Compare the chemistry of actinoids with that of the lanthanoids with special reference to
(i) electronic configuration,
(ii) atomic and ionic sizes and
(iii) oxidation state
(iv) chemical reactivity.
(i) Electronic configuration: The general electronic configuration of lanthanoids is [Xe]54 4f1-14 5d0-1 6s2 and that of actinoids is [Rn]86 5f0-14 6d0-1 7s2, lanthanoids . belong to 4 f series whereas actinoids belong to 5f-series.
(ii) Atomic and ionic sizes: Both lanthanoids and actinoids show decrease in size of their atoms or ions in + 3 oxidation state as we go from left to right. In lanthanoids, the decrease is called lanthanoid contraction whereas in actinoids, it is called actinoid contraction. The contratibn is greater from element to element in actinodes due to poorer shielding by 5f electrons.
(iii)Oxidation state: Lanthanoids show limited oxidation states (+ 2, + 3, + 4) out of which + 3 is most common whereas actinoids show +3, +4, +5, +6, +7 oxidation states.This is because of large energy gap between 4f 5d and 6s orbitals. However, actinoids show a large number of oxidation states because of small energy ap- between 5f 6d and Is orbitals.
(iv) Chemical reactivity: The earlier members
of the lanthanoids series are quite reactive similar to calcium but, with increase in atomic number, they behave more like aluminium. The metals combine with hydrogen when . gently heated in the gas. Carbides, Ln3C, Ln2C3 and LnC2 are formed when the metals are heated with carbon. They liberate hydrogen from dilute acid and burn in halogens to form halides. They form oxides M203 and hydroxides M(OH)3.
Actinoids are highly reactive metals, especially when finely divided. The action of boiling water on them gives a mixture of oxide and hydride and combination with most non-metals take place at moderate temperatures. HCl attacks all metals but most are slightly affected by nitric acid owing to the formation of protective oxide layers, alkalis have no action. Actinoids are more reactive than lanthanoids due to bigger atomic size and lower ionisation energy.
Assertion (A): Cu can not libirate hydrogen from acids .
Reason (R): because it has positive electrode potential.
Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
When a chromite ore (A) is fused with sodium carbonate in free excess of air and the product is dissolved in water, a yellow solution of compound (B) is obtained. After treatment of this yellow solution with sulphuric acid, compound (C) can be crystallized from the solution. When compound (C) is treated with KCl, orange crystals of compound (D) crystallise out. Identify A to D and also explain the reactions.
In the following questions, a statement of Assertion (A) followed by a statement of Reason (R) is given. Choose the correct answer out of the following choices:
(a) Both Assertion and Reason are true and the Reason is the correct explanation of Assertion.
(b) Both Assertion and Reason are true and the Reason is not the correct explanation of Assertion.
(c) Assertion is not true but the Reason is true.
(d) Both Assertion and Reason are false.
Assertion (A): Cu2+ iodide is not known.
Reason (R): Cu2+ oxidises I to iodine.
What may be the stable oxidation state of the transition element with the following delectron configurations in the ground state of their atoms: 3d3,3d5, 3d8 and 3d4?
Assertion (A): The highest oxidation state of osmium is +8.
Reason (R): Osmium is a 5d-block element.
Comment on the statement that elements of the first transition series possess many properties different from those of heavier transition elements.
Assertion (A): The highest oxidation state of osmium is +8.
Reason (R): Osmium is a 5d-block element.
Indicate the steps in the preparation of:
(i) K2Cr207from chromite ore
(ii) KMn04 from pyrolusite ore.
Generally, transition-elements and their salts are coloured due to the presence of unpaired electrons in metal ions. Which of the following compounds are coloured?
(a) kMnO4 (b) Ce(SO4)2 (c) TiCl4 (d) Cu2Cl2
Write down the electronic configuration of (i) Cr3+ (ii) Pm3+ (iii) Cu+ (iv) Ce4+(v) Co2+ (vi) Lu2+(vii) Mn2+ (viii) Th4+.
