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VCEasy

VISUAL
CHEMISTRY
Units 3&4

v1
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VCEasy
Electrolytic Cells VISUAL
CHEMISTRY
Key Knowledge point
Reactions are the OPPOSITE
OPPOSITE to those in the galvanic cell. 4.2.7
Reactions are non-spontaneous and require energy. Area of Study
Examples Galvanisation plating a thin film of metal over another metal to make it prettier or more resistant to corrosion

Extracting metals from ores mining Unit


Recharging rechargeable batteries including car batteries
Increasing the thickness of the surface oxide layer of aluminium e.g. cans

+
Diagram Power
supply
Electron
e flow

AN OIL RIG CAT: Anode loses electrons & is oxidised +


+
AN OIL RIG CAT: Cathode gains electrons & is reduced

100% At anode, tin is oxidised


Tin rod e

At cathode, tin is reduced


highly
original Sn(s) Sn2+(aq) + 2e

Anode is POSITIVE in this cell Sn2+


Sn2+(aq) + 2e Sn(s)

Cathode is NEGATIVE in this cell visual


quizzes content
e Object
e being
NO3
plated

Tin plating rod loses mass. A coating of tin forms around the can.
Tin nitrate solution (electrolyte)

Electrolytes Allow charged ions to flow between the electrodes


Molten Electrolytes
Large amounts of energy are
Aqueous Electrolytes
Little energy required.
100%
required to melt the
electrolyte
Cheaper than using molten
electrolytes.
When producing H2 and Cl2, a selective VCE.
Nothing
Examples Molten sodium electrolyte Examples Sodium chloride electrolyte membrane is placed in the middle of the
electrolyte to prevent the H2 and Cl2 from
reacting with each other.
Na3AlF6 (cryolite) electrolyte

Sulfuric acid electrolyte


Used in the electro-refining of copper.
98% pure blister copper is the anode;
99.999% pure copper is the cathode.
added.
the chemical principles, half-equations and overall equations of simple electrolytic cells;
comparison of electrolytic cells using molten and aqueous electrolytes, and inert and non-inert
electrodes

Key knowledge point copied exactly


from the VCAA Study Design
The
ethanoic
faster production
acid
and faster
is replaced
and
produces ofhigher
a substance
produces
with ethanoic
higher
yields, to be
toyields,
the usedthe
ethanoic as a medicine
ethanoic
acid acid
is replaced usually
withrequi
that the general
hydroxyl chemical
group reaction
in the salicylicform anFigure
acid ester
molecule is:
14.2 that isfunctions
replacedethanw
as
heapreferred
numberanhydride
anhydride of(acetic
chemical
inpathway
a reaction for steps,
(acetic
the
withsynthesis
anhydride). knownThisas
anhydride).
ethanoic is athe
synthetic
This is the
preferred
Felix pathway.
preferred
pathway
Hoffmann, whotofiYou should
pathway
for
rst the
synthesised rect
for
synth
asp
carboxylic acid + alcohol esteracid + water(acetic acid) form acetyls
that the general
of aspirin of aspirin
(Figures chemical reaction to form an ester is:pure form in 1897.
and water.(Figures
14.3, 14.4). 14.3, 14.4). a chemically
This reaction
carboxylic could
This is be
acid usedreaction.
a+ slow
alcohol toformester acetylsalicylic
Also the yieldacid.
+ water is low,Interestingly,
as the water it isfo t
hydroxyl to group
drive in thereaction
OOH theHO
salicylic
OH HO
acid molecule
backwards. In an that functions
alternative O
asO the3.1
reaction alcoh
pathw
ThisaCHreaction could be used toacid form(acetic
acetylsalicylic acid. Interestingly, it isac t
in CH reaction
33 Cfaster
C CH with C
C+ ethanoic
3 and produces CH 3+C+ higher
H 2OCH C CH acid)
3 yields,3 the3ethanoic
CH to Cform
CH acetylsalicylic
3 acid is replaced
C C CH3C VCE
+ H w2CO

Making Aspirin
hydroxyl
in aThis
reaction
group
and water.anhydride O
isOofa aspirin
Ethanoic slow
in
with
Ethanoic
acid
the O
O
salicylic
(acetic
ethanoic
reaction.
acid Also
Ethanoic
O(Figures
O
acid
Water
acid
anhydride).
the
molecule
(acetic
Ethanoic
acid yield
Thisacid)
acid is low,
that
is the to
Figure
functions
preferred
form
asO14.3
the water
as the
pathway for
acetylsalicylic
OO formed
alcoh
VISac
CHEMten
Wate
t
and water. 14.3, 14.4). O
to drive the reactionanhydridebackwards. In an alternativeEthanoic
Formation of ethanoic
reaction anhydride. which
pathway,
3.2
UNIT 3
Ethanoic Ethanoic
anhydride anhydride
Synthetic
This
was anis a Pathway
slow
extract reaction.
from coal Also
tarthe the yield
black, is
stickylow,
faster and produces higher yields, the ethanoic acid is replaced with ethan as
substancethe water
that is formed
produced ten
to when the
drive
anhydride coal is heated
reaction
(acetic in the absence
backwards.
OH
anhydride). HOThis ofthe
In isan air.preferred
Once hereaction
alternative had
pathway made salicylic
pathway,
for O acid
which
the synthe
he
faster replaced
O andOH
CH the OH
produces hydroxyl
C higher functional
+yields, theC group
O ethanoic
CH withacid anOHis
ester
CH 3 functional
replaced C withgroup 3.2
ethan
C C
of aspirin
OH (Figures
O 3 14.3, 14.4). OH3O
to form (acetic
anhydride acetylsalicylic O acid (Figure
anhydride). O
This is 14.4).
the This is pathway
preferred the compound for theknown
synthe w

C CH
condensation
C as aspirin. O CH O C C
prod
commercially Ethanoic
3
acid
3
Ethanoic acid
cond
ofO aspirin
C (Figures
CH
OH 14.3,
OH C
14.4). C OH O C OCH C
O
CH
O
O
re

The production
3
OH HOof a substance to SLOW
be used as a medicine O usually requires
3 3
Ethanoic
VCEasyanhydride
a 3number
CH O C
++ + CH3+
of chemical steps,
O CC known
CHO3 as a synthetic
H
CH3 pathway.C You CH3 + recall
+ should
O C 4.1.2CH
C CH
3 + H2O3
VISUAL
CHEMISTRY
Calculating H O
that the general
OH
O chemical
HO
CO reaction
CO to form an ester ! is: O O Exothermic negative H
gives out energy

CHEthanoic C acid +OH Ethanoic C acid CH3 CH C anhydride isC CH3by+combin


H2O
OEthanoic Oprepared
carboxylic acid + alcohol O Water
CH3ester + water
3 O 3 OH
O CHO3
EA!
Energy, H

(activation energy)

H = Hproducts Hreactants
Reactants

O O
CH3
two moleculesEthanoic anhydride
of ethanoic acid (Figure 14 H

This reaction O
acid could
C be usedEthanoic
to form acetylsalicylic C acid. Interestingly, it is the
Products

cetylsalicylic
Salicylic acidSalicylic
acid acidEthanoic
Ethanoic acid Acetylsalicylic
A water Acetylsalicylic
acid acid Ethanoic acidEth
Ethanoic Ethanoic acid Omolecule is O also produced. Water
hydroxyl group in
(aspirin) OHthe(acetic
anhydridesalicylic
C acid molecule
anhydride
acid) (aspirin) that functions
Effects of a Catalyst
O
(aspirin) C as CHthe 3 (aceticalcoholacid)(a
Ethanoic anhydride
in Alkanol
a reaction with ethanoic
+ acidO (acetic acid)Exothermic to form negative H acetylsalicylic +VCEasy + acid
! Solution

+ Carboxylic Acid Ester CH3


Water
4.1
A useful formula to use in calculations such as
Since the density of water is 1.00 g mL1, the mass of 120 mL of water is 120 g.
this is:
The energy required to raise the temperature of 120 g of water by 1C = 4.184 120

O OH O OH O
Energy (J) = 4.184 mass of water (g)
gives out energy = 502.0 J.
Calorimeters
temperature rise (C)

and water.
Figure 14.4Figure 14.4
or
VISUAL Since the temperature rises by (100.0 20.0) = 80.0C, the total energy required
Energy (J) = 4.184 volume of water (mL) = 502.0 80 = 40 160 J.
density of water CHEMISTRY
C
chemfact
The energy required to raise the temperature of the water to 100C is 40.2 kJ.
EA is4.2.2
CH
temperature rise (C).

CThisfrom
ylic acidStructural
(aspirin) is asalicylic
slow
Structural
equation forequation
3acid
the O forethanoic
reaction.
and Also
the
preparation the yield
preparation
Method
isacid low,
C of acetylsalicylic
of acetylsalicylic
Find out how much heat is being absorbed by the
(aspirin) as
calorimeter.
25.3 the
acidfrom water
(aspirin)
salicylic formed
The density of water varies with temperature.

from acid
decreased
The density of water at 5C is 1.0000 g mL1.

and tends
salicylic acid an
ethanoic EA!

O OH O OH Run an electric current through the calibration heater. Using E = (activation energy
Energy, H

Calibration

OH O of water.CH O CtoconvertedMeasuring
CH the heat
without a catalyst)

converted to todrive
(acetic)ethanoic
(acetic)
the acid
anhydride. anhydride.
by the
Unreacted
reaction Unreacted
ethanoic
C addition
backwards. ethanoic
anhydride anhydride
In 3an isalternative
converted
Reactants
isCalibration
VIt,
ethanoic
reaction
and by reading

released
the
VIt3
to
acid ethanoic
pathway,
thermometer,

during
find
by
the calibration

a Britain
acid
the addition
factor.

reaction was
by the
which isadd
ofOH
wate EA with catalyst

CH O During World
Factor =
T War
Units: J C
I, unable t 1

faster
C and produces
+ acid3 higher
Salicylic O yields, the ethanoic
Ethanoic C acid is= Calibration
Acetylsalicylic
Bomb replaced
and solution
+ T acid
H
FactorcalorimetryUnits:with
H stays
J CH ethanoic
C Eth
O obtain aspirin Changefrom its German manufac
the same
Quicker Synthetic Pathway
Energy Change Experiment

O 3

UNIT 4
Enthalpy changes are measured directly using an instrument called a

anhydride OH (acetic anhydride).


C anhydride
This is the preferred C pathway H =CH
(aspirin)
Products
Energy
3
n for the synthesis
Units: J mol OH (a
calorimeter. Figure 25.7a shows the components of a bomb calorimeter
1
used for reactions that involve gaseous reactants or products. The reaction

C In 1915, the British government


The exam could ask for either
H or Heat of Combustion
offered
O
vessel in a bomb calorimeter is designed to withstand the high pressures that
may be created during reactions. A calorimeter employed for reactions in

of aspirin +
(Figures 14.3, 14.4). +
Energy Change Heat aqueous
of
kJ g1
solutions is shown in Figure 25.7b. Both calorimeters are insulated
H = Units:

andMake acetic
The (ethanoic)
The
products, products,
acid, haveacetylsalicylic
acetylsalicylic to be
acid and acidacetic and acetic
(ethanoic) (ethanoic)
CH acid, have acid to
kJ L1

O
gram Combustion
C to reduce loss or gain of energy to or from the outside kJ environment.

reward of 20 000 to anyone who could


mol1

Ethanoic Anhydride
O CH
Unreacted
O ethanoic anhydride
energy profile diagrams andH gas 3 water
Wood 18 kJ mol
the= 143use
2 kJ mol

produced
When
ofis
High heat of combustion = better
1
fuel! a reaction takes place in a calorimeter, the heat
a rise or fall in the temperature of the contents of the calorimeter. Before
1

in
H notation including: activation energy; alternative
change causes

Figure 14.4
reaction pathways for catalysed reactions; the calorimeter and deduction
can be ofofuse,
Hwe for must
an overall reaction given
first determine how much energy
will react with water to
foreseparated
it can be separated
put the
and intoCandtablet
producttheformproduct
purifi and
ed purifi
before edit before
can be itput canacid intobe put
tablet into formtab 4.2
energy profiles or H of two related reactionsto change the temperature within a calorimeter by 1C. This is
is required
3
develop
produce aethanoic
workable E = VIt
manufacturing Oproc
condensati
known as the calibration factor of the calorimeter.
reaction E = VIt

Salicylic acid Structural Ethanoic


equation for the preparationAcetylsalicylic
of acetylsalicylic acid (aspirin) from salicylic acid an
Electric heater for Electric heater for
a b

acid Ethanoic acid


calibrating the Electric heater calibrating the

for aspirin Oso that the country could ma


calorimeter calorimeter

packagedpackaged for sale. for sale.


to ignite sample Stirrer Thermometer Stirrer

OH HO
Thermometer

OH HO
Oanhydride CH
(acetic) anhydride. Unreacted
3 ethanoic anhydride
(aspirin)
CH3its own
is converted to ethanoic (acetic
C supply. The
acid by acid)
the add
teless CH3
and C
is much +
Acetylsalicylic
Acetylsalicylic less isCvirtually
irritating
acid acidCH3
to is
the virtually
tasteless tasteless
andacid is much reward
andC isless CH3 +was
much H2O
less
irritating wonirrit
by
to
Salicylic acid Ethanoic Acetylsalicylic Ethanoic acid
Pressurised vessel

O O Melbourne pharmacist, George Nicholas


not until
stomach afterstomach
it
than has passed
than
salicylic salicylic
through
acid acid
the
itself. It itself.
is not It is not
until afteruntil after
it has it (acetic
passed hasWater
passed
through
Oxygen under
pressure

Figure 14.4 acid anhydride (aspirin) acid)


Ethanoic Ethanoic acid who Owent on to Omarket aspirin under th
Water

drolyses)
Structuralin
stomach stomach
the
that
equationalkaline
The it the
for that
reacts conditions
itwith
reacts
preparation
products, with
ofwater in(hydrolyses)
water
acetylsalicylic
acetylsalicylic acid (hydrolyses)
(aspirin)
acid
name and in the
from inname
salicylic
acetic
Aspro. The theAspro
alkaline
acid alkaline
and
(ethanoic) acidc
condition
ethanoic
comes
Sample in crucible

Ethanoic anhydride Insulated container

morethe effective
small the salicylic
small
intestine intestine
acid.
and and
returns returns
to the toedthe
more more
effective iteffective
salicylic salicylic
acid. ac
Insulated Glass bulb Solution of

(acetic)
Figure anhydride.
14.4 Unreacted ethanoic anhydride is converted to ethanoic acid by the addition of water.
container containing one reactant

Nicholas Products.
second reactant

25
separated and the product
React Ethanoic Anhydride with Salicylic Acid purifi before can be put into tab Figure 25.7
Bomb Calorimeter
Calorimeters used for measuring energy changes in reactions. Solution Calorimeter

Structural equation for the preparation of acetylsalicylic acid (aspirin) from salicylic acid and ethanoic
a A bomb calorimeter used for reactions that involve gases. b A solution calorimeter. Breaking the glass bulb starts the reaction.

