USE OF SULFUR

CLAUDk
Drptrrttttrttt

THE AND
VkILL0N
01 Cltetttrstrb

SALET PHENOMl3NON IN THE DETERMINATION OF PHOSPHORUS IN AQUEOUS AND ORGANIC SAMPLES

and
Utter

JC)llN
cwttv

Y
01

PARK*
Ilrtu\tott. Ilorr\tott.

7(*ucc\ 77004 (L 7 4 )

(Kccctvcd

Xlh Dcccmbcr

1971)

If a solution aerosol of some sulfur compound IS lntroduccd Into a rclatlvcly low-tcmpcraturc. fuel-rich hydrogen flame. and a cold obJcct IS placed near the flame core. an Intcn\c blue cmlsslon 1\ obscrvcd near the surface of the object. A slmllar cffcct occur4 with phosphoru\ compounds. 111this case rcsultmg In a green cmlsslon. Thcsc cmlsslons arlsc from the S z atld H PO molcculcs formed an the flame gases chilled by the rclativcly cold wall of the object Apparently the cold wall IS ncccssary for the formatlon and/or excltatlon of the S, or HP0 molcculcs. but it dots not appear to matter what the object IS made of Salct first obscrvcd this phcnomcnon over 100 ycurs ago, and no further lnvcstlgatcd the spectrum of dcvclopmcnt took place until 1907 when Gcutcr phosphorus 111flames. probably HPO. Much Inter. Fowlcr and Vadya dcscrrbcd the S2 spectrum. from the flame spectrum of carbon dtsulfidc Ludlam studrcd the and Idcntlficatlon wcrc wrong. Rumpf HP0 spectrum. although his analysts Invcstlyatcd the green bands of phosphorus (H PO) which hc erroneously attrlbutcd to PO Brlnslcy and Stcphcns obscrvcd the blue S2 bands at very low conccntratlon Invcstrgatcd the flame spectra 111 coal-gns flame Later. Sugdcn and Dcmcrdachc a of sulfur spcacs. and Lam Thanh and Pcyron Invcstlgatcd H PO cmlssIon Fcnrmorc and Jones attcmptcd to anulyzc the mcchanlsm of formatlou of HP0 In the airhydrogen flame Crtdcr lo rcdiscovcrcd Salcts phcnomcnon and developed a sensltlvc, sclcctrve dctcctor for monltorlng sulfur dloxrdc and sulfurrc acld In air samples Blody and dcvlscd gas chromatographlc dctcctors for sulfur and phosphorus based Chancy the dctcrmtnatron of sulfur inon the phcnomcnon. Dagnall et trl l2 Invcstlgatcd troduced as a solution aerosol into hydrogen flames diluted with mtrogcn or argon. and Iatcr completed an equally thorough study wtth phosphorus Syty and Dean Is made scvcral very mtcrcstlng obscrvatlons m the HPO. PO and S2 band cmtssions from shlcldcd ar-hydrogen and unshielded oxy-acctylcnc (PO only) flumes. Bowman and Bcroza I 5 used a comblnatlon of the Brody and Chancy dctcctors for slmultancous sulfur and phosphorus dctectlon In gas chromatographlc effluents. Fuwa and Vallcc used a long-path flame cell for momtormg SO2 molecular absorption. Aldous et al l7 mvcstlgatcd the cmlsslon spectra of organo-sulfur and organophosphorus compounds m mlcrowavc discharges. for possible use with gas chromatographic detectors
address

of this

type.
of

Brodle Chcml\try,

placed

a chlllcd

wall on a conventional
Paradcna. CalIf

* Prcwnt
91103. USA Atut1 Chttl

Dep~rtmcnt

CAlform~ Instltutc of Technology.

Ac I((. 60 (1972)

294 41ot burner

VLILLOl!

