I!- AD-AI12 275 QUEEN MARY COL.L LONDON (ENGLAND) DEPT OF CHEMISTRY F/s 7/3I KINETICS OF OXIDATION REACTIONS INVOLVING S AND Al CHALCONIDES. (U)

MOV SI A FORTN1'J M A CLYNE AFOSR-81-00OS5

UNWCLASSIFIEDFOSR TR-820131 NL

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MICROCOPY RESOLUTION TEST CHART

NAIIONAL prijAL[ OF IANI,)ARIlF' 6 A

AFOSRTL 8 2-0131

L Grant Number AFOSR-81-0035

KINETICS OF OXIDATION REACTIONS INVOLVING

B AND Al CHALCONIDES

Arthur Fontijn and the late Michael A. A. Clyne,Department of Chemistry,

Queen Mary College,Mile End Road,London El 4NS, UK

November 1981

Final Report, 1 October 1980 - 30 September 1981

Approved for public release; distribution unlimited

Prepared for: 12.1b

Air Force of Scientific Research, .. . ).

Bolling AFB, Washington DC 20332 -

and

European Office of Aerospace Research and DevelopmentLondon, England.

GXUAA Approyd for publie releuseAA distribut ion unIfted.

AIR FOP=~C D'PFIc ' Sr~rrpC FiSAFr

This techn~ical report has been revieioqd and i.: t-

approved for publtc release IAW Ayp ,~2Distribution is unlImItad.

TABLE OF CONTENTS

Page

I. INTRODUCTION - SCIENTIFIC OJECTIVES 1

II. BIBLIOGRAPHY OF PUBLICATIONS 2

III. DISCUSSION 3

A. Temperature range 3

B. Production and monitoring offurther radical species 4

IV. CONCLUSIONS 6

V. REFERENCES 7

Figure 1 9

Figure 2 10

"Kinetics of the ReactionBO + 02 + B02 + 0" (Appendix A) 11

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UNCLASSIFI~h" 'ECURITY CLASSIF ICA TI ON OF THIS'PAGE (Iii.,, Data, Kriter..d,

REPORT DOCUMENTATION PAGE READ INSTRUCTIONS________________________________________BEFORECOA~PLETING FORM

R ~2. GOVT A' -SS4jN No. 3. RECIPIENT'S CATALOG NUMBERl*R ~ -1R- 8 2 -01 3 1 4 9N 175-

4. TITLE (and Subtitle) 5. TYPE OF REPORT & PERIOD COVERED

1 Oct 80 - 30 Sep 81FINAL

KINETICS OF OXIDATION REACTIONS INVOLVING B AND 6. PERFORMING 01G. REPORT NUMBER

Al CHALCONIDES ________________

7. AUTHOR(s) 8. CONTRACT OR GRANT NUMBER(s)

ARTHUR FONTIJNMICHAEL A A CLYNE AFOSR-8 1-0035

9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT. PROJECT, TASKAREA & WORK UNIT NUMBERS

QUEEN MARY COLLEGE610F#DEPT OF CHEMISTRY 6102FA sab'MI-LE END RD. LONDON, El 4NS, UK 2308/A

It. CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATE

AIR FORCE OFFICE OF SCIENTIFIC RESEARCH/NA NOV 81BOLLING AIR FORCE BASE, DC 20332 .1 13. NUMBER OF PAGES

_____ ____ 16:0) 15. SECURITY CLASS. (of this report)

'~UNCLASSIFIED

I5a. DECL ASSI FIC ATI ONDOWN GRADING-SCHEDULE a~

16. DISTRIBUTION STATEMENT (of this Report)

Approved +for public release; distribution unlimited.

17. DISTRIBUTION STATEMENT (of the abstract entered in Block 20, If different from Report)

IS. SUPPLEMENTARY NOTES-

19. KEY WORDS (Contlinue on reverse side it necessary and Identify by block number)

BORON OXIDATIONREACTION KINETICSREFRACTORY FREE RADICALS

20. ABSTRACT (Continue on reverse side If necessary end Identify by block number)

Work on various problems in solid and air-breathing rocket development, e.g.,submicron particulate formation, requires the input of kinetic data over widetemperature ranges on the oxidation reactions of refractory free radical species.Various approaches for producing these species and investigating tieir kinetics,using laser-induced fluorescence and hl~h-temperature fast-flow reactors, arediscussed. To demonstrate the feasibility of a new discharge-flow reactormethod for producing such radicals~for kinetic studies, the kinetics of B0 + 0 2

