Scribd
Upload
20 views

D and F Block

Uploaded by

Satyam Mittal
Copyright
© © All Rights Reserved
Available Formats
Download as PDF or read online on Scribd
20 views

D and F Block

Uploaded by

Satyam Mittal
Copyright
© © All Rights Reserved
Available Formats
Download as PDF or read online on Scribd
You are on page 1/ 7
Chemisty nots for Ml by Rabindra Agrawal The d-block Elements (Transition Elements) ‘The d-block of the periodic table contains the elements of the group 3-12 in which the d-orbitals are progressively filled. They represent transition or change in properties from the most electropositive s-block elements to the least electropositive p-block elements and are, therefore, called transition elements. Strictly speaking, a transition element is defined as the one which has incompletely filled d-orbitals in its ground state or in ‘any one of its oxidation states. Zine (Zn), cadmium (Cd) and mercury (Hg) of group 12 have completely filled d-orbitals (a configuration) in their ground state as well asin their common oxidation states (Zn”, Cd™, Hq”) and hence, are not regarded os transition elements, However, being the end members of the three transition series, their chemistry is studied along with the chemistry of the transition elements. There are four series of the transition elements, 3d series (Sc to Zn), Ad series [Y to Cd), Sd series (La and Hf to Hg) and 6d series (Acand Rf to Cn). Electronic configuration: The general electronic configuration of transition elements is {n-1)d""* ns"? where ‘n’ is the outermost shell and (ris the penultimate shel, The electronic configurations corresponding tothe half and completely filed orbitals are relatively more stable. A consequence of this factor is reflected in the electronic configurations of 2«Cr (344s instead of 34° 43°) and y (aq) ; ByyH = enthalpy of hydration SAM=AjgH 4AM + Bye ‘The electrode potentials are a measure of total enthalpy change. ‘The relative stabilties ofthe transition metal ions indifferent oxidation states in aqueous solution can be compared in terms of standard reduction potential values. More negative the standard reduction potential for a particular oxidation state of the ‘metal, greater willbe its stability in aqueous solution, ‘There is no regular trend in the E°(M""/M) values due to Irregular variation in the jonisation enthalpies (IE, + I€;) and sublimation enthalpies across the series The general trend towards less negative E° values across the series Is related to the general increase in the sum of the first and second ionisation enthalpies ‘The unique behaviour of copper, having positive E° value Is due to the high energy required to transform Cu(s) to Cu’"(a) which is ‘not balanced by its hydration enthalpy, This also accounts for its inabilty to liberate H, from acid. ‘The values of €° for Mn, Ni and Zn are more negative than expected from the general trend. This is due to greater stability of hhalf-filled d-subshell (d*) in Mn’ and completely filled d-subshell (d") in Zn’. The exceptional behaviour of NI is due to its high negative enthalpy of hydration. } ‘Trends in the M™/M" Standard Electrode Potenti * The low value for €° (Sc""/Sc™) reflects stability of Sc'* on which has a noble gas configuration, I * The highest value for 2n is on account of very high stability of Zn" lon with d® configuration. * nin® with halffilled 4° configuration Is very stable, Le. Mn’ cannot be easily oxidised to Mn". Thus, €° (Mn”/Mn™) value is ‘comparatively high. Chemistry notes JorXby Robina mmber of unpaired electrons, Thus, among the dhvalent eat, ase In nul ith the incr ism as it has the maxim ‘The paramagnetic character increases with the incre rhe maximum paramagnets . in®* (a configuration) exhibits i eiteet skceenne the first series of transition Sone ee . ene Irepoted by magnetic fel) I ‘number of unpaired electrons. The last element Zn configuration) has all pared electrons re ea etettne Seria ie F magnetic moment {u) which is elated to the number of un y ‘The paramagnetis is expressed in terms of magn according to the following ‘spin-ony' formula: n= Yn ¥2) 8M (Bh Formation of Complex Compounds joht-magneton, unit of magnetic moment) i Lion binds 2 Transition metals frm a large number of complex compounds. Complex compounds are those in which a peat) pee acy ving complex species with characteristic properti number of anions oF neutral molecules (called Tigands) giving compl cera example Cu" [FAENR (AlN CU ee. The ih