Imp Reactions PDF

INORGANIC CHEMISTRY Important statements about actual solubility of Ionic salts in water
1. All alkali metal salts and NH4+ salts are water soluble except NaHCO3(white ppt sparingly soluble)
NaH2SbO4(white ppt) and MClO4  (white ppt) (Where M+ = K+, Rb+, Cs+).
XII (ALL) 2. All NO3–, MnO4–, HCO3–, HSO3– and HSO4– salts are water soluble except NaHCO3(white ppt sparingly soluble)
3. All Ag+, Hg22+ and Cu+ salts are water insoluble except respective NO3–, MnO4–, HCO3–, HSO3– and HSO 4–
salts and AgF (water soluble)
4. All CO 32– , SO 32– and 3ºPO43– salts are water insoluble except respective alkali metal salts and
NH4+ salts.
5. All SO42– salts are water soluble except BaSO 4 , SrSO 4 , PbSO 4  and sulphate salt of Ag+, Hg22+ & Cu+.
  
white ppt. (water in soluble)
6. All CrO42– salts water soluble except BaCrO 4 , SrCrO 4 , PbCrO 4  and CrO42– salt of Ag+, Hg22+ & Cu+.

yellow ppt .
TYPES OF REACTIONS
7. All S2 salts are water insoluble (usually coloured due to polarisation effect) except S2– salt of all s-block
spon
metals and (NH4)2S and Fe2S3 (does not exists at R.T.)  2FeS (black ppt) + 1/2 S.
R.T.
&
8. All OH– compounds are water insoluble except alkali metals hydroxide (being water soluble strong arhhenius
base), Ba(OH)2, Sr(OH)2 and NH4OH (weak arhhenius base).
SALT ANALYSIS 9. All Cl– salts are water soluble except AgCl , Hg 2Cl 2 , CuCl  and PbCl 2  and BiO
 
White ppt.
 
 –
Cl
, SbO

 –
Cl .
White turbidity
(sparingly water soluble)
10. AgBr  ; Hg
All Br– salts are water soluble except   2Br , CuBr , PbBr2 
2 
 
Pale Yellow White ppt.
11. All I – salts are water soluble except AgI  (yellow), Hg2I2 (Green), HgI2 (scarlet red), CuI (white),
spon.
PbI 2 (yellow), BiI3  (black), CuI2 (does not exist at R.T.)   Cu  + 1/2 I .
R.T. 2
white
12. AgCN ,Hg2 (CN)2 ,CuCN  and Pb(CN)2  and other d-block CN–
All CN– salts are water soluble except  
Whiteppt.
spon.
salts are also water insoluble except. Hg(CN)2 (water soluble),Cu(CN)2(doesnot exist)   CuCN  +1/2 (CN) .
R.T. 2
white
13. All CH3COO– salt are water soluble except CH3 COO – salt of Ag , Hg22 and Cu (all are white ppt)
14. All NO 2– salt are water soluble except NO2– salt of Ag , Hg22 and Cu (all are white ppt.)
15. All BO 33– salts of ammonium, alkali metals and alkaline earth metals are water soluble.
16. All S 2O32– salts of alkali metals and alkaline earth metals are water soluble except BaS2O3 (white ppt.)
and S2O32– salt of Ag+, Cu+, Hg22+, Hg2+, Pb2+ and Bi3+ (all are white ppt.)
VIBRANT ACADEMY (India) Private Limited 17. All C2O42– salts of alkali metals, (NH4)2C2O4 and BeC2O4, are water soluble except
Believe In Excellence MC 2 O 4  (M2  Mg 2 , Ca 2 , Sr 2 , Ba 2 ) and C2 O 42– salt of Ag ,Hg22  ,Cu  (all are white ppt.)
  
B-41, Road No.2, Indraprastha Industrial Area, Kota-324005 (Raj.) White ppt. White ppt.
Tel. : 06377791915, (0744) 2778899, Fax : (0744) 2423405 18. All F – salts of alkali metals, NH4F, BeF2 and AgF completely water soluble except MF2  (M2+ = Mg2+,
Email: admin@vibrantacademy.com Website : www.vibrantacademy.com
Website : dlp.vibrantacademy.com Ca2+, Sr2+, Ba2+) (all are white ppt.).
Vibrant Academy (I) Pvt. Ltd. "B-41" Road No.2, IPIA, Kota (Raj.) Ph. 06377791915 (www.vibrantacademy.com) [2]
TYPES OF REACTIONS INVOLVED IN Note : TiO2 and White Lead Pb(OH)2.2PbCO3 are also used as white pigment. However use of TiO2 and Lithophone
are prefered over White Lead due to following limitations.
INORGANIC CHEMISTRY (a) Pb compounds are toxic in nature.
(b) White Lead gets blackened on exposure to air due to formation of black PbS.
(1) Ion-exchange precipitation reaction (Non-redox double displacement reaction)

(2) Arrhenius acid-base neutralization reaction (Non-redox reaction)   Salt ppt  
Type-III A + B C + D
(3) Complex salt formation reaction (Usually non-redox reaction) Salt Salt ppt. Exchange Salt ppt. Salt
(a) Reaction w.r.t coordination sphere solution (Ksp) reaction (Ksp) solution
(b) Reaction w.r.t ionization sphere Mostly occur in Equilibrium shift forward when Ksp of product would be less than Ksp of reactant,
(4) Redox reactions aqueous phase Ksp(product) < Ksp (reactant)
(a) Intermolecular redox reactions
(b) Intramolecular redox reactions    
ppt
(5) Thermal decomposition (may be redox or non-redox reaction ) (i) PbCl2 + Na2SO4 PbSO4 + 2NaCl
Exchange
(6) Lewis-acid-base reaction (non-redox reaction) Mostly occur in non aqueous phase (white ppt) reaction (white ppt)
   
(1) Ion exchange reaction (non-redox double displacement reaction) : Conditions for ion exchange reaction. ppt
(ii) AgCl + Na3AsO3 Ag3AsO3 + 3NaCl
(a) In ion exchange reaction, at least one reactant salt must be water soluble. Exchange
(white ppt) reaction (yellow ppt)
(b) Reaction medium should be almost neutral other wise formed ppt may be dissolved in acidic or basic
medium of solution.
   
(c) All ion exchange reactions are non-redox reactions. ppt
(iii) PbCrO4 + 2NaOH Pb(OH)2 + Na2CrO4
Exchange
(yellow ppt) reaction (white ppt) (yellow solution)
  Single salt   Water soluble (amphoteric)
Type-I A + B C + D
Salt Salt Precipitation Salt Salt
solution solution reaction ppt solution × Water insoluble
Excess NaOH Na2[Pb(OH)4]
(Soluble Plumbite)
   
(i) BaCl2 + Na2SO4  BaSO 4 + 2NaCl

(white ppt) Equilibrium does not
(iv) PbS(black ppt) + 2NaOH solution No reaction (No dissolution)
   Established
(ii) CaCl2 + Na2CO3  CaCO3+ 2NaCl Note : All water insoluble lead salts are dissolved in excess alkali solution due to forming soluble plumbite salt
(white ppt) solution except PbS (Order of Ksp : Water insoluble Pb-salts > Pb(OH)2 > PbS  remember this order)
  
(iii) Pb(CH3COO)2 + K2SO4  PbSO4 + 2CH3COOK
(white ppt) Type-IV   Salt ppt  
A + B C + D
Salt Salt ppt. Exchange Salt ppt. Salt ppt.
solution (Ksp) reaction (Ksp) (Ksp)
  Both salt  
Type-II A + B C + D
Salt Salt Precipitation Salt Salt    
solution solution reaction ppt ppt ppt
(i) Ag2C2O4(white ppt) + MgCl2 MgC2O4(white ppt) + 2AgCl (white ppt)
Exchange
reaction
   
   
(i) ZnSO4 + BaS  ZnS + BaSO4 ppt
(ii) Ag2C2O4(white ppt) + CaS CaC2O4(white ppt) + Ag2S (Black ppt)
(white ppt) (white ppt) Exchange
reaction
   
Lithophone is used as white pigment in paint industry ppt
(iii) Ag2CO 3(white ppt) + MgS2O3 MgCO 3(white ppt) + Ag2S2O3 (white ppt)
    Exchange
(ii) 2AgF + MgCl 2  MgF 2(white ppt) + 2AgCl(white ppt) reaction
water Mg(OH) 2
  Note : MgCO 3 does not exist in Aq. solution because it readily hydrolysed into Mg(OH)2 due to its very
(iii) Ba(HCO3)2 + Na2SO4  BaSO4(white ppt) + 2NaHCO 3(white ppt) low K sp hence MgCO3 is prepared in dry condition (Non Aq. phase).
Vibrant Academy (I) Pvt. Ltd. "B-41" Road No.2, IPIA, Kota (Raj.) Ph. 06377791915 (www.vibrantacademy.com) [3] Vibrant Academy (I) Pvt. Ltd. "B-41" Road No.2, IPIA, Kota (Raj.) Ph. 06377791915 (www.vibrantacademy.com) [4]
  
   
(i) CaCO3 + 2CH3COOH  Ca(CH3COO)2 + H2CO 3 (CO 2 + H2O) (Ka data based reaction)
A + B  C + D
(W Acid salt) (W Acid)
salt salt salt salt
     
A + B  C + D (ii) Pb(CH3COO)2 + H2CO 3  No rxn. (because K a (CH3 COOH) = 1.8 × 10–5 > K a (H2CO3 ) = 4.3 × 10–7)
salt salt salt salt
No reaction (W Acid salt) (Weak Acid)
   
A + B  C + D Note : (1) Order of Ka value of few strong acid in aqueous medium.
salt salt salt salt HClO4(Ka = large value ) > HI (Ka = 3.2 × 109) > HBr (Ka = 1.0 × 109) > HCl (Ka = 1.3 × 106) >
   
A + B  C + D H2SO4 (Ka = 1.0 × 103) > HNO3 (Ka = 2.4 × 101) > H3PO4 (Ka = 7.1 × 10–3)
salt salt salt salt (2) Order of Ka value of few weak acid in aqueous medium.
H2CrO4(Ka = 1.8 × 10–1) > H2C2O4 (Ka = 5.4 × 10–2) > HCOOH (Ka = 1.8 × 10–4) >
   
No Reaction
CH3COOH (Ka = 1.8 × 10–5) > H2CO 3(Ka = 4.3 × 10–7) > HCN(Ka = 6.2 × 10–10) >
2NaCl(salt soln.) + MgSO4(salt soln.)  MgCl2(salt soln.) + Na2SO4 (salt soln.)
occurs NH4+ (Ka = 5.8 × 10–10) > HCO3– (Ka = 4.7 × 10–11)
(3) Ka(H2CO 3) < Ka(CH3COOH), All water insoluble CO 32– salts are dissolved in CH3COOH Acid.
Type-V      (4) Ka(H2CrO4) > Ka(CH3COOH), All water insoluble CrO 42– salts are not dissolved in CH3COOH Acid
A + B (Less volatile) Salt decomposition C D (More volatile) except SrCrO 4 (soluble in CH3COOH due to its relative high Ksp at R.T.)
(W Acid salt) (St. Acid) followed by (St. Acid salt) (W Acid)
no precipitation (5) Ka(H2C2O4) > Ka(CH3COOH), All water insoluble C 2O42– salt are not dissolved in CH3COOH Acid
except BaC 2O4 (soluble due to its relative high Ksp at R.T.)
(6) All water insoluble Ag + salt are dissolved in dil. HNO 3 by salt decomposition reaction except
  
AgX (X¯ = Cl¯ , Br– , I–) due to their very low Ksp at R.T. .
(i) BaCO3(white ppt) + 2HCl Salt dissolution BaCl2 + H2CO3 (H2O + CO2)
in acid (7) All water insoluble Pb2+ salts are dissolved in dil. HNO3 by salt decomposition reaction except
    PbSO4 due to its very low Ksp at R.T.
(ii) CH3COOAg(white ppt) + HNO3 Salt dissolution AgNO3 + CH3COOH
in acid
  
(iii) 2PbCrO4(yellow ppt) + 4HNO 3 Salt dissolution 2Pb(NO 3)2 + H2Cr 2O7(orange) + H2O Find missing product :
in acid
1. Pb(NO3)2 + 2NaOH  ............................. + 2NaNO 3
Type-VI     
A + B (Less volatile) Salt decomposition C D (More volatile) 2. Mn(NO 3)2 + 2NaOH  ............................. + 2NaNO3
(W Acid salt) (St. Acid) followed by (St. Acid salt) (W Acid) 3. BaC2O4 + CH3 COOH ............................. + H 2C2O4
precipitation
4. CuSO 4 + 2KCN  CuCN  + ............................. + K2SO4
   5. Pb(NO3)2 + 2KI ............................. + 2KNO 3
BaCO3 + H2SO4 No salt dissolution BaSO4 + H2CO3 (H2O + CO2)
(i) in acidic 6. CuSO 4 + 2KI .............................+ ½ I2 + K2SO4
(White ppt) (white ppt)
7. FeCl 3 + Na3PO4 .............................+ 3NaCl
   
(ii) CH 3COOAg  + HCl AgCl + CH 3COOH 8. 2AgNO3 + Na2C2O4  .............................+ 2NaNO 3
(White ppt) (white ppt)
9. PbCl2 + H2SO4 .............................+ 2HCl
    10. Ba(NO3)2 + Na2SO4 ............................. + 2NaNO3
(iii) 2PbCrO 4 + 2H2SO4 2PbSO 4 + H2Cr2O 7 + H2O
(Yellow ppt) (white ppt) (orange) 11. CaC2O4 + 2AcOH .............................
Weak acid salt + Strong acid Salt decomposition reaction 12. BaSO3 + H2SO4 ..................... + H 2SO3 (SO 2 + H2O)
Strong acid salt + weak acid No salt decomposition reaction 13. Pb(OAc) 2 + H2S ..................... + 2AcOH
Strong acid salt + Strong acid Ka data based reaction 14. Pb(NO3)2 + H2SO4 ..................... + 2 HNO 3
Weak acid salt + weak acid Ka data based reaction 15. BaCrO4 + HCl ..................... + H2Cr2O7 + H2O
16. CH3COOAg + HNO3 ..................... + CH 3COOH
Conditions for salt decomposition reaction :
17. BaSO4 + dil. HCl (exess) .....................
(1) Ka value of used acid must be more than corresponding acid of anion of salt.
(2) S of the reaction should be +ve therefore conc./dil. H2SO4 is better salt decomposition acid 18. Pb(CH3COO)2 + K 2SO4 ..................... + PbSO 4
due to its higher Ka value and low volatility. ( G = H – T S) 19. BaCrO4 + 2CH3COOH (excess) .....................
(3) Ksp of salt reactant, when it is water insoluble. 20. SrC2O4 + 2HCl ..................... + H2C2O4
(2) Arrhenius acid-base (neutralization) reactions : (Non-redox reactions) Difference between turbidity and ppt.
In ion exchange reaction, when both reactants are acid and base, then it is named as neutralisation / Turbidity ppt.
Arrhenius acid-base reaction. It is colloidal form of solution and never It being heavier settle down at the bottom
settle down at the bottom of test tube of test tube.
Acid + Base Neutralisation Salt + Water + Heat CO2 + lime water  CaCO 3 (turbidity) Na2CO3 + CaCl 2  CaCO3 (white ppt.)
reaction
Note : All turbid solutions are colloidal solutions.
KOH + HNO 3  KNO 3 + H2O + 13.6 kcal/mol
Q. Suggest method of preparation of following salts in Lab (Lab mathod) at room temperature and write
NaOH + CH3COOH  CH3COONa + H2O + (< 13.6 kcal/mol) reactions involved.
(i) MgSO 4 (ii) CaCO3 (iii) Ba(HCO3) (iv) NaCl (v) ZnSO4 (vi) PbSO 4
Ba(OH) 2 + H2SO4  BaSO 4 + 2H2O + (> 2 × 13.6 kcal/mol)
(white ppt)
Acidic and Basic oxides may also be involved in neturalisation reaction Find missing product :
BaO (Basic oxide) + 2HNO3  Ba(NO3)2 + H2O 1. Mg(OH)2 + 2HCl  .............................+ 2H 2O
2. BaO + 2HCl  .............................+ H2O

K2O (Basic oxide) + 2CH3COOH  2CH3COOK + H2O
3. BaO + 2AcOH  .............................+ H 2O

CaO (Basic oxide) + H2SO4  CaSO4 + H2O
excess CO2 4. BaO + H2SO4 .............................+ H 2O
CO 2 + Ca(OH)2  H2O + CaCO3 Ca(HCO3)2 (Eqm. shifting reaction)
passed in soln.
(acidic gas) (Lime water) (white turbidity) (Colourless solution) 5. Ca(OH)2 + 2HF  ............................. + H 2O
excess CO2 6. Ca(OH)2 + CO 2  ............................. + H 2O

SO2 + Ca(OH)2  H2O + CaSO 3 Ca(HSO 3)2 (Eqm. shifting reaction)
passed in soln.
(acidic gas) (Lime water) (white turbidity) (Colourless solution) 7. CaO + H2SO4  ............................. + H 2O
Note : Above reactions are used in lime water test.

