CH4+HO2
Ea-/\Hr+4
M - HCl + M
H + Cl +
SOURCE: Ritter et.al. (1989)
Cl + H2 - HCl + H
SOURCE: Kerr, Vol._, p.
C12 + H - HC1 + Cl
SOURCE: Kerr, Vol._, p.
Cl + C1 + M - C12 + M
SOURCE: Kerr, Vol.2, p. 2 3
0 + HC1
SOURCE: Kerr, Vol.1, p. 6 9
C10 + CO
OH + Cl
-
C02 + C1
SOURCE: DeMore et.al., 1985
C1 + H02 - HCl + 02
SOURCE: Kerr, Vol.2, p.55
CH3Cl + C10 - HOCi + .CH2C1
CH20 + C1 - HCl + HCO
SOURCE: Af appr. 4*Af for
CH3C1+OH; Ea-/\Hr+2
(NJIT group)
SOURCE: NJIT group
C2H4 + Cl - HC1 + C2H3
SOURCE: Sawersyn et.al.,1987
C10 + H2 - HOCi + H
SOURCE: Chang and Senkan, 1989
CH4 + C10 - HOCi + CH3
SOURCE: Af-0.5*Af for CH4+OH;
Ea-/\Hr+4 (NJIT group)
CH4 + C1 - HCi + CH3
SOURCE: NJIT group
236
TABLE A-5 continued
Cl + H202
HC1 + H02
-
C10 + H202
-
SOURCE: Kerr, Vol.1, p. 1 15
H02 + HOC1
SOURCE: Af-0.5*Af for OH+H202
Ea appr. Ea for
OH+H202
C10 + CH20 - HOCL + HCO
SOURCE: Af appr.0.3*Af for
OH+CH20; Ea appr.
Ea for OH+CH20
OH + HC1 - H20 + Cl
SOURCE: Baulch et.al., 1981
0 + C10 - Cl + 02
SOURCE: Baulch et.al., 1981
0 + C12 - Clo + Cl
SOURCE: Baulch et.al., 1981
COCi + 0 - C02 + Cl
SOURCE: Estimate (this work)
COCi + 02
SOURCE: DeMore et.al., 1985
=
C02 + Clo
237
REFERENCES FOR CH3Cl MECHANISM DEVELOPMENT
Allara, D.L. and Shaw, R., Journal of Physical Chemistry Reference
Data, Vol. 9, No. 3, p. 523 (1980).
Baulch,
D.L., Duxbury, J.,
Grant, S.J.,
and Montague, D.C.,
Journal of Physical Chemistry Reference Data, Vol. 10, Suppl. No.
1 (1981).
Bozzelli, J.W., and Dean, A.M., Second International Conference on
Chemical Kinetics, Gaithersburg, MD (1989).
and Senkan, S.M., Environmental Science and TechnolChang, W.D.
ogy, Vol. 23, No. 4, p. 442 (1989).
Dean, A.M.,
(1985).
Journal of Physical
Chemistry,
Vol.
Dean, A.M. and Westmoreland, P.R., International
Chemical Kinetics, Vol. 19, p. 207 (1987).
89,
p.
Journal
4600
of
DeMore, W.B., Molina, M.J., Watson, R.T., Golden, D.M., Hampson,
C.J., Ravishankara, A.R., Chemical
Kurylo, M.J., Howard,
R.F.,
Kinetics and Photochemical Data for Use in Stratospheric Modeling;
Evaluation No. 6, JPL Publication 85-37 (1985).
Kerr, J.A. and Moss, S.J., eds., Handbook of Bimolecular and
Termolecular Reactions, Vols. I and II, CRC Press, Boca Raton, FL
(1981).
Reid, R.C., Prausnitz, J.M., and Sherwood, T.K., The Properties of
Gases and Liquids, 3rd. ed., McGraw-Hill, New York (1977).
Sawersyn, J.P., Lafage,
Phsique, Vol. 84 (1987).
C.,
and Tighezza,
Setser, D.W. and Lee, T., Journal
Society, Vol. 89, p. 5799 (1985).
238
of the
B.A.,
J. de Chimie
American
Chemical
APPENDIX 6 --
COMPUTER PROGRAMS
+ Program B12:
PFR(JM)/PSR Hybrid Model (Micro-Vax)
+ Program PQBBB:
Probe Quench Calculation (Micro-Vax)
+ Program NS3DBLS: Data Collection /
Storage (White Elephant)
+ Program NS3TBLS: Data Collection / Testing (White Elephant)
+ Program GLOBAL:
Data Analysis / PDF Generation, Deconvolution
(White Elephant)
+ Program AFTTOX:
Temperature vs. Cross Section for C2H4/CH3C1
(White Elephant)
+ Program AFTC2H4: Temperature vs. Cross Section for C2H4
(White Elephant)
+ Program AFTCOH2: Temperature vs. Cross Section for CO/H2
(White Elephant)
239
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WRITE(LFINAL,1514)
WRITE (LFINAL,1519)
WRITE(LFINAL,4543) PA,TFEED
WRITE(LFINAL,7020)
DO IJ-1,KK
WRITE(LFINAL,2203) (KSYM(I,IJ),I-1,LENSYM) ,XFEED(IJ)
END DO
WRITE(LFINAL,1517)
WRITE(LFINAL,1378) DELT,TPFR1
WRITE(LFINAL,1518) VPSR1
WRITE(LFINAL,9752) FDRATEI,WTT1
WRITE(LFINAL,9770) PSRTEMP
WRITE(LFINAL,9800) FMM,SSPLIT
write(lfinal,9100) pfrtol,psrtol
write(lfinal,962) ifirst
C
WRITE(LFINAL,1520)
WRITE(LFINAL,1521)TP
DO IJ-1,KK
WRITE(LFINAL,2203) (KSYM(I,IJ),I-1,LENSYM),XP(IJ)
END DO
WRITE(LFINAL,1517)
C
CALL CKRHOY (P,TFEED,YMOLIC,IWORK,WORK,RHOFEED)
close(lfinal)
TSUR-TP
DO 4313 J-1,KK
YSUR(J)-YP(J)
4313 CONTINUE
C
6868 CONTINUE
C
WRITE(LFINAL,631)ICONV
T-TFEED
P-PA*PATM
Z(1)-T
DO 431 J-1,KK
Y(J)-YMOLIC(J)
Z(J+1)-Y(J)
431 CONTINUE
VPFR1-0.0
C
C
C
SET THE INTEGRATION CONTROL PARAMETERS FOR LSODE
8222 CONTINUE
NEQ-KK+1
MF-22
ITOL-1
IOPT-0
RTOL-1.E-4
ITASK-1
