IDENTIFICATION OF THE

CATION

ADALIN, EDGAR JERICHO B.

JUDAN, MERRENE BRIGHT D.

SUMMARY

RATIONALE
Principle of hard and soft acids and bases
Hard acid react much faster with a hard base
Soft acid react much faster with a soft base
A hard acid or base is a chemical species that is small, weakly
polarizable, and has a higher charge density. Reactions
between hard acids or bases are primarily charge-based or
electrostatic. Hard species tend to found in the early rows of
the periodic table.
Soft acids or bases are larger and more polarizable (highenergy, diffuse orbitals), and are found in the later rows of the
periodic table. They tend to react due to orbital overlaps

RATIONALE

RATIONALE
The classification of cations into Groups I, II, III, IV, and V is
based on the classifying the cations as:
very soft acids (Group I)
soft acids (Group II)
borderline acids, hard acids (Group III)
weakly acidic cations (Group IV)
non-acidic cations (Group V)
The corresponding softness or hardness of the cations would
determine whether or not they would react (precipitate) with
bases of varying softness.

CATIONS GROUP 3
BASE-INSOLUBLE SULFIDES AND
HYDROXIDES

Group 3
Cations of this group do not react either with dilute
hydrochloric acid, or with hydrogen sulphide in dilute mineral
acid medium. However they form precipitates with ammonium
sulphide in neutral or ammoniacal medium. Cations of this
group are iron(II), iron(III), cobalt(II), nickel(II), manganese(II),
chromium(III), aluminium(III), and zinc(II).

http://isite.lps.org/mschmid3/web/documents/groupivanalysis.pdf

DECANTATE (B)
Na+, K+, NH4+, Pb2+, Cu2+, Cd2+, Ni2+, Co2+,
Zn2+, Mn2+, Mg2+, Ca2+, Ba2+, Sr2+, Cr3+,
Co3+, Fe3+, Al3+,

+ H+
NH4+

proton

ammonium ion

Acid Catalyzed Hydrolysis of

Thioacetamide
Thioacetamide
source of H S
2

(aq)

H2S + 2 NH3 2 NH4+ + S2Concentrated NH3 makes the solution

basic
http://www.public.asu.edu/~jpbirk/qual/qualan

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

Base-insoluble sulfides and hydroxides. This group includes

hard
acids (Al3+, Cr3+, Fe3+) which react with the hard base OH- to
produce hydroxide precipitates, and borderline acids (Zn2+,
Ni2+, Co2+, Co3+, and Mn2+) with react with the very soft base
S2- to form insoluble sulfides.

Al(OH)3

Cr(OH)3

Fe(OH)3

CoS, NiS, Co2S3

MnS, ZnS

WHITE

GREEN

BROWN

BLACK

PEACH WHITE

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

The concentration of S2is the controlling factor in

determining whether an ion will precipitate. Consider the
dissociation equilibrium for hydrosulfuric acid:
H2S(aq)<==> 2H+(aq)+ S2(aq)
The more strongly acidic the solution, the lower the
concentration of S2. The sulfides that precipitate in base will
not precipitate in acid, because the concentration of S2is too
low. Those sulfides that precipitate in acid will also
precipitate in base because
the concentration of S 2is higher
http://www.public.asu.edu/~jpbirk/qual/qualanal/thioacet.htm

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

Addition of HNO3 dissolves the precipitate by oxidizing S2- to

S (residue)
Addition of NH3 forms complexes with Co2+, Co3+, Ni2+

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

dimethylglyoxime nickel neutral

complex (cherry red precipitate)

http://isite.lps.org/mschmid3/web/documents/GroupIIIProcedures_000.pdf

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

Complex is soluble in 1:1 water:EtOH

Any Fe3+ ions present will interfere with this test, forming
blood-red complex Fe(SCN)2+
During the test for cobalt, if iron is present the red iron
thiocyanate complex may form. In order to see the cobalt test
the iron must be removed in the form of the fluoride complex,
which is colorless: Fe +3 + 6SCN- -> Fe(SCN)6 -3 Fe(SCN)6 -3
+ 6F- -> FeF6 -3 + 6SCN