8. Ca(OH)2 + SO 2  .............................+ H 2O
excess CO 2
CO 2 + Ba(OH)2  H2O + BaCO3 Ba(HCO3)2 (Eqm. shifting reaction) 9. NaOH + CH3COOH  .............................+ H 2O
passed in soln.
(acidic gas) (Baryta water) (white turbidity) (Colourless solution)
excess CO 2
10. Mn(OH)2 + H2SO4  .............................+ 2H 2O
SO2 + Ba(OH)2  H2O + BaSO3 Ba(HSO3)2 (Eqm. shifting reaction)
passed in soln.
(acidic gas) (Baryta water) (white turbidity) (Colourless solution)
(3) Complex salt formation reaction w.r.t. coordination sphere :
(SA + SB / WA + WB) (Kf > K sp)

Simple Salt(K sp) + simple Salt (SA + WB / WA + SB) (Kf < Ksp)
Complex Salt(Kf) (Non-redox reactions)
CaO(Quick Lime) + H2O  Ca(OH)2(Slaked Lime) + Heat
Equilbirium shift forword when (Kf > Ksp) ; Equilbirium shift backword when (Kf < Ksp)
e)
Li m
ck ppt Kf > Ksp
ui (i) AgNO 3 solution + KCN solution reaction AgCN +
K [Ag(CN)2]
(Q (white ppt) KCN (Excess) Colourless
Heat O
Ca soluble complex
Lime water
(milky solution) ppt Spon Kf > Ksp
(ii) CuSO 4 solution + 2KCN solution Cu(CN)2 CuCN K3[Cu(CN)4]3–
Milk of Lime + reaction RT +3 KCN
Slaked Lime (Unstable) (White ppt) (excess) (Colourless
(high conc.)
soluble complex)
ppt Kf > Ksp
Milk of Lime = Lime water(with low conc. of Ca(OH)2) + Slaked Lime (with high conc. of Ca(OH)2) (iii) FeCl 2 solution + 2KCN solution 4KCN(Excess) + Fe(CN)2 K 4[Fe(CN)6]4–
reaction
Potassium Ferrocyanide
Note : Hydroxide and oxide of Hg 2+, Hg 22+, Fe2+, Fe3+, and Mn2+ do not further dissolve in excess NH3
ppt Kf > K sp
(iv) FeCl 3 solution + 3KCN solution 3KCN(Excess) + Fe(CN)3 K3[Fe(CN)6]3– solution because in such cases, eqbm remain backward.
reaction
ppt rxn. +2 +2 excess NH3 soln.
(Yellow solution) (i) 2HgCl2 + 4NH4OH 3NH4Cl + 3H2O + HgO.Hg(NH2)Cl No dissolution
(white basic amido (Kf < Ksp)
Potassium ferricyanide
mercury chloride)
Complexing Weak Arrh. + –
NH3 (L.Base)+ H 2O NH 4OH NH4(aq) + OH(aq) black ppt.
Reagent Base
solution +2 +2 Ex. NH3 soln.
dispron.
(ii) 2Hg2Cl2 + 4NH4OH 3NH4Cl + 3H2O + HgO.Hg(NH2)ClHg No
rxn. (black) (Kf < Ksp) dissolution
ppt Kf > K sp –
(White ppt.) (White basic
(v) CuSO4+2NH4OH Cu(OH)2 [Cu(NH3)4]2+ (Deep blue colour)+2OH (aq) + 4H2O amido mercury
reaction +4NH 4OH chloride)
ppt Kf > K sp eqbm

(vi) NiCl2 + 2NH4OH Ni(OH)2(ppt) [Ni(NH3)6]2+ + 2OH–(aq) + 6H2O()
reaction remains
+6NH 4OH ppt rxn. M(OH)  2+ 2+ 2+ 2+
2+ 2+ 2+
(iii) M (aq)(M = Fe ,Mn ) + 2NH4OH
2+
[M(NH3)6] (M = Fe , Mn )
 2
backward (less stable outer orbital complex)
(excess) ppt
Deep blue colour like [Cu(NH3)4]2+ cation] (Kf < Ksp) (limitation of CFT)
Kf
(vii) Co+3(NO 2)3 + 3KNO 2 
 K3[Co(NO 2)6]  (Fischer's salt) Eqm. remains
yellow ppt backward
3+ ppt +3 3+
(iv) Fe (aq) + 3NH4OH Fe(OH)3/ Fe2O3 .3H2O [Fe(NH3)6] (Kf < Ksp)
Kf 2+
 Co [Hg(SCN)4] + Co (aq) + 2NO3 (aq)
(viii) Hg(NO 3)2 + 2Co(SCN)2 
2+ –
(excess) rxn. (brown ppt with very low K sp) due to very low (Inner orbital
Deep blue ppt Ksp of Fe(OH)3 complex)
Kf < Ksp
(v) AgI (yellow ppt.) + 2NH4OH (conc.NH3soln.) No dissolution in excess NH3 solution because
IMPORTANT POINTS : eqbm does not established
1. Reaction of metal salt solution with NH3 solution (NH4OH) and alkali solution (like NaOH/KOH) : Reaction of Na2S2O3 Hypo solution (Chelating agent)
n.
Weak Arrh base
Kf > Ksp
complexing + – Na2S2O3 soln. + 2AgNO3 soln.  Ag2 S 2O 3  + 3Na 2 S 2O 3 2Na3[Ag(S 2O3)2]
H2O + NH3(St. ligand) NH4OH solution NH4 (aq) + OH (aq)
agent ( white ppt.) (excess)
y+ + + – ppt rxn. Kf > Ksp
M (aq) + NH4 OH(NH4 +OH ) / NaOH(Na + OH ) M(OH)y / M2Oy(with noble metal)
–
Na2S2O3 soln. + Pb(NO3)2 soln.  PbS 2O 3  + Na 2S 2O 3 Na2[Pb(S2O3)2]
(ppt)
( white ppt.) ( excess )
excess reagent Kf > K sp
excess NH3 solution Na2S2O3 soln. + Hg(NO3)2 soln.  HgS 2O 3  + Na 2S 2O 3 Na2[Hg(S2O3)2]
( white ppt .) (excess )
(NH3 + H2O)
excess NaOH Complex salt ppt reaction w.r.t ionization sphere :

S.A. + S.B. W.A. + S.B. + –
solution (Na + OH )
dissolution occurs no dissolution occurs
due to formation of because eqb
m
   
soluble ammoniated remains backward
complex Complex
Complex Salt + Simple Salt Salt ppt. Complex Salt ppt + Simple Salt
Basic
Amphoteric hydroxide reaction
hydroxide / oxide
Dissolution occurs No dissolution occurs Complex

by lewis acid - base rxn. because NaOH does not (i) [Ni(en)3](NO3)2(violet soln.) + Na2S2O3 solution [Ni(en)3]S2O3(violet ppt.) + 2NaNO 3
Salt ppt.
due to formation of soluble react with reaction
salt solution basic hydroxide / oxide
x–
Nax [M(OH)x+y]
or
NaxMO x+y + ( 2 ) H2O
x+y
(2)
+3 3+
Fe (aq)/[Fe (H2O)6 ] 3+
Fe4 [Fe (CN)6]3(Prussian blue)
2+
6. AgCl  + 2KCN (Excess) ......................... + KCl
(Pale yellow solution)
(Ferri ferrocyanide)
Fe2+(aq)/[Fe+2(H2O)6 ] O2 (Air) 7. Cd(CN)2 +2KCN .............................
K2Fe2+[Fe2+(CN)6](White ppt) Air oxidation prussian Blue
(Pale green solution)
(Ferro ferrocyanide)
2+ +2
Cu (aq)/[Cu (H2O)4 ] +2
8. AgI + 2Na2S2O3 .............................+ NaI
Cu2[Fe (CN)6](Chocalate brown ppt)
(Pale blue solution)
K4[Fe (CN)6]
+2
2+ +2 9. Cr(OH)3 + NH4OH (Excess NH3 solution) .............................
Complex salt pale Zn (aq)/[Zn (H2O)6 ] +2
Zn2[Fe (CN)6](White ppt)
yellow solution of (Colourless solution)
10. NiCl 2 + NH4OH (Excess NH3 solution) .............................
(ii) pot. ferrocyanide 2+ +2
Cd (aq)/[Cd (H2O)6 ]
Cd2[Fe+2(CN)6](Bluish white ppt) 11. Hg(NO3)2 + NH4OH (Excess NH3 solution) .............................
(Colourless solution)
+
Ag (aq)/AgNO3(aq)
+2
Ag4[Fe (CN)6](White ppt) (4) Redox reactions :
Oxidising and reducing property of oxidant and reductant depends upon their electrode potential and
electrode potential of species also depends upon following factors.
+3 3+
Fe (aq)/[Fe (H2O)6] +3 +3 (i) pH of reaction medium. (ii) Effect of pressure.
Fe [Fe (CN)6](Reddish brown solution)
(Pale yellow solution) (iii) Effect of temperature. (iv) Concentration of oxidant and reductant
(Ferri ferricyanide) (undissociated soluble complex)
Fe2+(aq)/[Fe+2(H2O)6] (i) Effect of pH on reaction : KMnO4 is oxidising agent is all three mediums as follows.
Fe2+3[Fe(CN)6]2(Turnbull's blue ppt)
(Pale green solution)
(Ferro ferrocyanide)
2+ 2+
Cu /[Cu (H2O)4] Acidic medium (nf=5)
Cu3[Fe(CN)6]2(Green ppt) Mn2+(aq) / [Mn+2(H2O)6]
(Pale blue solution)
K3[Fe+3(CN)6] (Colorless/light pink soln.)
2+ +2
Complex salt yellow Zn / [Zn (H2O)6]
No reaction Weak basic medium
(iii) solution of Potassium (Colourless solution) KMnO4 MnO2 .2H2O/ [Mn(OH)4]
ferricyanide neutral medium (nf=5)
2+
Cd /[Cd (H2O)6]
+2 Pink/Purple (Brown ppt)
No reaction
+
Ag /AgNO3(aq) Strong Basic medium (pH11)
Ag3[Fe(CN)6](Orange ppt) (nf=1) K2MnO4 (Green permanganate)
Note : (Stable in strong basic medium)
(1) Specific colour of above complexes are due to metal to metal charge transfer phenomenon. • K2MnO 4 disproportionates in acidic, neutral and less basic medium as followes.
(2) Both Prussian Blue and Turnbull’s Blue exist simuntaneously in solution due to partial redox reaction 3MnO 42–(aq) + 4H+(aq)
+
H medium / Neutral / Less basic medium MnO–4 (aq) + MnO2 + 2H2O
(between ferrous and ferric ion) and they are represented by common formula. Disproportionation reaction
Fe+34[Fe+2(CN)6]3 • K2Cr2O7 is oxidising agent only in acidic medium. It doesn’t act as oxidant in neutral and basic medium like
(Prussian blue) KMnO4.
Common –
Formula Fe[Fe(CN)6] Redox
K2Cr2O7(Orange) + 3H2O2(Reductant) + 4H2SO4 Cr2(SO4)3 + 3O2+ K2SO4 + 7H2O
reaction
+2
Fe 3[Fe (CN)6]2
+3
(Green)
(Turnbull's blue) 2–
Cr2O7 (Orange)+ 3H2O2 + 8H (aq)
+
OR 2Cr3+(Green) + 3O2 + 7H2O
O O
Non redox +6
Redox
Cr
Reaction O O Reaction
Find missing product :
O
Blue
1. Cu(OH)2+ 4NH4OH soln. .............................+ 2OH– compound
R R
O
2. Fe(CN)2  + 4KCN ............................. O O
Blue layer of CrO5is unstable in aqueous solution but stable in organic solvent like ether/pyridine Cr .
O O O
3. Fe(CN)3  + KCN .............................
aq. solution 7 H
2CrO5(Blue) Spon. O + Cr2 O3 (Amphoteric)   Cr3+(Green)
4. K4[Fe(CN)6] + ZnSO4 ............................. 2 2
Both CrO42– and Cr2O72– ions exist in equilibirium depending on pH of solution as follows.
5. K4[Fe(CN)6] + 2CuSO4  .............................

