Chapter 14

The Group 14 Elements

Group 14 Elements
Carbon
nonmetal

Silicon and Germanium

semimetals

Tin and Lead

weakly, electropositive metals

Group 14 Properties
Ability to form network covalent bonding and to catenate

Carbon (graphite)

Dichlorodimethyltin(IV)

Group Trends
Melting and boiling points
Element Melting Point (C) 1420 945 Boiling Point (C)

Carbon Silicon Germanium Tin Lead

232 327

Sublimes at 4100 3280 2850 2623 1751

Oxidation States
Multiple oxidation states are common
+4 for all the elements
covalent bonding CO2

-4 for C, Si, and Ge

covalent bonding CH4

+2 for Sn and Pb
ionic bonding PbF2

Stability of Oxidation States

Frost diagram
Most stable?

Most reducing?

Most oxidizing?

Carbon
Three common allotropes
Diamond Graphite Fullerenes and carbon nanotubes

Diamond
Covalent network of tetrahedrally, arranged covalent bonds

Diamond History
Graphite and diamond were thought to be two, different substances
In 1814, Humphry Davy burned his wifes diamond to prove it was indeed carbon C(s) + O2(g) CO2(g)

Diamond
Electrical insulator Very good thermal conductor High melting point
4000C

Regular diamond (cubic)

Lonsdaleite (hexagonal)

Diamonds in Nature
Found predominantly in Africa
Zaire is the largest producer
29%

Russia
22%

South Africa is the largest in terms of gemquality

17%

Diamonds in Nature
Crater of Diamonds State Park
Murfreesboro, Arkansas http://www.craterofdiamondsstatepark.com/

Synthetic Diamonds
Can make synthetic diamonds from graphite by adding heat (1600C) and pressure (5 GPa)

Tracy Hall GE

Synthetic Diamonds
Thin films of diamonds can be made at low temperatures

Diamond Jet Reactor

Synthetic Diamonds
New methods have become available to produce more gem-quality stones

Diamond Uses
Drill bits and saws Surgical knife coatings Computer chip coatings Jewlery

Graphite
Hexagonal layers of covalently bound carbon
similar to benzene delocalized pi system

Graphite Layers
Very weak interactions between the layers
335 pm interlayer distance van der Waals radius is ~150 pm

abab arrangment

Graphite Properties
Excellent conductor in two dimensions
due to the electron delocalization

Excellent lubricant
sheets slide

Absorber of gas

Graphite Reactivity
More thermodynamically stable than diamond More kinetically reactive than diamond Forms intercalation compounds

Graphite Sources
Mining
China Siberia North and South Korea

Graphite Production
Acheson Process

2500C, 30 hours

Graphite Uses
Lubricants Electrodes Lead pencils
clay mixtures
hard mixtures 2H soft mixtures HB

Fullerenes
Carbon atoms arranged in a spherical or ellipsoidal structure
five and six-membered rings

C60, Buckminsterfullerene

C70

Fullerenes
Named after R. Buckminster Fuller

Buckminster Fullers Dome 1967 Montral Expo

R. Buckminster Fuller (1895-1983)

Discovery of Fullerenes
David Huffman and Wolfgang Krtschmer
1982

Discovery of Fullerenes
Kroto, Curl, and Smalley

Discovery of Fullerenes
Kroto, Curl, and Smalley

Fullerene Production
Huffman and Krtschmer

Fullerene Properties
very weak intermolecular forces sublime when heated soluble in most nonpolar solvents give bright colors in solution

Fullerene Properties
C60 crystal lattice (fcc)
low density, 1.5 g/cm3 non-conductors of electricity strong absorber of light

Fullerene Chemistry
Interstitial
superconductors

[Rb+]3[C603-] superconductor

Fullerene Chemistry
Metal encapsulation
Li@C82 He@C60

Fullerene Chemistry
Reaction with gases C60(s) + 30F2(g) C60F60(s)