406

(acetic) packaged
anhydride. for sale. Supplying
Su
u and using energy
application of calorimetry to measure energy changes in chemical reactions in solution calorimetry

OH Unreacted
COOH ethanoic anhydride O is converted to ethanoic
COOH acidCOOH by the addition of water.
and bomb calorimetry, including calibration of a calorimeter and the effects of heat loss

O COOHCOOH OH
H CH
Acetylsalicylic acid is virtually tasteless and is much less irrit
O O
OH (ethanoic) acid, have to
TheCproducts,
stomach acetylsalicylic
OHO + than
O
salicylic acid
+ Hacid
and
COH 3
itself. acetic
OH
CH
C 3COOH
O C 2O + HO 2O It C
is notCHuntilOHafter it OH
+ CH has
3COOHpassed
+ CH3CO
mallseparated and the product
C purifi ed
CH3before
FAST within small itincan
smallbe put into tablet form a
OH 3
stomach
The products,
tinepackaged
that it reacts
CH 3
+ acetylsalicylic acid water
and acetic
intestine
(hydrolyses)
+ in
(ethanoic)
intestine
theCalkaline
CH acid, have toc
for
the sale.
small
O
intestinepurifi
and ed
returns O
toitthe more effective salicylic aca
3

separated and the product before Figure


can be14.5
put into tablet form
Acetylsalicylic acid is virtually tasteless and is much less irritating to t
C O
Acid
Ba (aq) + SO +example,
(aq)
For metal oxide
BaSO salt
the (s)
reaction + water
between dilute hydrochloric
Acid Formula Anions
3 3
water.
identifi
4
reaction
metal
In
can
the
cation
type,
beIn
case
an of of metal
reaction
example
represented
4
is given.
by the
carbonates,
products should carbon be dio ba
of supersaturate
Solution areequation:

VCEasy
This type of equation, in
Metal oxides which an
include aqueous
spectator Na2O,solution
ions
MgO, ofomitted,
CaO hydrogen
and ZnO. ischloride,
called nearly
exothermic
an ionic all
proc
Hydrofluoric HF Fproduced

in these groups, or reaction types, can be useful.
nc
Reaction is
type present
3 as ionsvirtually no molecules of hydrogen

e co
Step 1. equation.
Identify the possible products
Ionic equations Metal of the
oxides
are
2HCl(aq) reaction are
simpler
+ by
Zn(s) swapping
usually
than the
basic the positive
full
ZnCl oxides
2(aq)
and
+ Hnegative
since
equations they
2(g) and contain
focus the
on
Ethanoic CH3COOH CH3COO the reactions Solution Formula Reaction
The type
following
solution 1 is are
known six as of theDilution
the
hydrochloric more
the fullcommon
acid. Formu
h General reaction types involving
Volumetric Analysis
ions of the reactants: ion. Water-soluble
+ takes oxides tend to form hydroxide ion:
each+
actual reaction that place. Sometimes, however, equation
Acid
Acid
This metal
+equation,
reactive
reaction oxide
canIn this metal be
alsoreaction, salt
represented saltwater
hydrogen +byhydrogen
an
d t
ionicmolecule
chloride equatio
H! 2SO4 reaction type, a an forexample is given.
fin soln
Products:
is preferred. lead iodide
From and potassium
a full nitrate example, you can tell which particular
Sulfuric HSO4Step and2. SO 2
solution
Metal O the
oxides(aq) to+H O(l)
water
hydrochloric
include Na
molecule. 2OH
acid
2O, MgO, is(aq)
According
CaO ionised to the
and
anddilution
ZnO. BrnstedLowry
the zinc chlo
2

There are numerous ways in which acids = and


VISUAL
4 the correct formulas
Write of the reactants and possible products.
2
=when Conc. MetalinVolume Before

of a
Hydrogen gas is produced#from moles compound
metals will dissolve
Reactive water
metals
oxides chloride
areto usually
includeprovide Ca,
has acted aMg,
basic source
as an Kacid.
oxides and ofsince
an water
Zn
The ion.
but
they not Cu,
molecule
contain Ag
thehas or
oa
Reactants compound) is dissociated. The
When an acid is added to a metal oxide, a salt and water
Products equation can therefore be wri
Figu
are

n=cV c1V1 = c
Nitric the
HNOacid solution isNOdilute. Some acids give
Pb(NO3)2 and KI Reaction
however,When to
dilute
the group acids
hydrogen some
are added
chloride reactions
to main
molecule, together
group
so has metals,
acted ason
and th
aPrecip
base s
3 3 ion. Water-soluble
For example, type the 1
oxides
reaction tend to form
between the hydroxide
dilute nitric ion:
acid and so
CHEMISTRY
gases other than hydrogen when concentrated. PbI2 and KNO2H +3
(aq) + 2Cl (aq) + Zn(s) Zn 2+
(aq) + 2Cl
(aq) + H
Worked example themetals, 12.1bbubbles
reactants of
Hinvolved
hydrogen H gas are
andequation: released,
products
all atoms occurformed.
and a salt is form
Asni2
lead +

Hydrochloric HCl Cl Step 3. Write the equationAcid


both sides.
oxide
and
identifi
For
can
balance
O (aq)be
+cation
it sorepresented
reactive
example,
Theforchloride
+ that
ionof
equal
O(l)
the
isHCl(g)
the
by 2OH
numbers
metal
reaction
reactiononly
the of(aq)

between
spectator
O(l)
+ Hsolutions
products ion. VCEasy
salt
dilute
The
H Onitrate
should
(aq)
on
Cl+(aq) hydro
hydrochloric
+ionic equation
bearebap
2
2

+

Acids low F pH; mol sour


Write
taste;
an ionic equation
react
the reaction
with between
bases
the of lead Hand potassium

3.1.1
When 2HNO an (aq)
beacid is+ acid
CaO(s)
added
toby a the
metal Ca(NO oxide, ) (aq)
a salt + and O(l)
water
2 3

allows you to find out the concentration of a solution Hydrofl uoric HF = described
iodide mol
Pb(NO
metal
L)-1inReactive
+Worked
these
2KI
The

For
can
example
groups,
2H
calcium
+
metals
example,
PbI
represented
L oxide
(aq) 12.1a.
++ or Zn(s)
theisinclude
2KNO
reaction
reaction
a solid
base
Zn
so
2+
Ca,
between
the
equation:
mol
types,
(aq)
Mg,
ions
-1 (g)L VISUAL
LHcan
+dilute
K
are
2 be
and
nitric
not acid=
useful.
Zn
dissociated. but
and The m
no
soli 3 2
3

2 3
3 2 2


test your sample of unknown concentration with a volume of known concentration. oxide
The
2HCl(aq)
can be solution + Zn(s) by theZnCl
represented
Acidbase
following are conjugate
six
2(aq)
equation:
of pairs
the CHEMISTRY
+ H2basin
settling (g)
more common
BasesCH
Ethanoic 3COOH high CH3COO pH; Step
Step
bitter
4. Solution
Deduce,
the statetaste;
from Table is ionised
When
10.4,
react
which in
of dilute
the
inwith
products and
acidsis the
acids
calcium
are
precipitate. nitrate
added The is
to ionic
main
precipitate and
is therefore
group m
recall the Solution Formula (Unit 2.1.1c) & Brnsted-Lowry Theory (Unit 2.1.2). ! Precipitation
given
(aq).
Hydrogen gas is produced from metals when 2+ Include the
symbol
Rewrite themetals,
1. occurs
Pb (aq) + Acid
This
when
Reaction
when
solution
appropriate
The
Acid
For
reaction
(s) and
reaction
Reaction
equation
+
dissolved
+
2HNO
calcium
Reaction 2H
the
type,
bubbles
the
states
metal
metal
type
solubility
with type
in
(aq)
example,
type
(aq)can
soluble
Because
the 3an
soluble
hydrochloric
the
single
also be
+solution.
2CaO(s)
reactants
equation.
example
ofis
3hydroxide
+oxide
oxide +2NO
HCl
proton,
is +a solid
(aq)
the
+
So

and
and
hydrogen
extremely
ionic
represented
the
Cl
compounds
acid
theyso
salt
CaO(s)
reaction
are
is
can
is
equation
Ca(NO
product given.
ions
be
gas low
bybecomes:
the )formed
(aq)
state
areand
dissociated
ionised
salt
the+called
water a Ca
are not
between
+an

+(aq)
conjugate
H ionic
symbol
from
into
water
O(l)
released,
theions.
dissociated.
equatio
each other
zinc
+ acid/base
2NO (aq)
dilute
andchlo
The pa
h
+
b
+
3


2.1.2 3 2

2+
2

Indicators change colour


the acid solution depending
is dilute. Some acids give Pb(NO on )the 2NO
pH
isAcid
(aq) ionised of
3 (aq)
compound)
+ 2KI(aq) their
+
in
+hydroxides
metal
2K
is
H
solution
2
(aq)
oxide
environment
dissociated.
O are
PbI and
(s)

2I(aq)
also a The
calcium
O,+MgO,2KNO

conjugate
salt
equation
+nitrate
(aq)
PbI
pair.
water
can
A
+is2NO
(s)ZnO.
therefore
conjugate
ionic(aq)and + pairbe
therefore
2KHCl
is
(aq)
wri
two d
3 3

Reaction type 1 i.e.


+
The
Metal
Metal nitrate
oxides ions
includeare spectator
Na
include ions
NaOH, +CaO in this
and
Ca(OH) reaction
2+ 2 and3 and so the
Mg(OH) ionic.an 3 2 2 3
gases other than hydrogen when concentrated. metal
when Metal
can + be
dissolved
2Hoxides
(aq) by inrepresented
a2Cl
+are proton,
solution.
(aq) basic
usually + So H
Zn(s) the by
. For

oxides
the
2the
equation
sinceZn equation:
reaction
becomes:
(aq)
they
between
+ 2Cl
contain (aq)
the +2H
oxide (2
2

The hydroxide ions from metal hydroxides (H ) react rea

Definitions
pairs are shown as:
BrnstedLowry
Removetheory conjugate acids have gained aO(l)
proton
+
Stepions
2. to
Remove Conjugate
the acid/base
spectator
Metal pairs
ions,
oxides to+ give
include the
Na ionic
O,
equation
MgO,whenCaO for
and
mixing the
ZnO.reaction.
aqueous
+hydroxide solutions, ions can
2H (aq)
+equation: CaO(s) Ca

form(aq) H
+ofthe
+ 2+
the spectator get the simplified
Acid
The 2H
Metal
hydronium reactive
ion. Water-soluble
(aq) ion
chloride
oxides
ion,
oxides
Ionic equations
+ are
2NO
H (aq), metal
tend
(aq)
isusually
+ the onlyto
+ CaO(s)
from
basic
Reaction
the
Flocculation

spectator
2HCl(aq)
exchange
acids.
oxides
typein Ca
aion.
since
The salt
(aq)
The
+ Zn(s)
double
they
3the
In(s)
ion:
+
products 2NO
ionic hydro
(aq) +H
equation
displacement
contain ZnCl2(aq)
anreacti
oxide
acid
next reaction, between (
NH and+ HH2(g)O, the
+
3

2 2 2+
3

Pb (aq) + 2I (aq)O
(aq) +PbI
ion.anitrate
2+
H O(l) 2OH
Water-soluble
ExampleAny(aq)
resulting
-
solids are precipitates.
1water. 22oxides
2
HCl(g) tend ++/NH
Hto form
2O(l)
the hydroxide H 3O 3+ (aq)

ion:
+ ionsCl (aq) + 3 2
are
The salt and ions +are spectator Alum ions provides in this 2Al
Hreaction (aq) and soprocess
the ineach solut
ionic e
In the next Acids
reaction, between areNH proton donors
In the reaction between
3 and H2O, the conjugate acidbase This Acid
Reactive
the solutions
Reaction For
When
+2H
reaction metal
+

Oexample,
(aq)
2 metals
an typeacid
pairs
of oxide
Zn(s)
barium
+ H2isO(l)
are
4added
can
the include
acid

NH
chloride
also
reactionto 2OH
4
abasemetal
base be
3 salt
Flocculation
Zn 2+
Ca, Mg,
and
between
and
(aq)
2+ oxide,
sodium++
represented
H O/OH
water
2(g)
solutions
aCONJ.
acidsalt
is
KACIDsulfate,
and
and
the because
water Zn
of
base by sulfuric
are but an
produce nobac
io
ac
(aq)corresponding
(aq) ions to form
by
(aq) one a+proton.
precipitate of alumini
! 4+/NH3 and H2O/OH because the
B-L ACID B-L BASE CONJ. BASE
equation is often written as: 2H +
+ CaO(s) join
Ca together
(aq) H 2O(l)to form larger, h
pairs are NH each acid
chemfact differs from its
Acid
Metal For+
When metal
oxides
example, diluteinclude carbonate
the acids
Nato2O,
reaction
a are

