72 XF(I)-M/FR \ XF(2)-0 \ XF(3)-0.21*AIR/FR \ XF(7)-0. 73 XF(8)-0 \ XF(9)-0 \ XF(10)-TOX/FR \ XF(5)-0 \ XF(6)-0. 74 XF(4)-(0.79*AIR+Y)/FR. 75 SUMXF-O. 76 FOR ...
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
Sig~nature Certified by 07
redacted January 4,
1990
0- 000o~ '0 (;?" 00o°-yo ~ p;;fe~~~~ 0j~h~ 0P: 0L.;~~~ii _
_
Thesis Supervisor
Signature redacted Certified by .............. Yo .~!
••• : • ".
'fr~~~'
;d:i .F: .s~~~fi~
Thesis Supervisor
Signature redacted
Accepted by ..................................................... . Professor William M. Deen Chairman, Departmental Committee on Graduate Studies MASSACHUSETTS INSTITUTE OF TECHNtJ/.OGY
1
ARCHIVES
MAR 28 1990
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 concentrations of unburned fuel in excess of PSR predictions. 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 backrnixed 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
TABLE OF CONTENTS CHAPTER 1 -- MOTIVATION . . . . . . . . . 1.1. Importance of the chemistry I mixing interaction..
· . . 12 .12
1.2. Stirred reactor in combustion I incineration research
. . 12
1.3. Toroidal jet stirred combustor (TJSC)
. . 13
1.4. Importance of flame stability
.16
1.5. PSR and the approach to blowout
.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 -- OBJECTIVES AND APPROACH
· . . 26
3.1. Thesis objectives
· .26
3.2. Study of TJSC using system of known kinetics
.26
3.3. Desired data . . . . . . .
.26
3.4. TJSC characterization - model development
.28
3.5. Special application: CH3C1 oxidation in TJSC . . . . . . . 28 CHAPTER 4 - - LASER RAYLEIGH SCATTERING FOR TEMPERATURE 4.1. Brief review of LRS for flame thermometry 4.2. Description of the physics . . . . . . . . CHAPTER 5
EXPERIMENTAL SYSTEM
· .29 · . . 29
.30 .36
5.1. Optics I laser I electronics I signal sampling
· .36
5.2. TJSC with optical access.
· .40
5.3. Gas sampling and analyses
· .42
CHAPTER 6 -- OPTICAL SYSTEM PERFORMANCE / LIMITATIONS
.46
6.1. Optical calibration
· . . 46
6.2. System noise . . . .
· . . 50
6.3. Theoretical description of system noise
· . . 52
6.4. Observed fluctuations and PDF deconvolution CHAPTER 7
. . . . . 56
- - DATA / OBSERVATIONS FOR TJSC CHARACTERIZATION
.59
7.1. Introduction
.59
7.2. Mechanics of PSR modeling
.59
7.3. Oxidation of CO/H2
.60
7.4. Oxidation of C2H4
.82
CHAPTER 8 -- ORIGINAL MODELING FOR TJSC CHARACTERIZATION
. 117
8.1. Fluid mechanics or detailed chemistry?
. 117
8.2. TJSC modeling approaches . . . .
. 117
8.3. Important guiding observations.
. . 119
8.4. New PFR (jet mixing) / PSR hybrid model 8.5. Mechanics of PFR(JM)/PSR modeling 8.6. Results of new hybrid model
. 120 122 · 125
CHAPTER 9 -- SPECIAL CHEMISTRY \ MIXING INTERACTION PROBLEM. 137 9.1. Introduction . . . . . . . . . . .
137
9.2. Fuel lean CH3C1 oxidation mchanism development
· 137
9.3. C2H4/CH3C1 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
APPENDICES
· . 178
A.1. Experimental and computer procedures.
· . 179
A.2. Rayleigh data workup and PDF generation
· . 185
A.3. Applications of QRRK
· . 186
.....
A.4. Jet mixing equations for CHEMKIN
· . 224
A.s. Elementary reaction mechanisms.
· . 228
A.6. Computer programs
239
7
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 7-3: Feed and operating conditions for selected fuel lean C2H4 runs for laser data . . . .
. . . . . 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 7-6: 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/CH3C1 runs for laser data . . . . . . 141 9-2: Observed, PSR, and PSR+PQ concentrations for diluted fuel lean C2H4 and C2H4/CH3C1 cases
.152A
9-3: Parameters for PSR calculations of temperature vs. mass throughput for diluted fuel lean C2H4 and C2H4/CH3Cl runs 9-4: PSR calculated concentrations for diluted fuel lean C2H4 and C2H4/CH3Cl runs near blowout . . . .
8
155
. . 158
9-5: PSR calculated rates-of-production of OH for diluted fuel lean C2H4 and C2H4/CH3Cl 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/CH3Cl runs near blowout
.164
9-8: PSR calculated rates-of-production of Cl for diluted fuel lean C2H4/CH3Cl run near blowout
.166
9-9: PSR calculated rates-of-production of H for diluted fuel lean C2H4 and C2H4/CH3Cl 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-I: Reactions for CI/C2 Hydrocarbon Oxidation
. . 228
A-2: Species thermodynamic properties for CI/C2 hydrocarbon oxidation . . . . . . . . . . . . . . . . . 232 A-3: Reactions for fuel lean CH3CI oxidation
. . 233
A-4: Thermodynamic properties for chlorine containing species . . . . 235 A-5: Sources and notes on non-QRRK reactions in CH3CI mechanism . . . . 236
C)
LIST OF FIGURES 1-1: Cross section of toroidal jet stirred combustor
· . 14
1-2: Idealized performance curves for a PSR 2-1: TJSC water model with single jet air injection
. 18 · . 21
2-2: Fuel rich C2H4 combustion thermocouple traces in TJSC. 2-3: LIF data from cold flow studies in aluminum TJSC 4-1: Rayleigh scattering optical sample volume .
. 25 · . 31
5-1: Experimental apparatus for Rayleigh scattering 5-2: Electronic signal traces and sampling gate
23
37 · . 39
5-3: TJSC optical access . .
41
5-4: Flow system for current TJSC
· . 43
5-5: Gas sampling train
· . 44
6-1: TJSC optical calibration scheme .
. . 47
6-2: Optical calibration: Net mean signal vs. pressure
. . 49
6-3: Optical calibration: 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
. . 81
7-6 (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
7-8 (A-->E): Observed and deconvoluted Rayleigh PDF's for fuel lean C2H4 oxidation with increasing dilution 92
10
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: Cl+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 for selected fuel rich C2H4 oxidation
PDF's
7-14: Spatial thermocouple traces for C2H4: rich and lean
. . 109 . 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/CH3Cl runs
. 143
9-2: Spatial thermocouple traces for diluted C2H4 and C2H4/CH3Cl 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/CH3Cl oxidation. 160 A-I: Control volume for PFR(JM) enthalpy and mass balances . 225
II
CHAPTER 1 -- MOTIVATION
Importance of the Chemistry I The
Mixin~
Interaction
interaction of mixing and chemical reaction is of funda-
mental importance in chemical engineering, in combustion.
especially as
applied
On the most basic level, fuel and oxidant must be
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 I 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
of
i
a
a
simple
mass balance on that species between inlet and outlet
r.1 - m1 (y. 1 - y. * ) / (V W.) 1 where weight
m
- mass flow rate,
of i,
(1-1)
V - reactor volume,
Yi - mass fraction of i,
and
*
W.
1
molecular
represents the feed
condition.
A
series
of
elementary
reactions
account for each net reaction rate ri'
12
are
written
The set of reaction
to mass
balances are solved simultaneously for given feed conditions. temperature or
is determined from the corresponding enthalpy balance
can be measured.
then
The predicted outlet concentrations
compared to the observed concentrations y..
quality data,
Yi
Assuming
1
the
The
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.
(1984).
characteristics
key
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 Vaughn
(1985).
fundamental
combustion
chemistry
The fixation of nitrogen during fuel
combustion was
recently
studied
by
studied the formation of soot and
Sun poly-
cyclic aromatics during combustion of fuel rich C H and C H /ben2 4 2 4 zene (C H ) blends. Each study treated the TJSC as a PSR. 6 6 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
TORUS
FIGU~E
1-1:
Cross section of toroidal jet stirred combustor
TABLE 1-1 Characteristics and Range of operating Conditions of the Toroidal Jet stirred Combustor
REACTOR VOLUME (C~3) TORUS MINOR
DI~£TER
MEAN AXIAL FLOW VELOCITY
(c~)
(m/s)
3 MEAN RESIDENCE TIME (10-
250 3.2 100 - 2'00
5)
3 - 12
MASS FLOW RATE egis)
5 - 15
NUMBER OF FEED JETS JET TUBE
DIAMETER (c:n)
TURBULENT MIXINGS PER RESIDENCE TIME
32 0.1 40 - 60'
TAYLOR SCALE (10- 4 m)
5
5 KOLMOGOROV SCALE (10- m)
2
TEMPERATURE (K)
PRESSURE (atm)
I')
1200 - 1900
1
during C H 2 4
fuel rich C H operations. 2 4
02
and
conversions combustion
concentrations. greater
of
He
under-predicted
Darivakis
(1986)
observed
observed
fuel
than predicted by a PSR model for fuel
lean
equimo1ar mixtures of CO and
H . 2
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
highly recirculated flame stabilization zone just
from be
PSR has special implications for incineration
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 backrnixed
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 backrnixed into the incoming feed.
be
Stability is the key issue in the Special Problem section
to
Flame instability can lead to products
of
discussed
later.
incomplete combustion (PIC).
These can be as simple as excess CO
to complex and highly toxic chlorinated dioxins.
16
PSR and the Approach to Blowout Figure
1-2
illustrates the basic concept of
using idealized operating curves. on
PSR
stability
A stable operating point occurs
the high temperature branch when the reaction rate matches the
heat balance.
As the mass flow rate is increased and the tempera-
ture drops, blowout is approached. The plete
approach toward a blowout point for a PSR
reactor
assumes
homogeneity even up to and including the
com-
blowout.
Whether the TJSC behaves in this manner is an important issue research for two reasons. it
toward blowout,
istry
interaction.
under
these
emulates
a PSR.
First, by studying the TJSC as we push
we are
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.
This has serious
imp1i-
cations for hazardous waste incineration.
Special Interaction Problem: Ch1orocarbon Incineration Incineration
is
currently viewed as a practical option
the disposal of chlorinated hydrocarbon (C1HC)
wastes.
chlorine
has been shown to have a negative impact on
flames.
It
velocities
for
However, hydrocarbon
has been experimentally observed that laminar
flame
decrease as the Cl/H molar ratio in the fuel increases
(Va1eiras et.a1., 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
JIr
t
Blow-out limit
Unstable Branch
L.J.J
0::: ~
I-
ex:
0:::
L.J.J 0...
:E:
L.J.J I-
Stable low temperature Branch
/ MASS FLOW RATE
~
t
Unstable point
z:
o ......
IU
cr:
Enthalpy balance
L.J.J
0::: L.L..
o
Reaction Rate Equation
~
~
x
L.J.J
TEMPERATURE
~
equivalence ratios. The apparent
general slowing of the chemistry in C1HC flames
has important implications for incineration. cal
tool
for
associated PIC. istry
The TJSC is a 10gi-
research into C1HC 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 C1HC incinerators.
19
BACKGROUND
CHAPTER 2
Observed Deviation from PSR Behavior Deviations
from PSR performance were observed in the TJSC by
Darivakis (1986) and Kridiotis et.al.
(1989).
CO/H
the measured outlet concen-
2
(equimolar mixture) combustion,
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
coalescence-
With an arbitrary, yet physically reasonthe model satisfactorily predicted
observed CO and H2 concentrations. suffers
a
the
It was concluded that the TJSC
more from imperfect macro-mixing than
imperfect
micro-
This is consistent with the above suggestion of a degree
mixing.
of plug flow character. During (1988)
fuel rich C H / air combustion in the 2 4
TJSC,
Vaughn
underpredicted experimentally observed parent C H and 2 4
concentrations by assuming a PSR model.
O 2
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
rationalize suggested
the
concentration
use of the two PSR's
volume blown out.
and
temperature
in series model,
data,
Vaughn
with the
first
This approach did not sufficiently improve the
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
1650 ~ 1630 ~ 1610 .....,.....
~
-=:., 1590
l
2~
r
r--:
l
1c:..70! v
< 1550 I~
:
~
C-
1530
~ 1510
~
1490
~
r
r ~
i
1470 ~ 1450 r
• - . cp=2.0 0-0
2.06
---> 1.0
---> 0.516
PDF Fig.No.
Di1.N2 (scfrn)
11 19 12 10
7-2A
Di1.N2@ Ito tal
o
B
o
o o
C
0.8 1.6 2.4 3.2 4.3 4.9 5.6 5.6 6.2
0.06 0.11 0.16 0.20 0.26 0.28 0.31 0.31 0.33
D E F
9
(52.27 mole % CO, bal. H ) 2
---> 9.5
Run No.
18
#
8
G
17 13 16 14
H I J K
Total Mass (g/s) 6.66 6.66 7.11 7.55 8.00 8.45 9.06 9.39 9.79 9.79 10.12
standard conditions ---> 60 of, 1 atm $ corrected for conductive losses @ ratio of volumetric flows #
61
TIC Temp.$ (K)
1630 1580 1600 1510 1440 1370 1330 1290 1290 1240 1240
FIGURE 7-1: Deconvoluted PDF mean and thermocouple temperatures as a function of dilution for fuel lean CO/H2 (~- 0.52)
1.7 1.6 1.5
tl
~
J
~
~ ...........,
"'"
1.4
w~
et:c: ::>0
1-(1)
~5
w.c n..t~..........., w
1.3
1.2
tl~
1
o~ o
0"
f-
1.1 1
:~
0.9
o [J
0.04
0.08
0.12
0.16
0.2
0.24
0.28
DILUENT N2 FLOW / TOTAL FLOW THERMOCOUPLE + RAYLEIGH PDF MEAN
0.32 0' N
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 TjC,
was stable under these conditions and in no
suggested instability unless total TJSC blowout occurred. more The
highly
An even
diluted run (ratio - 0.31) is shown in Figure
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 TjC 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
8
RUN DATE.
7/15/99
, OF DATA POINTS.
1994
6
16.6417
-~
(10 -
..J
m
....
...J
m
< m c
6
(observed)
0::: .11.
2
o
~~~~--~~~----~----~----~------~----~--~~--~--~----~
300
520
740
960
IlBO
1400
TEMPERATURE
1620· 1840
2060
22BO
2500
(K)
FIGURE 7-2E: Rayleigh PDF's for fuel lean CO/H2 . (cP=0.52); T/C=1440 K; dil.N2/total=.16 37
PDF MEAN (K) - 1309.6 ST. DEV. (:). - 9. 7767 BIN SIZE (K) - 50
33.3
rms fluc. = 130 K 29.6
(deconvoluted)
25.9 22.2
>-
t:
...J
m
18.5
< m c 0:::
a..
14. Ii
ILS
11.1
7.4 .. 3.7
o
300
520
140
--
960
1180
1400
TEMPERA TURE CK)
1620
1840
2060
22BO
2500
70
12 NAME. RUN IS RUN DATE. 7/15/8S
10
, OF DATA POINTS. POF MEAN Ck). ST. DEV.
SIN SIZE
8
a
,..
lB. 1228
CX)· (k)
2024
1323.98
•
50
(observed)
...-' ...m to-
8.
FIGURE 7-6 THE FOLLOWING SERIES OF OBSERVED AND DECONVOLUTED PDF'S CORRESPOND TO THE CONDITIONS DESCRIBED IN TABLE 7-3
84
8
NAME. RUN 1 RUN OATE. 11/2/88
* OF
OATA POINTS.
1981
6
1630.59 15.6085
>-
I-
SO
d CO
< CO o
4
(observed)
Q::
a..
2
~----~------~----~~~--~----~------~------------~------~~--~
o
300
520
740
960
1180
1400
TEMPERATURE
1620
1840
2060
2280
2500
(K)
FIGURE 7-6A: Rayleigh PDF's for fuel lean C2H4 (q,=.53);· T/C=1625 K; dil.N2/total=O.O 54
POF MEAN (K) - 1548.77 ST. DEY. (%) - 5. 8566 BIN SIZE CK) - 50
48.6
rrns flue. = 85 K
43.2
(deeonvoluted)
37.8
8 32.4
>-
I-
d
co
-
.... ...J .... m I-
6
t-
0:: 20. 5
m m
< 0
0::
a..
16.4
12.3
8.2
4.1
0
r 300
520
740
960
1180
1400
TEMPERA TURE 00
1620
1840
2060
2280
2500
Such
narrow PDF's (rms fluctuations about 5.5 % of the mean)
also
consistent with the PDF of the L1F 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
(TIC)
(equivalence
ratio - 0.54) C H 2 4
was
burned
at
lower temperatures by addition of dilution N2 to the
feed.
Table 7-4 lists the feed rates and
thermocouple
TIC
measurements
temperatures.
Figure 7-7 shows that the
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/H2 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 C H 2 4 run (dilution ratio - 0.22).
As with the highly diluted CO/H2 run
(Figure 7-21), this C H deconvoluted PDF has a large rms fluctua2 4 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/H2 with dilution ratio - 0.20,
fluctuation - 130 K), rms
tempera-
fluctuation
notice that fuel lean C H yields a greater 2 4
and a greater probability of
than fuel lean CO/H
2
rms
localized
blowout
for about the same equivalence ratio (equiva89
TABLE 7-4 TJSC Oxidation of C2H4/Air Mixtures for Laser Data Base Feed Gas Rates (scfm):# Fuel Air Window N2 Equivalence Ratio Run No. 1 2 3 4 6
PDF Fig.No.
Di1.N2 (scfm)
7-8A B C
0 1.1 2.9 3.6 3.9
D
E
- --> ---> - --> - -->
Di1.N2@ Ito tal 0 0.07 0.17 0.21 0.22
0.468 12.47 1.0 0.536 Total Mass (g/s) 7.99 8.60 9.61 10.00 10.17
# standard conditions ---> 60 of , 1 atm $ corrected for conductive losses @ ratio of volumetric flows
90
TIC 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 (qp- 0.54)
1.7 1.6
1
0.9
o [J
0.04
0.12
0.08
THERMOCOUPL~ILENT
N2 FLOW
+
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
1
NAME. RUN 1
RUN DATE.
5/10/89 19S2
, OF DATA POINTS.
8
PDF MEAN 00 -
ST.OEV.
(X)
-
USS9. 39 1~.
sue
50
...~ ... ..J
(observed)
a:l
I 2
o300 ~----~----~-------..----------------------------~----~~--~ 520 7~0 Q60 1180 1~00 1620 18~0 2050 2280 2500 TEMPERA TURE
Rayleigh PDF's for fuel lean C2H4 (qp- 0.54); T/C - 1670 K; diluent N2 flow/total flow - 0.0
FIGURE 7-8A: 8S
O()
~
PDF MEAN 00 S583. 3e ST. DEV. a) - 5. 27323
8IN SIZE 00 -
78.5
-
50
(deconvoluted) ee
rms flue. = 85 K
SQ.!
8 ..
!51
...~ ... ..J
II)
I
0
50
N
40
+
30
u ~
u
20 10 0 0
0.02
0.04 D
0.06
0.08
0.1
0.12
0.14
0.16,0.18
0.2
DILUENT N2 FLOW / TOTAL FLOW MEASURED + PSR+PQ
o
0'
difference between CO/H the TJSC.
