Chapter

 4  

Carbon  Compounds  
Carbon  Compounds  

2
 Ice  on  Fire  
• In  November  2000,  the  fishing  trawler  Ocean  
Selector  pulled  up  a  surprising  catch  from  a  
depth  of  800  m  off  Canada’s  west  coast—a  net  
containing  1  tonne  of  large  hissing  and  frothing  
chunks  of  ice.  
• These  ice  chunks  burned  when  a  match  was  put  
to  them.  
• What  is  this  ice-­‐like  substance?  

3
 Ice  on  Fire  
A  Molecular-­‐Level  View:  

A  single  molecule  of  methane  in  a  clathrate  cage  of  water  

molecules  (leG).  Cages  of  different  sizes  occupied  by  
methane  molecules  are  linked  together  to  form  a  
methane  clathrate  hydrate  (right).  
4
 Ice  on  Fire  
A  Molecular-­‐Level  View:  
• Methane  clathrate  hydrate,  in  which  guest  methane  
molecules  are  trapped  inside  a  cage  made  of  host  water  
molecules.  
• The  bonding  in  methane  clathrate  hydrates  is  an  
example  of  supramolecular  or  host–guest  chemistry.  
• Carbon  dioxide  and  other  small  carbon  compounds  can  
also  form  clathrate  hydrates.  

5
 Ice  on  Fire  
• Gas  hydrate  or  clathrate  complexes  are  formed  in  
nature  when  the  host  water  and  the  guest  are  present  
at  the  right  concentraNons,  and  at  relaNvely  low  
temperature  and  high  pressure.  
• Massive  amounts  of  methane  are  stored  in  this  way  in  
nature.  This  is  potenNally  useful  as  a  source  of  energy  
and  potenNally  dangerous  to  our  climate  if  released  into  
the  atmosphere.  

6
 Ice  on  Fire  
Swapping  Guests  
• Replacement  of  methane  and  ethane  molecules  in  a  
clathrate  hydrate  with  carbon  dioxide.  Simplified  
representaNons  of  each  of  the  gas  molecules  as  single  
coloured  spheres  are  shown.  

• Spectroscopy  can  be  used  to  monitor  the  reacNon.  

7
 Ice  on  Fire  
Fishing  for  SoluEons  to  Pipeline  Clathrate  Plugs  
• An  anNfreeze  protein  produced  by  the  winter  flounder  
is  quite  effecNve  at  prevenNng  both  the  formaNon  and  
growth  of  methane  hydrate  crystals  in  laboratory  tests.  

8
 Methane:  Signature  of  Life  
Methane  
• A  tasteless,  odourless,  and  colourless  gas  
• It  belongs  to  the  hydrocarbon  subset  of  organic  
molecules;  its  molecules  consist  of  only  carbon  and  
hydrogen  atoms  joined  together.  
• It  is  the  principal  component  in  the  fossil  fuel  natural  
gas.  

Methane,  CH4  

9
 Methane  Fuelling  Human  AcEvity  
• Thermogenic  methane:  Methane  produced  by  buried  
decaying  organic  material,  exposed  to  heat  and  pressure.  
• CombusNon  of  methane  to  produce  energy  

• Valuable  feedstock  in  industrial  chemical  processes  to  

produce  H2(g)  and  CO(g)  

• Methane  exists  in  in  many  places  on  Earth—in  

underground  reservoirs,  the  oceans,  the  ArcNc  tundra,  
and  in  the  atmosphere.  
10
 Methane:  Signature  of  Life  
Methanogens  
• Most  of  the  methane  on  Earth  has  a  biological  origin.  
• Methane  resulNng  from  biological  acNvity  (life  
processes)  is  referred  to  as  biogenic  methane,  or  
biogas.  
• Methanogenic  organisms  are  typically  found  in  
environments  that  are  very  low  in  oxygen,  such  as  in  
ocean  sediments,  wetlands,  water-­‐logged  rice  paddy  
soils,  and  landfills.  

11
 Methane:  Signature  of  Life  
• Abiogenic  methane  is  produced  from  non-­‐
biological  processes,  such  as  volcanic  erupNons.  

• This  reacNon  depends    

on  temperature,    
pressure,  and  the    
presence  of  catalysts.  

