After studying this unit, you will be able to
• present informed opinions on the position of hydrogen in the periodic table;
• identify the modes of occurrence and preparation of dihydrogen on a small and commercial scale; describe isotopes of hydrogen;
• explain how different elements combine with hydrogen to form ionic, molecular and non-stoichiometric compounds;
• describe how an understanding of its properties can lead to the production of useful substances, and new technologies;
• understand the structure of water and use the knowledge for explaining physical and chemical properties;
• explain how environmental water quality depends on a variety of dissolved substances; difference between ‘hard’ and ‘soft’ water and learn about water softening;
• acquire the knowledge about heavy water and its importance;
• understand the structure of hydrogen peroxide, learn its preparatory methods and properties leading to the manufacture of useful chemicals and cleaning of environment;
• understand and use certain terms e.g., electron-deficient, electron-precise, electron-rich, hydrogen economy, hydrogenation etc.
Hydrogen has the simplest atomic structure among all the elements around us in Nature. In atomic form it consists of only one proton and one electron. However, in elemental form it exists as a diatomic (H2) molecule and is called dihydrogen. It forms more compounds than any other element. Do you know that the global concern related to energy can be overcome to a great extent by the use of hydrogen as a source of energy? In fact, hydrogen is of great industrial importance as you will learn in this unit.
9.1 Position of Hydrogen in the Periodic Table
Hydrogen is the first element in the periodic table. However, its placement in the periodic table has been a subject of discussion in the past. As you know by now that the elements in the periodic table are arranged according to their electronic configurations.
Hydrogen has electronic configuration 1s1. On one hand, its electronic configuration is similar to the outer electronic configuration (ns1) of alkali metals , which belong to the first group of the periodic table. On the other hand, like halogens (with ns2np5 configuration belonging to the seventeenth group of the periodic table), it is short by one electron to the corresponding noble gas configuration, helium (1s2). Hydrogen, therefore, has resemblance to alkali metals, which lose one electron to form unipositive ions, as well as with halogens, which gain one electron to form uninegative ion. Like alkali metals, hydrogen forms oxides, halides and sulphides. However, unlike alkali metals, it has a very high ionization enthalpy and does not possess metallic characteristics under normal conditions. In fact, in terms of ionization enthalpy, hydrogen resembles more
with halogens, ∆i H of Li is 520 kJ mol–1, F is 1680 kJ mol–1 and that of H is 1312 kJ mol–1. Like halogens, it forms a diatomic molecule, combines with elements to form hydrides and a large number of covalent compounds. However, in terms of reactivity, it is very low as compared to halogens.
Inspite of the fact that hydrogen, to a certain extent resembles both with alkali metals and halogens, it differs from them as well. Now the pertinent question arises as where should it be placed in the periodic table? Loss of the electron from hydrogen atom results in nucleus (H+) of ~1.5×10–3 pm size. This is extremely small as compared to normal atomic and ionic sizes of 50 to 200pm. As a consequence, H+ does not exist freely and is always associated with other atoms or molecules. Thus, it is unique in behaviour and is, therefore, best placed separately in the periodic table (Unit 3).
9.2 DIHYDROGEN, H2
9.2.1 Occurrence
Dihydrogen is the most abundant element in the universe (70% of the total mass of the universe) and is the principal element in the solar atmosphere. The giant planets Jupiter and Saturn consist mostly of hydrogen. However, due to its light nature, it is much less abundant (0.15% by mass) in the earth’s atmosphere. Of course, in the combined form it constitutes 15.4% of the earth’s crust and the oceans. In the combined form besides in water, it occurs in plant and animal tissues, carbohydrates, proteins, hydrides including hydrocarbons and many other compounds.
9.2.2 Isotopes of Hydrogen
Hydrogen has three isotopes: protium, 11H, deuterium, 21H or D and tritium,31H or T. Can you guess how these isotopes differ from each other ? These isotopes differ from one another in respect of the presence of neutrons. Ordinary hydrogen, protium, has no neutrons, deuterium (also known as heavy hydrogen) has one and tritium has two neutrons in the nucleus. In the year 1934, an American scientist, Harold C. Urey, got Nobel Prize for separating hydrogen isotope of mass number 2 by physical methods.
β– particles (t½, 12.33 years).
Since the isotopes have the same electronic configuration, they have almost the same chemical properties. The only difference is in their rates of reactions, mainly due to their different enthalpy of bond dissociation (Table 9.1). However, in physical properties these isotopes differ considerably due to their large mass differences.
There are a number of methods for preparing dihydrogen from metals and metal hydrides.
(i) It is usually prepared by the reaction of granulated zinc with dilute hydrochloric acid.
Zn + 2H+ → Zn2+ + H2
(ii) It can also be prepared by the reaction of zinc with aqueous alkali.
Zn + 2NaOH → Na2ZnO2 + H2
Sodium zincate
The commonly used processes are outlined below:
(i) Electrolysis of acidified water using platinum electrodes gives hydrogen.
(ii) High purity (>99.95%) dihydrogen is obtained by electrolysing warm aqueous barium hydroxide solution between nickel electrodes.
(iii) It is obtained as a byproduct in the manufacture of sodium hydroxide and chlorine by the electrolysis of brine solution. During electrolysis, the reactions that take place are:
at anode: 2Cl–(aq) → Cl2(g) + 2e–
at cathode: 2H2O (l) + 2e–→ H2(g) + 2OH–(aq)
The overall reaction is
2Na+ (aq) + 2Cl–(aq) + 2H2O(l)
↓
Cl2(g) + H2(g) + 2Na+ (aq) + 2OH–(aq)
(iv) Reaction of steam on hydrocarbons or coke at high temperatures in the presence of catalyst yields hydrogen.
e.g.,
The mixture of co and H2 is called water gas. As this mixture of CO and H2 is used for the synthesis of methanol and a number of hydrocarbons, it is also called synthesis gas or ‘syngas’. Nowadays ‘syngas’ is produced from sewage, saw-dust, scrap wood, newspapers etc. The process of producing ‘syngas’ from coal is called ‘coal gasification’.
The production of dihydrogen can be increased by reacting carbon monoxide of syngas mixtures with steam in the presence of iron chromate as catalyst.
