INORGANIC CHEMISTRY

TARGET JEE 2018

XIII

IMPORTANT NOTES ON
QUALITATIVE SALT ANALYSIS

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Dry Test :

Dry tests are preliminary test which are used for detection of s-block cations and coloured d-block paramagnetic cations, these tests are of following
types.
(i) Flame test (Usually applied for detection of s-block cations)
(ii) Borax Bead Test 
 Applied for coloured d-block paramagnetic cations)
(iii) Phosphate Bead Test 
(iv) Cobalt Nitrate Test (Applied for few specific cations)

(1) Flame Test :

It is performed with the help of platinum coated wire which is first dipped in conc. HCl and brought in contact with given solid mixture. In this way,
given salts are converted into more volatile chloride salt which impart characteristic colour to flame except Be2+ and Mg2+ cation(do not impart colour
due to high ionization energy )

Cations Colour of Flame

+
Li Carmine Red
+
Na Golden Yellow
+
K Lilac. (Pale violet)
+
Rb Raddish violet
+
Cs Blue
2+
Ca Brick Red
2+
Sr Crimson Red
2+
Ba Apple Green
2+
Cu Greenish blue
2+ 3+
Pb , Bi Blue

Page No.2
(2) Borax Bead Test :

Formation of Bead : When Borax is heated on platinum coated wire loop, then it first swells up due to loss of water of crystallisation and covers
entire portion of loop, which on further heating gives transparent crystalline Bead of sodium meta borate and Boric Anhydride (NaBO2 + B2O3).

Na 2 B 4O 7 .10H 2O  Na 2 B4O7 high temp. 2 NaBO 2  B2 O3

   10H O     
( Borax ) 2 (Swells up ) ( Transparent crystalline bead )

oxidising flame
Transparent crystalline bead
(NaBO2 + B2O3) Reducing flame
Ist step IInd step

Reaction in Oxidising Flame : (Ist Step)


Fe2(SO4)3 (Solid mixture)  3B O ( present in borax bead ) Fe 2O 3.3B 2O 3or 2Fe(BO 2 )3
Fe2O3 .3SO3 23          
( Yellow Bead of ferric meta borate
is formed in oxidising flame)
Volatile part is displaced
by boric anhydride present
in borax bead
Reaction in Reducing Flame :(IInd Step)
2Fe(BO 2 )3 
+ C  2Fe(BO 2 ) 2 + CO  + B2O3
yellow bead of Light green bead
Ferric metaborate of ferrous meta Borate
in reducing flame

Page No.3
 Coloured d-block Bead colour Bead colour Product transformation
cations in oxidising flame in reducing flame

Cu(BO2)2  Cu
2+
Cu Blue Red

Fe(BO2)3  Fe(BO2)2
3+
Fe Yellow Green

Cr3+ Green Green Cr(BO2)3  Cr(BO2)3

No No
change change
Co(BO2)2  Co(BO2)2
2+
Co Blue Blue

Ni(BO2)2  Ni
2+
Ni Brown Grey
+3 +2
Mn(BO 2)3  Mn(BO 2)2
2+
Mn Amethyst(violet) Colourless

Note : All above colour of bead are observed in their cold condition (without touching flame.)

(3) Phosphate Bead Test :


Na(NH 4 ) HPO 4 .4 H 2O  Na ( NH 4 ) HPO 4 High
 temp.
 NaPO 3 + NH3  + H2O
microcosmi c salt 4 H 2O 1 phosphate salt Phosphate Bead
(Sodium Metaphosph ate)


eg. Co(NO3)2 (solid mixture)  NaPO (Pr esent in Bead )
CoO . N2O5  3     NaCoPO 4 (orthophosphate)
Blue Bead of orthophosphate is formed
is oxidising flame and reducing flame

Note : Colour table of phosphate Bead test is same as Borax Bead test in cold condition (without touching the flame).

Page No.4
(4) Charcoal Cavity Test :

This test is based on the fact that metallic carbonates when heated in a charcoal cavity decompose to give corresponding oxides. The oxides appear as
coloured residue in the cavity. In certain cases, the oxides formed partially undergo reduction to the metallic state producing metallic scales.
Example
(a) 
ZnSO4 + Na2CO3  ZnCO3 + Na2SO4

ZnCO3  ZnO (yellow when hot, white when cold) + CO2 

(b) 
CuSO4 + Na2CO3  CuCO2 + Na2SO4

CuCO2  CuO + CO2 

CuO + C  Cu (Reddish scales) + CO 
Cobalt Nitrate Charcoal Cavity Test :
In case the residue is white during cavity test then one or two drops of cobalt nitrate solution is added and again heated in the oxidizing flame using
blow pipe, different metal salts give different coloured mass as given in the table.


ZnSO4 + Na2CO3  ZnCO3 + Na2SO4 S.No . Metal Colour of the mass
CoO .ZnO
 1. Zinc
ZnCO3  ZnO + CO2 Rinmann ' s green

CoO .Al 2 O 3
2Co(NO3)2  2CoO + 4NO2 + O2 2. Alu min ium
Thinard blue

ZnO + CoO  ZnO. CoO (or CoZnO2) CoO .MgO
(Cobalt zincate) (Rinmann’s green)

Page No.5
 Carbonate (CO32–) / Bicarbonate (HCO3–)
2–
1. All CO 3 salts are water insoluble except alkali metal carbonate salts and (NH4 )2 CO3 .
2. All metal bicarbonate salts are water soluble. Except NaHCO 3
H2CO3 is Observation [Colourless odourless gas evolves with brisk effervescence]
K2MnO4(green)
non-oxidising KMnO 4 + MnO 2 (a)
(Dispn.rxn.) (4)
and hence KMnO /H
+
(b) Test based on Identification of liberated gas (Lab test) (a) (b)
2–
CO3 /CO2 No redox rxn. 4
n redox prop. CO2 gas
(Pink sol ) (2)
does not act K2Cr2O7/H
+

as oxidant No redox rxn. n (c)

