d and f - BLOCK ELEMENTS CHAPTER - 11 d- BLOCK ELEMENTS : TRANSITION ELEMENTS 11.1 [TRANSITION METALS : Atransition metal may be defined as one that has an incomplete inner d-orbital. A transition metal is also called a transition element or a d-block element. The general electronic configuration of transition elements is (n-1)d!~!° ns!~2, whereas 12 12 1-6 the general electronic configuration of representative elements is ns!~2 or ns!~? ns? np In the case of d-block (transition) elements, electrons are added successively to the inner d-orbitals. The elements are called transition elements (Table 11.1) as they are placed between the s- and p-block elements and their properties represent a transition between the highly reactive electropositive elements of the s-block and the electronegative elements of the p-block. TRANSITION ELEMENTS ish arte | aaPt ro4RFf osha 06%} “ss >, su‘These transition elements are present in the periodic table in four series. Table : 11.2 Series of transition elements Series Number — Element present Electronic of elements configuration Ist Series (3d Series) 10 Sc) (Scandium) to Znyy (Zine) [Ar]3d! 14s! 2nd Series (4d Series) 10 Y3o(Yttrium) to Cdyo (cadmium) [Kr}4d!~ 1551? 3rd Series (5d Series) 10 La,(Lanthanum), Hf,(Hafnium) to Hggq (Mercury) [Xe]4pl4sa!10 63! 4th Series Acgg (Actinium),RF 94 and (6d incomplete series) newly discovered elements, [Rn]5f'4 6d! 10 751-2 AtNo. 105-110 Just after the transition element Lanthanum Las, ({Xe]4f°5d!6s?) (Table.11.2), the next transition element is Hafnium Hf [Xe]4f!45a76s. The elements occurring just after Lanthanum is Cerium, Cesg({Xe]4f°5d°6s”). A series of 14 elements from Ces to Luz), Lutetium ({Xe]4f!45d!6s2) ae called as Ist series of inner transition elements or f-block elements. These are known as Lanthanides or 4f-block elements. The 2nd series of inner transition elements are elements occurring just after the transition element Actinium, Acgg-These are the actinides or 5f-block elements beginning with Thorium, Thgo ({Rn]5/°6d75?) and ending till now in Lawrencium, Lwj93({Rn]5f!46d'7s?). Inner transition elements contain incomplete 4f and 5f orbitals respectively in addition to their incomplete (n-1)d orbitals. Inner transition elements are special type of transition elements. There are three transition series of elements (Table 11.2). The Ist series or 3d series begins with the element Scandium, Sey, ({Ar]3d!4s?) and ends with the element Zinc, Zn3g- ({Ar]3d!04s2), The 2nd series or 4d series begins with the clement Yttrium, Y 39 ([Kr]4d!5s?) and ends with the element Cadmium, Cdyg ((Kr]4d!°55°). The 3d series begins only with Lanthanum, Las7, ((Xe]4/°5d!6s7),and then begins with Hafnium, Hf, ([Xe]4f!45a76sTable : 11.3 The outer electronic configurations of the atoms and ions of the first transition series Elements Atomic Outer E.C Tons and their outer E.C number Tons E.c Tons E.C Scandium (Sc) 21 3p%3d!4s2 Sc3+ 3p®(non- transitional) Titanium (Ti) 22 3p®3d24s* TH+ 3p%d2Ti3+ 3p%a! Vanadium(V) 23 3p®3d34s2_— V+ 3p%3a3_v3+ 3p°3d? Chromium (Cr) 24 3p3d54s!_ cr? 3p%3dt cr 3p%3a3 Manganese (Mn) 25 3p03d54s2_—Mn?*— 3p®3d5.— ss Mn+ 3p%3a4 Iron (Fe) 26 — 3p03d°4s?_—Fe?* 3p°3d® ss Fe** 3p°3a> Cobalt (Co) 27 3p®3d74s2-_— Co** 3p%3d?_— Co3* 3p%3d® Nickel (Ni) 28 3p03d84s2_— Ni2+ 3p%3a8 Copper (Cu) 29 — 3p®3d!4s!_ Cu2* 3p%3d?_ Cut 3p%3al0 (non- transitional) Zinc (Zn) 30. 