Analitycal Chemistry

dr hab. Joanna Cybińska

dr hab. Małgorzata Guzik

SUMMARY
of qualitative analytical chemistry
 The full qualitative analysis scheme for the elements in the
periodic table.

Distribution of metal ions between analytical groups is based on different solubulity properties
between sparingly soluble chlorides, sulfides and carbonates. Therefore, HCl, H2S and (NH4)2CO3
are called group reagents.
 Cl Ag+ and Hg22+ are removed with
the Group I, even though they will
react with H2S.

Ksp=10–50 – 10–28

SnS2, As2S3,
As2S5
S2

+ NH4OH

Ksp= 10–26 – 10–16

+ (NH4 )2 CO3 CO32

NH4+
The order of addition of group reagents is very important in the systematic analysis
of cations.

The reagents of following groups may also precipitate cations of previous groups, if
they are not properly removed (check the completeness of the precipitation of
the group).
reaction with Nessler's reagent (solution of potassium
tetraiodomercurate(II) - K2[HgI4] in potassium hydroxide)
 The conditions of the I group (Ag+, Pb2+) recipitation:

1. Group reagent: 1 M HCl,

2. temperature: boiling.

ad 1.

The higher concentrations of HCl solution than1M can result in partial dissolution of
AgCl and PbCl2 precipitates.

AgCl + Cl  AgCl2

PbCl2 + 2Cl  PbCl42 

The sample with cations of all groups may contain precipitate due to
the presence of AgCl , Hg2Cl2, PbCl2 and basic salts of bismuth and tin,
which after addition of 1 M HCl and heating at 100 C go back into
solution.

BiOCl + 2H+ + 2 Cl  Bi3+ + 3Cl + H2O

Sn(OH)Cl + H+ + Cl  Sn2+ + 2Cl + H2O

However, increased temperature causes the dissolution of PbCl2,

therefore some of Pb2+ ions one can find in the II group.
 The conditions of precipitation the II group of cations:

1. Reagent group: H2S or AKT

2. temperature: boiling
3. pH: pH  0.5 if cHCl  0.3M

ad 1, 2.
AKT (amide of thioacetic acid) in aqueous solution is stable, while heated to the
temperature ~ 90 °C (boiling water bath) forms H2S

90 C
CH 3CSNH 2  2H 2O   CH 3COO   NH 4  H 2S

Precipitates are coarsely crystalline, easy filterable

ad 3.
pH ~ 0.5 is necessary due to the fact that at lower pH sulfide of Cd2+ can dissolve
(CdCl42); at higher pH arsenic sulfide may not precipitate.
In pH ~ 0.5, the ZnS with the lowest Ksp from sulfides of the group III is in solution.

Pb2+, Bi3+, Cu2+, Sn2+, Sn(IV), As(III), As(V) + III, IV and V groups

subgroup A: PbS, Bi2S3, CuS, SnS  react with HNO3

subgroup B: SnS2, As2S3, As2S5  amphoteric properties
of sulfides (react with both acids and bases)
There are two methods of separation group II into two
subgroups A and B.

Sulfides of subgroup II B are dissolved in:

KOH + H2O2  hydrogen peroxide oxidizes ions of subgroup II B increasing their

acidic properties (higher solubility in strong bases),
as well as SnS from II B

(NH4)2S2  ammonium polysulfide also oxidizes ions of subgroup II B and SnS

 The conditions of precipitation the III group of cations:

Zn2+, Co2+, Ni2+, Fe3+, Cr3+

Ba2+, Ca2+, Mg2+, K+, NH4+;
1. Reagent group: (NH4)2S or AKT
2. Environment: ammonia buffer (NH3H2O + NH4Cl)
3. pH: 8  pH  9
4. temperature: boiling

ad 1
In an environment of ammonium buffer at pH 8.3, the concentration of S2- ions is
sufficient to have exceeded the solubility products of III group cations

Ksp= 10–26 – 10–16

 ad 2, 3 NH4+ + S2 + H2O  NH3H2O + HS

In order to shift the reaction to the left (Le Châtelier’s principle), add NH3H2O,
but the excess of NH3H2O may cause precipitation of Mg(OH)2 .
Ksp = 1107, Mg(OH)2 begins to precipitate at pH 9.2.

