Principles of General Chemistry, 2nd ed. By M. Silberberg Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.

Lecture Goals
1. More About the Periodic Table Periodic Properties of the Elements 2. Atomic Radii 3. Ionic Radii 4. Ionization Energy 5. Electron Affinity 6. Electronegativity

Chemical Periodicity

Periodic Table
Arranged by Dmitri Mendeliv, a Russian Chemist Establish a classification scheme of the elements based on their electron configurations. Column: FAMILY or GROUP Row: PERIOD Certain characteristics are shared by each families & periods.

More About the Periodic Table

Representative Elements
are the elements in A groups on periodic chart.

will have their last electron in an outer s or p orbital have fairly regular variations in their properties

More About the Periodic Table

d-Transition Elements
on periodic chart in B groups

More About the Periodic Table

f - transition metals
sometimes called inner transition metals

each metal has d electrons.

ns (n-1)d configurations

make the transition from metals to nonmetals exhibit smaller variations from row-to-row than the representative elements
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have electrons in f orbitals & are being added two shells below the valence shell very slight variations of properties from one element to another.

The Periodic Table: Metals, Nonmetals, and Metalloids

1869 - Mendeleev & Meyer
The properties of the elements are periodic functions of their atomic numbers.

The Periodic Table: Metals, Nonmetals, and Metalloids

Groups or families
Vertical group of elements on periodic table Similar chemical and physical properties

The Periodic Table: Metals, Nonmetals, and Metalloids

Period
Horizontal group of elements on periodic table Transition from metals to nonmetals

Metals
Some chemical properties
1. 2. 3. 4. Outer shells contain few electrons Form cations by losing electrons Form ionic compounds with nonmetals Solid state characterized by metallic bonding

The Alkali Metals

Group IA metals: Li, Na, K, Rb, Cs, Fr example of a trend - their reactions with water
are all shiny, soft, silvery, highly reactive metals at standard T and P, and readily lose their outermost electron to form cations (+1)

The Alkaline Earth Metals

Group IIA metals - Be, Mg, Ca, Sr, Ba, Ra they are all shiny, silverywhite, somewhat reactive metals at standard temperature and pressure and readily lose their two outermost electrons to form cations with charge (+2)

Non Metals
Some chemical properties
1. 2. 3. 4. Outer shells contain four or more electrons Form anions by gaining electrons Form ionic compounds with metals and covalent compounds with other nonmetals Form covalently bonded molecules; noble gases are monatomic

Chalcogens
Group VIA nonmetals - O, S, Se, Te electronegative elements are strongly associated with metal-bearing minerals, where they have formed water-insoluble compounds with the metals in the ores

Halogens
Group VIIA nonmetals - F, Cl, Br, I, At the only periodic table group which contains elements in all three familiar states of matter at standard temperature and pressure

Noble, Inert or Rare Gases

Group VIIIA nonmetals - He, Ne, Ar, Kr, Xe, Rn have completely filled electron shells

The Periodic Table: Metals, Nonmetals, and Metalloids

Metals are to the left of stair step.
~ 80% of the elements

The Periodic Table: Metals, Nonmetals, and Metalloids

Non metals are to the right of stair step.
~ 20% of the elements

Best metals are on the far left of the table.

Best metals are on the far right of the table.

The Periodic Table: Metals, Nonmetals, and Metalloids

The Periodic Table: Metals, Nonmetals, and Metalloids

Metalloids have one side of the box on the stair step.

Periodic Properties of the Elements

By definition, periodic is appearing or recurring at regular intervals . to be discussed: Metallic Character Atomic Radii Ionic Radii Ionization Energy Electron Affinity Electronegativity
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Metallic Character
decreases

Atomic Radii
describes the relative sizes of atoms. decreases

Atomic Radii

increases

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increases

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Atomic Radii
increases (down a group) noted by the increase the number of shells occupied by e-s decrease (across a period) due to nuclear charge effect (moving across a period, each element has an increased nuclear charge and the electrons are going into the same shell (2s and 2p or 3s and 3p) shielding or screening effect - effective nuclear charge, Zeff, experienced by an electron is less than the actual nuclear charge, Z. - the inner electrons block the nuclear charges effect on the outer electrons.
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Ionic Radii
decreases

increases

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Ionic Radii
Cations (positive ions) are always smaller than their respective neutral atoms.
Element Atomic Radius () Ion Ionic Radius () Na 1.86 Na+ 1.16 Mg 1.60 Mg2+ 0.85 Al 1.43 Al3+ 0.68

