NAVODAYA VIDYALAYA SAMITI, NOIDA
E-CONTENT FOR CLASS-XI CHEMISTRY
UNIT-09
HYDROGEN
PREPARED BY:
YOGANAND H C
P.G.T CHEMISTRY
JNV,BIJAPUR
KARNATAKA
Introduction:
Hydrogen is the first element in the periodic table & is the lightest element known. It exist as diatomic molecule H2 and is called Dihydrogen.
It was discovered by Henry Cavendish in 1766 but the name Hydrogen was proposed by Lavosier, because it “produces water on burning with oxygen”.
In Greek: “hydro” means “water”, “gen” means “producing”.
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Unique position of Hydrogen in the periodic table:�
Hydrogen is the first element in the modern periodic table.
Its atomic number is 1.It has one proton & one electron. Its electronic configuration is 1s1.
It resembles both alkali metals and halogens and, therefore, its position is anomalous.
Resemblance with alkali metals:
1) Electronic configuration:
Hydrogen like alkali metals has one electron in its valence shell.
H (Z=1) =1s1
Li (Z=3) = [He] 2s1
2) Electropositive character:
Hydrogen like alkali metals is electropositive because it can lose one electron readily to form hydrogen ion (H+) as
H → H+ + e-
Na → Na+ + e-
3) Oxidation state:
Like alkali metals, hydrogen also shows an oxidation state of +1 in its compounds.
H+Cl →Hydrogen chloride
Na+Cl →Sodium chloride
4) Combination with electronegative elements:
Like alkali metals, hydrogen forms binary compounds with electronegative elements such as halogen, oxygen & sulphur.
Halides: HCl NaCl, KCl
Sulphides: H2S Na2S, K2S
Oxides: H2O Na2O, K2O
Resemblance with halogens:
1. Electronic configuration:
Like halogens, hydrogen has only one electron less than the nearest noble gas configuration.
H(Z= 1)=1s1 He(Z=2)=1s2
F(Z=9)= 1s2 2s2 2p5 Ne (Z=8)=1s2 2s2 2p6
2. Non-metallic character: like halogens, hydrogen is non-metallic in nature.
3. Atomicity(Diatomic nature): Hydrogen molecule is diatomic (H2) like halogen molecules (F2, I2, Cl2, Br2 ).
4. Electronegative character:
Hydrogen like halogens has tendency to accept electron to form monovalent anion.
By accepting an electron hydrogen as well as halogens acquire noble gas configuration.
H + 1e → H- (He gas configuration)
F + 1 e →F- (Ne gas configuration)
5. Oxidation state: Like halogens, hydrogen exhibits oxidation state of -1 in its compounds.
Na+H- Na+Cl-
Occurrence of Hydrogen:�
Hydrogen, the most abundant element in the universe (70% of the total mass of the universe) and the third most abundant on the surface of the globe (earth), is being visualised as the major future source of energy.
Isotopes of hydrogen:
Hydrogen has three isotopes namely;
1) Protium – (1H1)
2) Deuterium - (1H2) or D
3) Tritium - (1H3) or T
PREPARATION OF DIHYDROGEN
I) Laboratory preparation of dihydrogen:
a) It is usually prepared by the reaction of granulated zinc with dilute hydrochloric acid.
b) It can also be prepared by the reaction of zinc with aqueous alkali like NaOH.
Zn
��II)Commercial Production of Dihydrogen:�
a) Electrolysis of water:
Dihydrogen of high purity is usually prepared by the electrolysis of water using platinum electrodes in the presence of small amount of acid. A small quantity of acid is added to increase the conductivity of water.
During electrolysis, dihydrogen is collected at cathode & dioxygen is liberated at anode.
b) By the electrolysis of brine solution:
Hydrogen gas is obtained as by product in the manufacture of sodium hydroxide. When the aqueous brine is electrolysed NaOH,Cl2 & H2 are produced.
c) By the reaction of steam on hydrocarbons or coke :-
The reaction of steam with hydrocarbon like methane at very high temperature in the presence of catalyst like nickel results in the formation of water gas (mixture of CO & H2).
As this mixture of gas (mixture of CO & H2) is used for the synthesis of methanol & number of other hydrocarbons. Water gas nowadays is called syngas.
Nowadays, syngas is produced by using coal & that process is called “coal gasification”.
Coal gasification plant in India
Chemical properties of dihydrogen:
Dihydrogen is not very reactive due to high bond dissociation energy (435.88 kJ mol-1 at 298.2 K).
