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Nanotubes
nanotubes long, thin, hollow cylinders of atoms carbon nanotube = sp2 C in fused hexagonal rings
electrical conductors
Properties of BN and C
atomic radius decreases across the period electronegativity, ionization energy increase across the
period nonmetals on right of p block form anions in ionic compounds
often reduced in chemical reactions
making them oxidizing agents
Insulated Nanowire
Silicates
the most abundant elements of the Earths crust
are O and Si silicates are covalent atomic solids of Si and O
and minor amounts of other elements found in rocks, soils, and clays silicates have variable structures leading to the variety of properties found in rocks, clays, and soils
Tro, Chemistry: A Molecular Approach 7
Bonding in Silicates
Quartz
a 3-dimensional covalent
network of SiO4 tetrahedrons generally called silica formula unit is SiO2 when heated above 1500C and cooled quickly, get amorphous silica which we call glass
Aluminosilicates
Al substitutes for Si in some of the lattice sites SiO2 becomes AlO2 the negative charge is countered by the inclusion
of a cation
Albite = of Si replaced by Al; Na(AlO2)(SiO2)3 Anorthite = of Si replaced by Al; Ca(AlO2)2(SiO2)2
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when 3 O of each
Sheet Silicates
tetrahedron are shared, the result is a sheet structure called a phyllosilicate formula unit = Si2O52 sheets are ionically bonded to metal cations that lie between the sheets talc and mica
Tro, Chemistry: A Molecular Approach 14
Mica: a Phyllosilicate
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Silicate Structures
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Boron
Boron Trihalides
BX3 sp2 B
trigonal planar, 120 bond angles forms single bonds that are shorter and stronger than sp3 C some overlap of empty p on B with full p on halogen
Boron-Oxygen Compounds
form structures with trigonal
BO3 units in B2O3, six units are linked in a flat hexagonal B6O6 ring
melts at 450C
melt dissolves many metal oxides and silicon oxides to form glasses of different compositions
Tro, Chemistry: A Molecular Approach 19
compounds of B and H used as reagent in hydrogenation of C=C closo-Boranes have formula BnHn2 and form
closed polyhedra with a BH unit at each vertex
Boranes closo-Boranes
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Carbon
exhibits the most versatile bonding of all the
elements diamond structure consists of tetrahedral sp3 carbons in a 3-dimensional array graphite structures consist of trigonal planar sp2 carbons in a 2-dimensional array
sheets attracted by weak dispersion forces
Graphite
black 2.25 0.5 7.3 x 10-4
Buckminsterfullerene, C60
black 1.65
~10-14
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~3700 0.4 2.42 Kimberlite (S. Africa)
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~3800 0.0 Pegmatite (Sri Lanka) 800 sublimes 9.08 2.2 (600 nm) Shungite (Russia)
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anthracite coal has highest C content bituminous coal has high C, but high S heating coal in the absence of air forms coke
carbon and ash
Nanotubes
long hollow tubes constructed of fused C6 rings electrical conductors can incorporate metals and other small
molecules and elements
used to stabilize unstable molecules
Nanotubes
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Nanocars
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Carbides
Calcium Carbide
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Carbon Oxides
CO2
0.04% in atmosphere
increased by 25% over the past century
CO
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Carbonates
solubility of CO2 in H2O due to carbonate formation
CO2 + H2O H2CO3 H2CO3 + H2O H3O+ + HCO3 HCO3 + H2O H3O+ + CO32 doesnt decompose on heating
Elemental Nitrogen
N2
78% of atmosphere purified by distillation of liquid air, or filtering air through zeolites very stable, very unreactive
NN
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Elemental Phosphorus
P
white phosphorus
