R. K. MALIK’S JEE (MAIN & ADV.), MEDICAL + BOARD, NDA, IX & X Enjoys unparalleled reputation for best results NEWTON CLASSES in terms of percentage selection www.newtonclasses.net THE d- & BLOCK ELEMENTS [CLASS — XII] [NCERT CHEMISTRY SOLUTIONS] SOIT 1, Transition elements: Elements belonging to d-block lying between s and p-blocks are called transition metals. {(n ~ 1)d“ n 3°? J . Transition series: 1" series (34); n= 4 (;S¢~ 39Zn) 24 series (4d); 1t = 5 (oY — gC) 3" series (Sd); n = 6 (57L.a, 7Hf - Hg) 4 series (6d); n = 7 (g9Ac; yg4Ku onwards) Exceptional configuration of Gand Cu in 1" transition series: aaCr : [Ar]}® 4d 4s! oC : [Ar]"® 3d? 457, . Transition elements in terms of electronic configuration = Elements in which atoms or ions in their common oxidation states have incompletely filled d-subshell. For this reason, Zn, Cd, Hg are not transition elements. General Trends in Properties of Transition Elements: (@ Atomic and ionic radii: Atomic radii decrease in the series with increase in atomic no. because nuclear charges increases. Radii of 2"! and 3" transition series metals are nearly same due to lanthanoid contraction after lanthanum (Z ~ 57). (i) Metallic character: Both n s and (n ~ 1)d electrons participate. Greater the no. of unpaired ©, stronger are the metallic bonds. That is why Cr, Mo and w are hard whereas Zn, Cd and Hg are soft (Hg is liquid). (i) Melting and boiling points: High melting and boiling points. In any series, melting point first increase, rise to max. and then dec. This is of unpaired e”. Thus Cr, Mo & W have maximum melting points in their respective series (W > Mo > Cr). Melting point of aM < a6Fe or ysTe< Ru is due to pressure of half filled d-subshells of Mn and Teand hence are stable and form weak metallic bonds. Densities: Increases along a series because atomic size decreases whereas atomic mass increases Ionization enthalpies: Their ionization enthalpies are higher than s-block and less than p- block elements. They generally increase along the series as nuclear charge increases. The first ionization enthalpies of Zn, Cd and Hg are very high because of fully filled configurations. Standard electrode potentials (E*): In solid state, stability of 0.5 can be predicted from ionization enthalpies. For example IE, + IE, for sic Pt Hence, Ni(ll) compounds are more stable. Hence Pr(V) compounds are more stable. Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0661-2682623, 9635608812, 7546846949 NEWTONCR. K. MALIK’S NEWTON CLASSES F°(M*/N) donot show regular trend because I E, +E, and sublimation enthalpies do not show regular trend. In 3d series, only Cu has +ve E°/(M"*/N) becatise the sam D sub H+ D, His not balanced by Djyg. H. That is why it does not react with acids to give H, gas. E° (M™*/M”)) studies show that E°(SC*/SC” is very low showing stability of SC” E? (Mn*/Mn*) is high because of stable d° for Mn”. E°(Fe*/Fe”) is low due to extra stability of Fe (d°). For these reasons, Mn® and Co™ are strong oxidizing agents aqueous solution whereas Ti”, V* and Cr” are stongest reducing agents. Oxidising states: The first element of each series (SC, Y, La) shows an oxidation state of +3. The last element of each series (Zn, Cd, Hg) shows an 0.5 of +2 (Hg also shows + 1). All other elements show a no. of oxidation states, +2 being most common (due to 1") higher oxidation states are also found in concentration state and oxoandous e.g., Mn (VI) in MnO, and Or (VI) in CrO?? and Cr," . Oxygen stabilizes higher oxidation state more than flourine e.g Mn forms Mnf, but forms Min;O;, Catalytic properties: Most of the transition metals and their compounds are used as catalysts. This is mainly due to their variable OS. Reactant reacts with catalyst in one OS to form an intermediate in another OS. which reacts with catalyst in one oxydation state to form as catalysts. Coloured ions: Most of the transition metal compounds are coloured in solid states and in aqueous solution. This is due to presence of incomplete d subshell. In presence of anion, d subshell splits into two sets, one with lower energy called fy, one other with higher energy. For example, Cu” salts look blue as they absorb red colour or Ti* complexes are purple because they absorb yellow colour. Sc” and Ti* compounds