Cation Group II (Copper Arsenic

group )
Group IIA: Hg2+, Pb2+, Bi3+, Cu2+, Cd2+
Group IIB: Sn2+, Sb3+, As3+

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 ll 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 + H2O  H2S + CH3COONH4

Thioacetamide

H2S  2H+ + S2-

Group II cation Page 64

The real significance of the [H+] as a control of [S2-] can be seen
by examining the ionization of H2S.

H + 2 [S2− ]
K a= = 1.3 x 10−20
[H2 S]

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− ]
K a=
0.1
Or [H+]2+ [S2-] = constant

H2S  2 H+ + 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.

On the other hand, the addition of strong base shifls this

equilibrium to the fight with a resultant increase the [S 2-].
Group II cation Page 65
 Msl [M2+]+ [s2-]
Ksp = [M2+][S2-]

The metal will precipitate when the product of [M2+] and [S2-]
exceeds the solubility product. This means that the limiting factor
in precipitation is the sulphide ion concentration which is
controlled by the pH (the hydrogen ion conc.).

Therefore, to precipitate cations of group ll (having lower solubility

product than those of group llIB), we need relatively small amount
of sulphide ion.

If the [H+] is controlled to become 0.3 M. the [S 2-] will be 1 x 10-19

M. This is sufficient to precipitate the sulphides of the elements of
cation group ll.

Adjustment of the acidity

An increase in [S2-] by decreasing the acidity (< 6.3 M HCl)
results in:
a) Precipitation of sulphides of group lll.
b) Dissolution of sulphides of group IIa as thio-anions (see
group Ila).

Group II cation Page 66

A decrease in [S2-] by increasing the acidity (> 0.3 M HCI)
results in :

a) Prevention of the precipitation of CdS, PbS. SnS2;

(have higher solubility products).
b) Formation of stable soluble complexes as[CdCl4]2-,
[SnCl6]2-. [SbCl4]-. so they cannot precipitate by addition
of H2S.

Subdivision of cations group II intoIIA and IIB.

Cation group ll 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 (arsenic group). The
subdivision is based on the differences in the electronegativity
values. Thus, the members of the copper group have low
electronegativily 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).

Group II cation Page 67

NB. : The eleclronegativity and the acidity increases by increasing
the oxidation number.

The thio and oxyanions of group IIB are re-precipitated on

acidification acetic acid is used; since if strong HCl is used,
antimony and tin sulphides will dissolve forming soluble
complexes.

Group II cation Page 68

 Copper Subgroup

Cation group II

1. Boil with H2O2 and expel the excess

2. Adjustment the acidity
3. Add H2S

Residue

Sulphides of Group II

NaOH or Na2S
Residue Centrifuge

Ppt of sulphides of Soluble complexes of

subgroup IIA subgroups IIB

Flowchart for separation of cations group II

to subgroup IIA and IIB

N.B.:
(1) Unless Hg2+ is an element of group IIA, but it appears in
bothIIA and II B subgroups because its precipitate HgS in group
Group II cation Page 69
IIA is partially soluble in alkali sulphide (Na2S) and pass with
group IIB
HgS + Na2S  Hg(SNa)2
soluble salt

(2) 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 (Sn4+) 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
𝑺𝒕𝒓𝒐𝒏𝒈 𝒃𝒐𝒊𝒍𝒍𝒐𝒊𝒏𝒈
2 H2O2 2 H2O + O2 
H2O2 + H2S  So  + 2 H2O
colloidal sulphur

Group II cation Page 70

 Copper subgroup (Cation group II A)
Hg2+, Pb2+, Bi3+, Cu2+, Cd2+

HgS,
Adjustment the acidity
PbS, Black ppt
CuS, Add H2S
Bi2S3, Brown ppt
CdS Yellow
Heat with 1:1 HNO3/H2SO4
Residue Centrifuge

