ANORGANIC CHEMISTRY

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Group 1A: The Alkali Metals
 Important Reactions
• The alkali metals reduce H in H2O from the + I to the 0 oxidation state:
2 E(s) + 2 H2O(l) → 2E+(aq) + 2OH-(aq) + H2(g)
• The alkali metals reduce oxygen, but the product depends on the metal.
Li forms the oxide, Li2O; Na forms the peroxide, Na2O2; K, Rb, and Cs form
the superoxide, EO2 :
4 Li(s) + O2(g) → 2Li2O(s)
K(s) + O2(g) → KO2 (s)
In emergency breathing units, KO2 reacts with H2O and CO2 in exhaled air
to release O2.
• The alkali metals reduce hydrogen to form ionic (saltlike) hydrides:
2E(s) + H2(g) → 2EH(s)
NaH is an industrial base and reducing agent that is used to prepare other
reducing agents, such as NaBH4.
• The alkali metals reduce halogens to form ionic halides:
2E(s) + X2 → 2EX(s) (X = F, CI, Br, I)
• Sodium chloride is the most important alkali metal halide.
(a) In the Downs process for the production of sodium metal :
2NaCI(l) electricity 2Na(l) + CI2(g)
(b) In the chlor-alkali process :
2NaCI(aq) + 2H2O(l) → 2NaOH(aq) + H2(g) + Cl2(g)
(c) In its reaction with sulfuric acid :
2NaCl(s) + H2SO4(aq) → Na2SO4(aq) + 2HCI(g)
Sodium sulfate is important in the paper industry; HCI is essential in steel,
plastics, textile, and food production.
• Sodium hydroxide is used in the formation of bleaching solutions :
2NaOH(aq) + Cl2(g) → NaCIO(aq) + NaCI(aq) + H2O(l)
• In an ion-exchange process, water is "softened" by removal of dissolved
hardwater cations, which displace Na+ from a resin:
M2+(aq) + Na2Z(s) → MZ(s) + 2Na+(aq)
(M = Mg, Ca; Z = resin)
 Important Compounds
• Lithium chloride and lithium bromide, LiCI and LiBr. Because the Li+ ion is so small,
Li salts have a high affinity for H2O and yet a positive heat of solution. Thus, they
are used in dehumidifiers and air-cooling units.

• Lithium carbonate, Li2CO3 . Used to make porcelain enamels and toughened

glasses and as a drug in the treatment of bipolar disorders.

• Sodium chloride, NaCl. Millions of tons used in the industrial production of Na,
NaOH, Na2CO3, NaHCO3, Na2SO4, and HCI or purified for use as table salt.

• Sodium carbonate and sodium hydrogen carbonate, Na2CO3 and NaHCO3.

Carbonate used as an industrial base and to make glass. Hydrogen carbonate,
which releases CO2 at low temperatures (50 to 100oC), used in baking powder and
in fire extinguishers.

• Sodium hydroxide, NaOH. Most important industrial base; used to make bleach,
sodium phosphates, and alcohols.

