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Distribution authorized to U.S. Gov't.agencies only; Proprietary Info., ExportControl; 31 Jul 1967. Other requests shallbe referred to the Office of NavalResearch, Attn: Code 429 Power Branch, 800N. Quincy Ave, Arlington, VA 22217.

AUTHORITY4 May 1977, ONR, per ltr; ONR, per ltr dtd4 May 1977

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NOTICE: When government or other drawings, specifications or other

data are used for any purpose other than in connection with a defi-nitely related government procurement oper~ation, the U. S. Governmentthereby incurs no responsibility, nor any 'obligation whatsoever; andthe fact that the Government may have formulated, furnished, or in anyway supplied the said drawings, specifications, or other data is not]to be regarded by implication or otherwise as in any manner licensingthe holder or any other person or corporation, or conveying any rightsor permission to manufacture, use or sell any patented invention thatmay in any way be related thereto.

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AZA IVISION p'oF NrTH AmEimk.CAN, AVIATION. IN.

Best Ava-llabile Copy

r "\Tfl~t CGUoTt,` iWfNCIlA A 0 FTET`l r'iC W I) 'U.S OF 1iý CNNMTrl SVT,,-E7 W TH~ E o~. N orl THE

'7,E LP'.*:4. TIT',' I S . -CTIONS 793r AMD 7T,4, MI TRAHS-

CONFIDENTIAL

(Unclassified Title)

FINAL REPORT,

INORGC.NIC HMLOGEN OXIDIZERlS

(30 May 1966 through 29 May 1967)

Group 4Downgraded at 3-Year Intervals;

-Declassified After 12 Years-

Contract Nonr 4428(00)G.O. 8614

Sponsored by Office of Naval ResearchPower Branch

Code 4*29

PREPARED BY ______

D. Pilipovich lReproduction in whole or inC. J. Schack ipart is permitted for anyC. B. Lindahi :purpose of the UnitedH. H. Rogers Sttes Government.APPROVED BY

E. A. LawtonManager

Synthetic and Propellant ChemistryResearch Division

NO. OF PAGES722.x&i i REVISIONS DATE.31 JulY 1967

DATE REV. BY PAGES AFFECTED REMARKS

FOIA ONM f -0I ftCv. 4-64W "WN -f 1a 0 sq*'CONFIDENTIAL nLWs-B-.. 09"PUo .* rs11"W.0. 13

NOTICE

UNITED STATES PATENT OFFICE SECRECY ORDER

A patent application has beer, filed In the U, S. Patent Office by NorthAm.crtcar Atat:orn Inc. based upor, ubject matter included herin urrelated hereto, and the Secrecy Order appended heretohas been :suedthereon pursuart toTtite35. Unttedtaies Code (1952) SectIons 181-188.Fur•rer dissemination of said subject nmatter is prohibited except i.strict compliance with said order. The recipient of this document isreq,.esied to rotify all persons who willhave accessti this material ofthe Secrecy Order. Penaltties for vtolation oi a Secrecy Order includea fltoe of J•p to $10, 000 or imprtsonnment tar rot tore than two years.or both,

DEPARTMENT OF COMMERCE DEPARTMENT OF CObMMERCEUnited States Patent Office United tates Patent Office

Washington WashircLton

SECRECY ORDERPERMIT FOR PATENT APPLICATION

NOTICE: To the applicant above named, his heirs, and any and all CL:ASS•I,_EIBY GOV._yERNMENT-CON-.TRACThis assignees, attorneys and agents, hereinalfter designated principais:

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If prior tothe issuance of the secrecy order ary significant part ofthe subiedt matter has beenrevealed ioany petsion, the princip,Us shall

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This order should not be construed in any way to mean that theGovernment has adoptedor contemplates adoption of the alleged onven-tion disclosed Inthis app!lcation; nor is it any indicalionof the value of

such Invent nit.

CONFIDENTIAL*A DIViSION OF NORTH AMER!CAN AVIATION INC

The research reported herein was supported by the

Office of Naval Reseaych, Power Branch, Code 429,

with Mr. Richard L. Hanson as Scientific Officer.

This report was prepared in compliance with Section

H of Navy Contract Nonr 4428(00) and covers the

period 30 May 1966 through 29 May 1967. The pro-

gram manager was Dr. E. A. Lauton, Manager, Syn-

thetic and Propellant Chemistry. The work was

conducted in Oxidizer and Fluorine Chemistry with

Dr. D. Pilipovich, Principal Scientist as principal

investigator. Full-time staff members contributing

to the technical effort were Dr. H. H. Rogers, Dr.

C. J. Schack, and Dr. C. B. Lindahl.

A

R-7149 COFDETA

CONFIDENTIAL

CONFIDENTIALa

*A U ~I V 91 OF NORTH- AMER AP4 AVIATION~ IN C

New syntheses of CIF 0 were discovered utilizing ultraviolet-.3

initiated reaction of FC10 and FC1O In the presence of2 3'

P2, CIF3, or CIFs, FCIO2 gave ClF 0 in high conversions and

high yields. The most effective fluorinating agent was ClF5.

The same techniques were not successful in oxidizing ClF3 0

to C1F•0 or BrF.. to BrF There is considerable evidence

that FCIO is an intermediate in the synthesis of CIF_0 by

ultraviolet activation. More complete ultraviolet data

were obtained with the measurement of extinction coeffi-

cients of ClFs, BrFs, CIF0, FCI0, and CIF.

Corona discharge activation in the systems FCI02-F2 did not

result in ClF 0. Initial decomposition of FCl0 to Clf3 2followed by fluorination to either CIF or CIF. was ob-

3served.

A stable mass cracking pattern for COF 0 was obtained with

the most prominent peaks assignable to ClFO* (100 percent),

ClF 2 0+ (80.60 percent), C1 (29.35 percent), CiPF (21.23

percent), and CO" (14.78 percent).

The F 1 9 n.m.r. spectrum of gaseous ClF 0 revealed two bands3

at -276 (p and -317 0 with respective ratios of 2 and 1. These

bands could not be resolved further but support the proposed

Cs symmetry for CIF 0 rather than C symmetry alreadys 3 3v

partially excluded by infrared studies,

A novel process for forming NF 0 has been discovered. It was3

determined that the action of ClF 0 on difluoramine, IWF2 ,3 2

R-7149 v

CONFIDENTIAL ... .__ I

CONFIDENTIALWK 400 4 A OIVISION OF' NORIHI AWrMICAN AVIATION INC

reproducibly formed NF 3 0 in 80-percent yields at temperatures

below ambient. Perfluoroformamide, F2 NCFO, also reacted

with Cl•F0 to yield N. 0.3 3

Mass cracking patterns were obtained for both IF and IF.0.7

New, more precise physical properties were determined for

IF.0; the vapor pressure-temperature equation is log pmm =5

8.9874-1659.4/T. The preparation of IF302 was attempted by

reaction of IF.0 and SiO2 at elevated temperatures. The py-

rolysis of IF 0 yielded an unidentified volatile material5

which may be a new IF 0 compound. Reaction of IF 0 and ILHT

yielded FNO and N F as oxidation products.

A new, rapid method was developed for the synthesis of chlo-

rine nitrate, CIN0O The process utilizes the reaction of

C1F and ENO at temperatures above -112 C. A similar inter-3

action between BrF. and HNO 3 yielded limited amount.s of

BrNO Fluorination of BrNO led to a new solid complex of3' 3

the type NO2 BrF 0. A characterization of the complex N0,BrF2 x

was carried out to distinguish it from the above solid.

The solid obtained by reaction of C12 0 and AsF... has been

shown to be principally CI02AsF6 . A physico-chemical char-

acterization of the solid was conducted.

Preparation of CI¾T20 was attempted via a dissociative re-

organization process involving NF3 0 and PF CI. Instead, a

slow fluorination of the PF 4 CI to Py.. resulted, accompanied

by reduction of the NF 0 to FNO.

vi R-71149

CONFIDENTIAL

CONFIDENTIAL IE

Oxychiorine tri fluoride did not ionize in either BrF or IF3 5'

The specific conductivity of C19" 0 wa measured at 21K C, +he c

value obtained iasi x 10 ohms cm The reaction of

CIF 0 with AsF was complex, producing products including3 3

02' As, FClO 2 P, n l 2 0AF6 Atepts to prepare ClOAsF 6ýwere unsuccessful, All of the systems (ClF-AsF, CiF-AsF

59 3'and CIF -.AsF) involved redox reactions producing Cl2 and

'lF2As 6.

Severai piossible synthetic routes to the uncharacterized

ebloroayl l,'uoride (FUlG) were investigated. These encom-

passed reduction reactions of Florox using N F4 and Cl2 and

the oxidation of Cl 0 with the mild fluorinating agent2

CF (OF). Trace quantities of Compound C.~ ece to be

FClO, were occasionally detected.

Various aspects of the chemistry of C1-0 species have been

examined. Syntheses of Cl 0 3were conducted under static

and flow conditions. Study of the new class of complexes

of the MF-Cl 0 type has been expanded to include the systems

FRbF-C1 2 0, CsF-C10 an CsF-CO.fan Cs-Cl The vi-

orous fluorination of C10,) proceeded explosively to CIF,

Cl, and

Hydrolysis of KF-KClF 4resulted in the formation of a new

phase as shown by X-ray powder diffraction analysis which

is thought to be a KF-KClF 4 hydrate. Preparation of ClF 04 3

via oxygen-fluorine exchange reactions was unsuccessful.

(Confidential Abstract)

SJ

R-7149CONFIDENTIAL

!NFlDENTIAL a

""W I 4l;1K 3 T D• " a-- A fl!Vi %IO OF' NORTH AI [RICAN AVIATION INc

CONTrENT S

Foreword i

Abstract ... . . . vIntroduction .. .

Discussion ........... .................. ........ 3

Ultraviolet Activated Reactions. . ....... . . . 3. .

Corona Discharge Activation ........ . ...... ...... 13

CiF 0 Properties . . . . . .. . . ..3

Florox Chemistry .......... ............ ...... 19

Possible Synthesis of Chlorosyl Fluoride (FClO) . . . ..... 21

Iodine Fluorides and Oxyfluorides ........ ... .. ... 33

Preparation of BrNO. 3.......... 38.3

Fluorination of Bromine Nitrate ..................... 40

Chlorine Fluoride-Arsenic Fluoride Systems ............... 41

Alkali Metal Fluoride-ClO Complexes ..... ... ... 47

Miscellaneous Reactions ................ ... ... 48

Experimental. . . . . 51

Ultraviolet Irradiation 51

Corona Discharge Activation 52

Reaction of CIF 30 and IiNF 2 . .. .. .. .. .. .. .. .. .. .. .. .. 53

Reaction of CIF 30 and FCONT2 53

Preparation of IF ...................... . ..... 54

Preparation of IFO .............................. 524

Pyrolysis of IF 0 .......................... .... 55 75

References 7.......... ..... 27

Appendix A

A New Synthesis of Chlorine Nitrate ..................... A-1

Appendix B

A Redox Reaction of Dichlorine Oxide with Arsenic Pentafluoride:

£An Unusual Synthesis of CIO1AsF 6. . . . . . . ... .. .. B-1

R-7149 ix/x

CONFIDENTIAL

CMNFIDENTIAL =4- W X-W" "'W A 0 V , N RH 4 ME CANqh A!T 1 0 N~

TABLES

1. Extinction Coefficients . . . ..

2. Ultraviolet Activated IReactions. .. ......... 7

3. Mass Cracking Pattern of C1F0 ...... ........ 16

4. F1 9 NM.R. Data on ClF•0 . . . . . ........ 18

5. Reactions of Cl2 with CIF3 0 ... ...... ........ 22

6. Conductivity in the IF -CIF 30 System at 25 C ........... 25

7. X-ray Powder Data for KF-KCIF4 -H2 0 ................. 27

8. Mass Cracking Pattern of IF7 . .. .. .. .. .. .. . . . .. . 34

9. Mass Cracking Pattern of IFO ... . -......... .... . 34

10. Vapor Pressure of Cl2 0 Over RbF ............. .... 47

11. Vapor Pressure-Temperature Data for IFKO....... ... .. 54

R-7149 x/i

________CONFIDENTIAL

CONFIDENTIALSI , • A DIVISION OF NORTH AMEPiCAN AVIATION. INC I

N1R4MMUCTI ON

The effort reported herein reflects considerable activity in the area ofA

inorganic chemistry concerned with covalent fluorides. Particular empha-

sis has been placed on the reaction chemistry of interhalogen fluorides

and oxyhalogen fluorides. The chemistry of CIF 30 and IF.0 appeared to be

uniquely attractive with respect to reactions involving fluorination and/or

oxygenation. This was verified in the case of CIF 0 and the following dis-

cussion section reflects to some extent the unusual chemistry of this mate-

rial. Interest at Rocketdyne in IF 0 is focused on its potential utility

as an intermediate for preparing IF 3 02 and IF 0. These possibilities will32 3.

be discussed with respect to both reduction reactions and thermal decom-

position.

An intensive effort was conducted to utilize the coapounds FCl02 and FCIO3

as chemical intermediates for new oxidizers, The approach reflected in

this area involved the use of ultraviolet radiation for excitation. The

ultraviolet activation technique was successful to the extent that it re-

vealed FCO1 and FC1O to be intermediates for the preparation of CIF 0.2 3 3

The results in this area are presented in detail in the Discussion section

of this report.

In attemptina to reproduce reported results in synthesizina "ClOAsF," an

unusual rpdox reaction was uncovered inasmuch as the reaction of C1 20 and

AsF 5 yielded CIO 2AsF 6 . This led to a supposition fhat AF 5 mby catalyze

redox reactions in other chlorine (I) compounds; this was subsequently

demonstrated with ClF. The results will be discused in connection with

a variety of redox and complexing reactions involving CIO2 , AsF3 , ClF 0,3'

and AsF_.

R-7149

CONFIDENTIAL

CONFIDENTIALaI 9 B1*r nM11 "w M A DIJISION OF NONRH AMI4MRCAN AVIA!'ON INC

Additional spectral data were generated for the novel compound CIF 0. 1Previoun attempts to risolve Lhe F1 n.m.r. spectrum had always reAulted

in a complete collapse of the bond structures due to exchange initiated

by traces of HF. Vapor-phasc measurements resolved the problem and the

results will be discussed with particular emphasis on the techniques used

to obtain these conclusive data.

