AP Chemistry Chapter 7 Periodic Properties of the Elements

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Chapter 7. Periodic Properties of the Elements

Read Sec. 7.1 Development of the Periodic Table – read on your own

7.2 Effective Nuclear Charge– see your textbook for the details, and diagrams.

NOTE: You are welcome to use the shielding effect, rather than or in addition to “effective nuclear charge” to explain the trends in the periodic table. You need to be explicit about the components of the shielding effect. The terms “shielding effect” or “effective nuclear charge” are not sufficient as the total explanation when comparing properties of elements in the periodic table.

IMPORTANT: Do the POGILs before completing the sample and practice exercises in this packet. The concept of Coulombic attractions underpins periodic trends, and intermolecular forces (spring semester). • Effective nuclear charge = the net positive charge experienced by an electron. For the most part, we are

going to focus on the effective nuclear charge on valence electrons. • Three components affect the attraction of an electron to the nucleus:

1. attraction of the nucleus: the charge of the nucleus (# protons) 2. repulsion by the inner-shell electrons (= shield or screen) = shielding/screening effect 3. distance from the nucleus (Coulombic effect) – attraction of opposite charges decreases with the inverse

square root of the distance between them • As the average number of screening electrons (S) increases (see #2 above), the effective nuclear charge (Zeff)

decreases.

Zeff = Z – S • As the distance from the nucleus increases, S increases and Zeff decreases.

• S is called the screening constant which represents the portion of the nuclear charge that is screened from the valence electron by other electrons in the atom.

• The value of S is usually close to the number of core electrons in an atom.

7.3 Sizes of Atoms and Ions

• The apparent radius = the closest distances separating the nuclei during collisions. • =s the nonbonding radius, also called van der Waals radii. • In bonded molecules, bonding atomic radius = the distance between the two nuclei • It is shorter than the nonbonding radius (overlapping . • If the two atoms which make up the molecule are the same, then half the bond distance is called the

covalent radius of the atom.

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Figure 7.7

Sample Exercise 7.1 (p. 264) Natural gas used in home heating and cooking is odorless. Because natural gas leaks pose the danger of explosion or suffocation, various smelly substances are added to the gas to allow detection of a leak. One such substance is methyl mercaptan, CH3SH, whose structure is shown below. Use Figure 7.7 to predict the lengths of the C-S, C-H, and S-H bonds in this molecule.

Practice Exercise 1 (7.1)

Hypothetical elements X and Y form a molecule XY2, in which both Y atoms are bonded to atom X (and not to each other). The X-X distance in the elemental form of X is 2.04 Å, and the Y-Y distance in elemental Y is 1.68 Å. What would you predict for the X-Y distance in the XY2 molecule?

a) 0.84 Å b) 1.02 Å c) 1.86 Å d) 2.70 Å e) 3.72 Å

Practice Exercise 2 (7.1)

Using Figure 7.7, predict which will be greater, the P-Br bond length in PBr3 or the As-Cl bond length in AsCl3.

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Periodic Trends in Atomic Radii Bonding atomic radius tends to • ↓ from left to right across a period and • ↑ from top to bottom • Two factors at work: • The principal quantum number, n, shielding effect and • Zeff. • Down a group: distance of the outermost electron from the nucleus becomes larger. larger radius • Across the periodic table: same shielding effect, with ↑ nuclear charge ↑ attraction between the

nucleus and the outermost electrons pulls the electrons in tighter ↓ atomic radius

Sample Exercise 7.2 (p. 265) Referring to a periodic table, arrange (as much as possible) the following atoms in order of increasing size: 15P, 16S, 33As, 34Se. (Atomic numbers are given for the elements to help you locate them quickly in the periodic table.)

Practice Exercise 1 (7.2)

By referring to the periodic table, but not to Figure 7.7, place the following atoms in order of increasing bonding atomic radius: N, O, P, Ge.

a) N < O < P < Ge b) P < N < O < Ge c) O < N < Ge < P d) O < N < P < Ge e) N < P < Ge < O

Practice Exercise 2 (7.2) Arrange the following atoms in order of increasing atomic radius: 11Na, 4Be, 12Mg.