ATOL-1.E-15
ISTATE-1
TT1-WTT1
JCNT-0
NLINES-NLMAX+1
C
C
C
SET CONDITIONS FOR "SURROUNDINGS"
IF (IFIRST.EQ.1) GOTO 7621
243
CALL CKRHOX(P,TP,XP,IWORK,WORK,RHOP)
CALL CKRHOX(P,TBAR, SEGBAR, IWORK,WORK,RHOBAR)
SURPSR-1.0
SURPFR-FMM*1. 0*RHOBAR*VPFROLD/(VP*RHOP)
CALL MIX(KK,IWORK,WORK,SURPSR,SURPFR,XP,SEGBAR,
1
TP,TBAR,YP,YSEGBAR,TSUR,YSUR,SMSUR)
7621 CONTINUE
DO 550 J-1,KK
ZSUR(1+J) - YSUR(J)
550 CONTINUE
ZSUR(1)-TSUR
CALL CKRHOY (P,TSUR,YSUR,IWORK,WORK,RHOSUR)
C
C
C
INTEGRATION LOOP
250 CONTINUE
C
TT2-TT1+DELT
CALL LSODE(FUN,NEQ,Z,TT1,TT2,ITOL,RTOL,ATOL,ITASK,ISTATE,IOPT,
ELWRK,LRW,IELWRK,LIW,JAC,MF)
1
IF (ISTATE.EQ.2) GOTO 67
WRITE(LFINAL,1212) ISTATE
STOP
67 T-Z(1)
DO 400 K-1,KK
Y(K)-Z(K+l)
400 CONTINUE
JCNT-JCNT+1
CALL CKRHOY(P,T,Y,IWORK,WORK,RHOINC)
SNEWCUM-FDRATEI*587.*((RHOSUR/RHOFEED)**0.25)*(TT2**0.5)
VOLINC-DELT*SNEWCUM/RHOINC
VPFR1-VPFR1+VOLINC
write(lfinal,115)TT2,VPFR1
IF (ICONV.NE.2) GOTO 916
WRITE (LOUT,79)
WRITE (LOUT,77)TT2,T
WRITE (LOUT, 75)VOLINC,VPFR1, SNEWCUM
916 CONTINUE
CALL CKYTX(Y,IWORK,WORK,X)
write(lfinal,702)snewcum
IF (ICONV.NE.2) GOTO 407
WRITE(LOUT,80)
DO 407 L-1,KK
WRITE(LOUT,2203)(KSYM(I,L),I-1,LENSYM),X(L)
407 CONTINUE
IF(JCNT.LT.NTI) GOTO 250
DO 17 I-1,KK
SECBAR(I)-X(I)
17 CONTINUE
TBAR-T
LOOP-LOOP+1
IF (IFIRST.EQ.0) GOTO 127
SMDOTINPS-SNEWCUM
RATIO-0.0
GOTO 984
127 CONTINUE
RATIO-SURPFR/SURPSR
SMDOTINPS-(RATIO*FDRATEI+SNEWCUM)/(1+RATIO)
984 CONTINUE
write(lfinal,888) TBAR,LOOP,IFIRST
489
444
981
C
C
C
write(lfinal,672) SNEWCUM,RATIO,SMDOTINPS
CLOSE(LFINAL)
CALL CKXTY(SEGBAR, IWORK,WORK,YSEGBAR)
IF (VPFR1.LT.250.) GOTO 444
IF (IFIRST.EQ.0) GOTO 489
VPM-20.
GOTO 981
WRITE(LFINAL,555)
STOP
VPM-250.-VPFR1
CONTINUE
IF (IFIRST.EQ.1) GOTO 2525
IF (ICONV.EQ.2) GOTO 5858
READ OLD FILE TO COMPARE WIH NEW VALUES
DIFF - ABS(TBAR-TBAROLD)
IF (DIFF .GE. PFRTOL) GOTO 2552
ICONV -1
GOTO 2525
2552 CONTINUE
ICONV=O
2525 CONTINUE
TBAROLD-TBAR
CLOSE(LFINAL)
CLOSE(LOUT)
CLOSE(LPSRINP2,STATUS-'DELETE')
C
C
C
WRITE FILE FOR PSR #1 INPUT
WRITE (LPSRINP2,2225)
WRITE (LPSRINP2,2229) PA
WRITE (LPSRINP2,2231) PSRTEMP
WRITE (LPSRINP2,2226) VPM
WRITE (LPSRINP2,2227) SMDOTINPS
DO 3434 JK-1,KK
WRITE(LPSRINP2,2223) (KSYM(I,JK),I-1,LENSYM),SEGBAR(JK)
3434 CONTINUE
WRITE(LPSRINP2,2228)
CLOSE(LPSRINP2,STATUS-'KEEP')
CLOSE(LOUT)
CALL B3PSR
CLOSE(LOUT)
OPEN (LPSRBIN, STATUS-'OLD' ,FORM-'UNFORMATTED')
REWIND(LPSRBIN)
READ (LPSRBIN) DUMMY
READ (LPSRBIN) NNP
KKP-NNP-1
READ (LPSRBIN) EQUIVP, PP,TAUP,FLRTP,VP,QP
READ (LPSRBIN) TINP,(XINP(K),K-1,KKP)
READ (LPSRBIN) TP,(YP(K),K-1,KKP)
CLOSE (LPSRBIN,STATUS-'DELETE')
CLOSE (LPSRINP2,STATUS-'DELETE')
CALL CKYTX(YP,IWORK,WORK,XP)
IF (IFIRST.EQ.1) GOTO 499
DO 499 I-1,KK
IF (YP(I).LT.1.OE-10) GOTO 499
DIFF-(YPOLD(I)-YP(I))/YP(I)
IF (ABS(DIFF) .GE. PSRTOL) GOTO 2526
499 CONTINUE
245
IF (ICONV.EQ.1) ICONV-2
CLOSE(LFINAL)
CLOSE(LOUT)
2526 DO I-1,KK
YPOLD(I)-YP(I)
END DO
SMDOTOUT-FDRATEI
C
C
C
ANOTHER TRIP THROUGH THE LOOP
IFIRST-0
WRITE(LFINAL,705)TP,VP
VPFROLD-VPFR1
GOTO 6868
C
5858 CONTINUE
CLOSE(LOUT)
CLOSE(LFINAL)
C
C
C
WRITING OUTPUT FILES
WRITE (LFINAL, 628) ICONV, SMDOTOUT
WRITE (LFINAL, 2204) TBAR, SNEWCUM,VPFR1
DO 3436 JK-1,KK
WRITE(LFINAL,2203) (KSYM(I,JK) ,I-1,LENSYM) ,SEGBAR(JK)
3436 CONTINUE
WRITE(LFINAL,1984) TP,FLRTP,VP,TAUP
DO 3437 JK-1,KK
WRITE(LFINAL,2203) (KSYM(I,JK) , I-1,LENSYM) ,XP(JK)
3437 CONTINUE
C
C
C
SAMPLING FOR PROBE QUENCH
CALL CKRHOX (P,TP,XP,IWORK,WORK,RHOP)
CALL CKRHOX (P,TBAR, SEGBAR, IWORK,WORK,RHOBAR)
SMDOTSPSR - 1.0
SMDOTSPFR1 - 1.0*SSPLIT*RHOBAR*VPFR1/(VP*RHOP)
CALL MIX (KK, IWORK,WORK, SMDOTSPSR, SMDOTSPFR1,XP , SEGBAR,
1
TP , TBAR,YP ,YSEGBAR,TSAMPLE ,YSAMPLE,SMDOTSAMPLE)
CALL CKYTX (YSAMPLE, IWORK, WORK, XSAMPLE)
WRITE(LPQ,1515)PA,TSAMPLE
DO JK-1,KK
WRITE(LPQ,1516) (KSYM(I,JK) ,I-1,LENSYM) ,XSAMPLE(JK)
END DO
WRITE(LPQ,2228)
WRITE(LPQ,1513) .001, .0002
WRITE(LPQ,1517)
WRITE(LFINAL,2112)
WRITE(LFINAL,207)TSAMPLE
DO JK-1,KK
WRITE(LFINAL, 2203) (KSYM(I,JK) ,I-1,LENSYM) ,XSAMPLE(JK)
END DO
STOP
C
C
C
FORMATS
75 FORMAT(lX,'VOL.INCREM: ',F5.1,3X,'CUMUL.VPFR1:
1
2X,'CUM.MASS RATE: ',F8.2)
