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19-2

Figure 19.16
The general procedure for separating ions in qualitative analysis
Add
precipitating
ion
C
e
n
t
r
i
f
u
g
e

Add
precipitating
ion
C
e
n
t
r
i
f
u
g
e

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
19-3
A qualitative analysis scheme for separating cations into five ion groups
Add
6M HCl
C
e
n
t
r
i
f
u
g
e

Acidify to
pH 0.5;
add H
2
S
C
e
n
t
r
i
f
u
g
e

Add
NH
3
/NH
4
+

buffer(pH 8)
C
e
n
t
r
i
f
u
g
e

Add
(NH
4
)
2
HPO
4

C
e
n
t
r
i
f
u
g
e

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
19-4
Figure 19.17
A qualitative analysis scheme for separating cations
into five ion groups
Add
6M HCl
C
e
n
t
r
i
f
u
g
e

Acidify to
pH 0.5;
add H
2
S
C
e
n
t
r
i
f
u
g
e

Add
NH
3
/NH
4
+

buffer(pH 8)
C
e
n
t
r
i
f
u
g
e

Add
(NH
4
)
2
HPO
4

C
e
n
t
r
i
f
u
g
e

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
19-5
Using pH and complexation
to Separate Ions
For Qualitative Analysis
19-6
Hot water
Pb
2+
AgCl(s); Hg
2
Cl
2
(s)

Pb CrO PbCrO
aqueous aqueous solid
2
4
2
4
+

+
, ,
ppt
CrO
aqueous 4
2
,

19-7
NH
3
HgNH
2
Cl(s)

Ag(NH
3
)
6
+

Hot water
ppt
CrO
aqueous 4
2
,

Pb
2+
AgCl(s); Hg
2
Cl
2
(s)

( )
Ag NH AgNH
AgNH NH Ag NH
aqueous aqueous aqueous
aqueous aqueous
aqueous
+

+
+

+
+
+
3 3
3 3 3
2
19-8
Figure 19.18
Step 1
Add
NH
3
(aq)
C
e
n
t
r
i
f
u
g
e

C
e
n
t
r
i
f
u
g
e

Step 2
Add HCl
Step 3 Add
NaOH
C
e
n
t
r
i
f
u
g
e

Step 4
Add HCl,
Na
2
HPO
4

Step 5
Dissolve in
HCl and
add KSCN
A qualitative analysis scheme for Ag
+
,Al
3+
,Cu
2+
, and Fe
3+

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Valdosta State University
Background
Valdosta State University
General Unknown
Group II
Acid Insoluble Metal Sulfides
Group III
Alkaline Insoluble Metal
Sulfides and Hydroxides
Group IV
Soluble Metal
Ions
Group I
Insoluble Metal Chlorides
and Ammonia
HCl
HCl / H
2
S
NH
3
/ H
2
S
Valdosta State University
Background
Valdosta State University
For this experiment, the group III ions are Fe
3+
, Ni
2+
, Mn
2+
,
Al
3+
and Zn
2+
.
These ions initially precipitate as either metal sulfides (in
an alkaline environment) or metal hydroxides.
This requires the chemist to generate a small quantity of
sulfide ion to precipitate the metals.
A convenient source of S
2-
is thioacetamide, which
decomposes when heated to give hydrogen sulfide
(H
2
S) which yields S
2-
in chemical reactions.
A reagent that is made and consumed in the same
flask is said to be produced in situ.

Valdosta State University
Background Hydrogen Sulfide
Valdosta State University
C
C
N
S
H
H
H
H
H
C
C
O
O
H
H
H
H
+ 2 H
2
O + H
+
(aq) + NH
4
+
(aq) + H
2
S(g)
H
2
S(aq) + 2 H
2
O(l) D 2 H
3
O
+
(aq) + S
2-
(aq)
The addition of base to the second reaction consumes the hydronium ion
and drives the reaction to the right, increasing the concentration of S
2-
(aq).
Thioacetamide
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Group III Unknown
NiS, FeS, MnS, ZnS,
Fe(OH)
3
, Al(OH)
3

