Chapter 2

Hydrocarbon
(Irom C & H )
Aliphatic ; alkane, alkene, alkyne, cyclic
Aromatic the simplest ; CH
4
relatively inert
heat oI combustion : 213kcal
Iuel , H
2
, CO & H
2
acetylene
oxidation
( substitution )
can be the major product with
a large excess oI CH
4
alcohol NH
3
CH
4
Cl
2
CCl
4
CHCl
3
CH
2
Cl
2
CH
3
Cl
HCl

HCl

HCl

HCl

hor
structure :p40
nonpolar
low m.p.&b.p.
(van der Waals
force)
density:0.4
solublility
slightly
soluble
in H

O
very soluble
in organic liq.
halogenation



reactivity Ior halogenation E
2
CH
4

h
or
CH
3
Br CH
2
Br
2
CHBr
3
CBr
4
Br
2
Br
2
I
2
Cl
2
Rxn mechanism ; the detailed step-by-step decription oI a chemical rxn
diIIicult to prove
explain many results, oIIer good predictions and
have consistency well established
easily understand the complicated rxns.
improve the yield.
change the rxn courses ro get
the desired products.
Erom rxn mechamisms
Eor halogenation, the mechanism
should expain
1) no rxn in the dark at RT
2) rxn over 250
o
C or under UV at RT
3) to induce chlorination to dissociate Cl
2
4) O
2
slows down the rxn
5) one photon produces many CH
3
Cl molecules



CH
3
Cl
Cl
2
CH
4
CH
3

Cl
2
2 Cl
HCl
C
2
H
6
Cl
CH
3

CH
3
Cl
Cl
CH
3
CH
3
Cl Cl
Cl
2
Cl
CH
3
initiation
require energy
supplied by heat or h
propagation
termination
chain rxn
Iree radical ; unpaired odd electron, very reactive


CH
3
O
2
CH
3
O O
; slow down or stop the rxn
inhibitor , inhibition period
exothermic rxn ; readily occur
endothermic rxn ; not readily occur



CH
4

Cl
2
CH
3
Cl
HCl
H -25kcal occur only at a
high temp.
due to the cleavage
oI Cl
2
Cl
2
2 Cl
CH
4 Cl
CH
3 HCl
CH
3
Cl
2
CH
3
Cl
Cl

H 58
H 1
H -26

Cl
CH
3
H
Cl H
CH
3
H 1
E 4
(104) (103)
a collision must provide a minimum
amount oI energy Ior an eIIective rxn
activation
energy
Br
CH
3
H
(104)
Br H
CH
3
H 16
E 18
(88)
proper
oriention
Eig 2.3 , 2.4 & 2.5
(no bond-breaking or bond-Iorming)



chemical rxn
collisions oI suIIicient energy and proper orientation
rate collision Irequency energy Iactor probability Iactor
(orientation Iactor)
T (controllable)
E
concn or P
size
speed (weight & T)
size and weight
are not important
not vary widely
Ior closely related
rxns.



Eig 2.7
E the Iraction oI eIIective collcsions
rate PZe
-E

/RT
at 275
o
C
rate
5 10 15
10000 100 1
to increase a rxn rate
T E
concn
250
o
C 300
o
C rate 1.5 2 3
E the eIIect oI T
E

Cl
CH
3
H Cl H CH
3
H 1
E 4
Br
CH
3
H
Br H
CH
3
H 16
E 18
similar collision Irequency
probability Iactor
deIIerent energy Iactor
diIIerent relative
rate. why?


the order oI reactivity
CH
4
E
2
Br
2
I
2
Cl
2
X
2
2 X
X
CH
3
X
CH
3
X
HX
CH
3
X
2
X ; E , Cl , Br , I
-32 1 16 33
-70 -26 -24 -20
longer chain
more chain
chain length
alternative mechnism
Cl
CH
4
H
CH
3
Cl
H
Cl
2
HCl Cl
explained
by this step
E Cl Br I
shorter
H 20 , E 20
can not compete
H ; 38 58 46 36



CH
3
;
C H sp
2
~ sp
3
C
p ~ sp
3

a chemical rxn reactants products
continuous
process
intermediate
structure
transition state
(the top oI the energy hill)
any Iactor to stabilize the transition
state relative to the reactants lowers E
How much does the trasition state
resemble the products?
How Iar have bond-breaking and
bond-Iorming gone?
How Ilat is the methyl group?
How much does the methy group
carry the odd electron?
C
H
H
H
H X C
H
H
H
H
X

C
H
H
H
H
X
(reactant) (transition state)
(product)

diIIerence in structure
diIIerence in electronic distribution
diIIerence in energy
late
transtion
state
E reactant-like
early
transition
state
E reactant-like


ex)
Cl
E 4
Br
CH
4
CH
4 18

highly reactive reagents ; early transition state, reactant-like trasition state
poorly reactive reagents ; late transition stae, product-like trasition state
Molecular Iormula
qualitative elementary analysis
quantitative elementary analysis
molecular weight determination
Eig 2.12



400 ~ 750 nm
visible IR UV
250 nm 300 nm
absorbed
by N
2
& O
2
absorbed
by O
3
O
2
O
O O
2
M
h
O
3
O
2
O
O
3 M
*
O
h
propagation
( M O
2
, N
2
)
initiation
O O M O
2
M
O O
3 O
2

O
2
*
termination



CEC : CE
3
Cl, CECl
2
etc
CE
3
Cl
h
Cl
O
3
O
2
O
2

Cl
Cl
O
ClO
E
3
C
ClO
break the ozone-producing
chain