lCCSLkuWAl1.

CCM

lree radlcal subsLlLuLlon of chlorlne ln alkanes:
lnlLlaLlon, propagaLlon, LermlnaLlon

redlcLlng Lhe Lype of mechanlsm:
olar bonds always break heLerolyLlcally
A nucleophlle can aLLack Lhe d
+
aLom ln a polar bond
An elecLrophlle can aLLack an elecLron- rlch parL of a molecule - e.g. Lhe C=C bond ln alkenes

All reagenLs used ln AS chemlsLry (helpful Lo learn Lhem):
nucleophlles: CP
-
(aq),
nP
3 (alcohollc),
Cl
3,
na8r/P
2
SC
4
or 8r
3,
/l
2

LlecLrophlles: P
2,
x
2,
Px
CxldaLlon [C]: kMnC
4
/P
+
, k
2
Cr
2
C
7
/P
+

CLher: kCP ln hoL eLhanol, Cl
2
/ u.v llghL, 8C -C8/ u.v llghL (polymerlsaLlon)

CZCnL
Czone molecules - C
3

1he ozone layer ls aL Lhe edge of Lhe stratosphere
lL fllLers ouL mosL of Lhe harmful uv radlaLlon whlch can damage unA ln cells causlng skln
cancer and can also cause eye caLaracLs.
Czone ls formed when uv radlaLlon from Lhe sun hlLs oxygen molecules. 1hls forms Lwo free
radlcals. 1he free radlcals Lhen comblne wlLh oLher oxygen molecules Lo form ozone
molecules
C
2
+ u.v C* + C*
C
2
+ C* C
3

1he ozone layer ls consLanLly belng replaced, and Lhere ls a naLural balance beLween
formaLlon of new ozone and breakdown of ozone molecules : C
2
+ C* C
3

lL was dlscovered LhaL Lhe ozone layer ls Lhlnnlng ln places, and a hole ln Lhe ozone was
dlscovered over AnLarcLlca - Lhls means LhaL more harmful uv wlll reach Lhe earLh.
1he decrease ln ozone concenLraLlons ls due Lo ClCs - chlorofluorocarbons.
8ecause of Lhelr un-reacLlvlLy, ClCs don'L decay and reach Lhe upper aLmosphere and Lhe
ozone layer, where several reacLlons happen:
1) ClCs are broken down by uv llghL, formlng chlorlne free radlcals
CCl
3
l
2 (g)
CCl
2
l*
(g)
+ Cl*
(g)
2) 1he free radlcals are cata|ysts, and reacL wlLh ozone Lo form an lnLermedlaLe - ClC*, and C
2
P
+
= acldlfled
* = free radlcal
lCCSLkuWAl1.CCM
Cl*
(g)
+ C
3 (g)
C
2 (g)
+ ClC*
(g)

ClC*
(g)
+ C
3 (g)
2C
2 (g)
+ Cl*
(g)

3) 1he overall reacLlon ls: 2C
3 (g)
3C
2 (g)
(Cl ls Lhe caLalysL)



N|trogen ox|des are produced from car and a|rcraft eng|nes and thunderstorms. Llke
chlorlne radlcals, nC* also acL as caLalysLs :
nC* + C
3
C
2
+ nC
2
*


nC
2
* + C
3
2C
2
+ nC*

l8
Some molecules absorb energy from lnfrared radlaLlon. 1hls makes Lhe bonds vlbraLe
vlbraLlons occur ln one of 2 ways, a sLreLchlng vlbraLlon or a bendlng vlbraLlon
Lvery bond vlbraLes aL lLs own unlque frequency dependlng on:
1. 8ond sLrengLh
2. 8ond lengLh
3. Mass of aLom aL elLher end of Lhe bond
Cxygen C
2
, and nlLrogen n
2
don'L absorb lnfrared radlaLlon, buL CC
2
, P
2
C, nlLrlc acld (nC) ,
and meLhane (CP
4
) do absorb lnfrared radlaLlon. 1hey absorb l8 because Lhey change Lhelr
polarlLy as Lhey vlbraLe (due Lo Lhe movemenL of dlpoles ln polar bonds)
Cases LhaL do absorb l8 radlaLlon are called greenhouse gases - Lhey sLop some of Lhe
radlaLlon emlLLed by Lhe earLh from escaplng lnLo space.
WhaL Lhe specLrum look llke:
1he specLrum glves us 'peaks' whlch are acLually absorbance Lroughs.
1hese Lroughs are caused by a frequency of l8 llghL belng absorbed from a bond vlbraLlng
bond.
Lach 'peak' ls characLerlsLlc Lo a speclflc bond / aLoms








