Basic Inorganic Chemistry

PHR 125

Prof. Dr. Mona Bedair

1
 Analysis for anions (acid radical) and for cations (basic radical),
the two parts of inorganic qualitative analysis, are carried out separately.
Either part may be attacked first.
Cations are positively charged fragments or ions of salt or
compound. They are frequently referred to as the metals or basic
radicals.
In studying an unknown, a visual examination should come first.
If the unknown is a solution, what color is it ? Color is important
because some inorganic ions reveal their identities through color alone.
If the unknown is a solid, the color is also important, but it does
not necessarily indicate the colors of the individual ions. Thus, Pb 2+ and
I- are both colorless, but they combine to give the bright yellow PbI2.
Identification of cations can not be performed by tests on the
original substances (or salts), therefore we have to do some schemes for
the systematic separation of cations.
Flowcharts are used to represent the steps in qualitative analysis,
particularly for the analysis of cations, which is more systematic than the
analysis of anions. A flowchart is a schematic outline that begins with
the ions in question, indicated the reagents and the conditions for each
step, and gives the formulas for the chemical products that result.
In considering qualitative analysis and in carrying out the
procedures in the laboratory, keeping track of the analytical steps is
essential. We recommend that you refer to the flowcharts frequently.
Flowcharts can be written in various ways, in which precipitates or
undissolved solids are carried to the left and ions in solution are carried
to the right.

2
ANALYTICAL SEPARATION
OF CATIONS

3
 Common cations (basic radical) may be divided, for purposes of
qualitative analysis, into a number of groups, the members of any group
are precipitated by a particular group reagent. Thus by the addition of a
slight excess of dilute hydrochloric acid to a solution containing all the
common carions, a precipitate is obtained consisting of the chlorides of
silver, lead and mercurous, similarly by the use of the appropriate group
reagents, the remaining cations are separated into different groups.
Generally, analytical separation of cations depends on the varying
solubilities of their chlorides, sulphides, hydroxides and carbonates. The
various groups are summarised in the following Table.
Group Group ions Formula of
Reagent Precipitate
I Dilute HCl Ag+, Pb++, Hg2++ AgCl, PbCl2,
(Silver group) Hg2Cl2

II H2S in presence Hg++, Pb++, HgS, PbS, Bi2S3,

(Copper and of dilute HCl Bi+++, Cu++, CuS, CdS, SnS,
arsenic groups) Cd++, Sn++ As2S3, Sb2S3
As+++ , Sb+++
IIIA Aq. NH3 in Al+++, Al(OH)3,
(Iron group) presence of Cr+++, Cr(OH)3,
NH4Cl Fe+++, Fe(OH)3
Mn3+ Mn(OH)3

IIIB H2S in presence Ni++, NiS,

(Zinc group) of aq. NH3 and Co++, CoS,
NH4Cl Mn++, MnS,
Zn++ ZnS

IV (NH4)2CO3 in Ba++, BaCO3,

(Calcium group) presence of aq. Sr++, SrCO3,
NH3 and NH4Cl Ca++ CaCO3

V No particular Mg++, Na+, K+, different ppted.

(Alkali group) reagent NH4+ forms

4
 Ag+, Pb2+, Hg22+, Hg2+, Cu2+, Bi3+, Cd2+, Sb3+, Sn2+, As3+, Al3+, Cr3+, Fe3+, Mn2+,
Co2+, Ni2+, Zn2+, Ca2+, Ba2+, Sr2+, Mg2+, Na+, K+, NH4+
Cold, dil HCl
Residue Centrifugate
Hg2Cl2, PbCl2, AgCl Hg , Cu , Bi , Cd , Sb , Sn , As3+, Al3+, Cr3+, Fe3+, Mn2+,
2+ 2+ 3+ 2+ 3+ 2+

Co , Ni , Zn , Ca , Ba , Sr2+, Mg2+, Na+, K+, NH4+

2- 2+ 2+ 2+ 2+

Group I H2S/0.3 M HCl

Residue
Centrifugate
Bi2S3, HgS, PbS, CuS, CdS, Sb2S3 Al3+, Cr3+, Mn2+, Fe2+, Co2+,
Ni2+, Zn2+, Ca2+, Ba2+, Sr2+, Mg2+, Na+, K+, NH4+
As2S3, SnS NH4Cl/NH4OH
Group II

