D & F-BLOCK 12th Boards’ Notes¢ Y oe! O% t U-BLUCK ALOT OF COMMERCIAL AND IMPORTANT METALS THAT WE USE LIKE IRON(FE), GOLD(AU), SILVER(AG), COPPER(CU) ETC ARE TRANSITION ELEMENTS. AS ALL TRANSITION ELEMENTS ARE ESSENTIALLY METALS, THEY ARE ALSO CALLED TRANSITION METALS. 96 AO_C DEFINITION : Initially they were named “transition" elements because their properties were found to be transitional between s & p block elements. However, IUPAC definition is as follows, Transition metals are metals which have incomplete CBSE 2015 d subshell either in neutral atom or in their ions. Thus, elements which have one or more unpaired d electrons in their ground state or in their common oxidation state can be called transition elements. 2016(2),2014 A lot of elements do not possess unpaired electrons in their ground state but this definition helps identify them as transition elements. Eg- Copper (Cu) "ase 200712) Cu'‘s Electronic configuration is : 1s?2s22p®3s?3p&4s'3d'9 As we can see, it has a completely filled d orbital in its ground state but in its common Oxidation State i.e., +2, Cu+2 ‘s Electronic configuration is : 1s?2s?2p&3s?3p%4s03d9 and it has an unpaired electron thus it can be called a transition element. A similar case is observed for Silver, THSE20I7 The possession of unpaired d and f electrons makes transition elements different from s & p block elements and hence there study is carried out separately.SOME IMPORTANT DEFINITIONS AND CONCEPTS: These concepts would appear later in the chapter a lot so they should be understood before hand. (i) ENTHALPY O MISATION (aHat It is the change in enthalpy when one mole of bonds is completely broken to obtain atoms in the gas phase. It signifies the inter-atomic strength that the molecules of a compound possess. Lower aHat—+ weaker bonds —+ easier to break them. Melting Point, Boiling Point etc. depend hugely on aHat as they essentially are meant to weaken the inter-atomic attraction. It is a type of chemical bond formed between positively charged atoms in which the free electrons are shared among a lattice of cations. Strength of metallic bond depends on the size, the charge and the number of de- localisable (unpaired and not in a stable configuration) electrons that the metal has. Extent of metallic bond hugely influences 4H... CBSE 2017 It is defined as the reduction in the effective nuclear charge on the electron cloud, due to a difference in the attractive forces of the electrons on the nucleus. It is a very important phenomenon used in explaining atomic size variation in transition metals. As d-orbitals exhibit bad shielding effect to the outermost s-orbital, the outermost orbital experiences a stronger nuclear attraction, hence the size of atom decreases. The more than expected decrease in size of the lanthanoid series (from Lanthanum to Lutherium), due to the poor screening effect subjected on the outermost electrons by the f-subshell.In electrochemistry, standard electrode potential is defined as the measure of the individual potential of a reversible electrode at standard state with ions at an effective concentration of 1mol dm-? at the pressure of 1 atm. Basically, it is the tendency of an ion to become a neutral atom in aqueous medium. Negative E° value reflects the fact that the reversible process which we are studying is not feasible. E° is heavily affected by these properties and for a more negative E°: (i) Lower Enthalpy of Atomisation is required (ii) Lower lonisation Enthalpy is required (ii) Higher Hydration Enthalpy is required IUPAC gives several different definitions of oxidation: loss of electron, increase in positive value of oxidation state, decrease in negative value of oxidation state, loss of hydrogen, or gain of oxygen. So, gain of electron, decrease in positive value of oxidation state, increase in negative value of oxidation state, gain of hydrogen, or loss of oxygen are the various definitions of reduction. a enigma ae 1. ELECTRONIC CONFIGURATION: -The general outer electronic configuration of transition metals is (n- 1)d1-19ns1-2, -Although a lot of exceptions arise to this “formula” because there is very little energy difference between the ns and (n-1)d orbitals .. Eg — Copper(Cu) and Chromium(Cr): -The element just before Cr is Vanadium(V)-23 and its electronic configuration is, 1s?2s22p63s?3p%4s23d3 So according to Aufbau principle, Cr’s electronic configuration should be, 1s22s22p&3s23p64s23d¢ , but the actually found configuration is 1s22s?2p®3s?3p%4s'3d8. -This is because this configuration has a half filled d orbital which is very stable. -A similar anomaly is found for Cu. Nickel(Ni)-28, which is just before Cu, has the electronic configuration, 1s22s22p%3s?3p%4s23d8, -So the configuration of Cu should be, 1s22s?2p®3s23p®4s23a9, but the actual configuration is, 1s?2s22p63s23p%4s13d"0. -This is because there is a fully filled d orbital in this configuration which is highly stable.Are more influenced by the Due to unpaired e-these metals: surrounding than the s &p -showcase a wide variety of orbitals. Oxidation States. CBSE 2015,2017 -form coloured ions. Also they influence the -form complexes with a variety of neighbouring atoms or ligands. molecules more as compared tos & p orbitals. Transition metals and their compounds: lons of same dn electronic - have paramagnetic property configuration have similar - have catalytic property magnetic and electronic properties. 