Periodic Trends in Ionic Radii

• Cations are smaller than their parent atoms, due to: • removal of electrons from outermost principal energy level • ↑ effective nuclear charge • Anions are larger than their parent atoms. • Extra electrons in outermost principal energy level • ↑ electron-electron repulsion • For ions with the same charge (in the same group), ionic size ↑ down a group. • All the members of an isoelectronic series have the same number of electrons. • As nuclear charge ↑ in an isoelectronic series the ions become smaller:

O2– > F– > Na+ > Mg2+ > Al3+

AP Chemistry Chapter 7 Periodic Properties of the Elements

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Sample Exercise 7.3 (p. 265)

Arrange these atoms and ions in order of decreasing size: Mg2+, Ca2+, Ca.

Practice Exercise 1 (7.3)

Arrange the following atoms and ions in order of increasing ionic radius: F, S2-, Cl, and Se2-.

a) F < S2- < Cl < Se2- b) F < Cl < S2- < Se2- c) F < S2- < Se2- < Cl d) Cl < F < Se2- < S2- e) S2- < F < Se2- < Cl

Practice Exercise 2 (7.3)

Which of the following atoms and ions is largest: S2-, S, O2-?

Sample Exercise 7.4 (p. 267)

Arrange the ions S2-, Cl-, K+ and Ca2+ in order of decreasing size.

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Practice Exercise 1 (7.4)

Arrange the following atoms and ions in order of increasing ionic radius: Br-, Rb+, Se2-, Sr2+, Te2-. a) Sr2+ < Rb+ < Br-- < Se2- < Te2- b) Br- < Sr2+ < Se2- < Te2- < Rb+ c) Rb+ < Sr2+ < Se2- < Te2- < Br- d) Rb+ < Br- < Sr2+ < Se2- < Te2- e) Sr2+ < Rb+ < Br- < Te2 < Se2-

Practice Exercise 2 (7.4) Which of the following ions is largest? Rb+, Sr2+, or Y3+?

7.4 Ionization Energy

• The ionization energy of an atom or ion = the minimum energy required to remove an electron from the

ground state of the isolated gaseous atom or ion. • The first ionization energy, I1, is the amount of energy required to remove an electron from a gaseous atom:

Na(g) Na+(g) + e– • The second ionization energy, I2, is the energy required to remove the second electron from a gaseous ion:

Na+(g) Na2+(g) + e– • The larger the ionization energy, the more difficult it is to remove the electron. • There is a sharp increase in ionization energy when a core electron is removed.

Variations in Successive Ionization Energies • Ionization energies for an element increase in magnitude as successive electrons are removed. • As each successive electron is removed, more energy is required to pull an electron away from an

increasingly more positive ion. • A sharp increase in ionization energy occurs when an inner-shell electron is removed.

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Sample Exercise 7.5 (p. 269) Three elements are indicated in the periodic table below. Based on their locations, predict the one with the largest second ionization energy.

Practice Exercise 1 (7.5)

The third ionization energy of bromine is the energy required for which of the following processes?

a) Br(g) Br+(g) + e-

b) Br+(g) Br2+

(g) + e- c) Br(g) Br2+

(g) + 2 e- d) Br(g) Br3+

(g) + 3 e- e) Br2+

(g) Br3+(g) + e-

Practice Exercise 2 (7.5)

Which will have the greater third ionization energy, Ca or S?

Periodic Trends in First Ionization Energies

• Ionization energy ↓ down a group. • Bigger atom easier to remove an electron from the outermost principal energy level • The representative elements exhibit a larger range of values for I1 than transition metals. • Ionization energy generally ↑ across a period. • As we move across a period, Zeff increases, making it more difficult to remove an electron. • Two exceptions: removing the first p electron and removing the fourth p electron. • The s electrons are more effective at shielding than p electrons. So, forming the s2p0 configuration is

more favorable. • When a second electron is placed in a p orbital, the electron-electron repulsion increases. When this

electron is removed, the resulting s2p3 configuration is more stable than the starting s2p4 configuration. Therefore, there is a decrease in ionization energy.

