Qualitative Analysis of Anions

In inorganic qualitative analysis scheme, it is obviously necessary to consider

also the chemistry of anions, since the properties of the salts are a function of
the two components (thus, for example AgCl and AgNO3 can be separated on
the basis of their different solubility).

Therefore the anions will be identified on the basis of the properties of the
compounds which they form with certain cations.
 
While the analysis of cations involves two steps: separation and identification,
analysis of anions proceed differently:
 
1. it is excluded or ensure the presence of some anions on the basis of the color
of the sample, of the solubility and of the results of the analysis of cations (e.g.
knowing that is not present As you do not seek to identify AsO43-).
2. making a few preliminary tests
3. perform such tests
 Experiment Observation Inference

Colourless gas with pungent smell,

The gas evolved is
form white fumes with aqueous
HCl. This may be
ammonia when a glass rod dipped
due to the presence
in aqueous ammonia is shown
of Cl-.
over the mouth of the test tube.

The gas evolved is

Reddish brown gas with pungent Br2. This may be
To a small quantity of salt in a test smell, turns starch paper yellow. due to the presence
tube, add 1-2 ml of conc. of Br-.
sulphuric acid. The gas evolved is
Deep violet vapors with pungent I2. This may be due
smell, turns starch paper blue. to the presence of
I- .
The gas evolved is
Colourless gas which turns lime CO2. This may be
water milky. due to the presence
of C2O42-.
 Experiment Observation Inference
Colourless odourless gas The gas evolved is CO2. This
with brisk effervescence, may be due to the presence
turns lime water milky. of CO32-.
Colourless gas with
pungent smell, turns The gas evolved is SO2. This
acidified potassium may be due to the presence
dichromate paper or of SO32-.
solution green.
Take a small quantity of the salt in
Colourless gas with
a test tube and add 1-2 ml of dilute The gas evolved is H2S. This
smell like that of rotten
sulphuric acid. may be due to the presence
eggs, turns lead acetate
of S2-.
paper black.
Reddish brown gas with The gas evolved is NO2. This
pungent smell, turns
may be due to the presence
ferrous sulphate solution
of NO2-.
black.
CO32-, SO32-, S2-, NO2- etc
No gas is evolved.
may be absent.
The anions, that will be examined, are:
 
Acetate CH3COO- Nitrate NO3- Chloride Cl- Bromide Br-
 
Iodide I- Sulfate SO42- Carbonate CO32- Chrome CrO42-

The qualitative analysis of these anions will carried out by:

1. Solubility test:
 
As you observed during the qualitative analysis of cations, the solubility of a
substance, together with the knowledge of such cations are present in it, it
allows us to narrow the search field of the anions or even to identify directly
the anion present.
For example: in a colorless substance containing Ag+ and insoluble in HNO3
there will probably be Cl- (Kps 1.8 x 10-10). The only other Ag salt with similar
properties is Ag2SO4 which, however, is slightly soluble (Kps 1.20×10-5).
Keep at hand the table with the solubility products of the various salts can be a
very important element in the analysis of the salts.
2. Preliminary Test:
 
If the mixture to be identified is soluble in water, it is possible to make predictions of such
anions are present by treatment with reagents, that give characteristic reactions with
different anions. These reagents are H2SO4 solutions, AgNO3 and BaCl2.

Is it soluble in water?

The solubility tell us about the possible anions present in the substance
•Treatment of the solution with H2SO4 Anions
(Take a few drops of the known solution (the one given by the professor/assistent)
Some of the anions mentioned form volatile substances by reaction with H 2SO4
(exchange reaction or oxidation-reduction):
Anion Remark Reazioni
Effervescence. It releases a colorless gas
Cl- with a pungent smell that gives sour Cl- + H2SO4 ⇄ HSO42- + HCl
reaction
Effervescence. It releases a red-brown gas Br + H2SO4 ⇄ HSO4 + HBr
- -

Br- with a characteristic odor that gives sour 2HBr + H2SO4 ⇄ 2H2O + SO2 +
reaction Br2
Effervescence. The solid immediately I + H2SO4 ⇄ HSO4 + HI
- -

I- became dark brown, hydrogen sulfide odor, 8HI + H2SO4 ⇄ 4H2O + H2S + 4I2
purple iodine fumes 2HI + H2SO4 ⇄ 2H2O + SO2 + I2
Effervescence. It develops an odorless, CO32- + H2SO4 ⇄ H2O + SO42- +
CO 3
2-
colorless gas. CO2
2CrO42-+ H2SO4 ⇄ Cr2O72- + H2O
CrO 4
2-
Color change from yellow to orange-red.
+ SO42-
The use of hot H2SO4 allows the identification of the nitrate ion: this, in fact,
generates orange-brown NO2 fumes when heated with H2SO4.

