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.
(i) E ° value for Cr3+/Cr2+ is negative (-0-41 V) whereas E ° values for Mn3+/Mn2+is positive (+1.57 V). Hence, Cr2+ ion can easily undergo oxidation to give Cr3+ ion and, therefore, act as strong reducing agent whereas Mn3+ can easily undergo’ reduction to give Mn2+ and hence act as an oxidizing agent.
(ii) Co (III) has .greater tendency to form coordination complexes than Co (II). Hence, in the presence of ligands, Co (II) changes to Co (III), i.e., is easily oxidized.
(iii) The ions with dx configuration have the tendency to lose the only electron present in d-subshell to acquire stable d ° configuration. Hence, they are unstable and undergo oxidation or disproportionation.
Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
Assertion (A): Cu can not libirate hydrogen from acids .
Reason (R): because it has positive electrode potential.
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.
Comment on the statement that elements of the first transition series possess many properties different from those of heavier transition elements.
Indicate the steps in the preparation of:
(i) K2Cr207from chromite ore
(ii) KMn04 from pyrolusite ore.
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.
Assertion (A): The highest oxidation state of osmium is +8.
Reason (R): Osmium is a 5d-block element.
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?
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.
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.
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.
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
Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a transition element?
Which of the 3d series of the transition metals exhibits the largest number of oxidation states and why?
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.
Assertion (A): The highest oxidation state of osmium is +8.
Reason (R): Osmium is a 5d-block element.
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.
Write down the electronic configuration of (i) Cr3+ (ii) Pm3+ (iii) Cu+ (iv) Ce4+(v) Co2+ (vi) Lu2+(vii) Mn2+ (viii) Th4+.
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 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?
What are alloys? Name an important alloy which contains some of the lanthanoid metals. Mention its uses.
Use Hund's rule to derive the electronic configuration of Ce3+ ion, and calculate its magnetic moment on the basis of ‘spin-only' formula.
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+
On the basis of lanthanoid contraction, explain the following:
(a) Nature of bonding in La2O3 and Lu2O3.
(b) Trends in the stability of oxo-salts of lanthanoids from La to Lu.
(c) Stability of the complexes of lanthanoids.
(d) Radii of Ad- and 5d-block elements.
(e) Trends in acidic character of lanthanoid oxides.
(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.
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?
How would you account for the irregular variation of ionisation enthalpies (first and second) in the first series of the transition elements?
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.
What is meant by disproportionation? Give two examples of disproportionation reaction in aqueous solution.
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.
When KMnO4 solution is added to oxalic acid solution, the decolourisation is slow in the beginning but becomes instantaneous after some time because
(a) CO2 is formed as the product (b) Reaction is exothermic
(c) Mn04 catalyses the reaction (d) Mn2+ acts as autocatalyst
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
Transition elements form binary compounds with halogens. Which of the following elements will form MF3 type compounds?
(a) Cr (b) Co (c) Cu (d) Ni
Which of the following will not act as oxidizing agents?
(a) CrO3 (b) MoO3(c) WO3 (d) CrO42-
When a brown compound of manganese
(A) is treated with HCl, it gives a gas
(B) The gas taken in excess, reacts with NH3 to give an explosive compound
(C) Identify compounds A, B and C.
Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite difficult to separate them. Why?