PARK

and vicwcd the SZ and I IPO cml\\lon from the rcglon near the cold wall, using both ;ur hydrogen and nltrogcn -hydrogen cntralncd ;ur flames Taylor et trl I used atomic IIIKS produced 117mIcrowavc dlschargcs to analyze for sulfur by atomic CIIIISSIOII and absorption Sulfur and phosphorus dctcrmlnttlons arc normally drfficult or at Icast IIIconvcnIcnt analysts to pcrfol m on many organic and aqueous s,amplc\. involving ctc The Salct phcnomcnon \uch proccdulcs as ash~ng, rcactlng with rcagcnts. appears to offer ;I convcnlcnt means of anrllyz~ng for thcsc two clcmcnts, III a short pa-rod of time, at high scnsitlvlty diid with few Intcrfcrcnccs Analysts for sulfur arc. of course. tmportant III .gawous samples, \uch as ait-, and cvcn more \o 111 orgcinlc samples. one dcwlcs Cl rapid. hqulds such as g<lsol~nc and fud 011s With .lqucous scnsltlvc mcuns of sulfur analyses III water pollution studlcs Phosphorus analy\c\ arc important in aqueous samples to dctcrmlnc the cxtcnt of pollution by phosphltc detergents and phosphate wustcs from vuIons rndustrlal cfflucnts, or 1x1 organic samples for pcstlcldcs, to name but ;I few appllcatlons. Our objcctivcs III this work wcrc to Invcstrgatc this phcnomcnon furthor. vcrlfy some of the obscrvatlons made prcvlously by others. take ;I bllcf look at potcnttal Intcrfcrenccs, pcrhap$ shed some Ilght on the mcchanlsm of molcLulc production. and apply the tcchnlquc to an:~lyscs of aqueous and orgunrc samples. WC did not strlvc to ~K~ICVC the hlghcst possrblc scns:tlvlty, bccausc the apparatus used Icsultcd in scnsltlvltlcs which could bc surpassed by high apcrturc systems Nor was a rigorous and thorough study made of cmployinp Intcrfcrcncc filters Intct fcrcnccs bccausc, as will bc shown, the phcnomcnon I\ not yet well understood. conscqucntly. attempts at this point to optlrnlzc and crltlcally cvuluatc the Ilmltatlons of the phunomcnon would not bc of g-cat value.

Applolrtlrs

The spcctromctct system used conslstcd of 1 0 5-m focal Icngth Ebcrt monochromrltor, having LLI~ apc~ turc rutlo of l/X 6 The grating used had I I X0 gt ooves/mm. ~152 111111 52 mm ruled ;ue;t. blazed for 300.0 nm, and a dlspclslon x of I .6 nm mm in the first order. Slits wcte unllatcrally adJustablc, with curved JEWS, and width and hcght wcrc continuously varlablc over 0 005-0.4 mm and O-20 mm. rcspcctlvcly The photomultlpllcl detector cmploycd was a Type R 106 (HTV) with qual tz cnvclbpc. and was powacd by a rcgulatcd d c. power supply The convcntlonal dynode rcslstor 11rangcmcnt was cmploycd. and overall voltages bctwccn 3.50 and 900 V WCIC used, ~1srcquu-cd A mechamcal chopper modulated the emlsslon at 330 Hz and the rcsultmg a c signal was atnpllficd by a phasescnsltlvc, synchronous amplrfier tuned to the same frcqucncy (Model 120. Prmceton Appllcd Rcscarch Corp. Prlnccton, N. J ) Tlmc constants bctwccn 0.3 and 3 see wcrc used, and the output was drsplaycd on a 25-cm strip-chart rccordcr The rcfcrcncc slgml for the synchronous dctcctor was gcncrutcd by the clrcult dcscrlbcd prcvlously Bccausc of the low backgt ound cmlss1on of the rcglon vlcwcd, and the f/8 6 apcrturc ~atlo of the monochromator, the maximum spectral bandwidth of 0 64 nm was used for all mcasurcmcnts To avold mcasurlng room light, the burner-sheath assembly was mounted vcrtlcally 111an cnclosurc. open at the top and bottom. and