2
and C H in their respective behavior 2 4
For the same mixing energy (i.e.
inducing
instability in the CO/H
2
speed
mixing time scales),
fuel is more difficult than
C H due to the faster chemistry of H , 2 2 4 flame
in
data 364 cm/sec for H ; 2
in
as evidenced from laminar 78 cm/sec
for
C H ; 2 4
from
Gunther, 1974). Inferences sampling.
can also be made concerning the optical and probe
The
hydrocarbons
large calculated PQ effect on the residual for
the
cool fuel lean C H 2 4
cases
C ,C l 2
suggests
the
following: a) Accurate modeling of the PQ effect for these species in
such cases might not be feasible due to uncertainties
probe
reaction
hydrocarbons
dynamics;
C ,C 2 l
entering the probe during the diluted runs is
prob-
a factor of
the non-intrusive optical method,
clearly show localized blowout,
confirming the existence of significant amounts of
raises
and
c)
The consumption of hydrocarbons in
the level of CO,
based
on
blowout
the
10
The corresponding Rayleigh PDF's, obtained by
for cases #12,13).
material;
the
b) The actual concentration of
ably much greater than the measured amounts (e.g.
thus
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
%
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
C H /air runs. 2 4
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 C H /Air Mixtures for Laser Data 2 4 Run Number:
4,5
Run Date:
6
7
7.94
6.10
5.78
0.0673
0.0962
0.1095
0.1278
0.1451
0.1532
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 Rate (g/sec): Feed Mole Fractions:
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 o 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
NAME. RUN 4 RUN DATE. 11/2/88 OF DATA POINTS. 2007 PDF MEAN (K) - 1543.42 ST. DEV. ex) - 11.8523 BIN SIZE (K) - 50
12
*
10 Q ~
.-->-
.... ..J
....III
8
(observed)
#7) do not show any
temperature material.
This eliminates any speculation
that
the central core of the torus is blown out. Finally,
a
gas sample was taken under fuel rich C H condi2 4
tions (equivalence ratio - 2.01). operating
conditions,
Table 7-7 lists the feed
measured concentrations,
and PSR,
and
PSR+PQ
simulation results.
These data are consistent with those observed
by
Notice that the measured C H and 2 4
Vaughn (1988).
exceed
those
implications.
predicted by PSR+PQ. For the most part,
02
This has important
of .C H , 2 6
the PQ calculation has little effect
predicted composition for fuel rich C H combustion. 2 4
114
modeling
though, TJSC performance under
fuel rich C H conditions can be approximated by a PSR. 2 4 exception
levels
With the on
the
FIGURE 7-14 lHERMOCOUPLE TRACE 1.68
o
1.67
------------------ o
/
1.66
-- ---
1.65 /
1.64
o ____
1.63
(/
1.62
..-... ~
\"",.,..I'
..-...
1.61
w tJl 11::1)
1.6
:Jc
t-~
1.59
11::0
«:J
1.58
ll.b :l:
1.57
w£,
~
~_/
/+-
0
D~+~
1/
-0"
~+ +---+
1.56 1.55 1.54 1.53 1.52 1.51 1.5 1.49
0
20
o
40
DISTANCE ACROSS DIAMETER rtHor t LEAN C2H4
60
80
100
(%)
+
RICH C2H4 ~
116 TABLE 7-7 TJSC Oxidation of Fuel Rich C H /Air Mixtures 2 4 Case Number:
16
Feed Rate (g/sec):
6.24
Feed Mole Fractions: 0.0949 0.1418 0.7633 Equivalence Ratio:
2.01
T/C Temperature (K):$
1620
Residence Time (msec):#
7.8
Product Concentrations: * CO (mole %) Measured: PSR: PSR+PQ:
12.4 12.5 12.6
4
(ppm)
4200 2104 2345
H2 (mole %)
C H (ppm) 2 6
6.2 7.5 7.5
130 38 145
Measured: PSR: PSR+PQ: °2 Measured: PSR: PSR+PQ:
CH
(mole %) 0.9 0.4 0.3
C H (ppm) 2 4 2800 855 607
C H (ppm) 2 2 Measured: PSR: PSR+PQ:
17400 13300 13086
Corresponding PDF Figure Number: Decon.PDF rms flue. (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
well
as
Backmixing
the is
the PSR is an ideal
case,
simplest model we can consider
for
the
TJSC.
assumed to occur much faster than
any
reactions,
thereby ensuring homogeneity on all length scales. The selected
TJSC
has been shown to deviate from
experimental data.
conversions
of
PSR
behavior
Darivakis (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
O and C H concentrations for fuel rich C H cases with a 2 2 4 2 4
PSR model.
In the current work, we have shown that the PSR model
significantly
underpredicts observed fuel gas
cooled (diluted) fuel lean CO/H
2
concentrations
in
and C H cases. 2 4
B) Coalescence-Dispersion The et.al. the
first c-d model of the TJSC was developed by (1985).
reaction
cells,
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
not
of
elements,
up or
The population balance of
Monte-Carlo
technique.
from numerical oscillations and a large
tional load, even for the relatively small CO/H could
Pantelides
2
predict conversions in excess of PSR
This
computa-
reaction set. 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
combustion.
2
fluctuations
This
model did not produce Also,
and so no PDF's.
under fuel rich conditions.
temperature
the model became
unstable
As above, this c-d model also became
computationally ponderous for the simple CO/H ability
any
2
set.
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 accounted
for
conditions,
2
computational
line.
macroscopic
combustion.
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 C H (Figure 7-14). 2 4 In
the
current
environment model. jet with
project,
we have developed
a
new
mu1ti-
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 GuidinE Observations A number of TJSC experimental observations from this
project
and others were found to be important in developing the new mu1tienvironment model.
They are as follows:
1) Greater conversions of CO and H2 than predicted for a
119
PSR
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
equimolar CO/H 3) with
2
lean
and
rich
combustion.
Effectively
PSR behavior for fuel rich
C H 2 4
combustion
the exception of higher concentrations of parent C H and O 2 4 2
than predicted
for a PSR.
4) Non-uniform temperature profile across the torus for rich C H runs, 2 4
with a temperature dip
fuel
of as much as 100 K along
the centerline. 5) Rayleigh temperature PDF's fuel
near the torus centerline
for
rich C H which do not indicate low temperature material 2 4
or
localized blowout. 6)
Effectively PSR behavior for hot (undiluted),
fuel
lean
C H combustion. 2 4 7) Flat temperature profile for fuel lean C H combustion. 2 4 8)
Non-uniform LIF profile across the torus in a
room
tem-
perature mixing study (Bar-Ziv, 1989). 9)
Rayleigh
temperature PDF's
near the
torus
centerline
indicating localized blowout for cool (diluted) TJSC combustion. 10)
Observed
concentrations
of CO
and
light
hydrocarbons
higher than PSR predictions for cooled, fuel lean C H combustion. 2 4 11) Observed concentrations of CO higher than PSR predictions for cooled, fuel lean CO/H
2
combustion.
New PFR (Jet Mixing) I PSR Hybrid Model A schematic of the PFR(JM)/PSR model is shown in Figure 8-1. 120
FEED
PFR
,....... Ij\
1[\
1[\
,..... EXIT
..,..... PSR Ir\
...
,l!
'v
FIGURE 8-1: Schematic for PFR(JM)/PSR model; idealized flow sketch
/
/ 1/
./ /
/.-
./
,,
,
/'
/
//
/'
, I
I '/ I
121
/ /
'
/
A rationalization for this model can be obtained by accompanying TJSC flow sketch. entrains surrounding
examining the
The feed jet enters the torus
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
accounting
residual jet material entrained by the next jet. tent
with a number of observations:
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 which
new hybrid model uses an original overall driver program
combines the plug flow (or batch) CHEMKIN / LSODE
tion package of Kee et. borg et.
al.
(1986).
al.
(1980) with the PSR package of Glar-
The plug flow equations have been modified
to account for classical turbulent jet mixing, development
of
integra-
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
C /C hydrocarbon oxidation and 2 l
the
are
earlier.
the The
accompanying
species thermodynamic properties are listed respectively in Tables A-I 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 TIC
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
mechanism is about 5 minutes on the Room 66-125 MicroVax. considerably larger C H mechanism, 2 4
2
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 cases
3 cm .
is calculated by difference from 250
volume
studied,
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
second
governs
2
and
C H data set generated in 2 4
the
this
relative contributions of
PSR
the
study. and
The
PFR(JM)
outlet gases to the composition of the surrounding fluid which entrained
The ratio of the masses of
by the incoming jets.
is the
PFR(JM) outlet and PSR contributions is taken as
mass ratio Rl - f
*
rhopfr
*
vpfr /
(vpsr
*
where rhopfr - mass density of PFR(JM) outlet gas, volume, the
(8-1)
rhopsr)
vpfr - PFR(JM)
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
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.
gas
sample drawn into the probe.
sampling outlet
the
Best results were obtained
PSR gas and a small contribution from
the
gas to account for the large amounts of unburned
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
where g - the third parameter, cases.
*
vpfr / (vpsr
*
(8-2)
rhopsr)
which was set equal to 1.0 for all The mass ratio R2
The remaining terms are defined above.
is typically about 0.1. Results of New Hybrid Model The and
hybrid model results are presented for individual
cases
compared to the experimentally observed concentrations.
PFR(JM) volume (as % of total)
The
and outlet temperature are listed.
For comparison, the PSR and PSR+PQ values are repeated. A) Oxidation of CO/H Table runs
8-1
only
presents the hybrid model results for
made in this study.
PFR(JM)/PSR+PQ the
2
observed 50
For the hot (undiluted) case
results for H2 and CO are in good concentrations.
K lower than the PSR
the
CO/H
#5,
agreement
The PFR(JM) outlet temperature temperature. 125
Rapid
ignition
2
the with is and
TABLE 8-1 TJSC Oxidation of Fuel Lean CO/H /Air Mixtures 2 Case Number: Equivalence Ratio:
5
6
7
0.507
0.507
1.620
1640
1300
1760
7.9
6.7
8.3
0.0
0.30
0.20
1588
1169
1719
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
85
275
T/C Temperature (K):$ Residence Time (msec): Dil.N
2
#
flow/total flow:@
PFR(JM) Outlet Temp. (K) :
&
PFR(JM) Vol. (% of total):
&
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: Corresponding PDF Figure Number: Decon. PDF rms flue. (K):
*
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
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. The
rapid ignition in this case,
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
more
PSR+PQ.
PSR
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,
low
These data
suggesting localized blowout.
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 O , 2 not
available
for
PFR(JM)/PSR+PQ the
the
model
rich
CO/H2
run
#7.
However,
offers a slightly improved prediction
CO and H2 concentrations.
The PFR(JM) outlet temperature
only 40 K below the PSR value. rected
the limiting reagent, was
This is consistent with the
TIC trace of Figure 7-5 does not show any temperature
the for is cordip
in the center, as with rich C H . 2 4 B) Oxidation of C H 2 4 Consider
first the sequence of cases (#8 --> #13)
for
fuel
lean C H . Results with the hybrid model are presented in Table 82 4 2.
Figures
8-2
and 8-3 summarize the trends for
127
observed
and
TABLE 8-2 TJSC Oxidation of Fuel Lean C H /Air Mixtures 2 4 Case Number: Equivalence Ratio: T/C Temperature (K):$ Residence Time (msec): Dil.N
2
#
flow/total f1ow:@
& PFR(JM) Outlet Temp. (K):
PFR(JM) Vol. (% of total):
&
8
9
10
0.538
0.538
0.540
1670
1590
1530
6.6
6.4
6.3
0.0
0.08
0.13
1548
1432
1141
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
0.2 0.6 0.2 1.7 0.1
1.7 0.9 0.5 3.8 17.3
0.1
O. O. O.
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:
O. O. O.
C H (ppm) 2 6 Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
O. O. O. O. O.
O. O. O. O.
3.9 0.2
C H (ppm) 2 4 Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
0.3 31.5
0.1 37.5
0.1 43.4
O. O. O.
O. O. O.
1015. 2.1
128
O.
TABLE 8-2 continued
o.
o.
1.0
1.0
Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
o. o. o.
o. o. o.
Corresponding PDF Figure Number:
9A
9B
Decon. PDF rms f1uc. (K):
85
115
Case Number:
11
12
13
Equivalence Ratio:
0.540
0.537
0.543
T/C Temperature (K):$
1480
1440
1400
Residence Time (msec):#
6.2
6.1
6.2
Di1.N
0.16
0.19
0.21
2
flow/total flow:
0.1 0.9
o.
1.0
o.
PFR(JM) Outlet Temp (K):
1097
1067
1036
PFR(JM) Vo1.(% 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
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 H (ppm) 2 6 Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
7.0
1.0
1.3
o. o.
o. o.
o. o.
3.7 1.4
3.5 5.9
3.3 16.2
8.5 49.8 1053. 23.2
103. 55.9 0.2 1053. 110.
101. 64.2 0.6 1074. 274.
6.1 0.8
10.6 0.8
14.8 0.8
1.0 0.3
1.0 1.5
1.0 3.0
C H (ppm) 2 4 Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
o.
C H (ppm) 2 2 Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
o.
o.
o.
Corresponding PDF Figure Number:
9C
9D
Decon. PDF rms flue. (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 #
110
FIGURE 8-2: CO concentrations as a function of dilution for fuel lean C2H4 (qp - 0.54): observed, PSR+PQ, PFR{JM)/PSR+PQ
0.8
I
/
~
o
0.7
"""' ~ CD 0
E
0.6
'-"
/v
0
z
.-0«
0.5
n::
t-
Z W
u
Z 0
0.4
I
0.3
~
/
_D
U
0
u ~
0.2
o []
0.02
MEASURED
0.04
0.06
0.08
0.1
DILUENT N2 FLOW / + PSR+PQ
0.12
0.14
0.16
0.18
0.2
TOTAL FLOW PFR(JM)/PSR+PQ u)
FIGURE 8-3: CI+C2 hydrocarbon concentrations as dilution for fuel lean C2H4 (~-
a function of 0.54): observed,
PSR+PQ, PFR(JM)/PSR+PQ
350
"'"" E
I
,
300
0-
n.
~
U
z 0 u z 0
250
200
m 0:
tS
a
0:
150
Cl
~ N
u
+ ..... u
100
50
OIAl
o o
m-
1629
1037.31 26.2492 50
f-4
....m-I
t-
7
f-4
......J m
------------>
(0.19) [-0.11]
I
I I I
OR + OR
(0.71) [+0.023]
H
1---------------->
OR + 0
(0.52) [+0.10]*
o CR 2 4
----------------------------->
I I I OH I (0.17) I [+0.013] I \1/
(0.51) I [+0.035] I I R I (0.23) I [+0.015] I \1/
O
2
-------->
CR
3
+ RCa
I I I 0 I (0.80) I [+0.015] I \1/
OH
CR 0 + RCa
(0.87) [+0.006]
2
CH 20
I I I
--------> (0.49) [neg1]
HCO + H a 2
H I (0.38) I [-0.005]
I \1/
M
HCO
I /
---------> co
+ H
(0.60) [+0.10]
OH
co ----------> (0.99) [+0.34]
I
O2 I (0.19) I [-0.04]
I \//
*
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 f - kf/K where K - equilibrium constant. Therefore, a positiv~ TSC calculated from k means a positive TSC calculated from k . f r
1')9
FIGURE 9-5; Mechanistic pathways for C H /CH Cl oxidation 3 2 4 H, M
R
------------>
O2
H0 2
I (0.13) I [-0.12] I H I (0.53) I [+0.17]* I \11
1 1
---------->
OR + OH
(0.26) [+0.019]
Cl
1---------------------------> 1
Cl
1
1------------->
CIO + OH
(0.32) [+0.001]
OH + 0
HCl + O2
(0.30) [-0.016]
1
1
0
1
1--------->
Cl + O2
(0.93) [-0.005]
o ------------>
Cl CR
(0.21) [-0.004]
I I
3
--------->
+ HCO
(+0.96) [+0.0004]
I
-------------1
I [+0.009] I \11
I
I
H
1 1
(0.62) [negl]
1--------->
C H + HCl O2
1---------->
1---------> (0.18) [+0.002]
CH 0 + RCO
(0.93) [+0.007]
2
Cl
+ Cl
CH 0 + Cl 2
M
--------->
RCI + HCO
(0.81) [+0.004]
RCO 1 1 1 1
----------> 02
(0.20) [-0.07]
o
----------> (1.00) [+0.02]*
----------> (0.98) [+0.39]
H0 2 + CO
2 OH
OH HCl 1 1
OR
CO + H
(0.66) [+0.13]
1------------->
*
3
0
1
CO
CH
1
2 3
I I
I
I
o I (0.77) (0.61) [+0.025]
CH Cl + HCl 12
1 1
----------> (0.70) [-0.056] 0
1-------------> (0.19) [+0.017]
Temp. sens. coeff. calculated.for reverse reaction.
OR + Cl
160
TABLE 9-5 Disposition of OH in Case B'
Rxn.# 10. 51. 54. 55. 58. 62. 71. 132. 133. 134. 136. 137. 138. 139.
Normalized Fraction
Rate of Production (mo1e/cc-sec)
-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+0H CH20+0H-HCO+H20 CH20+0=HCO+OH HCO+OH=H20+CO HCO+O=CO+OH CO+OH=C02+H C2H4+0H=C2H3+H20 OH+H2=H20+H O+OH=02+H O+H2=OH+H OH+H02=H20+02 H+H02=20H O+H02=02+0H 20H=O+H20
NET RATE-OF-PRODUCTION (mo1e/cc-sec) == NET RATE-OF-CONSUMPTION (mo1e/cc-sec) -
9.77E-04 9.69E-04
Disposition of OH in Case A'
Rxn.# 10. 51. 55. 62. 71. 132. 133. 134. 137. 139. 166. l69. 185. 203.
Normalized Fraction
Rate of Production (mo1e/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. lIE-OS) (-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+0H CH20+0H==HCO+H20 HCO+OH=H20+CO CO+OH=C02+H C2H4+0H==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 (mo1e/cc-sec) NET RATE-OF-CONSUMPTION (mo1e/cc-sec) -
16 I
5.69E-04 5.66E-04
Figure even
9-5 shows this reaction to have a negative TSC though
consumed
it
is exothermic.
Only 33 % of the
by reaction with CO to form CO
tive TSC of +0.39.
In case B',
+ H,
2
however,
of
OH
-0.056
is
being
with a large posi-
the largest single
consumer (34 %) is reaction with CO to form CO
2
OH
+ 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 = CO
Notice, 2
+ 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
° atom
balance of
in
Table
9-6.
The
0 consumer (22 %) in case A' is reaction with HCl to form On the contrary, in case B', in the
OH + Cl with a TSC of +0.017. absence
shown
of chlorine,
with CH . 3
the largest
° consumer
(35 %)
is
reaction
Interestingly, note that the reaction OH + OH
produces 12 % of the
° in case B',
with a TSC of -0.014.
In case
A', however, where the OH concentration is 42 % lower than in case
B' (see Table 9-4), this reaction runs in reverse. % of the
It consumes 13
° in order to produce OH with a positive TSC of +0.02.
The
disposition
of H0 , 2
as shown in
Table
9-7,
further insight into the retarding effect of chlorine. the
two largest consumers (62 %) of H0
with Cl. seen
The reaction Cl + H0
on Figure 9-5.
in case A' are
Together, reactions
- HCl + 02 has a TSC of -0.016, as
In case A' ,
reacts with H to yield 2 OH, In case B',
2
2
provides
only 26 % of the available H02
which has a positive TSC of
+0.019.
without chlorine present, the reaction H + H02 - 2 OH
is the largest H02 consumer (71 %), with a positive TSC of +0.023. Table
9-4
shows
lower than in case
that the H0
2
concentration in case A' is
B' . 162
60
%
TABLE 9-6 Disposition of 0 in Case B'
Rxn.# 9. 54. 58. 59. 70. 82. 133. 134. 138. 139.
