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Zn which has the highest ionisation enthalpy in 3d series.The reason given in my textbook is:

The value of zinc is higher because it represent ionisation from 4s level.

This is not correct because for every 3d element ionisation is from 4s orbital. The explanation I found for this is from this site is:

https://www.chemguide.co.uk/atoms/properties/ies.html

Increase in nuclear charge outweigh the electron electron repulsion of 4s electrons rendering Zn an higher ionisation enthalpy than Cu.

This seems like a probable explanation but if Zn has higher ionisation enthalpy than Cu due to its increased nuclear charge.Why can't Zn have smaller atomic radius than Cu due to its increased nuclear charge which can decrease the size of the atom. But experimentally it has been found that Zn is bigger in size than Cu.

So why does Zn has the highest ionisation enthalpy in 3d series?

TEXT SOURCE:NCERT textbook (chapter:d and f block)

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    $\begingroup$ Where is the atomic radius of Zn rendered larger than that of Cu? In Wikipedia they are the same and so are a few preceding elements to boot. $\endgroup$
    – Oscar Lanzi
    Feb 10, 2020 at 0:55
  • $\begingroup$ In my textbook it's given that Zn has a higher atomic radii than Cu $\endgroup$
    – Grace
    Feb 10, 2020 at 1:48
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    $\begingroup$ The reference for the textbook being ... $\endgroup$
    – Oscar Lanzi
    Feb 10, 2020 at 2:02
  • $\begingroup$ The real reason for this happening is because the orbitals self overlap in the d-block; refer to the band theory. pci.tu-bs.de/aggericke/PC4e/Kap_II/Metalle.htm and check out this question that I've asked chemistry.stackexchange.com/questions/123802/… $\endgroup$
    – Reine Abstraktion
    Feb 12, 2020 at 11:18
  • $\begingroup$ I think a more suitable question would be "is atomic radii and ionization independent properties" $\endgroup$
    – Reine Abstraktion
    Feb 12, 2020 at 11:20

2 Answers 2

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There is band structure formed in the metallic lattice in the crystals of d and f block elements due to partially filled orbitals. But as you move along the periodic table to 'Zn' , you will find that the orbitals are completely filled hence there is no possibility for inter-orbital mixing. Another thing worth noting is that due to the filled d-orbital, zn and copper behaves more like s-block rather than d-block elements.

"The filled d-shells in these elements contribute little to interatomic interactions, which are dominated by the s-electrons through metallic bonds. Unlike metals with incomplete d-shells, metallic bonds in copper are lacking a covalent character and are relatively weak. "

An alternate explanation can be on the metallic lattice: Copper has a face centered cubic structure and zinc has a hexagonal close packed structure

reference : wikipedia

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  • $\begingroup$ why the downvote? $\endgroup$
    – Reine Abstraktion
    Feb 12, 2020 at 11:53
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In the Zinc atom, the levels $4s$ and $3d$ are completely occupied. This increases the stability of the atom. And electrons need more energy to be removed.

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