EXPERIMENTAL AND MECHANISTIC INVESTIGATION 

OF OPPOSED-FLOW PROPANE / AIR FLAMES 

BY PHOSPHORUS-CONTAINING COMPOUNDS 

Richard T. Wainner, Kevin L. McNesby, 

Robert G. Daniel, and Andrzej W. Miziolek 

US Army Research Laboratory 

Valeri 1. Babushoh 

National Institute of Standards & Technolog) 

ABSTRACT 

In this work. we repoil the results of experimental and con1put:itioiial studies on inhibition and extinction of 

opposed-flow propane (C&)-air tlaines by DMMP (CxH.,OIP). as well as N? and FM-200 (CIF7H) as reference 

inhibitors. For the dilute flame conditions used in this work (high Z,,), inhibitor effectiveness was si&rnificantly 

enhanced compared tu previous results with undiluted fuel. However, unlike the previous wwk. OH fluorescence 

signals. and thus concentrations. did not decrease as the inhibitant concentration wab increased, even near extinction. 

The cause for this i.emains to be determinrd. Modeling results for a I-D opposrd flow flainc ofthe smie conditions 

agree with the present results of strady OH levels, while having iilso predicted the decreasing levels fkr the pi-evious 

work with undiluted fuel. 

INTRODUCTION 

Data in the literature show a large number of phosphorus-containing compounds (PCC) to he 

very effective fire suppressants. A number of invcstigations were performed on liquid PCCs in 

premixed and diffusion flames in the 1960s [ 1-61. Since that time, a large amount literature on 

the use of solid PCCs as flame inhibitors has been amassed [7], while a number of compounds 

have seen use as fire retardants in materials and in dry chemical fire extinguishers 181. The references to phosphorus-conraining liquids or gases as flame suppressants are few [9-1 61. On a 

molar basis. PCCs have been shown to be more than 40 times more effective than Nz and 2- 

4 times more effective than CFjBr. Typically, the range of extinction concentralions is 0.5- 

5.0 vol%. 

A fast-acting, effective fire suppressant is what is required to meet the Army’s demand for the 

detection and extinguishment of a fuel fireball in the crew compartment of an armored vehicle in 

less than 250 ms. A demand exists for a safe fire inhibitor of this capability not only for the logic 

of using the most effective compound available, but also because one of thc most widely used 

chemically acting suppre nts, Halon 1301 (CF3Br), has been banned from production since 

1992 due to its stratospheric ozone-depleting capability [ 171. Halogens and phosphorus can also 

be blended, with a mixture of species or in the same molecule. Some research has been performed on the effcctivcncss of halogenated PCCs 16, I I, IS]. However, on a per weight basis, these 

performed no better than the unhalogenated PCCs [ 1 I]. Also, halogenated compounds tend to 

produce toxic products from combustion. It has been postulated that phosphorus-containing 

radical species catalyze the recombination of H and OH in the combustion zone and some evidence exists of H and OH being affected by PCC addition [6, 13, 16, 18. 191. Some data show 

the effectiveness of PCCs to decrease with higher flame temperatures [IO, 131. It has also been 

suggested that only the prcsence and availability of the P atom itself is the sole detcrminer of the 

concentration of species such as HP02, HOPO., and HOPO, and is thus the dominant requirement for flame inhibition [7, 14, 191. However, somc evidence indicates that aromatic phosphorus ring compounds may not be as effective for flame inhibition 113, 141. Particular attention is 

thus called to the different behavior of P-N ring compounds and P-0 compounds. One explanation mighi be that phosphorus atoms are more bound in these compounds. 

Halon Oplion\ Technical Working tontcrcnce 2-4 May 2000 I 4 1 
Several different methods exist for measuring the effectiveness of a potential flame inhibitor. 

The air side extinction concentration for diffusion flames generated by a cup burner is a longstanding gauge [20]. Other measures exist in the form of flame speeds for premixed flames, 

flame heat release, global oxidizer-side strain rate at extinction for diffusion flames, and radical 

species concentrations. This work will measure inhibitor concentrations at extinction and will 

employ planar laser-induced fluorescence (PLIF) for imaging the concentration of the OH radical 

through the flame. The determination of the inhibiting effectiveness of various PCCs and the 

effect of molecular structure is one goal of this research. Another goal is the development and 

validation of an accurate chemical mechanism for the prediction of phosphorus chemistry in a 

combustion environment. While the end objective of this research will be to look at a number of 

phosphorus compounds experimentally and computationally, including DMMP, P3N3F6, and 

P3N3(CH30)6, this report summarizes the current results obtained with DMMP in comparison to 

N2 and FM-200, as well as a comparison to model results with the current developed phosphorus 

chemistry mechanism. 