1) Reaction of dihydrogen with halogen:
Dihydrogen reacts with halogens in the presence of light to give hydrogen halides.
This reaction of hydrogen with fluorine occurs even in the dark, with iodine it requires a catalyst.
2) Reaction of dihydrogen with dioxygen:
Dihydrogen reacts with dioxygen to form water. This reaction is highly exothermic.
∆H= -285.9kJ mol-1
3)Reaction with diniotrogen:(Manufacture of Ammonia)
Dihydrogen reacts with dinitrogen in the presence of iron(as catalyst) & molybdenum (as promoter) at 673 K under 200 atm pressure forms ammonia.
Haber’s process
4) Reaction with metals:
Reactive metals like Na, K, Ca, Li reacts with hydrogen at a high temperature (500 K -550 K) to form hydrides.
5) Reactions with metal oxides & metal ions:
Dihydrogen acts as a strong reducing agent and therefore, it reduces metal oxides (less reactive than iron) to metals.
6) Reactions with organic compounds:
Dihydrogen reacts with many organic compounds in the presence of catalysts to give useful hydrogenated products of commercial importance.
i) Hydrogenation of oils:-
Vegetable oils are polyunsaturated in nature. The C=C bonds in oils can easily undergo oxidation and the oil becomes rancid i.e., unpleasant in taste & smell. Hydrogenation reduces the number of double bonds and there by reduces the rancidity.
Hydrogenation of vegetable oils using nickel as catalyst gives edible fats (margarine & vanaspati ghee).
ii) Hydroformylation of olefins to aldehydes:
Olefins are the group of unsaturated open chain hydrocarbons possessing one or more double bonds, the simplest of which is ethylene.
Olefins react with carbon monoxide and dihydrogen in the presence of octacarbonyl dicobalt [Co(CO)4]2 as catalyst under high temperature & pressure to form aldehydes.This reaction is called hydroformylation or oxo process.
The aldehyde ,thus formed is further reduced to alcohol by nickel.
HYDRIDES:�
The compounds of hydrogen with metals and non-metals are called hydrides.
Under certain conditions H2 combines with almost all the elements, except noble gases to form binary compounds called hydrides.
Types of hydrides:
There are three types of hydrides, they are
(i) Ionic or saline hydrides or salt like hydrides.
(ii) Covalent or molecular hydrides.
(iii) Metallic or non-stoichiometric hydrides.
Ionic or saline hydrides or saltlike hydrides:
Ionic or saline hydrides are the compounds of H2 formed with most of the s-block elements, which are highly electro positive in nature.
These are formed by elements of group I & II (except Be and Mg because they form covalent hydrides) by heating them in hydrogen. These are white colourless solids (crystalline) having high MP and BP.
These are easily decomposed by water, CO2 etc
CaH2 + 2H2O → Ca(OH)2 + 2H2
CaH2 + 2CO2 → (HCOO)2Ca (calcium formate)
Covalent & Molecular Hydrides:�
Covalent or molecular hydrides are the compounds of hydrogen formed with most of the p-block elements having higher electro negativity than hydrogen. Common elements are B,C,N,F,P,S,Ga,Ge etc
Molecular hydrides are further classified in to three types based on the relative number of electrons in their Lewis structure.
a) Electron deficient hydrides.
b) Electron precise hydrides.
c) Electron rich hydrides.
Electron deficient hydrides:�
These are the hydrides, which do not have sufficient number of electrons needed to form normal covalent bonds.
The hydrides of group 13 elements are electron deficient hydrides.
Examples: BH3 (Borane), AlH3 (Aluminium hydride) etc.
B2H6 (Diborane) structure
��Electron precise hydrides:� �
These are the hydrides, which have exact number of electrons needed to form normal covalent bonds.
The hydrides of group 14 elements are electron precise hydrides.
Examples: CH4,
SiH4 (silane or silicon tetra hydride)
Electron rich hydrides:�
These are the hydrides , which have greater/excess number of electrons than required to form normal covalent bonds. The excess electrons in these hydrides are present as lone pairs of electrons.
The hydrides of group 15 to 17 form electron rich hydrides.
Examples: NH3, PH3,H2S, HF, HCl,H2O etc
Metallic or non-stoichiometric hydrides:�
Metallic hydrides are formed by many d-block and f-block elements of the periodic table. The transition metals and rare earth metals combine with hydrogen to from interstitial hydrides.