Normalized Fraction
Rate of Production (mo1e/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-Os) (-1.s8E-Os) (-1.s8E-Os) (-1.slE-04) (-6.77E-06) ( 4.3sE-04) (-4.4sE-Os) (-2.71E-Os) ( s.94E-OS)
CH3+0-CH20+H CH20+0-HCO+OH HCO+O-CO+OH HCO+O-C02+H C2H4+0-CH3+HCO C2H3+0-CH2CO+H O+OH-02+H O+H2=OH+H O+H02=02+0H 20H=O+H20
NET RATE-OF-PRODUCTION (mo1e/cc-sec) NET RATE-OF-CONSUMPTION (mo1e/cc-sec)
-
4.99E-04 4.91E-04
Disposition of 0 in Case A' Normalized Fraction
Rxn.# 9. S4. 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=-C02+H C2H4+0-CH3+HCO C2H3+0-CH2CO+H O+OH-02+H O+H2-0H+H O+H02-02+0H 20H-O+H20 O+HCL-OH+CL O+CLO-CL+o2 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 (mo1e/cc-sec) NET RATE-OF-CONSUMPTION (mo1e/cc-sec) -
16--3
Rate of Production (mo1e/cc-sec) (-s.44E-Os) (-4.17E-06) (-4.77E-06) (-4.77E-06) (-2.87E-Os) (-3.36E-06) ( 2.80E-04) (-1.SSE-Os) (-S.3SE-06) (-3.62E-Os) (-6.30E-Os) (-4.26E-Os) (-8.96E-06) 2.83E-04 2.80E-04
TABLE 9-7 Disposition of H0
Rxn.# 23. 60. 76. 135. 136. 137. 138. 147.
2
in Case B'
Normalized Fraction
Rate of Production (mo1e/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)
CH20H+02=CH20+H02 HCO+02-H02+CO C2H5+02-C2H4+H02 H+02+M=H02+M OH+H02=H20+02 H+H02=20H O+H02-02+0H H+HO 2.....H2+0 2
NET RATE-OF-PRODUCTION (mo1e/cc-sec) == NET RATE-OF-CONSUMPTION (mo1e/cc-sec) Disposition of H0
in Case A'
Normalized Fraction
Rxn.# 23. 60. 135. 136. 137. 138. 147. 202. 203.
2
CH20H+02-CH20+H02 HCO+02=H02+CO H+02+M=H02+M OH+H02=H20+02 H+H02 ..... 20H O+H02=02+0H H+H02=H2+02 HO2+CL==HCL+O2 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 (mo1e/cc-sec) ..... NET RATE-OF-CONSUMPTION (mo1e/cc-sec)...
164
2.86E-04 2.86E-04
Rate of Production (mo1e/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 CH 0. 2
The major producer (55 %) of Cl is
the key reaction OH + HCl = H 0 + Cl. 2 Cl
atom
As shown in Table 9-4, the
concentration is high compared to
the
other
important
radicals H, OH, 0, and H0 . 2 Finally, In
case A',
consider the H atom disposition shown in Table 9-9. reactions of H + Cl + M
the
=
HCl + M and H + HCl =
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 H2 (Westbrook, 1982; Chang et.al., 1987).
C) Interpretation We
have seen that CH Cl can inhibit the stability of a 3
fuel
lean C H / air flame in the TJSC. As discussed earlier, and shown 2 4 in
Table 9-5,
much of the required OH in case A' is lost by
reaction OH + HCl - H 0 + Cl, 2 is
the
The HCl
which has a negative TSC.
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 backrnixed reactor. Further evidence of the impact of chlorine on reducing OH these cases comes from the disposition of H02 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 O+HCL=OH+CL O+CLO-CL+02 OH+HCL=H20+CL CH3CL+CL-HCL+CH2CL CH2CL+H-CH3+CL CH2CL+O=CH20+CL CH20+CL=-HCO+HCL C2H4+CL=HCL+C2H3 H02+CL=HCL+02 H02+CL=CLO+OH
Normalized Fraction
Rate of Production (mo1ejcc-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) (-7.00E-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 (mo1ejcc-sec) NET RATE-OF-CONSUMPTION (mo1ejcc-sec) -
166
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+0H CH20+H-HCO+H2 HCO+M-H+CO+M HCO+H-CO+H2 HCO+O-C02+H CO+OH-C02+H C2H4+H=C2H3+H2 H+C2H4=C2H5 C2H5+H-2CH3 OH+H2=H20+H O+OH-02+H O+H2-0H+H H+02+M=H02+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.# 9. 10. 52. 56. 57. 62. 69. 132. . 133. 134. 135. 137. 152. 154. 183.
CH3+0-CH20+H CH20H+H-CH3+0H CH20+H-HCO+H2 HCO+M-H+CO+M HCO+H-CO+H2 CO+OH=-C02+H C2H4+H-C2H3+H2 OH+H2-H20+H O+OH-02+H O+H2 ...0H+H H+02+M-H02+M H+H02-20H H+CL+M-HCL+M CL+H2-HCL+H CH2CL+H-CH3+CL
Normalized Fraction
Rate of Production (mo1e/cc-sec)
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
( 5.44E-05) ( 6.96E-06) (-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 (mo1e/cc-sec) -
167
5.48E-04 5.46E-04
tion
of
H02 is especially important during the
low
temperature
"induction period" (Warnatz, 1984) in many flames. In case B', the largest source (42 %) of OH,
second
which
The case A' temperature PDF of
provides 45 %, is H + H02 - 2 OH. Figures
°
after H + 02 - OH +
9-lC,D,E (runs #7,8,9) clearly shows the existence of low
temperature primarily
gases
«
consumed
chain terminating,
1000 K).
by Cl.
In
A' ,
case
however,
is
The reaction Cl + H02 - HCl + 02
hence the negative TSC.
is
By depleting H0 , Cl 2
is inhibiting the burnout of CO, which is necessary for TJSC flame stability. At this point, in
we conclude that chlorine inhibits combustion
our backmixed system through direct and indirect depletion
the
of
CO , 2
OH radical which dominates the oxidation of CO to
Use of New Hybrid Model new PFR(JM)/PSR model was applied to cases #18 --> #19T,
The with
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.
closely for
both
It does better with the HC in case #18, The probe quench
calculation
HC species especially fast in the presence
of
appears
but to
chlorine.
This suggests that the chlorine kinetics may need refinement.
It
also
PQ
shows
dynamics.
the
need for a more quantitative description
of
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 C H /CH C1/Air Mixtures 3 2 4 Case Number: Di1.N
2
flow/total flow:
18
19
19T
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
0.609
PFR(JM) Outlet Temp (K):
1046
1087
1058
PFR(JM) Vo1.(% 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
Product Concentrations: * CO (mole %) Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ: CO
2
(mole %) Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
CH
4
?
?
5.09 5.17 4.77 4.84
5.49 5.56 5.07 5.15
5.70 5.80 5.34 5.42
(ppm) Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
52 2.3 2.6 4.5 50.4
26 0.5
O.
7
0
O. O.
O. O.
6.7
O.
2.2 2.3 4.8 66.3
C H (ppm) 2 6 Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
3.5 12.4
1.1 5.3
O. O. 3.9 11.4
170
TABLE 9-10 continued C H (ppm) 2 4 Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
591 60.1 0.3 1073. 204.
202 25.4 O. 883. O.
59.2 0.1 1238. 141.
51 0.9 O. 1.0 2.7
99 3.0 0.2 3.0 7.1
1.3 O. 1.5 3.2
C H (ppm) 2 2 Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ: CH Cl (ppm) 3 Measured:@ PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
43 2.9 O. 222. O.
C H Cl (ppm) 2 5 Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ: C1
2
?
1.8 1.8 118. 121.
(mole %)
Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
?
0.0 0.12 0.0 0.04
HCl (mole %) Measured: PSR: PSR+PQ: PFR(JM)/PSR: PFR(JM)/PSR+PQ:
?
0.80 0.81 0.78 0.97
* water free basis @ GC/FID response factor assumed same as for CH ; 4 no standard available at analysis time
CHAPTER 10 -- FINAL DISCUSSION, CONCLUSIONS, AND RECOMMENDATIONS
A
summary
learned sented
discussion
is
now presented of
what
in this project about the nature of the TJSC.
has
been
Also
pre-
are the preliminary conclusions on the effect of
on backmixed hydrocarbon combustion.
Finally,
a few
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
reacting CO/H
conditions. the
very
2
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
the
jet
This is evident with the
under high temperature (undiluted) fuel
lean
The very rapid consumption of H2 begins early (recall high
laminar flame speed
enhances the CO conversion.
for
H , 2
364
cm/sec),
and
Conversions of CO and H2 greater than
predicted by a PSR model result. The slower
situation for C H is somewhat different because of 2 4 reactivity (laminar flame speed of 78 cm/sec).
temperature,
fuel
lean operation,
the
For a high
the C H reacts to CO in 2 4
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 H . 2 4
especially with
There is a correlation between large Rayleigh
fluctuations,
the
appearance
of
171
bursts
of
low
temperature temperature
material,
and
hydrocarbons not
the experimental observation of levels of in excess of PSR predictions.
available
entraining
CO
If sufficient heat is
in the recycled gas to initiate reactions
jet
as it breaks up,
and
then the potential
in
the
exists
for
localized blowout and excess levels of unburned fuel gas. An
important conclusion of this project is
that,
for
high
temperature stable operations, the TJSC flame is distributed. narrow
PDF's
(deconvoluted)
generated
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 C H combustion. 2 4
It
is
also true, to a good first approximation, for fuel lean CO/H . 2 The
TJSC
combustion. central
essentially
rich
C H 2 4
There is no localized blowout in the axial core.
temperature
affect
behaves as a PSR for fuel
dip observed in T/C traces appears
parent C H and 02 concentrations due to partial 2 4
The
to
only
sampling
from this zone. One the
of
impact
the most striking observations made in this work of the probe quench (PQ) calculation
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
CH Cl 3
on
fuel
lean
stability became evident at lower temperatures.
C H 2 4
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 backrnixing. 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
water
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
temperature
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 backrnixed combustion, it is recommended that accurate
CO
Measurements
2
measurements indicate
be
made
with
and
without
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 HC1.
173
is
This
impor-
tant finding would be greatly supported by accurate CO
2
data.
In
addition, the CH CI mechanism should be refined and experimentally 3 verified
in well defined kinetic experiments.
expanded to accomodate fuel rich chemistry. performed
under
such
conditions
to
It should also be
Experiments should be
determine
the
effect
of
chlorine here. From operated
the point of view of an experimental
kineticist,
in the absence of local instabilities,
as a good
approximation
the TJSC can be taken to be a PSR within
when first
all
the
other uncertainties of the experimental work, especially the probe quench,
for all the fuels studied in this project.
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. H ) when observed conversions incrementally exceed PSR 2 predictions.
174
REFERENCES Bar-Ziv, E., personal communication (1989). Benson, S.W., Thermochemical Kinetics, Sons, New York (1976).
2nd.
ed.,
John Wiley &
Chang, W.D., Karra, S.B., and Senkan, S.M., Combustion and Flame, Vol. 69, p.113 (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., Grear, 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. Ill, The Combustion Institute, Pittsburgh, PA (1965). Kee, R.J., Miller, J.A., and Jefferson, T.H., Sandia Report SAND80-8003, Sandia National Laboratories, Albuquerque, NM (1980). 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). Lam, F.W., Ph.D. Thesis, Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA (1988). 175
Levenspiel, 0., Chemical Reaction New York (1972).
En~ineerin~,
2nd ed., John Wiley
& Sons,
Longwell, J.P. and Bar-Ziv, E., Combustion and Flame, Vol. 78, p. 99 (1989). Miller, J.A. and Bowman, C.T., Science (1989).
Pro~ress
Muller-Dethlefs, K. and Weinberg, (Int.) on Combustion, p. 985, Pittsburgh, PA (1978).
in
Ener~y
and Combustion
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 En~ineerin~ Science, Vol. 40, No.3, p. 375 (1985). Raj an, 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 Optical Society America, Vol. 58, No.9, p. 1260 (1968).
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., the IEEE, Vol. 69, No.4, p. 432 (1981).
Proceedin~s
of
Sun, W. S., Ph.D. Thesis, Department of Chemical Engineering, 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 Technolo~y, Vol. 36, p. 123 (1984). Vaughn, C.B., Ph.D. Thesis, Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA (1988).
176
Warnatz, J., Combustion Chemistry, W.C.Gardiner, Jr., ed., p. 197, Springer-Verlag, New York (1984). Weiss, M.A., Lang, R.J., and Longwell, J.P., Industrial Engineering Chemistry, Vol. 50, No.2, p. 257 (1958).
and
Westbrook, C.K., Nineteenth Symposium (Int.) on Combustion, 127, The Combustion Institute, Pittsburgh, PA (1982).
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:
*
appendices
which
APPENDIX 1 -- 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
APPENDIX 5
JET MIXING EQUATIONS FOR CHEMKIN ELEMENTARY REACTION MECHANISMS
+ Table A-I: 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 -- EXPERIMENTAL AND COMPUTER PROCEDURES
This
section
contains detailed procedures for operation
of
the combustor, laser, optics, and electronics.
Various dedicated
computer
computer
programs
Elephant")
for
use
on the
IBM
9001
("White
during the experiments and subsequent data workup
also described.
are
Therefore, 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) at
spray 40 psig. Check
for
Turn
on main COOLING WATER pump.
about
20
Set
psig.
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
thermocouple
flow
of MAIN FUEL.
Look for
large
reading accompanied by a loud "pop" from
jump the
in
TJSC.
Turn off pilot H . 2 (6) For C H , 2 4 For
CO/H , 2
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
°c
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, optimize ("tweek-up") each detector
signal
using the various optical mount
collection optics train. the this
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
calibration
the variation of the net mean signal (Sd) with
room temperature.
Any observed offset
adjustment of the subtraction factor ~.
J[
is answered with an
This procedure uses the
All "White Elephant"
program NS3TBLS.BAS (Appendix 6).
pressure
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) channel 2,
The
laser
intensity monitor signal
is
input
to
with the Rayleigh signal Sd input into both channels 3
and 4. Turn
(5)
on vacuum pump,
and set pressure
in
vessel
using control valve. Turn
(6)
signals
on laser and observe laser intensity Using GATE MONITOR OUTPUTS on
on oscilloscope.
and
Sd
boxcar,
check for correct placement of electronic sampling gates.
offset
(7)
Obtain
(8)
Collect
Sd vs.
pressure.
Plot up and notice
any
1:.
eously.
Record
laser intensity monitor
signal
simultan-
mean monitor signal and PDF of 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 vs.
coordinates.
Record
jt
steps 7,
8,
and repeat steps 7 and 8. and 9 until
offset
~
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 Prior
to
collection
ignition,
the following steps
are
required
of Rayleigh scattering data during combustion.
recommended
that this effort not be pursued until
an
for 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 values
obtained at I atm in the Calibration.
If not,
those
check for
proper optical alignment, laser power, boxcar operation, etc. Load program NS3DBLS.BAS (Appendix 6),
(4)
ensuring no
change in boxcar parameter from desired values. (5) Collect and store reference (N
2
at room temperature,
I 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 wait for steady state (see thermocouple time trace). mended burn
It is recom-
that the Rayleigh data collection begin with a (equivalence ratio about 0.5) as a base point.
fuel When
lean ready,
carefully turn on laser and bring to desired power level. Observe
laser
Observe
oscope. reasonable
as
intensity monitor and Sd signals the
the
it and
is the
If the combustion Sd is low (absolute value),
the probable cause is dust / condensation on the viewing
osci11-
mean Sd and check if
compared to the thermocouple temperature
reference mean Sd. then
approximate
on
window.
If high,
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
ca1ibra-
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 N2 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
calculated.
program (Appendix 6)
represents the particular
addition to feed flow rates / composition, an
given
Use
the
the
set
burned.
In
in
fuel
[see
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
Decent values for
heating value of the input fuel rate). numbers
can
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
Rayleigh
Sd
This
highly
signals
and performs the deconvolution.
recalled from disk.
to
use
interactive temperatures,
The signal data
The following information is
composition / temperature parameters [equation
system (shot) noise calibration parameters [equation
requested:
(4-11)];
(b)
(6-7)];
(c)
decent guess at the deconvoluted PDF; (d) minimum likely signal Sd or
maximum likely temperature.
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
energy level diagram is also included for each
QRRK
reaction
system.
The QRRK derived rate parameters are valid
one atmosphere pressure,
non-QRRK reactions.
ten).
=
A
*
n
T
*
for
N2 bath gas, and an approximate tempera-
range of 700 - 1600 K.
k
the this
An
form
for
and unimolecular QRRK calculations performed in
project.
ture
APPLICATIONS OF QRRK
Also listed are the sources for
In all cases,
the rate constants are in the
exp(-EjRT) for the forward direction (as
3 1 K. . .1 Un1ts are 1n mo es, cm , sec, k ca,
writ-
All reactions used
in this study are written as reversible for CHEMKIN.
186
the
187 INPUT PARAMETERS FOR UNIMOLECULAR QRRK C2H3 - [C 2H3 J k
A
-
products
*
E
1.2 E+12
1
#
a
**
source
41.6
a
- l56l/cm
b
W PARAMETERS
c O
sigma - 4.19 A
elk - 228. K
(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:
*
3
bimolecular: cm /mole-sec unimolecular: l/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr)
Reaction
A (cm3/ mole-sec)
n
5.62E+3l
-6.06
E (kcal /mole) 51.72
H"
H-'C=C'H 106.3
/1o.
H+C2 H2
100
>-
'-.?
Q::
70
60
W Z W
67.1
INPUT PARAMETERS FOR UNIMOLECULAR QRRK CH CO - [CH CO]# - products 2 2 A*
E
5.0 E+1S
78.3
k
1
a
**
source a
"'" l193/cm
b
LJ PARAMETERS
c O
sigma = 4.23 A
elk
314. K
(a) For reverse: A=SE12, Ea=O (estimate); 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:
*
3
bimolecular: cm /mole-sec unimolecular: l/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr)
Reaction CH CO=CH +CO 2 2
A (cm3/ mole-sec)
n
2.01E+3S
-6.68
188
E (kcal /mole) 82.99
66.1
60
w "'"
CH 2 +CO
.-J
0
L
..............
---1
50 40
-
'-9
0:::
w
K,
z w
-12.4
CHZCO -20
189
INPUT PARAMETERS FOR BIMOLECULAR QRRK H + C Hs == [C H ] 2 2 6
#
... products E ** a
A*
k
source
1
1.8 E+14
O.
a
-1
1.26 E+16
100.1
b
2
7.94 E+16
89.8
c
3
3.0 E+12
78.
d
- ls09/cm
e
W PARAMETERS
f
sigma..., 4.34 AO
elk == 247. K
(a) Al from thermodynamics and A-I; Ea=O for barrierless radical/radical combination. (b) A-I from Dean (1985); Ea=/\Hr-RTm. (c) Ea==/\Hr-RTm; A2 from Dean (1985). (d) A3=3*(ekTm/h)*exp(/\S */R) with Tm=lOOO K and /\S * -7.5 eu (transition state theory); Ea=/\Hr+4s (e) From "CPFIT" program and Cp data. (f) Estimated from critical properties for C2H6, which were estimated by Lydersen method Prausnitz, and Sherwood). UNITS:
3
* bimolecular: cm /mole-sec unimolecular: l/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+C2Hs-[C2H61o
s.18E+3s
-6.83
6.81
H+C H -2 CH 3 2 s
8.73E+14
-0.08
3.08
H+C2Hs-C2H4+H2
s.9sE+2s
-4.22
8.86
190
(Reid,
90 80 70·
H···H . .