PHOSPHORUS CHEMISTRY 

The kinetic model of flame inhibition by PCCs (Appendix A) is based on the kinetic data used 

for the analysis of the influence of PH3 combustion products on the radical recombination rates 

in a hydrogen flame and on kinetic models used for describing destruction of DMMP and TMP 

in a low pressure hydrogen flame [18, 19, 21].* (Estimates were also used from selected references [19,21,22]). Reactions of phosphorus-containing species with radicals and intermediate 

species of hydrocarbon combustion have been included. Reactions have been added to the 

scheme to complete the reaction pathways for the consumption of some of the species. The data 

have been adjusted to take into account recent thermochemical and kinetic data for phosphoruscontaining species. Figure 1 shows an abbreviated map of the DMMP decomposition and inhibition reactions. Following decomposition, the main phosphorus -containing species in the flame 

are POz, HOPO, and HOP02. Numerical calculations for a premixed flame [7] and a sensitivity 

analysis show that the burning velocity is most sensitive to the rate of two recombination reactions: (1) H + PO2 + M Q HOPO + M (2) OH + PO2 + M Q HOP02 + M. One important 

characteristic of the model is that the inhibition properties of the PCC are determined by the 

phosphorus molecule content [7, 191. 

EXPERIMENTAL METHODS 

DIFFUSION FLAME 

Measurements were made in a sizeable, axisymmetric, counterflow diffusion flame. The nominally flat flame is produced by vertically aligned opposing jets of oxidizer and fuel. The burner 

head gas outlets are designed for essentially uniform and parallel flow. Gases are directed 

through a series of mesh and porous steel plates, with one of these porous plates serving as the 

final gas outlet. These ducts are 7.0 cm in diameter and are separated by a distance of 2.5 cm. 

* Mokrushin, V., Bolshova, T., Korobeinichev, 0. P., “A Kinetic Model for the Destruction of TMP in a 

Hydrogen/Oxygen Flame,” unpublished, 1998. 

142 Halon Options Technical Working Conference 2-4 May Zoo0 
DMMP + H, OH 

PCH,OCH,(OCH,)O 

4 

4 

k/\ 

CH,P(OCH,)O 

CH,PO,C CH, + 1’0, 

HOPO, HOP0 

PO, 

Figure I. Abbreviated DMMP decomposition and inhibition cycle. Most pathways 

are sustained by the chain carrying radical species H, 0, and OH. 

The heads themselves are enclosed in a large airtight steel chamber connected to an exhaust 

manifold and then to a vacuum pump. Four short arms protrude off the chamber with two exits 

to the exhaust manifold in each. These arms terminate in plates with windows mounted to them, 

providing optical access to the flame for diagnostics and visualization. A nitrogen purge is 

provided to the inside surface of the windows to prevent condensation and soot buildup. Each 

burner head can be translated in two directions and moved in unison, allowing optical and physical probes to investigate different regions of the flame while the probes remain fixed. Cooling 

water is provided to coils around the burner heads and around the outside of the burner chamber. 

The flow conditions for the nominally “neat” flame are 40.0 L/min of air from the upper (oxidizer) duct and 36.0 L/min nitrogen (N-.) plus 3.4 L/min propane (CiHx) from the lower (fuel) duct 

(-17 cm/s velocities). The vacuum pump holds the combustion chamber at moderate negative 

pressure (650 f 10 Torr) to evacuate the combustion products. The gas flows are metered by 

mass-flow controllers and calibrated with a wet test flow meter. These flowrates provide a set of 

opposed jets that are close to momentum-balanced (roVoZ = rFVFZ), yielding a stagnation plane 

for the colliding flows that sits at the center of the burner gap. When ignited, this provides a nonsooting, blue flame that sitsjust barely on the oxidizer side of the stagnation plane. While significantly different from a fuel fireball scenario, this dilute, and thus relatively cool, flame provides 

several advantages. Additive concentrations reaching the flame zone from the fuel side will he 

close to those achieved by oxidizer-side addition. There is no soot to interfere with optical measurements in situ, along the optical path, or on the windows. Secondly. previous work has shown 

some PCCs to he more effective flame suppressors (per mole inhibitor) at higher dilutions, and 

thus lower flame temperatures [9, IO]. Last, as a result, significant expense is avoided by using 

less inhibitor, as even very small vol% concentrations translatc to significant masses at these 

flowrates. 

