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Q5.19:
\([Cr(NH_{3})_{6}]^{3+}\) is paramagnetic while \([Ni(CN)_{4}]^{2-}\) is diamagnetic. Explain why?
Solution :
Step 1: Electronic Configuration and Ligand Field Analysis of [Cr(NH₃)₆]³⁺
First, we determine the oxidation state and electronic configuration of the central metal ion, Chromium ($Cr$). The complex is $[Cr(NH_{3})_{6}]^{3+}$.
- The oxidation state of $Cr$ is $x + 6(0) = +3 \implies x = +3$.
- Ground state of $Cr$ ($Z=24$): $[Ar] 3d^5 4s^1$.
- $Cr^{3+}$ ion: $[Ar] 3d^3$.
The ligand $NH_{3}$ is a strong field ligand. However, in $d^3$ configuration, the three electrons occupy the $t_{2g}$ orbitals singly in accordance with [Hund's Rule of Maximum Multiplicity].
| Orbital Set | Population |
|---|---|
| $t_{2g}$ ($d_{xy}, d_{yz}, d_{xz}$) | $\uparrow \uparrow \uparrow$ |
| $e_g$ ($d_{z^2}, d_{x^2-y^2}$) | (empty) |
Because there are 3 unpaired electrons ($n=3$), the magnetic moment $\mu = \sqrt{n(n+2)} = \sqrt{3(5)} = \sqrt{15} \approx 3.87 \, BM$. Since unpaired electrons are present, the complex is paramagnetic.
Step 2: Electronic Configuration and Ligand Field Analysis of [Ni(CN)₄]²⁻
Next, we analyze the complex $[Ni(CN)_{4}]^{2-}$.
- Oxidation state of $Ni$: $x + 4(-1) = -2 \implies x = +2$.
- Ground state of $Ni$ ($Z=28$): $[Ar] 3d^8 4s^2$.
- $Ni^{2+}$ ion: $[Ar] 3d^8$.
$CN^{-}$ is a strong field ligand, which induces pairing of electrons in the $3d$ orbitals. In a square planar geometry [Valence Bond Theory], the $d$ orbitals split such that the $d_{x^2-y^2}$ orbital is high in energy.
The configuration $[Ar] 3d^8$ under the influence of $CN^{-}$ leads to:
- $d_{xy}, d_{yz}, d_{xz}$ orbitals: Fully occupied (paired).
- $d_{z^2}$ orbital: Occupied (paired).
- $d_{x^2-y^2}$ orbital: Empty (reserved for hybridization).
Since all 8 electrons are paired ($n=0$), there is no net magnetic moment. Therefore, the complex is diamagnetic.
Step 3: Comparative Summary
The difference arises from the number of unpaired electrons determined by the interaction between the metal's $d$-orbital occupancy and the crystal field splitting energy ($\Delta$) imposed by the ligands.
- $[Cr(NH_{3})_{6}]^{3+}$: Presence of 3 unpaired electrons in $d$-orbitals causes paramagnetic behavior.
- $[Ni(CN)_{4}]^{2-}$: Strong field $CN^{-}$ causes pairing of all $d$-electrons, leaving no unpaired electrons, resulting in diamagnetic behavior.
Final Solution: [Cr(NH₃)₆]³⁺ is paramagnetic due to the presence of 3 unpaired electrons in its 3d subshell, while [Ni(CN)₄]²⁻ is diamagnetic because the strong field CN⁻ ligand forces the pairing of all 3d electrons, resulting in zero unpaired electrons.]
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?
- Q5.2: \(FeSO_{4}\) 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?
- Q5.2: ((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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