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6. HYDROGEN AND IT’S COMPOUNDS

Synopsis :
Hydrogen is the most abundant element in the universe. It is the 9th most abundant element in the earth's crust. It occurs only in the combined state except in volcanic gases where it occurs in free state. • It is the first element in the periodic table. • It is the lightest of all the elements. • It is the only element without neutrons i.e. Protium. • It is the element with ambiguious position in the periodic table, as it resembles both I-A and VII-A group elements. • Hydrogen should belong to the s-block as its electron configuration is 1s1. • The properties in which hydrogen resembles alkali metals are a) Like alkali metals it has one electron in s-orbital of valence shell. b) Like Alkali metals, it forms H+ ion. c) Like Alkali metals it forms monoxides and peroxides. d) Like Alkali metals, it acts as reductant. • The properties in which Hydrogen resembles Halogens are a) Like Halogens it exists as diatomic molecule (H2) b) Like Halogens it gains one electron to attain inert gas configuration c) The I.P value of "H" is similar to that of Halogens. d) Like halogens it forms univalent anion i.e H–. • Hydrogen has 3 isotopes. They are Protium Deuterium Tritium • • • • •
1 1H 1H 1H 2 3

Theoritically the number of possible Hydrogen molecules is six. They are H2, D2, T2, HD, HT and DT. Ordinary Hydrogen contains only 0.02% Deuterium. Hydrogen and Deuterium can be separated by gas diffusion principle. Hydrogen is more reactive than Deuterium. All the isotopes of Hydrogen have a) same chemical properties b) same atomic radii c) same bond lengths The isotopes of Hydrogen differ widely due to large difference in mass numbers. a) Number of neutrons b) Chemical reactivity 1

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Powered by www.myengg.com Hydrogen and its compounds c) Physical properties d) Nuclear radii e) Bond energy The properties or physical constants which are lower for hydrogen than that of deuterium are i) Molecular weight ii) Boiling point iii) Melting point iv) Latent heat of fusion v) Latent heat of vaporization vi) Bond energy vii) Activation energy Chemical reactivity is higher for hydrogen than that of Deuterium. On electrolysis of water, H2 is released six times faster than that of D2. Ordinary Hydrogen contains Tritium and protium in the ratio 1 : 1017. Tritium can be obtained in the nuclear transformations such as 14 1 12 3 7N + on →6C + 1T (occurs in nature) 6 1 4 3 3Li + on → 2He + 1T (takes place in nuclear reactors) The radioactive isotope of Hydrogen is Tritium. It is a beta emitter and its half life is 12.26 years 3 3 0 1T →2 He + - 1e (β - particle) Tritium is harmless, as it emits only low energetic β-radiation and will not emit harmful γ-rays. In the study of mechanism of various chemical reactions, Deuterium and Tritium are used as tracers. As the mass number increases the chemical reactivity decreases. So chemically least reactive isotope of Hydrogen is Tritium. Uses of Hydrogen Hydrogen is used i) in the manufacture of chemicals ii) in metallurgy iii) as a source of atomic energy iv) as a fuel. a) Synthesis of Ammonia by Haber's process. N2(g) + 3H2(g) b) Preparation of HCl
H2(g) + Cl2( g) → 2HCl(g) ⎯⎯ ⎯ → 2HCl(aq) ⎯
acid water

• •

• • • •

2 NH3(g)

c) Synthesis of Methyl alcohol:
3 H 2 + (CO + H 2 ) ⎯⎯ ⎯ ⎯⎯→ CH3OH

ZnO.CrO

water gas

(catalyst )

• • •

d) In the production of vanaspathi or Margarine: Synthetic petrol is prepared by Fischer-Tropsch process. Here Iron oxide is used to remove sulphur from a mixture of water gas and Hydrogen. Synthetic petrol is obtained by passing a mixture of water gas and Hydrogen free from sulphur over Cobalt catalyst. The heat of combustion of H2 gas is high (242 KJ/mole). Hence it is used as an industrial fuel. 2

