RU'I'N No. 7120 ~larch 1!J(,4

'l'lIllORY 01' (0I.UI<I.:LI FI.MII. PI~l)l.)UC'l'lUN

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DTIC

SELECTE"AUG 17 1982

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Aocession For

RDTN No. 7120 1-1al'ch 19M

s. NAVAL AMMUNITION DEPOTCrane, lndinna

AUNANNOUNCED

.. - - .NTIS GRM:!DTIC.TABUnalUloU11o!-Hl L1JustU1outiolL- -K·-t~~*VBY~ff;-Ol'\~'-l~ l u.Diotribut1ou!" ~

---A-~~llll\\J1l ity Codos - ..9_.- Avnil ulld/or ...- QJ

Dtst :';puu iUl

l'HUORY OF COLOIU::U FL/\l<W PIWllUCTION

Appr'oved for Public Re1easeiDistribution Unlimited

.y.~Research Chomical engineer

R~liARCH ANU U13VLil.OPMUNl' UliPARTMEN'I'

'lhc i"for~tion containod in this docua~nt repre,onts the opinionsof tho author and hence 'hould not be construed to represent theoHicial p<lUcy of any other individual or ol'il£nizati.on.

l'AtU..~ OF CONT~N'l'S

!tOTN NO. 71

AU::iTRAC'1'. • • . . · . · . . · . · . . · . . . . · . . . .Page

iii

1. PURPOSll . • . · · .. · • • • · · · · · · • • 1

2. INTROOUC1'ION • • • • • · · • • · · • • · · · · 1

3. COLOlUH> l1LA.M~ PRODUCTION. • · · · · • · · · · 2

a. Mothanbm • · · · · • · · • · · • · · · · 2

b. Spect1\81 vs limi t tcr. • · • • · · • .)

c. Emitters vs Temperature and l,;olor · • · · • · 6

d. Telllperature • • • • · • · · .. • · · • • • · · · · .,e. UneriY Definitions and Itc lationships. · · • · 8

f. lanhation. • · • • • • • · · • • · 12

¥. Ionization ~ut'for • · · • · · • · • 14

h. lhaloi tm Influences anu Gclct' Production · · · 1e>

(1) Barium-Strontium. • · • · • • · · • · 1b

(2) Alkali Metals • · • · · · • • · · • · · · 18

, (.l) Iioran • • • · · • · · • • • • · l~

(44) l'ha IliUlIl. · • • · • · • · • • • • · · 20

(5) Copper. · · • • • · · · • · · • • · • · 21

(0) ~kttt11 Halide Molcculo ~.ltdtut1on. 22

(7) Hdoaell Sde~tion,

23• · • · • · • · • · · ·i. CheMilUDinesconce • • · · • · • · • • · • · · · · 24

j • Emission Supprossion and Intensification. · · · · 25

k. FlamQ ~qu11ibria. · • • • • · · • • • • • · · • • 27

i

. . . . . . . . . . .. . . .• • • • • • • • • •APPI.lNUU 11

POSl'ULA'1'llS AND SUMMARY.

RDTN No. 71

\-laM 0

. • 28

31

la ~ 13:1

lb • 14b

. . . .

. .

. .. .

. . .. . . .

..• •

.. , . . . . . . .4.

m~pI:.1U~NCl1!). •

APPJ::NUIX J ••

ii

lUlTN No. 71

The theoTies and RttTibuto~ associated with tho pl'odut.tion of

colored flllmes are prosllnted. Particular attention is given to

flames containina strontium (red), barium (green), $odiwn (yQllow)

and copper (green ar blue). Thermal ex~itation of vapori~ed neutral

atollls, molecules and ions is correlated with the ol11iuion of lltolnir.:,

blind and icmic: spectra. "huc spcll:tra aru tabulated. The color

contribution of C-t)'pe cholllilUilinestence, lI. non·thermal ex.citation,

is described briefly.

l'he variability of ell1it~Clrs, olllhsions and color with th~ oper­

ating fl~o tOlilperatufe i$ discus~cd in relation to the thurmodynamic

properties of the reactants Ind th, products of combustion. l'helia

thct'lllal proportiea aro tabulated. Ionization is shown as a con·

tril.mtor to color dei~mO'tation. The use of an ioni:l:atiun buffer to

reduce ioni~ation is explained.

Uepemlini on fll1lll~ cOlldi t ions and the wctal bcin~ used, the in­

fluenco of halogons On thCl prodl.lction ot' COlOl' is dhlculisou. The in­

fluence 15 nut Il.1ways benlllHchl. Tho flue "quiUbl'iwu shift causod

by tllQ halOGens is dosc.ribed for oach ot' tho nlC,tals. Metals ami lI.nions

other than the hal1du il1't) dilcuuod in rolation to thl.lir ability to

intensify 01' suppress oahsion. lh. prefurred QlItittc;l'S fur ouch of

the webb are lbtod ancj id".li»tic postulate:> arc prestmtlild which apply

to tho proJuction of color in a flamu.

Hi

RUIN No. 7120 March 1964

1liEOR¥ Or COLORbO FLAMI:l PIWDUC'flON

a. 'rhc llurpol;0 of this pl'Q$cntation is to enullIerate and discuss

the theories Bnd Ilttributcs associ~tol.1 with tho production of C0101'0<.1

flwnos.

2. INTllOUUC'l'ION--rcr

a. lUlern ShU;;, " ••- colored flwn~ lJrodv ~tion is best:t with

Wl\l5Wll problems. These pl'oblolUS arc ellu$tld by the lad. of choicll)

in the available color-cnatival1 Illatcrials. the abllQrption of light by

the atlilosphero, the lilllits of clbcriminatiun by tho humlln uyo, I1nd the

I.:holJlhtry and l,hysics of tho Pl'QCCl!;S~$ and SUbstances involved. n '1'0

overcome the "lack. of choi~elf problem. additioniil cQloi:-crcll.tini

lIlatQrbls CoW be Jluf,l1c Ilvllilable hy inOTIl14llic, urianie am1 Illotal ..or~anic

chemical synthesis. In Qrdur to e~aluate new materials, it is necessary

to establish crit..'rill by whi.tb tho Iliaterial llay be jl.lIiKed.

b. If th~ chemistry and physics of tn~ processes involvud in coloreu

fl~~ production WOf8'Known in detail. it wa~ld not ue uiffic~lt to

~jtab1ish thll crJ.tcrh. Uecauso, howovcr. llOucn int'orl1latiun is not

availaule. it is often neces.ary to judi~ ~tcria15 by o~pirical methods.15

IUlern 5Ullllllarhed 1IOit of til. prob1e~ whon hu stated, "With incroasud

and fuller ~nowl.dae of the h~ats of formation. boilin¥ points and

diuociaUOd telllporatuf0$ of reaction products; am! with il:reator insii'ht

into the olllittinil c:haractul'btic$ ot· i"'~'oUll t'laJllOIl and at' liolid I,articlos,

we should tlventually be able to build fONulu in a lIlore.t rational lIU111UUf.

1

ROl'N No. 71

llven so, compromise, ~re unavoldable. ~~~imum heat output por unit volume,

hiihoSt stability, and lowest volatility of end products (lowest volatility

for white Baht, highost volatility for colored Baht). and desirablo be-

havior of original roactants, may not be attllinabl(l' in one formula".

Ono should not interpret this to moan that thar~ ~ a cumrl~to void of

knoll/ledgo of tlul chc~ical and physical prOCC5SC$ rQlated to colored lil'ht

production. <.:ertain facU and theorh' iUC available whi(;h Can be usod

first to describe tho procoss by which a colorou flall'J'l is produccl.! and

sQcondly to ovaluate un~ judie the value of new compounds intendod for usu

in colond lil.:ht fQrlIulations. It is for this PU1'POllil: that the theories

related to colored flame pro~u~tion wur~ collocted, formulated and discu$s~u

in this presentation.

~. COLOR131J FLAME PltOl>UCTION

a. ~If.'lchanhm

ll) Onl)' a tow at' thu lUore th.an 100 el4)lllonts aru used to impa.rt

a color to i pyrotechnic flame. lh~50 aro strontiw~ (rud), bari~\ (~ruen),

1;)capper (Kroon or bluo) and sodium (yellowJ. Ul1crn statui that lithium (reu).

uoron (iroen), thallium (are.n), rubi4i~ (red) and cesiuUl (blue) are also

strong color producers but that thoir use is not practical because of cost,

toxicity or the nature of the cOlJlpounl1s, All of these e10IUonts have cllrtaill

prop~rti~s and characteristics in common which ccntributQ to colored liiht

elllisdon.

el) <.:olorQd lhaos arc produced by excitation of lI'loUllic spectra.

At tho hiih temperaturo of the fllWlO, the salt or ~etal is v&porl~ed, and

part or all of the iascoU$ molQculos art prOaroJSlvely dissociatod to ~ive

2

ROTN No. 71

neutral atoms which are potentially emittin. species. Somo of the free

metal atolns unite with other raciicab or atoms present in the flallie. The

vupors of the neutral metal atoms. or of the molecules conri.inin~ the

uletal atolll~ aro then \)xci tad by tilt) thermal energy of the flame. lonha·

tion and ~itiltion of the neutral atOIllS may occur to !Oomo degree. Froul

the oxcited levels of tho atom, or molecule, or ion, u reversion takes

place to the around state· partly by imlJllct5 with other spociu$, partly2

Sl,ontanooudy by emission of liiht. The i>rucodin~ suquonce ot" ovrmts

occur~ in rapid suceollion. Fiiuro 1 ~ay help to visualize the entire

soquence if strontium chloride h used as the elilll\pl~.

figure"

lFrolU )(F lWllQ) ( ~ ~rOH(Gases)

(Fro~ )~

(Flame) srO(Gases) '=--

+U11

""""""",-

""~olid Gnseous Nr&'utral lonhcuMolacuhl~Mclocu1tlI_~ ~toll&". :~A~o~s •

SrCl:z ~ SrCl ~S~+ Cl ~-Sr + e

" ...........

..... ...."+U

SolidMetal

Sr

b. ~poct~~ vs llmittor

(1) lJifhnnt wavolol'ltns ot' radiation I1re Olnithd whonev~r

difforent evenU o~c:u),', No us.ful radiation, ('ti th ~5pec:t to colored'. ',#

£100:0, TOIU1 ta wh.uo tholll.tal or ••taUie QOIIPOWlQ is 11 loUd u)" liquid.

Ai loon ~. it h vaporhed. ""tful radiation ~y rl.lJiult. 1£ the compouml

fOlllalu.~. an ,Wldb.o~~nod v")1ol'bed aoloc:~l•• it producos a band spect1'\8.• .' .' " I . 'I .'

When lbo teaper.t~ri i' r.ac:h.~ wh1d, ~Ules tho COMpound to disso~i3te

IwrN No. 71

to vaporized neuttal atoms, a dif~erent spectrum rosults. NGutral

atOll)S produce an atollic spoctrUil composed of atomic (arc) lines.

Wh\JJl the teMperature is iller.ned further to the point that the eluctrol1

is cOllpletely rOllOvC:lQ £1'011\ tho influence of the nucleus, the atolll is

ioni~ed. [oni~eG atoll\~ produce an ionic spect~um composed of ionic

(s}~ark) lines.

(2) Now that a ipocific evont ha9 been describod as b~in&

assoc11tou with a specific ~~octrw~, the saquoncu of events shown in

figure 1 will bo ruvil:wcu. on,. soUd S1.·l> Il\utal or ::>rC12 tnolQculo is

\lapol"hud. The ~rCl, Illoltlculo dissuciatc$ to lJrCl. The gaseous

undluDciatQQ :;l'Cl llIOlecul.e:sollli t 11 bUllu spectrum. Thl.l gnsuuu5 ne.utral

lltows of St- olllit an atomic spe<;tnllil. Tho ¥G.seous neutral SrI. atoms

a~'c uutainuu h."OIn tho vaporization ot' the neutral ~ru metal or thu

dissociation gf the i~5COW; Src.:l molllcule. At thh point, onu of two

thinall can happen to the )luutrlll Sr" OltOlll. It call l.>~ !lol1ted until it

lanizu!!, at which tillle .it emits an ionic !>lJoctrwua or it cun combino

with lUl linion such l1i tho hydrodd<l. Oil, radil:al to fOIiIl moJllcular SrOli.

This nuw lllDloculo will o"tit a bal~d spoctrUlll 1\\1.1 will buha\',", like thu

SrC1 llIoleculus. A5 long as it remains as an undissociutod ~asoous

1llOlcculg, it will limit a band spec:trwu. When tho tempurature is raisou,

such ·that tho ~rOlI dissociate. into tht neutral ~rl> atou\ llnd tilu 011

radical, tho Sr wi 11 once aadn omit llil atomic SP(lct rum. 1t lihoulLl 1.10

obvioUIO by nQW that tho entire llIystt,m is tUllllloratur4.l dt.lpcmdent.

(3) Up to thi~ point~ 'pe~tra wire di$cuss~d in tQ'~S of

radiation ruul tini frOlll thcrwal exci taUon. 'Wlum r;a.diatlon resulU

fro~ non-ther-al excitation it i5 uesc~1b6Q as onu of thruu typo~ uf

4

RDl'N No. 71

chemiluminescence. ~or purposes of colored pyrotechnic flames, the31,36

C-typo cbel1lillJlDinuc:enc~ is most ill1portant. It results frolll the for-

mation of an excitod moleculo directly in the excited state in amounts

beadna little or no relation to tho iroWld-state concentrations. This

i$ • molocular, as opposed to an atomic, phono~non. Colorful b~nd

:iystcllls for aetdlic-OH Ulolecule5, particul,uly t'or barium, strontiwu5

6U'ul copper, arCJ probably due to 11l0loculos that have no indupendil.lllt

existenco outs;1.l!o the flWlle. An equatiun l:'eprcsentativl.l of the r,;-typc

chemiluminoscenco ii

Cu + OH + x---+ CuOH + X

whefCi X is a third bo.ly iuch as U2U' Uz or N2 MnQ CUOU i5 the dirCJctly fomed20,22

excited lllOlocule. ~ydon I1hcUl5U chumUwuinusconcu in relation to

flame reaction proco5sClI and eqUilibria.