Residue Centrifugate
Al(OH)3, Fe(OH)3, Cr(OH)3, Mn(OH)3 Co2-, Ni2+, Zn2+,
Ca2+, Ba2+, Sr2+, Mg2+, Na+, K+, NH4+
H2S/NH4Cl/NH4OH
Group IIIA
Residue
Centrifugate
CoS, NiS, ZnS, MnS
(NH4)2CO3/NH4Cl/NH4OH
Group IIIB
Residue
Centrifugate
CaCO3, BaCO3, SrCO3
Group IV GroupV Mg2,
K + Na+, NH4+
+

Flowchart for separation of cations into

groups

5
 Cation Group I
Silver Group
Mercurous Hg22+
Lead Pb2+
Silver Ag+

Cations Group I brings together three metal ions that form

chlorides which are insoluble in acidic solution. The group reagent is
cold, dilute hydrochloric acid, and this group is sometimes known as
the hydrochloric acid group, the chloride group, or the silver group. The
chlorides of all the other cations in our cation analysis scheme are
soluble in acidic solution.

Condition of precipitation
(1) Cold hydrochloride acid is used to prevent the solubility of
PbCl2 in hot solution.
(2) 6M cold hyrochloric acid
Use of a moderate excess of hydrochloric acid to precipitate the
group serves two purposes :
(1) The excess chloride ion encourages the precipitation of group I
(Le Chatelier’s principle) by the common ion effect of the Cl
i.e: (decrease the solubility of the chloride precipitates of group I)

Example :  AgCl AgCl Ag+ + Cl -

soluble
HCl H+ + Cl
moderate excess c.i.e.

7
 (2) Also, if the unknown contains Bi 3+ or Sb3+(from the subsequent
group) the hydrogen ion prevents precipitation of them as
oxychlorides.

Bi3+ + Cl- + H2O BiOCl  + 2H+

Sb3+ + Cl- + H2O SbOCl  + 2H+
HCl Cl- + H+
moderate excess c.i.e.

i.e. Solubility of BiOCl  or SbOCl  if these cations are present with

group I cations (Bi3+, Sb3+) by the common ion effect of the H+.

Too large excess of the acid is avoided :

(1) Dissolves the silver and lead chlorides by complex formation.
Mercury (I) chloride does not dissolve because the chloro
complexes of mercury (I) are very unstable.
Example :
 AgCl + Cl- [AgCl2]-
Large excess Silver dichloride
soluble complex

 PbCl2 + Cl- [PbCl3]- or [PbCl4]2-

Large excess Lead trichloride Lead tetrachloride
soluble complexes

(2) Also, if the unknown contains Cd 2+ and Sn4+ (from the subsequent
groups), the high chloride concentration forms stable soluble
complexes with them and inhibits the precipitation of CdS and
SnS2 by H2S/H+.

Cd2+ + Cl- [CdCl4]2-

or Sn4+ + Cl- [SnCl6]2

8
 Separation of Cation group I

Hg22+, Pb2+, Ag+

Cold 6M HCl (Procedure 1)

Residue Centrifugate

Hg2Cl2, PbCl2, AgCl (If only Cation Group I present,

all white ppt discard. Otherwise save for Cation
H2O, boil (Procedure 2) Group II)

Residue Centrifugate

Hg2Cl2, AgCl PbCl2

Conc. NH4OH Divide into 3 portions
(procedure 4) (Procedure 3)

Residue Centrifugate H2SO4 Cool K2CrO4

Hg + HgNH2Cl [Ag(NH3)2]++Cl-

black white PbSO4 PbCl2 PbCrO4 
white white yellow

 Dissolve in aqua regia HNO3 until acidic  Pb2+ present

 Evaporate, test with (Procedure 5)
1- SnCl2 AgCl
2- KI white
 Hg22+ present  Ag+ present

Flowchart for Analysis of Cation Group I

9
Procedure 1:
The solubility product of the precipitates of group I cations are
PbCl2 Ksp 1.6 x 10-5
AgCl Ksp 1.1 x 10-10
Hg2Cl2 Ksp 3.0 x 10-18
Solubility product constants indicate that lead (II) chloride is much
more soluble than the chlorides of mercury (I) or silver (I).

