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Introduction
In
a
solution
having
high
chloride
concentration,
cadmium
and
zinc
form
complex
anions
as
shown
below:
Zn+2
+
4Cl-
ZnCl4-2
Kst
=
0.71
Cd+2
+
4Cl-
CdCl4-2
Kst
=
51.0
These
complexes
can
be
exchanged
for
other
anions
on
anion-exchange
resin,
using
a
hydrochloric
acid
solution
of
appropriate
strength.
At
a
concentration
of
0.01M
HCl,
zinc
does
not
exist
as
the
anion
complex,
but
cadmium
does.
If
the
solution
of
zinc
and
cadmium
contains
chloride
and
hydroxide,
zinc
forms
mixed
complexes
such
as
[ZnCl3OH]-2
or
[(ZnCl3)2OH]-3.
Cadmium
doesnt
form
mixed
complexes.
Some
of
the
zinc
and
cadmium
form
hydroxy
complexes
as
shown
below:
Zn+2
+
4OH-
Zn(OH)4-2
Kst
=
2
x
1015
Cd+2
+
4OH-
Cd(OH)4-2
Kst
=
1
x
1012
We
can
take
advantage
of
the
differences
in
zinc
and
cadmium
chemistry
to
separate
a
mixture
of
zinc
and
cadmium.
Briefly,
a
sample
containing
zinc
and
cadmium
is
made
about
1.5
M
in
chloride
ion,
converting
all
of
the
zinc
and
cadmium
into
the
chloride
complexes.
This
solution
is
put
onto
the
top
of
a
column
of
Dowex
1-X8
anion-exchange
resin.
The
zinc
and
cadmium
complexes
stick
to
the
anion-exchange
resin.
A
suitable
solution
containing
sodium
hydroxide
and
sodium
chloride
is
passed
through
the
column.
The
zinc
forms
the
hydroxide
complex
and
the
mixed
chloride
and
hydroxide
complexes,
while
cadmium
forms
hydroxide
complexes
only.
The
cadmium
chloride
complex
binds
more
tightly
to
the
resin
than
does
the
various
zinc
complexes,
and
therefore
zinc
is
eluted
fairly
rapidly
from
the
column.
To
remove
the
cadmium,
the
cadmium
chloride
complex
must
be
destroyed.
After
all
zinc
has
been
separated,
dilute
nitric
acid
is
passed
through
the
column.
This
destroys
the
cadmium
chloride
complex,
releasing
cadmium
cation.
Cations
have
no
attraction
for
anion
exchange
resin,
and
therefore
the
cadmium
elutes
from
the
column
immediately.
The
chemical
reactions
describing
the
chemistry
of
this
separation
are
shown
below.
Sample
Addition
to
Anion-Exchange
Resin:
2R+Cl-
+
ZnCl4-2
(R+)2ZnCl4-2
+
2Cl-
2R+Cl-
+
CdCl4-2
(R+)2CdCl4-2
+
2Cl-
NOTE:
anion
exchange
resin
can
be
conveniently
pictured
as
an
ionic
compound,
composed
of
an
organic
cation
(R+)
and
an
anion
(Cl-
in
this
case,
although
other
types
of
resins
having
different
anions
are
available).
Elution
of
Zinc:
(R+)2ZnCl4-2
+
(R+)2CdCl4-2
+
6OH-
2R+OH-
+
(R+)2CdCl4-2
+
Zn(OH)4-2
+
4Cl-
NOTE:
the
zinc
chloride
complex
is
converted
into
the
zinc
hydroxide
complex.
The
zinc
hydroxide
complex
does
not
bind
to
the
anion-exchange
resin
as
tightly
as
the
zinc
chloride
complex,
and
therefore
the
zinc
hydroxide
complex
is
eluted
from
the
column.
The
cadmium
complex
remains
intact
and
bound
to
the
anion
exchange
resin.