(Orange sol )
Warm dil.HCl/H2SO4
(1)

2–
Distinction between CO3 & HCO3¯ Ca(OH) 2 Ba(OH)2
(5) CO32–(aq.)/ HCO3–(aq) (Lime water) (Baryta water)
Excess BaCl2
n
sol & filter
n
(Salt sol .) (3) CO2 CO2
Precipitation test BaCO 3
CaCO 3
(a) (b) (white turbidity)
(a) (b) (c) (white turbidity)
R.T.
excess CO2 excess CO2
BaCl2 soln Pb(OAc)2 sol. AgNO3 Soln
BaCO 3 If filtrate contains Ca(HCO3)2 Ba(HCO 3)2
–
white ppt. HCO3 ion BaCO3 PbCO3 Ag2CO3 (colourless sol )
n n
(colourless sol )
white white ppt. white ppt.
Boil Base(NH3 sol
n Boil Boil
dil.HCl dil.HNO3
few drops) CaCO3 BaCO 3
BaCl2 Pb(NO3)2 excess
BaCO 3 BaCO 3 n NH3 sol
n Boil (white turbidity) (white turbidity)
(sol ) n
(sol )
white ppt. white ppt. +
[Ag(NH3)2] Ag2O
(soluble) Brown ppt.
n
excess NH3 Sol
On standing +
1/2N2 + 3Ag explosion Ag3N [Ag(NH3)2] (aq)
I.M.R.
Silver nitride
(Fulminating silver)
2–
Note : 1. CO3 ion gives ppt. at room temp. whereas HCO 3¯ ion forms ppt. of carbonate on boiling. I.M.R. = Inter Molecular Redox
– Boil 2–
2HCO 3 CO 3 + CO2 + H2O
100°C
2. Water insoluble carbonate salts are soluble in soda water (CO 2 + H 2O) and CH 3COOH.
Page No.6
 Sulphite (SO32–)
2–
1. All SO3 salt are water insoluble except alkali metal sulphite salts and (NH4 )2 SO3

Colourless Observation [Colourless gas having suffocating odour of burning sulphur is detected by
Bleaching prop.
(i) 2– +
lime water test and Cr2O7 /H test]
material Coloured material
H2O2 (4)
H2O (ii)Rxn with Identification of gas by oxidising agents (Redox reaction)
Test based on
oxidants SO2 gas
Cl2/Br2/I2 redox prop. (2) (a) SO2 (b) SO2
HX (iii)
SO4 (aq)

3+
+ Fe (aq)
2–

Fe2+(aq) (iv) Warm (1) dil.HCl

CaOCl2 (v)
CaCl2 +
n
(Orange sol of (Pink soln of IO 3¯/H
H2 S 2–
SO3 (aq.) 2– +
S (i) Cr2O7 /H KMnO4/H
+ Colourless sol
n

Rxn. with turn green) is decolourised)

raductants (Soda Ext.) (c) Limited SO2
Tests based
Zn/dil.HCl (3) on ppt. Rn.
H 2S [H]
(ii)
(a) (b) (c) I3¯ soln (Brown)
BaCl2 soln n
AgNO3
Pb(OAc)2 sol soln
BaSO 3 PbSO3 excess of CCl4 Starch excess
Drop of SO2 gas
white ppt. white ppt. AgNO3 AgNO3
–
Deep blue
Ag2SO3 [Ag(SO3)] I¯+violet colouration I¯ (aq.)
2–
ppt. Exg.

SO3 act as layer (Colourless soln)

reaction

Oxid. Agt. NaOH Oxid. Agt.

dil. HCl (dil.HNO3)
bidentate ligand
excess Few drops
PbSO4 Cl2 water of Cl2 water
BaCl2 sol n
BaSO 4 Pb(OH)2
white ppt. more drop
white ppt. white ppt. Boil Excess
of AgNO3 HIO3 I3¯soln (Brown)
excess Cl2 water
dil. HCl Ag (Black)
excess NaOH conc. HNO3 Ag2SO3
No dissolution Sparingly
2–
BaSO4 is only water [Pb(OH)4] (aq) soluble Boil
insoluble braium salt Intra mol. redox rxn.
which is insoluble in Note : 1. As SO2 gas is more soluble in water, therefore effervescence is not observed during evolution of SO2 gas.
any dilute acid at RT
due to its low Ksp
2. Bleaching action due to oxidising property is permanent, whereas bleaching action due to reducing prop. is temporary.
3. H 2SO3/ SO2 exhibit better reducing properties and weaker oxidising property.
Page No.7
 Sulphide (S2–)
1. All S2– salts of s-block metals are water soluble and colourless whereas S2– salts of p-block & d-block are water insoluble and usually coloured due
to polarisation effect.
2. S2– salts of Al3+, Cr3+ and Mg2+ do not exist in aqueous solution because they readily hydrolysed into corresponding metal hydroxide due to their low
Ksp, hence they are prepared in dry condition. Fe3+ shows redox reaction with S2– ions. [Fe+3 + S2–  Fe+2 + S]
3. FeS  is the only black metal sulphide salt decomposed by non-oxidising acid (like dil.HCl/dil.H2SO4) whereas other remaining black sulphide are
dissolved in oxidising acid (hot and dil. HNO3) except HgS  (Insoluble in hot and dil. HNO3 but soluble in aquaregia and S2– salt solution)
FeS(black) + dil. 2HCl / dil. H2SO4(non-oxidising acid) Rxn
 . occurs in
  FeCl2 / FeSO4 + H2S 
Kipps apparatus

Cl2/Br2/I2 Observation [Colourless poisonous gas having rotten egg smell, turns Pb(CH 3COO) 2paper black (PbS)]
HX (a)

S CaCl2
CaOCl2 (b)
Test based on (5) Identification of gas by oxidising agents (Redox reaction)
White 2+
3+ reducing prop. (2) (a) H2S (b) H2S
Fe (aq)
turbidity Fe (aq) (c)

SO2 (g)
SYellow turbidity) (d) Warm (1) dil.HCl
conc.
 H2SO4
SO2 conc.H2SO4 S (e)
+
(4) [Orange solution [Pink solution IO3¯/H
H2O2 2–
H2SO4 excess (f) S (aq.) 2–
of Cr2O 7 /H
+ + n
[Colourless sol ]
of KMnO4/H
O3 turn green] is decolourised]
H2SO4 (st.O.A.) (g) (Soda Ext.) Tests based (c) Limited H 2S
(3) on ppt. Rn.