compe formation tendency of ansiven laments tothe comparatively smaller size and high ionic charge oftheie meta ions and the avalablity of orbitals for bond fo Formation of Coloured tons ‘Most of the compounds of transition metals are coloured both in solid state and in aqueous solution. itis due to the presence of Incomplete d-subshell due to which d-d transitions are possible. Under the influence of the ligands, the d-orbitals split into two sets of orbitals (t:,and e,) having slightly different energies. In the transition elements which have party filled d-orbitas, transition of electron can take place from a lower energy d-orbital to a higher energy d-orbital (d-d transition) by absorbing radiation ofa particular wavelength (colour) from visible light and specific colour, known as complementary colour is transmitted because of which the compound appears coloured. Complementary colours can be identified using Munsell colour wheel. Here opposite colours are ‘complementary. Note: 2n™, Ca, Hg”, Cu", etc are colourless/white as they have completely filed d-orbitals and so d-d transitions are not possible. Similarly, Sc” and T( are colourless/white as they have completely empty orbitals and so d-d transitions cannot occur. Catalytic Properties, Many transition metals and their compounds act as catalysts in various reactions, For example, V; 0s is used in the manufacture of sulphuric acid by contact process, finely divided iron is used in the synthesis of ammonia by Haber's process, finely divided nickel is used in the hydrogenation of unsaturated organic compounds, Le, hydrogenation of oils into fats, ete. The catalytic activity of transition metals and their compounds is primarily due to the following reasons (i) The transition elements with variable oxidation states may form unstable intermediates that pr ‘activation energy forthe reaction, a new path with lower (i 4p some cases, the transition metals provide a suitable large surface area for the reactants to be adsorbed and thus come: loser to one another for the reaction. This increases the concentration of the reactants at the catalyst surface and also. weakens the bonds in the reactant molecules Formation of interstitial Compounds Interstitial compounds are those which are formed when small atoms lke H,C, 8, N, etc are trapped inside the crystal lattices of Certain metals. Transition metals form interstitial compounds with elements such as H, C, 8, N, ete because they can easily ‘accommodate the small non-metallic atoms due to the empty spaces inside theie crystal lattices. For example: TiC, Mn, FesH, Voss TI, ete Formation of Alloys ‘As transition metals are quite similar in size, the atoms of one metal can substitute the atoms of another transition metal in the crystal lattice. So, many alloys are possible between transition metals. Chromium, vanadium, tungsten, molybdenum and ‘manganese are used for the production of variety of steels and stainless steel, Alloys of transition metals with non-transition ‘metals such as brass (copper-zinc) and bronze (copperctin are also of considerable industrial importance. ‘Some important Compounds of Transition Elements (4) Potassium Dichromate (KxCr,0,) Preparation: Potassium dichromate is prepared from chromite ore (FeCr,0,). The various steps involved are: {i}conversion of chromite ore into sodium chromat hydroxide inthe presence of air. ‘The chromite ore is fused (heated) with sodium carbonate or sodium AFeCrs04 + BNa,COs +70," + BNa,CIO, + 2Fe,0, + CO, a sod, chromate yl) % : scanned with Camscanne gow (ti) Conversion of sodium chromate into sodium dichromate: ' ee with sulphutic acid to get sodium dichromate, 2NajCtOs + HsS0, —+ NayCr,0, + NaSO, + 1,0 ‘The yellow solution of sodium chromate fs fitered and acidified Sod, dichromate (orange) (i with a calculated amount of potassium chloride, when potassium dicho Na,Cr.0) + 2KcI + K:Ch0; + 2Nact ot dehromate orange Conversion of sodium dichromate into potassium dichromate: Hot concentrated solution of sodium dichromate is treated mate being less soluble crystallizes out on cooling Properties (Effect of change in pH The dichromate ions (Cr,0;*) and chromate ions (Cr0,") exist in equilibrium with each other at pH. {n alkaline solution, the dichromate ions are converted into chromate ions and on acidifi , back into dichromate fons €1,0;* + 20H" = 2cr0," + H,0 lation, chromate ions are converted 2Cr0, + 2H? + Cr,0;* + H,0 (il) Oxidising properties: Potassium