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The d and f block elements The d-block of the periodic table contains the elements of the groups 3-12 in which the d orbitals are progressively filled in each of the four long periods. The elements constituting the f -block are those in which the 4 f and 5 f orbital are progressively filled. The names transition metals and inner transition metals are often used to refer to the elements of d and f-blocks respectively. There are mainly three series of the transition metals, 3d series (Sc to Zn), 4d series (Y to Cd) and 5d series (La to Hg, omitting Ce to Lu). The two series of the inner transition metals / f block elements, (4f and 5f) are known as lanthanoids and actinoids respectively. 1. Define transition element. A transition element is defined as the one which has incompletely filled d orbitals in its ground state or in any one of its oxidation states. 2. Zinc,cadmium and mercury are not regarded as transition metals.Why? Zinc,cadmium and mercury have full d10 configuration in their ground state as well as in their common oxidation states and hence, are not regarded as transition metals. 3. Write the general electronic configuration of transition element (n-1)d110ns12. The (n1) stands for the inner d orbitals which may have one to ten electrons and the outermost ns orbital may have one or two electrons. 4. On what ground can you say that scandium (Z = 21) is a transition element but zinc (Z = 30) is not? Scandium atom in its ground state (3d1) has incompletely filled 3d orbitals, hence it is regarded as a transition element. Zinc atom has completely filled d orbitals (3d10) in its ground state as well as in its oxidised state, hence it is not regarded as a transition element. 5. Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a transition element? [ Ag- 4d10 5s1, Ag+2 - 4d9] In +2 oxidation state, silver has incompletely filled d-orbitals (4d), hence a transition element. Properties of transition metals High melting and boiling points Form complexes High enthalpy of atomization. Show catalytic properties. Show variable oxidation states. Form alloys. Form coloured ions. Form interstitial compounds. Paramagnetic in nature. 6. Melting and boiling points of transition metals are high (or) Cr, Mo, W have high enthalpy of atomisation/ hard / less volatile. The high melting points of these metals are attributed to the involvement of greater number of unpaired electrons [ (n-1)d and ns electrons], stronger interatomic metallic bonding, hence high enthalpy of atomization. 7.The enthalpies of atomisation of the transition metals are high. Transition elements have large number of unpaired electrons, strong interatomicmetallic bonds. As a result, the enthalpy of atomization of transition metals is high. 8.In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the lowest, i.e., 126 kJ mol1. Why?

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Zinc has completely filled d10 configuration, no unpaired d eletrons,weak metallic bonding. While in all other metals, d electrons are always involved in the formation of metallic bonds. 9. The metals of the second (4d) and third series (5d) have much more frequent metal-metal bonding in compounds than do the 3d metals.Explain. The 4d and 5d series have large size than 3d elements.Thus the valence e-s are less tightly held and hence can form metal-metal bond more frequently [high enthalpy of atomisation]. 10.Why do transition elements show variable oxidation states? Transition elements show variable oxidation states due to incompletely filled d orbitals, both (n-1)d and ns electrons take part in bond formation (due to almost similar energy of ns and (n- 1) d orbitals) 11.Transition metals generally form coloured ions. Why? Due to the presence of unpaired d electrons, transition metal ions undergo dd transition of electrons by absorbing light from the visible region of electromagnetic spectrum. Metal ion with incomplete d orbital (d1 d9) is coloured . *Mn2+ is coloured .( electronic configuration is [Ar] 3d5). *Zn2+ is colourless(electronic configuration is [Ar] 3d10) 12.Transition metal ions are paramagnetic in nature.Why? Many of transition metal ions are paramagnetic due to the presence of unpaired electrons 13.The transition metals form a large number of complex compounds.Why? This is due to i) comparatively smaller sizes of the metal ions, ii) high ionic charges of metal ions iii) availability of vacant d orbitals for bond formation. 14.Transition metals and their many compounds act as good catalyst. Catalytic properties shown by transition metals can be explained due to (i) Presence of variable oxidation state and (ii) ability of elements to form complexes. (iii) Surface of metals where the reaction can occur. 15.Transition metals form alloys. Why? A)Transition metals form alloys because transition metals have similar radii and one transition metal can displace other transition metal from its lattice sites 16.Transition metals form interstitial compounds.Why? Due to the presence of voids which can trap small atoms like H, C,N 17. Name a transition element which does not exhibit variable oxidation states. Scandium (Z = 21) does not exhibit variable oxidation states. Sc 3+ stable d0 configuration. 18. Name the element of the first transition series (3d) which exhibits the largest no. of O.S. Why? Manganese [3d5 4s2] because it has maximum no. of unpaired electrons. 19. Name the element of the first transition series (3d) which exhibits +1 O.S most frequently. Why? Copper. Cu 1+ has stable 3d10 configuration. [Cu -3d10 4s1] 20. Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration. Cr2+ is oxidised to Cr3+[ d4 to d3], Cr3+ has stable half-filled t2g3 level .The change from Mn3+ to Mn2+ results in the stable half-filled d5configuration. 21.Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?

