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Q5.2:
\(FeSO_{4}\) solution mixed with \((NH_{4})_{2}SO_{4}\) solution in 1:1 molar ratio gives the test of \(Fe^{2+}\) ion but \(CuSO_{4}\) solution mixed with aqueous ammonia in 1:4 molar ratio does not give the test of \(Cu^{2+}\) ion. Explain why?
Solution :
Step 1: Analyzing the Formation of Mohr's Salt ($FeSO_{4} \cdot (NH_{4})_{2}SO_{4} \cdot 6H_{2}O$)
When an aqueous solution of ferrous sulfate ($FeSO_{4}$) is mixed with ammonium sulfate ($(NH_{4})_{2}SO_{4}$) in a 1:1 molar ratio, the resulting compound is a double salt known as Mohr's salt. The chemical reaction is defined as:
$FeSO_{4}(aq) + (NH_{4})_{2}SO_{4}(aq) + 6H_{2}O(l) \rightarrow FeSO_{4} \cdot (NH_{4})_{2}SO_{4} \cdot 6H_{2}O(s)$
[Per the definition of double salts, these compounds exist only in the solid state and dissociate completely into their constituent simple ions when dissolved in water.]
In aqueous solution, the dissociation follows:
$[FeSO_{4} \cdot (NH_{4})_{2}SO_{4} \cdot 6H_{2}O](aq) \rightarrow Fe^{2+}(aq) + 2NH_{4}^{+}(aq) + 2SO_{4}^{2-}(aq) + 6H_{2}O(l)$
Because the $Fe^{2+}$ ions are released into the solution as free, hydrated ions, they remain available to react with chemical reagents (e.g., potassium ferricyanide), thereby giving a positive qualitative test for iron(II).
Step 2: Analyzing the Formation of Tetraamminecopper(II) Sulfate
When an aqueous solution of copper(II) sulfate ($CuSO_{4}$) is mixed with aqueous ammonia ($NH_{3}$) in a 1:4 molar ratio, a coordination complex is formed:
$CuSO_{4}(aq) + 4NH_{3}(aq) \rightarrow [Cu(NH_{3})_{4}]SO_{4}(aq)$
[Per Werner’s Coordination Theory, ligands coordinate to the central metal ion via dative covalent bonds.]
In this coordination entity, the $Cu^{2+}$ ion is surrounded by four $NH_{3}$ ligands in a square planar geometry. The coordination entity $[Cu(NH_{3})_{4}]^{2+}$ is highly stable and does not dissociate into free $Cu^{2+}$ ions in an aqueous medium. The dissociation equilibrium is defined as:
$[Cu(NH_{3})_{4}]SO_{4}(aq) \rightarrow [Cu(NH_{3})_{4}]^{2+}(aq) + SO_{4}^{2-}(aq)$
Since the concentration of free $Cu^{2+}(aq)$ ions in the solution is negligible (governed by the instability constant $K_{inst}$ of the complex), the solution fails to yield the characteristic qualitative tests associated with free copper(II) ions.
Step 3: Comparative Analysis
| Compound Type | Dissociation in Water | Availability of Metal Ion |
|---|---|---|
| Double Salt (Mohr's Salt) | Complete (Into simple ions) | High ($Fe^{2+}$ present) |
| Coordination Complex | Incomplete (Complex ion remains intact) | Negligible ($Cu^{2+}$ sequestered) |
Final Solution: Mohr's salt is a double salt that dissociates completely in water, releasing free $Fe^{2+}$ ions which react to give their characteristic test. Conversely, $[Cu(NH_{3})_{4}]SO_{4}$ is a coordination complex that retains its identity in solution, sequestering the $Cu^{2+}$ ion within the stable coordination entity, thereby preventing it from reacting during standard qualitative testing.
More Questions from Class 12 Chemistry Coordination Compounds Exercises
- Q5.1: Explain the bonding in coordination compounds in terms of Werner’s postulates.
- Q5.1: Explain the bonding in coordination compounds in terms of Werner’s postulates.