(4) Th,re i5 a aroup of ~l~cul~r owitters that do not provide

@sinblo color~ tu pyrotochnic t"llUlleS. SOllie of those oll1it\:Ors are UII,

CO, 0;l' CH, C2 and 112u. l'boy ..ko up tho backsrouml l"ac.1iation 01' the

fliJIlij lind will b~ prosont II loni as or"anic bindors or llliltal-orjlanlc

~o~pow\ds are usod in colored fla~es. All of thuSG r~dicals and malo-

cules omit a bauu .p.ctl~.

(5) Anoth.~ .p~ctr~ that exists in colored flame pyrotechnics

h due to contiul.lOUi ra4iatiol\ and is called a. continuuulI spectrUlU or

contiru.lUlll. No ...Ul i. frot t'rom 4l continuoUJ 1l11111ctrwu, tl5plllcially

whell lU'tultnt i.o larie amounts. 'fhe continuous :;poctruDl is nOl1Oally ill.

very Wide, undifforontiatwd b¥nd.

(6) For dotail. concol'nini the theory ot' spectra, thu readur is18 29

referred to book. by Gaydan lind l'auHnlil'

HU1'N No. 71

(7) Not only do differont motals omit different spectra, but

111~o any iiven metal lUy radiate sQvcral spoctra simultaneously. '1'0

complicate the II\llttor even I!lore, all the lines and band' responsible for

thl) colors in coloTed flare £l&lllos have not been ass~~lbled in (:OlllpuSitc

f'Ol'1ll. 'l'herl,'lforc p to fill this void and to lI1ake infot'lllstioli fQuuily

available for refel'cnco in lator discussion, data was assl.\mble~l concerning

the importWlt lin~s, blinds an~ conti nuUlA for strontiw, bal'ium, copper,

5o<iium, lithium, boron, thallium, rubidium, ccsiWll and potassium. Thi!>

data is in Appc.m411X I.

c. Umittor~ Vi lGaperatur. and Color

(1) 'rhus filr. it h". b~on l:stablished that "usoous metals or

motallic COlllPOUUQI will emit various ~l)C)ctra whun oxcited in Q flame.

1110 difforollt t)'pu of .pl.lctra WDrt) introductd ill relation to thu dOKX'OC.l

or type of l,l"ibtion involved. l'h~ olOillonts which impart a strollg rud,

groen, yellow or blue color to a flame wore listed. It w~s also stru~scJ

that the HUM) sp~ctl·UiIl that r.JulU frOIl tho lIlotQ 1 excitation is t omperaturo

depond~nt• 1 f tho C<ill1pol!tition of tho n UJ'lle is k.IlOW\\ to the extent that

the oUlittor~ are 1de"tifiu~, the flawc ~p~ct~ ~orrcspQndin~ to those

l:Dlitter:.> will be compand prodOlllinantly of enor.y ruuiating in wavcluu~ths

which the uyo associates with a pnUculllr color. Thus, the apparent

color ot' Ii pYrotochnic rlW'110 \:&n bo uplainuu by relating tho wilvelcnc:ths

of clIll.lrgy which corr.5!J<lhc1 to that color with elllitters which l'adiate in

thlil.t WI1V(l hmgth. As lllont ionQQ prov:l.ously. tho ~)(.istonce in. or absl.lnco

frOlll, 61 fllWlO of' Il WiveJi olllittcr ~POci05 is 1'l~ll1t~d to tht) flll111tl tml!poraturo.

Thur~£ore. :in all effort to c1uscribe thu color production mochanislll, it

ill lIut only necessary to identify tho 8Illitt:l.lli liiP~Ci.U u~t &150 it is nl.iCOSSLUY

6

RUTN No. 71

to ~pccify tho flame t~~erature.

d. l'clllporatu1'O

(1) For purpo'Q' uf this c1iscwsion. colored pyrotechnic flamas

will be doscribod aUUlning a. flamo temperature of 2000°1\. Mo:.\t coloreJ

llyrotQchnic fllllll8s will prob&Lbl)' exceed that tomperaturc. In comparison

°to other fl~e., tho 2000K roferenco to~perature is equal to the temperature

01' an illuruin.tini aas-air fluo. The lI1adl'ALUll theoretical temperature1

of lAn oXY2en-hydrojen flame is about 30S00K and that of an oxygen-acetyleneU

flame is about 332S·K. Doan aivos 24S0·K as the operating tompcraturc

of an oxygon-hydro&en fllllO and 2800 0 K for an oxy&en-ac~tylenc flwne.

The seclQinily low rot'ennco tempeta'ture wns 501flcted primal'! ly to latur

show that many ~olocular substancos are decomposed below this teuql~raturQ

and, therot"oX'II, cannot be conflidured as elilittors at or abovu this tunl..23

porature. Tho ~ader il referred to G.ydon for in£ol~tion concerning the

moasurement of flame tompouturo.

(2) There are sovoral tomperatW'o..energy relationships that will

be usod for estimatin~ curtain occuronCfJil. ro~' OXtUllp1e, in nn oXYi(lm­3

acetylono flame (2600 DK), ••iasion is limiteu to linea whose excitation

potel\tial is loss than 1\1 ,5.S !:v or 121 K cd/mole. Uno olectron voltZl

pel: Uloloculo is equiValent to 23.053 kilocalories per &rWll molo. At

2000"11:. it is «uti.mated that lIo1eculolii with a dissociation oneray of

75 K CUl/ROl, (3.26 ;v/woloculo) or 1051 will not be p~oscnt in an

approciablo '''ount ....d that 1lW.'l1ecules with. dissociation C!I1'lOtKY of ~s

K cal/woll1 (•• 13 ev/aol.culo) and l.rae~ can bu formed and will b~

~tabl". Notlinally, tho 2000·lC flame is equaltud to 3.'" ,tv/molecule or ~5

7

ItDTN No. 71

301C cal/mole. for diatOlllic IIIolecules, the dissociation anergy is related

to the heat of formation anc to bond str~n~th.

(3) It is emphasized that the preceding re13tionship~ we~e pre­

:;entcd fllr ostima\.ini purposes lind lAust not b'l usod qunntiu.tively.

The reason fur this obvious lacll. of accuracy results from the lack of

complete \-ndcrstandina of pyrotechnic £la.lIe mel';hanisms. The high tem-·

perature chemistry in'JolVed is not always predictabh using room tuUl-12

per1turc theory. 6n\¥cr and Scar'cy were quoted as huving defined high

temporature chomittry as tho chemistry of syste~s at 3ufficicntly high

temperatures so that the oxidati<on states, compounds and gelaer.al cho.leal

behaviur differ appreciably f.Tom those at room temperature. Tnis Jefinition

clIIphasi..;cs tho probability that new and possibly unorthodox theorios UIUSt be

formulated to explain hiih telllperature phenollena.

e. EnoriY D6finitions and Rolationships

(1) Various onorgy terms nave already boen used in this presen­39

tatien. To make certain thBir usaa('l is undot'!Stood. they arc dQfin"d as:

(a) excitation ~otential • E~citation HnoraY:

1- 'rho energy necossary to bring an atom, moloculo. atomic

nucleus, etc., f~OlI the iround state into an excitc~ state. ~xample of

us.: 1'1 .\ppondi~ 1 the atOlllic spuctrum strontium lino 114607.3 1s shown

rdth an excitation potential of 2.7 e10ctl'on volts. 'l"hus, 2.7 E;\I/lilOloculc

is nec~~sary to oxcite thi~ strontium lino. From the vroceding discussion

of tomp~rature. a 2000·K flaulO v•• approximatud as 3.7 &\I/molecule Dr 85

K cal/mole. A 2000°K, fllUlle, thorefore, has sufficient energy to excite the

A4bO'l.3 atomic spectrum st~on~ium line but will not oxcite the 4.3 E~ atomic

8

lUlTN No. 71

spectrum strontium line A4832.1. With a ~nQwledge of the flanle tom·

l1erature and its relationship to energy. the excitation potential is a

lIIeasure used to determine whether ot' not a particular spectrum line will

be emitted.

(b) Ionhation Po'tential .. Ionhatian Energy:

.!.. Tho emer~y per Wlit charso, for a particular kind of

atom, necessary to rOlllQve an electron from the atolll to infinite distanco.

EJtalllple of uso: In Appendix 1 the ionic spectrUlll strontium line ),4077.7

is shown with an oxcitation );>otential of 8.7 E:'\l. Tho ionization poUlItilll

for strontium is shown as S.69 t~. 1bus. 5.69 tV is necessury to rcmlove

tho first electron fro~ tho influeilco of the strontiWll nucleus and an

additil)ual 3.01 tV is I\,cessary to oxcite the >..4077.7 ionic Une for

strontiUlll. The pnvioUl d.iscussion of telllperature c:.olUpared the oXYiOTlN

acetyltme flame t9 5.S &'J. .'l'hL15. tho oXYion-acety1enc flame cannot be

expected to excito the >..4077.7 ionic line to any appreciable degree. ~ome

ionhatiQn of st'l'onUWI\will. however. occur. The first ionhation poten N

2.7tia1s for the 10 elements bQ1ng discussed arv:

~ .,

.."

LithiuraSodiLllllPotQssil.\llRubidiuaCOSiUlll'1'haJliWllBariUlllStronti~~uron

Copper

(c)

II: cal/JAole---n'O-118.4100.0g6.369. '1

140.8120.1lSI.2·1~1. 2.17a',J

I,', 'I ,I"

. ~ ..: ,"""J.

-it. "

'. '""

electron voltsS.!§5.144.344.183.896.115.215.6!)8.291,. 7~,

, ..

IUJTN No. 71

each other of the two atolll$ fO'l'lDin¥ a diatomic moleculo, or for the

removal of an atolll or a group of atolllS fTom a polyatomic: moleculo, More

exactly, the dissociation onorgy is the difference between tho energy of

the molecule and "its dissociation products in their respective ground

state~. If, thorefore, th~ actual dissociation process leads to atoms lor

radicals) in excited states tho dissocillltion Oiler&y is the onerilY needod

for their separation .inus the oxcitation energy. Example of usc:

Uissociation enerSie~ f~r various uiatomic andpolyatomic molecules are

lisud in Appendix 11. 1'hOlSC values in conjunction with the heat of

formation and fre~ energy of fot"llUltion are useu to hypothe,ize the existenco

of mol~cule$ in a flaao. Sodium hydride, fOT e~~"plc, has a low Jis~ociatlon

oneriY and heat of fOrmAtion and slightl)' lll:gativc free eneTgy of formation.

'onvcr~el~'. those thermodynamic ch~ractoristics are numerically lari~ for

sodium fluoride. Thus, at blah temperatures, sodium fluoride would be

cxpechd to be stable whereas sodlUlllhydtide would btl expected to decom·

pOliC.

(d) Unthalpy • Heat Conunt. H.

1. The~oQynamic potontial Q0fincd as

H • ~ + PV

where: H h the illtu'na.1 enora;y of the system and PV is p~ossurc..volwnl:l.

(0) lint of Formation

1. "~e increall'l ot' heat content of the systl:im when Olle Ulole

of a substance 11 fo~ed fro. its clements. bXawplc of use: Hoats of

I:onnation for varioWl cOlIpounds are lhtod in Appondix 11. In a manner

sinli lar to that du.criboa for dissociation e~lcrKY. heat" of formation is u$cd

10

lU>TN No. 71

as a moasure to estiute the existence of a compound in a flamo at high

temperature. This means is soacwhat um'eliable because of untropy chan~es.

(f) llntropy, S.33

1. The encx-gy pea' degree of absolute tomperature that

cannot be l'eco'Ver~d as work. lliltrol~Y, S. is :r~lated to free energy and

cmtha lpy b}'

(a:) Free llneray of llormation. AF35

1. The froe cner~y chanao Ilc.companyina: the f.o1'lllation of tho

compound at unit activity from the clemants also llt unit activity. Froc

energy Ot fonaation is aefincd by the :l:'elationship

i:.&~ • AU - TAS.34

liXQnlplo of W10: The dan of the froe encrgy chan~e \)1" a process is vcry

s!inificant. A lIlinus siin denotes that the reaction tends to pl'ocoed

spontaneously. A po.iti~o .ii" indicates that the roaction is nonspon­

tanooUli and when AF • 0, tho system is at oquilibriwn. A nCiativo free

(mer"y ch&niO for Ii proceu doos not neccssarily lllOlln that the procau

will tall,., placu. It is IlIOroly an indication that the proccll's can occur,

provided thQ cond!Hons ar. riaht. 1t ill the s1&n of tho fret; energy

chanic which deter-iRQI whoth.r the potentiality to react exists and it

1s tho lOaan1tudo of the fl'tc cnoriY <:hanie which tell:> how lar~t'l that

potentiality b. Thus, the free enetiY of formation of Ii cOlllpounu lila)' bo

~.ll to hypothoaho tho .xhuncc: of tho cOIlIpound in a flUCl. }lroo

enCriiQl of forution at 2000·~ are iiven foJ' ullm)' compounds in Appl.mdix

11.

11

RUTN No. 71

f. Ionization

(1) l'en eleJllents have boen Il\clnticmed previously as being asso·

elated with the pr'Jdu~tion of a colorod flanle. It is intoresting to

notc that five of these are in Group I of the Periodic Tabh. l'hey are

li thium, $odiUlD, potalliUlll, rubidiUll and cesium. Two of the ton &Jlcllumts I

barium and strontium, no in Group 11 of tho Periodic 1'able. In addition,

thue seven also havo ionhation potentials of 5..ell magni tude that

ionization in a flaille can be ex.pected. Table 1 iivcs the pel'l;ont ionha­U

t10n of the afore.cntioned seven elements in relation to various operating

flame t~poratut.l.

