ransonetements comprise thse metals in groups’ to 12,4 oe ne .,the d-block elements, as well as the so— re vier transition elements? which are the lanthanides and actinides, also known asthe f-block elements “on are all metallic elements, so they are often called the transition metals, which are synonymous , ne transition. elements. These metals have crucial uses in industry and biology. Most of these metals are vain the form of solid inorganic compounds called minerals. Names of minerals are based on peat of their discovery, the person who discovered them, or some characteristic of the mineral. For ple, some minerals are named after their colours. The oxidation state of transition metals in minerals jrecommonly +1, +2 or +3. The study of the transition metals in solid state have been dominated by solid cate physicists, and is closely tied to important technical advances, such as the development of the first Jasers. Lo a Main groups jf i ups 6 ee element ii (p-block elements) 1 18 1A 8A 13 [14] 15 ]16 ] 17 [2 3a | 4A | 5A |6A | 7A | He Transition metal Se Gaigica. groups, | | 5 7[s]o (d- block elements) é Ne B|c|N|O|F |Ne 3]4]s]e[7]8]9]olule 15 | 16 3B | 4B | 5B | 6B |7B Teles ails 4 rT | 18 [2B] ai} si|P | s | ci] ar 2),)19 31 | 32] 33 | 34 | 35 | 36 aK Ga} Ge| As | Se | Br | Kr 37 , 49| 50) 31 | 52] 33 | sa Rb In| Sn] Sb] Te] 1 | Xe AS 8i| 82 | 83] say ss | 86 cs TL] Pb | Bil Po} At | Rn bh 87 fi3}tia [115116] 117 | 118 Fr Lanthanides Actinides:Lleevth publications The d— block elements (transition elements) The series of elements that are formed by filling the 3d, 4d and 5d subshells of electrons comy @-block elements. The elements which possess half filled d-subshells either in the atomic sia, a a oxidation state are called d-block elements. They are often called as ceagon elements beg, ual position in the periodic table is between s-block and p-block elements and their properties are val between the highly reactive metallic elements of the s-block, which form ionic compounds an cleme p-block which form covalent compounds. In s and p blocks, electrons add to the last shell, by 5, ay electrons are added to the penultimate shell. ‘The transition elements can be either typical transition elements or non-typical transit elem Elements of group 12 Zn, Cd and Hg have a completely filled (n-1) d subshell and hence, they anny included in the d-block. But, they show properties such as formation of complexes with ligands sug ammonia, amines and halide ions and are hence, studied along with d-block elements. These Clements elements of group 12, Zn, Cd and Hg, (even group 3 like Se, Y, La) are termed as non-typical trang elements and the other transition elements are termed as typical transition elements. Position in the periodic table The transition elements occupy the central part of the periodic table, bridging the gap between the s-block metals of groups 1 and 2 on the left and the p-block metals, semimetals, and nonmetals of 13~18 onthe right. Because the d subshells are being filled in this region of the periodic table, the trans elements are called d-block elements. Each d subshell consists of five orbitals and can accom 10 electrons, so each transition series consists of 10 elements. The first series (3d series) extends scandium to zinc and includes many familiar metals, such as chromium, iron, and copper. The second se (4d series) runs from yttrium to cadmium, and the third series (Sd series) runs from lanthanum to mexcur addition, there is a fourth transition series (6d series) made up of lawrencium through the recently discov element 112, copernicium (Cn). The fourth row of 6d is still incomplete. Electronic configuration of the d-block elements The d-block includes three series each of ten elements. These series are characterised by the partly filled! 4d, and 5d subshells and are named as 3d-(first series) Sc — Zn, 4d series (second set ‘Y—Cd and the Sd series (third series) La—Hg Tespectively. There is an incomplete fourth series in which! 6d subshell starts to fill at Ac.21 2 23 [Ar] 342 [Ar] 342 [Ar 3a4e2 24. BD) 26 [Ar] 3454s! [Ar] 3d°4s? [Ar] 3d%4s? [Ar] 3a"4s? 27 28 [Ar] 3d84s? 29 | [Ar] 3d!4s! {copper ne po [Ar] 31452 nic configurations of d-block elements (3d series and 4d series) The dand fBlock Elements Yutrium [Kr] 4d'5s? Zirconium [kr] 4¢P5¢? Niobium [Kr] 4a"ss! Molybdenum {Kr} 4a¥ss! Technetium {Kr} 4059? Ruthenium [Kr] 4475s! Rhodium [Kr] 4d¥5s! Palladium [Kr] 44° Silyer Ukr] 4d!°5s! Cadmium [Kr] 4a'°5s? able 2: Electronic config jurations of d-block elements (5d series and 6d series) [Lamhanum | La 57 | [Xe] 5a'6s? | Actinium Ae 89 [Rn] 6a'78? ‘Hafnium HE 72 | [Xe] 4f!* Sa%6s* |Rutherfordium | Rf 104 [Rn] 4f'* 627s? ‘tantalum | Ta 73 | [Xe] af" se%6s* [Dubnium Db 105 [Rn] 4£ 6°73? lrongsten | W | 74 | [Xe] 41" Sat6s* |Seaborgium | Sg 106 [Ra] 4fl* 6447s? Rhenium | Re | 75 | [Xe] 4f'*Sa%6s? |Bobrium Bh 107 [Rn] 4f"4 64572? losmium | Os 76 | (Xe] 4f!4 Sa%6s? |Hassium Hs 108 [Ra] 4f!4 60°73? eigium. Ir 77 _ | (Ke) 4f"* 5a’6s? |Meitnerium Mt 109 [Rn] 4f" 64775? Platinum | pix | 78 — | [Xe] 4f!45q?6s! |Darmstadtium } Ds 10 [Rn] 4f 6457s" Gold ‘Aut | 79 | [Xe] 4f!