Elution
of
cadmium:
(R+)2CdCl4-2
+
2NO3-
2R+NO3-
+
Cd+2
+
4Cl-
NOTE:
addition
of
nitric
acid
destroys
the
cadmium
chloride
complex.
The
nitrate
ion
binds
to
the
anion
exchange
resin,
while
the
cadmium
cation
is
strongly
repelled
from
the
organic
cation
(R+)
and
therefore
remains
in
solution.
Once
the
cadmium
and
zinc
are
separated,
a
quantitation
method
is
needed
to
determine
the
amount
of
cadmium
and
zinc
present.
The
classic
method
of
determining
zinc,
cadmium,
and
other
suitable
cations,
is
titration
with
a
standardized
solution
of
ethylenediaminetetraacetic
acid
(EDTA).
EDTA
has
the
structure
shown
below.
Instead
of
repeatedly
drawing
this
structure
or
writing
out
the
chemical
formula,
the
EDTA
molecule
is
represented
as
Y.
Each
acid
hydrogen
on
EDTA
can
be
removed,
producing
H3Y-1,
H2Y-2,
HY-3,
and
Y-4
ions.
The
disodium
dihydrate
of
EDTA,
Na2H2Y2H2O
is
commonly
used
to
prepare
standard
EDTA
solutions.
This
salt
is
readily
available
from
many
commercial
sources,
and
often
in
such
a
high
purity
that
solutions
need
not
be
standardized
for
routine
work.
Primary
standard
calcium
carbonate
can
be
used
to
standardize
EDTA
solutions,
but
high
purity
zinc
solutions
permit
faster
titrations
with
a
sharper
endpoint.
Therefore
zinc
is
preferred
for
standardization.
A
variety
of
indicators
are
used
for
EDTA
titrations.
In
this
titration,
we
will
be
using
Eriochrome
black
T
(EBT)
indicator,
having
the
structure
shown
below.
(H2In-)
Most
metals
form
wine
red
colored
complexes
with
Eriochrome
black
T,
while
the
unbound
indicator
is
blue
(See
Figure
1
below).
Metal
ions
bind
more
strongly
to
EDTA
than
to
EBT,
so
as
a
wine
red
solution
of
metal-EBT
is
titrated
with
EDTA,
the
color
changes
from
wine
red,
to
purple,
to
blue.
Figure
1.
Wine
red
and
blue
colors
for
Eriochrome
black
T
indicator.
The
zinc-EDTA
complex
has
a
stability
constant
of
3.26
x
1016.
While
other
procedures
for
titrating
zinc
with
EDTA
are
found
in
the
literature,
the
most
common
procedure
is
to
titrate
zinc
at
pH
10.
However,
the
solubility
product
(Ksp)
of
zinc
hydroxide
is
7.1
x
10-18,
and
at
pH
10
most
of
the
zinc
is
in
the
insoluble
zinc
hydroxide
form.
(In
most
cases,
zinc
will
start
to
precipitate
as
zinc
hydroxide
about
pH
7.)
In
order
for
the
zinc-EBT
complex
to
form,
the
solution
must
be
basic,
so
some
sort
of
auxiliary
complexing
agent
must
be
used
to
prevent
the
zinc
from
precipitating
as
the
hydroxide.
Ammonia
forms
a
tetra
amine
complex
with
zinc,
and
the
Kst
for
the
zinc
tetra
amine
complex
is
sufficiently
high
(4.2
x
108)
that
solutions
containing
1.0
M
ammonia
will
not
precipitate
zinc
hydroxide
at
a
pH
of
10.
The
titration
reaction
between
the
zinc
tetra
amine
complex
and
HY-3
(the
form
of
EDTA
predominating
at
pH
10)
is
shown
in
the
chemical
reaction
below.
Zn(NH3)4+2
+
HY-3
ZnY-2
+
NH4+
+
3NH3
The
conditional
stability
constant
for
this
reaction
under
the
experimental
conditions
(pH
=
10,
[NH3]
=
0.5M)
is
2.3
x
109.