THE

SALkT

PliENOMENON

295

cquippcd with a light trap on the back side matched to the aperture of the monochromutor and cntrancc optics The s,unplc introduction sy\tcm consisted of a hcatcd chumbci. mto which sample solution was spr,tycd by a pncumutlc ncbulizcr. conncctcd to a modilicd Fricdrichs condcn\cr for solvent rcmovul The rcsulttnp dry rla-osoI was conducted rnto the burner by the ncbulizing ga Thl\ cffictcnt system was llkc the one dcscrlbod gil\ pressure wa\ 40 pst. rcsultmg 111a gas flow carlicr z I. cxccpt th,lt the ncbuhzcr rate of 1 72 1 niln _ of air or 1 50 I min of ill go11 oxygen. and a solution uptukc rate of 1 1 ml rnin _ Ch,unbci hc,lt input was 288 W and t!lc condcnscl coolmg water wit\ rnaintaincd at 10 A direct system was Ao tried, conslstlng of the ncbulizcr and unhcatcd chutnbcr, with the aerosol conducted directly into the burner This \ystcm had poor cfficlcncy and rcsultcd in noisy signals. hcncc ,111mcasurcmcnts wcrc made with the hc,ltcd chamber- condcnscr \ystcrn

emlsslon

Vaitous configurationr for tho burners and sheaths wcrc tried, but the one shown in Fig 1 wa\ used for the mcasurcmcnts rcportcd hcrc Other configuratrons trlcd conslstcd of dtffcrcnt sheath dimensions. water-cooled :md air-cooled sheaths, sheaths mudc of botosillcatc gl,lss (shown), fused silica. copper, stainless steel. and one configuration in which the outer sheath was lcvcl with the burner tip and had provisions foi introducing a lamin~u- flow of inert gas (Ilkc argon) to cxcludc air cntrainmcnt by the flame Dimcnstons of the borosilicatc glass sheath used wcrc: I8 cm length. 2 5 cm o d and a l-cm opcnlng at the top No auxiliary cooling was provtdcd. The burner was fabncatcd from fused silica tubmg, with d 3mm o d. mncr tube and an 8-mm o d outer tube The burner was mounted in the sheath with 11 rubber stoppcl. with the burner tip about 5 cm above the bottom of the sheath Gas flow rates wcrc monitored with !5-cm, dual-range rotametcr% callbratcd Optimal flow rata were found to be as by the proccdute dcscrlbed previously2 fuel-rich us could bc obtalncd, maintaintng the flame within the sheath. This obscrvation agrees with that of Syty and Dc~m~, and the rates used wcrc : 1 72 1 rnin - of air and 2 20 1 rnin - of hydrogen for the air-hydrogen flame, and I .26 1 min - of argon, 0 24 1 inin - of oxygen and 2.20 I mm - of hydrogen for the argon-oxygcnA,ttrl C/lIHl nc Iti. 60 (1972)

296

VEILLON.

PARK

hydrogen flame In the latter, the argon and oxygen wcrc mlxcd and used In the place of all In the ncbullzcr Th15 synthctlc iur mtxturc, with argon rcplacrng the nitrogen. corresponds to a 16<, O2 -841<, Ar mixture, which was found to gave about 2-fold hlghcr \cnsrtlvlty and about X-fold lower dctcctlon lrmlts (owmp to much lower IIOISC) for both S2 and H PO cmls\ion The total mixture flow rate of I .50 I mln raultcd of air Bccausc of the approxttnatcly &fold lower dctcctlon Ilmlt, the Ar--OZ mtxturc was used throughout

The burner and sheath dlmcnslons wcrc found not to bc crltlcal Very llttlc dlffcrcncc tn srgnal lcvcls wcrc obtalncd when shcoths of boroslllcatc glass, fused s~llca and copper wctc used When a lamlnur gas sheath of argon was used to cxcludc cntralncd air. but wlthout II cold wall, the cffcct could not bc obscrvcd Cooling of a fused s~l~cashcath cvcn further with ;ur or ;LwatcrJackct h,ld llttlc cffcct Conscyucntly. all mc;l\urcmcnts rcportcd arc for the fused silica but ncr and borostllcatc glass sheath dcscrlbcd above and 111Fig With the configuration shown FIN 1, cmt\slon by S, and PO spcc~cs OCCUI t-cd outsldc the flame cow near the sheath wall Intcnslty was grcutcst at the bottom. slightly above the burner tip, and this was the rcglon v~cwcd A I I rmagc of the flame was focused onto the monochromator cntrancc slit. off-ccntcr 50 ;a not to view the 111nc1 COIIC of the flame, and the burner assembly posltton was acijustcd fat maximum signal-to-nolsc (S/N) ratlo Both IIOISC and background WCIC low, so that this posltlon usually corrcspondcd to maximal ~gnal as well The cmIsslon spectra of S 1 and H PO obtalncd wrth the apparatus dcscllbcd above and the air-hydrogen flame arc shown 111Fgs 2 and 3. rcspcctlvcly The 384.0-nm S1 and 526 5-11111 f-l PO band heads wcrc used 111 thl\ Invcstlgatlon , howcvcr. any of the labclcd S-, bands gave slmllar results

