1

E11 Qualitative Analysis

of Group II Cations
Collect:
5 centrifuge tubes
Blank labels
One test tube holder, one pair of crucible tongs
One evaporating dish
Latex gloves
Two droppers
Prepare:
Test tube rack, test tube, beaker
Take out centrifuge, keep away from sink
*Concentrated ammonia and hydrochloric acid: in hood
2
Objective
To learn the techniques of separating and identifying some
common cations
To understand the principles of precipitation and equilibrium of
complex formation
Techniques
Vortex mixer
Precipitation
Centrifuge
Decantation
Litmus and
universal indicator paper
Vortex Mixer
Decantation
3
Cationic Solutions
(I) Insoluble chlorides: Hg
2
2+
, Ag
+
, Pb
2+
(II) Insoluble sulfides in acidic medium: Hg
2+
, Pb
2+
, Cu
2+
, Bi
3+
, Cd
2+
,
As
3+
, Sb
3+
, Sn
4+
(metallic sulfide precipitates with smaller K
sp
)
(III) Insoluble sulfide or hydroxides in alkaline medium: Al
3+
, Fe
3+
, Co
2+
,
Ni
2+
, Cr
3+
, Zn
2+
, Mn
2+
(metallic sulfide precipitates with greater K
sp
)
(IV) Insoluble Carbonates: Ca
2+
, Sr
2+
, Ba
2+
(V) Soluble cations: Mg
2+
, NH
4
+
, Na
+
, K
+
Introduction: Qualitative Analysis of
Group I~V Cations
4
Group 2 cations Insoluble sulfides in acidic medium
HgS, PbS, CuS, Bi
2
S
3
, CdS, As
2
S
3
, Sb
2
S
3
, SnS
2
Copper subgroup Hg
2+
, Pb
2+
, Cu
2+
, Bi
3+
, Cd
2+
The sulfides are not acidic and thus insoluble in KOH
solution, only soluble in nitric acid
Arsenic subgroup As
3+
, Sb
3+
, Sn
4+
The sulfides are thioamphoteric that are soluble in
KOH(aq) and nitric acid
Mostly are toxic heavy metals
thus we only examine Cu
2+
, Bi
3+
, Sb
3+
, Sn
4+
Group 2 Cations
Copper and Arsenic Subgroup
Cationic Solution
Cu
2+
, Bi
3+
, Sb
3+
, Sn
4+
(2, 2, 2, 8 drops)
Ppt 2-1
Bi
2
S
3
, CuS, Sb
2
S
3
, SnS
2
Soln 2-1
Ppt 2-2 (copper subgroup)
Bi
2
S
3
, CuS
Soln 2-2 (arsenic subgroup)
SbS
3
3-
, SbO
3
3-
, SnS
3
2-
, SnS
2
OH
-
, (KOH)
(pH 0.5)
2 d 13%TA,
Centrifuge
Rinse ppt with 1 d 6 M NH
4
Cl and 20 d of water, cfg.
Add 10 d 0.5 M KOH to ppt, mix well
Heat in boiling water bath
Cfg. (Repeat this extraction with KOH once)
Flow Chart for Separating Copper and
Arsenic Subgroups
CH
3
COH + NH
4
+
+ H
2
S
(aq)
O
CH
3
CNH
2
+ H
+
+ 2H
2
O

S
Separating the
Copper Subgroup
Ppt 2-2 (Copper Subgroup)
Bi
2
S
3
, CuS
Soln 2-3
Bi
3+
, Cu
2+
Discard Residue
(Contains S)
Ppt 2-4
Bi(OH)
3(s)
(white)
Bi(s) (black)
Soln 2-4
Cu(NH
3
)
4
2+
(deep blue)
Add 15 M conc. NH
3(aq)
until basic
(confirm with litmus test)
Cfg.
NH
4
NO
3
/rinse ppt with water
Cfg. to get ppt.
Add 6 M HNO
3
Heat in boiling water bath to gas evolves
Cfg.
Add
sodium stannite reagent
Sn(OH)
3
-
(freshly prepared)
2Bi(OH)
3(s)
+ 3Sn(OH)
3

