ML20134K776

Summary of 850731 Meeting W/Util Re Open Item 4 Concerning Toxic Gas Evaluation of Chemicals.List of Meeting Attendees & Related Info Encl

ML20134K776
Person / Time
Site:	Vogtle
Issue date:	08/22/1985
From:	Mark Miller Office of Nuclear Reactor Regulation
To:	Office of Nuclear Reactor Regulation
References
NUDOCS 8508300433
Download: ML20134K776 (16)

Text

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l UNITED STATES

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! Y' NUCLEAR REGULATORY COMMISSION ,

i.. , E MSHINGTON, D. C. 20555

( ~ /jl August 22, 1985 l Docket Nos: 50-424 and 50-425 APPLICANT: Georgia Power Company FACILITY: Vogtle_, Units 1 and 2

SUMMARY

OF MEETING HE'.D JULY 31, 1985 ON T0XIC GAS EVALUATION OF CHEMICALS The staff met with the applicant and its representatives on July 31, 1985, to discuss Open Item 4, " Toxic gas evaluation of chemicals." The participants are listed in Enclosure 1.

The applicant described the location of its control building air intakes, the toxic gas (chlorine, hydrazine, and ammonia) stored onsite, and the intervening buildings. The intakes are located on I.evel 3 of the control building on either side of the northern end of the building. The closest chlorine is located approximately 615 feet southeast of the control building while the closest hydrazine is situated approximately 450 feet to the northeast.

Drawings used by the applicant in its introductory presentation are included as Enclosure 2. .

The applicant proceeded to describe a new analysis of the chlorine dispersion taking credit for the fact that chlorine is more than two times heavier than air and for the height differential between the ground and the intakes. In performing its calculation, the applicant used the Gaussian model of NUREG-0570.

The applicant performed a similar analysis for hydrazine. Hydrazine is approximately 10% heavier than air. Both analyses showed that concentrations of gas at the outside air intakes would be essentially negligible. A similar calculation was not necessary for ammonia since both the applicant's and staff's earlier calculations indicated that it would not be a problem for the control room.

The staff indicated to the applicant that its analysis as presented did not appropriately account for wake effects from intervenino buildings which may cause additional chlorine. rise to the intakes than accounted for by the applicant or point source releases at ground level associated with neutral or unstable atmospheric diffusion conditions which could diffuse the chlorine gas up to the intakes. Consequently, the staff directed the applicant to perform two types of analyses for the two chemicals

• as stated below.

• In a subsequent phone call on August 6, 1985, the staff told the applicant that a calculation for hydrazine was no longer necessary because the revised staff calculations indicated that it would not be a problem for the control room. Earlier staff calculations inadvertantly included the assumption that part of the aqueous hydrazine would flash into vapor upon tank rupture. This is not possible since the boiling point of aqueous hydrazine is higher than ambient temperature.

8508300433 850822 PDR ADOCM 05000424 A PDR 4

1 (1) Flat plain analysis -- assume a flat plain point source release with worst case stability and windspeed combinations which diffuses the chlorine to the intakes.

(2) Building wake model -- assume stable low windspeed conditions taking into account the wake effects of intervening structures such as the ,

containment building.

A telecon was established for 11:00 a.m. August 6, 1985, to discuss in detail the applicant's methodology for these calculations.

The staff and applicant also explored modeling differences for the hydrazine calculation. The applicant took credit for the structure surrounding the hydrazine container which would restrict its flow and therefore lower any release. The applicant also provided the staff with information regarding the evaporation of an aqueous solution of hydrazine. The excerpt in Enclosure 3 was provided by the applicant.

The staff and applicant also discussed infiltration and mixing in the control building. This information would prove helpful if the applicant's calculation showed that chlorine levels at the outside air intakes would be dangerous to the control room. The applicant has assumed 100% mixing in the spaces adjacent tt the control room. Flow rates for the control building HVAC are shown in Enclosure 4. The applicant stated that the pressure in these spaces is less -

than a positive 1/16 inch water gauge and therefore it expects exfiltration from these areas. The staff indicated that wind effects can overcome this pressure and that pathways to the outside should be identified. The staff will follow up on this item depending on the outcome of the applicant';

analysis and staff review.

The remaining portion of the open item concerning emergency procedures for the control room operator may not need to be addressed depending on the applicant's analysis results. The staff will follow-up as necessary.

Melanie A. Miller, Project Manager licensing Branch No. 4 Division of l_icensing

Enclosures:

As stated

< DESICl?., 3 ORIGIGTO Certified By ._

D l

Mr. Donald Foster

. Georgia Power Company Vogtle Electric Generating Plant CC:

Mr.'t. T. Gucwa Resident Inspector Chief Nuclear Engineer Nuclear Regulatory Commission Georgia Power Company P. O. Box 572 P.O. Box 4545 Waynesboro, Georgia 30830 Atlanta, Georgia 30302 Mr. Ruble A. Thomas Deppish Kirkland, III, Counsel Vice President - licensing Office of the Consumers' Utility Vogtle Project Council Georgia Power Company / Suite 225 Southern Company Services, Inc. 32 Peachtree Street, N.W.

