ee AY NCERT : MUST 1O MUG UP LINES BY OM PRABHU AlIMS DELHI SELECTION LEKE RAHENGE YE WADA HN HAMARA§ i & z he studying this Unit, you will be I ah the positions of the d- and folock elements in the periodic table; , now the electronic configurations of the transition (d-block) and the " {nner transition (f-block) elements; appreciate the relative stability of various oxidation states in terms of electrode potential values; “describe © the _ preparation, properties, structures and uses of some important compounds - such as K,Cr,0, and KMn0O,; understand the __— general _ characteristics of the d- and | flock elements and the general _ horizontal and group trends in them: describe the properties of the frblock elements and give a comparative account of the ~ lanthanoids and actinoids with ‘respect to their electronic configurations, ong tates “and Chemical Bey ans ee Tron, copper, silver and gold are among the transition elements that have played important roles in the development of human civilisation. The inner transition elements such as Th, Pa and U are proving excellent sources of nuclear energy in modern times. * The_d-block 9 the periodic table contains the elements which the d orbitals are progr ély-filled in each of the four long periods. ‘The elements constituting the f -block are those in which the 4 f and 5 forbitals are progressively filled in the latter two long periods; these elements are formal amemibers of group 3 from which they ‘have been taken out to form a séparate fblock of the-periodic table. “metals are often used to refer to the elements of d-and folks resp} There are mainly three series of the transition metals, 3d series (Sc to Zn), 4d series (Y to Cd) and 5d. series (La to Hg, omitting Ce to Lu). The fourth 6d series which begins with Ac is still incomplete. The two series of the inner transition metals, (4f and 5f) are known as lanthanoids gnd actinoids respectively. onligaration in their ground state as well as in-their ~common oxidation states and hence, are not regarded as transition metals. However, being the end members of the three transition series, their chemistry is studied along with the chemistry of the transition metals. The presence of partly filled d or f orbitals in their atoms sets the study of the transition elements andwie te ast Ul! fs their compounds apart from that of the main grouj elements. However, the usual theory of valence applicable to the main group elements can also 5 applied successfully to the transition elements. J Various precious metals such as silver, gold a platinum and industrially important metals Ike trom Copper and titanium form part ofthe transition meta iE In this Unit, besides introduction, we shall first deg with the electronic configuration, occurrence and gen ‘characteristics of the transition elements with specia emphasis on the trends in the properties of the row (3d) transition metals and the preparation a properties of some important compounds. This will b followed by consideration of certain general aspects such as electronic configurations, oxidation states ang chemical reactivity of the inner transition metals. THE TRANSITION ELEMENTS (d-BLOCK) 8.1 Dusition in the The d-block occupies the large middle section flanked by s- and p_ blocks in the periodic table. The very name ‘transition’ given to the elements of d-block is only- becquse of their position ‘between s- and 7G p_ Block elements. The d-orbitals of the penultimate energy level in « ., their atoms receive electrons giving rise to the three rows of the transition row of 6d is still incompletes pot metals, i.e, 3d, 4d and Sd. The fou \e ‘These defies of the transition elements are shown in Tabte 6.1. ~ B2Clectranic ag he electronic configuration of these elements is we ‘Ganfigutan in-1) stands for the inner d orbitals which may have aoe Z wns and the outermost ns.orbitalmay.have one or of the d-DIX\ Caectrons. However, this 6 thermore, hall and Pl more stable. A consequence of th configurations of Cr and Cu in the 3d series. Consid for example, which has 34° ‘4s! instead of 3d'4s*; the energy gap bet X I the two sets (3d and 4s) of orbitals is small enough to prevent electron pore . entering the Sd orbitals. Similarly in case of Cu, the configuration