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s
ls
JNNNlH
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THE
MANIPULATION
F
AIR.SENSITIVE
OMPOUNDS
SECOND
EDITION
D. F.SHRIVER
Nort hu'es
ertt U tt
vers
I
v
Evonstott.
Illinois
M. A. DREZDZON
Antoco
C
hetn cu s
Contpurty,
Nuperville, Illittois
A Wiley-lnferscience
ublicotion
JOHNWITEY SONS
New York
/
Chichester
/
Brisbqne
/
Toronlo
/
Singopore
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
4/334
Copvr ight
i ' 1986bv
John
Wile l
ct
Sons.
nc.
A l l r i gh t s ese rve 'd .
ub l i shed
in ru l t aneous l t
n Canada .
Reproduct ion
r t ranslat ion
of anv part of
thrs
u
ork
be1'ond
hat
pernr i t ted
b1'Sect ion107or l0U of
the
1976
United StatesCopl ' r ight
Acr
\ \ ' i thout
he
pcrnr iss ion
o f
the cop l ' r i gh t unc r s
un lau fu l . l cqucs t sor
pcrnr iss ion
r fur ther
in{ornrat ion
houldbc addressed
t,
t he Pe rm iss ions
epa r tmcn l .
ohn
Wi lo
& Sons . nc .
Libru4' td
Congre.ss
Cutaloging in Publication
Data:
Sh r i ve r ,D . F ' .
Du* ' a rd
F . ) . 193 .1 -
The
manipulat ionof
a i r -sensi t ive onrpounds.
A
Wile- , - - ln terscience
ubl icat ion.
lnc ludes
bib l iographical
eferences
nd index.
l . Chem is t r v -Man ipu la t i on .
2 . Vacuumtechno logy .
3 . P ro tec t i ve
tmosphe res . , { .
A i r - sens i t i ve
on tpounds .
I . D rezdzon .
M . A .
(Mark
A. )
I I . T i t l e .
QD6l .557
l9rJ6
542
lsBN
0- .171-86773-X
8 6 - 10 l 2
Pr inted n the Uni ted States f Amer ica
r0
9 8
7
6
5
,1
3 2 I
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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PREFACE
The continued
mportance
of research nd development
with
air-sensitive
om-
pounds,
coupledwith the
general
ack
of
publications r undergraduatenstruc-
tion
on the
techniques sed
n
this
area,
prompted
us
to
revise his monograph.
The
levelof
presentation
s designed o make he book useful o t he chemist
who
is
beginning
work in the field.
In
addition, considerableechnicaldata and
in-
formation are
given
that should aid chemistsat
all levels
of
proficiency
n the
design
of experiments.
In
the belief
that the beginner
needs
a selective pproachand the
more sea-
sonedworker will exercise is ngenuity,wehave efrained rom presenting rief
references
o
many
similar
items of equipment,
but
have attempted o
present
rational approaches
o the
common operations nvolved
n
the synthesis, epara-
tion, and characterization
f air-sensitivematerials,and to il lustrate hese
with
typical apparatus.
Whenever
possible,
heseexamples
are
based
on
equipment
with which we havehad experience r on firsthand
observation f
the equipment
usedby others.This has resulted n
a
somewhat
ersonalized
ccount,
which we
hope
will
ensure
eliability
without
being objectionable
o established
workers
with
different
preferencesn
equipment design.The techniques iscussed
ere
were
argelydeveloped
or
use
with
inorganic and organometallic ompounds;
however, hey are
generally
useful
or problens involving
gases
nd
air-sensitive
solidsor
liquids,
so
they find application n all areas
of
chemistry,as
well
as
biology and
physics.
We had two
goals n
mind
while
writing this second
dition. The first was
o
bring the
text
up to date. Alt hough there have been no
radical new develop-
ments, here
has
beena
steady mprovement
n
technique.
Our
second bjective
was
o make the book more accessibleo the reader
nterestedn a specifi c ech-
nique. Thus more sectionheadingsare used and more detailed
examplesare
given.
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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PREFACE
The
continued
mportanceof research nd
development
with air-sensitive om-
pounds,
coupled
with
the
general
ack of
publications
r undergraduatenstruc-
tion on the techniques sed
n this area,
prompted
us
to
revise his monograph.
The level
of
presentation
s designed
o make
he book
useful o the
chemist
who
is
beginning
work in
the
field. In addition,
considerableechnical
data and in-
formation are
given
that should aid chemists
at all levelsof
proficiency
n the
designof
experiments.
In the belief that
the beginnerneeds
a
selective
pproachand
the more sea-
sonedworker will exercise is ngenuity,we have efrained rom presenting rief
references
o
many
similar
items
of equipment,
but have attempted
o
present
rational
approaches
o
the common
operations nvolved
n
the
synthesis. epara-
tion, and characterization f air-sensitive
materials,and
to
il lustrate hese
with
typical
apparatus.Wheneverpossible,
heseexamples
are
based
on
equipment
with which we have
had
experience r on
firsthand
observation f
the
equipment
used
by
others.
This
has resulted n
a somewhat
ersonalized
ccount,
which we
hope will ensure
eliability without
being objectionable o established
workers
with
different
preferences
n equipment
design.
The techniques iscussed ere
were
argely
developed
or use
with
inorganic and organometall ic ompounds;
however, hey are
generally
useful
or
problems
nvolving
gases
nd air-sensitive
solids
or
liquids, so they find application n all areasof
chemistry,
as
well
as
biology and
physics.
We
had two
goals
n mind
while
writing
this second
edition. The first
was
o
bring
the
text up to date. Although there have been no radical new develop-
ments, here has beena
steady
mprovement n technique.Our
second bjective
was
o make
the
book more
accessible
o
the
reader nterestedn a speci fic ech-
nique. Thus more
section
headings
are used
and more detailedexamples
are
given.
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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PREFACE
In
the
preparation
of the
first
editionof
this book aid
u'as
eceivedrom nrany
people:
. L . Al l red,
F. Basolo,
R. L. Burwel l ,Jr . ,E. W. Schlag, au lTre ichel ,
R.
W.
Fowells,
and Shirley Shriver.
Useful suggestionsor
the
second
edition
were providedby L. Aspry, R. L. Burwel l , Jr . , P. Bogdan. N. J . Cooper,
D. Kurtz .
J.
Malm,
and S. H. Strauss.
or a id n
proofreading
e
appreciatehe
help
of Ann Crespi ,
Cynth iaSchauer,
Danie l Shr iver nd Ralph Spindler .
D. F. Ssnrvrn
M.
A.
DnpzpzoN
Evanston.
Illinois
Nuperville. Illinois
Februum,
I986
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CONTENTS
INTRODUCTION
PART INERT-ATMOSPHEREECHNIOUES
'l
grNcx-rop
NERT-ATMospHERETEcHNToUES
l . l Techniquesor
Purg ing
and Dry ing Apparatus,
1.2 Adaptat ions
f
StandardGlassware,
I
1.3 Syr inge nd Cannula
Techniques,3
1.4
Quant i ta t ive
Gas Manipulat ion,
24
I .5 Schlenk
Iechniques,
30
1.6
Cappable
Pressure eactors,4 l
l
7
Hot Tube and Sealed
ube
Technioues.
2
General
References.44
2
INERT-ATMosPHERELovEBoxEs
2.1
General
Designand Appl icat ions,
5
2.2 Replacement f Air by an
Inert
Atmosphere. 7
2.3 Sources f and Reduction
of
Impurities
n
Glove
Box
Atmospheres. 1
2.4 Glove
Box
Hardware and
Procedures, 9
2.5 Typical
Glove
Box Systems, 2
2.6 Equipmentand
Operat ions,
4
General References. 6
3
INERTASESNDTHErR
uRrFrcATroN
3 .1
Sources
nd
Pur i t y ,68
3.2
Pur i f icat ion f Gases. 9
45
68
vl l
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v i i i
3 .3 Inert-Gas
Pur i f icat ionSystems, 0
3.4 Detect ion
f
Impur i t ies,83
General
References.
3
4
puRrFrcATroN
F sotvENTs
NDREAGENTS
4.1
Solvent
Pur i f icat ion. 4
4.2
SolventStorage,
89
4.3 Detect ing
mpur i t ies,
89
4.4 Pur i f icat ion f Speci f ic o lvents,
0
4.5 Pur i f icat ion
f
Some
Commonly
Used
Gases,
2
4.6 AnhydrousMeta l Hal ides,
5
GeneralReferences.96
PART VACUUM
LINE
MANIPULATIONS
5
vAcuuM
LINE ESTeNND PERAIToN
5.1
GeneralDesign,
9
5.2 In i t ia l Evacuat ion.
03
5.3
Manipulat ionof
Volat i le
L iquidsand
Condensable ases.
