-.

b-

National Academy Of v

.,1

..__ Sciences 1-~ ~ ;: , , - National Ressarch Council .-1 I r g NUCLEAR SCIENCE SERIES .. ,3 J :; .. k .-1 1: ,:1 : i The Radiochemistry ;. .of the Rare Gases ,. s. -. ;r. ~ ., --i .. 1 .1 ..... ,
r r . ,. i ..

Ii

i i .-

COMMITTEE
L. F. CUR-, CkaJ~ National Bureau of ~anla

ON NUCLEAR SCIENCE
ROBLEY D. EVANS, Vh Ctinnas Mamaohuema Institute of Teohuology

J. A. IWUREN, Secrdury WeWl@mue Eleotrlc Corpratlon

C. J. BO~ M RI* Nadooal
J.

W. IRVINE,JR.
Illlanwa

Laboratory

Maeaachueetca

d Teohmlogy

ROBERT G. 00CHRAN Texan &@xhuml and Mechanical

E. D. IUEMA
Nortlmeutem W. WAYNE ~~ of Mkhlgan UntveralW

SAMUEL EPSTEIN California Inetituw of Teohuology U. FANO National Bureau

Untverslv

J. J. NICKSON Memorial HoEJ@tal,

NOW

York

of Studada

HERBERT GO-ED? Nuolear Development Amerioa

ROBERT L. PLATEMAN Iabmvltoire & Chhnie Phy81que of D. M. VAN PA77ER Bartol Reaearoh Foudulon

Co~ratlon

LIAISON
PAUL C. AEBER&XiO AtOmio Energy Comnlionion J. HOWARD MO~EN National Solence Foudatlon

MEMBERS
CHARLES K. HEED U. S. Air Fome
WIIJJAM

E. WRIGHT

OHlce of Naval Reoeamb

SUBCOMMITTEE
W.

ON RADIOCHEMISTRY
HAHOLD NIBBY Mad Uhcmatory GEORGE LEDDICOITE Oak RNational Labomtory JULIAN NIELSEN Hantbrd Laboratnrlen ELLIS P. STE~EHG &gonne National Laboratory PETER C. STEVENSON of California (L1vermore)

WAYNE MEINKE, Chfnwux

of Mlchlgan

Unlverally

GREGORY R. CHOPFlorlda State Unlven9i~ GEORGE A. COWAN Loa Akuoa 6Ci~1fi0

Laboratory

ARTHUR W. FADLHALL ~nlvemi~ of Waahbgton JEHOME HUDIS Brookhaven National Laboratory EARL HYDE Unlverni@ of California

University

(Berkeley)

LEO YAFFE McGUl LInlvareilg

CONSULTANTS
NATHAN BALL(XJ Cenma dEtuda de lEnergle Mol-Da& BalsIum Nucleaire JAMES DeVOE University of Michigau WILLIAM MARLow National Bureau of Smudards

d#6J M733r.
C,.1

The Radiochemistry of the Rare Gases

FLOYD F. MOMYER,

JR

Luwr6nc8 Radiaiia Labcwm WniveY8ity of Calijimtia Livermore, Calijbnch

,. . ... .,
CMober

Iwo

PROPERTY

u X   

Natimml Academy

subcommittee m Rndlochemistry of 8ciemces-Natiaid Research

AW8MWhM
titidlbohiod

Calncil

PrMdin LIM. PAoo$0.75. b-ws,~~f=-u-m~*.D.c..

FOREWORD

The Subcommittee on Radlochemlstry Is one of a number of subcommittees working under the Committee on Nuclear Science within the National Academy of Sciences - National Research council. Its members represent government, Wdustrial, ahd university laboratories in the areas of nuclear chemistry end analytical chemistry

The Subcommittee has concerned itself with those areas of nuclear science which involve the chemist, suchas the collection. and distribution of radiochemical procedures, the establishment of specifications for radiochemically pure reagents, availability of cyclotron time for service irradiations, the place of radiochemis.try in the undergraduate college program, etc.

This series of monographs has grown out of the need for up-to-date comptlationa of radiochemical information and procedures. The Subcommittee has endeavored to present a series which will be of maximum use to the working scientist and F@ch monowhich contains the latest available information. graph collects in one volumethe pertinent information required for-radiochemical work with en individual element or a group of closely related ,elements,

An expert h the radiochemistry has written the monograph, following by the Subcommittee. The Atomic~ergy the printing of the series.

of the partictiar a standard format Commission has

element developed sponsored

The Subcommittee is confident these publications useful not only to the radiochemist but also to the worker in other fields such as physics, biochemistry who wishes to use radlochemical techniques to solve problem.

will be research or medicine a specific

W. Wayne Meinke, Subcommittee on

Chairman Radlochemlstry

iii

INTRODUCTION
This pared report dealing with the radiochemistry of the rare gases was pre -

at the request Science on the early

of the Subcommittee of the National radiochemistry of this

on Radiochemistry Council

of the Committee of

on Nuclear monographs The rare gas

Research of all monograph

as one of a series

the elementE. are devoted to general reviews disare of

sections

propertied of separation

of interemt techniques

to the radiochemimt for rare gases of rare radioactive rare gases. from should .

and to some The gases rare last from three

general chapters

cussion

respectively cussion tion

a discussion used

of the removal for counting for

targets,

a dis-

of techniques

gases,

and a collec-

of radiochemical The author

procedures appreciate

would

receiving which

readers.

any additional in such

ina report

formation,

published

or unpublished, of the rare this

be included

on the radiochemistry The Mr. R. A. author takes

gases. to acknowledge of this monograph. the a,ble assistance of

opportunity

daRo za in the preparation

iv

CONTENTS
Foreword Introduction I. II. III. IV. V. VI. General Table Review Sample Counting Collection . . . . References of Isotopes of Features Solution Rare . . . . Pertinent of He, Ne, . . to Rare A, Kr, . . Gas Xe, . . . . . . . . . . . . Etry . . Gases . . . .
111 -

iv 1 2 5 27 29 34

Radiochemietry and Rn

of Interest

in Rare

Gas

Radiochemi . . . the Rare Air . and

and Exchange Gas Activities

with Carriers . Procedures . for from

of Radiochemical 1 Removal Their

Procedure

of Kr

and Xe

Subsequent

Separation

34

Procedure

1 A Removal Fission

and Separation from

Products

of Kr and Xe 235 Targets U and . Product . . Xe . Product . 6 H20 Fission Xe Targets Gases and its . . . ,

40

Procedure

2 The

Extraction, UBee

Industrial Procedure 3 Rapid Kr Procedure

of Kr

Purification 85 .

43

Removal U Foil

of Fission .

from

46

4 Recovery from

of Fission .

Product ,

UMetal Removal U03 or

46

Procedure

5 Rapid from

of Fission U02(N03)2

48 48

Procedure Procedure

6 Separation 7 Removal Collection Tube .

of Long-lived of Rn from on the .

Th Targets

Cathode . .

of a Discharge . Half-lives (II) . 51 . 49

Procedure

8 Determination by the Charged

of Active Wire

Gas

Technique

The Radiochemistry

of the Rare Gases

FLOYD F. MOMYER, JR Lawrence Radiation Laboratory

University Livermore, I. GENERAL H. Remy, REFERENCES Treatise Elsevier Vacuum of CaUforrda California TO RARE GAS RDIOCHEMISTRY by J. S.

PERTINENT

on Lnorganic Publishing Technique,

Chemistry, Co,

VO1. I (translated

Anderson),

, New York Wiley

(1956).
and Sons, New York, 1949.

S. Dushman,
R. T.

John

Sanderson, and Sons Dodd 2, Inc.

Vacuum , New L.

Manipulation York ( 1948).

of Volatile

Compounds,

John

Wiley R. E.

and P.

Robinson, Co.

Experimental , New York

Inor~anic (1954). Vql.

Chemistry

Chap. S.

Elsevier The

Publishing Adsorption

Brunauer,

of Gases

and Vapors, Princeton, Reinhold

.1,

IPhysical (1942), Co. ,

Adsorption, A. New I. M. York,

Princeton Keulemans, 1959, A. .-

University Gas

Press,

N, J.

Chromatography,

Publishing

2nd edition. llThe Ad~orption II Mound of Krypton Laboratory and Xenon report MLMon Activated

Lawrence Charcoal Miamisburg, A. Guthrie

Weller,

A Bibliography, Ohio, and R. 1959. K, Waker

1092,

ling,

editors, Series,

Vacuum Div. I,

Equipment Vol. 1,

and Tech-

niques, Book C. D. Co.

National

Nuclear

Energy 1949.

McGraw-Hill

, blC, , New and N,

York,

Coryell

Sugarman, Nuclear Book 154,

editors, Energy Co.

Radiochemical Series, , New Div. York,

Studies: IV, Vol.

The 9, Papers

Fission ~ooka 64-70,

Products, 2 and 3, 139,

National McGraw-Hill 145-50,

, Inc.

1951.

141,

and 311-17.

II.

TABLE

OF

ISOTOPES

OF

HELIUM, AND

NEON, ,*

ARGON

KRYPTON,

XENON

RADON

Isotope

Half -life 1.3

Type X10-4

of Decay ~Oatmos. wells) )

Method

of Preparation

He3

Stable

(abundance (abundance

Natural

1. 7X10-5% -looyo) PP+ P+

He4 He6 Ne18 Ne9 Ne20 Ne21 Ne22 Ne23

Stable -0.8 1.6sec -18 sec

(abundance sec

Natural Be9(n, a)

F 19(PF 2n) F19(p, Natural Natural Natural n)

Stable Stable Stable -40 sec

(abundance (abundance (abundance

90. 92%) 0.257 ~,)

8. 827) P-

Ne22(n, Na23(n,

y); p); p) n);

Ne22(d, Mg26(n,

p); a)

Ne24 A35 A36 A37

3.38 -1.8 Stable -35

min sec (abundance

PP+

Ne22(t, S32(a, Natural

C135(p,

n)

0.337%)
EC

day

S34(a, C137(p, Ca40(n,

n);

C137(d,

2n); a);

n); K39(d, a)

A38 A39 A40 A41

Stable -265 Stable -110

(abundance yr (abundance min

O. 063%) P99. 60070) P-

Natural A38(n#y); Natural A40(d, K41(n, P); A40(n, p) parent span) n) K 42 Y); K39(nFp)

A42 Kr76 Kr77 Kr78 Kr79

~3.5yr 9.7 hr

PEC EC-20~0, (abundance o. 3547,) EC 957, ~+57 ~+ -80910

A41(n)~); Y89(p, Se74(a, Natural Se76(a, Br79 n);

-1.2hr Stable 34,5hr

Br79(d, Kr78(d,

2n); p);

(p, n); y)

Kr78(n, Kr80 Stable (abundant e 2. 27~0) Natural

Listed Isotopes, Phys. 30, the ori~nal

are those nuclides having an IIAII or IIBII classification and G. T. Seaborg: D. Strominger, J. M, Hollander No. 2, Part II, April 1958. Further information and literature may be found in said article,

in llTable

of

Revs. Mod. references to

TABLE

OF

ISOTOPES

OF

He,

Ne,

A,

Kr,

Xe,

and Rn,

(Centd]

Isotope

Half - life

Type

of Decay

Method

of Preparation

Kr81 Kr1 Kr82 Kr83m

-10

.sec yr (abundance

IT EC 11. 56~0) IT

Brsl(p, Kr80(n,y) Natural Se80(a, Kr82(n, . Kr83; Br83;

n);

daughter

Rb

81

2.1X105 Stable

114 min

n); y);

Kr82(d, x-rays

p); on

fission ~aughte

U, daughter r Rb83 U U p); p); U,

Kr83 Kr84 Kr85m

Stable Stable 4.36

(abundance (abundance hr

11, 557.) 56. 90!70) ~-78~0, IT 22~0

Natural; Natural; Se82(a, Kr84

fission fission n); Kr84(d,

(n, y); a);

Rb85(n,

Sr88(n, daughter Kr85 Kr86 87 ,Kr 10.3 Stable 78 min yr (abundance 17. 377.) PKr84(n, Natural;

fission 85 Br fission U

y);

fission y); p); U, U, U, U, U, U, U PU

Pi=

Kr86(n, Rb87(n,

Kr86(d, fission Th Pu Pu Pu Pu, Pu Th

p); U

Kr88 Kr89 Kr90 Kr9 Kr92 Kr93 Kr94 Kr97 xe121 xe122 xe123 xe124 xe125m

2.8hr 3 min 33 9.8 aec sec

Fission Fission Fission Fission Fission Fission Fission

Pf3-

3. Osec 2.0 sec

l,4sec 1 sec 40 min 20 hr 2 hr Stable 55 aec (abundance O. 096~,)

PF F PP-

P+
EC EC, f3+

Fission U, 1127 (p, 7n) 1127 (p, 6n) 1127 (p, 5n)

IT

(?)

Natural 1127 (a,6n)Cs

125;

daugh-

xe125 xe126 xe127

18.0 Stable

hr (abundance o. 0907,)

EC

ter Cs125 Te122 (a, n) Xe 124(n, Natural 1127 (a,4n)Cs ter (Table Cslz7 on page 4)

y)

75 sec

IT

127;

daugh-

Continues

TABLE

OF

ISOTOPES

OF

He,

Ne,

A,

Kr,

Xe,

and Rn.

(Centd)

Isotope

Half - life

Type

of Decay

Method

of Preparation

~e127

36.41

day

EC

~e124 1127

(a, n);

1127( d,2n)

(p, n);

Xe Iz+n,y)

xe128 xe129m xe129 xe130 xe131m X=131 ~e132 xe133m xe133

Stable 8.0 day

(abundance

1, 919L70) IT 26. 447.) 4. 08~0) IT 21. 18%)

Natural xe128 Natural Natural xe131

(njy)

Stable Stable 12.0 Stable Stable -2.2 5.270

(abundance (abundance day (abundance (abundance day day

(n, n);

fission U

Natural;

fission

26. 89~~) IT 13-

Natural; fission U xe132 (n, y); fission U xe132 (n, y); Xe 132(d, p); ~e134 (n,2n); Te130(a, n); ca133 (n, p); Be 136(n, a); fission U fission (n, 2n); (n, a); (n, y); (n, 2n); U fission (n, y); U U, U, U U U 5n) , 4n) Th Th U U U y);

xe134 xe135m

Stable -15

(abundance

10. 4470) IT

min

Natural; xe136 Ba138

Xe 134(n, fission Xe134(d, Ba 138(n, U

~e135

9.13

hr

xe134 P~e136 fission

p); a);

xe136 xe137 xe138 ~e139 Xe 140 xe141 ~e143 8 Xe 144 Rn206 Rn207 Rn208 Rn209 ~n210 ~n21 1

Stable 3.9min 17 min 41 sec -10 -2 sec sec

(abundance

8. 8770) PPPPPPf3a65~0, EC 35~0 a470 a-20~o a 17~0 EC-4~o a26%

Natural; ~e136 Fission Fission Fission Fission Fission Fission *U197

fission

l. Osec -1 -6 -10 -22 sec min min min

EC 96~0, EC-80~0, EC 83~0, a-96~0, EC a (est. ) a

74~0,

(N14, *U197(N14 Span Spall Span Span Th; Th; Th; Th;

30 min 2.7 hr

16 hr 23 min -10-6sec

span) Pb(C12, .Pb(C 1, span) 12 Pb(C , span) .. span) Pb(C l,

Rn21 2 ~n215

SpaU Th; Pb(C12, SP1l) 232 U-2 27 chain from Th (a, %)

TABLE

OF

ISOTOPES

OF

He,

Ne,

A,

Kr,

Xe,

and Rn,

(Centd)

Isotope

Half-life

Type

of Decay

Method

of Preparation

~nz

16

-10-4sec

(est.

~228

chain

from

Th

232

Rnz17

10-3

sec

(a, 8n) ~229 chain (a, 7n) ~230 chain (a,

from

Th

232

Rn2

0.019

sec

from

Th

232

6n)
~235 decay

Rn2 Rnzzo

3.92

sec

Member chain

51.5sec

Member chain Thz32 Member chain

Th232

decay

~nzz Rnzzz

25 min 3.8229 day

~- -80~, a

a-20~o

(p, span) U238 decay

III.

REVIEW

OF

FEATURES

OF

INTEREST

IN RARE

GAS

RADIOCHEMLSTRY

The krypton, of half-life One gases can

rare xenon, long

gases,

Group

O of the periodic Helium and neon

table, possess

are

helium,

neon,

argon,

and radon; enough

no radioactive in the ordinary remaining

isotopes sense. rare

to permit

radio chemical the

studies

conceive

situations

in which and from by far

separation might

of the

four

from

contaminants problem

one another is the

be necessary.

