The d- and f- Block Elements 8.1 Position in the Periodic Table 84 8.2 Electronic Configurations of thed-Block Elements 8.5 83 General Properties of the Transition Elements 86 (d-Block) 87 = Number of ues eyeeeds Weightage Miract > Topic 8.3 and 8.4 are highly scoring topics. "> Maximum total weightage is of Topic 8.3 General Properties of the Transition Elements (d-Block). > Maximum MCQ,VSA, SA1,SA\II, LA type questions were asked from Topic 8.3 General Properties of the Transition Elements (d-Block). cee aise ‘TRANSITION ELEMENTS (d-BLOCK ELEMENTS) ‘© Elements in which the last electron enters any one of the five d-orbitals of their respective penultimate shell are known as transition elements or d-block elements. © Their general electronic configuration is (n - 1)d*~ ns?-?. © Transition series : d-block consists of four transition series, 1°* Transition series or 3d series Sc goZn 2™ Transition series or 4d series goY - ggCd 3" Transition series or 5d series s7La, 79Hf - gpHe 4" Transition series or 6d series goAc, yoqRf 1120[High due to strong metallic bonding. Enthalpies of atomisation |High due to strong interatomic interactions. lonisationenthalpies __|Generally increases from left to right ina series. (Oxi \Variable due to participation of ns and (n - 1)d electrons. ‘Atomic radii Decrease from left to right but become constant when pairing of electrons takes place. ‘Complex formation Form complexes due to high nuclear charge, small size metal ions and availability of empty| |d-orbitals to accept lone pair of electrons donated by ligands. (Coloured compounds —_| Form coloured compounds due to d-d transitions. ‘Magnetic properties Transition metal ions and their compounds are paramagnetic due to presence of unpaired lelectrons in the (n ~ 1)d-orbitals and it is calculated by using the formula, w= /n(n-+2) ‘where, nis the no. of unpaired electrons, Catalytic behaviour Due to variable oxidation states and ability to form complexes. Interstitial compounds —_|Due to empty spaces in their lattices, small atoms can be easily accommodated. ‘Alloy formation Due to similar atomic sizes. © Oxides in higher oxidation state of metal are acidic, in lower oxidation state are basic, whereas in the intermediate oxidation state are amphoteric. 298/34 “7 MnO MngO, MnO, Mn,O7 basic 1 aie amphoteric ‘© Some important compounds : Compounds Preparation __ Properties Uses Potassium dichromate | From sodium — dichromate| Orange red crystalline sol Indyeing, {K,Cr,0,) (obtained from chromite ore) _ | agent having melting point 398°C. photography an 2- | 4FeCr04+8Na,CO,+70, _ | Oxidising agent in acidic medium: and leather SSP, » 8NaCrO, + 2Fe,03 C1034 14H" + be" — 2cr°* + 7H,0_ | industry. ow BF 750 . +8COs] Oxidises : |” to Ip, HoS to S, Sn”* to Sn**| in| | 2NagCrO4+2H*—> one tore Na,Cr0, + 2Na* + H,0 Na,Cr0, + 2KC—> K,Cr07 + 2NaCl Potassium permanganate | From potassium manganate | Deep purple crystalline solid, oxidising| Asa (kMnO,) (obtained from pyrolusite) agent, having melting point 240°C. disinfectant, 9° 2MnOp + 4KOH + O9~> Oxidising agent in acidic medium germicide, ch 2K,MnOg + 2H,0| MnO4+ 8H" + Se——»Mn“*+4H,0 | and Baeyer’s o& Ilyo 2K2MnO, + Clp—> Oxidises: Ito |p, Fe” to Fe**, reagent 9 2KMnOg + 2KCI] c,.0% toCO,,S* to$,SO% toSO%,NO5| (alkaline toNO} KMnO,), it ‘Oxidising agent in faintly alkaline or|'® 280 used neutral medium: a MnO +2H,0 + 3e°—» MnO, + 40H my Oxidises :" to 103,8,03 to SO; , Mn? toMnO2> Volumetric titrations involving KMnO, are carried out only in the presence of dil. HySO, but not in the presence of HCI or HNO, because HCl is oxidised to Cl, and HNO is itself a strong agent and partly oxidises the reducing agent. H)SO, does not give any oxygen of its own tooxidise the reducing agent. > In CrO}” and CrO4 ion, Cr is present in +6 oxidation state and has d° configuration. Therefore, these ions should not be coloured but CrOJ" ion is yellow and CrOj ion in orange. Their colour can be explained on the basis of charge transfer. There is momentary transfer of negative charge from O-atom to Cr-atom (O* ion changes momentary to O” and oxidation state of Cr changes from +6 to +5, > In MnO; ion, Mn is present in +7 oxidation state and has d° configuration. MnO; is purple/violet in colour due to charge transfer (negative charge from O-atom to Mn-atom). > Chromyl chloride test : When K,Cr0, is treated with chloride and strong sulphuric acid, reddish brown vapours of chromyl chloride (CrO,Cl2) are obtained, USE OF TRANSITION METALS AND THEIR COMPOUNDS : > Zn,Cd and Niare used in the battery. > TiCly (Ziegler-Natta catalyst) is used in the manufacture of polythene. > Fe + Mo are used as catalyst in manufacture of NHg by Haber's process. INNER TRANSITION ELEMENTS (f-BLOCK ELEMENTS) > Lanthanoids : Last electron enters one of the 4f-orbitals. Cerium (at. no, 58) to lutetium (at.no. 74). > Actinoids : Last electron enters one of the 5f-orbitals. Thorium (at. no. 90) to lawrencium {at. no. 103). © General electronic configuration :(n ~ ayer (n- 4) “tas © General characteristics of lanthanoids : Atomic and ionic radii Decrease on going from La to Lu. Oxidation states Most common oxidation state of lanthanoids is +3. Some elements exhibit +2 and +4 oxidation states due to extra stability of empty, half-flled or fully-illed f-subshell, e.g, Ce** acts as an oxidising agent and gets reduced to Ce’, Eu**, Yb” act as strong reducing agents and get oxidised to Eu* and Yb. Action of air All the lanthanoids are silvery white soft metals and tarnish readily in moist ait. They burn in oxygen of air and form oxides (LO, type). Coloured ions ‘They form coloured trivalent metal ions due to f-ftransitions of unpaired electrons. La®* and Lu are colourless ions due to empty (4F°) or fully (4f"4) orbitals. Magnetic properties La, Lu® are diamagnetic while trivalent ions of the rest of lanthanoids are paramagnetic Reducing agents They readily lose electrons and are good reducing agents. Electropositive character Highly electropositive because of low ionisation energies. Alloy formation They formalloys easily with other metals especially iron. ‘Tendency to form Lanthanoids do not have much tendency to form complexes due to low charge density complexes because of their large size, The tendency to form complexes and their stability increases with increasing atomic number. - © Lanthanoid contraction : In lanthanoid series, with | Consequences : Their separation is difficult, they increasing atomic number, there is progressive decrease in atomicfionic radii (M** ions) from La®* to Lu®. » Reason : Due to addition of new electrons into f-subshell and imperfect shielding of one electron by another in the f-orbitals, there is greater effect of increased nuclear charge than screening effect hence contraction in size occurs. have small differences in properties and 4d and 5d transition series have almost same ato radii (Zr and Hf have similar properties due to ‘same size). © Uses of lanthanoids : Used in making mischmetal, an alloy of a lanthanoid metal (~ 95%) with iron (~ 5%) and traces of S, C, Ca and Al. It is used to make tracer bullets, shells and lighter flint.‘© General characteristics of actinoids : lonic radii Like lanthanoids, ionic radii decrease across the series. Actinoid contraction is greater due to poor sheilding effect of the 5f-electrons. Further, 5f-orbitals extend in space beyond 6s and 6p-orbitals whereas 4f-orbitals are burried deep inside the atom. Oxidation states —_| Like lanthanoids, most common oxidation state is +3. They also show oxidation state of +4,+5, +6 and +7, eg,,in Th, Pa, U and Np respectively. They show a large number of oxidation states because of very small energy gap between 5f, 6d and 7s subshells. Action of air, alkalies and acids Like lanthanoids they are also silvery white metals, tarnish rapidly in air forming oxide coating and are not attacked by alkalies and are less reactive towards acids. Coloured ions Coloured due to f-ftransition except Ac**(5F°), Cm™(5f7) and Th**(5f°) which are colourless. Magnetic properties | They are strongly paramagnetic. Density Allactinoids except thorium and americium have high den: ies. Melting and boiling points High melting and boiling points however there is no regular trend with rise in atomic number. lonisation energy They have low ionisation energies than lanthanoides. Reducing agents Allactinoids are strong reducing agents. Electropositive character Highly electropositive metals. © Chemical reactivity : Actinoids are highly reactive metals especially in the finely divided state. They reacts with boiling water to give a mixture of oxide and hydride. uBr, USz Ais o Br ee H, UO, + Hy (i) Which element in 3d series has lowest enthalpy of atomisation? (ii) Why do metals of the second and third series have greater enthalpies of atomisation? (ii) Why are enthalpies of atomisation of transition metals quite high? (Term Il, 2021-22) (Ap] Define transition metals. Why Zn, Cd and Hg are not called transition metals ? How is the variability in oxidation states of transition metals different from that of p-block elements ? (Term Il, 2021-22) (a) Write any two consequences of lanthanoid contraction. (b) Name the element of 3d series which exhibits the largest number of oxidation states. Give Feason. (Term II, 2021-22) Give reasons for the following statements : (a) Transition elements and their compounds act as, good catalysts. (b)__Efvn2*/Min) Value is highly negative as compared toother elements. (c) Cr?" is astrong reducing agent. (Term i, 2021-22) 45. Following ions are given: Cr?*, Cu?*, Cut, Fe**, Fe, Mn?* Identify the ion which is. (i) _astrong reducing agent. (ii) unstable in aqueous solution. (ii) a strong oxidising agent. Give suitable reason in each. Give reasons : (i) E° value for Mn®*/Mn?