Chapters 18/19 – "Representative Elements"

18.1) Survey of the Representative Elements

18.2) Group 1A Elements
18.3) The Chemistry of Hydrogen
18.4) Group 2A Elements
18.5) Group 3A Elements
18.6) Group 4A Elements (Si only)
19.1) Group 5A Elements
19.2) The Chemistry of Nitrogen
19.3) The Chemisty of Phosphorus
19.4) Group 6A Elements
19.5) The Chemistry of Oxygen
19.6) The Chemistry of Sulfur
19.7) Group 7A Elements
19.8) Group 8A Elements

General Overview:
Observed periodic
trends are related to the
numbers and types of
valence electrons

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 Figure 18.2

Trends in First Ionization Energy

for the Main Group Elements

2
 Trends in Electronegativity
for the Main Group Elements

Trends in Metallic Character of the Main Group Elements

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 Electron Affinity

Increasing exothermicity
H, -72 He, 21
Li, -60 Be, 241 B, -27 C, -122 N, 0 O, -141 F, -328 Ne, 29
Na, -53 Mg, 230 Al, -43 Si, -134 P, -72 S, -200 Cl, -349 Ar, 34
K,-48 Ca, 156 Ga, -29 Ge, -119 As, -78 Se, -195 Br, -325 Kr, 39
Rb, -47 Sr, 167 In, -29 Sn, -107 Sb, -103 Te, -190 I, -295 Xe, 40
Cs, -45 Ba, 52 Tl, -19 Pb, -35 Bi, -91 Po, -183 At, -270 Rn, 41

Metals - Metalloids - Nonmetals

See Figure 18.1

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General Overview:
Observed periodic
trends are related to the
numbers and types of
valence electrons

Metallic Behavior

5
Redox - Reduction and Oxidation

O 2 F2
Cl2
Br2
I2

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Elements’ Distribution (earth, sea, atmosphere)
Element Mass % Element Mass %
Oxygen 49.20 Chlorine 0.19
Silicon 25.67 Phosphorus 0.11
Aluminum 7.50 Manganese 0.09
Iron 4.71 Carbon 0.08
Calcium 3.39 Sulfur 0.06
Sodium 2.63 Barium 0.04
Potassium 2.40 Nitrogen 0.03
Magnesium 1.93 Fluorine 0.03
Hydrogen 0.87
Titanium 0.58 All others 0.47
See Table 18.1

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Average Elemental Composition of Human Body
Element Mass %
Oxygen 65.0
Carbon 18.0
Hydrogen 10.0
See Table 18.2
Nitrogen 3.0
Calcium 2.0
Phosphorus 1.0
Trace elements* 1.0

*Trace elements include: Arsenic, Chromium, Cobalt, Copper,

Fluorine, Iodine, Manganese, Molybdenum, Nickel, Selenium,
Silicon, Vanadium
- Most are necessary for health even at trace concentrations!!

Group 1A Elements
- ns1 valence electron configuration
H Nonmetal
Li
Na
K Alkali Metals
Rb
Cs
Fr
Sources and methods of preparation- Table 18.3
Selected physical properties- Table 18.4

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9
Properties Based Upon ns1 Electron Configuration
1. Low heat of atomization ( Hatom)
(Energy needed to convert the solid to individual gaseous atoms)
M(s) M(g) Hatom ( L i > Na > K > Rb > Cs )
2. Low IE and High charge density
a great decrease in size occurs when the one valence electron is lost!
Vol of Li+ is < 13% of that of Li - thus M+ ions are small with
3. High Lattice Energy a great charge density.
small cations pull very close to large anions, yielding large
quantities of energy liberated upon crystallization
Trend - as the cation becomes larger, the lattice energy becomes
smaller (less negative)
4. Hydration Energy E+(g) + H2O(l) E+(aq)
- HHydr ( Li+ > Na+ > K+ > Rb+ > Cs+ )
The smaller ions attract water molecules strongly enough to form
larger hydrated ions: Li+(aq) is larger than Cs+(aq)

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 Sodium reacts violently with water

Reactions of the Alkali Metals with water

All of the alkali metals react with water to form hydrogen and the
hydroxide ion. Li, Na, K, Rb, and Cs react I order of reactivity, The
largest atom Cs is the most reactive, and the reactivity decreases as they
get smaller and smaller, with Li being the least reactive.