MgO,
between added CaO
dilutesalt and to+ ionised
nitric water
main
ZnO.acid and +groupcarbon
solid calc m
solution
hydroxide the can hydrochloric
be represented by acid
the equation:is and th
concentration in ppm = mg L1 = chemfact
mg kg1
When an acid is added metal 3+oxide,
+a NH salt and water are produc
correspondingBasesbase by one proton.
Hydrogen gas is 12.1 are proton
produced Water
from metals acceptors
purification
when BaCl
react2(aq) + Na 2SOReaction
aoxide
iscompound)
4(aq)
metals, Metal
four-step can be
+ Example oxidestype
represented
BaSO 2 the
process
are
4(s) 2NH +usually by theH
3(aq) +
2NaCl(aq) under
basicAl
equation:
2O(l) oxides
(aq)
their 3OH own
since
4 (aq)
+ (aq) +weight
they OH

contain

(aq) Al(O
and Figu
th
Hbubbles of hydrogen gas are released, and
When acids with water, hydronium Metal (H For example,
3O )carbonates reaction
include Nabetween
2CO , MgCOdilute nitric
3 and
acid
CaCO and solid
3.O(l)
calc
summary
the acid solution is dilute. Some acids give Reaction
ion.
Acid 2SO
+ metal
Water-soluble type(aq) is dissociated.
+CaO(s)
4 2NaOH(aq)
oxides
hydroxide tend

to
3The
Flocculation
form Na equation
2SO
acid + water
the 4(aq)
hydroxide can + 2H canbe 2 there
ion: achiev
Possib
Aluminium the ionic salt hydroxide is produced
ions are produced. When bases react oxide
with can
2HNO be represented
4(aq) + by the equation:
Ca(NO ) (aq) + H O(l)
NH3(aq) + H2O(l) NH4 (aq) + OH (aq) However, when ionic substances Acids
For reacting
dissolve
example, with B-L
in themetalreaction
BASE
basewater, carbonates
B-L
acid ACID produce
compounds
CONJ.
between
ACID
carbon base dioxide g
CONJ. BASE
dilute h
concentration in ppb = g L1 = g kg1
+ 3 3 2 2
When acids react with water, hydronium (H3O+)
Acid a+ metal carbonate salt +that water +2+ carbon +2. 2td
water, hydroxide (OH) ions are produced. Strong acids
ions are produced. When bases react with gases6 other Reactionsthan hydrogen
acidof Acids
when concentrated.
base dissociate (Chapter 10)Metal
The
with intosulfuric
The salt
their
calcium2H
2HNO
O 2 + and
(aq) acid
ions
3oxide
(aq)(aq) +water.H is
+in ionised
+is2CaO(s)
asolution.
2Cl
O(l) solid (aq)sointhe
precipitate
neces
solution
This
2OH +ions
Ca(NO sary,
means
Zn(s) )2and
called
are
(aq) (aq) not lime.
+both the
dissociated.
H 2O(l) Lime
itsodium
fl
Znisoc, The
(aq) (Ca(OH
which hydroxnitric
base acid
metalReaction hydroxides
can type
be The 3include
Itrepresented
H +
ion in NaOH,
water by Ca(OH)
the
3
equation: and Mg(OH)

Flocculation
water, hydroxide (OH) ions are produced. free ions that are reacting sulfate
is
Metal ionised
For
to formare in
example,
carbonates ionic
asolution
precipitate, and
was
the
include and therefore
mentioned calcium
colour
reaction Naand source and
previously
the dissociated
nitrate
between some
that,
equation is
of ionic
when
a hydroxide in
2and
microorganisms
hydrogen
solution
is more solution.
thereforeof3ions
chloride nitric Water
dissoci
gas
inisfroth
bu
aci
2CO ,metal
MgCO 3 and CaCO .hydrogen
standard solutions have known concentrations Add & The
The
Acid The
When calcium
when dissolved
covalent + ions
chloride
hydroxide
metal
an
molecular
oxide
acidin oxide
through
ion
is a ions
is
solution.
solid
added
water,
substance
isZn(s)
the
sofrom
to
it
Sobethe
the
a
ionises
only
ions
3
salt
metal
equation
that
are not
oxide,
completelyvirtually
does LIME
spectator not
dissociated.
hydroxides
+inbecomes:
water a salt
ALUM
ionise ion. and
no The
react water
todioxide
The any
nitricreaar
chl
sign
io to was
1
The H+ When water of ionic compounds areaccurately
ion insolutions mixed, a reaction expressed as: magnesium Acids
is ionised The2HCl(aq) in carbonate
reacting notAmolecules
solution with
hydrogen
involved +and can
metal
in ion
calcium (or represented
thecarbonates
which
reaction proton)
nitrate isproduce
dissolves
remain ionic by
solution
in(aq)the
andsolutionequation:
carbon
inis HNO water
represented
therefore and are by
dissoci gaa
FULL EQUATION hydronium For example, ion, H the +
(aq),
remain
reaction from
(Figure
acids.
between
14.6a).
ZnCl
The Similarly,
dilute products pure
nitric + H
ofacid
and
(g)
an H
acid
and
SO 3 2

Acid ion+(or
occurs Metal
proton)
if oppositely saltions
charged +isHcombine to form + + 2Cl(aq)Metal
2+an insoluble So when
with
+ 2Na
the
a called
2H equation
a+dissolved
salt
2HNO
+
oxides and+(aq)
(aq)
spectator
++ 3SO
simply,
in
2NO
water.
include becomes:
covalent
solution.
+3ions.
HNa
(aq)
MgCO
+
Settling
molecular+ So
(aq) CaO(s)
2O,
andcompounds,
the
(s)MgO,
is
dissociation
called
equation CaO
Mg(NO
which the
Cabecomes:
2+
(aq)
and
also 2 ionise
hydronium
)2ZnO.
3is:
completely
+ 2NO3 (aq)ion.
(aq) + H2O(l) +2 CO
2+ HThein water
O(l)h

primary standards should be cheap, easilyb obtainable and easy to store A hydrogen in solution 2
represented a as BaH (aq)
3O (aq) or,
b more are
oxide salt(aq)
can and
be water.4 (aq)
2
represented 3by the equation:
a IONICb EQUATION
TheFor Metal 2Hexample, (aq)
+oxides
attracts +spectator
the
are Zn(s)
more
HCl(g) +
reaction between
usually water
H
O(l)
basic
molecules HZn O
oxides
(aq)
a2+(aq)
2+ and + Cl
solution
+asince
is
(aq) + H
further
they of (g) hydrated.
nitric
+

contain H2acid thH

simply, Hcompound. This Thereaction


nitrate ions
reaction + are can can 3 be
also ions
represented
+ CaO(s)
be
in +
this represented
eitherreaction
+ by and
full so
+ chemical the 3+by
ionic an
+ toequatio io
2 3
2H +
(aq) 2NO (aq) BaSO
The (s)
+H4water 2Na is
+ Ca
(aq) (aq) 2Cl 2NO

(aq) 32(aq) O(l)
(aq) and is called the hydronium ion. The hydronium ion itself + H then +left to stand allo
+
For 2H (aq)
example, SOthe 2
(aq)
reaction 2Na +
between (aq) 2OH solutions (aq) of sulfuric ac
The!insoluble
O+
O The nitrate ions are
molecules spectator
H4 SO (l) +not
are Alum
ions
O(l) as inCa(NO
strongly provides
this O
reaction
attracted
(aq) HSO
Al
and
+and
(aq)
(aq)
so
their the ions
ionic
numbe
+

aa b magnesium
ion. 2HNO carbonate
3(aq) +oxides can
CaO(s) be represented 2 4
by
3)
2
the
(aq) equation:
Hthe H 2O
O(l)
3 4

attracts more water moleculescompound andforms a precipitate,


is further hydrated.which However,cana be these water The Water-soluble
equation
nitrate isions or
+ are by an ionic
spectator which tend
(l) equation
+ions 2+ to
the
in this form
that
+ settledfocuses
reaction the 2Na +2and hydroxide
only soon
(aq)
+ (aq)
materials the +2SO ionic ion:
actual
form 2
(aq)a2++s
4 equatio
excess reagent is not completely consumed in a reaction. hydroxide 2H+(aq) can CaO(s)
be represented Ca (aq)by theH 2O(l)
equation:
solution + the hydrochloric
HNO H O(l)
acidH O (aq)
is NO
ionised and th
+
Barium
H Hsulfate, being insoluble, not appreciably dissociated
ions LIME to
3

form
2+ Ca(OH) into 2
its
a ions.
precipitate
(s)
3

Ca of (
3

Settling of the floc


O+ moleculescollected
are not as strongly attracted and their number is not constant. 2H (aq) + MgCO (s) Mg (aq) + H O(l) + CO (g)

2
Hydrogen bygasfiltration.
is produced from metals when ions reacting. +O(l) +dissociated. 2 +acids.
O H
It precipitates andFULL is Hwritten TheHas
H
compound)
2HNO
calcium
BaSO
O
2H 2
+ (aq)
(aq) (s)Some
3(aq)
oxide
+ + to
H
CaO(s)
Acids MgCO
is
indicate a common
3 solid
that
to
3(s) 2+
ionise
the
that
Ca so
completely
2OH fiit
(aq) the
ltering
is Mg(NO
+ a acids
ionsin solution
solid.
(aq)
H O(l) stage. 3)22
are
All (aq)
and
not
of
2 called
are
Thethe bases
H2O(l) strong
sludge COT
acc 2S(

isThe
Reaction
EQUATION ionic H2SO equation
4 type isacids dissociated.
+2acid. is therefore:
2 The equation 4(aq) + 2H
acidscan there
4 (aq) 2NaOH(aq) Na SO
17 2O(l)
O(l) donate protons easily. Solutions
2 of strong would contain
H H
the acid
Acid + solutionHydroxide
Metal is dilute. Some Vitamin
acids
salt
othergive+ HCO(C6H8are
substances O6)dissolved is aionised
Reactionmonoprotic
and intype
are solution
2

therefore4 and The


present calcium vitamin
as ions nitrate
Al in3+ 2C
(aq) is
solution. content
ionic
+ 3OH and of a
therefo
(aq)
limiting reagent is completely consumed in a reaction and which determines the amount of product formed. The nitrate ions are spectator tank and
ions ALUM in is removed.
this reaction and so the ionic e
H H
Some gases common acids and bases Figure 14.32 When
H O (aq) + an acid Acids
+has
with Ammonia
virtually
isandadded
acidbases
is

no behaving
unreacted
tocan aand metal
be
here acid
either
as a
oxide,
base
molecules
molecular
because
aas
remaining.
salt
it has
and
compounds
gained
Hydrochloric
water
a pro
aro
2+
+
H
key questions other than hydrogen whentablet concentrated. was determined IONIC EQUATION
Acid when
The
Reaction
Acid by
For+
titration
Hmetal
sulfuric (aq)
+metal
+dissolved acid
type OHin
4is
sulfuric
carbonate with (aq)
hydroxide
5solution.
ionised
donated aNaOH
and inSo

proton
nitric Hthe
solution
acid 2solution.
O(l)
are
so
salt equation
isthe and
+most
behaving water both
common0.300 salt
becomes:
+sodium
an strong
acid.
carbon gOnly of
acids. aasmall
+ofhydrox wat
dioxid
3

Figure 14.3
a The hydronium ion, H3O+, is the conjugate Reaction 2H
2H example,
(aq) (aq)
+type
sodium
+ofMgCO +
the
ammonia 2Cl carbonate
reaction
3(s)
(aq)

molecules Aluminium+between
(Na Mg Zn(s)
2CO
ionise so3),that
(aq)
+when
dilute
Ha21.0 hydroxide
O(l) M +Zn
dissolved
nitric
2+
CO2acid
solution (aq)
in
jelly-like,
(g) water,
is and
ammon +pr2 trr
Acids and bases can be either molecular compounds tablet or ions.
b H2O. For example,
required 19.62sulfate mL of are + ionic
0.0832 and
M+)ammonia therefore
NaOH for dissociated
complete in solution. Water
).reaction.
acid of water,
Figure 13.8 Acid
Acid ++ metal
metal as hydrogen
Weak
+carbonate
(Na 3acids
and Filtering +carbonate

carbonate saltions + (CO
water 2
+ The carbon+carbonate dioxid io

1133
a The hydronium ion, H3O+, is the conjugate Metal
oxide 2H
carbonates
can (aq)
be mostly
represented2NO
include (aq)
Na CO
by CaO(s)
the ,
molecules MgCO equation: and
together Ca
CaCO3 with
2+
(aq) .some 2NO
removes
ammonium 3 (aq)

co
sodium carbonate (Na2CO3), when dissolved in water, releases sodium ions
Calculate theofactpercentage covalent
Metal
The chloride molecular
hydroxides
ofcarbonates
vitamin Strong
ion
withC acids
substance
include
isin the
2
the precipitate
3
only that
oftablet. NaOH, does
3
spectator not called
Ca(OH) ionise
3

+3ion. the to The anyfl


and oc, Wa
sign
io M
3
Hydrogen gas is produced from the reaction Cl (aq)
Figure
hydroxide 14.4 aions.shows This some
is shown
salt common +3an
in thePure
water acids
equation and
by
carbonthebasesispresence and
dio th
of

acid of water, b H2O. Acids reacting Vinegar metal
is solutioncarbonates ethanoic produceacid. carbon
ethanoic dioxide
acid gas
2isathe
polar togecov
as (Na+1) and
a Namecarbonate ions (CO3formed
the precipitate
2
). Thewhen carbonate
aqueous ionsolutions
can as the
of a EQUATION
base. Metal 2 nitrate i type include Water
Na 2CO a3from
,weak
MgCO the
iiand and settling
CaCO tank
+ .and allow
aWrite a 3full chemical equation and ionic equation for
Filtering
some metals with dilute acid. FULL The
Reaction
So with the 2HNO
equation
salt and ions It are
arrows.
(aq)
water. Anbecomes:
was
molecular spectator
5+ equation
Ammonia
CaO(s)
mentioned
compound is ions

colour
showing
previously
that in this
base
Ca(NOthe
that,
ionises in reaction
3)some
water.
reaction
when
in water 2(aq)
hydrogen
to of amicroorgan
produce Hchloride
2O(l)
moleculeso
hydrogen gas or
ision
bu
ionio
Acid
Figure 14.4 shows + Metal
some common Oxide
acids salt
and +
bases H and
2 O their conjugates. TheAcids hydroxide
reacting with metal over ions
carbonates through
gravel. from produce
This metal
sand carbon
removes & hydroxide
gravel
dioxide
any gas
remain toge