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Because oxygen or fluorine has small size and high electronegativity and best oxidising elements, can oxidise the metal to its highest oxidation state 22.Why is the highest oxidation state exhibited in oxoanions of a metal ? Because oxygen has small size and high electronegativity and best oxidising elements, can oxidise the metal to its highest oxidation state 23.Which is a stronger reducing agent Cr2+ or Fe2+ and why ? Cr2+ is stronger reducing agent than Fe2+ because half filled t2g3 level (d3) of Cr3+is more stable than half filled d level (d5) of Fe3+ Reason: d4 d3 occurs in case of Cr2+ to Cr3+ But d6 d5 occurs in case of Fe2+ to Fe3+ 24.Why are Mn2+ compounds are more stable than Fe2+ compounds towards oxidation to their +3 state? Mn2+ is not oxidised to Mn3+ as Mn2+ has stable d5 configuration. [Third ionization enthalpy is very high]. Fe2+ [3d6] is easily oxidised to Fe3+ to give the stable d5 configuration. 25.Among the first transition metals, which divalent metal ion has maximum paramagnetic character and why? Mn2+, because of maximum number of unpaired electrons. 26.Predict which of the following will be coloured in aqueous solution? Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+ and Co2+. Give reasons for each. Except Sc3+and Cu+ all others will be coloured in aqueous solution because of incompletely filled 3d-orbitals, will give rise to d-d transitions. 27.Copper (I) compounds are white and diamagnetic but copper (II) compounds are coloured and paramagnetic. Why? [Cu -3d10 4s1 , Cu1+ -3d10 , Cu2+ -3d9] In copper( I )ion all orbitals are completely d10 filled so its compounds are white and diamagnetic. Copper (II) ion has one unpaired electron so it is paramagnetic and forms blue coloured compounds 28. Zn2+ salts are white while Cu2+ salts are blue.Zn2+ ion has completely filled d10 configuration, no unpaired e-, no d-d transition, hence white. In Cu2+ ion there is one unpaired d electron (3d9), d-d transition takes place.. 29.Sc forms no coloured ions, yet it is regarded as a transition element. Explain why? [Sc- 3d1 4s2] Sc in the ground state has one d e-, hence it is a transition element. Sc3+ has 3d0 configuration, no unpaired e- , no d-d transition , hence does not form coloured ions. 30.Copper (I) has d10 configuration, while copper (II) has d9 configuration, still copper (II) is more stable in aqueous solution than copper (I). (or) Cu (l) compounds undergo disproportionation in aqueous solution .why? (or) Explain why Cu+ ion is not stable in aqueous solutions? Cu2+ is more stable than Cu+ due to more negative hydration enthalpy of Cu2+ (aq) than Cu+(aq) which compensates for second ionisation enthalpy of copper. Cu+ being unstable undergo disproportionation to form Cu2+. 2 Cu+ Cu2+ + Cu 31. Explain why Cu has a positive Eo value. Due to its high enthalpy of atomization and high ionization enthalpy. The sum of the enthalpy of atomization and ionization enthalpy is high and is not balanced by low hydration enthalpy.

