1 CHAPTER 8 ATOMIC ELECTRON CONFIGURATIONS AND PERIODICITY 2 Chapter 8 Outline • Magnetic Spin • Periodic Trends –Effective nuclear charge –Atomic Radii Size –Ion Radii Size –Ionization Energy and Electron Affinities ATOMIC ELECTRON CONFIGURATIONS AND PERIODICITY 3 Arrangement of Electrons in Atoms Electrons in atoms are arranged as SHELLS (n) SUBSHELLS (l) ORBITALS (ml) 4 Arrangement of Electrons in Atoms Each orbital can be assigned no more than 2 electrons! This is tied to the existence of a 4th quantum number, the electron spin quantum number, ms. 5 6 Electron Spin Quantum Number, ms Can be proven experimentally that an electron has a spin. The two spin directions are given by ms where ms = +1/2 and -1/2. Electron Spin Quantum Number Diamagnetic: substance NOT attracted to a magnetic field. Paramagnetic: substance is attracted to a magnetic field. Substance has unpaired electrons. 7 Paramagnetic -vs- Ferromagnetic Unpaired electrons in an electric field alien themselves to the applied field Unpaired electrons in their normal, random orientation. ALL metals behave this way, the exception is Cobalt, the reason why Cobalt magnets are so VERY expensive. 8 9 QUANTUM NUMBERS n ---> shell 1, 2, 3, 4, ... l ---> subshell 0, 1, 2, ... n - 1 ml ---> orbital -l ... 0 ... +l ms ---> electron spin +1/2 and -1/2 10 Pauli Exclusion Principle No two electrons in the same atom can have the same set of 4 quantum numbers. That is, each electron has a unique address = set of 4 quantum numbers. Electrons in Atoms When n = 1, then l = 0 this shell has a single orbital (1s) to which 2e- can be assigned. When n = 2, then l = 0, 1 2s orbital 2e- three 2p orbitals 6e- TOTAL = 8e- 11 Electrons in Atoms When n = 3, then l = 0, 1, 2 3s orbital 2e- three 3p orbitals 6e- five 3d orbitals 10e- TOTAL = 18e- 12 Electrons in Atoms When n = 4, then l = 0, 1, 2, 3 4s orbital 2ethree 4p orbitals 6efive 4d orbitals 10eseven 4f orbitals 14eTOTAL = 32e- And many more! 13 14 Assigning Electrons to Atoms • Electrons generally assigned to orbitals of successively higher energy. • For H atoms, E = - C(1/n2). E depends only on n. • For multi - electron atoms, energy depends on both n and l. 15 Figure 8.4 16 Assigning Electrons to Subshells • In the H atom all subshells of same n have same energy. • In many-electron atom: a) subshells increase in energy as value of n + l increases. b) for subshells of same n + l, subshell with lower n is lower in energy. 17 Electron Filling Order Figure 8.5 18 Writing Atomic Electron Configurations Two ways of writing complete configurations. One is called the spectroscopic notation. SPECTROSCOPIC NOTATION for H, atomic number = 1 1 1s value of n no. of electrons value of l Writing Atomic Electron Configurations Two ways of writing complete configurations. Other is called the orbital box notation. 19 ORBITAL BOX NOTATION for He, atomic number = 2 Arrows depict 2 electron spin 1s 1s One electron has n = 1, l = 0, ml = 0, ms = + 1/2 Other electron has n = 1, l = 0, ml = 0, ms = - 1/2 20 21 Figure 8.7 22 Lithium Group 1A Atomic number = 3 1s22s1 ---> 3 total electrons 3p 3s 2p 2s 1s 23 Beryllium 3p 3s 2p 2s 1s Group 2A Atomic number = 4 1s22s2 ---> 4 total electrons 24 Boron 3p 3s 2p 2s 1s Group 3A Atomic number = 5 1s2 2s2 2p1 ---> 5 total electrons 25 Carbon Group 4A Atomic number = 6 1s2 2s2 2p2 ---> 6 total electrons 3p 3s 2p 2s 1s Here we see HUND’S RULE. When placing electrons in a set of orbitals having the same energy, we place them singly as long as possible. 