6650058 Chlorine Manual

8/3/2019 6650058 Chlorine Manual

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HOOKER CHLORINE

FORE'NORO

The purpose of this booklet is to provide useful information to anyone whobuys, uses, or handles chlorine. Everyone using chlorine should be thoroughlyfamiliar with safe methods of handling, storage and uses. In the preparationof this booklet special attention has been paid to safety in the handling anduse of chlorine.The information contained herein is, to the best of our knowledge, accurate

and should be helpful to the chlorine consumer. However, no guarantees asto completeness or accuracy are made, and Hooker Chemical Corporationassumes no responsibility or liability for the failure of any procedure, method,or equipment described herein. These suggestions should not be confused withFederal, State, municipal or insurance requirements.The assistance of The Chlorine Institute, Inc. in the preparation of this

booklet is gratefully acknowledged.

He inf c rmo tion presented herein, wMile not qvcr cnteed , is to the best of our kncwte dc e true and cccc r ote. No warrantyor guorol' tee expres-s or implied ,S made regarding t~e performance or stability of any product, sio ce the rno nn er of useand r c ndrtro ns of stor o qe and hondling ore beyond our ccntr ot. No svc qe s tion for product use, nor anything containedherern, s ho l l be construed o s 0 reco m rne n dotio n for its use in infringement of any exisfing potent.

Copvrigh t 1965, Hooher Chemical Corporation


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SECTION PAGE1 General Information. 2

2 Equipment for Handling Chlorine. . . . . . . 12

3 Shipping Containers. . . . . . . . . . . . 17

4 Safety in Handling Chlorine. . . . . . . . . 31

5 Preparation of Sodium Hypochlorite. . . . . . 35

6 Analytical Procedures . . . . . . . . . . . 40

7 Manufacture of Chlorine . . . . . . . . . . 42


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SECTION 1

." J /\ 1 ~ " " . ~J ~l ,

Liquid chlorine is a clear, amber-colored liquidabout one and one-half times as heavy as water. At6El F the vapor pressure of this element is 82pounds per square inch gauge.Chlorine enters into substitution and addition

reactions with a great variety of organic and in-organic materials. Dry chlorine does not reactappreciably with most metals at room tempera-ture. At elevated temperatures, or in the presenceof even small amounts of moisture, chlorine doesreact readily with many metals. Dissolved inwater, chlorine is an oxidizing agent of moderatestrength. It is nonexplosive, noncombustible anda nonconductor of electricity.

Commercial liquid chlorine contains in solutionsolid, liquid and gaseous impurities. The amountsof these impurities vary widely. The followingfigures on the principal impurities may be takenas illustrative:

Gaseous impurities:COcON"

0..50% by volume0.04 by volume0.07% by volume

Liquid impurities:.J O ppm, total. These are largely carbon tetra-

chloride, chloroform, and chloroethanes.Solid impurities:25 ppm, total. Largely hexachloroethane andferric chloride.The solid impurities may be troublesome, in

t hat they deposit in pipes, valves, and control in-struments. To 1 1 large measure these solid impuri-ties can be removed by a suitable trap or filter.A chamber, packed with alternate layers of acti-vated alumina and glass wool, plnc~d ahead ofthrottling valves and control instruments, helpsprevent dogging. A short length of pipe rto 6"

in diameter, packed with alternate layers of glasswool and Raschig rings, is also helpful.

SymbolAtomic WeightMolecular WeightCritical DensityCriticalTC'mperntufP

Critical Pressure

Compressibility

Specific Gravitv(gas)

Specific Gravity!liquid)Boiling Point(760 mm)

Freezing PointViscosity (gas,absolute)

Viscosity (liquid)

1 volume liquidchlorine

1 pound liquidchlorine1cubic ft. ofliquid chlorine

Ref.Cle35.45770.914.573 grams per Iitr-r 0)[H' C (~9J' F) U)

111S pounds p--r square (1)inch, (absolute)

.0 11S';;;) per unit vol. per (3)atrnosphe r increase at 20 C(bdween 0[00 a tmos.)

2.19 (air = 1) (2)JAl (at 20" C. water = 1) C O34.,5 C (--30.1' F) (t)

-100.9S C (-149.76" F) (5).000009t lbs. per sec. per ft. (6)at 68' F

.00023 Ibs. per sec. per ft. (7)at 6S'- F

=156,8 volumes chlorine gas (8)(at W C, 1 at mosp here-)= 4.98 cubic ft. chlorine ga3 (8)(at 0' C. 1atrnosp iu-rr-}

= = 91.64 pounds (at W C, (8)1 cubic ft. of gas{'ous = .2006 pounds (at W C.chlorine 1 atmosphere)

('i.'-I

L '~i : i ';1 , , ! :,\Grams per Pounds perT ( C) T ( 'Fl liter 1000 Gallons

10 50 9.96 83.220 68 7.30 60.740 104 4.55 38.060 140 3.24 27.080 176 2.16 18.1

'J


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Below 10' C (50' F) chlorine combines withwater, forming crystalline hydrates. One of thecommoner forms is the octahydrate (CL8H:,O).The chlorine hydrates (or "chlorine ice") are notstable above 9.5' C (49.1: F).

One pound of chlorine combines with:.83 pounds of commercial lime.1.10 pounds of commercial hydrated lime.1.13 pounds of caustic soda (100'/" 0laOH).2.99 pounds of soda ash.

Specific Heat (liquidchlorine)

Specific Heat (gaseouschlorine at constantpressure)

Specific Heat (;:;aseouschlorine at constantvolume)

Latent Heat of'/.1poriz:ltion

Heat of FusionThermal Conductivity

(gaseous chlorine)Heat of Rt'action withNaOH

Ref..226 BTT..:/lb.;' F (2)

.115 BTU,lb.;Fat 1atm., 59cF

(10)

.085 BTU/lb./oFat 1 atm., 59'F

( 10)

12:1.8BTC, lb. at-:!9.:3'F

11.2BTU/lb. at-150.7' F

.0043 BTU, fPlwr hr./F temp,drop/ft.

G26BTU/lb.chlorine gas

(:') \

(2)

(6\

Additional thermodynamic data availble in apaper by Kapoor and Martin, University of Michi-

gan, "Thermodynamic Properties of Chlorine."Copies may be obtained from Hooker ChemicalCorporation or the Chlorine Institute. This in-cludes entropy and enthalpy diagrams.

(1) Pellaton, M. - Constantes Physiques .lu ChIor .. Jour .cit' Chirnie Physique, 13:426 (1915).(2) National Research Council. Interna t ionn l CriicalTablps. McGraw-Hill Book Co., New York (Volume 1.192(;) .(3) ]\."at ional Rf'search Council. International CriticalTables . .\1cGraw-Hill Book Co., New York (Volume 3,1928),(4) ,1 . I. Lacey. Hooker El ectroohornical Company, Anal.Chern. 20: 379 (1948) .(5) Giuuquo. W. F., and Powell. T. M., - Chlorine. ThoHeat Capacity, Vapor Pressure, Heats of Fusion andVaporization and Entropy. Journal of American Chern.Society,61:1970 (19:39).(6) National Research Council. International CriticalTables . .\IcGruw-Hill Book Co., New York (Volume 5.1~)2'l).(7) National Research CounciL International CriticalTables. 1\!cGraw-Hill Book Co., Nr-w York (Volume 7.19:30).(8) Lange, N. A. - Ueber einize Eigenschaf'ton des vr-r-flussigt.en Chlo r. Z..itschr if t fur an guwandt e Chern ie,13:G83 (1900).(9) Landolt-Bornstein. Physikalish - Chomische Tube-llen5th edition Hauptwerk, Springer, Berlin (1923).(10) Lange, N. A. - Handbook of Chemistry. HandbookPublishers, Inc., Sandusky, Ohio.


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1.60 ,"""""_: ' + - : : : tJ . :- tr+r-J : :L -' -: ': P~ . .

t+t+: +t-t +r-t-r- j ,'_1';+ -+ -t+, L ; . ; _ +

rt ,7i~;:;c i.orrrt: m~+~:::Ff

I+-~"'-'~.,t1:fr.'*'

.90 t+ ~r - t - i -

T E M P E R A T U R E of

Fig. 1. Physical Properties of Liquid Chlorine


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T E M P E R A T U R E =c

240Ji+ - 1 1 230H-- 220

210:1 1 fir ~H+ 200

T-, ! I I !: : i !;j-L H+~ t v+ 190

30#+: : ' + + -20

~ tl+, ' " + - - - 'H+~+f-L+: + --. ~r-- I ' : !-1-' r'+ + - H+, -t-+-t- 20~:

30

' .t+ tW- ,10,~ -+-LI

o-40 -30 -20 -10 0 10 20 30 40 50 50 70 80 90 ICO 110 120 130 140

T E M P E R A T U R E ofFig. 2. Vapor Pressure of Liquid Chlorine

5


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T E M P E R A T U R E O(I0 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90

l i_j .

I I80.l -

. ! t ' 75-T

T E M P E R A T U R E ofFig. 3. Solubility of Chlorine InWater

(j


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a-~a_.J

VI_.J


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T E M P E R A T U R E -c_40-35-30-25-20-15-10 -5 0 +5 1015202530 354045505560

98

97

96

95

94

93

9291I-a90 0u,U89 ;: 0= >U

88 ~LUc,V87 ClZ= >

86 ac,85

84

83

B2

BI

80

-40 -30 -20 -10 0 + 10 20 30 40 50 60 70 80 90 100 110 120 130 140T E M P E R A T U R E of

Fig. 5. Density of Liquid Chlorine


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T E M P E R A T U R E =c-30 -20 -10 o +10 20 30 40 50 60 70 80 90 100

l-r- I-0 0..,\ 0u . . . u . . .U UCD CD:::J :::JU 4 U~ c : r : :UJ UJc, c,Vl Vl0 aZ Z: : : : : > : : : : : >0 :3 3 0o; c,

i ~! i;_:O~~--~~~~~~~~~~~~I~~u-~~~~~~~~~~~~~~O-20 o +20 40 60 80 100 120 140 160 180 200T E M P E R A T U R E of

fig. 6. Density of Saturated Chlorine Gas


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u, 200LU0::.::) 30-0::.LUa...~

40UI-

50

60

100

.30CENTIPOISES

.40 .45 .5035-40 ~J-~l Ie tf--~~H j - ~ I - ~ T t t f - - h - + + - H + - ~ - + - + - + '/I- I 17~._; .;-~tr

