LOCK ELEMEN’ All those elements in which the di nti-penultimate shell, belong to block. General electronic configuration of block elements (12 N n— I)aOCl ns? n= Ultimate shell (n= 1) = Penultimate shell (12) = Antipenultimate shell ‘There are two series in block called lanthanoid series and actinide series. ing electron (last electron) enters into (1 ~ 2) fsubshell ie., fsubshell of Atomic Number (58) —Le™hmoids atomic Number (71) (58) asl4 sgdorl 2 , inoids , Atomie Number (90) —Actoids _ Atomic Number (103) 5/14 g bork 7,2 Position of lanthanoids and actinoids in the periodic table may be given as : ops | 2 3 4 5 6 7 8 9 OH 13 1 15 6 17 18 Grotps Periods _s-block block elements Prblock + oaea eno 5 FNL F213] F P55] 77] YH] [7] HO RT| / RD] FR] PS] wS] Pwo al 87}f 88) [89] [109 fF03 frog To] Tos Toe (Tro [Try firs prv3 frva TTS] Tg fT TA 7 [Ac| 8] [59] [53] [54] [65] [65] [07] [68 7] tants EI FEB EIEIES 792] 9: ] 0 seins Pir el sl fe] Ea a Fig. 7.6 Position of Lanthanolds and Actinoids in the periodic table Lanthanoids belong to f-block, 6th period and third group while aetinoids belong to block, 7th period and third ‘group.Lanthanides Characteristics of lanthanides are described below : 7.8.1. Electronic Configuration What is the general electronic configuration of lanthanoids ? Important features of electronic configuration are (i) There is violation of Aufbau principle in these configurations. (i) Gd and Lu have half-filled and fully-filled -subshell alongwith Sd! Gdgs = [Xe] 4f7 Sd! 6s? Luy, = [Xe] 4f"4 5d! 65? These elements have extra stable electronic configuration. Wg [xe Gii) Eu and Yb are also found to possess extra stable electronic configuration. ‘ Eug3; —> [Xe] 4f7 6s? Hes Yb7) —> [Xe] 4/65? Table 7.13 Electronic configuration and oxidation state of lanthanoids Name of the element Symbol | Atomic number Electronic Oxidation configuration states Lanthanum: ) La 57 [Xe]5d! 6s? +3 Cerium 53 Ce 58 [Xe]4f" Sa! 65? 43,44 Praseodymium Pr 59 [Xe]4f? 6s? +3, +4 Neodymium Nd 60 [xe]4f* 65? 42,43, 44 Promethium Pm 61 [Xe]4f> 6s? +3 Samarium sm 62 [Xe]4/* 6s? 42,43 Europium Eu 63 [Xe]4f7 6s? 42,43 \ Gadolinium 54 Gd 64 [Xe}4f7 Sa! 65? +3 Terbium Tb 65 [Xe]4f? 6s? 43,44 Dysprosium Dy 66 [xe]4f!9 652 43,44 Holmium Ho 67 [Xe]4f"! 6s? $3 Erbium Er 68 [Xe]4f? 652 43 Thulium Tm 69 [Xe}4f!3 6s? 42,43 Yiterbium 2 Yb 70 [Xe}4p"4 632 4243 VLutetium © Lu 1 [Xe]4f4 Sa! 65? 437.8.2. Oxidation State How would you account for the following : Among lanthanoids, Ln(11) compounds are predominant, However, occasionally in solutions or in solid compounds, +2 and +4 ions are also obtained. (AISB 2012) ‘Though, the most common oxidation state of all the lanthanoids is (+3) yet the oxidation states +2 and +4 are also found in the compounds of some of these elements. The (+2) and (+4) oxidation states are stable in those elements which have 4/°, 4f7 and 4f'4 configuration ie., stable configuration. Example : Ce** (4/°), To (47) ; Eu2* (4/7) ; Yb?* (4f"4) are stable though they may undergo oxidation or reduction to acquire more stable (+3) state, Ce and Th** * good oxidising agent while Eu2* and vue are good reducing agent. Coat ge ee” C4 1 = (OA)So shose i pNote| Some cements whose ons do nat have /7 or f' configuration also possess +2 ad oxldation sats. For example : Dy** (47%); sm2*(4y5); NaM(4y2): Pr(4/!) (H Lanthanoids form mainly ionic compounds. Since energy gap between Sd and 4f'is signi cantly high hence lanthanoids show limited number of oxidation states, The overall decrease in atomic and ionic radii from lanthanum (57) to Tutetium (71) is known as Lanthanide