Module 2 : Group 1 – Cation Analysis

the solids. For example, the

INTRODUCTION precipitated metal

chlorides of group 1 cations,

containing Ag+, Pb2+, and Hg22+, are
all quite

The composition of relatively insoluble in water. Because PbCl 2 is

complex mixtures of metal ions can much more soluble in hot water than
be determined using qualitative are the other two chloride salts,
analysis, a procedure for however, adding water to the
discovering the identity of metal ions precipitate and heating the resulting
present in the mixture (rather than slurry will dissolve any
quantitative information about their PbCl2 present. Isolating the solution
amounts). The procedure used to and adding a small amount of
separate and identify more than 20 Na2CrO4 solution to it will produce a
common metal cations from a single bright yellow precipitate of PbCrO 4 if
solution consists of selectively Pb2+ were in the original sample
precipitating only a few kinds of (Figure 18.9.218.9.2).
metal ions at a time under given sets
of conditions. Consecutive When a small amount of
precipitation steps become Na2CrO4 solution is added to a
progressively less selective until sample containing Pb2+ ions in water,
almost all of the metal ions are a bright yellow precipitate of
precipitated. PbCrO4 forms.

Group 1: Insoluble Chlorides As another example, treating the

Most metal chloride salts are soluble precipitates from group 1 cations
in water; only Ag+, Pb2+, and with aqueous ammonia will dissolve
Hg22+ form chlorides that precipitate any AgCl because Ag+ forms a
from water. Thus the first step in stable complex with ammonia:
qualitative analysis is to add about 6 [Ag(NH3)2]+. In
M HCl, thereby causing AgCl, PbCl 2, addition, Hg2Cl2Hg2Cl2 disproportio
and/or Hg2Cl2 to precipitate. If no nates in ammonia
precipitate forms, then these cations
are not present in significant 2Hg2+2→Hg+Hg2+(18.9.1)
amounts. The precipitate can be (18.9.1)2Hg22+→Hg+Hg2+
collected by filtration or
centrifugation. to form a black solid that is a mixture
of finely divided metallic mercury and
Metal ions that precipitate together an insoluble mercury(II) compound,
are separated by various additional which is separated from solution:
techniques, such as forming
complex ions, changing the pH of Hg2Cl2(s)+2NH3(aq)→Hg(l)
the solution, or increasing the +Hg(NH2)Cl(s)+NH+4(aq)+Cl−(aq)
temperature to redissolve some of (18.9.2)(18.9.2)Hg2Cl2(s)
+2NH3(aq)→Hg(l)+Hg(NH2)Cl(s)
+NH4+(aq)+Cl−(aq) In qualitative analysis, the ions in a
mixture are separated by selective
Any silver ion in the solution is then precipitation. Selective precipitation
detected by adding HCl, which involves the addition of a carefully
reverses the reaction and gives a selected reagent to an aqueous
precipitate of white AgCl that slowly mixture of ions, resulting in the
darkens when exposed to light: precipitation of one or more of the
ions, while leaving the rest in
[Ag(NH3)2]+(aq)+2H+(aq)+Cl− solution. Once each ion is isolated,
(aq)→AgCl(s)+2NH+4(aq)(18.9.3) its identity can be confirmed by using
(18.9.3)[Ag(NH3)2]+(aq)+2H+(aq) a chemical reaction specific to that
+Cl−(aq)→AgCl(s)+2NH4+(aq) ion.

Similar but slightly more complex Cations are typically divided

reactions are also used to separate into Groups, where each group
and identify the individual shares a common reagent that can
components of the other groups. be used for selective precipitation.
The classic qualitative analysis
In qualitative analysis, the identity, scheme used to separate various
not the amount, of metal ions groups of cations is shown in the
present in a mixture is determined. flow chart below.
The technique consists of selectively
precipitating only a few kinds of
metal ions at a time under given sets
of conditions. Consecutive
precipitation steps become
progressively less selective until
almost all the metal ions are
precipitated. Other additional steps
are needed to separate metal ions
that precipitate together.