• Potassium nitrate, KNO3. Powerful oxidizing agent used in gunpowder and

fireworks
HYDROGEN, THE SIMPLEST ATOM
 Highlights of Hydrogen Chemistry
• Ionic (Saltlike) Hydrides
With very reactive metals, such as those in Group lA and the larger members of
Group 2A (Ca, Sr, and Ba), hydrogen forms saltlike hydrides-white, crystalline solids
composed of the metal cation and the hydride ion:
2Li(s) + H2(g) → 2LiH(s) ; Ca(s) + H2(g) → CaH2(s)
• Covalent (Molecular) Hydrides
Hydrogen reacts with nonmetals to form many covalent hydrides, such as CH4 ,
NH3 , H2O, and HF. Most are gases consisting of small molecules, but many
hydrides of boron and carbon are liquids or solids that consist of much larger
molecules. In most covalent hydrides, hydrogen has an oxidation number of + 1
because the other nonmetal has a higher electronegativity than hydrogen.
• Metallic (Interstitial) Hydrides
Many transition elements form metallic (interstitial) hydrides, in which H2
molecules (and H atoms) occupy the holes in the metal's crystal structure. Thus,
such hydrides are not compounds but gas-solid solutions.
Group 2A: The Alkaline Earth Metals
 Important Reactions
• The metals reduce O2 to form the oxides:
2E(s) + O2(g) → 2EO(s)
Ba also forms the peroxide, BaO2.
• The larger metals reduce water to form hydrogen gas:
E(s) + 2H2O(l) → E2+(aq) + 2OH-(aq) + H2(g) (E = Ca, Sr, Ba)
• The metals reduce halogens to form ionic halides:
E(s) + X2 → EX2(s) (X = F, CJ, Br, I)
• Most of the elements reduce hydrogen to form ionic hydrides:
E(s) + H2 (g) → EH2(s) (E = all except Be)
• Most of the elements reduce nitrogen to form ionic nitrides:
3E(s) + N2 (g) → E3N2(s) (E = all except Be)
• Except for amphoteric BeO, the element oxides are basic:
EO(s) + H2O(l) → E2+(aq) + 2OH-(aq)
• All carbonates undergo thermal decomposition to the oxide:
ECO3 (s) ∆ EO(s) + CO2 (g)
This reaction is used to produce CaO (lime) in huge amounts from naturally occurring
limestone.
 Important Compounds
• Beryl, Be3Al2Si6O18. Beryl, the industrial source of Be metal, also occurs
as a gemstone with a variety of colors. It is chemically identical to emerald,
except for the trace of Cr3+ that gives emerald its green color.

• Magnesium oxide, MgO. Because of its high melting point (2852°C), MgO
is used as a refractory material for furnace brick and wire insulation.

• Alkylmagnesium halides, RMgX (R = hydrocarbon group; X = halogen).

These compounds are used to synthesize many organic compounds.
Organotin agricultural fungicides are made by treating RMgX with SnCI4 :
3RMgCl + SnCl4 → 3MgCl2 + R3SnCl