Cluster Sizes
Many different sizes

Carbon Nanotubes
Sumio Iijima
1991

Nanotube Types
Single-walled (SWNT) Multi-walled (MWNT)

Nanotube Properties
excellent conductor molecular storage

Impure Carbon
Amorphous carbon (coke)
made by heating coal in an inert atmosphere mostly graphite with some hydrogen impurities
used in iron production removes oxygen 5 x 108 tons per year

Impure Carbon
Carbon black
fine, powdered carbon 3.65 x 109 tons annually

Impure Carbon
Activated carbon
high surface area
103 m2/g

removes impurities from organic reactions decolorizes chemicals

Carbon Isotopes
Three isotopes
carbon-12 (98.89 %) carbon-13 (1.11 %) carbon-14 (0.0000001%)
radioactive t1/2 = 5.7 x 103 years

14C

Radioactive Dating

Carbon Chemistry
Two important properties
catenation
a bonding capacity greater than or equal to 2 an ability of the element to bond to itself a kinetic inertness of the catenated compound toward or molecules and ions

multiple bonding

Catenation
An ability of an element to bond with itself
Carbon bonds
CC CO

Bond energy (kJ/mol) 346

358

Silicon bonds
SiSi SiO

Bond energy (kJ/mol) 222

452

Bond Energies
Important in determining the reactivity and/or relative stabilities of products CH4(g) + 4F2(g) CF4(g) + 4HF(g) not CF4(g) + 4HF(g) CH4(g) + 4F2(g)
Bond Bond energy (kJ/mol) Bond Bond energy (kJ/mol) CH 411 CF 485 FF 155 HF 565

Carbides
Binary compounds of carbon with more electropositive elements
typically hard with high melting points three types:
ionic covalent metallic

Ionic Carbides
Formed by the most electropositive elements
alkali and alkaline earth metals aluminum

Only reactive carbides

Na2C2(s) + 2H2O(l) 2NaOH(aq) + C2H2(g) Al4C3(s) + 12H2O(l) 4Al(OH)3(s) + 3CH4(g)

Covalent Carbides
Few examples
silicon carbide and boron carbide
only important nonoxide ceramic
7 x 105 tons produced annually

SiO2(s) + 3C(s) SiC(s) + 2CO(g)

Covalent Carbides
Silicon carbide uses
grinding and polishing agents high-temperature materials applications mirror backings body armor

Moissanite
SiC
hexagonal similar to lonsdaelite and ZrO2
Hardness (Mohs scale) C SiC ZrO2 10 9.25-9.5 8.5 Refractive index 2.24 2.65-2.69 2.15 Density (g/cm3) 3.5 3.2 5.8

SiC

C ZrO2

Metallic Carbides
Formed with transition metals
carbon atoms fit in the octahedral interstices in the metal lattice (interstitial carbides)
close-packed structure 130 pm metallic radius

shiny luster conduct electricity hard and high melting point chemical resistance

Metallic Carbides
Tungsten carbide
20,000 tons produced annually used in cutting tools

Metallic Carbides
Fe3C
cementite

Carbon Monoxide
Colorless, odorless gas Very poisonous
300-fold greater affinity for hemeglobin than oxygen

Carbon Monoxide
Carboncarbon triple bond
1070 kJ/mol 1.11 bond length

Carbon Monoxide Production

Incomplete combustion
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) CH4(g) + 3/2O2(g) CO(g) + 2H2O(l)

Dehydration of formic acid

HCOOH(l) + H2SO4(l) H2O(l) + CO(g) +H2SO4(aq)

Carbon Monoxide Reactivity

With oxygen 2CO(g) + O2(g) 2CO2(g) With halogens CO(g) + Cl2(g) COCl2(g)
phosgene

Phosgene
blister agent
Country Austria-Hungary British Empire France Germany Italy Russia USA Total Casualties 100,000 188,706 190,000 200,000 60,000 419,340 72,807 Death 3,000 8,109 8,000 9,000 4,627 56,000 1,462

