1. Copyright  2011 Pearson Education, Inc. Chapter 8 Periodic Properties of the Elements Roy Kennedy Massachusetts Bay Community College Wellesley Hills, MA Chemistry: A Molecular Approach, 2nd Ed. Nivaldo Tro

2. Copyright  2011 Pearson Education, Inc. Nerve Transmission Movement of ions across cell membranes is the basis for the transmission of nerve signals Na + and K + ions are pumped across membranes in opposite directions through ion channels Na + out and K + in The ion channels can differentiate Na + from K + by their difference in size Ion size and other properties of atoms are periodic properties – properties whose values can be predicted based on the element’s position on the Periodic Table 2 Tro: Chemistry: A Molecular Approach, 2/e

3. Copyright  2011 Pearson Education, Inc. Mendeleev (1834–1907) Order elements by atomic mass Saw a repeating pattern of properties Periodic Law – when the elements are arranged in order of increasing atomic mass, certain sets of properties recur periodically Put elements with similar properties in the same column Used pattern to predict properties of undiscovered elements Where atomic mass order did not fit other properties, he re-ordered by other properties Te & I 3 Tro: Chemistry: A Molecular Approach, 2/e

4. Copyright  2011 Pearson Education, Inc. Periodic Pattern a = acidic oxide, b = basic oxide, a/b = amphoteric oxide M = metal, NM = nonmetal, M/NM = metalloid LiBeBCNOF NaMgAlSiPSCl KCa H NMH 2 O a/b H2H2 1.0 MLi 2 O b LiH6.9 MNa 2 O b NaH23.0 MK2ObK2Ob KH39.1 MBeO a/b BeH 2 9.0 MMgO b MgH 2 24.3 MCaO b CaH 2 40.1 NMB2O3aB2O3a BH 3 10.8 M Al 2 O 3 a/b AlH 3 27.0 NMCO 2 a CH 4 12.0 M/NM SiO 2 a SiH 4 28.1 NMN2O5aN2O5a NH 3 14.0 NMP 4 O 10 a PH 3 31.0 NM H2SH2S 32.1 SO 3 a NM H2OH2O16.0 O2O2 NMCl 2 O 7 a HCl 35.5 NM HF19.0 4 Tro: Chemistry: A Molecular Approach, 2/e

5. Copyright  2011 Pearson Education, Inc. Mendeleev's Predictions 5 Tro: Chemistry: A Molecular Approach, 2/e

6. Copyright  2011 Pearson Education, Inc. What vs. Why Mendeleev’s Periodic Law allows us to predict what the properties of an element will be based on its position on the table It doesn’t explain why the pattern exists Quantum Mechanics is a theory that explains why the periodic trends in the properties exist and knowing Why allows us to predict What 6 Tro: Chemistry: A Molecular Approach, 2/e

7. Copyright  2011 Pearson Education, Inc. Electron Configurations Quantum-mechanical theory describes the behavior of electrons in atoms The electrons in atoms exist in orbitals A description of the orbitals occupied by electrons is called an electron configuration 7 1s11s1 principal energy level of orbital occupied by the electron sublevel of orbital occupied by the electron number of electrons in the orbital Tro: Chemistry: A Molecular Approach, 2/e

8. Copyright  2011 Pearson Education, Inc. How Electrons Occupy Orbitals Calculations with Schrödinger’s equation show hydrogen’s one electron occupies the lowest energy orbital in the atom Schrödinger’s equation calculations for multielectron atoms cannot be exactly solved due to additional terms added for electron-electron interactions Approximate solutions show the orbitals to be hydrogen-like Two additional concepts affect multielectron atoms: electron spin and energy splitting of sublevels 8 Tro: Chemistry: A Molecular Approach, 2/e

9. Copyright  2011 Pearson Education, Inc. Electron Spin Experiments by Stern and Gerlach showed a beam of silver atoms is split in two by a magnetic field The experiment reveals that the electrons spin on their axis As they spin, they generate a magnetic field spinning charged particles generate a magnetic field If there is an even number of electrons, about half the atoms will have a net magnetic field pointing “north” and the other half will have a net magnetic field pointing “south” 9 Tro: Chemistry: A Molecular Approach, 2/e

10. Copyright  2011 Pearson Education, Inc. Electron Spin Experiment 10 Tro: Chemistry: A Molecular Approach, 2/e

11. Copyright  2011 Pearson Education, Inc. The Property of Electron Spin Spin is a fundamental property of all electrons All electrons have the same amount of spin The orientation of the electron spin is quantized, it can only be in one direction or its opposite spin up or spin down The electron’s spin adds a fourth quantum number to the description of electrons in an atom, called the Spin Quantum Number, m s not in the Schrödinger equation 11 Tro: Chemistry: A Molecular Approach, 2/e

12. Copyright  2011 Pearson Education, Inc. Spin Quantum Number, m s, and Orbital Diagrams m s can have values of +½ or −½ Orbital Diagrams use a square to represent each orbital and a half- arrow to represent each electron in the orbital By convention, a half-arrow pointing up is used to represent an electron in an orbital with spin up Spins must cancel in an orbital paired 12 Tro: Chemistry: A Molecular Approach, 2/e

13. Copyright  2011 Pearson Education, Inc. Orbital Diagrams We often represent an orbital as a square and the electrons in that orbital as arrows the direction of the arrow represents the spin of the electron orbital with one electron unoccupied orbital orbital with two electrons 13 Tro: Chemistry: A Molecular Approach, 2/e