• Calcium carbonate, CaCO3. Occurs as enormous natural deposits of

limestone, marble, chalk, and coral. Used as a building material, to make
lime, and, in high purity, as a toothpaste abrasive and an antacid.
Group 3A: The Boron Family
 Important Reactions
• The elements react sluggishly, if at all, with water:
2Ga(s) + 6H2O(hot) → 2Ga3+(aq) + 6OH-(aq) + 3H2(g)
2TI(s) + 2H2O(steam) → 2TI+(aq) + 2OH-(aq) + H2(g)
Al becomes covered with a layer of Al203 that prevents
further reaction.
• When strongly heated in pure O2, all members form oxides:
4E(s) + 3O2(g) ∆ 2E2O3(S) (E = B, AI, Ga, In)
4TI(s) + O2(g) ∆ 2Tl2O(s)
Oxide acidity decreases down the group: B2O3 (weakly
acidic) >Al2O3 > Ga2O3 > In2O3 > Tl2O (strongly basic), and
the + I oxide is more basic than the + 3 oxide.
• All members reduce halogens (X2):
2E(s) + 3X2 → 2EX3 (E = B, AI, Ga, In)
2Tl(s) + X2 → 2TIX(s)
• Acid treatment of Al2O3 is important in water purification:
Al2O3 (s) + 3 H2SO4(l) → Al2(SO4)3(s) + 3 H2O(l)
In water, Al2(SO4)3 forms a colloid that aids in removing suspended
particles.
• The overall reaction in the production of aluminum metal is a redox
process:
2Al2O3(s) + 3C(s) → 4Al(s) + 3CO2(g)
This process is carried out electrochemically in the presence of cryolite
(Na3AIF6) which lowers the melting point of the reactant mixture and
takes part in the change.
• A displacement reaction produces gallium arsenide, GaAs :
(CH3)3Ga(g) + AsH3 (g) → 3CH4(g) + GaAs(s)
 Important Compounds
• Boron oxide, B2O3. Used in the production of borosilicate glass.
• Borax, Na2[B4O5(OH)4].8H2O. Major mineral source of boron compounds and
B2O3. Used as a fireproof insulation material and as a washing powder.
• Boric acid, H3BO3 [or B(OH)3]. Used as external disinfectant, eyewash, and
insecticide.
• Diborane, B2H6. A powerful reducing agent for possible use as a rocket fuel. Used
to synthesize higher boranes, compounds that led to new theories of chemical
bonding.
• Aluminum sulfate (cake alum), Al2(SO4)3.18H2O. Used in purifying water, tanning
leather, and sizing paper; as a fixative for dyeing cloth ; and as an antiperspirant.
• Aluminum oxide, Al2O3. Major compound in natural source (bauxite) of AI metal.
Used as abrasive in sandpaper, sanding and cutting tools, and toothpaste. Large
crystals with metal ion impurities often of gemstone quality. Inert support for
chromatography. In fibrous forms, woven into heat- resistant fabrics; also used to
strengthen ceramics and metals.
• Tl2Ba2Ca2Cu3O10. Becomes a high-temperature superconductor at 125 K, which
is readily attained with liquid N2.
Group 4A: The Carbon Family
 Important Reactions
• The elements are oxidized by halogens:
E(s) + 2X2 → EX4 (E = C, Si, Ge)
The +2 halides are more stable for tin and lead, SnX2 and PbX2.
• The elements are oxidized by O2:
E(s) + O2(g) → EO2 (E = C, Si, Ge, Sn)
Pb forms the +2 oxide, PbO. Oxides become more basic down the
group.
• Air and steam passed over hot coke produce gaseous fuel mixtures
(producer gas and water gas):
C(s) + air(g) + H2O(g) → CO(g) + CO2(g) + N2(g) + H2(g) [not
balanced]
• Hydrocarbons react with O2 to form CO2 and H2O. The reaction for
methane is adapted to yield heat or electricity:
CH4(g) + 2O2 (g) → CO2 (g) + 2H2O(g)
• Certain metal carbides react with water to produce
acetylene:
CaC2(s) + 2H2O(l) → Ca(OH)2(aq) + C2H2 (g)
The gas is used to make other organic compounds and as a
fuel in welding.
• Freons (chlorofluorocarbons) are formed by fluorinating
carbon tetrachloride:
CCI4(l) + HF(g) → CFCI3(g) + HCI(g)
Production of trichlorofluoromethane (Freon- 11), the most
widely used refrigerant in the world, is being eliminated
because of adverse effects on the environment.
• Silica is reduced to form elemental silicon:
SiO2(s) + 2C(s) → Si(s) + 2CO(g)
This crude silicon is made ultrapure through zone refining
for the manufacture of computer chips.
 Important Compounds
• Carbon monoxide, CO. Used as a gaseous fuel, as a precursor for
organic compounds, and as a reactant in the purification of nickel.
Formed in internal combustion engines and released as a toxic air
pollutant.

• Carbon dioxide, CO2. Atmospheric component used by

photosynthetic plants to make carbohydrates and O2 . The final
oxidation product of all carbon-based fuels; its increase in the
atmosphere is causing global warming. Used industrially as a
refrigerant gas, a blanketing gas in fire extinguishers, and an
effervescent gas in beverages. Combined with NH3 to form urea for
fertilizers and plastics manufacture.

• Methane, CH4. Used as a fuel and in the production of many

organic compounds. Major component of natural gas. Formed by
anaerobic decomposition of plants (swamp gas) and by microbes in
termites and certain mammals. May contribute to global warming.
• Silicon dioxide, SiO2. Occurs in many amorphous (glassy) and
crystalline forms, quartz being the most common. Used to make
glass and as an inert chromatography support material.

• Silicon carbide, SiC. Known as carborundum, a major industrial

abrasive and a highly refractory ceramic for tough, high-
temperature uses. Can be doped to form a high-temperature
semiconductor.

• Organotin compounds, R4Sn. Used to stabilize PVC, or poly(vinyl

chloride), plastics and to cure silicone rubbers. Agricultural biocide
for insects, fungi, and weeds.