pH<7 pH>7 Non-oxidising acids :Acids in which H+ potential is dominating over anionic potential and H+ being preferen-
CrO 42–(yellow) Cr2O72–(Orange) CrO42–(yellow) CrO42– / H+ Cr2O72–
pH>7 pH<7 tial oxidant evolve H2 gas with metal in redox reactions called non-oxidising acid.
(orange) (orange)
• conc / dil / very. dil HX(X = F, Cl, Br, I).
Note : Acidic medium is created by taking mostly H2SO4 acid however HCl and HNO3 acids are usually avoided due
– • Conc / dil H2CO 3 (CO2 being more stable oxide never acts as oxidant)
to reducing property of Cl– and oxidising property of NO3 ion.
Conc / dil. H3POn=3,4 (P4O6 & P4O10 being stable oxide do not act as oxidant)
(ii) Effect of Pressure :
It is considered when redox reaction occurs in gaseous phase. However, mostly redox reaciton ocurs in • dil H2SO4 (non oxidising acid)
aqueous phase. Therefore, effect of pressure is neglected.
Oxidising acids : Acids in which anionic potential is dominating over H+ potential and oxyanion being
(iii) Effect of temperature : preferential oxidant evolve other than H2 gas with metal in redox reaction is called oxidising acids.
on increasing temperature, oxidising and reducing property of species also increases
Conc. / dil. HNO3 (H2O + N2O5)
RT
M(Li, Na, K, Rb, Cs) + H2O (H+ /OH–) MOH + ½ H2() Conc. / dil. HNO2(H2O + N2O3)
G = –ve
RT Conc. H2SO4 (H2O + SO3)
No rxn
G = +ve
• Conc / dil / very dilute HXOn=1,2,3,4 (X= Cl, Br, I)
Mg + 2H2O (H+ / OH–)
warm Mg(OH)2 + H2 • order of oxidising property
G = –ve (white ppt)
HClO > HClO2 > HClO3 > HClO4 .
Warm
No rxn
G = +ve
Effect of concentration :
Zn + 2H2O (H+ /OH–)
Hot Zn(OH)2+ H2 H2SO4 (conc.)  SO2 + [O] + H2O. ...(1)
G = –ve (white ppt)
Zn + [O] ZnO (amphoteric oxidation step) ...(2)
Hot
No rxn ZnO + H2SO4 (aq) ZnSO4 + H2O ...(3)
G = +ve
3Fe + 4H2O (H+/OH–) Zn + 2H2SO4 (conc.) (aq) ZnSO4 (aq) + SO 2 + 2H2O ....(1) + (2) + (3)
Steam Fe3O4 (mixed oxide) + 4H2
In above redox reactions, conc. H2SO4 has its dual charactor. It acts as oxidant as well as neutralising acid.
In all above reactions as temperature increases oxidising and reducing property of oxidant and
reductant also increases.
Reaction of metals with non-oxidising acids :
(iv) Effect of concentration :
RT
Zn (mild reductant) + 2HCl (dilute) Redox rxn.
ZnCl 2 + H 2  more Li
active K
RT metals
Zn(mild reductant) + 2HCl (conc.) Redox rxn.
ZnCl2 + H2 
(Strong R.A.)
RT Al
Zn (mild reductant) + H2SO4 (dilute) Redox rxn.
ZnSO4 + H2 
Mn Redox
M (= Zn/Fe) + Non-oxidising acid H2 (G < O at RT)
RT moderate Zn (Red. agent) Rxn
Zn + 2H2SO4 (conc.) ZnSO 4 + SO2 + 2H2O. (molecular form) active Cr
Redox rxn.
metals Fe
OR (Mild R.A.) Sn
Zn + 4H+ (aq) + SO 42– (aq) SO2 + Zn2+ (aq) + 2H2O (ionic form) Pb
H
HCl(dilute) water
+ –
H (aq) + Cl (aq)
(weak O.A.) (R.A.)
Cu
less active Hg Redox
metals (Weak M (=Ag/Hg) + non-oxidising acid. No rxn (G > 0 at RT)
HCl(conc) water H+ (aq) + Cl–(aq) Ag
(Weak R.A.) Rxn
(weak O.A.) (R.A.)
Non oxidising R.A.) Au (weak OA)
acids Pt
H2SO4(dil) water 2H+ (aq) + SO42–(aq)
(preferential OA)
Note : Redox reaction in which both oxidant and reductant are weak then no reaction will take place
H2SO4 (conc.) water 2H+(aq) + SO42–(preferential O.A.) } oxidising acid because for such reactions G > O at R.T.
Reaction of metals with HNO 3 (oxidising acids) Text Question :Complete & balance the following reactions :
+5
conc. HNO3(70%) +4 (i) Fe + 6HNO 3 (conc)  Fe (NO 3)3 + ...................... + 3H2O
Li NO2 (major product)
more active metals K (strong Oxd. Agt.)
(strong Red. Agt.) +5 (ii) 4Fe + 10 HNO 3 (dil) 4Fe(NO3)2 + ...................... + 5 H2O
Al dil HNO3 (20%) +1
M = Zn/Fe N2O (major product)
(Mild Red. Agt.) (mild Oxd. Agt.)
Mn +5 (iii) 4Fe + 10 HNO3 (very dil) 4Fe(NO3)2 + ......................+ 3H2O
very dil HNO3 (6%) –3
+ HNO3
Zn NH3 gas NH4NO3
Cr (weak Oxd. Agt.)
more active metals (basic) (iv) Cu + (2 + 2) HNO3 (conc) ......................+ 2NO2 + 2H2O
Fe
(Mild Red. Agt.) Sn
Pb (v) 3Cu + HNO3 (dil) ......................+ 2NO + 4H2O
H +5
conc. HNO3(70%) +4
NO2 (major product)
Cu (strong Oxd. Agt.) (vi) Hg + (2 + 2) HNO3 (conc)  Hg (NO3)2 + ......................+ 2H2O
+5
Hg dil HNO3 (20%) +2
Less active metals Ag M = Ag/Hg NO (major product except Sn metal)
(Weak Red. Agt.) Au (weak Red. Agt.) (mild Oxd. Agt.) (vii) 6Hg + 2HNO3 (dil) 3Hg2(NO 3)2 + ......................+ 4H 2O
Pt +5
very dil HNO3 (6%) Ans. (i) NO2 (ii) N2O (iii) NH4NO3 (iv) Cu (NO3)2 (v) Cu(NO3)2 (vi) NO2 (vii) NO
do not react with HNO3 No reaction
(weak Oxd. Agt.)
IMPORTANT POINTS :
Zn + (2 + 2) HNO 3 (conc.) Zn(NO3)2 + 2H2O + 2NO2
(mild RA) (Strong OA) (90%) (80% + 20% other nitrogen oxides) (1) Pb metal are placed above hydrogen in reactivity series. However, their reactivity towards HNO3 is similar to
group metals placed below H in reactivity series.
4Zn + (8 + 2) HNO3 (dil) Zn(NO3)2 + 5H 2O + N2O
RT
(mild RA) (mild OA) (80% ) (80% + 20% other nitrogen oxides) (2) 2Cu+ (aq) 
disproportionation reaction
 Cu2+ (aq) + Cu(s)
4Zn + 10HNO3 (very dil) 4Zn(NO3)2 + 3H2O + NH4NO3

(mild RA) (weak OA) (< 80%) (80% + 20% other nitrogen hydrides) R.T. No disproportionation reaction
2+
Oxidation number range of N atom : (3) Hg2 (aq)
Warm 2+
Hg (aq) + Hg
+5 +4 + 3 +2 +1 0 –1 –2 –3
Ag + 2HNO3 (conc) AgNO 3 + H2O + NO 2 Text Question :Complete & balance the following reactions :
(Weak RA) (Strong OA) (> 90%) (85% + 15% other nitrogen oxides)
(i) Pb + HNO3 (conc) Pb (NO3)2 + ......................+ H2O
3Ag + 4HNO3 (dil) 3AgNO3 + 2H2O + NO
(Weak RA) (Mild OA) (85%) (85% + 15% other nitrogen oxides)
(ii) Pb + HNO 3 (dil)  Pb(NO 3)2 + ......................+ H2O
Ag + HNO 3 (very dil.) no rxn
(Weak RA) (Mild OA) 500ºC 1
(iii) PbO 2  ......................+ O / [O].
 2 2
Remember
(iv) PbO 2 + low H+ ......................
• Conc. HNO 3 (strong OA) + any reducing agent  NO2 (always major product)
(v)
• Conc. H2SO4(Mild OA) + any reducing agent  SO2 (always major product)
• dil HNO3 (Mild OA) + R.A. (any)  NO(+2) (major product)
(except metal placed above
(vi) Sn + HNO3 (conc.)  SnO2 + 2H2O / H4SnO4 + .................
Pb in reactivity series)
• dil HNO3(Mild OA) + M (metals placed above Pb in R.S.) N2O (major product) (vii) Sn + HNO3 (very dilute) Sn(NO 3)2 + ............... + H2O
Ans. (i) NO2 (ii) NO (iii) PbO (iv) No reaction

Text Question : Column-I Column-II (v) NO2, PbO2 (vi) NO2 (vii) NH4NO3
(1) Zn + conc. HNO 3  (P) N2O
(2) Zn + dil NHO 3  (Q) NO2
(3) Cu + dil NHO 3  (R) NO
(4) Cu + conc. HNO3  (S) Cu(NO3)2
(T) Zn (NO3)2
Ans. (1) -QT; (2) - PT; (3) - RS; (4) - QS
IMPORTANT POINTS : Warm
(ii) Pb3O4 (2PbO + PbO2) + 2H2SO4 (dil)   2PbSO4 + PbO 2 + 2H2O
(1) SnO and SnO2 both are amphoteric oxides. However, their reactivity towards acid and base is different. SnO being
more basic is neutralised by HNO3 acid forms Sn(NO3)2 , where as SnO2 doesn't get neutrallised by HNO3. RT 1
(iii) Pb3O4 (2PbO + PbO 2) + 6HNO3 (conc) 
 3Pb(NO 3)2 + O + 3H2O
(2) Noble metals Au & Pt do not react even with highly concentrated form of HNO3. However, they are dissolved 2 2
in aqua regia due to formation of soluble complex acid. Warm
(iv) Pb3O4 (2PbO + PbO 2) + 8HCl (conc.)   3PbCl 2(white ppt) + Cl2 + 4H2O
Aqua Regia Warm 1

(v) Pb3O4 (2PbO + PbO2) + 3H2SO4 (conc) 
 3PbSO4(white ppt) + O + 3H2O
2 2
• HNO3(conc.) + 3HCl (conc.) NOCl + 2H2O + 2[Cl]
1part 3part
PbO2
+ HCl +3
Insoluble layer of PbSO4 is formed
• Au + 3[Cl] (from Aqua Regia) AuCl 3 H[AuCl4]
(soluble solution) (complex acid) over PbO2, hence warming effect is
required to remove it
+ 2HCl +4
• Pt + 4[Cl] (from Aqua Regia) PtCl 4 H2[Pt Cl6]

(soluble solution) (complex acid)
(3) Ag metal dissolves in HNO3 but doesn't dissolve in aqua regia due to formation of insoluble AgCl.
1. Zn(s) + 2HCl  ...................... + H2
Ag + [Cl] (from Aqua Regia) AgCl  +HCl Not dissolved in Aqua Regia (Kf < K sp)
white ppt 2. Pb3O4 + HCl (conc.) 

Warm
 ...............+ Cl 2 + H2O
(4) Very dil HNO3 (< 2%) is non oxidixing acid and Mg and Mn metal evolve H2 gas on reaction with it.
Mg/Mn + very dil 2HNO 3 (<2%)  Mg(NO 3)2 / Mn(NO3)2 + H2 
3. Pb3O4 + HNO3(dil.) 
R.T.
 Pb(NO)3 + .................
(Non-oxidising acid)
(5) Six metals Be, Al, Fe, Cr, Ni and Co get inert with highly concentrated nitric acid (> 80%) due to formation of
protective layer of metal oxide. 4. PbO 2 + HCl (conc.) 
Warm
 .............+ Cl2  + H2O
RT
Highly conc. HNO3 (> 80%)   NO 2 + H2O + [O] (large amount)
5. H2S(g) + SO2(g)  ................. + 2H2O
M(Be, Al, Fe, Cr, Ni, Co) Steam

M 6. Fe(s) + H2O   ................ + H
100 º C 2
Kinetically inert
Protective layer of metal 7. Ag + HNO3 (very dil.)  ........................
oxide is formed over
metal
HNO
1 8. Fe + Very Dil. HNO 3 (6%)  gas  
3
 P salt
RT
PbO 2 (with H+in high concentration)   Pb2+ (aq) + O /[O] + H 2O
2 2
9. Hg + Dil. HNO3  ................. + 2NO + 4H2O
RT
PbO 2 (with low concentration of H+)   No reaction (because PbO2 is stable with low H+ conc.)
10. Pt + Conc. HNO3 + Conc. HCl  ................... + NOCl + H2O
Text Question : Write the balanced equation for the following reactions
(i) Pb3O4 ( 2PbO + PbO2) (Red Lead) + HNO3 (dil) 


RT Reactions of conc. HNO3 with Non-metal/metalloids :
Non-metals/metalloids being very weak reaductant react with conc. from of HNO3 at room temp.
Warm
(ii) Pb3O4 ( 2PbO + PbO2) (Red Lead) + H2SO4 (dil)   R.T.
• Non-metal/metalloid + HNO3(conc)   -ic form of oxy acid + NO 
2
(iii) Pb3O4 ( 2PbO + PbO 2) (Red Lead) + HNO3 (conc) 

RT (very weak reducing agent) (strong O.A.)
Warm R.T.
(iv) Pb3O4 ( 2PbO + PbO2) (Red Lead) + HCl (conc)   • Non-metal/metalloid + HNO3 (dil) 
 No Redox Rxn. (G > 0 at RT)
Warm
(very weak RA) (mild O.A.)
(v) Pb3O4 ( 2PbO + PbO 2) (Red Lead) + H2SO4 (conc)  
T100 º C
RT • Non-metal/metalloid + HNO3 (dil) hot
  -ic form of oxy acid + NO
Ans. (i) Pb3O4 (2PbO + PbO 2) + 6HNO 3 (dil)  2Pb(NO 3)2 + PbO 2 + 2H2O
(very weak RA) (strong O.A.)
(Above reaction is used in preparation of PbO2 (Brown solid)).
Text Questions : Write the balanced equation for the following reactions Disproportionation Reaction
(i) B + 3HNO3 (conc) 
R.T.
 H3BO3 + .................. Redox reaction in which one element from same oxidation state is converted to different oxidation state is
called disproportionation reaction.
(ii) C + 4HNO3 (conc) 

R.T.
 .............+ 2H2O + 4NO2
R.T.
Case-I Mixed oxide/anhydride (with uncommon O.S.) + Water  Disproportionation Reaction
Disp. reaction
(iii) Si + 4HNO 3 (conc.)  2NO2 + H2O  
 HNO3 + HNO2
R.T.
 H4SiO 4 / H2SiO 3 + H2O / SiO 2 + 2H2O + ........... R.T.
Silicic acid / Meta Silicic acid / Anhydrous Disp. reaction

2ClO2 + H2O    HClO3 + HClO2
R.T.
Disp. reaction
(iv) P4 + 20HNO3 (conc.)  2ClO3 + H2O  
 HClO 4 + HClO 3
R.T.
 ...............+ 20NO 2 + 4H2O R.T.
Case-II
(v) S8 + 48HNO3(conc.) 
R.T.
 ................. + 48NO2 + 16H2O Oxy acid with intermediate O.S.  
Disp. reaction
 -ic form of oxy acid + compound with lower O.S.