04
5.4 Lorv-Tenrperatureaths.109
5.5 Vapor Pressure
s
a
Characteristic
Property, l3
5.6
Manipulat ionof Noncondensableases,
l3
5 .7 Sa fe ty , 16
GeneralReferences.
l7
6
PUMPsoRRoUGH NDHIGH AcuuM
6.1
Rough-Vacuunl ystems,
l8
6 .2
H igh -Vacuum
ump ing
Sys tems ,
l 9
General References. 28
7 PRESsURENDFLOw
MEAsUREMENTND
IEAK
DETECTION
7.1
Manometry
l-760
torr) , 129
7 .2
Med ium-
and
High -Vacuum
Measuremen ts
10
r -10 6
to r r ) . 137
7.3
Leak
Detect ion.143
7.4
Flow
Measurement. 46
7.5 Flow Contro l . 149
GeneralReferences.
50
CONTENTS
. t . t8
84
99
t29
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CONTENTS
8
JorNTs,ToPcocKs,
ND ALVES
8 .1
Jo in ts , 52
8.2
Stopcocks, 61
8.3 Valves.
164
9 spEcrALrzED
AcuuM
LINE eutpMENT
ND pERATtoNs
.r68
9.1 Character izat ion.
68
9.2
Separat ions,
90
9.3
Storage
of Gases
and Solvents,
00
9.4
Sealed
Tube Reactions.
02
9.5
Miscel laneousechniques,
06
General
References.
08
'10
MEIAL
YsTEMS
l0 . l
Compressed
ases,
10
10.2 Cutt ingand BendingTubing, 214
10.3
Tubing,
Joints,and
Fit t ings,
215
10.4
Heavy-Wal led ubing
and
Pipe
Joints, 19
10 .5
Va lves .
22
10.6
Pressure
Gauges,
227
10.7
Typica l
Meta l
Systems,
27
General
References.
36
APPENDIX
SAFETY
I . l Combust ib les,37
I.2
Unstable
Compounds,
38
I.3 Some
Dangerous
Mixtures,
238
L4 Disposal
of
Reactive
Wastes,
239
I.5 High-Pressure
as
Cyl inders.
40
I.6 Asphyxiat ion
y Inert
Gases,
40
I.7 Ext inguish ing
ires,
240
General References.
41
APPENDIX
I GLASS ND
GLASSBLOWING
I I . l Propert ies
f
Glasses, 42
IL2 Equipment
and
Mater ia ls ,
45
II .3 Sequence
f Operat ions.
47
I I .4 Annea l ing ,247
l l .5 Cutt ing
Glass
Tubing,248
IL6 Bending
Glass
Tubing,249
II .7 Test-Tube
Ends
and Fire
Cutof fs .249
210
237
242
I X
152
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I I .8 End- to -End
ea ls . 51
IL9
T-Seals. 53
I I . l0
R ing
Sea ls . 53
I . I
I
ClosedCircu i ts .
255
II . l2 Meta l- to-Glass eals. 55
I I . l3
Heal ing
Cracksand Pin
Holes,
256
IL14
Seal ing ubing
under
Vacuum,257
General
References.
58
APPENDIX II PLASTICSAND ELASTOMERS
II I . I
Plast ics:
Genera l
Propert ies
nd Fabr icat ion.260
I lL2
Cel lu larPlast ics.
65
II I .3
Propert ies
f Speci f ic last ics, 67
I I I .4 E las tomers .272
l l l .5
Propert ies
f Speci f ic
lastonrers,
72
General
References.
74
APPENDIX
V
METATS
IV. l
Propert ies
f Speci f icMeta ls ,276
General References. 80
APPENDIX
V
VAPOR PRESSURES
F PURESUBSTANCES
V.l Analy'ticalRepresentation f Vapor
Pressure ata.
281
V.2 Least-Squares
itting Procedure or
the
Anto ine
Equat ion,28.1
V.3 Corre lat ion
nd
Est imat ion
f
Vapor Pressures,
86
V.4 Table
of
Vapor
Pressures.
89
V.5 Sources f Vapor
Pressure ata. 313
APPENDIX
I
PRESSURENDFLOW ONVERSIONS
INDEX
CONTENTS
259
275
28tl
3,15
3.19
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INTRODUCTION
A.
Generol
Mefhods. The mostwidelyusedmethods
or handlingair-sen-
sitive
compounds
are
based
on the useof an inert
gas
atmosphere
o excludeair.
This approachmay be
urther
subdivided nto
(
1)
hose echniques
which nvolve
bench-top
operationswith
special
glassware
often
called Schlenk
echniques,
Chapter
1)
and
(2)
glove
box techniques n
which
conventionalmanipulations
are
perfornred
n an inert-atmosphere
ox
(Chapter
2). Both
of these
methods
may be used
o
handle arge
quantities
of solids
and
liquids;
however, he
Sch-
lenk
type equipment s
generally
much more efficient
and
more
secure rom
the
atmosphere han the dry box. Th e
principal
advantages
f the
dry
box lie in its
use
or
intricate manipulationsof
solidsand for
the
containment
of
radioactive
and/
or highly
poisonous
ubstances.
More rigorous
exclusionof air and the
quantitative
manipulationof
gases
s
achieved
n a
previously
vacuated pparatus.
This vacuum
ine method s
out-
lined in Chapter5, where
he basicoperations
are described,
uch as
quantita-
tive
transferand
pressure-volume-temperature
easurement
f
gases,
rap-to-
trap separations of volatile materials,
and
the use of vapor
pressures
o
characteriz e ubstances. ucceeding hapters
6-8)
describe n
detail
the
indi-
vidual
vacuum ine components
uchas stopcocks,
oints,
diffusion
pumps,
and
manometers.Many accessorytems such as spectroscopy ells,vapor-pressure
thermometers, nd
gas-chromatography
pparatusare described
n Chapter
9.
This set
of
chapters,
plus
supplementary
material in
the Appendixes,
orm
a
guide
to modern
glass
vacuum ine
practice.
This
techniquehas
beenused
suc-
cessfully
n
the synthesis
nd
manipulationof hydrides,
halides,
and manyother
volatile substances.However,
glass vacuum
systems
are
not
appropriate
for
hydrogen luoride
and
someother
reactive
luorides.These
are best
handled n
the
metal or fluorocarbonapparatus
described n Chapter 10. The
strengths f
these
various
echniques
or
handling air-sensitive
materialsare summarized n
Table
l
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z
INTRODUCTION
Toble
1
Comporison
of lnert-Almosphere
nd Vocuum
LineTechniques
Technique
Exclusion
of
Air
Quantit ies
OutstandingFeatures
Schlenkand
syringe
Glovebox
Vacuum
ine
Good
to
very
good
Poor
to very
good
Very good
to
excellent
Medium
to
large
Small
to
very
large
Very
small
to
medium
Rapid
and easymanipulat ion
of solut ions;
imple ansfer
of sol ids
lntr icate transferoperat ions;
containmentof poisonous nd
radioact ive ubstances
Quantitat ive
gas
handling;
transferand
storage
f
volat i le
so lvents i thout
contamina l ion
Verysmal l , about I mgl smal l . about 100mgl medium, several ramsl arge,hundredsof grams;
very arge.
k i logranrs.
B. Plonning
lhe Expeliment. Whatevergeneral
echnique s used, t is
m-
portant
to
plan
each new
experiment n
detail.
Impasses
an
be
avoided
b1'
sketching
he
setup
at
eachstep
with
due attention
paid
to
the
method or
trans-
ferring materials.
f measurements
re nvolved,
a simple
estimate
f
the
poten-
tial errors shouldprecede
he
newly planned
experiment
o ensure hat
results
will
be determined
with
meaningful
accuracv.
Frequently.
uchan estimate
will
suggest onditions
and apparatus
designswhich will
minimize he
errors
without
in troducing
ny new
compl icat ions.
C.
Appololus
Design. Sometimes
t i s necessary
o designand
construct
specialapparatus.
Three criteria for
a
good
design
are:
(1)
Is
it the sinrplest
designconsistentwith its
intended purpose?
2)
Is it robust?
(3)
Is
it easy o
clean?
To
ensure
hat an item
is
sturdy t
shouldbe
designed
o
hat
stresses
re
not concentratedn small sections f glass.For pernranentnstallations, uchas
a vacuum ine.
a l l
heavy tents
are
ndiv idual ly
upported.
vh i le
he
ighter
sec-
tions
are
clampedat
the
minimum number
of
points
u'hich
suffice o
support
he
apparatusand
avoid
everage.
Generall,v.
ortableglass\Ä'are
houldbe designed
as
one
strong,
compact
unit \r 'hich
may
be supportednear a
point
of balance.