LB07+0 was investimated- A r~t r -r 4XIO_ 12 CM3 molecule- i'it 2 9 5k

DID I ~PIrAR7 1473 EWOtr0 Of I NOVA ISOSOLETEUNCLASq'I Ft F

SECURITY CLASSIFI ATION OF THIS PAGE (When Data Entered)

I. INTRODUCTION - SCIENTIFIC OBJECTIVES

The need for a reliable kinetic data base on reactions

of refractory metal atoms, metal oxide radicals and metal

halide radicals* for various aspects of solid and air

breathing rocket development has frequently been expressed,

e.g. Ref. 1. To provide such data for metal atoms, one of

us (AF) previously developed the HTFFR (High-Temperature

Fast-Flow Reactor) technique,2-4 which is uniquely useful

for measuring rate coefficients and their temperature

dependence within the temperature range of approximately

300 - 1900 K. Some data on a metal oxide radical, AlO, were

also obtained through the convenient expedient of observing

the two-step oxidation of Al atoms with the same oxidiser.

However, the need for more systematic means of studying

reactions of metal radicals in HTFFRs was obvious4 . The

visit, during the grant year, of AF to the laboratory of the

other of us (MAAC), with its state-of-the-art equipment for

laser-induced fluorescence (LIF) detection of free radicals,

presented a natural opportunity for such more systematic ex-

ploration. LIF currently represents the most sensitive

technique for monitoring of such radicals. Consequently,

the objectives for this program were to make a kinetic study

of a reaction of a refractory oxide radical (BO + 02 + B02 + 0)

*The word "metal" is used here in its propulsion technologysense, thus specifically including B, which is not ametallic element in the usual physico-chemical sense.

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and to explore means for future kinetic studies of

refractory radical species of significance to Air Force

development programs.

II. BIBLIOGRAPHY OF PUBLICATIONS

The present one year effort has resulted in the

following publication (Appendix A of this report):

I. P. Llewellyn, A. Fontijn and M. A. A. Clyne,wKinetics of the Reaction BO + 02 + B02 + 00,Chemical Physics Letters, in press.

"The reaction of BC13 + N + 0 was used to produce80 X2E+ radicals for study in a fast-flow reactor.Laser-induced fluorescence was used to follow theBO X2E+ radicals. The feasibility of kinetic studieson these radicals was demonstrated through a kineticstudy of the BO + 02 reaction, giving a rate

+4.7coefficient kI equal to ((4.4 ) x 10- 12 cm3

-3. 2

molecule-1 s-1 at 295 K."

Additionally considerable progress was made in the pre-

paration of a book chapter which discusses the status of

theory, experiments and predictive ability on the influence

of temperature on rate coefficients of bimolecular

reactions. The type of metal and metal radical reactions of

interest to the Air Force form an important subset of the

reactions discussed. This chapter and book are scheduled

for publication in late 1982. The reference will be:

A. Fontijn and R. Zellner, "Influence of Temperature onRate Coefficients of Bimolecular Reactions" inReactions of Small Transient Species (M. A. A. Clyneand A. Fontijn, Eds.), Academic Press, London, Chap.2.

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"Kinetic studies in recent years covering widetemperature ranges, have shown that the traditional expec-tations of near-Arrhenius behaviour, k - A T exp(-Ea/RT),are often unwarranted. Available data are reviewed in thelight of current theoretical and semi-empirical understanding."

III. DISCUSSION

The major complete results of the present work are

given in a publication (Appendix A). In addition to

providing ap important rate coefficient, this work has

demonstrated the practicality of a chemical production

method for a highly refractory oxide species (BO),

compatible with its subsequent kinetic studies in a

fast-flow reactor. This demonstration was made for one

species using a room temperature reactor. The two obvious

questions raised for future work thus are:

(i) what is the temperature range for which this type

of approach can be used, and

(ii) how can other radicals similarly be studied?

