This document discusses qualitative inorganic analysis of anions, specifically focusing on carbonates/bicarbonates and sulfur-containing anions. It describes: 1) Carbonates and bicarbonates react with acids to produce carbon dioxide gas, which turns limewater milky. Sulfur-containing anions like sulfides, sulfites and thiosulfates are reducing and react with acids. 2) Common tests involve adding reagents like barium chloride, silver nitrate, and iron (III) chloride to detect anions via formation of insoluble precipitates. 3) The document provides details on solubility rules and characteristic reactions for each group of anions to allow their identification in mixtures

1. Qualitative Inorganic AnalysisQualitative Inorganic Analysis

2. Analytical chemistry could be divided into three main parts;
qualitative, quantitative and applied.
Qualitative analysis deals with detection and identification of
different substances singly or in a mixture.
This part deals with the qualitative analysis of anions,
which could be defined as the negatively charged fragments
of salt or compound. Alternatively anions refer to acid radical.
An example is Nacl:
NaCl Na +
+ Cl-
Cation Anion
Basic radical Acid radical

3. Anions are divided into six groups:
1- Carbonates and Bicarbonates group
2- Sulphur-containing anions
3- Halides
4- Cyanogen anions
5- Arsinic and phosphorous containing anions
6- Nitrogen- containing anions

4. Carbonates and Bicarbonates group
CO3
2-
HCO3
-
I. General characters
1- Parent acid:
Carbonic acid (H2
CO3
) is a very weak volatile acid
(stronger than HCN and boric acid)
Heating of solution of H2
CO3
, CO2
will evolve.
H2
CO3
CO2
+ H2
O
Bicarbonates are considered to be the first step of ionization
of carbonic acid, while in the second step carbonates are formed
H2
CO3
H+
+ HCO3
- H+
+ CO3
2-

5. 2-Solubility:
All carbonated with the exception of those of the alkali metals
(Na+
and K+
) and of ammonium are insoluble in water.
All bicarbonates are soluble in water.
II. General Reactions
1- Dry Reactions
a- Action of dilute HCl
Decomposition with effervescence due to the evolution
of CO2
gas, for both CO3
--
and HCO3
-
CO3
--
+ 2H+
CO2
↑+ H2
O
This is a type of displacement reaction in which stronger
acid
liberates the very weak carbonic acid, which
spontaneously
decomposes to CO & H O.
NaHCO3+ H+
CO2 ↑ + H2O + Na+

6. Test for CO2 gas:
The solid substance is placed in a test tube, dilute HCl is
added, which immediately displaced the gas, which is evolved
(upon warming) and passed into lime water or baryta water
contained in another test tube.
The production of a turbidity indicates the presence of
carbonates or bicarbonates.
CO2
+ Ca(OH)2
→ CaCO3
+ H2
O
CO2
+ Ba (OH)2
→ BaCO3
+ H2
O
With prolonged passage of CO2, the turbidity formed due
to the insoluble carbonates, slowly disappears as a result
of the formation of a soluble bicarbonate.
CaCO3
+ CO2
+ H2
O Ca (HCO3
)2Boiling

7. 2-Wet Reactions
In order to carry out the wet reactions, a solution of the substance
in water must be done.
Bicarbonates are mostly decomposed on heating with the liberation of CO2
.
2HCO3
-
CO3
--
+ H2
O + CO2
↑ .
a- Reaction with AgNO3
A white precipitate of silver carbonate is immediately formed.
CO3
--
+2Ag+
→ Ag2CO3
The precipitate is soluble in mineral acids (nitric acid) and in ammonia.
Ag2
CO3
+ 2H+
→ 2 Ag+
+ CO2
+ H2
O
Ag2
CO3
+4NH3
→ 2[Ag (NH3)2
]+
+ CO3
2-
The precipitate becomes yellow or brown if the mixture is boiled.
Ag2
CO3
↓ Ag2
O +CO2
↑
boiling

8. b- Reactions with BaCl2
, CaCl2 and MgSO4
:
White precipitates of BaCO3
, CaCO3
and MgCO3
will be obtained
upon the addition of these reagents to samples of carbonate
solution.
BaCl2
+ NaCO3
→ BaCO3
+ 2 NaCl
Ca++
+ CO3
--
→ CaCO3
Mg++
+ CO3
--
→ MgCO3
The precipitate is soluble in mineral acids
For HCO3
-
; No ppt. on cold since all bicarbonates are soluble in
water
Ba++
+2HCO3
-
Ba(HCO3
)2
Soluble
H2
O + CO2
↑+ BaCO3 Boiling

9. III. Mixture of CO32-
& HCO-
3
Both anions haves similar reactions, but CO3
2-
form precipitates
immediately on cold upon the addition of CaCl2, BaCl2 or MgSO4,
while the bicarbonates of these metals are soluble.
Separation:
Add excess CaCl2
(BaCl2
or MgSO4
) to a solution of the
mixture
CO3
2-
/HCO3
-
a white ppt. indicates CO3
--
,
centrifuge or filter
Contrifugate White ppt.
May be HCO3
-
CaCO3
2-
H+
CO2 + H2O
Confirmatory test: 1) Boil
2)Add ammonia
solution white ppt.
Ca (HCO3)2 + 2 NH3 CaCO3+ (NH4)2 CO3

10. Sulphur-containing anions
This group of anions, are;
1- Sulphide (S2-
)
2- Sulphites (SO3
2-
)
3- Thiosulphate (S2O3
2-
)
4- Sulphates (SO4
2-
)
5- Perasulphate (S2O8
2-
).
I. General characters
1-Parent Acids: a- Hydrogren sulphide or Hydrosulphuric acid (H2
S)
It is a gas with offensive rotten egg odour and poisonous. In
solution
it gives a weak acid, which ionizes in two steps;
H2
S H+
+ HS-
(hydrosulphide ion)
HS-
H+
+ S--
(sulphide ion)
Both HS-
and S--
ions give the same reactions.

11. b- Sulphurous acid:(H2
SO3
)
This acid is only known in solution (like H2
CO3
). It has moderate
strong
acidity. Like H2
CO3
in water; present in equilibrium as follows:
H2
SO3 H+
+ HSO3
-
H+
+ SO3
--H2O + ↑SO2
heat
Acid sulphite
c- Thiosulphuric acid: (H2S2O3)
It is not known in the free form, and decomposes to give, H2O, SO2
and S.
It's more stronger than sulphurous acid in solutions.
It consists of SO3
2-
solution and S, which upon boiling gives S2O3
2-
.
d- Sulphuric acid: (H2SO4):
It's a colourless oily liquiud (B.P.
3300
C).General properties of H2SO4
1- Acid properties;
It is one of the strongest acids, ionize in dilute solutions in two
steps, H2
SO4
H+
+ HSO4
-
(hydrogen sulphate)
HSO4
-
H+
+ SO4
--
(sulphate)

12. Metals can liberate hydrogen from H2
SO4
solution.
H2
SO4
+ Zno
ZnSO4
+ H2
Being a strong acid can replace weak acids like, boric acids,
hydrocyanic acid and volatile acids or their decomposition
products
due to its high B.P.
2NaCl + H2
SO4
Na2
SO4
+ 2HCl
2- Dehydrating properties;
Conc. H2
SO4
has a great tendency to combine with water to from
stable
hydrates H2
SO4
.x H2
O. So it is used as a dehydrating agent for
certain substance, and used mostly in the dissectors.
It causes charring for certain organic substances as sugars due to
the vigorous abstracting of water from theses substances.
3- Oxidizing properties:
It's considered to be as moderately strong oxidizing agent when
heated
with most reducing agents
H2
SO4
H2
O + SO2
+ [O]
It is reduced to SO2
, while with active reducing agents it may
be
reduced to So
or H2
S.
heat

13. 2-Solubility:
All Na+
, K+
and NH4
+
salts of sulphur containing anions are
soluble
in water.
Sulphides : Other sulphides are in-soluble except those of Ca++
,
Ba++
, & Sr2+
dissolve due to hydrolysis.
Sulphites: Other sulphites are all in-soluble.
Thiosulphates: Most S2O3
2-
are soluble, Ag+
, Pb++
, Hg2+
& Ba++
salts
are slightly soluble.
Sulphates: All sulphates are soluble except Pb++
, Ba++
and Sr++
.
Ca++
& Mg++
salts are slightly soluble.