60
~
H-C!!:C-H
HH
r-'\
w
50
---1
0 L
~
--1
40
-
30
19 0:: W
z
20
w
12.5 10
o -fa -20.0
CZH6 191
INPUT PARAMETERS FOR BIMOLECULAR QRRK CH
3
+ CH
k
3
A
= [C H ]
#
= products
2 6
*
E ** a
source
1
2.6 E+13
O.
a
-1
7.94 E+16
89.8
b
2
1.26 E+16
100.1
c
3
3.0 E+12
78.
d
l509/cm
e
LJ PARAMETERS
f
-=
O
sigma - 4.34 A
elk - 247. K
(a) Al from thermodynamics and A-I; Ea=O for barrierless radical/radical combination.
(b) A-I from Dean (1985); Ea=/\Hr-RTm. (c) Ea-/\Hr-RTm; A2 from Dean (1985).
* (d) A3-3*(ekTm!h)*exp(/\S */R) with Tm-lOOO 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:
3
* bimolecular: cm /mole-sec unimolecular: l/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr)
N2
760.
A (cm3/ mole-sec)
n
E (kcal /mole)
CH 3+CH 3-=[C 2H6 ]o
2.68E+29
-4.95
6.13
CH +CH -H+C H 3 3 2 5
8.89E+18
-1.70
16.85
CH3+CH3=C2H4+H2
3.20E+25
-4.17
13.19
Reaction
192
(Reid,
19~
80.1
8···H H-C!!:C-H
HH
>'J
CL
W
Z W
194 INPUT PARAMETERS FOR BIMOLECULAR QRRK #
H + C2H4 - [C 2H5 J - products k
A
E ** a
*
source
1
3.98 E+13
2.6
a
-1
3.63 E+13
38.9
b
- l526/cm
c
PARAMETERS
d
LJ
O
sigma - 4.34 A
elk - 247. K
(a) AI, Ea from Dean (1985). (b) k-l 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:
*
3
bimolecular: cm /mole-sec unimolecular: l/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr)
Reaction
70 60 r"'\
w
50
-l
0
~
......... -l
40
~
U
::x:: '-'
>~
30[
0:::
w
z
w
2°1
A (cm3/ mole-sec)
n
E (kcal /mole)
5.4lE+35
-6.78
11.70
(Reid,
19'; INPUT PARAMETERS FOR BIMOLECULAR QRRK H + CH 3 - [CH 4 J k
A
#
*
E ** a
source
1
2.62 E+14
O.
a
-1
1.0 E+16
105.1
b
- 1957/cm
c
LJ PARAMETERS
d O
sigma - 1.46 A (a) (b) (c) (d)
UNITS:
- products
*
elk - 151. K
k-1 from thermodynamics and k1. A-I, 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). 3
bimolecular: cm /mole-sec unimolecular: l/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr)
N2
760.
A (cm3/ mole-sec)
Reaction
7.09E+3l
H+CH -[CH4 J o 3
100
L.!J -.J
80
H+CH3
KI q[CH 4 ]-r~
0
KSCM)
......
~
~
'-' c::: w :z: w
40 20
a -17.9 -20
CH 4
(Reid,
INPUT PARAMETERS FOR BIMOLECULAR QRRK H + COCI - [HClCO]# - products A*
k
Ea **
source
1
1.0 E+14
O.
a
-1
3.4 E+15
86.8
b
2
5.6 E+13
38.
c
3
1.1 E+15
78.
d
- 1089/cm
e
LJ PARAMETERS
f O
sigma - 4.34 A
elk - 361. K
(a) Al appro Af for H+.CH2Cl; Ea=O due to radical/radical recombination with no barrier. (b) Reverse reaction (k_ ) from thermodynamics and AI. l (c) Ea from Setser and Lee (1985); A2 1000 K (transition state theory). (d) Ea=/\Hr-RTm; and A(rev).
=
A(rev) from NJIT group;
ekTmjh with Tm = 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:
*
3
bimolecular: cm /mole-sec unimolecular: l/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr)
N2
760.
A (cm3/ mole-sec)
n
E (kcal /mole)
3.l3E+19
-2.93
1.77
H+COCl-CO+HCl
3.54E+16
-0.79
1.06
H+COCl-HCO+C1
3.42E+09
1.15
-0.18
Reaction H+COCl-[HClCO]
0
196
50
48.1
0
Kr
~ HCLC6jT
H+ COCl
..J-
-I
K~
40
39.'3
HCO+ Cl 30 20
-40
-39.3
HClCO - 48.5
-SO
CO+HCl 197
INPUT PARAMETERS FOR BIMOLECULAR QRRK Cl + HCO - [HClCO]# - products A*
k
E ** a
source
1
1.0 E+13
O.
a
-1
1.1 E+15
78.
b
2
5.6 E+13
38.
c
... 1089/cm
d
lJ PARAMETERS
e O
sigma = 4.34 A
elk == 361. K
(a) Al from NJIT group; Ea=O due to radical/radical recombination with no barrier. (b) Reverse reaction (k_ ) from thermodynamics and AI. l (c) Ea from Setser and Lee (1985); A2 = ekTm/h with Tm 1000 K (transition state theory).
=
(d) From "CPFIT" program and Cp data. (e) Estimated from critical properties for HC1CO, estimated using Lydersen's Method (Reid, Prausnitz, and Sherwood). UNITS:
*
3
bimolecular: cm /mole-sec unimolecular: l/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr) 760.
Reaction C1+HCO=[HC1CO] Cl+HCO-=CO+HC1
o
E (kcal /mo1e)
A (cm3/ mole-sec)
n
6.42E+17
-2.67
1.41
1.4lE+14
-0.35
0.51
198
so K,
40
39.3
HCO+ CL
~
~ [HCLCof'· -I
30
-3-
"-.? 0::
W
z. w
-20
209
INPUT PARAMETERS FOR BIMOLECULAR QRRK H0
2
+ .CH Cl - [CH ClOOH] 2 2
k
A
#
*
- products E
a
**
source
1
1.0 E+13
O.
a
-1
5.6 E+16
65.0
b
2
2.6 E+15
41.4
c
= 787/cm
d
LJ PARAMETERS
e O
elk - 598. cal
sigma - 4.90 A
(a) Al from NJIT group; Ea = 0 from barrier-less radical / radical recombination. (b) Reverse reaction (k_ ) from thermodynamics and k . l l (c) A-2 appro lE13 from NJIT group; Ea-2 barrier-less radical/radical recombination; thermodynamics and k-2.
o for k2 from
(d) From "CPFIT" program and Cp data. (e) Estimated from critical properties for CH2ClOOH, which were estimated by Lydersen method (Reid, Prausnitz, and Sherwood). UNITS:
*
3
bimolecular: cm /mole-sec unimolecular: l/sec
**
kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr)
A (cm3/ mole-sec)
Reaction
760. H0 +.CH Cl=[CH ClOOH]o 2 2 2 H0 +·CH Cl=CH ClO.+OH 2 2 2
210
n
E (kcal /mole)
9.88E+28
-5.97
3.56
5.l9E+14
-0.51
0.84
~ [CHZCLOOH] "* 'CHzCL + HO 2 -I ~K2 3Z.0
9.0----
CHZCLO· +OH >\..9 er: w
z
w - 32.4
CHzCLOOH -40
211
INPUT PARAMETERS FOR BIMOLECULAR QRRK # O + .CH 2Cl ... [CH ClOO.] - products 2 2 E ** A* a
k
source
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+ll
19.6
e
5
1.2 E+13
2.0
f
= 800/cm
g
LJ PARAMETERS
h O
sigma = 4.90 A
elk
=
598. K
(a) Al appro 0.5*Af for 02+.CC (Af=3E12) from Bozzelli and Dean (1989); Ea appro 0.5+Ea for 0 + CH2Cl. (b) Reverse reaction (k_ ) from thermodynamics and k . l l (c) A-2 appro 0.5*Af from 0+CH30. (Af-5E13) from Dean and Westmoreland (1987); A2 from A-2 and thermodynamics; Ef=/\Hr-RTm. (d) A4=1*(ekTmjh)*exp(/\S */R) with Tm=lOOOK and /\S *--4eu (transition state theory); Ea=18+7+6.5 (for ring strain+abstraction+/\Hr). (e) Reverse reaction (k_ ) from thermodynamics and k . 4 4 (f) Ea Ea for .CH200H --> CH20+0H from Dean and Westmoreland (1987); A-5 appro 0.5 * Af for OH+CH20. (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:
3
* bimolecular: cm /mole-sec unimolecular: l/sec
212
** kcal/mole
CALCULATED APPARENT FORYARD REACTION RATE CONSTANTS Bath P Gas (torr)
N2
A (cm3/ mole-sec)
n
E (kcal /mole)
4.59E+36
-8.22
6.73
°2+·CH2Cl-CH2ClO.+O
8.08E-IO
6.07
14.87
°2+·CH2Cl-.CH200Cl
1.20E+16
-2.96
8.56
°2+·CH2Cl-CH20+ClO
8.46E+13
-1.03
8.18
Reaction
760. °2+·CH2Cl-[CH2ClOO·]o
CHZCLO· -f- 0
60
61.7
K4
/K-4
40 W '" -.J
~ 30
~
~
·CH 2 CL + 0 2 29.1
-.J
«
20
h z
50
K,
[
~-I CHZCLOO~ f
1.0
"*
1
K [M] AS
'-'
>-
1..9 10
11.9
0:: W Z
W 0
3.7
CLO+CHZO -3.5
-10
P.E. DIAGRAM: -CH 2 CL +0 2
213
INPUT PARAMETERS FOR BIMOLECULAR QRRK CH3 + .CH 2Cl - [C 2HSCl] k
A
- Products Ea **
*
source
1
1.6 E+13
O.
a
-1
1.3 E+17
90.4
b
2
6.4 E+12
52.8
c
3
2.2 E+lS
83.S
d
= 108S/cm
e
PARAMETERS
f
LJ
sigma ... 4.84 A
elk - 379. K
(a)
A (forward) from 0.5 * high pressure A for H + from Allara and Shaw ( ).
(b)
Reverse reaction (k_ ) from thermodynamics l (forward).
(c)
A2=3*(ekTmjh)*exp(/\S*/R) with /\S*=-6.6eu (transition state theory); Ea=/\H -RTm with Tm=lOOOK Ea - /\ H -RTm; A (forwardJ from thermo and A (revr erse) ... h1gh pressure A factor for CH + 2-C H from 3 3 7 Allara and Shaw (1980). From "CPFIT" program and C data. Calculated from critical P properties for C H Cl 2 s (Reid, Prausnitz, and Sherwood).
(d)
(e) (f)
UNITS:
#
3
* bimolecular: cm /mole-sec unimolecular: l/sec
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr)
Reaction
A (cm3/ mole-sec)
n
E (kcal /mole)
-6.7S
8.08
CH +·CH Cl-C H +HCl 3 2 4 2
4.80E+24
-3.44
7.69
CH +·CH Cl-C HS+Cl 2 3 2
2.04E+19
-1.81
10.34
214
and
CH 4 9 A
70 60 50
40 H..·CL
H-~~C-H
30
H --=-..:R_-=26.0
20 10
r'\
W
-.J
0 L
O.
'"-.J
-I 0
- 9.5
>-
C2 H4 +HCL
'-9
. cc
-2 0
- 30
l:JJ
z w
-26,8
C2 HSCL 21t;
INPUT PARAMETERS FOR BIMOLECULAR QRRK
o
+ .CH Cl = [CH ClO.] 2 2
k
A
#
- products
*
E
**
source
a
1
2.0 E+13
0.5
a
-1
1.2 E+16
84.5
b
2
3.0 E+13
7.0
c
= l247/cm
d
LJ PARAMETERS
e
sigma - 4.61 AO
elk - 535. K
(a) Al appro 0.35*Af for O+CH3; Ea from Ea for 0 + (Dean and Westmoreland, IJCK, 1987).
CH3
(b) Reverse reaction (k_ ) from thermodynamics and AI. l (c) Use CCCC. ---> C2H5+C=C as analagous reaction (Af-2E13, Ea-/\Hr+7) from Dean (JPC, 1985). Take A2-1.5*Af; Ea appro /\Hr+7. (d) From "CPFIT" program and Cp data. (e) Estimated from critical properties for CH2ClOH, which were estimated by Lydersen method (Reid, Prausnitz, and Sherwood). UNITS:
3
* bimolecular: cm /mole-sec unimo1ecular: l/sec
** kca1/mo1e
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr) N2
760.
A (cm3/ mole-sec)
n
E (kcal /mole)
O+.CH 2Cl-[CH 2C10·]o
2.55E+15
-2.02
1.23
O+.CH Cl=CH 0+Cl 2 2
8.3lE+13
-0.18
0.80
Reaction
216
90.
80 70
KS[M]
60
"--1w
50
"u
40
'-'
30
0 L
-1
>-
19 0:: W
z w
20 10
z.z
o
1.1
-10
PE. DIAGRAM: -CHzCL + 0 217
INPUT PARAMETERS FOR BIMOLECULAR QRRK OH + .CH Cl 2
-=
[CH ClOH] 2
#
- products
A*
k
E ** a
source
1
1.6 E+13
O.
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
l200/cm
e
LJ PARAMETERS
f
=
sigma
-=
O
e/k"", 535. K
4.61 A
(a) Al appro same as Af for CH2Cl+CH3; Ea=O for barrierless radical/radical combination. (b) Reverse reaction (k_ ) from thermodynamics and k . l l (c) A4=1*(ekTm/h)*exp(/\S */R) with Tm-lOaa 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=lOOO K.
A-3;
(e) From "CPFIT" program and Cp data. (f) Estimated from critical properties for CH2ClOH, which were estimated by Lydersen method (Reid, Prausnitz, and Sherwood). UNITS:
3
* bimolecular: cm /mole-sec unimolecular: l/sec
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS
N2
E (kcal /mole)
A (cm3/ mole-sec)
n
3.l5E+28
-5.35
4.92
OH+.CH Cl-=CH O+HCl 2 2
4.l0E+2l
-2.57
3.74
OH+.CH Cl=.CH OH+Cl 2 2
9.24E+ll
0.38
2.97
Bath P Gas (torr)
Reaction
760. OH+.CH Cl=[CH ClOHJ0 2 2
218
*K
38.6
·CH 2 CL +OH
~I
[CH 2CLOHJ
*
~
29.4
·CH 2 0H +CL
>\..9
0:::
-20
zW w
-40 -49.8
-52.4
CH 2 CLOH
21C)
HCL+CH 2 0
INPUT PARAMETERS FOR BIMOLECULAR QRRK CIO + C H 2 4 k
#
[.CH CH 0Cl] - products 2 2 * A 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
U
-=
731/cm
f
PARAMETERS
g O
sigma -= 5.64 A
elk
-=
592. K
(a) A1 appro 0.5*Af for OH+C2H4 (Af=4E12,Ea=2 Benson, 1976); Ea appro Ea for OH+C2H4.