14. Copyright  2011 Pearson Education, Inc. Pauli Exclusion Principle 14 Tro: Chemistry: A Molecular Approach, 2/e No two electrons in an atom may have the same set of four quantum numbers Therefore no orbital may have more than two electrons, and they must have with opposite spins Knowing the number orbitals in a sublevel allows us to determine the maximum number of electrons in the sublevel s sublevel has 1 orbital, therefore it can hold 2 electrons p sublevel has 3 orbitals, therefore it can hold 6 electrons d sublevel has 5 orbitals, therefore it can hold 10 electrons f sublevel has 7 orbitals, therefore it can hold 14 electrons

15. Copyright  2011 Pearson Education, Inc. Allowed Quantum Numbers 15 Tro: Chemistry: A Molecular Approach, 2/e

16. Copyright  2011 Pearson Education, Inc. Quantum Numbers of Helium’s Electrons Helium has two electrons Both electrons are in the first energy level Both electrons are in the s orbital of the first energy level Because they are in the same orbital, they must have opposite spins 16Tro: Chemistry: A Molecular Approach, 2/e

17. Copyright  2011 Pearson Education, Inc. Sublevel Splitting in Multielectron Atoms The sublevels in each principal energy shell of Hydrogen all have the same energy or other single electron systems We call orbitals with the same energy degenerate For multielectron atoms, the energies of the sublevels are split caused by charge interaction, shielding and penetration The lower the value of the l quantum number, the less energy the sublevel has s (l = 0) < p (l = 1) < d (l = 2) < f (l = 3) 17 Tro: Chemistry: A Molecular Approach, 2/e

18. Copyright  2011 Pearson Education, Inc. Coulomb’s Law Coulomb’s Law describes the attractions and repulsions between charged particles For like charges, the potential energy (E) is positive and decreases as the particles get farther apart as r increases For opposite charges, the potential energy is negative and becomes more negative as the particles get closer together The strength of the interaction increases as the size of the charges increases electrons are more strongly attracted to a nucleus with a 2+ charge than a nucleus with a 1+ charge 18 Tro: Chemistry: A Molecular Approach, 2/e

19. Copyright  2011 Pearson Education, Inc. Shielding & Effective Nuclear Charge Each electron in a multielectron atom experiences both the attraction to the nucleus and repulsion by other electrons in the atom These repulsions cause the electron to have a net reduced attraction to the nucleus – it is shielded from the nucleus The total amount of attraction that an electron feels for the nucleus is called the effective nuclear charge of the electron 19 Tro: Chemistry: A Molecular Approach, 2/e

20. Copyright  2011 Pearson Education, Inc. Penetration The closer an electron is to the nucleus, the more attraction it experiences The better an outer electron is at penetrating through the electron cloud of inner electrons, the more attraction it will have for the nucleus The degree of penetration is related to the orbital’s radial distribution function in particular, the distance the maxima of the function are from the nucleus 20 Tro: Chemistry: A Molecular Approach, 2/e

21. Copyright  2011 Pearson Education, Inc. Shielding & Penetration 21 Tro: Chemistry: A Molecular Approach, 2/e

22. Copyright  2011 Pearson Education, Inc. Penetration and Shielding The radial distribution function shows that the 2s orbital penetrates more deeply into the 1s orbital than does the 2p The weaker penetration of the 2p sublevel means that electrons in the 2p sublevel experience more repulsive force, they are more shielded from the attractive force of the nucleus The deeper penetration of the 2s electrons means electrons in the 2s sublevel experience a greater attractive force to the nucleus and are not shielded as effectively 22 Tro: Chemistry: A Molecular Approach, 2/e

23. Copyright  2011 Pearson Education, Inc. Effect of Penetration and Shielding Penetration causes the energies of sublevels in the same principal level to not be degenerate In the fourth and fifth principal levels, the effects of penetration become so important that the s orbital lies lower in energy than the d orbitals of the previous principal level The energy separations between one set of orbitals and the next become smaller beyond the 4s the ordering can therefore vary among elements causing variations in the electron configurations of the transition metals and their ions 23 Tro: Chemistry: A Molecular Approach, 2/e

24. Copyright  2011 Pearson Education, Inc. Energy 1s 7s 2s 2p 3s 3p 3d 6s 6p 6d 4s 4p 4d 4f 5s 5p 5d 5f Notice the following: 1.because of penetration, sublevels within an energy level are not degenerate 2.penetration of the 4 th and higher energy levels is so strong that their s sublevel is lower in energy than the d sublevel of the previous energy level 3.the energy difference between levels becomes smaller for higher energy levels (and can cause anomalous electron configurations for certain elements) 24 Tro: Chemistry: A Molecular Approach, 2/e

25. Copyright  2011 Pearson Education, Inc. Filling the Orbitals with Electrons 25 Tro: Chemistry: A Molecular Approach, 2/e Energy levels and sublevels fill from lowest energy to high s → p → d → f Aufbau Principle Orbitals that are in the same sublevel have the same energy No more than two electrons per orbital Pauli Exclusion Principle When filling orbitals that have the same energy, place one electron in each before completing pairs Hund’s Rule

26. Copyright  2011 Pearson Education, Inc. Electron Configuration of Atoms in their Ground State The electron configuration is a listing of the sublevels in order of filling with the number of electrons in that sublevel written as a superscript. Kr = 36 electrons = 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 10 4p 6 A short-hand way of writing an electron configuration is to use the symbol of the previous noble gas in [] to represent all the inner electrons, then just write the last set. Rb = 37 electrons = 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 10 4p 6 5s 1 = [Kr]5s 1 26 Tro: Chemistry: A Molecular Approach, 2/e