II

2 R-7149

CONFIDENTIAL

CONFIDENTIALS• 0 Z X4C lK = K''•i M• MI• A DIVI SION OF NORTH AMERICAN AVIATION I NC

DISCUISSION

ULTRAVIOLET ACTIVATED REACTIONS

The purpose of this study was twofold. First, new syntheses of CiF 0 were3

sought that utilized intermediates other than covalent hypochlorites. By

using an initiator (in this case radiant energy) there exists a possibil-

ity of realizing more favorable reaction rates as well as obviating the

use of either Cl 0 or CIONO The second aspect of this study involved2

the possibility of synthesizing new hdlogen fluoride species such as CIF3 02 ,

ClF 0, and BrF The use of suitable radiation at low temperatures appeared

to offer a number of attractive features in achieving the objectives.

Absorption Spectra

Prior to conducting reactions by ultraviolet excitation, the spectra of

proposed reactants and possible products which could not be found in the

literature were determined. With a knowledge of the spectra, it was thought

possible that selective activation of reactants might be achieved during

irradiation.

Absorption spectra have been obtained for CIF, CIF5, CIF 3 0, FC0 2 , FC0 3 ,

and BrF 5 (Fig. i) using a Cary Model 14 Recording Spectrophotometer.

Extinction coefficients are presented in Table 1. The data for CIF5 ex-

tend the results reported by Gatti (Ref. 1) to wavelengths shorter than

2640 angatroms. The wavelengths for the strongest absorptions for all

compounds except CIF were below 2300 angstroms with indications that even

stronger absorption occurred below 1900 angstroms.

R-7149 3

CONFIDENTIAL

CONFIETI'Zq~m ',mwmm a A DIVISION OF NORlTH A' !7ICAN AVIATION. INC

0.01

E 01001

E

C1-Fzw

U-IA.

0

0CI

M 0.00001 ______

0.00000, E___ -11900 2000 2200 2400 2600 2800 3000 3200

WAVELENGTH, ANGSTROMS

Figure 1. Ultraviolet Absorption Spectra for CiF, CIF.. CLF.0, POLO,,FCb.., anid BiTF. 3'

4 1R-7149

Com~)ETA

CONFIDENTIALSIg]O===Tir",srm= A OIVIlION OF NORTH AMERICAN AVIATION, INC.

TABLE 1 1EXTINCTION COEFFICIENTS

Absorbance

Wavelength, Coefficient x 10-2,-1 -

Compound angstroms mm Hg cm

COF 2730 0.020 (Ref. 6)

Clf 5 2000 to 2100 1.1

CiF 0 2205 2.83

FC10 2 2225 6.02A

FCO 3 1860* 0.0903A

BrF5 2080 2.0

F 2 2845 0.035 (Ref. 4)

C.- 3 2231* 1.34 (Ref. 7)

OF2 2100* 0.075 (Ref. 5)

2

*Not a maxiwum; coefficient increasing toward

shorter wavelengths

R.-7149 5

CONFIDENTIAL .

CONFIDENTIALEP RO_. 1" D *rZ A DIVISION OF NQRTr AMERICAN AVIATION INC

Rpsctions

Reactions were investigated using CIF 3 0, FCIO2 , FCPO3 , and BrF1 as the

materials to be fluorinated. The mterials employed as sources of active

fluorine were F2 , CIF, ClF 3, ClF5, OF2 , and BrF5. Initial work was accom-

plished (Ref. 2) in irradiation cells with ielatively small windows (17-

millimeter-diameter openings). Because conversions in these cells were

small, even with overnight irradiations, a new cell with 4-inch-diameter

windows was built with which a large degree of conversion was nearly al-

ways obtained, Exposures were usually approximately 4 hours. Results

for the actual reactant combinations and conditions are presented in Table

2. A Pyrex filter was sometimes used to restrict the applied radiation

to wavelengths essentially longer than 3100 angstroms.

CIF3O/F2. Irradiation of CF 3 D0/F2 mixtures was conducted in an attempt to

prepare CIF 0. It was expected that the reaction might proceed by the5.

activation of F which would, in turn, react with CIF 0 forming CIF_0.2 3The small amounts of products obtained (Table 2), when the Pyrex filter

was used in an attempt to minimize CIF 0 activacion while maximizing F23

activation, suggest that the reaction probably does not proceed by a mech-

anism involving activated fluorine. The large yield of CIF. obtained when

the filter was not used indicates the probability that the CIF 30 was de-

composed by the radiation and that the reaction may have proceeded by a

route such as follows:

UVClF 0 - ClFF* (1)

3 3

C3F 0* CF* + 0 (2)

R-7149

CONFIDENTIAL

*CONFIDENTIAL

A I I I N O O T kN~C N A IT O N

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CONFIDENTIALa * A c2 V SION OF NORTH AMERICAN AVIATION INC

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R-7149

CONFIDENTIAL

CONFIDENTIAL IM9XC WW " M A DII IN OF" NORTH AMERICAN AVIATION INC

ClF 0 - ClF +(03)

ClF F ClF.. (4)3 2

Low temperatures (-40 C) were used for this reaction to determine if the

activation of CIF 3 0 might occur without its decomposition. It is possible

that the use of even lower temperatures during ultraviolet radiation would

cause the reaction to proceed in the following manner:

CIF3 0 ClF~o (03 3

CIF 30* + F2 - ClFO (6)

Unfortunately, the rather low vapor pressure of CIF 0 (less than 10 milli-3

meters at -60 C) would permi 'he formation at any one time of only small

quantities of the proposed compound, C1F_0. Because CXF-0 could be more3 71

volatile than ClF 0 and would, therefore, -emain in the vapor state, rapid

decomposition by iltraviolet radiation to CIF- and 02 would be expected.2

Therefore, the possibility of forming ClF.0 by reducing the temperature .2

below -40 C appears unlikely.

Reactions of FC02 Initial irradiations of FC10 at 25 C both alone and2'

with F (Ref. 2) indicated that partial decomposition of FCl 0 to CIF and2 1

02 occurred accompanied by fluorination to CIF andor CIF.. Because the2 3

objective of this work was the preparation of C1F 3 02 , the reactions were.

repeated at reduced temperatures where this compound shouldý be more stable.

No experimental evidence for the formation of CIF 3 02 was found. However,

substantial yields (up to 86 mole percent) of ClF 0 were obtained from3

R-7,1149 9

CONFIDENTIAL

CONFIDONTIALSRO ~ k' TD V'N • A DIVINION Oil NORTH A t Ir IC AN AVIATION 1 .4

irradiations of Cl02F with most fluorinating agents used (Table 2). These

experiments represent the first examples in which C1F 0 (Florox) has been

prepared in good yield from an intermediate other than a covalent hypo-

chlorite.

Chloryl fluoride is a stronger absorber than any of the materials used to

fluorinate it and its activation is considered to be the initial step in

the reactions. The proposed mechanism for the overall reaction (Eq. 7

through 10) involves the generation and subsequent fluorination of FC1O.

FClO .- --- EC10. (7)2 2

FCO 2* [FCl 0] + 0 (8)

22EClO2 +0 •- - •l]+ (9)--

[FCno] + F2 - ClF3 0 (I1)

The detection of a compound thought to be FCl0 (Ref. 3) during the ClF/

FC102 experiment tends to support the existence of FCl0 as an intermediate.

This compound may have also formed during the irradiation of FC10 2 (Table

2). The supposed FCl0 is known to be very reactive and relatively unstable

(Ref. 3) and the failure to observe it more frequently was not unexpected.

A flow experiment was conducted in an attempt to prepare FCl0; however,

neither FC1O nor CIF 0 was found.3

As at room temp-rature, the -60 C ultraviolet irradiation of FCIO0 alone

produced principally CIF and 02, but the efficiency of the lower tempera-

ture was demonstrated by the farmation of some CIF 0. Either FC10 itself

or the product CIF may have served as the active fluorinating a2ent.

10 R-7149

CONFIDENTIAL

CONFIDENTIAL, A DIV SION OF NORTH AMYLR!CAN AVIAIION INC

S@

The weaker group of ultraviolet absorbers (Table 1; F,,, OF,, and CIF) re-

suited in 20 to 30 percent conversion of FC10 to ClF 0 under approximately23

similar conditions. Of these, elemental fluorine yielded the best conver-

sions to Florox and unlike any other fluorine source also formed CiF.. Of

the three fluorinating agents in the group, only F2 was examined at F.jFCl02

ratios higher than two. These higher ratios were found to yield lesser

amounts of CIF 0 and more CIF,.. No satisfactory explanation of this re-3

suit can be made at this time because the presence of a large excess of

F would a priori lead to a predicted higher yield. Further, the limited2

number of exj iments and the lack of replicate runs preclude sufficient

evidence for advancing final conclusions. The low absorbtivity of Fo rela-

tive to FC102 (Table 1 and Fig. 1) eliminates the possibility that the F2

may be preferentially absorbing the available radiation.

The conversion of FC10 2 to CIF 0 using the strong absorbers CIF., CIFs,a2 3 :

Sand BrF. appears to be limited by the amount of the fluorinating agent in

the vapor phase and therefore capable of activation, Thus, ClF is more

effective than CiF while BrF_, which has only several millimeters vapor3D

pressure at the test temperature, did not produce any. ClF. despite the

fact that it reacted. The significance of ultraviolet activation of the

fluorine donor may be indicated by the fact that CiF- is a much better

fluorine donor than F2 itself. However, the greater efficacy of CIF.. may

be due to its ]oa'er activation requirements and chemical reactivity, This

consideration, coupled with the vapor concentration of the agent, may be an

important feature. In the latter interpretation, the role of the ultra-

violet radiation would be primarily involved in decomposing FC10o.

FC1O /C1F.. Following the encouraging results with FClOo,, an examination

of similar reactions with FCIO was initiated. Perchlor-l fluoride was,3

considered as a precursor to ClF 0 because its decomposition to an acti.-3 2

vated FC1O 2 capable of fluorination seemed possible. Although FCIO.ý

R-7149 11

CONFIDENTIAL- - -

- I!CONFIDENTIAL C

absorbs only weakly where other ClF compounds absorb gtrongly (Fig. 1),

reasonable radiation times did effect its decomposition. Both CIF and

some FCIO were formed. The latter is important because it demonstrates2

that the desired Cl0 bond cleavage does occu"., :Arge quantities could

not be expected because the strong absorptivity of FC0 2 results in its

own decomposition.

Fluorination of the activated FC10 was attempted with ClF. because of its3

proven effectiveness with FCIO 2 No unknown products were observed but it

was determined that CIF.0 was the major product. This is almost certainly

due to stepwise loss of oxygen from F10 to yield FC1O which is then3

fluorinated to CIF 0.

Thus, both FC10 2 and FC10 3 appear to undergo the progressive loss of oxygen

on ultraviolet irradiation. Once chlorosyl fluoride, FCl0, is formed, it

is sufficiently stable at -40 to -60 C to allow fluorination to ClF 0.3.

Florox is the most complex product obtained due to the fact that, it is

essentially frozen out and thus not subject to any extensive ultraviolet

activated reaction or decomposition. If CIF302 is to be synthesized,

activation of F2 without the activation of FC1O0 must be accomplished.

The use of filtered (more than 3100 angstroms) radiation appears to be

the most probable means of preventing extensive FCIO activatio,. While

this approach was attempted for the synthesis of C1F_.O from CIF~O and F),

it has not yet been utilized for the attempted preparation of 3 .0£.

BrF-/F2. It was thought possible that BrF7 might be formed by activation

of BrF. in the presence of F2 (Eq. 11 and 12).92

BrF - BrL.* (11)

BrF* + F2 BrF 7 (12)

12 R-7149

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CONFIDENTIALXR 014I j wEirik r w A DIV iSON OF NOWTH AMEN CA N AVIATION IN C

O:er5:onbelw;mbent:FtemerauesEwaempoye to woaximize the probotbil..

F.. urter, lage xces ofF -As aso sedto increase the chanices

Infrared analysis of the products from the irradiations conducted at -40

and -60 C indicated that no new products were formed. However, several

unidentified absorptions, probably caused by traces of impurities, were

found in the infrared spectra of the products obtained from most experiments. 0Observed absorptions were at .1028, 1220, l2j0, 1280, 1315, and 1910 cm

CORONA DISCIURGE ACTIVATION

Previous experiments on the corona-activated reaction of FClO with a large(Ref a)hadsuggste tht te prducs o th

excess of F2 (e.8 a ugse ta h rdcso h reaction wereprimiarily CIF and FC1O rather than the desired CIF 0 However, leaks in

3 32the reaction systeh have since been fowid which indicate the possibility

that the FC10. originated in a manner other than the disproportionation of-J

FC10 Therefore) the experiment -was repeated.2'

During one expcriment, the amount of FC102 which passed through the dis-

charge yielded the following product distribution: CIF. 3i m/o; ClF,

3 M~; CF9 0 m.'o FC 070. ni'o; FClO2 (unreacted), 37 m'/o; and SiFk

2.6 rn/a. The SiFk apparently resulted from reaction of the F with a4 2

Pyrex flowineter.

The rather good chlorine material balance (more then 85 percent) permits

a course of decomposition of FC10 to be postulated. First, the presence2

of only a trace amount of FC1O 3precludes a substantial disproporticnation

CONFIDENTIAL 1

CONFIDN ALm I =-ca•c-NIa ST r" 03 A ODIVIGION OF NORTH AMCRICAN AVtATION INC

of FC10 Therefore, the most probable route for the reaction involves ]the decomposition of ?0C0 am shown in the following mechanisms:

2

Corona Discharge .1+02 2

F+ F2 Corona Discharge C

CIF3 4 F2 Corona Discharge CIF

Thus, it appears that corona activation of FClO causes decomposition2

rather than providing a reactive excited species capable of being fluor-

inated to CIF 02o

CiF 0 PROPERTIES3

Mass Spectrum

Previous attempts to obtain a fragmentation pattern of CIF 30 were unsuc-

cessful (Ref. 9). At that time, it was suspected that the extremely cor-

rosive chemical was not reaching the isotron in the CEC 21-103C Mass

Spectrometer. This problem was compounded because only small quantities

of Florox were zhen available.