* couple is much more positive than that for Fe**/Fe**. Iron has higher enthalpy of atomization than that of copper. (iii) Sc* is colourless in aqueous solution whereas Ti?* is coloured. (2018) %) 47. Account the following : (i) Transition metals form large number of complex compounds. The lowest oxide of tran: whereas the highest oxide is amphoteric or acidic, value for the Mn**/Mn?* couple is highly positive (+1.57 V) as compared to Cr°"/Cr?", (3/5, Delhi 2017) 48. Following are the transition metal ions of 3d seri They Mn ce (Atomic numbers : Answer the following (i) Which ion is most stable in aqueous solution and why? (ii) Which ion is strong oxidising agent and why? (iii), Which ion is colourless and why? (3/5, Al 2017) (2020) 46. (i = 22,V = 23,Mn= 25, Cr= 24) 49. Account for the following, (i) Mn shows the highest oxidation state of +7 with oxygen but with fluorine, it shows the highest oxidation state of +4. (ii) Cr? is a strong reducing agent. (iil). Cu?* salts are coloured, while Zn?* salts are white, (3/5, 12016) 50. Eivztnn|_cr | Mn | Fe | Co | Ni | Cu 0.91] -1.18 |-0.44 |-0.28|-0.25 | +034 From the given data of £° values, answer the following questions (i) Why is Efe,21;cw Value exceptionally positive? (i), Why is Efvn2%y4n) Value highly negative as compared to other elements? Which is a stronger reducing agent Cr?* or Fe??Givereason, _ (NCERT, 3/5, Al 2015) 51. Assign suitable reasons for the following: (i) The Mn compounds are more stable than Fe** towards oxidation to their +3 state. (iii)(ii) In the 3d series from Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of Zn is the lowest. (NCERT) (iii) Sc3* is colourless in aqueous solution whereas Ti" is coloured. (Foreign 2014) 52. Give reasons for the following i) _Mn** isa good oxidising agent. i) E°y2yy values are not regular for first row transition metals (3d-series), (iil) Although ‘F" is more electronegative than ‘O; the highest Mn fluoride is Mn, whereas the highest oxide is MnO, (3/5, Al 2013) 53. Give reasons: (i) d-block elements exhibit more oxidation states than f-block elements. (ii) The enthalpies of atomization of the transition metals are high. ‘The variation in oxidation states of transition metals is of different type from that of the non- transition metals, (NCERT, 3/5, Al 2013C) HE (5 marks) 54. The elements of 3d transition series are given as Sc Ti V Cr Mn Fe Co Ni Cu Zn Answer the following () Write the element which shows maximum number of oxidation states. Given reason. Which element has the highest melting point? iii). Which element shows only +3 oxidation state? (iv) Which element is a strong oxidising agent in +3 oxidation state and why? (al 2016) 8.4 Some Important Compounds of Transition Elements (Amark) 55. Account for the following Chromates change their colour when kept in an acidic solution, (1/5, 2020) Orange colour of Cr 03” ion changes to yellow when treated with an alkali. Why? (1/5, Delhi 2017) 0) Complete the following equation 2Mn0; + 6H + 5NO5—> Complete the following equation 3Mn0g- + 4H —> Complete the following equation MnO; + 8H* + 5e"—» (4/5, Delhi 2014) Complete the following chemical equation: $0, +MnOj +H,0-—> (1/2,A1 2014C) Give reason Orange solution of potassium dichromate turns yellow on adding sodium hydroxide to it. (1/5, Al 2013) 56. 57. (1/2, Delhi 2015) 58. (1/3, Foreign 2015) 59. 61, EA 02 marks) 62. 65. 67. 69. 71. 7 73. Write the balanced chemical equations involved in the preparation of KMnO, from pyrolusite ore (MnO), (2020) Write the balanced ionic equations showing the oxidising action of acidified dichromate (Cr,0?") solutions with (i) iron (Il) ion and (i) tin (I) fon. (2020) When MnO, is fused with KOH in the presence of KINO, as an oxidizing agent, it gives a dark green compound (4). Compound (A) disproportionates in acidic solution to give purple compound (8). An alkaline solution of compound (8) oxidises KI to compound (C) whereas an acidified solution of compound (B) oxidises KI to (D). Identify (A), (B), (C) and (0). (NCERT, Delhi 2019) An) Complete and balance the following chemical equations (Fe? +Mn0q+H*—> (i), MnO +H,0.+1—> Complete the following equations (i) 2MnO%+ 16H" + 5S*°—> (i) Kno, Hee > (2/5, Al 2017) When chromite ore FeCr,0, Is fused with NaOH in presence of air, a yellow coloured compound (A) is obtained which on acidification with dilute sulphuric acid gives a compound (B). Compound (B) on reaction with KCI forms an orange coloured crystalline compound (C) () Write the formulae of the compounds (A), (B) and (0). (ii) Write one use of compound (C). (Delhi 2016) Complete the following chemical equations : (i) 8MnO, + 35,03 + H,O—> (il) Cr,0,?- + 35n2* + 14H" —> (2018) (Ap) (Delhi 2016) Complete the following equations. (i) 2MnO, + 4KOH +0,—*—» (i) Cry0F + 14H" + 6 — (2/5, Al 2016) Describe the oxidising action of _ potassium’ dichromate and write the ionic equations for its reaction with (i) an iodide (i) HS. (al 2015¢) How do you prepare (i) KgMnO, from MnO? {ii) | NagCr207 from NaCrO,? Complete the following equations () Cry07 + 20H —> (2/5, Delhi 2014) (ii), MnOg + 4H" + 3e°—> (Al 2014) Complete the following equations : (i) 2Mn0, + 55% + 16H*—> (ii) Cr,07° + 20H —> (Foreign 2014)74, Complete the following equations: (i) 2croz+2H*— (i) KMno, —He*> (3 marks) 75. Explain the method of preparation of sodium dichromate from chromite ore. Give the equation representing oxidation of ferrous salts by (al 2013) dichromate ion. (al2019) 76. Complete the following reactions. () MnO, +KOH+0,—> ii) MnO, +H! —> Cr20,?" + Sn?* + H*—> (Al 2019) 77. Complete the following chemical equations : (i) Cr} + 6Fe** + 14H" —> (i) 2croz- + 2H" (iii) 2MinOg + 5C,0f + 16H"—» (Delhi 2013) 78. Describe the preparation of _ potassium, permanganate from pyrolusite ore. Write balanced chemical equation for one reaction to show the oxidizing nature of potassium permanganate. (3/5, Al 2013C) REE (5 maris) 79. (a) Givereasons: ()) Transition metals and their compounds show catalytic activities. (ii) Separation of a mixture of Lanthanoid elements is difficult. (ili) Zn, Cd and Hg are soft and have low melting point. (b) Write the preparation of the following: {)) NagCrz0; fromNaxCrO, (ii) KjMnO, from MnO, 8.5 The Lanthanoids (1mark) 80. Give reasons for the following Eu** is a strong reducing agent. 81. Account for the following Zrand Hf have almost similar atomic radii, (1/5,A12015)(0) (2020)(Ap) (1/3, Delhi 2019) oR How would you account for the following : Zr (Z=40) and Hf (Z=72) have almost identical radii (1/3, Delhi 2013, 1/5, Al 2013C)(U) 82. Name a member of the lanthanoid series which is, ‘well known to exhibit +2 oxidation state. (1/5, Delhi 2014) 83. Name a member of the lanthanoid series which is ‘well known to exhibit +4 oxidation state. (1/5,A12014) 84, What are the different o» the lanthanoids? (2 marks) 85, What is lanthanoid contraction? What are its two consequences? (Delhi 2013¢) lation states exhibited by (1/3, Foreign 2014) oR ‘What is lanthanoid contraction and what is it due to? Write two consequences of lanthanoid contraction. (NCERT, 2/5, Delhi 2013C) (3 marks) 86. What is lanthanoid contraction? What are the consequences of lanthanoid contraction? (Delhi 2015C) 8.6 The Actinoids (Amark) 87. Write one similarity and one difference between the chemistry of lanthanoid and actinoid elements. (1/5, Delhi 2017)(R) 88. Chemistry of actinoids is complicated as compared tolanthanoids. Give tworeasons. (1/5, Delhi 2017) 89. Give reasons: Actinoids show irregularities in their electronic configurations. (1/3, Delhi 2016) 90. How would you account for the following: Actinoid contraction is greater than lanthanoid contraction? (1/3, Delhi 2015) OR Assign reasons for the following : From element to element actinoid contraction is greater than the lanthanoid contraction. (1/3,A12014C) 91. Give reasons for the following: Actinoids exhibit a greater range of oxidation states than lanthanoids. (1/3, Al2014C) BEAM 2 marks) 92. Why do actinoids show a wide range of oxidation states? Write one similarity between the chemistry of lanthanoids and actinoids, (2/5, A1 2015) 93. With reference to structural variability and chemical reactivity, write the differences between lanthanoids and actinoids. (2/5,A12014) HEMI (3 mars) 94. Give three points of difference between lanthanoids and actinoids. (3/5, 2020)8.2 Electronic Configurations of the d-Block Elements 4. Which of the following is the reason for zinc not exhibiting variable oxidation states? (a) Inert pair effect (b) Completely filled 3d subshell ()_ Completely filed 4s subshell (d) Commonion effect (2020-21) 8.3 General Properties of the Transition Elements (d-Block) 2. Which set of ions exhibit specific colours? (Atomi number of Sc = 21, Ti = 22, V=23, Mn = 25, Fe = 26, 28, Cu= 29 and Zn =30) (a) Sc*", Ti", Mn (b) Sc", Zn?