Tabla 1

Ionhation Air- Hydroien- Acetylone-Potential Propane OXYicn OXYllon

U!ell1cnt (\I 2200°" 24S0o K 2800·K--Lithium S.3~ <0.01 0.9 16.1SodtUlll S.14 0.3 S.O 2b.41iotaniWll 4.3. 2.5 31.9 82.1Itubidium 4.16 13.5 44.4 6~.tl

CesiUlll 3.l:i9 2a.3 b9.6 9b.4StrontiUlll 5.tJ9 <0.1 2.7 17.2UilriUill 5.21 1.0 a.o 42.li

Ihl» Sahal equation,

1QK II; • -SO~OB + ~, lu¥ l' - 6. SO + lOa~

where: lJ is the ionhation potential in electron volts, T the absoluto

temporature and the i terml are the statistical weight of tho ionized

atoul, thoo olectron Ilnd the noutral litO., is usud to doterlllinu the chu.nil: in

the deareo ot' ionization with temperature. F01' alkll.li (Group 1) llIetals

the final tt~ is ~oro~ for the ~lkalint earth (Group II) metals thQ final

tot'hl is 0.6.

12

lUrl'N No. 71

(2J At, 2200·(. :I¥,ept· for rubil1i\lll and cesiUll. Table 1 shO'is

v~ry little 1oni&.tio~.· Tb~. at the 2000·K referonce t~.p.ratu~e chosen

for· this pnMatatiGn. Ivtn leu ion,ization can be expectod. An incnase

of rela.tivlly few deane. to .:il4S0·~ shows II siinifi~ant inerean iil

l.oniz,&tion. thtrlfo~. ~l... thQ flaI'l is oporating nellr Ok' below 2200°1\.

a s~~~ificant ·a»o.~t.of .i~Q1tation must be anticipated,

(3) For purpose. of color*d n ... production, th6ro ate sovoral

flamo charlilctorisUCI,'UlfQciated with ioni:z.a.tion which uke ionhlAtion

un~••irable. This 11, of courso~ why pyrotuchnic formulator» hive always4

attOl!Ptell 'to create ''cool'' b~lJli c01ilpolaitions. l'he spoctrw of tho ion

15 oo-pl.telr,dit~.r.nt f~OM'th••poct~ of th~ neutral atom and roso~bles

tblt .~ctrum _toted by the ,e~~Dt of procedina atOlllic n\llllbcr. Howovor.

b.caUl~ of ~h. add1tlo~l positive en.ric Qn the nucleus. tho .ero energy

~.v~1'1s hi&b~T th~for ,the .1ewont of prtc~dina ato*ic ~ber, and con M

sequentl)' thO 01l1ld~ lin•• at. I1hplacec1 toward the ul tradol.t. Thoro­

foro, wh.n appr.c:ilbh ~onhat.ion oc;cur' II. nducod quantity of t,he desired

waY.l~nath af ....~ar-},•••itt.tUand ., a result, the flu. colQf dotoriorat.,S.

Thh occurs first bocau~. thCi ,ion it .llUttini an ionic lipoctrwu which, for

pyrotochp1c purpo••" is Un~.airable and J.~on~ll boeaus. of that lonlla­

don. a nductQ nUII'b4lT of ne¥t,t~l now. llr., lott to umit in thl' desired

atollllu ~PC;c:.t'l\aof to fo~ jaQl.culeu w,hld\ voulQ ••it the do:drec1 b~d

l~) Xf ioniaation ocour. ina tlaNe dependent on b~rium for it~

'color. th.,d.t~rlQr~tlon ~"color becOMeI .oro noticeabl~ th~\ it would

in a CPli.?at~loiOdl... or:,J.i:r'1:nUl.iIl depend.nt t'lartl becaus.:. . . : "... , • .' :. :..", :~ : t " '. ,. . .

(.~ '..-"y ,lIIIIi'd,9~'w1t,hin" the dlll:ii'rabl. atomic and banQ spectra ata" : ', ..

iWTN No. 71

in tho yel1owiah-areen wav.l_nath instoad of deep green to bluc-aroen

ami therefon do not, evon wadc:r ideal condition5~ provide II. larie

contralt with y~llow••••nd

(b) The lntonlity of the barium .p~ctrum ia lo¥s than that of

strontium or .odiUM and therefore any reduction in emission due to

ionization will b. IIOre notit:eable ••• and40

(e) Due to roduc~d lwdnow; efficiency aud incl'oas..d atlllosphtn'ic

attenuation in this wavQhmath, the visibility is rcducl.ld oven fux'ther.

~y COdparini the differonc., between the ionic and atomic spectrum for

barlU111 or strontiua. as Ihown in All1l0ndb 1, the rCOlder can l'eadily

visua11;e the color (wavolength) ihift. No ionic 'pectrum wa$ aiven

in Appundix 1 for lodiUM or tho other Group 1 alkali metals. These ionic

spectrl. as indi~ate4 earlie~, would bo expected to r~soable tho atomic

~poctra of the inert gase; with i Jhift toward tho ultraviolet. 1n any

IlIvent, a stroni.distlnc~ desinbh color would not be expttctad from ionizeu

alkal1 l'lIotah such as aro omitted by thoir neutral atOiliS '*s atomic spectra.

(5) Ionization tn t'l.llI\es ha$ boen studied very utonsiv~ly. The24 2S,32 t 37 26.38

readut is rof~rrod to Gaydon, SUiuon and othors for additional information

conccrnini such toniutton.

8. lonization Buff~r

(1) Occurrence of ionh.liou I)f li'ltal vapors~ QSpecidly the

ulkul1 metuls, stl~nti~ and barium. has alroady buon described. loni;ation

of ba,riWll has already been uesl:rib~d. Ionization of bariulll in Q bariWll

b••oQ £laDle has b••n t1aacribed as beina partiCUlarly detrblental to ollliS$ion

of tho desired arean color. ~\C .tan» f~r reducin~ ionization is to

14

RUIN No. 71

reloiuce tho temperature. Thill relationship was previous ly dUCl:ibcd. Fl'um

u prl1ctical standpoint. to redu.ce tho op~t'atini tOlllpeI'aturc to the point

that ionhation of blllriUlU would be nUKU~ible Ny result in an uns~rvic.ca\.llc

pyrotechnic for roasons other t1-UI) color. It is. therefore, ,losiraulc to

be able to suppress barium ionhatign L'y means othor thl1l1 tOllll)Cl'aturo8

reduction. This can bo accomplished by thQ addition of ~n easily ionizod

I'lI~Ul to the flallO. In MiHtary f'yrotecnnics. pota:H>iUl1l. usually in the:

fontl of tho perchlorate, is used to but'for the ionization. The selection of

the porchloratu salt of 1)ota551\111 instead, for cxa~plQ. the nitrat~ salt,

is to provido not only tho buffer eff~ct and oXYion supply but also a

haloaon supply. llalQi,n influ.nco, ~ill be ~i$cussed separately.

(2) Continuina with the ioni~ation butfer discussion, tho ionization

of barium can be d~scribod ~s:

1\& 4=t bat + .-.

Pota~sium, which is =von mort ru~dily 1oni~ablo than biri~. can be uos­

criboo in a si~il.r ~annor:

It' conditions which 1l1lprolleh oquilibriU1ll &)."0 "slilUl\cd. thllll\ by Le Chahlior' $

Law Of' t4au Action) tho e1clct.ron. r~lldUy producl!ld by the pQta~sil.W ionit.a­

tion will brina ~trou to bOll.r 011 the bariUlll equiUbriwn, th~r~by displacinH

the barium r.acti~n toward th~ neutral atQm. In ~o Qoi"¥~ less b~riun is

ionized leavin¥ moro bariua to ~nit its atQ~lc Ip.ct~ or to form II. com­

pound which will _it its band apectrWD.

(3) Tho effect I:i I)otauiw on color should be notod. Tho ionhcd

pota'li~, will .~t • ~pDctrya wh1d) ~e5~lol thQ ato~ic 5puctr~ for ar~on

lWTN No, 71

whose strongest lines are in tho deep red and neRr infrared. As soen

from tho thermodynamic properties li$tod in Appendix II, except for the

halogen SQlts, potasi1u. will exist as tho noutr~l ~to~ in flames over

200Q"K and, therefore, will ",.it the characteristic purplish-relol and bluish­

pUl:plo atoD\ic lines listod in Apponliix I. F11l1l1e ellniss ion spoctra f()},'

the l)OussiUlll-baloien salts could "ot u(: located. The ionic and atomic

potassium spoct~a will not causo ap~roci.bl~ interforonce ill a strontium-red

flLUIle. ~ollle\->let lK)re 1nte1'hrcncc would be ."}JocUd in a bariUlll-~reon

flal1e. FOi'tunl.t.ly, however, tho bonoHtI of thu ionic bw:£orini action

outwciih ths liiaacivanhllo of the of.f-~lor ionic and atomic spectral OlUlsSiol\s.

h. lIa10ien In£1uol'lcl.ls and Color Production

(1) Lon¥ aio, pyrotcchlllciMns startcIJ to add hal(,)~on~, in SOlliU

fQrm, to pyrot.chnic compoaitions in order to intensify or enhanco the

color. Chlor1no in the fQl"/Il ot' Q pOI'(:hlorate nlt is fn'luClntly useu for

this purpose. In addition, no".oxidi~ini chlorinateu aJditivos such a~

hoxuchlorob4mzen. and polyvinylchlurido aret !tho used. Although tbl.l effoct

b known, tho Il1Ilchaniaa 'is not CfJlllplot~l)'"mdur:n.ood.

(a) i~rium·Stro"tium

14!. t:l1ern cl'editod lIart as rct'Clrrh,~ to the rod flalllC as

d~ to ~lecular band. in tho red r.~iun, eau~ed by aglccular ~trurlti\W\

oxiuc lU~d chlodoll), ~nQ dUutell with other linus IUla b..nt.ls fr~ inclUll1ucwnt

l,artic:los. li.~'t abc )'0£'1'1'01.1 to tho gre,,)} Oac us lJo.l.ni' due to brisht

blue bands frOM ~opP'r ana bariua chlorili. in the 4000-5000 and 5000·550U

anastrom re~iou. Mo~e rvcent inforaatlon leads to Q ~liihtly uiff~r.nt

.xpl.n~tion,

16

RDTN No. 71

3.. Colored flame pyrotochnic cOlllpositions cont,ain organic

binders and chlorinated oraanic molecules. The combustion (oxidation)

ot' these organic r1C11eculos ]'lTovides the flamo 1l11ses with a 9ClUTCO of atomic

Ill''';! lIlolecular hydroicn, noutral anu negatively chaI'&ed hydroxyl radicals,

atomic and anionic chlorin~ and other matorials. The low. 57 K cal/molo,

dissociation oneriY cf aolocular chlorino as ahown in Appendix 11 leads

to tho absonco of ~l.cular chlorine from the flame. Usini barium as the

example metal, sovenl colDbinatiol\S can bo expected.

C1 + II + au~ HCl + 011

Oli + ~a~ UaOH

c.a 00- 11a 4' .. ~IlCl.

The combination of chlorino and hydrogon to fOl~ hydrochloric acid is

spontanoous at ~OOO·K since tho free onoriY of formation is -25.5 ~ cuI/mole.

Once fo~d. the Hel tan bo expected to bu stablo at temperatures in roa~

$onablo IX~~SS of 2000·K sin~e the di$sociation energy is about lOS

K cu.l/mole. The hiSh lik.Uhood of Hl,;l t'orlllaU,on plus the stability "t'tel'

fonnatto" caules an OXCClU of the au r~dical. 1'h15 exc(lss» in turn, repl'eS!'lOS

the dilAt.olnic aetal chlorido, l.laCl, formatil;ln and increasclS thlil triatomic

met"l hydroxidtl. aaou, t'oJ'lAit~on. Another con:s1l1oration with rospect. to

tho $uPP~'Slion ot' the ~aCl formaUon iJ th, low. ~1 K cal/l1lO1o. dis50ciation

~n,riY of the di.to~ic chloride. Bnhancement, tharcforu, rosults by $hiftin~

tho 6lquiHbriUlll townd the fO:n:laUon of l!aOU which, as shown in Appondix 11,

omits in the areen waVQ1enith. 1'1rQtochnich.il~ pr~for aaUH fomatillJl over

Ii"U t'o1.~lltion bee..... thli ».0 band spectrum encolllplUcS luany undesiralilo wave­

lcnll.thl. aao would probably form in aro&tn quantities if the llaOU for-

17

IUn'N No. 71

luation wero not promoted hy thCl oquilibriUlll shift cuused l.Iy the chlorine

addition. As a consoquonce, if ijaQ!-i fOI'llllLtion is increased at the CXpOnllQ

of aaO, this. in its.1f, will result in a lUOre dosirablc oX' enhanced

color.

1. Ual0ifln onhancement ot' stt'ontium is analogous to that

de,cribed ±\,r bar! WII. In both ins tanco$. 1>ec~U!$C the pyrotochnic COIUpOS i­

tions are usually nturated with tht.l meta l ami ha lOHen. a very substantiu 1

WIlOunt of th, metal hali.l.le will. bo prustmt in th" flame in addition to

the hydroxide. Tho baUc.ie fOl'lllation with bariulil and stl"Ontium is not

objectionable because th~se moleculus furtunately also omit onorgy as

defined by th.ir aolotular b~,d spoctrum in the dosired wavQlon~th.

lb) Alk~11 Metals

1. ThQl baloa~1\ offe<:t with reSlH!ct tu thl: alkali metals

11 different frOll that just describe!! t'or bariUIII ami strontiwn. liuUQrally,

b~,auso the l1oah'abla oll'hsion from tho alkali lllotu.1S 15 th~ atomic spuch"\IIU

of til. neutral atglllS, the Qlddition of a halogen will not result in on-

IUlncomont. ThCl dalireui ••hsion of thl,l atolilic spott1U~ will bu substantially

rodu~ed bocaulc of »alt fo~tion.

1. All thlll alkali QU1.I will not bohuvo ldonti,,;ully31

iJlilcaU150 at" thCl stability differencos in their hyl1roxidB. SUiuun paint»

out that lilt 2245·1(., LiOli is very .tablo WlUll:.lllli NaUIl is 10 Wlstable as to

be offcGtively ~sQnt fr~ thu flamu. Aauna the alk~li mutals, the

stability in uocro&Jins order i$

1.10U)oC.OH>1~baH~K0I1>N"lJll.