Final ly , he mater ia ls
f
construct ion
ust v i thstand
he chemicals nd so lvents
which
are to
be
handled. The
most f requent problems
ar ise
with
stopcock
greases,\'axes,
ubbers,
and
plastics.
These
problen'ls
may
be minimized
by se-
lectingmaterialson
the
basisof
the information
on chemicaland solvent
esis-
tance
which is preserrted
n
Chapter
8 and Appendix
IIl. To aid in
the
proper
choiceof metals, nformationon their corrosion esistancesgiven n Chapter10
and Appendix
V.
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A
PARII
Inert-Atmosphere
Techniques
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8 eENcH-Top
NERI-ATMoSpHERE
EcHNtoUE
evacuat ion f the
apparatus, nd f there
are
no eaks n
the apparatus,
repet i -
tions of
the
pump-and-fil l
process
will reduce
he
fraction
of
atmospheric ases
A ,
to
The
second
method
or removing
atmospheric
ases
nvolves weeping
ir out
of
the apparatusby a flush of inert gas.
The
factors
which nfluence
his type of
process
re discussedn
detail
in
Chapter
2.
For
the
present. t is
adequate
o
note
that a conti nuous lush of inert gas, u'hich pushes
he atmospheric
ases
from
one extremeof
the apparatus
o an outlet
on
another
extreme,
as in Fig.
1.1,
s most
ef f ic ient . h is
so-cal led
lug
low
s
dif f icu l t
o achieve
i th
s ingle-
neck
lasksand
similar
apparatus.
A
flow of inert
gas
which
bypasses
art
of
the
apparatus
s
relatively
nefficient.
B.
Purging on
Open Vessel. In
many
operations
described
n
this chap-
ter,
it
is necessary
o open he apparatus
briefly
while
an
inert-atmosphere
lush
is maintained out
of
the opening o minimize the entranceof air. Even under
conditions
n
which
there is
litt le
turbulence
n
the flowing
inert gas
stream,
Iner l -gas
rn le t
2
+
To
nooo
--\
+
( l )
\
water
Mine ra l
o i l bubb le r
F ig.
l . l . Three-necked
eact ion
lask wi th
dropping
funnel .
st i r rer ,
and ref lux condenser .With
the dropping
unnel stopcock
n
the
open posi t ion.
a f lou
of iner t gas
rom in let I through
he min-
era l o i l bubbler
ef f ic ient lypurges
he
apparatus
of atmospher ic ases.
Dur ing
react ion
and subse-
quent cool ingof the react ionmixture. a s low low of inen gas ronr in let 2 through he mineraloi l
bubbler prevents
tmospher ic
ases rom
backing
up into the system.
nd th is
conf igurat ion
mini-
mizes
exposure f
the react ion
mixture to impur i t ies
n thc-
ner t gas.
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TECHNIOUES
ORPURGING
ND DRYING PPARATUS
therewill be
countercurrent
diffusion
of atmospheric
ases.
An
estimateof
the
flow
rate
necessaryo maintain the
partial pressure
P11
f
an atmospheric om-
ponent
at somedesired
partial pressure
P inside
he apparatus s
given
by
the
equationl
L
-
-(ADt.2/X)ln(P/Po)
Q)
where,4 s he cross-sectionalreaof the tube hroughwhich hegas s ssuing,X
is
he lengthof this tube, and D1.2 s
the diffusioncoefficient
f
the mpurity
gas
I in
the
inert
gas
2. In round
numbers, the diffusion coefficient
of
oxygen n
nitrogen
s 0.2 cm2ls at I atm
total
pressure,
nd
a
desirable
artial pressure
or
oxygenwithin
the apparatusmight
be
10-r
orr. If
we
assume
hat the
neck
of a
flask s 1.5
cm
in
diameterand 5 cm long. Eq.
(2)
ndicates
hat a
nitrogen low
rate
of only 50 cm3/min would
be
required
o
maintain
this
low level
of oxygen.
Experience eaches s
that
far larger low rates
are
required;
somethingon the
order
of several
iters
per
minute would
be typical under heseconditions.Even
though Eq.
(2)
doesnot appear
o apply o the rather argeopenings ommon o
many preparative- scalepparatusdesigns, t is probably much more accurate
for the
less
urbulent flow
of
gas
from
smaller-diameterubing. The
general
form of t he equation s sensible,
uggestinghat the
entrance f air is reduced
by
a lon g-necked lask with
a small
cross
section
or
this
neck.
C. Monifold fot
Inert
Gos ond Vocuum.
Pure nert gas.generally
itro-
gen
but sometimes
rgon or helium,
is required or the
operations
escribed n
this
chapter. As describedearlier, equipment
s fi l led with
the
gas
by
purging
with a large volume of
gas,
or
evacuation
ollowed
by fi l l ing
with
the
gas.
To
accomplish hesepurging operations n an efficientmanner t is handy o have
an
inert-gasmanifold
with
severalheavy-walledlexible vinyl or rubber
tubes
attached o
provide
nert gas
o separate
ieces f
apparatus.A mineraloil bub-
bler,
or occasionally mercurybubbler, is attached o
the
gas
outlet on
the
ap-
paratus
o
protect
against
excessive
ressure.
When
the
pump-and-fil l
technique
s used,
a
more complexmanifold or the
distribution
of
inert gas
and vacuunl s
generally
mployed,
n
conjunction
with
a
liquid nitrogen-cooled
rap,
mechanical acuum
pump,
and
pressure
elease
bubblers
Fig.
1.2) .
This manifold
can be used o
purge
several
ieces
f apparatus
at once,
and
the two-way stopcocksor valvesprovide a ready means of switching between n-
ert
gas
and vacuum.
Sources
f
purified i nert gas and vacuum
are
attached
o
this
manifold.
An oil bubbler
on
the
nert gas
nlet
serves
s
an approximate
low
indicator.
The inert
gas s controlledat the tank
with
a high-quality
dual-stage
diaphragm
regulator
which is designed
or
good
regulation
around 3
psig
(915
torr).
A
pressure elease ub bler
is often included on
the inert
gas
ine. Glass
stopcocks
ttached o these
manifolds
will becomedislodged
y the small
posi-
tive
pressure f
inert gas.Therefore,
t is essential
o
secure hese
topcocks,
nd
rG.
Antos.
Ph.D.
Thesis,Nor thwesternUnivers i tv .1973.
I
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,10
BENCH.TOPNERT-ATMOSPHERE
ECHNIQUES
To vacuum
pump
Pressure
elease
bubbler
To
apparatus
Low-temoerature
trao
Fig.
1.2. Mani fo ld for medium vacuumand
nert
gas.A
low-temperaturerap,
on the r ight s ide
of
the igure, s used
n the vacuum ine
o
protect
he
pump
from
harmful
vapors.When
the apparatus
is
being i l led
u ' i th gas
or
purged * ' i th
iner t gas.
he
valveon the pressure e lease
ubbler
(uhich
conta ins
checkvalve
o
prevent
i l
f rom
backingup into
the
ine) s opened o avoid
excess
ressure
u'h ichwould
blo*
the apparatus pär t . Of len a mineralo i l bubbler
nol
shownhere)
s
connected
n
l ine u ' i th
the
iner t -gas
ource o
providevisual ndicat ion
of the iner t -gas
low.
al l o thers used on
inert-atmosphere
quipment,
wi th h igh-qual i ty p lug
retainers.2
Details on
the
purification
of
inert gases
can
be found in
Chapter
3. The
source
of vacuum s
generally
a rotary
mechanical
acuum pump. The pump is
protected
rom
chemicals
nd solvent apor
by
means
of
a
trap cooled y
Dry
Ice
or,
preferably,
iquid nitrogen.
CAUTION: A
liquid nitrogen rap
must
neverbe
connected
o
a
manifold
where
he
vacuum
sourcehas been
urned
off. Failure to
remove
a
liquid
nitrogen
trap from a manifold
after shutting
off
the
vacuum
will
result
in the
condensationof liquid
air
in
the trap. If warmed
up,
this liquid
air
will evaporateand may pressurize he apparatus, presentingan extreme explo-
sion hazard.
It
is
desirable or
this
trap to
be
deepenough o extend o the bot-
tom of
a
l-L
Dewar, thus permitting
ong-term
cooling.
The
trap shouldbe eas-
ily removed
so that accumulated
ondensables an
be
readily
(and
frequently)
discarded.
D. PUrging
Sylinges. Syringes
re
conveniently
urged
rom an inert-gas
source
uch sa tube
with
a
rapidly
lowing nert-gas
tream
r
a special eptum
attached
o
the
nert-gas
anifold.Two
or threecycles f filling, emoving
he
'Excel lent
reta iners
K-809000) .
which
must
be used
u' i th
stopcock
lugs
ront
the
sanremanufac
turer , are avai lable ronr
KontesGlassCo. Vineland
NJ.
