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Reactions of Anions of the First Analytical Group

Sulphate-(SO42), sulphite-(SO32), carbonate-(CO32), phosphate-(PO43), oxalate-(C2O42),


thiosulphate-(S2O32), tetraborate-(B4O72), arsenite-(AsO33), arsenate-(AsO43), fluoride-(F),
tartrate-(C4H4O62), citrate-(C6H5O73), chromate-(CrO42), dichromate-(Cr2O72), and silicate(SiO32) ions constitute the first analytical group of anions. These anions form precipitates with
barium chloride. Formed precipitates are soluble in mineral acids, exclude barium sulphate. These
anions react with the group reagent in neutral or slightly alkalic environment.

Reactions of sulphate-ions detection:


1. Action of barium chloride. With barium salts sulphates form insoluble in acids and alkalis white
precipitate:
Na2SO4 + BaCl2 = BaSO4 + 2NaCl
For sulphates detection to investigated solution adds concentrated chloride or nitrate acid. The
reaction sensitivity rises in addition of drop of KMnO4 solution BaSO4 precipitate is painted in
the violet colour.
2. Action of lead acetate. Lead salts from sulphates solutions precipitates white sediment, soluble
at heating in alkalis and solution of ammonium acetate:
Pb(CH3COO)2 + Na2SO4 = PbSO4 +2CH3COONa
PbSO4 + 4NaOH = Na2PbO2 + Na2SO4 + 2H2O
PbSO4 + 2CH3COONH4 = Pb(CH3COO)2 + (NH4)2SO4
Reactions of sulphite-ions detection:
1. Action of barium chloride. With barium salts sulphites form white precipitate soluble in acids:
Na2SO3 + BaCl2 = BaSO3 +2NaCl
BaSO3 +2Cl = BaCl2 + SO2 + H2O
2. Action of chloride acid. The mineral acids decompose soluble and insoluble sulphites with SO2
elution. SO2 is reducer and discolours 2 and KMnO4 solutions:
Na2SO3 +2Cl = 2NaCl + SO2 + H2O
SO2 + I2 +2H2O = H2SO4 + 2HI
5SO2 + 2KMnO4 + 2H2O = 2MnSO4 + 2H2SO4 + K2SO4
3. Action of iodine solution. Sulphite-ion as reducer discolours iodine solution:
Na2SO3 + I2 + H2O = Na2SO4 + 2HI
4. Action of sodium nitroprusside. Sodium nitroprusside Na2[Fe(CN)5NO]2H2O paints neutral
solutions of sulphites in pink-red colour. Addition of ZnSO4 solution surplus arise the colour
intensity. If to add still a drop of K4[Fe(CN)6] solution, red precipitate appears. Acids destroy
colouring that is why it is needed to neutralise acidic solutions. Mechanism of this reaction is
not while still cleared up.
1

5. Action of fuchsine. Sulphites reduce dyes (fuchsine, malachite green). At sulphites presence
disappears dye colouring. Fuchsine thus forms fuchsine-sulphite acid a colourless salt of Nsulphine acid of p-fuchsineleucosulphoacid (at pH 3-6):
_
+ .
NH2 Cl

H2N

H3C

+ 2Na2SO3 + HCl

NH2

H2N

NH-SO2-Na

H3C

+ 2NaCl + 2H2O

NH2-SO2-Na

Reactions of thiosulphate-ions detection:


1. Action of barium salts. Barium chloride, added in surplus, with thiosulphate-anions forms white
precipitate:
Na2S2O3 + BaCl2 = BaS2O3 +2NaCl
2. Action of mineral acids. Acids liberate thiosulphate acid 2S2O3, which decomposes to water
sulphur dioxide, and sulphur. The sulphur falls in sediment and solution becomes turbid:
Na2S2O3 +2Cl = 2NaCl + SO2 + S + H2O
3. Action of oxidants (iodine, potassium permanganate). Thiosulphates are strong reducers.
Solution of sodium thiosulphate discolours iodine solution:
2Na2S2O3 + I2 = Na2S4O6 + 2NaI
Potassium permanganate is discoloured by thiosulphate-ion:
5Na2S2O3 + 8KMnO4 + 7H2SO4 = 8MnSO4 + 5Na2SO4 + 4K2SO4 + 7H2O
4. Action of silver nitrate. Silver nitrate with thiosulphate-ions forms white precipitate, which
gradually transforms in Ag2S; the precipitate quickly turns yellow, grows brown and becomes
black (a process is accelerated at heating):

Na2S2O3 + 2AgNO3 = Ag2S2O3 +2NaNO3


Ag2S2O3 + H2O = Ag2S + H2SO4
The black precipitate Ag2S dissolves at heating in diluted nitrate acid:
3Ag2S + 8HNO3 = 6AgNO3 + 2NO + 3S + 4H2O
5. Action of iron(III) chloride. Iron(III) chloride with thiosulphate-ions forms at first soluble
iron(III) thiosulphate and solution is painted in the dark-violet colour. Later the solution is
discoloured as a result of iron(III) reducing to iron(II), and thiosulphate oxidizes to
tetrathionate:
2FeCl3 + 2Na2S2O3 = 2FeCl2 + Na2S4O6 + 2NaCl

Reactions of carbonate-ions detection:


1. Action of barium chloride. With barium salts carbonates form the white precipitate BaO3,
soluble in acids:
Na2O3 + BaCl2 = BaO3 +2NaCl
BaO3 +2Cl = BaCl2 + O2 + H2O
2. Action of mineral acids. The acids, includes acetic, decompose carbonates with the 2 elution:
Na2O3 +2Cl = 2NaCl + O2 + H2O
Exposed carbon dioxide detects by reaction with dimness of lime or barium water, that are saturated
water solutions of Ca(OH)2 and Ba(OH)2:
Ca(OH)2 + O2 = CaO3 + H2O
Ba(OH)2 + O2 = BaO3 + H2O
3. Action of silver nitrate. Silver nitrate with carbonate-ions forms white precipitate Ag2O3,
soluble in acids (except HCl):
Na2CO3 + 2AgNO3 = Ag2CO3 +2NaNO3
4. Action of magnesium sulphate. Magnesium sulphate forms in solutions of carbonates the white
precipitate MgCO3:
Na2CO3 + MgSO4 = MgCO3 +Na2SO4
Precipitate is soluble in acids.

Reactions of phosphate-ions detection:


1. Action of barium chloride. Barium chloride in presence alkalis or NH4OH forms with Na2HPO4
solution precipitate Ba3(PO4)2, which dissolves in acids (except H2SO4):
3BaCl2 + 2NaOH + 2Na2HPO4 = Ba3(PO4)2 + 6NaCl + 2H2O
2. Action of silver nitrate. In the alkaline environment silver nitrate with O43-anion forms yellow
precipitate:
3

Na3O4 + 3AgNO3 = 3Ag3O4 + 3Na NO3


Precipitate is soluble in nitrate acid solution, and also in the ammonium hydroxide solution.
3. Action of magnesial mixture. Magnesial mixture with phosphate-ions forms white crystalline
precipitate MgNH4O4, soluble in chloride acid:
Na2HO4 + MgCl2 + NH4OH = MgNH4O4 + 2NaCl + H2O
4. Action of molybdenum liquid. In acidic environment ammonium molybdate with phosphateions forms yellow crystalline precipitate, soluble in the reagent surplus:
12(NH4)2 MoO4 + (NH4)3O4 + 24HNO3 = (NH4)3O412MoO3 + 24NH4NO3 + 10H2O

Reactions of oxalate-ions detection:


OH

Structural formula of oxalic acid:

OH

1. Action of barium chloride. Oxalate-ions with barium ions forms white crystalline precipitate:
(NH4)2C2O4 + BaCl2= BaC2O4 + 2NH4Cl
Precipitate is soluble in boiling acetic acid (difference from calcium oxalate) and in solutions of
strong acids with formation of oxalic acid.
2. Action of calcium chloride. Calcium chloride with oxalates forms white small-crystalline
precipitate of calcium oxalate, soluble in mineral acids and insoluble in acetic acid:
(NH4)2C2O4 + aCl2= aC2O4 + 2NH4Cl
3. Action of potassium permanganate. Potassium permanganate in acidic environment with
oxalate-ions at heating is discoloured as a result of reducing to Mn+2:
5(NH4)2C2O4 + 2KMnO4 +8H2SO4= 2MnSO4 + K2SO4 + 10CO2 + 5(NH4)2SO4 + 8H2O

Reactions of borate- and tetraborate-ions detection:


1. Action of barium chloride. Barium chloride with Na2B4O7 solution forms white precipitate of
barium methaborate (Ba(BO2)2) soluble in acids:
BaCl2 + Na2B4O7 + 3H2O = Ba(BO2)2 + 2H3BO3 + 2NaCl
2. Action of silver nitrate. Silver nitrate forms white precipitate AgBO2, soluble in nitrate acid and
in ammonium hydroxide:
2AgNO3 + Na2B4O7 + 3H2O = 2AgBO2 + 2H3BO3 + 2NaNO3

3. Flame test. The volatile boron compounds (H3BO3, BF3, H3BO3 ethers) paint gas-ring flame in
green colour. Concentrated sulphate acid and ethanol (or methanol) acting on dry sodium borate
forms boron-ethylic (boron-methylic) ether, which gives to flame character green colour:
H3BO3 + 3H3OH = B(OCH3)3 + 3H2O

Reactions of arsenite- and arsenate-ions detection


(see Reactions of arsenic () and arsenic(V) detection).

Reactions of fluoride-ions detection:


1. Action of barium chloride. Barium chloride with fluoride-anions forms voluminous white
precipitate BaF2, soluble in surplus of mineral acids and ammonium salts solutions:
BaCl2 + 2NaF = BaF2 + 2NaCl
2. Action of calcium chloride. Calcium chloride forms the white precipitate aF2, which heavily
dissolves in the mineral acids and does not dissolve in acetic acid:

aCl2 + 2NaF = aF2 + 2NaCl


3. Reaction with iron thiocyanate. The fluoride-ions can be detected by reaction of destruction
(discoloration) of iron() thiocyanate red colour as a result of formation of stabile colourless
complex [FeF6]3 :
FeCl3 + 3NaCNS = Fe(CNS)3 + 3NaCl
Fe(CNS)3 + 6NaF(saturated) = Na3[FeF6] + 3NaCSN

Reactions of chromate- and dichromate-ions detection:


1. Action of barium chloride, silver nitrate, and lead acetate. Chromate-anions form heavy soluble
yellow precipitates with ions of barium() and lead(), and orange-red colour with silver()
ions, which do not dissolve in acetic acid:
Na2CrO4 + BaCl2 = BaCrO4 + 2NaCl
Na2CrO4 + Pb(NO3)2 = PbCrO4 + 2NaNO3
Na2CrO4 + AgNO3 = Ag2CrO4 + 2NaNO3
Barium chromate dissolves in chloride acid, lead chromate dissolves in nitrate acid and alkalis,
silver chromate dissolves in nitrate acid and solution of ammonium hydroxide.
2. Reaction of perchromic acid formation. Hydrogen peroxide on acidic solution oxidises
dichromate-ions to chrome peroxide CrO5 (or perchromic acid 2CrO6):

2Cr2O7 + 4H2O2 = 2CrO5 + 5H2O


If to the reactionary mixture add a mixture of isoamyl alcohol with diethyl ether and shake up, an
overhead layer is painted in the dark blue colour as a result of transition of the chrome peroxide
(perchromic acid) to alcohol-ether layer.
5