LESSON 1: GROUP
PRECIPITATION OF GROUP 1
CATIONS
One common task in analytical
chemistry is the identification of the
various ions present in a particular Note that Ag+Ag+, Pb2+Pb2+,
sample. For example, if you are an and Hg2+2Hg22+ are called the
environmental chemist your job may Group I cations since they are the
be to recover soil or water samples first group separated from the larger
in order to determine the presence of mixture. Since these ions all form
toxic ions such as Pb2+ or Hg2+2. A insoluble chlorides, their separation
common experimental method used from all other ions may be
to identify ions in a mixture is accomplished by the addition of 6
called qualitative analysis. M HClHCl (aq) resulting in the
precipitation these accumulate rapidly, and it is
of AgClAgCl (s), PbCl2PbCl2 (s), very easy to get tubes and/or
and Hg2Cl2Hg2Cl2 (s): solutions mixed up. It is also
suggested that students keep a
Ag+(aq)+Cl−(aq)⟶AgCl(s) “waste” beaker near their work area
Hg2+2(aq)+2Cl−(aq)⟶Hg2Cl2(s) in which to discard all solutions
Pb2+(aq)+2Cl−(aq)⟶PbCl2(s) locally, and then pour their combined
waste solutions into the large waste
The sample must then be container provided by the instructor
centrifuged (spun rapidly), which at the end of the lab.
separates the solid precipitates from Finally, be sure to clean out and
the ions still in solution. The solids thoroughly rinse all glassware
settle to the bottom, and the solution (including stirring rods!) with
containing the remaining ions deionized water between uses.
(Groups 2 – 5) remains on top of the Cross-contamination is one of the
solid. This solution is called the most common causes of false
supernatant solution and must be observations leading to incorrect
carefully decanted (poured off conclusions.
without disturbing the solid), and
saved for further study. The Group I Part A: Analysis of Known Mixture
cations contained within the of Group I Cations – A Positive
collected precipitate must then be Control
separated from each other in order
for the presence of each ion to be Experiment - Precipitation of
confirmed. Group 1 Cations

General Instructions 1. Prepare a mixture of Group I

In this lab, you will first prepare a cations by adding 1.0 mL of
solution containing all three Group I each of the following aqueous
cations and analyze it by following solutions to a small test tube:
the above procedure. The results 0.1 M AgNO3AgNO3, 0.2
you obtain will serve as a “positive M Pb(NO3)2Pb(NO3)2 and
control”. Then you will be supplied 0.1 M Hg2(NO3)2Hg2(NO3)2.
with an unknown sample that Note that 1.0 mL is generally
contains one, two, or perhaps even between 10-15 drops.
all three of the Group I cations. You 2. Pour 1.0 ml of the above
will determine which cations are mixture into a second small
present in the sample by following test tube and then add 2
this procedure a second time, and by drops of 6 M HClHCl to this
comparing the results you obtain to test tube.
those observed (positive tests) in the 3. Centrifuge the mixture from
known control mixture. Step 2 in order to completely
separate the solid precipitate
To get correct results in this lab, from the solution. Make sure
good organizational skills and that you balance the
techniques are essential. Be sure to centrifuge before you start.
label all tubes and solutions because Balancing is done by placing
 a test tube containing water confirmed by the formation of a
opposite to the test tube yellow precipitate
containing the precipitate in of PbCrO4PbCrO4 upon the addition
the centrifuge. The two test of aqueous K2CrO4K2CrO4:
tubes should have
approximately equal weights. Pb2+(aq)+CrO−42(aq)⟶PbCrO4(s)
4. Add one more drop
of HClHCl to ensure that the Next, Hg2+2Hg22+ and Ag+Ag+ cati
precipitation is complete. If ons can be separated by adding 6
more precipitate is observed M NH3NH3 (aq) to the solid mixture
then centrifuge the mixture of the two chlorides. Silver chloride
again. will dissolve since it forms a soluble
5. Decant the supernatant complex ion with ammonia:
solution into another small
test tube and save the AgCl(s)+2NH3(aq)⟶Ag(NH3)+2(aq)
precipitate for further study. +Cl−(aq)
The supernatant solution may
be discarded in the lab waste However, mercury(I) chloride reacts
container. with the ammonia yielding what
appears to be a gray solid which is
actually a mixture of black HgHg (l)
and white HgNH2ClHgNH2Cl (s).
LESSON 2: SEPARATION OF The presence of this gray solid is
GROUP I CATIONS confirmation of the presence
of Hg2+2Hg22+.

