Qualitative Analysis

of Group II Cations
Collect: (2016/03/03 revised)

5 centrifuge tubes Centrifuge tube

Labels
Evaporating dish
Latex gloves
Two droppers Test tube
Test tube holder and crucible tongs
Prepare:
Test tube rack, test tubes, and beaker
Take out centrifuge
*Conc. NH3(aq) and HCl: in hood 1
 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 Vortex Mixer Decantation
universal indicator paper
2
 Introduction: Qualitative Analysis of
Group I~V Cations

Cationic Solutions
(I) Insoluble chlorides: Hg22+, Ag+, Pb2+
(II) Insoluble sulfides in acidic medium: Hg2+, Pb2+, Cu2+, Bi3+,
Cd2+, As3+, Sb3+, Sn4+ (metallic sulfide precipitates with
smaller Ksp)
(III) Insoluble sulfide or hydroxides in alkaline medium: Al3+,
Fe3+, Co2+, Ni2+, Cr3+, Zn2+, Mn2+ (metallic sulfide
precipitates with greater Ksp)
(IV) Insoluble Carbonates: Mg2+, Ca2+, Sr2+, Ba2+
(V) Soluble cations: NH4+, Na+, K+

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 Group 2 Cations
- Copper and Arsenic Subgroup
Group 2 cations Insoluble sulfides in acidic medium
HgS, PbS, CuS, Bi2S3, CdS, As2S3, Sb2S3, SnS2

Copper subgroup Hg2+, Pb2+, Cu2+, Bi3+, Cd2+

The sulfides are insoluble in KOH solution, only
soluble in nitric acid

Arsenic subgroup As3+, Sb3+, Sn4+

The sulfides are thioamphoteric that are soluble in
KOH(aq) and nitric acid
Mostly are toxic heavy metals
thus we only examine Cu2+, Bi3+, Sb3+, Sn4+

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 Flow Chart for Separating
Copper and Arsenic Subgroups
S Cationic Solution
Cu2+, Bi3+, Sb3+, Sn4+
CH3CNH2 + H+ + 2H2O
(2, 2, 2, 8 drops)
O
(pH 0.5)
2 d 13%TA,
CH3COH + NH4+ + H2S(aq) Centrifuge and separate
(Repeat 13%TA precipitation once)

Ppt 2-1
Soln 2-1
Bi2S3, CuS, Sb2S3, SnS2

Wash ppt with 1 d 6 M NH4Cl and 20 d of water, cfg.

Add 10 d 0.5 M KOH to ppt and mix well
Heat in boiling water bath
Cfg. and separate the ppt and supernatant
(Repeat this extraction with KOH once)

Ppt 2-2 (copper subgroup) Soln 2-2 (arsenic subgroup)

Bi2S3, CuS SbS33-, SbO33-, SnS32-, SnS2OH, (KOH)

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Separate and
Ppt 2-2 (Copper Subgroup)
Identify Cu2+ and Bi3+ Bi2S3, CuS
Wash ppt with NH4NO3/water
CuS, Bi2S3 + NO3- Cfg. to get ppt.
Cu2+, Bi3+ + S + NO Add 5 d. 6 M HNO3/ 5 d. H2O
Heat in boiling water bath
Cfg. and obtain soln

Soln 2-3 Discard Residue

Bi3+, Cu2+ (Contains S)
Add and mix with 15 M conc. NH3(aq) until basic
(confirm with litmus test)
Cfg. and separate ppt and supernatant

Ppt 2-4
Bi(OH)3(s) (white) Soln 2-4
Cu(NH3)42+ (deep blue)
Add
sodium stannite reagent
Sn(OH)3- (freshly prepared)

Bi(s) (black) 2Bi(OH)3(s) + 3Sn(OH)3 + 3OH

2Bi + 3Sn(OH)62- 6
Separate and Identify
Sn4+ and Sb3+ Soln 2-2 (arsenic subgroup)
SbS33-, SbO33-, SnS32-, SnS2OH
SbS33- + H+ Sb2S3(s)
Sb2S3(s) + H+ + Cl- 2SbCl4(aq) 1520 d of conc. HCl
Heat in boiling water bath, till ppt
dissolves
Cfg, pour supernatant into evaporating dish

