A FIBFIS Sampling Study of Formation of Nitric-Oxide in a Premixed

Fuel-Rich Methane-Air Flame

A thesis submitted in partial


of the requirement for the degree Raster of Science in Engineering

Ivan A. Gargurevich


The thesis of Ivan A. Gargurevich is approved.

U, D. Van Vorst

Ouen I, Smith

Eldon L. Knuth, Committee Chair

University of California, Los Angeles 1980

To Horn and Dad, Lucia, Cynthia, Irene, Sergio,
and Carmen,


ix xii

xiii i



The Formation of NO in Fuel-Lean Flames .

2.2 Prompt NO Formation ........... 2.3 Formation of NO in Fuel-Rich Flames ...

2.4 Mechanisms of Methane Oxidation ..... 2.4.1 Methane Oxidation in Fuel-Lean Flames .............. 2.4.2 Methane Oxidation in Fuel-Rich


Flames .............. 34 CHAPTER 3. 3.1 EXPERIMENTAL APPARATUS 44

An Introduction to Sampling Techniques in Combustion Studies .......... 44


Possible Composition Distortions in MBMS Sampling of Flames 3.2.1 ........... 53

Free-3et Expansion ........ 54


PAGE 3.2.2 Chemical Relaxation in Supersonic Expansion ............. 3.2.3 3.2.4 3.2.5 3.2.6 3.2.7 3.2.8 3.2.9 Species Condensation Pressure Diffusion Relaxation Phenomena Skimmer Interference Mach-Number-Focusing ....... ........ ....... 59 63 65 69

. . . . . 0 . 71 „ . 72 76

Background Scattering ....... Flame Perturbations by Sampling Cones

77 .... 83


The U.C.L.A. MBMS Sampling System



4.1 Composition Measurements ......... 4.2 Temperature Measurements ......... 4.3 Calibration Procedures .......... EXPERIMENTAL RESULTS ... . .


5.1 Temperature Measurements in the Flame 5.2 Stable Species Profiles 5.3 . .

Formation of Nitric-Oxide in the Flame . . 112 . .. . 124 .... 130 136 . . . . . 140

5.4 C2H2, C2H6 Profiles 5.5

CH. and H2CO Species in the Flame .... .


LIST OF FIGURES FIGURE 1. 2. node of coal formation The dependence of CH20, C2H4, C2H2, and H2 peak concentrations on flame equivalence ratio 3. ................... 40 PAGE . 3

The dependence of peak C2H,, C2H2, and H2 on peak 0.56 JCH-, } for a range of flames $ =

to 1.25

\ 41
..... 50

4. 5.

The U.C.L.A. MB[*]S sampling system

Temperature ratio as function of dimensionless flou time for free jet gas flows from orifice 52 55

6. 7.

Free-jet shock structure .......... Schematic diagram of model considered in Mach-number-focusing

74 . . 89

8. 9.

Intensity vs. electron energy for Argon

Temperature profile measured using TDF technique ..... ......... 93


Temperature profile measured using TOF techniques 100


Normalized Oxygen profile (tip dia. = 2.0
mm, d^ = 0.24 mm)


Normalized Oxygen profile (tip dia. = 0.5 mm, d^. = 0.30 mm) ........ . . ..... 105




C02 normalized profile (tip dia. = 2.0 mm, d# = 0.24 ram) ................ IDS


Normalized C02 profile (tip dia. = 0.5 mm,

d^. = 0.30 mm)

. . . . . .107

02, CI-L, and C02 mole-fraction profiles for CH^-Air flame ................ ill

16. 17. 18. 19. 20. 21.

NO concentration profile

.......... 114

NI-U concentration profile .......... 115 HCN concentration profile .......... lie Normalized m/e = 30 profile 117

Normalized m/e = 17 profile ......... 119 Normalized m/e = 43 profile ......... 123 ......... 126

22. C2H2 concentration profile 23. 24.

Normalized m/e = 27 profile . .... . . . . 127 Normalized m/e = 30 profile 129 ........ 131

25. C-atom concentration profile 26. CM concentration profile 27. 28. CH2 concentration profile Normalized m/e = 15 profile

.......... 132 133 134


TABLE 1. 2.

PAGE Methane oxidation in fuel-lean mixtures ... 35 Methane oxidation in fuel-rich mixtures ... 36

\M 1


speed of sound calibration constant appearing in Eq. (56)

d d.£ d, D E C3
# E
f h I. ID k.

effective source-orifice diameter cone orifice diameter skimmer entrance diameter binary diffusion coefficient electron energy in ev
activation energy mole fraction of heavier species total enthalpy ion signal intensity of species i electron emission in mamp foruard reaction rate coefficient for the ith reaction

k__ •

reverse reaction rate coefficient for the ith reaction

K Kn '"Id m m. m/e n

equilibrium constant Knudsen's number skimmer entrance - detector distance mean molecular ueight molecular ueight of species i mass to charge ratio number density

n, n, p j Re S

number density at detector number density at skimraer entrance pressure mass density Reynolds number speed ratio speed ratio perpendicular to jet axis Schmidt number temperature static temperature perpendicular to jet axis static temperature parallel to jet axis time most probable velocity of molecules diffusion velocity
nach disk location

Sj_ Sc T Tj^ T,, t u v


r-lach disk diameter diameter of the barrel shock

thermal diffusivity u~~t n 0 enrichment factor as defined in Eq. calibration factor appearing in Eq. (49) (56)

(Fuel/Air) actual/(Fuel/Air) stoich., equivalence ratio

0 'u in,p V

heat capacity ratio, C /c relaxation time at constant h,p


relaxation time at constant T.p mean time between collisions of A and B molecules

\ cr

mean free path hard sphere collision cross section


eq 0 1

denotes equilibrium values denotes stagnation conditions denotes conditions at skimmer entrance frozen process

ACKNOULEDGPIENTS I uould like to express ray gratitude to Dr. Eldon Knuth for his continued guidance and encouragement during the time this uork was performed.
Also, I uant to thank all members of the Molecular Beam Lab. for their cooperation, and especially to Dr. 0. Smith, Fir. Uayne E. Rodgers, and Ph.D. stu-

dent S. Yoon for sharing their knowledge and useful information. This study uas supported by NSF under Grant No. ENG-7709190.


ABSTRACT OF THE THESIS A MBWS Sampling Study of Formation of Nitric-Oxide in a Premixed Fuel-Rich Methane-Air Flame

Ivan A. Gargurevich Plaster of Science in Engineering University of California, Los Angeles, 1980 Professor Eldon L. Knuth, Chair The formation of NO in a fuel-rich, premixed methane-air flame at one atmosphere uas studied using molecular-beam-mass-spectrometric (MBMS) sampling techniques. A flat flame of equivalence ratio 1.37 uas

sampled uith particular attention given to NO, HCN, HNCO, and MB., species. The onset of formation of HCN uas

found to occur prior to the formation of NO, approximately at the same time as the formation of NH,, and very near the primary reaction zone of the flame. Decay of

HCN leads to NH- formation, and, to a lesser extent, to iJ NO formation. HNCO is observed at very lou concentrations

in the post-flame gases, and acts as an intermediate in HCN decay. The peak mole fractions of HCN and NH^

about 67 and 44 ppm., respectively,and Nitric-

Oxide reaches a mole fraction of 56 ppm. after all of the HCN, and NH^ have decayed. The Zeldovich mechanism,

taking into account radical overshoot, accounts, at most, for 10 ppm. of the NO formed in the flame; the rest is the result of HCN decay. The same flame uas sampled for C, CH } and CI-U« CH,-,,

The peak mole fractions of C, CH, and CH-

were found to be about 206, 481, and 908 ppm., respectively, uith an uncertainty of a factor of approximately 2. Because of their greater concentrations, CH and CH~ The con-

are the most likely to lead to HCN formation.

tribution to the CH., profile from CH, could not be totally eliminated, even at electron energies as lou as 13.3ev. No effort uas made to estimate its mole fraction in the flame. mary reaction zone. The flame uas also sampled for H-CO. Its The CH-, profile peaks uithin the pri-

formation is observed to occur before the formation of CHr, and upstream from the reaction zone of the flame.

The rate of formation CH-, does not reach significant levels until most of the formaldehyde has decayed. A relatively large concentration of acetylene (2100 ppm.) uas found; its formation and decay occurred Ethane, in

mostly uithin the primary reaction zone.

much smaller concentrations, uas also observed in the same region. The tuo-carbon species provide additional


paths for the decay of CH- and must be included in the kinetic modeling of fuel-rich hydrocarbon flames,
Visible attachment of the flame to the quartz cone uas observed for the flame of equivalence ratio 1.37. Temperature measurements, made using time-of-

flight (TOF) techniques, shoued that the effect of attachment is to decrease the measured temperature gradient within the reaction zone. A cone of smaller Relative inten-

tip diameter minimizes this effect.

sity profiles shoued also smaller measured gradients uithin the primary reaction zone for a cone of relatively large tip diameter. Attachment of the flame to the

cone persisted approximately until the end of the primary reaction zone.



In the last decade, in order to satisfy an ever-increasing continuing demand for energy, and as a result of of crude

decline in the domestic production

oil, the United States has been forced to import crude oil and refined products in increasing amounts. It is 83 forecast that, in 1980, thirty percent of our total energy uill come from the Middle East Nations. Fur-

thermore, since 1972, the fraction of the energy used for producing the U.S. GiMP uhich has been based on imported oil has doubled, increasing from a level of about 13£o of the U.S. GNP in 1972 to about 26% of

the U.S. GNP in 1978.

Since the end of 1978 the OPEC

cartel has raised the price of its exported crude by 61j£, and it is estimated that by 1985 it uill reach

In 1985 the U.S. could be import83 ing as much as 15 million barrels per day and, with an estimated price of $40 per barrel, the cost for 1985 would be $220 billion. By comparison, the value

340 per barrel


of oil imports into the U.S.A. in 1972 uas $4.5 billion, The finite limits of U.S.A. oil and natural 84 gas reserves are fairly well established ; both could

be exhausted in ten years if they uere worked to their fullest capacity. However, the estimated resources Btu.

of coal amount to approximately 90,000 x 10

(or about 430 billion tons) which at the present consumption rates would last for about 666 years. In the near future, the U.S.A. will have to find or exploit alternative sources of energy if it is to play an important role in the world community. In Duly 1979, President Carter announced his Energy Plan. The main objectives of the Plan were to dimin-

ish oil imports, to accelerate the conservation of oil fuel, and to spend $88 billion over ten years to promote synthetic-fuel production from coal and shale rock. According to Carter's Energy Plan for about the

next ten years, oil imports would be kept at the 1977 level of 8.2 million barrels per day; 2,5 million bbl./ day would be gained by synthetic fuel production and 2 million bbl./day through conservation and conversion measures. Carter's Plan would require coal production (in 1979 coal production was 625

to double by 1985

million tons per year) °r, in the seven-year period 1979-1986, 107 million tons of new capacity would have to be added every year.







U S —• 3 i ~J M ! N G U S —"A r-JTH= AC ~ KIGH M=D.
C5A 80

%C 60 %0 Ci!-CR:riC I2CCO VALUE



1200 o

15 I4OCO


3 S55GC

Fig, 1. Mods of coal formation . ( Source : Ref. 85 .)

It is clear then that combustion of coal and products derived from coal and shale rock will be playing an important role in the U.S. energy picture for years to come. (Nuclear energy supplies about 3% of the Its devel-

total energy produced in the U.S. today.

opment, however, has encountered much opposition and it is unlikely that construction of new nuclear plants uill be started in the 1980's). marily from plants. formation. Coal originates pri-

Fig. 1 shows the steps in coal

Through a series of evolutionary changes,

the primary products of the original decomposed plant matter becomes transformed sequentially into peat, lignite, subbituminous coal, bituminous coal, and finally to anthracite. Uith these transformations the

carbon content increases and the oxygen content decreases.
n j-


' indicate that there is some correlation be-

tween coal rank and its aromaticity, 40-50^5 aromatic carbon content for subbituminous coal and 90% aromatic carbon content for anthracite. These studies showed

no correlation between H/C mole ratio and percent aromatic carbon. Oxygen occurs predominantly as pherolic Sulfur found in coal has Sulfur conNitrogen

or etheric groups in coal.

a similar functional chemistry to Oxygen. tent in coal varies from 2 to 3 percent.

occurs predominantly as pyridine or pyrrolic type rings, and coal contains typically from 1 to 2 percent nitrogen

by ueight.

Coal structure is consistent with highly


substituted aromatics uhich are not highly condensed. Coal undergoes primary decomposition in the temperature range 400 - 450 C. The realization of limited and non-reneuable energy resources and the increasing role of combustion in the years ahead uill require extensive research in the areas of energy conservation and combustion problems. As a result of President Carter's Energy

Plan, there uill be a shift to direct coal burning by the Utilities Companies and Industry. The health,

safety and environmental threats posed by mining and burning of coal are severe. Increased coal burning

uill result in larger emissions of sulfur dioxide, carbon dioxide, and nitric oxide into the atmosphere. The accumulation of carbon dioxide might result in the so called "Greenhouse" effect predicted by many scientists. The large amounts of ash that uill result

from coal burning uill have to be disposed of in an environmentally safe manner. The production of syn-

thetic fuel uill also cause environmental problems. Furthermore, the production of synthetic fuel might require huge amounts of uater for hydrogen production. The strain on existing uater supplies might be considerable and one can foresee legal battles for uater rights betueen the coal-producing states.

In 1974,

transportation accounted for 54/5
n £!

of the total liquid fuel consumption ' in the


It is most likely that transportation uill depend primarily on liquid fuels in the near future. Most of

the liquid fuel being consumed today in America is lou in aromatics content and has a high H/C content (the average H/C ratio being 1.9). Houever, unless

extensive hydrocracking and hydrogenation are conducted, the properties of synthetic fuels are different from those of the fuels being used today in transportation. Synthetic fuels are high in aromatics content and have a H/C ratio of about 1.2-1.5. Transformation of syn-

thetic fuels from coal into more "gasoline-like" fuel Rfi results in an energy loss of about 2Qfa of the heat of combustion of the syncrude being processed. The

elimination of restrictions on H/C ratio and boiling range in fuel manufacture uould result in a considerable reduction in the cost of the fuel. As a result

of its properties, synthetic fuel combustion uould result in the emission of large amounts of soot by the internal combustion engine . Thus, extensive research

is needed to eliminate the need for high levels of hydrogenation and boiling range conversion in the manufacture of fuels from coal. Furthermore, more research

is needed in the chemistry of soot formation and burnout.

It is evident that, in the future, ue uill have to burn prime fuels more efficiently with less pollution and ue shall also have to burn much material that is not nou considered suitable fuel at all. As UeinoY berg points out, progression in combustion systems is in the direction of more controllability. The pro-

gression has been from diffusion flames (the reaction zone is aluays near stoichiometric, corresponding to the maximum possible flame temperature and hence the largest NO emission) to premixed flames, uhich allows

one to vary flame temperature, burning velocity, ignition temperature, and stability criteria by controlling the fuel/air ratio to the uell-stirred reactor. Uein-

berg proposes that the next step should be breaking auay from this dependence on initial fuel/air ratio and control the reaction rates in the flame independently. To take this desirable step on combustion systems, ue must control the reaction rate independently by making the temperature in the reaction zone a separate parameter, using variable heat recirculation, injection of free radicals, radiation, etc. This study is concerned with the kinetics of formation of nitric oxide in an atmospheric, fuel-rich, premixed, methane-air flat flame, and it is part of a series of studies that are being conducted in U.C.L.A. with regards to nitric oxide formation from fuel-ni-

trogen in flames.