are colourless because they have completely filled d orbitals. ‘Magnetic properties: Compound of transition metals are generally paramagnetic or some of them are dimagnetic. Paramagnetism is due to presence of unpaired & while dimagnetism is due to presence of no unpaired Why KMnO, cannot be used in presence of HCl or HNO, in titrations? Oxygen produced from KMnO, + HCI not only oxidizes the reducing agent but is also partly used for oxidation of HCI to Cl). HNO, itself is an oxidizing agent. Reason for colour of MnO, ~. Mn in MnO; isin oxidation state +7 with a° configuration. Hence, colour is not due to d-d transition but due to charge transfer (from © to Mn) changing Mn from +7 to +6. Lanthanoids and Actinoids: (F-block elements/Inner transition elements) General E.C = (1-2) "4 (n= 1) d?" ns?, Lanthanoids (58-71, La-Lu) are elements in which Sforbitals are progressively filled. Lanthanoids (58-71) are also called rare earths. Actinoids are radioactive and show many oxidation states and hence their only study is complicated. Lanthanoids: (50 —71, La—Lu) EC = [Xe] 4f°™4 5a" 65%. Oxidation States of Lanthanoids: Typical is +3 but +2 and +4 are also found. However, they tend to change to T3. That is why Sm”, Eu" and Yb* are reducing agent while Ce” and 'T6* are oxidizing agents. Due to large energy gap between 4fand 5d, they show limited number of onidation states. Atomic ard lonic Radii of Lanthanoids: Lanthanoid contraction. The small regular decrease in atomic and ionic radii of lanthanoids is called lanthanoid contraction. The small net Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2835608812, 7546845949, NEWTONCTHE d- & f-BLOCK ELEMENTS [CLASS — XI] [NCERT CHEMISTRY SOLUTIONS] decrease is due to increase in nuclear charge which outweighs the inperfect shielding by Felectrons. Due to this contraction, atomic radii of elements of the 3“ transition series (after La) are nearly same as those of 2" series in the same group. Some Characteristics of Lanthanoids: (i) They are silvery white metals. Most of the triva- lent metal ions are coloured due to f - f-transition. Those with xf electrons have same colour as with (14 ~ x) f-electrons. (i) Except La” (f°) and Lu” (f"), all show paramagnetism due to presence of unpaired electrons. Magnetic moment, = j45(SH) +L (L +1) BM where S = spin quantum number and L = orbital quantum number. (ii) They form basic hydroxides. As size decreases from La® to Lu® the covalent character of hydroxides increases and hence basic strength decreases. Thus, La (OH); is most basic while Lu(OH), is least basic. Uses of Lanthanoids: They are used only alloys. The most common being misch metal (Ln = 95%) Fe=5% S, C, Cd, Al trace). Itis used in making Mg based alloy. Itis pyrophoric alloy (vemits spark when struck), used in making bullets, shells, lighter, flints, etc. Actinoids: (89-103, Ac — Lr) E.C = [Rn] 5f*""* 6d" 78°. Oxidation states of Actinoids: Like lanthanoids most common is +3. They also show oxida- tion state of +4, +5, +6 and +7, ¢ in Th, Pa, U and Np respectively. They show a large number of oxidation state because of very small energy gap between 5, 6d and 7s subshells. Ionic Radii and Actinoids Contraction: It is similar to lanthanoids contraction but contrac tion is greater due to poor shielding effects of 5f electrons. Further, 5f orbitals extend in space beyond 6s and 6p orbitals whereas 4 f orbitals are buried deep. Some Characteristics of Actinoids: They are silvery white metals. Their cations are caloured due to f— f transition. Ac” (5f°), Cm™ (5f and Th® (5°) are colourless. They are strongly paramagnetic. Uses of Actinoids: Th is used in atomic reactor and treatment of cancer. U and Pu are used as fuel in nuclear reactor. SGT em" Seu Silver atom has completely filled d-orbitals (4d 's ground state. How you can say that itis a transition element? The outer electronic configuration of Ag (Z = 47) is 4d!95s'. In addition to +1, it shows an oxidation state of +2 (eg, AgO and AgF> exist). In #2 oxidation state, the configuration isd’, ie, the d subshell is incompletely filled. Hence, it is a transition element. In the series Sc (Z=21) to Zn (Z=30), the enthalpy of atomisation of zincis the lowest, ie, 126 kJ mol. Why? In the series, Sc to Zn, all elements have one or more unpaired electrons except zine which. has no unpaired electron as its outer electronic configuration is 3d'° 4s*, Hence, atomic intermetalic bonding (metal-metal bonding) is weakest in zinc. Therefore, enthalpy of atomisation is lowest. Which of the 3d series of the transition metals exhibits the largest number of oxidation states and why? .: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546845949, NEWTONCR. K. MALIK’S NEWTON CLASSES Manganese (Z.