(Usually -ous form of oxy acid) (Remember)
(vi) X2( = Cl2, Br2, I 2) + 10HNO3 (conc) 

 ............... + 10NO2 + 4H2O
R.T.
When oxysalts are heated then products with highest & lowest O.S. are formed.

(i) H2C2O4   H2O + CO2 + CO
(vii) As + 5HNO3 (conc) 
RT
 H3AsO4 + ............... + H2O
Arsenic acid
H2CO3
(viii) Sb + 5HNO 3 (conc) 

 ................. +
RT 5NO2 + H 2O 
(ii) 3HNO2   HNO3 + 2NO + H2O
Ans. (i) NO2 (ii) CO2 (iii) 4NO2 (iv) 4H3PO4

(iii) 4H3PO3   3H3PO4 + PH3
(v) 8H2SO4 (vi) 2HXO3 (vii) 5NO2 (viii) H3SbO4
 Highest and Lowest O.S. compounds are formed.
Test Questions : Write the balanced equation for the following reactions (iv) 2H3PO2   H3PO4 + PH3
(i) 3H2S + 2HNO 3 (dil) 3S  + ...............+ 4H 2O glass 
conc (v) 3H2SO3   2H2SO4 + S + H2O
rod
H2SO4 
(ii) 6KX + 8HNO3 (dil) ............. + 2NO+ 6KNO3 + 4H2O Oxy acid / Respective Salt acid anhydride + H2O / M2Ox (salt)
(with highest O.S.) Non Redox Reaction
Brown ring (usually -ic form except
(iii) SO2 + 2HNO3 (conc) H2SO4 + ..............
NaNO 3
complex halogen)
+
FeSO 4
(iv) H3PO3/2 + HNO3 (conc) ............ + NO2 R.T.
(i) H2CO3 (conc.) H2O + CO2 (stable oxide)
(non oxidising acid) Non Redox
(v) 6FeSO4 + 2 HNO 3 (dil) + 3H2SO4(conc.)  .............. + 2NO + 4H2O HNO3(dil.)
30ºC  1
(vi) FeSO4(aq) + NaNO3 (aq)  .................. (ii) 2HNO3 (conc.) H2O + N2O5 (less stable) 2NO2 + O / [O]
Non-redox 40ºC 2 2
(oxidising acid)
(vii) 6FeSO4 + 2NaNO 3 + 4H2SO4 (conc) 
Re dox reacion
 ................... + 2NO + Na2SO4 + 4H2O.
  
[Fe(H2O)6] SO4 (Remaining part) + NO ................................... (iii) 4H3PO4 (conc.) 220ºC Pyro form Meta form 6H2O + P4O10 (stable oxide)
320ºC >320ºC
(non oxidising acid)
(FeSO4 is absorber of NO gas) Exp.  = 15 BM.
Ans. (i) 2NO (ii) 3X2 (iii) 2NO2  (iv) H3PO4 (v) 3Fe(SO4)3 (vi) No reaction 444ºC > 800ºC 1
(iv) H2SO4 (conc.) H O + SO3 SO2 + 2 O2 / [O]
Non-redox 2
(vii) 3Fe2(SO4)3, [Fe(H2O)5 (NO)]SO4 (Brown Ring complex) (mild oxidising acid)
Note: Salt of oxidixing acid cannot act as oxidant under water at RT. However, they act as oxidant in non-aqueous
phase at high temperatrue due to evolution of O2.
Text Question : Write the balanced equation for the following reactions  Oxidation :

(i) 3HXO  HXO 3 + .................. 1
(i) P4 
Oxidation
 H3 PO 2 (basicity = 1) 
 NaOH
 NaH2 PO2 (Sodium hypo phosphite)

(ii) 3HClO3   HClO4 + ............. + H2O
 (ii) S8 
Oxidation
 H2S2O3 
NaOH
 Na2S2O3 (Hypo solution)
(iii) 4Na2SO3   ............... + Na2S
Sodium Sulphide Oxidation
(iii) X2   HXO  
KOH  KOH
 HX + HXO 3   KX + KXO3
R.T. hot

(iv) NaH2PO3   Na3PO4 + ................

(v) NaClO  ............... + NaCl Reaciton of Halogens (non-metals) with water :

F2 evolves ozonide oxygen with water whereas Cl 2 and Br2 disproportionates with water and I 2 remains
(vi) H4SiO4  ............. + 2H2O
insoluble with water (G > 0 at RT) therefore iodine solution is prepared in KI not in water.
(non-oxidizing acid)
R.T.
Warm 7 (i) F2(Very Strong Oxd. Agt.) + H2O (H+ /OH–)   2HF  [O] [O 2 (90%)  O3 (10%)]

(vii) 2HClO4   .............. + H2O   .............. + O2 Redox rxn.
2 (ozonide oxygen)
(oxidising acid)
R.T. rd

(viii) 2H3BO3 (conc.)   ............ + 3H2O (ii) Cl2 (Strong Oxd.Agt.)  H2O(H / OH– ) 
Re dox rxn.
 HCl + HClO (incomplete 2/3 dispron. rxn.)
(non oxidixing acid) colorless chlorine water
R.T.
(iii) Br2(Mild Oxd. Agt.) + H2O (H+ / OH–) 
Re dox rxn.
 HBr + HBrO (incomplete 1/3 dispron. rxn.)
rd
(ix) Brown color bromine water
RT
(iv) I2(Weak Oxd. Agt.) + H 2O. (H+/OH–) no redox reaction (G = +ve at RT)
(x)
• I2 dissolves in KI solution by lewis acid-base reaction and brown solution of I3¯ is formed and I3– solution is
 brown due to charge transfer phenomenon.
(xi) 4Na2S2O3 3Na2SO4 +..............
Sodium Redox Reaction
Thiosulphate
Ans. (i) 2HX (ii) 2ClO2 (iii) 3Na2SO4 (iv)PH3 (v) NaClO3
(vi) SiO2 (stable oxide) (vii)Cl2O7, Cl2 (viii) B2O3 (stable oxide)
(ix) Mn2+ (aq), MnO 2 (x) (less stable oxide) (xi) Na2S5
• All halogens are coloured due to HOMO-LUMO transition. However, their respective compounds are colorless
RT
Case-III Non-metal + Alkali solution (like NaOH, KOH, Na2CO3 solution)   Disproportionation reaction. (except few interhalogen compounds).
(i) P4 + 3NaOH + 3H2O

inert atmosphere
  3NaH2PO2 + PH3(small amt. of inflammable P2H4 is also formed) • Other non-metals in elemental form except halogens do not react with water and remain inert into water
of CO 2
(G > 0, at R.T.).
(ii) S8 + 12NaOH 4Na2S + 2Na2S2O3 + 6H2C
Other non-metals (in elemental form like B, C, N2, P4, S8) + water No reaction (G > 0, at R.T.).
RT(cold)
(iii) X2 ( = CI2, Br2, I2) + 2KOH(dil) 
dispr rxn KX + KXO + H2O
hot
(iv) 3X2 (= Cl 2, Br2, I2) + 6KOH(conc) 
dispr n rxn
 5KX + KXO + 3H O
3 2
 Reduction :
Re duction NaOH Re duction NaOH
(i) P4     PH3 (basic)   No reaction. (ii) S8      H2S(acidic)   K2S
Re duction Re duction
(iii) X2 R   HX (acidic)  (iv) X2    HX (acidic) 
KOH KOH
 KX.  KX.
.T. hot
Comproportionation reaction Non existence of few metal iodides at room temperature :
These metal iodide never exist at RT because G for such reactions is negative at RT (G < 0 at RT) due to
Redox reaction in which an element from different oxidation state is converted into same oxidation state is
combination of metal cation acts as strong oxidation agent and iodide anion acts as strong reducing agent.
called comproportionation reaction. Hence they are converted into more stable iodide salt via intramolecular redox reaction.
Reduction
4
–2 +4
spon
Pb  4 (does not exist at RT)   Pb 2   yellow ppt    2 (intramolecular redox reaction)
(i) 2H2S(g) + SO2(g) inter mol. compn. rxn. 3S + 2H2O RT
 stable 
(Red. agent) (weak O.A.)
oxidation
2
1
spon
Cu  2 (does not exist at RT) 
RT
 Cu   white ppt   2 (intramolecular redox reaction)
– +2 Zn salt (catalyst)  stable  2
(ii) MnO (aq) + Mn (aq)
4 MnO2
(inter mol.compron rxn.)
+3
spon 1
Fe I 3 (does not exist at RT) I + Fe I 2 (intramolecular redox reaction)
RT 2 2 (water soluble )
(iii)
–3 +3
 0
spon
NH4 NO2 intramolecular N2 + H2O AuI3 (does not exist at RT) RT
AuI+ I2 (intramolecular redox reaction)
R.A OA Avg. oxidation state (applicable when
cation and anion are of same element)
spon
AgI3 (does not exist at RT) AgI(yellow ppt.) + I2 (intramolecular redox reaction)
(iv)
–3 +5
 +1 RT
NH4 NO3 intramolecular N2O + H2O
R.A OA
3
(N2O is better supporter of combustion than air)
spon
T  3 (does not exist at RT) 
RT
 T   black ppt    2 (intramolecular redox reaction)
 stable 

N2 + [O] (33% > Air)
5
Al metal metal   non
spon
Bi  5 (does not exist at RT)   Bi3  black ppt    2 (intramolecular redox reaction)
Heat + Al2O3 RT
 metal  stable 
M2Ox + heat N2Ox + heat
 Similarly, compounds whose iodide are not exist at R.T., their cyanide are also not exist at R.T.
Metal + N2O Metal oxide + N2 + Heat
4
 spon
Pb  4 (does not exist at RT)   Pb 2   yellow ppt    2
Nonmetal + N2O Nonmetal oxide + N2 + Heat RT
 stable 
Average O.S. rule : It is applicable when given salt contains cation and anion of same element. Pb  CN  4 (does not exist at RT) 
spon
RT
 Pb  CN 2    CN 2
 white ppt 
–2 +3
N 2H 5NO 2(Hydrazinium nitrite)  HN 3(Hydrazoic Acid) + 2H2O
spon 1 Excess KI
Cu 2 (does not exist at RT) 
RT
  2  Cu  [CuI4]3–
2  white ppt 
1 Ex. KCN
Cu  CN 2 (does not exist at RT) 
spon
RT
 CN2  CuCN  [Cu(CN)4]3–
NaOH/KOH/Na2CO3 2  white ppt 
(Alkaline soln.) Ca(OH)2 (slaked line)
dispn. rxn. dispr n rxn. at 40ºC
spon.
Fe  3 (does not exist at RT) 
RT
 Fe2 (aq.)  3 brown  (Exception Fe(CN)3 exists as brown ppt. at RT)
X2 X (aq) + XO (aq) and
– –
Cl2 Ca(OCl)Cl./CaOCl 2
(X2= Cl2, Br2 , I2) (R.A.) (O.A.)
(Bleaching powder)
(compr reaction)
n
(compn rxn.)
Acidic medium Acidic medium (dil HCl/H2SO4)
dil HCl / H2SO4
Pattern of change in oxidation state of s-block , p-block & d-block elements in redox reactions Text Question : Predict the products of following redox reactions :
occur in aqueous solution.
(i) MnO 4– (aq) Red.Agt./H+ ...............
• s-block metals exhibit constant O.S. +1/+2.
(ii) MnO 4– (aq) Red. Agt./Strongly Basic medium ...............
Metal with zero O.S. Oxidation Metal cation with +1/+2
(elemental form). oxid. state. – Red. Agt./neutral or weakly basic medium
(strong reducing agent) electrolytic (very weak oxd. agent) (iii) MnO4 (aq) ...............
reduction
Red. Agt. / acidic medium
• d-block metals exhibit variable O.S. (iv) Cr2O72– (aq) .................
Oxidation Red. Agt. (any)

metal with zero stable metal (v) HNO3 (conc) ..................
oxidation state cation with lower +ve O.S.
(elemental form). Reduction (oxd. agent / Red. agent) +3 Red. Agt.
(vi) HNO2 (better oxd. agent ..................
(mild reducing agent)
weaker red. agent)
Reduction
Oxidation
Red. Agt.
(vii) O 3 ........... + [O]
Red. Agt.
metal with higher (+ve) (viii) H2O2 (Better Oxd. Agt. and Weaker Red. Agt.) ...............
O.S. in oxy. anion (Oxd. Agt.)
+6 Red. Agt. Red. Agt. [H]

• p-block element exhibit variable O.S. (ix) Conc. H 2SO 4(Mild Oxd. Agt.) S
St. Red. Agt.
Red. Agt. Red. Agt.

Oxidation mostly non-metal with zero O.S. (x) HXOn=1, 2,3,4(St. Oxd. Agt.)
non-metals with (-ve)
oxidation state (elemental form) (X2=Cl2 ,Br2,I2)
(reducing agent) Reduction (oxd. agent/red. agent)
Ans. (i) Mn2+ (aq) (ii) MnO42– (green colour) (iii) MnO4 2H2O / Mn(OH)4 (Brown) (iv) Cr 3+ (aq)
Reduction
Oxidation
(Hydrated pyrolusite)
+4 –2
+2
(v) (vi) NO (vii) O2 (viii) H2O (ix) SO 2 , H2S (x) X2 and HX / X¯(aq)
non-metals with highest (+ve)

oxidation state in oxy anion /-ic form of Text Questions : Predict product of following reaction
oxy acid. (oxidising agent)
Oxd. Agt.
(i) s-block metals ...............
warm R.T. Oxd. Agt.

