I have seen a variety of reactivity series of elements online and also have consulted some books regarding the arrangement of the elements. I understand that the arrangement of elements is based on degree of reactivity of elements with cold water, steam, oxygen, dilute acids etc. Lithium is less reactive with respect to the criteria mentioned above yet it is placed on the top of more reactive elements in the reactivity series that I have observed. What is the reason for the position of Lithium above let us say potassium and sodium which are more reactive. Link to one of the references: https://kaiserscience.wordpress.com/chemistry/metal-reactivity-series/
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$\begingroup$ The electrode potentials in water, really aqueous acid, are free energy deltaG[0] changes of the reaction with H2 or H+ ions Everything in their standard states, to equilibrium. If it sounds complicated it is because it is complicated. It takes into account all the various heats and entropies. What is of limited importance is the apparent reactivity. Li reacts more sedately than Na or K or frightenly reactive Cs[The differences really are very small] but seems to go farther when done. The relative energies will change if products change by changes in solubility or by complexation $\endgroup$– jimchmstCommented Mar 23 at 22:33
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The reason that lithium is on the top of the activity series is due to its behavior in aqueous reactions with water and acid. Due to the lithium atom's very small size (only two energy levels), the lithium ion interacts well with water forming ion-dipole interactions. The lithium atom's small size compared to sodium and potassium is more entropically favorable in the formation of ion-dipole interactions with water and consequently so are reactions involving lithium ion formation favored to to other alkali metals.
The reasoning behind this is that reactions favor a greater state of entropy (disorder) in the universe. With larger cations, more water molecules have to become ordered around the cation to form the appropriate ion-dipole interaction. However, due to the lithium cation's small size, less water molecules are required to form the ion-dipole interaction, thus less order, being more favorable in terms of entropy.