Mg2+ + 2NH3·H2O  2NH4+ + Mg(OH)2

To prevent it, add NH4Cl, which lowers the pH.

Le Châtelier’s principle states that the position of an equilibrium always shifts

in such a direction as to relieve a stress that is applied to the system.
Adding NH4Cl, as the electrolyte, prevents the formation
of colloidal hydroxides and sulfides of group III cations, too.

2Cr3+ + 3S2- + 6H2O  2 Cr(OH)3 + 3H2S

ad 4
Increased temperature:
a) carried out CoS and NiS in sparingly soluble forms of ;
b) favors the formation of precipitates that are easy to filtration and
centrifugation.
 The conditions of precipitation the IV group of cations:

Ba2+, Ca2+, Mg2+, K+, NH4+

1. Reagent group: (NH4)2CO3

2. Environment: ammonia buffer (NH3H2O + NH4Cl)
3. pH: 8  pH  9
4. temperature: 60C.

(NH4)2CO3 undergoes hydrolysis:

NH4+ + CO32 + H2O  NH3H2O + HCO3

 NH4+ + CO32 + H2O  NH3H2O + HCO3

In order to shift the reaction to the left (Le Châtelier’s principle), add NH3H2O but
the excess of NH3H2O may cause precipitation of Mg(OH)2.
To prevent it, the NH4Cl is added and lowers the pH.
The aqueous solution of (NH4)2CO3 contains some ammonium carbamate
(NH2COONH4) and NH4HCO3 that are decomposed at 60 C.

NH2COONH4 + H2O  2NH4+ + CO32

The higher temperature (> 60 °C) may decompose (NH4)2CO3 and cause
volatilization of NH3 from the buffer.
 Classical qualitative analysis of anions

In contrast to cations, the anions are analyzed without systematic separation

(no analytical groups of anions).

The analysis of anions is carried out by elimination, using their certain common
chemical properties.
Anions are:
 volatile;
 precipitated by Ag+;
 precipitated by Ba2+;
 oxidizing;
 reducing.
 Preliminary reactions

1. A sample is acidified with dilute HCl (2 M) or H2SO4 (1 M)

If there is no odor or visible evolution of gas, there are no anions:

S2–, CO32–, SO32–, NO2–, CH3COO–

2. Reaction with AgNO3

insoluble in HNO3 (Cl, Br, l, SCN)
soluble in HNO3 (S2–, PO43–, NO2–, CO32–, C2O42–, CrO42–, AsO43–, AsO33–)
 Preliminary reactions

3. Reactions with BaCl2

SO42–: white, insoluble in diluted and concentrated HCl

White precipitates soluble in HCl:

SO32–, CO32–, C2O42–, PO43–, AsO33–, AsO43–

CrO42–: yellow, soluble in HCl

 Preliminary reactions

4. Reaction with KMnO4  reaction of detection of anions with reducing

properties

1-2 drops of 0.1 M KMnO4 add to a slightly acidified solution with H2SO4.
Decoloration of the pink solution occurs when the following anions are present:
Br–, I–, SCN, S2–, SO32–, NO2–, AsO33–

Discoloration occurs when heated !!! Cl–, C2O42–

NO2 + H2O  NO3 + 2H+ + 2e /5

MnO4 + 8H+ + 5e  Mn2+ + 4H2O /2

5NO2 + 5H2O + 2MnO4 + 16H+  5NO3 + 10H+ + 2Mn2+ +8H2O

5NO2 + 2MnO4 + 6H+  5NO3 + 2Mn2+ + 3H2O

 Preliminary reactions

5. Reaction with I2  reaction of detection of anions with strong

reducing properties

To the solution add few drops of I2 in 10% KI and starch. Discoloration of the navy
blue solution occurs when the following anions are present:

S2–, SO32–, AsO33–,

 Preliminary reactions

6. Reaction with KI  reaction of detection of anions with oxidizing

properties

1-2 drops of 2% KI and starch add to a slightly acidified solution with H2SO4. The
solution will be navy blue in the presence of the following anions:

NO2–, AsO43–, CrO42–, Cr2O72–

NO2 + 2H+ + e  NO + H2O /2

2I  I2 +2 e /1

2NO2 + 4H+ + 2I  2NO + 2H2O+ I2

 Identification reactions

The identification reactions of anions should be performed after

preliminary reactions.

1. Identification of CO32  reaction with diluted acid (HCl)

CO32+ 2H3O+  3H2O + CO2

identification of CO2 with limestone-water

CO2↑+Ca2+ + 2OH  CaCO3 (white) + H2O

 2. Identification of SO42  reaction with BaCl2 in 6 M HCl

Ba2+ + SO42  BaSO4

3. Identification of CH3COO
reaction with diluted H2SO4 which displaces from the acetate ion the free acetic
acid; when heated identified by the smell

CH3COO + H3O+  CH3COOH + H2O

reaction with FeCl3 solution which in neutral solutions gives a red-brown color of
iron(III) acetate;
Fe3+ + 3CH3COO + 2H2O  Fe(OH)2CH3COO + 2CH3COOH

I i NO2 interfere with the reaction

 4. Identification of Cl  reaction with AgNO3 solution in 2 M HNO3

Cl + Ag+ AgCl (white)

The white precipitate turns dark as a result of photochemical reaction (metallic

silver is isolated):
2AgCl   2Ag0 + Cl2
AgCl is dissolved in dilute solution of NH3H2O and (NH4)2CO3

AgCl +2 NH3H2O  Ag(NH3)2+ + Cl

Ag(NH3)2+ + Cl + 2H+ (from HNO3)  AgCl + 2 NH4+

5. Identification of I  reaction with AgNO3 solution in 2 M HNO3

I + Ag+ AgI (yellow)

AgI is insoluble in dilute and concentrated solution of NH3H2O.

6. Identification of C2O42  reaction with CaCl2 solution

Ca2+ + C2O42 CaC2O4 (white)

The white precipitate is not dissolved in dilute CH3COOH.

7. Identification of SO32  reaction with acids (HCl) that decomposes SO32 to
SO2.
SO2 may be detected after decolorization of filter paper moistened with a
solution of iodine or a manganate(VII):

3SO32 + 6H3O+ 3SO2 + 9H2O

8. Identification of NO3 (ring reaction)  reaction with

a saturated solution of Fe(NH4)2(SO4)2 in the presence of concentrated H2SO4

Br, I, CrO42, Cr2O72 ions interfere; the ions are removed by
precipitation with a solution of Ag2SO4.
 3Fe2+ + NO3 + 4H3O+  3Fe3+ + NO + 6H2O

Fe2+ + NO Fe(NO)2+  brown colored complex

Experiment: few drops of the solution add to the saturated solution of

Fe(NH4)2(SO4)2, then gently drop the concentrated H2SO4 on the wall of the tube
(under hood).
At the point of contact of the two liquids the brown ring will occur.
The ring reaction (even with dilute acid) also gives the NO2 ion.
Before the detection of NO3, the NO2 ions must be removed by boiling with solid
NH4Cl.
NO2 + NH4+ → N2↑ + 2 H2O

9. Identification of AsO43
reaction with Ag+ ions

3Ag+ + AsO43 Ag3AsO4 chocolate-brown precipitate

reaction with a mixture of magnesium

AsO43 + Mg2+ + NH4+  MgNH4AsO4 white precipitate, which does not give AsO33
10. Identification of AsO33 :

reaction with Ag+ ions

3Ag+ + AsO33 Ag3AsO3 (yellow precipitate)

reaction with AKT in 6 M HCl

AsO33 + 6H3O+ As3+ + H2O

2As3+ +3H2S + 6H2O As2S3 + 6H3O+ (yellow precipitate)
 Analysis of unknown X ,Y anions

1. H+:  solution becomes yellow very slowly;

2. AgNO3 :  no precipitate, or very low cloudy;

3. BaCl2:  no precipitate;

4. MnO4+ H2SO4:  discoloration of solution; there are reducers;

5. I2 + starch:  no discoloration; there are no strong reducers;

6. I + H2SO4 +starch:  becomes colored in dark blue; there are oxidants;

7. identification reactions of X? and Y?