27. Copyright  2011 Pearson Education, Inc. Order of Sublevel Filling in Ground State Electron Configurations 1s1s 2s2s2p2p 3s3s3p3p3d3d 4s4s4p4p4d4d4f4f 5s5s5p5p5d5d5f5f 6s6s6p6p6d6d 7s7s Start by drawing a diagram putting each energy shell on a row and listing the sublevels, (s, p, d, f), for that shell in order of energy (left-to-right) Next, draw arrows through the diagonals, looping back to the next diagonal each time 27 Tro: Chemistry: A Molecular Approach, 2/e

28. Copyright  2011 Pearson Education, Inc. Electron Configurations 28 Tro: Chemistry: A Molecular Approach, 2/e

29. Copyright  2011 Pearson Education, Inc. Example: Write the full ground state orbital diagram and electron configuration of manganese Mn Z = 25, therefore 25 e − Based on the order of sublevel filling, we will need the first seven sublevels 1s1s 2s2p2p 3s3s3p3p3d3d 4s4s4p4p4d4d4f4f s sublevel holds 2 e − p sublevel holds 6 e − d sublevel holds 10 e − f sublevel holds 14 e − 2 e − +2 = 4e − +6 +2 = 12e − +6 +2 = 20e −  1s1s2s2s2p2p3s3s3p3p4s4s    Therefore the electron configuration is 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 5 +10 = 30e − 3 d  29 Tro: Chemistry: A Molecular Approach, 2/e

30. Copyright  2011 Pearson Education, Inc. Practice — write the full ground state orbital diagram and electron configuration of potassium. 30 Tro: Chemistry: A Molecular Approach, 2/e

31. Copyright  2011 Pearson Education, Inc. Practice — write the full ground state orbital diagram and electron configuration of potassium, answer K Z = 19, therefore 19 e − Based on the order of sublevel filling, we will need the first six sublevels 1s1s 2s2p2p 3s3s3p3p3d3d 4s4s4p4p4d4d4f4f s sublevel holds 2 e − p sublevel holds 6 e − d sublevel holds 10 e − f sublevel holds 14 e − 2 e − +2 = 4e − +6 +2 = 12e − +6 +2 = 20e −  1s1s2s2s2p2p3s3s3p3p4s4s   Therefore the electron configuration is 1s 2 2s 2 2p 6 3s 2 3p 6 4s 1 31 Tro: Chemistry: A Molecular Approach, 2/e

32. Copyright  2011 Pearson Education, Inc. Valence Electrons 32 Tro: Chemistry: A Molecular Approach, 2/e The electrons in all the sublevels with the highest principal energy shell are called the valence electrons Electrons in lower energy shells are called core electrons Chemists have observed that one of the most important factors in the way an atom behaves, both chemically and physically, is the number of valence electrons

33. Copyright  2011 Pearson Education, Inc. Electron Configuration of Atoms in their Ground State Kr = 36 electrons 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 10 4p 6 there are 28 core electrons and 8 valence electrons Rb = 37 electrons 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 10 4p 6 5s 1 [Kr]5s 1 For the 5s 1 electron in Rb the set of quantum numbers is n = 5, l = 0, m l = 0, m s = +½ For an electron in the 2p sublevel, the set of quantum numbers is n = 2, l = 1, m l = −1 or (0,+1), and m s = −½ or (+½) 33 Tro: Chemistry: A Molecular Approach, 2/e

34. Copyright  2011 Pearson Education, Inc. Electron Configuration & the Periodic Table The Group number corresponds to the number of valence electrons The length of each “block” is the maximum number of electrons the sublevel can hold The Period number corresponds to the principal energy level of the valence electrons 34 Tro: Chemistry: A Molecular Approach, 2/e

35. Copyright  2011 Pearson Education, Inc. 35 Tro: Chemistry: A Molecular Approach, 2/e

36. Copyright  2011 Pearson Education, Inc. s1s1 s2s2 d 1 d 2 d 3 d 4 d 5 d 6 d 7 d 8 d 9 d 10 s2s2 p 1 p 2 p 3 p 4 p 5 p6p6 f 2 f 3 f 4 f 5 f 6 f 7 f 8 f 9 f 10 f 11 f 12 f 13 f 14 f 14 d 1 12345671234567 36 Tro: Chemistry: A Molecular Approach, 2/e

37. Copyright  2011 Pearson Education, Inc. Electron Configuration from the Periodic Table P = [Ne]3s 2 3p 3 P has five valence electrons 3p33p3 P Ne 12345671234567 1A 2A 3A4A5A6A7A 8A 3s23s2 37 Tro: Chemistry: A Molecular Approach, 2/e

38. Copyright  2011 Pearson Education, Inc. Transition Elements For the d block metals, the principal energy level is one less than valence shell one less than the Period number sometimes s electron “promoted” to d sublevel 4s4s3d3d Zn Z = 30, Period 4, Group 2B [Ar]4s 2 3d 10 For the f block metals, the principal energy level is two less than valence shell two less than the Period number they really belong to sometimes d electron in configuration Eu Z = 63, Period 6 [Xe]6s 2 4f 7 6s6s4f4f 38 Tro: Chemistry: A Molecular Approach, 2/e

