nonmetals chapter 22 chemistry of the nonmetals. nonmetals except for hydrogen, the nonmetals are...
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Nonmetals
Chapter 22Chemistry of the
Nonmetals
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Nonmetals
Nonmetals
Except for hydrogen, the nonmetals are found in the upper right-hand corner of the periodic chart.
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Nonmetals
Periodic Trends
Within a group, smaller atoms are more likely to form -bonds because they can get closer to other atoms.
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Nonmetals
Periodic Trends
As a result, CO2 contains two -bonds, and SiO2 is a network solid with only -bonds.
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Nonmetals
Hydrogen
• Discovered by Henry Cavendish (1731-1810)
• Three isotopesProtium (1H) 99.98% of
all hydrogenDeuterium (2H) 0.016%Tritium (3H) Radioactive
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Nonmetals
Properties of Hydrogen
• UniqueDoes not belong to any group
• Very low melting (-259C) and boiling (-253C) points
• Very large bond enthalpiesReacts slowlyReactions are generally quite exothermic
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Nonmetals
Hydrogen Production• Commercially produced from reaction of methane
(CH4) with steam at 1100C or carbon and steam above 1000C
CH4 (g) + H2O (g) CO (g) + 3 H2 (g)
CO (g) + H2O (g) CO2 (g) + H2 (g)
C (s) + H2O (g) H2 (g) + CO (g)
• Production from electrolysis of water not energy-efficient
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Nonmetals
Uses of Hydrogen
• Most hydrogen used to produce ammonia (NH3) in the Haber process
• Also used to produce methanol (CH3OH)
CO (g) + 2 H2 (g) CH3OH (g)
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Nonmetals
Uses of Hydrogen
• Using hydrogen as a fuel would have many advantages:Highly exothermic reactionWater is only product
• Problem: How will we make the H2?
2 H2 (g) + O2 (g) 2 H2O (g) H = -483.6 kJ
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Nonmetals
Hydrides
• Three typesIonicMetallicMolecular
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Nonmetals
Ionic Hydrides• Formed between
hydrogen and alkali metals or heavy alkaline earth metals (Ca, Sr, Ba)
• Very strong bases and reducing agents
• React readily with water, so must be stored free from moisture
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Nonmetals
Metallic Hydrides
• Formed between hydrogen and transition metals, often in unusual ratiose.g., TiH1.8
• Retain electrical conductivity and other metallic properties
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Nonmetals
Molecular Hydrides
• Formed between hydrogen and nonmetals or metalloids
• Usually gases or liquids at room temperature and normal atmospheric pressure
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Nonmetals
Noble Gases• Extremely stable and
unreactive• Liquid He (boiling
point 4.2 K) used as a coolant
• Ne used in electric signs
• Ar used in light bulbs and as insulating gas between panes in thermal windows.
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Nonmetals
Xenon Compounds
• Of all noble gases, Xe can be forced to form compounds most easily
• KrF2 also known, but decomposes at -10C
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Nonmetals
Halogens
• Have outer electron configurations of ns2np5
• Large electron affinities and ionization energies
• Tend to accept one electron to form anion
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Nonmetals
Halogens
• All have -1 oxidation state
• All but fluorine also have positive oxidation states up to +7 when bonded to more electronegative atoms
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Nonmetals
Properties of Halogens
• Tend to be good oxidizers, due to their electronegativity
• Can oxidize anions of halides below them on periodic chart
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Nonmetals
Properties of Halogens
• Fluorine has unusually high reduction potential• It can easily oxidize water:
F2 (aq) + H2O (l) 2 HF (aq) + 1/2 O2 (g) E = 1.80 V
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Nonmetals
Uses of Halogens
• Fluorine reacts to form fluorocarbon compounds used as lubricants, refrigerants and plastics.
• Teflon is a polymer of fluorocarbons.
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Nonmetals
Uses of Halogens
• Chlorine is the most-used halogen.HClPlasticsBleachesWater purification
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Nonmetals
Uses of Halogens
• Bromine is the anion for silver in photographic film.