In ~ ~auner .1Nilar to that used {or ba~l~ and .trontl~, and u~lnj

18

HU1'N No. 71

rubidium a~ the .~pl~ metal, $everal combinations cnn ba expected

Cl .. II • OH.. '1lCl + 011

C1 + Rb * )RbCl

lIel .. Rb (=::t lu>(';l .. 1'1

au .. Rb~ IlbU11

The oquilibril.llll of til" last equation will ,111ft .::onsidel'llbly t'or diffllrollt

alkali Illotah because of the proviou51Y montioned stabi lit)' difference:;.

The variation in thill equUibdUill will (Iffoct tho quantity of halu~"n

salt fol'1llou. Sodiwu will form Nael wi.th little or no NaO:! fUX1Ilatioll,

wh~rou l1thiua- will fol'1ll LiOH ~Ild a dinit'icant aml.>unt of t.iC1. In any

ovent. whuthor it be hydroxidCl oX' hal1de formMtion. thl: fonllutioll of any

alh1:l. lUtal co.pound will reduco the llIIlOunt of alkali llIobl l1Qutrlll atom:;

available to radiate ~l.it atQ~C Ivoctr~. HecaU5e halides stimulat~

alkali motal c~pound for-at ion. the haloions must bo clas50u a~ nOK~tivo

enhancement lliontJ ill lllllllOs conuinin~ illkdi luctals. In conh';.ll>t,

halogons ArC pOllitlve .nbanelli.nt Ilient~ in t'lamoll ..:ontaining tho alkalinu

ullrth metals bec.l&uu, um.ler thosu ~onditionsQ the hyu¥'oxide and balidu

lJ-.n<.1 Ipectra M1'O proferrod over tho atomic spec.tnwt.

(c) ~ot:on

1. \~h'll bOlrOl1 11 ildded to " fl(1luo. thj,l Ilruun colur which

results b ~u. 1'11:ouolilinantly to 6tO~. ~QIAO ~o is probably also 1'O).'III\)<.1 1lIhich

omits JiU)nly in the blul) to \l1tr.vio~~t. IlrOlll thermodynamic dM.tlI. listed ill

Al'P~nub 11, it b COlu:l~..~ ,thu the boron L):d~e:5 Ilre 110t only \'U1')I

likely to fot'lll (A~HLah) bl.italsu v~ry.nalJlQ llli¥h l!is~oc.ilf.ti.OI\.nux~y).'. . " .

lJxs:cpt fot iod1n., tho bQroR .haliJol aho' ar~ llluntHiud with hiah 1'1'00, . .

t J.~ ..• I., I ,'01

., '

RUTN N(). 71

cnetiY of forution l1lnd diuociation "nora>,. If the nll.liu.u band

sl'ectna wo1'o predOlllinlantly i1'cH,m in natures the addition of a halide

would be uenuficill1. On til .. contrary~ hOIl/l)ver, llF has an ulI(\~sirabla

yu 110w system and ~ar Ilnd OCI om!. t pd~ril)' in ncur 1.11 triviolet •.

If, therefore. lo\ balogCltl other thM ioliline WCllre introduced, a stable

halide would form. This, in turn. would reducu tho t\nlount of the oxil!u

present which was rlldiatini in the beneficial green \lIavelen~ths. '1'ho

net result woulJ. bo " shift tawllrd \>1uo with a noll11tiV~ enhancemont

(") '1'haIUwn11

.!.. 'l'h. ir~at bulk of the thll1liullI ill lit nam~ is \l)'e~cl\t

u tho ireo ulo_nt. 'l'ho gro.n flua color is. therot'ol'Q. i.luo to tho

n.utnl atoll' atolllic :>[l~ctma. Oxido lUlU hydrodJ~ fOrl1\lAtion rJo not

OCC'-lX' in thu t'lllll10 to any apllrcchble l.h~ir"o. 'fhe moru clect.roneiativlJ

haloaenl& will {Otlll ruasollably tbble hillil1\;)s ill the name. 'I'helle Can

UQ uxpeehd to emit blUlu spoctra. ThaUiwn fluori<.1o, chloridQ an~

brolll1dc fOmit in til. c.leull blue to ""ar ultraviolut wlAvtllengtb. 'l'ho~c

\)lniulons llro of no I'articubr value for anon flulile prolluction. Thus,

whun a halojon is introduced, liOllll:l lIubl. halillu i'01'\1I5. This in turn

nJut.. the lllIWunt of th.a nQutrll.l atolllS which are radiatill¥ in thu

ulUi red aruun 11)\01. Tho nut 1'1,ulUlt 11 a $hift toward blue with u

nOilltivu unhanColllOnt with rupect to auen.

36l. lh, &rlat bulk of thu copp~r in u flame is prusunt

ill. tho frulll atO!ll wi th not 11I01'0 than 10\ a5 ~UU. Appendix 1 show£ Ill'

umlesirablo tianJ 5poCt~ fOl' cuu in th" oran~o 1'UII\iol\ and w",I,k bWlds

2U

RDTN No. 71

in the ~reen region. The free coppor atoms emit a weak green line

"at 51051.. l'h. cOlllpoillito of those emissions woull.l inuicilte a WQ:lK

polluted greEinish color. <.:ontrary to this. copper. when introduced into

a t'lnllll~, exhibits a Itrona yel&owish K).'een color, '11\i5 is attribut~H.l to

<.:UOll molocular ol\1ssion. Noto that CuOH fOrll\ation is recoanhcd ovon

in the ab~gnc~ of' haloioJU. In liluitod amounts, this is true :1150 of

uuriUlll, strontiwa and lithlUlll.

!. DuJ'ini tho discussion of the other 1l10ta1.s, thortllall y

stablo salt formation was dQ5Cribed IlS a result 01 h4110gun addition.

Appendix II show I a_nerally low dissociation energios for copper ~om·

P0lmus. This accounu for tho fllM CQmvo~itioll bein~ prcdoliliuuntly fr~c

copper. When hilloaens are addod to ~ coppel' flame, the color chanKcs

from irQtn to blue. ay tho postulato, laid down for bariwa and strontium,

tho addition of haloi"n to a copper fllJlle would be oJopccttll;l to form the

halidu acid cau~ln~ oxens ali Which, in turn, would comLd.ne with thl,) lIIutnl

to Qrulanc~ the color emil.ion by r~diatini the band spuctrunl. HeC3USC of

the low ~1s.ociation onoray, tho halide salt would not bo e~pccted tQ

form in 1arae liUllounU. 111h exp lanution based on thermal cons ic..lol'lltions

and room teillporature thooTy does not appoar to Ito Lei trul;l for C01)P01'. This

is obvious bocause blue color results inl6tead. ot' an enhullced ~ru"m.

!. WlULt appears to be a serious flaw in the ar&Wllont is,

in fact, ~upport i'or the theory of cho~il\&lllin"'$cencc anu is readily \lX­

plai'll.d w'i thou", deviation from thu bailie kr"Ulnont. Whon halogon is arldl'rl

to Ii fllllWl conUinina coppor~ a sull IIllDunt of th" copper haUd" suIt will

fonn. A 5.11 WIOWlt (lUl contrllsted to lar~e) is toruultJ b~C.a.USll of the low

21

IWTN No. 71

dissociation enoriY. Thus the equilibrium favors dissociation. rhe

sn~ll amOuilt of ~alide s~lt formed emits a blue band spectrum. This

emission dominates that of the CuOl! emission which leads to tho con-

~lusion that C\~i is probably present in an extremely small quantity.

As in the case of bariUlll and strontium, the haloicn combines ~ith hydrogen

to form tho halide acid, thereby causing an Oli excess which, in turn,

contribt:.tes to fOX'll'lation of more CuOH. Also, as in tho calle of barium

aml strontiwn, althouih more metl1lhydro:ddo is fonlled, the metal halide

is formed in even iroater 8ll1Ounts. Uecause the litrontium and barium

uletal halides emit in desirable wavelengths, the net result is a quanti­

tative inc1'Oase of omission in desirable wavelengths. In the case of

capper, however, the incroase in CUOH is ol.1t.wcighE:u by the increase in

I;.oppor !lalidG f01'lllation, thus resulting in a shift froUl Cu.Oll ~recn emission

to blue copper halide omission.

4. Tho pr~cedini discussion was based on thermal eon­_. l~

siderations. Gaydon, in discussing carbon monoxide flames, sugf,ostuo a

catalytic offoct Which should be considered in addition to thermal

PQssibilitiCl1l. H" stated, "Mother pCll'sistcnt impurit)' in the spectl'a

ot' CO flames is Cuel. These bUilds llrc l:\tron~est in the blue and blue-

green and ar~ dOQradod to the red. The reason Why these bands occur so

readily' in CO but not other £lallles is somothing of a mystery; it is

possible that cuel nets as a catalyst in the oxidation and receives eX-

citation eUC1'WY frolll the pl.·occult •

(f) Metal Halido Moleculo excitation5

1. Dean stat~s that tho halide ndical will tend to lesson

RU'l'N No, 71

the attraction of the electron to tho nucleus and thus renucr oasiur

the excitation procoss. This feature is of importance plll'ticularly

in £lames containing bariUlll or strontiunl. In these flamus a major part

of tho color is due to llIOlecullir excitation and a significDnt portion of

the emittini mollrlcull)s are the halid~ salt. Thu fact that thl;) excitation

process is made ouler by the halido loads '.:0 a net increase in emission.

This increase is also considered to l>e halide t:nhancemont •

.!.. 'l'he colur of pyrotechnic flamos is dopunuunt on the

volatile ltIaterial in the flame. 1'h15 matel.'illl Il1ny be the noutral a.tom,

a diatomic or polyatomic lllOlocule or ions. Color then is dependent 011

the ",uility to keop tho materLtl volatilhed within the flalile. Tho ability

to keep material vol~tillz.d within the fl~e is, among other things,

relatod to its boiling point 'and heat Ot fusion. It is loaical to concludo

that, for a. flaJl'O with ~ aiven arAOunt ot' en"rt:Y, the alIIl>unt of th~ material

in the f 1alll8 is a <Joel"casing function of 1ts \,)oilini point, Thus L\ low

\Joiling paint favors & laraer qwmtity of volatilheu lRattor in the £lamo,

1.. It b.s 'already Loen established that h&lt>gens aro

added to l'yrotechnlc colored flare COlllPOlli tions to bonon t from th\)i r

onhancom&lnt effect. Whellth@ ~ta1 halide it \lSed as an cmittof, it is

Qoairabl~ tok61llp it vol.tilhed, Sinel,) the morQ eloctroncl'ative halogens

fOI'1l1 salts with hiahor boiling points, 'the electronegativity of thu halo­

~en will bo relatol' to tho quantity of halide salt which a fluu", can

ke~p vol.ti1ilO~. ,The haloa~n ~lQttronOiQtlvity scale 1»:'. <'I' " .

", , 1'>(;1>lir"'1

, .• 'I'

,"'1.

IWTN No. 71

'rhe complote oloctronMjativity scale uf th~ elements has uoen tabulated28

by I)uulin~. Witbout con5i.deTin~ other factors. iodine would be tho

best cho~ce to provil.ie a low boiling matorial. Sec Appendix 11 for ~

listini of t1lll1tin~ and boiling points. SOlllC iodides arc, however, un-

stable Qt tho flame te~).raturc. A more electronegative halogen must,

thorefore, be solectou, Another imp()rtant con~il.leration is the band

spectrWll that tho motal hlLlide will Ci1ll1t. These band spcctl"a l~rc dcscrib~H.I

in Appondix 1. Althouah, for example, ~ lIIetal iodide is stable, its

spectrum may not be benoficisl to the ~esirod color. In this instance,

a cOlllproll\h" will probably r05ul1:. A lIlore electroneglltive haloien with

Ii hiaher bollini point will prob2bly be sdoc:teu in o~'dor to obtain a

preferred "pectrUlli. The $C lection of thlt hll1oion. therefore. 1$ not

an arbitrary lUtter, Consideration lllUSt be ¥ivcn t" such facton as

stability, ~pectrum an~ boilin~ point of its salt.

!. C0I111l0dto U&IIIe spectra for e0rller ~ bariUll\ ami

litrontiUll\ are 1ncludec in Appendix 1. '1'hose hypothotical spectra would

only oxist if All of the halo¥-~ms W4.lro prosent in tho fla.llle simultljnuously.

Sl..1ch u condition would have no practical advantalje, 1'huy were included,

however, to il1ustrat", wavclenith shifts which can be expected lJy halot,:c:m

Vlu.'htion,

i. Chcmiluwlnesc.nco

(1) Cb'lAih.in~.cenc:o Will discuSleci briefly in tho SpQctruDl

vs 1:!11Iittor Se4Wtion. This I,h.nolilonon was also ,"~ntioned in the do~crip.

don of coppel' color production. The chllruhrhUc of C-l'ypo cMlllir­

lumine~cencf. that 1~ uf p.rti~ul_r i~Qrtance is tho ubility of

lUJ'l'N No. 71

a small number of mol.~ule$ to emit an ubnormally lar~e amount of radiation.

Tho effect is relllark.blc. aaO has a dissociation energy of 124 K cal/mole

;'lOci UaOIl is estimated to have a dissociation cnerp,y (into Ua and UIl) 1)1'3b

less than 60 I< cal/mole. !:iugden based on that data estimated the ratio

of ~aO:~a;~aOH in a typical flame to 00 roughly 103:1:10.3• It, thorofare,

is romarkable that such a small quantity Ot ~aOH will emit such an in~

tens~ ,,~etln color. C-Typtl chomill.Winnc.cmce is, thorefore. su¥ga~ted.

(2) It is cUlphashod th&4t C-l'ype cheDli,lumintl$cence re»ults hom

the fo~tion of an excitod molocul~ diroctly in the excit~J state ill

«mounts boarina little or no relation to the ground-state concQntrations.