.r'
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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ADAPTATIONS
F STANDARD LASSWARE
needle rom the inert-gas
source,
and expelling he gas
are sufficient.
f
the sy-
ringe
is
going
to be used
o remove
iquid
fronr
a flask
which is
being
rapidly
flushed,
he
inert gas
may be
drawn from
the
flask and expelledoutside
of the
flask
to
purge
the syringe.
When
highly
moisture-sensitive aterials,
such
as
aluminum alk yls and activeborohydrides,
are being
handled,
he
syringeparts
should
be
stored in
a
drying oven
around 130"C and removed
ust
prior
to
purging.
E. Drying
Glosswore. The
purging procedures
escribed
hus far remove
relatively itt le of
the moisture
which
is adsorbed
n
glass
surfaces.When
han-
dling compoundswhich
are
highly
moisture sensitive.
uch as
aluminum hy-
drides.
borane
adducts, and
lithiunr
alkyls,
t is often
n'rportant
o employspe-
cial drying
procedures.
A drying oven
set at around
l30oC can
be
used
o bake
out
glassware
or severalhours
prior
to use. This
glassware
hould be flushed
with dry inert
gas
as t cools.To prevent
apparatus rom
sticking
ogether,stan-
dard taper
joints,
stopcocks,and
syringes hould be completelydisassenrbled
before hey are placed n the oven.
Alternatively,
he
glasswaremay
be
flushed while
it is
being heatedwith
a
Bunsen
burner
or
heat
gun.
CAUTION: When
using a Bunsen
burner or heat
gun
to dry
glassware,
all flammable
materials must be removed
rom
the area.
If
the glassware
has been rinsed with
a volatile
solvent, such
as acetone
or metha-
nol, to aid the drying
process,
he residual
solvent vapors should
be removed
from the
glassware rior
to
drying by
purging
severalminutes
with inert
gas.
The
heating s startednear he nert-gas nlet and
carriedalong
he apparatus
ou'ard
the gasout le t .
Silylating
agentshavealsobeenused o treatglassrvareeforehandlingnrttis-
ture-sensi t ive
ompounds.
or example,
ch lor ine-ternr inated
ol-yd inteth-y l
i -
loxane s
avai lab le
ontnterc ia l ly . r
lhese
reagents
uppress
he basic i t l 'o f
he
glass
and
provide
a
hydrophobicsurface.
4.2
ADAprATroNs
FsTANDARDrAsswARE
Many operations
vith
air-sensitiveiquids
can be
perfornred
n
standard
aper
glassware
itted
with
a bubbler and inert-gas
ource.NOTE: To avoid blowing
apparatus apart, stills and reaction pots should be vented to a bubbler before
they
are heated.Figure I . i l lustrates
a typical
setup
or
a
three-neck eaction
flask equipped vith
a dropping funnel,
stirrer, and reflux
condenser. his
ar-
rangementprovides
several mportant features
or
safeand
efficientoperation.
Inert-gas nlet
I and the
oulet
hrough
the mineral oil
bubbler are
positioned
or
efficient nitial
purge.
Pressure
uildup, especially
uring heating, s
avoided y
allowingpressure
eleasehrough the
bubbler. A constant
slow low of inert
gas
rThis
nrater ia l s so ld under
he
nanre
Glassclad v Petrarch
Slstcms. nc. .
Bar t ranrRoad. Br isto l .
PA 19007.
1 1
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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o
HJ
St r
-head
the rmomete r
Insu la ted
v
rgera
x
c o l u m n
t o
nooo
Iner l -ga
in le t
3
Mrne ra l
o i l bubb le r
Receiver
Heatrng
man t le
Fig. 1.3. Dist i l la t ion
under iner t a tnrosphere
sing modi f iedstandard
aper
r 'are.Note
he
side-
arnr added o
the
standard
single-necked t i l l
pot
and
receiver .
he s idearmon the st i l l
pot
a l lows
ef f ic ient n i t ia l
purg ing
of
the
apparatus,
whi le
he s idearmon the receiver l lou 's
ne
o mai ntain a
br isk iner t -gas
low over he d ist i l ledsolventwhen
he receiver
s
renroved rom the st i l l .
The
appa-
ratus
s
ni t ia l l l '
purged
as o l lon
s:
(
)
The
ent i reapparatus,
xcept
or the receiver.s assembled.
2)
Iner t -gas n let
I
is
opened
uhich
purges he
st i l l
pot . co lunrn,
and
condenser .
3)
The receiver
s
at tached o inen-gas n let
3 and
purged
separate ly.
4)
Af ter
both the
receiver nd the main
pan
of
the
apparatus
have been suf f ic ient lypurged
(about
3-5 min) , the receiver s at tached
o
the main
apparatus
'h i le
mainta in ing he iner t -gas low
fronr both in lets and 3.
When
the
receiver
s at-
tached, here
wi l l
be
a
vigorous ner t -gas lou '
through
the mineral o i l bubbler .
(5)
A
slow
low of
iner tgas
s
star ted
rom in let 2. The ner t -gas lou ' f rom inlets and
3
is nou terminated.
Dist i l la t ion
may nou be gin.The
slo* f lo* of iner t -gas rom
inlet 2 through he mineral
o i l
bubbler
wi l l prevent
a ir
from
backing
up into
the
apparatus h i le
min imiz ing
exposure f
the
solvent
o any
impur i t ies
present
n the iner t gas.
I f the
iner t -gas
lou is mainta ined
hrough
he st i l l
pot
dur ing
the
dist i l la-
t ion, the
ef f ic iency
f
the
separat ion
ould
be degraded.
When
the d ist i l la t ion s complete. he ner t -
gas low
from in let
J is
resunred
eforedisconnect ing
he
receiver
rom the
apparatus.
1 2
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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SYRINGEND
CANNULA
ECHNIOUES
:hrough
nlet
2,
with no
flow
from inlet 1,
prevents
ir
contaminationduring
the
.rru15. *
the
reaction
while not
exposing he entiresystem o any
mpurities
hat
:rav
be
present n
the
inert-gas tream.This slow nert-gas
low from inlet 2
also
rrevents
air
from
being sucked
n while
the apparatus
s coolingafter
he
reac-
:ron
l' las
been
completed.
Finally,
this arrangement
prevents
he depletionof
:
iqhly
volatilesolvents.
An apparatus
or disti l lation under
nert
atmosphere,
llustrated n Fig. 1.3,
:ncorporates
he
same eaturesseen n
the
inert-atmosphere
eactionapparatus
Fig. l . l ) . The d is t i l la t ion apparatus
also
conta inssome s l ight ly
modif ied
round-bottom
lasks
or
more efficient
nitial purging. Thesemodificationswill
re
discussedn
greater
detail
n
the
following
section.
To minimize eakage,
oints
areeither ightly
greased
r equipped
with
Teflon
.lc-eves,
nd are
held ogether
with
springs, pecial
l ips,or r ubber bands.
When
rr
can be used,
grease
rovides
he tightest
seal;
however,
eflon sleeves re
gen-
.:rally
used or
connections o stil l
pots
and
similar
harsh
environnents.
The
rarious
types of
stopcock
grease,
ncluding the
new
solvent-resistant
eflon-
hased ubricants, are summarized n Chapter8. Greased tandard aper oints
rre
readilyavailableand are
adequate or mos t
purposes;
owever,
O-ring
oints
.rre
superior
or most inert-atmosphere pparatus.
The
advantages
f
O-joints
are
hat they are
resistant o solvents, nd the clamps
usedwith
these
oints
hold
rhe
apparatus ogether
much more
positively
han do the
springsand other
de-
rices
usedon
standard aper
oints.
Very
satisfactory peration
s
possible
with
either standard O-joints
or
the
Teflon-supportedO-ring
joints
(Solv-Seals).
These
ypesof
joints
are described urther
in
Chapter8. If
standard
O-joints
are
used, the O-ring material
should match the solventsbeing
handled;
again,
Chapter
8
should
be
consulted
or
details.
The principal drawbacksof the standard apparatus s that it is diff icult to
flush
efficiently
and
liquid
transfer
operationsare awkward.
With litt le
addi-
rional
complexity, he
apparatuscan be adapted
or
efficient
purging and solu-
tion
transfer
by syringeor
cannula.
{ ,3
syRrNeE
ND
ANNULA
EcHNrouEs
A.
TypicolAppololus.
A simplemodification
which mproves
he
util ity of
a
one-neck
til l
pot
or solvent eceiver
s
a sidearm,which
can
be used
or flush-
ing the flask. This simple modification acilitates he initial f lush of the appa-
ratus
shown
n
Fig. 1.3. Furthermore,
he sidearm
provides
everal lternatives
for the
removalof
solvents
rom
a receiver, uch as lushing he
flask while sol-
vent
s removed hrough the
standard aperjoint, or
removal
of solve nt hrough
the
sidearm,
as
llustrated n
Fig.