ig + '@. The outer electronic configurations of the OH BO 3d°°4s' and not oe transition elements are given in Table 8.1. Bn? gyoN" - Yor qLarant ¢ fons of the Transition Elements (ground state) wr Table 8.1: Outer Electronic Configurat eeeSg | age, | 07, ml | uz 2 2 2 | 2 2 2 ee ers SaEaieee 5 | 6 7 8 10 | 10 Akole RD ay ground can you say that scandium (Z = 21) is a transitio Example Bt | ifent but zinc (Z = 30) is not? & ‘onthe basis of incompletely filled $d orbitals in case of scandium atom Soliinu ‘Inits ground state (3d’), i E 2 book. ry © hit hr ‘the eestronic Sonfiratfons of, init ig ave roittetea By the general formula (n-1)d'ns*. The orbitals in these elements are completely filled in the ground state as well as in their common oxidation states. Therefore, they are not regarded as fransition-elements. The d orbitals of the transition elements project to the periphery of an atom more than the other orbitals (i.e., s and p), hence, they are more influenced by the surroundings as well as aflecting the atoms or molecules surrounding them. In some respects, ions of a given d” configuration (n = 1 - 9) have similar magnetic and electronic properties. With partly filled d orbitals these elements exhibit certain characteristic properties such as display of a variety of oxidation states, formation of coloured ions and entering into complex formation with a variety of ligands. The transition_metals and their compounds also exhibit catalytic property and paramagnetic behaviour. All these characteristics have been discussed in detail later in this Unit. ‘There are greater horizontal similarities in the properties of the transition elements in contrast to the main group elements. However, some group similarities also exist. We shall first study the general characteristics and their trends in the horizontal rows (particularly 3d row) and then consider some group similarities. it is regarded as a transition element, On theol fott Sstcde ‘Silver atom has completely filled d orbitals (4d") in its ground sta How can you say that it is a transition clement? 3-3 Physical Properties Nearly all the transition elements display typical re al play typical metallic adn clus ith the exceptions 0 ig thev have one or more typical metallic structure normal tem} tures. » Lattice Structures of Transition Metals v ce Mo bx co ee bee bee =X bee cep, PEP She transition metals (with the excep of Zn, Cd and Hg) are very much_hard ‘volatility. Their melting and boil are high. Fig. 8.1 depicts the mel of the 3d, 4d and 5d transition mete se to a maximum at d° except anomalous values of Mn and Tc and regularly as the atomic number incies They have high enthalpies of atomisation wit 1 are shown in Fig. 8.2. The maxima at abs of cach series indicate that 0 Fig BAe. Tr ee f — [inpaired electro} per d orbital is particu's rans bnpalred oS metals Chemistry guvonlsy Ppprtowas— to Meaic_— MP = War foy AS Cone. Contagt - => © 5 of mom arastic > Muttalie aH Oingaséad) Qerdog a 16) Rut Mn £ Te dow! done mck Vn Guin Putfod.favourable for strong interatomic al teraction. In stronger Is the resu ¢ enthalj rh sorrento ne ahaa i + Metals with very high enthal 7 Py ofatomisation {L.c.. very high bolling Le.._very. boi Factions (see later for electrode polenta) “endto-be noble in thelr Another generalisation that may be drawn from Fi Beneral, greater ther lant _bonding. Since 400: AH'/kJ mol! —> 300- Atomic number —> Tay be that the shielding effect of a L effective, hence the net eléctrosiatic altraction between the nuclear charge and the outermost electron increases and the ionic rddtus-decreases. The same trend {s observed in the atomic radii of a given series. However, the variation within a series Is quite small. An interesting point emerges when atomic sizes of one series with those of the corresponding elements in the other series. The curves in Fig. 8.3 show an increase from the first (3d) to the second (4d) series of the elements ‘but the radii of the third (5d) series are virtually the same as those of the corfsponding-members-of Wie stcomd-sertes. Thi Rowe plenomenon Js associated with the an of the.4) ri be filled before ie 5d series of clements begin. i ly. compensa i) cambyes a aged 3, The d- and J ble te oo £2 ements