14. 3-Complexing agent:
Thiosulphate form complex with Fe3+
Fe3+
+ 2S2
O3
--
(Fe(S2
O3
)2
)-
purple color
4-Reducing agent:
Sulphides, sulphites and thiosulphates are reducing agents.
They reduce solutions of I2, KMnO4 and K2Cr2O7 with varying activities
in acidified solutions.
I2+S2-
2I-
+So
lodine (brown) Colourless
H+
2KMnO4
+ 5S2-
+ 16H+
2Mn++
+ 5SO4
--
+ 8H2
O +2K+

15. I2
+SO3
2-
+H2
O SO4
2-
+2I-
+2H+
2 MnO4
-
+ 5 SO3
--
+ 6H+
2Mn++
+ 5SO4
--
+ 3H2
O
Cr2
O7
--
+ 3SO3
2-
+ 8H+
2Cr3+
+ 3SO4
--
+4H2
O
I2
+2S2
O3
-- H+
S4
O6
2-
+2I-
Tetrathionate
Fe3+
+2S2O3
2-
S4O6
2-
+Fe2+H+
8MnO4
-
+ 5 S2
O3
--
+ 14H+
8Mn++
+10SO4
--
+7H2
O
4Cr2
O7
2-
+ 3S2
O3
2-
+ 26H+
8 Cr3+
+6SO4
--
+ 13 H2
O

16. II. General Reactions
1- Dry Reactions
a- Action of dilute HCl
1.Sulphide; S2-
H2
S gas; evolved upon adding dil. HCl to a solid sample.
The gas evolved has its characteristic rotten egg odour, and could be
identified by 1- blackening of filter paper moistened with lead acetate sol.
S--
+ 2H+
H2
S
2- alternatively, a filter paper moistened with cadmium acetate
solution,
turns yellow
H2
S + Cd++
CdS
Yellow
H2S has reducing character, It reacts with l2 solution, acid KMnO4,
acid K2Cr2O7
H2S+Pb++
PbS black

17. It bleaches the brown color of l2
solution, changes the pink color of
acid KMnO4
into colorless and changes the orange color of acid
K2
Cr2
O7
into green.
H2
S + l2
2l-
+ 2H+
+So
5H2
S + 6H+
+2 MnO4
-
2Mn++
+ 8H2
O + 5So
3H2
S + 8H+
+ Cr2
O7
--
2Cr3+
+ 7H2
O + 3So
2- Sulphite: SO3
2-
Upon treatment of SO3
--
with dil. HCl, SO2
gas will evolve, due to the
decomposition of the liberated unstable H2
SO3
SO--
3
+ 2H+
H2
SO3
SO2
+H2
O
The evolved SO2
gas has a characteristic bunt sulphur odor and turbid
lime water (like CO2
) due to the formation of the insoluble CaSO3 which
is soluble upon prolonged passage of SO2
due to the formation of soluble
calcium bisulphite.
Ca (OH)2
+SO2
CaSO3
+ H2
O

18. CaSO3
+ SO2
+ H2
O Ca(HSO3
)2
.
SO2 like H2S has reducing character, bleaches the brown color of iodine,
reacts with acid KMnO4 and acid K2Cr2O7.
l2 + SO2 + H2O SO3 + 2H+
+ 2l-
2MnO4
-
+ 5 SO2 + 6H+
2Mn++
+ 5SO3 + 3H2O
Cr2O7
2-
+3 SO2 + 8H+
2Cr3+
+ 3SO3 + 4H2O
3- Thiosulphate; S2O3
2-
No immediate change on cold, but on warming with dil. HCl or standing,
the solution become turbid due to the liberated yellow colloidal sulphur
with evolution of SO2
gas. This is due to the decomposition of the
produced unstable thiosulphuric acid.
S2O3
--
+ 2H+
H2
S2
O3
H2
O + SO2
+ So
Thiosulphate has the same action of sulphite with HCl in addition to
formation of yellow colloidal precipitate.

19. 4- Sulphate: SO4
2-
No reaction with dil. HCl.
2-Wet Reactions
a- Reaction with BaCl2: Add BaCl2 reagent to neutral sample solution:
1- S2-
: No visible reaction
2-SO3
2-
: White ppt. of BaSO3 is formed which is soluble in dil.
HCl.
Ba++
+ SO3
2-
BaSO3
3- S2
O3
--
: No ppt. in dilute solution, but a ppt. is formed from very
concentrated solution.
4- SO4
--
: A white ppt. of BaSO4 is formed which is insoluble in dil. HCl,
even upon boiling.
Ba++
+ SO4
--
BaSO4
White

20. b- Reaction with AgNO3: Add AgNO3 reagent to the neutral sample solution
1-S2-
: a black ppt. of Ag2S is formed which is soluble in hot dil. HNO3,
insoluble in ammonia and KCN solution
2 Ag+
+ S--
Ag2
S
black
2- SO3
2-
: A white crystalline ppt. of Ag2SO3 is formed, which on boiling with
water undergoes self oxidation reduction with the production
of grey ppt. of metallic silver.
2Ag+
+ SO3
2-
Ag2
SO3 White
2 Ag2
SO3
boil
2 Ago
+ Ag2
SO4
+ SO2

21. Silver sulphite is soluble in nitric acid, ammonia and in excess sulphite
to give a complex salt, which on boiling gives a grey ppt. of metallic silver
Ag2
SO3
+ SO3
--
2(AgSO3
)-
2(AgSO3
)- boiling
2Ago
+ SO4
--
+ SO2
3- S2
O3
--
: Forms white ppt. of silver thiosulphate which changes its color
on standing to yellow, brown and finally black, due to the
formation of Ag2
S.
Ag2
S2
O3
is soluble in excess S2
O3
--
to give a complex ion.
2 Ag+
+ S2
O3
--
Ag2
S2
O3
Ag2
S2
O3
+ H2
O Ag2
S + H2
SO4
Ag2
S2
O3
+ 3S2
O3
--
2(Ag(S2
O3
)2
)3-

22. 4- SO4
2-
: No ppt. in dil solution, but a ppt. may be formed in a very
concentrated solution.
c- Reaction with FeCl3: Add FeCl3 reagent to the neutral sample solution
1-S2-
: a black ppt. of Fe2S3 is formed which is soluble in dil. HNO3
2Fe3+
+ 3S--
Fe2
S3 black
2- SO3
--
: A drak red color of ferric sulphite is produced on cold.
2Fe3+
+ SO3
--
Fe2
(SO3
)3
3- S2O3
2-
: A purple color of complex ferric thiosulphate is produced
which disappears on boiling as tetrathionate and Fe2+
are formed
from the oxidation of S2O3
2-
with Fe3+
, even on cold
Fe3+
+ 2S2O3
2-
(Fe(S2O3)2)-
2 S2
O3
--
+ 2Fe3+
2Fe++
+ S4
O6
--
4-SO4
2-
: do not react with FeCl3.

23. d- Reaction with lead acetate:
Adding lead acetate reagent to the neutral sample solution.
1- S--
: A black ppt. of PbS is produced
Pb++
+ S--
PbS
2- SO3
2-
: A with ppt. of lead sulphite which is soluble in cold HNO3.
On boiling oxidation to PbSO4 which is a white ppt. occurs.
SO3
--
+ Pb++
PbSO3
3- S2
O3
--
: A white ppt. of lead thiosulphate is formed which is soluble
in cold HNO3, on boiling a black ppt. of PbS is formed.
Pb++
+S2
O3
--
PbS2
O3
4- SO4
--
: A white ppt. lead suphate, which is insoluble in cold dil. mineral
acids, but soluble in ammonium acetate and hydroxide solutions
(Na+
and K+
)

24. Pb++
+ SO4
2-
PbSO4
PbSO4
+ 4 CH3
COO-
(Pb (CH3
COO)4
)2-
+ SO4
2-
PbSO4
+ 3OH-
HPbO2
-
+ H2
O +SO4
2-
Plumbites
III. Special Tests
1.Sulphide; S2-
Cadmium carbonate
test :
The sulphide solution is shaken with CdCO3
powder, a canary
yellow ppt. of CdS is produced.
S--
+ CdCO3
CdS + CO3
2-
This test could be used for the identification and separation of S2-
when present in a mixture with other sulphur containing anions,
or those anions which do not react with CdCO3
.

25. 2- Sulphite: SO3
2-Zinc nitroprusside test :
Add to cold saturated ZnSO4 solution, equal volume of K4[Fe (CN)6[
solution, add few drops of 1% sodium nitroprusside solution. This
solution
is added to the SO3
2-
solution,a salmon-colored ppt. of zinc
nitroprusside
is formed Zn (Fe(CN)5 NO). The latter reacts with moist SO2 to give a
red ppt. of Na5[Fe(CN)5 SO3[
3- Thiosulphate; S2O3
2-
Formation of thiocyanate :
By boiling with KCN solution (poison), in the presence of NaOH,
Cool,
acidify and add FeCI3, a blood red color of ferric thiocyanate
complex
is produced. S2
O3
--
+ CN- OH-
SCN-
+ SO3
--
boil
Fe3+
+ SCN- Cool
Fe(SCN)2+

26. 4- Sulphate: SO4
2-
Hepar’s test
Sulpate is reduced by carbon to sulphide by heating on a piece
of
charcoal in the presence of Na2CO3 in the reducing zone of the
flame
MSO4+ Na2
CO3
Fusion
Na2
SO4
+ MCO3
Na2
SO4
+ C Na2
S + 4 CO
Transfer the fusion product to a silver coin and moisten with a little
water, a brownish black stain of Ag2S results.
S--
+ 2H2
O 2 OH-
+ H2
S
H2
S + 2 Ag Ag2
S +H2

27. IV. Analysis of Mixtures
1-Mixture of S2-
, SO3
2-
, S2O3
2-
and SO4
2-
:Separation is carried first shaking the mixture solution with CdCO3
powder. The centrifugate is allowed to react with BaCl2 solution
which
will precipitate BaSO4 and BaSO3 leaving S2O3
2-
as soluble
centifugate.
The precipitated BaSO4 and BaSO3 can be separated by the
solubility
of BaSO3 in excess dil. HCI.
S2-
, SO3
2-
, S2O3
2-
, & SO4
2-
Solution + CdCO3
Yellow ppt.
S2- Centrifugate
+ BaCI2
Centrifugate
S2O3
2-
SO2 + So
HClHeat
White ppt.
BaSO3+BaSO4
HCl
White PPt
SO4
2-
Centrifugate SO3
2-
confirm by reducing character

28. 2- Mixture of CO3
2-
and SO3
2-
or S2O3
2-
This type of mixtures are considered to be difficult, due to the interference
occur upon the addition of dil. HCI which liberates CO2 and SO2 gases
which turbides lime water and disappears on prolonged passage.
SO2 can be detected by its reducing characters as discussed before,
but CO2 has non reducing characters.
Therefore SO3
2-
or S2O3
2-
ions must be firstly oxidized into SO4
2-
by
an oxidizing agent such as H2O2,K2Cr2O7 or KMnO4 and dil. H2SO4
and warm, CO2 will only evolve which can be test with lime water.
3- Mixture of H2S and SO2 gases:
In order to differentiate between these two gases which evolve upon
the addition of dil. HCI to sulphides, sulphites and thiosulphates and
having similar reducing properties. A paper moistened with lead
acetate
solution changes into black when exposed to H2S gas, SO2 can
cause
turbidity to lime water

29. Halides
This group of anions, are;
1- Fluoride (F-
)
2- Chloride (Cl-
)
3- Bromide (Br-
)
4- Iodide (I-
)
Fluorides, chlorides, bromides and iodides are known as halogens.
They are characterized by their higher electronegativityAs the ionic size increases, the tendency to loose electrons increases
and therefore iodide ion is firstly and easily oxidized into free I2 by
loosing
readily an electron followed by Br -
when present in a mixture.
However it's difficult to oxidize F-
into F2, hence F-
ions are highly stable
to held strongly a proton.
Therefore the order of stronger halogen acid is from HI > HBr > HCl >
HF.

