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ANALISIS KUALITATIF

ANION
Kimia analitik dapat dibagi menjadi tiga bagian utama;
kualitatif, kuantitatif dan terapan

Analisis kualitatif berkaitan dengan deteksi dan identifikasi


zat tunggal atau campuran berbeda.
Bab ini berkaitan dengan analisis kualitatif anion,yang
dapat didefinisikan sebagai fragmen bermuatan
negatif garam atau senyawa. Atau lihat anion asam
radikal.
Contohnya adalah NaCl:
NaCl Na + + Cl-
Cation Anion
Basic radical Acid radical
Anion dibagi menjadi 6 kelompok

1- Carbonates and Bicarbonates group

2- Sulphur-containing anions

3- Halides

4- Cyanogen anions

5- Arsinic and phosphorous containing anions

6- Nitrogen- containing anions


Ion Karbonate and Bikarbonate group

CO32- HCO3-
I. Sifat Umum

1- Keasaman:
Asam karbonat (H2CO3) mrp asam volatil yang sangat lemah
(lebih kuat dr HCN dan asam borat)
Pemanasan larutan H2CO3, CO2 akan menguapkan.
H2CO3 CO2 + H2O
Asam karbonat mula2 akan terurai mjd bikarbonat,
kemudian terionisasi kembali mjd ion karbonat

H2 CO3 H+ + HCO3- H+ + CO32-


2-Kelarutan:
Semua karbonat kecuali karbonat dari logam alkali
(Na+ and K+) dan ammonium tidak larut dalam air.
Semua bikarbonate larut dalam air.
II. Reaksi Umum
1- Reaksi kering
A-Reaksi dengan HCl encer
Terurai membentuk buih karena terbentuknya
CO2 baik CO3 -- dan HCO3-
CO3-- + 2H+ CO2 + H2O
NaHCO3+ H+ CO2  + H2O + Na+
Merupakan tipe reaksi yg mengubah dari asam karbonat kuat
terurai secara spontan menjadi CO2 & H2O.
Uji untuk gas CO2 :

Tempatkan zat padat dalam tabung reaksi, tambahkan HCl encer


segera akan terbentuk gas, yang terbentuk dg pemanasan lewati
ke dalam air kapur atau air barit yg diletakkan dalam tabung
reaksi lain
Jika terbentuk kekeruhan menunjukkan adanya karbonat
dan bikarbonat
CO2 + Ca(OH)2  CaCO3 + H2O
CO2 + Ba (OH)2  BaCO3 + H2O

CO2 yang terbentuk akan membentuk endapan dari


karbonat yang tak larut, perlahan2 kana membentuk
bikarbonat yang larut dalam air

CaCO3 + CO2 + H2O Ca (HCO3)2


Boiling
2- Wet Reactions
In order to carry out the wet reactions, a solution of the substance
in water must be done.
Dengan adanya pemanasan Bbcarbonat akan terurai membebaskan CO2.

2HCO3- CO3-- + H2O + CO2  .


a- Reaksi dg AgNO3
Akan terbentuk endapan putih perak karbonat.
CO3 -- + 2Ag+  Ag2CO3
Endapan larut dalam asam mineral (asam ntrat) dan dlm ammonia.
Ag2CO3 + 2H+  2 Ag+ + CO2 + H2O
Ag2CO3+4NH3  2[Ag (NH3)2]+ + CO32-

Endapan akan mjd kuning atau coklat jka didihkan.


