79 39 INVESTIGATION OF GASEOUS C LORINE COMPOUNDS BY N -R Y vRBSORPT ION SPECTROSCOPY(U) BOEING AEROSPACE CO SEATTLEMA F N LYTLE ET AL. 26 MAR 67 TR-5 NMf14-03-C-02070RL.SFIED F/O 7/4ClllliniimnML

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Arlington, VA 2221711. TITLE tInciude Security Caaification, Investigation of

IChlorine CAmounds by X-ray Absorption SpectroscopyPERSONAL AUTHOR(S)

.rrel, W. Lytle, Robert B. Greegor, Edward C. Marques, and Donald R. Sandstrom

I 3. TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Yr.. Mo.. Day) 15. PAGE COUNT

Technical FROM SePt.'86roAug.' 8 7 3/20/87 1016. SUPPLEMENTARY NOTATION

S Submission to 1986 SSRL Activity Report17. COSATI CODES 18. SUBJECT TERMS (Continue on revuere if .ecesgary and identtfy by block number)

FIELD GROUP SUe. G. X-ray abscion-spectroscopy, chlorine edge, e-yield detection,flucrescence gaseous chlorine, carbon tetrachloride, ethylene chloride,double resonance (T ,a), C-Cl band distance.

19. ABSTRACT (Continue on reverse f necesear and idenatfy by block number)

See attached.

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Contract N00014-85-C-0207

R&T Code 413a001---01

Technical Report No. 5

INVESTIGATION OF GASEOUS CHLORINE COMPOUNDSBY X-RAY ABSORPTION SPECTROSCOPY

by

Farrel W. Lytle, Robert B. Greegor, F,%,ession ForEdward C. Marques and Donald R. Sandstromt -TIS ci,&i

DT'IC TABUllannouncedJust ification __

Boeing Aerospace Company ISeattle, Washington 98124 ByDitribution/

Availability C

Avail and/or

Dist Special

published in 0 -1986 SSRL Activity Report

Stanford Synchrotron Radiation Laboratory Q"

March 1987

Reproduction in whole or in part is permitted forany purpose of the United States Government

*This document has been approved for public release and sale;its distribution is unlimited.

-6

Proposal No. 944

INVESTIGATION OFGASEOUS CHLORINE COMPOUNDS BY X-RAY ABSORPTION SPECTROSCOPY

C , " o -) WF.W. Lytle, R. B. Greegor, E. C. Marques and 0. R. Sandstrom

The Boeing Co., Seattle, WA 98124/ ,l.' G. P. Huffman, F. E. Huggins, University of Kentucky, Lexington, KY 40506

W u meaud the x-/ay absorption spectra of gas-

( eous I CCIT) and e4C2C12 The samples were mixed.witJi f at approximat-iT oO0 ppm concentration and

_jffowed through the detector/sample cello.$. This 4 3consisted of a cavity In a 1.3 cm Lucite block coy-

ered front and back with 6(3 aluminized Mylar win- I

- dows. At the center was a thin electron-collecting, 0 gridofa.kjiesh. The windows were connected to -45 V

V -~ *'1 lb.20.--while the positive battery terminal was connected to .'the ground of the electrometer. e e-yield signal c \

was collected at 10 gain from he mesh. ccAbsorption and fluorescent mode data were detu

, , 0CC

to reduce harmonics. A 1 m entrance slit gave an - --- --------------------

energy resolution AE/E=0.5 eV(2). Early data for C12gas was published by Stephenson et al.(3). Their 4data was obtained in the absorption mode, cranking .-

the spectrometer and recording the data by hand. Al- 2dthough their first peak was attenuated by the thick- ENERGY. eVness effect, the spectra are comparable with ours to Fig. 1 Near edge spectra of gas phase C 2 , CC14,

10 eV. In the region from 10-24 eV we found an in- H4C2C12 and Ar all normalized to unit edge

teresting double series resonance which is blown up Jump. The it and a maxima are indicated.in scale in the inset to Fig. 1. By analogy to N2 The Ar Is3p edge is marked by the vertical

data(4) these features are due to transitions to un- arrow. A region of the C12 spectrum is

filled orbitals of the molecule in its various blown up in the inset to illustrate acharged states. double series resonance.

The data of Fig. 1 were placed absolutely in

energy by noting the impurity Ar is resonance at

3203.3 eV(5) at the end of each scan. The zero ofNY

energy of Fig. 1. is 2833.4 eV. The n resonance I C1peaks were located at -2.6, 0.0 and 0.2 1 0.2 eV for .Cl2, CCl4, and H4C2C12, respectively. The areson-

ance energy as defined by Sette et al.(6) moves with 44bond distance as noted for smaller molecules(6). The

Ar K-edge spectrum is shown for comparison, E0.3203.3

Note that no feature similar to the Ar double elect-

ron ionization (ls3p) at 23 eV (the vertical arrow)

occurs in the Cl spectra. The EXAFS of Fig. 2 wasterminated by the ubiquitous Ar impurity In the x-ray .path. Considerably more EXAFS could be measure if K,

this could be corrected. The Cl-Cl phase-corrected.._ Fig. 2. Normalized EXAFS of gas phase Cl2 , CC14 and

, . H4C2C12 •

1/9

I

References

1. F. W. Lytle et al.. "GAS PHASE X-RAY ABSORPTION

SPECTROSCOPY WITH AN ELECTRON YIELD DETECTOR",

presented at Ifth Int. EXAFS Conf., Fontevraud,

10. France, July 1986.UC 2. F. W. Lytle et al., Nucl. Inst. Methods 226, 542

(1984).3. S. T. Stephenson et al., Phys. Rev. 84,806 (1951).

4. M. Nakamura et al., Phys. Rev. 178, 80 (1969).

A. Bianconi et. al., Chem. Phys. Lett. 58, 263

(1978). A. P. Hitchcock et al.. J. Elec. Spec.

Cl 18, 1 (1980).5. R. D. Deslattes et al., Phys. Rev. A27, 923 (1983)

6. F. Sette et al., Chem. Phys. Lett. 110, 517 (1984)

CO14

H4C2C12

2 6RADIAL DISTANCE,

Fig. 3 K1, Cl-Cl phase corrected Fourier transforms

of gas phase Cl2 , CCl 4 and H4C2C12 all plotted

to the same scale.

7 Fourier transforms are given in Fig. 3. The Cl peaks

were found at the expected distances of 1.99, 2.90

and 2.97 R, top to bottom. The shorter Cl-C bonds

are clearly resolved and could easily be analyzed.

Any sample with appreciable vapor pressure may be

introduced into an ion chamber with a diluent gas.

With a long beam path a sensitivity of 1 ppm is

possible. This remarkable sensitivity occurs be-

cause of the nominal 4n collecting efficiency.

Research funded by NSF and ONR

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