5&6 Analisis Kation

Analisis Kation
Figure19.16
The general procedure for separating ions in qualitative analysis
19-2
Add
precipitating
ion
Centrifuge
Centrifuge
Add
precipitating
ion
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
A qualitative analysis scheme for separating cations into five ion groups
19-3
Add
(NH4)2HPO4
Centrifuge
Add
NH3/NH4+
buffer(pH 8)
Centrifuge
Centrifuge
Centrifuge
Add
6M HCl
Acidify to
pH 0.5;
add H2S
A qualitative analysis scheme for separating cations

into five ion groups
19-4
Add
NH3/NH4+
buffer(pH 8)
Add
(NH4)2HPO4
Centrifuge
Centrifuge
Centrifuge
Add
6M HCl
Acidify to
pH 0.5;
add H2S
Centrifuge
Figure19.17
Using pH and complexation

to Separate Ions
For Qualitative Analysis
19-5
Hot water
AgCl(s); Hg2Cl2(s)
Pb2+
C rO
2
4 ,a q u e o u s
ppt
P b a2 qu e o u s C r O
19-6
4 ,a q u e o u s
P bC rO
4 ,s o lid
Hot water
AgCl(s); Hg2Cl2(s)
Pb2+
NH3
C rO
HgNH2Cl(s)
2
4 ,a q u e o u s
ppt
Ag(NH3)6+
Ag
aqueous
AgNH
NH
3aqueous
19-7
3aqueous
NH
AgN H
3aqueous
3aqueous
A g N H
2 aqueous
Centrifuge
Centrifuge
Figure19.18 A qualitative analysis scheme for Ag+,Al3+,Cu2+, and Fe3+

Step 1
Step 2
Add
Add HCl
NH3(aq)
Step 3 Add
NaOH
Centrifuge
Step 4
Add HCl,
Na2HPO4
19-8
Step 5
Dissolve in
HCl and
add KSCN
Background
General Unknown
HCl
Group I
Insoluble Metal Chlorides
and Ammonia
HCl / H2S
Group II
Acid Insoluble Metal Sulfides
NH3 / H2S
Group III
Alkaline Insoluble Metal
Sulfides and Hydroxides
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Group IV
Soluble Metal
Ions
Background
For this experiment, the group III ions are Fe3+, Ni2+, Mn2+,
Al3+ and Zn2+.
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 S2- is thioacetamide, which
decomposes when heated to give hydrogen sulfide
(H2S) which yields S2- in chemical reactions.
A reagent that is made and consumed in the same
flask is said to be produced in situ.
Background Hydrogen Sulfide

S
H
H
C
H
+ 2 H2O +
H+(aq)
H
H
C
H
+ NH4+(aq) + H2S(g)
Thioacetamide
H2S(aq) + 2 H2O(l) 2 H3O+(aq) + S2-(aq)
The addition of base to the second reaction consumes the hydronium ion
and drives the reaction to the right, increasing the concentration of S2-(aq).
Background Group III Separation Scheme

Group III Unknown
NH3, H2S,
heat
NiS, FeS, MnS, ZnS,
Fe(OH)3, Al(OH)3
Group IV ions
HCl, HNO3, heat

Ni2+, Fe3+, Mn2+, Zn2+, Al3+
Waste
6 M NaOH
Fe(OH)3, Ni(OH)2,
Mn(OH)2
Al(OH)4-, Zn(OH)42-
HNO3
Divide
sample
HNO3
NaBiO3
NH3
MnO4purple
Conc.
NH3
HCl /
NH4SCN
Fe(OH)3
Ni(NH3)62+
H2DMG
Fe(SCN)63blood red
Ni(DMG)2
strawberry red
ppt.
Al(OH)3
aluminon,
NH3
Al(OH)3aluminon
cherry red ppt.
Zn(NH3)42+
K4Fe(CN)6
K2Zn3[Fe(CN)6]2w
hite ppt.

