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Q4.17(ii):

For \(M^{2+}/M\) and \(M^{3+}/M^{2+}\) systems the \(E^{o}\) values for some metals are as follows:

Use this data to comment upon: (ii) the ease with which iron can be oxidised as compared to a similar process for either chromium or manganese metal.

Solution :

Step 1: Data Extraction and Thermodynamic Framework

To evaluate the ease of oxidation for the metals Cr, Mn, and Fe from the neutral state ($M^0$) to the dipositive state ($M^{2+}$), we must analyze the standard electrode potentials ($E^o$) provided for the $M^{2+}/M$ redox couple. The oxidation half-reaction is represented as:

$M(s) \rightarrow M^{2+}(aq) + 2e^-$

The standard potential for this oxidation is given by $E^o_{ox} = -E^o_{red}$. [Per the principles of Electrochemistry, a more negative reduction potential $E^o_{M^{2+}/M}$ signifies a greater tendency to undergo oxidation.]

Step 2: Comparative Analysis of $E^o$ Values

Based on the provided data, we extract the reduction potentials ($E^o_{M^{2+}/M}$):

Metal $E^o$ ($M^{2+}/M$) in Volts
Chromium ($Cr$) $-0.90$
Manganese ($Mn$) $-1.18$
Iron ($Fe$) $-0.44$

Step 3: Calculating Oxidation Potentials

The oxidation potential ($E^o_{ox}$) represents the ease of losing electrons. The higher the positive value of $E^o_{ox}$, the easier the metal is to oxidize.

  • For $Cr$: $E^o_{ox} = -(-0.90\text{ V}) = +0.90\text{ V}$
  • For $Mn$: $E^o_{ox} = -(-1.18\text{ V}) = +1.18\text{ V}$
  • For $Fe$: $E^o_{ox} = -(-0.44\text{ V}) = +0.44\text{ V}$

Step 4: Interpretation of Results

Comparing the oxidation potentials: $E^o_{Mn} (+1.18\text{ V}) > E^o_{Cr} (+0.90\text{ V}) > E^o_{Fe} (+0.44\text{ V})$.

The magnitude of the oxidation potential is directly proportional to the thermodynamic feasibility of the oxidation process. Since the oxidation potential of Iron ($+0.44\text{ V}$) is significantly lower than that of both Manganese ($+1.18\text{ V}$) and Chromium ($+0.90\text{ V}$), it follows that Iron is the most resistant to oxidation among the three.

Fe (+0.44V) Cr (+0.90V) Mn (+1.18V) Ease of Oxidation increases ->

Final Solution: Iron ($Fe$) is less easily oxidized than Chromium ($Cr$) or Manganese ($Mn$) because its standard oxidation potential ($+0.44\text{ V}$) is lower than the oxidation potentials of both Chromium ($+0.90\text{ V}$) and Manganese ($+1.18\text{ V}$), indicating a lesser thermodynamic tendency to lose electrons compared to the other two metals.


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