To give the reader an idea of the

magnitude of this NO formation, in the study of methaneair flat flames by R. Gay at U.C.L.A., a concentration

of 140 ppm. uas reported in the post-flame gases of a mixture of equivalence ratio 1.1. In this same flame, by the

the primary reaction zone uas characterized

rapid formation and decay of formaldehyde uith a maximum concentration of 540 ppm., and NO formation uas restricted to the post-flame region. The primary reac-

tion zone uas located uithin the first 5mm. from the burner surface. In the study of NO formation in a fuel-

rich flame, the coupling betueen the NO-formation reactions and the combustion reactions must be considered. This requires a knouledge of the combustion mechanism, and for methane combustion, although extensively studied, there are questions regarding the rate-determining step, the f^CO-decay mechanism, the fate of CH~ species, and the role of t^ hydrocarbons. Nitric oxide above

that predicted by the Zeldovich mechanism is said to form via the formation and decay of HCN. The forma-

tion mechanism for this species has been studied but very little is knoun about its decay mode. Experiments

indicate that NHj_ species and OCN-species might play an important role in the decay of HCN. It is the aim of this study to ansuer or clarify some of the questions regarding the kinetics

of NO formation in fuel-rich, premixed methane-air flames. It is hoped that this uill be of some value in the study of NO formation in flames containing fuel-nitrogen. The study of flames uill be conducted using a molecular-beam-mass-spectrometer (MBNS) sampling system. This system has been shoun to meet all the

requirements for sampling of high temperature systems uith excellent balance. The use of MBFIS sampling sys-

tems could undoubtedly play an important role in combustion research in the near future. MBPIS sampling

techniques allou one to follou stable and radical species uith minimum distortion. This is valuable help

in the study of (a) oxidation mechanisms and (b) rate coefficients of elementary reactions. As mentioned

above, MBNS sampling techniques are being used at U.C.L.A. to study the fate of nitrogen-bearing species and, more recently, sulfur-containing species in flames.

These studies uill no doubt help determine more efficient and more clean uays to burn fuels such as coal or liquid fuels derived from it.



The Formation of NO in Fuel-Lean Flames It is generally accepted that the formation

of nitric

oxide in the post-flame gases of lean or

near-stoichiometric hydrocarbon-air flames is modeled by reactions originally proposed by Zeldovich .
(1) (2)

0 + N2 # NO •»• N N + 02 £ NO + 0

From experimental data, Zeldovich and co-uorkers concluded that the rate of MO formation in fuel-lean or near-stoichiometric hydrocarbon flames uas much slouer

than the combustion rate, and that the NO-formation rate could be calculated assuming equilibration of the combustion reactions. Lavoie, Heyuood and Keck


have indicated that the reaction

N -f OH £ NO + H


also can contribute to NO production, especially in near-stoichiometric and fuel-rich mixtures, and it is nou generally included in kinetic studies of NO formation. Uestenberg


studied the kinetics of NO forma-


tion in lean, premixed hydrocarbon flames.

Using re-

actions ( ) ( ) and ( ) he derived equation (4) 1, 2, 3, for the rate of NO formation



1"(ND)2/K(02)(N2) k2(02)+k3(OH)



where K is the equilibrium constant for the overall reaction Nj + Oj v1 2ND. In the derivation of equation

( ) it is assumed that (i) the reactions occur under 4, constant-volume conditions, (ii) d(N)/dt is close to zero; and (iii) Reaction (5) is equilibrated in the post-flame gases.
0 + OH ^ H + 02 (5)

The fact that condition (iii) is quickly attained in the secondary zone of flames has been amply demonn Tn

strated ' .

Calculation of the NO formation rate

by Equation (4) requires values of the local temperature and concentrations of 02, N 2 , 0, and OH. Houever,

as first suggested by Zeldovich, Uestenberg took final equilibrium values of the temperature, and of the N 2 , 0~, OH, and 0 concentrations.

Using the equilibrium approximation of IM2, 0?, OH, and 0 concentrations, Bowman obtained the

following NO formation rate (using data from Ref. 4)


d(NO) dt



T ~"2expf^69,090/T "l x ( 0 0J) r eq k eq/ 2 'eq


cm sec


Elevated temperatures and high 02 concentrations in the post-combustion gases result in relatively high NO-formation rates. Experimental studies of NO for-

mation in the post-combustion zone of laboratory flames support this simplified mechanism. Neuhall and Shaded studied the formation

of nitric oxide in the immediate vicinity of a flame front propagating through a high-pressure combustion vessel in order to investigate the formation of nitric oxide under conditions similar to those occurring in internal combustion engines. Spectroscopic techniques Experimental

uere used to determine NO concentrations.

data uere obtained for hydrogen-air mixtures at pressures of 240, 325, and 340 psia, and 0.7, 0.9 and 1.0 equivalence ratios respectively. from 2000°K to 2500°K. Temperatures ranged

They found that under these

conditions NO is formed primarily in the post-flame gases, and that the rate of NO formation can be predicted by the Zeldovich mechanism, uith oxygen- and nitrogen- atom concentrations set equal to their chemical-equilibrium values. *> Livesey et al s t u d i e d the f o r m a t i o n of NO


in atmospheric-pressure,

premixed, oxy-propane flames.

They used many small diameter stainless steel tubes as flameholders.
H§r -

An outer shield of argon uas used to

prevent outside nitrogen from reaching the combusted gases. Gas samples uere taken through a uater-cooled method.

probe and analyzed for N0X by the Saltzman v

Temperatures in the burned gas region uere determined spectroscopically from the temperatures of rotationally excited OH. Temperatures uere in the vicinity of 2800°K.

They shoued that reactions (1) and (2) are sufficient to explain the rate of formation of NO in the postflame gases. The effects of combustion -modifications on the formation of nitric oxide in CH^/air flames uere studied by England uas used. . A 250,000 Btu/hr ring-type burner

Nitric oxide in the flue gas uas measured

uith a long-path infrared analyzer at concentrations from 2 to 500 ppm. Gas samples uere uithdraun by a He found that nitric oxide

uater-cooled quartz probe.

emissions could be reduced by 9Q?0 from peak levels by burning very fuel-rich flames, and that by reducing the air preheat from 650°F to 50°F, peak nitric-oxide levels dropped 67%. The louer NO levels at louer air

temperatures uere due to louer flame temperatures. England also obtained data for NO concentrations uhen up to 32/o of the combustion gases uere recirculated.

Nitric oxide in a flame burning uith a combustion air temperature of 650°F uas reduced by B2% from the peak levels by 32^ recirculation. Nitric-oxide production

uas lowered uith product-gas recirculation because of a reduction in the methane-air flame temperature. These results could have been predicted from Equation (6); louer flame temperature, Teq , results in a smaller Dn Reduction in the

rate of formation of nitric oxide.

oxygen level has a similar effect on the rate of NO formation.



"Prompt" NO Formation That the formation of NO in the primary re-

action zone might involve a mechanism other than the

Zeldovich mechanism uas first indicated by Fenimore in the Thirteenth Symposium (international) on Combustion. He measured the formation of NO in premixed

atmospheric flames of ethylene, methane, and propane uith N2 " ^2 mixtures. Post-flame gases were uithdraun

by a quartz microprobe and collected in an evacuated flask. NO and N02 concentrations uere determined by Temperatures uere measured by the

chemical analysis.

Sodium-line reversal method 20 and uere constant over the region investigated. Fenimore found that the kin-

etics of NO formation in the post-flame region is described by the Zeldovich mechanism, Houever, extra-

polation of the measured NO formation curves back to zero time gave positive intercepts, indicating, as Fenimore suggested, a transient formation of NO in the primary reaction zone, the growth rate of uhich uas too fast to be explained by the Zeldovich mechanism. Since

He labeled this intercept NO as "prompt" NO.

positive intercepts uere not found in hydrogen or CO flames, Fenimore suggested reactions such as
CH + N2 ^ HCN + N C2 + N 2 ^ 2CN

(7) (8)


to explain the "prompt" NO. Controversy aroused regarding "prompt" NO, and numerous investigators have made experimental studies to prove or disprove "prompt" NO formation. Bowman 12 investigated the formation of NO " in shock-induced combustion of H2/02/N2 Concentration time-histories of NO, OH, and H?0 uere measured during reaction using spectroscopic techniques,, NO formation rates uere found to exceed the rates predicted by the post-flame zone mechanism. It uas shoun

that the observed rates uere consistent uith reactions (1) through (3), if 0 rectly determined. and OH concentrations uere cor-

In the region of rapid NO formation,

observed radical concentrations uere in excess of calculated equilibrium values. Hence, the rapid NO forma-

tion rates uere found to be the consequence of non-equilibrium combustion chemistry. Further evidence for non-equilibrium chemistry in the reaction zone of flame uas gathered by Bouman and Seery 21 . They studied shock-induced combustion of CH/L - 0? - N 2 mixtures dilutad in argon. Concen-

tration histories of NO, OH, and C02 uere measured using spectroscopic techniques. Initial temperature

uas in the range 2600 - 3200^, and the initial pressure uas 3.5+ 0.5 atm. They found NO-formation rates (2), and (3).

to be consistent uith reactions (1),


Furthermore, discrepancies between observed NO formation rates and those using an "equilibrium" model for NO formation uere explainable in terms of "radical overshoots" in the reaction zone. They did not find

evidence to suggest that other reactions uere of importance in the NO-formation mechanism. Sarafim and Pohl one atmosphere studied NO formation in

premixed methane-air flat flames of to 1.15, Gases uere burned

equivalence ratios from 0.89

on a water-cooled porous-disk, flat-flame burner. Gas samples uere withdrawn through a water-cooled stainless-steel probe. NO concentrations were determined

by a modified Saltzman method; other species were measured using a gas chromatograph. They found that the peak rates of NO formation in the flame zone were one to two orders of magnitude greater than the values in the post-flame zone, and to be consistent with the modified Zeldovich mechanism (Reactions (1) - (3)), when free-radical concentrations (of 0, OH, and H) were correctly estimated. The "Radical Overshoot Theory" requires a detailed consideration of the kinetics of the fuel combustion, or the use of other suitable approximate methods to compute the non-equilibrium concentrations of 0, OH, and H near the primary reaction zone in order to determine NO formation rates. Detailed combustion


mechanisms are known for only a feu fuels —

H?, CO,

and CFL (methane oxidation will be discussed in a later section), and a simplified approach involving the "partial equilibrium" of Reactions (9) - (11) in most cases. is used

H + 02 £ OH + 0 0 + H2 ^ OH + H
H2 + OH £ H20 + H


(10) (11)

In the "partial equilibrium" approach, the radical reactions (9) - (11) in the flame. are considered to be equilibrated

This is not to say that the radical

concentrations are equal to their equilibrium values, rather the ratio of the products to reactants concentrations for each of the reactions (9) - (11) to the reaction equilibrium constant. is equal

The concentra-

tions of 0 and OH then can be related to the concentrations of stable species uhich are readily measured. 11 Sarofim and Pohl obtained good agreement betueen observed and calculated "partial equilibrium" NO formation rates in lean and slightly rich hydrocarbon flames, Pesters and Flahnen 27 conducted sampling of lean and . stoichiometric CH,/02 flames and observed "partial equilibrium" of Reactions (9) - (11). Recently, Gay et al 13 studied one-atmosphere ' premixed methane-air flat flames using a molecularbeam-mass-spectrometer (MBPIS) sampling system. A ua-


ter-cooled, copper porous-plug burner urns used.


gas temperature immediately dounstream from the primary reaction zone uas measured using the molecular-beamtime-of-flight technique. 0.8, 1.0, 1.1, For equivalence ratios of a

tuo distinct regions uere found:

primary reaction zone uhere formation and consumption of H~CO takes place, and a secondary reaction zone uhere NO is formed. Their studies shou that contrary

to the "prompt NO" involved by other investigators, the formation of NO (if any) in the primary reaction zone is negligible for flames of equivalence ratio <I.1. They concluded that the modified Zeldovich mechan-

ism explains NO formation rates in the secondary reaction zone if radical concentrations and temperature

during combustion are properly evaluated. Iverach, Basdin, and Kirov studied the

validity of the Zeldovich mechanism in fuel-lean and fuel-rich hydrocarbon flames in order to end the controversy surrounding "prompt" NO. Propane, ethylene,

acetylene, 6Qfa Ho/40/o ChL, and mixtures of hydrogen and carbon monoxide uere burned uith air on a uatercooled, Neker-type burner. Samples uere taken through NO, CO, C^ concentra-

a uater-cooled aluminum tube.

tions uere determined uith infrared analyzers, 0^ uith a paramagnetic analyzer, and hydrocarbons uith a flameionization detector. Temperatures uere determined by


the sodium-line reversal method and theoretical procedures. Their experiments showed the following:

(1) for nonhydrocarbon flames, the extended Zeldovich mechanism is applicable for all fuel-air equivalence rates, (2) for hydrocarbon flames, the mechanism is applicable, for both in-flame and post-flame regions,

for #£l,15, and for post-flame region for 0<1.5, provided that the B^-atom concentration is determined correctly, and (3) for all regions of fuel-rich hydrocar-

bon flames ( > . ) and for regions in the vicinity $15, of the primary reaction zone of moderately rich flames ($>1.15), the mechanism is not tenable because it requires improbably high &-atoms concentrations. They

concluded that reactions such as ( ) ( ) and possi7, 8,
bly (12)

C + N£ £ CN + N 9


might be responsible for the large rate of NO formation in fuel-rich flames and the primary reaction zone of moderately rich flames (j8>1.15). 28 Ay and Sichel carried out a numerical analysis of the combustion of methane in nitrogen-oxygen mixtures in order to clarify the relationship between prompt NO and overshoots in radical concentrations. Diffusion and heat conduction, which are important in laminar flames, were neglected in their analysis; nevertheless, their results show the link between rad-


ical overshoot, flame temperature, and the NO formation rate. Their analysis agrees with the experiments , namely, "prompt" NO in near-stoichi-

of Iverach et al

ometric and lean flames, which is related to the high rates of NO formation in the recombination and postflame zones, can be explained by the Zeldovich mechanism provided the appropriate free radical concentrations are used; for rich mixtures the NO concentrations computed using the detailed kinetics were far belou experimentally observed values, and the Zeldovich mechanism fails to explain NO production in rich mixtures.


Formation of MO in Fuel-Rich

Flames and later , "prompt"

As indicated first by Fenimore

supported by the experiments of Iverach et al

NO formed in fuel-rich hydrocarbon flames cannot be explained by super-equilibrium concentrations of the

radicals 0, OH, and H since the concentrations required to explain the observed NO-formation rates uould be significantly larger than "partial equilibrium" values. The forementioned investigators proposed that reactions such as (7), (8), and (12) played an important role

in the NO formation process

CH + N


( 7) ( 8)

+ N

C + N 2 £ CN 4- N

uith subsequent reactions of N-atoms-via Reaction (3) to form nitric oxide. The production of NO in these

flames then requires a detailed combustion mechanism for the fuel in consideration. (This is also true Methane com-

of some leaner flames, see Section 2.2).

bustion mechanisms are considered in the next section, and as the reader uill find out, there still are uncertainties regarding the rate determining step and the rate coefficients mechanisms. of reactions involved in the

The rapid NO formation rate near the re-

action zone of rich flames requires that reactions


such as (7) - (12) be very fast.