*, NPY (VV, Fee (a) Ti, TH, NY (2020-21) 3. Which of the following is a diamagnetic ion? (Atomic numbers of Sc, V, Mn and Cu are 21, 23, 25 and 29 respectively.) fa) V(b) Sc#* EEN (3 marks) 4 (a). Why are fluorides of transition metals more stable in their higher oxidation state as ‘compared to the lower oxidation state? (b) Whichone of the following would feel attraction when placed in magnetic field: Co”, Ag’, Ti", Zn** (€)_Ithas been observed that first ionisation energy of 5d series of transition elements are higher than that of 3d and 4d series, explain why? oR (On the basis of the figure given below, answer the following questions : (cud) Mn (2020-21) ‘Atomic number—> (Source : NCERT) (a) Why manganese has lower melting point than chromium? (b) Why do transition metals of 3d series have lower melting points as compared to 4d series? (c) Inthe third transition series, identify and name the metal with the highest melting point. (Term 1, 2021-22) 3) ‘Account for the following : {a)_ Ti(IV) ismore stable than the Tit) or Tit). (b)_ Incase of transition elements, ions of the same charge in a given series show progressive decrease in radius with increasing atomic number, (©) Zinc is a comparatively a soft metal, iron and chromium are typically hard. (Term ll, 2021-22) Give reasons for the following: (i) Transition elements act as catalysts. (ii) It is difficult to obtain oxidation state greater than two for copper. (ili) Cr05° is a strong oxidising agent in acidic medium whereas WOx and MoOg are not, oR Observed and calculated values for the standard electrode potentials of elements from Ti to Zn in the firstrreactivity series are depicted inthe given figure: 05 Standard electrode potentialV Voc Mn Fe Co Ni cu Zn m8 Observedvalues © Caleulated values (Source : NCERT) Explain the following observations (i) The general trend towards less negative E° values across the series. (ii) The unique behaviour of copper. (iii). More negative E° values of Mn and Zn. at (2020-21) U) 8.5 The Lanthanoids (Smarks) (a) What happens when Manganate ions (MnOJ) undergoes disproportionation reaction in acidic medium? ii) Lanthanum is heated with sulphur?(b) Explain the following trends in the properties of the members of the first series of transition elements : (i) € (M**/M) value for copper is positive (40.34 V) in contrast to the other members of the series. (ii) Cr?" is reducing while Mn** is oxidising, though both have d“ configuration. (ii) The oxidising power in the series increases in the order VO} < Cr,03” < MnO4. _ (2019-20) (U) 8.6 The Actinoids HEE (5 mariss) (a) When a chromite ore (A) is fused with an aqueous solution of sodium carbonate in free excess of air, a yellow solution of compound (B) is obtained. This solution is filtered and acidified with sulphuric acid to form compound (©). Compound (C) on treatment with solution of KCI gives orange crystals of compound (0). Write the chemical formulae of compounds A toD. (b) Describe the cause of the following variations with respect to lanthanoids and actinoid () Greater range of oxidation states of actinoids as compared to lanthanoids, (il) Greater actinoid contraction as compared to lanthanoid contraction (ii) Lower ionisation enthalpy of early actinoids as compared to the early lanthanoids. (2019-20) (Ap) Detailed | SO! Uy I fe x a 1. Zn, Cd, Hg are considered as d-block elements but not as transition elements because they do hot have partly filled q-orbitals in their atomic state or their coirimion oxidation states (i, Zn”", Cd", Hg”). CaE® 2 Theelectronic configuration of the elements should be well known, 2. Elements which have incompletely filled d-orbitals in their ground state or in any one of their oxidation states are called transition elements. Characteristics of transition elements (i) They show variable oxidation states. (ii) They exhibit catalytic properties. 3. (¢) EkeyPoints ') © In 3d series, Mn has maximum number of oxidation state because number of unpaired electrons is ‘maximum in Mn (34°, 45%), 4. (c):Because of strong metallic bonding present in atoms of transition elements, they have high melting, points. Transition elements show variable oxidation states. 5. Zn, Cd and Hg do not have partly filled d-orbital in their ground state or common oxidation state. 6. Scandium (Sc) exhibits only (+3) oxidation state. 7. The transition metals and their compounds, are known for their catalytic activity. This activity is ascribed to their ability to adopt multiple oxidation states, ability to adsorb ithe reactanit(s) and ability to form complexes, Vanadium (V) oxide (in Contact Process), finely divided iron (in Haber's Process), and nickel (in catalytic hydrogenation). 8, Strong metallic bonds between its atoms of transition elements are responsible for the high melting points (except Zn, Cd and He). 9. Zn?" ion has completely filled d-subshell andro d-a transition is possible. So zinc salts are white, Configuration of Cu* is [Ar] 3d?. It has partly filled d-subshell and hence it is coloured due to d-d transition, 10. Zine 14. Cull) compounds have completely filled d-orbitals and there are no vacant d-orbitals for promotion of electrons whereas in Cul(!!) compounds have one unpaired electron which is responsible for colour formation. 2 ded transition responsible for the colour formation of transition elements. 12. Oxoanion of chromium in which it shows +6 oxidation state equal to its group number is Crs? (dichromate ion) 13. Formula of oxoanion of manganese is MnO}. Oxidation state of Mn in this oxoar Group number of Mn is 7. 14, Due to presence of vacant d-orbitals\ and aa transitions, compounds of the transition metals are generally coloured, ‘When an electron from alower energy d-orbital is excited to a higher energy d-orbital, the energy of excitationcorresponds to the frequency which generally lies in the visible region. The colour observed corresponds to the complementary colour of the light absorbed. The frequency of the light absorbed is determined by the nature of the ligand. 45. Zn®* ion has completely filled d-subshell but Cu’ jon has partly filled d-subshell. 2+ 6. Transition elements can use’ their ns and (n ~ 1) d-orbital electrons for bond formation therefore, they show variable oxidation states. Because, the energy difference between (n ~1)d orbital and ns orbital is small. For example, $c has ns(n ~ 1) d* electronic configuration. It utilizes two electrons from its ns subshell then its oxidation state = +2. When it utilizes both the electrons then its oxidation state = +3, 17. (hh:Co = [Ar]3d74s? Co? = [Arlsd” sa Tate ay tpt Unpaired electrons ie, there are three unpaired electrons (n = 3). Hence, = ynin-+2) BM, = (3842) =3.87 BM. 18. (j) Sc has 3d? outer electronic configuration, therefore it is diamagnetic in nature whereas Cr°* has 3d? outer electronic configuration. So, it is paramagnetic due to presence of unpaired electrons. (ii) Ina particular series, the metallic strength increases, upto middle with. increasing number of unpaired electrons, ic, upto d° configuration. After Cr, the number of unpaired electrons goes on decreasing. Accordingly, the mpt and bpt. decrease after middle (Cr) because of increasing pairing of electrons. (i) Transition metals form alloys because they have similar atomic radii. (ii) Basic nature of oxides decreases and acidic nature increases with increase in oxidation state of the metal. Oxidation state of Mn in MngO, is +3 while in MnO, is, +7. (i) Cr?*is a stronger reducing agent than Fe" Exjyc2+_ fs negative (-0.41. V) whereas ERs is positive (+ 0.77 V). Thus, Cr2* is easily oxidized to Cr?" but Fe®* cannot be easily oxidized to Fe". Hence, Cr** is stronger reducing agent than Fe**, (il) More positive s the value of E% reaction will be more feasible. As E%¢o24;co% is maximum, thus Co** ion is most stable. 21. (i) Variable oxidation states of transition metals arise due to incomplete filing of d-orbitals and it differs from each other by unity eg., V(V), V(IV}, VIII}, VID. In p-block elements oxidation states differ generally by a unit of two. eg., Sn(ll), Sn{IV), PCls, PCIs, etc i) In aqueous solution Cu" undergoes disproportionation to form a more stable Cu** ion. 2CUijaqy —? CuiZ, + Co, Hydration enthalpy of Cu* is higher than Cu* that is Cu?" is more stable in aqous solution. () Transition elements can use their ns and (n ~ A}d orbital electrons for bond formation therefore, they show variable oxidation states. For example, Sc has ns”(n - 1) d* electronic configuration. It utilizes two electrons from its ns subshell then its oxidation state = +2. When it utilizes both the electrons then its oxidation state = +3. (ii) tn Zn, Cd and Hg, all the efectrons in d-subshell are paired. Hence, the metallic bonds are weak. That is why they are soft metals with ow melting and boiling points. (i) Manganese can form px dr bond with oxygen by utilising 2p-orbital of oxygen and 3d-orbital of manganese due to which it can show highest oxidation state of +7. While with fluorine it cannot form such pr dre bond thus, it can show a maximum of +4 oxidation state. (i) Transition elements can use their ns and (n ~ 1)d orbital electrons for bond formation therefore, they show variable oxidation states. For example, Sc has ns*(n ~ 1) d’ electronic configuration. It utilizes two electrons from its ns subshell then its +2. When it utilizes both the electrons oxidation state = +3. (i) Transition elements can use their ns and (n - 1}d orbital electrons for bond formation therefore, they show variable o For example, Sc has ns(n ~ 1) d* electronic configuration. It utilizes two electrons from its ns subshell then its oxidation state = +2. When it utilizes both the electrons then its oxidation state = +3, (i) In aqueous solutions, Cu* undergoes disproportionation to form a more stable Cu’* ion. 2Cujog) > Cua + Cy Cu** in aqueous solutions is more stable than Cu’ io because hydration enthalpy of Cu”* is higher than that of Cu’. It compensates the second ionisation enthalpy of Cu involved in the formation of Cu* ions. Transition elements can use their ns and (n ~ 1) orbital electrons for bond formation therefore, they show variable oxidation states. For example, Sc has ns“(n ~ 1) d! electronic configuration, It utilizes two electrons from its ns subshell then its oxidation state = +2. When it utilizes both the electrons, then its oxidation state = +3. ‘Among the 3d series manganese (Mn} exhibits the largest, number of oxidation states from +2 to +7 because it has maximum number of unpaired electrons, Mn ~ [Ar] Sa 4s”26, (i) Manganese can form pn - dx bond with oxygen by utilising 2p-orbital of oxygen and. 3d-orbital of manganese due to which it can show highest oxidation state of +7. While with fluorine it cannot form, such px - drt bond thus, it can show a maximum of +4 oxidation state. (ii) The transition metals and their compounds, are known for their catalytic activity. This activity is ascribed to their ability to adopt multiple oxidation states, ability to adsorb the reactant(s) and ability to form complexes, Vanadium (V) oxide (in Contact Process), finely divided iron (in Haber’s Process), and nickel (in catalytic hydrogenation) are some of the examples. 