• 2[H] + O2 H2O2 H2O + [O] (ii) NH3 ..............
(Better O.A.
weaker R.A) Oxd. Agt.
(iii) N2H4 ............
Amphoteric metal + Non-oxidising acid/alkali solution [H] (Strong reducing agent) Oxd. Agt.
(iv) HNO2 ................
+3
[H] (strong Reducing agent) Oxd. Agt.
(v) HPO32– (aq) ..............
Oxidising agent Species with lowest O.S.
like oxy anion Amphoteric metal + Acid/Alkali solution
+1 Oxd. Agt.
(vi) H 2PO 2– (aq) ..............
Excess SnCl2 (strong R.A.)
Metal Cation placed Metal atom
below hydrogen in R.S. (vii) AsO33–(aq) Oxd. Agt. ...............
(Oxd. Agt.)
Oxd. Agt.
(viii) SO2 .................
2+ 2+ + 3+ 3+
eg. Cu (aq), Hg (aq), Ag (ag), Bi (aq), Au (aq) excess SnCl2
Cu / Hg / Ag / Bi / Au Oxd. Agt.
St. Red. Agt. (red) (grey) (Black) (Black) (Purple (ix) SO32– (aq) ...............
(Metal cation placed below hydrogen in R.S. ) of cassius)
Oxd. Agt. Oxd. Agt.
(x) H2S .............. H2SO4
CuSO4 Sol. ........................
Oxd. Agt. Oxd. Agt. +5
(xi) HX (X=Cl, Br, I) ............ HXO3
testing of Glass rod dipped ........................
(xxi) NH3gas
Strong Oxd. Agt. ............ NH3 gas in dil HCl
(xii) X2
Nesselar's reagent ........................
Strong Oxd. Agt. 2– K2 [HgI4]+OH¯
2– – .......... + SO (aq)
4
(Cr2O7 , MnO , Cl2, Br2)
4 (turbidity)
2– Oxd. Agt.
(xiii) S2O3 (aq)
Ans. (i) M+ (alkali metal cation) /M2+ (alkali earth metal cation)
(S=+6, S=–2) Weak Oxd. Agt./ Mild Oxd. Agt.
(better Red. Agt. but ................ (ii) N2 (no further oxidation due to its more stability)
3+ 2+
very weak Oxd. Agt.) (I2, Fe , Cu (aq)) (iii) N2(no further oxidation due to its more stability)
(iv) HNO3 (v) H3PO4 (vi) H3PO4 (vii) AsO43– (aq)
(viii) H2SO4 (ix) SO42– (aq) (x) S (xi) X2
10% H2O2 (oxidising agent)/OH¯
+6
(xiv) O O
+5
(xii) HXO3 (xiii) S, S4O62– (aq) Blue color
2– + 2– Cr
CrO4 /H Cr2O7 (aq) O (unstable in aq-sol)
3+
Cr (aq) 2– O
CrO4 (aq) (Orange) (Orange) O
(Reducing agent)
+
(xiv) 3% H2O2/H +6 2–
+4
(reducing agent) (xv) MnO 4 (green) MnO2 (Brown) (xvi) H2S (acidic gas with rotten egg smell)
Redox ..................... (xvii) H2S (acidic gas turns blue litmus red) (xviii) H2S (acidic gas with rotten egg smell)
Rxn.
–3
(xix) NH3 (Basic gas with pungent smell) (xx) NH3 (Basic gas with pungent smell)
Oxd. Agt. Cl2/O3 [Cu(NH3)4]
2+
................ (xxi) , NH4Cl (White dense fumes), HgO. Hg(NH2) I (Basic amido-mercury iodide)
Strongly Basic Medm. deep blue solution (Brown ppt)
2+ Strong Oxd. Agt. (PbO2, Pb3O4, NaBiO3) +7

–
(xv) Mn (aq) MnO4 (aq)
+
H / acidic medium Distinction between NH3 and PH3 gas (NCERT reactions)
Oxd. Agt. ................ Oxd. Agt. / H+

Weak Basic Medium Acidic Medium ppt rxn NH3(excess) 2+ –
(by NH3 gas) CuSO4 solution + NH3 gas Cu(OH)2 [Cu (NH3)4] + 2OH (aq)
+
(NH4 +OH¯) (SA + SB)
(deep blue solution)
[H] (Strong Red. Agt.) .............. NaOH
(xvi) SO2 Na2S
(Zn + NaOH soln.)
ppt
3CuSO4 solution + 2 P gas Cu3P2 + 3H2SO4
rxn (Black ppt)
2– [H] (Strong Red. Agt.) H
(xvii) SO 3 ......... H H
(Al + dil. HCl)
dil HCl
(xviii) Na2S (salt decomposition rxn)
[H] (Strong Red. Agt.) H2SO4

(xix) NaNO3 .............................. (NH4)2SO4
Zn + H2SO4 (dil)
[H]/Strong Red. Agt.

(xx) NH4NO x=2,3 NH3 (Basic gas turns red litmus blue)
(Zn+ KOH)
Strong alkali solution (NaOH / KOH soln.)

Non-redox salt decomposition rxn.
(5) Thermal decomposition reaction (usually occurs in non-aquated phase) : T< 444ºC 444ºC  800ºC
(v) (NH4)2 SO4 2NH3+ H2SO4   H2O + SO 3  SO2 + 1/2O 2 /[O]
Heating effect on NH4 salts
+
non-redox rxn
Case-I If anionic part of ammonium salt is strong oxidising agent (like Cr2O72– , MnO 4– , NO3– , NO2– , ClO–n=1,2,3,4) 220ºC 320ºC high temp
(vi) 4(NH4)H2PO4 non redox 4NH3 + 4H3PO4 2H4P2O7 (HPO3)4 PO
then its thermal decomposition is intramolecular redox reaction and product is mostly N2 gas. but in –2H2O Pyro form –2H2O Meta form –2H2O
4 10
(1º phosphate salt) rxn (solid at R.T.)
(Liquid at RT) (Solid at RT)
case of NH4 NO3 salt it is N2O (Avg. O.S.).
oxidise 
(vii) (NH4)3 PO4 3NH3+ H3PO4 (H4P2O7 /(HPO3)4 /P4O10).
non-redox rxn
(NH4)2 Cr2O7  N2 + Cr2O3(green solid) + 4H2O + heat
(i) (Orange solid)
Red. Agt. Oxd. Agt. Intra mol. redox. rxn Heating effect on 1º, 2º and 3º metal phosphate salts
NaH2PO4  NaPO3 + H2O
Reduce
(1º Phosphate salt)
oxidise
2Na2HPO 4  Na4P2O7 + H2O
–3 +3
NH4 + NO2 –  (2º phosphate salt)
(ii) N2 + 2H2O
Red. Agt. Oxd. Agt. Intra mol. redox. rxn
Na3PO4  No decomposition
Reduce (3º phosphate salt) (3º metal phosphate salts are thermally stable)
oxidise +NH3 gas 

500ºC N + 1/2 O (33%) NaH2PO4 Na(NH4)2PO4 NaPO3 + 2NH3 + H2O
2 2 (1º phosphate) (1º phosphate) (meta phosphate
salt)
NH+4 NO–  NO + 2H2O
(iii) Red. Agt. Oxd. Agt. (Explosive substance)
3
2
Intra mol. redox. rxn (better source
of oxygen
like air) +NH3 gas 
2Na2HPO4 2Na2(NH4)PO4 Na4P2O7 + 2NH3 + H2O
(2º phosphate) (2º phosphate) (Pyro-phosphate salt)
Reduce
oxidise  high temp.

Na(NH4)HPO4.4H2O Na(NH4)HPO4 NaPO3 + NH3 + H2O
(Microcosmic salt) –4H2O (1º phosphate) (Sodium meta phosphate)
(iv) 2 NH+4 ClO4– 

N2 + Cl2 + 2O2 + 4H2O It is used in qualitative analysis of cations in phosphate bead test.
Red. Agt. Oxd. Agt. Intra mol. redox. rxn
Reduce
Case-II If anionic part of ammonium salt is weak or non-oxidising agent, then its thermal decomposition is
non-redox reaction and products are ammonia (base) and respective acid. More than One correct :
1. On heating Pb(NO3)2 gives :
(A) PbO (B) NO 2 (C) O2 (D) NO

(i) NH4Cl (solid) NH3  + HCl (Leaves no residue on heating)
Non redox. rxn
2. Nitrogen gas is liberated by thermal decomposition of :
 (A) NH4NO2 (B) NaN3 (C) (NH4)2Cr2O7 (D) All
(ii) (NH4)2S 2NH3 + H2S(Leaves no residue on heating)
non-redox rxn
3. Among the following compounds, which on heating do not produce N2 ?

(iii) (NH4)2 CO3 2NH3 + CO2 + H2O (A) (NH4)2Cr2O7 (B) NH4Cl + NaNO2 (C) NH4Cl + Ca(OH)2 (D) Ba(N3)2
non-redox rxn
H2CO3

(iv) (NH4)2 C2O4 2NH3 + CO2 + CO + H2O
non-redox rxn
H2C2O4
Paragraph (4 to 6) : (6) Lewis Acid-Base Reaction (usually occurs in non-aqueous phase) :
Most metal oxides are thermally stable at temperature upto 1000°C but the oxide of metals below hydrogen • Hydrolysis of covalent compound (Lewis acid-base reaction)
in the electrochemical series decompose fairly easily. Thus HgO and Ag2O decompose on heating. When covalent compounds are hydrolysed, then water molecule act as nucleophile and such Lewis
acid-base reactions are named as nucleophilic substitution reactions.
4. Which of the following salt does not give NO2 gas on heating ?
(I) SN2 reaction (Nucleophilic substitution reaction of molecularity = 2)
(A) Pb(NO3)2 (B) Zn(NO3)2 (C) AgNO3 (D) KNO3 In this reaction, first step is bond formations with nucleophile. For this step positively charged atom
(acceptor atom) within covalent compound (lewis acid) must have vacant orbital (atomic orbital or anti bonding
5. Which of the following compound cannot be thermally decomposed even at high temperature ? M.O.) and these reactions occurs under ordinary conditions (at R.T.)
(A) CsHCO3 (B) Rb2CO3 (C) Li2CO3 (D) (NH4)2CO3
+3 R.T. tautomerism +3
(i) PF3 + 3H2O SN2 reaction
3HF + P(OH)3 H3PO3
6. Correct code for following thermal decomposition reaction(s) evolving gas having equal number of -and (L.acid) (L.base) (phosphorous acid)
-bonds is : Mechanism :

(i) BeCO 3   (ii) ZnSO4   F H
T  800C
3
O H
sp O RT

P P sp3d
(iii) FeSO 4 
300C
 (iv) (NH4)2Cr2O7   + H H SN2 Reaction
F F F
(A) (i), (ii) (B) (i), (iii), (iv) (C) (i), (ii), (iii) (D) All of these F F
(T.S.)
Subjective :
(P=O)BE > (P–OH)BE –HF
7. How many following Ammonium salts will evolve N2 gas on heating ?
H
(NH4)2CO 3, (NH4)2Cr2O7, NH4NO 2, NH4ClO4, NH4Cl , (NH4)2S, (NH4)2C2O4 H transfer +2H2O
P(OH)F2
P P 2HF
8. How many following Ammonium salts will evolve NH3 gas on heating ?
O OH HO OH
OH OH
(NH4)2CO3, (NH3)2Cr 2O7, CH3COONH4, NH4ClO4, NH4Cl, (NH4)2S, (NH4)2C2O4, (NH4)2SO4, NH4NO3
II form (major%) I form (minor%)
Match the column :

4 4
RT
9. Match the column : (ii) SF4  3H2 O   H2 SO 3  4HF
S 2 reaction N
sulphurous
acid
Column-I Column-II
(Reactions) (Characteristics of any one product) Mechanism :
(A) 
(NH4)2Cr 2O7  (P) Amphoteric species H (S=O) BE > (S–OH)BE
H
O
F
3
sp d F F F (It is formed
(B) 
FeSO4  (Q) Basic species –HF +H2O –H2O
 S + H2O RT 3 2
S sp d S(OH)F3 S(OH)2F2 on partial
SN2 reaction –HF S
F F F O hydrolysis)
F F F
(C) 
Pb(NO3)2  (R) Non-polar gas

(T.S.) +H2O –2HF
NaOH SNAE
(D) P4 
 (S) Polar acidic gas
O (formed on
(T) Coloured residue S complete
HO OH hydrolysis)
(iii) SF6 (Never lewis acid) + H2O  No hydrolysis reaction because SF6 is
kinetically inert and never acts as lewis acid
(II) SN1 reaction (Nucleophilic substitution reaction of molecularity = 1) Cl
In this reaction, first step is bond breaking within covalent compound, therefore such reactions occur at high +4
RT
Si + H2O Si(OH)4 / H4SiO4 + 4HCl
temperature under drastic condition. SN 2 rxn
Cl Cl (Silicic acid)
+3 R.T. Cl
(iv) NF 3 + H 2O No hydrolysis at R.T. via SN2 reaction because water molecules cannot reach to
Note : CCl 4 is also commercially named as pyrene and used as fire extinguisher. However, CCl4 and water
A.B.M.O. of N–F bond lying at higher enegy level.
cannot be used simultaneously to extinguish fire due to formation of poisonous phosgene gas.
high temperature
(v) 2NF3  3H2O 
S 1rxn
 N2O 3 (NO  NO2 )  6HF
N
In general, hydrolysis reactions are non-redox reaction. In few cases, they may be redox reaction
Mechanism :
(I) Non redox hydrolysis reaction :
high temperature –2H
+
4H2O
2 N +
2NF2 + 2H 2O 2 N 2N(OH)F2 2 N +3 RT +3
H
–
SN1 reaction (–2F )  –4HF (i) IF3 + 2H2O HIO2 + 3HF
F F F O HO OH SN
2
F F OH
H
(N=O)BE> (N–OH) BE –2H2O

+5 RT +5
(ii) IF5 + 3H2O 2 HIO3 + 5HF
SN
–30°C +6 RT +6
high temp.
NO + NO2 N2O3 2 N (iii) CrO2Cl2 + 2H2O H2CrO4 + HCl
R.T. –H2O SNAE
O OH Chromic acid
• HNO2 acid is decomposed by two ways :

  +6 RT +6
NO + 2HNO3 2NO2+ H2O + [O] (iv) SO2Cl2 + 2H2O H2SO4 + 2HCl
Disproportionation SNAE Sulphuric acid
reaction
2HNO2acid
Warm
N2O3(NO + NO 2) + H 2O (reaction occurs under water) +4 RT +4
aq. soln. (v) SOCl2 + 2H2O H2SO3 + 2HCl
SNAE Sulphurous acid
Text Question : Why does SiCl4 undergo hydrolysis under ordinary condition whereas CCl4 doesn't at room temperature?
(II) Redox Hydrolysis reactions :
Cl
4 5 3
C +H2O RT No hydrolysis at R.T, because H2O molecule cannot attack on (i) dispron. rxn.
2NO2 (mixed oxide)  H2 O  HN O 3  H N O2
Sol. SN2 rxn R.T.
Cl Cl A.B.M.O. of (C–Cl)bond due to steric crowding.