-- t--- I-- r.Li,,J~ H - I . ,_- I- I-- -L.--,--- i ;- 1/4-- I-_L I . I i F + j ~ ~. . .1 I ,, T~ , 1--- i ( - ~f-l- 7--'_+ I---~I I ~i-~ , + + 1 7i--~- , ';--r---'-h T I l-- i 17,-i---i- "; --~-r---+---u-;-I ,

. I !~~7 r- --i- - - ~--- ._ --i----.,----- --I .r T_,..__ r-

I t - - - - + - - p - - ; - . - ' - - 1 - f--c----+-- - L 1 ~ t-- -.---~ f--~-~~;J , Li- ~~_;_-, ~~F t = : - ~ ! I , H--~i~ I .t---+ l- ii 1 - ~~__;_T, i ~I--t - + - - t - - - - - - - t - " T . . trlT , f -~ -- T . r = = - - = - ~ = LI--~L --t-,,--+- _ i : - _ _ --~"u"f---t_ -r--- '/t -+ -----,-- ~ --~"r - + - L r -r-----:-- r F + ~-- ~ ~ , /' + f-, ,- - ___ --t----.---._"I -- t- ;- -- -T - , ,~T '-;- I-~ 1-- ' .l._" : j . I I T ~ L - : ~ : =-, _ '/, ~ T - _ ; : - = L 1- __ .. . ; ._f+ If: 1--- --; ,- + ~.;-~ir-j--~+- t- -. ' ....~+.--+- , ------t-I I It~ I! : ,-- f-- 1 . -~ .-j- I - f - = ~ =-; p-+ . -~P=Lr - + 1,-1 ~ . .. - , _ _ _ j _ 'T - ~ L ~ .-+--+. - f . _ _ J _ -J r '.-~~ +~-~: r - ~ - - r . -__~-~--I -. r-rt- + rr f - + - - + " 1-- 1- '--'--' ;t ~ + - + L T _ .__ i _ _ _= = - . '- - - ; - tH -/t~ 1 1- ; , + . ~ .. J ,-:--t--r---t- , +i- --t---- -,.-- --- 4-"-!+---~ . 1 , .1 -; . _ J _ _ _ _ _ .-

I : -- j IJ I1 , I - - _ , .L~ ~ t - ~ - = + _ _ _ , ,T t~i- : : = r- t - f - - f - - ~ ~ ~L~. ,-- .I--'~_,T_1 -'- . ' - t - ,. . . -c~ ~--r T -~I ! .. - - I---~ . . i--- -, .,_--,---- _ ; ,~~ 'L~L.~ t-~- I + 1. '- -t -- -+ - t 1-- -r - -. T r --r- ,,i v , ,lti ' i-- ,._ --~ - " -/:_ , ~ 1 - - ft--Lf '-I _ +---- ____T "+ - - + - . ~ ! 1 f--_:_-~.- i. ;~i-'~~~- - ~. '--1 -t---,I 1 , : i I s rI : - I--C- 1---- ~ . . 1 - - - ~ T i.: I I J ' - - - + =. - L L! ! d = _ - t I-L-f--~ .~..; t .~ " - .- 1_"- .:I I--f f--'-" f-+- I-T .~1:i f- ;~f- I - - r - l ~ -l L- - 1 -j i !-- t I . f ~ J t [: i f I l h t 1~1-t i } : , f-- - ; _ _ - i - -i IL-+ E r - +--j- t - i-!--. , :~H - ; + - - I--- c I ; - - - - i ' T . t - - , - l ; = 1 . :, f tl ~..,I+~'--1. I l H ' I n i r = .-L IT , I---tT1--- f-- t - +-I ~ t r t - F + ~ l f.!---I-- . -. 1- F E f- ...._ E ~ _ - H - .. ~~-~- t-- f-H ~- t- ---1-- i- f---t---- f - + - - + ~. ~L i- J-- I '- t-- - .- 1 -. -.-~'i , , ~'L:-t .. . I ~c::~~-- t - ~ _ ~ L _ ~ - ; --_j__ .; __ - . --


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-40 35 -30 -25 -20 -15 -10 -5T E M P E R A T U R E =co +5 10 15 20 25 30 35 ~

120.+ -

45 so c,s 6D122.

H-+b$~,-

: : >t-eO

94f-


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SECTION 2

The specifications here listed are general only.Detailed specifications may be obtained fromHooker's Technical Service Department.

Dry ChlorinePIPE: All pipe shall be extra heavy ISchedule80) butt or lap welded seamless carbon steelpipe.FITTINGS: 1~'2" and under - 3000 poundforged steel screw type. 2" and over - 300pound cast steel flanged or Schedule 80 steelbutt welding type.FLANGES:Series :30steel, tongue and groovedor raised face.REDUCERS:1 1 / 2 ' 1 and under - 3000 poundforged steel screw type. 2" and over - 300pound cast steel flanged or Schedule 80 steelbutt welding type.CNIONS: 1%" and under - 3000 poundforged steel, steel to steel seat, screw type.2 /1 and over-300 pound steel flanged tongueand grooved, or raised face.VALVES:O.S. and Y. globe valves with forgedsteel body, bonnet and yoke; Monel' stemand Hastelloy "C"~ valve plug and seat withTeflon' on stem, Crane No. 1644-TF orequivalent.PACKINC:Teflon impregnated braided asbes-tos, twisted or braided graphitized asbestos,Teflon chevron.PRESSUREGAUGES:Dial type with silver dia-phragm protector.GASKETS: 1/16" thick 3% antimony lead,1 8" bonded asbestos fiber. Garlock 900 orequal.PIPE THREADS:Threads should be cut withnew. clean dies to assure a good joint withno leakage.

l Lnt ornn t iona! :\ickel Co.C ('nion ('arbidi' C(JqL

E I. .lu POllt de 2\f,'I11UUI":'; and Co.. [n('.

1 ' " 7 . , . - 1-~~~\~

Wet ChlorineWet chlorine is very corrosive to all of thecommon construction metals. Generally it canbe handled at low pressures in chemical stone-ware, glass, porcelain, or rubber-lined steel.Hooker Hetron polyester resin, unplasti-ci zed polyvinyl chloride, Havegl, KeI F\Saran", and Teflon have been used success-fully. Gold, platinum and silver are resistant.Titanium is resistant only to wet chlorine andtantalum is inert to both wet and dry chlorineup to 300" F. Applications of this type arevery special and the chlorine or equipmentmanufacturer should be consulted. Recom-mendations can be made after all of the fac-tors have been studied.

To insure rigidity and lessen the possibility ofleaks, extra heavy fittings and pipe should be usedwhen chlorine handling systems are installed.Forged steel fittings and extra heavy carbon-steelpipe, being economical and readily available, arenormally used.Long pipe lines for carrying liquid chlorine

should be avoided.When long pipe lines must be used, it must be

remembered that liquid chlorine expands about0.15 per cent in volume for every degree Fahren-heit increase in temperature. A closed-off sectionof pipe that is full of liquid chlorine could beruptured by the resulting hydrostatic pressure ifit were subjected to a sufficient rise in temperature.Such an occurrence may be prevented by installingproperly designed and heated expansion chambers.They should be installed vertically between shut-off valves and above the highest point of the line.These chambers should be designed for 20 per centof the pipe line volume and fabricated in accord-ance with the code for Unfired Pressure Vessels,No valve shall be installed between the chlorine1 Havpg Corp.

.,:nr Company" The Dow Chemical Co.

12


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rESTING OF is f MBefore a chlorine handling system is put into

service, it should be:( 1) Thoroughly dried with air having a dew

point of -40' F until the wet and dry bulb tem-peratures leaving correspond to the wet and drybulb temperatures entering.

(2) Free of leaks detectable with a soap testafter the system has been filled with compressedair.

(3) Free of leaks detectable when small quanti-ties of gaseous chlorine are present in the lines.Leakage is shown by the formation of white fumeswhen an ammonia swab is brought close to a joint.The desired test pressure is built up with drycompressed air.

(4) Tested with sufficient full strength gaseouschlorine to fill the lines at the desired test pres-sure until all leaks are stopped.

HEATED __ /EXPANSIONCHAMBER

PRESSURE GAUGES

I I

(5) Thoroughly flushed with gaseous chlorine toeliminate all air pockets.

(6) Tested with liquid chlorine when the linesare to be used for liquid service.'.!R SYSTEM FOR UNLOADING LIQUID CHLORINENormally, a tank car is loaded with chlorine atlow temperature and pressure. In the wintermonths, the low air temperatures prevailing donot permit sufficient heat transfer through theinsulated tank to increase the pressure within thetank car. When this is the case, the user resortsto air padding to produce the pressure required todischarge the liquid chlorine. A typical air paddingsystem is shown in Fig. 10 below. The pressure ofthe gas discharged from the evaporator can be con-trolled either by careful regulation of the pressureon the tank car or by regulating the gas pressuredownstream from the evaporator. For a specificrecommendation, consult your chlorine supplier.

. .. ..- BAROMET RIC LOOP

~ I . ! : = = = = ~ I I -EACT ION VES SELAIR - CHLORINE CHECK VALVE

CALCIUM CHLORIDE DRYER---- DRYERS -US E ONE S ECT ION WH ILEREGENERAT ING TH E OT HER S ECT ION

A IR C OM PR ES S O RRES ERVOIR COOLER AND

PRESSURE CO I' HROL

Fig. 10. Typical Arrangement for Unloading Liquid Chlorine Tank Cars

1t


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A separate compressor system should be usedfor padding chlorine tank cars. If regular plant airis used there may be times when the pressure inthe car is greater than in the air line. This wouldcause chlorine gas to flow back through the airline, causing corrosion to other plant equipmentand discomfort to plant personnel.For most installations, a maximum air pressure

of 100psig should be adequate. The air should bedried to a dew point of approximately -400 F tominimize corrosion. Suitable commercial air dry-ing units are available. These units have twodrying cartridges in parallel and one can be re-generated while the other is being used. Any airdryer system should be checked regularly to seethat it is operating properly. Suitable pressureswitches and an oil filter should be included withthe compressor. A check valve in the line willminimize the chance of chlorine getting back tothe compressor.

