CHAPTER—4 SL AND f BLOCK ELEMENTS INTRODUCTION: d block elements are present from fourth period onwards there are mainly three series of the transition metals, 3d series (Sc to Zn), 4d series (Y to Cd) and 5 d series (La to Hg omitting Ce to Lu). d block elements are also known as transition elements. Electronic configuration of the d block elements is (n-1)d'"° ns '* but Zn, Cd, Hg are d block elements, but not transition metals because these have completely filled d orbitals in its atomic and ionic state. GENERAL PROPERTIES OF THE TRANSITION ELEMENTS. 1. ATOMIC AND IONIC RADII: In transition metals, left to right net nuclear charge increases due to poor shielding effect. Due to this, the atomic and ionic radii for transition elements for a given series show a decreasing trend is between the s block and p block elements.Hf and Zr are having same size due to lanthanoid contraction. 2, ENTHALPIES OF ATOMISATION Transition elements exhibit higher enthalpies of atomization because of large number of unpaired electrons in their atoms they have stronger interatomic interaction and hence stronger bond. 3, IONISATION ENTHALPIES In a series from left to right, ionization enthalpy increases due to increase in nuclear charge. The irregular trend in the first ionization enthalpy of the 3d metals, through of little chemical significance, can be accounted for by considering that the removal of one electron alters the relative energies of 4s and 3d orbitals. 4, OXIDATION STATES Transition metals shows variable oxidation state due to incomplete outermost shells. Only stable oxidation states of the first row transition metals are Sc(+3), Ti(+4), VES), Cr4+3,+6), Mn(+2,+7), Fe(+2,+3), Co(+2,+3)NiG+2), Cu(+2) and Zn(42). The transition in their lower oxidation states (+2 & +3) usually forms ionic compounds. In higher oxidation state compounds are normally covalent. Only Os and Ru show +8 oxidation states in their compounds. Ni and Fe in Ni(CO)4 and Fe(CO)5 show zero oxidation state. 5, TRENDS IN THE STANDARD ELECTRODE POTENTIALS The standard reduction potentials of divalent ions of 3d series generally becomes more and more positive from L to R. Variations occur at V2+,Mn2+ and Zn2+. This is due to less enthalpies of atomization of Mn and V and irregular variations of sum of first two ionization enthalpy terms. The unique behaviour of Cu, having 14. accounts for its inability to liberate H2 from acids. Only oxidising acids (nitric and hot concentrated sulphuric) react with Cu, the acids being reduced. The high energy to transform Cu(s) to Cu2+(aq) is not balanced by its hydration enthalpy. 6. TRENDS IN STABILITY OF HIGHER OXIDATION STATES:The higher oxidation number are achieved in TiXs, VFs and CrFs. The +7 state for Mn is not represented in simple halides but MoO3F is known and beyond Mn no metal has a trihalide except FeX; and CoF;, The ability of fluorine to stabilise the highest oxidation state is due to either higher lattice energy and the ability of oxygen to form multiple bonds to metals Increasing order of oxidizing power in the series is VO:" Cu2+ + Cu. The stability of Cu2+ (aq) rather than Cu+ (aq) is due to the much more negative hydration enthalpy of Cu2+ (aq) than Cu+ , which more than compensates for the second ionisation enthalpy of Cu 7. MAGNETIC PROPERTIES When a magnetic field is applied to substances, mainly two types of magnetic behavior are observed: diamagnetism and paramagnetism. Paramagnetism due to presence of unpaired electrons each such electron having a magnetic moment associated with its spin angular momentum. ‘The magnetic moment is determined by the number of unpaired electrons. Magnetic moment (1) = Vn(n + 2) where n is the number of unpaired electrons. Tf all electrons are paired, substance will be diamagnetic and magnetic moment will be zero. 8, FORMATION OF COLOURED IONS d block elements are coloured due the presence of unpaired electrons. When an electron from a lower energy d orbital is excited to a higher energy d orbital, the energy of required wavelength is absorbed and rest light is transmitted out. Therefore the colour observed corresponds to the complementary colour of the light absorbed. In V205 , V is in +5 oxidation state. It is coloured due to defects in crystal lattice. 