1.

1 Atomic Structure
Details of the three sub-atomic (fundamental) particles
Particle Position Relative Mass Relative Charge
proton nucleus 1 +1
neutron nucleus 1 0 -=:G:
6G:
K6G>DJH
electron orbitals 1/1840 -1 BD9:AH
;DG
6IDB>8
HIGJ8IJG:
An atom of Lithium (Li) can be represented as follows:

Mass number 7 Li Atomic symbol

Atomic number 3
-=: -)'$
(.' +
3
>H
I=:
CJB7:G
D;
EGDIDCH
>C
I=:
CJ8A:JH
-=: ',,
(.' + 
>H
I=:
IDI6A
CJB7:G
D;
EGDIDCH
6C9
C:JIGDCH
>C
I=:
6IDB
Number of neutrons = A - Z
Isotopes
$HDIDE:H
6G:
6IDBH
L>I=
I=:
H6B:
CJB7:G
D;
EGDIDCH
7JI
9>;;:G:CI
CJB7:GH
D;
C:JIGDCH

$HDIDE:H
=6K:
H>B>A6G
8=:B>86A
EGDE:GI>:H
7:86JH:
I=:N
=6K:
I=:
H6B:
:A:8IGDC>8
HIGJ8IJG:
-=:N
B6N
=6K:
HA><=IAN
K6GN>C<
E=NH>86A
EGDE:GI>:H
7:86JH:
I=:N
=6K:
9>;;:G:CI
B6HH:H

#
-$'
)!
!&$"#-
',,
,* -+)' - +

Ionisation Acceleration Detection -=:
B6HH
HE:8IGDB:I:G
86C
7:
Ion drift area area
area area JH:9
ID
9:I:GB>C:
6AA
I=:
>HDIDE:H
EG:H:CI
>C
6
H6BEA:
D;
6C
:A:B:CI
6C9
ID
I=:G:;DG:
Ion >9:CI>;N
:A:B:CIH
detector

$I
C::9H
ID
7:
JC9:G
6
K68JJB
DI=:GL>H:
6>G
E6GI>8A:H
LDJA9
Heavy Light >DC>H:
6C9
G:<>HI:G
DC
I=:
ions ions 9:I:8IDG

Time measurement
-=:
;DAADL>C<
6G:
I=:
:HH:CI>6A

HI:EH
>C
6
B6HH
HE:8IGDB:I:G
&:6GC
6AA
I=:H:
HI:EH
 )($,-$)( 86G:;JAAN
-=:
H6BEA:
86C
7:
>DC>H:9
>C
6
CJB7:G
D;
L6NH
-LD
D;
I=:H:
I:8=C>FJ:H
6G:
:A:8IGDC
>BE68I
6C9
:A:8IGDHEG6N
>DC>H6I>DC

& -+)(
$'*- A:8IGDC
>BE68I
>H JH:9
;DG
:A:B:CIH

• K6EDG>H:9 H6BEA:
>H
>C?:8I:9
6I
ADL
EG:HHJG: 6C9
HJ7HI6C8:H
L>I=
ADL
;DGBJA6 B6HH
•C
:A:8IGDC
<JC
;>G:H =><=
:C:G<N
:A:8IGDCH
6I
I=:
H6BEA: A:8IGDC
>BE68I
86C
86JH:
A6G<:G
DG<6C>8
•-=>H @CD8@H DJI
6C DJI:G :A:8IGDC BDA:8JA:H
ID
;G6<B:CI
•!DGB>C< *),$-$/ >DCH
L>I=
9>;;:G:CI
8=6G<:H
: < -> <
-> < :S

&-+) ,*+2 )($,-$)(

• -=:
H6BEA: >H $,,)&/  >C
6 KDA6I>A:
EDA6G ,)&/ (-
A:8IGD HEG6N >DC>H6I>DC
>H
JH:9
• >C?:8I:9
I=GDJ<=
6 ;>C: ( & <>K>C<
6
;>C:
B>HI DG 6:GDHDA
EG:;:G67AN
;DG
A6G<:G
DG<6C>8
• I=:
I>E D;
C::9A:
=6H #$"#
/)&-"
BDA:8JA:H
-=:
THD;I:GU
8DC9>I>DCH
• 6I
I=:
I>E
D;
I=:
C::9A:
I=: H6BEA:
BDA:8JA:
' "$(,
 *+)-)(
#
;GDB
I=:
D;
I=>H
I:8=C>FJ:
B:6C
HDAK:CI ;DGB>C<
'#
;G6<B:CI6I>DC
9D:H
CDI
D88JG
• '<

#
'#<
• -=: HDAK:CI
:K6EDG6I:H
6L6N
L=>A:
I=: '# >DCH BDK: IDL6G9H
6
C:<6I>K:
EA6I:

( "D6A7N 8=:BG:K>H: DG< 

 
 & +-$)( ">K:C
I=6I
6AA
I=:
E6GI>8A:H
=6K:
I=:
H6B:
@>C:I>8
:C:G<N
I=:
•*DH>I>K:
>DCH
6G:
688:A:G6I:9
7N
6C
:A:8IG>8
;>:A9 K:AD8>IN
D;
:68=
E6GI>8A:
9:E:C9H
DC
>IH
B6HH
&><=I:G
E6GI>8A:H
•-D
6
8DCHI6CI
@>C:I>8
:C:G<N =6K:
6
;6HI:G
K:AD8>IN
6C9
=:6K>:G
E6GI>8A:H
=6K:
6
HADL:G
  P K:AD8>IN

 
@>C:I>8
:C:G<N
D;
E6GI>8A:
%
 
B6HH
D;
I=:
E6GI>8A:
@< 2DJ
9D
CDI
C::9
ID
A:6GC
I=:H:
:FJ6I>DCH
7JI

K:AD8>IN
D;
I=:
E6GI>8A:
BHS B6N
7:
6H@:9
G:6GG6C<:
I=:B
6C9
JH:
I=:B
>C
6
86A8JA6I>DC

+:6GG6C<:9
<>K:H

 &$"#-
.
•-=:
EDH>I>K:
>DCH
L>I=
HB6AA:G
B O
K6AJ:H
L>AA
=6K:
I=:
H6B:
@>C:I>8
:C:G<N
6H
I=DH:
L>I=
A6G<:G
B O

6C9
L>AA
BDK:
;6HI:G
•-=:
=:6K>:G
E6GI>8A:H
I6@:
ADC<:G
ID
BDK:
I=GDJ<=
I=:
9G>;I
6G:6
•-=:
>DCH
6G:
9>HI>C<J>H=:9
7N
9>;;:G:CI
;A><=I
I>B:H

= / Combining the two equations


I>B:
D;
;A><=I
H gives you
 
A:C<I=
D;
;A><=I
IJ7:
B

K:AD8>IN
D;
I=:
E6GI>8A:
B
HS


 - -$)(
-=:
>DCH
G:68=
I=:
9:I:8IDG
6C9
<:C:G6I:
6
HB6AA
8JGG:CI
L=>8=
>H
;:9
ID
6
8DBEJI:G
;DG
6C6ANH>H
-=:
8JGG:CI
>H
EGD9J8:9
7N
:A:8IGDCH
IG6CH;:GG>C<
;GDB
I=:
9:I:8IDG
ID
I=:
EDH>I>K:
>DCH
-=:
H>O:
D;
I=:
8JGG:CI
>H
EGDEDGI>DC6A
ID
I=:
67JC96C8:
D;
I=:
HE:8>:H

!DG
:68=
>HDIDE:
I=:
B6HH
HE:8IGDB:I:G
86C ,DB:I>B:H
ILD
:A:8IGDCH
B6N
7:
B:6HJG:
6 '3
',,#+"
+-$) 6C9
6C G:BDK:9
;GDB
6
E6GI>8A:
;DGB>C<
6

>DC
'< L>I=
6

8=6G<:
LDJA9

=6K:
6
.((
B O
D;


1'*& 
H6BEA: D; C>8@:A
L6H 6C6ANH:9
6C9 DC:
D;
I=:
>HDIDE:H
;DJC9
L6H (>
-=: >DCH
L:G:

688:A:G6I:9
ID
=6K:

M
  %
D;
@>C:I>8
:C:G<N
6C9
IG6K:AA:9
I=GDJ<=
6
;A><=I
IJ7:
I=6I
L6H

B
ADC<
#DL ADC<
LDJA9 DC:
>DC
D; (> I6@: ID
IG6K:A
6ADC< I=:
;A><=I IJ7:
-=:
KD<69GD
8DCHI6CI
&

  ×   BDAS

'6HH
D;
DC:
>DC
D; (>  B6HH
D;
DC:
BDA:
D; (>

-=:
KD<69GD
8DCHI6CI


   ×  

 1  <

 1  @<

I

V  1  M  M 

I 1  H

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8=:BG:K>H: DG< 
Calculating Relative Atomic Mass
-=:
G:A6I>K:
6IDB>8
B6HH
FJDI:9
DC
I=:
E:G>D9>8
I67A:
>H
6
L:><=I:9
6K:G6<:
D;
6AA
I=:
>HDIDE:H

!><
HE:8IG6
;DG

B6<C:H>JB ;GDB
B6HH
    HE:8IGDB:I:G

24Mg+

67JC96C8:


$;
6H@:9
ID
<>K:
I=:
HE:8>:H
;DG
6
E:6@
 >C
6
B6HH
HE:8IGJB
I=:C
<>K: #+"
25Mg+ 26Mg+ 6C9 ',,
(.' + : < '<
  
 

BO
  

R.A.M =
(isotopic mass x % abundance) .H:
I=:H:
:FJ6I>DCH
ID

LDG@
DJI
I=:
+  '
100

!DG
67DK:
:M6BEA:
D;
'<
+  '

4 
M


 
M


 
M
5


 

R.A.M =
(isotopic mass x relative abundance)

$;
G:A6I>K:
67JC96C8:
>H
JH:9
>CHI:69
D;
total relative abundance E:G8:CI6<:
67JC96C8:
JH:
I=>H
:FJ6I>DC

1'*&  6A8JA6I:
I=:
G:A6I>K:
6IDB>8
B6HH
D;
I:AAJG>JB
;GDB
I=:
;DAADL>C<
67JC96C8:
96I6
 -:
G:A6I>K:
67JC96C8:

 -:

G:A6I>K:
67JC96C8:

 -: G:A6I>K:
67JC96C8: 
 -: G:A6I>K:
67JC96C8: 

R.A.M = [(124x2) + (126x4) + (128x7) + (130x6)]

19
= 127.8

1'*&  DEE:G
=6H
ILD
>HDIDE:H
 J
6C9
 J
-=:
G:A6I>K:
6IDB>8
B6HH
D;
8DEE:G
>H
 

6A8JA6I:
I=:
E:G8:CI6<:
67JC96C8:H
D;
I=:H:
ILD
>HDIDE:H
 

N 

 N 
 


N

 N
 


 N
N

 
N



67JC96C8:
 J
  67JC96C8:
 J


 

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8=:BG:K>H: DG< 
 ,,
,* -+
!)+
& (
+
A
=6H
ILD
>HDIDE:H
A 
6C9
A G
=6H
ILD
>HDIDE:H
G  
6C9
G 

-=:H:
A:69
ID
I=:
;DAADL>C<
HE:8IG6
86JH:9
7N
I=:
9>6IDB>8
BDA:8JA:H
GG

GG

AA
 G:A6I>K:
G:A6I>K: 67JC96C8:
67JC96C8: AA
 GG
 GG

AA


   BO BO
  

-=:

E:6@
=6H
9DJ7A:
I=:
67JC96C8:
D;
I=:
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E:6@H
7:86JH:
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EGD767>A>IN
D;
 G G  6H
86C
7: 7DI=
G G 6C9 G G

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=6K:
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HE68:
EGD7:H

HD
I=6I
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DC
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86C
7:
>9:CI>;>:9

A:B:CIH
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86C
=6K:
6
9>;;:G:CI
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 ,.+$("
-#
 )!

')& .&

* -+
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$;
6
BDA:8JA:
>H
EJI
I=GDJ<=
6
B6HH
HE:8IGDB:I:G L>I=
6C & -+)( $'*-
$)($,-$)(
,-" >I L>AA
D;I:C
7G:6@ Mass spectrum for butane
JE
6C9
<>K:
6
H:G>:H
D;
E:6@H
86JH:9
7N
I=:
;G6<B:CIH
-=:
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B O
=DL:K:G 43
L>AA
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6C9
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 D; I=:   
BDA:8JA:
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DG
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58

$;
6
BDA:8JA:
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6
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8=:BG:K>H: DG< 
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-+.-.+
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#
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6GG6C<:9
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E
9
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L=>8=
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ID

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CJB7:G:9
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JE
ID

:A:8IGDCH >CID

>H
8ADH:HI
ID
CJ8A:JH DEEDH>I:
HE>C
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ID

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ID

:A:8IGDCH

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I=:
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A:K:A     B6I=:B6I>86A
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E
9 H
E
9
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9
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ID
9G6L
I=:
H
H
E
H
E
H
9
E
H
9
E H=6E:
D;
DG7>I6AH
EG:8>H:AN

Writing electronic structure using letters and numbers •s sublevels are

Number of electrons spherical
in sub-level
For oxygen 1s2 2s2 2p4

Number of main Name of

energy level type of • p sublevels are shaped
sub-level like dumbbells

For calcium 1s2 2s2 2p6 3s2 3p6 4s2

Using spin diagrams

!DG
;AJDG>C: An arrow is one electron
2p
Box represents one
2s orbital

The arrows going in the

opposite direction represents
1s the different spins of the
electrons in the orbital

0=:C
;>AA>C<
JE
HJ7
A:K:AH
L>I=
H:K:G6A
DG7>I6AH
;>AA
:68=
DG7>I6A
H>C<AN
7:;DG:
HI6GI>C<
ID
E6>G
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I=:
:A:8IGDCH

2p


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8=:BG:K>H: DG<
 The periodic table is split into blocks.
A s block element is one whose outer electron is filling a s-sub shell e.g. sodium 1s2 2s2 2p6 3s1

A p block element is one whose outer electron is filling a

p-sub shell e.g. chlorine 1s2 2s2 2p6 3s2 3p5

A d block element is one whose outer electron is filling a

d-sub shell e.g. vanadium 1s22s22p63s23p6 4s23d3

Electronic structure for ions

When a positive ion is formed electrons are lost When a negative ion is formed electrons are gained
from the outermost shell. O is 1s2 2s2 2p4 becomes O2- is 1s2 2s2 2p6
Mg is 1s2 2s2 2p6 3s2 becomes Mg2+ is 1s2 2s2 2p6

Electronic structure of d-block elements

The electronic structure of the d-block has some complications. As mentioned earlier, conventionally we
say that 4s fills before 3d and so we write them in that order. There is, however, disagreement in the
scientific community about whether this is true.
If you look at the electronic structures below you will see both chromium and copper have an unusual
arrangement in having a half filled 4s sub shell.
You will also see that when d-block elements form ions they lose the 4s electrons first.
You may find if you research different reasons for these observations. It may well be many of the reasons
are false and we have to accept that some things in chemistry don’t neatly follow patterns we can explain.
You do need to learn these electronic structure though!

,8 HHEHE H9 ,8 4G5
H 9

-> HHEHE H9 -> 4G5
H 9
/

HHEHE H9 / 4G5
H 9
G

HHEHE H9 G 4G5
H 9
'C HHEHE H9 'C 4G5
H 9
!:

HHEHE H9 When
!: 4G5
H 9
forming ions
D

HHEHE H9 lose 4s D 4G5
H 9
(>

HHEHE H9 before 3d (> 4G5
H 9
J

HHEHE H9 J 4G5
H 9
3C

HHEHE H9 3C 4G5
H 9

(
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8=:BG:K>H: DG< 
 )($,-$)(
( +"$ ,
 !$($-$)(
$+,-
$)($,-$)(
( +"2 +:B:B7:G
I=:H:
9:;>C>I>DCH
K:GN
86G:;JAAN
The first ionisation energy is the enthalpy change when one mole of gaseous
atoms forms one mole of gaseous ions with a single positive charge
-=:
:FJ6I>DC
;DG
HI
>DC>H6I>DC
This is represented by the equation: H(g)
H+ (g) + e- :C:G<N
6AL6NH
;DAADLH
I=:
H6B:
E6II:GC
$I
9D:H
CDI
B6II:G
>;
I=:
6IDB
9D:H
AL6NH
<6H:DJH CDI
CDGB6AAN
;DGB
6

>DC
DG
>H
CDI
<6H:DJH
 !$($-$)(
 )(
$)($,-$)(
( +"2
The second ionisation energy is the enthalpy change when one mole of
gaseous ions with a single positive charge forms one mole of gaseous
ions with a double positive charge

This is represented by the equation: -> 

->

:

-)+,
-#- !! -
$)($,-$)( ( +"2
-=:G:
6G:
I=G::
B6>C
;68IDGH
 -=:
6IIG68I>DC
D;
I=:
CJ8A:JH
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BDG:
EGDIDCH
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I=:
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I=:
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The first Ionisation energy of the elements
The shape of the graph for periods two and
three is similar. A repeating pattern across a
Ionisation energy kJ mol-1

period is called periodicity.