27. Disproportionation reaction involves the oxidation and reduction of the same substance. The examples of disproportionation reaction are : 2Cuj4q—> Cuyy + Cufiny 28. (i) Electronic configuration of Mn** is 3d° which is half filled and hence stable. Therefore, third tonization enthalpy is very high, ie, 3 electron cannot be lost easily. In case of Fe*", electronic configuration is 3d°. Hence, it can lose one electron easily to give the stable configuration 34°. (ii)_ Zine (Z = 30) has completely filled d-orbital (Sd*°), so orbitals do not take part in interatomic bonding, Hence, metallic bonding is weak, This is why it has very low enthalpy of atomisation (126 kJ mol), 29. (I) Characteristics of transition elements : {They show variable oxidation states. (i) They exhibit catalytic properties. (ii) Zn, Cd, Hg are considered as d-block elements but, not as transition elements because they do not have partly filled d-orbitals in their atomic state or their ‘common oxidation states (ie., Zn”, Cd”, He") 30. (2) The atoms of transition metals have strong, metallic bonds between them, thus these have high melting and boiling points. (il) Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of different 3d-configurations (eg. d°, d°, d' are exceptionally stable). 21 () In aqueous solution Cu" undergoes disproportionation to form a more stable Cu** jon. 2Cjeg) —> Cua * CU Hydration enthalpy of Cu?" is higher than Cut that is why Cu?" is more stable in aqueous solution. (il) This is due to ability of oxygen to form multiple bonds with metals. 82. (i) Transition elements can use their ns and (n ~ 1) d-orbital electrons for bond formation therefore, they show variable oxidation states. Because, the energy difference between (n~1)d orbital and ns orbital is small For example, Sc has ns(n ~ 1) d’ electronic configuration. It utilizes two electrons from its ns subshell then its oxidation state = +2. When it utilizes both the electrons then its oxidation state = +3. (ii) The tendency to form complexes is high for Coftt!) as compared to Co(II). Co”* ions are very stable and are difficult to oxidise, Co™" ions are less stable and are reduced by water. In contrast many Co(ll) complexes are readily oxidised to Collll) complexes and Colt) complexes are very stable, eg., [Co(NH,),]** “> [Co(NH3)4)°* This happens becausé the crystal field stabilisation energy of Coil!) witha d°(t6,) configuration is higher than for Co(ll) with ad” (t8, ¢) arrangement. 33. (i) In aqueous solution Cu’ _ undergoes disproportionation to form a more stable Cu”* ion, 2CUjegy —> Cutz) + CUyy Hydration enthalpy of Cu** is higher than Cu* that is why Cu”* is more stable in aqueous solution. (ii) Transition elements have more number of unpaired electron in their valence shells than alkali metals, that is why transition elements make strong metallic bonds, which results in extreme hardness as compared to alkali metals. 34, (i) The transition metals and their compounds, are known for their catalytic activity. This activity is ascribed to their ability to adopt multiple oxidation states, abi to adsorb the reactant(s) and ability to form complexes. Vanadium (V) oxide (in Contact Process), finely divided iron (in Haber's Process), and nickel (in catalytic hydrogenation), (il) Due to presence of vacant d-orbitals, there is dd transitions in the compounds of the transition metals that is why they are generally coloured, When an electron from a lower energy d-orbital is excited to a higher energy d-orbital, the energy of excitation corresponds to the frequency which generally lies in the visible region. The colour observed corresponds to the complementary colour of the light absorbed. The frequency of the light absorbed is determined by the nature of the ligand 35. (i) Copper exhibits +1 oxidation state in its compounds. Electronic configuration of Cu in the ground state is 3d° 4s". So, Cu can easily lose 4s! electron to give a stable 34° configuration. Thus, it shows +1 oxidation state. {ii) Only those ions will be coloured which have pattial filed orbitals Facitating bd taneltiony Oba gad and d’° will be colourless. From electronic configuration of the ions, V°"(3d") and Mn?*(3d"), are all coloured. Ti**(3d) and Sc*(3d°) are colourless. > 3d? and 3d’ are colourless while 3d* to 3a” are coloured,‘Transition elements can use their ns and (n~ 1) orbital electrons for bond formation therefore, they show variable oxidation states. Because, the energy difference between (n ~1)d-orbital and ns-orbital is small, For example, Sc has ns*(n ~ 1}d° electronic configuration, It utilizes two electrons from its ns subshell then its oxidation state = +2. When it utilizes both the electrons then its oxidation state = +3. (i) The transition metals and their compounds, are known for their catalytic activity. This activity is ascribed to their ability t6 adopt multiple oxidation states, ability {0 adsorb the reactant{s) and ability to form complexes. Vanadium (V) oxide (in Contact Process), finely divided iron (in Haber's Process), and nickel (in catalytic, hydrogenation) Colour of transition metal ions is due to the dd ns. lons which do not involve in d-d transitions ate colourless. Ti** : 30°4s°, no d-d transition, colourless Cr: 3a, d-d transitions occur as shown below : 3441 Ground state Hence, Cr ion is coloured. V3": a?, d-d transition occur as shown below : 1 2 2 wy oy Hence, V*" ion is coloured. In other words, Generally the ions having completely ‘empty d-orbitals or no unpaired electron in d-orbitals of transition element are colourless. (i) Mn** (308) > Mn>*(ad") More stable Less stable Mn* is more stable in 3d” state, hence shows resistance towards oxidation. Fe*" (3°) > Fe (3d) Lessstable More stable Fe** is more stable hence gets oxidised easily. (ii) Highest oxidation state of transition element is shown with oxides and fluorides, because oxygen and. flourine are small in size and have high electronegativity. 27. (i) 9 > 31 Excited state (Silver atom has outer electronic configuration 4d?°5s" in its ground state, but silver in +2 oxidation state has electronic configuration 4d°. So in +2 oxidation state, silver has incomplete d-orbital, Hence, silver is considered as a transition element. (i) Mn?* ion has stable halt-filled (3d°) electronic configuration whereas Zn®* has completely filled a! configuration. Hence, EXjazijqq and E%,24/7_ are more negative than expected. (iii) Transition metals form alloys because they have similar atomic radii, 39. (a)_In case of copper, the sum of enthalpy of atomisation and ionisation enthalpy is greater than enthalpy of hydration. That is why R244 for Cu Is positive. So, copper does not displace hydrogen from acids, (b) Transition metals and most oftheir compounds contain unpaired electrons in the (n ~ 1)d-orbitals. Hence, they show paramagnetic behaviour, (©) In Zn, Cd and He, all the electrons in d-subshell are paired, Hence, the metallic bonds are weak. That is why they are soft metals with low melting and boiling points. 40. (i) The high melting points of transition metals are attributed to the involvement of greater number of (n = 1}d electrons in addition to ns electrons in the interatomic metallic bonding. In any row, the melting points of these metals rise to a maximum at d° except for anomalous values of Mn and Te and fall regularly as the atomic number increases. (il) Due to presence of vacant d-orbitals and dd transitions, compounds of the transition metals are generally coloured. Whenan electron from a lower energy d-orbitalis excited to a higher energy d-orbital, the energy of excitation corresponds to the frequency which generally fies in the visible region. The colour observed corresponds to the complementary colour of the light absorbed. The frequency of the light absorbed is determined by the nature of the ligand. (iil) E° value of Mn®*/Mn?* is + 1.57 V. Mafia + @° 3 Mrvgiay + £° = +£1.57 V This value is highly positive because Mn** (a) has a very high tendency to get reduced to Mn?