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Powered by www.myengg.com Hydrogen and its compounds Liquid Hydrogen is used as fuel in the rocket. In “SATURN-V" that took Neil Armstrong to the moon liquid hydrogen is used. OXY hydrogen torch produces a very high temperature of 28000C. It is used for welding purpose and for melting platinum and Quartz. The fuel gases containing H2 is the important constituent of many fuel gases such as a) Coal gas b) Water gas c) Carburetted water gas d) Semi water gas Coal gas: It is obtained by the destructive distillation of coal The composition of Coal gas is H2 = 45 - 55% CH4 = 25-35% CO = 4 - 11% Coal gas has highest calorific value Water gas: It contains H2 and CO in 1 : 1 ratio by volumes. It is prepared by passing steam over white hot coke or coal. Carburetted water gas is obtained by adding gaseous Hydrocarbons to water gas. The calorific value of carburetted water gas is more than that of water gas due to the presence of Hydrocarbons. Semi water gas: It is obtained by passing a mixture of air and steam over red hot coke. It is the mixture of CO, H2, N2. % by volume : N2 > CO > H2 The calorific value of semi water gas is low. It is used as a fuel in steel industry. Fuel cells:- In these cells heat energy produced by burning of fuel gases is converted into electrical energy. The fuel cell which involves the burning of H2 and O2 is used in Apollo series of rockets. The water formed in the combustion of Hydrogen is condensed and used as drinking water by astronauts. In Hydrogen - oxygen fuel cell, carbon electrodes and NaOH electrolyte is used. Electrode reactions: At anode : 2(H2+2OH → 2H2O + 2e- )
e ⎯ At cathode : O2 + 2H2O ⎯4⎯→ 4OH Cell reaction : 2H2 + O2 → 2H2O The efficiency of fuel cells is very high because the heat energy is directly converted into electrical energy. Theoretically the efficiency of fuel cell should be 100 % but practically an efficiency of 60 - 70% has been achieved so far. Hydrogen is used as a reducing agent in the extraction of heavier metals like Molybdenum and Tungsten. WO3 + 3H2 → W + 3H2O The energy emitting from sun and stars is due to nuclear fusion reactions involving Hydrogen nuclei.

• • •

• • • • • • • • • • •

Fusion reaction 2 2 4 1H + 1H →2He

Energy released 23 × 108 KJ / mole of 3

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Powered by www.myengg.com Hydrogen and its compounds "He" + 1H →2He 1 + 0n 17.2 ×108 KJ / mole of "He" 41H1 →2He4 + 2 0 1e 26 × 108 KJ / mole of "He"
1H 2 3 4

Hydrogen bomb involves hydrogen nuclei fusion. The binary compounds of hydrogen with other elements are called hydrides. The hydrides have the formula MHx or (Mm Hn) These are formed by i) all main group elements except the noble gases and probably Indium and thallium. ii) All lanthanides and Actinides. iii) Transition elements such as Sc, Y, La, Ac, Tc, Zr, Hf and to lesser extent V, Nb, Ta, Cr, Cu and Zn • On the basis of their physical and chemical properties and types of bonding they are classified into the following four types. 1) Ionic hydrides (or) saline hydrides. 2) Covalent (or) molecular hydrides. 3) Metallic (or) Interstitial hydrides. 4) Polymeric hydrides. IONIC HYDRIDES (or) SALINE HYDRIDES : • These are formed by elements of group IA, IIA (except Be and Mg) and lanthanides by heating the metal in hydrogen.
573 K 2Na + H2 ⎯⎯⎯→ 2NaH

• • •

673K 2K + H2 ⎯⎯⎯→ 2KH 1073 K Ca + H2 ⎯⎯⎯⎯ CaH2 → 1123 K Sr + H2 ⎯⎯⎯⎯ SrH2 → These are white colourless solids (crystalline) having high melting point and boiling point easily decomposed by water, alcohol, CO2 (or) SO2

CaH2 + 2H2O ⎯⎯ Ca(OH)2 + 2H2 → CaH2 + 2C2H5OH ⎯⎯ Ca(OC2H5)2 + 2H2 → • • • • • • • CaH2 + 2CO2 ⎯⎯ (HCOO)2Ca → Except LiH. all ionic hydrides 400°C-500°C (on strong heating) into their constituent elements. Electrolysis of these molten hydrides produce hydrogen gas at anode.
− 2H(molten) ⎯⎯ H2(g) ↑ + 2e →

decompose

at

This reaction provides chemical evidence for the presence of H– in these hydrides This type of hydrides are formed only by elements with electronegativity value that is less than 2.1. Hydrogen compounds of high electropositive metals may be regarded as the metal hydride. The density of these hydrides is greater than that of the metal from which they are formed. These ionic hydrides are stoichiometric and have high heats of formation. 4

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Powered by www.myengg.com Hydrogen and its compounds They act as powerful reducing agents especially at high temperature. Ex. 1) NaH reduces CO and CO2 to formates on heating
Δ 2CO + NaH ⎯⎯ HCOONa + C →
Δ → CO2+NaH ⎯⎯ HCOONa + C (Sodium formate) 2) Reduces sulphates to sulphide

PbSO4 + 2CaH2 ⎯⎯ PbS + 2Ca(OH)2 → 3) Reduces some halides and oxides
Δ → SiCl4 + 4NaH ⎯⎯ SiH4 + 4NaCl 4) Reduces organic acids to alcohols