Ag2CO3  Ag2O +CO2 
boiling
b- Reaksi2 dg BaCl2, CaCl2 dan MgSO4:

Endapan putih dr BaCO3, CaCO3 and MgCO3 akan terbentuk dg


penambahan reagen2 ini ke dalam sampel

BaCl2 + NaCO3  BaCO3 + 2 NaCl


Ca++ + CO3 --  CaCO3
Mg++ + CO3 --  MgCO3
Endapan larut dalam asam mineral
Utk HCO3- ; tidak ada endapan yg terbentuk krn semua bicarbonat larut
dalam air
Ba++ +2HCO3- Ba(HCO3)2
Soluble
H2O + CO2 + BaCO3 Boiling
III. Campuran dari CO32- & HCO-3
Kedua anions mempunyai reaksi yg mirip, tp CO32- membentuk
endapan pada penambahan CaCl2, BaCl2 or MgSO4, sedang
bikarbonat larut dalam air

Separation:
Tambahkn scr brlebih CaCl2 (BaCl2 or MgSO4) kedlm campuran
CO32- /HCO3- ppt end putih. Mnujukkan CO3-- , centrifuge or filter

Contrifugate White ppt.


May be HCO3- CaCO32-
Confirmatory test: 1) Boil H+
2) Add ammonia
solution white ppt. CO2 + H2O

Ca (HCO3)2 + 2 NH3 CaCO3+ (NH4)2 CO3


Anion2 yg mengandung sulfur

Anion2 dlm grup ini adalah;


1- Sulfida (S2-)
2- Sulfhit (SO32-)
3- Thiosulphate (S2O32-)
4- Sulphates (SO42-)
5- Perasulphate (S2O82-).
I. Sifat Umum
1- Keasaman:
a- Hidrogen sulfida atau asam sulfida (H2S)
IMrp gas berbau spt telur busuk dan bersifat racun.Dalam larutn bersifat
asam lemah dan terionisasi dlm 2 langkah ;
H 2S H++ HS- (hydrosulphide ion)

HS- H++ S-- (sulphide ion)

Both HS- and S-- ions give the same reactions.


b- Asam sulfit:(H2SO3)
Asam ini hanya dikenal dlm btk larutn (spt H2CO3). Kekuatan asamnya seda
.Spt H2CO3 dlm air; keberadaannya sesuai dg persamaan reaksi berikut

heat
H2O + SO2 H2SO3 H++ HSO3- H++ SO3--
Acid sulphite

c- Asam tiosulfit: (H2S2O3)


Bentuk bebasnya tidak diketahui , dan terurai mjd, H2O, SO2 and S.
Keasamanannya lebih kuat dr pd asam sulfida dalam larutan.
Terdiri dr SO32- dlm btk larutan dan S, jk dididihkan akan menghslkn S2O32-.

d- Asam sulfat: (H2SO4):


Mrpkn larutan spt minyak dan tdk berwarna(B.P. 3300C).
Sifat Umum H2SO4
1- Sifat keasaman;
Salah satu asam kuat, ionisasi dalam lar encer tjd dlm langkah ,
H2SO4 H++ HSO4- (hydrogen sulphate)
HSO4- H++ SO4-- (sulphate)
Dg adanya logam dpt dibebaskn hidrogen dari larutan H2SO4
H2SO4+ Zno ZnSO4+ H2
Asam kuat ini bs menggantikan asam2 lemah spt: asam borat, asam
sianida dan asam2 mdh menguap lainnya atau terurai dan menghasilkan
produk tergantung dr titik didihnya

2NaCl + H2SO4 Na2SO4+ 2HCl


2-Sifat Dehidrasi;
H2SO4 pekat mempunyai kecenderungan besar utk berkombinasi dg
air mbtk hitrat yg stabil H2SO4.x H2O. Jd digunakan sbg a dehydrating
agent untuk bahan2 tertentu dan byk digunakan sbg dissectors
Oleh sebab itu digunakan utk memutihkan senya.org tertentu seperti gula
yg kejernihannya akan berkurang jk mengandung air dlm seny ini
3- Sifat Oksidasi:
Merupakan agen pengoksidasi yg cukup kuat bila dipanaskan dg
beberapa pereduksi agent
H2SO4 heat H2O + SO2 + [O]

