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CHEM 1411 General Chemistry
Chemistry: A Molecular Approach by Nivaldo J. Tro
Periodic Properties of the Elements
Chapter Objectives: • Learn how to write electron configurations for neutral atoms and ions. • Learn how to predict trends in atomic radius, effective nuclear charge, ionic radius, ionization energy, electron affinity, and metallic character from the positions of the elements on the periodic table.
Mr. Kevin A. Boudreaux
Angelo State University
• A number of element and ion properties vary in a periodic, predictable way across the periodic table. These include: – atomic radius – effective nuclear charge – ionic radius – ionization energy – electron affinity – metallic character – electronegativity (Ch. 9)
Chapter 8 Notes
The Development of the Periodic Table
• It has long been known that many of the elements have similar chemical properties. – Lithium, sodium, and potassium all perform the same reaction with water, 2M(s) + 2HOH(l) → 2MOH(aq) + H2(g) the only difference being the masses of the metals themselves and the vigor and speed of the reaction.
Potassium warp speed
Chapter 8 Notes
The Invention of the Periodic Table
• In 1869 Dimitri Mendeleev published a table in which the elements that were known at the time were arranged by increasing atomic mass, and grouped into columns according to their chemical properties. The properties of the elements varied (more or less) in a periodic way in this arrangement.
H Li Be B C N O F Na Mg Al Si P S Cl K Ca As Se Br
Atomic Weight 1 7 9.4 11 12 14 16 19 23 24 27.3 28 31 32 35.5 39 40 75 78 80
Chlorides HCl LiCl BeCl2 BCl3 CCl4
Mendeleev’s Periodic Table
• Mendeleev noticed that when he grouped the elements by their properties, there were some “holes” which he guessed corresponded to as-yet-unknown elements. • Mendeleev predicted some of the properties for two of these, ekaaluminum (?=68), and eka-silicon (?=72), which corresponded well to gallium (Ga, discovered in 1875) and germanium (Ge, 1886)
Na3N Na2O NaF
NaCl MgCl2 AlCl3 SiCl4
Na3P Na2S NaCl Na3As Na2Se NaBr
and with the development of X-ray spectroscopy.0983 g/mol) is slightly lighter than argon (39. It was also possible to count protons.948 g/mol). 7 The Modern Periodic Table of the Elements 8 . it was discovered that the periodic table could be written in order of increasing atomic number. it was sometimes necessary to exchange the order of the elements. potassium (39.Chapter 8 Notes The Periodic Table by Atomic Number • To make the properties of the elements “line up” properly. and see exactly how many “missing” elements there were. so by increasing atomic weight. – For instance. with no need to “play around” with the order of the elements. potassium should be in Group 8A. and argon in Group 1A. but that clearly doesn’t fit their observed properties. • After the discovery of the nucleus and the proton.
etc. the 3s.) the energy of the orbital depends only on n. (Orbitals having the same energy are said to be degenerate. etc. The 2s and 2p orbitals have the same energy.Chapter 8 Notes Electron Configurations 9 Energy Levels of One-Electron Atoms • In one-electron atoms (H.) 10 . 3p. He+. and 3d orbitals all have the same energy.
12 . and are lowered in energy because of their greater penetration of the inner atomic core.) • These energy differences result from a balance of attractive forces between electrons and the nucleus. 11 Energy Levels of Multi-Electron Atoms • There is some crossover of energies from one shell to another. • Having more protons in the nucleus lowers the energy of close-lying electrons. • Adding more electrons increases electron-electron repulsions. (A 3d orbital in some atoms is higher in energy than a 4s orbital. • Orbitals which have a greater electron density near the nucleus experience more of the nuclear charge.Chapter 8 Notes Energy Levels of Multi-Electron Atoms • In multi-electron atoms the orbital energy depends on n and l (s<p<d<f). so there are differences in energy between the subshells. and repulsive forces between electrons.
