Redox
(–) ve ON of metals GeH4 (–4), CuH (–1),
Rule: Oxidation Number [Co(CO)4]– (–1), [Ru(CO)4]– (–1)
ON of H = +1 [Except metallic hydride (–1) e.g. ON of Fe in Na2FeO4 = +6
NaH, CaH2, LiAlH4, NaBH4] NO in iron complex has +1 OS. Eg [Link]
ON of O = –2 [Note here Fe has +1 OS]
Exception Like peroxide S has – 1 OS in Na2S2, FeS2.
Peroxides (–1) O.N of metals in metal carbonyl = 0. E.g.
[O22–, –O–O–, Na2O2, H2O2, BaO2, SrO2] Ni(CO)4, Fe(CO)5 Cr(CO)6 etc.
Superoxides (–½), [KO2, RbO2, CsO2] ON of metals in amalgam = 0
O2F2 (+1) ON of metals in alloy = 0
OF2 (+2)] Os, Ru & Xe shows maximum O.N. in whole
Ozonide (O3–) [NaO3, KO3, CsO3] = –1/3 periodic table OsO4, RuO4, H4XeO6 (perxanic
ON of free elements = 0, eg. H2, O2, O3, N2, X2, acid), Perxanic acid exist as XeO2(OH)4 and its salt is
P4, S8 etc. XeO64– (perxanate ion, Ba2XeO6 – barium perxanate)
ON of neutral compounds = 0 e.g. H2O, H2SO4, ON cannot be greater than +8.
CO2 etc.
ON of radical/ion = No of charge with sign. E.g. N.B.
SO4 2– = –2, NH4+ = +1 The highest known oxidation state is reported to
ON of sulphur as sulphide (S2–) = –2 e.g. H2S, be +9 in the tetroxoiridium (IX) cation (IrO4+).
CuS, FeS, NH4HS
ON of halogen (F, Cl, Br, I) = –1 (generally) The lowest oxidation state is −5, as for boron
ON of F = –1 (always), e.g. CaF2, Ca5(PO4)3F, in Al3BC.
Li3Na3(AlF6)2, Na3AlF6 etc.
Stability of O.N in p-block (Inert
Oxidation Number in PT Pair Effect)
ON of group 1/IA [alkali metal(ns1) – Li, Na, K, The inert pair effect means non-participation of
Rb. Cs and Fr] = +1. the outer most ns2 electrons in chemical bonding.
ON of group 2/IIA [alkaline earth metal(ns2) – Mainly found in Gr 13, 14 & 15.
Be, Mg. Ca, Sr, Ba, Ra] = +2. Cause of Inert Pair Effect: due to poor shielding
ON of group 13/IIIA [Boron family (ns2np1) – B, effect of ‘d’ or ‘f’ orbitals, the effective
Al, Ga, In, Tl] = +1, +3 nuclear charge on outer most ‘s’-electrons act
ON of group 14/IVA [Carbon family (ns2np2) – strongly. That is, the nucleus bind or pull the ‘s’-
C, Si, Ge, Sn, Pb] = min(–4) to max (+4) electrons strongly. Consequently, this two ‘s’-
ON of group 15/VA [Nitrogen family (ns2np3) – electrons show a less tendency to participate in
N, P, As, Sb, Bi] = min(–3) to max (+5) chemical reaction. That is, the two ‘s’-electrons
ON of group 16/VIA [Oxygen family (ns2np4) – remain inert basically.
O, S, Se, To, Po] = min(–2) to max (+6) [Except – O] Due to inert nature of ns2 e– down the group
ON of group 17/VIIA [Halogen family (ns2np5) – stability of OS decreases i.e. in group 13 B 3+ is more
F, Cl, Br, I, At] = min(–1) to max (+7) [Except – F] stable than B+ while In3+ is less stable than In+.
ON of group 18/0 [Inert gas (ns2np6) – He, Ne Similarly in group 14 stability order, C4+ > C2+, Pb2+
Ar, Kr, Xe, Rn] = 0 [ except Xe = +2, +4, +6, +8] > Pb4+.