= 25) shows maximum number of oxidation states, This is because its elec- tronic configuration is 3d” 4s*. As 3d and 4s are close in energy. It has maximum number of electrons the lose or share (as all the 3d electrons are unpaired). Hence, it shows oxidation states from +2 to +7 (#2, +3, +4, 45, +6 and +7) which is the maximum number. The E® (M7 M) value for copper is positive (+0.34V). What is possible reason for this? (Hint: Consider its high A,H® and low A,,4H®) E® (M*" + M) for any metal is related to the sum of the enthalpy changes taking place in the following steps: M(s)+4,H > Mig) (4, H= Enthalpy of atomisation sublimation) M(g)+4,H— M?* (g), (4, H = lonisation enthalphy) M™ (g) +aq— M™ (aq) + Saya (Anya H= hydration enthalpy) Copper has high enthalpy of atomisation (ie., energy absorbed) and low enthalpy of hydration, (ée., energy released). The high energy required to transform Cu (s) toCu" (aa), i.e,, sum of enthalpies of sublimation and ionisation is not balanced by its hydration en- thalpy. Hence E®(Cu*"/Cu) is positive. How would you account for the irregular variation of ionisation enthalpies (first and second) in the first series of the transition elements? Irregular variation of first ionisation enthalpy: On moving from left to right along the first transition series as effective nuclear charge increases, it is expected in general that the first ionization enthalpy should show an increasing tend. However, the trend is irregular because removel of the electron alters the relative energies of 4s and 3d orbitals. Thus there is a reorganisation energy accompanying ionization. This results in to the release of ex- change energy which increases as the number of electrons increase in the d configuration and also from the transference of s-electrons in to d-orbitals Cr has low first ionisation energy because loss of one electron gives stable electronic configuration (3d). Zn has very high ionisation energy because electron has to be removed from 4s orbital of the stable configuration (34° 4s"). Irregularities of second ionization anthalpy: After the loss of one electron, the removal of second electron becomes difficult. Hence second ionisation enthalpies are much higher and in general increase from left to right. However, Cr and Cu show much higher values because the second electrons has to be removed from 4s orbital of the stable configuration of Cr'(3d°) and Cu+ (3d). Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only? ‘Oxygen and fluorine have small size and heigh electronegativity. Hence, they can oxidize the metal to the highest oxidation state. Which is a stronger reducing agent Cr™ or Fe™ and why? Cr* is stronger reducing agent than Fe*. Reason E° Cr*/Cr* is -ve (-0.41V) whereas E° Fe*/Fe** is +ve (+0.77 V). Thus, Cr°" is easily oxidized to Fe™* but Fe* cannot be easily oxidized to Fe”. Hence Cr* is stronger reducing agent than Fe”. Q.8.8 Calculate the ‘spin only’ magnetic moment of M™,q) ion (Z= 27). Ans. Electronic configuration of M atom with Z = 27 is [Ar] 3d” 4s*. Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2895608612, 7546845949, NEWTONCTHE d- & f-BLOCK ELEMENTS [CLASS — XI] [NCERT CHEMISTRY SOLUTIONS] +. Electronic configuration of M”* will be [Ar] 3d” ie, [TU] ]t [1 [7]. Thus, ithas three unpaired electrons. + Spin only magnetic moment (1) = i (1+ BM= 3642) - V15 BM.