When large amounts of gaseous chlorine arerequired for a process, the chlorine should be with-drawn from the container in liquid form and con-verted to a gas in an evaporator.The Hooker Chemical Corporation has devel-

+.,NN

Fig.l1. Air-Chlorine Check Valve and Filter Unit

CI2VAPOROUTt

WATEROVERFLOW

I II I

LIQUID CI2INLET

Fig. 12. Chlorine Evaporator

oped an efficient, durable chlorine evaporator. SeeFig. 12. It consists of manifolds for the chlorinewhich are completely surrounded by heated waterat atmospheric pressure. If a chlorine leak occurs,it is readily discovered before irreparable damagecan result because the absorbed chlorine is readilydetectable in the water bath overflow. This fea-ture has the advantage of protecting the chlorinesystem from corrosion because the chlorine, beingat a higher pressure, will prevent moisture fromentering the chlorine lines. At the same time, thesteam heating system used to heat the water isprotected since the chlorine absorbed by the waterescapes to the atmosphere rather than enteringthe steam lines. If a chlorine leak develops in themanifolds and is not discovered before they aredamaged beyond repair, new ones may be readilyand easily installed without replacing the entireevaporator assembly.The liquid chlorine enters the evaporator

through a bottom inlet into a special evaporating

15


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manifold. When the water bath is at operatingtemperature, evaporation takes place immediately.The evaporated gas flows through passages sur-rounded by the thermostatically-controlled hotwater bath. This contact with the heated surfacesuperheats the gas, thereby assuring a gas freeof entrained liquid chlorine. The gas leaves theevaporator manifold through a top outlet.The temperature of the gaseous chlorine is con-

trolled by regulating the temperature of the waterbath. A Mercoid control in the gas line automati-cally opens and closes a solenoid valve in thesteam line to maintain a constant gas tempera-ture. When no gas flows, another Mercoid controlin the water bath maintains the temperature con-stant thereby holding the evaporator ready todeliver gaseous chlorine upon demand.The Hooker Chemical Corporation has also de-

veloped another evaporator which vaporizes liquidchlorine using steam as the direct heating medium.The steam pressure is maintained lower than thechlorine pressure to prevent entrance of moistureinto the chlorine system in case of a leak. Thisevaporator also automatically controls the chlorinetemperature, is more compact than the other type,has no moving parts to get out of order, and iseasily accessible for cleaning.

I ND IC AT IN G T EM PE RA TU RE C ON TR OL

CHLO RINE GAS ,

THERMOWElL

HA NG ER BR AC KE TS \ I ' - ~ ITO B E LO CAT ED TO iS U IT I NS T AL LA HO N k

b;"

C ONDENSAT E

Gaseous chlorine may be metered and controlledeither automatically or manually. Automatic con-trol is accomplished best by first evaporating theliquid to gaseous chlorine. Because constant pres-sure and temperature are essential to accuratemetering, a spring- or air-operated pressure con-trol valve is installed before the metering equip-ment. Metering is accomplished with either visual-or orifice-type flowmeters with or without record-ing instruments. Flow rates may be readilycontrolled by the installation of reputable air-opera ted flow con trollers. Our technical andengineering staff will gladly assist with any par-ticular application.Hooker is primarily engaged in the manufacture

of chemicals, not equipment. However, we havedirectly supervised the stringent tests specifiedfor the two types of specialized evaporators fabri-cated to date. This policy has helped insure a highlevel of performance for the units installed.The flow of gaseous chlorine can be measured

readily and many instrument companies makesuitable flow meters for this service. Metering ofliquid chlorine has been considered impracticaldue to the high pressures and low temperaturesrequired to maintain the liquid state.

--_ .- -- LOWPRESSURES T EAM

4-7/8' - 2 . :-'= --P~P-S ~FE TY VALVE

LIQU ID- - - C HLO RINE

INLET

Fig. 13. Type "C" Evaporator

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SECTION 3

Chlorine in commerce is a liquefied gas underpressure. All types of containers used in the trans-portation of chlorine, as well as all means oftransportation, are strictly governed by the regu-lations and specifications of the Interstate Com-merce Commission.Liquefied chlorine in containers has both a liquid

phase and a gas phase. Temperature affects boththe vapor pressure and the volume of liquidchlorine.As the temperature of liquid chlorine increases,

the chlorine gas above the liquid exerts a greaterpressure. For example, the gauge pressure on achlorine container is about 82 pounds per squareinch at 68 F and is about 140 pounds at 100 F.The pressure on a container is not a measure ofthe amount of liquid chlorine in the container.The volume of liquid chlorine becomes greater

as its temperature increases. Thus, in a loadedcontainer at 1000 F, the gas space is reduced toless than 8 per cent. The gas space would becomecompletely filled with liquid if the temperaturereached 153.4 F (See Fig. 4, page 7).Because of these characteristics, chlorine con-

tainers should be handled with care and never beheated. The greatest danger from chlorine occursthrough the development of leaks, since strongconcentrations of chlorine in the atmosphere maycause serious physiological effects.Itis illegal to ship a full or partially full con-tainer which is leaking or which has been exposedto fire. Under certain circumstances the Bureauof Explosives may allow shipment of a leakingcontainer to which a device from a safety kit hasbeen applied. Consignees must report promptly tothe Bureau of Explosives all instances of improperstaying and broken, leaking, or defective contain-ers received by them. In all of these cases thechlorine supplier should be notified immediately.Hooker chlorine is shipped in three different

types of shipping containers - single unit tankcars, ton containers (TMU cars), and cylinders.

The following are points of similarity among thethree types:(1) All containers are made of steel.(2) All containers, when loaded, have about 12

per cent free space at 68 F. This is necessarybecause liquid chlorine expands markedly as itstemperature rises. The 12 per cent outage is suffi-cient to prevent hydrostatic pressure from de-veloping at temperatures under 150 F.(3) All containers are equipped with safety

devices.(4) All containers are inspected before refilling,

and are pressure-tested at regular intervals.(5) All containers are intended for use by the

customer in delivering chlorine to process, thuseliminating any need for intermediate storagetanks. Use of chlorine storage tanks between theshipping container and process is hazardous andunnecessary.

Construction: These are built in three differentcapacities; 16, 30 and 55 tons net. They are pro-vided with insulation, generally four inches ofcork, or four inches of fiber glass or two inches ofHooker Hetrofoam polyester resin and an outersteel jacket. The only opening in the tank is themanway at the center on top of the car. Thisopening is closed by the dome plate which issealed by an antimonial lead gasket and a ring ofbolts.

ICC Spe c if ic a tion:105A500105A300

105A500 W105A300 W

V a lv e A r ra n ge m e nt : All valves are located on thedome plate.The four angle valves are made of forged steel

with monel seats and stems. The end of the stem

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. r T t t - - - - - - - - - ~ 1 ; _ - SA FETY VALVE

PLAN AT DOME

LIQUID CHECK VALVE

INSULATION

~---------------------------------------------------- A -----------------------

Fig. 14. TYPical Dimensions of Chlorine Tank Cars

I S


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A B C D E16 T. C AR 32 ' 6-1/4" 9 ' 10-9/16" 1 0' 8-1/2" 9' 1 " 9' 3"30 T . C AR 33' 6-1/4" 11 ' 5-1/16" 1 2' 4-1/2" 1 0' 7" 9' 3"55 T . C AR 40' 11-1 /2" 1 2' 8-3/4 " 14 ' 10-1/2" 12 ' 0" 9' 8"

S AFE T Y VALVE

LIQUID OUTLET VALVE

S AFE T Y PLAT FO RM

PLASTICS

E

19

v


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acts as the plug. Outlet threads are I" femalestandard tapered pipe threads. All valves arebolted to the plate and sealed by tongue andgroove flanges and an antimonial lead gasket. Pipeplugs are provided for each angle valve and shouldbe securely in place except when the valve is beingused. The two valves on the longitudinal centerline are used for unloading liquid chlorine. Thetwo valves on the transverse center line will deliverchlorine gas and may be used to introduce clean,dry compressed air when it is desirable to increasethe pressure in the tank to maintain the desiredflow of liquid.The safety valve in the center is of the spring-

loaded type and may be combined with a breakingpin assembly. This valve is intended to releasepressure in the car rather than allow it to build upto the point where the tank itself may be de-stroyed. On cars stencilled 105A300 or 105A300W,the valve is designed to discharge at 225 psig andreseat at 180 psig. On cars stencilled 105A500 or105A500Wit is designed to start discharge at 375psig and reseat at 300 psig. These safety valvesrequire no adjustment by the consumer and shouldnot be tampered with. On some 55-ton cars, oneangle valve (gas) is sometimes replaced with asecond safety valve.Excess Flow Valves: These are rising ball type

and are mounted to the dome plate under eachliquid valve. The eduction pipe is mounted to thebottom of the excess flow valve and extends tothe bottom of the car. As liquid is unloaded itpasses through the eduction pipe and the excessflow valve. This valve is designed to close whenthe rate of flow is about 7,000 pounds per hour.This is a protective device designed to close againstthe outward flow of liquid chlorine if the anglevalve is damaged or under certain conditions if theunloading pipe line is broken. The angle valveshould be fully open when withdrawing chlorine,as any restriction will impede the operation of theexcess flow valve in the event of a line failure.This valve may close if the angle valve above itis opened too quickly. The angle valve should al-

ways be opened very slowly until the pressure inthe line is equal to the car pressure. This is mostimportant during the summer months when thecar pressure increases greatly as the temperaturerises,

If the valve does close, the ball will generallydrop back down if allowed to stand for a shorttime. If this fails, the ball may be freed by tappingthe cover plate near the angle valve. Under no

circumstances should any part of the angle valvebe tapped. If the ball still does not release, theother angle valve can be used.For users close to or exceeding 7,000 pounds per

hour, both angle valves may be used in parallel.Unloading Requirements (ICC Regulations): The

following items are excerpts from the ICC regu-lations. For full requirements refer to Sections No.74.560 through No. 74.563 of Agent T. C. George'sFreight Tariff."No tank car containing compressed gas may be

unloaded unless the car is consigned for deliveryand unloading on a private track ... ""Unloading operations should be performed only

by reliable persons properly instructed and maderesponsible for careful compliance with theseregulations.""Brakes must be set and wheels blocked on all

cars being unloaded.""Caution signs must be so placed on the track

or car as to give necessary warning to personsapproaching car from open end or ends of sidingand must be left up until after car is unloaded anddisconnected from discharge connection. Signsmust be of metal, at least 12 x 15 inches in size,and bear the words 'STOP - Tank Car Con-nected', or 'STOP - Men at Work', the word'STOP' being in letters at least 2 inches high. Theletters must be white on a blue background.""Unloading connections must. be securely at-

tached to unloading pipes on dome . . . . beforedischarge valves are opened.""Tank cars must not be allowed to stand with

unloading connections attached after unloading iscompleted, and throughout the entire period ofunloading, or while car is connected to unloadingdevice, the car must be attended by the unloader."