from
(b) Reverse reaction (k_ ) from thermodynamics and k . l 1
. Tm-lOOO K and /\S-* (c) A4-l*(ekTm!h)*exp(/\S */R) w1th 7.5 eu (transition state theory); Ea-16+7 (for ring strain+abstraction). (d) Reverse reaction (k_ ) from thermodynamics and k . 4 4 (e) Ea5 appro Ea, A-s appro Af for CH3+C2H4-->1-.C3H7H (Af-1.2E11, Ea-7.7 from Allara and Shaw 1980); ks from thermodynamics and k-5. (f) From "CPFIT" program and Cp data. (g) Estimated from critical properties for C2HsOCl, which were estimated by Lydersen method (Reid, Prausnitz, and Sherwood). UNITS:
3
* bimolecular: cm /mole-sec unimolecular: l/sec
220
** kcal/mole
CALCULATED APPARENT FORWARD REACTION RATE CONSTANTS Bath P Gas (torr)
N2
A (cm3/ mole-sec)
Reaction
n
E (kcal /mole)
760. C1O+C H -[·CH CH OC1]o 2 2 2 4
1.7SE+32
-6.32
7.90
C1O+C H4-[CH 2C1CH 2O·]o 2
S.40E+24
-4.99
8.87
C1O+C H -·CH Cl+CH O 2 2 2 4
9.26E+18
-1.98
8.43
40 30
W '" -1
0 L:
20
-..... -1
10
>-
1..9
0
CLI 0:,
CHAN #3 - #4" GOTO 1070 FLAG-3 GOSUB 2500 \ PRINT#2,"BS 4" \ WAIT 1 \ GOSUB 3500 PRINT "BASELINE SUBTRACTION ACTIVE --> CHAN #3 - #4"
1055 1057 1070 1071 1072 1074 1090 1096 1098 1100 1105 1110 1115 1120 1121 1125 1145 1150 1155 1160 1165 1170 1175 1180 1185 1190 1220 1222 1225 1230 1250 1255 1260 1262 1270 1300 1305 1310 1313 1315 1320 1325 1330 1332 1333 1334 1335 134"2 1350 1400 1401 1402 1403 1405 1410 1412 1420 1430 1432 1434
GOTO 1070 PRINT INPUT INPUT INPUT
"NOM CURVE LENGTH (CL .. ) (MAX-1024): " LINE C$ \ GOSUB 3000 "RAYL CHANNELS #3 & #4 SENS (VOLTS) - ";RSEN "LASER CHANNEL SENSITIVITY (VOLTS) - ";LSEN
INPUT "QUIT(Y/N) OR RESTART(ST)?";J$ IF J$-"Y" GOTO 8000 IF J$-"ST" GOTO 600 REM*************EXPERIMENTAL DATA ACQUISITION************ MAT A - ZER \ MAT RAY - ZER \ MAT LAS - ZER MAT PLT - ZER \ MAT VLT - ZER CLS PRINT GOSUB PRINT GOSUB PRINT GOSUB PRINT GOSUB
"CLEAR DATA BUFFER" \ BXC-1 2500 \ PRINT#2,"ZAP" \ WAIT 5 "BEGIN COLLECTING DATA" 2500 \ PRINT#2,"C" \ WAIT 1 \ "BEGIN DATA TRANSFER TO IBM" 2500 \ PRINT#2,"DPS" \ WAIT 1 "DATA COLLECTION AND TRANSFER 6000 \ PRINT "RSP - ",RSP
\ GOSUB 3500 GOSUB 3500 \ GOSUB 3500 COMPLETE" \ BXC-O
IF FLAG-1 GOTO 2000 IF FLAG-2 GO TO 1250 IF FLAG-3 THEN GOTO 1400 ELSE GOTO 1096 REM***CHECK BASELINE SBUTRACTION ZERO*********** FOR I-I TO (RSP-20) \ A(I)-A(I+20) \ NEXT I RSP-RSP-20 \ RES-RSP/2 SMNLR-O \ S~O FOR 1-1 TO RSP IF 2*INT(I/2)-I GOTO 1315 LAS-A(I) \ S~SMNLL+LAS \ GOTO 1320 RAY-A(I) \ SMNLR-SMNLR+RAY NEXT I RBK-SMNLRjRES/32768*RSEN*1000 LBK-SMNLLjRES/32768*LSEN*1000 PRINT "AVER NON-LASER RAYL BCKGR (mV) - ",RBK PRINT "AVER NON-LASER LAS BCKGR (mV) - ",LBK GOTO 1096 REM****CORRECT FOR LASER INTENSITY FLUCTUATION**** REM*********INTERACTIVE DATA EXAMINATION********** REM********CALCULATE AVERAGE RAYL SIGNAL********** REM********GENERATE RAYLEIGH SIGNAL PDF************ FOR I-1 TO (RSP-20) \ A(I)-A(I+20) \ NEXT I RSP-RSP-20 \ RES-RSP/2 FOR 1-1 TO RSP IF 2*INT(I/2)-I THEN RAYT(I/2)-A(I) ELSE LAS«I+1)/2)-A(I) NEXT I
2';6
1440 1450 1452 1454 1456 1458 1520 1522 1550 1552 1554 1556 1560 1570 1575 1580 1590 1600 1605 1610 1615 1620 1630 1640 1645 1650 1660 1670 1672 1680 1700 1705 1710 1900 2000 2005 2010 2012 2015 2020 2022 2024 2026 2028 2030 2040 2042 204q 2050 2052 2054 2060 2070 2100 2500 2520 2530 2540 2550 2560
SUMlAS-O FOR K-1 TO RES SUMLAS-SUMLAS+LAS (K) NEXT K AVLAS-SUMLAS/RES LASSR-1000*AVLAS*LSEN/32768 INPUT "CORRECT FOR LASER FLUCTUATIONS (Y/N)?";CLF$ IF CLF$-"Y" GOTO 1570 FOR I-I TO RES \ RAY(I)-RAYT(I) \ NEXT I GOTO 1600 FOR I-I TO RES FLUC-LAS(I)/AVLAS \ RAY(I)-RAYT(I)/FLUC NEXT I GOSUB 6100 \ PRINT "RAYL SIGNAL DATA" INPUT "WANT INTERACTIVE DATA REVIEW (Y/N)?";IDR$ IF IDR$-"N" GOTO 1620 GOSUB 6500 \ GOTO 1600 PRINT "# OF DATA POINTS USED - ",RES SUMRAY-O FOR I-I TO RES \ SUMRAY-SUMRAY+RAY(I) \ NEXT I AVRAY-SUMRAY/RES \ RAYMV-AVRAY*1000*RSEN/32768 PRINT "AVER LAS MON SIGNAL (mV) - ",LASSR PRINT "AVER RAYL (#3-#4) SIGNAL (mV) - ",RAYMV INPUT "WANT PDF (Y/N)?";PDF$ IF PDF$-"N" GOTO 8000 GOTO 6700 REM******SET INDIVIDUAL CHANNEL ZEROS************** FOR 1-1 TO (RSP-30) \ A(I)-A(I+30) \ NEXT I RSP-RSP-30 \ RES-RSP/3 SMLAS-O \ SMRA-O \ SMRB-O FOR J-1 TO RES LAS-A(3*J-2) \ RAYA-A(3*J-l) \ RAYB-A(3*J) SMLAS-SMLAS+LAS \ SMRA-SMRA+RAYA \ SMRB-SMRB+RAYB NEXT J AVRA-SMRAjRES*1000*RSEN/32768 AVLAS-SMLAS/RES*1000*LSEN/32768 AVRB-SMRB/RES*1000*RSEN/32768 PRINT "AVER CHAN #2 SIGNAL (mV) - ",AVLAS PRINT "AVER CHAN #3 SIGNAL (mV) - ",AVRA PRINT "AVER CHAN #4 SIGNAL (mV) - ",AVRB GOTO 1096 REM**CHECK IF COMMAND DONE BY CHECKING VALUE OF BIT 0** REM**DO THIS BY CHECKING IF FPK%(8) IS ODD OR EVEN***** REM*****************TAKE SERIAL POLL******************* GOSUB 6000 IF FPK%(8)-2*INT(FPK%(8)/2) GOTO 2540 RETURN
2S7
2570 3000 3005 3010 3015 3020 3025 3030 3035 3040 3050 3060 3070 3080 3090 3100 3110 3120 3125 3500 3505 3510 3520 3530 3540 3550 4000 4010 4020 4030 4040 4050 4060 4070 4080 4090 4110 4120 5000 5005 5020 5030 5040 5050 5060 5070 5072 5080 5200 6000 6005 6010 6020 6030 6035 6040 6050 6060 6100 6105
REM***********DRIVER SUBROUTINE #1********************* RSP-O \ NX-l GOSUB 3050 GOSUB 4000 GOSUB 5000 RETURN REM***************"OUTPUT" SUBROUTINE****************** REM**CHECK IF COMMAND DONE BY CHECKING VALUE OF BIT 0** REM**DO THIS BY CHECKING IF FPK%(8) IS ODD OR EVEN***** REM*****************TAKE SERIAL POLL******************* GOSUB 6000 IF FPK%(8)-2*INT(FPK%(8)/2) GOTO 3080 PRINT#2, C$ \ WAIT 1 RETURN REM*************DRIVER SUBROUTINE #2******************* RSP-O \ NX-2 GOSUB 4000 GOSUB 5000 RETURN REM***************"ENTER" SUBROUTINE******************* REM*****CHECK FOR RESPONSES FROM BOXCAR**************** REM******************TAKE SERIAL POLL****************** GOSUB 6000 REM**CHECK FOR RESPONSE BY CHECKING VALUE OF BIT 7***** REM**DO THIS BY CHECKING IF FPK%(8) IS > 128*********** IF FPK%(8) 32 THEN Q-32 ELSE Q-RSP FOR J-1 TO Q \ PRINT J,A(J) \ NEXT J RETURN REM**************SERIAL POLL SUBROUTINE**************** CALL SYSFUNC(2,FPK%(I» WAIT 0.005 CALL SYSFUNC(2,FPK%(10» IF BXC-1 GOTO 6050 PRINT "STATUS BYTE- ", FPK%(8) RETURN REM************RAW DATA PLOT SUBROUTlNE****************
2'58
6120 6130 6135 6140 6150 6160 6170 6180 6190 6200 6210 6220 6225 6230 6240 6250 6260 6270 6280 6290 6300 6310 6320 6330 6335 6340 6350 6360 6370 6450 6500 6505 6510 6515 6520 6525 6530 6540 6545 6550 6555 6560 6565 6570 6600 6700 6705 6710 6712 6714 6715 6740 6742 6744 6746 6748 6750 6758 6760 6762
L-ABS(RAY(I» \ M-ABS(RAY(I» FOR K-2 TO RES PLT-ABS(RAY(K» IF PLT > L THEN L-PLT IF PLT < M THEN M-PLT NEXT K W-l.05*L \ U-O.95*M \ J-W-U \ X--U/J \ BA-440*X \ B-30+BA ZZ-440/(W-U) \ Y-710/RES \ Q-RES/I0 \ S-(W-U)/10 T-440/(W-U) CLS FOR I-I TO (RES-I) PLT-ABS(RAY(I» \ PLTT-ABS(RAY(I+l» LINE (30+Y*I,ZZ*PLT+B,30+Y*(I+l),ZZ*PLTT+B) NEXT I LINE (50,25,760,25) LINE (55,30,55,470) FOR I-I TO RES STEP Q TEXT (30+(Y*I),15,"IIt) TEXT (30+(Y*I),5,NUMl$(I» NEXT I TEXT (630,40,"TIME") FOR I-U TO W STEP S TEXT (65,B+(T*I),"I",I,I) IJ=INT(I) TEXT (I,B+(T*I),NUMl$(IJ),I,O) NEXT I TEXT (90,300,"INTENSITY",I,I) RETURN REM************INTERACTIVE DATA REVIEW************* INPUT "MAX DESIRED VALUE (ABS. VALUE): ";RAWMX INPUT "MIN'DESIRED VALUE (ABS. VALUE): ";RAWMN CNT-O FOR I-I TO RES IF ABS(RAY(I» > RAWMX GOTO 6560 IF ABS(RAY(I» < RAWMN GOTO 6560 CNT-CNT+l RAY(CNT)-RAY(I) NEXT I RES-CNT RETURN REM********PDF GENERATION AND CRT PLOT SUBROUTINE****** FOR I-I TO RES VLT(I)-(ABS(RAY(I»)/32768*RSEN*1000 NEXT I AL-VLT(I) \ AM-VLT(I) FOR 1-2 TO RES IF VLT(I) > AL THEN AL-VLT(I) IF VLT(I) < AM THEN AM-VLT(I) NEXT I RESOL-O.Ol*RSEN*1000 \ MAXX-RSEN*1000 \ NB-MAXX/RESOL MAT P - ZER FOR J-1 TO RES
2c)c)
6764 6766 6768 6770 6772 6774 6776 6790 6840 6842 6844 6848 6850 6860 6865 6867 6870 6873 6875 6880 6883 6885 6887 6890 6895 6905 6910 6915 6920 6925 6930 6935 6940 6945 6947 6950 6955 6960 6965 6970 6975 6980 6985 6990 6995 7000 7005 70rO 7015 7500 7505 7510 7515 7520 7530 7540 7542 7544 7546 7550
FOR I-I TO NB VOLT-I*RESOL IF VLT(J) > VOLT GOTO 6774 P(I)-P(I)+1 GOTO 6776 NEXT I NEXT J SUMP-O FOR L-l TO NB SUMP-SUMP+P(L) \ P(L)-P(L)/RES NEXT L PRINT "SUMPROB - ",SUMP PL-P(I) FOR 1-2 IF P(I) IF P(I) NEXT I
\ PM-P(I) TO NB > PL THEN PL-P(I) < PM THEN PM-P(I)
FOR J-l TO NB IF P(J)-PL THEN XPEAK-J NEXT J XPEAK-XPEAK*RESOL-RESOL/2 \ YPEAK-PL*100 ZZ-440/(1.2*PL*100) \ AL-MAXX \ Y-700/(1.2*AL) Q-INT(I.2*AL/I0) \ T-ZZ R-IE-3*INT(I.2*PL*100/10*IE3) \ MSS-INT(I.2*AL) MPS-IE-3*INT(I.2*PL*100*IE3) CLS FOR L-l TO NB AA-L*RESOL-RESOL \ AB-AA+RESOL YY-P(L)*100 \ YZ-P(L+l)*100 LINE (45+Y*AA,ZZ*YY+25,45+Y*AB,ZZ*YY+25) LINE (45+Y*AB,ZZ*YY+25,4S+Y*AB,ZZ*YZ+25) NEXT L LINE (45,25,745,25) LINE (45,30,45,470) FOR K-O TO MSS STEP Q TEXT (45+(Y*K),15,"I") TEXT (45+(Y*K),5,NUMl$(K» NEXT K TEXT (230,40,"SIGNAL (mV)") FOR K-O TO MPS STEP R TEXT (55,25+(T*K),"I",I,I) TEXT (0,25+(T*K),NUMl$(K),1,0) NEXT K TEXT (90,300,"PROBABILITY (%)",1,1) REM********CALCULATE SAMPLE MEAN AND VARIANCE******* SUM-O \ VAR-O FOR I-I TO RES \ SUM-SUM+RAY(I) \ NEXT I MEAN-SUM/RES FOR K-l TO RES VAR-VAR+(RAY(K)-MEAN)**2 NEXT K VAR-VAR/(RES-l) SIGMA-SQR(VAR) \ DEV-SIGMAjMEAN*100
260
7555 7560 7568 7580 7585 7586 7600 7700 7705 7710 7715 7720 7725 7730 7735 7740 7745 7750 7755 7760 7765 7770 7775 7780 7790 7795 7800 7805 7810 7820 7825 7830 7835 7840 7845 7850 7855 7856 7860 7865 7870 7875 7880 7885 7890 7895 7909 7905 7910 7912 7914 7916 7925 7940 7950 7951 7952 7953 7954 7955
MEAN-MEAN/32768*RSEN*1000 PRINT "SAMPLE MEAN (mV)",MEAN PRINT "SAMPLE DEV (%)",DEV INPUT "WANT HARDCOPY PLOT OF PDF (Y/N)?";HCP$ IF HCP$-"N" GOTO 8000 REM********PDF HARDCOPY PLOT SUBROUTINE************ MSV-MAXX \ MPV-INT(110*PL) IF MPV > (2*INT(MPV/2» THEN MPV-MPV+1 RV-MPV/10 \ Q-0.1*MSV PRINT #3, "IN;SP1;IP 600,600,9500,7400;SC O,",MSV,O,MPV FOR 1-0 TO MSV STEP Q PRINT #3,"PA",I,0,"TL 0.5,0;XT;PD" NEXT I PRINT #3, "PU;PA 0,0" FOR 1-0 TO MPV STEP RV PRINT #3, "PA",O,I,"TL 0.5,0;YT;PD" NEXT I PRINT #3, "PU;PA 0,0" PRINT #3, "SM ;" FOR J-O TO MPV STEP RV PRINT #3, "PA O,",J PRINT #3, "CP-5,-.25;LB";J;CHR$(3) NEXT J PRINT #3, "CP8,-17.5;DIO,1;LBPROB*100";CHR$(3);"DI1,0;" FOR K-O TO MSV STEP Q PRINT #3, "PA",K,O PRINT #3, "CP-1.5,-1.0;LB";K;CHR$(3) NEXT K PRINT #3, "CP-50,-1.0;LBSIGNAL (mV)";CHR$(3);"PU" PRINT #3, "SM ;PA 0,0" FOR L-1 TO NB AA-L*RESOL-RESOL \ AB-AA+RESOL \ YY$-NUM1$(P(L)*100) PRINT #3, "PA" ,AA, YY$; "PD" PRINT #3, "PA",AB,YY$ NEXT L PRINT #3, "PU;" A-0.3*MSV PRINT #3, PRINT #3, PRINT #3, PRINT #3,
\ B-MPV*0.9 "PA",A,B;"LBPDF MEAN - ";MEAN;CHR$(3) \ B-B-O.3*RV "PA",A,B;"LB# DATA PTS USED: ";RES;CHR$(3) \ B-B-0.3*RV "PA",A,B;"LBST.DEV. (%) - ";DEV;CHR$(3) "PU;SPO;PA 0,0;"
PRINT #1,CHR$(10) \ PRINT #1, "PDF POINTS (X,Y)" FOR L-1 TO NB STEP 2 AA-L*RESOL-RESOL/2 \ AAB-AA+RESOL PRINT #1,CHR$(10) PRINT #1,AA,(P(L)*100),AAB,(P(L+1)*100) NEXT L PRINT#1,CHR$(10) PRINT#1,"AVER LAS MON SIGNAL (mV) - ",LASSR PRINT#1,CHR$(10) PRINT#1,"AVER RAYL (#3-#4) SIGNAL (mV) - ",RAYMV PRINT#1,CHR$(10) \ PRINT#1,"# DATA PTS USED - ",RES PRINT#1,CHR$(10) \ PRINT#1,"SUMPROB - ",SUMP
261
7956 7958 7970 8000 8001 8002 8003 8005 8010 8015 8020 8030
PRINT#1,CHR$(10) \ PRINT#l,"SAMPLE MEAN (mV),MEAN PRINT#1,CHR$(10) \ PRINT#l,"SAMPLE DEV (%),DEV REM****************PROGRAM DISPOSITION**************************** INPUT "REDO ANALYSIS OF CURRENT DATA (Y/N)?";RAC$ IF RAC$-"Y" GOTO 1550 INPUT "RUN AGAIN (Y/N)?tI;X$ IF X$_tlNtI GOTO 8030 CLS \ GOTO 600 CLOSE #1 \ CLOSE #2 \ CLOSE #3 \ END
262
1 2 3 3 4 15 20 25 30 33 105 110 120 125 130 135 140 145 160 195 200 205 220 225 230 240 250 255 260 270 275 280 285 290 295 305 310 315 320 325 330 335 340 350 355 360 365 37"() 380 385 390 395 400 440 450 470 480 490 500 600
REM**** REM**** REM**** REM**** REM****
PROGRAM "NS3DBLS" STATIC GATE INTERFACE ROUTINE - 3 CHANNEL BASELINE SUBTRACTION DATA COLLECTION AND STORAGE ONLY UPDATED 9/21/88