The experimental

data of Bachmaier et al 29 support this proposal. Hayhurst and McLean studied a fuel-rich 3/1/4.75 and

flame of unburnt composition H2/02/N2:

a flame of the same composition except that 1% of the hydrogen uas replaced by acetylene. The flame uas

burnt at atmospheric pressure on a uater-cooled burner made from stainless-steel hypodermic tubes. gas temperature reached 2000°K. through a uater-cooled The burnt

Gas samples uere taken

probe (made of quartz) into a They found that the

chemiluminescent NO analyzer.

amount of NO in the acetylene seeded flame uas over that formed in the Hz/00/N0 flame via the modified 0 z /. Zeldovich mechanism. Based on thermochemical data alone, they proposed reactions

CH + N2 £ HCN + N

( 7)

CH2 + N 2 ^ HCN + NH
folloued by

N + OH ^ NO + H
NH + OH £ N + H20
to explain the "prompt" NO formation.



they suggested that HCN is coupled to CN by equilibration of

HCN + H £ CN + H2
uith NO resulting tions


from one of the tuo exothermic reac-


CN + 02 £ CO -f NO


CN + OH ^ CO + NH
Reaction (17) is followed by (14)

and then by reaction

Haynes et al

detected the presence of cyano Uarious pre-

species in fuel-rich hydrocarbon flames.

mixed hydrocarbon-air and nonhydrocarbon-air flames (including a CH, - H2 air flame with equivalence ratio of 1.42) uith and without the addition of small amounts

of pyridine were burnt on a water-cooled Fleker-type burner. Samples were withdrawn from the post-flame

gases via water-cooled probes (silica or Alumina), analyzed continuously for CO and C02 (NDIR analyzers),
-.- -

02 (paramagnetic), and NO (chemiluminescent).

The con-

centrations of cyano species and NH. species in the post-flame gases were determined chemically, and Hatoms concentrations by the Li/LiOH absorption techf~y *~f
O /i


' . Temperatures uere determined uith Na-line They found NO, HCN, and NH. (The

reversal measurements.

concentrations in excess of equilibrium values.

measured values of NH. concentration are viewed with caution, however, since they were highly susceptible to sampling conditions). The observed NO formation

rates were larger than predicted by the Zeldovich mechanism with 0-atom concentrations inferred from measured H-atoms concentrations using a partial-equilibrium ap-


proximation for the system H - OH - 0 - H2 - H20. The formation of cyano-species uas found to be related to the decay of hydrocarbons and in very rich flames occurs well into the post-flame gases. Furthermore,

it uas concluded that HCN decays via CN and the ratedetermining reaction
CN + C02 £ OCN + CO



also studied fuel-rich flames, in-

cluding CH, - 02 ~ MO flames with equivalence ratios from 1.20 to 1.95. A method involving direct sampling

of natural flame ions into a mass spectrometer uas used to calculate the concentrations of HCN, NH 3 , and NO. He found that the HCN concentration is proportional

to the N2 concentration independent of the fuel type, that the HCN concentration increases uith increasing equivalence ratio, and that HCN-decay leads to both INUand NO, the relative proportions depending on the equivalence ratio. quence,
CH + N2 <* HCN + N

Morley suggests the reaction se-


HCN + H ** CN + H2 HCN + OH £ CN -i- H20

(15) (19)

uhere (15) and (19)

are balanced, to explain the formaThe subsequent de-

tion of HCN and CN in the flame.

cay of HCN is consistent uith the reaction
CN + OH £ NCO + H



being the rate-limiting step, and it leaves the nitrogen from HCI as N H - . Nitric oxide and nitrogen are

produced by reactions involving the NH. species and Reaction (3)

N + OH ,-• NO + H ( 3) 17 ("ligauchi et al modeled the combustion of
CH^ - Qj " No f-'-ames using a 40-reaction mechanism. They studied flat flames burning on a cooled stainlesssteel porous plate at 0.1 atm. pressure. quartz probe to sample the flame. NO

They used a

uas detected

using chemiluminescence; H, OH, and 0 using ESR; CNspecies using chemical means, and stable species using gas chromatography. to 1.42, For equivalence ratios from 0.88

they concluded that the Zeldovich mechanism

is inadequate to predict "prompt" NO formation, and that HCN is formed prior to NO. (13) They favored Reaction

over Reaction ( ) on thermochemical grounds and ?

pointed out the violation of the spin-correlation rule by Reaction (7). Other species like C, C2 did not con-

tribute significantly to "prompt" NO formation because of their low concentrations in the flame. gested that H2CO + M
CO + H2 H- M

They sug-


is the rate determining step in methane oxidation. 95 Pecters, Blauuens, and Smets measured the concentrations of NO, 0, and fuel fragment radi-


icals such as CH, CH2, C2, by means of molecular-beam sampling and mass spectrometric detection in a number of hydrocarbon/02/N2 flames. ethane, or methane. The fuel uas ethylene,

They found that even in hot, fuel-

lean flames, the Zeldovich mechanism cannot account for the rapid NO formation in the flame front. They

derived an expression for the NO generation rate in the flame front of all flames investigated in terms of the CH2 or CH radical concentrations. both of the processes
CH + N 2 * HCN + N

They concluded that


CH2 + N 2 £ HCM + NH


in each case followed by rapid oxidation of the products, may be the principal source of NO in the flame front, and that other hydrocarbon fragments, C, C2, C 2 H do net contribute to "prompt" NO formation because of their lou concentrations in the flame front. The actual mechanism of decay of hydrogen cyanide in hydrocarbon-air mixtures is uncertain. The studies by Haynes and Morley previously mentioned are in contradiction in regards to uhich reaction is the rate-determining step in the decay. In order to

elucidate the HCN-decay mechanism uhich concludes uith 2 fi the formation of NO, Haynes recently conducted a study of premixed hydrocarbon flames burning on a uater-cooled neker-type burner seeded uith fuel-nitro-



gen in the form of pyridine, ammonia, or nitric oxide in amounts up to 2000 ppm. of nitrogen species in the post-flame gases, A water-cooled silica probe uas NO uas determined continu-

used to sample the gases.

ously by a nondispersive infrared analyser (l\IDIR). Cyano species and total amine species uere determined using chemical means. H-atom concentration in the

hot gases uas determined by the Li/LiOH absorption method, Post-flame temperatures were determined by the Sodiumline reversal method. Based on the experimental re-

sults, Haynes proposed two parallel rate-controlling steps: tion one which is first order in OH, possibly reac-

(22) HCN + OH *• HOCN + H (22)

the other which is second order in OH:

HCN + OH * CN + H20
CN + OH *• OCN + H

(23) (24)

The relative contributions of (22) and (24) vary with temperature, uith Reaction (24) dominating at high temperatures.

The OCN- species decay very rapidly

to form NH.-species

+H HOCN (cyanic)^HIMCO (isocyanic)^ NH2 -f CO
OCN + H % NH + CO


As Haynes points out, measurements of OCN and NH. species are required to confirm the proposed mechanism.


("lorley cies.

considers the fate of the NH. spe-

He indicates that the nitrogen hydrides can

be interconuerted by reactions of the type,
NHX + H ± NHX — X + H^- , x=l,2,3 V V , 9 (27)

which may or may not be balanced, and the oxidation and the formation of N^ taking place by

N + OH £ NO + H
NHo + NO ^ N 2 + H20 '2
NH + NO * N 0 + OH

( 3)
(28) (29) (3U)

N + NO ^ N 2 + 0

Furthermore, at relatively lou temperatures, the above reactions might lead to a build-up of amine species. Experimental measurements are needed.



Mechanisms of Methane Oxidation In order to predict the formation of nitric oxide

in fuel-rich flames and some lean flames of hydrocarbons (see Sections 2.2, 2.3), the concentration histories of the The kinetics of methane oxygen

free radicals are necessary.

systems have been studied extensively over the years. Nevertheless, many uncertainties remain, both with respect to the oxidation mechanism and the rates of the elementary reactions which form part of the mechanism. Furthermore,

in the richer methane flames, C^-hydrocarbon decay and formation has to be accounted for, and the mechanism grous in complexity.


Methane Oxidation in Fuel-Lean Flames Studies include shock-tube experiments by Cooke

and Williams Brokau


, Bouman


, Heffington et al


, Brabbs and

, molecular-beam-mass-spectrometer sampling of 27 flames by Peeters and Mat-men , numerical analysis and flou

reactor experiments of Uestbrook et al vey of Engleman 35


, the kinetic sur9697 .

, and recent uork by other authors

In Table 1 (p. 35), the 23 reaction mechanism for the shock-initiated reproduced.

31 CH,-oxidation proposed by Bouman " is

This mechanism has been used extensively by Bowman's analysis shows that, in the

other investigators.

temperature range 1900 - 2400°K, this mechanism correctly


predicts the time of occurring and magnitude of the radical (0, OH, H) concentration overshoots, and also predicts a departure from a "partial equilibrium" state during the initial stages of the radical concentration overshoots. Boni and Penner ^ fi conducted a sensitivity analysis of the mechanism proposed by Bowman at 2QOO°K. Their

analysis showed that Reactions (Rl), (R7), (R16) and (R25) are the most important reactions for all of the species

CH4 + n £ CH3 + H + N

(Rl) (R7)
(R16) (R25)

H + 02 £ 0 + OH
CH3 + 02 £ H 2 CO + OH H2CO + PI £ HCO + H + M

In addition Reaction (R15) is important for the major free radical species, i.e., OH, 0, and CH20. The 0-atom profile

is dominated by Reactions (Rl), (R7), (R16), (R25), (R15) (as cited by Bowman) plus Reactions (R24) and (R3) CH3 + 0 £ H2CO + H (R15)

HCO + fl £ CO + H + N CH4 + H £ CH3 + H2


The mechanism of Reaction (R16) has recently been studied and the oxidation of methyl radicals was shown to occur through the steps CH^ + 0 * CH<- 0 + H 9 \J CH3 + 02 ^ CH30 + 0 CH3 + 0 £ CH20 + H2

98 ,


The methoxy radicals produced react by means of
CH3D + M £ CH20 + H + M CH30 + 02 £ CH20 + H02

The reaction of CM, uith 02 and the thermal decomposition of CI-UO are the most important pathways of methyl radical oxidation, Peeters and Mai-men 27 measured the concentration of all species, stable as uell as unstable, throughout the reaction zone of lou-pressure lean methane-oxygen flames. The results of their analysis shou that (i) CH, reacts 15% uith OH, 15% uith 0, and 10% uith H; (ii) CH, is destroyed O by 0 atoms; (iii) CH90 disappears 4Q?o by thermal decompo* sition, 40% by reaction uith OH, and 20% by 0 attack; (iv) CHO reacts mostly uith 02; (u) H02 is destroyed 45% by OH, 40% by 0, and 15% by H, Their studies shou that the rate

limiting step is the decomposition of formaldehyde
CH20 + N = CO + H2 + 1*1 They argued that Reaction (31) (31)

explains quantitatively the

function of Hz in the flame, and the activation energy of 9
Reaction (31) is in good agreement uith the overall "acti-

vation energy" of lean-CH^/02 flames (about 40 kcal/mole). On this basis, they rejected reactions such as CH20 + 0 £ CO + H + HO
CHO + N ^ C O + H + N


Furthermore, they pointed out that Reaction (R25) of Bouman

may uell be the rate-determining

step in shock studies,

and Reaction (31) cannot contribute significantly to the removal of CH20 in shock tubes since the major part of the CH20 is consumed by H atoms in a chain mechanism initiated by Reaction (R25). Their results also shou that C02 is

formed mostly via Reaction (R9)
CO + OH £ C02 + H


The important reactions in Peeters mechanism are
CH4 H- OH £ CH3 + H20

CH4 + 0 £ CH3 + OH

CH3 + 0 £ CH20 + H CH20 + N $ CO + H2 + M CH20 + OH(0) £ CHO + H20(OH)
CHO + 02 £ CO + H02

H02 + OH(0) * 02 + H20(OH)
H02 + H ^ 20H

H + 02 ^ OH + 0 0 + H2 ^ OH + H
OH + H2 £ H20 + H OH + OH £ H20 + 0 CO + OH £ C02 + H
• C 7

(For extensive kinetic data see England

). Further

support for Reaction (31) as the rate-determining step in flames can be found in the investigations of Migauchi et al . They studied premixed CH4/02/N2 flames at 0.1

atm. and equivalence ratios between 0.88 and 1.42. They found the rate-controlling reaction of methane oxidation

to be Reaction (31) uith a rate constant k31=2.1x!015 exp (-17,620/T) mol"1cm3sec"1.


Methane Oxidation in Fuel-Rich Flames In the combustion of fuel-rich hydrocarbon

flames,the -concentrations of hydrocarbon fragments are high enough that their recombination reactions become important and hydrocarbons higher than the original fuel are found as intermediates. In CH^-oxidation, the chemistry of C2-hydrocarbons becomes important in the fuel-rich mixtures. Gardiner

and Olson 37 have conducted a series of shock tube experiments and numerical analysis of fuel-rich CH,/02/Ar mixtures. The reactions of CH 2 » C^H,, and CoH- were found to

play an important role in their shock tube experiments. The result of their experiments can be modeled by a sixtythree-reaction mechanism which is reproduced in Table 2 (18000<T<2700°K). They omitted species CH and C2 on the

basis that their concentrations and reaction rates are too small to affect the overall course of reaction. The speTheir

cies ChUO and d-U02 were omitted on similar bases. sensitivity analysis showed primary sensitivity

to the py-

rolysis reactions (1) and (30), and to the oxidation reactions (7) and ( 8 . 4) Additional sensitivity is present for

TABLE 1, Methane oxidation in fuel lean mixtures

Reaction CH,-i-H+M
2. 3. 4. 5. 6. 7. 8. 9. flO. 11. 12.

Rate constant, kf* 2X1017 exp(- 44 500/77) 6X10" exp(- 6290/2T) 2.24X10*7'' ex p ( - 4 400/7") 2.1X10" exp( -4 560/r) 2.9X10" exp( -5530/T) 3.2X10'< exp( -7540/r) 2.2X10" exp( -8 450/r) 5.5X10" exp( -3520/r) 4.0X10U exp( -4030/T) 5.9X10"exp( -2060/D 7.9X1011 exp(-52770/r) 2.2X10" exp(-4S300/r)
1X10" 2X10" 4X10"

tH. 15. 16.

18. 19.

21. 22. 23. 24. 25. 26. 27. |2S.
f29. t30.

CH4+H-»CH,+H, CH,+O— CH,+OH H,+OH—H+H,O O+Hj—H+OH H+Oj—O+OH O H + O H —O+H.O CO+OH— CO,+H CO+O4-M— CO.+M H+OH+Ar— H,O+kr H+OH+H,O-»HzO-}-H,O Oi+Ar-^O+O+Ar H,+Ar—H+H+Ar CH.+O-^HjCO+H CH.+O)— H,CO+OH CH.+OH— HjCX^+H, H,CO+O— HCO+OH H,CO+OH— HCO-1-Hrf) H-CO+H— HCO+H, HCO+O— CO+OH HCO+OH— CO+H^) HCO+H—CO+H, HCO+M— CO+H+M H,CO+M-» HCO+H +M H+HO,-*OH+OH H+O.+M—HO.+M C,H,— CH4+CH, C-H.+O— C^H^+OH HCO+O,— CO+HO,

5X1011 exp(-2300/r) 5.4X10" exp(-3 170/r) 1.35X10" exp(-l 890/7") 1X10" 1X10" 2X10" 5XlOue.xP(-9570/r) 4X10 U exp(-lS500/r) 2.5X10"exp(-950/r) 1.5X10" exp(500/r) 8X10" exp(-4 500/r) 4X10"exp(-32SO/r) 4.2X10"exp(-7200/7')

Units: cm, cal, °K, mole, sec.

t Re.iction not included in final mecnanism.