77 FORMAT(lX,'TIME: ',E9.3,2X,'TEMP: ',F8.1)
79 FORMAT(lX,'TIME-TEMP PROFILE IN PFR1')
',F5.1,
80 FORMAT(lX,'MOLE FRACTIONS IN PFR1')
FORMAT(lX,'FEED MOLE FRACTIONS SUM:',E12.6)
FORMAT(lX,'TT2:',E1O.3,5X,'VPFR1:',F5.1)
FORMAT(lX,'PSR#2 RES. TIME:',E10.3,5X,'VOL:',F5.1)
FORMAT(lX,'EQUIVALENCE RATIO: ',F6.2)
FORMAT(lX,'SAMPLE TEMPERATURE: ',F8.1)
FORMAT(lX'VTS IMPOSSIBLY LARGE..CHECK TPFR AND FEEDRATES')
FORMAT(lX, 'ICOUNTER: 'I3)
FORMAT(2X,'ICONV: ',13,2X,'MASS RATE OUT OF MODEL: ',F8.2)
FORMAT(2X,'ICONV: ',13)
FORMAT(lX,'SNEWCUM: ',F8.2,2X,'RATIO: ',F8.5,2X,'SMDOTINPS: ',
1
F8.2)
701 FORMAT(lX,'PSR#2 TEMP: ',F7.1,2X,'VOL: ',F5.1,
1
2X,'MASS RATE: ',F8.2,2X,'RES.TIME: ',E9.3)
702 FORMAT(lx,'SNEWCUM:',f8.3)
705 FORMAT(2X,'PSR TEMP: ',F7.1,2X,'PSR VOL: ',F7.1)
787 FORMAT(lX,'MASS BALANCE IS NOT CLOSED')
888 FORMAT(lx,'PFR OUT Temp:',F8.1,5X,'LOOP #:-',13,5X,'IFIRST:',i3)
962 FORMAT(lx,'ifirst: ',i3)
1212 FORMAT('ISTATE-',I4)
1378 FORMAT(lX,'DELT:',E1O.2,5X,'TPFR1:',E1O.2)
1513 FORMAT(lX,Ell.3,2X,Ell.3)
1514 FORMAT(lX,'ENTERING LOOP WITH THIS STARTING GUESS')
1515 FORMAT(lX,F3.1,3X,F7.1)
1516 FORMAT(lX,10A1,1X,Ell.4)
1517 FORMAT(lX,'END')
1518 FORMAT(lX,'VPSR: ',F7.1)
1519 FORMAT(lX,'FEED CONDITIONS')
1520 FORMAT(lX,'SURROUNDING FLUID')
1521 FORMAT(lX,'TEMP: ',F7.1)
1801 FORMAT(lX,'CUMULATIVE MASS RATE g/s - ',F8.2)
1984 FORMAT(lX,'PSR#1 TEMP: ',F8.1,2X,'MASS RATE: ',F8.2,
1
2X,'VOL: ',F5.1,2X,'RES.TIME: ',E9.3)
2112 FORMAT(1X,'SAMPLE')
2203 FORMAT(lX,1OA1,1X,Ell.4)
2204 FORMAT(1X,'PFR1 OUT TEMP: ',F7.1,2X,'MASS RATE OUT: ',F8.2,
1
2X,'PFR1 VOL: ',F5.1)
2222 FORMAT(A)
2223 FORMAT('REAC' ,1X,10A1,1X,Ell.4)
2225 FORMAT('TGIV')
2226 FORMAT('VOL ',1X,Ell.4)
2227 FORMAT('FLRT',1X,Ell.4)
2228 FORMAT('END')
2229 FORMAT('PRES',1X,Ell.4)
2231 FORMAT('TEMP' ,1X,Ell.4)
4543 FORMAT(lX,'PRES (atm):',F5.1,5X,'TFEED (K):',F7.1)
7003 FORMAT(lH1)
7?10 FORMAT(//,2X, 'FIXED PRESSURE PROBLEM' ,//)
7020 FORMAT(2X,'INPUT MOLE FRACTIONS')
7100 FORMAT(3X,6HT(SEC),6X,6HTMP(K),6X,5(lX,lOA1))
7105 FORMAT(12E11.3)
7110 FORMAT(27X,5(lX,1OA1))
7115 FORMAT(22X,1OE11.3)
7500 FORMAT(10A1,E10.0)
7600 FORMAT(80A1)
7610 FORMAT(4X,80A1)
7620 FORMAT(2X,'INPUT PRESSURE(ATM) AND TEMPERATURE(K)')
7700 FORMAT(10X,50HINITIAL MASS FRACTION GIVEN FOR AN UNKNOWN SPECIES)
8400 FORMAT(lX,'ERROR IN XNUM')
8731 FORMAT(lX,'VPSR2:',F6.1)
111
115
159
186
207
555
581
628
631
672
247
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0016
01706
0Z06
0106
0006
HTOL-0.
DO I-1,KK
YTOL(I)-0.
END DO
C
C
C
CALCULATE TOTAL ENTHALPY AND MASS FRACTIONS
DO 100 I-1,KK
HTOL-HTOL+Yl(I)*HMS1(I)*SMDOT1+Y2(I)*HMS2(I)*SMDOT2
YTOL(I)-(Yl(I)*SMDOT+Y2(I)*SMDOT2)/(SMDOT1+SMDOT2)
100 CONTINUE
C
C
C
CALCULATE FIRST GUESS FOR MIX TEMPERATURE
110
120
90
130
TI-SMDOT1/(SMDOT1+SMDOT2)*Tl+SMDOT2/(SMDOT1+SMDOT2)*T2
DO 120 IJ-1,1000
HTOLG-0.
CALL CKHMS(TI,IWORK,WORK,HMLTOL)
DO 110 I-1,KK
HTOLG-HTOLG+HMLTOL(I)*YTOL(I)*SMDOTTOL
CONTINUE
DIFF-(HTOL-HTOLG)/HTOL
IF (ABS(DIFF).LE.O.05) GOTO 130
TI-(1.+.005*DIFF)*TI
CONTINUE
WRITE(LFINAL, 90)
FORMAT(lX,'TEMPERATURE NOT CONVERGED IN MIX')
STOP
CONTINUE
RETURN
END
C
C
-
SUBROUTINE B3PSR
IMPLICIT REAL*8 (A-H,O-Z)
PARAMETER (LENLWK-150, LENIWK-7000, LENRWK-9000)
DIMENS ION LWORK(LENLWK), IWORK(LENIWK), RWORK (LENRWK)
DATA LIN/10/, LOUT/6/, LRSTRT/14/, LSAVE/15/, LRECOV/16/,
1
LINKCK/25/
OPEN(UNIT-LIN, STATUS-'OLD', FORM-'FORMATTED')
OPEN(UNIT-LOUT, STATUS-'NEW', FORM-' FORMATTED',
1
DISPOSE-'DELETE')
OPEN(UNIT-LRSTRT, STATUS-'OLD', FORM-'UNFORMATTED',READONLY)
OPEN(UNIT=LSAVE, STATUS-'NEW', FORM-'UNFORMATTED')
OPEN(UNIT-LRECOV, STATUS-'NEW', FORM-'UNFORMATTED')
OPEN(UNIT-LINKCK, STATUS-'OLD', FORM-'UNFORMATTED', READONLY)
CALL PSR (LIN, LOUT, LINKCK, LRSTRT, LSAVE, LRECOV, LENLWK, LWORK,
1
LENIWK, IWORK, LENRWK, RWORK)
RETURN
END
249
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C
READ INITIAL MOLE FRACTION
251
C
C
C
C
C
40 CONTINUE
WRITE(LOUT,7020)
READ(LIN,7600,END-45) (ICHAR(N) ,N-1,NCHAR)
WRITE(LOUT,7610) (ICHAR(N) ,N-1,NCHAR)
IF(ICHAR(l).EQ.lHE .AND. ICHAR(2).EQ.lHN .AND.