Ia akan terduksi mjd SO2, sementara agen pereduksi mereduksi


So or H2S.
2-Kelarutan:
Semua garam Na+, K+ and NH4+ dg anion sulfat larut dalam air
Sulphides : Kecuali Ca++, Ba++, & Sr2 semua garam sulfida larut dalam
air
Sulphites: semua sulfit tidak larut dalam air

Thiosulphates: kebanyakan S2O32-larut, Ag+, Pb++, garam Hg2+ & Ba++


tidaka larut

Sulphates: semua sulfat larut kecuali garam Pb++, Ba++ dan Sr++.
Ca++ & Mg++ sedikit larut.
3-Agen pengkomplekson:
Tiosulfat membentuk kompleks dg Fe3+

Fe3++ 2S2O3-- (Fe(S2O3)2)- warna ungu

4. Agen pereduksi:
Sulfida, sulfit and thiosulfat adalah agen pereduksi .

Bisa mereduksi I2, KMnO4 and K2Cr2O7 dg bebagai variasi btk dlm larutan
asam
H+
I2+S2- 2I-+So
lodine (brown) Colourless

2KMnO4+ 5S2-+ 16H+ 2Mn+++ 5SO4--+ 8H2O +2K+


I2+SO32-+H2O SO42-+2I-+2H+

2 MnO4-+ 5 SO3--+ 6H+ 2Mn+++ 5SO4--+ 3H2O

Cr2O7--+ 3SO32-+ 8H+ 2Cr3++ 3SO4--+4H2O

I2+2S2O3-- H+ S4O62-+2I-
Tetrathionate

+
Fe3++2S2O32- H S4O62-+Fe2+

8MnO4-+ 5 S2O3--+ 14H+ 8Mn+++10SO4--+7H2O

4Cr2O72-+ 3S2O32-+ 26H+ 8 Cr3++6SO4--+ 13 H2O


II. Reaksi Umum
1- Reacksi-reaksi kering
a- Action of dilute HCl
1.Sulfida; S2-
Gas H2S ; akan menguap dg penambahan HCl encer kedlm sampel padt.
gas ini ditandai dg sifatnya yg berbau spt telur busuk dan dpt diidentifikasikan
identified by 1- blackening of filter paper moistened with lead acetate sol.
S-- + 2H+ H 2S

H2S+Pb++ PbS black


2- alternatively, a filter paper moistened with cadmium acetate solution,
turns yellow
H2S + Cd++ CdS
Yellow

H2S has reducing character, It reacts with l2 solution, acid KMnO4,


acid K2Cr2O7
Imenghilangkan coklat lar. I2, mengubah warna pink dr KMnO4 mjd
Tdk berwarna dan mengubah warna orange K2Cr2O7 mjd hijau

H2S + l2 2l- + 2H+ +So


5H2S + 6H+ +2 MnO4- 2Mn++ + 8H2O + 5So

3H2S + 8H+ + Cr2O7-- 2Cr3+ + 7H2O + 3So

2- Sulfit: SO32-
SO3-- dg . HCl encer, akan melepaskan gas SO2 , due to the
decomposition of the liberated unstable H2SO3
SO--3 + 2H+ H2SO3 SO2 +H2O
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 + H2O
CaSO3 + SO2 + H2O 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-
2 MnO4- + 5 SO2 + 6H+ 2Mn++ + 5SO3 + 3H2O
Cr2O72- +3 SO2 + 8H+ 2Cr3++ 3SO3 + 4H2O

3- Thiosulphate; S2O32-
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+ H2S2O3 H2O + SO2 + So
Thiosulphate has the same action of sulphite with HCl in addition to
formation of yellow colloidal precipitate.
4- Sulphate: SO42-
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- SO32- : White ppt. of BaSO3 is formed which is soluble in dil. HCl.


Ba+++ SO32- BaSO3
3- S2O3-- : 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
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-- Ag2S


black
2- SO32-: 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.