'l'hl.> lllolecular emuions are probably due to molucules that have no in-

deponuent existent" outaido th", fllUl10. The phellolllcmun is not a thermal

type excitation and, thorefor,,_ must be considered as a radiation source

in 1I,ddiUQn to thermal r.diation~. Tho stronl/. strontiUlll red. bariUIII greon

and copper areen color~ in a flwme havo been attriuuted pri~arily to

C-Type chomilUlllinell;once of StOll, UaOH and CuUH.

j. Lillliuion Suppression Qod Inten!iification

(1) ~yrotechnicians o~pirically lOQ1UCU to uvoid tho uso of

various compQW\dli in colored flamo composi Uons. When und, sorious

de¥QI\II1I'ation of tho co10%' often results. 1i.lnission suppl'cssion of alkulino7

earth nuiation» is caused by elOlll~l'its such as alwninum. boron, chrolll,iUDI.

phosphonu., silicon. iron. ber)'lliUll1 and sulfur. Tho suppression npptlars

to be hued on the fOl'llilltion of molecular cOIlIpounds with the ,alkalino

earth 1JloUls which are either difficult to ovaporate or di1'ficult to

dissociate. Many of the slippr05&Ol" possess the abiU ty to fOl')ll flnions

25

Itul'N No. 71

such as the alWllinatel, borates, phosphatt$, chromates and sulfatos.

This phenollllllnon is one of th0 rensons vhy llIaincsiwn is used as a fuel

instead of nluminum and why pyrotechnicians have been unable to color

the £lamo from standard day-niiht tY}>Gs phosphoI'u$ cOlnpositions.17

(2) Tho :red burnina nilroad "fusee" is shuwn by lHlem to

,"ontain 10% sulfur. Sulfur is describod doni with other ~aterial::; as

havin¥ desirable propClrtics from tho viewpoint of beini slow and (;001 ..

burning. l'hcse references to succo$lSful cOI1IIIlorical uso in 11 coloroc.l

flall1e composition and to its dosir~hlu proporties omphaai~e that an element

01' its compound IU)' be used to ilJvanuao when tho supprcsdon propbrti~s

a.re outwciihoG by desirable thermodynamic, chl.lluicl'l1 and l'hysi~al propertie:i.

When ultil¥lilU perfo1'lllance is rcquire~the U50 of any of the IhteiJ

suppre$lors should be cunsidcred ~ory carQf~ll)'.

~

(3) Although tho oXAlato anion i$ r~portcJ to $criousiy rcpr0s~

sodium ewission. sodium oxal~te is f~uquently us~~ is Q sodi~\ donor

in yellow flame fOl'lllulations. From a prQctical standpoint, the

suppression can frequently be tolorl1ted beeaulSc of the extremely hi~h

intundty of thl!l sodiUlll atolllic lincs. Tile oxalute ion does not appeal' to

serio~ly auppress .tronti~ or b~rium emission.

(4) l'hosphato, and sulfatos stron~l)' inhibit the emissions oj:'lU

most metals althouah sulfate has been reportud us an intensifier of

!Joron omission. 'l'he acetate anion is ¥onorally consider4.ld to be an in­

tensifier. Thill sUiielU ttUlt for yellow {lUll105. soJiwu acetato lIl3y be

betten' than SOdtWll oXOllate. fior that IIlI1tter. sOllie lIunefiU inKy bo

realized fro~ u»ini nt1'ontium or barium acotatc instuad of their oxal~tes.

2b

IWTN Nu. 71

k. Flame ~quilibria

(1) Throuahout the discussions, molecule fo~ations. dis­

sociations, ionization and limilar evants weru des~ribed by in~icating

whether or not the event would ta.ke placo. Since IllOSt uf the roactions

in tho fla~~ arc reversible, an ~quilibriua for each event must be con­

sidered. Uecauao, fOf oxamplo, of incomplete combustion and turbulQncc,

tnore is dQparturo from oquilibriuw within the flame.

(2) A quad-equillbriUII is probably establisho,l betweon tho

roactants and reaction pruuucts. In ad~ition. there ar~ te~peraturc

~rM.dients within tho flalllc which t<md to uput ostablished .quilibl'iI&.

lt woul" lle an advant"ae to des-::ribc each occununce in a t'liullo with. an

equilibriUlll constant. Undu iivC'ln and constant name conditions, it

would then be pou1b1e, for Qxamplo, to calcubttl the quantity of II

reactMnt or reatUon product in the flame. be.::uuso I however, of dera1'tuTo

t'rolll cquilibriwn, tellpet'aturo KrI&l.liunts. turbu.lencu. incOlilplute lnuwledjlo

of uxistini r~action. in tho flame and other causes of variabilityp

ubsolut~ state~nts of quultity w~re not usod to doscribe events within

thl) flame.

(3) Whon it w~s statod that ,," event would or would not

occur, tho roaaer .ust recoiniz~ that these jud~m.nt' urc not absolute

with rl,lSpoct to quantity. In addi Hon, Illllny events W8lrU dU$criui'd USillg

),'l.lh.tivc.l quantity doscripUonj. In moat instanC<l5, the assessment was

lIUIl.le uas\lu on the11iOliynM.lllic pruperties of tho mlltel'ials involveu. For

uxample. it wa. statod that the low. 57 K cal/wolo dissociation energy

of llIOlocular chlorine lead. to it. abs...~ce t'rWll the flallll'. This shtwaont

21

lUHN No. 71

\~a5 1111<10 bCCllUS~ of the rfllativdy la rio soparat ion btttwoen tho 57

K call1lOlu dinociation onel'iY and the en.ray of Ii 2000·K flalllO which

\~a~ n0ll1inl111y equated to as I( c:.ll/lllo1o. If tho dissociation eneray of

~12 had beon \)ven low.r, an evon Slllllll\)r lUl\ount ot" (;1 2 woull1 fol'lll.

l.:ul\vorliely, th" \<\01'0 tho dissociation enng)' h laracr than tho nominal

t'lIlJl\C onniY, the 1IIOt'cl likely it i:t that tlUi flallle will not diuociat~

tbe material, thel'cby allowini more uf tho lllatcrial to be pre~"nt in the

flouue. It 15 in luch ~ relativo IlI&nnor that each u'r'cnt I s occurrence WOl::i

dI)5cril>ed.

a. An i~lJdly i'ol"Jluh.ted pyrottlchni~ colored flulnc cUJIlposition h

one which, whon burn"d, produc:u cOlllbv.stion produl.:ts all ut" which roadily

ClIllt ndhtiun in the wavtlQllith ot the cJoslrecJ color. lhc prefQrrc:u

~~ittor5 of various ulc~ent~ arc:..

l.i thiUlll l.i red0

~QUiWll Nu )'1,) 11uw..

Rubidium \{u rudtl

CodWll Cs blue

lladUlll UaX, UllOH xreon

I;;tronUUIJI ~r~, ~rOu ruu

lWren llo2 l\ rlten•

l1ulll iWll '1'1 &r.,~m

II

<,:upp~r (;u an'" ~uOI1 ~rltcm Cull. bluu

X • lu&lo1Lon

10n1le<1 potalliUl'/l, rwi<1i'Ulll iUHl cc:lIiw ure useful ionhlltiull buH~n.

28

IHHN No. 71

To prepare officient foruwlations. pyrotechnics lllust be cOlilpounded to

form tho neutral .tou or molecules in large &IIlounts. '1'" do this~ th"

approach wi 11 vary with tho demont used to I1rCJJucc the color. Certain

postulates apply which di$rOiard all practice 1 material considcrutions t

su&:h as :;onsitivity, stability, hygrQscopicity, cOllluustion prol,crtics,

CUit and toxicity. Such pOliltulates which apply olll)' to tho product.i on

of color in a flame are:

(1) l:ormu.lato the composition so that n maximulll Wlluunt of the

preforrc.>d ellli tt,u' b l)rollucod in the flamo as a vapor.

(2) Adjust the name 0pol'3tin~ tcmpuraturo ill relation to tlu)

pro~ul:tion of tho llIoIl.dlllWll amlJWlt of excited cmiu('r. 'l'hb ruquirli;s that

thl) tOlilperaturo be hpt low to rQQuco ioni:l.ation .md that it UQ kept hiih

cnouih to prolluce vaporization IolnQ oJ'citation 01 pr~forted 5pt~cies allu

<.1i5'ociation of unwant~d .oloculo~.

l~) U~e ~n ioni~ation b~ffur to ~iu in ionitution sUPllros~ion.

l'his is ot particullir 1"lval\UiU "hen the color is thLl rfJliiult of tho alkali

or alkulinu curth motals.

(4) for oll'Plonts wbos~ color gupends on the neutral atoUi. Olvoid

thl) l1ddition of IlUltor1l1h whose elolllont:i can cOllluinfJ with thl) neutral

atulils 'to form IllQlacules. 1101' the rOlll&inini ul~l'IIontl, adll waturial.s WhUlllJ

olen~nts will combine to fOlill tho pro{urrod Inolu~ules.

lS) \;orUlUlate to benefit i"rom Ch••UUlllinllscCllce anu onhanCUllllmt

(6) SlOloct ll1i1.Uriah to rcduca umiSliou sup!ll'euion which results

from m~ny anions and numero~ ~otals.

LUYl'N No. 71

(7) 00 not introduce .u;eri&~ which is not essential to th~

production t)£' colClt. Th1s will reduco unwllnted ei'\iuiol\s and bllckgl'ounu

radiation.

b. With cansiue~ation only to color production. it is concludQ~

that ,1111ultl1l'u~ous cOJaplb.nee \IIith all thCl pustulate:; is :l.1I1pouible.

'I'hi:s l'UIUOl\ alon~ uk.:s cornp)."Ot4he 1IllUHhatory. Whan consicleratioilli

'tc1uted to practicality ato inU'(,)u\!,ccd, adliltiollal concou ions resul t •

It is, thcr"fou a fortLlnllte for the author that the purpou of this

prosentatioll is to d.~licribe ortly tho theory ot' c;~lo.·ed flalll~ production.

Thus, it is not nOCO~$ary tu list flar~ formulae ~hich will prouuce

I:l)~or,,'" O;'Ull.' LanIoWX' all c:on.4I:~ivablo coml1tion» and in fuHill~unt of

a11 l'oquh·clllonts. A bottu undcntandinj of th", cnemicg.l and physical'

pro~o~$~$ involved in ~olored fl~o p~o~uction will, howover, enlbl0

tho p'1'opilitlAtio'l gf c<*}i()d tiollS itl 11 Illor" rationa 1 llWlnel'. H was i'tl1'

thi~ purpl>le that the tlLcO"hl5 ~nu llttdbut"" LLuocillted with colond

rllllllCl productiojL IIIIU'C dbcUI"lu'\ anc.l etllUlllo:t'OltliJ.

30

m)1'~ Nt). 71

lUi FLIUiN l:f~S

1.. Uellll, J. A., F1anwa Yhotoilletl")', ~\,"Graw lUll Uook Cnmp:\IIY, Inc"

N~w Yo~k, lU60, p. 11

2. ibid., p, 31

3. ibid., p. S3

4. ibill., p. :56

~. ibid., 11. 3'/

0, ibid., 1). 40!

7. ibid. j p. 41» lU7

S. ibid., p. 104

~. ibhl., p. 16(;

LU, ibid., p. 22U·230

11. ibid., p. ZSi

12. Ut'OWW.l"t, J. ",ntJ GoluHIl~l.lr. "., fl.nl\ulll R"vi<.lW of Physical \:ht.llllistry,

i\nnud !«lvioWI. lnc •• Palo Al to, ~a1iforl\iG, .!It.. 4S~ (l!)o2)

13. l;l1ol'n, It' r Modorn PYl.·otochnics, <.:h/jlllical 1'l.1blhhin~ Co., Inc.,

New York, 19b1, ~. 7~

14. ibid., p. 81

IS. ibid., p. YO

16. ibid •• p. 9b

17. ibhi., i'. 1J7~ 27S

l~. (JaYUOl1, A. G•• Thill Sl,octI:Ur.lCopy oS:' )'IluD1"S~ Juhn I~ilcy , Sons, lnc.:.,

Nuw York. 19S7, p. 4a~72

l~. ibid., p. U2

20, ib!u., fl. H~!>

:u

IUHN No. 71

2L l;aydon, A. li. , llis50chtion L::l\cr~i.es and Spectra I,)f IHatOlllic

Mo1ecul",s, Chapll1&U and 110.11 Ltd. , LOl1don, 1953, p. 3

22. Gayuoll, A. G. and IVol fhard, II. Ii. , Flullln; l'huir Structu:n:,

ltadiation and l'empera.tl.lfC, Chapmun anu Hall Ltl.1. , L.ondon, l!JbO,

23. ibiJ., p. 234-301

24. ibid., p. 302-323

25. (,reen, J. A. and SUidel\, 'I'. ~1., Nintl\ ::iyllljlosium llntcl'nll.tionlllJ 011

~olllll\,lHl0n, Acadomic Puu. Nuw Yo&"k, l\H);~, p. u07-tl21

2u. Ureenu, S. A., A l.itUfiltUTO Survoy (If 100s In Flumus, Aorospuc~

I,;orporatiun Rtlpm:t No. l'LlR-l()!) lS31S3-01jl'N-S. Contl'act No.

Al'-U4(b~IS) .. lbU. 15 JWlC I1JlJ3. :icu A::InA AIJ41032U

27. l'llulini, L., l'hu Nature ot' Tho ChemicMI Uoml Ami The ~tructurc (If

MolecUles And Cryatllls, Conloll Univur$ity Pros», Ithaca, ~QW York

I1Jl.>O, p. 57

211. ibid., p. ~:s

2Y. ibid., p. 51.14.601

30. ibid., p. Cil2

:U. Pildluy, P. J. lind SUidun, 'I.'. M., Seventh li)'IUpo!iiulII (lntornational)

on CollllJust1on, lSutturworthli :)-.:hmtific l'ubliclltiollS. l.onuon, 1!.l5~,

p. 235·244

::;2. I'adluy, P. J. and l)ual1&ln, 'l'. M•• Ul£hth ~YIl4POsiWII (Internation..1J

on COll1l.1u.stioll, 'fho Wlllili&llllt and ~Wllki.. s COllpllny, Ualtimuru, Hlu:Z,

p. 164-171)

33. Prutton, C. II. amI Maron, ti, II., 1:Ul1~cmtll.l Pril\cipl~s of I'hysica1

l.:lulmistry, fUClllillan COIUpal1)', New \'0.1.';;, HlS6, p. 2~b

:52

1W1N No. 71

34. Prutton. «.:. p. and ~lllron. ~. II., FundWllcnUl Principles of Physicul

Ch,uuhtry. MuclIliUan COlllpany, New York, 1~S6. p. 318

35. ibid •• p. 331

3<-1. Sl.lic.1en, T. 101., Allnulll Review 01 I'l\ysical ~1\L;l\uistTY, Annual !\uviows,

II\c •• PdQ Alto, California, .!!. 381·382 ll!.l(2)

37. tiu~ucn. 1'. M•• liifth Symposiwl\ (lntet'nationalj on Combustion,

Iloinhold Publishing COll) •• New York. 1:J5!:1. p. 40b-40a

3~. VOID l'iil:clen, A•• 101\ Production anI! Concl.lJltX'ation in I' lalllC~s,

Univenity of L.ouvllin l~e1giUll\j. Ann\,llll SW1I1IlOlt)' Hcport No. 2. ~untrl1ct

No. AP.~llOS2)·3~~. May 1962. ~Qe ASTIA AUZ78417.