3p®3d!04s2—Zn?2+ 3p%3d!9 — (non- transitional)11.2 [GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS = ‘Transition elements are solid metals hard.malleable and ductile, They have relatively high densities, high melting points and high boiling points. These properties indicate that the atoms in these elements are held together by strong metallic bonds. Such metallic bonds are even present in their molten states. The properties of transition (d-block) elements are intermediate between the properties of s and p block elements. Table : 11.4 Properties of elements of the first transition metal series Element Property Sc Ti V Cr Mn Fe Co Ni Cu Atomic mass 45.00 47.88 50.95 52.00 54.94 55.85 58.93 58.69 63.54 Atomic radius, A° 1.64 1471.35 1.29 1.26 1.261.251.2428 Tonic radius,A°M2* — 0.80 0.73 — 0.90 085 080 0.76 0.69 M* 0.69 0.63 0.62 062 063 063 056 — = |stIonisationenergy kimol"! 685 659650 654.713.762.759 736745, Densitygce! 34S 60 69 T4719 878989 Melting point, K 1200 16601710 1600 126015351490 1450, 1083 Boiling point. 2730 3260 3450 2660 2150 3000 2900 2730 2600 1. Atomic ra ‘The atomic radii of the transition elements of a particular series decrease slightly with increase in atomic number. In the case of these elements, the electrons are added successively to the inner (n-1)d orbitals and these electrons screen the outer ns electrons from the nucleus. The effective nuclear charge thus increases slightly. Therefore, there is a slight decrease in atomic radi a6 +2 CHEMISTRY (VOL.- 1) In the first transition series the atomic radius value increases from Ni (1.24) to Cu (1.28). This is due to increased force of repulsion between added electrons which overcome effective nuclear charge (nuclear attraction force).2. Tonisation enthalpy : Jonisation enthalpies of transition elements increase across a transition series with increase in atomic number. This trend is, however, not regular. This is because though the nuclear charge increases, the screening effect of added electrons also increases. These two effects almost cancel each other. Ionisation enthalpies are in between s- and p- block elements and these elements are less electropositive than s-block elements. Zinc, cadmium and mercury have comparativly higher ionisation enthalpy values, because they have stable outer electronic configuration, (n-1)d!ns?. There is a general increase in the second ionisation enthalpy as the atomic number increases. The exception is manganese. The second ionisation enthalpy of Cr and Cu involves the removal of one electron from the 4s orbital and another electron from the half-filled and completely filled 3d-orbital respectively. The half-filled and filled orbitals have extra stability associated with them. ‘Therefore, the second ionisation enthalpy of these elements are relatively larger. Eventhough transition elements form ionic compounds, the tendency is less than the s-block elements. In higher valency state, there is also a tendency for covalent bond formation. 3. Metallic properties : Transition elements are all hard metals except mercury which is a liquid. These elements are harder and more brittle than s-block elements. The atoms in these elements are held together by strong metallic bonds. The strength of such metallic bonding depends upon the interaction between the electrons in the outermost shell. In general, the greater the number of valence electrons available, the stronger is the bond. Further electrons in the d-orbitals form stronger metallic bonds. In transition elements, a minimum of three electrons, (n-1)d* ns? are available for interaction with other atoms for the metallic bond formation. Again greater the number of unpaired electrons greater is the strength of the bond. In the first transition series Cr is very hard having five unpaired d- electrons. In the case of Znyy (3d!