The general procedure for separating ions in qualitative analysis

Add Add
precipitating precipitating
ion ion
Centrifuge

Centrifuge
A qualitative analysis scheme for separating cations into five ion groups

Acidify to Add
Add
Add pH 0.5; NH3/NH4+
(NH4)2HPO4
add H2S buffer(pH 8)
6M HCl
Centrifuge

Centrifuge

Centrifuge

Centrifuge
 A qualitative analysis scheme for separating cations
into five ion groups

Acidify to Add
Add
Add pH 0.5; NH3/NH4+
(NH4)2HPO4
add H2S buffer(pH 8)
6M HCl
Centrifuge

Centrifuge

Centrifuge

Centrifuge
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Group I Kation

Hot water

AgCl(s); Hg2Cl2(s) Pb2+

NH3 C rO 2
4 ,a q u e o u s

HgNH2Cl(s) P b a2 qu e o u s  C r O 2 
4 ,a q u e o u s  P b C rO 4 ,s o lid

Ag(NH3)6+
Putih Yellow
 
Ag aqueous  NH 
3aqueous  AgN H 3aqueous

A g N H 
 
AgN H 3aqueous  NH 
3aqueous  3 2 aqueous
 Group II Kation

Sub Golongan Tembaga

PbS CuS Bi2S3 CdS

Hitam Hitam Hitam Kuning

Na2S2

CuS Bi2S3 CdS PbS HgS

Hitam Hitam Kuning Hitam Hitam

AsS4-3 HgS2-2 SbS4-3 SnS3-2 As2S3 As2S5 Sb2S3 SnS2

Kuning Kuning Orange Kuning
Sub Golongan Arsen
 Group II Kation
Sub Golongan Tembaga

PbS CuS Bi2S3 CdS

Hitam Hitam Hitam 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)
putih
putih
3
Cu(NH3)4+2 Cd(NH3)4+2

HCl (6M), K4Fe(CN)6 KCN, H2S

Cu2Fe(CN)6 CdS
 Group II Kation
Sub Golongan Arsen

AsS4-3 HgS2-2 SbS4-3 SnS3-2 HgS As2S3 As2S5 Sb2S3 SnS2

Hitam Kuning Kuning Orange Kuning

HCl encer

dibuang As2S5 HgS Sb2S3 SnS2

HCl pekat

As2S5 HgS Sb+3 Sn+2

As. Oksalat, H2S Mg, HCl (6M)

Sb2S3 Sn+2
Sb, Mg
dibuang HgCl2

Hg Hg2Cl2
Group III Kation
Group III Separation Scheme
 Background – Group III Separation Scheme
Group III unknown A – Preparation of Group III cations

NH3, H2S, Heat • The group III ions are initially separated
from the bulk solution by precipitation as
either insoluble metal sulfides or
NiS, FeS, MnS, Fe(OH)3,
Group IV ions
hydroxides.
Al(OH)3, ZnS

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
Group III unknown A – Preparation of Group III cations

NH3, H2S, Heat

• Since iron has two common oxidation states,

its chemistry in this step is more complex.
NiS, FeS, MnS, Fe(OH)3, • If iron(III) is present it is reduced to iron(II)
Group IV ions
Al(OH)3, ZnS and elemental sulfur in produced.

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

 Background – Group III Separation Scheme
B1 – Separation of Group III cations
NiS, FeS, MnS, Fe(OH)3,
Al(OH)3
• Following the precipitation, the metal
HCl, HNO3, Heat ions are combined with acid to form the
free (and soluble) metal ions.
Waste 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
B2 – Separation of Group III cations
Ni2+, Fe3+, Mn2+, Zn2+, Al3+
• Aluminum and zinc ions are amphoteric.
6 M NaOH
• This means that at high acid or base
concentrations, these metals form soluble
Fe(OH)3, Ni(OH)2, Mn(OH)2 Al(OH)4-, Zn(OH)42- 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
B2 – Separation of Group III cations
Ni2+, Fe3+, Mn2+, Zn2+, Al3+
• Aluminum and zinc ions are amphoteric.
6 M NaOH • This means that at high acid or base
concentrations, these metals form soluble
complexes, but precipitate at moderate pH.
Fe(OH)3, Ni(OH)2, Mn(OH)2 Al(OH)4-, Zn(OH)42- • 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
B2 – Separation of Group III cations
Ni2+, Fe3+, Mn2+, Zn2+, Al3+

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
B2 – Separation of Group III cations
Ni2+, Fe3+, Mn2+, Zn2+, Al3+

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
C1 – Test for Mn2+, Fe3+, Ni2+
Fe(OH)3, Ni(OH)2, Mn(OH)2

HNO3, KNO2
• The precipitate is redissolved by adding
Fe3+, Ni2+, Mn2+
acid to the precipitate.
• The addition of nitric acid neutralizes the
sodium hydroxide and regenerates the
Divide free cations.
Sample
• 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
C2 – Test for Mn2+
Fe3+, Ni2+, Mn2+
• If sodium bismuthate is added to a
Divide solution containing manganese(II), a
Sample redox reaction occurs resulting in the
NaBiO3 formation of the purple permanganate
ion.
MnO4-
purple

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+
• The nickel and iron ions can be
Divide separated by the addition of ammonia.
Sample • The increased pH causes the formation
Conc. NH3 of the insoluble iron(III) hydroxide.
• The nickel ion combines with ammonia
to form a soluble complex ion,
Fe(OH)3 Ni(NH3)62+
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
Divide confirmed by the addition of ammonium
Sample
thiocyanate.
Conc. NH3 • If iron(III) is present, a blood red solution
forms.

