Compare the chemistry of actinoids with that of the lanthanoids with specialreference to:
(i) electronic configuration
(ii) atomic and ionic sizes
(iii) oxidation stateand
(iv) chemical reactivity.
(i) Electronic configuration
The general electronic configuration for lanthanoids is [Xe]544f0-145d0-16s2 and that for actinoids is [Rn]865f1-146d0-17s2. Unlike 4forbitals, 5f orbitals are not deeply buried and participate in bonding to a greater extent.
(ii) Oxidation states
The principal oxidation state of lanthanoids is (+3). However, sometimes we also encounter oxidation states of + 2 and + 4. This is because of extra stability of fully-filled and half-filled orbitals. Actinoids exhibit a greater range of oxidation states. This is because the 5f, 6d, and 7s levels are of comparable energies. Again, (+3) is the principal oxidation state for actinoids. Actinoids such as lanthanoids have more compounds in +3 state than in +4 state.
(iii) Atomic and lonic sizes
Similar to lanthanoids, actinoids also exhibit actinoid contraction (overall decrease in atomic and ionic radii). The contraction is greater due to the poor shielding effect of 5f orbitals.
(iv) Chemical reactivity
In the lanthanide series, the earlier members of the series are more reactive. They have reactivity that is comparable to Ca. With an increase in the atomic number, the lanthanides start behaving similar to Al. Actinoids, on the other hand, are highly reactive metals, especially when they are finely divided. When they are added to boiling water, they give a mixture of oxide and hydride. Actinoids combine with most of the non-metals at moderate temperatures. Alkalies have no action on these actinoids. In case of acids, they are slightly affected by nitric acid (because of the formation of a protective oxide layer).
Explain why Cu+ ion is not stable in aqueous solutions?
Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a transition element?
The Eθ(M2+/M) value for copper is positive (+0.34V). What is possibly the reason for this? (Hint: consider its high ΔaHV and low ΔhydHV)
How would you account for the following:
(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidising.
(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.
Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
Which is a stronger reducing agent Cr2+ or Fe2+ and why?
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.
Give examples and suggest reasons for the following features of the transition metal chemistry:
(i)The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
(ii)A transition metal exhibits highest oxidation state in oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxoanions of a metal.
Predict which of the following will be coloured in aqueous solution?
Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+ and Co2+.
Give reasons for each.
Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of increasing pH on a solution of potassium dichromate?
For the reaction R → P, the concentration of a reactant changes from 0.03 M to 0.02 M in 25 minutes. Calculate the average rate of reaction using units of time both in minutes and seconds.
Write the formulas for the following coordination compounds:
(i) Tetraamminediaquacobalt (III) chloride
(ii) Potassium tetracyanonickelate(II)
(iii) Tris(ethane-1,2-diamine) chromium(III) chloride
(iv) Amminebromidochloridonitrito-N-platinate(II)
(v) Dichloridobis(ethane-1,2-diamine)platinum(IV) nitrate
(vi) Iron(III) hexacyanoferrate(II)
(i) Write structures of different isomeric amines corresponding to the molecular formula, C4H11N
(ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different pairs of amines?
Why are solids rigid?
Write any two characteristics of Chemisorption.
Write the structures of the following compounds.
(i) α-Methoxypropionaldehyde
(ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentane carbaldehyde
(iv) 4-Oxopentanal
(v) Di-sec-butyl ketone
(vi) 4-Fluoroacetophenone
Which of the ores mentioned in Table 6.1 can be concentrated by magnetic separation method?
Why are pentahalides more covalent than trihalides?
Glucose or sucrose are soluble in water but cyclohexane or benzene (simple six membered ring compounds) are insoluble in water. Explain.
Write structures of the following compounds:
(i) 2-Chloro-3-methylpentane
(ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert. Butyl-3-iodoheptane
(iv) 1,4-Dibromobut-2-ene
(v) 1-Bromo-4-sec. butyl-2-methylbenzene
Why copper matte is put in silica lined converter?
Which acid of each pair shown here would you expect to be stronger?
(i) CH3CO2H or CH2FCO2H
(ii)CH2FCO2H or CH2ClCO2H
(iii) CH2FCH2CH2CO2H or CH3CHFCH2CO2H
(iv)
Classify the following amines as primary, secondary or tertiary:
(i)
(ii)
(iii) (C2H5)2CHNH2
(iv) (C2H5)2NH
Calculate the mass percentage of aspirin (C9H8O4) in acetonitrile (CH3CN) when 6.5 g of C9H8O4 is dissolved in 450 g of acetonitrile (CH3CN).
Write the conditions to maximize the yield of H2SO4 by Contact process.
FeSO4 solution mixed with (NH4)2SO4 solution in 1:1 molar ratio gives the test of Fe2+ ion but CuSO4 solution mixed with aqueous ammonia in 1:4 molar ratio does not give the test of Cu2+ ion. Explain why?
Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4 in 2 liter of water at 25° C, assuming that it is completely dissociated.
Explain the term copolymerisation and give two examples.
Give the disproportionation reaction of H3PO3.
How is dacron obtained from ethylene glycol and terephthalic acid?