+ Number of groups 10 * Electronic configuration : (n - 1) d?2 ns! + Also called as ‘transition elements Reason : Position in the periodic table is between s-block and p-block elements Zn group has d*° configuration in their ground state as well as in stable oxidation state, they are not considered as transition elements but they are d-block ‘elements. + Metauic character : They are all metal and good conductor of heat & electricity + MP. CrCd>Hg te (In group) lowest due to no‘unpaired efor metallic bonding Variation in atomic radius : Sc Ti V Cr Mn Fe Co Ni Cu Zn al AE Ad zie o 2k Pte — : P>T tonto ere: A= c< Tel * TE M>T OU Sc Ti v Cr Mn Fe Co Ni cu Zn b Vv v Aa A v v Vv A v v a Y 2r Nb Mo Te Ru Rh Pd Ag Cd TE) vy | an Jatlal a a oa fal aoa ta | uf |ta| |w] Re Os ir |pt| Au He v Ac +| Tick VON] BKQS 2n Hg r2m redDensity : * Highest density Os (22.57 gm cm) and Ir (22.61 gm cm). * In3d series lowest density — Sc Highest density—Cu “ Enthalpy of atomization, A,H-/kJ mol [Maximum : V (515) Minimum : Zn (126) Order of enthalpy of atomization (A,,H) : The amount of enthalpy change when a compound's bonds are broken and the component atoms are separated into single atom. % | 1-15 <-TS < Ill-TS (In general) Oxidation state : @ Oxidation states of the I* transition series most common ones are in bald types :_ . Se Ti Vo Cr! Mn Fe “Co Ni Cu! Zn j isl i j i+lj i PSSTEDESDESOT SRT SR SRS e Tea 2 $3) 4ST SS TSST SS TS SST ST - Sasa iva ya yaya +45 PESTS 45 PMR ee oon He +7 9 Stall, & nicheos TerOxidation state : i (i) 4 Ind-block down the group stability of higher oxidation state increases. Ex. in group 6, Mo(VI) and W(VI) are found to be more stable than Cr(VI). Thus Cr(VI) in the form of dichromate in acidic medium is a strong oxidising agent whereas MoO, and WO, are not. (ii) Low oxidation ; states are found in compound having|synergic bonding. | Example, in Ni(CO), and Fe(CO)., the oxidation state of nickel and iron is zero. (iii) Manganese (in middle) exhibits all the oxidation states from +2 to +7. (iv) | The lesser number of oxidation states : At the extreme ends (Sc, Ti) or (Cu, Zn). (v)_ fe Sc (Il) is unknown and Ti (IV) is more stable than Ti(IIl) or Ti(Il). (vi) Zinc is +2 (no d electrons are involved). (vii) #The variability of oxidation states, arises out of incomplete filling of d orbitals. (vii) Maximum oxidation state +8 : Os and Ru Trends in Stability of Higher Oxidation state : (i) Highest oxidation number are archived : Ti: +4 (TIX,) V:45 (VFs) Cr: +6 (CrF,) Mn : +4 (MnF,) Mn : 47 is possible in MnO,F but not in simple halides. | ™ Fe : +3 (FeF,) Co: +3 (CoF; Ni: +2 (NiX,) Cu : +2 (Cux,) (Except I) Cu : +1 (Unstable in aqueous solution & Undergo disproportionation) Zn: +2 (ZnX,)Trends in Stability of Higher Oxidation state : @ (ii) Highest oxidation number are archived : Sc : +3 (Sc,03) Ti: +4 (TiO,) te [245 (V,0.4-- Cr: +6 (CrO,) Mn : +4 (Mn,0,) Q.5.P. : Beyond group (VII) no higher oxides a possible. ge| Fe :+3 (FE,0,) +— Q.5.P. : [FeO,}- are formed in alkaline medium but readily decomposes to Fe,0; & O,. Co: +3 (Co,0,) + > Ni: +2 (NiO) Cu: 42 (CuO) Zn : +2 (ZnO) v Catalytic properties : Catalyst Used TiC; _— Ziegler-Natta catalyst in the production of polythene. v,0, * —> Contact process Convert SO, to SO, in the making of H,SO,. MnO, % —> Used as a catalyst to decompose KCIO; to give O,. Fe % —> Haber-Bosch process iron is used in the for making NH;. FeCl, — Used in the production of CCI, from CS, and Cl,. PdCl, te—> Wacker process for converting C,H, + H,O + PdCl, to CH,CHO + 2HCI + Pd. Pd — Used for hydrogenation (e.g. phenol to cyclohexanone). Pt/PtO % —> Adams catalyst, used for reductions. Pt —> Formerly used for SO, —-+ SO, in the contact process for making H,SO,.Pt/Rh te — Formerly used in the Ostwald process for making HNO, to oxidize NH, to NO. cu —> Is used in the direct process for manufacture of (CH;),SiCl, used to make silicones. Cu/V —> Oxidation of cyclohexanol/cyclohexanone mixture to adipic acid which is used to make nylone-66 CuCl, te | —» Deacon process of making Cl, form HCI Ni —» Raney nickel, numerous reduction processes (e.g. manufacture of hexamethylenediamine, production of H, from NH3, reducing anthraquinone to anthraquinol in the production of H,0,) FeS0,+H,0% —> Used as Fenton’s reagent for oxidizing alcohols to aldehydes. 10,2 / CrO, @ Preparation : Step (i) 4FeCr,0, + 8Na,CO, +70, (chromite ore) 1000°C 8Na,CrO, + 2Fe,0,+8CO,T red hot in presence of air Dissolve in water & filtered Filtrate (Na,CrO,) Residue (Fe,0,) Q.S.P. :Lime (CaO) added with Na,CO, which keeps the mass porous so that air has access to all parts and prevents fusion.Step (ii) 2Na,CrO, +H,SO,—> N,SO,1 +Na,Cr,0, + H,0 Cone. It’s solubility upto 32° increases Hence, suitable temp. is to be employed to crystallise out and then decreases Na,S0, first. Step (iii) Na,Cr,0, + 2kcl_ —““"" fk cr,0, }+ 2Nacl ep mn az decomposition -2— 27) 2 NaCl crystallizes out first and filtered off. Then K,Cr,O, crystallized out on Colling. In laboratory K,Cr,O, is used mainly not Na,Cr,0,. Why ? Na,Cr,0, is deliquescent enough and changes its concentration and can not be taken as primary standard solution whereas K,Cr,0, has no water of crystallization and not deliquescent.4 Effect of Ph: @ 2CrO,2- +2H* > Cr,0,7 +H,0 Cr,0,2- + 20H- -» 2Cr0,2- +H,0 Potassium dichromate is used as a primary standard in volumetric analysis. In acidic solution, its oxidising action can be represented as follows. Cr,0,2- + 14H" + 6e~ > 2Cr>* + 7H,O (E© = 1.33 V) Structure : 2 : 2 S 126" ‘Chromate ion Dichromate ionMANGANATE & PERMANGANATE Preparation of Manganate (MnO, y: Kon Mn0, —— Gq MnO,* green melt Ainpresence of air 2MnO, + 4KOH + 0, -» 2K,MnO, + 2H,0 MnO, + 2KOH + KNO, -> K,MnO, + KNO, +H,0 3MnO, + 6KOH + KCIO, > 3K,MnO, + KCI + 3H,0 Structure : ‘Terabedral Tetrahedrl sanganate permanganate (green) ion (purple) ion :|K,MnO, is quite stable in alkali, but in pure waver and in presence of acids shows disproportionation at ay 3K,MnO, + 2H,O — 2KMnO, + MnO, + 4KOH +6 ue purple dark brown 3K,MnO, + 2H,SO, —> 2KMnO, + MnO, + 2K,SO, + 2H,0 — Effect of Ph: Electrolytic oxidation in alkaline solution Mno,- —=Sneseuon > ~Mn0,- Manganate permanganate ionOxidising Prop. of KMnO, : (in acidic medium) (i) (ii) (iii) (iv) (v) (vi) MnO," + Fe*? + H* > Fe" + Mn‘? +H,0 MnO, +I-+H*—> Mn‘? +1, +H,0 MnO, + H,0,+H* > Mn‘? +0, +H,0 Mn0O,- + SO, + H*—> Mn*? + H,SO, MnO,- + NO, + H* > Mn‘? + NO, +H,0 MnO,” + H,C,0,+H* > Mn‘? +CO, + H,0 MnO," +H,S > Mn‘? +S) +H,0 Mn0,- +$,0,> — Mn‘? +S/+S0,2- Manganous salt is oxidised to MnO,; the presence of zinc sulphate or zinc oxide catalyses the oxidation: 2MnO,- + 3Mn?* + 2H,O —> SMnO, + 4H*Oxidising Prop. of KMnO, : (in neutral or faintly alkaline solution) 2MnO,- + 2OH-—> 2MnO,?" + H,0 +O Then 2MnO,- +2H,0->2Mn0,|+ 40H- +20 (i) 2KMnO, +H,0+ KI > + 2KOH + KIO; (ii) 2KMn0O, + 3H,0, —> 2KOH + 2Mn0, |+ 2H,0+ 30, (iii) | Thiosulphate is oxidized almost quantitatively to sulphate : 8MnO,- + 3S,0;2-+ H,0 > 8MnO, + 6S0,2-+ 2HO- Heating effect : A * 2kMnO, <> K,MnO, + MnO, +O, green black atred 2k,MnO,——> 2K,MnO; ef +0,