RCOOH + 2LiH ⎯⎯ RCH2OH + Li2O → USES OF IONIC HYDRIDES : • Metal hydrides are used in laboratory to remove traces of water from solvents and inert gases such as N2 and Ar. • Alkali metal hydrides are used to prepare other hydride compounds Like - LiAlH4, NaBH4 etc. • Since they evolve hydrogen when heated and therefore ignite spontaneously they are used as solid fuels. MOLECULAR (OR) COVALENT HYDRIDES : • These hydrides are formed by the combination of elements of comparatively higher electronegatively as p-block elements. (IIIA to VIIA groups) Ex. NH3, HCl, CH4, H2O, HF, B2H6, AsH3 • Their molecular formula can be written as MHn (or) MH8–n n = group number of element in short form of periodic table • The molecular hydrides are classified into three categories. • Electron – precise compounds: In these compounds all the electrons of the atom are involved in bond formation. Ex. CH4 (methane), C2H6 (ethane) • Electron – deficient compounds: In these compounds the available number of valence electrons are less than the number required for covalent bond formation (or) writing the Lewis structure of the molecule. Ex. B2H6, (AlH3)n • Electron rich compounds: In these compounds the valence electrons on the central atom are more than that are required for bond formation. i.e. lone pair present on the central atom. Ex. NH3, H2O • The bonds present in this hydrides are mostly covalent in character. • Covalent hydrides like HF, HCl are partly ionic in nature. • The molecules are held together by weak van der Waal’s forces. PREPARATION OF COVALENT HYDRIDES : 1) By direct combination of elements H2 + F2 ⎯⎯ 2HF → 3H2 + N2 ⎯⎯ 2NH3 → 5

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Powered by www.myengg.com Hydrogen and its compounds 2H2 + O2 ⎯⎯ 2H2O H2 +Cl2 ⎯⎯ 2HCl → → 2) By the hydrolysis of metal borides, carbides, nitrides, phosphides etc. Mg3B2 + 6H2O ⎯⎯ 3Mg(OH)2 + B2H6 →
Diborane

Al4C3 + 12H2O ⎯⎯ 4Al(OH)3 + 3CH4 → Ca3P2 + 6H2O ⎯⎯ 3Ca(OH)2 + 2PH3 →
phosphine

3) By reduction of certain compounds by nascent hydrogen (or) by using reducing agent like LiAlH4 (ether solution) AsCl3 + 6(H) ⎯⎯ AsH3 + 3HCl →
ether SnCl4 + LiAlH4 ⎯⎯⎯→ LiCl + AlCl3 + SnH4

s tan nane

Nomenclature and classification of covalent hydrides • The systematic (or) IUPAC name of these hydrides are usually formed from the name of the element and the suffix – ane Element B C N P As Sb O S F Cl Group No. in the P.T. III (13) IV (14) V (15) V (15) V (15) V (15) Vi (16) VI (16) VII (17) VII (17) Formula of the hydride B2H6 CH4 NH3 PH3 AsH3 SbH3 H2O H 2S HF HCl Name of the hydride IUPAC Diborane (6) Methane Azane Phosphane Arsane Stibane Oxidane Sulphane Hydrogen Fluoride Hydrogen chloride Common Diborane Methane Ammonia Phosphine Arsine Stibine Water Hydrogen sulphide Hydrogen fluoride Hydrogen chloride

• Molecular hydrides are soft, have low melting point and low boiling point. • Molecular hydrides are volatile in nature have low electrical conductivity. METALLIC HYDRIDES: • Most of the d-block elements and f block elements from metallic hydrides on reacting with hydrogen. Ex. CrH, CrH2, ZnH2, ThH2 • Metallic hydrides are normally prepared by heating the metal with hydrogen under high pressure. • Most of the metallic hydrides are metallic conductors and have variable composition. • These hydrides have properties similar to those of parent metals. • Metallic hydrides are hard, have metallic lustre and have magnetic properties. • The density of these hydrides is less than that of the parent elements. 6