30. I. General characters
1-Parent Acids: a- Hydrofluoric acid; HF:
It's coloress fuming highly corrosive and itching liquid (B.P.
19.4o
C).
Soluble in water producing the weakest acidic solution in the
halogen
acid series. b- Hydrochloric acid : HCl
Colorless gas with irritating odor, fumes in moist air, extremely
soluble
in water to form acidic solution. Concentrated HCI contains 37% of
HCI gas. c- Hydrobromic acids : HBr
Colorless gas with irritating odor, fumes in moist air and is extremely
soluble in water forming very strongly acidic solution.
On standing the solution becomes yellow due to the oxidation to
bromine.
d- Hydroiodic acid: HI
Colorless gas with irritating odor, fumes strongly in moist air, soluble
in
water forming the strongest acidic solution of the haloacid series.
the solution is colorless, becomes brown on standing due to the
liberated
iodine.

31. 2-Solubility:
All the salts of CI-
, Br-
and I-
are soluble except Ag+
, Hg2
2+
, & Cu+
salts,
their lead salts are slightly soluble in cold water, soluble in hot water.
The alkali metal salts of fluorides, ammonium and silver salts are soluble,
other salts are insoluble or sparingly soluble.
3-Reducing agent:
Cl-
has very weak reducing character.
Br-
and I-
have reducing character, they can react with oxidizing agent like
chlorine water to give Br2 or I2.
I-
has strong reducing power than Br-
so it react with FeCl3, H2O2 and
nitrite solutions.
II. General Reactions
1- Dry Reactions
a- Action of dilute HCl
Hydrochloric acid shows no reaction upon treatment of the solid
sample with it even on heating. This reaction can differentiate
carbonate and sulphur group from halides.

32. b- Action of concentrated H2SO4:Decomposition of the halides occurs upon the addition of
the strong
non-volatile concentrated H2SO4 to the solid sample, this
occurs in
the cold, completely on warming with the evolution of HX
which can
be recognized by a) the fumes evolved.
b) Confirmatory chemical test
2X-
+ H2SO4 = 2 HX + SO4
2-
X = may be CI-
, I-
, Br-
and
F-
1-For Fluoride:
Fluoride gives a characteristic reaction when treated with conc. H2SO4.
Hydrofluoric acid is produced which is colorless and fumes with moist air.
due to the corrosive and itching action of the gas on the glass in presence
of H2O, the test tube or the glass rod subjected to the evolved HF gas
acquire oily appearance due to the formation of silicic acid and
hydrofluorosilicic acid.
This test is considered to be specific for fluoride anion, even in the
presence
of other halides.2 F-
+ H2
SO4
2H F ↑ +
SO4
--
4HF + SiO2
SiF4
+
2H2
O
glass3 SiF4
+ 3H2
O H2
SiO3
+ 2 H2
SiF6
silicic acid hydrofluoro silicic acid

33. 2- For chloride :
HCI gas is evolved upon treatment with conc. H2
SO4
which can be
identified by :
2CI-
+ H2
SO4
2 HCI + SO4
--
1- Formation of white fumes with moist air due the formation of droplets of
hydrochloric acid.
2- Pungent irritating odor.
3- Changing a blue moistened litmus paper into red.
4- Formation of white fumes of NH4CI when a glass rod moistened with
ammonium hydroxide solution is exposed to the evolved gas.
NH4OH + HCI NH4CI + H2O
3- For Bromide:
A mixture of HBr and Br2 may be formed which have characteristic
brown color especially on warming. At the same time sulphuric acid
will be reduced into SO2, H2S or S
2 Br-
+ H2
SO4
2 HBr +
SO4
--
2 HBr + H2
SO4
Br2
+ SO2
+ 2 H2
O

34. 4- For iodide:
Since HI is the most active reducing agent, so it is readily oxidized to
iodine which appears as violet fumes. I2 can be detected by exposing
the evolved gas to paper moistened with starch solution, it changes
into blue.
2I-
+ H2SO4 2 HI + SO4
2-
2HI + H2SO4 I2 + SO2 + 2H2O
6HI + H2SO4 3 I2 + S + 4H2O
8HI + H2SO4 4 I2 + H2S +
4H2O
c- Action of concentrated H2SO4 and MnO2:
If the solid halide is mixed with an equal quantity of precipitated
manganese dioxide, concentrated H2SO4 added and the mixture
gently warmed. Chlorine, bromine and iodine are evolved from CI-
, Br-
and I-
but F-
liberates HF since it has no reducing properties.
2X-
+ 4H+
+ MnO2
Mn++
+ 2H2
O +X2
X = may be CI-, Br- and I-

35. The free halogen, (X2) could be detected by:
1- Bleaching of a moistened colored litmus paper.
2- Suffocating, and irritating odor.
3- Characteristic color of Br2 (brown), I2 (violet) and CI2 gas (greenish tint).
4- I2 changes starch paper into blue, Br2 turns it orange.
5- CI2 and Br2 change a starch – KI into blue due to the oxidation of I-
to I2 produce a blue adsorption complex.CI2
+ 2KI 2KCI
+ I2
Br2
+ 2KI 2KBr + I2
2-Wet Reactions
a- Reaction with AgNO3: To 1ml of the salt solution add AgNO3 reagent.
1- Fluoride: No precipitate, since AgF is soluble in water.
2- Chloride: A white curdy ppt. of AgCI which is insoluble in nitric acid,
soluble in KCN and Na2S2O3 as other silver halides.
The precipitated AgCI is soluble in dil. ammonia solution to give the
ammine complex.

36. Ag+
+ CI-
AgCI
AgCI + 2NH3
[Ag(NH3
)2
[CI
Silver ammine
chloride
[Ag(NH3
)2
[ CI + 2H+
2 NH4
+
+ AgCI
AgCI is reprecipitated upon treatment of the ammine complex with
acid.AgX + 2CN-
[Ag (CN)2
[-
+X- Soluble
complex
AgX + 2 S2
O3
--
[Ag(S2
O3
)2
[3-
+X-
3- Bromide: A curdy, pale yellow precipitate of AgBr, sparingly soluble
in dilute, but readily soluble in conc. ammonia solution
Ag+
+ Br-
AgBr
AgBr + 2 NH3 [Ag(NH3)2[+
+
Br-
4- Iodide: A curdy yellow ppt. of AgI is formed which is insoluble in
dil. ammonia but very slightly soluble in conc. ammonia solution.
Ag+
+ I -
AgI

37. There is a periodicity in character of three silver halides. Since AgI
is the most insoluble one, followed by AgBr and AgCI. Therefore
AgCI
will be dissolved in dil. ammonia, followed by AgBr in conc.
Ammonia
solution but AgI does notThis is also attributed to that the conc. of silver ions (Ag+
) produced
form
the dissociation of silver ammine complex according to its instability
constant is insufficient to exceed the high solubility product of AgCI,
approach that of AgBr (partially soluble) but exceeds that of AgI.
[Ag(NH3
)2
[+ Ag+
+ 2NH3
Instability constant = (Ag+
) (NH3)2
_________________
[Ag(NH3)2[+
Therefore when Br-
or iodide solutions are added to AgCI, yellow
ppt. of
AgBr or AgI are formed.
AgCI + Br-
(or I-
) AgBr (or AgI) + CI-
AgBr + I-
AgI + Br-

38. b- Reaction with BaCI2 solution:
Only fluoride gives a white gelatinous ppt. when BaCI2 reagent is
added
to sample solution. Ba++
+ 2F-
BaF2
The white gelatinous BaF2
ppt. is partially soluble in dil. HCI or
HNO3
No ppt. is formed in case of other halides.c- Reaction with FeCI3:
Add few drops of FeCI3 reagent to concentrated sample solution.
1-F-
: a white crystalline ppt. of the complex salt, which is sparingly
soluble
in water
Fe3+
+ 6 F‑
[FeF6[3-
2- CI-
and Br-
: do not react with FeCI3
3- lodide reacts with FeCI3, due to its strong reducing action with
the liberation of I2.
d- Reaction with lead acetate
Precipitates of Pbx2 are formed in cold solution when lead acetate reagent
is added to sample solutions.

