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Quim. Nova, Vol. 36, No.

6, 894-896, 2013


Hugo Orofino, Sergio P. Machado e Roberto B. Faria*
Instituto de Química, Universidade Federal do Rio de Janeiro, 21941-611 Rio de Janeiro – RJ, Brasil

Recebido em 25/9/12; aceito em 2/2/13; publicado na web em 24/5/13

Rich and Suter diagrams are a very useful tool to explain the electron configurations of all transition elements, and in particular,
the s1 and s0 configurations of the elements Cr, Cu, Nb, Mo, Ru, Rh, Pd, Ag, and Pt. The application of these diagrams to the inner
transition elements also explains the electron configurations of lanthanoids and actinoids, except for Ce, Pa, U, Np, and Cm, whose
electron configurations are indeed very special because they are a mixture of several configurations.

Keywords: periodic table; electronic configuration; Rich and Suter diagrams.

The electronic configuration of chemical elements is a very
important and initial topic in all introductory chemistry courses.
To obtain them, the Aufbau principle is used in connection with the
orbitals energies. However, the explanation of the s1 ground-state
electron configurations of Cr and Cu is generally based on the special
stability attributed to a half-filled and filled subshell, respectively.1-3
Otherwise, these configurations can be explained by the very elegant
Rich and Suter diagrams.4 These and some other authors clearly
state that there is no extra stability for a filled or half-filled subshell
compared with a subshell containing one electron less.4–7 The s1 and
s0 electron configurations of neutral isolated atoms of some transition
elements can be explained by considering that each subshell energy
level is split into two levels, a and b, related to the spin of the elec-
trons, as can be seen in Figure 1. The Coulomb energy on account
of the pairing of two electrons in the same orbital is assigned to the
b level, because of which this level appears to be at a higher energy
than the a level. In Figure 1a, the number 6 at the crossing point
between the 3da and 4sa lines has the meaning 3da5 and 4sa1, and
the same meaning applies to Figure 1c.
This type of diagram is very easily grasped by students and
makes the explanation of the “anomalous” s1 and s0 electron con-
figurations of transition elements much more reasonable. As can
be seen in Figure 1a, the 4s2 3d3 vanadium electron configuration
comes from the fact that both levels, 4sa and 4sb, have a lower
energy than 3da. As we move to the right on the periodic table,
the atomic number increases and all the levels go down. Because
the 3d levels are closer to the core, they decrease faster than the 4s
level, and the 3da level crosses the 4sb level when passing from V
to Cr. It causes that for Cr, the 3da level must be completely filled
with five electrons before we can put any electrons in the 4sb level.
Because Cr only has six electrons in the valence shell, there is no
electron to occupy the 4sb level, which results in the 4s1 3d5 electron
configuration of Cr. The same situation occurs upon going from
Ni to Cu. For Ni, the 4sb level is below 3db, whereas for Cu these
levels cross and 3db becomes lower than 4sb. This means that the
levels must be filled in the sequence: 3da5 4sa1 3db5, and because
there are no more electrons, the Cu electron configuration is 4s1 3d10.
Using the Rich and Suter diagram for the second transition period
(Figure 1b), it is also easy to explain why Pd has a 5s0 4d10 electron
configuration. Because the two levels 4da and 4db are lower than the Figure 1. Rich and Suter diagrams for the isolated atoms of transition elements
5s level, the ten electrons of the Pd valence shell fill the 4d levels, in their ground state. (a) 3d period; (b) 4d period; (c) 5d period. (Parts (a)
and (b) adapted with permission from R. L. Richer and R. W. Suter, J. Chem.
*e-mail: Educ. 1998, 65, 702. Copyright 1988 American Chemical Society.)