39. Copyright  2011 Pearson Education, Inc. Electron Configuration from the Periodic Table As = [Ar]4s 2 3d 10 4p 3 As has five valence electrons 4s24s2 Ar 3d 10 4p34p3 As 12345671234567 1A 2A 3A4A5A6A7A 8A 39 Tro: Chemistry: A Molecular Approach, 2/e

40. Copyright  2011 Pearson Education, Inc. Practice – Use the Periodic Table to write the short electron configuration and short orbital diagram for each of the following Na (at. no. 11) Te (at. no. 52) Tc (at. no. 43) 3s3s [Ne]3s 1 5s5s5p5p 4d4d [Kr]5s 2 4d 10 5p 4 5s5s4d4d [Kr]5s 2 4d 5 40 Tro: Chemistry: A Molecular Approach, 2/e

41. Copyright  2011 Pearson Education, Inc. Irregular Electron Configurations We know that because of sublevel splitting, the 4s sublevel is lower in energy than the 3d; and therefore the 4s fills before the 3d But the difference in energy is not large Some of the transition metals have irregular electron configurations in which the ns only partially fills before the (n−1)d or doesn’t fill at all Therefore, their electron configuration must be found experimentally 41 Tro: Chemistry: A Molecular Approach, 2/e

42. Copyright  2011 Pearson Education, Inc. Irregular Electron Configurations Expected Cr = [Ar]4s 2 3d 4 Cu = [Ar]4s 2 3d 9 Mo = [Kr]5s 2 4d 4 Ru = [Kr]5s 2 4d 6 Pd = [Kr]5s 2 4d 8 Found Experimentally Cr = [Ar]4s 1 3d 5 Cu = [Ar]4s 1 3d 10 Mo = [Kr]5s 1 4d 5 Ru = [Kr]5s 1 4d 7 Pd = [Kr]5s 0 4d 10 42 Tro: Chemistry: A Molecular Approach, 2/e

43. Copyright  2011 Pearson Education, Inc. The properties of the elements follow a periodic pattern elements in the same column have similar properties the elements in a period show a pattern that repeats The quantum-mechanical model explains this because the number of valence electrons and the types of orbitals they occupy are also periodic 43 Properties & Electron Configuration Tro: Chemistry: A Molecular Approach, 2/e

44. Copyright  2011 Pearson Education, Inc. The Noble Gas Electron Configuration The noble gases have eight valence electrons. except for He, which has only two electrons We know the noble gases are especially non-reactive He and Ne are practically inert The reason the noble gases are so non-reactive is that the electron configuration of the noble gases is especially stable 44 Tro: Chemistry: A Molecular Approach, 2/e

45. Copyright  2011 Pearson Education, Inc. Everyone Wants to Be Like a Noble Gas! The Alkali Metals The alkali metals have one more electron than the previous noble gas In their reactions, the alkali metals tend to lose one electron, resulting in the same electron configuration as a noble gas forming a cation with a 1+ charge 45 Tro: Chemistry: A Molecular Approach, 2/e

46. Copyright  2011 Pearson Education, Inc. Everyone Wants to Be Like a Noble Gas! The Halogens The electron configurations of the halogens all have one fewer electron than the next noble gas In their reactions with metals, the halogens tend to gain an electron and attain the electron configuration of the next noble gas Forming an anion with charge 1− In their reactions with nonmetals, they tend to share electrons with the other nonmetal so that each attains the electron configuration of a noble gas 46 Tro: Chemistry: A Molecular Approach, 2/e

47. Copyright  2011 Pearson Education, Inc. Eight Valence Electrons Quantum mechanical calculations show that eight valence electrons should result in a very unreactive atom an atom that is very stable the noble gases have eight valence electrons and are all very stable and unreactive  He has two valence electrons, but that fills its valence shell Conversely, elements that have either one more or one less electron should be very reactive the halogen atoms have seven valence electrons and are the most reactive nonmetals the alkali metals have one more electron than a noble gas atom and are the most reactive metals  as a group 47 Tro: Chemistry: A Molecular Approach, 2/e

48. Copyright  2011 Pearson Education, Inc. Electron Configuration & Ion Charge We have seen that many metals and nonmetals form one ion, and that the charge on that ion is predictable based on its position on the Periodic Table Group 1A = 1+, Group 2A = 2+, Group 7A = 1−, Group 6A = 2−, etc. These atoms form ions that will result in an electron configuration that is the same as the nearest noble gas 48 Tro: Chemistry: A Molecular Approach, 2/e

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50. Copyright  2011 Pearson Education, Inc. Electron Configuration of Anions in Their Ground State Anions are formed when nonmetal atoms gain enough electrons to have eight valence electrons filling the s and p sublevels of the valence shell The sulfur atom has six valence electrons S atom = 1s 2 2s 2 2p 6 3s 2 3p 4 To have eight valence electrons, sulfur must gain two more S 2− anion = 1s 2 2s 2 2p 6 3s 2 3p 6 50 Tro: Chemistry: A Molecular Approach, 2/e

51. Copyright  2011 Pearson Education, Inc. Electron Configuration of Cations in Their Ground State Cations are formed when a metal atom loses all its valence electrons resulting in a new lower energy level valence shell however the process is always endothermic The magnesium atom has two valence electrons Mg atom = 1s 2 2s 2 2p 6 3s 2 When magnesium forms a cation, it loses its valence electrons Mg 2+ cation = 1s 2 2s 2 2p 6 51 Tro: Chemistry: A Molecular Approach, 2/e