39. F-
, Cl-
and Br-
form a white ppt with lead acetate, sparingly soluble in cold
more soluble in hot water, crystallize on cooling
Pb++
+ 2 F-
PbF2Pb++
+ 2 CI-
PbCI2
Pb++
+ 2 Br-
PbBr2
Iodide forms a bright yellow ppt of PbI2 ↓ which is soluble in hot water
and crystallizes on cooling as golden spangles.
e- Chlorine water test:
Iodide react first with chlorine water before bromide as it has more
reducing character.
Chlorine water oxidizes I-
and Br-
into I2 and Br2 which can be extracted
with chloroform or carbon tetrachloride as violet color or brown or
yellow color of I2 and Br2, respectively.
Chloride and Fluoride do not react with chlorine water .

40. Chlorine water reagent is added drop wise to a solution of iodide or bromide as
excess chlorine water converts Br2 into yellow bromine monochloride or into
colorless hypobromous acid or bromic acid and the organic layer turns pale
yellow or colorless. Also, excess chlorine water oxidized I2 to colorless
iodic acid.
2Br-
+ CI2
Br2
+
2CI-
Br2
+ CI2
2 BrCI
(yellow)Br2
+ CI2
(excess) + 2H2
O
2HOBr+2HCI
Br2
+ 5CI2
(excess) + 6H2
O 2
HBrO3
+10HCI
bromine monochloride
hypobromous acid
bromic acid
Colorless
2I-
+ CI2
I2
+ 2CI-
I2+ 5CI2 (excess) + 6H2O 2 HIO3+10HCI
iodic acid

41. III. Special Tests
1-For Fluorides:
Boron fluoride
test:
When fluoride is mixed with borax and moisten with conc. H2SO4.
The formed HF and boric acid react to produce boronfluoride gas.
If the mixture introduced into the flame tinged green by BF3 gas.
Na2
B4
O7
+ H2
SO4
+ 5H2
O
4H3
BO3
+Na2
SO4
Borax boric acid2NaF+ H2
SO4
2HF +
Na2
SO4
H3
BO3
+ 3HF BF3
+ 3H2
O
2- For chlorides:
Chromyl chloride test:
This test is a specific test for chloride even in the presence of other
halides. It's classified as dry reactions test because, it is carried out
on the solid sample:

42. sulphuric
acid is added, the tube is attached to another tube by a pent tube,
dipped into a NaOH solution. The deep red vapors of chromyl
chloride
CrO2CI2 which are evolved are passed into sodium hydroxide
solution.
The resulting yellow solution in the test tube contains sodium
chromate;
this confirmed by perchromic acid test, which is carried out by
acidifying
with dil. H2SO4, adding 1-2 ml alcohol or ether, followed by a little
H2O2
solution. The organic layer is colored blue.
4CI-
+ Cr2
O7
--
+ 6H+ cond.
2CrO2
Cl2 ↑ + 3H2
O
CrO2
CI2
↑ + 4OH-
CrO4
--
+ 2CI-
+ 2H2
O
2 CrO4
--
+ 2H+
Cr2
O7
--
+
H2
O Cr2
O7
--
+ 7H2
O2
2 CrO8
3-
+ 5H2
O +
4H+
Blue in ether or amyl
alcohol
It is possible to test for CrO4
--
also by lead
acetate CrO4
--
+ Pb++
Pb
CrO4
Yellow

43. N.B.
1-Some CI2 may also be liberated owing to the reacting.
6CI-
+ Cr2O7
--
+ 14H+ 3CI2+ 2Cr3+
+ 7H2O
and this decreases the sensitivity of the test.
2- Fluorides give rise to the volatile CrO2F2 which is decomposed by water,
and hence should be absent or removed.
3- Nitrites and nitrates interfere, as nitrosyl chloride may be formed.
4- Bromides and iodides give rise to the free halogens, which yield
colorless or pale yellow solution with NaOH.
6 Br-
+ Cr2
O7
--
+ 14H+
2 Cr3+
+ 3Br2
+
7H2
O6 I-
+ Cr2
O7
--
+ 14H+ 2Cr3+
+ 3I2
+
7H2
O
Br2
+ 2OH-
OBr-
+ Br-
+ H2
O
(hypobromide)
I2
+ 2OH-
OI-
+ I-
+ H2
O (hypoiodide)

44. 3- For iodides:
A) lodide is readily oxidized in acid solution (dil. H2
SO4
) with nitrite
solution
or H2
O2
into free l22I-
+ 2NO2
-
+ 4H+
I2
+ 2NO +
2H2
O
2I-
+ H2
O2
+ 2H+
I2
+ 2H2
O
B) I-
reacts with Cu++
forming a whit ppt. of Cu2
I2
, the I-
being oxidized
to
free I2
. Thus a white ppt. in brown solution is formed on treating I-
with
CuSO4 solution.2Cu++
+ 4I-
Cu2
I2
↓+I2
C) I-
reacts with mercuric chloride solution mercuric iodide HgI2 will be
precipitated as yellow-scarlet red ppt. which dissolves in excess iodide
forming soluble colorless complex.
HgCI2
+ 2I-
HgI2
+ 2CI-
Scarlet redHgI2
+ 2I-
(HgI4
)2-
Soluble
complex
Nessler's

45. IV. Analysis of Mixtures
1- Mixture of F-
, Cl-
, Br-
and I-
:
a) The F-
is separated by treating the mixture solution acidified with
CH3
COOH with Ba(NO3
)2
or Ca (NO3
)2
Centrifuge
White PPt. Centrifugate
BaF2 CI‑
, Br-
and I-
Confirmed by
Conc.H2SO4 test
b) for the centrifugate ( Cl-
, Br-
and I-
), carry out chlorine water test for
both I-
and Br –
( or get rid of I-
by oxidation to I2 using H2O2 or nitrite and
extract I2 by chloroform then test for Br-
in aqueous solution
c) For CI-
, carry out chromyl test on a solid sample.

46. 2- Mixture of chlorine / chloride and Br2 / Br-
:
Chlorine is tested for by its smell, bleaching effect, while Br2 is tested by
shaking with chloroform, it give brown color. CI-
and Br-
could be tested
after removal of chlorine and bromine by shaking with metallic mercury
(till the smell of CI2 disappears and the liquid doesn't bleach litmus paper).
Insoluble Hg2CI2 and/or Hg2Br2 are formed. Test for CI-
and or Br-
in the
clear supernatant (centrifugate(.
CI2
+ 2Hgo
Hg2
CI2
↓
Br2
+ 2Hgo
Hg2
Br2
↓
3- Mixture of chloride and iodide :
Add AgNO3 to the mixture, AgCl and AgI are precipitated. Add to precipitate
dil ammonia solution and filter
Filterate Cl
onfirmed by chromyl chloride test
Precipitate
Yellow ppt. I-

47. Cyanogen anions
This group of anions, are;
1- Cyanide (CN-
)
2- Thiocyanate (SCN-
)
3- Ferrocyanide [Fe(CN)6]4-
4- Ferricyanide [Fe(CN)6]3-
All cyanide containing anions are highly poisonous. In all experiments in
which the gas is likely to be evolved or those in which cyanides are
heated, should be carried out cautiously in the fume cupboard.
I. General characters
1-Parent Acids:
a) Hydrocyanic acid: HCN
It's very poisonous. It's colorless volatile liquid (B.P. 26.5o
C). It has an
odor of bitter almonds. It is not stable in solution due the formation
of ammonium formate. Any dil. mineral acid can replace HCN in its
solution.

48. On passing CO2 to CN-
solution HCN is produced with HCO3
-
.
CN-
+ CO2
+ H2
O HCN + HCO3
-
b) Thiocyanic acid: HSCN
It is colorless toxic liquid (B.P. 85o
C) with unpleasant odor.
It is as strong as HCI but unstable. It is soluble in ether after the
addition
of HCI to an aqueous solution of SCN-
.
On standing its aqueous solution is decomposed to HCN and yellow
solid polymer.
3 HCNS HCN + H2
N2
C2
S3
c) Ferrocyanic acid: H4 [FeCN)6]
It's white crystalline solid. Its aqueous solution is strongly acidic.
The first two protons are nearly completely ionized.
d) Ferricyanic acid: H3 [Fe(CN)6]
It's browinish crystalline solid, soluble in water to give strongly acids
solution. The three protons are nearly completely ionized.