Silver (I) ion (Ag+)

Reactions Important in the Separation and Identification of Ag+

Group Precipitation
Ag+ + Cl- AgCl 
white
Dissolution by Complex Ion Formation
1- AgCl  + 2NH3 (aq) [Ag(NH3)2]+ + Cl-
silver diammine

2- AgCl  + 2KCN [Ag(CN)2]- + K+

silver dicyanide

3- AgCl  + xss HCl [AgCl2]- + H+

silver dichloride

10
Reaction with NaOH
 Produces black precipitate insoluble in excess NaOH.

Ag+ + NaOH Ag2O 

black

Ag2O + excess NaOH insoluble

(non amphoteric)

Lead(II) ion (Pb2+)

 Its oxide is amphoteric (dissolves in both acid and alkali)

Reactions Important in the Separation and Identification of

Lead (Pb2+)

group Precipitation
cold
Pb 2+
+ 2Cl -
PbCl2 in group I

Pb2+ + S2-/H+ PbS in group IIA

Dissolution
By oxidation of sulphide

PbS + HNO3 Pb2+ + So + NO + H2O

Reaction with sodium hydroxide
Pb+2 + NaOH Pb(OH)2 

Pb(OH)2 + excess NaOH [HPbO2]- or [Pb(OH)3]-

Reaction with ammonium hydroxide

Produces white basic salts (ppt) which is insoluble in excess

NH4OH

11
 PbCl2 + NH4OH Pb(OH) Cl
Lead hydroxychloride
white basic salt
Confirmatory Tests
1- Pb2+ + SO42- PbSO4 
white
CH3COOH

2- Pb2+ + CrO42- PbCrO4 

yellow
The reaction of Pb2+ with chromate gives yellow precipitate in
weakly acidic medium (dil acetic acid).
 As if we use strong acidic medium (mineral acids) as dil HNO 3, it will
dissolve the yellow precipitate of PbCrO4 and transform it to soluble
dichromate salt.

PbCrO4  + HNO3 PbCr2O7 + H2O

lead dichromate (soluble)
 Also if we use strong alkaline medium, the yellow precipitate of
PbCrO4 will dissolve (amphoteric character)

 3- Pb2+ + KI PbI2
yellow
 lead iodide

PbI2 + excess KI (PbI4)2-

soluble complex lead tetraiodide

12
Mercurous (I) ion, Hg22+
Mercuric (II) ion, Hg2+
The mercurous ion is precipitated as chloride in the silver group;
the mercuric ion is precipitated as sulphide in the copper-arsenic group.
Each mercury atom has two (6s). The loss of two electrons by a mercury
atom produces the mercuric ion (Hg2+). The loss of one electron by a
mercury atom gives a mercurous ion (Hg22+) which is unique among
ions in that it has a single (6s) electron in its outermost orbit. Two of
these ions combine to form the ion (+Hg:Hg+) or simply Hg22+, in which
the two mercury atoms are bonded together by a pair of shared electrons
(a covalent metal-metal bond).
The Hg22+ ion is found in a number of solid compounds. In
aqueous solutions, its existence is limited to the pH region below about 3
to 4. At higher pH values, a disproportionation reaction with water or
hydroxide ion takes place:
H2O
Hg22+ Hgo  + Hg2+
mercury mercuric ion
metal

This also may called self oxidation-reduction reaction.

Therefore precipitation reactions involving mercurous ion are
complicated by disproportionation reactions yielding elemental mercury
and mercuric compounds.
Example :

Hg2Cl2 + 2NH3 HgNH2Cl  + Hgo + Cl-

white black
mercuric mercury
amino chloride metal

13
Reactions Important in the Separation and Identification of
Mercurous (Hg22+)

Group Precipitation
Hg22+ + 2Cl- Hg2Cl2 
white
mercurous chloride

Complex formation
Hg22+ + 4CN- Hgo + [Hg(CN)4]2-
mercuric
tetracyanide

Hg22+ + 4I- Hgo + [HgI4]2-

mercuric
tetraiodide

Reaction With NaOH (non amphoteric)

Hg22+ + 2OH- Hgo + HgO  + H2O
mercury yellow
metal mercuric oxide

Confirmatory Test

Hg2Cl2 + 2NH4OH Hgo  + Hg(NH2)Cl  + NH4+ Cl-

black white
mercury mercuric
metal amino chloride

Reactions Important in the Separation and Identification of

Mercuric (Hg2+)

14
 Mercury(II) sulfide (group II) is the least soluble sulfide. It is not
soluble in either dilute nitric acid or hydrochloric acid, but dissolves in
hot aqua regia with the formation of a chloro complex.