2 Ag++ SO32- Ag2SO3 White

2 Ag2SO3 boil 2 Ago + Ag2SO4 + SO2


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- S2O3-- : Forms white ppt. of silver thiosulphate which changes its color
on standing to yellow, brown and finally black, due to the
formation of Ag2S.

Ag2S2O3 is soluble in excess S2O3-- to give a complex ion.

2 Ag+ + S2O3-- Ag2 S2O3


Ag2S2O3+ H2O Ag2S + H2SO4
Ag2S2O3+ 3S2O3-- 2(Ag(S2O3)2)3-
4- SO42- : 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-- Fe2S3 black

2- SO3--: A drak red color of ferric sulphite is produced on cold.


2Fe3++ SO3-- Fe2(SO3)3
3- S2O32-: A purple color of complex ferric thiosulphate is produced
which disappears on boiling as tetrathionate and Fe2+ are formed
from the oxidation of S2O32- with Fe3+, even on cold
Fe3++ 2S2O32- (Fe(S2O3)2)-
2 S2O3--+ 2Fe3+ 2Fe+++ S4O6--
4-SO42- : do not react with FeCl3.
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- SO32-: 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- S2O3--: A white ppt. of lead thiosulphate is formed which is soluble


in cold HNO3, on boiling a black ppt. of PbS is formed.

Pb+++S2O3-- PbS2O3
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+)
Pb+++ SO42- PbSO4
PbSO4+ 4 CH3 COO- (Pb (CH3COO)4)2-+ SO42-
PbSO4+ 3OH- HPbO2-+ H2O +SO42-

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 + CO32-

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.
2- Sulphite: SO32-
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 SO32-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; S2O32-
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.
S2O3--+ CN- OH- SCN-+ SO3--
boil

Fe3++ SCN- Cool Fe(SCN)2+


4- Sulphate: SO42-
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+ Na2CO3 Fusion Na2SO4+ MCO3


Na2SO4+ C Na2S + 4 CO

Transfer the fusion product to a silver coin and moisten with a little
water, a brownish black stain of Ag2S results.

S--+ 2H2O 2 OH-+ H2S

H2S + 2 Ag Ag2S +H2


IV. Analysis of Mixtures
1- Mixture of S2-, SO32-, S2O32- and SO42- :
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 S2O32-as soluble centifugate.
The precipitated BaSO4 and BaSO3 can be separated by the solubility
of BaSO3 in excess dil. HCI.
S2-, SO32-, S2O32- , & SO42-
Solution + CdCO3

Yellow ppt.
Centrifugate
S2-
+ BaCI2

White ppt. Centrifugate


BaSO3+BaSO4 S2O32-
HCl
Heat HCl
White PPt Centrifugate SO32- SO2 + So
SO42- confirm by reducing character
2- Mixture of CO32- and SO32- or S2O32-
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 SO32- or S2O32- ions must be firstly oxidized into SO42- 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
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 electronegativity
As 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.
I. General characters
1- Parent Acids:
a- Hydrofluoric acid; HF :
It's coloress fuming highly corrosive and itching liquid (B.P. 19.4oC).
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.
2-Solubility:
All the salts of CI-, Br- and I- are soluble except Ag+, Hg22+, & 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.
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 + SO42- 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-+ H2SO4 2H F  + SO4-- 4HF + SiO2 SiF4+ 2H2O
glass
3 SiF4+ 3H2O H2 SiO3+ 2 H2 SiF6
silicic acid hydrofluoro silicic acid
2- For chloride :
HCI gas is evolved upon treatment with conc. H2SO4 which can be
identified by :
2CI-+ H2SO4 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 + H2SO4 Br2 + SO2+ 2 H2O


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 + SO42-
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+++ 2H2O +X2

X = may be CI-, Br- and I-


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.
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 S2O3-- [Ag(S2O3)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
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 not
This 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-


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.
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- PbF2
Pb+++ 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:

Chloride and Fluoride do not react with chlorine water .


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.