The S, cmlssion

Intcnslty

was obscrvccl

to vary as the squat-c In

of the sulfur

,I.0

WAVELENGTH,nm

420.0

4)

WAVELENGTH,

nm

5800

THE

SALET

PHENOMENON

297

conccntratlon proportional I=hCY which

below 10 mg ml - The cmlsslon intensity (I) of any spcc~cs ~111 bc to some power (X) of the conccntratlon (C) of the cmlttlng spcacs

15 cqulvalcnt

to

Plotting log (signal) z~s log (sulfur concentration) results 111il Itncar curve with a slope of exactly 2 (F1.g 4) Beyond about 10 mg ml - , d change of slope occurs. indicating 1 change tn the mcchanlsm of formation of the S, spcc~cs
TABLI I

lI,SOJ N,I,S,O, CISO, NISC N (Nlj.,),SO, Mg\OJ

22 23 24 20 22 50

The rcsponsc was found to bc csscntlCllly Indcpcndcnt of the sulfur compound cmploycd (Table I) For thcsc mca\urcmcnts. the sulfur conccntratlon m cuch cast was the same (50 /lg ml - ) and the 384 0-nm band head was used Rcad~ngs agreed m the cast of magncslum sulfate. which gave abnormally high to + IO,, cxccpt rcadlngs bccdusc of atomic cmlsslon by magncslum at 383.0-nm This Intcrfcrcncc by magncslum dlsappcarcd when the 374 l-nm Sz band head was uccd. with llttlc loss 111\cnslttvlty Normally one might not cxpcct that magncslum atoms would bc produced III this low-tcmpcrnturc flame. slncc the MgO formed when magncslum

1600

1200

400

02

04

06

04

1 0

log (S,

pg

ml-)

PERCENT

ETHANOL

(vol.)

4 Log tr:itlon

i-lg

log plot of re4ponw

I 9 sulfur conan-

F1.g 5 Effect of orgunlc

solvent

on S, cmlsaon

38
sulfatc

VPILLON.

PARK

dccomposcs should dtssoctatc very slowly Howcvcr, Hall\ and Townshcnd 3 have shown that Mg atom\ and OH arc produced by the gas phase rcactton of H and Mg0. and Bulcwtcir and Sugdcn have suggcstcd the tnduccd chcmtlumtncsccnt rcactton