asGy Neet $1 WL q sok : (6 size with increasing atomic number. The net resuj contraction is somewhat similar to that observes in an ordinary transition series and is attribute 17 & to similar cause, L.e.. themperfect shielding ¢ 16 @ _one electron by anc set.of orbita Z e shielding of one 4f electron § other is Tess than that of one_d-electro — Sc Ti V Cr Mn Fe Co Ni Cu Zn Y Zr Nb Mo Te Ru RhPd Ag Cd ~~~ La Hf Ta W Re Os Ir Pt Au Hg, from titanium (Z'= 22) to copper (Z = 29) Fig. 8.3: Trends in atomic radii of significant Increase the density may be note transition elements goad ‘Table 8.2: Electronic Configurations and some other Properties of the First Series of Transition Elements Atomic number 21 22 23 24 25 26 27 28 Bleetronle configuration tr salts? saP4s* Sd4s? adés! ad'4st ad’as? Sa'dst 3d'as" ad*as! 3a Me dias! adPas! Seas! ad? ScPas! das! 3d’4s' Sd'as' 9d 3d" mM 3d" 3d 3d° 3d‘ 3d* ad° 3d” 3° 3d° 3a’® uM Wasa se se sa dh Be Enthalpy of atomisation, JH /kJ mol” 326 -473«515 «997-281-416 425° 430999 Jonisation enthelpy/A,Hf/kJ mol” 758 736 «745906 ant 1 631 656 «650. «653717762 AH u 1235 1309 1414 1892 1509 1561 1644 1752 19581794 an m 2303 2657 2833 2990 3260 2962 3243 3402 3556 3829 Metallicfionlc = M 164147, «185—«129,«s137«126-S «125125128187 radil/pm u™ - - 79 62 82 77 74 70 78 7 u™ 73 67 «464 «662 «(65 HCC = - Standard electrode M™/M = 1.63 -1.18 -0.90 -1.18 -0.44 -0.28 -0.25 +0.34 0.76 potential B'/V M™/MY 0 - 0.87 0.26 -0.41 41.57 40.77 41.97 ~ a - 41 607 7.19 721 78 87 89 89 7.1 Density/g cm”jay do the {ransitionsvclementst exhibit" higher enthalples-of 4 their atoms they, |Su, pe stronger interatomic interaction and hence stronger bonding weveen atoms resulting in higher enthalpies of atomisation, 82 In the series Sc (Z = 21) to Zn (Z = 30}, the enthalpy of atomisation N TOR of zinc is the lowest, 1.e., 126 kJ mol’. Why? Enthalpies ‘of the Inner cl series rat the transition eB ese ives het nfiny small variations occur, Table 8.2 gives the values fer the first \ three ionisation enthalpies of the first row elements. These. es show that the successive enthalpies of these el do not increase as steeply oi ae ~ealalpy. ir alt nitude-of-the-increaseinthe stcond and third lonisation enthalpies for the successive-clements, in general, is much higher. 6S The irregul irregular trend in the first ionisation enthalpy of the 3d metals, though of little chemical significaneé] can be accounted for , \STonisation = Due-to-an Joerese in nuclear charge which accompanies the filling enthalpy So the ‘unipositiv: onfigurations with no 4s electrons. There is thus, lecirans in ere Is the generally expected increasing srendnin the values as the effective nuclear charge increases, However, [the value of Cr is lower be of the absence of any change in the ‘configuration and i value for Zn higher because it represents an common oxidation state of thesé‘metalsis~ "x27 form-the Moris from the gaseous atoms; the sum of the firstahd second ionisation energies is required in addition to the enthalpy of atomisation for each element. The dominant term is the second ionisation enthalpy which shows unusually high values S for Cr.and Cywhere the d° and d”° configurations of the M’ ions are Omi! disrupted, with considerable 108s of exchange energy. The value for . Zn is correspondingly low as the ionisation consists of the removal of an electron which allows the production of the stable d'° configuration. The trend in the third jonisation enthalpies is not 5. complicated by the 4s orbital factor and shows the greater difficulty ey of removing an electron from the d° (Mn™) and d”° (zn”) jons superimposed upon the general increasing trend. (n general, tne a_markesStates Wet gourt Ade ust 245 “Spe tel adit iUs difficult to obtain oxidation stat r_than two for these elements. “Although tontsation enthalpies give ve some guidance concerning the relative stabilities of oxidation states, this problem 1s very complex and not amenable to ready generalisation. One of the notable features of a transition clement fs the great variety of oxidation states it may show in its compounds. Table 8.3 lists the common oxidation states of the first row transition elements. Table 8.3: Oxidation States of the first row Transition