2. GENERAL PROPERTIES : Et co re Ce ee) Atomic number 21 22 23 24 25 26 27 28 29 30 Electronic configuration M Bellas? ad's! ad's? 3d°4s? dds? 3d?4s? 3d!%4s' 3d"? M 3d'4s 3a* 3d’4s' 3d*4s! 3d’ 3d'*4st M™ 3a!" 3a! 3d? sd’? we tas} ae" 3a = . Enthalpy of atomisation, 4,!/°/kJ mo! 326 473° 515 397 281 416 425° «430 339126, Ionisation enthalpy/A,H’/kJ_ mol" 1 631 656-650. G53 717-762, 758736745906 " 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734 Mm 2393 2657 2833 2990 3260 2962 3243 3402 3556 3829 Metallic/ionic = M 164 «147, 135129137126. 125125128137 radii/pm Me - - 79 82 8200 7707470 73 75 uM 73 67 Gi 62 65 65 GI 60 = . Standard electrode _ MyM - -1.18 -0.90 -1.18 -0.44 -0.28 -0.25 40.34 -0.76 potential E/V M™/M™ - 0.26 -O41 41.57 40.77 +197 - - - Density/g em? 3.43 607 7.19 7.21 78 87 89 89 7.1 All the general properties of the first transition seriesAlmost all transition metals show general metallic properties like : - ductility - malleability - lustre - high tensile strength ~ thermal and electrical conductance -The elements of grp-712 (Zn, Cd, Hg), due to their fully-filled d orbitals show anomaly from the rest of the elements with respect to properties. -This is because metallic properties are directly dependent upon the extent of metallic bond that a metal can exhibit and the extent of metallic bond in turn is directly dependent on the number of unpaired electrons that a metal possesses . -All transition metals except Mn and Grp-12 elements, have one or more typical metallic structures at normal temperatures and all of these, except Grp-12 metals, are very hard and show very low volatility i.e. have high boiling and melting points. Vv a Mn vy Lo ee 4. hep hep bee bee xX bee cep cep ecp xX (bee) (bee) (bee, cep) (hep) (hep) (hep) bs zr bd Mo Tc bist 2 Ba. I hep hep bee bee hep hep ecp cep ecp xX (bee) (bec) (hep) net Hf yyy ws BST) io) Ss b3 yo bg hep hep bee bee hep hep cep ecp cecp x {eep.bec) (bec) Lattice structures of Transition metals -Generally, transition metals have a high Melting and boiling point because of strong metallic bonds that they form using the ns and (n-1)d electrons.-Ina row, generally increases from the first element to the element with d§ electronic configuration and then falls regularly from there to last. -The reason attributed to this is that because the d§ configuration forms the strongest metallic bonding, melting point becomes very high. -Metals with very high enthalpy of atomisation tend to be noble in their reactions. tase 2019 Exception — Mn & Tc 's Melting Point is less than the previous element in their respective period despite having a c® configuration. This is because these elements have a stable half filled configuration due to twhich these electrons do not participate in bonding ,thus the atom- atom attraction of these metals is weaker and hence its easier to break their metallic bonds leading to a low Melting Point and hence the metals preceeding these(Cr and Mo) have the highest melting points. case 2016 (c) ENTHALPY OF ATOM ON: | Transition metals have a high enthalpy of atomisation. Order : 3d series <<< 4d series < Sd series This is because 4d and Sd series’ elements exhibit a stronger metallic bond(abundance of unpaired electrons) and it is more and more difficult toatomise them. CBSE 2019 -Within a series/period, as expected, ionic and atomic size decreases as the atomic number increases . -The poor shielding that the (n- 1)d electrons offer, lead to further penetration of outermost ns electrons and decrease in size. Although the variation in size observed in a series is quite small. -We observe an increase from the 3d to the 4d series of the elements but the radii of the Sd series are virtually the same as those of the corresponding members of the 4d series. This is observed due to a phenomenon called LANTHANOID CBSE 2017 CONTRACTION. -Lanthanoid Contraction is caused because of the screening effect that the f-orbitals (even weaker screening than d-orbitals) exhibit which leads to a shrinking in size of the atom and thus compensates for the expected increase in size. -This also leads to a lot of similarities in properties between the corresponding 4d and the Sd series elements.From this information, we see that, moving left, there is an increase in the atomic mass and decrease in atomic radii among the transition elements. Thus, there is an increase in density observed as we move from Titanium(Ti)-22 to Copper(Cu)-29. -There is an increase in ionisation enthalpy along each series of the transition elements due to an increase in nuclear charge because of filling of the inner d-orbitals, although the increase observed is quite less than the increase along a period of non-transition elements. -This is because the increase in nuclear charge is partly cancelled out by the shielding effect of the d-subshell electrons. -The three terms responsible for the value of ionisation enthalpy are attraction of each electron towards nucleus, repulsion between the electrons and the exchange energy. -Exchange energy is responsible for the stabilisation of energy state. -Knowledge of lonization Enthalpy helps us identify the most stable oxidation state of a metal and understand its ease to exist in a certain Oxidation State. For eg- @ The 2nd I.E. of Cu(29) is found to have an abnormally high value. This is because in Cut, copper achieves the d'° stable configuration and a further loss of electron will lead to instability. Gi) The 2nd I.E. of Cr(24) found to have an abnormally high value. This is because in Cr*, chromium achieves the d§ stable configuration and a further loss of electron will lead to instability. (iii) The 3rd |.E. of Mn(25) is found to have an abnormally high value. This is because in Mn?