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Powered by www.myengg.com Hydrogen and its compounds • Metallic hydrides exhibit metallic properties and are powerful reducing agents. • Metallic hydrides are non-stoichiometric compounds and their composition varies with temperature and pressure. Ex. (BeH2)n, (MgH2)n, (AlH3)n • Be and Mg of s-block and aluminium also form metallic hydrides. • In these hydrogen exist in the atomic rather than ionic form. • These are interstitial compounds as the hydrogen atom occupy interstitial positron in the metal lattices. • This is due to small size of hydrogen atoms compared to metal atom. • The finely divided metals obtained by thermal decomposition of these hydrides are used as catalyst and in metallurgy. • The formation of the metallic hydrides and their capacity to release hydrogen at higher temperature are utilized in purification of H2 ((Pd –Ag alloys is used) and for storing hydrogen. POLYMERIC HYDRIDES : • These are solids containing molecules linked together in two (or) three dimensions by hydrogen bridge bonds. (BeH2)n, Mg(H2)n and (AlH3)n HYDROGEN AS FUEL : • Hydrogen readily burns in air gives large amount of heat 242 kJ mol–1. • It does not give any polluting bi products. Therefore it is used as fuel. • Hydrogen is potential fuel for automobiles than gasoline because it can provide large amount of energy per unit mass without producing biproducts such as CO2, CO, SO2 and unburnt hydrocarbons which causes pollution. • Hydrogen is an important component of many industrial fuels like coal gas, water gas, carburetted water gas and semiwater gas. • Hydrogen burnt with O2 gives a flame temperature of 2800°C. this flame is called oxy hydrogen blow torch. • Oxy hydrogen torch used for welding works and to melt substances like pt, quartz etc. • Atomic hydrogen torch used as oxy-hydrogen blow torch. INDUSTRIAL FUEL GASES – CALORIFIC VALUES: • Coal gas: Preparation : destructive distillation of coal Composition : H2 → 45 – 55% CH4 → 25 – 35% CO → 3 – 11% Calorific value : 21,000 KJ m–3 • Water gas: Preparation : passing steam over red hot coke (1000°C) or coal Composition : H2 → 45 – 50% CO → 40 – 50% Small amount of CO2 and N2 Calorific value : 13,000 KJ m–3 7

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Powered by www.myengg.com Hydrogen and its compounds Semiwater gas: Preparation : A mixture of steam and air passed over red hot layers of coal. Composition : H2 → 10 – 12% CO → 25 – 28% CO2 → 4 – 5% N2 → 50 – 55% CH4 → 1 – 2% Calorific value : 75.24 KJ mol–1 • Carburetted water gas: Preparation : Hydrocarbons from the cracking of petroleum oils are mixed with water gas. Composition : water gas + hydrocarbons Calorific value : 15,048 KJ mol–1 FUEL CELLS: • In the combination of fuel gases like H2, CO and methane energy produced is converted into electrical energy in the fuel cells. • A fuel cell consist of porous carbon electrodes suspended in NaOH solution. H2 and O2 gases are bubbled at the surface of electrodes. • Electrodes are embedded with suitable catalyst. • The electrode reaction in hydrogen fuel cell
+4e At cathode : O2(g) + 2H2O(l) ⎯⎯⎯ 4OH–(aq) →

At anode •

−2e : 2×[H2(g) + 2 OH–(aq) ⎯⎯⎯ 2H2O(aq) →

→ 2H2(g) + O2(g) ⎯⎯ 2H2O(l)

In fuel cells the heats of combustion of fuel materials are directly converted into electrical energy. • In the traditional methods of generating electricity by H2 (or) C by nuclear reactor there is a loss of energy in such process. • The fuel cell have more efficiency and prevents the atmospheric pollution. • In spite of the fuel value of hydrogen (heat combustion of H2 = 242 KJ mol–1). It is not used frequently due to the following reasons. 1) Hydrogen elements is not present in the free state in nature. 2) The storing and Transportation of hydrogen gas is dangerous and involves risks. WATER : Water is called as universal solvent because it is an excellent solvent for ionic compounds and polar covalent compounds. 3/4th of earth's surface is covered by water. Purest form of natural water is rain water. Potable water means which is for drinking. Hardness of water: • Chemically soap is sodium stearate. • Water which gives good lather readily with soap is known as soft water. 8

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Powered by www.myengg.com Hydrogen and its compounds Water which does not give lather readily with soap but precipitates soap is known as hard water. When soap is added to hard water Na+ of soap are replaced by Ca2+ or Mg2+ ions and precipitates as Ca or Mg soap. The disadvantages of using hard water are a) It produces boiler scales b) It causes wastage of soap in laundries Hardness of water is expressed in terms of ppm of CaCO3. That means the number of grams of CaCO3 (or) its equivalent part present in 1 million grams of water is known as hardness. Hardness is of two types. They are 1) Temporary hardness 2) Permanent hardness Temporary hardness of water is due to the presence of the bicarbonates of Ca and Mg. Permanent hardness of water is due to the presence of the chlorides and sulphates of Ca, Mg, Fe. Temporary hardness of water can be removed by 1) Boiling 2) Clark's Method Boiling removes the temporary hardness as soluble bicarbonates convert into insoluble carbonates Ca(HCO3)2 ⎯Δ CaCO3↓ + H2O + CO2↑ ⎯→ Mg(HCO3)2 ⎯Δ MgCO3↓ + H2O + CO2↑ ⎯→ • In Clark's method temporary hardness can be removed by adding a calculated quantity of milk of lime. Ca(HCO3)2 + Ca(OH)2 → 2CaCO3↓ + 2H2O If excess of lime is added it will cause permanent hardness. Using Na2CO3 both temporary and permanent hardness can be removed. • The methods used for removing permanent hardness are a) Permutit method b) Ion exchange method c) Calgon method • a) Permutit is an artificial zeolite. Chemically permutit is hydrated sodium aluminum ortho silicate. Its formula is Na2 Al2 Si2 O8. x H2O. b) Gan's permutit process is also known as Base exchange process. Na2Al2Si2O8.xH2O + Ca2+ → CaAl2Si2O8.xH2O + 2Na+ • The exhausted permutit is regenerated by treating 10% NaCl solution [Brine solution] • Calgon is sodium hexameta phosphate. Its formula is Na2 [Na4(PO3)6)] or (NaPO3)6 • Calgon removes hardness by forming complex compounds with the Ca2+ and Mg2+ ions of hard water or by adsorption. Ion exchange method: • Deionised water is obtained in ion exchange method. It is free from all ions. It can be used in place of distilled water. • Cation exchange resin is RCOOH or RSO3H and anion exchange resin is RNH3OH. 9