This is called water-gas shift reaction. Carbon dioxide is removed by scrubbing with sodium arsenite solution.
Presently ~77% of the industrial dihydrogen is produced from petro-chemicals, 18% from coal, 4% from electrolysis of aqueous solutions and 1% from other sources.
Dihydrogen is a colourless, odourless, tasteless, combustible gas. It is lighter than air and insoluble in water. Its other physical properties alongwith those of deuterium are given in Table 9.1.
The chemical behaviour of dihydrogen (and for that matter any molecule) is determined, to a large extent, by bond dissociation enthalpy. The H–H bond dissociation enthalpy is the highest for a single bond between two atoms of any element. What inferences would you draw from this fact ? It is because of this factor that the dissociation of dihydrogen into its atoms is only ~0.081% around 2000K which increases to 95.5% at 5000K. Also, it is relatively inert at room temperature due to the high H–H bond enthalpy. Thus, the atomic hydrogen is produced at a high temperature in an electric arc or under ultraviolet radiations. Since its orbital is incomplete with 1s1 electronic configuration, it does combine with almost all the elements. It accomplishes reactions by (i) loss of the only electron to
give H+, (ii) gain of an electron to form H–, and (iii) sharing electrons to form a single covalent bond.
The chemistry of dihydrogen can be illustrated by the following reactions:
Reaction with halogens: It reacts with halogens, X2 to give hydrogen halides, HX,
While the reaction with fluorine occurs even in the dark, with iodine it requires a catalyst.
Reaction with dioxygen: It reacts with dioxygen to form water. The reaction is highly exothermic.
2H2(g) + O2 (g) 
2H2O(l);
= –285.9 kJ mol–1
Reaction with dinitrogen: With dinitrogen it forms ammonia.
This is the method for the manufacture of ammonia by the Haber process.
Reactions with metals: With many metals it combines at a high temperature to yield the corresponding hydrides (section 9.5)
H2(g) +2M(g) → 2MH(s);
where M is an alkali metal
Reactions with metal ions and metal oxides: It reduces some metal ions in aqueous solution and oxides of metals (less active than iron) into corresponding metals.
Reactions with organic compounds: It reacts with many organic compounds in the presence of catalysts to give useful hydrogenated products of commercial importance. For example :
(i) Hydrogenation of vegetable oils using nickel as catalyst gives edible fats (margarine and vanaspati ghee)
(ii) Hydroformylation of olefins yields aldehydes which further undergo reduction to give alcohols.
Problem 9.1
Comment on the reactions of dihydrogen with (i) chlorine, (ii) sodium, and (iii) copper(II) oxide
Solution
(i) Dihydrogen reduces chlorine into chloride (Cl–) ion and itself gets oxidised to H+ ion by chlorine to form hydrogen chloride. An electron pair is shared between H and Cl leading to the formation of a covalent molecule.
(ii) Dihydrogen is reduced by sodium to form NaH. An electron is transferred from Na to H leading to the formation of an ionic compound, Na+H–.
(iii) Dihydrogen reduces copper(II) oxide to copper in zero oxidation state and itself gets oxidised to H2O, which is a covalent molecule.
• The largest single use of dihydrogen is in the synthesis of ammonia which is used in the manufacture of nitric acid and nitrogenous fertilizers.
• Dihydrogen is used in the manufacture of vanaspati fat by the hydrogenation of polyunsaturated vegetable oils like soyabean, cotton seeds etc.
• It is used in the manufacture of bulk organic chemicals, particularly methanol.
• It is widely used for the manufacture of metal hydrides (Section 9.5)
• It is used for the preparation of hydrogen chloride, a highly useful chemical.
• In metallurgical processes, it is used to reduce heavy metal oxides to metals.
• Atomic hydrogen and oxy-hydrogen torches find use for cutting and welding purposes. Atomic hydrogen atoms (produced by dissociation of dihydrogen with the help of an electric arc) are allowed to recombine on the surface to be welded to generate the temperature of 4000 K.
• It is used as a rocket fuel in space research.
• Dihydrogen is used in fuel cells for generating electrical energy. It has many advantages over the conventional fossil fuels and electric power. It does not produce any pollution and releases greater energy per unit mass of fuel in comparison to gasoline and other fuels.
Dihydrogen, under certain reaction conditions, combines with almost all elements, except noble gases, to form binary compounds, called hydrides. If ‘E’ is the symbol of an element then hydride can be expressed as EHx (e.g., MgH2) or EmHn (e.g., B2H6).
The hydrides are classified into three categories :
(i) Ionic or saline or saltlike hydrides
(ii) Covalent or molecular hydrides
(iii) Metallic or non-stoichiometric hydrides
These are stoichiometric compounds of dihydrogen formed with most of the s-block elements which are highly electropositive in character. However, significant covalent character is found in the lighter metal hydrides such as LiH, BeH2 and MgH2. In fact BeH2 and MgH2 are polymeric in structure. The ionic hydrides are crystalline, non-volatile and non-conducting in solid state. However, their melts conduct electricity and on electrolysis liberate dihydrogen gas at anode, which confirms the existence of H– ion.
Saline hydrides react violently with water producing dihydrogen gas.
Lithium hydride is rather unreactive at moderate temperatures with O2 or Cl2. It is, therefore, used in the synthesis of other useful hydrides, e.g.,
8LiH + Al2Cl6 → 2LiAlH4 + 6LiCl
2LiH + B2H6 → 2LiBH4
Dihydrogen forms molecular compounds with most of the p-block elements. Most familiar examples are CH4, NH3, H2O and HF. For convenience hydrogen compounds of non-metals have also been considered as hydrides. Being covalent, they are volatile compounds.
Molecular hydrides are further classified according to the relative numbers of electrons and bonds in their Lewis structure into :
(i) electron-deficient, (ii) electron-precise, and (iii) electron-rich hydrides.
An electron-deficient hydride, as the name suggests, has too few electrons for writing its conventional Lewis structure. Diborane (B2H6) is an example. In fact all elements of group 13 will form electron-deficient compounds. What do you expect from their behaviour? They act as Lewis acids i.e., electron acceptors.