A Preparation of Group III cations
Group III unknown

NH3, H2S, Heat
NiS, FeS, MnS, Fe(OH)3,

Al(OH)3, ZnS
Group IV ions
The group III ions are initially separated

from the bulk solution by precipitation as
either insoluble metal sulfides or
hydroxides.
Ni2+(aq) + S2(aq) NiS(s) (black)

Fe2+(aq) + S2(aq) FeS(s) (black)
Zn2+(aq) + S2(aq) ZnS(s) (white)
Mn2+(aq) + S2(aq) MnS(s) (pink)
Al3+(aq) + 3 OH(aq) Al(OH)3(s) (white, gel)

Group III unknown

NH3, H2S, Heat

Al(OH)3, ZnS
Group IV ions
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 Fe3+(aq) + H2S (aq) 2 Fe2+(aq) + S(s) + 2 H+(aq)

Group III unknown
Alternately, the iron(III) can combine with the

hydroxide ion and precipitate as iron(III)
hydroxide.
NH3, H2S, Heat

Al(OH)3, ZnS
Group IV ions
Fe3+(aq) + 3 OH-(aq) Fe(OH)3 (rust color)

Al(OH)3
HCl, HNO3, Heat
Waste
B1 Separation of Group III cations

Following the precipitation, the metal
ions are combined with acid to form the
free (and soluble) metal ions.
Ni2+, Fe3+, Mn2+, Zn2+, Al3+
3NiS(s) +8H+(aq) + 2NO3(aq) 3Ni2+(aq) + 2NO(g) + 3S(s) + 4H2O(l)

FeS(s) + 2 H+ (aq) Fe2+(aq) + H2S(aq)
3Fe2+(aq) + 4H+(aq) + NO3(aq) 3Fe3+(aq) + NO(g) + 2H2O(l)
MnS(s) + 2 H+(aq) Mn2+(aq) + H2S(aq)
ZnS(s) + 2 H+(aq) Zn2+(aq) + H2S(aq)
Al(OH)3(s) + 3 H+(aq) Al3+(aq) + H2O(l)

Ni2+, Fe3+, Mn2+, Zn2+, Al3+
6 M NaOH
Fe(OH)3, Ni(OH)2, Mn(OH)2
Al(OH)4-, Zn(OH)42-

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.
Fe3+(aq) + 3 OH(aq) Fe(OH)3(s) (rust-color)

Ni2+(aq) + 2 OH(aq) Ni(OH)2(s) (green)
Mn2+(aq) + 2 OH(aq) Mn(OH)2(s) (light brown)

Ni2+, Fe3+, Mn2+, Zn2+, Al3+
6 M NaOH
Al(OH)4-, Zn(OH)42-

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.
Al3+(aq) + 3 OH(aq) Al(OH)3(s) (white, gelatinous)

Zn2+(aq) + 2 OH(aq) Zn(OH)2(s) (white)

Ni2+, Fe3+, Mn2+, Zn2+, Al3+
6 M NaOH
Al(OH)4-, Zn(OH)42-
Excess Acid
Al(OH)3(s) + 3H+(aq) Al3+ + 3 H2O(aq)
Zn(OH)2(s) + 2H+(aq) Zn2+ + 2 H2O(aq)

Ni2+, Fe3+, Mn2+, Zn2+, Al3+
6 M NaOH
Al(OH)4-, Zn(OH)42-
Excess Base
Al(OH)3(s) + OH(aq) Al(OH)4-(aq)
Zn(OH)2(s) + 2OH(aq) Zn(OH)42-(aq)

HNO3, KNO2
Fe3+, Ni2+, Mn2+
Divide
Sample
C1 Test for Mn2+, Fe3+, Ni2+

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
Mn2+, Fe3+ and Ni2+ to be separated;
therefore, the sample is divided.

Fe3+, Ni2+, Mn2+
Divide
Sample
NaBiO3
MnO4purple
C2 Test for Mn2+

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) + 2Mn2+(aq) + 5BiO3-(s) 2 MnO4-(aq) + 5Bi3+(aq) + 7H2O(l)

D1 Separation of Fe3+ and Ni2+
Fe3+, Ni2+, Mn2+
Divide
Sample
Conc. NH3
Fe(OH)3
Ni(NH3)62+
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).
Fe3+(aq) + 3NH3(aq) + 3H2O(l) 3NH4+(aq) + Fe(OH)3(s) (brown)

Ni2+(aq) + 6NH3(aq) Ni(NH3)62+(aq) (blue)

D2 Test for Fe3+
Fe3+, Ni2+, Mn2+
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.
Divide
Sample
Conc. NH3
Fe(OH)3
Ni(NH3)62+
HCl / NH4SCN
Fe(SCN)63blood red
Fe3+(aq) + 6SCN-(aq) Fe(SCN)63-(aq) blood red