+ 3OH

2Bi+ 3Sn(OH)
6
2-
CuS, Bi
2
S
3
+ NO
3
-

Cu
2+
, Bi
3+
+ S+ NO

Separating the
Arsenic Subgroup
Soln 2-6
SnCl
6
2-
, SbCl
4

Discard
Residue
SbTest Sn test
Sb
2
S
3(s)
(orange)
Soln 2-2 (arsenic subgroup)
SbS
3
3-
, SbO
3
3-
, SnS
3
2-
, SnS
2
OH

Evaporate till approx. 4 d left

Add water and divide into 2 parts
1015 d of conc. HCl
Heat in boiling water bath, till ppt dissolves
Cfg, pour supernatant into evaporating dish
small spatula H
2
C
2
O
4(s)
2 d 13%TA
Warm in water bath
Hg
2
Cl
2(s)
(white)
Hg (black)
Small Al strip /6 M HCl
Heat in boiling water bath to dissolve
Cfg.
Add 0.1 M HgCl
2
to solution
SbS
3
3-
+ H
+
Sb
2
S
3(s)
Sb
2
S
3(s)
+ H
+
+ Cl
-
2SbCl
4

(aq)
SnCl
6
2-
+3H
2
C
2
O
4

Sn(C
2
O
4
)
3
2-
(stable)
SbCl
4
-
+ H
2
S Sb
2
S
3
(orange)
Sn
2+
+2HgCl
2

Hg
2
Cl
2(s)
+Sn
4+
+2Cl
-
8
Procedure 1: Separating Copper and
Arsenic Subgroups
Add 13%TA
Warm in hot water
Produce sulfide ppt
Centrifuge
Balance diagonally
Separate ppt and
liquids by decantation
1) 1 d 6 M NH
4
Cl/20 d H
2
O to
wash ppt, then cfg.
2) 10 d 0.5 M KOH to ppt
3) Heat in boiling water bath
4) Cfg.
Sulfide ppt
Ppt 2-2
Copper subgroup
CuS, Bi
2
S
3
Soln 2-2
Arsenic subgroup
Contains Sn
4+
, Sb
3+
9
Separating Copper Subgroup:
Using HNO
3
to dissolve CuS, Bi
2
S
3
3(CuS, Bi
2
S
3
)
(s)
+ 2NO
3
-
(aq)
+ 8H
+
(aq)

3(Cu
2+
Bi
3+
)
(aq)
+ 2NO
(g)
+ 3S+ 4H
2
O
The water bath should be at boiling
Mix the HNO
3
and ppt thoroughly
Heat to the black sulfides disappear, and the solution appears to be
off-white for elemental sulfur forms
Heat till reaction starts
(starts to bubble)
Ppt is dissolved and appears
white and milky
Add 5 d water and 6 M HNO
3
Heat in boiling water bath
Ppt 2-2
Copper
subgroup
CuS, Bi
2
S
3
1 d 0.2 M NH
4
NO
3
/
20 dH
2
O to wash ppt, cfg.
10
Separating and Identifying:
Cu
2+
and Bi
3+
Centrifuge
Cfg. and
take
supernatant
Contains
Cu
2+
, Bi
3+
Sodium stannite reagent: freshly prepared, NaSn(OH)
3
Do not add more NaOH when dissolved. (Approx. 3 d)

3(aq)
NaOH
2(s)
NaOH
2(aq)
Sn(OH) Sn(OH) SnCl
(aq) (aq)
Add conc.
ammonia to
basic
Cu(NH
3
)
4
2+
Bi
Add sodium
stannite reagent
(confirm with litmus test)
11
Separating and Identifying:
Sn
4+
and Sb
3+
in Arsenic Subgroup
SbS
3
3-
+ SbO
3
3-
+ 6H
+
Sb
2
S
3(s)
(orange) + 3H
2
O
SnS
2
OH
-
+ H
+
SnS
2(s)
(yellow) + H
2
O
Copper
subgroup
Arsenic
subgroup
Soln 2-2
Contains
Sn
4+
, Sb
3+
Add conc.
HCl slowly
Evaporate
Dissolves when
heated
Excess conc.
HCl
1/4small spatula H
2
C
2
O
4(s)
2 d 13%TA
Heat
Small Al strips / HCl
Heat till dissolve, cfg.
Add HgCl
2
to liquid portion
Sb
Sn
12
Holding the Evaporating Dish
Using Crucible Tongs
13
Evaporating Dish and Crucible Tongs
14
Reagent
Cations
13 % TA HNO
3(aq)
Ammonia Sodium stannite
Bi
3+
Black-brown
ppt
2Bi
3+
+ 3S
2-
Bi
2
S
3(s)
Ppt dissolves
Bi
2
S
3(s)
+ NO
3
-
Bi
3+
+ S
(s)
+
NO
(g)