Electron-precise compounds have the required number of electrons to write their conventional Lewis structures. All elements of group 14 form such compounds (e.g., CH4) which are tetrahedral in geometry.
Electron-rich hydrides have excess electrons which are present as lone pairs. Elements of group 15-17 form such compounds. (NH3 has 1- lone pair, H2O – 2 and HF –3 lone pairs). What do you expect from the behaviour of such compounds ? They will behave as Lewis bases i.e., electron donors. The presence of lone pairs on highly electronegative atoms like N, O and F in hydrides results in hydrogen bond formation between the molecules. This leads to the association of molecules.
Problem 9.2
Would you expect the hydrides of N, O and F to have lower boiling points than the hydrides of their subsequent group members ? Give reasons.
Solution
On the basis of molecular masses of NH3, H2O and HF, their boiling points are expected to be lower than those of the subsequent group member hydrides. However, due to higher electronegativity of N, O and F, the magnitude of hydrogen bonding in their hydrides will be quite appreciable. Hence, the boiling points NH3, H2O and HF will be higher than the hydrides of their subsequent group members.
These are formed by many d-block and f-block elements. However, the metals of group 7, 8 and 9 do not form hydride. Even from group 6, only chromium forms CrH. These hydrides conduct heat and electricity though not as efficiently as their parent metals do. Unlike saline hydrides, they are almost always non-stoichiometric, being deficient in hydrogen. For example, LaH2.87, YbH2.55, TiH1.5–1.8, ZrH1.3–1.75, VH0.56, NiH0.6–0.7, PdH0.6–0.8 etc. In such hydrides, the law of constant composition does not hold good.
Earlier it was thought that in these hydrides, hydrogen occupies interstices in the metal lattice producing distortion without any change in its type. Consequently, they were termed as interstitial hydrides. However, recent studies have shown that except for hydrides of Ni, Pd, Ce and Ac, other hydrides of this class have lattice different from that of the parent metal. The property of absorption of hydrogen on transition metals is widely used in catalytic reduction / hydrogenation reactions for the preparation of large number of compounds. Some of the metals (e.g., Pd, Pt) can accommodate a very large volume of hydrogen and, therefore, can be used as its storage media. This property has high potential for hydrogen storage and as a source of energy.
Problem 9.3
Can phosphorus with outer electronic configuration 3s23p3 form PH5 ?
Solution
Although phosphorus exhibits +3 and +5 oxidation states, it cannot form PH5. Besides some other considerations, high ∆aH value of dihydrogen and ∆egH value of hydrogen do not favour to exhibit the highest oxidation state of P, and consequently the formation of PH5.
A major part of all living organisms is made up of water. Human body has about 65% and some plants have as much as 95% water. It is a crucial compound for the survival of all life forms. It is a solvent of great importance. The distribution of water over the earth’s surface is not uniform. The estimated world water supply is given in Table 9.2
It is a colourless and tasteless liquid. Its physical properties are given in Table 9.3 along with the physical properties of heavy water.
The unusual properties of water in the condensed phase (liquid and solid states) are due to the presence of extensive hydrogen bonding between water molecules. This leads to high freezing point, high boiling point, high heat of vaporisation and high heat of fusion in comparison to H2S and H2Se. In comparison to other liquids, water has a higher specific heat, thermal conductivity, surface tension, dipole moment and dielectric constant, etc. These properties allow water to play a key role in the biosphere.
The high heat of vaporisation and heat capacity are responsible for moderation of the climate and body temperature of living beings. It is an excellent solvent for transportation of ions and molecules required for plant and animal metabolism. Due to hydrogen bonding with polar molecules, even covalent compounds like alcohol and carbohydrates dissolve in water.
In the gas phase water is a bent molecule with a bond angle of 104.5°, and O–H bond length of 95.7 pm as shown in Fig 9.1(a). It is a highly polar molecule, (Fig 9.1(b)). Its orbital overlap picture is shown in Fig. 9.1(c). In the liquid phase water molecules are associated together by hydrogen bonds.
Fig. 9.1 (a) The bent structure of water; (b) the water molecule as a dipole and
(c) the orbital overlap picture in water molecule.
The crystalline form of water is ice. At atmospheric pressure ice crystallises in the hexagonal form, but at very low temperatures it condenses to cubic form. Density of ice is less than that of water. Therefore, an ice cube floats on water. In winter season ice formed on the surface of a lake provides thermal insulation which ensures the survival of the aquatic life. This fact is of great ecological significance.
Ice has a highly ordered three dimensional hydrogen bonded structure as shown in Fig. 9.2. Examination of ice crystals with X-rays shows that 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.
Water reacts with a large number of substances. Some of the important reactions are given below.
(1) Amphoteric Nature: It has the ability to act as an acid as well as a base i.e., it behaves as an amphoteric substance. In the Brönsted sense it acts as an acid with NH3 and a base with H2S.
The auto-protolysis (self-ionization) of water takes place as follows :
acid-1 base-2 acid-2 base-1
(acid) (base) (conjugate acid) (conjugate base)
(2) Redox Reactions Involving Water: Water can be easily reduced to dihydrogen by highly electropositive metals.
Thus, it is a great source of dihydrogen.
Water is oxidised to O2 during photosynthesis.
6CO2(g) + 12H2O(l) → C6H12O6(aq) + 6H2O(l) + 6O2(g)
With fluorine also it is oxidised to O2.
2F2(g) + 2H2O(l) → 4H+ (aq) + 4F–(aq) + O2(g)
(3) Hydrolysis Reaction: Due to high dielectric constant, it has a very strong hydrating tendency. It dissolves many ionic compounds. However, certain covalent and some ionic compounds are hydrolysed in water.
(4) Hydrates Formation: From aqueous solutions many salts can be crystallised as hydrated salts. Such an association of water is of different types viz.,
(i) coordinated water e.g.,
(ii) interstitial water e.g.,
(iii) hydrogen-bonded water e.g.,
in 
Problem 9.4
How many hydrogen-bonded water molecule(s) are associated in CuSO4.5H2O?
Solution
Only one water molecule, which is outside the brackets (coordination sphere), is hydrogen-bonded. The other four molecules of water are coordinated.