dichromate acts as a strong oxidising agent in acidic medium since Cr,0;* ions take up seven KiCra0y + 4H;SOq— KzSO, + Cr,(SO,)3 + 4H,0 + 3(0] ‘oF, C0; + 14H" + Ge" 9 2Cr** + TH;0 woes * lodides to iodine: Cry0;" + 14H" + 61 2¢7*" + 7H,0 + 31; "HAS toS: Cr,0;" + BH” + 3H,S —» 2C1 + 7H,0 +35 * Stannous salts, Sn{Il) to stannic salts, Sn(1V): Cr0;" + 14H" + 35n”* > 2¢r°* + ‘7H,0 + 35n* Ferrous salts to ferric salts: Cr.0," + 14H" + 6Fe" > 2Cr°* + 7H,0 + 6Fe™* Structures of Chromate and Dichromate Ions oo The drorte on, OF hes evra srucwe noe ite davomae | | | [Xo ion consists of two tetrahedra sharing one comer with C-O-crbond angle of | Ch ae ps es} [o ss Potassium Permanganate (KMnO,) Preparati (i) Conversion of pyrolusite into potassium manganate: Pyrolusite is fused with potassium hydroxide in the presence of air or an oxidising agent lke potassium nitrate, otassium permanganate is prepared on a large scale from the mineral, pyrolusite, MnO;, The steps involved are: 2MnO; +4KOH +0;—"> 2K,MnO, + 24,0 potimangamate iereen) (1) Oxidation of potassium manganate to potassium permanganate: Potassium manganate solution is oxidised electrolytically to potassium permanganate, Kuno. =20° + no. dau HO = Ht + OF Atanode: 2Mn0," —+2Mn0, + 26° Atcothode: 2H" +2e°” —+ Hy The purple solution containing KMIn0. Is filtered and evaporated under controlled conditions to obtain erystals of potassium permanganate, Properties {i) Action of heat: When heated to 513K, it readily decomposes giving oxygen. 2kNnO, —*+ KsMn0y + MnO, + O, (i) Oxidising nature: KMnO. acts as a powerful oxidising agent in acdc, neutral and alkaline media, Oxidation in acidic medium: 2KMInO, + 3H,50.+ K:S0, + 2MnSO, +3H,0 +5[0] of, MnO,” + 8H" + Se”-» Mn+ 41,0 Inacidie medium, KMIn0 oxidises: + Potassium iodide to iodine: 2MnO,” + 16H! + 101°» 2M” + 84,0 + Si + Ferrous salts to ferric salts MnO," + 8H’ + 5Fe'* — min + 4H,0 + 5Fe™ § Scanned with CamScanne nisin wee, bet The paramagnetic chao sgn +80 #3000: 322 2 Ss » 42M0 EEG . 4 5C0: amnde +364 jo vam +8140 *55 sorts rors 10 C08 antnoy #364455 a gH + 5500 5108 anne #6448808 7s 340+ SNOP q sg snoy2MM rosulpotes ‘ow +64 # NO! + suphtes annde to nats ee Liat itoxiises 420 +105 ayaalae 3105+ = gy oo 7 2MnO2 » inneutrat or fant 2 anor + HO Toe T0H +6508 i oes oft: anor +3810" +H * ; ates: 4 24,0 7 5Mn0: + 4H oN + risulpates to suPhate nox +3Mn® +2#20 Ma SO « monganous sts to MnO: a oe lee om ; ganate ons sion Peangente 1 . Manganactes pra) ‘of Manganate and Permat manganate ionsare tetrahedral structures ‘he manear ergy level, Le. (n-2) Forbitals are tthe outers! waar a rents following lanthanum from cerium (Ce) t oo wrencium (Lr), 2 = 90 to from thorium (Tih) t0 1a timate (second outermost) shell and ate and per lock Elements) npr aon samen 184 - "heme Tra el cron eerste ntepeiate (N ate ye of wa coe are Se an cols ie 14 elements ol no Met 25 58721 ton eles a5 the orl ne fo = = f they forma series within the transition series (block elements ) ocuen eer seme wun nudes any dxason of annanad se closely resembles Mc anthanam thou re srthanoid. similarly, actinium s studied along with actinoiés ke ‘The Lanthanolds (Ln) ina figuration of lanthanoids is f*"* sd” 6s f + Electronic configuration: The general electronic conf 42 and +4ons In solution orn ion state of lanthanoids is +3. However, occasionally, ff empty (f), half-filled (F) or + oxidation state: The most common oxidat extra stability of fe solid compounds are also obtained. This irregularity arises mainly from the completely filed (*) orbitals. For example: configurations respectively when they attain +4 oxidation state, (a) Cerium (Ce) and terbium (Tb) attain f and fs cet (xe) f° and Tb": [Xe] 4” (i) Europium (Eu) and yterbium (Yb) attain and f* configuration respectively when they attain +2 oxidation state Eu : [Ke] 4f” and Yo™ : [Xe] 4f"* ‘Although afew lanthanoids exhibit oxidation states of +2 and +4, yet they have the tendency to revert to the oxidation state of > 13 because the +3 oxidation state is the most stable for al lanthanolds. For example, Ce" and Tb have a strong tendency to goin electrons to attain the more stable +3 oxidation state and hence are strong oxidising agents Is aqueous solution. Similarly, 7" and ¥6* have a strong tendency to lose electrons to attain the more stable +3 oxidation state and hence are strong reducing \ gents in ogueous solution. + Atomic/lonic radii and lanthanold contraction: There is a steady and gradual decrease