; RP. K. MALIM'S (i ramanovy, neorenrs 2oano, non mex NEWTON CLASSES Enjoys unparalleled reputation for best results in terms of percentage selection www.newtonclasses.net THE d- AND f- BLOCK ELEMENTS [DRILL ASSIGNMENT] CLASS — XI TARGET CBSE _ The d Block Elements 1. Three series of elements ae formed by fling the 34, 4d and Sd shel of electrons and these comprise the d-block elements “The block nthe perlodic table contains elements fom Groups 3-12. ‘They re often called “transition elements" because ther position inthe perodic table is between the s- and p-block elements. ‘Ther properties are transitional between the highly reactive metallic elements of thes block which typically form fan com Pounds and the elements ofthe p-black which are largely covalent. Inthe s-and p-block elements, electrons are added tothe outer shel of the atom. Inthe c-black, electrons are added tothe pen Llimate shel expanding it from & to 18 electrons. Typically the transition elements have an incompletely filed d subse Three ofthe transition metals are very abundant inthe earth’ crust: Fe fourth most abundant) (ninth most abundant) and Mn (awelth mest abundant) by weight ‘The general electronic configuration of¢-blockelementsisin~ Nd! "ns! 2, All the transition elements are metals and ae, therefore, good conductor of electrety nd hest, havea metalic ister and are hard, strong and ductile, They also form alloys with other metals. ‘Thetons of the same charge in a given series show progressive decrease in radius with increasing atomic number They have high melting and boiling points and high enthalpies of atomization The ionization enthalpies ofeach series incrances from left toright ‘Thetranstion elements usally exist in several ferent oxidation states. Compounds are regarded as stable fthey exist atom temperature, are ot oxidized by the a, are not hydrolyzed by water vapor and do not disproportionate or decompose at normal ‘temperatures Within each ofthe Groups 3-12, theresa cifference instability ofthe various oxidation tates that exist. ln general {the second and third row elements exhibit higher coordination numbers, and their higher oxidation states are more stable than ‘the coresponding fist ow elements, They exhibit two kinds of magnetic behavior, lamagnetlsm and paramagnetism and lso ferromagnet extreme form of paramagnetism. The transtion elements have an unparalleled tendency to form coordination compounds with Lewis bases, that wlth groups ‘which are able to donate an electron pair. These groups are called ligands. They form interstitial compounds. These are compounds which are formed wien small atoms like hydrogen, carbon or nitrogen, fare trapped inside the crystal latices of metals, for example, TiC, MngN, FesH, et - Many ofthe metals are sufcientl electropositive to react with mineral acids, berating H,- A few have low standard electrode Potentials and remain unreactive or noble. The ease wth which an electron may be removed from atransition metal atom (le, Is Tonizaton enthalpy is intermediate between those ofthe s-and p-blocks Many ionic and covalent compounds of transition elements ae colored. Many transition metas and their compounds have catalytic properties. Some important compounds of transition elements are potassium dichromate (K;Ci.0;) and potassium permanganate (Kun0). Office.; 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-t, Ph.; 0661-2662523, 9635508812, 7546645949 NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES ) For preparation of potassium dichromate, the chromite ore (FeCr,0,)is fused to form sodium chromate with sodium carbon ate in air which is further treated with sulphuric acid to give sodium dichromate. Since sodium dichromate is soluble in water, itis teated with KC! to form potassium dichromate. Both potassium and sodium dichromates are stiong exidzing agents Potassium dichromate mainly used in volumetric analysis i leather industry and in preparation of az0 compounds, Potassium permanganate is prepared by fusing MnO, with KOH in the presence of@ strong oxilzing agent {KNOs) which results in the formation of potassium manganate which then forms potassium permanganate in neutral or acide solution Potassium permanganateisa strong oxidizing agent and in acid solutions it forms fodine from potassium iodide, converts Fe? {oe In neutral oralkaline solutions, it conver iodide to lodate, thiosulphate to sulphate, etc itis mainly used as an oxidiz ing agent and in bieaching of textiles and for decolorization of is. ‘The Flock Elements The Flock elements ae those in which 4fand Sf orbitals are progressively filed They are formally members of Group 3 which have been separated to form another block. They are also called inner transition metals, ‘he two series of ier transition metals (4f and 5) are called lanthanolds and actinolds, e:pectiely Lanthanoids and actinoids {are unique inthe fact that they are relatively rare compared to other elements Lanthanoids ae the fourteen elements following lanthanum. (a) Their general electronic configuration isa common 6s and variable occupancy of (b) The atomieand ionic radi decrease fom lanthanum tolutetium whichis known as lanthanold contraction Mainly Lai) and Lt are observed in lanthanoies (@)_ They are silvery white soft metals but thei hardness increases with an increase in atomic number. They taensh api in at. {They are good conductors of heat and elect (e) Trvslent lantnancids are often colored. (f), They are basic in nature anc form oxides, hydroxides, hydrogen halides, et. (9) They are mainly used for making ally steel for plates and pipes (eg, mischmetad, Actinolds consist of fourteen elements following actinium, (a) These ae radioactive elements (b) Their general electronic configuration is 75? with variable occupancy of Sfand 6d subshells. (ec) The gradual decrease in the size of atoms or los fom actinium to lawrencium is called aetinold contraction, (The oxidation state ofthe elements in general is +3, buta range of states exis. (e) They ae silvery and highly reactive metals and show magnetic properties. (0) The ionization enthalpy of early actnoids slower than that of early lanthanolds. The and block elements are used in making of ste! alloys, n pigment industry, dry battery cells and as catalysts. 8.2 ELECTRONIC CONFIGURATIONS OF d-BLOCK ELEMENTS. Conceptual Questions 1. Explain why transition elements have many regularities in their electronic configuration Solution In the case of transition elements, the (n- 1d and ns subshels are involved and since the eneray diference between them Ie very less 50 the incoming electron may enter ns or (n— 1}dsubshell Hence, they show regulates in their electronic configuration. 