DTIC ADA432801: Reaction Chemistry of HN3 with HF, Halogens and Pseudohalogens

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by  Defense Technical Information Center

RREEAACCTTIIOONN CCHHEEMMIISSTTRRYY OOFF HHNN WWIITTHH HHFF,,
33
HHAALLOOGGEENNSS AANNDD PPSSEEUUDDOOHHAALLOOGGEENNSS
WWiilllliiaamm WW.. WWiillssoonn,, KKaarrll OO.. CChhrriissttee,, JJeerrrryy
AA.. BBooaattzz,, RRaallff HHaaiiggeess
EERRCC,, IInncc aanndd PPrrooppeellllaannttss BBrraanncchh,,
PPrrooppuullssiioonn DDiirreeccttoorraattee,,
AAiirr FFoorrccee RReesseeaarrcchh LLaabboorraattoorryy,,
EEddwwaarrddss AAiirr FFoorrccee BBaassee,, CCAA
aanndd
UUnniivveerrssiittyy ooff SSoouutthheerrnn CCaalliiffoorrnniiaa
LLooss AAnnggeelleess,, CCAA
DDIISSTTRRIIBBUUTTIIOONN AA:: AApppprroovveedd ffoorr ppuubblliicc rreelleeaassee,, ddiissttrriibbuuttiioonn uunnlliimmiitteedd
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1. REPORT DATE 3. DATES COVERED
DEC 2004 2. REPORT TYPE -
4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER
Reaction Chemistry of HN3 with HF, Halogens and Pseudohalogens
5b. GRANT NUMBER
5c. PROGRAM ELEMENT NUMBER
6. AUTHOR(S) 5d. PROJECT NUMBER
William Wilson; Karl Christe; Jerry Boatz; Ralf Haiges 2303
5e. TASK NUMBER
0423
5f. WORK UNIT NUMBER
7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION
Air Force Research Laboratory (AFMC),AFRL/PRSP,10 E. Saturn REPORT NUMBER
Blvd.,Edwards AFB,CA,93524-7680
9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR’S ACRONYM(S)
11. SPONSOR/MONITOR’S REPORT
NUMBER(S)
12. DISTRIBUTION/AVAILABILITY STATEMENT
Approved for public release; distribution unlimited
13. SUPPLEMENTARY NOTES
14. ABSTRACT
N/A
15. SUBJECT TERMS
16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF 18. NUMBER 19a. NAME OF
ABSTRACT OF PAGES RESPONSIBLE PERSON

a. REPORT b. ABSTRACT c. THIS PAGE 27
unclassified unclassified unclassified
Standard Form 298 (Rev. 8-98)
Prescribed by ANSI Std Z39-18
BBaacckkggrroouunndd oonn FFNN
33
•
FN was first prepared and studied by J. F. Haller at Cornell
3
University in 1942
•
Very little work was done with FN because of its extreme
3
shock sensitivity and thermal instability
•
Characterized by D. J. Benard at Rockwell’s Science
Center in 1986, and by H. Willner at Universität Hannover in
1987 on very small scale
•
Yields were low, and purification and handling presented
major problems
•
Development of a safe high yield process for pure FN was
3
mandatory for studying its reaction chemistry
17th Winter Fluorine Symposium, St. Petersburg Beach, Florida
14 January, 2005 Approved for Public Release; Distribution Unlimited 2
Theoretical Heat of Reaction
for FN
3
• Thermochemical Calculation for Reaction of HN with F
3 2
to give FN (Jerry Boatz, AFRL)
3
[B3LYP(5)/6-311++G(2d,p)]
HN + F FN + HF
3 2 3
.
?H (0K) = -57.2 kcal/mol (±5 kcal/mol)
17th Winter Fluorine Symposium, St. Petersburg Beach, Florida
14 January, 2005 Approved for Public Release; Distribution Unlimited 3
PPrreevviioouuss AApppprrooaacchheess ttoo FFNN
33
•
Haller, Benard, Willner, 1942, 1985, 1986
Gas Phase, N Diluent
HN + F 2 FN + HF
3 2 3
Metal Catalyst, RT
•
Pankratov, 1966
NaN + F [FN ] + NaF
3 2 3
•
AFRL, 2002
HF
NF SbF + 2 HN [FN ] + NF + H N SbF
4 6 3 3 3 2 3 6
(N ) SnF FN + N SnF + N
5 2 6 3 5 5 2
D
17th Winter Fluorine Symposium, St. Petersburg Beach, Florida
14 January, 2005 Approved for Public Release; Distribution Unlimited 4
NNeeww RReessuullttss
•
Repeating previous preparations was found to give impure
products and yields of 50% or less
•
Carrying out the fluorination reactions in solution at low
temperatures resulted in quantitative yield and high purity of
FN
3
•
HF is not a good solvent because it protonates HN to give
3
H N +HF -
2 3 2
17th Winter Fluorine Symposium, St. Petersburg Beach, Florida
14 January, 2005 Approved for Public Release; Distribution Unlimited 5
RRaammaann SSppeeccttrruumm ooff HH NN ++HHFF -- iinn HHFF
22 33 22
N
H N + Cation N
2 3 * N
Vibn’l Modes
p.
o.
o.
n = 3137 cm-1 d
7 5
1
n = 3036 cm-1 N 4
1 -
N