+, manganese achieves the d§ stable configuration and a further loss of electron will lead to instability. (iv) The 1st I.E. of Grp-12 elements is found to have an abnormally high value. This is because, grp-12 elements have a stable (n-1)d!9 ns? configuration and any loss of electron will lead to instability. -As after the second ionization, the only left electrons left to give up are the (n-1)d subshell electrons, which shield each other very poorly because d-orbitals are aligned in different direction, generally there is a jump observed in the 2nd(or higher) ionization enthalpy of transition metals. ‘Scanned with CamScarnerException — Fe's 3rd and Mn’s 2nd lonization Enthalpy is relatively low as these ionisations lead to a stable d° configuration for both the elements. ~The lowest common oxidation state of these metals is +2. -To form the M?* ions from the gaseous atoms, the dominant term needed is the 2nd ionisation enthalpy. EBS (i) Cu and Cr prefer forming +1 rather than +2 Oxidation State because in +1 state they have very stable d'° and d> configurations, respectively and hence do not disturb this configuration. (i) The 2nd I.E. of Grp-12 Metals is relatively low because it leads to an extremely stable d'° configuration. -Concluding, any ionisation which leads toa d§ and d!° configuration brings about much stability for an element thus its |.E. is relatively lower and that Oxidation State will be preferred by that element and vice-versa -One of the notable features of a transition elements is the great variety of oxidation states these may show in their compounds. -The elements which give the greatest number of oxidation states occur in or near the middle of the series as they have more number of unpaired electrons. Eg-Manganese, exhibits all the oxidation states from +2 to +7. CBSE 2015 -The lesser number of oxidation states at both the ends of a series is observed because they have either too few electrons to lose or share (eg-Sc, Ti), or too many d electrons, hence leading to fewer orbitals available in which to share electrons with others (eg-Cu, Zn). +2 | 42 | 42 #2 0 42 | 42 | 42 | 41 | 42 +3 +3 | 43 | 43 430 +30 43 | 43 +2 +4) 44 +4 +4 +4 +4 | 44 +5 +5, +5 +6 +6 +6 47 (The most common Oxidation States are in bold types)- Elements to the extreme left like Sc and Ti are found to exhibit only 1 O.S. or are significantly more stable in only one of them . Eg- (i) Scis only found in +3 O.S., its+2.O.S.isnotfound. CBSE 2016 (i) Ti although shows +2, +3 and +4 O.S. , +4 O.S. is way more stable. - Elements to the extreme right like Zn, mainly exist in 1 or 2 O.S. Eg- Zn is found only in +2 O.S. andit never disturbs its d10 electrons. - Inthe 3d series, upto Manganese, the maximum reasonably stable oxidation state that can exist corresponds to the sum of 4s and 3d electrons in the element. Eg- Vanadium(V)-23 : 3d%4s?. So maximum O.S. which is stable : 2+3 = 5——>+5 - Metals following Manganese, show an abrupt decrease in the most stable O.S. Stable O.S. of the following metals are- () Fe-+2and+3 (ii) Co - +2 and+3 (ii) Ni- +2 (iv) Cu- +1 and +2 (v) Zn - +2 ~ The variability of oxidation states, a characteristic of transition elements, arises out of incomplete filling of d-orbitals in such a way that their oxidation states differ from each other by unity. Eg- Vanadium-23 ‘s O.S. : V#ll, Vill, V+V, V+V, - This is in contrast with the variability of oxidation states of non-transition elements where oxidation states normally differ by a unit of two. CBSE 2016 - Astriking dissimilarity arises in transition elements here. The heavier members of the d block prefer higher ©.S. more than the lighter elements Eg- In Grp-6, Cr’ acts as an Oxidising agent in acidic medium because it is more stable in +3 O.S. while W*6 and Mo‘ are stable.- Low oxidation states are found when a complex compound has ligands capable of m-acceptor character in addition to the o-bonding. Eg - in Ni(CO), and Fe(CO);, the oxidation state of nickel and iron is 0. - Transition elements have a negative E° as metals do not have a tendency to get reduced to their neutral form. - Generally, as we move right in a series, E° becomes less -ve, i.e., metals start developing more tendency to undergo neutralisation. ~ This is because the combined 1st and 2nd I.E. of the metals increase as we move rightwards in a series and thus it becomes less energy efficient for a metal to stay in the ionic form. CBSE 2017 *Exception- CBSE 2017(3), 2019(2), 2018, 2020 Cu's E’ is positive i.e., itis not stable in its ionic form and it readily tries to convert back into its neutral atom. This is because Cu—*Cu** transformation has a high value of combined 1st and 2nd I.E. and a very low Hydration Enthalpy. “Exception - The E® value of Ni —+*Ni2+, Mn —+*Mn?+ and Zn —*Zn?