2000

1500 The pattern in the first ionisation energy

gives us useful information about
1000 electronic structure
500
You need to carefully learn the
0 patterns
5 10 15 20
Atomic number

Q. Why has helium the largest first ionisation energy?

A. Its first electron is in the first shell closest to the nucleus and has no
shielding effects from inner shells. He has a bigger first ionisation Many questions can be
energy than H as it has one more proton answered by application of
the 3 factors that control
Q. Why do first ionisation energies decrease down a group? ionisation energy

A. As one goes down a group, the outer electrons are found in shells
further from the nucleus and are more shielded so the attraction of
the nucleus becomes smaller

Q. Why is there a general increase in first ionisation energy across a period?

A. As one goes across a period the electrons are being added to the same
shell which has the same distance from the nucleus and same shielding
effect. The number of protons increases, however, making the effective
attraction of the nucleus greater.

Q. Why has Na a much lower first ionisation energy than neon?

This is because Na will have its outer electron in a 3s shell further from
the nucleus and is more shielded. So Na’s outer electron is easier to
remove and has a lower ionisation energy.

Q. Why is there a small drop from Mg to Al?

Al is starting to fill a 3p sub shell, whereas Mg has its outer electrons in the 3s
sub shell. The electrons in the 3p subshell are slightly easier to remove because
the 3p electrons are higher in energy and are also slightly shielded by the 3s
electrons
Learn carefully the
explanations for
Q. Why is there a small drop from P to S?
these two small
With sulfur there are 4 electrons in the 3p sub shell and the 4th is starting to doubly fill drops as they are
the first 3p orbital. different to the
When the second electron is added to a 3p orbital there is a slight repulsion between usual factors
the two negatively charged electrons which makes the second electron easier to
remove.
3p 3p
3s 3s
Two electrons of opposite spin in
the same orbital
phosphorus 1s2 2s2 2p63s23p3
sulfur 1s2 2s2 2p63s23p4
(
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8=:BG:K>H: DG< 
Patterns in the second ionisation energy.

If the graph of second ionisation or each successive element is plotted then a similar pattern to the first
ionisation energy is observed but all the elements will have shifted one to the left.
5000
Na
2nd Ionisation energy
4500
4000
(kJ/mol) 3500
3000 Ar
2500 S
P
2000 Al Cl
1500
Mg Si
1000
10 12 14 16 18 20
Atomic Number

The group 1 elements are now at the peaks of the graph

Lithium would now have the second largest ionisation of all elements as its second electron
would be removed from the first 1s shell closest to the nucleus and has no shielding effects
from inner shells. Li has a bigger second ionisation energy than He as it has more protons.

(
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 1.3 Bonding
Mg goes from 1s2 2s2 2p63s2
Definition: Ionic bonding is the electrostatic force of attraction
between oppositely charged ions formed by electron transfer. to Mg2+ 1s2 2s2 2p6

Metal atoms lose electrons to form +ve ions. O goes from 1s2 2s2 2p4 to
Non-metal atoms gain electrons to form -ve ions. O2- 1s2 2s2 2p6

Ionic bonding is stronger and the melting points higher when the ions are smaller and/ or have higher
charges. E.g. MgO has a higher melting point than NaCl as the ions involved (Mg2+ & O2- are smaller and
have higher charges than those in NaCl , Na+ & Cl- ) greater attraction between nucleus and e- means smaller ion

Definition: covalent bond

A covalent bond is a shared pair of electrons

Dative Covalent bonding .. +

A Dative covalent bond forms when the O
shared pair of electrons in the covalent bond
H H
come from only one of the bonding atoms. A
dative covalent bond is also called co-ordinate H

bonding.

Cl H
Common examples you should be able to
draw that contain dative covalent bond (e.g.
NH4+, H3O+, NH3BF3)
Cl B N H

Cl H

The direction of the arrow

The dative covalent bond acts like
goes from the atom that is
an ordinary covalent bond when
providing the lone pair to the
thinking about shape so in NH4+
atom that is deficient
the shape is tetrahedral

Metallic bonding

Definition: Metallic bonding is the electrostatic force of attraction between the

positive metal ions and the delocalised electrons

The three main factors that affect the strength of metallic bonding are:
1. Number of protons/ Strength of nuclear attraction.
The more protons the stronger the bond
2. Number of delocalised electrons per atom (the outer shell electrons are delocalised)
The more delocalised electrons the stronger the bond
3. Size of ion.
The smaller the ion, the stronger the bond.

Example
Mg has stronger metallic bonding than Na and hence a higher melting point. The
Metallic bonding gets stronger because in Mg there are more electrons in the outer shell
that are released to the sea of electrons. The Mg ion is also smaller and has one more
proton. There is therefore a stronger electrostatic attraction between the positive metal
ions and the delocalised electrons and higher energy is needed to break bonds.


%",
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Bonding and Structure
Bonding Structure Examples

Ionic : electrostatic force of Sodium chloride

attraction between Magnesium oxide
Giant Ionic Lattice
oppositely charged ions

Covalent : shared pair of Simple molecular: Iodine

electrons With intermolecular forces (van der Ice
Waals, permanent dipoles, hydrogen Carbon dioxide
bonds) between molecules Water
Methane
Covalent : shared pair of Macromolecular: Diamond
electrons giant molecular structures. Graphite
Silicon dioxide
Silicon
Metallic: electrostatic Magnesium, Sodium
force of attraction between Giant metallic (all metals)
the metal positive ions and lattice
the delocalised electrons

Only use the words molecules and intermolecular forces when talking about simple molecular substances

Property Ionic Molecular (simple) Macromolecular Metallic

boiling and high- because low- because of high- because of high- strong electrostatic forces
melting of giant lattice weak intermolecular many strong covalent between positive ions and sea of
points of ions with forces between bonds in delocalised electrons
strong molecules (specify macromolecular
electrostatic type e.g van der structure. Take a lot
forces waals/hydrogen of energy to break the
between bond) many strong bonds
oppositely
charged ions.

Solubility in Generally generally poor insoluble insoluble

water good

conductivity poor: ions poor: no ions to diamond and sand: good: delocalised electrons can
when solid can-t move/ conduct and poor, because move through structure
fixed in lattice electrons are electrons can-t move
localised (fixed in (localised)
place) graphite: good as free
delocalised electrons
between layers

conductivity good: ions can poor: no ions poor (good)

when molten move

general crystalline mostly gases and solids shiny metal

description solids liquids Malleable as the positive ions in
the lattice are all identical. So the
planes of ions can slide easily
over one another
-attractive forces in the lattice are
the same whichever ions are
adjacent


%",
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Shape of molecules

Name No No lone Diagram Bond angle Examples

bonding pairs
pairs
linear 2 0 Cl Be Cl 180 CO2, 

 
Trigonal 3 0 Cl Cl 120 
 

planar 

B

Cl
Tetrahedral 4 0 H 109.5  

,
NH4+

H H

Trigonal 3 1 .. 107     

pyramidal  

N

H
H

Bent 2 2 .. .. 104.5  

  

O  

H H

Trigonal 5 0 F 120 and 90 PCl5

Bipyramidal F
P F
F

F
F
Octahedral 6 0 90 SF6
F F

F F

How to explain shape 1. State number of bonding pairs and lone pairs of electrons.
2. State that electron pairs repel and try to get as far apart as possible (or to a
position of minimum repulsion.)
3. If there are no lone pairs state that the electron pairs repel equally
4. If there are lone pairs of electrons, then state that lone pairs repel more than
bonding pairs.
5. State actual shape and bond angle.

Remember lone pairs repel more than bonding pairs and so reduce bond angles (by about 2.5o
per lone pair in above examples)

%",
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 Occasionally more complex shapes are seen that are variations of octahedral and trigonal
bipyramidal where some of the bonds are replaced with lone pairs. You do not need to learn the
names of these but ought to be able to work out these shapes using the method below

X X
X X

X

Square planar Bond angle ~89O Bond angle ~89O Bond angles ~119 + 89O
Bond angle 180O
Bond angle 90O (Reduced by lone pair) (Reduced by lone pairs) (Reduced by lone pair)

e.g XeF4 e.g. BrF5 e.g I3- e .g.ClF3 e.g. SF4 & IF4+

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 Electronegativity and intermediate bonding

Definition F, O, N and Cl are the

most electronegative
Electronegativity is the relative tendency of an atom in a covalent bond atoms
in a molecule to attract electrons in a covalent bond to itself.
The most electronegative
Electronegativity is measured on the Pauling scale (ranges from 0 to 4) element is fluorine and it
is given a value of 4.0
Factors affecting electronegativity
Electronegativity increases across a period as the number of protons increases and the atomic radius
decreases because the electrons in the same shell are pulled in more.
It decreases down a group because the distance between the nucleus and the outer electrons increases and
the shielding of inner shell electrons increases

Intermediate bonding

Ionic and covalent bonding are the extremes of a continuum of bonding type. Differences in
electronegativity between elements can determine where a compound lies on this scale

A compound containing elements of similar electronegativity and hence a small

electronegativity difference will be purely covalent

A compound containing elements of very different electronegativity and hence a

very large electronegativity difference (> 1.7) will be ionic

Formation of a permanent dipole – (polar covalent) bond The element with the
larger
A polar covalent bond forms when the elements in the bond have different electronegativity in a
electronegativities . (Of around 0.3 to 1.7) polar compound will
be the δ- end
When a bond is a polar covalent bond it has an unequal distribution of δ+ δ–
electrons in the bond and produces a charge separation, (dipole) δ+ δ-
ends.  

Polar and Non Polar molecules

Symmetric molecules

A symmetric molecule (all bonds identical and no lone

pairs) will not be polar even if individual bonds within
the molecular ARE polar.
CO2 is a symmetrical molecule and
The individual dipoles on the bonds ‘cancel out’
is a non-polar molecule
due to the symmetrical shape of the molecule.
There is no NET dipole moment: the molecule is
NON POLAR

e.g. CCl4 will be non-polar whereas CH3Cl will be polar H

δ+
C δ-
H Cl
H


%",
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Intermolecular Forces

Van der Waals’ Forces Van der Waals forces occur between all molecular substances and noble gases.
They do not occur in ionic substances.

These are also called transient, induced dipole-dipole interactions. They occur between all simple
covalent molecules and the separate atoms in noble gases.
In any molecule the electrons are moving constantly and randomly. As this happens the electron density
can fluctuate and parts of the molecule become more or less negative i.e. small temporary or transient
dipoles form.
These instantaneous dipoles can cause dipoles to form in neighbouring molecules. These are called
induced dipoles. The induced dipole is always the opposite sign to the original one.

Main factor affecting size of Van der Waals

The more electrons there are in the molecule the higher the chance that temporary dipoles will form. This
makes the Van der Waals stronger between the molecules and so boiling points will be greater.

The increasing boiling points of the halogens down the group 7 series can be explained by the
increasing number of electrons in the bigger molecules causing an increase in the size of the Van der
Waals between the molecules. This is why I2 is a solid whereas Cl2 is a gas.
The increasing boiling points of the alkane homologous series can be explained by the increasing
number of electrons in the bigger molecules causing an increase in the size of the Van der Waals
between molecules.
The shape of the molecule can also have an effect on the size of the Van der Waals forces. Long chain
alkanes have a larger surface area of contact between molecules for Van der Waals to form than compared to
spherical shaped branched alkanes and so have stronger Van der Waals.

Permanent dipole-dipole forces

•Permanent dipole-dipole forces occurs between polar molecules
•It is stronger than Van der Waals and so the compounds have higher boiling points
•Polar molecules have a permanent dipole. (commonly compounds with C-Cl, C-F, C-Br H-Cl, C=O bonds)
•Polar molecules are asymmetrical and have a bond where there is a significant difference in
electronegativity between the atoms.

Permanent dipole-dipole
forces occurs in addition to
Van der Waals forces

Hydrogen bonding
It occurs in compounds that have a hydrogen atom attached to one of the three most
electronegative atoms of nitrogen, oxygen and fluorine, which must have an available lone pair of
electrons. e.g. a –O-H -N-H F- H bond. There is a large electronegativity difference between the
H and the O,N,F

Always show
the lone pair of
electrons on the
O,F,N and the
dipoles and all
the δ- δ+
charges
Hydrogen bonding occurs in addition to van der waals forces


%",
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 400
Hydrogen bonding is stronger than the other two
H2O
types of intermolecular bonding.

Boiling point K
300 HF H2Te
The anomalously high boiling points of H2O, H2Se SbH3
NH3 and HF are caused by the hydrogen NH3 H2S
HI
bonding between the molecules AsH3
200 HBr
PH3 HCl SnH4
The general increase in boiling point from H2S GeH4
SiH4
to H2Te is caused by increasing Van der Waals
forces between molecules due to an increasing 100 CH4
number of electrons.
Alcohols, carboxylic acids, proteins, amides all
can form hydrogen bonds 25 50 75 100 125
Molecular mass

Four types of crystal structure: ionic, metallic, molecular and giant covalent (macromolecular).

You should be able to draw the following diagrams or describe the structure in words to
show the four different types of crystal. You should also be able to explain the properties of
these solids. The tables earlier in the revision guide explain these properties.
Ionic: sodium chloride

Giant Ionic lattice showing alternate

Na+ and Cl- ions

Metallic: magnesium or sodium

Use this
Giant metallic lattice showing close
diagram
packing magnesium ions
for any
metal Molecular: Ice This is a difficult diagram
to draw.
Molecular: Iodine H H The main point to show is
O a central water molecule
with two ordinary covalent
bonds and two hydrogen
Regular arrangement of I2 H bonds in a tetrahedral
molecules held together by H arrangement
O O
weak van der Waals forces H
H H The molecules are held
HO O further apart than in liquid
H H water and this explains the
lower density of ice
Macromolecular: diamond Macromolecular: Graphite

Planar arrangement of carbon

Tetrahedral arrangement of atoms in layers. 3 covalent bonds
per atom in each layer. 4th outer
carbon atoms. 4 covalent
electron per atom is delocalised.
bonds per atom Delocalised electrons between
layers.

Both these macromolecular structures have very high melting points because of strong covalent
forces in the giant structure. It takes a lot of energy to break the many strong covalent bonds.


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1.4 Energetics
Definition: Enthalpy change is the amount of heat energy
taken in or given out during any change in a system provided the
pressure is constant.

If an enthalpy change occurs then energy is

In an exothermic change energy is transferred from transferred between system and surroundings. The
the system (chemicals) to the surroundings. system is the chemicals and the surroundings is
everything outside the chemicals.
The products have less energy than the reactants.
In an endothermic change, energy is transferred
from the surroundings to the system (chemicals).
They require an input of heat energy e.g. thermal
Energy

Activation decomposition of calcium carbonate.

Energy: EA The products have more energy than the reactants.

reactants
Activation
Energy:
∆H EA

Energy
products

Progress of Reaction reactants ∆H

In an exothermic reaction the

∆H is negative In an endothermic reaction
the ∆H is positive
Common oxidation exothermic processes are the
combustion of fuels and the oxidation of
Progress of Reaction
carbohydrates such as glucose in respiration.