However, re-

the most sulting each with wise

common from fission The

separation from other

of krypton fission

and xenon

of heavy

elements on rare detailed and xenon. varies helium gas

products is largely

and from concerned will like-

other. this

literature and most krypton

radiochemistry in this gas

problem, around

discussion As rare

monograph

center

separations

generally manner application if required. will be found gases reactions them. as one of

depend proceeds

on some through

property

which from

greatly

and in a regular the further be simple

the group

to radon, will often

the procedure Reviews in most are texts

to include of the

other

rare

gases

Ichemical

on inorganic inert. They

of the rare gases propertiesil 1 chemistry. In a practical sense, will remain impurities chemically other unaltered than rare

the rare in any

chemically

chosen

to quantitatively

remove

gases

from

However, their

rare

gas

atoms

do interact these

with

other

atoms,. are

molecules,

or ions

in

neighborhood. or Ivan existence Hydrates and der

Whether Waal!sr

inter actionfi

properly here.

considered +

chemical The established. to exist, high.

in nature

is of no concern such as HeH

in discharges for the four

of species heavier

and He2

has

been

members

of the group of solvents with are

are

known

solubilities

of rare solvent

gases

in a number

relatively number on solof

Volubility

in a given

generally of rare

increase~ gas volubility gas

atomic

the rare vent, plicable

gas. A number

of studies

dependence (Henr yls One for

temperature, over wide

and partial ranges ) have

pressure appeared

of the rare

law is apof the more krypton stream

in the literature. system

comprehensive and xenon of organic from liquid

studies gas

also

outlines by their 2

a proposed absorption

recovering

streams

in a counter-current

(kerosene). rare contact gases, with

in handling remember condensation moval ical for of rare occlusion. essentially from that

especially liquids or

tracer solids

amounts, (including

one does system may

well or

to

walls) result

from gases

the gas from

phase the gas

of other phase

liquids through rare

or solids solution, gas are carriers added

in reor phys added

adsorption are

Thus

in quantitative reasons that

work

usually

the same solutions.

carriers

for

species

to be

separated

A series of substances known as clathrates has received 3,4 study, Clathrates of argon, krypton and xenon have been crystallizing Rare gas quinol atoms of these (one rare are under an atmosphere in cages an upper of the within limit rare gas

considerable prepared by

at high ulting

pressure. the gas in the

contained setting atom gae for

the re;

crystal,

number crystal

cages gas

on the amount quinol molecules). markedly than

of rare The

ever y three crystal

actual of

concentration crystallization Clathrates sources suits

of rare

in the

depends less

on the conditions limit. for use

and is usually

considerably krypton The have

the theoretical been prepared

of fission-product 85 5 activity. of Kr concentrations

recently

as

preparation equal to 25%

described

in the

reference limit.

re This

in krypton

of the theoretical

corresponds pressure product powder few parti

to the concentration and results in 3 curies is about loss

of Kr

in the gas phase at about 25 atmospheres 85. per gram of clathrate (using fission The material may be ground is to a only and a

krypton with

which

5~0 Kr 85). of activity

no appreciable per

and the 10Ss is protected

on standing from

per .million. which

day if the material quinol.

water

other

substances The chemical

dissolve

operations

involved

in separating other must (usually than

and purifying rare gases.

rare The

gases separa of -

are tion

performed of the rare

on elements gases from physical

or compounds one another property

be accomplished vapor pressure

on the basis or extent of

differences

in some

adsorption). rate rare the ical some gas. rare

It may or all Thus

often

happen

that this other

physical rare nor

separation gases most step from

will

also

sepa -

of the impurities it is often neither as

than

a particular to purify -

necessary

convenient or steps

gases

chemically Depending

a group

as the first contaminating operations rare

in a radiochem amounts

procedure. be possible

upon the

species

and their will

it may

that no chemical may

whatever gases are phase

be necessary. to those which of

Substances may exist

which

contaminate

limited at the

in appreciable At said to denote

concentrations temperature appreciable vapor

in the gas this will

temperature the term their

the experiment. being critical 2) used here

include:

1) gases, above

amounts pressures vapor

of substances greater pressures than are

temperature vapors, but which partial

or having

1 atmosphere; less than one

unsaturated

substances are present are with

whose

atmosphere that their rated

in amounts less than or their

appreciable vapor

but small and

enough 3) satu-

pressures

pressures;

vapors

in equilibrium The word

solids

liquids

having

appreciable of course is a large The volatile

vapor be decategory, rare species

pressures. fined in the

Iappreciablelr

in the foregoing Although encountered the constituents

must

context

of the experiment. usually from such from

the above is quite of air, hydrogen

the number gases must

of contaminants often be purified dissolution

small. from halides

involved

in target

as hydrogen, small amounts

and otides and trace below which for each

of nitrogen, amounts of these. been useful. 1) with (ea.

and occasionally halogens.

of hydrocarbons are listed

of elemental The list

Methods complete that

of removal as regards

is by no means

methods

have to be

or could

be used,

but it is hoped

it is representative

enough

Nitrogen: sponge, has been

Mole

amounts mesh 6 are glaes

may at

be quantitatively 1000 -11 OOC. is also Use

removed of lower

by reacting temperatures

titanium 850C)

14-20 reported.

Oxygen necessary es . The

removed

quantitatively. are above and to

Quartz the

or ceramic point

furnaces of Pyrex must

as these reaction rate

temperatures is quite

softening

exothermic controlled

so the temperature prevent to remove passive this phase destruction nitrogen through is

be monitored

and flow Calcium

of the gas been

of the furnace. (400 -5.00 C).

has

often

used tend

satisfactorily

Calcium films.

does, For

however, small

to become of impurities

formation

of surface

amounts

problem with

sometimes circumvented by conducting the reaction in the gas 7 Ca vapor. Clean uranium turnings at 800 C will also react with hydrocarbons). be removed with copper monoxide, with nitrogen in the above 350C reactions CUO. Passage . Oxy-

nitrogen 2) gen also 3)

(and decompose Oxygen: reacts Will rapidly

turnings light

above pa,raffin

to give

Hydrogen,

carbon

hydrocarbons:

of the gas rapidly. temperature moval

stream

over

CUO will

at 500C

will

oxidize in like

HZ to H20 manner

and CO and C02

to C02 but a reenough

Hydrocarbons of 900C may

be oxidized

to H20

is necessary be necessary that

to achieve

rapid

reaction.

Subsequent if high over

of oxygen are

(and is easily

accomplished), of oxygen

temperatures appreciable. 4) often not

used

the dissociation

pregsure

CUO becomes

Water: specific

In addition enough), .

to condensation water P205, may

of water

in cold

traps

(a method any one

be removed

by passage and CaC12 are

through

of a number with

of desiccants

Mg(C104)2;

representative,

equilibrium partial pressures of water over them at room temperature -5 and O. 2 mm Hg respectively. Ofzxlo , 5 x 10-4, P205 and CaC12 repthe extremes achieved of efficiency wide use in common desiccants enough . for Magnesium practically per all pur-

resent chlorate poses Where CaC12 maining

has

as it is efficient by distilling are involved, and then

and is easily large amounts

regenerated of water

the water gases with are

off in vacuo often dried

at 220-C, first with re -

to remove traces Carbon

most

of the water

Mg(C104)2

to remove

of moisture. dioxide: May be removed commercial hydrotide. be used. by passing preparation Sofnolite, Sweeping the gas which through is a trap

5) containing asbestos mixture solution leas

Ascarite, impregnated of NaOH of alkali

a granular with
sodium

essentially a a

or soda-lime, the gas through

and CaO metal

may

also

hydroxide systems May

is also than

effective. solid

Solutions

are

sometimes

convenient 6)

in vacuum halides:

materials, in the same

however. manner as carbon

Hydrogen

be removed

diotide. 7) Oxides of N of nitrogen: O, NO and Dissolution NO Its 2 of targets in nitric . acid N20 will result occurs

in evolution in relatively reduction solution

2 small

in varying removal may to NO

proportions

usually

amounts.

be accomplished by scrubbing

by catalytic with N02 a may

with

hydrogen

or by oxidation agent such #tream

the gas NO and

of strong

oxidizing

as permanganate. through will flask. a solution in fact

be removed ide.

by sweeping the back

the gas

of sodium a good methods of nitric

hydroxportion of

Performing oxides available

solution into

under

reflux

wash

the higher tion are

the dissolver most

If alternate to avoid the use volatile, from

of soluacid, halogases in the

it is often Free

convenient are all

8) Halogens: gens are the gas may often

halogens in trace solution

relatively in targets leaves

and active which rare

be present If the state,

amounts process

to be removed. zero oxidation

them

partly

or entirely Sweeping

the gas of sodium species with their

stream hydroxide (halide

will

be contaminated. rapidly

through

a solution

will

halogens change

to non-volatile of the halogens

and hypohalite halides

convert all the free 10 The rapid ex). in solution is another

corresponding

useful

means

of decontamination by contact for this

from with

tracer

halogens

11, 12

Iodine have

is

quan been

titatively used

removed

silver

(silvered Iodine

Raschig is reduced

rings

as a trap

packing

purpose).

to iodide

in NaHS03

solution. Where pleted reaction rates it may are S1OW enough that purification the may not be comfrom most target

in one pass, through for

be necessary train.

to circulate The classic,

off gases

dissolution useful, with

a purification circulation

and still is the

device

(or transfer) per minute

of gases may

Toepler Other been only

generally 13 pump, circulat-

which

rates which

of about may

a liter

be obtained. have

ing pumps These flow

be useful

in particular

instances

designed. unidirectional within the

consist of gas

essentially

of a chamber of producing

designed periodic

to permit

and a means Alternate flow

pressure

changes

chamber. used

heating rates

and cooling of O. 5 liters

of the gas per hour.

to achieve

in the chamber has been 13 An iron piston enclosed rates of a few in the rates by high liters

in glass per

and electromagnetically operated has 14 Pressure differentials developed minute, probably small. Another by means achieves of a mylar

produced were.

not noted high flow

reference by pulsing pressure

but are

similarly diaphragm

gas.

the chamber 15

pressure

driven

Ultimately properties of interest.

the radiochemist gases.

must Table

concern

himself some

with data

the physical which may be

of the rare 16

1 summarizes

Table

He Atmospheric (Volume Boiling Melting %) Point Point ( C) ( C) abundance 5.25 x 10 -269 -272 (25 Atomic crystal diameter (angstroms) in 3.57 atm. -4

Ne 1.82 Xlo -246 -249 ) 3.20 -3

A~ 0.934

Kr 1.14 Xlo -4

Xe 8.7 Xlo -107 -112 -6

w 6 x 10-18

-186 -189

-153 -157

-65 -71

3.82

3.94

4.36

----

Distillation for separation

and adsorption of the rare gases.

techniques The pure

are rare

those gases

which have

first

come

to mind been with gases decay

of course

successfully the exceptions and radon

produced of helium is

commercially which

by the fractional from

distillation Texas

of air, natural

is extracted

certain

which

obtained

as a member

of the 4n+2

natural

radioactive

series. istry

Fractional

distillation

is discussed gases from

in most air

texts

on physical

chem -

and the fractionation 17-20 places . Glueckauf air and ads orption

of rare used

is discussed fractional

in numerou8 distillation of

a procedure

combining

tents need there

techniques in the determination of krypton and xenon con21 It is very ~likely that the radiochemist will have of the atmosphere. such low temperature fractionation here. and condensation gases processes or effecting pressures commonly is referfor data vapor of below Rn at low as will columns in the laboratory so

to use will

be no discussion hand,

of the method simple distillation

On the other be used rough in practically

every Thus

experiment ( for low

in transferring t~mperatures and other

separations.

a plot for

) of vapor species The and

a function encountered red

of temperature till prove

rare handy

gases

volatile

very

to the radio chemist. of Chemistry 781

reader 22

to the generally for data such for

available a plot. a number

Handbook Dushman23 of substances vapor

Physics ) also

necessary pressure decreasing the critical and C02,, temperatures

(page

et seq.

tabulates In order

at low temperatures. pressure at a given N2, vapor

volatility

(decreasing

temperature Kr, Xe,

temperature) and H20. which Gases are

the common listed

gases

are

A and 02, pres sure

in pairs

have

curves

very

similar. such as the transfer to the of a gaseous are species conby the

Efficiencies tained relation pressure ample, in a system

of processes to a cold partial or liquid trap

attached

system

determined

of the initial of its solid

pressure after

of the

species

in the system trap.

to the vapor As an ex-

condensation Kr at -195C

in the cold is 2-3 may

the vapor

pressure

of solid at 20 cm As

mm Hg,

so roughly in an attached conat krypton

99V0 of the Kr small cold

in a system at - 195C.

Hg pressure nitrogen

be collected

trap

liquid Kr

is generally

the coldest

veniently this

available

refrigerant, The resultant

is often

manipulated with

by condensation increasing systems may initial

temperature. and may of krypton that the y are

losses,

decrease

pressure amounts enough must

be minimized carrier

by using the --

smallest they

and the [argest small If one Hg from

practicable for the

usually

be made

acceptable krypton

sake

of speed

and convenience. to 2-3 mm

of necessity he must such as

collect resort

at pressures temperature pumps. lower

comparable refrigerants, Presence rates

a system, absorbents

to lower

refrigerated of small amounts sea

charcoal, may

or Toepler seriously

of noncondensible such eous pres as the above inter diffusion sure orders

gases krypton

the

of transfer slowness system pressures

proces

condensation, Thus lower

due to the relative one wishes than a vacuum vapor

of gas with a base

processes. of magnitude

the lowest Systems and will

involved of

in manipulations he may wish to perform. -6 10-5 to 10 mm Hg are easily constructed

with base suffice for

pressures

the, rnamipula-

IQ

tions than

involved tracer Removal

in most

rare are

gas

radiochemistry

(assuming

that

macro

rather

amounts of only

involved). volatile species its from vapor that a gas stream is is feasible sufficiently is are essen higher -

the least

when less tially than

a temperature than its partial

can be found pressure

at which

pressure

in the gas pressures

stream

condensation constituents equilibrium phase, separation the fraction

complete, their partial

while

the vapor over

of other

pressures of the other

the trap:

Ass uming

conditions of the simply.

and insolubility gqs stream

speciee trap

in the condensed the desired conditions, stream) pres

passage quite

through

the cold under the trap

effects

Lf condensation lost pres (passing sure

occurs through

equilibrium with to its the gas partial

of species of its vapor gases. and and to beads bails satby of To

i~ the ratio

at trap

temperature

sure flow

in the influent rates are

improve cold traps

the approach packed with

to equilibrium some material

conditions, to provide

limited area wool, steel very

a large materials. purpose. have

contact Glass Stainless also

prevent or rings (3/16

mechanical are

blow-through commonly with suitable has

of condensed used glass for this

materials

in. ) combined Such

wool

plugs

proved

isfactory. the induction condensed must under movable always

a packing

the ,advantage in it to achieve

that the rapid

steel

may

be warmed removal

of eddy

currente Time before

and efficient to be reached As cooling

materials. be allowed may such fashion often volatile

for

thermal initiating

equilibrium gas flow.

in traps packings re-

of trap

vacuum gas

be quite as helium several

slow,

temporary heat

introduction transfer

of some

easily

to improve condensed

is often

useful. volatil -

Ln like ities may

materials,

of widely

differing

be separated components the

by warming into another

to a suitable cold trap.

temperature It is often

and distilling necessary each to time com(e. g. ,

the more melt

and refreeze

condensate material

remaining evolved

behind

several cold

times,

removing plete

the volatile

to the other traces condensate should

trap,

to effect materials

removal

of occluded of C02 of trap 8C), dry

or dissolved C02 -ice

of the volatile at dry-ice

the distillation The nitrogen in most nitrogen and neon. evaporation mediate are ice subject (- 195.

from

temperature). Liquid available

refrigerants ice (-78.

be touched (OC) lower rare

on briefly. are commonly that other will

5-C),

and ice

laboratories. will usually

Fortunately not be required be noted triple point

temperatures in handling

than gases

of liquid than helium cool it by inter and or dry -

It might to its

that pumping (-2 10, 9*C, dry

on liquid 96.4 ice, mm and ice liquid

nitrogen Hg). are with

Temperatures often liquid necessary nitrogen Slush solid or

to those

of liquid

nitrogen,

commonly to obtain

obtained a partially provide

by cooling frozen heat

a suitable

Ilslushll transfer

at the melting from the trap

point. than

liquid

refrigerants

better

refrigerants,

xl

thus -78.

dry 5C.

ice

is usually

mixed

with acetone

to provide

a slush

refrigerant

at

Discussion are useful

techniques titularly

of cold bathe may be found in most texts where vacuum 24, 25 discussed. The author has found the following baths par in working - 160c. most will convenient flow with to refrigerate liquid nitrogen, on the line. for traps dry ice, through or ice which since large such at need with rare gases: acetone, -95 *C, n-pentane, -130 C,

and isopentane, It is usually quantities traps other take are of gas easily

replenished may

in place

Slush- cooledl operations where

traps they

temperatures up only small

usually

be reserved

amounts

of heat.

Adsorption By far ture have

and Adsorption the majority employed available, surface gases

Techniques of separations of rare gases to be found number been used in the litera -

adsorption activated area adsorb gas

techniques. charcoal (largest has

Of the large most often

of adsorbent because it and

materials has

the largest the rare a given

adsorptive

capacity)

per

unit mass extents.

because For per

on charcoal and adsorbent

to widely material

differing

adsorbate

the amount as Hg)

adsorbed

unit mass

of adsorbent,

called

v and usually

expressed mm

cc STP of gas per

(Standard gram

Temperature

and Press

ure, i. e. , OC and 76o

adsorbent,

is a function over

of temperature Three

of the ad~orbent functional showing relating P . the P

and partial among of v v; of

pres sure these on and P

of the gas are

the adsorbent.

relationships dependence T

variables at constant 3 ) Isobars

of interest:

1) Isotherms 2) Isosteres at constant usually

temperature; relating v and

and

at constant studies

Ln experimental at a series be obtained of adsorption

adsorption tures. The sure

the isotherms these data

are

most

determined may heats

of temperaif desired. and the pres -

From Clausius change

the other equation

relationships also relates

-Clapeyron with

temperature of equations

(shape have

of the isostere). used to express first adsorption derived isotherms, the hyperbolic 26 adThe , or to on is of low

A number most of which for

been

are

empirical

in nature. from later

Langmuir theoretical derived

isotherm Brunauer, sorption hfierbolic P/v form =

monolayer

Emmett, which reduce

adsorption 27 and Teller to Langmuir

considerations. for

equations in the case tbP) ,

multilayer

Is equation v

of a monolayer. P = vfi(vs required dependent The since last v)

isotherm l/bv s + P/vs

may ,

be written v~

= vsbP/(1 cc STP and

where gram

is the

of adsorbate b is a constant

a monolayer

per

of adsorbent, of the adsorbate

temperature particularly P/v versus

and the nature useful P for

and adsorbent.

form

the extension

of data by interpolation or perhaps more

the plot

is linear.

At low pressures,

definitively

12

v,

it is found plot or of

that adsorption P versus less

obeys

Henryfs

law

(v = kP), be noted isotherm equation

and interpolation that for P much

.on less

a linear than l/b,

v is possible. than

It will

v much

v~ , the hyperbolic parabolic

reduces

to Henryrs in where

s nature) is often useful for 1/n . it is obeyed: v = KP krytpon equation 2 for and from xenon their

law with

k equal

to bv

Freundlicha linear Peters

(semi-empirical plot in cases

interpolation 28 and Weil

on a log -log studied the

the adsorption

of argon,

on charcoal data

and calculated

constants These

in the Fr eundlich are given in Table are

at several Adsorption

temperatures. data 23 for The

handy

reference.

a number adsorption adsorption

of gases process

on charcoal releases with

tabulated and as creasing es with with order

in Chapter expected from

8 of Dushman. LeChatelier other

heat in-

IS principle remaining

decreases Ad~orption tends

temperature, increasing

factors

constant. gases

increas

pressure. volatility points 2.

