Hydrogen

Hydrogen & Its Compound

Hydrogen (H2)
 Form stable oxides – H2O, Na2O, K2O2, H2O2.
 Good reducing agent.

Differences with Alkali metals:

Introduction  Hydrogen > Alkali Metal (I.E)
 Size of H+ <<< alkali metal ion.
 Lightest element
 Colourless, odourless and tasteless gas. Resemblance with Halogens:
 Atomic number – 1  Like halogens, Hydrogen’s acquires noble gas
 Electronic configuration – 1s1 configurations by gaining one electron.
 Atomic weight – 1.008  I.E. of Hydrogen is of same order as Halogen.
 Group – 1 or IA  Diatomic.
 Combines with carbon (CH4, CCl4)
 Period – 1
 Hydrogen can be substitute by halogens as halogen do.
 Oxidation number – +1
FeCl3
[exception: –1 in metallic hydride ] C6H6 + Cl2 C6H5 + HCl
 Electronegativity – 2.20 (Pauling scale)
 H2 molecule – diamagnetic Difference with Halogens
 Allotropic form – ortho and para hydrogen.  Hydrogen has lower electron affinity compared to
halogens.
 B.P – -252.87 °C or 20.28 K,
 M.P – -259.14 °C or 14.01 K
 Density – 0.08988 g/L
 Insoluble in water
Preparation of Hydrogen
 Enthalpy of fusion – 0.117 kJ mol−1 Laboratory Method
 Enthalpy of vaporization – 0.904 kJ mol−1 Zn + H2SO4  ZnSO4 + H 2 
 Molar heat capacity– 28.836 J mol−1 K−1 Granulated Diluted
 Bond length (H – H) – 74 pm Zinc
 Bond energy (H – H) – 436 kJ/mole.  Conc. H2SO4 is not used because H2 is oxidised to H2O
 Ionization energies – 1312.0 kJ mol−1 by conc. H2SO4
 Covalent radius – 31±5 pm H2SO4 + Zn = ZnSO4 + H2
 Van der Waals radius – 120 pm H2SO4 = H2O + SO2 + O
 Isotopes – 1H (99.985%), 2H (0.015%), 3H (traces) H2 + O = H2O
2H2SO4 + Zn = 2H2O + SO2 + ZnSO4
N.B.
Antihydrogen – normal hydrogen is made up of one  Nitric acid cannot be used for the same reason
electron and one proton while antihydrogen is made up of 2HNO3 + Zn = Zn(NO3)2 + 2H
one positron (antiparticle of electron) and one anti proton 2HNO3 = H2O + 2NO2 + O
(antiparticle of proton). H2 + O = H2O
4HNO3 + Zn = Zn(NO3)2 + 2NO2 + 2H2O
Occurence N.B.
 Giant planets jupiter and saturn, sun and other stars Mg and Mn are the only two metals which gives H2 with
mostly consists of Hydrogen.
dil. HNO3.
 Earth crust and atmosphere - Free state – H2
 Combined state - H2O, H2O2, Hydride, Coal,  Conc. HCl is not oxidising acid but it also cannot be
Petroleum, vegetable. used. Conc. HCl is highly volatile and the produced H2
gas gets contaminated with HCl vapour.
Resemblance with Alkali metals:  Pure Zn is not used because the rate of formation of H2
 Valence electron = 1 is very slow and its forms a very thin film on pure Zn
 Form cation. surface which stops the reaction.
 Valency/ON = +1

Cool Chemistry 9051122547/9339228404 1

 Hydrogen
 Moist H2 is dried by P2O5.
 Moist H2 cannot be dried by conc. H2SO4 because it 3Fe + 4H2O Fe3O4 + 4H2
red hot steam Ferrosoferric Oxide
oxidises H2 to H2O
H2SO4 = H2O + SO2 + O Zn + H2O ZnO + H2
H2 + O = H2O red hot steam
H2SO4 + H2 = 2H2O + SO2
N.B.
# From Acids
 Na and K reacts so vigorously that it causes explosion.
 Metals (having negative standard reduction potential)
To control this amalgam of metals are used.
above hydrogen in electrochemical series produces H 2
 Couples like aluminium-mercury (Al-Hg) and zinc-
gas with dil. HCl or H2SO4.
copper (Zn-Cu) couple also gives H2 with water.
Mg + H2SO4 MgSO4 + H2,
# Electrolysis of Water
Fe + H2SO4 FeSO4 + H2  Aq solution of H2SO4, NaOH or Ba(OH)2 is
2Al + 6HCl 2AlCl3 + 3H2 electrolysed. (N.B. here acid or base is used only to
Zn + 2HCl ZnCl2 + H2 make water conductor as pure water is bad conductor
of electricity.)
N.B.
Na and K are not used because the reactions are vigorous H2O H+ + OH-
and explosion may takes places.
At Cathode: 2H+ + 2e H2
# From Alkalis At Anode: 4OH - 4e -
2H2O + O2

2NaOH + Zn Na2ZnO2 + H2
# From Metallic Hydride
hot and conc.