52. Copyright  2011 Pearson Education, Inc. Trend in Atomic Radius – Main Group 52 Tro: Chemistry: A Molecular Approach, 2/e There are several methods for measuring the radius of an atom, and they give slightly different numbers van der Waals radius = nonbonding covalent radius = bonding radius atomic radius is an average radius of an atom based on measuring large numbers of elements and compounds Atomic Radius Increases down group valence shell farther from nucleus effective nuclear charge fairly close Atomic Radius Decreases across period (left to right) adding electrons to same valence shell effective nuclear charge increases valence shell held closer

53. Copyright  2011 Pearson Education, Inc. 53 Tro: Chemistry: A Molecular Approach, 2/e

54. Copyright  2011 Pearson Education, Inc. Shielding 54 Tro: Chemistry: A Molecular Approach, 2/e In a multi-electron system, electrons are simultaneously attracted to the nucleus and repelled by each other Outer electrons are shielded from nucleus by the core electrons screening or shielding effect outer electrons do not effectively screen for each other The shielding causes the outer electrons to not experience the full strength of the nuclear charge

55. Copyright  2011 Pearson Education, Inc. Effective Nuclear Charge The effective nuclear charge is net positive charge that is attracting a particular electron Z is the nuclear charge, S is the number of electrons in lower energy levels electrons in same energy level contribute to screening, but very little so are not part of the calculation trend is s > p > d > f Z effective = Z − S 55 Tro: Chemistry: A Molecular Approach, 2/e

56. Copyright  2011 Pearson Education, Inc. Screening & Effective Nuclear Charge 56Tro: Chemistry: A Molecular Approach, 2/e

57. Copyright  2011 Pearson Education, Inc. 57 Tro: Chemistry: A Molecular Approach, 2/e

58. Copyright  2011 Pearson Education, Inc. Quantum-Mechanical Explanation for the Group Trend in Atomic Radius The size of an atom is related to the distance the valence electrons are from the nucleus The larger the orbital an electron is in, the farther its most probable distance will be from the nucleus and the less attraction it will have for the nucleus Traversing down a group adds a principal energy level The larger the principal energy level an orbital is in, the larger its volume  quantum-mechanics predicts the atoms should get larger down a column 58 Tro: Chemistry: A Molecular Approach, 2/e

59. Copyright  2011 Pearson Education, Inc. Quantum-Mechanical Explanation for the Period Trend in Atomic Radius The larger the effective nuclear charge an electron experiences, the stronger the attraction it will have for the nucleus The stronger the attraction the valence electrons have for the nucleus, the closer their average distance will be to the nucleus Traversing across a period increases the effective nuclear charge on the valence electrons  quantum-mechanics predicts the atoms should get smaller across a period 59 Tro: Chemistry: A Molecular Approach, 2/e

60. Copyright  2011 Pearson Education, Inc. 1. N or F 2. C or Ge 3. N or Al 4. Al or Ge? opposing trends 1. N or F 2. C or Ge 3. N or Al, Al is farther down & left 1. N or F 2. C or Ge, Ge is farther down Example 8.5: Choose the Larger Atom in Each Pair 1. N or F, N is farther left Tro: Chemistry: A Molecular Approach, 2/e60

61. Copyright  2011 Pearson Education, Inc. Practice – Choose the Larger Atom in Each Pair C or O C is farther left in the period Li or K K is farther down the column C or Al Al is farther left and down Se or I ? opposing trends C or O Li or K C or Al Se or I 61 Tro: Chemistry: A Molecular Approach, 2/e

62. Copyright  2011 Pearson Education, Inc. Trends in Atomic Radius Transition Metals Atoms in the same group increase in size down the column Atomic radii of transition metals roughly the same size across the d block much less difference than across main group elements valence shell ns 2, not the (n−1)d electrons effective nuclear charge on the ns 2 electrons approximately the same 62 Tro: Chemistry: A Molecular Approach, 2/e

63. Copyright  2011 Pearson Education, Inc. Electron Configurations of Main Group Cations in Their Ground State Cations form when the atom loses electrons from the valence shell Al atom = 1s 2 2s 2 2p 6 3s 2 3p 1 Al 3+ ion = 1s 2 2s 2 2p 6 63 Tro: Chemistry: A Molecular Approach, 2/e

64. Copyright  2011 Pearson Education, Inc. Electron Configurations of Transition Metal Cations in Their Ground State When transition metals form cations, the first electrons removed are the valence electrons, even though other electrons were added after Electrons may also be removed from the sublevel closest to the valence shell after the valence electrons The iron atom has two valence electrons Fe atom = 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 6 When iron forms a cation, it first loses its valence electrons Fe 2+ cation = 1s 2 2s 2 2p 6 3s 2 3p 6 3d 6 It can then lose 3d electrons Fe 3+ cation = 1s 2 2s 2 2p 6 3s 2 3p 6 3d 5 64 Tro: Chemistry: A Molecular Approach, 2/e

65. Copyright  2011 Pearson Education, Inc. Magnetic Properties of Transition Metal Atoms & Ions Electron configurations that result in unpaired electrons mean that the atom or ion will have a net magnetic field – this is called paramagnetism will be attracted to a magnetic field Electron configurations that result in all paired electrons mean that the atom or ion will have no magnetic field – this is called diamagnetism slightly repelled by a magnetic field 65 Tro: Chemistry: A Molecular Approach, 2/e