12
 Methane  in  Our  Atmosphere  
• Methane  is  the  predominant  hydrocarbon  found  in  the  
earth’s  atmosphere.  
• Most  of  that  methane  is  biogenic;  about  70%  comes  
from  human  acNvity,  including  energy  and  livestock  
producNon.  
• The  average  lifeNme  of  a  methane  molecule  in  our  
atmosphere  is  about  10  years.  
• When  released  into  the  atmosphere,  methane  is  
eventually  removed  by  reacNon  with  hydroxyl  radicals.  

13
 Methane  in  Our  Atmosphere  

Placeholder
Atmospheric concentration over the
past 2000 years plot, p.96
(Figure 4.4)

Atmospheric  concentraNon  of  CH4  (ppb),  CO2  (ppm),  and  

N2O  (ppb)  over  the  past  2000  years.  

14
 IdenEfying  a  Methane  Sample  
How  can  a  chemist  tell  whether  a  sample  of  
methane  is  biogenic,  thermogenic,  or  abiogenic?  
• Isotope  RaNo  Mass  Spectrometry  
– For  example,  biogenic  methane  contains  a  
larger  isotopic  abundance  of  12C  atoms  
(depleted  in  13C)  than  does  abiogenic  methane.  

15
Climate  Change  and  “Greenhouse  Gases”:  
Earth’s  RadiaEon  Balance  
• Our  knowledge  of  the  earth’s  temperature  over  
geological  Nmescales  comes  from  measuring  the  18O/
16O  isotope  raNo  of  water  molecules  in  ice  cores.    

• Carbon  dioxide  levels  are  found  by  chemical  analysis  of  

the  bubbles  trapped  in  those  same  ice  cores.  A  strong  
correlaNon  exists  between  CO2  (g)  levels  and  
temperature  over  the  past  half-­‐million  years.    
• Evidence  suggests  that  human  acNvity  over  the  past  250  
years  is  driving  new  changes  in  the  earth’s  climate.  
16
 Earth’s  RadiaEon  Balance  

Long-­‐wave   Short-­‐wave  
RadiaNon   RadiaNon  

Long-­‐  and  short-­‐wave  radiaNon  scanning  radiometer  images  of  Earth,  

collected  by  the  CERES  instrument  from  March–May  2001.    
Courtesy  of  the  Atmospheric  Sciences  Data  Center  and  the  CERES  Science  Team  at  
NASA  Langley  Research  Center.  
17
Climate  Change  and  “Greenhouse  Gases”  

Historical  
trends  in  
atmospheric  
temperature  
and  CO2(g)  
concentraNon  
on  geological  
and  recent  
Nmescales  

18
 Earth’s  RadiaEon  Balance  

Global  mean  temperature  changes  since  1850,  relaNve  to  the  

1961–1990  normals.  
19
Climate  Change  and  “Greenhouse  Gases”  
Chemists  can  contribute  in  five  ways:  
• Understanding  the  formaNon  and  behaviour  of  aerosols.  
• Understanding  the  absorpNon  of  infrared  radiaNon  from  
the  earth  by  “greenhouse  gases”  (e.g.,  CH4,  CO2,  N2O).  
• Carrying  out  experiments  and  models  to  understand  the  
effect  of  increased  CO2(g)  on  life  in  the  oceans.  
• Developing  methods  to  capture  carbon  compounds.  
• Advancing  the  science  and  technology  needed  to  
implement  alternaNve  forms  of  energy.  
20
Climate  Change  and  “Greenhouse  Gases”  
ReflecEon  of  Visible  Light  by  Earth’s  Atmosphere:  
Clouds,  Ice,  and  Aerosols  
•The  fracNon  of  sunlight  reflected  by  Earth  is  called  its  
albedo.  
•Atmospheric  aerosols,  made  of  fine  droplets  of  liquid  or  
dust  suspended  in  the  atmosphere,  cause  cooling  by  
reflecNng  incoming  visible  light  from  the  sun.    
•The  atmospheric  lifeNme  of  parNcles  depends  on  their  
size.  
21
Climate  Change  and  “Greenhouse  Gases”  
ReflecEon  of  Visible  Light  by  Earth’s  Atmosphere:  
Clouds,  Ice,  and  Aerosols  

Energy  distribuNon  of  radiaNon  arriving  from  the  sun  and  

emiled  by  Earth.  
22
 AbsorpEon  of  Infrared  RadiaEon  by  
“Greenhouse  Gases”  
• The  principal  gases  making  up  99%  of  the  earth’s  
atmosphere  (N2  and  O2)  do  not  directly  absorb  IR  
radiaNon,  and  are  therefore  not  “greenhouse  gases.”  
• Most  of  the  trace  carbon  compounds  in  the  atmosphere  
are  “greenhouse  gases.”  They  are  capable  of  absorbing  
the  infrared  radiaNon  that  would  otherwise  escape  into  
space  and  cool  the  planet.  