A. Temperature range

Figure 1 shows a simple means for extending the

temperature range of the studies. Compared to the work of

Appendix A, the Pyrex reactor has been replaced by a ceramic

reactor, surrounded by a high temperature furnace. At the

upstream end the free radical species (MeX) flows in from a

preparation line, which for BO would be identical to that of / --s

the present work. Any desired oxidant Oz, C02, NO2 , HCl, / .-"

etc. can be introduced, generally independent of the MeX

production method. An HTFFR based on this model was

COP ',ls c O _ .. . . . -

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4

designed, constructed and tested during the course of the

grant, but insufficient time was available to study the

BO/O2 reaction in this apparatus. The reaction tube and BO

inlet were made from impervious mullite (Morgan Refractories

Ltd.) and the three-zone furnace was made of Kanthal-A

elements (Bulten-Kanthal AB) surrounded by Triton blanket

and board insulating material (Morgan Refractories Ltd.).

This combination of materials allows work up to about 1500

K. The observation fluorescence cell was replaced outside

the heated zone. This was done to facilitate joining of the

reactor to existing laser-induced fluorescence apparatus at

Queen Mary College, not because of a principal advantage. A

previously used 3,4 modular HTFFR is shown in Figure 2. It

is obvious that the "source section" of that reactor can be

removed and the reactor section joined to a preparation line

as in Figure 1, resulting in a constant high temperature

zone including the observation region.

Thus there appears to be no reason in principle why the

metal radical work could not be extended over the full

temperature range of some previous HTFFR work (300 - 1900 K)3,4 .

The choice of apparatus design will depend on the radical of

interest, as will be discussed now.

B. Production and monitoring of further radical species

The traditional way of producing metal oxide and halide

radical species is by evaporation of inorganic compounds5 .

This approach could be practised with an original 3'4 modular

BTFFR, Figure 2, in which the vaporizer contains the

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5

inorganic parent compound. Thus, SnO can be produced by

dissociative evaporation of SnO2 , or else from Sn/SnO 2

mixtures where the Sn acts as a reducing agent; these

methods can be used at about 1400 K(6). Such vaporization

methods are in principle similar to those used in metal atom

HTFFR work 3'4 .

A number of methods for refractory radical production

have been developed in recent years in the area of

preparative metal-organic chemistry. These can best be

utilized with a preparation line approach, Figure 1. They

can be divided into two groups: gas-solid reactions and

pyrolysis5 7. An example of the former is the production of

BF by passage of BF3 through solid B granules at - 2000 K,

and one of the latter is the production of BC1 by passing

B2C14 through a quartz tube at - 1300 K (also yielding

BCl3). In HTFFR studies it is of course necessary to

ascertain that the other species present, BF3 and BC1 3 in

these examples, do not interfere with the reactions studied,

which is in general not likely for such thermally rather

stable compounds. These groups of methods can be expanded

by the use of laser photolysis, a method apparently not yet

used in studies of reactions of inorganic free radicals, but

one for which the basic technology has reached a high degree

of development in recent years 8 ,9.

It is important to note that neither the literature on

evaporative, nor on the preparative, methods appears to

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6

contain any information on the production of BO, the species

investigated experimentally in the current study (Appendix

A). Only B202 could be produced in metal-organic synthesis

work7 . The discharge-flow reaction method developed here

for BO, i.e. reacting BC1 3 with a flow of N/O/N2, was

attempted on the basis of observations that BO emission

spectra can be produced in the reaction of BC13 with active

nitrogen containing traces of oxygen i0 , while the reaction

Of BC3 with 0/02 mixtures only appears to produce B02.11

For many radicals such emission spectroscopic observations1 0

could be adapted to discharge-flow methods for production of

their respective ground states. Often the yields will be

very low, as was found to be the case for BO. However,

coupled with the extremely sensitive monitoring method,

which is LIF, low radical concentrations need not be a

drawback.

In the above we have emphasised the preparation and

monitoring of diatomic radicals. However, triatomic

radicals can be produced by similar methods and again LIF

offers currently the most sensitive detection technique.

For these larger species there is currently less information

available from earlier work. That this situation is

changing may be illustrated from the above mentioned Ba2

studies1" and the recent work by Hirota 12 on BOCI.

IV. CONCLUSIONS

In this work the practicality of producing a highly

refractory fret, radical species, BO, by a preparation line

GXUAAP

7

method has been demonstrated and k,.netic data on its

reaction with 02 have been obtained. The technical

possibilities for more extensive studies of rate

coefficients, and their temperature dependence, for

refractory radical species of Air Force interest are highly

promising. A large variety of radical production methods

can be combined with HTFFR methodology and laser-induced

fluorescence monitoring to achieve this goal.

