Periodic Properties

Chapter 7
Overview
Periodic Table
Electron Shells & Sizes of Atoms
Ionization Energy
Electron Affinities
Metals, Nonmetals & Metalloids and
Trends
Periodic Table
1869 -- Dmitri Mendeleev & Lothar Meyer
published classification schemes of elements
based on order of increasing elemental atomic
weight
which follows atomic number
some missing elements were discovered based
upon prediction that they should be there
Henry Moseley
related energy of nuclear x-rays to atomic
number
Sizes of Atoms
Electron Shells
quantum mechanical model predicts shells of
electron density
as number of protons increases, inner shells are
held more tightly, closer to nucleus
Sizes of Atoms
atom boundaries are difficult to assess
define atom size as the distance between
nuclei of two bound atoms
+ +
Cl Cl
Atomic radii = distance between the nuclei
r
General Trends of Physical
Properties
most trends are related to Z
eff
, effective nuclear
charge
due to increase in distance from nucleus and
shielding, Z
eff
decreases going down a group
due to ineffective shielding by electrons in the
same shell, Z
eff
increases going across a row
Z
eff
increases
decreases
Compare valence e
-
s of Na and Cs
which will be held more tightly by nucleus?
the e
-
that is closest to the nucleus
which will be closest to the nucleus?
Nas 3s electron
Compare last electron of C and F
which has more protons interacting?
Z
F
= 9 while Z
C
= 4
do e
-
in the same subshell shield their fellow e
-
s very
well?
no
so which last e
-
will experience the greatest Z
eff
?
F
General Trends in Atomic Size
radius increases on going down a group (Z
eff

decreases)
radius tends to decrease on going left to right
across a row (Z
eff
increases)
size
decreases
increases
We know that Z
eff
decreases going down a
group, how does that affect size?

As Z
eff
(on a valence e
-
) decreases, it is less
tightly held, hence can expand somewhat

We know that Z
eff
increases going across a row,
how does that affect size?

As Z
eff
(on a last e
-
) increases, it is more tightly
held, hence contraction occurs and atom is
smaller

Compare valence e
-
s of Na and Cs
which experiences the greatest Z
eff
?
Nas 3s electron (bec. it is closest to nucleus)
which atom will be smaller?
Na < Cs
Compare last electron of C and F
which has more protons interacting?
Z
F
= 9 while Z
C
= 4
do e
-
in the same subshell shield their fellow e
-
s very
well?
no
so which last e
-
will experience the greatest Z
eff
?
F
which atom will experience greatest contraction?
F will be more contracted, hence smaller
Trends in Ionization Energy
ionization energy decreases going down (Z
eff

decreases)
ionization energy increases going across (Z
eff

increases)
I.E.
increases
decreases
Ionization Energy -- endothermic process
first ionization energy, I
1
-- to remove first
electron
M M
+
+ 1e
-

second ionization energy, I
2
-- to remove second
electron
M
+
M
2+
+ 1e
-

third ionization energy, I
3
-- to remove third
electron
M
2+
M
3+
+ 1e
-


I
1
< I
2
< I
3


Note: removal of inner core electrons is very
energy expensive

Element I
1
I
2
I
3
I
4

Na 496 4560
Mg 738 1450 7730
Al 578 1820 2750 11,600

The more tightly an e
-
is held, the more energy
it takes to remove it
in other words, greater Z
eff
= greater I.E.
Compare valence e
-
s of Na and Cs
which has greater Z
eff
?
Na
which has greater I
1
?
Na (Css 6s electron is further away, less tightly
held and easier to remove than Nas 3s electron)
Compare last e
-
of C and F
which has greater Z
eff
?
F
which has greater I
1
?
F (more tightly held, more energy to remove)
transition metals and f-block metals show
small variation in ionization energies across
rows

representative elements show a larger range of
values for I
1


irregularities in ionization energies occur due
to shielding
I
1
for Al < I
1
for Mg -- removal of p versus s
electron
I
1
for O < I
1
for N -- removal of p electron to
produce stable configuration
Electron Affinities
energy change associated with adding an
electron to gaseous atom
measures attraction of atom for the added
electron
Cl
(g)
+ 1e
-
Cl
-
DE = -349 kJ/mol
exothermic process
most electron affinities are exothermic
some exceptions & irregularities
nobel gases
Be & Mg
Group III elements
Metals
general trends and properties
to the left on periodic table
ability to lose electrons (low ionization energies)
-- what kind of ions?
have a metallic or shiny luster, ductile
form crystalline solids
have good thermal and electrical conductivity
transition metals vary in charge
most have +2 in addition to other charges (+1 to +5)
form ionic compounds with non-metals
especially with oxides or halides
metal oxides are called basic oxides
react with water to form basic hydroxides
Na
2
O
(s)
+ H
2
O
(l)
2NaOH
(aq)

