Chapter 5, Problem 5.3PR

(a)

Interpretation Introduction

Interpretation:

The standard potential of the silver-silver chloride may be determined by plotting $E+\left(\frac{RT}{F}\right)\ln b$ against $b^{1/2}$ has to be shown.

Concept Introduction:

Nernst equation:

  $E_{cell}orEMF=E^{\Theta }-\frac{2.303RT}{nF}\log Q$

Where,

n = Total no. of electrons lost or gained in the overall reaction

Q = Reaction co-efficient $=$ $\frac{\left[OS\right]}{\left[RS\right]}$

$\left[OS\right]=$ Concentration of oxidized state

$\left[RS\right]=$ Concentration of reduced state

$\begin{array}{l}1F=96500C\\ \\ T=298K\\ \\ R=8.314J/K\end{array}$

Now the equation can be written as

  $E_{cell}orEMF=E^{\Theta }-\frac{0.0591}{n}\log Q$

Ionic strength:

  $I=\frac{1}{2}\Sigma m_i{Z}_i^2$

Where,

$m=$ Molality

$Z=$ Charge of the ion

Debye-Huckel limiting law:

The mean activity coefficient is given by

  $\log {\gamma }_{\pm }=-A\left|Z_{+}{Z}_{-}\right|\sqrt{I}$

(b)

Interpretation Introduction

Interpretation:

The standard potential of silver-silver chloride electrode has to be determined.

Concept Introduction:

Nernst equation:

  $E_{cell}orEMF=E^{\Theta }-\frac{2.303RT}{nF}\log Q$

Where,

n = Total no. of electrons lost or gained in the overall reaction

Q = Reaction co-efficient $=$ $\frac{\left[OS\right]}{\left[RS\right]}$

$\left[OS\right]=$ Concentration of oxidized state

$\left[RS\right]=$ Concentration of reduced state

  $\begin{array}{l}1F=96500C\\ \\ T=298K\\ \\ R=8.314J/K\end{array}$

Now the equation can be written as

  $E_{cell}orEMF=E^{\Theta }-\frac{0.0591}{n}\log Q$

Ionic strength:

  $I=\frac{1}{2}\Sigma m_i{Z}_i^2$

Where,

$m=$ Molality

$Z=$ Charge of the ion

Debye-Huckel limiting law:

The mean activity coefficient is given by

  $\log {\gamma }_{\pm }=-A\left|Z_{+}{Z}_{-}\right|\sqrt{I}$