HYDROGEN It is the most abundant element in the universe. It is the lightest element. About 70% of the total mass of the universe is H,. Hydrogen behaves as electropositive elements like alkali metals as it can lose the single electron as well as it behaves like halogen as it can gain one more electron to complete it’s 1s orbital. Preparation : © Byaction of metal on water a. Reaction with active metals like Na, K, Ca etc. They react with cold water. These metals are used in amalgumated form to reduce reactivity. ° Na+ H,O > NaOH + \/2H, b. Mg, Al, Zn react with boiling water. Mg +H,O—> MgO+H, c. Fe,Ni, Sn, Cr, Mn react with steam. 0 3Fe + 4H,O — Fe,0,+ 4H, Ni+ HO NiO+H, © By reaction of dil. acid on metals : Metals lying above hydrogen in reactivity series s H, fromacid solution. e.g., Fe, Al, Mg, Zn— granules etc Al+ 3H1C1 > AICI, + (302) Hi Zn+ HSO, (dil) > Z2nSQ AH, IfZnis treated with cone. H,SO, ), or cone. HCI, hydrogenis not evolved. Explanation: a. ZnSO, fo reacts with cone H7,SO, and reduces it to SO,. With eOREVHCI, ZnCI, produced forms coating on Zn. The reaction stops immediately. Zn + 2HCI— ZnCl, d+ Hy. © Reaction with atkati Metals like A/, Zn, Sn, Pb ete react with NaOH to evolve Hy: Al+ NaOH —*°-5 NadlO, + H, Zn + NaOH —°_5 Na,ZnO, + H, Sn+ NaOH —"® 5 Na,SnO, + H, Pb + NaOH —*®_, Na,PbO + H, CLASS MATERIAL CHEMISTRY _ HYDROGI© Byhydrolysis ofmetal hydrides : NaH 225 NaOH + Hy Call, —2%9_, Ca(OH), + 2H, * Byelectrolysis of water using Pr - electrode gives pure H, . Here little amount of acid, base, salt is added to increase conductivity : HO = +08 Cathode: 2H" +2e-» H, (reduction) Anode: 20H > H,0+ 1/20, + 2e (oxidation) Electrolysis ofaq. Ba(OH), solution gives 99.95% pure H, using Ni- electrode. ©, isalso obtained as by-product in the electrolysis of brine solution to get NaOH and Ci. \ INDUSTRIAL PROCESS : * _ LANE’S PROCESS 0 3Fe + 4H,0(steam)—> FexOx + 4H 2H, + CO} beararm |teweneration of Fe) 3 ranosenl\Y * BOSCH PROCESS: Hydrocarbon or SAM Ci (called Water Gas Shift reaction) Red Hot Coke (Fex0s/ Cr20s) ‘On+ Hh Hz + CaCOsgrrough Time water toremove CO: Properties of H, : + Ithashighest single bond energy amongst elements. * Metals which are less electropositive than Fe are reduced by H,. eg. H, 5 Pd+ 2 H, —“-> Cu+ HO CLASS MATERIAL CHEMISTRY _ HYDROGI© Formation ofhydrides : * —‘Types- I: Ionic Or Salt-like Hydrides : * These are formed by group I /I metals. e.g., Lill, NaH, Calf, ete. * Li, Bel, MgH, have appreciable covalent character. * Bel, and MgH, ate polymeric in solid state. * These hydrides are conductors in molten state. * ‘Types - IL: Covalent Hydrides : * These are formed by non-metals, ie., mainly p-block elementse.g : BH,, NH1,, CH, etc. * ‘They are also called molecular hydrides. * BH, Electrondeficient hydride NH, Blectrontich hydride CH, > Electron precise hydride. * Hydrogen reacts with X, to give HLY. -. order of reactivit F, reacts even in dark. J, reacts in presence of catalyst * ‘Types - III : Metallic Or Interstitial Hydrides : * These do not have fixed fornmla and so * — Theyare formed by transition and inner’ * Here hydrogen occupies the voids in the crystal lattice of the metals. But recently its seen that they have different lattice stru the parent metal. * — Theycan conduct heat and ‘ity but to lesser extent than the metal it.self. e.g: H, adsorbed oer Pi j, Peete are metallic hydrides. bara’ © Orttto Hydr 1. BASED ON PROTON ae are called Nuclear Spin Isomers. a. Ortho Hydrog m: this form, the protons inside the nuclei have same spin. But they have opposite spin of we OB © Para Hydrogen : Inthis form, the protons have opposite spin in the nuclei. They have opposite electron «= @O© * Ordinary hydrogen isa mixture of both Ortho and Para hydrogen. © Atroomtemperature, ordinary hydrogen isa mixture of 75% ortho form and 25% para form. © Para formas lower energy content and is more stable at lower temperature. At 0K, 100% para isomer can be obtained. But as temperature increases, percentage of ortho form increases and reaches a limiting value of 75% ortho & 25% para. CLASS MATERIAL CHEMISTRY HYDROGEN 3* Preparation of Ortho and Para Hydrogen : . H,{e) pony para —H, isadsorbed * Atomic H+ Para H, > Ortho H, + H-atom Properties : + Vapour pressure and specific heat of ortho-formis higher at room temperature. * Conductivity ofortho-formis lower. 