(a) (b) I3¯solution (Brown)

Specific tests CaCl 2/BaCl2 Pb(OAc)2 AgNO3
Solution solution solution
(i) (ii) (iii)
No ppt. PbS  (Black) Ag2S (Black) CCl4 Starch Excess
Acidified Na2[Fe(CN)5(NO)]

H2S gas
Alkaline Na2[Fe(CN)5(NO)]

Insol.in Ex. NaOH

Methylene Deep blue
blue test conc.HNO3 I¯+violet colouration I¯ (aq.)
Hot and Hot & dil. NH3 soln. NaCN layer
Me2N or Colourless
dil.HNO3 HNO3 Soln.
Excess. H2O2/O3 No Reaction Excess Cl2 water
NH2 Few drops
Pb(NO3)2 + S  + NO PbSO4  AgNO3 + S  + NO Na[Ag(CN)2] Cl2 water
White ppt. excess
HIO3 I ¯solution (Brown)
Cl2 water 3

Negative test Na4[Fe(CN)5(NOS)] Blue

Purple solution colouration

Note : 1. Mn+ (p and d-block metal cation) forms metal suphides with H2S gas depending upon acidic, neutral, basic medium of solution
2. PbS  (black) is insoluble in excess NaOH solution or excess NH4OH solution due to its low Ksp
3. Specific test with Na2[Fe(CN)5NO] (sodium nitroprusside) requires high conc. of S2– ion, hence neutral H2S and acidified H2S gives negative test, whereas alkaline H2S gives
purple colouration. Page No.8
 Thiosulphate (S2O32–)
1. All S2O32– salts of s-block are water soluble except : BaS2O3  (white ppt.)
2. S2O32– salts of Ag+, Cu+, Hg22+ , Hg2+, Pb2+, Bi3+ and Ba2+ are water insoluble.
Cl2 /Br2 water 2–
Observation [Colourless gas having suffocating odour of burning (a) Brown Cl¯ / Br¯(aq) (Colourless) + SO 4 (aq.) + S 
2– +
sulphur is detected by lime water test and Cr 2O 7 / H test
Excess Cl2
(b) NaHSO4 + HCl
2+ FeCl3 CN¯(aq.) / OH¯
[Fe(SCN)(H2O)5] solution SCN¯(aq.) (a)
SO2 gas + S 

Specific test
St.Oxd.Agt Acidified KMnO 4 2+ 2–
or Fe(SCN)3 (SO +S) (c)
2– Pink Mn (aq.) (Colourless) + SO 4 (aq.) + S 
Blood Red colouration Warm 4
(1) dil.HCl 2–
(I.M.R.) +
Excess Cr 2O 7 / H 3+ 2–
Na3[FeF6] (White ppt.) (d) Cr (aq.) (Green) + SO 4 (aq.) + S 

reducing prop.
Tests based on
NaF Orange
2+
Hg (aq.) 2– Co
2+
(aq) (4) 2– (3)
[Hg(SCN)4] Co[Hg(SCN)4] S2O3 (aq.)
(blue ppt.)
3+

Tests based on ppt. reaction

2– 3+
C2 O4 (aq.) 3– Ex.Fe (aq) (Soda Ext.) (e) Fe (aq.) (+3)
Excess 2–
[Fe(C2O 4)3] Fe2(C2O 4)3 Yellow [Fe(S2O3)2]¯ 3+
Fe2+ (aq) + S 4O 6 (aq.)
Chelating Agt
(blue ppt.) Violet complex Fe (aq.) (Pale green)
Mild Oxd.agt. (f) I2 / I3 ¯ 2–
2– Brown I¯ (aq.) + S4O 6 (Rxn occurs in iodimetric titration)
S4O6 (aq.)
2–
(2) +1 Excess S2 O3 (aq.) +1 4–
3– AgBr
(g) CuSO4 soln. Cu2S2O3 [Cu6(S2O3) 5]
(b) –S4 O62– (aq.) (Chelating agent)
[Ag(S2O 3) 2] (White ppt.) (Colourless complex)

(Soluble complex)
Hypo is used as fixing agent
in photography

(a) (b) (c) (d) (e)

CaCl2 solution BaCl2 solution Pb(OAc)2 solution AgNO3 solution Hg(NO3)2 solution [Ni(en)3 ](NO3 )2
(Complex reagent)
No ppt. BaS2O3  PbS2O3  Ag2S2O3  Hg S2O3 
(Distinction b/w (White ppt.) (White ppt.) (White ppt.) (White ppt.)
[Ni(en)3]S2O3 
2– 2–
(Thermally unstable) (Violet ppt.)
SO3 and S2 O3 ) (Thermally stable) (Thermally unstable) (Thermally unstable)

Warm or standing Excess Warm or standing Excess Warm or standing Excess

Hypo Hypo Hypo
2– 3– 2–
PbS(Black) [Pb(S2O3)2] Ag2S(Black) [Ag(S2O3)2] HgS(Black) [Hg(S2O3)2]
+ H2SO4 (Soluble complex) + H2SO4 (Soluble complex) + H2SO4 (Soluble complex)

Note : 1. Na2S2O3(Hypo. soln) mainly exhibits reducing character.