Standard Enthalpy Change of Formation

The standard enthalpy change of formation of a compound is the Mg (s) + Cl2 (g)
MgCl2 (s)
enthalpy change when 1 mole of the compound is formed from 2Fe (s) + 1.5 O2 (g)
Fe2O3 (s)
its elements under standard conditions (298K and 100kpa), all
reactants and products being in their standard states. The enthalpy of formation
Symbol
fH of an element = 0 kJ mol-1

Standard Enthalpy Change of Combustion

The standard enthalpy of combustion of a substance is defined as CH4 (g) + 2O2 (g)
CO2 (g) + 2 H2O (l)
the enthalpy change that occurs when one mole of a substance is
combusted completely in oxygen under standard conditions. Incomplete combustion will lead to
(298K and 100kPa), all reactants and products being in their soot (carbon), carbon monoxide and
standard states. water. It will be less exothermic than
complete combustion.
Symbol
cH
When an enthalpy change is
measured at standard
Enthalpy changes are normally quoted at standard conditions. conditions the symbol is
Standard conditions are: used
• 100 kPa pressure Eg
H
• 298 K (room temperature or 25oC)
• Solutions at 1mol dm-3
• all substances should have their normal state at 298K


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Measuring the Enthalpy Change for a Reaction Experimentally
Calorimetric method This equation will only give the
energy for the actual quantities
used. Normally this value is
For a reaction in solution we use the following equation converted into the energy
energy change = mass of solution x heat capacity x temperature change change per mole of one of the
Q (J) = m (g) x cp (J g-1K-1) x
T ( K) reactants. (The enthalpy
change of reaction,
Hr)

Calorimetric method Practical

One type of experiment is one in which substances are This could be a solid dissolving or reacting
mixed in an insulated container and the temperature rise in a solution or it could be two solutions
measured. reacting together

General method
 washes the equipment (cup and pipettes etc) with the solutions to be used
 dry the cup after washing
 put polystyrene cup in a beaker for insulation and support
 Measure out desired volumes of solutions with volumetric pipettes and transfer to
insulated cup
 clamp thermometer into place making sure the thermometer bulb is immersed in solution
 measure the initial temperatures of the solution or both solutions if 2 are used. Do this
every minute for 2-3 minutes
 At minute 3 transfer second reagent to cup. If a solid reagent is used then add the
solution to the cup first and then add the solid weighed out on a balance.
 If using a solid reagent then use ‘before and after’ weighing method
 stirs mixture (ensures that all of the solution is at the same temperature)
 Record temperature every minute after addition for several minutes

If the reaction is slow then the exact temperature rise can be

difficult to obtain as cooling occurs simultaneously with the
reaction.

To counteract this we take readings at regular time intervals

and extrapolate the temperature curve/line back to the time
the reactants were added together.

We also take the temperature of the reactants for a few

minutes before they are added together to get a better
average temperature. If the two reactants are solutions then
the temperature of both solutions need to be measured
before addition and an average temperature is used.

Errors in this method Read question

carefully. It may be
• energy transfer from surroundings (usually loss) necessary to describe:
• approximation in specific heat capacity of solution. The method assumes all • Method
solutions have the heat capacity of water. • Drawing of graph
• neglecting the specific heat capacity of the calorimeter- we ignore any with extrapolation
energy absorbed by the apparatus. • Description of the
• reaction or dissolving may be incomplete or slow. calculation
• density of solution is taken to be the same as water.


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Calculating the enthalpy change of reaction, H from experimental data
The heat capacity of water is
4.18 J g-1K-1. In any reaction
General method where the reactants are
dissolved in water we assume
1. Using q = m x cp x
T calculate energy change for quantities used that the heat capacity is the
same as pure water.
2. Work out the moles of the reactants used
3. Divide q by the number of moles of the reactant not in excess to give
H Also assume that the solutions
have the density of water,
4. Add a sign and unit (divide by a thousand to convert Jmol-1 to kJmol-1 which is 1g cm-3. Eg 25 cm3 will
weigh 25 g

Example 1. Calculate the enthalpy change of reaction for the reaction where 25.0cm3 of 0.200 mol dm-3
copper sulfate was reacted with 0.0100mol (excess of zinc). The temperature increased 7.0 oC .

Step 1: Calculate the energy change for the amount of reactants in the calorimeter.
Q = m x cp x
T Note the mass is the mass of the copper sulfate
Q = 25 x 4.18 x 7 solution only. Do not include the mass of zinc powder.
Q = 731.5 J

Step 2 : calculate the number of moles of the reactant not in excess.

moles of CuSO4 = conc x vol If you are not told what is in excess, then you need to
= 0.20 x 25/1000 work out the moles of both reactants and work out
= 0.005 mol using the balanced equation which one is in excess.

Step 3 : calculate the enthalpy change per mole which is often called the enthalpy change of reaction

H = Q/ no of moles
= 731.5/0.005
= 146300 J mol-1
Remember in these
= 146 kJ mol-1 to 3 sf
questions: sign,
Finally add in the sign to represent the energy change: if temp increases unit, same sig figs
the reaction is exothermic and is given a minus sign e.g. –146 kJ mol-1 as data given.

Example 2. 25.0cm3 of 2.00 mol dm-3 HC
was neutralised by 25.0cm3 of 2.00 mol dm-3 NaOH.
The temperature increased 13.5oC
Calculate the enthalpy change per mole of HC
.
Step 1: Calculate the energy change for the amount of reactants in the calorimeter.
Q = m x cp x
T Note the mass equals the mass of acid + the
Q = 50 x 4.18 x13.5 mass of alkali, as they are both solutions.
Q = 2821.5 J

Step 2 : calculate the number of moles of the HC
.

moles of HC
= conc x vol

= 2 x 25/1000
= 0. 05 mol
Step 3 : calculate
H the enthalpy change per mole which might be called the enthalpy change of neutralisation

H = Q/ no of moles
= 2821.5/0.05
Remember in these
= 56430 J mol-1
questions: sign, unit,
= -56.4 kJ mol-1 to 3 sf Exothermic and so is given a minus sign
same sig figs as data
given.


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 Measuring Enthalpies of Combustion Using Calorimetry

Enthalpies of combustion can be calculated by using calorimetry. Generally the fuel is burnt and the flame
is used to heat up water in a metal cup.

Example 3. Calculate the enthalpy change of combustion for the reaction where 0.650g of propan-1-ol
was completely combusted and used to heat up 150g of water from 20.1 to 45.5oC

Step 1: Calculate the energy change used to heat up the water.

Q = m x cp x
T
Note the mass is the mass of water in the
Q = 150 x 4.18 x 25.4 calorimeter and not the alcohol
Q = 15925.8 J

Step 2 : calculate the number of moles of alcohol combusted.

moles of propan-1-ol = mass/ Mr

= 0.650 / 60
= 0.01083 mol

Step 3 : calculate the enthalpy change per mole which is called
cH (the enthalpy change of combustion)

H = Q/ no of moles
= 15925.8/0.01083
= 1470073 J mol-1
Remember in these
= 1470 kJ mol-1 to 3 sf
questions: sign,
Finally add in the sign to represent the energy change: if temp increases unit, same sig figs
the reaction is exothermic and is given a minus sign eg –1470 kJ mol-1 as data given.

Errors in this method

• Energy losses from calorimeter

• Incomplete combustion of fuel
• Incomplete transfer of energy
• Evaporation of fuel after weighing
• Heat capacity of calorimeter not included
• Measurements not carried out under standard conditions as
H2O is gas, not liquid, in this experiment


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Hess’s Law
Hess’s law is a version of the first
Hess’s law states that total enthalpy change for a reaction is
law of thermodynamics, which
independent of the route by which the chemical change takes place
states that energy is always
conserved.

2H (g) + 2Cl(g)
On an energy level diagram the directions of the arrows can
show the different routes a reaction can proceed by.
a
In this example one route is arrow ‘a’
H2 + Cl2 b The second route is shown by arrows ΔH plus arrow ‘b’

ΔH So a = ΔH + b
2HCl (g) And rearranged
ΔH = a - b

ΔH
H+ (g) + Br - (g) H+ (aq) + Br - (aq) Interconnecting reactions can also be
shown diagrammatically.
a
d
In this example one route is arrow ‘a’ plus ΔH
The second route is shown by arrows ‘c’ plus arrow ‘d’
H (g) + Br (g) HBr (g)
c So a+ ΔH = c + d
And rearranged
ΔH = c + d - a

Often Hess’s law cycles are used to measure the enthalpy change for a reaction that cannot be measured
directly by experiments. Instead alternative reactions are carried out that can be measured experimentally.

H reaction This Hess’s law is used to work out the

CuSO4 (s) + 5H2O (l) CuSO4.5H2O (s) enthalpy change to form a hydrated salt
from an anhydrous salt.

-66.1 kJmol-1 + aq + aq +11kJmol-1

This cannot be done experimentally
because it is impossible to add the
CuSO4 (aq) exact amount of water and it is not easy
to measure the temperature change of
a solid.

H reaction + 11kJmol-1 = -66.1 kJmol-1

H reaction = -66.1 - 11
Instead both salts are dissolved in excess
water to form a solution of copper sulfate.
= -77.1 kJmol-1 The temperature changes can be measured
for these reactions.


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 Using Hess’s law to determine enthalpy changes from enthalpy changes of formation.

H reaction
Reactants Products

H reaction = Σ
fH products - Σ
fH reactants
Σ
fH reactants Σ
fH products

Elements in standard states

Example 4. Calculate the enthalpy change for this reaction

Al2O3 + 3 Mg
3 MgO + 2 Al
H reaction
Remember Al2O3 (s) + 3 Mg (s) 3 MgO (s) + 2 Al (s)

H = Σ
fH products – Σ
fH reactants elements have

f H = 0
fH(Al2O3) 3 x
fH (MgO)

H = 3 x
fH (MgO) –
fH (Al2O3)

H = (3 x –601.7) – –1675.7
fH(MgO)= -601.7 kJ mol-1 2Al (s) + 3 Mg (s) + 1.5O2 (g)
= -129.4 kJ mol-1
fH(Al2O3) = -1675.7 kJ mol-1

Example 5. Using the following data to calculate the enthalpy of combustion of propene

fH C3H6(g) = +20 kJ mol-1
f HCO2(g)= –394 kJ mol-1
fH H2O(g)= –242 kJ mol-1
C3H6 + 4.5 O2
3CO2 + 3H2O

cH
C3H6 (g) + 4.5 O2 (g) 3 CO2 (g) + 3 H2O (g)

cH = Σ
fH products – Σ
fH reactants

cH = [3 x
fH (CO2) + 3 x
fH (H2O)] -
fH (C3H6) 3 x
fH (CO2)

fH(C3H6) 3 x
fH (H2O)

cH = [(3 x –394) + (3 x –242)] – 20
= -1928 kJ mol-1 3C (s) + 3 H2 (g) + 4.5 O2 (g)

Using Hess’s law to determine enthalpy changes from enthalpy changes of combustion.

H reaction
Reactants Products

H reaction = Σ
cH reactants - Σ
cH products +O2 +O2

Σ
cH reactants Σ
cH products

Combustion Products

Example 6. Using the following combustion data to calculate the enthalpy of reaction
CO (g) + 2H2 (g)
CH3OH (g)

cH CO(g) = -283 kJ mol-1
cH H2 (g)= –286 kJ mol-1
cH CH3OH(g)= –671 kJ mol-1

H reaction

H reaction = Σ
cH reactants - Σ
cH products CO (g) + 2H2(g) CH3OH(g)

H =
cH (CO) + 2 x
cH (H2) -
cH (CH3OH) +O2 +O2

cH(CO) +
cH(CH3OH)

H = -283+ 2x –286 - -671 2x
cH (H2)
CO2 (g) + 2 H2O (l)
= -184 kJ mol-1


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 Example 7. Calculate the enthalpy of formation of propene using the following enthalpy of combustion data
3C (s) + 3H2 (g)
C3H6 (g

cH C (s) = -393kJ mol-1
cH H2 (g)= –286 kJ mol-1
cH C3H6(g)= –-2058 kJ mol-1

f H

H = Σ
cH reactants - Σ
cH products
3C (s) + 3H2 (g) C3H6 (g

fH = 3 x
cH (C) + 3 x
cH (H2 ) -
cH (C3H6)
3 x
cH (C) +
cH(C3H6)

fH = 3x -393+ 3x –286 - -2058 3 x
cH (H2 )

= +21 kJ mol-1
3 CO2 (g) + 3 H2O (l)

Mean Bond energies

Definition: The mean bond energy is the enthalpy needed to These values are positive because
break the covalent bond into gaseous atoms, averaged over energy is required to break a bond.
different molecules.
The definition only applies when the
We use values of mean bond energies because every single bond in substances start and end in the
a compound has a slightly different bond energy. E.g. In CH4 there gaseous state.
are 4 C-H bonds. Breaking each one will require a different amount
of energy. However, we use an average value for the C-H bond for
all hydrocarbons.
Gaseous atoms
Gaseous atoms
Energy
Energy

Energy
Energy
breaking Activation In an exothermic reaction Energy
breaking Activation making
bonds Energy Energy the sum of the bonds in Energy
bonds products bonds
reactants making
bonds
the reactant molecules

H will be less than the sum
H
products of the bonds in the reactants
product molecules.
Progress of reaction
Progress of reaction
Reaction profile for an Reaction profile for an
exothermic reaction endothermic reaction

In general (if all substances are gases)

H = Σ bond energies broken - Σ bond energies made

H reaction
Reactants Products

Σbond energies Σbond energies

broken in reactants made in products

Gaseous atoms of
elements

H values calculated using this method will be less accuate

than using formation or combustion data because the mean
bond energies are not exact


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Example 8. Calculate the enthalpy of combustion of propene using the &% %
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following mean bond enthalpy data.
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H H
O  
H C C C + 4.5 O O 3 O C O + 3
H H   
H H
H
 

H = Σ bond energies broken - Σ bond energies made
= [E(C=C) + E(C-C) + 6 x E(C-H) + 4.5 x E(O=O)] – [ 6 xE(C=O) + 6 E(O-H)]  

= [ 612 + 348 + (6 x 412) + (4.5 x 496) ] – [ (6 x 743) + (6 X 463)]  

= - 1572 kJmol-1  

Example 9. Calculate the enthalpy of formation of NH3 using the following mean bond enthalpy data.
½ N2 + 1.5 H2
NH3 (note the balancing is to agree with the definition of enthalpy of formation (i.e. one mole of product)

E(N≡N) = 944 kJ mol-1 E(H-H) = 436 kJ mol-1 E(N-H) = 388 kJ mol-1

H = Σ bond energies broken - Σ bond energies made

= [0.5 x E(N≡N) + 1.5 x E(H-H)] – [ 3 xE(N-H)]

= [ (0.5 x 944) + (1.5 x 436) ] – [ 3 x 388)]
= - 38 kJmol-1

A more complicated example that may occur

This is a more complicated
Working out ΔfH of a compound using bond enthalpies and other data example of the type in example 9

f H Compound in
Elements
standard state
The
H’s can be
combinations of

H to turn elements
H to turn
compound into different data
into gaseous atoms
gaseous atoms
Gaseous atoms

Can be bond energies

E(Cl-Cl) Cl2
2Cl  bond energies of
Or atomisation energies ΔatH (if compound + (
H to turn to
the substance is not diatomic gas if compound is not
gaseous)
C(s)
C(g)

Example 10
Calculate ΔfH for propane, C3H8(g), given the following data. &% - - -
C(s)
C(g) ΔatH = 715 kJ mol-1
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3C (s) + 4H2 (g)
C3H8(g),

Σ
H to turn elements - Σ
H to turn compound

f H =
into gaseous atoms into gaseous atoms

fH = (3x
atH [C] + 4 x E[H-H] ) – (2 x E[C-C]+ 8 x E[C-H] )

= (3x715 + 4 x 436 ) – (2 x 348+ 8 x 412 )
= -103 kJ mol-1


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 Enthalpies of Combustion in a Homologous Series

When comparing the enthalpies of combustion for successive members of a homologous series such as
alkanes or alcohols there is a constant rise in the size of the enthalpies of combustion as the number of
carbon atoms increases.

H H O 1 C-C, 5C-H 1C-O 1O-H and 3 O=O

H C C O H + 3 O O 2 O C O + 3
H H
bonds are broken
H H 4 C=O and 6 O-H bonds are made
ethanol ΔHc = -1365 kJ mol-1

H H H 2C-C, 7C-H 1C-O 1O-H and 4.5 O=O

O bonds are broken
H C C C O H + 4.5 O O 3 O C O + 4
H H 6 C=O and 8 O-H bonds are made
H H H
ΔHc = -2016 kJ mol-1
Propan-1-ol

H H H H
3C-C, 9C-H 1C-O 1O-H and 6 O=O
H C C C C O H + 6 O
4 bonds are broken
O O O C O+ 5 H H
H H H H
8 C=O and 10 O-H bonds are made
Butan-1-ol
ΔcH = -2677 kJ mol-1

As one goes up the homologous series there is a constant amount and type of extra bonds being broken and
made e.g. 1C-C, 2C-H and 1.5 O=O extra bonds broken and 2 C=O and 2 O-H extra bonds made, so the
enthalpy of combustion increases by a constant amount.

calculated If the results are worked out experimentally

using a calorimeter the experimental results
combustion kJ mol-1
Enthalpy of

will be much lower than the calculated ones

because there will be significant heat loss.
There will also be incomplete combustion
experimental which will lead to less energy being
released.