• KI is added to table salt as a dietary supplement.
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Nonmetals
Hydrogen Halides• Aqueous solutions of HCl,
HBr, and HI are, of course, strong acids.
• HF and HCl can be produced by reacting salts with H2SO4.
• Br- and I- oxidize too easily, so one must use a weaker oxidizing acid, like H3PO4.
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Nonmetals
HF• Hydrofluoric acid
reacts with silicates, components of most types of glass.
• This reaction causes glass to etch.
• Therefore, HF is usually stored in plastic containers.
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Nonmetals
Oxyacids and Oxyanions
• Oxyacid strength increases with increasing oxidation number of central halogen
• Oxyacids are strong oxidizers.• Oxyanions generally more stable than
corresponding acids
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Nonmetals
Perchlorates
While generally quite stable, perchlorates become exceedingly strong oxidizers when heated, and are used as rocket fuel.
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Nonmetals
Oxygen
• Joseph Priestley discovered oxygen in 1774.
• Lavoisier give it its name, which means “acid former.”
• Most commercial oxygen is obtained from air.
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Nonmetals
Oxygen
• Exists as one of two allotropes, O2 and O3 (ozone)
• Forms very strong bondsReactions of oxygen-containing
compounds have high activation energiesReactions can be very exothermic, even to
point of being explosive
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Nonmetals
Uses of Oxygen
• Oxidizing agentBleach pulp and
paperMedical usesWelding (with
acetylene)
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Nonmetals
Ozone• Bluish gas with sharp odor• Extremely irritating to
respiratory system
• Stronger oxidizer than O2
Used to purify water
• Used in organic synthesis• Absorbs UV light in upper
atmosphere
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Nonmetals
Oxides• Oxygen is second-most
electronegative elementAlways has negative
oxidation state except when bonded to F
• Acidic oxides like SO2 and SO3 form acids when exposed to water.
• Basic oxides like BaO form hydroxide ion when they react with water.
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Nonmetals
Peroxides
• Oxygen has oxidation state of -1
• O-O bond very weakDecomposition of
peroxides can be dangerously exothermic
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Nonmetals
Superoxides• Oxygen has oxidation
state of -1/2 • The most active metals
(K, Rb, Cs) form superoxides through reaction with O2
• React with H2O to form O2
Source of O2 in self-contained breathing devices
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Nonmetals
Other Group 6A Elements
• Have oxidation states of -2 as well as several positive oxidation states
• Can have expanded octets
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Nonmetals
Selenium and Tellurium
• Anions in minerals with Cu, Pb, Ag, and Au
• Found as helical chains of atoms
• Selenium not electrically conductive in dark, but quite so in lightUsed in light meters,
photosensors, and photocopiers
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Nonmetals
Sulfur
• Solid, yellow compound found in 8-membered ring
• As heated to melting, ring breaks and sulfur becomes viscous, reddish-brown liquid
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Nonmetals
Sulfur
• Most sulfur used for H2SO4 and for vulcanization of rubber
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Nonmetals
Pyrites
• Contain disulfide ion, S2
2-, the sulfur analog of peroxide
• Found in minerals like iron pyrite (fool’s gold)
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Nonmetals
Sulfides
• To say that many sulfides have rather unpleasant odors is a gross understatement.H2S is emitted by rotten eggs.
• Many minerals like galena (PbS) and cinnabar (HgS) are sulfides.