Iodide react first with chlorine water before bromide as it has more
reducing character.
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) bromine monochloride
Br2+ CI2 (excess) + 2H2O 2HOBr+2HCI
hypobromous acid
Colorless
Br2+ 5CI2 (excess) + 6H2O 2 HBrO3+10HCI
bromic acid

2I- + CI2 I2+ 2CI-

I2+ 5CI2 (excess) + 6H2O 2 HIO3+10HCI


iodic acid
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.
Na2B4O7+ H2SO4+ 5H2O 4H3BO3+Na2SO4
Borax boric acid
2NaF+ H2SO4 2HF + Na2SO4

H3BO3+ 3HF BF3+ 3H2O

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:
The solid chloride is mixed with three times its weight of powdered
potassium dichromate in a tube, an equal bulk of concentrated 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-+ Cr2O7--+ 6H+ cond. 2CrO2 Cl2  + 3H2O


CrO2CI2  + 4OH- CrO4-- + 2CI- + 2H2O

2 CrO4-- + 2H+ Cr2O7--+ H2O

Cr2O7--+ 7H2O2 2 CrO83-+ 5H2O + 4H+


Blue in ether or amyl alcohol
It is possible to test for CrO4--also by lead acetate
CrO4--+ Pb++ Pb CrO4
Yellow
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-+ Cr2O7--+ 14H+ 2 Cr3++ 3Br2+ 7H2O
6 I-+ Cr2O7--+ 14H+ 2Cr3++ 3I2+ 7H2O

Br2+ 2OH- OBr-+ Br-+ H2O (hypobromide)

I2+ 2OH- OI-+ I-+ H2O (hypoiodide)


3- For iodides:
A) lodide is readily oxidized in acid solution (dil. H2SO4) with nitrite solution
or H2O2 into free l2
2I-+ 2NO2-+ 4H+ I2+ 2NO + 2H2O
2I-+ H2O2+ 2H+ I2+ 2H2O

B) I- reacts with Cu++ forming a whit ppt. of Cu2I2, the I- being oxidized to
free I2. Thus a white ppt. in brown solution is formed on treating I- with
CuSO4 solution.
2Cu+++ 4I- Cu2I2 +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 red
HgI2+ 2I- (HgI4)2-
Soluble complex
Nessler's reagent
IV. Analysis of Mixtures
1- Mixture of F-, Cl-, Br- and I- :
a) The F- is separated by treating the mixture solution acidified with
CH3COOH 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.


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 Hg2CI2 

Br2+ 2Hgo Hg2Br2 

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- Precipitate


Confirmed by chromyl chloride test Yellow ppt. I-
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. 26.5oC). 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.
On passing CO2 to CN- solution HCN is produced with HCO3-.
CN-+ CO2+ H2O HCN + HCO3-

b) Thiocyanic acid: HSCN


It is colorless toxic liquid (B.P. 85oC) 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 + H2N2C2S3

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.
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)-
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)2Sx or thiosulphate (S2O3--)
they give thiocyanate ion
CN-+ (NH4)2Sx (NH4)2Sx-1+ SCN-
CN-+ S2O32- 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
II. General Reactions
1- Dry Reactions
a- Action of dilute HCl
a) 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.
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--+ H2O NH4++ 2HSO4-+COS


Carbonyl Sulphide
c) Ferrocyanide and Ferricyanide:
On heating with conc. H2SO4, CO will be evolve which burns with a blue
flame. SO2 is produced in case of ferrocyanide.