TABLE 2. Methane oxidation in fuel rich mixtures
Rate Constant0 Reaction
(1) CH 4 + M = CH3 + H + M



46,900 7,600 3,840 1,010 0 46,900 4,530 7,600 0 0 0 0 1,860 36,235 1,660 2,300 6,540 7,400 0 0 0 0 80.020 4,715 3,070 1,810 10,820 13,390 2,445 0 0 39,810 48.600 7,300 1.360 0 15,850 0 53,850 250 1,860

(2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41)

CH 4 + H = CH3 H- H 2 CH4 + O = CH3 + OH CH4 + OH = CH3 + H 2 O b CH4 + CH 2 = CH3 + CH3C CH3 + M = CH 2 + H + M c ' d CH3 + O 2 = CH 2 O + OH CH3 + H = CH 2 + H 2 c ' e CH3 + O = CH 2 O + H CH 3 + OH = CH 2 O + H 2 CH 3 + C H 2 = C 2 H 4 + H CH 2 + C H 2 = C 2 H 2 + H 2 CH 2 + O 2 = CH 2 O + 0 CH 2 0 + M = CHO + H + M CH 2 0 + H = CHO + H 2 CH 2 O + 0 = CHO + OH CH 2 O + OH = CHO + H 2 O C H O + M = H +CO + M CHO + O 2 = HO 2 -i-CO CHO + H = CO + H 2 CHO + O = CO + OH CHO + OH = C O + H 2 O C 2 H 6 + M = CH 3 -t-CH 3 + M / ' C2H6 + H = C2H5 + H2 C 2 H S + O = C 2 H 5 + OH CoH 6 + OH = C 2 H 5 + H20g C 2 H 6 * CH3 = C 2 H 5 -H CH4h C 2 H 5 + M = C 2 H 4 + H + M1 C 2 H 5 + O 2 = C 2 H 4 + HO 2 C 2 H 5 + H = CH3 + CH 3 C 2 H 5 + H = C2H4 + H2 C2H4 + M = C2H2 + H2 + M C2H4 + M = C2H3 + H + M C 2 H 4 + H = C2H3 + H 2 C2H4 + 0 = C H 3 i - C H O C 2 H 4 + OH = CH3 + CH2O C 2 H 3 + M = C2H2 * H + M C->H 3 + H = C 2 H 2 + H2C C2H2 + M = C 2 H - H H + M C 2 H 2 + H = CoH + H2;' C 2 H 2 + O = CH 2 + CO

17.67 14.86 7.07 3.54 13.00 16.67 11.84 14.86 13.83 12.87 13.30 13.50 14.00 16.70 13.30 13.70 15.70 14.47 12.53 13.30 13.48 13.48 111.29 14.12 13.26 13.80 14.74 14.67 12.18 13.57 12.27 17.32 17.41 14.84 13.35 13.00 14.90 13.00 16.62 0.89 13-72

0 0 2.1 3.1 0 0

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 -25.3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3.2 0



Rate Constant0 Reaction Iog10>l


(42) (43) (44) (45) (46) (47) (48) (49) (50) (51) (52)

C 2 H 2 + OH = CH3 + CO C2H2 + C 2 H 2 = C4H3 + ff C 2 H 2 + C2H = C 4 H 2 + H C 4 H 3 + M = C 4 H 2 - | -H + M/ C 4 H 2 + M = C 4 H + H + U> H 2 + O2 = OH + OH H + O 2 = OH + O O + H 2 = OH + H OH + H 2 = H 2 O + H OH + OH = H 2 O + O H + O 2 + M = HO 2 + M
4- \t

/C'i'V T >_ \,j j ) ti r O U -i- \i — rio^-* kj n T jvi — TJ f~}


(54) (55) (56) (57) (58) (59) (60) (61) (62) (63)

H2 + M = H + H + M O2 + M = O + O + M CO + Oo = CO2 + O CO + OH = CO2 + H k CO + O + M = CO2 + M H 2 + HO 2 = H 2 O + OH H + H0 2 = OH + OH H + H0 2 = H 2 + O 2 OH + H0 2 = H 2 O + O 2 O + H0 2 = OH + O 2

12.08 13.00 13.60 15.93 17.54 13.23 17.08 - 14.34 13.72 13.74 15.40 23.88 12.35 .11.27 11.08 12.60 13.45 11.86 14.40 13.40 13.70 13.70

0 0 0

0 0 0 -0.91 0 0 0 0 -2.6 0.5 0.5 0 0 0 0 0 0 0 0

250 22,650 0 30,200 40,260 24,210 8,370 6,895 3.270 3,520 0 0 46,600 48,165 17,615 4,025 -2,285 9,410 960 350 500 500

Rate constants in the form A X 7" exp (-6/7"), in cm, mol, s, and K units. The reverse reaction rate constants were computed using J A N A F thermochemica! data where possible and locally computed thermochemical data otherwise. b The T3 factor may extrapolate the rate constant loo high at higher temperatures, but is used here because this expression goes through the high-temperature data. c Estimate. No sensitivity to the rate of this reaction was observed. ^Estimated to be equal to frj/10. e Estimated to be equal to Jr 2 . ^ This reaction is in the pressure-dependent falloff region of a unimolecular decomposition. This rate expression is from Olson et al. [9] for experiments over the range 1330 < T < 2500 K and 0.10 <P < 0.50 a tm. Care must be taken that this rate-constant expression be used only for the pressure and temperature conditions for which it is valid. * This is a low-temperature value that agrees with the few high-temperature data. h Strongly curved Arrhenius behavior is observed for this reaction. 1 This rate-constant expression was obtained by RRK calculations of the falloff from the experimental high-pressure limit expjession of Glanzer and Troe [ 4 7 J . ^ Preliminary results. k See Baulch and Drysdale [621 for a review of the literature on this reaction.



the CH2 reactions

(ll) and (13), and reactions (14) and ( ) 2.

Literature values for rate constants uere used for Reactions ( ) (2), (13), (14), (30) and ( 8 . 1, 4) The authors

cautioned that the H2CO-decay mechanism is uncertain and insufficient experimental data is available. The numeri-

cal values for the rate constants of Reactions (7) and (11) uere found by numerical analysis. They believe their re-

sults to give k? to uithin +5Q% and k, , uithin a factor of

Harvey and Maccoll

studied the formation of C?

hydrocarbons uithin methane-oxygen flames of equivalence ratios 0.56 to 1.25 at 20 torr. Their experiments shoued

that for their experimental conditions the reaction CH3 + CH3 + N £ C2Hg + 1*1 is uell into the fall-off region resulting in a lou reaction rate (the maximum mole fraction of ethane in the stoichiometric flame uas 5 x 10 ). Their results enabled

them to propose the following ethylene forming reactions

CH3 + CH2 £ C2H4 + H The ChU and CI-U concentrations in these flames are in equilibrium via


-x v*

pit L»MO


Figure 2 shows the dependence of CH20, C2H4, C2H2 and H2 peak concentrations on flame equivalence ratio.


Figure 3 shows the dependence of C 2 H < , C2H2, and hU on peak fCH for a range of flame equivalence ratios.

They also pointed out that at higher pressures the rate of the combination of methyl radicals (CH, -f- CH,, + PI

£ C 2 Hg + M) to ethane uill become competitive uith the other sources of C2 hydrocarbons, and acetylene is formed in the flame via + CHo x~ CoHo 4- HO



o o



O 5








Fig. 2. The dependence of CH2O

,C2 H 2 , and H2

peak concentrations on flame equivalence ratio .



Fig. 3. The dependence of peak C_H 4 C H and HS on peak 2 2 2 2 ' ( CHS ) for a range of flames £ Z 0.56 to 1.25 .


Shock-tube studies of the early stages of pyrolysis and oxidation of methane were conducted by 39 Tabayashi and Bauer . Temperatures ranged from 1950 to 2770°k, total densities (2.37 - 8.91) x ID"6 mol



, and CH^/CU ratios 3.3 and 6.7.

From their pyroly-

sis experiments in CH^/Ar mixtures, they concluded that methane decomposes mainly via

+ Pi £ CH, + H + n


2H5 + ^ * C2H4 *H * N

C2H3 + Fl £ C2H2 + H + M methylene is produced mostly by the reaction
CH2 -r H2 £ CH3 + H

and consumed via reactions with CI-L and species generated during ChL-pyrolysis. Their oxidation studies

show that oxygen reacts only with the fragments of methane pyrolysis, and under the methane rich condition oxidation starts predominantly via the reaction CH3 + 02 £ H2CD + OH rather than

H + 02 £ OH + 0
and the resulting OH radicals react rapidly with methane uhich is present in large excess,
CH4 + OH £ CH3 + H20

thereby generating more methyl radicals, uhich reinforce the pyrolysis chain. Their calculated species profiles

best fit the observed profiles if the reaction rate constant for the methyl radical-oxygen reaction is given a value of 2.7 x ID12 x exp (-12,000/RT) cm3moi""1s~1. Regarding the fate of formaldehyde, they found that thermal decomposition of formaldehyde uas in agreement with their experimental results and computer simulations CH20 + M = CO + H2 + PI Houever, an alternative mechanism consisting of the following reactions
CH 2 0 + M £ CHO + H + 1*1 CHO + M ^ C O + H + IV1
CHO + 0 2 £ CO + H 2 0 CHO -f H £ CO + H2

CH20 + H £ H2 + HCO could not be excluded. The role of CH2 in CH^-oxidation uas found to be ambiguous. This study also shous that oxidation

of CO to CO- occurs mainly via the reaction
CO + OH £ C02 -f H



An Introduction to Sampling Techniques in Combustion Studies As Knuth

has suggested, specifications for

the ideal instrumentation for flames studies might include the following broad requirements: (a) monitor

all chemical species, including intermediate and freeradical species, (b) function in temperature, pressure and composition ranges typical of flames, (c) resolve spatial measurements small in comparison uith the flame thickness, and (d) monitor uithout disturbing the (nonequilibrium) thermodynamic state of the system. Shock tubes have been shoun to be suitable for studies of high temperature processes, and excellent revieus and books are available that describe their applicability in chemistry and physics. method of studying high-temperature The shock-tube

processes possesses at least four major advantages over other methods41 ~: (1) The equilibrium temperature in the after-shock region can be calculated accurately and reliably from the measured shock speed and

conservation of mass, energy, and momentum

considerations, (2) The "slug" of gas behind the primary shock is very uniform in pressure and temperature. Uall effects are negligible because of the short time scale.
(3) Practically any gas mixture can be heated

to any selected temperature by using the appropriate shock strength. (4) The heat release by the shock impact is initially in the form of kinetic energy, i.e., translational energy of the molecules. The major disadvantage is the short observation time, which for the after-shock region, is usually betueen 1QD and 400^sec, Thus, optical spectroscopy

is by far the most useful method of following the production and/or consumption of individual species behind shock waves. itored. Typically, three or four species are mon-

If only one optical path is available, then

a oiven set of conditions must be repeated for each of the species monitored. Ono of the principal problems with spectroscopic studies is that of determining absolute concentrations, since absorption coefficients are known only for atoms, most diatomic molecules, and a few simple poly-atomic species. In the absence of this knowledge This is dif-

it is necessary to calibrate the system.


ficult because radical concentrations of knoun values are hard to obtain, the production of the radical itself might be an experimental challenge, and it is necessary to calibrate over the temperature range to be studied since the temperature dependence of absorption coefficients of complex molecules is unknown. One also

has to find absorption lines in the available spectral regions uhich are not obscured by other species. Hence

the use of shock tubes in conjunction with optical spectroscopy satisfies requirement (d) most closely, requirement (a) least closely. In an alternative technique, gas samples are withdrawn from the flame using a sampling probs. Probe

sampling is a straightforward process; the sample is withdrawn, quenched, and analyzed. The chief advantage

of this technique is that a wide variety of analytical instruments can be used to follow the fates of species within the flame. The main disadvantage is that compo-

sition changes due to additional chemical reactions during transport from the flame to the analytical instrument^) are inevitable. Probes also have perturb-

ing effects on the flame that have to be considered: aerodynamic, thermal, and catalytic effects. Some of

these have been eliminated by the use of very fine mi9n croprobes made of quartz. The relative effects of several different probe designs on flames have been studied

by England

, Malta

, and Allen


The use of sampling

probes meets requirement (a) relatively closely and requirement (d) relatively poorly. Sampling of ions from flames is another technique used by investigators to study the processes occurring in the combustion mixture. In a typical appa-

ratus, the gas is sampled through a small hole at the tip of a cone and expanded into a vacuum chamber at 10 to 10 torr. The system is designed to obtain The ions are formed

critical flow through the nozzle.

into a beam by an electrostatic lens and focused through a small hole, typically 2mm. in diameter, into a second chamber at 10 torr. which holds a quadrupole mass specBoth positive and

trometer and electron multiplier.

negative ions can be detected by reversing the polarities of various voltages. Ideally the expansion of the

gas into the vacuum should be fast enough to quench any chemical reactions so that the expanded gas has approximately the same composition as that in the flame. This is usually the case for neutral molecules, but because ion-molecules reactions are typically 1-2 orders of magnitude faster than those betueen neutral molecules considerable distortion of ion signal can occur .

This is particularly important for negative ions because of the possibility of fast associative reactions. Fur-

thermore, the boundary layer that exists on the sampling


cone uill have an additional effect on the flame gas composition before it expands through the nozzle .

This and the effects previously described can be minimized by proper design of the sampling system, giving this technique an advantage over some other flame-sampling techniques, probe sampling for example. The chief

disadvantage of ion sampling is that it can be used only for species uhose concentrations are known functions of measurable ion concentrations. Hence this

technique satisfies requirement (d) most closely and requirement (a) least closely. The molecular-beam-mass-spectrometer (MBFIS) sampling system satisfies the abovementioned requirements uith better balance. The U.C.L.A. MBfIS sampling system

has been employed in the study of reactive mixtures since 1969, and numerous studies have been conducted in this

laboratory to eliminate or minimize all those effects uhich might either distort the gas composition during sampling or make the interpretation of measurements a confusing task. A discussion of these perturbing

effects is left for the next section, and only a description of the system uill be made here. The FIBMS sampling system consists typically (see Figure 4) of a sampling cone (uhich might be en-

closed in a chamber for lou-pressure studies), source chamber, skimmer, collimating orifice, detector chamber,

and quadrupole mass spectrometer detector.


of an effusive source and a uheel-chopper in the collimation chamber allows calibration of gas mixtures and phase-sensitive detection. The source gas (at pressures

of up to several atmospheres and temperatures of several thousand degrees Kelvin) expands through the sampling orifice into the source chamber (uhere background pressure is typically 10—3 to 10-1 torr.) and the core of the resulting jet is skimmed and transferred into the collimation chamber (uith background pressure from 10"~ to 10 ' torr.). The molecular beam is chopped in the

collimation chamber for phase-sensitive detection, and the collimating orifice admits these molecules flying along the system centerline into the detector chamber. The mass-spectrometer detector generates a signal proportional to the species density in the beam at the detector. As uas mentioned in the discussion of ion sampling from flames, the intention here is to lower suddenly the temperature and pressure of the reaction mixture, so that further chemical changes are prevented and the composition of the expanded gas approximates, that of the flame.

