Adsorption (extent

of different tends

to increase in the same

decreasing as

of adsorption

to increase

the boiling Table

of the gases). constants v = KP for argon, 1/n krypton

Adsorption

and xenon:

T C Argon -80 -18 0 -80 -18 0 -80 -18 0 ,

K 0.500 0.0764 0.0581 2.927 0.497 0.340 15.99 2.458 1.583

1/n

Krypton

Xenon

0.950 1.0 1.0 0.711 0.885 1,0 0.574 0.692 0.77

Theoretical a monolayer surfaces, is its

treatments

discuss

adsorption 2)

in terms formation pores. of the

of:

1) formation

of

of adsorbate and 3) capillary

on the

surface,

of multilayers Adsorption same type

on plane of a gas

condensation Waals

in small forces

considered condensation.

the result The

of van der magnitude

involved

in is

of the interactions of adsorption gas , are

resulting

in adsorption

indicated heat over therm) of the models a key

by the fact

that heats for a given

generally

comparable may

to the conform isovalues

of condensation wide for ranges Euitable thus

Experimental equations

isotherms (as

to theoretically values of the are

derived constants often For

the hyperbolic However, to the physical

in the equation. related

constants used

obtained

not easily

in the derivations.

discussion the book reader

of adsorption is referred

in general

and 7 and

to the literature on the subject 23 or to S. Brunausls 8 in Dushman

on physical

to Chapters 29 adsorption.

13

Some These ous ods heat than with are

comments mostly from from

on the nature two recent

of activated review articles. may

charcoal 30,31

may There

be worth are

while. -

ntimer

materials

of preparation, in the absence carbon steam of

which activated 32 For example, of air to remove .

charcoal

be prepared with

and many shells

methand

one might the greater The resulting specific gram) such is

start part

coconut

of the elements is then

other activated (of as specific

as volatile

materials The meters

material surface area

at 7OO-1OOOC. 1000 square

large per

of charcoal porosity, large

the order opposed surface per gram

due to its black

high

to the nonporous area is the result black

absorbents of extremely is a marked

ae lamp

whose

small function

particle

size.

Thus particle

the surface size, of

of lamp

of the average is almost area

whereas particle resides follows Thus therm, coal

the specific size. in pores that

surface

of activated most of the

charcoal surface

independent

Furthermore, with diameters expect

in charcoal

apparently It

comparable principally

to molecular

dimensions.

one might

monolayer

adsorption

on charcoal. isoof a charof pyrolysis. generally porous ) still

adsorption and does

on charcoal so over on both hardwoods, porosity. capacity material wide

might

be expected The

to obey

the hyperbolic structure

ranges.

potential

pore

is dependent from

the starting nutshells The material

material

and the conditions grades of coal (though consists

Charcoals give has

and certain after

the highest low adsorptive

pyrolysis of activation open

and the process in order which will .Steam

essentially or to enlarge

of burning existing (perhaps reaction pects depend

out more

to either

new pores adsorbate

pores both

to diameters processes

accommodate is widely

molecules as One the ex-

occur). and better

used control

for

activation

is endothermic, that

temperature

is possible.

then

the properties on materials pyrolysis area as jhe many

of the material ueed

he receives but also

in the laboratory very markedly on

not only of its

in preparation

the history remove through

and activation. than it creates,

Excessive

activation capacity

can in fact going of pores

more

surface

the adsorptive Since

a mafimum includes sieve!!

activation

proceeds.

the distribution to molecular extent. for for Thus

as to size

with

diameters

comparable to some too small

dimensions, some larger may been pores

a Bimolecular will

effect a given

may

be expected but are

accommodate During

molecule

a slightly various has

molecule. therefore referred percents other

activation

the adsorptive in the same ratio.

capacity

species

not be increasing to as an allotrope of carbon always are sulfur,

Charcoal

in the past indicate low as

of carbon, less thh

but elemental 100%

analyses as

atom The

and eometimes

757..

elemente

present

principally chlorine,

hydrogen

and oxygen, ash may

but appreciable also are be preeent. not carbon and

amounts It appears surfacee

of nitrogen, likely

and inorganic adsorption

that the

surfaces e urfacee

on which modified

occurs

but hydrocarbon

by the presence

of oxygen

lJ+

traces likely

of other

elements.

This

implies

that all

adsorption

sites

are

very

not identical. Activated charcoal may is thus vary impair a class of substances wide limits. whose Let chemical UH hasten The not and to add

physical that this tive that tion, intent sorptive literature.

properties does

within its

rather usefulness

not really of

as an adsorbent. systems will are usually

adsorpso critical

properties even

charcoals like

in separation

variations such

factors

of two or more affect

result

in loss in detail,

of separaThe if the adin the at room

though

variations

certainly

the prQcedure should

is to point properties

out that the experimenter of his study charcoal differ

not be surprised he sees quoted

from

those

In one

of the adsorption per gram

of xenon

on seven

charcoals

temperature, varied as much

the amount as a factor

of five.

of charcoal adsorbed at a given pressure 33 These charcoals were of course chosen and preparations . Ln order that early expected to produce may be

on the ba,sis a range used

of differences

in materials

of adsorption with

characteristics fair accuracy wise

experience in systems a quantity

to predict dates,

the course to originally

of separations purchase

built

at later coal

it is probably for use many years

of char -

sufficient Before

needs. successive uses it is necessary with small materials to outgas char-

and between

coal, gases whose

both from

to prevent pretious

contamination runs may

of samples

amounts (such

of residual as water) of the

and to remove adversely should affect

adsorbed

accumulation This further in vacuo is

the adsorptive as

properties to change

charcoal. through gassing gassing judged

process activation.

not be so extreme which has

the material is outthe outless as

A routine

proved -4

satisfactory Laboratory mm Hg or

at 350-400C. continued

At Lawrence until the pressure gauge ways

Radiation is 10

routinely

by a thermocouple One may operate

vacuum in various

in the vacuum to achieve (or any are

system

manifold. of gases through

separations other

differences prove arations chemists analogies useful

in the adsorption to point out that in solution familiar

on charcoal such

adsorbent). similar The resins many will

It may to sepradioclose

separations ion

basically resins, such

of species who even are

using

exchange using used.

with

separations

note

in the various procedures from that

techniques must

Separation mind was -adsorption earlier size,

be designed of gas

with

kinetic

considerations process.

in It

a stream

is not an instantaneous of charcoals of adsorption increases phase does will the

stated

the adsorptive expected

capacity that rates

not depend be so dependexterior paths in

on particle ent.

but it is

A reduction (per gram

in the average adsorbent), along cites

particle presented which

diameter to the gas

surface through order

and shortens must diffuse

cracks to reach

and pores adsorption

adsorbate

molecules interior.

in the particle

Approach

to equi -

15

librium creased

conditions contact

should time with small low

thus

improve

with

smaller

particle flow in high beds rate),

size

and in-

the adsorbent particle size

(decreased will result

A compromise to gas

is necessary flow, In flow

as too systems

resistance

temperature

adsorbent

may enters

not be maintained the bed at ele processes trans -

in thermal vated

equilibrium

with

the refrigerant of heat

if the gas from affecting it is

temperature is hi,gh. thus

or if the rate Flow rates

release

the adsorption the rate certainly the kinetics

occurring fer est are and

and conditions respect.

of heat of great

important

in this

Although

inter -

long-range the more

usefulness practical

to understand and faster

in detail approach

of these empirical. and the kinetics which the

processes, Design

to design insofar factors

is

factors

are chosen

to improve

the kinetics succeeds,

as possible affecting under

experiment are usually

is tried. not varied is

Lf the experiment to determine Thus

the extreme in places sizes such

conditions

procedure where stood flow that

satisfactory.

as the Detailed be quoted but may

Procedures be under-

rates these should rare

and charcoal are sufficient

particle for

may

it should or may

the separation, make

not be

necessary Most the gases problems variations, adsorbent in this steps will

other gas

considerations will

changes with this

desirable. total adsorption one may of all minimize

separations

commence trap. k

of interest arising

in an adsorbent non-uniform kinetics

manner

from

introduction by using lower

of sample,

temperature and more steps

and adsorption than should really

temperatures all

be necessary.

By treating

adsorption

manner slow

one tends may

to reduce affect

10S ses , since of the

in subsequent separation

deaorption in detail but

processes

the history

not result In their

in actual early work could

loss

of sample. gases, Peters and Weil 28 showed that argon,

on rare be

krypton resorption

and xenon

separated activated

by total charcoal.

adsorption They gas

followed

by fractional the mixture on 38 grams

in vacuum at - 190 C

from

adsorbed was used

on charcoal of charcoal) the gases fer may speed them

(roughly

10CC STP

of each

and then using

raised

the trap diffusion

to a suitable pump backed

temperature by a ToepleT

and desorbed p~p to trans each gas -

a mercury buret IIpure!i for

to a gas

measurement. are

Temperatures somewhat

at which

be desorbed

of the others -removal

a compromise krypton

between at -800c amomts the could

and separation

factor

of argon

at -93 c,

and xenon of adsorbent adsorbent calculate gas

at OC would and of each bed

be typical. adsorbate before

From initially, each

knowledge

of the isotherms, with pump which one

and the volume lift of the Toepler

is equilibrated

in a straightforward and gaseous onthe

but laborious phases adsorbent. after

fashion each Even

the composition stroke, assuming examination

of the uniform of the

in the adsorbed

distribution

of the gases

cursory

16

isotherms duce gases

suggests which obtainable be noted in which

that while are around

separations 99% pure,

performed separation

in this factors

manner of about

may

pro-

100 are

the limit It might a system series neon lar

not be satisfactory in most 34 analyzed mathematically that Glueckauf rare traps gases are successively such a system adeorbed for

and would

radio chemistry. the operation and desorbed helium of

on a and

of charcoal as the final

and used

separating

step later

system

was

in the determination of their abundance in air. A simi35 used for the Heparation of argon, krypton and xenon the relative yields of krypton and xenon gases isotopes and

in an experiment from later traps uranium mass waa

to determine fission by volume

measurements In these

on the separated procedures 28 a series

spectrographic required.

analysis.

of many

A sidelight point shown they out a matter 222 that Rn out,

in the work of safety. adsorbed gel

of Peters They

and Weil

. 1s worth

mentioning in which silica

to it was

performed from

an experiment liquid air ont~

quantitatively was used because

gel.

As of to use

point

silica

of the explosive hazard it seems

potentialities advisable charcoal

charcoal liquid traps when

and liquid

oxygen. than in case

Because liquid air

of this

nitrogen,

rather

or oxygen,

to refrigerate

as a safeguard introducing of liquid techniques been air air

of breakage, trap itself.

and to operate cooled in liquid

at reduced nitrogen

pressure con-

to a charcoal in the trap of Peters

to avoid

densation The have today

and Weil may

and of

Glueckauf termed

mentioned

above

replaced usually

by what involve

be generally

chromatographic on one gas later end of an the

techniques. adsorbent column

These column,

adsorption passage

of a sample of some eluent in his

and subsequent separation. contents

through

to achieve and Xe

In fact,

Glueckauf21 separated

determination gases by elu -

of the Kr tion from

of the atmosphere rather

the rare used book

a charcoal already to the

column

than by the method Keulemans recent

determination an introduction source some tionary gas

mentioned. subject of gas

in the He and Ne 36 will serve as

chromatography a few remarks

and as an up-to-date will be made here and

of literature journal bed

references. cited. solid

Only

references of liquid Rare or

Chromatographic through

separations which involve a stream a stream

involve

a sta: or moving

adsorbent

of liquid of gas

moves.

gas

separations of solid

on charcoal and thus would

through

a packed

column Methods

be classified

as

gas -solid will genera and

chromatography. ally fall into

of operating categories: separated carrier

chromatographic 1 ) Elution

columns

one of three to be

development at one set

in which

sample a flow 2)

of the gases of slightly analysis

is adsorbed gas (eluent) of gas

end of the column the column.

adsorbed

up through the

Frontal

in which a stream

containing

sample

mixture

17

is

continuously the flow sample

passed

through

the column.

3)

Displacement column

development

in

which uous

mixture of gae

is adsorbed more strongly results

at one end of the adsorbed than

and a continin the the with

initiated Elution

any of the gaees emergence (diluted from

sample. column eluent) enough each cent

development or lpeaksi of their

in the eventual components

of bands

of the sample increasing it is possible

of course

in the order in their

adsorption. under proper

If the components conditions eluent

differ

adsorption in pure

to obtain from adjagas in

component peaks.

form

as a peak consists gases,

separated

by pure

If the stream

of gas

of an unadeorbed frontal analysis adsorbed which

carrier first

addition emergence diluted sorbed ed with position. pure

to the mixture of pure carrier. breaks

of sample

results sample

in the

carrier

and then

of the least

component, least ad-

with also all

Eventually through, and

the component so on until

is next

to the

the column

is completely have may the

saturatsame com-

components Only a sample

and the influent of the least

and effluent adsorbed

gaBes

component

be obtained bands of in the pure

of other

sample

components. by zones in order Partial

In displacement containing

development,

the components adjacent displacer bands

separated emerge .

a mixture adsorption. pure

of the species Eventually

of increasing of fairly

emerges

recovery

components

is possible. separations Ilidealll

Theoretical vary

predictions isotherm reversible) were

as to the details is linear or

of chromatographic

as the adsorption

or nonlinear, Linear 37

and the process -ideal

(thermodynamically ideal chromatography

Inon-idealll. by Wilson treated

treated has been

and by de Vault.

non-ideal

chromatography non-ideal

by a number

and nonlinear 38 Linear of investigatorfl , 39-46 47 ~ be

and nonlinear very large

chromatography are involved,

by Klinkenberg adsorption is also likely often

and Sjenitzer, will

amounts Gas -solid

of gas

isotherms

usually as the

nonlinear. attainment stantaneous cerned sible linear insight on page given

chromatography between things. with

to be non-ideal cannot

of equilibrium , among other

the phases Thus

be considered may well

in-

the radiochemist non-ideal theory

be conaccescase of

in his

separations theoretical

the nonlinear The

case, of the provides

the least simplest useful 36 treats

to accurate -ideal into

treatment. for a single

chromatography the processes of his

adsorbate

qualitative this case

occurring, book.

however. account

Keulemans

112 et seq.

A brief

of the reasoning

w-ill be

here. Consider an adsorbent uniformly packed into a cylindrical column of

constant is present ~ection, phase

diameter in some it will

and at conmtant small cylindrical itself

temperature element

throughout. of the column

If an ads orbate taken in cross -

distribute ( 1 -~)

so that a fraction As

o of the total a fraction

is in the gas o of the adsorbate

and a fraction

on the adsorbent,

3.8

is in the gas with the gas

phase, phase

a given

adsorbate

molecule

resides It then is just

in and thus follows that

moves the rate flow ~ the

o of the time through

on the average, the element the perfect available e . Pa per

of movement rate and F F ,

of adsorbate gas . Ge

o times one

the linear calculate and Ae

of eluent Let

Assuming

gas

laws,

may gas

us call

the volume

to the moving ie the partial

weight and

of adsorbent

in the element adsorbed in

pres

sure The

of adeorbate factor for

v the amount gae may in the . As

cc STP

gram

of adsorbent. temperature mm Hg). Ge of The

converting conditions adsorbate CPa Ge)-l the A same

volumes be called gas

in cc-mm C

of Hg at column K X 76o

to standard fraction of

= 273K/(T. will then be

phase

o = C Pa Ge/(GPa packed the ratio

+ vAe) Ae/Ge

= (1 +vAe/ will be weight

.

the column

is uniformly volume G

in any element to total for

of column void all space

and equal

to the ratio Furthermore, in which case, in the ~ .

of total
V/Pa

of adsorbent

in the column, is linear,

k will

be constant

v if the isotherm law constant.

case

k may, -1

be referred

to as the Henryle at constant

In thie

(1 + kA/CG)

and is the same of adsorbate q L/C length GPtot,

temperature The linear flow cc

everywhere flow rate

column will L be

regardlese F = column is total rate of

concentration. where

of eluent per minute, void

q is the gas G Hg, is the and C

in cc STP

is the Ptot The

in centimeters, in mm of adsorbate In most to

of total

column

space, above.

gas pressure movement (C G -1- U). sion simplifies is

is the constant OF . ( 1 + kA/C 0<< Ptot. 1, or (kA/C

defined G)-

is then instances

1 (q L/C

G Ptot) so that

= q L/Ptot expres-

G) >> 1, the

this

OF = q L/kA

In either along

case

rate

of adsorbate of the concenpoints travel in a along

movement tration band the

constant

everywhere It follows

the column rate

regardless of all its

of adsorbate. is the same,

that the shape

of movement

and the band

does

not change

during

column. In ideal chromatography, of adsorbate frontal at cons&nt analysis results in the gradual the column, extenassum-

sion

of a band

concentration partial total plus

down

ing constant in the gas column of length where this

column entering

temperature the column. present column, of flow

and constant By equating phase at , la

pressure

of adsorbate introduced phase to tbe

ads orbate adsorbent

to the amount fa on the

in the gas one arrives

in a band t ,

= (q L/Pto~(CG case . of a linear

+ vA/Pa)-l isotherm is

t is total la

time = OFt , is

in minutes

In the expects

is just

as one intuitively conetant everywhere

Even

if the isotherm for Pa constant.

nonlinear, formula stant

(v/Pa) is thus gas

in the band, in this case if

This

a useful entering All

approximation the column, discussion of a second

in the

and the isotherm is strictly for may

is known and cona is known at column adsorbate, the adsorption as .

temperature. appreciable of the first.

the above

a single affect

concentrations

adsorbate

19

In many ner

experiments, to frontal development. Kr and After

the

sample

introduction with subsequent

is accomplished separation 1 (see last

in a manof the com in

corresponding by elution air containing

analysis, De@i Xe

ponents which period and Xe

Led Procedure

chapter) over

is admitted

to a charcoal of the sample into

column

a long the Kr with

is an example. are separated

the admission

is complete, receptacle

and recovered temperatures. is that

by elution

a suitable.

helium for

at suitable

column operation

In such

cases

a minimal of least column

requirement subThus the

satisfactory be less

the length

of the band than

adsorbed length.. than

stance

at the end of sample 1, the final In the are length

introduction

the

in Procedure column for two length.

of the band

of krypton elution of

must

be less

subsequent OIF and

separationby 02F,

the rates emergence

of movement can be

adsorbates For the front

so that times the rear where

calculated. overtake gence band

separation

to be achieved band,

of the first T

band for fz

must emeris the

of the second of the first highly length -ideal

Thus

is the time where

of the rear width

band,

T OIF = T 02F component. separation

+ 12 = L, Thus

of the more column

adsorbed in which case. with as

L = 12k2~kZ

kl) may be

is the minimum achieved, If, then of the es. v/P

of two components

in the linear as is usually

the case Thus, with

charcoal,

the isotherm toward vs

is hyperbolic, (that is, 25), the fraction v/Pa decreascon-

=b(vs v). a surface covered be seen regions that

v increases becomes as

adsorbate

appreciable v increases, ideal

It will

o thus

increase~ faster. sharp of

and the more conditions tail.

centrated suit tical region emerge

in a band band

move

Assuming front

the re -

is an emergent sense,

with

a very

and a long from time,

In a praclow pressure front tail will where will

if one has

used

a value

k obtained

the linear the peak of the peak rate

of the isotherm earlier than lie that

to estimate calculated. linear

the emergence In the latter

portions

concentrations approximate

in the

region

of the isotherm,

of movement

calculated. from ideality in the gas 1! such as those due to appreciable mass travel, can transfer usually give cases. emerging might rates of

Departures longitudinal phases result

diffusion

or non-instantaneous during of these motion their

between

in broadening fashion.

of bands

in a nearly qualitanonthan -

symmetrical tive pictures

Superposition and their lead As

effects

useful

of the bands conditions

in the various bands one

Thus earlier

linear, under gence then tail

non-ideal linear first -ideal

to asymmetric to peak shape,

conditions. in which front,

expect

the emer slowly, a long

of a region main peak

adsorbate steep

concentration main peak

increases back,

a eteep in which There

a less

and finally

adsorbate are

concentration approaches

s lowly

approaches rigorous

zero. theoretical treat-

two general

to more

ment

of chromatography.