(Fe(CN)6)4-+ 6H2O +22H++ 10 SO42- Fe2++6NH4++ 10 HSO4-+ 6 CO 

2Fe2++ 4H++ SO4-- SO2+ 2H2O + 2Fe3+


(Fe(CN)6)3-+ 6H2O + 22H++ 10 SO42- 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
H+
Ag++ CN-  AgCN CN- (Ag(CN)2 )- HCN+ AgCN
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


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.
3CN-
Fe3++ 3 CN- Fe (CN)3 [Fe(CN)6]3-
Ferricyanide
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.
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-, PO43- , 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
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- K2Fe[Fe(CN)6]


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 yellow
2CU (CN)2 Oxid-red Cu2 (CN)2 + (CN)2
white cyanide cyanogen
Cu2(CN)2  + 4CN- 2 (Cu (CN)3)2-
Excess cuprocyanide complex Soluble
As 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-+ H2O


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)2
2 Cu (SCN)2  unstable  Cu2 (SCN)2+ (SCN)2
decomposition white gummy mass

3- 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
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, cobaltocyanide
-
Co2++ 2CN-+ 2H2O Co (CN)2. 2H2O 4CN [Co (CN)6]4-
soluble complex.

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
red ppt.
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 SO32-; 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 +  H2S+ S--
b) Vogel’s reaction
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.
2[Fe(CN)6]3-+ 2I- 2[Fe(CN)6]4-+I2

IV. Analysis of Mixtures


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.
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. Centrifugate


[Fe (CN)6]4-

blood red color brown solution


extractable with
ether SCN- SnCI2

blue ppt.
[Fe (CN)6]3-
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.
Arsinic and phosphorous containing anions
This group of anions, are;
1- Arsenate (AsO43-)
2- Arsenite (AsO33-)
3- Phosphate (PO43-)
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.

-H2O -H2O
2H3AsO4 H4As2O7 2HAsO3
+H2O +H2O
(Orthoarsenic acid) (Pyro arsenic acid) (Meta arsenic acid)
Arsenic acid and arsenate ion are mild oxidizing agents.
Three series of arsenates exist, the primary arsenate H2AsO4-,
the secondary arsenate (HAsO42-) and the tertiary arsenate (AsO43-).

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.

As4O6+ 6H2O 4H3AsO3 4HAsO2+ 4H2O

(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]**


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+
(H+)
2AS3++ 3Sn2+ 3Sn4++ 2Aso
(OH-)

c) Orthophosphoric acid :H3PO4


It is crystalline solid, its aqueous solution is acidic & ionises into:
H3PO4 H++ H2PO4- [dihydrogen phosphate]
H2PO4- H++ HPO42- [monohydrogen phosphate]
HPO42- H++ PO43- [tribasic phosphate]
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 (AsO43-) ions oxidises iodide into iodine; but the redox reaction is
reversible due to the narrow difference in Eo values of the two redox systems.
H+
AsO43- +2H++ 2I- AsO33- + H2O +I2
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- PO43- : no visible reaction
2- AsO43-:On hot arsenate ion oxidises HCI into free CI2, while it will be
reduced to arsenite
2CI-+ AsO43-+ 4H+ CI2  +AsO2- + 2H2O
3- AsO33- : Arsenite will react and vapour of arsenious chloride is evolved.

AsO2-+ 3CI- + 4H+ AsCI3  + 2H2O

c- Action of conc. H2SO4


1- PO43- and AsO43-: no visible reaction
2- AsO33- : Arsenite on heating, some reduction to SO2 may occur.

2- Wet Reactions
a- Silver nitrate solution:
3Ag++ PO43- Ag3PO4  (yellow ppt)
3Ag++ AsO43- Ag3AsO4  (chocolate ppt.)
3Ag++ AsO33- Ag3AsO3  (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
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.
PO43-+Mg2++ NH4+ Mg (NH4) PO4
[magnesium ammonium phosphate]
AsO43-+ 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 40oC)
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.
MoO3 produced from the action of acid on ammonium molybdate.
(MoO42-)+ 2H+ H2MoO4 MoO3+ H2O

3 NH4++ 12 MoO3+ PO43- (NH4)3PO4.12MoO3

3NH4+ + 12 MoO3+ AsO43- (NH4)3ASO4.12MoO3


Chloride and reducing agents, such as S2-, SO32-,[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+ 3H2S As2S3 + 4H2O


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.
H2AsO4-+ H2S H2AsO3S-+ H2O
H2AsO3S-+ H+ HAsO2+ H2O +S 
2HAsO2+ 3H2S As2S3 + 4H2O
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.