2. Which out ofthe following is/are transition element/s and why: Zn, Au? Solution ‘Out ofthese, Au isa transition element asit contains partially filed dsubshel 8, Silver atom has completly filed d orbitals (4d) in its ground state, How can you say thatit sa transition element? (NCE) Solution ‘Tre outer electronic configuration of Ag is 4d5s'_Ag shows 12 oxidation statein addition to +1 oxidation state. In +2 oxidation state, the configuration of Aq ise? which implies dsubshel is incompletely filed and hence itis transition element 4. Write down the electronic configuration ofa) Cr, b) Cut, c)Co™, fl) Mn.) Pm (F Ce (g) Lu, TH (ncerr) 3 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2562623, 9836608612, 7646846949 NEWTONCLASSES.NET‘THE d- AND f- BLOCK ELEMENTS [DRILL ASSIGNMENT] CLASS ~ XI Solution CeEIANBe——b) Cuts(Ana? fe) COPIA (a) Me? tar Le) PmMspxelar® Ge fxe) (a) Lu: (xeaP4sd! th) TH: Rn] 5. Inwhat way ithe electronic configuration ofthe transition elements different from that ofthe non-ransition elements? (NCERT) Solution In the case of transition elements, they have partially filed d subshellin any common oxidation state. Their general configuration is (= Nid“ while the non-transtion elements have no dsubshel and havens! o ns? np! in their outermost shel 8.3 GENERAL PROPERTIES OF THE TRANSITION ELEMENTS (d-BLOCK) Conceptual Questions 1. Why does Mil) show maximum paramagnetic character amongst the bivalent ons of the fist transition series? Solution Paramagnetism is shown by the compounds having unpaired numberof electrons In the case of Mn”, the number of unpaired clectrons are five, that i, 3? whichis maximum among al the bivalent ions of the frst transition seres, 2, Why are Zn?* salts white while N?* salts are blue? Solution 2n sats are white while N* sls ae blue because Zn has completely filed d orbital whlch means no unpared clecton.s0.4-d ‘eanstion not posible Whereas nthe case of Ni, the orbitals partial filed, that 50 d-d ans s posible os or tain unpaired electrons. Giving reasons indicate which one ofthe following would be colored: Cu, VO, Sc™*, NP* (Atomic numbers of Cu = 28, =29, Se 21.Ni=28) {4") No unpaired electrons, therefore, not colored (34?) -No unpaired electron, therefore, nat colored (34%) No unpaired electrons, therefore not colored. N#*=(Gd")—Contains unpaired elections, therefore, colored. 44 Most ofthe transition metals do not displace hydrogen from lute acids. Why? Solution ‘Ametal can displace hydrogen fram dilute acids only fit has lower eduction potential or negative reduction potential, and since the reduction potential of transition metals positive, they cannot clsplace hydrogen from lute aces. 5. substance found to have # magnetic moment of 3.9 BM. How many unpaired electrons does it contain? Solution Using the formula for magnetic moment (1) = Ynin-2}, we get a9=\mavDn=3 6. Why do transition elements show variable oxidation states? Solution In the case of transition elements, the (n~ 1jd and ns subshels are involved and since the energy difference between them Is very less, soelectrons from elther (1 ~7}d or ns subshells can participate in bonding, Hence, they show variable oxidation states. 7. The melting and boing points of Zn, Cd and Hg arelow. Why? Solution All the electrons in d orbitals are pared in the case of 2n, Cd and Ha. So, the bond (Le, metalic bond) present in them is weak and hence they have low melting and boling points. |8. The paramagnetic character in 3d transition series elements increases up to Mn and then decreases. Explain why. Solution Paramagnetism depends on the number of unpaired electrons. As we move from Se to Ma, the number of unpaired electrons increases (fom 1 to 5) and so does the paramagnetic character. After Min, (due to Huns rule of maximum multiplicity) paling of electrons takes place, Thus, the number of unpaired electrons decreases and hence paramagnetism decreases Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES Which ofthe two: VIV) or ViV) is paramagnetic? Give reasons. (Atomic number of =23) Solution V atomicnumber 23% (An3dP4s* ‘Yv):[AN3a! has one unpaired electron, so its paramagnetic in nature VV): 1Ar3¢ has no unpaired electron, soit is diamagnetic in nature. (a) Ofthe ons Ag®, Co? and T*, which one willbe colored in aqueous solutions? (Atomic numbers of Ag. () teach one of the above lonk species isin turn placed in a magnetic fel, how wilt respond and why? Solution (a) Ag= (Kniss! Iki4a"® means no unpaired electro, Com tnriad’as? 1130” means three unpaired electrons. Tia TAnsas? [Ar] 3c? means no unpated eletron, Hence, Co wil be colored because it contains unpaired electrons. (b) When each one ofthe above ionic species isin turn placed ina magnetic fled, Co* will be attracted by magnetic feld because thas unpaired electrons, whereas Ag’ andi willbe repelled by the magnetic fl 1) toZn 2 = 30) the enthalpy of atomization of zincis the lowest thats, 1.26 Kimo". Why? (Ncert) Solution Enthalpy of atomization depends upon the interatomic attraction, which in turn depends upon the number of unpaired electrons. ‘On going from Se to Zn al the elements in between have unpaired electrons; but in the case of zing, the configuration is 3a" 4s, ‘which means all electrons are paired, So, interatomic attraction and hence enthalpy of atomization i the weakest fr zine 112. Which ofthe 3d series ofthe transition metals exhibits the largest number of oxidation states and why? (weer) Solution ‘The largest number of oxidation states exhibited by Mn (Z= 25) 3d°4s?.t can lose 2to 7 electrons as (n~ 1d and ns orbitals are close in energy. That is why, It exhibits maximum number of oxidation states from +20 17 (2, +3, +4, 5,46, 47) 113. The (M2"/M) value for copper i postive (+0.34V). What I possibly the reason for this? (NcerT) Solution The values the sum of enthalpy f atomization 4,H, Ionization enthalpy AH and hydration enthalpy Aya AS Cu has high 3! value and low Aj value, hence, the Z (Cu/Cu) fs positive. The high energy required to transform Cul) to Cua) i not ba anced by its hydration ethapy. How would you account forthe iegular variation of fonization enthalpies (fst and second) in the ist series ofthe transition ele ments? (NcERT) Solution ‘The oniation enthalpy should increase on moving from lft to right along the fst transition series because of increase in effective nuclear charge. However, the trend i regular on account of exchange energy which Increases as the numberof elections in configuration increases. For example, Cr has low ist ionization enthalpy because after losing an electron it acquires stable alec- tonic configuratian( 3d, while Zn has high value of ionization enthalpy due to filed stable configuration 3a 4s, After removing an electro, the removal of second electron becomes more dificult So, the second ionization enthalpy is even higher, for example, (Cras high second ionization enthalpy because the second electron has to be removed from the stable configuration of 3% 15. Why isthe highest oxdation state ofa metal exhibited nits oxide or fluoride only? (weerr) Solution The highest oxidation state ofa metals exhibited in ts oxide or fuoride form only because oxygen and fluorine are highly electro negative atoms and small in size. So, they oxidize the metal tothe highest oxidation state. 