white, soft, waxy solid that is flammable and toxic stored under water to prevent spontaneous combustion 2 Ca3(PO4)2 (apatite) + 6 SiO2 + 10 C P4(g, wh) + 6 CaSiO3 + 10 CO tetrahedron with small angles 60
red phosphorus
formed by heating white P to about 300C in absence of air amorphous mostly linked tetrahedra not as reactive or toxic as white P used in match heads
black phosphorus
formed by heating white P under pressure most thermodynamically stable form, therefore least reactive layered structure similar to graphite
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Phosphorus
Hydrides of Nitrogen
ammonia, NH3
pungent gas basic NH3 + H2O NH4+ + OH
used as chemical fertilizers
hydrazine, N2H4
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Hydrazine
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formed by reaction of N2 or NOx with O2 all unstable and will eventually decompose into N2 and O2 NO = nitrogen monoxide = nitric oxide NO2 = nitrogen dioxide
2 NO2 N2O4 red-brown gas free radical important in living systems free radical
Oxides of Nitrogen
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Nitric Acid
HNO3 = nitric acid
produced by the Ostwald Process 4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g) 2 NO(g) + O2(g) 2 NO2(g) 3 NO2(g) + H2O(l) 2 HNO3(l) + NO(g) strong acid strong oxidizing agent concentrated = 70% by mass = 16 M
some HNO3 in bottle reacts with H2O to form NO2
NO3 = nitrate
ammonium nitrate can decompose explosively 2 NH4NO3 2 N2 + O2 + 4 H2O metal nitrates used to give colors to fireworks very soluble in water oxidizing agent NaNO2 used as food preservative in processed meats
and other nitrates
NO2 = nitrite
kills botulism bacteria keeps meat from browning when exposed to air can form nitrosamines which may increase risk of colon cancer??
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Phosphine
PH3
colorless, poisonous gas that smells like rotting fish formed by reacting metal phosphides with water Ca3P2(s) + 6 H2O(l) 2 PH3(g) + 3 Ca(OH)2(aq) also by reaction of wh P with H2O in basic solution 2 P4(s) + 9 H2O(l) + 3 OH(aq) 5 PH3(g) + 3 H2PO4(aq) decomposes on heating to elements 4 PH3(g) P4(s) + 6 H2(g) reacts with acids to form PH4+ ion does not form basic solutions
Tro, Chemistry: A Molecular Approach 45
Phosphorus Halides
Phosphorus Oxides
P4 reacts with O2 to make P4O6(s) or P4O10(s)
get P4O10 with excess O2
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white solid that melts at 42C concentrated = 85% by mass = 14.7 M produced by reacting P4O10 with water or the reaction of Ca3(PO4)2 with sulfuric acid P4O10(s) + 6 H2O(l) 4 H3PO4(aq) Ca3(PO4)2(s) + 3 H2SO4(l) 3 CaSO4(s) + 2 H3PO4(qa) used in rust removal, fertilizers, detergent additives and food preservative
sodium pyrophosphate = Na4P2O7 sodium tripolyphosphate = Na5P3O10
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Oxygen
2 s 22 p 4
6 valence electrons
second highest electronegativity (3.5) very high abundance in crust, and highest
abundance of any element on Earth found in most common compounds
Tro, Chemistry: A Molecular Approach 50
Elemental Oxygen
O2
nonpolar, colorless, odorless gas freezing point 183C at which it becomes a pale blue liquid slightly soluble in water
0.04 g/L
can be synthesized by heating metal oxides, chlorates, or nitrates HgO(s) Hg(l) + O2(g) 2 NaNO3(s) 2 NaNO2(s) + O2(g) 2 KClO3(s) 2 KCl(s) + 3 O2(g) used in high temperature combustion
blast furnace, oxyacetylene torch
medical treatment
lung disease, hyperbaric O2 to treat skin wounds
Tro, Chemistry: A Molecular Approach 51
Oxides
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O3
Ozone
toxic, pungent, blue, diamagnetic gas denser than O2 freezing point 112C, where it becomes a blue liquid synthesized naturally from O2 through the activation by ultraviolet light
mainly in the stratosphere protecting the living Earth from harmful UV rays
spontaneously decomposes into O2 commercial use as a strong oxidizing agent and disinfectant formed in the troposphere by interaction of UV light and auto exhaust