E Test for Ni2+
Fe3+, Ni2+, Mn2+
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.
Divide
Sample
Conc. NH3
Fe(OH)3
HCl / NH4SCN
Ni(NH3)62+
H2DMG
Fe(SCN)63blood red
Ni(DMG)2
strawberry red ppt.
Ni(NH3)62+(aq) + 2 HC4H7N2O2(aq) 4NH3(aq) + 2NH4+(aq) + Ni(C4H7N2O2)2(s) (red)

Al(OH)4-, Zn(OH)42HNO3
NH3
Al(OH)3
Zn(NH3)42+
F1 Separation of Al3+ and Zn2+

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.
Al3+(aq) + 3 NH3(aq) + 3 H2O(l) 3 NH4+(aq) + Al(OH)3(s)

Zn2+(aq) + 4 NH3(aq) Zn(NH3)42+(aq)

Al(OH)4-, Zn(OH)42NH3
HNO3
Al(OH)3
Zn(NH3)42+
NH3,
aluminon
F2 Test for Al3+

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(OH)3 aluminon
cherry red ppt.
Al3+(aq) + 3 NH3(aq) + 3 H2O + aluminon(aq) 3 NH4+(aq) + Al(OH)3aluminon(s) (red)

F2 Test for Al3+
Al(OH)4-, Zn(OH)42-
To confirm that the red precipitate is the

aluminum complex, ammonium carbonate
is added.
If the red color does not fade, aluminum is
present.
NH3
HNO3
Al(OH)3
Zn(NH3)42+
NH3,
aluminon
Al(OH)3 aluminon
cherry red ppt.

G Test for Zn2+
Al(OH)4-, Zn(OH)42NH3
HNO3
Al(OH)3
NH3,
aluminon
Zn(NH3)42+
K4Fe(CN)6
Al(OH)3 aluminon
cherry red ppt.
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.
K2Zn3[Fe(CN)6]2
white ppt.
3 Zn2+(aq) + 2 K+(aq) + 2 Fe(CN)64 (aq) K2Zn3[Fe(CN)6]2 (s)
Zn2+
Al3+
Ni2+
Fe3+
Mn2+
Background
Group IV Unknown
Flame Test K+
lavender flame
Flame Test Na+

orange-yellow flame
HC2H3O2,
K2CrO4
BaCrO4
yellow ppt.
6M HCl
Ba2+
Flame Test
apple - green
6M H2SO4
(NH4)2C2O4
BaSO4
white ppt.
CaC2O4
white ppt.
Mg2+
NH3(aq), NaH2PO4,
heat
6M HCl
Flame Test
red-orange
Ca2+, Mg2+
MgNH4PO46H2O
white ppt.
Background Group IV Separation Scheme

A Flame test for Na+ and K+
Group IV Unknown
Flame Test K+
lavender flame
Flame Test Na+

orange-yellow flame
Na
Insoluble salts of sodium and potassium

are not known.
One method of determining the presence
of these ions is the flame test.

B Test for Ba2+
HC2H3O2,
K2CrO4
The formation of a yellow precipitate on

the addition of potassium chromate
indicates the presence of the barium ion.
BaCrO4
yellow ppt.
6M HCl
Ba2+
Flame Test
apple - green
6M H2SO4
BaSO4
white ppt.
Ba2+(aq) + K2CrO4(aq) BaCrO4(s) + 2K+(aq)

B Test for Ba2+
HC2H3O2,
K2CrO4
A flame test (apple green) is used to

confirm the presence of the ion.
BaCrO4
yellow ppt.
6M HCl
Ba2+
Flame Test
apple - green
6M H2SO4
BaSO4
white ppt.