Fe(OH)3 Ni(NH3)62+

HCl / NH4SCN

Fe(SCN)63-
blood 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
Divide confirmed by the addition of
Sample dimethylglyoxime.
Conc. NH3
• Dimethylglyoxime combines with the
nickel ion to form a complex which forms
a strawberry red precipiate.
Fe(OH)3 Ni(NH3)62+

HCl / NH4SCN H2DMG

Fe(SCN)63- Ni(DMG)2
blood red strawberry red ppt.

Ni(NH3)62+(aq) + 2 HC4H7N2O2(aq)  4NH3(aq) + 2NH4+(aq) + Ni(C4H7N2O2)2(s) (red)

Background – Group III Separation Scheme
F1 – Separation of Al3+ and Zn2+
Al(OH)4-, Zn(OH)42-

• Careful control of pH allows for the

HNO3
separation of aluminum and zinc ions.
NH3 • The solution is made very slightly basic.
• At these conditions, the aluminum ion
precipitates as aluminum hydroxide.
Al(OH)3 Zn(NH3)42+ • 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
F2 – Test for Al3+
Al(OH)4-, Zn(OH)42-
• A successful test for aluminum requires
that the previous reactions and their pH
NH3
control were properly performed.
• If not, false positive tests result.
HNO3 • The test for aluminum requires the free
aluminum ion to react with ammonia in the
presence of a reagent called aluminon and
Al(OH)3 Zn(NH3)42+ form a red precipitate.
• Be careful, if there is iron or zinc left in the
NH3,
aluminon
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)3aluminon(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
NH3 aluminum complex, ammonium carbonate
HNO3
is added.
• If the red color does not fade, aluminum is
present.

Al(OH)3 Zn(NH3)42+

NH3,
aluminon

Al(OH)3 aluminon
cherry red ppt.
Background – Group III Separation Scheme
G – Test for Zn2+
Al(OH)4-, Zn(OH)42- • To test for the zinc ion, a solution of
potassium hexacyanoferrate(II) is
NH3 added to the test solution.
HNO3
• If zinc is present a white precipitate
forms.
• The exact color of the precipitate can
vary depending on the presence of
Al(OH)3 Zn(NH3)42+
other ions.
NH3,
• If iron is present the color can change to
aluminon K4Fe(CN)6 yellow, green or blue.
Al(OH)3 aluminon K2Zn3[Fe(CN)6]2
cherry red ppt. 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 Separation Scheme
B – Test for Ba2+
HC2H3O2,
K2CrO4 • The formation of a yellow precipitate on
BaCrO4 the addition of potassium chromate
yellow ppt. indicates the presence of the barium ion.
6M HCl
Ba2+(aq) + K2CrO4(aq)  BaCrO4(s) + 2K+(aq)
Flame Test
Ba2+
apple - green

6M H2SO4

BaSO4
white ppt.
 Group IV Separation Scheme
B – Test for Ba2+
HC2H3O2,
K2CrO4 • A flame test (apple green) is used to
BaCrO4 confirm the presence of the ion.
yellow ppt.

6M HCl

Flame Test
Ba2+
apple - green

6M H2SO4

BaSO4
white ppt.
 Background – Group IV Separation Scheme
B – Test for Ba2+
HC2H3O2,
K2CrO4 • The final test for barium is the formation of
BaCrO4 a white precipitate on the addition of a
yellow ppt. sulfate to the solution.
6M HCl
Ba2+(aq) + H2SO4(aq)  BaSO4(s) + 2H+(aq)
Flame Test
Ba2+
apple - green

6M H2SO4

BaSO4
white ppt.
Background – Group IV Separation Scheme
C – Test for Ca2+
Ca , Mg
2+ 2+

• The calcium ion is separated from

(NH4)2C2O4
magnesium by precipitating calcium
oxalate.
CaC2O4 Mg2+
Ca2+(aq) + (NH4)2C2O4(aq) 
CaC2O4(s) + 2NH4+(aq)

6M HCl

Flame test
red-orange
Background – Group IV Separation Scheme
C – Test for Ca2+
Ca , Mg
2+ 2+

• A flame test (red-orange flame) is used to

(NH4)2C2O4
confirm the presence of the calcium ion.

CaC2O4 Mg2+

6M HCl

Flame test
red-orange
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)
6M HCl
Na2HPO4(aq)

Flame test MgNH4PO4–6H2O

red-orange white ppt.
Group V Kation
 Group IV Unknown A – Flame test for Na+ and K+

Flame Test K+ Flame Test Na+

• Insoluble salts of sodium and potassium
lavender flame orange-yellow flame are not known.
• One method of determining the presence
of these ions is the flame test.

Na K
 (NH4)2SO4 (NH4)2C2O4

HCl
Zn(Ac)2 , UO2(Ac)2 Na3Co(NO2)6
BaSO4 CaC2O4
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 1
Add Step 2
NH3(aq) Add HCl

Centrifuge
Centrifuge
Step 3 Add
NaOH
Step 4 Step 5
Add HCl, Dissolve in
Na2HPO4 HCl and
add KSCN
Centrifuge
 A qualitative analysis scheme for Ag+,Al3+,Cu2+, and Fe3+
Step 1
Add Step 2
NH3(aq) Add HCl

Centrifuge
Centrifuge
Step 3 Add
NaOH
Step 4 Step 5
Add HCl, Dissolve in
Na2HPO4 HCl and
add KSCN
Centrifuge

19-41 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
19-42