1.4. The
sidearmalso
permits
he
flask to
be
maintainedunder a constant lush of
inert
gas
when it is attached o another
p iece
f
apparatus
Fig.
1.5) .
43
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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BENCH.IOPNERT.ATMOSPHERE
ECHNIOUE
Fig. 1.4. Transfer
of so lvent y syr inge rom
a storage
lask u ' i th
he exclusion
f a i r .
(a)
Solvenl
s
removed hrough he neck of the
storage
lask whi le
mainta in inga br isk f lorvof iner t
gas
rom
the
sidearnt .
6)
Solvent
lso
may be
removed hrough
he
sidearmwhi le r ra inta in ing
atm of
pressure
in the
lask
by admit t ing ner t gas
hrough
he n let . n both
(a)
and
(b) ,
the syr inge
s
ni t ia l ly
purged
by sampl ing ner t
gas
rom the storage lask
and expel l ing h is
gasouts ide
he storage lask.
B. Septo
ond Olher Closules. Rubber septamay be attached
n
a
variety
of
ways,
as llustrated n Fig. 1.6. The
flat
variety s held n
place
by screw aps,
crinped
caps,
or
beveledholders. Various manufacturers
provide
apparatus
with
these
ypesof septumclosures.a
f
greater
versatil ityare
he sleeve eptum
stoppers
Fig.
1.7), which
can
be attached o
straight
ubes or standard aper
joints
without any
special ixtures.s
Two problems
with
all septaare
heir sensitivityo solvents nd
chemicals
nd
leakage
hrough the
punctured
septum. Flat
compositesepta
minimize
these
problenrs.
These
consistof
a central coreof a
compliant
rubber,
such
as a
soft
( b )
aSpecia l
septum closures nd apparatuswith
these
closures
re
manufactured y
Ace
Aldr ich
Chenr ica lCo. .
KontesGlassCo., and WheatonGlass
Co.
in the
Uni ted
States,
in France.
sSleeve- type
septunr
c losures re
u ' ide ly
avai lable rom
chemicaland hospi ta l
supply
excel lent leeve eptunr
topper,producedby
the
Suba
Seal
Co.
n
the
Uni ted
Kingdom,
there rom
Gal lenkamps
and
from
Strem ChemicalCo. in
the Uni ted States.
GlassCo.,
and Sovire l
houses.
An
is avai lable
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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SYRINGEND CANNUTA
ECHNIOUES
Fig. 1.5. Jo in ing wo
pieces
f equipmentunder ner t -gas lush. Both
pieces
re
in i t ia l ly purged
with inert gas separately before joining. Note the use of wire hooks and rubber bands to secure
indiv idual
p ieces
f
g lassware.
f the
glasswares constructed
sing O-r ing
oints,
the O-r ing
oint
c lampshold the apparatus ogether .
silicone ubber, sandwiched etween hin sheets f Teflon. The
silicone
ubber
imparts
good
sealingaction, and the Teflon s highly resistant
o solvents nd to
permeation
by atmospheric
gases.
Direct
contactof solventswith septashould
be
minimized and septa
should
be replaced
often.
When
organic solvents re
being used,
one must
be
wary of impurities
extracted
rom
septa,
oints,
and
tubing. Theseextracted mpurities may foul reactionsand causeconsiderable
confusion n the interpretation f IR and NMR spect ra.The
prime
offenders re
hydrocarbon
nd sil icone topcock
reases,
ibutyl
phthalate
and similar
plasti-
cizers
rom Tygon
tubing, and
various
extracts
rom rubber goods.
Somespec-
tral
methods or identificationof
these
nuisances
re collected
n Table 1.1. The
pickup
of impurities from septacan be
greatly
minimized by
prior
extraction
with
an appropriate
hot
solvent
ollowed
by
pumping
off the absorbed solvent
beforeuse.Septa
make
poor
closures
or
containers sed or
the
long-termstor-
age of highly air-sensitivematerials, since
atmospheric
gases
diffuse through
,15
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R u b b e r
e P t u m
G l o s s
T o ooDoro tus
( o )
F ig.
1.6.
Methods or at taching
ubber septa o
glass
apparatus.
a)
A modi f ied
Swagelok- type
f i t t ing. The
l ip on one end of the
f i t t ing is turned
dorvnon a
lathe, and the
septum
eplaces
he
ferru les.
On the
other
end,
a
Tef lon ront fer ru le
s used
o
nrake he
connect ion
th a
glass
ube.
ä)
An a l l -g lass
eptunr o lder .
c)
Cross ect ion
f a
plast ic
hreaded
ap
septumholder
on a threaded
glass
sidearm
manufactured
y
Wheaton
Glass
Co.) .
F ig, 1.7. Secur ing
Suba-seal
nto
a
glass
ube.
(a)
Cross ect ion f
Suba-seal
s
t is nser ted nto a
glass
ube.
(b)
Af ter inser t ing.
he
lap
on the
Suba-seal
s
oldedover he
tube.
(c)
The f lap
may be
secured o the tube
by
wirc.
Ioble '1.'l SpeclrolSignolures f lmpuriliesrom SfopcockGreoseond
Rubber
ond
Ploslic
fems
Source Ni r ture
f Inrpur i t Spectroscopicdent if cat ion
\ _
/ @ \
t_ lT l
ltt
Itl
U/r
( b )
nn
W
NN
\trN
( a )
( b )
Rubber septa
or
tub ing
T_vgon nd other
f lex ib le
o ly (v iny l
ch lor ide) ub ing
Stopcocks nd
jo in ts
Dyes.ant iox idants ,
etc.
D ibuty l phtha la te
nd
other
plast icizers
Sil icone
rease
Apiezon
L
Vis-UVabsorption
NMR:
Mult .
7 .5.
ub.
.5
M u l t .
. l - 1 . 9 ,
Mult .0 .92
pm
NMR:
ca .0 .1
ppm
NMR:ca.
1.25,
.9
ppm
t i 6
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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SYRINGEND
CANNULA
ECHNIOUES
\cpta
and the
rubber is l ikely
to
undergo
chemical
breakdown.
One
possible
.:rception
o this
statement s the use of unpunctured Teflon-coated epta as
>c'als;
ut even
here one is better off using sealed
lass
ampules
or
storage.
C. Syringes.
The principal
variations
n
available yringes re n
the
design
,rf
he tips and
plungers.
For
most preparative-scale
ork, syringes ith remov-
ableneedles re employed.The removable eedlewith a female oint hub is at-
rached
o
a male
tapered
oint
on
the syringe.
This male Luer
tip
may
be a
straight nner
oint
fashioned rom
glass
or metal or a metal
oint
with
surround-
ing
locking devicewhich holds
the
needlesecurely n
place.
The metal locking
variety
is
preferable
because
t prevents
the detachment of the needle during
critical
transfer
operationsand
the
metal
tip
is more robust
than a
glass
ip.
Glass
ips are desirable
when highly
corrosive
iquids
are
handled. The
Luer
taper
oints
are
widely
adopted but not universal .Nonstandard
apers
do not
sive
an air
tight
seal f mixed with
a
Luer
component.Microliter syringes,
hich
are
useful
or
sampling small volumesof
liquids,
often
have needleswhich
are
permanentlyattached o the barrels.
The
standard small syringesare often constructedwith individually matched
plungers
and barrels which are
given
matching
code
numbers.Theseplungers
and
barrels are
not interchangeable
with
those
from other syringes.Larger
sy-
ringes
often have interchangeable
parts.
Leakage of air
past
the
plunger
is a
constant
problem
with
these ypesof syringes.
When
a light coatingof mineral
,ri l
on the
plunger
can be tolerated,
his
provides
an effective
means
of reducing
the leakage. t al so s
possible
o
reduce
he entranceof air
past
he
plunger
by
forcing
he
solution nto
the syringe
with
a small
positivepressure
ather
than
sucking he material nto the syringe
y
pulling
on the
plunger.
For example, he
three-needleechnique llustrated n Fig. 1.8 may be used o fil l a syringeunder
controlled
positivepressure.
he
variousmethodsof forcing he solution nto
the
svringe
are done
with
the
greatest
control
by
using
a
metal
syringe
holder which
limits
plunger
raveland thus avoids
he
possibil ity
f
the
plungerpopping
out of
the syringe
one
such holder s i l lustrated n
Fig.
1.9).
t is especially elpfulto
use
a
metal
syringe
holder when pyrophoric
materials,
such
as neat
aluminum
alkyls,are transferredby syringe.The metal holder
also
has
he convenience f
permitting
one-handed
perationof the syringe.