Pb2+, Bi3+, Cu2+, Cd2+

HgS, HgO
Ethanol/ H2SO4

Dissolve in aqua regia Residue Centrifuge

Test for Hg2+
1) SnCl2 PbSO4 Bi3+, Cu2+, Cd2+
2) NH4OH White ppt
3) KI
Conc. NH4OH
Dissolve in ammonium Residue
acetate Centrifuge
Test for Pb2+
1- Acetic acid +K2CrO4
Bi(OH)3
2- KI
white gelatinous ppt [Cd(NH3)4 ]2+ colourless
dissolve in HCl [Cu(NH3)4]2+ blue
Test for Bi3+
1- Xss H2O
2- Sodium stannite

Test of Cu2+ in presence of Cd2+ Test for Cd2+ In presence of

1) Acetic acid + ferrocyanide Cu2+ KCN + H2S
2) KI

Flowchart for analysis of cation group IIA

Group II cation Page 71

Mercuric (ll) Ion (Hg2+)
Previously discussed with cation group I

Bismuth (Ill) ion (Bi3+)

Reactions Important in the Separation and Identification

of Bismuth (Bi3+)

1. Group reagent
3+ 𝟎.𝟑 𝑴 [𝑯+]
Bi + H2S Bi2S3  + H+
dark brown
2. Dissolution
 Oxidation of sulphides
BiS3  + HNO3  Bi3+ + So + NO + H2O

 Complex formation reaction

BiCl3 + conc. HCl  [BiCl4]-
bismuth te-trachioride
soluble complex
3. Confirmatory Test:

1- Reaction with conc. NH4OH

Bismuth is separated from Cu2+ and Cd2+ by precipitation with
Group II cation Page 72
conc. NH4OH The precipitate is insoluble in excess of the reagent
(no ammine complex).

Bi3+ conc. NH4OH  [BiCl4]-

white gelatinous

We dissolve this precipitate in HCI

 Bi(OH)3 + HCl  BiCl3 + H2O

Two tests for bismuth by:

 Oxysalt formation
Addition of large excess water will give white turbidity soluble in
excess acid by common ion effect of the H+

BiCl3 + H2O  BiOCl  + 2 H+

soluble large white turbidity
excess bismuth oxyehioride

BiOCl  + HCI  BiCl3 + 2H+

or HNO3 soluble

 Sodium Stannite Test

Bi3+ + [HSnO2]-  Bi°  + [Sn(OH)6]2-
Stannite reagent black stannic hexahydroxide
bismuth metal soluble complex

Group II cation Page 73

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 + 2 NaOH  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 𝒂𝒖𝒕𝒐𝒙𝒊𝒅𝒂𝒕𝒊𝒐𝒏
[Sn(OH)4]2 Sno  + [Sn(OH)6]2-
black

4. Reaction with NaOH

the bismuth hydroxide is formed which is insoluble in excess

NaOH (not amphoteric)

Group II cation Page 74

 Bi3+ + NaOH  Bi(OH)3 
 xss NaOH
Insoluble

Copper (II) ion (Cu2+)

Copper (I) and copper (II) are known in solid compounds.

Copper(ll) is the only common species in aqueous solution.
The Cu2+ ion in solution is blue in colour, while the anhydrous
cupric salts are white.
In acidic solution, Cu+ and Cu2+ are related by a redox
disproportionation equilibrium like that of the mercury.

2Cu+  Cu (s) + Cu2+

[𝐂𝐮+ ]𝟐
𝐊= =
[𝐂𝐮𝟐+ ]
At equilibrium the concentration of Cu2+ is always (1.4 x 106)
[Cu+]2 .

The volatile compounds of some elements give characteristic

colors when the compound or its solution is exposed to a flame.

Group II cation Page 75

This usually is done by dipping a clean platinum wire into the
compound or its solution and holding we wire ine the oxidizing
part of a Bunsen burner flame. Copper (II) nitrate gives a bright
blue flame color; copper (ll) chloride gives a green flame color.

