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Exercise · Q2

Q.From the ligands Cl−\text{Cl}^-, NH3\text{NH}_3, ethylenediamine (en\text{en}), and EDTA4−^{4-}, identify which ones are chelating ligands. Explain briefly why chelate complexes such as [Ni(en)3]2+[\text{Ni}(\text{en})_3]^{2+} are generally more thermodynamically stable than the corresponding complex with an equal number of monodentate ligands, such as [Ni(NH3)6]2+[\text{Ni}(\text{NH}_3)_6]^{2+}.

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A chelating ligand must have at least two donor atoms capable of binding the same metal ion at once, forming a ring. Of the four given, only en (bidentate, 2 N) and EDTA4−^{4-} (hexadentate, 6 donors) qualify; Cl−\text{Cl}^- and NH3\text{NH}_3 are both monodentate and can never form a ring, so they are not chelating. The chelate effect is the experimentally observed extra thermodynamic stability of a chelate complex compared with an analogous complex built from the equivalent number of monodentate ligands. Comparing [Ni(en)3]2+[\text{Ni}(\text{en})_3]^{2+} (3 bidentate en molecules, 6 donor atoms total) with [Ni(NH3)6]2+[\text{Ni}(\text{NH}_3)_6]^{2+} (6 monodentate NH3\text{NH}_3 molecules, also 6 donor atoms total): the enthalpy of the two reactions is very similar (six similar Ni-N bonds form in each case), but the entropy change is very different. Forming [Ni(en)3]2+[\text{Ni}(\text{en})_3]^{2+} from [Ni(H2O)6]2+[\text{Ni}(\text{H}_2\text{O})_6]^{2+} releases 6 water molecules while consuming only 3 en molecules — a net increase of 3 free particles in solution. Forming [Ni(NH3)6]2+[\text{Ni}(\text{NH}_3)_6]^{2+} releases the same 6 water molecules but consumes 6 NH3\text{NH}_3 molecules — no net change in the number of free particles. The chelate reaction therefore has a substantially more positive ΔS\Delta S, making its ΔG=ΔH−TΔS\Delta G = \Delta H - T\Delta S more negative (more spontaneous, more stable) than the equivalent monodentate reaction, even though the metal-ligand bonding itself is comparable. [!ANSWER] en and EDTA4−^{4-} are chelating ligands (bidentate and hexadentate respectively); Cl−\text{Cl}^- and NH3\text{NH}_3 are not. The chelate effect arises mainly from a favourable entropy increase — replacing several monodentate ligands with fewer chelating ligands releases more free solvent/ligand particles into solution.

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