contraction ot Lanthanoid contraction, radii of Lanthanoids fea -radit (pm) | Tonic radii (pm) (M™*) 187 106 13 28 3s _'> 182 lol” 181 255m 99 181 98 180 96 199 95 180 oF 178 92 7 o1 176 89 175 88 174 87 173 86What is the cause of lanthanide contraction? \“"S"™* N/m Co de et imines Lanthanide contraction is due to inclusion of fourteen elements between lanthanum and hafnium, there is regular in atomic size cerium to lutetium ; filling of electrons take place in f-subshell of antipenultimate shell (with poor shi effect) hence effective nuclear charge increases. Owing to increase in effective nuclear charge, atomic and ionic ng; 5" qecreases towards right of lanthanide series Hyvdetdeyy 2% Fisanes ) S05" Consequences of Lanthanoid contraction : fr Fre, Gn iret them omy Copais What are major consequences of lanthanoid contraction ? Ken (i) Basic strength of hydroxides : lonic radii decreases from Ce** to Lu’* hence the covalent character of (M—04) bond increases, therefore, basic strength of hydroxides decreases towards right of the series. >. jeureavin2( v2) Ce(OH); —> Most basic hydroxide % mane ae Lu(OH),; —>+ Least basic hydroxide Coa dire d Uaytbancoll. (ii) Similarity in chemical properties : Atomic and ionic radii of lanthanoids are nearly same (insignificantly differ hence their chemical properties are similar. Thus, it is very difficult to separate these elements in pure state, on the basi of their chemical properties. They are separated on the basis of physical properties like solubility, fractional crystallisation chromatography etc. Similarity in second and third transition series : The atomic radii of post lanthanum clements in Sd series at almost similar to the atomic radii of corresponding elements in 4d-series. Because of similar atomic size and similar electronic configuration, the physical and chemical properties of post lanthanum elements of Sd series are similar to the correspondic clements in 4d-series. 3 4 $s cma Se (114 pm) Y (CART Zr Nb re (162 pm {f(s pm (134 pm) (130 pm La(Lanthanides)*> ue Ta Ww (168 pm) (144 pm) (134 pm (130 pm) (iv) Occurrence of Yttrium with heavy lanthanoids : Yttrium is located in 3rd group of d-block in the periodic table! occuts unexpectedly alongwith heavy lanthanoids Ho, Er ete. in nature, This unusual occurrence is a consequence of lanthan0i contraction. The size of Y2* (88 pm) is similar to Ho (89 pm); Er** (88 pm) and Tm** (87 pm). Owing to similar size there # *, Tm, yttrium occurs with these lanthanoids. Moreover separation of yttrium fro™ close resemblence between Y**, Ho’, Er these lanthanoids is difficult due to similar erystal structures, chemical properties and solubilities of their compounds.7.8.4. Paramagnetic Behaviour Lanthanoids and theit ions have paramagnetic behaviour due to presence of one or more unpaired electrons. The ionic species like La*', Lu**, Ce** and Yb** do not have unpaired electrons hence they do not show paramagnetic behaviour. 7.8.5. Colours of Lanthanoid ions What is the principle bel ind coloured compounds of lanthanoids ? Lanthanide ions (Ln'*) having one or more unpaired electrons in 4f subshell are coloured in solution as well as it solid-state, It is due to ff transition, ‘The ionic speci having /®, /” and /"* configuration are colourless. For Example : La’ (4f°) ; Ga?" (4/7) ; Lu* (4/") are colourless.Table 7.15 Colours of Tripositive Ions of Lanthanum and Lanthanoids Ton No. of unpaired Colour Ton [Link] unpaired Colour 3 fees electrons | | electrons | ve oa) Colourless =| ku ary Colourless Ce rar Colourless | ye | rar) Colourles j Pee | 24) Green Tm | 