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Chemistry 1050 Periodic Chemical Properties Text: Petrucci, Harwood, Herring, 8th Edition Suggested Text Problems Review Questions: 5,6 7, 9 !17 Exercises: 1. 29, 31, 33, 35, 37, 39, 41, 43, 45, 51(b) (c) (d), 62, 68 Write ground state electron configurations in spdf notation for the following: Use shorthand for elements found in period # $ 4 cations: Be2+, Na+, Zn2+, Ti3+, Cr2+, Cu+ anions: O2-, P3-, IG 2. Write equations to represent the four successive ionization energies of beryllium. 3. Write balanced equations to represent the following processes: (a) (b) (c) (d) (e) (f) (g) (h) The first ionization energy of F, I1 = 1680 kJ molG1 The third ionization energy of K, I3 = 4410 kJ molG1 The fifth ionization energy of P, I5 = 6240 kJ molG1 The first ionization energy of Na+, I1 = 4560 kJ molG1 The first ionization energy of ClG, I1 = 348 kJ molG1 The electron affinity of C, EA = !123 kJ molG1 The electron affinity of OG, EA = 744 kJ molG1 The electron affinity of Al3+, EA = !2750 kJ molG1 4. Arrange the following in order of increasing atomic radius as well as increasing first ionization energy: He, As, F, P, and N. Use general period and group trends. 5. Explain why the effective nuclear charge felt by valence electrons is fairly constant for elements in the same group but tends to increase across a period. 6. (a) (b) 7. Give brief explanations for the following observations: Hint: First determine the electron configuration of any element or ion named. It is always an important clue to any explanation. Also look to see if a pair of elements are in the same period or family or if a pair of species are isoelectronic. On what 2 factors does the electron affinity of an atom depend? Explain why the Noble Gases and the Alkaline Earth Metals have no tendency to gain an electron. 1 (a) The first ionization energy of oxygen (1314 kJ molG1) is greater than the first ionization energy of sulfur (999.5 kJ molG1). (b) The first ionization energy of beryllium (899 kJ molG1) is greater than the first ionization energy of lithium (520 kJ molG1). The first ionization energy of helium (2373 kJ molG1) is much greater than the first ionization energy of lithium (520 kJ molG1). (c) (d) The fourth ionization energy of boron (25,000 kJ molG1) is much greater than the fourth ionization energy of carbon (6220 kJ molG1). (e) The atomic radius of argon (98 pm) is larger than the atomic radius of neon (70 pm). (f) The atomic radius of aluminum (143 pm) is larger than the atomic radius of silicon (132 pm). (g) The first ionization energy of aluminum (577.9 kJ molG1) is less than the first ionization energy of magnesium (738.1 kJ molG1). (h) The first ionization energy of sulfur (999.5 kJ molG1) is less than the first ionization energy of phosphorus (1012 kJ molG1). (i) The ionic radius of the calcium ion, Ca2+, (99 pm) is smaller than the atomic radius of the calcium atom (197 pm). (j) The ionic radius of the sulfide ion, S2G, (184 pm) is larger than the atomic radius of the sulfur atom (127 pm). (k) Determine which of the following species are isoelectronic with neon: Mg2+, ClG, Kr, N3G, K+. (l) The ionic radius of the oxide ion, O2G, (140 pm) is larger than the ionic radius of the aluminum ion, Al3+, (50 pm). (m) The first ionization energy of neon (2080 kJ molG1) is greater than the first nation energy of the fluoride ion, FG (333 kJ molG1) but less than the first ionization energy of the sodium ion, Na+, (4560 kJ molG1). (n) Sodium reacts vigorously with non-metals to form ionic compounds containing the Na+ ion. No ionic compound containing the Na2+ ion exists. (o) Potassium is more reactive than calcium but less reactive than cesium in all respects. (Hint: these metals react with non-metals to form cations). 2 (p) 8. The electron affinities of the halogens are very exothermic. Element M is a third period element with the following successive ionization energies: I1, = 786 kJ molG1 I2 = 1577 kJ molG1 I3 = 3232 kJ molG1 I4 = 4355 kJ molG1 I5 = 16,091 kJ molG1 I6 = 19,784 kJ molG1 I7 = 23,766 kJ molG1 I8 = 29,251 kJ molG1 (a) (b) Identify element M. Justify your choice. Determine the energy required in kJ molG1 for the following process: M(g)+ 6 M5+(g) + 4 eG (c) Explain why the second ionization energy of element M is greater than it's first ionization energy. 9. Classify the following as paramagnetic or diamagnetic: F, Zn, Ti2+, S2G. 10. Define or explain metallic radius, covalent radius, ionic radius, effective nuclear charge, electron screening, electron penetration, first ionization energy, electron affinity, diamagnetic species and paramagnetic species. 11. Explain why the atomic radii of transition elements tend to be the same across a period. A few unusual exceptions occur. Explanations for the exceptions are beyond Chem 1050. Answers 1. cations Be2+ (Z = 4, 2eG) 1s2 Na+ (Z= 11, 10eG) 1s22s22p6 Zn2+ (Z = 30, 28eG) [Ar] 3d10 Te3+ (Z = 22, 19eG) [Ar] 3d1 Cu+ (Z = 29, 28 eG) [Ar] 3d10 anions O2G (Z = 8, 10 eG) 1s22s22p6 P3G (Z = 15, 18 eG) 1s22s22p63s23p6 IG (Z = 53, 54 eG) [Kr] 4d105s25p6 2. 3. Be(g) → Be+(g) + eG Be+(g) → Be2+(g) + eG Be2+(g) → Be3+(g) + eG Be3+(g) → Be4+(g) + eG (a) F(g) 6 F+(g) + eG 3 4. 5. 6. 