;)9 ...._... , International ~ncyclop~dia of Chulllical :)dulll.:~, I). VOin

NOltl"anu COIllllW'lY, 1m:., New York 1~b4

40. - ••••• 1'h, Sdonce of Color, Thomas Y. ~rowel1 ~olllpliny. Nuw Yo1'lo,.

1!.154. p. ~27 and 30~

.'

IW'l'N No. 71

APPl.:.NlJIX. 1

l. Contents

a. Spectra l'uk\e

Lithium 4a

Sodiwn 4a

l'0t assiUIl1 '401

Rubidium Sa

l;c$iUlll ~.:l

l'halliWil Sa

UariUlll 6a

Strontium lja

!loron lUa

Cl,....vper lla

b. 'tu·olllaticity lJata Oiai:ralll 1311.

~. SYlIlbuls

A • Wavolol1ith in An~strolU

1 • Rulatlvo intensity

1;;\1 • cloctron volt~

u

f\ Ii Anastrolll..

~ ~ Milli~lc~on Ii loA

3. Rut'erunces

a. lloin, J, A., Pllllll/,) Photomet ry. MI.:Ul'llw-11111 l!ouk Compan)', [nc.,

Nuw Yor.k, 1960

b. Guydon, A. u., The S)lQct'1·os~up'y of JilWiIl.':l, JOhll \'o'Ucy And Sons,

Inc" New York, 1957

c. Gilbert. P. 1·,. 171W11C-t Spectra of tho Ul~u'Lcnts, Uulletin 7S3-A,

UeckllUUI InatrUlllents, Inc., Fullerton, CalU'ornia, 1961

111

tWTN No. 11

U. Harrison, G. R., ~tll.asachusotts Institute of Technolo~y

Wavelength Tables, John Wiley anu Sons, Inc., New York. 1~5b

Q. Paulinll. L., The Nature of tho Chemicll1 llonrJ, Cornoll

University Press, Ithaca, New York, 1960

f. Pearse, k. W. 6. and Gayuon, A. G., Tho Identification of

Molecular ~pectra. John Wiley and SOI\la, Inc., New York, Hlb3

4. Discussion of Contonts

a. The atomic and ionic spectra woro 51: lect~d from thll Ml'l' i~.lVC.

l~n~th Tablos. l'h~ cleJnllntul ionization potentials were c111culateJ

from the clllUo'2ies listeu in 1'ab10 2·~ frullI Pa':.llinl:' l'hl;t elUl.:tl'on voH,

10':\1. \)ntry Ihteu with the atolllic and ionic spoctra is the excitation

potontial or 4!mer~y require\! to oxdte that pllrticulll'r li110. Thus\)

oneriY levels were selected from tho Ml1' l'ubltls. '!hll ~and :SPllct~'u WLlrl.l

collectcu frOlll Poarse, Llcan, Gardon unJ Gilbert. I.latlll cOl1cerllini

continl.1wlI were selecUd from Gaydon and /,)uin.

b. tho int~n,itlos. 1, are ~y~ ustimates ba$~d on a scale of IV

for the lIItron¥llst line or band in the systelll. Ul.lcausc thu values wor~'

colloctQU frolll sllIvl:lral source!;, tho valutls In'Q vcry unl'olillolo 11liU shoulJ

not bu 1.1$0<.1 fur any quantitative purposos. For that matter, tlwy uro even

unr~UlLl>l(,l for quaUtlilUV\l purposes,

c. Compositl:l fl~ SPllctl'll wure pr~lJlu:ud fOl' ba'riUlli. 5trontiUl1\ and

~opP()'l'. flU,IlUU will pll'obabl)' nover corrusl,ond to thoso composi\:os sillce

all halolitmJil will W\doubt~\lly never bo prosent in one pyrotochnic composi­

tion. Tho information was, however, collocted into its cOl1lpositc form

so that by viuwi~l¥ ono paJ'0' tho reaut'X' clln visulIlhe the Lnca'doll of

vari.ous 11Iol"cules with rOlpltct to the ~u.vulonuth llnd color which they

2a

!tUTN Ho. n

emit and in relation to one wlothcr. These composito spQct:ra do not

include continuum or banu e~issions from ll101ucular and free radical

products of combustion froln ol'ganic compounds.

d. All olDissions for. t:l specific elcl\lent or molccul(~ are not

listed in this coll~ction. Only the more intense and persistent lines

a.nd bands have b~en mentioned. roX' exatllple~ 175 lines at'c listed for

l.>odiUlll in the MIT W::'.velength Tables whereas only six U'C listed herein.

For extensive list:i n~s of clnhs ion cia ta. the mT Wave l(mgth Tables und

simHar docUillonts lTiu!St be consuH.ed.

(:. A Chromaticity Data diajtX'a1u which relates wllvl:lcngth to coloX'

was included to aid. the roac.1er to visualhc the color in relation to

variou:o ru.di.ation wavelengths.

3a

1. Lilolllental Li.thi Wll

Atomic Spoctl'l.Il1A. tV I

6707. a 1:8 1'0'"6103.6 3.~ 54603.0 4.5 43232.6 3. B :5

1. elemental Sodium

Atomic Spcct1'UlllA &\i 1

5895.9 27i '958S9.9 2.1 105688.2 4.35682.1 4.33303.0 3.7 43302.3 3.7 4

1. Ulemontal Potassium

Atomic SpectlWll>. tV I

7699.0 176 9'7664.9 l.b 104047.2 3.0 44044.1 3.1 S

ItDTN No. 71

I..ITHIUM

Ioniz.ation Potential 5.39 E\l

Ionic Spectrum(None Located)

Continuum 460 to 320 mv

SOUIU~1

loni~ation Potontial 5.14 cv

Ionic Sp~ctnml

(None Located)

Continuum 602 to 360 m~

POTASSIUM

loni~ation PotQntial 4.34 ~v

Ionic ~pcctt'Ulll

(NOhO Locuttld)

Continuwl1 570 to 340 m\.l

4a

1. blemontal Rubidiwu

,IWTN No., 71

RUHIUIUM

IOllitation Potential 4.lH l:V

Atomic).

7947.67800.2b298.64215.6420J..~

Sp",ctrum£\1 I

176" 101,.tJ 10

52.9 82.11 8

Ionic Spec:trUlll(None Located)

1. elemental Cesium Ionization l'utontial 3.8~ £\1

AtOluic).

8!1l43.58521.14593.24555.4

Spcctrwllt\l 1

1:4 101.4 102.7 72.7 a

1oni c Spcct 1"UIIl(Nono l.ocated)

1'HAl.LlUM

1. lllolllontal "hIl1UUIlI

Atolllic Spectrum). £\1 I

5350.5 3:1 1037"/5.7 3.3 !,l

3519.2 4.5 73229.8 4.1l2!HIl. :s 5.2 22767. 'J 4 C' 2.'-J

Ionization Potential 6.11 ~v

Sa

IWTN No. 71

liARIUM

1. lliumental Barium

AtOlllic SpectrWll>. tV 1

5777.7 378 9'5535.6 2.2 10S5H).1 3.8 65424.b 3.8 13U71.b 4.0 1

loni~ation Potential 5.21 tV

Ionic SpectrWll" C\I I

4934.1 777 '4"4554.0 7.9 104130.7 10.9 0.53891.8 10.~ 0.22335.3 11.2 0.6

2. BaCH ~and SpcctruDlGroon bands, maxima 487, 512, SIS and 527 wu

3. BaO Band S!>ectrwlI

" I A I " I109"7.4 ! 6039.tJ '9 534S.7 '86782.8 8 5976.3 3 5214.7 76493.1 9 SSM.S 10 5086.7 66291.0 a S805.1 6 4!)()S.4 36224.7 U 5701.0 8 4850.b 6b16S.1 6 5644.1 9 4680.3 S6102.3 5 5492.7 10

4. ~llriUl1l Uxide (emitter spcciQ:i Wtc~r1ain)

U~~ ~roups at 4800, 5020 an~ 5500 A. The 5500 ~roup show~ twolI1ain band:. at 5445-5452 and 5482-5488. Uand hQad$ hllVO boen observedfrolll 4730 to 4855 lUUJ frOlll 5007 to S018.

S. DiBt' ~und Spectnw

A IS4rS.~ 4'5360.1 10S30S.S C.i

6. OaCl Uand Spocttum

>. 15320. a r5240.5 105213 1S167 2

" 152'6'0.6 4'5208.2 105156.4 5

" 1S13!:1.2} J-OSl:SeJ }S06b 1

RorN No. 7l

7. UaF Band Spoctrum

Croon Systelll). I

sooa.\! '84992.1 54950.8 10

extreme Red Systemh I >. 1

1430.8 ·'i 69S8.1 ()

"142.0 10 0935.1 <l711!) .2 10

B. 8aI ~and l)poctrwah X

5609.5 10S31H.7 75260Sl(jU

9. Uari~ Co~posite ~l~c Spe~trum

A I SRec~ A 1 Spudes ?:. 1 :iKtlCieS7430.l:l .,. Rail 5644.1 1J UaO 5208.2 10· ~aar

7142.0 10 8aF Sti09.S 10 Bal 5167 2 ~nCl

71l~. 2 10 liaF SS3S.b 10 tla. 5160 tiaI1097.4 S allQ 5$19.1 2 ~a 515b.4 S lIaBrQ9S~.7 6 UIlF 5.92.7 10 UaO 5150 ~aOH

693~.1 6 aaF 5424.6 1 I.lll SUt>.2l 10 l!a(,;lb7ti2.S I:l baO S41S.9 4 ~aUr S136 )64V3.1 ~ DaO S~tU.1 7 ~al 5120 ))QUI Ib2lJl.0 a IhtU 5360.1 11,) Udr 501£6.7 6 BaO62.24.7 6 /JaO 5349.7 I:i ~.o S06~ 1 ~a(;l

6165.1 6 bllO S:S;ZO. U S aael ~OOO.6 8 li<1FulO2.;) S !JaO 5305.5 b Uaiir 4~n.l S lJaFoO)!J.b 9 11aO 5270 lUl,Olt 4Jl'>!) ,4 3 ~aliJ

5976.3 3 HaO ~260.6 4 ~al1r 4~50.8 10 Ball5864.5 10 IhtO 5260 Sa! 49~4.1 4 »11+.5~O5.1 b 1).1,) 5240. :i 1 UIlCI 487U ... 1J~OH

5777.7 S aa S214.'1 ., !Sa.O 41iSO.6 b 1!IlO5701.0 a 'lau S:Z13 1 liaC;l 4()gO.3 5 6aO

4554.0 10 ur;.+

':; ::',;:.~< ...

1. Elemental St~ontium

IUHN Nu. 71

~TRON1'lUM

lonhatioll Potent ial S .b!> C v

Ionic Sl1eCh"u»Atomic ~peiCtrwn

A cv I4~j62.:5 473 '34872.5 4.3 24832.1 ~ • .) S4007.3 2.7 10

A430'5.54215.54077.13474.93464.6331W.7

1::\1 I(["0 U74

1$.6 3ij.7 4

12.2 1l.1:l12.2 212.2 1.5

2. ~rBr Uand ~puctrum

A II.Itl6b.7 106~13.0 10

3. tirt:l llamL Spuct rU&llA 1

6755.6 3"6744.7 SIJ61Y.Y 5ubU.7 10

4. ~rV ~and SpoctrumA 1

bOSS.b '1b632.7 106527.6 7<l512.0 10

S. Sri Band S)lc~t rwnA I

70~4.0 ':f7011.0 10b930.2 lUb1l47.7 10

b. ::irOll liand ~pocttulll

A68i'U667S051106460

7. :ir"U2 Uand ::;[)~CU'l.