2H2AsO4-+ 5H2S +2H+ As2S5  +8H2O

However, if the solution is heated under the same conditions,


mixture of As2S3 and As2S5 is formed.
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]+H2O Cu2O + H3AsO4+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.
This test provides an excellent method of distinction of phosphate and
arsenate from arsenite, which does not give a precipitate with the reagent.
PO43-+ UO22++ NH+4 UO2(NH4)PO4
AsO43-+ UO22++ 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.
PO43++ 4Mg (heat) 4MgO + P3-

P3-+ 3H2O PH3  + 3OH-


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.
H+
AsO43-+ 2I-+ 4H+ ASO2-+ I2+ 2H2O
HCO3-
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.
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++ 4H2O
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:

AsO33-+ 3Zno+ 9H+ H3As  + 3Zn2++ 3H2O


(heat)
2H3As  2Aso + 3H2 
IV. Analysis of Mixtures
1- Mixture of arsenite and arsenate :
Ammoniacal solution of the mixture + magnesia mixture &
filter

Filtrate
White PPt.
1- Acidify with dil. HCI & Pass H2S 
Mg(NH4)AsO4
immediate yellow ppt. of As2S3 Arsenite
Wash with dil Ammonia
Solution+ AgNO3 acidified
(or) 2- Add 5-7ml of 30%H2O2 soI.+ magnesia
With acetic acid
mixture drop by drop (10ml) with

stirring  a white crystalline ppt.
Chocolate brown
of Mg(NH4) AsO4  produced by
ppt. of Ag3AsO4
Oxidation of arsenite.
Aresnate
(or) 3- Addition of NaHCO3 sat. sol.+few
drops of I2 sol.  The brown colour of I2
disappears  arsenite
2- Mixture of arsenite and phosphate:
1- With magnesia mixture ( as the mixture of AsO33- and AsO43-) 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 AsO33- 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 H2S for 5 minutes.
Dilute with 25 ml H2O & filter.

Yellow ppt. Filtrate, evaporate to dryness, dissolve


of As2S5 in conc. HNO3
 Arsenate add ammonium molybdate
& warm  canary yellow ppt.
 Phosphate.
4- Mixture of arsenite, arsenate and phosphate:
Ammoniacal solution + magnesia mixture & filter

White ppt of Filtrate


Mg (NH4) PO4  test for AsO33-
Mg (NH4) AsO4  as in mixture (1)
Wash with dil ammonia
Solution. Dissolve in conc. HCI.
Boil & pass H2S; proceed exactly
As mixture of PO43- and AsO43-
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. 83OC), decomposes on aging to nitrogen dioxide
(NO2). Its solution in water are strongly acidic.
4HNO3 4NO2  + O2  +2H2O
b) Nitrous acid :HNO2
The pure acid has never been isolated, due to its thermal instability.
2HNO2 NO  + NO2  + H2O
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.
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  +H2O
2NO  + O2  2NO2 
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  + 2H2O
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++ 2H2O
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.
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+ 2H2O
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+


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-+ 2H2O
zincate ions

3NO3-+ 8Alo+ 5OH-+ 2H2O 3NH3 + 8 [AlO2]-

In acidic solution ( CH3COOH), nitrate can be reduced with Zno to nitrite.


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-+ 3H2O
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 +3H2O
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 + 2H2O


d) Thiourea test:
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-+ 2H2O


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+
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
80oC. The halogen is removed by boiling or extraction with organic solvent.
S2O82-+ 2Br- Br2+ 2SO42- S2O82-+ 2I- I2 + 2SO42-
The Halide-free solution is tested for NO3- by the brown ring test