Group Precipitation
H+
Hg2+ + H2S HgS + 2H+
black
mercuric sulphide

Dissolution by :
1- Aqua regia (1:3) Conc. HNO3 : Conc. HCl
Oxidation of S2- and complex ion formation with mercuric
boil
3HgS + 8H + 12Cl + 2NO3  3[HgCl4]2- + 4H2O + 3So + 2NO
+ - -

___________________
aqua regia slightly ionized

2- Hypochlorite reagent

HgS  + NaOCl [HgCl4]2- + SO2

Confirmatory Tests
1- With ammonium hydroxide NH4OH

HgCl2 + 2NH4OH HgNH2Cl  + NH4+ + Cl-

white
2- With stannous chloride reagent SnCl2

HgCl2 + SnCl2  Hg2Cl2  + [SnCl6]2-

white
mercurous stannic hexachloride
chloride
Hg2Cl2 + SnCl2  Hgo + [SnCl6]2-
xss. black stannic hexachloride

15
 mercury
metal

It is an oxidation-reduction reaction.

3- With potassium iodide

HgCl2 + KI HgI2 
scarlet red

HgI2 + KI [HgI4]2-
xss mercuric tetraiodide
soluble complex

 Differentiate between mercuric and mercurous.

 How can you separate and identify mixture of Hg22+ / Hg2+ ??

16
 CATION GROUP II
COPPER-ARSENIC GROUP

Group IIA :
Mercury Hg2+
Bismuth Bi3+
Copper Cu2+
Cadmium Cd2+
Lead Pb2+

Group IIB :
Arsenic As3+ , As5+
Antimony Sb3+ , Sb5+
Tin Sn2+ , Sn4+

17
 This analytical group of cations is composed of eight cations
which are subdivided into the copper group consisting of mercuric,
bismuth, cadmium, copper and lead; and the arsenic group consisting of
arsenic, antimony and tin.
The group reagent (precipitating agent) of cation group II is
hydrogen sulphide in acid medium (0.3 M HCl). Thioacetamide may
also be used; it is hydrolysed in acid solution to give hydrogen sulphide

CH3CSNH2 + 2H2O H2S + CH3COONH4

thioacetamide.

H2S 2H+ + S2-

The real significance of the [H+] as a control of [S2-] can be seen
by examining the ionization of H2S.
[H+]2 [S2-]
_____________________
Ka = = 1.3 x 10-20
[H2S]

A saturated solution of H2S is approximately 0.1 M; therefore, for

a saturated solution of H2S, the expression may be simplified to,
[H+]2 [S2-]
_____________________
Ka =
0.1

or [H+]2+ [S2-] = constant

H2S 2H+ + S2-

HCl H+ + Cl-
c.i.e.
According to the theory of common ion effect, increasing the
concentration of H+ ions in solution of H2S in water, shift the equilibrium
to the left, decreases the dissociation of H 2S in H2O and hence decreases
the sulphide ion concentration.

18
 Adjustment of the acidity
An increase in [S2-] by decreasing the acidity (< 0.3 M HCl)
results in :
a) Precipitation of sulphides of group IIIB.
b) Dissolution of sulphides of group IIB as thioanions (see group IIB).
A decrease in [S2-] by increasing the acidity (> 0.3 M HCl)
results in :
a) Prevention of the precipitation of CdS, PbS, SnS 2 (have higher
solubility products).
b) Formation of stable soluble complexes as [CdCl4]2-, [SnCl62-], [SbCl4]-,
so they can not precipitate by addition of H2S.

19
 Subdivision Of Cation Group II
into IIA and IIB
Cation group II contains eight elements; this large number is too
difficult to analyse satisfactorily unless it is subdivided into two
subgroups: group IIA (copper group) and IIB (aresnic group). The
subdivision is based on the differences in the electronegativity values.
Thus, the members of the copper group have low electronegativity values
and are, therefore, insoluble in alkali sulphides or alkali hydroxides. On
the other hand, the members of the arsenic group are sufficiently
electronegative to dissolve in alkali sulphides giving thioanions, and in
alkali hydroxides giving both thioanions and oxyanions (amphoteric
sulphides).
N.B. : The electronegativity and the acidity increases by increasing the
oxidation number.