Chapter 8 Notes Energy Levels of Multi-Electron Atoms • Repulsion of the outer-shell electrons by ones in lower-lying shells cause the outer-shell electrons to be pushed father away from the nucleus. resulting in the ground-state configuration of the atom. 14 . building-up) guides the order in which orbitals are filled. Part of their attraction for the nucleus is canceled. and to be held less tightly. Figure 8. and we say that these electrons are shielded from the nucleus by the inner electrons. • A set of rules called the aufbau principle (German.4 13 Putting Everything Together • Knowing the relative energies of the various orbitals allows us to predict the electron configuration for any atom or ion — a list of how the electrons in that atom are distributed among its orbitals. • Each successive electron added to an atom occupies the lowest-energy orbital available.
or a square).) 15 Writing Electron Configurations • To write an element’s electron configuration. (This is a consequence of the mutual repulsion between like charged-electrons. 16 . 5s. 4f. 3p. one electron goes into each orbital (spin up) until all are half-full. only then does a second electron fill one of the orbitals.g. write in the orbitals that are occupied by electrons. which must have opposite spins (Pauli exclusion principle). 2p. 7s. followed by a superscript to indicate how many electrons are in the set of orbitals (e. 5f • An orbital can hold only two electrons. 4s. 6p. and the electrons as arrows pointing up (↑) or down (↓) (indicating the electron spin). The order in which the orbitals are filled is: 1s. 4p.. 5p. H 1s1) • Another way to show the placement of electrons is an orbital diagram. 3s. 6s. 4d. in which each orbital is represented by a circle (or a line. 5d. • Hund’s Rule: If two or more degenerate orbitals (orbital at the same energy level) are available.Chapter 8 Notes The Aufbau Principle • Lower-energy orbitals fill before higher-energy orbitals. 3d. 2s.
Using the diagram on the next page. write the electron configuration and orbital diagram for the following elements. Li B C N O F Ne 17 1s22s1 1s22s22p1 Be 1s22s2 18 . and state whether they are diamagnetic or paramagnetic.Chapter 8 Notes Examples: Electron Configurations 1.
this configuration can be abbreviated as: Ba: [Xe] 6s2 • Abbreviated electron configurations are always based on the nearest preceding noble gas. because this sequence can be read from the periodic table in the following fashion: 20 .Chapter 8 Notes Abbreviated Electron Configurations • For atoms following neon. the full electron configuration can be extremely cumbersome to write: Ba: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6 6s2 • Since everything up to the 5p6 is exactly the same electron configuration as the noble gas xenon (Xe). 19 Electron Configurations and the Periodic Table • It is not necessary to memorize the orbital order in the aufbau scheme.
and state whether the element is diamagnetic or paramagnetic.Chapter 8 Notes Electron Configurations and the Periodic Table 1s 1s n (n)s (n-1)d (n)p (n-2)f 21 Examples: Electron Configurations 2. For the following elements. orbital diagram. provide the abbreviated electron configuration. Na Mg Al Cl Ar Fe Sn Pb I 22 .
6 23 Periodic Table of Valence Shell Configurations Figure 8.7 24 .Chapter 8 Notes Valence Electrons • Valence electrons are the electrons in the outermost shell (with the highest value of n). and do not participate in bonding. and therefore have similar chemical properties. • Core electrons are those in complete principal energy levels. Fig. 8. All the elements in the same group on the periodic table have similar electron configurations for their valence shells.
– The Group 2A elements (ns2) lose their two valence electrons to form 2+ charges. 25 The Explanatory Power of the QM Model • The chemical properties of elements are largely determined by the number of valence electrons they contain.Chapter 8 Notes Some Anomalous Electron Configurations • Half-filled and filled subshells have special stability. leading to some unexpected electron configurations: – Cr [Ar]3d44s2 – Cu [Ar]3d94s2 – Ag [Kr]4d95s2 – Au [Xe]4f145d96s2 actual: [Ar]3d54s1 actual: [Ar]3d104s1 actual: [Kr]4d105s1 actual: [Xe]4f145d106s1 • Most of the anomalous electron configurations occur in elements with atomic numbers greater than Z = 40. forming 1+ charges. 26 . – The Group 8A elements are inert because their valence shells are already full. where the energy differences between subshells are very small. In all of these cases. – The Group 7A elements (ns2np5) gain one electron to complete their valence shells. – The Group 1A elements (ns1) can attain a noble gas configuration by losing their single valence electrons. the transfer of an electron from one subshell to another lowers the total energy of the atom because of a decrease in electron-electron repulsion.