26 Nitrogen 3p 3s 2p 2s 1s Group 5A Atomic number = 7 1s2 2s2 2p3 ---> 7 total electrons 27 Oxygen Group 6A Atomic number = 8 1s2 2s2 2p4 ---> 8 total electrons 3p 3s 2p 2s 1s 28 Fluorine Group 7A Atomic number = 9 1s2 2s2 2p5 ---> 9 total electrons 3p 3s 2p 2s 1s 29 Neon Group 8A Atomic number = 10 1s2 2s2 2p6 ---> 10 total electrons 3p 3s 2p 2s 1s Note that we have reached the end of the 2nd period, and the 2nd shell is full! 30 Electron Configurations Noble gas configuration: filled s and p levels. Electron configs. are shortened by using the noble gas configuration to represent the core electrons. The remaining electrons are valence electrons. Notations: Spectroscopic Orbital Box Examples: Boron 1s22s22p1 1s 2s 2p Noble Gas Valence [He] 2s22p1 2s22p1 31 Quantum Numbers 32 If we use positive values of ml and ms first, the set of four quantum numbers can be determined for the “last electron in” for a given element. This is called the “last-electron-in” game!!! 33 Electron Configurations of p-Block Elements 34 Sodium Group 1A Atomic number = 11 1s2 2s2 2p6 3s1 or “neon core” + 3s1 [Ne] 3s1 (uses rare gas notation) Note that we have begun a new period. All Group 1A elements have [core]ns1 configurations. 35 Aluminum Group 3A Atomic number = 13 1s2 2s2 2p6 3s2 3p1 [Ne] 3s2 3p1 All Group 3A elements have [core] ns2 np1 configurations where n is the period number. 3p 3s 2p 2s 1s 36 Phosphorus Group 5A Atomic number = 15 1s2 2s2 2p6 3s2 3p3 [Ne] 3s2 3p3 All Group 5A elements have 3p 3s [core ] ns2 np3 configurations where n is the period number. 2p 2s 1s 37 Calcium Group 2A Atomic number = 20 1s2 2s2 2p6 3s2 3p6 4s2 [Ar] 4s2 All Group 2A elements have [core]ns2 configurations where n is the period number. Relationship of Electron Configuration and Region of the Periodic Table • • • • Gray = s block Orange = p block Green = d block Violet = f block 38 Transition Metals Table 8.4 All 4th period elements have the configuration [argon] nsx (n - 1)dy and so are “d-block” elements. Chromium Iron Copper 39 Transition Element Configurations 3d orbitals used for Sc - Zn (Table 8.4) 40 41 Figure 8.9 42 43 Lanthanides and Actinides All these elements have the configuration [core] nsx (n - 1)dy (n - 2)fz and so are “f-block” elements. Cerium [Xe] 6s2 5d1 4f1 Uranium [Rn] 7s2 6d1 5f3 44 Lanthanide Element Configurations 4f orbitals used for Ce - Lu and 5f for Th - Lr (Table 8.2) Ion Configurations To form cations from elements remove 1 or more e- from subshell of highest n [or highest (n + l)]. P [Ne] 3s2 3p3 ---> P3+ [Ne] 3s2 3p0 + 3e- 1s 2s P 2p 3s P3+ 3p 45 46 Ion Configurations For transition metals, remove ns electrons and then (n - 1) electrons. Fe [Ar] 4s2 3d6 ---> Fe2+ [Ar] 4s0 3d6 + 2e1s 2s Fe2+ 2p Fe 3s 3p 4s 3d 47 Ion Configurations How do we know the configurations of ions? Determine the magnetic properties of ions. Ions with UNPAIRED ELECTRONS are PARAMAGNETIC. Without unpaired electrons DIAMAGNETIC. 48 Sample Question Give the electron configuration for Ni+4. Include the valence box diagram and state if the ion is paramagnetic or diamagnetic. 1s 2s Ni4+ 2p Ni 3s 3p 4s 3d 49 PERIODIC TRENDS Movies on these later!! General Periodic Trends 1. Atomic and ionic size 2. Ionization energy 3. Electron affinity Higher Z*. Electrons held more tightly. Larger orbitals. Electrons held less tightly. 50 51 Atomic Size • Size goes UP when going down a group. See Figure 8.9. • Because electrons are added further from the nucleus, there is less attraction. • Size goes DOWN when going across a period. SIZE Effective Nuclear Charge: relating to Atom radii The reason for the difference in energy for 2s and 2p subshells, for example, is the effective nuclear charge, Z*. 