"If necessary to discontinue unloading a tankcar for any reason, all unloading connections mustbe disconnected. All valves must first be tightlyclosed ... ""As soon as a tank car is completely unloaded,

all valves must be made tight, the unloading con-nections must be removed, and all other closuresmade tight ... ""All tools and implements used in connection

with unloading should be kept free from oil, dirt,and grit."Unloading Recommendations (Hooker): Chlorine

cars hooked up for unloading should be protectedby a derail, at least one car length away, at eachopen end of the siding. This is a desirable pre-caution to prevent possible fracture of the unload-

20


22/47

ing line due to any error or accident in switchingoperations.The pipe connected to a tank car discharge

valve should be no longer than 18 inches, andshould be screwed in with a pipe wrench not largerthan an 18-inch size. Use of longer connectinglines and larger wrenches may result in tilting thetank car valve on its gasket, causing a chlorineleak.A flexible arrangement should be provided, at

the tank car end of the unloading line, to accom-modate vertical rise of the tank car as its springsdecompress during unloading. This flexibility maybe provided by a seamless copper loop of Hookerdesign (Customer Part No. 101) or by a suitablearrangement of three Barco joints, packed forchlorine service, which provides 20 freedom ineach of three planes.Extra heavy black iron or steel pipe is recom-

mended for chlorine service. All threads should beclean and sharp, preferably cut with new dies.An operating platform should be provided at the

unloading point to provide easy access to the domefor connecting and disconnecting the unloadinglines, and for operation of valves. This platformshould be of such height that it is suitable forworking on cars of any of the three sizes. (See Fig.14,pages 18-19.)

If night operations are essential, the area wherethe tank car is hooked up should be adequatelylighted.Chlorine piping should be painted a distinctive

color to guard against accidents due to mistakes inidentifying pipe lines. Yellow is the color com-monly used.Hooker Preparation of Empty Chlorine Tank Cars

for Loading:(1) Any chlorine gas remaining in a tank car

is snuffed down and sent to the chlorine disposalsystem.(2) All four angle valves are removed and sent

to the valve reconditioning shop.(3) The tank interior is carefully inspected, by

use of a drop light, for signs of foreign material.(4) Fully reconditioned valves are installed on

the car. These valves have been disassembled andtheir parts and threads inspected by careful, ex-perienced workmen. Valve stems are ground intothe seats, and the stem threads are lubricated withgraphite. Valves are then reassembled, packed withfresh valve packing, and are tested at 300 poundspressure.

(5) At least every two years, every tank car inthe Hooker chlorine fleet is washed, pressure-tested, and dried. At this time, cover plate gasketsand safety valves are renewed.This procedure is followed to help guarantee to

Hooker customers clean chlorine delivered in safe,troublefree equipment.. TONMULnUrlif CM~S (Ton Containers)ICC Specification: 106A500 Approximate Tare

Weight 1550 lbs.ICC Specification: 27 Approximate Tare Weight

13501bs.Dimensions: 29-3/16" ID, 30" OD, 81-1/2" long.

These dimensions may vary slightly among variouscontainers.Markings: The specification number, serial num-

ber, registered symbol, water capacity, and tareweight are marked on each container.A ton multi-unit (TMU) car consists of an

underframe on which are mounted 15 detachabletanks, each containing one ton (2000 pounds) ofchlorine. Consumers using 30 tons or more ofchlorine per year may find it advantageous to usethis shipping container rather than cylinders. Sincea multi-unit car is classified as a tank car, freightis charged only on the 15 tons of chlorine. Theempty containers on returning underframes travelon a free freight movement. In addition, chlorine inton containers costs less than cylinder chlorine.While bulkier to handle, each ton container holds13 to 20 times as much chlorine as does a cylinder.Thus, less handling, connecting, and disconnectingis required.Under some conditions, delivery of one or more

ton containers may be made by truck.Valves and Fusible Plugs: On one end of each

ton container are two brass valves having special%" male outlet threads. Each container also hasthree fusible plugs on each end.Each valve is connected to a Y z " extra heavyeduction pipe. When the container is in a hori-

zontal position with the valves in a vertical line,the top valve delivers gaseous chlorine. The bottomvalve delivers liquid chlorine. (NOTE: The valveoutlet threads are SPECIAL, NOT STANDARDPIPE threads. Never use standard pipe fittings formaking connection. Suitable connector parts aresupplied by Hooker at nominal cost.)The fusible plugs are 1200 apart on each end.

These plugs are safety devices. The fusible metal

21


23/47

has been designed to soften or melt at between1,s8~F and 1605"F, allowing the contents of thecontainer to discharge. The fusible plugs shouldnot be tampered with under any circumstances.Containers must not be subjected to steam orother direct heat, nor to high temperatures.

Unloading: The 15 full containers are deliveredon a rail underframe to the customer's plant. Thefull containers are removed from the underframeby means of a lifting hook in combination with ahoist on a trolley or a jib boom. Ton containerswhich must be trucked from the siding to thestorage area should be placed on saddles on thetruck and preferably clamped down to preventshifting and rolling.A full complement of 15 empty containers is

placed on the underframe for return to the ship-per's plant.

Storage: Ton containers should be stored in acool, dry place and should be protected againstexternal heat sources. They should be stored ontheir sides on a level rack, which may be con-structed of I-beams or two railroad rails properlysupported, a few inches off the ground.Containers should not be stored where they areexposed to continuous dampness.Valve protection hoods should always be kept

in place except when the containers are beingemptied.Store full and empty containers in different

places to avoid confusion in handling them. Itisgood practice to tag empties.Do not store or use containers near elevators or

gangways or in locations where heavy objects mayfall and strike them.Never store containers near powdered metals,

Anhydrous Ammonia, combustible or flammablematerials.

Fig. 15. Chlorine Tank Car

22


24/47

The storage room should be well ventilated, andthe containers so arranged that any container canbe removed with a minimum of handling of othercontainers. 'Where practical, the storage roomshould be fireproof. Storage in sub-surface loca-tions should be avoided.Containers stored out of doors should be pro-tected against direct exposure to the sun and

against accumulation of snow or other materialwhich may build up around them. They should bekept clean and should be inspected regularly.Never store containers or place leaking con-

tainers where the fumes can enter a ventilatingsystem, nor where the wind can carry fumes topopulated buildings or residential areas.Using: Use containers in the order in which they

are received.Never tamper with the safety devices on con-

tainers.Open container valves slowly. The use of large

wrenches, or pipe wrenches of any size will dam-age the valves. One complete turn of the valvestem in a counterclockwise (left-hand) directionopens the valve sufficiently to permit maximumdischarge. Do not use a wrench longer than 6inches on a container valve.For making a connection to the valve outlet,

either threaded connections or clamps and adap-ters are satisfactory. If threaded connections areused, make sure that the threads on appliancesand unions are the same as those on the containervalve outlets. Never force connections that do notfit. The outlet threads on the valves of containersare NOT tapered pipe threads. Suitable union orclamp and adapter connectors can be obtainedfrom this company at moderate cost.Containers or valves should never be repaired

or altered by the consumer.Gas leaks around the valve stem may usually

be checked by tightening the packing nut.To test for chlorine leaks: Attach a cloth to one

end of a stick, soak the cloth with fresh ammoniawater, and apply to the suspected area. A whitecloud of ammonium chloride will result if there isany chlorine gas leakage.As soon as containers are empty, close their

valves, disconnect, and test for chlorine leaks asdescribed above, at the valve outlets. If no leak-age is indicated, apply cap nuts to valve outlets,and attach valve protection hoods securely in theirproper places. Hoods should always be kept inplace except when the container is being emptied.The open end of the line leading from the con-

tainer should be plugged or capped immediately tokeep moisture from entering the system.Return empty containers promptly by reverse

routing.Use only reducing valves and gauges designed

for chlorine. Consult this company for details.Never apply direct heat to any container. Con-tainers should be discharged in a room which is at

a temperature of about 70c F. If the rate of gasevolution from a single container is not sufficient,consult us.

If chlorine is being absorbed in a liquid, thereis a tendency for the liquid to suck back into thecontainer when the container becomes empty, dueto creation of a partial vacuum. This should beavoided, as it has resulted in numerous accidents.As soon as the container is empty and pressure onit has dropped to zero, the container valve shouldbe shut. Then air should be vented into the lineleading from the container, after the valve hasbeen shut off, to prevent liquid from "suckingback" into the line. For this purpose, a "vacuum-break" valve should be installed on the chlorinatorwell line.Always empty ton containers on a scale, in order

to know at all times the amount of chlorine in thecontainer.The pressure in a container is NOT a measure

of the amount of chlorine in the container. Thepressure varies with the temperature of the chlor-ine. At any given chlorine temperature, the pres-sures on containers holding one pound and 2000pounds of chlorine will be the same.Rate of Discharge: Rate of discharge from ton

containers varies with temperature and with thehead against which the chlorine flows. Rates whichwill be attained at various temperatures andagainst various heads may be computed by refer-ring to Figs. 22 and 23 on page 29.Hooker Preparation of Empty Ton Containers

When an empty ton container is to be preparedfor refilling, all remaining chlorine is first snuffeddown and sent to the chlorine disposal system.Fusible plugs are inspected carefully for flaws orsigns of leakage. One of the fusible plugs is thenremoved, and the interior of the container is care-fully examined, using an extension light. If anyforeign material or moisture is noted, the con-tainer must be cleaned and dried. Containerswhich are clean and dry can be refilled. Both valvesare removed and sent to the reconditioning shop.New or fully reconditioned and tested valves areinstalled.

23


25/47

KEYGAS VALVES - Gl & G2LIQUID VALVES - Ll & L2SAFETY RELIEF VALVE -S

NOTE: ON 55 T. CARS ONE GASVALVE MAY SE REPLACED WITH ASECOND SAFETY RELIEF VALVE

1DETAIL A

tLIQUID AIROUT INLETPIPING CONNECTIONS FOR UNLOADING

LIQUID CHLORINE TANK CARS

PART NO. 606ROCKWOOD UNION(D-l0555-C)

r--ll"-j.~ U

4'7" DETAIL "S"

1" SEAMLESSCOPPER TUSING

PART NO. 606ROCKWOOD UNION(D-l0555-C)

DETAIL "A"

1" ANGLE VALVE

RATE CHECK VALVE

Fig. 16. Chlorine Tank Car Valves and Piping Connections

24


26/47

Every five years, each Hooker ton container iswashed and tested in accordance with regulationsof the Interstate Commerce Commission.