28 .Chapter 8 Notes Atomic Radius and Effective Nuclear Charge 27 Atomic Radius • The atomic radius of an atom can be measured either by taking one-half of the distance between atoms in an atomic solid (the nonbonding atomic radius or van der Waals radius) or by taking one half of the distance between two identical bonded nuclei or between atoms in a metallic crystal (the bonding atomic radius or covalent radius).
• When the atomic radius is graphed against the atomic number (Figures 8.Chapter 8 Notes Trends in Atomic Radii • An average atomic radius for a particular element can be determined from the measurement of a large number of elements and compounds. there is a periodic pattern to the radii across a group: – the radius is largest for the Group 1A elements.9 30 .9 and 8.10). the size increases from top to bottom within the group. – for elements in a particular group. and becomes smaller as we move towards the Group 8A elements. 29 Trends in Atomic Radii Figure 8.
Chapter 8 Notes Atomic Radius: Top to Bottom • As we add larger valence shells (larger values of n). 31 Effective Nuclear Charge • The net nuclear charge actually felt by an outer-shell electron. the size of the atom increases. called the effective nuclear charge (Zeff). because the core electrons “shield” the outer electrons from the full effect of the nuclear charge: Zeff = Zactual . is often substantially lower than the actual nuclear charge Z. Therefore.11 32 . atomic size increases as we move from top to bottom in a group.Electron shielding Figure 8.
Zeff increases from left to right across a period. but no increase in shielding (the number of inner electrons isn’t changing. valence electrons inner electrons nucleus • An increasing Zeff means there is a stronger attraction between the nucleus and the valence electrons.10 34 . 33 Trends in Atomic Radii Figure 8. Therefore.Chapter 8 Notes Atomic Radius: Left to Right • As we move to the right in a period. atomic radius decreases from left to right in a period. and valence electrons don’t shield each other). there are more protons in the nucleus.
Chapter 8 Notes Effective Nuclear Charge and Atomic Radius 35 Examples: Atomic Radii and the Size of Atoms 3. Which atom is larger. Al or Ge? 7. Rb. Si or Ge? 5. Which atom is larger. 36 . Arrange the following elements in order of increasing size: Cs. Which atom is larger. C or N? 4. Which atom is larger. Sr. Mg or Ba? 6. Ca.
core electrons (inner shell) do not usually play a role in chemical bonding. and so are the ones which are most exposed to other atoms. and are on average the farthest away from the nucleus. the electrons gained in forming anions are added to the valence shell. the electrons lost in forming cations are taken from the valence shell. – For main-group nonmetals.Chapter 8 Notes Properties of Ions 37 The Valence Shell • The electrons in the outermost or valence shell (the one that has the highest value of n) have the highest energies. • The inner. – For main-group metals. 38 .
• The chlorine atom accepts an electron into its 3p subshell. main-group elements react so that they attain a noble gas e. MOV: Formation of Sodium Chloride 39 The Octet Rule • The Na+ and Cl.ion’s electron configurations are the same as that of the nearest noble gas (the ions are said to be isoelectronic with the nearest noble gas). the 3s1 electron in sodium is lost. filling the n=3 shell: Cl 1s22s22p63s23p5 + e. with 8 e-’s in the valence shell.1s22s22p63s23p6 – The Cl. with 8 e-’s in the valence shell. Atoms “prefer” to have a filled outermost shell because this is more electronically stable. • There are many exceptions to the octet rule. producing an sodium ion : Na 1s22s22p63s1 → Na+ 1s22s22p6 + e– The next shell down (n=2) is now the outermost shell. – That is.ion the same electron configuration as the noble gas argon. but it is useful for making predictions about some chemical bonds. which is full.configuration with filled s and p sublevels in their valence electron shell. 40 . • This can be generalized into the octet rule: Maingroup elements tend to undergo reactions that leave them with eight outer-shell electrons.→ Cl. – The Na+ ion has the same configuration as the noble gas neon. there is little tendency to lose more electrons.Chapter 8 Notes The Formation of Sodium Chloride • When sodium reacts with chlorine.