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32.The observed E value for Mn, Ni and Zn are more negative than expected. Explain Due to extra stability of the half filled d sub shell in Mn2+ and the completely filled d sub shell in Zn 2+ they have lower ionisation enthalpy and hence more negative Eo values whereas for Ni, E is negative due to high negative hyd H value. 33.How would you account for the increasing oxidising power in the seriesVO2+ < Cr2O72 < MnO4_ This is due to the increasing stability of the lower species to which they are reduced. 34.For the first row transition metals the E values are: E V Cr Mn Fe Co Ni Cu (M2+/M) 1.18 0.91 1.18 0.44 0.28 0.25 +0.34 Explain the irregularity in the above values. The E (M2+/M) values are not regular because of irregular variation of ionisation enthalpies and the sublimation enthalpies which are relatively much less for manganese and vanadium. 35.Why is the E value for the Mn3+/Mn2+ couple much more positive than that for Cr3+ /Cr2+ or Fe3+ /Fe2+ ? Explain. Because of larger third ionisation energy of Mn due to stable d5 configuration of Mn2+. Cr2+ is easily oxidized to Cr3+ to have stable t2g3 level. Fe2+ is easily oxidized to Fe3+ to have stable d5 configuration. 36. What is meant by disproportionation of an oxidation state? Give an example. When a particular oxidation state becomes less stable relative to other oxidation states, one lower, one higher, it is said to undergo disproportionation. 3 MnO42 + 4 H+ 2 MnO4+ MnO2 + 2H2O 2Cu+ Cu2+ + Cu 37.Cobalt(II) is stable in aqueous solution but in the presence of complexing reagents (ligands) it is easily oxidised. Co(III) has greater tendency to form complexes than Co(II). Hence in the presence of ligands, Co(II) changes to Co(III).[ie, the CFSE more than compensates the third IE] 38. With the increase in atomic number the atomic radius does not change very much in the transition series. Why? As atomic number increases, the nuclear charge increases but the addition of electron in d-subshell increases the screening effect which counterbalances the effect of increased nuclear charge. 39.How does ionisation enthalpies of transition elements varies in a series? Due to an increase in nuclear charge which accompanies the filling of the inner d orbitals, there is an increase in ionisation enthalpy along each series of the transition elements from left to right. 40. How would you account for the irregular variation of ionization enthalpies (first and second) in the first series of the transition elements? Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of different 3dconfigurations (e.g., d0, d5, d10 are exceptionally stable). 41.Second ionization is difficult from Cu and Cr whereas it is easy for Zn. Cr - 3d5 4s1 and Cu- 3d10 4s1. Removal of second electron disturbs the stable d5/d10 configuration which requires high enthalpy whereas Zn- 3d104s2. Removal of second electron gives Zn completely filled d10 configuration. Therefore second ionization is easier for Zn but difficult for Cr and Cu 42.Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic number is 25.

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A)With atomic number 25, the divalent ion in aqueous solution will have d5 configuration (five unpaired electrons). The magnetic moment, is M -3d5 4s2, M2+ - 3d5 =n(n+2) = 5(5 + 2) = 5.92BM 43. Calculate the spin only magnetic moment of M2+ (aq) ion (Z = 27). M -3d7 4s2, M2+ - 3d7 [3 unpaired electrons] =n(n+2) = 3(3 + 2) = 3.87BM 44.What are interstitial compounds? Interstitial compounds are those which are formed when small atoms like H,C or N are trapped inside interstitial site of the crystal lattice of metals. Eg TiC,Mn4N 45. Write some characteristics of interstitial compounds. Some characteristics of interstitial compounds are (i) They have high melting points. (iii) They retain metallic conductivity. (ii) They are very hard. (iv) They are chemically inert. 46.Explain the variation in Atomic and Ionic Sizes of Transition Metals Atomic and ionic radius decreases with increasing atomic number. This is because the new electron enters a d orbital each time, the nuclear charge increases by unity, poor shielding of d electrons. 47.Name the oxometal anions of the first series of the transition metals in which the metal exhibits the oxidation state equal to its group number. Vanadate VO3 ,chromate CrO42- , permanganate MnO448. How is the variability in oxidation states of transition metals different from that of the non transition metals? Illustrate with examples. 1. The variability in oxidation states of transition metals is due to incompletely filled d orbitals. The oxidation states of transition elements differ from each other by unity.Eg: Mn - +2, +3, +4, +5, +6, +7. The oxidation states of non transition elements differ by 2. E.g. Pb+2, Pb+4,[ or +3, +5 or +4, +6] etc. 2. In transition elements, the higher oxidation states are more stable for heavier elements in a group, eg: in gp 6, Mo(VI) & W(VI) are more stable than Cr(VI). In p block elements, the lower oxidation states are more stable for heavier elements in a group due to inert pair effect. Eg: Pb2+ is more stable than Pb 4+. 49.To what extent do the electronic configuration decides the stability of oxidation states in the first series of transition elements? In a transition series, the oxidation states which leads to exactly half filled or completely filled d-orbitals are more stable. For example in the first transition series, Mn - 3d5 4s2, shows oxidation states +2 to +7 but Mn2+is most stable because it has the half filled 3d5configuration. 50.The d1 configuration is very unstable in ions. The ions with d1 configuration have the tendency to lose one d electron to acquire stable d0 configuration (stable noble gas configuration) 51.Why do transition elements show similarities along the period [horizontal similarities] and vertical similarities? Horizontal similarities - Because in transition metals electrons enter in d-oribital of second last shell but outer shell electronic configuration remains the same. Vertical similarities- similar electronic configuration. 52.The lowest oxide of transition metal is basic, the highest is acidic.