2NaNO3 + H2SO4 ⇄ Na2SO4 + 2HNO3

4HNO3 ⇄ 2H2O + O2 + 4NO2

The formation of acetic acid by reaction of acetates with H2SO4 is evidenced

by the characteristic smell of vinegar.
b) Treatment of anions solution with AgNO3

GROUP OF HYDROCHLORIC ACID

(Take a few drops of the known solution (the one given by the
professor/assistent)
The Ag salts of the anions, that you must recognized in this lab (except
CH3COO-, NO3-, SO42-) are insoluble in water.
NO3- very soluble
SO42- lightly soluble Kps = 1.20×10-5
CH3COO- slightly soluble Kps = 1.94×10-3
I- ppt light yellow Kps=8,5 • 10-17
Br- ppt crem Kps=3,3 • 10-13
CO32- ppt white Kps=8,2 • 10-12
CrO42- ppt brown-red Kps=1,9 • 10-12
Cl- ppt white Kps=2,8 • 10-10
Place 10 drops of the aqueous solution of anions in a centrifuge tube and add 3-4
drops of 0.2 M AgNO3.

If no precipitate is formed Cl-, Br-, I-, CO32- and CrO42- , they are absent.
If a precipitate forms, all the anions may be present.
If the precipitate is white, Br-, I- and CrO42- they are absent.

The Ag2CO3 is white but unstable decomposes quickly forming silver oxide (black)
and CO2. If the precipitate were to become black, then CO32- is present.
Centrifuge and discard the solution. Wash the precipitate with cold H 2O and add 5-
6 drops of 3M HNO3 shaking with the glass rod until the end of the effervescence.

 If you were to completely dissolve the precipitate then halides are absent;
 If the precipitate does not completely cliffs then centrifuge and discard the
precipitate.

Make weakly alkaline solution, with 15M NH3, then weakly acidic with 5M
CH3COOH, and add 5-6 drops of 0.2M AgNO3.
The formation of a red-brown precipitate test the presence of CrO42-. The
carbonate ion reacts with nitric acid to form carbon dioxide and it has not therefore
b) Treatment of anions with BaCl2 solution
The barium salts of Cl-, Br-, I-, CH3COO-, NO3- are soluble in water and in
alkaline solution, while the salts of other anions are insoluble.
 
BaSO4 is insoluble in strong acids, such as HCl or HNO3 diluted, while the
others, being anions of weak acids, are soluble.
BaCrO4 is the only colored barium salt (yellow), while the others are all
white.
  
Put 4-5 drops of the solution in a test tube, make it slightly alkaline with 5M
NH3 and shake well with the glass rod. It is important that the solution is not
acidic because all the barium salts which are insoluble in water, except the
sulphate, they are soluble in strong acids. If you were to form a precipitate
separating it by centrifugation and discard.
 
Add 3-4 drops of 0.2M BaCl2:
the formation of a precipitate indicates the possible presence of SO 42-, CO32-,
CrO42-If the precipitate is yellow then there is the CrO42-ion.
 
Make the acid mixture by adding 2M HCl:
If the precipitate dissolves completely then it is absent the SO42- ion.
 Specific tests for anions

These assays can be eliminated if the previous preliminary treatment

indications on the presence or absence of certain species.

The order in which you perform the various assays is determined by the
interference of some anions with the reagents, used to identify other. For
example: the anions Br- and I- interfere with the analysis of Cl-; I- interferes
with the analysis of Br-.
The assays for the identification of the halides are performed in the order:
iodide, bromide, chloride.
Test for the chrome ion CrO42-
Put 2 drops of the test solution (known solution) in a test tube, add 5-10
drops of water and make the weakly acidic solution with 3M HNO 3.
Add 5-6 drops of ethyl ether and 3-4 drops of 3% H 2O2 and stir well
with a glass rod. The blue color of the ether layer is indicative of the
presence of chromate ion CrO5.
 