Ionic Radii
Anions (negative ions) are always larger than their neutral atoms.
Element Atomic Radius() Ion Ionic Radius() N 0.75 N31.71 O 0.73 O21.26 F 0.72 F11.19

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Ionic Radii
cation (positive ions) radii decrease from left to right across a period. increasing nuclear charge attracts the electrons and decreases the radius.
Ion Ionic Radii() Rb+ 1.66 Sr2+ 1.32 In3+ 0.94
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Ionic Radii
anion (negative ions) radii decrease from left to right across a period. increasing electron numbers in highly charged ions cause the electrons to repel and increase the ionic radius.
Ion Ionic Radii() N31.71 O21.26 F1.19
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Atomic Radii and Ionic Radii

Arrange these elements based on their atomic radii. Arrange these elements based on their ionic radii. Ga, K, Ca Se, S, O, Te Ga3+ < Ca2+ < K+ O < S < Se < Te Cl, Se, Br, S P, Cl, S, Si Cl- < S2- < Br1- < Se2-

Ionization Energy
1st ionization energy (IE1)
the minimum amount of energy required to remove the most loosely bound electron from an isolated gaseous atom to form a 1+ ion.

Symbolically: Atom(g) + energy Mg(g) + 738kJ/mol

ion+(g) + eMg+ + e32

Cl < S < P < Si

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Ionization Energy
2nd ionization energy (IE2)
the amount of energy required to remove the second electron from a gaseous 1+ ion

Ionization Energy
1. IE2 > IE1 It always takes more energy to remove a second electron from an ion than from a neutral atom. 2. IE1 generally increases moving across a period. Important exceptions at Be & Mg, N & P, etc. due to filled and half-filled subshells. 3. IE1 generally decreases moving down a family. IE1 for Li > IE1 for Na, etc.
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Symbolically:

ion+ Mg+

+ energy

ion2+

e-

+ 1451 kJ/mol

Mg2+ + e-

Atoms can have 3rd (IE3), 4th (IE4), etc. ionization energies.

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Ionization Energy
increases decreases

Ionization Energy

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Ionization Energy
Group and element IE1 (kJ/mol) IE2 (kJ/mol) IE3 (kJ/mol) IE4 (kJ/mol) (IA) Na 496 4562 6912 9540 (IIA) Mg 738 1451 7733 10,550 (IIIA) Al 578 1817 2745 11,580 (IVA) Si 786 1577 3232 4356
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Ionization Energy
The reason Na forms Na+ and not Na2+ is that the energy difference between IE1 and IE2 is so large.
Requires more than 9 times more energy to remove the second electron than the first one.

The same trend is persistent throughout the series.

Thus Mg forms Mg2+ and not Mg3+.

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Ionization Energy
What charge ion would be expected for an element that has these ionization energies?
IE1 (kJ/mol) IE2 (kJ/mol) IE3 (kJ/mol) IE4 (kJ/mol) IE5 (kJ/mol) IE6 (kJ/mol) IE7 (kJ/mol) IE8 (kJ/mol) 1680 3370 6050 8410 11020 15160 17870 92040
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Ionization Energy
Arrange these elements based on their first ionization energies. Sr, Be, Ca, Mg Sr < Ca < Mg < Be Al, Cl, Na, P Na < Al < P < Cl B, O, Be, N B < Be < O < N
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Electron Affinity
is the amount of energy absorbed when an electron is added to an isolated gaseous atom to form an ion with a 1- charge. is a measure of an atoms ability to form negative ions. Symbolically: atom(g) + e- + EA ion-(g)

Electron Affinity
increases

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decreases

Electron Affinity
Two examples of electron affinity values: Mg(g) + + EA EA = +231 kJ/mol eMg(g)

Electron Affinity
e-

Br(g) + Br (g) + EA EA = -323 kJ/mol

If electron affinity > 0, energy is absorbed; if < 0, energy is released.

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Electronegativity
is a measure of the relative tendency of an atom to attract electrons to itself when is measured on the Pauling scale
Fluorine is the most electronegative element. Cesium and francium are the least electronegative elements.

Electronegativity
increases

decreases

chemically combined with another element

* for representative elements

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Electronegativity

Electronegativity
Arrange these elements based on their electronegativity.

Se, Ge, Br, As Ge < As < Se < Br Be, Mg, Ca, Ba Ba < Ca < Mg < Be
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In summary

Value has a value only if Chemical its value is valued.

Brian G. Dyson President and CEO, Coca-Cola Enterprises

Periodicity

questions?
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