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The lower oxide of transition metal is basic because metal atom has low oxidation states (can donate electrons) and highest oxide is acidic because metal atom has highest oxidation states(can accept electron). For example MnO is basic and Mn2O7 is acidic 53. The lowest oxidation state of manganese is basic while the highest is acidic. In its highest oxidation state manganese can only accept electrons and so is acidic in behaviour. Similarly in its lowest oxidation state, it can donate electrons and hence is basic. 54.What is the basic difference between the electronic configuration of the transition and inner transition metals? In transition metals last electron enters the d-orbital of the second last shell (n-1) but in the inner transition metals the last electron enters the f-orbital of the third last shell (n-2). 55.What is the basic difference between the electronic configuration of the transition and non transition metals? 56.There is in general an increase in density of element from titanium (Z = 22) to copper (Z = 29). On moving from titanium (Z = 22) to copper (Z = 29), electrons get added to the 3d orbital. So, the mass per unit volume increases. As a result, density also increases. 57.The greatest number of oxidation states are exhibited by the members in the middle of a transition series. The elements at the extreme ends of a series exhibit fewer oxidation states because they have less number of electrons or too many d electrons, and hence, fewer orbitals for bonding. The greatest number of oxidation states is exhibited by the members in the middle of a transition series because of greater no. of unpaired electrons. THE INNER TRANSITION ELEMENTS ( f-BLOCK) The elements in which the extra electron enters ( n- 2 )f orbitals are called f- block elements. These elements are also called as inner transition elements because they form a transition series within the transition elements. The f-block elements are also known as rare earth elements. These are divided into two series. i) The Lanthanide series (4f-block elements) ii) The Actinide series (5f- block elements ) Lanthanoids- 14 elements following lanthanum filling takes place in 4f orbitals in 6th period.[Ce-Lu] Electronic Configurations. (n-2)f1-14 (n-1)d0-1 ns2 [54 Xe ]4f1-14 5d0-1 6s2 Lanthanum( La) 5d16s2 Gadolinium(Gd ) 4f 75d16s2 1 1 2 Cerium (Ce ) 4f 5d 6s Ytterbium (Yb) 4f 146s2 7 2 Europium (Eu) 4f 6s Lutetium (Lu) 4f 145d16s2 Oxidation states The common oxidation state exhibited by all the lanthanides is +3, also exhibit +2 and +4 states to attain stable f0, f7, f14 configurations. La - +3, Ce - +3, +4, +2, Pr - +3, +4, Nd - +3, +4, +2 Actinoids- 14 elements following actinium filling takes place in 5f orbitals in 7th period.[Th-Lw] 58. Name a member of the lanthanoid series which is well known to exhibit +4 oxidation state. Cerium (Ce - 4f15d16s2 ,Ce4+ -4f0) 59 .What is the lanthanoid contraction? What are its causes? Lanthanoid contractions The regular decrease in size or radii of Lanthanoids [La Lu] with increase in atomic number due to poor shielding effect of 4f electrons, the effective nuclear charge increases is called Lanthanoid contraction. [The shape of f orbitals is diffused].