Rain water is almost pure (may contain some dissolved gases from the atmosphere). Being a good solvent, when it flows on the surface of the earth, it dissolves many salts. Presence of calcium and magnesium salts in the form of hydrogencarbonate, chloride and sulphate in water makes water ‘hard’. Hard water does not give lather with soap. Water free from soluble salts of calcium and magnesium is called Soft water. It gives lather with soap easily.
Hard water forms scum/precipitate with soap. Soap containing sodium stearate (C17H35COONa) reacts with hard water to precipitate out Ca/Mg stearate.
It is, therefore, unsuitable for laundry. It is harmful for boilers as well, because of deposition of salts in the form of scale. This reduces the efficiency of the boiler. The hardness of water is of two types: (i) temporary hardness, and (ii) permanent hardness.
Temporary hardness is due to the presence of magnesium and calcium hydrogen-carbonates. It can be removed by :
(i) Boiling: During boiling, the soluble Mg(HCO3)2 is converted into insoluble Mg(OH)2 and Ca(HCO3)2 is changed to insoluble CaCO3. It is because of high solubility product of Mg(OH)2 as compared to that of MgCO3, that Mg(OH)2 is precipitated. These precipitates can be removed by filtration. Filtrate thus obtained will be soft water.
(ii) Clark’s method: In this method calculated amount of lime is added to hard water. It precipitates out calcium carbonate and magnesium hydroxide which can be filtered off.
It is due to the presence of soluble salts of magnesium and calcium in the form of chlorides and sulphates in water. Permanent hardness is not removed by boiling. It can be removed by the following methods:
(i) Treatment with washing soda (sodium carbonate): Washing soda reacts with soluble calcium and magnesium chlorides and sulphates in hard water to form insoluble carbonates.
(ii) Calgon’s method: Sodium hexameta-phosphate (Na6P6O18), commercially called ‘calgon’, when added to hard water, the following reactions take place.
The complex anion keeps the Mg2+ and Ca2+ ions in solution.
(iii) Ion-exchange method: This method is also called zeolite/permutit process. Hydrated sodium aluminium silicate is zeolite/permutit. For the sake of simplicity, sodium aluminium silicate (NaAlSiO4) can be written as NaZ. When this is added in hard water, exchange reactions take place.
Permutit/zeolite is said to be exhausted when all the sodium in it is used up. It is regenerated for further use by treating with an aqueous sodium chloride solution.
(iv) Synthetic resins method: Nowadays hard water is softened by using synthetic cation exchangers. This method is more efficient than zeolite process. Cation exchange resins contain large organic molecule with - SO3H group and are water insoluble. Ion exchange resin (RSO3H) is changed to RNa by treating it with NaCl. The resin exchanges Na+ ions with Ca2+ and Mg2+ ions present in hard water to make the water soft. Here R is resin anion.
The resin can be regenerated by adding aqueous NaCl solution.
Pure de-mineralised (de-ionized) water free from all soluble mineral salts is obtained by passing water successively through a cation exchange (in the H+ form) and an anion-exchange (in the OH– form) resins:
In this cation exchange process, H+ exchanges for Na+, Ca2+, Mg2+ and other cations present in water. This process results in proton release and thus makes the water acidic. In the anion exchange process:
OH–exchanges for anions like Cl–, HCO3–, SO42–etc. present in water. OH– ions, thus, liberated neutralise the H+ ions set free in the cation exchange.
The exhausted cation and anion exchange resin beds are regenerated by treatment with dilute acid and alkali solutions respectively.
Hydrogen peroxide is an important chemical used in pollution control treatment of domestic and industrial effluents.
It can be prepared by the following methods.
(i) Acidifying barium peroxide and removing excess water by evaporation under reduced pressure gives hydrogen peroxide.
(ii) Peroxodisulphate, obtained by electrolytic oxidation of acidified sulphate solutions at high current density, on hydrolysis yields hydrogen peroxide.
This method is now used for the laboratory preparation of D2O2.
(iii) Industrially it is prepared by the auto-oxidation of 2-alklylanthraquinols.
In this case 1% H2O2 is formed. It is extracted with water and concentrated to ~30% (by mass) by distillation under reduced pressure. It can be further concentrated to ~85% by careful distillation under low pressure. The remaining water can be frozen out to obtain pure H2O2.
In the pure state H2O2 is an almost colourless (very pale blue) liquid. Its important physical properties are given in Table 9.4.
H2O2 is miscible with water in all proportions and forms a hydrate H2O2.H2O (mp 221K). A 30% solution of H2O2 is marketed as ‘100 volume’ hydrogen peroxide. It means that one millilitre of 30% H2O2 solution will give 100 mL of oxygen at STP. Commercially marketed sample is 10 V, which means that the sample contains 3% H2O2.
Problem 9.4
Calculate the strength of 10 volume solution of hydrogen peroxide.
Solution
10 volume solution of H2O2 means that 1L of this H2O2 solution will give 10 L of oxygen at STP
2×34 g 22.7 L at STP
68 g
On the basis of above equation 22.7 L of O2 is produced from 68 g H2O2 at STP
10 L of O2 at STP is produced from 
Therefore, strength of H2O2 in 10 volume H2O2 solution = 30 g/L = 3% H2O2 solution
Hydrogen peroxide has a non-planar structure. The molecular dimensions in the gas phase and solid phase are shown in Fig 9.3
Fig. 9.3 (a) H2O2 structure in gas phase, dihedral angle is 111.5°. (b) H2O2 structure in solid phase at 110K, dihedral angle is 90.2°.
It acts as an oxidising as well as reducing agent in both acidic and alkaline media. Simple reactions are described below.
(i) Oxidising action in acidic medium
(ii) Reducing action in acidic medium
(iii) Oxidising action in basic medium
(iv) Reducing action in basic medium
H2O2 decomposes slowly on exposure to light.
In the presence of metal surfaces or traces of alkali (present in glass containers), the above reaction is catalysed. It is, therefore, stored in wax-lined glass or plastic vessels in dark. Urea can be added as a stabiliser. It is kept away from dust because dust can induce explosive decomposition of the compound.
Its wide scale use has led to tremendous increase in the industrial production of H2O2. Some of the uses are listed below:
(i) In daily life it is used as a hair bleach and as a mild disinfectant. As an antiseptic it is sold in the market as perhydrol.