I- is most desirable to obtain one measurement that in itself leads to an

u, biguous identification. The availability of larger quantities of Florox

couple4 with a modification of the inlet system to the previously mentioned

mass spectrometer enabled this to be achieved. The difference in corrosiv-

ity between CU?3 0 and ClF5 toward the micromanometer is demonstrated by the

14 R-7149

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CONFIDENTIALA DIVISION OF NORTH AMIEMICAN AVIATION INC

fact that stable patterns could be obtained for CUF while C1FO couipietely

decomposed in the inlet system. Elimination of both the micromanometer and

a 3-liter expansion volume made it possible to obtain a stable mass crack-

ing pattern reproducibly, using an ionizing current of 10.5 microamoeres

and an ionizing voltage of 70 electron volts. The composite apectrogram

obtained is presented in Table 3.

The spectral pattern in Table 3 is normalized to the most intense peak ob-

tained at high mass range using a magnet current of 0.60 ampere. The spec-

trum of C1F3 0 was corrected for the following impurities: SIF4 , YC10 3,

SC ,and. HF. It was apparenit, from several patterns,

that little variation in relative intensity was observed for the key masev/

charge pattern ratios corresponding to ClFO+ and CIF 0 +, ome variation4-2was noted in the calculated intensity of the C1O peak after correcting

for Cl-0 containing impurities. Further refinement in the determination

of this value is dependent on a more accurate accounting of impurity con-

tributions to this peak.

F1 9 n.m.r. Study of Florox

The F 1 9 n.mr. spectrum of the gas phase of CIF 0 was obtained to substan-3

tiate the proposed C symmetry. A Varian DP60 spectrometer was used which

was equipped with a high-resolution 56 M.z radio-frequency unit and high-

resolution magnet. To detect the weak signals from the gaseous sample, a

Princeton Applied Research lock-in-amplifier was used operating at 1.5 Hz

to allow observation of any possible fine structure in the spectrum. The

samples were the gas phases in equilibrium with the liquid phases of two

purified ClF30 samples containing different amounts of HB, and a gas-phase

sample which had no liquid present. To observe the gas-ph:,se resonances

of the liquid samples, the n.m.r. probe was inverted and Lhe sample main-

tained in place with a piece o? tape. Calibration was effected with a

R-7149 15

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CONFIDENTIALT * A tIVt1ON Cr N O H A M tM I C A AV I A T ION IN C

TABLE 3

MkSS CRACKING PATTERN OF C^IVO

Mass/Charge Relative Intensit3, percent Ion

16 13.19

19 27.29

35 29.35 Il3

37 7.58 Cl,

51 1 .7(8 C10O

53 •4.32 CIOj

54 21.23 CIF

7.10 CIFI

70 100.CO C iFO

72 32.05 CMFO

89 8o .6(1 C I ,0 -

91 26.22 CIF2O0

108 -

110

NOTE: The sensitivity factor was not calculated becauseno accurate pressure measurement was made

16 R-7149

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sample of CC1F contained in a capillary tube; surface tension held the3

liquid up in the top of the tube in the inverted probe. Sidebands at

W. 9600 Hz generated from an auxiliary low-frequency oscillator, were usedfor magnetic field sweep calibration. The results are presented in Table 4..

Some of the features in the n.m.r. spectra of both gas and liquid are

noteworthy. The sample containing only a gas phase revealed two different

spectra. The initial spectrum showed F 1 9 peaks at -223, -262, and -300 (0,

Upon aging for 2 days, the -223 ppm band disappeared. Subsequent gas-

phase measurements on samples containing liquids revealed two peaks at

-276 and -317 0. The first measurements were less precise than the latter

because they involved the use of a much lower side-band frequency (1200 vs

9600 Hz for the others). Thus, the -262 and -300 0 bands are the subsequently

observed bands at -276 and -317 0.

No assignment is readily available for the -223 4 (actually -24,7 0). It

could possibly be assigned to the high field band of ClF. However, its

disappearance, as well as the absence of splitting, make this unlikely.

(There is a remote possibility that C n• 'may "disappear" through disolution

into the Kel-F tube walls). Another possibility, however remote, is the

presence of an isomeric species.

1he liquid spectra revealed only one line and are unremarkable except for

the fact that the chemical shift is consistent with the measured HF con-

centration. The complete collapse of the doublet in the liquid phase,

caused by the exchange initiated by the low HF content, may preclude the

resolution of liquid spectra. Additicnal SLudies will be conducted with

samples containing alkali fluoride salts in anticipation that their bi-

fluorides are completely insoluble in the Florox sample.

R-7149 17

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CONFIDENTIALElk •. O! 9 A DIVISION OF NOR'TM AltAIERCAN AVIATION INC

TABLE 4

F19 N.M.R. DATA ON CIF 0(a)3

' ~~~~HF(b) F19Chicl Pk

Sample Phase in F Chemical PeakDescrptin Probe Concentration Shifts, 1 Intensit.Proeptnenraio

Gas I G.s -223 ' 0

-262 2, -300 1

Gas(c) Gas -- - 2 6 2(d)

-300

Liquid Gas Gas -- -276 2

-3171

Liquid + Gas Liquid 0.015 Molar -276 --

Liquid + Gas Liquid M0.000 Molar -289

(a)All spectra taken at ambient temperature(b)Measured by proton n.m.r.

(2)Same as preceding sample, only 2 days "older"

Side-band frequency of 1200 Hz used

18 R-7149

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Specific Conductivity of C1p 3 0

The specific conductivity of CIP 0 at 25 C has been measured at Rocketdyne

and a preliminary value of 2 x 10 ohms cm has been determined. The

apparatus used was that described in Ref. 10.

FLOROX CHEMISTRY

Reaction of CiF 0 With NPF2 Compounds (A New Synthesis of f T0)

Studies of the reactions of chlorine fluorides and difluoramine have been

shown to proceed as follows (Ref. 9):

CIF + (2x + 1)HNF -C--- C1N (2x)NXF,, F (2x + l)HF

2x 1 2 22

where

x = 0,11 or 2

The course of these reactions appears to involve reduction of the CIFx

moiety to CIF followed by condensation to yield ClNF 2. Because Florox is

similar to the chlorine fluorides chemically, it was proposed that a simi-

lar reaction sequence might occur. However, after the reduction of ClF 03

to FC10, a condensation with •nT2 might yield OCINT2 :

CIF 0 + 2HNF2-. - 2lF + N2F + FC103 2 2 4

IF]FCIO + HNF 2 •- F + OC1NF 2 C1F 2 NO F3NO

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Accordingly, a 1:1 reaction of ClF 0 and HNoF was conducted at low pressure

and below 0 C. A smooth reaction foilowed, yielding no noncondensables.

No unreacted WF was observed and 55 percent of the CIF.0 was recovered.2

The N-F containing products consisted of equal proportions of ClN'F and

NF 0 and a small amount of X F3 24

Thus, the course of the reaction appeared as follows:

2WN ClFQ0 2P + W30 + Cl\-o2 3 3

Based on this equation, the yield of NF 0 and CINTF was 80 percent. The .a

3concomitant oxygenation and fluorination of an XF, group is intriguing

because of the possible reaction intermediates involved. It appears prob-

able that the final fluorination step involves Cl.NF 1 O, as in the precedingequation, or the ONT2 radical. The mild reaction conditions coupled with

2the high yield of NF 0 are unprecedented during all previous 3vntheses of'

3NF3 0

Several repetitions of this experiment. using higher IM-F2 to CF3 0 ratios

(2 to 2.7:1) yielded similar results, The reaction temperature was variedbetween -78 and -112 C. One of the experiments at -112 C yielded only 75

percent of the anticipated total of NoF', CINT0 , and N..0 when pumped on

at that temperature. The remaining \T materials were obtained only on-

warming above that temperature. This indicated that a ClF.0-IL 0 complex

may exist at the low temperature. An attempt to confirrm this on a scaledup reaction at -112 C was unsuccessful. This may have resulted from in-

sufficient cooling through the relatively thick walled Kel-F reactor. Theuse of a thinner wall Teflon or alumina container as well as a lower tem-

perature (-125 C) will constitute a final attempt at stabilizing any pos-

sible complex.

20 R-7149

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CONFIDENTIAL.o mr 1Tri '"w mI A OIVISION OF NORT64 AMCrftCAN AVIATION. INC

The possible general reaction of CIF 0 with NF compounds to yield NF 0

was also considered. To test this possibility, a reaction with perfluoro-

formamide, FCONF2 , was performed. The products were NF3 0, CINF 2 , N2F4,

and C0F Assuming a stoichiometry as follows:

CIF 30 + 2FCONF2 - - 2COF2 4- NF 30 + ClN 2

32

the NF3 0 yield was 21 percent. Although this yield is somewhat low, it

does confirm the utility of ClF 0 as a versatile oxygenating and fluori-3nating agent.

POSSIBLE SYNTHESIS OF CHLOROSYL FLUORIDE (FC1O)

An unidentified compound, referred to as Compound C, has been observed on

a number of occasions (Ref. 3). Infrared evidence is consistent with the

proposed chlorosyl fluoride (FCl0) as well as reaction enviroiunents from

which it is obtained. However, this material is elusive in that all pre-

parative methods have thus far been irreproducible. The pursuit of this

material, while not an all encompassing end in itself, offered the pos-

sibility of exploring a wide variety of reactions of ClF C as well as

other halogen fluorides.

Reduction Reactions of CIF3 0

One reducing agent that appeared to be of interest in exploring the reduc-

tion of CiF 0 was N2F . It has already been shown that ClF. undergoes3 2 4'smooth reduction to ClF as in the following equation (Ref. 11).

3

CIF + N2 F4 - CIF 3 + 2NF3

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The obvious analogy, then, is the oxidation of N F, with Florox:24

CIF0 + NF . -- FCO + 2NF3 2 4 3

Tetrafluorohydrazine and ClF 3 0 do not react at ambient temperature. To

produce appreciable reaction, tests were conducted at 100 C. Even at 100 C

over a 24-hour period, 85 percent of the CiF 0 was recovered unchanged. A

trace of Compound C was found among the products which also included NFV,and unreacted N P . At 130 C and after 65 hours, the CIF O-N2F, reaction

produced FN0, FNO2 , NF3 0, NY, and CiF. No Compound C was formed and 46

percent of the CiF 0 was recovered.3

The reduction of CIF 0 with Cl was re-examined in the hope that the3 2

following reaction could be observed:

?C1F30 + C1 -- FC10 + 2ClF3 2

During previous experiments (Ref. 3) no reaction of Cio was observed at

ambient temperature with either CIF 30 or its CsF complex. The results of

a series of experiments at elevated temperatures are presented in Table 5.

TABLE 3

REACTIONS OF Cl2 WITH CIF 30

Temperature, C Time, hours t-CiF 0 Reacted Products

71 120 i 27 FC10 2 CIF 32 3

100 42 37 FC102, CIF 3

150 i 21 25 Trace C, FC1OI,CIF 3

"200 16 100 .ClF, 0- - 2

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During the one run at 150 C, a trace of Compound C was produced, but no

other run produced evidence for this elusive species. At or below 150 C,

FC10 2 and CIF. were produced from partial reaction of C1F 0; while at2

200 C, the CiF 0 reacted completely with Cl2 to produce CIF as in:32

Cl + CIF0 -3C1F + 1/2 022 32

Attempted Syrnthesis of Florox

Oxygen-fluorine exchange reactions as possible routes to orvchlorine flu-

orides were studied using the reaction systems FIO -CIF. and 1205-C1F_.2 5

The desired reactions were:

2ClF + F•o 2CIF0 + IF5 2 3 5

5C1F5 + 10 5CIF0 + 21F.5 2 5 3 5

These exchanges were based on the known reaction of Fl0 2 (Ref. 12):

2SeF + FIo - 2SeOF2 + IFLi 2 2

No CIF 0 was observed as a product in either reaction. The reaction be-3

tween CIF5 and KO02 produced FClo2 and lesser amounts of FClO . With

I105 and CIF_, primarily FCIO with smaller amounts of ClO resulted.25 2

Mixed Interhalogens

Complex interhalogen fluorides based on CIF 30 would form an interesting

type o2 compound, therefore, the acid-base equilibria of ClF 30 (a moderately

33.• ~~~~strong base) with the strong acids, Br3adIFhaebnstdd. oh

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systems were miscible, vielding clear sol..t.on with extended l-quidus

ranges. However, vapor pressure measurements revealed that the solutions

were nonideal, Conductivity measurements were then used to asseas the

extent of any possible ionization.

In the BrF -CIF 0 system, the addition of 4l mole percent ClF.O to BrF_3 3)

increased the resistance of the solvent slightly. On this basis, it was

concluded that the self-ionization of BrF is unaffected, and the resis-3

tance increase is caused by the addition of the less conductive ClFO.

Thus, the following equation does not appear to be operative:

CF 0 +BrF - CIFO+ + BrF43 +r3

Elucidation of the IF -CIF 0 system was complicated by difficulty in puri-5 3

fying and transferring the IF.. Several measurements were made and are

shown in Table 6. The widely differing values for the initial resistance

of IF 5 apparently indicate the material was impure. In each case, the

addition of C1F 0 resulted in a lowering of the resistance of the IF_.3

However, it was not quantitatively reproducible and certainly does not

suggest ionization of the C1F.0. In addition, removal o1' the CIF-O did

not raise the resistance of the IF.

It is therefore apparent that lowering of the resistance of' the IF- was

caused by impurity addition and that the following equilibrium exists

slightly, if at all:

ClF 0 IF_ . CIF20 +IF63 2 * 6

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TABIE 6

CONDUCTIVITY IN THE IF -CIF 0 SYSTIM AT 25 C A5- 3

IF Resistance, Rtesistsnce After Floroxohms Addition, ohms

76 44

59 55

173 120

293 236

Hydrolysis of MCIF 4

Another possible route examined for the preparation of FCIO involved con-

trolled hydrolysis of anionic interhalogen fluoride specieF. The systems

studied were KC1F -H2 0 and CsClF -H20. The desired react.i%,,s %;ere:

MC1F + 120- -- MC1F 0 21Ff

with possible displacements as in:

MCF 20 + 1fF - 2 -•FC10

Static reactions have been run where H 20 was added both to CsC1F 4 and

KClF 4 In addition, a flow reaction was run where H 20 saturcted N was

passed through CsClF4 at ambient temperature. In the flow run, large

amounts ol ClO and Cl were generated.2 2

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Results on the static systems wkre variable. Approximately three to five

molar equivalents of water were added to three KCIFJ samples. Upon pumping,

unreacted water and approximately 6, 18, and !,5 percent of the original

tetrafluorochlorate chlorine were evolved Ps volatile chlorine containing

species. Similarly, with three CsCIF4 samples 2, 75, a:ld 85 percent of

the original tetrafluorochlorate was evolved. TVe volatiles were princi-

pally elemental chlorine with smaller amounts of CIO, in two cases, and

FC10 in one, The variation in evolved chlorine may be caused by thetechnique of water addition. If the water reacts slowly and smoothly,

hydrates are -probably formed. However, if the reaction is rapid, hot

spots might develop which could cause violent reaction and yield elemental

chlorine as a product.