The
stability
constant
for
the
zinc-
EBT
complex
under
these
conditions
is
5.6
x
106.
The
indicator
forms
a
weaker
complex
with
zinc
ions
than
does
the
EDTA,
therefore
the
free
indicator
is
produced
at
the
end
point
of
the
titration,
causing
the
color
to
change
at
the
appropriate
point.
Solutions
needed
for
this
experiment:
Solutions
prepared
by
the
student
Solutions
provided
by
the
instructor
0.01M
disodium
EDTA
(standardized
by
12M
Hydrochloric
acid
student)
6M
Hydrochloric
acid
50%
Sodium
hydroxide
solution
Dilute
(<0.10M)
sodium
hydroxide
8.5M
NH3-NH4Cl
Buffer
and
~
1
M
sodium
hydroxide
0.5M
Hydrochloric
acid
Eriochrome
black
T
indicator
1M
Nitric
acid
0.12M
HCl-10%NaCl
solution
Standard
Zn
solution
2M
NaOH-2%NaCl
solution
Concentrated
nitric
acid
Specialized
equipment
needed:
In
this
experiment,
you
will
be
using
a
chromatography
column
(see
Figure
1
below).
There
are
three
separate
pieces
to
the
chromatography
column;
a
long
(~30
cm)
glass
tube,
a
valve
and
stopcock
assembly,
and
a
delivery
tip.
Assemble
the
pieces
as
shown
in
the
figure,
and
test
the
column
by
filling
it
with
water.
If
the
column
leaks,
notify
your
instructor
so
that
the
column
can
be
replaced.
Figure
1.
Chromatography
column
showing
glass
tube,
valve
and
stopcock
assembly,
and
delivery
tip.
6
Experimental
Procedure
Preparation
and
standardization
of
0.01
M
EDTA
solution.
1.
Using
the
top
loading
balance,
weigh
between
3.6
and
3.7
grams
of
disodium
EDTA
dihydrate
into
a
clean
1
L
plastic
bottle.
EDTA
will
leach
metal
ions
from
soft
glass
containers,
and
should
never
be
stored
in
glass
containers.
Add
1
L
of
deionized
water.
EDTA
dissolves
SLOWLY.
Shaking
or
stirring
the
solution
vigorously
speeds
the
dissolution
process.
Heating
the
solution
to
50
60
oC
also
speeds
the
process.
Nevertheless,
even
under
these
conditions
EDTA
dissolves
SLOWLY.
It
is
strongly
recommended
that
you
prepare
the
EDTA
solution
several
hours
or
even
the
day
before
you
plan
on
using
it.
Before
use,
check
the
solution
to
make
sure
that
all
solid
EDTA
has
dissolved.
2. Using
the
analytical
balance,
weigh
out
~0.5
grams
of
high
purity
zinc
metal
and
transfer
the
metal
to
a
150
mL
beaker.
The
actual
mass
of
metal
used
is
not
important
provided
that
the
mass
is
precisely
known.
3. Working
in
the
hood,
slowly
add
10
mL
of
6M
hydrochloric
acid
to
the
zinc
metal,
and
cover
the
beaker
with
a
watch
glass.
Allow
the
zinc
metal
to
dissolve
completely,
which
may
take
some
time
(an
hour
or
more).
The
initial
reaction
is
vigorous,
and
zinc
solution
can
be
lost
by
splattering
if
the
beaker
is
not
covered
quickly
with
a
watch
glass.
When
it
appears
that
dissolution
is
complete,
carefully
check
that
all
small
zinc
particles
have
been
dissolved.
Hydrogen
gas
is
produced
by
this
reaction.
This
gas
is
flammable
and
can
form
explosive
mixtures
with
the
air.
4. After
the
zinc
has
dissolved,
analytically
transfer
the
solution
to
a
500.00
mL
volumetric
flask
and
QS
with
DI
water.
Mix
thoroughly,
and
store
the
solution
in
a
plastic
bottle.
Label
the
solution
with
the
molar
concentration
of
zinc.
