How would you account for the irregular variation of ionisation enthalpies (first and second) in the first series of the transition elements?
There is a irregularity in the IE's of 3d-series due to alternation of energies of 4s and 3d orbitals when an e-1 is removed. Thus, there is a reorganisation energy accompanying ionization. This results into release of exchange energy which increases as the number of e-1 s increases in the dn configuration. Cr has low 1st IE because loss of 1 e- gives stable EC (3d6). Zn has very high IE because e~ has to be removed from 4s orbital of the stable configuration (3d10 4s2) After the loss of one e–, removal of 2nd e–, becomes difficult. Hence, 2nd IE's are higher and in general, increase from left to right. However, Cr and Cu show much higher values because 2nd e– has to be removed from stable configuration of Cr+ (3d5) and Cu+ (3d10)
Assertion (A): Cu can not libirate hydrogen from acids .
Reason (R): because it has positive electrode potential.
A solution of KMnO4 on reduction yields either a colourless solution or a brown precipitate or a green solution depending on pH of the solution. What different stages of the reduction do these represent and how are they carried out?
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
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.
Comment on the statement that elements of the first transition series possess many properties different from those of heavier transition elements.
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
What is meant by disproportionation? Give two examples of disproportionation reaction in aqueous solution.
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?
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.
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
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.
Which of the following will not act as oxidizing agents?
(a) CrO3 (b) MoO3(c) WO3 (d) CrO42-
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+
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.
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.
How would you account for the irregular variation of ionisation enthalpies (first and second) in the first series of the transition elements?
Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
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?
Gadolinium belongs to 4f series. Its atomic number is 64. Which of the following is the correct electronic configuration of gadolinium?
Which of the following actinoids show oxidation states up to +7?
(a) Am (b) Pu (c) U (d) Np
General electronic configuration of actinoids is (n – 2)f1-14 (n – 1 )d0-2 ns2. Which of the following actinoids have one electron in 6d orbital?
(a) U (Atomic no. 92) (b) Np (Atomic no. 93)
(c) Pu (Atomic no. 94) (d) Am (Atomic no. 95)
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.
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.
Write down the electronic configuration of (i) Cr3+ (ii) Pm3+ (iii) Cu+ (iv) Ce4+(v) Co2+ (vi) Lu2+(vii) Mn2+ (viii) Th4+.
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
Compare the stability of +2 oxidation state for the elements of the first transition series.
Metallic radii of some transition elements are given below. Which of these elements will have highest density?
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
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 fluorine is more electronegative than oxygen, but the ability of oxygen to stabilize higher oxidation states exceeds that of fluorine. Why?
Although +3 oxidation states is the characteristic oxidation state of lanthanoids but cerium shows +4 oxidation state also. Why?
Assertion (A): Separation of Zr and Hf is difficult.
Reason (R): Because Zr and Hf lie in the same group of the periodic table.
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.
(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 briefly how+2 state becomes more and more stable in the first half of the first row transition elements with increasing atomic number?