9, FORMATION OF COMPLEX COMPOUNDS Transition metals have small size, nuclear charge and availability of incompletely filled d orbital which facilitates the acceptance of lone pait of electron from ligands. 10.CATALYTIC PROPERTIES Transition metals have variable oxidation states and form intermediates with low activation energy, therefore used as a catalyst. Transition metals are small and also provide larger surface area for the reactant to be adsorbed. 115ee Ee Ae Ne DONA SON: See SONNE RE 115 11.FORMATION OF INTERSTITIAL COMPOUNDS Small size of nonmetals (H,C,N) fit into the voids of crystalline solid of tranasition metals and form interstitial compounds. The principal physical and chemical characteristics of these compounds are as follows: a. They have high melting points, higher than those of pure metals. b. They are hard some borides approach diamond in hardness. c. They retain metallic conductivity d. They are chemically inert. 12.ALLOY FORMATION Alloy is the homogenous mixture of two or more metals. Transition metals have approximate same size therefore, in molten form they can fit to each other crystalline structure and form homogenous mixture and form the alloy. Example brass (copper and zinc) and bronze (copper and tin) etc., SOME IMPORTANT COMPOUNDS OF TRANSITION ELEMENTS POTASSIUM DICHROMATE A. ORE: Ferrochrome or chromite (FeO.Cr,0s) or (FeCr20,) B. PREPARATION 4FeO.Cr,03 + 8NaxCO3 +7 02 — 8Na,CrO, + 2 FexO3+8CO (Yellow) 2Na;CrO, + 2H" >Na;Crz O7 +2Na* +H,0 (Orange) Na,Cr,0, +2KCI +K2Cr,0, +2NaCI Sodium dichromate is more soluble than potassium dichrmoate and so , potassium dichrmoate can be prepared by treating the solution of sodium dichromate with potassium chloride. C. PROPERTIES Chromates and dichromates are interconvertible in aqueous solution depending upon pH of the solutions. 2. CrO,? + 2H" — Cr,0;? + H20 CrO,* +2 OH 2 Cr0,” +20 Sodium and potassium dichromates are strong oxidising agents, thus acidified K2Cr207 will oxidise iodides to iodine, sulphides to sulphur, tin(II) ti tin(IV) and iron (II) salt to iron(II). CrO +14H+ +60 —-2Cr3+ +7H20 +31,‘THE INNER TRANSITION ELEMENTS (F BLOCK) The f block consists of the two series lanthanoids and actinoids. Lanthanoids are known as rare earth metals and actinoids are known as radioactive elements. (Th to Lr) LANTHANOIDS GENERAL CHARACTERISTICS > > > > General configuration (Xe) 4f"""*, 5d™1, 6s” This is known as lanthanoid contraction All the lanthanoids are silvery white soft metals and tarnish rapidly in air. Many trivalent lanthanoid ions are coloured both in the soild state and in aqueous solutions. Neither La * nor Lu *ion shows any colour but the rest do so. ‘The overall decrease in atomic and ionic radii from lanthanum to lutetium due to ineffective shielding of 4f orbital electron is known as lanthanoid contraction. The radii of the members of the third transition series to be very similar to those of the corresponding members of the second series. The almost identical radii of Zr (160 pm) and Hf (159 pm), a consequence of the lanthanoid contraction, account for their occurrence together in nature and for the difficulty faced in their separation. Jon other the f ° type (La** and Ce**) and the f'‘ type (Yb”* and Lu*) are all paramagnetic. The paramagnetism arises to maximum in neodynium. Oxidation states of Ce“* is favoured by its noble gas configuration but it is a strong oxidant reverting to the common +3 state. The standard potential value for Ce“'/Ce* is +1.74V the reaction rate is very slow and hence, Ce(IV) is a good analytical reagent, Pr, Nd,Tb and Dy also exhibit +4 state but only in oxides, Eu >* is formed by losing the two s electrons and its f” configuration account for the formation of this ion. However Eu ™ is a strong reducing agent changing to the common 43 state. Similarly Yb ** which has f '* configuration is a reductant. ‘Tb * has half filled f orbitals and is an oxidant. Lanthanoid are very reactive metals like alkaline earth metals. Misch metals contain lanthanoids about 90-95% and 5% Fe and traces of