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The general procedure for separating ions in qualitative analysis

Add
precipitating
ion

Add
precipitating
ion

Centrifuge

Centrifuge

A qualitative analysis scheme for separating cations into five ion groups

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
Add
(NH4)2HPO4

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Centrifuge

Add
NH3/NH4+
buffer(pH 8)

Centrifuge

Centrifuge

Centrifuge

Add
6M HCl

Acidify to
pH 0.5;
add H2S

Group I Kation

Hot water

AgCl(s); Hg2Cl2(s)

Pb2+

NH3

C rO

HgNH2Cl(s)

P b a2 qu e o u s C r O

2
4 ,a q u e o u s

4 ,a q u e o u s

P b C rO

Ag(NH3)6+
Putih

Ag

aqueous

AgN H

NH

3aqueous

3aqueous

NH

AgN H

3aqueous

3aqueous

A g N H

2 aqueous

Yellow

4 ,s o lid

Group II Kation

Sub Golongan Tembaga

PbS CuS Bi2S3

Hitam

Hitam

Hitam

CdS
Kuning

Na2S2

CuS
Hitam

AsS4-3

HgS2-2

SbS4-3 SnS3-2

Sub Golongan Arsen

Bi2S3 CdS

PbS HgS

Hitam Kuning Hitam Hitam

As2S3

As2S5

Sb2S3 SnS2

Kuning

Kuning

Orange

Kuning

Group II Kation
Sub Golongan Tembaga
PbS CuS Bi2S3

Hitam

Hitam

Hitam

CdS
Kuning

HNO3 encer (6M)

S

Pb+2 Cu+2 Bi+3 Cd+2

dibuang

H2SO4 pekat
PbSO4
PbSO
putih 4

Cu+2 Bi+3 Cd+2

putih

NH4OH berlebih
PbSO4
Bi(OH)
3
putih
putih

Cu(NH3)4+2 Cd(NH3)4+2
HCl (6M), K4Fe(CN)6
Cu2Fe(CN)6

KCN, H2S
CdS

Group II Kation
Sub Golongan Arsen
AsS4-3

HgS2-2

SbS4-3 SnS3-2

HgS

As2S3

As2S5

Hitam

Sb2S3 SnS2

Kuning

Kuning

Orange

Kuning

HCl encer

dibuang

As2S5 HgS Sb2S3 SnS2

HCl pekat

As2S5 HgS

Sb+3 Sn+2
As. Oksalat, H2S

Sb2S3

Mg, HCl (6M)

Sn+2

Sb, Mg
dibuang

HgCl2

Hg

Hg2Cl2

Group III Kation

Group III Separation Scheme

Group III Unknown

NH3, H2S, heat

Group IV ions
NiS, FeS, MnS, ZnS, Fe(OH)3, Al(OH)3
HCl, HNO3, heat
Ni2+, Fe3+, Mn2+, Zn2+, Al3+
Waste
6 M NaOH

Al(OH)4-, Zn(OH)
Fe(OH)3, Ni(OH)2, Mn(OH)2

HNO3
Divide sample
NaBiO3
NH3
MnO4Conc.NH3
purple
Fe(OH)3Ni(NH3)62+
HCl / NH4SCNH2DMG
Fe(SCN)63Ni(DMG)2strawberry
red pp
blood
red

Al(OH)3Zn(NH3)42
aluminon, NH3
K4Fe(CN)6
Al(OH)3aluminon
K2Zn3[Fe(CN)6]2w
cherry red ppt.

Background Group III Separation Scheme

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) D NiS(s) (black)

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

Background Group III Separation Scheme

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

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)

Background Group III Separation Scheme

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

Background Group III Separation Scheme

Ni2+, Fe3+, Mn2+, Zn2+, Al3+
6 M NaOH

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

Al(OH)4-, Zn(OH)42-

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.

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

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

Background Group III Separation Scheme

Ni2+, Fe3+, Mn2+, Zn2+, Al3+
6 M NaOH

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

Al(OH)4-, Zn(OH)42-

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.

