Analytical Chemistry Qualitative Analysis

General Laboratory Directions:

 Scale of the operations:

semi micro (1 drop(0.05mL) - 1mL)

 Apparatus:

10mL test tubes

long droppers(12cm)with the tip of 1.5mm

stirring rods(small 125x3mm)

Precipitation

 Is done in 10 mL test tubes

 Precipitating reagent is added to the sample solution dropwise with constant stirring until no
more precipitate is formed.

Heating of Solutions

 Must be done in water bath

Evaporation

 Solution is transferred to a porcelain casserole and heated over an open flame.

 When a small amount of solution is left, the flame is removed and the heat of the casserole
is allowed to finish the evaporation process.

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Centrifuge

 In a semi micro analysis the process of filtration is replaced by centrifugation

 Centrifugation is the process with which precipitate is settled in the bottom of a small test
tube by centrifugal force and the centrifugate is then remove by a dropper without
disturbing the precipitate.

 When centrifuging, solutions should be balanced by placing another test tube containing
water of the same quantity on the opposite hole.

Washing of the Precipitate

1. After separating the solid from the supernatant liquid, the solid may still be contaminated
with ions from the centrifugate.

2. Wash the precipitate with distilled water(5drops) and mixed thoroughly by stirring.

3. The washing is then removed by the dropper and discarded. This is done once or twice.

How to do flame test

1. Make a loop on one end of the nichrome wire.

2. To clean the wire, dip the loop in conc. HCl and heat in flame until red hot.

3. Dip the wire into the solution to be tested. Make sure a thin film of the solution is in the loop
of the wire. Insert the wire into the blue cone of the burner flame. Repeat the operation several
times to confirm the color of the flame

Groupings of the Ions

 Groupings was established by the use of group reagents which precipitates related ions:

1. Group I Cations is composed of ions whose chlorides are insoluble in acid.

2. Group IV Cations are cations of alkaline earth metals and Magnesium and its phosphate salts
are insoluble in water

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3. Group V cations are not precipitated by chlorides, sulfide and phosphate. Sometimes called
as the soluble group. There is no precipitating agent for the group.

4. Group II anions are the chromate and sulfate anions which are precipitated by Barium
acetate as barium chromate and barium sulfate.

5. Group III anions are anions whose cadmium salts are insoluble in slightly basic and neutral
solutions. These includes sulfide, ferrocyanide and ferriccyanide.

EXPT. 1 QUALITATIVE ANALYSIS OF GROUP 1 CATIONS

 Procedure:

Addition of HCl to precipitate Ag+, Hg+2, Pb+2

Ag+ + Cl- AgCl

Hg2+2 + 2 Cl- Hg2Cl2

Pb+2 + 2 Cl- PbCl2

 Analysis:

- Separation and test for the presence of Pb+2

- Add 6-7drops of water and heat.

- PbCl2 soluble in hot water

- Add K2CrO4

Pb+2 + CrO4-2 PbCrO4

yellow ppt.

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 GROUP 1 CATIONS

Chloride Form Ksp

PbCl2 1 X 10 -4

Hg2Cl2 2 x 10 -18

AgCl 1.56 x 10-10

*NOTE:

 Lead chloride solubility in water at varying temperatures:

0.673g/100mL at 0OC to 3.34g/100mL at 100OC

 Lead is seldom separated completely

Separation and test for the presence of Ag+ and Hg+2

 Add 10 drops 3F ammonia

Ag+ is removed from the ppt by conversion to:

Ag+ + NH3 Ag(NH3)2+

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Make acidic with HNO3.

*Solution must be acidic to convert Ag(NH3)2+ to AgCl

Ag(NH3)2+ + Cl- + H3O+ AgCl + 2NH4+ + 2H2O

white ppt.

Separation and test for the presence of Hg +2

 Procedure:

1. Wash with 10 drops of water.

2. Dissolve ppt in 2 drops conc. HNO3

3. Dilute with 5 drops water. Add 1 to 2 drops SnCl 2.

*Black residue after the removal of Ag+ maybe Hg and HgNH2Cl:

Ammonia water does not only react with AgCl but also auto redox reaction with Hg 2Cl2 to form
black ppt

Hg2Cl2 + 2NH3 Hg NH2Cl + Hg + NH4+ + Cl-

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Final reaction:

Hg2Cl2 + SnCl4- Hg + SnCl6-

 Gray residue is the combination of Hg, Hg2Cl2, Hg NH2Cl

 White or gray precipitate confirms the presence of Hg+2

EXPT. 2 QUALITATIVE ANALYSIS OF GROUP IV CATIONS

 Ca+2, Ba+2, Sr+2 and Mg+2 ions of alkaline earth metals.

 Forms insoluble phosphate salts with (NH4)2HPO4

 Separation of individual cations is difficult due to a very small difference of K sp values.