Fig. 4. The UCLA MBMS sampling system.

Thus, applicability of MBMS sampling techniques to the study of chemical reactions in flames results largely from the rapidity with uhich the gas temperature and pressure decrease during the expansion through the orifice in the sampling cone. perature ratio T/To A plot of the tem-

versus dimensionless time, taken

from reference 40, is shoun in Figure 5. T is the gas temperature, a is sound speed, t is flou time (zero at the throat), x is axial distance (zero at the throat), d is throat diameter, and subscript o refers to source (stagnation) conditions. Furthermore, a point that

should be stressed is that, uhile in the sampling of ions one is actually measuring average properties of the gas that flous through the sampling orifice, in MBMS sampling only that small fraction of the sampled gas that flous in the vicinity of the orifice centerline reaches the quadrupole mass spectrometer detector. This results, as uill be explained in more detail in the next section, in the detection of molecular-beams that are much more representative of the flame gas.


Fig. 5 Temperature ratio as function of dimensSonless flow time for free-jet gas flows from orifice.



Possible Composition Distortions in_ flBNS. Sampling of Flames. In an idealized model4 of molecular-beam

sampling, the sampled gas undergoes an isentropic freejet expansion through the source orifice and the specific-heat-ratio, ^Tf remains a constant throughout this expansion. Flou remains a continuum upstream from the

skimmer entrance and becomes free-molecular downstream from this surface. There is assumed to be no background

scattering of the free jet and the molecular beam. The beam composition at the detector is the same as the source-gas composition.

In the design of a flBHS sampling system, various departures from the above model must be considered. As the combustion mixture flous from the source to the detector, the following are encountered: sampling-probe-

induced distortions of the gas composition, chemical reactions during the expansion of the gas into the vacuum, species condensation, pressure diffusion, freezing of vibrational, rotational or translational degrees of freedom (in this order), skimmer interference, Flachnumber focusing, and scattering by background gases (in any one of the lou-pressure chambers). Except for

probe-induced distortions, all of the above considerations are treated in the paper by Knuth , and the dis-


cussion is based mostly on this reference and uork by other authors with the U.C.L.A. MBMS sampling system.


Free Get Expansion. Before proceeding into the discussion of com-

position distortions in MBMS sampling, the reader might benefit from a brief introduction to the problem of unconfined expansion from a sonic orifice into a lou-pressure chamber. As Sherman indicated, the problem of trans-

onic flou through an orifice or axisymmetric nozzle remains unsolved. Houever, the supersonic region of the

flou is very little influenced by the transonic region, and the method of characteristics can be applied in the inertia-dominated region of high-Flach-number isentropic flou. The free-jet shock uave structure is shoun in Figure 6. As pointed out above, the method of char-

acteristics is applied to the region inside the barrel shock. Ouen and Thornhill were the first to carry

out the computations for gases uith T = 7/5 assuming slightly supersonic flou at the orifice (M = 1 leads to a singularity). Sherman and Anderson report

calculations for other values ofj. of these calculations

The main feature

is that about one nozzle diameter

from the orifice the streamlines appear to radiate from a "source" at x . Furthermore, the density decreases

along each streamline in proportion to the inverse square distance from this "source." The isentropic core of the

flou appears to pass from the nozzle exit through a barrel, the sides of uhich are the shock uaves generated by the coalescence of compression uaves originated at the jet boundary as the reflections of the initial expansion fan. The Mach disk is formed by the intersec-

tion of the lateral shock uaves.



Fig. 6. Free-jet shock structure.


The variation of the mach number, M, along the jet axis with distance x has been carried out by Sherman and Ashkenas ' for'"/" = 5/3, 7/5, and by AnThey used

derson49 for If = 1.30, 1.20, 1.10, and 1.05. the best fitting formula


TlP —1
i«M»™»» I ^


d* xl
where A, and x are constants which can be obtained o from the above references. For other values ofT, one ,

may use the following equation suggested by Knuth


Note that Equation (33) has a singularity at x = x , and therefore it is only applicable if x >1. d* ' It is important to point out effects that are not considered in the ab'ove analysis of free-jet expansion. (1) Boundary-layer growth on the converging nozzle.

The effect of this boundary layer will be to change the effective orifice size (see Ref. 51 for a comprehensive analysis) and distort the flow pattern near the orifice. In equations (33) and (34) an effective ori-

fice diameter then must be used. (2) Freezing of vibrational, rotational, and translational degrees of freedom (always in this order). Freez-

ing of degrees of freedom will cause T to change in the


expansion and not be constant as assumed In Thornhill's analysis. Freezing of translational degrees of free-

dom causes the flou to transit from continuum to freemolecular. Equations (33) and (34) for the centerline

Flach number do not hold in the free-molecular flou region. It should be noted, houever, that the density

keeps decreasing as the inverse square of the distance as a consequence of the source-point nature of the flou. (3) To the author's knowledge the determination of

jet boundaries for gas mixtures uith diffusive separations (e.g., ba rodif fusion) has not been solved theoretically. Sherman 46 determined the location of the Mach disk empirically,

p p

= stagnation pressure = ambient pressure ^17,000.

This is independent of v and holds for 15 ^ P0/0 Bier

52 and Schmidt determined, from photographic studies

of jets, empirical relations for the nach-disk diameter y and the maximum diameter of the barrel shock y Q 7 m a 3 for 10 ± p / <. 10 . ^ 0.598 v £n = 0.252 fp I d*




d *

- 0 316

Sometimes, values for the Mach number near the sonic orifice (upstream of the effective "source" at x ) and upstream of the orifice are needed. dicated above, Equation (33) As in-

is restricted to x/d*^l.

Values for M in these tuo regions have been determined experimentally by Sherman and Ashkenas and Anderson ' f or 1) = 5/3. Sharma for o = 7/5,

arrived at ex-

pressions for T/T

in terms of x/d* in these tuo regions His calculated Plach

from theoretical considerations.

numbers are larger than experimentally determined ones.


Chemical Relaxation in Supersonic Expansion Successful nBHS sampling requires that all

chemical reactions occurring in the sampled gas mixture are quenched, i.e., that they "freeze," as early as

possible in the free jet expansion through the sampling orifice. If the chemical reaction is frozen upstream

of the sonic orifice, then the sampled gas is most representative of the undisturbed gas composition. However,

if the reaction proceeds at large rates it uill be able to follow changes in temperature and pressure up to the nozzle throat, and in some cases several throat diameters downstream.



studied the occurrence of chemical

reactions in the supersonic expansion of a gas into a vacuum. of HjO4" H30++ H20 + M # HgQ* + PI (38) His investigation focused on the hydration

in an atmospheric premixed H2/02 flame uith nitrogen added as a diluent. be equilibrated Reaction (38) is fast enough to

in the flame.

For this purpose it is

necessary to calculate the variation of temperature, pressure, and density of the gas in the free jet expansion. Hayhurst arrived at a complete description of

the isentropic flou field by the method of characteristics. authors (The free-jet problem has been treated by other ' ). Note that in the high temperature and

pressure regions of the expansion, reaction (38) can be assumed to be equilibrated at all times. Hayhurst

concluded, "The calculations described above shou that there is continuum flou in the expansion of the gas through -.7 the sampling nozzle for about 5 x 10 sec, after uhich the flou is molecular. Consequently, if the relaxa-

tion time of any chemical reaction is much greater _7 than 5 x 10 sec at atmospheric pressure, the reaction

uill not proceed during the expansion.

If such condi-

tion holds for all possible chemical reactions, composition uill not be affected by sampling. sents the case of ideal sampling. This repre-

Houever, a reaction


uith a relaxation time less than 5 x 10 sec uill be

at equilibrium in the flame, where the time available _3 is about 10 s, and uill be able to follow any changes of temperature, etc., up to the nozzle throat. The

relaxation time of a reaction similar to (38) uill increase once inside the nozzle, because of the fall in gas pressure and temperature, so that a point eventually be reached at uhich equilibrium can no longer be maintained and the composition uill become "frozen." Consequently, the composition observed uill not necessarily be that of the original sanple, but uill correspond to conditions at some point in the sampling nozzle." Ions from flames have also been sampled by f'lorley 45 . His results are in agreement uith those of Hayhurst. In vieu of the importance of chemical relaxation in systems at high temperature and pressure, Knuth studied the chemical relaxation process in He identified the proper relaxation , the relaxation time at constant

flou systems.

time as being^ .

enthalpy and pressure, rather thariTy p , relaxation time at constant temperature and pressure. (Relaxa-

tion time is defined as the time required for the de\

viation from equilibrium to reduce to 1/e its initial value if the existing thermodynamic constraints uere maintained.) Knuth combined Bray's sudden-freezing

model uith Phinney's 57 relaxation-time-freezing point



§tYh>p -C (39)

uhere D/Dt is the hydrodynamic derivative and C is a constant, to arrive at a chemical relaxation equation, with C given a value of 0.5. Equation (54) of 40 Knuth provides a criterion for the early freezing of a reaction. This equation is characterized by tuo

parameters; namely, the kinetic parameter defined as the ratio of the chemical activation energy to the random thermal energy, and the scaling parameter defined as the ratio of the floui time to the collision time. 58 Young used a last-activated-collision model to determine a criterion for the freezing of a chemical reaction. In this model, a given chemical reac-

tion freezes approximately at the location uhere the sample molecule encountered its last activated collision, Young studied chemical freezing of bimolecular reactions involving an activation energy. The number of

activated collisions of a molecule uas computed along the free-jet centerline. The results of this calcula-

tion indicate that chemical freezing in the free jet is characterized by the kinetic and scaling parameters as defined by Knuth. Furthermore, the analysis reveals

that complete chemical freezing in the free-jet is obtained if the ratio of the logarithmic scaling factor


divided by the kinetic parameter is less than



~ / E*


•V" = scaling parameter = d*/a E* = Too
— .

kinetic parameter = E*/kT

— mean time between collisions of A and B molecules

E* = activation energy d* =, diam. of sonic orifice ( ) denotes stagnation conditions

These results can be used as a design criterion to develop a sampling system uhich avoids composition distortion by chemical reaction in the expansion.


Species Condensation

Species condensation in supersonic molecular 59 beams uas first observed by Bier et al in 1956. Condensation uould make the interpretation of measurements very complicated, but fortunately, as Knuth concludes in his revieu, the probability of condensations in FIBFIS sampling of high temperature systems is very small . The classical theory of homogenous condensation postulates that a critical size nucleus is spontaneously formed uhich has the properties of the bulk phase. Such theory cannot be applied to the rapid ex-


pansion occurring in a free jet for it leads to critical sizes that are of the same order of magnitude as the molecular diameters approach ' . Instead a kinetic theory

has been used to predict condensation

in the free jet, and the rate limiting step is the formation of dimers by termolecular collisions, not only for monoatomic gases, but also for polyatomic gases. Once the dimer is formed, tuo body reactions can produce trimers and larger clusters which lead to the formation cf a condensate. Knuth shows that the ratio of the flou time d*/a to the mean time,'f" , between consecutive three

body collisions is the relevant dimensionless scaling parameter in dimer formation. The smaller the flou time,

relative to the mean time between termolecular collisions, the smaller is the dimer production. This hy-

pothesis is supported by experiments conducted by several
{• I /- o




They found that the excess dimer mole

fraction (relative to the equilibrium mole fraction in the source) is approximately a linear function of p d*. Note that the scalina parameter d*/y a is re~o o o r\ lated to P by equation (56) of Reference 40. Furthermore, these experiments show that for d*/^Oa0 ^50 dimer formation is insignificant (see Table I of Ref. 40 for example), and that this rate decreases as TQ .63, 64, 65 increases






For theoretical treatment of separation effects in free jets and shocks, the reader is referred to the continuum analysis by Sherman Takashima
Fi R fi 7


, Mikomi and

, and the kinetic theory approach to a shock. Our aim

uave structure in binary mixtures by Oberai

here is to present the reader with the main results of the above experiments and theory. In his treatment of the free-jet of a binary gas mixture, Sherman combines the continuum flou

conservation equations (Navier-Stokes), uith the binary diffusion equation (41) based on the Chapman-Enskog theory of diffusion,

fv A

f D A B Tf(l-f) fmA"mB
1 m

V Inp



Uhere the subscript A refers to the heavier species; f is the mole fraction of the heavier species, m is the mean molecular mass given by
m = fm ft
H cj

+ (l-f)m Q

D Q R and(A-are the binary diffusion coefficient and

thermal diffusivity, respectively; V. is the diffusion velocity of the heavier species. Examination of Equa(1)

tion ( 1 leads to the following conclusions: 4)

In the free-jet expansion and in a shock transition,


the temperature and pressure gradients are in the same direction. Thermal diffusion opposes barodiffusion

under these circumstances.

Houever, an order-of-magas applied to the free-

nitude analysis of Equation (41),

jet or the shock uave, shou that barodiffusion is the dominant separation mechanism. (2) In the free-jet

expansion, the temperature and pressure gradients exist in the radial direction outuard from the centerline. The higher pressures and temperatures occur on the axis and decrease radially outuard as the Mach number increases. Thus, barodiffusion in the free-jet uill

cause an enrichment of the heavy molecules along the jet centerline (in barodiffusion the heavy molecules regions).

diffuse to higher-pressure

Sherman obtained an expression for f, the mole fraction of the heavy species, along the centerline of the jet, by expanding all variables in terms of inverse pouers of the Reynolds number based on stagnation conditions and orifice diameter, d*, and solving for the first-order perturbation term in the mole fraction, f, by integrating the equations (the zeroth order approximation leads to isentropic flous, and homogenous mixtures). in Ref. 66. This expression can be found

The theoretical results of Sherman have 70 been validated by the experimental results of Rothe ,




, and Campargue


. These results show that

the heavier species are enriched along the jet centerline as predicted from the diffusion equation and that most of the separation occurs over a distance of three throat diameters from the sonic orifice. Furthermore,

negligible separation in the free jet was found for

Knuth that for

40 considers Sherman's results and shous

C Sc
mass separation due to



= o(i) (42)

barodiffusion near the source 2 orifice is negligible for Re £ 10 . This criterion

is conservative for x/d* > 3 due to ordinary diffusion (Sherman neglected ordinary diffusion in his theoretical treatment. Ordinary diffusion, houever, may have In Equation (42),

to be considered for x/d* ^> 3).

C is a constant, and subscript o refers to stagnation conditions. Extensive experimental studies of the shock structure in binary gas mixtures (see Ref. 40 for an extensive literature review) shou the validity of the theoretical treatment of Sherman following features should be noted: fact that and Oberai (1)

Ouing to the

barodiffusion accelerates the heavier mole-

cules through the shock, and the light species in the


opposite direction, the shock and the jet boundary are enriched with the light gas molecules. (2) The over-

all shock thickness, in terms of upstream properties, is larger than for a pure gas under similar conditions. 40 Knuth argues, "Effects of pressure diffusion in the barrel shock are important in sampling studies if the relative enrichment of light species extends to the jet centerline." He continues, "The important role

of the pressure gradient through the barrel shock suggests that a suitable criterion for no reversed separation effects at the jet centerline might be provided by the criterion for a diffuse shock structure. As shoun 70 by Rothe , the shock thic thickness, o , is related to the flou parameters as follows




J3* ^

A diffuse shock is realized ifJ /X_ is sufficiently 5 large. Furthermore, for
^P« I/Re o / P i s

reversed separation will be insignificant along the jet centerline. (Separation effects due to the shock

structure have been called "reversed separation" and "background invasion.")