16. Which sa stronger reducing agent CF or Fe** and why? (wert) Solution Reducing character depends upon the F value. More negatives the value, more i the reducing power of the element. °(Cr"/ Ce) is-0.41V and E*(Fe™"/Fe) is 40.77 V. Hence, CP is stronger reducing agent than Fe 117. Calculate the“spin only’ magnetic moment of M*(aq)ion (2= 27) wncerr) Solution ‘Atomic number (2) of M:27 Electronic configuration of Mi 30°4s* Electronic configuration of M*: 3d” which implies thas three unpaired electrons. ‘Magnetic moment (st) = Vnin 2) 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836508812, 7546846949 NEWTONCLASSES.NET‘THE d- AND f- BLOCK ELEMENTS [DRILL ASSIGNMENT] CLASS ~ XI 118. Explain why Cu" ion isnot stable in aqueous solutions? Solution Cu*fon is unstable and undergoes disproportionation reaction. reat cut +cu u?"aq) is much more stable than Curaq) because although secon ionization enthalpy of coppers large In the case of Cu, ‘yt or Cu Is much mere negative than that fr Cus hence it more than compensates for the second ionization enthalpy of copper 19. Why are Min compounds more table than Fe" tonard oxidation to thelr +3 state? (cern) solution Inthe cas ofr, the configuration 3 whichis al led thats sexta stable Whereas. inthe case ofFe the coniguation is 34, which means tan lose one electron easly t attain extra stable configuration. Thats why, hn compounds are mre sable ‘than Fe towards oxidation to their +3 state 20. Explain brief how 42 state becomes mare and mae table in the st half ofthe fst row Hanson elements wth increasing atomie number? twcent) Solution Except scandium al other ist row tanston elements show an onldation state of «2. This i duet the lass of wo 4 electrons the rsthal.as we moveffomTi"to nthe electronic configuration changes rom 3 3 thats more and more of dra are hal filed imparting greater and greater stability to» 2 oxidation state Inthe second hal thats ftom Fe*toZ0™ the electronic Coniiguation changes fom Seto 3d. Hence the tbl of state decreases. |. To what extent do the electronic conigutations decide the stably of oxdation satesin the rst senes ofthe tans element? iustrate your answer with examples (ween) Solution Inthe case of ransion elements the oxidation tate which leads tothe formation of half or ful ile orbitasis mre sable. Mn shows +2 oxidation state because removal oftwo electrons leads to a halle configuration (A/]34°%, although other oxidation states are also possible in ths case 22. What may be the stable oxidation stat of the ransition element with the following d electron configurations inthe ground sate of theiratoms: 34, 34°, 3d and 3d? (NCERT) Solution adm adas= 5 ad 23d 4s! or dee 23. Name the oxometal anions ofthe first series ofthe transition metals in which the metal exhibits the exidalon state equal to its sroup number. (NCERT} Solution ‘The orometa anions are Cr,0;* and Cr0,* In both of them, the group number and oxidation state of Cris 6 and in MnO, the ‘group number and oxidation state of Mn is +7 24. How isthe variability In oxidation states of transition metas different from that of the non-transtion metals? Mustrate wlth examples. (NCERT) Solution Inthe case of transition elements, the variability in oxidation states due to partial filed d orbital, such that thelr oxidation states siffer by one unit. For example, Fe and Fe** and alzo the higher oxidation states ate more sable fr heavier elements fr example. Moi) s more stable than C(V. Whereas, inthe case of non-transtion elements, the oxidation state differs by two unit for exarn- pile, Pb and Pb* and lower oxidation states are more stable in heavier elements due to inert pair effect. For example, Pl is more stable than PBIV). For Mim and M™/MP systems, the E values for some metals are as follows cA'cr=—09V Pte =-04V Mn/Min=—1.20 Mo /Mai= 41.5 Fe /Fe=-04V Feet =108V Use ths data to comment upon: (a) The stability of Fein acid solution as compared to that of Cr** or Mn+. (b) Te ease with which iron can be oxidized as compared toa similar process for either chromium or manganese metal (NCERT) Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES (a) CP°/Ce™ has a negative reduction potenti Hence, Crcannot be reduced tC. Mn"/n* has large postive Evalue Hence Mn’ canbe easly reduced to Mn. The & valuefor Fe” Fs positive butsmall Hence, f°" s more table than Mn” butless stable than Cr" (b) The orderisWin> Cr> Fe 26, Predict which of thefllowing wl be colored in aqueous sluton: TH Vn, Se Mn Fe and Co? Give rasan for ech. (wcerr) Solution COnly thse fons wil be colored whch have unpaired electrons in the dsubshel Fort? the configuationis{Alad! For, the configurations tA]3¢ For Sc the configuration (a? For Mn, the configuration IB For Fe, the configurationis tse For Ca, the configurations tal34? ‘As szen rom tei configurations, ony Se” does not have ary election in the dsubshel Soi wil be colores Rest ll il eco ‘ted in aqueous solution due tod~ d ranstion. MnO willbe colored due to charge tans, . How would you account forthe allowing {a} Ofthed! speces,cr*is strongly reducing while manganese strongly oxidzng {) Coban table in aqueous solution but inthe presence of complexing reagent itis easly oxidized (6) Thea! configuration very unstable none (weenn) Solution (0), Reducing nature depends on the Eval. the E valu is negative then the metals reducing. Inte case of =" and Mn Ce" haca negative vale edition potenti thats, =-0'41V whereas Evalue for Mini postive (+ 57¥). Thats why 4 species, CP" is stongly reducing whereas manganese is strongly oxidizing {) Because Cod has a grester tendency to form coordination complexes than Clin the presence of ligands, Colts oxldzed s9.coat (<) The d! configuration s very unstable in ions because they can lose electron easly to acauted configuration and undergo lsproportonation action 28, What smean by"dlsproportionation"? Give two examples of dsproportionaion reaction in aqueous solution wcerr) Solution Disroportonaton reaction reaction in which the oxidation numberof an element increases and decreases to give eferent prod ucts Forexample nai solution Mn(Vn MnO" changes to MV inthe product MnO; and to MV) in the product MnO SMnO- + 4H" 2¢n0, + MO, +240 29, Whieh metal inthe fist series of ranstion metals exhibits +1 oxidation state mast frequently and hy? (weer, Solution The 1 oxidation states mot frequently exhibited by Cu because thas the coniguaton {a]3d"% andlosing one electron gives stable fled configuration 20, Caleuat the number of unpaired electrons the flowing gaseous ions: Mn," Vand T# Which ane ofthese ithe most stable in aqueous solution? (neeRn) Solution Nn! = 344 unpaired electrons P= 3? =3 unpated electrons 23d =2 unpaired electrons 8 =30'=1 unpaired electron Since Cr has ha filed ty configuration () ive examples ane suggest reasons forthe following festures of the transition meta chemistry: (a). The lowest oxide of transition metal is basi the highest is amphoteri/acie () The highest oxidation states exhibited in ox0-anions of a metal (NceRT) Solution (a) Asthe oxidation number of metal increases, the ionic character decreases. In the low oxidation state ofthe metal, some ofthe valence electrons ofthe metal atom are not involved in bonding. Hence it can donate electrons and behave as a base. In the higher oxidation state, valence electrons are involved in the bonding and are not available. Instead, effective nucle charges high, Hence, can accept electrons and behave as acid. For example in MnO, the oxidation state of Minis +2 which means basic and in Mn;0;, the oxidation state of Mnis-+7 which means its acidic in nature, (Oxoanion ofa metal is formed by the combination of metal with oxygen. As oxygen is highly electronegative and a strong ‘oxidizing agent, hence, the highest oxidation stat is exhibited in oxoanions af a metal, For example in MnO, the oxidation state of Minis +7. its the most stable in aqueous solution. 