Metals (the most common ones are in bold-types) to Jose or share (Sc, Th ‘oF too m: ‘ons orbitals available in which to share electrons with others) for higher valence (Cu. Z early in the series scan: is virtually unkno t the other end, the dnff-oxidation state of zinc is +2 {no d electrons are involved). The maximum oxidation states of reasonable stability correspond in value to the sum of the s and delectrons upto manganese (TiO, V'O;", cr'o,7, MnO,) followed by a rather abrupt decrease in stability of higher oxidation states, so that the typical species to follow are Fé Co", Ni", Cul". Zn". The variability of oxidation states, a characteristic of transition elements, -arises out of-incompleté filling of d orbitals in such a way that their oxidation states differ from each other by unity, e.g., V", V", V", V. This is in contrast with the variability of oxidation states of non transition \ents where oxidation states normally differ by a unit of two. An interesting feature in the variability of oxidation states of the d-block elem ugh 10). Althougir in the p-block.the lower oxidation states are favoured by the heavier members (que to inert pair effegi). the opposite is true in the groups of d-block. For example, in group 6/\Mo(VIl_and W(VI) are found to be more stable than ; Thus CHV) in The Maro dichromate in acidic medium is a stron "Lov :\ Aekod Ww Tee Vatu 2072. a transition element which }does not exhibit variably Caumple & ion states. : Se Bina ;dium (Z = 21) does not exhibit variable oxidation states. Solution o HO - oo rin t Which of the 3d series of the transition metals exhibits the ( largest number of oxidation states and why? oS ( evap HNDg : \ Hop Gore ‘Trends in the M”/M Standard Table &,4 contains the thermochemical toGx. Electrode Potentials parameters__related to the "2 5 > transformation of the solid metal atom : to M’ ions in solution and their /\ standard electrode potentials. The 0 1 observed values of E° and those calculated using the data of Table 8.4 are compared in Fig. 8.4. The_unique behaviour of Cu, having a positive E>, accounts Tor i inabitity to liberate_H, cid ¢ general trend towards less negative E° values across the Tet, series is related to the general increase in the sum of the’ first and second a Observed and calculated values for the s fonisation enthalpies. It is interesting —Ti V oCr Mn Fe Co Ni Cu Zn {@ Observed values ‘® Calculated values electrode potentials to note that the value of E” for Mn, Ni * — M®) of the elements Ti to Zn and_Zn “are _more_negative than i es Ce expe from thé-trend.—— Wor kt SS 7 30 ity is Cr reducing and Mn™ oxidising when both have d* configuration’ is reducing as its configuration changes from d' to d’, the latter a half-filled ty, level (see Unit 9) . On the other hand, the change Mn” to Mn® results in the half-filled (4) configuration which has stability. ee ‘i iw hutext_ Question 4 The E°(M™/M) value for copper is positive (+0.34V). What is | Teason for this? (Hint: consider it 2)% The d- and f Block ElementsTable 8.4: Thermochemical data (kJ mol") for the first row Transitio, Elements and the Standard Electrode Potentials for the Reduction of M" to M. The stability of the half-filled d sub-shell in Mn™ and the complete) filled a’? configuration jo Zt ste related to their E° values, whereag E* for Niis related. ighest negative bu} An examination of the E°(M"*/M”) values (Table 8.2) shows the varying trends. The low value for Sc reflects the ‘stability of Sc* which has a noble gas configuration. The highest value for Zn is due to the remova of an electron from the stable d'° configuration of Zn®. The comparatively high value for Mn shows that Mn*(d°) is particularl stable, whereas comparatively low value for Fe shows the extra stability of Fe (d). The comparatively low value for V is related to the stabilit of V* (half-filled t, level, Unit 9). Table 8.5 shows the stable halides of the 3d series of transition metals ‘The highest oxidation numbers are achieved in TiX, (tetrahalides), VF, and CrF,, The +7 state for Mn is not represented in simple halides but MnO,F is known, and beyond Mn no metal has a trihalide except Fe undergo hydrolysis to give oxohalides, VOX,. Another feature of fluorides is their instability