2NaOH + Si + H2O Na2SiO3 + 2H2 CaH2 + 2H2O Ca(OH)2 + 2H2

hot and conc. Hydrolith
2NaOH + 2Al + 2H2O 2NaAlO2 + 3H2 NaH + H2O NaOH + H2
hot and conc.

# From Water # Lane’s Process (Large Scale Preparation)

 Metals (alkali and alkaline earth metal) at top of Step 1 – Oxidation period (Production of H2)
electrochemical series (having high negative standard 750 oC
reduction potential) like Na, K gives hydrogen H2 with 3Fe + 4H2O Fe3O4 + 4H2 + Heat
1 atm
red hot steam 99% pure
cold water
ordinary Step 2 – Reduction period (Regeneration of Fe)
2K + 2H2O temperature 2KOH + H2
ordinary Fe3O4 + 4(CO + H2) 6Fe + 4CO2 + 3H2O
2Na + 2H2O temperature 2NaOH + H2 water gas
ordinary
Ca + 2H2O temperature Ca(OH)2 + H2
# Bosch Process (Large Scale Preparation)
 Metals at the middle of electro chemical series like Al, 1400 oC
Mg gives H2 with boil water. C + H2O CO + H2
white hot steam
water gas
2Al + 6H2O 2Al(OH)3 + 3H2
boiling
 Then water gas is mixed with steam where CO is
Mg + 2H2O Mg(OH)2 + H2 oxidised to CO2.
boiling
Fe2O3 (catalyst) + 500 oC
 Metals relatively low position in electrochemical series CO + H2O CO2 + H2 + Heat
Cr2O3 (promoter)
like Fe, Zn etc gives H2 with steam.
 The produced CO2 is removed from mixture by using
caustic soda.

Cool Chemistry 9051122547/9339228404 2

 Hydrogen
# From Natural Gas (CH4) [2H]
o CH2=CH2 CH3CH3
Ni + 900 C Ni
ethene ethane
CH4 + 2H2O 4H2 + CO2
20-30 atm

Chemical Properties of Unsaturated

glycerides
[H]
Ni
Saturated
glycerides

# Occlusion of Hydrogen
Hydrogen  Pd, Pt, Ni, Au can adsorb large amount of H2 gas.
 The phenomenon of adsorption of H2 gas by metal is
# With Metallic Oxides (Reducing Property) termed as Occlusion and the gas so adsorbed by metals,
CuO + H2 Cu + H2O is termed as occluded or adsorbed hydrogen.
 Decreasing order of occlusion property of metals is
PbO + H2 Pb + H2O colloidal Pd > Pd > Pt > Au > Ni
Fe2O3 + 3H2 2Fe + 3H2O  Occluded hydrogen is very active and more powerful
reducing agent than ordinary hydrogen.
# With Metals (Oxidising Property)  Ordinary hydrogen requires catalyst when treated with
I2 but occluded H2 reacts with I2 even in dark.
2Na + H2 2NaH NaH + H2O NaOH + H2
Ca + H2 Ca(OH)2 + 2H2 H2 + I2 2HI
CaH2 CaH2 + 2H2O
occluded

Here metal loses electron and hydrogen gains electron.  Ordinary H2 cannot reduce yellow solution FeCl3 but
Na – e = Na+ (oxidation) occluded H2 can reduce Fe3+ to Fe2+.
H + e = H– (reduction)
FeCl3 + H FeCl2 + HCl
occluded
# With Non-Metals
dark  Ordinary H2 cannot reduce HgCl2 but occluded H2 can
H2 + F2 2HF
do.
sunlight
H2 + Cl2 2HCl
HgCl2 + 2H Hg + 2HCl
heat
H2 + Br2 2HBr occluded

H2 + I2
Pt-catalyst
2HI # Nascent Hydrogen
 The hydrogen at the moment of its liberation from a
550 oC / 200 atm compound is known as nascent hydrogen.
N2 + 3H2 2NH3 + Heat  Stronger reducing agent than ordinary H2.
Fe (catalyst)
Mo (promoter)  Preparation
Zn + H2SO4  ZnSO4 + 2H
H2 + S H2S Na + H2O  NaOH + H
molten Na + C2H5OH  C2H5ONa + H
Sn + HCl  SnCl2 + 2H

2H + O2 2H2O
# Active hydrogen:
 When a stream of hydrogen gas at ordinary
electric
2C + H2 C2H2 temperature is subjected to silent electric discharge at
spark the 30000 volt, active hydrogen is formed.

# Hydrogenation # Atomic Hydrogen

[2H]
 Preparation
CH3CHO CH3CH2OH (i) It can be prepared by exposing ordinary hydrogen at
Ni ethanol
acetaldehyde a low pressure to a high tension electric discharge.
(ii) It can be obtained by passing molecular hydrogen
through an electric arc set up between tungsten rods at
3500-4000oC

Cool Chemistry 9051122547/9339228404 3

 Hydrogen
(iii) In recent method, hydrogen containing mercury Hfusion (kJ mol–1) 0.117 0.197 0.250
vapour is subjected to radiations shifted from a Hvaporisation (kJ mol–1) 0.904 1.226 1.393
mercury vapour are in a discharge tube. Hdissociation (kJ mol–1) 435.9 443.4 446.9
Hg + hv  Hg* Density (gL–1) 0.09 0.18 0.27
Hg*+H2 2H+Hg Vapor Pressure 54 5.8 -
(mm Hg)
N.B.
Reducing power of Hydrogen
Molecular hydrogen (H2) < Nascent hydrogen < Atomic
hydrogen.
Hydrides
Hydrogen can form binary hydrides of MHx or MmHn type
with nearly all elements except noble gases and with
# Allotropes of Hydrogen metals of group 7, 8 and 9.