*5a'%6s! |Roentgenium | Rg mt [Rn] 4f!4 6a!°7s! Mercury | He | 80 | (Xel4f"*Sd!963?|Copernicium | Cn 112 [Rn] 4£ 607s? Irregular electron configurations ‘We know that, because of sub-level splitting, 4s fills before the 3d. But the difference electronic configurations in which the ns only their electronic configuration must in energy is not large. Some of the ds sub-level is lower in energy than the 3d. Therefore, the the transition metals have irregular partially fills before the (n —1)d of does not fill at all. Therefore, ‘be found experimentally. Elements marked with asterisk have anomalous re aLJeevit publications configurations. These are attributed to factors like nuclear-electron and electron-electron int, and stability of half filled and fully filled orbital. For example, copper and chromium have g ‘a in 4s-orbital. This is due to the gain of additional stability by the atom having either half-fjeq or completely filled (10 electrons) d-subshell. °c t ing Anomalous configurations of some d-block elements Se aS TC os Wi Cr=[Ar]3d°4s' Cu=[Ar]3d"4s! Cr=[Ar}3d*. Cus [Ar]3d°4s* Mo = [Kr]4d“5s? Mo = [Kr]4d*5s! Ru=[Kr]4d’5s' Pd = [Kr}4d"°5s° Ru =[Kr]4d°5s* Pd = [Kr}4d°5s* Note: All transition elements are d block elements but all d block elements are not transition clemen, es, Illustrations (NCERT Examples) 1. Zine, cadmium and mereury are generally not considered as transition metals. Give reasons, Solution: The electronic configurations of Zn, Cd and Hg are represented by the general form (n— 1)d!9 ns?, The d-orbitals in these elements are completely filled in the ground state as wel). their common oxidation state of +2. Therefore, they are not regarded as transition elements, 2. Though copper, silver and gold have completely filled sets of d-orbitals yet they are considered ag transition metals. Why? ‘Solution: These metals in their common oxidation states have incompletely filled d-orbitals c.g. Cu hag 3d? and Au* has Sd configuration. 3. Onwhat ground can you say that scandium (Z = 21) isa transition element but zinc (Z = 30) isnt Solution: In Sc, the incompletely filled 3d orbital in its ground state (3d). Hence, itis regarded asa transition element. On the other hand, zine atom has completely filled d orbitals (34"°) in its ground state as well as in its oxidised state. Hence it is not regarded as a transition element. General characteristics of the transition elements (d-block elements) 1. The properties of transition metals are largely dependent on the electronic configuration of th in the outer shell and in the penultimate shell. Except mercury, all transition metals are solid in nat with typical metallic crystal structure. With the exceptions of Zn, Cd, Hg and Mn, they have one ‘more typical metallic structures : face centered cubic (fee), hexagonal close packed (hep) an bod centered cubic (bcc). These properties reveal that both metallic and covalent bonding are present int ‘atoms of transitional elements. \ 2, They are good conductors of heat and electricity as there are many free electrons per atom (0 © thermal or electrical energy. 3. They have high tensile strengths (i., they can be hammered or bent into any shape directional property of metallic bond). nf ily due 10mThe d and flock Elements melting points and boiling points. This is because the bonding between the atoms in isis very strong, The strong attractive force between the atoms is only weakened at high hence the high melting points and boiling points. Mercury is a liquid at room temperature. ly hard, tough and strong because of the strong metallic bonding. g bonding between the atoms in transition metals, they are tightly held together to give ally lustrous/shiny solids (or liquids), , yaialeble and ductile, pave high enthalpy of atomization. The higher enthalpy values of atomization for the second ma series account for the occurrence of much more frequent metal - metal bonding in 4 mounds of the heavy transition series, ¢ of large number of unpaired electrons in their atoms they have stronger interatomic d hence stronger bonding between atoms resulting in higher enthalpies of atomisation. in atomic and ionic sizes of transition metals {phe atomic radii and ionic radii of d-block elements in any series decrease with increase in the siomie number. The decrease however, is not regular. The atomic radii tend to reach minimum near wen of the series, and increase slightly towards the end of the series. 200 rm y aos |S d series] i del 2 3 2 ‘Sobre ais oe = ' q 5 Nb ss Ag < ‘Mo’ 2 a se et Za Wy be Tr cs Tia feris 125 ee = Cu cr Ni 100 >. 5 ae an GB) (48) (SB)—«(6B)— (7B) (8B) (8B) (8B) (1B) (2B) Group numbers Fig. 8.2 Variation of atomic radii in 3d, 4d and Sd series of elements with increase in atomic number “ D>.Jeouthpubscatons Explanation: When we go in any transition seri by one unit at each elements. The added electro added electrons shield the outermost electrons from the nuclear charge tends to reduce the atomic radii, white the a At the beginning of the series, due to smaller number of elec ue nuclear charge predominates, and the atomic radii decrease. Later In the series, when the ,, 1" d-electrons increases, the increased shielding effect and the increased repulsion between the cj.,,, to increase the atomig radii, Somewhere in the middle ofthe series, therefore, the atomic rai 41 a minimum value as observed. 