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

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

Background Group III Separation Scheme

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

B2 Separation of Group III cations

6 M NaOH

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

Al(OH)4-, Zn(OH)42-

Excess Acid
Al(OH)3(s) + 3H+(aq) D Al3+ + 3 H2O(aq)
Zn(OH)2(s) + 2H+(aq) D Zn2+ + 2 H2O(aq)

Background Group III Separation Scheme

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

B2 Separation of Group III cations

6 M NaOH

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

Al(OH)4-, Zn(OH)42-

Excess Base
Al(OH)3(s) + OH(aq) D Al(OH)4-(aq)
Zn(OH)2(s) + 2OH(aq) D Zn(OH)42-(aq)

Background Group III Separation Scheme

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

Background Group III Separation Scheme

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)

Background Group III Separation Scheme

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) D Ni(NH3)62+(aq) (blue)

Background Group III Separation Scheme

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) D Fe(SCN)63-(aq) blood red

Background Group III Separation Scheme

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)

Background Group III Separation Scheme

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) D 3 NH4+(aq) + Al(OH)3(s)

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

Background Group III Separation Scheme

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) D 3 NH4+(aq) + Al(OH)3aluminon(s) (red)

Background Group III Separation Scheme

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
NH3,
aluminon
Al(OH)3 aluminon
cherry red ppt.

Zn(NH3)42+

Background Group III Separation Scheme

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) D K2Zn3[Fe(CN)6]2 (s)

Background Group III Separation Scheme

Zn2+

Al3+

Ni2+

Fe3+

Mn2+

Group IV Kation

Group IV Unknown
Flame Test Na+
Flame Test K+lavender flame
orange-yellow flame
HC2H3O2, K2CrO4
BaCrO4yellow ppt.
6M HCl
Flame Test
Ca2+, Mg2+
Ba2+
apple - green
6M H2SO4
(NH4)2C2O4
BaSO4
white ppt. CaC2O4white ppt.
Mg2+
NH3(aq), NaH2PO4, heat
6M HCl
MgNH4PO46H2O
Flame Testred-orange
white ppt.

Group IV Separation Scheme

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+
6M H2SO4
BaSO4
white ppt.

Flame Test
apple - green

Ba2+(aq) + K2CrO4(aq) BaCrO4(s) + 2K+(aq)

Group IV Separation Scheme

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+
6M H2SO4
BaSO4
white ppt.

Flame Test
apple - green

Background Group IV Separation Scheme

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+
6M H2SO4
BaSO4
white ppt.

Flame Test
apple - green

Ba2+(aq) + H2SO4(aq) BaSO4(s) + 2H+(aq)

Background Group IV Separation Scheme

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)

Background Group IV Separation Scheme

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+

Background Group IV Separation Scheme

C Test for Mg2+

Ca , Mg
2+

2+

K2C2O4

The magnesium ion is precipitated as a

white solid (ammonium phosphate) in an
alkaline solution.
CaC2O4

Mg2+

Mg2+(aq) + NH3(aq) + HPO42-(aq) MgNH4PO4(s)

NH3(aq)
Na2HPO4(aq)

6M HCl

Flame test
red-orange

MgNH4PO46H2O
white ppt.

Group V Kation

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.

(NH4)2SO4 (NH4)2C2O4

HCl

BaSO4 CaC2O4

Zn(Ac)2 , UO2(Ac)2

Na3Co(NO2)6

Test Nyala : Na &K

NaZn(UO2)3(Ac)2.6H2O

K3Co(NO2)6

NaOH
Bau khas amoniak
Merubah lakmus merah menjadi biru
Original sample

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

Step 2
Add HCl
Centrifuge

Centrifuge

Step 1
Add
NH3(aq)

Step 3 Add
NaOH

Centrifuge

Step 4
Add HCl,
Na2HPO4

Step 5
Dissolve in
HCl and
add KSCN

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

Step 2
Add HCl
Centrifuge

Centrifuge

Step 1
Add
NH3(aq)

Step 3 Add
NaOH

Centrifuge

Step 4
Add HCl,
Na2HPO4

19-41

Step 5
Dissolve in
HCl and
add KSCN

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

19-42