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

In the evaporation of the solution in step 5, Fe +2 is converted back

to Fe +3 : 3Fe +2 + 4H+ + NO3 - -> 3Fe +3 + NO + 2H2O
HNO3 acts as an oxidizing agent to remove any remaining S 2- ions
present in solution, preventing later reformation of sulfide
precipitates
Initial 4 M NaOH precipitates all ions to hydroxide precipitates Mn+2
http://isite.lps.org/mschmid3/web/documents/GroupIIIP
+ 2OH- -> Mn(OH)2

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

Excess NaOH causes amphoteric Al(OH)3 and Zn(OH)2 to form

complexes, therefore becoming soluble
Al(OH)2 + OH- -> Al(OH)4- (colorless)
Cr(OH)3 + OH- -> Cr(OH)42Zn(OH)2 + 2 OH- -> Zn(OH)42-

(green)
(colorless)
http://isite.lps.org/mschmid3/web/documents/GroupIIIP

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

Hydrogen peroxide (H2O2) is added to the mixture to oxidize the

manganese hydroxide to manganese dioxide and the chromite ion
Cr(OH)4- , to the chromate ion CrO42Mn(OH)2 + H2O2 -> MnO2 + 2 H2O
2 Cr(OH)4- + 3 H2O2 + 2 OH- -> 2 CrO42- + 8 H2O
http://isite.lps.org/mschmid3/web/documents/GroupIIIP

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

HNO3/NO3- dissolves the precipitates as an acid/oxidizing agent

NaBiO3, which becomes soluble in acid, acts as an oxidizing agent
The manganese is identified in the presence of iron by oxidizing it to
the purple permanganate ion MnO4-, by reaction with sodium
bismuthate in a nitric acid solution:
MnO2 + 2 H+ + NO2- -> Mn2+ + NO3- + H2O
2+

+ http://isite.lps.org/mschmid3/web/documents/GroupIIIP
3+

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

The manganese is identified in the presence of iron by oxidizing it to

the purple permanganate ion MnO4-, by reaction with sodium
bismuthate in a nitric acid solution:
MnO2 + 2 H+ + NO2- -> Mn2+ + NO3- + H2O
2 Mn2+ + 5 BiO3- + 14 H+ -> 2 MnO4- + 5 Bi3+ + 7 H2O
http://isite.lps.org/mschmid3/web/documents/GroupIIIPro

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

http://isite.lps.org/mschmid3/web/documents/GroupIIIPr

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+, Co2+,
Zn2+, Mn2+, Mg2+, Ca2+,
Ba2+, Sr2+, Cr3+, Co3+,
Fe3+, Al3+,

Addition HOAc acidifies the solution, leading to

the formation of the water-complexes of
Al(OH)4
Addition of NH3 precipitates the white
gelatinous Al(OH)3, and forms the complex
[Zn(NH3)4]2+
The decantate is acidified to break up the
hydroxyl complexes and convert the aluminum
and zinc to their cations:
Al(OH)4- + 4 H+ -> Al3+ + 4 H2O
In this stephttp://isite.lps.org/mschmid3/web/documents/GroupIIIPr
the chromate ion is converted to

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

Aluminum hydroxide is dissolved in acetic acid

and then reprecipitated in the presence of the
organic dye aluminon which colors the
precipitate red:
Al(OH)3 + 3 H+ -> Al3+ + 3 H2O
Al3+ + 3 OH- -> Al(OH)3

http://isite.lps.org/mschmid3/web/documents/GroupIIIProcedures_000.pdf

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
hydroxide precipitates Al3+,