23
 Molecular-­‐Level  View  of  How  
“Greenhouse  Gases”  Cause  Warming  

CO2  absorbs  photons  of  infrared  radiaNon  if  they  are  of  exactly  the  
right  energy  to  cause  stretching  or  bending  vibraNons.  Atmospheric  
warming  takes  place  due  to  collisional  de-­‐excitaEon  of  CO2(g).  
24
 AbsorpEon  of  Infrared  RadiaEon  by  
“Greenhouse  Gases”  

The  increase  in  global  emissions  of  carbon  from  fossil  fuels  
since  the  Industrial  RevoluNon.  
25
 Global  Warming  PotenEal  and  Infrared  
“Windows”  
• The  combined  infrared  spectra  of  water  vapour  and  
CO2(g)    leaves  only  several  “windows”  where  infrared  
radiaNon  can  escape  into  space.  
• Trace  carbon  compounds  in  our  atmosphere  absorb  
infrared  radiaNon  in  these  “windows,”  thereby  warming  
our  planet.  
• The  effect  of  a  “greenhouse  gas”  on  climate  depends  on  
– Its  concentraNon  
– How  strongly  and  where  in  the  infrared  region  it  absorbs  energy  
– Its  atmospheric  lifeNme  
26
Global  Warming  PotenEal  and  Infrared  
“Windows”  
Atmospheric  LifeNme  and  Global  Warming  PotenNal  of  
“Greenhouse  Gases”  

27
Global  Warming  PotenEal  and  Infrared  
“Windows”  

Global  average  esNmates  for  the  change  in  radiaNve  

forcing  of  anthropogenic  “greenhouse  gases”  and  other  
important  contributors  between  1750  and  2005.  

28
 Controlling  Methane  Sources  
• Methane  has  global  warming  potenNal  72  Nmes  
that  of  carbon  dioxide  (over  a  20-­‐year  horizon).  
• Reducing  thermogenic  and  biogenic  methane  has  
become  a  priority  
– Beler  maintenance  of  natural  gas  pipelines  
– Controlling  methane  emissions  during  coal  and  
petroleum  producNon  
– Modifying  rice  producNon  techniques  
– Changing  feed  and  developing  vaccines  for  livestock  
29
 Capturing,  Storing,  and  Recycling  
Carbon  Compounds  
• Carbon  dioxide  (CO2(g))  levels  in  the  atmosphere  
can  be  reduced  by  finding  ways  to  capture  and  
store  it  in  the  ocean,  in  geological  formaNons,  
and  by  conversion  to  other  chemical  species.    
• A  great  deal  of  research  is  also  directed  toward  
reducNon  of  emissions  of  methane  and  other  
“greenhouse  gases.”  

30
 Capturing,  Storing,  and  Recycling  
Carbon  Compounds  
Geological  CO2  storage  in  aquifers  and  salt  caverns.  

31
 Capturing,  Storing,  and  Recycling  
Carbon  Compounds  
Chemistry  of  Carbon  Capture  and  Storage  
• CO2(g)  may  be  stored  in  a  way  that  its  molecular  
structure  is  unchanged  or  converted  into  other  
compounds  containing  carbon.  
• When  deposited  into  the  ocean,  CO2  might  form  
clathrate  compounds,  or  more  likely  would  react  
directly  with  water  …  
CO2(g) + 2 H2O(ℓ) ⇌ HCO3‒ (aq) + H3O+(aq)

HCO3‒ (aq) + H2O(ℓ) ⇌ CO32‒ (aq) + H3O+(aq)

32
 Carbon  Dioxide  as  a  Feedstock  and  
Solvent  
• Chemists  are  working  on  the  challenge  of  recycling  
carbon  dioxide    
– Presently,  less  than  1%  of  CO2(g)  produced  by  human  acNviNes  
is  used  as  a  starNng  material  in  the  synthesis  of  other  carbon  
compounds.  
• SupercriNcal  CO2(ℓ)  can  replace  many  other  organic  
solvents,  and  it  can  be  recaptured  and  reused.  
• Other  challenges,  e.g.,  collecNng  concentrated  forms  of  
carbon  dioxide.  

