D & F Block Elements PDF

D & f block elements #BOUNCEBACK Sakshi Vora IIT Roorkee ❏ 7+ years Teaching experience ❏ 10th, 12th CBSE State Topper ❏ KVPY fellow Join with us in Telegram Telegram Channel t.me/unacademyatoms Complete Notes and Lectures livedaily.me/atoms  Personal Guidance...

D & f block elements #BOUNCEBACK Sakshi Vora IIT Roorkee ❏ 7+ years Teaching experience ❏ 10th, 12th CBSE State Topper ❏ KVPY fellow Join with us in Telegram Telegram Channel t.me/unacademyatoms Complete Notes and Lectures livedaily.me/atoms  Personal Guidance Study Planner Get one on one Customized study plan guidance from top exam with bi-weekly reviews experts Live Classes Weekly Tests ICONIC PLUS Structured Unlimited Courses Access Test Analysis Study Material Get one on one Specialised Notes & guidance from top exam Practice Sets experts Experts' Guidelines Study booster workshops by exam experts SAKSHI SAKSHI Transition Elements Transition elements Old definition : all d - block elements were called transition elements. New definition : d block elements having unpaired e- or partially filled d-orbital in any O.S. Transition elements - Zn, Cd, Hg are not transition elements but they are d-block elements. The First transition series (3d series) involves the filling of 3d orbitals and has 10 elements from scandium (Z=21) to zinc (Z=30) The second transition series (4d series) involves the filling of 4d orbitals and has 10 elements from yttrium (Z=39) to cadmium (Z=48). Electronic Configuration General electronic configuration : (n - 1)d 1-10 ns0-2 Exceptions of e- configuration : Nb Cu Cr Rg Mo Tc Ru Rh Pd Au Ag Pt All have 1e- difference from n + l rule Pd has 2e- difference from n + l rule Physical properties Atomic Size Atomic Size Atomic size - Sc Ti V Cr Mn Fe Co Ni Cu Zn d10 No. of unpaired e- ↑ No. of unpaired e- ↓ M-M bonding ↑ M-M bonding ↓ Attraction ↑ Attraction ↓ Size ↓ Size ↑ Radius ↓ Radius ↑ Atomic Size Sc Ti V Cr Mn Fe Co Ni Cu Zn Factor 1 - left to right, zeff ↑, attraction ↑ size ↓ Factor 2 - unpaired ↑ size ↓ unpaired e- ↓ size ↑ Atomic size : Sc to Cr : Both factors overlap size ↓ Mn to Ni : Both factors oppose size ≈ Ni to Zn : Size inc rapidly Sc Zn Size Cr Ni Z⟶  Metallic Radius : metallic radius Z⟶ Mn : solid state structure is not defined The atomic radius of Ag is closest to : A. Au B. Ni JEE Main 2020 C. Cu D. Hg Melting Point Melting Point : Sc Ti V Cr Mn Fe Co Ni Co Zn No. of unpaired e- ↑ No. of unpaired e- ↓ M-M bonding ↑ M-M bonding ↓ Attraction ↑ Attraction ↓ M Pt ↑ M Pt ↓ Typical Solid State structure ∴ breaks easily Less melting point Melting Point : Zn : lowest Melting point Cr Fe Mn MPt Sc Zn Z⟶ Melting Point : 3d < 4d < 5d (in a group) Down the group, Zeff ↑ M - M bonding ↑ M.Pt ↑ Exception : d10 Cu > Au > Ag Zn > Cd > Hg Density Density Down the group 3d < 4d < 5d - Mass ↑↑ - Size first inc then constant ∴ overall d ↑ Left to right - Size 1st decreases then constant - Mass increases continuously - ∴ generally density increases Special case of configuration Configuration of Transition metals of M+1 actually Fe : 3d6 4s2 Fe+ should be : 3d64s1 But Actually is 3d7 Ionization Energy Ionization Energy of 3d : Sc < Ti > V < Cr < Mn < Fe > Co > Ni < Cu < Zn 631 656 650 653 717 762 758 736 745 906 Ionization Energy of 3d : 1. In general left to right zeff ↑ so I.E ↑ 2. Additional effect is observed due to increment in no of exchange due to shifting of e- from ns to (n-1)d 3. Due to additional effect in some cases, the decrement is