Types of Hydrides
# Saline or ionic hydride (MHn)
 These are also called salt-like hydrides or electrovalent
 In ortho hydrogen the nuclear spin is in same hydrides.
direction but in para hydrogen it is in opposite  These are formed by s-block metals. (that is, low
direction.  electronegativity elements) by the transfer of an
 Para hydrogen has lower energy, therefore it is more electron from these elements to hydrogen atom.
stable and its formation is favoured at low 2Li + H2  2LiH
temperature. At room temperature, formation of Ca + H2  CaH2
ortho hydrogen is favourable due to higher  During the formation of such hydrides a part of the
molecular energy of it. energy is liberated which makes hydrogen molecules
 At ordinary temperature the ratio of ortho and para hyperactive.
hydrogen is 3 : 1 but on decreasing temperature, the  These are non-volatile, non-conducting crystalline
percentage of para hydrogen increases. solids having rock salt like structure.
 At absolute zero the gas contains 100% of the para
form. N.B.
 BeH2, MgH2, LiH are covalent and have a covalent
polymeric structure.
# Isotopes of Hydrogen  Thermal stability of such hydrides decrease down the
 Hydrogen has three isotopes: group.
1H
1
1H
2
1H
3  CaH2 is known as hydrolith.
Protium Deuterium Tritium
n=0 n=1 n=2 # Metallic or interstitial hydrides

 In nature, the isotopes of hydrogen occur in a ratio of  These are formed by transition and inner transition
1 2
1H : 1H = 6400 : l
elements which at elevated temperatures absorb
 Urey discovered heavy hydrogen or deuterium. hydrogen which easily fits in the interstitial sites of
their lattices. For example, ScH2, LaH2,VH.
7N + 20n  6C + 1H
14 1 12 2
 These hydrides have metallic appearance and posses
 Oilphant, Harteck, Rutherford prepared tritium as almost similar properties to the parent metal atom.
follows  Such hydrides in solid state are good conductors of
electricity and are used to store hydrogen in fuel
1H + 1H  1H : 1H
2 2 3 1
cells.
 Half life of 1H3 – 12.32 years  Metallic hydrides are non-stoichiometric in nature.
 Isotopic effect Due to isotopic effect, the rate of For example, TiH1.5–1.8, ZrH1.3–1.75, LaH2.87, YbH2.55,
reaction is slower in case of heavy isotopes. VH0.56, NiH0.6–0.7, PdH0.6–0.8 etc.
2 3
Property 1H1 1H 1H
Abundance 99.985% 0.0156% –15
10 % # Covalent or molecular hydrides
 These hydrides are formed by all p-block non-metals
Atomic Mass 1.008 2.014 3.016
except zero group elements. For example, CH4, NH3,
MP (K) 13.96 18.73 20.62
HF.
BP (K) 20.39 23.67 25.0
 These hydrides have a general formula MH8-n (n =
Bond Length (pm) 74.14 74.14 74.14 number of valence electrons). For example, CH4, NH3,

Cool Chemistry 9051122547/9339228404 4

 Hydrogen
HX. oleic (C17H33COOH).
 Such hydrides can be easily formed by hydrogen in  These salt when comes in contact with calcium,
direct combination with these p-block non-metals or by magnesium and iron salts present in hard water, forms
the action of water on the compounds of these elements
insoluble salt which separates out as curdy white
or by the reduction of their compounds with nascent
hydrogen. precipitates.
N2 + 3H2  2NH3 CaCl2 + 2C17H35COONa 2NaCl+Ca(C17H35COO)2
 Such hydrides are volatile and have low melting and Present Sod. Stearate Calcium Stearate
boiling points. in hard (soap) White ppt.
water
N.B.
MgSO4+2C15H31COONa Na2SO4+Mg(C15H31COO)2
 Hydrides of group III (AlH3, B2H6) being electrophiles Present Sod. palmitate Magnesium palmitate
behave like Lewis acids. in hard (soap) White ppt.
 Group 7, 8 and 9 which doesn’t form hydride is called Water
hydride gap.
 MgH2, CuH, ZnH2, CdH2 and HgH2 have properties in
 When all the Ca2+. Mg2+ and Fe2+ ions are removed
between metallic and covalent hydrides.
from hard water, then only soap produces lather