Reaction Important in the Separation and Identification

of Copper (Cu2+):

1. Group Precipitation

2+ 𝟎.𝟑 𝑴 [𝑯+]
Cu + H2S CuS  + 2H+
black
2. Dissolution :

 Oxidation of sulpide reaction

CuS(s) + NO3-(aq)  Cu2+(aq) + SO42-(aq) + NO(g)

 Complex formation reaction

o With NH4OH
Cu2+ + 4 NH4OH  [Cu(NH3)4]2+ + 4 H2O
blue:
copper tetramine (soluble complex)

Group II cation Page 76

 o With KCN
Cu2+ + KCN  [Cu(CN)4]3-
cuprocyanide complex
(tetracyanocuprous complex)
stable complex.

KCN is called masking reagent

3. Confirmatory Tests:

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

deep - blue colour

 Cu2+ + 2 SCN  Cu(SCN)2 

thiocyanate black

 Cu2+ + KI  Cu2I2  + I2
white
cuprous iodide brown solution

𝑯𝑨𝑪
Cu2+ + [Fe(CN)6]4- Cu2 [Fe(CN)6] 
chocolate

Group II cation Page 77

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(NH3)4]2+ + dil. 4 CH3COOH  Cu2+ + CH3COONH4

 Reaction with NaOH

xss NaOH insoluble (not amphoteric)

𝑯𝑨𝑪
Cu2+ + NaOH Cu2 (OH)2  blue
CuO 
Black

Group II cation Page 78

Cadmium II ion,Cd2+
Reaction Important in the Separation and identification
of cadium (Cd2+)

Group precipitation and Confirmatory Test

2+ 𝟎.𝟑 𝑴 [𝑯+]
Cd + H2S CdS  + 2H+
Cadmium sulphide
Canary yellow
Dissolution :

 By Oxidation of sulphide

CdS + dil. HNO3  Cd2+ + NO + H2O + So

 Complex Formation

With NH4OH
Cd2+ + 4 NH4OH  Cd(NH3)4]2+ + NO + H2O + So
cadium tetramine
complex

Group II cation Page 79

 with conc. HCI

Cd+ + conc. HCl  [CdCl4]2-

with KCN

Cd2+ + 4 KCN  [Cd(CN)4]2-

cadium tetracyanide
unstable complex

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

Group II cation Page 80

 Arsenic subgroup

The elements of this group are arsenic, antimony, and tin

As3+, As5+ , Sb3+ , Sb5+ , Sn2+
Airsenious, Arsenic , Antimonous ,Antimonie ,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 , As2S5 ], [Sb2S3 , Sb2S5 ], SnS2

Yellow ppt orangeppt brown ppt

Because of their high electroneganvities, 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).

Group II cation Page 81

 As2S3 + NaOH  AsS2- + AsO2-
thioarsenite oxyarsenite

As2S5 + NaOH  AsS3- + AsO3-

thioarsenatc oxyarsenate

Sb2S3 + NaOH  SbS2- + SbO2-

thioantimonite oxyantimonite

Sb2S5 + NaOH  SbS3- + SbO3-

thioantimonate oxyantimonate

 SnS + NaOH  sparingly soluble

 SnS2 + NaOH  [SnOS22-]2-

Thio oxystannate

N.B. :
Re-precipitation of the Arsenic Group Sulphides
The alkaline solution, containing the ions of the arsenic group in
the form of soluble complex thio- or oxy-anions, is acidified to

Group II cation Page 82

destroy these complex ions and to re-precipitate the sulphides of
the arsenic group.

3 AsS3- + AsO3- + 4H+  2 As2S3  + 2 H2O

5 AsS3- + AsO3- + 6H+  2 As2S5  + 3 H2O

3 SbS2- + SbO2- + 4H+  2 Sb2S3  + 2 H2O

5 SbS3- + SbO3- + 6H+  3 Sb2S5  + 3 H2O

SnOS22- + 2H+  SnS2  + H2O

In acidification of the previous soluble complex solutions, dilute

acetic acid is preferred to HCl. As HCl will form soluble
complexes with Sn4+ and Sb3+, so prevent their reprecipitation as
sulphide salt (are lost with the discarded centrifugate.)