20

The alent species The

Iplate

theory platesti

treats in each

the column of which of their

as

a series

of juxtaposed factor between

equivtwo

theoretical

a separation distribution

corresponding

to the ratio

coefficients

is achieved. for

distribution

coefficient

is a ratio

of concentrations

in the two phases

a substance. The convection them. their The rate theory takes and into sets account up partial the physical differential processes equations such as

and diffusion, solution

to desaribe and

of these with time

equations and axial

(in the ads orbate distance along the

concentrations column

derivatives, is then

as independent

variables) Both references might effects highly be

essayed. involve given noted various simplifying accounts ass umptions, The journal It the

approaches to theory

earlier

include

specifically

that one article

of both treatments. 48 deals with by Glueckauf

of heating radioactive One

on movement gas might such say

and shapes of peaks when the adsorb ate is a 85 are sharpened and separations as Kr . Peaks that as the latter portions gas, with of the band there.

improved. move The

qualitatively by passage faster has

through tail would

regions thus

warmed

of the active and catch up

o is larger the after main

tend

to move

peak. to

In the high xenon Mev

event

that

the radiochemist it. might found

need

to use

charcoal

exposure and with

radiation

fields, was

be noted

that the adsorption by previous 49 gram). of the

of krypton irradiation

on charcoal electrons The

to be unaffected watt-hr per

1-

(doses

up to 1350 predicts

rate

theory

the nature

dependence plateli

of column

effifac-

ciency tors

(i. e. , the fheight such as eluent flow of the

of an equivalent rate, eluent adsorbent gas, etc.

theoretical, particle Although size,

) on various

COIUmn inlet development

and outlet of the

pressure, theory

nature becomes

the

mathematically relatively

fairly simple. will

complicated, The

application

of the results to make inter -

to practice much e sting use

is often of gas

radiochemist find study

who plans

chromatography

certainly

of the theory

and profitable. However, one actually to separate needs rare ,only a bare The acquaintance with the theory are written and For prove to

build for

a system

gases. a problem

following

paragraphs rare gas

the

radiochemist to solve

who meets it with

involving

separations,

who wishes this purpose The

a minimum given earlier

expenditure for

of time -ideal

and effort. case may

the equations assumption reality

the linear

useful. departure overly actually keep

of linear-ideal in most cases,

conditions

is of course

a cormiderable earlier one also values is

from

and the treatment for these

recorded

simplified determines

in some

respects

even

conditions. charcoal, or more

Unless he must from

the adsorptive may vary

properties by factors

of his of two

in mind

that these

quoted

21

in the literature. erature for Kr

The and (such Xe as

author

is in fact

unaware lees

of adsorption -80C.

data

in the litat lower ex-

at temperatures - 195C) must thus

than

Isotherms by rather

temperatures trapolations. The adsorbent written

be estimated

dubious

distribution phase

of rare

gases systems all

will

generally rate

be heavily of band may

in favor

of the may be withfor

in separation Not efficiency. of gas

so that

movement

OF

q L@~t. column rate might

of these Thus

quantities theory

be varied an optimum flow rates

at will value

out impairing the of linear flow

predicts Linear this

through

the column, typical,

of the order is not par -

10 cm/sec

be considered be varied drops with

though

parameter

titularly effect. increased impaired around diameter, fully used

critical Column linear at very 1 cm

and may efficiency flow large than

by factors rapidly

of two or three near the optimum

without value

serious with

less

decreased diameters. efficiency

linear

flow.

Efficiency are

is also generally of

column Again,

Column

diameters varying have

or less,

is not a rapidly diameter in last O, 5

q

function

and columns (e. g. ,, Detailed

of several Procedure lies

centimeters 1, in the given range per

been A*

successthe bulk it follows found 10. his In system. in

chapter). O, 2 gm/cm3, of charcoal, a factor of

density that

of charcoal values

generally of L/A, columns

extreme

column will

length

gram about one has pressure

various addition, Columns above

satisfactory L/A are

differ varied with

by only once

is not conveniently most often operated

constructed of eluent and with to 760 mm

an inlet

sufficiently atmospheric Hg. One

atmospheric

pressure Thus rate

to sustain ~tis

the desired always

flow, close

pressure wishes along

at the outlet. the linear flow of the

nearly

of eluent

to be as nearly desirable As

constant

as possible of inlet

the

length pressure inlet

column,

and it is thus unity is as possible. required it follows Band wide r~tio

that the ratio a certain

to outlet between a given are most ature,

be as near

difference flow in

out outlet roughly in this

pressure speaking,

to maintain that higher for

the desired operating

column,

pressures are

preferable conveniently

respect. over the

velocities

a given the

adsorbate column

varied

ranges v/Pa

by adjusting which

temper-

i. e. , by changing

= k

in the case rapidly several for Kr per

of a linear with orders at 1 mm are Thus for decreasof Hg

isotherm

is a constant.

Adsorption velocities temperature

generally will

increasee vary . Thus

ing temperature, magnitude partial about over

and band accessible over

often

ranges of

pressure O. 1 at 25C,

charcoal,

the values and

v in cc STP guess)

gram

3 at -80C

100 ( a rough one may ate

at -195C. find some

a typical at which suitable

chromatographic the band retention velocity time.

column

generally of interest

temperature a

of an adsorb

is such

as to give

22

In addition achieve improve initial

to adjusting sample

band

velocity, Increases

one

may

adjust

column will

length usually times are

to

retention. of several

in column also, band since

length

,9eparatione to L, 1/2 L . examples

components length, while

retention

proportional roughly as A few timating below. tory

the column

broadening

increases

of prior

calculations

which

one might

perform are

in es given -

the performance If &e calculations

of a proposed indicate

chrornatographic

column

that the proposed column parameters directions

operation and/or before with

is unsatisfac operating conof the margin of width

or borderline, may

then various

ditions system. safety, small In the

be adjusted

in the indicated appears regards

construction a suitable in a band

If the operation particularly with latter respect caee, as

to be satisfactory initial retention the system which trial may runs. given

of

of sample. might

to column further

length,

be tried

as proposed. can probably

changes few

prove

necessary

be made The

on the basis length 1,

of a very

of an adsorbate and for

band

was

earlier

as

la

= (q L t/Ptot) this may this be re form inIf v

(C G + vA/Pa)written

the usual as is

case la

where

G G << vA/Pa

to a close

approximation length

= (q Pa t/Ptot)(vA/L)the total per cc STP

1.

it is obvious troduced the partial may

that the band by the

eimply

of adsorbate length.

divided

cc STP

on the adsorbent is constant is known

unit column sample

pressure

of adsorbate if the isotherm required Assume C, for that and that Hg. The

during

introduction,

be determined quantities

at column of band in air sure of

temperature. length are

Values experimento a chargas

of other tally coal is

the calculation 100 cc STP the partial column of at

accessible. column

of Kr pres

is introduced Kr

at -195

in the influent of charcoal per

constant

at O. 02 mm length. of charcoal,

contains Kr under = The

5 grams

centimeter per gram

If the adsorption one arriveq

lKr

2 cm

at the end of sample as the adsorption The foregoing 1,

introduction. isotherm corresponds

these conditions is 10 cc STP 100 cc STP Kr gin/cm] = (10 cc STP Kr/gm)(5 an value of v used above is strictly known at this in of col tem-

estimate perature. Detailed radioactive umn

is not experimentally t~ a typical using a f3-y sample survey are

introduction meter

Procedure Kr, used

however, of a very

and few

on bands The actual

widths

centimeters 1 is about uncertainties

noted.

length

in Detailed thus being

Procedure allowed for

25 cm,

a considei-able calculations of Kr and in con

margin variations the gas tains gae

of safety from entering

in the

run to run in such factors the column. of Xe. Let us assume same

as the partial

pressure sample

that the above

also

100 cc STP partial

Under of for

the

conditions

of temperature rare gases Thus are it is

and rare typically safe to say

pressure, of

values

v for

neighboring

about

a factor

10 greater

the heavier

of the two.

23

that

Xe

till this, will vS,

be initially no statement be attempted. the cc STP per gram

retained

in a band

narrower disposition v being

than the band of Kr and here

of Xe are

Kr. on the comparof are

Beyond column able to

as to the actual The required values of

discussed which

to form The

a monolayer, portions

is of the order involved is the fact rare gas

100 cc STP unknown,

of charcoal. ly nonlinear.

of the isotherms complication

but definite

A more

serious

that at these will certainly

concentrations be affected of large retained

on the adsorbent by the presence

the adsorption

of each

of the other,

and by the adsorption

on the column Having their ties, most band

quantities the Kr and

of air. Xe in suit~bly may small portions As of the column, -

separation and thus conditions, Wiling. to Xe

by elution the band

development differ

be attempted. an order obtained, the purity

the adsorptive under for

velocities,

by about are easily

of magnitude even of the allowing Kr

sufficient However may

separations , because

of this

tailing

with of the

respect Xe for with most

be expected The

to be better purity of both

in general fractions given

than the purity will usually for 2

respect purposes.

to Kr.

be sufficient column to the con-

Although separation, less use

the equation L = 12 k2/(k2

earlier

minimum refers

length more

to achieve and

k~) where may

1!111 to the it is of little

adsorbed with rare

component, gases 2,

be useful

in other

nections, discussion. be less duction. umn only

in the mode the calculated gas

of operation minimum

under length will

If k2/kl the band is,

is greater width

than

than

of the less

adsorbed case,

at end of sample could be eluted leaving

intro off a colpure xenon. be take

That a few all

in the

linear-ideal longer than

krypton width

percent

the band

of xenon, have left

However, fore

but a few

percent

of the krypton Elution

would

the column would

the end of sample long

introduction. time at - 195C,

of Kr from the

a column column

an unnecessarily in order mated example to bring retention below.

so one raises minutes.

temperature of estisecond

the Kr time

off in a few

A sample

calculation in the

during

the e lution

development

appears

Adams, moving retaining release system Kr and

Browning, Xe until fission

and Ackley products

50

recently

reported

on a system reactor off-gases

for

reand

from

homogeneous have decayed necessary before given

them

radioactive

species

sufficiently in this trial.

to permit case that the

to the atmosphere. be designed used

It was

of course as possible

as accurately in designing

Some

discussion

of the theory ence ideal

the system

is

to a more

detailed

treatment

of the theory

in the article and a refer51 is noted. While the linear use in design in this case,

it

approximation provides

would

not be satisfactory illustration experiment.

for of the Fission

nevertheless .of the rough

a useful with

calculations gases

and a comparison in a stream

predictions

contained

24

of oxygen and 25 C) Each Bisted The

flowing were

at a rate passed

of 2 liters

per

minute series

(at

1 atmosphere

pres sure charcoal. and coni. d. pipe. and the equal of are

through contained pipe,

two parallel a total 40 ft of of 520 l-in.

of pipes

containing charcoal

series

of pipes

lb of activated pipe, internal bulk

of 40 ft of O. 5-in. was at 25C.

and 60 ft of 6-in. volume density L/A

charcoal

From

the total

of the pipes of the charcoal in each

weight

of charcoal

one arrives Aaauming

at an average uniform -section packing in cm2).

to O. 69 gm/cm3. pipe thus In the 1. 50/k in the coal is l/(bulk

the ratio Values

section

density O. 5-in. pipe OF

)(cross pipe,

of L/A

in cm/gm

1. 14 for O. 5-in.

O, 285

for

= qL/lAPtot OF is

in cm/min. 6 -in. pipe. column, resides As

Similarly there

l-in. pipe, and O. 00792 for 6-in. pipe. 1000 cm3/min. X 1. 14 cm/gm . = Xk 60 = O. 375/k in the ~%.~ipe and O. 0104/k 1 cm3 that of void a few space percent per gram of char-

roughly

in the

one may

calculate phase. time

only

of the adsorbate formula the length above for

in the column OF is thus d~8i~:d

in the gas Retention Total

Use

of the simpler section equals TR The O. 08 for pressure). for This of Henrys nature

justified.

in each

of pipe ~ values of +

by band k =

velocity.

retention ) = 1.3 mm for

time

is thus

0.0104 ) of k given adsorbate retention tention tains

1.80

X 105 X k(min. are about per

125 X k (days). for Xe and

= ~ + ( experimental Kr

in the article per times gram are were

(in cc STP The

charcoal thus

Hg adsorbate Kr and

calculated reconwith

10 days

163 days

Xe.

Observed also constant partial

times

10 days

and 60 days data

respectively.

article law

interesting

experimental moisture content

on variations

temperature, pressure

of the adsorbent,

of carrier,

of krypton,

Koch on charcoal posited 1 -cm 1.6 gent times

and Grandy using

and the adsorbent used. 52 recently reported studies of 85 and Xe133. The tracer tracer Kr of charcoal and eluted helium of 25C,

Kr

and

Xe

separations were deof about

rare off using eluent O-C

gases

at one diameter

end of a column and lengths

columns

of 5,

16 or 43 cm,
temperatures

flow and

of O. 6 or Emerand

liters/rein. peaks for were

, and operating observed

-80C. stream,

by measuring peak maximum were

radioactivity and

in the exit actitity

breakthrough, Satisfactory

1~0 of peak in all

in the tail , To of cal1.6 we density volmm Hgxk . cm/min and the max .

recorded. culate

separations approximations 43-cm. = lA~t/q. charcoal is

obtained retention

the trials

the linear-ideal helium TR flow,

for

times column

in the case temperature, (bulk)

liter/rein. may write

column,

and 25C

= L/oF

In the article estimated

the effective 1 gm/cm3. Tfor time

K

of the 40 to 50 mesh ume 20.4k from Xe ima is estimated (in rein, the last retention were ).

at about Thus 1.3

aeometricallv . Using k as

to be 43 cm3. for Kr Kr times and

column 43 gmX760 1600 1.6 min.

0.08

Xe is

example, time

the calculated Observed , respectively.

retention for

26 min. 20 min.

emergence

of the peak

2. 1 and

25

The by means Keulemans technique changes For

emergence

of various

components change

from

a column

may

be detected gas. used detects it. 53, 54

of the corresponding discusses involves various a thermal

in some

property The

of the effluent moBt widely which

methods conductivity

of detection, cell

(katharometer)

in the thermal gases

conductivity another chamber

y of the effluent is to paea a counter leave

gae es pas sing the gas of some

through

radioactive

method or near

through activities

an ionization

leaving the column 55 sort to detect the

of the various

components

as they

the column. impurities argon, other oxygen from than rare

Ln separations gases adsorb will interfere

by charcoal in certain different

chromatography cases. the Thus while

and nitrogen large krypton amounts and

to slightly

extents,

separation

of argon

of oxygen xenon are

and nitrogen of interest Methane

is best

accomplished

chemically. to remove air from

If only before krypton must

it is not necessary is very difficult thus

the chromatographic by adsorption be separ -

separation. on charcoal ated from remove water, from rare

to separate

or by distillation, from before krypton. its

light

hydrocarbons materials

usually

chemically the gas

Certain

should since they

always are

be removed difficult to

introduction

to charcoal

from charcoal and their accumulation tends 50 oxides of nitrogen, HCl). Most impurities the mixture of rare after gasee their before elution. their This

to poison may either

it (e. g. , be removed the separated

adsorption choice may

or from be made

gas

fractions

as a matter

of convenience Though the only Silica those been which gel

in the particular charcoal one.

experiment. generally is a very useful general same adsorbent property order of radon class it is by no means of surfaces. of magnitude has already as

is the most Adsorption areas less (its

possible has

specific

than but of the

of activated mentioned).

charcoal 28 There

use

in the adsorption one other

ie in particular

of adeorbents

should be mentioned. These are the so-called Bimolecular sieve ma56, 57 terials, now commercially available from Linde Air Products Company, Tonawanda, New York. Actually these are extent Si02, zeolites and as such their adsorp23 Thus, the 5A is a sodium

tion Linde

properties Molecular

are

discussed is CaO.

to some A1203.

by Dushman. and the 4A is that

Sieve

Sieve

alumino-silicate. water Thue of hydration a highly

Their

peculiar

property with

removal

of the original lattice structure.