Mr of alcohol

Remember that calculated values of enthalpy of combustions will

be more accurate if calculated from enthalpy of formation data than
if calculated from average bond enthalpies. This is because
average bond enthalpy values are averaged values of the bond
enthalpies from various compounds.


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1.5 Kinetics
Collision theory

Energy
Reactions can only occur when collisions take place Activation
between particles having sufficient energy. The energy is Energy:
usually needed to break the relevant bonds in one or EA
either of the reactant molecules. reactants
This minimum energy is called the activation energy.

∆H
The activation energy, EA, is defined as the minimum
products
energy which particles need to collide to start a reaction.

Maxwell Boltzmann Distribution Progress of Reaction

The Maxwell-Boltzmann energy distribution shows the spread of energies that

molecules of a gas or liquid have at a particular temperature
Learn this curve
carefully
Emp this is the most
probable energy (not the
same as mean energy) The area under the curve
represents the total number of
A few have low particles present
energies because
collisions cause some Most molecules have energies
Fraction of molecules

particles to slow down between the two extremes but the

distribution is not symmetrical (normal)
with energy

Only a few particles

have energy greater
than the EA
Emp Collision energy

EA

The energy distribution

The mean energy of The energy distribution should
should go through the
the particles is not at never meet the x axis, as there is
origin because there are
the peak of the curve no maximum energy for molecules
no molecules with no
energy

Q. How can a reaction go to completion if few particles have energy greater than EA?
A. Particles can gain energy through collisions
Increasing Temperature As the temperature increases the distribution shifts
towards having more molecules with higher energies

At higher temps both the Emp and mean energy shift to higher energy
Lower temperature
Fraction of molecules

values, although the number of molecules with those energies decrease.

T= 25OC
Fraction of molecules
with energy

higher temperature

T= 1067OC
with energy

mean

Collision energy

EA
Collision energy

The total area under the curve should remain constant
because the total number of particles is constant At higher temperatures the molecules have a wider
range of energies than at lower temperatures.


 
  


 Measuring Reaction Rates

The rate of reaction is defined as the change in concentration of a substance in unit time
Its usual unit is mol dm-3s-1

When a graph of concentration of reactant is plotted vs

time, the gradient of the curve is the rate of reaction.

concentration
The initial rate is the rate at the start of the
reaction where it is fastest. rate = gradient of
tangent to curve
Reaction rates can be calculated from graphs of
concentration of reactants or products, by drawing a
tangent to the curve (at different times) and calculating
the gradient of the tangent.
time

In the experiment between sodium thiosulfate and hydrochloric acid we usually measure reaction rate as
1/time. The time is the time taken for a cross placed underneath the reaction mixture to disappear due to
the cloudiness of the sulfur .    

 

 



This is an approximation for rate of reaction as it does not include concentration. We can use this because
we can assume the amount of sulfur produced is fixed and constant.

Effect of Increasing Concentration and Increasing Pressure

At higher concentrations(and pressures) there are more particles per

unit volume and so the particles collide with a greater frequency
and there will be a higher frequency of effective collisions.

Note: If a question mentions a doubling of concentration/rate

then make sure you mention double the number of particles Higher concentration
Number of molecules

per unit volume and double the frequency of effective

collisions.
lower concentration
If concentration increases, the shape of the energy distribution
with energy

curves do not change (i.e. the peak is at the same energy) so

the Emp and mean energy do not change.

They curves will be higher, and the area under the curves will
be greater because there are more particles.
Collision energy

EA
More molecules have energy > EA (although not a greater proportion)

Comparing rate curves

Need to calculate/ compare
Amount of initial moles of reactants to
product e.g. A
distinguish between different
Volume of B finishing volumes.
gas
e.g. the amount of product is
Different volumes of the C proportional to the moles of
D
same initial concentrations reactant
will have the same initial
rate (if other conditions are Time (secs)
the same) but will end at The higher the concentration/ temperature/
different amounts surface area the faster the rate (steeper the
gradient)


 
   

 Effect of Increasing Temperature

Lower temperature

Fraction of molecules
At higher temperatures the energy of the particles
increases. They collide more frequently and more
often with energy greater than the activation energy.

with energy
More collisions result in a reaction.
higher temperature
As the temperature increases, the graph shows
that a significantly bigger proportion of particles
have energy greater than the activation energy,
so the frequency of successful collisions
increases. Collision energy

EA

Effect of Increasing Surface Area

Increasing surface area will cause successful collisions to occur more frequently between the
reactant particles and this increases the rate of the reaction.

Effect of Catalysts
Definition: Catalysts increase reaction rates without getting used up.

Explanation: They do this by providing an alternative route or mechanism with a lower

activation energy.

Activation
Comparison of the activation energies for an Energy:
uncatalysed reaction and for the same reaction with uncatalysed
a catalyst present.

reactants EA catalysed

∆H
products

Progress of Reaction
If the activation energy is lower, more
particles will have energy > EA, so
there will be a higher frequency of With a lower activation
effective collisions. The reaction will be energy more particles have
Fraction of molecules

faster. energy greater than the

activation energy
with energy

Collision energy

EA un catalysed
catalysed EA


 
   

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Equilibrium Equations
Equilibrium constant Kc Kc = equilibrium constant
Example 1
For a generalised reaction
mA + nB pC + qD [ C]p [D]q N2 (g) + 3H2 (g) 2 NH3 (g)
Kc=
m,n,p,q are the stoichiometric balancing [ A]m [B]n
numbers [NH3 (g)]2
Kc=
A,B,C,D stand for the chemical formula [N2 (g)] [H2 (g)]3
[ ] means the equilibrium concentration

The unit of Kc changes and depends on the equation.

Working out the unit of Kc

Put the unit of concentration (mol dm -3) into the Kc equation
Cancel out
[NH3 (g)]2 units 1
Kc= [mol dm-3]2 Unit = [mol dm-3]-2
Unit = Unit =
[N2 (g) ] [H2 (g)]3 [mol dm-3]2
[mol dm-3] [mol dm-3]3
Unit = mol-2 dm+6

Example 2: writing Kc expression

Working out the unit
H2 (g) +Cl2 (g) 2HCl (g) [HCl (g)]2
Kc= [mol dm-3]2
Unit Kc= = no unit
[H2 (g) ] [Cl2 (g)]
[mol dm-3] [mol dm-3]

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H2 (g) +Cl2 (g) 2HCl (g)
For the following equilibrium
In a container of volume 600cm 3 there were initially 0.500mol of H2 and 0.600 mol of Cl2.
At equilibrium there were 0.200 mol of HCl. Calculate Kc

H2 Cl2 HCl
It is often useful Using the balanced equation if 0.2 moles of
Initial moles 0.5 0.6 0
to put the mole HCl has been formed it must have used up
data in a table. 0.1 of Cl2 and 0.1 moles of H2 (as 1:2 ratio)
Equilibrium moles 0.2

Work out the moles at equilibrium for the reactants moles of reactant at equilibrium = initial moles – moles reacted

moles of hydrogen at equilibrium = 0.5 – 0.1 = 0.4 moles of chlorine at equilibrium = 0.6 – 0.1 = 0.5

H2 Cl2 HCl If the Kc has no unit then there are equal numbers of
reactants and products. In this case you do not have to
Initial moles 0.5 0.6 0 divide by volume to work out concentration. Equilibrium
moles can be put straight into the Kc expression.
Equilibrium moles 0.4 0.5 0.2

Equilibrium 0.4/0.6 0.5/0.6 0.2/0.6

[HCl (g)]2
concentration (M) =0.67 =0.83 =0.33 Kc=
[H2 (g) ] [Cl2 (g)]
Finally put = 0.332 = 0.196 no unit
Work out the Kc
concentrations into 0.67x0.83
equilibrium
conc = moles/ vol (in dm3) Kc expression
concentrations

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N2 (g) + 3H2 (g ) 2 NH3 (g)
For the following equilibrium
Initially there were 1.50 moles of N2 and 4.00 mole of H2, in a 1.50 dm3 container. At
equilibrium 30% of the Nitrogen had reacted. Calculate Kc

N2 H2 NH3
30% of the nitrogen had reacted = 0.3 x1.5 = 0.45 moles reacted.
Initial moles 1.50 4.0 0 Using the balanced equation 3 x 0.45 moles of H 2 must have
reacted and 2x 0.45 moles of NH3 must have formed
Equilibrium moles

Work out the moles at equilibrium for the reactants and products
moles of reactant at equilibrium = initial moles – moles reacted

moles of nitrogen at equilibrium = 1.5 – 0.45 = 1.05 moles of hydrogen at equilibrium =4.0 – 0.45 x3 = 2.65

moles of product at equilibrium = initial moles + moles formed

moles of ammonia at equilibrium = 0 + (0.45 x 2) = 0.9

N2 H2 NH3
Finally put concentrations into Kc expression
Initial moles 1.5 4.0 0

Equilibrium moles 1.05 2.65 0.9 [NH3 (g)]2

Kc=
Equilibrium 1.05/1.5 2.65/1.5 0.9/1.5 [N2 (g) ] [H2 (g)]3
concentration (M) =0.7 =1.77 =0.6

Kc
= 0.62 = 0.0927 mol-2 dm+6
Work out the 0.7x1.773
equilibrium
conc = moles/ vol (in dm3)
concentrations

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Using algebra it is possible to work out the amounts of each

component in an equilibrium mixture using the value of Kc

Example 5

For the following equilibrium H2 (g) + Br2 (l) 2HBr (g)

0.200 mol of H2 and 0.200 mol of Br2 are mixed and allowed to reach equilibrium. If Kc = 0.210
calculate the equilibrium amounts, in mol, of each substance.

[HBr (g)]2 Make x = moles of H2 that have reacted

Kc=
[H2 (g) ] [Br2 (l)] at equilibrium
V = volume of container

(2x/V)2 This reaction is equimolar (same number

0.21 = (0.2-x)/V . (0.2-x)/V of moles of reactant as products) so it is
possible to cancel out the volume V
(2x)2
0.21 =
(0.2-x) . (0.2-x)

(2x)2
0.21 = Square root both sides
(0.2-x)2

2x
√0.21 = Rearrange to give x
0.2-x

0.458(0.2-x) = 2x
This example has been carefully set up to
0.0917 - 0.458x = 2x avoid the formation of a quadratic equation.
0.0917 = 2x + 0.458x It is not on the A-level syllabus to solve
quadratic equations.
x = 0.0917/2.458
x = 0.0373

So at equilibrium
Moles of H2 = 0.2000- 0.0373 Moles of Br2 = 0.2000- 0.0373 Moles of HBr = 2x 0.0373
= 0.163 mol = 0.163mol = 0.0746mol

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Finally calculate the equilibrium constant.
To work out equilibrium concentrations divide the equilibrium amounts by the total volume. Then put in
Kc expression.

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[CH3CO2H] [CH3CH2OH]

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1.7 Redox
Oxidation is the process of electron loss: Reduction is the process of electron gain:
Zn
Zn2+ + 2e- Cl2 + 2e-
2Cl-
It involves an increase in oxidation number It involves a decrease in oxidation number

Rules for assigning oxidation numbers

1. All uncombined elements have an oxidation number of zero eg . Zn, Cl2, O2, Ar all have oxidation numbers of zero

2. The oxidation numbers of the elements in a compound add In NaCl Na= +1 Cl= -1
up to zero Sum = +1 -1 = 0

3. The oxidation number of a monoatomic ion is equal to the

e.g. Zn2+ = +2 Cl- = -1
ionic charge
4. In a polyatomic ion (CO32-) the sum of the individual e.g. in CO32- C = +4 and O = -2
oxidation numbers of the elements adds up to the charge
sum = +4 + (3 x -2) = -2
on the ion
5. Several elements have invariable oxidation numbers in their
common compounds.

Group 1 metals = +1
Group 2 metals = +2
Al = +3 We use these rules to
H = +1 (except in metal hydrides where it is –1 eg NaH) identify the oxidation
numbers of elements that
F = -1 have variable oxidation
Cl, Br, I = –1 except in compounds with oxygen and fluorine numbers.

O = -2 except in peroxides (H2O2 ) where it is –1 and in compounds with fluorine.

Note the oxidation number of Cl

What is the oxidation number of Fe in FeCl 3
in CaCl2 = -1 and not -2 because
Using rule 5, Cl has an O.N. of –1 there are two Cl’s
Using rule 2, the O.N. of the elements must add up to 0 Always work out the oxidation
per one atom of the element.
Fe must have an O.N. of +3
in order to cancel out 3 x –1 = -3 of the Cl’s

Redox equations and half equations

Br2 (aq) + 2I- (aq)
I2 (aq) + 2 Br- (aq)

Br2 (aq) + 2e-
+ 2 Br- (aq) 2I- (aq)
I2 (aq) + 2 e-

Br has reduced as it has gained electrons I has oxidised as it has lost electrons

A reduction half equation only shows the parts An oxidation half equation only shows the reducing agents are
of a chemical equation involved in reduction. parts of a chemical equation involved in electron donors
The electrons are on the left oxidation.
The electrons are on the right
oxidising agents are
electron acceptors
The oxidising agent is Bromine The reducing agent is the Iodide
water . It is an electron acceptor ion. It is an electron donor
When naming oxidising
and reducing agents
An oxidising agent (or oxidant) is the A reducing agent (or reductant) is the
species that causes another element to species that causes another element always refer to full name
oxidise. It is itself reduced in the reaction. reduce. It is itself oxidised in the reaction.. of substance and not
just name of element or
ion



    
Balancing redox equations
Writing half equations
1. Work out oxidation numbers for element being oxidised/ reduced 

Zn changes from 0 to +2

2. Add electrons equal to the change in oxidation number

For reduction add e’s to reactants
Zn
Zn2+ + 2e-
For oxidation add e’s to products

3. check to see that the sum of the charges on the reactant side
equals the sum of the charges on the product side 0 +2 –2 =0

More complex half-equations

If the substance that is being oxidised or reduced contains a varying amount of O (eg In acidic conditions
MnO4-
Mn2+ ) then the half equations are balanced by adding H+, OH- ions and H2O. use H+ and H2O

Example: Write the half equation for the change MnO4-
Mn2+
Mn changes from +7 to +2
1. Balance the change in O.N. with electrons Add 5 electrons to reactants MnO4- + 5e-
Mn2+

2. Add H2O in products to balance O’s in MnO4- MnO4- + 5e-
Mn2+ + 4H2O

3. Add H+ in reactants to balance H’s in H2O MnO4- + 8H+ + 5e-
Mn2+ + 4H2O

4. check to see that the sum of the charges on the reactant side
equals the sum of the charges on the product side -1 + 8 -5 = +2 +2

Example: Write the half equation for the change SO42-
SO2
S changes from +6 to +4
1. Balance the change in O.N. with electrons Add 2 electrons to reactants SO42- + 2e-
SO2

2. Add H2O in products to balance O’s in SO42- SO42- + 2e-
SO2 + 2H2O

3. Add H+ in reactants to balance H’s in H2O SO42- + 4H+ + 2e-
SO2 + 2H2O

4. check to see that the sum of the charges on the reactant side
equals the sum of the charges on the product side -4 + 4 = 0 0

Combining half-equations
To combine two half equations there must be
To make a full redox equation combine a reduction
equal numbers of electrons in the two half
half equation with a oxidation half equation
equations so that the electrons cancel out
Example 1

Reduction MnO4- + 8 H+ + 5 e-
Mn2+ + 4 H2O x2

Multiply the half equations to get
Oxidation C2O42-
2 CO2 + 2 e- x5 equal electrons

2MnO4- + 16 H+ + 5C2O42-
2Mn2+ + 10 CO2 + 8 H2O Add half equations together and cancel
electrons
Example 2
Reduction SO42- + 10H+ + 8e-
H2S+ 4H2O Multiply the half equations to get
equal electrons
Oxidation 2I-
I2 + 2 e- x4
Add half equations together and
8I- + SO42- + 10H+
H2S+ 4I2 + 4H2O cancel electrons



    
 2.1 Periodicity
Periodicity is the repeating pattern of physical or
chemical properties going across the periods

Classification of elements in s, p, d blocks

Elements are classified as s, p or d block, according
to which orbitals the highest energy electrons are in.