Example
SbS2- + SbO2- + conc. HCl  [SbCl4]-
SnOS22- + conc.HCl  [SnCl4]2-
soluble complex

Group II cation Page 83

 Centifugate of Cation Group II
acidify with acetic acid
add H2S
Residue Centrifuge

As2S3 , Yellow ppt

As2S5 , Discard
Sb2S3 orange ppt
Sb2S5 ,
SnS2 brown ppt Heat with 1:1 HCl
Just before boiling

Residue
Centrifuge
As2S3 ,
SbCl3 ,
As2S5 , SnCl4 ,
Heat to dissolve alkalinization
in conc. HNO3 with NH4OH
Test for arsenic Test for stannic
in presence of Test for Sb in presence of sn
1. Ammonium
Sb3+ (boil with
molybdate reagent 1. Oxalic acid + H2S
conc, HCl and
2. Magnesia mixture 2. Acetic acid and solid
iron wire
reagent sodium thiosulphate
3. Battendroff reagent 3. Excee water

Flowchart for analysis of cation group IIB

Group II cation Page 84

Arsenious (Ill) ion and Arsenic (V) ion, As3+, As5+

Reactions Important in the Separation and

Identification of As3+, As5+

1. Group precipitation

3+ 𝑯+
2As + 3 H2S As2S5  + 6H+
5+ 𝑯+
2As + 5 H2S As2S5  + 10 H+
yellow

2. Dissolution by:

A- Complex formation:

(1) Alkali sulphide (Na2S)

 As2S3 + S2-  AsS2-
 As2S5 + S2-  AsS3-

(2) Alkali hydroxide (NaOH)

 As2S3 + NaOH  AsS2- + AsO2-
 As2S5 + NaOH  AsS3- + AsO3-

Group II cation Page 85

 (3) Yellow ammonium sulphide

(Poly ammonium sulphide) (NH4)2Sx it is mixture of ammonium

sulphide and sulphur. The later has an oxidizing power. All the
products of the dissolution will give the soluble complex of the
higher oxidation state, (thio and oxy arsenate)

As2S3 + (NH4)2Sx 

AsS3- + (NH4)2Sx-1
As2S5 + (NH4)2Sx 

B- Oxidation by conc. HNO3

As2S3 + conc. HNO3 

H3AsO4
As2S5 + conc. HNO3

4. Separation and Confirmatory Tests

The arsenious sulphide and arsenic sulphide are insoluble in l2 M
HCl (differ from sulphides of antimony and tin), but by boiling they
are partially soluble.

Group II cation Page 86

To confirm the presence of arsenic several tests can be done.

1- Gutziet Test

The arsenic sulphide is dissolved by conc. HNO3 and treated with

zinc dust in acid medium (strong reducing agent).
A filter paper moistened 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
If Sb3+ is present it will give the same reaction with the production
of stibine gas which also reduced AgNO3 to Ag°.

Flietmann Modification

To prevent the interference of Sb3+ in the test, we use zinc dust

in alkaline medium or aluminium in alkaline medium (mild

Group II cation Page 87

reducing agent) which can reduce the arsenic and not the
antimony.

2- Ammonium molybdate Test

∆ 𝒄𝒐𝒏𝒄.𝑯𝑵𝑶𝟑
H3AsO4 + (NH4)8MoO4  (NH4)3AsO4.12MoO3
canaly yellow
ammonium arsenomolybdate

3- Magnesia mixture Test

Mixture of (NH4OH, NH4Cl, MgCl2)

H3AsO4 + NH4+ + Mg2+   MgNH4AsO4

white crystalline ppt
magnesium ammonium arsenal

4- Battendroff test

The stannous chloride in conc. l-lCl, reduces arsenic salts to

metallic arsenic

Group II cation Page 88

 H3AsO4 + SnCl3 + HCl   Aso + SnCl62- + H2O
It is an oxidation-reduction reaction.

