Ch. 7 Chemical Periodicity

E
Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten 
Periodic 
Properties 
of the 
Elements 
Chemistry, The Central Science, 10th edition 
Chapter 7 
Periodic Properties 
of the Elements 
John D. Bookstaver 
St. Charles Community College 
St. Peters, MO 
ã 2006, Prentice Hall, Inc.
Development of Periodic Table 
• Elements in the 
same group 
generally have 
similar chemical 
properties. 
• Properties are not 
identical, however. 
Periodic 
Properties 
of the 
Elements
Development of Periodic Table 
Dmitri 
Mendeleev and 
Lothar Meyer 
independently 
came to the 
same conclusion 
about how 
elements should 
be grouped. 
Periodic 
Properties 
of the 
Elements
Development of Periodic Table 
Periodic 
Properties 
of the 
Elements 
Mendeleev, for instance, predicted the 
discovery of germanium (which he called eka-silicon) 
as an element with an atomic weight 
between that of zinc and arsenic, but with 
chemical properties similar to those of silicon.
Periodic 
Properties 
of the 
Elements 
Periodic Trends 
• In this chapter, we will rationalize 
observed trends in 
Sizes of atoms and ions. 
Ionization energy. 
Electron affinity.
Periodic 
Properties 
of the 
Elements 
Effective Nuclear Charge 
• In a many-electron 
atom, electrons are 
both attracted to the 
nucleus and repelled 
by other electrons. 
• The nuclear charge 
that an electron 
experiences depends 
on both factors.
Periodic 
Properties 
of the 
Elements 
Effective Nuclear Charge 
The effective nuclear 
charge, Zeff, is found this 
way: 
Zeff = Z − S 
where Z is the atomic 
number and S is a 
screening constant, 
usually close to the 
number of inner 
electrons.
Periodic 
Properties 
of the 
Elements 
Sizes of Atoms 
The bonding atomic 
radius is defined as 
one-half of the 
distance between 
covalently bonded 
nuclei.
Periodic 
Properties 
of the 
Elements 
Sizes of Atoms 
Bonding atomic 
radius tends to… 
…decrease from left to 
right across a row 
due to increasing Zeff. 
…increase from top to 
bottom of a column 
due to increasing value 
of n
Periodic 
Properties 
of the 
Elements 
Sizes of Ions 
• Ionic size depends 
upon: 
Nuclear charge. 
Number of 
electrons. 
Orbitals in which 
electrons reside.
Periodic 
Properties 
of the 
Elements 
Sizes of Ions 
• Cations are 
smaller than their 
parent atoms. 
The outermost 
electron is 
removed and 
repulsions are 
reduced.
Periodic 
Properties 
of the 
Elements 
Sizes of Ions 
• Anions are larger 
than their parent 
atoms. 
Electrons are 
added and 
repulsions are 
increased.
Periodic 
Properties 
of the 
Elements 
Sizes of Ions 
• Ions increase in size 
as you go down a 
column. 
Due to increasing 
value of n.
Periodic 
Properties 
of the 
Elements 
Sizes of Ions 
• In an isoelectronic series, ions have the same 
number of electrons. 
• Ionic size decreases with an increasing 
nuclear charge.
Periodic 
Properties 
of the 
Elements 
Ionization Energy 
• Amount of energy required to remove 
an electron from the ground state of a 
gaseous atom or ion. 
First ionization energy is that energy 
required to remove first electron. 
Second ionization energy is that energy 
required to remove second electron, etc.
Periodic 
Properties 
of the 
Elements 
Ionization Energy 
• It requires more energy to remove each 
successive electron. 
• When all valence electrons have been removed, 
the ionization energy takes a quantum leap.
Trends in First Ionization Energies 
• As one goes down a 
column, less energy 
is required to remove 
the first electron. 
For atoms in the same 
group, Zeff is essentially 
the same, but the 
valence electrons are 
farther from the 
nucleus. 
Periodic 
Properties 
of the 
Elements
Trends in First Ionization Energies 
• Generally, as one 
Periodic 
Properties 
of the 
Elements 
goes across a row, it 
gets harder to 
remove an electron. 
As you go from left to 
right, Zeff increases.
Trends in First Ionization Energies 
Periodic 
Properties 
of the 
Elements 
However, there are 
two apparent 
discontinuities in this 
trend.
Trends in First Ionization Energies 
• The first occurs 
between Groups IIA 
and IIIA. 
• Electron removed from 
p-orbital rather than s-orbital 
Periodic 
Properties 
of the 
Elements 
Electron farther from 
nucleus 
Small amount of 
repulsion by s 
electrons.
Trends in First Ionization Energies 
• The second occurs 
between Groups VA 
and VIA. 