INHIBITOR AI~DITION 

Additives to the neat conditions are introduced on the oxidizer side only. This is representative 

of a real world extinguisher delivery system. However, while Nz and FM-200 can be delivered 

easily in gaseous form (FM-200 has -50 psig vapor pressure), the vapor pressure of DMMP at 

room temperature is not large (<I Torr). Therefore, DMMP addition to the airstream was perH:hn Option& Techniczil Wrvking Confcrcncc 2-4 May 2000 143 
formed as illustrated in Figure 2. An injection pump capable of metering between 0.001 and 

2000 pl/min delivered preheated DMMP into the preheated air stream. The injected DMMP 

vaporizes and mixes with the incoming air. Heating tape (with thermocouple feedback control) 

held the additive, incoming air, and mixture lines at 80 OC all the way to the burner. 

Figure 2. Schematic of setup for introducing and metering liquid inhibitors of low 

vapor pressure. For the DMMP additions of this work, air and additive 

lines beyond the injection pump exit valve are held at 80 "C. 

OH LIF 

OH concentrations in the flame zone were monitored with varying inhibitor concentrations up to 

flame extinction via planar laser-induced fluorescence (PLIF) imaging. The observed PLIF 

signals were generated by the frequency-doubled output of a narrow-linewidth dye laser, which 

was pumped by a XeCl excimer laser (Lambda Physik models SCANmate 2 and COMPex 102, 

respectively). The pump laser, and thus output beam, were run at IO Hz. Coumarin 153 dye was 

employed to produce output wavelengths near 565 nm (doubled output near 282.5 nm). The 

tuning resolution of the dye laser is 0.001 nm. For OH imaging, the UV beam was tuned to an 

absorbing transition in the (1,O) band of the A2C++X211 electronic transition, specifically the Q1 

branch (J"=4.5) at 282.439 nm. The wavelength tuning was computer controlled and monitored. 

Several excitation wavelength scans were performed to ascertain the exact delivered wavelength 

by comparing to a simulated excitation scan from published transition data [23]. The computer/ 

motor control had some offset error (-,025 nm) and some hysteresis. Hysteresis was monitored 

by imaging a small fraction of the beam (picked off with a microscope slide) through an airspaced etalon, changing the beam into an Airy ring system, and into a monochromator with 

imaging detector. This also showed the spectral width of the beam to be 0.0085 nm FWHM. 

The laser energy varied from 1.25 to 0.85 mJ, due to dye degradation. 

The output beam (-1 mm dia.) is directed into the center of the burner gap through an aperture 

and spread vertically into a sheet with a cylindrical lens (70 mm f.1.) (Figure 3). The beam was 

sufficiently spread that the entire distance between the burner heads (-1 mm wide sheet) was 

illuminated and that the intensity across the reaction (OH-containing) zone was essentially 

uniform. Laser power was monitored between times of data recording with a volumetrically 

absorbing power meter. Shot-to-shot intensities were stable to within 7%. 

144 Halon Options Technical Working Conference 2-4 May Zoo0 
XeCl Excimer Laser 

Fuel + NI (+ additive) + 

---_......_---- 

Figure 3. Laser-induced fluorescence experimental setup. Flow conditions Cor "neat" 

flame are 40 Umin air (upper head) and 36 L/min Nz + 3.4 L/min CiHx 

(lower head). Combustion chamber pressure is typically at 650 Torr. Laser 

excitation is at 282.438 nm. Optical filtering may also be applied to light 

reaching the camera. 

OH fluorescence signals were recorded with an intensified CCD camera (Princeton Instruments 

ITE-CCD) as close as possible to the window at a right angle to the laser beam. Fluorescence 

emission was recorded broadband, over the full temporal and spectral region of OH LIF. The full 

burner gap was imaged and most of the width (Figure 4). Pixel resolution is 81 pm. Images are 

100-shot accumulations. Some background signal level existed from scattering and dark counts. 

These contributions were subtracted from the acquired images and day-to-day signals were 

normalized by the laser energy. The laser energies used in all of these measurements were within 

the range of linear response of OH signal LO laser energy. OH concentration profiles across the 

flame were obtained by integrating signals along a 0.5 cm (60 pixel) width near the center of the 

flame, at a relatively flat portion of the flame, as represented by the rectangle superimposed on 

the image of Figure 4. Overall OH signal levels for each measured set of flame conditions are 

achieved by integrating over the 2-D profile just described, resulting in a single data point. Only 

relative signals are reported in this work. Future measurements will entail a calibration with a 

line-of-sight OH absorption measurement. 

NUMERICAL MODELING 

The phosphorus kinetic model under development was tested in two separate efforts. First, the 

model was included in a previously developed kinetic model for the combustion of CI to Cd 

hydrocarbons and run in a commercially available 1 -D opposed-flow flame code. namely 

OPPDIF [24]. The conditions in this simulation were defined to match the experiments of this 

work. Secondly, the model was run for the methane-air flame conditions of MacDonald et al. 19, 

IO] for both plug flow and potential flow boundary conditions using the procedure developed by 

Nishioka et al. [25]. 