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Nonmetals
Sulfur Oxides, Oxyacids, and Oxyanions
• SO2 is a poison, particularly to lower organisms.Used to sterilize dried fruit and wineDissolves in H2O to form H2SO3
• Sulfites and bisulfites added to foods and wines to kill bacteria
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Nonmetals
Sulfur Oxides, Oxyacids, and Oxyanions
• Sulfuric acidStrong acidGood dehydrating agentDecent oxidizer
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Nonmetals
Sulfur Oxides, Oxyacids, and Oxyanions
• Thiosulfate ion resembles sulfate ion (a S replaces one of the O’s in sulfate)
• Sodium thiosulfate pentahydrate (Na2S2O35 H2O) used in photography to remove unexposed AgBr from film as soluble complex of thiosulfate
Sulfate
Thiosulfate
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Nonmetals
Nitrogen
• Discovered in 1772 by Daniel Rutherford
• Makes up 78% of Earth’s atmosphere
• Can exist in oxidation states from -3 to +5
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Nonmetals
Nitrogen• Many nitrogen-
containing compounds strong oxidizers
• N2 made into NH3 in Haber processNH3 is
precursor to many other compounds
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Nonmetals
Ammonia
• Hydrazines made from ammoniaOne intermediate is
chloramine (NH2Cl), poisonous compound produced when household ammonia and hypochlorite ion in bleach are mixed
• Hydrazines are strong oxidizers used in rocket fuels
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Nonmetals
Oxides and Oxyacids
• Nitrous oxide (N2O; laughing gas) was the first general anesthetic.
• It is also used in aerosol products like whipped cream.
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Nonmetals
Oxides and Oxyacids• Nitric oxide (NO) is a slightly toxic, colorless gas.
Recently shown to be neurotransmitter in humans involved in vasodilation
• Reacts with O2 in air to produce nitrogen dioxide, NO2
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Nonmetals
Oxides and Oxyacids• Nitric acid
Strong acid and oxidizer
Used in fertilizer and explosive production (TNT, nitrocellulose, nitroglycerine)
• Nitrous acidLess stable, yet
weaker acid than HNO3
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Nonmetals
Other Group 5A Elements
This group contains nonmetals (N and P), a metal (Bi), and metalloids (As and Sb).
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Nonmetals
Phosphorus
• Two allotropesWhite phosphorus
(P4)• Highly strained• Bursts into flames if
exposed to O2 in air
Red phosphorus• Very stable
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Nonmetals
Oxyphosphorus Compounds
Phosphorus(III) oxide (P4O6) and phosphorus(V) oxide (P4O10) are anhydride forms of phosphorous (H3PO3) and phosphoric (H3PO4) acids
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Nonmetals
Oxyphosphorus Compounds
• These acids condense to form polymeric forms.
• Phosphoric acid and phosphates are found in detergents, fertilizers, and important biomolecules like DNA, RNA, and ATP.
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Nonmetals
Carbon
• Exists as four allotropes:GraphiteDiamondFullerenesCarbon nanotubules
• Graphite converted to diamond (at 100,000 atm and 3000C) for industrial uses
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Nonmetals
Carbon Oxides• Carbon monoxide (CO)
Odorless, colorless gasBinds preferentially to iron in hemoglobin,
inhibiting O2 transport
Used as fuel, reducing agent in metallurgy, and precursor to organic compounds
• Carbon dioxide (CO2) Used to carbonate beverages, decaffeinate
products (in its supercritical form) and as a refrigerant (as Dry IceTM)
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Nonmetals
Carbonic Acid and Carbonates
• Dissolved CO2 in water is in equilibrium with carbonic acid, H2CO3
• Carbonates found as minerals like calcite, CaCO3, the primary constituent of limestone
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Nonmetals
Silicon
• Second most abundant element in Earth’s crust
• Semiconductor used in making transistors and solar cells
• Purified by zone-refining
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Nonmetals
Silicates
• Have a central silicon surrounded by 4 oxygens
• In disilicate, two tetrahedral structures share one oxygen
Silicate
Disilicate
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Nonmetals
Silicates
• These units can further connect into sheets or strands.
• Talc and asbestos are two examples of molecules containing these structures.
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Nonmetals
Boron• The only nonmetallic
Group 3A element• Compounds of boron
and hydrogen are called boranes.
• Because boron does not have a filled octet, structures such as diborane, in which two borons share one hydrogen are possible.
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Nonmetals
Boron
Borane anions, such as borohydride, BH4
-, are good reducing agents and sources of hydride ion.