1
ICHAR(3).EQ.lHD)GO TO 45
CALL SYMNUM(KK,LENSYM,NCHAR,1,KSYM,ICHAR,ISYM,KSPEC,VALUE)
X(KSPEC)-VALUE(1)
GO TO 40
45 CONTINUE
NORMALIZE THE MOLE FRACTIONS
XTOT-O.OEO
DO 50 K-1,KK
XTOT-XTOT+X(K)
50 CONTINUE
DO 55 K-1,KK
X(K)-X(K)/XTOT
55 CONTINUE
C
C
C
SET UP INITIAL CONDITIONS
CALL CKXTY (X, IWORK, WORK, Y)
DO 60 K-1,KK
Z(K)-Y(K)
60 CONTINUE
C
C
C
SET INITIAL TIME,FINAL TIME, AND PRINT INTERVAL
WRITE(LOUT, 9000)
READ(LIN,7600) (ICHAR(N),N-1,NCHAR)
WRITE(LOUT,7610) (ICHAR(N) ,N-1,NCHAR)
C
CALL XNUM (ICHAR, NCHAR, 2, VALUE, IERR)
IF(IERR .EQ. 0) GO TO 100
WRITE(LOUT,8400)
100 CONTINUE
T2-VALUE(1)
DT - VALUE(2)
T1-0.
C
C
C
SET THE INTEGRATION CONTROL PARAMETERS FOR LSODE
NEQ-KK
MF-22
ITOL-1
IOPT-0
RTOL-l.E-4
ITASK-1
ATOL-1.E-15
ISTATE-1
TT1-Tl
NLINES-NLMAX+1
C
C
C
INTEGRATION LOOP
250 IF(NLINES.LT.NLMAX)GO TO 270
C
PRINT PAGE HEADING
C
NLINES-0
WRITE(LOUT,7003)
DO 200 Kl-1,KK,NK
K2-Kl+NK-1
IF(K2.GT.KK)K2-KK
IF(Kl.GT.1)GO TO 180
WRITE(LOUT,7100) ((KSYM(L,K) ,L-1,LENSYM),K-Kl,K2)
NLINES-NLINES+1
GO TO 200
180 CONTINUE
WRITE(LOUT,7110) ((KSYM(L,K),L-1,LENSYM),K-Kl,K2)
NLINES-NLINES+1
200 CONTINUE
C
C
C
PRINT THE SOLUTION
270 DO 300 Kl-1,KK,NK
K2-Kl+NK-1
IF(K2.GT.KK)K2-KK
IF(Kl.GT.1)GO TO 280
WRITE(LOUT,7105)TT1,T,(X(K),K-K1,K2)
NLINES-NLINES+1
GO TO 300
280 CONTINUE
WRITE(LOUT,7115)(X(K),K-Kl,K2)
NLINES-NLINES+1
300 CONTINUE
C
C
C
IMPOSED TEMPERATURE PROFILE
TT2-TT1+DT
TCOOL-315.
BM-55.
CM-(TIN-TCOOL)/TCOOL
TOLD-TCOOL*(1.+CM*EXP(-BM*TT1**0.5))
TNEW-TCOOL*(1.+CM*EXP(-BM*TT2**0.5))
T-0.5*(TOLD+TNEW)
IF (T.LT.373.) T-373.
C
C
C
CALL THE DIFFERENTIAL EQUATION SOLVER
IF (TT2.GT.T2) GOTO 9999
CALL LSODE(FUN,NEQ,Z,TT1,TT2,ITOL,RTOL,ATOL,ITASK,ISTATE,IOPT,
1
ELWRK,LRW,IELWRK,LIW,JAC,MF)
IF (ISTATE.EQ.2) GOTO 350
WRITE (6,1234)ISTATE,TT1
STOP
C
C
C
CONVERT INTERNAL PARAMETERS MOLE FRACTION
350 CONTINUE
DO 400 K - 1, KK
Y(K) - Z(K)
400 CONTINUE
CALL CKYTX (Y, IWORK, WORK, X)
C
IF(TT1.LE.T2) GOTO 250
C
9999 STOP
C
C
C
FORMATS
1234
7003
7100
7105
7110
7115
7500
7700
7620
7010
7020
7600
7610
8400
9000
FORMAT(1X,'ISTATE: ',13,1X,'TT1: ',E15.5)
FORMAT(lH1)
FORMAT(3X,6HT(SEC),6X,6HTMP(K),6X,5(lX,10A1))
FORMAT(E1O.2,3X,F6.1,3X,10E11.3)
FORMAT(27X,5(lX,1OA1))
FORMAT(22X,1OE11.3)
FORMAT(10A1,E10.0)
FORMAT(10X,50HINITIAL MASS FRACTION GIVEN FOR AN UNKNOWN SPECIES)
FORMAT(2X,'INPUT PRESSURE(ATM) AND TEMPERATURE(K)')
FORMAT(////,2X, 'FIXED PRESSURE PROBLEM' ,//)
FORMAT(2X,'INPUT MOLES OF NEXT SPECIES')
FORMAT(80A1)
FORMAT(4X,80A1)
FORMAT(' ERROR IN XNUM')
FORMAT(2X,'INPUT FINAL TIME AND DT')
END
C
SUBROUTINE FUN(N,TIME, Z , ZP)
IMPLICIT REAL*8(A-H,O-Z)
DIMENSION Z(N), ZP(N), Y(75), WDOT(75)
COMMON /WRK /IWORK(6000), WORK(5000)
COMMON /PARAM /KK , P, T
COMMON /DUM /WT(75)
C
C
C
C
C
C
VARIABLES IN Z ARE
Z(K)-Y(K)
CALL CHEMKIN SUBROUTINES
CALL CKRHOY (P, T, Z, IWORK, WORK, RHO)
CALL CKWYP (P, T, Z, IWORK, WORK, WDOT)
C
C
C
FORM GOVERNING EQUATION
DO 110 I-1,KK
ZP(I) - WDOT(I)*WT(I)/RHO
110 CONTINUE
RETURN
END
253
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1440
1450 SUMLAS-0
1452 FOR K-1 TO RES
1454 SUMLAS-SUMLAS+LAS(K)
1456 NEXT K
1458 AVLAS-SUMLAS/RES
1520 LASSR-1000*AVIAS*LSEN/32768
1522
1550 INPUT "CORRECT FOR LASER FLUCTUATIONS (Y/N)?";CLF$
1552 IF CLF$-"Y" GOTO 1570
1554 FOR I-1 TO RES \ RAY(I)-RAYT(I) \ NEXT I
1556 GOTO 1600
1560
1570 FOR I-1 TO RES
1575 FLUC-LAS(I)/AVLAS \ RAY(I)-RAYT(I)/FLUC
1580 NEXT I
1590
1600 GOSUB 6100 \ PRINT "RAYL SIGNAL DATA"
1605 INPUT "WANT INTERACTIVE DATA REVIEW (Y/N)?";IDR$
1610 IF IDR$-"N" GOTO 1620
1615 GOSUB 6500 \ GOTO 1600
1620 PRINT "# OF DATA POINTS USED - ",RES
1630
1640 SUMRAY-0
1645 FOR I-1 TO RES \ SUMRAY-SUMRAY+RAY(I) \ NEXT I
1650 AVRAY-SUMRAY/RES \ RAYMV-AVRAY*1000*RSEN/32768
1660
1670 PRINT "AVER LAS MON SIGNAL (mV) - ",LASSR
1672 PRINT "AVER RAYL (#3-#4) SIGNAL (mV) - ",RAYMV
1680
1700 INPUT "WANT PDF (Y/N)?";PDF$
1705 IF PDF$-"N" GOTO 8000
1710 GOTO 6700
1900
2000 REM******SET INDIVIDUAL CHANNEL ZEROS**************
2005
2010 FOR I-1 TO (RSP-30) \ A(I)-A(I+30) \ NEXT I
2012 RSP-RSP-30 \ RES-RSP/3