7 (ii) The atomic radii increases while going down in each group. However, in the third transi, from hafnium (Hf) and onwards, the elements have atomic radii nearly equal to those of th transition elements. Explanation: The atomic radii increase while going down the group. This is due to the introducris, additional shel at each new element down the group. Nearly equal radii of second and third tansig elements is due to a special effect called Janthanide contraction. (Refer page number I - 85) from left to right, the nuclear charge incr. enter the same penultimate shell, (inner 4 i * Bay attraction of the nuclear charge," \dded electrons tend to inc trons in the dorbitals, the eto." Se the Mo, OM se 1 se Tonic radii: The ionic radii of the d-block elements follow the same trend as their atomic radi disc. above. Forions carrying identical charges, the ionic radius decreases slowly with increase in atomic nung in the same transition series. 3d-series of elements Electronic configuration of 3d series of elements. ‘The general valence shell electronic configuration of 3d series of elements is [Ar]!* 3d!-1° 4s! rations of elements and their ions in 3d series es Fy Table 3: Electronic confi M M* M* M* Scandium Sc 21 [Ar] 3a!4s? [Ar] 3d!4s! [Ar] 3a! [Ar] Titanium Ti 2 [Ar] 3074s? | [Ar] 3474s! [Ar] 3a [Ar] 3a! Vanadium | V 23 [Ar] 344s? | [Ar] 30°45! [Ar] 34° [Ar] 3° Chromium] « Cr* 4 [Ar] 354s! | [Ar] 3a [An 3¢! [ar] 34° Mangancee ik 25 [Ar] 3a%4s? | [Ar] 304s | [Ar] 30° [Ar] 3a {iron Fe 26 [Ar] 3a%4s? | [Ar] 3d%4s! [Ar] 30° [Ar] 3° Cobalt Co 27 [Ar] 3d74s? | [Ar] 3074s! [Ar] 3d7 [Ar] 3° Nickel Ni 28 [Ar] 3484s? | [Ar] 3d84s!- | [Ar] 3d* [ar] 3d” Caper ee 29 [Ar] 3a!%4s! | [Ar] 3a" [ana 5 ee Zn 30 [Ar] 31452 | [Ary 3d!4s! | [ar] 3a"‘The dand fBlock Elements q and chromium have a single electron in 4s orbital. This is due to the gain of additional 1 pate om having either haf filled (5 electrons) or completly filled (10 electron) d-subshell "i a ele character ‘ igements are metals. These metals have close packed structures (fee, hep or bee type). The yt ighmelting and boiling points of d-block elements suggest the presence of strong binding forces it gals, The hardness of these metals suggests the presence of covalent bonds. The unpaired , won ‘may overlap and form covalent bonds, The number of such covalent bonds will be a measure of re ‘pond streneth and hardness of the metal, In 3d series, the number of unpaired d-electrons increases as wee fom 3d!4s* to 3d°ns! after which pairing starts. As a result, the metallic lattice becomes stronger ve rongerupro crancl thereafter strength decreases progressively. These are all good conductors of electricity cess metallic lusture. Both these properties are an account of delocalisation of their outer ‘s’ electrons 908 oP entre crystal lattice. cryst yer qrends in properties of 3d sereis (first row transition metals) Lattice structures of transition metals (3d series) aw Gr [oMa [Fe Co Ni cut Zn hep | bec] bee | xX | boc | cop | cep | cop x (bec) (bee,cep)} (hep) | (hep) (hep) soble Mt > ionisation enthalpies mization energy is the minimum energy required to remove the most loosely held electron from the ground state of one mole of the isolated atom, molecule or ion in the gaseous state. }, Successive removal of further electrons are termed as second, third etc., ionization energies, 1, Ionization energy decreases with the increase in the size of the atom. 3, Ionization enthalpy is greater as the nuclear charge or effective nuclear charge increases. 4, More energy is required to remove the electron from the half filled or completely filled shell and hence the ionization energy also is higher. ‘Transition elements have high ionization energy due to their small size. Their ionization potentials lie between those of and p block elements. Thus, they are less electropositive than the s-block elements. The ionisation cathalpy of 3d series increase as we move across each series from left to right. This is due to the increase in nuclear charge which accompanies the filling of the inner d orbitals. The second ionisation energies of the first transition series also increases with the increase in atomic number. But this trend is not regular and there are some irregular variations. 1. Second ionization enthalpy of Cr and Cu are sufficiently higher than those of their neighbours. This is due to their stable electronic configuration (d° in Cr and d'° in Cu). The first ionisation enthalpy of chromium is lower because the removal of one electron produces extra Stable d& configuration and that of zinc is higher because the removal of electron takes place from fully filled 4s orbital.teow pumtcatons: Cre Mi as! —> Cre aS Bana Mae ——4 Zn = Ad? enthalpy of Zn is less than second ionization enthalpy of Cu. 7),, table d'® configuration while the removal of so." in exchange enemy t0 form, j.