• Tetraethyllead, (C2H5)4Pb. Once used as a gasoline additive to

improve fuel efficiency, but now banned because of its inactivation
of auto catalytic converters. Major source of lead as a toxic air
pollutant.
Group 5A: The Nitrogen Family
 Important Reactions
• Nitrogen is “fixed" industrially in the Haber process:
N2 (g) + 3H2 (g) ↔ 2NH3 (g)
• Halides are formed by direct combination of the elements:
2E(s) + 3X2 → 2EX3 (E = all except N)
EX3 + X2 → EX5 (E = all except N and Bi with X = F and CI,
but no BiCl5; E = P for X = Br)
• Oxoacids are formed from the halides in a reaction with water that is common to
many nonmetal halides:
EX3 + 3H2O(l) → H3EO3(aq) + 3HX(aq) (E = all except N)
EX5 + 4H2O(l) → H3EO4(aq) + 5HX(aq) (E = all except N and Bi)
• Phosphate ions are dehydrated to form polyphosphates:
3NaH2PO4 (s) → Na3P3O9 (S) + 3H2O(g)
• When P4 reacts in basic solution, its oxidation number both decreases and
increases (disproportionation):
P4 (s) + 3OH-(aq) + 3H2O(l) → PH3(g) + 3H2PO2-(aq)
Analogous reactions are typical of many nonmetals, such as S8 and X2 (halogens).
 Important Compounds
• Ammonia, NH3. First substance formed when atmospheric N2 is
used to make N-containing compounds. Annual multimillion-ton
production for use in fertilizers, explosives, rayon, and polymers
such as nylon, urea-formaldehyde resins, and acrylics.
• Hydrazine, N2H4. Like NH3 , it is a weak base, forming N2H5+ and
N2H62+ ions with acids. Hydrazine is also used to make
antituberculin drugs, plant growth regulators, and fungicides, and
organic hydrazine derivatives are used in rocket and missile fuels.
• Nitric oxide (NO), nitrogen dioxide (NO2), and nitric acid (HNO3).
Oxides are intermediates in HNO3 production. This acid is used in
fertilizer manufacture, nylon production, metal etching, and the
explosives industry.
• Amino acids, H3N+ -CH(R)- COO- (R = one of 20 different organic
groups). Occur in every organism, both free and linked together into
proteins. Essential to the growth and function of all cells. Synthetic
amino acids are used as dietary supplements.
• Phosphorus trichloride, PCI3 . Used to form many organic
phosphorus compounds, including oil and fuel additives,
plasticizers, flame retardants, and insecticides. Also used to
makePCl5, POCI3, and other importam P-containing compounds.
• Tetraphosphorus decaoxide (P4O10) and phosphoric acid (H3PO4).
• Sodium tripolyphosphate, Na5P3O10. As a water-softening agent
(Calgon), it combines with hard-water Mg2+ and Ca2+ ions,
preventing them from reacting with soap anions, and thus
improving cleaning action. Its use has been curtailed in the United
States because it pollutes lakes and streams by causing excessive
algal growth.
• Adenosine triphosphate (ATP) and other biophosphates. ATP acts to
transfer chemical energy in the cell; it is necessary for all biological
processes requiring energy. Phosphate groups also occur in sugars,
fats, proteins, and nucleic acids.
• Bismuth subsalicylate, BiO(C7H5O3). The active ingredient in Pepto-
Bismol, a widely used remedy for diarrhea and nausea.
Group 6A: The Oxygen Family
 Important Reactions
• Halides are formed by direct combination:
E(s) + X2 (g) → various halides (E = S, Se, Te; X = F, Cl)
• The other elements in the group are oxidized by O2 :
E(s) + O2(g) → EO2 (E = S, Se, Te, Po)
SO2 is oxidized further, and the product is used in the final step of H2SO4
manufacture :
2SO2(g) + O2(g) → 2SO3(g)
• Sulfur is recovered when hydrogen sulfide is oxidized:
8H2S(g) + 4O2 (g) → S8(s) + 8H2O(g)
This reaction is used to obtain sulfur when natural deposits are not
available.
• The thiosulfate ion is formed when an alkali metal sulfite reacts with
sulfur, as in the preparation of "hypo," photographer's developing
solution:
S8(s) + 8Na2SO3(aq) → 8Na2S2O3(aq)
 Important Compounds
• Water, H2O. The single most important compound on Earth.
• Hydrogen peroxide, H2O2. Used as an oxidizing agent, disinfectant, and bleach,
and in the production of peroxy compounds for polymerization.
• Hydrogen sulfide, H2S. Vile-smelling toxic gas formed during anaerobic
decomposition of plant and animal matter, in volcanoes, and in deep-sea thermal
vents. Used as a source of sulfur and in the manufacture of paper.
• Sulfur dioxide, SO2. Colorless, choking gas formed in volcanoes or whenever an S-
containing material (coal, oil, metal sulfide ores, and so on) is burned. More than
90% of SO2 produced is used to make sulfuric acid. Also used as a fumigant and a
preservative of fruit, syrups, and wine. As a reducing agent, removes excess Cl2
from industrial wastewater, removes O2 from petroleum handling tanks, and
prepares ClO2 for bleaching paper. Atmospheric pollutant in acid rain.
• Sulfur trioxide (SO3) and sulfuric acid (H2SO4). SO3, formed from SO2 over a
K2O/V2O5 catalyst, is then converted to H2SO4. The acid is the cheapest strong
acid and is so widely used in industry that its production level is an indicator of a
nation's economic strength. It is a strong dehydrating agent that removes water
from any organic source.
• Sulfur hexafluoride, SF6 . Extremely inert gas used as an electrical insulator.
Group 7 A: The Halogens
 Important Reactions
• The halogens (X2) oxidize many metals and nonmetals. The reaction with
hydrogen, although not used commercially for HX production (except for
high-purity HCl), is characteristic of these strong oxidizing agents:
X2 + H2(g) → 2HX(g)
• The halogens disproportionate in water:
X2 + H2O(l) ↔ HX(aq) + HXO(aq) (X = CI, Br, I)
In aqueous base, the reaction goes to completion to form hypohalites and,
at higher temperatures, halates; for example:
3CI2(g) + 6OH-(aq) ∆ CIO3 -(aq) + 5CI-(aq) + 3H2O(l)
• F2 is produced electrolytically at moderate temperature:

2HF (as a soln of KF in HF) electrolysis 90oC H2(g) + F2(g)

A major use of F2 is in the preparation of UF6 for nuclear fuel.
• Glass (amorphous silica) is etched with HF:
SiO2(s) + 6HF(g) → H2SiF6(aq) + 2H2O(l)
 Important Compounds
• Fluorspar (fluorite), CaF2 . Widely distributed mineral used as a flux in
steelmaking and in the production of HF.
• Hydrogen fluoride, HF. Colorless, extremely toxic gas used to make F2,
organic fluorine compounds, and polymers. Also used in aluminum
manufacture and in glass etching.
• Hydrogen chloride, HCI. Extremely water-soluble gas that forms
hydrochloric acid, which occurs naturally in the stomach fluids of
mammals (humans produce 1.5 L of 0.1 M HCI daily) and in volcanic gases
(from reaction of H2O and sea salt). Made by reaction of NaCI and H2SO4
and as a by-product of plastics (PVC) production. Used in the "pickling" of
steel (removal of adhering oxides) and in the production of syrups, rayon,
and plastic.
• Sodium hypochlorite, NaCIO, and calcium hypochlorite, Ca(CIO)2.
Oxidizing agents used to bleach wood pulp and textiles and to disinfect
swimming pools, foods, and sewage (also used to disinfect the Apollo 11
on return from the Moon). Household bleach is 5.25% NaCIO by mass in
water.
• Ammonium perchlorate, NH4CIO4. Strong oxidizing agent
used in the space shuttle program.
• Potassium iodide, KI. Most common soluble iodide. Added
to table salt to prevent thyroid disease (goiter). Used in
chemical analysis because it is easily oxidized to I2, which
provides a colored end point.
• Polychlorinated biphenyls, PCBs. Mixture of chlorinated
organic compounds used as nonflammable insulating
liquids in electrical transformers. Production discontinued
because of persistence in the environment, where they
become concentrated in the tissues of fish, birds, and
mammals, and cause reproductive disturbances and
possibly cancer.
Group 8A: The Noble Gases