Others

10,000

1,000

Carbon Monoxide Reactivity

With sulfur CO(g) + S(s) COS(g) As a reducing agent Fe2O3(s) + 3CO(g) 2Fe(l) + 3CO2(g)

Carbon Monoxide Reactivity

With hydrogen CO(g) + 2H2(g) CH3OH(g) OXO process CO(g) + C2H4(g) + H2(g) C2H5CHO(g)
10 million tons of chemicals synthesized using a similar process

Carbon Monoxide Reactivity

With transition metals
highly toxic used for preparation of other transition metal complexes

Mo(s) + 6CO(g) Mo(CO)6(s)

Carbon Dioxide
Dense, colorless, odorless gas
low reactivity
will not combust

2Ca(s) + CO2(g) 2CaO(s) + C(s)

Carbon Dioxide
No liquid phase at atmospheric pressure
sublimes

Water

Carbon Dioxide

Carbon Dioxide Use

40 million tons in the U.S. annually
50% in refrigerant applications 25% in the soft drink industry 25% in the aerosol, life raft, and fireextinguishing industries

Carbon Dioxide Sources

Byproduct of manufacturing processes
ammonia, molten metals, cement, sugar fermentation

Reaction of an acid with a carbonate

2HCl(aq) +CaCO3(s) CaCl2(aq) + H2O(l) + CO2(g)

Carbon Dioxide Testing

Limewater test
CO2(g) + Ca(OH)2(aq) CaCO3(s) + H2O(l) CO2(g) + CaCO3(s) + H2O(l) Ca2+(aq) + 2HCO3-(aq)

Carbonic Acid
Used to carbonate soft drinks
H2CO3(aq) + H2O(l) H3O+(aq) + HCO3-(aq) HCO3-(aq) + H2O(l) H3O+(aq) + CO32-(aq)

Carbon Dioxide Reactivity

With bases
2KOH(aq) + CO2(g) K2CO3(aq) + H2O(l) K2CO3(aq) + CO2(g) + H2O(l) 2KHCO3(aq)

Introduction
A supercritical fluid (SCF) is any substance at a temperature and pressure above its critical values
Critical temperature of a compound is defined as the temperature above which a pure, gaseous component cannot be liquefied regardless of the pressure applied. Critical pressure is defined as the vapor pressure of the gas at the critical temperature.

Introduction
The temperature and pressure at which the gas and liquid phases become identical is the critical point. In the supercritical environment only one phase exists.
The fluid, as it is termed, is neither a gas nor a liquid and is best described as intermediate to the two extremes. This phase retains the solvent power common to liquids as well as the transport properties common to gases.

Table 1. Comparison of physical and transport properties of gases, liquids and SCFs.
Property Gas SCF Liquid

Density (kg m-3)

Viscosity (cP) Diffusivity (mm2 s-1)

1
0.01 1-10

100-800
0.05-0.1 0.01-0.1

1000
0.5-1.0 0.001

What does scCO2 look like?

Here we can see the seperate phases of carbon dioxide. The meniscus is easily observed.

What does scCO2 look like?

With an increase in temperature the meniscus begins to diminish.

What does scCO2 look like?

Increasing the temperature further causes the gas and liquid densities to become more similar. The meniscus is less easily observed but still evident.

What does scCO2 look like?

Once the critical temperature and pressure have been reached the two distinct phases of liquid and gas are no longer visible. The meniscus can no longer be seen. One homogenous phase called the "supercritical fluid" phase occurs which shows properties of both liquids and gases.

Extraction and Chromatography

1970s were first used commercially
to decaffeinate coffee

Media have been used successfully to extract analytes from a variety of complex compounds through manipulation of system pressure and temperature.
By comparison, conventional methods (e.g., Soxhlet extraction and vacuum isolation) are more complicated and time and energy intensive.