P.O. Box 2625 Atlanta, Georgia 30303 Birmingham, Alabama 35202 James E. Joiner Mr. R. E. Conway Troutman, Sanders, lockerman, Senior Vice President - Nuclear & Ashmore Power Candler Building Georgia Power Company 127 Peachtree Street, N.E.

P.O. Box 4545 Atlanta, Georgia 30303 .

Atlanta, Georgia 30302 Douglas C. Teper Mr. J. A. Bailey GeorgiansAgainstNucle$rEnergy Project licensing Manager 1253 lenox Circle Southern Company Services, Inc. Atlanta, Georgia 30306 P.O. Box 2625 Birmingham, Alabama 35202 laurie Fowler, Esq.

218 Flora Avenue, N.W.

Ernest L. Blake, Jr. Atlanta, Georgia 30307 Bruce W. Churchill, Esq.

Shaw, Pittman, Potts and Trowbridge 1800 M Street, N.W.

Washington, D. C. 20036 Tim Johnson Mr. G. Bockhold, Jr. Executive Director Vogtle Plant Manager Educational Campaign for l Georgia Power Company a Prosperous Georgia Route 2, Box 299-A 175 Trinity Avenue, S.W.

Waynesboro, Georgia 30830 Atlanta, Georgia 30303 Regional Administrator, Region II U.S. Nuclear Regulatory Commission 101 Marietta Street, N.W., Suite 2900 Atlanta, Georgia 30323

_~

r ENCLOSURE 1 PARTICIPANTS NRC Southern Company Services C Miller J. Bailey T. Quay R. Thomas K. Campe K. Kopecky K. Dempsey 0. Batum A. Brauner-I. Spicker Georgia Power Company J. Fairobent D. Hudson W. I.eFave Bechtel

5. Cereghino T. Luke T. Mark A. Cinar Y. J. Lin o

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i rue Chemisoy or Hydrazine -

i L. F. AUDRIFTII Professor of Chemistry Unimaity of luinais I l

{ IIE'ITY ACKERSON (H;t; l' , Research Associate l, Unimssty of illinois f

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GENEftAL CIIElllCAL PROPERTIES los Cll APTER 5 ,,yd,,,,,e is , me,iz, base th,n ,mmonia, mhich mi,ht be cn,i,i.

pated from the fact that hydrazine may be regarded as an ammon. .

derivative in which one of the hydrogen atoms has been replace.1 by the more negative Nil: group. The second ionization constani for hydrazine in aqueous solution has a value of about 10- in Properfies of Arjucous Solutions "9"".us solution hydrazine resembles ammonia, however, more than it does the orgame diamines. It is pnmanly a mononcel base, attimugh a goally numiser of salta containing two moles of of jfy,/,,asine IlX per mole of hydrazine have been prepared. Theec, howeni, are stable only in the solid state. Alany salts of hydrazine haw Solutions . f hydrazine in water are available commercially in been isolated and characterized and will be discussed in none ecveral cone. 'tn lions containing 40,85, and 100 per cent hydra. detail in Chapter 8.

zine hydrate reqectively. Although it, is doubtful if hydrazine Itclated to this tendency on the part of hydrazine to coonlinate hydrate (N.Ila-11:0) as such exists in aqueous solution or as a the hydrogen ion to form the corresponding onium ion, Nall..ll ',

pure liquid r- nip..und, t his convention has long Icen used to specify is its ability to act as an electron pair donor in the formation of the strength f s..httions of hydrazine containing less than 50 mole metallic ion complexes. In forming such hydrazinates it behaws per cent h3 .1 izine. Ilydrazine hydrate in the indicated concen- very 1 rgely as a bidentato molecule. hloet of the coordination trations is u- ful .linctly for a variety of chemical reactions, such compo. ids contain only half as many molecules of hydrazine as as those inwived in the synthesis of azides by reaction with required for the coordination number of the metallic ion. hlany nitrous aci.I a$.1 nitrites, and for solvolytic reactions in which hydrazinates have been isolated and characterized and are dir-the ester gn op er an active halogen in an organic compound is cussed in Chapter 9.