* (d?) which has a stable half - filled electronic configuration. ()__ Enthalpy of atomisation depends on the number of unpaired electrons in the valence shell. Greater the number of valence electrons, stronger is the resultant bonding and higher will be the enthalpy of atomisation. In 4d series, zinc has no unpaired electrons in valence shell 0, it has lowest enthalpy of atomisation. (i) The enthalpies of second and third transition series are high because of the poor shielding of electrons in 4d and Sd orbitals in comparison to electrons in 3d orbital which results in strong metallic bonding. (ii) Transition metals have high enthalpies of atomisation because of presence of unpaired electrons and poor shielding effect of d-orbitals. Elernents which have incompletely filled d-orbitals in their ground state or in any one of their oxidation states are called transition elements, Zn, Cd, He are considered as d-block elements but not as transition elements because they do not have partly filled orbitals in their atomic state or their common oxidation states (ie, Zn", Cd”, He"), Variable oxidation states of transition metals arise due to incomplete filing of d-orbitals and it differs from eachother by unity eg. VV), VIIV), VIII, VII). In p-block elements oxidation states differ generally by a unit of two. eg, Sn(l), Sn{IV), PCla, PCls, etc. 40, (a) Lanthanoid contraction : The steady decrease in the atomic and ionic radii of lanthanoid elements with increase in atomic number is called lanthanoid contraction. (I) Atomic radii of second and third transition series element are almost identical. As a result they occur in nature together and their separation from mixutre different. (il) The small difference in atomic radii of lanthanoids is. responsible for difference in their basic properties. (b) Among the 3d series, Mn exhibits largest number of, oxidation states from +2 to +7 because it has maximum number of unpaired electrons. 44, (a). The transition metals and their compounds, are known for their catalytic activity. This activity is ascribed to their ability to adopt multiple oxidation states, ability to adsorb the reactant{s) and ability to form complexes. Vanadium (V) oxide (in Contact Process), finely divided iron (in Haber's Process), and nickel (in catalytic hydrogenation) are some of the examples. Catalysis involves the formation of bonds between reactant ‘molecules and atoms at the surface of the catalyst. (b) Mn?" ion has stable half-filled (3d°) electronic configuration. Its ionisation enthalpy value is lower in comparison to hydration enthalpy. Hence ERy,2t van iS more negative. (c) Cr®* is reducing agent since its configuration is converted to d° from d‘.d° has half filled tp, configuration with higher stability. 5. (i) Cr is reducing since its configuration is converted to d° from d*.d? has half filled tzg configuration with higher stability. (i) Cu* is unstable in aqueous solution In aqueous solutions, Cu’ undergoes disproportionation to form a more stable Cu” ion. 2Cuijag) > Ctl) + CU (iii) Mn" is a strong oxidising agent because electronic configuration of Mn** is 34° which is half filled and hence stable. Therefore, third ionization enthalpy is very high, ie, 3° electron cannot be lost easily. wae ®@® © Species tends to act as oxidising and reducing agent to attain most stable oxi <6, (i) From the relation, AG More positive is the value of E°, reaction will be feasible. Mn 22min? 5 Fe 425 Fee ad ad? 3d° oe more stable more stable tha fled) "ha led) Hence, E?aiye for Mn°*/Mn** couple is much more positive than that for Fe*/Fe**, (ii) Greater the number of unpaired electrons, stronger is the metallic bond and therefore, higher is the enthalpy of atomisation, Since, iron has greater number of unpaired electrons than copper hence has higher enthalpy of atomisation. Only those ions are coloured which have partially filled d-orbitals facilitating dd transitions, Sc” has no unpaired electron but Ti** has one unpaired electron and Transition metals form a large number of complex compounds due to following reasons : ~ Comparatively smaller size of metal ions. ~ High ionic charges. = Availability of d-orbitals for bond formation. (ii) Lowest oxidation compounds of transition metals, are basic due to their’ ability to get Oxidised to higher oxidation states. Whereas, the higher oxidation state of metal and compounds gets reduced to lower ones and hence are acidic in nature. eg, MnO is basic whereas Mn,O; is acidic. (iii) E? value of Mn**/Mn?* is + 1.57 V. Mnifjq) + €° —> Mnigiy s E° = 1.57 V ‘This value is highly positive because Mn (d*) has a very high tendency to get reduced to Mn?* (d?) which has a stable half - filled electronic configuration. 48. (i) Ti* has highest oxidation state among the given ions. Ti** has stable inert gas configuration and hence, most stable in aqueous solution. On the other hand, V*, Mn®, Cr°* have unstable electronic configuration and hence, are less stable. (il) Due to presence of highest oxidation state of Ti, it acts as the strongest oxidising agent among the given ions. (iii) Due to absence of unpaired electron in Ti™, it is a colourless ion EC. of Ti = [Ar]3q%4s° () Manganese can form pr - dx bond with oxygen by utilising 2p-orbital of oxygen and ‘3d-orbital of manganese due to which it can show highest oxidation state of +7. While with fluorine it cannot form, such pr ~ drt bond thus, it can show a maximum of +4 oxidation state. (ii) Cr* is reducing since its configuration is converted to d° from d*. d° has half filled ta, configuration with higher stability. (ii) Zn?* ion has completely filled d-subshell and no ded transition is possible. So zinc salts are white, Configuration of Cu?" is [Ar] 3d”. It has partly filled d-subshell and hence it is coloured due to d-d transition. 50. (i) In case of copper, the sum of enthalpy of atomisation and ionisation enthalpy is greater than enthalpy of hydration. That is why E%j2jy for Cu is positive(ii) _Mn** ion has stable half-filled (34°) electronic configuration. Its ionisation enthalpy value is lower in comparison to hydration enthalpy. Hence E}4n2*jvin is more negative, (iii) Cr?* is a stronger reducing agent than Fe?*. Etsy is negative (-0.41 V) whereas Efespe2 is, positive (+ 0.77 V). Thus Cr?" is easily oxidized to Cr°* but Fe** cannot be easily oxidized to Fe*". Hence, Cr?" is stronger reducing agent than Fe”. Exe > Cupty is more stable than Cuja,) due to the more negative value of Ayjyq H® of Cu?* than Cu’. 51, (i) Electronic configuration of Mn** is 34° which is half filled and hence stable. Therefore, third ionization enthalpy is very high, ie, 3" electron cannot be lost easily. In case of Fe", electronic configuration is 34°, Hence, it can lose one electron easily to give the stable configuration 3°. Zinc (Z = 30) has completely filled d-orbital (347°), so orbitals do not take part in interatomic bonding, Hence, metallic bonding is weak. This is why it has very low enthalpy of atomisation (126 kJ mol’). (iii) Only those fons are coloured which have partially, filled d-orbitals fac ing d-d transitions. Sc** with 3d° configuration is colourless while Ti** (3a) is coloured. 52. (i) Mn? is more stable due to half filled d° configuration and Mn** easily changes to Mn** hence, it is a good oxidising agent. (ii) The E4y2+y4 values are not regular which can be explained from the irregular variation of ionisation enthalpes ie., IE, + IE) and also the sublimation enthalpies which are relatively much less for manganese and vanadium. (iii) Manganese can form px - dx bond with oxygen by utilising 2p-orbital of oxygen and 3d-orbital of manganese due to which it can show highest oxidation state of +7. While with fluorine it cannot form such pr-- di bond thus, it can show a maximum of +4 oxidation state. 53. (i) All transition elements except the first and the last member in each series show a large number of variable oxidation states. This is because difference of energy in the (n ~ 1)d and hs orbitals is very little. Hence, electrons from both the energy levels can be used for bond formation. whereas f-black elements have large energy gap between F and d-subshell. (ii) As transition metals have a large number of unpaired electrons in the d-orbitals of their atoms they have strong. interatomic attraction or metallic bonds. Hence, they have high enthalpy of atomization. (iii) The variability in oxidation states of transition metals is due to the incomplete filling of d-orbitals. Theit oxidation states differ from each other by unity. 54. (i) Mn shows maximum no. of oxidation states from +2 to +7 because Mn has maximum number of unpaired electrons in 3d sub-shell. (ii)_Cr has maximum melting point, because it has 6 Uunpaired electrons in the valence shell, hence it has strong interatomic interaction. (ii) Scshows only +3 oxidation state BECaus® aFLEFIOSINR electrons, it has noble gas electronic configuration. {iv)_ Mn is strong oxidising agent in +3 oxidation state because change of Mn®* to Mn* give stable half filled (d°) electronic configuration, SV. 55. In aqueous solution, Eivedtaadh = Cr0} + HO =—=* 2CrO} + 2H Dievomate fon Chromate fon (Orange red) ‘yellow When an acid is added (ie. pH of solution decreased), the concentration of H"* ions is increased and the reaction proceeds in the backward direction producing an orange red dichromate solution. 56. Orange colour of Cr:07" ion changes to yellow when an alkali such as NaOH is added because on addition ofan alkali, the concentration of H’ fons decreases and hence, the reaction proceeds in the forward direction producing, yellow solution containing CrO,. ions. Crj03+ 20H” —> 2CrO%+ H,0 orange yellow 57. 2MnO, + 6H" + 5NO3 —» 2Mn®* + 5NO3 + 3H,O 58. 3MnO3+ 4H* —> 2MnO4 + MnO, + 2H,0. 59% MnO, + 8H" + Se —> Mn?" + 4H,0 60. 2MnOj + 550, +2H,0 —> 2Mn®* + 5502+ 4H? 61. Orange colour of Cr;07” ion changes to yellowwhen an alkali such as NaOH is added because on addi in alkali, the concentration of H ions decreases and hence, the reaction proceeds in the forward direction producing yellow solution containing CrO;_ ions. 2 Cr,0F ion (orange colour) 2 CrOF ion (yellow colour) 62. Preparation of potassium permanganate : Potassium permanganate is prepared by the fusion of MnO, (pyrolusite) with potassium hydroxide and an oxidising agent like KNOs to form potassium manganate which disproportionates in a neutral or acidic solution to form permanganate. 2MnOy + 4KOH + 0 > 2KzMnOy + 2Hz0 3MnO2" + 4H*—> 2MnO, + MnO, + 2H,0 oF, 3K,MnOg + 4HCI—> 2KMnO, + MnO, + 2H,0 + 4KCL65. (i) Crg07+ 14H" + 6Fe*—> 2Cr™ + 6Fe™* + 7H20 Cr,0F + 3Sn?* + 14H" > 2Cr* + 35n** + 7,0. 