2. Hypo solution acts as Antichlore (removes excess Cl2 from bleached cotton fabric) like SO2.
Page No.9
 Acetate (CH3COO–)

1. All CH3COO– salts are water soluble except CH3COO– salt of Ag+ , Hg22+, Cu+

CH 3COOH (Vinegar smelling colourless vapours)

Warm + Neutral Warm

3Fe(OH)2 (CH3COO)  [Fe3(OH) 2 (CH3COO) 6] FeCl3 solution (a) (1) dil HCl / dil.H2SO4
Basic ferric acetate Blood red colouration
(blood red ppt.)
Specific test
CH3COO¯ (aq)
(3)

(Soda Ext.) (2)

C 2H 5OH + conc. H 2SO 4
CH3COOC 2H5 Esterification
(b) Precipitation
(Fruity smell) reaction

CaCl2 soln. BaCl2 soln. Pb(NO 3) 2 soln. AgNO 3 soln.

No ppt. No ppt. No ppt. CH 3COOAg (white ppt.)

(Soluble in dil. HNO3 and
complexing agents)

Note : Deep red colouration is obtained by reaction of Fe3+ cation with SCN– (aq) and CH3COO– (aq).

Page No.10
 Nitrite (NO2¯) and Nitrate (NO3–)
1. All NO2¯ salts are water soluble except NO2¯ salt of Ag+, Hg22+, Cu+
2. All NO3¯ salts are water soluble.

ppt. reaction +1 +1
AgNO2 (white ppt.) Deep blue [Fe(H 2O) 5(NO)]SO 4
AgNO 3 soln. NH3 gas
soln. (Brown ring complex)

3+

(Zn/Al + NaOH)
St. Oxidising agents 2+
(2) 2– NO3 ¯ (aq.) + Cr (aq.) / Mn (aq.)

[H] (st. R.A.)

p .
Acidified Cr2O7 (aq.)

pro

KI + starch
NO2(brown gas) –
/ MnO4 (aq.)

ed.
H2S FeSO 4 + conc. H 2SO 4
r
Warm on (a) S  + NO  (Brown ring specific test)
(3)
d
dil.HCl/dil.H 2SO 4
ase

(1) (Yellow turbidity)

st b

KI + Starch
Te

(b) Deep blue solution + NO

(4) (a) (b) (c)

Test based on Oxd. prop.

Test based on FeSO4 + dil.H 2SO 4 +1 +1
NO2¯ (aq) NO2¯ (aq.) Oxidising property (c) (Brown ring specific test)
[Fe(H 2O) 5(NO)]SO 4 NO2(brown gas)
(Brown ring complex)
(Soda Ext.) [H] (st.R.A.) Warm
(d) NH3 gas (2) conc.H2SO4
(Zn/Al + NaOH) (1)
dil.HCl/dil.H2SO4
(5)
R.T.
[HNO 2 H 2 O + N2 O 3 ] + NO 3¯ (aq) NO3¯ (s)
Urea / H
Pale blue (a) CO2 + N 2 + H 2O conc.
Disprop.

transient colour
Warm

(Soda Ext.) H2SO4

(b) HOSO 2NH 2 ppt. reaction
H2SO 4 + N2 + H 2O No ppt. reaction
Test with compounds Sulphamic acid because all nitrates HNO 3
containing – NH 2 gp. are water soluble
HNO3 + NO + –H2O 30°C
Colourless Thio Urea / H
(c) HSCN + 2H2 O + N 2
FeCl3 soln. N 2 O5
Air (Mouth of
Blood red colouration
test tube) + –½O2 40°C
(d) RNH 2/H
ROH + N 2 + H 2O With piece of filter paper or copper turnings
NO2 (brown gas) NO 2 (brown gas)
evolution of reddish brown gas is intensified

Note: 1. Aq. soln. of M(NO2)2 / M(NO3)2 salts (M2+ = Ba+2, Sr+2, Pb2+) do not give brown ring test because these cations form insoluble SO42– salts with H2SO4 used in ring test,
formation of ppt. will create turbulence in soln. therefore, brown ring complex is not formed. In such cases, above test can be modified by first adding Na2SO4 soln. Now
obtained filtrate can be used for ring test.
2. Ring test for NO3– ion in presence of NO2–(aq) should not be done however ring test for NO2– (aq) ion in presence of NO3– (aq) can be performed.
3. HNO2 exhibits better oxidising character and weak reducing character.
Page No.11
 Chloride (Cl–) , Bromide (Br–) and Iodide (I–)
1. All Cl– salts are water soluble except AgCl  , Hg2Cl2  , PbCl2  , CuCl  (all are white ppt.)
2. All Br– salts are water soluble except AgBr  (pale yellow) PbBr2  (white), Hg2Br2  (white), CuBr  (white)
3. All I– salts are water soluble except AgI  (yellow), PbI2(yellow), HgI2  (scarlet red), Hg2I2(green), BiI3  (black), CuI  (white)
spontaneou s (R . T .)
MClx (solid) +K2Cr2O7 (s) + CuI2  (yellow)       CuI  + 1/2 I2
conc.H2SO4 (few drop)
(IMR)
CrO2Cl2 Warm
(a)
(Reddish brown fumes)

Chromyl chloride test for Cl¯ ion Test for Br¯, I¯

NaOH
soln. (excess)

Na2CrO 4 + NaCl
(yellow soln.)
(i) CH3COOH
Cl¯(s) If we want halogen (X 2)
(ii) Pb(OAc)2 (a) HCl(white fumes with pungent odour)
then St. Oxd. Agt. like
PbCrO 4(Yellow ppt.) Br¯(s) MnO 2 is used and
Warm
(Soluble in dil. HNO3 and ex, NaOH soln.
(4) (1) (b) SO2+HBr+Br2Reddish brown fumes) if we want HX then
but insoluble in CH3COOH) conc. non-oxd. acid H 3PO 4
H2SO4 I¯(s)
SO2+HI+I2Violet vapours) + S  (Small Amt.)