°"" X_ The second ioni removal of second electron in Zn proxtuces in Cu disrupts the a" configuration with a considerable loss configuration, 4. Second ionization enthalpy of Mn (Z: second electron in Mn produces half filled d° S. Third ionisation enthalpy of Mn is more than that of Fe, This Ma disrupts stable a configuration but in Fe removal of third electron ge = 25) is less than that of Fe (2 = 26). This is because ,, configuration but Fe produces o (less stab sis because removal of third oie... forms stable con. uray 3. Oxidation states All the transition elements, except the first and last members states. They show variable valency in their compounds. of the series, exhibit a number of oxid Cause for variable oxidation states 1. The valence electrons of the transition elements are in (n= in energies. Both energy levels can be used in bond formation. They show the +2 oxidation state due to the 2 electrons in ns orbitals where the electrons of (yj remain unaffected. 3, The higher oxidation state from +3 to +7 is due to the use of all 4s and unpaired 3d electrons jg transition series of elements. In the excited state, the (n — 1) d electrons become bonding and sive variable states to the atom, Thus the variable oxidation state is due to the participation of boty, and (n- 1) d orbitals in bonding. Table 5: Some basic oxidation states of the first transitior in table 1dandas orbitals which have lite di 2 n series elements are given be| +2, 43 42,4344 42,43, 44,45 +2, +3, +4, +5, +6 42,43, +4, +5, +6, +7 +2, +3, +4, +5, +6 +2,43, +4 +2, 43, +4 +1, +2 +2ne The d and f Block El t features of oxidation state of transition metals are a FE on oxidation state of 3d series is +2 posteormon Oi s is +2 except scandium, due to the loss of tw: Hyows that orbitals are more stable than s orbitals after scandium, nes er i von ee e ally formed in lower oxidation +2 and +3 state while the covalent bonds are inhigher oxidation states. Covalent bonds are formed by the sharing of d-electrons. g me \ quis he oxidation pe oo i increasing atomic number of element, reaches maximum in the middle mote sa i as shown in the Table 4, Highest oxidation state is the number of electrons in and ‘unpaired electrons in the (n ~ 1)d orbi i is ee orbitals. For example, chromium has atomic number 24 ee i, x rs a i] 3d? 451 oe to more stable half filled orbitals. They show oxidation e#2,+3,+4,+5,+ 6. Generally Chromium forms compounds with oxidation state +2, +3 and +6- spe #2 state of chromium is easily oxidized in aqueous solution tothe +3 state. The +3 and +6 states ‘emote stable in chromium. qe elements in the beginning of the series exhibit less oxidation state because of having small number afeleotrons to lose or contribute, The elements in the middle of the series show the highest oxidation «sae, For example; Min shows all the oxidation states from +2 to +7. Iron has atomic number 26 and the electronic configuration is [Ar] 3d® 4s. Iron has 4 unpaired electrons in 3d orbital and 2 paired electrons in 4s. So the possible oxidation states are + 2, + 3, + 4, + 6 but generally it shows {42and +3 oxidation state. ‘The maximum oxidation state of reasonable stability in 3d series is equal to the sum of sand d electrons up toMn followed by decrease in the stability of higher oxidation states. ‘The higher oxidation states are more stable in heavier elements. For example, Mo (V1), ‘W (VI) are more stable than Cr (VI). [ninteresting feature in the variability of oxidation states ofthe d-block elements is noticed among the groups (groups 4 to 10). Although in the p-block the lower oxidation states ars favoured by the heavier members (due to inert pair effect), the opposite is true in the groups of d-block. For example, in group 6 Mo(VI) and W(V1) are found to be more stable than Cr(V1). Thus Cr(VI) in the form of dichromate in aeidic medium is a strong oxidising agent, whereas MoO, and WO, are not, § Lowoxidation states are found when a complex compound has ligands capable of n-acceptor character inaddition to the o-bonding. For example, in Ni(CO), and Fe(CO), the oxidation state of nickel and iron is zero. 9, The relative stability of metal ion in its various oxidation states and those of different metal ions in the same oxidation state can be found by consideration of standard electrode potential values. illustrations (NCERT Example) 1. Name a transition element which does not exhibit variable oxidation states. Solution: Scandium (Z = 21) does not exhibit variable oxidation states. )) | ie — OSJeevith publications 4, Magnetic properties A substance which is attracted by magnetic field is called paramagnetic substance. The substance, a i repelled by magnetic field are called diamagnetic substances. Paramagnetism is due to the 5, ition elements and their «. unpaired electrons in atoms, ions or molecules. Most of the tra show paramagnetism, The paramagnetism first increases in any transition element series, and they, ‘The maximum paramagnetism is seen around the middle of the series. The paramagnetism j, oy in Bohr Magneton (BM) units. The paramagnetic moments of some common ions of first trans ion are given in Table 8. The magnetic moment of any transition element or its compoundiion is ajo, from the orbital magnetic moment). spin only formula (assuming no contrib = /n(n+2) BM where nis the number of unpaired electrons, Calculation of magnetic moment in Cr** ion (Cr(Z=24) — : Electric configuration = [Ar]!