Compare the chemistry of the actinoids with that of lanthanoids with reference to:
(i) electronic configuration
(ii) oxidation states and
(iii) chemical reactivity.
Electronic configuration
The general electronic configuration for lanthanoids is [Xe]544f0-145d0-16s2 and that for actinoids is [Rn]865f1-146d0-17s2. Unlike 4 forbitals, 5f orbitals are not deeply buried and participate in bonding to a greater extent.
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 7slevels 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.
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
What happens when H3PO3 is heated?
Analysis shows that nickel oxide has the formula Ni0.98 O1.00. What fractions of nickel exist as Ni2+and Ni3+ions?
Write the chemistry of recharging the lead storage battery, highlighting all the materials that are involved during recharging.
How will you distinguish between the following pairs of terms:
(i) Hexagonal close-packing and cubic close-packing?
(ii) Crystal lattice and unit cell?
(iii) Tetrahedral void and octahedral void?
The melting points and solubility in water of amino acids are generally higher than that of the corresponding halo acids. Explain.
Conductivity of 0.00241 M acetic acid is 7.896 × 10 - 5 S cm - 1. Calculate its molar conductivity and if Amº for acetic acid is 390.5 S cm2 mol - 1, what is its dissociation constant?
Explain the difference between Buna-N and Buna-S.
What is a biodegradable polymer? Give an example of a biodegradable aliphatic polyester.
Arrange the compounds of each set in order of reactivity towards SN2 displacement:
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 3-Bromo-2- methylbutane
(iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-3-methylbutane.
Write the IUPAC names of the following coordination compounds:
(i) [Co(NH3)6]Cl3
(ii) [Co(NH3)5Cl]Cl2
(iii) K3[Fe(CN)6]
(iv) K3[Fe(C2O4)3]
(v) K2[PdCl4]
(vi) [Pt(NH3)2Cl(NH2CH3)]Cl