64. (A)is KxMnOg, (B) is KMnOg, (C) is KIO and (0) is Ip. MnO, +2KOH + KNO3——» K;MnO, + KNO, + H,0 a 3K.MnO, + 2H,S0, —> 2KMnO, + MnO, + 2K,SO, @) +2H,0 2KMnO, + H,0 + KI—> 2MnO, + 2KOH + KIO, ic) 2KMnO4 + BHSO, + 10KI—> 6K,S0, + 2MnSO, +8H,0 +51, © 65. (i) 5Fe**+ MnO, + 8H" — Mn** + 4H,0 + 5Fe** (i) 2MnO;+H,0 +1 20H" + 2MnO, +105 66. (i) 2Mn0%+ 16H" + 5S?" 2Mn?* + 8H,0 + 5S. (ii) 2KMnO,—"2*> KyMnO, + MnO, +05 67 (i). AFeCr0, + 16NaOH +70,» 8Na,CrO,, + 2Fe,0, + 8H,0 “ 2NazCrO4 + H,SO,—> NaCr,0, + NaySO, + HO @ NagCry07 + 2KCI—> KyCry07 + 2NaCl © Potassium dichromateis used as a powerful oxidising idustries and for staining and tanning of leather. Students must remember the equations involved in the preparation of potassium dichromate. ©) BMNO5 faq) + 350% on) + HO > MNO ri + 6 SO% py + 20H) Cr,0F + 35n?* + 14H" — 2Cr** + 3Sn"* + 7H,0 (i) 2MnO, + 4KOH + O24» 2K,MnO, + 2H,0 Cr,03+ 14H" + 6 —> 2Cr* + 31, + 7H,0 © Potassium dichromate is a strong oxidising agent. In the presence of dilute sulphuric acid, one molecule of K,Cr207 gives 3 atoms of available oxygen. +35?" + 14H" —> 2cr*+ a5n"* + 7H,0 (il) KjCrj0,+3H,S + 4H,S0,~>Cry(SOq), + 35+ K,SO, +7H,0 6) 6 Thamttory ometits roast eplipe c=DvbthOdy taael tonne | AON Von able ork Caatigthe. noguasiian Tesseg aebveion RP tas Tro Aut ae ¥ the AAwctlon woe oe shtionats fate. 71. (i) 2MnO, + 4KOH + O,—4» 2K,MnO, + 2HO (ii) Sodium dichromate can be crystallised out from sodium chromate solution by acidifying it with sulphuric acid. 2Na,CrO, + 2H* > Na,Cr,0, + 2Na" + HO 72. (i) Crg0F" + 20H —> 2Cr0?* + H,O (ii) MnOg + 4H* + 3e° —3 MnO, + 2H,0 73, (i) ~HaS—> 2H" +S? 5S? + 2MnOj + 16H" —> 2Mn”* + 8H,0 + 5S (ii) Crg0? + 20H” —> 2Cro#* + HO 74, (i) 2CrOZ + 2H*—+ Cr,0F" + HO (i) 2KMnO,—> KzMnO, + MnO, +O, 75. The yellow solution of sodium chromate is acidified ith sulphuric acid to give a orange solution of sodium dichromate Na,Cr0, which is crystallised 2NagCrO, + HySOq —> NazCr,07 + NaySOq + HO Sodium chromate Sodium dichromate The solution of sodium dichromate is treated with potassium chloride to obtain potassium dichromate. NayCrj07 + 2KCI—> K,Cr,07 + 2NaCl Potassium dichromate Cr,0F" + 35n?* + 14H" > 2Cr** + 35n* + 7H,0. 76. (i) 2MnO, +4KOH +0,» 2K,MnO,+2H,0 (i) 2Mnoj + 101" + 16H" + 512+ HO (ii) Cr0% + 3Sn?* + 14H* —> 2cr* + 35n* + 7H,0 77 (i) Cr0%joq) + 14H jeg) + OFF —> 2Cr Fa) + 6Fefag + 7H2O (9 2CrO}" + 2H* —+ Cr40,2"+H,0 Ui) 260; + 5C,0% + 16H" —3 2M?" +840 1000, 78. Preparation of potassiuin permanganate : Potassium permanganate is prepared by the fusion of MnO, (pyrolusite) with potassium hydroxide and an oxidising agent like KNOg to form potassium manganate which disproportionates in a neutral or acidic solution to form permanganate, 2MnO, + 4KOH + Oy ~» 2KyMnO, + 2H,0 3MnO}" + 4H" 2MnO4 + MnO, + 24,0 of, 3K;MnO, + 4HCI—> 2KMnO, + MnO, + 2H,0 + 4KCI Oxiclising nature of KMnO, 2MnO4 + 5C,02° + 16H" > 2Mn?" + 10CO, + BH,O (i) MOLL Omnd MANE Masa (agadoAay A AK Aderfee eosin — log meketb fe borat Bacto tin tos 80. EU" has a strong tendency to lose electrons to attain the more stable +3 oxidation state of lanthanoids hence, itis a strong reducing agent. 81. Due to lanthanoid contraction the elements of 4d and 5d-series have similar atomic radii e.g., Zr = 145 pm and Hf = 144 pm. 82. Europium (Eu) is well known to exhibit +2 oxidation state due to its half-filled f orbital in +2 oxidation state. 83. Lanthanoids showing +4 oxidation state are sgCe, 9Pr, gsTb and geDy. 84. Lanthanum and all the lanthanoids predomi nantly show +8 oxidation state. However, some of the lanthanoids also show +2 and +4 oxidation states in solution, or in solid compounds. This irregularity arises mainly due to attainment of stable empty (4f°), half-filled (4f7) and fully filled (4f%4) sub shell eg, CoM: af, Eu: af” Th :4f7, Yb%: 4p 85. Lanthanoid contraction : The steady decrease in the atomic and ionic radii of lanthanoid elements with increase in atomic number is called lanthanoid contraction. It is caused due to imperfect shielding of nuclear charge by 4f-electrons, Consequences of lanthanoid contraction : (i) The basic strength of oxides and hydroxides. of lanthanoids decrease with increasing atomic number. (i) Atomic and ionic sizes of 4d transition series elements and 5d series elements are similar. eg, atomic radi of zirconium(Zr) is same as that of hafnium Hf. [Topper’s Answer, 2020] 86. Lanthanoid contraction : The steady decrease in the atomic and ionic radii of lanthanoid elements with increase in atomic number is called lanthanoid contraction. Consequences of lanthanoid contraction : (i) The basic strength of oxides and hydroxides of lanthanoids decrease with increasing atomic number. (ii) Atomic and ionic sizes of 4d transition series elements and 5d series elements are similar. eg., atomic radii of zirconium(Z1) is same as that of hafnium Hf. 87. Similarity : The elements of both the series are electropositive in nature. They are reactive metals and act as strong reducing agents. Difference : Lanthanoids except promethium are non- radioactive elements, while all actinoids are radioactive elements. 88. Chemistry of actinoids is more complicated than, lanthanoids because (i) actinoids show greater number of oxidation states due to the comparable energies of 5f, 6d and 7s orbitals. (ii) most of the actinoids are radioactive and the study of their chemistry in the laboratory is difficult. 59. The irregularities in the electronic configurations of actinoids are due to extra stabilities of the f°, f” and F" orbitals. 90. The actinoid contraction is more than lanthanoid contraction because 5f-electrons are more poorly shielded than 4f-electrons,7. ‘ctinolds exhibit greater range of oxidation states than lanthanoids. This is because there is less energy difference between 5f and 6d orbitals in actinoids than the energy difference between 4f and 5d orbitals in case of lanthanoids, 92. ‘Aétinoids exhibit greater range of oxidation ‘states than lanthanoids. This is because there is less energy difference between 5f and 6d orbitals in actinoids than the energy difference between 4f and 5d orbitals in case of lanthanoids, Similarity : The elements of both the series are electropositive in nature. They are reactive ‘metals and act as strong reducing agents. 93. Structure : All the lanthanoids are silvery white soft metals. Hardness of Lanthanoids increases with increasing atomic number. The actinoid metals are all silvery in appearance but display a variety of structures. The structural variability is due to irregularities in metallic radii which are greater, than that of lanthanoids, Chemical reactivity : Earlier members of lanthanoid series are quite reactive similar to calcium but with increasing atomic number they behave more like aluminium. The actinoids are highly reactive in finely divided state. 94. Difference between lanthanoids and actinoids are following () Electronic configuration : The general electronic configuration of lanthanoids is (xeJ4f*™ 5d! 65? whereas, that of actinoids is [Rn] Sf !"'* 6d" 752, Thus, lanthanoids involve the filling of 4f-orbitals whereas, involve the filing of 5f-orbitals Oxidation states : Lanthanoids have principal oxidation state of #3. In addition, the lanthanoids show limited oxidation states such as +2 and +4 because of small energy gap between 4f and 5d subshells. On the other hand, actinoids show a large number of oxidation states because of small energy gap between 5f and 6d subshells, (iii) Chemical reactivity : First lanthanoids are quite reactive almost like calcium, whereas, actinoids are highly reactive metals especially in the finely divided state. Lanthanoids react with dilute acids to liberate H gas whereas actinoids react with boiling water to give a mixture of oxide and hydride. > Inactinoids, neptunium (Np) and plutonium (Pu) show maximum oxidation states upto +3 to #7. me Este 1 ) (1) 2. (): V8", V", Fe* possesses two, three and five unpaired electrons in 3d-subshell. Hence, they will give coloured solution (1) few members of ‘3. (BV: 3d" = No. of unpaired electrons = 3 => paramagnetic Sc** : 3d? — No. of unpaired electrons is zero => diamagnetic Cu : 3a? =» No. of unpaired electron = 1 = _ paramagnetic Mn** : 3a = No. of unpaired electrons = 4 (a) => paramagnetic 4. (a) The ability of fluorine to stabilise the highest oxidation state is attributed to the higher lattice energy or high bond enthalpy. cl) (b) Co** has three unpaired electrons so it would be paramagnetic in nature, hence Co** ion would be attracted to magnetic field, Rest all ions are diamagnetic in nature. (y (0) Thetransition elements of Sd series have interver 4forbitals. Thereis greater effective nuclear chargeacting, on outer valence electrons due to the weak shielding by 4f electrons. Hence, first ionisation energy of 5d series of transition elements are higher than that of 3d and 4d series, (a) oR (a) Mangnese has five unpaired electrons in its d-orbital which is completely half filled and having more stability, Hence, these electrons are not free to participate in ‘metallic bonding, So, Mn has less heat of atomization and its melting point is lower than chromium. () (b) The 4d and 5d transition elements have larger size than that of 3d elements they form metal-metal strong, bond which required more energy to break bond, That is why 3d series have lower melting point than 4d series. (1) {c)_ Tungsten (W). (a) 5. (a) Tiishaving electronic configuration [Ar]3d? 4s? which on loss of four electrons will lead to the formation of Ti’ [Ti(IV)] which is more stable as it acquires nearest noble gas configuration, ( (b) In case of transition elements, ions of the same charge in a given series show progressive decrease in