3. Action of potassium iodide in acidic environment. Iodides oxidise dichromate-ions in acidic


environment to free iodine, as a result solution is painted in brown colour:
K2Cr2O7 + 6KI + 7H2SO4 = Cr2(SO4)3 + 3I2 + 4K2SO4 + 7H2O

Reactions of tartrate ions detection:


O

OH

Structural formula of tartrate acid:

OH

HO

OH

1. Action of iron(I) sulphate and hydrogen peroxide. Iron() hydroxide with tartrates forms dark
blue complex compounnd:
HO
OH
OH
O
O + 2H2O
O
OH + Fe(OH)3
HO
O O

OH

Fe

OH

2. Action of resorcinol in acidic environment. Crystals of tartrate acid salt with resorcinol or
pyrogallol at presence of concentrated sulphate acid and at heating give a violet product of
condensation of resorcinol or pyrogallol with glycol aldehyde, which forms from tartrate acid
under action of sulphate acid:
O

HO

OH

+ H2SO4

OH +

HO

OH

OH

+ CO2 + Na2SO4 + 2H2O


OH

Cool solution and outpour in water; colouring solution changes on red.


3. Action of silver nitrate. Silver nitrate with tartrate-ions forms yellow insoluble salt:
Na2C4H4O6 + 2AgNO3 Ag2C4H4O6 + 2NaNO3
The precipitate dissolves in ammonia solutions.
4. Action of potassium chloride. Crystalline potassium chloride with concentrated solutions of
tartrates at ethanol presence from white crystalline precipitate:
NaH446 + KCl KC4H4O6 + NaCl
A fall of precipitate is accelerated in case of cooling and rubbing walls of test tube by glass stick.

Reactions of citrate ions detection:

HO
O
HO
Structural formula of citrate acid:

OH

OH

1. Action of calcium chloride. Calcium chloride with salts of citric (lemon) acid forms soluble in
acids white precipitate:
H3657 + CaCl2 CaHC6H5O7 + 2HCl
2. Action of acetic anhydride. Acetic anhydride and citrates at heating with concentrated sulphate
acid form acetylsalicylate with character smell:

HO

OH
H3C

OH

O
+

HO

O
OH

O
O

OH
H2SO4

H3C

+ CH3COOH

O
OH

H3C

Reactions of Anions of the Second Analytical Group


To the second analytical group belongs sulphide- (S2), chloride- (l), bromide- (Br),
iodide- (), cyanide- (CN), thiocynate- (SCN) and benzoate- (C6H5COO) ions. A group reagent
is silver nitrate solution, acidified by 2 solution of nitrate acid. Anions of the first analytical
group are also precipitated by silver cations; however their precipitations dissolve in nitrate acid.

Reactions of chloride-ions detection:


1. Action of silver nitrate. Chlorides with silver nitrate form white amorphous precipitate:
AgNO3 + NaCl = AgCl + NaNO3
Silver chloride insoluble in diluted nitrate acid, easily soluble in ammonia solutions and in
ammonium carbonate:
AgCl + 2N4O = [Ag(N3)2]Cl + 2H2O
In case of addition of acid or potassium iodide to formed ammoniac solution the AgCl or AgI
precipitates falls out:
[Ag(N3)2]Cl + 2HNO3 = AgCl + 2N4NO3
[Ag(N3)2]Cl + 2KI = AgI + 2N3 + KCl
2. Action of potassium of dichromate and diphenylcarbazide. Potassium dichromate in acidic
environment oxidises the chloride-ions to free chlorine, which, eluting, oxidizss diphenylcarbazide
to diphenylcdarbazone:
K2Cr2O7 + 6NaCl + 7H2SO4 = Cr2(SO4)3 + 3Cl2 + 4NaSO4 + 7H2O
N N
H H