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836508812, 7546846949 NEWTONCLASSES.NET‘THE d- AND f- BLOCK ELEMENTS [DRILL ASSIGNMENT] CLASS ~ XU 32. Use Hund’ rule to derive the electronic configuration of Ce?” lon and calculate its magnetic moment on the bass of spin-only” formula (NCERT) Solution We know that e (2 =$8)=(Kel4/Sa'6s? and Ce? =(Xel4 Therefore, the numberof unpaired electrons =1.The magnetic moment isoiven by = SOD = JAH = 5 1.73 33, Write down the number of 3d electrons in each of the following ions: T?*,V*, Ci", Mi? Fe Fe, COM, NP* and Cu Indeae how would you expect the five 34 orbitals tobe occupied fr these hydrated ions (octahcdraD. (NCERT) Solution Ti" =3¢?, the numberof d electrons =2: occupancy of 3d orbital <3, de number fd eleons = ocapanc of 34 oral = Ce =34% thenumber of eeewons = occupancy of orb = ty =3¢7, the numberof d electrons =$; occupancy of 3d orbital = Sef, the number of deletion: 3, the umber of elecrons=5: occupancy of 3¢ orbital 3d, the number of d electrons =7; occupancy of 3d orbital =3¢7, the numberof d electrons =8 occupancy of 3d orbital = 3 d*, she number of deectons = 9; occupancy of Sd orbital = |. Comment on the statement that elements ofthe fs renstion series possess many properties ferent from those of heavier tran sition elements (NCERT) Solution (a) The atomic radius of heavier transition elements (4 and 5d series) is larger than the fst transition series ()Enthaloy of atomization of heavier transition elemeatsis higher then the ist transition seis {1 Melting and boiling points of heavier transition elements are greater than the fist ransition series. (4), lontzation enthalpy of 5 series s greater than the 4d and 3d transition sees. 35, What can be inferred from the magnetic moment values of the following complex species? ‘Magnetic Moment KalMnnCN] 22 IFettong 53 KalMnC) 59 Solution For K«(Mo(CN)g, oxidation state of Mn=x+6(-1) =—4, therefore, x=+2. Electronic configuration of Mn =3¢*4s*and that of Mn = 30° x Inthe presence of strong field CN" ligand, electrons in 3d pair up and hence the magnetic moment isles, u “ ” wocne RINT) ) ‘Therefore there is one unpaired electron, the hybridization is dsp” and inner orbital octahedral complex s formed. For IFetH,0},)", oxidation state of Fe =x-+ 6 (0)= 42 therefore, x= #2 Electronic configuration of Fe = 34°" and that of Fe” rer [Ne tt H,0 ia weak eld ligand, sono paling of electrons in 3d takes place. Also, Ihas high value of magnetic moment, which suggests presence of four unpaired electrons Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES “ » rerow (NIT) De It has sp°d? hybridization and forms outer orbital octahedral complex. For K:IMn(CN)gl", oxidation state of Mn =x +4 (-1)=-2, therefore, Electronic configuration of Mn = 3°43 and that of Mn = 3° x “ we TTT) ‘The high value of magnetic moment (5.9) indicates it has five unpaired electrons. uw “ woe (tt tittt)] be thas sp? hybridization and the complex is formed with tetrahedral geometry Textbook Exercises 1. How would you define a transtion element? List the properties associated with transition elements Solution ‘Atranstion elements defined as an element having partial filed d subshell in its common oxidation state. They comprise d-biock ‘elements. The genera configuration isn 1}4!" ns, The characteristic properties ofthe transition elements are: They ae hard have high melting and boling points, high electrical conductivity and malleabilty, exhibit wide range of oxidation states, form com= plexes, form colored compounds, possess catalytic properties form interstitial compounds and alloys 2 Comment on the following properties for transition elements: (a onic character: (b) physical properties: cstailiy of the various ‘oxidation states (d) ability to form complexes? Solution (a) The lonic character decreases wit increase in oxidation state because asthe oxidation state Increases, more and more valence shell electrons are involved in bonding, (0) Allthe transition elements are metals and ar, therefore, good conductor of electricity and heat, havea metalic lustre and are ‘hard, strong and ductile They alzo form alloys with other metals, The ions ofthe same charge in given series show progresive ‘decrease in adius wth increasing atomic number. They have high melting and boiling points and high enthalpies of atomiza tion. The ionization enthalpies of each series increase from left to right. Many ofthe metals are sufciently electroposiive to reactwith mineral acids liberating Hi Afew have low standard electrode potentials and remain unreactive. The ease with which {an electron may be removed from a transition metal atom (.e, its fonization enthalpy) is intermediate between those of the '5-and p-block elements. Many ionic and covalent compounds of tansiton elements ae colored. Many transition metals and ‘their compounds have catalytic properties, ‘lltansition elements except the first andthe last member ofthe series, exhibit a number of oxidation states. Thsis because the transition elements have their valence electrons in two different orbitals Le, (n-1)d and ns. Since there is very litle dfer ‘ence in the energies ofthese orbitals, both eneray levels can be used for bond formation. In simple compounds, the two ‘electrons from ns orbital ofa transition element are used to give an oxidation state of +2 and the (9=1)d electrons remaln unaffected. But the higher oxidation states lke +3, +4, +5, +6 and +7 correspond tothe use of all 4s and 3 electrons inthe transition series of the elements. n the excited state, the (n-1}d elections become bonding thus give variable oxidation states tothe atoms. ‘The transition metals form a large number of complex compounds in which the metal ons bind with a number of anions or ‘neutral species called ligands. These ligands donate a pair of electrons tothe metal ion to forma caordinate bond, This tendency ‘0 form complexes is due to comparatively smaller sizes of transition metal ions, thee high tonic charges and availabilty of orbital for bond formation 3. Why do the second and thied row transition elements resemble each other much more closely than they resemble the fist row? Solution ‘The second and third row transition elements resemble each other much more closely than they resemble the fist row because 35. ‘the number of shel increases, the atomic radius increases. The atomic radius of second and third transition series are nearly the same ‘due to lanthanoid contraction The expected increase in atomic size with inereasing atomic numer is compensated by decreste in ‘atomic radi due to intervention of 4F orbitals which ae filed before the Sd orbitals. Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NET‘THE d- AND f- BLOCK ELEMENTS [DRILL ASSIGNMENT] CLASS ~ XI |4, Explain the correlation between in size ad the number of d electrons. Solution ‘As the number of electrons increase, the size ofthe ion decreases. Tisis because the electrons are pulled move towards the nucleus le to poor shielding effect of electrons. 