Subsequent reaction of three of thc residual solids with excvqs I1F yielded

H20. Thus, it appears probable that stable hydrates were forined, Becausethe hydrolytic reactions of the CIF ion, in general, proved to be com-

plex and vigorous, the study in this area has been limited io examining

the postulate of the formation of stable hydrates. Reference samples for

KF-KCIF and KF-H 2 0 were prepared and their X-ray powder patterns were ob-

tained. Although the patterns were complex, comparison of the KF-KClF,-120

data listed in Table 7 with KF-KCIFP and KF-H 0 reference patternis revealed

that another phase ias present. Comparison of ASTM re'eference patterns for

UF'2H02 , KH2, KC10 2 , KC1O 3 , KC10, K02 , and KO. has also revealed that

these compounds do not account for the unreforenced lines. Thi: X-rav

evidence for a new phase and the chemical observation that the KF-KCIF,

mixture hydrolyzed only slightly with water indicated the high probability

of the formation of hydrate(s) of the type KClF .xl 0. Halocarbon mulls

of the solid product on two occasions showed only the halocarbon peaks in

the infrared and no OH stretching vibrations were observed.

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X-RAY POWiDER~ DATA, ?OR KF-KClF h-H 0

Observed Diffraction, -

angsntroms Relative Intensityr

5.1 3

4.9 3

4.6 3

4,45 3

4.2 3

3.16 40

3.o6 100*

2,78 30

2.58 10

2.41 10*

2.33 30

2.24 8

2.08 60*

2.04 10

2.00 5

1.82 5

1,75 5

1.70 10*

1,65 10

1.61 3

1.58 3

1.45 20*

1.42 10

1.34 5

1.32 10*

1.20 5

1.13 3

*Peaks of intensity 10 or greater which cannot be referenced

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Hydrolysis of UIF7

The reaction of uncomplexed CIP was examined with 11H0 to test the hypoth-32

eses that a condensation would evolve an follows:

ciF + 110 - FCIO + 2HF

The first reaction, using excess CIF at ambient temperature, yielded traceamounts of Compound C and CiF. Four additional runs, however, conducted

both at ambient temperature and at -18 C produced only Cl2, CI02, CIF, and -FC202 .

Chlorine Sesquioxide

A paper (Ref. 13) entitled "Chlorine (i1i) Oxide, a New Chlorine Oxide"was recently published. The tentatively identified material, Cl 0 was

2 3formed by the ultraviolet irradiation of CIO,) in a Pyrex bulb with a cold

finger held at -45 C. The stoichiometry reported was:

30 102 4 C01206 + 6C1 203 + 902 + 5c12

Because of the postulated structure, i.e., a catenated chlorine compound,

the utility of Cl2 03 as an intermediate in several areas of research -as

of interest.

The reported synthetic technique was used and produced trace amounts of

the nr-" species formed as a brown solid ring at the neck of the -45 C cold

bath "owever, only extremely small amounts of the material were produced

by thi.a method. rMcd1ale and Von Elbe (Ref. 13) produced approximately 0.2

mmole (0.024 gram) in their rune.] Attempts to increase the quantity of

38 R-7149CONFIDENTIAL

CONFIDENTIAlA DIVISION OP NORTH AMERICAN AVIATION INC

FR

product involved raising the quantity of CIO irradiated, lowering the

reaction temperature, using a KeI-F reactor, and use of flow systems. An

F attempt to increase the quantity of product by irradiating approximately

fR I milliliter of C10 2 resulteL in a violent explosion.*

*CAUTIONARY NOTE: In this attempted preparation, approximately1 liquid milliliter of chlorine dioxide, contaiLed in a 250-ccPyrex reaction vessel, was slowly warmed from -196 to -45 Cwhere it has a reported vapor pressure of 37 millimeters. Theultraviolet lamp was then turned on. After approximately 5minutes, the C10 2 exploded with sulficient force to shatterthe 1/4-inch Plexiglas safety shield surrounding it at a dis-tance of 1 foot. In later preparations, much smaller qu•antitiesof ClO were used.

2

Employing a lower reaction temperature (-64 C) than that of McHale and von

Elbe (-45 C) led to more reproducible results. However, the amounts of

Cl203 formed remained small. In a typical experiment at -64 C, irrcdia-

tion of 3.3 mmoles of C1 2 produced 1.34 mmoles of ClI. Thus, less than220 percent of the starting C10 2 was converted to solid chlorine-containing

species, and the yield of C1203 was less than 0.31 mmole. Attempts to

sublime the brown solid even very short distances resulted in its decom-

position.

To raise product output and still maintain a low concentration of the

treacherous CIO2 , the preparation was converted from a static system to

a recirculating flow system. Passage of Cl2 through NaCl0. produces ClO2.

Thus, Cl2 could be continually fed into the system and passed through NaC10 2

producing ClO w2hich is then irradiated. Unreacted ClO2 and Cl2 would be

recirculated at low pressure through the NaCIO 2 and irradiation areas.

Oxygen produced could be removed by an occasional bleedoff. With only a

low pressure of CIO in the system, it should be possible to prepare mod-2

erate amounts of C1 0 Sevcral runs were made using the recirculating2 3'

system, however, in only one case was any material produced, and continued

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reaction caused it to decompose, Keeping sufficient ClO,, in the irradiated

volume was the apparent problem. This was, in turn, dependent on the rate

of formation of C10 and the efficiency of pumping. Because of the lack2

of success, the recirculating system was abandoned,

Chemical reaction of Cl 0 was attempted by allowing it to react uith CsF.

This would occur by either of the following routes:

CSF + Cl 0 - CsOCl + FC1022 3

CsF +C1 2 03 -0 CsClO2 IClO---

Formation of Cl 0 in a reaction vessel containing CsF ias .ucressful.9 3While no reaction was observed with CaF, this may have been caused by

failure to achieve a suitable contact between the solid reactant.-:.I

To provide a medium for reaction and to allow possible transfer from the

glass system, an attempt was made to dissolve the matprial in CFC15; how,-

ever, little, if any, solubility was observed in the CFCl. Because of

this solubility problem, difficulties in handling CIOo,, and die ttificmtlty

in preparing even trace quantities of ih,, niw material. i v'esi , t i oi ()I

Cl 0 was terminated.2 3

Oxidation of C12 0 With CF2 (01F) 2

Mild fluorinations of Cl 0 or other appropriate ClO species offer an addi-2`4

tional route to chlorosyl fluoride. Previous experiments in this mode

utilized fluorine with excess C12 0 (Ref. 3). Complexes and low tempera-

tures were thought to be conducive to moderatina the reaction such that a

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chlorine (III) compound would resulL. Results with F revealed, however,2

that once reaction was initiated, oxidation was complete to CIF 0. This

strongly implied that the molecule CIOO was much more susceptible to oxi-

dation than Cl 20.

Rather than using F2 as the fluorinating agent, the use of CF,(OF) 2 was

considered. Over a period of 15 days at Dry Ice temperature, CiO0 decom-

posed completely to Cl and 0 with a very small amount of FCIO formed.2 2 2

The CF2 (OF) 2 was recovered essentially unchanged.

Fluorination of Chlorine Dioxide

Because C102 has been observed in some reactions which produced small

"amounts of Compound C (FCIO?), it was thought that fluorination of C1O2

under certain reaction conditions mih produce FCIO accordi-i- t o:/ ')

CIO12 + 1/2 F2 C PIO + 1/2 02

Vigorous conditions would, however, be required because mild conditions

produced FCI 2 (Ref. 14).23

Separate experiments with an excess of either F. or CIO. resulted in rapid

reactions. In these experiments, CIO2 and F were placed in separate 300-2 2

milliliter, stainless-steel bombs and allowed to mix rapidly by a simple

turn of a valve. In each case, a clang gimilar to hitting the bombs to-

gether occurred upon mixing, indicating rapid explosive reaction. In the

run at ambient temperature with excess fluorine, the products found were

CIF and FCIO2 in a ratio of approximately 5:1. Thus, the reactions ob-

served were:

C10 2 + 3/2 F2 - CIF3 + 02 (major reaction)

C10 2 + 1//2 F2 - FCIO2

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With exces3 ClO10 an experiment at ambient temperature yielded only ele-

mental Cl (> 90-percent yield) as a product. Another experiment at 0 C2

produced Cl 2 (> 90-percent yield) and approximately 2-percent FC1O Underthe condition employed, the principal net reaction was cxplosive decomposi-

tion of C10 2 :

CiO explosion 1,/2 C1 + 02 2 2

' ItI

32 R-7149

____ CONFIDENTIAL _

CONI'MENTIAL__ EkI I "• ]l l A OIVISION OF NONTH AMERICAN AVIATIOp INC

£uDINE 1FLUORIDES AND OXYFLUORIDES

Iodine dioxide trifluoride, 1F 3 0 2 , represents an tn"c.oum composition forhalogen oxyfluorides. A limited effort was conducted to synthesize thiscompound as a complement tu the concurrent elfort to prepare Cl' 0.). Theknoun compound, IF 0, offered a convenient starting liaterial, Samples ofIF were first prepared from IF and F The IF- was converted to IF-0as follows (Ref. 15):

21F. + SiO0 -. 21F.0 + SiP

Significant discrepancies were noted betw'en the reported vapor pressuresof these compounds and the observed values. ihe 2:.eaýsared Va I 's for I.1_were approximately twice those reported, despite the i'act that tie only

(9 detectable impurity, IF.0, %us present only in trace ilia'titiec An exactdetermination of the vapor pressure was not riad, h,:tt tile alvl'itl eisn •o nl-

verted to IF_0. Following initial vacuu. fraction,a-ition final trace±s ofSir2 and HW were removed from the IFO by treatt!uenii ý,'ith lIa. Analysis of)

this material by near infrared spectroscopy revealed ls.4 thain 0.7 !!1 o 11F.The sample was tensionetrical ly homogencous, tie inf'a'vdl ojiecttlj:] r ,-.s itsreported (Rief. 16). and the vapor density yielded a Xfl tc(tlai wuiJi. of'246 g/mole (23B calculated). The corrected vapor' ,'('MlIre-,,'l:li~erat ,'eequation for IF.d0 is log P 8.987), - il63O.' IeI i Tfa -;!!)L1r.;uat i onis 7.59 kcal/rmole and a sublimation pressure of 76(0 !:c is oi)LLajtiled at i.', C.

Additional information concerning both IF- and IF:o %,was obtained. iii par-ticular, the previously unreported mass craclking patterrns ,ere deter::ined.The inlet system of the ,ass spectrometer was altered as described earlier(Ref. 17) and the sane operating conditions were e::ployed. The mas. spec-trum of IF5 was first determined as a comparative reference (lIef. 18).

Reproducible spectra were obtained for both IlF- and 11"_0 and are shown in

Tables 8 and 9.

R-7149 33

CONFIDENTIAL

CONFIDENTIALUK ~ *A O:i.NOF N.CRTý A..Ell CAN A\ A' N

FL SS CPACKING PATTERN OF IF-

Relative Intensity,

Mass Charge • percent Ion

260 No parent IF-+

241 73,68 I F'-+o'2219,31, I F-

203 100.00 IF 4

184 7.50 IF _++

165 6.4 ItIF,+

146 35.13) 1'F

127 50.26 IA

TABLE 9

MASS CI{CKING PATTFRN OF IFO

-Relative Intensity,Kass,/Charge percent Ion

238 32.05 IF-o+

222 2.60 It-I

219 17.4 0 I 0,,

203 i00.00 ii,

200 1j4.38 IF-0

1811 21.92 I-U+)+

181 17.95 IF,)O

165 10. l'i

162 28.77 lE-O+

* 143 12.19 10+

127 48.25 [

34 R-71'i9

CONFIDENTIAL

CONFIDENTIAL" " , A DIVISION OF NORTH AMERICAN AVIA'ION I NC

,IIIn the case of IF and IF 0, parent ions were observed. Previous work

5 5with chlorine fluorides with this instrumentation never yielded parent

ions. Recombination reactions were not observed and therefore no IFxO2 ionfl

were observed. Only very minor quantities of impurities (Sip4 and COF 2 )

were found and these could not be confused with mass/charge values of

iodine-containing ions. The spectral patterns are normalized to the most

intense peak.

The attempts to prepare IF3 02 utilized the reaction of IF.0 and SiO

(either Cab-O-Sil or 80 mesh silica) at elevated temperature. Because

the formation of IF 0 from IF and SiO occurs readily at ambient tempera-5 7 2

ture, it appeared that additional oxygenation of the central iodine atom

might well occur under slightly more vigorous conditions:

21F 50 + Sio 2-- 21F 302 + SiF4

Reactions were conducted at 130 C (Cab-O-Sil) and 145 C (silica). In

each case, only a very small amount of SiF. formed and unreacted IF-0

was partially recovered. However, very extensive thermal decomposition

of the IF.0 was noted and simply involved loss of orygen.

IF_---0--IF_ + 1/20/ 2

Thus no new covalent I-F-0 material was obtained.

To ascertain the types of reactions that IF 0 might undergo and therebyI5

gain insight into the methods most likely to be successful in converting

it to IF 02 , the potential acid/base characteristics were also examined.

It was observed that IF.0 does not react with either the base, CsF, or

the acid, AsF Thus, IF 0 is more "neutral" than any other known inter-5* 5

halogen fluoride.

R-7149 35

CONFIDENTIAL

CONFIDENTIALi • •,0 • M413 T • ac W-11 ",, K_ A [)V ! •O N OF N ORýTH A ~lr P' [C ANi~ AN., IA"t ION IN C

Another reported method (Ref. 15) of preparing IF.0 is as follows;

3IF + I2 -0 31F50 + 21F 0

The supposed by-product of the reaction is iodine oxytrifluoride. Earlier

efforts to form covalent IF 0 only resulted in the formation of the ionic

I0 2 +IF6 (Ref. 9). Therefore, this reaction was examined as a possible

route to the expectedly covalent IF.0. lAcking any experimental details,

it was decided to use initially a reaction temperature of 130 C.