2s?) Green | Nae 3 4p) Reddish | eet | 3caf") Reddish Pm** | 4caf) | Pink yellow Ho | 4(af") Pink yellow | Sm 5 (af) | Pale yellow | py | 5 (49?) Pale yellow Eu 6 (af) Nearly colourless | Tb’ af’) Nearly colourless, | Ge 747) Colourless Ga 707?) Colourless Note’ ( Ions having f" and f+ configuration have same number of unpaired electrons hence have almost same colour, + og p2 344 3: 3+ 4,755) 3+ ¢4 76 | e on) a netar i sara’ Yellow war Papi Tm* 47") Er af") py** ay?) tw as) (ii) The ions mainly Ce** (4/1) and Yb** (4f") are colourless though these ions contain unpaired electrons. It is an exceptional behaviour. According to Main Smith, Ce™* and Gd** ions are colourless because they absorb ion in the ultraviolet region while Yb** is colourless because it absorbs in infrared region. All other tripositive ions are coloured because they absorb radiation in visible region. (Gil) The colour of cations from La** to Gd** repeat themselves from Lu** back to Gd?*.6. lonisation Energy e caline ea low ionisation Ionisation energy of lanthanoids is fairly low and it is comparable to those of alkaline earth ine i alec enetBY, lanthanoids are highly clectropositive. Thus, these elements react with water 10 liberate hydrogs ionisation enthalpics in lanthanoids does not show a regular pattern in the series. pote: Eat /1n eS between -2-2 V to -2-4 V except for Eu which has (-2-0 V) of standard reduction potential. 7.8.7. Physical Properties Lanthanoids are silvery white metal and undergo rapid tarnishing. Hardness of these metals increases with the stomig umber. Melting point of these metals lis inthe range of 1000 K to 1200 K, except samarium; which melts at 1623 K. \: fwolee ware 18.8. Chemical Properties Write dow All Lanthanoids show almost similar chemical reactivity. Heated with carbon important chemical reactions of lanthanoids Carbides like LngC, LngC, LC, Reaction with dil acid <> Hy gas liberated > La(OH); is formed alongwith H gas i Burning in air Ln,0; Heated with Np ie ‘ pees _ Heated with sulphur caled with halogen > 283 Heated with alegen 5 ‘Action of water Note; Lanthanofds have poor tendency of complex formation because cations of Janthanoids have low charge density.Uses of Lanthanides What is the composition of Misch metal ? Give its use, ; om aaa 1. Misch metal: It is important alloy containing 90% lanthanoid (50% La and 40% Ce) about 7% iron and 3% of , Ca and S. These alloys are used in the manufacture of ignition devices; tracer bullets and flints of lighter. An alloy containing magnesium and 3% misch metal is used in the manufacture of jet engine parts. * Pyrophoric alloys : These alloys contain rare earth metals alongwith iron, aluminium, chromium, calcium, silicon an carbon etc. These alloys are used in ignition devices such as tracer bullets, shells and flints for lighters. Composition of th alloy is : 40.5% (lanthanum + neodymium); iron (45%); aluminium (0.5%) and traces of other elements. 2. Mixed oxides of lanthanoids are used as catalyst in petroleum cracking. 3. CeO, is used in 4s mantles. 4, Some oxides of lanthanoids show phosphorescence and are used in the screen of coloured TV tubes. 5. Cerium phosphate is used as catalyst in petroleum industries. 6. NdO, and Pr203 are used for making coloured glass and for making optical fibres. 7. Cerium salts are used in qualitative and quantitative analysis. It is also used in medicines.—,. 