4 5 3
Cl dispron. rxn.
(ii) 2ClO 2 (mixed oxide)  H2O  HClO 3  HClO 2
R.T.
high temperature (SN1 reaction)

CCl 4  H2O(steam) 
(partial hydrolysis)
 COCl2   2HCl 6
dispron. rxn.
5 7
Phosgene gas (iii) 2ClO3 (mixed oxide)  H2 O  HClO3  HClO 4
R.T.
(Poisonous )
Mechanism : 1 1
R.T.
(iv) X2 (Cl 2, Br2) + H2O 
dispn. rxn.
 HX HXO (incomplete disproportionation reaction)
Cl Cl 
OH 2
C high temp. 
+H2O Cl OH
C –H+ +H2O
C C(OH)Cl3 C
Cl Cl SN1 rxn (–Cl) Cl Cl –HCl RT  90% 10% 
Cl Cl Cl Cl OH (v) F2 + H2O 
redox rxn
 2HF   O 2  O3  ozonised oxygen, because [O] liberated in large amounts
Cl  
–H2O 1 0 1 90% 10%

40C RT
(vi) F2 + H2O   HO F   2HF  (O 2  O3 )
(Analogous to oxy acid) (ozonised oxygen)
O
C R.T.
(vii) I2 + H2O  No reaction (G > 0)
Cl Cl
Phosgene gas
(Poisonous)
Reaction of XeFn = 2, 4, 6 with water : XeF 2 and XeF 4 give redox hydrolysis reaction with water whereas Text Question : What are hydrolysed product of BF3 and SiF4 when they undergo partial hydrolysis at room temperature.
XeF 6 undergo non redox hydrolysis reaction with water. RT
(i) BF3  3H2O 
 B(OH)3  3HF
(vii) XeF2 gives redox reaction with water 3BF 3(remaining part) + 3HF  3H+[BF 4]– (complex acid)
+2 Redox 1 R.T.
XeF2 + H2O Xe + 2 O2 + 2HF 4BF3 + 3H2O 3H[BF4] + B(OH)3
Rxn Partial hydrolysis
complex acid Boric acid
XeO
(unstable at RT) Out of 4 mole of BF3, only one mole BF 3 is hydrolysed (partial hydrolysis) whereas other Boron halides BX3
(viii) XeF 4 undergoes disproportionation reaction with water (X = Cl, Br, I) undergo complete hydrolysis with water because similar complex acids H[BX4] (X = Cl, Br, I) do
not form due to steric hinderance.
+2 +8
dispron. rxn
3XeF4 + 6H2O 2XeO + XeO4 + 12HF
RT (ii) SiF4  4H2 O 
RT
 Si(OH)4  4HF
(unstable (unstable
at RT) at RT) (silicic acid)
1 2x(SiF4  2HF  H2 [SiF6 ] )

2Xe + O2 XeO3+ 2 O2
Complex acid
3 RT
3XeF 4 + 6H2O  2Xe + O + XeO 3 + 12HF (Complete hydrolysis reaction) 3SiF4  4H2 O   Si(OH)4  2H2 [SiF6 ]
2 2 Partial hydrolysis
silicic acid complex acid
(ix) XeF6 gives non redox reaction with water

Out of 3 moles of SiF4, only one mole SiF4 is hydrolysed (partial hydrolysis) whereas other silicon halides
XeF 6 + 3H2O 
RT
 XeO 3(less stable and explosive) + 6HF SiX4(X = Cl, Br, I) undergo complete hydrolysis with water because similar complex acid H2[SiX6] (X = Cl, Br, I)
do not form due to steric hindrance
xenon oxyfluoride are formed on partial hydrolysis
Text Question : What are hydrolysed products of Marshell's acid (H2S2O8) when it undergoes partial and complete
partial
XeF 6 + H2O XeOF 4 + 2HF hydrolysis?
hydrolysis
O H H
O O O
S O OH RT O
partial + H O S O
XeOF4 + H2O XeO 2F2 + 2HF HO O S 2
SNAE S
hydrolysis O O O OH
O OH O
complete (T.S.)
XeO 2F2 + H2O XeO3  2HF
hydrolysis
Partial
complete hydrolysis
• XeF6  3H2 O 
hydrolysis
 XeO3  6HF (Complete hydrolysis reaction)
Hydrolysis of XeF6 in basic medium : O (Caro’s acid)

XeO 3 being acidic oxide is further neutralised by base and HXeO4– (Xenate ion) is formed, which further S
H2SO4 + OH O
8 HO H
O H
disproportionates in basic medium into XeO64  (Perxenate ion) O
+H2O
8 complete
neutralisation
Xe O3  OH 
reaction
  HXeO4 (Xenate ion) hydrolysis
6 8 2 2H2SO4 + H2O2
dispn rxn
3H Xe O 4  5OH 
RT
2 Xe O64  XeO(unstable at R.T.)  4H2O
1
Xe + O2
2
2 gaesous products
Text Question : What are hydrolysed product of P 4O10 when it undergoes step wise hydrolysed? Text Question : Complete the following reaction :
P4O10  6H2O 

RT
 4H3PO4 (i) BeCl2 + 2H2O RT 2HCl + Be(OH)2(amphoteric)
NaOH
Na2[Be(OH)4]
Nu.addition Hydrolysis in basic
(white ppt.) medium Sodium Berylliate
O Mechanism :
HO O
P P H H
O O O O O
H +2
RT O OH O H2O –HCl +H2O NaOH
O P P O + 2H2O Cl—Be—Cl Be Be(OH)Cl Be(OH)2 Na2[Be(OH)4]
P P SN2 reaction –HCl
Nu. addition sp (amphoteric) (sod. berylliate)
OO HO O¯ Cl Cl
O O O O
RT
P P (ii) BCl3  3H2O   H3BO3  3HCl
Boric acid
O O OH
Mechanism :
H2O H
Cl O
Cl
H2O H –HCl +2H2O
O O O O B sp3 B B(OH)Cl2 B(OH)3 (Boric acid)
Cl Cl SN2 reaction Cl Cl –2HCl
P P P P
Borate ion not formed as in acidic medium due to common ion effect equilibrium remains backward.
HO O O O OH
OH OH OH OH RT NaOH
(iii) AlCl3 + 3H2O 3HCl + Al(OH)3(amphoteric) Hydrolysis in basic
Na[Al(OH)4] or (NaAlO2 + 2H2O)
(Tetrapolyphosphoric acid)
(white ppt.) medium
Mechanism :
O O O O O O O
H
+H2O Cl O
P P P P P P P + H3PO4 Cl
H2O H –HCl +2H2O
OH OH
OH Al sp3 Al Al(OH)Cl2 Al(OH)3
HO O O O OH HO O O
H H
OH OH OH OH OH OH OH Cl Cl SN2 reaction Cl Cl –2HCl amphoteric

(Tripolyphosphoric acid) white gelatinous ppt
(Tetrapolyphosphoric acid)
Complete
RT hydrolysis
(iv) PCl 5 + 4H2O    2HCl + POCl3 H3PO 4 + 5HCl
+H2O partial hydrolysis
Mechanism :
O O
H H
P P + H3PO4 + H3PO4 Cl O
HO OH
OH
OH Cl Cl Cl
OH OH SN2 –HCl
P Cl + H2O P P(OH)Cl 4
RT
Cl Cl Cl
+H2O Cl Cl
+H2O
2H3PO4 + 2H3PO4 –HCl
O O –H2O
P 3H2O P P(OH)2Cl3
4H3PO4 HO OH –3HCl Cl Cl  (BE P = O > P–OH)
OH SN AE Cl
(Phosphoric acid)
3  SO
NOTE : Hydrolysis of P4O10 is reverse order of heating effect of H3PO4. (v) SO3 + H2O  H2SO4   H2S2O7 (Oleum) + H2O  2H2SO4
O
RT O O
4H3PO4
220°C
2H4P2O7
320°C
(HPO3)4 (s) > 320°C P4O10 S + H2O
–2H2O –2H2O Nu. addition S + Heat
(meta form) –2H2O O O HO OH
O O
H2SO4
Nu. addition S S +H2O SNAE 2H2SO4
HO O OH
O O
+NaOH (Eqm forward)
F¯ donor and acceptor property of xenon-compounds and inter-halogen compounds. • excess HCl
Similarly AlCl3 soln.    Al(OH)3   Na[Al(OH)4] / (AlO 2– + 2H2O)
+HCl (Eqm backward)
(amphoteric)
XeFn = 2, 4, 6........ XFn = 1, 3, 4, 6........
(Xenon-compounds) (Inter-halogen compounds) In presence of organic compound (cis 1, 2-diol) like catechol, glucose, fructose etc., eqbm shifts much more
+ + + + +
forward due to formation of stable chelate complex with AlO2– ion and now Al(OH)3 cannot be reprecipitated
M+ F– (M = Na , K , Rb , Cs ) –
even by adding HCl acid.
M [XeFn+1] (F acceptor w.r.t. metal fluoride)
+ –
Non Redox Rxn.

–
BF3 +
[XeFn–1] [BF4]
– OH HO O– O– 
 + 2H O
3+
Non redox reaction –
+ Al O2 + Al 2
PF5
Non redox reaction
+
[XFn–1] [PF6]
–
–
F donor wrt
non-metal fluorides (catechol)
OH HO
(catechol)
O– O–

stable chelate complex
HF + –
[XeFn–1] [HF2]
Non Redox Reaction
Note : In ethylene glycol, –OH groups remain at anti-position, therefore it cannot form stable chelate
Flourinating property of xenon-compounds and inter-halogen compounds in dry condition. complex with BO2– and AlO2– ions.
OH
XeFn = 2, 4, 6........ XFn = 1, 3, 5, 7........ CH2—OH
(Xenon-compounds) (Inter-halogen compounds)
 CH2 CH2
HO—CH2
Pt Metal OH
PtF4
Redox Rxn.
Text Question : Complete the following reactions
Au Metal As change density of central atom decrease Lewis acid character also decrease. Hence ease of hydrolysis
AuF3
Redox Rxn.
decrease.
Fluorinating property of
..
PF3 Xenon Fluorides / Interhalogen Fluorides +
PF5 RT
Redox Rxn. (i) NCl3 + 3H2O N NH3 + 3HOCl
complete H
hyd. Cl Cl Cl—O
H
SF4
SF6
Redox Rxn. .. complete
(ii) PCl3 + 3H2O H PO (phosphorous acid) + 3HCl
hydrolysis 3 3
Text Question. How boric acid gets stronger acid by adding organic compound (cis 1,2-diol) like catechol, explain.
..
Ans. 
 (iii) AsCl3 + 3H2O complete As(OH)3 (Arsenous acid) + 3HCl
 [B(OH)4]–/ (BO2– + 2H2O) + H+ (weak acid)
B(OH)3 + H2O  hydrolysis
Boric acid is weak acid in water and its acidic strength increases appreciably by adding organic compound
(cis 1, 2-diol) like catechol, glucose, fructose, etc. due to formation of stable chelate complex with meta
Partial SbO+Cl –
(v) SbCl3 + H2O + 2HCl
(white turbidity) As metallic charactor of
borate ion and now it can be titrated against alkali solution by using suitable indicator. Hydrolysis
C.A. increases, therefore
hydrolysed products are
– Partial – ionic compounds.
BiO+Cl
OH HO O–
3+
O–  + 2H O (vi) BiCl3 + H2O
Hydrolysis (white turbidity)
+ 2HCl
+ BO2 +
–
B
 2
(catechol)
OH HO
(catechol)
O– O–
 Note: White turbidity of Antimonyl chloride (SbO+Cl –) and Bismuthial chloride (BiO+Cl –) is dissolved in dilute HCl
and acetic acid due to shifting equilibrium backward. However, they can be distinguished w.r.t. tartaric acid.
stable chelate complex
Distinction between Sb 3+ and Bi3+ cation
In above condition H+ ion concentration increases appreciably, now boric acid is stronger acid.
+ –
SbO Cl (white turbidity) + tartaric acid dissolution occurs due to
m
shifting eqb backward
+ –
BiO Cl (white turbidity) + tartaric acid no dissolution because eqbm remains
unaffected by tartaric acid.
• Hydrolysis of Ionic Salt Note : S2– and CO32– salts of Al 3+ , Fe3+ , Cr 3+ and Mg2+ do not exist in aqueous solution because they readily
Ionic compounds are hydrolyssed by salt hydrolysis (ion exchange reaction) and mostly water insoluble hydrolysed into corresponding metal hydroxides M(OH)x due to their low Ksp (except Fe2S3). Therefore
metal hydroxide and corresponding volatile product is formed. carbonate and sulphide salts of Al3+, Cr3+, Fe3+ and Mg2+ cations are prepared in dry condition, never in
salt aqueous condition.
Mg3N2 + 6H2O 3Mg(OH)2 + 2NH3
hydrolysis 3+ 3+
Al ,Cr ,Fe ,Mg
3+ 2+
white ppt 2– 2–
CO3 / S + 2H 2O H2CO3 / H 2S + 2OH¯(aq) M(OH) x
(ppt.)
salt
MgS + 2H2O Mg(OH)2 + H2S Fe2S3 never exist and decomposed spontaneously like FeI3 at R.T.
hydrolysis
white ppt Fe2S3 spon.
2FeS(black ppt.) + S (intramolecular redox rxn)
RT
salt spon.
CaH2 + 2H2O Ca(OH)2 + 2H2 FeI3 FeI2(water soluble) + 1/2 I2 (intramolecular redox rxn)
(hydrolyth) hydrolysis RT
white ppt
salt 3Ca(OH)2 + 2PH3

Ca3P2 + 3H2O
hydrolysis white ppt. (small amount of highly PH3  C2H2
inflamable P2H4 is also formed) gas combination was
Single Choice Question :
used in Holme's signal
High temp .
salt 1. 2NF3  3H2O   A  6B
CaC2 + 2H2O Ca(OH)2 + C 2H2 ( steam )
(acetylide) hydrolysis white ppt. (Inflammable)
Incorrect statement regarding above reaction is
salt (A) Compound ‘A’ is anhydride of nitrous acid

Al4C3 + 12H2O 4Al(OH)3 + 3CH4 (Methane)
(Methanide) hydrolysis white ppt. (B) Compound ‘A’ has two sp2 hybridised nitrogen atoms
(C) ‘A’ is monobasic acid
Mg2 C3 + 4H2O salt 2Mg(OH)2 + C3H4  (propyne) (D) The first step of this reaction is elimination of F– ion
(Allylide) hydrolysis (white ppt.)
2. In which of the following cases hydrolysis takes place through SN2 and SN1 mechanism respectively.
IMPORTANT POINTS :
Precipitation of heavier p & d-block metal cation Mx+(aq) with acidified, neutral and alkaline H2S (A) P4O10, SiCl 4 (B) NCl 3, NF3 (C) SiCl 4, SiF4 (D) SF4, TeF6
Metal cation precipitated by acidified H2S can also be precipitated by neutral and alkaline H2S. However,
3. Which of the following is an uncommon hydrolysis product of XeF2 and XeF 4?
metal cation precipitated by alkaline H2S cannot be precipitated by neutral & acidified H2S due to relative
(A) Xe (B) XeO3 (C) HF (D) O2
high Ksp of metal sulphide.
Acidified H2S
M2Sx One or more than one correct :
(C.I. effect)
4. Which of the following statement is correct regarding the complete hydrolysis of Marshall's acid.
II group
cations (A) Caro's acid is an intermediate product.
(B) Two molecules of H2SO4 and one molecule of H2O2 are the final product.
Alkaline / neutral H2S
M2Sx (C) Hybridisation and oxidation state of central atom remain unchanged in the final product.
H2S + NH4OH = (NH4)2S
x+ H2S gas
M (aq) (D) Both final products can act as oxidising as well as reducing agent.
pptn rxn
x+ Alkaline H2S (H2S/OH )
– Comprehension (Q.5 to Q.7)
(where M is p & d-block 3+
M2Sx / M(OH)3(M = Al , Cr
3+ 3+
metal cation) H2S + NH4OH = (NH4)2S Covalent compounds undergo in hydrolysis via SN1 (unimolecular nucleophilic substitution) or SN2 (Bimolecular
III group cations)
nucleophilic substitution) mechanism, for SN2 mechanism within the molecule atom should have at least
III & IV group
cations
one vaccant orbital, if it is not there then hydrolysis takes place via SN1 mechanism (dissociative step) in
drastic condition.
Neutral/Acidified H2S
No ppt 5. What are the hydrolysed products of BeCl2 formed during hydrolysis
(I) [Be(OH)4]2– (II) Be(OH)2 (III) HCl (IV) BeH2
(A) I, II, III (B) II, III (C) I, III (D) II, III and IV
6. Least probable product formed on hydrolysis of BCl3