Water(H2O) N.B.
 Water containing HCl or H2SO4 or ZnSO4 or Al2(SO4)3
also behaves as hard water.
 Also known as
 Oxidane (IUPAC) # Types of Hardness of Water
 Hydrogen oxide  Temporary Hardness – due to presence of soluble
 Dihydrogen monoxide bicarbonates of calcium, magnesium and iron.
 Hydrogen monoxide  Permanent Hardness – due to presence of soluble
 Dihydrogen oxide
chlorides, sulphates of calcium, magnesium and iron.
 Hydrogen hydroxide
 Neutral oxide
 Weak electrolyte # Removal of Hardness of Water
 Density – 1000 kg/m3(4 °C) Boiling
 Melting point – 0 °C, 32 °F, 273.15 K process
 Boiling point – 99.98 °C, 211.97 °F , 373.13 K
temporary
 Acidity (pKa) – 15.74
Clark's
Removal of Hardness of Water

 Basicity (pKb) – 15.74

process
 Refractive index – 1.3330
 Dipole moment – 1.85 D
 Dielectric constant – 88.00 ε0 at 0 °C Washing soda
 Bond angle – 104.4776° permanent process

# Hard and Soft Water

 Soft water – dissolves and readily forms lather Permutit
process
 Hard water – instead of lather forms white scum.
 Hard water forms lather after consuming a considerable temporary
&
amount of soap. Calgon
permanent
process
# Cause of Hardness of Water
 Due to presence of dissolved salts like chlorides,
Ion Exchange
sulphates and bicarbonates of calcium, magnesium and process
iron.
 Soaps are soluble sodium salts of higher fatty acids like
palmitic (C15H31COOH), Stearic (C17H35COOH) and

Cool Chemistry 9051122547/9339228404 5


# Boiling Process
 Removes temporary hardness
 On boiling hard water soluble bicarbonates
decomposes to insoluble carbonates which settles down
at the bottom and filtered.
Ca(HCO3)2 = CaCO3  + CO2 + H2O
Mg(HCO3)2 = MgCO3  + CO2 + H2O
Fe(HCO3)2 = FeCO3  + CO2 + H2O
N.B.
 As MgCO3 is not completely insoluble in water,
hardness due to Mg(HCO3)2 cannot be completely
removed by boiling.
# Clark’s Process
 Removes temporary hardness
 Hardness removed by adding requisite amount of
slaked lime Ca(OH)2.
Ca(HCO3)2 + Ca(OH)2 = 2CaCO3  + 2H2O
Mg(HCO3)2 + 2Ca(OH)2 = Mg(OH)2  + 2CaCO3  +
2H2O
N.B.
 Calculated amount of slaked lime should be added,
otherwise the excess of slaked lime will absorb CO2 of
air to form soluble Ca(HCO3)2 which goes into water
making it hard again.
Ca(OH)2 + 2CO2 = Ca(HCO3)2
# Washing Soda Process
 Removes permanent hardness
 Addition of sodium carbonate converts calcium and
magnesium chloride, sulphate into insoluble carbonates
which are filtered off.
CaCl2 + Na2CO3 = CaCO3  + 2NaCl
MgCl2 + Na2CO3 = MgCO3  + 2NaCl
CaSO4 + Na2CO3 = CaCO3  + Na2SO4
# Lime Soda Process
 Removes temporary as well permanent hardness.
 Lime soda = Lime + Na2CO3.
 Addition of lime soda forms insoluble carbonates
which are filtered off.
CaCl2 + Na2CO3 = CaCO3  + 2NaCl
CaSO4 + Na2CO3 = CaCO3  + 2Na2SO4
MgCl2 + Na2CO3 = MgCO3  + 2NaCl
Ca(HCO3)2 + Ca(OH)2 = 2CaCO3  + 2H2O
N.B.
 As MgCO3 is lightly soluble in water, hardness due to
magnesium is removed by adding NaOH.
MgSO4 + 2NaOH = Mg(OH)2  + Na2SO4
Cool Chemistry 9051122547/9339228404
Hydrogen
Mg(HCO3)2 + 2NaOH = Mg(OH)2  + 2NaHCO3
# Permutit Process
 Removes temporary as well permanent hardness.
 Zeolites = complex substance containing sodium and
aluminium silicate.
 Artificial zeolite – permutit
 Permutit = Na2Al2Si2O8.xH2O (sodium aluminium
ortho silicate)
 When hard water is allowed to flow over zeolite, the
sodium ions of zeolite are displaced by Ca2+, Mg2+ and
Fe2+ ions of hard water.
 As zeolites are insoluble in water, the Ca2+, Mg2+ and
Fe2+ ions in hard water are removed and thus hard
water is made soft.
Na2(permutit) + CaCl2 = Ca Permutit  + 2NaCl
Na2(permutit) + MgSO4 = Mg Permutit  + Na2SO4
Na2(permutit) + MgCl2 = Mg permutit  + 2NaCl
Na2(permutit) + Ca(HCO3)2 = Ca permutit  +
2NaHCO3
 After long use, the sodium permutit loses its ability to
soften hard water as most of the Na+ ions of the
permutit are replaced by Ca2+, Mg2+ and Fe2+ ions of
hard water. The inactive permutit is reactivated by
passing a strong solution of NaCl (10%).
Ca Permutit + 2NaCl = Na2permutit + CaCl2
(Inactive) (Activated)
Mg permutit + 2NaCl = Na2 permutit + MgCl2
(Inactive) (Activated)
# Calgon Process
 Here, calcium and magnesium are hidden or masked by
calgon reagent that is, sodium hexametaphosphate
(Na2[Na4(PO3)6]) or sodium polymetaphosphate
(NaPO3)x. (x > 100).
 CaCl2 + Na2[Na4(PO3)6] Na2[Ca2(PO3)6] + 4NaCl
# Degree of Hardness
 Number of parts by weight of calcium carbonate or its
equivalent present in 106 parts by weight of water.
 Hardness of water in ppm =
 General soft water – 0 to 5 ppm
 Medium hard water – 10 to 20 ppm
 Hard water – 20 to 30 ppm
 Very hard water – more than 30 ppm
6
 Hydrogen
Chemical Properties of Water # With Non-Metals
C + H2O = CO + H2
white hot steam water gas
# With Acidic Oxides (Non-metallic Oxides)
Si + 2H2O = SiO2 + 2H2
 Non metallic oxides + water = acid white hot
CO2 + H2O = H2CO3
Cold Carbonic acid
Cl2 + H2O = HCl + HOCl
SO2 + H2O = H2SO3
Cold Sulphurous acid
Sunlight
2HOCl 2HCl + O2
P2O3 + 3H2O = 2H3PO3
Cold Phosphorous acid # With Metallic Hydrides
2P2O3 + 6H2O = PH3 + 3H3PO4  Metallic hydrides + H2O = metallic hydroxides + H2
Boiling phoshine phosphoric acid NaH + H2O = NaOH + H2
P2O5 + H2O = 2HPO3 CaH2 + 2H2O = Ca(OH)2 + 2H2
Cold Metaphosphoric acid