Period 2 = Li, Be, B, C, N, O, F, Ne

Period 3 = Na, Mg, Al, Si, P, S, Cl, Ar

Atomic radius 0.18

0.16

atomic radius (nm)

Atomic radii decrease from left to right across a
0.14
period, because the increased number of protons 0.12
create more positive charge attraction for electrons 0.1
which are in the same shell with similar shielding. 0.08
0.06
0.04
0.02
Exactly the same trend in period 2 0
Na Mg Al Si P S Cl Ar

1st Ionisation Energy

There is a general trend across to increase. This is due to 1600
1st ionisation energy

increasing number of protons as the electrons are being 1400

added to the same shell. 1200
(kJ/mol)

1000
There is a small drop between Mg + Al. Mg has its outer 800
600
electrons in the 3s sub shell, whereas Al is starting to fill the
400
3p subshell. Al’s electron is slightly easier to remove
200
because the 3p electrons are higher in energy. 0
Na Mg Al Si P S Cl Ar
There is a small drop between phosphorous and sulfur.
Sulfur’s outer electron is being paired up with an another Exactly the same trend in period 2 with
electron in the same 3p orbital. drops between Be & B and N to O for
When the second electron is added to an orbital there is a same reasons- make sure change 3s
slight repulsion between the two negatively charged and 3p to 2s and 2p in explanation!
electrons which makes the second electron easier to remove.

Melting and boiling points

For Na, Mg, Al- Metallic bonding : strong bonding – gets 3000
stronger the more electrons there are in the outer shell that 2500
Melting and boiling

are released to the sea of electrons. A smaller sized ion with 2000
points (K)

a greater positive charge also makes the bonding stronger.

1500
Higher energy is needed to break bonds.
1000
Si is Macromolecular: many strong covalent bonds between
500
atoms, high energy needed to break covalent bonds– very
0
high mp +bp
Na Mg Al Si P S Cl Ar
Cl2 (g), S8 (s), P4 (S)- simple molecular : weak van der waals
between molecules, so little energy is needed to break them – Similar trend in period 2
low mp+ bp Li,Be metallic bonding (high mp)
S8 has a higher mp than P4 because it has more electrons B,C macromolecular (very high mp)
(S8 =128)(P4=60) so has stronger v der w between molecules N2,O2 molecular (gases! Low mp as
small v der w)
Ar is monoatomic weak van der waals between atoms Ne monoatomic gas (very low mp)

 
   
2.2 Group 2
Melting points
Melting points decrease down the group. The metallic
Atomic radius
bonding weakens as the atomic size increases. The
Atomic radius increases down the group.
distance between the positive ions and delocalized
As one goes down the group, the atoms have more
electrons increases. Therefore the electrostatic
shells of electrons making the atom bigger.
attractive forces between the positive ions and the
delocalized electrons weaken.

1st Ionisation Energy

The outermost electrons are held more weakly because they are successively further from the nucleus
in additional shells.
In addition, the outer shell electrons become more shielded from the attraction of the nucleus by the
repulsive force of inner shell electrons

Group 2 reactions Reactivity of group 2 metals increases down the group

Reactions with oxygen.
Mg will also react slowly with oxygen without a flame.
The group 2 metals will burn in oxygen. Mg ribbon will often have a thin layer of magnesium oxide on it
Mg burns with a bright white flame. formed by reaction with oxygen.
2Mg + O2
2MgO 2Mg + O2
2MgO
This needs to be cleaned off by emery paper before doing
MgO is a white solid with a high melting reactions with Mg ribbon.
point due to its ionic bonding. If testing for reaction rates with Mg and acid, an un-cleaned Mg
ribbon would give a false result because both the Mg and MgO
would react but at different rates.
Mg + 2HCl
MgCl2 + H2
MgO + 2HCl
MgCl2 + H2O

Reactions with water. Make sure you learn the difference between the reaction of
magnesium with steam and that of warm water

Magnesium reacts in steam to produce Mg will also react with warm water, giving a different
magnesium oxide and hydrogen. The Mg magnesium hydroxide product.
would burn with a bright white flame. Mg + 2 H2O
Mg(OH)2 + H2
Mg (s) + H2O (g)
MgO (s) + H2 (g) This is a much slower reaction than the reaction with
steam and there is no flame.

The other group 2 metals will react with cold water with One would observe:
increasing vigour down the group to form hydroxides.
•fizzing, (more vigorous down group)
Ca + 2 H2O (l)
Ca(OH)2 (aq) + H2 (g)
•the metal dissolving, (faster down group)
Sr + 2 H2O (l)
Sr(OH)2 (aq) + H2 (g)
•the solution heating up (more down group)
Ba + 2 H2O (l)
Ba(OH)2 (aq) + H2 (g)
•with calcium a white precipitate appearing
The hydroxides produced make the water alkaline (less precipitate forms down group with
(if they are soluble in water) other metals)


# -
!&*'#& 
Using Magnesium to Extract titanium
Titanium cannot be extracted with carbon
Titanium is a very useful metal because it is abundant,
because titanium carbide (TiC) it is formed
has a low density and is corrosion resistant – it is used for
rather than titanium .
making strong, light alloys for use in aircraft for example.
Titanium cannot be extracted by electrolysis
because it has to be very pure.
Titanium is extracted by reaction with a
more reactive metal (e.g. Mg).

Steps in extracting titanium TiO2 + 2 Cl2 + 2 C  TiCl4 + 2 CO

1. TiO2 (solid) is converted to TiCl4 (liquid) at 900°C:
2. The TiCl4 is purified by fractional distillation in an argon
atmosphere. TiCl4 + 2Mg  Ti + 2 MgCl2
3. The Ti is extracted by Mg in an argon atmosphere at 500°C

Titanium is expensive because TiO2 is converted to TiCl4 as it can

be purified by fractional distillation,
1. The expensive cost of the Mg TiCl4 being molecular (liquid at
2. This is a batch process which makes it expensive because the room temperature) rather than
process is slower (having to fill up and empty reactors takes ionic like TiO2 (solid at room
time) and requires more labour and the energy is lost when the temperature).
reactor is cooled down after stopping
3. The process is also expensive due to the argon, and the need to
remove moisture (because TiCl4 is susceptible to hydrolysis).
4. High temperatures required in both steps

This all makes titanium expensive even though it is a relatively abundant metal.
It is only therefore used to a limited amount even though it has useful properties.


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Solubility of Hydroxides
Group II hydroxides become more soluble down the group.
All Group II hydroxides when not soluble appear as white precipitates.

Magnesium hydroxide is classed as insoluble in water.   
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It is safe to use because it is so weakly alkaline. It is
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preferable to using calcium carbonate as it will not produce

carbon dioxide gas.
Barium hydroxide would easily dissolve
in water. The hydroxide ions present
would make the solution strongly alkaline.
Solubility of Sulfates
Ba(OH)2 (S) + aq
Ba2+ (aq) + 2OH-(aq)
Group II sulfates become less soluble down the group.
BaSO4 is the least soluble.

An equation for the formation of the precipitate can be written as a full equation or simplest ionic equation
Full equation : 

  
 


  
Ionic equation: Sr2+ (aq) + SO42-(aq)
SrSO4 (s).

BaSO4 is used in medicine as a ‘Barium meal’ given to patients who need x-rays of their intestines. The barium
absorbs the x-rays and so the gut shows up on the x-ray image. Even though barium compounds are toxic, it is
safe to use here because its low solubility means it is not absorbed into the blood.

If barium metal is reacted with sulfuric acid it will only react slowly as the insoluble barium sulfate produced
will cover the surface of the metal and act as a barrier to further attack.
Ba + H2SO4
BaSO4 + H2
The same effect will happen to a lesser extent with metals going up the group as the solubility increases.
The same effect does not happen with other acids like hydrochloric or nitric as they form soluble group 2 salts.

Testing for Presence of a Sulfate ion

BaCl2 solution acidified with hydrochloric acid is used as a reagent to
Other anions should give a
test for sulphate ions.
negative result which is no
If acidified barium chloride is added to a solution that contains sulfate ions a precipitate forming.
white precipitate of barium sulfate forms.

Simplest ionic equation

Ba2+ (aq) + SO42-(aq)
BaSO4 (s).

The hydrochloric acid is needed to react with carbonate impurities that are often found in salts which
would form a white barium carbonate precipitate and so give a false result. You could not use sulfuric acid
because it contains sulfate ions and so would give a false positive result.

 


 



 Fizzing due to CO2 would be observed if a carbonate was
  
present.

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Insoluble salts can be made by mixing appropriate solutions of ions so that a precipitate is formed
barium nitrate (aq) + sodium sulfate (aq)
barium sulfate (s) + sodium nitrate (aq)
These are called precipitation reactions. A precipitate is a solid

There are some common rules for solubility of salts. No syllabus requires these to be learnt but a
good chemist does know them.
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When making an insoluble salt, normally the salt would be removed by filtration, washed with
distilled water to remove soluble impurities and then dried on filter paper
Filtration
Filter
paper Buchner
residue
funnel
Filter Filter paper
funnel
Buchner flask (has Air outlet to
thicker glass walls water pump
than a normal flask
filtrate to cope with the
vacuum )

This is gravitational filtration. This is vacuum filtration. The apparatus is

Use if small amounts of solid connected to a water pump which will
are formed. produce a vacuum. Use if larger amounts
of solid are formed.

For both types of filtration apparatus AQA expect filter paper to be drawn on the diagram

Writing Ionic equations for precipitation reactions

We usually write ionic equations to show precipitation Spectator ions are ions that are
reactions. Ionic equations only show the ions that are • Not changing state
reacting and leave out spectator ions. • Not changing oxidation number

Take full equation Ba(NO3)2 (aq) + Na2SO4 (aq)
BaSO4 (s) + 2 NaNO3 (aq)

Separate (aq) solutions Ba2+(aq) + 2NO3-(aq) + 2Na+ (aq)+ SO42-(aq)
BaSO4(s) + 2 Na+(aq)+ 2NO3- (aq)
into ions

Cancel out spectator ions leaving

Ba2+ (aq) + SO42-(aq)
BaSO4 (s).
the simplest ionic equation


# -
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 2.3 Halogens Fluorine (F2): very pale yellow gas. It is highly reactive
Chlorine : (C2) greenish, reactive gas, poisonous in high concentrations
Bromine (Br2) : red liquid, that gives off dense brown/orange poisonous fumes
Iodine (I2) : shiny grey solid sublimes to purple gas.

Trend in melting point and boiling point Trend in electronegativity

Increase down the group Electronegativity is the relative tendency of an atom in a

molecule to attract electrons in a covalent bond to itself.
As the molecules become larger they have
more electrons and so have larger van der As one goes down the group the electronegativity of the
waals forces between the molecules. As the elements decreases.
intermolecular forces get larger more energy As one goes down the group the atomic radii increases due
has to be put into break the forces. This to the increasing number of shells. The nucleus is therefore
increases the melting and boiling points. less able to attract the bonding pair of electrons.

1. The displacement reactions of halide ions by halogens.

A halogen that is a strong oxidising agent will The oxidising strength decreases down the group.
displace a halogen that has a lower oxidising Oxidising agents are electron acceptors.
power from one of its compounds.
know these
Chlorine will displace both bromide and iodide ions; bromine will displace iodide ions observations !

Chlorine (aq) Bromine (aq) Iodine (aq) The colour of the solution in
the test tube shows which free
potassium Very pale green Yellow solution, no Brown solution, halogen is present in solution.
chloride (aq) solution, no reaction no reaction Chlorine =very pale green
reaction solution (often colourless),
potassium Yellow solution, Cl Yellow solution, no Brown solution, Bromine = yellow solution
bromide (aq) has displaced Br reaction no reaction Iodine = brown solution
(sometimes black solid
potassium Brown solution, Cl Brown Solution, Br Brown Solution,
present)
iodide (aq) has displaced I has displaced I no reaction

Be able to write these reactions as two half

C2(aq) + 2Br – (aq)
2C – (aq) + Br2(aq)
equations showing oxidation or reduction
C2(aq) + 2I – (aq)
2C – (aq) + I2(aq) e.g. 2Br - (aq)
Br2 (aq)+ 2e-
Br2(aq) + 2I – (aq)
2Br – (aq) + I2(aq) C2 (aq)+ 2e-
2C- (aq)

2. The reactions of halide ions with silver nitrate. The role of nitric acid is to react with any carbonates
present to prevent formation of the precipitate
This reaction is used as a test to identify which halide ion Ag2CO3. This would mask the desired observations
is present. The test solution is made acidic with nitric
2 HNO3 + Na2CO3
2 NaNO3 + H2O + CO2
acid, and then silver nitrate solution is added dropwise.

Fluorides produce no precipitate The silver halide precipitates can be treated with ammonia
Chlorides produce a white precipitate solution to help differentiate between them if the colours look
Ag+(aq) + C- (aq)
AgC(s) similar:
Bromides produce a cream precipitate Silver chloride dissolves in dilute ammonia to form a
Ag+(aq) + Br- (aq)
AgBr(s) complex ion
Iodides produce a pale yellow precipitate AgC(s) + 2NH3(aq)
[Ag(NH3)2]+ (aq) + C- (aq)
Ag+(aq) + I- (aq)
AgI(s) Colourless solution
Silver bromide dissolves in concentrated ammonia to form a
complex ion
AgBr(s) + 2NH3(aq)
[Ag(NH3)2]+ (aq) + Br - (aq)
Colourless solution
Silver iodide does not react with ammonia – it is too insoluble.


 
   

3. The reaction of halide salts with concentrated sulfuric acid.
The halides show increasing power as
Explanation of differing reducing power of halides
reducing agents as one goes down the
A reducing agent donates electrons.
group. This can be clearly demonstrated in
The reducing power of the halides increases down group 7
the various reactions of the solid halides with
They have a greater tendency to donate electrons.
concentrated sulfuric acid.
This is because as the ions get bigger it is easier for the
Know the equations and observations of outer electrons to be given away as the pull from the nucleus
these reactions very well. on them becomes smaller.

Fluoride and Chloride

F- and Cl- ions are not strong enough reducing agents to reduce the S in H2SO4.
No redox reactions occur. Only acid-base reactions occur.

NaF(s) + H2SO4(l)
NaHSO4(s) + HF(g)

These are acid –base reactions and
Observations: White steamy fumes of HF are evolved.
not redox reactions. H2SO4 plays the
NaCl(s) + H2SO4(l)
NaHSO4(s) + HC(g) role of an acid (proton donor).
Observations: White steamy fumes of 
 are evolved.

Bromide
Br- ions are stronger reducing agents than Cl- and F- and after the initial acid-base
reaction reduce the sulfur in H2SO4 from +6 to + 4 in SO2
Observations: White steamy
Acid- base step: NaBr(s) + H2SO4(l)
NaHSO4(s) + HBr(g) fumes of HBr are evolved.
Redox step: 2 HBr + H2SO4
Br2(g) + SO2(g) + 2 H2O(l) orange fumes of bromine are also
evolved and a colourless, acidic gas
Ox ½ equation 2Br -
Br2 + 2e- SO2

Re ½ equation H2SO4 + 2 H+ + 2 e-
SO2 + 2 H2O Reduction product = sulfur dioxide

Note the H2SO4 plays the role of acid in the first step producing HBr
and then acts as an oxidising agent in the second redox step.

Iodide
I- ions are the strongest halide reducing agents. They can reduce the sulfur from
+6 in H2SO4 to + 4 in SO2, to 0 in S and -2 in H2S.