20
 Cation group II
1) Biol with H2O2 and expel the excess
2) Adjustment of the acidity
3) Add H2S or thioacetamide

Residue

Suphides ppt of group II

NaOH
or Na2S

Residue
ppt of sulphides
of subgroup IIA
Centrifugate
soluble complexes
of subgroup IIB
(continue as scheme for
subgroup IIB separation)

Flowchart for separation of cation group II

to subgroup IIA and II B

21
 N.B. :
Stannous sulphide is not amphoteric so, it is incompletely soluble in
either NaOH or Na2S. Therefore, to separate stannous with the
subgroup IIB cation sulphides, we have to oxidize stannous to
stannic (Sn4+) by boiling with hydrogen peroxide. The stannic (Sn 4+)
has higher oxidation number and higher electronegativity).
HCl
Sn2+ + H2O2 Sn4+ + H2O

The excess H2O2 must be decomposed by boiling, otherwise it will

oxidize the H2S reagent to colloidal sulphur which is difficult to separate.
docompose
2H2O2  2H2O + O2 
xss strong boiling

H2O2 + H2S So  + 2H2O

colloidal
sulphur

22
 Copper Subgroup (Cation Group IIA)
Hg2+ , Bi3+ , Cu2+ , Cd2+ , Pb2+
1) adjustment of the acidity
at 0.3 M [H+]
2) add H2S

HgS , CuS , PbS, Bi2S3 , CdS

black ppt brown ppt yellow ppt
heat with 1:1 HNO3

Residue Centrifugate
HgS , HgO Bi3+ , Cu2+, Cd2+ , Pb2+
dissolve in ethanol, H2SO4
aqua regia
or hypochlorite Residue Centrifugate

PbSO4  Bi3+ , Cd2+ , Cu2+

Test for Hg2+ white
1) SnCl2 dissolve in
2) NH4OH ammonium Conc. NH4OH
3) KI acetate
Test for Pb2+
1- acetic acid + K2CrO4
2- KI

Residue Centrifugate

 Bi(OH)3 [Cd(NH3)4]2+ colourless

white gelatinous [Cu(NH3)4]2+ blue
dissolve in HCl

Test for Bi3+ Test for Cu2+ Test fo Cd2+

1- xss H2O in presence of Cd2+ in presence of Cu2+
2- Sodium stannite 1) Acetic acid + KCN + H2S
ferrocyanide
2) KI

Flowchart for analysis of cation group IIA

23
Mercuric (II) ion (Hg2+)
Previously discussed with cation group I

Bismuth (III) ion (Bi3+)

Reactions Important in the Separation and Identification of
Bismuth (Bi3+)

 Group reagent
0.3 M
Bi3+ + H2S Bi2S3  + H+
[H+] dark brown
 Dissolution
By oxidation of sulphide

BiS3  + HNO3 Bi3+ + So + NO + H2O

 Confirmatory Test
1- Reaction with conc. NH4OH
Bismuth is separated from Cu2+ and Cd2+ by precipitation with
Conc. NH4OH. The precipitate is insoluble in excess of the reagent (no
ammine complex).

Bi3+ + Conc. NH4OH Bi(OH)3  + NH4

white gelatinous
We dissolve this precipitate in HCl

Bi (OH)3 + HCl BiCl3 + H2O

Test for bismuth by two tests :
2- Oxysalt formation
Addition of large excess water will give white turbidity soluble in
excess acid by common ion effect of the H+.

24
 BiCl3 + H2O BiOCl  + 2H+
soluble large white turbidity
excess bismuth oxychloride

BiOCl  + HCl BiCl3  + 2H+

or HNO3 soluble

3- Sodium Stannite Test

Bi3+ + [HSnO2]- Bio  + [Sn(OH)6]2-

stannite reagent black stannic hexahydroxide
bismuth metal soluble complex

This is an oxidation-reduction reaction where the bismuth ion is

reduced to metallic bismuth (black precipitate) and the stannous ion is
oxidized to stannic.
N.B. : Sodium stannite reagent must be freshly prepared.