2015 SMLAS-0 \ SMRA-0 \ SMRB-0
2020
2022 FOR J-1 TO RES
2024 LAS-A(3*J-2) \ RAYA-A(3*J-1) \ RAYB-A(3*J)
2026 SMLAS-SMLAS+LAS \ SMRA-SMRA+RAYA \ SMRB-SMRB+RAYB
2028 NEXT J
2030
2040 AVRA-SMRA/RES*1000*RSEN/32768
2042 AVLAS-SMLAS/RES*1000*LSEN/32768
2044 AVRB-SMRB/RES*1000*RSEN/32768
2050 PRINT "AVER CHAN #2 SIGNAL (mV) - ",AVLAS
2052 PRINT "AVER CHAN #3 SIGNAL (mV) - ",AVRA
2054 PRINT "AVER CHAN #4 SIGNAL (mV) - ",AVRB
2060
2070 GOTO 1096
2100
2500 REM**CHECK IF COMMAND DONE BY CHECKING VALUE OF BIT 0**
2520 REM**DO THIS BY CHECKING IF FPK%(8) IS ODD OR EVEN*****
2530 REM*****************TAKE SERIAL POLL*******************
2540 GOSUB 6000
2550 IF FPK%(8)-2*INT(FPK%(8)/2) GOTO 2540
2560 RETURN
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\ PRINT#1,"SAMPLE MEAN (mV),MEAN
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REM****************PROGRAM DISPOSITION****************************
INPUT "REDO ANALYSIS OF CURRENT DATA (Y/N)?";RAC$
IF RAC$-"Y" GOTO 1550
INPUT "RUN AGAIN (Y/N)?";X$
IF X$-"N" GOTO 8030
CLS \ GOTO 600
CLOSE #1 \ CLOSE #2 \ CLOSE #3 \ END
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610 INPUT "RUN (Y/N)?";A$ \ IF A$-"Y" GOTO 970
620 INPUT "SET(S) OR CHECK(K) BOXCAR PARAMETERS?";B$
630 IF B$-"S" GOTO 660
640 IF B$-"K" GOTO 750
650
660 REM***************SET PARAMETERS********************
670
680 INPUT "SET PARAMETERS?";D$ \ IF D$-"N" GOTO 720
690 PRINT "PARAMETER IS:
700 INPUT LINE C$ \ GOSUB 3000
710 GOTO 680
720 INPUT "CHECK STATUS(K) OR START(T)?";E$
730 IF E$-"K" GOTO 750
735 IF E$-"T" GOTO 970
740
750 REM**************CHECK PARAMETERS*******************
770
800 PRINT "STATUS OF:
810 INPUT LINE C$ \ GOSUB 3000
820 INPUT "CHECK OTHER PARAMETERS (Y/N)?";G$
825 IF G$-"Y" THEN GOTO 800 ELSE GOTO 950
950 INPUT "SET PARAMETERS(S) OR START(T)?";H$
960 IF H$-"S" GOTO 660
964 IF H$-"T" GOTO 970
967
970 REM*************PREPARING TO START EXPERIMENT************
973
980 CLS
1010 INPUT "SET ZERO ON EACH BOXCAR CHANNEL (Y/N)?";SBZ$
1012 IF SBZ$-"Y" GOTO 1030
1014 INPUT "NON-LASER BACKGROUND OR #3-#4 ZERO (Y/N)?";NL$
1016 IF NL$-"Y" COTO 1040
1018 INPUT "MEASURING RAYL SIGNALS (Y/N)?";LS$
1020 IF LS$-"Y" THEN GOTO 1050 ELSE GOTO 1096
1025
1030 FLAG-1
1032 GOSUB 2500 \ PRINT#2,"BS 1" \ WAIT 1 \ GOSUB 3500
1033 PRINT "BASELINE SUBTRACTION DISABLED"
1035 GOSUB 2500 \ PRINT#2,"CL 32" \ WAIT 1 \ GOSUB 3500
1036 GOTO 1072
1038
1040 FLAG-2
1042 GOSUB 2500 \ PRINT#2,"BS 4" \ WAIT 1 \ GOSUB 3500
1043 PRINT "BASELINE SUBTRACTION ACTIVE -- > CHAN #3 - #4"
1045 GOTO 1070
1047
1050 FLAG-3
1052 GOSUB 2500 \ PRINT#2,"BS 4" \ WAIT 1 \ GOSUB 3500
1053 PRINT "BASELINE SUBTRACTION ACTIVE -- > CHAN #3 - #4"
1055 GOTO 1070
1057
1070 PRINT "NOM CURVE LENGTH (CL - ) (MAX-4096):
1071 INPUT LINE C$ \ GOSUB 3000
1072 INPUT "RAYL CHANNELS #3 & #4 SENS (VOLTS) ";RSEN
1074 INPUT "LASER CHANNEL SENSITIVITY (VOLTS) ";LSEN
1090
1096 INPUT "QUIT(Y/N) OR RESTART(ST)?";J$
1098 IF J$-"Y" GOTO 7900
1100 IF J$-"ST" GOTO 600
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SUMLAS-0
FOR K-1 TO RES \ SUMLAS-SUMLAS+LAS(K) \ NEXT K
AVLAS-SUMLAS/RES \ LREF-AVLAS
CNT-0
INPUT "RAYL SIGNALS + (P) OR - (N) ? ";RSS$
IF RSS$-"P" THEN XYX-1 ELSE XYX--l
FOR I-1 TO RES
FLUC-LAS(I)/AVLAS \ RSIG-VOLT(I)/FLUC*XYX
IF RSIG <- 0 GOTO 900
CNT-CNT+l \ VOLT(CNT)-RSIG
NEXT I
RES-CNT \ PRINT#1,CHR$(10)
PRINT "# OF DATA PTS BEFORE REVIEW - ",RES
PRINT#1,"# OF DATA PTS BEFORE REVIEW - ",RES
GOSUB 5500 \ PRINT "REFER RAYL SIGNAL DATA"
INPUT "WANT INTERACTIVE DATA REVIEW (Y/N)?";IDR$
IF IDR$-"N" GOTO 1000
GOSUB 5100 \ GOTO 980
PRINT "# OF DATA POINTS USED - ",RES
PRINT#1,CHR$(10) \ PRINT#1,"# OF DATA PTS USED - ",RES
SMREF-0
FOR J-1 TO RES \ SMREF-SMREF+VOLT(J) \ NEXT J
REFER-SMREF/RES \ PRINT#1,CHR$(10)
PRINT "AVER RAYL REFER SIGNAL - ",REFER
PRINT#1, "AVER RAYL REFER SIGNAL - ",REFER
LASSR-1000*AVLAS*LSEN/32768 \ PRINT#1,CHR$(10)
PRINT "AVER LAS MON SIGNAL (mV) - ",LASSR
PRINT#1,"AVER LAS MON SIGNAL (mV) - ",LASSR
REFERR-1000*REFER*RSEN/32768 \ PRINT#1,CHR$(10)
PRINT "AVER RAYL REFER SIGNAL (mV) - ",REFERR