A5950S!I()!l

(Ka~ a weak violet system)

A 1u41:l2'.9 '4"302.4 S6358.7 10b23~.3 2

). ! Ab419.0) :- 57'l,'j .5o3!>".7} 5772 .0~306.l} I:l S622 to 567062aS.!}

). 1IJ7b7.'d 106691 .~ I!6662.3 Il6177. :5 4

). .\ 16114.2 6109. ti T6111.8 6101.1 36109.8 6095.9 4oI07.!.l 6USY.!) 66107.5 6084.7 106105.2 6076.6 8

6U50 Stroll&

lun'N No. n

~. Stl'ontium COlUr0site Flame SpectrUlil

>. I ~eec:ie5 >. I :3J)~ci2 >. 1 Species70U'4.0 ! SrI 6527.b "7 Srr 6107.~ STOll7011.0 10 ~rl tlS13.0 10 5rl1r 6107.5 S~'01l

u!.l30.2 10 SrI CJS12.U 10 Srr 6105.2 SrOlIh847.7 10 SrI 6482. !J 4 SrCl 0095.9 4 ::lrOLIuti2U S:OlI ()460 ~rrJII 6089.9 6 ~rl,)H

6767.8 10 SrI 6419.0)8 SrF 6084.7 lU SrOH

tJ7S5.o 3 SrCl 6394.7} (1076.0 l:I Srl)ll6744.7 5 SrCl 6362.4 ~ SrCl 60SV SrOllM)91.~ Ii SrI 6358.7 10 SrCl 5779.~ .:>rFu67S SrU!l 630().1 }

8 SrF 5772.0 SrFub6b.7 10 Sr~r 62S3.U 5bn} Srfu662.3 8 SrI 623!1.3 2 :::irCl Sb70}obS5.b 7 Sr)~ 6177.3 4 ~rl 49b2.3 3 :::irob3:l.7 10 tirF 6114.2 1::1'011 411n.~ 2 ::ir661~.9 5 SrCl 6111.8 SroH 4832.1 5 51.'6613.7 10 SrCl 610~.8 SrOU 4bUi'.3 10 Sl'o5~O ~r<JH 610l:l.b 1 srOu

9a

lu)'n~ No. 7l

lial~uN

1. Lilclllontal 6eren loni:Ll1tion Potelltial li.2~ C\J

AtOlllic SpectrUlU 10nic Spoctrl.lll1>. £\1 1 A i:'I> I

24!J7.7 4:9 S 3451.4 20':'9 0.052496.8 4.9 4

2. IW (may be I.W2 or UF3) UAnu ~rectl"Ulll

'J'CIl1ow ~ystelll

A 1 X 1 ), 1S~\)3.8 "8 S~i2.1 1"0 5803.1) b5984.4 (I SlHS .1 & 5M>4. U bSti2S.7 7 S807.:S b

Llluo l>ru,)n :;ystclIl>. 1 >. 1 >. 1

5470.8 (;' 54S6.a if 44t>1.4 bS4ClO.l 4 4464.!J 8 444:S.5 6

3. I,;UZ ~and Spuctnw>. 1 >. .\ 1

0200 OS" 5450 rr 4710 3bU30 7 51110 l:l 4:)20 1SUUO 7 4~30 ~

lOa

IUlTN No. 71

(;UPI'Lm

1. ~lelnentl11 Copper ll)ni~ation Potential 7. n 10:1,1

AtOt'lic tipeetrUtll Ionic !:ipoctrwa>. ~ 1 A ~I,J

~2l0.1 '4 -SZl'.2 6.2 5 2247.0 IS. ~)

5153.2 CJ.2 4 21!.l2. ;) 1(... 2SlUS.S 3.6 4 213Cl. U 10.2.3274.0 3.8 93247.& 3.8 10

2. CuUr Uand Sputtf~

>. 1 ~ 1 ). IS032.l '3 4883.4 4' 4~UO.4 241154.7 4 48?~.3 H 4;)41.1 10

42til:l.u 73. CuCl ~and Sptetrum

I. I A I ). 1S2u2.~ () "Sli1.S '4 4S1S.9 55152 .3 4646.U S 4433.~ ~

4U82.2 2 4788.~ 2 43-53. ~ 104~46.1 1 . 4155.7 1 42~O.!) ~

AJJit1Qn~1 ban~s tawar~ the ultr~violot.

4. CuI ~un~ Spoct~). 1 A 1 ). 1

S4!1l4.1 "3 S.H2.4 ! 5117.3 '35471.1 • S2U7.5 ti !JI01.9 .3S4lJ1.3 ~ 521:l3. a 4 5072.1:1 105402.2 S 52"1.0 :s J()34.1I 35486-.5 6 S22().1 5 501:1.7 75371.5 S SZ12.2 7 4~1:l3.!J 45357.4 3 SlSS.8 3 4\.llla.:s ::;5328.50 3 51~1.1 7 4!iIl~.1 3

AdQit1~n.l b~ld5 o~i.t toward tho ultraviolet.

S. cue Uand ~pecuUlll

UraXlllo ",ua-iQIl). 1 ). I ). 1.

tJ&47 b~76.~ i bOS·9.3 1UbS30 tJ~~".U S 0045.1 !)

6493.4 1 6ZliU.\) 1 5847.tl .3tl430.0 S b16l.S ~ 5832.7 2tl40U.4 5 b1464~ a 5~27.'J 1

Gr-..n ltc¥i()\\: Lari:0 m.uabllll' of week. bll\dS~ indudinu f.1 Uttluil'\)ul' of I'telhu u.tw-r un lUlU 5228 , and haa!!, at 5344, S313,S30ti, 527U an~ S,74 • ~ittor unctrtaiu.

111

IH.lTN :40. 71 '

O. CuUU 'Sand Spect'r~1

0

Strolli diffuse band in ireon at S3S0 to SSSO A ,ll\d a wua\band in th~ or~n~.-r~Q at glSo to 6250 A. Wide ban~s h:also b~en reportod at 505 ~ and 524 mp.

7. ':\1(1 kSW\d SpQC.tNII\~ 1 " I ). I

~6~4.3 6' 508b•• ! 4~3i.o i5685. 'I 6 5061.1 7 49Z6.H U5677 .2 S S052.3 6 49()l.:S S

4781. u 4

8. ewl Uan~ System at 428U X.9. Copper Compos ito Porsi$tent Flllll1e SpoctXUl'l\

). I ~ecics 11 I Species " 1. ~poci:s

6400.4 S ~ 5312.4 '5 CuI 5USi' .3 (i" CuF6294.0 oS CUO S108 CUO SO~O CuOH62S0} (;UOH 5297.5 b Cul SU1~.7 7 {;ul6150} 5223.8 4 l:ul 4Yij3.~ 4 l:ul6161.5 9 CUO S27~ CUU 4!)6S.3 5 l:ul614().a S CUO 5274 CUO 49~4.7 4 l:ul.lr6U~g.3 10 Cull 5262.3 6 Cu\,;l 4!)32,.O 8 l.:uF6045.1 9 Cuu 5240 ,\lOU 4no.1i () Cu1:S1l94.3 6 cur 523"} CuI,) 41)01.3 5 (.;u\:SLJtlS.7 6 CuP 5228} 48li3.4 4 l:ulirSu77.2 S cur 5226.1 5 l:ul 48lH .5 4 Cuel5SS0}

CuOJl5220.1 4 Cu 4019.3 8 CuUr

S3S0} S21Ii.2 4 Cu 471H .!J 4 l.:ull5477 .1 .- Cui 5212.2 " CuI 4al~.~ S CuCl!i402.2 5 CuI 5153.2 4 Cu 4433.1i ~ CuC154116.5 6 CuI 5141.1 "I Cui 43S3.~ 10 CuelS371.5 S CuI 510::1.5 4 <.:U 4341.1 10 \,;ulh'5344 (;UO S072.H 10 CuI 42H8.b 7 CUU1'S313 cue 5061.1 7 CuF 4280.H !) Cuel

42HO.U Cull

12a

CHROMATICITV DATA 1\ D1 f,) Nl.:. III

o.~oo ---.,. --~---1

_UuO.........

.700.aoo,400

--1----- -

.oo

~oo-

:suo

400

,IlOU

,liOU' -_. _._-- ."- _. ---~--_H

G'U;I;;N

,IUO -_.+._-....;1\

,(jUC+,~.....~11001.1

!I

13&

, 1. Contents

lUHN No. 71

b. lbcrmodrn~mic and Physical Properties

Carbon. Hydroion and G~so~

LithiUlll

SQdiUlll

PotuldUll

Strontium

4b

5b

lib

7b

ab

lOb

~oron

,ThalliUlll

Coppn

2. Symboh

~ • Gal> ::It.to

1 .. Liquiu ~tato

c • ~rystallin~ »tate

8K .. U~irous Kelvin

u .. l.1ocolllpolun

AUf .. Heat of fo l'Illation ,

"

,\ ,

.,..

llb

,12b

13b

l4b

AI' • JitQC ont:riY of fOl'llllltion

U w U1SIociution ~n.r&y

Ib,

RU'I'N No. 71

3. References

~upl.lrscript if.

Uayuon, A. G. and Wolt'lard, H. G., Flames, 'l'hcir btructure.

Rulliation anu Temperature, Lhupillall and 1I1l11 Ltli •• Londoll, lUllU.

~,uJlcrscript ~.

Gaylion , A. li., Uhsociation 1.:.nOl"llilJs anu SIH~l:tra of Uiatolflic

~lolcculo5, ~hapl\lan and Hall l.td •• l,onJon. l~S:';.

:.iuperscript In.

~lullor, J. W., A COlUprchonsivlJ lrol.1tisCi on Inol'811llic unu lhL1ur~ticlIl

(;hernistl'y, John WHoy anu Sons, Inc •• New York, 16 VOIUlUUS, 1~37-1:lu1.

Superscript t.

Ilossid, I). ct al., Suloctuu Vuluc:s of Chelllical l'hul'Plouynulllic

Propc:rth$. National liUl'IH&U ot" btanJarus l.:irculal' ~,oo. Fob. 1951.

~upcrscril)t st.

~tull. lI. H. anu Sillk", G. c., 'l'h~r.molJynalllic Pl'opcrties of thlJ

lllullIonh, American Chumicul Sociot}', Ad.Vllllcu!I in Chundstr)' Series 11:1,

1956,

I,U'l'N I\U. "11

tiupcrscript s.

SuaQUIl, '1'. ~1., ~ifth S>"lllposiwn llntllrnntional) on l;ombustion,

Reinhold Publ.i.shillg (;orp., Nolol York, l~SS. pal,:() 4Uu.

~upurscript w.

Wilkins, R. L., ThoOl'ctical IJvaluation uf t;lu,lmil.:al PropellanU.

PrQntico~jall, Inc., ~nKluwood ~liffs. ~. J •• lYuJ.

:-jupllucril't j.

:itull, ll. H. ot Ill., JANAV: ThcfllIOl;lu,llUll:0 1 Data, lJOW Cl\l.lllllCal C\).,

Midland, Mil;.h., 1~60-I~uJ. I'rl.lpareJ uml..,l' Al1vanclJu I~osl,)arl.':h l'l'UjlJcts

AiollCY I'ro~rl&lll. U. S. Air Fore". (,;ontract Nu. i\FH({,l(j)wblr~U.

,I", I

IWTN No. 71

CARUON. ll'iUIWGEN li GI\::lb~

Free Encrgyj DissociationOf ronnation Hoat of Formation energyJ!. cPil/lIlo1e) (K cnl/Qlole) (1\ cllIl/lIlo1c)

~pecies 2000"K 0°1' 208.15°1(. Q"K 298.1S"K

1'12° ..32.4 -57.1 .57.8 219.3 221.5

ga () 0 103.2 104.2• 2.16 ~·lO.O +9.Jj . 10O.b 101.0

UP ..67.2 ..64.2 .65.1) 134.2 134.0Hel ..25.5 -22.0 ..2~.1 102.2 103.1liar .. a.o r 86.411~ll +b.7r +().2 r 70.4&F 0 0 36.7 36.7d 0 0 57.1 S7.~:2

0 0 45.4i.~r212 0 0 3S.6g

N2 ,0 0 225.0 225.90 ·0 :0 118.0 119.1'cO ..68.4 -27.2 ' -26.4 :lS6.2 257.:3CO2 ·.94.7 -~4.0 -94.1 381.~ 384.5

All gas statu.

References: Wilkins except ll~ noted by superscript.

4b

Rl.>TN No. 7l

L.ITIUU/l-I

Free 6nergyi Heat DissociationOf Pormation Of Pormation Un.crgy Uoilin~ Mn 1till~:

(K cal/mole) (K cal/mole) (II: cal/r.Qole) Point I'oint

Species~ 2000 0 K 29H.1SoK 0°1\ 01\ uK- --~-_.- ~--

Li... 142.bi

16SaJ 4S4 j

Li;lO c -64.2 276 1700jAf chanie$ sign from .. to + at :WOOa~

2()O\.l~fLi-,O & .. 37.1j

noLin c +:23.0 ..21.7 !.ISi/.oJ

AP changu s 19l~ from .. j to + at 12UO"'K"u124SJLid 1 +15.6 -15.1

At: chang@s si~n from Ujto + at 1300°1\Lill ~ 1'10.7 . +32.1. 5b()S&}

7.HJLiOH i:: -3' .ti -116!6J 263..102

"IIl~SUjLiOll 1 ... 46.0 -1l4.1 j

AF ChllU)iOS si¥n from -.to + at 3100 0 KLiU1L III -50.0 _57.7J :HS

1121,iLiF ,: -~:S.!.J -14<> 202.. 140~ 137&

1\)66)L:l.l: 1 -98.~) -14\)) .LiF

'"-98.0 -~o.s~ 80. '/

880 jL.iCl c ..50.1 -97·f llSg-IlS .

16SSiL.iel 1 ..55.1 -93.4)AF d\~Ul~CS (ranI ... to oj. .• at. 3700°1\

L1e1 i -62.8 • 43.8)l.il>r c ..83

t7X' lOO~ 8:231'

I,i~lt' g -41 lS831°

Lil C _04.81' Sll: 122rt.il W. _!tl r 1444:t'

P.lllh~onceli : Wilkins excopt a, not~d or ~uperscript.

Sb

IWl'N No. 71

SODIUM

Frllo UnCr~yj Jlellt LJis5IJciationOf '~o1"lUation Of Formation ~~nl.':rllY Iloilina Melting(I< cd/mole) (1\ cal/mole) (I\. cat/lUole) Point Point

Sr~cios~ 2000·" 2!:Hl.1S"1\, aOK oK oKV7F'f

Na 117'lj 371NauO c -1l1.\) d373Rl

Na2 2 c -120. ti d 13:\NU20 c -1.67 .9!,).4, >1623ffi l1!,)OJ

Na20 1 -8.tlO -93.2 J~p cnan;t0li siil\ from -.to + at 2200 0 K

NaB c -13.53 47& u700.1+21.1. at lS00"K. toF chang~s 5i811 fronl - to ... at 70Uol\

Nail ~ +1£1.4 +29.8NaOH ~: -:Zl.6 -102 S:J3

.83~.

NaOH 1 ..24.~ _1003 "'14S0411 chllnlilcs din f'rorA - j to ... Ilt 2uOUoK

NaOIl .Ii -:58.0 ·Sli.41285JNil'" c ... 71..7 .136 107i

_122 5

2100 j12tlSm

NaF 1 -77 .2 .UljNal~ g -73.2 .67)

lOtn jNaCl c ...41.1 ..!)S.2 ~ 7• ()&_961.1

1790JlO7'7'n

Nuc.:l 1 ... 46,'8 ..U3.Z j

AF Ch.UlieS iiiill il'om - to + at 37UO"'Kl~ar.:l K -$2.0 -43.5 1738NaUr c -8b 87,54,: lO20hl

N~ar g -36 1665Nal c -69 70.6" nsNa1 i .21 1577

R~i:'Cl=~mccs: ({ouini oxcept a~ notud by sUl1~rsct'iI't.