observed in IE A. Co B. Fe JEE Main 2020 C. Ni D. Mn Oxidation State Variable oxidation state : Sc Ti V Cr Mn Fe Co Ni Cu Zn +3 +2 +2 +2 +2 +2 +2 +2 +1 +3 +3 +3 +3 +3 +3 +3 +2 +2 +4 +4 +4 +4 +4 +4 +4 +5 +5 +5 +6 +6 +6 +7 max os = ns e- + (n-1)d e- unpaired. The element that usually does not show variable oxidation states is : A. Cu B. Ti JEE Main 2019 C. Sc D. V Standard Electrode Potential  Standard Oxidation/Reduction potential Eo, Standard electrode potential M/M2+ : Standard oxidation potential M(s) ⟶ M+2(aq) atom Hydration M(g) ⟶ M2+ (g) IE1 + IE2 Standard oxidation potential: - Ti V Cr Mn Fe Co Ni Cu 1.63 1.18 0.90 1.18 0.44 0.28 0.25 -0.34 - From left to right, Zeff ↑, IE ↑, E0 ↓, reactivity in H2O ↓ - Mn2+(d5) , IE2 is v less (half filled) Standard oxidation potential: Eo M2+ / M3+ M2+ (aq) M+3 (aq) IE HE +3 M(g) if IE > HE if IE < HE req > released req < released Eo M+2 /M+3 - Eo M+2 / M+3 + non - spon spon ∴ M+2 is more stable than M+3 M+3 is more stable than M+2 Which of the following ions does not liberate hydrogen gas on reaction with dilute acids ? A. Ti2+ B. V2+ JEE Main 2017 C. Cr2+ D. Mn2+ Magnetic Behaviour Magnetic Behaviour : Spin only magnetic moment : √n(n+2) BM n = no. of unpaired e- For d1 to d5 expected = experimental For d1 to d9 expected < experimental A. B. JEE Main 2019 C. D. Catalytic property Catalytic Properties : Transition metals are used as catalyst due to 1. Variable o.s property 2. Active surface valency Fe N2 + NH3 H2 V2O5 SO2 + O2 SO3 Al(C2H5)3 + TiCl4 Ziegler Natta catalyst Deacon’s process HCl + O2 Cl2 + H2O  JEE Main 2019 A. B. C. D. Colour of Transition metal compounds Colour of Transition Metal ions in aqueous solution : - aqueous solution ⟶ H2O as a ligand - CNo = 6 octahedral - d - orbital splitting - coloured because of d - d transition - do , d10 are colourless - d5 - WFL coloured LMCT Colour of Transition Metal ions : d0, d10 colourless d1, d9 Blue d2, d8 green Cu+2, Cr2+ blue Mn2+, Co+2 Pink Fe2+, Ni+2 green Cr3+ violet Fe3+ Pale yellow Complex formation Complex formation Tendency: d block metals have - (n-1)d vacant orbitals - High Zeff Thus, can act as lewis acids and form complex A. B. JEE Main 2019 C. D. Alloy formation Alloy formation: - Atoms having size diff < 15% are used to make alloy. - d block metals have almost same size so they are used to make alloy. Brass = copper-zinc Bronze = copper - tin Halides of 3d series Halides of 3d series : Halides of 3d series : - In max. O.S generally only F- exist CrF6 , VF5 - MnF7 , MnF6 , MnF5 do not exist due to steric crowding. - TiF2 , CuF does not exist due oxidising nature of ‘F’ - So many Br- , I- do not exist due to reducing nature of iodide and bromide FeI3 , CuI2, CuBr2, MnCl4, MnBr4, MnI4 , CrCl6 , VI4 Oxides of 3d series Oxides of 3d series : 3 4 5 6 7 8 9 10 11 +7 Mn2O7 +6 Cr2O 3 +5 V2O2 +4 TiO2 VO2 CrO2 MnO2 +3 Sc2O3 Ti2O3 V2O3 Cr2O3 Mn2O3 Fe2O3 +2 TiO VO CrO MnO FeO CoO NiO CuO Cu2O A. JEE Main 2017 B. C. D. Potassium Dichromate Potassium Dichromate Chromite ore molten FeCr2O4 + Na2CO3 Na2CrO4 + Fe2O3 + CO2 (↑) Or FeO. Cr2O3 Filterate Residue Na2CrO4 Fe2O3 K+ K2Cr2O7 (↓) ← Na2Cr2O7 H+ Potassium Dichromate do do LMCT LMCT Yellow Orange Tetrahedral Bridged Tetrahedral All angles 109 JEE Main 2020 Reactions of Potassium Dichromate HCl / HBr / HI Cl2 , Br2 , I2 HNO2 / H2SO3 / H2C2O4 HNO3 / H2SO4 / CO2 Fe2+ / Sn2+ Fe3+ / Sn4+ H2S / S S / SO2 Itself K2Cr2O7 Cr3+ Potassium Permanganate Potassium Permanganate : fused MnO2 + KOH + air / KNO3 / KClO3 