66. Copyright  2011 Pearson Education, Inc. Transition Metal Atoms and Ions: Electron Configuration & Magnetic Properties Both Zn atoms and Zn 2+ ions are diamagnetic showing that the two 4s electrons are lost before the 3d Zn atoms [Ar]4s 2 3d 10 Zn 2+ ions [Ar]4s 0 3d 10 Ag forms both Ag + ions and, rarely, Ag 2+ Ag atoms [Kr]5s 1 4d 10 are paramagnetic Ag + ions [Kr]4d 10 are diamagnetic Ag 2+ ions [Kr]4d 9 are paramagnetic 66 Tro: Chemistry: A Molecular Approach, 2/e

67. Copyright  2011 Pearson Education, Inc. 4s4s3d3d Fe atom = [Ar]4s 2 3d 6 Unpaired electrons Paramagnetic 4s4s3d3d Fe 3+ ion = [Ar]4s 0 3d 5 Unpaired electrons Paramagnetic Example 8.6c: Write the electron configuration and determine whether the Fe atom and Fe 3+ ion are paramagnetic or diamagnetic Fe Z = 26 Previous noble gas = Ar 18 electrons 67 Tro: Chemistry: A Molecular Approach, 2/e

68. Copyright  2011 Pearson Education, Inc. Practice – Determine whether the following are paramagnetic or diamagnetic 4s4s3d3d Mn Sc 3+ Mn = [Ar]4s 2 3d 5 paramagnetic Sc = [Ar]4s 2 3d 1 Sc 3+ = [Ar] diamagnetic 68 Tro: Chemistry: A Molecular Approach, 2/e

69. Copyright  2011 Pearson Education, Inc. Trends in Ionic Radius 69 Tro: Chemistry: A Molecular Approach, 2/e Ions in same group have same charge Ion size increases down the column higher valence shell, larger Cations smaller than neutral atoms; anions larger than neutral atoms Cations smaller than anions except Rb + & Cs + bigger or same size as F − and O 2− Larger positive charge = smaller cation for isoelectronic species isoelectronic = same electron configuration Larger negative charge = larger anion for isoelectronic species

70. Copyright  2011 Pearson Education, Inc. Periodic Pattern – Ionic Radius (Å) Tro: Chemistry: A Molecular Approach, 2/e70

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73. Copyright  2011 Pearson Education, Inc. Quantum-Mechanical Explanation for the Trends in Cation Radius When atoms form cations, the valence electrons are removed The farthest electrons from the nucleus then are the p or d electrons in the (n − 1) energy level This results in the cation being smaller than the atom These “new valence electrons” also experience a larger effective nuclear charge than the “old valence electrons,” shrinking the ion even more Traversing down a group increases the (n − 1) level, causing the cations to get larger Traversing to the right across a period increases the effective nuclear charge for isoelectronic cations, causing the cations to get smaller 73 Tro: Chemistry: A Molecular Approach, 2/e

74. Copyright  2011 Pearson Education, Inc. Quantum-Mechanical Explanation for the Trends in Anion Radius When atoms form anions, electrons are added to the valence shell These “new valence electrons” experience a smaller effective nuclear charge than the “old valence electrons,” increasing the size The result is that the anion is larger than the atom Traversing down a group increases the n level, causing the anions to get larger Traversing to the right across a period decreases the effective nuclear charge for isoelectronic anions, causing the anions to get larger 74 Tro: Chemistry: A Molecular Approach, 2/e

75. Copyright  2011 Pearson Education, Inc. Example 8.7: Choose the larger of each pair S or S 2− S 2− is larger because there are more electrons (18 e − ) for the 16 protons to hold the anion is larger than the neutral atom Ca or Ca 2+ Ca is larger because its valence shell has been lost from Ca 2+ the cation is always smaller than the neutral atom Br − or Kr the Br − is larger because it has fewer protons (35 p + ) to hold the 36 electrons than does Kr (36 p + ) for isoelectronic species, the more negative the charge the larger the atom or ion 75 Tro: Chemistry: A Molecular Approach, 2/e

76. Copyright  2011 Pearson Education, Inc. Practice – Order the following sets by size (smallest to largest) Zr 4+, Ti 4+, Hf 4+ Na +, Mg 2+, F −, Ne I −, Br −, Ga 3+, In + same column & charge, therefore Ti 4+ < Zr 4+ < Hf 4+ isoelectronic, therefore Mg 2+ < Na + < Ne < F − Ga 3+ < In + < Br − < I − 76 Tro: Chemistry: A Molecular Approach, 2/e

77. Copyright  2011 Pearson Education, Inc. Ionization Energy 77 Tro: Chemistry: A Molecular Approach, 2/e Minimum energy needed to remove an electron from an atom or ion gas state endothermic process valence electron easiest to remove, lowest IE M(g) + IE 1  M 1+ (g) + 1 e - M +1 (g) + IE 2  M 2+ (g) + 1 e -  first ionization energy = energy to remove electron from neutral atom; 2nd IE = energy to remove from 1+ ion; etc.