Titration Method
following compounds are 18 mixedAn together: through water, it ionises completelyvirtually no hydrogen chl
antacid
Acid contains IONIC Metal
Acid
magnesium
EQUATION Foreach +hydrogen
2H
2H +of(aq)
metal+
example,
(aq) theused following
carbonates
ethanoate
hydroxide
+ the +
hydrogen
CaO(s)toZn(s)
demonstrate
reaction precipitation
(acetate)
include
ions.
carbonate
(Mg(OH)
between Ca acid
2+ Zn reactions:
NaHCO
(aq)aoracid, base
solution
2+
+ )
(aq)
H as 3, the
O(l) KHCO
behaviour+
of H
nitric (g)
active of and
3 acid the Ca(H
react
and s
An equation showing the reaction of a molecule or ion with b water can beThe
with
hydronium calcium
a salt and Polyprotic
oxide
water.
molecules
In
+covalent a is
1.0 a+ be solid
remain
M solution acids so acid
(Figure
+representedof the 14.6a).
ethanoic ions are
Similarly,
+2acids. only a not
pure
small dissociated. T
HNO
proportion
2 and
(less H SO
than
3ion, H (aq), from The product
Acids 2H +
(aq)
added SO +metal
2
(aq) 2Na +
(aq) 22OH 2
(aq) 3 2
i K2S acidand MgCl Fora example,
magnesium AgNO carbonate(aq)oftoFor NaCl(aq)
example,
can hydrogen the carbonates
Hwhich
by SO
+contains the : equation: (also
+proportion known inas bis
Settling salt water carbon 2 diox
4 molecular compounds, 4also ationise completely water
used to demonstrate or base ingredient.
2 behaviour of the reacting species.
0.138a protongtoof isantacid
ionised was
in solution crushed
the
the ethanoic
reaction
and
acid
Chlorination and molecules
between
calcium added are ionised
adonating
nitrate solution to
2Na is 20 any
of
+ionic
(aq) mL
one
nitric time
+and SO of acid(Figure
therefo
(aq)and 14.6
+
236 Strong acids
Acids donate form: Some acids are capable of a more than one 4ofproton
ii CuCl and AgNO also produce
b CuSO carbon
(aq) +
1.0 M HCl(g) dioxide
solution
Na CO of
(aq) together

ethanoic acid with a salt
high and water. ethanoic
HClThis mixtureClare aH O(l)salt and water.
+ + H O(l) H O (aq) + Cl +
(aq) +
For example, the acid H2SO4:3
+
magnesium 2HNO carbonate
(aq) MgCO Hcan 3be(s) represented Mg(NO by3and
) 2the
(aq) equation:
H O(l) CO (g)
2
water. required
when dissolved 18.923 4 molecule
in mLsolution.
2SO of
2and
(l) +0.200
4(l)
3are +SoH 2O(l)toM
the Hhydrochloric
equation HSO 4becomes:

(aq) + H3acid O ions.+
(aq)
2 3

Metal molecules and some said


hydrogen be polyprotic.
ions ethanoate The 2 number
(acetate) of2 hydrog
At 25
Reaction chydrogen type carbonates
46 include NaHCO ,then
KHCO and Ca(H

4 of liquid
The water is left togas stan
2

Acids donate a proton to form: iii KOH and AlCl3 Reaction


The For ionic example, 4type
(NHequation)(aq)
2SO
the
(aq)
aIt41.0
was H
is reaction
+solution
SO
BaCl
therefore:
mentioned H O(l)
(aq) fiinbetween
previously that, O (aq) solutions
when + 3HSO
hydrogen (aq)of 3hydrochlor
chloride
+
is (aq
bu

Reaction + 3 type
Macid
2 After base ltering, )the clear water is us
2 4
of ethanoic acid, the 2
concentration of 3 4

For example, acid can donate


the 2depends
reaction on the structure
H between
ofso2the acid.
solutions +CH COCOO ob

H2SO4(l) + H2O(l) Water HSO4(aq) + Hfor H2SO4 FULL EQUATION


HSO
14The

nitrate
2HNO ions are + spectator
MgCO 3(s) ions this
Mg(NO reaction 2(aq) + and +(also
H the
O(l) ionic equatio
(g)
neutralisation. Calculate Acids (aq)the
(aq) 1percentage
added Hto metal hydrogen by masscarbonates of Mg(OH) known in as bica
3
3O (aq)
+ a Equation +
+through add chlorine gas
HNO water,
(l) it
H ionises
O(l) completelyvirtually
O 3(aq) NO
is(aq) noin hydrogen
+
chl
HCl Cl
Acid iv + Metal Carbonate sodium
NO3Acid d +2H hydrogen
metal + 2NO carbonate
carbonate
(aq) is
3 (aq)
only +can
CaO(s)
approximately
+

which be represented

0.004
the salt M. Ca
This
+
settled
2+ by
water
(aq)
shown the
+and 2+
2NO equation
an
materials carbo
2
3 (aq)
equation

Chlorination
MgSO and NaOH K S(aq) Monoprotic
Pb(NO ) (aq) acids can donate 3
only 2
one proton 3
include hy 3

+
1 pipette one solution into a conical flask (the sample !antacid. Acidic
CH COO
Hoxide (non-metal destroy bacteria.
oxide) Chlorine
base reacts wit
sa

HNO3 molecules remain 2(Figure 14.6a). Similarly, pure HNO and H SO
acid base +and
+are the base O : Mg
3
4 2 3 2
also
The produce (aq) carbon OH dioxide
(aq) together H O(l)

with aalsosalt and water.
+
hydroxide + can be represented by the equation: +
IONIC EQUATION presence of
reversible arrows:
Acid nitrate
metal
ions
hydroxide
spectator ions in this +inH(HF),
reaction and + are so
salt2the ionic
wat
HSO4 Acids that ionise completely solution called strong3)equatio acids. S
the 2H (aq) MgCO 3(s) 2(aq) 2O(l) CO (g)(HNO
+ 2+ 3 2
H2SO4 acid (HCl), hydrofl uoric acid nitric acid and eth
+
+
b Write a full balanced chemical equation H 3for each reaction.
O H 2O
The
Metal
H O(l)eHCl(aq)
nitrate CaCl
carbonates ions(aq) + covalent
NaHCO
are
acids Na PO
molecular
spectator
donate
include (aq)
(aq)
protons
Na
compounds,
toions the
easily.in
CO fi
which
NaCl(aq)
this
Solutions
,Hacid
MgCO ltering reaction +
of strong ionise
and H stage.
completely
O(l)
and
acids
CaCO + so
would
The
CO the
in water
(g) slu
ion
contain
3.
NO3 ThisCHis3COOH
an example of+ a hydrolysis For
reaction. example, 2 (CH
the COOH).
reaction
3 4 +2between solutions of +hydrochloric
HNO3
Osalt : +H ! 2OFigure
+ CO PO4++O
2
3 2 2
and the base 2
(aq) +2include CH 3 COOH(l)

SO ,such
2SO
Cl
H 2+ (g)
O(l)
H 2+O(l)
CH3COO (aq)
+ remaining. H O HOCl(aq(aq) +

3,sulfuric and CO 2. equation:


Acidic oxides H+ O(l) + OH
f(aq)2H MgCO 3(s) Mg 2(aq) H O(l) CO 2(g)
2 CH2COO +
with O 2
virtually (aq) +no H O(l)
unreacted 3 OH
molecules Cl(aq) (aq)Hydrochloric
13.8 +carbonate
H O (aq) +
HCl(g) 3
(aq) (aq) 2 + 3 3

213
13
NaOH(aq) Pb(NO 3)2(aq)
is called an aliquot, and it has known concentration)
+ H
3
Diprotic acids, as 2acid2
(H 2SO 4) and
3
carbonic acid
H3O H2O
A hydrolysis reaction is oneHCO sodium
in The H O water
which Acids hydrogen
reacting
is a withacid
+include metal tank
2can base
be
carbonates and
represented +isHremoved.
10
produce by the
carbon dioxid +M
+

H2CO3
2Reaction
sodium H2SO type and4(aq)
+5 chloride
sulfuric
3
acid 2NaOH(aq)

and ions
nitric are
acid spectator
are the most ions
common Na in 2SO
this
strong
4(aq)
reaction
acids.
HMetal hydroxides CaNaOH, asCa(OH) 2 and
Hydrogen gas is+produced from the reaction ofof Equation When
2H +
(aq)
non-metals CaO(s)
can base
H SO
donate (l)
react
+
two H acid
O(l)
protons.
with
2+
(aq)H
oxygen,
O (aq) +
2O(l)
HSO
they
(aq) +

oftend to produ
3
CH2COO O2(aq) + H2O(l) This reaction is used to test
(aq)for the presence + The main purpose chlorination
kills bacteri

5 a burette
CH3COOH OH(aq) OH CH COOH(aq)
Ethanoic acid is, therefore,
2 4
described
2
a weak acid
3
in water.
4

12
1
H+ reactant. with aequation
salt and3+is: water.
3

HCO3 somedioxide.
metals When Titration
with dilute acid.
H3PO4
curves a
FULL EQUATION 2POionic
Acid
4
+HCl(aq)
metal hydrogen
NaHCO
HNO (l)acids
Triprotic
3(aq)
H O(l)
carbonatecan
donate HO
NaCl(aq) (aq) + NO
three +protons.
(aq)
H2O(l)These + COinclude
+

2(g)
p

acid carbon carbon dioxide


NH4+ is bubbled Weak acids
3 2 3 3
H2CO3 base NHThat Reaction
The is, when type
hydroxide 5(H
these oxides
)isand ions
the are from
hypochlorous added tosolution
metal water,
acid they
hydroxide
(HOCl) form tha
2 titrate the other solution into the conical flask using H3PO4
NH4+
H2PO4
NH3
Acid + Metal throughHydrogen Carbonate
calcium hydroxide
Hard
or limewater,
water HCO3 it Figure
is caused
The
IONIC EQUATION
14.6
3
2
The
CO3The Acid
by
Reaction
hydronium
sulfuric
For (aq) example,
H O(l) H (aq) +
Cl

Ca + 2+
acid isreactions
magnesium
a In a 1 M solution, hydrochloric
sulfate
sodium
virtually
+
metal
a 1 are
ions.
type
and
acid
of
Strong
Amphiprotic
HCO

hydrogen
Polyprotic
ion,
carbonate
ionic
Vinegar
acids
2
the
Acids

Ca
4
these
chloride
is
3POthat

(aq)
3 is
donate
Hand
2+
ionised
4reaction
bases
aacids
+the
can
ionise
with
ions
solution
protons
(aq),
boric
do Filtering
cell
be
therefore
salt
substances
carbonate
binds bases
are
not
of
(H
in
between
completely
Hdonate
ethanoic
easily.
walls
from
arepresented
2
+
O(l)
to
solution
3BO3)in
water
the
produce
spectator
Solutions
acid.
+ CO
all
acid.
of
acids.
a
solution
their
Pureof+
stearate
indissociated
ions
by
2strong
microorganisms
are
carbon
(g) a
protons
and
ethanoic
The
the
called
salt
in acids
both
atand
this
acid
of
strong
dioxide
of
once,
would
nitric
sodi
is a water.
reaction
product
equation: in
but
polar
sod
acids.
contain
and
solu
do
cov
a
S

+ H2O + CO2 During a titration, completelythe


ionised in pH ofFor Hthe Msolution in the reaction flas ask
forms a precipitate of calcium carbonate. The The
molecular
with ionic
virtually compound no unreacted sodium
that oxide
ionises (Na
water O)changes
todissociates
produce as
in water,
hydrogen rele
ion
HCO3 CO32 Amphiprotic salt substances H2O OH
water. b However,
ionic
Metal
solution of ethanoic acid, onlyAcid
Oinequation
hydrogen
+example,
metal
when
is:
Some carbonates reacting
the
substances
carbonate
with
include
reaction ) Water
cansalt

base.
NaHCO +acid
between
behave water
from
molecules
salt3, either
KHCO ).+ carbon
the
+
remaining.
carbon and
settling
acids
water or
Hydrochloric
dioxide
Ca(HCO
dioxide
+
bases, carbotankdepe3)
2
a2
236 After )chlorination, water is consid
(aq) +

3 continue titrating until equivalence point is reached (which is


sodium ions (Na and oxide ions (O +
The oxide ions react comp
(active ingredient of soap) to produce calcium stearate, w
2
precipitate forms a suspension which makes a small proportion ethanoate
sulfuric
3
Sulfuric acid (acetate)
and
acid (H ions.
nitric SO acid are
is the
diprotic, most common
meaning 3
itstrong
has acids.
two protons
H2O OH more solution isof ethanoic
badded from
acid molecules are
covalent
are ionised.
calcium athe
Acids salt
H+burette.
2HNO and
molecular
added
hydroxide3(aq)
to water.
+reacting
with In+
metalConsider
the MgCO
with,
a 1.0 aM substance
hydrogen
water, and
accepting
solution
the
(s)2diprotic
can
of
4
carbonates titration
a therefore
proton
ethanoic
+that
Mg(NO
acidacid, to (also
form
only does
donate )small of3 and
(aq)
2known
hydroxide
ain 20.00
or +not H2bicarbona
as
receive
ions
proportion O(l)
(OH mL
ionis + C
(lessproto
): than
3(limewater) can be represented by the 3)2e
Bases accept a proton to form: donate to base. 3A ionises 3 two stages, for exampl
Some substances can behave as either
the limewater lookacids or bases,
milky. depending what they are Metal hydrogen
(aq) carbonates
HCO (aq)
include over HNaHCO
2O(l)gravel. 3, KHCO
CO 2This
(g) removes Ca(HCO an

6 so
222 Bases accept a proton to form: reacting with, and can therefore Water donate ofor0.10 MOH
receive HCl with

protons. 0.10HSo
Such substances M also produce
2OMetal
The For
NaOH.
the carbonates
example,
(aq) equation
Acids
Cl nitrate
carbon
are Weak
of thedioxide
Initially,
addedions to saidinclude
Stage
aremetal the
O2to acids
ethanoic
the
1(aq)
becomes:hydrogen
spectator
together
acid
HNa2O(l)CO ,
be+ reaction
amphiprotic.
pH with
molecules
2ions ofacid the
OH
carbonates
3in
a
are
MgCO
between
(aq)
this
salt
ionised
fl ask
+ OH
(also
reaction3
and
at (aq)water.
any
and one
contents
known CaCO
and
time (Figure 14.6
solutions . ethanoic
assobicarbona
the
3of iono
approximated as being the end point of the indicator
1.0 M basesolution of ethanoic contains a high proportion
Acidic non-metal oxide + base chemistry y in action For example,
H O(l) CO (aq)Vinegar the
+InCa(OH) reaction acidbetween
2(aq)
solutions
CaCO of3(s)
hydrochloric
+carbon
+ H O(l) acid

NH3 EQUATIONNH4 +
also Acids
produce reacting
2 carbon with equation
H2isSO
dioxide a metal
solution H1,
together
+ ofwater
carbonates
ethanoic
with readily
acid.
a produce
Pure
salt accepts
and ethanoic
+ Hwater. a 2proton
acid a dioxid
is ions.polarAtfromcov
are saidW to be amphiprotic. molecules 4(l)
and some 2O(l)
hydrogen HSO
ions and 4 (aq)

ethanoate 3O(acetate)
(aq) 25
OH Water will beof1.0 CO3(the pH of anHCO hydroxide
0.10 M HCl can
solution). be representedAs NaOH aby
is the
added, equation:the pH
2
H2O
NH3 NH4+ In equation 1, water readily accepts role a proton water
2
in
from sulfuric
! maintaining
H+ acid and
sodium

with
3 For a 2H
life hydrogen
salt
2H
+
(aq)
in
example,+and
acts
the
(aq)
carbonate
The
+molecular
awater.
1.0
the
+
Sulfuric
as
MgCO aoxide
environment
Mreaction
SO
solution
acid
ion
compound
base.
3(s)
can is an

