Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory:
(i) [Fe(CN)6]4-
(ii) [FeF6]3-
(iii) [Co(C2O4)3]3-
(iv) [CoF6]3-
(i) [Fe(CN)6]4-
In the above coordination complex, iron exists in the +II oxidation state.
Fe2+ : Electronic configuration is 3d6
Orbitals of Fe2+ ion:
Hence, the geometry of the complex is octahedral and the complex is diamagnetic (as there are no unpaired electrons).
(ii) [FeF6]3-
In this complex, the oxidation state of Fe is +3.
Orbitals of Fe+3 ion:
Hence, the geometry of the complex is found to be octahedral.
(iii) [Co(C2O4)3]3-
Cobalt exists in the +3 oxidation state in the given complex.
Orbitals of Co3+ ion:
Hence, the geometry of the complex is found to be octahedral.
(iv) [CoF6]3- Cobalt exists in the +3 oxidation state.
Orbitals of Co3+ ion:
Again, fluoride ion is a weak field ligand. It cannot cause the pairing of the 3d electrons. As a result, the Co3+ ion will undergo sp3d2 hybridization. sp3d2 hybridized orbitals of Co3+ ion are:
[NiCl4]2- is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral. Why?
Explain on the basis of valence bond theory that [Ni(CN)4]2- ion with square planar structure is diamagnetic and the [Ni(CN)4]2- ion with tetrahedral geometry is paramagnetic.
Draw figure to show the splitting of d orbitals in an octahedral crystal field.
Write down the IUPAC name for each of the following complexes and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex:
(i) K[Cr(H2O)2(C2O4)2].3H2O
(ii) [Co(NH3)5Cl]Cl2
(iii) CrCl3(py)3
(iv) Cs[FeCl4]
(v) K4[Mn(CN)6]
The oxidation number of cobalt in K[Co(CO)4] is
(i) +1
(ii) +3
(iii) -1
(iv) -3
[Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2- is diamagnetic. Explain why?
Discuss the nature of bonding in metal carbonyls.
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)
Predict the number of unpaired electrons in the square planar [Pt(CN)4]2- ion.
Using IUPAC norms write the formulas for the following:
(i) Tetrahydroxozincate(II)
(ii) Potassium tetrachloridopalladate(II)
(iii) Diamminedichloridoplatinum(II)
(iv) Potassium tetracyanonickelate(II)
(v) Pentaamminenitrito-O-cobalt(III)
(vi) Hexaamminecobalt(III) sulphate
(vii) Potassium tri(oxalato)chromate(III)
(viii) Hexaammineplatinum(IV)
(ix) Tetrabromidocuprate(II)
(x) Pentaamminenitrito-N-cobalt(III)
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.
(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?
Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a transition element?
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
How will you convert?
(i) Benzene into aniline
(ii) Benzene into N, N-dimethylaniline
(iii) Cl-(CH2)4-Cl into hexan-1, 6-diamine?
Write reactions of the final alkylation product of aniline with excess of methyl iodide in the presence of sodium carbonate solution.
Account for the following:
(i) pKb of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv) Although amino group is o, p- directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m-nitroaniline.
(v) Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.
Classify the following into monosaccharides and disaccharides.
Ribose, 2-deoxyribose, maltose, galactose, fructose and lactose
Accomplish the following conversions:
(i) Nitrobenzene to benzoic acid
(ii) Benzene to m-bromophenol
(iii) Benzoic acid to aniline
(iv) Aniline to 2,4,6-tribromofluorobenzene
(v) Benzyl chloride to 2-phenylethanamine
(vi) Chlorobenzene to p-chloroaniline
(vii) Aniline to p-bromoaniline
(viii) Benzamide to toluene
(ix) Aniline to benzyl alcohol.
19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in the freezing point of water observed is 1.0°C. Calculate the van't Hoff factor and dissociation constant of fluoroacetic acid.
Illustrate how copper metal can give different products on reaction with HNO3.
Given the standard electrode potentials,
K+/ K = - 2.93V,
Ag+/ Ag = 0.80V,
Hg2+ / Hg = 0.79V
Mg2+ / Mg = - 2.37 V,
Cr3+ / Cr = - 0.74V
Arrange these metals in their increasing order of reducing power.
What modification can you suggest in the Hardy-Schulze law?
State Henry's law and mention some important applications?
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