Group IV ions
Ni
2+
, Fe
3+
, Mn
2+
, Zn
2+
, Al
3+

Waste
Al(OH)
4
-
, Zn(OH)
4
2-

Fe(OH)
3
, Ni(OH)
2
,
Mn(OH)
2

MnO
4
-

purple
Fe(OH)
3

Divide
sample
Ni(NH
3
)
6
2
+

Ni(DMG)
2

strawberry red
ppt.
Fe(SCN)
6
3-

blood red
Al(OH)
3
Zn(NH
3
)
4
2+

Al(OH)
3
-aluminon
cherry red ppt.
K
2
Zn
3
[Fe(CN)
6
]
2
white ppt.
NH
3
, H
2
S,
heat
HCl, HNO
3
, heat
6 M NaOH
NaBiO
3

Conc.
NH
3

HCl /
NH
4
SCN
H
2
DMG
HNO
3

NH
3

aluminon,
NH
3

K
4
Fe(CN)
6

HNO
3
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Group III unknown
NiS, FeS, MnS, Fe(OH)
3
,
Al(OH)
3
, ZnS

Group IV ions
NH
3
, H
2
S, Heat
A Preparation of Group III cations
The group III ions are initially separated
from the bulk solution by precipitation as
either insoluble metal sulfides or
hydroxides.

Ni
2+
(aq) + S
2
(aq) D NiS(s) (black)

Fe
2+
(aq) + S
2
(aq) D FeS(s) (black)

Zn
2+
(aq) + S
2
(aq) D ZnS(s) (white)

Mn
2+
(aq) + S
2
(aq) D MnS(s) (pink)

Al
3+
(aq) + 3 OH

(aq) D Al(OH)
3
(s) (white, gel)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Group III unknown
NiS, FeS, MnS, Fe(OH)
3
,
Al(OH)
3
, ZnS

Group IV ions
NH
3
, H
2
S, Heat
A Preparation of Group III cations
Since iron has two common oxidation
states, its chemistry in this step is more
complex.
If iron(III) is present it is reduced to iron(II)
and elemental sulfur in produced.
2 Fe
3+
(aq) + H
2
S (aq) 2 Fe
2+
(aq) + S(s) + 2 H
+
(aq)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Group III unknown
NiS, FeS, MnS, Fe(OH)
3
,
Al(OH)
3
, ZnS

Group IV ions
NH
3
, H
2
S, Heat
A Preparation of Group III cations
Alternately, the iron(III) can combine with the
hydroxide ion and precipitate as iron(III)
hydroxide.


Fe
3+
(aq) + 3 OH
-
(aq) D Fe(OH)
3
(rust color)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
NiS, FeS, MnS, Fe(OH)
3
,
Al(OH)
3
Ni
2+
, Fe
3+
, Mn
2+
, Zn
2+
, Al
3+
Waste
HCl, HNO
3
, Heat
B1 Separation of Group III cations
Following the precipitation, the metal
ions are combined with acid to form the
free (and soluble) metal ions.

3NiS(s) +8H
+
(aq) + 2NO
3

(aq) 3Ni
2+
(aq) + 2NO(g) + 3S(s) + 4H
2
O(l)

FeS(s) + 2 H
+
(aq) Fe
2+
(aq) + H
2
S(aq)

3Fe
2+
(aq) + 4H
+
(aq) + NO
3

(aq) 3Fe
3+
(aq) + NO(g) + 2H
2
O(l)

MnS(s) + 2 H
+
(aq) Mn
2+
(aq) + H
2
S(aq)

ZnS(s) + 2 H
+
(aq) Zn
2+
(aq) + H
2
S(aq)

Al(OH)
3
(s) + 3 H
+
(aq) Al
3+
(aq) + H
2
O(l)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Ni
2+
, Fe
3+
, Mn
2+
, Zn
2+
, Al
3+
Al(OH)
4
-
, Zn(OH)
4
2-
Fe(OH)
3
, Ni(OH)
2
, Mn(OH)
2
6 M NaOH
B2 Separation of Group III cations
Aluminum and zinc ions are amphoteric.
This means that at high acid or base
concentrations, these metals form soluble
complexes, but precipitate at moderate pH.
Iron, manganese and nickel form insoluble
hydroxides at high pH.
Fe
3+
(aq) + 3 OH

(aq) D Fe(OH)
3
(s) (rust-color)

Ni
2+
(aq) + 2 OH

(aq) D Ni(OH)
2
(s) (green)