~y;:;Chlorine cylinders are shipped in either carload

or less than carload lots. A minimum carload offull chlorine cylinders, as specified by rail freighttariffs, has a gross weight of 30,000 pounds. A min-imum carload of empty cylinders is 36,000 pounds.Markings: The specification number, serial num-

ber, registered symbol, last inspection date, andtare weight are stamped into the shoulder of eachcylinder.A deposit may be required on each cylinder

shipped, which deposit will be refunded when thecylinder is returned, in good condition, within oneyear of the date of shipment.All chlorine cylinders are of seamless steel con-struction, must comply with the specifications of

the Interstate Commerce Commission, and areequipped with valves developed by The ChlorineInstitute, Inc. Fig. 21. These valves, which havebrass bodies and Monel metal stems, are regardedas standard for chlorine cylinders. This valve issimilar to the ton container valve, except that theinternal opening is smaller, and each valve isequipped with a fusible plug. This plug is a safetydevice which has been designed to soften or meltbetween 1580 F and 1650 F, allowing the contentsof the cylinder to discharge. The fusible plugshould not be tampered with under any circum-stances.Handling: Never drop cylinders or permit them

to strike each other with any force.To move cylinders about, use a properly bal-

anced hand truck preferably with a clamp supportat least two-thirds of the way up the cylinder.

To unload cylinders from a truck or car bydropping to a mat is hazardous, and should beavoided.

Storage: Cylinders should be stored in a coolplace protected against external heat sources.Cylinders should be stored upright.Cylinders should not be stored where they are

exposed to continuous dampness.Valve protection caps should always be kept in

place except when the cylinders are in use. Donot hoist cylinders by the cap.Never use a lifting magnet or sling (rope or

chain) when handling cylinders.Store full and empty cylinders in different

places to avoid confusion in handling them. It isgood practice to tag empties.Do not store or use cylinders near elevators organgways, or iIi.locations where heavy objects may

fall and strike them.Never store cylinders near combustible or flam-

mable materials.The storage room should be well ventilated, and

the cylinders so arranged that any cylinder can beremoved with a minimum of handling of othercylinders. Where practical, the storage roomshould be fireproof. Storage in subsurface loca-tions should be avoided.Cylinders stored out of doors should be pro-

tected against direct exposure to the sun andagainst accumulation of snow or other materialthat may build up around them. They should bekept clean and should be inspected regularly.Never store cylinders where, in the event of a

leak, fumes can enter a ventilation system. Neverplace leaking cylinders where fumes can enter aventilation system.

T AB LE I: C HL OR IN E C YL IN DE RSICC Specification: No.25 No. 25 No.3A480Net Content: 100 Ibs. 150 Ibs. 150 Ibs.Average Tare Weight: 97 Ibs. 116 Ibs. 125 Ibs.Average Gross Weight: 197 Ibs. 266 Ibs. 275 Ibs.Over-all Height: 53 ins. 53 ins. 53 ins.Diameter: 8;(. ins. 107i. ins. 107{. ins.

25


27/47

Using: Use cylinders in the order in which they,are received.

Never tamper with the fusible plugs oncylinders.Open cylinder valves slowly. The use of large

wrenches, or pipe wrenches of any size will dam-age the valves. One complete turn of the valvestem in a counterclockwise (left-hand) directionopens the valve sufficiently to permit maximumdischarge. Do not use a wrench longer than 6inches on a cylinder valve.In making a connection to the valve outlet,

either a clamp and adapter or a union connectormay be used. If threaded connections are used,make sure that the threads on appliances andunions are the same as those on cylinder valveoutlets. Never force connections that do not fit.The outlet threads on cylinder valves are NOTtapered pipe threads.Cylinders or valves should never be repaired or

altered by the consumer.Gas leaks around the valve stem may usually

be checked by tightening the packing nut.To test for chlorine leaks: Attach a cloth to one

end of a stick, soak the cloth with fresh ammoniawater, and apply to the suspected area. A white

cloud of ammonium chloride will result if there isany chlorine gas leakage.As soon as cylinders are empty, close their

valves, disconnect, and test for chlorine leaks atthe valve outlets. If no leakage is indicated, applycap nuts to valve outlets and attach valve protec-tion caps securely. These caps should always bekept in place except when the cylinder is beingemptied. The open end of the line leading fromthe cylinder should he plugged or capped immedi-ately to keep moisture from entering the system.Return empty cylinders promptly.Use only reducing valves and gauges designed

for chlorine. Consult this company for details.Never apply heat directly to any cylinder. Cyl-

inders should be discharged in a room which has atemperature of about 70C F. If the rate of gasevolution is not sufficient, two or more cylindersmay be manifolded to provide 3. higher rate of gasdelivery. Cylinders delivering liquid chlorineshould NOT be manifolded.Cylinders will deliver chlorine gas when un-

loaded in an upright position, and will deliverliquid chlorine when unloaded in an inverted posi-tion. Inversion of cylinders should be effected onlyby the use of proper tilters, which can be readily

Fig. 17. Hooker TMU Car Loaded with Ton Containers

26


28/47

6 S AFE TY PLU GS ,3 EACH END

2' 6"

Fig. 18. Chlorine Ton Container

made. Prints of a suitable tilting device will besupplied upon request.

If chlorine is being absorbed in a liquid, thereis a tendency for the liquid to suck back into thecylinder due to creation of a partial vacuum whenthe cylinder becomes empty. This should beavoided as it has caused serious accidents. As soonas the cylinder is empty and pressure on it hasdropped to zero, the cylinder valve should be shut.Air should be vented into the line leading from thecylinder, after the latter has been shut off, toprevent liquid from "sucking back" into the line.This is done by the use of a "vacuum-break" valveinstalled on the chlorine well line.Rate of Discharge: The rate of discharge from

cylinders varies with the head against which theCI~ flows and with the temperature. In addition,circulation of the air around the cylinders greatlyincreases the maximum rate of discharge. Fig. 22shows this effect. Fig. 23 shows variation of dis-charge rate with the discharge head. The data forthese curves were obtained in experiments atHooker's Niagara Falls plant.Chlorine Cylinder Filling Operation:

When empty cylinders are returned to a plant,they are thoroughly cleaned, dried, and recondi-tioned before refilling.Any chlorine remaining in a cylinder is snuffeddown and sent to the disposal system. Valves areremoved and sent to the reconditioning shopwhere they are disassembled and cleaned. Valveseats are inspected, and are reground when neces-sary. Valve bodies with defective threads arescrapped. Valve stems are cleaned and inspected.The valves are then reassembled with new packingand are tested against 500 pounds pressure.Cylinders from which the valves have been re-

moved are thoroughly cleaned with hot water andsteam, then dried with bone-dry air. Interiors andexteriors are carefully examined for dirt and flaws.Neck threads are examined and gauged. Cylindershaving inefficient threads or other flaws arescrapped.Reconditioned or new valves are screwed into

the clean, dry cylinders which are cleaned ex-ternally and repainted. The cylinders are thenfilled to the proper weight, check weighed, andtested for leaks. After 24 hou~s' storage in a warmroom the cylinders are again tested for leaks. This,along with other precautions, helps to assure thecustomer of freedom from mechanical difficultiesand troublesome leaks.

Fig. 19. Chlorine Institute Ton Container Valve

27


29/47

1-1/2" 7 'S" IRON

2-1/2" DIA, HOLE7/S" P lATE (i)

t-----------------Os"-----------------if--------------." ------------; ~l/2'

Fig. 20. Sling Beam and Hook for Ton Containers

Fig. 21. Chlorine Institute Cylinder Valve

.... -_ VALVE ST EM

US E S PE C IAL WRENCH O NVAL VE S T EM (3/8" S O . S HANK)

28


30/47

150140130120

0110wo 100::- cI 90~0 80VI0 70Z: : :>0 60"-

50403020100

1501401301201101000w 90

0:: 80UVI 700VI 600Z: : :> 500c 40

3020100

I " L . , . . o o , . . . . ~ , . . . .I ~ ./ /' ~ . . . . .B V ~,/._ 1-"'"/ Df ~"...i..< r-..~~ J ~ C V/ "" /1/ /1/ /1/ / V FLOW OF GASEOUS CHLORINEFROM ISO LB CYLINDER1/ /// TEMP. 2SoC = 7JOF WITH AIR CIRCULATED -1/ -1/1/ BY FAN BLOWING AGAINST CYLINDER -II I I I I I I I I I I I I I I I I I I IvvI 1/ CURVE A - NO BACK PRESSURE'IJI/ B - 10 PSIG BACK PRESSUREV C - 20 " " "Nt / D - 30 " " "/

II

2 4 6 8 10 12 14ELAPSED TIME - HOURS

206 18

Fig. 22. Flow of Chlorine Gas from 150 lb. Cylinder (no back pressure)

", . . . .i,..- ~!/ . . . . . .

A, ~/ ~) . . . . .""..".V l,;"J . . . -

B FLOW OF GASEOUS CHLORINE l-I-I V~ FROM 150 LB CYLINDER I- . . . . .I V I I I I I I I I I I I I I I I I--. . , - TEMPERATURE 2SoC = 7JOF1/ ,/V NO BACK PRESSUREI IIl11IIIIIllLJl~ CURVE A - AI~ CIRCULATED BY FAN

I BLOWING AGAINST CYLINDERI CURVE B - WITHOUT AIR CIRCULATIONI

2 4 18 208 10 12 14ELAPSED TIME - HOURS 16

Fig. 23. Flow of Chlorine Gas from 150 lb. Cylinder (with back pressure)

29


31/47

TIl.. l~aIIon lO r .w'" " '1 '0 " 0 " '. " J rOU won w o._OrtII ...... nd otdoI1.... ~ ........... "......1ntI on ob....

..0.....10 v . -,,:, . .~-...,_". ., .. . ".. . '", .. .. , . _ ~__""f ,~,~ . ...-_ _ ~. . . . . . . . . . . . .