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60 .Explain the consequences of lanthanide contraction i)Second and third transition series have similar radii and similar properties .Eg: Due to lanthanoid contraction Zr(160 pm) and Hf (159 pm) have almost similar radii and similar properties, occur together in nature and difficult to separate. ii) Due to lanthanoid contraction, the basic character of hydroxides of lanthanides decreases from La(OH)3 to Lu(OH) 3. As ionic size decreases from La 3+ to Lu 3+, basic strength of hydroxides decreases because covalent character of the hydroxides increases. Thus La(OH)3 is most basic while Lu (OH) 3 is the least basic. 61. Zr and Hf have identical sizes./ Zr and Hf occur in nature together./ Separation of Zr and Hf from a mixture is difficult. Explain Due to lanthanoid contraction, Zr(160 pm) and Hf (159 pm) have almost similar radii and similar properties. 62. La(OH)3 is more basic than Lu(OH)3 Due to lanthanoid contraction. As ionic size decreases from La decreases because covalent character of the hydroxides increases.
3+ 3+

to Lu

, basic strength of hydroxides

63. What is actinoid contraction? The regular decrease in atomic and ionic radii with increase in atomic number from actinium to lawrencium due to poor shielding effect of 5f electrons, the effective nuclear charge increases is called actinoid contraction. 64.Actionoid contraction is more than lanthanoid contraction. Give reason.(or) The gradual decrease in size (actinoid contractions) from element to element is greater among the actinoids than among the lanthanoids (lanthanoid contraction). The actinoid contraction is more than Lanthanoid contraction due to poor shielding power of 5f electrons than by 4f electrons. 65 .The second and third transition series elements have almost similar atomic radii. In the third transition series after lanthanum there is lanthanoid contraction, due to poor shielding of f electrons. 66.The chemistry of actionoids is more complicated than lanthanoids. Why? (or) Briefly explain why the EC of actinoids are not known with certainity. The complications in the actinoid series is due to i) Existence of a wide range of oxidation states due to small energy difference between 5f, 6d and 7s subshells ii) Their radioactivity. 67.Electronic configuration of actinoids are irregular why? This due to extra stability of f , f7 and f 14 orbitals and almost identical energy of 5 f ,6d and 7s orbitals 68.Actinoids show larger number of oxidation states than lanthanoids. Why? (or) The chemistry of the actinoids elements is not so smooth as that of lanthanoids. Justify this statement by giving some examples from the O.S of these elements. Actinoids exhibit greater range of oxidation states [+3,+4,+5,+6,+7, most common-+3] because the 5f, 6d and 7s sub-shells present in actinoids are of comparable energy(almost same energy). Thus, they can take part in bonding.Eg: Np shows+3,+4,+5,+6,+7 O.S Lanthanoids shows limited no of oxidation states [+2,+3,+4, most common-+3] because the 4f, 5d and 6s sub-shells have large energy difference. 69.Compare the chemistry of the actinoids with that of lanthanoids with special reference to 1. Electronic configuration 2. Oxidation states 3. Atomic sizes 4. Reactivity Lanthanoids Actinoids

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Electronic configuration Oxidation states 4f1-14 5d0-1 6s2 4f orbitals are progressively filled Lanthanoids shows limited no of O.S [+2,+3,+4, most common-+3] because the 4f, 5d and 6s sub-shells have large energy difference. The regular decrease in atomic and ionic radii with increase in atomic numberlanthanoid contraction 5f1-14 6d0-1 7s2 5f orbitals are progressively filled Actinoids exhibit wide range of O.S [+3,+4,+5,+6,+7, most common-+3] because the 5f, 6d and 7s subshells have small energy difference (almost same energy). The regular decrease in atomic and ionic radii with increase in atomic number- actinoid contraction. The actinoid contraction is more than Lanthanoid contraction due to poor shielding power of 5f electrons than by 4f electrons. Actinoids are more reactive than lanthanoids due to bigger size and lower IE They are all radioactive

Atomic and ionic size

Reactivity Radioactivity

Less reactive than actinoids.

