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Electron Structure of the Atom:

Periodic Properties
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Periodic Properties of Atoms Atomic size and ionic size Ionization Energy Electron affinity Metallic Property Relative reactivity

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Atomic Size
Atomic size is usually reported as atomic radius, estimated as one-half the distance between the centers of two bonded atoms.

Figure 7.29
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Atomic Size
Defining metallic and covalent radii

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Atomic Radii of the Main-Group Elements

Atomic Size

Figure 7.30
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Worksheet #2-9
Atomic Sizes and the Periodic Table I:
Graph the following data and then make a conclusion regarding atomic radius of the element and its position on the periodic table. Let the x-axis be the atomic number.
Element
Lithium Sodium Potassium Rubidium Cesium Francium

Atomic Size
152 pm 186 227 248 265 270

Element
Beryllium Magnesium Calcium Strontium Barium

Atomic Size
112 pm 160 197 215 222

Element
Fluorine Chlorine Bromine Iodine astatine

Atomic Size
72 pm 100 114 133 140

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Answers Worksheet #2-9


atomic size 300 250 200 150 100 50 0 0

Family 1A
19 3 11

atomic size 250 87 200 150 100 4

Family 2A
20
11 38 56

37

55

50
0 20 40 60 Axis Title 80 100

20

40

60

atomic 160size 140 120 100 80 60 40 20 0 0

Family 7A
53 35 85

17
9

Conclusion: Top to bottom, atomic radius?

20

40

60

80

100

Worksheet #2-10
Atomic Sizes and the Periodic Table II:
Graph the following data and then make a conclusion regarding atomic radius of the element and its position on the periodic table. Let the x-axis be the atomic number.
Element
Lithium Beryllium Boron Carbon nitrogen Oxygen Fluorine neon

Atomic Size
152 pm 112 85 77 75 73 72 71

Element
Sodium Magnesium Aluminium Silicon phosphorus Sulphur Chlrorine Argon

Atomic Size
186 pm 160 143 118 110 103 100 98

Element
Potassium Calcium Gallium Germanium Arsenic Selenium Bromine krypton

Atomic Size
227 pm 197 135 122 120 119 114 112

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Answers Worksheet #2-10


Period 2
200 150 100 50 0 0 2 4 6 8 10 12 50 0 10 12 14 16 18 20 200 150 100

Period 3

Period 4
250 200 150 100 50 0 19 24 29 34 39

Conclusion: Left to right, atomic radius?

Atomic Size
Periodicity of atomic radius

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Atomic Size
Atomic size increases down a group because valence electrons are in orbitals that extend further from the nucleus. Atomic size decreases from left to right because electrons are held closer to the nucleus by the increasingly greater charge of the nucleus.
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Figure 7.31

Sample Problem
Which has the larger atomic radii?
a) Mg or Ca b) O or F c) S or F Ca O S

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Worksheet #2-11a
PROBLEM:

Arrange each set in order of increasing atomic size:


a) Rb, K, Cs

b) C, O, Be
c) Cl, K, S

d) Mg, K, Ca

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Answers Worksheet #2-11a

Answers: a) K < Rb < Cs b) O < C < Be c) Cl < S < K d) Mg < Ca < K

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Ionic Size
Depicting ionic radius.

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Ionic Radii for the Main-Group Ions

Ionic Size

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Ionic Size and Atomic Size

Ionic vs. atomic radius.


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Ionic Size
Cations are smaller than their neutral atoms. (why?) Anions are larger than their neutral atoms. (why?)

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Ionic Size
Conclusions:
1. Ionic size = family and period? 2. Ionic size and atomic size = cations? Anions?

Trends in Ionic Size


The general trend for ionic size (or radius) is
- Ionic size increases from top to bottom in the periodic table. Ions : Atom Size > Cation Size Atom Size < Anion Size

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Ionic Size: Isoelectronic Ions

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Ionic Size
For any iso-electronic series, as the number of protons increases, the ion size decreases. For cations, as the charge increases, the ionic size decreases.

For anions, as the charge increases (becomes more negative), the ionic size increases.