SnCl2 + 2NaOH Sn(OH)2 

Stannous hydroxide

Sn(OH)2  + xss NaOH [HSnO2]- or [Sn(OH)4]2-

stannite

On standing (by time), the sodium stannite reagent under goes self
oxidation-reduction and black precipitate of tin is formed
by time

2[Sn(OH)4] 2-
Sno  + [Sn(OH)6]2-
autoxidation
black
 Reaction with NaOH, the bismuth hydroxide is formed which is
insoluble in excess NaOH (not amphoteric)

Bi3+ + NaOH Bi(OH)3 

 xss NaOH
insoluble

25
Copper (II) ion (Cu2+)

Reaction Important in the Separation and Identification of

Copper (Cu2+)
 Group Precipitation
0.3 M
Cu 2+
+ H2S CuS  + 2H+
[H+] black

 Dissolution :
By oxidation of sulpide reaction

 CuS + dil HNO3 Cu2+ + 2NO + H2O + So

 Complex formation reaction

* with NH4OH

Cu2+ + 4NH4OH [Cu(NH3)4]2+ + 4H2O

blue
copper tetramine (soluble complex)
* with KCN

Cu2+ + KCN [Cu(CN)4]3-

cuprocyanide complex
(tetracyanocuprous complex)
stable complex.

KCN is called masking reagent

Confirmatory Tests
1- Cu2+ + 4NH4OH [Cu(NH3)4]2+
deep - blue colour

2- Cu2+ + KI  Cu2 I2 + I2
white
cuprous iodide brown solution

26
 HAC
3- Cu 2+ 4-
+ [Fe(CN)6] Cu2 [Fe(CN)6] 
choclate

N.B. :
To carry out the test with ferrocyanide on the soluble copper
ammine complex we have to acidify first with dil acetic acid (until the
blue colour disappear) to decompose the copper complex, and liberate
the free Copper ion in the medium

[Cu(NH)42+] + dil 4CH3COOH Cu2+ + CH3COONH4

 Reaction with NaOH
xss NaOH
 insoluble (not amphoteric)
Cu2+ + NaOH Cu(OH)2 blue

 CuO 
black

Cadmium II, ion, Cd2+

Reaction Important in the Separation and Identification of

Cadium (Cd2+)

Group precipitation and Confirmatory Test

0.3 M
Cd2+ + H2S CdS 
+
[H ] cadmium sulphide
yellow

 Dissolution :
By Oxidation of sulphide

 CdS + dil HNO3 Cd2+ + NO + H2O + So

27
 Complex Formation
* with NH4OH

Cd2+ + 4NH4OH [Cd(NH3)4]2+

cadium tetramine
complex
* with Conc. HCl

Cd2+ + Conc. HCl [CdCl4]2-

* with KCN (masking agent)

Cd2+ + 4KCN [Cd(CN)4]2-

cadium tetracyanide
unstable complex

N.B. :
How can you separate and identify a mixture of CdS, CuS ?

28
 Arsenic Subgroup
Cation Group IIB
The elements of this group are arsenic, antimony, and tin
As3+ , As5+ , Sb3+ , Sb5+ , Sn2+
Arsenious, Arsenic , Antimonous , Antimonic , Stannous

When group II is boiled with H2O2, the acidity is adjusted at 0.3 M

HCl and H2S or thioacetamide is added, the following amphoteric
sulphide precipitates of subgroup IIB are formed.
AS2S3
yellow ppt
AS2S5

Sb2S3
orange ppt
Sb2S5

SnS2 brown ppt

Because of their high electronegativities, their sulphides (except SnS) are

amphoteric.
These precipitates are soluble in NaOH (separation of subgroups
IIA & IIB) (or Na2S) producing a mixture of thio- and oxysalts
(centrifugate in the separation of subgroup cation precipitate of IIA &
IIB).

29
 Group IIB Cations
As+3, Sb+3, Sn+4

1- acidification with acetic acid ... (1)

2- add H2S or thioacetamide

Residue Contrifugal

As2S3 , Sb2S3 , SnS2 discard

As2S5 Sb2S5
yellow orange brown
ppt ppt ppt

heat with 1:1 HCl (12 M)

Just before boiling ..... (2)

Residue Contrifugate

As2S3  SbCl3, SnCl4

As2S5 
heat to Alkalinize with
dissolve in NH4OH
Conc. HNO3 ... (3)
Test for arsenic
1- Ammonum molybdate reagent.
2- Magnesia mixture reagent.
3- Battendroff reagent

Test for Sn4+ in Test for Sb3+ in

presence of Sb3+ presence Sn4+
- boil with Conc. HCl 1- oxalic acid and H2S ... (5)
and iron wire ....... (4) 2- acetic acid and solid sodium
add HgCl2 thiosulphate
3- excess H2O