With the exception of promethium, they are all non-radioactive. 70.What is the composition of mischmetall? Give its one use. (or) Name an important alloy which contains some of the lanthanoid metals. Mention its uses. Mischmetall is an alloy of a Lanthanoid metal which contains 95% lanthanoid metal, 5% iron and traces of S, C, Ca & Al. It is used in Magnesium based alloy to produce bullets, shell and lighter Flint. 71.What may be the possible oxidation states of the transition metals with the following d electronic configurations in the ground state of their atoms: 3d34s2, 3d54s2 and 3d64s2 Indicate relative stability of oxidation states in each case. In a transition series, those oxidation states are stable which lead to exactly half-filled or completely-filled d orbitals. 3d34s2: Oxidation states: +2, +3,+4,+5 Stable oxidation states: +2, +5 3d54s2: Oxidation states:+2,+3,+4,+5,+6,+7 Stable oxidation states: +2, +7 3d64s2: Oxidation states: +2, +3, +4, +6 Stable oxidation states: +2, +3

72.What is the effect of lanthanoid contraction on the chemistry of the elements which follow lanthanoids? As a result of the lanthanoid contraction,second and third transition series have similar radii and similar properties .Eg: Due to lanthanoid contraction Zr(160 pm) and Hf (159 pm) have almost similar radii and similar properties,occur together in nature and difficult faced to separate, 73.Similarities between lanthanoids and actinoids: 1. Both are electropositive elements and are quite reactive. 2. The +3 oxidation state is the most common oxidation state in both the series. 3. The atomic size of elements keeps decreasing on moving from left to right in both the series. This is known as lanthanoid and actinoid contraction. 74..Among the lanthanoids, Ce(III) is easily oxidised to Ce(IV). Because Ce(IV) has extrastability due to empty f 0 orbital(noble gas configuration) . 75. Ce4+ is used as an oxidizing agent in volumetric analysis. Ce4+ has the tendency to attain +3 oxidation state (common oxidation state of lanthanoids) and so it is used as an oxidizing agent in volumetric analysis. 76. What is the basic difference between the electronic configuration of the transition and inner transition metals?

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In transition metals last electron enters the d-orbital of the second last shell but in the inner transition metals the last electron enters the f-orbital of the third last shell. 77. CrO42- is a strong oxidizing agent while MnO42- is not. Oxidation state of Cr in CrO42- is +6. This is its maximum oxidation state and it can only gain electrons. Oxidation state of Mn in MnO42- is +6. Mn can further loose electron to become 7+ which is its highest oxidation state 78. Out of Ag2SO4, CuF2 , MgF2 and CuCl, which compound will be coloured and why? CuF2 .In CuF2, Cu2+ (3 d9) has an unpaired electron. 79.What is the most common oxidation state shown by lanthanoids and actinoids?+ 3 80. Write the uses of lanthanoids. 1. The best use of the lanthanoids is for the production of alloy steels for plates and pipes. 2.A well known alloy is mischmetall which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al. Mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint. 3. Mixed oxides of lanthanoids are used as catalysts in petroleum cracking. 4. Ln oxides are used as phosphors in television screens and similar fluorescing surfaces. 81. Explain briefly how +2 state becomes more and more stable in the first half of the first row transition elements with increasing atomic number?

Potassium dichromate K2Cr2O7 82. .Describe the preparation of potassium dichromate from iron chromite ore. Step I: preparation of sodium chromate: Chromite ore (FeCr2O4) is fused with sodium or potassium carbonate in free access of air to give sodium chromate. 4 FeCr2O4 + 8 Na2CO3 + 7 O2 8 Na2CrO4 + 2 Fe2O3 + 8 CO2 Step II: conversion of sodium chromate into sodium dichromate: The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a solution from which orange sodium dichromate, Na2Cr2O7. 2H2O can be crystallised. 2Na2CrO4 + 2 H+ Na2Cr2O7 + 2 Na+ + H2O Step III: conversion of sodium dichromate into potassium dichromate: Potassium dichromate is prepared by treating the solution of sodium dichromate with potassium chloride. Na2Cr2O7 + 2 KCl K2Cr2O7 + 2 NaCl Orange crystals of potassium dichromate crystallise out. 83.What is the effect of pH on chromate and dichromate ions? The chromates and dichromates are interconvertible in aqueous solution depending upon pH of the solution. In acidic pH (When PH decreases),yellow chromate ion gets converted into orange dichromate ion. 2 CrO42 + 2H+ Cr2O7 2 + H2O In basic pH(When PH increases) orange dichromate ion gets converted into yellow chromate ion. Cr2O72 + 2 OH- 2 CrO42 + H2O 84. Explain Oxidising property of potassium dichromate