7.8. Actinides “The actinoid elements belong to second inner transition series in which electrons ent into antipenultimate (5f) substell {from atomic number (90) to (103)}. Actinium (Z = 89) has electronic configuration [Rn] 5f9 6d) 7s*; it has no electron in 5 subsell ence elements from atomic number (90) ae considered in the actinide series. : Except Ac, Th, Pa and U which occur in nature, all other actinoids are ‘man-made and synthesised by artificial transmuts- tion, All actinoids are radioactive elements. lectronic Configuration Write down general electronic configuration of actinides. General electronic configuration of actinoids may be given as [Ray Sf! 6-1, 75? tn case of first four elements Th, Pa, U, Np the energy difference between Sfand 6d are small hence electrons may occupy so 6d-evels or some times both. However from Pu onwards the 5f subshell fills in a regular manner. The electron configuration of these elements are tabulated below : ‘Table 7.16 Electronic configuration and oxidation states of actinides Element ‘Symbol | Atomic number Electronic Oxidation configuration states Prowactinium Pa a1 [Rn] 57° 6d! 752 43,44, +5 Uranium U 92 [Rn] 5/9 6d! 75? 43,44, +5, +6 ‘Neptunium Np 3 {Rn] 5/* 6d! 7s? 43, +4, +5, +6, +7 Plutonium: Pu 94 [Rn] 5f° 7s? 43, +4, +5, +6, +7 Americium: Am 95 [Rn] 5/7 7s? 42, 43,44, +5, +6 Corium cm 96 [Rn] 5/7 6d! 75? 43,44 Berkelium Bk 7 [Rn] 5/73? 43,44 Californium ce 98 [Rn] 5f*° 75? 42,43 Einseinium Es 99 [Ra] 5f!! 752 42,43 Fermium Fm 100 [Rn] 5f!? 7s? 42,43 Mendelevium Md 101 [Rn] 5/3 7s? 42, +3 Nobelim No 102 [Rn] 5f"4 732 2, 8 Lawrencium ir 103 [Rn} Sf" 6d! 7s? #81.9.2. Oxidation State is not always most stable (i Like lanthanoids, the actinoids also possess the most common oxidation state of +3, however ‘sate as for the first four elements i.e., Th, Pa, U and Np. (i The most stable oxidation state of Th, Pa and U are +4, +5 and +6 respectively. (iii) Plutonium shows all the oxidation states from +3 to +7, however its most stable state is +4. yy (i) Americium (Am) shows the oxidation states from +2 to +6. Am?* ion has stable configuration ($/7). (v) Americium and almost all remaining elements show (+3) state as most stable state. ol (vi) +4 state exists for all the elements from Th to Bk. at | (vii) +2 state in Cf, Es, Fm, Md, No exist in solution only, they resemble with alkaline earth metal in this state. (viii) The elements from Pa to Am possess +5 state in solid state but not in the solution. MO} ions exist in the pH range of 1-4, Those ions undergo disproportionation. 2U0; +4H*—> u* + U0} +2H,0 CS) of (+6) (Gx) +6 state is found in the fluorides of U, Np, Pu and Aim. This state is mainly found in the ions like MO3* and are stable ‘solution as well as in solid state. 18.3. Magnetic Behaviour The ions of actinides having one or more unpaired electrons show paramagnetic behaviour. ie, Am* (5/4) ; Np® (5/2), U>* (5/3) ; Pat* (5) ; Pu** (54) — show paramagnetic behaviour. The ions which have only paired electrons show diamagnetic behaviour. _ ce Le (5714) ; US (57%) ; ThY* (5/9) ; Ac (57%) > show diamagnetic behaviour.7.9.4. Colour of the lons Actinide ions are normally coloured and their colour depends on the number of electrons present in 5/subshell. Ions havin 5f° and 5f7 configuration are colourless. For example : Cm** (5/7) and Th** (5°) are colourless. Actinide ions having 2 to 6 electrons are coloured. For example : U* (593) — Red Pu* (5f5) —> Violet Np (Sf) —> Purple Am** (5°) —> Pink Np** (53) — Yellow green Cm* (5f7) —> Colourless U* (5f2) —> Green Complex Forming Behaviour Why the actinides have stronger tendency of complex formation as compared to that of lanthanides ? Actinides have stronger tendency to form complexes as compared to those of lanthanoids because actinides form ions wih small size