Excess ammonium
aluminum and zinc hydroxides, converts the
dichromate ion back to chromate and
redissolves the zinc hydroxide by forming the
soluble zinc tetraamine complex ion:
Cr2O72- + Ba2+ -> BaCrO4
Zn2+ + 2 OH- -> Zn(OH)2
Zn(OH)2 + 4 NH3 -> Zn(NH3)42+ + 2 OH-

The chromium is confirmed by precipitation as

http://isite.lps.org/mschmid3/web/documents/GroupIIIProcedures_000.pdf

DECANTATE (B)
Na+, K+, NH4+, Pb2+,
Cu2+, Cd2+, Ni2+,
Co2+, Zn2+, Mn2+,
Mg2+, Ca2+, Ba2+,
Sr2+, Cr3+, Co3+, Fe3+,
Al3+,

Acidifying the solution breaks down the zinc

tetraamine complex:
Zn(NH3)42+ + 4 H+ -> Zn2+ + 4 NH4+

The presence of zinc is confirmed by the formation

of the mixed salt potassium zinc ferricyanide:
3 Zn2+ + 2 K4Fe(CN)6 -> K2Zn3[Fe(CN)6]2 + 6 K+
A gray-white precipitate is formed with
ferrocyanide ion. The precipitate may be bluegreen if traces of iron ions are present:
The formation of the sulfide precipitate confirms
the presencehttp://isite.lps.org/mschmid3/web/documents/GroupIIIPr
of Zn2+, as Fe3+ (which does not form

CATIONS GROUP 4
I N S O L U B L E C A R B O N AT E S A N D
P H O S P H AT E S

Group 4
Cations of this group do not react with the reagents of Groups
1, 2, and 3. They form precipitates with ammonium carbonate
in the presence of ammonium chloride in neutral medium.
Cations of this group are calcium(II), strontium(II), and
barium(II).

http://isite.lps.org/mschmid3/web/documents/gro

DECANTATE (C)
Ca2+, Ba2+, Sr2+,
Na+, K+, NH4+,
Mg2+

HCl + NH3 -> NH4Cl

Group Precipitation The ions of Group IV form insoluble
carbonates:
M2+ + CO32- MCO3
where M2+ = Ba2+ , Ca2+ , or Sr2+
The Group IV cations can be precipitated from a solution of
(NH4)2CO3 made slightly alkaline with NH3. The concentrations of
the ions formed by the dissociation of (NH4)2CO3 in aqueous
solution is governed by the following reaction:
NH4+ + CO32- HCO3- + NH3
A slight excess of ammonia is added
to increase the CO 2http://isite.lps.org/mschmid3/web/documents/gro

DECANTATE (C)
Ca2+, Ba2+, Sr2+,
Na+, K+, NH4+,
Mg2+

Before precipitation, centrifugate from Group 3 analysis

must be evaporated to dryness and ammonium salts
sublimed via ignition (Ba and Ca carbonates insoluble in
excess ammonium)
Addition of NH3 (buffering with NH4+) prevents precipitation
of Mg(OH)2 with carbonate precipitates

http://isite.lps.org/mschmid3/web/documents/groupivanalysis.pdf

DECANTATE (C)
Ca2+, Ba2+, Sr2+,
Na+, K+, NH4+,
Mg2+

Dissolving the Group Precipitate The Group IV

carbonates are readily soluble in acidic
solutions:
MCO3 + 2 H+ M2+ + CO2 + H2O where M2+ =
Ba2+ , Ca2+ , or Sr2+
Acetic acid is used instead of a strong acid so
that the H+ concentration will not be high
enough to prevent the precipitation of BaCrO4
during the next step.
The acidic nature ofhttp://isite.lps.org/mschmid3/web/documents/gr
the solution keeps [CrO42-]