49. 2-Solubility:
CN-
: All cyanides are water insoluble except alkali metals (Na+
, K+
),
ammonium
salt, alkaline earth metals ( Ba2+
, Sr2+
and Ca2+
) and mercuric cyanide.
SCN-
: All thiocyanates are water soluble except AgSCN, Hg2(SCN)2 &
Cu2 (SCN)2. Pb (SCN)2 as PbCI2 is sparingly soluble in cold water,
but soluble in hot water.
Ferro and Ferricyanides:
All are insoluble in water except those of alkali metals, ammonium salt and
alkaline earth metals.
3-Complexing agent:
Cyanide ion has strong tendency to the formation of complexes which
may be double cyanides or complex cyanides.
1- Argentocyanide complexes: Double cyanides
When a ppt. is formed upon reacting CN-
with Ag+
, at first white turbidity
is formed which is AgCN. According to the medium, if CN-
ions are present
in excess a soluble complex is formed.
AgCN + CN-
(Ag (CN)2
)-

50. 2- Complex cyanides:
Stable metallo-cyanogen complexes can be formed by reacting FeSO4
with CN-
in alkaline medium to give stable ferrocyanide complex.
Similar complex is formed with Fe3+
to give ferricyanide.
Therefore [Fe(CN)6
]4-
and [Fe(CN)6
]3-
are considered to be stable complexes
from CN-
ions. Also Co++
can form stable complexes with CN-
.
Fe2+
+ 6 CN-
[Fe(CN)6
]4-
Fe3+
+ 6CN-
[Fe(CN)6
]3-
When cyanides are heated with polysulphides (NH4
)2
Sx
or thiosulphate (S-2
O3
--
)
they give thiocyanate ion
CN-
+ (NH4
)2
Sx
(NH4
)2
Sx-1
+ SCN-
CN-
+ S2
O3
2-
SO3
--
+ SCN-
4-Oxidizing agent:
Ferricyanides has oxidizing effect, they can oxidizes I-
into I2
5-Reducing agent:
Ferrocyanides has mild reducing effect, they can be oxidized to ferricyanide
by oxidizing agents, such as MnO4
-
, NO3
-
, H2O2 and Cl2

51. II. General Reactions
1- Dry Reactions
a- Action of dilute HCla) CN-
:
HCN gas evolved with characteristic bitter almond odor and can be
tested
by:
1- Converting HCN evolved into SCN-
, by exposing the evolved HCN gas
to a paper moistened with ammonium polysulphide.The resulted SCN-
can
be tested by adding dil. HCI and a drop of FeCI3 solution, a blood red color
is produced.2- By passing the evolved gas into AgNO3
solution, a white ppt. of
AgCN is
formed insoluble in dil. HNO3
, soluble in ammonia solution.HCN + AgNO3
AgCN +
HNO3
AgCN + 2NH3
(Ag(NH3
)2
)CN
3- Prussian blue test: The evolved HCN gas is passed into NaOH solution,
add drops of FeSO4 solution, heat to boiling, the HCN is converted into
ferrocyanide which can be tested by adding drops of FeCl3 solution to produce
a prussian blue ppt.

52. b) SCN-
: No reaction as SCN-
is as strong as HCl
c) Ferrocyanide and Ferricyanide:
With cold dil. HCI, no gases, but may be precipitation of hydro
ferrocyanic
and hydroferricyanic acid occur.(Fe(CN)6
)4-
+ 4H+
H4
(Fe(CN)6
)
(Fe(CN)6
)3-
+ 3H+
H3
(Fe(CN)6
)
b- Action of conc. H2SO4:
a) CN-
; All cyanides are decomposed on heating.
CN+ -
2H+
+ H2O NH4
+
+CO
b) CNS-
: Decomposition with evolution of carbonyl sulphide, which burns
with a blue flame.
SCN-
+ 4H+
+ 2SO4
--
+ H2
O
NH4
+
+ 2HSO4
-
+COS
Carbonyl Sulphide

53. On heating with conc. H2SO4, CO will be evolve which burns with a
blue
flame. SO2 is produced in case of ferrocyanide.
c) Ferrocyanide and Ferricyanide:
2Fe2+
+ 4H+
+ SO4
--
SO2+ 2H2O + 2Fe3+
)Fe(CN)6
)4-
+ 6H2
O +22H+
+ 10 SO4
2-
Fe2+
+6NH4
+
+ 10 HSO4
-
+ 6
CO ↑
(Fe(CN)6
)3-
+ 6H2
O + 22H+
+ 10 SO4
2-
Fe3+
+ 6NH4
+
+ 10 HSO4
-
+ 6CO ↑
2-Wet Reactions
a- Silver nitrate solution:
1- CN-
& SCN-
: form white ppts. of silver cyanide and silver thiocyanate.
AgCN is soluble in excess CN-
, ammonia solution, but insoluble in dil. HNO3
Ag+
+ SCN-
↓ AgSCN
Ag+
+ CN-
↓ AgCN CN-
(Ag(CN)2
)- H+
HCN+ AgCN

54. 2- Ferro- and Ferricyanides:
Both [Fe(CN)6]4-
and [Fe(CN)6]3-
react with AgNO3 solution with
the
formation of a white ppt. and orange red ppt., respectively
4 Ag+
+ [Fe(CN)6
]4-
↓ Ag4
[Fe(CN)6
]
Insoluble in dil. ammonia
Insoluble in dil. HNO3
3 Ag+
+ [Fe(CN)6
]3-
↓ Ag3
[Fe(CN)6
]
Orange red ppt.
Insoluble in dil. HNO3
Soluble in dil. ammonia
The solubility of silver ferricyanide ppt. can be used for the separation
of ferrocyanide and ferricyanide when present in a mixture. Oxidation of
the white ppt. of Ag4 [Fe(CN)6] by warming with few drops of conc. HNO3,
leads to orange red ppt. of Ag3 [Fe(CN)6] which becomes soluble in
dil. ammonia solution.
b) Reaction with BaCI2: No observed reaction

55. c) Reaction with FeCI3: This reaction is very important, since it is
diffrantiating reaction.
The diluted sample solution is added to a 1ml of FeCI3 reagent.
1- CN-
: iron (III) cyanide will be formed form dil. solution as a ppt. which is
dissolved in excess cyanide forming ferricyanide.
Fe3+
+ 3 CN-
Fe (CN)3 [Fe(CN)6]3-
Ferricyanide
3CN-
2- SCN-
: This reaction is specific for iron(III) and SCN-
in the absence of
other interfering ions.
A cold acidic solution of SCN-
is treated with FeCI3 reagent,
a blood red color is produced which is extractable with ether.
The formed color is subjected to have the following structures:
Fe3+
+ SCN-
[Fe(SCN)]++
or Fe(SCN)3
or [Fe(SCN)6
]3-
In order to increase the sensitivity of the test the following precautions must
be done:
1.Ensure the presence of iron in the Fe3+
state.

56. 2- Acidification of the medium (dil. HCI is preferable).
3- Cooling of the solution befor testing.
4- Removal of intreferring ions by precipitation or complexation.
F-
, PO4
3-
, oxalate and tartrate bleach the colour, therefore it must be absent
F-
for e.g, reacts with iron to form stable complex.6 F-
+ Fe3+
(FeF6
)3-
other ions which react with SCN-
e.g, Hg2+
which form unionized Hg
(SCN)2
which is colorless.
Iodides also interferes by being oxidized by Fe3+
into the brown colour
I2
. 2I-
+ 2Fe3+ H+
I2
+ 2Fe2+
3- Ferro and
Ferricyanides:
A Prussian blue characteristic ppt. is formed form acidic solution
of [Fe(CN)6
]4-
, which is insoluble in dil. HCI, but soluble in alkali hydroxide.
3[Fe(CN)6
)4-
+ 4Fe3+
Fe4
[Fe(CN)6
]3
Prussian blue
In case of Ferricyanide, a brown color is formed of the non-ionised ferricyanide
Fe3+
+ [Fe(CN)6]3-
Fe[Fe(CN)6
] Brown color
This test can be used to differentiate between ferro and ferricyanide

57. d) Reaction with FeSO4 reagent:
1- CN-
: Cyanide forms with FeSO4 solution a yellow brown ppt. at first
which is then form ferrocyanide, this reaction is enhanced by
heating or addition of alkali.
2CN-
+ Fe2+
Fe(CN)2
4CN-
[Fe(CN)6
]4-
2-SCN-
: No reaction.
3- Ferri and Ferrocyanide: Ferricyanide forms with FeSO4 reagent a
similar blue ppt. (turnbulls blue), as that of Prussian blue, but differ
in the distribution of iron-different oxidation state is varied.
[Fe(CN)6]3+
+ Fe2+
Fe3+
+ [Fe(CN)6]4-
Turanbull's blue Prussian blue
Ferrocyanide forms white ppt. of ferrous ferrocyanide.
2K+
+Fe++
+ [Fe(CN)6
]4-
K2
Fe[Fe(CN)6
]

58. e- Reaction with CuSO4:
To the sample solution, add CuSO4 reagent dropwise.
1- CN-
: In acidic medium, CN-
likes I-
, reacts with Cu++
which oxidizes
CN-
into cyanogens (CN)2 or cyanate CNO-
(in alkaline medium).
Cu++
+ 2CN-
Cu(CN)2 ↓
Greenish
yellow2CU (CN)2
Oxid-red Cu2
(CN)2
↓+ (CN)2
white cyanide
cyanogen Cu2
(CN)2
↓ + 4CN-
2 (Cu (CN)3
)2-
Excess cuprocyanide complex
SolubleAs a conclusion of this reaction, cupric ions react with excess
cyanide
to form soluble complex cuprocyanide and cyanogen.
2Cu++
+ 8CN-
2[Cu (CN)3
]2-
+ (CN)2
In alkaline medium cyanogen is converted to CN-
& cyanate CNO-
.
(CN)2
+ 2OH-
CN-
+ CNO-
+ H2
O

59. 2- SCN-
: Thiocyanate reacts with CuSO4 reagent, to form a green
color
which changes into a black ppt Cu (SCN)2 with excess
CuSO4
reagent Cu (SCN)2 decomposes gradually to white cuprous
thiocyanate Cu2(SCN)2 and separation of thioyanogen as a
gummy mass
Cu++
+ SCN-
Cu
(SCN)22 Cu (SCN)2 ↓ unstable
↓ Cu2
(SCN)2
+ (SCN)2
decomposition
white gummy
mass3- Ferro and Ferricyanides:
Both ferro and ferricyanides form brown and green ppts. of copper
ferro
and copper ferricyanides, respectively. Both ppts. are insol. in dil.
acids [Fe(CN)6
]4-
+ 2Cu++
Cu2
[Fe(CN)6
]
Brown
2 [Fe(CN)6
]3-
+ 3Cu++
Cu3
[Fe(CN)6
]2
green