They exhibit metallic properties and are powerful reducing agents. They are non-stoichiometric hydrides and their composition varies with temperature and pressure. In these hydrides law constant composition does not hold good.
Examples: LaH2.87, TiH1.73,ZrH1.75
Metals of group 7, 8 and 9 do not form hydrides and this region of the Periodic Table is called hydride gap.
Water:
Water is the most abundant and widely distributed on the earth. It occurs in all the three physical states. Human body has about 65% of water and some plants have as much as 95%water.
STRUCTURE OF WATER:�
H2O is a covalent molecule consists of two hydrogen atoms bonded to oxygen atom by covalent bonds.
The oxygen in the water molecule is sp3 hybridised. Out of four sp3 hybrid orbitals, two sp3 hybrid orbitals form covalent bond with s-orbitals of two hydrogen atoms and remaining two lone pairs of electrons.
Due to the presence of two lone pairs of electrons on the oxygen atom, there is repulsion with two bonded pair of electrons. Due to this repulsion, the tetrahedral structure of water gets distorted & hence the geometry of water appears bent or angular with a bond angle 104.5⁰ & O-H bond length is 95.7pm.
Structure of ice:-
Ice has highly ordered three dimensional hydrogen bonded structure as shown below. Each oxygen atom is surrounded tetrahedrally by four other oxygen atoms at a distance of 276 pm.
Hydrogen bonding gives ice a rather open type structure with wide holes. These holes can hold some other molecules of appropriate size interstitially.
Chemical Properties of Water:�
1. Water is amphoteric in nature:
It has the ability to acts as an acid as well as a base i.e., it behaves as an amphoteric substance.
With NH3 it acts as an acid & with H2S or HCl , it acts as base.
H2O(l) +H2S(aq) H3O+(aq) +HS- (aq)
The auto-protolysis (self ionisation) of water takes place as follows;
H2O(l) +H2O(aq) H3O+(aq) +OH- (aq)
2. Redox reactions involving water:
Water can be easily reduced to H2 by highly electropositive metals.
3. Hydrolysis reaction:
Due to high dielectric constant, it has a very strong hydrating tendency .It dissolves many ionic compounds.
P4O10(s) + 6H20(l) 4H3PO4(aq)
Tetraphosphorus decaoxide Phospharic acid
SiCl4(l) + 2H2O(l) SiO2(s) + 4HCl(aq)
Silicon tetrachloride
4. Hydrates formation:-
From the aqueous solutions, many salts can be crystallized as hydrated salts. It is of different types.
a) Coordinated water: Example; [Cr(H2O)6]3+ 3Cl-
b) Interstitial water: Example; BaCl2.2H2O
c) Hydrogen bonded water:
Example; [Cu(H2O)4]2+ SO42-. H2O in CuSO4.5 H2O
Hard & Soft Water:-�
The water which contains dissolved salts of bicarbonates, sulphates and chlorides of calcium and magnesium is called hard water. Hard water does not produce lather with soap solution.
Examples: Borewell water,
Soft water is free from bicarbonates, sulphates and chlorides of calcium and magnesium. It produces lather with soap solution easily.
Examples: distilled water, rain water.
Types of hardness:-�
The hardness of water is of two types
(i)Temporary hardness:
Due to presence of soluble bicarbonates of calcium and magnesium. Temporary hardness can be removed by simple boiling.
Temporary hardness of water is also called carbonate hardness.
(ii)Permanent hardness
Due to presence of chlorides and sulphates of calcium and magnesium. Permanent hardness of water can be removed by special treatments.
Permanent hardness is also called non-carbonate hardness.
Softening of water:-
The process of removal of Ca2+ and Mg2+ ions from hard water is called softening of water.
I. Removal of Temporary Hardness of water:
Temporary hardness of water is due to the presence of magnesium and calcium bi carbonates. It can be removed by the following processes;
(a) By boiling:
During boiling, the soluble Mg(HCO3)2 is converted into insoluble Mg(OH)2 and Ca(HCO3)2 is changed to insoluble CaCO3. Thus soluble bicarbonates of Ca & Mg are converted into Ca & Mg insoluble carbonates. These precipitates can be removed by filtration. The filtrate thus obtained is soft water.
Ca (HCO3)2 Ca CO3 + H2O + CO2
Insoluble
Mg (HCO3)2 Mg(OH)2 + 2CO2
Insoluble
(b) By Clark’s method: or calcium hydroxide method
In this method, calculated amount of lime[Ca(OH)2 ]is added to hard water .It precipitates out calcium carbonate and magnesium hydroxide which can be filtered off.