CCl4 layer
(c) is used.
Violet More Brown Few drop of Specific
layer drop of Cl2 layer of I3¯ Cl2 Water fo
rI tests Cl¯(aq), Br¯(aq), I¯(aq)
of I2 ¯

Excess Cl 2
(b) (Soda Ext.)
Reddish
r¯

Cl2
rB

Brown layer (2) (3)

fo

HIO3 Water + +
of Br2
Tests based on ppt. MnO4¯/H , Cr2O7 2– / H ,
(colour less) Oxidising agent H O , CaOCl , MnO
(a) reactions (b) 2 2 2 2
PbO2, Pb2O3, Pb3 O4
Pb(OAc)2 soln. AgNO3 soln.
Cl¯ Br¯ I¯

Cl¯(aq) Br¯(aq) I¯(aq) Cl¯(aq) Br¯(aq) I¯(aq)

Cl2 Br2 I2
greenish Reddish Violet vapours
PbCl2 PbBr2 PbI2 AgCl AgBr AgI yellow gas Brown vapours
white ppt. white ppt. yellow ppt. conc. having having
excess NH3
Hot very hot Boiling NH3 suffocating Irritating
dil.NH3 soln.
water water water + soln. soln. odour odour Starch
Soluble Soluble Soluble [Ag(NH3)2]
No dissolution KI + starch
Starch iodide
paper
dil. conc.
+
Deep blue Deep blue Deep blue
No [Ag(NH3)2](aq) colouration Paper colouration
dissolution

Note : 1. AgCl  , PbCl 2  , Hg 2Cl 2  , CuCl  , HgCl 2(pred. covt.) PbCl 4(pred. covt.) SnCl 4(pred. covt.) do not give chromyl chloride test due to low concentration
of Cl– ion.
2. CH3COOH used in chromyl chloride test neutralises excess NaOH otherwise yellow ppt. of PbCrO4  is not formed.
Page No.12
 Fluoride (F–)

1. MgF2, CaF2, SrF2 and PbF2 are water insoluble fluoride

(1) Specific Test for F¯ ion.

Solid mix (F¯ salt) + conc. H 2SO 4 (few drops) salt
Glass rod dipped n
HF
into water decomp SiO2
Paste is taken on glass rod
Etching present
White deposition of H 2SiO 3 of glass in glass

SiF 4 Moisten glass rod

conc. H2SO4 H2 [SiF 6] + H2SiO3 SiF4
complex acid (Partial hydrolysis)
white waxy
Oily or deposition of
greasy HF metasilicic acid
appearance
F¯ (g)
(Soda Ext.)

(a) Test based on precipitation reaction (b) (c)

FeCl3(aq) with with oxidising
excess NaF agents
(i) (ii) (iii) (iv) (i) (ii)
MgCl2 CaCl2 Pb(OAc)2 AgNO3 Na3[FeF6]  Acidified Electrolytic
soln. soln. soln. soln. MnO4¯/Cr 2O7
2– oxidation
SCN¯(aq.)
MgF2 CaF2 PbF2 No ppt. No reaction No redox F2
white ppt. white ppt. white reaction

Note : HF is only acid which reacts with glass (Etching of glass) therefore in Lab it is kept in wax coated glass vessel.
SiO2 + HF  SiF4 (aq) + H2O
(glass)

Page No.13
 Oxylate (C2O42–)
1. Oxalate salt of alkali metals are water soluble.
2. Oxalate salts of alkaline earth metals are either water insoluble or sparingly water soluble except BeC2O4 (completely water soluble)
MgC 2O 4  CaC 2O 4   SrC 2O 4  BaC2O 4  BeC2O 4
order of solubility in water :     (order is similar to F¯ salt)
Water inso lub le water solub le

3. BaC2O4  is only water insoluble oxalate salt dissolved in weak acetic acid due to its relative high Ksp at R.T..
4. Oxalate salts of Ag+ , Hg22+, Cu+, Pb 2+ are water insoluble. Being inflammable burns with blue flame
Warm
H2C2O4 CO2 + CO + H2O
Dehyd. Agt.
Conc. H 2SO 4 Colourless gases
(1)

(a) dil. H2SO4

2– (2) Warm H2C2O4
C2O4 (aq.) MnO2 + dil. H2SO4
(b) CO2 + MnSO4
(Soda Ext.)
(3)
Test based on Precipitation reaction Test based on Reducing prop.
(a) (b)
(i) (ii) (iii) (iv) 60ºC KMnO4+ dil. H2SO4
n n n n
CaCl2 sol . BaCl2 sol . Pb(OAc)2 sol . AgNO3 sol .
MnSO4 + CO2 + H2O
CaC2O4 BaC2O4 PbC2O4 Ag2C2O4
(White ppt) (White ppt) (White ppt) In above Redox titration MnSO 4
(White ppt)
acts as self catalyst and KMnO 4
acts as self indicator
dil. dil. dil. excess dil. excess
AcOH AcOH
HCl HCl HNO3 NaOH
HNO3 NH3 soln. NaCN soln. Hypo soln.
+ 3–
CaCl2 Insoluble BaCl2 Soluble Pb(NO3)2 Na2[Pb(OH)4] AgNO3 [Ag(NH3)2] [Ag(CN)2]¯ [Ag(S2O3)2]
(solution) (solution) (solution) (solution)
Note : H2C2O4 / C2O42– can act as reductant but does not act as oxidant.