PRINT#1, "AVER RAYL REFER SIGNAL (mV) - ",REFERR
INPUT "REFER. RAYL. CROSS SECTION: ";RRCS
GOTO 350
REM****RECALL RAYL SIGNAL DATA FROM DISKETTE*******
REM***CORRECTION FOR LASER INTENSITY FLUCTUATION***
REM********INTERACTIVE DATA EXAMINATION************
REM*******CALCULATE AVERAGE RAYL SIGNAL************
REM********GENERATE RAYLEIGH SIGNAL PDF************
INPUT "DATA FILE TO BE READ (#:****.DAT): ";ODF$
PRINT#1,CHR$(10) \ PRINT#1,"RAYL COMB DATA FILE: ",ODF$
OPEN ODF$ AS FILE #5
FOR I-1 TO RSP
INPUT #5, DAT
IF 2*INT(I/2)-I THEN RAY(I/2)-DAT ELSE LAS((I+1)/2)-DAT
NEXT I
CLOSE #5
FOR I-1 TO RES \ LAS(I)-LAS(I)-NLLBCK
SUMLAS-0
FOR K-1 TO RES \ SUMLAS-SUMLAS+LAS(K)
AVLAS-SUMLAS/RES
\ NEXT I
\ NEXT K
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1476 PRINT#1,CHR$(10) \ PRINT#1,"STD DEV (K): ",SIGMA
1477 PRINT#1,CHR$(10) \ PRINT#1, "PEAK (X,Y): ",XPEAK,YPEAK
1480 PRINT#1,CHR$(10) \ PRINT#1,"SUMPROB: ",SUMP
1482 PRINT#1,CHR$(10) \ PRINT#1,"SMOOTHING INTERVAL: ",DEL
1484 PRINT#1,CHR$(10) \ PRINT#1,"PDF BIN SIZE (K): ",RESOL
1490
1495 INPUT "WANT HARD COPY PLOT OF PDF (Y/N)?";PF$
1500 IF PF$-"N" GOTO 1510
1505 GOSUB 7100
1510 INPUT "WANT DECONVOLUTION (Y/N)?";DCV$
1515 IF DCV$-"Y" GOTO 7900
1520 GOTO 9990
2000
3000 PRINT "ERROR ENCOUNTERED"
3005 GOTO 350
4000
5100 REM************INTERACTIVE RAW DATA REVIEW*************
5105
5107 PRINT "CURRENT # OF POINTS (RES): ",RES
5110 INPUT "MAX DESIRED VALUE (ABS. VALUE): " ;RAWMX
5111 INPUT "MIN DESIRED VALUE (ABS. VALUE): " ;RAWMN
5112 INPUT "INDEX OF FIRST KEEPER POINT: ";IFKP
5113 INPUT "INDEX OF LAST KEEPER POINT: ";ILKP
5120
5125 CNT-0
5130 FOR I-IFKP TO ILKP
5140 IF ABS(VOLT(I)) > RAWMX GOTO 5160
5145 IF ABS(VOLT(I)) < RAWMN GOTO 5160
5150 CNT-CNT+1
5155 VOLT(CNT)-VOLT(I)
5160 NEXT I
5165 RES-CNT
5170 RETURN
5200
5500 REM************RAW DATA PLOT SUBROUTINE****************
5503
5510 L-VOLT(1) \ M-VOLT(1)
5515 FOR K-2 TO RES
5520 IF VOLT(K) > L THEN L-VOLT(K)
5525 IF VOLT(K) < M THEN M-VOLT(K)
5530 NEXT K
5535
5540 W-1.05*L \ U-0.95*M \ J-W-U \ X--U/J \ BA-440*X \ B-30+BA
5545 ZZ-440/(W-U) \ Y-710/RES \ Q-RES/10 \ S-(W-U)/10
5550 T-440/(W-U)
5555 CLS
5560 FOR I-1 TO (RES-1)
5565-LINE (30+Y*I,ZZ*VOLT(I)+B,30+Y*(I+1),ZZ*VOLT(I+1)+B)
5570 NEXT I
5575 LINE (50,25,760,25)
5580 LINE (55,30,55,470)
5585 FOR I-1 TO RES STEP Q
5590 TEXT (30+(Y*I),15, "I")
5595 TEXT (30+(Y*I),5,NUM1$(I))
5600 NEXT I
5605 TEXT (630,40,"TIME")
5610 FOR I-U TO W STEP S
5615 TEXT (65,B+(T*I),"I",1,1)
5616 IJ-INT(I)
5620 TEXT (1,B+(T*I),NUM1$(IJ),1,0)
5625
5630
5635
5645
5650
5800
5801
5805
5810
5812
5814
5815
5820
5830
5832
5834
5836
5838
5840
5850
5852
5854
5856
5858
5860
5862
5864
5865
5870
5875
5880
5882
5884
5886
5888
5890
5892
5894
5896
5900
5901
5902
5905
5920
5922
5924
5925
5926
5927
5928
5930
5932
5940
5950
5952
5954
5956
5958
5970
5980
NEXT I
TEXT (90,300,"INTENSITY",1,1)
274
RETURN
REM***********CONVERSION OF RAYL SIGNALS TO VOLTAGES*********
REM********ELIMINATION OF EXTREMELY LOW VOLTAGE VALUES*******
INPUT "TEMP-COMP PARAMETER ALPHA: ";ALPHA
INPUT "TEMP-COMP PARAMETER BETA: ";BETA
GAMMA-REFERR*300/RRCS
INPUT "PDF BIN SIZE (K): ";RESOL
INPUT "CALC OR INPUT MIN ALLOWED SIGNAL (mV) (C/I)?";CMS$
IF CMS$-"I" GOTO 5870
INPUT "error parameter GM: ";GM
INPUT "error parameter GB: ";GB
INPUT "max adiabatic flame temp (K): ";MAFT
SRBAR-GAMMA*BETA/MAFT+GAMMA*ALPHA
DELSR-0.01*SRBAR*(10.**(GM*LOG10(SRBAR)+GB))
DELT-GAMMA*BETA*DELSR/(SRBAR-ALPHA*GAMMA)**2
A-0.001*DELT*SQR(2*PI)/RESOL
MDEV-DELT*SQR(-2*LOG(A))
TMAX-MAFT+MDEV
MRS-GAMMA*BETA/TMAX+GAMMA*ALPHA
GOTO 5880
INPUT "MIN ALLOWED RAYL COMBUSTION SIGNAL (mV)
-
";MRS
CLS \ CNT-0
FOR I-1 TO RES
SIGV-VOLT(I)*RSEN*1000/32768
IF SIGV < MRS GOTO 5892
CNT-CNT+1
VOLT(CNT)-SIGV
NEXT I
RES-CNT
REM********CONVERT VOLTAGES TO TEMPERATURE************
REM*****CORRECTION OF TOO LOW CALC. TEMPS.************
REM********TEMP PDF GENERATION AND CRT PLOT **********
CNT-O
FOR J-1 TO RES
TEMP-GAMMA*BETA/(VOLT(J) -GAMMA*ALPHA)
IF TEMP >- FTEMP GOTO 5928
RANDOMIZE
TEMP-FTEMP+RND*100.
CNT-CNT+1 \ VOLT(CNT)-TEMP
NEXT J
RES-CNT
AL-VOLT(1)
FOR 1-2 TO
IF VOLT(I)
IF VOLT(I)
NEXT I
\ AM-VOLT(1)
RES
> AL THEN AL-VOLT(I)
< AM THEN AM-VOLT(I)
INPUT "WANT SMOOTHING (Y/N)?";SM$
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6514 PRINT "SUMPROB - ",SUMP \ PRINT "RES - ",RES
6516 PRINT "NLRBCK - ",NLRBCK \ PRINT "MRS (mV) - ",MRS
6518 MEAN-SUM/RES
6520 PRINT "MEAN TEMP (K) - ",MEAN
6530
6540 FOR K-1 TO RES
6542 VAR-VAR+(VOLT(K) -MEAN)**2
6544 NEXT K
6546 VAR-VAR/(RES-1) \ SIGMA-SQR(VAR) \ DEV-SIGMA/MEAN*100
6548 PRINT "DEV (%) - ",DEV
6550 PRINT "ST.DEV. (K) - ",SIGMA
6570
6572 INPUT "REDO PDF WITH NEW PARAMETERS (Y/N)?";NBV$
6574 IF NBV$-"N" GOTO 6590
6576 INPUT "NEW RAYL BACKGR (NLRBCK): " ;NLRBCK
6584 GOTO 1220
6590 RETURN
6600
6700 REM********MILD SMOOTHING PROCEDURE**************
6701 REM**********TEMP PDF GENERATION*****************
6705
6720 INPUT "MAX PLOT TEMP (MAX 2500) (K): ";MAXX
6725 MAT P - ZER \ NB-MAXX-300
6730
6740 FOR K-1 TO RES
6742 TL%-INT(300) \ TU%-INT(MAXX)
6744 IF (TU%-TL%) > INT(1) THEN TM%-INT((TU%+TL%)/2) ELSE GOTO 6750
6746 IF VOLT(K) > TM% THEN TL%-TM% ELSE TU%-TM%
6748 GOTO 6744
6750 I-TL%-300
6752 P(I)-P(I)+1
6754 NEXT K
6770
6780 INPUT "SMOOTHING INTERVAL: ";DEL
6785
6790 FOR I-1 TO NB
6792 IF P(I) > 0 GOTO 6796
6794 NEXT I
6796 FB-I
6798 FOR I-NB TO 1 STEP -1
6800 IF P(I) > 0 GOTO 6804
6802 NEXT I
6804 LB-I
6810
6820 FOR J-FB TO LB
6822 SUM-0
6824 FOR N--DEL TO DEL
6826 -SUM-SUM+P(J+N)
6828 NEXT N
6830 P(J)-SUM/(2*DEL+i)
6832 NEXT J
6840
6850 INPUT "SMOOTHED PDF BIN SIZE (K): ";RESOL
6852 NBB-(MAXX-300)/RESOL
6855
6860 CNT-1
6870 FOR I-1 TO NBB
6872 SUM-0
6874 FOR N-1 TO RESOL
6880 SUM-SUM+P(CNT)
276
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NEXT J
PRINT #2,
FOR K-300
PRINT #2,
PRINT #2,
NEXT K
PRINT #2,
PRINT #2,
"CP-5,-.25;LB";J;CHR$(3)
"CP5,-17.5;DIO,1;LBPROBABILITY (%)";CHR$(3);"DI1,0;"
TO MSV STEP Q
"PA",K,0
"CP-2.5,-1.0;LB";K;CHR$(3)
"CP-60,-1.5;LBTEMPERATURE (K)";CHR$(3);"PU"
"SM ;PA 300,0"
FOR L-1 TO NB
AA-300+L*RESOL-RESOL
AB-AA+RESOL \ YY$-NUM1$(PLT(L)*100)
PRINT #2, "PA",AA,YY$;"PD"
PRINT #2, "PA",AB,YY$
NEXT L
PRINT #2, "PU;
"
8738
8740
8742
8744
8746
8748
8750
8752
8754
8756
8760
8762
8764
8766
8768
8770
8772
8774
8780
8781
8782
8783
8784
8785
8790
8795
8800
8801
8802
8803
8810
8812
8814
8816
8818
8820
8822
8825
8830
8832
8834
8835
8840
8845
8850
8852
8854
8856
8858
8860
8865
8866
8870
8872
8874
8876
8878
8880
8882
8884
A-0.2*MSV
PRINT #2,
PRINT #2,
PRINT #2,
PRINT #2,
\ B-0.95*MPV
"PA",A,B;"LBPDF MEAN (K) - ";MEAN;CHR$(3) \ B=B-0.3*RV
"PA",A,B;"LBST.DEV. (%) - ";SIGMA;CHR$(3) \ B=B-0.3*RV
"PA",A,B;"LBBIN SIZE (K) - ";RESOL;CHR$(3)
"PU;SPO;PA 0,0;"
IF FLG$-"A" GOTO 8810
PRINT#1,CHR$(10)
PRINT#1,CHR$(10)
PRINT#1,CHR$(10)
\ PRINT#1,"REGEN. OBSV. PDF"
\ PRINT#1,"PDF MEAN (K): " ,YCSUM
\ PRINT#1,"STD. DEV. (%): ",YCSIG
PRINT #1,CHR$(10) \ PRINT #1,"PDF POINTS (X,Y)"
IF FLG$-"B" THEN NB-NDR
FOR L-1 TO NB STEP 2
AA-300+L*RESOL-RESOL/2 \ AAB-AA+RESOL
PRINT #1,CHR$(10)
PRINT #1,AA, (PLT(L)*100) ,AAB, (PLT(L+1)*100)
NEXT L
IF FLG$-"B" GOTO 8910
INPUT "WANT REGEN. OF OBSV. PDF (Y/N)?";RGN$
IF RGN$-"N" GOTO 8910
REM*********REGENERATION OF OBSV. PDF**********
FOR N-1 TO NDR
SUMHX-0
FOR M-1 TO NDR
SUMHX-SUMHX+H(N,M)*X(M)*100
NEXT M
YC(N)-SUMHX
NEXT N
YCSUM-0 \ YCSUS-0
FOR N-1 TO NDR
TEMP-TF+(N-1)*RESOL
YCSUM-YCSUM+YC(N)/100*TEMP
YCSUS-YCSUS+YC(N)/100*TEMP**2
PLT(N)-YC(N)/100
NEXT N
YCSIG-SQR(YCSUS-YCSUM**2)/YCSUM*100
282
8886
8890
8892
8894
8896
8898
8900
8905
8910
8912
8914
8916
8918
9990
9992
9994
9996
9998
9999
INPUT "MAX PLOT TEMP (max 2500) (K): ";MAXX
CLS \ FLG$-"C"
PRINT "REGEN. MEAN TEMP: ",YCSUM
PRINT "STD. DEV. (%): ",YCSIG
MEAN-YCSUM \ SIGMA-YCSIG
GOTO 8520
REM*****DECIDE WHETHER TO REDO ORIG DATA ANALYSIS*******
INPUT "REDO ORIGINAL DATA ANALYSIS (Y/N)?";RODA$
IF RODA$-"Y" GOTO 1220
REM****************PROGRAM TERMINATION****************************
INPUT "RUN AGAIN (Y/N)?";X$
IF X$-"N" GOTO 9999
CLS \ GOTO 100
CLOSE #1 \ CLOSE #2 \ END
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390
392
394
395
396
398
400
402
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406
408
410
412
414
NEXT K
ALPHA-(A*CNT-CC*D)/(B*CNT-CC**2)
BETA-(B*D-A*CC)/(B*CNT-CC**2)
CCOEF-(CNT*A-CC*D)*((CNT*B-CC**2)*(CNT*E-D**2))**-0.5
PRINT "TEMP-COMP PARAMETER ALPHA - ",ALPHA
PRINT "TEMP-COMP PARAMETER BETA - ",BETA
PRINT#1, CHR$(10)
PRINT#1, "TEMP-COMP PARAMETER ALPHA - ",ALPHA
PRINT#1, CHR$(10)
PRINT#1, "TEMP-COMP PARAMETER BETA - ",BETA
PRINT "LINEAR CORR COEFF - ",CCOEF \ PRINT#1,CHR$(10)
PRINT#1, "LINEAR CORR COEFF - ",CCOEF
450
500 INPUT "RUN AGAIN (Y/N)?";RAG$
501 IF RAG$-"Y" GOTO 16
502 CLOSE #1 \ END
287
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255
260
261
262
265
270
271
272
280
285
286
287
290
295
300
305
310
315
320
325
330
332
334
336
338
340
342
345
350
355
360
362
370
372
380
382
388
390
392
394
395
396
398
400
402
404
406
408
410
412
414
450
500
501
502
TS-1000.