+ is higher than expected. Reasons: @ Mn achieves the stable d§ configuration with this ionisation thus it has amore negative E°. CBSE 2017, 2019(2) (ii) Ni has the highest value of Hydration Enthalpy, thus it leads to a more negative E°. IMPORTANT CASE: CBSE 2014, 2020 -Cr** is reducing and Mn+ is oxidising but both have d* configuration. -3d° configuration leads to a stable half-filled t,, configuration (tz, configuration is more stable than dS in aqueous state) (CBSE 2017(3),2016, -3d5 configuration leads to a stable half-filled d-subshell configuration. -So while trying to achieve stability from the d* configuration, can either lose an electron(to attain d) or gain an electron(to attain dS). -Cr* - 3d44s° with 24 protons thus losing one more electron is easier as lesser nuclear attraction. Cae emU -Mn$+ - 3d44s° with 25 protons thus losing one more electron is not easy as there is more nuclear attraction so gains one instead. So Cr?+——+ Cr + e- —————+ oxidation Mn + e- —> Mn?+ —————+ reduction ‘Scanned with CamScarner1S+/M?* Standard Electrode tentials(E): - Sc has a negative E° value for Sc3+ —+ Sc? . This is because Sc3+ is an already stable ion as it has a noble gas configuration. - Zn has a very highly positive E° value because Zn** is achieved after losing an electron from the stable d'° configuration. ~ Fe has a low positive E° value because Fe* is a stable ion due toa stable d§ configuration and Fe** disrupts. - Mn has a high positive value because Mn?* is a stable ion due to a d> configuration and Mn* disrupts this stability. CBSE 2012,2017(3),2018 - V has a low value because V+ has a half filled es configuration. () TRENDS IN STAB! (HALIDES: - Fluorine especially is able to stabilise higher Oxidation States because of either very high lattice energy (like in CoF 3) or very high bond enthalpy values for higher covalent bonds(like in VF; or CrF,). Eg- Mn doesn't show +7 as a simple halide compound but in MnOsF. - After Mn, no element except Fe and Co, forms trihalides. - Although V*S is represented only by VF5, the other halides, however, undergo hydrolysis to give oxo-halides, VOX3. - Another feature of fluorides is their instability in the low oxidation states. Eg- VX, and the same applies to CuX. (X= Cl, Br, |) +6 cr, +5 VF, CrP +40 TX, VX, CX, MF, +3 0 TIX, VX, GFX, | MF, FeX', CoP, +20 TK" VX, CrX, MX, FeX; CoX, NIX, CuX," ZX +1 cux* Oxidation States observed in Halides -All Cull halides are known except the iodide. -In this case, Cu** oxidises |- to Ip: 20u2* + 4l- —+ Cuply (s) +l -However, many copper (|) compounds are unstable in aqueous solution and undergo disproportionation. 2Cut ——> Cu + Cu+-The stability of Cu2(aq) rather than Cut(aq) is due to the much more negative hydration enthalpy of Cu2*{aq) than Cur. CBSE 2016,2018 (i) OXIDES: -Oxygen has the ability to stabilise the highest Oxidation State. The highest oxidation number in the oxides coincides with the group number and is attained in Sc,O, to Mn,O;. ~Beyond Group 7, no higher oxides of Fe above Fe,O3, are known, although ferrates (VI) (FeO,)2-, are formed in alkaline media but they readily decompose to Fe,O3 and Op. -Besides the oxides, oxo-cations stabilise VW” as VO,*, V'Y as VO and Ti’ as TiO**, Mn,0, cro, X05 10, V0, Cr, xno, SO, TO, V0, Cr, _MnO, Fe, MnO, FeO; C00; FeO CoO MO CUD_ Zn cu,o +2 TIO VO (cro) M Oxidation States observed in Oxides -The ability of O to stabilise high oxidation states exceeds that of F. Thus the highest Mn fluoride is MnF,(IV) while the highest oxide is Mn,0,(VII). CBSE 2016 ~The ability of oxygen to form multiple bonds by pn-dm bonding with metals explains its superiority in stabilising higher O.S. of metals. CBSE 2016, 2017 -In the covalent oxide Mn,O;, each Mn is tetrahedrally surrounded by O's including a Mn—O-Mn bridge. The [MO,]*~ ion is tetrahedral. -Generally, an oxide with higher oxidation state is more acidic than the compound of that element with lower oxidation state. This is because, as the oxidation state increases the charge density of that atom also increases which in turn strongly pulls electron density towards itself from other specie that comes closer or in contact with it. CBSE 2017 -Transition metals vary widely in their chemical reactivity. -Many of them are enough electropositive to dissolve in mineral acids, although a few are ‘noble'—that is, they are unaffected by single acids. -The first series metals with the exception of copper are reactive and are oxidised by 1M Ht, though the actual rate of getting oxidised is sometimes low. Eg- Titanium and Vanadium are passive to dilute non oxidising acids.-The E> values for M?*/M indicate a decreasing tendency to form divalent cations across the series. This is due to the increase in the sum of the first and second ionisation enthalpies leading to less tendency to exist in the divalent state. -The E- values for Mn, Ni and Zn are more negative than expected from the general trend. -This behaviour can be explained for : kel, due to it havi oasia -From the M3+/M?* Standard Electrode Potentials, we conclude that: (a)Mn%* and Co ions are strong oxidising agents in aq. solutions . (b)Ti2+, V2+ and Cr2+ are strong reducing agents . Eg- Cr2+(aq) + 2 Haq) —+ 2 Cr+(aq) + H,(g) ) MAGNETIC PROPERTIES: -Most of the transition metals 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 magnetic moment is determined by the number of unpaired electrons and is calculated by using the ‘spin-only' formula only, and that is, ‘n’ is the number of unpaired electrons and p is UW = y[n(n + 2)] os ura the magnetic moment in units of Bohr Magneton (BM). -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. () FORMATION OF COLOURED COMPOUNDS: -When an electron from a lower energy d-orbital is excited to a higher energy d-orbital, the energy of excitation corresponds to the frequency of light absorbed. -While interacting with groups called ligands, the d-orbitals lose there degeneracy and an energy difference is observed between some of them.