B Test for Ba2+
HC2H3O2,
K2CrO4
The final test for barium is the formation of

a white precipitate on the addition of a
sulfate to the solution.
BaCrO4
yellow ppt.
6M HCl
Ba2+
Flame Test
apple - green
6M H2SO4
BaSO4
white ppt.
Ba2+(aq) + H2SO4(aq) BaSO4(s) + 2H+(aq)

C Test for Ca2+
The calcium ion is separated from
magnesium by precipitating calcium
oxalate.
Ca , Mg
2+
2+
(NH4)2C2O4
CaC2O4
6M HCl
Flame test
red-orange
Mg2+
Ca2+(aq) + (NH4)2C2O4(aq)
CaC2O4(s) + 2NH4+(aq)

C Test for Ca2+
A flame test (red-orange flame) is used to
confirm the presence of the calcium ion.
Ca , Mg
2+
2+
(NH4)2C2O4
CaC2O4
6M HCl
Flame test
red-orange
Mg2+

C Test for Mg2+
Ca , Mg
2+
2+
The magnesium ion is precipitated as a

white solid (ammonium phosphate) in an
alkaline solution.
K2C2O4
CaC2O4
Mg2+
Mg2+(aq) + NH3(aq) + HPO42-(aq) MgNH4PO4(s)

NH3(aq)
Na2HPO4(aq)
6M HCl
Flame test
red-orange
MgNH4PO46H2O
white ppt.
Sample Problem 19.12
Separating Ions by Selective Precipitation
PROBLEM: A solution consists of 0.20M MgCl2 and 0.10M CuCl2. Calculate

the [OH-] that would separate the metal ions as their hydroxides.
Ksp of Mg(OH)2= is 6.3x10-10; Ksp of Cu(OH)2 is 2.2x10-20.
PLAN: Both precipitates are of the same ion ratio, 1:2, so we can compare
their Ksp 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 Cu2+ remains in solution.
SOLUTION:
Mg(OH)2(s)
Mg2+(aq) + 2OH-(aq) Ksp = 6.3x10-10
Cu(OH)2(s)
Cu2+(aq) + 2OH-(aq)
[OH-] needed for a saturated Mg(OH)2 solution =

= 5.6x10-5M
Ksp = 2.2x10-20
6.3x1010
2
0.20
[Mg ]
K sp

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Analisis Kation

The general procedure for separating ions in qualitative analysis

A qualitative analysis scheme for separating cations

Using pH and complexation

Figure19.18 A qualitative analysis scheme for Ag+,Al3+,Cu2+, and Fe3+

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Background Hydrogen Sulfide

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Background Group III Separation Scheme

HCl, HNO3, heat

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Background Group III Separation Scheme

Group III unknown

NiS, FeS, MnS, Fe(OH)3,

The group III ions are initially separated

Ni2+(aq) + S2(aq) NiS(s) (black)

Background Group III Separation Scheme

Group III unknown

NiS, FeS, MnS, Fe(OH)3,

Since iron has two common oxidation states,

2 Fe3+(aq) + H2S (aq) 2 Fe2+(aq) + S(s) + 2 H+(aq)

Valdosta State University

Background Group III Separation Scheme

Group III unknown

Alternately, the iron(III) can combine with the

NH3, H2S, Heat

NiS, FeS, MnS, Fe(OH)3,

Fe3+(aq) + 3 OH-(aq) Fe(OH)3 (rust color)

Valdosta State University

Background Group III Separation Scheme

B1 Separation of Group III cations

Ni2+, Fe3+, Mn2+, Zn2+, Al3+

3NiS(s) +8H+(aq) + 2NO3(aq) 3Ni2+(aq) + 2NO(g) + 3S(s) + 4H2O(l)

Background Group III Separation Scheme

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

B2 Separation of Group III cations

Fe3+(aq) + 3 OH(aq) Fe(OH)3(s) (rust-color)

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Background Group III Separation Scheme

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

B2 Separation of Group III cations

Al3+(aq) + 3 OH(aq) Al(OH)3(s) (white, gelatinous)

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Background Group III Separation Scheme

B2 Separation of Group III cations

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

Valdosta State University

Background Group III Separation Scheme

B2 Separation of Group III cations

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

Valdosta State University

Background Group III Separation Scheme

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C1 Test for Mn2+, Fe3+, Ni2+

Background Group III Separation Scheme

C2 Test for Mn2+

14H+(aq) + 2Mn2+(aq) + 5BiO3-(s) 2 MnO4-(aq) + 5Bi3+(aq) + 7H2O(l)

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Background Group III Separation Scheme

Fe3+, Ni2+, Mn2+

The nickel and iron ions can be

Fe3+(aq) + 3NH3(aq) + 3H2O(l) 3NH4+(aq) + Fe(OH)3(s) (brown)

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5&6 Analisis Kation

5&6 Analisis Kation