in the low oxidation states e.g., VX; (K=CI-Br or I Table 8.5: Formulas of Halides of 3d Metals - = aaa VFs | CrFs VX, CrX, MnF, : VX, CX, MF, FeX', CF, Vs CrX; = MMX, = FeX,— CoX; NIX ei ZX, C Key: X= FOR Xe Fo Bre HR CL X= C141 Chemistry 218, : x ug akooC, downat eu and the same applies to CuX, On the known except the fodide. In_this-case, Cu’ oxtdises” TP to Le 2Cu"* +41” + Cuyl, (8) +1, However, many_copper-() compounds are unstable in_aqueous. , vou) solution and undergo disproportionation, as 9 2Cu’ > Cu” + Cu olerq OF oxygen to stabilise the highest oxidation state is (LN2 demonstrated in the oxides. The highest oxidation number in the oxides (Table 8.6) coincides with the group number and {s attained in Sc,O, yo to. Mn,0,. Beyond Group 7, no higher oxides of Fe above Fe,0,, Known, although ferrates [Vi\(FeO,)" are formed in alkaline media but. they readily decompose to Fe,0, and Oz, Besides the oxides, oxocations stabilise V' as VO,", V" as VO and Ti” In the covalent oxide Mn,O,, each Mn is tetrahedrally SGrrounded by O's including a Mn-O-Mn bridge. The tetrahedral MO Rae cr, Mn‘, Mn" and Mn™ Re 8.6: Oxides of 3d Metals Oxidation str V.05 +4 TIO, V,0, CrO, MnO, © +3 Sc0; 710; V,0; Cr,0; -Mn,0, Fe,0, : Mn;O, Fe,0,' Co,0," +2 TIO VO (Cro) MnO FeO CoO NIO CuO ZnO ao ) cu,0 xa Ue a h 0 4 oge eg ye v e increasing oxidising power in the Cyample_ 8.5. aod pat is is due to the increasing stability of the lower species to which they Sulution are reduced, | Intex. Question low would you account for the irregular variation of ionisation enthalpies (first and second) in the first series of the transition elements? 219, The d- and f- Block Elements8.3.8 Seanical Transition metals vary widely in their chemical reactivity. Many of and pe” —_themare sufficiently electropositive to dissolve in mineral acids, although aaa 2 a Tew are ‘noble—that ts, they aré unaffected by single acids. J ‘The metals of the first series with the exception of copper are relatively more reactive _and_are oxidised by IM H’, though the actual rate at” which these metals react will oxidlsing agents like hydrogen ion (i) “sometimes slow. For example, titanium and vanadium, in practic are (Tete wana ive to dilute Fion oxidising acids at room temperature. The E° values for Ne bie indicate_a decreasing tendency to form divalent gations acmess the series This ‘general trend towards less negative p° ee ¥ fated to the increase in the sum of the first and secong XN ionisation enthalpies. It is int lues for Mn, Ni and_Zn are more negative than expected from the general trend, Whereas the stabilities of halffilled d subshell (J in Min’ and completely filled ¢Subshell (din zine are related to their E‘ values; for Hidkel, E* 7 WK value is related to the highest negative enthalpy of hydration, : * pyee we na gid f the E values for the redox couple M™/M"™ (Table 8.0 For the first row transition metals the E° values are: E v cr Co ON cu (M*/M) -1.18 -0.91 -1.18 -0.44 -0.28 -0.25 40.34 Explain the irregularity in the above values. Solution The E° (M2"/M) values are not regular which can be explained from the irregular variation of ionisation enthalpies (A,H, + A,H,) and also the sublimation enthalpies which are relatively much less for manganese and vanadium. Why is the E° value for the Mn™/Mn” couple much more positive than that for Cr*/Cr* or Fe“/Fe”? Explain. Solution Much larger third ionisation energy of Mn (where the required change G¥as dé to a) is mainly responsible for this. This also explains why the ver] V4 state of Mn is of little importance. Intoxt Questions : ‘Why is the highest oxidation state of a metal exhibited in its oxide =| 2 fluoride only? wv, ich is a stronger reducing agent Cr” or Fe” and why Gia 8.3.9 Magnetic When a magnetic field is applied to substances, mainly two types of Properties magnetic behaviour are observed: diamagnetism and paramagnetism (Unit 1). Diamagnetic substances are repelled by the applied field while the paramagneUc substances are attractedSubstances which are Chemistry 220;attracted very strongly are said to be ferromagnetic. In fact, ferromagnetism is an extreme form of paramagnetism. Many of the transition metal ions are paramagnetic. Paramagnetism arises from the presence of unpaired