Calculate the number of unpaired electrons in the following gaseous ions : Mn3+, Cr3+, V3+ and Ti3+. Which one of these is the most stable in aqueous solution.
Calculate the number of unpaired electrons in the following gaseous ions : Mn3+, Cr3+, V3+ and Ti3+. Which one of these is the most stable in aqueous solution.
Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite difficult to separate them. Why?
How would you account for the following:
(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidizing.
(ii) Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents it is easily oxidised.
(iii) The d1 configuration is very unstable in ions.
Which of the following ions show higher spin only magnetic moment value?
(a) Ti3+ (b) Mn2+ (c) Fe2+ (d) Co3+
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.
Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of increasing pH on a solution of potassium dichromate?
In the form of dichromate, Cr (VI) is a strong oxidizing agent in acidic medium but Mo (VI) in MoO3 and W (VI) in WO3 are not because
(a) Cr (VI) is more stable than Mo(VI) and W(VI)
(b) Mo(VI) and W(VI) are more stable than Cr(VI)
(c) higher oxidation states of heavier members of group-6 of transition series are more stable
(d) lower oxidation states of heavier members of group-6 of transition series are more stable
Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a transition element?
What are interstitial compounds? Why are such compounds well known for transition metals?
Describe the oxidising action of potassium dichromate and write the ionic equations for its reaction with:
(i) iodide
(ii) iron (II) solution and
(iii) H2S
Metallic radii of some transition elements are given below. Which of these elements will have highest density?
(a) Transition metals can act as catalysts because these can change their oxidation state.
How does Fe(III) catalyse the reaction between iodide and persulphate ions?
(b) Mention any three processes where transition metals act as catalysts.
Explain giving reasons:
(i)Transition metals and many of their compounds show paramagnetic behaviour.
(ii)The enthalpies of atomisation of the transition metals are high.
(iii)The transition metals generally form coloured compounds.
(iv)Transition metals and their many compounds act as good catalyst
Predict which of the following will be coloured in aqueous solution? Ti3+, V3+,Cu+, Sc3+, Mn2+, Fe3+ and Co2+ Give reasons for each.
What are inner transition elements? Decide which of the following atomic numbers are the atomic numbers of the inner transition elements: 29,59,74,95,102,104.
Which is the last element in the series of the actinoids? Write the electronic configuration of this element. Comment on the possible oxidation state of this element
Name the members of the lanthanoid series which exhibit+4oxidatk>nstatesandthosewhichexhibit +2 oxidation states. Try to correlate this type of behaviour with the electronic configurations of these elements.
Explain why does colour of KMnO4 disappear when oxalic acid is added to its solution in acidic medium?
Mention the type of compounds formed when small atoms like H, C and N get trapped inside the crystal lattice of transition metals. Also give physical and chemical characteristics of these compounds.
What are the characteristics of the transition . elements and why are they called transition elements? Which of the d-block elements may not be regarded as the transition elements?
Which of the following lanthanoids show +2 oxidation state besides the characteristic oxidation state +3 of lanthanoids?
(a) Ce (b) Eu (c) Yb (d) Ho
Although +3 is the characteristic oxidation state for lanthanoids but cerium
also shows +4 oxidation state because
(a) it has variable ionization enthalpy
(b) it has a tendency to attain noble gas configuration
(c) it has a tendency to attain f ° configuration
(d) it resembles Pb4+
Although +3 oxidation states is the characteristic oxidation state of lanthanoids but cerium shows +4 oxidation state also. Why?
While filling up of electrons in the atomic orbitals, the 4s orbital is filled before the 3d-orbital but reverse happens during the ionization of the atom. Explain why?
In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the lowest, i.e., 126 kJ mol-1 . Why?
The chemistry of the actinoid elements is not so smooth as that of the lanthanoids. Justify this statement by giving some examples from the oxidation state of these elements.
Gadolinium belongs to 4f series. Its atomic number is 64. Which of the following is the correct electronic configuration of gadolinium?