In
of be that
ethanoic
between
ions. +
isapproximately
a strong
(aq)
represented
example
equation Mg
acid
ionises
2Na
of(aq)
2+
-0.004
acid, 2, strong
in
maintaining
the
solutions
in water
water
water byH
+and the
base.
todonates
concentration2O(l)
ofso
Strong
produce
Chlorination
equation:
hydrochloric
is+shown
this stage +ofbases
CO hydrogen
aoccurs
water
CH accept
proton
(g)acid
COO
32
ion
qprctb
(aq
to
+(aq) +2OH (g) (aq)
2 +M. This
salt + H2O2, water donates rises aslowly atthe
fiCalcium
Fluoridation
PO43
rst,
Aqueous + solutions
but then
of bases
HPOare Table
rises
2called alkalis.
(aq)13.4
very lists
easily.
ethanoate
H +
sharply
(aq) some
is only(acetate)common
at the acidic
equivalence oxides and
a point.
in an the
equation anio
choose your indicator carefully!) see page 11 of data booklet
4Conical therefore acts as
an acid.
sodium hydrogen Strong
+Virtually
carbonate acids
4H
2can 4 be represented Hby the asequation:
CH COO
HCl(aq) NaHCO (aq) NaCl(aq) O(l) CO

CO32 HCO3 For example, the 3reaction between aonly 2solution 2of nitric
acts as a base. In equation proton to
+a+
boxide ion and Sodium no SO
hydroxide molecules
is sometimes are found
referred ain toan aqueous
strong solution.
base.
(less How
carbonate will react with acids, but is In a 1.0of
+ M solution of ethanoic

acid, small proportion than
3

PO43
+ H+
HPO42
solubility, CH3precipitation
COO not considered an alkaliCH reactions,
in
3COOH
because reactions.
flask H
itHis+ insoluble
totally SO pH (aq)
presence
ItH +is
Stage evident
partially
2. 2NaOH(aq)
reversible
The After
that
HSO
arrows:
water
ion fi
formedltering,
are ionised at any one22Na
can act
in as
Stage Na and
the
either
1
some
canSO clear
analso (aq)
4 (aq)
+
acid
act wa
or
as an a
therefore acts as an acid. At that point, O2 the
in water.pH is OH 7,Reaction
because
magnesium
The sodium
dissociated HCl(aq)
2
the
carbonate
and +1.0
type
Indicator solution
according
chloride
NaHCO
It was
5
dissociated
correct CH
to
can
(aq)
mentioned
to 33say
the
4 of the ethanoic acid molecules
ionsthat
COOH(l) contains
BrnstedLowry
be
are +aH
sodiumrepresented
spectator
4
previously NaCl(aq)
2O(l)
that,water,
hydroxide
defi
ions
when+CH
nition
isH by
an in
O(l)
hydrogen
a3COOionic sodium
of
the
this
acids
examples
(aq) CO
and
time (Figure
equation:
reaction
+compound+H 2(g)
chloride O+(aq) ions
bases,
gas
thatand
it
is
14.6 is
aso
is bub s
! the 1.0 solute
M M solution,
solution present. only
of
destroy
If
ethanoic smalltheacid solute bacteria.
proportion
contains is a
of stronger
highthose
Chlorine
ions
proportion acid
3react of than
further
ethanoic
re w
2
CH3COO CH3COOH
It is evident that water can act as either an acid or a base, depending on H O (aq)

4 repeat the whole process several times


+

ionic equation is: through water, it ionises completelyvirtually no hydrogen chl


and chloride ions onlyall neutral species. Beyond . theions equivalence point,
3

Many water supplies The


have sulfuric
fl uoride ions acid is ionised
acid andbase base
in14.6a). solution and both sod
H O(l)
of Othe+ strong
molecules some OH
hydrogen and ethanoate (acetate) ions. At 25
Amphiprotic substances H
Strong and Weak Acids and Bases
ions and SO ions.
2
O2 OH
The TThe ionic + equation
react as asolution
base.is 3If, therefore:
however,
the solute is a stronger andbase th
2

the solute present. If theTABLE


solute13.5
is a Commonly
stronger acid used than
Figurewater,
14.4 then water will Acid ABLE sodium
13.4
2HNO metal and
Some
3(aq)
chloride
hydrogen
molecules
3
a 1.0 +common
MMgCO
ions
remain are
(s)
of
(Figure
4 spectator
carbonate
acidic
ethanoic oxides
acid,Mg(NO ions
Similarly, and
the concentration
in
3)2(aq)
this
purethe reaction
+of
HNOanions
H CH 3 O(l) and H +2(aq
theySO so
C
3COO
CH COOH(aq) 2
Ethanoic acid is,compounds,
therefore, described as
This
added isthan
an
to example
them ofthe
inwater a hydrolysis
fithe
nalionic stages reaction.
before Cl (g) +aionise
weak
H acid
2HO(l)
in water.
an
in waterH
3

ofaisas more NaOH is added, pH rises slowly 4 again. A 14.5 graph 4of pH change
equation
H +
(aq) + react
is:covalent
HCO 3as

(aq)molecular
isan acid. Figure H22O(l)
O(l) +0.004
COwhich SOalso
lists
(g) some completely
+ common amphip
examples
react as a base. If, however, the solute ionic equations
a stronger Somebase
common ! and
water,
acids bases.
sulfate
will are ionicWeak
H +
(aq) HSO
andbases
only (aq)
therefore
+H
approximately
salt + +
22dissociated
M. This
2
(aq) is shown 3O
+and
+
(aq)
in
soin
equation
solu dib
+water carbon
react ascan donate
Figure or accept proton Acidic CH
oxide
COO (aq)
Acid formed when oxide isreaction
added Anion produ

Figure 14.4
Aamphiprotic
hydrolysis OHreaction isweakone to The inaSTRONG nitrate
which ions are spectator ions in this the ion
+ water ispresence
aHSO
3

+ACID
is usually considered be base. However,
+
Strong HCl(g) + H2O(l)
ofreversible
bases arrows: H3O (aq) Cl(aq)

an acid. 14.5 lists some common being released for
substances. household H
use. (aq)
It has OH (aq) H O(l)
or bases with the isaddition ofsolution,
NaOH is
a shown intofiwater gure 3.2.7 and H3is an example ofbases
Some common acids and bases. H (aq) + HCOAmmonia
(aq)
is
is a
a weak H
covalent O(l)
acid. +
A
molecular CO
solution (g)
compound of sulfuricthat acid,
ionises therefor
in wate
covalent acidOis .virtually +molecular substance The Othat
2+ main does
purpose +not +of ionis
Figure 14.6
can be acids Reactants 1Ionic
Burette
equation
reactant.
2a InPipette
it can act as a verydelivers acid by donating its 3 4
H2SO4(l) + H2O(l)

2 + 2
2
(aq) + HSO 4 (aq)

with chlo
in water. bMetal ahydrogen carbonates include NaHCO , KHCO and
2(g) Ca
a 1toMform hydrochloric
been shown proton
thationisedcertain
the very strong
levels
base 2H
in of (aq) hydrogen
fluoride +accepting
3MgCO CH3a ions,
proton.hydrogen
3(s) has
COOH(l) +H
This 2O(l)sulfate
ionisation
Mg (aq)ions
can CH +and
be H
3COO sulfate
represented
O(l) (aq) +ions. HbyCO
3O the(aq) equation
2

filled with aknown volume ofWEAK ACID The Indicator


Donates
ionic compound sodium 4HoxideThe (Na end 2O) 32point
Amphiprotic dissociates has in3 water, rele
aHtitration curve. Notice that near the a equivalence POpoint the pH rises
H O (aq) +

acid 3(l) +acid
HNO H2O(l) 3O (aq) + NO3 (aq)
+
completely However, 1M
(Na+) is the 4) hypochlorous acid (HO
3

So the equation becomes:


Phosphoric
proton (Hbase can ionise in
2 substancethree stages and is called
Donates Figure 13.8 Acid and metal +
+ OH
(aq) reactant. (aq) solution sodium ionsadded. and 3oxide ions (O ).reached.
The oxide ions react comp

13
1 31144
only aCO Acids added Carbonic
to metal acid (H CO ) described Carbonate (C
one the been +hydrogen carbonates
been (also known as
of other reactant
ethanoic acid, small proportion
Amphiprotic in drinking waterAccepts reduce dental decay

Back Titrations
NH 3(aq)ionise Hacid
2O(l) NH (aq) inas+water,
OH (aq)
+

sharply from pH 3
of ethanoic
ato pH
acid molecules
11. WEAK
are ionised. 2 COOH(aq)
CH
The BASE
sudden acid.
with toPhosphoric
Acids form:
change
the
Ethanoic that
water,
3
acid
acidin
accepting
is, completely
2is
pH
therefore,aa 3proton
weak
at
inacidsolution
that
to
4
form a are
point
hydroxide
weak called
andacid strong
so,
could
ions
in in(OH
water. 1.0

): MS
a acids.
a proton
to form:Hydrogen gashydroxide substance
is produced from the reaction of H2O(l)into flask.
proton
also H
produce
O(l)
carbon
acids
phosphoric donatedioxide
base protons
acid, the
only together
easily.
a cell
small Solutions walls
with
proportion of a of
strong
ofsalt themicroorgani
and
acidsprotons water.
would arecontain
dona
!in children. The fluorideReaction is incorporated
2

+ type 5virtually

1144
2

occur with the addition


to form:
of as SO STRONG2little 2H BASE (aq)
as Sulfurous
with
one
Strong
OH
+the
O (aq) 2
SO
drop acid
+noH2O(l)
(aq)
of (Hextent
unreacted
NaOH 2SO+ 32Na )acid
OH(aq) + OH(aq)
ofsolution. (aq)
+ ionisation
molecules Hremaining.
O
+2 2OH Any
Sulfi teprogress
(aq) (SO3
Hydrochloric
2

4OOTHDECAY
some metals Acidwith
anddilute
metalacid.
H2O 2H (aq) +
+
CO3 the
2
(aq) are
Figure 14.6 For
H O (aq) example, ionisation base bases
stage.
2 reaction
+
CO3 acid 4and nitric acid
The
acid
Afterbetween the
chlorination, solutions water decreases
of hydrochl
into enamel 3O of theAcid teeth, +reducing
sulfuric are the most HCO3 strong acids.
common
(Na
3
OH +
metal
Titration Curves
hydrogen carbonate
! Amphiprotic a In a 1 MHsolution,
substances sometimes
hydrochloric called
acid is virtually Stages 1 2to 3.
2Na (aq) 4+
+equatio
water. bsodium
SO hydrogen carbonate
Sulfuric acid ion is(H can
2SO4used be represented
) oxide 4 by the
Sulfate (SOrele
Ha+strong +
HCOindicator H2that changes CO3 in colour 3 in this range 4 could be for this titration.
+H 2
CO32 carbonate
+ CO ! (g)H2ionised
O(l) susceptibility
ampholytes. completely However, in a 1 M The The
ionic
HPO oxidecompound an example
sodium of O)
base.
H2PO Strong
dissociates bases
in accept
water, pr
+ their to attack by acids.
2
Amphiprotic substances are sometimes called
HPO42 H+ Figure
3
3.5
+H
2 ofsolutions
solution
Aqueous ethanoic acid,
of basesonly a
aresmall
called
Polyprotic proportion
alkalis.
acids can Weak
easily.
sodium
PO (1)
3ions
acids
H PO (Na (aq)
) and+H oxide
salt +
O(l)ions (O ).HThe
water HPO 4 + carbon di
PO oxide
(aq)
2 +ions
3 H Oreact(aq)comp
4
+
2
2
2 4

3
+

246
H2PO4 H3acid
POmolecules 4
Acid and metal 2H in an+acidbase
(aq) HCO HCl(aq) + NaHCO (aq) NaCl(aq) + H O(l) + CO (g)
3 (aq)
ampholytes. + Sodium hydroxide is sometimes referred to as a strong base. ):2How
4 will react
Pdonate
4O
with the2 water,
Phosphoric accepting
3 acid
(aq)of+(H
a
H3PO
proton to
4) acid.
form hydroxide ions (OH
Phosphate (P

Steps Fluoridation of
of ethanoic
Calcium
titration. Hwater
carbonate
supplies
are ionised.
with acids,
has
Cl (aq)but is
been a
some acids are so weak that they dont produce a236sharp end chemistry y in action alkali The ionic equation is+ Htherefore:

PO43 HPO 4 not considered


Water
W 2POan 4 because it is10 >1
insoluble proton. SO4(2)
Vinegar
according is Ha
to
PO
solution
the BrnstedLowry
O(l)
ethanoic defi PureHPO
nition
HSO
of 4 (aq)
ethanoicacids
+ HisOa (aq)
2 acid
2
and 4

polar
bases, it cov
is 2 4
2
3
+

H2O(l) + CO Metal
TheFor hydrogen
example: carbonates
O (aq) include
O(l) NaHCO
OH (aq) + OH (aq)
, (aq)
KHCO and isCa
2
SO42 hydrogen HSO4 12 controversial 2(g)
issue
in water. H SO
2 4 in many communities,
sodium and
molecular
chloride
correct (3)
to HPO
base
compound
say thations
(aq)
acid +that
sodium are
ionises
H O(l)
hydroxide in water
spectator is anPO 3to
ions
ionic produce + Hthis
in
compound Ohydrogen
22
3(aq) reacti
that
4
ion
as 2 4
3
3
+

ethanoate (acetate) ions.


carbonate Acids
After H added
+writing
+to
(aq)Substances
the metal
ofFigure strong
ionic
OH
basehydrogen
equations
(aq)
OH
. carbonates
forofHaastrong
number
O(l) (also known
of bases
specifi aspr
cthanre

point. These need to be back-titrated. sinceFluoridation


similar !b effects can beequationachieved
ionic is:So
In
Theafar,
1.014.5
we
oxide M have
solution
ion only
is an of discussed
ethanoic
example acid,the relative
only a small
base. strengths
proportion
Strong ofaccept
acids
(less a
Figure 14.5 Water 2 Th The other h solution l Aqueous is ofd dispensed also
are calledproduce
basesnotice d slowly
that l many lWeak
carbon
water.
of theinto
easily. It must
ethanoic
are
that the
dioxide
the h
are
be
acid titration
together
amphiprotic.
noted,
same.molecules however,
In
2
with fl
that
are ionised
most ask
a k
when
at salt
any
situations, from
f and
added
one timeto a
water.
a base14.6
(Figure
each typ str
bases
!