2 M(s) + 2 H2O(l) H2 (g) + 2 OH-(aq) + 2 M+(aq)

Lithium and Sodium are less dense than water, and react on the water
surface, Potassium is so reactive it catches the hydrogen released catches
Fire from the exothermic reaction. Rubidium and Cesium literally
explode when they come in contact with water. They all produce
solutions of the alkali metal hydroxides, but the reactivity increases down
the group.
This reactivity increase is due to the increasing diameter of the atoms,
So that the attractive forces on the one valence electron is much less, and
It is free to leave.

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12
Fig. 14.3 (P 547)

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 Reactions of Alkali Metals with Oxygen - I
All alkali metals will form oxides in the form of M2O, but only
lithium will form this oxide in excess oxygen:

4 Li(s) + O2 (g) 2 Li2O(s)

Sodium in an excess of oxygen will form the peroxide:

2 Na(s) + O2 (g) Na2O2 (g)

The Peroxide anion reacts with water to from Hydrogen

peroxide and hydroxide anions.

Na2O2 (s) + 2 H2O(l) 2 Na+(aq) + 2 OH-(aq) + H2O2 (aq)

Reactions of Alkali Metals with Oxygen - II

Potassium, Rubidium and Cesium react with oxygen to form super-oxides
With the general formula of MO2 for example potassium:

K(s) + O2 (g) KO2 (S)

The superoxides release oxygen gas when they react with water or
carbon dioxide gas. For this reason they are very useful in emergency
breathers for fireman or emergency workers.

2 MO2 (s) + 2 H2O(l) 2 M+(aq) + 2 OH-(aq) + O2 (aq) + H2O2 (aq)

4 MO2 (s) + 2 CO2 (g) 2 MCO3 (s) + 3 O2 (g)

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 Important Reactions of the Alkali Metals - I

1. The alkali metals reduce hydrogen to form ionic (salt like) hydrides:
2 M(s) + H2 (g) 2 MH(s)

NaH is an industrial base and reducing agent that is used to prepare

other reducing agents, such as NaBH4.

2. The alkali metals reduce halogens to form ionic halides:

2 M(s) + X2(-) 2 MX(s) ( X = F, Cl, Br, I)
3. Sodium chloride is the most important alkali halide.
a) In the Downs process for the production of sodium metal, by the
electrolysis of molten NaCl:
electricity
2 NaCl(L) 2 Na(L) + Cl2 (g)

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Important Reactions of the Alkali Metals - II
3. continued
b) In the chlor-alkali process, NaCl(aq) is electrolyzed to form several
key industrial chemicals:
electricity
2 NaCl + 2 H O
(aq) 2 (l) 2 NaOH + H
(aq) 2 (g)+ Cl2 (g)

c) In its reaction with sulfuric acid, NaCl forms two major products:
2 NaCl(s) + H2SO4 (aq) Na2SO4 (aq) + 2 HCl(g)

Sodium sulfate is important in the paper industry; HCl is essential

in steel, plastics, textiles, and food production.
4. Sodium hydroxide is used in the formation of bleaching solutions:
2 NaOH(aq) + Cl2 (g) NaClO(aq) + NaCl(aq) + H2O(l)
5. In an ion-exchange process water is “softened” when Na+ is displaced
by “hard-water” ions (M2+):
Mg2+(aq) + Na2(resin)(s) Mg(resin)(s) + 2 Na+(aq)

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Important Compounds of the Alkali Metals
1. Lithium chloride and lithium bromide, LiCl and LiBr. Because the Li+
ion is so small, Li salts have a affinity for H2O and yet a positive heat
of solution, so they are used in dehumidifiers and air-cooling units.
2. Lithium carbonate, Li2CO3. Used to make porcelain enamels and
toughened glasses and as a drug in the treatment of manic-depressive
disorders.
3. Sodium chloride, NaCl. Millions of tons used in the industrial
production of Na, NaOH, Na2CO3/NaHCO3, Na2SO4, HCl, and
purified for use as table salt.
4. Sodium carbonate and sodium bicarbonate, Na2CO3 and NaHCO3.
Carbonate used as an industrial base and to make glass. Bicarbonate,
which releases CO2 at low temperatures (500 to 1000), used in baking
powder and in fire extinguishers.
5. Sodium hydroxide, NaOH. Most important industrial base; used to
make bleach, sodium phosphates, and alcohols.
6. Potassium nitrate, KNO3. Powerful oxidizing agent used in gunpowder
and fireworks.

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