52 53 Screening or Shielding effect: helps explain periodic trends in a period Figure 8.6 54 Effective Nuclear Charge, Z* • Z* is the nuclear charge experienced by the outermost electrons. • Explains why E(2s) < E(2p) • Z* increases across a period owing to incomplete shielding by inner electrons. • Estimate Z* by --> [ Z - ( # inner electrons) ] • Charge felt by 2s e- in Li Z* = 3 - 2 = 1 • Be Z* = 4 - 2 = 2 • B Z* = 5 - 2 = 3 and so on! The nuclear charge increases 55 56 Atomic Size Size decreases across a period owing to increase in Z*. Each added electron feels a greater and greater + charge. 57 Trends in Atomic Size Radius (pm) 250 K 1st transition series 3rd period 200 Na 2nd period Li 150 Kr 100 Ar Ne 50 He 0 0 5 10 15 20 25 Atomic Number 30 35 40 58 Sizes of Transition Elements • 3d subshell is inside the 4s subshell. • 4s electrons feel a more or less constant Z*. • Sizes stay about the same and chemistries are similar! 59 60 Ion Sizes Li,152 pm 3e and 3p Does the size go up or+down when losing an Li + , 60 pm electron 2e and 3 p to form a cation? Ion Sizes • CATIONS are SMALLER than the atoms from which they come. • The electron/proton attraction has gone UP and so size DECREASES. 61 Ion Sizes F,64 pm 9e and 9p Does the size go up or down when gaining an electron to form an F- , 136 pm anion? 10 e and 9 p 62 63 Ion Sizes • ANIONS are LARGER than the atoms from which they come. • The electron/proton attraction has gone DOWN and so size INCREASES. 64 Figure 8.13 Ion Sizes For an isoelectronic series • Size decreases as the atomic number increases • Example: N-3 to Al+3 65 66 Redox Reactions Why do metals lose electrons in their reactions? Why does Mg form Mg2+ ions and not Mg3+? Why do nonmetals take on electrons? Ionization Energy See Figure 8.12 IE = energy required to remove an electron from an atom in the gas phase. Mg (g) + 738 kJ ---> Mg+ (g) + e- A(g) ---> A+(g) + e- I.E. = +E 67 Ionization Energy IE = energy required to remove an electron from an atom in the gas phase. Mg (g) + 738 kJ ---> Mg+ (g) + eMg+ (g) + 1451 kJ ---> Mg2+ (g) + e- Mg+ has 12 protons and only 11 electrons. Therefore, IE for Mg+ > Mg. 68 69 Ionization Energy Mg (g) + 735 kJ ---> Mg+ (g) + e- Mg+ (g) + 1451 kJ ---> Mg2+ (g) + eMg2+ (g) + 7733 kJ ---> Mg3+ (g) + e- Energy cost is very high to dip into a shell of lower n. This is why ox. no. = Group no. 70 71 Trends in Ionization Energy • IE increases across a period because Z* increases. • Metals lose electrons more easily than nonmetals. • Metals are good reducing agents. • Nonmetals lose electrons with difficulty. 72 Trends in Ionization Energy • IE decreases down a group • Because size increases. • Reducing ability generally increases down the periodic table. • See reactions of Li, Na, K Figure 8.11 73 74 Lithium Periodic Trend in the Reactivity of Alkali Metals with Water Sodium Potassium Here are those movies promised! Electron Affinity 75 A few elements GAIN electrons to form anions. Electron affinity is the energy involved when an atom Gains an electron. A(g) + e- ---> A- (g) Note: Both EA’s and IE’s are “-”. E.A. = -E Cl E.A. = -349 kJ/Mol 76 Electron Affinity of Oxygen E is Exothermic because O has an affinity for an e-. EA = - 141 kJ O- ion [He] + electron O atom [He] 77 Electron Affinity of Nitrogen EA = 0 kJ E is zero for N due to electronelectron repulsions. N- ion [He] + electron N atom [He] Trends in Electron Affinity • See Figure 8.12 • Affinity for electron increases across a period (EA becomes more negative). • Affinity decreases down a group (EA becomes less negative). 