NaI(s) + H2SO4(l)
NaHSO4(s) + HI(g) Observations:

2 HI + H2SO4
I2(s) + SO2(g) + 2 H2O(l) White steamy fumes of HI are evolved.
6 HI + H2SO4
3 I2 + S (s) + 4 H2O (l) Black solid and purple fumes of Iodine are
8 HI + H2SO4
4 I2(s) + H2S(g) + 4 H2O(l) also evolved
A colourless, acidic gas SO2
A yellow solid of sulfur
Ox ½ equation 2I -
I2 + 2e- H2S (Hydrogen sulfide), a gas with a bad egg
Re ½ equation H2SO4 + 2 H+ + 2 e-
SO2 + 2 H2O smell,

Re ½ equation H2SO4 + 6 H+ + 6 e-
S + 4 H2O

Reduction products = sulfur dioxide, sulfur
Re ½ equation H2SO4 + 8 H+ + 8 e-
H2S + 4 H2O and hydrogen sulfide

Note the H2SO4 plays the role of acid in the first step producing HI and
then acts as an oxidising agent in the three redox steps.

Often in exam questions these redox reactions are

worked out after first making the half-equations


 
   

4. The disproportionation reactions of chlorine.

Disproportionation is the name for a reaction where Reaction with water in sunlight
an element simultaneously oxidises and reduces. If the chlorine is bubbled through water in the
presence of bright sunlight a different reaction
Chlorine with water: occurs.
C2 (g) + H2O (l)
HCO (aq) + HC (aq) 2C2 + 2H2O
4H+ + 4C- + O2
The same reaction occurs to an equilibrium mixture
of chlorine water when standing in sunlight. The
Chlorine is both simultaneously reducing and oxidising greenish colour of chlorine water fades as the C2
reacts and a colourless gas (O2) is produced.
If some universal indicator is added to the solution it will
first turn red due to the acidity of both reaction products. It The greenish colour of these solutions is
will then turn colourless as the HCO bleaches the colour. due to the C2

Chlorine is used in water treatment to kill bacteria. It has been used to treat drinking water and the water in
swimming pools. The benefits to health of water treatment by chlorine outweigh its toxic effects.

Reaction of chlorine with cold dilute NaOH solution:

C2,(and Br2, I2) in aqueous solutions will react with cold sodium hydroxide. The colour of the halogen
solution will fade to colourless.

C2 (aq) + 2 NaOH (aq)
NaC (aq) + NaCO (aq) + H2O (l)

The mixture of NaC and NaCO is used as bleach and to disinfect/ kill bacteria.

Naming chlorates/sulfates

In IUPAC convention the various forms of sulfur and chlorine compounds where oxygen is
combined are all called sulfates and chlorates with relevant oxidation number given in roman
numerals. If asked to name these compounds remember to add the oxidation number.

NaCO: sodium chlorate(I)

NaCO3: sodium chlorate(V)
K2SO4 potassium sulfate(VI)
K2SO3 potassium sulfate(IV)


 
   

3.1 Organic: Basic Concepts
Basic definitions
Hydrocarbon is a compound consisting of hydrogen and carbon only to know

Saturated: Contain single carbon-carbon bonds only Unsaturated : Contains a C=C double bond

Molecular formula: The formula which shows the actual number of each type of atom

Empirical formula: shows the simplest whole number ratio of atoms of each element in the compound

General formula: algebraic formula for a homologous series e.g. CnH2n

Structural formula shows the minimal detail that shows the arrangement of atoms in a
molecule, eg for butane: CH3CH2CH2CH3 or CH3(CH2)2CH3,

Displayed formula: show all the covalent bonds and atoms present in a molecule

Drawing displayed formulae Remember that the shape around the

carbon atom in saturated hydrocarbons is
H H H H tetrahedral and the bond angle is 109.5o
When drawing organic
H C C C C H compounds add the
hydrogen atoms so that H H
H H H
H C H each carbon has 4 bonds
H C C H
H

H H

Skeletal formula shows the simplified organic formula, shown by removing hydrogen atoms from alkyl chains,
leaving just a carbon skeleton and associated functional groups.

OH

But-2-ene Butan-1-ol
2-methylbutane cyclohexane cyclohexene

Functional group is an atom or group of atoms which when present in different molecules
causes them to have similar chemical properties

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group and same general formula.
•They show a gradual change in physical properties (e.g. boiling point).
• Each member differs by CH2 from the last.
• same chemical properties.

prefix / suffix
homologous functional example
(* = usual use)
series group
Alkane
CH3CH2CH2CH3
C C
-ane butane

H H
Alkenes C C Suffix* -ene C C propene
H
H C
H
H

suffix* -ol H H H propan-1-ol

Alcohols prefix hydroxy-
C OH H C C C O H
OH
H H H

Prefix* H H H
Halogenoalkanes chloro- 1-chloropropane
C halogen H C C C Cl
bromo-
iodo- H H H Cl

suffix -al H O
O
Aldehydes O ethanal
C H
prefix formyl- H C C H

suffix* -one
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O propanone
prefix oxo-
H C C C H
Ketones C

H H

suffix* -oic acid

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H
OH
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O
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Esters C O
H C C O C H

H H
O

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chain), with all others taking the prefix form. However, double and triple C-C bonds only take suffix form.
Order of priority highest first:
Carboxylic acids >aldehydes>ketones>alcohols>alkenes>halogenoalkanes

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 Introduction to Mechanisms
To understand how the reaction proceeds we must first understand how bonds are broken in organic mechanisms
There are two ways to break a covalent bond:
1.Homolytic fission:
each atom gets one electron from the covalent bond
one headed arrow shows
movement of one electron
Y X Y
X

The bond has broken in a process called homolytic fission.

When a bond breaks by homolytic fission it forms two free radicals. Definition

Free radicals do not have a charge and are represented by a A free radical is a reactive species
which possess an unpaired electron
2. Heterolytic fission: (one atom gets both electrons)

X Y X: - Y+
two headed arrow shows
movement of pair of
OR - electrons
X Y X+ Y:

+ -
xx xx

x
+ Cl

xx
Cl Cl Cl
xx
x

xx xx

Heterolytic fission produces ions

Most organic reactions occur via heterolytic fission, producing ions

The mechanism: To understand a reaction fully we must look in detail at how it proceeds step
by step. This is called its mechanism
A curly arrow will always
We use curly arrows in mechanisms to show the movement of an electron
start from a lone pair of
pair showing either breaking or formation of a covalent bond;
electrons or the centre
of a bond

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The effect of EZ stereoisomerism on physical properties
E-Z stereoisomers can have differing melting and boiling points.
δ- δ-
Cl δ- Cl Cl H

δ+ C C δ+ δ+ C C δ+

H H H Cl δ-
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3.2 Alkanes
Refining crude oil fuel gas (bottled)
20
C

Fractional Distillation: Industrially petrol/gasoline

40
C
naptha (chemicals)
Petroleum is a mixture consisting mainly
Crude 110
C
of alkane hydrocarbons
oil kerosene (jet fuel)
180
C
Petroleum fraction: mixture of hydrocarbons with diesel oil
a similar chain length and boiling point range 250
C
fuel oil
300
C
Furnace
lubricating oils
340
C
• Oil is pre-heated Key points to learn
• then passed into column. bitumen
• The fractions condense at different heights
• The temperature of column decreases upwards
• The separation depends on boiling point. This is a physical process
involving the splitting of
• Boiling point depends on size of molecules.
weak van der waals forces
• The larger the molecule the larger the van der waals forces
between molecules
• Similar molecules (size, bp, mass) condense together
• Small molecules condense at the top at lower temperatures
• and big molecules condense at the bottom at higher temperatures.

Vacuum distillation unit Vacuum distillation allows

heavier fractions to be further
• Heavy residues from the fractionating column are distilled
separated without high
again under a vacuum.
temperatures which could
• Lowering the pressure over a liquid will lower its boiling break them down.
point.

Fractional Distillation: In the laboratory

Fractional distillation is used
• Heat the flask, with a Bunsen burner or electric
to separate liquids with
mantle
different boiling points
• This causes vapours of all the components in the
mixture to be produced.
• Vapours pass up the fractionating column.
• The vapour of the substance with the lower boiling
point reaches the top of the fractionating column
first.
• The thermometer should be at or below the boiling
point of the most volatile substance.
• The vapours with higher boiling points condense
back into the flask.
condenser
• Only the most volatile vapour passes into the
condenser.
fractionating column
• The condenser cools the vapours and condenses to
a liquid and is collected.

flask

  
    

 Cracking
Cracking: conversion of large hydrocarbons to smaller hydrocarbon molecules by breakage of C-C bonds

High Mr alkanes
smaller Mr alkanes+ alkenes + (hydrogen)

Economic reasons for cracking

• The petroleum fractions with shorter C chains (e.g. petrol and This is a chemical process
naphtha) are in more demand than larger fractions. involving the splitting of
• To make use of excess larger hydrocarbons and to supply demand strong covalent bonds so
for shorter ones, longer hydrocarbons are cracked. requires high temperatures.
• The products of cracking are more valuable than the starting
materials (e.g. ethene used to make poly(ethene), branched alkanes
for motor fuels, etc.)

There are two main types of cracking: thermal and catalytic. They need different conditions and are
used to produce different products

Thermal Cracking Catalytic Cracking

Conditions: Conditions:
High pressure (7000 kPa) Slight or moderate pressure
High temperature (400°C to 900°C) High temperature (450°C)
Zeolite catalyst
produces mostly alkenes e.g. ethene used
for making polymers and ethanol Produces branched and cyclic
sometimes produces hydrogen used in the alkanes and aromatic hydrocarbons
Haber Process and in margarine manufacture.
Used for making motor fuels
Example Equations
Branched and cyclic hydrocarbons burn more
C8H18
C6H14 + C2H4
cleanly and are used to give fuels a higher octane
C12H26
C10H22 + C2H4
number
Bonds can be broken anywhere in the molecule Cheaper than thermal cracking because it saves
by C-C bond fission and C-H bond fission. energy as lower temperatures and pressures are used

Combustion
Alkanes readily burn in the
Fuel : releases heat energy when burnt
presence of oxygen. This
combustion of alkanes is highly
Complete Combustion exothermic, explaining their use
In excess oxygen alkanes will burn with complete combustion as fuels.

The products of complete combustion are CO2 and H2O.

C8H18(g) + 12.5 O2(g)
8CO2(g) + 9 H2O(l)

Incomplete Combustion Incomplete combustion produces

less energy per mole than
If there is a limited amount of oxygen then incomplete combustion
complete combustion
occurs, producing CO (which is very toxic) and/or C (producing a sooty
flame)
Carbon (soot) can cause global
CH4(g) + 3/2 O2(g)
CO(g) + 2 H2O(l)
dimming- reflection of the sun’s
CH4(g) + O2(g)
C(s) + 2 H2O(l)
light

  
    

Pollution from Combustion
Sulfur containing impurities are found in petroleum fractions which
Coal is high in sulfur content, and
produce SO2 when they are burned.
large amounts of sulfur oxides are
S+ O2
SO2 CH3SH+ 3O2
SO2 + CO2 + 2H2O emitted from power stations.

SO2 will dissolve in atmospheric water and can produce acid rain.

SO2 can be removed from the waste gases from furnaces (e.g. coal fired
power stations) by flue gas desulfurisation. The gases pass through a The calcium sulfite which is
scrubber containing basic calcium oxide which reacts with the acidic formed can be used to make
sulfur dioxide in a neutralisation reaction calcium sulfate for
plasterboard.
SO2 + CaO
CaSO3

Nitrogen Oxides NOx

Nitrogen oxides form from the reaction between N2 and O2 inside the car engine.
The high temperature and spark in the engine provides sufficient energy to break strong N2 bond

N2 + O2
2NO N2 + 2O2
2NO2

Pollutant Environmental consequence

Nitrogen oxides (formed when N2 in the air NO is toxic and can form acidic gas NO2
reacts at the high temperatures and spark in NO2 is toxic and acidic and forms acid rain
the engine)
Carbon monoxide toxic
Carbon dioxide Contributes towards global warming
Unburnt hydrocarbons (not all fuel burns in the Contributes towards formation of smog
engine)
soot Global dimming and respiratory problems

Catalytic converters
These remove CO, NOx and unburned hydrocarbons (e.g. octane, C8H18) Converters have a ceramic
from the exhaust gases, turning them into ‘harmless’ CO2, N2 and H2O. honeycomb coated with a thin
layer of catalyst metals
2 CO + 2 NO
2 CO2 + N2
platinum, palladium, rhodium
C8H18 + 25 NO
8 CO2 + 12½ N2 + 9 H2O – to give a large surface area.

Global warming
Carbon dioxide (CO2), methane (CH4) and water vapour (H2O) are all greenhouse gases.
Water is the main greenhouse gas (but is natural), followed by carbon dioxide and methane.
Mechanism of greenhouse effect
UV wavelength radiation passes through the atmosphere to the Earth’s surface and heats up Earth’s surface.
The Earth radiates out infrared long wavelength radiation.
The C=O Bonds in CO2 absorb infrared radiation so the IR radiation does not escape from the atmosphere.
This energy is transferred to other molecules in the atmosphere by collisions so the atmosphere is warmed.

Carbon dioxide levels have risen significantly in recent years due to The Earth is thought to be getting
increasing burning of fossil fuels. warmer, and many scientists believe it
Carbon dioxide is a particularly effective greenhouse gas and its is due to increasing amounts of
increase is thought to be largely responsible for global warming. greenhouse gases in the atmosphere.

  
    

  
     
Reaction of alkanes with bromine / chlorine in UV light

In the presence of UV light alkanes react with chlorine to form a In general, alkanes do not react
mixture of products with the halogens substituting hydrogen atoms. with many reagents.
This is because the C-C bond
Overall Reaction and the C-H bond are relatively
This is the overall reaction, but strong
 a more complex mixture of
 

   
products is actually formed
methane chloromethane

To understand this reaction fully we must look in detail at how it proceeds step by step.
This is called its mechanism
It proceeds via a series of steps:
Step one: initiation
The mechanism for this reaction is called a free radical substitution Step two: propagation
Step three: termination

Step one: Initiation The UV light supplies the energy to break the Cl-Cl bond. It is
  
  


broken in preference to the others because it is the weakest.
 
 
The bond has broken in a process called homolytic fission.

each atom gets one electron from the covalent bond

DEFINITION
When a bond breaks by homolytic fission it forms free radicals.
A free radical is a reactive species which
Free radicals do not have a charge and are represented by a
possess an unpaired electron.

Step two: Propagation

The chlorine free radicals are very reactive and remove
an H from the methane leaving a methyl free radical
  
 

  
 
 



  The methyl free radical reacts with a  molecule to
  produce the main product and another  free radical

All propagation steps have a free radical in the reactants and in the products.

As the Cl free radical is regenerated, it can react with several more

alkane molecules in a chain reaction.

Step three: Termination Collision of two free radicals does not generate further free radicals:
the chain is terminated.
 

 
 
 
  

Minor step leading to impurities of ethane in product.
    Write this step using structural formulae and do not
use molecular formulae.

  
    

Applying the mechanism to other alkanes
The same mechanism is used: Learn
Example: Write mechanism of Br2 and propane the patterns in the mechanism

STEP ONE Initiation

Essential condition: UV light
Br2
2Br
. Br2 splits in the same way as Cl2

STEP TWO Propagation

.
CH3CH2CH3 + Br
HBr + CH3CH2CH2
.
Remove one H from the alkane to produce a radical
.
CH3CH2CH2 + Br2
CH3CH2CH2Br + Br
.
To the radical produced in the previous step add a Br
STEP THREE Termination
.
CH3CH2CH2 + Br
CH3CH2CH2Br
.
. .
CH3CH2CH2 + CH3CH2CH2
CH3CH2CH2CH2CH2CH3

Propagation steps for substituting a halogen on a ‘middle’ carbon

.
CH3CH2CH3 + Br
HBr + CH3CH CH3
.
If the question asks for the halogen to be substituted
.
CH3CH CH3 + Br2
CH3CHBrCH3 + Br
. onto a middle carbon in the chain, it is important to
put the free radical ‘dot’ on the correct carbon in the
propagation stages.

