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Important Notes On Salt Analysis
Important Notes On Salt Analysis
XIII
IMPORTANT NOTES ON
QUALITATIVE SALT ANALYSIS
by PMS
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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)
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 )
Page No.2
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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).
oxidising flame
Transparent crystalline bead
(NaBO2 + B2O3) Reducing flame
Ist step IInd step
Fe2(SO4)3 (Solid mixture) 3B O ( present in borax bead ) Fe 2O 3.3B 2O3or 2Fe(BO 2 )3
Fe2O3 .3SO3 23
( 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
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Cu(BO2)2 Cu
2+
Cu Blue Red
Fe(BO2)3 Fe(BO2)2
3+
Fe Yellow Green
Ni(BO2)2 Ni
2+
Ni Brown Grey
+3 +2
Mn(BO2)3 Mn(BO2)2
2+
Mn Amethyst(violet) Colourless
Note : All above colour of bead are observed in their cold condition (without touching flame.)
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
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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 CuCO3 + Na2SO4
CuCO3 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
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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 NaHCO3(Sparingly soluble)
H2CO3 is Observation [Colourless odourless gas evolves with brisk effervescence]
K2MnO4(green)
non-oxidising KMnO4 + MnO2 (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
+
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 BaCO3
CaCO3
(a) (b) (white turbidity)
(a) (b) (c) (white turbidity)
R.T.
excess CO2 excess CO2
BaCl2 soln Pb(OAc)2 sol. AgNO3 Soln
BaCO3 If filtrate contains Ca(HCO3)2 Ba(HCO3)2
–
white ppt. HCO3 ion BaCO3 PbCO3 Ag2CO3 (colourless sol )
n n
(colourless sol )
white white ppt. white/yellow ppt.
Boil Base(NH3 sol
n Boil Boil
dil.HCl dil.HNO3
few drops) CaCO3 BaCO3
BaCl2 Pb(NO3)2 excess
BaCO3 BaCO3 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 HCO3¯ ion forms ppt. of carbonate on boiling. I.M.R. = Inter Molecular Redox
– Boil 2–
2HCO3 CO + CO2 + H 2O
3
100°C
2. Water insoluble carbonate salts are soluble in soda water (CO2 + H2 O) and CH3COOH.
Page No.6
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Sulphite (SO32–)
2–
1. All SO3 salt are water insoluble except alkali metal sulphite salts and (NH 4)2SO 3
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–
Page No.7
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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(CH3COO)2 paper black (PbS)]
HX (a)
S CaCl2
CaOCl2 (b)
Test based on (5) Identification of gas by oxidising agents (Redox reaction)
White 2+
3+
Fe (aq) reducing prop. (2) (a) H2S (b) H2S
turbidity Fe (aq) (c)
SO2 (g)
SYellow turbidity) (d) Warm (1) dil.HCl
conc.
H2SO4
SO2 conc.H S (e)
2 SO4 [Orange solution
+
H2O2 (4) 2– [Pink solution IO3¯/H
H2SO4 excess (f) S (aq.) of
2– +
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 H2S
(3) on ppt. Rn.
H2S gas
Alkaline Na2[Fe(CN)5(NO)]
Excess. H2O2/O3
blue test I¯ (aq.)
conc.HNO3
Hot and Hot & dil. NH3 soln. NaCN layer Colourless
Me2N dil.HNO3 HNO3 Soln.
No Reaction Excess Cl2 water
or
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
Specific test
St.Oxd.Agt Acidified KMnO4 2+ 2–
or Fe(SCN)3 (SO +S) (c)
2– Pink Mn (aq.) (Colourless) + SO4 (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) + SO4 (aq.) + S
reducing prop.
Tests based on
NaF Orange
2+
Hg (aq.) 2–
2+
Co (aq) (4) 2– (3)
[Hg(SCN)4] Co[Hg(SCN)4] S2O3 (aq.)
(blue ppt.) 3+
(Soluble complex)
Hypo is used as fixing agent
in photography
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–
SO3 and S2 O3 )
2–
(Thermally stable) (Thermally unstable) (Thermally unstable) (Thermally unstable) (Violet ppt.)
Page No.9
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Acetate (CH3COO–)
1. All CH3COO– salts are water soluble except CH3COO– salt of Ag+ , Hg22+, Cu+
Note : Deep red colouration is obtained by reaction of Fe3+ cation with SCN– (aq) and CH3COO– (aq).
Page No.10
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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(H2O) 5(NO)]SO4
AgNO3 soln. NH3 gas
soln. (Brown ring complex)
3+
(Zn/Al + NaOH)
St. Oxidising agents 2+
(2) 2– NO3¯ (aq.) + Cr (aq.) / Mn (aq.)
pro
KI + starch
NO2(brown gas) –
/ MnO4 (aq.)
ed.
H2 S FeSO4 + conc. H2SO4
r
Warm on (a) S + NO (Brown ring specific test)
(3)
d
dil.HCl/dil.H2SO4
ase
KI + Starch
Te
transient colour
Warm
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
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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 (yellow), 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)
Na2CrO4 + NaCl
(yellow soln.)
(i) CH3COOH
Cl¯(s) If we want halogen (X2)
(ii) Pb(OAc)2 (a) HCl(white fumes with pungent odour) then St. Oxd. Agt. like
PbCrO4(Yellow ppt.) Br¯(s) MnO 2 is used and
Warm
(Soluble in dil. HNO3 and ex, NaOH soln.
(4) (1) (b) SO2+HBr+Br2Reddish brown fumes) if we want HX then
but insoluble in CH3COOH) conc. non-oxd. acid H3PO4
H2SO4 I¯(s)
SO2+HI+I2Violet vapours) + S (Small Amt.) is used.
CCl4 layer
(c)
Excess Cl2
(b) (Soda Ext.)
Reddish
r¯
Cl2
rB
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, Pb3O4
Pb(OAc)2 soln. AgNO3 soln.
Cl¯ Br¯ I¯
Note : 1. AgCl , PbCl 2 , Hg2Cl 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
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Fluoride (F–)
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
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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 so lub 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 2SO4 Colourless gases
(1)
Page No.14
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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)
3– 2–
BO3 /B4O7
Page No.15
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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.
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
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Phosphate (PO43–)
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
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2– 2–
O +6 O
Chromate (CrO4 ) / Dichromate (Cr2O7 ) 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+, Sr2+, Ba2+, Pb2+ are water insoluble. 2–
(St. O.A.) CrO4 (aq)
4 2 Cr3+ (aq) + O2
2– 2– (yellow)
(green)
NO2¯ (aq) 3. CrO 4 & Cr2O ion exist in equilibrium depending upon pH of solution.
7
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
C2O
2–
(aq) Specific + dil. H2SO4 Redox
(green)
4 O O
CO2 (g) CrO42–/H+ Cr2O72– 2–
CrO4 (aq) 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
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Permanganate (MnO4–)
H2O2
+ (ix) O 2
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/S2O /BiO3¯ (St. Oxd. Agt.)
8 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