HYDROGEN AND ITS COMPOUNDS INTRODUCTION Hydrogen is the lightest element and also the lightest gas in the periodic table. It is the lightest non-metal. It is the simplest element in periodic table having only le 1p & no neutron. Electronic configuration of H is 1s! Number of @ = 1 Number of orbital = 1 Number of shells = 1 Number of subshell =1 It is discovered by Henry Cavendish & it was called inflammable element The name hydrogen was given by Lavoisier Hydrogen —4—__, Hydro (Water) Gene (Producer) or generator means according to Lavoisier the gas which produce water on buming with oxygen. 1 H, +50, >H,0 Order of Abundance of H Hydrogen is the most abundant element in the universe (70% of the total mass of the universe.) Order of abundance of H Universe > Sun atm > Earth The planet Jupiter 8 Saturn consist mainly of H,, Similarly about half the mass of the sun & some other stars is made up of hydrogen. In Sun's atomsphere & in universe, It is found in atomic forrn, While in earth it is generally found in molecular form. At Sun, the stratosphere is made up of H (atomic hydrogen) & they undergoes fusion & converted into He rhuclel & this reaction is exothermic so lot of amount of energy is liberated. It is the ninth element on earth in order of abundance. Earth does not posses enough gravitational force to retain live hydrogen molecule i.e. why it is not found in earth atomosphere in atomic form. Hydrogen is the most reactive elements in atomic form but it is less reactive in molecular form because of very high bend dissociation energy due to 1s -1s overlapping, POSITION OF H, IN PERIODIC TABLE Hydrogen is the first element of Periodic table but still it could not be assigned a proper position either in Mendeleef periodic table or in Modem periodic table because of following reasons. It may kept in TPYIA or 17°/VIIA. group due to following reason, Resembeles with 1*/IA Alkali metals. (i) Electronic configuration Like alkali metals hydrogen also has only one electron in outer most shell = H= 1s K = ds = Li = 2¢ Rb = 5s! as! = Na = 38 (ii) Electropositive characters : Like alkali metals hydrogen also have the tendency to loose one electron to form cation, °(an) (wv) w (wid eg. Na > Nai + e@ H > H + e (Proton) Oxidation numbers : Like alkali metals hydrogen can also exhibit the oxidation number of +1 in most of its compound. eg. Na‘Cl KCl HCl aH Reaction with electronegative elements (non-metals) : Like alkali metals H also reacts with Oxygen, Sulphur, Halogens to form oxides, sulphides and halides respectively © sis, HO, like Na,O, KO S whe, HS, like NaS, KS. with halogen 28, HX, like NaX, KX Liberation at Cathode 2Na Cl sso, 2Na + a Uiberated at cathode) (liberated at anode} 2H Cr estes tH, + cl) like alkali metals H also get liberated at cathode on electrolysis Reducing nature : Like alkali metals H, also have reducing nature. CuO +H, —> Cu + HO Due to resembling of these properties with alkali metals H can be placed in IA/group Jelkali metals group. Resembles with halogen/ VIIA/17" (i) Electronic configuration Electronic configuration of halogen H —> 1s! —> nsinp? both these requires one electron to attain the stable configuration of their nearest inert gas. H—> lst le tesiion He (155) F—+ 2p __1e weit, Ne (2p) > Gp? Te essthan Ar (Sp) (ii) Electronegative character : Both halogen & Hydrogen has the tendency to gain one e F+e —>F H+e—>H i.e. why both will act as electronegative species (Gis) Ionization potential : [onization potential of hydrogen is almost similar to halogen. (iv) Oxidation number : Both halogen & hydrogen can exahibit ~1 oxidation number. Hydrogen in metal hydride shows ~1 oxidation state NaH —> Na’ +H NaCl —> Na’ + Cl () Diatomic molecule : Both halogen & hydrogen have the tendency to exist as diatomic molecule. eg. Fy, Cl, Bry L, & Hy (vi) Liberation at anode : Whenever Alkali metals halides & hydrides undergoes electrolysis, both halogen and hydrogen will liberate at anode.2Na’ Cl —> 2Na + Cl, (anode) 2Ne’ H —> 2Na +H, (anode) (vii) Reaction with highly electropositive metals : Hydrogen reacts with highly electropositive element (i.e. s-block elements) & forms their hydrides like their halides. 