White ppt
Bi
3+
(aq)
+ OH
-

Bi(OH)
3(s)
Black ppt
2Bi(OH)
3(s)
+
3Sn(OH)
3
-
+
3OH
-
2Bi
(s)
+
3Sn(OH)
6
2-
Cu
2+
Black ppt
Cu
2+
+ S
2-

CuS
(s)
Ppt dissolves
CuS
(s)
+NO
3
-
Cu
2+
+ S
(s)
+
NO
Dark blue
solution
Cu
2+
+ 4NH
3
Cu(NH
3
)
4
2+
Theoretical Results and
Chemical Equations
15
Reagent
Cations
13 % TA KOH
(aq)
Concentrated ammonia
Sb
3+
Orange ppt
2Sb
3+
+ 3S
2-

Sb
2
S
3(s)
Ppt dissolves
Sb
2
S
3(s)
+ 6OH
-
SbS
3
3-
+ SbO
3
3-
+ 3H
2
O
Produces orange ppt first, then
disappears
SbS
3
3-
+ SbO
3
3-
+ 6H
+
Sb
2
S
3(s)
+ 3H
2
O
Sb
2
S
3(s)
+ 6H
+
+ 8Cl
-
SbCl
4
-
+ 3H
2
S
Sn
4+
Yellow ppt
Sn
4+
+ 2S
2-

SnS
2(s)
Ppt dissolves
SnS
2(s)
+ OH
-

SnS
2
OH
-
SnS
2(s)
+S
2-

SnS
3
2-
Produces yellow ppt first, then disappears
SnS
2
OH
-
+ H
+
SnS
2(s)
+ H
2
O
SnS
2(s)
+ 4H
+
+ 6Cl
-
SnCl
6
2-
+ 2H
2
S
Theoretical Results and
Chemical Equations
16
Reagent
Cations
Al + H
+
HgCl
2
H
2
C
2
O
4
+ TA
Sb
3+
Orange ppt
SnCl
6
2-
+ H
2
C
2
O
4

Sn(C
2
O
4
)
3
2-
+ 6H
+
+ 6Cl
-
(stable)
SbCl
4
-
+ 3H
2
S
Sb
2
S
3(s)
+ 6H
+
+ 8Cl
-
Sn
4+
Clear solution
Sn
4+
+ Al
Sn + Al
3+
Sn + 2H
+

Sn
2+
+ H
2
White(Hg
2
Cl
2
) black(Hg)
ppt
Sn
2+
+ 2HgCl
2

Hg
2
Cl
2(s)
+ Sn
4+
+ 2Cl
-
Sn
2+
+ Hg
2
Cl
2

2Hg
(s)
+ Sn
4+
+ 2Cl
-
Theoretical Results and
Chemical Equations
17
Cu
2+
Bi
3+
Sb
3+
Sn
4+
Expected Results
Save the
resulting
solutions for the
TA to check
18
Using the Centrifuge
Use centrifuge tubes (pointed ended), do not use normal
test tubes (round ended)
Centrifuge tubes should be placed in opposite sides to
keep balanced
The lid should be closed during use; the centrifuge should
be started from slow to check if there are unusual sounds,
then the speed can be increased
If there are unusual sounds or movement in the centrifuge,
the power should be turned off first for it to be fixed
There must be at least one person watching the centrifuge
when in use
Centrifuge for approx. 1~2 min, open lid when the
centrifuge has completely stopped
Methods for mixing solutions completely:
(1) Use stirring rod, (2) shake/flick, (3) Use Vortex mixer
Wear gloves
Always use test tube holders, test tube racks,
and crucible tongs
Do not take excess chemicals to avoid
pollution
Add reagents on top of the centrifuge tube to
avoid contamination of chemicals
Label the centrifuge tubes
Solutions must be mixed thoroughly after
adding reagents: flicking, vortex mixer, or
stirring rod
Dip solution on testing paper to determine
acidity
All heating should be done in the hood
Conc. ammonia and HCl is in hood
Recycle heavy metal waste
19
Cautions