78. Copyright  2011 Pearson Education, Inc. General Trends in 1 st Ionization Energy The larger the effective nuclear charge on the electron, the more energy it takes to remove it The farther the most probable distance the electron is from the nucleus, the less energy it takes to remove it 1st IE decreases down the group valence electron farther from nucleus 1st IE generally increases across the period effective nuclear charge increases 78 Tro: Chemistry: A Molecular Approach, 2/e

79. Copyright  2011 Pearson Education, Inc. 79 Tro: Chemistry: A Molecular Approach, 2/e

80. Copyright  2011 Pearson Education, Inc. 80 Tro: Chemistry: A Molecular Approach, 2/e80

81. Copyright  2011 Pearson Education, Inc. Quantum-Mechanical Explanation for the Trends in First Ionization Energy The strength of attraction is related to the most probable distance the valence electrons are from the nucleus and the effective nuclear charge the valence electrons experience The larger the orbital an electron is in, the farther its most probable distance will be from the nucleus and the less attraction it will have for the nucleus  quantum-mechanics predicts the atom’s first ionization energy should get lower down a column Traversing across a period increases the effective nuclear charge on the valence electrons  quantum-mechanics predicts the atom’s first ionization energy should get larger across a period 81 Tro: Chemistry: A Molecular Approach, 2/e

82. Copyright  2011 Pearson Education, Inc. 1. Al or S 2. As or Sb, As is farther up 1. Al or S 2. As or Sb 3. N or Si, N is farther up & right 1. Al or S 2. As or Sb 3. N or Si 4. O or Cl? opposing trends Example 8.8: Choose the atom in each pair with the larger first ionization energy 1. Al or S, S is farther right Tro: Chemistry: A Molecular Approach, 2/e82

83. Copyright  2011 Pearson Education, Inc. Mg or P Ag or Cu Ca or Rb P or Se Practice – Choose the atom with the largest first ionization energy in each pair ? 83 Tro: Chemistry: A Molecular Approach, 2/e

84. Copyright  2011 Pearson Education, Inc. Which is easier to remove an electron from, N or O? Why? Exceptions in the 1 st IE Trends Be  1s1s2s2s2p2p B 1s1s2s2s2p2p  N 1s1s2s2s2p2p  O 1s1s2s2s2p2p  Which is easier to remove an electron from B, or Be? Why? 84 Tro: Chemistry: A Molecular Approach, 2/e First Ionization Energy generally increases from left to right across a Period Except from 2A to 3A, 5A to 6A

85. Copyright  2011 Pearson Education, Inc. Exceptions in the First Ionization Energy Trends, Be and B Be  1s1s2s2s2p2p B 1s1s2s2s2p2p  Be +  1s1s2s2s2p2p To ionize Be you must break up a full sublevel, costs extra energy B+B+  1s1s2s2s2p2p When you ionize B you get a full sublevel, costs less energy 85 Tro: Chemistry: A Molecular Approach, 2/e

86. Copyright  2011 Pearson Education, Inc. Exceptions in the First Ionization Energy Trends, N and O To ionize N you must break up a half-full sublevel, costs extra energy N+N+  1s1s2s2s2p2p  O 1s1s2s2s2p2p  N 1s1s2s2s2p2p   O+O+ 1s1s2s2s2p2p  When you ionize O you get a half-full sublevel, costs less energy 86 Tro: Chemistry: A Molecular Approach, 2/e

87. Copyright  2011 Pearson Education, Inc. Trends in Successive Ionization Energies Removal of each successive electron costs more energy shrinkage in size due to having more protons than electrons outer electrons closer to the nucleus, therefore harder to remove Regular increase in energy for each successive valence electron Large increase in energy when start removing core electrons 87 Tro: Chemistry: A Molecular Approach, 2/e

88. Copyright  2011 Pearson Education, Inc. 88 Tro: Chemistry: A Molecular Approach, 2/e

89. Copyright  2011 Pearson Education, Inc. Electron Affinity 89 Tro: Chemistry: A Molecular Approach, 2/e Energy released when an neutral atom gains an electron gas state M(g) + 1e −  M 1− (g) + EA Defined as exothermic (−), but may actually be endothermic (+) some alkali earth metals & all noble gases are endothermic, WHY? The more energy that is released, the larger the electron affinity the more negative the number, the larger the EA

90. Copyright  2011 Pearson Education, Inc. Trends in Electron Affinity Alkali metals decrease electron affinity down the column but not all groups do generally irregular increase in EA from 2 nd period to 3 rd period “Generally” increases across period becomes more negative from left to right not absolute Group 5A generally lower EA than expected because extra electron must pair Group 2A and 8A generally very low EA because added electron goes into higher energy level or sublevel Highest EA in any period = halogen 90 Tro: Chemistry: A Molecular Approach, 2/e

91. Copyright  2011 Pearson Education, Inc. 91 Tro: Chemistry: A Molecular Approach, 2/e

92. Copyright  2011 Pearson Education, Inc. Properties of Metals & Nonmetals 92 Tro: Chemistry: A Molecular Approach, 2/e Metals malleable & ductile shiny, lusterous, reflect light conduct heat and electricity most oxides basic and ionic form cations in solution lose electrons in reactions – oxidized Nonmetals brittle in solid state dull, non-reflective solid surface electrical and thermal insulators most oxides are acidic and molecular form anions and polyatomic anions gain electrons in reactions – reduced

93. Copyright  2011 Pearson Education, Inc. Metallic Character Metallic character is how closely an element’s properties match the ideal properties of a metal more malleable and ductile, better conductors, and easier to ionize Metallic character decreases left-to-right across a period metals are found at the left of the period and nonmetals are to the right Metallic character increases down the column nonmetals are found at the top of the middle Main Group elements and metals are found at the bottom 93 Tro: Chemistry: A Molecular Approach, 2/e