replacest by he hydrati.le radical: One of the very characteristic reactions of hydrazine in aqueno4 solution is its ability to act as a reducing agent. Aqueous solo-IlONO iItONO, etc.) + N ll. + KOli - KN + 3110 2 tions of hydrazine have been employed to elTect reduction of various metallic ions to the metallic state, as for instance in iho Itt OOll' + N ll. -+ llCON ll: + lt'Oli i

case of copper, a,dver, gold, and the platinum metals. Ilydrazine IP 'OX + 2Nall. -+ ltCON:lla + N lle IlX also brings about the reduction of strong oxidizing agents such a<

permanganate, iodate, hypoiadite, iodine, cerate, and the like.

hiany of these reactions have been used for the quantitatiw CENER41. Cili. MICA 1. PitOPEttTIES determination of hydrazine, but only under very Npecial conditions Solution < .4 hydrazine in water nre basic. Ileaction between Utidation of hydrazine does not ahvays proceed directly to nitrogen hydrazine anal water is represented by the following equilibrium but may give a variety of products, including nitrogen as well as

• for nhich tir dismciation constant of hydrazine as a base has been ammonia and, in some instances, hydrazoic acid. Fornmtion i.f calculated: ' hydrazoic acid takes place most readily in strongly acid solutions containing the hydrazonium ion when such oxidizing agents as Nall. + 1I 20 ;e Nails + + 011- hydrogen peroxide and peroxydisulfate are employed.

Aqumus a lutions of hydrazine undergo autoxidation quite i

K -[Nll.+l[Oll 1 - 8.5 X 10-' (at 25*C.)

i

{N ll.]

g .

rapidly to yield some hydrogen peroxide as an initial product ..f the reaction. I)ilute solutions of hydrazine. therefore. underp.

rapid delcrioration on contact with the atmosphere. This faci A.

103 pit 0PEftTIES OF iQUEOUS SOI.tiTIONS OF llYDitAZlig PIIYSIOLOGICAL EFFEUm 90 must be kept in mind aben aqueous solutions of hydrazine are employed in synthetic reactions and when hydrazine is to I.e PIIYSIOLOGICAL EFFECN

• determined quantitatively as a base by titration uith stamlant Precautionary measures must be taken in I.oth .1.e manufaen...

seid. Deterioration can be prevented imly by Lecping such solu- and the use of hydrasine amt its salts. Ily.f raz.. .- vapor u t t.n .'s tions under an atmosphere of nitrogen. The usidation of hydra- the nose and throat upon inhalation. t hirin : 11. . m ly op ra n.. .

zine is an intriguing subject and is iliscuwd in some detail in of the German Gersthofen plant, it was rep rted that wo kno n Chapter G. exposed to the vapors of hydrazine hydrate wen likely to not.. i Iteference has already been made to the fact that the anhydrous from a delayed action on the eyes. No etTects wer. Irlt for a pai-1 base is a thermodynamically unstable compound. Ilydratine tends of Perhaps 10 hours1.157407e-4 days <br />0.00278 hours <br />1.653439e-5 weeks <br />3.805e-6 months <br />, after which the eyes l<cm :r intlamed .u.1 to undergo decomposition even in aqueous solution, esp ially in swollen, and discharged pus. Temp.rary blindi . ss for alu.ut i the presence of catalytically active metals. The exact ..ature of days often foHowet Patients usuaHy n cot ,ed fully in almoi a

~

the producta obtained is dependent up.n the pil of the solution. yee can as wm taken to pmwnt We es. . .e of the valw m ag w una a al um vqu to un e

- Dilute solutions of hydrazine in watq decomimse in accordance gas masks identical with those used for amrion a 8 Contart ..I wu the equathn:

the liquid hydrazine on the skin has also Inn toumi to can .

9 ,

3Nell. --+ 2 Nil3 FN2 + 11 5

varying conditions of dermatitis, depending upon the individo.a -

2 I sensitivity to the chemical.

~ As the hydroxyl ion concentrati .n is incre(ased, more and more Since hydrasine reacts with compounds coutui sing a carinaai nitrogen and hydrogen are obtained in propertion to the quantity group, it might have been expected to have so:ne o tion on organ At a high pil, the catalytic decompeition of hydra- isms. Loew

• found that seedlings, algae, fission oiganisms, mol.1-

. ' ofzineammonia.

in dilute aqueous solution approaches complete decomposition and lower water organisms are destroyed rapi.dy by a dihae into nitrogen and hydrogen as the limiting reaction. This subject sohition of hydrasine sulfate, but Raciboraki

• i! aimed that i h.-

is also taken up in Chapter G. salts are not invariably poisonous; some fungi ariuully assimd..w The instability of aqueous solutions of hyd.arine has developed them.

into a problem of some importance. Not only must care be taken Physiologists and biochemists have investigated the toxicit3 ..i to avoid contact with the atmosphere because of reaction with hydrasine administered internally to animals and have attemph d oxygen and absorption of carbon dioxide, but many other impuri, to explain its action. Loew