electrons, each _ such electron having a magnetic moment associated with its spin angular momentum and orbital angular momentum:For‘the-compounds of the first Series of transition metals, the contribution of the orbital angular momentum is éliectively quenched and hence is of no sigitificance. For «these, the magne Toment i determined by the number of unpaired eledtrons culated by using the ‘spin-only’ formula, i.e., ye a fh D . Toypiiyse where n is the numero deeititons and p is the magnetic moment in units‘s A single unpaired electron has a magnetic moment ol Bohr magn , - The magnetic moment increases with the increasing number of unpaired electrons. Thus, the observed magnetic moment gives a useful indication about the number of unpaired electrons’ present in the atom, molecule or ion. The magnetic moments calculated from the ‘spin-only’ formula and those derived experimentally for some ions of the first row transition elements are given in Table 8.7. The experimental data are mainly for hydrated ions in solution or in the solid state. Table 8.7: Calculated and Observed Magnetic Moments (BM) ae Cotitante tarot avert tle ects tet TS te | electron(s)'| Calculated! | = o 1.75 2.76 3.86 4.80 5.96 5.3 - 5.5 4.4 - 5.2 29-34 18 - 2.2 | | j ncalase the magnetic moment of a divalent ion in aqueous solution Cxample if its atomic number is 25. With atomic number 25, the divalent ion in aqueous solution will have Sulijtiv @ configuration (five unpaired electrons). The magnetic moment, 1 is n= 56 +2) =5.92BM ZF and J- Block ElementsIitesst_Question 8.8 Calculate the ‘spin only’ magnetic moment of M"q fon (Z = 27), 8.3.10 Formation When an electron from_a lower_energy-d. orbital is excited to a higher! of Coloured energy d orbital, the energyof excitation corresponds o the frequency Tons of lightabsorbed (Unit 9). This frequency generally lies in the visibj region. The colour observed corresponds to the complementary colour qu solutions where watermalecules are |) : the ligands, the colours @<@ a of the ions observed-are << * listed in Table 8.8.A few loured solutions of Fig. 8.5: Colours of some of the first roi d-block elements are ‘transition metal ions in aqueous solutions, illustrated in Fig. 8.5. left to right: V*",V".Mni",Fe”*,Co™,Né“and Cu Table 8.8: Colours of Some of the First Row (aquated) ‘Transition Metal Ions (Cutt: oo” 3d" purple “blue . green violet violet violet blue pink yellow green bluepink green 8.3.11 Formation Complex compounds are those in which the metal ions bind a number! of Complex of anions or neutral molecules giving complex species with Compounds characteristic properties. A few examples are: [Fe(CN).I”, [Fe(CNl* [Cu(NH,),]”" and [PtCl,]*. (The chemistry of complex compounds Is Chemistry ,222,dealt with in detail in Unit 9). The transition metals form a large number of complex compounds. This is due to the compe gmaller_sizes_of the.metal_ions,_their_high-Tonlc_charges_and availability of d orbitals for bond formation. 312 Catalytic- The transition metals and their compounds are known for their catalytic “properties _ activity. This activity is ascribed to their ability to adopt multiple ~ oxidation states and to form comple, vanadium oxi Canta [8° ~CalalyStS-ata solid surface “\) involve the formation of bonds between reactant molecules and atoms yst (first row transition metals utilise 3d and This has the effect of increasing” the ‘Also because the transition metal ions can change their oxidation states, they become more effective as catalysts. For example, iron(II) catalyses the reaction between iodide and persulphate ions. 21 +S,0," > 1, +2 80,7 An explanation of this catalytic action can be given as: 2Fe" +27 32 Fe" +]y 2 Fe* + S,0,7 + 2 Fe* + 250," .13 Formation (Interstitial compounds are those which are formed when small atoms of like H, C or N are trapped inside the crystal lattices of metals. They are Interstitial Usually non stoichiometric and are neither typically ionic nor Covalent, quoted do nol, of course, correspond to any normal oxidation state of the metal. Because of the nature of their composition, these compounds are referred to as interstitial compounds.