5. Explain why certain igands such as F>tend to bring out the maximum oxidation state of an element, while others such as CO and dipyridy| bring out the lowest oxidation states. Solution F tend toring out the maximum oxidation state ofan element, while others such a CO and dipyridl bring out the lowest oxidation states because uorineissmallin size and highly electronegative. So, the element tends to lose more electrons and gain higher oxida ton sats, 6. Give examples of (a) Two transition metals used a catalyst (b) Three transition elements used in forming alloys. (c)_ Two interstitial compounds of transition metal. Solution (a) Vanadium and cobat. {() Chromium, vanadium and molybdenum, {q)_ Titanium hydride (Ti) and manganese nitride (Mn). - Justify the following: {a} Transition metals can exhibit very low oxidation states such as +1 and, (b)Fehas higher melting point than Cu (el NP* haslower magnetic moment than Co. Solution ))Tansition metals can exhibit very low oxidation states such as +1 and O due tothe stability associated with half and completely filled ¢ orbitals For example, in the case of Zn (2 = 30, the oxidation number i zero because it has filed d oPital which iz extra stable. Aza inthe caze of Cr (Z=24), losing one electron wil give ita stable halilled configuration, (b)Fenas four unpaired electrons (3 4) while in the case of Cu (3d 4s) there i only one unpaired electron. Now, the strength ‘of metalic bonding depends upon the number of unpaired electrons. Greater the number of unpaired electrons, greater isthe ‘metalic bonding, and hence greater is the melting point. (q)_Inthe case of Ni" (2, there ae two unpaired electrons while in the case of Co (3d), there are three unpaited electrons. More the number of unpaired electrons, greater is the magnetic moment. So, its greater for Co™ or in other woeds, NP" has lower ‘magnetic moment than Co. Give reasons fr (8) Transition metas form complexes. {b} C042 Is srongly oxidizing while MnO} Is not. {)_ Chromium group elements have the highest melting points in their respective series Solution (0) Transion metal frm complexes because they ae smalin sae, heve high onc charge have igh chargesiae ati, tei dort als ar vcant 0 a8 to sczep the lone pals donated by ligands (b) CP (ondation state of Crim CrOj can be changed into C°" by guning electrons and Cia very stable state of Cr Hence, is strong oridzng agent. While in MnO; Minin 46 oxidation sate and ths oxidation tates vey unstable and sit gets oeized to MnO; Therefore, tacts asa reducing agent. {c) Because Cr has halfflld stable d configuration an maximum number of unpied electrons, that i 5. Now, the stwength of metal bonding depends upon the numberof unpated electrons. Greater the number of unpaired electrons. greater isthe metalic bonding and hence greater isthe melting point. ‘8. What elements would you expect rutherfordium atomic number 104) and the elements of atomic nribers 105, 106, 107 and 112t9 resernbe? Solution Rutherfordium (7= 104 electronic configuration fs (56a 752 DDubnium (2= 105) electronic configuration i [RS 6? 7° Seaborgium (2106 electronic configuration i [Rn5h* a7 Bohwium (Z= 107) eletronic configuration sist 6°75? Ununbium (= 112) electronic configurations ils" 6a'° 75? Althete elements belong 06d transition series as they have electonsin orbitals thats they are block elements. Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NET10 R. K. MALIK’S NEWTON CLASSES 10. Which out the following will be colored and why: Ag,S0,,CuF CuCl, MgCl? Solution CuF, will be colored because it has one unpaired electron due to which it undergoes ad-d transition. In AgSO, and CuCl, Ag” and Cu" do not contain unpaired electrons in d orbitals and in Mal, Mg does not have d orbitals. So inal these compounds ded trans tions are not possible and the compounds are not colored. ‘Account forthe following: {a} Atomic radius of Cu is greater than that of, but te ionic radius of Cr" is greater than that of Cu™ (b) In ransition metals the melting points fst increase, show a dip inthe midale and then decrease Solution (2) The electronic configuration of Cis 3494s. As the dobital is completely filled which meansit does not contain any unpaired electron Whereas in the case of Cr, the configuration is 3d 4s, means d electrons are not paired. inthe case of Cu, the ded «electron repulsion is more than in Cx. That is why the atomic radius of Cus greater than that of Cr. ter losing two electors, the configuration of Cu becomes 3, while inthe cae of Crit becomes 3. Inthe ese of Cu", d-drepulson becomesiess due to the presence of one unpeited electron and also the attraction is more due to 29 protons. While in the case of Cr, three Lnpaired electrons are atracted by 24 protons Hence. the ionic radius of CF" is grater than tha of Cu” ‘The strength of metalic bonding depends upon the numbe of unpoired electrons. Greater the numberof unpaired elections, (i, Cu? (aq) faq) (©), How would you account forthe following: {i) The oxidizing power of exoanions isin the order VO} Explain the folowing observations: Ui) Transition element are known to form many interstitial compounds. Li) With the same a configuration, Cr" ion seducing while Mn" ion is oxdiing. ii) Theenthalpiesof atomization of he transition elements are quite high. 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836508812, 7546846949 NEWTONCLASSES.NETTHE d- AND f- BLOCK ELEMENTS [DRILL ASSIGNMENT] CLASS ~ X11 Fe?" (aq)+ MnO (aa) + 8H"(aq)—> Mn? (ag)+5Fe™(aa)+ 44,0 (0% (aq)+ 14 (acy +66" 9 2CP* (aq) +7H,0 “Transition metas form large number of itesttal compounds in which small atoms such as hydrogen, carbon, boron and rittogen occupy the empty spaces in their latices. They are very hard and rigid They have high melting and boing points For Cr, the +3 oxidation states more stable than +2 state. Thus, C1" changes to Cr” and itbehaves ke a strong reducing Agent. However, for Mn, the +2 oxidation states mare stable than +3 state, So, Mn changes to Nn#* and behaves asa strong oxidizing agent. li) The transition elements exhibit high enthalpies of atomization as theyhave large number of unpaid eecvons and sal ie. ‘Due tothe presence ofthese electrons they have stronger interatomic interaction and strong bonding between thei atoms 4. (a) Complete the folowing chemical uations: ii C,O% (a) +4519) on)» )tnOys)s KOH ag) +05» {b) Explain the folowing observations: {)-Transtion metas form compounds which aeusaly colored (i) Tanston meas exible vale oxidation sates. {i Theactnods exits greater ange of excation tats than he lanthanols (c9s€2009) i) 0% taq)+3H,51g)+ 8H” (aq) 2Cx"*(aq) 35()+7H40. {i 2N1n0 Js) + 4KOH(aq) + 0,16) > 2K,4nO4(aq) + 24,0 (i) Transition elements form compounds which are usually colored due to excitation of electron from lower energy d atomic orbital to higher energy d atomic orbital the same subshell The frequency ofthe light absorbed les nthe visible region. ‘The color observed Is due tthe color ofthe complementary light. 0) Inthe case of transition elements, the (n~1)dand ns subshel2re involved and since the energy difeence between thems very less 0 electrons from ether in 1d rns subshels can participate in bonding. Hence they show variable oxidation states. ii) Actinoids exhibit larger numberof oxidation states because in these elements, the energy gap between Sf, 6d and 75 subshells is very smal. So all their electrons can participate in bond formation. Whereas, lanthanoids show a limited numberof oxidation states because the energy gap between 4F and Sd subshells i large and all the electrons in these subshells cannot participate in bonding, Assign reason fr the following: (a) The enthalpies of atomization of transition elements ae high. () The transition metals and many of thelr compounds act as good catalysts [e)_ From element to element the actinoid contraction f greater than the lanthanold contraction, [) The vale forthe Mn?" /Mn?