1144
with regular use of
solutions
flwilluoride toothpaste
alkalis.
is+(aq) or+water, of
Hexample, HCO 3 (aq) 2O(l) +solutions
Hacid CO 2(g)
M asolution
Substances that are amphiprotic.
Figureand 13.8 bases: proton burette. Calcium carbonate
OH is usually considered react with
to be For
acids,
a base. but
However, 1.0
theweak
Sodium
reactionacid
hydroxide willisionise
ethanoic sometimes
between to a greater
contains extent.
a high
referred as a For
to proportion example,
strong
of ofbase.
hydrochl ethanoicas
How

13 114
13
acids transfer; common reactions
have a particular of acids;
ionic strong
equation. and
The weak
more common acids of these
react an aliquot of your sample solution with an excess of a 10 tablets. inproton it H
is O(l)

1
not
it considered
can act as a an alkali
very weak because
acid by insoluble
donating its molecules
Ammonia
according 2
and
is
to a
thesome hydrogen
covalent
BrnstedLowry ions
molecular and
defi
such as OH , will accept the second proton from H SO and the s ethanoate
compound
nition of (acetate)
that
acids ionises
and ions.
bases, inAtit 25
wate
is
sodium O . flhydrogen 1.0carbonate can be represented byofthe theequatio
2 4

Hydrogen
and bases; gas is produced 3 from
polyprotic Theacids;
the Many
equivalence
reaction ofwater
amphiprotic
Fluoride
water.
point supplies
to form
is added issubstances
the
the very strong
to in have
base
the point
Table water uoride
during
13.5. ions
acorrect
the
Mto
accepting
third proton titration
solution
pH asay
2
thatofsodium
range
proton.
from ethanoic
This
H PO for when
acid,
ionisation
.hydroxide the
the
canis be solutions
concentration
anrepresented
ionic compound byCH COO is (aq
equation
that as

COO (aq) in theH


3
3 4
of (aq)
the is onlybase
strong aapproximately
OHbase . 0.004 +
M. toThis is shownextent in an equation
if addedb
244been

CH Similarly, weak
will ionise a greater
some metals with dilute acid. have added
mixed to them
in thein the mole fi nal stages
ratioHCl(aq) before
shown + NaHCO by the
phenolphthalein
3(aq) reaction

arrows: NaCl(aq) equation.
NH(8.310) + (aq)
H2O(l) The + CO2(g)
strong base
3
presence NH of(aq) + H O(l)
reversible (aq) + OH +

form of different compounds, includingacid. 3 2 4

244 being
!
ItbyWeak
base
bases acid
to+judge     + H  
flreleased forsodium household use. has
Water
W
volume 813.2 of solution delivered H by (aq) the burette It isCH diffi
isatcult
known H O(l)how
asspectator
themany
titre.
protons (aq)can be(aq)donated

4
COOH(l) CH COO O +
sodium uoride
OH is usually(NaF),
considered to The
be a base. silicofl
sodium
O However,

uoride
and chloride +
ions are ions 3
in ionises
this reacti 2 3 3

summary looking aitscovalent


formula alone. Ethanoic acidthat (CH COOH) co
3

Water
W acid is base 9EAR
equivalence ispoint
Ammonia molecular compound in wate

titrate a strong acid of known concentration into the excess


it can act as a very weak acid by donating its

2 been shown that certain levels of


). fluoride
3
4 To minimise (Na 2SiFerrors,
6) and proton to the
calcium
form the very titration
strongionic
fluoridebaseCH O equation
(CaF
.COOH(aq)
2repeated is:Ethanoic
hydrogen
accepting several
aatoms,
2
proton.
acid is,
3 yet times
each
This ionisation
therefore, and
molecule can can
described the
be average
adonate
asrepresented
weak only
acid inone
by the
water. proton
equation

236 an ethanoate ion (CH3COO ) and is therefore a monoprotic acid

pH
in drinking
titre found. 246 water reduce dental
H (aq) +decay
HCO (aq) 12.5
Figure H O(l) + CO (g) + NH (aq) + H O(l) NH4+(aq) + OH
(aq)
6 Strong bases hydrogen 3 3that is part of the
2 highly polar 2OH bond is donated a

(unreacted) strong base


2
Figure 14.6 base acid
For example, in in
children. The fluoride is incorporated Comparison of tooth decay trends (decayed, missin
the reaction: a InWa 1 M solution, hydrochloric acid is virtually in water. In general, each hydrogen ion that is donated by an acid

1144
Water
4OOTHDECAY

Water Some generalisations can be made about the likely products of acid +use
that metal
fl carbonate
uoridated
salt +water.
or unfluoridated + ca
waterSource completely ionised in water. b However, in a 1 M The ionic compound
is involved in a very sodium oxide (Na
polar bond (Figure 2O) dissociates
14.8). in water, rele
into +the enamel ofthe NaCl(aq)
teeth, reducing solution of ethanoic acid, only a small proportion sodium ions (Na ) and oxide ions (O ). The oxide ions react comp
+ 2

(and vice-versa: the same thing can be done for weak bases) HCl(aq)
some reactions involving
4
acid + reactive metal
acids and
their
NaOH(aq)
bases:
susceptibility
246+ hydrogen
salt to attack by
+ H O(l)
acids.
acid + metal hydrogen carbonate
pH range for salt + wate
of ethanoic acid molecules are ionised. with the water, accepting a proton to form hydroxide ions (OH):
2
O2(aq) + H2O(l) OH(aq) + OH(aq)

1122
the equivalence
acid + metal point
hydroxide Fluoridation
salt +!WWater ofiswater
water reached supplies when the areactants
has been methyl
base acid
acidic oxide have
orange been
(3.14.4)
+ base salt mixed
+ waterin
The oxide ion is an example of a strong base. Strong bases accept pr
the mole
acid + metal oxide ratio given
controversial
salt + water by the
issue equation
in many
Aqueous solutions of bases are called alkalis.
(the
communities, stoichiometic
easily. ratio). At this point
n(HCl)2= n(NaOH) since similar = 1.effects
Calcium carbonate will react with acids, but is
not considered an alkali becausecan be achieved
it is insoluble
Sodium hydroxide is sometimes referred to as a strong base. How

Acid-Base Titrations
according to the BrnstedLowry definition of acids and bases, it is
Similarly,with in regular
thein water.
reaction:
use of fluoride toothpaste correct to say that sodium hydroxide is an ionic compound that is a so
orstrong base OH .
224 0 tablets.
of the

2HCl(aq) + Ca(OH) (aq) CaCl2(aq) Weak + bases


2H2O(l)
chemistryy in action !
Acids also react with many compounds such as metal hydroxides and
metal carbonates. A salt is again produced with each of these, together with

Water
W 2
0 Fluoride 10 to beto
is considered
added the 20
water inAmmonia
the is a covalent molecular 30
water. In the case of metal carbonates, carbon dioxide is also formed.

General reaction types involving acids OH is usually a base. However,


compound that ionises in wate


the equivalence point is reached
it can act as a very weak acid by donating its
when the mole ratio can n(HCl(aq) ) the: equation
There are numerous ways in which acids and bases react. It is possible,

proton to formvolume of Olife0.10 Mincluding


NaOH added (mL)
form ofand different compounds,
however, to group some reactions together on the basis of the similarity of

Acids in the environment in everyday


the very strong base . accepting a proton. This ionisation
2
be represented by
the reactants involved and products formed. As long as we remember that

use the indicators on page 5 of the formula booklet


TABLE 13.3 Tthe
ABLE 13.3 Some acids and
Some acids and Acids also react with many compounds such as metal hydroxides and
identifi
Acids cation of react
also reactionwith
products should be based on experimental data,hydroxides and
anions they produce againmany compounds
with each of such as metal

) =fluoride
metal carbonates. A salt istypes, produced these, together with

n(Ca(OH)2(aq) 2 : 1.(NaF), In this case,silicofl the uoride


equivalence point is reached when 
the anionsAcid
they produce these groups, or reaction can be useful.

   


Formula Anions metal
water. carbonates.
TheInfollowing
Asix
the case ofare salt
metal istheagain
carbonates,
of
produced
morecarbon
common
with
dioxide is alsoeach
reaction
of
formed.
types.
these, together with
For each

sodium sodium
Acid Formula Anionsproduced in water. Intype,
reaction theancase of metal
example is given.carbonates, carbon dioxide is also formed.

Figure 3.2.7 Titration curve for a strong acid with a strong base. base
General reaction types involving acids
NH (aq) + H O(l) NH (aq) + OH (aq)
reactions
produced in +
Sulfuric H2SO4 HSO4 and SO42
General
Reaction
reaction types involving acids
type 1 ways in which acids and bases react. It is possible, 3 2 4
9
reactions

n(HCl(aq) )(Na = 2n(Ca(OH) (aq) ). find(CaF


There are numerous
+ reactive salt + hydrogen
Sulfuric
Nitric
H2SO4
HNO3 NO
HSO4 and3 SO42
Acid
however, metalreactions
to group some together on the basis of the similarity of
acid

could use a pH meter for improved accuracy & precision SiF ) and calcium fluoride many). examples of the reactions of the types of reactions d
There
the are
reactants numerous
involved
includeand ways
Mg, Kin
products which
formed. acids
Zn butAsnot Cu,asand
long bases
weorremember react.
that It is possible,

2 We can
Hydrochloric HCl Cl
Reactive metals Ca, and Ag Au.

1144
TABLE 13.3 Some
Nitric HNOuoric
3
acids NOand identifi
Acids
however,
When cationalso
to
diluteof acids
reaction
react
group some
are products
with
added many should
reactions
to main be based
compounds
together
group metals,onsuch
on experimental
andthe as
some metal
basis data,hydroxides and
of the similarity of
transition
HF 3 F

Redox Titrations
the anionsHydrofl
they produce these groups, or of
reaction types, can be useful.and a salt is formed.
Hydrochloric Ethanoic
Acid
HCl
Formula Anions
CHCl
3COOH CH3COO

metals,
metal
the
water.
For
identifi
reaction
bubbles
carbonates.
reactants
The
In
following
example,
the
cation
type, case
an of
hydrogen
areA
involved
the
salt
six of
reaction
of metal
reaction
example
gas
and are
istheagainreleased,
moreproduced
products
between common
carbonates,
theproducts
is given.
formed. withAseach
reaction
dilute hydrochloric
longof
types. asthese,
acid For
and each
zinc
carbon dioxide is also formed.
equation: should be based on experimental data,
together with
we remember that
2 6 2
the environment and in everyday life:
metal can be represented by
Hydrofluoric HF Fproduced

in these groups, or reaction types, can be useful.
2HCl(aq) + Zn(s) ZnCl2(aq) + H2(g)
General reaction types involving acids
Reaction type 1 are six of the more common reaction types. For each

Consider now the titration of 20.00 mL of 0.10 M ethanoic


Figure 12.5acid (CH COOH)
reactions

Identifying the equivalence point


Ethanoic CH3COOH CH3COO The following
This + reactive
Acidreaction can metalalso be representedsalt +byhydrogen
an ionic equation. In aqueous
Sulfuric H2SO4 HSO4 and SO42 reaction
solution thetype, an example
hydrochloric acid is is given.
ionised and the zinc chloride (an ionic

The reaction between an acid and a metal oxide is used to remove


There
Reactive are numerous
metals include Ca,ways
Mg, Kinandwhich
Zn but acids
not Cu, and
Ag or bases
Au. react. It is possible,
Nitric HNO3 NO3
compound) is dissociated. The equation can therefore be written as:
however,
When dilute
Reaction to group
(aq)type
acids are
1
someadded reactions together
to main group metals,on andthe
somebasis of the similarity of
transition
3
NaOH. Ethanoic acid is a weak acid. Comparison of toothofdecay trends (dec
metals, 2H +
bubbles + of (aq) + Zn(s)
2Clhydrogen gas
are released, + 2Cl
Zn2+(aq)and a

(aq)is+formed.
salt H2(g)

with 0.10 M246 The product its reaction


the reactants involved and products formed. As long as we remember that
Hydrochloric HCl Cl Acid
TheFor
identifi +cation
reactive
example,
chloride ionof isthe
the metal
reaction ion.dilute
between
only spectator
reaction
VCEasy
salt
The + hydrogen
hydrochloric
ionic equation acid
is theand zinc
Acids low by theproducts
equation: should be based on experimental data,
F pH; sour taste; react be with bases
oxide from steel before soldering.
metal can represented
VISUAL

Strong Ac d Weak Ac d
Hydrofl uoric HF these groups,
Reactive metals or reaction
include types, can be useful.
Ca, ZnCl2Mg,(aq) +K H2and
(g) Zn but not Cu, Ag or Au.
of thetoCHEMISTRY
2HCl(aq) + Zn(s)
BasesCH
Ethanoic 3COOH high CH3COO pH; bitter taste; The following
Whenreact dilute with are are
acids six added
acids more
maincommon
group metals, reaction
and types. For each
some transition
thatuse fluoridated or unfluoridated wa

2.1.2
If the solutions being titrated are colourless, asis(CH
is
Water
W
often the). case in acidbase
This reaction can also be represented by an ionic equation. In aqueous

with NaOH is a weak base, ethanoate ion COO At the equivalence po


! reaction
metals, type,
solutionbubbles anofexample acid is
hydrogen is given.
gas areand released,
the zincand a salt
(anisionic
formed.

Calcium hydroxide used 3to reduce acidity in soils.


the hydrochloric ionised chloride
Hydrogen gas is produced from metals when
Indicators change colour
the acid solution depending
is dilute. Some acids give on the For
pH of
compound) example,
their the reaction
environment
is dissociated. The equation between dilute
can therefore hydrochloric
be written as: acid and zinc
Reaction betype 1 + Zn(s)by

could use acidified potassium


gases other than hydrogen when concentrated. metal can
2H+(aq) +represented
2Cl(aq) theZnequation:
2+
(aq) + 2Cl(aq) + H2(g)
BrnstedLowry theory

titrations, an indicator
themust be Magnesium
added
in thetoreaction
the reaction mixture to detect the bas
Acid +2HCl(aq)
reactive metal + hydrogen
saltionic

of this titration, products isflused


askto will include inthis weak
The chloride ion is+the only
spectator ion. The equation is therefore:
Zn(s) ZnCl 2(aq) + H2(g)

!
Acids are proton donors Reactive
This
2H+(aq) + Zn(s) Zn2+(aq) + H2(g)
metalscan
reaction include Ca,represented
also be Mg, K and Zn bybutan not Cu,
ionic Ag or Au.In aqueous
equation. hydroxide reduce acidity our stomachs.