1he Cl free radlcal ls regeneraLed
and goes on Lo aLLack oLher ozone
molecules. 1hls shows LhaL one
ClC molecule can desLroy
Lhousands of ozone molecules
lCCSLkuWAl1.CCM
Ident|f|cat|on of funct|ona| groups:
We have [usL seen LhaL Lhe peak on an l8 specLra are due Lo speclflc bonds (and aLoms)
vlbraLlng or sLreLchlng.
1he frequency aL whlch you flnd an absorbance peak ls Lherefore unlque Lo bonds and
aLoms aL each end of Lhe bond.
1hls means LhaL funcLlonal groups wlll glve speclflc peaks.
8ond Iunct|ona| group Wavenumber]frequency
C=C Aldehydes, keLones, carboxyllc aclds 1640 - 1730
C- n Crganlc compounds 2830 - 3100
C- n Carboxyllc aclds
2300 - 3300
(very broad)
C- n Alcohols (hydrogen bonded) 3200 - 3330 (broad)
N-n Amlnes 3200-3300
C-k Palogenoalkanes 300-1000
A|coho|s:
1he l8 specLrum for meLhanol, CP
3
CP ls shown below:

1he peak aL 3230 - 3300
represenLs an C - P group ln
alcohols.


A|dehydes and ketones:

1he l8 specLrum for propanal,
CP
3
CPC ls shown:
1he peak aL 1680 - 1730
represenLs a C=C group ln
aldehydes and keLones.
lCCSLkuWAl1.CCM
A|dehydes and ketones:
1he l8 specLrum for propanolc acld,
CP
3
CP
2
CCCP ls shown:
1he peak aL 2300 - 3300
represenLs an C - P group ln
a carboxyllc acld.
1he peak aL 1680 - 1730
represenLs a C=C group ln a
carboxyllc acld.

Mass spec
lonlsaLlon ln a mass specLroscope ls usually done by elecLron bombardmenL.
LlecLron bombardmenL knocks anoLher elecLron ouL of Lhe molecule produclng a poslLlve
mo|ecu|ar |on -M
+
.
C
2
P
3
CP + e
-
! C
2
P
3
CP
+
+ 2e
-

1he molecular lon has Lhe same mass as Lhe Mr of Lhe molecule.
As we have a mass and a charge we can use a mass specLromeLer Lo deLermlne Lhe Mr (m/z).
Iragmentat|on:
Lxcess energy from Lhe lonlsaLlon process causes bonds ln Lhe organlc molecule Lo vlbraLe
and weaken.
1hls causes Lhe molecule Lo spllL or fragment lnLo smaller pleces.
Iragmentat|on glves a poslLlvely charged molecular fragmenL lon and a neuLral molecule:
C
2
P
3
CP ! CP
3
+ CP
2
CP
+
1he fragmenL lon, CP
2
CP
+
has a mass and charge so we can use a mass specLromeLer Lo
deLermlne Lhe Mr (m/z) of LhaL fragmenL.
lragmenL lons can be broken up furLher Lo glve a range of m/z values.
1he m/z values correspond Lo Lhe Mr's of Lhe molecule and lLs fragmenLs.
1he Mr of Lhe molecule ls always Lhe h|ghest m]z va|ue - l.e. Lhls molecule has noL been
fragmenLed so lL musL have Lhe hlghesL Mr.
1he one below ls for eLhanol. lL has a m/z of 46 whlch ls also lLs Mr.




lCCSLkuWAl1.CCM
Iragmentat|on patterns:
Mass specLroscopy ls used Lo ldenLlfy and deLermlne Lhe sLrucLures of unknown compounds.
AlLhough 2 lsomers wlll have exacLly Lhe same M
+
peak, Lhe fragmenLaLlon paLLerns wlll be
unlque Lo LhaL molecule, llke a f|ngerpr|nt.
ln pracLlce mass specLromeLers are llnked Lo a daLabase and Lhe specLra ls compared unLll an
exacL maLch ls found:


1hese are Lhe mass specLra for penLane and a sLrucLural lsomer of penLane, 2 meLhylbuLane.
1he M
+
peak ls Lhe same for each buL Lhe fragmenLaLlon paLLerns are dlfferenL.
Ident|fy|ng fragment |ons:
When you look aL a mass specLrum, oLher peaks seem Lo look more lmporLanL Lhan Lhe M
+

peak.
1hese fragmenL peaks glve clues Lo Lhe sLrucLure of Lhe compound.
Lven slmple sLrucLures glve common peaks LhaL can be ldenLlfled:
m/z
value
osslble ldenLlLy of Lhe
fragmenL lon
13 CP
3
+