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Sample Exercise 7.6 (p. 270) Referring to a periodic table, arrange the following atoms in order of increasing first ionization energy: Ne, Na, P, Ar, K.

Practice Exercise 1 (7.6)

Consider the following statements about first ionization energies: (i) Because the effective nuclear charge for Mg is greater than that for Be, the first ionization energy of

Mg is greater than that of Be. (ii) The first ionization energy of O is less than that of N bcause in O we must pair electrons in the 2p

orbitals. (iii) The first ionization energy of Ar is less than that of Ne because a 3p electron in Ar is farther from the

nucleus than a 2p electron in Ne.

Which of the statements (i), (ii), and (iii) is or are true? a) Only one statement is true. b) Statements (i) and (ii) are true. c) Statements (i) and (iii) are true. d) Statements (ii) and (iii) are true. e) All three statements are true.

First ionization energy versus atomic number.

The red dots mark the beginning of a period (alkali metals), the blue dots mark the end of a period (noble gases), and the black dots indicate other representative elements. Green dots are used for the transition metals.

Trends in first ionization energy

First ionization energies for the s- and p-block elements in the first six periods. The ionization energy generally increases from left to right and decreases from top to bottom. The ionization energy of astatine has not been determined.

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Practice Exercise 2 (7.6)

Which hs the lowest first ionization energy, B, Al, C, or Si? Which has the highest first ionization energy?

Electron Configurations of Ions • derived from the electron configurations of elements with the required number of electrons added or

removed from the most accessible orbital. • Li: [He]2s1 Li+: [He] • F: [He]2s22p5 F-: [He]2s22p6 = [Ar] • Transition metals tend to lose the valence shell electrons first and then as many d electrons as are required to

reach the desired charge on the ion. • Thus electrons are removed from 4s before the 3d, etc.

Sample Exercise 7.7 (p. 271)

Write the electron configuration for the

a) Ca2+ ion;

b) Co3+ ion;

c) S2- ion.

Practice Exercise 1 (7.7)

The ground state electron configuration of a Tc atom is [Kr]5s24d5. What is the electron configuration of a Tc3+ ion?

a) [Kr]4d4 b) [Kr]5s24d2 c) [Kr]5s14d3 d) [Kr]5s24d8 e) [Kr]4d10

Practice Exercise 2 (7.7) Write the electron configuration for the

a) Ga3+ ion;

b) Cr3+ ion;

c) Br- ion.

AP Chemistry Chapter 7 Periodic Properties of the Elements

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7.6 Metal, Nonmetals and Metalloids

• Metallic character refers to the extent to which the element exhibits the physical and chemical properties

of metals. • Metallic character ↑ down a group. • Metallic character ↓ from left to right across a period.

Metals

• shiny, lustrous, malleable, ductile, solids at room temperature (exception: mercury is liquid at room temperature; gallium and cesium melt just above room temperature), very high melting temperatures. • low ionization energies and tend to form cations easily. • tend to be oxidized when they react. • Compounds of metals with nonmetals tend to be ionic substances. • Metal oxides form basic ionic solids. • Most metal oxides are basic:

Metal oxide + water metal hydroxide Na2O(s) + H2O(l) 2NaOH(aq)

• Metal oxides are able to react with acids to form salts and water: Metal oxide + acid salt + water

MgO(s) + 2HCl(aq) MgCl2(aq) + H2O(l)

Sample Exercise 7.8 (p. 276)

a) Would you expect scandium oxide to be a solid, liquid, or gas at room temperature?

b) Write the balanced chemical equation for the reaction of scandium oxide with nitric acid.