5. Pipette
25.00
mL
of
standard
zinc
solution
into
a
250-mL
Erlenmeyer
flask.
Using
dilute
sodium
hydroxide
solution
(~
0.1M)
raise
the
pH
of
the
solution
until
a
very
slight
turbidity
persists.
(Alternatively,
until
the
pH
of
the
solution
is
~
10).
The
exact
amount
of
sodium
hydroxide
solution
depends
on
the
acid
concentration
of
your
zinc
standard
and
the
concentration
of
sodium
hydroxide
solution
used,
but
should
be
~25
mL.
Addition
of
sodium
hydroxide
should
be
stopped
at
the
first
appearance
of
zinc
hydroxide
precipitate
or
when
the
pH
is
~
10,
whichever
occurs
first.
7
6. Add
10
mL
of
8.5M
NH3-NH4Cl
buffer.
This
buffer
has
been
prepared
for
your
use.
CAUTION!
This
buffer
is
dangerous;
it
is
caustic
and
ammonia
can
cause
pulmonary
paralysis
(it
can
interfere
with
your
ability
to
breath).
Exercise
caution
in
handling
and
dispensing
this
buffer!!
From
the
known
mass
of
zinc,
and
the
1:1
stoichiometry
between
zinc
and
EDTA,
you
should
be
able
to
readily
calculate
the
molarity
of
the
EDTA
solution.
Calculate
the
average
molarity
and
label
your
EDTA
solution
appropriately.
Column
preparation
anion
exchange
resin.
1. Weigh
out
15
20
g
of
Dowex
anion
exchange
resin
(chloride
form)
into
a
150
mL
beaker.
Add
~10
mL
of
deionized
water
and
stir
for
a
few
minutes
to
thoroughly
wet
the
resin.
Decant
and
discard
the
supernatant
liquid.
The
volume
of
the
wet
resin
should
be
~25
mL.
2. Add
50
mL
of
0.5M
hydrochloric
acid
to
the
resin,
stir,
allow
the
resin
to
settle,
and
decant
and
discard
the
supernatant
liquid.
Repeat
this
washing
process
until
the
supernatant
liquid
is
colorless.
3. Assemble
your
chromatography
column.
Into
the
bottom
of
the
column
tamp
a
small
plug
of
glass
wool.
The
glass
wool
should
be
tight
enough
and
large
enough
to
prevent
any
of
the
resin
particles
from
passing
through
and
clogging
the
stopcock
or
tip,
but
loose
enough
and
small
enough
not
to
impede
the
flow
of
liquid
through
the
column.
4. Using
0.5M
hydrochloric
acid
as
a
wash
liquid,
transfer
the
wet
resin
slurry
to
the
chromatography
column.
Rinse
down
the
insides
of
the
column
and
allow
the
resin
to
settle
under
gravity.
A
20
cm
column
of
well-packed
resin
should
result.
If
the
column
is
shorter
than
this,
add
more
resin.
Wash
the
completed
column
once
with
0.5M
hydrochloric
acid.
DO
NOT
ALLOW
THE
LEVEL
OF
LIQUID
IN
THE
COLUMN
TO
FALL
BELOW
THE
RESIN
BED.
Keep
the
liquid
level
~
1
cm
above
the
resin
bed
at
all
times.
5. Wash
the
resin
column
with
two
20-mL
portions
of
0.12M
HCl
10%
NaCl
solution,
draining
the
liquid
to
about
0.5
cm
above
the
top
of
the
resin
bed.
(This
solution
has
been
prepared
for
your
use.)
Sample
Addition
and
Separation.
1. Pipette
a
2.00
mL
aliquot
of
the
unknown
cadmium-zinc
solution
onto
the
top
of
the
column.
This
can
best
be
achieved
by
holding
the
tip
of
the
pipette
about
1
cm
above
the
resin
bed
and
running
the
tip
around
the
inner
circumference
of
the
chromatographic
column
while
the
sample
is
draining
out
of
the
pipette.