Halan Oplions Tcchnical Working Conlerence 2-4 May 2000 145 
Figure 4. Left: Sample 100-shot OH fluorescence image for “neat” conditions. Right: 

Flame luminescence. (Window opposite camera is uncovered. Light streak is an 

air tube outside the window. Nonuniformities in the flows can be seen in the 

slight wrinkling of the flame. This develops as portions of the porous plate 

become somewhat clogged.) Signal intensities for both images are inversely 

scaled from light to dark. Scattered laser light from the lower burner head can be 

seen at the bottom of the left image. Rectangle represents region of horizontal 

integration for extracting OH profiles. 

RESULTS 

The first experiment performed entailed an effort to visualize the stagnation plane and mixing 

zone. This was achieved by introducing acetone vapor into each gas stream, successively. 

Acetone fluorescence was induced by a laser sheet directly from the excimer laser (308 nm, 

210 mJ). Figure 5 is a processed image resulting from the multiplication of images acquired with 

fuel side and air side addition. The stagnation plane and region of significant diffusion (mixing 

region) are apparent. These flows were nonreacting. 

Figure 5. Image resultant from the product of images of acetone 

fluorescence with fuel- and air-side seeding. 

Figure 6 compares model results with experimental data for the given flame inhibited by DMMP. 

Figure 6a is a comparison of OH concentration profiles for the “neat” conditions. The experimental data have been normalized to the peak level of the model data. While the experimental 

distribution is slightly wider than the model result, the agreement is relatively good. Contrary to 

expectations, however, no decrease in OH signal level was observed for increasing amounts of 

DMMP delivered to the flame. Figure 6b shows that within measurement error, the signals were 

146 Halon Options Technical Working Conference 2-4 May 2000 
2000 I I 1.5 I 

I 

E 

2 1000 

‘z 1500 C 

0 

._ - 

C 

a 

0 

C 6 500 

r 

0 

0 

. -. . model (OPPDIF) 

-experiment 

0 0.5 1 1.5 2 2.5 

Distance from Fuel Side (cm) 

(6a) 

Extinction 

at 150 ppm 

al 

ao 

0 50 IO0 150 

DMMP Concentration (ppm) 

(6b) 

Figure 6. OH concentrations. (6a): Model result for OH concentration through the flame 

compared to experimental OH LIF signals for the “neat” flow conditions. Data are 

normalized at the peak. (6b): Integrated OH LIF signals (experiment) and concentrations (model) versus amount of DMMP added to the flame. 

relatively flat. Interestingly, the model results agree with this lack of response. The reason for 

the behavior of each is unknown at this time. 

The above results support the accuracy of the model. Also, the numerical simulation indicates 

that while OH levels hold steady, phosphorus-containing radicals do increase with added 

DMMP. The compound does seem to act in a chemical manner. The flame is put out with only 

IS0 ppm DMMP. This is not because the flame is right on the edge of thermal stability. A much 

greater amount (8%) of Nz (physically acting molecule) is required to suppress the tlame. Measurements were also performed for FM-200, indicating an extinction concentration of 52.5 ppm. 

FM-200 inhibition also did not reveal any changes in OH levels. The relative effectiveness of the 

two chemically acting compounds is much closer than in previous work with the undiluted flame 

(0.3 and 5.3%). An effort was made to run a less diluted flame for comparison to previous work, 

hut soot in the burner chamber and on the windows became a problem for propane concentrations 

greater than 20%. Initial measurements with PjNj(CH30)6 were also made, but due to a low 

vapor pressure, additive seeding and metering is a challenge. The initial attempt shows that the 

extinction concentration is greater than 100 ppm. Table 1 displays the relative extinction 

concentrations for the current and previous work. normalized to the N: data. 

TABLE I. RELATIVE EXTINCTION CONCENTRATIONS FOR VARIOUS PCCS. 

DATA ARE NORMALIZED TO THE RESULTS FOR Nz. 

Relative Extinction Conceiitrations 

N2 FM-200 DMMP PN Meth Hexa-F PN 

Thi? Work I .O i 0.056 0.0065 i 0.0001 9 * > 0.00 I3 

0.000 I9 0.0001 3 

Previous Work I .o L 0.35 0.23 f 0.0 130 * 0.1 17 L 0.043 

0.043 0.0017 

Haiirn Oplions Tcchnical Working Crmlercncc 2-4 May ?OOO 147 
As mentioned, numerical simulations were also conducted for the PCC-inhibited flames of other 

current research [9, 101. The aim was to obtain the dependence of the extinction strain rate as a 

function of inhibitor concentration for plug- and potential-flow boundary conditions and to 

compare with experimental data. These experiments [9, IO] showed that the addition 0.15% 

DMMP reduces the extinction strain rate by 35%. Calculations with the suggested kinetic model 

and the same conditions indicate a decrease in the extinction strain rate of approximately 30% for 

the same concentration of DMMP. Figure 7 displays the dependency of the normalized global 

strain rate on flame temperature for an inhibited and uninhibited flame. An increase in DMMP 

concentration leads to a decrease in the global strain rate. The turning point of the curve 

corresponds to the extinction conditions. 