Mn
2+
(aq) + 2 OH

(aq) D Mn(OH)
2
(s) (light brown)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Ni
2+
, Fe
3+
, Mn
2+
, Zn
2+
, Al
3+
Al(OH)
4
-
, Zn(OH)
4
2-
Fe(OH)
3
, Ni(OH)
2
, Mn(OH)
2
6 M NaOH
B2 Separation of Group III cations
Aluminum and zinc ions are amphoteric.
This means that at high acid or base
concentrations, these metals form soluble
complexes, but precipitate at moderate pH.
Iron, manganese and nickel form insoluble
hydroxides at high pH.
Al
3+
(aq) + 3 OH

(aq) D Al(OH)
3
(s) (white, gelatinous)

Zn
2+
(aq) + 2 OH

(aq) D Zn(OH)
2
(s) (white)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Ni
2+
, Fe
3+
, Mn
2+
, Zn
2+
, Al
3+
Al(OH)
4
-
, Zn(OH)
4
2-
Fe(OH)
3
, Ni(OH)
2
, Mn(OH)
2
6 M NaOH
B2 Separation of Group III cations
Excess Acid
Al(OH)
3
(s) + 3H
+
(aq) D Al
3+
+ 3 H
2
O(aq)

Zn(OH)
2
(s) + 2H
+
(aq) D Zn
2+
+ 2 H
2
O(aq)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Ni
2+
, Fe
3+
, Mn
2+
, Zn
2+
, Al
3+
Al(OH)
4
-
, Zn(OH)
4
2-
Fe(OH)
3
, Ni(OH)
2
, Mn(OH)
2
6 M NaOH
B2 Separation of Group III cations
Excess Base
Al(OH)
3
(s) + OH

(aq) D Al(OH)
4
-
(aq)

Zn(OH)
2
(s) + 2OH

(aq) D Zn(OH)
4
2-
(aq)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Fe(OH)
3
, Ni(OH)
2
, Mn(OH)
2
Fe
3+
, Ni
2+
, Mn
2+
C1 Test for Mn
2+,
Fe
3+,
Ni
2+
HNO
3
, KNO
2
The precipitate is redissolved by adding
acid to the precipitate.
The addition of nitric acid neutralizes the
sodium hydroxide and regenerates the
free cations.
There is no easy method which will allow
Mn
2+
, Fe
3+
and Ni
2+
to be separated;
therefore, the sample is divided.

Divide
Sample
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Divide
Sample
MnO
4
-

purple

NaBiO
3
C2 Test for Mn
2+
If sodium bismuthate is added to a
solution containing manganese(II), a
redox reaction occurs resulting in the
formation of the purple permanganate
ion.
14H
+
(aq) + 2Mn
2+
(aq) + 5BiO
3
-
(s) 2 MnO
4
-
(aq) + 5Bi
3+
(aq) + 7H
2
O(l)
Fe
3+
, Ni
2+
, Mn
2+
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Divide
Sample
D1 Separation of Fe
3+
and Ni
2+
Fe(OH)
3
Ni(NH
3
)
6
2+
Conc. NH
3
The nickel and iron ions can be
separated by the addition of ammonia.
The increased pH causes the formation
of the insoluble iron(III) hydroxide.
The nickel ion combines with ammonia
to form a soluble complex ion,
hexaamminenickel(II).
Fe
3+
(aq) + 3NH
3
(aq) + 3H
2
O(l) 3NH
4
+
(aq) + Fe(OH)
3
(s) (brown)

Ni
2+
(aq) + 6NH
3
(aq) D Ni(NH
3
)
6
2+
(aq) (blue)
Fe
3+
, Ni
2+
, Mn
2+
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Divide
Sample
D2 Test for Fe
3+
Fe(OH)
3
Ni(NH
3
)
6
2+
Conc. NH
3
Fe(SCN)
6
3-

blood red

HCl / NH
4
SCN
The presence of the iron(III) ion is
confirmed by the addition of ammonium
thiocyanate.
If iron(III) is present, a blood red solution
forms.
Fe
3+
(aq) + 6SCN
-
(aq) D Fe(SCN)
6
3-
(aq) blood red
Fe
3+
, Ni
2+
, Mn
2+
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Divide
Sample
E Test for Ni
2+
Fe(OH)
3
Ni(NH
3
)
6
2+
Conc. NH
3
Fe(SCN)
6
3-

blood red

HCl / NH
4
SCN
Ni(DMG)
2

strawberry red ppt.
H
2
DMG
The presence of the nickel ion is
confirmed by the addition of
dimethylglyoxime.
Dimethylglyoxime combines with the
nickel ion to form a complex which forms
a strawberry red precipiate.