Maximum ON of an element = Group Number Gr - 13 Gr – 14 Gr - 15
(Except O, F & Xe) ns2np1 ns2np2 ns2np3
+1 +3 +2 +4 +3
Minimum ON of an element = Group number – B B C C N N+5
+1 +3 +2 +4 +3
8 (Except metals) Al Al Si Si P P+5
+1 +3 +2 +4 +3
d- block elements shows variable oxidation Ga Ga Ge Ge As As+5
+1 +3 +2 +4 +3
number (Most Common ON is +2) In In Sn Sn Sb Sb+5
+1 +3 +2 +4 +3
f- block elements - variable oxidation number Tl Tl Pb Pb Bi Bi+5
(Most Common ON is +3)
N.B.
Cool Chemistry 9051122547/9339228404 1
Redox
Consequences of Inert Pair ON of NSC
Effect Fe0.93O
Fe0.95O
AlCl3 is more stable than InCl3 Ni0.98O
TlCl is more stable than TlCl3 Sn4.44O8
CO2 is more stable than PbO2
PbO, SnO is more stable than PbO2, SnO2.
SnCl2 is more stable than SnCl4. Oxidation NO Based on
Pb4+ and Sn4+ are good O.A.
PF5 exist but BiF5 does not exist. Structure
O O O
ON by Bonding Concept || || || S
O = Br - Br - Br = O ||
More EN (–1) and Less EN (+1) per covalent || || || O-S-O
||
bond O O O O
+2(Donor & Less EN) –2(Acceptor & More Br3O8 S2O32-
EN)
Tribromine Octoxide Thiosulphate
If Donor is more EN & Acceptor is less EN, then
coordinate bond contribution is neglected.
O O
O O || ||
|| || S S
H-C=O CH3 - C - CH3 ̅ O-S-S-S-S-O
| || || ||
H - C - OH O O O HO HO
| S4O62- H2S2O4
H - C - OH ̅
| Tetrathionate Dithionous acid
H - C - OH
| O
O O O O
H - C - OH || || || ||
| H-O-S-O-H S S S
S
H - C - OH
| O O O
H O H N C HO HO HO HO
H2S2O5 H2S2O6
Disulphurous acid Dithionic acid
O=C=C=C=O
O O
|| || O
Absolute & Average ON S S
O ||
||
S S
CH3COCH3 O O HO O
NH4NO3 HO O O O HO O
Ca(OCl)Cl Pyrosulphuric acid HO
(Disulphuric acid) Peroxodisulphuric acid
H2S2O7 (Oleum) H2S2O8 (Marshall's acid)
ON of Mixed Oxides
Fe3O4
Mn3O4
Pb3O4
Pb3O
Cool Chemistry 9051122547/9339228404 2
Redox
O
|| N.B.
S K3CrO8 [CrO83– is tetraperoxo compound
O OH Cr(O2)43–]
O
HO
Peroxomonosulphuric acid ON Based on Nitrosyl (+1)
H2SO5 (Caro's acid)
NOClO4
Na2[Fe(CN)5NO]
O O
|| || [Fe(H2O)5NO]2+
P P [Link]
HO HO HO HO
H4P2O6 ON of Metals in Complex
Hypophosphoric acid K[Co(C2O4)2(NH3)2]
[Co(Cl)(CN)(NO2)(NH3)3]
O O K2[Cr(NH3)(CN)2O2(O2)]
|| ||
P O P Q. Find ON of Bold Elements
HO HO V(BrO2)2
HO HO Cs4Na(HV10O28)
H4P2O7
Ba(1–x) KxBiO(3 – y)
Pyrophosphoric acid
Oxidation, Reduction, Oxidising
O O
|| ||
O
|| Agent, Reducing Agent
P O P O P
Oxidation = ON
HO HO HO = Reducing Agent (Reductant)
HO HO
H5P3O10 Reduction = ON
Triphosphoric acid = Oxidising Agent (Oxidant)
Maximum & Minimum O.N
O
|| O Maximum ON = No of valence electron
P O || O Minimum ON = 8 – No of Valence electron
H2S RA NH3 RA
HO HO O - H Cr
S B N2H4 B
Peroxo mono O O
CrO5 SO2 B N2 B
phosphoric acid Chromium SO3 B NO2 B
H3PO5 Peroxide H2SO4 OA N2O5 OA
KMnO4 OA HNO2 B
3- K2Cr2O7 OA HNO3 OA
Maximum OS = OA
O O Minimum OS = RA
O O Intermediate OS = Both
Cr Exception – Maxm OS but non-oxidising agent
O O
O +5 +4 +6
O H2CO3 H2SO4
H3PO4
CrO83-
Chromium Tetraperoxo N.B.