Relaxation Phenomena Considerations of relaxation effects in the

free-jet expansion are most relevant in FIBMS sampling of combustion systems. This uill be more apparent af-

ter the discussion of Mach number focusing and the timeof-flight temperature measurements. Consider the free-jet flou of a gas with vibrational, rotational, and translational degrees of freedom active at source conditions. Recall from the Kinetic

Theory of gases that to achieve relaxation, i.e.,equilibrium, of all degrees of freedom the number of collisions required is the largest for vibration and the least for translation. One can characterize the relaxation

process by a characteristic time *• (the time for the deviation from equilibrium to be reduced to 1/e its initial value if existing thermodynamic constraints are maintained). Furthermore, one can define a relaxation Kinetic Theory

time for each of the degrees of freedom.

also shous that as the temperature and pressure of the system decrease the relaxation time increases, since collisions necessary for energy transfer between the degrees of freedom become less frequent. Thus, if a significant change in temperature or pressure is realized in a very short time, as it is in the case of a HEMS free-jet expansion (see Fig. 5),


and as uas shown above, the relaxation of specified degrees of freedom will lag considerably from the change in the thermodynamic constraints. Uhen this occurs, the degree

of freedom is said to be "frozen," and the proper criterion for freezing is that I for the degree of freedom be much larger than the flow time through a given state. Since vi-

bration requires the largest number of collisions for relaxation, it freezes first, and it is folloued by freezing of rotational and translational degrees of freedom. As uas discussed in Section 3.2.2, Knuth oped a freezing point criterion, namely devel-

uhere c is a constant of order unity.

As Knuth points out,

this criterion is valid for all relaxation processes occurring in flou systems. For each relaxation process, the flou"

terms "partial-equilibrium flou," and "partial-frozen

are used to identify flou upstream and dounstreara, respectively, from the freezing surface of the relaxation process. Prediction of the location of each of the freez-

ing surfaces requires criterion (39), and the temperature dependence of the collision number for the degree of freedom of interest. Furthermore, the variation

of the centerline Mach number uith distance along the jet axis must be knoun. Expressions to predict The

the Wach number can be found in Section 3.2.1.


prediction of freezing-point locations is beyond the scope of this discussion, and the reader is referred to the uorks by Knuth et a!50»


7 4

and Sharma54.


Skimmer Interference Most of the literature pertinent to the free-

jet interference by the skimmer has been reviewed by 4D Knuth . Criteria uhich facilitate the design of systems uith minimum skimmer interference can be found in this reference. As Knuth points out, consequences

of this interference are (1) decrease of beam intensity, (2) widening of the velocity distribution, and (3) distortion of the beam composition, listed in order of decreasing sensitivity to skimmer interference. The aim here is to skim the isentropic core of the free-jet uith minimum interference by the following considerations: (1) The length of the skimmer

must be such as to minimize stand-off shock (.due to free-jet-interactions ence. (2) The shock structure must be attached to the skimmer with the chamber wall) interfer-

tip in order to effectively sample the isentropic core of the jet. This puts a restriction on the external

cone angle one can use depending on the Mach number. (3) The beam can be attenuated effectively by colli-

sions with molecules reflected off the inner surface


of the skimmer.

This effect is minimized if the in-

ternal angle is sufficiently large. The effects of orifice size uere studied by Fisher 75 and Knuth . For a conical skimmer, the skimmer-induced decrease in measured Plach number is less than


3^ if KnQ^ (= X ol/d,), uhere the mean-free-path A is based on molecular density at the skimmer and on


collision cross section at source temperature, is greater than about 0 3 0 4 .-.. The first three considerations

lead to Equations (60) - (62) of Knuth.


Mach-Number-Focusing Composition distortion due to Mech-number-

focusing is an unavoidable consequence of the different velocity distributions of the heavier and lighter species in the free-jet. The lighter species have a

greater tendency to fly auay from the centerline than the heavier species. The end result is an enrichment

of the beam uith the heavier molecules. Studies of P l a c h - n u m b e r - f o c u s i n g have b e e n made by Stern and Waterman

for the case of parallel

continuum flou at the skimmer, Sharma for mixtures 73 of C02, Knuth et al for mixtures of monoatomic gases, and Yoon and Knuth for mixtures of diatomic gases.

In examining the effects of Plach-number-focusing the follouing flou model is considered as de-


picted in Fig. ( ) ?: () 1 For a given species, transition from continuum

to free-molecule flou may or may not occur upstream from the skimmer entrance. (2) If transition occurs, then it takes place at a

surface uhich is spherical uith origin at the source orifice. (3) The molecular velocity distribution at the skimmer

entrance is, in general, a steady tuo temperature Plaxuellian distribution superimposed on a spherically symmetric radial hydrodynamic velocity. Before free-molecule flou is realized in the free-jet expansion, the translational temperatures Ti and Ttl are equal. But, as the expansion proceeds,

the flou deviates from isentropic flou due to a large decrease in the collision rate. earlier than Tj_ . T,t becomes frozen

Further dounstream, the variation

of T_L uith distance suitches from nearly isentropic to a collisionless type dependence uhere Tj_ decreases (due to geometrical cooling) uith a slope of -2. In

Rach-number-focusing studies, the relevant temperature
is Tj_


has shoun that the ratio of molecular

number density at the detector, n ,, to the molecular number density at the skimmer entrance, n,, for a given species can be expressed by


{The angles amax and £max are defined respectively by the line of sight from the detector to the skimmer lip and by a radial line from the source to the skimmer lip.)

Fig. 7. Schematic diagram of model considered in Mach-number focusing .



Where the geometrical parameters are defined in Fig. (7), and S^,, the speed ratio for the given species

at the skimmer entrance, is given by



i.e., the ratio of the hydrodynamic velocity to the most probable random speed perpendicular to U, at the skimmer entrance. Writing Eg. (45) for a minor species A and

the major species B and taking the ratio of these tuo expressions, one arrives at the enrichment factor 0 . (,

) (47)

The enrichment factor depends on both system geometry and the speed ratios. The effect of the speed ratios

on ®C , is knoun as Mach-number-focusing. For the spe2 ,2 . cial case that Sj, <^max -^ ^or ^ anc' B » ^-^' C47) 'De~


—, 2

i.e., independent of system geometry. Three cases are generally considered: (1)


Continuum-flou up to the skimmer. to free-molecule Transition


Transition (3)

flou upstream from the skimmer.

of free molecule flou for only one of tuo The analysis through which

species in a binary mixture.

^ ± is obtained for each of the above three cases can be very complicated. The reader uill find comprehen-

sive treatment of Mach-number-focusing effects in freejets in the references given at the beginning of this section.




Scattering of beam molecules by background molecules may occur in all of the FIBMS sampling system chambers. In practice, only scattering in the source

chamber might result in significant beam attenuation. If the beam has intensity I in the absence of back-

ground scattering, Anderson and Fenn


showed that

the effect of scattering can be expressed by

I = Io exp (-o- nx)


Uhere I is the observed intensity, n is the number density of scattering molecules,xis the distance over uhich scattering occurs, and cr is the effective scattering cross section. Note that in a gas mixture, scattering might result in distortion of the relative densities of the


several beam species.


has developed criteria

to minimize this effect and the beam attenuation in the source and collimating chambers.


Flame Perturbations By Sampling Cones Feu studies have been made regarding the ef-

fect of sampling cones on flames.

Furthermore, as

uill be shown, some of the theoretical studies that have been made are not totally relevant to FIBMS sampling systems. Biorde et al

investigated the effects of atm. They compared

probes on CFL/O^/Ar flames at 0.04

the relative effects of a quartz-microprobe uith the effects of quartz sampling cones of various angles and orifice sizes. Comparisons uere made uith respect to

(1) visual perturbation of the flame, (2) stable species concentration profiles, (3) temperature profiles, and (4) sensitivity to radicals. Species profiles uere The measured

obtained by MEMS sampling techniques.

temperatures in the absence of a probe uere compared uith temperatures measured tuo probe-orifice diameters upstream of the sampling cone by means of a thermocouple. Biordi et al.argue that this is the relevant Their experiment led them to the follou-


ing observations:



As the cone angle increases, the reaction zone

appears to shift dounstreara and becomes narrower, and the concentration gradients steepen. As they concluded,

"These effects may be rationalized in a qualitative fashion as due to the cooling ahead of the probe and 'attachment' of the flame to the probe." The cooling

would only result in the translation of the concentration profile (the probe is actually sampling flame gases corresponding to a point upstream of its actual physical location). Attachment causes non-uniform

motion of the flame, and the relative changes in the concentration profiles are a result of it. As Biordi

indicates, attachment is disastrous if one requires the information obtainable from the slopes of the species profiles, (2) The perturbed and unperturbed temperature profiles

differed by about 200°K in the low-temperature region and by about 100°K in the high-temperature region. Houever, for the cone for which visible attachment occurred, the effect on the temperature uas so great that it would be impossible to relate the temperature with the composition profiles to the accuracy required to calculate rates in the primary reaction zone. (3) It uas possible to detect radical species, e.g.,

0 , OH, H, with all the cones investigated.

The mi-

croprobe resulted in a 9Q% loss via wall and internal


collisions before a beam uas produced. They found that a quartz sampling cone uith 40 total angle and thin leading edge minimized all

of the abouementioned distortions for their experimental conditions, and that radical concentrations uere more in agreement uith those obtained by other means. Higher

pressures would allou the use of larger cone angles and thicker leading edges. 79 8D Hayhurst et al ' studied distortions caused by a sampling cone (1 to 2 mm. in length) projecting from a flat plate into 1 atm. H2 - 0- - N« flames. Ions formed in the flame uere formed into a beam by the use of electrodes and focused through a small hole into a detection system. The flow field model consisted

of a hemispherical point sink adjacent to a flat plate. Their flou-field studies shou that in order to minimize aerodynamic disturbances of the flame and boundarylayer effects the use of long sampling cones of relatively small external angles uith large orifice sizes is required. These external effects include heat transdistortions Hou-

fer, catalytic reactions, and composition

due to chemical reaction in the boundary layer.

ever, as pointed out, efforts to reduce boundary layer effects are in conflict uith efforts to minimize composition distortions during the gas expansion through the sonic orifice uhich require large internal cone


angles and small orifices


This is because the resi-

dence time of the gases before molecular flou is attained is prolonged by making the cone more pointed or by enlarging the orifice. chemical relaxation).
81 Smith " analyzed the problem of a long sampl-

(See section 3.2.2


ing cone in lou-pressure ChL/02 flames.

Smith's model

consisted of a sink located at the tip of an infinitely long cone with arbitrary cone angle. The main result

of his analysis is that the stagnation streamline moves towards the cone tip as either the cone angle or the sink strength is decreased. (The stagnation stream-

line separates that portion of the field that enters the cone orifice from that uhich does not enter it.)

Smith's results shou that a compromise must be made between disturbances of the sample before and after it passes through the sampling orifice. This is in agree-

ment uith Hayhurst's results discussed above, namely, that during the expansion chemical freezing occurs earlier if large cone angles and small orifices are used. However, consideration of distortions on the flame before expansion require the opposite. The studies by Hayhurst et al,and Smith can be used to predict the extent of cooling of the sampled gas and of composition distortion due to the presence


of the cone when one is measuring the average properties of the gas that flows through the sampling orifice. This is the case for the sampling of ions that are focused into an ion beam. Thus, for example, Smith

shous that if the fraction of sampled gas that has a smaller residence time in the thermal boundary layer than a given relaxation time for some chemical reaction is large, then one can expect little composition distortion due to cooling in the boundary layer before sampling. (The thickness of the thermal boundary layer

is approximately equal to that of the momentum boundary 79 layer since Pr/^1), The average temperature drop in the sampled gas due to boundary-layer cooling can also be estimated from their results. In MBRS sampling of flames, the free-jet is skimmed along its centerline by the skimmer. Thus,

only a very small fraction of the gas that flous through the sampling orifice ever reaches the detector. 82 fraction can be uritten as follous skimmer-orifice flou sampling-orifice flou This

= f(T)

Where d, = diameter of skimmer orifice, x, = distance from sampling orifice to skimmer orifice, and f(7~) is a function of specific-heat ratio. The ratio o^/x. ™T «~2 has values that range, from 10 " to 10 , and f(7")


has typically values of 1 or less.

Thus the fraction

( 0 is indeed small, and one may question the validity 5) of using the analysis by Hayhurst or Smith to predict distortions in MBF1S sampling systems when measuring neutral-species concentrations. That the use of aver-

age values is not justified for DBMS sampling of neutral species is shoun by considering the influence of the gas flowing along the sampling cone surface on the gas flowing near the orifice centerline. The extent

of the forementioned influence can be estimated from the ratio of tp, a characteristic time for flow through the region in the vicinity of the sampling orifice d*, to t_., the characteristic time for diffusion from 82 the uall to the centerline. Knuth ' has shoun that the value of tp/tp is of the order 10—2 . the above argument. This supports

(The lack of information on probe-

induced distortion in MBHS sampling of 1 atm. premixed flames has motivated a study uhich uas being carried out at the U.C.L.A. molecular beam lab. at the time this paper uas being uritten.)



The U.C.L.A. 1*181*13 Sampling System The MBMS sampling system uhich uas used to

sample the premixed atmospheric methane-air flat flames described here is depicted in Fig. 4. The background —3 -1 pressure is of the order of 10 to 10 torr. in the source chamber, 10~ to 10~' torr. in the collimating —R —7 chamber, and 10 ' to 10 in the detector chamber. The flame gas undergoes free-jet expansion through the sonic nozzle, and only molecules flying along the center-line of the system reach the detector. The design of the U.C.L.A. MBMS sampling system used here uas achieved by the considerations discussed in Section 3.2. The quartz sampling cone uas

selected on the basis of experiments, concurrent with this study, carried out at the U.C.L.A. Molecular-Beam Laboratory. It included a cone of total angle of 110°,

height of 50 mm., flat tip of 1.5 mm. of diameter, orifice diameter of 0.27 mm., and a channel length of 0.3 mm. More uill be said regarding sampline cones The source chamber is pumped by a 16The skimmer-to-

in Chapter 5.

inch-diameter Stokes diffusion pump.

nozzle distance can be varied so as to maximize the signal intensity at the detector. (orifice diameter 0.041 The brass skimmer

in.) transfers the core of

the free jet into the collimating chamber uhich is

pumped by means of a 10-inch diameter CUC diffusion pump. The skimmer uas designed to minimize its interference uith the beam. The skimmer internal half angle is 16°;

its external half-angle is 20°.