*3d°4s! nae : Electronic configuration =[Ar]"*3d"4s° The number of unpaired electrons in 3d sublevel is f t] t 3d u=/n(n+2) 1= 362) 1=3-87 BM Calculation of magnetic moment in Fe** ion Fe(Z=26) : [Ar]"*3d°4s” Fe; [Ar]*3d°4s° ‘Number of unpaired electrons in Fe tl t t t t ie, n1=4 n= Jnqn+2) = J4(4+2) =4.-90 BM Itis evident that the magnetic moment (j1) increases with increase in the number of unpa electrons.‘The dand fBlock Elements ind orbitals belonging to a particular energy level, there can be maximum of five unpaired electrons in &. Therefore, paramagnetism in any transition series first increases, reaches a maximum value for d° cases and then deereases thereafter. Thus, observed magnetic moment gives useful information about the number of unpaired electrons present in the atom or molecule or ion. illustrations (NCERT Example) 1. Caleulate the magnetic moment of a divalent ion in aqueous solution if its atomic number is 25. Solution: With atomic number 25, the divalent (five unpaired electrons). The magnetic moment, Z =25 [Ar] 3054s? M* = [Ar] 38 +, there are five unpaired electrons (n = 5) 38 = ATTA = Jfn(a +2) W=5+(5+2) = /35 =5-92 BM ion in aqueous solution will have d® configuration hisJeevth publications 5. Formation of coloured ions carat ured in th AP AMONE two es, Most of transition metal compounds are ites ns in it and the pee oe Es ee ‘metal ions is due to the presence of unpi ites of energy needed fore Bf, i Y CAN be « ‘same d-subshell is small. Therefore, aah a hin the samme: se cis ed a fo ai ital to higher energy d-o ne : ha cree cntour Lee catates a ee om . c Z in Tat _ colour of some transition metal ions are specified i ation oF slid form. The cojy,. it Ss Table 7 : Colour of some transition element: Te might be noted that cadmium, zine, an absence of vacant d orbitals to which e absence of unpaired d-electrons, © Smatt size‘The dand /Black Elements ‘of vacant inner d-orbitals of suitable energy, where the electrons donated by ligands a jes with lone pair of electrons which they readily donate. These species can be neutral oe jes sueh as NH, 1,0. NO, CO, etc, or ions such as F-, Cl’, CN-, etc, The compounds containing ex fons are termed as coordination compounds. Na,[Fe(CN),], {Cu(NH,),]SO,, [Cr(NH,),ICl, 2Mn“"O*+Mn"O, +2H,0 Some important compounds of transition elements Potassium dichromate (K,Cr,0;) Potassium dichromate is an industrially important compound mainly used in leather industry and oxidizing agent for the preparations of many azodyes. m dichromate from chromite ore Manufacture of pota: Finely powdered chromite ore (FeCr,O,) is mixed with soda ash (anhydrous Na,CO,) and burnt in exc air. Yellow mass due to the formation of sodium chromate is obtained. 4FeC1,0, +8Na,CO, +70, —>8Na,Cr0, +2Fe,0, + 8CO, The yellow mass is extracted with water and filtered. The filtrate contains sodium chromate and is aci with dilute sulphuric acid to get an orange coloured sodium dichromate solution. 2Na,CrO, + 2H’ —Na,Cr,0, +2Na*+H,Ore The dand Block Elements solution is concentrated and cooled. Na,Cr,O, . 2H,O crystals are formed. SAMTEE bodium oi i ‘ nl ao dichromate is treated with potassium chloride to get potassium jum. mate being less soluble than NaCl crystallizes out on standing. 2:0; +2H’ —>Cr,0;+H,0 (Acidic medium, pH <7) €x,0; +20H” —>2Cr0> +H,0 (Basic mecium, pH > 7) _ Oxidation state of Cr in chromate and dichromates is same , oxidising Properties jumand sodium dichromates are powerful oxidizing agents. In the presence of acids, oxidizing action can BC written as cg0} 4A? +6" —92Cr*+7H,0 (EP =1.33V) (9) Adidfied K,Cr,0, oxidises iodides to iodine G,0} +141" +6e° —52Cr**+7H,0 6F 31, + 66° G0} H14H" +61 —331, +2CP" +7H,0 ‘Bxample: K,Cr,0, +7H,SO, + 6KI—>4K,S0, +Cr,(SO,), +31, +7H,0 (b) Acidified K,Cr,0, oxidies Fe (II) salts Fe (IID) salts (©,0% +141" +6¢° —32Cr""47H,0 Fe" —>6Fe™ + 60° C0} + 14H" + 6Fe* 3 6Fe™ 42Cr* +7H,0 Example: K. (©) Itoxidises hydrogen sulphide to pale yellow precipitate of sulphur, 0, + TH,SO, + 6FeSO, —>K,80, +Cr, (SO, ), +3Fe,(SO,), +7H,0 C,0% +1411" + 66° —>2Cr* +7H,0 3H,S 96H" +38 +6" (Cr,0} +8H* +3H,S—>3S | 42Cr** +7H,0. Example: K,C1,0,+4H,SO, +3H,S—>K,S0, +Cr,(SO,), +7H,0+384Joovith publications (@)_Toxidises Sn (11) salts to Sn (IV) salts CRO; +14H* + 6e° —4 2Cr* +7H,0 3Sn™* —>3Sn** +6e Rae SN 0S ee ee yO; +14H* +38n* —435n** +2Cr* +7H,O RS eed Potassium permanganate (KMnO,) Preparation Fs fused with Koy, in Itis prepared, in large scale, from the mineral pyrolusite, MnO,, When MnO, Presence of oxidising agent like KNO,, potassium manganate is formed. 2MnO, +4KOH +0, —>2K,MnO, +2H,0 The potassium manganate undergoes disproportionation in acidic or neutral medium to give pery,, 3MnO} +4H* —>2MnO, +MnO, + 2H,0. The purple solution so obtained is concentrated to get dark purple crystals of KMnO, Physical properties 1. Action of heat It is weak temperature dependent as it decomposes at 513 K. 2KMnO, —>K,MnO, +MnO, +O, 2. Oxidising properties Potassium permanganate is a powerful oxidising agent in acidic, basic and neutral medium. 