in atomic radi (with some ‘regularties) and ionic radi of tripositivelanthanoid ions (M") on moving from La to Lu. The steady decrease In the atomic and ‘onic radi of lanthanoid elements with increase in atomic number is called lanthanold contraction. Cause of lanthanold contraction: Lanthanold contraction Is due to the Imperfect shielding of one Af electron by another with Increase in nuclear charge along the series, ‘alnatian hs we mov ‘fom one element o another slong the lnthanld series, the nulear charge increases with atomic scent aed electrons enter int the nerf oritals which have very poor sheng effect Thus, the effective ‘nuclear charge experienced by each a electron increases and the el use a inet aa lectron cloud shvinks, This results in gradual decrease in size Consequences of Lanthanold Contraction: 1) Resemblance of second and thir ee fia aa i id anton sels: esto anthanold contraction, the elements of Second and third eben lea have amos equal al and resemble eachother much more than the elements of fst and ition series. For example, the almost identical radii i pene I st Identical radi of 2r (160 pm) and HF (259 pm) is a consequence of lanthanoid (i) Difficulty in separation of lanthanoi ft anthanoids: Because of very small change in radi ofl i i Quite smiar which makes tel separation nthe pure state feu em ee 6 scanned with Camscanne yo ee Se ea * Colou ted lons: M4 ost of eis notes fr i by Rena Aarowel F Partly filed f-orbitals Mrrenet Janthanoid ions are coloured both in the solid state and in aqueous solutions. This Is due bshell respectively due tet Wanston La” 4P)and LaF) fons ae colures ue to vacant and Fly filed af Mice: due to which there is no possibilty of ff transitions. 'ghetic properties: La", "Ce" ions wil ee i Sie they have no era cet mth af canguraton and on wit a configuration are diamagnetic in nature cd electrons. Al other . other lanthanoid ions with unpaired electrons are paramagneticin nature lonisation e . nthalpies: Rerrcca ao The first fonisation enthalpies of lanthanoids are around 600 kimof” and the second about 1200 kimol FIPS err tera pce rie ate thi er er on ne ts stability due to empty (*), halt: ee completely filled (f) (orbitals. This is reflected in the abnormally low value of third fonsation enthalpy of num (4°), gadolinium (af) and lutetium (af. General Chemical Reactions of Lanthanolds Ln, ‘. La(orn, + Hh inn ‘The Actinoids ‘The chemistry of the actinol oxidation states in these elements. Moreover, investigations is limited. sds is much more complicated compared to lanthanoids due tothe occurrence ofa wide range of all of them are radioactive and therefore, their accessibility for laboratory 10 of actinoids is [Rn] 51° 6d”? 7°. The irregularities in the The general electronic configuratios ‘are related to the stabilities of the ® ” and f actinoids, ike those in the lanthanoids, * Electronic configuratior electronic configuration of the occupancies ofthe Sf orbitals. + oxidation states: The most common oxidation state of these elements fs +3, similar to lanthanoiés Howth they also exhibit vcelation sates of 4,45, +6 and 47. Thus, unlike lnthanoids, actinolds exhibit greater range of oxidation state Thisis due to cee foct that, 6d and 7s sub-shell are of comparable energies and more elecrons are availabe for ond formation gradual decrease inthe sizeof tripostive actinoid ions (M™) across the series contraction), This contraction is, however, greater from element to ns compared to Af electrons (as Sf orbitals are more diffused than 4f * tonic radii and actinoid contraction: There is @ which is known as actinold contraction (like fanthanoid element in the series due to poorer shielding by Sf electro orbitals) pifferences between Lanthanoids and Actinoids Property, Tanthanoids ‘Actinoids Besides the most common 43 oxidation state, some of them exhibit oxidation states of +2 and +3, 7) Oxidation states Besides +3 oxidation state, they show higher oxidation states of +4, +5, +6 and 4, Except promethium, they are non-radioactive, All of them are radioactive. 2) Radioactivity 3) Tendency to form oxecations | They do not form oxocaions, They form oxocations like UO," PuO.™ ate. “The earlier members of the series ave quite reactive similar to calcium but with increasing ‘atomic number, they behave more like aluminium. “4) Chemical reactivity They are highly reactive metals, especially | lin the finely divided state | | Scanned with CamScanne

You might also like