* couple s much more positive than that for CP"/Cr". (e) Scandium 221) doesnot exhibit variable oxidation states and yet tis regarded a a transition element. (CBSE 2008) Solution {a} The transition elements exhibit high enthalpies of atomization because they have lage numberof unpaired electronsin ther atoms because of their smaller size. Due tothe presence ofthese electrons, they have stronger interatomic interaction, Hence, they have trong bonding between their atoms, (©) Many transition metals and ther compounds act as catalysts. The catalytic activity ls due to thelr ablty to exhibit multiple oxida- tion states, They form unstable Intermediate compounds and provide a new path with lower activation energy For example, V,0s is used in Contact process to manufacture suiphuric acid (el. Aetinold contraction I similar to lanthanoid contraction. Actinoid contraction takes place because of poor shielding by 5 le: {tons and lanthanoid contraction is caused by poor shielding of 4 electrons As the shielding caused by 4 electrons is slightly better than 5f electrons, more contraction is observed inthe case of actinoid () The ll flled and hal-led orbitals are more stable. In Vn, two clectronsare present in 4s orbital and 5 electrons are presentin 3d orbital. Ate losing two s electrons, Mn has 3d° configuration in which the orbital is exactly halle, becomes dificult ‘to ake out this extra electron. Therefore, much greater eneray is required for this (e).Anelement scolled transition element fitcontainselectronsin the dorbtalin ts ground or common oxidation state Scandium (2=21)isa transition metal as thas incompletely filed 3dorbitals inthe ground state (3). ‘Additional Questions 1. Chromium i typical hard meta while mercury i liquid. Explain why? Solution ‘Chromium is typical hard metal, hile mercury i liquid because the case af mercury the d orbitals are filed, which means weak metalic bonding and inCrthed orbitals are half filed so, ithas trong metalic bonding Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETa R. K. MALIK’S NEWTON CLASSES 2, The £ values in respect ofthe electrodes of chromium (2= 24), manganese (Z= 28) and iron (2 = 26) are C"/CH* —-04 V, Mn**/ n#*-= +1. Vand Fe*/Fe* » +038. On the bass ofthe above information compare the feasbltes of further oxidation of thei 2 oxidation states Solution "Negative £® value means thatthe element can be oxidized easly Positive value of Mn'*/Mn* indicates that it Is more stable in +2 ‘oxidation state So, the order of stably of +2 oxidation states Cr* < Fe” < Min or the ease of oxidation from-+? state to + states inthe order CF Fe? > Mn, 3, White all possible oxidation states ofan element having atomic number 25, Solution ‘The electronic configuration of element with atomic number 25 is, Mn = Ar]3¢* 452. The possible oxidation states are +2, +3, +4, +5, 46.47 “4, Why is +2 oxidation state of manganese quite stable while the same is not true for ron? {Atomic number of Mn = 25, Fe= 26] Solution Inthe case Mn, losing two electrons wil gve stable half filed d configuration, thats, 3¢° while this is not true for ron Losing only single electron will give ton a stable configuration, thats, 3. 8.4 SOME IMPORTANT COMPOUNDS OF TRANSITION ELEMENTS. Conceptual Questions 1. Inthe titration of Fe’* ions with KM. in acidic medium, why dilute H,S0, is used and not dilute HCI? Solution Dilute HCI cannot be used in the ttation of F'* ons with KM, in cic medium because it wil be oxidized to Cl, and H0 by Kin, whereas H550, is not oxides by KM, 2. Give the relationship between the equivalent weight and molecular weight of KMnO, in (a acid, (b) alkaline and (c) neutral mea, Solution {a} Acidicmedia Mn0g + 8H" +5e°—>Min#* +440 Equivalent weight =Molecular weight5=158/5 =31.6 () Strongly alkaline media Mn0z +e" Mn03- Equivalent weight=Molecular weight = 158 Weakly alkane media Mn0;+2H,0+ 36° > MnO, +40H" Equivalent weight=Molecular weight /3 = 158/3 =5267 (e)_ Neutral media MnO;+2H,0 +36" MnO, + 40H" Equivalent weight=Molecular weight/3 = 158/3 = 52.67 3. Why isKinO, used in cleaning surgical instruments in hospitals? Solution Fon, is used in cleaning surgical instruments in hospitals because Its adsinfectant and i also used a8 a germicide. |& Whats the effect of pH on the solution ofK,Cr,0; solution? Solution Lotus consider the following reaction Gr,0}> + 0 — 2103+ 2H* Dicomateion——Chvomateon (On increasing the pH of the solution orn other words decreasing the concentration of H” ions according to Le Chatalir’s principle ‘action proceeds inthe forward direction giving yellow chromate solution Whereas, on decreasing the pH ofthe solution or when the ‘encentration of Hons is increased, the reaction proceeds inthe backward direction and gives an orange-red dichromate salution, Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETTHE d- AND f- BLOCK ELEMENTS [DRILL ASSIGNMENT] CLASS ~ XI 5. Why is there a covalence between Mn and oxygen in permanganate ion? Solution In permanganate io, there isa covalence between Min and exygen because MnO, undergoes 5p” hybridization In which oxygen ‘atoms are arranged tetrahedally around manganese, (6. Describe the oxidizing action of potassium dichromate and write the ionic equations fo its reaction with (2) iodide, (b) ronal) solu= tion and (eH. (CERT) Solution ,C,0;is a powerful oxidizing agent. n presence of dute H,S0, one molecule ofK,0, ges thre atoms of oxygen or inion reaction C0} ion takes up electrons and acta stong oxdzing agent. K,C10, +4H,$0, 9,50, +Ch{$0,), +4H,0 +30 o yo} + aie 466° 20°" +7140 (0) lode OF bait 46m 9 260" 4 74,0435 (2) ond solution OF + Fe +14h! ace + 6Fe +7440 fa Hs CO} +08 4 3445-92cr* 674,035 Textbook Exercises 1, Give chemical reactions forthe following: (a), An alkaline solution of KMnO, reacts with an iodide. Ub) K,Cr,0, s heated with sodium chloride and concentrated sulphuric acid (el. Raided KMn0, is heated with oxalic acid Solution (a) 2k0dn0, +H,0+KI->2Mn0, + 2KOH+ KO, (0) K;ChO, +6NACI+ 6H,50, -»2Cr0,CI, + 2KCI+ 6NAHSO, +3H,0. e)_ 2k0dn0, + 34,50, +5C3H,0, ->K:50, +2MNSO, + 8H0+10CO, - Complete the following equations: (al C0} (aq)+ H,Sig)—> (b)_Fe’*laq) + MnO;laq——> —(c)_ MaOj{aq)+ 5,03 "(aq)" Solution (a) CO} + BH" + 3H,S > 260” 4740435 (bo) 10Fe# + 2nno}- + 16H" 2Mn* + 8H,0+10Fe* (c)_ 8Min0} + 38,03 +H40-+ahn0, +6503" +204 Previous Years’ CBSE Questions (a) What may be the possible oxidation states ofthe transition metals with the fllowing d electronic configurations inthe ground State of thet atoms: 34°45, 3d°4s! and 3cP4s". indicate relative stbilty of exidation states in each case ) Write steps involved inthe preparation of) Na;CrO, from chromite ore and () K,MnO, from pyroluste ore. (CBSE2008) Solution (a) Ina transition series, those oxidation states are stable which lead to exactly halffiled or completely-filed d orbital For3d4s? Oxidation states:42,43,+4,45 Stable oxidation states:+4,+5, For3d'4s? Oxidation states:42,+3,+4,45,+6,47 Stable oxdation states: +2, 47 For3d'4st Oxidation states: 12,43, 4,46 Stable oxidation states: 42,3, {1b} (The powdered oe is heated with sodium carbonate and quick ime in the presence ofa to get yellow colored sodium chro> mate Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES AFeCrs04 + 8NajCO3 + 70, ——> BNajC10, +2Fe,03 + BCO, Chromite ore Sedum chromate (i) Potassium permanganate canbe prepared by the fusion of pyrolusite ore (MnO, with an alkali metal hydronde (KOH) and ‘an oxidizing agent such as KNO,, This gives dark green K,MInO, which alsproportionates in a neutral a aie solution ro dive permanganate. MnO, +2KOH +KNO, >K,MnO, +KNO, +H,0 MnO} + 4H" 204 + MnO, +2440 Commercial ts prepared by the alkaline oxidative fusion of MnO, followed by the electrolytic oxidation of manganate Vi eS a mF Manganate lon ripe Sof Permagante ion MnO 8.5 THELANTHANOIDS Conceptual Questions -Whatie the general vend ofthe lonization enthalpies inthe lnthanolds? Solution The ionization enthalpies increase from lanthanum to lutetium due tothe decrease in ther sizes, However, the decrease isnot very prominent. 