S,C,Ca,Al. Mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint. ACTINOIDS > > > > General configuration [Rn]5f"", 6d°?, 7s” Actinoids exhibit a range of oxidation states due to comparable energies of 5f,6d and 7s orbits. The general oxidation state of actinoids is +3. Alll the actinoids are strong reducing agents and very reactive. Actinoids also react with oxygen, halogen, hydrogen and sulphur etc., like lanthanoids.Cr,0? + 3H)S +8H'2Cr* +3S+ 7H20 Cr07 + 14H? +3Sn*~38n** +2Cr°* +7H20 D. USES > potassium dichromate is used as oxidizing agent in volumetric analysis. > it is used in mordant dyes, leather industry, photography (for hardening of film) > Itis used in chromyl chloride test > Itis used in cleaning glassware. POTASSIUM PERMANGANATE (KMn04 ) Ore pyrolusite (M02) 2MnO, + 4KOH +O, >2K2MnO, + 2H20 (Green) 3MnO,” +4H* >2MnO, + MnO, +2H20 (purple) PROPERTIES KMn04 acts as strong oxidising agent. A.In presence of dilute sulphuric acid potassium permanganate is reduced to manganous salt. Acidified KMnO4 solution oxidises oxalates to CO; iron(II) to iron(II), nitrites to nitrates and iodides to iodine. The half reactions of reductants are ©,0,* + CO, +2e Fe — Fe™ +e NO; — NOs; + 2e- wo bh + 2e To acidify KMnO, only sulphuric acid is used and not hydrochloric acid or nitric acid because hydrochloric acid reacts with KMnO, and produce chlorine while nitric acid itself acts as oxidizing agent. B. In alkaline medium, KMnO, is reduced to insoulble MnO2. ‘Alkaline or neutral KMnO, solution oxidises I- to IO;, $:0;* to SO,?* Mn™* to MnO ect USES > In laboratory preparation of chlorine > KMn0, is used as oxidising agent, disinfectant > In making Baeyers reagent> Actinoids are radioactive in nature in nature and therefore, it is difficult to study their chemical nature. MULTIPLE CHOICE QUESTIONS AND ANSWERS: 1, The element of 3d series which forms a colorless 3+ ion is a)Fe — b)Co c)Mn d) Sc Ans: d) Se 2. Which among the following is not a transition element? a)Mn bv ©) Cr aC Ans: d) Cd 3. Zn has lowest enthalpy of atomization among the 3d elements, because a) It has high melting point ) it has no unpaired electrons to participate in active inter-atomic metallic bonding c) It has got incompletely filled d subshell d) it is not a transition element ‘Ans: b) it has no unpaired electrons to participate in active inter-atomic metallic bonding 4, Among Zn**, Ni**, Cu** and Mn” the one with largest size is a) Zn’ b) Cu* c) Mn™* d) Ni* ‘Ans: c) Mn** 5.The E°M”*/M reduction potentials of Cu, Ni*, Zn™* and V™* are +0.34V, - 0.25V 119-0.76V,-1.18V respectively. The pair of ions with least and highest oxidising power is a)Ni** andCu* by V**andCu* ~~) Cu** and Zn**—d) Zn’* and Ni* Ans: b) V** and Cu* 6. Which among the following has similar atomic radii? a) Scand Y b)NbandTa c)Zrand Hf d) Ni and Pt Ans: c) Zr and Hf 7. The stability of highest Oxidation state of transition elements down a group a) decreases _b) Increases c) remains same d) doesn’t show any regular trend Ans: b) Increases 8. The no. of oxidation states exhibited by a transition element is maximum in the middle of a Series. This is because of a) the presence of more no. of electrons in d and s subshells b) the presence of more no. of unpaired electrons in d subshell c) Availability of empty orbitals in valence shell d) All of these Ans; d) All of these 9. Which has more ionisation enthalpy, Cr* or V* or Mn*? a)V°—b)Cr’— sc) Mn* 4) both Cr* and Mn* ‘Ans; b) Cr* 10. E°vin3.mn2+ is more positive than those of Ti**/Ti* and V**/V**. This is because of a) Change in d configuration from d* to d°, the d° system being more stable by loss of energy through spin exchange b) Change in d configuration from d° to d* c) Change in d configuration from d’ to d’, d° system being more stable due to symmetrical distribution of electron density d) Both a and c Ans: d) Botha andc 11. The lowest common oxidation state shown by 3d series elements is a)t+l b)+2 c) +3 d)i4 Ans: b) +2 12. Cu’ is less stable than Cu™* in aqueous solution. This is because of a) More negative Hydration enthalpy of Cu* ion b) More negative Hydration enthalpy of Cu* ion c) Less negative Hydration enthalpy of Cu”* ion d) Less enthalpy atomization of Cu Ans: _ b) More negative Hydration enthalpy of Cu ion 13. The ion that shows paramagnetic character is a)Zn™* —b)Sc* —c) Ti* d)Ti* Ans: d) Ti* 12014. A dipositive ion 3d series element has s spin only magnetic moment of 5.91 BM. The metal Ion is a)Co™* —b) Fe* ~—c) Ni* d) Mn?