radius with increasing atomicnumber.As thenewelectron enters in d-orbital each time the nuclear charge increases by unity. The shielding effect of a d electrons is not that effective, hence the net electrostatic attraction between the nucleus and the outermost electron increases and the ionic radius decreases, (1) (tron and chromium are having high enthalpy of atomization due to the presence of unpaired electrons, which accounts for their hardness. However, zinc has low enthalpy of atomization as it has no unpaired electron. Hence, zinc is comparatively a soft metal. () 6. (i) The transition elements are known for their catalytic activity. This activity is ascribed to their ability to adopt multiple oxidation states, ability to absorb the reactant(s) and ability to form complexes. ( (ii) Due to high value of third ionisation enthalpy. (1)(iii) Mo(V1) and W(V1) are more stable than Cr(Vi). (1) (The general trend towards less negative £° values across the series is related to the general increase in the sum of first and second ionization enthalpies. ( (i) Copper has high positive reduction potential ( value) and this show that copper is least reactive metal, Electrode potential (E°) value is the sum of three factors. (a) Enthalpy of atomisation, A,H for Cupy ~> Cuyy. {b)_lonisation enthalpy, AH for Cu) -> Cue {0} Hydration enthalpy, Apygtt for Cu > Culfan In case of copper the sum of enthalpy of atomisation and ionisation enthalpy is is not balanced enthalpy of hydration, This is why E%2,_for Cu is positive, a (ili) Mn?" ion and Zn** ion has stable half-filled(3d°) and fully-filled (34°) electronic configuration. Hence ER4q2%/man and 3,229 1s more negative. (1) (a) ( MnOJ* ions disproportionate in acidic medium to give permanganate ions and manganese(IV) oxide. (2) 3MnOF + 4H* > 2MnO; + MnOz + 2H,0. (1/2) (i) Lanthanum sulphide is formed when lanthanum is heated with sulphur. (4/2) ata 35H > Lays, (u2) (0) () Copper has high enthalpy of atomisation and low enthalpy of hydration, Since, the high energy to transform Cu) 10 Cu%iq) is not balanced by hydration enthalpy, therefore [E° (M*/M)] value for copper is positive (40.34 V), (a) (il) Cr?" is reducing agent as its configuration changes from d4 to d®, the latter having more stable half-filled ty, level. On the other hand, the change from Mn** to Mn?* results in extra stable d° configuration. (ay ill) This is due to the increasing stability of the species of lower oxidation state to which they are reduced. (1) 8 (a) 2FeCry0, +4NagCOg+ 40, = ” Fej0q + 4NazCrO, + 4COy ® 2NayCrO, + HySO, ~» NayCr07 + Na,SO, + HO 6) o | NagCrgOz + 2KCI > KyCr07 + 2NaCl o Hence, A= FeCr,O4 (C) (b) ())5f,6dand 7s levels in actinoids are of comparable energies. am (ii). This is due to poorer shielding by 5f-electrons actinoids as compared to shielding by 4f-electrons in lanthanoids. (a) (iii) In actinoids, 5f-electrons are more effectively shielded from the nuclear charge than the 4f-electrons of the corresponding lanthanoids. Since, the outer electrons are less firmly held, they can easily come out from the atom in the case of actinoids. (a)oell ASSessment Case Based Questions (5 marks) 1. Read the passage given below and answer the following questions : ‘Transition metal oxides are compounds formed by the reaction of metals with oxygen at high temperature. The highest oxidation number in the oxides coincides with the group number. In vanadium, there is a gradual change from the basic V0, to less basic VO, and to amphoteric V,05V20, dissolves in acids to give VO" salts. Transition metal oxides are commonly utilized for their catalytic activity and semiconductive properties. Transition metal oxides are also frequently used as pigments in paints and plastic. Most notably titanium dioxide. One of the earliest application of transition metal oxides to chemical industry involved the use of vanadium oxide for catalytic oxidation of sulfur dioxide to sulphuric acid. Since then, many other applications have emerged, which include benzene oxidation to maleic anhydride on vandium oxides; cyclohexane oxidation to adipic acid on cobalt oxides. An important property of the catalyst material used in these processes is the ability of transition metals to change their oxidation state under a given chemical potential of reductants and oxidants. (i) Which oxide of vanadium is most likely to be basic and ionic? (a) vo (b) V205 (9) VO, (d) V205 (i) Vanadyl ion is fa) vo*" (b) Vo}. ( V,0" (d) Vos” {iill Which of the following statements is false? (a). With fluorine vanadium can form VFs. (6) With chlorine vanadium can form VCls, (c)_ Vanadium exhibits highest oxidation state in oxohalides VOCly, VOBr3 and fluoride VF, (d) With due to oxidising power of V°" and reducing nature of iodine vanadium cannot form Vis (iv). The oxidation state of vanadium in Vz0s is () 45/2 (b) 47) 45 @) 46 (v) Identify the oxidising agent in the following reaction. V20s + 5Ca— 2V + 5Ca0 (a) V205 (b) Ca ov (4) None of these 2. Read the passage given below and answer the following questions : Transition elements are elements that have partially filled d-orbitals. The configuration of these elements corresponds to (n ~ 1)d*?° ns*. It is important to note that the elements mercury, cadmium and zine are not considered transition elements because of their electronic configurations, which corresponds to (n-1)d'ns*. Some general properties of transition elements are These elements exhibit many oxidation states ; These elements can form coloured compounds and ions due to d-d transition; These elements exhibit many oxidation states ; These elements exhibit paramagnetic or diamagnetic properties which depends on no. of unpaired electron in atom or ion. A large variety of ligands can bind themselves to these elements, due to this, a wide variety of stable complexes formed by these ions. The boiling and melting point of these elements are high. These elements have a large ratio of charge to the radius. General electronic configuration (n-2)f*-* (n 1d ns? ()) Although Cr°* and Co** ions have same number of unpaired electrons but the magnetic moment of Cr" is 3.87 BM. and that of Co” is 4,87 BLM. Why? (mark) 0) Although +3 oxidation states is the character- istic oxidation state of lanthanoids but cerium shows +4 oxidation state also. Why? (2 marks) (ii) The magnetic nature of elements depends on the presence of unpaired electrons. Identify out of 3d’, ad%, 34° and 3d configuration of transition element, which shows highest magnetic moment. (amark) (iv). Metallic radii of some transition elements are given below. Which of these elements will have highest density? Element Mn Fe Co Cu Metallic radii/pm 137 126 125 128 (amark) A&R Questions (1 mark) In the following questions, a statement of assertion followed by a statement of reason is given. Choose the correct answer out of the following.fa) (b) 2) (d) Multiple Choice Ques VSA Type Questions 10. 11. 12. Assertion and reason both are correct statements and reason is correct explanation for assertion. Assertion and reason both are correct statements but reason is not correct explanation for assertion. Assertion is correct statement but reason is wrong statement. Assertion is wrong statement but reason is correct statement. Assertion : Separation of Zr and Hf is difficult. Reason : Because Zr and Hf lie in the same group of the periodic table. Assertion : Actinoids form relatively less stable complexes as compared to lanthanoids. Reason : Actinoids can utilise their 5f orbitals along with 6d orbitals in bonding but lanthanoids do not use their 4f orbital for bonding. ns (1mark) Interstitial compounds are formed when small atoms are trapped inside the crystal lattice of metals, Which of the following is not the characteristic property of interstitial compounds? (a) They have high melting points in comparison to pure metals. (b) They are very hard. (c) They retain metallic conductivity. (d) They are chemically very reactive. When acidified K,Cr0y solution is added to Sn”* salts then Sn** changes to (a) Sn (b) Sn (c) Sn* oR Electronic configuration of a transition element X in #3 oxidation state is [Ar]3d°. What is its atomic number? (a) 25 (b) 26 = @) 27d) 24 The magnetic moment is associated with its spin angular momentum and orbital angular momentum, (a) sn* Spin only magnetic moment value of Cr** ion is (a) 2878M. (b) 3.87 BM, (0 3.47BM. (@) 3578.M, There are 14 elements in actinoid series. Which of the following elements does not belong to this series? (@) Ub) Np) Tm (d) Fim Generally transition elements form coloured salts due to the presence of unpaired electrons. Which of the following compounds will be coloured in solid state? (2) Ag,SO, (©) ZnF (@) (b) CuF, CuCl, (mark) Cul, is not known. Why ? What are coinage metals? Why are they so called? Second ionisation enthalpy for Cr and Cuis unusually high. Explain. ‘SA I Type Questions (2 marks) 13. Trivalent lanthanoid ions are coloured. Why? 14. Discuss the consequences of lanthanoid contraction. 15. lonisation enthalpies of actinoids are lower than that of corresponding lanthanoids. Why? 16. How is potassium permanganate prepared in laboratory? 17. What happens when KMnO, is heated? OR Electronic configuration of actinoids are irregular. Why? SA II Type Questions 18. () Complete the following reactions (a) 2MnO, + 3Mn?* + 2H,O——> (b) SNO; +2Mn0, + 6H? —> (ii) Give two uses of KMnO,. 