Electron = Configurations T he quantum model of the atom improves on the Bohr model because it describes the arrangements of electrons in atoms other than hydrogen. ‘configuration, Because atoms of different elements have different num- bers of electrons, a unique electron configuration exists for the atoms of each element. Like all systems in nature, electrons in atoms tend to assume arrangements that have the lowest possible energies. HEIIOWESE ‘energy arrangement of the electrons for each element is called the ele~ ‘ment's ground-state electron configuration. A few simple rules, combined ‘with the quantum number relationships discussed in Section 2, allow us to determine these ground-state electron configurations. Rules Governing Electron Configurations ‘To build up electron configurations for the ground state of any particular atom, first the energy levels of the orbitals are determined, Then electrons are added to the Ossectives © List the total number of elec- trons needed to fully occupy each main energy level. © State the Aufbau principle, the Pauli exclusion principle, ‘and Hund’s rule © Rescrie the electron configurations for the atoms of any element using cotbital notation, electron- configuration notation, and, when appropriate, noble-gas notation, orbitals one by one according to three basic rules (Remember that real atoms are not built up by adding protons and electrons one at a time.) Energy ——» Figure 16 shows the atomic orbitals in order of increas- ing energy. The orbital with the lowest energy is the 1s orbital. In a ground-state hydrogen atom, the electron is in this orbital. The 2s orbital is the next highest in energy, then the 2p orbitals. Beginning with the third main energy level, 1 =3, the energies of the sublevels in different main energy levels begin to overlap. Note in the figure, for example, that the de sthlevel is atomic sublevels i shown on the vertical axis Each lower in energy than the 3d sublevel. Therefore, the 4s orbital is filled before any electrons enter the | FIGURE 16 The order of increasing energy for 3d orbitals. (Less energy is required for two electrons to pair up in the 4s orbital than for those two electrons to individual box represents an o ARRANGEMENT OF ELECTRONS IN ATOMS (111FIGURE 17 According to the Pauli exclusion principle, an orbital can hold two electrons of opposite spin states. In this electron contfigu- ration of a helium atom, each arrow represents one ofthe atom's two electrons. The direction of the arrow indicates the electron's spin stat, FIGURE 18 The figure shows HOW 112) cHaprer 4 ‘occupy a 3d orbital.) Once the 3d orbitals are fully occupied, which sublevel will be occupied next? ‘The second rule reflects the importance of the spin quantum num- ber. According to the Pauli exelusion principle, 110 nwo electrons in the ‘same atom can have the same set of four quantum numbers. The princi- pal, angular momentum, and magnetic quantum numbers specify the energy. shape; and orientation of an orbital, The two values of the spin quantum number reflect the fact that for two electrons to occupy the same orbital, they must have opposite spin states (see Figure 17), ‘The third rule requires placing as many unpaired electrons as possible in separate orbitals in the same sublevel. In this way, electron-electron repulsion is minimized so that the electron arrangements have the low- est energy possible. According to Hund’s rule, orbitals of equal energy are each occupied by one electron before any orbital is occupied by a second electron, and all electrons in singly occupied orbitals must have the same spinistate. Applying this rule shows, for example, that one electron wil enter each of the three p orbitals in a main energy level before a second electron enters any of them. This is illustrated in Figure 18. What is the ‘maximum number of unpaired electrons in a d sublevel? TL) Mitt) Met @ ro) © Representing Electron Configurations ‘Three methods, or notations, are used to indicate electron configura- tions. Two of these notations will be discussed in the next two sections {or the first-period elements, hydrogen and helium. The third notation is used mostly with elements of the third period and higher. It will be discussed in the section on third-period elements. Orbital Notation In orbital notation, an unoceupied orbital is represented by a ine, with the orbita’s name written underneath the line. Amorbital gontaining one electron is represented as 1. An orbital containing two electrons isitepresented'as “l_yshowing the electrons paired and with opposite spin states. The lines are labeled with the principal quantum number andsublevel letter. For example, the orbital notations for hydrogen and ‘helium are written as follows. t nN Boy Meo Electron-Configuration Notation he Electron-configuration notation eliminates the lines and arrows of CHEMISTRY Cg? ‘orbital notation Instead, the number of electrons ina sublevel is shown = by adding a superscript to the sublevel designatior. The hydrogen con- Module 2: Models of the Atom figuration is represented by 1s. The superscript indicates that one elec~ tron is present in hydrogen’s 1s orbital. The helium configuration is, represented by 1s? Here the superscript indicates that there are two clectrons in helium’s Is orbital. BUT a TES For more help, go