(activation) medium size.

occurs results The

little

change the pores

in the are have

porous

in which 4A and

of remarkably pores areas of rotighly as great of adof

uniform

(and molecular)

5A materials Specific been

4 and 5 angstroms as those sorption of many for

diameter, activated gas

respectively. charcoals have

surface

reported. on the degree at nearly are

The

extent

a given

is strongly goes

dependent

of dehydration complete

the adsorbent tion. Because

and in fact the pores

through

a maximum occurs

dehydradimen ,

in which

adsorption

of molecular

26

sions,

the

size

of the adsorbate the ad~orptions from may

molecule of two

strongly species

influences may be quite

the extent different

of rela impoe which -

adsorption. tive sible will ane.

Thus

to one another on charcoal illustrate

the adsorptions

on charcoal,

and separations

the point.

be feasible. A recent article gives an example 58 The mixture studied was nitrogen-krypton (20 C), later the nitrogen came off first Molecular

-meth-

On a charcoal

column

and the krypton Sieve (27, followed of all sievell were

and methane water

considerably at 20 C,

but together.

On 5A

by weight) later could

the nitrogen

and krypton then

came

off together,

considerably three gases

by the methane. be achieved further

It was

found

that the separation of Bimolecular of the peaks

by using found

a mixed

adsorbent

and charcoal. quite ent. close in

It was to those

that the

relative

positions percents of the peak sieves from

calculated to obtain The

by using a weighted

the weight average molecular

of the two adsorbpositions or mixed samples using absorb-

the mixture adsorbent. be useful

the pure ents

possibility separation

that

could

in the author

of rare of any

gases such

is worth procedures

keeping in the

in mind. literature

The

is unaware

radiochernical

to date.

IV. The of target has clear must which ods

SAMPLE radiochemist

SOLUTION may though method have most

AND need usually for

EXCHANGE to recover from bringing Since

WITH rare

C-RLERS from a variety fission a gases

gases

materials, #my may

heavy

elements

in which

occurred. solution

suitable

the target the recovery

material

into

be used

in principle. products gaseous

of, the rare

be effected produce

from

the volatile tractable for

of solution, products are

solution

procedures Methand re -

the more

to be desired.

reported

in the literature gases

covery problems

of the rare likely targets initial

the solution of spent fuel elements 55 certainly exemplify the most therefrom as regards volatile usually gases done products of dissolution.

extreme With of

to be met that the containment of metal

the small complete

radiochemist of the is

encounters will often

the feasibility simplify If the are

evolved usually

matters. is to

Solution available handle

targets from nitric

with

acid. acid easily

choice simpler

the products than those with

solution acid.

with hydrochloric Thus uranium added is

dissolved

in consimPIY 9270 gaseous prodcatch-

centrated removed H3P04 product. ucts

HC1 with in a trap has also

a few

drops

of 30%

H202

and the HC1 fumes

containing found

caustic. satisfactory nicely

been

Solution of uranium in warm 59 and hydrogen is the only in 6N NaOH, may again with for

Aluminum

dis solves This method

no gaseous aluminum clad

by hydrogen. or as

of solution

be useful targets

er foils large

a preliminary of aluminum.

to the solution

of small

in relatively

amounts

27

Solution the rare The their gases

must are

be carried removed

out in a closed the effluent work may

system gas

or a system prior

in which

from

stream

to venting. of carriers and

former

is preferable with

in quantitative rare gases

as introduction be effected phase.

exchange

the active are

before With

any chemical the rare gases

or adsorption one has problem and active change nate

operations with

performed

on the gas between

no problems is simply gases gas .

rates

of exchange complete

chemical miting slow, mixing must

states.

The

one of achieving As phase diffusion

physical relatively

of the carrier thorough (as ex-

processes insured

are

in the

is usually of parts

by convective One

by alterthe

cooling

and heating

of the system). active gases from

also

consider

complete least gases has the

removal complete

of the tracer exchange

the target carrier. gases law

solution, Removal such

or at ~f rare.

of dissolved through

gases inert from

with carrier Ficks

from

solutions

by bubbling

as helium and exof re -

been

studied

theoretically It was found is

(starting as

of diffusion) that the

perimentaUy.,60 tracer moval lives Boiling methods ium) have xenon are

expected with

theoretically time, Thus swept

depletion for with with the half-

in solution

exponential minutes. are

and half-times gas eous species

of the order than a few

of a few minutes

of more

often

out of solution

helium. other

the clear for

solutions rare 60

is also gases Loss found

effective. from targets from

Efficiencies (specifically uranium Thus removed freshly

of various xenon

removing studied.

from

uranof may be by

been

of xenon to be

on the formation uranium from metal

the hydride converted some hydride boiling chloride The ally

at 300C first

was

1~~ or

less. then

to the hydride Amalgamation or solution

and the xenon of uranium of uranium dissolves amount

the hydride uranium and cupri-

method.

from

decomposed

and boiling, are satisfactory.

hydride

in aqueous

AgC104

Uranium

in saturated of hydrogen.

with

the evolution of rare

of a small gases from

potassium 61

diffusion

metals may

at low temperatures generally if this there be evacuated

is generwith From loss the uranat

negligible. in place metal than

Thus before

dissolver solution gaseous At higher is

systems

target ium les~

commenced products

is desirable. is no detectable of rare Negligible

1000C.

containing 62

fission

temperatures

evolution

gases

begins,

accompanied from most

by swelling metals might

and cracking be expected rare gases

of the sample. at room

diffusion di-

temperature larger must than thus

as the atomic interatomic

ameters in metal

of the heavier lattices. in the

are

often gases

distances

Movement lattice.

of rare

be mainly

through

I,microcracksll

A particularly been salts (more reported of heavy rapidly

neat method for removing rare gases from 63 recently. It is based on the fact that long-chain emanate rare gas es quantitatively from solutions). and very Removal

targets fatty

has acid

metals than

rapidly of more

gases

can be swept

28

than

997D of the 3. 9-see targets yields There

Rn

219

was

achieved catchers

from were

barium used .

stearate. in studies

Uranyl of inde-

Htearate pendent

and barium in fission

stearate

chains a few

containing comments added much

rare

gases

are

perhaps

to be made for gas rare

concerning of interest need

the

addition are usually sub-

of carriers. determined sequent yields

Amounts

of carriers of how

gases

by consideration operations

one will

to perform Actual

counting are

accurately interest

and c~nveniently. complete

percentage of carrier cc STP to

of no primary Rather, The

assuming are may

interchange

and activity. yield of gas.

ones

needs

expreseed vary should

in terms

of so many from

yields

required

considerably be kept

experiment when than one finds amoonts in a

experiment it desirable previously procedure ual pressure certain gas

and one point to reduce used are with the

in particular amount .

in mind less

of c,arrier

to something that most in terms

success

It often may

happens

of the

losses

of the type left behind

which

be expressed

of a certain

residor a the no

in a given of a gas are

volume in the exit

in a transfer stream from

by condensation, a trap of ga~ in which and bear

partial

pressure These

ia condensed,

losses gas

in terms added.

of cc STP Thus

relation

to the amount with his yield

of carrier 100 cc STP activity (10

if one obtains

90-7. yield wishhe may essentially of the

in an experiment es to increaHe find that his limit

of carrier, by using rather than one may

and in a later only 20 cc STP

experiment of carrier There is

specific
is only.50%

18 cc ST P), u8e without (where

a lower procedure cipal

to the amount losses

of carrier of the type

modification are

to reduce

mentioned

the~e

the prin-

losses).

V. Method~ veniently termined activity, 1) Muller which into

COUNTING have been

R-E

GAS

ACTIVITIES rare gas activities of method may will be conbe delevel of

used

to count

divided

several

categories.

The

choice

by the usual half - life

considerations and type rare

of kind

and energy

of radiation,

of activity, of the counter:

of information

desired, in the filling involves of a Geige~one in all faced for texts of of

Incorporation

g as to be counted The use of this

or proportional of counter

technique The

the problems the first on the course favorable and often which such time subject.

construction

and filling. in detail must will

experimenter

with these problems 64,65 Only a few efficient means

be referred be made here.

to standard This is

comments of counting of absorption of low

the moat

gaseous losses.

activities

as a result desirable

geometry necessary radiations

and absence in the assay of short Both

It is thus

levels

of activity

or of active

species

emit as

range Geiger

(soft

beta-emitters,

or alpha-emitters counting have been

radon

isotopes).

and proportional

29

used,

each

having with

advantages counters do have fairly losses slow high

and disadvantages. is simpler a greater levels

The

electronic

equipment However, some-

associated proportional times wish

Geiger

and less

expensive,

counter~ to count

range of activity,

of usefulness since

if one may

dead-times count~

and the in this if very gas for actives-

resulting manner many

coincidence is relatively

are in any The

smaller. case, time

Since

performing are

savings

important

samples

must

be run.

counter and

fillings some

containing method must

the rare be found

ity will tablishing ed. pulse x-rays)

of course

vary

in composition counting

reproducible conditions observed

conditions

if the best at least

accuracy

is to be obtainby using the 55 (as Fe more time

Counting height

can be reproduced with some suitable

as accurately radiation as by running Geiger

monoenergetic levels

to set high plateaus.

voltages This

and discriminator method is applicable with

consuming al counters, more voltage

to both as gas

and proportionvary with type

but is more with voltage

accurate

the latter

multiplications do pulse heights

rapidly

in the proportional As usual

region

than easier

in the Geiger with

region. whose

it is much

to calibrate

this

of counter counting If absolute effects

samples

as say

is lmown than

and to reproduce to attempt are

the same counting. for walj end

conditions counting

in as saying must

unknowns,

absolute necessary and for

be attempted,

corrections

(electric on the

field

distortion

at the tube

extremities)

effects and be

depending

specific

ionization

of the radiation required for

in the counter Counters radial

filling may

the minimum constructed of field General theoretical Staub6 ically tubes discus

number with active

of ion pairs volumes with

detection. is

over

which

the field

concentric sion

the wire

and held

at the proper including may be found

by installation 66, 67 voltage. an approximate in Ros si and empir contechioneffect, -

of end effects of wall Appendix aliquots

and wall

effects,

derivation (page 234,

effect 9).

corrections effects are

End

generally

determined

by counting except tubes

of the same lengths, diameters per

struction nique ization depends

for

different

sample in two tubes of identical 68 and wall effects by a similar (remembering unit path length, that the average and thus the wall

using

of different by the

produced

radiation

on pressure fillings

and composition may be made

of the filling). using any of the rare gases and a suitable as to 68 op-

Counter quench. preclude

Positions brief

and shapes here. probably

of plateaus Some find

depend

on so many appear

factors

discussion till

examples some

in the literature, necessary as by his

but the researcher timum fillings will

experimentation as well Purity as

as

be determined

by his

electronics counting).

counter

construction especially form quench

(particularly from highly

in proportional electronegative

of materials, which tend to

species A large

such

oxygen

negative materials

ions , is important. may be used.

variety

of polyatomic are

gaseous among the

Light

saturated

hydrocarbons

30

most

copmon.

It might

be noted used

that krypton

and

xenon

purified fillings

according with

to

Detailed

Procedure

1 are

in proportional Laboratory ae quench

counter

no further

purification. (roughly Argon, junction portions rate

At Lawrence

Radiation is used

technical-grade after drying with been

isopentane sodium used smaller to allow wire.

20 cm Hg pressure) krypton, with this and xenon quench. gas,

pressures Plateaus

up to 20 cm are generally

Hg have better

in conproaccu-

at the

of rare

but several measurement 85 of Kr level of Kr

cm Hg pressure of the aliquot are 85

is desirable counted.

and convenient When low

levels

that the atmospheric this liter level in 1954 was

to be counted it should be borne in mind . IS now appreciable. In the Paris region /min. 69 and in One where carrier 1958 should 4200 d/m Kr per 85

1200

disintegrations

of krypton used work

removed

from

the atmosphere. for this background to use for

assay

in carriers low level moved

and correct

necessary. krypton which

In very was re-

it may

be necessary

from 2)

the atmosphere counting

at an, early in fixed or

date. reproducible geometry: beta-emitting whose geometry Practically counting For rare higher gases, respect con-

External

levels the gas

of activity may

of gamma-emitting in a thin-walled is accurately small

or energetic container reproducible. volumes,

be counted counter

with such

to .a thin-walled tainers are As are

70

limited lower

to fairly than with

and overall tubes method be 71

efficiencies next.

generally will be

the rfixed advantage

geometryif of this may

to be described over the use in rapid

seen: below tubes

the main

of ! fixed succesin a must

geometry sion on one

is that a series (say used

of samples

counted

counter

by constructing for plated is thus and solid

containers samples ).

to fit the shelves The effort which

counter

ordinarily

be expended For be affixed available Counter for

in calibration best accuracy

considerably efficiency counting with

reduced. the container tube, for the gas may

counting

permanently thin-walled

to a thin-walled counting Skokie, Combined tubes

as in commercially

concentric Reynolds

Laboratories, 85 counting Kr . counting counter

Illinois). geometry of 5-20~0 Kr85

glass jackets (Radiation 72 used this type of tube factors resulted in an

and absorption with jacket with

e~timated mg/cm2

efficiency wall. Thus

volumes specific

of 3-10 activities

cc and 30 as low as

samples per cc STP

100 to 200 These The

disintegrations/minute were used

could

be accurately

assayed. work. for and

counters counter was

in the Geiger into being

region

in the aforementioned system

sealed

permanently sample are

a vacuum counted for

and provisions of expansions the activity

reducing dilutions itially too

the aliquot with inert

of the carrier

by a seriee where

described

cases

is in-

great. Radiation the decay Laboratory of a variety these of rare same gas tubes activities. are used They for are countsuit-

At Lawrence ing and following

31

ably

filled

and used curves

as proportional to be taken used,

counters from initially

to reduce higher

coincidence activities.

losses With the

and

permit particular taining

decay

electronics equal . volumes Absorption but overall

filling

with

10 cm

Hg pressure gives

of a mixture y counter radiation still

conchar be-

of argon losses

and isopentane vary with for

satisfactory of the beta are may

acteristics ing counted,

the energy various

efficiencies tube

activities which

in the range into

quoted

by Reynolds. circuitry,

Each

is fitted connection to allow

with

a base

be plugged with a stop-

the counting cock

and the ball joint

to the jacket easy attachment of many may

is fitted

and ground-glass systems a panel .

to and removal in rapid

from -

vacuum sion,

To facilitate, which

the counting of tubes

samples

succes and a As is diffiglass

into

a number allows rapid

be plugged

is provided, to be counted. Kr 85m

switching resolution cult walls

arrangement of fission

product tubes Kr

2. 80-hour were 85m 88 .

selection 88 Kr

of the tube from with

4. 35-hour special 200

and tedious, to remove

a few the

purchased betas This

mg/cm2

softer

by absorption brings up one curves As

and permit special

simpler

accurate

determination 88 the counting of Kr . definitely statistical decay curves beyond

of Kr It was

noticed

that

decay

point concerning 88 of Kr exhibited s catbecame Xe33 and assumed 18. O-rein. after its on the deposiwalls resulted pursued of in

tering roughly xe135

statistical the decay

expectation. reached the Kr

the scattering tail, and

when

85m

behaved

statistically decay curves

in the same was

counter with

it wag the

that the behavior Rb88 daughter. 7374

of the Kr As the R~8~

associated

1s expected

to be ionized

immediately of local

formation glass tion walls

It was

hypothesized

that accumulation

charges

of the jacket containing the gas was resulting 88 of the Rb on the walls. It was found that silvering to provide for a conducting 88 Kr conforming walls are surface enclosing .

in irregular the internal sample was

the jacket decay farther

the gas The matter

curves

to statistics always provided

but conducting in high

for

containers

in which

no 88 Kr

is to be counted It was of 10~0,

geometry. that the efficiency of these counters made was of the order

stated

above

but it should efficiency in some

be noted accurately. suitable

that no effort The

is ordinarily are

to determine for each nuclide are proce re-

the actual ofinterest produced dures are are

counters

calibrated counting Such

manner

and the same

conditions counting

in subsequent undoubtedly

counting familiar for

of unknown to most rare

samples.

radiochemists Thus,

in other if one has counts

contexts the Kr

essentially target

no different in which later

gases.

and 88 from

a U235 neutrons,

a known determine with

number

of fissions

been

induced which

by thermal occurred (using fac88

he can target tube

the number thermal ).

of such

fissions

in a U235 the tor same

irradiated counting involves

neutrons The

by counting

the Kr 88

and case

conditions the number

calculation f,

of the calibration AO, of Kr

k in this

of fissions

the activity

extrapolated

back

to a suitable

zero

time(

the midpoint

of the irradiation

for

sufficiently ehort irradiations ), and a suitable aliquot factor. Thus, f = kl X Ao ~ cc STP carrier = k X AO X cc STP carrier/POoC. The actual volume V/ 7 6

o c x

of the counter

jacket

provides calibration

no useful factor

information without actual

in most

cases

and its saves in the It is often solution

inclusion considerable counter possible for some

in the counter work. to

determination

Poc
OC

is

the measured

pressure

of the carrier

corrected

~rom

the temperature of fissions counters

of measurement. f by assaying

to determine fission

the number for which

the target been

product Ultimately,

have

already

calibrated a direct detercan count-

(e. g. , M099). mination achieve ers has

of course, must

experiments have been all counter in a short accurate

involving

of fiseions accuracy the obvious counting due

in targets sufficient drawback for

performed. purposes, must time

While

one

practically that each

the uBe of these

be separately requires

calibrated for each

and that sample

a number

of samples for

a tube

to the time

required g ases

manipulation in a glow or foils activities

of gases. discharge: used are Trace

3) amounts in a glow a glow

Deposition of rare

of rare may

on the cathode on wires rare hundred helium). gas

gases

discharge

be deposited 5. chamber. Tracer along with a few air,

as the cathode collected of some volts dc in gas

discharge

tube

microns A few

pressure hundred

to support potential for a few is

the discharge is applied minutes. surprisingly

(nitrogen, a glow

to cause Deposition high

discharge

and the discharge of the gaseous range for for

maintained on the re -

and retention (in the percent

activities Heating at room

cathode moves ature. tions

Rn 222). days

the activity, The of rare 4) technique gas

but it is quantitatively has proved useful 76, 77 .

retained in studies

temper and radia-

of the half-lives

activities study

Indirect

of rare

g as activities rare gases rare

through

their

daughters: cognizance should daughrare

Although be taken ter gas

not a method of the feasibility Thus product

of counting

themselves, through

of studying early

gases

counting

their

activities. fission with

some daughter gas

experiments

were

performed

in which

E were

coaxial could

a moving from

stream: rates

coilected on a negatively charged wire 78, 79 Rough half-lives for the rare gases and the daughter chain ,of rare emanate gases yields gas activity have also as a function been studied of through metal

be obtained along

flow

distance the

the wire.