• found that a dose of 0.1 g. of hyih.,

lies also cause rapid deterioration. Decomp >sition is brought sine sulfate peutralised with sodium carbonate and administem.1 about by contact of aqueous solutions of hydrazine with metallic subcutaneously to a guinea pig caused death in 2!i hours; a d.. .

oxides and such metals as copper, iron, un I steels. . Statements are f 0.5 g. ad:ainistered to a puppy in a similar manner cau-I also reconled in the literature that hydrazine solutions are sus- death in 2M , hours. When small doses (0.0 > g per kilo b..dv ceptible to decomposition in glass containers. !i, houever, the **'E ## u amusly m aa sbne glass (especially Pyrex glass) is carefully cleaned, 85 per cent a i n wa8 Produced; .m large doses (0.1 g. per kilo) the stag.-

of stimulation was more intense and was followe.1 by depres.4n.

hydrazine hydrate wd. l undergo no decompe.t ion over periints as long as 6 months.' It is ymte probable that such decompwtion Mi in d dd w-lein 2 4 Giv.m h mA u produced salivation and sickness. The heart beat was more rapa as may have been noted is due o the fact that rare was not take" at first, then slowed gradually and became irregular; body teni-to insure clean glass surfaces. binee hydrazine attacks rul la r*

cork, and organic maten. als .m general, such suletances must be

• The authors daire to expreme their appreciation to Dr. V. Thomas Au o.i of the Carle Memorial Clinic, Urbana, Illinois, for his ami tance in revica n.,r avoided when hydrazine is subjected to storage. the material on the physiological properties of hydrazine.

9

- d

304 PituPEltTil'8 OP AQUEOUS SOLIITIONS IN llYDRAZINE Tile IlYDitAZINDWATElt bYhTENI t v, 3rrature decren el. The respiratory movements were observed to in some w:y.88 It has also been noticed, after the administrati n be similar to tirme caused by asthma. of hydrazine to dogs, that fat in the blood is markedly incre:c.a llydrazine salta cause hyperglycemia and reduce hepatic glyco- the maximum being coincident with the hyperglycemia conditi..n "

grn, which is nel due to a transference of glycogen to the muscles it is interesting to note that phenythydrazine causes hemolv +

since here tin the glycogen is reduced? Since the glyoxalase of mature red cells and has tan used extensively in the treatni. ne nelivity of the liser is not markedly altent!, however, by the action of polycythemia vera; yet this efTect is apparently a specific ..n-of the hydrazine, the explanation must lie elsewhere

• The and is not shared by hydrazine iiself.

respiratory quotient of hydrazinized dogs indicates that the hyperglycemia and loss of glycogen might be due to an increased combust on of rurtnhydrate? PilYSICAL PHOPEHTIES OF EllE IIYDHAZINE-WATER SYSIDi The most des p-seated changes occur in the liver, where hyper. Ileference was made in Chapter 4 to the fact that hydrazine i-emia is observed to take place? Acconting to Wells," the cyto- an associated liquid. Water is also highly associated. In interpn i .

plasm of the liver cells undergoes a profound metamorphosis after ing the behavior of any but the very dilute solutions of hydrazmr the subcutaneous injection of hydrazine into dogs. Ilydrazine ,

in water consideration must be given to the fact that both hy.hv wems to have I ttle ofTect on other than the hepatic cells and does zine and water are associated liquids and that some reaction b.~

not cause any appreciable destruction of red corpuscles; slight tween the two components does occur at all concentrations inv..lv-hemorrhsges nie occasionally produced, but much less than by ing (1) limited formation of ionic species that can be only hydr e other liver poisons. It attacks only the cytoplasm of the liver, zonium and hydroxyl ions and (2) hydrogen bonding bete n never affecting the nucleus primarily, and causes pn,found fatty simple and polymerized molecular species of both hydrazine and degeneration. in,this respect, it resembles phosphorus, but di1Ters water, in two important particulars. Ilydrazine attacks first the cells Considerable hydrogen bonding does take place in a liipod in the center el the lobules, whereas phosphorus shows its first solution of hydrazine and water as indicated by several outsinnd.

an.1 most marked effects upon the peripheral cells; second, phos- ing properties of the, hydrazine-water system. Ilydrazine an.!

phorus usually causes marked fatty changes throughout the body, water form a constant boiling mixture with a maximum imihne ubereas the erect of hydrazine is limited largely to the liver. point at 120.5'C. (771 mm. pressure), corresponding tu a mimur