At this temperature, vigorous reaction occurred but proceeded as follows:

IFt + 1205 - IF- + 2F10, + i/'2 0 ,re

Thus, neither IF_0 or IF 0 were obtained. Any further attempt to secure9 3

IF.0 via these reactants will require milder co,,ditions.

Among the unexplored properties of IFL0 is its thermal stabiiitv and sus-

ceptibility to pyrolytic breakdown. The latter was considered as a simple,

straightforward route to IF 0:3

IF_0 -- IF.O + F9

The alternative mode of thermal cleavage was also expected, especially in

view of the results with SiO0 , although this effect may have heen catalytic.

IF.0 -'--IF + 1/"2 0O

The first test of the basic thermal stability revealed that IF.U could

be quantitatively recovered after 5 days at 75 C in a stainless-steel

cylinder. Therefore the pyrolysis experiments were planned at consider-

ably higher temperature (250 to 500 C) in a flow reactor. A supply of IF-.O

36 R-7149

CONFIDENTIAL

o 21= CONFIDE64TIAL

COANFIDEIBIAOFNOT AMERICAN AVIATION, INC

was maintained at -78 C in a cylinder attached directly to the hot tube

which was preheated to the desired temperature. The IF.0 was pumped

through the heaied zone. at a rnte determined by the vapor pressure of

IF.0 at -78 C, and quenched at -196 C shortly thereafter. Temperatures

below 340 C were found to cause d&composition cleanly to IF- and 0,. Frum340 to 500 C. breukdown of the IF to 1,) became noticeable and at thre

5 'highest temperature was essentia'ly complete. Many experimentts produced

traces of a volatile compound, which was identified as chrowy'l fluoride

(Cr0OFj) by infrared and mans spectral analysis (Ref. 19). Its formation

is due to fluorination of chromium oxides obtained by reaction of chromitm

metal in the stainles-steel tube. The CrOjF,) was cowpletely eliminated

when the reactor tube was thoroughly passivated and therefore it appears

that the decomposing IF '_O is not capable of producing both active fluorine

and oxygen for converting the chromium to CrO,)Fj.

To induce loss of fluorine al3ne from IF-0 and possibly also obtain oxygen

transfer, flow pyroly.ses were carried out using CuO-packed hot 1lube,. At

temperatures of 250 to 350 C, it was found that small 1uuntittie. of another

volatile unknown were produced. This cowpound exl•ibited ana iintrared absorp-

tion at ,45 c-ID (PtQt) which overlaps the 1I) ab.horption ol If'5U (9225) m-1

PQR). It is possible that the proximity of inirared hands is indicative

of the unknown being a new IF 0 species. Alter'nate sqteiL c'iidit.lons

are bein.g sought tI increase the yield. .

II

Reaction of IF_. and tINF,,I)-

The success attained with the CIF O-IMF, reactions prompted an examinaltt ions

of the corresponding IF'0-HNF0 system. Iodine oxypentafluoride represents

the only other ox)yhalogen fluoride of the type ON... The reaction proceeded

R-7149 37

CONFIDENTIAL __ __

r________ __.____

CONFIDENTIAL ACI~.AIO N

A D2IVIION OF NORTH M ERCNAITO

smocthty at -78 C. The products were N.F. FN'O. IF. and HF and maY

involve many of the reactions shown below,:

1F-0 +IIN\F 0 --) IF 0- + -NF,) + ff

1F..O + ..\,F, -O\Tr) + IF-.

IF4 0+ ~ - 0.\I' + IF,

OF,) ENO +F

IF, + F. I

2T, - N! F

Thus.I the primary di fference' between ClLU0 and I 1Kb in thei it tac tiun with4

HimF, is that C11-0. is a suf ft ici eft. i react i%- yi (101'1141a1 ill lt-11 LOe toCOnvert

ONF,2 to NX- .. whilIe 1F..U and I F-. are no t Ithe ro tore, the -10M`., d e c npulo e s

Preparation of' CINO3

A new, simpi i tied preparat ion of 0hilotito' IllI ta IIt lioiii CI F andI IDa..0 it~

demonstrated . The method and resulits are preCsentedO ini ilkeoit ol aiit Ilijit-

script lit Appendix~ A,

PREPAUATIA)N 01 IfrNOI

Some Leffort has beenl di rertetid to e11ec 1*1 heC ',I(, I lies i., o f pit re hfiNO.

Previous efforts vi i ded impure ýua teial il inIow yieold Otle 1. 5i). hill 1111(h

it possible to ob~tain the previouslY tiIItrportvid uifit rtid spekc 11 null. 111 isA

38 R1-71 49

CfiHENATA _

CONFIDENTIALIi •• * A DIVIBION OF NORTH AMtCICAN AVIATION INC

has facilitated the identification of products in alternate syntheses.

The best synthesis has utilized BrF- and IN0-, but prodtct separation wusD j

difficult. The discovery of the following reaction (Rlef. 2.t0):[

2CIF + Pb(N0) 2 -.---- PbF,) + 2C10..

led to an attempt to utilize BrF- in an analogous system,.

2W. ) lb(N0 2 + PbF i1÷ 2 (NO5 !

4 •BrXO31 2F,1 + BrNO0.

I3rF 0 + I.NO,3 -

Bromine nitrate formed in this mannier would be readily sepainiLtd froi(1

unreacted starting materials and by-protlucts. Agitaiio of the r1actiits

at -45 C resulted in a dispersion but little or no rea1tio., OU waring

to ambient temperature. a mild reaction ensued, as evidel,'id Iy a ita(lrual

increase in the pressure of the system. After oso,' time. the vo latile

products were fractionated, and some BrNO~X wos obtained. luwev,,r. most)

of the gaseous producI.., were -196 C noncondesaubles and decompositiowi

products of BrNO3 (NO,). N:O5, Br,) . Ther, fore, it ,ill be nocvssravy io- -i

achieve reaction at lower temperatllies aliiIc thliel'l pi' c]ýI e thisl . Sv(Collda"r\

decomposition. This way be achieved by thv reaction ot llrF as dehrited

from the Br,). BrF3 equilibrium. An examination of tie Nai.'O ind lil"-

system revealed that, when at room temperature. the i(,a(i io(l was too sl 11g-

rgish to yield any appreciable BrNO

- CI

i • ._ ... FID..NTIAL

CONFIDENTIAL g.CNAIIO IC

FLUORINATION OF BROMINE NITRATE

Despite the failure to secure pure BrNO fluorination reactions were con-

ducted using the impure material (contaminants being any or all of the

following: BrF5 , Br 2 . FN0 2 . 1NO3, N20 5 ). Fluorine was used at a presoure

of several atmospheres. At, -80 C, no reaction was observed und some BrNO.

was not recovered, Two reactions at ambient temperature yielded bromine

pentafluoride and a solid, This solid was off-white to pale green (prob-

ably because of metal fluoride contamination). It has no vapor pressure

at room temperature but heating to 50 to 60 C with pumping caused evolution

of FNO 2 Br,., and noncondensables. The infrared spectrum of the solid in

the 2- to 15-micron region revealed the presence of the NO,)" cation

(2385 :10 cm -1). The assignment as NO is hased both on 1hw evolution of'

FN O2 and the infrared band position. Nitroniuw ion absorptiis have been

noted in this region for similar compounds, NO,, BY." 2380 c.i- (neht. -2' )

and NO'+ CIO 2360 cm- 1 (Ref. 22); while nitrosoniwn iLon absorpttions are

at somewhat lower frequencies, NO+CIF2- 2279 cm-I (Re '. 23). and N\4 Bl", -

2340 cm (Ref. 21). This differentiation is important because only onVn

ambient temperature, stable solid compound conLainin N. 0. Ilr. and 1'

functions has been reported, i.e.. NO(Br (tef. 2!). Tlicre fore. LhiIS

solid appears to be a new complex of the type OlP C. A "horougi

characterization of NO,) BrFh, Uls carried out (Ilef. 25) and It w'as fi'id

to be quite different from this solid.

In an attempt to liberate the, complexed bromine specites, a dispiacemejit

reaction similar to that reported (Ref. 2)A) for NO'BrF, I- was attempted:

SiF (g) + 2NOnrF (s) (NO),,SiF((s) + M-1"(1).4

The solid obtained from the fluorination of B~rNO_ iwas exposed to Si~lj at

room temperature for several hours. No reaction occurred and thv Sil",

was recovered quantitatively.

40 11-7149

CONFIDENTIAL

CONFIDENTIALM4930cq wl"r'," a A OIVISION OF' NORTH AMERICAN AVIATION INC

_It ham been demonstrated that CIF is a weaker F acceptor than CiF.30

(Ref. 3) and a similar trend might be expected for BrF3 O-BrF_. There-S+ - ) + .

fore. because NO2 BrF 4 is unstable it is probable that NO,, BrF, 0 wouldbe more unstable. This indicates that the solid may be an oxygenLted

bromine (III) species, which arises as follows:

BrONO2 + F0 0 2NO + FBrO

SN0 + FBrO NO2 BrF2 0

Bromine nitrate of improved purity is needed to confirna this.

CIHLORIT FLUORIDE-ARSENIC EI. ORIDE SYSTEMS

-- In the course of examining potentially synthetically usef'ul chlorine oxide

species. an attempt was made to study the reported ('IU-Asl cozple~x (Ret'. 26).

The results of this investigation are presented iii Appendix B1. As a cor-

ollary to this study, the interaction of chlurire Ifluorides, izicludii g

Florox, and arsenic fluorides were considered as routes to vual•nbl e

intermediates.I!Reaction of Florox and Arsenic Trifiluoride

The reaction of CIF 0 with AsF was studied as a possible synlihetic roILe

3 3+to either FC10 species (such as the unknown 'lto"k S ) or other solidspecies which might be fluorinated to produce Cll'1'0 or ClI.U. Several

experiments were conduicted tit differeiit reaci~unt r'atios aiid the tormation

of FICI0 AsFR, 0 and white solid• was noted. The p.rvsence ,I, 010,+Asi'-

in the solid was -onfirmed both physically by infrucid spectra of n,,Ils

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and chemically by displacement of C10 2 by N,0 addition. An X-ray powderSt 2 4

pattern of the solid has lines due to GAO, 6s swl sohrhewhich have not yet been identified. These lines could correspond to

species such as ClF2 _AF 6 . CF AsF ClAsF 6 and AsCl,,AsF 6 r to

CIO+AsF 6 , a source of FCI0,6=

A sample of the preceding solid was fluorinated at -78 C for 12 days pro-

ducing no volatile species, Addition of CiF and later CIF_ produced small

quantities of FC10 2 but no other volatiles. Finally. the N2,U, addition

to the solid was repeated to determine if any change had occurred as n

result of the fluorinations, It was determined that now nto (Cl1, was

evolved but instead, Cll".O was produced. Other voLntile products were

FN02•'And FCIO which probably arose by reaction of CIF"_O with N, and

33CIO02. The C1F 30 evolved by N,2 04 addition eithie crat ClN 'V011 "oxygn.NItaitionl"

of C1F species by N.Q0,. from fluorination of the CI O•, se-ies. 1'from

simple displacement from species such as CII,0 + AS ,F . or o'1' litoriniatioit

of a new reduced Cl-O species (such as CIO+). in a1y catse. i)[iok* to theF2 . CIF. and CIF treatment. . 2) displaced only CIt,, from the solid while I

23 '

after these reactions CIFO. ENO,). and FCIO, were prodce'd. As a resul. .

various aspects of this reaction were studied bot.h to te lt'idlal h' tle' iter-

esting chemistry involv'ed and to determine if' a new l-otite to 11"0 wL•U'er

present.

To help clarify the preceding reactions il Lh,, tilt' _O-AslI_ .V.lteut. reactions

betý.een chlorinp fluorides (CiF and CIF-) anid nts¢liiic fll!o'ides (A.I.i and

AsFs) were studied. The following reaction (Itef. '-"7) is tHie ,ely (-,e1

reported in the literature:

CIF3 + AEF.. C.IF 6 js

42 11-7149

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Arsenic Pentafluoride-Chlorine Fluoride

Aresenic pentafluoride was reacted with CIF with the expectation that tile

reaction would proceed as:

AsP + ClF CL4,sP56

However, wihat was observed was a slow, rather uinusuial vedux reaction which

appeared to follow the equation:

AsF, + 3ClF - I -" + cl,,

For example, after a 13-day reaction period at anijiejit temperature using

equimolar amounts of reagents, one third of' the ClIF and much of L1h0 ASF-

was recovered along with Cl,) and a nonvolatile sol1id,. Trett110( of' the

solid with FNO01 displaced CiF.. confirming the presence of the CIF,, salIt.

In a subsequent reaction. a ratio of 3.1 CIFAslK. was found. couuirrming

the expected stoichioinetry.

Arsenic Trifluoride-Chiorine Fluoride

The reaction of AsF.. and CIF produc2ed Clq. AsiK. and it nonvulat ~42 so~l id,

It is apparent that the reaction proceeds as:

2ClF + AsF- - AsF + Cl,,F)5 -I

This is then followed by the reaction between CIF azid AsF to yield

ClFAsF6 and Cl,). 6I£-194

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CONFIDENTIALMdO0Rc. *wir"wmw A 01VIGION OP" NOTM AMIlIClCAN AVIATION INC Li

Arsenic Trifluoride-Chlorine Trifluoride

Equimolar amounts of AsF and CIF- were also allowed to react to detcrmine

if they formed a complex. C1FAsF 4 . Instead, an oxidation-reduction reac-

tion was observed producing AsF_ and Cl,). .lthoitgh the sulid prodUct was

not examined, the stoichiometry of the reaction is such that the fullowing

is proposed:

3IF3 + 2AsF--- sF.. + Cl,1 + CIF, \4F"

This suggests a possible overall reaction ratio of; I5CIF- + 3As _-- 3---- CI"" t -I- CI,,

when sulfficient Cll is available.3~

Reaction of the Cl12,,AslF With N.,O

6

"Oxygenat~ion" of' complexod CIF1 s-pecies with N2O•, ::,:i--ht he it )ossthlblX - I

source of CIF 0. Accordingly, a sariple of' ('"-\sl" '

and Asf'-... Reactions 0 of the solid vith N,,O. pOir itt'd ('II. CII. I a Irace of

FCI(0),. and poss hi ly 1I,). lhe ovw. all ael il 11111a [ ill)[utilr d III 1h'1

2C IFAsI N: 0 -- 2N0AsF( + CII. + CI1_iI

The production of ClI' and CIF- .may arise as if: Ihe 1,ol lowinhg st-11lUenc:

C~~s6 + *2 61+ 2

F\NO 2 +[ICIA s F64-. >NO,)A " ` + C' 1

fmO) + CIl' A.\st - NOAF• + CIl"F6I 6

Ht-7149

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Fluorinatiou of ClO.AsF 6

A sample of CIO2 AsF 6 as prepared by reaction of FClO0 and AsF-. Three

fluorination experiments were conducted on this salt to determine if this

is a possible route to CIF 0. The runs were conducted for -)1,2 days at3ambient temperature and for 2ý1/2 and 27 days at -78 C. In all cases.

only small amounts of CIO and FCIO were produced as volatile products

in the fluorination reactions, Subsequent displacement reactions usingf

CIF N 0,, and .N02 also failed to produce any evidence for fluorination

of the C102+ species.

