Analytical

Chemistry
PHCMp 101

Cations Identification
Lab 1

Group I Cations

Safety First!
White Lab coat
Eye goggles
Gloves
Closed shoes

Group I Cations

Donts!
Shorts, skirts,
short dresses

Eating, drinking
or chewing gum

No slippers,
ballerinas,
sandals

GIRLS:

Tie back long hair and

avoid jewellery

Group I Cations

Safety facilities:
2
2
1
1
1

exit doors
fire extinguishers
safety shower
eyewash station
first aid kit
Accidents OR injuries: report all accidents
to your teaching assistant.
Unauthorized experiments: NEVER
perform an unauthorized experiment in
the lab.
Pouring: NEVER pour solutions above eye
level.
Waste disposal: ALWAYS discard your

Group I Cations

To keep the lab clean and tidy:

If you spill it, clean it up.
If you opened it, close it.
If you used it, clean it.
If you break it, replace it.
If you borrow it, return it.
If you turned it on, turn it off.
If you took it, put it back where it belongs.

Group I Cations

Group I Cations

Group I Cations

Grades distribution
50% Practical exam
30% Theoretical exam
20% Evaluation:
10% Lab results and report
10% Safety and lab conduct

Group I Cations

Analytical Chemistry?
It is the study of :

Separation
Identification
Quantification
of the chemical components of natural or artificial materials

Qualitative
analysis:

Quantitative
analysis:

Identification of
unknown compounds
(CATIONS AND
ANIONS)

Determination of the
amount of a certain
component.

Group I Cations

Analytical identification of
cations
What are cations?
Positive ions or metal ions (ex: Na+ )
How will we identify the cations?
Cations (metal ions or basic radicals) are classified
into several groups on the basis of their behavior
against some reagents (group reagents).
What is this behavior?
Classification is based on whether a cation reacts
with the group reagent by formation of ppt or not .
It can therefore be said that the classification of
cations is based on the differences of the
solubilities of their chlorides, sulphides, hydroxides
and carbonates.
Group I Cations

Grp

Group reagent

Ions

Formulae of
precipitates

Distinguishing features

Cold dil HCl

Ag+, Pb++,Hg2++

AgCl, PbCl2, Hg2Cl2

Chlorides insoluble in cold dil

HCl

H2S in presence of
HCl (0.2-0.3 M)

Subgroup IIA Cu++,Cd+

+
,Hg++,Bi++,
Pb++
Subgroup IIB
++
Sn , Sn4+, Sb3+, As3+,
As5+

CuS, CdS, PbS, HgS,

Bi2S3, SnS, SnS2,
Sb2S3,
Sb2S5,

Precipitated as Sulfides in acidic

medium (0.2-0.3 M HCl)

NH4OH in
Presence of
NH4Cl

Al3+, Cr3+, Fe3+

Al(OH)3, Cr(OH)3,
Fe(OH)3

Precipitated as Hydroxides by
NH4OH in presence of excess
NH4Cl

H2S in Presence of
NH4OH

Ni++, Co++, Mn++, Zn++

NiS, CoS, MnS, ZnS

Precipitated as Sulfides by H2S

from ammoniacal solution in
presence of NH4Cl

(NH)2CO3 in
presence of
NH4OH &NH4Cl

Ba++, Ca++, Sr++

BaCO3, SrCO3,
CaCO3

Precipitated as Carbonates in
alkaline medium by NH4OH in
presence of NH4Cl

No particular
reagent

Na+, K+, NH+4 , Mg++

Different precipitated
forms

Ions not precipitated in previous

groups
Group I Cations

Why did HCl precipitate Ag+

+
but did not precipitate Cu
?+

AgCl is a precipitate but CuCl2 is a

solution
This depends on the solubility product (Ksp) of the two
salts
CuCl2 has a high Ksp while AgCl has a
low Ksp
+
AgCl
Solid

What is Ksp?!!
AgCl
Solid

Ksp:

AgCl
saturated
solution

Ag and Cl
ions

Ag+ and Clions

The product of the concentration of ions in a

saturated solution, at a given temperature.
Ksp= [Ag+][Cl-]
Group I Cations

To summarize briefly the applications of the

principle of the solubility product in analytical
separations these maybe collected in three
main uses:
1. In order to precipitate a slightly soluble electrolyte,
the product of the ions must exceed the solubility
product constant ( for the given temperature)
2. When the product is just reached, but not exceeded,
the solution is saturated.
3. To dissolve a precipitate, the product of the
concentrations of the ions must be kept below the
solubility product constant of the precipitate.

Group I Cations

Group I
Ag+ , Pb2+
Silver , Lead
Group reagent: Cold dil. HCl
Precipitation:
To the clear unknown soln. (containing single cation of
gp.I) add cold dil. HCl dropwise with constant shaking
where a white ppt. is formed.
Pb+ +2ClAg+ + Cl+

PbCl2
AgCl

white ppt
white ppt

.Add slight excess HCl to the test tube

Group I Cations

Why do we use cold dil. slight excess

HCl for the precipitation of gp I
cations?
Cold HCl is used to avoid the dissolution of PbCl2
which dissolves on hot (solubility of PbCl2 in H2O
at 100 C is 33.4 g\L while only 9.9 g\L at 20C).
Dil. HCl is used because the presence of excess
Cl- in soln.(if conc.HCl is used) leads to the
dissolution of PbCl2 by complex formation and it
escapes to gp. II
PbCl2 + Cl-

PbCl3- + Cl-

PbCl42Group I Cations

Precipitation is done using a slight excess of

HCl to:
Ensure complete precipitation.
Prevent the precipitated chlorides from
going into the colloidal state i.e to prevent
peptization of ppt.

Group I Cations

Identification:
White ppt (PbCl

or AgCl)

Add water and boil

If ppt. dissolves => PbCl2

New portion of the sample

If the ppt is insoluble in

boiling water =>AgCl
ppt. + conc. NH4OH
shake

+ dil CH3COOH
+ KI
+ K2CrO4

ppt. dissolves
=> [Ag(NH3)2]

Yellow ppt.
Yellow ppt
of PbCrO4
of PbI2

+
dil. HNO3

white ppt. of AgCl

Group I Cations

HCl is preferred to any other chloride

because:
It prevents the peptization of ppt.
It prevents the introduction of a foreign
cation.
(if NaCl for example is used for precipitation)

It prevents the precipitation of oxy salts of

bismuth,tin and antimony (cations of gp.IIB )

Group I Cations

Group I Cations

Group I Flow Diagram

(Ag+,Pb+2)
Add dil. HCl

White ppt.;
AgCl or PbCl2

Solution;
contains other
ions

Add water and boil

White ppt.;
AgCl
Conc.NH4OH

Solution;
contains Pb2

OR

Add KI

Yellow ppt
indicates Pb++

Solution
contains
[Ag(NH3)2] +
dil.HNO3
+

White ppt
indicates Ag

dil CH3COOH +
K2CrO4

Yellow ppt
indicates Pb++
Group I Cations

DEMO
Group I Cations