Page No.14
 Borate (BO33– / B4O72–)

1. Borate salts of s-block are water soluble and other borate salts are either water soluble or sparingly water soluble.
2. Very few borate salts derived from boric acid (H3BO3) are known, mostly borate salts are derived either from metaboric acid (HBO2) or tetraboric
acid (H2B4O7)

H3BO3 (white fumes)

Conc. H2SO4 Warm
(1)

3– 2–
BO3 /B4O7

(Soda Ext.) (2)

Test based on Precipitation reaction Specific flame test with given Solid mixture.
(a) (b)
(i) (ii) (i) (ii)
AgNO3soln. Pb(OAc)2soln. 2– 2–
Solid B4O salt +
7 Solid B4O7 salt +
AgBO2(white ppt) Pb(BO2)2(white ppt) Warm
Conc. H2SO4 + ROH Warm Conc. H2SO4 (few drops)
(Silver Metaborate) (Lead Metaborate) + CaF2(s)
Soluble in dil. HNO3, (R = – CH3, – C2H5)
NH3 soln., CN¯ soln. & B(OR)3(Trialkyl borate)
Hypo soln.
Oxidising BF3+ Ca(HSO4)2
flame it being volatile burns with BF3 being extremely volatile
B(OR)3 burns green edge colour on
burns with green colour without
Reducing touching the flame
with green touching the flame.
edge flame flame (Modified confirmatory test
for borate ion even in the
2+ 2+
presence of Cu , Ba )

Page No.15
 SO42– (aq) Anion

All SO42– salts are water soluble except sulphate salts of Ba2+, Sr2+, Pb2+ and Hg2+

2–
SO4 (aq.)
(1)
(Soda Ext.)
(a) Specific test (Lab test) (b) Test based on Precipitation reaction (c)
BaCl2(soln.) Pb(OAc) 2 soln. Hg(NO3)2soln.

BaSO4 PbSO4(white ppt) 2HgO.HgSO 4 (yellow ppt)

(white ppt.) (Basic mercuric sulphate)
(i) (ii) (iii) conc. excess
dil. HNO3 NaOH
HCl
Hot &  Coke
conc.H2SO4
Sparingly Na2[Pb(OH) 4] (aq)
soluble Soluble Sodium Plumbite

No Ba(HSO4)2 BaS
dissolution (water soluble) (white scales)

Note : BaSO4  , SrSO4  and PbSO4  salts are insoluble in any dil. acid at room temp. due to their low Ksp.

Page No.16
 Phosphate (PO43–)

1. 1°, 2° and 3° phosphate salts of alkali metals are water soluble.

2. 1° phosphate salts or alkaline earth metals are water soluble whereas their 2° and 3° phosphate salts are water insoluble.
3. 3° phosphate salts are water insoluble except alkali metal phosphate salts and (NH4)3PO4.

3–
PO4 (aq.)
(1)
(Soda Ext.)
Test based on Specific test with Ammonium
(a) Precipitation reaction molybedate soln. (lab test) (b)
(Precipitation Reaction)
(NH 4) 2MoO 4 +
T < 40°C
conc. HNO3

(NH4)3PO4.12MoO3
(i) (ii) (iii)
P O ate)
4 or
H sph (NH4)3P(Mo3O10)4
AgNO3 soln FeCl3 soln  N a pho
2
MgCl2 + NH4Cl + NH3 soln (canary yellow ppt.)
(Magnesia mixture) º
(2
Ag3PO4 FePO4 Mg(NH4)PO4 (white ppt)
(yellow ppt) yellow ppt. 2º phosphate) 2+
Vth group filtrate with Mg cation
Soluble in 2+
Mg + is called magnesia mixture
dil. HNO3, NH3 soln., NH4Cl +

2+
(Specific Test for Mg )
CN¯ soln. & Hypo soln. NH4OH
(White solid) Mg2P2O7 + 2NH3 + H2O
Above Reaction, occur in estimation of
PO43– ion by gravimetric analysis

Note : AsO43– ion also give same colour ppt. with ammonium molybedate soln. but on boiling (distinction between PO43– and AsO43–ion)

Page No.17
 2– 2–
O +6 O
Chromate (CrO 4 ) / Dichromate (Cr 2O 7 ) Cr
On
O O O s t
H2 S
+
2–
(a) 1. All CrO salts of s-block are water soluble except BaCrO4 (yellow ppt.) (Blue)

SO H

an
S

din
4

2
O

g
and SrCrO4(only yellow chromate salt soluble in weak acetic acid.)

H2

2
H
SO2
H2SO4 (b) 2. CrO 2– salts of Ag+, Hg 2+ , Pb2+ , Ba2+ , Sr2+ are water insoluble. 2–
(St. O.A.) CrO4 (aq)
4 2 Cr3+ (aq) + O2
2– 2– (yellow)
(green)
NO2¯ (aq) 3. CrO 4 & Cr2O 7 ion exist in equilibrium depending upon pH of solution.
NO3¯ (c)
+
2–
CrO4
2– (H ) Cr2O7
2–
S2O3 (aq) (aq) (aq)
SO 4
2–
+ S (d) (Yellow) (OH )
–
(Orange)

Br¯ (aq)
Br2 (e)
3+ Test based on
Cr (aq.) O
I¯ (aq) Oxd. prop.
3% H2O2 O O On standing
green I2 (f) (3) Cr (aq) + O2 
3+
Cr
2–
C2O4 (aq) Specific + dil. H2SO4 Redox
(green)
O O
CO2 (g) CrO42–/H+Cr2O72– CrO4 (aq)
2– test
deep blue
(Lab test)
2+
(1) organic layer of
3+ Fe (aq) pyridine/ether
Fe (aq.) (h) (Soda Ext.)
O
O O
H2O2 Deep blue colour persists in org.
O2 (i) Cr layer as CrO5 is stabilized
(2) O O
SnCl2 (j) O
SnCl4 R R
Test based on
(a) Precipitation reaction (b) (c)
2+ 2+ n
MCl2 (soln.) (M = Ba , Sr )
2+
Pb(OAc)2sol . AgNO3 sol
n.