-The principal physical and chemical characteristics ol these compounds are as follows: An alloy is_a_blend of metals prepared by mixing the components. Alloys may be homogeneous solid solutions in which the atoms of one metal are distributed randomly among the atoms of the ‘other. Such y_these metalsPThe igh melting points. The best known are ferrous alloys: chromium, vanadium, tungsten, molybden and manganes (223 The d- and f- Block Elements Compounds for example. TiC, Mn,N, Fe,H, VHo.ss_and TiH,;, etc. The formulas ee7 Tete, Sh epee fan oxidation state? Give an Csuinple_SQ What is meant by ‘disproportionation’ o| example, Top wn state becomes less stable relative to othe r Solution When a particular oxidatior oxidation states, one lower, one higher, it Is ‘said to undergo disproportionati For example, manganese (VI) becomes unstable yelative to manganese(VIl) anq manganese (IV) in acidic solution. a 3 _Mn"0,7+4H' 72 Mn“o7, + Mn™Oz x oO we G 8.4 Some Important Campounls 4 Taisen + 2H,0 8.9 Explain why Cu’ ion is not stable in aqueous soluti ion: 3h, Be i al 5 and Oxoanions of Metals by the reaction of metals 8.4.1 Oxide: Clements Mn,0;)Beyont ier oxides of iron above Fe,0, {re oxocations stabilise v" as VO, V ‘As the oxidation number of a metal increases, jonic chara decreases. In the_case of Mn. have low melt minant. minan' ote V0, and to amphoteric V,0Z V0. Similarly, V,Os reacts with alkalies as we spectively. The well characterise < te K,Cr;07 ery important chemical used in leat pojustry and as an oxidant for preparation of many azo compotin Di are generally prepared from chromate, which in turn obtained by the fusion of chromite ore (FeCr,0,) with, odium| vrasstum carbonate in free access of air The reaction with, goal carbo a as SONOS 0 yu Tm 44 FeC1,0. + 8 NajCOs +70: 78 Na,CrO, + 2 Fe,0, +8¢ Rg ‘The yellow solution of Sodium chromate is filtered and acidif ane with sulphuric acid to give a ‘solution from which orange sodi Vv Yichromate, Na,Cr,0r. 24,0 can be crystallised. + 2.Na* + H,O PUB, 2NalIOs 42H 2 — fotos sere Potassium dichromat Potassium. dichromate is a v Chemistryi. eee eee ' y treating the solution of sodium i L222 dichromate with potassium chloride. y VW _Na,Cr.0; + 2 KCI K,Cr,0; + 2 NaCl | Toe _ Orange crystals of potassium dichromate crystallise out. The tort chromates and dichromates are interconvertible in aqueous solution depending upon pH of the solution, The oxidation state of chromium. in chromate and dichromate is the same. 2 CrO,” + 2H° > Cr,0;> + H,0 Cr,0;7 + 2 OH 2 CrO,? + H,0 2 2 The structures of - of - chromate ion, CrO,? and the dichromate ion, Cr,0,” i 2- QR 6G LY : = below 5 are~shown— below-The cy D chromate ion is tetrahedral 4 aN S whereas the dichromate ion DG sR Ag consists of two tetrahedra 7a! : sharing one corner with Dichromate ion “Cr=O-Cr bond angle of 126°. anal neeasassa | ° J“ e-Cr,0,7 + 14H" + 6e 3 2Cr* + 7H,0 (E = 1.33V) Thus, acidified potassium dichromate will oxidise iodides to iodine, sulphides to sulphur, tin({I) to tin(IV) and iron{ll) salts to iron(II). The half-reactions are noted below: GT +31,+6e¢; 3 Sn™ > 3Sn" +6 3 H,S > 6H’ + 3S + 6c"; 6 Fe* — 6Fe* + 6 ‘The full ionic equation may be obtained by adding the hall-reaction for Potassium dichromate to the half-reaction for the reducing agent, for e.g... Cr,0;* + 14 H’ + 6 Fe* 2 Cr + 6 Fe* + 7 HO Potassium permanganate KMnO, Potassium permanganate is prepared by fusion of MnO, with an alkali ‘thetal hydroxide and an oxidising agent like’ KNO,. This produces the dark green K,MnO, which disproportionates in a neutral or acidic solutio: ive permanganate. ©. Cina) AKOH + 0, + 2KMnO, + 24,0] Lp api, WO BMnO? + 4H > 2MMOe + MnO, + 2H] as Commercially it is prepared by the alkaline oxidative fusion of MnO, + followed by the electrolytic oxidation of manganate (V1). 225, The d- and f- Block Elementsso ee fnee™ oo (ceed a 0 ao, 40°" in the laboratory. a manganese (II) ion salt ts oxidised by Que (ot Peroxodisulphate to permanganate. 