Chapter 8 Notes Group 1A-3A Cations • Elements with similar outer shell configurations form similar ions. thus attaining a pseudo-noble gas configuration. 4A Sn [Kr]4d105s25p2 Sn2+ [Kr]4d105s2 Sn4+ [Kr]4d10 4A Pb [Xe]4f145d106s26p2 Pb2+ [Xe]4f145d106s2 Pb4+ [Xe]4f145d10 5A Bi [Xe]4f145d106s26p3 Bi3+ [Xe]4f145d106s2 Bi5+ [Xe]4f145d10 42 . or from both the s and p subshells. • For instance. the valence s1 electron is the one that’s lost: 1A Li 1s22s1 1A Na 1s22s22p63s1 Li+ 1s2 Na+ 1s22s22p6 1s22s22p63s23p6 1A K 1s22s22p63s23p64s1 K+ • The Group 2A and 3A metals also tend to lose all of their valence electrons to form cations. 2A Be 1s22s2 2A Mg 1s22s22p63s2 3A Al 1s22s22p63s23p1 Be2+ 1s2 Mg2+ 1s22s22p6 Al3+ 1s22s22p6 41 Group 4A and 5A Cations • The Group IV and V metals can lose either the electrons from the p subshell. the alkali metals form ions with a +1 charge.
Chapter 8 Notes Transition Metal Cations • Transition metals lose their ns electrons before the (n-1)d electrons. Fe [Ar] 3d64s2 Fe2+ [Ar] 3d6 Fe3+ [Ar] 3d5 —————————————————————— Zn [Ar] 3d10 4s2 Zn2+ [Ar] 3d10 —————————————————————— Ag [Kr] 4d10 5s1 Ag+ [Kr] 4d10 43 Nonmetal Anions and Noble Gases • The Group 6A – 8A non-metals gain electrons until their valence shells are full (8 electrons).1s22s22p6 F1s22s22p6 • The Group 8A noble gases already possess a full outer shell. 4A 5A 6A 7A C N O F 1s22s22p2 1s22s22p3 1s22s22p4 1s22s22p5 C4. Some can also lose electrons from their highest d levels. usually forming 2+ charges.1s22s22p6 N3. so they have no tendency to form ions. 8A 8A Ne 1s22s22p6 Ar 1s22s22p63s23p6 44 .1s22s22p6 O2.
(sim. Ni2+ e. La2+ . 8. Ti4+ f. N3g. Ra2+ b. What 2+ ion has the ground-state electron configuration 1s22s22p63s23p63d10 ? 46 . Mn2+.6) a.Chapter 8 Notes Examples: Predicting Ion Configurations 8. Mn3+ d. Predict the ground-state electron configuration for each of the following ions. to Ex. La3+ c. and state whether they are diamagnetic or paramagnetic. Te245 Examples: Predicting Ion Configurations 9.
13 48 . – Ionic size decreases for cations across a period. Fe3+ < Fe2+).12 Figure→ 8. since electrons are being removed from the valence shell. • The greater the ionic charge. • Anions are larger than their parent atoms. since the number of electron-electron repulsions increases when electrons are added. MOV: Gain and Loss of Electrons 47 ←Figure 8. – Ionic size decreases for anions across a period.g. • Trends in ion size are the same as for neutral atoms: – Ionic size increases down a group. the smaller the ionic radius (e.Chapter 8 Notes Ionic Radii • Cations are smaller than their parent atoms..
Arrange the following ions in order of increasing size: O2-. Sn2+ or Sn4+? 14. Rb+ or Br-? 15. Ar. Which species is larger. Arrange the following in order of increasing size: Ca2+. S2-. Cl-. S2-. As3-. Which species is larger. Na or Na+? 12. 50 . Br or Br-? 49 Examples: Predicting Periodic Trends 13. 11. K+.Chapter 8 Notes Examples: Predicting Periodic Trends 10. Which species is larger. P3-. Which species is larger.