2Na +H, —> 2NaHi 2Na + Cl, —> 2NaCl This reaction shows oxidising character of hydrogen, (viii) Formation of covalent compound : Both Hydrogen & halogen on reaction with non metals to form covalent compounds bike. CH,, NH,, H,0 CCl, NCI,, C10 Conclusion : The position of hydrogen is still in controversy & no proper position is assigned to H in petiodic table i. why itis also called notorious or rogue elements ISOTOPES OF HYDROGEN There are 3 isotopes of H, Protium or Deuterium/ Tritium ordinary hydrogen | Heavy hydrogen Symbol iH HYD yD H Dy r Property Protium or | Deuterium or Tritium ordinary heavy hydrogen hydrogen Atomic number 1 1 1 Mass umber 1 2 3 Exact atomic mass 1.008123 2.0142 3.0170 Symbol iW 2H 2D SH or 37 Molecular formula H, D, y No. of protons in. the nucleus 1 1 1 No.of neutrons in the mucelus Nil 1 2 No. of electron 1 1 1 Electronic configu. Is Is! Is! Relative abundance 99.984% 0.016% 10 % Stability Stable Stable Unstable(Radioactive) Properties H, D. MP. ~ 259°C = 254.3°C ~ 252.4°C BP. ~ 252.6°C ~ 249.3°C ~ 248.0°C Bond length (H- H) 74 pm 74 pm 74 pm Bond energy (HH) 436.0 KJ mol? 443.3 KJ mot 446.9 KJ mol Heat of fusion & vaporisation Minimum, H Here also only a fraction is increased But in case of hydrogen mass increased to 2 to 3 times in their isotopes. Isotopic effect is found in (HH (2)N (3) c (4) All {1) Which of the following reaction is fast & why ? () CH, + CL —> CHC + Hel (i) CD, +O, — CD,C1 + Dal {i) because C-H bond energy is less in comparison to C-D bond energy. Different forms of Hydrogen (a) Based on oxidation Number. There are three types of hydrogen H H H Proton Hydride Atomic hydrogen Number of electon] 0 2 1 Oxidation number +1 -1 o Formation HoH +eH+e HH, —>2H Note : In the aqueous state proton (H') exist as H’ (H,O), Where n is a large number, if een — H,0 n=2 — HHO), In the equeous solution hydrogen ion exist as (1) Ho (2) HHO), (3) HH,0), 4) All 4) (b) Based on reactivity Hydrogen 4 ‘Atomic Hydrogen ‘ Simple atomic H Nascent hydrogen Adsorbed/OccofludedSa Atomic hydrogen (1) Simple atomic hydrogen ~ It is formed by simple dissociation of hydrogen. 3000-5000 H, 2H Favourable comaition ~ Favourable condition are high temp & low pressure. (ii) Nascent hydrogen ~ Hydrogen at the moment of its birth it called nascent hydrogen means which forms at the instant is known as Nascent hydrogen, It is formed only by some specific chemical reaction. (a) Acid + Metals Zn 0, > 2nS0, + 2H (b) Base + element 2NaOH + Be —> Na,BeO, + 2H (©) CH,OH + Alkali metal C\H.OH + Na —> C,H,ONa + H (iii) Adsorbed/Occluded hydrogens Concentration of H is more Adsorbed His hydrogen present at the outer surface of metal Occlusion ~ The property of metal to adsorb any gas is called occlusion. Reactivity order Atomic hydrogen > Nascent hydrogen > Molecular hydrogen (c) Based on Nuclear spin (Nuclear isomers) Hydrogen Ortho Para (2) Ortho hydrogen ~ The molecular form of hydrogen having same spin of proton is called ortho hydrogen. (b) Para hydrogen - The molecular form of hydrogen having opposite spin of proton is called para hydigen. In ortho hydrogen spin of proton is same, so they will repel each other & because of this repulsion, intemal energy of ortho hydrogen increases. So ortho hydrogen has more internal eneray. Stability of ortho & para hydrogen Stability of ortho & para hydrogen depends