-Thus, for electrons to jump between two of such orbitals, energy of a certain frequency is required. CBSE 2017, 2015 -This required frequency generally lies in the visible region, thus transition metal compounds are generally coloured. -The colour observed corresponds to the complementary colour of the light absorbed. Eg- If 516 THz (frequency of Yellow colour) frequency is absorbed by a compound, it will show purple as purple is yellow’s complementary. -The frequency of the light absorbed is determined by the nature of the ligand. -Compounds of certain metal ions like Sc3+ and Zn?* are colourless. Sc%+ — 4s° 39: No d-electron thus, no d-d transition is possible. CBSE 2018 Zn2 — 45° 3d" : d-orbitals fully-filled,no d-d transition is possible. Case 2017 au? 3a? at sil’ colourless colourless CBSE 201712) purple blue 3d green sd? violet Colours shown by metals in an at oe aqueous solution, i.e., when salt blue water molecules act as ligands. sa* Mn* pink at ro gellow 3a* re green d's? Co*Co” bluepink sat Ba" aa” ren blue colourless. ‘Scanned with CamScarner-Complex compounds are those in which the metal ions bind a number of anions or neutral molecules giving complex species. -The transition metals form a large number of complex compounds. -This is due to the comparatively smaller sizes of the metal ions, theircase 2017(2),201 high ionic charges and the availability of d orbitals for bond formation. 2019 Eg- [Fe(CN),]®-, [Fe(CN)g]*-, [Cu(NHg)4]?* and [PtCl,]?-. 1) CATALY -The transition metals and their compounds are known for their catalytic activity. -This activity of theirs is ascribed to their ability to adopt multiple oxidation states and to form complexes. CBSE 2019, 2016 7 -Catalysts at a solid surface involve the formation of bonds between reactant molecules and atoms of the surface of the catalyst. -This has the effect of increasing the concentration of the reactants at the catalyst surface and also weakening of the bonds in the reacting molecules (the activation energy is lowering). -Also because the transition metal ions can change their oxidation states, they become more effective as catalysts. Eg- () Vanadium(V) Oxide [V2Os] in Contact Process. (ii) Finely divided Iron in Haber's Process (iii) Nickel in various hydrogenation processes. (iv) Iron(|II) catalyses the reaction between iodide and persulphate ions. Reaction- 2- + S,O,2——+>+ | + 20,2 Step-1: 2Fe3+ + 2l-—> 2Fe + |, Step-2: 2Fe2+ + S,0,2——> 2Fe3+ + 250,2- Fe+ is regenerated and is just being used to create a pathway for the reaction to occur faster or have a better yield.-Interstitial compounds are those which are formed when small atoms like H, C or N are trapped inside the crystal lattices of metals. -They are usually non-stoichiometric and are neither typically ionic nor covalent. Eg- TIC, Mn,N, FesH, VHo.s¢ and TiH, 7 -The formulas quoted above do not, of course, correspond to the 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 of these compounds are as follows: (i) They have high melting points, higher than those of pure metals. (ii) They are very hard, some borides approach diamond in hardness. (iii) They retain metallic conductivity. (iv) They are chemically inert. MATION: = Analloy 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 alloys are formed by atoms with metallic radii that are within about 15 percent of each other which works in favour of transition metals as they are very similarly sized. CBSE 2019 The alloys so formed are hard and have often high melting points. —Ferrous alloys: chromium, vanadium, tungsten, molybdenum and manganese are used for the production of a variety of steels. Transition metals also form alloys with non-transition metals such as brass (copper-zinc) and bronze (copper-tin). -These oxides are generally formed by the reaction of metals with oxygen at high temperatures. -Allthe metals except scandium form MO oxides which are ionic.-The highest oxidation number in the oxides, coincides with the group number and is attained in Sc,O, (III) to Mn,O,(VII). CBSE 2017 ~Beyond group 7,no higher oxides of iron above Fe,O, are known. -Besides the oxides, the oxo-cations stabilise VY as VO", VV as VO2+ and Ti’ as TiO*. -As the oxidation number of a metal increases, ionic character decreases. -In the case of Mn, MnO; is a covalent green oll. Even CrO,(VI) and. VO; have low melting points. -In these higher oxides, the acidic character is predominant. Thus, Mn,O7 gives HMnO, and CrO3 gives H»CrO, and HyCr2O7. -V2Os is, however, amphoteric though mainly acidic. -In vanadium there is gradual change from the basic V2O3 to less basic V2O4 and to amphoteric V2Os. -V,O, dissolves in acids while V.Os reacts with alkalies as well as acids. -The well characterised CrO is basic but Cr,O, is amphoteric. Potassium dichromate is a very important chemical used in leather industry and as an oxidant for preparation of many azo compounds. (Preparation: CBSE 2016, 2019, 2017(2), 2020 -Dichromates are generally prepared from chromate, which in turn are obtained by the fusion of Chromite Ore (FeCr,O,) with sodium or potassium carbonate in free access of air. The reaction with sodium carbonate occurs as follows: 4 FeCr,0, + 8 Na,CO; + 70,-—+8 Na,CrO, + 2 Fe,0; + 8 CO, CBSE 2016 -The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a solution from which orange sodium dichromate, NazCr,O7. 