MCrO4 (yellow ppt) PbCrO4 (yellow ppt) Ag2CrO4 (Brick red ppt)

SrCrO4 BaCrO4 dil. HCl dil. Excess dil. excess excess Hypo
AcOH HNO3
n
NaOH sol . AcOH HNO3 NaOH NH3soln. Soln
AcOH AcOH
MCl2 soln. + 3–
Insoluble Pb(NO3)2soln. Na2[Pb(OH)4]soln. Insoluble AgNO3 Ag2O [Ag(NH3)2](aq) [Ag(S2O3)2] (aq)
Soluble Insoluble soln. (brown)

Heating Effect : K2Cr2O7 (solid) K2CrO4(s) + Cr2O3(s) + O2 (g)
(Orange) (Yellow) (Green)
Page No.18
 Permanganate (MnO4–)

1. All MnO4– (permanganate) salt are water soluble.

2. KMnO4 decomposes photochemically into MnO2 hence it is stored in dark bottle in Lab.
Conversion :
H2 S
H2O2/H
+
2+
(i) S
MnO4¯ (aq.) Mn (aq.) Colloidal sulphur
(Purple) (Light Pink) SO2
(ii) H2SO4
Electrolytic H2O2/OH– In acidic medium NO2¯ (aq)
oxidation in Cl2/O3 (from NH3) (a) NO3¯(aq.)
(iii)
alkaline med. Cl¯(aq)
Fusion with (iv) Cl2
K2MnO4 MnO2
KNO3(s) in
Green solid Black Br¯ (aq)
presence (v) Br2
of KOH (s)
I¯ (aq) Mn2+ (aq.)
(vi) I2
light pink/colourless
MnO 4¯ (aq.) –2
C2O4 (aq)
Test best on
(Purple/Pink) (vii) CO2
Oxd. prop.
(St. Oxd. Agt.)
(Soda Ext.) (1) 2+
Fe (aq) 3+
(viii) Fe (aq.)

H2O2
+ (ix) O2 
H2O2/H
SnCl2
(x) SnCl4
2–
2+
(xi) S2O3 2–
SO4 + S
MnO4¯ (St. Oxd. Agt.) Mn (Reducing Agt.)
(Light Pink/Colorless)
(Purple/Pink) I¯ (aq)
(i) IO3¯(aq.)
Acidified In neutral or –2 + MnO2
2– (b) faintly alkaline (ii) S2O3 (aq) 2–
SO4 (aq)
PbO2/S2O8 /BiO3¯ (St. Oxd. Agt.) mdm. (Ref. NCERT)
++
(iii) Mn (aq) MnO2(Compn. Rxn)
 ZnSO4
Heating Effect : 2KMnO4 (solid) K2MnO4(s) + MnO2(s) + O2 (g) (catalyst)
(Purple) (Green) (Black)
Page No.19
WET TEST FOR CATION : (Classification of Cations)
Cations are classified into 6 groups on the basis of increasing order of Ksp of precipitated salt with respective to different group reagent at room temperature
Group No. Cations Group Reagent Precipitated salt
st (white ppt.) AgCl (dissolved in NH3 soln.)
I Group +
Ag , Pb , Hg2
2+ 2+
dil. HCl
(3 cations) (white ppt.) PbCl2 (dissolved in Hot water)
(white ppt.) Hg2Cl2 (Turns Black with NH3 soln.)
2+ 2+ 3+ 2+ 2+
II (A) Pb , Cu , Bi , Hg , Cd CuS, PbS, Bi2S3, HgS (all are black sulphide)
H2S in acidic medium
M2Sx are insoluble in YAS
+
nd
H2S/H (C.I. effect)
II Group All back sulphide are dissolved in
3+ 5+ 2+ 4+ 3+ 5+ +
II (B) Sb , Sb , Sn , Sn , As , As 3+ H2S/H hot & dil. HNO3
Fe (aq) Fe (aq) + S
2+

(11 cations) M2Sx are soluble in YAS Redox except HgS (dissolved in aqua regia)
After Boiling off H2S gas 1 or 2 drops CdS (Yellow ppt)
conc. HNO3 is added
2+ 1 or 2 drops 3+ Dissolved in dil. HNO 3
Fe Conc. HNO3
Fe

rd
NH4 Cl(solid) + NH4OH (white ppt.) Al(OH)3
III Group Dissolved in
(brown ppt.) Fe(OH)3
3+ 3+ 3+
(3 cations) Cr , Al , Fe C.I. effect dil. HCl acid
(green ppt.) Cr(OH)3
H2S in basic medium ZnS(white ppt.) Dissolved in
H2S/OH¯  (NH4)2 S non-oxid.
MnS(light pink/buff. coloured ppt)
th
IV Group 2+ 2+ 2+ 2+
acid dil. HCl
(4 cations) Ni , Co , Mn , Zn
NiS(Black ppt)
CoS(Black ppt) Dissolved in hot & dil. HNO3

MCO3 (M = Ba , Sr , Ca ) white ppt

2+ 2+ +2 +2
th (NH4)2CO3 in presence of
V Group 2+ 2+ 2+
Ba , Sr , Ca (NH4Cl + NH4OH)
(3 cations) after dissolving white ppt. in
CH3COOH acid B.S.C. order is applied
th
VI Group +
Na , Mg , K
2+ + No common group reagent No common ppt.
(3 cations)
n
Alkali sol. NH4 + OH¯ Salt decomp .
+

Zero Group + by base NH3 gives brown ppt.