Dil H2SO4 is not an OA but conc. H2SO4 is a
O=C=C=C=C=C=O mild OA.
Cool Chemistry 9051122547/9339228404 3
Redox
# Disproportionation Reaction
Non-Redox Reaction X2 + 2NaOH NaX + NaOX + H2O
Acid-Base Reaction/Neutralisation Reaction 3X2 + 6NaOH 5NaX + NaXO3 + 3H2O
P4 + 3NaOH + 3H2O PH3 + 3NaH2PO2
HCl + NaOH ⟶ NaCl + H2O
2H2O2 2H2O + O2
NH3 + H2SO4 ⟶ (NH4)2SO4
Hg2Cl2 Hg + HgCl2
CuO + H2SO4 ⟶ CuSO4 + H2O
2NO2 + H2O HNO3 + HNO2
Double Displacement Reaction / Ion interchange
KClO3 2KClO4 + KCl
reactions of various types, such as precipitation
HCHO + NaOH CH3OH + HCOONa
NaCl + AgNO3 ⟶ AgCl + NaNO3
C6H5CHO + NaOH C6H5CH2OH +
2KI + Pb(NO3)2 ⟶PbI2 + 2KNO3
C6H5COONa
[Cr(NH3)4Br2]SO4 + BaCl2
S8 + OH– S2– + S2O32–
⟶[Cr(NH3)4Br2]Cl2 + BaSO4
Thermal decomposition of carbonates
# Comproportionation Reaction
MCO3 ⟶ MO + CO2 [M = alkaline earth metal]
MnO4– + Mn2+ → MnO2
Titration of acid with carbonate or bicarbonate
2H2S(g) + SO2(g) → 3S(s) + 2H2O(g)
Acid + CO32– / HCO3– ⟶ Salt + CO2 + H2O IO3− + 5I− + 6H + → 3I2 + 3 H2O
H2SO4 + Na2CO3 ⟶ Na2SO4 + CO2 + H2O Ag2+(aq) + Ag(s) → 2Ag+(aq)
2HCl + CaCO3 ⟶ CaCl2 + CO2 + H2O
HCl + NaHCO3 ⟶ NaCl + CO2 + H2O
Oxidisng Agent
Polar molecule insert/ejection. The most common
case is hydrolysis and reverse reactions. OA Condition Reaction
PCl5 + 4H2O⟶ H3PO4+5HCl X2 X2 + 2e– 2X–
CO2 + H2O ⟶ H2CO3 H2O2 Acidic H2O2 + 2H+ + 2e– 2H2O
SO3 + H2O ⟶ H2SO4 KIO3 Acidic IO3– + 6H+ + 6e– I– + 3H2O
K2Cr2O7 Acidic Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
Reorganization of bonds between atoms of same KMnO4 Acidic MnO4– + 8H+ + 5e– Mn2+ + 4H2O
type - Polymerisation KMnO4 Neutral MnO4– + 2H2O + 3e– MnO2 + 4OH–
3C2H2⟶C6H6 KMnO4 Alkaline MnO4– + e– MnO42–
nCH2-CH2 ⟶ (-CH2-CH2-)n MnO2 Acidic MnO2 + 4H+ + 2e– Mn2+ + 2H2O
Complex Formation NaClO ClO– + H2O + 2e– Cl– + 2OH–
Cu2+ (aq) + 4NH3(aq) ⟶ [Cu(NH3)4]2+ (aq) HNO3 Conc NO3– + 2H+ + e – NO2 + H2O
Tetra ammine HNO3 Dil NO3– + 4H+ + 3e– NO + 2H2O
copper complex
(deep Blue Solution)
Ni + 4CO ⟶ Ni(CO)4 Reducing Agent
Ligand exchange
[Fe(H2O)6]3+ + 6CN−⟶[Fe(CN)6]3− + 6H2O RA Reaction
H2 H2 2H+ + 2e–
HI 2I– I2 +2e–
Types of Redox H2O2 H2O2 2H+ + O2 +2e–
# Intermolecular Redox Reaction FeSO4 Fe2+ Fe3+ + e–
2KMnO4 + 10FeSO4 + 8H2SO4 K2SO4 + SnCl2 Sn2+ Sn4+ + 2e–
5Fe2(SO4)3 + 2MnSO4 + 8H2O Na2S2O3 2S2O32– S4O62– + 2e–
K2Cr2O7 + 6FeSO4 + 7H2SO4 K2SO4 + H2SO3 SO32– + H2O SO42– + 2H+ + 2e–
Cr2(SO4)3 + 3Fe2(SO4)3 + 7H2O HNO2 NO2– + H2O NO3– + 2H+ + 2e–
(COOH)2 C2O42– 2CO2 + 2e–
# Intramolecular Redox Reaction H2S S2– S + 2e–
2KClO3 2KCl + 3O2 Zn Zn Zn2+ + 2e–
PCl5 PCl3 + Cl2 Al Al Al3+ + 3e–
(NH4)2Cr2O7 N2 + Cr2O3 + 4H2O
Cool Chemistry 9051122547/9339228404 4
Redox
The end point in these titrations is determined by
Titrations the use of organic dyes which are either weak acids
The process of addition of the known solution or weak bases.
from the burette to the measured volume of solution
of the substance to be estimated in the presence of an Back Titrations/Indirect Titration
indicator until the reaction between the two is just
