Electronic Structure of Atoms (Electron Configurations) Quiz

PDF page 324: Electrons in successive atoms on the periodic table tend to fill low-energy orbitals first. Thus, many students find it confusing that, for example, the 5p orbitals fill immediately after the 4d, and immediately before the 6s. The filling order is based on observed experimental results, and has been confirmed by theoretical calculations. As the principal quantum number, n, increases, the size of the orbital increases and the electrons spend more time farther from the nucleus. Thus, the attraction to the nucleus is weaker and the energy associated with the orbital is higher (less stabilized). But this is not the only effect we have to take into account. Within each shell, as the value of l increases, the electrons are less penetrating (meaning there is less electron density found close to the nucleus), in the order s > p > d > f. Electrons that are closer to the nucleus slightly repel electrons that are farther out, offsetting the more dominant electron–nucleus attractions slightly (recall that all electrons have −1 charges, but nuclei have +Z charges). This phenomenon is called shielding and will be discussed in more detail in the next section. Electrons in orbitals that experience more shielding are less stabilized and thus higher in energy. For small orbitals (1s through 3p), the increase in energy due to n is more significant than the increase due to l; however, for larger orbitals the two trends are comparable and cannot be simply predicted. We will discuss methods for remembering the observed order. The arrangement of electrons in the orbitals of an atom is called the electron configuration of the atom. We describe an electron configuration with a symbol that contains three pieces of information (Figure 6.25):

PDF page 323: The energy of atomic orbitals increases as the principal quantum number, n, increases. In any atom with two or more electrons, the repulsion between the electrons makes energies of subshells with different values of l differ so that the energy of the orbitals increases within a shell in the order s < p < d < f. Figure 6.24 depicts how these two trends in increasing energy relate. The 1s orbital at the bottom of the diagram is the orbital with electrons of lowest energy. The energy increases as we move up to the 2s and then 2p, 3s, and 3p orbitals, showing that the increasing n value has more influence on energy than the increasing l value for small atoms. However, this pattern does not hold for larger atoms. The 3d orbital is higher in energy than the 4s orbital. Such overlaps continue to occur frequently as we move up the chart.

PDF page 323: The energy of atomic orbitals increases as the principal quantum number, n, increases. In any atom with two or more electrons, the repulsion between the electrons makes energies of subshells with different values of l differ so that the energy of the orbitals increases within a shell in the order s < p < d < f. Figure 6.24 depicts how these two trends in increasing energy relate. The 1s orbital at the bottom of the diagram is the orbital with electrons of lowest energy. The energy increases as we move up to the 2s and then 2p, 3s, and 3p orbitals, showing that the increasing n value has more influence on energy than the increasing l value for small atoms. However, this pattern does not hold for larger atoms. The 3d orbital is higher in energy than the 4s orbital. Such overlaps continue to occur frequently as we move up the chart.

PDF page 323: The energy of atomic orbitals increases as the principal quantum number, n, increases. In any atom with two or more electrons, the repulsion between the electrons makes energies of subshells with different values of l differ so that the energy of the orbitals increases within a shell in the order s < p < d < f. Figure 6.24 depicts how these two trends in increasing energy relate. The 1s orbital at the bottom of the diagram is the orbital with electrons of lowest energy. The energy increases as we move up to the 2s and then 2p, 3s, and 3p orbitals, showing that the increasing n value has more influence on energy than the increasing l value for small atoms. However, this pattern does not hold for larger atoms. The 3d orbital is higher in energy than the 4s orbital. Such overlaps continue to occur frequently as we move up the chart.