Calculated extinction concentrations for flow rates of 30cm/s are the following: 2.2% (molar 

percentage, plug-flow boundary conditions) and 3.6 (potential-flow boundary conditions) (Figure 7). The calculated suppression concentration for premixed flames is in the range 2.8-3.2% 

using critical burning velocity criteria and represents an intermediate value. Calculations of 

DMMP and CF3Br inhibited flames also demonstrate that an increase in inhibitor concentration 

leads to a shift of the OH concentration profile away from the oxidizer side and to a decrease of 

flame thickness. This was observed in orevious exueriments along I 

with a downward trend of OH 

concentration - with increasing inhibitor [ 161. 

2150 

1950 

Y 

.? 

; 1900 

- Ij 

. 

(Y P 

E 

Z 1850 

(Y 

y I800 

I l800 1750 I 

0 $000 10000 ti000 20000 25000 30000 35000 10000 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 

Normllizea wain we. 11s DMMP concentration (ppm) 

(7a) (7b) 

Figure 7. (7a): Dependence of a maximum flame temperature (inhibited and unihibited) on the 

normalized global strain rate. Methane/Air flame conditions as in Refs. 9 and 10. 

Burner gap is 0.95 cm. (7b): Flame temperature dependence on DMMP addition for 

plug- and potential-flow boundary conditions (30 cm/s flows). 

CONCLUSIONS 

Chemical inhibition experiments were performed in a near atmospheric pressure, low strain, 

dilute opposed-flow flame. These conditions proved to be very sensitive to the addition of 

inhibitive agents. For DMMP, 150 ppm was sufficient to extinguish the flame. Though the 

flame is cool, the strong inhibition effectiveness should not be due to being near the physical 

(thermal) extinction limit, as a full 8% Nz addition is required to extinguish the flame. The 

increased effectiveness of the chemical inhibitors relative to Nz compared to the undiluted flame 

work is of much interest. 

148 Halon Options Technical Working Conference 2-4 May 2000 
While the flame seems more sensitive to chemical inhibition, the concentration of the radical 

species OH shows no signs of being affected by the concentration of inhibitor, right up to the 

point of extinction. Broadband, planar, laser-induced fluorescence emissions from OH are 

essentially constant as inhibitor concentration is varied. An explanation for this behavior is not 

apparent. However, a numerical model ofthe same conditions with a newly developed model for 

phosphorus chemistry show the same OH insensitivity to DMMP concentration. 

Calculations of extinction concentrations were performed for opposed flow diffusion flames with 

different boundary conditions. Extinction concentrations (tlow rate 30cmis) are the following: 

2.270 (molar percentage, plug-flow boundary conditions) and 3.6% (potential-flow boundary 

conditions). The calculated extinction concentration for a premixed flame represents an intermediate value (2.8-3.2%). The modeling of extinction strain rates corresponds to the experimental data of MacDonald et ai. [9, IO]. 

ACKNOWLEDGMENTS 

This work is supported by the Next-Generation Fire Suppression Technology Program (NGP) 

and the American Society for Engineering Education (ASEE). 

I. 

2. 

3. 

4. 

5. 

6. 

7. 

8. 

9. 

10 

REFERENCES 

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Rosser, W.A.. Jr., Inami, S.H., and Wise, H., “The Quenching of Premixed Flames by 

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150 Halon Optionr Technrcal Working Contcrence 2-4 May 2000 
APPENDIX A. KINETIC MODEL FOR FLAME INHIBITION BY DMMP ~ 

n ~ 

0. 

0. 

0. 

0. 

c. 

0. 

0. 

Reactions 

DMMP-PHCH3OCH3O +CH2(I 

A!f Icra,s,mol)l 

3.6E12 

Ref 

. 

3 

DKMP=PCH3OCH3 (OCH2) O+F 

PCH2OCH3 !OCHZ)O=CH3P IOCh3)O+C?lZO 

PCE3OCH3 IOCHZI O-CHiOlOPCS3OCH3 

PCH3 IOCH3) 2OiiiPOHCH30CH30iCH3 

POHC~3OCH30=CH30YO2+~~II~ 

POHCH3OCH3O=CH3PO2+CH3OH 

P (OH) 20=H20iPO:, 

CH30PO=CF?,PO? 