Worksheet #2-11b
PROBLEM:

Rank the ions in each set in order of increasing size and explain your ranking: (a) Li+, K+, Na+

(b) Se2-, Rb+, Br (c) O2-, F-, N3-

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Answers Worksheet #2-11b


Answers: a) Li+ < Na+ < K+
b) Rb+ < Br_ < Se2c) F- < O2- < N3-

Ionization energy and electron affinity


Main-group ions and the noble gas configurations.

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Ionization Energy
Ionization energy (IE) is a measure of the energy required to remove a valence electron from a gaseous atom.
Mg(g) Mg+(g) + 1e IE = 738 kJ/mol

In general, atoms with low ionization energies do not bind their electrons very tightly, and are, therefore, very reactive.
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Ionization Energy

Figure 7.26
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Ionization Energy
Periodicity of first ionization energy (IE1)

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Ionization Energy

Ionization Energy
Ionization energy increases up a group because the valence electrons become increasingly closer to the nucleus. Ionization energy increases from left to right in a period because the valence electrons are increasingly held more tightly by the nucleus, which is increasing in the number of protons.
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Sample Problem
Which has the greater ionization energy?
a) Mg or Ca b) O or F c) S or F Mg F F

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Worksheet #2-12
PROBLEM:

Arrange each set of atoms in order of increasing IE1: a) Sr, Ca, Ba b) N, B, Ne c) Br, Rb, Se d) As, Sb, Sn

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Answers Worksheet #2-12

a) Ba < Sr < Ca
b) B <N < Ne c) Rb < Se < Br d) Sn < Sb < As

Successive Ionization Energies


2nd Ionization energy (IE2)
Mg+(g) Mg2+(g) + 1e IE2 = 1451 kJ/mol

3rd Ionization energy (IE3) Mg2+(g) Mg3+(g) + 1e

IE3 = 7733 kJ/mol

Generally, IE3 > IE2 > IE1


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Successive Ionization Energies

The first three ionization energies of beryllium (in MJ/mol).

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Successive Ionization Energies

What do these values tell us about the stability of core (inner) electrons?
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Sample Problem
PROBLEM:

Write the full electron configuration of the Period 2 element with the following succesive IEs (in kJ/mol):
IE1 801 IE2 2427 IE3 3659 IE4 25022 IE5 32822

Answer: 1s2 2s2 2p1 (boron, B)

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Electron Affinity
Electron Affinity
The energy change accompanying the addition of one mole of electrons to one mole of gaseous atoms or ions.

Atom(g) + e- ion-(g)

E = EA1

Cl (g) + e- Cl- (g)

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


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Electron Affinity
Electron affinities of the main-group elements.

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Electron Affinity

Trends?

Metallic Property

Figure 2.18

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Metallic Property

Figure 2.20

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Metallic Property
Trends in metallic behavior.

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Sample Problem
PROBLEM:

Which element would you expect to be more metallic? a) Ca or Rb

b) Mg or Ra
c) Br or I

Answer: a) Rb b) Ra c) I

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Chemical Reactivity
From the activity series we see that the most active metals are those in Groups IA and IIA. The more active the metal, the more easily it loses electrons to form ions.

Figure 7.24

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Chemical Reactivity
The alkali metals form +1 ions since they all have 1 valence electron.
Oxides of the alkali metals: Li2O, Na2O, K2O, Rb2O, Cs2O

The alkaline earth metals form +2 ions since they all have 2 valence electrons.
Oxides of the alkaline earth metals: BeO, MgO, CaO, SrO, BaO
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Sample Problem
Explain the changes in reactivity of these metals in terms of ionization energy:
Figure 7.25

Li

Na K Rb Cs 2M(s) + 2H2O(l) 2MOH(aq) + H2(g)

Ionization energy decreases down the group (from Li to Cs), making the elements increasingly reactive.
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Summary: Trends

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Worksheet # 2-13
Given the following elements: Rb, K and Ga Arrange the elements according increasing a) Atomic size b) Ionization energy c) Metallic property

Worksheet # 2-13: Answers


Given the following elements: Rb, K and Ga Arrange the elements according to increasing a) Atomic size: Ga < K < Rb b) Ionization energy: Rb < K < Ga c) Metallic property: Ga < K < Rb

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