2. BASED ON ENERGY CONTENT & IT’S STATE OF EXISTENCE : Nascent Hydrogen: Hydrogen produced in SITU ie. reaction medium itself. It is highly reactive and ‘can not be isolated. * — Ttcanreduce many substances. e Nascent “H” —"“2-5 FeCl, + HCI Nascent “H’ —##2_ K,S0,+ MnSO, + H,0 180, 2 Nascent A?” S22" 50, + Cr(50) f) * Ordinary H, can not decolorise MnO, or 8a hydrogen can. © Adsorbed Hydrogen (occluded) : * ‘Theyare more reactive than ordinary hydrogen. CH, = CH, +H, "5 C, H, + Ch, “> 2HC1 © Atomic Hydrogen : al tal surface like Pr, Fe, Ni, Pdete. ‘When ordinary hydrogen is subj electric spark then the large amount of heat produced, dissociates H, to ‘H’ atoms which: hydrogens. It can be isolated but it is highly reactive and highly energetic. Note: + 01 ® Atomic H> Nascent H> Adsorbed H, > Ordinary H, © doesnot exist fiéely due to it’s small size [F1,0" or H,O,"] * Order of melting Point, AH, , bond energy is : 1 2CaCO,) + HO Mg(HCO,), + 2CaO > Mg(OH),4 + 2CaCO,S e Lime should not be used in excess as it can absorb atmospheric CO, t on hardness. Removal of Permanent Hardness * By Boiling with Na,CO, or NaOH or Na,PO, : CaCl, 882 CaCO, 4 + 2NaCT 0 MgCl, 2 Mg(OH), + + 2NaCl MgCl, —®2_5 Mg(PO,), ¥ + 6NaCl © Byusing Sodium Zeolites : [Permutit Method] * Sodium zeolite or permit or sodiun silicate is Na,AI,Si,0, .xH,O. Cat or Mg** 23, Gal St OjH,0 + 2Nat ),OpxHO * Sodium zeolite isa cation exebanger. * Spent zeolite is reg@nerated by treating it with aqueous NaC. CaAl,Si,0,.XH,Q + INa’ > Na,Al,Si,0,.xH,O + Co mhexametaphosphate i.e., Na,[Na,(PO,),] vation exchanger. process of removing Ca" or Me™ is called SEQUESTRATION. + Using cation and anion exchange resin : Cation and anion exchange resins are complex organic acids or bases which can exchange Ca* or Me™ for H* and SO,* or Ch for OF. 2R ~SO,H1 (Cation exchange resin) + Ca** > (R-SO,),Ca+ 2H 2R~*NH,OH (anion exchange resin) + SO-—> (R ~*NH,),SO, + 20H * The Hand OH" ions produced combine to form H,0. This process is used to obtain de-mineralised water. ‘The spent resin can be regenerated by treatment with acid or base. (R-SO,),Ca + 2HCI—> 2R-SO,H * CaCl, resin resin) CLASS MATERIAL CHEMISTRY HYDROGENHEAVY WATER(D,O) ‘Comparision of physical properties of H,0 and D,O: Melting and boiling point of D,0 is higher than 1,0. Density and viscosity of D,O are higher than 0. ,O forms stronger hydrogen bonds than 7,0. Latent heat of vaporisation of D,O higher than #1,0, Latent heat of fusion of D,0 is lower than H,O due to difference of lattice structure. Surface tension of D,O is lower than 11,0. Dielectric constant of H,O is higher than D,O. Due to this ionic compounds are more soluble in H,O Tonic product of H,0 [K, = [H*][ OH] is higher than D,O by approximately three times. er aweenye * Chemical Properties of #7,0 and D,O are Same. © Chemical properties of D,O D,O —*-» NaOD + 1/2D, D,O_, H-D+NaOD D,O 2-5 2NaOD 0 D,0 5 ND, +3Li0D D,0 8% Ca(OD), + D-C=C-D * Concentration of D,O in ordinary water is 1 in{6000 parts + Ieeiscrystaline form of water, © Inice, every water molecul * Atatmospherie press in. eubie form. ‘Hydrogen - bonds; two using oxygen and two using hydrogen. ‘allises in Hexagonal formand at very low temperature, ice crystalises gon a j a a y fe sf om 1, os CLASS MATERIAL CHEMISTRY _ HYDROGIHydrates : There are compounds containing water of crystallisation. © There are obtained when salts are crystallised from their aqueous solution. Types of Hydrates : 4. Co-ordinated water: ‘These are the hydrates in which 7,0 forms co-ordinates bond to the central metal