upon temperature condition, ‘At low temp : para hydrogen is mote stable than ortho hydrogen while at high temp ortho hydrogen is more stable than para hydrogen T > = Ortho Para AL25C 75% 25% At -253 C/20K 0 100%eae! ° Ans. Imp. Note : (i) We can obtain 100% pure para hydrogen at low temp but can't ortho because at high temp parahydrogen will dissociate into atomic hydrogen. (i) Ortho & Para hydrogen differs only in physical properties but have same chemical properites. Method of preparation 1. From acids : The metal which are placed about H, in electrochemical series react with dil acids they berate H., eg. Fe +H,S0, — FeSO, + H, (ai) Cu +H,0, > (No reaction) Lab preparation : When impure Zn reacts with dil H,SO, it forms H, Zn + HSO, + ZnSO, + F (impure) (ai) Why we use impure Zn. Because the rate of reaction with pure Zn is very slow. By alkalies : Only (Be, Zn, Al, Sn, Pb, Si) (Amphoteric metal) react with boiling NaQH or KOH they evolve H,, Zn + 2NaOH > Na,Zn0, + Ht (sodium zincate) 2A + 2NaOH + 2HO —> Naalo, + 3H, (odium meta ahuminate) Sn + 2NaOH + H,0 —> Na,Sn0, + 2H, (Godium stannate) Pb + 2NaOH + HO —» Na,PbO, + 2H, (sodium plumbate) Si + 2NaOH + H,O —> Na,SiO, + 2H, (eodlum siicate) Be + 2NeOH —> Na,BeO, + H, (sodium beryliate) From water : All the metals which are placed above than H, when react with water the evolve H, Zn + H,O —> Zn0 + Ht Three type of water is used {i) Cold water : The temperature of cold water is 7 to 25C this water is used for highly reactive metals. Such as Li, K, Ba, Sr, Ca, Na, means alkall metals of alkali earth metal. The reaction with alla metals are vigorous to minimum the rate of reaction these metals are used in the form of amalgam. 2Naltig) + HO —> 2NaOH + Ht {ii) Hot water : The temperature of hot water is 25 C to 90.C. This water is used for reactive metals, such as Mg, Al, Mn, Zn, Cr. (ii) Steam : The temperature of steam is more than 100 C. This form of water is used for very less reactive metals bke Fe, Ca, Co, Ni, So, Pb Condition for best yield of Hy {Cold water —> With highly reactive metals (i) Hot water —> With reactive metals Gi) Steam —> With less reactive metas‘4. On Ionic hydride Whenever ionic hydride reacts with water then form H,, Cali, + 2H,0 —+ Ca(OH, + H, (Hydrolith) NaBH, + HO —> NaBO, + 4H, Method to prepare pure hydrogen 1, Electrolysis of water : To prepare pure hydrogen we use impure water (2. having 15-20% solution of alkali or acid) 4H,0 1 4H’ + 40H at cathode 4H + 4e —> 2H, at anode 40H —> 2H,0 + ©, + 4e The SO,? oF K’ Jon present in acid or alkali does not move towards anode or cathode as their discharge potential is higher than of OH’ lons or H’ ions rescpectively 2, By reaction of Magnesium with dil, H,S0, Mg + H.SO, —> MgSO, + H, 3. B reaction of NaH with water NaH + HO —> NaOH + H, 4. Uyeno method : This method is used for miltary purpose 2Al + 2KOH + 20 —> 2KAIO, + 3H,t (Potassium meta aluminate) Because by this reaction we can prepare H, in a rapid nanner Commercial or industrial method to prepare H., (i) Lane process : Steam is passes over hot iron it converts into Fe,O, & H,, 3Fe + 4H,0 —> Fe,0, + 4H, Iron is regenrated by reducing Fe,O, into Fe by water gas (CO + H) 2Fe,0, + 4CO + 4H, —> 6Fe + 4C0, + 44,0 Fo,0, + 2CO + 2H, —> 3Fe + 2CO, + 2H,0 This process is @ continuous process (li) Bosch Process + In this process initially steam is passed over red hot coke then water gas is formed C+HO—>Co+H, ‘Then water gas is mixed with more stem in presence of Fey can obtain more Hy CO +H, + H,0 —> CO, + 2H, (ili) From Natural gas Hyp + HHO —> nO + (2n + 1H, 5. PHYSICAL PROPERTIES OF HYDROGEN (9) Hydrogen isa lightest, colourless, odourless and tasteless gas. It is sparingly soluble in water: It is inflammable and less reactive gas. i) Its fp. (© 259.2%) and b.p. 252°C) are very low indicating less intermolecular attraction, Due to low fp. liquid hydrogen is used as a eryogenic fluid (to produce low temperature) (ii) HH bond energy | 104 Keal mot] and 436 KiJ/m (i) H.