(A) [B(OH)4]¯ (B) HCl (C) B(OH)3 (D) None of these
7. CCl4 is inert towards hydrolysis under ordinary condition because Salt Analysis
(I) No vaccant atomic orbital on attacking site of C-atom.
(II) H2O molecule can not approach to the anti-bonding M.O. of C–Cl bond due to steric crowding
(Qualitative analysis)
(III) Bond dissociation energy of C–Cl bond is very high Detection of cation and anion present in given salt mixture having one or more salt is called salt analysis or
(IV) CCl 4 is non polar and does not react with polar H2O molecule qualitative analysis.Cation and anion are also named as basic and acidic radicals respectively because
Select correct code: during salt formation cation comes from base and anion comes from acid.
(A) I, II and IV (B) I and IV (C) I and II (D) I, II, III and IV Acid + Base Salt + water + Heat of Neutralisation.
Match the Column :
8. Match the Column-I with Column-II when given compounds undergo complete Hydrolysis. KOH + HNO3 KNO3 + H2O + 13.6 Kcal/mol.
(Base) (Acid) (salt)
Column-I Column-II
(A) NCl3 (P) Hybridisation of central atom does not
change during complete hydrolysis
(B) CIF3 (Q) Oxidation state of central atom does not change NaOH + CH3COOH CH3COONa + H2O + (<13.6 Kcal/mol.)
(Base) (Acid) (salt)
during complete hydrolysis
(C) XeF6 (R) Oxyacid can be formed on hydrolysis
(D) SF 4 (S) Hydraacid is formed on hydrolysis Salt
(T) Hydrolysis occurs at room temperature
9. Column-I (Hydrolysed Products) Column-II (Compounds that undergo hydrolysis) Cation (Basic Radical) Anion (Acidic Radical)
All cations are detected from single original All anions are detected from separate soda extract
(A) H2 gas is evolved (P) CaH2 solution (testing solution for cations) except solution (testing solution for anions) except Co32–and
+
(B) Proton donor oxyacid is formed (Q) POCl3 NH4 cation (detected directly from given salt mixture) HCO3ion (detected directly from given salt mixture)
–
(C) Halogen acid is formed (R) NCl3

Analysis of anion is performed first followed by detection of cation because if any interfering radical
(D) Back bonding is present in formed oxyacid (S) B2H6
(F – , C2O42– , BO33– , PO43–) is present in given salt mixture, then it will interfere the test of III group cations
(T) R2SiCl2
onwards when solution gets basic.
10. Each entry of Column I & Column II is uniquely matched. If any of these interfering radical is present, in given salt mixture, then analysis of third group cations onwards
Column I Column II will be wrong, hence it has to be removed before performing test of III group cations (removeal of interfering
(A) Undergoes in hydrolysis via SN2mechanism (P) BCl3 radical not in syllabus). Which is possible only when analysis of anions is done first.
(in normal condition)
Classification of anions (Acidic radicals)
(B) Undergoes in hydrolysis via SN1mechanism (Q) NCl3 It is not as systematic as that of cation. However their tendency to form volatile product with acid by salt
(in drastic condition) decomposition reaction they are classified into two class A and B.
Classification of Anions
(C) Hybridisation of central atom in transition state (R) SF4
changes during hydrolysis
(D) Only proton donor acids are formed as final (S) NF3 Class A Class B
Anions form volatile product (acid vapour / gas) Anions do not form volatile product with acid and
hydrolysed products
with acid by salt decomposition reaction they are detected by their reaction in aqueous solution.
Sub group I Sub group II Sub group I Sub group II

(8 anions) (7 anions + 8 anions of anions are detected by their anions are detected
anions form volatile subgroup ( I))
n
ppt reaction in aq. solution. by their redox rxn.
product with anions form volatile 2– 3–
eg : SO 4 , PO 4 , AsO 4
3– in aq soltuion.
dil HCl/ dil. H 2SO4 product with conc. H 2SO4 – 2–
eg : MnO 4 , Cr 2O 7 / CrO 4
2–
(non-oxidising (mild oxidising acid)

acids)
Wet test (occurs under water)
Test for anions (Acidic radical)
3–
Few Dry test ( like CrO2Cl 2 test and BO3 ion test)
Wet test for anions of subgroup (I) of class A (dil. acid group) Preparation of soda extract :
2–dil H2SO4 ZnS + BaCl2 + water Ba2+(aq) + 2Cl–(aq) + ZnS (water insoluble)
CO3 (aq) CO2 (odourless)
warm
Salt mixture
– dil H2SO4
HCO3 (aq) CO2 (odourless)
warm Aq. solution of above salt mixture doesn’t give positive test of sulphide ion because ZnS is water insoluble.
dil HCl Hence, it is clear that if any water insoluble salt is present in given salt mixture it has to be made water
SO32–(aq) SO2 (burning sulphur odour)
warm
soluble which is done by preparation of soda extract.
– dil HCl
HSO3 (aq) SO2 (burning sulphur odour) All are colourless
warm ZnS + BaCl2 + solid Na2CO3
gases formed by
salt decomposition
salt mix. (3 part)
2– dil HCl salt mix (1 part)
S (aq) H2S (rotten egg odour) reaction. +
warm Na2CO3
Boil (Ion exchange rxn.)
2– dil HCl 0 +4
S2O3 (aq) S + SO2 (burning sulphur odour)
warm
(S=+6, S=–2)
(Intra mol. redox) Na2S + NaCl + BaCO3 + ZnCO3
– dil HCl water soluble water insoluble

CH3COO (aq) CH3COOH (acid vapour with vinegar odour) salt solution residue
warm
dil HCl warm

N2O3 warm NO + NO2
–
2NO2 (aq) 2HNO2 (brown gas) ZnCO3/BaCO3 (Residue left behind on funnel)
warm –H2O
funnel
Anions of subgroup (II) of class A (conc. acid group)
Remaining part This testing solution is used as soda

conc. H2SO4 of conc H2SO4 extract and used for detection of all
F–(aq) Salt decomp. rxn.
HF. (very weak R.A.) No redox rxn (G > 0) Na+(aq) 2– –
(mild OA) 5-6 mL S2– (aq) anion except CO3 /HCO3 ion
–
Cl (g)
Remaining part soda 2–
CO3 (aq)
conc. H2SO4 of conc H2SO4 extract
Cl –(aq) Salt decomp. rxn.
HCl (weak R.A.) No redox rxn (G > 0)
(mild OA)
Remaining part Test for SO3 ion
2–
conc. H2SO4 of conc H2SO4 H2S + CO2

Br–(aq) HBr (Mild R.A.) SO2+ HBr  + Br2(Brown colour) add HCl
Salt decomp. rxn. (mild OA)
Remaining part
conc. H2SO4 of conc H2SO4
I–(aq) HI (Strong R.A.) SO 2+ HI  + I2(Violet colour)
Salt decomp. rxn. (mild OA) This combination
CO2 + lime water + ve test
will conforms SO32– ion
Remaining part H2S + Cr 2O72–/H+ + ve test (wrong analysis)
conc. H2SO4 of conc H2SO4 (D.A.)
C2O42–(aq) H2C2O4 CO(inflammable) + CO2 (Non inflammable)
Salt decomp. rxn. –H2O Therefore, we add 1–2 drops CH3COOH to remove CO32– , now.
conc. H2SO4 CO32– (not present) + lime water  –ve test.
BO33– / B4O72–(aq) H3BO3 (acid vapour)
Salt decomp. rxn.
H2S + Cr2O72– +ve test.
conc. H2SO4 30º 40º
NO 3–(aq) HNO3 H2O + N2O5 NO2 (brown gas)
Salt decomp. rxn.
Distinction between Br2 and NO2 gases Preparation of soda extract (testing solution for anion)
H2O
Br2 Brown soln. (Few Br2 remains in water) Soda extract is prepared by taking 1 part given solid mixture alongwith 3 part solid Na2CO 3 in porcelain bowl
incomplete
(brown gas) disproportionation and further heated with excess amount of water upto boiling. On boiling, ion exchange reaction will take
Soda extract + conc.H2SO4
place. In this way all anions of given salt mixture are combined with sodium cation and cations are combined
H2O
NO2 colourless soln. (HNO3 + HNO2) with carbonate ion. Sodium salt being water soluble are passed into filtrate and metal carbonate being water
complete
(brown gas) disproportionation insoluble are left behind as residue on funnel.
• All anions are detected from separate soda extract solution (testing solution for all anions) except CO 32– and In this way, cation & anion of given salt mixture are separated and obtained filtrate is called soda extract
HCO3– . (Detected directly from given salt mixture). which is used for detection of all anions except CO32– and HCO3– .
• All cation are detected from single original solution (testing solution for all cations) except
NH4+ cation (Detected directly from given salt mixture)
Neutralisation of soda extract before performing test for any anion: Before performing test of any WET TEST FOR CATIONS : (Classification of Cations)
anion from soda extract, it must be neutralised by suitable acid (1-2 drops) [anion of acid must be different Cations are classified into 6 groups on the basis of increasing order of Ksp of precipitated salt with respective
than the radical that has to be detected] to different group reagent at room temperature.
Usually 1-2 drops of acetic acid is used as neutralising acid because it decomposes CO32– ion
selectively and retains other anions in soda extract solution.
Anions 1 or 2 drops acid used for Reagent used for pptn

neutralisation
–
Cl ion
Cl¯ CH 3COOH / dil.H2SO4 AgNO 3sol. AgCl
(white ppt)
Br– ion Insoluble in

Br¯ CH 3COOH / dil.H2SO4 AgNO3 sol. AgBr conc. HNO3
(pale yellow ppt)
I ion
–
I¯ CH 3COOH / dil.H2SO4 AgNO3 sol. AgI

(yellow ppt)
2–
C2O 4 ion
C2O42– CH 3COOH / dil.H2SO4 CaCl 2sol. CaC 2O4 (insoluble in CH3COOH)
(white ppt)
2–
SO4 ion
SO42– CH 3COOH / dil.HCl BaCl2sol. BaSO4 (insoluble in dil. HCl)
(white ppt)
Note :
(i) BaSO4 is only water insoluble barium salt not dissolved in dil HCl.
(ii) AgCl , AgBr , AgI insoluble in dil./conc. HNO 3 due to their very low Ksp of AgX (X– = Cl –,Br– , I–)
Analysis of cations
Wet test (confirmatory test)
Tests for cation (Basic radical)
Dry test (Preliminary test)
Preparation of original solution (testing solution for cations)

Original solution is prepared by dissoluring given salt mixture into suitable solvent (water, dil. HCl, conc. HCl)
as follows
–
+ Y
B re
– + ixtu
+ X
m
A alt
s
Suitable solvent
+
water dil HCl conc. HCl
A (aq),  
B+(aq)
 
X–(aq),
Y–(aq)
Above solution is named as original solution and used for detection fo all cations except
NH4+ cation (dected directly from given salt mixture).
Important points for wet test of cations :
; where (Mx+ (aq) = Hg2+ (aq) Cu2+ (aq) Pb2+ (aq) Cd2+, Bi3+ (aq) , As3+(aq), As5+(aq) , Sb3+(aq) Sb5+ (aq), Sn2+ (aq), Sn4+ (aq))
1. Group cations which are ppted by corresponding group reagent, can also be precipitated by lower group
reagent but never be ppted by upper group reagent.
CdS, As2S3, As2S5, SnS2  All yellow ppt

 All black ppt
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 precipitated in second group in the form of black PbS.
Sb2S3, Sb2S5 (Both are Orange ppt)

3. NH4 cation is placed in separate zero gp. because it is only cation identified by volatile product ammonia
(basic gas) formed by salt decomposition reaction with alkali.
4. Metal cation which are precipitated by acidified H2S can also be precipitated by neutral and alkaline H2S
CuS, PbS, Bi 2S3, HgS

whereas metal cation which are precipitated by alkaline H2S can not be precipitated by acidified H2S and
neutral H2S.
Acidified H2S/Neutral H2S
M2Sx(ppt.)
SnS (Brown ppt)
I & II gp.
Reactions involved in the detection of basic radicals
cations H2S/OH
–
(NH4)2S
x+ reaction M2Sx(ppt.)
M (aq)
+ Cl – (aq)
with H2S H2S/OH

–
(NH4)2S
M2Sx(ppt.)/M(OH)3(ppt)
(p or d-block metal cation) III & IV gp. 3+ 3+ 3+
cations (where M : Al , Cr )
Acidified H2S/Neutral H2S
MS, (where M2+ (aq) ; Zn2+ (aq), Mn2+ (aq), Co2+ (aq), Ni2+ (aq))
3M (NO3)2 + 3S+ 2NO(g) + 4H2O, (where M2+ (aq) : Co2+(aq) Ni 2+(aq))

No ppt.
5. All black metal sulphide (M2Sx) are dissolved in Hot & dil. HNO3 except HgS (soluble in aquaregia and S 2–
salt soln.).
 (where M2+ (aq) : Ca2+(aq), Sr2+(aq), Ba2+(aq))

M(OH)3  (where M3+ (aq) = Al 3+ (aq) Cr3+ (aq), Fe3+ (aq))
AgCl + 2NH3 (aq) 
x+ 2+ 2+ 3+ 2+ 2+ 2+ Hot
M 2Sx(M = Cu , Pb , Bi , Hg , Ni , Co ) + HNO3(dil.) M(NO 3)x + NO + S + H2O
Metal sulphides of II B (Arsenic group) dissolve in yellow ammonium sulphide (YAS)
(Black ppt.)
+ 6KI + NH4I + H2O

HgS (Black ppt.) + 2[Cl] (from Aquaregia) + H2O HgCl 2(soluble soln.) + H 2SO4
+ 2Na+ (aq) + H2O

+ 3NH4Cl + 3H2O
m
Eq shift
HgS   S2– (aq) [HgS2]2– (Colourless soluble soln.)
MnS + 2H+ (aq) (from dil HCl / CH3COOH) Mn2+(aq) + H2S(g)
Forward
(Black)
DecreasingOrder of Ksp of black M2Sx

Soluble in both Insoluble in both
As2S5 + 2 (NH4)2S 
oxidising and FeS NiS CoS CuS PbS Ag2S HgS oxidising and
NH3(g) + Na+(aq) + H2O
non-oxidising acid non-oxidising acid

Soluble in oxidising acid
2Fe3+ (aq) + H2S(g) 2Fe2+ (aq) + S+ 2H+(aq)
Relative High Ksp Relative Very low Ksp

like conc. HNO3
 + 2H+ (aq)
6. If white turbidity appears during preparation of original solution in water and it disappears on adding dil HCl
ZnCl 2 + H2S ;
(first group reagent), then it is concluded that first group cation is absent and second group cation either Bi3+
+ 3H2O
or Sb3+ cation is present in the given salt mixture.