Hg2Cl2(s)+2NH3(aq)⟶Hg(l)
+HgNH2Cl(s)+NH+4(aq)+Cl−(aq)

The presence of Ag+Ag+ can be

confirmed by the appearance of a
Separation and Confirmation of white precipitate upon adding 6
Group 1 Cations M HNO3HNO3 (aq) to the solution.
The nitric acid reacts with the
Lead(II) chloride can be separated ammonia and thus destroys the
from the other two chlorides based complex-ion containing the silver
on its increased solubility at higher cation. Once in the solution again
temperatures. This means that the silver cation precipitates with the
lead(II) chloride will dissolve in hot chloride as indicated by the following
water, leaving the mercury(I) reactions:
chloride and the silver chloride in
solid form: Ag(NH3)2+(aq)+2H+(aq)⟶Ag+(aq)
+2NH+4(aq)
PbCl2(s)⟶Pb2+(aq)+2Cl−(aq)
Ag+(aq)+Cl−(aq)⟶AgCl(s)
The presence of Pb2+Pb2+ in the
aqueous solution can then be
 Separation precipitate is confirmation of
of Pb2+ from Hg2+2and Ag+ the presence of
the Pb2+Pb2+ ion.
6. Wash the precipitate from
Step 5 to remove Separation and Identification
contaminants that may be of Hg2+2
trapped within the solid. This
can be accomplished by 10. Add 10-12 drops of 6
adding 1.0 mL of deionized M NH3NH3 to the precipitate
water, stirring, and then from Step 8 and mix
centrifuging. Once again thoroughly with your stirring
decant the supernatant rod.
solution into a small test tube. 11. The appearance of a gray
Save the precipitate and solid is confirmation of the
discard the supernatant presence of Hg2+2Hg22+.
solution. Centrifuge the mixture and
7. Prepare a hot water bath by decant the supernatant
adding tap water to a 250 mL solution into another small
beaker. Add water until the test tube. Save the
beaker is about one-half full. supernatant solution since it
Assemble a stand, ring clamp, now contains silver in the
and wire gauze to heat the form of the
water over the Bunsen burner aqueous Ag(NH3)+2Ag(NH3)
until it is boiling. Add 2.0 mL 2+ ion.
of deionized water to the test
tube containing the clean
precipitate and place it in the
hot water bath. Periodically
stir the mixture in the test tube
for 3-4 minutes.
8. Remove the test tube from Identification of Ag+
the hot water bath and
immediately centrifuge the hot 12. To the solution obtained in
mixture. Carefully decant the Step 11, slowly add 6
hot supernatant solution into M HNO3HNO3 until the
another small test tube. Save solution is acidic to litmus
both the precipitate and the paper. The acidity can be
supernatant solutions for tested by dipping a stirring rod
further study. into the solution and then
9. In order to confirm the touching it (with a drop of
presence of Pb2+Pb2+, add 1 solution) to a piece of blue
drop of 6 litmus paper resting on a
M HC2H3O2HC2H3O2 to the clean, dry watch glass. If the
supernatant solution obtained solution is acidic, it will turn
in Step 8. Next, add 3-4 drops blue litmus paper red or it will
of 1 M K2CrO4K2CrO4. The have no effect on red litmus
formation of a bright yellow paper. The formation of a
 white precipitate of AgCl in
the acidic solution is
confirmation of the presence
of Ag+.

Module 3: Group 11 – Cation Analysis

Group II cations can be divided into
INTRODUCTION two sub-groups by the action of
KOH.  Group II-A contains cation
whose sulfide compounds are
insoluble in KOH while the sulfide
compound of Group II-B dissolves in
KOH solution.