MOV: Ionization Energies 52 . ΔH° = IE (always > 0) • Ionization energy is a positive energy value (an endothermic process). Electron Affinity.Chapter 8 Notes Periodic Properties: Ionization Energy. energy must be provided in order to remove an electron from an atom. and Metallic Character 51 Ionization Energy • Ionization Energy (IE) — the amount of energy needed to remove an electron from a mole of neutral atoms in the gas phase: M(g) → M+(g) + e-(g). • The energy required to remove the first electron is the first ionization energy (IE1).
ionization energy increases as we move from left to right across a period. and are harder to remove. • As we move left-to-right across a period. Atomic Number Figure 8. atomic size increases. those with high ionization energies (nonmetals) tend to form anions.14 54 .Chapter 8 Notes Trends in First Ionization Energy • As we move down a group. since they are farther from the nucleus. the outer electrons are held more tightly. As a result. ionization energy decreases as we move down a group. Therefore. Therefore. so the outermost electrons become easier to remove. Zeff increases and atomic size decreases. • Atoms with low ionization energies (metals) tend to form cations. 53 MOV: Periodic Trends Ionization Energies Ionization Energy vs.
the variations result from the ionization of atoms which have either one electron in a p subshell (B. or are one electron away from being half-filled (O. Al).Chapter 8 Notes Trends in Ionization Energy Figure 8. 56 .15 55 Exceptions to Trends in First Ionization Energy • There are some variations in the general trends. S).
• Large jumps in ionization energy occur when we are trying to remove electrons from filled shells.Chapter 8 Notes Higher Ionization Energies • Of course. it is possible to form more than just 1+ cations: M(g) → M+(g) + e-(g) M+(g) → M2+(g) + e-(g) first ionization energy (IE1) second ionization energy (IE2) M2+(g) → M3+(g) + e-(g) third ionization energy (IE3) • More energy is required for each successive ionization step (IE3 > IE2 > IE1) because it is harder to remove an electron from a positively charged ion. 57 Higher Ionization Energies • Why is the third ionization energy of Be so much higher than the second and first? Be 1s2 2s2 IE1 Be+ 1s2 2s1 IE2 Be2+ 1s2 IE3 Be3+ 1s1 58 .
Chapter 8 Notes Higher Ionization Energies 59 Higher Ionization Energies 60 .
but the trend is not as smooth as for ionization energy and size. and increases from left to right.Chapter 8 Notes Electron Affinity • Electron Affinity (Eea) — the energy change accompanying the addition of electrons to 1 mole of atoms in the gas phase: M(g) + e-(g) → M-(g). • In general. ΔH° = Eea (usually < 0) • Electron affinity is usually a negative energy value (an exothermic process).16 62 . MOV: Periodic Trends Electron Affinity 61 Electron Affinity Figure 8. the greater the tendency of the atom to accept an electron and the more stable the resulting anion will be. electron affinity decreases as we move down a group. • The more negative the electron affinity. energy is usually released when an electron is added to a neutral atom.
are often shiny. 63 Trends in Metallic Character Figure 8. making electrons more likely to be lost. ionization energy decreases. Therefore.Chapter 8 Notes Trends in Metallic Character • Metals are good conductors of heat and electricity.17 64 . their physical states vary from solid to gas. ionization energy increases and electron affinity becomes more negative. • Nonmetals are poor conductors of heat and electricity. they are malleable and ductile. • As we move down a group. • Moving from left to right across a period. metallic character decreases as we move from left to right across a period. metallic character increases as we move down a group. and they tend to gain electrons in chemical reactions. Therefore. and easily lose electrons in chemical reactions.
Chapter 8 Notes Trends in Metallic Character Figure 8.18 65 Summary of the Periodic Trends 66 .
Which atom has the larger IE: O or Cl? 20.Chapter 8 Notes Examples: Predicting Periodic Trends 16. Sr. Which atom has the larger IE: As or Sb? 18. Rb? 67 Examples: Predicting Periodic Trends 21. Which atom has the larger IE: Al or S? 17. Be. Which element is more metallic: Sn or Te? 24. Which element is more metallic: Ge or In? 68 . Arrange the following in order of increasing IE: F. Which atom has the largest IE: Na. Which has the larger electron affinity. O or F? 23. 22. Cl. S. Which atom has the larger IE: N or Si 19.
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