AVHT-1-(0.01*HL)
IF PHI > 1.0 THEN HEAT-160170. ELSE HEAT-316240.
SF-O \ SFP-0 \ CT-1
FOR I-1 TO 7
SF-SF+XP(I)*(A(I)*(TS-300)+B(I)*(TS**2-300**2)/2+C(I)*&
(TS**3-300**3)/3)
NEXT I
F - AVHT*(CONETH*HEAT+PREHT)/TPM - SF
FOR I-1 TO 7
SFP-SFP+XP(I)*(A(I)+B(I)*TS+C(I)*TS**2)
NEXT I
FP--SFP
NTS-TS-F/FP
IF ABS((NTS-TS)/TS) < 0.01 GOTO 330
IF CT - 1000 THEN GOTO 315 ELSE GOTO 320
PRINT "NO CONVERGENCE AFTER 1000 CYCLES"
TS-NTS \ CT-CT+1 \ GOTO 265
\ GOTO 500
IF PHI > 1.0 THEN BASIS-OXID ELSE BASIS-FUEL
FCF-CONV/BASIS*100. \ PRINT#1,CHR$(10)
PRINT "FUEL OR OXID CONVERSION (%) - ",FCF
PRINT#1, "FUEL OR OXID CONVERSION (%) - ",FCF
PRINT "AD FL TEMP (K) - ",NTS \ PRINT#1,CHR$(10)
PRINT#i, "AD FL TEMP (K) - ",NTS
AFT(CNT)-NTS
RETURN
REM********LINEAR REGRESSION OF SIGMAP VS. AFT**********
A-0 \ B-0 \ CC-0 \ D-0 \
E-0
FOR K-1 TO CNT
A-A+AFT(K)*SIGMAP(K) \ B-B+AFT(K)**2
CC-CC+AFT(K) \ D-D+SIGMAP(K) \ E-E+SIGMAP(K)**2
NEXT K
ALPHA-(A*CNT-CC*D)/(B*CNT-CC**2)
BETA-(B*D-A*CC)/(B*CNT-CC**2)
CCOEF-(CNT*A-CC*D)*((CNT*B-CC**2)*(CNT*E-D**2))**-0.5
PRINT "TEMP-COMP PARAMETER ALPHA - ",ALPHA
PRINT "TEMP-COMP PARAMETER BETA - ",BETA
PRINT#1, CHR$(10)
PRINT#1, "TEMP-COMP PARAMETER ALPHA - ",ALPHA
PRINT#1, CHR$(10)
PRINT#1, "TEMP-COMP PARAMETER BETA - ",BETA
PRINT "LINEAR CORR COEFF - ",CCOEF \ PRINT#1,CHR$(10)
PRINT#1, "LINEAR CORR COEFF - ",CCOEF
INPUT "RUN AGAIN (Y/N)?";RAG$
IF RAG$-"Y" GOTO 16
CLOSE #1 \ END
290
1 REM***
2
3
4
5
7
9
10
11
12
13
14
15
16
17
18
19
20
22
23
24
25
26
27
28
29
30
31
32
33
34
35
40
41
42
45
46
47
48
49
50
51
55
60
61
65
70
7r
75
76
77
78
79
80
81
82
84
85
86
87
REM***
REM***
REM***
REM***
PROGRAM "AFTCOH2"
CALCULATE SIMPLE ADIABATIC FLAME TEMPERATURES,
EFFECTIVE CROSS SECTIONS, FEED-BASED RESIDENCE
TIMES FOR CO/H2 COMBUSTION
3/24/89
***
***
DIM A(6),FPK%(5),XF(6),XP(6),B(6),SIGF(6),SIGP(6),C(6),CP(6)
DIM SIGMAP(15),AFT(15)
OPEN "#SER01" AS FILE #1
FPK%(1)-20 \ FPK%(2)-6 \ FPK%(3)-22 \ FPK%(4)-200
CALL SYSFUNC(1,FPK%(1))
\ FPK%(5)-O
INPUT "RUN NAME: ";RUNNAM$
PRINT#1,CHR$(10) \ PRINT#1,"RUN NAME: " ,RUNNAM$
INPUT "RUN DATE: ";RUNDAT$
PRINT#1,CHR$(10) \ PRINT#1,"RUN DATE: " ,RUNDAT$
INPUT "EQUIVALENCE RATIO: ";PHI
PRINT#1,CHR$(10) \ PRINT#1,"EQUIVALENCE RATIO - ",PHI
INPUT "MOLAR CO/H2 RATIO: ";R
PRINT#1,CHR$(10) \ PRINT#1,"MOLAR CO/H2 RATIO - "R
INPUT "FEED RATE OF CO (GMOLES/MIN): ";M
PRINT#1,CHR$(10) \ PRINT#1,"CO FEED RATE (GMOLES/MIN) - ",M
INPUT "WINDOW/DIL N2 (GMOLES/MIN): ";Y \ PRINT#1,CHR$(10)
PRINT#1,"WINDOW AND/OR DIL N2 RATE (GMOLES/MIN) - ",Y
INPUT "MEASURED T/C TEMPERATURE (K): ";TEMP
PRINT#1,CHR$(10) \ PRINT#1,"T/C TEMPERATURE (K) - ",TEMP
INPUT "EST FEED PREHEAT TEMP (K): ";TFEED
PRINT#1,CHR$(10) \ PRINT#1,"EST FEED TEMP (K) - ",TFEED
INPUT "EST HEAT LOSS (%): ";HL
PRINT#1,CHR$(10) \ PRINT#1,"EST HEAT LOSS (%) - ",HL
REM************CALCULATE TOTAL FEED RATE AND***********
REM**************FEED BASED RESIDENCE TIME*************
FR-M*(1+1/R)*(1+2. 381/PHI)+Y
PRINT "TOTAL FEED RATE (GMOLES/MIN) - ",FR \ PRINT#1,CHR$(10)
PRINT#1,"TOTAL FEED RATE (GMOLES/MIN) - ",FR
TAU-(250*60)/(TEMP*FR*0.0821)
PRINT "FEED BASED RESID. TIME (MSEC) - ",TAU \ PRINT#1,CHR$(10)
PRINT#1,"FEED BASED RESID. TIME (MSEC) - ",TAU
COMPONENT INDEX ORDER AS FOLLOWS:
REM********
REM******** 1-CO, 2-H2, 3-02, 4-N2, 5-C02, 6-H20 ********
REM***CALCULATE EFFECTIVE CROSS SECTION OF FEED***********
XF(1)-M/FR \ XF(2)-(M/R)/FR
XF(4)-1-(XF(1)+XF(2)+XF(3))
SIGF(3)-XF(3)*5.175
SIGF(4)-XF(4)*6.216
SIGMAF-0
FOR I-1 TO 6 \
\ XF(3)-M*(1+1/R)*(0.5/PHI)/FR
\ XF(5)-O \ XF(6)-0
\ SIGF(5)-XF(5)*14.24 \ SIGF(1)-XF(1)*7.767
\ SIGF(6)-XF(6)*4.446 \ SIGF(2)-XF(2)*1.352
SIGMAF-SIGMAF+SIGF(I) \ NEXT I
PRINT "FEED EFFECTIVE CROSS SECTION - ",SIGMAF \ PRINT#1,CHR$(10)
PRINT#1, "FEED EFFECTIVE CROSS SECTION - ",SIGMAF
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