- Q5.10 (i): Draw the structures of optical isomers of: ([Cr(C_{2}O_{4})_{3}]^{3-})
- Q5.10 (ii): Draw the structures of optical isomers of: ([PtCl_{2}(en)_{2}]^{2+})
- Q5.10 (iii): Draw the structures of optical isomers of: ([Cr(NH_{3})_{2}Cl_{2}(en)]^{+})
- Q5.10(i): Draw the structures of optical isomers of: \([Cr(C_{2}O_{4})_{3}]^{3-}\)
- Q5.10(ii): Draw the structures of optical isomers of: \([PtCl_{2}(en)_{2}]^{2+}\)
- Q5.10(iii): Draw the structures of optical isomers of: \([Cr(NH_{3})_{2}Cl_{2}(en)]^{+}\)
- Q5.11 (i): Draw all the isomers (geometrical and optical) of: ([CoCl_{2}(en)_{2}]^{+})
- Q5.11 (ii): Draw all the isomers (geometrical and optical) of: ([Co(NH_{3})Cl(en)_{2}]^{2+})
- Q5.11 (iii): Draw all the isomers (geometrical and optical) of: ([Co(NH_{3})_{2}Cl_{2}(en)]^{+})
- Q5.11(i): Draw all the isomers (geometrical and optical) of: \([CoCl_{2}(en)_{2}]^{+}\)
- Q5.11(ii): Draw all the isomers (geometrical and optical) of: \([Co(NH_{3})Cl(en)_{2}]^{2+}\)
- Q5.11(iii): Draw all the isomers (geometrical and optical) of: \([Co(NH_{3})_{2}Cl_{2}(en)]^{+}\)
- Q5.12: Write all the geometrical isomers of \([Pt(NH_{3})(Br)(Cl)(py)]\) and how many of these will exhibit optical isomers?
- Q5.12: Write all the geometrical isomers of ([Pt(NH_{3})(Br)(Cl)(py)]) and how many of these will exhibit optical isomers?
- Q5.13: Aqueous copper sulphate solution (blue in colour) gives: (i) a green precipitate with aqueous potassium fluoride and (ii) a bright green solution with aqueous potassium chloride. Explain these experimental results.
- Q5.13: Aqueous copper sulphate solution (blue in colour) gives: (i) a green precipitate with aqueous potassium fluoride and (ii) a bright green solution with aqueous potassium chloride. Explain these experimental results.
- Q5.14: What is the coordination entity formed when excess of aqueous \(KCN\) is added to an aqueous solution of copper sulphate? Why is it that no precipitate of copper sulphide is obtained when \(H_{2}S(g)\) is passed through this solution?
- Q5.14: What is the coordination entity formed when excess of aqueous KCN is added to an aqueous solution of copper sulphate? Why is it that no precipitate of copper sulphide is obtained when ((H_{2}S(g))) is passed through this solution?
- Q5.15 (i): Discuss the nature of bonding on the basis of valence bond theory: ([Fe(CN)_{6}]^{4-})
- Q5.15 (ii): Discuss the nature of bonding on the basis of valence bond theory: ([FeF_{6}]^{3-})
- Q5.15 (iii): Discuss the nature of bonding on the basis of valence bond theory: ([Co(C_{2}O_{4})_{3}]^{3-})
- Q5.15 (iv): Discuss the nature of bonding on the basis of valence bond theory: ([CoF_{6}]^{3-})
- Q5.15(i): Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory: \([Fe(CN)_{6}]^{4-}\)
- Q5.15(ii): Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory: \([FeF_{6}]^{3-}\)
- Q5.15(iii): Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory: \([Co(C_{2}O_{4})_{3}]^{3-}\)
- Q5.15(iv): Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory: \([CoF_{6}]^{3-}\)
- Q5.16: Draw figure to show the splitting of d orbitals in an octahedral crystal field.
- Q5.16: Draw figure to show the splitting of d orbitals in an octahedral crystal field.
- Q5.17: What is spectrochemical series? Explain the difference between a weak field ligand and a strong field ligand.
- Q5.17: What is spectrochemical series? Explain the difference between a weak field ligand and a strong field ligand.
- Q5.18: What is crystal field splitting energy? How does the magnitude of \(\Delta_{o}\) decide the actual configuration of d orbitals in a coordination entity?
- Q5.18: What is crystal field splitting energy? How does the magnitude of (\Delta_{o}) decide the actual configuration of d orbitals in a coordination entity?
- Q5.19: \([Cr(NH_{3})_{6}]^{3+}\) is paramagnetic while \([Ni(CN)_{4}]^{2-}\) is diamagnetic. Explain why?