Tighter
seals etween he
plunger
and barrel are achievedwith so-called
as
tight syringesn which a Teflon-tippedplunger
or an O-ring-equipped
lunger s
employed.Very good leak resistances also displayed
by the
inexpensive dis-
posable
yringes,"which consistof
a
polypropylene
hell and a
rubber-tipped
plunger.
Unfortunately, the rubber swellsand sticks n
the barrel
when most
organic
solventsare transferred; but
these
disposable
syringesare excellent
or
work
with aqueous
solutions.
D. Sytinge Needles. Syringe
annulae,
which will
be referred
o
asneedles
throughout
his
discussion, re most commonly
constructed
rom
stainless teel
tubing fitted to a metal or
plastic
hub. Chromium-plated rasshubs are
perhaps
1 7
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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Ne --r
Ven t
S e r u m b o t t l e
c o p
\ w i r s
Fig,
l .E. The three-needle
echnique or
u i thdrau ' ing
iquid f rom a storage
ube.
The
syr inge
s
in i t ia l lypurged
by sampl ing ner tgas rom
the ube and expel l ing he
gas
outs ide he ube.To f i l l the
syringe, he vent is briefly covered
with
a finger, forcing
the
solution
into the syringe.
B - D
C o r n w o l l
e t o l
/ , p r P e t t r n g
h o l d e r
l /
1
C Cs t z e
- o o o o
o o o S N \
o o o o o
' \
G r o d u o t i o n s , c c
L u e r - L o k
v o l v e
8 - D
N oM S 0 9
B - D Y o l e e g u l o rp o r n
2 0
g o u g e
h y p o d e r m i cn e e d l e
( L u e r - L o k )
n .
o n g
A s s e m b l e dh y p o d e r m r c
y r i n g e
n m e t o l
p r p e f t i n g
h o l d e r
P l u n g e r
T e n s r o n
p r r n g
R e t o n e . w o s h e r
B - D
C o r n w o l J
y r r n g e
L u e r - L o k )
t
c c s j z e
P l u n g e r
o s s e m b l y
F ig . 1 .9 .
Assembled hypodermic
syr inge
in
meta l
p ipet te ho lder .
,t8
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SYRINGE
ND CANNUTA
ECHNIQUES
rhe
most common
variety.Leaks n
the
Luer taper
oint
between he needle
and
svringe
ody nraybe
minimized
by the
useof a s mall amount of stopcock
rease
on
the
syringe
oint.
A check
or
gross
eaks
s
performed
by
pulling
air
into
the
svringe,
nserting the needle
nto
a
rubber stopper, compressing he
syringe
plunger
o
about half of the original volume,
and noting
whether
he
plunger
returns
o
its
original volume
mark when
released.Poorly itt ing needles
r
sy-
ringeparts shouldbe discarded.Needle ips are easilyblunted and bent
over n
rhecourse
f laboratorywork, so a small,
ine-grained
whetstone
hould
be kept
handy
o
resharpen he
point.
A needle ip that
is
curled back
or has
a
burr on
rhe
point
is
especially
amaging
o
septa.
A sharp needlenot only makes
nser-
tion easier
but also
reduces eakage
hrough
the
punctured
septum.
The so-
callednoncoring
or deflecting ip,
which has
a side
openingor
a
l2o
beveled
ip,
is
preferredoverother ypesof needles ecause
t does he leastdamage
o septa.
A flat-cut
point
should
be avoided.
When
working
with
unstable r reactive
ub-
stances,
t is important to flush a needle
and syringe
with pure
solvent
mntedi-
ately after
use. Stiff metal cleaning
viresare often
providedwith
neu'
needles
and are useful or removingdeposits rom the interior of the needle.
The
outside
diameterof the
needle s
generally
pecified
n
the United
States
by its wire
gauge. Table 1.2
presents
he
metric equivalentof comnron
wire
gauges nd the
sizesof matching syringes.
The latter are
provided
as
a conve-
nient
guide and not as a setof
rules.Teflon
needles
re convenient
or transfer-
ring highly corrosive
materials;however.
heseare
not
general
substitutes
or
metal
syringes
ecause
hey cannot
penetrate epta.
A rangeof
special
syringe
fitt ings s
available. uchas
crosses,ilters,
T's. and stopcocks.b
he
small
stop-
cocks r
va lvesind use
n reta in ing iqu ids
n syr inges. hese reespecia l ly
se-
fu l in
conjunct ion
with large-volume
syr ingesor
u 'hen handl ing
highly
pyrophor icmater ia ls , uch as a luminum alky ls .A setup ncludinga syr inge
stopcock
longwith a syr inge
olderhasalready
een l lustrated
Fig.
1.9) .
An-
other application
of these
tems s
the adapter
or the removalof aluminum
al-
kyls
and
other
reactive iquids from a small
cylinderdescribed
n
the
following
example.
Iob le
'1 .2.
Needle
Sizes
nd Molching syr inges
Gauge
o.d.
(nrnr )
Approx i r r ra te
o lunre f Match ingSv l inge
19
25
23
20
l 8
l 4
0.46
0 .57
0 . 8 1
1 . 0 2
r . 6 3
Microliters
0.2-2nL
l -5 mL
5-50nrl
50-100 rL
'The
construct ion
f a largesyr inge
or
dispensing
ases
s descl ibed 1 'G.
W.
Kranter ,J.
Chcm'
Edac. .50.
221
\1973) .
Syr inge
T's, s topcocks. nd
needlestock or cannulaeare avai lablc
rom
Ald r i chChen r i ca l
o . . P .O . Box
355 .
M i l uaukcc .
Wl
53201 .
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20 BENCH.TOPNERT-ATMOSPHERE
ECHNIQUES
Lead
gaskel
32 hread
Stopcock
Lue
- lo
Iner t
gas
Me ta lcy l r nde r
Wrench
o r
va l ve
Three
way
Lue r - l ok
Syr inge
needle
5
l 6
@'
{u---'
t fl-ll n
Ht /
r - 1 \ l /
@iM
l+J'
V
E. Exomple:
Wifhdrowol
of
Highly Reoclive iquids from Mefol
Tonks. Highly
reactive iquids
such as aluminum alkyls can be
withdrawn
from
a
low-pressure
yl inder
using he apparatus hown
n
Fig.
l . l0a. CAU-
TION: Highly reactive
liquids should be handled in a hood
which
contains a
minimum
of
flammable
material
or chemicals.
After
attaching the syringe
appa-
ratus
to
the
cylinder,
the
needle
s
purged with
inert
gas
for severalminutes.
While purging, he needle s nserted hrough he septum nto the reaction lask.
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'QINGE
ND
CANNULA
ECHNIOUES
Fig.
1.10, Transfer of a i r -sensi t iveiquids
from metal cy l inders.
a)
A
three-way
metal
stopcock
. , 'nstructed or usewith syr ingesmay be modif ied by the addi t ion of a threaded i t t ing so that i t
: ra tes
with
a lecture
bot t le .
The s ide
nlet
s used
o
purge
he
apparatus n i t ia l ly
and to
blou, l iqu id
,ut
of
the
syr inge
eedle
t
the complet ion f
the t ransfer .
The cyl inder
s
put
under a lou '
pressure
I
:ncr t
gas before
he t ransfer
s
begun.
(ö)
Somet imes i r -sensi t ive
iquids
are sold in s iphon- type
;r l inders,and
the l iqu id
f ronr
such a cyl indercan
be
dispensed s shownhere.As wi th
the
previous
rrample, iner t gas s
used
o
force he
l iquid
out
of the cyl inder .
The three-wayvalve s then switched o allow liquid dispensing.When the de-
sired
quantity
of
liquid has been
removed
rom
the cylinder,
the
cylinder
is
closedand
the three-way
alveswitchedback
to
inert gas,
so hat
the
needle
s
purged
by inert
gas
before
it
is
removed rom
the
reaction
flask.
An
apparatus or
the
withdrawal
of reactive iquids
rom metal cylinders
av-
ing
a
siphon tube is shown
n
Fig.
1.10ä.
This setup s operated n
much
the
same
way as he syringeapparatus,
he main
difference
eing he useof
inert gas
to
force
he
liquid
out
of the
cylinder
containing
he siphon
ube.
24
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22
BENCH.TOP
NERT.AIMOSPHERE
ECHNIQUES
F.
Liquid
llonsfer Connuloe. The
transfer
of l iquids
between
wo flasks
may be accompl ished
i th a cannulaalone
Fig.