'l be presence of adrenaline can also still be demonstrated in the containing 58 5 mole per cent hydrazine. This imlicates that yap a n.henals in the case of hyttrazine poisoning. 0 pressures of hy_drazine-water mixtures exhibit a negative devinin.n Ilydrazine in ik.gs causes an increase in the blood concentration y. from Itaoult's law and that these vapor pressures, or the IIIosi d (nnhydremia), ahich is ascribed to fluid h>ss and failure of fluid gi pressures of each of the constituents, are theiefore less than :nie retention. It is probable that concentration of the blood may be L be calculated from the mole fractions of each. The data given in a prominent fai tor contributing to the usual fatal outcome of this Tables I and 2 represent the only published information on ihr intoxication. 'l here is no necessary relationship between the degree i( vapor-liquid equilibria in the binary system at approximatriv of 1, hod concentration and the extent of hyperglycemia, although atmospheric pressure. The older data accumulated by I ohiv generally bhui concentration is at its maximum when hyper- dc!truyn and Dito u give the boiling points of various mixtun -

gl3cemia is m.rt marked. Previous to the decrease in blood sugar , up to 7(i mole per cent hy Irazine. The more recent informat n.n content, a tran ient condition of hyperglycemia prevails without any evidence of kidney lesion or appearance of sugar in the urine."

j presented by lljarkman " does not extend beyond 48 mole per cent hydrazine. It is apparent that ordinary fractional diotall o

.\f ter the disappea ance of the anhydremia, a slight reduction in "

tion of dilute solutions will make impossible concentration of a the bloal cell c amt may occur,u and it has been stated that both , residual liquor beyond the composition of the constant boihng m3 hemogloliin and methemoglobin are changed by the hydrazine ,

mixture.

9 a.m

106 Pitol'Ellll'.S OF AQl'EOUS SOLUTIONS OF IIYDRAZINE THE HYDItAZINE. WATER BYSrTEh! Ita inrpection . l the slensity. composition data also d:monstrates the general observ tion th:t physical properties of the bin av lhat the hinary ystem is far from ideal in its behavior. hf axirr. im system show a maximum or minimum value in the region of J.a

<!rn<ities corre ond to mistures approaching the composition of a mole per cent. corresponding to N 4H II 0. The existence ..f a monohydrale. l'he older data by Dito " and values determined . maximum for a composition containing 33 mole per cent hydranne ley Semi 4in  : e 0 . 25*, and 50*C. are given in Table 3. might lead to the assumption that a 2-hydrate, Nall 4.211.ii.

should form (and indeed, such a compound was assumed to c'.P TABLEI

' TABLE 2 , , ,

l' .u.i m I%:xia or vac N ll..Il:0 Srsitu i

f,i .

L8 QUID-VAPos Equn.asa 4 roa vuz N H.-Ili o Brerzu ,

secus. ling in Lobry deBruyn and Dito is)

Trnilr s ure. Atole per cent Nelle (At 700 mm.)

Pnnure.

% in m. Li.iuid Vapor (According to Dj6rkman H)

.8 Weight per cent Nelle 5! ole per cent Nell. Temperaturr.

3: . 755.5 I In.

• 7 ,5.5 1.6 Lirluid Vapor Li.luid Vapor *C.

107 85 755.5 19.5 2.7 4.56 0.14 2.6 0.1 ....

lui 11 755.5 3.g 3f' 18.2 2.45 11.1 1. 4 . 104.9 til 'l 755.5 0.2 19.73 2.62 11.9 1.5 100.2 .

114 'i 117 11 755.5 75a.5 31.0 41.7 13.8.

25.0

\ 28'5 38.0 031 10.5 \

18.3 24.1 4.0 '

10.0 -

~ioTil 114.2

.(

Ilx -

7td.0 42.9 30.3 45.2 ~2 E7MJ~ 7 ~313 ~ ~15.5 - 110.1 Ilt' 2 e 7td.0 45.2 34.9 s 46.2 26.4 32.6 16.8 116.8 II" - .id.0 50 3 41.7 46.7 28.6 33.2 18.4 - IIG.8 12tt ' 770.8 St.8 44.6 . 50.8 31.2 30.7 22.0 - 118.0 13' ti 770.8 53.3 48.75 55.4 44.3 41.1 30.9.

138 15 770.8 54.8 52.8 . 59.3 52.9 45.0 38.7 119.7 13Li 770.8 56 0 53.0 62.0 56.2 47.9 41.9 120.2 13Li 58.5 58.5 62.I 56.8 48.0 42.5 - 121.7 12n 15 771.1 G2.5 12tL25 771.1 65.8 72.0 $ by Curtius), but the melting point diagram reveals no evidence l i t* >l 771.1 68.3 75.5 - for the existence of such a molecular species.