+ Cl2

N N
H H

O
N N

N N
H H

+ 2HCl

O
Reaction performance. Investigated substance place in test tube, add 0,2 g of potassium
dichromate and 1 ml of sulphate acid. The test tube opening cover a filtration paper impregnated
with 0,1 ml of diphenylcarbazide solution. A paper is painted in the violet-red colour.
2. Action of potassium permanganate. Strong oxidants in acidic environment oxidise chlorides to
free chlorine:
2KMnO4 + 10KCl + 8H2SO4 = 2MnSO4 + 5Cl2 + 6K2SO4 + 8H2O
Free chlorine detects by smell or by turning in blue colour of iodine-starch paper, which contains
and starch.

Reactions of bromide-ions detection:


1. Action of silver nitrate. Silver nitrate with bromide-ions forms the yellow precipitate, hardly
soluble in solution of ammonium hydroxide (unlike chloride-ions):
AgNO3 + KBr = AgBr + KNO3
2. Action of oxidisers. Solutions of chlorine water, or chloramines, or potassium permanganate, or
potassium dichromate, or other oxidants in environment of sulphate acid oxidise bromine ions
to free bromine:
KBr + Cl2 = Br2 + KCl
2KMnO4 + 10KBr + 8H2SO4 = 2MnSO4 + 5Br2 + 6K2SO4 + 8H2O
K2Cr2O7 + 6KBr + 7H2SO4 = Cr2(SO4)3 + 3Br2 + 4K2SO4 + 7H2O
It is possible to detect free bromine by such methods:
free bromine paints water solutions in brown;
organic solvents (chloroform, benzene) are painted by the free bromine in orange colour;
free bromine with fuchsine-sulphite acid forms bromine-derivatives halving red-violet colour:
2KBr + PbO2 + 4CH3COOH Pb(CH3COO)2 + Br2 + 2CH3COOK + 2H2O
H2N

NH-SO2-Na

H3C

+ Br2 + 2H2O

NH-SO2-Na

+
_
NH2 . Br

H2N

H3C

+ 2NaHSO4 + HBr

NH2

yellow-green fluoresceine under action of free bromine changes in red tetrabromofluoresceine.

Reactions of iodide-ions detection:


1. Action of silver nitrate. Silver the nitrate with iodide-ions forms yellow precipitate, insoluble in
solution of ammonium hydroxide (unlike chloride-ions):

AgNO3 + K = Ag + KNO3
2. Action of lead salts. Lead salts with iodides form yellow precipitate, which re-crystallise from
water and as gold like scales:
Pb(NO3)2 + 2K = PbI2 + 2KNO3
3. Action of oxidisers. Solutions of potassium dichromate and potassium permanganate in
environment of sulphate acid, and sodium nitrite in acetic environment oxidize iodides to free
iodine:
K2Cr2O7 + 6K + 7H2SO4 = Cr2(SO4)3 + 32 + 4K2SO4 + 7H2O
2KMnO4 + 10K + 8H2SO4 = 2MnSO4 + 52 + 6K2SO4 + 8H2O
2HI + 2HNO2 = I2 + 2H2O + 2NO
Oxidization of iodide-ions by nitrites in environment of acetic acid is specific and distinguishes
iodides from chlorides and bromide. Free iodine detects by turn in blue of starch solution.
Chloroform is painted in violet colour.
4. Action of mercury() nitrate. Iodides are precipitate from solutions of mercury() salts with
formation of brown-green colour sediment:

g2(NO3)2 + 2KI = g2I2 + 2KNO3,


which dissolves in surplus of potassium iodide with formation of the complex compound (named
the Nesslers reagent) and elemental mercury:

g2I2 + 2KI = K2[gI4] + g


Reactions of sulphide-ions detection:
1. Action of silver nitrate. Silver nitrate with silver sulphide forms black precipitate:
2AgNO3 + (N4)2S = Ag2S + 2N4NO3
Silver sulphide does not dissolve in sulphides and polysulphides of alkaline metals, mineral acids,
unless nitrate acid:
3Ag2S + 8NO3 = 6AgNO3 +2NO +3S + 42
2. Action of cadmium salts. Cadmium salts with sulphides form yellow precipitate:
Cd(NO3)2 + Na2S = CdS + 2NaNO3
3. Action of mineral acids. The acids liberate hydrogen sulphide from sulphides:
Na2S + 2HCl = H2S + 2NaCl
4. Action of sodium nitroprusside. Sodium nitroprusside [sodium nitrozopentacyanoferrate()]
with sulphides form red-violet complex:
Na2S + Na2 [Fe(CN)5NO] = Na4 [Fe(CN)5NOS]
10

Reactions of thiocyanate-ions detection:


1. Action of silver nitrate. Silver nitrate with thiocyanate-ions forms white amorphous precipitate,
insoluble in diluted nitrate acid, but soluble in solution of ammonium hydroxide:
AgNO3 + N4SCN = AgSCN + N4NO3
AgSCN + 2N4OH = [Ag(NH3)2]SCN + 2H2O
2. Action of iron() chloride. Salts of iron() paint solutions of thiocyanates in blood-red:
FeCl3 + 3 N4SCN = Fe(SCN)3 + 3N4Cl
3. Action of cobalt nitrate. Cobalt salts with thiocyanate-ions form dark blue complex ion
[Co(SCN)4]2, which is well extracted by butanole or pentanole:
CoCl2 + 4N4SCN = (N4)2[Co(SCN)4] + 2N4Cl

Reactions of detection of cyanide-ions:


Reactions of cyanide-ions detection needs keeping strictly to the established order with the
poisonous substances using. In acidic environment at temperature higher 30 forms volatile
N. That is why necessary to perform all reactions in alkaline environment.
1. Action of silver nitrate. Silver nitrate with cyanide-ions forms white amorphous precipitate. The
complete sedimentation is achieved only at the large surplus of AgNO3, since AgCN precipitate
dissolves in surplus of cyanides with complex K[Ag(CN)2] formation. In case of subsequent
addition of AgNO3 the complex ion decomposes and forms AgCN precipitate:
AgNO3 + KCN = AgCN + KNO3
AgCN + KCN = K[Ag(CN)2]
K[Ag(CN)2] + AgNO3 = 2AgCN + KNO3
That is why detection of cyanide-ion by this reaction it is the best to conduct, adding explored
solution to the nitrate silver solution, instead of vice versa.
The silver cyanide does not dissolve in nitrate acid, but easily dissolves in solution of ammonium
hydroxide, sodium thiosulphate, and solutions of cyanides of alkaline metals with formation the
proper complex compounds.
2. Reaction of cyanides transformation to thiocyanates. Under action of ammonium polysulphide
solution on cyanides of alkaline metal the cyanide-ion transforms to thiocyanate-ion. The
thiocyanate-ion detects by reactions with Fe3+ or Co2+ ions:
KCN + (N4)2S2 = KSCN + (N4)2S
FeCl3 + 3 KSCN = Fe(SCN)3 + 3KCl
CoCl2 + 4KSCN = K2[Co(SCN)4] + 2KCl
3. Reaction of Berlin blue formation. For conducting this reaction the cyanide-ions translate in the
complex ion [Fe(CN)6]2 co-operation of cyanide-ions with FeSO4 in the alkaline environment
and after it enter in reaction with FeCl3 in acidic environment:
FeSO4 + 2NaOH = Fe(OH)2 + Na2SO4
11

Fe(OH)2 + 6KCN = K4[Fe(CN)6] + 2KOH


4FeCl3 + 3K4[Fe(CN)6] = Fe4[Fe(CN)6]3 + 12KCl

Reactions of benzoate- ions detection:


COOH
Structural formula of benzoic acid:

1. Action of iron(III) chloride. Iron() chloride in neutral environment with benzoates forms
yellow-pink precipitate:
COO-FeCl2

COONa

+ NaCl

+ FeCl3

2. Action of concentrated sulphate acid. Investigated substance places in test tube and wets by 0,2
0,3 ml of concentrated sulphate acid, carefully heat a bottom of test tube; the white raid appears
on inner walls of the test tube.
COOH

+ H2SO4 conc.
- H2 O

+ CO2

3. Action of chloride acid. Investigated substance dissolve in 10 ml of water. To obtained solution


add 0,5 ml of chloride acid. Formed precipitate after re-crystallisation from warm water and
drying in vacuum has a melting temperature of from 120 to 124 :

COONa

COOH
+ HCl

+ NaCl

12

Reactions of Anions of the Third Analytical Group


To the third analytical group belong nitrate- (NO3), nitrite- (NO2), acetate- (CH3COO),
permanganate (MnO4), and salicylate- (C6H4(O)COO) ions. This group has not a group reagent.

Reactions of nitrate-ions detection:


1. Action of diphenylamin. Diphenylamine reduces nitrates, oxidizing thus to diphenylbenzidine,
and then to dark blue compound:

NH

+ NaNO3 + H2SO4

+ Na2SO4 + NO2 + H2O

2. Reaction of brown ring formation with iron(II) sulphate. Iron sulphate in acidic environment
reduces nitrates to nitrogen(II) oxide:
2NaNO3 + 6FeSO4 + 4H2SO4 = 3Fe2(SO4)3 + Na2SO4 + 2NO + 4H2O
The nitrogen() oxide forms with FeSO4 brown complex [FeNO]SO4:
FeSO4 + NO = [FeNO]SO4
Reaction performance: investigated solution and concentrated sulphate acid carefully layer on
FeSO4 crystals. The brown ring thus appears.
3. Reaction with metallic zinc and concentrated solution to sodium hydroxide. Zinc, magnesium,
and aluminium in alkaline environment reduce nitrate-ions to ammonia, which turn colour of
litmus paper from red to blue:
NaNO3 + 4Zn + 7NaOH + 6H2O = NH3 + 4Na2 [Zn(OH)4]
4. Reaction with antipyrine. In environment of concentrated sulphate acid nitrates with antipyrine
form red colour nitroantipyrine:

H3C

H3C

NO2

+ NaNO3 + H2SO4

H3C

N
C6H5

+ Na2SO4 + H2O

H3C

C6H5

Reactions of nitrite-ions detection:


1. Action of antipyrine in acidic environment. In environment of concentrated sulphate acid
nitrates with antipyrine give green colour nitrozoantipyrine:
13

H3C

H3C

NO

+ NaNO2 + H2SO4

H3C

+ Na2SO4 + H2O

H3C

C6H5

C6H5

2. Action of mineral acids. Mineral acids liberate nitrite acid from nitrites:
2NaNO2 + H2SO4 = 2SO4 + 2NO2
Nitrite acid is unstable and decomposes with formation of nitrogen oxides and water:
2NO2 = NO2 + NO + H2O
3. Action of potassium permanganate. Potassium permanganate in acidic environment oxidiszes
nitrites to nitrates; thus solution of potassium permanganate is discoloured as a result of Mn2+
ions formation:
5NaNO2+ 2KMnO4 +3H2SO4 = 2MnSO4 + K2SO4 + 5NaNO3 + 3H2O
4. Reaction of brown ring formation with iron(II) sulphate. Iron sulphate in acidic environment,
like nitrates, reduces nitrites to nitrogen(II) oxide:
2NaNO2 + 2FeSO4 +2H2SO4 = Fe2(SO4)3 + Na2SO4 + 2NO + 2H2O
Nitrogen() oxide with FeSO4 forms brown complex [FeNO]SO4:
FeSO4 + NO = [FeNO]SO4
Reaction performance: explored solution and concentrated sulphate acid carefully layer on FeSO4
crystals. The brown ring thus appears.
5. Action of potassium iodide. Potassium iodide in acidic environment reduces nitrites to
nitrogen() oxide, oxidizing thus to free iodine, which turns water solution to brown or starch
solution to blue:
2KNO2 +2KI +2H2SO4 = I2 + 2K2SO4 + 2NO + 2H2O
6. Action of diphenylamine. Diphenylamine reduces nitrites, like nitrates, oxidizing thus to
diphenylbenzidine, and then to dark blue compound:

NH

+ NaNO2 + H2SO4

+ Na2SO4 + NO + H2O

14

7. Reaction with sulphanylic acid and - or -naphthole (Griss test). Sulphanylic acid with
sodium nitrite in acidic environment forms diazonium salt, which enters in reaction of azoconjugation with naphtholes. In this reaction bright red azo-dye forms:

N N

NH2

Cl

+ NaNO2 + HCl

+ NaCl + H2O

SO3H

SO3H

OH
+

N N

OH

N N

+ NaCl + H2O
Cl +

SO3H

+ NaOH
SO3H

Reactions of acetate-ions detection:


1. Reaction of ethyl acetate formation. In presence of concentrated sulphate acid ethanol (butanol,
pentanol and other alcohols) with acetic acid forms ethyl acetate having character pleasant
smell:
2CH3COONa + H2SO4 = 2CH3COOH + Na2SO4
CH3COOH + C2H5OH = CH3COOC2H5 + H2O
2. Action of iron(III) chloride. Iron() chloride transforms acetates in red-brown complex:
FeCl3 + 3CH3COONa = Fe(CH3COO)3 + 3NaCl
3Fe(CH3COO)3 + 2H2O = [Fe3(CH3COO)6(OH)2](CH3COO) + 2CH3COOH
3. Action of oxalic acid. At heating acetates with equal quantity of oxalic acid forms acetic acid
having character smell:
2CH3COONa + H22O4 = 2CH3COOH + Na22O4
4. Action of silver nitrate. Silver nitrate forms white precipitate of silver acetate only in
concentrated solutions:
AgNO3 + CH3COONa = CH3COOAg + NaNO3

15

Reactions of permanganate-ions detection:


1. Action of reducers (potassium iodide, oxalate acids, sodium nitrite). Reducers in acidic
environment reduce MnO4 ions that have the violet-red colouring, to colourless Mn+2-ions:
2KMnO4 + 10K + 8H2SO4 = 2MnSO4 + 52 + 6K2SO4 + 8H2O
5H2C2O4 + 2KMnO4 +3H2SO4= 2MnSO4 + K2SO4 + 10CO2 + 8H2O
5NaNO2+ 2KMnO4 +3H2SO4= 2MnSO4 + K2SO4 + 5NaNO3 + 3H2O

Reactions of salicylate-ions detection:


COOH

OH

Structural formula of salicylic acid:

1. Action of iron(III) chloride. Iron() chloride with salicylate-ions forms iron() salicylate
having indigo or red-violet colour (depending on composition).
FeCl

COO

COOH

OH

+ 2HCl

+ FeCl3

Colouring disappears in case of chloride acid addition (formation of precipitate of salicylic acid)
and is saved in case of acetic acid addition.
2. Action of chloride acid. Chloride acid from salicylates solutions deposits white precipitate,
which after re-crystallisation from the hot water and drying in vacuum has a melting point from
156 C to 161 C:
COONa

COOH

OH

OH

+ HCl

+ NaCl

3. Reaction of methyl salicylate formation. In presence of concentrated sulphate acid methanol


with salicylic acid forms methyl salicylate having character smell:
COO-CH3

COOH

OH

OH

+ CH3OH

H2SO4 conc.

+ H2 O

16