7. (b) K2+(g) 6 K3+(g) + eG (c) P4+(g) 6 P5+(g) + eG (d) Na+(g) 6 Na2+(g) + eG (e) ClG(g) 6 Cl(g) + eG (f) C(g) + e! 6 CG(g) (g) OG(g) + eG 6 O2G(g) (h) Al3+(g) + eG 6 Al2+(g) lowest I1 As < P < N < F < He highest I1 smallest r He < F < N < P < As largest r As one goes down a group, the increase in nuclear charge is nearly balanced by a corresponding increase in the number of core electrons. As one goes across a period, additional electrons go into the same shell where they provide little additional shielding against the increasing nuclear charge. (a) Factors: 1. nuclear attraction for added electron 2. repulsions of atom’s electrons, especially the valence electrons for added electron. (b) The added electron for the Noble gases must enter the ns orbital of the next higher electron shell. The added electron for Group 2A goes into the valence np subshell where it is well shielded by the core and valence ns electrons from the nucleus. (a) same family, Zeff of valence electron removed about the same. I1 decreases with nvalue as an electron in shell further from nucleus is easier to remove. (b) same period, n(constant). Zeff Be > Zeff Li (period trend) (c) ls electrons of He are poorly screened from nucleus. They are very close to nucleus and strongly held. The 2s electron of Lithium is well screened by its core electrons, is in a shell further from the nucleus and it is weakly held. (d) A strongly held core electron is removed from B vs well screened valence electron removed from C. (e) same family, argon has one more electron shell. (f) same period, n(constant). Zeff Si > Zeff Al (period trend) (g) same period, 3p electron of Al does not penetrate inner shells as well as 3s electron of Mg. It feels a lower Zeff and a weaker nuclear attraction. (h) same period, paired electron removed from oxygen experiences greater repulsions due to close proximity of electrons in same orbital vs the unpaired electron removed from nitrogen. This lowers its Zeff and the nuclear attraction for it. (i) Ca2+ has only 3 electron shells occupied vs 4 for Ca. (j) S2G has extra 2 electrons. They increase repulsions and decrease Zeff of the valence electrons. The electrons are not held as tightly and they spread out. (k) Mg2+, N3G (l) isoelectronic species: Al3+ has more protons (13) vs O2G which has only 8. A larger # protons means a greater nuclear attraction pulling the electrons in closer. (m) isoelectronic species: Na+ has the most protons (11) and the greatest nuclear attraction to overcome. FG has the least protons (9) and the weakest nuclear attraction to overcome. (n) weak nuclear attraction for well screened valence 3s electron. Very strong nuclear attraction for core 2p electrons (o) metals react to form K+, Ca2+, Cs+ ions. I1(Cs) < I1 (K) < (I1 + I2) (Ca). Reactivity would increase as the energy required in the reaction to form the product cation decreases making Cs most reactive and Ca least reactive. 4 (p) 9. The effective nuclear charge on the valence np electrons of a Halogen is quite large so the nuclear attraction for the added electron is relatively strong. Also, a filled np subshell and a noble gas electron configuration results which is very stable. Silicon I5 >> I4 (b) E = 25,255 kJ·molG1 (Sum of I2, I3, I4 and I5) Use Hess’s Law. (c) The second electrons must be removed from a positively charged species (M+). This is more difficult to do and requires more energy. paramagnetic: F, Ti2+ diamagnetic: Zn, S2G 10. metallic radius: 8. One half the internuclear distance between identical atoms in a metallic crystal. covalent radius: One half the internuclear distance between identical atoms joined by a single covalent bond. ionic radius: radius of an ion as determined by properly apportioning the distance between the nuclei of a cation and anion in an ionic bond. By making an initial guess of the radius of a single ion, e.g. O2G, one can estimate the size of other ions bonded to it. These estimated values can be used to determine the size of additional ions. The initial guess can then be revised to give consistent results. effective nuclear charge: The number of protons an electron actually feels is pulling it towards the nucleus. electron screening: The screening or shielding of the nuclear charge by electrons between a given electron and the nucleus. electron penetration: Ability of an electron to get close to the nucleus. This ability decreases as the electron’s l-value increases. first ionization energy: The energy required to remove an electron from an isolated, gaseous atom (or ion). electron affinity: The energy change that results when an isolated, gaseous atom (or ion) gains an electron. diamagnetic species: An atom, ion (or molecule) in which all electrons are paired. It is weakly repelled by a magnetic field. paramagnetic species: An atom, ion (or molecule) which has one or more unpaired electrons. It is attracted into an external magnetic field. The more unpaired electrons present, the greater the attraction. 12. Additional electrons go into an inner shell, i.e. they are added to the (n-1) d subshell where they effectively screen the ns valence electrons from the increase in nuclear charge. The ns valence electrons (usually two, sometimes one) feel a roughly comparable force of attraction to the nucleus. Developed by: Dr. Chris Flinn 5