9
2. Drain
the
sample
to
within
0.5
cm
of
the
top
of
the
resin
bed.
Use
5
mL
of
0.12M
HCl
10%
NaCl
solution
to
wash
down
the
inside
walls
of
the
column,
draining
the
column
to
within
0.5
cm
of
the
top
of
the
resin
bed.
Repeat
the
washing
with
a
2
mL
aliquot
of
0.12M
HCl
10%
NaCl
solution.
The
resin
may
or
may
not
change
colors,
depending
on
factors
that
arent
important
to
this
analysis.
3. Pass
150
mL
of
2M
NaOH
2%
NaCl
eluting
solution
through
the
column
at
a
rate
of
~
3
mL/minute.
Collect
the
eluate
in
a
clean
250.00
mL
volumetric
flask
and
QS
with
DI
water.
The
2M
NaOH
2%
NaCl
has
been
provided
for
you.
This
solution
contains
the
zinc
metal
from
your
unknown
sample
and
should
be
labeled
appropriately.
4. Wash
the
resin
column
with
~
50
mL
of
deionized
water
to
remove
most
of
the
sodium
hydroxide
solution.
Drain
the
wash
water
from
the
bottom
of
the
column
and
discard.
5. Pass
150
mL
of
1M
nitric
acid
through
the
column,
collecting
the
eluate
in
a
separate,
clean,
250.00
mL
volumetric
flask.
QS
with
DI
water.
This
solution
contains
the
cadmium
metal
from
your
unknown
sample
and
should
be
labeled
appropriately.
6. When
you
have
completed
the
separation,
throw
the
used
resin
in
the
trashcan.
Analysis
of
cadmium
and
zinc.
1. Pipette
a
50.00
mL
aliquot
of
the
zinc
solution
into
a
250-mL
Erlenmeyer
flask.
Use
6M
hydrochloric
acid
to
adjust
the
solution
to
~pH
9.
Titrate
the
zinc
solution
according
to
the
instructions
for
the
standardization
of
EDTA
starting
with
step
6
(the
addition
of
8.5M
NH3-NH4Cl
buffer.
Perform
this
analysis
in
triplicate.
2. Pipette
a
50.00
mL
aliquot
of
the
cadmium
solution
into
a
250-mL
Erlenmeyer
flask.
Use
sodium
hydroxide
solution
to
adjust
the
solution
to
~pH
9.
Titrate
the
cadmium
solution
according
to
the
instructions
for
the
standardization
of
EDTA
starting
with
step
6
(the
addition
of
8.5M
NH3-
NH4Cl
buffer).
Perform
this
analysis
in
triplicate.
Calculations
Since
EDTA
forms
a
1:1
complex
with
either
metal
under
these
experimental
conditions,
the
millimoles
of
metal
present
can
be
found
by
calculating
the
number
of
millimoles
of
EDTA
consumed
during
the
titration
using
the
equation:
10
Since
the
total
volume
of
the
eluate
has
not
been
titrated,
the
millimoles
of
metal
titrated
(calculated
from
the
above
equation)
are
the
millimoles
present
in
the
aliquot
used.
A
dilution
factor
must
be
used
to
calculate
the
total
number
of
millimoles
of
metal
present
in
the
250.00
mL
volumetric
flask:
Total
millimoles
metal
=
millimoles
metal
X
(250.00
mL/50.00
mL)
Once
the
total
number
of
millimoles
of
metal
present
in
the
sample
is
calculated,
the
mass
in
milligrams
of
metal
present
is
readily
determined.
In
your
report,
make
sure
you
report
the
milligrams
of
cadmium
and
zinc
separately
(do
not
report
the
total
of
cadmium
and
zinc
combined).
Laboratory
report.
A
sample
report
is
shown
at
the
end
of
the
procedure.
WASTE
DISPOSAL:
All
solutions
containing
cadmium
or
zinc
must
be
disposed
of
in
the
aqueous
metals
container.
11
12