***** ***** ***** ***** *****
DIM A(8200),FPK%(25) REM***************SET I/O PORTS**************************** OPEN "#BUSB?" AS FILE #2 REM**********SERIAL POLL FUNCTION PACKET******************* FPK%(1)-22 \ FPK%(2)-21 \ FPK%(3)-13 \ FPK%(4)-16 FPK%(5)-$423F \ FPK%(6)-8 \ FPK%(7)-24 \ FPK%(9)-0 FPK%(10)-28 \ FPK%(11)-23 \ FPK%(12)-20 \ FPK%(13)-0 BXC-O REM*************CHECK FOR COMMAND ERRORS******************* FOR 1-1 TO 8200 \ A(I)-O \ NEXT I GOSUB 2500 \ PRINT#2,"ZAP" \ WAIT 5 \ GOSUB 3500 GOSUB 6000 SPD=INT(FPK%(8)/2) IF SPD==2*INT(SPD/2) THEN GOTO 270 ELSE PRINT "COMMAND ERROR" GOTO 7900 REM*************SET INITIAL BOXCAR PARAMETERS************** GOSUB GOSUB GOSUB GOSUB GOSUB GOSUB
2500 2500 2500 2500 2500 2500
\ \ \ \ \ \
PRINT#2,"AC PRINT#2,"MM PRINT#2,"AM PRINT#2,"NT PRINT#2,"DD PRINT#2,"TR
0,1,1,1" \ WAIT 1 \ GOSUB 3500 2" \ WAIT 1 \ GOSUB 3500 3" \ WAIT 1 \ GOSUB 3500 2" \ WAIT 1 \ GOSUB 3500 13" \ WAIT 1 \ GOSUB 3500 5E-3" \ WAIT 1 \ GOSUB 3500
GOSUB GOSUB GOSUB GOSUB
2500 2500 2500 2500
\ \ \ \
PRINT#2,"CH 2" \ WAIT 1 \ GOSUB 3500 PRINT#2,"Z 1E6" \ WAIT 1 \ GOSUB 3500 PRINT#2,"SP 3.05E-3" \ WAIT 1 \ GOSUB 3500 PRINT#2,"GW 2E-5" \ WAIT 1 \ GOSUB 3500
GOSUB GOSUB GOSUB GOSUB
2500 2500 2500 2500
\ \ \ \
PRINT#2,"CH 3" \ WAIT 1 \ GOSUB 3500 PRINT#2,"Z 1E6" \ WAIT 1 \ GOSUB 3500 PRINT#2,"SP 3.05E-3" \ WAIT 1 \ GOSUB 3500 PRINT#2,"GW 2E-5" \ WAIT 1 \ GOSUB 3500
GOSUB GOSUB GOSUB GOSUB
2500 2500 2500 2500
\ \ \ \
PRINT#2,"CH 4" \ WAIT 1 \ GOSUB 3500 PRINT#2,"Z 1E6" \ WAIT 1 \ GOSUB 3500 PRINT#2,"SP 2.8E-3" \ WAIT 1 \ GOSUB 3500 PRINT#2, "GW 2E-5" \ WAIT 1 \ GOSUB 3500
GOSUB GOSUB GOSUB GOSUB GOSUB
2500 2500 2500 2500 2500
\ \ \ \ \
PRINT#2,"TL 1" \ WAIT 1 \ GOSUB 3500 PRINT#2,"TRR" \ WAIT 1 \ GOSUB 3500 PRINT#2,"TZ" \ WAIT 1 \ GOSUB 3500 PRINT#2,"TM" \ WAIT 1 \ GOSUB 3500 PRINT#2,"AC" \ WAIT 1 \ GOSUB 3500 . REM***************SET UP ROUTINE********************
605 610 620 630 640 650 660 670 680 690 700 710 720 730 735 740 750 770 800 810 820 825 950 960 964 967 970 973 980 1010 1012 1014 1016 1018 1020 1025 1030 1032 1033 1035 1036 1038 1040 1042 1043 1045 1047 1050 1052 1053 1055 1057 1070 1071 1072 1074 1090 1096 1098 1100
INPUT "RUN (Y/N)?";A$ \ IF A$-"Y" GOTO 970 INPUT "SET(S) OR CHECK(K) BOXCAR PARAMETERS?";B$ IF B$-"S" GOTO 660 IF B$-"K" GOTO 750 REM***************SET PARAMETERS******************** INPUT "SET PARAMETERS?";D$ \ IF D$-"N" GOTO 720 PRINT "PARAMETER IS: " INPUT LINE C$ \ GOSUB 3000 GOTO 680 INPUT "CHECK STATUS(K) OR START(T)?";E$ IF E$-"K" GOTO 750 IF E$-"T" GOTO 970 REM**************CHECK PARAMETERS******************* PRINT "STATUS OF: " INPUT LINE C$ \ GOSUB 3000 INPUT "CHECK OTHER PARAMETERS (Y/N)?";G$ IF G$=-"Y" THEN GOTO 800 ELSE GOTO 950 INPUT "SET PARAMETERS(S) OR START(T)?";H$ IF H$-"S" GOTO 660 IF H$-"T" GOTO 970 REM*************PREPARING TO START EXPERIMENT************ CLS INPUT "SET ZERO ON EACH BOXCAR CHANNEL (Y/N)?";SBZ$ IF SBZ$-"Y" GOTO 1030 INPUT "NON-LASER BACKGROUND OR #3-#4 ZERO (Y/N)?";NL$ IF NL$-"Y" GOTO 1040 INPUT "MEASURING RAYL SIGNALS (Y/N)?";LS$ IF LS$-"Y" THEN GOTO 1050 ELSE GOTO 1096 FLAG-1 GOSUB 2500 \ PRINT#2,"BS 1" \ YAIT 1 \ GOSUB 3500 PRINT "BASELINE SUBTRACTION DISABLED" GOSUB 2500 \ PRINT#2,"CL 32" \ YAIT 1 \ GOSUB 3500 GOTO 1072 FLAG-2 GOSUB 2500 \ PRINT#2,"BS 4" \ YAIT 1 \ GOSUB 3500 PRINT "BASELINE SUBTRACTION ACTIVE --> CHAN #3 - #4" GOTO 1070 FLAG-3 GOSUB 2500 \ PRINT#2,"BS 4" \ YAIT 1 \ GOSUB 3500 PRINT "BASELINE SUBTRACTION ACTIVE --> CHAN #3 - #4" GOTO 1070 PRINT INPUT INPUT INPUT
"NOM CURVE LENGTH (CL - ) (MAX-4096): " LINE C$ \ GOSUB 3000 "RAYL CHANNELS #3 & #4 SENS (VOLTS) - ";RSEN "LASER CHANNEL SENSITIVITY (VOLTS) - ";LSEN
INPUT "QUIT(Y/N) OR RESTART(ST)?";J$ IF J$-"Y" GO TO 7900 IF J$-"ST" GOTO 600
264
1105 1110 1115 1120 1125 1130 1132 1134 1136 1140 1145 1150 1155 1160 1165 1170 1175 1180 1185 1190 1220 1222 1225 1230 1250 1252 1255 1260 1262 1264 1270 1280 1285 1290 1295 1300 1305 1307 1308 1310 1313 1315 1320 1322 1325 1330 1332 1334 1336 1338 1345 1350 1360 1400 1401 1405 1410 1412 1416 1420
REM*************EXPERIMENTAL DATA ACQUISITION************ FOR I-I TO 8200 \ A(I)-O \ NEXT I INPUT "WRITE UPCOMING DATA TO DISK (Y/N)?";UD$ IF UD$-"Y" GOTO 1136 NOSV-1 \ GOTO 1145 NOSV-O CLS PRINT GOSUB PRINT GOSUB PRINT GOSUB PRINT GOSUB
"CLEAR DATA BUFFER" \ BXC-1 2500 \ PRINT#2,"ZAP" \ WAIT 5 "BEGIN COLLECTING DATA" 2500 \ PRINT#2,"C" \ WAIT 1 \ "BEGIN DATA TRANSFER TO IBM" 2500 \ PRINT#2,"DPS" \ WAIT 1 "DATA COLLECTION AND TRANSFER 6000 \ PRINT "RSP - ",RSP
\ GOSUB 3500 GOSUB 3500 \ GOSUB 3500 COMPLETE" \ BXC-O
IF FLAG-1 GO TO 2000 IF FLAG-2 GOTO 1250 IF FLAG-3 THEN GOTO 1400 ELSE GO TO 1096 REM***STORE NON-LASER DATA ON FLOPPY DISKETTE*** REM***CALCULATE NON-LASER AVERAGE BACKGROUND**** FOR I-I TO (RSP-8) \ A(I)-A(I+8) \ NEXT I RSP-RSP-8 RES-RSP/2 IF NOSV-1 GOTO 1300 INPUT "NEW FILE NAME FOR N-L DATA (l:****.DAT): ";NDF$ OPEN NDF$ AS FILE #3 SMNLR-O \ SMNLL-O FOR I-I TO RSP IF NOSV-1 GOTO 1310 PRINT#3, A(I) IF 2*INT(I/2)-I GO TO 1315 LAS-A(I) \ SMNLL-SMNLL+LAS \ GOTO 1320 RAY-A(I) \ SMNLR-SMNLR+RAY NEXT I CLOSE #3 NLRBCK-SMNLR/RES \ NLLBCK-SMNLL/RES NLRB-NLRBCK/32768*RSEN*1000 NLLB-NLLBCK/32768*LSEN*1000 PRINT "AVER NON-LASER RAYL BACKGR (mV) - ",NLRB PRINT "AVER NON-LASER LASER BACKGR (mV) - ",NLLB GOTO 1096 REM****STORE RAYL SIGNAL DATA ON DISKETTE****** REM***OPTIONAL PLOT OF RAYLEIGH SIGNAL DATA******** FOR I-I TO (RSP-8) \ A(I)-A(I+8) \ NEXT I RSP-RSP-8 RES-RSP/2
26':;
1450 1455 1457 1460 1465 1470 1472 1474 1476 1478 1480 1485 1490 1500 1505 1510 1515 1520 1522 1530 1540 1545 1550 1555 1560 1900 2000 2005 2010 2012 2015 2020 2022 2024 2026 2028 2030 2040 2042 2044 2046 2048 2050 2055 2060 2100 2500 2520 2530 2540 2550 2560 2570 3000 3005 3010 3015 3020 3025 3030
IF NOSV-1 GOTO 1465 INPUT "NEW FILE NAME FOR RAYL DATA (l:****.DAT): ";NDF$ OPEN NDF$ AS FILE #5 SMRAY-O \ SMLAS-O FOR 1-1 TO RSP IF NOSV-1 GOTO 1476 PRINT#5, A(I) IF 2*INT(I/2)-I GOTO 1480 LAS-A(I) \ SMLAS-SMLAS+LAS \ GOTO 1485 RAY-A(I) \ SMRAY-SMRAY+RAY NEXT I CLOSE #5 AVRAY-SMRAY/RES \ AVLAS-SMLAS/RES RAYMV-AVRAY/32768*RSEN*1000 LASMV-AVLAS/32768*LSEN*1000 PRINT "AVER RAYL (#3-#4) SIGNAL (mV) - ",RAYMV PRINT "AVER LASER (#2) SIGNAL (mV) - ",LASMV INPUT "PLOT RAYL DATA (Y/N)?";PRD$ IF PRD$-"N" GOTO 1560 GOSUB 6100 \ PRINT "RAYLEIGH DATA" GOTO 1096 REM******SET INDIVIDUAL CHANNEL ZEROS************** FOR I-I TO (RSP-12) \ A(I)-A(I+12) \ NEXT I RSP-RSP-12 \ RES-RSP/3 SMLAS-O \ SMRA-O \ SMRB-O FOR J-1 TO RES LAS-A(3*J-2) \ RAYA-A(3*J-1) \ RAYB-A(3*J) SMLAS-SMLAS+LAS \ SMRA-SMRA+RAYA \ SMRB-SMRB+RAYB NEXT J AVRA-SMRA/RES*RSEN*1000/32768 AVLAS-SMLAS/RES*LSEN*1000/32768 AVRB-SMRB/RES*RSEN*1000/32768 PRINT "AVER CHAN #2 SIGNAL (mV) - ",AVLAS PRINT "AVER CHAN #3 SIGNAL (mV) - ",AVRA PRINT "AVER CHAN #4 SIGNAL (mV) - ",AVRB GOTO 1096 REM**CHECK IF COMMAND DONE BY CHECKING VALUE OF BIT 0** REM**DO THIS BY CHECKING IF FPK%(8) IS ODD OR EVEN***** REM*****************TAKE SERIAL POLL******************* GOSUB 6000 IF FPK%(8)-2*INT(FPK%(8)/2) GOTO 2540 RETURN REM***********DRIVER SUBROUTINE #1********************* RSP-O \ NX-1 GOSUB 3050 GOSUB 4000 GOSUB 5000 RETURN
266
3035 3040 3050 3060 3070 3080 3090 3100 3110 3120 3125 3500 3505 3510 3520 3530 3540 3550 4000 4010 4020 4030 4040 4050 4060 4070 4080 4090 4110 4120 5000 5005 5020 5030 5040 5050 5060 5070 5072 5080 5200 6000 6005 6010 6020 6030 6035 6040 6050 6060 6100 6110 6112 6114 6116 6118 6120 6125 6130 6135
REM***************"OUTPUT" SUBROUTINE****************** REM**CHECK IF COMMAND DONE BY CHECKING VALUE OF BIT 0** REM**DO THIS BY CHECKING IF FPK%(8) IS ODD OR EVEN***** REM*****************TAKE SERIAL POLL******************* GOSUB 6000 IF FPK%(8)-2*INT(FPK%(8)/2) GOTO 3080 PRINT#2, C$ \ WAIT 1 RETURN REM*************DRIVER SUBROUTINE #2******************* RSP=O \ NX-2 GOSUB 4000 GOSUB 5000 RETURN REM***************"ENTER" SUBROUTINE******************* REM*****CHECK FOR RESPONSES FROM BOXCAR**************** REM******************TAKE SERIAL POLL****************** GOSUB 6000 REM**CHECK FOR RESPONSE BY CHECKING VALUE OF BIT 7***** REM**DO THIS BY CHECKING IF FPK%(8) IS > 128*********** IF FPK%(8) INT(l) 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)+l 6754 NEXT K 6770 6780 INPUT "SMOOTHING INTERVAL: ";DEL 6785 6790 FOR I-I 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-O 6824 FOR N--DEL TO DEL 6826 -.sUM-SUM+P(J+N) 6828 NEXT N 6830 P(J)-SUM/(2*DEL+1) 6832 NEXT J 6840 6850 INPUT "SMOOTHED PDF BIN SIZE (K): ";RESOL 6852 NBB-(MAXX-300)/RESOL 6855 6860 CNT-1 6870 FOR 1-1 TO NBB 6872 SUM-O 6874 FOR N-1 TO RESOL 6880 SUM-SUM+P(CNT)
276
6882 6884 6895 6900 6905 6910 6915 7000 7100 7101 7102 7105 7108 7110 7115 7117 7120 7125 7130 7135 7140 7145 7150 7155 7160 7165 7170 7175 7180 7190 7195 7200 7205 7210 7220 7225 7230 7235 7270 7272 7275 7280 7281 7285 7290 7350 7480 7482 7484 7495 7500 7505 7510 7520 7530 7540 7542 7544 7546 7548
CNT-CNT+1 NEXT N P(I)-SUM NEXT I
277
NB-NBB GOTO 6130 REM********PDF HARDCOPY PLOT SUBROUTINE************ REM*******PRINT OUT TEMP PDF PLOT PAIRS************ REM*******STORE TEMP PDF POINT PAIRS ON DISK******* MSV-MAXX MPV-INT(110*PL) \ RV-2 \ Q-(MSV-300)/10 IF MPV > (2*INT(MPV/2» THEN MPV-MPV+1 PRINT #2, "IN;SP1;IP 600,700,9500,7400;SC 300,",MSV,0,MPV FOR I-300 TO MSV STEP Q PRINT #2,"PA",I,0,"TL 0.5,0;XT;PD" NEXT I PRINT #2, "PU;PA 300,0" FOR 1-0 TO MPV STEP RV PRINT #2, "PA",300,I,"TL 0.5,0;YT;PD" NEXT I PRINT #2, "PU;PA 300,0" PRINT #2, "SM ;" FOR J=O TO MPV STEP RV PRINT #2, "PA 300,",J PRINT #2, "CP-3,-.25;LB";J;CHR$(3) NEXT J PRINT #2, "CP5,-17.5;DIO,I;LBPROBABILITY (%)";CHR$(3);"Dll,0;" FOR K-300 TO MSV STEP Q PRINT #2, "PA" ,K, PRINT #2, "CP-2.5,-1.0;LB";K;CHR$(3) NEXT K PRINT #2, "CP-60,-1.5;LBTEMPERATURE (K)";CHR$(3);"PU" PRINT #2, "SM ;PA 300,0"
°
FOR L-1 TO NB AA-300+L*RESOL-RESOL AB-AA+RESOL \ YY$-NUMl$(P(L)*100) PRINT #2, "PA" ,AA, TI$; "PD" PRINT #2, "PA" ,AB, TI$ NEXT L PRINT #2, "PU;" A-O.7*MSV PRINT #2, PRINT #2, PRINT #2, PRINT #2, PRINT #2, PRINT #2, PRINT #2,
\ B-0.9*MPV \ C-O.25*RV "PA" ,A,B;"LBNAME: ";RNM$;CHR$(3) \ B-B-C "PA",A,B;"LBRUN DATE: ";RDT$;CHR$(3) \ B-B-C "PA",A,B;"LB# OF DATA POINTS: ";RES;CHR$(3) \ B-B-C "PA",A,B;"LBPDF MEAN (K) - ";MEAN;CHR$(3) \ B-B-C "PA",A,B;"LBST.DEV. (%) - ";DEV;CHR$(3) \ B-B-C "PA",A,B;"LBBIN SIZE (K) - ";RESOL;CHR$(3) "PU;SPO;PA 0,0;"
PRINT #1,CHR$(10) \ PRINT #1, "PDF POINTS (X,Y)" FOR L-l TO NB STEP 2 AA-300+L*RESOL-RESOL/2 \ AAB-AA+RESOL PRINT #1 ,'CHR$ (10) PRINT #1,AA, (P(L)*100),AAB, (P(L+l)*100)
7550 NEXT L 7552 7600 RETURN 7800 7900 REM****************DECONVOLUTION OF TEMP PDF********** 7901 7905 REM*************GET CURRENT OBSV TEMP PDF VALUES******* 7910 7912 PRINT #1,CHR$(10) \ PRINT #1, "PDF POINTS (X,Y)" 7914 FOR L-1 TO NB STEP 2 7916 AA-300+L*RESOL-RESOL/2 \ AAB-AA+RESOL 7918 PRINT #1,CHR$(10) 7920 PRINT #l,AA, (P(L)*100),AAB, (P(L+1)*100) 7922 NEXT L 7930 7940 REM****************INPUT SELECTED PARAMETERS********** 7942 7944 INPUT "# of non-zero data point pairs NDP: ";NDP 7946 INPUT "first temp (K) of analysis range TF: tt ;TF 7948 INPUT "last temp of analysis range (max 2475) TL: ";TL 7950 INPUT "first non-zero temp (K) TA: ";TA 7952 INPUT "last non-zero temp (K) TZ: ";TZ 7960 INPUT "error parameter GM: tt ;GM 7962 INPUT "error parameter GB: ";GB 7964 7966 INPUT "RE-ENTER ANY OF THESE PARAMETERS (Y/N)?";CAP$ 7968 IF CAP$-flY" GOTO 7940 7970 7975 NDR-(TL-TF)/RESOL+1 7980 7982 FOR 1-1 TO NDR \ Y(I)-P(I)*100 \ NEXT I 7984 SUMY-O 7986 FOR 1-1 TO NDR \ SUMY-SUMY+Y(I) \ NEXT I 7988 FOR J-1 TO NDR \ Y(J)-Y(J)/SUMY*100 \ NEXT J 7990 8000 REM*******SETUP THE GAUSSIAN BLURRING MATRIX******* 8001 8002 INPUT "want new GAUSSIAN matrix (Y/N)?";NGM$ 8003 IF NGM$-"N" GOTO 8080 8005 8010 NDA-(TA-TF)/RESOL+1 8012 NDB-(TL-TZ)/RESOL+1 \ NDC-NDA+NDP-1 8014 NLRBK-NLRBCK/32768*1000*RSEN*XYX 8016 MAT H - ZER 8020 8022 INPUT "use NLRBK (Y/N)?";UNLR$ 8024 IF UNLR$-"N" THEN NLRBK-O 8028 .. 8030 CNT-O 8032 FOR M-NDA TO NDC 8034 TBAR-TA+CNT*RESOL 8036 SRBAR-GAMMA*BETA/TBAR+GAMMA*ALPHA 8038 SRBAR-SRBAR+NLRBK 8040 DELSR-10.**(GM*LOG10(SRBAR)+GB) 8042 DELSR-DELSR*O.Ol*SRBAR 8044 DELT-GAMMA*BETA*DELSR/(SRBAR-ALPHA*GAMMA)**2 8046 A-RESOL/(DELT*SQR(2*PI» 8048 FOR N-1 TO NDR 8050 DEV-TF+(N-1)*RESOL-TBAR 8052 B-EXP(-0.5*(DEV/DELT)**2)