n = 2291 cm-1 n
2 9
4
n3 = 1554 cm-1 NH2 H2 11 *
N
n nnn8456 ==== 1 1nn13oo40tt99 oo ccbbmmssdd--11 137 NHnasym2 036 NHnsym2 2291 N=Nn 1554 dsciss 1309 das * ** *
3 3
n = 415 cm-1
9
* = sapphire
4000 3000 2000 1000
W a v e n u m b eDrs (ccmm-1)-1
17th Winter Fluorine Symposium, St. Petersburg Beach, Florida
14 January, 2005 Approved for Public Release; Distribution Unlimited 6
NNeeww RReessuullttss ((ccoonntt))
•
Repeating previous preparations was found to give impure
products and yields of 50% or less
•
Carrying out the fluorination reactions in solution at low
temperatures resulted in quantitative yield and high purity of
FN
3
•
HF is not a good solvent because it protonates HN to give
3
H N +HF -
2 3 2
•
Suitable solvents are fluorocarbons that are compatible with
F
2
•
Product purity was established by Raman spectroscopy
17th Winter Fluorine Symposium, St. Petersburg Beach, Florida
14 January, 2005 Approved for Public Release; Distribution Unlimited 7
RRaammaann SSppeeccttrruumm ooff FFNN
33
iinn CCFFCCll aatt --3300°°CC
33
•FN3 was generated by fluorinating HN in CFCl and was
3 3
stable at ¡ -30°C
N
=
N

FN Vibn’l Modes n
3 4 N
3 N
n1 = 2034 cm-1 20 Np.
[n = 1085 cm-1] di.
2 6
5
6
[n = 853 cm-1]
3
n = 656 cm-1
4
[n = 246 cm-1]
5
[n = 504 cm-1]
6
[ ] hidden by
solvent peaks
4000 3000 2000 1000
Wavenumbers (cm-1)
D cm-1
17th Winter Fluorine Symposium, St. Petersburg Beach, Florida
14 January, 2005 Approved for Public Release; Distribution Unlimited 8
RRaammaann SSppeeccttrruumm ooff FFNN
33
iinn CCFF CCHHFFCCFF aatt --6644°°CC
33 33
N
N
FN Vibn’l Modes N
3
nn12 == 21003875 ccmm--11 037 N=Nn 085 N-Nn 653 di.p. 246 FNNd
[n = 853 cm-1] 2 1
3
n = 653 cm-1
4
n = 246 cm-1
5
[n = 504 cm-1]
6
[ ] hidden by
solvent peaks
4000 3000 2000 1000
W a v e n u mDbe crs m(cm--11)
17th Winter Fluorine Symposium, St. Petersburg Beach, Florida
14 January, 2005 Approved for Public Release; Distribution Unlimited 9