LESSON 1: PRECIPITATION OF
GROUP II CATIONS

Group II cations are precipitated as

Group II cations consist of 8 cations: sulfides in acidic solution.  H2S is
Hg2+, Pb2+, Bi3+, Cu2+, Cd2+, As3+, generated in solution through the
Sb3+, and Sn4+. They form very hydrolysis of thioacetamide in
insoluble sulfides so they can be solution.
precipitated by low amounts of
sulfide ion.  This can be achieved by
adding an acidic solution of H 2S.  In
the laboratory, thioacetamide,
CH3CSNH2, is generally used to
supply S2- to avoid the direct use of
H2S gas because of its toxic and This convenient method of
unpleasant odor.   Thioacetamide generating hydrogen sulfide is used
hydrolyzes in solution according to to minimize the escape into the
the reaction below. atmosphere of the highly toxic and
unpleasant smelling gas.  Sulfides of
very low solubility will precipitate
from acidic hydrogen sulfide
solutions, while sulfides of greater
solubility will remain in solution and
will precipitate only in basic solution.
Controlling the concentration of H+,
therefore, can be used to separate
ions on this basis of differences in
the solubility of their sulfides.
LESSON 2: GROUP II-A ANALYSIS

In the laboratory, Group II cations

are analyzed in one solution.  The
experiment involves separating the
ions and performing a confirmatory
test for the ion isolated.  

Below is a sample procedure for the

analysis of Group II cations.

You usually encounter procedures

like this in chemistry laboratory
manuals.  One way to understand
the procedure better is to convert it
into a schematic diagram as shown
below.  In this activity, we will study
the separation and confirmatory LESSON 2.1: SEPARATION AND
tests for the following ions: Bi 3+, Cu2+, CONFIRMATORY TESTS FRO II-A
Hg2+, and As3+, Sb3+
Mercury (Hg2+)
Bismuth (Bi3+)

Copper (Cu2+)

LESSON 3: GROUP II-B ANALYSIS

 Module 4: Group III– Cation Analysis
with excess potassium hydroxide
INTRODUCTION (KOH) solution to form a soluble
group.  Iron, nickel, manganese, and
cobalt are not amphoteric enough to
dissolve in excess KOH and form an
insoluble group.  

Group III contains seven cations:  LESSON 1: PRECIPITATION OF

Mn2+,  Fe3+, Co2+, Ni2+, Zn2+, Al3+, and GROUP III CATIONS
Cr3+.  They are precipitated in
solution either as insoluble metal Group III cations are precipitated as
sulfides or hydroxides in a basic sulfides or hydroxides in a basic
solution saturated with H2S.   This is solution saturated with H2S gas.  In
achieved in an ammoniacal solution this experiment, a solution
buffered with ammonium chloride containing 5 drops each of Al 3+,
and with thioacetamide as the Mn2+,   Fe3+, and Co2+ test solutions
source of H2S.  are precipitated in a basic solution
using thioacetamide as a source of
The precipitated cations are divided H2S.  The precipitated cations are
into sub-groups by the action of a separated into sub-groups by the
strong base. Chromium, zinc, and action of KOH.  Chromium, zinc, and
aluminum have amphoteric aluminum are soluble in excess KOH
character and form stable complexes solution to form a soluble
group.  Iron, nickel, and manganese
do not dissolve in excess KOH and
from an insoluble group.  The
solubility behavior of both groups in
KOH is based on the amphoteric
nature of the ions.  

As you have seen in the video, both

Al3+ and Zn2+ are precipitated initially Group III-B
but redissolves in the presence of an Fe3+, Mn2+, and Co2+
excess strong base.  This is due to Dissolution
the ability of Al3+ and Zn2+ to form The addition of HCl re-dissolves the
stable complex ions with a strong hydroxides of iron, manganese, and
base. The separation of Group III cobalt.    Once the ions are back in
ions into sub-groups depends on this solution then, the confirmatory tests
character of Al3+ and Zn2+. for each ion can be done. 

CONFIRMATORY TESTS Fe3+

Ferric ions react with excess
Identification of the Ions thiocyanate ions to produce a dark-
reddish brown complex.
Group III-A
Al3+
The aluminum-hydroxo complex ion
is destroyed by the addition of HCl, 
and produces free Al3+ in solution.
Subsequent addition of ammonia
buffered with ammonium acetate
precipitates Al3+  to Al(OH)3
Al(OH)3 has the property of forming
a complex with alizarin dye which
serves as the confirmatory test for
the aluminum ion.

Test for Aluminum Ion Mn2+

Manganous ions in acid solution are
oxidized to permanganate by sodium
bismuthate.