(ii) It is used to manufacture chemicals like sodium perborate and per-carbonate, which are used in high quality detergents.
(iii) It is used in the synthesis of hydroquinone, tartaric acid and certain food products and pharmaceuticals (cephalosporin) etc.
(iv) It is employed in the industries as a bleaching agent for textiles, paper pulp, leather, oils, fats, etc.
(v) Nowadays it is also used in Environmental (Green) Chemistry. For example, in pollution control treatment of domestic and industrial effluents, oxidation of cyanides, restoration of aerobic conditions to sewage wastes, etc.
It is extensively used as a moderator in nuclear reactors and in exchange reactions for the study of reaction mechanisms. It can be prepared by exhaustive electrolysis of water or as a by-product in some fertilizer industries. Its physical properties are given in Table 9.3. It is used for the preparation of other deuterium compounds, for example:
Dihydrogen releases large quantities of heat on combustion. The data on energy released by combustion of fuels like dihydrogen, methane, LPG etc. are compared in terms of the same amounts in mole, mass and volume, are shown in Table 9.5.
From this table it is clear that on a mass for mass basis dihydrogen can release more energy than petrol (about three times). Moreover, pollutants in combustion of dihydrogen will be less than petrol. The only pollutants will be the oxides of dinitrogen (due to the presence of dinitrogen as impurity with dihydrogen). This, of course, can be minimised by injecting a small amount of water into the cylinder to lower the temperature so that the reaction between dinitrogen and dioxygen may not take place. However, the mass of the containers in which dihydrogen will be kept must be taken into consideration. A cylinder of compressed dihydrogen weighs about 30 times as much as a tank of petrol containing the same amount of energy. Also, dihydrogen gas is converted into liquid state by cooling to 20K. This would require expensive insulated tanks. Tanks of metal alloy like NaNi5, Ti–TiH2, Mg–MgH2 etc. are in use for storage of dihydrogen in small quantities. These limitations have prompted researchers to search for alternative techniques to use dihydrogen in an efficient way.
In this view Hydrogen Economy is an alternative. The basic principle of hydrogen economy is the transportation and storage of energy in the form of liquid or gaseous dihydrogen. Advantage of hydrogen economy is that energy is transmitted in the form of dihydrogen and not as electric power. It is for the first time in the history of India that a pilot project using dihydrogen as fuel was launched in October 2005 for running automobiles. Initially 5% dihydrogen has been mixed in CNG for use in four-wheeler vehicles. The percentage of dihydrogen would be gradually increased to reach the optimum level.
Nowadays, it is also used in fuel cells for generation of electric power. It is expected that economically viable and safe sources of dihydrogen will be identified in the years to come, for its usage as a common source of energy.
Summary
Hydrogen is the lightest atom with only one electron. Loss of this electron results in an elementary particle, the proton. Thus, it is unique in character. It has three isotopes, namely : protium (11H), deuterium (D or 21H) and tritium (T or3 1H). Amongst these three, only tritium is radioactive. Inspite of its resemblance both with alkali metals and halogens, it occupies a separate position in the periodic table because of its unique properties.
Hydrogen is the most abundant element in the universe. In the free state it is almost not found in the earth’s atmosphere. However, in the combined state, it is the third most abundant element on the earth’s surface.
Dihydrogen on the industrial scale is prepared by the water-gas shift reaction from petrochemicals. It is obtained as a byproduct by the electrolysis of brine.
The H–H bond dissociation enthalpy of dihydrogen (435.88 kJ mol–1) is the highest for a single bond between two atoms of any elements. This property is made use of in the atomic hydrogen torch which generates a temperature of ~4000K and is ideal for welding of high melting metals.
Though dihydrogen is rather inactive at room temperature because of very high negative dissociation enthalpy, it combines with almost all the elements under appropriate conditions to form hydrides. All the type of hydrides can be classified into three categories: ionic or saline hydrides, covalent or molecular hydrides and metallic or non-stoichiometric hydrides. Alkali metal hydrides are good reagents for preparing other hydride compounds. Molecular hydrides (e.g., B2H6, CH4, NH3, H2O) are of great importance in day-to-day life. Metallic hydrides are useful for ultrapurification of dihydrogen and as dihydrogen storage media.
Among the other chemical reactions of dihydrogen, reducing reactions leading to the formation hydrogen halides, water, ammonia, methanol, vanaspati ghee, etc. are of great importance. In metallurgical process, it is used to reduce metal oxides. In space programmes, it is used as a rocket fuel. In fact, it has promising potential for use as a non-polluting fuel of the near future (Hydrogen Economy).
Water is the most common and abundantly available substance. It is of a great chemical and biological significance. The ease with which water is transformed from liquid to solid and to gaseous state allows it to play a vital role in the biosphere. The water molecule is highly polar in nature due to its bent structure. This property leads to hydrogen bonding which is the maximum in ice and least in water vapour. The polar nature of water makes it: (a) a very good solvent for ionic and partially ionic compounds; (b) to act as an amphoteric (acid as well as base) substance; and (c) to form hydrates of different types. Its property to dissolve many salts, particularly in large quantity, makes it hard and hazardous for industrial use. Both temporary and permanent hardness can be removed by the use of zeolites, and synthetic ion-exchangers.
Heavy water, D2O is another important compound which is manufactured by the electrolytic enrichment of normal water. It is essentially used as a moderator in nuclear reactors.
Hydrogen peroxide, H2O2 has an interesting non-polar structure and is widely used as an industrial bleach and in pharmaceutical and pollution control treatment of industrial and domestic effluents.
Exercises
9.1 Justify the position of hydrogen in the periodic table on the basis of its electronic configuration.
NEETprep Answer9.2 Write the names of isotopes of hydrogen. What is the mass ratio of these isotopes?
NEETprep Answer9.3 Why does hydrogen occur in a diatomic form rather than in a monoatomic form under normal conditions?
NEETprep Answer9.4 How can the production of dihydrogen, obtained from ‘coal gasification’, be increased?
NEETprep Answer9.5 Describe the bulk preparation of dihydrogen by electrolytic method. What is the role of an electrolyte in this process ?