Flowchart for analysis of cation group IIB

30
 }
Arsenious (III) ion and Arsenic (V) ion, As3+, As5+
Reactions Important in the Separation and Identification of
As3+, As5+

Group precipitation
H+
2As3+ + 3H2S As2S5  + 6H+
H+
2As5+ + 5H2S As2S5  + 10H+
yellow

Dissolution oxidation by Conc. HNO3

 As2S3 + Conc. HNO3
H3AsO4
 As2S5 + Conc. HNO3
arsenic acid

Separation and Confirmatory Tests

1- Gutziet Test
The arsenic sulphide is dissolved by Conc. HNO 3 and treated with
zinc dust in acid medium (strong reducing agent).
A filter paper moistend with AgNO3 is exposed to the arsine gas
produced from the previous reaction, Blackening to the filter paper
occurs.

H3AsO4 + Zno / H+ AsH3  + Zn2+

arsine gas

AsH3 + AgNO3 Ago  + H3AsO3

black

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2- Magnesia mixture Test
Mixture of (NH4OH, NH4Cl, MgCl2)

H3AsO4 + NH4+ + Mg2+ MgNH4AsO4 

white crystalline ppt
magnesium ammonium arsenate

3- Battendroff Test

The stannous chloride in conc. HCl, reduces arsenic salts to

metallic arsenic

H3AsO4 + SnCl2 + C. HCl Aso  + SnCl62- + H2O

It is an oxidation-reduciton reaction.

Antimonous (III) ion and Antimonic (V) ion (Sb3+, Sb5+)

Reaction Important in the Separation and Identification of
Sb3+, Sb5+

Group precipitation
H+
2Sb3+ + 3H2S Sb2S3  + 6H+

H+
2Sb5+ + 3H2S Sb2S5  + 10H+
orange

Separation and Confirmatory Test

1- Oxysalt formation

SbCl3 + H2O SbOCl  + H+

large excess white turbidity
antimony oxychloride
basic salt

This reaction is reversed by adding HCl

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 SbOCl  + HCl SbCl3 + H2O
or HNO3 soluble
(common ion effect of H+)

2- Iron wire Test

H+
Sb3+ + 3Feo Sbo  + 3Fe2+
black deposit
Oxidation-reduction reaction

3- Test for Sb3+ in presence of Sn4+

Here we test for Sb3+ by H2S to give orange ppt. But the Sn 4+
interferes and give the brown ppt of SnS 2. To get rid of this interference,
we add oxalic acid which forms two complexes with Sb 3+ and Sn4+. The
complex with Sn4+ is stable, while that with Sb3+ is unstable, so on
passing H2S, orange ppt of Sb2S5 is formed.
COO-
Sn4+ +  [Sn(C2O4)3]2-
COO-
stable

COO-
Sb3+ +  [Sb(C2O4)3]3-
COO-
oxalate unstable
+ H2S
  Sb2S3
orange

Oxalic acid is called masking agent.

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Stannous II ion, Stannic (IV) Ion (Sn2+,Sn4+)
Reaction Important in the Separation and Identification of
Sn2+, Sn4+

Group precipitation

Sn2+ + H2O2 + 2H+ + Sn4+  + 2H2O

H+
Sn4+ + H2S SnS2 
brown

Separation and Confirmatory Test

1- Mercuric chloride test

We have to reduce the Sn4+ to Sn2+ using iron wire in acid medium.
Then HgCl2 oxidizes Sn2+ to Sn4+ and being reduced according to the
amount of HgCl2 used. The test may give white ppt (Hg 2Cl2) or grey ppt
(Hg2Cl2 + Hgo) or finally black ppt (Hgo) (oxidation-reduction reaction).

Sn4+ + Feo + H+ Sn2+ + Fe2+

(iron wire/H+) white

Sn2+ + HgCl2  Hg2Cl2 + [SnCl6]2-

white
Hg2Cl2 + xss SnCl2 Hgo + [SnCl6]2-
black

4- Test for stannic in presence of Sb3+

We have to boil with iron wire (Feo) in acid medium for two reasons:
H+
Sb3+ + 3Feo + Sbo  3Fe2+
removed by filtration
H+
Sn4+ + 2Feo Sn2+  2Fe2+

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