94. Copyright  2011 Pearson Education, Inc. 94 Tro: Chemistry: A Molecular Approach, 2/e

95. Copyright  2011 Pearson Education, Inc. 95 Tro: Chemistry: A Molecular Approach, 2/e

96. Copyright  2011 Pearson Education, Inc. Quantum-Mechanical Explanation for the Trends in Metallic Character Metals generally have smaller first ionization energies and nonmetals generally have larger electron affinities except for the noble gases  quantum-mechanics predicts the atom’s metallic character should increase down a column because the valence electrons are not held as strongly  quantum-mechanics predicts the atom’s metallic character should decrease across a period because the valence electrons are held more strongly and the electron affinity increases 96 Tro: Chemistry: A Molecular Approach, 2/e

97. Copyright  2011 Pearson Education, Inc. 1. Sn or Te 2. P or Sb, Sb is farther down 1. Sn or Te 2. P or Sb 3. Ge or In, In is farther down & left Example 8.9: Choose the more metallic element in each pair 1. Sn or Te 2. P or Sb 3. Ge or In 4. S or Br? opposing trends 1. Sn or Te, Sn is farther left Tro: Chemistry: A Molecular Approach, 2/e97

98. Copyright  2011 Pearson Education, Inc. Practice – Choose the more metallic element in each pair Mg or Al Si or Sn Br or Te Se or I ? 98 Tro: Chemistry: A Molecular Approach, 2/e

99. Copyright  2011 Pearson Education, Inc. 99 Trends in the Alkali Metals Atomic radius increases down the column Ionization energy decreases down the column Very low ionization energies good reducing agents, easy to oxidize very reactive, not found uncombined in nature react with nonmetals to form salts compounds generally soluble in water  found in seawater Electron affinity decreases down the column Melting point decreases down the column all very low MP for metals Density increases down the column except K in general, the increase in mass is greater than the increase in volume Tro: Chemistry: A Molecular Approach, 2/e

100. Copyright  2011 Pearson Education, Inc. Alkali Metals 100 Tro: Chemistry: A Molecular Approach, 2/e

101. Copyright  2011 Pearson Education, Inc. 101 Trends in the Halogens Atomic radius increases down the column Ionization energy decreases down the column Very high electron affinities good oxidizing agents, easy to reduce very reactive, not found uncombined in nature react with metals to form salts compounds generally soluble in water  found in seawater Reactivity increases down the column React with hydrogen to form HX, acids Melting point and boiling point increase down the column Density increases down the column in general, the increase in mass is greater than the increase in volume Tro: Chemistry: A Molecular Approach, 2/e

102. Copyright  2011 Pearson Education, Inc. Halogens 102 Tro: Chemistry: A Molecular Approach, 2/e

103. Copyright  2011 Pearson Education, Inc. Reactions of Alkali Metals with Halogens Alkali metals are oxidized to the 1+ ion Halogens are reduced to the 1− ion The ions then attach together by ionic bonds The reaction is exothermic 103 Tro: Chemistry: A Molecular Approach, 2/e

104. Copyright  2011 Pearson Education, Inc. 104 Example 8.10: Write a balanced chemical reaction for the following Reaction between potassium metal and bromine gas K(s) + Br 2 (g)  K(s) + Br 2 (g)  K + Br  2 K(s) + Br 2 (g)  2 KBr(s) (ionic compounds are all solids at room temperature) Tro: Chemistry: A Molecular Approach, 2/e

105. Copyright  2011 Pearson Education, Inc. Reactions of Alkali Metals with Water Alkali metals are oxidized to the 1+ ion H 2 O is split into H 2 (g) and OH − ion The Li, Na, and K are less dense than the water – so float on top The ions then attach together by ionic bonds The reaction is exothermic, and often the heat released ignites the H 2 (g) 105 Tro: Chemistry: A Molecular Approach, 2/e

106. Copyright  2011 Pearson Education, Inc. 106 Example 8.10: Write a balanced chemical reaction for the following Reaction between rubidium metal and liquid water Rb(s) + H 2 O(l)  Rb (s) + H 2 O (l)  Rb + (aq) + OH  (aq) + H 2(g) 2 Rb (s) + 2 H 2 O (l)  2 Rb + (aq) + 2 OH  (aq) + H 2(g) (alkali metal ionic compounds are soluble in water) Tro: Chemistry: A Molecular Approach, 2/e

107. Copyright  2011 Pearson Education, Inc. 107 Example 8.10: Write a balanced chemical reaction for the following Reaction between chlorine gas and solid iodine Cl 2 (g) + I 2 (s)  Cl 2 (g) + I 2 (s)  ICl write the halogen lower in the column first assume 1:1 ratio, though others also exist 2 Cl 2 (g) + I 2 (s)  2 ICl(g) (molecular compounds are found in all states at room temperature, so predicting the state is not always possible) Tro: Chemistry: A Molecular Approach, 2/e

108. Copyright  2011 Pearson Education, Inc. 108 Trends in the Noble Gases Atomic radius increases down the column Ionization energy decreases down the column very high IE Very unreactive only found uncombined in nature used as “inert” atmosphere when reactions with other gases would be undersirable Melting point and boiling point increase down the column all gases at room temperature very low boiling points Density increases down the column in general, the increase in mass is greater than the increase in volume Tro: Chemistry: A Molecular Approach, 2/e

109. Copyright  2011 Pearson Education, Inc. Noble Gases 109 Tro: Chemistry: A Molecular Approach, 2/e