which has been the subject of specific studies to explain its occurrence. 6s2 5d2. the crossing point involving the levels 4fa chemistry textbooks. such Similar diagrams can be constructed for lanthanoids and actinoids. and Cm. which cannot be explained by using In Figure 3. The use of such diagrams eliminates the traditional half-filled and filled subshell argument. which turns into 4s0 3d3 for vanadium(II). before the next one can start to be occupied. the Ce spectra has approximately transition elements. however. that the correct electron configurations of these elements are indeed justifying the fact that the coordination chemistry of these transition special. of the lanthanoid element Ce or the actinoids Pa.9-13 In this figure. as the assignment of the split of lines by the presence of a magnetic as can be seen in Figure 3 for the first case. the application of Hund’s rule predicts a 3H term as the most stable one for a 6s2 5d1 4f1 configuration. U. 6L11/2. we would also like to mention in this article that 25000 lines. Students usually do not know that it is not a simple task to elements in oxidation states higher than zero does not involve any determine the electron configuration of an element. For example. 6 The use of Rich and Suter diagrams to explain the electron configurations of transition elements 895 namely 4da5 4db5. similar to that shown in Figure 3. Rich and Suter diagrams are a very useful tool to explain the electron configurations of all the transition elements. Np (7s2 6d1 5f4). No. 5L6o. As can be energy level until it is complete. After two of them have Cm (7s2 6d1 5f7) present the same difficulty. the predicted Ce electron explanation of the electronic configurations of transition elements. Np. and that it requires electrons in the 4s orbitals. seen in Figure 1a. The same the Rich and Suter diagram cannot explain the electron configurations diagram also explains the electron configurations of Nb (5s1 4d4). ACKNOWLEDGEMENTS Figure 3. U. between La and Ce). the fun- damental energy level is a mixture of several electron configurations. accounting for only 55% of the composition of the neutral Ce ground level. CAPES and FAPERJ for financial their ground state. and that all electrons must go to the lower configuration. which are the 3d3 electrons. in contradiction with the experimental configuration of 6s2 As far as we know. giving the 4d10 electron configuration. and approximately 15000 lines were mainly assigned to transitions from high levels to terms belonging to the lowest confi- gurations 6s2 5d1 4f1 and 6s1 5d2 4f1. respectively. considering the energy separation of different spin levels and sition elements after they lose two electrons to form M2+ ions their crossing as we move along a transition-element period. configuration will be 6s2 4f2. field (Zeeman effect) and the determination of associated g values..12 Nevertheless. the electron configuration of Ce is predicted to be the half-filled or filled subshell argument. a been removed. and Rh (5s1 4d8). Rich and Suter diagram for the isolated atoms of lanthanoids in The authors thank CNPq. respectively. Rich and Suter diagram for the isolated atoms of first-period tran. U. and gives the impression that the 4s electrons have been removed Because Rich and Suter diagrams are a better—but still sim- during the oxidation process. U (7s2 6d1 5f3). presented in an inorganic chemistry the accepted electron configuration for this element. which is again in disagreement with The diagrams are. and Cm have the low-energy terms 4K11/2.11 In addition. Ru (5s1 4d7). and 9D2o.15 In conclusion. in agreement with Hund’s rule. . It helps students to substitute the “electron configu- rations dogma” by the correct view that the electron configuration of an element is the description of the atomic electronic structure based on a theoretical model. Using Rich and textbook by Miessler and Tarr. The electron configuration for Ce is not correct support. and there is no reason for this because they and 5da has been positioned between Ce and Pr. the elements Pa. which eventually results in a 4s0 3d3 electron configuration electrons. vanadium has a 4s2 3d3 electron electrons.e. contrary to the accepted 1G4o term. These diagrams are easy to draw and are based on the orbitals’ relative Figure 2. The rea- elements apparently lose their 4s2 electrons when they go to a hi. these diagrams are not presented in general 5d1 4f1. the electrons to be removed must be those with a The elements Pa (7s2 6d1 5f2). the levels with lower principal quantum 5f (a and b) subshells. The lowest energy term 1G4o is not a pure term. This makes the 3d levels go not possible to let a small number of electrons go into levels 6da and below the 4s level so that the electrons can now occupy the lower 5fa because these levels must be completely filled with five or seven 3da level. the model needs to consider that for these atoms. the atom’s positive charge causes a decrease in all Rich and Suter diagram can be constructed for the 6d (a and b) and the orbital energy levels. This same reasoning can be applied to plified—way to explain electron configurations. Despite its success in explaining the electron configurations of To give an idea of these difficulties. the correlation of experimental line spectra and theoretical work. however. Np. and Cm is an additional subject that leads to a richer and deeper understanding of electron configurations. Because these spectra become more complex for heavier elements. Np. if it is are simple and contribute to a much more logical reasoning in the moved to the left (i. energies. son for this is that these two levels can accommodate seven and five gher oxidation state. Pa. and higher energy.8 Suter diagrams. we must be aware all the first-period transition elements (as can be seen in Figure 2). This means that Ce has a very special electron configuration of the kind ns2 (n-1)d1 (n-2)fx.Vol. The discussion of the electron configurations of Ce. 36. Again. which is intended to explain the experimental line spectra. which does not have any physical support.14 For these actinoids. which does not follow this rule. there is no way to obtain an electron configuration Rich and Suter diagrams also explain why the first transition containing one electron on each of the levels 4fa and 5da. it is number being more sensible (Figure 2).

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segue abaixo a Figura 1c. 194. 21941-611 Rio de Janeiro – RJ. Brasil A pedido do autor. p. Sergio P. No. 2013: *e-mail: faria@iq. 36. 2014 THE USE OF RICH AND SUTER DIAGRAMS TO EXPLAIN THE ELECTRON CONFIGURATIONS OF TRANSITION ELEMENTS Errata Hugo Orofino. Universidade Federal do Rio de Janeiro. Nova. Machado e Roberto B. Vol. . Quim. Faria* Instituto de Química. 1. 6. corrigida. do artigo publicado no vol. 37. 894-896.ufrj.