60. f- Reaction with Cobalt Nitrate:
To the sample solution, add excess Co(NO3)2
reagent.
1- CN-
: A buff ppt., of cabaltous cyanide dihydrate is formed, which is
soluble
in excess CN-
to form soluble complex, cobaltocyanideCo2+
+ 2CN-
+ 2H2
O Co (CN)2. 2H2
O
[Co
(CN)6]4-
soluble
complex.
4CN-
2- SCN-
: Vogel's Reaction
The reaction of Co++
with SCN-
to produce a characteristic blue
color
extractable with ether or amyl alcohol; known as vogel's reaction.
Other cyanogen anions form precipitates with Co (NO3)2 reagent.Co2+
+ 4SCN-
[Co (SCN)4
]2-
Extractable with ether
(blue)3- Ferro and Ferricyanide:
Both form greyish green and red ppts. of cobalt ferrocyanide
and
cobalt ferricyanide.
2 Co2+
+ [Fe(CN)6
]4-
Co2
[Fe(CN)6
]
greyish
green
3 Co2+
+ 2[Fe(CN)6
]3-
Co3
[Fe(CN)6
]2

61. III. Special Tests
1- For Cyanides:
a) Prussian blue test: This test is specific for CN-
which can be converted
into ferrocyanide and allowed to react with Fe3+
.
b) Iron thiocyanate:
This test for CN-
depends on the direct combination of alkali cyanides
with sulphur (ammonium polysulphide). A blood red coloration is
produced upon addition of FeCI3 reagent. This blood red color is
extractable with ether. This test is applicable to CN-
in presence of S2-
or SO3
2-
; if SCN-
is originally present, the CN-
must be isolated first by
precipitation e.g. as zinc cyanide.
2- For thiocyanate:
a)Reduction Test: This reaction depends on the reduction of SCN-
with
metallic zinc and dil. acid into H2S and HCN which can tested for.
Zno
+ 2H+
2 (H) + Zn2+
2SCN-
+4(H) 2 ↑ HCN + ↑ H2
S+ S--
b) Vogel’s reaction

62. 3- For ferrocyanides:
As mild reducing agents:
It can be oxidized to ferricyanide by oxidising agents, such as, MnO4
-
,
NO3
-
, H2O2 and CI2.
2[Fe(CN)6
]4-
+ CI2
2[Fe(CN)6
]3-
+ 2CI-
4- For Ferricyanides:
As oxidizing agents:
For example, [Fe(CN)6]3-
can oxidizes I- into a brown colored I2
which
identified by starch or CHCI3.
IV. Analysis of Mixtures
2[Fe(CN)6
]3-
+ 2I-
2[Fe(CN)6
]4-
+I2
1-Mixture of CN-
, SCN-
, [Fe(CN)6]4-
& [Fe (CN)6]3-
CN-
must be tested at first, then removed from the mixture. This is done
depending on its strong affinity to protons, low ionization and volatility
of HCN.

63. The following procedure could be applied.
a- Passing CO2 in the mixture solution using acetic acid or NaHCO3
and heat, until no more HCN evolved which can be confirmed by:
i- Passing in AgNO3 solution acidified dil. HNO3 which gives a white ppt.
ii- Passing in NaOH, adding FeSO4 solution heating, followed by HCI
then FeCI3 solution (Prussian blue).
b- To the remaining solution, after removal of CN-
, acidify with dil.
HCI, cool and add FeCI3
solution and centrifuge
Deep blue ppt.
[Fe (CN)6]4-
Centrifugate
blood red color
extractable with
ether SCN-
brown solution
SnCI2
blue ppt .
[Fe (CN)6]3-

64. 2-Mixture of SCN-
, CI-
, Br-
and I-
SCN-
is tested for by reacting with FeCI3, to give blood red color which is
extractable with ether and removed. In presence of I-
, I2 is also formed
which
can be extracted with CHCI3 (Violet color).
The blue complex formed with Co2+
can also be used to detect and
remove
SCN-
by extraction with ether or amyl alcohol.
The halides are tested for in the usual way after the removal of SCN-
,
since it interferes with their precipitation.
After testing for SCN-
, it is removed by igniting the mixture till no more
blackening or no odor of burnt sulphur is observed.
The residue will contain only CI-
, Br-
, I-
, and test for CI-
by chromyl
chloride
test for I-
and Br-
, carry out chlorine water test.

65. Arsinic and phosphorous containing anions
This group of anions, are;
1- Arsenate (AsO4
3-
)
2- Arsenite (AsO3
3-
)
3- Phosphate (PO4
3-
)
I. General characters
1-Parent Acids:
a) Orthoarsenic acid: H3AsO4
Its aqueous solution is a moderately strong acid, slightly weaker than
phosphoric acid. It has the tendency for condensation and formation of
pyroarsenic acid, H4As2O7, and meta-arsenic acid, HASO3 by gentle heating.
2H3
AsO4
H4
As2
O7
2HAsO3
+H2O +H2O
-H2O-H2O
(Orthoarsenic acid) (Pyro arsenic acid) (Meta arsenic acid)

66. Arsenic acid and arsenate ion are mild oxidizing agents.
Three series of arsenates exist, the primary arsenate H2AsO4
-
,
the secondary arsenate (HAsO4
2-
) and the tertiary arsenate
(AsO4
3-
).
b) Arseneous acid: H3AsO3
It exist in aqueous solutions, cannot be isolated as such because
of thermal decomposition to the anhydride, As2O3, sometimes written
as As4O6. The oxide is slightly soluble in water yielding ortho arsenious acid
and meta arsenious acid.
As4
O6
+ 6H2
O 4H3
AsO3
4HAsO2
+ 4H2
O
(ortho arsenious acid) (meta arsenious acid)
Two series of salts of arsenites exist, orthoarsenites H2AsO3
-
,
meta arsenites AsO2
-
, both respond similarly to different reactions.
**[Arsin-containing acids and salts are highly poisonous]**

67. Reduction of As5+
and As3+
:
Pentavalent arsenic salts, or anions containing, can be reduced first to
the
trivalent arsenous, or the corresponding anion containing it, and finally
to the metalic form.
As5+
+ 2e As3+
+ 3e Aso
↓
The reduction can be made using reducing agents with lower redox-potential
e.g. saturated solution of stannous chloride, a powerful reducing agent in the
presence of conc. HCI.
As5+
+ Sn2+
Sn4+
+ As3+
2AS3+
+ 3Sn2+
3Sn4+
+ 2Aso
(H+
)
(OH-
)
c) Orthophosphoric acid: H3PO4
It is crystalline solid, its aqueous solution is acidic & ionises into:
H3PO4 H+
+ H2PO4
-
[dihydrogen phosphate]
H2PO4
-
H+
+ HPO4
2-
[monohydrogen phosphate]
HPO4
2-
H+
+ PO4
3-
[tribasic phosphate]

68. The intermolecular loss of water from two molecules of orthophosphoric
acid, will give pyrophosphoric acid (H4P2O7) and metaphosphoric acids
(HPO3).
Orthophosphoric acid forms three series of salts in which one, two or three
hydrogens are replaced by metals, for example, NaH2PO4, Na2HPO4
and Na3PO4. these salts are known respectively as primary, secondary and
tertiary orthophosphates.The aqueous solution of the primary salt is acid,
that of the secondary is slightly alkaline while in the case of the tertiary salt,
the solution is strongly alkaline.
2-Solubility:
All their salts are insoluble in water except those of Na+
, K+
and NH4
+
beside
the alkali dihydrogen salts as Ba(H2AsO4)2
3- Redox-reaction with I2/I-
:
Aresnate has oxidizing effect and aresnite has reducing effect
Arsenate (AsO4
3-
) ions oxidises iodide into iodine; but the redox reaction is
reversible due to the narrow difference in Eo values of the two redox systems.

69. AsO4
3-
+2H+
+ 2I-
AsO3
3-
+ H2
O +I2
H+
NaHCO3
Arsenate oxidise iodide into iodine in acid medium, while arsenite
(mild reducing agent) reduces iodine into iodide in alkaline medium.
II. General Reactions
1- Dry Reactions
a- Action of dilute HCl
No visible reaction, since phosphates, arsenates and arsenite acid are
non volatile.
b- Action of conc. HCl
1-PO4
3-
: no visible reaction
2- AsO4
3-
:On hot arsenate ion oxidises HCI into free CI2, while it will be
reduced to arsenite
2CI-
+ AsO4
3-
+ 4H+
CI2
↑ +AsO2
-
+ 2H2
O

70. 3-AsO3
3-
: Arsenite will react and vapour of arsenious chloride is evolved.
AsO2
-
+ 3CI-
+ 4H+
AsCI3
↑ + 2H2
O
c- Action of conc. H2SO4
1-PO4
3-
and AsO4
3-
: no visible reaction
2-AsO3
3-
: Arsenite on heating, some reduction to SO2 may occur.
2-Wet Reactions
a- Silver nitrate solution:
3Ag+
+ PO4
3-
Ag3PO4
↓ (yellow ppt)
3Ag+
+ AsO4
3-
Ag3
AsO4
↓ (chocolate ppt.)
3Ag+
+ AsO3
3-
Ag3
AsO3
↓ (yellow ppt.)
All the precipitates are soluble in dil. HNO3 due to the fact that the
corresponding acids (phosphoric, arsenic and aresnious acids) are weaker
than nitric acid in the presence of which they yield lower concentration of
their ions insufficient to precipitate their silver salts

71. All the precipitates are soluble in ammonia solution, due to the
formation of the complex ion [Ag (NH3)2]+
, which yields lower
concentration of silver ions insufficient to precipitate their silver salts.
3Ag+
+ 6NH3
3[Ag(NH3
)2
]+
These precipitates are insoluble in acetic acid.
b) Reaction with BaCI2:
White precipitates of the secondary salt (BaHPO4, BaHAsO4, BaHAsO3)
from neutral medium, or of the more insoluble tertiary salt (Ba3(PO4)2,
Ba3(ASO4)2 or Ba3(AsO3)2) from ammoniacal or dilute alkaline solutions.
The precipitates are soluble in dilute acids including acetic acid.
c) Reaction with Magensia Mixture:
Magnesia mixture reagent is formed of MgCI2, NH4CI and NH4OH
[Mg2+
, the precipitating ions, NH4OH, to render the medium ammoniacal;
NH4CI, to reduce OH-
concentration by common ion effect to be
insufficient to ppt. Mg (OH)2]. The reagent solution form white crystalline
precipitate with phosphates and arsenates in neutral or ammoniacal solution
The precipitate is soluble in acetic acid and in mineral acids.
No precipitate is formed with arsenites.