HOW TO HMD..!",~~~~ .:...::~::;:::::" ~ - . : t . ' - - : - - i : . : ! ' * ' "~;....."-;::,~:',;"_;~'~':~:.:,",.C~': :s - "' __ ' '' ''-t " -~ ., .... ....... _. '" . , .J . w . ." " ' . . ...,f ........" .< --_. 4. , .__" . "" .. l ., .. .. .. 4 - -_ ~"? ......'~

r ,~ "

! : . . -- ' ' : : - : ' : ' ' : ' ' '~_;'~Y',:?. .T~';::;;:~:::~;t?~.;;~~~~...~ - - " " ~. . . . . . . . - - . . . . . . , . , _,._ "" ,...J. . , ~ . . . , < , " ' , ~ . _ , _ ,10 > -__ ," --- - . _ _ _ , _ . _ ~---"..,_,.. _ "'.';:'..;:;...';_~:j~,:.;~::::.."..;..___o~,~~".;~"~::'~~~'r ;;''':.''':;:.~" , . .. ... .. .. - .. . . .. "" _""~_ . .. , .. .. .. ' f _ __~E;!:._~:-:.;.::::!.!~~~~ ...~~'_2'!';;-;.!'.!...:"-"'" ......,._..L "_--~ _ ~ . . . -1 - '> ~ ~, ..< .... " .... .... _.. :_ ... .. __ c . . . . . .. ... ... . ob-" "'I . . "" .. . " I".,...,.""_~ ..;~}~ :.: : :1'~:;; :' !.: ':'::':7- ...,.~~~,:::;:,;,,-,_:,;::.:..'::/'::",,:::-~.'~c.~,,%'-::;..: ' :Z ' :; A : :; ~., 1_= ..... . ., l .. .. . " "" '. ._ _ . .. , .. ." "' . __ ~ .":;':::'~j.z:~..;:-_:.~.~';':"~,~::

__ ""_ ... _y~.eI~M.rl'ft 11.~ , r . . . . . ,d

,.....,~- "_._-'---"_-.--.-.._~--:---. . . . . . . .~. ~.-:;.~

Copies of this 16" by 23" wall chart and the Hooker Chlorine Safety Manualare available upon request.

30

-.


32/47

SECTION 4

The hazards involved in the handling and use ofchlorine are moderate if proper precautions areobserved. The relatively few accidents involvingchlorine have in most instances been due to lackof knowledge of its properties or failure to followrecognized safety precautions.

Chlorine gas is classified as a respiratory irn-tant. In an atmosphere containing this gas, shortshallow breathing should be used. As chlorine isparticularly irritating to persons afflicted withasthma and certain types of bronchitis, such per-sons should not be employed where it is possibleto be exposed to chlorine.When a sufficient concentration of chlorine gas

is present in the atmosphere, it will irritate themucous membranes, the respiratory system, andthe skin. Relatively small amounts of chlorine canbe detected because of the characteristic odor ofthe gas. Larger amounts cause irritation of eyes,coughing, and labored breathing. If the durationof exposure or the concentration of chlorine gas isexcessive, it will result in general excitement of theperson affected and will be followed by restless-ness, throat irritation, sneezing, and copious sali-vation. The symptoms of advanced stages ofexposure are retching and vomiting followed bydifficult breathing. In extreme cases, the difficultyof breathing may increase to the point where deathcan occur from apparent suffocation. Chlorineproduces no cumulative effects and complete re-covery occurs from mild exposure. The physiologi-cal effects of various concentrations of chlorine gasare shown below.When liquid chlorine is exposed to the atmos-

phere, it vaporizes rapidly to chlorine gas and theresulting physiological effects will be those de-scribed above. Should liquid chlorine come incontact with skin or clothing, it may cause burns.Contaminated clothing should be removed imme-diately and the affected skin should be washedwith large quantities of water.

PARTS OFCHLORINE GASPER MILLION

EFFECT PARTS OF AIRLeast detectable odor 3.5Least amount required to cause irritationof throat

Least amount required to cause coughingLeast amount required to produce slightsymptoms (of poisoning) after severalhours' exposure

Maximum amount that can be breathedtor one hour without serious effects

Amount dangerous in 30 minutes to onehour

Amount likely to be fatal after a few deepbreaths

15.130.2

1.04.0

40 to 601000.

NOTE: The above data have been taken from the UnitedStates Bureau of Mines Technical Paper 248. "Gas Mashsfor Gases M et in Fighting Fires."

Canister gas masks of a type approved by theU.S. Bureau of Mines for chlorine service shouldalways be readily available where chlorine is beingstored, transported, or used. Gas masks should belocated outside the probable area of contaminationso that it will be possible to reach them in case ofemergency. Where chlorine is used over wide areas,masks should be available in several locations.Gas masks of the canister type do not supply

oxygen; they absorb the chlorine present in theair leaving clean air to breathe. Where the chlorinecontent of the air is greater than 1per cent, a self-contained oxygen breathing apparatus or fresh airhose mask should be used. Itis suggested that,whenever possible, each chlorine consumer have atleast one such device available in his plant.All personnel who may be required to use gas

masks should be properly instructed and requiredto practice their application and use.

31


33/47

A poor gas mask is worse than no gas mask atall. Since the active materials in a canister becomeinactive when exposed to chlorine or air, canistersshould be kept sealed and should be renewed aftereach use.

In an emergency, telephone Hooker ChemicalCorporation, Niagara Falls, New York 716-285-6655, Tacoma, Washington, 206-383-2661, orMontague, Michigan 616-893-1415.In case of fire, remove chlorine containers from

the fire zone immediately.As soon as there is any indication of the pres-

ence of chlorine in the air, steps should be takento correct the condition. Chlorine leaks never getbetter. Chlorine leaks always get worse if notcorrected promptly. Telephone this company ifyou need help.Keep on the windward side of the leak and

higher than the leak. Since gaseous chlorine isapproximately two and one-half times as heavyas air, it tends to lie close to the ground.When a chlorine leak occurs, authorized, trained

personnel equipped with gas masks should investi-gate. All other persons should be kept away fromthe affected area until cause of the leak has beendiscovered and corrected. If the leak is extensive,all persons in the path of the fumes should bewarned.Water should not be sprayed on a chlorine leak.To do so will make the leak worse because of the

corrosive action of wet chlorine. The heat suppliedby even cold water will cause liquid chlorine tochange to gas at a faster rate.When a leak occurs in equipment in which

chlorine is being used, the chlorine container valveshould be closed immediately.If a chlorine container is leaking in such a posi-tion that chlorine is escaping as a liquid, the con-tainer should be turned so that the chlorine gas

escapes. The quantity of chlorine escaping froma gas leak is about one-fifteenth the amount thatescapes from a liquid leak through the same sizehole.

If a chlorine leak occurs in transit in a congestedarea, it is recommended that the conveyance keepmoving if possible until it reaches an open areawhere the escaping gas will be less hazardous. If achlorine leak occurs in transit and the conveyingvehicle is wrecked, the container or containersshould be shifted so that gaseous chlorine, ratherthan liquid, is escaping. If possible, the containersshould then be transferred to a suitable convey-ance and taken to the open country.Leaks at valve stems may often be stopped by

tightening the valve packing nuts and/or closingthe valve. (See Fig. 21, page 28.)This company has emergency kits which make

it possible to stop almost any leak on a chlorinecylinder, ton container, or tank car. These kits,with skilled technicians to apply them, can bedelivered to any consumer's plant within a fewhours in an emergency. Some consumers find itadvisable to secure such kits for themselves andto train employees in their use. Drawings of theparts for these kits will be supplied upon request.The cost of such equipment may be more thanrepaid by prevention of a personal injury or pos-sible shutdown at a later date.The severity of a chlorine leak may be lessened.

by reducing the pressure on the leaking container.This may be done by absorbing chlorine gas, fromthe container, in caustic soda solution or milk oflime. Evaporation of some of the liquid chlorinecools the remaining liquid, reducing its pressure.At regular points of storage and use, emergency

preparations for disposing of chlorine from leakingcylinders or ton containers should be made. Chlor-ine may be absorbed in caustic soda, soda ash, orhydrated lime solution. Caustic soda solution ispreferred as it absorbs chlorine most readily, The

TAB LE II: RECO M M EN DED ALK ALIN E SO LUTIO N S FO R AB SO RB IN G CHLO RINEChlorine Container Caustic Soda Soda Ash Hydrated Lime

Size - Pounds No.: Pounds, Water, Pounds, Water, Pounds Water,100% Gallons 100% Gallons Gallons100 125 40 300 100 125 125150 188 60 450 150 188 188One Ton 2500 800 6000 2000 2500 2500

32


34/47

proportions of alkali and water recommended aregiven in Table II.A suitable container to hold the solution should

be provided in a convenient location. The chlorinemay be passed into the solution through an ironpipe or rubber hose properly weighted to hold itunder the surface. We shall be glad to discuss thedetails with you, upon request.

Chlorine is not a serious industrial hazard ifworkers are adequately instructed and supervisedin proper means of handling the chemical.Properly designed emergency showers and eye

baths should be placed in convenient locationswherever chlorine is used. Such equipment shouldbe inspected frequently to make sure it is inproper working condition.Asthma, bronchitis and other chronic lung con-ditions or irritations of the upper respiratory tract

suggest that the person(s) in whom they are ob-served should not be employed where exposure tochlorine vapors might occur. Physical examina-tions, including chest X-ray, should be providedfor applicants and employees handling chlorine.

Chlorine gas irritates mucous membranes, therespiratory system and, in sufficient concentration,the skin. BEFORE working with chlorine, knowfirst aid procedures.

1. If chlorine has been inhaled, victim maycough violently, or even vomit, and may perspireprofusely. Carry him to an uncontaminated area.Use blankets to protect him from chilling. Keephim quiet. Make him rest.2. Place victim on back with head and back

raised. Or, he may prefer sitting position. Calldoctor immediately.3. If splashed with liquid chlorine or chlori-

nated water, remove any contaminated clothing.Flush skin with water.4. If available, oxygen should be administered

by a person competent to do so until victim stopsperspiring and can take a deep breath withoutcoughing.5. An anti-acid preparation in water may give

some relief. If unavailable, use milk. Also, a warmdrink such as coffee may be helpful.6. If victim seems to have stopped breathing,

start artificial respiration immediately. RESCUEBREATHING, mouth-to-nose or mouth-to-mouth

is most effective and all personnel should betrained in its use. If Silvestor Chest Pressure-Arm Lift method is used, be sure that an airway ismaintained and that vomitus, blood or blood clotsare not inhaled. A positive-pressure mechanicalresuscitator may take over if manned by a compe-tent operator.7. If eyes are affected, immediately flush withteeter at least 15 minutes, holding eyelids apart if

necessary. Do not attempt to neutralize the chlor-ine. Refer to an eye physician. If available, a fewdrops of a topical anesthetic such as 1~ per centPortocaine may be instilled in the eyes to relievepain and permit more thorough flushing of theeyes with water. While waiting for the eye physi-cian, flush the eyes with water another 15minutes.Then apply cold water compresses. No oils or oilyointment should be used unless ordered by aphysician.8. Swallowing of liquid chlorine is very unlike-ly. However, if chlorine has been swallowed, ANDVICTIM IS CONSCIOUS, immediately givecopious amounts of limewater, milk ofmagnesia. orplain water, but no sodium bicarbonate. NEVERGIVE ANYTHING BY MOUTH TO AN UN-CONSCIOUS PERSON.9. Give whatever other first aid your company

doctor has recommended until the doctor arrives.

The following lists are presented for the con-sideration of all chlorine consumers. Itis recom-mended that an inspection of chlorine handlingmethods and equipment be made at least once ayear, to guard against deviations from approvedsafe practices.These lists are suggestive and are not necessarily

complete, nor are the items necessarily in order ofimportance. The lists are offered as examples ofhow each chlorine user may arrange a check listappropriate to his particular plant.

Item PageTank Car OperationsGas Masks (location, condition, employee

knowledge of use) .Employee knowledge of emergency meas-

ures.

31

3233mployee knowledge of First Aid measures.


35/47

Item PageTanh Car OperationsLocation and condition of piping, includ-

ing internal and external inspection ofpiping (corroded? rusted? vulnerableto blow by falling object, truck, etc.?).

Use of vacuum-break valve.Track and car (derails, warning flag, hand

brake, and wheel blocks).Use of flexible unloading connections.C se of expansion chambers.Air compressor equipment (check valve in-

stalled. tank checked for water and oilevery 8 hours, setting of pressure con-trol). 14

Operation of evaporation equipment andcontrols (temperature, pressures,maintenance) .

Procedure for hooking-up tank cars (in-cluding length of the connector pipeand size of wrench used, presence ofoperating platform, and adequate light-ing at unloading siding).

Gas Masks (location, condition, employeeknowledge of use) .

Employee knowledge of emergency meas-ures.

Employee knowledge of First Aid measures.Location and condition of piping, includ-

ing internal and external inspection ofpiping (corroded? rusted? vulnerableto blow by falling object, truck, etc.").

1223

202112

1 . 5

21

:n

] 2

Item PageUse of vacuum-break valve. 23Unloading procedure. 22Location and condition of storage area. 22Use (installation and practices, safety of

location). 23Periodic inspection of piping. 12-14Use of expansion chambers. 12Use of proper connector parts.Operation of evaporation equipment and

controls, where used.

Cylinder OperationsGas Masks (location, condition, employeeknowledge of use) .Employee knowledge of emergency meas-

ures.Emplovee knowle-dge of First Aid measures.Location and condition of piping, including

internal and external inspection ofpiping (corroded? rusted? vulnerableto blow by falling object, truck, etc.").

Use of vacuum-break valve.Unloading procedure.Location and condition of storage area.Use (installation and practices, safety of

location) .Use of proper connector parts.

34

23

15

31

323.3

12232525

2626


36/47

SECTION 5

Sodium hypochlorite (soda bleach) is prepared byreacting gaseous or liquid chlorine with a solutionof caustic soda. The chemical reaction is:2NaGH + Cl, =NaGCI NaCl +H2G + HeatSodium hydroxide plus chlorine yields sodium

hypochlorite plus sodium chloride plus water.When preparing sodium hypochlorite, several

factors have to be considered to assure a satisfac-tory solution.Solutions of hypochlorite may be prepared to

contain from 10 to 200 grams per liter "availablechlorine." The term "available chlorine" is ameasure of the oxidizing power of a bleach solu-tion. From the equation it may be noted that halfthe chlorine reacts to form sodium hypochloritewhile the other half forms sodium chloride. How-ever, since the oxidizing action of NaGCl is ac-complished by the dissociation of NaGCI toNaCl +G, the "available chlorine," as measured,is considered equal to the total chlorine used toprepare the solution.

Several factors influence the stability of hypo-chlorite solutions, chiefly among which are:(a) Degree of solution alkalinity(b) Contaminants which catalyze decomposi-

tion(c) Temperature(d) Concentration of the solution(e) Direct exposure to lightTheoretically, 1.128pounds of sodium hydroxide(caustic soda) are required per pound of chlorine

for complete combination. However, excess alka-linity is beneficial to the stability of the hypo-chlorite solution. Best results have been obtainedwhen the alkalinity of the bleach solution has beenat a pH of 10 to 11. Irrespective of the alkalinity,low concentration hypochlorite solutions are morestable than high concentration solutions.To prepare stable hypochlorite solutions, mate-

rials of construction that do not contaminate the

solution should be used. Metals which act asdecomposition catalysts and impair the stabilityof the solution must be avoided, particularly inthe case of hypochlorite solutions of more than 50gpl strength. Nickel, copper, manganese and iron,in particular, are highly detrimental to the sta-bility of the solution. Careful preparation of thecaustic soda solution is another factor influencingthe stability of the solution.When sodium hypochlorite is made, heat is

evolved, first, when the caustic soda is diluted, andsecondly, when the caustic solution is chlorinated.The heat of solution resulting from the dilution ofthe caustic soda will vary with the concentrationfinally obtained. In general, this evolution of heatis disregarded because the caustic soda is' dilutedprior to chlorination. The solution is allowed tocool to room temperature before chlorination.In the preparation of solutions of higher con-

centration the heat of chlorination may result ina solution temperature in excess of 30 C (860 F).To help insure a stable solution this heat shouldbe removed. In the case of dilute hypochloritesolutions provision for dissipation of heat is usuallynot necessary.As a general rule, the heat of combination of

chlorine and caustic soda is sufficient to raise thetemperature of the solution approximately 10 C forevery 3 grams per liter of "available chlorine"added. Actually, computations, based on availabledata, disclose that the heat evolved when gaseouschlorine combines with a 4 1 4 % caustic soda solu-tion amounts to 626 BTU per pound of chlorine. Ifliquid chlorine is injected into a 414% causticsoda solution, the heat evolved will be 510 BTUper pound of chlorine.When proper precautions and controls are exer-

cised, and the final temperature of the chlorinatedsolution is not permitted to rise above 30 C(860 F) a stable and clear hypochlorite solutioncan be produced. The lower concentrations (3 to.5 gpl) may exceed this limiting temperature to

35


37/47

95 F if immediate use is contemplated. The finaltemperature of the chlorinated solution may becontrolled by:1. Cooling the caustic solution before chlorina-

tion with mechanical refrigeration or ice.2. Cooling the caustic solution before chlorina-

tion and the hypochlorite during chlorina-tion with mechanical refrigeration or ice.

Generally, the first method is adequate for hypo-chlorite 100 gpl (10%) or less in strength. Forhigher concentrations, the second method mayprove more desirable.A flow diagram for a sodium hypochlorite plant

is shown in Fig. 24. The size of the equipment isdependent upon the requirements.All tanks may be made of steel. Painting the

interior surface of the caustic tanks with alkaliresistant paint will avoid excessive iron contami-nation. Coating the interior surfaces of the chlori-nating and storage tanks with a suitable rubber orvinyl plastic lining will prevent corrosion of thesteel and decomposition of the hypochlorite.Concrete tanks. while used in some installa-

tions, are not recommended because they are sub-ject to cracking and slow erosion.The chlorinating tank should be designed to

provide a minimum of 5 feet submersion for thechlorine inlet (sparger) pipe. This will help pre-

vent free chlorine from bubbling through thecaustic solution. The chlorine is usually intro-duced through an inlet tube.Silver, certain vinyl plastics, and saran have

proven more serviceable than lead for this chlorineinlet tube.Glass, special ceramic, saran, hard rubber and

Duriron', being resistant to sodium hypochlorite,may be used for pumps, piping, and valves.Flake caustic soda or 50% liquid caustic soda

is convenient for preparing the caustic solutionto be chlorinated. The required concentration isobtained by diluting with water. In localitieswhere the dilution water contains undesirable im-purities, it may be necessary to provide specialtreatment of the dilute caustic solution before itis pumped to the chlorinating tank.The following tables show the approximatequantities of raw materials required to produce

sodium hypochlorite at various concentrations.Each installation will have its particular variableswhich must be considered to determine exact re-'luirements and operating procedures.Because each installation may have some par-

ticular governing factor. it is suggested thatHooker Chemical Corporation be consulted whenthe erection of a hypochlorite plant is contem-plated or when some specific problem arises.

1Duriron Company


38/47

HEATEDEXPANSIONCHAMBER

BAROMETRIC LOOPjPRE SS URE GAU GE

CHLORINATIt'-JGTANK

LIQUID CHLORI~"EFROM TANK CAROR TON CONTAINER t

C' l l t====[ :x- :_Jo ==~'==========~

IIIIIII I

IiI ICOOLl~~G

TANKDILUTIONTANK

WATER

MEASURING

PUMP

50C("STORAGE

Fig. 24. Sodium Hypochlorite Plant

PUMP

50% CAUSTIC SODAFROM TANK CAR OR TRAILER

STEAMII


39/47

TABLE III: HEAT EVOLUTION AND METHODS OF DISSIPATION -BTU PER 1000 GAL. SODIUM HYPOCHLORITE

Temperature of Caustic Solution Before ChlorinationG.P.L. Ht. of f-------------------- -----------,-~- -------------------.-----------------Ave. Formation 40 F 500 F 70 F 86 F_~h- ~.T~~~ __ -~~~_~ - L - ~ ~C ~~~ = l ~ ~ B Y~:~~~o~--t---;~':-;:==~~~~~:~~-;-C~-

I ' 128,00030 128,000 ALL - ALL - ALL - - 6501bs.----r- ------t------- -------- ~ ----I---------r-- --- - ---- -- -- -----, 148,000 255,00060 255,000 AL L L - ALL - 107,000: 750 Ibs. - 1300 Ibs.-------- --------- ------ -----.- ------ 1-------------- f---------- ----------+--------- -----f-------------I 39,500 128,000 II 286,000 383,00090 I 383,000 343,500 l 200 Ibs. 255,000 650 lbs. 97,000 i 1450 lbs, - 19501bs.-----t-------- ..---~---------------r----------r-------- ----------1----------I I 207,000 I 286,000 i 420,000 510,000

- ; : ~ \ 1 . : : : : : : : I : : ~ ~ : : : I ~ ; ~ : o ~ f ' G : : , : : :~ ~ : ~ ~: ~ ~ : ~ ~ ~ ~ : o ~ f ". . . . ~ ~ ~ : o : ~ ;-------------.-- -- -----------+ -- ------ ------------------- -- - - - - - - - - i j _ _ - - - - - - - - - - ---------.--1--------1515,000 582,000 690,000 765,000180 I 765,000 250,000 2600 Ibs. 183,000 2950 Ibs. 75,000 3500 Ibs. - 3900 Ibs.

1. Table indica t-s the amount of ice required to limit HIP final tcm pe-r.rtu r of tit" hypochlorite to 86 F'when temperature of solution before chlorination is as indicated and liquid chlorine is used. If gaseouschlorine is used multiply figures by 1.24.2. The addition of the amount of ice shown in the 86' F' column will maintain the final temperature ofthe hypochlorite at the same temperature the solution was before chlorination.3. Ice cooling capacity equivalent to 197.5 BTU per pound of ice.

