d-block facets

This page looks at some of the problems with the usual way of explaining the electronic structures of the d-block elements based on the order of filling of the d and s orbitals. The way that the order of filling of orbitals is normally taught gives you an easy way of working out the electronic structures of elements. However, it does throw up problems when you come to explain various properties of the transition elements. This page takes a closer look at this, and offers a more accurate explanation which avoids the problems.

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The Order of Filling Orbitals

The aufbau principle explains how electrons fill low energy orbitals (closer to the nucleus) before they fill higher energy ones. Where there is a choice between orbitals of equal energy, they fill the orbitals singly as far as possible (Hunds rules). The diagram (not to scale) summarizes the energies of the orbitals up to the 4p level.

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Figure 1: Electronic energies orbitals.

The oddity is the position of the 3d orbitals, which are shown at a slightly higher level than the 4s. This means that the 4s orbital which will fill first, followed by all the 3d orbitals and then the 4p orbitals. Similar confusion occurs at higher levels, with so much overlap between the energy levels that the 4f orbitals do not fill until after the 6s, for example.

Everything is straightforward up to this point, but the 3-level orbitals are not all full - the 3d levels have not been used yet. But if you refer back to the energies of the orbitals, you will see that the next lowest energy orbital is the 4s - so that fills first.

K 1s22s22p63s23p64s1
Ca 1s22s22p63s23p64s2


d-block elements

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Figure 2: Periodic table of periods 2-4.

d-block elements are thought of as elements in which the last electron to be added to the atom is in a d orbital (actually, that turns out not to be true! We will come back to that in detail later.) The electronic structures of the d-block elements are shown in the table below. Each additional electron usually goes into a 3d orbital. For convenience, is used to represent 1s22s22p63s23p6.

Sc 3d14s2
Ti 3d24s2
V 3d34s2
Cr 3d54s1
Mn 3d54s2
Fe 3d6 4s2
Co 3d74s2
Ni 3d84s2
Cu 3d104s1
Zn 3d104s2

d-block ions

This is probably the most unsatisfactory thing about this approach to the electronic structures of the d-block elements. In all the chathamtownfc.netistry of the transition elements, the 4s orbital behaves as the outermost, highest energy orbital. The reversed order of the 3d and 4s orbitals only seems to apply to building the atom up in the first place. In all other respects, the 4s electrons are always the electrons you need to think about first.

When d-block (first row) elements form ions, the 4s electrons are lost first.


When discussing ionization energies for these elements, you talk in terms of the 4s electrons as the outer electrons being shielded from the nucleus by the inner 3d levels. We say that the first ionization energies do not change much across the transition series, because each additional 3d electron more or less screens the 4s electrons from the extra proton in the nucleus.

The explanations around ionization energies are based on the 4s electrons having the higher energy, and so being removed first.






Summary

In each of these cases we have looked at, the 3d orbitals have the lowest energy, but as we add electrons, repulsion can push some of them out into the higher energy 4s level.

If you build up the scandium atom from scratch, the last electrons to go in are the two 4s electrons. These are the electrons in the highest energy level, and so it is logical that they will be removed first when the scandium forms ions. And that"s what happens. The 4s electrons are also clearly the outermost electrons, and so will largely define the radius of the atom. The lower energy 3d orbitals are inside them, and will contribute to the screening. There is no longer any conflict between these properties and the order of orbital filling.

The difficulty with this approach is that you cannot use it to predict the structures of the rest of the elements in the transition series. In fact, what you have to do is to look at the actual electronic structure of a particular element and its ions, and then work out what must be happening in terms of the energy gap between the 3d and 4s orbitals and the repulsions between the electrons.


The common way of teaching this (based on the wrong order of filling of the 3d and 4s orbitals for transition metals) gives a method which lets you predict the electronic structure of an atom correctly most of the time. The better way of looking at it from a theoretical point of view no longer lets you do that. You can get around this, of course. If you want to work out a structure, use the old method. But remember that it is based on a false idea, and do not try to use it for anything else - like working out which electrons will be lost first from a transition element, for example.


Example (PageIndex3): Vanadium

Vanadium has two more electrons than scandium, and two more protons as well, of course. Think about building up a vanadium atom in exactly the same way that we did scandium. We have the nucleus complete and now we are adding electrons. When we have added 18 electrons to give the argon structure, we have then built a V5+ ion.

Now look at what happens when you add the next 5 electrons.

V5+
V4+ 3d1
V3+ 3d2
V2+ 3d3
V+ 3d4
V 3d34s2

The energy gap between the 3d and 4s levels has widened. In this case, it is not energetically profitable to promote any electrons to the 4s level until the very end. In the ions, all the electrons have gone into the 3d orbitals. You couldn"t predict this just by looking at it.



Conclusion

The current method of teaching students to work out electronic structures is fine as long as you realize that that is all it is - a way of working out the overall electronic structures, but not the order of filling. You can say that for potassium and calcium, the 3d orbitals have a higher energy than the 4s, and so for these elements, the 4s levels fill before than the 3d. That, of course, is entirely true! Then you can say that, looking at the structures of the next 10 elements of the transition series, the 3d orbitals gradually fill with electrons (with some complications like chromium and copper). That is also true. What is not right is to imply that the 3d levels across these 10 elements have higher energies than the 4s. That is definitely not true, and causes the sort of problems we have been discussing.

See more: An Electrolytic Cell Is Different From A Voltaic Cell Because In An Electrolytic Cell


References

R. N. Keller: Textbook errors, 38: Energy Level Diagrams and Extranuclear Building of the Elements: J. chathamtownfc.net. Educ., 1962, 39 (6), p 289, published June 1962 W. H. Eugen Schwarz: The Full Story of the Electron Configurations of the Transition Elements: Journal of chathamtownfc.netical Education, Vol. 87 No. 4 April 2010.