The collimating oriThe

fice (6 mm, diameter) can be closed by a valve.

detector chamber is pumped by a 6-inch-diameter NRC-UHS oil-diffusion pump. The baffle between the detector

chamber and its oil diffusion pump is refrigerated using Freon-12 to reduce background interference. The

mass spectrometer ionizer is placed uithin a liquidnitrogen cooled copper shroud uhich is itself attached by means of a "cold finger" to a four-liter deuar (enclosed by a vacuum uall) containing the liquid-nitrogen. The shroud reduces the background pressure in

the immediate vicinity of the mass spectrometer ionizer by approximately a factor of five. The ionizer is

kept clean by constant heating uith a small coiled-tantalum-uire heater. The above features have alloued Con-

detection of species in very lou concentrations.

tamination of the detector-chamber walls can be reduced by baking the walls externally. The flat-flame burner has been designed and its operation characterized by S, Saremi. Briefly,

it consists of a 2,30 inch disk (test section) of porous brass, a burner housing, and a uater-cooling copper


Uniform mixing of fuel and air is achieved by

passing the mixture through a 15-foot teflon tubing connected to the burner. An EAI Quad. 250 mass spectrometer is used for mass separation of the ions produced at the ionizer. Its output is amplified by an electron multiplier ating ab -3kv. oper-

The signal is further amplified by an

100 mega-ohms, 15pf. pre-amplifier and fed into a lockin amplifier. The beam chopper in front of the colliThe fore-

mating orifice permits signal modulation.

mentioned lock-in amplifier is synchronized with the beam chopper by means of a photodiode triggering system. The lock-in amplifier allous time-averaging the modulated signal from the pre-amplifier for periods up to 125 sec. The signal is finally fed into a channel converter connected to a LSI-11

of an analog-to-digital

computer uhich stores the data. An effusive source consisting of a ceramic tube uith an 0.040-in.-diameter orifice near its bottom can be placed on or off the system centerline. The effusive beam is used to calibrate the system and/or to study fragmentation patterns of molecules as a function of temperature. The ceramic tube is heated by A chromel-alumel thermocouple

means of a tantalum uire.

is used to measure the temperature of the gas in the source and a thermocouple gage to measure the pressure.


The source-gas temperature is measured by the time-of-flight technique (TDF). For this purpose,

a TOP experimental set-up is placed along the system centerline in the collimating chamber. This set-up

consists of an aluminum rod 25.6 cm. long uith a Bendix magnetic strip electron multiplier detector at one end and an electron-compact excitor at the other end. The aim is to produce metastable species (mostly M^) in the molecular beam by electron bombardment. The

ions in the beam are diverted by means of a small magnet attached to the aluminum rod before the detector. Thus, the signal generated at the detector is produced by the metastables alone. The electrons from the fila-

ment are collected by an anode connected to a uave generator uhich generates square uaves of uidth 1-5/Xsec. at 1 msec, time intervals. The signal from the detector

is amplified by a pre-amplifier (100 mega-ohms, 15pf.) and then fed into a Fabritek signal-averaging computer (model 1602) uhich includes a signal digitizer and a sueep control unit. The output from the uave

generator is used to trigger the averaging procedure of the Fabritck computer. The computer stores in mem-

ory the signal intensity as a function of time at preset time intervals (4^Wsec.) and averages it. The

output can be displayed on an oscilloscope or recorded on graph paper by a plotter.




Composition Measurements Partial automation and recent addition of

a LSI-11 computer have simplified the collection of experimental data and data-reduction. A servo-mechanism is

used to move the burner surface closer to or further from the tip of the sampling cone. The burner can

be moved faster or slower as required by the experiment. A voltage signal indicating the burner position

is sent to one channel of an analog-to-digital converter of the computer. A total of 100 data points can be

taken in the axial direction of the burner in a span of 0.6 cm. and stored in the LSI-11 computer. As men-

tioned in Section 3.3, the output from the electron multiplier is amplified by a pre-amplifier and then fed into a lock-in-amplifier for phase-sensitive sis. analy-

The net ion signal from the lock-in amplifier

is finally fed into a second channel of the analogto-digital converter of the LSI-11 computer and stored in the computer memory. oped for this purpose. The present detection system can resolve Computer programs were devel-


species uhich differ by 1 amu.

Species which differ

by less than 1 amu. e.g., CN (m/e = 26.0177) and C2H2 (m/e - 26.0378), cannot be resolved; their mass-spectrometric signals uill be detected at the same m/e ratio, i.e., at m/e = 26 for the species in the above example. The signal intensity at a given mass-to-charge ratio might be due to contributions of ions from stable species, radical species, and fragments from a parent molecule (fragmentation being a temperature dependent process).
1 -Z

Contributions from isotopes of rnajor




H A , CO

, also must be considered.

The separa-

tion of these contributions to the signal intensity at a given m/e ratio is facilitated in some instances by the formation and decay of the different contributing species in different spatial regions of the flame, and in some instances by differences in the electron energy for the ionization processes (ionization, fragmentation) for different species. An extensive com-

pilation of ionization potentials (IP) and appearance potentials (AP) of ions can be found in Ref. 88. The electron energy scale uas calibrated using the spectroscopically determined ionization potential of Ar, 15.76 ev. ionization efficiency For this purpose, several

curves of Argon uere obtained. The tail

One of these curves is reproduced in Fig. 8.


•—» 09



(5 i_


M 0 ^

3.0 2.0



* » )) | 1 • « 1 1 1 J







electron energy (ev) (uncorrected)

Fig. 8 . Intensity vs electron energy for Argon .


of the curve is due to the finite uidth of the electron energy distribution (about 1.5 - 2.0 ev). No ef-

fort uas made to reduce the uidth of this distribution. A correction factor for the energy scale uas obtained by comparing the electron energy at which the Argon signal first appears uith the literature value of


The experiments uer e carried out at an electron energy uhich minimizes, in some cases, fragmentation of the molecule and contribution of other species. This uas accomplished solely on the basis of appearance and ionization potentials. Because of the uidth

of the electron energy distribution, the signal of species that differ in IP or AP by less than 2 ev could not be totally resolved (unless the species occurred in different regions uithin the flame).



Temperature Measurements The temperature of the flame gases uas de-

termined experimentally by TOF techniques. imental set-up uas described in Section 3,3.

The experIn this

section, the analytical procedure used to determine the temperature uill be described. The time-of-flight

for the metastable species uas determined from the Fabritek computer output. To facilitate data reduc-

tion, the time of rise of the electronics uas determined and the time scale uas calibrated by means of room temperature measurements. The energy equation for adiabatic gas expansion may be uritten



U^ 2

= hjL +


^ ^

uhere the enthalpy includes rotational, vibrational, and translational contributions. For nitrogen, the

characteristic vibrational temperature is 3340 K so that relatively little energy is stored in the vibrational degrees of freedom at flame temperatures. Fur-

thermore, freezing of the vibrational modes is expected to occur very early in the expansion. ergy equation reduces to

Thus, the en-






so that, uith freezing of rotational and translations! degrees of freedom,

( c rot,o

+ c


+ R)T


= c

rot,oo Trot,eo 2 + (C, tr,oo +R)!,. tr,<»3 -t-NU1 (53) 2

where the subscript <^> refers to frozen conditions, Substituting for the values of the specific heats,
+ 3R + R\J
f) ' O

= R T



+ 5 RT.


+ MU





or the flame temperature TO To = •=• Trot,©o + is T. 2 5 tr,cx3 n r + FID, 2 1

(55) x


The most probable velocity of the molecules, U-,, is determined from the TOF experiments. The terminal

rotational and translational temperatures, T rot, oo and T. trjcxo respectively, uere estimated using the "sudden freeze" model described in Chapter 3. This proce-

dure is described in more detail in Refs. 74 and 82. (Note that if no freezing of rotational and translational degrees of freedom occurs, then the energy equa2 tion reduces to T = P1U-, /7R). o •*• TOF temperatures measurements have the advantage over other temperature measurements, e.g., thermocouple measurements, that one is measuring the temperature of gas at the same location and under the same conditions as during the sampling experiment.



C.alibrat 1 on Procedures The mass spectral signal intensity observed

for a particular ion, i, may be written NXj^


Where n is a constant that relates the number denIP sity of the parent neutral species in the ion source to the number density in the flame, C. a constant that includes gain factors and geometrical factors pertinent to the ion source, 0*. the ionization cross section, T. the transmission efficiency of ion i through the mass filter, 'TP- number of secondary electrons ejected at the conversion dynodes of the multiplier, N the number density at the gas source (the flame in this case), and X. the mole fraction of the species i. In a methane-air flame, the mole fraction of Argon remains approximately constant throughout the different flame regions since it is an unreactive species. Thus, the Argon signal uas used to normali.e.,

ize all other species intensity signals,

uith X A constant. Calibration of the MBF1S sampling system enknoun to good approximation, and C. ^ C Ar =


tailed experimental determination of the first tuo ratios on the right-hand side of Egn. ( 7 . For simplicity 5) i / Ar the ratio n /n will be called (n )i, and the racS

i S

tio qT i Y i /0^ r T Ar >^ r uill be called ( n E F F ) i .

Then, (58)


The factor (ng)i includes effects such as pressure diffusion in the free jet expansion, Mach-number-foThe factor (n^ppji u includes effects due only to the detection system. Calibration of the ["IBMS sampling system for a given species i can be done in two different manners. In the first, a source gss of known composition similar to the composition of the flame is sampled with the F1BF1S system. This allows determination of the cusing, and skimmer interference.

product (n )i(r]r-pp)i since all other variables in Eq. (58) are known. In the other method, an effusive source

is used to determine the detection system factor (hr-rr)i> and then (n )i can be obtained from the product (h )i (nrrrji or from a plot of (n )i vs. molecular weight. rr (The reader is referred to the discussion in Chapter 3, where (n-)i is shown to depend largely on the molecular weight of the species). Stable species in the flame were calibrated by the first method above, i.e., mixtures of known


composition uere put through the MBMS system and the product (1)1 ( n r - ) i was determined. The effusive

source allowed the determination of (nrrr)i for the

\P cular weight could be obtained.

species i; thus (n )i, and a plot of (n s )i vs. mole-

v/ The mole fraction

of stable species i in the flame was computed from 1


i M_miI-Lm"JJI

A, _ n

where X n , and I./I.

M 37

are also knoun.

For radicals, the mole fraction uas determined as follows: First, the beam factor (n s )i uas determined from a I plot of (n )i vsi m.. Then, (nrpp\i was estimated from the literature values for the total ionization crosssections of Argon and the species i, and from the sensitivity of the detector T. T"j/T"nr Tfcr » which uas estimated from the experiments conducted uith the stable species as a function of molecular ueight. (TJote that

s a lso a function of the molecular structure. Ar This introduces some uncertainty in this calibration


The radical mole fraction is then given
f • *i ^xAr yi- X



The uncertainty in this procedure is approximately a factor of 2.



The measurements were made using a room-temperature, one-atmosphere, premixed flat methane-air flame of equivalence ratio 1.37.

The flou rates uere SCFH for air.

kept at 5.12

SCFH for methane and 35.6

Air was used as the shroud gas in order to minimize the effect of buoyancy in the post-flame gases. The

flou rate of this shroud gas was set to minimize the deformation of the edge of the flat flame. The MBMS sampling system uas calibrated directly for the stable species CH^, 02, CQ-2, NH 3 , HCN and NO. For other species, eg, radical species, the

calibration procedure described in Section 4.3 uas used. As mentioned before, the species profiles uere taken uith the burner moving auay from the sampling cone. The electron energies uere selected to min-

imize fragmentation of the parent molecules, and to resolve the various contributions at a given m/e ratio.



Temperature Measurements in the Flame A temperature profile for the flame with

conditions as described above uas measured using the TOF techniques. Fig. 9 shows this profile when a probe orifice diameter 0.24 mm., channel

of total angle 80°,

length 1.1 mm., and tip diameter of 2.0 mm. is used. The post-reaction zone temperature corresponds approximately to the adiabatic flame temperature.





2 o a



(b 11.37

3-0.24MM *~ TIPDIA.I2.0MM








Distance (mm) Fig. 9 . Temperature profile measured using TOF technique .


During experiments, visible attachment of the flame to the quartz sampling cone uas observed. The attachment persisted up to a distance of about 0.35 cm. from the burner surface (for the above cone)

at which point the flame could be seen to detach itself from the cone tip. Furthermore, when the cone uas in

its closest position to the burner surface (0.013 cm.), the flame surrounding the cone uithin a radius dependent on cone geometry showed discoloration.

Temperature profiles for cones of different geometrical parameters (total angle, tip diameter, orifice diameter, and channel length) can give useful information regarding the effects of the forementioned parameters on the flame. Fig. 10 depicts the tempera-

ture profile obtained uith a quartz cone of the same total angle as the corresponding to Fig. 9 but uith a tip diameter of 0.5 mm., an orifice diameter of mm., and a channel length of 1.4 mm. The following observations can be made from Figs. 9 and 10. The uidth of the primary reaction zone 0.30

(defined as the region between the steepest temperature gradient and the post-flame temperature) for the measurements made with the cone of the larger tip diameter is approximately 0.5 mm. larger than that observed from the measurements made with the smaller tip diameter. Furthermore, the slope of the temperature pro-






I 1000

$-1.37 TIPDIAZ0.5MM








Distance (mm) Fig. 10. Temperature profile measured using TOF technique .


file for measurements made uith the cone of smaller tip diameter is greater. Note, houever, that the post-

reaction-zone temperature is approximately the same for both cones.


Observations of the cones during the temperature measurements shoued that for the cone uith the smaller tip diameter the surface area of the cone that uould glou red uas limited to the very tip of the cone in contrast to the cone uith the larger tip diameter for uhich a larger surface area uas observed to glou red. Furthermore, uith the cone in the closest posi-

tion to the burner, the forementioned discoloration of the flame uas least for the cone uith smaller tip diameter. (The diameter of this region uas approxiAlso, the

mately 0.5-1.0 cm. for the larger tip.)

detachment of the flame from the cone surface occurred approximately 0.5 mm. earlier for the smaller tip diameter than for the larger tip diameter as the burner moved auay from the cone tip. Further insight into probe-induced distortions of the flame is provided by the intensity profiles of C02 and 02 measured uith the tuo different quartz cones. These are shoun in Figs. 11-14. The effect of the larger

tip diameter is to reduce the measured rate of decay of 02 and rate of formation of C02 uithin the reaction zone of the flame. (The intensity profiles of C02 and

02 as uell as all other species intensity profiles, are normalized by the Ar signal to eliminate the effects of temperature variation uithin the flame. For

this flame, the Argon mole fraction is approximately


8134 ppm.)
In conclusion, for a flame uith conditions as described here, a cone uith a smaller tip diameter uill reduce the extent of flame attachment to the quartz cone. Attachment of the flame to the sampling cone

results in a decrease in the measured slopes of the concentration profiles and temperature gradient uith— in the primary reaction zone.




— O.oOmamp


Ti o


co tl o


dx=0.24 mm).





Distance (mm) Fig. 11. Normalized Oxygen profile ( tip dia-2.0 mm




zO.30 mamp









Distance (mm)



Fig. 12. Normafized Oxygen profile (tip diazO.5 mm,

d ~ 0.30 mm ) .



»e —0.30mamp


8 \


II 0



Distance (mm)



Fig. 13. CO2 Normalized profile ( tip diaz 2.0mm, djp 0.24mm ) .


Ee 120.50 ev —0.30mamp

tl o



! 0.!