- Q5.19: ([Cr(NH_{3})_{6}]^{3+}) is paramagnetic while ([Ni(CN)_{4}]^{2-}) is diamagnetic. Explain why?
- Q5.2: ((FeSO_{4})) solution mixed with ((NH_{4})_{2}SO_{4}) solution in 1:1 molar ratio gives the test of ((Fe^{2+})) ion but ((CuSO_{4})) solution mixed with aqueous ammonia in 1:4 molar ratio does not give the test of ((Cu^{2+})) ion. Explain why?
- Q5.20: A solution of \([Ni(H_{2}O)_{6}]^{2+}\) is green but a solution of \([Ni(CN)_{4}]^{2-}\) is colourless. Explain.
- Q5.20: A solution of ([Ni(H_{2}O)_{6}]^{2+}) is green but a solution of ([Ni(CN)_{4}]^{2-}) is colourless. Explain.
- Q5.21: \([Fe(CN)_{6}]^{4-}\) and \([Fe(H_{2}O)_{6}]^{2+}\) are of different colours in dilute solutions. Why?
- Q5.21: ([Fe(CN)_{6}]^{4-}) and ([Fe(H_{2}O)_{6}]^{2+}) are of different colours in dilute solutions. Why?
- Q5.22: Discuss the nature of bonding in metal carbonyls.
- Q5.22: Discuss the nature of bonding in metal carbonyls.
- Q5.23 (i): Give the oxidation state, d orbital occupation and coordination number of the central metal ion: (K_{3}[Co(C_{2}O_{4})_{3}])
- Q5.23 (ii): Give the oxidation state, d orbital occupation and coordination number of the central metal ion: (cis-[CrCl_{2}(en)_{2}]Cl)
- Q5.23 (iii): Give the oxidation state, d orbital occupation and coordination number of the central metal ion: ((NH_{4})_{2}[CoF_{4}])
- Q5.23 (iv): Give the oxidation state, d orbital occupation and coordination number of the central metal ion: ([Mn(H_{2}O)_{6}]SO_{4})
- Q5.23(i): Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complexes: \(K_{3}[Co(C_{2}O_{4})_{3}]\)
- Q5.23(ii): Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complexes: cis-\([CrCl_{2}(en)_{2}]Cl\)
- Q5.23(iii): Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complexes: \((NH_{4})_{2}[CoF_{4}]\)
- Q5.23(iv): Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complexes: \([Mn(H_{2}O)_{6}]SO_{4}\)
- Q5.24 (i): Write down the IUPAC name for the complex and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: (K[Cr(H_{2}O)_{2}(C_{2}O_{4})_{2}].3H_{2}O)
- Q5.24 (ii): Write down the IUPAC name for the complex and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: ([Co(NH_{3})_{5}Cl]Cl_{2})
- Q5.24 (iii): Write down the IUPAC name for the complex and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: ([CrCl_{3}(py)_{3}])
- Q5.24 (iv): Write down the IUPAC name for the complex and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: (Cs[FeCl_{4}])
- Q5.24 (v): Write down the IUPAC name for the complex and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: (K_{4}[Mn(CN)_{6}])
- Q5.24(i): 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: \(K[Cr(H_{2}O)_{2}(C_{2}O_{4})_{2}].3H_{2}O\)
- Q5.24(ii): 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: \([Co(NH_{3})_{5}Cl]Cl_{2}\)
- Q5.24(iii): 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: \([CrCl_{3}(py)_{3}]\)
- Q5.24(iv): 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: \(Cs[FeCl_{4}]\)
- Q5.24(v): 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: \(K_{4}[Mn(CN)_{6}]\)
- Q5.25: Explain the violet colour of the complex \([Ti(H_{2}O)_{6}]^{3+}\) on the basis of crystal field theory.
- Q5.25: Explain the violet colour of the complex ([Ti(H_{2}O)_{6}]^{3+}) on the basis of crystal field theory.
- Q5.26: What is meant by the chelate effect? Give an example.
- Q5.26: What is meant by the chelate effect? Give an example.
- Q5.27: Discuss briefly giving an example in each case the role of coordination compounds in: (i) biological systems (iii) analytical chemistry (ii) medicinal chemistry and (iv) extraction/metallurgy of metals.