Periodic 
Properties 
of the 
Elements 
Electron removed 
comes from doubly 
occupied orbital. 
Repulsion from other 
electron in orbital helps 
in its removal.
Periodic 
Properties 
of the 
Elements 
Electron Affinity 
Energy change accompanying addition of 
electron to gaseous atom: 
Cl + e− ¾¾® Cl−
Periodic 
Properties 
of the 
Elements 
Trends in Electron Affinity 
In general, electron 
affinity becomes 
more exothermic as 
you go from left to 
right across a row.
Periodic 
Properties 
of the 
Elements 
Trends in Electron Affinity 
There are 
again, 
however, two 
discontinuities 
in this trend.
Periodic 
Properties 
of the 
Elements 
Trends in Electron Affinity 
• The first occurs 
between Groups IA 
and IIA. 
Added electron must 
go in p-orbital, not s-orbital. 
Electron is farther 
from nucleus and 
feels repulsion from 
s-electrons.
Periodic 
Properties 
of the 
Elements 
Trends in Electron Affinity 
• The second occurs 
between Groups IVA 
and VA. 
Group VA has no 
empty orbitals. 
Extra electron must 
go into occupied 
orbital, creating 
repulsion.
Properties of Metal, Nonmetals, 
Periodic 
Properties 
of the 
Elements 
and Metalloids
Periodic 
Properties 
of the 
Elements 
Metals versus Nonmetals 
Differences between metals and nonmetals 
tend to revolve around these properties.
Periodic 
Properties 
of the 
Elements 
Metals versus Nonmetals 
• Metals tend to form cations. 
• Nonmetals tend to form anions.
Periodic 
Properties 
of the 
Elements 
Metals 
Tend to be lustrous, 
malleable, ductile, 
and good 
conductors of heat 
and electricity.
Periodic 
Properties 
of the 
Elements 
Metals 
• Compounds formed 
between metals and 
nonmetals tend to 
be ionic. 
• Metal oxides tend to 
be basic.
Periodic 
Properties 
of the 
Elements 
Nonmetals 
• Dull, brittle 
substances that are 
poor conductors of 
heat and electricity. 
• Tend to gain 
electrons in 
reactions with 
metals to acquire 
noble gas 
configuration.
Periodic 
Properties 
of the 
Elements 
Nonmetals 
• Substances 
containing only 
nonmetals are 
molecular 
compounds. 
• Most nonmetal 
oxides are acidic.
Periodic 
Properties 
of the 
Elements 
Metalloids 
• Have some 
characteristics of 
metals, some of 
nonmetals. 
• For instance, silicon 
looks shiny, but is 
brittle and fairly poor 
conductor.
Periodic 
Properties 
of the 
Elements 
Group Trends
Periodic 
Properties 
of the 
Elements 
Alkali Metals 
• Soft, metallic solids. 
• Name comes from 
Arabic word for 
ashes.
Periodic 
Properties 
of the 
Elements 
Alkali Metals 
• Found only as compounds in nature. 
• Have low densities and melting points. 
• Also have low ionization energies.
Periodic 
Properties 
of the 
Elements 
Alkali Metals 
Their reactions with water are famously exothermic.
Periodic 
Properties 
of the 
Elements 
Alkali Metals 
• Alkali metals (except Li) react with oxygen to 
form peroxides. 
• K, Rb, and Cs also form superoxides: 
K + O2 ¾¾® KO2 
• Produce bright colors when placed in flame.
Periodic 
Properties 
of the 
Elements 
Alkaline Earth Metals 
• Have higher densities and melting points than 
alkali metals. 
• Have low ionization energies, but not as low 
as alkali metals.
Periodic 
Properties 
of the 
Elements 
Alkaline Earth Metals 
• Be does not react 
with water, Mg 
reacts only with 
steam, but others 
react readily with 
water. 
• Reactivity tends to 
increase as go down 
group.
Periodic 
Properties 
of the 
Elements 
Group 6A 
• Oxygen, sulfur, and selenium are nonmetals. 
• Tellurium is a metalloid. 
• The radioactive polonium is a metal.
Periodic 
Properties 
of the 
Elements 
Oxygen 
• Two allotropes: 
O2 
O3, ozone 
• Three anions: 
O2−, oxide 
O2 
2−, peroxide 
O2 
1−, superoxide 
• Tends to take electrons 
from other elements 
(oxidation)
Periodic 
Properties 
of the 
Elements 
Sulfur 
• Weaker oxidizing 
agent than oxygen. 
• Most stable allotrope 
is S8, a ringed 
molecule.