11331
122
Whenthe
solution dilute acids are added
hydrochloric acid istoionised
main group
and the metals,
zincand some transition
chloride (an ionic
are proton acceptors

14
14
Basesgas is produced
Hydrogen from metals when Reaction type 2of hydrogen gas are released, and a salt is formed.

equivalence
hence thepoint (Chapter 4).7,
The
dueindicator must bebecause
chosen raincarefully to diox
metals, bubbles

Natural rainfall is slightly acidic dissolves carbon


compound) is dissociated. The equation can therefore be written as:

pH will be above to the reaction:


permanganate solution as an oxidant/
the acid solution is dilute. Some acids give Acid + metal hydroxide salt + water
gases other than hydrogen when concentrated. For example, the reaction between 2+ dilute hydrochloric acid and zinc
2H+(aq) +include
Metal can
hydroxides 2Cl(aq) + Zn(s)
NaOH, andZn (aq) +2. 2Cl(aq) + H2(g)
metal be represented byCa(OH)
the equation:
2 Mg(OH)
The hydroxide ions from metal hydroxides react readily with the
The chloride
ion,ion isZn(s)
the only spectator
(aq)ion.ofThe ionic equation
reaction is therefore:
1 produce carbonicatacid (H2CO3):the
2HCl(aq)
hydronium H++(aq),
from acids. ZnCl +H
The products (g)
an acidbase

ensure that the point during the titration which indicator changes
FULL EQUATION 2 2
Acid + Metal salt + H2 are a salt
IONIC EQUATION 2Hand
+ water.
(aq) + Zn(s) Zn2+(aq) + H (g)
ThisForreaction canreaction
example, the also be represented
between 2
solutions ofby an ionic
sulfuric acid andequation.
sodium In aqueous

CH COO (aq) + H O(l) CH COOH(aq) + OH (aq)


!

colour, calledindicator
hydroxidethe
solution can be represented by acid
hydrochloric the equation:
is ionised and the zinc chloride (an ionic

2
Hydrogen gas is produced from metals when

Equ va ence Equ va ence


compound)
Reaction is dissociated.
type
H SO (aq) 2
+ 2NaOH(aq) TheNaequation canO(l)
SO (aq) + 2H therefore be written as:

the end point, closely


COmatches the
equivalence
H CO (aq)point of the
Strong Base
!!
the acid
Acid solutionHydroxide
+ Metal is dilute. Some
acids
saltgive
+ H2O
2 4 2 4 2

3 2 3
Figure 13.10 (g) + H O(l)
gases other than hydrogen when concentrated. Acid +2Hmetal
The sulfuric(aq) + 2Clhydroxide
+ acid is ionised
in solution
(aq) + Zn(s) and
salt
both sodium +hydroxide
Zn2+(aq) water
+ 2Cland sodium
(aq) + H2(g)
sulfate are ionic and therefore dissociated in solution. Water, however, is a

1133
covalent
Metal
The molecular
ion substance
hydroxides
chloride isinclude that
the only does not
NaOH, ionise
Ca(OH)
spectator ion.toThe
any signifi
2 and
cant
Mg(OH)
ionic extent.
2.
equation is therefore: 2 2 2 3
3 Acid + Metal Oxide
So the equation becomes:
The hydroxide ions
+from metal hydroxides react readily with the
Natural rainfall is slightly acidic. reaction. With redox reactions (Chapter 5), the end point can often be
2H+(aq) + Zn(s)
+ SO4H + 2Na
Zn2+2OH
(aq) + H
(aq) +acids. 2(g)

hydronium
2H+(aq)ion, (aq),
(aq) from The
(aq) products of an acidbase reaction
2 +

po nt = pH 7 po nt > pH 7
2Na+(aq) + SO42(aq) + 2H2O(l)
236 are a salt and water.

4
The ionic equation is therefore:
Reaction typethe
For example, 2 reaction between solutions of sulfuric acid and sodium

224
Water
Acid + Metal Carbonate

identifi ed by a colour change in one of the reactants.


+ OH H2O(l)
H+(aq)can (aq)


Acid +
hydroxide metal behydroxide
represented salt + water
by the equation:
Figure 13.8

13
13
H2SO4(aq) +include
2NaOH(aq) Na2SO4(aq) + 2H2O(l)
Hydrogen gas is produced from the reaction of Metal hydroxides NaOH, Ca(OH)2 and Mg(OH)2.

5
some metals with dilute acid.
Acid + Metal Hydrogen Carbonate TheThe hydroxide
sulfuric ions from
acid is ionised metalandhydroxides
in solution both sodium react readilyand
hydroxide with the
sodium

To minimise the effect of errors, titrations are repeated several times and
hydronium
sulfate ion, H
are ionic and
+
(aq), from acids.
therefore The products
dissociated of anWater,
in solution. acidbase reaction
however, is a
236 are a salt molecular
covalent and water.substance that does not ionise to any significant extent.

6 Water
W
Water For equation
So the example, becomes:
the reaction between solutions of sulfuric acid and sodium

could also use acidified sodium


Acidic non-metal oxide + base


hydroxide+ can be represented by the equation:

13Weak
133 Base D ficu 238 the results averaged. Once the unknown concentration has been determined
2H (aq) + SO4 (aq) + 2Na (aq) + 2OH (aq)
2 +

o
H2SO4(aq) + 2NaOH(aq) Na22Na (aq) ++ 2H
SO4+(aq) SO24O(l)

Equ va ence
2
(aq) + 2H2O(l)

113
The sulfuric
The acid is ionised
ionic equation in solution and both sodium hydroxide and sodium
is therefore:
sulfate are ionic and therefore dissociated in solution. Water, however, is a

by volumetric analysis, the solution can be used as a standard solution for


H+(aq) + OH(aq) H2O(l)

dichromate solution
covalent molecular substance that does not ionise to any significant extent.

measu e yp ca y
Water
Figure 13.8 So the equation becomes:

13
131144 13
1 3
Hydrogen gas is produced from the reaction of

114
4 po nt < pH 7
2H+(aq) + SO42(aq) + 2Na+(aq) + 2OH(aq)

other titrations.
some metals with dilute acid.
2Na+(aq) + SO42(aq) + 2H2O(l)

236
Water
The ionic equation is therefore:
H+(aq) + OH(aq) H2O(l)
no done
1144
Figureand
13.8 bases: proton transfer; common reactions of acids; strong and weak acids

13 114
13
acids
Hydrogen gas is produced
and bases; polyproticfrom acids;
the reaction of
amphiprotic substances
some metals with dilute acid.

4 1413
1413
236

114
4
Water

13
13
volumetric
114
4 analysis including determination of excess and limiting reagents and
titration
13
13 curves: simple and back titrations, acid-base and redox titrations
VCEasy
Gravimetric Analysis VISUAL
CHEMISTRY
3.1.2
Measuring Water Content
Repeatedly heat and weigh until constant mass is achieved.
The mass lost was the mass of water in the sample.

Measuring the Mass of a Precipitate


Grind sample and dissolve in solvent.
Filter to remove the precipitate (using a vacuum pump) and air dry to constant mass.
The mass of precipitate in the original sample can now be measured.

Measuring the Mass of a Particular Ion Species


This method involves deliberate precipitation.
!
For example, to measure Cl ions, add excess AgNO3 to the sample.
An AgCl precipitate will form.
Measure the mass, find the number of moles of precipitate and calculate the number
of Cl ions in the original sample
!
The chosen precipitate must have:
known formula
low solubility
maintain stability when heated
not form precipitates with any other ions that are present

gravimetric analysis
6.02 10 = NA CHEMISTRY
a big number with 3 names = 1 mole 1.1.3 VCEasy
Calculating
Definition Amounts
1 mole is the no. of atoms in exactly 12 g of 12C VISUAL
CHEMISTRY
Mole Formula 1 Mole Formula 2 3.1.3
mass (g)
no. of moles
m no. of moles
no of atoms/ions/
(mol) particles/molecules/ 6.021023
(mol)

n=
anything

M N = n NA
molar mass (g/mol)

Empirical formula: simplest whole-


number ratio CH3 CH2O
Units of Pressure H2O
Units of Volume CO2VCEasy
Gases C H
1 atm 1 m3 VISUAL
actual number = 760 mmHg = 103 dm3 CHEMISTRY
Molecular formula: C H12O HO CO2 2.2.4
5
of atoms in the = 1.01310 Pa = 103 L
molecule 2 =6101.3 kPa 6 6= 106 cm32
= 1.013 bar = 106 mL

To find an empirical formula from mass composition:


Temperature All temperatures must be in kelvin.
conversion K = C + 273
Absolute zero is 0K or 273C, at
which particles stop vibrating

Avogadros Law Molar volume occupied by one


mole of gas at certain
Volume is proportional to number of moles volume (Vm) temperature and pressure

V1 n1 Two sets of temperature and pressure are

=
commonly used. Theyre called STP and
SLC and their details are all in the Chemistry
data booklet on page 5.

V2 n2
Boyles Law
Mmolecule
Combined gas equation
Extension: multiplyPressure
this ratio by to get
is inversely proportional to volumethe molecular formula
Combination of Boyles & Charles Laws
Mempirical

P1V1 = P2V2 1 1
the mole concept including empirical and molecular formulas, percentage
composition, Avogadros constant
P V P2V2
=
T1 T2
Charles Law Ideal Gas Equation
Volume is proportional to temperature (K)
constant in data book

V1 V2 pressure Volume no. of moles Temperature

= pV = nRT
T1 T2
calculations including those involving gas laws, molar volume (VM) at STP and SLC,
the General Gas Equation, volume-volume and mass-volume stoichiometry

calculations including amount of solids, liquids and gases; concentration; volume,


pressure and temperature of gases
Cl (g) + 2eto remember 2Cl (s)that an overall equation
each copper atom Worked
It that
is important is oxidised
example
2
16.2b loses two VCEasy electron
Write
When half
a equations
strip of
+ copper forelectrons
The this
wirechlorinereaction
is suspended
transferredthe
has therefore andwirebeen
identify
isin a the
solution
electrons
reduced. lostsubstances
inof thesilver
oxidation ox
nitr
Balanced Redox
each Ag (aq) ion When that Equations
a strip
the reduction is reduced
of copper
reaction. gains
suspended inone electron.
a solution of
VISUAL silver nitr
metal Ag
Two can+(aq) be observed. ions
metal
mustThe
In thesolution
can be observed.changes
therefore
example
The solutionto
of 16.2b be
copper and a
reduced thepale
changes to a blue
solution
pale blue
CHEMISTRY
to take
of colour
colou
silver u
Solution Worked
of Cu (aq) ions.
2+ example
3.1.4
of Cu (aq) ions. each copper atom that is oxidised loses two
VCEasy electron

OIL RIG
2+
by each copperanatom Write
When each
half that
equations
a strip
Agof(aq) copper
+ isionwire
for oxidised.
this
that
reaction
is suspended and
is reduced To
identify
ingains write
the
a solution
one
substances an
ofelectron.
silver ox
nitr
The
Write first
half half equationforTwo
equations forthis
metal this reaction
canreaction
be observed. and is for
The identifythe
solution
cat copper metal formi
the
changes substances
to a pale blue oxu
colou
this reaction, the Solution half Ag
of Oxidation
Cueach
equation
(aq)
+

(aq) copper
2+
ions.
ions must involving
therefore be the reducedVISUAL
reductio
to take

multiplied Cu(s)
he copper(II) ionsby
a factor
as these
by
Cu
The fi
Writeloss
collide. rst (aq)
halfof
2+ half
is Reduction
e 2 the +
equation
ofequations
2e
before
atom thisthat
for
forhalf
gain this
is is oxidised.
combining
reaction
of ereaction
is for
andinvolving the CHEMISTRY
identify theit
To write an
copper with
metal
substances oxt
formi
Solution this reaction, equation the reductio

The
setting up an apparatus as shown
oxidation
This represents
fi rst half
of Cu:
the
equation for
If oneCu(s)
multiplied
Solution
oxidation
oxidation
This
reactant
another
this
represents
by
reaction,is
reaction
of Cu: the
aisfactor
reduced.
oxidised,
Cu (aq)
is
oxidation
2+

since
of 2 +before
for the
reaction,
2e

each copper
since each
2.1.4
combining it with t
copper atom
metal
copper atom
has
formihas
ng copper(II) ions are in separate The first half equation for this reaction is for the copper metal formi
a Cu ion.of copper(II)
2+
e solutionCu(s)
ions, aCu 2+
Cu is ion.
2+
(aq)
Cu(s) + 2eCu (aq) + 2e
2+

Cu(s)
Redox
Half-Equations Cu
The 2+Cu(s)2.
second (aq) half + The 2e
equation (aq) + 2e series Oxidation
Cu 2+
electrochemical
involves

the aqueous silver ions is
Oxidation is
forming
The second +half forequation involves (aq) the + e aqueous Ag(s))silver ions forming ss
Cu is a reductant
Cu is a reductant
2 loss of
e
nometera (Ag meter (aq) detecting
+ eExamples: a (Ag Ag(s)) +
2 loss of e

na asolution
mples:silver nitrateofsolution
zinc chloride, is Thisalsorepresents (aq)the eoxidation
+equation reaction, since each copper atomis hasE
Reduction
TheAg Ag(s)
+
overall is: Ag is an oxidant
This represents the oxidation two ion.reaction, since Ag is each copper atom is has
gain of e

Reduction
Ag +
(aq) + ine thea Cu Ag(s)
2+
erofcrystals.
wire. The solutions
The The overall equation is: an oxidant
gain ofione forming

anThis represents half+the reduction reaction, since
(aq) each Agions has gains
+
2+ Overall
salt bridge Redox Equation
contains The
ionicsecond Cu(s) 2Ag
equation +
(aq)
involves Cuaqueous
the 2+
+silver
2Ag(s)
at bridge
Cu ion. between the solutions neutral
Example:
to silver
Will beatom. Will be
This
n a silverrepresents
The Cu(s)
nitrate
second solution
half + the 2Ag
equation reduction
+
(aq) Remember reaction,
(aq) +that
oxidised
Ag +
e
reduced