DECANTATE (C)
Ca2+, Ba2+, Sr2+,
Na+, K+, NH4+,
Mg2+

2 BaCrO4 + 2 HCl -> BaCr2O7 +

BaCl2 + H2O
Concentrated HCl dissolves the
Ba precipitate by forming
dichromate (Cr2O7) from all
chromate ions in acid
BaCr2O7 + H2SO4 -> BaSO4 +http://isite.lps.org/mschmid3/web/documents/gr

DECANTATE (C)
Ca2+, Ba2+, Sr2+,
Na+, K+, NH4+,
Mg2+

2 BaCrO4 + 2 HCl -> BaCr2O7 +

BaCl2 + H2O
Flame Test Green

http://isite.lps.org/mschmid3/web/documents/groupiva

DECANTATE (C)
Ca2+, Ba2+, Sr2+,
Na+, K+, NH4+,
Mg2+

Addition of NH3 converts all dichromate

(orange) ions to chromate (yellow).
Higher [CrO42-] now permits precipitation
of SrCrO4

http://isite.lps.org/mschmid3/web/documents/gr

DECANTATE (C)
Ca2+, Ba2+, Sr2+,
Na+, K+, NH4+,
Mg2+

Addition of ethanol helps decrease the

solubility of SrCrO4 by hydrogen
bonding to some of the water
molecules:
Sr2+ + CrO42- --> SrCrO4

http://isite.lps.org/mschmid3/web/documents/

DECANTATE (C)

Yellow SrCrO4 is
precipitated by
shifting the Cr2O72- +
H2O 2 CrO42- + 2
H+ equilibrium to the
right by addition of
OH- ions used to
reduce the H+
concentration.

Ca2+, Ba2+, Sr2+,

Na+, K+, NH4+,
Mg2+

http://isite.lps.org/mschmid3/web/documents/gro

DECANTATE (C)
Ca2+, Ba2+, Sr2+,
Na+, K+, NH4+,
Mg2+

SrCrO4 + HCl -> SrCr2O7 +

SrCl2 + H2O
Flame Test crimson red
http://isite.lps.org/mschmid3/web/documents/gr

DECANTATE (C)
Ca2+, Ba2+, Sr2+,
Na+, K+, NH4+,
Mg2+

Calcium is precipitated
from the remaining
buffered solution as the
oxalate.
Ca2+ + C2O42- -->
CaC2O4

http://isite.lps.org/mschmid3/web/documents/groupivanalysis.pdf

DECANTATE (C)
Ca2+, Ba2+, Sr2+,
Na+, K+, NH4+,
Mg2+

CaC2O4 + 2 HCl CaCl2 +

H2C2O4
Flame Test Red orange

http://isite.lps.org/mschmid3/web/documents/gr

CATIONS GROUP 5
A L K A L I M E T A L I O N S , S O L U B L E S A LT S

Group 5
Common cations, which do not react with reagents of the
previous groups, form the last group of cations, which includes
magnesium(II), lithium(I), sodium(I), potassium(I), and
ammonium(I) ions.

http://isite.lps.org/mschmid3/web/documents/gr

Addition of these reagents

precipitates out any remaining
Group 4 ions
NH3(aq) + HPO42-(aq) NH4+(aq) + PO43(aq)

If the solution is made too basic

with ammonia, a precipitate may
not form.
Mg2+(aq) + HPO42-(aq) + NH3(aq)
MgNH4PO4(s)

DECANTATE (C)
Na+, K+, NH4+,
Mg2+

DECANTATE (C)
Na+, K+, NH4+,
Mg2+

MgNH4PO4 + NaOH + titan yellow Mg(OH)2

+ NH3 + NaPO3

Fresh Original Unknown

Solution
Na+, K+, NH4+

Flame Test
Yellow

K+ Pale Violet

Na+ Intense

Fresh Original Unknown

Solution
Na+, K+, NH4+
If NH4+ is present, the addition of NaOH will
form NH3, which can volatilize upon heat
and come in contact with a piece of litmus
paper adhered to a watch glass covering
the solution