1 5 lj 6

8. The parachor values calculated from surface tension and ihr 118.3 771.1 76.0 .. density data of Semishin 88 do pass through a minimum at appn.si.

mately 50 mole per cent hydrazine. Values are given in Table i "

Data for the erfractive indexes of hydrazine-water mixtures may It might be well to consider the question of the existence ..I also be expected to exhibit some deviation from a linear Irlation. hydrazine hydrate in this con vetion. The maximum boibne '

ship. 51ost marked, however, are the deviations from ideal composition is close to that re<pired for a 1:1 compound of hy ha-twhavior in the viscosities of mixtures of hydrazine and water. zine and water. Afaximum deviations in the physical properne-Values go through a maximum, and this maximum becomes more  ; (with the exception of surlace tension) of hydrazine-water mixtni.'

pronounced the lower the temperature.is in the liquid state also lie in the range of 10 per cent of th+c hieasurement of surface tension " of hydiazine-water mixtures corre.sponding to a composition containing equimolar proportioir, at 25*C. reveal.~ the existence of a maximum at a concentration of of the two constituents. The lower the temperature, the snore 30 to 35 mole per cent hydrazine. This is the only exception to definitely does the locus of the maximum deviation approximate a

,' s ,, <Y, ,v

's f.y s y w'

, q ,, v M.

IOS P!ws'Eltril'8 0F AQUEOUS BOLUTIONS OF llYDRAZINE  ! TIIE !!YDilAZINE. WATER BYffrE51 las Y J' 1:1 combination. It b probable, however, that a compound . f

, g 87,1f TABLE 3 '

hydrazine and water in a 1:1 ratio exists only in the solid slate, r- as detennined from the melting point diagram of the system. Thi,

-a ' '\D Drumas or Nellcll:0 Maxromma

- / (According to Dito p) does not rule out the existence in the liquid state of an equilibrium :

d' 3 Wright ler .vnt g c Weight per <ut N II4 II:O ::: N II. + II O g;.3 Nell. \df N II. dP

'>' which is displaced to the right n:th rise in temperature. '

I4 0 1.or 2 G7.4 1.0164

\ 'g

([3 8.2.

26f ,M) 1.03 0 72 0 74.9 1.0440 1.0121 g,

1*

TAlllE 4

'%3 1.0339 78 5 1.0100 SunraesTzanson Ano PAmAcnomor AquzovaIlronmse Gottmon Ar 25 C

.lG. I 1.0125 80.0 1.0379 55 3 1.0161 84.0 Ele ler cent Pararbor of Parachor of 1.0358 59 9 Nille dP

• y Solution llydrasine 1.01G1 90.8 1.0300 04.1 0.0 0.0971 71.90 52.6 1.0170 100.0 1.0114 0.7 1.0046 73.11 55.1 91.1 10.5 1.0087 73.68 5G.6 90.5 (Aerording to Semishin ") 20.5 1.0184 75.10 00.3 U0.4 2G.5 1.0228 75.41 G2.5 Ele ler o . N:II. d' dP dE 90.4

> 28.7 1.0241 75.47 03.3 90.0 10n.'r 1.0211 1.p r24 0.9801 33.0 1 1.0274 73.47 G5.3 10.2 8' t Sa.I-I .n:10 7 1.0 01 0.9888 i 40.1 1.0294 75.28 67.7 ' 10.3 I . 0:55 1 1.0161 0. U'600 48.8 1.0317 74.18 70.G

• 89.5 77.x 1.0105 1.0205 3.0005 49.1 1.0318 74.24 70.8 90.2 78

• 1.0813 1.0248 1.0056 63.0 1.0298 72.38 76.3 00.0 69 l' I .O lGI 1.0208 1.0074 i 09.7 1.0207 71.88 78.8 10.3 G1

• I.0473 1.0298 1.0119 83.1 1.0101 09.97 Ikl .5 UI.0 0: t- I.0179 1.01 4 1.0126 84.9 1.0146 09.81 85.3 91.3 Ssi . ' l 0 ISO l . 0.81 8 1.0133 r 57 E2 91.4

51. 1.0111 1.u i22 1.0136 91.5 4L'- 3.0177 1.0119 1.0137 k

• Densities taken from Semishin>8 47.2- 1.0873 1.0 163 1.0135 I '

4a.: 1.0100 1.0105 1.0133 3 Study of the spectrum of hydrazine hydrate in the near infrared

, to o. 1.0154 1.0293 1.0128 36 8. 1.0110 1.u278 1.0120 gives rather definite evidence for the existence of N-II- s e lionds. IL may thus be assumed with certainly that apprecial.h-In 10 7 0 , hydrogen bonding with formation of N-il-N, N-li-0, and 2s r 1.0382 1.0246 1.0095 0-11-0 bonds does take place in the liquid system. The situa.

2i. . ' - I .0 :G1 1.0231 1.0084 , lion is still somewhat confused with respect to the nature of th.-

28.l- 1.n::oS 1.0192 1.0042 vapor over hydrazine-water mixtures. Older vapor density data IG..

