Compare the general characteristics of the first series of the transition metals with those of the second and third series metals in the respective vertical columns. Give special emphasis on the following points:
(i) electronic configurations,
(ii) oxidation states,
(iii) ionisation enthalpies, and
(iv) atomic sizes.
(i) In the 1st, 2nd and 3rd transition series, the 3d, 4d and 5dorbitals are respectively filled.
We know that elements in the same vertical column generally have similar electronic configurations.
In the first transition series, two elements show unusual electronic configurations:
Cr(24) = 3d5 4s1
Cu(29) = 3d10 4s1
Similarly, there are exceptions in the second transition series. These are:
Mo(42) = 4d5 5s1
Tc(43) = 4d6 5s1
Ru(44) = 4d7 5s1
Rh(45) = 4d8 5s1
Pd(46) = 4d10 5s0
Ag(47) = 4d10 5s1
There are some exceptions in the third transition series as well. These are:
W(74) = 5d4 6s2
Pt(78) = 5d9 6s1
Au(79) = 5d10 6s1
As a result of these exceptions, it happens many times that the electronic configurations of the elements present in the same group are dissimilar.
(ii) In each of the three transition series the number of oxidation states shown by the elements is the maximum in the middle and the minimum at the extreme ends.
However, +2 and +3 oxidation states are quite stable for all elements present in the first transition series. All metals present in the first transition series form stable compounds in the +2 and +3 oxidation states. The stability of the +2 and +3 oxidation states decreases in the second and the third transition series, wherein higher oxidation states are more important.
For example are stable complexes, but no such complexes are known for the second and third transition series such as Mo, W, Rh, In. They form complexes in which their oxidation states are high. For example: WCl6, ReF7, RuO4, etc.
(iii) In each of the three transition series, the first ionisation enthalpy increases from left to right. However, there are some exceptions. The first ionisation enthalpies of the third transition series are higher than those of the first and second transition series. This occurs due to the poor shielding effect of 4felectrons in the third transition series.
Certain elements in the second transition series have higher first ionisation enthalpies than elements corresponding to the same vertical column in the first transition series. There are also elements in the 2nd transition series whose first ionisation enthalpies are lower than those of the elements corresponding to the same vertical column in the 1st transition series.
(iv) Atomic size generally decreases from left to right across a period. Now, among the three transition series, atomic sizes of the elements in the second transition series are greater than those of the elements corresponding to the same vertical column in the first transition series. However, the atomic sizes of the elements in the third transition series are virtually the same as those of the corresponding members in the second transition series. This is due to lanthanoid contraction.
Give simple chemical tests to distinguish between the following pairs of compounds.
(i) Propanal and Propanone
(ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid
(iv) Benzoic acid and Ethyl benzoate
(v) Pentan-2-one and Pentan-3-one
(vi) Benzaldehyde and Acetophenone
(vii) Ethanal and Propanal
A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate the freezing point of 5% glucose in water if freezing point of pure water is 273.15 K.
How the following conversions can be carried out?
(i) Propene to propan-1-ol
(ii) Ethanol to but-1-yne
(iii) 1-Bromopropane to 2-bromopropane
(iv) Toluene to benzyl alcohol
(v) Benzene to 4-bromonitrobenzene
(vi) Benzyl alcohol to 2-phenylethanoic acid
(vii) Ethanol to propanenitrile
(viii) Aniline to chlorobenzene
(ix) 2-Chlorobutane to 3, 4-dimethylhexane
(x) 2-Methyl-1-propene to 2-chloro-2-methylpropane
(xi) Ethyl chloride to propanoic acid
(xii) But-1-ene to n-butyliodide
(xiii) 2-Chloropropane to 1-propanol
(xiv) Isopropyl alcohol to iodoform
(xv) Chlorobenzene to p-nitrophenol
(xvi) 2-Bromopropane to 1-bromopropane
(xvii) Chloroethane to butane
(xviii) Benzene to diphenyl
(xix) tert-Butyl bromide to isobutyl bromide
(xx) Aniline to phenylisocyanide
A solution of glucose in water is labelled as 10% w/w, what would be the molality and mole fraction of each component in the solution? If the density of solution is 1.2 g mL-1, then what shall be the molarity of the solution?
Henry's law constant for CO2 in water is 1.67 x 108Pa at 298 K. Calculate the quantity of CO2in 500 mL of soda water when packed under 2.5 atm CO2 pressure at 298 K.
Calculate the mass of a non-volatile solute (molar mass 40 g mol-1) which should be dissolved in 114 g octane to reduce its vapour pressure to 80%.
The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively, at 350 K. Find out the composition of the liquid mixture if total vapour pressure is 600 mm Hg. Also find the composition of the vapour phase.
Calculate the mole fraction of benzene in solution containing 30% by mass in carbon tetrachloride.
How many mL of 0.1 M HCl are required to react completely with 1 g mixture of Na2CO3 and NaHCO3 containing equimolar amounts of both?
If NaCl is doped with 10-3mol % of SrCl2, what is the concentration of cation vacancies?
Boiling point of water at 750 mm Hg is 99.63°C. How much sucrose is to be added to 500 g of water such that it boils at 100°C.Molal elevation constant for water is 0.52 K kg mol-1.
Analysis shows that nickel oxide has the formula Ni0.98 O1.00. What fractions of nickel exist as Ni2+and Ni3+ions?
The decomposition of NH3on platinum surface is zero order reaction. What are the rates of production of N2and H2if k = 2.5 x 10-4mol-1L s-1?
Write structures of the products of the following reactions:
(i)
(ii)
(iii)
What do you mean by activity and selectivity of catalysts?
What is lanthanoid contraction? What are the consequences of lanthanoid contraction?
For a reaction, A + B → Product; the rate law is given by, r = k [A]½ [B]2. What is the order of the reaction?
A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate the freezing point of 5% glucose in water if freezing point of pure water is 273.15 K.
Draw the structures of optical isomers of:
(i) [Cr(C2O4)3]3-
(ii) [PtCl2(en)2]2+
(iii) [Cr(NH3)2Cl2(en)]+
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)