Periodic 
Properties 
of the 
Elements 
Group VIIA: Halogens 
• Prototypical nonmetals 
• Name comes from the Greek halos and 
gennao: “salt formers”
Periodic 
Properties 
of the 
Elements 
Group VIIA: Halogens 
• Large, negative electron 
affinities 
Therefore, tend to oxidize 
other elements easily 
• React directly with metals 
to form metal halides 
• Chlorine added to water 
supplies to serve as 
disinfectant
Periodic 
Properties 
of the 
Elements 
Group VIIIA: Noble Gases 
• Astronomical ionization energies 
• Positive electron affinities 
Therefore, relatively unreactive 
• Monatomic gases
Periodic 
Properties 
of the 
Elements 
Group VIIIA: Noble Gases 
• Xe forms three 
compounds: 
XeF2 
XeF4 (at right) 
XeF6 
• Kr forms only one stable 
compound: 
KrF2 
• The unstable HArF was 
synthesized in 2000.
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Ch. 7 Chemical Periodicity

  • 1. Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten Periodic Properties of the Elements Chemistry, The Central Science, 10th edition Chapter 7 Periodic Properties of the Elements John D. Bookstaver St. Charles Community College St. Peters, MO ã 2006, Prentice Hall, Inc.
  • 2. Development of Periodic Table • Elements in the same group generally have similar chemical properties. • Properties are not identical, however. Periodic Properties of the Elements
  • 3. Development of Periodic Table Dmitri Mendeleev and Lothar Meyer independently came to the same conclusion about how elements should be grouped. Periodic Properties of the Elements
  • 4. Development of Periodic Table Periodic Properties of the Elements Mendeleev, for instance, predicted the discovery of germanium (which he called eka-silicon) as an element with an atomic weight between that of zinc and arsenic, but with chemical properties similar to those of silicon.
  • 5. Periodic Properties of the Elements Periodic Trends • In this chapter, we will rationalize observed trends in Sizes of atoms and ions. Ionization energy. Electron affinity.
  • 6. Periodic Properties of the Elements Effective Nuclear Charge • In a many-electron atom, electrons are both attracted to the nucleus and repelled by other electrons. • The nuclear charge that an electron experiences depends on both factors.
  • 7. Periodic Properties of the Elements Effective Nuclear Charge The effective nuclear charge, Zeff, is found this way: Zeff = Z − S where Z is the atomic number and S is a screening constant, usually close to the number of inner electrons.
  • 8. Periodic Properties of the Elements Sizes of Atoms The bonding atomic radius is defined as one-half of the distance between covalently bonded nuclei.
  • 9. Periodic Properties of the Elements Sizes of Atoms Bonding atomic radius tends to… …decrease from left to right across a row due to increasing Zeff. …increase from top to bottom of a column due to increasing value of n
  • 10. Periodic Properties of the Elements Sizes of Ions • Ionic size depends upon: Nuclear charge. Number of electrons. Orbitals in which electrons reside.
  • 11. Periodic Properties of the Elements Sizes of Ions • Cations are smaller than their parent atoms. The outermost electron is removed and repulsions are reduced.
  • 12. Periodic Properties of the Elements Sizes of Ions • Anions are larger than their parent atoms. Electrons are added and repulsions are increased.
  • 13. Periodic Properties of the Elements Sizes of Ions • Ions increase in size as you go down a column. Due to increasing value of n.
  • 14. Periodic Properties of the Elements Sizes of Ions • In an isoelectronic series, ions have the same number of electrons. • Ionic size decreases with an increasing nuclear charge.
  • 15. Periodic Properties of the Elements Ionization Energy • Amount of energy required to remove an electron from the ground state of a gaseous atom or ion. First ionization energy is that energy required to remove first electron. Second ionization energy is that energy required to remove second electron, etc.
  • 16. Periodic Properties of the Elements Ionization Energy • It requires more energy to remove each successive electron. • When all valence electrons have been removed, the ionization energy takes a quantum leap.
  • 17. Trends in First Ionization Energies • As one goes down a column, less energy is required to remove the first electron. For atoms in the same group, Zeff is essentially the same, but the valence electrons are farther from the nucleus. Periodic Properties of the Elements
  • 18. Trends in First Ionization Energies • Generally, as one Periodic Properties of the Elements goes across a row, it gets harder to remove an electron. As you go from left to right, Zeff increases.
  • 19. Trends in First Ionization Energies Periodic Properties of the Elements However, there are two apparent discontinuities in this trend.
  • 20. Trends in First Ionization Energies • The first occurs between Groups IIA and IIIA. • Electron removed from p-orbital rather than s-orbital Periodic Properties of the Elements Electron farther from nucleus Small amount of repulsion by s electrons.