78 Figure 8.12 79 Trends in Electron Affinity • See Appendix F Atom EA • Affinity for electron F -328 kJ increases across a period Cl -349 kJ (EA becomes more Br -325 kJ negative). -295 kJ • Affinity decreases down a I group (EA becomes less negative). These numbers are for the ion forming the atom. 80 81 Practice Problems 1. Write the electron configurations: a. Orbital box notation for C b. Spectroscopic notation for Mg c. Noble Gas notation for Sc d. Noble Gas notation for P e. Valence notation for Pb 82 Practice Problems 2. Answer the following about the elements in question 1: a. number of unpaired electron's b. arrange according to size (small to large) c. arrange according to ionization energy (small to large) d. predict ions that each elements will form e. determine the set of 4 quantum numbers for the last electron. 83 Practice Problems 3. Give the symbol of the element with the lowest atomic number that has a. a half filled p sublevel b. 3 filled 4d orbitals c. unpaired electrons in 2 or more sublevels 84 Practice Problems Answers 1. a. 1s 2s 2p b. 1s22s22p63s2 c. [Ar] 4s23d1 d. [Ne] 3s23p3 e. 6s26p2 or 6s24f145d106p2 2. a. 2, 0, 1, 3, 2 b. C, P, Mg, Sc, Pb c. Pb, Sc, Mg, P, C d. -4, +2, +2 and +3, -3, +2 and +4 85 Practice Problems Answers 2. e. C 2, 1, 0, +1/2 Mg 3, 0, 0, -1/2 Sc 3, 2, 2, +1/2 P 3,1,-1,+1/2 Pb 6, 1, 0, +1/2 3. N, Pd, Cr 86 Electrons and Quantum Numbers n l ml 1 1 0 0 0 0 ms +1/2 -1/2 1s 87 Electrons and Quantum Numbers n l ml ms 2 2 0 0 0 0 +1/2 -1/2 2s 2 2 2 2 2 2 1 1 1 1 1 1 1 0 -1 1 0 -1 +1/2 +1/2 +1/2 -1/2 -1/2 -1/2 2p 88 Hydrogen “Group 1A” Atomic number = 1 1 electron 1s 1s1 89 Helium “Group 8A” Atomic number = 2 2 electrons 1s 1s2 90 Lithium Group 1A Atomic number = 3 3 electrons 1s 2s 1s22s1 91 Beryllium Group 2A Atomic number = 4 4 electrons 1s 2s 1s22s2 92 Boron Group 3A Atomic number = 5 5 electrons 1s 2s 1s22s22p1 2p 93 Carbon Group 4A Atomic number = 6 6 electrons 1s 2s 1s22s22p2 2p 94 Nitrogen Group 5A Atomic number = 7 7 electrons 1s 2s 1s22s22p3 2p 95 Oxygen Group 6A Atomic number = 8 8 electrons 1s 2s 1s22s22p4 2p 96 Fluorine Group 7A Atomic number = 9 9 electrons 1s 2s 1s22s22p5 2p 97 Neon Group 8A Atomic number = 10 10 electrons 1s 2s 1s22s22p6 2p Sample Question Give the spectroscopic notation for P. 1s22s22p63s23p3 Determine the set of 4 quantum numbers for the “last electron in”. (3, 1, -1, 1/2) Give a box diagram for the valence electrons. 3s 3p 98 99 Sodium Group 1A Atomic number = 11 11 electrons 1s 2s 1s22s22p63s1 2p 3s 100 Magnesium Group 2A Atomic number = 12 12 electrons 1s 2s 1s22s22p63s2 2p 3s 101 Aluminum Group 3A Atomic number = 13 13 electrons 1s 2s 2p 1s22s22p63s23p1 3s 3p 102 Silicon Group 4A Atomic number = 14 14 electrons 1s 2s 2p 1s22s22p63s23p2 3s 3p 103 Phosphorus Group 5A Atomic number = 15 15 electrons 1s 2s 2p 1s22s22p63s23p3 3s 3p 104 Sulfur Group 4A Atomic number = 16 16 electrons 1s 2s 2p 1s22s22p63s23p4 3s 3p 105 Chlorine Group 7A Atomic number = 17 17 electrons 1s 2s 2p 1s22s22p63s23p5 3s 3p 106 Argon Group 8A Atomic number = 18 18 electrons 1s 2s 2p 1s22s22p63s23p6 3s 3p 107 Potassium Group 1A Atomic number = 19 19 electrons 1s 2s 2p 1s22s22p63s23p64s1 3s 3p 4s 108 Calcium Group 2A Atomic number = 20 20 electrons 1s 2s 2p 1s22s22p63s23p64s2 3s 3p 4s 109 Scandium B Group Atomic number = 21 21 electrons 1s 2s 2p 3s 3p 4s 3d 1s22s22p63s23p64s23d1 Sample Questions 1. Write the noble gas configuration for [Ar] 4s23d104p2 a) Ge b) Cs [Xe] 6s1 c) Pb [Xe] 6s24f145d106p2 110 Sample Questions 2. What element has (4, 2, 1, -1/2) as its last electron in? Use a valence box diagram and give the valence configuration for this element. 4d 4d7 2 1 0 -1 -2 5s2 or 5s24d7 Rh 111 Sample Questions 3. Give the symbol of the element with the lowest atomic number that a. is a noble gas with no p electrons. b. is in period 3 and has 2 unpaired electrons. c. is in period 2 and has 2 filled p orbitals. d. has 4 electrons in level 2. He Si F C 112