• • •

• •

• • • •

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Powered by www.myengg.com Hydrogen and its compounds • In cation exchange resin, the cations of hard water get replaced by H+ ions. 2RCOOH + Ca2+ → (RCOO)2 Ca + 2H+ Resin (from hard water) • In anion exchange resin the anions of hard water get replaced by OH– ions. (RNH3)OH + Cl– → (RNH3)Cl + OH Resin (from Hard water) • The exhausted cation exchange resin can be regenerated by moderately concentrated H2SO4 solution. Degree of hard ness: It is expressed in PPM in terms of CaCO3. It is the number of parts by weight of CaCO3 in one million parts by weight of water Degree of hardness in PPM =
weight of CaCO3 × 106 weight of H2O

100g CaCO3 = 162 g Ca(HCO3)2 ; = 111 g of CaCl2 = 136 g of CaSO4 ; = 95 g of MgCl2 = 120 g of MgSO4 ; = 146g of Mg(HCO3)2 Heavy water: • Heavy water was discovered by Urey. • Heavy water is Deuterium oxide • Source of heavy water is normal water • Natural water contains I part of heavy water in 6000 parts of ordinary water. • Heavy water is also found in Himalayan snow melting areas and in the leaves of banyan trees, rain water. • Theoretically possible number of water molecules by using all the 3 isotopes of hydrogen and all the 3 isotopes of oxygen (O16, O17, O18) are 18. Theoretically possible number of heavy water molecules are six. T2O is super heavy water. They are D2O16, D2O17, D2O18, HDO16, HDO17, HDO18. Preparation of D2O Preparation of D2O can be obtained by two methods. They are a) Exhaustive electrolysis of alkaline water. b) Exchange process. • Heavy water is prepared by the exhaustive electrolysis of water containing N/2 NaOH. • In the preparation of heavy water by electrolytic method, the cathode is steel vessel and anode is a perforated cylindrical Nickel sheet. • 30 litres of water on electrolysis gives 1 ml. of D2O. Electrolysis occurs in 7 stages. • At the end of 1st stage, volume becomes 1/6. Alkali present in the water is neutralised by passing CO2 gas. • During electrolysis bonds in H2O are broken 18 times faster and H2 gas is released about six times faster than that of D2. • In the electrolysis, H2 and D2 are liberated at cathode and O2 is liberated at anode. 10

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Powered by www.myengg.com Hydrogen and its compounds • • At the end of 7 stage, 99% D2O is obtained. D2O can be prepared by exchange reactions. When H2S gas is passed through hot water, the hydrogen atoms in H2S exchange with deuterium from D2O present in water. Thus H2S becomes D2S. On passing D2S through cold water, the deuterium from D2S and Hydrogen from H2O exchange and the cold water becomes richer in D2O. The process is repeated. The reaction in which interchange of the isotopes of an element take place between two compounds is known as an isotopic exchange reaction. Isotopic exchange reactions occur more readily with compounds containing active or labile Hydrogens. Eg.: HCl + D2O → HDO + DCl NaOH + D2O → NaOD + HDO NH4Cl + D2O → NH3DCl + HDO The reaction of salt with D2O is known as Deuterolysis Eg.: AlCl3 + 3D2O → AI (OD)3 + 3DCl Salts like CuSO4. 5H2O, MgSO4.7H2O are known as deuterated salts or salt deuterates. Heavy water is toxic to micro organisms. Both H2O and D2O are associated liquids due to Hydrogen (or Deuterium) bonds. But the boiling point of water is less than that of D2O. This is because the molecular weight of D2O is greater than that of H2O. Chemical Properties of D2O:
⎯⎯ ⎯ ⎯ ⎯→ D 2 ↑ + O 2 ↑ ⎯
⎯⎯ → D 2 + ⎯
2 ⎯⎯ ⎯ → ⎯

