Qualitative Analysis

of Group II Cations
Collect: (2020/05/08 revised)

 5 centrifuge tubes Centrifuge tube

 Evaporating dish
 Test tube holder
 Crucible tongs
 Two droppers Test tube
 Latex gloves
 Labels
Prepare:
 Test tube rack, test tubes, and beaker
 Take out centrifuge
1
*Conc. NH (aq) and HCl: in hood
 Objective
 To learn the techniques of systematic 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+

3
 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+

4
 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)

5
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↓
Sb2S3↓ + H+ + Cl- → 2SbCl4－(aq) Add ca. 20 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↓ + Sn4+ + 2Cl-
SbTest Sn test

¼ 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)
Sb2S(s) (orange)
Hg (black)
7
 Step 1 Separate Sulfide into
Copper and Arsenic Subgroups

• Cu2+, Bi3+, Sn4+, Sb3+ soln • Separate ppt and

• Centrifuge 1 min.
• Add 13%TA supernatant by
* Balance diagonally
• Heat in warm water decantation
• Produce sulfide ppt

1) Add 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
8
CuS, Bi2S3 Contains Sn4+, Sb3+
 Step 2-1 Analysis of Copper
Subgroup

Ppt 2-2
Copper • Add 5 d water and 5 d 6 • Heat till reaction starts to
subgroup evolve bubbles*
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 keep boiling
 Mix the HNO3 and ppt thoroughly
 Heat to the black sulfides disappear, and the solution appears off-white for
elemental sulfur forms 9
 Step 2-2 Separate and Identify
Cu2+ and Bi3+
Add conc.
Cfg. and take NH3 to basic Centrifuge
supernatant

Test with
Contains litmus paper
Cu2+, Bi3+ Cu(NH3)42+

Add sodium stannite

reagent*

*Prepare sodium stannite freshly: Bi

Excess NaOH
SnCl2(aq) + NaOH(aq) → Sn(OH)2(s) Sn(OH)-3(aq)

Add no more NaOH while ppt dissolved.

10
 Step 3 Separate and Identify
Sn4+ and Sb3+
1) Add excess conc.
Add conc. HCl HCl (ca. 20 d)
drop by drop
2) Heat to ppt. dissolve
Insoluble sulfide 3) Transfer to
Soln 2-2 appears* evaporating dish
Contains
Sn4+, Sb3+ * SbS33- + SbO33- + 6H+ → Sb2S3↓ (orange) + 3H2O
* SnS2OH- + H+ → SnS2↓(yellow) + H2O

1) ¼ small spatula H2C2O4(s) Sb

2) 2 d 13%TA
3) Heat in water bath

1) Evaporate to 4 d

2) Add 1 mL H2O
3) Separate into Sn
2 tubes 1) Small Al strips / 6 M HCl
2) Heat till dissolve Al
3) Cfg. to get soln
11
4) Add HgCl2 to liquid portion
Expected Results Condensed report

• Keep the final

resuls for TA to
Cu2+ Bi3+ Sb3+ Sn4+ check
• Record all the
observations, i.e.
malfunction
color of soln or
ppt, rxn rate etc.

12
Notice
 Wear gloves and goggles at all time
 Always use test tube holders, test
tube racks, and crucible tongs
 Add reagents on top of the
centrifuge tube to avoid
contamination
 Do not take excess chemicals to
reduce chemical waste
 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 13
 T8 - Centrifugation

T8 Video on YouTube (Click)

 Check the casing inside the machine is intact. If corrosion causes holes in casing
or there is an unknown object inside, clean or replace the casing.
 Use centrifuge tubes in centrifugation, do not use test tubes.
 Centrifuge tubes should be placed in opposite sides to keep balancing.
 The lid should be closed during use; the centrifuge should be started from slow
rate to check if there is any malfunction, then the speed can be increased.
 If there are unusual sounds or shaking in the centrifuge, the power should be
turned off first in order to fix up.
 There must be at least one person look after the centrifuge when in use.
 Centrifuge for approx. 1~2 min, open lid when the centrifuge has completely
stopped. 14
 T5 - Decantation

T5 Video on YouTube (Click)

 Decantation is a simple method in lab to separate solids and solutions.

When specific gravity of the solid precipitate is large, the solid settles
quickly and tightly. When the solid settles to the bottom of the liquid and
is no longer suspended in the solution, the liquid can be carefully
poured out and the solid will left in the vessel and therefore separates
liquid and solid.
 Stand the suspended solution by allowing the solid to settle to the
bottom of the mixture
 Pour off the particle-free part of the liquid. 15
 T15 - Litmus Paper
 Litmus paper is filter paper which has been treated with a T15 Video on
natural water-soluble dye obtained from lichens. YouTube (Click)
 Blue litmus paper will turn red when encountering acidic
substances.
 Red litmus paper will turn blue when encountering basic
substances.
 Another widely used universal indicator paper which is a
combination of a variety of indicators to obtain various color
changes.
 Stick solution with a clean glass rod and touch it on a litmus
paper or universal indicator paper to observe the color.
 Do not dip litmus paper into solution directly to avoid
contaminating the solution.
 When testing with gas, wet the litmus paper first then place
it on the opening of vessel. After the gas goes out and
absorbed by litmus paper, the acidity and alkalinity can be
judged by color change. 16