1. _Inacidic solutions, oxidation of MnO; ion can be written as MnO, +8H" +5e°-—> Mn” +4H,O (a) MnO; oxidises iodide to iodine [MnO; +8H* +5e°- —>Mn™ +4H,0]x2 [27 —1, +261x5 RRA A Ae AS hi 2MnO; +101 +16H* —> 2Mn** +8H,0+5I, (b) It oxidises Fe?* ion (green) to Fe** (yellow). ‘MnO; +8H* +5e> —>Mn™ +4H,O [Fe* —>Fe™* +e"]x5 MnO, +5Fe™ +8H* —> Mn” +5Fe™ +4H,O., at: The d ick jon or oxalic acid is oxidised to CO, at 333 K by Mn Se i - . @ y, + BH! +50" —> Mn” +4H,0]x2 et? “5 Si... 1 iP ft. 2 M0; +5C:08 +16H* —>2Mn’* +8H,0+10C0, el @ ysrogen sulphide is ox lised to yellow precipitate of sulphur by MnO; ion (H,S—>2H' +S”) jad; +88 +52—> Min” + 4H,0}%2 MnO; +5S" +16H” —>2Mn* +581 +8H,0 sp neatral oF faintly alkaline solutions: i) MaO; oxiises 1 toate by reducing itself to MnO, MnO; +H,0+1 —>2Mn0, + 20H” +10; (p) Thiosulphate is oxidised to sulphate quantitatively by MnO, fon in neutral medium. §Mn0; +3S,0; +H,0—>8Mn0, + 6SO{ +20H™ Note: Permanganate titrations in presence of hydrochloric aid are not done done because HCLis oxidised by MnO, ion to Cl. The f-block elements (inner transition elements) elements in which the differentiating electron enters the anti-penultimate energy level, i.e., ic Dpf ate called f—block elements. These are often called as inner transition elements or rare earth ‘The differentiating electron in inner transition elements may enter either 4f or Sf orbitals based -alled lanthanides d tpnnvihich they are differentiated into lanthanides and actinides. Af series of elements are c: ind sfseries of elements are called actinides. ‘he lanthanide series consists of 14 elements which starts from cerium (atomic number 58) and ends with ‘uetium (atomic number 71). Similarly, actinides consist of 14 elements from thorium (atomic number 90) ‘plawrencium (atomic numbers 103), which follow actinium. Most ofthe actinides are synthesised through nuclear reactions, not available naturally. Electronic configuration General electronic configuration of f-block elements is (n2)f-M( = 1}? Inst Table 8: Lanthanide and actinide series of elements: alse ls] 0] | a] @ | «| o | mtbanite) | ce | pr | Na | Pm | Sm | Ba | Ga} To | Dy | Ho | Ho | Er 389 | 140. | 140.9 | 1442 | 145) | 1504] 1520 | 157.3 | 1589 | 1625 |164.9 | toto [167.3 sl oo | ov | 2 | 52 | Sem mama ame ei peo | 200" tons fae. face (eye oe | uo |p| me | Am] cm | ak | cr} Bs | Fm | Mi | No} No | be Jaz | ax | e3n | ce | 227 | 240 |x) | ean | xn | asn | 52] es | @88) | 259] 25) |) 168.9] 173.0] 175.0LJeevih publications The lanthanoids (Lanthanides) ‘ — Jack mineral was found j The lanthanides were first discovered in 1787 when an unustal a PAHO lanthanide hi by, This mineral, now known as gadolinite, was later separated Dina ite Professor Gadolin obtained yttria, an impure form of yttrium owt spectra of 4% Klaproth secluded the first cerium compound. Later, Moseley echt "the PAG ic cin, en, Prove tat there were fourteen elements between lanthanum and ofall REE OF hele, oy Separated from the same mineral, These elements were fist clasiied & 3F° CNH” duc ay, obtained by reasonably rare minerals. However, this can be oe ati nating from the fis," Practically unlimited abundance. The term lanthanides was adopted, on8 Steleme series, lanthanum. Electron configuration pee 1450-163? The general electronic configuration of lanthanides is: [Xel4/* established through experiments. Th, The electron configurations of these elements were. ee reveals the energy change iny, i Jn line in the emission spectrum . used is based on the fact that eacl Nparoiee Howeves te poten wih his wc transition of an electron from one energy level ane respect to the lanthanide elements is the fact that the 4fand 5d sub-shells have very similar enery, 91. which can make it hard to decide the difference between the two [Table 9] all the tripositive (stable oxidation state is +3) are oF the fp, However the electronic configurations. o (@=1-14). Lanthanoids Table 9: Electronic configurations and Radil of Lanthanum and Lanthan a 5d'6s? 4f'5d'6s? 4p6s? 4f'os? 4f'6s? fos 4f'6s? 4f'5d'6s* 4f6s? 4f6s? 416s? 46s? 4f°6s? 4pt6s? 4f'45d!6s?es ae eI ‘The dand Block Elements jand ion is determined by both the nuclear charge and by the number of electrons that nic sh Within the shells, the degree ‘of occupancy will also affect the size. In the lanthanides, gse in atomic size from 1a to Lu [Table]. This decrease is known as the lanthanide contraction. pdin periodic table is that the atomic radius decreases as we move from left to right. Therefore, this trend with the rest of the elements, ontraction jonic radii of tripositive lanthanide ions show a steady and gradual decrease with the spumber from 1-ato Lu. Tonic radii decrease steadily from Lato Lu. The gradual decreasing janthanides with increasing atomic number is called lanthanide contraction. fe contraction is due to the increase in effective nuclear charge (Z.,,) with increasing atomic 4fsubshell is filled. Towards the end of lanthanides, the size decreases due to a large Zeip ly compensates for the expected size increase due to an added quantum shell of electrons. s of the third transition series have radii very similar to those of the second transition The radii generally decrease with increasing atomic number. 