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
(i) Magnetic properties: Transition elements and many of their compounds are paramagnetic, i.e., they are weakly attracted by a magnetic field. This is due to the presence of unpaired electrons in atoms, ions or molecules. The paramagnetic character increases as the number of . unpaired electrons increases. The paramagnetic character is measured in terms of magnetic moment and is given by
(ii) Because of large number of unpaired electrons in d-orbitals of their atoms they have stronger interatomic intefactions and hence stronger metallic bonding between atoms resulting in higher enthalpies of atomisation.
(iii) Formation of coloured compounds (both in solid state as well as in aqueous solution) is another very common characteristics of transition metals. This is due to absorption of some radiation from visible light to cause d-d transition of electrons in transition metal atom. The d-orbitals do not have same energy and under the influence of ligands, the d-orbitals split into two sets of orbitals having different energies; transition of electrons can take place from one set of d-orbitals to another set within the same sub-shell. Such transitions are called d-d transitions. The energy difference for these d-d transitions fall in the visible region. When white light is incident on compounds of transition metals, they absorb a particular frequency and remaining colours are emitted imparting a characteristic colour to the complex. Zn2+ and Ti4+ salts are white because they do not absorb any radiation in visible region.
(iv)Catalytic properties: Many of transition metals and their compounds act as catalyst in variety of reactions, e.g., finely divided iron in manufacture of NH3 by Haber's process, V2O5 or Pt in manufacture of H2S04 by Contact process, etc.). The catalytic activity is due to following two reasons.
(a)The ability of transition metal ion to pass ” easily from one oxidation state to another
and thus providing a new path to reaction with lower activation energy.
(b)The surface of transition metal acts as very good adsorbent and thus provides increased concentration of reactants on their surface causing the reaction to occur.
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?
Although fluorine is more electronegative than oxygen, but the ability of oxygen to stabilize higher oxidation states exceeds that of fluorine. Why?
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?
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.
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?
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.
Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a transition element?
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
Compare the chemistry of actinoids with that of lanthanoids with reference to:
(i) Electronic configuration
(ii) Oxidation states
(iii) Chemical reactivity
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
Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite difficult to separate them. Why?
A violet compound of manganese (A) decomposes on heating to liberate oxygen and compounds (B) and (C) of manganese are formed. Compound (C) reacts with KOH in the presence of potassium nitrate to give compound (B). On heating compound (C) with cone. H2SO4 and NaCl, chlorine gas is liberated and a compound (D) of manganese along with other products is formed. Identify compounds A to D and also explain the reactions involved.
What is meant by disproportionation? Give two examples of disproportionation reaction in aqueous solution.
Comment on the statement that elements of the first transition series possess many properties different from those of heavier transition elements.
Which of the following will not act as oxidizing agents?
(a) CrO3 (b) MoO3(c) WO3 (d) CrO42-
(a) Answer the following questions:
(i) Which element of the first transition series has highest second ionization enthalpy?
(ii) Which element of the first transition series has highest third ionization enthalpy?
(iii) Which element of the first transition series has lowest enthalpy of atomization?
(b) Identify the metal and justify your answer:
(i) Carbonyl M(CO)5 (ii) MO3F
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
Although Cr3+ and CO2+ ions have same number of unpaired electrons but the magnetic moment of Cr3+ is 3.87 BM and that of CO2+ is 4.87 BM. 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?
Assertion (A): The highest oxidation state of osmium is +8.
Reason (R): Osmium is a 5d-block element.
How would you account for the irregular variation of ionisation enthalpies (first and second) in the first series of the transition elements?
Compare the stability of +2 oxidation state for the elements of the first transition series.
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.
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
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?
Assertion (A): The highest oxidation state of osmium is +8.
Reason (R): Osmium is a 5d-block element.
When an oxide of manganese (A) is fused with KOH in the presence of an oxidizing agent and dissolved in water, it gives a dark green solution of compound (B). Compound (B) disproportionates in neutral or acidic solution to give purple compound (C). An alkaline solution of compound (C) oxidises potassium iodide solution to a compound (D) and compound (A) is also formed. Identify compounds A to D and also explain the reactions involved.
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?
Metallic radii of some transition elements are given below. Which of these elements will have highest density?
KMnO4 acts as an oxidizing agent in acidic medium. The number of moles of KMn04 that will be needed to react with one mole of sulphide ions in acidic solution is
Assertion (A): Actinoids form relatively less stable complexes as compared to lanthanoids.
Reason (R): Actinoids can utilize their 5d orbitals along with 6d orbitals in bonding but lanthanoids do not use their 4f orbital for bonding.
Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of increasing pH on a solution of potassium dichromate?
For M2+/M and M3+/M2+ systems the E ° values for some metals are as follows:
Cr2+/Cr –> -0.9 V
Mn2+/Mn –> -1.2V
Fe2+/Fe –> -0.4 V
Cr3+/Cr2+ –> -0.4 V
Mn3+/Mn2+ –>+ 1.5V
Fe3+/Fe2+ –>+ 0.8V
(ii) the ease with which iron can be oxidised as compared to a similar process for either chromium or manganese metal.
Indicate the steps in the preparation of:
(i) K2Cr207from chromite ore
(ii) KMn04 from pyrolusite ore.
Gadolinium belongs to 4f series. Its atomic number is 64. Which of the following is the correct electronic configuration of gadolinium?