Further substitution reactions

Excess Cl2 present will promote further substitution and could produce   
   
 

These reactions could occur Example propagation steps that would lead to
further substitution



  



  
 

  
 

      

  
 
   

Overall reaction equations

You should be able to write overall reaction equations for various reactions
Example 1. Write the overall reaction equation for the formation of CCl4 from CH4 + Cl2

  

 
  
 

Example 2. Write the overall reaction equation for the formation of CFCl3 from CH3F + Cl2
 


 
   
 

Note  is always the side product – never H2

  
    

3.3 Halogenoalkanes
Naming Halogenoalkanes H H H
H

H C H
H H H
Based on original alkane, with a prefix indicating halogen atom: H C C C H
H C C C C H
Fluoro for F; Chloro for C; Bromo for Br; Iodo for I.
Br H H H Cl H H
Substituents are listed alphabetically
 
Classifying halogenoalkanes
Halogenoalkanes can be classified as primary, secondary or tertiary depending
on the number of carbon atoms attached to the C-X functional group.
H
H H H H H H
H C H
H H H
H C C C H H C C C H
H C C C C H

Br H H H Br H H Cl H H

Primary halogenoalkane Secondary halogenoalkane Tertiary halogenoalkane

One carbon attached to the Two carbons attached to the Three carbons attached to the
carbon atom adjoining the carbon atom adjoining the carbon atom adjoining the
halogen halogen halogen

Reactions of Halogenoalkanes Halogenoalkanes undergo either Organic reactions are

substitution or elimination reactions classified by their
mechanisms
1. Nucleophilic substitution reactions
Substitution: swapping a halogen atom for another atom or groups of atoms

Nucleophile: electron pair donator e.g. :OH-, :NH3, CN-

:Nu represents any nucleophile – they
The Mechanism: We draw (or outline) mechanisms to always have a lone pair and act as
show in detail how a reaction proceeds electron pair donators

Nu:-
The nucleophiles
H H The carbon has a small
attack the positive H H positive charge because
carbon atom
of the electronegativity
H C C δ+ X δ- H C C Nu + X- difference between the
carbon and the halogen
H H
H H

We use curly arrows in mechanisms (with

A curly arrow will always start
two line heads) to show the movement of
from a lone pair of electrons or
two electrons
the centre of a bond

The rate of these substitution reactions depends on the strength %$
$)"&+


of the C-X bond !#%"
The weaker the bond, the easier it is to break and the faster the reaction.
 
' 
The iodoalkanes are the fastest to substitute and the
fluoroalkanes are the slowest. The strength of the C-F bond is  
such that fluoroalkanes are very unreactive
 


%"+
#'* (%' 
 Comparing the rate of hydrolysis reactions

Hydrolysis is defined as the splitting of a molecule ( in this Water is a poor nucleophile but it can
case a halogenoalkane) by a reaction with water react slowly with halogenoalkanes in a
substitution reaction
CH3CH2X + H2O
CH3CH2OH + X- + H+

Aqueous silver nitrate is added to a halogenoalkane. The CH3CH2I + H2O  CH3CH2OH + I- + H+

halide leaving group combines with a silver ion to form a Ag+ (aq) + I-(aq)  AgI (s) - yellow precipitate
silver halide precipitate.
The precipitate only forms when the halide ion has left the The iodoalkane forms a precipitate with
halogenoalkane and so the rate of formation of the precipitate the silver nitrate first as the C-I bond is
can be used to compare the reactivity of the different weakest and so it hydrolyses the quickest
halogenoalkanes.

  )  
 (
%'#
) 
 )  AgI (s) - yellow precipitate
') %$
$
)   
 ) "%$%"!$ AgBr(s) – cream precipitate forms faster
The rate of these substitution reactions depends on the strength AgC(s) – white precipitate
of the C-X bond . The weaker the bond, the easier it is to break
and the faster the reaction.

Nucleophilic substitution with aqueous hydroxide ions

Change in functional group: halogenoalkane
H H H
H H H
alcohol
Reagent: potassium (or sodium) hydroxide
H C C C Br 
 H C C C OH 

Conditions: In aqueous solution; Heat under reflux H H H H H H
Mechanism: Nucleophilic Substitution
 
Type of reagent: Nucleophile, OH-

H H The aqueous conditions needed

δ+ δ- is an important point. If the
-
H3C C Br H3C C OH + :Br solvent is changed to ethanol
- an elimination reaction occurs.
HO:
H H

Alternative mechanism for tertiary halogenoalkanes You don’t need to learn this but
there have been application of
Tertiary halogenoalkanes undergo nucleophilic substitution in a different way understanding questions on this

CH3 CH3 CH3 Tertiary halogenoalkanes

+ - undergo this mechanism as the
H3C C Br H3C C :OH H3C C OH tertiary carbocation is stabilised
CH3 CH3 by the electron releasing methyl
CH3
groups around it. (See alkenes
The Br first breaks topic for another example of this).
The hydroxide Also the bulky methyl groups
away from the
nucleophile then prevent the hydroxide ion from
halogenoalkane to
attacks the positive attacking the halogenoalkane in
form a carbocation
carbon the same way as the mechanism
intermediate.
above.


%"+
#'* (%' 
Nucleophilic substitution with cyanide ions

Change in functional group: halogenoalkane
H H H H H H

nitrile
Reagent: KCN dissolved in ethanol/water mixture H C C C Br 
  H C C C CN 

Conditions: Heating under reflux H H H
H H H
Mechanism: Nucleophilic Substitution
 
Type of reagent: Nucleophile, :CN-

Note: the H H This reaction increases the length of

mechanism is δ+ δ- the carbon chain (which is reflected in
identical to the H3C C Br H3C C CN + :Br - the name) In the above example
above one - butanenitrile includes the C in the
NC:
H H nitrile group

Naming Nitriles

Nitrile groups have to be at the end of a chain. Start

numbering the chain from the C in the CN. Note the naming: butanenitrile and not
butannitrile.
CH3CH2CN : propanenitrile

H3C CH CH2 C N 3-methylbutanenitrile

CH3

Nucleophilic substitution with ammonia

Change in functional group: halogenoalkane

amine H H H
H H H

Reagent: NH3 dissolved in ethanol NH2 

H C C C Br 
  H C C C  
Conditions: Heating under pressure (in a sealed
tube) H H H
H H H

Mechanism: Nucleophilic substitution propylamine

Type of reagent: Nucleophile, :NH3

Naming amines:
In the above example
H H propylamine, the propyl shows
H
δ+ δ- the 3 C’s of the carbon chain.
CH3 CH2 C Br +  
CH 3CH2 C N H Sometimes it is easier to use the
3HN: IUPAC naming for amines e.g.
H H H Propan-1-amine
:NH3

Further substitution reactions can

occur between the halogenoalkane
H and the amines formed leading to a
lower yield of the amine. Using
CH 3 CH 2 C NH 2  
 excess ammonia helps minimise this.
H


%"+
#'* (%' 
2. Elimination reaction of halogenoalkanes Elimination: removal of small molecule
(often water) from the organic molecule
Elimination with alcoholic hydroxide ions
H H H H H H
Change in functional group: halogenoalkane

alkene H C C C H 
  H C C C 



Reagents: Potassium (or sodium) hydroxide H H Br H H
Conditions: In ethanol ; heat
 
Mechanism: Elimination
Type of reagent: Base, OH-

Note the importance of H H H H

the solvent to the type of
reaction here. CH3 C C H 
  

CH3 C C H
Aqueous: substitution
Br H
Alcoholic: elimination -
:OH

Often a mixture of products from both elimination and substitution occurs

2-methyl -2- H
chlorobutane can give
H H C H
With unsymmetrical secondary 2-methylbut-1-ene and H H H
and tertiary halogenoalkanes H C H 2-methylbut-2-ene
H H H C C C C H
two (or sometimes three)
H C C C C H H
different structural isomers can H H
H
be formed H Cl H H
H C H
H H H

H C C C C H

H H

The structure of the halogenoalkane also has an effect on the

degree to which substitution or elimination occurs in this reaction.
Primary tends towards substitution
Tertiary tends towards elimination


%"+
#'* (%'
 Uses of Halogenoalkanes
Chloroalkanes and chlorofluoroalkanes can be used as solvents. Halogenoalkanes have also been
used as refrigerants, pesticides
CH3CC 3 was used as the solvent in dry cleaning.
and aerosol propellants
Many of these uses have now been stopped due to the toxicity of
halogenoalkanes and also their detrimental effect on the atmosphere.

Ozone Chemistry

The naturally occurring ozone (O3) layer in the upper Ozone in the lower atmosphere
atmosphere is beneficial as it filters out much of the sun’s is a pollutant and contributes
harmful UV radiation. towards the formation of smog.

Man-made chlorofluorocarbons (CFC’s) caused a hole to form in the ozone

layer.
Chlorine radicals are formed in the upper atmosphere when energy from
ultra-violet radiation causes C–C bonds in chlorofluorocarbons (CFCs) to  

 

break.

The chlorine free radical atoms catalyse the


 

 


decomposition of ozone, due to these reactions, 
 

  

because they are regenerated. (They provide an
alternative route with a lower activation energy) 
 




These reactions contributed to the formation of a
hole in the ozone layer. The regenerated C radical means
that one C radical could destroy
many thousands of ozone molecules.

Legislation to ban the use of CFCs was supported by HFCs (Hydro fluoro carbons) e.g.
chemists and that they have now developed CH2FCF3 are now used for refrigerators
alternative chlorine-free compounds. and air-conditioners. These are safer
as they do not contain the C-C bond.

The C-F bond is stronger than the C-C bond and is not affected by UV.


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3.4 Alkenes
Alkenes contain a carbon-
Alkenes are unsaturated hydrocarbons General formula is CnH2n carbon double bond
somewhere in their structure.
H H H H

C C
C C C H The arrangement of bonds around the
Ethene Propene
H H H
>C=C< is planar and has the bond angle 120o
H H
H H H H
Numbers need to be H
added to the name when H C C C C H But-2-ene
C C C C H But-1-ene
positional isomers can
occur. H H H H H H H H

π bonds are exposed and have high

C=C double covalent bond electron density.
consists of one sigma (σ)
bond and one pi (π) bond. They are therefore vulnerable to attack
by species which ‘like’ electrons: these
species are called electrophiles.

Stereoisomerism

Stereoisomers have the same structural formulae Alkenes can exhibit a type of isomerism
but have a different spatial arrangement of atoms. called E-Z stereoisomerism

E-Z isomers exist due to restricted E-Z stereoisomers arise when:

rotation about the C=C bond (a) There is restricted rotation around the C=C double bond.
(b) There are two different groups/atoms attached both ends of
Single carbon-carbon covalent the double bond.
bonds can easily rotate

H H

H H
two different groups H C C H But-1-ene
H C C H attached either end of
C C
the restricted double H H
C C H
bond- leads to EZ H two identical groups attached to
H H H H isomers one end of the restricted double
Z- but-2-ene bond – no E-Z isomers

But-1-ene is a structural isomer of But-2-

H
H These are two ene but does not show E-Z isomerism.
C H isomers as the lack
H of rotation around Naming E-Z stereoisomers
C C the double bonds
H
means one cannot First determine the priority groups on both sides of
H C
be switched to the the double bond
H
H other.
Priority Group: The atom with the bigger
E -but-2-ene Atomic number is classed as the priority atom

  Cl H
 Cl Cl 

 
 C C
C C

H H H Cl

If the priority atom is on the same side of the If the priority atom is on the opposite side of
double bond it is labelled Z from the german the double bond it is labelled E from the
zusammen (The Zame Zide!) german entgegen (The Epposite side!)


  
    

Electrophilic Addition Reactions of Alkenes
Definition Electrophile: an electron pair acceptor
The double bonds in alkenes are areas with high
electron density. This attracts electrophiles and the
Addition reaction: a reaction where two
alkenes undergo addition reactions.
molecules react together to produce one
1. Reaction of Bromine with Alkenes
H H
Change in functional group: alkene
dihalogenoalkane
H H
Reagent: Bromine
Conditions: Room temperature (not in UV light) C C + Br2
H C C H

Mechanism: Electrophilic Addition

H H Br Br
Type of reagent: Electrophile, Br
+
1,2-dibromoethane

As the Br2 molecule H H

H H H H
approaches the alkene,
the pi bond electrons + The INTERMEDIATE
C C H C C H H C C H formed, which has a
repel the electron pair in
the Br-Br bond. This positive charge on a
H Brδ+ H Br carbon atom is called a
INDUCES a DIPOLE. Br2 Br Br
becomes polar and :Br - CARBOCATION
ELECTROPHILIC (Brδ+). Brδ-
2. Reaction of Hydrogen Bromide with Alkenes
Change in functional group: alkene
halogenoalkane H H H H H H
Reagent: HCl or HBr
H C C C C H 

H C C C C H
Conditions: Room temperature
Mechanism: Electrophilic Addition H H H H H H Br H
Type of reagent: Electrophile, H
+ But-2-ene 2-bromobutane

HBr is a polar
H H
H H H This reaction can
molecule because H
Br is more lead to two
H3C C C CH3 +
electronegative H3C C C CH3 H3C C C CH3 products when the
than H. The H δ + is δ+ alkene is
attracted to the H H Br H unsymmetrical
-
electron-rich pi Br δ :Br -
bond.

‘Markownikoff’s Rule’ :Br -

H
In most cases, bromine will be added to the + H H H H
carbon with the fewest hydrogens attached to it C CH2
Major
If the alkene is H C C C C H
H3C CH3 product
unsymmetrical, δ+ δ- :Br - 90%
addition of hydrogen H Br H H Br H
bromide can lead to H H
two isomeric
H2C CH CH2 CH3 C
+
C CH2 CH3 CH2 CH2 CH2 CH3 Minor
products. product
H Br 10%
H
Why? In electrophilic addition to alkenes, the major product is
This carbocation intermediate H H H formed via the more stable carbocation intermediate.
is more stable because the
methyl groups on either side H C C C H In exam answers
of the positive carbon are +
•Draw out both carbocations and identify as primary, secondary
electron releasing and reduce and tertiary
H H
the charge on the ion which •State which is the more stable carbocation e.g. secondary more
stabilises it. stable than primary
•State that the more stable carbocation is stabilised because the
The order of stability for carbocations is methyl groups on either (or one) side of the positive carbon are
tertiary > secondary >primary electron releasing and reduce the charge on the ion.
•(If both carbocations are secondary then both will be equally 
stable and a 50/50 split will be achieved)

  
   
 3. Reaction of Sulfuric acid with Alkenes
Stage 1
Stage 2
Change in functional group
Change in functional group
alkene
alkyl hydrogensulfate alkyl hydrogensulfate
alcohol
Reagents: concentrated H2SO4 Reagents: water
Conditions: room temperature Conditions: warm mixture
Mechanism: Electrophilic Addition Type of reaction: hydrolysis
Type of reagent: Electrophile, H2SO4
   


 

 
  
 
   

Stage 1: electrophilic addition

H2SO4 is best
H H H H H drawn as
H

H3C C C H
+
H3C C C H
H-OSO2OH
H3C C C H
in exams. Its real
δ+ H H
H OSO 2OH structure is
-
:OSO2OH H O O
OSO 2OH
δ-
S
Stage 2: hydrolysis
H O O
H H H

H3C C C H + H2O H3C C CH3 + H2SO4 Overall role of sulfuric

acid is that of a
H OH catalyst (as it is
OSO 2OH regenerated)

With unsymmetrical alkenes a minor and major product can also be formed similar to the
addition of HBr. The same explanation applies.

Definition: Hydrolysis – a reaction where the molecule is split by the addition of water

Direct industrial hydration of alkenes to form alcohols This reaction can be called
Industrially alkenes are converted to alcohols in one step rather than the hydration: a reaction where
two in the above sulfuric acid reaction. They are reacted with water in the water is added to a molecule
presence of an acid catalyst.
Essential Conditions
CH2=CH2 (g) + H2O (g)
CH3CH2OH High temperature 300 to 600°C
(l)
High pressure 70 atm
Catalyst of concentrated H3PO4

The high pressures needed mean this cannot be done in the laboratory. It is preferred industrially, however,
as there are no waste products and so has a high atom economy. It would also mean separation of products
is easier (and cheaper) to carry out. See equilibrium chapter for more on the industrial conditions for this
reaction.
Testing for Alkenes with Bromine water
Bromine water decolourises in the presence of a double bond. This can be used as a
test for the presence of an double bond in a molecule. It can be used quantitatively to
show the presence of multiple double bonds in compounds like polyunsaturated oils.