4f subshell fills; Z,, increases 7 [Pm” g so" ; su 3 100 a 2 Dy a Ee” Tin 90 Be. W 1 57 38 59 60 61 62 63 64 65 66 67 68 69 10 7 Atomic number zz - = ——a Fk Jeevith pubsications Cause of lanthanide contraction The major: a eee contraction is due to the poor shielding of the Afelectrons duc ;, = tals. As the atomic number increases in lanthanide series, for every proton in extra electron goes to 4f-orbitals. hte imp ny Ney ao inner shells and are rather ineffective in screening the outer elec, OS beicus tor ae in the effective nuclear charge experienced by the outer electrons, So «), a DS peat in the outermost shell increases asthe atomic number increase a results in gradual deorease in sizeof lanthanides with ineteasing atom," raph). The decrease in sive is not regular throughout the lanthanides. rapid decry." ase ig only in first six elements compared to the rest of the elements. i Consequences of lanthanide contraction 1. Similarity of second and third transition series - Generally the size of atoms increases dow, So the size of an atom of element of second transition series is larger than any atom of ea 3 series but the size of atom of third transition series is nearly same as that of atom of second = series. The similarity in the size of atoms of the elements belonging t0 the same group of the a third transition series is due to the effect of lanthanide contraction. a 2. Difficulty in the separation of lanthanides — Except for small change in the ionic radii, lanthanide, separation of elements in the pure state difcu 4 similar chemical properties. This makes the contraction makes the slight difference in the properties like solubility, complex formation, hydra te. on this basis itis possible to separate them by ion exchange methods. —_ Oxidation states ‘Some elements show +2 and +4 ions in soltig Lanthanides show +3 oxidation state in their compounds. solid compounds. This irregularities arise due to extra stability of (2) emp\y ‘Fesubshell (b) half fi fsubshell and (c) completely filled f-subshell. oured by its nol Te oxidises water slowly. Eu2* is formed by losing two s electrons to form stable half filled f7 configuration. It acts as s reducing agent by changing its oxidation state +3. 3, Yb% is formed by losing two s electrons to form stable completely fi reductant. Tb (+4) has half filled f-orbitals (f7) and is oxidant. of lanthanides ble gas configuration (f°) but it is a strong oxi 1. The formation of Ce (+4) is fava Hence Ce(IV) is a good analytical rea reverting to the common +3 state. e led f '* configuration. It 4. General characteristic properties Physical properties 1. All lanthanides are silve1 ry white metals that tamish when exposed to air, forming their oxides, Hardness increases with increasing atomic number. Samarium 1S 2 They are relatively soft metals. hard.The d and /Block Elements jarium melts at 1623 K. metallic structure and are good conductors of heat and electricity. anthanide ions are coloured in solution and solid state due to the presence of unpaired ®) and Lu” (f"*) ions donot show colour due to the absence of unpaired electrons. are paramagnetic except in f° type (La and Ce) and f' type (Yb% and Lu). gnetism is noticed in neodymium, ‘They liberate hydrogen from dilute acids. [n+ dilute acids —shydrogen gas. , They bum in halogens to form halides. 2Ln+3X,— 2LnX, 6 They react with water to form hydroxides with the liberation of hydrogen. 21n+6H,0—>2Ln(OH), +3H, 7. They form nitrides when they are heated with nitrogen. 2Ln+N, —>2LnN & They react with sulphur when they are heated to form corresponding sulphides. ‘2a +3S—> Ln, Actinides (Actinoids) The actinide series contains elements with atomic numbers 89 (Ac) to 103 (Lr). The series forms the row telow the lanthanide series, which is located undemeath the main body of the periodic table. Lanthanide and actnide series are both referred to as rare earth metals. These elements have a high diversity in oxidation states and all are radioactive. The most common and known element is uranium. Uranium is used as a nuclear fuel whe! ~ into plutonium, through a nuclear reaction. aJeevith publications Electronic configuration of actinides The electron configurations of the actinides is (Rn) Sf'-'* 6d °! 78% 1. The energy in the 6d orbitals is higher in energy than in the Sf orbitals. 2. They fill Sf orbitals, 6d orbitals, then 7s orbital. 3. The Sforbitals are not shielded by the filled 6s and 6p subshells. 4. There is a small energy gap between the 5f* 7s? and Sf! 6d 7s? configurations, 5. The 5forbitals do not shield each other from the nucleus effectively. 