2H,O can be crystallised. 2Na,CrO, + 2H* ——+ Na,Cr,0, + 2 Na* + HO CBSE 2016 -Sodium dichromate is more soluble than potassium dichromate. The latter is therefore, prepared by treating the solution of sodium dichromate with potassium chloride. Na,Cr,0, + 2 KC|——+ K,Cr,0, + 2 NaCl -Orange crystals of potassium dichromate crystallise out.Important - (The chromates(ORANGE) and dichromates(YELLOW) are interconvertible in aqueous solution depending upon pH of the solution. The oxidation state of chromium in chromate and dichromate is the same. 2CrO,2- + 2H* Cr0,2- + HO Cr,0,2- +2 OH- 2CrO2+H,O —CaSE 2014, 201712) fr ° a oe r ok oi Ke 9 @ Chromate lon Dichromate lon (i) The chromate ion is tetrahedral whereas the dichromate ion consists of two tetrahedra sharing one corner with Gr-O-Cr bond angle of 126°. Acidified potassium dichromate oxidises ~Sodium and potassium iodides to iodine, sulphides to sulphur, dichromates are strong oxidising tin(I!) to tin(IV) and iron(II) salts to iron(II) agents 6-31, + 6e-; CASE 201s, 2016 3. Sr?-— 3Sn** + Ben CASE 2016 3H,S ——> 6H’ + 3S + Ger; CBSE 2015 SFe——PGre+Ge CaEAO Properties Full reaction are of the type: -Potassium dichromate is used (CnO72- + 14 Ht + 6 Fe%* —2 Or? +6 Fe*=7H0 asa primary standard in volumetric analysis. Cr,0 7+ + 14H + 66-208 + 7H, (i)Preparation: CASE 2015 -Fusion of MnO, with an alkali metal hydroxide and an oxidising agent like KNO3 produces the dark green K2MnQO, which disproportionates in a neutral or acidic solution to give permanganate. 2MnO, + 4KOH + O2—+ 2K MnO, + 2H,0 3MnO,2- + 4H* ——* 2MnO,- + MnOz + 2H20. CBSE 2020, 2019-Commercially: Alkaline oxidative fusion of MnO, followed by the electrolytic oxidation of Manganate(VI) produces Permanganate(VI) MnOz——+ MnO,?>—+ Fused with KOH, oxidised with air or KNO, ‘ase 2018 MnO,2 MnO, —> Electrolytic oxidation in alkaline solution -Laboratry: A manganese (II) ion salt is oxidised by per-oxo- disulphate to permanganate. 2Mn2 + 5S,0_2- + 8170 ——+ 2MnO,- + 10SO,2- + 16H* It has two physical properties of Forms dark purple (almost black) considerable interest: its intense crystals isostructural with KCIO,. colour and its diamagnetism along The saltis not very soluble (tn with temperature-depencent weak water, but when heated it para-magnetism. decomposes. KMnO,———+ K, MnO, + MnO, + O2 The manganate and permanganate ions are tetrahedral. The m bonding takes place by overlap of p-orbitals of oxygen with dorbitals of manganese. Hydrogen ion concentration of the solution plays a very important part in influencing the redox reactions of the permanaganate ion. Properties, The green manganate is a . paramagnetic because of one Oxidising reactions in ACIDIC MEDIUM: unpaired electron but the @10l- +2MnO,- + 1GH* ——»2Mn?-+ 8H,0 + SI, ae : permanganate is diamagnetic due to (i) SFee + MnO. + BH! ——PMoi- + 4H,0+5Fe™ case ong the absence of unpaired electron. Gi) $0,0,2- + 2MnO,- + 16H? ——> 2Mn?* + BHO +1000, case amis CES eet ch ra Coe aul KMnOQ, should oxidise water at ‘SS2- + 2MnO,- + 16H*——> 2MIn# + BH,0 + 5S - . : [H*]=1 but in reality the reaction (9 8S0,% + 2NnO- + 8H —> 2M" + 3H.O + S50 ae rogresses very slowly unless (vi) SNO,-+ 2MnO.- + 6H» 2Min* + SNO- + GH_CORSE 2015 MnO,2- is present or the solution's Oxidising reactions in NEUTRAL OR heated: FAINTLY ALKAKLINE MEDIUM: (@2MnO,- +H,0 + —> 2MnO,+20H-+1O,- SE 2018 Gi) BMnO,- + 38,0,2 + H;O—+ BMnO, + 6SO?- + 20H - (CSE 2016 Gi) 2MnO,- + 3Mn# + 2H,O ——5MnO, + 4H: ~Zinc Sulohate or Zinc Onde act as catalyst.? vhs Manganate lon (GREEN) Mn in +6 Used in analytical chemistry in the technique of titration. Titration using KMnO, in the presence of HC! and HNO; often leads to unsatisfactory results as Cl of HCl is oxidised to Cl, and as HNO3 is itself an oxidising agent, it oxidises the titrand and does not let KMnO, exhibit its oxidising property, C8SE 200712) oO ir Mi oll ~o) o Permanganate lon (PURPLE) Mn in +7 Used as a favourite oxidant in preparative organic chemistry. USES: Used for the bleaching of wool, cotton, silk and other textile flores and for the decolourisation of oils, as a result of its strong oxidising power.F-BLOCK (The Inncr-Transition Mctals) LANTHANOIDS ACTINOIDS (The 14 clements following Lanthanum) (The 14 clements following Actinium) INTRODUCTION: -Lanthanum resembles the Lanthanoids, and Actinium the Actinoids, thus it is common to study them with their respective following groups. -The lanthanoids resemble one another more than the members of ordinary transition elements in any series. They have only one stable oxidation state. -The chemistry of the actinoids is much more complicated. The complication arises because of the occurrence of a wide range of oxidation states in these elements and because of their radioactive properties. 