- Q5.27(i): Discuss briefly giving an example in each case the role of coordination compounds in: biological systems
- Q5.27(ii): Discuss briefly giving an example in each case the role of coordination compounds in: medicinal chemistry
- Q5.27(iii): Discuss briefly giving an example in each case the role of coordination compounds in: analytical chemistry
- Q5.27(iv): Discuss briefly giving an example in each case the role of coordination compounds in: extraction/metallurgy of metals.
- Q5.28: How many ions are produced from the complex \(Co(NH_{3})_{6}Cl_{2}\) in solution?
- Q5.28: How many ions are produced from the complex (Co(NH_{3})_{6}Cl_{2}) in solution?
- Q5.29: Amongst the following ions which one has the highest magnetic moment value?
- Q5.29: Amongst the following ions which one has the highest magnetic moment value?
- Q5.3: Explain with two examples each of the following: coordination entity, ligand, coordination number, coordination polyhedron, homoleptic and heteroleptic.
- Q5.3: Explain with two examples each of the following: coordination entity, ligand, coordination number, coordination polyhedron, homoleptic and heteroleptic.
- Q5.30: Amongst the following, the most stable complex is
- Q5.30: Amongst the following, the most stable complex is
- Q5.31: What will be the correct order for the wavelengths of absorption in the visible region for the following: \([Ni(NO_{2})_{6}]^{4-}\), \([Ni(NH_{3})_{6}]^{2+}\), \([Ni(H_{2}O)_{6}]^{2+}\)?
- Q5.31: What will be the correct order for the wavelengths of absorption in the visible region for the following: ([Ni(NO_{2})_{6}]^{4-}), ([Ni(NH_{3})_{6}]^{2+}), ([Ni(H_{2}O)_{6}]^{2+})?
- Q5.4: What is meant by unidentate, didentate and ambidentate ligands? Give two examples for each.
- Q5.4: What is meant by unidentate, didentate and ambidentate ligands? Give two examples for each.
- Q5.5 (i): Specify the oxidation numbers of the metals: ([Co(H_{2}O)(CN)(en)_{2}]^{2+})
- Q5.5 (ii): Specify the oxidation numbers of the metals: ([CoBr_{2}(en)_{2}]^{+})
- Q5.5 (iii): Specify the oxidation numbers of the metals: ([PtCl_{4}]^{2-})
- Q5.5 (iv): Specify the oxidation numbers of the metals: (K_{3}[Fe(CN)_{6}])
- Q5.5 (v): Specify the oxidation numbers of the metals: ([Cr(NH_{3})_{3}Cl_{3}])
- Q5.5(i): Specify the oxidation numbers of the metals in the following coordination entities: \([Co(H_{2}O)(CN)(en)_{2}]^{2+}\)
- Q5.5(ii): Specify the oxidation numbers of the metals in the following coordination entities: \([CoBr_{2}(en)_{2}]^{+}\)
- Q5.5(iii): Specify the oxidation numbers of the metals in the following coordination entities: \([PtCl_{4}]^{2-}\)
- Q5.5(iv): Specify the oxidation numbers of the metals in the following coordination entities: \(K_{3}[Fe(CN)_{6}]\)
- Q5.5(v): Specify the oxidation numbers of the metals in the following coordination entities: \([Cr(NH_{3})_{3}Cl_{3}]\)
- Q5.6 (i): Using IUPAC norms write the formulas: Tetrahydroxidozincate(II)
- Q5.6 (ii): Using IUPAC norms write the formulas: Potassium tetrachloridopalladate(II)
- Q5.6 (iii): Using IUPAC norms write the formulas: Diamminedichloridoplatinum(II)
- Q5.6 (iv): Using IUPAC norms write the formulas: Potassium tetracyanidonickelate(II)
- Q5.6 (ix): Using IUPAC norms write the formulas: Tetrabromidocuprate(II)
- Q5.6 (v): Using IUPAC norms write the formulas: Pentaamminenitrito-O-cobalt(III)
- Q5.6 (vi): Using IUPAC norms write the formulas: Hexaamminecobalt(III) sulphate
- Q5.6 (vii): Using IUPAC norms write the formulas: Potassium tri(oxalato)chromate(III)