278
8054 8056 8058 8060 8062 8064 8070 8080 8082 8083 8085 8086 8090 8100 8102 8104 8106 8108 8110 8112 8114 8116 8120 8122 8124 8126 8130 8132 8234 8236 8240 8300 8301 8305 8310 8320 8322 8324 8326 8328 8330 8332 8340 8344 8346 8348 8350 836Q 8362 8364 8370 8380 8382 8384 8386 8388 8390 8392 8400 8410
H(N,M)-A*B IF H(N,M) >- 1.0E-10 GOTO 8060 H(N,M)-O. NEXT N CNT-CNT+1 NEXT M REM*********INPUT PDF GUESS AND OTHER PARAMETERS******** PRINT "INPUT NEW PDF GUESS IF ENTERING DECON" INPUT "WANT TO INPUT A NEW PDF GUESS (Y/N)?";CGP$ IF CGP$-"N" GOTO 8130 PRINT "INPUT DECON TEMP PDF GUESS" MAT X - ZER FOR 1-1 TO NDR TEMP-TF+(I-1)*RESOL PRINT "TEMP (K): ",TEMP INPUT "PROB (%): ";X(I) ZX(I)-X(I) NEXT I SUMX-O FOR 1-1 TO NDR \ SUMX-SUMX+X(I) \ NEXT I FOR J-1 TO NDR \ X(J)-X(J)/SUMX*100 \ NEXT J INPUT "desired minimum temp (K) DMT: ";DMT INPUT "desired maximum temp (K) DXT: ";DXT INPUT "# of iterations NI: ";NI INPUT "magic factor LAMBDA: ";LAMBDA REM**********DECONVOLUTION WITH CONSTRAINTS********* FOR J-1 TO NI FOR N-1 TO NDR SUMHX-O FOR M-1 TO NDR SUMHX-SUMHX+H(N,M)*X(M) NEXT M HX(N)-SUMHX NEXT N SUMHX-O FOR L-1 TO NOR \ SUMHX-SUMHX+HX(L) \ NEXT L FOR L-1 TO NOR \ HX(L)-HX(L)/SUMHX*100 \ NEXT L FOR N-1 TO NOR X(N)-X(N)+LAMBOA*(Y(N)-HX(N» NEXT N FOR N-1 TO NOR TEMP-TF+(N-1)*RESOL IF TEMP < OM! GOTO 8390 IF TEMP > OXT GOTO 8390 IF X(N) >- 0 GOTO 8392 X(N)-O NEXT N SUMX-O
279
8412 8414 8420 8425 8426 8430 8435 8436 8450 8451 8460 8462 8464 8466 8468 8470 8472 8474 8476 8480 8490 8492 8494 8496 8498 8500 8502 8504 8506 8508 8520 8521 8530 8532 8534 8536 8538 8540 8550 8552 8554 8556 8558 8560 8562 8564 8566
FOR L-1 TO NDR \ SUMX-SUMX+X(L) \ NEXT L FOR L-1 TO NDR \ X(L)-X(L)/SUMX*100 \ NEXT L PRINT "ITERATION NEXT J
# -
280
",J
FOR N-1 TO NDR \ X(N)-X(N)/100 \ NEXT N REM********CALCULATE STATS FOR PDF*********** YSUMM-O \ YSUMS-O \ XSUMM-O \ XSUMS-O FOR N-1 TO NDR TEMP-TF+(N-1)*RESOL YSUMM-YSUMM+TEMP*Y(N)/100 YSUMS-YSUMS+Y(N)/100*TEMP**2 XSUMM-XSUMM+TEMP*X(N) XSUMS-XSUMS+X(N)*TEMP**2 PLT(N)-X(N) NEXT N YSIGMA-SQR(YSUMS-YSUMM**2)/ySUMM*100 XSIGMA-SQR(XSUMS-XSUMM**2)/XSUMM*100 MEAN-XSUMM \ SIGMA-XSIGMA INPUT "MAX PLOT TEMP CLS \ FLG$-"A"
(max
2500) (K): ";MAXX
PRINT "OBSV.MEAN: ",YSUMM \ PRINT "STD.DEV.(%): ",YSIGMA PRINT "CALC.MEAN: ",XSUMM \ PRINT "STD.DEV.(%): ",XSIGMA REM*******CRT PLOT OF DECONVOLVED TEMP PDF******* PL-PLT(1) \ PM-PLT(1) FOR N-l TO NDR IF PLT(N) > PL THEN PL-PLT(N) IF PLT(N) < PM THEN PM-PLT(N) NEXT N NB-(MAXX-300)/RESOL \ ZZ-440/(PL*100) \ AL-MAXX YP-700/(AL) \ Q-INT(AL/10) \ T-ZZ R-1E-3*INT(PL*100/10*1E3) \ MSS-INT(AL) MPS-1E-3*INT(PL*100*1E3)
FOR L-1 TO NB AA-300+L*RESOL-RESOL \ AB-AA+RESOL YY-PLT(L)*100 \ YZ-PLT(L+1)*100 LINE (45+YP*AA,ZZ*YY+25,45+YP*AB,ZZ*YY+25) 8568~INE (45+YP*AB,ZZ*YY+25,45+YP*AB,ZZ*YZ+25) 8570 NEXT L 8572 LINE (45,25,745,25) 8574 LINE (45,30,45,470) - 8576 FOR K-O TO MSS STEP Q 8578 TEXT (45+(YP*K),15,"I") 8580 TEXT (45+(YP*K),5,NUMl$(K» 8582 NEXT K 8584 TEXT (230,40,"TEMPERATURE (K)") .. , 8586 FOR K-O TO MPS STEP R 8588 TEXT (55,25+(T*K),"I",1,1) 8590 TEXT (0,25+(T*K),NUMl$(K),1,0) 8592 NEXT K
8594 8596 8600 8605 8610 8611 8612 8613 8614 8616 8620 8630 8632 8634 8640 8645 8647 8650 8655 8657 8660 8670 8672 8673 8674 8675 8676 8677 8678 8679 8680 8681 8682 8683 8684 8685 8686 8687 8688 8689 8690 8700 8701 8702 8705 8709 8710 8711 8714 8716 8718 8720 8722 8724 8726 8728 8730 8732 8734 8736
TEXT (90,300,"PROBABILITY (%)",1,1)
281
IF FLG$-"C" GOTO 8645 INPUT "REDO DECONV. WITH NEW PARAMETERS (Y/N)?";NBV$ IF NBV$-"N" GOTO 8630 INPUT "GO BACK TO ORIG. DATA ANALYSIS (Y/N)?";GBO$ IF GBO$-"Y" GOTO 1220 FOR J-1 TO NDR \ X(J)-ZX(J) \ NEXT J GOTO 8000 INPUT "REGEN. ORIG. PDF (Y/N)?";VRP$ IF VRP$-"N" GOTO 8645 FLG$-"C" \ GOTO 8840 INPUT "WANT HARDCOPY OF CURRENT PDF (Y/N)?";HCP$ IF HCP$-"N" GO TO 8610 IF FLG$-"C" THEN FLG$=-"B" IF FLG$="B" GOTO 8700 PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#l,CHR$(lO) PRINT#1,CHR$(10) PRINT#l,CHR$(lO)
\ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \
PRINT#l,"RESOL: ",RESOL PRINT#l,"DMT: ",DMT PRINT#l,"DXT: ",DXT PRINT#l,"NI: ",NI PRINT#l,"NDP: ",NDP PRINT#l,"LAMBDA: ",LAMBDA PRINT#l,"TF: ",TF PRINT#l,"TL: ",TL PRINT#l,"TA: ",TA PRINT#l,"TZ: ",TZ PRINT#l,"BETA: ",BETA PRINT#l,"GAMMA: ",GAMMA PRINT#l,"ALPHA: ",ALPHA PRINT#l,"OBSV MEAN (K): ",YSUMM PRINT#l,"STD. DEV. (%): ",YSIGMA PRINT#l,"CALC. MEAN (K): ",XSUMM PRINT#l,"STD. DEV. (%): ",XSIGMA PRINT#l,"GM: ",GM PRINT#l,"GB: ",GB
REM********PDF HARDCOPY PLOT SUBROUTINE************ REM*******PRINT OUT TEMP PDF PLOT PAIRS************ MSV-MAXX MPV-INT(llO*PL) \ RV-MPV/IO \ Q-(MSV-300)/10 IF MPV > (2*INT(MPV/2)) THEN MPV-MPV+1 .. PRINT #2, "IN;SP1;IP 600,700,9500,7400;SC 300,",MSV,0,MPV FOR I-300 TO MSV STEP Q PRINT #2," PA" , I , "TL 0. 5 , XT ; PD" NEXT I PRINT #2, "PU;PA 300,0" FOR 1-0 TO MPV STEP RV PRINT #2, "PA",300,I,"TL 0.5,0;YT;PD" NEXT I PRINT #2, "PU;PA 300,0" PRINT #2, "SM ;" FOR J-O TO MPV STEP RV PRINT #2, "PA 300,",J
°,
°;
8738 8740 8742 8744 8746 8748 8750 8752 8754 8756 8760 8762 8764 8766 8768 8770 8772 8774 8780 8781 8782 8783 8784 8785 8790 8795 8800 8801 8802 8803 8810 8812 8814 8816 8818 8820 8822 8825 8830 8832 8834 8835 8840 8845 8850 8852 8854 8856 8858 8860 8865 8866 8870 8872 8874 8876 8878 8880 8882 8884
PRINT #2, NEXT J PRINT #2, FOR K-300 PRINT #2, PRINT #2, NEXT K PRINT #2, PRINT #2,
"CP-5,-.25;LB";J;CHR$(3) "CP5,-17.5;DIO,1;LBPROBABILITY (%)";CHR$(3);"DI1,0;" TO MSV STEP Q "PA",K,O "CP-2.5,-1.0;LB";K;CHR$(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;" A-0.2*MSV PRINT #2, PRINT #2, PRINT #2, PRINT #2,
\ B-0.95*MPV "PA",A,B;"LBPDF MEAN (K) - ";MEAN;CHR$(3) \ B=B-O.3*RV "PA",A,B;"LBST.DEV. (%) - ";SIGMA;CHR$(3) \ B=B-O.3*RV "PA",A,B;"LBBIN SIZE (K) .. ";RESOL;CHR$(3) "PU;SPO;PA 0,0;"
IF FLG$-"A" GO TO 8810 PRINT#l,CHR$(lO) \ PRINT#l,"REGEN. OBSV. PDF" PRINT#1,CHR$(10) \ PRINT#l,"PDF MEAN (K): ",YCSUM PRINT#1,CHR$(10) \ PRINT#l,"STD. DEV. (%): ",YCSIG PRINT #1,CHR$(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 #l,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$-"N" GOTO 8910 REM*********REGENERATION OF OBSV. PDF********** FOR N-1 TO NDR SUMHX-O FOR M-1 TO NDR 5UMHX-SUMHX+H(N,M)*X(M)*100 NEXT M YC(N)-SUMHX NEXT N YCSUM-O \ YCSUS-O FOR N-1 TO NDR TEMP-TF+(N-l)*RESOL YCSUM-YCSUM+YC(N)/100*TEMP YCSUS-YCSUS+YC(N)/lOO*TEMP**2 PLT(N)-YC(N)/IOO NEXT N YCSIG-SQR(YCSUS-YCSUM**2)/yCSUM*100
282
8886 8890 8892 8894 8896 8898 8900 8905 8910 8912 8914 8916 8918 9990 9992 9994 9996 9998 9999
INPUT "MAX PLOT TEMP (max 2500) (K): ";MAXX CLS \ FLG$-"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$-"N" GOTO 9999 CLS \ GOTO 100 CLOSE #1 \ CLOSE #2 \ END
28~
1 2 3 4 5
REM*** REM*** REM*** REM*** REM***
PROGRAM "AFTTOX" CALCULATE SIMPLE ADIABATIC FLAME TEMPERATURES, EFFECTIVE CROSS SECTIONS, FEED-BASED RESIDENCE TIMES FOR C2H4/CH3CL COMBUSTION 3/26/89
*** *** *** *** ***
284
7
9 DIM A(10) ,FPK%(5),XF(10),XP(10) ,B(10),SIGF(10) 10 DIM SIGMAP(15),AFT(15),SIGP(10),C(10),CP(10) 11 12 OPEN "#SEROl" AS FILE #1 13 FPK%(I)-20 \ FPK%(2)-6 \ FPK%(3)-22 \ FPK%(4)-200 \ FPK%(5)-0 14 CALL SYSFUNC(I,FPK%(I» 15 16 INPUT "RUN NAME: "; RUNNAM$ 17 PRINT#I,CHR$(10) \ PRINT#I,"RUN NAME: ",RUNNAM$ 18 INPUT "RUN DATE: ";RUNDAT$ 19 PRINT#I,CHR$(10) \ PRINT#I,"RUN DATE: ",RUNDAT$ 20 INPUT "AIR FEED RATE (GMOLESjMIN): ";AIR 21 PRINT#I,CHR$(10) \ PRINT#I,"AIR RATE (GMOLES/MIN) - ",AIR 22 INPUT "FEED RATE OF C2H4 (GMOLES/MIN): ";M 23 PRINT#I,CHR$(10) \ PRINT#I,"C2H4 FEED (GMOLES/MIN) - ",M 24 INPUT "WINDOW/DIL N2 (GMOLESjMIN): ";Y \ PRINT#I,CHR$(10) 25 PRINT#I,"WINDOW AND/OR DIL N2 RATE (GMOLES/MIN) =- ",Y 26 INPUT "FEED RATE OF CH3CL (GMOLES/MIN): ";TOX 27 PRINT#I,CHR$(10) \ PRINT#I,"CH3CL RATE (GMOLES/MIN): ",TOX 28 INPUT "MEASURED T/C TEMPERATURE (K): "; TEMP 30 PRINT#I,CHR$(10) \ PRINT#I,"T/C TEMPERATURE (K) - ",TEMP 31 INPUT "EST FEED PREHEAT TEMP (K): ";TFEED 32 PRINT#I,CHR$(10) \ PRINT#I,"EST FEED TEMP (K) - ",TFEED 33 INPUT "EST HEAT LOSS (%): ";HL 34 PRINT#I,CHR$(10) \ PRINT#I,"EST HEAT LOSS (%) - ",HL 35 40 REM************CALCULATE TOTAL FEED RATE AND*********** 41 REM**************FEED BASED RESIDENCE TIME************* 42 43 PHI-(3*M+l.5*TOX)/(0.21*AIR) 44 PRINT "EFF. EQUIV. RATIO - ",PHI 45 PRINT#I,CHR$(10) \ PRINT#I,"EFF. EQUIV. RATIO - ",PHI 46 R-TOX/M \ FR-M+AIR+Y+TOX 47 PRINT "TOTAL FEED (GMOLESjMIN) - ",FR \ PRINT#I,CHR$(10) 48 PRINT#I,"TOTAL FEED RATE (GMOLESjMIN) - ",FR 49 50 TAU-(250*60)/(TEMP*FR*0.0821) \ PRINT#I,CHR$(10) 51 PRINT "FEED BASED RESID. TIME (MSEC) - ",TAU 52 PRINT#I,"FEED BASED RESID. TIME (MSEC) - ",TAU 55 60 REM******** COMPONENT INDEX ORDER AS FOLLOWS: ******** 6} REM******** l-C2H4, 2-H2, 3-02, 4-N2, 5-C02, ******** 62 REM******** 6-H20, 7-CO, 8-CL2, 9-HCL, 10-CH3CL ******** 65 70 REM***CALCULATE EFFECTIVE CROSS SECTION OF FEED*********** 71 72 XF(I)-M/FR \ XF(2)-0 \ XF(3)-0.21*AIR/FR \ XF(7)-0 73 XF(8)-0 \ XF(9)-0 \ XF(10)-TOX/FR \ XF(5)-0 \ XF(6)-0 74 XF(4)-(0.79*AIR+Y)/FR 75 SUMXF-O 76 FOR I-I TO 10 \ SUMXF-SUMXF+XF(I) \ NEXT I 77 PRINT "SUM OF CALC. FEED MOLE FRAC.: ", SUMXF \ WAIT 20 78 XF(4)-I-(XF(I)+XF(3)+XF(10» 79
""----
-~
80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 104 105 106
SIGF(3)-XF(3)*5.175 \ SIGF(5)-0 \ SIGF(9)-0 \ SIGF(8)-0 SIGF(4)-XF(4)*6.216 \ SIGF(6)-0 \ SIGF(1)-XF(1)*37.15 SIGF(10)-XF(10)*40.57 \ SIGF(2)-0 \ SIGF(7)-0 SIGMAF-O FOR 1-1 TO 10 \ SIGMAF-SIGMAF+SIGF(I) \ NEXT I PRINT "FEED EFFECTIVE CROSS SECTION - ",SIGMAF PRINT#1,CHR$(10) \ PRINT#l,"FEED EFF.CROSS SECT.: ",SIGMAF REM***********HEAT CAPACITY COEFFICIENTS********************* A(1)-2.830 \ A(2)-6.947 \ A(3)-6.148 \ A(4)-6.524 A(5)-6.214 \ A(6)-7.256 \ B(1)-28.60E-3 \ B(2)--0.2E-3 B(3)-3.102E-3 \ B(4)-1.250E-3 \ B(5)-10.396E-3 \ B(6)-2.298E-3 C(1)--8.726E-6 \ C(2)-0.481E-6 \ C(3)--0.923E-6 \ C(4)--0.001E-6 C(5)--3.545E-6 \ C(6)-0.283E-6 \ A(7)-6.420 \ B(7)-1.665E-3 C(7)--0.196E-6 \ A(8)-7.576 \ B(8)-2.424E-3 \ C(8)--0.965E-6 A(9)-6.732 \ B(9)-0.433E-3 \ C(9)-0.370E-6 \ A(10)-4.827 B(10)-18.8E-3 \ C(10)--4.810E-6 REM*****CALCULATE FEED PREHEAT BASED ON ONE MOLE OF FEED********
PREHT=O FOR I-I TO 10 PREHT-PREHT+XF(I)*(A(I)*(TFEED-300)+B(I)*(TFEED**2-300**2)/2& +C(I)*(TFEED**3-300**3)/3) 107 NEXT I 109 110 REM****CALCULATE EFFECTIVE CROSS SECTION FOR MIXTURE AT******* III REM****GIVEN CONVERSION LEVEL ** ONE MOLE OF FEED - BASIS***** 113 114 MAT SIGMAP - ZER \ MAT AFr - ZER \ CNT-O 120 IF PHI> 1.0 GOTO 165 125 . 130 FUEL-XF(1)+XF(10) \ INCR-FUEL*O.l 132 FOR CONV-O TO FUEL STEP INCR 134 CONTOX-(R/(R+1»*CONV \ CONETH-(1/(R+1»*CONV 136 TPM-1+0.5*CONTOX 138 XP(l)-(XF(l)-CONETH)/TPM \ XP(2)-0 \ XP(7)-0 \ XP(8)-0 140 XP(3)-(XF(3)-3*CONETH-1.5*CONTOX)/TPM 142 XP(5)-(2*CONETH+CONTOX)/TPM \ XP(6)-(2*CONETH+CONTOX)/TPM 144 XP(9)-CONTOX/TPM \ XP(10)-(XF(10)-CONTOX)/TPM 146 XP(4)-XF(4)/TPM 148 SUMXP-O 150 FOR I-I TO 10 \ SUMXP-SUMXP+XP(I) \ NEXT I 151 PRINT "SUM OF CALC. PROD. MOLE FRAC.: ",SUMXP \ WAIT 20 152 XP(4)-1-(XP(1)+XP(3)+XP(5)+XP(6)+XP(9)+XP(10» 15~ HEAT-CONETH*316240.+CONTOX*154320. 156 GOSUB 210 158 NEXT CONV 160 GOTO 360 161 165 OXID-XF(3) \ INCR-OXID*O.l 167 FOR CONV-O TO OXID STEP INCR 170 CONETH-(1/(1+R»*CONV*0.5 \ CONTOX-(R/(R+1»*CONV*0.8 172 TPM-1.0+CONETH+0.75*CONTOX 174 XP(l)-(XF(l)-CONETH)/TPM \ XP(2)-CONETH/TPM \ XP(4)-XF(4)/TPM 176 XP(3)-(XF(3)-CONV)/TPM \ XP(7)-(CONETH+0.5*CONTOX)/TPM 178 XP(5)-(CONETH+0.5*CONTOX)/TPM \ XP(6)-(CONETH+CONTOX)/TPM 180 XP(8)-0 \ XP(9)-CONTOX/TPM \ XP(10)-(XF(10)-CONTOX)/TPM
28S
182 183 184 185 186 188 190 192 200 210 211 212 213 214 215 220 221 222 225 230 231 235 250 255 260 261 265 270 271 272 280 285 286 287 290 295 300 305 310 315 320 325 330 332 334