Ni(NH
3
)
6
2+
(aq) + 2 HC
4
H
7
N
2
O
2
(aq) 4NH
3
(aq) + 2NH
4
+
(aq) + Ni(C
4
H
7
N
2
O
2
)
2
(s) (red)
Fe
3+
, Ni
2+
, Mn
2+
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Al(OH)
4
-
, Zn(OH)
4
2-
F1 Separation of Al
3+
and Zn
2+
Al(OH)
3
Zn(NH
3
)
4
2+
NH
3
HNO
3
Careful control of pH allows for the
separation of aluminum and zinc ions.
The solution is made very slightly basic.
At these conditions, the aluminum ion
precipitates as aluminum hydroxide.
The zinc ion remains in solution.
Al
3+
(aq) + 3 NH
3
(aq) + 3 H
2
O(l) D 3 NH
4
+
(aq) + Al(OH)
3
(s)

Zn
2+
(aq) + 4 NH
3
(aq) D Zn(NH
3
)
4
2+
(aq)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Al(OH)
4
-
, Zn(OH)
4
2-
F2 Test for Al
3+
Al(OH)
3
Zn(NH
3
)
4
2+
NH
3
HNO
3
Al(OH)
3
aluminon
cherry red ppt.

NH
3
,
aluminon

A successful test for aluminum requires
that the previous reactions and their pH
control were properly performed.
If not, false positive tests result.
The test for aluminum requires the free
aluminum ion to react with ammonia in the
presence of a reagent called aluminon and
form a red precipitate.
Be careful, if there is iron or zinc left in the
sample, a red precipitate will form resulting
in a false positive.
Al
3+
(aq) + 3 NH
3
(aq) + 3 H
2
O + aluminon(aq) D 3 NH
4
+
(aq) + Al(OH)
3
aluminon(s) (red)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Al(OH)
4
-
, Zn(OH)
4
2-
F2 Test for Al
3+
Al(OH)
3
Zn(NH
3
)
4
2+
NH
3
HNO
3
Al(OH)
3
aluminon
cherry red ppt.

NH
3
,
aluminon

To confirm that the red precipitate is the
aluminum complex, ammonium carbonate
is added.
If the red color does not fade, aluminum is
present.

Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Al(OH)
4
-
, Zn(OH)
4
2-
G Test for Zn
2+
Al(OH)
3
Zn(NH
3
)
4
2+
NH
3
HNO
3
Al(OH)
3
aluminon
cherry red ppt.

NH
3
,
aluminon

K
2
Zn
3
[Fe(CN)
6
]
2

white ppt.

K
4
Fe(CN)
6
To test for the zinc ion, a solution of
potassium hexacyanoferrate(II) is
added to the test solution.
If zinc is present a white precipitate
forms.
The exact color of the precipitate can
vary depending on the presence of
other ions.
If iron is present the color can change
to yellow, green or blue.
3 Zn
2+
(aq) + 2 K
+
(aq) + 2 Fe(CN)
6
4
(aq) D K
2
Zn
3
[Fe(CN)
6
]
2
(s)
Valdosta State University
Background Group III Separation Scheme
Valdosta State University
Zn
2+
Al
3+
Ni
2+
Fe
3+
Mn
2+
Valdosta State University
Background
Valdosta State University
Group IV Unknown
BaCrO
4
yellow ppt
.

Flame Test Na
+

orange-yellow flame
Ca
2+
, Mg
2+

HC
2
H
3
O
2
,
K
2
CrO
4

Ba
2+

Flame Test
apple - green
BaSO
4

white ppt.
6M HCl
6M H
2
SO
4

CaC
2
O
4

white ppt.
Mg
2+

MgNH
4
PO
4
-6H
2
O
white ppt.
(NH
4
)
2
C
2
O
4

NH
3
(aq), NaH
2
PO
4
,
heat
Flame Test
red-orange
6M HCl
Flame Test K
+

lavender flame
Valdosta State University
Background Group IV Separation Scheme
Valdosta State University
A Flame test for Na
+
and K
+
Insoluble salts of sodium and potassium
are not known.
One method of determining the presence
of these ions is the flame test.
Group IV Unknown
Flame Test Na
+

orange-yellow flame
Flame Test K
+

lavender flame
Na K
Valdosta State University
Background Group IV Separation Scheme
Valdosta State University
B Test for Ba
2+
The formation of a yellow precipitate on
the addition of potassium chromate
indicates the presence of the barium ion.