Practice Exercise 1 (7.8)

Suppose that a metal oxide of formula M2O3 were soluble in water. What would be the major product or products of dissolving the substance in water?

a) MH3(aq) + O2(g) b) M(s) + H2(g) + O2(g) c) M3+

(aq) + H2O2(aq) d) M(OH)2(aq) e) M(OH)3(aq)

Practice Exercise 2 (7.8)

Write the balanced chemical equation for the reaction between copper(II) oxide and sulfuric acid.

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Nonmetals

• more diverse in their behavior than metals. • nonlustrous, poor conductors of heat and electricity, lower melting points than metals. • Seven nonmetallic elements exist as diatomic molecules under ordinary conditions: • H2(g), N2(g), O2(g), F2(g), Cl2(g), Br2(l), I2(s) • When nonmetals react with metals, nonmetals tend to gain electrons:

Metal + nonmetal salt 2Al(s) + 3Br2(l) 2AlBr3 (s)

• Compounds composed entirely of nonmetals are molecular substances. • Most nonmetal oxides are acidic: Nonmetal oxide + water acid

P4O10(s) + 6H2O(l) 4H3PO4(aq) CO2(g) + H2O(l) H2CO3(aq)

• Nonmetal oxides react with bases to form salts and water: Nonmetal oxide + base salt + water CO2(g) + 2NaOH(aq) Na2CO3(aq) + H2O(l)

Sample Exercise 7.9 (p. 277)

Write the balanced chemical equations for the reactions of solid selenium dioxide with

a) water

b) aqueous sodium hydroxide

Practice Exercise 1 (7.9)

Consider the following oxides: SO2, Y2O3, MgO, Cl2O, N2O5. How many are expected to form acidic solutions in water?

a) 1 b) 2 c) 3 d) 4 e) 5

Practice Exercise 2 (7.9)

Write the balanced chemical equation for the reaction of solid tetraphosphorus hexoxide with water.

Metalloids • properties intermediate between those of metals and nonmetals, e.g. Si has a metallic luster but it is brittle.

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7.7 Group Trends for the Active Metals • The alkali metals (group 1A) and the alkaline earth metals (group 2A) are often called the active metals. Group 1A: The Alkali Metals

• soft • Their chemistry is dominated by the loss of their single s electron: M M+ + e– • Reactivity ↑ move down the group. • react with hydrogen to form hydrides. • In hydrides, the hydrogen is present as H–, called the hydride ion: 2M(s) + H2(g) 2MH(s) • react with water to form MOH and hydrogen gas: 2M(s) + 2H2O(l) 2MOH(aq) + H2(g) • produce different oxides when reacting with O2: • 4Li(s) + O2(g) 2Li2O(s) (oxide) • 2Na(s) + O2 (g) Na2O2(s) (peroxide) • K(s) + O2 (g) KO2(s) (superoxide) • emit characteristic colors when placed in a high-temperature flame: see list of colors in “memorize” sheet • The s electron is excited by the flame and emits energy when it returns to the ground state. • The Na line occurs at 589 nm (yellow), characteristic of the 3p 3s transition. • The Li line is crimson red (2p 2s transition). • The K line is lilac (4p 4s transition).

Sample Exercise 7.10 (p. 280) Write balanced chemical equations that predict the reactions of cesium metal with

a) Cl2(g)

b) H2O(l)

c) H2(g)

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Practice Exercise 1 (7.10)

Consider the following three statements about the reactivity of an alkali metal M with oxygen gas:

(i) Based on their positions in the periodic table, the expected product is the ionic oxide M2O. (ii) Some of the alkali metals produce metal peroxides or metal superoxides when they react with oxygen. (iii) When dissolved in water, an alkali metal oxide produces a basic solution.

Which of the statements (i), (ii), and (iii) is or are true?

a) Only one statement is true. b) Statements (i) and (ii) are true. c) Statements (i) and (iii) are true. d) Statements (ii) and (iii) are true. e) All three statements are true.

Practice Exercise 2 (7.10)

Write a balanced chemical equation that predicts the products of the reaction between potassium metal and elemental sulfur.