RU'l'N No. 7l

POl'A~SlUM

Pree Unorgyj Heat Ui~saciation

Of Pormation Of FOrlllation Uncrgy Uoiling ~lultini:

(K c:al/illole) (1\ cal/mole) (~ cuI/mole) Point l'oint

Spl.'dcs~ 2000·K 7.~8.1So~ O~K oK 01\

K lO39st 330K2U c -8b.4 !>ubliml's US4

iiiiJ <100 IIUli

K;l°Z c -118 d1052m 703K~03 c .. 125 d~Alm 70.3II.U.., Co -134 dY,)3m <J531l1

Kll· C -13.S j 42.~~ J6!.lOJ+2.3.6 a.t 1500°1(. ~F chanics :Iign frolll - to + at 7UO"1\

KJl g +21.7 +2U.41J~~jKUlI c -101.8

..865

1<011 1 -2S.U _!JU.7J l6UUKF c -134.5 115& 1775 1l;.':!)

.. 126s

KC1 ~ -51.6 161:10Kt.:l \~ -104.2 lU1.4~ 104:531

_100s

l<ur c, -~3.7 90.01: 10!)<J },O01\1\1\1 C -78.3 7b.4g 15\)7 US8

!toforonccs: Rossini oxcapt IiIli l1\;rcuu l>y suporscript.

11,1.' . ..,.

", '1b ." "

' ..

lW'l'N No. 71

l~UIU1)lUM

Heat l)issociationOf FOJ'lllation I;nergy Uoiling Melting(K cal/lllo1e) (Ii. cal/mole) Voint lloint

?J.>(l(:iClll~ 298.1S"K 0°1\ -K 0",

ab ~14st 312RbZO c -78.~

Itb202 c -101.7 d121Wll 9HiliRbZOS C -116.7 dllU In 7621n

Rb204 C .126.2 1.1143011\ 6BSJn

Rbll g +~3 39~

RbOH c .Y8.9 ~74

.88$RbF C -131.3 1231l loSI lO411

.124s .RbCl c; -102 j 9 1036: 1(,54 990

.. 104RbBr Co .93.0 Y2~ 1£J25 YS3RbI c -78.5 nlJ. 1517 ~13

Rcforuncu: Rossini UXClJpt as noted uy sUJlf,lrscript.

8b

RUTN No. 71

l,;~~1LJ'-1

Hellt DissociationUf formation UnuriY aoiling Melting(K cd/mole) (K cal/molu) Point Point

Sp4ldos ~tate 298.1S Dt;. U"K Dr,: DK- --

es 1 ~SHst 302st

(;52U c .15.9 703(;52°2 c ..96.2 d.13471U &671ll

CS20S C -111.2 d13331ll 77501

CS204 C ..124.2 dI5:iH'u 705n1

C!tl'l g +29 41 11CsUH c: -97.2 S4S

..9),5

t,;sF C .126.~ 127~ IS24'u 955.. 1211s

esCI c .. 103.5 106bl 1573 91tl-10S5

Csllr c -94.3 ~Sll 1573 ~O~

Csl c -80.5 7ijill 1573 tI!)4

Rot'orOllel51 RDssini oxcupt u.s noted by sup~rscript.

RUTN No. 71

STRON1'IUM

Heat UissuciationOf Ponation llnerar Uoililli Maltini(I( call1'llOlc) t~ cIl1/laOle) Point Point

Sfecies~ 29S.1S·lC, 0"1<. .", oK- ...........

51' 1640st

1043srO c -141 lO6f: 3273111 2688srO c -153srftO c -IS.Sr i +52 :S8~

srHO

c ..42Sr( Hh c ..22gSrF a ·s 62~

SrF I: ..290 l673'>rCI i +9 SijiSrCl c ·198 1141:1srlir~ c ..111 ~l()

Sr12 c ..l~ 7aaSrl 4bW

l~rGrlnC'i: ROSlini exc~pt ~I noted by superscript.

lOb

RUIN No. 71

llAlUUM

Heat Uislioc:iationOt' Fonaat1on Ellelo°n lioilina Meltil\i(li. c.:al/llOlo) (1\ cal~lIOlfl) Point Point

SL.lOcios~ 25Hi.1S'lK O'll:, 01( oK

Iia 191011t !l83,ta.a c -133 124~ 2273A1

21~O

UIl08 c -ISOu:a c ..147& . i .S:z 41&tlaH c -41all,3HJ 2 c ..226 681~.P i ..liJ b!i~

aaPi c -287 1673111 1593aae i +24~Cl c ..111 Sli"aC12 c ..205 1235aaBI'2 c ..180 11230&12 ~ -144 IOU

Ret'.rellee.: ROllin! oxcept a. noted uy superscript.

llb

RUTN No. 71

BORON

PriO cnuiy j Hoat DissociationOf Jlol1ll&tion Of Fomation EneriY Iioilbli(II: cI1/llIOle) (K eal/lIlole) (K clll/llIo1o) "oint

Spccicla Stat" 2000·K 2!HI.1S"1{ 01( oK-~ (2313r ~.1tini point) 3~49.9j~o a -39.1 +:S.74J 18a (17S~)

(UO)Z iAF ~LaniO$ Iii" from + jO • at 200"~

Not lsolateliln.119.8 -11U.8 .91AF chani~$ sian fr~ - to + at S800"K

(723"f ja2°;5 l: ·1118.6 -SOS 7<4~

.301;11101 Ung noillt

82°3 1 -11J4.0 2S20i f

All chana.' din frOlll • to .. at 4eUC"K

~i03 lo'o ·177.5 .;ZOti 652a .S1J.7 +106 j 68 (f,91t )

8112 j ...U.O +btl.OJIiH3 Sl +33.3 ... 11:1 270tlF II. -87 •• -4S.S j 196lif2 i -149 -134j 327lUl~ a ·2.0 -270 458 174r

at:! a ·l.S +42.S j UBiAF ~anie. »lin fr~ +.to .. at 2000 0 K

tlt.:l;l i -39.1 -20.7~liC1 3 a -72.e» -tl7.l J 28S.6r

AF chanao5 liin from • to ... at 4~OO·Kl.ilir i +2S r ~7i

364.4)lUlrJ 1 -S7.9J-3~.S at 1500w~ j

~ar3 i -37.2 -4~.7

AF chanae, ai~rt frOd -jto ... at 420U"KU1 3 K +lS.0 +lS.O

b_tw••n 298·~ lad bUUO"K, AF 1» nCHativd onlyin "OO·a:; to 6UO·~ rang~. 11\ that rani" it~.ch....xi~ n_gQtivo .1.o~4.

~ c w 1Il. S .6D.~ 30bAf chanW.' stiP fr~ - to • at 2~UO"K

W'l " +lS4 ~2.S(9J~)

I~~ ferences: WilUal ucept u notod by I",pltneri pt: •

llb

IWTN No. 71

1'1W,l.l U~,

Heat OissociationOf formation linoriY lloi U"" Moltins(I( c81/liole) (t:- ed/_ole) Point Point

~peciu$~ 298.1S"~ O"K ·K er-

Tl 1740st S77st

no c -41.~ 773 573'1'l ~O3 -0 I!D 1073\1\ 9~O

TlH & +48 4()~

nUll c ..56.91'1 tOB).3 c -122TlF i ·33 lO9 11 ~23 bOOnc.;l i -16

~7ilO7~

703 1111'1c.:l C -49TlC13 c -83.UTU~r S ·S lOli9118r' c ·.u 74& 7321U

Tl~r:s c -S9TU i +7 10U~

T11 II ·30 t)O~ 7l31ll

Koferoncos; ~lUIini excopt as noted by $~lerscr1~t.

13b

IWl'N No. 71

(;OIJI'l:R

Hoat IJhsuciationOf FOJ'liation ~noraY Uoilin& Mltltini(K <:&l/llWle) (K. c:ll1/lllOlc) Point IJoint

Spoc~es~ 2~8.15·k: -K "K -K

Cu 2aSS l~Stl

CuD i +Z5cue ~ -37.1 lUi I\o280ll111 133 illc:.:u 0 c -J!I.8 IoU073$ 1502C~ i +11 ~2~

Cu(OH) 2 c ..107Cull c: +044 u~~ subli~o$ 1473w 1181 lU

CuP c: -127 0773 to CUplilcud i .J2CuCl c -32 ~Si

r~q703

1327CUC1 2 c: -49 U 7711l

CuBr j +38Cul.lr c ·2S 7iji:

r~~"l761

1227711

111Culh'2 c .:U dCuI i +62CuI c: -16 4CJi

r~~2.j ij61

CuI2 -1.7l04S III

c: Soli~ not i501~t~cl

RU{Q'i'OIlCUII: ltoUllll n.cept III nut,d by iupelnc:ript.

, ,I

.,1 ,

.' /.t····

"" "

, "

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14b

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... ; , '"

u.s. :!aV2\1 A!Io::uniUc;n C"pot. en"". Ir.d"lUl4(!!I7T~ .'Ca. 11)

'j'rrmRY OF COLORED FLAHK PllOOucrIOll13ernard E. Doudll, 2Q !'4Tell 196433 p D. lll'j:!!...>dix 1 ft 11 l:n<:1auifii!d

The th2cri~ and attTil""t~1 ossOlc1A;:ed withc~lored flage pTOductien are presanted.Variab1l1ty of "'''litters, .....i ..sior.. sill! rolor"j:h fl""", t".,peral:'.Jr'! is discussed In-reo etion to :het1'Odynar'liC :>t"O;>"rtles of thereectar.tli and eo=UJstlon pcod:lcb.

u.s. !lA_I "-nlUoD De~. tun... Inl!i&Dll(en~. n) .

r.xn (]I C(l(.C«m F1..AHE HtClOOCTIO!f!lernar.! t. Douda, 20 HaTdl 19~33 P C a~l~ I 0 Il l~l....ifled

1 , Yle.mes. Colored2. Flare, Col~3. E!&sslor..4. ~t~erw

5. 5p-eetY'a, fl~

I. !'1':leII, ?J1T5:~. 71Ill. ~da. ~.S.

1. r~, ColcT3f2. F1.e.rtI. Cel"nd3. ::....iUloM4. !.::t!tte~

.5. S,ec.trol!., of ~ &""':S

u.s. :{e.V!l1 ~dU~" t-«.,et. C...,•• "nctiaaa(!UmI !foe 11>T'!J:CJlY CF CO\..C>iE:I Fl.»!! ~OO~a.!!>er.'lar.S !. :>ou:i~. 20 Me..en 1564;3 p Ii. ";,~r.:l1Jl I .. 11 ::=1aniUd

!;,e cl::~rtea and ,,~trHntu !l.IJs<>cut<od with~~1oreO flaoe ?rod~~tion !lre pres.~t~~.

"·art~~Hi:Y of e"'!1tters. ~Ui:Tt'.. &.-K! c01"rwi,;n £1""" t",..,erat;,!'!' !s ~15c;us8d 1..re' "'!:ion to 1:h2~yru:..-.:tc ;>~rtilSS of ther~~C-:3r.ta and co.c:atiol! prOC:::Jets.

'J.S. Y.a...,.1 ~nitioll ::epot. Crm:a. hdiUoa{!Imr 1io. 7l)

T1~"'Y I:!r COLcu:I) E"..A.'2 amocnOll~rr...n !.!4lda. 21J Mllrell li6433 P & a;>peMb 1 '" n !:nclasrlf1~

1. n......... Colftnd2. 11=e, Col"r3d3. ~..iOM

~. ~tt.",. $~eetrs. fl~~

!. '7i1:1eI1. iWT/f No. 71III. t~~a. B.~.

1. n~. Col91'*f2, Flu·... Color8f3, !£u1or.t1~ • !.oa!tt..~.5. S;>eet:n. i 1"'3l

~i'::e'The thl!.ort~ and &:tr'<.Jt.... 83scclal:ed witbcolored fl~ productlon are pre5.nt~.

Vartal:Uity of en1tters. "",,1.. ic"ca aD<! colo1'rith flame t£~rat.ure is di5CURm inA:,.Uon to 1:.1",~~c pTt'po:!rtlu of there.;ct/1r:~ ~ =..a:-...t'LCO prodUCts,

1. 7!t':'en. ~!l "",. 71111. ~da. ~.3,

The thertu a.-..1 attri~tu an:>datld vUlt""tared fla= ?rn<h~t1oD are "1"l!."nl:~,','art~bility of ~t~nl.....lui-otIS si><! coler~th fla~ teJ!Pera~re is cHsc-..:a:sed int"l!;.at':"n to t""~~e .,n.....rtlea <Ii ~.r!!.:eta"t....-..1 eo.e-.atiDa prodl.l~ts.

I,11,Ill.

;;,rmr :to. n:~. 3.::.

FLAI'JI.4 PRODUCnON20 ~1arch 1964

& 11 Uncla6~ifled

u.s. N,'lVnl Ammunition Depot. Cro.ne.(lW'l'H No. 71)','[mORY Ill" COLOR rIDBnrnnrd 1~. Douel.!!.,13 l' (:. llppondix !

lod i (lllf.l It'lUl1\t\l; I ColoredFlnt'c, ColoredEmissiontll';mi tters~~pl.!ctri'\, f 1amn

1'hf' ';::'maorietl and ~I:tr.l.butll' aSliloc::1atad \~ith

cQl()rar.l l:lll.lllU prtlduction arB Pl.·08t!llltad.V"t'i~\bility ,)£ umittun, ernia.. :1,otll> and C010l'

with f!.\llilG ttlll\l)(\rlll:url~ tt.! diacuNIl03d 1nr') 11\1:'1011 til tl1'Jrmodynnmic proporties of t~HI

\'e!lctunt/i J.nd cOlullutJtion jlt\)ducta,

l.U.llr.

'l'i II t:

lUY.1'N No. 7\{Ioud'.\ l l). r::.