29 C
2
P
3
+

43 C
3
P
7
+

37 C
4
P
9
+

17 CP
+

luncLlonal groups are a good place Lo sLarL, CP = m/z of 17
Some fragmenLs are more dlfflculL Lo ldenLlfy as Lhese wlll have undergone molecular
rearrangemenL.
Ident|f|cat|on of organ|c structures:
A mass specLrum wlll noL only Lell you Lhe Mr (from Lhe M
+
peak), buL lL can also Lell you
some of Lhe sLrucLural deLall.
1hese peaks have been labelled wlLh a leLLer:
lCCSLkuWAl1.CCM




1he mass specLrum above has been produced from hexane.
1he followlng reacLlons show how Lhe molecule could fragmenL Lo form Lhe fragmenL lons
37 and 43:









Creen ChemlsLry
rocesses ln Lhe chemlcal lndusLry are belng relnvenLed Lo make Lhem more susLalnable or 'greener'
by:
1. Changlng Lo renewable resources: e.g. plasLlcs made from crude oll can be made from planL
producLs
2. Maklng more efflclenL use of energy. L.g. ln Lhe pharmaceuLlcal lndusLry mlcrowave
radlaLlon ls used Lo heaL Lhe reacLlng mlxLure d|rect|y raLher Lhan uslng convenLlonal heaLlng
sysLems whlch heaL Lhe reacLlon vessel whlch passes on heaL Lo Lhe reacLlon mlxLure - less
efflclenL.
3. llndlng alLernaLlves Lo very hazardous chemlcals e.g. some chemlcals can harm humans,
oLher llvlng organlsms or Lhe envlronmenL.
4. ulscoverlng caLalysLs for reacLlons wlLh hlgher aLom economles. 1hls ls lmporLanL because a
hlgh aLom economy means less wasLe ls produced and Lhls makes Lhe besL use of resources.
3. 8educlng wasLe and prevenLlng polluLlon of Lhe envlronmenL. L.g. creaLlng recyclable or
uslng producLs Lo conserve raw maLerlals and where posslble wasLe should be recycled or
blodegradable.

lCCSLkuWAl1.CCM
LffecLs of greenhouse gases:
Infrared rad|at|on Ik from Lhe sun has a shorL wavelengLh and mosL of lL passes Lhrough Lhe
aLmosphere and ls absorbed by Lhe earLh's surface.
1he earLh heaLs up, and re-em|ts |onger wavelengLh l8. Any greenhouse gases ln Lhe
aLmosphere effect|ve|y ref|ect Lhe longer wavelengLh l8 whlch warms Lhe aLmosphere.
1he relaLlve greenhouse effecL of a gas varles because molecules absorb l8 dlfferenLly.
1he g|oba| warm|ng potent|a| of a gas comblnes lL ab|||ty to absorb Ik wlLh lLs ||fet|me |n
the atmosphere. 1he concenLraLlon of a gas ln Lhe aLmosphere also affecLs CW. L.g. CC
2

has a low global warmlng poLenLlal, buL Lhe concenLraLlons of lL are lncreaslng. ClCs have a
much hlgher CW buL Lhe overall concenLraLlons are very low.

AnLhropogenlc and naLural cllmaLe change:
AnLhropogenlc: resulLs from human acLlvlLles, e.g. burnlng fossll fuels and deforesLaLlon.
1hese lncrease levels of CC
2,
meLhane and oLher gases over relaLlvely shorL Llmescales.
naLural cllmaLe change: naLural processes such as dlssolvlng of CC
2
ln sea waLer or
formaLlon of carbonaLes ln rocks over hundreds of years. volcanlc erupLlons can also cause
cllmaLe change.
Carbon neuLrallLy and carbon fooLprlnL:
A carbon neuLral fuel ls one for whlch Lhe release of CC
2
ln lLs manufacLure and burnlng
equals Lhe absorpLlon of CC
2
as Lhe raw maLerlal ls grown or Lhe fuel formed. Cnly cerLaln
blofuels can be consldered carbon neuLral
A carbon neuLral process occurs when Lhere ls no overall carbon emlsslon lnLo Lhe
aLmosphere.
A carbon fooLprlnL ln general ls a measure of Lhe amounL of carbon dloxlde emlLLed Lhrough
Lhe use of fossll fuels. lL ls ofLen measured ln Lonnes of carbon dloxlde, and can be calculaLed
for an lndlvldual, a household, an organlsaLlon or over a producL llfecycle for manufacLured
goods.
1he fuel petro| ls deflnlLely noL carbon neuLral - releases CC
2
lnLo aLmosphere whlch was
Lrapped ln Lhe earLh mllllons of years ago.
8|oethano| ls more or less carbon neuLral- produced by fermenLaLlon of sugar from crops.
lL's LhoughL of as belng carbon neuLral as Lhe CC
2
released when burnL was removed by Lhe
crop as lL grew. Powever, Lhere are sLlll carbon emlsslons when conslderlng Lhe whole
process.
Pydrogen gas can be carbon neuLral .



"