NEETprep Answer9.6 Complete the following reactions:
(i) 
(ii) 
(iii) 
(iv) 
9.7 Discuss the consequences of high enthalpy of H–H bond in terms of chemical reactivity of dihydrogen.
NEETprep Answer9.8 What do you understand by (i) electron-deficient, (ii) electron-precise, and (iii) electron-rich compounds of hydrogen? Provide justification with suitable examples.
NEETprep Answer9.9 What characteristics do you expect from an electron-deficient hydride with respect to its structure and chemical reactions?
NEETprep Answer9.10 Do you expect the carbon hydrides of the type (CnH2n + 2) to act as ‘Lewis’ acid or base? Justify your answer.
NEETprep Answer9.11 What do you understand by the term “non-stoichiometric hydrides”? Do you expect this type of the hydrides to be formed by alkali metals? Justify your answer.
NEETprep Answer9.12 How do you expect the metallic hydrides to be useful for hydrogen storage? Explain.
NEETprep Answer9.13 How does the atomic hydrogen or oxy-hydrogen torch function for cutting and welding purposes ? Explain.
NEETprep Answer9.14 Among , H2O and HF, which would you expect to have highest magnitude of hydrogen bonding and why?
NEETprep Answer9.15 Saline hydrides are known to react with water violently producing fire. Can CO2, a well known fire extinguisher, be used in this case? Explain.
NEETprep Answer9.16 Arrange the following
(i) CaH2, BeH2 and TiH2 in order of increasing electrical conductance.
(ii) LiH, NaH and CsH in order of increasing ionic character.
(iii) H–H, D–D and F–F in order of increasing bond dissociation enthalpy.
(iv) NaH, MgH2 and H2O in order of increasing reducing property.
NEETprep Answer9.17 Compare the structures of H2O and H2O2.
NEETprep Answer9.18 What do you understand by the term ’auto-protolysis’ of water? What is its significance?
NEETprep Answer9.19 Consider the reaction of water with F2 and suggest, in terms of oxidation and reduction, which species are oxidised/reduced.
NEETprep Answer9.20 Complete the following chemical reactions.
(i) 
(ii) 
(iii) 
(v) 
(vi) 
Classify the above into (a) hydrolysis, (b) redox and (c) hydration reactions.
NEETprep Answer9.21 Describe the structure of the common form of ice.
NEETprep Answer9.22 What causes the temporary and permanent hardness of water ?
NEETprep Answer9.23 Discuss the principle and method of softening of hard water by synthetic ion-exchange resins.
9.24 Write chemical reactions to show the amphoteric nature of water.
NEETprep Answer9.25 Write chemical reactions to justify that hydrogen peroxide can function as an oxidising as well as reducing agent.
NEETprep Answer9.26 What is meant by ‘demineralised’ water and how can it be obtained ?
NEETprep Answer9.27 Is demineralised or distilled water useful for drinking purposes? If not, how can it be made useful?
NEETprep Answer
9.28 Describe the usefulness of water in biosphere and biological systems.
NEETprep Answer9.29 What properties of water make it useful as a solvent? What types of compound can it (i) dissolve, and (ii) hydrolyse ?
NEETprep Answer9.30 Knowing the properties of H2O and D2O, do you think that D2O can be used for drinking purposes?
NEETprep Answer9.31 What is the difference between the terms ‘hydrolysis’ and ‘hydration’ ?
NEETprep Answer9.32 How can saline hydrides remove traces of water from organic compounds?
NEETprep Answer9.33 What do you expect the nature of hydrides is, if formed by elements of atomic numbers 15, 19, 23 and 44 with dihydrogen? Compare their behaviour towards water.
NEETprep Answer9.34 Do you expect different products in solution when aluminium(III) chloride and potassium chloride treated separately with (i) normal water (ii) acidified water, and (iii) alkaline water? Write equations wherever necessary.
NEETprep Answer9.35 How does H2O2 behave as a bleaching agent?
NEETprep Answer9.36 What do you understand by the terms:
(i) hydrogen economy (ii) hydrogenation (iii) ‘syngas’ (iv) water-gas shift reaction (v) fuel-cell ?
NEETprep AnswerEXAMPLAR
1. Hydrogen resembles halogens in many respects for which several factors are responsible. Of the following factors which one is most important in this respect?
(a) Its tendency to lose an electron to form a cation.
(b) Its tendency to gain a single electron in its valence shell to attain stable electronic configuration.
(c) Its low negative electron enthalpy value.
(d) Its small size.
NEETprep Answer2. Why does H+ ions always get associated with other atoms or molecules?
(a) Ionisation enthalpy of hydrogen resembles that of alkali metals
(b) Its reactivity is similar to halogens
(c) It resembles both alkali metals and halogens
(d) Loss of an electron from hydrogen atom results in a nucleus of very small size as compared to other atoms or ions. Due to small size it cannot exist free
NEETprep Answer3. Metal hydrides are ionic, covalent or molecular in nature. Among LiH, NaH, KH, RbH, CsH, the correct order of increasing ionic character is
(a) LiH > NaH > CsH > KH > RbH
(b) LiH < NaH < KH < RbH < CsH
(c) RbH > CsH > NaH > KH > LiH
(d) KH < NaH < RbH < LiH < CsH
NEETprep Answer4. Which of the following hydrides is electron-precise hydride?
(a) B2H6
(b) NH3
(c) H2O
(d) CH4
NEETprep Answer5. Radioactive elements emit , and rays and are characterised by their half-lives. The radioactive isotope of hydrogen is
(a) protium
(b) deuterium
(c) tritium
(d) hydronium
NEETprep Answer6. Consider the reactions
(i)
(ii)
Which of the following statements is correct about H2O2 with reference to these reactions? Hydrogen peroxide is ______.
(a) an oxidising agent in both (i) and (ii)
(b) an oxidisng agent in (i) and reducing agent in (ii)
(c) a reducing agent in (i) and oxidising agent in (ii)
(d) a reducing agent in both (i) and (ii)
NEETprep Answer7. The oxide that gives on treatment with dilute is
(a)
(b)
(c)
(d)
NEETprep Answer8. Which of the following equations depict the oxidising nature of ?
(a)
(b)
(c)
(d)
NEETprep Answer9. Which of the following equation depicts reducing nature of ?