V. REFERENCES

1. Air Force Sxstems Command Research Planninz Guide,HQ AFSC TR 80-01, February 1980, Sections 5.1 and 5.2

2. A. Fontijn and S. C. Kurzius, "Tubular Fast-Flow ReactorStudies at High Temperatures. 1. Kinetics of the Fe/0 2Reaction at 1600 KO, Chem. Phys. Lett., 13, 507 (1972).

3. A. Fontijn, "High-Temperature Fast-Flow Reactor Studiesof Elementary Reactions", in High Temperature Metal HalideChemistry, (D. C. Hildenbrand and D. D. Cubicciotti,Eds.), The Electrochemical Society, Princeton, 1978, p.484.

4. A. Fontijn and W. Felder, "High Temperature Flow Tubes.Generation and Measurement of Refractory Species", inReactive Intermediates in the Gas Phase. Generation-and4norin,(D. W. Setser, Ed.), Academic Press, New York,

TM, lap.2.

5. K. J. Klabunde, Chemistry of Free Atoms and Particles,Academic Press, New York, 1980.

6. J. M. Dyke, University of Southampton, Private Communi-cations to the authors.

7. P. L. Timms, "Techniques of Preparative Cryochemistry"in Cryochemistry (M. Moskovits and G. A. Ozin, Eds.),6hn Wiley, New York, 1976, Ch.3.

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8

8. M. N. R. Ashfold and G. Hancock, "Infrared MultiplePhoton Excitation and Dissociation: Reaction Kineticsand Radical Formation" in Gas Kinetics and EnergyTransfer, Vol. 4 (P. G.-shmore and R. J. Donovan,Eds.), The Royal Society of Chemistry, London, 1981,Chap. 3.

9. R. J. Donovan, "Ultraviolet Multiphoton Excitation:Formation and Kinetic Studies of ElectronicallyExcited Atoms and Free Radicals", Ibid., Chap. 4.

10. R. W. B. Pearse and A. G. Gaydon, The Identificationof Molecular Spectra, 4th ed., Chapman and Hall,London, 1978.

11. M. A. A. Clyne and M. C. Heaven, "Laser-InducedFluorescence of the BO and 802 Free Radicals",Chem. Phys., 51, 299 (1980).

12. E. Hirota, Discussion comment in Faraday Discussions71, to be published.

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9

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TABrLE 1

Susiy of 30 + 02 _. .02 + 0 Rate Coefficient Eeaeuremsas

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l ) (a s2) (--) (10 -3) (arbitrary units) (10-12 3

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2.8 16 67 89 2.2 0.6 - 20 0.18 3.9 -0.962.7 16 67 90 3.1 3 - 34 0.20 9.6 -0.99

2.3 16 33 s0 S.5 1 - 14 0.23 1.-1 -0.992.9 16 67 87 2.9 8 - 21 0.23 3.7 -0.90

2.8 16 33 53 S.5 7 - 13 0.40 0.7 -0.972.8 16 33 53 5.9 S - 22 0.43 4.3 -0.982.8 16 33 53 6.1 3 - 40 0.54 1.8 -0.94

2.8 14 33 53 4.8 2 - 40 0.62 1.5 -0.98

2.7 is 18 37 7.0 3 - 40 0.46 0.7 -0.862.8 15 18 35 9.1 2 - 50 1.0 1.5 -0.982.6 27 18 S1 6.0 4 - 50 1.0 7.4 -0.81

2.6 27 18 52 5.2 4 - 25 0.30 7.S -0.98

2.6 27 18 52 4.8 2 - 23 0.41 3.7 -0.99

2.5 27 18 S3 4.3 2 - 30 0.39 10.6 -0.96

2.7 28 35 69 3.5 0.7 - 4 0.12 9.3 -0.9s1.9 22 18 65 3.7 2 - 20 0.20 7.7 -0.99

2.0 22 18 60 5.3 0.7 - 4 0.14 8.6 -0.934.1 22 18 30 9.3 2 - 12 0.23 1.9 -0.914.0 22 18 30 7.9 2 - 20 0.12 5.0 -0.944.1 22 18 30 6.7 4 - 40 0.13 5.6 -0.905.3 22 96 64 1.2 1 - 20 0.29 2.2 -0.965.5 22 96 64 3.6 2 - 13 0.64 2.0 -0.99

5.5 22 96 63 2.9 1 - 17 0.89 1.0 -0.89

all Torr 133.3 Pa b)mean pluq flo velocity c) intia. Be, ofuoriscenceiatensity

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