Distance (mm)



Fig. 14. Normalized CC^profile (tip diaz0.5mm



The effect of channel length and cone angle
have been studied by Yoon and Knuth 82 in a study sub' sequent to the preliminary experiments conducted in this paper. As a result of their uork, the cone of to-

tal angle 110 , cone tip diameter 1,5 mm,, orifice diameter 0,27 mm,, and channel length p.3 mm, was selected as that which minimizes probe-induced distortions of the three cones described here. (The shorter channel

length uas observed by Yoon and Knuth to minimize chemical relaxation effects), Yoon and Knuth found also that the properties of the sampled gas for a stoichiometric flame are those of the gas about five orifice diameters upstream from the probe tip. Thus, temperature and concentration

profiles shown here and in the chapters to follow should be shifted upstream by a distance about five tiroes the orifice diameter of the probe. Note that the use of a FIBMS sampling system to obtain concentration profiles and flame temperatures makes the data so obtained more self-consistent than concentration profiles and temperatures obtained by two different experimental techniques, e.g., WBFIS sampling system for sampling of the flame, and a thermocouple to measure temperatures. Thus, temperature

and concentration profiles obtained by FIBFIS sampling


techniques makes data evaluation an easier task,



Stable Species Profiles Fig. 15 depicts the mole fraction profiles

for the stable species CI-L, CU*


nd CCU*

Methane and

Oxygen are totally consumed before the end of the reaction zone. The post flame mole fraction of carbon di-

oxide is near its equilibrium value of 5% (see Ref. 19).



Mole fraction

o o


o 3

§ oo




p o i



a «y 3 O * ^

H ?

r\i• < •

Sr t / O V I*m M
• • • •



of-*" < 1« .-• *. • •

* .•

ro p b o>


^t -t o

erOJh £

• •



• • ««



o •©1 , 1 1

: 0.40mamp

; 1.37


•o ^


m. p "*•..

o o

i i


p O



p O




b -^






Mole fraction


Formation of Nitric-Oxide in the Flame The concentration profiles for NO, NH3, HCN

are shoun in Fig. 16, 17, and 18, respectively.


NO (l.P. 9.25 ev)profile uas taken at an electron energy of 13.56 ev; at this lou energy lev/el, contributions of N15N15 and C12018 are effectively eliminated. In

the flame region uhere NO is observed to form, one could expect a significant contribution from C2Hg. Fig. 19 shous the relative intensity profile for m/e=30 at 13.56 ev. The first peak is attributed to HoCO, The C2Hg in the flame

and the second peak to C2Hg.

is all consumed at a distance of 0.45 cm. from the burner surface, thus making no contribution to the NO peak. (The first peak approximately 0.10 cm. is due to an ethane impurity, 0.12% in the methane and in this experimental uork). Further support for the H2CO assign-

ment to the first peak can be found in Fig. 6 of Ref.

The HCN (l.P. 13.73 ev) profile uas obtained at an electron energy of 14.76 ev. In the region 0.35-

0.45 cm. from the zero burner position, the relative contributions of HCN and C2H3 (uhich might include contributions from other C2-hydrocarbons) could not be resolved. Houever, by extrapolation of the portion

of the HCN profile to uhere there is no hydrocarbon


contribution, the onset of HCN formation can be seen to occur at approximately 0.35 cm. from the burner surface.


Concentration (ppm)

3 *P

1 ,



en O








en O

z 0
o 0

Ps —

O 4, O


I 1 I'
-I 0 Oi
-*• b "^



o « 3



« en "

• *

• * * • •


2. 3 3 3

£1 3'

3 en ~

° ,-s




* » *

* *








Concentration (ppm)

Z! *>
M <*-• 3"

1 J
/ *i ^-"

cn 0


O 0




O fl»





=r 5


$ ^

. •*

•S o











? (D °> 3


Concentration (ppm)




cn O


o o
3 O 0)

3 O O





5* 3
T> O^


11 1 1


o 3

O) (D


C5 O



(j) Z1-37

E^H 13.56ev

0.4 0.3

H 2 CO

!e z 0.


s 02 O CO






Distance (mm)




19. Normalized m/er30 profile.


The concentration profile for NH-, (I.P. 10.19ev) O uas obtained at an electron energy of 13.16 ev. In the

region uhere NHU forms, contributions from H90 fragmentation and OH radical species are possible, Hou-

ever, at 13.16 ev, fragmentation of H20 to OH (A.P. 18.3 ev) would be negligible even at flame temperatures. 89 The uork of Milne and Greene supports this assumption. The hydroxyl radical (I.P. 13.17) might possibly contribute to the peak at this electron energy. The rela-

tive intensity profile for m/e - 17 for the entire region 0.0 - 0.6 cm. is shown in Fig. 20. Since OH

contribution is limited to the region 0.20-0.40 cm. from the burner surface, the peak at about 0.55 cm. is solely due to NH^j. The concentration profiles for NO, NHg, and HCN have not been corrected for fragmentation of the parent molecules. Fragmentation of [10 is not likely to occur There-

until an electron energy of 20 ev is reached.

fore, at 13.56 ev, NO fragmentation uould be negligible at flame temperatures. The A.P. of CN from fragmenta-

tion of HCN (I.P. 13.73 ev) is quoted to be 19.36 ev90. Thus, HCN fragmentation at 14,76 ev is likely to be negligible even at flame temperatures. The absolute par-

tial ionization cross sections for Ammonia by electron impact, from the threshold energy up to 180 ev, have 91 been determined by Mark et al . At 19 ev, this partial









II o


E e - 13 - 16e v je Z0.40mamp



Ti c




• '











Distance(mm) Fig. 20. Normalized m/ez17 profile.


ionization cross section for fragmentation of NH X to

I\IH2 is about 21% of the total ionization cross section of NH. occurs. At and belou 19 ev, only ionization of MH, Thus, IMHU - fragmentation in the flame is

not likely to be important if the electron energy is kept lou, and at 13.16 ev is believed to be negligible,


The relative intensity signal for m/e=43 is shoun in Fig. 21, The electron energy uas 20.5 ev.

The signal in the region 0-0.20 cm. can be attributed to propane fragmentation, present as an impurity in the methane gas. The peak at approximately 0.25 cm. is The last peak at 0.55 cm. from the

most likely C^H--,.

burner surface is attributed to HMCO (I,P. 11.60 ev). The assignment is based upon the fact that HCM is also seen to form and decay at this distance from the burner surface, and HCN decay is likely to lead to the formation of HNCO. Measurements made at 11.7 ev further

support the assignment of the second peak to C-7Hi7. O Houever, the peak attributed to HNCO uas not aluays reproduced. Direct calibration of HNCO uas not carried

out, but its peak mole fraction has been estimated from Fig. 21 to be approximately 5 ppm. The results of the experiments conducted in this study support the mechanism by uhich the onset of HCN formation preceeds the formation of "prompt NO," and HCN decay results in the formation of the "prompt NO" near the reaction zone. Furthermore, PJH-, is observed The rapid

as the intermediate product of HCN decay.

build-up of Ammonia in the post-reaction zone, houever, seems to indicate that the formation of NO and N 2 from NH- species does not take place quickly compared uith the rate of HCN disappearance at a flame temperature


of 2000°k and ^ = 1.37.

HNCO seems to play no importconcentration

ant role in the decay of HCN since its in the flame is so lou.


(J) m.37
Ee- 20,5ev



I e H 0.30 mamp





Ti 0.5 O




Distance (mm)



Fig. 21, Normalized m/e=43 profile.



C2H2, C2Hg Profiles The concentration profile for acetylene in

the flame is presented in Fig. 22.

The profile uas Since the

obtained at an electron energy of 17.7ev.

system uas not calibrated directly for C2H2, the cross section data of Tate and Smith 95 uere used to obtain the mole fraction. quartz cone of 80 meter. This profile uas measured uith the total angle and 2.0 mm. tip dia-

The peak concentration of C2H2 in the flame This concentration level

is approximately 2100 ppm.

is in agreement uith the results of Harvey and Maccoll There is not sufficient data in the literature regarding the fragmentation of C2H2 and C 2 H- to calculate

the importance of each at flame temperatures. Houever, as mentioned above, the peak concentration of C-Ho obtained here is in agreement uith the measurements of Harvey and flaccoll. Fig. 23 shous the relative intensity profile for m/e = 27 at 20.50ev. The HCI\I contribution in This profile uas

the post-reaction zone can be seen.

also obtained uith the cone of 80° total angle, and 2.0 mm. diameter (cf. Section 5.1). Uith the burner

positioned at the point uhere the maximum signal intensity uas observed, an intensity vs. electron energy



profile uas measured.

The signal uas observed to vanev. Thus, C2H3 (l.P. 9.45ev)

ish at approximately 14.5

concentrations in the flame are likely to be negligible relative to those for C2H., and the signal presented in Fig. 23 is mostly due to the fragmentation of C2H. species.


Concentration (ppm)

Cn O
iQ* •




Cn O









X 10 *.
0 |\J

^om"e" II 41 II





S a s o ~GJ


w -Nj . o -^ g o «J -^


W rj H


» «




• . • * • ' .

s ao



^» O*


• —. » *





. '



(j)Z 1.37

E e Z 20.50ev [e ~0,30mamp


8 0.02

n o




profile .

Fig. 23. Normalized m/ez27


Figures 19 and 24 shou the relative intensity profiles for m/e = 30 at 13.56 spectively. and 12.10 ev. re-

As was mentioned in Section 5.2, the second

peak is assigned to C9H,Fragmentation and cross£• o. section data for C2Hg at lou electron energies are not available in the literature. Thus, an upper-bound

on the concentration of C0H,- was estimated from the £. b cross section data of Ref.92 and the fragmentation data of Berry and Osberghaus 93 . The maximum concentration of tfle was estimated to be 200 ppm. uas estimated to be a factor of 2. The uncertainty


r 1.37
r I2.10ev IT O.SOrnamp

03 O










I .





Fig. 24. Normalized rn/ezSO profile .



C»i and H2CO Species in the Flame The system uas not calibrated directly for

the species C, CH, CH 2 «

The cross sections uere es-

timated by additive methods from the data of Rapp and Kieffer


The uncertainty in these mole fractions The electron energy

is estimated to be a factor of 2.

uas kept low (about 2-3 ev. above the I.P. of the species) to avoid fragmentation of the molecule by electron impact. The concentration profiles for C, CH, Fragmentation of ChL

CH2 are shoun in Figs. 25 - 27. to C, CH, and ChU uas

observed to occur prior to the Thus, the peaks

formation of each of these species.

identified as C, CH, and CH2 have no methane contribution. As mentioned earlier, the cross section for

ionization of each of the CH- species uas estimated by additive methods. It is believed that the cross

sections estimated here are likely to be larger than the actual cross sections; hence, this estimate uill lead to lower mole fractions of the species in the flame.


Concentration (ppm)

•n •P
10 01 •

Cn O O '-O

cn O




•g o

11 H



I %

^ •*•S I




Concentration (ppm)



__ 0 O


rv> 0 O,
i i





en 0 0


i- jn -e""""

3C O



• i




S 3

O 3

0 W « —»



ru ~~
_• •


§. I" TJ








• , •


9 * «



Concentration (ppm)

•n G5' •
ro •-4
00 OJ

o o o o o O o o o o o o o o o o o o ~r i r


it H


O O 3 O


w o

U t± O 3


3 ts

3 rt> o <




(t) = 1-37
E Z 13.30ev
rt o o


le — O.SOmamp




II o




Distance (mm) Fig. 28. Normalized rn/en15 profile.


The relative intensity profiles for H?CO and CH|7 are shoun in Figs, 24 and 28 respectively.

These profiles uere taken uith the 80° total angle cone of 2.0 mm. tip diameter. No effort uas made to

estimate the absolute concentrations of these species. From Fig. 28, it can be observed that the CH, contribution cannot be totally eliminated even at lou electron energies. (This profile uas obtained at 13.3 ev.)

From Fig. 24 the H2CO formation is seen to occur prior to ChU formation. This profile uas obtained at an elecev. The disturbance by the probe

tron energy of 12.10

in this region of the flame for the cone used in this measurement is likely to be large (see. Ref.82), so that the uncertainty in the mole fraction that one uould estimate also uould be large.



The experiments show conclusively that,near the primary reaction zone of fuel-rich flames, NO formation occurs by a mechanism other than the Zeldovich mechanism. The amount of NO formed via the Zeldovich

mechanism, taking into account radical overshoot near 2R the reaction zone, uas predicted by Ay and Sichel in their computer analysis. From their Fig. 4, the NO

formed by the foreraentioned mechanism is approximately 10 ppm. The experimental NO concentration in the flame

after all HCN and NH3 in the flame have decayed uas determined in the study conducted here, to be approximately 56 ppm. Furthermore, the rate of NO forma-

tion uas observed to be largest near the reaction zone of the flame, prior to the decay of HCN, leveling off after all the HCN and NH 3 have been consumed. Ammonia 1.37,

uas observed in the post-reaction zone of the 0 = CH./Air flame as a consequence of HCN decay. The

rapid build-up of NH3 (peak mole fraction of 44 ppm.) suggests that the decay of NH. species, interconverted by reactions of the type,
NH X + H £ NH X-1 + H2



x = 1, 2, 3
via reactions

N + OH £ NO + H
NH2 + NO £ N2 + H20
NH + NO £ N2 + OH

(28) (29) (30)

N + NO £ N2 + 0

does not occur rapidly at flame temperatures. The onset of formation of HCN occurs prior to that of NO and approximately at the same time as NH- formation. Houever, the decay of HCN is too slou

for it to be consumed completely before the onset of NO formation. The flame uas sampled for HNCO.
o fi

Its peak mole fraction uas estimated to be approximately 5 ppm. This indicates, as suggested by Haynes ,

that HNCO decays by extremely rapid reactions, and that the initial weakening of the C-N bond in HCN to form the OCN - species is the rate limiting step in HCN oxidation. Concentration profiles uere obtained for the species C, CH, CH~. The maximum mole fractions

of C, CH, and CH2 are approximately 206, 481, and 908 ppm., respectively. The most likely reactions

leading to the formation of HCN are

C + N2 £ CN + N
CH + N2 £ HCN + N

( 7)

CH3 + N 2 £ HCN + NH


The rate constants of Reactions (7) and (13) were calculated by Peeters et al. from experimental data at 1820°K. Their values are given by

k? = 8 x ID11 exp (-11,000 /RT) k13 = 2.8 x 1012 exp (-22,500 /RT) in units of mole -1 cm3 sec-1 , uith a probable error of a factor of 2. It is likely that the formation of

HCN can be explained by Reactions (7) and (13), uith Reaction (13) dominating because of the larger concentration of ChU in the flame. Reaction (12) uould also

contribute, but to a lesser extent. C^-hydrocarbons uere observed to form and decay mostly uithin the primary reaction zone of the flame. The peak £^2

^e fraction uas estimated to The C2-hy-

be 2100 ppm., uncertain by a factor of 2.

drocarbons provide additional paths for the consumption of the methyl radical uhich contribute to keeping the ratio of CO molecules to hUO molecules formed from CH* oxidation equal to 0.5. Thus, this study

further indicates that C2 chemistry has to be considered in the kinetic modeling of methane oxidation in fuel-rich flames. The experimental data obtained from the flame gives insight into the mechanism of CH,-oxidation in fuel-rich flames. The formation of the methyl radical


does not reach significant rates until most of the formaldehyde in the flame has been consumed, (The hUCO-

forming reaction(s) keep the CHU concentration level very low). Furthermore, the HUCO profile attains a

maximum before the primary reaction zone of the flame is reached. The lou 0-atora concentrations in the re-

gion uhere FUCO rapidly forms suggests that the reaction of CH3 uith oxygen is the main path for H~CO formation. Visible attachment of the flame to quartz cones of total angles 80°, and 110° uas observed in

the course of these experiments, for a flame of equivalence ratio 0 = 1.37. The attachment to the cone per-

sisted throughout the primary reaction zone of the flame and resulted in a decrease of both temperature and concentration gradients uithin the primary reaction zone. Quartz sampling cones of small tip diameters

reduce the attachment effects.


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