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Potassium dichromate is a strong oxidising agent. In acidic solution, its oxidising action can be represented as follows: Cr2O72 + 14H+ + 6e 2Cr3+ + 7H2O Thus, acidified potassium dichromate will oxidise iodides to iodine, sulphides to sulphur, tin(II) to tin(IV) and iron(II) salts to iron(III). The half-reactions are noted below: 6 I 3I2 + 6 e ; 3Sn2+ 3Sn4+ + 6 e + 3 H2S 6H + 3S + 6e; 6 Fe2+ 6Fe3+ + 6 e

Examples: Oxidises iodide to iodine Oxidises iron (II) solution to iron (III) solution i.e., ferrous ions to ferric ions Oxidises H2S to sulphur

85. Explain preparation of Potassium permanganate from pyrolusite ore From pyrolusite ore: Potassium permanganate is prepared by fusion of MnO2 with an alkali metal hydroxide and an oxidising.agent like KNO3.This produces the dark green K2MnO4. 2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O K2MnO4 then disproportionates in a neutral or acidic solution to give purple crystals of permanganate. 3MnO42 + 4H+ 2MnO4 + MnO2 + 2H2O 86. Explain commercial method of preparation of Potassium permanganate

1. Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the electrolytic oxidation of mangana (Vl).

2. Electrolytic oxidation of manganate ion in alkaline solution give purple clour permanganate.

87. Explain Laboratory method of preparation of Potassium permanganate In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.

88. What happens when KMnO4 is heated? When heated it decomposes at 513 K to give potassium manganate(Green coloured) 2KMnO4 K2MnO4 + MnO2 + O2 89. Explain Oxidising property of potassium permanganate Potassium permanganate is a strong oxidising agent in acidic,alkaline and neutral medium. *In acidic medium, its oxidising action can be represented as follows: MnO4 + 8H+ + 5e Mn2+ + 4H2O * A few important oxidising reactions of KMnO4 are given below:

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1. In acid solutions: (a) Iodides oxidizes to free iodine (Reaction with potassium iodide, KI) 10I + 2MnO4 + 16H+ > 2Mn2+ + 8H2O + 5I2 (b) Fe2+ ion is converted to Fe3+ (Reaction with ferrous sulphate) 5Fe2+ + MnO4 + 8H+ > Mn2+ + 4H2O + 5Fe3+ (c) Oxalates oxidizes to carbondioxide(Reaction with oxalic acid) 5C2O42 + 2MnO4 + 16H+ > 2Mn2+ + 8H2O + 10CO2 d)Hydrogen sulphide is oxidised to sulphur 5S2 + 2MnO4 + 16H+ > 2Mn2+ + 8H2O + 5S (e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid: 5SO32 + 2MnO4 + 6H+ > 2Mn2+ + 3H2O + 5SO42 (f) Nitrite is oxidised to nitrate: 5NO2 + 2MnO4 + 6H+ > 2Mn2+ + 5NO3 + 3H2O 2. In neutral or faintly alkaline solutions: It oxidises: 1. Iodide to iodate: 2MnO4 + H2O + I > 2MnO2 + 2OH + IO3 2. Thiosulphate is oxidised to sulphate:

3. Manganous salt is oxidised to MnO2; the presence of zinc sulphate or zinc oxide catalyses the oxidation: 90. Permanganate titrations in presence of hydrochloric acid are unsatisfactory.Why? Permanganate titrations in presence of hydrochloric acid are unsatisfactory since hydrochloric acid is oxidised to chlorine. 91.What is the effect of adding a base to potassium dichromate? When a base is added to orange coloured potassium dichromate its colour changes to yellow due to formation of potassium chromate. 92.Draw the structure of chromate and dichromate ions?

93. Draw the structure of manganate and permanganate ions?

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94. What is the ore of K2Cr2O7 and KMnO4 ? Potassium dichromate Chromite ore (FeCr2O4) Potassium PermanganateMnO2pyrolusite. 95 .Why the chromates in acidic solution becomes orange and dichromates in alkaline solution becomes yellow? Because chromates in acidic medium are converted into dichromates and the dichromates in alkaline solution are converted into chromates.