P2O5 + 3H2O = 2H3PO4 # With Metallic Carbides

Boiling phosphoric acid  Metallic carbides + H2O = metallic hydroxides + CxHy
2NO2 + H2O = HNO2 + HNO3
Cold Nitrous acid Nitric acid Al4C3 + 12H2O = 4Al(OH)3 + 3CH4
Methane
3NO2 + H2O = 2HNO3 + NO
Boiling Nitric acid Be2C + 4H2O = 2Be(OH)2 + CH4
Methane
N2O5 + H2O = 2HNO3
cold Nitric acid CaC2 + 2H2O = Ca(OH)2 + CH≡CH
Acetylene
SO3 + H2O = H2SO4
cold Sulphuric acid Mg2C3 + 4H2O = 2Mg(OH)2 + CH3C≡CH
Propyne
# With Basic Oxides (Metallic Oxides)
 Metallic oxides + water = alkali N.B.
Na2O + H2O = 2NaOH CaCN2 + 3H2O = CaCO3 + 2NH3
Calcium cynamide
K2O + H2O = 2KOH (Nitrolim)
CaO + 2H2O = Ca(OH)2 (reacts with hissing sound)
2Na2O2 + 2H2O = 4NaOH + O2
# With Metallic Nitrides
# With Metals  Metallic nitrides + H2O = metallic hydroxides + NH3
 Already done in Preparation of H2. Mg3N2 + 6H2O = 3Mg(OH)2 + 2NH3
Ca3N2 + 6H2O = 3Ca(OH)2 + 2NH3
K, Ca , Na Mg, Al, Zn, Fe Pb, Cu, Hg, Ag, Au AlN + 3H2O = Al(OH)3 + NH3

react with water react with boiling Do not react with # With Salts
water or steam in red water.
at ordinary temp.  Salt + H2O = Acid + Base
hot
FeCl3 + 3H2O = Fe(OH)3 + 3HCl (Acidic)
Na2CO3 + 2H2O = 2NaOH + H2CO3(Alkaline)
 Metal + water = metallic oxide or hydroxide + H2
# Test of water
2Na + 2H2O = 2NaOH + H2  A colourless liquid which freezes at 0oC and boils at
2K + 2H2O = 2KOH + H2 100oC at 1 atm pressure is water.
Ca + 2H2O = Ca(OH)2 + H2  When comes in contact with anhydrous CuSO4 gives
2Al + 6H2O = 2Al(OH)3 + 3H2 blue colour.
Mg + 2H2O = Mg(OH)2 + H2
3Fe + 4H2O = Fe3O4 + 4H2 CuSO4 + 5 H2O  CuSO4.5H2O
Anhydrous Copper Sulphate Hydrated Copper Sulphate
Zn + H2O = ZnO + H2
White Blue

 Quick lime reacts with water with a hissing sound.

