Detecting cations

According to their properties, cations are usually classified into

six groups.[1] Each group has a common reagent which can be
used to separate them from the solution. To obtain meaningful
results, the separation must be done in the sequence specified
below, as some ions of an earlier group may also react with the
reagent of a later group, causing ambiguity as to which ions are
present.this happens because cationic analysis is based on the
solubility products of the ions.As the cation gains its optimum
concentration needed for precipitation it precipitates and hence
allowing us to detect it. The division and precise details of
separating into groups vary slightly from one source to another;
given below is one of the commonly used schemes.
1st analytical group of cations
1st analytical group of cations consists of ions that form insoluble
chlorides. As such, the group reagent to separate them is
hydrochloric acid, usually used at a concentration of 12 M.
Concentrated HCl must not be used, because it forms a soluble
complex ion ([PbCl4]2-) with Pb2+. Consequently the Pb2+ ion
would go undetected. NH3 is also included in ZERO group of
cation (according to NCERT textbooks). The most important
cations in 1st group are Ag+, Hg2+
2, and Pb2+. The chlorides of these elements cannot be
distinguished from each other by their colour - they are all white
solid compounds. PbCl2 is soluble in hot water, and can therefore
be differentiated easily. Ammonia is used as a reagent to
distinguish between the other two. While AgCl dissolves in
ammonia (due to the formation of the complex ion [Ag(NH3)2]+),
Hg2Cl2 gives a black precipitate consisting of a mixture of chloromercuric amide and elemental mercury. Furthermore, AgCl is
reduced to silver under light, which gives samples a violet colour.
PbCl2 is far more soluble than the chlorides of the other two ions,
especially in hot water. Therefore, HCl in concentrations which
completely precipitate Hg2+
2 and Ag+ may not be sufficient to do the same to Pb2+. Higher
concentrations of Cl cannot be used for the before mentioned
reasons. Thus, a filtrate obtained after first group analysis of
Pb2+ contains an appreciable concentration of this cation,
enough to give the test of the second group, viz. formation of an
insoluble sulfide. For this reason, Pb2+ is usually also included in
the 2nd analytical group.
This group can be determined by adding the salt in water and
then adding dilute hydrochloric acid. A white precipitate is
formed, to which ammonium hydroxide is then added. If the

precipitate is insoluble, then Pb2+ is present; if the precipitate is

soluble, then Ag+ is present, and if the white precipitate turns
black, then Hg2+
2 is present.
Confirmation test for lead:
Pb2+ + 2 KI PbI2 + 2 K+
Pb2+ + K2CrO4 PbCrO4 + 2 K+
Confirmation test for Silver:
Ag+ + KI AgI + K+
2Ag+ + K2CrO4 Ag2CrO4 + 2 K+
Confirmation test for dimeric mercury ion:
Hg2+
2 + 2 KI Hg2I2 + 2 K+
2 Hg2+
2 + 2 NaOH 2 Hg
2O + 2 Na+ + H2O
3rd analytical group of anions
The 3rd group of anions consists of SO204, PO34 and BO33.
They react neither with concentrated nor diluted H2SO4.
Sulfates give a white precipitate with BaCl2 which is insoluble in
any acid or base.
Phosphates give a yellow crystalline precipitate upon addition of
HNO3 and ammonium molybdate.
Borates give a green flame characteristic of ethyl borate when
ignited with concentrated H2SO4 and ethanol.
References
^ a b E. J. King "Qualitative Analysis and Electrolytic Solutions"
1959, Harcourt, Brace, and World, New York.
^ C. Parameshwara Murthy (2008). University Chemistry, Volume
1. New Age International. p. 133. ISBN 8122407420.
Qualitative inorganic analysis
From Wikipedia, the free encyclopedia
Classical qualitative
inorganic
analysis is
a
method
of analytical chemistry which seeks to find elemental composition
of inorganic compounds. It is mainly focused on detecting ions in
an aqueoussolution, so that materials in other forms may need to
be brought into this state before using standard methods. The
solution is then treated with various reagents to test
for reactions characteristic of certain ions, which may cause color
change, solid forming and other visible changes.[1]
Qualitative inorganic analysis is that branch or method of
analytical chemistry which seeks to establish elemental
composition of inorganic compounds through various reagents.

The formation of precipitates with the ions of an unknown salt in aqueous solution and other reagents can be used to help identify
and separate the ions of the unknown salt.
Chloride Precipitation: Chloride ions, CL, can be added to a solution of an unknown salt. Inspection of the general solubility table
(Appendix A) indicates the chloride salts of Ag+, Pb2+, and Hg22+ are insoluble in water. Therefore, it is possible to detect the presence
of Ag+ and Pb2+ by adding CL ions. To differentiate between Ag+ and Pb2+ additional tests (see complex ions section of Project 6) can
be carried out.