19. Give reasons : Anhydrous cobalt compounds appear blue while hydrated compounds appear red. 20. Transition metals have very high melting and boiling points. Why? 21. Compare qualitatively the first and second ionisation potentials of copper and zinc. Explain the observation. (3 marks) oR () Give two reactions in which potassium dichromate acts as oxidising agent. (ii) What happens when dichromate ion is dissolved in alkali? LA Type Questions (S marks) 22. () The second and third rows of transition elements resemble each other much more than they resemble the first row. Explain why? (ii) E° of Cuis + 0.34 V while that of Zn is - 0.76 V. Expl When Cu" ion is treated with KI, a white precipitate is formed. Explain the reaction with the help of chemical equation. The halides of transition elements become more covalent with increasing oxidation state of the metal, Why? (ii) Although fluorine is more electronegative than oxygen, but the ability of oxygen to stabilise higher oxidation states exceeds that of fluorine. Why? The halides of transition elements become more covalent with increasing oxidation state of the metal. Why? Explain why does colour of KMnO, disappear when oxalic acid is added to its solution in acidic medium? (iii) 23. ti) (i) 24. (i)Why does copper not replace hydrogen from acids? Reactivity of transition elements decreases almost regularly from Sc to Cu. Explain. How do the oxides of transition elements in lower oxidation states differ from those in higher oxidation states and why? (ii) Why is KMnO, better bleaching agent than’ chlorine? (iii), When orange solution containing Cr,07 ion is treated with an alkali, a yellow solution is 25. i) formed and when H’ ions are added to yellow solution, an orange solution is obtained. Explain why does this happen? OR (What is Lanthanoid contraction? Write down’ its two consequences? (ii) Explain: (a) Whyis europium (Il) more stable than cerium (I)? (b)_ Whyis +3 oxidation state of gadolinium (2 = 64) and lutetium (2 = 71) especially stable? Detailed eit TIONS | 1 (i) (a) sOxide of V in lowest oxidation state, ie,, VO is basic and ionic in character. (ii) (a):Vanadyl ion is VO?* where V is in +4 oxidation state. (iii) (b) Ww) © ™ (a) Due to symmetrically electronic configuration no orbital contribution in Cr°* jon. However appreciable contribution takes place in Co”* ion. (ii) Formation of Ce** is favoured by its noble gas configuration. Ce ~ [Xel4f" 5d" 6s, Ce" becomes f° hence along with +3 oxidation state it also shows +4 O.S. (ili) 3d° electronic configuration has highest number of unpaired electrons hence it has highest magnetic, moment: (iv) Cuwill have highest density. 3. (b): Separation of Zr and Hi same size. difficult as both have 4. (c) Actinoids are more reactive and show greater, range of oxidation states. 5. (dj:Interstitial compounds are chemically inert. 2 6. le} CrgO7 + 14H* + 3Sn?* —> 3sn** + 2Cr3* + 7H,0 oR (b) .X* = [Ar]3a°, X = [Ar]3d$ 4s? hence atomic number of element is 26, 7. (b):Cr* (344) with 3 unpaired electrons. = ynlns 2) = /3(8+2)=3.87B.M, 8 (c):Tm (Thulium) isa lanthanoid, 9. (b) Cu?" has 4 unpaired electron in CuF;,, hence, it is coloured in solid state Cur" - 3d? 10. Culy is not known because Cu”* oxidises I to Ip. 2Cu?* + 41" > Cuigly + lp 11, Elements of group-11 (Cu, Ag, Au) are called coinage metals. They are so called because they were used in making coins. 12. After losing one electron Cr possesses half filled and Cu possesses fully filled d-orbital. So, itis difficult, to remove an electron from it further. So, 2" ionisation enthalpy of Cu and Cr are unexpectedly high. Cr* [Ar] 3d? Cut > [Ar] 3d? 413. Trivalent lanthanoids are coloured due to presence of electrons. The excitation of electron in f-level imparts, colour to them. This colour is caused due to Ff transition. Some compounds show colour due to charge transfer also. 14, (i) Due to lanthanoid contraction, the radii of elements of 4d and 5d series transition elements are almost same and hence they have similar physical properties. (il) They occur in nature together. (ii) Their separation is difficult 15, The Sf-electrons are more effectively shielded from the nuclear charge than the 4f-electrons of lanthanoids., Because the outer electrons are less firmly held hence their ionisation enthalpy is low. 16. In laboratory a manganese (I) ion salt is oxidised by peroxodisulphate to permanganate. 2Mn** + 55,02 +8H,0 > 2MnO; + 1050, + 16H" 17. 2KMn0O, 513K, K,MnO, + MnO, +O, oR This is due to extra stability of f°, f7 and f™* sub levels and almost identical energy of 5f and 6d- orbitals. 18. () (a) MnO, + 3Mn?* + 2H,O > SMnO, + 4H* {b) 5NOz + 2MnO, + 6H" > 2Mn** + SNO3 + 3H,0 (i) (a) Bleaching of wool {b)_ Decolourisation of oils. 419. If a substance absorbs wavelength corresponding to, red light, the transmitted light will consist of wavelengths corresponding to blue colour. The substance will, therefore, appear blue. The transmitted light has complementary colour to that of the absorbed light. Anhydrous cobalt (ll) compounds absorb red light and transmit radiations of wavelength corresponding to bluecolour. (which is complementary to red colour), therefore, appear blue. The hydrated cobalt(II) compounds,however,, absorb radiations of wavelengths corresponding to blue colour and, therefore, appear red. 20. The high melting and boiling points of transition metals are attributed to the involvement of greater ‘number of electrons from (n ~ 1) d-orbital in addition to thens electrons in the strong interatomic metallic bonding (d-d overlap) 21, The electronic configuration of Zn and Cu are : Zn: 15? 2s? 2p® 3s? 3p% 3d"? 4s? Cu: 15% 2s? 2p 35? 3p® 3d! as? From the above configuration it is clear that first ionisation energy of Znis greater than that of Cu (because of 4s? and 4s" configuration of Zn and Cu respectively). More energy is needed to remove an electron of 4s” than that of 4s". ‘The second LE. of Cuis higher than that of Zn because for Cut the configuration is 15? 2s* 2p 35? 3p® 3d and for Zn’ the configuration is 1s 2s? 2p® 35? 3p® 3a 4s}, it is easier to remove 4s" electron of Zn’ than a 3d-electron from 3d" (stable configuration). OR (i) (@) 6 +Cr,03" + 14H" 3p + 2Cr* + 7H1,0 {b) 3Sn?* + Cr,03° 4 14H" > 35n4* + 2Cr°* + 7HO (ii) When dichromate ion is dissolved in alkali it forms chromate ion Cry0,? + 20H” —> 2CrO,4 + H,0 (orange) (yellow) 22. (i) Due to Lanthanoid contraction, the atomic radii of second and third row transition elements is almost same. So their properties are similar to each other much more as compared to first row elements, In case of Zn, when two electrons are removed from 4s orbital, 3d" configuration is acquired which is stable hence zinc undergoes oxidation with E° value of -0.76 V. In case of Cu, the the sum of sublimation enthalpy and ionisation enthalpy to transform Cu to Cui, is very igh and is not balanced by its hydration enthalpy. (ii) First cupric iodide is formed which decomposes to give cuprons iodlide and iodine. CuSO, + 2KI—> Culy + KSO4] x 2 2Cull > Cigly + ly 2CUSO4 + AKI—> Cigly + 2K,SO4 +1 or 2Cu* +4 —> Cu2ly + lp White pot. 23. (i) As the oxidation state increases, size of the ion of transition element decreases. As per Fajan's rule, as the size of metal ion decreases, covalent character of bond formed increases, (ii) The ability of oxygen to stabilise higher oxidation states exceeds that of fluorine. It is due to the ability of ‘oxygen to form multiple bonds to metals. (iii) As the oxidation state increases, size of the ion of transition element decreases. As per Fajan’s rule, as the size of metal ion decreases, covalent character of bond, formed increases, 24, (ii) KMnO, acts as an oxidising agent. It oxidises oxalic acid to CO, and itself gets reduced to Mn?* ions which are colourless. 5C,07° + 2MnO, + 16H! ~» 2Mn?* +8H,0 + 10CO, Coloured Colourless i) Copper has a positive E° value. It is below hydrogen in the reactivity series. It does not reduce H* of acids toHy. (ii) Due to regular increase in ionisation enthalpy the reactivity decreases along the row. 25. (i) In the lower oxidation state, the transiti ‘metal oxides are basic and they are acidic ifthe metal isin, higher oxidation state. The oxides are amphoteric when, the metal is in intermediate oxidation state. For example, ‘3 4a 7 Mn,0, MnO, Mn,0, Basie” Amphoteric Acie In case of lower oxide of a transition metal, the metal atom has a low oxidation state. This means some of the valence electrons of the metal atom are not involved in bonding, hence, these can be used for donation. Thus, these are act as bases. (ii) Chlorine may form some harmful compounds during bleaching of textiles. These compounds may cause water pollution whereas the bleaching by KMnO, is harmless. (iii) On treating with alkalies dichromate ions are converted to chromate ions which are yellow in colour. On acidifying yellow colour again changes to orange. 1,03 ot croz Dichromate (orange) 1” Chromate (yellow) oR (i) Lanthanoid contraction : The steady decrease in the atomic and ionic radii of lanthanoid elements with increase in atomic number is called lanthanoid contraction. It is caused due to imperfect shielding of nuclear charge by 4f-electrons. Consequences of lanthanoid contraction : (a) The basic strength of oxides and hydroxides of lanthanoids decrease with increasing atomic number. (b) Atomic and ionic sizes of 4d transition series elements and 5d series elements are similar. e.g., atomic radii of zirconium(Zr) is same as that of hafnium Hf. (ii) (a) Europium (Il) has electronic configuration [Xe}4F’5a° while cerium (I!) has electronic configuration [Xe]4f "Sd", In Eu", 4f subshell is half filled and 5d-subshell is empty. Since half filled and completely filled electronic configurations are more stable, hence Eu?* ions is more stable than Ce* (b) This is because gadolinium in +3 state has half filled 4f-subshell (4f’) and lutetium in +3 state has completely filled 4f-subshell which are very stable configurations. 20ers —