?OH IO< 

OPCH30CHI=CHC 

OICH30CH3-Chl 

CH3P lGCSlO=i 

CH~OPO~=HOPO~CH~O 

LE14 

J.7E14 

1 .Ei14 

LE13 

I. 7Ei12 

1.7112 

I. ?E+l>? 

I .E+12 

:.El! 

1 7Eil2 

1.0Ei14 

0.lEli 

l.Z:14 

1 .OE+ll 

1. IE12 

LEI1 

I .OEl? 

L.OEl? 

I. GEl2 

LE17 

I.0E-14 

LEI3 

3.0Ei12 

LE13 

3.0E+12 

3.0Eil2 

3. Oer 12 

2.0E~ll 

1.0Eill 

l.OE+i/ 

3. 0Ei 12 

l.OE+lL 

LE14 

?.E23 

2.Eill 

1. OEil4 

l.El:: 

LE24 

1.81E+2? 

2.2E30 

3.16E1113 

3.16Ei13 

LE13 

3 ~ 16Ei13 

9.73ti23 

3.16Eii3 

3.161113 

6.4ELC 

3.16E111 

5. 

6. 

39000. 

3Y03C. 

40000. 

27000. 

39000. 

8. 

9. 

IO 

11 

12 

13. 

14. 

23 

?1 

21 

I1 

23 

. L, -, ., :H3)20=CH30POZ+CH33H 

!+CH3PC'I 

:CPO+CUI 

18000. 

3081IC 

JO000 

390m 

200c0. 

4000. 

8000. 

3C00 

18000. 

4000 

21 

23 

21 

21 

23 

22 

L> .> . 

JH3POLICHI 

OPOH'H3+M=ROPOICH:,rM 

OF 101') ?OCHi=HOPO?+CH33H 

DIIMPIS-PCH30CHi (OCH? 1 0-HZ 

POI3 !OCSi3)20+H~OP (OH1 2OCH3iCH3 

OP !OH) 2OCH3+H=OP (OH) 3tCE3 

OP~HC~:~=IIOPO+CH~ 

15. 

16. 

11 

-8. 

0 

0. 

0 

0. 

19. 

20. 

2:. 

II '> 

"1 

_. . 

.. i 

24 

26 

27. 

28. 

79. 

1H30 

23 

21 

2: 

21 

21 

73 

3. 

8000 

4000. 

8000 

4030 

18000. 

8C00 

43i;o. 

12000. 

10000. 

40011. 

CIIIPO?+H=OPOHCH3 8000 

CH'3OPO2+H=HOFO+CHIO 

CH30PO2 *H-C?33P02rOH 

C".30P02+H-HOP02+Cii3 

~HCII30CH3311I-OPCH3OCS~~~ El 

CH3P IO(J113) OiH I +X) =PHCH3OCH3CI u. 

c.0 n 

C. 

0 

0 

36. 

3 7 

38. 

39. 

40. 

41. 

42. 

43. 

8000 

4000 

645. 

0. 

1330 

4320 

8000 

11930. 

23 

23 

2 3 

21.19 

-1 

- 2.04 

-I. $5 

-4. 2a 19,fiZ 

23 

15,21 

23 

23 

73 

15 

19, flt 

23 

23 

23 

U. 

c. 

0. 

(1 

0. 

- 2.04 

H+HOPO=H?O+PO 

3-P IOH) 2O=H7+HOPO? 

H+HOPO~=HZO+PO~ 

HOPOL+H+M=F (OH) 2OiF 

HtHPO=-I2~PO 

HIPH=III+P 

H+I+M=PH+M 

44 

45. 

46. 

47. 

48. 

0. 

8000 

2500. 

5000 

1740 

12000. 

9000 

3620. 

10645 

0 

49. -1. ~17 

50 

51 

52 

:3. 

'14. 

55. 

56. 

57 

0. 

0. 

-3.66 

3.16F,+ 13 

1.2E25 

3.14E113 

3.16E+:3 

5 16E113 

4. GF.36 

I .E12 

LE13 

I .E13 

LEI2 

19,flt 

15 

23 

23 

15,fic 

4150. 

4000 

200l1. 

4000. 

4300. 

4000. 

15000. 

to90 

21 

21 

11 

73 

12 

21 

2? 

21 

I, 3 L/ 

58 

5% 

60. 

61 

62 

63 

64 

65 

66 

67. 

68. 

65. 