72. PO4
3-
+Mg2+
+ NH4
+
Mg (NH4
) PO4
[magnesium ammonium phosphate]
AsO4
3-
+ Mg2+
+ NH4
+
Mg(NH4
)AsO4
[magnesium ammonium
arsenate]
If the white precipitates are treated with AgNO3 (in acetic acid medium),
that of the phosphate will be transformed into yellow ppt. while that of
the arsenate into chocolate ppt. due to the transformation to the less
soluble Ag3PO4 and Ag3AsO4 respectively.
d) Reaction with ammonium molybdate:
The addition of a large excess (2-3ml) of this reagent in conc. HNO3
to a small volume (0.5ml) of the test solution acidified with HNO3 and
heat gradually, produces a canary yellow crystalline precipitates of
ammonium phosphomolybdate (NH4)3PO4. 12MoO3 (on warming to 40o
C)
and of ammonium arsnomolybdate (NH4)3 AsO4. 12MoO3 (on boiling)
in case of phosphates and arsenates respectively.
No precipitate is formed with arsenites.
The precipitates are soluble in ammonia or alkali hydroxides,
in excess phosphates or arsenates respectively and on boiling with
ammonium acetate solution, insoluble in HNO3.
MoO produced from the action of acid on ammonium molybdate.

73. (MoO4
2-
)+ 2H+
H2
MoO4
3 NH4
+
+ 12 MoO3
+ PO4
3-
3NH4
+
+ 12 MoO3
+ AsO4
3-
(NH4
)3
ASO4
.12MoO3
MoO3+ H2O
(NH4)3PO4.12MoO3
Chloride and reducing agents, such as S2-
, SO3
2-
,[Fe(CN)6]4-
and tartarates,
seriously affect the reaction, and should be destroyed before carrying out
the test.
e) Reaction with H2S:
Acidify the test solution with dilute HCI and pass H2S.
No precipitate is formed in case of phosphate.
Aresnites, produce immediate yellow ppt. of arsenious sulphide As2S3.
The ppt. is soluble in HNO3 and alkali hydroxides insoluble in hot conc.
HCI.
2HAsO2
+ 3H2
S As2
S3
+ 4H2
O

74. Arsenates, not produce any immediate visible change, but after prolonged
passage of H2S, yellow ppt. of AS2S3 is produced. It is evident that the first
action of H2S is to reduce the arsenate into arsenite through the formation
of thioarsenate ion H2AsO3S-
which decomposes slowly arsenious acid
and suphhur.
H2
AsO4
-
+ H2
S H2
AsO3
S-
+ H2
O
H2
AsO3
S-
+ H+
HAsO2
+ H2
O +S ↓
2HAsO2
+ 3H2
S As2
S3
+ 4H2
O
If the acid concentration is high and the strean of H2S is rapid,
no preliminary reduction to arsenite occurs and arsenic pentasulphide
precipitate (As2S5) is produced.
2H2
AsO4
-
+ 5H2
S +2H+
As2
S5
↓ +8H2
O
However, if the solution is heated under the same conditions,
mixture of As2S3 and As2S5 is formed.

75. f) Reaction with CuSO4 solution:
Phosphates and arsenates form bluish-green ppt. of the cupric
phosphate
or arsenate, CuHPO4, or CuHAO4, respectively. On adding an excess of
NaOH, the ppt. assumes a pale blue color but dose not dissolve,
and on boiling no red ppt. is produced.
The ppt. is soluble in mineral acids and in ammonia.
Aresnites from yellowish green ppt. of copper arsenite CuHAsO3 from
the
sample solution just alkaline with NaOH. The ppt. is soluble in excess
NaOH to give deep blue color of CuO.HAsO2. On boiling red ppt. is
formed
due to the reduction of CuO into cuprous oxide (Cu2O), the arsenious
acid
is simultaneously partially-oxidised to arsenic acid.
Cu2+
+ AsO2
-
+ OH-
CuHAsO3
=[CuO.HAsO2
]
2[CuO.HAsO2
]+H2
O Cu2
O ↓+ H3
AsO4
+HAsO2
g) Uranyl acetate solution:
Light yellow, gelatinous precipitate of uranyl ammonium phosphate
Uo2(NH4) PO4 or arsenate UO2 (NH4) AsO4 in case of phosphates and
arsenates repectively, in the presence of excess ammonium acetate.
The precipitate is soluble in mineral acids, but insoluble in acetic acid.

76. This test provides an excellent method of distinction of phosphate and
arsenate from arsenite, which does not give a precipitate with the reagent.
PO4
3-
+ UO2
2+
+ NH+
4
UO2
(NH4
)PO4
AsO4
3-
+ UO2
2+
+ NH4
+
UO2
(NH4
) AsO4
III. Special Tests
1- For phosphate:
Magnesium test:
It depends on reduction of the stable phosphates into phosphide (P3-
),
by mixing with magnesium powder and heat in an ignition tube. Moisten the
cold mass with water, phosphine gas (PH3) is produced which has
unpleasant odor and is inflammable.
PO4
3+
+ 4Mg (heat)
4MgO +
P3-
P3-
+ 3H2
O PH3
↑ + 3OH-

77. 2- For arsenate:
Potassium iodide test: To the test solution (2ml) add 1 ml of chloroform,
3ml KI solution and 5ml conc. HCI. Shake
vigorously
and allow to settle, a violet color of free iodine
appears in the organic layer.
AsO4
3-
+ 2I-
+ 4H+ ASO2
-
+ I2
+ 2H2
O
HCO3
-
H+
The test can be used for the detection of arsenate in presence of
phosphate and arsenite (in absence of other oxidizing agents).
3- For arsenite:
a) Iodine test:
Add 0.5 ml of saturated NaHCO3 solution to 3 ml of the sample
solution.
Add few drops of I2 solution. The brown color of I2 disappears
immediately
due to the reducing effect of arsenite. This reaction is the reverse of
that
for arsenate. In absence of other reducing agents this test can be used
to
distinguish arsenite from arsenate or phosphate.

78. b) Bettendorf's test:
A few drops of the test solution are added to 4ml of conc. HCI, and 1
ml
of saturated stannous chloride solution is added. The solution is gently
warmed; it becomes drak brown and finally black ppt. of arsenic is
formed.
Strong reducing agents as SnCI2 reduce arsenite in presence of conc.
HCI
to elemental arsenic.3 Sn2+
+ 8H+
+ 2AsO2
- (heat)
2As ↓ +3Sn4+
+ 4H2
O
This test is also positive with arsenates, being first reduced into arsenites.
However, the test can be made use of to establish the presence of
arsenic-containing anions.c) Marsh's reaction: [ for small amounts of arsenic.]
In acidic solution arsenic (III) and (V) compounds are reduced by
hydrogen to the poisonous hydrogen arsenide gas (H3As) with garlic
like
odor which when heated dissociates to elementary arsenic and
hydrogen:
AsO3
3-
+ 3Zno
+ 9H+
H3
As ↑ + 3Zn2+
+ 3H2
O
(heat) 2H3
As ↑ 2Aso
+ 3H2
↑

79. IV. Analysis of Mixtures
1-Mixture of arsenite and arsenate:
Ammoniacal solution of the mixture + magnesia mixture &
filter
White PPt.
Mg(NH4)AsO4
Wash with dil Ammonia
Solution+ AgNO3 acidified
With acetic acid
↓
Chocolate brown
ppt. of Ag3AsO4
∴Aresnate
Filtrate
1-Acidify with dil. HCI & Pass H2S →
immediate yellow ppt. of As2S3 ∴Arsenite
(or) 2- Add 5-7ml of 30%H2O2 soI.+ magnesia
mixture drop by drop (10ml) with
stirring → a white crystalline ppt.
of Mg(NH4) AsO4 ↓ produced by
Oxidation of arsenite.
(or) 3- Addition of NaHCO3 sat. sol.+few
drops of I2 sol. → The brown colour of I2
disappears ∴ arsenite

80. 2- Mixture of arsenite and phosphate:
1- With magnesia mixture ( as the mixture of AsO3
3-
and AsO4
3-
) with the
only exception that when the ppt. of Mg (NH4) PO4 treated with AgNO3
acidified with acetic acid, yellow ppt. of Ag3 PO4 is produced.
OR
2- Pass H2S in the solution of the mixture acidified with dil. HCI, immediate
yellow ppt. of As2S3 indicates AsO3
3-
filter. Drive off the excess H2S by
boiling and test for phosphate by the general test (amm. molybdate).
3- Mixture of arsenate and phosphate:
Dissolve in conc. HCI (10 ml), boil, pass H2
S for 5 minutes.
Dilute with 25 ml H2
O & filter.
Yellow ppt.
of As2S5
∴ Arsenate
Filtrate, evaporate to dryness, dissolve
in conc. HNO3
add ammonium molybdate
& warm → canary yellow ppt.
∴ Phosphate.