13.o 1.tr250 1.tr207 1.0152 1.0121 1.0022 1.0000 led to the conclusion that hydruzine hydrate is dissociated ini..

water and hydrazine to the extent of 58 per cent at 100'C. an 1 01 { g mpletely at 110*C.88 13ut hydrogen bonds are usually destroyi d 1.:e I.0025 0.9995 0.9903 in the vapor state. It has furthermore been observed that the 0.es. 0.0999 0.9971 0.9881 absorption spectrum of hydrazine hydrate in the vapor phaw d

. - U

, . i M -1r :: *~' . .

rt. p i TERNARY SYSTE518 III 110 lftOPERTIES OF AQUEOUS BOLUTIONS OF llYDRAZINE consista of tir superposition of the spectra of hydrazine and of v melting point of -58'C., corresponding to a mixture containin;-

m ater " Until a more definitive investigation is made, it may be 69 per cent hydrazine by weight (56 mole per cent). The exart assumed that no association occurs in the vapor state. composition of the water-rich cutectic could not be determinnt because of the viscous nature of solutions containing 35 to 19 ges ,

TABLE 5 cent hydrazine by weight. Data given in Tabic 5 and depicted m Figure I repersent the most recent determinations." Values f..r FaHHNQ POI *rFS OF Taz N 11cil:0 SusTna , , ,

Freezing Weight per hlote per Freezing l l 4 4 4 l i i Weight per 3 tole per cent Nell. eent Fall. Point *C. cent Nelle cent N:ll. Point. C. l

_ - 10 - y ._

~

3.11 - 3.80 57.4 43.0 - 53.7

• 5.40 - 20 -

6.40 3.71 - 4.30 58.1 43.9 - 53.4 3.83 - 5.30 59.9 45.8 - 52.6 .C 4 /

7.60 -

7.70 4.19 - 5.40 tu.6 4G.5 - 52.2 \ f

- 6.40 63.1 49.1 - 51.7 - 40

\ I 8.70 5.10 -

\

7.01 -g.80 61.2 50.2 - 51.7 11.9 7.51 - 10.3 68.7 50.8 - 52.0 - 50 A 12.6 -

g l -

8.32 - 12.8 GG.5 52.8 - 52.2 13.9 d.53 - 12.7 66.6 52.9 - 52.7 t 60 -

13.3 -

II.g -19.1 67.6 54.0 - 52.6 g , , , , , , , ,

18.4 l l .t. - 20.4 69.2 55.8 - 50.3 0 20 40 60 80 100 19.0 12.1 - 22.0 69.6 56.2 - 52.8 neole per cent N,H.

19.7 12.2 - 22.2 70.3 57.1 -4G.8 / Faouns 1. h1 citing-point diasmm for the hydrazino-water system. - , dain 19.9 12.5 - 22.3 70.4 67.1 - 40.2 , data by blohr and Auilricth."

20.3 by Scanishin88; 21.4 13.3 - 28.7 70.7 57.6 -48.2 83 8 59j by Semishin; marked dilTerences are to be noted, however, in

[ 2599 3 2[6 2 .2

- 30.8 74.8 62.5 - 38.1 the water-nch range of mixtures.

24.1 15 2 15 1 - 33.3 75.0 62.8 - 32.7 24.8 16 5 37.3 81.0 70.5 - 20.4 2G 0 TERNARY SYS1 TRIS 26.2 16 1. 34.9 88.1 74.9 - 15.6 ,

17 l- -416 85.1 76.2 - 14.8 27.5 -

Addition of sodium hydroxide to certain hydrazine-water mix.

.g 0 0 l turce results in the formation of two liquid phases at temperaturs g g ~. 46 3 .

N 45.0 23.

31.4

- 65.9

- 75.8 98 4 99.0 97 1 98.2

"'20 o.90 i

above 00*C. The upper hydrazine-rich phase can easily be segu-ratal from the heavier solution containing the greater part of th"

- 61.7 99.6 99.3 1.60 49.3 35.4

• water and added alkali, thus affonling a simple procedure for the concentration of hydrazine 28 (See page 50.) The summary . f plait points and limiting compositions of the conjugate liquid Fn ezing i oint data for the hydrazine-water system '8 reveal the phases is given in Table G.

