Question:

The standard emf of the cell $ (E^{\circ}_{cell} $ and equilibrium constant $ (K_{eq}) $ of the following reaction of $ 298\, K $ $ Cd^{2+} + 4NH_{3} {\rightleftharpoons} Cd (NH_{3})^{2+}_{4} $

Updated On: Jul 29, 2023
  • $ E^{\circ}_{cell}=1.0V, K_{eq}=126\times10^{7} $
  • $ E^{\circ}_{cell}=0.21 V, K_{eq}=126\times10^{7} $
  • $ E^{\circ}_{cell}=1.0 V, K_{eq}=6.60\times10^{33} $
  • $ E^{\circ}_{cell}=0.21 V, K_{eq}=6.60\times10^{33} $
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The Correct Option is B

Solution and Explanation

(we assume that standard emf of the cell \(E^{\circ}_{cell}\) is known) 
For the given equilibrium, 
\(Cd^{2+}+4NH_{3} {<=>} Cd(NH_{3})^{2+}_{4}\) 
At equilibrium, 
\(E^{\circ}_{cell}=0\) 
Hence, we can calculate the equilibrium constant for reaction as follows : 
\(E^{\circ}_{cell}=\frac{0.0591\,V}{n} log \,K_{c}\) 
Where, \(K_{c}\) is unknown 
\(E^{\circ}_{cell}=0.21\,V\)
\(0.21\,V=\frac{0.0591}{2}log K_{c}\)
\(log\,K_{c}=\frac{0.21\times2}{0.0591}\)
\(log\,K_{c}=\frac{0.42}{0.0591}=7.1065\)
\(K_{c}=1.27\times10^{7}\)

The largest potential difference between two electrodes of a cell, while no current is being pulled from the cell, is known as the electromotive force, or EMF. The charges in an electric circuit move, and in order for the charges in a specific electric circuit to move, we must apply an external force to that electric circuit.

A battery or any other possible difference-making mechanism can serve as the source of an external force. The electromotive force, which is applied by the external electric source and accelerates the charges, is a physical force. 

Considering the formula for electromotive force as,

ε = V + Ir

Where

  • The voltage of the cell is V.
  • Current across the circuit is I.
  • The internal resistance of the cell is R.
  • The electromotive force is ε.

Kp is the equilibrium constant determined from the partial pressure of the equation of a reaction. It's a mathematical expression to determine the relation between product and reactant pressures. Although it connects the pressures, it is a unitless number. 

Kc is the equilibrium constant for a reversible reaction, which depicts the ratio of the equilibrium concentrations of products over the concentrations of reactants, where each is raised to the power of their stoichiometric coefficients.

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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.