1.11).These annulae
sual ly
are constructed
rom syringeneedlestock which is
commerciallyavailable
n
convenientengths.6n addition o simple iquid transfer,special i ltration can-
nulaecan
be
constructed. n a
recent
designby M. L. H. Green,a
stainless-steel
cannula is cemented
with
epoxy
resin
to a
short length
of heavy-walled
lass
capillary tubing
which
has a slightly flared and
fire-polishedopening
Fig.
l. l2a). This opening
s covered
y
hardened ilter
paper which is
neatly
olded
back
on
the
glass itt ing
and
wired n place,
as
llustrated n Fig.
|.l2b . A sleeve-
type
septum stopper s
pushed
onto this fi lter apparatus,
with
the
stopperend
toward the fi lter. This assemblymay then be attached o a
receiver nd flask as
i l lustrated
n
Fig. 1 .11. Fi l t ra t ionwith more convent ional
quipment
s i l lus-
trated
n Fig. 1 .13.
In comparisonwith syringe echniques, he useof cannulaeprovidesbetter
air exclusion
and
greater
convenience
or
the
transferof
large
volumes
of
solu-
tion. However,syringe echniquesare much
better suited or the
quantitative
dispensing f
Iiquids,
as demonstrated
n
the
following example.
G. Exomple: Quonlitotive Dispensing of
Liquids. Moderate accuracy
in liquid-transfer
operationscan be achievedusing syringe
graduations.
Air
should first be expelled
rom
the
fil led syringeby
pointing
the
needle
up and
squirtingout all bubbles.Higher
accuracy an
be
achieved
y
weighing he dis-
pensed
iquid. The syringe s fi l led and
the
needle ip
is stoppered y insertion
into a small rubber
stopper.
This
assembly
s weighed, he
iquid dispensed, nd
the syringe
plus
rubber
stopper s
reweighed. f
the
syringe s not
going
o be
re-
Fig. L l l .
Solut ion tansferus ing
a sta in less
teel
annula.The so lut ion s
forced
hrough he nee-
dle by meansof the
pressute
differential
createdby opening he inert
gas nlet,
which pressurizes
he
right-hand lask. The receiv ing lask is e i ther maintainedat I a tm by opening he s idearm o a
bubbler, or is
mainta inedat s l ight ly ess
han
I
atm by
opening
he s idearm
brie f ly
to
a vacuum
source.
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SYRINGE
ND
CANNULA ECHNIQLJES
lr rt
l lu ra l l
l f
Lösausecanr
| |
| | , -Eporv
cement
| |
11 K / - t \ -wr re t re .down
l l l l , -Grassr t tng W^
ä5
@FrterPaPer
( D )
Fig. 1.12. Assenrbly
f a f i l ter cannula
or
"Green
f i l ter . "
(a)
A
piece
of
g lass
capi l lary
ubing,
u
hich
hasbeenblou 'nopenand f i re-pol ished
o form
a
l ip
on one
end. s attached
o the
cannulau i th
cpoxycement.
ä)
F i l tcr
paper
s fo lded
over
he
glass
api l lar l
and secured i th u ' i re .
I ne r t
gas
T o
bubb le r
t
i g . 1 .13 . Va r ia t i on
n
the
cannu la
echn iquc . heg lass
ubc
u i t h
f r i t t ed
i l t e rand
he
g lass
e l i r -
- : \ 1ubesa rea t t ached to theg lasss tanda rd tape r jo in t sbJ 'meanso fp las t i cadap to r s (e .g . ,
on tesK-
I- ' rE00) .
The f lex ib lc p last ic
ubing connect ing
he t$o
par ts
should be inrper i ' ious
o solvents.
I
r i lon
tubing
is
bestand.
to
prcvcnt
contaminat ion
f thc f i l t ra te, T1 'gon
ubing
should
be avoided
r r r ' l l
, r gan i c
o l ve r r t s
rc
used .
used mnlediately, t should be rinsed u' ith degassed olvent mmediatelyafter
use,
o avoid
the buildup of
depositsof
decomposition
roducts
n
the syringe
and needle.
However, f it
is to be re-used
oon
with
the same
solution,
he stop-
per
may
be
left
on
the
needle
ip and both rinsing
and inert-gas lush
may
be
omitted
before
he syringe s fi l led
again.
H.
Specfloscopic
Meosuremenls.
The
sampling
of air-sensitiveiquids
for
NMR
and IR spe ctroscopys
often most
conveniently erformed
by syringe.
Small ubber
septa
are availablewhich
it 5-mm
and other sn.rall MR
tubesand
23
( 4 . )
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2A
BENCH-TOPNERT-ATMOSPHERE
ECHNISUE
also i t the Luer n letson
IR cel ls . he NMR tubemay
be purged
y
purnp-and
f i l l
operat ions,
'hereas
R cel lsareeasi ly lushed y
inert
gas.The
i l l ing of the
IR
cell
s
accornplished y
inserting
he syringe
eedle nto
the septum
on
the
cel
in le t .and he out le tseptum s p ierced vi tha smal lneedle. n excess f l iqu id s
f lushed
hrough he cel l o exc lude
as
bubbles.
A
somewhat
ess i r - f ree pera
t ion
is achieved
y
f lushing
he cel land then at tachine
svr inge onta in inghe
l iqu id by
jo in ing
he Luer
f i t t ings
on the syr inge
nd cel l .
An
empty
syr inge
s
attached o the cell exit
to
serveas a
reservoir or
excess
iquid u'hich s force
through he cel l .
Once the ce l l
is f i l led.
the
in let
and out le t
are capped v i t
Teflon stoppers.Conventional isible-UV cells can also be fitted
rvith
syring
caps
or air-freespectroscopy.
visible-UV cell
that
has
been
used
or
a
u'id
variety
of air-sensitivenorganicand biologicalcon.rpounds
s il lustrated n Fig
1.14.More
sophist icatedpectroscopic
e l ls .
ome
of
rvh ich
resui tab le or us
in conjunctionwith syringe echniques.are described n Chapter9.
4 4
euANTrTATrvEASMANIPULATToN
A. Dispensing
Goses. The d ispensing f
gas
o a so lut ion an
be accom
pl ished
n severa l 'ays.
For example, so lut ionmay be saturated y bubbl in
N e e d l e
-
v o l v e
l - c m
, s i n g l e -
p i e c e
C U V C T T E
R e s e T v o r r ' :
F ig. L l4.
Evacuable e l l or UV-r ' is ib le
pectra. ' I 'h is e l l
s
evacuated
nd
hen
lushed hroughar
iner t -gas nlct at tached o thc O-r ing oint .
' l 'he
Tef lon stenrof the valvc s removedunder f lush
solut ions
re ntroducr-d hrough
his opening.and then
t ipped over nto the culet te af ter he
valr
stem has bcen replaced.
Al tcrnat ive l l . c t>ndensablet> lve 'ntsnd
solutcsma1'
e condensed
nto th
reservoir n a vacuunr ine.
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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:,
ANIITAIIVE
AS
MANIPULAIION
-::
through it from a syringeneedleattached
o a tube and low
pressure as
u rce
F ig .
1 .15 ) .
'f
he
quantitative
delivery
of a
gas
s somewhatmore nvolved.While it
is true
'-
JI a vacuumsystem
ften
permits
he mostsatisfactory
method
of
quantitative
-,,:
handling, some
adequate
procedures
xist
which
are
based
on simple, con-
:
ntional
nert-atmosphere
pparatus.A
large
gastight
syringe s oneof the most
rvious
devices
or
the
measurement f
an aliquot of
gas.bA
sampleof
gas
may
^.:drawn nto the syringe rom a streamof the gasconnectedo an exit bubbler.
\nother
method
or
dispensing
iven quantities
of gas s
a
gas
buret, similar
to
re described ater
in connection
with
the measurement f evolved
ases.T
til l
i:r()ther
implescheme s to
flush
a bulb of known volume
with
the
desired
gas,
,nd
then
bubble
this
gas
into
the
reaction
lask by meansof
a slow
nert-gas
.:ream
Fig
1.16).
Condensable
ases
may
be trapped.measured y vo lume
of
'.re
liquid,
and dispensed y
controlledwarming
of
the
gas.A
suitableapparatus
',r
this
purpose
s il lustrated n
Fig
1.17.
Gases
which
are condensable
t
Dry
:re
temperature,
78oC,
can be handled
by th is
technique.
Finally, it is often possible o generatequantitatively he desiredgas from
:reasured
mountsof l iquid
or
solid eagents. he generated as
s then
quanti-
:. lt ively ransferred
by
inert-gas
lush
into
a reaction mixture. The
automatic
:lsimeter
developed y C.
S.
Brown and H. C. Brown s usefulwhen t is
neces-
.rrv
to kno w the
quantity of gas
consumed n the
course
of
a reaction.sThis
rpparatus
can
be applied o
the
generation
of a varietyof
gases,
uch
as
H2,E
Tobubbler
_>
Fig. 1.15. Dispensing as
direct ly
rom
a tank. l -he
needle
alve
s
used o contro l
he
gas
low nto
thc solut ion,
and a
mercury- f i l led
ubbler prevents
xcessive
ressure
ui ldup.