and high charge density. Actinides form frequent chelate complexes with ligands like EDTA and DMG. 7.9.6. Chemical Reactivity Actinides are highly reactive and highly electropositive metals because of their low ionisation energy. These elements a as strong reducing agents. Actinides undergo tamishing in presence of atmospheric oxygen, to form a protective layer of oxide. Thorium, plutonium and uranium are Passive towards oxidising acid like nitric acid. Actinides however react rapidly with hydrochloric acid, ree |Note| "Chemical properties of actinides is not well studied because these elements are radioactive: } 7.9.7. Actinide Contraction , eh einice Contraction ‘ Hat é is fe Atomic and ionic radii of actinides decreases gradually along the series with increase in atomic number; it is om A ia nuclear charge isnot properly shielded by Sf electtons. The decrease in atomic and ionic radii across the series from I Fehtis called Actinide contraction, Actnides possess high density also, 7.9.8, Uses of Actinides 19.8. Uses of Actinides 1g Used as fuel in nuclear reactors, (i) U5 is used as fix (Gil) Thorium and its com () Thorium dioxide cor ‘the manufacture of gas mar (°) ThOsis used for making incandescent gas mantles, (+i) Uranium salts are also used in glass, cer f sare, , = nuclear or atomic bombs. pounds are . j "pound reused inthe teatment of cancer. seu lame, Tus this mixture is 4 ates 1% CeO: emits briliant white tight when heated in £05 les.Comparison between Lanthanides and Acti 7.10.1. Differences between Lanthanides and Actinides 2019) Give to differences between Lanthanoids and actinoids. ss Tanthanides Actinides 1. Differentiating elecizon enters into 47 subshell 1. Differentiating electron enters into 2. These elements belong to sixth period 2. These elements belong to seventh period. ‘: 3. Except thorium and uranium, all actinides are man mat or synthetic. 3. Except promethium (Pm), all lanthanoids are natural Only promethium (Pm) is radioactive lanthanide. 4, Allactinides are radioactive elements. Lanthanides have poor tendency to form complexes. 5. Actinides have strong tendeney to form cominides and hyclroxides are less basiee - O% YyAoxides are less basic, 6. Oxides and hydroxides are strony! In audition (© (43) state, these , J (#4) stat slements also show | 7. tn aldtion to (1) atate, these elements also show (42). ee (44), (45), (16) an (17) staten. .Actinides form oxo-ions such as PuO}', UO}! « UO" + basic ithanidd sg La do not form oxo-ions, 8 UO}. These ate stable in aqucows and acide medium 9, Some of an Most of ions of actinides have brilliant colour. oid ions are futly coloured. 40.2. Similarities Between Lanthanides and Actinides (i) General electronic configuration of both lanthanides and actinides are same de., (n= 2p Bn Ports? y they have three incomplete shells je, ultimate, penultimate and antipenultimate shells, However in lutetium and lawrencium, he fsubshell is fully filled. (ii) Lanthanides and actinides both have a common oxidation state of +3. (ii) Lons with unpaired electrons have paramagnetic behaviour (iv) Lanthanides and actinides are electropositive in nature and they have reducing character. (0) Hydroxides, fluorides and carbonates of both lanthanides and actinides are insoluble in water, However, on the other ad, sulphates nitrates and perchlorates of lanthanides and actinides are water soluble. (vi) In both lanthanide and actinide series, contraction in atomic and ionic radii (M3*) tal Homic number. place with increase in the (vii) Phenomena of ion exchange is observed in both actinides and lanthanides,