Fractional

relative

amounts (from which

of daughters rare gases of rare where

activities rapidly) the

found

in heavy

stearates where

very

the decay may

products be useful are are too

leaving

stearate

and on container walls 63 Such deposit. or where or the rare subsequent

techuiquee gases decay

gas

counting to count, for

is inconvenient

themselves products

short-lived

but the immediate radiochemical assay.

of reasonable

half-life

33

5) gases main

Rare been

g as

scintillation to be

counting: satisfactory

It ia interesting scintillants

to note

have

found

in counters.

that the rare 80, 81, 82 The of heavy property

usefulness such output

of such as fission

scintillants fragments. only

promises They on total

to be in the counting have the highly expended desirable

particles that tion light

is dependent

energy

(and not on ioniza-

denmity). 6) The feasibility into in specific solid samples instances of their of counting parent rare gas activities for were and plated samples

which

have

grown should

counting, studied out for was

in this counting

be borne in mind. For example Xe 83, 84 manner. Fission product iodine as Ag I or Pd12. for Radioxenon even

activities, 135 and was

plated Xe133

separated

growing

into the plated

retained

quantitatively

weeks,

in vacuo.

VI.

COLLECTION

OF FOR

RADIOCHEMICAL RARE GASES with

PROCEDURES

THE

The of which er ences

largest the author

collection is aware

of papers is found of this were

dealing

rare

gaa

radiochemistry General Ref-

in the last monograph. chosen for

one of the nine

given

at the beginning procedures

The calling author

following

description

with

a view

to The should

attention would

to as many

useful

techniques concerning

and operations other

as possible. which

appreciate in such

information

procedures

be included

a collection.

PROCEDURE AND

1 REMOVAL THEIR

OF

Kr

AND

Xe FROM

AIR

SUBSEQUENT

SEPARATION

Source

F.

F.

Momyer,

Jr,

, et al.

unpublished more,

work

at

Lawrence

Radiation

Laboratory,

Liver

California

Figure standard nitrogen, obtain along

1 shows

a photograph

of the

system

used

in the reparation. in liquid

pumping

arrangement diffusion of train 10 -5

consisting pump, to 10

of a trap

refrigerated

a mercury pressure

a base

and a mechanical forepump is used to -6 mm Hg. Proceeding from Left to right and label 2) wool coil; 3) Tl, plugs Cl, 4) for a trap purposes packed fine of later with 3/16 in. of but small -

the separation

let us designate 1) a flowmeter; glass

discussion stainless condensates containing

the following: steel balls

and suitable

to retain a trap

particles to Tl three

and preceded 100 grams

by a glass

similar

of activated

charcoal;

C z,

C3, and,c4,

34

Fig. 1 Separat;onsystena

used

in Procedures

1 and

1A.

35

PROCEDURE er traps trap each containing 10 grams three;

1 (Continued) of activated 6) charcoal; 7) 5) T2, an unpacked for sample

similar and the

to the preceding 8) a mercury trap

a ZOO-CC bulb; Helium left. This

an outlet

removal; through

manometer. lower from

is admitted trap is cooled

to the line in liquid nitro-

charcoal trace

at the

gen to remove charcoal off from photograph flow may trap the

impurities

the helium. between It is 1 certainly T

Partially

obscured may

by this be closed the

is another system with

manometer a stopcock.

and C ~ which not obvious so arranged

from

but connections be directed

and stopcocks any charcoal

have trap,

been

that helium chamber to by seen

through into

through charcoal

an ionization trap,

(unseen

behind

the drape), The

any

subsequent

and thence is amplified partially

the atmosphere. a vibrating at the right chamber reed

current

through whose

the ionization output drives record To the left and meter. of 22-mm

chamber the recorder of activity

electrometer Thus

of the bench.

a continuou6

in the ionization is the are and

during

a ~eparation gauge

ia obtained. power supply traps

of the recorder The o. d. large glass traps tubing,

thermocouple constructed their

vacuum of 41-mm

and the small are about

respective activated mesh system

lengths

25 and 20 cm. ground

The

char coal mill

is Columbia and sieved to

Grade-G yield

charcoal material. is used for

(6- 14 mesh),

in a ball

20-50 The

the

separation

of rare below

gases

from does

various not treat of

types a

of samples, problem sample tion work has

and the procedure encountered. flow rates

described It was chosen

admittedly

often size, been

to represent of rare

the extremes gases for which

and partial achieved number feet

pressures with

separa-

successfully which

the system,

and to afford could

a frame-

within The

the largest is 100 cubic

of operatiom of air

be described. into a bottle con-

sample

(STP)

compressed of active The

taining yields

100 cc STP are about

of active for

krypton and

and 75 cc STP
95~0

xenon.

Average for the heated

90%

krypton 8 hours Before

for

xenon. are

time

required

the separation sample into

is about the system.

of whibh the

3 hours

Bpent in bleeding traps have been

run all

charcoal vacuum

to 350 C and pumped is pinned 1. the glass coil (probably Gallon coils.

on until less

the

thermocouple 10-4 mm Hg). are

gauge

in the manifold

than

dewars The

of liquid

nitrogen level

placed be above

on T ~ and C ~, including the connection from

refrigerant

should

to trap. 2. Through line below a pressure gauge and reducing Sample 35 cm Hg. valve into the sample is cormect equithe r -

ed to the librium

the flowrneter, C ~ is about

is bled Wait

T ~ and C ~ until minutes until

pressure

o~er

a few

36

PROCEDURE mal equilibrium is reached nitrogen. pump as evidenced

1 (Continued) by steady pressure and decreased

boiling 3. establish 35 cm liquid used

of the liquid Using sample

a mechanical flow through Reduced

on the exit

from

C ~ and

suitable minute

valving, at about of is

T ~ and C ~ of pressure

15 liters

S.TP per to avoid

Hg pressure. air

is neceaaary Rotary Gas of air the

condensation (4 cfm) periods.

in the system. the necessary nitrogen

An NRC-4S large

Ballast over

Pump* prolonged

to handle

amounts

Keeping until

the liquid

replenished, is about

bleed

sample

in at the above Pumping for

rate

the pressure with

in the bottle open

one atmosphere. will reduce

a few

minutes to about rare

all valves This

completely

the pressure

in the bottle of the

10 cm Hg. from Close

represents

sufficiently

quantitative

removal

gases 4.

the bottle. the manometer on C2, traps. by C ~ and the stopcock C3 and C4, Thermal of helium flow of 1250 and introduce at the helium efit at side 1-2 of T ~, gauge will

place to all

liquid

nitrogen

psi

the charcoal

and pres sure flow into

equilibrium

in the traps

be evidenced 5. ization flow is

by cessation

the system. per minute through C ~, When the ionsteady

Set up helium chamber, established C2

cc STP

in liquid

nitrogen,

and thence nitrogen avoids from high

to the air. C ~. Allow

remove 5-10

the liquid (This

C ~ to warm system on C ~). be obrapidly

slowly from After served

in air too

for

minutes.

pressures STP of air

in the

rapid

resorption immerse

of the roughly C ~ in chamber dropping 10-20C in about off more

30 liters water.

adsorbed will rising

10 minutes

Krypton

activity

in the ionization and then When

5 minutes,

the activity

to a miximum about

S1OW1y (full -width than

at half-maximum value ( 10-15

2 minutes). ), 6.

the activity

is lees

1% of the peak

minutes

the elution

is halted. flow of 750 cc STP per minute through C2 in liquid the ice-

Set up helium into

nitrogen, liquid acetone from up, C2. stop 7.

the ionization from (-78.

chamber,

and thence

to the air. immerse

Remove C2

nitrogen slush

C2 and after 5C). Elute

a couple

of minutes

in dry air

approximately

ten minutes chamber with

to remove this

If activity the elution

appears immediately

in the ionization and proceed (750 cc/rein)

before step.

period

is

the next

Direct

the helium

flow

so that the

sequence

is C2

in

*
61,

National

Research .

Corporatio~

Equipment

Division,

Newton

Highlands

Massachusetts

37

PROCEDURE dry air. The ice-acetone, Remove krypton the ionization the dry activity ice-acetone will appear chamber, from in 1-2

1 (Continued) C3 in liquid C2 and replace nitrogen, with and out to the water.

1O-2OC

minutes

in the ionization . value Elute until

chamber. activity in the than ten

Full-width ionization minutes 8. ),

at half-maximum chamber and stop Repeat is less

is about than

30 seconds

1% of the peak

(should

take

less

the elution

at that point. krypton from C3 to C4.

Step

7 to elute

9. mocouple require with

With

C4

still gauge

in liquid

nitrogen,

pump is less

until

the pressure micron. of helium

on the therThis should 4 in less C

vacuum less

in the manifold and results does

than one

than five of krypton.

minutes

in the removal not pump down

from

no loss

Lf the trap

to one micron step.

than five 10. and some warming

minutes, Place residual C4

discontinue T2 in liquid The

pumping nitrogen. removal the

and proceed At this of air is point

to the next C4 contains

the krypton by

air.

essentially through

accomplished T2 in liquid

HLOWIY, pas sing any krypton in the

evolved

gases

nitrogen about

to conden~e

evolved, system

and every

time

the pressure the gas the open in T2

reaches

112 atmosphere ing the be borne krypton liquid which nitrogen tion time stopcock in mind in the nitrogen

beyond manifold is

T2 pumping through condensed

off briefly position.

by rotatIt should

to the vacuum that once

krypton is 2-3

the partial pres sure to keep

pressure of krypton time

of at

system

beyond

mm one

Hg (the vapor thus wishes losses.

temperature)

and that

the total

one pumps from C4

on T ~ to a minimum and allow use the trap

to reduce to warm

Remove minutes above,

the liquid until evolu-

in air

a few

of gas begins, evolution

the pump slows down

in the manner

described

and each the trap to water,

of gas higher

u peed
(dry 40 C). pump in the slowed

the process ice-acetone, When off the system. by any

by heating room

successively and finally pres 2-3 from air). ume sure mm C4

temperatures -is about steady,

temperature

warm in the

water system

the trap last (The

is at 40C of air,

and the leaving

vestiges

Hg pressure to T2 will 5-10 be

of krypton seriously for

distillation pressure of krypton.

of krypton of residual Lf the vol between C4 o: be

observable

Allow

minutes has

the

complete

distillation

of the system be

been Tz

measured warmed

beforehand,

the stopcock

and TZ may krypton about outlet

closed,

to room determination

temperature, of the bulb from

and the pres yield. attached the line. to base Yield

sure

measured 907.. and 11, Distill cooled Place

to get a rough the krypton in liquid boiling

should

into

an evacuated and remove and C4

to the system

nitrogen, on C2

water

and pump

down

pressure

38

PROCEDURE to remove in liquid 12. temperature, air. The The time traces nitrogen, of krypton. and admit flow Cool helium of 1250 chamber,

1 (Continued) the traps to speed cc STP C2 to room the per temperature, then place

cooling. minute through C ~ at room to the an hour. in a than l%

Set up helium

the ionization xenon may will

in liquid

nitrogen water

and thence in about rapidly to less

be eluted

to C2 from 30 min.

C ~ in boiling by heating of 350C.

be reduced

to about

C ~ more Elute

furnace of peak

set

to reach

an eventual

temperature

activity. 13. Set up helium the ionization flow of 750 C4 cc STP per minute nitrogen, krypton either through C2 in liquid to air. appears or a

nitrogen, Warm (less

chamber,.

in liquid any

and thence peak boiling

CZ to about than five

40 C and throw Elute

away

Bmall using

which water

minutes).

xenon ).

to C4

furnace

as in Step 14.

12 (15 to 30 min. in liquid

T2 is cooled

nitrogen,

C4

warmed

to 100C,

residual

air

pumped Xenon

off if any is present, losses are slight is only in this about

and the xenon process

distilled

to T2 in 10-15 pressure the xenon for removal

minutes. nitro-

as the vapor Measure bulb

af liquid yield from

gen temperature be 9570 or greater)

50 microns. to an evacuated

(should the line.

and distill

Comments 1. higher For smaller samples in which the rare fraction gas partial pressures may are originally

over

T ~ the pos sIibilit y that a large in T ~ at -195 krypton pressure If this xenon since C should its vapor over

of the xenon

be condensed occurs with

be noted. pressure the trap

(It seldom is higher should also

happens (2-3 mm

that this Hg) at -195*C, with

but partial each one more The glass

of krypton occurs

be considered recovery from C ~.

sample). could distill

and one wishes s=rting from

qutitative the elution

of the xenon It is usually

to C ~ before

convenient fastest coil -y before

to recover to accomplish T ~ in liquid balls

the xenon the

T ~ and C ~ separately from Tl is as follows: coil

however. Cool the eddy tem-

recovery Use

nitrogen. heat

an induction rapidly have been

to produce above room

currents perature. sate water into liquid

in the steel Pump off

and thus air

them may

to well

residual coil Distill to the

which

occluded carbon from

in the condenand at -78.5 in or C

through into a bulb

the glass

and then xenon outlet

distill

the xenon, dioxide left

dioxide, coil

the coil. attached

and carbon at the upper

the

of the

rack times

and cooled until

nitrogen. gases

Thaw are

and refreeze

the water

several remove

occluded from the

dissolved xenon

removed.

On another

rack

the C02 from

by passage

through

Ascarite

or by distilling

the xenon

a bath. at

39

PROCEDURE about -150 C into lzq-aid nimogen. (- 160-C) The

1 (Continued) vapor preo n me of xenon at mopemane at a One may

Kr

nlimh few C

temperature Iugher use Moot Cron

in only

a few aaed

mm

Hg no liq~id

isopemane

temperature dry ice-acetone carbon

M usually on 11 diotide

to speed water pas

u

the dintillauon. without C ~. fracfiono

of coarse and Xe. 2. been

to remove -11 then

condemning

of the
q

onto

-contamunon of their

of the krypton radioactltity. dismlled observed

and xenon In one directly

ham never krypton

obmerved

in terms

run unth reactive

and active from the

xenon,

the krypton activity in thio

wan was one

off of C7 afrer

the elimon limlt It thun m for

C ~ and no xenon Reparation quite factor likely

m the krypton.

A lower

elanon

of 5 x 103 was elutions

calculated.

appears many

that the wo

suboequeni

could

be eliminated

experiments. 3. The inclusion to allow of a thermal detection conductivity cell in series elated As with from the loruza the char the

tion coal

chamber

of nonra&oactive tid trapa in many

opecies

haH proved of air

to be a valuable the charcoal

operauono. Kr

an example,

elution efficiently rare

from

conralmng

can be performed peakl-.. Also,

more with one cell

if one

can obo erve not active elu~on

the emergence

of the am

gaa

u ampleo
the

q nough
on the

to register

in the ionization in &e thermal

chamber.

can observe
rather nmem. 4. of tie of 30-60 than

peaks of the carriers

purely hams

conductivity retention

operating

of prewously

obo qrved

In a recent

modiflcarlon small Molecular long. of each) the mixture

wtich charcoal Sieve

promioes trap,

to improve C3 # wao glass

the versatility with about 60 gramo 1 cm (typon C,

system, mesh

the. second 5A Linde

replaced cohmn

in a coiled

in diameter ically *1E about column.

and

120 cm

Separanone have been C2

of methane-krypton performed to the very

mixturen

50 cc STP Eluting

satisfactorily col~

from m

top of thm dichloride minute

at -195 the

and then follotig several 3rnin.

raioing eluuon r-am:

the temperature data Kr, peak with

-36 C

(ethylene cc SIP per

slush..), were

He I1OW of 600 rime

fo-and in

peak

retenmm time

18 mm.

, full-width

at half -maxim-m 8 h.

;CH

~,

rerention

35 min.

, full-width

at half -rnaxim~

PROCEDURE

1A REMOVAL PRODUCTS for U 235

AND FROM

SEPARATION U235

OF

Kr

AND

Xe

FISSION This and clad procedare

TARGETS of 100 mg m weight

is used

targets

of the order

in a few though

hundred only

milhgrams of the rare

of 2S alummum. gasea is of interefir it m the pracnce to

Even

one

PROCEDURE add carriera amount for both to circumvent is determined to be performed

1A (Continued) the vagaries by the later, of tracer behavior. The concerning of krypton

of carrier

added

usual but

considerations 100 cc STP ., each

the co~ting and xenon The precauti~ns of breakage left glass funnel

operation would ByBtem

be typical. as Bhown in Figure Bhielding 1 may be used to catch diBsolver a 34/45 for

the separation. solutions at the

Safety in caBe

Buch as must

and containers The with

active flask

of course round

be provided. flask 34/45 outlet fitted joint for

extreme ground-

is a 250-ml joint, has

bottom

inner-tapered

fitting been

an outer The 18/9

into

the top of which gases is The

a 8eparatory an arm at of

sealed. an

evolved ball

through trap

the top fitted

with

ground-glass

joint.

to the right

the fLaBk is packed 1. rack. fitted A bulb target

with

Ascarite. the carriers is attached at the upper joints left of the and This iB

containing is placed Air

The

in the flask from

and the tapered the entire

greased

together. with

is evacuated targets

dissolver

system. gases from

permissible at room the

most

as the diffusion The Tl other

of the rare alternative in dry

uranium air in

temperature onto

is negligible.

is to pull and

the

system

C ~ at -195C.

is cooled

ice-acetone

C ~ in

liquid

nitrogen. 2. With the stopcock through HCL before the rest with a few C ~ closed, of the drops or open the carrier Start the added. A wet bulb solution Rate towel to allow by dr,ipof reaccontain-

carriers ping tion

to expand

system.

in concentrated may be controlled be -appeal back above

of 30L70H202 the flask.

by warming around into

cooling

ing ice and acid with more essary the final 3. other boil orous -ice

may

the neck

of the flask Inclusion

to reflux

most

of thewater cooled

fumes water

the solution.

of a reflux

condenser

the dissolver

is more

esthetically

pleasing

and probably it may 4 below). be necDilute bath.

efficient. to transfer few cc

If hydrogen some

pressure

approaches the cc solution. cold

atmospheric (See water Note

to C ~ during to 20-30 bulb

of solution the carrier

with

and cool for

in an ice Pull

Close onto

to retain few mm It was this

some

carrier

flushing.

gases warm boiling 4.

C ~ to a residual if necessary. during

Hg of hydrogen. originally cooled

The solution to avoid

should

slightly and

too vig-

splashing stopcock

operation. the carrier bulb. Again pull all

Close Cl. Close the

the

to C ~ and open

gases

onto 5.

the

stopcock funnel. flush

to C ~ and admit Pull of the the air system

a few onto

cm

Hg of air (Provisions

to the for

system the use

through of helium

separator this final

C ~.

for

would

be desirable).

41

PROCEDURE

1A (Continued) and air are now on C at liquid 1 starting from very little dry of the nitrogen Step 4.

6.
temperature The final

Krypton,

xenon,

hydrogen

, and one follows steps will. be simpler

the previous

procedure contains

as the sample removed necessary As

air,

and the

hydrogen 7. are

is nearly

quantitatively analyses

by the elution for

from

ice-acetone. experiment Kr

Radiochemical

the purpose

performed

on the target assay Mo

solution. 99

an example, the number fission

in calibrating of fis Oions to have

88

counters target, vioasly

one might assuming determined.

to determine for this

in the been pre -

calibration

factors

product

Notes 1. guishable The (the system same has given results from was in calibration those runs which are indistinsys to

to within

2-37)

obtained

with an earlier system entire prior

tern in which solution, finally the flushed 2. krypt~n liquid

a portion rest

of the carriers through C ~ with of air =gon

admitted solution, bubbled has been

to the

bubbled

the clear heliurxi

and the

system

out through

in through used

the solution. argon, and xenon C. The at

In the absence and xenon. The

the system is adsorbed

to separate

along

with

the krypton at -78.5

nitrogen

temperature, from are

and eluted nitrogen used

off the charcoal and oxygen if air

ar -

gon will this case 3.

not be separated chemical meana

is present;

and in

to purify Xe 135

the argon. within has a few hours of

In experiments no evidence

irradiation,

of I

involving 135

s eparationa the charcoal

reaching

ever

been

observed. to

Results of the experiments performed were 1135 contamination, however. Ln e~eriments affected by s light more iodine closely. contamination Detaile,d

generally where

not very results

sensitive would this

be greatly should of

of the xenon Procedures

fraction,

point

be checked other

4 and

5 contain

examples

effective 4...

means

of iodine a syetem

removal. for the solution inclusion of wrious ahead types and sizes of

In building the author

targets, with

would

recommend

of T ~ of a trap to water,

packed

CUO and heated filled with

to 500 C for a desiccant,

conversion such

of hydrogen

followed The size not contains

by a trap target limited only

as magnesium

per chlorate. volume

which

may

be dissolved

in a system evolved amount

of convenient , and the fact

is then

by the volume gases simplifies quantitative successfully

of hydrogen and a small the total transfer for

that the a ystem after

the rare

of unburned of carrier to

hydrogen

dissolution as well has grams. as

is complete the been ultimate used

interchange

and activity C ~. Such

of the carriers

a system. up to a few

the dissolution

of targets

weighing

42

PROCEDURE

Z THE AND

EXTRACTION, USES OF

PURIFICATION Kr85

Industrial

Source

E. K.

J.

Wilson,

G. report

Evans, AERE

J.

Chadwick, 2216

J,

Eakins,

J. Taylor,

I/R

(1957).

The product

procedure from

described kilogram

in thim paper amounts involved scale

ie for

the recovery uranium. to point

of fission metal. A brief which

krypton

of irradiated is given below

description may

of the operations to smaller 2.3 -kilogram

out methods

be applicable 1. Three

experiments. slugs containing fission Dissolution The product krypton

uranium stainless

are

dissolved with

in a 70-liter roughly

steel

container. at 104C.

is accomis car,oxygen used to

plished ried over

12 liters with Note

of 10N IZN03 to oxides

dissolution

out IIfumelesslyi[ the solution acid is (See fumes

respect 1).

of nitrogen 6 liters

by admitting of ~ter during are

Approximately them back into

recombine Solution nitrate

and wash in about

the vessel result

solution. of uranyl to mainsystem to

complete

20 hours

and the final excess

is a solution is used

in approximately to the purification fluehed with train. leaving

3N HN03. train

A slight during

of oxygen

tain flow is finally

dissolution complete

and the dia solver of fission

helium

to effect

removal

gases

the purification 2. which carbon ing ~th per bons they Gases

the dissolver

are

circulated 1) rough

around drying

an apparatus with CaC12, 3) final with

in 2) drycop-

receive

the following with

treatment:

dioxide

removed

Sofnolite 4)

(an NaOH-CaO removal from

mixture),

magnesium

perchlorate, 5)

of oxygen

by reaction

turnings removed

at 600 C, with

any water 6)

oxidation

of hydrogen

or hydrocar

Sofnolite, by reaction adsorbed remaining The inflated

traces with

of hydrocarbons uranium

and gaseous at about temperature. to the point

compounds 800 C, From of entry of the pres of

of nitrogen and 7) rare

removed gases trap,

clean

turnings nitrogen return

on charcoal gases

at liquid helium)

the charcoal from helium. sure about ing

(mainly

the dissolver. A loosely

system balloon

is initially attached

f i~with

one atmosphere maintains gases parallel which .

to the system of evolved

at one one

atmosphere per hour

during

sudden bursts

Circulation pumps consistii

liter

is maintained

by two identical flow within

bf a chamber by periodic 3. Upon

permitting heating

unidirectional and cooling. of the dissolving

the pressure

varied

completion trap

and flushing the fission used for

the dis solver krypton will

with and xenon. also be

helium Argon

the charcoal present

will

contain

all

product

ae an impurity

in the oxygen in fact

dissolving the bulk

adsorbed

on the charcoal

and till

constitute

of the adsorbed

43

PROCEDURE

2 (Continued)

gaHes

(several

hundred gases

cc STP).

The

charcoal the

trap

is removed in boiling may

from water

the line and di-

and the rare evacuating rectly volume transfer rare

desorbed

by warming pump. The

charcoal gases

with

a Toepler

desorbed with large,

be transferred pump,

to the final of the rare the gases

purification gas first fraction

apparatus is very

the Toepler it may bulbs.

or if the total to of

be most The

convenient aliquots

to a series bulbs

of storage may then

smaller singly as

gases

contained

in these

be purified

convenient.

4. traps. but the graphic long

The All are

final

purification

apparatus

consists

of a train before second

of five

charcoal all -

heated are

and outgassed in liquid

to a vacuum nitrogen. The

the run and then trap is the about

second column.

cooled

chromato 20 cm The sample

It contains to -50

10 grams a dry

of charcoal

in a column

and is cooled gases

C with

ice-chlorobenzene to the first to saturate per hour all

mixture. charcoal charcoals set

of rare in liquid pheric train

to be separated Helium and a flow traps. the bulk

is transferred is introduced of 3.5 liters lowering to the dewar

trap

cooled the

nitrogen.

at atmos up through the first and in

pressure of charcoal first upon bands 5.

of helium

Gradual

of the dewar chromatographic the remaining

around

trap

transfers finally diffuse

of the argon of the

column, gases

complete

removal

deposit

at the head

of the column. Ieawing exit line the column from the is monitored charcoal. the column As charcoal Until with a GM is

Radioactivity suitably placed gas

in the gas near the

counter n,oted coal

activity

in the effluent trap (a precaution the flow

the flow in case

is directed

from

to the last soon

char -

of an error through

in judgment). all three

as activity subsequent

is noted to the in 2-3

is changed Activity

to pass

traps

column. more

appears elution

in about is stopped

an hour at this

and approaches point with most

background of the krypis

hours from

The

ton removed pumped

the column traps

and all the xenon while still cooled contain

still

adsorbed.

Helium

off the charcoal

in liquid a few

nitrogen. percent from of hydro krypton -

6.
carbons by charcoal cent.aining uraniun phoric fication steady

The

krypton

may at this

point

volume

pretiouely

undecomposed

by uranium These water are

and unseparated by warming the evolved

chromatography. charcoals in boiling

removed

the kryptongases
over

and circulating hydrocarbons,

over pyro Puria

turnings uranium

at 800 C to decompose at room temperature when

and then

to remove the pressure

any hydrogen

resulting. reaches

is considered state. 7. Krypton

complete

in the system

is transferred

to suitable

etorage

bulbs

with

a Toepler

pump,

44

,
or by adsorption nitrogen

PROCEDURE on charcoal contained

2 (Continued) in the Btorage bulbs and cooled to liquid

temperature.

Notes 1. The The dissolution in of uranium in nitric acid has been studied in detail. equation: NZ +2.25 is H20. + 85

dissolution HN03

11. 7M HN03 + 1.57

proceeds NO +0.84

according

to the following NZO +0.043 the reaction are

U +4.5 k 3/2

U02(N03)2 of oxygen, + H20,

NOZ +0.0005 for

the pre Bence 02

however, so that

the equation ofides

U + 2 HN03 in the

~ U02(N03)2

of nitrogen

not present

productB. 2. at 100C after Xenon could of course In this have be recovered from the chromatographic the uranium column

if desired. activities

particular largely

procedure

iB die solved with high levels of

xenon

decayed describing 86 Aside levels

to avoid

working

radioactivity. amounts remote very

There is a report 133 of Xe from uranium. introduced The As same is

the early from

recovery

of multi-curie and is is

problems

o~ shielding

control similar. used.

by the high dissolving so much

of radioactivity, purification adsorbed

the procedure apparatus the with final

and preliminary more strongly

in fact argon

xenon

than argon, gases The

is removed at -90 C,

by pumping rather

on the

charcoal from

containing a charcoal

the rare column. product (after gases

the trap xenon present

than by elution some As argon

fraction in the

contains sample.

and most step

of the fission

krypton the Bteps removed of a C . A

the final

in the procedure other for this chips than step rare

all are

in the Kr85 with

purification) getter. crucible 7

trace The

impurities apparatus

a calcium steel

consists

essentially to 550-600 glass

stainless Imirrori! Cleanup gauge

containing is deposited

calcium

and heated cold pyrex

of calcium is followed

on an adjacent pressure

surface. a McLeod B.

by taking

periodic when of Xe

measurements

with

and is To

considered smaller gram

complete amounts amounts

obtain of 10-20

no further pressure decrease occur 133 (of the order of 50 millicuries), uranium Effluent was gases carried were out with passed water

solution nitric through vapor the trap

of irradiated system. rings

acid

and oxygen packed

in a smaller with glaBs

a trap and N02.

and cooled was

to -80 again was

C to remove

Complete

removal

of xenon

effected

by sweeping a charcoal

solution at -509C same

with h,eliurn, to adsorb pattern

and the helium

stream

paBsed

through

ed the a dde d.

t e xenon. Subsequent purification of the xenon followi except that O. 03 cc STP of inactive xenon carrier was

45

PROCEDURE

3 RAPID Kr

REMOVAL FROM H.

OF

FISSION

PRODUCT

U FOIL Lazar, and E. (1956) Rb 89 for this useful for purpose. in other Eichler,

Source

G.

D.

OKelley, Rev.

N. 102,

Phys.

223-227

This study The

procedure operation for

was

used are

to obtain

samples

of the

15-min.

and the technique

briefly

described from

below

as given may

removal

of krypton

the target

prove

context~. The eter target is a uranium film at one (O. 3 mg/cm2) deposited on a 1. 6-cm-diamrecoil chamber This with

Pt disk.

It is mounted Al foil

end of a vacuum-tight and the Xe fission into the the etit recoil

a 3. 12 mg/cm2 amount passage serum

between

the uranium should stop

chamber.

of aluminum of the krypton bottle cap is

absorber fission

fragments chamber.

but permit A rubber end of

fragments

recoil line

used from

to cover the target.

and seal

at the opposite

the recoil 1. neutrons 2.

chamber Target for The

and recoil

chamber half-life

are

placed 89

in a pile . 1s 2.6

and irradiated

with

3 minutes. target

(The

of Kr

min.) via a pneumatic out for with tube through tube 3 min. a of the the a an

is removed shorter-lived cap sealing needle.

rapidly than the

and krypton 3.

isotopes rubber

Kr

from 89

the pile allowed

to decay

The

recoil

chamber

is punctured the center exits

double-walled hype, coafial trap and air outer

hypodermic containing annulus with cell. glass The

Air

is flushed

down

the krypton

in the recoil The effluent

chamber gases are

of the needle. wooi 89 for and cooled daughter 3 min.

passed

through into

packed

evacuated charged Due

Rb

of Kr The

in dry 89 foil

ice-acetone is collected removed

and thence

strip

of Al foil some

is

on a negatively 89 and Rb counted. chamber, and a

to straggling

few percent

by activity

recoils penetrate to the recoil 138 of Cs is found on the foil.

xenon

PROCEDURE

4 RECOVERY Xe FROM

OF

FISSION

PRODUCT

U METAL Sugarman, The Fission Div. (1 !?

Source

E.

J.

Hoagland

and N. Studies: Energy

Paper

147:

Radio chemical National Book This iodine procedure fiesion 2, Nuclear

Products, IV, 51) pp. Vol. 9,

Series, New York

McGraw-Hill, rapid

1035.

effects

dissolution It was

of the target for

and separation

of

and xenon yield

dent fission

products. 135 of Xe .

designed

studies

of the indepen-

46

PROCEDURE 1. attached The uranium target line is placed in which apparatus

4 (Continued) in the dissolver separation and helium flask, and the flask Air

to the vacuum from

the

is to be performed. is then admitted

is evacuated one half 2. amount ual ofide cone.

the entire pressure.

to about

atmosphere The of 1or target for

is dissolved

in concentrated After

HC1

containing is dissolved of a small during

a small any amount residof

!Iholdbackli may found in low

carrier.

the metal

carbide It was

be dis solved that iodide

by the addition ion was

ERQ03.

not onidized

dissolution

if present 3. -85C,

originally The a cone.

concentration. are passed in succession solution, two through cold ,a cold traps trap 300 The trap at

liberated NaOH

gases solution, trap

an NaHS03

at -85C, at -195 C.

an activated When

charcoal

at -85 C,

and an activated is (See 10 min. closed swept Note after off. are

charcoal about

dissolution Hg over

is complete a period

the solution of 3-4 min.

with

cc of helium procedure

at 10 cm to this The

1, below).

point

can be completed flask

within

the end of an irradiation.

dissolver 4. All

is immediately and some

the xenon

of the krypton is

now second

on the charcoal charcoal to 250C trap

trap at

at -85c. - 195C. desorbed evacuated thin-window 5. h

The this

remainder procedure (containing bulb.

of the krypton the first

on the trap

charcoal

is heated

and the pump to an

gases storage

all the xenon) Aliquots of xenon from growing

transferred for counting

by a Toepler are taken

by filling

gas -tight The amount

containers of Xe 135

the storage into

bulb. solution from known I 135 may time

the target

be determined after Early tion, irradiation

by repeating

the helium

sweeping

at a suitable

later

and counting indicated solution.

experiments or NaHS03

an aliquot of the xenon fraction so obtained. 135 no I reached the first cold trap, NaOH soluThus the helium to the storage sweep bulb, containing the xenon for activ-

ity may taken.

be transferred

directly

and aliquots

counting

Note 1. The double -etided closed dissolver end is flask used may used for be in this procedure of the target 180 through disk is illustratand storage. the

ed in the article. For sweeping atis with

The

solution

helium

the flask

rotated

through system glass two

about

horizontal glass helium joint. may

of the

sidearm then

qpnnecting rests

it to the

a tapered which the

The

solution

on a sintered bulb between

through below

be introduced.

A small

stopcocks

47

PROCEDURE

4 (Continued)

sintered Efficiency

glass

disk

is used removal

to measure

out aliquots sweep

of helium was found

for

sweeping. 9570. ,

of xenon

by the helium

to be about

PROCEDURE Xe FROM

5 RAPLD U03

REMOVAL

OF

FISSION

PRODUCT

OR UOZ(N03)2

- 6H20

TARGETS

Source

F.

Brown

and L.

Yaffe,

Can.

J.

Chem.

.31,

242

(1953).

This of Xe135. enclosed The carrier, started dissolve gen for

procedure The targets

was

also

designed 200-300

for

studies mg of U03

of the independent or U02(N03)2

yield . 6H20

used

were

in thin-walled target attached bubbling the

aluminum

capsules. containing about 50 mg of KI as holdback evacuated. acid admitted while H2 to hydrois

is placed

in a flask

to the vacuum through the

system,

and the apparatus 1:1 sulfuric solution

solution

and hot

capsule

and contents Effluent cooled

rapidly. gases pass

The

is boiled

is bubbled rough

through. a trap

through

a reflux

water

condenser

drying,

to dry-ice traps 30 min.

temperature,

a trap

containing in succession. Charcoal off with Kr cool-

NaOH H2

pellets,

and two is continued

charcoal until

at dry-ice after

temperature

bubbling are

the end of irradiation. pressure and sealed trap,

traps

evacuated in place. on the

to less Kr and

than Xe

5-microns are

ant still Xe coal

activities xenon

on the first is counted

and

but no char be by

activity trap

second.