H+Oll+Mg

H20-i-Mg

from thctr obscrvutton of strong magncstum cmts\ton tn nttrogcn oxygen -hydrogen flame\ From tht5, the rcductng condttton\ wtthtn the \hcath. and the apparently low tcmpuratutc of the argon-oxygen hydrogen flame used. tt \ccrns ltkcly that approctable tn;tgncbtum cmtsston would occur. The result\ shown tn Table I gcncrally agree wtth the obscrvattonr made by BrodtcX. but both Syty and Dean l4 and Dagnall et (11 2 obscrvcd varytrrg stgnCtlb for dtffcrcnt salt\ contatntng sulfur. Stncc the tcmpcraturc tn the rcpton v~cwcd could not bc rcltably mcasurcd no cxplunatton of fhcsc dtffcrcnccs tn obscrvcd salt cffccts can bo offcrcd In organtc solvents. the S2 cmtsston was constdcrably less than that obtatncd tn aqucou5 soluttons Wtth the alcohols. 1hc scnstttvtty dccrca\ccl by about 4-fold. whtlc tn n-butyl acctutc tt dcctcuscd by about 30-fold As an cxutnplc. the S, ctnl\\ton tntcnstty from sample soluttons tn ethanol was about 4-fold lower than that obtatncd wtth aqueous satnplcs Whtlc thts was not a large overall cffcct. the dcprcqston wit\ rapid at low conccntrattons of cth,tnol tn water--cthitnol tntxture. as shown tn Ftg. 5. The dccrcasc appcarccl to bc cxponcnlial and rcachcd tts final value at about lo;, flame tcmpcraturc. but (volutnc) clhittlol III W~~CI Pc~haps tilts IS due to tncrcascd the sharp tnltial dccltnc tndtcatcs that organo-radtcals produced III the fltmc tnay play cl tnajor role in lowcrtng the S_ cmtsston and/or formatton , Gtlbcrt has suggcstcd that the cnhancctncnt of the HP0 ctntsston by a shtcld IS due not to the aclton of the surface as a third body but to the cooling cffcct of the wall or of an cntratncd tncrt gas Syty and DcantJ \uggcst that the third body can bc ctthcr nttrogcn or the shtcld wit11 Wt1h regard to S2 cmtssion. whtch m,ty bc analogous, tt was found that shcathtng the burner wtth argon gas, wtth the cut-off sheath mcnttoncd carltcr, to the cxtcnt that no air cntratnmcnt rcachcd the arca vtcwcd, prcvcntcd 1hc S2 cmtsston Wtth the burner opcraftng wtthout the sheath, lnsct ttng a cool ObJcct tnlo the flame rcsultcd tn S_ ctntsston , at the surface of the object At Icitst for sulfur, thts would tndtcatc that prcvcnttng atr cnt~atnmcnt IS not lmpot lant, but cooltng of the flitnlc ts From the prcscnt results wrth sulfur, tt would LX cxpcctcd that the cooltng IS not the only rcqutrcmcnt. but that ;I thttd body (CJ a CJ. cold wall) IS ncccssary for Ihc formatton of S, Obvtously. much more work IS nccdcd. stncc thqsc lcsults nctthcr vcrtfy nor nulltfy the catltcr results on phosphorus

One obvious appltcatton of S&ts phcnomcnon would bc to the dctcrminatton of sulfur trt fuels, espeaally tn lht\ ttmc of concct n about alt pollutton, and constdcring the corrostvc cffccts of sulfut oxtdcs tn high-sulfur fuels for dicscl and Jet cngtncs At the prcscnt stage of dcvclopmcnt. the analysis of sulfur m organtc mcdta rcprcscnts a non-tdcal situatton. owtng to the rcduccd scnstttvtty of the method in organtc mcdta. but to test the m&hod and apparatus dtscusscd hcrc, analysts for sulfur tn pctrolcum fracttons was undcrtakcn Three analyzcci samples of known

THE

S4LF.T

PHENOMENON

299

sulfur content wcrc obtalncd and analyzed by the standard add9t9on techn9quc. w9th a standard soIut9on of carbon dlsulfidc 9n ethanol The samples consisted of a kcros9nc fraction of 322 [cg S ml - . a 200-250 fraction containing 45 6 /cg S ml- . and ;I rcsldual fuel 091 containtng 2 14 :, S. All of these samples had bcc99 analyzed by cotlvcntlonal tcch999qucs (e CJ., m9crocoulomctrlc) 9n five laboratoncs. The kcros9nc sample and the rcs9dual fuel 091 sample wcrc d9lutcd with ethanol 10 1 and 1000: 1. rcspcct9vcly. bcforc analys9s The results of the analys9s arc shown 991 Table II. The agrccmcnt IS qu9tc satisfactory cotls9dcrlng that an unideal system of reh9t9vcly low apcrturc was used. as well as an organtc solvent system. with the result999g dccrcasc 191 scnsitlvlty
TABLI II

frdctron 200 250 Kcroslnc

I~C!SldU.ll

456

ppm

44 p p m 37Oppm 2 I I,,

- 3 5 , -t 2 5,,

322 0 p p m
2

fuel 011

94,,

- 2 (I,,

Var9ous phosphorus compounds, such as phosphoric ac9d and metal phosphatcs, wcrc dctcrmlncd 191 aqueous solutions Esscnt9ally the same sctls9tlv9ty was obtarncd 9n each cast. w9th the cxccpt9o99 of alkal9nc earth salts, wh9ch dcprcsscd the HP0 cm9ss9o99 Organtc solut9o99s of phosphor9c acid and triphcnyl phosphltc in methanol. ethanol. propanol, n-butyl acetate, acctonc, methyl 9sobutyl kctonc. cthylbenzcnc, c *md scvcral alkancs wcrc compared In each case, the HP0 cmissio99 from the two phosphorus compounds was the same (with9n loy,),), but the scns9ttv9ty with thcsc organtc solvents was 2- and 5-fold lower than with aqueous solutions It should be po9ntcd out that organ9c solutions w9th solvents havi99g low flash po9nts such 99s ketones, ethylbcnzcnc and alkancs, arc datlgcrous when asp9ratcd into the hcatcd glass chamber 9n the presence of oxygen. In these casts, 9t is rccommcndcd that argon (or nitrogen) bc used as the nebullztng gas, and the ncccssary oxygen be added downstream from the conderlscr. No problems were encountered w9th the alcohols or n-butyl acctatc. Add9tro99 of the ncccssary oxygen beyond the condcnscr 9s dcs9rable s9ncc optimal cond9t9ons require a pcrccntage of oxygen less than that 9n atr. Of course. use of a convcnt9onal. unhcatcd chamber would elim9nate the problem, but the loss 9n dctcction limit amounts to about S-fold with many solvctlts. Rcsponsc in all casts was 19ncar wrth phosphorus conccntrat9on, up to at least 100 /cg ml-. The detcct9on 19m9t for phosphorus 9n aqueous solutions was 1 3 pug ml- 991 organrc solvents.
Analysis of mxctlcde

A commcrc9al methyl-6-pyr9m9ci999yl)

9nsectic9dc containing 0.50< O,O-diethyl O-(2-9sopropyL4phosphorothloate (Diaz9non) 999 a pctrolcum solvent was

300

VEILLON.

PAKK

dllutcd 50: 1 with ethanol and analyzed by the standard addition method, with standard solutions of phosphoric acrd In ethanol. The average value for 10 samples was 0 49(, Dlazlnon, with a rclatrvc standard dcvlatlon of 4 7 I<,
CONCLUSIONS

The results rcportcd hcrc do not cxphun the role played by the sheath wall In SZ and H PO cmls5lon and/or formation. Nor is the role of the gas species clear, although this seems to have ;I much smalIcr effect than the sheath wall. The dcprcsslon of S2 and H PO cmlssion by organic spcacs 15qurtc cvldcnt, but It IS not yet clear if the cffcct IS due to tcmpciaturc or organo-radicals produced 111 the flame. Ail of the obscrvcd cffccts, and the dlffcrcnccs reported, lndlcatc that much more work IS nccdcd on the S&t phcnomcnon. Elucidation of thcsc many points would allow optlmlzation and evaluation of the tcchnquc, and Icad to a practical. rapld, convcnicnt method for detcrmmmg both sulfur and phosphorus m a varlcty of samples at high scnsltivity. The authors wish to thank Sam Hastmgs and Tom Hcndrlx of Humble 011 Company (Baytown. Texas) for the pctrolcum samples. Special thanks arc also due to Paul Gtlbcrt of Beckman for his assIstancc In obtaining rcfcrcnccs to carllcr work on the phcnomcnon Th15 work was supported in part by the Petroleum Re5carch l.und admimstcred by the Amcrrcan Chemical Soaety, in part by the Robert A Welch Foundation and In part by the NatIonal Science Foundation This work was taken tn part from the Ph.D. dlsscrtatlon of J Y P (May, 1971).
SUM MARY

The history of the Salet phenomenon IS summarlzcd. Various cxpcrimcntal configurations are studied for the mcasurcment of the S2 and HP0 emlsslon from dlffctent sulfur and phosphorus spcacs in low-tempcraturc flames. Analysis of petrolcum fractions for sulfur, and Insecticides for phosphorus 15 discussed

