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Chapter 24: Problem 21

(a) What is meant by the term chelate effect? (b) What thermodynamic factor is generally responsible for the chelate effect? (c) Why are polydentate ligands often called sequestering agents?

Short Answer

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(a) The chelate effect is the increased stability of a complex formed by a polydentate ligand when compared to a complex formed by monodentate ligands, due to the formation of a ring structure. (b) The thermodynamic factor responsible for the chelate effect is entropy, as the reaction with polydentate ligands produces fewer particles, leading to an increase in entropy. (c) Polydentate ligands are called sequestering agents because they form stable ring structures with metal ions, effectively trapping and controlling their availability in various systems.

Step by step solution

01

(a) Defining the Chelate Effect

The chelate effect refers to the increased stability of a complex formed by a polydentate (multi-dentate) ligand when compared to the stability of a complex formed by an equivalent combination of monodentate (single-dentate) ligands. A chelate complex is formed when a polydentate ligand coordinates with a central metal ion and forms a ring structure.
02

(b) Thermodynamic Factor Responsible for the Chelate Effect

The chelate effect is generally attributed to entropy. When a polydentate ligand forms a complex with a metal ion, fewer particles are produced compared to the reaction with monodentate ligands. The increase in entropy due to the release of a larger number of displaced monodentate ions or molecules is mainly responsible for the higher stability of the chelate complexes.
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(c) Polydentate Ligands as Sequestering Agents

Polydentate ligands are often called sequestering agents because they can form stable ring structures with a central metal ion, effectively "sequestering" or trapping the metal ion in a chelate complex. This strong binding makes it difficult for the metal ion to participate in any undesired reactions, hence controlling its availability in systems such as industrial processes, biochemistry, and environmental chemistry.

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Most popular questions from this chapter

For each of the following metals, write the electronic configuration of the atom and its \(2+\) ion: (a) \(\mathrm{Mn},(\mathrm{b}) \mathrm{Ru}\), (c) Rh. Draw the crystal-field energy-level diagram for the \(d\) orbitals of an octahedral complex, and show the placement of the \(d\) electrons for each \(2+\) ion, assuming a strong-field complex. How many unpaired electrons are there in each case?

Sketch all the possible stereoisomers of (a) tetrahedral \(\left[\mathrm{Cd}\left(\mathrm{H}_{2} \mathrm{O}\right)_{2} \mathrm{Cl}_{2}\right]\), (b) square-planar \(\left[\mathrm{IrCl}_{2}\left(\mathrm{PH}_{3}\right)_{2}\right]^{-}\), (c) octa- hedral \(\left[\mathrm{Fe}(0 \text { -phen })_{2} \mathrm{Cl}_{2}\right]^{+}\)

Carbon monoxide is toxic because it binds more strongly to the iron in hemoglobin (Hb) than does \(\mathrm{O}_{2}\), as indicated by these approximate standard free-energy changes in blood: $$ \begin{array}{clrl} \mathrm{Hb}+\mathrm{O}_{2} \longrightarrow \mathrm{HbO}_{2} & & \Delta G^{\circ}=-70 \mathrm{~kJ} \\ \mathrm{Hb}+\mathrm{CO} \longrightarrow \mathrm{HbCO} & \Delta G^{\circ}=-80 \mathrm{~kJ} \end{array} $$ Using these data, estimate the equilibrium constant at \(298 \mathrm{~K}\) for the equilibrium $$ \mathrm{HbO}_{2}+\mathrm{CO} \rightleftharpoons \mathrm{HbCO}+\mathrm{O}_{2} $$

Write names for the following coordination compounds: (a) \(\left[\mathrm{Cd}(\mathrm{en}) \mathrm{Cl}_{2}\right]\) (b) \(\mathrm{K}_{4}\left[\mathrm{Mn}(\mathrm{CN})_{6}\right]\) (c) \(\left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right)_{5} \mathrm{CO}_{3}\right] \mathrm{Cl}\) (d) \(\left[\mathrm{Ir}\left(\mathrm{NH}_{3}\right)_{4}\left(\mathrm{H}_{2} \mathrm{O}\right)_{2}\right]\left(\mathrm{NO}_{3}\right)_{3}\)

Pyridine \(\left(\mathrm{C}_{5} \mathrm{H}_{5} \mathrm{~N}\right)\), abbreviated py, is the following molecule: (a) Why is pyridine referred to as a monodentate ligand? (b) Consider the following equilibrium reaction: \(\left[\mathrm{Ru}(\mathrm{py})_{4}(\mathrm{bipy})\right]^{2+}+2 \mathrm{py} \rightleftharpoons\left[\mathrm{Ru}(\mathrm{py})_{6}\right]^{2+}+\) bipy What would you predict for themagnitude of the equilibrium constant for this equilibrium? Explain the basis for your answer.
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