Extraction and Chromatography

The limiting property of sc-CO2 is that it is only capable of dissolving nonpolar organic-based solutes.
The addition of small amounts of a cosolvent such as acetone has been shown to significantly improve the solubility of relatively polar solutes.

Micelle Formation
Solubility of ionic compounds such as aqueous metal salts has been enhanced through inverse micelle formation using fluorinated surfactants.

Extraction
SCF extraction has also been applied to environmental remediation such as removing organics from water and soil. To extract metal contaminants, a chelating agent is commonly added to the fluid, with the soluble metal complex being removed from the SCF following system depressurization.

Other Uses for scCO2

Catalysis Materials synthesis Chemical vapor deposition (CVD)

The Greenhouse Effect

Radiation trapping

Molecular Vibrations
Only heteronuclear, polyatomic molecules absorb infrared energy
dinitrogen, dioxygen, and argon do not

Earths Infrared Spectrum

Sources of Carbon Dioxide

Volcanoes Burning of vegetation Burning of fossil fuels

Carbon Dioxide Levels

Kyoto Protocol
Results of a meeting of 161 countries in 1998 on greenhouse emissions Aims
reduce the emmissions of carbon dioxide, methane, dinitrogen oxide, hydrofluorocarbons, perfluorocarbons, and sulfur hexafluoride reduce emissions by 5% of those in 1990

Kyoto Protocol
Solutions to the problem
place a greater dependence upon the generation of power from non-carbon-based fuels
wind, water, and nuclear power

use carbon resources in a more efficient manner

hybrid-fuel passenger vehicles biodiesel fuels

Kyoto Protocol
Other solutions
if an industrialized nation helps a devloping country reduce its emissions, then that industrialized country can count part of the benefits towards its own reduction goal emission-reduction credits are tradable like stocks removing greenhouse gases by increasing forestry can also be credited

Kyoto Protocol
Signed by all nations except the U.S.
U.S. produces 25% of the worlds emissions

Carbon Dioxide Sequestration

Storage of emitted carbon dioxide
increasing photosynthetic absorption
planting trees iron enrichment in seawater

developing chemical technology to convert carbon dioxide into useful products

limited due to quantities produced and energy needed

Carbon Dioxide Sequestration

Storage of emitted carbon dioxide
storing the gas in underground geological formations
separating CO2 from methane in natural gas

pumping CO2 into oceans

Carbon Dioxide Sequestration

Pumping into oceans
will greatly decrease the pH of the oceans CO2(aq) + H2O(l) H3O+(aq) + HCO3-(aq) CO2(aq) + CO32-(aq) 2 HCO3-(aq)

Hydrogen Carbonates
Prepared by reaction of the carbonate with carbon dioxide and water
CaCO3(s) + CO2(aq) + H2O(l) Ca(HCO3)2(aq)

All hydrogen carbonates decompose to the carbonate upon heating

Ca(HCO3)2(aq) CaCO3(s) + CO2(aq) + H2O(l)

Hydrogen Carbonates
Amphoteric HCO3-(aq) + H+(aq) CO2(g) + H2O(l) HCO3-(aq) + OH-(aq) CO32-(aq) + H2O(l)

Carbonates
Basic in solution due to hydrolysis CO32-(aq) + H2O(l) HCO3-(aq) + OH-(aq)
washing soda

Carbonates
bonding

Carbonates
Molecular orbitals
1 total pi bond
1/3 per oxygen atom

Carbonates
Properties
most insoluble
except alkali metal and ammonium carbonates

most decompose upon heating to give the oxide CaCO3(s) + heat CaO(s) + CO2(g) for weakly electropositive metals, Ag2CO3(s) + heat Ag2O(s) + CO2(g) Ag2O(s) + heat 2Ag(s) + 1/2O2(g)