- Q5.6 (viii): Using IUPAC norms write the formulas: Hexaammineplatinum(IV)
- Q5.6 (x): Using IUPAC norms write the formulas: Pentaamminenitrito-N-cobalt(III)
- Q5.6(i): Using IUPAC norms write the formulas for the following: Tetrahydroxidozincate(II)
- Q5.6(ii): Using IUPAC norms write the formulas for the following: Potassium tetrachloridopalladate(II)
- Q5.6(iii): Using IUPAC norms write the formulas for the following: Diamminedichloridoplatinum(II)
- Q5.6(iv): Using IUPAC norms write the formulas for the following: Potassium tetracyanidonickelate(II)
- Q5.6(ix): Using IUPAC norms write the formulas for the following: Tetrabromidocuprate(II)
- Q5.6(v): Using IUPAC norms write the formulas for the following: Pentaamminenitrito-O-cobalt(III)
- Q5.6(vi): Using IUPAC norms write the formulas for the following: Hexaamminecobalt(III) sulphate
- Q5.6(vii): Using IUPAC norms write the formulas for the following: Potassium tri(oxalato)chromate(III)
- Q5.6(viii): Using IUPAC norms write the formulas for the following: Hexaammineplatinum(IV)
- Q5.6(x): Using IUPAC norms write the formulas for the following: Pentaamminenitrito-N-cobalt(III)
- Q5.7 (i): Using IUPAC norms write the systematic names: ([Co(NH_{3})_{6}]Cl_{3})
- Q5.7 (ii): Using IUPAC norms write the systematic names: ([Pt(NH_{3})_{2}Cl(NH_{2}CH_{3})]Cl)
- Q5.7 (iii): Using IUPAC norms write the systematic names: ([Ti(H_{2}O)_{6}]^{3+})
- Q5.7 (iv): Using IUPAC norms write the systematic names: ([Co(NH_{3})_{4}Cl(NO_{2})]Cl)
- Q5.7 (ix): Using IUPAC norms write the systematic names: ([Ni(CO)_{4}])
- Q5.7 (v): Using IUPAC norms write the systematic names: ([Mn(H_{2}O)_{6}]^{2+})
- Q5.7 (vi): Using IUPAC norms write the systematic names: ([NiCl_{4}]^{2-})
- Q5.7 (vii): Using IUPAC norms write the systematic names: ([Ni(NH_{3})_{6}]Cl_{2})
- Q5.7 (viii): Using IUPAC norms write the systematic names: ([Co(en)_{3}]^{3+})
- Q5.7(i): Using IUPAC norms write the systematic names of the following: \([Co(NH_{3})_{6}]Cl_{3}\)
- Q5.7(ii): Using IUPAC norms write the systematic names of the following: \([Pt(NH_{3})_{2}Cl(NH_{2}CH_{3})]Cl\)
- Q5.7(iii): Using IUPAC norms write the systematic names of the following: \([Ti(H_{2}O)_{6}]^{3+}\)
- Q5.7(iv): Using IUPAC norms write the systematic names of the following: \([Co(NH_{3})_{4}Cl(NO_{2})]Cl\)
- Q5.7(ix): Using IUPAC norms write the systematic names of the following: \([Ni(CO)_{4}]\)
- Q5.7(v): Using IUPAC norms write the systematic names of the following: \([Mn(H_{2}O)_{6}]^{2+}\)
- Q5.7(vi): Using IUPAC norms write the systematic names of the following: \([NiCl_{4}]^{2-}\)
- Q5.7(vii): Using IUPAC norms write the systematic names of the following: \([Ni(NH_{3})_{6}]Cl_{2}\)
- Q5.7(viii): Using IUPAC norms write the systematic names of the following: \([Co(en)_{3}]^{3+}\)
- Q5.8: List various types of isomerism possible for coordination compounds, giving an example of each.
- Q5.8: List various types of isomerism possible for coordination compounds, giving an example of each.
- Q5.9 (i): How many geometrical isomers are possible? ([Cr(C_{2}O_{4})_{3}]^{3-})
- Q5.9 (ii): How many geometrical isomers are possible? ([Co(NH_{3})_{3}Cl_{3}])
- Q5.9(i): How many geometrical isomers are possible in the following coordination entities? \([Cr(C_{2}O_{4})_{3}]^{3-}\)
- Q5.9(ii): How many geometrical isomers are possible in the following coordination entities? \([Co(NH_{3})_{3}Cl_{3}]\)
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