Question:

The logarithm of equilibrium constant for the reaction $Pd ^{2+}+4 Cl ^{-} \rightleftharpoons PdCl _4^{2-}$ is (Nearest integer) Given : $\frac{230RT }{ F }=006 V$ $Pd _{\text {(aq) }}^{2+}+2 e ^{-} \rightleftharpoons Pd ( s ) \quad E ^{\ominus}=083 V$ $PdCl _4^{2-} \text { (aq) }+2 e ^{-} \rightleftharpoons Pd ( s )+4 Cl ^{-} \text {(aq) } E ^{\ominus}=065 V$

Updated On: Sep 14, 2024
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Correct Answer: 6

Approach Solution - 1

The correct answer is 6


....(1)


Net Reaction (aq.) (aq.) (aq.)


...(2)
Also .....(3)
Using equation (1), (2) & (3)
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Approach Solution -2

The equilibrium constant, K, for a reaction, can be related to the standard Gibbs free energy change, \(ΔG°\), by the equation:
\(ΔG\degree = -RT\) ln K
where R is the gas constant, T is the temperature in Kelvin, and ln is the natural logarithm.

Using the Nernst equation, we can also relate the standard reduction potentials of the half-reactions to the equilibrium constant:
\(\text{E° cell} = \text{E° reduction (cathode) - E° reduction (anode)}\) \(ΔG° = -nF \text{ }E°cell\)
where n is the number of electrons transferred in the reaction and F is the Faraday constant.

We can use these equations to find the logarithm of the equilibrium constant for the given reaction:
\(Pd^{2+} + 4 Cl^{-} ⇌ PdCl_{4}^{2-}\)

The overall reaction involves the reduction of \(Pd^{2+}\) to \(Pd\), and the oxidation of \(Cl^{-}\) to \(Cl^{2}\). We can write the half-reactions and their standard reduction potentials as follows:
\(Pd^{2+} + 2 e^{-} ⇌ Pd(s) \text{E° reduction} = 0.83 V2 Cl^{-} ⇌ Cl^{2} + 2 e^{-} \text{E° reduction} = -1.36 V\)

The overall cell potential is the sum of these reduction potentials:
\(\text{E° cell} = 0.83 - (-1.36) = 2.19 V\)

We can use the Nernst equation to relate this cell potential to the equilibrium constant:
\(\text{E cell} = \text{E° cell} - \frac{RT}{nF}\)
ln Q where Q is the reaction quotient, which is the concentration of products raised to their stoichiometric coefficients divided by the concentration of reactants raised to their stoichiometric coefficients.

For the given reaction, we have:
\(Q = \frac{[PdCl_{4} ^{2-}]}{([Pd^{2+}][Cl^{-}]^{4})}\)
Substituting the values given in the question, we get:
\(2.19 V = 0.83 V - \frac{2.30RT}{F}\text{ ln K}\)
\(\text{ln K} = \frac{(0.83 - 2.19) V}{\frac{2.30 RT}{F}}\)
\(\text{ ln K} = -0.497\)
Taking the antilogarithm of both sides, we get:
\(K = 0.61\)

Therefore, the nearest integer to the logarithm of the equilibrium constant for the reaction is -1.

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Concepts Used:

Electrochemical Cells

An electrochemical cell is a device that is used to create electrical energy through the chemical reactions which are involved in it. The electrical energy supplied to electrochemical cells is used to smooth the chemical reactions. In the electrochemical cell, the involved devices have the ability to convert the chemical energy to electrical energy or vice-versa.

Classification of Electrochemical Cell:

Cathode

  • Denoted by a positive sign since electrons are consumed here
  • A reduction reaction occurs in the cathode of an electrochemical cell
  • Electrons move into the cathode

Anode

  • Denoted by a negative sign since electrons are liberated here
  • An oxidation reaction occurs here
  • Electrons move out of the anode

Types of Electrochemical Cells:

Galvanic cells (also known as Voltaic cells)

  • Chemical energy is transformed into electrical energy.
  • The redox reactions are spontaneous in nature.
  • The anode is negatively charged and the cathode is positively charged.
  • The electrons originate from the species that undergo oxidation.

Electrolytic cells

  • Electrical energy is transformed into chemical energy.
  • The redox reactions are non-spontaneous.
  • These cells are positively charged anode and negatively charged cathode.
  • Electrons originate from an external source.