Group 2A: The Alkaline Earth Metals

• harder and denser than the alkali metals. • Their chemistry is dominated by the loss of two s electrons: M M2+ + 2e–

Mg(s) + Cl2(g) MgCl2(s) 2Mg(s) + O2(g) 2MgO(s)

• Reactivity ↑ down the group. • Be does not react with water. • Mg will only react with steam. • Ca and the elements below it react with water at room temperature as follows:

Ca(s) + 2H2O(l) Ca(OH)2(aq) + H2(g)

7.8 Group Trends for Selected Nonmetals Hydrogen • Hydrogen is a unique element. • It most often occurs as a colorless diatomic gas, H2. • Reactions between hydrogen and nonmetals can be very exothermic:

2H2(g) + 2O2(g) 2H2O(l) ∆Ho = –571.7 kJ

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• It can either gain another electron to form the hydride ion, H–, or lose its electron to become H+: 2Na(s) + H2(g) 2NaH(s) 2H2(g) + O2(g) 2H2O(l)

• H+ is a proton. • The aqueous chemistry of hydrogen is dominated by H+(aq).

Group 6A: The Oxygen Group • metallic character increases down the group: O2 is a gas, Te is a metalloid, Po is a metal. • two important forms of oxygen: O2 and ozone, O3., which are allotropes • Ozone can be prepared from oxygen: 3O2(g) 2O3(g) ∆H = +284.6 kJ • Ozone is pungent and toxic. • Oxygen (or dioxygen, O2) is a potent oxidizing agent since the O2– ion has a noble gas configuration. • There are two oxidation states for oxygen: –2 (e.g., H2O) and –1 (e.g., H2O2). • Sulfur is another important member of this group. • The most common form of sulfur is yellow S8. • Sulfur tends to form S2– in compounds (sulfides).

Group 7A: The Halogens

• halogens ("salt formers"). • The chemistry is dominated by gaining an electron to form an anion: X2 + 2e– 2X– • Fluorine is one of the most reactive substances known:

2F2(g) + 2H2O(l) 4HF(aq) + O2(g) ∆H = –758.9 kJ • All halogens consist of diatomic molecules, X2. • Chlorine is the most industrially useful halogen. • The reaction between chorine and water produces hypochlorous acid (HOCl), which is used to disinfect

swimming pool water: Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)

• Halogens react with hydrogen to form gaseous hydrogen halide compounds: H2(g) + X2 2HX(g) • Hydrogen compounds of the halogens are all strong acids with the exception of HF.

Elemental sulfur. At room temperature, the most common allotropic form of sulfur is an eight-member ring, S8.

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Group 8A: The Noble Gases

• noble gases. • nonmetals and monoatomic. • notoriously unreactive because they have completely filled s and p subshells.

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Sample Integrative Exercise 7 (p. 287)

The element bismuth (Bi, atomic number 83) is the heaviest member of group 5A. A salt of the element, bismuth subsalicylate, is the active ingredient in Pepto-Bismol, an over-the-counter medication for gastric distress. 1. The covalent atomic radii of thallium (Tl) and lead (Pb) are 1.48 Å and 1.47 Å, respectively. Using these values what might you expect for the bonding atomic radius of bismuth? 2. What accounts for the general increase in atomic radius going down the group 5A elements? 3. Another major use of bismuth has been as an ingredient in low-melting metal alloys, such as those used in fire sprinkler systems and in typesetting. The element itself is a brittle white crystalline solid. How do these characteristics fit with the fact that bismuth is in the same periodic group with such nonmetallic elements as nitrogen and phosphorus? 4. Bi2O3 is a basic oxide. Write a balanced equation for its reaction with dilute nitric acid. If 6.77 g of Bi2O3 is dissolved in dilute acidic solution to make up 500 mL of solution, what is the molarity of the Bi3+ ion? 5. 209Bi is the heaviest stable isotope of any element. How many protons and neutrons are present in this nucleus?

6. The density of Bi at 25oC is 9.808 g/cm3. How many Bi atoms are present in a cube of the element that is 5.00 cm on each edge? How many moles of the element are present?