Test for sulfate ion SO42-
Place 5 drops of the test solution (known solution) in a test tube, acidify
with 6M HCl and then add 1 drop of 0.2M BaCl2. A white precipitate
indicates the presence of BaSO4 sulfate ion.
Test for carbonate ion CO32-

Place a small amount (2-3 drops) of the test solution (known solution) on
watch glass. Draw water of barite -Ba(OH)2- with a clean pipette (your
pipette and no the pipette of the bottle). Keep in suspension (at the tip of
the pipette) a drop of this reagent and place a short distance from the slide.
Acidify with HCl 2M test solution. the drop of water of barite, in suspension
on the watch glass, become turbid in the moment in which the gas formed
(CO2) touch it. The gas, which is formed, the drop indicating the presence
of BaCO3.
Test for iodide ion I-

Place 5 drops of the test solution (known solution) in a test tube and slightly
acidify with 5M CH3COOH, then add 2 drops of 0.2M KNO2. A red-brown
color, due to the formation of molecular iodine, indicates the presence of I -. If the
color is too pale, add 10 drops of CHCl3 and shake well. The purple color of the
organic phase indicates the presence of iodine.
Test for the bromide ion Br-
 
Since the iodide ion I- interfere with this assay, it must be removed before
analysis for Br ion.
For removal, proceed as follows: acidify the solution with 3M HNO 3, add
drop by drop and stirring continuously 0.2M KNO2 until you notice any
change in more brown coloration of the solution. Add 5 drops of CHCl 3,
mix well and leave to settle the aqueous phase in which it was extracted
iodine. Withdraw with a dropper, the aqueous phase, put it into the
melting pot and boil to evaporate off all the iodine. When the solution has
become colorless, run the following essay for the bromide ion.
Place 2-3 drops of the solution into a test tube and add 5 drops of NaClO.
A yellow-brown coloration test the presence of Br2. If the solution is
extracted with about 10 drops of the CHCl3 format it will be extracted
from the organic phase by coloring.
Test for chloride ion Cl-
 
Br- and I- interfere with the Cl- test. For this reason they must first be removed to
be able to proceed with the essay.

Place 15 drops of the test solution in a melting pot and add 15 drops of 5M
CH3COOH and then 30 drops of H2O and boil it. Add a few crystals of K2S2O8
(dipotassium peroxodisulphate) and heat. A brown color due to the formation of
I2, test the presence of I-.

Boil the solution until it becomes colorless, that is, until no evidence of I 2, while
maintaining a constant volume by adding H2O drop.
When you are sure of the complete elimination of I2 add 15 drops of 2M H2SO4
and few K2S2O8 crystals and heat to boil again: the presence of Br- is
demonstrated by the appearance of red-brown color characteristic of Br2.
Boil the solution until it becomes colorless, that is, until no evidence of Br 2,
while maintaining a constant volume by adding H2O drop.

When also Br- has been completely removed, the cold solution is acidified with
3M HNO3, then adding 2-3 drops of 0.2 M AgNO3. A white precipitate test the
In acidic solution the redox potential of S2O82- / 2SO42- worth, in fact, E ° =
1,91V and can be the following reactions:

•2I- + S2O82- ⇄ 2SO42- + I2 ∆E°=1,374V

•2Br- + S2O82- ⇄ 2SO42- + Br2 ∆E°=0,845V

•2Cl- + S2O82- ⇄ 2SO42- + Cl2 ∆E°=0,55V

The reaction 3, thermodynamically not favored, does not take place under the
conditions.
Test for nitrate ion NO3-

Some anions, such as iodide, bromide and chromate, interfere with the assay and must
be removed before proceeding.

Put 8 drops of the solution in a centrifuge tube and add Pb(CH 3COO)2 up to complete
precipitation of PbCrO4. Centrifuge and discard the precipitate, containing PbCrO4.
Add the saturated solution of Ag2SO4 to the test solution until complete precipitation of
the respective halide of Ag. Centrifuge and discard the precipitate (containing AgBr,
AgI, PbSO4) and transfer the decanted in a crucible.
Evaporate the solution to a volume of approximately 2 drops, add us 2 drops H 2O and
transfer to a test tube.

Acidify the solution with 2 drops of 2M H2SO4 and saturate adding FeSO4 until the
appearance of the bottom body. Incline the tube and slide along the side of the tube, a
few drops of 18M H2SO4 (NOT shake the tube). The appearance of a brown color at
the interface between solid FeSO4 and concentrated H2SO4 shows the presence of
nitrate (unstable complex).
In the presence of concentrated H2SO4 following reactions occur:

3Fe2+ + NO3- + 4H+ ⇄ 3Fe3+ + NO + 2H2O

Fe2+(excess) + NO + nH2O ⇄ [Fe(H2O)n(NO)]2+

The iron-nitrosyl complex is unstable at high temperatures, therefore it is

important to operate at room temperature.