* Ans: d) Mn™* 15. Match the following: ELEMENT PROPERTY A) Zine 1) Stable +3 state B) Copper 2) Lowest AHa C) Manganese 3) Paramagnetic moment is 1.732 BM D) Chromium 4)Shows maximum +4 with flourine and +7 oxidation state with oxygen L a) A-2: B-3 : C-4: D-1 c)A-4;B-2;C-3;D-1 Ans: a) A-2: B-3 : C-4: D-1 16. Mischmetall contains a) a lanthanoid element and Zinc b) a lanthanoid element and Tron c) an actinoid element and Mn d) an actinoid element and Mg Ans: b) a lanthanoid element and Iron 17. Ti * ion forms a complex in aqueous solution and is purple colored . This is due to a) d-dtransition b) f-f transition c) L-+M charge transfer d) ML charge transfer Ans: a) d-d transition 18. KMn04 forms a purple colored solution with water. This is due to a) d-dtransition b) f-f transition c) LM charge transfer d) ML charge transfer Ans: c) LM charge transfer 19. Which of the following is most stable in aqueous solutions? a)Mn* b)Cr* c) V* d) Ti** Ans: b) Cr* 20. The oxidation state of Cr in the final product formed by the reaction of KI and acidified K,Cr,0;is a) +4 b) +6 c) +2 d) +3 Ans: d) +3 21. The correct order of second Ionisation enthalpy of Ti, V,Cr and Mn is a) V>Mn>Cr>Ti_—-b) Mn>Cr>Ti>V_c) Ti>V>Cr>Mn d) Cr>Mn>V>Ti Ans: d) Cr>Mn>V>Ti 22. The heaviest transition element is a)Zn b) Sc C)Ta d) Os Ans: d) Os23. Which of the following statements related to lanthanoids is incorrect? a) Eu shows +2 oxidation state b) Pr(OH)3 to Lu(OH),, basicity decreases ) Alll lanthanoids are more reactive than Al d) Ce ** is an oxidizing agent Ans:c) All lanthanoids are more reactive than Al 24. Intersitial compounds are non-stoichiometric compounds formed by Transition elements when atoms like H,C,N are trapped in the interstitial sites of transition metal lattices. Which of the following is not a property of interstitial compounds? a) They are very hard b) They retain metallic conductivity c) They have high melting points d) They are chemically very reactive : d) They are chemically very reactive 25. Ti** in aqueous solution forms a complex ion with water. The purple color of this complex is due to the d-d transition ie., the electronic transition from a) bg toe D) €g to tog Cc) ty to eg d) eg to ty ANS: a) thy to ey 26. Which among the following oxides of Vanadium is amphoteric a) V20s b) VO, c) V203 d) V204 Ans; a) V20s 27. Which is most covalent Mn.O, or MnO2 or MnO? a) Mn,0, b) MnO c) MnO, d) Both MnO and MnO, Ans:a) Mn,0; ASSERTION AND REASONING QUESTIONS: Note: In the following questions a statement of assertion followed by a statement of reason is given. Choose the correct answer out of the following choices. a) Both A and R are correct statements and R is the correct explanation of A b) Both A and R are correct statements but R is not the correct explanation of A c) Both A and R are false statements d) A is true R is false. 1. Assertion : Cr** is a good reducing agent Reason : Cr°* donates one electron to become Cr** which in tum is a stable half filled), system. Ans: a2. Assertion : Actinoid contraction is greater from element to element than Lanthanoid contraction Reason: The shielding effect of 5f orbitals is poor in comparison to 4f orbitals Ans; a 3. Assertion : The E°¢c4,,ce3, feduction potential is more positive Reason : Ce “* can act as an analytical agent Ans: b 4, Assertion: Cr in +6 oxidation state is a better oxidizing agent than Mo in +6 oxidation state Reason : In transition elements, the stability of highest oxidation state increases down a group Ans: a 5. Assertion: MnF, is unknown whereas KMnO4 is known Reason: Oxygen, though being less electronegative than Fluorine, is versatile in stabilizing Highest oxidation states of transition metals by forming multiple bonds with metal atom. Ans:a 6. Assertion : MnO; is more acidic than MnO Reason : Higher the oxidation state of the