The ionization

activity

by placing

the

in a well -ty-pe for determination

chamber. activity

Later

samples into

of xenon the

may

obtained repeating

of the xenon sweep.

growing

solution

the hydrogen

PROCEDURE

6 SEPARATION

OF

LONG

-LIVED

FISSION

GASES

Source

J.

A.

Ayres

and 1. B. Studies: Energy

Johns, The

Paper Fission Div.

311: Products, IV, Vol. pp. 9,

Radiochemical National Book This of xenon The tilling procedure from was 3, Nuclear

Series, New York

McGraw-Hill, in studies metal,

(1951),

1763. methods to 2-3~0 in a dis removed by or .

used

of the and gave

efficiencies results

of various reproducible is placed Air is

removal uranium

uranium

sample

containing connected with

fission

product

xenon train.

flask,

and the flask the entire

to the purification C02. The uranium

by flushing running

apparatus the rate

is then

dissolved

in 92~o H3P04,

of reaction

being

controlled

by warming

48

PROCEDURE

6 (Continued)

cooling the acid. enter

the flask Xenon,

as

required.

Dissolution and some

is very

fast

at the boiling iodine

point

of

hydrogen, train.

fission

product

and tellurium NaHS03 H20, amounts

the purification removes is condensed gases are

Bubbling Passage

the gases over

through

a saturated

solution which

I and Te.

hot CUO The

o~dizes xenon KOH. from

the Hz to and small

in a subsequent then collected

flask.

active over swept

of other ium

in a audiometer behind is

After the

the uraninto

is dissolved,

any xenon with C02.

remaining After

solution

the audiometer air The into being may

the C02 to provide

is removed an easily

by reaction handled

with KOH, of gas . chamber

be swept

in if necessary

volume

sample which

is withdrawn an Al finger-type

to an evacuated GM counter from

bulb is

connected The

to a counting aliquot

sealed.

of the xenon of the counting

counted

may

be calculated rest

knowledge containing

of the volume the sample.

chamber

and of the

of the system

PROCEDURE COLLECTION

7 REMOVAL ON THE

OF

Rn FROM OF

Th TARGETS A DISCHARGE

AND TUBE

ITS

CATHODE

Source

F.

F.

Momyer

and E.

K.

Hyde, Chemistry,

Journal 1, 274-95

of Inorganic (1955),

and Nuclear

The has proved

overall useful,

yield

of this

procedure for the

is no more and

tl@n

a few

percent. gases,

It on ,

however,

collection

retention gas

of rare nuclides.

wires

or foils The

in studies metal

of decay target

characteristics , irradiated with

of rare 340-Mev

thorium

proto,ns flask,

to produce

radon

isotopes

by spallation, concentrated

is placed

in the dissolver

the EyEtem catalyst sodium

evacuated, dropped hydroti,de passed

and hot

HC 1 containing Evolved a trap cooled

ammonium gases are

fluosilicate through

in to dissolve solution,

the thorium. passed through traps

bubbled.

cooled

in dry

ice/acetone, After closed are shut

and then solution off and the off from by

through

3 succe~sive

in liquid, nitrogen. solution The are traps

is complete 4 cold traps

the dissolver pumped down

and sodium to 10. -

hydroxide mm Hg.

10-5

the pump keeping of this cooled warmed, cathode. counting

and gases it immersed

condenmed in liquid distilled The

in the traps nitrogen into

are

distilled

to the

last .

trap

and warming

the others discharge closed to collect in this

The tube

contents which is

trap

are

finally nitrogen.

a tip on the glow tube a few is then

in liquid

discharge run for

off,

the tip radon on the under pro-

and a glow This

discharge has

minutes earlier

technique

been

discussed amounts

monograph impurities

procedures.

Usually,

small

of condensed

49

PROCEDURE

7 (Continued)

tide

a few

hundred one may

microns add some

pressure gas

to support

the disc~r.ge. or helium

If this

is not

the case,

much as air, tube. trap

nitrogen Any

to achieve on the

the necea~ary cathode for use may

prea~ure be frozen

in the discharge back into the last

radon

not deposited

at liquid

nitrogen

temperature

in later

experiments.

Notes 1, ment Stoner with and Hyde nitrogen heated 76 studied iaotope~ of radon produced gold was from by bombarddissolved in

of gold

ions

in similar

fashion. to remove

The

mercury 2,

while

being

by induction studied 100-Mev

the radon x~non

the target. produced The from pro-

Matt+ur

and Hyde77 of KI with with water

neutron protons

deficient uEing

isotopes procedure. removed radon

by bombardment KI was dissolved

a similar

in a closed the same

system series

and the xenon used

solution cedure. 3. -195 ments C

by pumping The The should NaOH

through scrubbing

of traps

in the

was

omitted. of trace amounta also of rare observed interfering gases in traps at

observed

retention

be commented product from rare radon

upon. gases

It was

in the radon ~-y activity all

expericould

that fission removed

and their

be largely briefly

by warming

the trap into meter

containing another

the gases C. the of The pres -

in air

and distilling monitored ceased product

the fission with a ~ -y

products survey

trap

at -195 until
90~0

Distillation activity the rare vapor sures in the

was

and continued Well

in the trap gas fission

to drop activity gases of rare

rapidly

(about

30 see). could

over

in the, radon at - 195C gases

be removed exceed

thus.

pressures

of the rare amounts

certainly

the partial

of the tracer cold traps

in the above

experiments. solids. further

Retention Speculation experimenis not on or

is thus mechanism worth

not due to condensation involved calling seems

of the pure without

as to the exact tal data. a result

pointless to the fact

It seems of processes with trace

attention the rare must

that the retention (that is, adsorption

involving

gases

alone

condensation under system which

other xenon, are

substances for e=mple,

be involved), might

so that

circumstances of a

not be held

up in a portion

at -195C

possible.

PROCEDURE

8 DETERMINATION BY THE CHARGED R. M.

OF WIRE

ACTIVE TECHNIQUE

GAS

HALF

-LIVES

(H) and A. Turkevich,

Source

C.

R,

Dillard, 68:

Adams,

H.

Finston, The Div. pp.

Paper National

Radiochemical Nuclear Energy New York

Studies: Series, (195 1),

Fission IV, Vol.

Products: 9, Book 2,

McGraw-Hill,

624.

A number short-lived rare

of the earlier gases were

experiments performed is

to determine using this

the half-lives technique.

of

interesting

A solution over vessel a 10-ft center tera placed a porous

of uranyl graphite

nitrate

contained which .syatem, diameter. volta

in a small may

polystyrene be bubbled. spray copper

vessel The to the

disk

through a baffle inner

nitrogen

ia connected aluminum of the tube of gaaeoua

through tube of

to prevent A fine to effect The

carry-over, wire down

1 -in.

ia maintained passing

at -1000 through

collection entire

of the daugh apparatua ia

activities

the tube. with

in a reactor flow rate

and the

a olution through

irradiated the ayatem.

neutrons

while

maintaining data the by

a constant linear cutting relative lived fair flow

of nitrogen of gaa

From tube may lengths

experimental be calculated.

through into

the aluminum a number activity

Thus the

the collector amounta gaa

wire

of equal

and determining

of daughter a daughter

on each

piece, half-life

the half-life may

of a shortwith

rare

with

of appreciable

be determined

accuracy.

51

REFERENCES
1

H.

Remy,

Treatise Eleevier and J. B.,

on Inorganic Publishing Manowitz, Sot.

Chemistry, Co. Ind. London, , New Eng. p.

Vol. York, Chem. 298,

1,

(translated

by J.

S.

Anderson), 2 3 4 M. H. Steinberg M.

(1956]. , 51, 300, 47-50 468 (1959).

Powell,

Chem.

(1950).

H. M. Powell, J. Chem. Sot. London, Part 2, 2658 (1954). 5 D. J. Ghleck and C, A. Ziegler, Nucleonica 17 (1959). ~ No. 9,.130 6 S. Katcoff and W. Rubinson, Phys. Rev. 91, 1458-69 (1953). ,, 7 F. Soddy, Proc. Roy. Sot. A78, 429 (1906). 8 A. S. Newton, AEC report series M. D.,D. C. 724. 9 I!Reduction. of CUO by Hydrogen. II. W. D. Bond and W. E. Clark, Conversion Laboratory 10 F. R. Bruce, of Hydrogen report J. to Water over Fixed Beds. Oak Ridge National

ORNL-2816 M. Fletcher, Progress or Pergamon Yaffe, J, Can.

(1960). H. H. Hyman, and J. J. Katz; editors,

Process Hill, llF. 12 ,0. A. New Brown E. C.

Chemistry, York, and L.

in Nuclear Press, J. Chem.

Energy,

Series p.

111, McGraw345.

London, 31,

(1956), 242-9

(1953), Applied and Sons, to Chemistry, Inc. New York,

Myers Wahl pp.

and R. and N.

Prestwood,, Editors,

in Radioactivity John Wiley

Bonner,

(195~, 13E. 14 N. 15 A. 16 N. J. S.

28-29. Vacuum 3, 287-88 (1953). Feb. Instr. 28, and 1959. 758-64 Their (1957). Compounds, Vol. I,

Wilson, Corney,

et al: , AERE-C/M-364, S. The Wu, Rev. Sci.

Sayres V.

and C.

Sidgwic~, Clarendon Allen and

Chemical (1950),

Elements p, JACS 27, 1. 53,

Oxford, 17F. 18 F. 19 M. 20 J. J,

Press B.

P. Ind.

Moore,

2512-22

(1931). / Clarendon

Metzger,

Eng.

Chem.

112-16

(1935). Otiord,

Ruhemann, (1949). Cady

Separation

of Ga~es,

2nd Edition,

Press G. H.

and H.

P.

Cady,

I.nd.

Eng.

Chem.

, Anal.

Ed.

1~,

760-6

(1945).

21

E.

Glueckauf

and G.

P.

Kitt,

Proc.

Roy.

Sot.

(London)

A234,

557-65

{1356). 22 Handbook Rubber 23 S. 24 R, 25 of Chemistry Publishing Co, and Physics, , Cleveland, Technique, Robinson, , New 39th Ohio. Jo~ Wiley and Sons, . New York, (1949). Edition, 1957-58, Chemical

Dushman, E. Dodd

Vacuum and P. L.

llE~perimentil Inorganic Chemistry, _

York, (1954). of Volatile Compounds, John

Elsevier R. S.

Publishing Sander son,

Co. Vacuum

Manipulation ( 1948). (1918); and E. Physik.

Wiley 26 27 28 I. S. K.

and Sons,

New

York,

Langmuir, Brun~uer, Peters

JACS P. and K. H.

40,

1361,

also Teller, Chem.

Chem. JACS 148(A),

Revs. 60,

13, 309

147

(1933).

Emmett Z.

(1938). available

Weil.

1-26

(1930)

as AEC-tr-2470 29 S. Brunauer,

(35 pages). The Adsorption of Gases and Vapors, Press, Vol. I, I!Physical N. J. ~

Adsorption, (1 943). . . 30W. 31. J. 32 V: 33 F. J. R. Wolff, Kipling, Deitz,

!, Princeton,

Princeton

university

,Princeton~

J.

Phys.

Chem.

62,

829-33 (Chem.

(1958). Sot. London) 190010, 1942, 1-26 (1956).

Quarterly llBibliograpb

Retiews

y of Solid

Absorbents, D. C. , 317: Energy pp. A185, 1944.

National

Bureau R. A.

of Standards, Ladd and T. F.

Washington, Young,

Paper

Radiochernical Series, 1833. 98 Can. (1946). J. Div.

Studies: IV, Vol.

The 9,

Fission Book 34 35 E. W. 3,

Products, McGraw-Hill, Proc. K. F.

National New Roy.

Nuclear York Sot.

(1951), (London)

Glueckauf, J, Arrol,

Chackett,

and S.

Epstein,

Res.

27B, ,

757-63

(1949). 36 A. I. M. Keulemans, , New JACS JAGS Gas York 62, 65, Chromatography (1959). 1583 532 L. (1940). , 2nd Edition, Reinhold Pub-

lishing 37J. 38D. 39 A. N.

Corp. Wilson,

de Vault, J. P.

(1943). M. Sy-ngej Biochem J. (Londonj 35 1358

Martin

and R.

(1941). 40S. 41 E. 42 L. 43 E. 44 W. Mayer and E. Trans. and N. R. R. Tompkins, 50C. 51, J. JACS 69, 2866 (1947).

Glueckati, Lapidus Gluecka&,

Far.

34 (1=55). Phys. Chem. 56, of Ion Exchange London, S. S. S. R. 5-7th (Compt. ,, 984 (1952).

Amundson,

l~principles

of Operation

coIu~,

paper

read N. sci. 45 J. C. N.

at the Conference Tunitskii, 99,

on Ion Exchange, Akad. Nauk.

April,1954.
rend. acad.

Doklady 577 (1954).

URSS)

Giddings

and H.

Eyring,

J.

Phys.

Chem.

59,

416

(1955).

46

J. Sci.

J.

van ~,

Deemter, (1956 ).

F.

J.

Zuiderweg,

and A.

Klinkenberg,

Chem.

Eng.

271

47

A.

Klinkenberg Glueckauf, B. E. Amphlett Adams,

and F. AERE

Sjenitzer, C/R F. 2435 (4)

Chem. ( 1958).

Eng.

Sci.

~,

258

(1956).

48E. 49C. 50 R. 51 ~ 51 W. 52 R. 53 A. 54 E. Vol. 55 E.

and B. W. E.

Greerdikld, Jr.

AERE-C/R-2632 and R. D. Ackley,

(July Lnd.

1958). Eng. Chem.

Browning,

1467-70 E. C, L. R.

(1959).

Browning Koch

and C.
F. L. and A.

C.

Bolts,

ORNL-2116

(1956).

and G.

Grandy,

Nucleonics Ind.

Lindsay Weaver, II,

Bromley, Methods Inc. , J.

18, No. 7, 76-80 (1960). Eng. Chem. 42, 1508 (1950), Analysisi pp. W. 387-437. J. Taylor, G. Berl, ed. ,

Physical Press, Evane

in Chemical New York J.

Academic C.

(1951), Eakins

J.

Wilson, I/R 2216

Chadwick,

and K.

AERE 56 57 R. D. M: W.

(1957). and A. W. 78, G. B. Robins, R. Trans. M Far. Milton, Sot. T. 49, B. 807 (1953} and T. L.

Barrer Breck, JACS K,

Eversole,

Reed

Thomas, 58 M. Krejci,

5963-77

(1956). Janak, 2nd Biannual 2, p. 105, international Instrument Gas Society

T es arik

and J.

Chromatography bf America, 59J. A. Ayres

Symposium Pittsburgh, and 1. B.

( 1959)

Vol.

Pennsylvania. Johns, Paper 311: Energy (1951), 1823. Epstein, Can. J. Res. 27B, 757-63 pp. Radio chemical Series, 1763. Div. Studies: IV, Vol. The 9,

Fission Book 60 61 3,

ProductB, McGraw-Hill, 59, K.

National New 316, Chackett

Nuclear York pp.

Reference W. J. Arrol,

Paper F.

and S.

(1949). 62 63 64 M. A. S. B. C. A. Reynolds, Wahl, Korff, J. Nut. lnorg. Sci. and Eng. Chem. ~, 374-84 ~, (1956). (1958). Nostrand Inc. New York

and Nut. and Nuclear

263,-77 Van

Electron

Counters,

(1946). 65 B. B. Ros si and H. Energy Sikkema, Cockcroft Mann H. Staub, Div. Instr. C. Ionization V, ~, Vol. 2, Chambers McGraw-Hill, (1957). Sci. Sci. Instr. I.nstr. sci. 22, 20, 37 (1951). 41 (1949). No. 30, and Counters, New York National (1949).

Nuclear

Series, Nuclear and S. B.

66 C.
67 68 69 A. W. G.

P. L. B.

148-51 Rev. Rev.

Curran,

and G. and C,

Parkinson, Bull.

Delibrias (1959) Rosen 59,

Jehanno,

inform.

et tech.

(PariB)

14-15 70 71 72 F. D.

(in French). and W. Book Davis, 2, Paper 1201 Jr. K-678 pp. (Nov. 1052. 1950).

Reference M. B.

150, (Sept.

Reynolds,

KAPL-

1954).

73

A. for

Wattenberg Jan. H, F. , Feb.

and W.

H.

McCorkle, 1950,

editors, Argonne

PhyBics

progress

report ANL-4437.

, and h4arah

National

Laboratory,

74 75

A. F.

Snell

and F. Jr.

Pleaaofiton, and E. K,

Phys. Hyde,

Rev. J.

107, 740-5-(1957). and Nut. Chem ~, 274-95

Momyer,

Inorg.

(1955). 76 77 78 A. H. R. W. B. Stoner Mathur and E, and E. and L. K. K. Hyde, Hyde, J. Inor& and Nut. 96, Chem 126 ~, 77-83 (1957).

Phya. Paper

Rev. 67:

(1954}. Studies: IV, Vol. 9, The

Overstreet

Jacobson,

Radiochemical Series, 621. Div.

Fiesion 79 80 81 Book . Itnd, J. J. A. A. 2,

Products, McGraw-Hill, 68, pp.

National New 624.

Nuclear York

Energy (1951), pp.

Paper

Northrop Northrop, 81-7

and JuditE J. C.

C.

Gureky, and ~.

Nut. E.

Instr.

~,

207-1~ IRE

(1958).
Nut. Sci. ,

Gursky

Johnsrud,

Trans.

NS-5, 82 A.

(1958). and C. S. Wu, 139, 1005. 85, 97, and 356. and E. J. Wilson fiRE I/R 2224 (1957). Rev. pp. Sci. 984. Instr. 28
No.

Sayrea

10,

758-64

(1957).

83 Reference 78, Paper 84 Ibid, Paper 141, pp. 85 Reference 86H. p. 10, pages J.

Dibbs,

D. Eakins .