6. The energies of the Sforbitals drop rapidly with increasing atomic number. i, The irregularities in the electronic configurations of the actinoids are related to the stabilities og £°,f7 and f' occupancies of the Sf orbitals. Thus, [Rn] 4773? and [Ra] 5f76d!732 the electronic configurations of Am ang ¢ in Oxidation states Unlike lanthanides, actinides show a variety of oxidation states from +3 to +6 due to the very smal en ‘gap between 5/, 6d and 7s sub-shells. The principal oxidation states are +3 and +4. The +3 oxidation sy the most stable. The +4 oxidation state is the most stable in Th and Pu. +5 in Pa and Np and +6 is seen In actinides, the distributions of oxidation states are highly uneven. Table 10: Some properties of Actinium and Actinolds | Atomic ee Spore ti [Radin Soe ; p M* I 89 Actinium 0 m | o Thorium 687s" of? 99 Protactinium 5f 26d! 75? of! 96 Uranium, Sf 6d'Is? Sf? 103 | 93 Neptunium 5f 6d'7s* Si 101 2 Plutonium Pirie oe 100 90. Americium SP Ise i 99 89 Curium Sf 16d'7 Sf? 99 | 8 Berkelium 57s? oH 98 | 87 Californium yey st fs 98 86 Einstenium 5f "75? oe - a Fermium 5f 7782 Bf? - a ‘Mendelevium| Sf 372 ofl! - - Sf 782 5f? - q of te Sf 46d'7s?Ld EA he pty ws ts wie es a ge Toe Ths anty Aevsesen bn ini: 151i wits crease ia senaie, sromtoen A wteaihes 16 Zen enwn Peet Ne \eathcmae 1 mis we Seem “eae We AMI 6 We 7 cing rs A Sf cers by oe safes to eae toch ” gametes iootive Pauchend i ws tes ima seSicms in sire A toe Cessecms Sart. Vis 0 once: elem 0 Ome VEYA 8 28 Ly crnchs, wanes 4f criss me twwtieh tery iid toe BO nn pene Som Cemend to mens in this vessen tose wo yx seeding Oy Sf CDIEOE: pharwcderistics A neAinides wat pales wei atin re ra sive ata na goto A Minne Waker On wcAinien yyver mixture oA oxide ants hydride, ‘they vom: With THO HOM medals ah mere temipexatunen, i actinides are ailecsed by hydrociloric acid tut slightly aflecten by nitric aid due to passivity donation A pronerAive ovide layers on them), ‘ey bowen have any ution with alkalies, |, Memagnetlc properties of the actinides are due to unpaired electrons in 5f electrons. comparison of actinides and lanthanides wonane seen the characteristics of actinides and lanthanides, It can be seen that lanthanides and actinides in hich the 4f und 5f orbitals, being filled show certain similarities and also certain differences. Here is the ‘inptivon of the lanthanides nd actinides, comparison of lanthanides and actinides Binding enerpies of Af electrons are higher. Maximum oxidation state exhibited by lanthanides is +4, example, Ce, Binding energies of 5f electrons are lower. Due to lower binding energies, they show higher oxidation states such as +4, +5 and +6. Example, uranium exhibits +6 oxidation state in UF, and v0,C1L, 5f-electrons have poor shielding effect. They are also paramagnetic but their magnetic properties are very difficult to interpret. 4felectrons have greater shielding effect.They are paramagnetic but magnetic properties can be easily explained. ‘They do not form complexes easily. They have much greater tendency to form complexes. Except promethium, they are non-radioactive. ‘Their compounds are less basic. All of them are radioactive. Their compounds are more basic. . | ‘They do not form oxocations. ‘They form oxocations such as UO%", UO*, NpO}, Pus.LJeevith publications Similarities between lanthanides and actinides 1. Both the series show +3 oxidation state. In both the series the (orbitals are filled gradually. Tonic radius of the elements in both the series decrease with the increase in atomic ny, The electronegativity ofall the elements in both the series is low and are highly reacyi,. The nitrates, perchlorates and sulphates ofall the elements are soluble, while the hcg, es, and carbonates are insoluble, to Question bank for | oe Questions carrying one mark each 2. aA we 10. u. 12. Write the electronic configuration of Mn?* ion (atomic number of Mn = Why is the third ionisation energy of Manganese (Z = 25) is unexpectedly high? [Hints The third electron is to be removed from stable configuration Mn** (34°). It requires higher ene oxidation state? (Rit ; ‘Which element among transition elements exhibits the highest 4 Gold has completely filled d-orbitals (5d) in its ground state, How can you say that itis a transition ee Out of Cr, Co and Zn, identify the element which does not exhibit variable oxidation state? ‘The first ionization enthalpies of 5d series elements are higher than those of 3d and 4d series elements [Hint: Increasing value of effective nuclear charge due to lanthanoid contraction}. Why Mn?* compounds are more stable than Fe* compounds towards oxidation to their +3 state? What are interstitial compounds? ‘What is the most probable oxidation state of actinides? ‘Mention the name of the element among lanthanides known to exhibit +4 oxidation state. Why are Cd? salts white? Titanium shows magnetic moment of 1.73 BM in its compound. What is the oxidation number of Ti ‘compound? [Hint : O.N. of Ti= +3]. Questions carrying two marks each L 2 Ba Explain CuSO, is blue while ZnSO, is colourless? Calculate the magnetic moment of Cr>* (Z = 24) on the basis of “Spin-only” formula. ‘The transition metals and their compounds are known for their catalytic activity. Give two specific reasot justify the statement. ‘Write the chemical equation for the reaction of thiosulphate ions and alkaline potassium permanganate: