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Analysing the oxidation enthalpies for $\ce{Li}$, $\ce{Na}$ and $\ce{K}$, we have their respective values:

  1. $\ce{Li} = \pu{162 kJ/mol}$
  2. $\ce{Na} = \pu{202 kJ/mol}$
  3. $\ce{K} = \pu{188kJ/mol}$

Sodium has the largest positive oxidation enthalpy, which means that its oxidation will be less likely to happen according to its Gibbs free energy. But, why does this happens to sodium?

Gaurang Tandon
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Bruno
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  • These are all negative I'm afraid. – Mithoron Jun 30 '17 at 20:56
  • I don't think they are... Take Lithium, for example: Dh(sublimation) = 161 kj/mol. Dh(ionization) = 520 kJ/mol. Dh(hydration) = -519 kJ/mol. – Bruno Jun 30 '17 at 21:46
  • Considering that Dh(oxidation) is: Dh = Dh(subli) + Dh(ioniz) + Dh(hydr), it will be positive... – Bruno Jun 30 '17 at 21:47
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    Maybe, no idea why you didn't use standard electrode potentials. – Mithoron Jun 30 '17 at 22:05
  • Currently, i am making an analysing of the Dh, Dg and the standard electrode potentials to explain why the elements of the group 1 are the best reducing agents. This was easy to explain, but when i go through the elements of group 1, the Sodium is the problem, because he has a higher Dh(oxidation) and a lower Standard Electrode Potential. This is what i am really stuck, because those two factors will tell that Sodium is the worst Reducing agent on group 1 – Bruno Jun 30 '17 at 22:09
  • https://chemistry.stackexchange.com/questions/28568/why-is-lithium-the-most-reducing-alkali-metal-and-not-caesium – Mithoron Jun 30 '17 at 22:12
  • Here are the values http://imgur.com/a/6GIKx – Bruno Jun 30 '17 at 22:13
  • Yes, this explains very well why Lithium is a stronger reducing agente. But, this still doesn't explain why Potassium, for example, is a better reducing agent than Soudium, you see? Considering that he has a larger size than Sodium. – Bruno Jun 30 '17 at 22:18
  • Why are you looking at enthalpy?! – Zhe Jun 30 '17 at 22:24
  • I am looking at it to make a analysis of the DGoxidation (Considering that DGox = Dhox - T*Ds). I was able to explain why group 1 have the best reducing agents, but now i have to see the case for sodium. – Bruno Jun 30 '17 at 22:28
  • And even if i try to explain it using Standard Electrode Potential, it will still be lower for Sodium than for the other elements of group 1. – Bruno Jun 30 '17 at 22:29
  • The type of analysis that i am making have to consider things like: What factor on the DH(oxidation) will be more relevant or primary to explain why the elements of group 1 are the best reducing agents? The conclusion that i brought up was: the Dh(ionization) and the Dh(sublimation) says that the elements of group 1 are the best reducing agents. But, the Dh(hydration) says they are the worst. So, Dh(ion) and Dh(subli) are the primary factors to explain this... – Bruno Jun 30 '17 at 23:06
  • Reduction potentials are related to free energy not enthalpy. Looking at enthalpy is wrong unless you are going to undertake the impossible task of quantifying ion solvation... – Zhe Jun 30 '17 at 23:10
  • Yes, true. I am just using the enthalpy because i have to make a analysis of it, really. I have just to consider that, if the enthalpy is more positive, it will contribute less to the Free energy, you know? I'm making this question based on the enthalpy just because i have to make analysis of the group 1 based on it, and relate this to the Free energy. – Bruno Jun 30 '17 at 23:13
  • I think that this will make it more clear: When you analyse the Dh(oxidation) of Lithium you have: His Dh(ion) is the more positive between the elements of the group. His Dh(Subl) is the more positive between the elements of the group. So, what will make his Dh(oxidation) less positive? The DH(hydration), which is exothermic, right? So, when you sum those 3, the result is that Lithium have a less positive Dh(oxidation). This means that his Dh(hydration) was able to compensate the Dh(ion) and Dh(sublimation). – Bruno Jun 30 '17 at 23:21
  • I don't understand why on sodium this compensation didnt happened so well. His Dh(hydration) is higher than for K, Rb andCs. But, still it wasn't enough to make his Dh(oxi) less positive than for K, Rb and Cs. I don't see why this happened to him, you see? – Bruno Jun 30 '17 at 23:23

1 Answers1

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The general trend in the reactivity of the group 1 elements is that it increases down the group. This can be attributed to the decrease in 1st ionisation energy as the atomic radius increases.

Reducing power can be measured by the standard electrode potential E0. This refers to the half - cell:

$$M^+(aq)+e⇌M(s)$$

If you look at the values for group 1 we see a different pattern:

Electrode Potential (V) Li. -3.02 Na. -2.71 K. -2.92 Rb. -2.99 Cs. -3.02

Lithium has an anomalously large and negative electrode potential. After Li the values become more large and negative, indicating, as you rightly say, that sodium has the lowest reducing power.

The reason for the unusual value for lithium is that E0 values are measured in solution whereas ionisation energies are measured in the gaseous phase.

To turn a metal atom in the solid state into an aqueous ion we can think of a 3 step process:

The metal is atomized. $\ce{Li(s)→Li(g)}$

The metal is ionised. $\ce{Li(g)→Li+(g)+e}$

The ion is hydrated. $\ce{Li+(g) +(aq)→Li+(aq)}$

Steps 1 and 2 are both endothermic, i.e. they require energy. Step 3 is exothermic as it is a bond forming process. It is referred to as the enthalpy of hydration.

The small size of the lithium ion gives it a large charge density and so water molecules are strongly attracted giving a large, negative enthalpy of hydration.

This is the main factor responsible for lithium's large, negative electrode potential.

In aqueous conditions it is as reducing as cesium though much less reactive in anhydrous conditions.

This anomaly accounts for sodium having the lowest reducing power, but only in aqueous conditions.

Glorfindel
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