Cool Chemistry 9051122547/9339228404 7

 Hydrogen
N.B.
 The maximum possible number of Hydrogen bonds a
water molecule can form is four.
(H2O2)
 IUPAC name – dihydrogen dioxide


Heavy Water
Appearance - Very light blue colour
 Colourless in solution
 Density – 1.110 g/cm3 (20 °C, 30-percent)
1.450 g/cm3 (20 °C, pure)

(D2O)
 Melting point – –0.43 °C, 273 K, 31 °F
 Boiling point – 150.2 °C, 423 K, 302 °F
 Soluble in water, ether, alcohol etc.
 Pure hydrogen peroxide has a pH of 6.2
 Preparation – When water is electrolysed, H2 is  Acidity (pKa) – 11.62
liberated much faster than D2, and the remaining water  Refractive index (nD) – 1.34
thus becomes enriched in heavy water.  Viscosity – 1.245 cP (20 °C)
 When the process continued until only a small volume  Dipole moment – 2.26 D
remains, then almost pure D2O is obtained.  Standard enthalpy of formation ΔfHo298 – 4.007 kJ/g
Physical Constant of H2O & D2O  Specific heat capacity – 1.267 J/g K (gas)
Property H2O D2O 2.619 J/g K (liquid)
MP(oC) 0 3.82
BP(oC) 100 101.4
Density at 20oC (g/cc)
Temp of Maxm Density (oC)
0.917
4
1.017
11.6
Structure of Hydrogen
Kw at 25oC 1.0 x 10–14 3.0 x 10–15
Dielectric Constant
Viscosity (centipoise)
78.39
0.8903
78.06
1.107
Peroxide
–1
Hformation (kJ mol ) –285.9 –294.6  All the four atoms in H2O2 do not lie in the same plane.
Hvaporisation (kJ mol–1) 40.66 41.61 It’s like an open book.
–1
Hfusion (kJ mol ) 6.01 -

Chemical Properties of D2O

 D2O + Na  NaOD + O2
 D2O + Na2O  2NaOD
 D2O + CaC2  C2D2 + Ca(OD)2
 D2O + Al4C3  CD4 + Al(OD)3
 D2O + AlCl3  DCl3 + Al(OD)3
 D2O + Mg3N2  ND3 + Mg(OD)2
 D2O + SO3  D2SO4 Structure and dimensions of the H2O2 molecule in
 Exchange Reaction the gas phase
D2O + H2O2  D2O2 + H2O
D2O + CH3COCH3  CD3COCD3 + H2O
D2O + NH4+  ND4+ + H2O
D2O + CH3COOH  CH3COOD + H2O
D2O + C2H2  C2D2 + H2O

Hydrogen Peroxide Structure and dimensions of the H2O2 molecule in

the solid phase

 H2O2 is a tautomeric mixture of two forms of structure.

Cool Chemistry 9051122547/9339228404 8

 Hydrogen
impurities present in BaO2 and which catalyse the
H H decomposition of H2O2 are removed as insoluble
O O O O phosphates.
H
H
Bayer # Merck’s Process
Kingzett
structure structure BaO2 + CO2 + H2O = BaCO3  + H2O2

Preparation of Hydrogen # From Sodium Peroxide

Na2O2 + H2SO4 = Na2SO4 + H2O2
Ice Cold 20% diluted 30% (Merck’s Perhydrol)

Peroxide  30% of H2O2 is sold in market under the trade name

Merck’s Perhydrol.
# Laboratory Method  Calculated amount of Na2O2 should be used otherwise
BaO2 + dil. H2SO4 = BaSO4  + H2O2 excess Na2O2 will reacts with water to produce NaOH
Ice cold Ice cold which acts as a positive catalyst in the decomposition
 Conc. H2SO4 or conc. HNO3 is not suitable for of H2O2.
preparation of H2O2 because conc. H2SO4 or conc. Na2O2 + 2H2O  2NaOH + H2O2.
HNO3 oxidises H2O2.
# Electrolytic Process (Large Scale Preparation)
H2SO4 = H2O + SO2 + O2  Raw material – 50% H2SO4
H 2O 2 + O = H2O + O2 – Copper as cathode
H2SO4 + H2O2 = SO2 + 2H2O + O2 – Platinum as anode
 Reactions
2HNO3 = H2O + 2NO2 + O
2H2SO4 2H+ + 2HSO4-
H 2O 2 + O = H2O + O2
2HNO3 + H2O2 = 2NO2 + 2H2O + O2 At cathode: 2H+ + 2e = H2
 Conc. or dil. HCl is not suitable for preparation of
At anode: 2HSO4- - 2e = 2HSO4
H2O2 because it produces BaCl2 which is soluble in
water and cannot be easily separated from aqueous 2HSO4 H2S2O8(perdisulphuric acid)
solution of H2O2.
H2S2O8 + 2H2O = 2H2SO4 + H2O2
 The temperature during the reaction is kept at 0oC
because H2O2 is presence of heat rapidly decomposes N.B.
into H2O and O2. During hydrolysis of perdisulphuric acid, permono
2H2O2  2H2O + O2 sulphuric acid (Caro’s caid) is also formed
 At the end of reaction between BaO2 and dil. H2SO4 H2S2O8 + H2O = H2SO4 + H2SO4
the final solution is kept slightly acidic because acid H2SO5 + H2O = H2SO4 + H2O2
acts as negative catalyst and retards the rate of
decomposition of produced H2O2.
 The paste of BaO2 is added to the acid solution but the # Auto Oxidation Process (Large Scale
reverse is not done - when paste of BaO2 is added, Preparation)
there is excess of H2SO4 remains in the mixture which
O OH
retards the decomposition of H2O2. II C2H5 I C2H5
2H
# From BaO2 and Orthophosphoric Acid pd cat
II
3BaO2 + dil. 2H3PO4 = Ba3(PO4)2  +3 H2O2 O
I
OH
Ice cold Ice cold
2 ethyl anthraquinone 2 ethyl anthraquinol
 H2SO4 acts as a catalyst for decomposition of H2O2.
Therefore, some weak acids such as H3PO4 is preferred
over H2SO4 for preparing H2O2 from peroxides.
 Further this method has the advantage over BaO2-
H2SO4 method since all the heavy metal (e.g. Pb, Bi)