DMMP+OP-POH lOCH31 LOICH3 

POH IOCJH3120 iOIl-OP (OH1 20CH3+CH30 

P 10Iil 20+OH-HOPO2IE23 

P (OH1 2O+OH+M=OP (O!?) 3iK 

PCJH3OCH3 lOLll2 I O+OH=~~H2G+POHCH30CM30 

POHCE'?OCfl3O+OH=OP IOH) 2CHllCH30 

OP IOfI) 2CH310H-OP !OH> ?+CH3 

PHLH?OCH~~TOH=OPCH~OC~~+H~~ 

CH30PO2+OH=HOP02 i CH3G 

CII3POL'+OS=HOPG2+CII'~ 

OH+PO2rM-HOPO2+M 

OHiPOi I.l=ilOPo +M 

OH~HOPO-II~OI pO2 

39+PO=H+P3? 

OH iP-li+?O 

PHCII~OCH~~+OH=CH~P (0cii;i ~~20 

". 

285 

0. 

4000. 

4000. 

C. 

I1 

0 

3.EilZ 

LE413 

3.E13 

3.0E+l7 

3.0L+l% 

1. hC+?4 

0. 21 

0 21,"lod 

40110. 

8000 

285 

1390 

21 

21 

21,19 

21, i9 

23 

14 

70. 

11 

72 

J '3 

7$ 

~~ 

1 15Fi0 

3.Li12 

3.16Ei I1 

? 16Eii3 

0. 