Mg2+ (aq) + Na2HPO4 + NH4OH
Partial + –
BiO Cl + 2HCl
2Hg2Cl2  + 4NH4 OH 
BiCl 3 + H2O
Hg22+ (aq) + 2HCl (aq) 
Distinction between
Pb2+ (aq) + 2HCl (aq) 
Hydrolysis white 3+ 3+
Sb and Bi cation
Ag+(aq) + HCl (aq) 
turbidity
M(OH)3 + 3HCl 
M2+ (aq) + (NH4)2 CO3
can be done w.r.t.

NH4+ (s) + NaOH (aq)
Partial
3MS+ 8HNO3 (dil)
+ –
M3+ (aq) + 3NH4OH
SbCl3 + H2O SbO Cl + 2HCl tarteric acid.

2Mx+ (aq) + H2S(g)
M2+ (aq) + H2S (g)

ZnS+ 2HCl (dil)
Hydrolysis white
turbidity
+
7. Mg2+ cation can not be ppted as MgCO3 & Mg(OH)2 in presence of ammonium salt (NH4Cl), due to buffer
action of NH4+ cation.
NH4+(aq) + CO32–(aq) HCO3–(aq) + NH3(aq)
eg.
Group VI.
Group-III.
Group-IV.
Group-V.
Group-II
NH4+(aq) + OH–(aq) H2O(aq) + NH3(aq)

Group-I
Zero :
COLOURS OF DIFFERENT COMPOUNDS Green Colour Compounds
QUESTIONS FOR PRACTICE -7
Black Colour Compounds 1. Ni(OH)2 
2. Cr(OH)3 
SINGLE CORRECT QUESTIONS : 1. PbS 
2. Bi2S3 3. Cr2O3
1. Fe(OH)3 can be separated from Al(OH)3 by addition of :
3. Ag2S  4. Cr 2(SO4)3 (Green in Aq. Solution)
(A) BaCl 2 (B) Dil. HCl (C) NaOH solution (D) NH4Cl & NH4OH 5. FeSO4 · 7H2O or [Fe(H2O) 6]SO4 . H2O
4. CuS 
5. NiS  6. FeSO4· (NH4)2SO4·6H2O(Mohr’s salt)
2. When a KI solution is added to a metal nitrate, a black precipitate is produced which dissolves in an excess 6. CoS  7. B(OC2H5)3 (Burns with green edge flame)
of KI to give an orange solution. The metal ion is : 7. HgS  8. CoO · ZnO (Riemann’s green)
(A) Hg2+ (B) Bi3+ (C) Cu2+ (D) Pb2+ 8. FeS  9. K2MnO4 (green colour is due to mangante ion)
9. Cu3P2 
10. BiI 3  Blue Colour Compounds
3. An aqueous solution of a substance, on treatment with dilute HCl, gives a white precipitate soluble in hot 11. MnO2 (a) Light Blue Compunds
water. When H2S is passed through the hot acidic solution, a black precipitate is formed. The substance is 12. Hg  + HgO.Hg(NH2)Cl  1. Cu(OH)2 
(A) Hg22+ salt (B) Cu2+ salt (C) Ag+ salt (D) Pb2+ salt 13. FeO 2. Cu(NO3)2 (Light Blue in Aq. Solution)
14. CuO 3. CuSO4·5H2O (Blue Vitriol)
15. Cu(SCN)2 4. CoCl2 (Anhydrous)
NH Cl Na O Lead
4. CrCl3 
NH OH  (A) 
4
H O  (B) 
2 2
acetate  (C)
4 2 White Colour Compounds (b) Deep Blue Compounds
In this reaction sequence, the compound (C) is : 1. BaCO3  1. Fe4[Fe(CN)6]3 (Prussian’s blue)
(A) Na2CrO4 (B) Na2Cr2O7 (C) Cr(OH)3 (D) PbCrO4 2. SrCO3  2. Fe3[Fe(CN)6]2 (Turnbull’s blue)
3. CaCO3  3. Na4[Fe(CN)5(NOS)](Violet or Purple)
5. Which one among the following pairs of ions cannot be separated by H2S in dilute HCl ? 4. MgCO3 
4. [Cu(NH3)4](OH)2(Schweitzer's reagent)
(A) Bi3+, Sn2+ (B) Al 3+, Hg2+ (C) Zn2+, Cu2+ (D) Ni2+, Cu2+ 5. ZnCO3 
5. [Ni(NH3)6](NO3)2(Deep Blue colour like
6. CaC2O4 
7. BaC2O4 [Cu(NH3)4]2+ cation)
6. Salt (A) gives brick red fumes (B) with conc. H2SO4 and K2Cr2O7 which gives yellow solution (C) with NaOH Orange Coloured Compounds
and it gives yellow ppt. (D) with acetic acid and lead acetate. What is (C) ?
8. SrC2O4
9. Ag2C2O4  1. Sb2S3 
(A) Na2CrO4 (B) CrO2Cl2 (C) PbCrO4 (D) NaCl
10. Be(OH)2  2. Sb2S5 
11. Mg(OH)2  3. KO3
7. When a nitrate is warmed with zinc powder and an NaOH solution, a gas is evolved. Which of the following
12. Ca(OH)2  4. CsO2
reagents will be turned brown by the gas ?
13. Bi(OH)3  5. K[BiI4] (Yellow Complex)
(A) Sodium nitroprusside (B) Sodium cobaltinitrite
14. PbSO4  Yellow Coloured Compounds
(C) Nessler’s reagent (D) Barium chloride 15. SrSO4  1. As2S3 
16. BaSO4  2. As2S5 
8. To avoid the precipitation of hydroxides of Ni 2+, Co2+, Zn2+ and Mn2+ along with those of Fe3+, Al3+ and Cr3+ the 17. ZnS 
third group solution should be :
3. CdS 
18. AgCl 
(A) Heated with a few drops of conc. HNO3 4. PbCrO4 
19. AgNO2 
(B) Treated with excess of NH4Cl 20. PbCl2  5. BaCrO4 
(C) H2S gas is passed into solution 21. PbBr 2  6. SrCrO4 
(D) None of these 22. CuI  7. PbI2 
23. Ag2S2O3  8. Ag3PO4 
9. Which of the following ions is responsible for the brown colour in the ring test for a nitrate ? 24. PbS2O3  9. Ag3AsO3 
(A) [Fe(H2O)5NO]2+ (B) [Fe(CN)5NO]2– (C) [Fe(NO2)6]4– (D) [Fe(H2O)5NO 2]+ 25. Zn(OH)2  10. CuI2 / Cu(CN)2 (Unstable yellow compound)
26. Al(OH)3 (White gelatinous ppt.) 11. AgBr (light yellow)
10. A colourless water soluble solid ‘X’ on heating gives equimolar quantities of Y and Z. Y condense with fumes 27. Cd(OH)2 (Dirty White) 12. AgI (Dark yellow)
HCl and Z does so with NH3. Y gives brown precipitate with Nessler’s reagent and Z gives white precipitate 28. Pb(CN)2  13. K3[Co(NO2)6] (Fischer’s salt)
with nitrates of Ag+, Pb2+ and Hg+. ‘X’ is : 29. Bi2(S2O3)3  14. PbO (in Hot)
(A) NH4Cl (B) NH4NO3 (C) NH4NO2 (D) FeSO4 30. Zn2[Fe(CN)6] 
15. ZnO (in Hot)
16. (NH4)2Sx (where x = 2 to 5)(YAS)
17. (NH4)3PO4· 12MoO3  (Ammonium phospho molybdate) Aquated d-block coloured metal cation by (d – d)
18. HgO  ANSWER KEY
transition. PRACTICE-1
19. Na2CrO4 (Yellow colour is due to CrO42– ion)
20. FeS2(Fool’s gold) 1. [Sc(H2O)6]3+ or Sc3+(aq.) — colourless
1. Pb(OH)2 2. Mn(OH)2  3. Ba(CH3COO)2 4. (CN)2 
Red Colour Compounds 2. [Ti(H2O)6]4+ or Ti4+ (aq.) — colourless
5. PbI2  6. CuI  7. FePO4 8. Ag2C2O4 
1. Hg2CrO4  3. [Ti(H2O) 6]3+ or Ti3+ (aq.) — purple 9. PbSO4 10. BaSO 4  11. No Reaction 12. BaSO4 
2. Ag2CrO4 (Brick red)
4. [V(H2O) 6]2+ orV2+ (aq.) — violet 13. PbS 14. PbSO4 15. BaCl2 16. AgNO3
3. HgI2 (Scarlet red)
4. [Ni(DMG)2] (Rosy red) 5. [V(H2O) 6]3+ or V3+ (aq.) — green 17. No reaction 18. CH3COOK 19. No Reaction. 20. SrCl2
5. Pb3O4 (2PbO + PbO2) (Red Lead) 6. [Cr(H2O) 6 ]2+ or Cr2+ (aq.) — blue
6. CrO2Cl2 (Reddish brown gas) PRACTICE-2
7. [Cr(H2O)6]3+ or Cr3+ (aq.) — violet
7. Fe(SCN)3 (Blood red colouration)
8. [Mn(H2O)6]2+ or Mn2+ (aq.) — light pink 1. MgCl2 2. BaCl2 3. Ba(OAc)2 4. BaSO4 
8. Cu2O (Red solid)
5. CaF 2  6. CaCO3  7. CaSO4 8. CaSO3 
9. PbO (Red litharge) 9. [Mn(H2O)6 ]3+ or Mn3+ (aq.) — violet
9. CH3COONa 10. MnSO4
10. [Fe(H2O)6 ]2+ or Fe2+ (aq.) — light green
Brown Coloured Compounds 11. [Fe(H2O)6]3+ or Fe3+ (aq.) — light yellow
1. SnS  PRACTICE-3
2. Fe(OH) 3 (Reddish Brown) 12. [Co(H2O) 6]2+ or Co2+ (aq.) — pink
1. [Cu(NH3)4]2+ 2. K4[Fe(CN)6] 3. K3[Fe(CN)6] 4. Zn2[Fe(CN)6]
13. [Ni(H2O) 6]2+ or Ni2+ (aq.) — green
3. KI3 / I 3 (Brown coloration) 5. Cu2[Fe(CN)6] 6. K[Ag(CN)2] 7. K2[Cd(CN)4] 8. Na3[Ag(S2O3)2]
14. [Cu(H2O)4]2+ or Cu2+ (aq.) — Pale blue 9. [Cr(NH3)6]3+ 10. [Ni(NH3)6]2+ 11. HgO.HgNH2NO3
4. Cu2[Fe(CN)6] (Chocolate brown) 
+ 15. [Zn(H2O) 6]2+ or Zn2+ (aq.) — colourless
O
5. Hg Hg I¯  PRACTICE-4
NH2
6. PbO2 (Brown solid) 1. ZnCl2 2. PbCl 2  3. PbO2 4. PbCl2 
7. Fe2O3 (Reddish Brown solid) 5. S 6. Fe3O4 7. No Reaction
8. Ag2O (Brown solid) 8. gas (NH3), NH4NO 3(P) 9. Hg2(NO3)2 10. H2[PtCl6]
9. Ag3AsO4 (Reddish Brown)
10. [Fe(H2O)5 (NO)]SO4 (Brown ring complex) PRACTICE-5
Pink Coloured Compounds
1. ABC 2. ABCD 3. C 4. D
1. Mn(OH)2 
5. B 6. C 7. 3 8. 6
2. MnS 
9. A-PRT; B-QRST; C-PRST; D-Q
3. MnO 4 (aq.) (Pink or purple in aq. solution)
PRACTICE-6
1. C 2. B 3. B 4. ABC
5. B 6. A 7. C
8. (A) P,Q,R,T ; (B) Q,R,S,T ; (C) Q,S,T ; (D) Q,R,S,T
9. (A) P,S ; (B) Q, R ; (C) Q,T ; (D) R, S 10. (A) Q ; (B) S ; (C) P ; (D) R
PRACTICE-7
1. C 2. B 3. D 4. D
5. A 6. A 7. C 8. B
9. A 10. A

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INORGANIC CHEMISTRY Important statements about actual solubility of Ionic salts in water

(1) Ion-exchange precipitation reaction (Non-redox double displacement reaction)

2. BaO + 2HCl  .............................+ H2O

3. BaO + 2AcOH  .............................+ H 2O

excess CO2 6. Ca(OH)2 + CO 2  ............................. + H 2O

Note : Above reactions are used in lime water test.

(SA + SB / WA + WB) (Kf > K sp)

ppt Kf > K sp eqbm

excess NaOH Complex salt ppt reaction w.r.t ionization sphere :

Dissolution occurs No dissolution occurs Complex

5. K4[Fe(CN)6] + 2CuSO4  .............................

4Zn + 10HNO3 (very dil) 4Zn(NO3)2 + 3H2O + NH4NO3

Ans. (i) NO2 (ii) NO (iii) PbO (iv) No reaction

Aqua Regia Warm 1

• Pt + 4[Cl] (from Aqua Regia) PtCl 4 H2[Pt Cl6]

white ppt 2. Pb3O4 + HCl (conc.) 

M(Be, Al, Fe, Cr, Ni, Co) Steam

(i) Pb3O4 ( 2PbO + PbO2) (Red Lead) + HNO3 (dil) 

(ii) C + 4HNO3 (conc) 

Silicic acid / Meta Silicic acid / Anhydrous Disp. reaction

(vi) X2( = Cl2, Br2, I 2) + 10HNO3 (conc) 

(viii) Sb + 5HNO 3 (conc) 

(ix) Brown color bromine water

(i) P4 + 3NaOH + 3H2O

Oxidation Red. Agt. (any)

+6 Red. Agt. Red. Agt. [H]

Red. Agt. Red. Agt.

non-metals with highest (+ve)

warm R.T. Oxd. Agt.

2+ Strong Oxd. Agt. (PbO2, Pb3O4, NaBiO3) +7

Oxd. Agt. ................ Oxd. Agt. / H+

[H] (Strong Red. Agt.) H2SO4

[H]/Strong Red. Agt.

Strong alkali solution (NaOH / KOH soln.)

oxidise +NH3 gas 

oxidise  high temp.

(iv) 2 NH+4 ClO4– 

Match the column :

(N=O)BE> (N–OH) BE –2H2O

• HNO2 acid is decomposed by two ways :

Cl Cl A.B.M.O. of (C–Cl)bond due to steric crowding.

high temperature (SN1 reaction)

–H2O 1 0 1 90% 10%

1 2x(SiF4  2HF  H2 [SiF6 ] )

(ix) XeF6 gives non redox reaction with water

Hydrolysis of XeF6 in basic medium : O (Caro’s acid)

P4O10  6H2O 

OH OH OH OH OH OH OH Cl Cl SN2 reaction Cl Cl –2HCl amphoteric

Non Redox Rxn.

salt 3Ca(OH)2 + 2PH3

salt (A) Compound ‘A’ is anhydride of nitrous acid

6. Least probable product formed on hydrolysis of BCl3

(C) Halogen acid is formed (R) NCl3

Sub group I Sub group II Sub group I Sub group II

(non-oxidising (mild oxidising acid)

– dil HCl water soluble water insoluble

dil HCl warm