°4s?), the metal is not hard because there is complete pairing of 3d electrons. In the third transition series Hggq(5d!6s?)having complete pairing of 5d electrons exists as a liquid. These metals are, as expected, good conductors of heat and electricity.5. Variable oxidation states : Transition elements show more than one oxidation states in their compounds. The oxidation states shown by the first transition series are given in (Table9.5)The most usual oxidation states are indicated as bold. Tabe : 11.5 Different oxidation states of elements of first transition series Elements ——> Se_ Ti v Cr Mn Fe _ Co +200 42, +2042 Oxidation states +20 42 +2 +3 +3043 +3 4300-43043 +4 4 +4 +4 +4 +5 +5 +6 +6 +6 +7 Transition metals have their valence electrons in two different sets of orbitals ns and (n-1)d which have nearly the same energies. All these elements use their two ns electrons and thus show +2 oxidation states. When oxidation states are greater than +2, the unpaired (n-1)d electrons are involved in bonding in addition to the ns electrons. The elements thus show +3 and higher oxidation states besides +2 oxidation state. Scandium has exclusively an oxidation state of +3. In the case of tansition elements the oxidation states vary by one unit whereas in some of the p-block elements variable oxidation states marked by a difference of two units. This is due to the inert pair effect. Thallium shows oxidation states +1 and +3 and lead has two oxidation states +2 and +4.6. Formation of coloured compounds : Majority of transition metal compounds are coloured. In contrast the compounds of s-and p-block elements are often colourless or are generally not strongly coloured. When a compound absorbs light of a particular wavelength,it is able to promote and electron from one energy level to another higher energy level. IfE, is the energy associated with the electron in one energy level and E,, the energy associated with the eletron in the higher energy level, then E>~E =A Ei.e. energy of absorbed light or radiation. Since AE = hv =h —, the energy of absorbed radiation is inversely proportional to the wavelength 4. Coloured substances such as compounds of transition elements absorb in the visible region 4000-7500A °or longer wavlength. Colourless substancees such as compounds of s— and p- block elements absorb in the u.v(ultraviolet) region below 4000A° or shorter wavelength. The compounds of transition metals are coloured due to the presence of unpaired d- electrons in the partly filled d- orbitals of the metal. Here the light radiation is absorbed in the visible region ( 4, =4000 -7500 A ) with a fairly small energy to promote d— electron to ahigher energy level within the d- orbital, resulting d—d transitions of electrons. The colour of the compound is complementary to the observed colour. CuSO4.5H,0 is blue in colour since it absorbs orange colour from visible light (4 =6000 - 6500A° ) and emits the complementary colour blue (blue is complementary to orange). Relation between absorbed and observed colours Wave length (A°) Absorbed colour Observed complementary colour 4000- 4500 violet yellow 4500-5000 blue orange 5000- 5500 green ted 5500- 6000 yellow violet 6000- 6500 orange blue 6500-7000 red greenThe compounds of Sc3*+ (3° 45%) and Zn7*( 3d! 45° ) are colourless because they do not contain any unpaired d-electron . In case of s~ and p~ block elements, there may not be a d- orbital, if any one is completely full. For such elements there cannot be any d-d transition of electrons. However, 5 or pelectron can be promoted to a higher energy level provided the element receives much greater energy corresponding to wavelengths of ultraviolet region. Here there is no absorption of radiation from the visible region. Therefore compounds of s— and p—block elements do not appear