react with acid to form water and salt
Nonmetals
general trends and properties
to the right on periodic table
ability to gain electrons -- what kind of ions?
non-conductors and thermal insulators
have lower melting points are molecular solids
rather than ionic solids
seven exist as diatomic molecules
H
2
, N
2
, O
2
, F
2
, Cl
2
, Br
2
, I
2

form molecular compounds with other nonmetals
such as oxides, halides & hydrides
nonmetal oxides are called acidic oxides
react with water to form acids
CO
2(g)
+ H
2
O
(l)
H
2
CO
3(aq)

react with bases to form salt and water
CO
2(g)
+ 2NaOH
(aq)
Na
2
CO
3(aq)
+ H
2
O
(l)


Metalloids
have a mixture of properties some metallic,
some not
Group Trends for Active
Metals
Group 1A -- Alkali Metals
very reactive, only found in nature in oxidized
form (compounds)
metals produced by electrolysis of molten
compounds
reactivity increases down the group
react rapidly with water
2K
(s)
+ 2H
2
O
(l)
2KOH
(aq)
+ H
2(g)

react with acid:
2K
(s)
+ 2HCl
(aq)
2KCl
(aq)
+ H
2(g)

react with hydrogen to form hydrides
2K
(s)
+ H
2(g)
2KH
(s)

react with oxygen in different ways
4Li
(s)
+ O
2(g)
2Li
2
O
(s)
containing O
2-

this is the more common reaction
other alkali metals form peroxides, O
2
2-

2Na
(s)
+ O
2(g)
Na
2
O
2(s)

K, Rb, Cs form superoxides, O
2
-

K
(s)
+ O
2(g)
KO
2(s)

peroxides and superoxides are not as common
most alkali metal compounds are colorless
Group 2A -- Alkaline Earth Metals
reactive less than alkali metals (ionization
energies higher)
reactivity increases down the group
heavier metals react with water to form bases
Ca
(s)
+ 2H
2
O
(l)
Ca(OH)
2(aq)
+ H
2(g)

lighter metals react similarly with hot water or
steam
react with acids:
Mg
(s)
+ 2HCl
(aq)
MgCl
2(aq)
+ H
2(g)

react with O to produce oxides
2Mg
(s)
+ O
2(g)
2MgO
(s)

Trends for Nonmetals
Hydrogen
nonmetal, diatomic, colorless gas
high ionization energy (no shielding)
typically forms molecular compounds with
other nonmetals
these reactions are fairly exothermic
2H
2(g)
+ O
2(g)
2H
2
O
(l)
DH
o
= -571.7 kJ/mol

forms hydrides (H
-
) with metals
2Na
(s)
+ H
2(g)
2NaH
(s)

Group 6A: Oxygen Group
density increases, metallic character increases
down group
oxygen is diatomic, & the only gas in the group
allotrope (different form) is ozone, O
3

3O
2(g)
2O
3(g)
DH
o
= +284.6 kJ/mol
is ozone more or less stable than O
2
?
ions are in different forms
O
2-
, oxide
O
2
2-
, peroxide
O
2
-
, superoxide
less

Group 7A: Halogens
increased nonmetallic character
lighter elements are diatomic gases & more
reactive than heavier elements
have very exothermic electron affinities and
gain electron easily
F has highest electron affinity
2Na
(s)
+ F
2(g)
2NaF
(s)
DH
o
= -1147 kJ
2H
2
O
(l)
+ 2F
2(g)
4HF
(aq)
DH
o
= -758.7 kJ
Cl reacts somewhat more slowly
Cl
2(g)
+ H
2
O
(l)
HCl
(aq)
+ HOCl
(aq)

Group 8A: Noble Gases
all are monotomic, quite stable and unreactive
Xe was the first noble gas compound identified
XeF
6

Kr is less reactive & has one known compound
KrF
2

no compounds of He, Ne or Ar are known
however, there have been implications of a possible Ar
compound