Displacement Reactions Using FNO2

Excess FN02 .as allowed to react with the CIF_0.AsF. solid product to dis-

place the chlorine-containing species (perhaps including .C10) cumplexed

by AsF. Quantitative displacements were obtained on severai diflerenitS5

samples. The liberated products were ClF_0 and FICO1, (e.,,.. itilizing

0.63 gram of solid; 1.76 mmoles of CIF ., and o.-)6 amole o•l lClo, were

found; the calculated weight of solid for 1.76 ninoles Cl11',,UA F and 0.96 amnole

CIO0 AsF 6 is 0.63 gram). These data reveal thai the soli ds prliared were

mixtures of variable ratios of CIOuAsF6 and €uli (Asi: aid contaiuned no

CIOAs F6 . The oxidation-reduction reaction observed is e-xpirssLd I)Y the

very general reaction:

xASF.. + (X-y) ('l-.- XASF. + - o + (3, ± C100I I :' " -

Of course, complexes between AsF- and FCIO,) or CUll-.U are formed as in:

C1F 30 + AskL5 - CII"2 OA sF6

FC10, + AsF -- Cl0,Asl"6

R__7149__ _ _CONFIDENTIAL 45

CONFIDENTIALS MO34=m:•lqr=1%1ftWllrl *A DIVIIION OF NORiTIH AMICAN AVIATION INC

The relative amnounts depend upon the ratio of the reactants and the cOulrse

of the reaction. Tho~erefore. the C1.P-0 found ill the initial sovie. of reac-

tions arose by displacement from the initially formed ClF2,Asl:U

Reaction of CIF 2 OAsF 6 With Cl0,,

In an attempt to pro(Iuce ClN(. 5s" 6 , CI0, was allowed In v'ct wit Cii"('l;hsF

in anticipation of the following:

2C 10 + C IF()S1F -Z-2FC10, + Cl(A sV6

however it was de torImined that Id I v 1 ClI',, (A s is trea tedv wi th I2 ePqI i via-

lents of lUU0 ,, l:Cl 0, is formed in slightly greaterI than a Il: .• )i Chi ,motry .

In addition. Cl, and 0 , are fzr:med ill the reaction. Oil tile ha.i.s off lhe

liberation of CIO,. when the resulting solid is treated with i-NO, llth fol-

lowing reaction appears to offer the only logical e(Luhciice:

CI1PO + AsI`- - CI I",AsI"6

2CI10 + CLI ",OAI' U- Y 2"lO PC0 C I( :II-6- +CltAsl.6 i. Ftll)--,, -- CI0OrsF( + 1"(10

1-CI0 + Ci 0,,- 1-- I'C •, + L,'2 (Cl, + 1 2 O,

The ov'rall reaclioi; (CIO, + ( IIUsF(-) :ax hbe expressed as:

3tit,, + CIF,,-AsF 2FCIU,l ) + C1G.i\j l) + L.'2 1l1, + 1 2 O,)

The last reaction predi ts all iCl(O,, Cl0I,) ratio of 0).66;. Ohscrved were

0.61 and 0.54. It doe6 not appear likely thai the salt CI(AsF6 will be

readily made. Ar46 ..- 7149

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1k M04Cz&,WzV1rqdW A DIV I StON OFP NORTH AM E RICA N AVI ATION. INr

ALKALI METAL ELUORTDE-(r1O (COMPOTRYPS

The previously reported (Ref. 3) cesium fluoride-~clloririe maonoxide complex

represents a new type of compound. In an effort to extend this class of'

compounds, investigations y, of related systems (Ci O0-IhF. Cl) -CsF. andI

ClONO2-CsF) have been conducted. Tbe stoichiometry and structurie of' these

compounds are of interest not only because of their unique nature but

also because they may provide insight into the paths leading to the for-

mation of oxychlovine fluorides upon fluorination.

Chil'rine monoxide in contact with RbF at -'18 C for 5 days could Still be

completely pumped off at that temperature. 10iile this oinly indicates that

a stable, undissociated complex is not formed. it contrasts shiarply to the

1.5:1 eomplex ratio observed for C1 0 0O-CsF under thiesec (mIditiont;. This

K RbF sample was commercial material that had been powdered ill tiwV dry box.

Other measuremenitý onl this system using "activated" ltF ( Fned4 aimll theiipowdered in the dry Lnx)yielded the results shm.-n inl Table 10.

TA13LE 1L)

VAPOR lPIPSS'.tE 01' Clt) OVE 0\11 11b

Temperatr, Pressnriu :i! I ianetersC Pure C1 20* G10over Wit~

-64 I 21, 16

4571 653

240 2

The reporteil rre-,s:2res are approximate due to slow, efluili brium and thus

it can only be concli.'- -,hat complexing is vecry weai~.

R-7149 47

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The interaction of CI0O and excess CsF was studied at -23 C with no vupor

pressure reduction noted, An experiment at -45 C yielded inconclusive

results. A problem encourntered during this work was the apparent aboorp-

tion of CIO in the Teflon reactor; the absorbed CIO,, cannot easily be2-removed by pumping, thus complicating measurements.

A previously reported CINO -CsF complex (Ref. 3) formation was re-examined.

After 6 days contact at -78 C. it was still possible to recovvei all the

CINO3 by pumping. In addition, no reduction in the vapor proesure of

CINO over excess CsF was observed at -78. -64. and -. 'Ll C. Again, a3

deficiency of CsF surface area may be responsible J'or 1his m11eII'Vrelciblo

behavior.

An additional experiment was conducted to elucidate the Csl. .l. l)coni- um'19plex. In these experiments. F n.m.r. was tised to aitlvyzt , hi• co::plex

in both CH3 CN and CILNOJ at approximately -30 C. %o I'F .resoVnance was

observed, apparently due to the slight solubility oI CslF in the.te solveiit.s.

No more experiments are planned in the Cl,2U-CI' s ystemu. IJ. Imhit ecn con-

cluded that CIO,) and CIONO, do not, form complcxe.s with ('si" and thatf. addi-

tional st.ructural data for CsF. I.5CI,O0 complex will he difficult I0 obltill.

MISCELIAN'EOUS REACTIONS

Reaction of NF-O and Pl',,CCl

The preparation of CINF,0 'was sought because of its potential titility as

a reactive source of the ONl0', group. This %,as at eunp ted 1Y reactLiuon w- II

PF C1 through a dissociative reorganization process.

'3

NTI + PF Cl- F OPF-Cl -• lCIN,)O + PF_

R-7149

CONFIDENTIAL

CONFIDENTIALX_ 93O - =XZlt"t M= 6 A DIVISION OF NOOlT04 AMERICAN AVIATION. INC¢

"7 The preparation of PF Cl itself was only recently reported (Ref. 29) using

PF Cl, and SbF. It was thought that a simpler route would be.

PF. + CIF - PF Cl4

Experiments verified this concept, and 40 to 50-perceni yvelds were

obtained in minutes by reaction at -142 C in Kel-F. The by-ptoducts were

PF C1 and PFt.. It is almost certain that increased yields could be

attained at lower reaction temperatures but sulficient material for the

present purposcs was prepared in the indicated manner.

The conversion of N%.10 to ClNF.o0 was attelupted undor a v'kriei y of condi-

tions. Experiments were conducted at -80 C. -1,26 to -70 (C and albo by

repetitive cycling from -126 to -196 C. with thv, duration ilrviu_ from

several hours to severail days. To completn ely consa•n eithoi, reIc talitk generally required 2 days. No appreciable complexin.g ol the reactants

was detected. Trifluorazine oxide was completely strippid ou' its h'luorille

and the P.,Cl converted to PF_. Thus. thil roact on did not take tile

desired course and only resulted in the slow flitor;inaion II1 PI, ;

NF0 + 2PF, Cl - Cl2 + PF 5 , N01'l"

At higher temperattlrcs . the obse rved coul c I ii t his I •toim tii l L in d 1lci red

only slightly as indicated below:

2NF.0 + 5PI?, CI - 2C1, + CINO - 'd' " + N01.1') I ) . I

R-7149 49

CONFIDENTIAL _w

E1 MC InKAW U A vISV1i0k OF NlO4TM AMEliCAN AVIATIV4. 104C

Rtiari,innq i.f Ci-F and N-0 Species

r_ Several vigorous reactions of Cl-F (CIF 3/FCIO, mixtures) fnd N-O (N,-,.

N 205 mixtures) species were found to give rise to all Unklmi' volatile corm-

pound as indicated by unidentifiable infrared absorbances at 5.8 mlicrolns(N-O?) and 9.7 microns PQR (CI=O?). It appeared the compound ,might be

o0ClONO. Purification of the material was not afhieved because of xts2 2

continual decomposition. Several synthetic approaches were then examined

as possible means of preparing this compound.

PClO2, + ILNO - Hr + O,)ClO\OJ

FClO2 + N205 - FNO2 + 0,2CONO,,2 52

2FC10,2 + Pb(N0 3 ) 2 - PbF2 + 20,,CIONO2

All these reactions failed to produce the tinkoun ol" allY o the1r nlv% :nliteviul.

Only mixtures of known CI-0 and N-O degradation poductiS Wero obSerlved.

Because no simple. reproducible method was found for the .y'litlesis of, this

unlknon mLaerial, and because it has only been observed in trliace qu1tanti-

ties. a concentrated effort to determine its chlaitcttr was not. coinsidretod

feasible. Further synthetic efforts were suspended.

50 R-7149

CO NFIDENTIAL

*A Of VI $ION Of N 04 Y AMERMICAN AVIY(ON IN C

EXPERIIMENTAL

UTrAVIMT IRRiADIATION

Cells

F ~Initial irradiations and spectrophotometric data were olbtajinei with cel ls

having a path length of 10 centimeters fabricated fion 1-ijicli-Ol) nickel.

tubing. The windows were 0.02~-inch-tbick, 1-inch-diameter'. alti'a~iolet-

grade Linde sapphire, and appeared completely unaffected by the reactanits

used. The winldows were held in place with flauigos and Tefllon 0-r-ing

Hoke WiS2M Monel bellows valves were fouind SatjSfaCtIF'iv as Cell Ciosill-eS

An additional cell with a sapphire windcw at one end only i was aiiiso flati -

cated . It. could be cooled during irradiation by illuimersi on in it suiitable

cooling bath and provision was made for hilowing dry ni trogen pas~t 'Aie

window to prevent fogging by atmospheric mo1iSture1-. Blecause the wiindow

opening was 0.66 inch in diameter and the lell-tli 0o the collI 7.5 iziclic's,

only a small1 percentage of the available rad iaton reached hle reactants.

Therefore, a new stainl ess-steel cell was bulilt WI1i thi i11-tluEt(t

ultraviolet-grade sapphire window (thickness: 0).125 inchi). Ilie cell laid

a -window opening of 3.5 inches and a depth of' 2.9) j ncli(. The ailoujit of

radiation reaching thc reactants was greatly increased ats at resulit of the

much larger window area and shorter lpnlgth. Copper coils were soLdered

to the cell w~allis and bottom so that the cell couldl be coo ledl. :%n auto-

mutically controlled circulating methanol system has been) used to main-

tain cell tenperature within 3 C of the set temperature which was conltin-

uously variable from room temperature to at least -60 C. F.irigof the

window was prevented by circulating dry nitrogen between the sapphire win-

dow and an additional window placed above it.

R-714~9 51

CONFIDENTIAL

fI. ft rzbWMW 9 A IIVISION OP NORTH AMEIqICA#4 AVIATION IN C

Ultraviolet Source

Work was conducted with a tlanovia utility lamp No. 30620 (power input =

100 uatts) with the protective housing removed to move the lamp as close

as possible to the cell.

Materials

The materials used are described in Ref. 2 and 8. Purification of F'IO,,

was carried out by pumping off the Cl, impurity while holdin ighe FCI:),,

at -78 C. The chromatographic purity of the colorless liquid %us better

than 99.9 percent. The CIO 3F was purchased fro, Peniisalt. The CIF was

prepared by corona discharge From CI,, and V,, and puri lld bY Tidyta'ionatlol,

CORONA DISCHARGE ACTIVATION

The apparatus previously used for corona discharge e.Xperiimenjts . re. I)

was also employed for this work. The "Large Gas Ticacvir" (i. 'I. idt. 3).

which was immersed in a -78 C bath during the e.\pPihll-'lLs. MIas sotppl ted

with enerQ" from the Audio-Frequency Pulse Generator (Rlef. 1. i 8).

The generator ,as modified for higher pulse repvtition talv•s a meais

of increasing energy output by decreasing thit induc tamve Ul t(ie 0.117 Ii

choke to 25 inh or 67 114m. selectable by means of an added -oil ch The

trigger generator was modified to cover a range of -- to 'WOOi i1z by Chang-

ing the 0.01-microfarad capacitor to 0.005 microkarad. A Cemico 79S0()

induction coil was used to generate the high-voltage pioises.

52 R-7149

CONFIDENTIAL

a A DIVIBION OF NOATb AUIPgICAN AVIATION 14C

- I-- ;&CTIUN OF CIFO and M.NP

P2

A prepassivated Kel-F container fitted with a Teflon valve was used to

avoid the incompatibility of CIF 3 0 (and generated iR) with glass and IN•,,

Swith metal. Florox (30 cc) was first condensed in at -196 C from the

metal vacuum line and then IMN•2 (29 cc) was condensed in from the glass

line at -142 C. The reaction was then allowed to proceed at a higher tern-

perature for several minutes prior to fractionation on the aetal line.