= H bond length | 74 pm so Fi, is less reactive and require high temp for reaction. /Cr,0, then CO will convert into O, & we Chemical properties of H, ©) Hi is neutral in nature Le. why it does not react with acids & bases. = Hydrogen is very less reactive in nature because of very high bond dissociation energy. °a) (w) « () (i) «at Combustible nature : H, is highly combustible in nature & it burns with oxygen or ar with pale blue flame to give water. 1 H, + 50,—> HO Reaction with highly electropositive metals 1A & IIA group elements are called highly electrpositive metal, Whenever H reacts with these metals they form tonic hydrides. 2Na +H, —> 2NaH Ca +H, > GH, Reaction with non-metal (a) Reaction with halogen H, +X, —> 2Hx Fy Ch, Br) order of reactivity of halogen with hydrogen F,> CL, > Br, >I, (b) Reaction with sulphur H,+S—>HS (c) With nitrogen ~ (Haber process) 683K N+ 3H, poyo-zous? 2NHB Reducing nature (CuO +H, —> Cu + H,0 Reaction with carbon mono oxide 2n0/Cr404 373K Hydrogenation of unsaturated hydrocarbon, CH, + 2H, —> CH, 2H, + CO > CH,OH (MethanoD Ni/Pb/Pt GH, + Hy a? CH, When unsaturated hydrocarbon having C = C or C = C reacts with hydrogens in the presence of Ni/Pd/Pt forms saturated hydrocarbons, Imp. Hydrogenation of vegetable oll. Vegetable oils are also called polwnsaturated oils because they contain many C = C bond. When these oil are exposed to air for a long time then double bond will get oxidized and the oil becomes. Rancid (having fowl smell or unpleasant test) in nature. So to avoid this vegetable oil are converted into edible fats (Vanaspati Ghee) Vegetable oils +H, Ny cate fats sold (liquid) This whole process is known as hydrogenation or hardening of ofl USES OF HYDROGEN + 1. Hydrogenation of vegetable oil to form solid fats i.e. vanaspati ghee. 2. In liquid form as a rocket fuel. (Liquid H, + Liquid 0.) 3. Ina air ship of halloons as a mixture of Hydrogen & Helium [15% H, + 85% He) 4. Formation of different compounds. Like > NH,, (Haber process) alkane, alcohol and other hydrocarbonbe ats “The compounds of hydrogen with diferent elements are called hydrides. ‘These are of three types (1) Ionic/Salt like/Saline hydrides Compounds of hydrogen with s-block elements except berylum & magnesium are called ionic hydrides. LIH, NaH, KH, RbH, CsH, CaH,, SeH,, Ball, BeH,, MgH, are covalent polymeric hydride Structure of these hydrides are similar to rock salt, so they are also called salt like/saline hydrides. Down the group size? Lattice energy! stability Melting point! Boiling point) On electrolysis of these hydrides, hydrogen is Hberated at anode. (On reaction with water these hydrides will form hydrogen NaH + HO —> NaOH + H, These hyerides forms complex hydrides which are very good reducing agents. 4LH ~ AICI, —> LAH, + SLIC1 NaBH, —> Sodium borohydride LiAIH, —> Lithium aluminium hydride. (2) Mettalic / Interstitial hydrides : Sa They are the compounds of d & flock elements dS (e x ooee . In these hydrides hydrogen occupies interstitial sites present in metallic lattice, so they are called interstitial hydrides. © Properties of these hydrides are similar to parent metals, so they are also known as metalic hydrides. © These hydrides are non. stochiometric in nature (i.e, having variable composition) Zrkix (x = 1.3 - 1.75) Ti («= 18 - 2) © Metals of group 7.8,9 donot form any hydrides so this particular part of periodic table is known as hydride gap. (3) Covalent/Moleculer hydrides © They are the compounds of hydrogen with p-block elements CH,, NH,, H,0, HF, ete. © These