81. 4- Mixture of arsenite, arsenate and phosphate:
Ammoniacal solution + magnesia mixture & filter
White ppt of
Mg (NH4) PO4 ↓
Mg (NH4) AsO4 ↓
Wash with dil ammonia
Solution. Dissolve in conc. HCI.
Boil & pass H2S; proceed exactly
As mixture of PO4
3-
and AsO4
3-
Filtrate
test for AsO3
3-
as in mixture (1)

82. Nitrogen- containing anions
This group of anions, are;
1- Nitrate (NO3
-
)
2- Nitrite (NO2
-
)
I. General characters
1-Parent Acids:
a) Nitric acid: HNO3
Colorless liquid (B.P. 83O
C), decomposes on aging to nitrogen dioxide
(NO2
). Its solution in water are strongly acidic.
4HNO3
4NO2
↑ + O2
↑ +2H2
O
b) Nitrous acid: HNO2
The pure acid has never been isolated, due to its thermal instability.
2HNO2
NO ↑ + NO2
↑ + H2
O
However addition of a strong acid to a solid nitrite or its solution in the cold
yields a transient pale-blue liquid (due to the presence of free HNO2 acid or
its anhydride, N2O3) and the evolution of brown fumes of NO2.

83. 2-Solubility:
All nitrates are soluble in water. Also all nitrites are soluble in water
except AgNO2 which is slightly soluble.
3- Redox-reaction :
The nitrate ion contains in its highest oxidation state of + 5, thus reacts
only as oxidizing agent, while nitrite ion contains nitrogen which has
oxidation number + 3, it can therefore act either as a reducing or
as oxidizing agent.
II. General Reactions
1- Dry Reactions
a- Action of dilute HCl
No reaction case of nitrates, with nitrites, brown fumes of nitrogen
dioxide NO2 evolve and a transient pale blue liquid.
2NO2
-
+ 2H+
2HNO2
NO ↑ + NO2
↑ +H2
O
2NO ↑ + O2
↑ 2NO2
↑

84. H+
ions from dil. acids (including acetic acid) displace nitrous acid from its
salts. The acid spontaneously decomposes to colorless monoxide NO &
brownish NO2 gases. The brown fumes intensify when getting in contact
the atmosphere due to combination of NO with O2 of air.
b- Action of conc. H2SO4
Nitrate: Nitric acid is formed and some of it decomposed with evolution
of brown fumes of NO2 with characteristic odor.
NO3
-
+ H+
HNO3
4HNO3
4NO2
↑ + O2
↑ + 2H2
O
When copper turnings are added, and the mixture heated to boiling, the
brown fumes of NO2 are increased due to the reduction of HNO3 by Cuo
metal
which is oxidized to Cu2+
ions, which imparts a blue color to the solution.
2NO3
-
+ 4H+
+ Cuo
2NO2
+ Cu2+
+ 2H2
O
Nitrite: The reaction is the same as with dil HCI, but it takes place with
considerable violence. On adding Cuo
metal, the same occurs as
with nitrates.

85. 2-Wet Reactions
a) Reaction with Ag2SO4 solution:-
Nitrate: No ppt.
Nitrite: White crystalline ppt. of AgNO2 form concentrated solutions.
NO2
-
+ Ag+
AgNO2
b) Reaction with BaCI2 solution:
No precipitate is formed with either NO3
-
nor NO2
-
c) Reaction with KI solution:
Acidify the test solution (3 ml) dil. H2SO4, then add Kl solution and few
drops starch solution.
Nitrate: No reaction.
Nitrite: I2 is liberated imparting blue color to the starch.
2NO2
-
+ 2I-
+ 4H+
2NO ↑ + I2
+ 2H2
O

86. d) Reaction with Fe SO4 solution. (Brown Ring Test):
Acidify the test solution (5ml) with dil. H2SO4, add (1ml) freshly
prepared
FeSO4 solution.Nitrate: No visible change in case of using only dil. H2SO4, but on adding
conc. H2SO4 cautiously down the sides of the test tube, a brown ring is
formed at the interface.
Nitrite: Brown colour in the whole solution if FeSO4 solution is not
cautiously added or a brown ring at the junction of the two liquids,
if cautiously added.
FeSO4 reduces nitrate or nitrite ions to nitrogen monoxide, NO; nitrate ion
is not reduced except in solutions containing a high H+
ion concentration,
that is conc. H2SO4. The excess Fe2+
ions then combines with the NO
produced to form the unstable brownish-black complex ion [Fe (NO)]2+
,
readily decomposed by heat.
3Fe2+
+ NO3
-
+ 4H+
3Fe3+
+ NO ↑ + 2H2O
Fe2+
+ NO2
-
+ 2H+
Fe3+
+ NO ↑+ H2O
Fe2+
+ NO ↑ [Fe (NO)]2+

87. This test differentiates NO3
-
ion from NO2
-
ion, since the latter gives
the brown ring in presence of dil. H2SO4 or even acetic acid, while NO3
-
ion dose not form the ring except in presence of conc. H2SO4.
(NO2
-
, I-
and Br-
ions will interfere)
III. Special Tests
1- For Nitrate:
Ammonia test:
If solution of NO3
-
is boiled with Zno
or Alo
metals and NaOH solution,
NH3 will be evolved which can identified by its odor or with red litmus
paper (nitrites interfere).
NO3
-
+ 4Zno
+ 7 OH-
3NH3
+ 4[ZnO2
]2-
+ 2H2
O
zincate ions
3NO3
-
+ 8Alo
+ 5OH-
+ 2H2
O 3NH3
+ 8 [AlO2
]-
In acidic solution ( CH3COOH), nitrate can be reduced with Zno
to nitrite.

88. 2- For Nitrite:
a) Permanganate test:
When a dilute potassium permanganate solution is added to an acid
solution of nitrite, its pink color is bleached. In this test, the
permanganate is reduced by the nitrite into colorless manganous
Salt and the nitrite is oxidized into nitrate.
2MnO4
-
+ 5NO2
-
+ 6H+
2Mn2+
+ 5NO3
-
+ 3H2
O
Pink colorless
b) Urea test:
When a solution of a nitrite is treated with urea and the mixture
acidified with dilute HCl, the nitrite is decomposed, and N2
and CO2
are
evolved.
CO (NH2
)2
+ 2HNO2
2N2
+ CO2
+3H2
O
c) Ammonium Chloride
test:
By boiling a solution of a nitrite with excess of the solid reagent,
N2
is evoled and the nitrite is completely destroyed.
NO2
-
+ NH+
4
N2
+ 2H2
O

89. When a dil. acetic acid solution of a nitrite is treated with a little
thiourea,
N2 is evolved and thiocyanic acid is produced. The latter may be
identified
by the red color produced with dil. HCl and FeCl3 solution.
CS (NH2
)2
+ HNO2
N2
+ H+
+ CNS-
+ 2H2
O
N.B: Thiocyanates and iodides interfere, and if present must be removed
either with Ag2SO4 (solid) or dil AgNO3 solution.
IV. Analysis of Mixtures
1-Mixture of Nitrate and Nitrite:
Nitrite can be tested for in presence of nitrate (by treatment with dil HCI,
KI, KMnO4, FeSO4 in dil. H2SO4); and by the special tests for nitrite.
Nitrate cannot be tested for in presence of nitrite, since nitrite gives all
the reactions of nitrate (conc. H2SO4, brown-ring test and ammonia test).
Therefore nitrite be removed before testing for nitrate by:-
1- Decomposition of NO2
-
through its brown complex with FeSO4 formed in
dil. H2SO4 or acetic acid by heat and shaking.
[Fe (NO)]2+ heat
NO + Fe2+

90. 2- Decomposition of NO2
-
through its reduction to nitrogen by boiling with
NH4CI or warming with urea and few drops of dilute H2SO4 or warming with
little sulphamic acid.
HO.SO2. NH2+ HNO2 N2 + H2SO4+ H2O
2- Mixture of Nitrate and Bromide or / and lodide:
Br-
and I-
can be detected in presence of NO3
-
by chlorine water test.
NO3
-
can be detected in presence of Br-
and I-
by the ammonia test.
On the other, the brown ring test for nitrates cannot be applied in the
presence of Br-
and I-
, since the liberation of free halogen with conc. H2SO4
will obscure the brown ring due to NO3
-
Therefore Br-
and I-
must be first removed by either:
1- Addition of saturated solution of silver sulphate, where AgBr and AgI
are precipitated and then filtered off, the excess Ag+
is precipitated
with Na2CO3
OR 2- Adding potassium persulphate and dil. H2SO4 and warming to about
80o
C. The halogen is removed by boiling or extraction with organic solvent.
S2O8
2-
+ 2Br-
Br2
+ 2SO4
2-
S2O8
2-
+ 2I-
I2
+ 2SO4
2-
The Halide-free solution is tested for NO3
-
by the brown ring test