th

• • • •

electrolysis

Na

NaOD Sodium-deuteroxide

Na O

NaOD Ca(OD)2 Calcium deuteroxide

⎯⎯⎯→
SO3

CaO

⎯⎯⎯→ D 2 SO 4 Deutero sulphuric acid

DNO3 Deutero Nitric acid Mg3N D2O ⎯⎯ ⎯2 → Mg(OD ) + ND ⎯ 3 2
2 5 ⎯⎯ ⎯ → ⎯

N O

Deutero Ammonia
⎯⎯ ⎯ → Ca(OD) 2 + PD 3 ⎯
Ca3P2

Deutero phosphine
⎯⎯ ⎯ → Ca(OD)2 + C2D2 ⎯
CaC2

Deutero acetylene
3 ⎯⎯4⎯ → Al(OD) 3 + CD 4 ⎯

Al C

Deutero methane
⎯⎯ ⎯ → Be(OD)2 + CD 4 ⎯
Be2C

Deutero methane Uses of D2O: i) D2O is used as a moderator in nuclear reactors to slow down the neutrons. ii) As tracer in studying reaction mechanisms. Ex.: Mechanism of electrophilic substitutions of Aromatic compounds, Metabolic processes. 11

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Powered by www.myengg.com Hydrogen and its compounds iii)The basicity and structures of H3PO2 & H3PO3 are studied by the exchange reactions of D2O. iv) D2O is used in the preparation of Deuterium. HYDROGEN PEROXIDE • H2O2 was discovered by Thenard. • H2O2 is also known as oxygenated water. • (O- - O-) bond is known as Peroxy bond. • H2O2 is a weak dibasic acid. Its molecular weight is 34 and its equivalent weight is 17. • Substances containing peroxy linkage are H2O2, Na2O2, BaO2, NaHO2, H2SO5, H2S2O8, HNO4, H3PO5, CrO5, H2TiO4 • Perchloric acid (HClO4), MnO2, PbO2, TeO2, KMnO4 etc are not true peroxides as they do not contain peroxy bond. Laboratory preparation of H2O2: i) In the laboratory H2O2 is prepared by the action of ice cold dil. H2SO4 on Na2O2 (or) hydrated Barium Peroxide [BaO2.8H2O]. ii) H2O2 can also be obtained by passing CO2 gas through a suspension of Barium peroxide in water. • In the preparation of H2O2 from BaO2, phosphoric acid is preferred to dil H2SO4. This is because H3PO4 stabilizes the formation of H2O2. Auto - oxidation process: • In auto oxidation method the starting substance is 2 - ethyl anthraquinone. • 2 - ethyl anthraquinone is reduced to 2 - ethyl anthraquinol with H2/Pd. • On aerial oxidation 2-ethyl anthraquinol gives H2O2 and 2-ethyl anthraquinone back. Electrolytic Method: • H2O2 is manufactured by the electrolysis of 50% H2SO4 (or) a mixture of (NH4)2SO4 + dil. H2SO4 using platinum anode and lead cathode. • Electrodes are separated by porous stoneware diaphragm. • The product at anode is H2S2O8 and at cathode is H2 gas.
lonisation ⎯ a) 2H2SO4 ⎯⎯ ⎯ ⎯ → 2H+ + 2HSO− 4

At cathode
2H + + 2e − ⎯⎯ ⎯ ⎯⎯→
Re duction

H2

At anode
⎯ 2HSO− ⎯⎯ ⎯ ⎯ → 4
Oxidation

H2S2O8 + 2e-

b) Peroxy disulphuric acid (Marshall's acid) on distillation gives H2O2. Caro's acid (H2SO5) is intermediate product. H2S2O8 + H2O → H2SO4 + H2SO5 (Caro’s acid) H2SO5 + H2 O → H2SO4 + H2O2 During the electrolysis of 50% H2SO4, the pH of the solution increases because the concentration of acid decreases. 12