e.g., CrCl,.6H,0 which exists as [Cr(H,0),|Cl, 5. Interstitial water: In these hydrates, the 1,0 molecules occupies voids in the crystal lattice of compound. e.g BaCl,.2H,O ¢ Hydrogen Bonded water: _Inthese hydrates, the #7, molecules are attached through hydrogen bonds. e.g., CuSO,.5H,0. It exists as [Cu(H,0),]SO,-H,O HYDROGEN PEROXIDE (H,0,) . Preparation : \ © ByreactionofNa,O, with Cold, dil. H,SO,: Na,O, + H,SO, > Na,SO,* 0, + Byreaction of CO, with ice cold paste of BaO, BaO, + CO, + H,O > HO, + Baco,d © Byreacting BaO, with HPO, : 3BaO, + 2H,PO, > BaPO,), V+ 31,0, + Byreaction of BaO, 8H, Owith 7,50, BaO,8H,O + HSO,—> BaSO 0%: HQ, + 8H,0 Note: _Itisnot preferredas in 1 OfBaSO, produced, HO, is decomposed as BaSO, acts as catalyst forit’s decomposition, © Byelectrolysis of equi of H,SO, and (NH), SO, . (NH),SO, + (HWSO, NHHSO, SOp +H Cathodes 2 (Reduction) Anode? [80° > (NH,),8,0, + 2e (NHL,) 8,0, + 2H,0 > 2NH,HSO, + H,O, © ByOkidation6facidified sulphate solution : ° ° sor ain, n-0-)-0-0-}-0-1 hydrolysis 2HSOe + 2H" + HzO: * ForD,O,: —_-K,8,0, + 2D,0 > 2KDSO, + D,O, CLASS MATERIAL CHEMISTRY _ HYDROGI* Byauto oxidation of 2-ethylanthraquinol. oH COOm oH Physical Properties : * _Itisapale blue or colourless liquid. * It issoluble in H,0 + It’sconcentration is expressed in terms of ‘volume strength”. e.g.,30% H,O, = 100 vol It ismore dense and viscous than /7,0 ast forms stronger H-bond, * Boiling point of17,0, is higher but melting point of H,0, is lower than 7 \ * Dipole moment of H,O, (2.1D) is more than that of HO (1.84). © 1,0, ismore acidic than H,0. It isa dibasic acid * Dielectric constant of 7,0 greater than /1,0, 0 * Electrical conductivity of 7,0 is greater than H7,0, Chemical Properties : © It canact both as oxidising agent as well as rediicing agent. However it isa better oxidising agent than reducing agent. [7,=2] a. As Oxidising agent : i. Inacidic medium 2H +2e —* 5 2H,0 ii, Inacidic medium ), + 2e 2» 20H" Reactions : "oes 1), HO wig, AL FA(CM] + H,0* K,S0, —Baacs'st_> Cr (Blue) + KHSO, + H,O 32,804 Cas HO, S15 PhSO (White) + H,O {This reaction is used to regain white colour of lead paintings) H,O,—*# > $+H,O HO, 5 Na,SO, + H,O HO, —"°-y NaNO, + H,O HO, "8° Na,AsO, + HO CLASS MATERIAL CHEMISTRY _HYDROGIH,O,—“°-y HCOOH + H,O H,O, "> Hg0 + H,0 * Oxidising Action Basic Medium : * HO, +Cr{SO,),(green) “5 Na,CrO, (yellow) + Na,SO,+H,0 * Fe +H,O, > 2Fe* + 20H * MiP*+ HO,» Mn'* + 20H b. —AsReducing agent : i Inacidie medium : HO, > 2 + 0, +20 ii, Inbasie medium: H,0, + 20H" > 2H,0 + 0, +2€ © Reaction: HO, sci MnSO {colourless) + O, + Ky! HO, Rael) >CH{S0,), (green) + H,0,—%->H,0+ 0, HO, 225 HCI (or 2HBr) + [his property of H,O, to reduge Cl, * tichlor Property] HO, "25 HCL+ “ee HO, 4224 0, 7 Ho, 22 10+0, . Reducit in medium : ; + > 2I-+2H,0+ 0, 2MnO, %3H,O, > 2MnO, + 30, + 20H~ , + kyLFe(CN),] 2k, [Fe(CN),] + H,0 + 0, 2. HO, acts asbleaching agent as it gives our nascent oxygen. [Permanent bleaching agent] HO, >H,0,+(0] ‘Use : Perhydrol (as 30 % solution of 7,0, isused as an Antiseptic. TESTS OF H,0, : 1. Itliberates /, fiom X7solution, which gives blue colour with Starch solution. 2. Whenethereal solution of #0, is treated with cold / acidic solution of K,Cr,O,, BLUE COLOUR appears due to formation of CrO,. 3. When brought incontact with /7,0, solution, black stain of lead sulphide tums white, 4, It decolourises acidified solution of KMnO,, (pink to colourless) CLASS MATERIAL CHEMISTRY _ HYDROGISTORAGE OF 1,0, : It is stored in wax lined glas or plastic vessel in dark to avoid it’s decomposition : HO, —"> H,0+ 1/20, (ight) Alkali catalyses decomposition & Urea decreases the rate of decomposition. STRUCTURE OF 11,0, : + Ithas openbook like structure. * It contain both polar and non-polar bond : H 0 CsPolar bond 1 Near bon Ithas different bond length and bond angle in gas and solid phase. e GAS SOLID H 95 pm Note : Insolid due to H-bonding, the O—H bon« - In gas phase the dihedral angle is larger. ye