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O
(Soluble) (Insoluble)
Mg(HCO3)2 + 2Ca(OH)2 → 2CaCO3 + Mg(OH)2 + 2H2
(Soluble) (Insoluble) (Insoluble)
II.Removal of Permanent Hardness of water:�
Permanent hardness of water is due to the presence of chlorides and sulphates of magnesium and calcium. Permanent hardness of water cannot be removed by boiling but can be removed by special methods as shown below;
1) By washing soda (Na2CO3.10H2O) treatment:
In this method, water is treated with a calculated amount of washing soda(Na2CO3),which converts the chloride & sulphates of calcium and magnesium into their respective insoluble carbonates.
CaCl2 + Na2CO3 → 2CaCO3 + 2NaCl
(Insoluble)
MgSO4 + Na2CO3 → MgCO3 + Na2SO4
(Insoluble)
2) By Calgon’s process(Sequestration):�
This is the most modern method of the softening of water. In this method , the Ca2+ and Mg2+ ions present in the hard water are sequestered (rendered ineffective) in the form of soluble complexes by adding sodium poly metaphosphate(commercially called Calgon-meaning calcium gone).
Commonly used calgon is sodium hexametaphosphate Na6P6O18 or Na2[Na4(PO3)6] ,which combines with calcium and magnesium ions to form complex ions ,which are soluble in water .
Na2[Na4(PO3)6] + 2 Ca2+ → Na2[Ca2(PO3)6] + 4 Na+
Na2[Na4(PO3)6] + 2 Mg2+ → Na2[Mg2(PO3)6] + 4 Na+
3) Ion- exchange method:( permutit method or Zeolite method)(Inorganic cation exchanger)
In this method, the ions responsible for the hardness of water are exchanged by certain less damaging ions present in some chemical compounds called ion exchangers like zeolites.
Zeolites are the hydrated sodiumaluminium
silicates (Na2Al2Si2O8.X H2O )
which have interesting property of
exchanging cations such as Ca2+
and Mg2+ ions present in the
hard water with Na+ ions.
Zeolites are naturally occurring, where as artificial zeolites which are artificially synthesised is called Permutit.
Na2Al2Si2O8 + CaCl2 → Ca(Al2Si2O8)2 + 2NaCl
Zeolite Settles at bottom
Na2Al2Si2O8 + MgCl2 → Mg(Al2Si2O8)2 + 2NaCl
Zeolite Settles at bottom
4) Synthetic resin method or organic ion exchanger (ion exchange resins):-
Synthetic resins are the insoluble polymeric solids having giant hydrocarbon network containing reactive acidic or basic groups. These are superior to Zeolite, because they can remove all types of cations as well as anions present in water. This resulting water is known as demineralised or deionised water.
These are two types of resins namely:
a)Cation exchange resins:
b) Anion exchange resins:
a)Cation exchange resins:
They have acidic groups such
as COOH (carboxyl group) or SO3H
(sulphonyl group). They may be
represented as Resin-H+.
These are capable of exchanging the H+ ions with cations of the hard water (Ca2+ and Mg2+ ions) and hence are called cation exchange resins or cation exchangers.
Ca2+ + 2H-Resin → Ca(Resin)2 + 2H+
Cation exchanger
Mg2+ + 2H-Resin → Mg(Resin)2 + 2H+
Exhausted cation exchange resin beds are regenerated by treatment with dilute acid solutions.
b) Anion exchange resins:
They have basic groups such as –OH- or –NH2. They may be represented as Resin—OH- or Resin—NH3+OH-
These are capable of exchanging the OH- with anions of the hard water (SO42- and Cl- ions) and hence are called anion exchange resins or anion exchangers.
SO42- + 2HO-Resin → SO4 (Resin)2 + 2OH-
anion exchanger
Cl- + HO-Resin → Cl (Resin) + OH-
anion exchanger
Exhausted anion exchange resin beds are regenerated by treatment with dilute alkali solutions.
Hydrogen peroxide [H2O2]:�
Hydrogen peroxide was discovered by French chemist J.L. Thenard in 1818. It is an important chemical used in pollution control treatment of domestic and industrial effluents.
Methods of preparation:
1) From Barium peroxide:-
Hydrogen peroxide was first prepared by J. L. Thenard in 1818 by acidifying barium
Peroxide using H2SO4 and removal of excess water by evaporation under reduced pressure.