hydrides exist as molecules, so they are also known as molecular hydrides. There hydrides are non-conduetor of electricity Nomenclature ~ element + Suffix (ane) PH, —> Phosphane NH, —> Azane H,0 —+ Onidane These hydrides are again divides into 3 categories (@) Electron deficient hydrides They are the hydrides of group 13 elements, BH, AIH,, Gall, ~ In these hucrides central element does not have complete octet. i. why they are called electron deficient compounds, (b) Electron precise hydrides - They are the hydrides of group 14 element eg. CH,, SIH, GeH, In these type of hydrides central elements has Sein their outer most shell. (€) Electron rich bycrdes : These are the hydrides of group 15, 16, 17 eg. NH, H,O, HE: ete. In these hydrides lone pair are present on central dement which can be given to others. So they ate called electron rich hydrides. °Water (H,O ) Properties of pure water (a) Physical properties {) Pure water is colourless, tasteless and odourless. It gives blush tinge in thick layers. (i It freezes at 0 C and boils at 100 C. (i ts maximum density is 1.00 at 4 C. (iv) Itis a polar molecule and has V-shaped structure, The bond angle is 104.5 .(v)Ithas a high dielectric constant, The polar character of water makes it an excellent sokent for polar and ionic substances. (vi) It is a poor conductor of electricity. (i) It has the tendency to associate It exists in the liquid state not as a single H,O molecule but as associated molecules through hydrogen bonding. The existence of hydrogen bonding is responsible for high values of specific heat, the latent heat of fusion and latent heat of vaporisation, (b) Chemical properties () Water is neutral in nature, pH of the pure water is 7. It s a weak electrolyte and feebly ionises into H and OH HO = H+0H In pure water [H'] = [OH] = 107 at 25 C. (i) With metals : it reacts with active metals and evolves hydrogen. The reaction is exothermic in the case of alkali and alkaline earth metals. 2Na+ 2H,O—> 2NaOH +H, Ca + 2H,O—> CalOH), +H, (ii) Reaction with non metals Chlorine decomposes cold water forming HCl and HCIO. cl, +HO—>Hal + HCIO When steam is passed over red hot coke (1000 C), water gas is formed C+H,0 > CO+H, (iv) Action on nonmetalic oxides : Acidic oxides combine with water to form acids CO, +H,0 = H,00, (Carbonic acid) s 50, + H,O—>H,S0, (Sulphurous acid) 1,80, (Sulphuric acid) P,0,+3H,O—> 2H,PO, (Orthophosphoric acid) N,0, + H,O—> 2HNO, (Nitric acid) CLO, +H,O—> 2HCI0, Perchloric acid {¥) Action on metallic oxides : basic oxides combine with water to form alkalies, Na,O + H,O—> 2NeOH C20 + H,O—> CalOH, (i) Action on hydrides, carbides, nitrides, phosphides : Water decomposes these compounds with liberation of hydrogen, acetylene (or methane, ammonia, phosphine respectively CoH, + 2H,O—> Ca(OH), + 2H, Ca, + 2H,O—> CalOH), * CH, ALC, + 12H,0— > 4AN0H), + 3CH,Mg,N, + 6H,0—> 3MglOH), + 2NH, CaP, + 6H,O—> 3Ca(OH), + 2PH, (ui) Hydrolysis : Many salts specially the salts of strong bases with weak acids,weak bases with strong acids and ‘weak bases with weak acids undergo hydrolysis with water. CH,COONa + H,0 = CH,COOH + NaOH CH,COONH, + O = CH,COOH + NH,OH Halides of nonmetals are decomposed by water, PCl, + 4H,0—> HPO, *5HCI PCI, + 3H,0—> HPO, + 3HCL Hard and soft water ‘A.water is said to be a soft water if it produces sufficient lather with the soap and water is described as being hard if it forms an insoluble scum before it forms a lather with soap. The hardness of natural water is generally caused by presence of bicarbonates, chlorides and sulphates of calcium and magnesium but infact soluble salts that form a scum with soap ‘cause hardness CaP aq) + 2C,,H,,COO (aq) —>(C, H_,C00),Ca Mg** (aq) + 2C7Hy.COO”(aq)—> C,,H,,COO),Mg Sacto Ponies Soap will