(a)
(b)
(c)
(d)
NEETprep Answer10. Hydrogen peroxide is _____.
(a) an oxidising agent
(b) a reducing agent
(c) both an oxidising and a reducing agent
(d) neither oxidising nor reducing agent.
NEETprep Answer11. Which of the following reactions increases production of dihydrogen from synthesis gas?
(a)
(b)
(c)
(d)
NEETprep Answer12. When sodium peroxide is treated with dilute sulphuric acid, we get _____.
(a) sodium sulphate and water
(b) sodium sulphate and oxygen
(c) sodium sulphate, hydrogen and oxygen
(d) sodium sulphate and hydrogen peroxide
NEETprep Answer13. Hydrogen peroxide is obtained by the electrolysis of ______.
(a) water
(b) sulphuric acid
(c) hydrochloric acid
(d) fused sodium peroxide
NEETprep Answer14. Which of the following reactions is an example of use of water gas in the synthesis of other compounds?
(a)
(b)
(c)
(d)
NEETprep Answer15. Which of the following ions will cause hardness in water sample?
(a) Ca2+
(b) Na+
(c) Cl-
(d) K+
NEETprep Answer16. Which of the following compounds is used for water softening?
(a)
(b)
(c)
(d)
NEETprep Answer17. Elements of which of the following group(s) of periodic table do not form hydrides?
(a) Groups 7, 8, 9
(b) Group 13
(c) Groups 15, 16, 17
(d) Group 14
NEETprep Answer18. Only one element of ______ forms hydride.
(a) group 6
(b) group 7
(c) group 8
(d) group 9
NEETprep Answer19. Which of the following statements are not true for hydrogen.
(a) It exists as diatomic molecule
(b) It has one electron in the outermost shell
(c) It can lose an electron to form a cation which can freely exist
(d) It forms a large number of ionic compounds by losing an electron
NEETprep Answer20. Dihydrogen can be prepared on comercial scale by different methods. In its preparation by the action of steam on hydrocarbons, a mixture of CO and H2 gas is formed. It is known as _____.
(a) water gas
(b) syn gas
(c) producer gas
(d) industrial gas
NEETprep Answer21. Which of the following statement(s) is/are correct in the case of heavy water?
(a) Heavy water is used as a moderator in nuclear reactor
(b) Heavy water is more effective as solvent than ordinary water
(c) Heavy water is more associated than ordinary water
(d) Heavy water has lower boiling point than ordinary water
NEETprep Answer22. Which of the following statements about hydrogen are correct?
(a) Hydrogen has three isotopes of which protium is the most common
(b) Hydrogen never acts as cation in ionic salts
(c) Hydrogen ion, H+, exists freely in solution
(d) Dihydrogen does not act as a reducing agent
NEETprep Answer23. Some of the properties of water are described below. Which of them is/are not correct?
(a) Water is known to be a universal solvent
(b) Hydrogen bonding is present to a large extent in liquid water
(c) There is no hydrogen bonding the frozen state of water
(d) Frozen water is heavier than liquid water
NEETprep Answer24. Hardness of water may be temporary or permanent. Permanent hardness is due to the presence of
(a) chlorides of Ca and Mg in water
(b) sulphates of Ca and Mg in water
(c) hydrogen carbonates of Ca and Mg in water
(d) carbonates of alkali metals in water.
NEETprep Answer25. Which of the following statements is correct?
(a) Elements of group 15 form electron deficient hydrides
(b) All elements of group 14 form electron precise hydrides
(c) Electron precise hydrides have tetrahedral geometries.
(d) Electron rich hydrides can act as Lewis acids.
NEETprep Answer26. Which of the following statements is correct?
(a) Hydrides of group 13 act as Lewis acids
(b) Hydrides of group 14 are electron deficient hydrides
(c) Hydrides of group 14 act as Lewis acids
(d) Hydrides of group 15 act as Lewis acids
NEETprep Answer27. Which of the following statements is correct?
(a) Metallic hydrides are deficient of hydrogen
(b) Metallic hydrides conduct heat and electricity
(b) Ionic hydrides do not conduct electricity in solid state
NEETprep Answer28. How can production of hydrogen from water gas be increased by using water gas shift reaction?
NEETprep Answer29. What are metallic/interstitial hydrides? How do they differ from molecular hydrides?
NEETprep Answer30. Name the classes of hydrides to which , and belong.
NEETprep Answer31. If same mass of liquid water and a piece of ice is taken, then why is the density of ice less than that of liquid water?
NEETprep Answer32. Complete the followings equations
(i)
(ii)
NEETprep Answer33. Give reasons
(i) Lakes freeze from top towards bottom.
(ii) Ice floats on water.
NEETprep Answer34. What do you understand by the term 'auto-protolysis' of water? What is its significance?
NEETprep Answer35. Discuss briefly de-mineralisation of water by ion exchange resin.
NEETprep Answer36. Molecular hydrides are classified as electron deficient, electron precise and electron rich compounds. Explain each type with two examples.
NEETprep Answer37. How is heavy water prepared? Compare its physical properties with those of ordinary water.
NEETprep Answer38. Write one chemical reaction for the preparation of D2O2.
NEETprep Answer39. Calculate the strength of 5 volumes H2O2 solution.
NEETprep Answer40. (i) Draw the gas phase and solid phase structure of H2O2.
(ii) H2O2 is a better oxidising agent than water. Explain.
NEETprep Answer41. Melting point, enthalpy of vaporisation and viscosity data of H2O and D2O is given below
|
H2O |
D2O |
Melting point/K |
373.0 |
374.4 |
Enthalpy of vaporization at (373 K)/kJ mol-1 |
40.66 |
41.61 |
Viscosity/centipoise |
0.8903 |
1.107 |
42. Dihydrogen reacts with oxygen (O2) to form water. Write the name and formula of the product when the isotope of hydrogen which has one proton and one neutron in its nucleus is treated with oxygen. Will the reactivity of both the isotopes be the same towards oxygen? Justify your answer.
NEETprep Answer43. Explain why HCl is a gas and HF is a liquid?
NEETprep Answer44. When the first element of the periodic table is treated with dioxygen, it gives a compound whose solid state floats on its liquid state. This compound has an ability to act as an acid as well as a base. What products will be formed when this compound undergoes autoionisation?