HC
2
H
3
O
2
,
K
2
CrO
4
BaCrO
4

yellow ppt.
Ba
2+
6M HCl
Flame Test
apple - green
BaSO
4

white ppt.

6M H
2
SO
4
Ba
2+
(aq) + K
2
CrO
4
(aq) BaCrO
4
(s) + 2K
+
(aq)
Valdosta State University
Background Group IV Separation Scheme
Valdosta State University
B Test for Ba
2+
A flame test (apple green) is used to
confirm the presence of the ion.
HC
2
H
3
O
2
,
K
2
CrO
4
BaCrO
4

yellow ppt.
Ba
2+
6M HCl
Flame Test
apple - green
BaSO
4

white ppt.

6M H
2
SO
4
Valdosta State University
Background Group IV Separation Scheme
Valdosta State University
B Test for Ba
2+
The final test for barium is the formation of
a white precipitate on the addition of a
sulfate to the solution.
HC
2
H
3
O
2
,
K
2
CrO
4
BaCrO
4

yellow ppt.
Ba
2+
6M HCl
Flame Test
apple - green
BaSO
4

white ppt.

6M H
2
SO
4
Ba
2+
(aq) + H
2
SO
4
(aq) BaSO
4
(s) + 2H
+
(aq)
Valdosta State University
Background Group IV Separation Scheme
Valdosta State University
C Test for Ca
2+
The calcium ion is separated from
magnesium by precipitating calcium
oxalate.
Ca
2+
, Mg
2+
CaC
2
O
4
(NH
4
)
2
C
2
O
4
Mg
2+
Flame test
red-orange
6M HCl

Ca
2+
(aq) + (NH
4
)
2
C
2
O
4
(aq)
CaC
2
O
4
(s) + 2NH
4
+
(aq)
Valdosta State University
Background Group IV Separation Scheme
Valdosta State University
C Test for Ca
2+
A flame test (red-orange flame) is used to
confirm the presence of the calcium ion.
Ca
2+
, Mg
2+
CaC
2
O
4
(NH
4
)
2
C
2
O
4
Mg
2+
Flame test
red-orange
6M HCl

Valdosta State University
Background Group IV Separation Scheme
Valdosta State University
C Test for Mg
2+
The magnesium ion is precipitated as a
white solid (ammonium phosphate) in an
alkaline solution.
Ca
2+
, Mg
2+
CaC
2
O
4
K
2
C
2
O
4
Mg
2+
Flame test
red-orange
6M HCl

Mg
2+
(aq) + NH
3
(aq) + HPO
4
2-
(aq) MgNH
4
PO
4
(s)
MgNH
4
PO
4
6H
2
O
white ppt.
NH
3
(aq)
Na
2
HPO
4
(aq)

Sample Problem 19.12 Separating Ions by Selective Precipitation
SOLUTION:
PROBLEM: A solution consists of 0.20M MgCl
2
and 0.10M CuCl
2
. Calculate
the [OH
-
] that would separate the metal ions as their hydroxides.
K
sp
of Mg(OH)
2
= is 6.3x10
-10
; K
sp
of Cu(OH)
2
is 2.2x10
-20
.

PLAN: Both precipitates are of the same ion ratio, 1:2, so we can compare
their K
sp

values to determine which has the greater solubility.
It is obvious that Cu(OH)
2
will precipitate first so we calculate the
[OH
-
] needed for a saturated solution of Mg(OH)
2
. This should
ensure that we do not precipitate Mg(OH)
2
. Then we can check
how much Cu
2+
remains in solution.
Mg(OH)
2
(s) Mg
2+
(aq) + 2OH
-
(aq) K
sp
= 6.3x10
-10

Cu(OH)
2
(s) Cu
2+
(aq) + 2OH
-
(aq) K
sp
= 2.2x10
-20

[OH
-
] needed for a saturated Mg(OH)
2
solution =


K
sp
[Mg
2+
]

=
6.3x10
10
0.20
= 5.6x10
-5
M