All the IMF was converted to an approximately 2:2:1 mixture of NYF 0.23

C1NF2, and N4F11 When the CIF 30 to HiNF2 ratio was greater lhau approxi-

mately 1:2.5, unreacted CIF 0 was recovered. Some ICIO., was found and3

probably arose from decomposition of CIF.- in incompletely pau.-.ivaied

parts of the line. Very minor quantities of CIF_ were observed and imat"

indicate a secondary reaction path throgh oxygen abstraction Irmn CII"o.

When the reaction was conducted at -112 C with ClI.O F0(27.5 co) and IM',

(36.5 cc), only 75 percent of the total \'F product jifi \tire was re-,-ove'l

after 15 minutes pumping at that temperature. Tht' remaining 25 percent

was obtained on warming the reactor. An attempt was made to confirm this

indication of a low-temperature complex but i,,as unstic(cesslul. ['se •f' al

even lower temperature will be attempted but the very l), v•apOr pressure

of IM2 at lower temperature may cause contact probl er!: bpcnuise both

reactants would be solid. 2

REACTION OF ClF.O AND FCONT,

Florox (35.5 cc) and perfluoroformamide (4•6 cC) were reacted in the hel-

container for 15 minutes while warming to -0 C. A snmall amount of noncon-

densables was observed. Based on 2 moles of ICo0I,) reacting with I mole

of CIF 0 the yield of NF3 0 N.as 21 percent. The major N" products wereClINT 2 and N2 F,. No FCONT was recovered, conversion to COF,) b.cing complete.

R-7149 53

CONFIDENTIAL

ONFIOENTIALSi 0"C i *kE W W W lM W A rIVI $ DN OF t4(UMf7- AMtRICAN, AVIATION INIf

PREPAPATION OF IF-

Iodine pentafluoride and exeess F. were heated at 130 C i;j Hoil or

stainless-steel cylinders for several hours. Conversion to IF- was nearly

quantitativp. Rough purification was achieved by vacilum f5'actionation.

Small samples, containing barely detectable amounts of 0F'_ and no 111'

after Kr treatment. exhibited a vapor pressure of 160 nmn at ( C compared

to the literature value of 3,05 mn (Ref. 13). Mass . p'•,?-tral nn, seusrenclt.o s

and vapor density indicated no additional impurities.

PREPARATION OF If.o

Iodine heptafluoride and excess SiO,~ (Cah-0-Sil) were eItcted in stainless-

steel cylinders overnight at ambient temperature . Nust Id" 1i1L, bY-prt0dil1,t

SiF, was removed by vacuum firactionation: the final traces atoll" wil i a11l%

]{F were removed by complexing with KF. This ma iterial n ,as p ire Iby all

measurevuents. Because of the wide discrepancy hetween the observed and

the reportd (el 1'. 15) vDpor pressure, the vapor prt ssu re- leitipe ialurtic

relationship was redeteirmiined. The observed data and derived eqlUmttioU

are presented in Table 11.

LJLE I I

VAPOR P1I.ESSMLE-TEXPEBATIT1I1L I)ALX FOR IF_()

Teiperature, Obset'ved Pressure, Calculated Prssur,C ....... . -- _

G7. 1 3 2I0M

-46. () 46 '1 .0!

_-2 .7 2-)0

-10. 11 ')1 ',170

0.0 824 81.

log Pr= 8. 987111 1V0). '1 .:T

54 R-7149

CONFIDENTIAL_

__ _ _ __=-.- - ----- -

CONFIDENTIALMc~kCý WWv W A 0OilkIl6N OFP N00TH AMERI~CAN AVIATION I N C

PYROLYSIS OF IFs

A cylinder containing IF 0 was attached to a straight stainless-steel5

(30 inches long. 12-~iiich heated zone) tube passing through a furnace and

then connected to a Teflon I'-trap and the vacuum line. The tube was

heated to test befflperaLure and passivated with CIF_. When chlorine oxides

were no longer generated, the system was completely pumped down. The IF 0

cylinder was cooled to -78 C and the U-trap was cooled to -196 C. Con-

tinuous pumping was maintained and a flow of IF 0 was begun (calibrated

rate = 5.5 cc/min), Separate flow experiments were of 20 to 30 minutes

duration.

R-714,9 55/56

CONFIDEN tIAL

CONFIDENTIALS4 A DI 11ý D' ý 04j '~~~ RICA%' AVIAT ON I N

S1W , FLER-ŽCE S3

•j i, Cratti, Ft., e t aL , d.inorgi, .Nue I Chem.. .L 653- (19)6 )

11 R-6736-3, Quart erly_ Progress Report, In o r ga i i i a l ei Oeid(Iizers

Contract Nonr 4l42•0(O), Rochetdyue, a Division of North American

Aviation, Inc, Canoga Park, California. 50 Mnrchi 10)67, C(ONIDL ,'LAL.

3. 11-66•1-1l, Annual Sumary Report. Tnoiganic hblnci- O."icizi.di s,

Contract Nonr 4d42B(00). Rocketdyne, a Division of' North American

Aviation, Inc.. Canoga Park. California. 31 Jly 1066. ('ONFIDI'I:N1 IL.

!j. Steuunenberg. R. K., and R. C. Vogel. 1. Am. Che!-;. S ., 7_,. ()(1 (1t):6).

5. Glissman. A\.,and 1i. J. Schwnacht'r. Z. Piysi.;, Che:ii.. L'&i, 52 8 (lo)Si).

6. Schmitz. IT.. and 11. J. Schumacher. Ana l. A\soc, ii.. Argegntinat 58,

61-66 (196o).

7. Schmitz. If.. and It. 41. Schum-acher, ,.an 1. Asoc. Quinu. . A,',_enti na 5.14.

363 (1950).

8. 11-6639. Final Report, Research in 1lliurine ichcmistrv. lilocktdvyle, u

Division of North American Aviation. Iici.. Canoi-a Jarl, (al lforiia.

30 July 1066. CONFIDENTIAL.

9. R-6258, Annual Report. Inorganic Ilaliien 0.\ xidizers. (Conicailt Nuin !i.128(t)).

locketdyne, a Division of Nol'Ii Anerican Aviation. Inc.. ¶iln(in Par:%.

California. 30 Jul% 1963, CONFIDEMiLIL.

10. AFWPL-TR-65-5i, Preparation and Characteriza ti on of a Neu hhligh-ELergv

Oxidizer. Rocketdyne. a Division of North A!:wriocan Aviation. hio.,

Canoga Park. California. April 1965. CONFIDENT'IAL.

11. AIRPI-4'R-65-125, Physico-Chemical Characterization of hliirh-Enerlrv

Storable Propellants. Rlochetdyne. a Division of North American Avia-

tion, Inc., Canoga Park. California. May 1965. (ONILDLNDEAL.

R-7149 57

CONFIDENTIAL

CONFID£TJW,SA OlVIUON Of NORTH AMERICAN AVIATION. INC

12. Ay...cy, E. L. . oiu n S. Sam J. ,h, Chem. Soc., .509 .() 3).

13. Mclale. E. T., and G. Von Elbe, J. Am Chem. Soc.. 8. -79 (1967).3

II. Schmitz. IH. and H. J. Schumacher, Z. Anorg. i A Ilguw 'heom . .

'138 (1942,,-)

15. Bartlett, N., and L. E. Levchuk, Pro. Cmoc 32 (13).

16. Smith, D. P., and G. M. Begun, J. Chem. Phys.. 43. 2001 (1065),

17. 11-6736-1, Quarterly Progress Report, Inorganic lhallgon Oxidi-,•rs.

Contract Nonr W1428(00). Roclcetdyne, a Division ot' North Anmrican

Aviation, Inc.. 30 Soptehber 1966, CONFIDENrIAL.

18. Irsa, A. P.. and L. Friedman. J. Inorg. and NLci . ('lInn.. 0. 77 (1958).

19. Hobbs. W. E.. J. Chem. Phys.. 28. 1220 (195•).

20. U-6780-1, First QuarLerly Report. VerificaLion or it New Liquid

Oxidizer. Contract NOw'60-0659-d, Rochetdvsse. a )ivi iim of ' North

American Aviation. Inc.. Canoga Park, Catiil'orija. 5U {ctuth' v 1066,

21. EvansD J. et al.. Inorg. (hem., 3, 857 (191;).

22. Nehgen. .1. 6.. pt al.. Inorg. Chem. 1796 (1965).

23. Christie. K. 0. and J. P, Guertin. Inor,:;. Chem-. I. 9035 (1965).

2 . Chretieri. A. and 1). iluy. Compt. rend.. 2%. 2 {I V .

.25. R1-6736-2. quarterly Progreos Report, _loirganic Iiatogen Oxidizore•,

Contract .onr Vi-a28(00). Rocketdyne, a Division of* Noistl Americant

Aviation. Inc., Canoga Park. California. 50 December N(60. CONFIDE.\ILUI,.

26. Schweisser. M., W. Fink, and K. Brandle. A:ia eo. Clvii. 61. 780 (1097).

=

58 1-71&9

CONFIDENTLRL

CONFIDENTIALmcom WwIt * A OIVI6ION OF NORTH AMERICAN AVIATION. INC

210 (1965).I

28. Goodeve. C. P., J, Chern._Soc., 2733 (1930).

29. Carter. Jr., R. P.. and it. R. Holmies. Inorg, Chem., 4, 738 (1965).

R-7149 59/60

CONFIDENTIAL

ftco~C-mwi~w = A DIVISION OF NOIRT? AMER'C;AN AVIATION INC

APPENDI IX A

A NTW SY1'ITHESIS OF CHLORINE INITRUF

Carl J.Schack

TOPrevious methods for the preparation of chlorine niitrate' involved

the reaction of either Cl 0 or dlO with NO,)o N 01 I u Cricuvnvtt the2 '2 -

()(a ) H. Martin, Angeul. Chem.,70 Z297 98.()M cmlsInorg, Syn., 9. 127 (1967. -(l). ()MShese.

the use of these hazardous chlorine oxidet;. al 11eW louto to this CollipoUnd

was sought as indicated by the following eqJUMAtio.

CIF + INIO -ý C1\O + RFf

3

It has been found that this reaction constitutes a rapid awl coriveil-

ient synthesis of chlorine nitrate. The reaction occurs on Contact of the

CiF with solid I0.. in 85 to 95 percent viel d. The prodtict C1NO~ was puni-

fied by vacuum fractionation. The vapor pressure was measured over a

considerably broader range (-80o to 260) than that ill the lituratUre

(-70' to -250). The temperatures and %apor presquires are: -~70 ,).' I ir~

-63.9 , 6 m:-46..2 5.2 o;-39 5un 9J,'02 21: l.0~' 326 rim;

described by1log9p 5.!w92-,5().'k()

10

Chlorine ni trate has a b .p. of 22.30 (vs. literature e.\trapoiativa

of 180) with a heat of vaporization of' 6.9 kcal. m-,ole and a Trnutozn Con-

stant of 23-4. The compound is stable inl metal slysteiis after pretreatment

with some CLNO .Long-term storage in metal or glass at approx\imately -~It0.3

R-7149 A-i

a *`4tWRW"Wr A CIVIUION OF NOM'H AMERICAN~ AVIATION I NC

_Fhas not resulted in any significant decomposition. Ln~iiit' !:O- an,*,

(2) W. Kwasnik, "Handbook of Preparative Inorganic Clienmitry, " G. 111-:tlier.Ed., Vol. 1, Academic Press, Newý York. N.Y.. 196), p. It9 .

chlorine oxides, no explosiv'e incidents have been experiencedt with ('lXO-,

HUWi. he - Id be handled withi care in the absence oi

geln.,itivitv test relp

Experimental

Chlorine monofluoride at,( nominally anhydrous tM).. (approximately 981

percent) were separately condensed at -1960 into at swiuniess.-steel oil

Kel-F cylinder attachod to a metal-Teflon vacuum line'. Thme cvlinder %;it

closed and the temperatare was changed to 8onic hi-gher ronmtammt. Itempera ntlT

in the range -112O to 0 . The reactor wais then helId ai -780 alnd the jproduct aSpumped out rapidly and trapped at -0-3. Li L11 01- or o 111 Wa s

removed from the reactor in this mannier as evidenced It-iv fie fai I 'ice t o

generate SiF, when the product was subsequently handled ill --Iass . oic

times HF was removed by allowing the products to stakd ()Vill' Nal' [or at

period. The identity of the product was es tab Ii liedib livt- irili cred

specCtr=)m and mjolccular e i-ght from vapor dlenisi t% !:i'leaSUimmeue, S. Vatpor

(3) K. Brandle, M . Schmeisser and W. L~uttke.(lie. hr. Ber , I)-) 517)o) (Pi60)._

phase chrotmat ography, usi~ng a colIummi paclied oi iti i~\IIHil I r a iiolii

Oil 4-11V and Kel-F low density molding po\ýdei' accoidimig to [laval anld

Neale gave an analvsis or £ INO...9 ( C,), i . Mii . I- or ill plmrpo.-rc ()i*

(It) V. H. Day-Ln and B, C. Nealo , A\dvances ill (hV!!!S trV Serie(-, No. 5'1,American Chemical Society, Washington. D. C. . 100(. . 221),

determining the stoichiometry. the more vCCamaite1 ci :IeaSnrahle)1 (Al Uias USed

as the limiting reagent. Typically, 11.9 mmnoles of CHI was- reacted with-

A-2 11-7149J

zw43o~~ ~ 4=ScAr * oI VISION OF NORTH AAIM!NICAN AVI ATION. IN C

approximtiely 14 UW11oles Of MIOand yielIded i0.6 Mmoles of C1N0. (89 per-

cenit). in an alternative procedure, the 11N0 was maintained at -780 whi I e

CiF gas was gradually admitted to the reactor. Uhea the pressure ceased

to drop, the reaction was complete. Workup was as above. The syntheois

has been succesafully conducted on a scale of several liters.

Ac~mwledgement. This workt was supported by the Office of Naval

Ntsearch. PowAer Branch.