-387BM. Explain why Cut ion is not stable in aqueous solutions? Cu (a9) is much more stable than Cu**(ay). This is because although second ionization enthalpy of copper is large but Ayyg H for Cu” (aq) is much more negative than that for Cu’ (aq) and hence it more than compensate for the second ionisation enthalpy of copper. Therefore, many copper (1) compounds are unstable in aqueous solution and undergo disproportion as follows: 2Cu’ —> Cu? +Cu. Actinoid contraction is greater from element to element than lanthanoid contraction. Why? This is due to poor shielding by 5felectrons in the actinoids than that by 4felectrons in the lanthanoids. Deis aus S eel oS See Ee eel) Q.8.1 Write down the electronic configuration of: @ oe Git) Cur @) Co* (vif) Mn (i) Pm* (io) Ce (wi) Lu (wii) Th* Ans, () [Ar]3d° (ia) [Arjad'® () [Ar]3a” (vii) [Ar]3d* Wi) (Xe (iv) [Xe] (wi) [Xe}4f4 5d" (ati) [Rn] Q.8.2 Why are Mn™ compounds more stable than Fe” towards oxidation to their +3 state? Ans. Electronic configuration of Mn™ is 3d° which is half filled and hence stable. Sv, 3% ionization enthalpy is very high i., 3" electron cannot be lost easily. In case of Fe”, electronic configuration is 34°. Thus, it can lose one € easily to give the stable configuration 32° Q.8.3 Explain briefly how +2state becomes more and more stable in the first half of the first row transition elements with increasing atomic number? Ans. As the atomic number increases from 21 to 25, the no. of e“in the 3d orbital also increase from 1 to. As the no. of d-electron in 42 state increases from Ti to Mn, the stability of +2 state increases (d-orbital gradually becoming half filled). Elements No. of in+2state | Oxidation states Sc 3d +3 Ti 3a 42,4344 Vv 3a 42,43,44,45 Cr 3a 12,43, 44, 45,46 Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608812, 7546846949, NEWTONCR. K. MALIK’S NEWTON CLASSES To what extent do the electronic configurations decide the stability of oxidation states in the first series of the transition elements? Illustrate your answer with examples. In a transition series, the oxidation states which lead to exactly half filled or completely filled d-orbitals are more stable. For example, the electronic configuration of Fe(Z ~ 26) is [Ar]3d*4s*. It shows various oxidation states but Fe(III) is more stable because it has the configuration [Ar]3d°, What may be the stable oxidation state of the transition element with the following d-electron configurations in the ground state of their atoms: 3d°, 3d°, 3d® and 3d"? Stable oxidation states 30° (vanadium) +2, +3, +4, +5 3d° (chromium) +3, +4, +6 3at° (manganese) +2, +4, + 6,+7 3d (cobalt) +2, +3 (in complexes) 3d* there is no d* configuration in the ground state. Name the oxometal anions of the first series of transition metals in which the metal exhibits the oxidation state equal to its group number. Cr,0/* and CrO,** (group no. = oxidation state of Cr = 6) MnO," (group no. = oxidation state of Mn=7) ‘Vanadate: VO," (group no. = oxidation state of V = 5). What is lanthanoid contraction? What are the consequences of lanthanoid contraction? ‘The consequence of lanthanoid contraction are as follows: @ The properties of second and third transition series are similar. (i) Basic strength decreases from La(OH), to La(OH);. What are the characteristics of the transition elements and why are they called transition elements ? Which of the d-block elements may not be regarded as the transition elements? The d-block elements are called transition elements because these elements represent change in properties from the most electropositive s-block elements to the least electropositive p-block elements. The electronic configuration of Zn, Cd and Hg are represented by general formula (11) ns, Therefore, they are regarded as transition elements. In what way is the electronic configuration of the transition elements different from that of the non-transition elements? ‘Transition elements contain in completely filled d-subshell, their electronic configuration is (n-1) dn s** whereas non-transition elements have no. d-subshell or their subshell is completely filled and have ns! ~? or ns* np'“ in their outermost shell. What are the different oxidation states exhibited by the lanthanoids? +2,43 and +4 (+3 being most common). Explain giving reasons: (@ Transition metals and many of their compounds show paramagnetic behaviour. (i The enthalpies of atomisation of the transition metals are high. Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2895608612, 7546845949, NEWTONCTHE d- & -BLOCK ELEMENTS [CLASS — XI] [NCERT CHEMISTRY SOLUTIONS] (i) The transition metals generally form coloured compounds. (@) Transition metals and their many compounds act as good catalyst. Ans. Transition metals and many of their compounds show paramagnetic behaviour because these elements have unpaired electrons. Each unpaired clectron has a mag- netic moment associated with its spin angular momentum and orbital angular mo- mentum, In transition elements, there are a large number of unpaired electrons in their atoms, thus they have stronger interatomic interaction and thereby stronger bonding between the atoms. Due to this they have high enthalpies of atomisation. Formation of coloured compounds by transition metals is due to partial adsorption of visible light. The electron absorbs the radiation of a particular frequency and jumps into next orbital. Because of availability of d-orbitals, they can easily form intermediate products w1 are activated. The size of transition metals, atoms and ions are also favourable for transition complex formation with the reactants and hence, transition metals and their many compounds act as good catalysts. ‘What are interstitial compounds? Why are such compounds well known for transition metals? Interstitial compounds are these in which small atoms occupy the interstitial sites in the crystal lattice. Interstitial compounds are well known for transition metals because small- sized atoms of H, B, C, N, etc. can easily occupy position in the voids presentin the crystal lattice of transition metals. How is the variability in oxidation states of transition metals different from that of the non-transition metals? Illustrate with examples. The oxidation states of transition elements differ from each other by unity (due to incom- plete filling of d-orbitals) whereas oxidation states of non-transition elements normally differ by two units. Describe the preparation of potassium dichromate from iron chromite ore, What is the effect of increasing pH on a solution of potassitim dichromate? From preparation of potassium from iron chromite. In aqueous solution, dichromate and chromate ions exists in equilibrium. On increasing the pH. i.e., on making the solution alkali, dichromate ions (orange coloured) are converted into chromate ions and thus, the solution hence yellow. Describe the oxidising action of potassium dichromate and write the ionic equations for its reaction with (i) iodide (i) iron (I1) solution and (iii) HS. () CrO3" +14 H* +61" — 2Cr*’ +7H,0 + 31, (i) CxO} +14 H* + 6Fe* — 2Cr3 +7H,0+ 6Fe™* (i) Cr03" +8 H* + 3H,S— 2Cr’ + 7H, 0 + 38. Describe the preparation of potassium permanganate. How does the acidified perman- ganate solution react with (i) iron (ID) ions (ii) SO, and (iii) oxalic acid? Write the ionic ‘equations for the reactions. 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836608812, 7546846949 NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES (@) MnO; +8H"+5Fe* —> Mn +4H,0+5Fe* (i) 2MnOj+2H,O+5S0, —> 2Mn*+4H" + 5S0%- coo (ii) 2MnO, + 16H" +5 | — > 2Mn”* +8H,0+10C0, coo Q.8.17 For M"/M and M*/M™ systems the E® values for some metals are as follows: CriCr Crice ~04V Mn*/Mn Mne/Mn® | 41.5 V Fev/Fe ; Fee/Fe™ +08V Use this data to comment upon: (@ the stability of Fe™ in acid solution as compared to that of Cr or Mn™* and the ease with which iron can be oxidised as compared to a similar process for either chromium or manganese metal. Eg,»yce is negative (0.4 V). It shows the stability of Cr™ ions, ie, Cr” in solution cannot be reduced to Cr” ions. Further Mn™ has high positive E° value so it is easily converted to Mn” as compared to the conversion of Fe” into Fe. Thus the order of relative stabilities of different ions is Mn* Cr>Fe Q.8.18 Predict which of the following will be coloured in aqueous solution? Ti’, V", Cu’, Sc™, Mn™, Fe* and CO™. Give reasons for each. Ans. Only those ions be coloured have incompletely filled d-orbitals, Those with fully-filled or empty d-orbitals are colourless. Hence Ti”, V*, Mn®, Fe* and CO* are all coloured. Ma0; is also coloured due to charge transfer. Only Sc™ (3d°) is colourless. Q. 8.19 Compare the stability of +2 oxidation state for the elements of the first transition series. Ans. The stability of +2 state decreases from left to right except for Mn and Zn. Stability decreases towards right due to decreasing negative value of standard reduction potential. The decrease in the negative value of standard reduction potential is due to increase in sum of first and second ionization enthalpy. Mn*and Zn* have extra stability due to having half-filled and fully filled 3d-subshell respectively. Q.8.20 Compare the chemistry of actinoids with that of the lanthanoids with special reference to: (@ electronic configuration (i) atomic and ionic sizes (ii) oxidation state and (i) chemical reactivity. Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2895608612, 7546845949, NEWTONCTHE d- & f-BLOCK ELEMENTS [CLASS — XI] [NCERT CHEMISTRY SOLUTIONS] ‘Ans Lanthanoids Actinoids — | (i) Electronic Configuration silXe] 4f 14 5d 652 For example s-La= [Xe] 5d" 63? Ce = [Xe] 4f 5d! 6s Electronic configuration sel Rn] 5f- 6d 754 For example wAc= [Rn] 62" 7s* Th = [Rn] 6d? 7s* (i) Atomic and ionic size Size of atom/ion decreases across the period In the group, size of lanthanoid element is. smaller than actinoid of its own group. ‘Atomic and ionic size Size of atom/ion decrease along the period Actinoid has largest size in its own group. |" Gil) Oxidation state Most common oxidation state = +3 Other oxidation states = +2, +4 ‘Oxidation state ‘Most common oxisation state = +3 Other oxidation states = +4, +5, +6 \" Go) Chemical Reactivity (@) Less tendency towards complex | formation (H) Except promenthium, they are non- radioactive (0) They do not form oxocations (@) Oxides and hydroxides are less basi ‘Chemical reactivity (@) Stronger tendency towards complex formation (@) All the actinoids are radioactive (©) They form oxocations like UO:”, PuOz", UO* etc. (@ Oxides and hydroxides are more basic. Q.8.21 How would you account for the following: ( Ofthe d' species, Cr* is strongly reducing while manganese (III) is strongly oxidising. (Cobalt (1) is stable in aqueous solution but in the presence of complexing reagents it is easily oxidised. The d' configuration is very unstable in ions. Cr** is reducing in nature as its configuration changes from d* to d°. On the other hand, Mn** is oxidising in nature as the configuration changes from d' to d°. Strong ligands force cobalt (Il) to lose one more electron from 3d-subshell and thereby induce d”dp*-hybridization. The ions with d’ configuration try to lose the only electron on d-subshell in order to acquire stable inert gas configuration. Q.8.22 What is meant by ‘disproportionation’? Give two examples of disproportionation reac- tion in aqueous solution. Those reactions in which the same substance undergoes oxidation as well as reduction, ie, the oxidation number of an element increases as well as decreases, is called disproportionation. vi vow () + 3MnO}-+4H —> 2MnO; +MnO, +2H,0 2Cu? — Cu*+Cu a 2 0 Oxidation state of MnO; Gia Ans. () ii) (i Ans, Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608812, 7546846949, NEWTONCR. K. MALIK’S NEWTON CLASSES i) 3CrOP+8 H* —s 2CrOF+Cr*+4H,0 o Oxidation state of Cr in CrO}= (5) Q.8.23 Which metal in the first series of transition metals exhibits +1 oxidation state most frequently and why? ‘Ans. Cu has the electronic configuration 3d" 4s!. It can easily lose 4s" e” to give the stable 3d°° configuration. Hence its shows + oxidation state. Q.8.24 Calculate the number of unpaired electrons in the following gaseous ions: Mn”, Cr, Vand Ti. Which one of these is the most stable in acqueous solution? 3d orbitals No. of unpaired Ans. Mn™ (Z=25)=(Ar]3a*[4 [1174 3 ce Z=24)= [Arad [4 [414 3 v* (z=23)=far3? [114 | 2 Ti (Z=22)=[Arj3d' [4 1 Out of these species, Cr” is most stable in aqueous solution due to its tendency of complex formation. Q.8.25 Give examples and suggest reasons for the following features of the transition metal chemistry: (@ The lowest oxide of transition metal is basic, the highest is amphoteric/acidic. (i) A transition metal exhibits highest oxidation state in oxides and fluorides, (if) The highest oxidation state is exhibited in oxoanions of a metal. Ans. ())_ Acidic strength of oxides increases with the increase in oxidation state of the element For example MnO(Mn”’) is basic whereas Mn,O,{Mn*) is acidic in nature. (i) A metal exhibits higher oxidation states in oxides and fluorides as oxygen and fluorine are highly electronegative elements and small in size that is act as strong oxidising