BaO2.8H2O + H2SO4 BaSO4 + 8H2O + H2O2
2) From sodium peroxide (Merck’s process):-
Sodium peroxide on acidification with sulphuric acid to form hydrogen peroxide. This method of preparation of hydrogen peroxide is called Merck’s process.
Na2O2 + H2SO4 → Na2SO4 + H2O2
(20% ice cooled solution) (30% solution)
3) By auto oxidation of 2-alkylanthraquinols:- (Ex: 2-ethyl anthraquinol)�
Industrially hydrogen per oxide is prepared by the auto oxidation of 2-ethylanthraquinol.
This is a reversible reaction, after the removal of hydrogen per oxide, the oxidised product 2-ethylanthraquinone is reduced to 2-ethylantraquinol using hydrogen in the presence of palladium catalyst.
Store of Hydrogen peroxide:-�
a) It must be kept in wax lined coloured bottles because the rough glass surface causes its decomposition (2H2O2 → 2H2O + O2 ).
b) A small amount of phosphoric acid, glycerol or acetanilide is generally added which retard the decomposition of H2O2. These are also called negative catalysts. Sometimes urea is also added as stabiliser.
Structure of hydrogen peroxide:�
Hydrogen peroxide has a non planar structure, in which two H-atoms are arranged in two directions almost perpendicular to each other and to the axis joining the two oxygen atoms.
The O-O linkage is called peroxide linkage. In the soild phase, dihedral angle is reduced to 90.2⁰ from 111.5⁰ in the gas phase.
Chemical properties of Hydrogen peroxide:-�
1) Acidic nature:
It is weakly acidic in nature and pure hydrogen peroxide turns blue litmus red.
2) Oxidising agent :
It acts as a strong oxidising agent in acidic as well as in basic medium.
i) Oxidising action in acidic medium: H2O2 oxidises the ferrous sulphate to ferric sulphate.
2Fe2+ + 2H+ + H2O2 → 2 Fe3+ + 2H2O
PbS + 4 H2O2 →PbSO4 + 4H2O
ii) Oxidising action in basic medium:
In basic medium,H2O2 oxidises chromium salts to chromates.
Cr2(SO4)3 + 3 H2O2 + 10 NaOH → 2Na2CrO4 + 3 Na2SO4 + 8 H2O
Chromium sulphate Sodium chromate
In basic medium, H2O2 oxidises manganese sulphate to manganese dioxide.
MnSO4 + H2O2 +2 NaOH → 2MnO2 + Na2SO4 + 2 H2O
2) Reducing agent :�
It acts as a strong reducing agent in acidic as well as in basic medium.
i) Reducing action in acidic medium:
H2O2 reduces acidified Potassium permanganate solution to colourless manganese sulphate
ii) Reducing action in basic medium:
In basic medium, H2O2 reduces potassium permanganate to manganese dioxide.
2KMnO4 + 3 H2O2 → 2MnO2 + 2 H2O + 3O2 + 2KOH
Uses of hydrogen peroxide:�
1) Domestically hydrogen peroxide is used as hair bleach and disinfectant.
2) It is used as bleaching agent in industries such as textile, paper, leather etc
3) It is used as antiseptic to wash wound, teeth, ear under the name perhydrol.
4) It is used in the manufacture of sodium perborates & percarbonates, which are the constituents of very high quality detergents.
5) It is used in the manufacture of cephalosporins antibiotics & food products such as tartaric acid.
6) Nowadays, it is used in pollution control treatment of domestic and industrial effluents, oxidation of cyanides & restoration of aerobic conditions.
Heavy Water [D2O]:�
Chemically heavy water is deuterium oxide. It was discovered by Urey in 1932.
It can be prepared by exhaustive electrolysis of ordinary water using nickel electrodes.
It is colourless, odourless, tasteless liquid.
Uses of Heavy Water:
It is used
1. in nuclear reactors to slow down the speed of neutrons and called moderator.
2. as a tracer compound to study the mechanisms of many reactions.
Structure of heavy water
Hydrogen as a Fuel:
Hydrogen Economy:
The basic principle of hydrogen economy is the transportation and storage of energy in the form of liquid or gaseous dihydrogen. Advantage is that energy is transmitted in the form of dihydrogen and not as electric power.
Advantage as a fuel:�– It is used as fuel cells for the generation of electric power.�– One major advantage of combustion of hydrogen is that it produces very little pollution and there is not any emission of unburnt carbon particles in the form of smoke.�– 5% of dihydrogen is mixed in CNG for use in four wheeler vehicles.
THE END