V-74 -/-

"NNW=~ a

E~? ~ *A DIVISION QF NO~tH AMERICAN AVIATION INC

A ITfDOX REACTION OF DICIELORINE OXIDE WITH ARSELNIC PL\'TALtOIII11DE:

AN LUNI'SUAL SYNTBESIS Of CIU0AsI

C. J. Schacl; and D). Pilipovich

Dichiorine oxide (or chlorine monoxide) has been reportod to forni at

complex with AsF. at -8anid at about -30O formed an odd ino Lecule,

ClOAsF-., through elimination of Cl o. Inference of the StrICture0 as being,

(1 ) M. Schnieisser, W. Fink arJ K. Ijrandle. Apeu- Chemi. Q. 7,40 00)~7)

the postulated odd molecule .ub drawn from the observed racuc ion stIoichi-

ome try and the fact that the postulated odd niolocule reacted %otfi NO,, to

give CIN'O

We were inteiested in studying various aspocts of the pinoloseli odd

molecule particularly as a ready source of the ('10 raidical . iowvervs.,I, w

felt that, prior to utilizing Mlksl`. as ani intermedijate. it moile cori.p~vLet

characterization isas in order.

Materials . Chlorine monoxide was prep~ared fro! CtM anid yellow IILrU

using a modified procedure.- Arsenic pentitofi onijie wa!I ptiicluise(I fromt

(2) C. J . Schack and C. B. Lindahi , Inr.iuInd Nuc I. ChIem~'. I.e Iters.

in press.-

Ozark-Mahoning and used without pun ficatioai iater griw chrom!;a1.i),rraphv

indicated a purity of better than 9().51, (Ijoryl Iltioride wsas Prepared

R-714i9 B-1

"W M * A b!V'SION OF -400TH AMCRN:CAN AV IAT.OF4 IN c

from KCl I otind F and purified bY tract ional condenisation. N'i t r o)gen32

(3) A. Engelbrecht. Anger., Chem. 66. Vi42(P3)- - - - - -- - - - - - - - - - - - - - - - - - -

tetroxide was purchased from the Matheson Cu. and purified hy fractional

condensation. Phosphorus dichloride trifluoride was lc(rWVcl froM IT and cl.)

(4) R. It. Holmes and W. 1). Gallavher, Inorgi. Chemi... 2.. 4-55 ( 196-).

Apparatus. Experiments were conducted in two vactinin systems, one

constructed of glass, the other of stainless steel-TeflIon. SolIids we re

handled in an inert atmosphere glove box. tnt ruled sp'ct ra were takenl sll

a Perkin-Elmer 137 Infracord usin"- 5-cm gas cell1r fitti-d wit[h A_,CI wixndows

or Ikil1 ca rbon oil miull s between AgCI piat es. Debyi'-Scelieir poiswderi X-ray

dififraction patterns were obtaiined with it G. LC. .'JD5 instrFauntw lsing,-

Cu-O r-adiuatiuon.

apo r phase chroma tography of reac tants5 and prl-iucii uwas cal-ri ed iii t

01. it columnu packed wih 111 of - Hal oca4 I'on Oil 'i - lI uiid ho -F l ow

deicsj ty mloldinzg powder ac cor d ing to Day-an andl Ný In oi

()V. 11. Dayan and B. C. Nun is. Advances ill Clioiiiist-ur SVIecs, No . S)'J.American Chemical Society. Washingaton. D. C' .-1060. p. 22-5.

Reactions 01' CI,, () cud ASK.. NeaSured club!n itf i:. td' Ci)tt (11I c-,c-.

5.22 mmioles) and AsY (83 . cc. 1.79 limoles) uerv seilnhil c l\ c-iailenlsed

into the reactor (alass or leftlon tubes ) at -he 14-1 inzpsrat tilv wasG

changed to -78 and it %,as observed that the !1 ~xed -otis- inn I gi-ailu i\

developed a dark red color, Pumpingi on the mlixturI e after n 1ew hiours at

-780 resulted in the recoveryv of' sonme of the starlln rig nterijais aiid much

Cl 0 . Subsequent warming of the reaction to ambieit I efiipeintciie grave addi-

tional. small amounts of gaseou6 materials and a cihili' solid. Little or rio

B-2 11-7149

W I *A DIVISION OF NORTH AMERICAN AVIATION IN C

-1960 non-condensable gases were observed throughout the reaction, In

all, 1l1 cc of volatile products were obtained. Infrared and gas chro-

matographic analysis indicated these products to be a mixture of AsF-

(17.5 cc, 0.78 inmoic) and Cl2 (93.5 cc, 11.17 mmoles) With, a trace of CIO,

and no C1 0. The observed reactant-produIct ratio Of Cl,UO:Asr :(71,) was5.00:2.89:4.01. Slimilar reacti.on ratios were obane htiCn UA sue

as the excess reagent, The solid product %howed two infrared builds1 -

120 m~(m, doublet) and 690 to 700 cm (,broad). Based til the

observed stoichiometry of the reaction and the knouin infrared frequenc ies6 7

Of Cl-O and AsF compounds, it appeared the solid migxht he principally

(6) E. A. Robinson, Can, J. Chem., 41., 3021 (196-5).

(7) R. Peacock and D. Sharp. J. Chem. Soc.. 2766 (1919).

CIO2As 6 ccordingly, an authentic sample was prepared.

Preparation of C102AF. Chioryl fluoride (1l1 cc, 'I.96 ninnles)

and AsF5 (63.7 cc. 2 .81 mmls) were separately conden.,ed iuito a Teflon

ampoule at -1960. After I hour at room tempterature, the :Inieactedl gases

were removed and measured (48.0 cc, 2.14i mmoles). Ani infrared specirtun

showed only FCIO The white, solid product had ani iuufrared spectrtum

identical to that of the solid from the Cl, 0-As.:- reactiou. Ini add it ion,

both solids fumed in airn and exploded on coil Ladt with N,-ai er. I Io wdeI r

X-ray patterns of both solids were obtained aud were idenitical . llue

observed spacings and relative intensities are griven in Iiable I.

Reaction of CI0,,AsF( and NO2 Weighed amtounis of' C(t1AsY. and excess

NO2 gas were reacted for I hour at 00. The expected displac 11emnt8 01, CMu,

(8) M2. Schmeisser and W. Fink. Angew. Chem., 69'. 781) (19)57).

was achieved but in poor yield; 20.1 for the solid from the CI,t.) reaction

and 35ý for zhe solid from the FClO0, reaction.

R-7149 B-3

W I~*A DIVISION OF P40RY AAM[ rCAN AVi AiON IN C

TABLE1

X- MY ~ ER DIFFRACTION DAIA F'OR CIO,,AsF 6

0T Relative re~a-tiv15TdA Intensity d, A Intensitv

7.50 30 2.30 flo

5.55 30 2.08 605.10 30 2.05 60

4.40 70 Lý95

4.02 '0 1.87 1

3.63 100 1.811 10

3.57 90 1 .80 10

-3.119 10 1 .76 I

3.03 50 1.70 20

2.910 .91

2".7-V ~ 10 .J

Rleacti on of PF Cl and Cl1, 0. A 1:1 i .xtt no ol' PF CI, anid Cl Uo was3 2-

allowed to warrm to room temperature at which point. an igifrarod spect r~ui:Wa

taken. The only infrared absorbing material present .. jis 1101... Noiie of

the Pk C1 2 a strong infrared absorber. r'wauintd. 1[1v lo-.piouiic t 1.1,,

byRsut and Discussion1-79

Tereaction of Cl 0 w.ith AsF.. does not rive the odd molecule ClIOksIK)

folow hestoichiometry shown in equation 1:5C190 + 3AsF. - 2C10,AsY~ + 'Ici, + AsOF-.i

a * A OIVISION OF NORTH AMERICAN AVIATION~ INC

The reaCL~on stoichiometry does not appear to be dependent on the experi-

Mental reactanit ratios, The formation of Cl0,ytsF6 confirmed by pre-6 a

paring an authentfic sample and comparing their X-ray patternsL0

FCIO0 + AsF - C 10 AS F6 (2)

In the reaction of C1 0 with AsF.. the evolution of Cl,. apparently involves

a much more complex process than a s itple Cl-0 bond rupture. The equation1 . 0.reported for this procesb at -30 is shown in equation 3.'

C1)0'AsF..- CIG~sF. + i/2 Cl,,()

We would prefer to propose an initial step that ijifer., iti olonh/at-ion of1

C1 0 0. i.e., an ionic complex is obttained. perhaps ClO+AsF..Cl:

Cl 0 + AsF. ClIAsF..Cl 42

The oxidation of the ClO+ species could theu proceed with add: tijoial C 1,0:

Cl00 + ClOASY.1-l CIO,,AsfIKCI + Cl (-3)2 2

This step (equation 4) should not be considered unusual inasatich as ot~thr

chlorine oxides are capable of redox (e'.V.. CoiO 'ci yes somle (A .( oil22

photolysis 9 ).

---------- -------------------------------------------------------- ------ - -- - -- -- -- -----(9) H. J. Schumacher. and G. Stiezer, L. Physik, Chem., 6 1T)--------- --------------------------------------------------------- ------ - -- - -- -- -- -----The most. difficult rationale is the formation of the AsF ini the reaction.a

62Admittedly a multiplicity of diverse reaction sequences could he prooPI.sed

most of which would be difficult to experimentally verify. One possible

path offered involves tile dissociation of ClO0 A's1LCl into its components

with the subsequent reactions noted:

R-7149 -I

WR ~0 A DIVISION OF NORTH4 AME!RICAN AVIATION INC~

C1P,:,AsF Cl FIC1O + AsF Cl (6)2 4

2AsF, Cl - AsFCl + AsF_ (7)32

AsF_ + FCIO, CIO,2AsF (8)26

AsFCl + Cl 0 -- AsF 0 + 2Ci, (9)32 2 3

It is readily seen that the sum of equations 4 through 9. suitably

weighted. gives equation 1,

The identity of AsOF was not established as a product since it is a non-3

volatile X-ray amorphous solid. In addition, we did not wish to further

(10) K. Dehticke and J. Wiedlein, Z. Anorg. allg. chem.. 3'"2. -223 (1966).

complicate matters by studying the reaction of AsF CI, with Cl, U as a test32

of equation 8 inasmuch as AsF Cl2 "goes ionic" and is formulated as

AsCi 'AsF6 We did feel. however, that a suitable teot of elqua~lior 84 6

(11) H. M. Dess, R. W. Parry, and G. L. Vidall, J. Am. Chem. 6oc.. 78.5730 (1956).

would be the reaction of PF3C2l and Cl90. Indeed. the rapid conversion

of PF..C12 to POLF and Cl, as in equation I0:

PF3 C1, + C1,• POF3 + 2, (0)

strongly suggests that "covalent" AF Cl would react simiiaPlY. The3 2

reaction conditions are such that the reorganization of Asl",,;l. postulated

as an intermediate in equation 6. would give initially the covlent structure.

B-6 t-7149

ffff A DIVISION Or F40RTH AMLOICAIN AVIATION. IC

The initial report on the preparations of "ClasF" did offer the

reaction of N02 as a proof of the radical present

C1OASF + 2N0 N02As CiN (II)

5 2 2 sF

The existence of NOAsF has already been questioned seriuusly and appar-

ently disproved , Further. the formation of some CINO. should be expected

(12) S. I. Morrow and A. R. Young. Inorg. and Nucl. Chem. Letters ,=_ )•~~39 (966) .. ....

from CI0,AsF6 and NO2 inasmuch a8 the reaction of eO 2 and NO0 gives

CNO 13. It is quite likely that the reaction observed by Schxeisser e a3.

(13) H. Martin and Th. Jacobsen, Angew Chem., 67, 524 (1955).

was the initial displacement of C102 from CIO2As"6 by NO2 followed by a

reaction of CIO2 with NO2. the overall reaction being:

CIO0 .sF6 02 NOc,AsF 6 + ClNO_ + 1/2 o (12)

Except for the formation of the oxygen, the reaction in equation 12 has

the same stoichiometry of NO2 to "solid" as •hat reported in equation 11.

Thus. the proof of "CIOAsF-" through its reactions or its synthesis is

not conclusive.

Summary

The action of Cl 2 O or AsF. does not give the odd molecule C1(•sF_ as

has been reported in the literature. Instead. the salt ClO sF_ is obtained.As•-6-

A rationale for the formation ol the AsF ion was offered and involves6reorganization reactions of arsenic chlorofluorides.

Acknowledgement. This work was supported by the Office of Naval Research, A

Power Branch.

R-7149 B-7/B-8

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G. REPO PT DATE ?o. OTA6 NO OP PAGES 76. WO Ov maps

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I I 1UPP-L dMNTANY NOTES 12 SPONSORING MILITARY ACTIVITY

Office of Naval ResearchPower Branch Code 429

___________________ Washinm~ton. D.C.13 ANSRAT(C-)New syntheses of ClF 0 were discovered utilizing ultraviolet-initi-Zated reaction of FC100 and FClO3 . In the presence of 1`2 CIF.~ or ClF5, FCIO,,gave CI 3O0 in high conversions and high yields. The same techniques were niot-successful in oxidizing ClF 3O to ClF.O or BrF. to BrF. There is considerableevidence that FICl3 is an intermediate in the synthesis of CIF 0 by ultravioletactivation. Corona discharge activation of FC1O 2-F0) did not result in C.-F 0. Astable mass cracking pattern for CIF 30-aobindwith the must prominent peaksassignable to CIFU+ and ClF 2 O+. TeF9nmr. spectrum of gaseous CllK.Urevealed two bands at -Q'~ad-l~wt esetv aiso and 1. These

bands support the proposed C symmetry for C1F-0. Novel processes were dis-covered for forming NT 0 at Tow tempe'rature from CiF 0 and 11NT, or FCbN%'c,. Masscracking patterns of'I an IF 0 were determined. ?he va~por pres-~ure-te-mperaartequation for IF- )0 was deterrninea as log pmm=8. 987'i-l6 39 .4 ,,T. Pyrolysis of 1F-Oyielded an unidentified volatile material which may Le a new IF 0 compound.Reaction of IF-0 and 01F, yieldad FNO and NQF 4 as oxidation proaucts. A newmethod for the esyntheisi-of ClNO3 was dee-pdusing ClF and IN 3 A similarreaction of flrF- and WO gave limited amounts of BrNO-. Fluorination of BrNG.

gaea new oidof the Zype NO2BrF.O. The solid, NO iF,,wachatrid.Reaction of C1 20 and AsF~ gives principally CIO.),AsF~ which was characterized.O'ýychlorine trifluoride aid not ionize in BrF3 or IL1. The reaction of ClF 0 and

4ý JAeF- produced CIF O.uF and cther products involý-ing redox reactions. S3iai~arIredt x reactions wire encountered in other ClFx-AsF3 5 systems~. Hydrolysis of

lKT-~rCFL agutpjin hp ionnf ne Dh~p ouzt to be a KF-KClFh hydraw

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