0 

5970 

4650. 19 

Halon Option\ Tcchnical Working C~mlcrcnce 2-4 May 2000 15 I 
78. OH+HPO=H+HOPO 

79. OH+PH=HEO+P 

80. OH+PH=H+HPO 

81. OHiHZPOH=H2O+HPOH 

83. OH+PH+M=HPOH+M 

84. DMMP+0=PCH30CH310CH2lO+OH 

85. O+OPOHCH3=0H+CH3P02 

86. O+CH3P02+M=CH30P02+M 

87. O+CH3P02=CH3+PO3 

88. O+CH3P02=CH20+HOPO 

89. O+P (OH) 20=HOP02+0H 

90. O+OPOHCH3=CH3+HOPO2 

91. O+CH30PO=CH20+HOPO 

52. OtCH30P02=HOP02tCH20 

93. O+PO+M=POZ+M 

54. O+HOPO+M=HOP02+M 

55. O+HOP02=02+HOPO 

56. O+HOPO=OH+P02 

57. O+HPO=OH+PO 

98. OtHPO=HtPOZ 

95. O+P03=02+P02 

lOO.O+PH=PO+H 

lOI.OtPH=OH+P 

102.0+H2POH=OH+HPOH 

103.0+HPOH=H+HOPO 

104.O+P02+M=P03+M 

105.0+P+M=PO+M 

106.0 + PH t M = HPO + M 

107.0+HPOH=OHtHPO 

108.H02+P02=02+HOPO 

105.H02+PO2=0+HOP02 

llO.H02+P02=OH+P03 

lll.H02tPO=02+HPO 

112 .HOZ+PO=O+HOPO 

113.H02+PO=OH+PO2 

114.H02+HOPO=OH+HOPO2 

115.H02tP03=02+HOP02 

116.H02+HPO=O2+HPOH 

117.HO2+P=02+PH 

118.H02+P=OH+PO 

115.H02+PH=OH+HPO 

12O.H02tPH=HPOH+O 

121.H02+HPOH=02+H2POH 

122,DMMP+CH3=PCH30CH3(OCHZ)O+CH4 

123.CH3+P02=CH3P02 

124.CH3+P03+M=CH30PO2+M 

125.CH3+P03=POZ+CH30 

126.CH3+HPO=CH4+PO 

127.CH3+HOPO=P02+CH4 

128.CH3+HOPOZ=P03+CH4 

129.Po2+P=Po+Po 

130.02+P=O+PO 

I3I.HOPO2+P=PO+HOPO 

132.P + PO3 = PO + PO2 

133.P + HPO = PO t PH 

136.P + HPOH = HPO + PH 

137.02iPH=O+HPO 

138.PH + PO2 = PO t HPO 

139.PH i PO2 = HOPO + P 

140.PH + HOP02 = HOPO + HPO 

141.PH + PO3 = PO2 + HPO 

142.PH + PO3 = HOP02 + P 

143.PH + HPOH = P + HZPOH 

144.PO+HOP02=P02+HOPO 

82. OH+HPOH=HSO+HPO 

145.02+PO=O+PO2 

146.PO+HPOH=HOPO+PH 

147.PO + HPOH = HPO + HPO 

145~PO + 02 +M = PO3 tM 

148.~0 + PO^ = POZ + POZ 

~~~ ~. ~~ ~~ 

150,POtCH30=CH3+P02 

151.P02 + HPO = PO + HOP0 

i52.PO2 i HZPOH = HOPO + HPOH 

153.P02 + HPOH = HOPO + HPO 

154.P02 + HPOH = HOP02 + PH 

l55.P02+H202=HOPOZ+OH 

156.P02+CH30=HOPO+CH20 

3.16Eill 

3.16Eill 

3.E+12 

3.16E+ll 

3.16Etl1 

3,16E+ll 

3.16Eill 

3.16E+ll 

7. /E17 

5.E12 

3.E12 

1.E13 

3.E12 

2 .E12 

1.E13 

3.E12 

1.E12 

].E12 

4.9325 

4. BE31 

LE13 

3.16E113 

3.16Et13 

3.16E+13 

3.16E113 

3.16Eii3 

3.16Et13 

3.16Et13 

3.16E+13 

6.E33 

1.5E23 

7.4E14 

3.16Et13 

3.16E+ll 

3.16Eill 

3.16Etll 

3.16E+ll 

3.16Eill 

3.16Etll 

3.16Eill 

3.16Eill 

3.16Etll 

3.16E+13 

3.16E+11 

3.16Eill 

3.16Eill 

3.16Etll 

5.E12 

LE12 

LE16 

1.Ei3 

LE13 

3.E12 

3.E12 

3.16E113 

3.16Et13 

3,16E+13 

3.16E13 

3.16E13 

3.16E13 

3.16E+ll 

3.16Ell 

3.16Ell 

3.16Ell 

3.16Ell 

3.16Ell 

3.16Ell 

3.16Etll 

3.16E+ll 

3.16EilI 

3.16Ell 

3.16Ell 

1 .El5 

LE13 

3.16Ell 

3.16Ell 

3.16Ell 

3.16Ell 

3.E12 

1.E12 

0. 

0. 

0. 

0. 

0. 

-3.55 

-4.34 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

-5.12 

-2.28 

-0.414 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0 -. 

a. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

0. 

9700. 

6000. 

0. 

12000. 

2430 

4545. 

1600. 

3280 

1530 

8000. 

0. 

0. 

0. 

0. 

5000. 

0. 

0. 

3580 

4400. 

10000. 

0. 

0. 

12000. 

6000 

U. 

2387. 

3720. 

2800 

0. 

5190. 

2330. 

420. 

4600 

630 

0. 

2500. 

6750. 

0. 

3700. 

inoo 

0. 

10200. 

6800 

1580 

1830 

0. 

5280. 

10000. 

0. 

0. 

12000. 

4000 

8000. 

20000. 

4510. 

4200 

6850 

40. 

6900. 

9700 

5723 

4800. 

70. 

6700 

0. 

0. 

6900. 

9730 

10000. 

0. 

10100. 

0. 

0. 

3000. 

0. 

0. 

1800. 

0. 

10000. 

0. 

19 

23 

23 

15 

19 

15 

19 

19 

23 

23 

23 

23 

23 

23 

23 

23 

23 

19. fit 

19.fit 

15, fit 

23 

15 

23 

19 

19 

19 

15 

19 

15 

19,fit 

15,fit 

19,flt 

19 

19 

19 

23 

19 

15 

19 

19 

19 

15 

19 

19 

19 

15 

19 

23 

23 

23 

23 

23 

23 

23 

19 

19 

19 

19 

19 

19 

19 

19 

19 

19 

19 

19 

19 

19 

23 

19 

19 

19 

23 

23 

15 

19 

19 

19 

23 

23 

152 Halon Options Technical Working Confcrence 2-4 May Zoo0 
157.OH+HOE02=H20+PO3 

158.H+HOPO?=ll2.+il03 

159.PO3 + HOPO = PO2 + HOPO? 

160.POi 

161.POS 

162.EO3 

163. E03 

164 .PO3 

165. PO3 

166 .HE0 

l6'l.HPO 

+ HPO ~ PO ~i HOf 

i HZPOH = HOPO? 

i HPOfl = HOPO? i 

+CH3O=HOPO?+CHZO 

+C2H6-HOPO?+C2€!5 

iflCO=HOP02+C0 

+ HPOH = PO +HZE 

'02 

* HPOH 

HPO 

'OF. 

?.CI? 0. 

3.E12 0. 

3.16Ell 0. 

'3 . I 601 1 0. 

3.16tll 0 

3.16E11 0. 

LE12 0. 

5. El2 0. 

LEI3 3. 

5.lCEll 0. 

l.il3 0 

5.El2 0. 

3. I6E11 0. 

9000 

18000. 

1450. 

U. 

0. 

0. 

0 

8000 

0 

4950. 

500i 

9000 

7 roo. 

H;il(rn Optirmh Technical Working Cimlcrencc 2-4 M;iy 2000 153