TABLE IV: PRODUCTION OF SODIUM HYPOCHLORITE USING STANDARD CHLORINE CONTAINERSGallons of Sodium Hypochlorite SolutionProduced With:.P.L.AvailableChlorineDesired

'---,-----_._--------------,-_ ------------------- ---------------TO N (2000 LB.)CONTAINERS

HALF LIFE DA YS *(? i 25 C (77 F)100 LB .CYLINDERS 150 LB .CYLINDERS6000 400 8000 1700

300 40000 200 700-------~- --------

200 26660 133 250

150 200020 100 180

150 120 1600 1000-----

180 66 100 1330 60

"Number of days required to decompose the solution to half strength.


40/47

TABLE V:QUANTITIES OF MATERIALS FOR MAKING 1000 GALLONS OF SODIUM HYPOCHLORITE

Pounds Caustic Soda Dilution Water Solution forAvailable Chlorine Chlorine Finished BleachReqd, Required Reqd. Gals. Chlorination

TRADE G.P.l. WEIGHT flAKE LIQUID USING USING I GALS. % I EXCESS I NaOCl SPEC.% % 98%- 50%- FLAKE 50% NaOH CAUSTIC WEIGHT GRAV.LBS. GALS. lIQ. \ G.P.l. % @ 700 F2 20 1.9 167 200 31 984- 961 I 985 i 2. 34 1 1 I 2.03 1.03I i i I3 30 25 0 300 i 978 I 3.50 I i 1.04-.9 46 977 943 1.5 i 3.00I I i4 40 3.8 334 400 62 973 I 925 971 4.62 2 I 3.94- 1.06i iI

I I50 4.7 417 500 77 966 906 964- 5.75 2.5 4.87 1.07!I 3 I 1.0860 5.5 500 600 92 960 I 887 957 6.90 I 5.76

7 70 6.4 584 700 108 951 868 949 8.00 3.5 6.64- 1.10

8 80 7.2 667 800 124 944l 849 I 942 9.08 4 7.50 I 1.11i I9 90 8.0 751 900 138 939 830 935 10.20 4. 5 ! 8.34- 1.13I

10 100 8.8 834- 1000 154 931 812 928 11.30 5 9.16 1.14

11 110 9.5 917 1100 169 925 791 920 12.32 5.5 10.05 1.15

12 120 10.3 1001 1200 184 916 773 913 13.40 6 10.76 1.17

13 130 11.0 1084 1300 20 0 911 752 906 14.40 6.5 11.53 1.18

14 140 11.7 1168 1400 21 6 904 736 899 15.45 7 12.28 1.20,15 150 12.4 1251 1500 231 900 717 892 16.45 7.5 13.03 1.21

16 160 13.1 1334- 1600 24 6 892 699 885 17.45 8 13.75 1.22

17 170 13.8 1418 1700 262 883 679 877 18.42 8.5 14.45 1.2418 180 14-.4 1501 1800 276 878 659 870 19.50 9 15.14 1.25

19 190 15.1 1585 1900 29 3 871 64-1 863 20.50 9.5 15.83 1.26

20 20 0 15.8 1668 2000 308 865 624 856 21.40 10 16.50 1.27

:3 9


41/47

SECTION 6

'-:11 J

, \ 1

The maker of hypochlorite solutions is interestedin the available chlorine content of his finishedsolution. The term, available chlorine, which is amisnomer, is actually a measure of the oxidizingstrength of the solution. The maker is also ofteninterested in the free alkali content of his product.

'l,vailable Chlorine Determination:Description: Available chlorine is deter-mined by titration with alkaline arsenite solution.

Starch-iodide solution acidified with acetic acid isused as an outside indicator.REAGENTS

SODIUM ARSENITE, N/I0. -Dissolve 4.945grams of pure arsenious oxide (As:,O,) and 20grams of anhydrous sodium carbonate in 250 mlof distilled water over a steam bath. Dilute to oneliter with distilled water. This gives a standardsolution, one ml of which is equivalent to 0.003546grams of chlorine. This solution is stable for twoor three months.

STARCH-POTASSIUM IODIDE INDICATOR.-Grind .5grams of soluble starch, C. P., with 25-:30mls of distilled water, transfer to a IIi) literbeaker, add one liter of boiling water, stir - vigor-ously on a hot plate or steam bath until thestarch is dissolved. Add ;) grams of potassiumiodide, C. P., crystals and a small teaspoon ofcarbolic acid crystals and stir to dissolve. Thissolution will keep for a month.

ACETICACID,1-1. - Glacial acetic acid, C. P.,diluted with an equal volume of water.

POTASSIU:vrODIDE,C. P., CRYSTALS.SVLFURIC ACID. 5N. - Dilute HO ml of

fLSO" C. P .. 9iV~. to one liter with distilledwater.

SODIUMTHIOSULFATE,N/I0. - Dissolve 25grams of Na:,S:,O:l'5H,,0, C. P., in one liter offreshly boiled, cooled, distilled water. Standardizeagainst N/I0 iodine solution.

PHENOLPHTHALEININDICATOR. Dissolve 5grams of phenolphthalein in one liter of ethanol'2B ethanol is satisfactory. 'NITRICACID,DILUTE.-Dilute one volume of

C. P. HN01, approximately 70%, with four vol-umes of distilled water.

SODIUMBICARBONATE,OWDERED.-NaHCO:l,C. P., powdered, or baking soda will do.POTASSIUMCHROMATEINDICATORSOLUTION.

- Dissolve 10 grams of the C. P. crystals in 100ml of distilled water.SILVERNITRAT'E,N/I0. - Dissolve 17 grams

of silver nitrate, C. P. crystals in distilled waterand dilute to one liter. Standardize againstweighed quantities of pure sodium chloride.

HYDROCENPEROXIDE,NEUTRALIZED,3%. -Neutralize with dilute NuOH to the phenolphtha-lein endpoint. Hydrogen peroxide, U. S. P. gradeis satisfactory.

HYDROCHLORICCID,N/I0. - Dilute 9.5 mlof hydrochloric acid, C. P., sp. gr. 1.18 to one literand standardize against anhydrous sodium car-bonate, using methyl red as indicator.

BARIUMCHLORIDE,N. - Dissolve 122 gramsof BaCL2H:.'0, C. P. crystals, in one liter of dis-tilled water.

Dilute a sample of the proper size (see tableVI, page 41) to 100-200 ml in a casserole.

Titrate with sodium arsenite cutting downthe separate additions of the reagent to 0.2 mlnear the endpoint. Add a drop of starch-potassiumiodide solution and a drop of 1-1 acetic acid toeach of the holes on a white spot plate. Test thesolution being titrated by adding a drop from the


42/47

stirring rod to the indicator solution on the spotplate. The endpoint has been reached when theindicator solution will no longer be turned blue.Save the titrated solution for a total chlorinedetermination.

ml arsenite 1000--------- = gpl ava ilable Cl-ml of sampleThis may be shortened in practice to-

fil arsenite 3.55ml of sample =gpl available Cl;

A method which is better suited to factoryoperations depends on displacing iodine frompotassium iodide with the chlorine in the hypo-chlorite. The iodine thus released is titrated withsodium thiosulfate.

The sample (see table below) is pipetted intoa 250 ml Erlenmeyer flask where it is diluted with25-50 ml of distilled water. A few C. P. reagentgrade potassium iodide crystals are added fromthe point of a clean spatula. (The correct amountis about the bulk of the eraser on the end of a leadpencil.) The solution is then acidified with 5 mlof :'iN sulfuric acid. The resultant brown colora-tion is discharged by the addition of N/10 sodiumthiosulfate solution measured out of the burette.The endpoint, which is clear and sharp, is evi-denced by the disappearance of the brown color.

ml Na~S:20:l solution 3.546---------- = gpl available Cbml of sampleTOTALCHLORINEDETERMINATION.- To the

residue from the available chlorine determinationusing arsenite, add 2-3 drops of phenolphthaleinindicator and add dilute nitric ; light red-brown color:

ml N!10 siJ,er nitrate 0.00854G, 1000ml of sample-

pe r li .'


43/47

SECTION 7

Chlorine does not commonly exist in the free statein nature, although it has been reported to befound in the gases of certain active volcanoes. Amember of the halogen (salt-forming) group ofelements, it is the most strongly electronegativeof all elements except for its fellow halogen,fluorine. Found abundantly in combination withother elements as carnallite (KMgCb-6H20), syl-vite (KCl), and common salt (NaCl}, it is ob-tained from chlorides by electrolysis or by the

o 'F' ~ ' ' ' ' ' ,action of oxidizing agents.Over one-third of the chlorine of commerce is

produced from common salt brine in Hooker Type"8" Diaphragm Cells. The brine is decomposed bydirect electric current, yielding hydrogen, causticsoda, and chlorine. The chlorine comes from thecells as a green-yellow gas, which after being thor-oughly dried and purified, is liquefied andpackaged.

Hooker Type SA Cells

,12


44/47

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45/47

Niagara Falls, N. Y. Plant, Eastern Chemical Division

r"'~

. '" ._.' ~" ::.~: ,.~~'""'~....' _...s-

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46/47

ANOLYTELEVELINDICATOR

CHLORINE GAS OUTLET

HYDROGEN OUTLE.T

ASBESTOSCOVERE.DCATHODE

CONCRETE TOP

BRINE FEED LINE

Fig. 26. Hooker Tvpe S~ Cell. Diagrammatic Section

15


47/47

TAB LE VII: TEM PERATURE CONVERSIO N TAB LES-459.4 to 0 - 5.5 7 1.6 37 . 1 210. 2 426 147 2 827 I 27 68 1226 4064

. . 5 . 0 7 3 . 4 3 7 . 7 212. 0 432 1490 83 1 27 86 123 1 4082C - 4.4 7 5.2 438 1508 83 8 2804 1237 4100-273 - + . : ; / ' .1 - 3 .9 7 7 . 0 100 to 1000 44 3 '):F1 1526 84 2 2822 1242 4118-268 3.3 78.8 449 1544 849 2840 1248 4136-262 - 2.8 80.6 C 454 1562 85 3 ) 2 8 58 1253 . 4154-257 . . 2 . 2 82.4 38 212 460 i~ 0\.J 1580 860 1 2876 1259 4172-251 - 1. 6 84.2 43 23 0 465 1598 864 1 2894 1264 'J 4190-246 1. 1 86. 0 49 248 471 1616 87 1 2912 1270 4208-240 .6 87. 8 54 j

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6650058 Chlorine Manual

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