metal less is the acidic character. ‘Ans: d 7. Assertion : Transition metals and their compounds can act as good catalysts Reason: Transition metals can adopt multiple oxidation states. Ans: a 8. Assertion : Transition metal ions can form complex compounds with ligands Reason : Transition metal ions have large size, low charge and completely filled d orbitals Ans: d 9. Assertion : Transition metals show variable oxidation states. Reason : This is due to the incompletely filled d orbitals Al2 MARKS QUESTIONS AND ANSWERS: 1) What are d and f block elements? Write their general electronic configurations. The elements present in groups 3 to 12 and in the periods 4 to 7 of modem Periodic Table are called d and f block elements. General electronic configuration of d block elements: (n-1)d'""° ns'? where n= 4,5,6.7 General electronic configurationof f block elements: (n-2)f ''* (n-1)d °' ns? where n= 6,7 2) Group 12 elements are not considered as transition elements. Why? Zn, Cd and Hg have completely filled d subshell in its atomic state as well as in its ionic states. So they are not considered as Transition elements. 3) Sc is a transition element whereas Zn is not. Why? Sc has incompletely filled d subshell (d') in its ground state where as Zn has got completely filled d subshell in both ground state as well as excited state (d"°) 4) Silver atom has completely filled d orbitals in the ground state (4d'°). How can you say that it is a transition element? Though silver has 4d'° configuration in its ground state as well as +1 excited state, in its +2 state it has a d’ configuration. So it is considered as a transition element. Note; A transition element should have incompletely filled d subshell either in its atomic state or in one of its ionic states. 5) In 3d series, the melting point and enthalpy of atomisation of Manganese is less compared to those of its immediate neighbors. Why? 124Mn has a half filled d subshell(d°) which is stable. Therefore the willingness of electrons in 45 system to actively participate in inter atomic metallic bonding will be less. 6) What is Lanthanide contraction? What is its consequence? ‘The gradual decrease in atomic and Ionic sizes of lanthanoid elements(from L to Rin 4f series) due to imperfect shielding of 4f orbitals is called Lanthanoid contraction. Consequence: 1.4d and 5d series elements will have similar atomic/ionic sizes. Physical separation of 4d and 5d series elements from each other becomes difficult as the sizes are similar. Eg: Zr and Hf have similar atomic radii and their physical separation from each other is difficult 2.Basic character of lanthanum hydroxide decreases from La to Lu 7) Why do transition elements show variable oxidation states? This is due to incompletely filled d orbitals and the participation of both (n-1)d and ns electrons in the bonding process as they have comparable energies. 8) Why is Cr°* reducing whereas Mn** oxidizing when both have d‘ configuration? , Cr’ is a reducing agent because it donates one electron to become Cr** which in turn is characterized by half filled ty, orbitals,(a stable system). On other hand, Mn** is an oxidizing agent because it accepts one electron to become Mn** which is characterized by a stable half filled d subshell ie., a 9) The E°ysune reduction potential of Cu” reduction is most positive (+0.34V) among E°x2/ reduction potential values of divalent ions in 3d series. Why? 125The energy invested in creating +2 state of Cu ( AHa + AHi(1) + AHi(2)) is more in comparison to the energy released during hydration of Cu2+ ion in water (Hydration enthalpy) 10) How would you account for the irregular variation of first ionisation enthalpies in the first series of the transition elements? Inegular variation of ionisation enthalpies is mainly due to varying degree of stability of different 3d configurations (d° ,d° and d'° are exceptionally stable) 11) Which is a stronger reducing agent Cr™* or Fe™* and why? Cr’* is a stronger reducing agent than Fe** The E® values are E%es,ca = O.41V and Epes = 0.77V. The transition Cr?">Cr* +e _ iis easier as Cr°+ is stable by the virtue of having having half filled ty, orbitals. ‘The transition Fe" Fe** + eis comparatively less because it involves losing of an electron from Fe2+ with EC d® to d° configuration. 