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Powered by www.myengg.com Hydrogen and its compounds • Concentration of H2O2: H2O2 obtained above is very dilute and so it is to be concentrated. Hydrogen peroxide is unstable and decomposes easily. If organic impurities are present, they catalyze the decomposition of H2O2 which may lead to explosion. ∴ H2O2 solution is concentrated carefully in the following 3 stages. • The stages present in the concentration of H2O2 are a) Freezing of water b) Evaporation of water c) Distillation under reduced pressure d) Crystallisation of H2O2 • 20 - 30% H2O2 is obtained by evaporating dilute H2O2 on water bath at reduced pressure, using fractionating column. • H2O2 decomposes below it's boiling point if it is distilled at ordinary pressure therefore, the above 20 - 30% H2O2 is distilled at reduced pressure i.e. 15mm Hg (vaccum distillation at 70°C) and 90% H2O2 is obtained. • 100% H2O2 is obtained by crystallisation of 90% H2O2 by using a freezing mixture of solid CO2 and diethyl ether. (from this needle shaped crystals of 100% pure H2O2 separate out). Physical properties of H2O2: It is colorless syrupy liquid concentrated H2O2 has bluish tinge. It forms stronger H - bonds than H2O. It's B.P is higher and M.P is lower then compared with H2O. It is completely miscible with water. It is feebly acidic and will not blue litmus to red. • The strength of H2O2 can be expressed in a) Volumes b) Molarity c) Normality d) Weight - Volume Percentage • The volume of O2 gas at S.T.P. obtained by the decomposition of 1 c.c. of H2O2 solution is known as its volume strength. It is denoted by V. Sample of H2O2 5.6 vol. H2O2 11.2 vol. H2O2 22.4 vol. H2O2 10 vol. H2O2 100 vol. H2O2 • • % strength (w/v) Molarity, M 1.7% w/v 3.4% w/v 6.8% w/v 3% w/v 30% w/v 0.5 M 1M 2M 0.89 M 8.9 M Normality, N 1N 2N 4N 1.78 N 17.8 N

Perhydol is 30% (w/v). Its Morality is 8.9M Normality is 17.8 N and it contains 300g/lit (or) 0.3g/ml. On long standing or on heating H2O2 undergoes decomposition. The equation for the decomposition of H2O2 is 2H2O2 → 2H2O + O2 13

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Powered by www.myengg.com Hydrogen and its compounds • The substances which retard the decomposition of H2O2 are Acetanilide, Glycerol, Urea, Alcohol, H3PO4, sodium stannate Pyrophosphates etc. They act as negative catalysts. They are known as inhibitors (or) stabilisers. • Alkalies, silica, MnO2, metals (Fe, Mn), graphite, alumina etc. catalyse the decomposition of H2O2. • Dilute aqueous solution of H2O2 is fairly stable in acid Medium of alcohol or ester. Alkaline solution of H2O2 are selectively not very stable. • Precautions to be taken in storing H2O2. a) The glass bottle must have wax coating on the inner side, so that the surface is smooth. b) Plastic bottles are preferred to glass bottles. It is because the Na2O in glass being alkaline, catalyses the decomposition of H2O2 c) A small quantity of acetanilide or urea is added as a stabiliser. • 90% H2O2 is used as an oxidant for rocket fuel with hydrazine. • The boiling point of H2O2 is 1520C. • Anhydrous H2O2 and dilute solutions of H2O2 are neutral to Litmus. They do not turn blue litmus to red colour. But Conc. H2O2 turns blue litmus to red colour. • H2O2 exhibits a) Oxidising properties b) Reducing properties c) Bleaching property d) Acidic Property It doesn’t exhibit dehydrating property. • H2O2 has greater reactivity in basic medium. It is because bases catalyses the decomposition of H2O2. • H2O2 is a stronger oxidizing agent and a weaker reducing agent. • The antiseptic action and the bleaching action of H2O2 involve the oxidizing properties Chemical properties of H2O2: • Stability: H2O2 is unstable and decomposes easily. 2H2O2 → 2H2O + O2 Metals, graphite, MnO2, silica, alkalies are positive catalysis. Urea, Glycerol, acetanilide, alcohol, H3PO4, Pyrophosphates are negative catalyses or Inhibitors. • Acidic nature: Pure H2O2 is weak dibasic acid. It gives two types of salts with alkalies. H2O2 + NaOH → NaHO2 + H2O H2O2 + 2NaOH → Na2O2 + 2H2O • During decomposition, H2O2 undergoes disproportionation. • When H2O2 acts as an oxidising agent it undergoes reduction. • The reaction in which H2O2 acts as a reducing agent, there will be the liberation of O2. • H2O2 → 2H+ + O2 + 2e- E0 = - 0.67V represents the reducing property of H2O2. • The fundamental equation for oxidising property of H2O2 is H2O2 → H2O + (O)

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Powered by www.myengg.com Hydrogen and its compounds The oxidising properties of H2O2 in both acidic and basic media are due to
acidic medium
H2O2 Oxidant

2H+ + 2e- + O2 (E0 = +1.77v)