T. N. Sorre l l
and
M.
R. Malachou'ski ,norg. Chem., 22. l88J
(1983) ,
provide
a recent
descr ipt ion
, , f
gasuptake
exper iments
with
a
gas
buret .
'C .
A . B rownand H . C .
Bro$ 'n , . / .O rp . Chem. .31 .3989
196b ) .
To
hood
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26
BENCH.TOP
NERT.ATMOSPHEREECHNIOUES
T o reac t r on
vesse
Reagent
as
rn
e I
Ca l i b ra ted
o lume
--.>
V
Tobubbler
In hood
Fig. 1.16, Gas-sampl ing ube.
The
tube
is f lushed
with
the
reagent
as
by
opening
o the
reagent
gas
nlet and
vent ing
o a
mineralo i l bubbler . Af ter severalminutes,
he flush s terminated
by f i rs t
c losing he in let s topcock, hen the out le t s topcock.
This
ensures
hat the
pressure
nside he
(ube
equals hr- aboratoryatmospher ic
pressure.)
he laboratorJ
eniperatureand
pressure
re
then
measured
or
use n calculat ing he anount of gasdispensed.
inai iy . he known
quant i t ] '
o f
reagent
gas
s d ispensedo the
react ion essel y opening he n let stopcock o
iner t
gas.
he out le t s topcock
to
the react ionvessel ,
nd
f lushing
he tube
rv i th ner t gas or seYeral r inutes.
CO,e
hydrogen
al ides,r0 ' r
02,
2
ethy lene,rrnd SOt,
r
but notgases h ich eact
with mercury. By
meansof
a
clever
iquid
inlet
device,
gas s produced n
the
generator n
response
o
the
amount consumed n
an
attached
eactor.This liq-
u id in le tva lve
Fig.
1.18),
onsis ts f
a tube
part ia l ly
i l led u ' i th mercury.The
tube
has
provision
or the
nlet
of l iquid from a needle ttached o a buret and for
the controlled l or.r ' f
this
liquid into
the reaction
vessel ia several
mall
holes
above he mercury evel.
Liquid from
this
inlet
valve
drops nto the
gasgenera-
tor, and the
evolved
as
s
conducted rom there o a reaction lask.
The flou'of
liquid
can be initially
adjusted
by
the depth o
which
the needle
rojects
nto the
mercury
pool
of the
valve.When
the
system
s
properlybalanced. he
pressure
drop caused
y
gas
consumption n the reactorpulls
the
reagent
or gasgenera-
tion
in
through
the liquid
control valve.As the
pressure
uilds
up,
this
flow
of
reagent
stops,
only
to resumeagain when
the
reactionconsumes ome
of
the
generated as.
When
the
quantitative
measurement f ga s consumption
s
re-
quired, the exit bubbler serves nly as a safety evice nd the systemmust be set
up so hat there s no gasexpelled
hrough he bubbler during the course
f
the
reaction.
B.
Meosuremenf
of
Evolved
Goses.
The measurement f
evolved
ases
provides
a
ready
meansof
conductingcertainanalyses
nd following he course
' qM .
W.
Ra thke
and H .
C .
Broun . , / .
An t .
Chen t .Soc . . 88 .2606
1966 ) .
l "H .
C .
Bro * ' nand
N. -H .
Re i , " / .
O re . Chen t . , 31
1090
19b6 ) .
I rG.
W. Kranter . A. B. Levv,and M. M. Mid land. in H. C. Brorvn,Organr 'c . i . r ' r r / l tcsesiaBorunes,
Ne l 'Yo rk l
W i ley ,
1973 , .
218 .
r2H .
C .
Brown .M . M . M id land ,
and G .
W.
Kaba lka , . An t . Chen t .Soc . . 93 ,
1024
1971 ) .
t
Inert
gas
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
36/334
OUANIITATIVEAS MANIPULAIION
To
reactron
VESSCI
To
gas
absorber
or hood
Ar . r t rDac
u
p
t rap
Mercury
bubbler
Ca l rb ra ted
ow
empera tu re
t r ap
to r
l t qu r t t ed
as
Fig. 1.17.
Apparatus or
d ispensing
noun quant i t ies
f condensable ases. he
trap
may
be
cal i -
'orated
by using
water
( for
large volumes)
or mercury
for
smal l
vo lumes) .
A
nrercury
bubbler is
rncluded o pre\ent
b lowing the apparatusapart.
Af ter assembl ing
he apparatus, he ent i resystem s
thoroughly
purgcdui th
iner t gas.Stopcock
B is
then turned
to route
gas
o a h ood or
gas
absorber ,
he
iner t -gas low is
ernr inated,
nd
a
slou
f lou
of the desired
gas s
adnr i t ted ronr a
cyl inder
equippedwith a
pressure
egulatorand
needle
ra lve
or f lou 'contro l .
A
Deuarconta in ing
efr igerant apable f l iqu i fv ing he gas
see
able
5. I )
is
then ra isedaround the trap. Af ter the desired o lumeof l iqu id is co l lected, he reagent as lou is
terminated, topcockA
is
closed,and stopcockB is turned to d i rect gas o
the react ion
essel . he
Dewar s then owered
rom the t rap.
a l lorv ing
he col lected
as
o boi l o f f . The rate of
vapor izat ion
mayby contro l led y rais ingand ower ing
he
Deuar. When
the t rap appears o
have
beenempt ied.
a f lush of
iner t gas
nray be used o f lush out
remain ing
eagent apor .
of a reaction.For
example, he analysis f activehydrides
and alkyl compounds
can often be conductedby
quantitative
hydrolysis
o
produce
hydrogen
or
al-
kane.A simple
gas
buret system,
llustrated n Fig. 1.19, s useful or
these ypes
of measurements.t alsomaybe used o dispense pecific uantitiesof gas o an
inert-gas tream or introduction nto a reactionmixture.
The
procedure or us-
ing this
gas
buret
apparatus or
the analysisof active hydridesor alkyl com-
pounds
by hydrol ysis s
described
n
the followingexample.
C.
Exomple:Anolysis
f AcfiveHydrides r AlkylCompounds sing
o
Gos Bure l . This
procedure t i l izes
he
gas
buret
l lustratedn
Fig.
l . l9
to
analyze ctive
hydrides
or
alkyls.First,
the
water evels
n
the
reservoir nd buret
s ides re
adjusted
o
equal
height
and an n i t ia l
buret eading s
aken.
A
sample
of known
weight s
ntroduced
nto
the
hydrolysislask usinga syringe.
After
gas
27
I ne r t ' gas
n le t
,1,
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
37/334
Reagentnlet
trom
buret
Reagent verflow
o
generator
lask
ng
Fig. I .18.
Bro*nl gas
generator
ncl
apparatus
or react ions
with
gases.
Reagents
re mixed
n the
gas
generator
nd the resulr ing
ases
re
passed
nto
the react ion essel .
he nrercurv
ubbler
on
the
far le f t
has
a f loat check
valYe vhich
prevents
nrcrcury
and
air f ronr
being
suckedback
into
the
react ion essel . he key to th is apparatus s the automat ic iqu id intetvalve,shou'n n deta i lon the
r ight .
A drop in
gas pressure
vi th in
he apparatus
pul ls
iquid
fronr
the
buret
through
he
syr ing
needle
nd the
ntercurv.
The rate
of
del iver t
of reagent
s
adjustedby ra is ing
or lower ing
he
bure
and
at tached
s-yr inge
eedle.
React ionessel
28
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
38/334
t ig . 1.19. A gas buret for the measurement r del iveryof gases.When the e lbou (on lef t ) is at-
' ' r rhed
to the
top of
the
buret , gas
s
col lected
nd
i ts vo lume
s measured
f ter
equal iz ing
he mer-
' u r r l e v c l s . F o r e x a n r p l e , a h y d r o l y s i s f l a s k s i n r i l a r t o t h e r e a c t i o n f l a s k i n F i g .
l . l 8 m a y b e a t t a c h e d
'
'
lh ls
e lbow.When
the
stopcock
ssembly
s
used
ar
the
r ight) ,
the
buret
can be i l led
ui th
sas
and
,
n)easured
oluntc
of th is gas
can
be in jected
nto
a stream
of f lou, ing
ner t gas.
29
8/16/2019 Shriver, The Manipulation of Air-Sensitive Compounds BOOK
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30
BENCH.TOP
NERT.AIMOSPHERE
ECHNIQUES
evolutionhas ceased.
he
water
evels re again
matched.and
both a buret and
barometric
pressure
measurement re
aken.
A correction
must
be made
or
the
vapor pressure
f the solventused
n
the
system, specially
f
the solvent
s
very
volatile.
'1
,5 scHLENK
EcHNToUES
A. Bosic Apporolus.
The