12) Why is Cut unstable in aqueous solutions? In aqueous solution, Cu+ undergoes disproportionation reaction. 2Cu* > Cu* + Cu The higher stability of Cu * (aq) is due to higher negative hydration enthalpy of Cu** in comparison to that of Cu+. 13) Actinoid contraction is greater from element to element than lanthanoid contraction. Why? In actinoids, the poor shielding effect of 5f orbitals cause more contraction in sizes of actinoids as we move from left to right across the 5f series. The 5f electrons have poor shielding effect as compared to 4f electrons. 14) How is the variability in oxidation states of transition metals different from that of non-transition elements? In transition metals the oxidation state vary by unity (due to in completely filled d orbitals) In non- transition elements this variation is selective, differing by 15)Why is the highest oxidation state of a metal exhibited in its oxide and fluoride only? 126This is due to a) high electronegativities of Fluorine and Oxygen and ability of oxygen to form multiple bonds b) high lattice energy as in the case of CoF3 or high bond enthalpy terms in covalent fluorides like VFsand CrF 3 MARKS QUESTIONS AND ANSWERS. 1. Give reasons: Transition metals a) form complexes b) their compounds act as catalysts c) form coloured compounds Ans: a) Transition metal ions have high charge, small size and availability of incomplete d orbitals b) Transition metals have variable oxidation states and form intermediates with low activation energy, therefore used as a catalyst. Transition metals are small and so provide larger surface area for the reactant to be adsorbed. c) Transition metal ions have unpaired electron and undergo d-d transition. 2. Explain by giving reasons: a) Transition metals and many of their compounds show paramagnetic behavior b) The enthalpies of atomization of transition metals are high c) Transition metals form alloys and Interstitial compounds Ans; a) They have unpaired electrons and show paramagnetic behavior b) Unpaired electrons in ultimate and penultimate shells actively participate in inter-atomic metallic bonding and due to strong M-M bonding the enthalpies of atomization of transition metals are high ¢) Transition metal atomic sizes do not vary much. So alloys are easily formed among transition metals. They form interstitial compounds because the interstitial sites in transition metal lattices can accommodate smaller atoms like H,C,N etc 3. Suggest reasons: a) The lowest oxide of transition metal is basic, the highest amphoteric or acidic b) The highest oxidation state is exhibited in oxoanions of transition metal c) For the 3d series elements the E°y2,. reduction potentials are irregular 127Ans: a) In lowest oxide, the oxidation state of the transition metal is less and the metal can donate electrons as some electrons are not involved in bonding whereas in highest oxide the oxidation state is high as the electrons are involved in bonding and can’t be donated. So they are amphoteric. In some highest oxides the oxidation state is so high that the metal can receive electron density from other species and thus behaving like acidic oxides b) Oxygen, the second most electronegative element and it can form multiple bonds with metal atom. ©) The reduction potentials are not regular which can be explained from the irregular variation of Ionisation enthalpies (AHi(1) + AHi(2)) and also the sublimation enthalpies which are relatively less for Mn and V. 4, List the differences between Lanthanoids and actinoids LANTHANOIDS ACTINOIDS 4f subshell gets progressively filled up | 5f sub shell progressively gets filled up with electrons. and _—_anthanoid | with electrons and actinoid contraction contraction takes place takes place Less reactive than actinoids More reactive than lanthanoids +3 state is more common along with +2 | Can show O.S from +2 to +7 which are and +4 not uncommon 5. Explain the oxidizing action of acidified KyCr20; with a) Iodide ions b) H»S c) Fe* Ans: a) Dichromate ions oxidise Iodide ions