coloured in the visible region. Table : 11.6 Colour shown by some hydrated transition metal ions. Ton se3+ Tot Outer electronic Configuration 3a° 3a! 3a? 3a 3a* 3a° 3a° 3° 3a? 3a8 3a? 3410 3q10 No. of unpaired electrons 0 1 (a Colour Colourless Purple Green Violet Violet Pink Yellow Green Pink Green Blue Colourless Colourless9. Paramagnetism : Transition metals and their compounds are paramagnetic in nature i.e. they are attracted by magnetic field. Paramagnetism arises due to the presence of unpaired d- electrons. These electrons can be regarded as spinning around their axes, just as an electric current through a wire generates a magnetic moment. Magnetic moment due to electron spin is given by per = s/n(n+2) where n = number of unpaired electrons.A substance become strongly paramagnetic if it contains more number of unpaired electrons.Mn2* (3d° 48° ) and Fe>* (3d? 48° Jare most 10 45° and Zn>* a! 45° ) are diamagnetic in nature. A paramagnetic, whereas scot (3d diamagnetic (non-magnetic) substance is repelled by a magnetic field. In such cases, the paired electrons pos: S Opposite spins and cancel the magnetic moments. In the case of Fe, Co and Ni the spins of the unpaired electrons are much pronounced.As a result, these elements are much more paramagnetic than the rest of the elements. These element are called ferromagnetic which means that they can be magnetised.11.3 [POTASSIUM DICHROMATE K,Cr,0, : It is an important oxidant used for preparation of many azo compounds. Besides it finds its use in leather industry. Preparation : Steps involved (i) Chromite ore (FeCr,O,) is fused with sodium or potasium carbonate in free access of air producing sodium chromate. 4FeCr,0, + Na,CO, + 70, 8Na,CrO, + 2Fe,O, + 8CO, Gi) The yellow solutions of Sodium dichromate is filtered and acidified with Sulphuric acid to give a solution from which orange sodium dichromate Na,Cr,O,.2H,O can be crystallised. 2Na,CrO, + 2H"—> Na,Cr,O, + 2Na* + H,O (iii) The hot saturated solution of Na,Cr,O, is treated with KCI to produce potasium dichromate. Sodium dichromate is more soluble than potasium dichromate. Na,Cr,O, + 2KCI > K,Cr,O, + 2NaCl Sodium chloride precipitates out from the hot solution and is removed by filtration. On cooling the mother liquor orange crystals of K,Cr,O, crystllise out. The oxidation state of chromium in CrO,* and Cr,O,* is the same. These ions are interconvertible in aqueous solution depending upon pH of the solution. 2Cr10?- + 2H" Cr,0- +H,0 Cr,0,> + 20H--> 2Cr10, + H,O Structure of CrO> & Cr,0,2- O 2- 2 J OP Ze. o” | So o” Oy oO ‘chromate ion dichromate ionPhysical properties : Potasium dichromate form orange red crystals melting at 671K. It is moderately soluble in cold water but highly soluble in hot water. Chemical properties : On strong heating it decomposes to chromic oxide and oxygen 4K,Cr,0, —* 5 4k,Cr0, + 2C1,0, +30, Itreacts with hydrochloric acid evolving chlorine K,Cr,0, + I4HCI > 2KCI + 2CrCI, + 7H,0 + 31, ‘When heated with Cone. H,SO, and a soluble chloride such as NaCl, gives red vapours of chromyl chloride. K,Cr,0, + 4NaCI + 6H,SO, > 2KHSO, + 4NaHSO, + 2Cr0,Cl, + 2H,0 In volumetric analysis itis used as a primary standard. It is a powerful oxidising agent. In acidic solution ie the presence of dilute H,SO, its oxidising action is represented as Cr,0,° + 14H" + 6 + 2Cr* + 7H,O ‘Some oxidation reactions are given below. wi (i) ii) It liberates I, from KI solution 6 31, + 6e Cr,0, + 14H" + 6e > 2Cr* + 7H,O ~Cr,0,-+ 6F + 14H > 2CP* + 7H,0 +31, Itoxidises Fe* to Fe él > 6Fe™ + 6 1,02 + 14H" + 6e + 2Cr* + 7H,O Cr,07 + 14H + 6Fe™ — 2Cr* + 6Fe™ + 7H,0 It oxidises H,S to S & SO, to sulphuric acid. 3H,S > GH? +38 + 6e 