2. One among the lanthanoids, Cll) cen be easly oxidized to CelV) atomic numberof Ce = 58). Explain why? Solution e(l) has the configuration 456s, After loss of one electron it will acquire stable configuration and the oxidation number will change toW.Thatis why, itcanbe easly oxidized 10 Ct). 3. Why do 2r and Hfor Nb and Te exhibit similar properties? Solution In general the size of the atoms increases down the group wit increase in atomic number. However, de to lanthanoid entation, the atomic sizeof any element ofthe third transition series is nearly same as that of the corresponding element in fourth wranstion series. Thus the sizeof atoms of Zr 2= 40) and Hf (2= 72) and that of Nb (Z = 41) and Ta (= 73) are similar and they exhib simi properties 4. Which out ofthe two, La{OH); and Lu(OHy is more basic and why? Solution La(OH), is more basic than LulOH), because according to Fajans'ule. the smaller the size ofation and larger the sizeof an anion, ‘greater ists covalent character. As the sizeof anthanoid ions decreases from La” to Lu, the covalent character ofthe hydroxides increases and the basic strength decreases from La(OH}), to LUOH), 5. Why are Sm ut and Yb ions in solution good reiucing agents but n aqueous solution of Ce" sa good oxidiuing agent?” Solution ‘The most stable oxidation states of lanthanoids i +3. Hence, joni the +2 oxidation state tend to change to 3 oxidation state by loss ofan electron and are good reducing agents. ons in +4 exdation state tend to change t0+ oxidation state by gaining an ele: ‘ron and are good oxidizing agents. {5 What ae the diferent oxidation states exhibited by the lanthanids? (weer) Solution ‘The typical oxidation state exhibited by lanthanoids is +3, while +2 and +4 oxidation states are also exhibited by some ofthe ele: ‘ments. For example, Eu shows an oxidation state of +2 and Ce shows an oxidation state of +4 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836508812, 7546846949 NEWTONCLASSES.NETTHE d- AND f- BLOCK ELEMENTS [DRILL ASSIGNMENT] CLASS ~ X11 15 17. What are alloys? Name an important allay which contains some of the lanthanoig metas. Mention is uses. (NCERT Solution ‘An lloy is @ homogenous mixture of two or mere metals or metals and non-metals. An important alloy which contains 95% lantha ‘old metal and 59% Fe along with races ofS, C, Ca and Als mischmetal. It is used in Mig-based alloy to produce bullets, shells and lighter fins {8 Name the members of the lanthanold series which exhibit +4 oxidation state an those which exhibit +2 oxidation state. Try to cor relate this typeof behavior ith the electronic configurations ofthese elements. (NCERT) Solution ‘The +4 oxidation state is exhibited by Ce, Pr N6, Tb and Dy. They will lose four electrons to acquite stable configuration. For exam, the configuration of Ce is el 4F #54652, which on losing four electrons will acquite stable gas configuration of Xe. The 12 oxidation sate is exhibited by Nd, Sm, Eu, Tm and. They vil lose two electrons to get stable configuration. For example. the configuration of ui ke] 4F” Se 6 which on losing two electrons will have electronic configuration [Xe] 4'5d°¢s! Since the Fshell IshaFflled, there is extra stably. Textbook Exercises 11. Name the lanthanoid elements in the correct ordet, and giv ther chemical symbols, atomic and electronic structures Solution Thame ofthe vanchanoid Symbol “Electron Structure Lanthanum a Presa est Cerium ce he] 4? 50° 6s Praseodymium Pr he) 4P 50° 652 "Neodymium Ne me} 5d? 65? Promethium (radioactive) Pm ela? 5426s" Samarium sm ear sd 62 Europium eu [ne] 47 506 Gadolinium Gd (ea a 6s? Terbium To De] 4F? 54% Dysprosium vy Pte] 4F?° sd ot Holmium Ho (fe) a7" 50° 6s bia & te af 549 6 Thalium ™m Me} af? 5d 6s? Yererbum vo ine af 5? 2 Lutetium w 7” (Xe) 4 5d 62 2, Imwhat way are the observed oxidation states of the lanthanoids related to ther electronic structures? Solution The electronic structure decides the oxidation tates ofthe lanthanoids. For example, Ce has the configuration [Xe 4° Sf é?, which ‘on losing four electrons will lead to stable noble gas configuration of Xe While in the case of Tb the general configuration i [Xe] 4F? 53 6, which on losing four electrons wil give 4f” configuration which has extra stably due to hal-led occupancy 3. What isthe lanthanold contraction? What effect does it have on the chemistry oflater elements? Solution “The regular decrease inthe atomic and ionic radi of lanthanoids with increasing atomic numbers known as lanthanold contraction. his consequences areas follows: (a) There is dlitficulty in separation of lanthanoids because due to lanthanold contraction their chemical properties become very similar, ‘Theres similarity in the size of elements belonging to the same group of second and third transtion series, thatis, the siz of any atom of tied transition series is nearly the same as that ofthe element lying in the same group of second transition series. Te elect on the basic strength of hydroxides: La(OH), fs more basic than Lu(OM), because according oFajans ule, the smaller isthe sizeof cation, larger isthe sie ofan anion, and greater sts covalent character. s the sizeof lanthanoid decreases from La** to Lu es covalent character increases andthe basic strenath decreases. Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NET16 R. K. MALIK’S NEWTON CLASSES 44. Work out the number of unpaired electrons inthe ground state ofthe following lons: La, Ce, Lu, Yb, Ga, Eu Th Solution La Ike] has no unpaired electron Ce: Xe} has no unpaired electron Lu? [ke] 4f has no unpaired electron ‘Yo: [Ke] 4f has no unpaired electron 4°": [Xe] 4F” has seven unpaired electrons Eu: Xe] 4/7 has seven unpaired electrons Tht: [Xe] 4/7 has seven unpaired electrons What are inner transition elements? Why are they so called? Give thelr general electronic configuration, Solution Inner transition elements are those in which the last electron enters (n ~ 2) orbital and they form a transition series within the d block elements. They ae called so because the last electron enters into inner penultimate energy level. Tele general configuration is(n—2 (nnd ne, 6. Inwhat ways does the filing ofthe 4f energy level affect the rest of the pelodic table? Solution Due tothe filing of the 4feneray level the elements belonging to same group of second and third transition series are similar in size, Hence, they exhibit similar chemical properties, ‘Additional Questions 1. Briefly explain why electronic configurations of lanthancids are not known with certainty Solution ‘The electronic configurations of lanthanoids are not known with certainty becouse in the ease of lanthanolds, the Gs orbital remains filed with two electrons while 4nd Sd subshells are vey close in energy so thatthe electrons can easily jump from 4f 10 5d or from Sd tof. Further itegularities in electronic configurations are also relate to the stablities of, #7 and #™ occu pancy of forbitals. - Why isthe separation of lanthanoid elements dificult? Solution Due to lanthanoid contraction, the chemical properties of lanthanoids become very similar and also change in atomic rion ais very small which makes it ficult co separate ther, 3. Explain why lanthanoids are paramagnetic in nature? Solution Paramagnetism arises due to presence of unpaired numberof electrons Alllanthanci contain unpaired numberof electrons with the exception of La and tu. Give reasons for each ofthe following (a) Size of trivalent lanthanoi cations decreases with increase In the atomle number. (b) Transition metal fluorides are ionic in nature, whereas bromides and chlorides are usually covalent in nature. (el. Chemistry of all the lanthanoids is quite similar. Solution (a) ‘Size ofrivalentlanthanoid cations decreases with increase nthe atomic number due tolanthanold contraction. Ina lanthanold seties the electron fs added to the same inner 4fsubshell Asa result the atraction onthe eletrons by the nucleus increases and this tends to decrease the size Als, there san imperfect shielding of one election by the other due to shape of orbitals, hich is unable to counterbalance the effect of increased nuclear charge. Therefore, the net result i a contraction inthe sre though the decrease is very small Ionic character of transition metal halides follows the order M-F> M-CI> M-Br because the electronegatiity decreases in the ‘order F > Cl> Br. Hence, the transition metal fluorides ar ionic in nature, whereas bromides and chloride ae usually covalent in (Chemistry ofall the lanthanoids is quite similar due to lanthanoid contraction and also because the electrons are added into inner 4fsubshell, ‘5. The outer electronic configurations of two members ofthe lanthanoid series areas follows: 4! Sa 6s? and 4 Se? What are their _atomnic numbers? Predict the oxidation states exhibited by these element in their compounds, Solution ‘Atomic number of fist lanthanold = 58(Ce): (Ke sa" 6s? Oxidation states: +2, +3 and +4 ‘Atomic number of second lanthanid = 63Eul[Xel4? 5c? 6s? Onidation states: 42.3, 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836508812, 7546846949 NEWTONCLASSES.NETTHE d- AND f- BLOCK ELEMENTS [DRILL ASSIGNMENT] CLASS ~ X11 8.6 THE ACTINOIDS Conceptual Questions 1. The electronic configurations of atinod elements are not known with certainty. Explain. Solution In the case ofactinoids, Sf and 6a subshels are involved and the energy gap between them I very small so thatthe electrons can easly mp from 5fto 4d or vce versa Further integularties in the electronic configurations ae also related tothe stables of f°,” and" occupancy of 5 orbitals. Asa resul, they show alge number of oxidation states and ther electronic configuration cannot be stated with certainty, How would you account fr the fact that actinoids exhibit a larger numberof oxidation states than the corresponding lanthanids? Solution Actinoids exhibit larger numberof oxidation states because in the case of actinoids, the energy gap between Sf 6 and 7s subshells isvery small So al ther electrons can participate in bond formation. Whereas lanthanoids show aimited numberof oxidation states because the energy gap between 4f and Sd subshelsis large and all the electrons in these subshells cannot participate in bonding Compare the chemistry of actinoids with that of the lanthanolds with special reference to: (a) lectionic configuration, b) oxidation slate (¢ atomic and ionic sizes and (d) chemical reactivity. (NCERT) Solution | Electronic configuration: The general configuration of lanthancids is [Xe)t"“*5e-'6s? while for actinoids itis [nst"“Mee-"7 (b) Oxidation states: The oxidation states shown by lanthanoids are limite, thats, +2, +3, +4 ou of which #3 i the most common while in the case of actinolds the energy gap between Sf 6 and 7s subshels is very small Soll their electron can participate in ‘bond formation. Hence, in addition to +3 oxdation states, they show lage number of ther oxidation states, that 54,15, +617 (e)_ Atomic and lonic sizes: There Isa decrease In atomic ad ionic sizes (in +3 oxidation states) ofboth lanthanoids and actinoids ‘with inereasing atomic number. Inthe case of lanthanoids, this decrease is called lathanold contraction while inthe case of ‘ctinolds this decrease is called actinold contraction, Actinold contraction is greater than lanthanold contraction due to poor shielding by Sf electrons in the actinoids as compared to that by electrons inthe lanthanoids ‘Chemical reactivity: Lanthanolds combine with hydrogen. They form carbides on heating with carbon and form halides on| heating with halogens. They eact with dilute acids to liberate hydrogen. They form oxides of the general formula M,O, and hydroxides ofthe general formula M(OH), which are basic in nature. ‘Actinoids react with boiling water to give a mixture of oxide and hydride. They combine with almost all the non-metals and are attacked by hydrochloric acid. The effect of HNO, i very small due tothe formation ofa protective layer on them. They do not react with alkalis. “4 Which isthe lst element inthe series ofthe actnoids? Weite the electronic configuration of his element. Comment on the possible ‘onidation state of this element (weeRT) Solution, “The last element inthe series of the actinolds Is lawrencium (2 = 103). ts electronic configuration I: [Rn 6d 75%. The possible ‘oxidation sates +3 (attained by losing one 6d and two 7s electrons) 5. Wite the electronic configurations ofthe elements withthe atomic numbers 61, 91,101 and 109. weert) Solution [Atomic number 61: (Promethium, Phas electronic configuration Xela Se 6s ‘Atomic number 9: Protactium Pa) has electronic configuration [Rn] 5/6! 75? ‘Axomic number 101(Mendelevium, Ma) has electronic configuration tRn] 5” 6? 75? ‘Atomic number 103:(Meitnerum, Mt) has electronic configuration [Rn] Sf" 2s¢ Textbook Exercises 1. Name the actinoid elements in their corect order, and give their chemical symbols. Solution Element Name Actinium ‘Thorium Protactinium Uranium Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES ‘Element Nome ‘Atomic Number “Neptunium UND so Plutonium Pu 9% Americiums am 95 curium cm 98 Berkelium 8k 7 Calfornium c 98 Einsteinium 5 cy Fermium Fm 100 Mendelevium md 101 Nobelium No 102 Lawrencium ue 103 2. Which +3 lon has its shell hal full What oxidation states do the preceding and succeeding elements show? Solution ‘Americium {Am?"I (Rnl5f” 6d? 732 and Curium [CmKORnIS? 6d 759. The preceding and suceeeding elements show exidation slates of +3, +445, 46,47. Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NET