not produce lather with water until all the calcium and magneslum fons have been precipitated. Hard water thus wastes soap. Hardness of water is of two types {@) Temporary hardness (0) Permanent hardness {@) Temporary hardness : This is due to the presence of bicarbonetes of calcium and magnesium, Temporary hardness in water is easily removed by boing, as the bicarbonates decompose readily and the insohible carbonates are precipitated CalHCO,), + CaCO, + H,0+CO, MaiHCO,), —™ +MgCO, +H,0 +CO, ‘Temporary hardness can also be remaved by Clark's process which invohes the addition of slaked lime [Ca(OH]. CafF#C0,), + CHOHI, —> 2CaCO * 24,0 GaEO It is essential to add only the calculated amount of Ca(OH), because excess will cause artificial hardness. (8) Permanent hardness: Permanent hardiness is infroduced when water passes aver rocks containing the sulphates or chlorides of both of calcium and magnesium. This type of hardness cannot be removed by boiling or by the addition of slaked lime. “The various water softeners are (i) Washing soda : It removes both the temporary and permanent hardness by converting soluble calcium and magnesium compounds into insoluble carbonates. °w aw) (wo) CaCl, + NaCO, = CaCO, + 2NaCl (CaSO, + Na,CO, = CaCO, + Na, 0, CalHICO), + Na,CO,~ CaCO + 2NaHCO, In place of sodium carbonate, caustic soda or sodium phosphate can also be used. MgCl, + 2NaOH—> Mg(OH), + 2NaCl MgSO, + 2Na,PO,—> Mg, (PO,), +3Na,SO, Calgon : The complex salt of metaphosphoric acid, sodium hexametaphosphate (NaPO)), is known as calgon. Itis represented as Na,{Na,(PO)),. Calcium and magnesium salts present in hard water react with calgon to give complex sats ‘2CaSO, * No,{Na,(PO,),) —> Na,{Ca{PO,)]+ 2Na,SO, 2MgSO, + Na,[Na,(PO,), —> Ne,{Mg,{PO,)+2No,S0, Permutit process : Permutit is hydrated sodium akumino sicate Na,ALSi,0, xH,0} Hard water — INa,0.AL0, 25:0, xH,0] NaCl solution Permit also known as sodium zeolite (Ne,2). means Zeolite is Al,Si,O,-xH,O. Naz water In this process when hard water is poured Gayo into chamber, it may contain organic impurities lke plant. This impurities can be removed by gravel Impurities On moving upwards hard water will react with Na,Z during this reaction Na’ ions of Na,Z. will replace Mg’? & Ca"? of impurities 7 NaZ. + CaCl, —> 2NaCI + Caz NaCl is dissolved in water & water becomes soft This soft water is fit for washing purpose but not fit for drinking purpose After some time when Na,Z is completely converted into CaZ. Process is stopped and for regeneration of Na,Z. We use NaCl solution. 2NaCl + Caz —> CaCl, + Naz Jon exchange resin + By this process we can remove both cation & anion of hardness This process contain two chamber. (a) Cation exchange resin : This resin contains granular insoluble organic acid having giant molecules with COOH group. (b) Anion exchange resin : This resin contain glant organic molecules with basic groups derived from amines R-NH,OH Process : When hard water is poured into first chamber the cation of hardness (Mg. Ca“) removed by H" ions of organic acid 2R-COOH' + CaCl, —> R-COO),Ca+ 2H + 2C1 +MgSO, —>(R-COO),Mg + 2H' + $0,#Impure water HY Cr, SO se Ca, Na’, SOL CL Caton exchange regeneration Dilute acid for y i Waste Waste Pure water ‘This water becomes soften but not used for drinking purpose because this water contain the impurity of acid, To remove anion of hardness this acidic water then passed through another bed containing anion ‘exchanger. This exchanger removes anion lke Cr, $0, & HCO, R-NH,OH +H’ + Cl —> R-NH,'Ch= H'0H This waters foe from impurities & can be used for drinking purpose. After some times when both resin gets exhausted process is stopped Regenration of resin @) Cation exchange resin: We use dil acd 2H'Cl + R-COO},Ca—> 2A COOH + CaCl, (8) Anion exchange resin: We use dil NOH solution R-NH, Cl + Na'OH' —> Na'Cl + R-NH, OH Heavy water (D,O) Method of preparation Repeated electrolysis of H,O : On clectroisis of water impure) HO dissocite into HT part of D,O will dissoctate into D' & OD & OH while a fractional HO = H+ 0H D,0 = D'+ 0D ’ & OD: due to more mass have less mobily i.e. why H’ & OH will move towards cathode & anode respectively while D* & OD willbe in sohition This process will peated for sx ime Properties of Heavy water Physical properties : (a) Heavy water is a colourles, odourless and tasteless mobile liquid, (b) Nearly all the physical constants are higher than the corresponding values of ordinary water. Chemical properties : Heavy water is chemically similar to ordinary water, However, D,O reacts more slowiy than H,0 in chemical reactions. {@) Action of metals : D,O reacts with alkali and alkaline earth metals Uberates heavy hydrogen2D,0+2Na—> _2NaOD_, +D, 2D,0+Ca—> CalOD), +, (6) Action with metallic oxides : D,O reacts slowly with basic oxides to form heavy alkalies. Na,O+D,0—> 2Na0D CaO +D,0—+ CaOD), (© Action with nonmetallic oxides : D,O reacts slowly with acidic oxides to form deutero acids N0,+D,0O— P,0,+3D,0—> 2D,PO, $0,+D,0—> _ D,SO, (@ Action with metallic carbides, phosphides, nitrides, arsenides, ete. : Like H,O heavy water reacts with carbides, phosphide nitrides, arsenides, etc. to form corresponding deutero compounds, Cae, + 20,0 —> COD), C.D, ALC, + 12D,0—> 4Al(0D),* _ 3CD, Mg.N, + 6D,0—> 3MgiOD),+ _2ND., AIN+3D,0—>AKOD),> ND, CaP,+6D,0—> 3Cx{0D),+ 2PD, NaAs*8D,0—> 3N20D+ AsD, (€) Electrolysis : A solution of heavy water containing Na,CO, when electrolysed evolve heavy hydrogen at cathode 20,02" 5 2D, + 0, Uses : As a neutron moderator : Fission in uranium-235 is brought by slow speed neutrons. The substances ‘which are used for slowing down the speed of neutrons are called moderators. Heavy water is used for this purpose in nuclear reactors.+ H,O, (Hydrogen Peroxide) Laboratory method : In laboratory, HO, is prepared by adding calculated amounts of sodium peroxide to ice cold dikite (20%) solution of 180, Na,O, + H.SO, —> Na,S0, + H,0, By the action of sulphuric acid or phosphoric ac on hyxtrated barium peroxide BaO, SHO (Merck process) 2) BaO,8H,0+H,$0,—> BxS0,1+H,0, +8H,0 ‘Anhydrous barium perexide does not react readity with sulphuric acid (because a coating of insohible barium sulphate is formed on its surface which stops further action ofthe acid). Therefore, hydrated barium peroxide, BaO, 8H,O must be wed (b) 8820, + 2H,PO, —> Ba/PO,), + 34,0 Ba (PO), + 3H,S0,—> 3BaSO, + 2H,PO, Phosphoric acid is preferred over H,SO, because soluble impurities like barium persulphate {Ba0, $H,0 -H,SO,) tends to decompose H,O, while H.PO, acts as preservative (negative catalyst) for H,0,, [Industrial Method! (Auto oxidation of 2 butyl anthraquinol ( cyclic process) OH ary OH (i) Oxidation of isopropyl aleohol = CH—CH—CH, + 0, —> I OH (ii) Electrolytic Process : Used 50% H,$O, in electrolytic cell using Pt as anode graphite as cathode. 2H,S0, ——> 2H" + 2HSO° ‘At Cathode 2H" + 2e——>H, T At Anode 2HS0,- Physical property (Pure HO, is colour less, odourless liquid and impure with bhush layer. (i) It has more Hydrogen bonding then H,0, So. order of boiling point H,0, > D,O > H,0) (ii) It is soluble in H,O, alcohol and ether (iv) It has bitter test and harmful for skin () [tis a dibasic weak acid (wi) Ithas @ oxidising as well as reducing property (wi) H,0, easily decompose in presence of light and temperature, So HO, aluays kep in dork bottles and kept at cool places, (cil) 30% solution of HO, is called Perhydrol °° Chemical property 1 Stabily : It is unstable in nature decompose on standing and heating. It is an example of auto