to the Math Tutor at the end of Chapter 5. ‘The electron configuration of boron is 1s72s72p!. How many electrons are present in an atom of boron? ‘What is the atomic number for boron? Write the orbital notation for boron. SOLUTION The number of electrons in a boron atom is equal to the sum of the superscripts in its lectron-configuration notation:2 +2+ 1 =5 electrons The number of protons equals the number of electrons in a neutral atom. So we know that boron has 5 protons and thus has an atomic number of 5. To write the orbital notation, first draw the lines representing orbitals. ee rere ap Next, add arrows showing the electron locations. The first two electrons occupy 1 level and fill the 1s orbital, ‘The next three electrons occupy the n ‘energy 2s orbital. The third occupies a higher-eneray p orbital tw t 1 is 2s PRACTICE | Answers in Appendix E 1. The electron configuration of nitrogen is 1s°2s*2p°, How many electrons are present in a nitrogen atom? What is the atomic num- ber of nitrogen? Write the orbital notation for nitrogen. 2. The electron configuration of fluorine is 1s°2s?2p. What is the atomic number of fluorine? How many ofits p orbitals are filled”? energy {60 0 [Link] for ‘more practice problems that deal with electron configurations. Keyword Hcoanex ARRANGEMENT OF ELECTRONS IN ATOMS (113The Noble Decade By the late nineteenth century. the science of chemistry had begun to be organized. In 1860, the First International Congress of Chemistry established the field's first stan dards. And Dmitri Mendeleev’s periodic table of elements gave chemists across the globe a systematic understand- ing of matter’s building blocks. But many important findings—including the discovery of a family of rare, unreactive gases that were unlike any substances known, atthe time—were yet to come Cross-Disciplinary Correspondence ‘In 1888, the British physicist Lord Rayleigh encountered a small but significant discrepancy in the results of one of his experiments. In an effort to redetermine the atomic mass of nitrogen, he measured the densities of several samples of nitrogen gas. Each sample had been prepared by a diferent method. ll samples that had been isolated from chemical reactions exhibited similar densities, But they were about one-tenth of a percent less dense than the nitrogen isolated from air, which atthe time was believed to be a mixture of nitrogen, oxygen, water vapor, and carbon dioxide. This excerpt from Lord Rayleigh’ letter was originally pub lished in Nature magazine in 1892. Saprannen 2p, 1859 WATORE LETTERS TO THE EDITOR. me aa See ree ree Y sd Oy Mis corepomdets. iter cam Mt wader eee Facet ora See eee aca ‘ering Pass, Witham, September 24 ISTORICAL CHEMISTRY Rayleigh was ata loss to explain his discover. Finally, in 1892, he published a letter in Nature magazine to appeal tchis colleagues for an explanation. A month ater, he received a reply from a Scotish chemist named Wiliam Ramsay. Ramsay related that he too had been stumped by the density difference between chemical and atmospheric nitrogen. Rayleigh decided to report his findings to the Royal Society. ‘AChemist’s Approach With Rayleigh’s permission, Ramsay attempted to remove all known components from a sample of ar and to ana Iyze what, if anything, remained, Having removed water \apor, carbon dioxide, and oxygen from the ai, Ramsay repeatedly passed the sample over hot magnesium. The nitrogen reacted with the magnesium to form solid mag nesium nitride. As a result, all of the then-known compo- nents of air were removed, What remained was a minuscule portion of a mysterious gas. Ramsay tried to cause the gas to react with chemically active substances, such as hydrogen, sodium, and caustic seda, but the gas remained unaltered. He decided to name this new atmospheric component argon (Greek for “inert” or “idle”), Periodic Problems Rayleigh and Ramsay were sure that they had discovered a new element. But this created a problem, hei calculations indicated that argon had an atomic mass of about 40. However as it appeared in 1894, the periodic table had no space for such an element. The elements with atomic masses closest to that of argon were chiorine and potassium Unfortunately, the chemical properties of the families of each ol these elements were completely cssimilarto those ofthe strange gas. Ramsay contemplated argon’s lack of reactivity. He knew that Mendeleev had created the periodic table on the basis, cl valence, or the number of atomic partners an element bonds with in forming a compound, Because Ramsay could ot cause argon to form any compounds, he assigned ita valence of zero. And because the valence ofthe elements inGrours|m|1v|v|vy{vu) vr [1] an{rv| v)vafvn) of + | Periods blb|b [he [oF |ne|na| pls|cifarx Ti] v [celal Feconi |culzn| a Gel s| sear kr| Rb sr Zr|wolMol Te] Ru Rh Pd [ag| cn | sn sb sire |aulvig| Pb] wi [Po] at) Rn] [Ra ole le Te] 1 [xe sea Riel = = iz i ( in 1893 Scotch chemist Wiliam Ramsey isolated @ previously unknown 6 i Kas! ‘Strontium St Ey] a 6 2 Ukr]5e Nitin ¥ » 2 6 f 2 Inebarse Ziconivm = Ze “ > 6 &@ 8 Ines Niobions = NB a > 6 &@ © Ines! Molybdenum Mo 2 2 6 5s - (eas! Tenet Te 6 > 6 68 - Ines! Rutbenium Ru a > 6 7 0 [nepal I 6 Pot (ears! Patadum Fa ‘6 > 68 Ww Ieper? Siver ss a > 6 wm © [ea st cadmium a « > 6 m 2 Tea 82 Indium B ® ee) i a 0 st et lho — Aaicay 8 a ef oe Thum 2 eee Iodine 1 3 ee Ikea *s25pe EUSA SEER For more help, go to the Math Tutor at the end of Chapter 5. a, Write both the complete electron-configuration notation b. How many electron-contai pletely filled? How many unpaired electrons are there in an atom of iron? \d the noble-gas notation fo mn, Fe. 1g orbitals are in an atom of iron? How many of these orbitals are com- in which sublevel are the unpaired electrons located? 