1,0," + 14H" + 6e > 2Cr* +71 Cr,0,* + 8H* + 3H,S > 2Cr* + 38 +7H,0 380, + 6H,O - 3S0,> + 12H’ + 6e 1,0, + 14H" + 6e > 2Cr* + THO 1,0 + 2H" + 380, > 2Cr* + H,0 + 380,Uses : @ (i) ii) (iv) w) 4 (iv) Ttoxidises sulphite ion to SO, ion. cee tgs + 380° + 8H* > 2Cr+ + 3S0,- +4H,O In dichromate solution Cr,0,* ions are in equilibrium with Cr? ions. Cr,0,> + H,O = 2Cr0> + 2H" Orange red Yellow (a) Onaddition of alkali the orange colour changes to yellow 1,0, + 2KOH > 2K,CrO, + H,0 Orange red. Yellow (b) On addition of acid to the above solution the yellow colour again changes to orange red. 2K,CrO, + 2H,$0, > K,Cr,0, + K,SO, + H,0 Yellow Orange red, In volumetric analysis for estimation of Fe**, I ions. In the preparation of several chromium compounds like ZnCrO,, PbCrO, etc. In photography. Asacleansing agent (K,Cr,0, + Cone H,SO,) for gl In dyeing, chrome tanning etc. [POTASSIUM PERMANGANATE (KMn0,) : Method of preparation : @ (i) is prepared from K,MnO, by the action of dil H,SO, 3K,MnO, + 2H,SO, — 2K,SO, + 2KMnO, + MnO,4 +2H,O MnO, is removed by filtration, Potassium permanganate being less soluble than K,SO,, crystallises out first. Solid manganese (IV) oxide is fused with KOH and the melt is stirred in contact with air 2MnO, + 4KOH + 0,» 2K,MnO, + 2H,0 Chlorine gas is then passed through green solution of potassium manganate to produce potassium permanganate, 2K,MnO, + Cl, > 2KCI + 2KMnO, ‘Since KCI is more soluble than KMnO,,, on concentrating the solution KMnO, separates out first leaving behind KC1 in solution.Physical properties : Potasium permanganate forms dark purple (almost black) crystal isostructural with those of KCIO,. It is not very much soluble in water, about 6.4 gms dissolving in 100 gms of water at 293K. Both manganate and permanganate ions are tetrahedral. The green manganate is paramagnetic with one unpaired electron whereas the purple permanganate is diamagnetic. The x bonding is due to overlap of p-orbital of oxygen with d-orbital of manganese. oO oO th, A o” | No of | No Tetrahedral manganate ion (green) Tetrahedral permanganate ion (purple) Chemical properties : 1. It decomposes evolving oxygen when heated alone or with alkali. 2KMnO, —\-> K,MnO, + MnO, + 0, 4KMn0O, + 4KOH > 4K,Mn0O, + 2H,0 + O, 2. When treated with Conc H,SO, it produces Mn(VII) oxide which decomposes explosively when heated. 2KMna0O, + H,SO, > Mn,O, + K,SO, + H,O© Examples : In acidic solution : In acidic solution MnO, ion is reduced to Mn({I) ion, 2MnO, + 6H* — Mn** + 3H,0 + 5[0] ‘The best acid to be used is dilute sulphuric acid, Permanganate titrations with HCl are not s factory since HC1 is oxidised to Cl, during the titration, 2KMnO, + 3H,SO, + K,SO, + 2MnSO, + 3H,0 + 5{0] Most of the volumetric analysis in carried out in acid medium, The end point is marked by change of colour from purple (MnO) to almost colourless [Mn (II) ion] a 2) 3) a) (5) 6) @ a) Q) @) 4) (5) Fe’ ion is converted to Fe™ ion. SFe* + MnO, + 8H" 2Mn* + 4H,O + 5Fe* green yellow I, is liberated from KI. 101 +2 MnO, + 16H*—> 2Mn** + 8H,O + 51, Oxalic acid is oxidised to CO,. 2MnO, + 16H’ + 5C,O,—> 2Mn* + 8H,O + 10CO, Sulphites are oxidised to sulphates 2MnO, + 6H’ + SSO,» 2Mn* + 5SO2-+3 H,O HLS is oxidised to sulphur HS > 2H" +S* 5S* + 2MnO, + 16H'—> 2Mn™ + 8H,O +58 SO, is oxidised to H,SO, 2MnO,- + 5SO, + 2H,O — 2Mn* + 580+ 4H* Nitrites are oxidised to Nitrates. 5NO,; + 2MnO,- + 6H" 2Mn* + SNO, + 3H,O In qualitative analysis for detection of halides, sulphites, oxalates ete. In volumetric estimations, In the manufacture of saccharine, benzoic acid, acetaldehyde ete. Asa disinfectant. Alkaline KMnO, soln. is Bayer’s reagent which finds its use in organic reactions.