PDF page 324: For example, the notation 2p (read "two–p–four") indicates four electrons in a p subshell (l = 1) with a principal

PDF page 325: To determine the electron configuration for any particular atom, we can “build” the structures in the order of atomic numbers. Beginning with hydrogen, and continuing across the periods of the periodic table, we add one proton at a time to the nucleus and one electron to the proper subshell until we have described the electron configurations of all the elements. This procedure is called the Aufbau principle, from the German word Aufbau (“to build up”). Each added electron occupies the subshell of lowest energy available (in the order shown in Figure 6.24), subject to the limitations imposed by the allowed quantum numbers according to the Pauli exclusion principle. Electrons enter higher-energy subshells only after lower-energy subshells have been filled to capacity. Figure 6.26 illustrates the traditional way to remember the filling order for atomic orbitals. Since the arrangement of the periodic table is based on the electron configurations, Figure 6.27 provides an alternative method for determining the electron configuration. The filling order simply begins at hydrogen and includes each subshell as you proceed in increasing Z order. For example, after filling the 3p block up to Ar, we see the orbital will be 4s (K, Ca), followed by the 3d orbitals.

PDF page 326: Following hydrogen is the noble gas helium, which has an atomic number of 2. The helium atom contains two protons and two electrons. The first electron has the same four quantum numbers as the hydrogen atom electron (n = 1, l = 1 0, ml = 0, ms = + ). The second electron also goes into the 1s orbital and fills that orbital. The second electron 2 1 has the same n, l, and ml quantum numbers, but must have the opposite spin quantum number, ms = − . This is in 2 accord with the Pauli exclusion principle: No two electrons in the same atom can have the same set of four quantum numbers. For orbital diagrams, this means two arrows go in each box (representing two electrons in each orbital)

PDF page 326: Following hydrogen is the noble gas helium, which has an atomic number of 2. The helium atom contains two protons and two electrons. The first electron has the same four quantum numbers as the hydrogen atom electron (n = 1, l = 1 0, ml = 0, ms = + ). The second electron also goes into the 1s orbital and fills that orbital. The second electron 2 1 has the same n, l, and ml quantum numbers, but must have the opposite spin quantum number, ms = − . This is in 2 accord with the Pauli exclusion principle: No two electrons in the same atom can have the same set of four quantum numbers. For orbital diagrams, this means two arrows go in each box (representing two electrons in each orbital)

PDF page 327: and the arrows must point in opposite directions (representing paired spins). The electron configuration and orbital diagram of helium are:

PDF page 327: The n = 1 shell is completely filled in a helium atom. The next atom is the alkali metal lithium with an atomic number of 3. The first two electrons in lithium fill the 1s orbital and have the same sets of four quantum numbers as the two electrons in helium. The remaining electron must occupy the orbital of next lowest energy, the 2s orbital (Figure 6.26 or Figure 6.27). Thus, the electron configuration and orbital diagram of lithium are:

PDF page 327: Carbon (atomic number 6) has six electrons. Four of them fill the 1s and 2s orbitals. The remaining two electrons occupy the 2p subshell. We now have a choice of filling one of the 2p orbitals and pairing the electrons or of leaving the electrons unpaired in two different, but degenerate, p orbitals. The orbitals are filled as described by Hund’s rule: the lowest-energy configuration for an atom with electrons within a set of degenerate orbitals is that having the maximum number of unpaired electrons. Thus, the two electrons in the carbon 2p orbitals have identical n, l, and ms quantum numbers and differ in their ml quantum number (in accord with the Pauli exclusion principle). The electron configuration and orbital diagram for carbon are:

PDF page 328: the lowest-energy subshell available, the 3s orbital, giving a 1s 2s 2p 3s configuration. The electrons occupying the outermost shell orbital(s) (highest value of n) are called valence electrons, and those occupying the inner shell orbitals are called core electrons (Figure 6.28). Since the core electron shells correspond to noble gas electron configurations, we can abbreviate electron configurations by writing the noble gas that matches the core electron configuration, along with the valence electrons in a condensed format. For our sodium example, the symbol [Ne]

PDF page 328: represents core electrons, (1s 2s 2p ) and our abbreviated or condensed configuration is [Ne]3s .