2Mn2+(aq)  +  5NaBiO3  ↔ 2MnO4- 

+5Bi3+(aq)  +  5Na+(aq)  +7H2O
visual result: purple solution
Ferric ions interfere with the
confirmatory tests for cobalt and
nickel.  This interference is
prevented by converting ferric ion Co2+ + 4SCN- ↔  [Co(SCN)4]2-
into a stable ferrifluoride ion by the
addition of excess sodium fluoride.

Fe3+  +  6F- ↔ FeF4-

When alcoholic ammonium

thiocyanate is added to the test
solution without mixing, an intense
blue-colored complex, Co(CNS)42-, is
formed at the interface of two
liquids.  
Module 5: Analysis of Anions
identified are approximately 0.01 M
INTRODUCTION in an aqueous solution. The
"semimicro" level of qualitative
analysis employs methods used to
detect 1-2 mg of an ion in 5 mL of
solution.
   
Just like any other qualitative
chemical analysis (ex. Cation
Analysis that have been discussed in
the previous modules), Anion
analysis makes use of many
different processes which involves
various important principles and laws
 Anions are negatively charged of chemistry. A thorough
species, which may be monoatomic understanding of these is necessary
or polyatomic. They are usually to obtain better results in the
prepared from dissolving acids or laboratory. Anion Analysis is made
salts in water. The procedures for up of series of separations of anions
detecting ions in aqueous solution is into groups and subgroups and
called Anion Analysis. In an eventually into individual ion followed
educational setting, the by identification of each ion.
concentrations of the ions to be
 salts are insoluble in neutral
or basic solution ex. CaSO3,
CaC2O4, CaAsO4
 Precipitating agent is calcium
LESSON 1: SEPARATION OF acetate, Ca(Ac)2
ANIONS ACCORDING TO THEIR  Divided into 2 subgroups by
SOLUBILITY GROUPS action of diluted HAc:
o Group IA – soluble in
Separations of anions rely on HAc (sulfite, arsenate)
different characteristics of the o Group IB – insoluble in
individual ions. These may involve dil HAc (oxalate)
redox reactions to change oxidation
state, differential solubility in an acid, Group II Anions
base, or water, or precipitating  Chromate and sulfate ions
certain ions. There are 21 commonly  Include ions whose Ca salts
occurring anions. These are: are soluble but whose Ba
 Arsenate AsO4-3                       salts are insoluble in slightly
 Arsenite AsO3-3                         basic solution
 Borate BO3-3  Are precipitated by Ba(Ac)2,
 Bromide Br- the precipitating agent, as
 Carbonate CO3-2 BaCrO4 and BaSO4 in a
 Chlorate ClO3- slightly basic solution
 Chloride Cl-
 Chromate CrO4-2 Group III Anions
 Ferricyanide Fe(CN)6-2  Sulfide, ferrocyanide (and
 Ferrocyanide Fe(CN)6-4 ferricyanide)
 Are ions whose Ca and Ba
 Fluoride F-
salts are soluble but whose
 Iodide I-
Cd salts are insoluble in
 Nitrate NO3-
neutral or slightly basic
 Nitrite NO2- solution
 Oxalate C2O4-  Precipitated by Cd(Ac)2 as
 Phosphate PO4-3 CdS and Cd2Fe(CN)6
 Sulfate SO4-2
 Sulfite SO3-2 Group IV Anions
 Sulfide S-2  Thiocyanate, iodide (and
 Thiocyanide CNS- chloride, bromide, thiosulfate)
 Thiosulfate S2O3-2         Are ions whose Ca, Ba and
Cd salts are soluble but Ag
CLASSIFICATION OF ANIONS salts are insoluble in slightly
acid with nitric acid
Group 1 Anions  Precipitated by AgAc as
 Sulfite, oxalate, arsenate AgCNS and AgI
(carbonate, arsenite,
phosphate, fluoride)
 Distinguished from other
groups because their calcium
Group V Anions
 Chlorate, borate (and nitrite,
nitrate)
 Are not precipitated by any of
the precipitating agent for
groups I to IV
 Designated as water-soluble
group since most common
salts of theses anions are
soluble in water and acid
 Anions whose Ca, Ba, Cd and
Ag salts are soluble in water
and acid