complete, is termed as titration. Back titration is a titration method where
An endpoint is one where the test substance has the concentration of an analyte is determined by
been completely reacted with the analyzing regent. reacting it with a known amount of excess reagent.
A student estimating the concentration of a The remaining excess reagent is then titrated with
sample taken in the conical flask. The reagent added another, second reagent. The second titration's result
from burrete to estimate is called as a titrant. The shows how much of the excess reagent was used in
substance to be estimated is called titrand/titrate. the first titration, thus allowing the original analyte's
The solution consisting the substance to be concentration to be calculated.
estimated is termed unknown solution. Back titration is used when the molar
The solution in which an accurately known concentration of an excess reactant is known, but the
amount of the reagent (titrant) has been dissolved in a need exists to determine the strength or concentration
known volume of the solution is termed standard of an analyte.
solution. Back titration is typically applied in acid-base
Primary Standards Solution: These can be titrations.
accurately weighed and their solutions are not to be
standardised before use. Oxalic acid (H2C2O4.2H2O),
Potassium dichromate (K2Cr2O7), Silver nitrate Oxidation-reduction Titrations /
(AgNO3), Copper sulphate (CuSO4·5H2O), ferrous
ammonium sulphate [FeSO4.NH4HSO4·6H2O], Redox Titration
Sodium thiosulphate (Na2S2O3,5H2O), etc., are the The titrations based on oxidation-reduction
examples of primary standards. reactions are called redox titration.
(b) Secondary standards: The solutions of these Four types
reagents are to be standardised before use as these Permanganate Titrations
cannot be weighed accurately. The examples are Dichromate Titrations
sodium hydroxide (NaOH), potassium hydroxide Iodimetric Titration
(KOH), hydrochloric acid (HCl), sulphuric acid Iodometric Titration
(H2SO4), potassium permanganate (KMnO4), iodine,
etc.
Permanganate Titrations
# Types of Titration
1. Acid-base titrations or acidimetry and alkalimetry These are titrations in which potassium
2. Oxidation-reduction titrations or redox titrations permanganate is used as an oxidizing agent in acidic
3. Precipitation titrations medium.
4. Complexometric titrations. The medium is maintained by the use of dilute
sulphuric acid.
Appearance of pink colour indicates the end
Acid-base Titrations point.
Potassium permanganate acts as a self-indicator.
When the strength of an acid is determined with 2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 +
the help of a standard solution of base, it is known as 3H2O + 5[O]
acidimetry. MnO4– + 8H+ + 5e– Mn2+ + 4H2O
When the strength of a base (alkali) is KMnO4 is used to for the estimation of ferrous
determined with the help of a standard solution of an salt, oxalic acid, oxalates, hydrogen peroxide, etc.
acid, it is known as alkalimetry.
