What is lanthanoid contraction? What are the consequences of lanthanoid contraction?
As we move along the lanthanoid series, the atomic number increases gradually by one. This means that the number of electrons and protons present in an atom also increases by one. As electrons are being added to the same shell, the effective nuclear charge increases. This happens because the increase in nuclear attraction due to the addition of proton is more pronounced than the increase in the interelectronic repulsions due to the addition of electron. Also, with the increase in atomic number, the number of electrons in the 4f orbital also increases. The 4f electrons have poor shielding effect. Therefore, the effective nuclear charge experienced by the outer electrons increases. Consequently, the attraction of the nucleus for the outermost electrons increases. This results in a steady decrease in the size of lanthanoids with the increase in the atomic number. This is termed as lanthanoid contraction.
Consequences of lanthanoid contraction
(i) There is similarity in the properties of second and third transition series.
(ii) Separation of lanthanoids is possible due to lanthanide contraction.
(iii) It is due to lanthanide contraction that there is variation in the basic strength of lanthanide hydroxides (Basic strength decreases from La (OH)3 to Lu (OH)3).
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
Give the structures of A, B and C in the following reactions:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
Arrange the following compounds in increasing order of their boiling points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
The reaction between A and B is first order with respect to A and zero order with respect to B. Fill in the blanks in the following table:
Experiment |
A/ mol L - 1 |
B/ mol L - 1 |
Initial rate/mol L - 1 min - 1 |
I | 0.1 | 0.1 |
2.0 × 10 - 2 |
II | -- | 0.2 |
4.0 × 10 - 2 |
III | 0.4 | 0.4 | -- |
IV | -- | 0.2 |
2.0 × 10 - 2 |
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
What role does the molecular interaction play in a solution of alcohol and water?
The decomposition of dimethyl ether leads to the formation of CH4, H2and CO and the reaction rate is given by
Rate = k [CH3OCH3]3/2
The rate of reaction is followed by increase in pressure in a closed vessel, so the rate can also be expressed in terms of the partial pressure of dimethyl ether, i.e.,
Rate = k (PCH3OCH3)3/2
If the pressure is measured in bar andtime in minutes, then what are the units of rate and rate constants?
A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
Heptane and octane form an ideal solution. At 373 K, the vapour pressures of the two liquid components are 105.2 kPa and 46.8 kPa respectively. What will be the vapour pressure of a mixture of 26.0 g of heptane and 35 g of octane?
Classify the following as primary, secondary and tertiary alcohols:
(i)
(ii) CH2C = CH - CH2OH
(iii) CH3 - CH2 - CH2 - OH
(iv)
(v)
(vi)
Complete the following reactions:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
Consequences: ii) separation of lanthanoids is NOT POSSIBLE due to lanthanoid contraction.