  
    

Addition Polymers
Poly(alkenes) like alkanes are unreactive due to
Addition polymers are formed from alkenes the strong C-C and C-H bonds
This is called addition polymerisation
be able to recognise the repeating unit in a poly(alkene)

H H H H H H
Monomer Polymer
Ethene polyethene C C C C C C
H H H H
CH3 H CH3 H CH3 H
n C C C C

H CH3
H CH3 n
propene
poly(propene)
Add the n’s if writing an equation showing the
Poly(propene) is recycled
reaction where ‘n’ monomers become ‘n’ repeating
units

H H
If asked to draw one
repeating unit, don’t add
the n on to your diagram, C C
because n represents a
large number H CH3

It is best to first draw out H CH3

You should be able e.g. For but-2-ene the monomer with groups H CH3
to draw the polymer of atoms arranged around
C C C C
repeating unit for any H3C CH CH CH3 the double bond
alkene H3C H
CH3 H

Poly(chloroethene) is a polymer that is water proof, an electrical

insulator and doesn’t react with acids.
H H In its pure form it is a rigid plastic due to the strong intermolecular
bonding between polymer chains prevents them moving over each
C C other. In this un-plasticised form it is used make uPVC window frame
coverings and guttering.
If a plasticiser is added the intermolecular forces are weakened which
H Cl allows the chains to move more easily, resulting in more flexibility in the
polymer. In this form PVC is used to make insulation on electrical wires,
and waterproof clothing.


  
    

3.5 Alcohols General formula alcohols CnH2n+1OH

Naming Alcohols
OH
These have the ending -ol and if necessary the position
butan-2-ol
number for the OH group is added between the name stem CH3 CH CH2 CH3
and the –ol 1 2 3 4

O
If the compound has an –OH group in addition to other H3C CH C 2-hydroxypropanoic acid
functional groups that need a suffix ending then the OH can be
named with the prefix hydroxy-): OH OH

HO CH2 CH2 OH ethane-1,2-diol

If there are two or more -OH groups then di, tri are used. H2C OH
Add the ‘e’ on to the stem name though
propane-1,2,3-triol
HC OH

H2C OH

Bond angles in Alcohols

H The H-O- C bond is 104.5o (bent line
All the H-C-H bonds and C- H shape), because there are 2 bonding
C-O are 109.5o (tetrahedral O H pairs of electrons and 2 lone pairs
shape), because there are 4
109.5O C 104.5O
C repelling to a position of minimum
bonding pairs of electrons H
repulsion. Lone pairs repel more than
repelling to a position of H bonding pairs so the bond angle is
minimum repulsion. H reduced.

Boiling points

The alcohols have relatively low volatility and δ- δ+ δ-

O H δ+
high boiling points due to their ability to form O H
hydrogen bond between alcohol molecules. H
C Hδ +
H H
C Smaller alcohols can dissolve in
H water because they can form
H hydrogen bonds to water molecules.
Different types of alcohols
H

H H H O
H H H H H

H C C C H
H C C C O H H C C C H

H H H H O H H H
H C H
propan-1-ol H
H
Primary propan-2-ol
Secondary methylpropan-2-ol
Tertiary
Primary alcohols are alcohols Secondary alcohols are alcohols Tertiary alcohols are alcohols
where 1 carbon is attached to where 2 carbon are attached to where 3 carbon are attached to
the carbon adjoining the the carbon adjoining the oxygen. the carbon adjoining the oxygen.
oxygen.

 
 
Oxidation Reactions of the Alcohols
The exact reaction, however, depends on the
Potassium dichromate K2Cr2O7 is an oxidising agent type of alcohol, i.e. whether it is primary,
that causes alcohols to oxidise. secondary, or tertiary, and on the conditions.

Partial Oxidation of Primary Alcohols

H
O
An aldehyde’s name ends
Reaction: primary alcohol
aldehyde in –al
Reagent: potassium dichromate (VI) solution and dilute H C C
It always has the C=O bond
sulfuric acid. on the first carbon of the
Conditions: (use a limited amount of dichromate) warm H
H chain so it does not need a
gently and distil out the aldehyde as it forms: ethanal number in its name.

H H O Observation: the
H H H
orange dichromate ion
+ [O] H C C C + H2O
H C C C O H (Cr2O72-) reduces to
H H H the green Cr 3+ ion
H H H
OH + [O] O + H2O

CH3CH2CH2OH + [O]
CH3CH2CHO + H2O

propan-1-ol propanal

Write the oxidation equations in a simplified form using [O] which represents O from the oxidising agent

When writing the formulae of aldehydes in a condensed way write CHO and not COH e.g.CH3CH2CHO

Distillation It’s important to be able to

In general used as separation technique to separate draw and label this
an organic product from its reacting mixture. In order apparatus accurately.
thermometer Don’t draw lines between
to maximise yield collected, only collect the distillate
flask, adaptor and
at the approximate boiling point of the desired condenser and across
aldehyde and not higher. thermometer.

The bulb of the thermometer should be at

the T junction connecting to the Liebig condenser
condenser to measure the correct boiling
point.

Note the water goes in to the bottom of the

condenser to go against gravity. This allows Water
more efficient cooling and prevents back flow out
of water.
Round Water in
Electric heaters are often used to heat organic bottomed
chemicals. This is because organic chemicals flask
are normally highly flammable and could set on Heat
fire with a naked flame.
The collection flask can be
cooled in ice to help improve
the yield of distillate

 
 
Full Oxidation of Primary Alcohols
H H
O
Reaction: primary alcohol
carboxylic acid
Reagent: potassium dichromate(VI) solution and dilute H C C C
sulfuric acid
Conditions: use an excess of dichromate, and heat H H
O H
under reflux: (distil off product after the reaction
has finished) propanoic acid

H H H H H O
+ 2 [O] H C C C + H2O Observation: the
H C C C O H
orange dichromate
H H H H H O H
ion (Cr2O72-)
OH + 2[O] OH reduces to the
+ H2O green Cr 3+ ion
O
CH3CH2CH2OH + 2[O]
CH3CH2COOH + H2O
propan-1-ol propanoic acid

Reflux
Reflux is used when heating organic reaction mixtures for long Water out
periods. The condenser prevents organic vapours from escaping
by condensing them back to liquids.
condenser
Never seal the end of the condenser as the build up of gas
pressure could cause the apparatus to explode. This is true of any
apparatus where volatile liquids are heated including the distillation
set up.

Water in
Anti-bumping granules are added to the flask in both distillation and
reflux to prevent vigorous, uneven boiling by making small bubbles
form instead of large bubbles.
Round
bottomed
flask
It’s important to be able to draw and label this apparatus
accurately.
• Don’t draw lines between flask and condenser.
• Don’t have top of condenser sealed
Heat
• Condenser must have outer tube for water that is sealed at
top and bottom
• Condenser must have two openings for water in and out
that are open

 
 
Oxidation of Secondary Alcohols
Ketones end in -one
H O H
Reaction: secondary alcohol
ketone When ketones have 5C’s
Reagent: potassium dichromate(VI) solution and H C C C H
or more in a chain then it
dilute sulfuric acid. H H needs a number to show
Conditions: heat under reflux the position of the double
propanone bond. E.g. pentan-2-one

H H H

H O H
H C C C H
+ [O] Observation: the
H C C C H + H2O orange dichromate
H O H ion (Cr2O72-) reduces
H H to the green Cr 3+ ion
H
propanone
propan-2-ol

There is no further oxidation of the ketone under these conditions.

Tertiary alcohols cannot be oxidised at all by potassium dichromate: This is because there is no hydrogen
atom bonded to the carbon with the -OH group

Distinguishing between Aldehydes and Ketones

Aldehydes can be further oxidised to carboxylic acids whereas ketones cannot be further oxidised. This is the
chemical basis for two tests that are commonly used to distinguish between aldehydes and ketones.

Tollens’ Reagent Fehling’s solution

Reagent: Fehling’s solution containing blue Cu 2+
Reagent: Tollens’ reagent formed by mixing ions.
aqueous ammonia and silver nitrate. The
Conditions: heat gently
active substance is the complex ion of
Reaction: aldehydes only are oxidised by
[Ag(NH3)2]+ .
Fehling’s solution into a carboxylic acid. The
Conditions: heat gently copper (II) ions are reduced to copper(I)
Reaction: aldehydes only are oxidised by oxide .
Tollens’ reagent into a carboxylic acid. The Observation: Aldehydes :Blue Cu 2+ ions in
silver(I) ions are reduced to silver atoms solution change to a red precipitate of Cu2O.
Ketones do not react
Observation: with aldehydes, a silver mirror
forms coating the inside of the test tube. CH3CHO + 2Cu2+ + 2H2O
CH3COOH + Cu2O + 4H+
Ketones result in no visible change

CH3CHO + 2Ag+ + H2O
CH3COOH + 2Ag + 2H+

The presence of a carboxylic acid can be tested by addition of sodium carbonate. It will fizz and produce
carbon dioxide.

 
 
Reaction of Alcohols with Dehydrating Agents

Reaction: Alcohol
Alkene

Dehydration Reaction: removal of a
water molecule from a molecule
Reagents: Concentrated sulfuric or phosphoric acids
Conditions: warm (under reflux)
Role of reagent: dehydrating agent/catalyst
Type of reaction: acid catalysed elimination
H
H
H H H
H C
H C C C O H H
C C
+ H2O
H H H
H H
propan-1-ol propene

CH3CH2CH2OH
CH2=CHCH3 + H2O

H H
H C
Some 2o and 3o butan-2-ol but-1-ene
alcohols can give H H H H C C C H
more than one
product, when the H C C C C H H
H H
double bond H H
forms between H H O H H H
different carbon C C
atoms H
H H
C C
Butan-2-ol can form both alkenes
although more but-2-ene would be but-2-ene
H H
formed
But-2-ene could also exist as E and Z
isomers

Producing alkenes from alcohols provides a possible route to polymers without using monomers derived from oil.

Acid catalysed elimination mechanism

H
H H H H H
H3C C CH3 CH3 +
H3C C H C C CH3 H C C CH3

O H +
O H H H+
:

H+
H

The H+ comes from the conc H2SO4 or conc H3PO4

 
 
Forming ethanol Comparing two methods for producing ethanol: Fermentation or industrial formation from ethene

Fermentation From ethene

glucose
ethanol + carbon dioxide Reagent: ETHENE - from cracking of
C6H12O6
2 CH3CH2OH + 2 CO2 fractions from distilled crude oil

The conditions needed are: CH2=CH2 (g) + H2O (g)
CH3CH2OH (l)
•Yeast Type of reaction: Hydration/addition
•No air
•temperatures 30 –40oC Definition: Hydration is the addition of water
to a molecule
Type of reaction: Fermentation
Essential Conditions
The optimum temperature for fermentation is around high temperature 300 °C
38oC
At lower temperatures the reaction is too slow. high pressure 70 atm
At higher temperatures the yeast dies and the enzymes strong acidic catalyst of conc H3PO4
denature.
Fermentation is done in an absence of air because the Advantages:
presence of air can cause extra reactions to occur. •faster reaction
It oxidises the ethanol produced to ethanoic acid •purer product
(vinegar). •continuous process (which means cheaper
manpower)
Advantages
•sugar is a renewable resource Disadvantages:
•production uses low level technology / cheap •high technology equipment needed (expensive
equipment initial costs)
•ethene is non-renewable resource (will become
Disadvantages more expensive when raw materials run out)
•batch process which is slow and gives high production •high energy costs for pumping to produce high
costs pressures
•ethanol made is not pure and needs purifying by
fractional distillation
•depletes land used for growing food crops

Acid catalysed addition mechanism for hydration of ethene

H H H H H H
H H
+
H C C H H C C H H C C H
C C
+
H H H H H O H H O H+
O
H+ H H
H

The H+ comes from the conc H3PO4

 
 
Ethanol as biofuel

A biofuel is a fuel produced from plants The term carbon neutral refers to “an activity that
has no net annual carbon (greenhouse gas)
emissions to the atmosphere”

Ethanol produced from fermentation is a biofuel.

It can be argued that ethanol produced from this method is classed as
carbon–neutral because any carbon dioxide given off when the biofuel is
burnt would have been extracted from the air by photosynthesis when the
plant grew. There would be no net CO2 emission into the atmosphere.

Equations to show no net contribution to CO 2

Removal of CO2 by photosynthesis 6 CO2 molecules are removed from the atmosphere
when the plants grow by photosynthesis to produce one
6 CO2 + 6 H2O
C6H12O6 + 6 O2 molecule of glucose.

Production of CO2 by fermentation and combustion

C6H12O6
2 CH3CH2OH + 2 CO2 When 1 molecule of glucose is fermented 2 molecules of CO2 is

2 CH3CH2OH + 6O2
4 CO2 + 6 H2O emitted. The two ethanol molecules produced will then produce
4 molecules of CO2 when they are combusted.
Overall for every 6 molecules of CO2 absorbed, 6 molecules of CO2 are emitted. There is no net
contribution of CO2 to the atmosphere.

This does not take into account any energy needed to irrigate plants, fractionally distil the ethanol
from the reaction mixture or process the fuel. If the energy for these processes comes from fossil
fuels then the ethanol produced is not carbon neutral.

 

 
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0283
 
2; 

Use spectra to identify particular functional groups and to identify

impurities, limited to data presented in wavenumber form

Spectra for
butanal

O
H3C CH2 CH2 C
H

2000 1500

C=O

Absorption or trough in between 1680-1750 cm-1 range indicates presence of C=O bond

Always quote the wave number range from the

data sheet

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 Spectra for
O-H absorptions tend ethanoic acid
to be broad
O
Absorption or trough in
between 2500-3000 cm-1 range H3C C
indicates presence of O-H OH
bond in an acid

C=O
“rogue” absorptions can also occur and are indicators of Absorption or trough in between 1680-
impurities 1750 cm-1 range indicates presence of
C=O bond

The absorption of infra-red radiation by bonds in this type of spectroscopy is the same absorption that
bonds in CO2, methane and water vapour in the atmosphere do - that causes the green house effect.

Mechanism of greenhouse effect

UV wavelength radiation passes through the atmosphere to the Earth’s surface and heats up Earth’s surface.
The Earth radiates out infrared long wavelength radiation.
The C=O Bonds in CO2 absorb infrared radiation so the IR radiation does not escape from the atmosphere.
This energy is transferred to other molecules in the atmosphere by collisions so the atmosphere is warmed.

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 Mechanism Summary for AS AQA Chemistry
 
  
     
  
   


  
 
 

H H H H
δ+
δ- δ+ δ- -
H3C C Br H3C C OH + :Br - H 3C C Br H 3C C CN + :Br
- -
NC:
HO: H
H H H

 
  
   



  
   
  
H H H  
  

δ+ δ- +
CH3 CH2 C Br CH3 CH2 C N H H H H H
3HN:
H H CH3 C C H CH3 C C H
H
:NH3

  

Br H
H :OH-
CH3 CH2 C NH2 
 


 
  


  
  


 
 
H H H H H H H H
H H
+
C C H C C H H C C H H3C C C CH3 +
H3C C C CH3
H H Br δ+
Br δ+ Br Br H H
:Br - δ- :Br -
Br
Br δ-
H H

 
  



 H3C C C CH3

H H Br H
H H
+
H3C C C H H3C C C H
δ+ H 
  
  
 


H -
:OSO2OH
OSO 2OH STEP ONE Initiation
δ- Essential condition: UV light
H H
Br2
2Br
.
H3C C C H
H STEP TWO Propagation
OSO 2OH .
CH3CH3 + Br
HBr + CH3CH2
.
.
CH3CH2 + Br2
CH3CH2Br + Br
.

STEP THREE Termination

.
CH3CH2 + Br
CH3CH2Br
.
.
CH3CH2 + CH3CH2
CH3CH2CH2CH3
.
 
  
 
  
 

H
H H H H H
H3C C CH3 CH3 +
H3C C H C C CH3 H C C CH3

O H +
O H H 
:


H

 



 


 

 
  

  

  



H H H H H H
H H
+
H C C H H C C H H C C H
C C
+
H H H H O H H O 
H
 O H H
H

 



 

  #
diol
poly(alkene) KOH aqueous
heat under reflux
nucleophilic substitution
high pressure
catalyst
dihalogenoalkane
alkene

alkane
1 H2SO4
conc H2SO4 or 2 H2O warm
conc H3PO4 Electrophilic
Acid catalysed Br2, Cl2 UV light
Addition
Free radical
Elimination
Substitution

KOH aqueous

alcohol
heat under reflux
nucleophilic substitution halogenoalkane


! Alcoholic NH3
" 

  " heat under pressure
nucleophilic substitution nucleophilic substitution

nitrile amine

aldehyde ketone

If primary alcohol or aldehyde

K2Cr2O7/H+
heat under reflux
+ excess oxidising agent
Oxidation

carboxylic acid