K2MnO4 H+ Cl2 / O3 / electrolysis KMnO4 + MnO2 KMnO4 Compounds of Mn : Tetrahedral Tetrahedral manganate permanganate (green) ion (purple) ion d1 d0 d-d transition LMCT dπ - pπ dπ - pπ A. B. C. D. JEE Main 2020 Oxidising nature of KMnO4 : H+ KMnO4 Mn+2 E1o H2O / OH- MnO2 E2o OH MnO42- E3o - Oxidising reactions of KMnO4 : HCl / HBr / HI Cl2 / Br2 / I2 HNO2 / H2AsO3 HNO3 / H2AsO4 H2C2O4 / SO2 CO2 / H2SO4 H2S / I2 S / HIO3 Fe2+ / Sn2+ Fe3+ / Sn4+ itself KMnO4 Mn+2 JEE Adv 2016 Decomposition of KMnO4 : A. B. JEE Main 2019 C. D. A. Mn B. Cr JEE Main 2018 C. V D. Ti Which of the following combination will produce H2 gas ? A. Fe metal and conc. HNO3 B. Cu metal and conc. HNO3 JEE Adv 2017 C. Zn metal and NaOH(aq) D. Au metal and NaCN(aq) in the presence of air A. B. C. D. JEE Adv 2019 f block elements f - block elements : 4f series - Lanthanoids (Ln) Atomic number 58 to 71 General electronic configuration [xe]4f1-14 6s2 Exception La Ce Gd 57 La ⟶ [Xe] 4f1 6s2 but is [Xe] 5d16s2 The lanthanide ion that would show colour is : A. Gd3+ B. Sm3+ JEE Main 2019 C. La3+ D. Lu3+ A. B. JEE Main 2020 C. D. Lanthanide Contraction Lanthanide Contraction A. B. C. D. JEE Main 2019 Properties of Lanthanides Properties of Lanthanides : - all are silvery soft metals - found in earth’s crust (rare earth metals) - Reactivity > H2 - Aqueous solutions are generally coloured due to f-f transition Except fo, f14 - Common OS +3 also show +4(act as OA), +2(act as RA) Reactions of Lanthanides Reactions of Lanthanides : 1. Ln + H2O ⟶ Ln(OH)3 + H2 2. Ln + O2 ⟶ Ln2O3 3. Ln + N2 ⟶ LnN 4. Ln + H2 ⟶ LnH3 5. LnH3 + H2O ⟶ Ln(OH)3 + H2 6. Ln + S ⟶ Ln2S3 7. Ln + Cl2 ⟶ LnCl3 8. Ln + HCl ⟶ LnCl3 + H2 Uses of Lanthanides Uses of Lanthanides Uses - Lanthanides are used to make alloy 95% Ln + 5% Fe = mischmetal used to make bullets :- Ln oxides have property of phosphorescence Used to make TV screen - Ln oxidesane used as catalyst in petroleum cracking  JEE Main 2020 A. B. C. D. Actinides Actinoids : 5f series 90 - 103 All are radioactive post uranium (92) ⟶ 93 manmade elements Actinides : Ac Rf Db Sg Bh Hs Mt Ds Rg Cn General electronic configuration : [Rn] 5f1-14 6do/1/2 7s2 Exception : Ac Th Pa U Np Cm Ac should be [Rn]7s25f1 but is [Rn] 7s26d1 Actinide Contraction Actinides : - Decrement in size of 5f series is due the poor shielding of 5f e’s is called Actinoid contraction. - Actinoidcontration is more effective than lanthanide contraction (4f) The correct order of atomic radii is : A. N > Ce > Eu > Ho B. Ho > N > Eu > Ce JEE Main 2019 C. Ce > Eu > Ho > N D. Eu > Ce > Ho > N Oxidation States of Actinides  Oxidation state : Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 3 3 3 3 3 3 3 3 3 3 3 3 3 3 4 4 4 4 4 4 4 4 5 5 5 5 5 6 6 6 6 7 7 They show a variety of OS because of low gap between 5f, 6d and 7s A. B. JEE Main 2019 C. D. The lanthanide that does not show +4 oxidation state is : A. Dy B. Ce JEE Main 2020 C. Eu D. Tb Mischmetal is an alloy consisting mainly of : A. Lanthanoid metals B. Actinoid and transition metals JEE Main 2020 C. Lanthanoid and actinoid metals D. Actinoid metals A. B. JEE Main 2020 C. D. SAKSHI SAKSHI  Personal Guidance Study Planner Get one on one Customized study plan guidance from top exam with bi-weekly reviews experts Live Classes Weekly Tests ICONIC PLUS Structured Unlimited Courses Access Test Analysis Study Material Get one on one Specialised Notes & guidance from top exam Practice Sets experts Experts' Guidelines Study booster workshops by exam experts NVLIVE