 Analysis

Procedure:

To the clear sample, add 10 drops 0.5 F (NH4)2HPO4 conc. Ammonia until strongly
ammoniacal. Centrifuge, and test for complete precipitation by adding a few more drops of 0.5 F
(NH4)2HPO4

 Precipitate:

Ca3(PO4)2

Ba3(PO4)2

Sr3(PO4)2

Mg3(PO4)2

 Discard Centrifugate

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Separation of Ba+2

Procedure:

1. To the precipitate, wash once with 5 drops of water.

2. Discard washings .

3. Treat precipitate with 5 drops of concentrated HC2H3O2, stir thoroughly.

4. Dilute the solution to 2mL, and add 5 drops of 1F K 2CrO4 and stir for 1min.

5. Centrifuge and test for complete precipitation.

6. BaCrO4 formed was volatilized by addition of conc. HCl and subsequent evaporation. Ba +
ions emit yellow green flame on flame test.

Centrifugate :

 Ca+2, Sr+2 and Mg+2 and excess chromate ions. Make solution strongly ammoniacal with
ammonia, centrifuge. Discard centrifugate

Precipitate:

 Phosphates of Ca+2, Sr+2 and Mg+2 dissolve in 5 drops conc. HC2H3O2; dilute with 5 drops of
water. Add 5 drops 1 F (NH4)2SO4 heat to boiling in water bath, cool and centrifuge. Test for
complete precipitation by adding 1 drop of (NH4)2SO4 to the clear centrifugate.

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EXPT. 3 QUALITATIVE ANALYSIS OF GROUP V CATIONS

Objectives: To analyze the soluble cations which were not precipitated by the chloride, sulfide
and phosphate

Identification of sodium and potassium ions

 to 2mL of unknown solution add 1 drop of conc. HCl and make a flame test for sodium and
potassium ions

 clean a nichrome wire until it gives no color to a non-luminous flame.

 Test for the presence of Na+ by flame test and is confirmed by intense yellow flame
persisting for 5 sec.

 In the absence of Na+, K+ flame test will give pale violet color.

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 Test for the presence of K+ by flame test is confirmed by reddish violet flame persisting for 2
sec. viewed with cobalt glass.

Identification of NH4+:

 Place 5 drops of the original solution in small beaker and 5 drops of water.

 Make the solution alkaline with 3F KOH.

 Immediately cover the beaker with a watch glass to which adheres a moistened red litmus
paper in the inner side in contact with the fumes coming from inside the beaker.

 Warm solution gently for 1min.

 Even shading of litmus paper from red to blue confirms the presence of ammonium ions

EXPT NO. 4 QUALITATIVE ANALYSIS OF GROUP II ANIONS

Objectives: To separate and detect the presence of group II anions in a sample solution

Procedure:

 To the given sample solution add 1M Ba(C2H3O2)2 dropwise until precipitate is complete.
Centrifuge, discard the centrifugate.

 Precipitate

 Wash precipitate with 10 drops of water. Discard washings . Add 5 drops of 3M HCl stir and
centrifuge.

 Precipitate

 White residue indicates the presence of sulfate. Wash precipitate with 10 drops 3M HCl. If
white residue remains, presence of sulfate is confirmed

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* BaSO4 is insoluble from 3M HCl

PRECIPITATION OF GROUP II ANIONS

Centrifugate:

 Add 10 drops of 2.5 M NaC2H3O2. The presence of a yellow precipitate confirms presence of
chromate.

*NaC2H3O2 buffers the hydronium ions of the solution sufficiently to precipitate chromate ions

EXPT. 4 QUALITATIVE ANALYSIS OF GROUP III ANIONS

Objectives:To separate and detect the presence of Group II anions in a sample solution

Procedure:

 From the sample solution, transfer 10 drops to a test tube.add 1M Cd(C2H3O2)2 dropwise
until precipitation is complete.

 Centrifuge

 Wash precipitate twice with hot water, discarding washing.

 Divide precipitate into three portions.

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First portion

Add 3 drops of 3M HCl. Cover with strip of filter paper moistened with 0.5 M Pb(C 2H3O2)2
brown or black coloration in the paper caused by PbS formation confirms the presence of Sulfide

Second portion:

Transfer in a spot plate. Add 1 drop of 3M HCl. Add 1 drop of 1 M FeCl3. Appearance of dark
blue precipitate (Fe4[Fe(CN)6]3) confirms the presence of ferrocyanide.

Third portion:

Dissolve with 1drop of 3M HCl. Add 3 drops of water and small crystals of ferrous sulphate
to the solution dark blue precipitate (Fe3[Fe(CN)6]2) confirms the presence of Ferricyanide.

Notes:

 Ferricyanide, ferrocyanide, sulfide, anions of gp. III is precipitated fairly completely with
cadmium.

 Ferricyanide and sulfide cannot exist together in solution. Ferricyanide will oxidize the sulfide
ion to free sulfur. The ferricyanide is then reduced to ferrocyanide.

 Sulfide is converted to H2S which is detected on lead acetate paper to produce a black lead
sulfide.

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