1. ELECTRONIC CONFIGURATION: -In neutral state, all lanthanoids have fully-filled 6s orbital but, are found with variable occupancy of 4f and Sd subshells because the energy difference between the orbitals of these subshells is very low and electron can shift between them very easily to achieve the most stable electronic configuration. ~ In X8+, which is their most stable Oxidation State, they have the configuration 4f* (n=1,2,3...,14).65 | Tertium m |aroe | a | art | apt | az | 92 66 | Dysprosium py fartee | ae | at | art | azz | on 67 | Hotmiim We fare | ag | are 176 | #9 os | Erbium er jatar | a | ay 175 | sx 69 | Thum tm artes fae | ay ia | 87 7m |¥ ve | aptoe | ars | ag 17a | 86 71 | teu ta | arsatos? | asa] a | - | - | - Electronic Configurations and Radii of Lanthanum and Lanthanoids 2. |ONIC AND ATOMIC RADII: -There is an overall more than expected decrease in the size of lanthanoids as we move right from Lanthanum to Luterium and this is called lanthanoid contraction. -It has consequences in the chemistry of the Sd series elements as well. -The decrease in atomic radii is not quite regular as it is regular in MS ions. -This contraction is, of course, similar to that observed in a transition series and is attributed to the same cause, the imperfect shielding of one electron by another in the same sub-shell. However, the shielding of one 4f electron by another is less than one d electron by another with the increase in nuclear charge along the series. -There is fairly regular decrease in the sizes with increasing atomic number. -Due to Lanthanoid Contraction, the Sd series elements have a size almost equal to their corresponding group members from the 4d series. Eg- Hf(159 pm) and Zr(160 pm) have an almost identical atomic size due to lanthanoid contraction and because of this they are found to exist together in nature and itis difficultto separate them. CBSE 2016, 2013 Trends in ionic radii of lanthanoids2012,2017(2), 8. OXIDATION STATES: 2016,2019(2), -Predominantly, they exist as XS or X2* . -However, occasionally in the solid phase or in a solution, they are found in +2 or +4 states. -This irregularity arises mainly from the extra stability of empty, half-filled or filled f subshell. -These reasons are also responsible for the irregular ionisation enthalpies. Eg- (a)The formation of Eu2+ and Yb?* is favoured because of their half-filled and fully-filled 4f configuration respectively. Eu — 4f? 632 —> Eu? - 4f7 639 —* Half-filled configuration Yb — 4f!4 652. —+ Yb? - 4f!4 639 —+ Fully-filled configuration. However, Eu2* and Yb2* are strong Reducing Agents i.e., prefer being oxidised to the +3 ion . [8S 2017, 2019 (b) The formation of Tb** is favoured because of its half-filled 4f configuration. Tb — 4 6s? ——+ Tb* - 4f7 6s° —— Half-filled configuration However, Tb** acts as an oxidising agent i.e., prefers getting reduced to the +3 state. (c) CelV ‘s formation is favoured because of its noble gas configuration, Ce — [Xe] 4f! Sd! 6s?—+ Cet* - [Xe] 4f5d0 6s°—+ [xe] Stray — Noble gas configuration. Practically, Ce*¢ acts as an Oxidising Agent, i.e. prefers being reduced to Ce**. In fact, Ce** can even oxidise water, still it is used in analytical chemistry because it is kinetically very slow. tase 2019 (d) Sm, like Eu, exhibits +2 and +3 Oxidation States. (e) Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2. (4) GENERAL CHARACTERISTICS: -All the lanthanoids are silvery white soft metals and tarnish rapidly in air. -The hardness increases with increasing atomic number, samarium being steel hard. -Their melting points range between 1000 to 1200 K but samarium melts at 1623 K. -They have typical metallic structure and are good conductors of heat and electricity. -Density and other properties change smoothly except for Eu and Yb.-Many trivalent lanthanoid ions are coloured(except La3* and Lu$*) both in the solid state and in aqueous solutions. Colour of these ions may be attributed to the presence of f-electrons. -The lanthanoid ions other than the f° type (La3+ and Ce**) and the fl4 type (Yb?* and Lu*+) are all paramagnetic. -The first and second ionisation enthalpies of the lanthanoids are comparable with those of calcium. ~The third ionisation enthalpies indicates that the exchange enthalpy considerations, appear to impart a certain degree of stability to empty, half-filled and completely filled orbitals . -Chemically, the earlier members of the series are similar to calcium but, with increasing atomic number, they behave more like aluminium. -The metals combine with hydrogen when gently heated in the gas. -The carbides, LngC, LnyO3 and LnC, are formed when the metals are heated with carbon. -They liberate hydrogen from dilute acids and burn in halogens to form halides. -They form oxides MzOs, sulphides MS, and hydroxides M(OH) 3. G88 2020 -The hydroxides are definite compounds, not just hydrated oxides. They are basic like alkaline earth metal oxides and hydroxides. The basic property of hydroxides decrease as we go from La to Lu because of decrease in size due to LANTHANOID CONTRACTION. ease 2018 - General reactions of Lanthanoids are as follows: Ln,0, H, Ln; Lnx, Ln Enc, Ln(OH), +H, Chemical reactions of the lanthanoids= Production of alloy steels for plates and pipes. A well known alloy is misch-metall which ase an16 consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, A good deal of Misch-metall is used in Mg-based alloy to produce bullets, shell and lighter flint. USES Some individual Ln oxides are used as phosphors in television screens and similar fluorescing surfaces. Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking. - Includes the fourteen elements from Thorium to Lawrencium. - The actinoids are radioactive and showcase a variety of oxidation states, thus their chemistry is complex. CBSE 2017 -As the latter members could be prepared only in nanogram quantities, they are difficult to study. . ELECTRONIC CONFIGURATION: - All the actinoids are believed to have the electronic configuration of 7s? and variable occupancy of the Sf and 6d subshells. -The addition of fourteen electrons with increasing atomic numbers, is done to Sf. *Thorium is an exception to this as the new electron that comes to it while moving from actinium(89) to it, goes to the 6d orbital. -The irregularities in the electronic configurations of the actinoids, like those in the lanthanoids are related to the stabilities of the f?, f? and f!4 occupancies of the 5f orbitals. CBSE e016, 2019 Eg- The configurations of Am and Cm are [Rn] Sf 7s? and [Rn] Sf? 6d! 7s? respectively. -Although the 5f orbitals resemble the 4f orbitals in their angular part of the wave-function, they are not as buried as 4f orbitals and hence Sf electrons can participate in bonding to a far greater extent.2. IONIC SIZE: -There is a decrease in the size of atoms or M* ions across the series. -This may be referred to as the Actinoid Contraction The effect of Actinoid Contraction is greater than Lanthanoid Contraction because of even poor ee by Sfelectrons. CBSE 2015, 2020 terrae m1 se | on toa | Lawrencinm tr aemine se fo |e Electronic Configurations and Radi of Actinium and Actinoids 3. OXIDATION STATES: -There is a greater range of oxidation states exhibited by the actinoids, because of the fact that the 5f, 6d and 7s levels are of comparable energies and electrons of all these 3 subshells can interact while reacting. CBSE 2020, 2019, 2012 Sy 3 3 a5 9) Ss) sas 4 5 6 cy The known oxidation states of Actinium and _ Actinoids . -The actinoids generally show +3 oxidation state. The elements, in the first half of the series frequently exhibit higher oxidation states. Eg-The maximum oxidation state increases from +4 in Th to +5 in Pa,+6 in U and +7 in Np. The successive elements show a decrease in their maximum oxidation states. -Have more compounds in +8 state than in the +4 state. However, +3 and +4 ions tend to hydrolyse. -The distribution of oxidation states among the actinoids is very uneven. ‘Scanned with CamScarnerREACTIVITY: -The actinoids when finely divided are highly reactive Eg- With boiling water they form a mixture of oxide and hydride. -The combination with most non-metals takes place at moderate temperatures. (4) GENERAL PROPERTIES ATTACK OF ACIDS AND ALKALIES: Hydrochloric acid attacks all metals but most are slightly affected by nitric acid owing to the formation of protective oxide layers. Alkalies, however have no action. PHYSICAL: The actinoids are all silvery in appearance but display a variety of structures. This structural variability is obtained due to irregularities in metallic radii which are far greater than in lanthanoids MAGNETIC PROPERTIES: The magnetic properties of the actinoids are complex. The variation in the magnetic susceptibility, with the number of unpaired 5f electrons, is roughly parallel to the IONISATION ENTHALPIES: corresponding results for the -The ionisation enthalpies are lanthanoids, but the latter has lower than the early lanthanoids. higher values. ~Because of the fact that the outer electrons of actinoids are less firmly held, they are available for bonding. CBSE 2020 5. COMPARISON WITH LANTHANOIDS: ease 2017(2), 2015 -The behavioural similarities become evident after the second half of the actinoid series. Although, like lanthanoids, even the early actinoids show close similarities with each other and gradual variation in properties not involving change in oxidation state. -The lanthanoid and actinoid contractions, have extended effects on the sizes, thus also on the properties of the elements succeeding them in their respective periods. -The lanthanoid contraction is more important because the chemistry of elements succeeding the actinoids are much less known and studied.-The photographic industry relies on the special light- sensitive properties of AgBr. TiO is manufactured for the pigment industry and MnO, for use in dry battery cells. The battery industry also requires Zn and Ni/Cd. Steel Production: It is based on the reduction of iron oxides, the removal of impurities and the addition of carbon and alloying metals such as Cr, Mn and Ni. 6. APPLICATIONS OF TRANSITION AND INNER TRANSITON METALS: Many of the metals and/or their compounds are essential catalysts in called the coinage metals the chemical industry: although Ag and Au are {@) V,0s catalyses the oxidation of SO, in the maniectinecteliphticasd restricted to collection items. (©) ICL with ACH), forms the basis of the Zioglor catalysts used to manufacture poyetnylene (polythene) (c}lron catalysts are used in the Haber process for tho production of ammonia from N,/H, mixtures. (d) Nickel catalysts enable the hydrogenation of fats. (olin the Wacker process the oxidation of ethyne to ethana iscatalysedby PIC, (fNicke! complexes are useful in the polymerisationof alkynes and other organic compounds such as benzene. The elements of Group 11 are