Collision Theory Reaction Rate of Rate = Zaa e Energy Barrier Js Rate = PZap e#* RT + Collision frequency (Z):-The number of collisions taking place per second per unit volume of the reaction mixture is known as collision frequency (2), RT Where Z=collision frequency and -E,/RT =Fraction of molecule having equal or more then activation energy. J+ Fora collision to be effective, the following two barriers are to be cleared, 2,Orientation Barrier }+ To account for the orientation factor for the collision to be effective , Probability or Orientation or Steric factor(P) has been introduced UNIT-4-dand f- BLOCK ELEMENTS T_] @ block elements are called transition elements | as they have incomplete d-orbitals in neutral or most stable oxidation state, 2 |Z, Hg Gd, are not included as transition | as they have filled d-orbitals in neutral and most stable +2 elements and why? oxidation state, 3] Sc has d° configuration but it is transition | Because of partially illed d' configuration of Sc metal | First series transition elements shows irregular | Due to shielding effect of inner 3d electrons which trend of atomic radii overcome ENC 5 | Atomic radii of Zr to Hfare almost same. due to Lanthenoid Contraction. 6 _| First series transition elements shows irregular | Itis because of mutual exchange of energy between d and? trend of IE orbitals after removal of one electron, 7 | Transition metals have strong metallic bond, | due to presence of unpaired electrons. have high enthalpy of atomization and melting point. 8 | Zn, Cd, Hg are not very hard and have low MP. | Due to presence of all paired clectrons they have least and BP. enthalpy of atomization, very weak metallic bond & are not very hard with low M.P. and BP. 9 _| &block elements shows a large no. of oxidation | due to presence of unpaired electrons or partially filed d- state orbitals. 10| Which first series transition metal shows | Mn shows highest number of oxidation state due presence highest number of oxidation states and why? _| of highest number of unpaired electrons. TI | Which first series transition metal do not show | Se, due to achieving noble gas configuration in +3 0.5, variable oxidation states and why? 12 | Gi is more stable as compared to Gr due to stable half filled to, configuration 13 | Cutis more stable in solution than Cu due to high hydration enthalpy of Cu ionin solution, 14 | Which first series transition metal shows +1 | Cu shows +1 oxidation state in gaseous form due to stable oxidation states and why? full filled 341° configuration. 15 | Higher oxidation states of transition metals | because higher oxidation states stabilized by highly found in their oxides and fluorides electronegative elements such as 0 and FT6 | higher oxidation states are more common in | due to formation of div-pw bond between metal and oxygen, oxides rather than fluorides of transition metals. 17 | +2 OS becomes more stable in first series | as number of unpaired electrons decreases. transition elements moving from left to right 18 | Write oxoanions of first series transition metals | MinOy, Cra07#, VOy, CrOv in which group number and O.N. of transition metal are same- 19 | Moving from left to right E° for M@/M becomes | trends due to irregular variation of IE; + [Es less negative but it shows irregular trend 20 | For copper EP Cu /Culs +ve (+0.34V) tis due to low hydration enthalpy of Cu® which cannat compensate Assl®+ IEs + IE. 21 | For Mn, E)Mn®/Ma® is ve ‘because by converting into Ma® it achieves half filled configuration. 22 | For Gr, BCrh/Cr is ve because Cr is more stable due to half filled ty configuration. 23 | Most of the compounds of transition metal are | Itis due to d-d transition coloured in solid state as well as in their solution form. 24 | (Se™, TIF) does not exhibit any colour Tons with vacant d-orbitals (d°) as d-d transition is not possible in this type of ions. 25 | (Zn™, Cu") does not exhibit any colour Tull filled d-orbitals (d) as d-d transition is not possible in this type of ions. 26 | Transition metals or ions are paramagnetic in | Due to presence of unpaired electrons (@™) nature 27 | Transition metal form large number of | High charge by mass ratio, availability of vacant d-orbital & coordination complexes Variable oxidation state 28 | What are Interstitial compounds? Compounds in which small elements like H, B, C, N trapped in the interstitial space of metal lattice. 