33
Biopolymers:  Carbon  Dioxide  Storage  
and  ReacEons  in  Nature    
What  causes  atmospheric  CO2  oscillaNons  with  Nme?  

34
 Capturing,  Storing,  and  Recycling  
Carbon  Compounds  
What  causes  atmospheric  CO2  oscillaNons  with  Nme?  
•Atmospheric  CO2  can  be  very  efficiently  captured  by  plants  
and  some  other  organisms.  Captured  CO2  is  stored  by  plants  
in  the  form  of  glucose,  through  the  process  of  
photosynthesis.  
6 CO2(g) + 6 H2O(ℓ)  C6H12O6(s) + 6 O2(g)

Glucose:

35
 Capturing,  Storing,  and  Recycling  
Carbon  Compounds  
• Glucose  monomers  are  converted  into  polymers  
for  structural  purposes  and  for  energy  storage.  
Cellulose:
Glucose:

• Research  on  converNng  CO2(g)  to  biomass.  

36
 Alkanes:  Saturated  Hydrocarbons  
• Alkanes  
– Chains  formed  by  carbon  atoms  
– Saturated  hydrocarbons  
– General  formula:  CnH2n+2  

• Alkanes  make  up  natural  gas  and  form  the  

carbon  skeletons  for  many  important  natural  and  
syntheNc  materials.  

37
Alkanes:  Saturated  Hydrocarbons  
Methane:   Ethane   Propane  
CH4   C2H6   C3H8  

38
 Alkanes:  Saturated  Hydrocarbons  
The  petroleum-­‐refining  process:  

• FracNonal  disNllaNon    
separates  petroleum  into    
mixtures  of  alkanes  based    
on  boiling  points.  

39
 Alkanes:  Saturated  Hydrocarbons  
Names  and  States  of  Selected  Straight-­‐Chain  Alkanes  

40
 Alkanes:  Saturated  Hydrocarbons  
• Different  connecNvity  palerns  lead  to  isomers.  
• Compounds  like  butane  and  2-­‐methylpropane,  whose  
atoms  are  connected  differently,  are  called  
cons7tu7onal  or  subs7tu7onal  isomers.  

Butane:   Isobutane  
(2-­‐methylpropane)  

How  many  different  isomers  are  there  of  C6H14?  

41
 Alkanes:  Saturated  Hydrocarbons  
RepresentaEons  of  Alkanes  
• Butane:  

C4H10  

CH3CH2CH2CH3  

CH3(CH2)2CH3  

42
 Alkanes:  Saturated  Hydrocarbons  
Nomenclature  (Names)  of  Alkanes  
• IUPAC  system  of  nomenclature:  

43
Polymers  and  Unsaturated  Hydrocarbons  
• Compounds  whose  molecules  contain  double  bonds,  
triple  bonds,  or  rings  are  called  unsaturated  
compounds.    
• Alkenes  (e.g.,  ethene)  contain  carbon–carbon  double  
bonds  and  can  react  with  many  other  alkenes  to  form  
polymers.    
• Alkynes  are  compounds  with  carbon–carbon  triple  
bonds.  

44
Polymers  and  Unsaturated  Hydrocarbons  
ClassificaEon  of  Hydrocarbons  by  Structural  
Features  and  General  Formula  

45
Polymers  and  Unsaturated  Hydrocarbons  
• An  important  polymer  made  from  ethene  monomer  
units  is  a  macromolecular  substance  called  
polyethylene.  

• At  high  temperatures  and  pressures  (in  the  presence  of  

a  catalyst),  ethylene  is  converted  to  polyethylene  
polymers  with  molecular  weights  up  to  several  million.  
46
 Where  There  Is  Methane,  Is  There  Life?  
• Methane  is  a  substance  that  
signifies  life  on  Earth.  
• Methane  and  liquid  water  are  
detected  on  Mars.  Is  there  life?  
• Chemists  are  designing  
experiments  to  verify  the  
detecNon  of  methane  on  other  
planets  and  determine  whether  
The  MarNan  atmosphere   it  has  been  produced  by  recent  
forms  of  life.  
47