NEETprep Answer45. Rohan heard that instructions were given to the laboratory attendent to store a particular chemical, i.e., keep it in the dark room, add some urea in it, and keep it away from dust. This chemical acts as an oxidising as well as a reducing agent in both acidic and alkaline media. This chemical is important for use in the pollution control treatment of domestic and industrial effluents.
(i) Write the name of this compound.
(ii) Explain why such precautions are taken for storing this chemical.
NEETprep Answer46. Give reasons why hydrogen resembles alkali metals?
NEETprep Answer47. Hydrogen generally forms covalent compounds. Give reason.
NEETprep Answer48. Why is the ionisation enthalpy of hydrogen higher than that of sodium?
NEETprep Answer49. Basic principle of hydrogen economy is transportation and storage of energy in the form of liquid or gaseous hydrogen. Which property of hydrogen may be useful for this purpose? Support your answer with the chemical equation if required.
NEETprep Answer50. What is the importance of heavy water?
NEETprep Answer51. Write the Lewis structure of hydrogen peroxide.
NEETprep Answer52. An acidic solution of hydrogen peroxide behaves as an oxidising as well as reducing agent. Illustrate it with the help of a chemical equation.
NEETprep Answer53. With the help of suitable examples, explain the property of H2O2 that it is responsible for its bleaching action?
NEETprep Answer54. Why is water molecule polar?
NEETprep Answer55. Why does water show high boiling point as compared to hydrogen sulphide? Give reasons for your answer.
NEETprep Answer56. Why can dilute solutions of hydrogen peroxide not be concentrated by heating? How can a concentrated solution of hydrogen peroxide be obtained?
NEETprep Answer57. Why is hydrogen peroxide stored in wax lined bottles?
NEETprep Answer58. Why does hard water not form lather with soap?
NEETprep Answer59. Phosphoric acid is preferred over sulphuric acid in preparing hydrogen peroxide from peroxides. Why?
NEETprep Answer60. How will you account for bond angle in water?
NEETprep Answer61. Write redox reaction between fluorine and water.
NEETprep Answer62. Write two reactions to explain amphoteric nature of water.
NEETprep Answer63. Correlate the items listed in Column I with those listed in Column II. Find out as many correlations as you can.
Column I |
Column II |
A. Synthesis gas |
1. |
B. Dihydrogen |
2. Oxidising agent |
C. Heavy water |
3. Softening of water |
D. Calgon |
4. Reducing agent |
E. Hydrogen peroxide |
5. Stoichiometric compounds of s-block elements |
F. Salt like hydrides |
6. Prolonged electrolysis of water |
|
7. |
|
8. |
|
9. Synthesis of methanol |
|
10. Mixture of CO and H2 |
64. Match Column I with Column II for the given properties/applications mentioned therein.
Column I |
Column II |
A. H |
1. used in the name of perhydrol. |
B. H2 |
2. can be reduced to dihydrogen by NaH. |
C. H2O |
3. can be used in hydroformylation of olefin. |
D. H2O2 |
4. can be used in cutting and welding |
65. Match the terms in Column I with the relevant item in Column II.
Column I |
Column II |
A. Electrolysis of water produces |
1. atomic reactor |
B. Lithium aluminum hydride is used as |
2. polar molecule |
C. Hydrogen chloride is a |
3. recombines on metal surface to generate high temperature |
D. Heavy water is used in |
4. reducing agent |
E. Atomic hydrogen |
5. hydrogen and oxygen |
66. Match the items in Column I with the relevant item in Column II.
Column I |
Column II |
A. Hydrogen peroxide is used as a |
1. zeolite |
B. Used in Calgon method |
2. perhydrol |
C. Permanent hardness of hard water is removed by |
3. sodium hexametaphosphate |
|
4. propellant |
67. Assertion (A) Permanent hardness of water is removed by treatment with washing soda.
Reason (R) Washing soda reacts with soluble magnesium and calcium sulphate to form insoluble carbonates.
(a) Statements A and R both are correct and R is the correct explanation of A
(b) A is correct but R is not correct
(c) A and R both are correct but R is not the correct explanation of A
(d) A and R both are false
NEETprep Answer68. Assertion (A) Some metals like platinum and palladium, can be used as storage media for hydrogen.
Reason (R) Platinum and palladium can absorb large volumes of hydrogen.
(a) Statements A and R both are correct and R is the correct explanation of A
(b) A is correct but R is not correct
(c) A and R both are correct but R is not the correct explanation of A
(d) A and R both are false
NEETprep Answer69. Atomic hydrogen combines with almost all elements but molecular hydrogen does not. Explain.
NEETprep Answer70. How can D2O be prepared from water? Mention the physical properties in which D2O differs from H2O.Give at least three reactions of D2O showing the exchange of hydrogen with deuterium.
NEETprep Answer71. How will you concentrate ? Show differences between structures of and by drawing their spatial structures. Also mention three uses of .
NEETprep Answer72. (i) Give a method for the manufacture of hydrogen peroxide and explain the reactions involved therein.
(ii) Illustrate oxidising, reducing and acidic properties of hydrogen peroxide with equations.
NEETprep Answer73. (i) What mass of hydrgen peroxide will be present in 2 L of a 5 molar solution?
(ii) Calculate the mass of oxygen which well be liberated by the decomposition of 200 mL of this solution.
NEETprep Answer74. A colourless liquid 'A' contains H and O elements only. It decomposes slowly on exposure to light. It is stabilised by mixing urea to store in the presence of light.
(i) Suggest possible structure of A.
(ii) Write chemical equations for its decomposition reaction in light.
NEETprep Answer75. An ionic hydride of an alkali metal has significant covalent character and is almost unreactive towards oxygen and chlorine. This is used in the synthesis of other useful hydrides. Write the formula of this hydride. Write its reaction with .
NEETprep Answer76. Sodium forms a crystalline ionic solid with dihydrogen. The solid is non-volatile and non-conducting in nature. It reacts violently with water to produce dihydrogen gas. Write the formula of this compound and its reaction with water. What will happen on electrolysis of the melt of this solid?
NEETprep Answer
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