oxidation-reduction Reaction; H,0, > HO + 0 Note : Nascent oxygen working as colourless agent Decomposition of H,0, ; 2H,0, —=*2H,O + 0, Note : This is retarded by R-OH, acetenilide, glycerol Oxidizing nature : HO, is a powerful oxidant in acidic as well as in alkaline medium, (Inacid) HO, + 2H'+2e fst, HO Ely =1.77V (In alkal) © H.O+HO, +2e _S=_, 3HO- Et, 3v Thuse HO, is more powerful oxidant in aciic medium. The simple interpretation of H,O, as oxdant can be shown by the equation - H,0,—>1,0+0 Following are some important examples of oxidant action of HO, (a) 1,0, oxdises blac lead sulphide PS) to white lead uiphate(POSO,). Ths reaction is used in restoring the white colour of old paintings which have blackened due to the formation of lead sulphide by the action of H,S present ano, >H,0-0} PeS+40 PESO, PbS + 4,0, ——> POS, + 4H,0 }) HO, oxidises suiphites into sulphates H,0,. —>H,0+0 Na,SO,+O———> Na,S0, Na,SO, + H,0, ——> Na,S0, +H,0 (HO, oxidises nitrites to nitrates, H,0,.—>,0+0 Na,NO,+O— > NaNo, Na,NO, + HO, Na,NO, + H,0 (@ HO, oxidises H,S into sulphur 10, ———> H,0+0 HS+0 > HFS HS+H,0, > 2H,0+8 Reducing nature : It can also act as @ reducing agent towards powerful exidising agents H,0, 9 2H' +0, +26 (2) Itreduces Ag,O to sive. Ag, +H,0,—> 2Ag*H,0+0, ()—Itreduces ozone to oxygen. H.0, +0, —>H,0+ 20,[Structure of Hydrogen Peroxide’ H 95.0pm 147.5pm is? (a) Gas phase (a) Solid phase The vapour density as determined by Victor Meyer method at 90 is 17. Hence, the molecular mass of H,O, is 34. The calculated vakie of the single bond O-O distance is 147.5 pm and X-ray measurements shows what in hydrogen peroxide, O-O bond distance is 1.46 + 0.08A, The value of dipole moment of HO, is 2.1 D. This suggests that all the four atoms do not lie in the same plane, The molecule can be pictured as ling on the spine of a book open to an angle of 111.5. The hydrogen atoms are present one on each cover and H-O bonds making angles of 94.8 with the O-O bond as shown in fig. The bond distance between O-H is 95 pm Precautions @ HO, can not be stored in simple glass bottles since rough surface of glass [alkali oxides present in it] excited by light and decomposed H,0,. So the HO, usually stored in coloured, paraffin wax coated, plastic bottle. (i) Always with HO, add small quantity of inhibitor or negative catalyst to stay decomposition of Uke H,PO,, acetaniides ete Uses Bleaching agent (i) Hair dying (ii) HO, + N,H, as Rocket propellent iv) HO, as oxidant and reductant (v) Antiseptic DIHYDROGEN AS A FUEL :~ Dihydrogen releases large quantities of heat on combustion. The data on energy released by combustion of fuels like dihydrogen, methane, LPG ete. are compared in terms of the same amounts in mole, mass and volime, are shown in Table THE ENERGY RELEASED BY COMBUSTION OF VARIOUS FUELS IN MOLES, MASS AND VOLUME Energy released on —_Dihydrogen Dihydrogen LPG CH, gas Octane combustion in kd (in gaseous (in liquid) (in tiquid state) state) state) per mole 286 285 2220 sso 5511 per gram 143 142 50 47 per litre 12 9968 25590 35 34005ol o 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 ioxygen 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 lke NaN, Ti~TIH,, Mg-MgH, 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 altemative. The basic principle of hydrogen economy isthe transportation and storage ‘of energy in the form of liquid or gaseous dihydrogen. Advantage of hydrogen economy is that eneray is transmitted in the form of dihydrogen and not as electric power. Iti for the first time in the history of India that a pilot project using dihydrogen 2a 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, itis also used in fuel cells for generation of electric power. I 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.