29 | Transition metals form Interstitial compounds. | due to availability of interstitial space in metal lattice, 30 | Why interstitial compounds are found to be | These compounds have high MP as compared to pure more useful than pure metal? metals, These are very hard, Retain metallic conductivity and are Chemically inert. 31 | Transition metals and their compounds are | Due to large surface area, variable oxidation state & widely used as catalyst Availability of vacant d-orbitals 32 | transition metals form alloy. Due to comparable metallic radii 33] Why oxides of Higher oxidation states of | Higher oxidation states are more polarizing in nature . transition metals are acidic in nature whereas | hence are acidic in nature whereas lower OS. are less lower 0.S.are basic in nature? polarizing hence are basic in nature. 34 | Actinoids shows greater number of oxidation | Due to comparable energy of Sf, 6d, and 7s orbitals, states then lanthanoids35 | [tis difficult to study chemistry of actinoids, Due to radio active nature and small halflife 36 | Ce(IV) is a good oxidizing agentin aq, sol” because in aq, solution its Bt is +1.74V 37 | Actinold contraction is greater from element to element as compared to lanthanoids because of poor shielding by Sf orbitals due to its superficial position. Pe um Dichromate [K2Cr; Its prepared from chromite ore : FeCri0s / FeO cr0s Step: 4FeC1204 + BNaxC5 +702 4BNaACO4 + 2Fe20) + 8cOz ‘Step 2: 2NazCrO, (Yellow)+ H2S0,—4 NasCr.0,(Orange)+ NazSO. + 1.0 Step 3:NaxCrO> + 2KCl ——> KaCriOr + 2NaCl Orange Orange Effect of pH: CrzOr% (Orange) + 20H" — 2Cr0,?- (Yellow) + #20 2CrO, (Yellow) + 2Ht —+ Crz0,? (Orange) + 20 Oxidizing Character: Dichromate ion acts as strong oxidizing agent in acidic medium. Cra072 + 14H + Ge ——> 2Cr% + 7H20 CrOrt+ 14H" + 6! — 2Cr% + 7H,0 + Ble Crz072 + 14H + 6Fe? 4 2Cr3*7H,0 + 6Fe™ CriOy%+ 14H? + 38n% —4 2¢r 7H20 + 38n" Cr072 + BH + 3H2S —4 2Cr°* + 7H.0 + 38 Potassium Permanganate [KMn0.J Preparation: from pyrolucite ore [Mn02] Step 1 2Mn0; (Black)+4KOH+0,—4 2K.Mn0; (Green)+ 24.0 Step 2: 3Mn0,?- (Green)+4H* 4 2MnO+( Purple)+MnO2+ 2H20 Oxidizing Character: (Oxid: in acidic medium MnO. + 8H! +5e-——® Mn? + 411.0 Eq. mass of KMnOs = 158/5 = 31.6 MnO.-+5Fe?+8H! — Mn2+5Fe%+ 44120 2MnOr + 10CI + 16H* —¥ 2Mn? + 8H20 + SCle 2MnOy +5C:0.2+ 16H!'—4 2Mn?++10C02+ 8H20 2MnOy-+5SOs+6H* —4 2Mn2* + 5S0,2 + 3H20 2Mn0,+5NOr+6H* > 2Mn* + SNOx + 3H:0 2MnOy+5S"+16H* —4 2Mn? + 5S + BHO 2MnOy +3H,0+ k —¥2Mn0; +10 + 20H: BMnOy +35,05?-+1120 —48MnO2 + 650," + 2041 2MnOy +3 Mn2++2 HO —495Mn0; +41 ‘EBlock Elements General configuration (m - 2) f 4 (n-1)d ©" ns? ola [Ke] 5d¥6s? | we [Rn] 6d¥ 72 - saCe [Xe] 4fSd* 6s? | 9:Pa [Rn] Sf? 6d! 7s? goku [Xe] 47 Sd? 6st | oo [Rn] 5 6d 752 eGd [Xe] 40° Sd! 6s? | ogPu [Rn] Si 6a 75? Yb [Xe] 414 5d 6s? Lanthanoid Contraction Regular decrease in atomic or ionic radii of Lanthenoid with increase in atomic number is called Lanthenoid contraction. Cause: It is due to imperfect shielding of one 4f orbital by another 4f orbital due to which ENC regularly increases with increase in atomic number. ‘Consequences: 1, Resemblance in the properties of second and third transition series from Zr & Hf) atomic size of 2» and 3+ transition series become same, 2, Similarity in the properties of Lanthanoids:- The decrease in atomic radii from Lanthenoid to Lanthenoid is very less hence itis very difficult to separate these elements in pure state. 3, Basie strength of hydroxides of Lanthanoids decreases from Lanthenium (La) to Lutesium (Lu). Misch Metal - It is alloy of Lanthanoids(95%) with iron (S%Jand Trace of S, C, Al Ca Lanthenoid - 95% Metal + Trace of S,C, Al Ca + Iron -5% Uses- making bullet shells and flinter of lighters. Tanthanoids ‘Actinoids Tast electron enters in 4f orbital Tast electron enters in Sf orbital “Are natural elements and non radioactive In nature ‘Are radioactive in nature and alter Np they are synthetic elements Shows less number of oxidation states [+2,+3,+4] Shows greater number of oxidation states [-3,-4-5+6,7] Element to element lanthanold contraction Is less Element to element actinold contraction is more