Cool Chemistry 9051122547/9339228404 9

 Hydrogen
OH O
which decomposes to give nascent oxygen.
I C2H5 II C2H5 H2O2  H2O + [O]
O2
+ H2O2  From the given standard reduction potential it is clear
air
I II
that H2O2 is a strong reducing agent.
OH O
H2O2 + 2H+ + 2e 2H2O E0 = 1.77 volt

O2 + 2H+ + 2e H2O2 E0 = 0.68 volt

HO2- + H2O + e 3OH E0 = 0.87 volt

 In acidic medium oxidising action is slow while in

basic medium, it is fast.
 Only in presence of very strong acid (like KMnO4)
behaves as reducing agent.
# Stability of Hydrogen Peroxide  In acidic
 Unstable due to presence of peroxo bond.  Oxidises black lead sulphide to white lead sulphate.
 At ordinary temperature decomposes
2H2O2  2H2O + O2 + 46.1 kcal 4H2O2 = 4H2O + 4O
 Thermodynamically, process is spontaneous
PbS + 4O = PbSO4
H2O2(l)  H2O(l) + ½ O2(g) ; G = –122.6 kJ -2 -6
 Positive catalyst – alkali, MnO2, Au, Pt, Heat, light, PbS + 4H2O2 = PbSO4 + 4H2O
rough surface.
 Negative catalyst – acid, alcohol, glycerol. N.B
 H2O2 is stored in a wax coated glass bottle or in a H2O2 is used for restoring colour of old paintings – old
polythene bottle to avoid its decomposition by the oil paintings contains white lead pigment [2PbCO3,
alkali present in glass. Pb(OH)2]. On prolonged exposure to atmosphere H2S
reacts with this compound of lead converting it into

Chemical Properties of
black PbS.
PbCO3 + H2S  PbS + CO2 + H2O
Pb(OH)2 + H2S  PbS + 2H2O

Hydrogen Peroxide H2O2 converts black PbS to white PbSO4, as a result

the blackened oil paintings get their original colour.
# Acidic Property PbS + 4H2O2  PbSO4 + 4H2O
 Very weak acid  Oxidises acidified ferrous salt to ferric salt.
 In aqueous solution, its is more acidic than water
H2O2 = H2O + O
+ - -12
H2O2 H + HO 2 K = 1.5 x 10 2FeSO4 + H2SO4 + O = Fe2(SO4)3 + H2O
+2 +3
H2O H+ + OH- K = 1 x 10-14 2FeSO4 + H2O2 + H2SO4 = Fe2(SO4)3 + 2H2O

 Turns blue litmus red Similarly

 Reacts with base to give salt and water.
2NaOH + H2O2 = Na2O2 + 2H2O H2O2 = H2O + O
Ba(OH)2 + H2O2 = BaO2 + 2H2O 2FeCl2 + 2HCl + O = 2FeCl3 + H2O
NH3 + H2O2 = NH4O2H +2 +3
2FeCl2 + H2O2 + 2HCl = 2FeCl3 + 2H2O
# Peroxidising Property colourless yellow
Na2CO3 + H2O2 = Na2O2 + CO2 + H2O
 Oxidises acidified KI or NaI to free I2.
# Oxidising Property
 Strong oxidising agent due to presence of peroxo bond

Cool Chemistry 9051122547/9339228404 10

 Hydrogen
H2O2 = H2O + O H2O2 = H2O + O
2KI + O = K 2 O + I2 SnCl2 + 2HCl + O = SnCl4 + H2O
K2O + 2HCl = 2KCl + H2O +2 +4
SnCl2 + 2HCl + H2O2 = SnCl4 + 2H2O
-1 0
2KI + H2O2 + 2HCl = 2KCl + I2 + 2H2O
colourless brown N.B.
H2O2 is reduced to water in all of the above reactions.
Similarly
2NaI + H2O2 + 2HCl  2NaCl + I2 + 2H2O # Reducing Property
 Oxidises nitrite to nitrates.  Pink colour acidified potassium permanganate is
reduced to colourless manganous salt.
H2O2 = H2O + O
KNO2 + O = KNO3 2KMnO4 = K2O + 2MnO + 5O