2 4 5S,0,? + 8H,0 + 2Mn0, + 10SO,” + 16H" \ganate forms dark purple (almost black) crystals which ural with those of KCIO,. ‘the salt is nol very soluble in water JO, + K,MnO, + MnO, + Or Ithas two physicakproperties of considerable-interest: its inlense colour and its weak temperature dependent paramagnetism. These can be expl ined by the use of molecular orbital theory which is beyond the present scope, ‘The manganate_and_permanganate ions are tetrahedral, the green manganate_is_ paramagnetic one unpaired electron-butthe-permanganate js diamagnetic. —— The x-bonding takes placc_by overlap of p orbitals of oxygen with d orbitals-of-manganese. wanate solution oxidises oxalates to carbon dioxide, coo - 5[ —>10CO, + 10¢ coo 5 Fe + 5 Fe* + Se 5NO, + 5H,O > 5NO; + 10H" + 10e" , 10F > 5h, + 10e° _ The full reaction can be written by adding the half-reaction for KMn0, to the half-reaction of the reducing agent, balancing wherever necessary. ? If we represent the reduction of permanganate to manganate, manganese dioxide and manganese({l) salt by half-reactions, ~~ OMn0O, + & > Mn0,* é AE = + 0.06 V) MnO, + 4H" + 3e" > MnO, + 2H,0 (E° = + 1.69 v) MnO, + 8H’ + 5e” > Mn” + 4H,O (Ee 1.52 V) We can very well see that the hydrogen ion concentration of the solution plays an important part in influencing the reaction. Although many reactions can be understood by consideration of redox potential, Kinetics of the reaction is also an important factor. Permanganate at ~ [H'] = 1 should oxidise water but in practice the reaction is extremely slow unless either manganese{ll) ions are present or the temperature is raised. ‘A few, important oxidising reactions of KMnO, are given below: 1. Inf {@) lodine is Hberated fromp6tassium iodide = + 10 +2Mn0, + 16H’ ——> 2Mn™ + 8H,O + 5, 0) Feifentges) ls converted EP" yallwt> |v 5Fe™ + MnO, + 8H’ —> Mn™ + 4H,0 + 5Fe* Chemistry 226,(0 Oxalate‘ton or oxalic acid is oxidised at 333 K: FT 5C,0," 4 2Mn0, + 16H’ —> 2Mn”" + 8,0 + 190, (d) Hydrogen sulphide is oxidised, sulphur being precipilated: H,S —> 2H" + S® 5S? +2MnO, + 16H’ —> 2Mn” + 8H,0 +5S (©) Sulphurous acid or sulphi sulphuric acid: 550,” +2MnO, + 6H’ —> 2Mn™ + 3H,0 + 5SO,” a) z x (0 Nitrile is oxidised to nitrate: . oe 5NO, +2MnO, + GH* —> 2Mn” + 5NO, +3H,0 = 25 gon 2 Infieu milly alkaline solutions: SPs ‘A nolable reaction is the oxidation of iodide to iodate: 2MnO, +H,0 + —>2Mn0, + 20H +10; (b)Thiosulphate is oxidised almost quantilatively to sulphate: x tt 8MnO, + 38,0, + HO —> 8MnO; + 6SO,” + 20H {© Manganous salt is oxidised to MnO,; the presence ofzinc sulphate yw S or zine oxide catalyses the oxidation: >Z—> KT TIO} on¢ set 2MnO, + 3Mn* +2H,0—>6MnO. 54H Qu 71) 2D". oo Note: Pernlanganate titrations in presence of hydrochlori Pare unsatisfactory since hydrochloric acid is oxidised to chlorine. ow 3S is oxidised to.a sulphate or = “jv [low Besides its use in analytical chemistry, potassium permanganate is used as a favourite oxidant in preparative organic chemistry. Its uses for the breaching or Wool, cotton, silk and other textile fibres and for the decol: ition of oils are also-dependent on its strong oxidising power, = * THE INNER TRANSITION ELEMENTS (fBLOCK) ce ‘The £block consists of the two series,'iinthanoids (the fourteen elements ihe two series. Janthanoi ds a ol _Janthanum)_and_actinoids (the fourteen elements following, “actiniuip)- Because lanthanum closely resembles the Tanthanoids. it is usually includgd~: cay’ discussion of the IanUvanordssfor‘which the ‘oficn used. Similarly, a discussion of the actinoids includes actinium besides the fourteen elements co ing the serics. ‘Tie tanthanoids resemble one another mor ‘Closely than do the members of ordinary transition elements in any series. They have only one stable itlation state and their chemistry provides an excellent opportunity to cxaminc the effect of small changes in size and nuclear charge along a series of otherwise similar elements. ‘The chemistry of the actinoids is, on the other hand, much more complicated. The complication arises partly ing 10 the occurrence of a wide range-of oxidation states in these fements and partly because. their radioactivity creates special problems in their study; the two series will be considered separately here. 5 The The names, symbols, electronic configurations of atomic and some Fanthanoids Sonic states and atomic and tonte radii of lanthanum and lanthanoids Lanthanoids: (ip which the general symbol Ln is used) are given in Table 8.9. (22%) The d- and jf bloc ik Elements: gg Ghote t Lommanues GR SE LN Crolumut 2: Rchiniun ve te AST debi