SUMXP-O FOR I-I TO 10 \ SUMXP-SUMXP+XP(I) \ NEXT I PRINT "SUM OF CALC. PROD. MOLE FRAC.: ",SUMXP \ WAIT 20 XP(4)-1-(XP(1)+XP(2)+XP(3)+XP(5)+XP(6)+XP(7)+XP(9)+XP(10» HEAT-CONETH*190810.+CONTOX*120500. GOSUB 210 NEXT CONV GOTO 360 SIGP(3)-XP(3)*5.175 SIGP(1)-XP(1)*37.15 SIGP(4)-XP(4)*6.216 SIGP(7)-XP(7)*7.767 SIGP(9)-XP(9)*13.70
\ \ \ \ \
SIGP(5)-XP(5)*14.24 SIGP(2)-XP(2)*1.352 SIGP(6)-XP(6)*4.446 SIGP(8)-XP(8)*40.68 SIGP(10)-XP(10)*40.57
SUMP-O \ CNT-CNT+1 FOR I-I TO 10 \ SUMP-SUMP+SIGP(I) \ NEXT I SIGMAP(CNT)-SUMP PRINT "PROD EFF CROSS SECTION - ",SUMP \ PRINT#1,CHR$(10) PRINT#l, "PRODUCT EFFECTIVE CROSS SECTION - ",SUMP REM*******CALCULATE AD.FLAME TEMP. USING NEWTON'S METHOD******* TS-1000. AVHT-1-(0.01*HL) SF-O \ SFP-O \ CT-1 FOR I-I TO 10 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*(HEAT+PREHT)/TPM - SF FOR I-I TO 10 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 GO TO 330 IF CT - 1000 THEN GOTO 315 ELSE GOTO 320 PRINT "NO CONVERGENCE AFTER 1000 CYCLES" \ GOTO 500 TS-NTS \ CT-CT+1 \ GOTO 265
IF PHI> 1.0 THEN BASIS-oXID ELSE BASIS-FUEL FCF-CONV/BASIS*100. \ PRINT#1,CHR$(10) PRINT "FUEL OR OXID CONVERSION (%) - ",FCF 33~ PRINT#l, "FUEL OR OXID CONVERSION (%) - ",FCF 338 PRINT "AD FL TEMP (K) - ",NTS \ PRINT#1,CHR$(10) 340 PRINT#l, "AD FL TEMP (K) - ",NTS 342 AFT(CNT)-NTS 345 350 RETURN 355 360 REM********LINEAR REGRESSION OF SIGMAP VS. AFT********** 362 370 A-O \ B-O \ CC-O \ 0-0 \ E-O 372 380 FOR K-1 TO CNT 382 A-A+AFT(K)*SIGMAP(K) \ B-B+AFT(K)**2 388 CC-CC+AFT(K) \ D-D+SIGMAP(K) \ E-E+SIGMAP(K)**2
286
390 392 394 395 396 398 400 402 404 406 408 410 412 414 450 500 501 502
NEXT K ALPHA-(A*CNT-CC*O)/(B*CNT-CC**2) BETA-(B*O-A*CC)/(B*CNT-CC**2) CCOEF-(CNT*A-CC*O)*«CNT*B-CC**2)*(CNT*E-O**2»**-0.5 PRINT "TEMP-COMP PARAMETER ALPHA - ",ALPHA PRINT "TEMP-COMP PARAMETER BETA - ",BETA PRINT#l, CHR$(10) PRINT#l, "TEMP-COMP PARAMETER ALPHA - ",ALPHA PRINT#l, CHR$(10) PRINT#l, "TEMP-COMP PARAMETER BETA - ",BETA PRINT "LINEAR CORR COEFF - ",CCOEF \ PRINT#1,CHR$(10) PRINT#l, "LINEAR CORR COEFF - ",CCOEF INPUT "RUN AGAIN (Y/N)?n;RAG$ IF RAG$-ny" GOTO 16 CLOSE #1 \ END
287
1 2 3 4 5
REM*** REM*** REM*** REM*** REM***
PROGRAM "AFTC2H4" CALCULATE SIMPLE ADIABATIC FLAME TEMPERATURES, EFFECTIVE CROSS SECTIONS, FEED-BASED RESIDENCE TIMES FOR C2H4 COMBUSTION 5/3/89
*** *** *** *** ***
7
9 10 11 12 13 14 15 16 17 18 19 20 22 25 26 27 28 29 30 31 32 33 34 35 40 41 42 45 46 47 48 49 50 51 55 60 61 65 70 71 72 73 75 77 78 79 80 81 82 84 85 86 87 90
DIM A(7),FPK%(5),XF(7),XP(7),B(7),SIGF(7),SIGP(7),C(7),CP(7) DIM SIGMAP(15),AFT(15) . OPEN "#SER01" AS FILE #1 FPK%(1)-20 \ FPK%(2)-6 \ FPK%(3)-22 \ FPK%(4)-200 \ FPK%(5)-0 CALL SYSFUNC(1,FPK%(1» INPUT "RUN NAME: "; RUNNAM$ 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$(10) \ PRINT#1,"EQUIVALENCE RATIO - ",PHI INPUT "FEED RATE OF C2H4 (GMOLES/MIN): ";M PRINT#1,CHR$(10) \ PRINT#1,"C2H4 FEED (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+14.29/PHI)+Y PRINT "TOTAL FEED (GMOLES/MIN) - ",FR \ PRINT#1,CHR$(10) PRINT#1,"TOTAL FEED RATE (GMOLES/MIN) - ",FR TAU-(250*60)/(TEMP*FR*0.0821) \ PRINT#1,CHR$(10) PRINT "FEED BASED RESID. TIME (MSEC) - ",TAU PRINT#1,"FEED BASED RESID. TIME (MSEC) - ",TAU REM******** COMPONENT INDEX ORDER AS FOLLOWS: ******** REM**** 1-C2H4, 2-H2, 3-02, 4-N2, 5-C02, 6-H20, 7-CO **** REM***CALCULATE EFFECTIVE CROSS SECTION OF FEED*********** XF(1)-M/FR \ XF(2)-0 \ XF(3)-M*(3.0/PHI)/FR \ XF(7)-0 XF(4)-1-(XF(1)+XF(2)+XF(3» \ XF(5)-0 \ XF(6)-0 SIGF(3)-XF(3)*5.175 \ SIGF(5)-XF(5)*14.24 SIGF(1)-XF(1)*37.15 \ SIGF(2)-0 \ SIGF(7)-0 SIGF(4)-XF(4)*6.216 \ SIGF(6)-XF(6)*4.446 SIGMAF-O FOR 1-1 TO 7 \ SIGMAF-SIGMAF+SIGF(I) \ NEXT I PRINT "FEED EFFECTIVE CROSS SECTION - ",SIGMAF \ PRINT#1,CHR$(10) PRINT#1, "FEED EFFECTIVE CROSS SECTION - ",SIGMAF REM***********HEAT CAPACITY COEFFICIENTS*********************
288
91 92 93 94 95 96 97 98 100 101 104 105 106
A(1)-2.830 \ A(2)-6.947 \ A(3)-6.148 \ A(4)-6.524 A(5)-6.214 \ A(6)-7.256 \ B(1)-28.60E-3 \ B(2)--0.2E-3 B(3)-3.102E-3 \ B(4)-1.250E-3 \ B(5)-10.396E-3 \ B(6)-2.298E-3 C(1)--8.726E-6 \ C(2)-0.481E-6 \ C(3)--0.923E-6 \ C(4)--0.001E-6 C(5)--3.545E-6 \ C(6)-0.283E-6 \ A(7)-6.420 \ B(7)-1.665E-3 C(7)--0.196E-6 REM*****CALCULATE FEED PREHEAT BASED ON ONE MOLE OF FEED********
PREHT-O FOR I-I TO 7 PREHT-PREHT+XF(I)*(A(I)*(TFEED-300)+B(I)*(TFEED**2-300**2)/2& +C(I)*(TFEED**3-300**3)/3) 107 NEXT I 109 110 REM*********CALCULATE EFFECTIVE CROSS SECTION FOR****** 111 REM***********MIXTURE AT GIVEN CONVERSION LEVEL******** 112 REM***************BASIS IS ONE MOLE OF FEED************ 113 114 FOR J-1 TO 15 \ SIGMAP(J)-O \ AFT(J)-O \ NEXT J 115 CNT=-O 120 IF PHI> 1.0 GOTO 165 125 130 FUEL-XF(l) \ INCR-FUEL*O.l \ TPM-1.0 135 FOR CONV-O TO FUEL STEP INCR 140 XP(l)-(XF(l)-CONV)/TPM \ XP(2)-0 142 XP(3)-(XF(3)-3*CONV)/TPM \ XP(7)-0 144 XP(5)-2*CONV/TPM \ XP(6)-2*CONV/TPM 146 XP(4)-1-(XP(1)+XP(2)+XP(3)+XP(5)+XP(6» 148 CONETH-CONV 150 GOSUB 210 152 NEXT CONV 153 GOTO 360 160 165 OXID-XF(3) \ INCR-oXID*O.l 170 FOR CONV-O TO OXID STEP INCR 171 TPM-1.0+CONV*0.67 172 XP(1)-(XF(1)-0.56*CONV)/TPM \ XP(2)-0.42*CONV/TPM 174 XP(3)-(XF(3)-CONV)/TPM \ XP(7)-0.93*CONV/TPM 176 XP(5)-0.18*CONV/TPM \ XP(6)-0.7*CONV/TPM 178 XP(4)-1-(XP(1)+XP(2)+XP(3)+XP(5)+XP(6)+XP(7» 180 CONETH-0.56*CONV 182 GOSUB 210 184 NEXT CONV 186 GOTO 360 200 210 SIGP(3)-XP(3)*5.175 \ SIGP(5)-XP(5)*14.24 211 SIGP(1)-XP(1)*37.15 \ SIGP(2)-XP(2)*1.352 212 SIGP(4)-XP(4)*6.216 \ SIGP(6)-XP(6)*4.446 213 SIGP(7)-XP(7)*7.767 215 220 SUMP-O \ CNT-CNT+l 221 FOR I-I TO 7 \ SUMP-SUMP+SIGP(I) \ NEXT I 222 SIGMAP(CNT)-SUMP 225 230 PRINT "PROD EFF CROSS SECTION - ",SUMP \ PRINT#I,CHR$(10) 231 PRINT#I, "PRODUCT EFFECTIVE CROSS SECTION - ",SUMP 235 250 REM*******CALCULATE AD.FLAME TEMP. USING NEWTON'S METHOD*******
289
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 4(f6 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-O \ CT-1 FOR I-I 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-I 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 GO TO 330 IF CT - 1000 THEN GOTO 315 ELSE GOTO 320 PRINT "NO CONVERGENCE AFTER 1000 CYCLES" \ GOTO 500 TS-NTS \ CT-CT+1 \ GOTO 265 IF PHI> 1.0 THEN BASIS-OXID ELSE BASIS-FUEL FCF-CONV/BASIS*lOO. \ PRINT#1,CHR$(10) PRINT "FUEL OR OXID CONVERSION (%) - ",FCF PRINT#l, "FUEL OR OXID CONVERSION (%) - ",FCF PRINT "AD FL TEMP (K) - ",NTS \ PRINT#l,CHR$(lO) PRINT#l, "AD FL TEMP (K) - ",NTS AFT(CNT)-NTS RETURN
REM********LINEAR REGRESSION OF SIGMAP VS. AFT********** A-O \ B-O \ CC-O \ D-O \ E-O 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#l, CHR$(10) PRINT#l, "TEMP-COMP PARAMETER ALPHA - ",ALPHA PRINT#l, CHR$(lO) PRINT#l, "TEMP-COMP PARAMETER BETA - ",BETA PRINT "LINEAR CORR COEFF - ",CCOEF \ PRINT#l,CHR$(lO) PRINT#l, "LINEAR CORR COEFF - ",CCOEF INPUT "RUN AGAIN (Y/N)?";RAG$ IF RAG$-"Y" GOTO 16 CLOSE #1 \ END
2C)O
1 2 3 4 5 7 9 10 11 12 13 14 15 16 17 18 19 20 22 23 24 25 26 27 28 29 30 31 32 33 34 35 40 41 42 45 46 47 48 49 50 51 55 60 61 65 70
REM*** REM*** REM*** REM*** REM***
PROGRAM "AFTCOH2" CALCULATE SIMPLE ADIABATIC FLAME TEMPERATURES, EFFECTIVE CROSS SECTIONS, FEED-BASED RESIDENCE TIMES FOR CO/H2 COMBUSTION 3/24/89
*** *** *** *** ***
DIM A(6),FPK%(5),XF(6),XP(6),B(6),SIGF(6),SIGP(6),C(6),CP(6) DIM SIGMAP(15),AFT(15) OPEN "#SEROl" AS FILE #1 FPK%(I)-20 \ FPK%(2)-6 \ FPK%(3)-22 \ FPK%(4)-200 \ FPK%(5)=0 CALL SYSFUNC(I,FPK%(I» INPUT "RUN NAME: "; RUNNAM$ PRINT#I,CHR$(10) \ PRINT#I,"RUN NAME: ",RUNNAM$ INPUT "RUN DATE: ";RUNDAT$ PRINT#1,CHR$(10) \ PRINT#1,"RUN DATE: ",RUNDAT$ INPUT "EQUIVALENCE RATIO: ";PHI PRINT#1,CHR$(10) \ PRINT#I,"EQUIVALENCE RATIO - ",PHI INPUT "MOLAR CO/H2 RATIO: ";R PRINT#1,CHR$(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#I,"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#I,"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#I,"TOTAL FEED RATE (GMOLES/MIN) - ",FR TAU-(250*60)/(TEMP*FR*0.0821) PRINT "FEED BASED RESID. TIME (MSEC) - ",TAU \ PRINT#1,CHR$(10) PRINT#1,"FEED BASED RESID. TIME (MSEC) - ",TAU REM******** COMPONENT INDEX ORDER AS FOLLOWS: ******** REM******** I-CO, 2-H2, 3-02, 4-N2, 5-C02, 6-H20 ******** REM***CALCULATE EFFECTIVE CROSS SECTION OF FEED***********
7r 75 76 77 78 79 80 81 82 84 85 86 87
XF(I)-M/FR \ XF(2)-(M/R)/FR \ XF(3)-M*(1+1/R)*(0.5/PHI)/FR XF(4)-I-(XF(1)+XF(2)+XF(3» \ XF(5)-0 \ XF(6)-0 SIGF(3)-XF(3)*5.175 \ SIGF(5)-XF(5)*14.24 \ SIGF(I)-XF(1)*7.767 SIGF(4)-XF(4)*6.216 \ SIGF(6)-XF(6)*4.446 \ SIGF(2)-XF(2)*1.352 SIGMAF-O FOR I-I TO 6 \ SIGMAF-SIGMAF+SIGF(I) \ NEXT I PRINT "FEED EFFECTIVE CROSS SECTION - ",SIGMAF \ PRINT#l,CHR$(lO) PRINT#I, "FEED EFFECTIVE CROSS SECTION - ",SIGMAF
2C)1
90 91 92 93 94 95 96 97 100 101 104 105 106
REM***********HEAT CAPACITY COEFFICIENTS********************* A(1)-6.420 \ A(2)-6.947 \ A(3)-6.148 \ A(4)-6.524 A(5)-6.214 \ A(6)-7.256 \ B(1)-1.665E-3 \ B(2)--0.2E-3 B(3)-3.102E-3 \ B(4)-1.250E-3 \ B(5)-10.396E-3 \ B(6)-2.298E-3 C(1)--0.196E-6 \ C(2)-0.481E-6 \ C(3)--0.923E-6 \ C(4)--0.001E-6 C(5)--3.545E-6 \ C(6)-0.283E-6 . REM*****CALCULATE FEED PREHEAT BASED ON ONE MOLE OF
FEED*******'~
PREHT-O FOR I-I TO 6 PREHT-PREHT+XF(I)*(A(I)*(TFEED-300)+B(I)*(TFEED**2-300**2)/2& +C(I)*(TFEED**3-300**3)/3) 107 NEXT I 109 110 REM*********CALCULATE EFFECTIVE CROSS SECTION FOR****** III REM***********MIXTURE AT GIVEN CONVERSION LEVEL******** 112 REM***************BASIS IS ONE MOLE OF FEED************ 113 114 FOR J-1 TO 15 \ SIGMAP(J)-O \ AFT(J)-O \ NEXT J 115 CNT-O 120 IF PHI> 1.0 GOTO 165 125 130 FUEL-XF(1)+XF(2) \ INCR-FUEL*O.l 135 FOR CONV-O TO FUEL STEP INCR 140 CONVH2-(1/(1+R»*CONV \ CONVCO-(R/(R+1»*CONV 145 TPM-1-0.5*CONV 150 GOSUB 190 152 NEXT CONV 153 GOTO 360 160 165 OXID-XF(3) \ INCR-OXID*O.l 170 FOR CONV-O TO OXID STEP INCR 172 CONVH2-(1/(1+R»*CONV*2 \ CONVCO-(R/(R+1»*CONV*2 175 TPM-1-CONV 176 GOSUB 190 177 NEXT CONV 178 GOTO 360 180 190 XP(l)-(XF(l)-CONVCO)/TPM \ XP(2)-(XF(2)-CONVH2)/TPM 192 XP(5)-CONVCO/TPM \ XP(6)-CONVH2/TPM 194 XP(3)-(XF(3)-0.5*(CONVCO + CONVH2»/TPM 196 XP(4)-1-(XP(1)+XP(2)+XP(3)+XP(5)+XP(6» 200 210 SIGP(3)-XP(3)*5.175 \ SIGP(5)-XP(5)*14.24 \ SIGP(1)-XP(1)*7.767 211 SIGP(4)-XP(4)*6.216 \ SIGP(6)-XP(6)*4.446 \ SIGP(2)-XP(2)*1.352 215 220 SUMP-O \ CNT-CNT+1 221 FOR I-I TO 6 \ SUMP-SUMP+SIGP(I) \ NEXT I 222 SIGMAP(CNT)-SUMP 225 230 PRINT "PROD EFF CROSS SECTION - ",SUMP \ PRINT#1,CHR$(10) 231 PRINT#1, "PRODUCT EFFECTIVE CROSS SECTION - ",SUMP 235 250 REM*******CALCULATE AD.FLAME TEMP. USING NEWTON'S METHOD******* 255 260 TS-1000. 261 AVHT-1-(O.Ol*HL) 265 SF-O \ SFP-O \ CT-1
292
270 FOR 1-1 TO 6 271 SF-SF+XP(I)*(A(I)*(TS-300)+B(I)*(TS**2-300**2)/2+C(I)*& (TS**3-300**3)/3) 272 NEXT I 280 F-AVHT*(CONVCO*67636.+CONVH2*57798.+PREHT)/TPM - SF 285 FOR 1-1 TO 6 286 SFP-SFP+XP(I)*(A(I)+B(I)*TS+C(I)*TS**2) 287 NEXT I 290 FP--SFP 295 300 NTS-TS-F/FP 305 IF ABS«NTS-TS)/TS) < 0.01 GOTO 330 310 IF CT - 1000 THEN GOTO 315 ELSE GOTO 320 315 PRINT "NO CONVERGENCE AFTER 1000 CYCLES" \ GO TO 500 320 TS-NTS \ CT-CT+1 \ GOTO 265 325 330 IF PHI> 1.0 THEN BASIS-OXID ELSE BASIS-FUEL 334 FCF-CONV/BASIS*100. 336 340 PRINT "FUEL OR OXID CONVERSION (%) - ",FCF 341 PRINT#1,CHR$(10) 342 PRINT#l, "FUEL OR OXID CONVERSION (%) - ",FCF 343 PRINT "AD FL TEMP (K) - ",NTS \ PRINT#1,CHR$(10) 344 PRINT#l, "AD FL TEMP (K) - ",NTS 345 AFT(CNT)-NTS 346 350 RETURN 355 360 REM********LINEAR REGRESSION OF SIGMAP VS. AFT********** 362 370 A-O \ B-O \ C-O \ D-O \ E-O 372 380 FOR K-1 TO CNT 382 A-A+AFT(K)*SIGMAP(K) \ B-B+AFT(K)**2 388 C-C+AFT(K) \ D-D+SIGMAP(K) \ E-E+SIGMAP(K)**2 390 NEXT K 392 395 ALPHA-(A*CNT-C*D)/(B*CNT-C**2) \ BETA-(B*D-A*C)/(B*CNT-C**2) 396 CCOEF-(CNT*A-C*D)*«CNT*B-C**2)*(CNT*E-D**2»**-0.5 397 400 PRINT "TEMP-COMP PARAMETER ALPHA - ",ALPHA 402 PRINT "TEMP -COMP PARAMETER BETA - ", BETA 404 PRINT#l, CHR$(10) 406 PRINT#l, "TEMP-COMP PARAMETER ALPHA - ",ALPHA 408 PRINT#l, CHR$(10) 410 PRINT#l, "TEMP-COMP PARAMETER BETA - ",BETA 41Z PRINT "LINEAR CORR COEFF - ",CCOEF \ PRINT#1,CHR$(10) 414 PRINT#l, "LINEAR CORR COEFF - ",CCOEF 450 500 INPUT "RUN AGAIN (Y/N)?";RAG$ 501 IF RAG$-"Y" GOTO 16 502 CLOS-E #1 \ END
29~