existence ..I .i t. hydrate as a solid phase, melting at -51.7T. Data for the ternary system at 100*C. are depicted graphically Two cuteri ~ compositions consisting of Nall.-N i lle ll:0 and in Figure 2. One important reason for undertaking a study of the IIso-N.II .110 2also form. The hydrazine-rich eutectic has a ternary system, N lle-II 0-NaOll, was to determine if concentra-0 9

lit kitoPl;l's IES OF AQt'EOUS SOI.UTIONS OF IlYDRAZINE F

hydrazine, tirit b, those ia chich h drazine 3 acts as the calvent g nnd water n- the :*. lute. Since hydrazine is a strongly basic sol- CII APTER U sent, we mi:' '. esivet under the circumstances that water would I have as a cak acid in anhydrous hydnzine, especially since the hy haze im ion is the bearer of acidity in solutions of an-hydrous h.ut- ine. Thi4 fact should I.e borne in mind if and w hen any ex'r -i. . wool, i< undertaken to detennine the exact nature and behmin i r. lution4 that contain an excess of hydrazine. OXIIIntION 0[llyffraziFle; Catalytic Decomposition REFEttENC.I.S I. Schsr:.tres

• ii. Alefr. CAsm. tefa,19,173-182 (1936).

2. I'. A. lir.. . Tbis, University of Illi.e.in,1947. The ability of hydraz.me to act as a powerful reducing agent

3. Oft.c7 of it l'ul I. cation Iloard, Department of Commerce, Washington, has always been recognized as one of its outstanding chemical D. C., e ' uti. Tri ,215, l Iteport 80. propertics. Early workers paid little attention, however, to ih.-

4.1-3, Ito. 23,1383-32i6 (189u).

5. Itant.or+ Wl'. AmJ. Sci., Cramic, 1906, 733-770; J. CAem. Soc., 92 fate of hydrazine, that is, to the oxidation products resulting from (sil, 3s1 ' IM ) such reductions. When Curtius " discovered that hydrazoic ari.!

6. Ilv riwm, ? pA ,W.4 CAe m.,19, 4%510 (1894). Could be obtained *uy the action of nitrous acid upon hydrazine,

7. I:n.lcil.iti. - ad CAcm , 17, 293-294 11914).

s. Ir n.lc.i,iii . .I II. gan, J. s,or. CA,m., 20,20>215 (1915). Nzil + llONO -s [NO Nzliz] --a llN Ns

9. L*ndrelutt i. . I'liturnin, J. Biol. CAcm., 22, 499-504 (1915).

tu Lits, J. f. .11r.l.,10, 457-4GI (1908). investigators studied such presumed oxidation reactions to deter.

II. I'n.lctlutt - at han lite, J. Biol. CArm., 58, 147-150 (1923).

I2 ui> e maml 23 I mine if other nitrogen-containing oxidants might be employed for

, , , I synthesizing hydrazoic acid from hydrazine. It was taken f .r I l. L*n lcrhal i .-l Itaunumn, J. Biol. CArm , 27. 169-172 (1916). granted that a mirogen-contam_mg compound was necessary. This

15. lot.ry siclinsyn s nd Dito, Proc. K. A Aa.l. Il'elensch. A msterdam, 5,171 hypothesis seemed well established after it had been found that til (l.pi. .; Al ed, ll'rtrasch. Amsterilam rerst.,11 (Book 1),155 (1902). nside could be obtained by the decomposition of hydrazine nitrate *

16. lijGekm n. vn * &m. TsJ., 59,211-215 (1917).

17. Iolery ilclicayn sis.J Dito, Proc. K. Ala.l. It'etenerh. Amsterdam, 4,75G- and of hydrazine sulfate in the presence of strong nitric acid : anel 7M (1.nr. i: A1..J. II .trasch. A matenfam reral.,10 (11ook 2),830 (19u2). L by interaction of nitrogen trichloride

• with hydruzinc.

IS. Semi >hin, J Cc.a. CArm. (USSR), 8, G5 8 061 (1933). In 1905 A. W. llrowne

• found that hydrogen peroxide coul.1 19.11oLer aral 6dbert, J. Am. CAcm. Soc., 62, 2479-2180 (1980). I also be made to react, with hydrazine in acid solution to giu-

20. Giguire. 7, sea. by. Sur. Can. (111),35,1-8 (194I).

21. Scutt, J. t t as. Scr., 88. 913 (1904)-

hydrogen aside. Ilrowne and Shetterly" subsequently studic.l the action of many other nonnitrogen-containing oxidizing ngents

. i . J. m. C e , 'l I 4 1 47 (1949).

Won mz ne, pnenWy in ucM sdubn, in an dod to hmine what sort of mecham,sm might be devised to account for the c

L formation of this pnxluct. Only a limited number ucre found t..

c give hydrogen azide; nitrogen and ammonia were genendly i.l.

t tained. In only a few cases was nitrogen found to be the sol" oxidation product To gain a clearer insight into the mechanism of the oxidation

.of hydrazine, it is desirable to consider a number of related factors 115 L'

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r.D MEETING

SUMMARY

DISTRIBUTION

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%.9ecket flo(s):?*~50-424/4251 f?

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