agents. For example, chromium shows an oxidation state +6 in CrF, and osmium shows an oxidation state of +8 in OsO,. (ii) This is also due to high electronegativity of oxygen, for example, Chromium exhibits ‘oxidation states of +6 in oxoanion [CrO,]* and manganese shows oxidation state of +7 in oxoanion [MnO,J. Q.8.26 Indicate the steps in the preparation of: K,Cr,0, from chromite ore. (i) KMnO, from pyrolusite ore. Ans. () Preparation of K,Cr,O, from chromite ore (a) Potassium dichromate is obtained by the fusion of chromite ore (FeCr,0,) with sodium/potassium carbonate in the presence of excess of air AFeCr,O, + 8NaxCO, +70, —+ 8Na,CrO, + 2Fe,O, + 8CO, (0) 2Na,CrO, +2H" —+ Na;Cr,O, +2Na’ +H, (From H, SO,) Sodium dichromate (2) Na,Cr,0, + 2KC1 —> K,Cr,0, +2NaCl Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2895608612, 7546845949, NEWTONCTHE d- & f-BLOCK ELEMENTS [CLASS - XIl] [NCERT CHEMISTRY SOLUTIONS] (i) (@)2MnO, +4KOH+0, S25 2k,MnO,+2H,0 (0)3MnO? +4H* ~ 2MnO; + MnO, +2H,0 Or 3K:MnO, +2H;SO, > 2KMnO, +2K,S0, + MnO, +2H,0 What are alloys? Name an important alloy which contains some of the lanthanoid metals. Mentionits uses. An alloy is homogenous mixture of two or more metals or metals and non-metals. 5% iron along with traces of S, C, Ca and Al. It is used in Mg-based alloy to produce bullets, shells and lighter fruits What are inner transition elements? Decide which of the following atomic numbers are the atomic numbers of the inner transition elements: 29, 59, 74, 95, 102, 104. The f-block elements i, in which the last electron enter into f-subshell are called inner transition elements. These include lanthanoids (58 - 71) and actinoids (90 - 103) thus, elements with atomic numbers 59, 95 and 102 are inner transition elements. The chemistry of the actinoid elements is not so smooth as that of the lanthanoids. Justify this statement by giving some examples from the oxidation state of these elements. Lanthanoids show a limited no, of oxidation state. This is because of large energy be- tween 4s, 5d and 6s subshells. The dominen oxidation state of actinoide is also +3. This is due to small energy difference between 5f, 6d and 7s subshells of the actinoides. Which is the last element in the series of the actinoides? Write the electronic configura tion of this element. Comment on the possible oxidation state of this element. Last actinoid = Lawrencium (Z = 103) Electronic configuration = s<[Rn] 5f** 6d! 7s*. Possible oxidate state = +3. Use Hund’s rule to derive the electronic configuration of Ce” ion, and calculate its ‘magnetic moment on the basis of ‘spin-only’ formula. seCe = 54[Xe] 4f' 5d°6s”. Ce* = 54[Xe] 4f, ie, there is only one upaired electron ie, 1=1 p= ntr+2) = 1d = V3 = 1.73 BM, ‘Name the members of the lanthanoid series which exhibit +4 oxidation states and those which exhibit +2 oxidation states. Try to correlate this type of behaviour with the electronic configurations of these elements. +4 saCe, giNd, oT, ggDy +2= (GN, «Sm, «Eu, Yb +42 oxidation state is exhibited when the lanthanoid has configuration 54° 6s* so that 2 electrons are easily lost. +4 oxidation state is exhibited the configuration left is clase lo 4f° (eg... 4f°, If), uf?) or close to 4f7 (e.g. = 4f7 or 4f*), Compare the chemistry of the actinoids with that of lanthanoids with reference to: (electronic configuration (oxidation states and iii) chemical reactivity. 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836608812, 7546846949 NEWTONCR. K. MALIK’S NEWTON CLASSES Lanthanoids Actinoids (i) Electronic Configuration salXe] 4-4 5d™ 65? For example «La = [Xe] 5d 6s* sxCe= [Xe] 4f' 5d 65? Electronic configuration edRn] Sf 6d™ 75? For example ssAc = [Rn] 61! 