Antimonous (III) ion and Antiomnic (V) ion (Sb3+,

Sb5+)

Reaction Important in the separation and Identification

of Sb3+, Sb5+

Group precipitation

3+ 𝑯+
2 Sb + 3 H2S  Sb2S3 + 6 H+
5+ 𝑯+
2 Sb + 3 H2S  Sb2S5 + 10 H+
orange

Dissolution by complex formation

1- Alkali sulphide (Na2S)

 Sb2S3 + S2-  SbS2-
 Sb2S5 + S2-  SbS3-

Group II cation Page 89

2- Alkali hydroxide (NaOH)
 Sb2S3 + NaOH  SbS2- + SbO2-
 Sb2S5 + NaOH  SbS3- + SbO3-

3- Yellow ammonium sulphide (NH4)2Sx

 Sb2S3 + (NH4)2Sx 

SbS3- + (NH4)2Sx-1
 Sb2S5 + (NH4)2Sx 

4- Conc. HCl
 Sb2S3 + conc. HCl  SbCl4- + H2S
 Sb2S5 + conc. HCl  SbCl6- + H2S

Separation and Confirmatory test:

1- Oxysalt formation

SbCl3 + H2O  SbOCl + H+

large excess white turbidity
antimony oxychlotidc
basic salt

Group II cation Page 90

The reaction is reversed by adding HCl
SbOCl  + HCl  SbCl3 + H2O
or HNO3 soluble
(common ion effect of H+)

2- Sodium thiosulphate Test

Sb3+ + S2O32- + H+  SbOS2
solid orange
antimony oxysulphide

3- Iron wire Test

3+ o 𝑯+
Sb + 3 Fe  Sbo + 3 Fe2+
black deposit
Oxidation-reduction reaction

4- Test for Sb3+ in presence of Sn4+

Here we test for Sb3 by H2S to give orange ppt. But the Sn4+
interferes and gives the brown ppt. of SnS2. To get rid of this
interference, we add oxalic acid which forms two complexes with
Sb3+ and Sn4+, The complex with Sn4+ is stable, while that with
Sb3+ is unstable, so on passing H2S, orange ppt. of Sb2S5 is
formed.

Group II cation Page 91

Sn4+ +  [Sn(C2O4)3]2-
stable

Sb3+ +  [Sb(C2O4)3]3-
oxalate unstable
H2S
 Sb2S3
orange
Oxalic acid is called masking agent.

Stannous (II) ion, Stannic (IV) Ion (Sn2+,Sn4+).

Reaction Important in the Separation and Identification

of Sn2+,Sn4+.

Group precipitation
Sn2+ + H2O2 + 2H+  Sn4+ + 2 H2O
4+ 𝑯+
Sn + H2S  SnS2
brown

Group II cation Page 92

Dissolution by complex formation

1- Alkali sulphide (Na2S)

 SnS + S2-  sparingly soluble
 SnS2 + S2-  SnS32-

2- Alkali hydroxide (NaOH)

 SnS + NaOH  sparingly soluble

 SnS2 + NaOH  SnoS22-
Thio oxystannate complex

3- Yellow ammonium sulphide (NH4)2Sx

 SnS + (NH4)2Sx 

SnS32- + (NH4)2Sx-1
 SnS2 + (NH4)2Sx 

4- Conc. HCl
 SnS + conc. HCl  [SnCl4]2-
 SnS2 + conc. HCl  [SbCl6]2-

Group II cation Page 93

Separation and Confirmatory Test

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. (HgCl2) or gray ppt. (Hg2Cl2+ Hgo) or finally black ppt. (Hgo)
(oxidation-reduction reaction).

Sn4+ + Fe° + H+  Sn2+ + Fe2+

(iron wire/H+) white
Sn2+ + HgCl2   Hg2Cl2 + [SnCl6]2-
white
 Hg2Cl2 + xxs HgCl2   Hgo + [SnCl6]2-
Black

4- Test for stannic in presence of Sb3+

We have to boil with iron wire (Fe°) in acid medium for two
reasons;
3+ o 𝑯+
Sb + 3 Fe  Sbo + 3 Fe2+
removed by fiitration
4+ o 𝑯+
Sn + 3 Fe  Sn2+ + 2 Fe2+

Group II cation Page 94