HA + BOH BA + H2O
Acid Alkali Salt Water Dichromate Titrations
Cool Chemistry 9051122547/9339228404 5
Redox
These are titrations in which potassium This type of titrations are based on the formation
dichromate is used as an oxidizing agent in acidic of insoluble precipitates.
medium. AgNO3 + NaCl AgCl + NaNO3
The medium is maintained by the use of dilute White ppt
sulphuric acid. AgNO3 + NH4CNS AgCNS + NH4NO3
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3 + White ppt
4H2O + 3[O] N.B.
Cr2O72– + 14H+ + 6e 2Cr3+ + 7H2O Titrations involving silver nitrate are called
KMnO4 is used to for the estimation of ferrous argentometric titrations.
salt and iodides.
In case of titration with ferrous salt either an
external indicator (Potassium ferricyanide) or an Complexometric Titrations
external indicator (diphenyl amine) is used.
A titration, in which an undissociated complex is
formed at the equivalence point, is called
Iodimetric Titrations complexometric titration.
These titrations are superior to precipitation
These are the titrations in which free iodine is titrations as there is no error due to co-precipitation.
used. Hg2+ + 2SCN– Hg(SCN)2
As it is difficult to prepare the solution of iodine Ag+ + CN– [Ag(CN)2] –
because it is volatile and sparingly soluble in water, it EDTA is a useful reagent which forms
is dissolved in potassium iodide solution. complexes with metals.
KI + I2 KI3 In the form disodium salt, it is used to estimate
With this solution substance such as sulphite, Ca2+ & Mg2+ ions in presence erichrome black-T as
thiosulphate, arsenite, etc, are estimated. an indicator.
N.B.
Eriochrome Black T (EBT) is a
Iodometric Titrations complexometric indicator that is used in
In this method, an OA is allowed to react in complexometric titrations.
neutral or acidic medium with excess of KI to liberate Formula: C20H12N3O7SNa
Free I2.
KI + OA I2
4KI + 2CuSO4 Cu2I2 + 2K2SO4 + I2
K2Cr2O7 + 6KI + 2H2SO4 Cr2(SO4)3 +
2K2SO4 + 7H2O + 3I2
Free I2 is titrated against a standard reducing
agent usually with Hypo (sodium thiosulphate –
Na2S2O3).
It is an azo dye.
Halogens, oxyhalogens, cupric ion, peroxides,
In its protonated form, Eriochrome Black T is
etc can be estimated by this method.
blue. It turns red when it forms a complex with
calcium, magnesium, or other metal ions.
N.B.
In both Iodimetric and Iodomertric titrations, Double Titrations
starch solution is used as indicator which gives
blue/violet colour with free I2. Double titration is a method of determining the
At the end point blue/violet colour disappears amount of substance present in the form of a solution
when iodine is completely changed to iodide. along with another solution. It can be used in the case
of a mixture of bases
involving NaOH, Na2CO3 or NaHCO3. These bases
are titrated against strong acids with proper
Precipitation Titrations indicators. Generally a single indicator is not
sufficient so two indicators are used.
Cool Chemistry 9051122547/9339228404 6
Redox
Titration Curve
# Running SA into SB
# Running WA into WB
# Running SB into SA
N.B.
There isn't any steep bit on this graph. Instead, there
is just what is known as a "point of inflexion". That
lack of a steep bit means that it is difficult to do a
# Running SA into WB titration of a weak acid against a weak base.
# Titration curves of adding hydrochloric
acid to sodium carbonate solution
Equation for Part A in Graph
Na2CO3 (aq) + HCl (aq) NaCl (aq) + NaHCO3 (aq)
Equation for Part B in Graph
NaHCO3 (aq) + HCl (aq) NaCl (aq) + CO2 (g) + H2O (l)
# Running WB into SA Overall equation
Na2CO3 (aq) + 2HCl (aq) 2NaCl (aq) + CO2 (g) + H2O (l)
# Running WA into SB
# Running SB into WA
Cool Chemistry 9051122547/9339228404 7
Redox
# Titration Curve of adding sodium
hydroxide solution to dilute ethanedioic acid
All The Best
Cool Chemistry 9051122547/9339228404 8