  • 21. Trends in First Ionization Energies • The second occurs between Groups VA and VIA. Periodic Properties of the Elements Electron removed comes from doubly occupied orbital. Repulsion from other electron in orbital helps in its removal.
  • 22. Periodic Properties of the Elements Electron Affinity Energy change accompanying addition of electron to gaseous atom: Cl + e− ¾¾® Cl−
  • 23. Periodic Properties of the Elements Trends in Electron Affinity In general, electron affinity becomes more exothermic as you go from left to right across a row.
  • 24. Periodic Properties of the Elements Trends in Electron Affinity There are again, however, two discontinuities in this trend.
  • 25. Periodic Properties of the Elements Trends in Electron Affinity • The first occurs between Groups IA and IIA. Added electron must go in p-orbital, not s-orbital. Electron is farther from nucleus and feels repulsion from s-electrons.
  • 26. Periodic Properties of the Elements Trends in Electron Affinity • The second occurs between Groups IVA and VA. Group VA has no empty orbitals. Extra electron must go into occupied orbital, creating repulsion.
  • 27. Properties of Metal, Nonmetals, Periodic Properties of the Elements and Metalloids
  • 28. Periodic Properties of the Elements Metals versus Nonmetals Differences between metals and nonmetals tend to revolve around these properties.
  • 29. Periodic Properties of the Elements Metals versus Nonmetals • Metals tend to form cations. • Nonmetals tend to form anions.
  • 30. Periodic Properties of the Elements Metals Tend to be lustrous, malleable, ductile, and good conductors of heat and electricity.
  • 31. Periodic Properties of the Elements Metals • Compounds formed between metals and nonmetals tend to be ionic. • Metal oxides tend to be basic.
  • 32. Periodic Properties of the Elements Nonmetals • Dull, brittle substances that are poor conductors of heat and electricity. • Tend to gain electrons in reactions with metals to acquire noble gas configuration.
  • 33. Periodic Properties of the Elements Nonmetals • Substances containing only nonmetals are molecular compounds. • Most nonmetal oxides are acidic.
  • 34. Periodic Properties of the Elements Metalloids • Have some characteristics of metals, some of nonmetals. • For instance, silicon looks shiny, but is brittle and fairly poor conductor.
  • 35. Periodic Properties of the Elements Group Trends
  • 36. Periodic Properties of the Elements Alkali Metals • Soft, metallic solids. • Name comes from Arabic word for ashes.
  • 37. Periodic Properties of the Elements Alkali Metals • Found only as compounds in nature. • Have low densities and melting points. • Also have low ionization energies.
  • 38. Periodic Properties of the Elements Alkali Metals Their reactions with water are famously exothermic.
  • 39. Periodic Properties of the Elements Alkali Metals • Alkali metals (except Li) react with oxygen to form peroxides. • K, Rb, and Cs also form superoxides: K + O2 ¾¾® KO2 • Produce bright colors when placed in flame.
  • 40. Periodic Properties of the Elements Alkaline Earth Metals • Have higher densities and melting points than alkali metals. • Have low ionization energies, but not as low as alkali metals.
  • 41. Periodic Properties of the Elements Alkaline Earth Metals • Be does not react with water, Mg reacts only with steam, but others react readily with water. • Reactivity tends to increase as go down group.
  • 42. Periodic Properties of the Elements Group 6A • Oxygen, sulfur, and selenium are nonmetals. • Tellurium is a metalloid. • The radioactive polonium is a metal.
  • 43. Periodic Properties of the Elements Oxygen • Two allotropes: O2 O3, ozone • Three anions: O2−, oxide O2 2−, peroxide O2 1−, superoxide • Tends to take electrons from other elements (oxidation)
  • 44. Periodic Properties of the Elements Sulfur • Weaker oxidizing agent than oxygen. • Most stable allotrope is S8, a ringed molecule.
  • 45. Periodic Properties of the Elements Group VIIA: Halogens • Prototypical nonmetals • Name comes from the Greek halos and gennao: “salt formers”
  • 46. Periodic Properties of the Elements Group VIIA: Halogens • Large, negative electron affinities Therefore, tend to oxidize other elements easily • React directly with metals to form metal halides • Chlorine added to water supplies to serve as disinfectant
  • 47. Periodic Properties of the Elements Group VIIIA: Noble Gases • Astronomical ionization energies • Positive electron affinities Therefore, relatively unreactive • Monatomic gases
  • 48. Periodic Properties of the Elements Group VIIIA: Noble Gases • Xe forms three compounds: XeF2 XeF4 (at right) XeF6 • Kr forms only one stable compound: KrF2 • The unstable HArF was synthesized in 2000.