On pr@sente un brcf historquc du phCnomknc dc Sulet Dlvcrscs conflgurattons exptirlmentnles sent &tudl&cs pour la mesure dtimisslon SZ et HP0 de cllff&-ents compos&s sulfurcs et phosphor&s, dans des flammes ii bassc temp&raturc. On exammc Ianalyse de fractions dc petrole pour le soufre, ct dlnsectlades pour le phosphore.
ZUSAMMENt-ASSUNG

Es wird an hlstorlschcr ijberbllck fiber das Salet-Phhnomcn gegebcn Vcrschtedene experlmentelle Anordnungen werden untersucht fur die Messung der S2 - und HPO-Ermssion von verschledenen schwefel- und phosphorhaltlgen Spezles m Flammen medriger Temperatur. Die Analyse von Erddlfraktlonen auf Schwefel und von Inscktiziden auf Phosphor wn-d dlskutlert. rlrrtrl C/II/U A<111. (1973) 60

THE RLFI I Ci 73 2 P 3 A 4 I: 5 K 6 F 7 T X M 5) C IO W II S I2 R I3 R I4 A I5 M I6 K I7 K I8 K IY H 10 C 21 C 21 C 23 D 24 I 25 P
Atrcrl

SALET RENCCS

PHENOMENON

301

%lct. ( I< hX (1X6)) 404 fj1t// so< C/n,,, Ft I 1 (I SOY) 302 IfI, P/I\\ 177 (1X69) I71 ( fi. (1871) 1056 Gcutcr. % WI\\ Phofoqr. 5 (lYO7) I Fowlcr and W M Vadya. Proc R Sot (f.omh). A I32 (I93 I) 3 IO H Ludldm, J C /~,ttt P/IV\ , 3 (1935) 617 Rumpf, % PII\ 5 Clrta,~. B38 (193X) 469 Brln\lcy .md S Stcphcns. Ntrfttrca. I57 (I 946) 622 M C;ugdcn and A Dcmcrd.~chc. Ncr/rtrr. I95 (1967) 596 L,rm Th,mh ,~ncf M Icyron. J C/IPIII P/IV\ , 59 (1962) 6%. 60 (1963) 1789. 61 (1964) I.531 P Fcnlmorc and G W Joncs. Comh14~1 F /tr~~w. 8 (I 964) 137 L C rldcr. At114/ C/uw . 37 (I 965) 1770 S Hrody .;nd J I- Chancy J <;(I$ C'hrotmttru~r . 4 (1966) 42 M D,lgn,lll. K C Thompson and T S Wet. rl~~trl\~sr 92 (1967) 506 M I>,~gndl. K C Thompson and T S Wet. Arrcdv\t, 93 (1968) 72 Syty dnd J A &an. Appl Opt. 7 (lY6H) !33l C ljowm.in ,ind M &I of,:. Arurl Clreu~. 40 (1968) 144X Fuw.1 and Is L V,dlcc Amr/ Chw 41 (1969) I88 M Aldour. H M D.lgn.lll S J Pratt and T 5 West Atrtrl Chenr . 41 (1969) 1851 G 13rodIc. Krsontrnce fade\. Vol 1. No 3 Vx1.m Tcchtron. W.llnut Crcck. Cd~f. I96Y I Tiylor. J I-l G~b\on and R K Skogcrboc And C IJLWI 42 (1970) IS69 , Vc~llon ,~nd M M,lrgo\hc\, Spa trre hrm AC tu. 2313 (196X) 503 Vc~llon ,111d M M:trgo+x Spa trot hrm Ac tu 2313 (1968) 5.53 Vc~llon and J Y P,lrk. Arut/ Chm . 42 (1970) 6X4 .I l_(,ills .md A Town\hcnd Am/ C/IWI Ac ta 36 (I 966) 27X M l~ulcwrc/ ,11x1 7 M Sugdcn. Trtrtls I cwcctltr~ Jot 5s (1959) 720 -r Gllhcrt. prlv.ltc CommunICatton
Cli~rtr Ac tu. 60

( lY72)