 Analysis of solid samples

Transform the solid sample into solution in the simplest way:

a) dissolving in H2O, NaCl  Na+ + Cl

b) dissolving in CH3COOH (carbonates)

CaCO3+ 2CH3COOH  2CH3COO + Ca2+ + CO2 + H2O

c) dissolving in non-oxidizing acids (HCl, H2SO4):

ZnS + 2H3O+  Zn2+ + H2S +2 H2O
Al(OH)3 + 3H3O+  Al3+ + 6H2O
Zn + 2H3O+  Zn2+ + H2 + 2H2O
d) dissolving in oxidizing acid (HNO3 noble metals):
3CuS + 8H3O+ + 2NO3  3Cu2+ + 3S + 2NO + 12H2O
3Cu + 8H3O+ + 2NO3  3Cu2+ + 2NO + 12H2O

e) dissolving in aqua regia (HCl + HNO3; 3:1)

3CoS + 8H3O+ + 18Cl + 2NO3  3CoCl64 + 2NO + 3S + 12H2O

f) dissolving in bases
Al(OH)3 + OH  Al(OH)4
Al2O3 + 2OH  2AlO2 + H2O
2 Al + 2OH + H2O  2AlO2 + 3H2
After dissolving of the solid sample identify the cation (scheme of analytical groups of
cations), possible anions and remember about ions that are introduced during sample
dissolution.

Sometimes the heavy metal ions disturb in the analysis of anions and have to be
separated using the so-called sodium extract.

Sodium extract – boiling with a saturated solution of Na2CO3.

In order to separate the heavy metal ions that interfere with the analysis of anions,
e.g. Cu2+ ions interfere with the detection of oxidizing anions:

2Cu2+ + 4I  2CuI + I2

 Examples of questions on laboratory and exam tests

Describe and briefly discuss the conditions for precipitation of the IVth (IIIrd,
IInd, Ist) analytical group of cations. Write appropriate reactions.

Describe a preliminary probe used for detection of oxidizing anions (reducing

anions, strongly reducing anions) present in solution.
Indicate the results of this test for the following anions:

a) nitrate(III), b) sulfate(VI), c) arsenate(V), d) carbonate, e) sulfate(IV), f)

arsenate(III), g) iodide.
For positive results, write the equation of the reaction.
Give one example of the complexation reaction using for:
a) dissolving a hardly soluble precipitate,
b) masking of cations.
Write the appropriate equations of reactions.
Give an example of the complexation reaction and the redox reaction using for
identyfication of ions. Write the appropriate equations of reactions.

Give two examples of using the amphoteric properties for the separation of
hardly soluble precipitates. Write the appropriate equations of reactions.
Dissolve in the easiest way the following substances:
a) iron, b) zinc hydroxide, c) ammonium chloride d) copper(II) sulfate(VI).
(a) zinc, b) magnesium hydroxide, c) lead(II) chloride, d) potassium sulfate(VI).
(a) copper, b) potassium hydroxide, c) cobalt(II) sulfate(VI), d) barium
carbonate.
For one of the two salts given above write reaction equations which
unequivocally identify the cation and the anion.
Give the definition of the solubility product. For an example chosen by you,
discuss the influence of pH on the precipitate solubility (common-ion effect;
salt effect; hydrolysis of precipitate; complexation).

Dissolve in the easiest way the mixture of the following substances and
unequivocally identify them:
1) copper(II) chloride and iron,
2) ammonium nitrate(V) calcium acetate and copper.