SnCl62- + 3H2C2O4 Soln 2-6 Discard

Sn(C2O4)32- (stable) SnCl62-, SbCl4 Residue
SbCl4- + H2S Sb2S3 (orange)
Evaporate till approx. 4 d left
Add 1 mL water and divide into 2 parts
Sn2+ + 2HgCl2
Hg2Cl2(s) + Sn4+ + 2Cl-
SbTest Sn test

small spatula H2C2O4(s) Small Al strip /6 M HCl

2 d 13%TA Heat in boiling water bath to dissolve
Warm in water bath Cfg. and obtain soln
Add 0.1 M HgCl2 to solution

Hg2Cl2(s) (white)
Sb2S3(s) (orange)
Hg (black)
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 Separate Copper and Arsenic
Subgroups

Add 13%TA Separate ppt and

Centrifuge
Heat in warm water supernatant by
Balance diagonally
Produce sulfide ppt decantation

1) 1 d 6 M NH4Cl/20 d H2O to
wash ppt, then cfg.
2) Add 10 d 0.5 M KOH to ppt

3) Heat in boiling water bath

4) Cfg. and separate Ppt 2-2 Soln 2-2
Sulfide ppt 5) Repeat KOH extraction once Copper subgroup Arsenic subgroup
CuS, Bi2S3 Contains Sn4+, Sb3+
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 Copper Subgroup: Use HNO3
to Dissolve CuS, Bi2S3

Ppt 2-2
Copper Add 5 d water and 5 d 6 Heat till reaction starts
subgroup (starts to bubble)
CuS, Bi2S3
M HNO3
Heat in boiling water bath Ppt is dissolved and
appears white and milky
1 d 0.2 M NH4NO3/20
d H2O to wash ppt,
Cfg. to get ppt.
3(CuS, Bi2S3)(s) + 2NO3-(aq) + 8H+(aq)
3(Cu2+Bi3+)(aq) + 2NO(g) + 3S + 4H2O
The water bath should be keep boiling
Mix the HNO3 and ppt thoroughly
Heat to the black sulfides disappear, and the solution appears to be
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off-white for elemental sulfur forms
 Separate and Identify Cu2+
and Bi3+
Add conc.
Cfg. and take NH3 to basic Centrifuge
supernatant

Contains
Cu2+, Bi3+ (confirm with litmus test) Cu(NH3)42+

Add sodium
stannite reagent*

* Prepare sodium stannite reagent freshly : Bi

NaOH NaOH
SnCl 2(aq)

(aq)
Sn(OH) 2(s)
(aq)
Sn(OH) 3(aq)
Do not add more NaOH when ppt dissolved 10
 Separate and Identify Sn4+
and Sb3+
Add conc. Excess conc. HCl
HCl slowly (ca. 15-20 d)

Dissolve when heated

Transfer to
Soln 2-2 evaporating dish
Contains
Sn4+, Sb3+ SbS33- + SbO33- + 6H+ Sb2S3(s)(orange) + 3H2O
SnS2OH- + H+ SnS2(s)(yellow) + H2O

1/4small spatula H2C2O4(s) Sb

2 d 13%TA
Heat in water bath

Evaporate to 4 d

Add 1 mL H2O
Separate into 2 Sn
tubes Small Al strips / HCl
Heat till dissolve,
Cfg. to get soln 11
Add HgCl2 to liquid portion
 Expected Results

Keep the
resulting
Cu2+ Bi3+ Sb3+ Sn4+
solutions for TA
to check
Record all the
observations, i.e.
color, ppt, rate
etc.

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 Manipulate the Centrifuge
Use centrifuge tubes in centrifuge, do not use test tubes
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 to fix
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

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Notice
Wear gloves
Always use test tube holders, test
tube racks, and crucible tongs
Add reagents on top of the
centrifuge tube to avoid
contamination of chemicals
Do not take excess chemicals to
avoid pollution
Solutions must be mixed thoroughly
after adding reagents
Dip solution on testing paper to
determine acidity
All heating should be done in the
hood
Conc. NH3(aq) and HCl(aq) are in
hood
Recycle heavy metal waste 14