oxidation damages skin, lungs, eyes, and cracks plastics and rubbers
Tro, Chemistry: A Molecular Approach 53
Sulfur
large atom and weaker oxidizer than oxygen often shows +2, +4, or +6 oxidation numbers in its
compounds, as well as 2 composes 0.06% of Earths crust elemental sulfur found in a few natural deposits
some on the surface
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Frasch Process
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Allotropes of Sulfur
several crystalline forms the most common naturally occurring allotrope has S8 rings
most others also ring structures of various sizes
viscosity when heated above 150C, rings start breaking and a dark brown viscous liquid forms
darkest at 180C above 180C the liquid becomes less viscous
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sulfur at ~150C
sulfur at ~180C
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Amorphous Sulfur
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roasted in absence of air forming FeS(s) and S2(g) roasted in air to make SO2(g), which is later reduced react with acids to make H2S most insoluble in water used as bactericide and stop dandruff in shampoo
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Metal Sulfides
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SO2
Sulfur Dioxide
colorless, dense, acrid gas that is toxic produced naturally by volcanic action and as a byproduct of industrial processes
including electrical generation by burning oil and coal, as well as metal extraction
acidic
SO2(g) + H2O(l) H2SO3(aq) forms acid rain in the air 2 SO2(g) + O2(g) + 2 H2O(l) 2 H2SO4(aq) removed from stack by scrubbing with limestone CaCO3(s) CaO(s) + O2(g) 2 CaO(g) + 2 SO2(g) + O2(g) 2 CaSO4(g) used to treat fruits and vegetables as a preservative
Tro, Chemistry: A Molecular Approach 62
Sulfuric Acid
most produced chemical in the world strong acid, good oxidizing agent, dehydrating agent used in production of fertilizers, dyes, petrochemicals,
paints, plastics, explosives, batteries, steel, and detergents melting point 10.4C, boiling point 337C
oily, dense liquid at room temperature
Dehydration of Sucrose
Production of H2SO4
complete using V2O5 catalyst S(g) + O2(g) SO2(g) 2 SO2(g) + O2(g) 2 SO3(g)
Halogens
most reactive nonmetal group, never found in
elemental form in nature come from dissolved salts in seawater
except fluorine, which comes from minerals fluorospar (CaF2) and fluoroapatite [Ca10F2(PO4)6]
atomic radius increases down the column most electronegative element in its period, decreasing
down the column fluorine only has oxidation states of -1 or 0, others have oxidation states ranging from -1 to +7
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Fluorine
F2 is a yellow-green toxic gas F2 is the most reactive nonmetal and forms binary compounds
with every element except He, Ne, and Ar
including XeF2, XeF6, XeOF4, KrF2 so reactive it reacts with other elements of low reactivity resulting in flames even reacts with the very unreactive asbestos and glass
stored in Fe, Cu, or Ni containers because the metal fluoride that forms coats the surface protecting the rest of the metal
exothermic small ion size of F leads to large lattice energies in ionic compounds produced by the electrolysis of HF
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Hydrofluoric Acid
HF
produced by the reaction of fluorospar with H2SO4 CaF2(s) + H2SO4(l) CaSO4(s) + 2 HF(g) crystalline HF is zig-zag chains HF is weak acid, Ka = 6.8 x 10-4 at 25C F can combine with HF to form complex ion HF2
with bridging H
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Halogen Compounds
tend to be explosive OF2 only compound with O = +2 oxidation state ClO2(g) is strong oxidizer used to bleach flour and wood pulp
explosive so diluted with CO2 and N2 produced by oxidation of NaClO2 with Cl2 or the reduction of NaClO3 with HCl 2 NaClO2 + Cl2 2 NaCl + 2 ClO2 2 NaClO3 + 4 HCl 2 ClO2 + 2 H2O + 2 NaCl
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