Carbon Disulfide
Sulfur analogue of carbon dioxide
colorless, highly flammable, low-boiling sweet smell when pure, foul when not highly toxic CH4(g) + 4S(l) + heat CS2(g) + 2H2S(g) used in the production of cellophane, rayon polymers, and carbon tetrachloride
1 million tons annually

Carbonyl Sulfide
S=C=O, or COS
most abundant sulfur-containing gas in the atmosphere
5 x 106 tons

low reactivity only sulfur-containing gas to penetrate the stratosphere

Carbon Tetrahalides
Carbon tetrahedrally bound to four halogen molecules
properties are dependent upon the dispersion forces present
CF4 is a colorless gas CCl4 is a dense, oily liquid CBr4 is a pale, yellow solid CI4 is a bright, red solid

Carbon Tetrachloride
good, nonpolar solvent
very carcinogenic was used in fire extinguishers
oxidized to form poisonous carbonyl chloride, COCl2

greenhouse gas and ozone depleter

Carbon Tetrachloride
Production
FeCl3 catalyzed reaction CS2(g) + 3Cl2(g) CCl4(g) + S2Cl2(l) CS2(g) + 2S2Cl2(l) + heat CCl4(g) + 6S(s) reaction of methane with chlorine CH4(g) + 4Cl2(g) CCl4(l) + 4HCl(g)

Carbon Tetrachloride
Reactivity
very inert CCl4(l) + 3H2O(l) H2CO3(aq) + 4HCl(g) G = -380 kJ/mol SiCl4(l) + 3H2O(l) H2SiO3(aq) + 4HCl(g) G = -289 kJ/mol

Chlorofluorocarbons
First prepared in 1928 by GM chemist Thomas Midgley, Jr.
CCl2F2
very good refrigerant completely unreactive nontoxic

Chlorofluorocarbons
Nomenclature
The first digit represents the number of carbon atoms minus one The second digit represents the number of hydrogen atoms plus one The third digit represents the number of fluorine atoms Structural isomers are distinguished by a,b, etc

Chlorofluorocarbons
Nomenclature
Cl Cl F Cl F F Cl Cl F F2C Cl F2C C F2 F2 C CF2 Br CF2 Br F F

1,1,2-trichlorotrifluoroethane Perfluorocyclohexane Trichlorofluoromethane Dibromodifluoromethane Freon 113 Freon 11 Freon C5112 Freon 12B2

Chlorofluorocarbons
Ozone depleters Cl + O3 O2 + ClO ClO Cl + O Cl + O3 O2 + ClO ClO + O Cl + O2

CFC Alternatives
HFC-134a
CF3CH2F
costly to produce current equipment needs to be replaced greenhouse gas

Methane
CH4
colorless, odorless gas
only detectable by addition of impurities

major source of thermal energy (natural gas) CH4(g) + 2O2(g) CO2(g) + 2H2O(g) fastest growing gas in the atmosphere
cattle and sheep by-products

Cyanides
HCN
toxic but useful
over 1 million tons annually

Almond-like odor liquid at room temperature due to hydrogen bonding

H CN H CN

HCN Production
Degussa Process
CH4(g) + NH3(g) + Pt HCN(g) + 3H2(g)

Andrussow Process
2CH4(g) + 2NH3(g) + 3O2(g) 2HCN(g) + 6H2O(g)

Andrussow Process

Hydrogen Cyanide
Acidic in water
HCN(aq) + H2O(l) H3O+(aq) + CN-(aq)

Neutralization produces sodium cyanide

HCN(aq) + NaOH(aq) H2O (l) + NaCN(aq) used in the extraction of gold and silver from ores

Hydrogen Cyanide Uses

70% in polymer production
Nylon Melamine Acrylic plastics

15% in NaCN production

Hydrogen Cyanide History

The Peoples Temple

Hydrogen Cyanide Gas Chambers

2NaCN(aq) + H2SO4(aq) Na2SO4(aq) + 2HCN(g)