+3 +5 5H2O2 + 5O = 5H2O + 5O2

KNO2 + H2O2 = KNO3 + H2O
2MnO + 2H2SO4 = 2MnSO4 + 2H2O
Similarly +7 -1 +2 0
2KMnO4 + 5H2O2 + 3H2SO4 = K2SO4 + 2MnSO4 + 5O2 + 8H2O
HNO2 + H2O2  HNO3 + H2O pink colourless
 Oxidises acidified potassium ferrocyanide to potassium
ferricyanide.
 Orange coloured acidified potassium dichromate is
H2O2 = H2O + O reduced to green colour of chromic salt.
K2Cr2O7 + H2SO4 = H2Cr2O7 + K2SO4
2K4[Fe(CN)6] + O = 2K3[Fe(CN)6] + K2O
H2Cr2O7 + 4H2O2 = 2CrO5 + 5H2O
K2O + 2HCl = 2KCl + H2O K2Cr2O7 + H2SO4 + 4H2O2 = 2CrO5 + K2SO4 + 5H2O
Orange
+2 +3
2K4[Fe(CN)6] + H2O2 + 2HCl = 2KCl + 2K3[Fe(CN)6] + 2H2O 4CrO5 + 6H2SO4 = 2Cr2(SO4)3 + 7O2 + 6H2O
(green)

 Oxidises sulphurous acid to sulphuric acid.

 Sodium or potassium hypobromite is reduced to
H2O2 = H2O + O bromide
H2SO3 + O = H2SO4 +1 -1
+4 +6 NaOBr + H2O2 = NaBr + H2O + O2
H2SO3 + H2O2 = H2SO4 + H2O
 Acidified MnO2 is reduced to MnSO4
 Oxidises sulphites to sulphates.
+4 +2
MnO2 + H2SO4 + H2O2 = MnSO4 + 2H2O + O2
H2O2 = H2O + O
Na2SO3 + O = Na2SO4  Silver oxide is reduced to metallic silver.
+4 +6 H2O2 = H2O + O
Na2SO3 + H2O2 = Na2SO4 + H2O Ag2O + O = 2Ag + O2
Ag2O + H2O2 = 2Ag + O2 + H2O
 Oxidises H2S to free S.
 Lead dioxide is reduced to lead monoxide
H2O2 = H2O + O
PbO2 + H2O2 = PbO + H2O + O2
H2S + O = S + H2O
 Bleaching powder is reduce to calcium chloride
-2 0
H2S + H2O2 = S + 2H2O Ca(OCl)Cl + H2O2 = CaCl2 + H2O + O2

 Oxidises acidified SnCl2 to SnCl4.  Alkaline potassium ferricyanide is reduced to

potassium ferrocyanide.

Cool Chemistry 9051122547/9339228404 11

 Hydrogen
 ‘x volumes of H2O2’ means x ml of O2 is liberated on
+3 +2
2K3[Fe(CN)6] + 2KOH + H2O2 = 2K4[Fe(CN)6] + 2H2O + O2 decomposition of 1 mL of H2O2.
 ‘10 volumes of H2O2’ means 10 ml of O2 is liberated
on decomposition of 1 mL of H2O2.
 Ozone is reduced to oxygen.  ‘20 volumes of H2O2’ means 20 ml of O2 is liberated
O3 + H2O2 = 2O2 + H2O on decomposition of 1 mL of H2O2.
 Chlorine or bromine reduced to HCl or HBr.  Conversion factor –
Cl2 + H2O2 = 2HCl + O2 1 volume of H2O2 = 0.3036% strength
Br2 + H2O2 = 2HBr + O2 1 volume of H2O2 = 3.036 gL–1
(N) of H2O2 =
N.B.
H2O2 is oxidises to O2 in all of the above reactions. (M) of H2O2 =

# Formation of Addition Compounds

HF + H2O2  HF.H2O2
(NH4)2SO4 + H2O2  (NH4)2SO4.H2O2
Ammonium sulphate

CO(NH2)2 + H2O2  CO(NH2)2.H2O2

Urea

# Bleaching Property
 H2O2 can bleach silk, wool etc due to nascent oxygen.
H2O2 = H2O + O
[O]
Coloured matters Bleached substance

# Test of Hydrogen Peroxide

 H2O2 liberates free I2 when treated with acidified KI or
NaI. Starch when comes in contact with I2 turns blue.
2KI + 2HCl + H2O2 = 2KCl + I2 + 2H2O
I2 + starch  blue substance
 When H2O2 is shaken with acidified solution of
K2Cr2O7 with little ether, the ether layers turns blue due
to formation of CrO5 (perchromic acid).
K2Cr2O7 + H2SO4 = H2Cr2O7 + K2SO4
H2Cr2O7 + 4H2O2 = 2CrO5 + 5H2O
Perchromic acid

Blue

The blue turns green as the produced CrO5 is converted

to chromic sulphate
4CrO5 + 6H2SO4 = 2Cr2(SO4)3 + 7O2 + 6H2O
Chromic sulphate

Green

 On adding few drops of H2O2 to titanium sulphate, the

colourless solution turns orange red
Ti(SO4)2 + 2H2O2 = TiO3 + 2H2SO4 + ½O2

# Strength of Hydrogen Peroxide

 The strength of H2O2 in volume, is the volume of
oxygen in cm3 at NTP which is evolved by the
decomposition of one cm3 of H2O2 solution by the
application of heat or by contact with a catalyst.

Cool Chemistry 9051122547/9339228404 12