7s? seh = [Rn] 6d? 75? (i) Oxidation states Most common oxidation state = +3 Other oxidation states = +2, +4 Oxidation state Most common oxisation state = +3 Other oxidation states = +4, +5, +6 (iii) Chemical Reactivity (a) Less tendency towards complex formation (b) Except promenthium, they are non- radioactive (6) They do not form oxocations Chemical reactivity (2) Stronger tendency towards complex formation (b) All the actinoids are radioactive (0) They form oxocations like UO:", PuO;*, UO' ete. (@) Oxides and hydroxides are more basic. (@) Oxides and hydroxides are less basic Q.8.34 Write the electronic configurations of the elements with the atomic numbers 61, 91, 101 and 109. Z= 61 (Promethium, Pm) E.C = [Xe] 4f5d° 6s*, Z= 91 (Protactium, Pa) E.C = [Rn] 5f* 6d! 7s’. Ans. Z= 101 (Mendeleviun, Md) E.C = [Rn] 5f” 6d’ 7”, Z= 109 (Meitnerium, Mt) E.C = [Rn] 5f** 6d” 7s”, Q.8.35 Compare the general characteristics of the first series of the transition metals with those of the second and third series metals in the respective vertical columns. Give special emphasis on the following points: (Electronic configurations (i) Oxidation states (ii) Tonisation enthalpies and (Atomic sizes. Ans. (Electronic configuration: First series: [Ar] 3d" 4s! 2 Cr(3d°, 4s!) and Cu(3d" 4s!) Second series: [Kr] 4d"? 55°! °"? Third series: [Xe] 4f°° 6d" 751"? ‘Oxidation states: Generally within the transition series, the highest oxidation state increases with the increase of atomic number, reaching to a maximum in the middle anid then start decreasing. In a vertical column, the higher oxidation states are more stable for heavier elements. The elements of group IIT B and I! B do not show variable oxidation state while the rest of groups show variable oxidation states. In +2 and +3 Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2895608612, 7546845949, NEWTONCTHE d- & f-BLOCK ELEMENTS [CLASS — XI] [NCERT CHEMISTRY SOLUTIONS] oxidation states, the bonds formed are mostly ionic and in higher oxidation states, the bonds formed are covalent. Ionisation enthalpies: The ionisation enthalpies increase from left to right in each series. In vertical column, the first ionisation enthalpy decreases from first member to second member. The third member has higher value then second member. This is due to weak shielding of nucleus of 4f electrons in the 5d series. Atomic size: Generally ions of the same charge or atoms in a given series show pro- gressively decrease in radius with increasing atomic number though the decrease is, quite small. But the size of the atom of the 4d series is larger than the corresponding, elements of the 3d series whereas those of corresponding elements of the 5d series are nearly the same as those of 4d series due to lanthanoid contraction. Q.8.36 Write down the number of 3d electrons in each of the following ions: Ti, V*, Cr, Mn’, Fe”, Fe™*, Co™, Ni* and Cu™, Indicate how would you expect the five 3d orbitals to be occupied for these hydrated ions (octahedral). Ans. Configurations | No. of 3d electrons Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608812, 7546846949, NEWTONC4 R. K. MALIK’S NEWTON CLASSES 0.8.37 Commenton the statement that elements of the first transition series possess many prop- erties different from those of heavier transition elements. Ans: Atomic radii of the heavier transition elements (4d and 5d series) are larger than those of the corresponding elements of the first transition series through those 4d and 5d series are very close to each other. Enthalpies of atomisation of 4d and 5d series are higher than the corresponding elements of the first series. ‘Melting and boiling points of heavier transition elements are greater than those of the first transition series due to stronger intermetallic bonding. What can be inferred from the magnetic moment values of the following complex species? Example ‘Magnetic Moment (BM) K,[Mn(CN),] 22 [Fe (H,0),* 5.3 K, [MnCl] 5.9 © K,IMn (CN): Here Mn is +2 oxidation ie,, as Mn” = 2.2 BM shows that it has only one uppaired electron. Hence then CN" ligands approach Mn* ion, the electron is 34 pair up. 36 4s é T t T 1 & sp hybridization (i [Fe (H,0),)*: In this complex, Fe is in +2 state. b= 5.3 BM shows that there are four unpaired electrons. This means that the electrons in 3d do not pair up when the ligands, HO molecules approach. Thus H,0is a weak ligand. 34 4s tT TW Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2895608612, 7546845949, NEWTONCTHE d- & f-BLOCK ELEMENTS [CLASS — XI] [NCERT CHEMISTRY SOLUTIONS] (i) K, [MnCIk: Here Mn is in +2 state i as Mn** 1 = 5.9 BM shows that there are five unpaired electron, Hence, the hybridization involved will sp” and the complex will be tetrahedral. 3d 4s 4p t 1] Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608812, 7546846949, NEWTONCLASSES.NET