આ MCQ મોડ્યુલ આના પર આધારિત છે: Stability Applications
Stability Applications
આ મૂલ્યાંકન આના પર આધારિત હશે: Stability Applications
મૂલ્યાંકન બનાવવામાં તેમની સામગ્રી સામેલ કરવા ચિત્રો, PDF અથવા Word દસ્તાવેજ અપલોડ કરો.
Stability Applications
5.7 Bonding in Metal Carbonyls — The Synergic Effect
Most transition metals form homoleptic carbonyls in which CO is the only ligand. They have well-defined geometries:
| Carbonyl | Metal oxidation state | Geometry |
|---|---|---|
| [Ni(CO)4] | 0 | Tetrahedral |
| [Fe(CO)5] | 0 | Trigonal bipyramidal |
| [Cr(CO)6] | 0 | Octahedral |
| [Mn2(CO)10] | 0 | Two square pyramids joined by Mn–Mn bond |
| [Co2(CO)8] | 0 | Co–Co bond bridged by two CO groups |
Synergic σ–π bonding
The metal-carbon bond in carbonyls has dual character:
- σ-bond: the lone pair on the carbonyl carbon donates into a vacant metal hybrid orbital (CO → M).
- π-bond: a filled metal d-orbital donates back into the empty antibonding π* orbital of CO (M → CO).
This synergic effect reinforces both bonds — the σ donation increases the d-electron density on the metal, making π-back-donation easier, and the π-back-donation removes some of that electron density, making the next σ donation stronger. The result is a particularly strong, short M–C bond and weakened C–O bond (longer than in free CO).
5.8 Stability of Coordination Compounds
The thermodynamic stability of a complex in solution is described by its formation constant (β) — the equilibrium constant for the overall replacement of solvent (water) by ligand:
\[ M^{n+} + nL \rightleftharpoons [ML_n]^{n+}, \qquad \beta_n = \frac{[ML_n^{n+}]}{[M^{n+}][L]^n} \]Larger β means a more stable complex. Typical trends (in order of increasing β for a given metal): F− < Cl− < Br− < I− for "soft" metal ions; chelates always > comparable monodentate complexes (chelate effect).
| Equilibrium | log β | Comment |
|---|---|---|
| Cu²⁺ + 4NH₃ ⇌ [Cu(NH₃)₄]²⁺ | ≈ 11.6 | Deep-blue colour test for Cu²⁺. |
| Cu²⁺ + 4CN⁻ ⇌ [Cu(CN)₄]³⁻ | ≈ 30 (very high) | So stable that H₂S no longer precipitates CuS. |
| Ag⁺ + 2CN⁻ ⇌ [Ag(CN)₂]⁻ | ≈ 21 | Used in electroplating & gold extraction. |
| Fe³⁺ + 3C₂O₄²⁻ ⇌ [Fe(C₂O₄)₃]³⁻ | ≈ 20 | Chelated → very stable (chelate effect). |
| Ca²⁺ + EDTA⁴⁻ ⇌ [Ca(EDTA)]²⁻ | ≈ 10.7 | Hardness titration of water. |
The chelate effect
Replacing several monodentate ligands by one polydentate (chelating) ligand always increases stability — even when the donor atoms are chemically identical. The driving force is mostly entropic: one large polydentate ligand displaces several small monodentate ligands, increasing the number of free particles in solution and \(\Delta S^\circ\).
5.9 Importance and Applications of Coordination Compounds
1. Analytical chemistry
EDTA, dimethylglyoxime (DMG, brick-red Ni complex), α-nitroso-β-naphthol and cupron form characteristic coloured complexes used in qualitative tests and instrumental analysis.2. Hardness of water
Ca2+ and Mg2+ form stable EDTA chelates with different formation constants, allowing selective complexometric titration of total hardness using Na2EDTA.3. Extraction of metals
Gold: 4Au + 8CN− + O2 + 2H2O → 4[Au(CN)2]− + 4OH−; gold is then displaced by zinc. Silver is extracted similarly.4. Purification of nickel — Mond's process
Impure Ni + CO at 50–60 °C → [Ni(CO)4] (volatile). Heating the carbonyl to ~230 °C decomposes it back to pure Ni and CO (recycled).5. Catalysis
Wilkinson's catalyst [(PPh3)3RhCl] selectively hydrogenates alkenes. Many industrial processes (Wacker, hydroformylation) rely on coordination chemistry.6. Electroplating
Plating with silver and gold from [Ag(CN)2]− and [Au(CN)2]− baths gives much smoother, evener deposits than from solutions of free metal ions.7. Photography
In black-and-white photography, the developed film is "fixed" with hypo (Na2S2O3) which dissolves undecomposed AgBr by forming [Ag(S2O3)2]3−.8. Medicine — chelation therapy
EDTA — for lead poisoning. D-penicillamine and desferrioxime B — for excess Cu and Fe (Wilson's disease, β-thalassaemia). cis-platin and related Pt(II) complexes — anti-cancer drugs.5.9.1 Coordination Compounds in Biology
| Bio-molecule | Metal centre | Function |
|---|---|---|
| Haemoglobin / Myoglobin | Fe2+ in porphyrin ring | O2 transport (RBC) / O2 storage (muscle) |
| Chlorophyll | Mg2+ in porphyrin ring | Light absorption for photosynthesis |
| Vitamin B12 (cyanocobalamin) | Co3+ in corrin ring | Anti-pernicious-anaemia factor; methyl-group transfer |
| Carboxypeptidase A, carbonic anhydrase | Zn2+ | Enzymes catalysing peptide hydrolysis / CO2 hydration |
Setup: Aqueous CuSO4 (blue) is divided into three test tubes. To tube 1 add aqueous KF; to tube 2 add aqueous KCl; to tube 3 add excess aqueous KCN, then bubble H2S through the resulting solution.
Tube 1 (KF): Cu2+ + 4F− → [CuF4]2−; the solution turns green-pale (a green precipitate of CuF2 can also form initially).
Tube 2 (KCl): Cu2+ + 4Cl− → [CuCl4]2−; bright green solution (Cl− gives a different absorption).
Tube 3 (KCN): 2Cu2+ + 10CN− → 2[Cu(CN)4]3− + (CN)2 (CN− reduces Cu(II) to Cu(I)). The very high formation constant (~1030) means [Cu+] is so low that Ksp of CuS is not exceeded — no CuS precipitate on bubbling H2S.
This shows how a high-stability complex effectively removes a metal ion from "free-ion" chemistry.
🔧 Interactive: Application Explorer
Pick an application area; the simulation shows the relevant coordination compound, the chemistry behind it, and a real-life example.
Worked Example 5.10 — Coordination compound formed by excess CN⁻ on CuSO₄
What is the entity formed when excess KCN is added to aqueous CuSO4? Why does H2S no longer precipitate CuS from this solution?
Worked Example 5.11 — Why do Fe²⁺ tests work on Mohr's salt but not on K₄[Fe(CN)₆]?
K4[Fe(CN)6] is a complex; the [Fe(CN)6]4− ion has β ≈ 1035. Free [Fe2+] is too low to be detected by standard tests. Similarly, with CuSO4 + 4 NH3 the deep-blue [Cu(NH3)4]2+ forms and no Cu2+ spot test works.
🎯 Competency-Based Questions
Q1. The metal ion at the centre of haemoglobin is: L1 Remember
Q2. Which complex has the highest stability? L3 Apply
Q3. In the Mond process for nickel refining, the role of the coordination compound is: L3 Apply
Q4. A patient with chronic lead poisoning is treated with EDTA. Explain the chemistry. L4 Analyse
Q5. HOT (Create): Design a school-lab demonstration to estimate Ca²⁺ + Mg²⁺ "total hardness" of tap water in mol L⁻¹. List apparatus, indicator, and one observation. L6 Create
🧠 Assertion–Reason Questions
Choose: (A) Both true, R explains A. (B) Both true, R doesn't explain A. (C) A true, R false. (D) A false, R true.
A: Gold can be extracted from its ore by treating with NaCN solution and air.
R: Gold forms a soluble complex [Au(CN)2]− from which it can later be displaced by zinc.
A: Cisplatin is used as an anti-cancer drug.
R: Only the cis isomer of [Pt(NH3)2Cl2] can bind two adjacent guanine bases on DNA.
A: Chelate complexes are more stable than complexes containing the same number of monodentate ligands of the same donor atom.
R: Formation of a chelate increases the entropy of the system because several free monodentate ligands are released when a single polydentate ligand binds.
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