to elemental Iodine CrO;* + 14H* + 61-3 2Cr* + 31, +7H,0 b) Dichromate ions in acidic conditions oxidize HS to elemental sulfur Cr07* + 8H* +3H2S— 2Cr*+3S +7H,0 c) Ferrous ions are oxidized to Ferric ions by acidified K,Cr,O, Cr,0;* + 14H* + 6Fe**— 2Cr* + 6Fe* +7H,0 6.What is meant by the term lanthanoid contraction? What is it due to and what consequences does it have on the chemistry of elements following lanthanoids in the periodic table? Ans. Lanthanoid contraction: Steady decrease in the size of the lanthanoids ions with increase in the atomic number across the period. The electrons of 4f orbitals offer imperfect / poor shielding effect in the same subshell as we go from La to Lu. Consequence: i) Due to this 5d series elements have nearly same radii as that of 4d series. 128ii) Decrease in the basic strength from La (OH)3 to Lu(OH)3. iii) Due to similar atomic size there is difficulty in separation of lanthanides. 7.a.For the first row of transition metals the E” values are:- E’ values V Cr Mn Fe Co Ni Cu M2+/M -1.18 -0.91 -1.18 -0.44 -0.28 0.25 +0.34 Explain the irregularity in the above values b. Transition elements show high melting points. Why? c. Zinc is soft whereas Cr is hard. Why? Answer a. The Standard Electrode Potential E” values for M2+/M as depend on the thermochemical parameters such as enthalpies and ionization energies. There is no regular trend in the E° values of first transition element. It is because, their ionization enthalpies (IE1 + IE2) and sublimation enthalpies do not show any regular trend. The general trend towards less negative EO values along the series is due to the general increase in the sum Of first and second ionization enthalpies. b. Due to strong metal-metal bonding c. Zn has completely filled d-orbital; hence d orbital electrons are not involved in metallic bonds while Cr has half-filled d-orbital and can form metallic bonds. Since metallic bonds make a metal hard, Cr is hard and Zn is soft. 5 Marks Question Q. 1- Assign reasons for the following: a) The enthalpies of atomization of transition elements are high. b) The transition metals and many of their compounds act as good catalysts. c) There is a gradual decrease in the atomic sizes of transition elements in a series with increasing atomic number. 4d) The transition elements have great tendency for complex formation. e) Transition metals generally form coloured compounds. Ans- a) This is because transition elements have strong metallic bonds as they have large number of unpaired electrons, therefore they have greater interatomic overlap. b) The catalytic activity of transition metals is attributed to the following reasons i) Because of their variable oxidation state, transition metals form unstable intermediate compounds and provide a new path with lower activation energy for the reaction, ii) In some cases, the transitions metal provides a suitable large surface area with free valencies on which reactants are adsorbed. 129c) There is a gradual decrease in the atomic sizes of transition elements in a series with increasing atomic numbers due to poor shielding effects of the d-electrons, the net electrostatic attraction between the nucleus and the outermost electrons increases. d) Incompletely filled d orbitals of suitable energy, small size of cations and higher nuclear charge. e) Due to presence of unpaired electrons in d-orbitals which undergoes d-d transition. CASE BASED QUESTIONS: 1. Potassium dichromate is a very important chemical compound used in leather industry. It is used as an oxidant. It is also used in the preparation of many azo compounds. It is a crystalline ionic solid with bright color. It is not deliquescent in contrast to Sodium dichromate. The conversion of chromate ions to dichromate ions and vice versa is pH sensitive. Potassium dichromate in acidic condition is a milder oxidising agent than acidified Potassium permanganate. This fact is revealed by their corresponding standard reduction potential values which can be extracted from any chemical literature pertaining to Inorganic chemistry. i) If the pH of the solution containing chromate ions is decreased, what is it converted to? Ans: Itis converted to dichromate ions. 2CrO,* + 2H* +C1,0;7 + H,O ii) What is the oxidation state of Cr in KjCr:0;? 