O2 + 2H2O + 2e- (E0=+0.87v) basic medium

The standard reduction potential values indicate that H2O2 is a strong oxidising agent in acidic medium and weak oxidising agent in basic medium. Oxidising properties of H2O2:
⎯⎯ ⎯ ⎯⎯→ H 2 O + PbSO 4 white
⎯⎯ ⎯ ⎯ ⎯⎯→ Fe 2 (SO 4 )3 + H 2 O
Ferrous salts FeSO 4 +H2SO 4 KI+H O
2 ⎯⎯ ⎯⎯→ l 2 + KOH
2 3 ⎯⎯ ⎯ ⎯ → H2O + Na2SO 4 ⎯

black PbS

Na SO

Sod.sulphi te

H2O2

2 ⎯⎯ ⎯ → H 2 O + KNO 3 ⎯

KNO

Pot.Nitrite

3 ⎯⎯ ⎯ ⎯3 → H 2 O + Na 3 AsO 4 ⎯

Na AsO

sod. Arsenite K [Fe(CN)

4 6 ⎯⎯ ⎯ ⎯ ⎯ → H2O + K 3 [Fe(CN)6 ] ⎯

]

pot.Ferrocyanide

potassium ferri-cyanide
2 2 7 ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯ → blue coloured CrO5 ⎯

acidified K Cr O

(or )chromicacid
HCHO

in ether

alkaline pyrogallol C H / FeSO

⎯⎯ ⎯ → HCOOH + H 2 ↑ ⎯

6 6 4 ⎯⎯ ⎯ ⎯ ⎯ ⎯ → C 6H5 OH + H 2 O ⎯

• • • • •

The bleaching action of H2O2 is due to its oxidising nature. H2O2 → H2O + (O) H2O2 is used to bleach silk, wool, ivory and hair. H2O2 is used to bleach black hair to golden yellow colour under the common name Auricome. The fundamental equation for reducing property of H2O2 is H2O2 + (O) → H2O + O2 In both acidic and basic media, H2O2 shows reducing properties as
(oxidation) − + − ⎯ H 2 O 2 ⎯⎯ ⎯ ⎯ ⎯ → O 2 + 2H 2 O + 2e (basic )

(oxidation) H2O2 ⎯⎯ ⎯ ⎯ ⎯ → O2 + 2H+ + 2e− (E° = −0.67 V ) ⎯ (acidic )
(E° = +0.08V )

2OH

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Powered by www.myengg.com Hydrogen and its compounds The reducing properties of H2O2 are
4 ⎯⎯ ⎯ ⎯ ⎯ ⎯⎯→ Mn 2 + + O 2

acidified KMnO Cl

⎯⎯2 → HCl + O 2 ⎯

⎯⎯2 → HBr + O 2 ⎯
3 6 ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ → K 4 [Fe(CN)6 ] + O 2 ⎯

Br

2 ⎯⎯ ⎯ ⎯ ⎯ → Ag + O 2 ⎯

moist Ag O

alkalineK [Fe(CN)

]

pot Ferrocyanide

H2O

⎯⎯ ⎯ → NaCl + O 2 ⎯ ⎯⎯ ⎯⎯→ NaBr + O 2
2 ⎯⎯ ⎯ → PbO + O 2 ⎯

NaOCl

NaOBr

PbO

2 ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ → Mn2+ + O2 ⎯ 3+ alkaline Fe (Ferricsalts ) ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ → Fe 2+ (Ferrous ) + O ⎯

acidified MnO (black )

⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯→ O2 + H2O

O 3 (disproportionation )

2

Formation of addition compounds: It forms addition compounds with some organic and inorganic compounds. On adding H2O, these addition compounds give back H2O2. i) H2O2.Na2HPO4 ii) H2O2.(NH4)2 SO4 iii) H2O2.(NH2)2 CO (Hyperol) Tests for H2O2: i) H2O2 oxidises acidified K2Cr2 O7 solution to blue CrO5 in ether. ii) H2O2 turns acidifed TiO2 solution to orange coloured pertitanic acid [H2TiO4] iii)H2O2 turns starch - Iodide paper to blue colour. iv) It decolorises KMnO4 in acid medium. • Bleaching property : It's bleaching action is due to it's oxidising nature. H2O2 → H2O + 'O' 'O' + color → colorless • Disinfectant action: It's antiseptic properties are also due to its oxidising behaviour. • The structure of H2O2. in gaseous state can be shown as: H 94 .48
0 1

O O 1.48A° H Open book structure of H16

1110.301

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Powered by www.myengg.com Hydrogen and its compounds

The H – O – O bond angle is 94o 481 • The dihedral angle is 111o301 • The O - O bond length is 1.48 Å and the O - H is 0.97 Å. • In liquid and solid states the bond lengths and bond angles are slightly changed due to hydrogen bonding. • In crystalline H2O2 the dihedral angle is reduced to 90°. Uses Of H2O2: As disinfectant and germicide In cleaning of wounds As bleaching agent for textiles, silk, wool, wood pulp etc. Mixture of H2O2 and hydrazine is used as rocket fuel. To restore color of old oil paints As Oxidising agent Mixture of H2O2 and NH3 solution is used to bleach humain hair into golden yellow color.

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