NH (NaOH/KOH) with nesselor's rgt.
(1 cation) 4
Basic gas) (K2HgI4 + OH¯)

Page No.20
REACTIONS INVOLVED IN THE DETECTION OF BASIC RADICALS
Group-I Ag  (aq)  HCl(aq) 
 AgCl  AgCl  2 NH 3 (aq )  [ Ag( NH 3 ) 2 ]  Cl ¯(aq )
White So lub le

Pb   ( aq )  2 HCl ( aq ) 
 PbCl 2  Hg 2  (aq)  2HCl(aq) 
 Hg 2Cl 2  2H  (aq)
White ppt .
White

2 Hg 2 Cl 2   4 NH 4 OH 
 2 Hg   HgO .Hg ( NH 2 )Cl   3 NH 4 Cl  3H 2 O
  
black White
  
Grey

Group-II 2Mx+ (aq) + H2S dil

.HCl
 M 2Sx  ; where (M (aq) = Hg , Cu , Pb , Cd , Bi , As , Sb , Sb , Sn , Sn )

x+ 2+ 2+ 2+ 2+ 3+ 3+ 3+ 5+ 2+ 4+

( coloured ppt )

2Fe3+ (aq) + H2S(g) Re 2+

 2Fe (aq) + S + 2H (aq)
dox
+

Sulphides of II B (Arsenic Sub-group) dissolve in yellow ammonium sulphide (YAS)

Re dox
eg. As2S3 + 2 ( NH 4 ) 2 S2   As2S5 + 2 (NH4)2S As2S5  ( NH 4 ) 2 S  ( NH 4 ) 3 AsS5
YAS Rxn . Thioacid Thiobase Amm.thioarsena te
(So lub le )

M3+(aq) + 3NH4OH NH  M (OH)3 (where M (aq) = Al , Cr , Fe )

Group-III Cl 3+ 3+ 3+ +3
 4
M(OH)3 + 3HCl  MCl3 + 3H2O
So lub le

Group-IV M2+(aq) + H2S (g) NH

 4OH  NH 4Cl 2+ 2+ 2+ 2+ 2+
  MS, (where M (aq) = Zn (aq), Mn (aq), Co (aq), Ni (aq))
ZnS + 2HCl (dil) R
.T.
  ZnCl2 + H2S;
MnS + 2H (aq) (From dil HCl/CH3COOH)  Mn2+ (aq) + H2S(g)
+

3MS + 8HNO3(dil) Hot 2+ 2+ 2+

 3M (NO3)2 + 3S + 2NO(g) + 4H2O, (where M (aq) : Co (aq) Ni (aq))

M2+ (aq) + (NH4)2 CO3 NH  MCO 3  (where M (aq) : Ca (aq), Sr (aq), Ba (aq))
Group-V Cl 2+ 2+ 2+ 2+
 4
White ppt .

Group-VI Mg2+ (aq) + Na2HPO4 + NH4OH NH Cl

 4
+
 Mg( NH 4 )PO 4 + 2Na (aq) + H2O
White
Zero : +
NH4 (S) + NaOH (aq)  NH3(g) +
warm Na+ (aq) + H2O
2K2[HgI4] + 2KOH + NH3  HgO.Hg( NH 2 )I  + 6Kl + NH4I + H2O
Brown
Page No.21
Note :
1. Group cations which are precipitated by corresponding group reagent, can also be precipitated by successive group reagent but never be precipitated
by upper
preceedinggroup reagent.

2. Pb2+ is only cation placed in both first and second group because all Pb2+ cation cannot be precipitated in first group as white ppt of PbCl2 which being
sparingly soluble , few Pb2+ cations are passed into first group filtrate which are further precipiated in second group in the form of black PbS.

3. NH4+ cation is placed in separate zero group because it is only cation identified by volatile product ammonia (basic gas) formed by salt decomposition
reaction with alkali, and detected by test using original solution.

4. Metal cation which are precipitated by acidified H2S can also be precipitated by neutral and alkaline H2S whereas metal cation which are precipitated
by alkaline H2S can not be precipitated by acidified H2S and neutral H2S.

Acidified H2S/Neutral H 2S
M2Sx (ppt.)
IIgp.
cations H2S/OH¯  (NH4)2S
M2Sx (ppt.)
reactions
Mx+ (aq)
with H2S
Acidified H2S/Neutral H 2S
No (ppt.)
(p or d-block metal cation) III & IVgp.
cations H2S/OH¯  (NH4)2S
M2Sx (ppt.) / M(OH)3 
(where M 3+ = Al+3 , Cr+3)

5. All black sulphide (M2Sx) are dissolved in Hot & dil. HNO3 except HgS (soluble in aquaregia and S2– salt soln).
3MS  (M2+ = Cu2+, Pb2+, Ni2+, Co2+) + 8 HNO (dil) Hot
 3M(NO3)2 + 2NO + 3S + 4H2O

( Black ) 3

Eqm shift 2–
HgS  2[Cl] (from Aquaregia) + H2O  HgCl2 + H2SO4 HgS + S (aq) [HgS2] (Colourless solution.)
2–

( Black) So lub le (black) Forward

Page No.22
 Decreasing Order of K sp of black M 2X x 

NiS CoS CuS PbS Ag2S

FeS HgS
Relatively High Ksp Relatively Very low Ksp
Soluble in oxidising acid
Soluble in both like dil. / conc. HNO3 Insoluble in both
oxidising and oxidising and
non-oxidising acid non-oxidising acid
(Soluble in aquaregia
2–
and S salt solution)

6. If white turbidity appears during preparation of original solution in water and it disappears on adding dil HCl (first group reagent), then it is
concluded that first group cation is absent and second group cation either Bi3+ or Sb3+ cation is present in the given salt mixture.

Partial
BiX3 + H2O +
BiO X¯ + 2HX
Hydrolysis white Distinction between
turbidity Sb3+ and Bi3+ cation
can be done using
Partial tarteric acid
SbX3 + H2O SbO+ X¯ + 2HX
Hydrolysis white
turbidity

Page No.23
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