120 SOLUTION a. The complete clectron-configuration notation of iron is 1s?2s?2p"373p"3d"As?, The CHAPTER 4 periodic table inside the back cover of the text reveals that 1s°2s72p°30°3p* is the electron configuration of the noble gas argon, Ar. Therefore, as shown in Table 5, iron’s noble-gas notation is [Ar]3d°4s?. 9. An iron atom has 15 orbitals that contain electrons. They consist of one 1s orbital, one 2s orbital, three 2p orbitals, one 3s orbital, three 3p orbitals, five 3d orbitals, and one 4s orbital. Eleven of these orbitals are filled, and there are four unpaired electrons. ‘They are located in the 3d sublevel. The notation 3d° represents‘Answers in Appendix E 1. a. Write both the complete electron-configuration notation and the noble-gas notation for iodine, 1. How many inner-shell elee- trons does an iodine atom contain? b. How many electron-containing orbitals are in an atom of iodine? How many of these orbitals are filled? How many unpaired electrons are there in an atom of iodine?” . a. Write the noble-gas notetion for tin, Sn. How many unpaired electrons are there in an atom of tin? b. How many electron-containing d orbitals are there in an atom of tin? Name the elemert in the fourth period whose atoms have the same number of electrons in their highest energy lev- els that tin’s atoms do, . a. Write the complete electron contiguration tor the element with atomic number 25. You may use the diagram shown in Figure 19. b. Identify the element deserbed i . a. How many orbitals are completely filled in an atom of the ele- ‘ment with atomic number 18? Write the complete electron con- figuration for this element. 'b, Identify the element deserbed in item 4a, -m 3a, oto gozrwucom for mor practic problems that deal with eecton contacter QI Kevword: ARR Elements of the Sixth and Seventh Periods ‘The sixth period consists of 32 elements. It is mach longer than the periods that precede it in the periodic table. To build up electron con- figurations for elements of this period, electrons are added first to the 65 orbital in cesium, Cs, and barium, Ba, Then, in lanthanum, La, an electron is added to the Sd orbital. With the next element, cerium, Ce, the 4f orbitals begin to fill, siving cerium atoms a configuration of [Xe}4f!5¢'6s°. In the next 13 elements, the 4f orbitals are filled, Next the Sd orbitals are filled and the period is completed by filling the 6p orbitals. Because the 4f and the Sd orbitals are very close in energy, numerous deviations from the simple rules occur as these orbitals are filled. The electron configura- tions of the sixth-period elements can be found in the periodic table inside the back cover of the text ‘The seventh period is incomplete and consists largely of synthetic ‘elements, which will be discussed in Chapter 21. ARRANGEMENT OF ELECTRONS IN ATOMS 121Bea eS For more help, go to the Math Tutor at the end of Chapter 5. 4, Write both the complete electron-configuration notation and the noble-gas notation for a rubidium atom, ». Identify the elements in the second, third, and fourth periods that have the same number of highest- ‘energy-level electrons as rubidium. SOLUTION a. 15°2s°2p%s?3p%3al4s24p%55!, [Kr]Sst b, Rubidium has one electron in its highest energy level (the fifth). The elements with the same outermost configuration are, in tae second period, lithium, Liin the third period, sodium, Na; and in the fourth period, potassium, K PRACTICE | Answers in Appendix E 1. a, Write both the complete electron-configuration notation and the noble-gas notation for a barium atom, b. Identify the elements in the second, third, fourth, and fifth peri- ods that have the same number of highest-energy-level elec- trons as barium, 2. a. Write the noble-gas notation for a gold at a, Write the noble-gas notation for a gold atom. ne ‘more practice problems that del with electron configurations. b. Identify the elements in the sixth period that have one unpaired electron in their 6s sublevel Ea 5. Identity the elements having the following 1. a. What is an atom’s electron configuration? (See SLE 'b, What three principles guide the electron a. 15725?2p%35?3p? configuration of an atom? bards! 2, What three methods are used to represent . contains four electrons in its third and outer the arrangement of electrons in atoms? rsalearay eral ag es SL Se rs a d. contains one set of paired and three unpaired elements contain an octet of electrons? electra rile otiar ret caary late 4. Write the complete electron-configuration copay notation, the noble-gas notation, and the Gitical Thinking ctbital notation for te following elements: 6. RELATING IDEAS Write the electron configuration Apo py oe for the third-period elements Al, Si, PS, and Cl 1s there a relationship between the group number of teach element and Une number of electron in the outermost energy level? 122) cHaprer 4