1) 42 2) 43 3) +4 4) +6 ANS: +6 iii) Write balanced chemical equations for the reaction of acidified Potassium dichromate reactions with a) KI b) Sn’* ions ANSWER: a) Cr,07" + 61+14H" — 2Cr* + 312 + 7H20 b) CO; + 14H’ + 3Sn”* > 2Cr* + 3Sn** + 7H,0 2) Potassium permanganate is an inorganic crystalline salt with purplish black color that dissolves in water to produce K+ and MnO- ions. The aqueous solution is intensely pink to purple in color. Potassium permanganate is a powerful oxidizing agent in acidic and basic conditions. As a strong oxidant that does not generate toxic by products , Potassium permanganate has many niche uses. It is used in the treatment of Dermatitis and in treatment of water. It is also called as Bayer’s reagent. i) Alkaline oxidative fusion of MnO) gives ---------- 1301)MnO; 2) MnO,” 3)MnO 4) Mn,0; Ans: MnO,” (Manganate ion) ii) Assertion: KMnO, in acidic condition is a good oxidizing agent Reason : It can oxidize Iodide ions to elemental Iodine a) Both A and R are correct statements and R is the correct explanation of A b) Both A and R are correct statements but R is not the correct explanation of A c) Both A and R are false statements d) A is true R is false. Ans: b iii) Write the balanced chemical equations for the reaction of acidified KMnO4 with 1) Fe” 2) C07 Ans 1) MnO, +5Fe™* +8H'—> Mn™ +5Fe* +4H,O 2) 5C,0,* + 2MnO,° + 16H* — 2Mn™ +8H,0 + 10CO, HOTS QUESTIONS AND ANSWERS: 1, When a chromite ore (A) is fused with Sodium carbonate in free excess of air and the product Is dissolved in water, a yellow solution of the compound(B) is obtained. After treatment of this yellow solution with Sulfuric acid, compound (C) can be crystallized from the solution. When compound (C) is treated with KCI, orange crystals of compound(D) crystallize out. Identify A to D and also explain the reactions. A= Fe,Cr04, B= Na;CrO,, C= Na;Cr,0;, D= KxCr,0; a) 4Fe,CrO, +8Na,CO; +70; —> 8 Na,CrO, + 2Fe;03+ 8CO; b) 2Na;CrO, +2H* — NajCrO, +2.Na* +H,0 ©) NaCr,0, + 2KCI— K,Cr,0; + 2NaCl 2. When an oxides of Manganese (A) is fused with KOH in presence of an oxidizing agent and dissolved in water , it gives a dark green solution of compound (B). The compound (B) disproportionate in neutral or acidic solution to give purple compound(C). An alkaline solution of Compound (C) oxidizes KI solution to a compound (D) and compound (A) is also formed. Identify compounds A to D and also explain the reactions involved. Ans: A= MnOz, B= K;MnO,, C= KMn04 and D = KIO; 131a) 2MnO; + 4KOH + 0, >2K,Mn0O, + 2 HO b) 3MnO,' + 4H* > 2 MnO, + MnO, + 2H,0 c) 2MnO, + H,0 + KI-+ 2Mn0, + 20H’ + KIO; 3. Why does Cu not displace Hydrogen from acid? E? c2vcu is more positive than E°y.0. Thevesag atomic rime —— a. In the above graph which all the transition series have same size. Why? b. Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite difficult to separate them. Why? c. Transition elements exhibit higher enthalpies of atomization. why Answer a. 4d and 5d series, due to Lanthanoid contraction b. Due to Lanthanoid contraction the increase in size from second to third series vanishes. So Zr and Hf have almost similar size and it is difficult to separate. c. Due to the presence of unpaired electrons and d-d transition. IMPORTANT CHEMICAL EQUATIONS: 1, 4FeCrO, + 8Na;COs +70; — 8 NazCrO, + 2Fe:03 + 8CO2 2Na,CrO, + 2H" — Na;Cr,07 +2 Na* +H,0 Na;Cr,O, + 2KCI> K;Cr,07 + 2NaCl 2. C107" + 14H" + 6e > 2Cr** + 7H2O ( oxidising action of dichromate in acidic medium) 3.Cr07° +20H — 2Cr0,” + H,0 132(Orange) (yellow) 4. Cr,0;" + 8H* + 3 NO, — 2Cr* +3 NOs + 4H,O 5. C07" + 3Sn™* + 14H* > 2Cr* + 3Sn** + 7H,0 6. Cr,0;" + 3H,S + 8H" > 2Cr* + 3S + 7H20 7. Cr,0;* + 6Fe* +14H* > 2Cr* + 6Fe* + 7H;0 8. Cr?" + 6T+14H* — 2Cr* + 31, + 7H;0 9. MnO; + 8H" +5Fe™* + Mn™ +5Fe* + 4H,0 10. 2MnO,' + 101 + 16H*—> 2 Mn™ + SI, + 8H,0 11. 2MnOs +H,O +I 2MnO,+20H +105 12, 2MnO, + 3Mn”* + 2H,O > 5 MnO, + 4H™ 13.2 MnO,’ + 16H* + 5C,0,"—> 2 Mn” + 8H,0 + 10CO2 14, 2MnO, + 4KOH + 02 > 2K2MnO, + 2H;0 15.2KMn04 — K,MnO, + MnO, + O, ( decomposition on heating) 133