Cu since
in2+ both
(aq)Ag(s) each
half
+ andAg
Oxidised
2Ag(s) ionequations
+Reduced
overall has gain f
be something as simple as a piecethe number of atoms of each element present in thes
involves the aqueous silver ions forming
er crystals.
neutral
ssium
mple: nitrate. silver atom. WillThis
Will beNumbers
Oxidation Writing
be the
free represents
elements an
are zero
number
the 2 overall
(N ,reduction
He,
present
O etc) reaction,
2
onOxidised in the redox since each
is +3)reactants.
Reduced
equation
Ag ion has gain
Atoms
+
are cons
Remember that in both half and overall equations f
monoatomic ions = charge the ion (Al3+
c cell They oxidised
Ag
orhelp to +
(aq) + e oxygen
electrochemical
identify oxidants reduced
and
reductants in a reaction When

cell.
neutral
metals A =
weAg(s)
silver
valency
reactions.
= 2
atom.
(often
write
fluorine
+2)
= 1equations
hydrogen = +1for redox reactions, we nor
separates There the are oxidant fromin athe

1166
the number of
Six Big Rules:
atoms ofsumcharge
each
molecule, sum of oxidation number = 0
element onpresent in the
Writing an overall redox equation
half the total
equations fiofrst on
and the =product
then add
charge them ion side NO of
together the 1)toequa
get
He,Writing anon tooverall redox ofequation
in polyatomic ions, oxidation numbers (e.g. totals

into electrical energy. When this 3

This represents
free elements are zerothe (N2,reduction
ItO2istotal
etc) reaction,
charge
important the since
reactant
remember each sideAg
that an
+
the ionequation.
overall has
equation gain
Ch
the
monoatomic number
ions = charge present
onelectrons
thechemical
ionIonsintransferredthe
(Al 3+ the +3)reactants.
isreactions. electrons Atoms lost in are
the cons
oxidation
neutral
metals = silvervalency atom.
Balancing Redox Equations
(often +2) When we
Water write
(to balance equations
oxygens) for redox reactions, we nor
When
oxygenreactions.
Balance
= 2wefluorine
redox
write
equations in
= 1equations
this easy the
order:reduction
hydrogen
half
Protons
equations = +1
Electrons
(to
(addfor
reaction.
balance
fiasrst
manyredox
hydrogens)
and need) reactions,
as youthen add them together wetonor get
in a molecule, sum of oxidation It number
isIn the =example0 of copper and thatthe solution of silver
the total
half equations firstelectrons charge and on important
the
then to remember
product
addthat them side anof
together overall
the equation
equa
toelectron
get
Writing an overall redox equation
in polyatomic ions, sum of oxidation numbers
each copper = charge
atom on ion (e.g.
is oxidised NO totals 1)
lostloses two
3
transferredthe electrons in the oxidation
It istotal charge Apply on the reactant side of the gains equation. Ch
zinc strip
important to the remember
Redox
each
reduction Ag (aq)
Equations
+
reaction. ionthat
to Volumetric
that isan overall
reduced
Analysis equation
one electron.
TwoInAg the(aq)
+
example ions must of copper thereforeand the be solution
reduced of to silver
take u
electrons
ns
When chemical
use Ions
all
wethe
Water
same
write
(to
reactions.
transferredthe
equipment
Beaker B equations
balance
as a
byfrom:
oxygens)
titration
each copper
each copper electrons
(burette,
for pipette
atom
atom redox etc)
that
lost
that is
in
reactions,
is theloses
oxidised.
oxidised
oxidation
Totwo we
write nor
electronan
observe a colour change either
a dilute solution of
the
order:reduction
half the Protons
colour of (to
equations
the Electrons
zincreaction.
the
additionofzinc
balance
chloride this
fi
reactants
(add
an strip rst
as many
indicator.
hydrogens)
and reaction,
or products
each then
Ag
as you need)
(e.g(aq) theion
acidified
+
add half equation
them
potassium
that involving
together
dichromate
is reduced solution);
gains onethe
to reductio
orelectron.
get
multiplied
Two Ag (aq) + byions a factor mustoftherefore
2 beforebe combining
reduced to it withtake tu
It isInimportant the example by
ofeach
to oxidation
remember copper of Cu:and
copper thatthe
atom thatanissolution
overall
oxidised. To
of
equationsilver
write an
K Electrochemical Series SEE DATA
Mg each copper
electrons transferredthe atom that
this reaction, is
Cu(s) electrons
the oxidised
half
Cu (aq)
2+
lost
equation loses
+ 2e

ininvolving
the two electron
oxidation
the reductio
BOOK
Zn multiplied by
When a+ factor
eyou ofAg(s))
connect 2 before
anytwo 2 combining
half-cells with it witha t
the each
Fe reduction Ag
the stronger (aq)
zinc+chloride
reaction.
reductants
solution
(on top) can reduce
ion that
the oxidation ofwire
(Ag is (aq)
+
reduced
Cu:and a salt bridge:
gains one electron.
Sn
TwoCu In the(aq)
Ag + underneath
metals
example ions must ofThe copper
Cu(s)therefore
overall
and
reaction equation on top be
Cu (aq)
2+the reduced of
is: forwards
goes
+ solution
2e
to silvertake u
by Au
each
each
xidationreduction copper
copper
reactions. atomatom that
(Agthat
Cu(s) (aq)
+ + 2Ag
is ise (aq)
+
+oxidised
the writing of balanced chemical equations, including the use of oxidation numbers

oxidised.
Cu (aq)
Ag(s)) 2top
2+

loses To two write


+ 2Ag(s)
one gets reduced
electron to
an
this
devicewrite
eachreaction,
in which
om a spontaneous
redox chemical
Ag
gravimetric analyses
+
(aq)
equations,the andhalf
energy
ion
redox reactionthe
theRemember
that
The equation
application
is
overall ofthat
reduced
equation in involving
chemical both half and
is:gains
equations
is number of atoms of each element present in the one the
overall
to volumetric reductio
equations
electron.
and f
bottom one gets oxidise
multiplied
onverted into+electrical by energy.
a factor of
Cu(s) 2 + before
2Ag +
the number present in the reactants. (aq) combining
Cu 2+
(aq) + 2Ag(s)
Atoms it with are const
s the VCEasy
Thin Layer Chromatography (TLC) VISUAL
CHEMISTRY
All chromatographic techniques have:
3.1.5a
u are mobile phase (aqueous)

her a
desorb continuous
process adsorb stationary phase (solid)

t can
ns A
Solvent front
m the
the

reen
10 cm
rom 7 cm

ause 3 cm
oved X
, the Origin

ts. 3
Rf (blue component) = 10 = 0.3
ance
Rf (red component) = 7 = 0.7
d by 10

To identify the components of the mixture, compare the Rf


values of each spotFigure
against6.3
a set of standards.
Calculation of the Rf values of components on a
chromatogram.
principles and applications of chromatographic techniques (excluding features of
instrumentation and operation), and interpretation of qualitative and quantitative data
from: !thin layer chromatography (TLC), including calculation of Rf
4 5 56 2-methylhexane
7

VCEasy
Recor
HPLC & GC High Performance Liquid Chromatography
1 2 4
3
&1Gas Chromatography
butane
5 VISUAL
CHEMISTRY
Recorder response

2 2-methylbutane

3.1.5b
3 hexane

0No need to learn how the machines work


4 benzene
5 2-methylhexane
5 10 15 Figure 6.12 20
Results graphs
Number of carbon atoms
look very similar
Time (min) Chromatogram of a reference sample
containing a mixture of butane, 2-methylb
4 5 6 hexane, benzene and 2-methylhexane.
7
0 5 10 15 20
Time (min)
Number of carbon atoms 4
4 5 1 2 6 7

4
Recorder response

1 2
Recorder response

3
3
5 5

Figure 6.13
Petrol sample spiked with benzene.

0 5 10 15 20
Time (min)
Number of carbon atoms
0 4 55 6 10 7 15 20
Retention timeTime (min)
(min) (Rt)
Example 6.3
Number of carbon atoms
Each 4 compound 5 has a unique retention time 6 7
The concentration of benzene in a sample of petrol was determined by gas chromatography.
A series of standards with an accurately known concentration of benzene were run under the
same conditions asPeak
Example 6.3 area tells you the
the sample. You need a calibration curve to
concentration
The chromatogram of each
of the sample and thecompound convert
standards is shown in Figure 6.14. peak areas into concentration
The concentration of benzene in a sample of petrol was determined by gas chromatography.
A series of standards with an accurately known concentration
8.0 of benzene were run under the
(Fig
same conditions as the sample. the
(cm2)

The chromatogram of the sample and the standards


6.0 is shown in Figure 6.14. the
area
area
Peak

4.0

06
06
Figure 6.14
can
Peak

Chromatogram of standard samples of be


and an unknown sample.
Sample Tog
0.2% 0.4% 0.8% 1.2% Sample
2.0
qua
info
0.2 0.4 0.6 0.8
and
1.0 1.2 Chromatograp
Concentration of benzene (%) Ch

Figure 6.15
Calibration(excluding
principles and applications of chromatographic techniques graph for benzene
featuresinofpetrol.
instrumentation
and operation), and interpretation of qualitative and quantitative data from: high performance liquid
0.2%
chromatography 0.4%
(HPLC) and gas chromatography0.8%(GC) including1.2%
Rt and the use ofSample
a calibration
graph to determine amount of analyte
nstruments.
e element
The energy of a photon of light emitted by an excited electron VCEasy ha
AAS equal
xed value,
Atomic Absorption Spectroscopy
to the difference in energy between the CHEMISTRY VISUAL ene
higher
vel and the lower energy level to which it returns. The light consequen
as a specific wavelength and colour. Electrons in an atom can
3.1.6a
be excited
Absorption Emission
electron is promoted to
of energy a higher energy level

Energy
emitted

slit select Detector measures


avelength pulsed light

Sample
Energy from absorbs light of
the flame promotes then re-emits
The electron quickly the energy
returns to a as
certain wavelengthslevel.
an electron to a higher energy >1 energy
lower photons with
level, shorter
emitting light
of a particular colour.
wavelengths

Absorbance

10 Calibration graph shows the


absorbance at a certain wavelength
8
of standard solutions

6
owing is an Sample
4
processor.
was filtered 2 Absorbance of
standard solutions
thode lamp
A significant
5 10 15 20
Concentration of lead (ppm)
nt solutions
re graphed Figure
principles and applications 7.14
of spectroscopic techniques (excluding features of instrumentation and
operation), and interpretation of qualitative and quantitative data from: atomic absorption
The variation
spectroscopy (AAS) including of transitions
electron absorbance and against
use of calibration graph to determine amount
. Are these
of analyte concentration, showing measurements for the
VCEasy
IR Infra-Red Spectroscopy VISUAL
CHEMISTRY
acid the broad absorption band from 2700 cm1 to 3600 cm1 is due to 3.1.6b
the OH bond. This broad absorption band partly masks the absorption
due to CH bonds. The C=O stretch in propanoic acid produces a peak
at a different wavenumber from the C=O stretch in methyl ethanoate.
a 100
90
Fingerprint Region
80
(%)

70
Transmittance (%)
transmittance

60
50
broad
40 O H

30
20
narrow Noisy signal
10 C H C O Unique for every compound
0
4000 3000 2000 1500 1000 500
wavenumber (cm
Wavenumber (cm1
1
))
b 100
90
80 Look up the wavenumbers on page 7 of the data
booklet and find their corresponding bonds
70
Transmittance (%)

60
50 C H

40
30
20
10
C O
0
4000 3000 2000 1500 1000 500
Wavenumber (cm1)

Figure 7.29 and applications of spectroscopic techniques (excluding features of instrumentation and
principles
operation), and interpretation of qualitative and quantitative data from: infrared spectroscopy (IR)
Infrared spectra of a propanoic acid and b methyl ethanoate.
including use of characteristic absorption bands to identify bonds
VCEasy
1H NMR Spectroscopy Proton Nuclear Magnetic
VISUAL
Resonance Spectroscopy
CHEMISTRY
Analyses environments of hydrogen 3.1.6c
The energy required to excite a nucleus to a higher energy level (by
changing the nucleus magnetic alignment) depends on the atoms
ion theenvironment.
NMR spectrum ofEach
ethanol shows more detail.
environment hasThea unique nuclear shielding effect.
protons is split into three fine peaks, while the peak due
is spit into four fine peaks (Figure 7.43b).
Spectrograph
b
ethanol H H 3H
CH3
3 Things to Look Out For
C H
H

CH2
O
H
C
H 1 chemical shift (ppm)
Tells you the environment of those protons (CH , NH , etc) 3 2
2H

area under peak (e.g. 2H)


for calibration
purposes
HO 2
1H TMS Tells you how many protons are in that environment
3 mini peaks minus one
Tells you how many neighbouring protons there are
Only visible on high-resolution
spectrographs. Low-resolution NMR
spectrographs dont have mini peaks.

5 4 3 2 1 0
Chemical shift (ppm)
Interpretation
3 protons are in a CH3
Example
H H
ctrum2ofprotons
ethanol. are in a resolution
b High
environment and they
CH2 spectrum of ethanol showing
have peak splitting.
2 neighbours
neighbouring C H
environment and they protons are bonded H
have 3 neighbours 1 proton is in an OH
environment and it has to adjacent carbon O C
f peaks caused by splitting equals n + 1, where n is the
ms on the neighbouring atoms, i.e.:
no neighbours
atoms. this proton has H
ignal from hydrogens attached to adjacent atoms into two
two neighbours H
13
C NMR spectroscopy
signal from hydrogens
Carbon-13 attached
is a naturally occurring to adjacent
isotope atoms
of carbon that into spin. It
has nuclear

within
signal from
13C
a molecule.
hydrogens NMR Spectroscopy
is used in NMR spectroscopy to identify different carbon atom environments
The chemical shift to
attached fromadjacent
the TMS reference
atoms isinto
dependent
Carbon Nuclear Magnetic
on a carbon atoms environment within a molecule. Chemical shifts range Resonance Spectroscopy
from 0 ppm to 200 ppm (Table 7.10). The peaks in the spectrum are a single
line produced for each different carbon atom environment.

Analyses environments of carbon


providesThe H NMR and
information
1
about
13
C NMR spectra for agroup
the functional particular compound are
to which
different. The 1H NMR spectrum for ethanol, CH3CH2OH, was given in
H is attached
Figure 7.43b; the 13C NMR spectrum is shown in Figure 7.50. The proton
ives information
NMR shows three about the
sets of neighbouring
peaks protons
representing the three different hydrogen
e information
environments.about the number
The carbon-13 of equivalent
NMR shows hydrogenthe two
two peaks respresenting

Just 1 Thing to Look Our For


carbon atom environments.
CH2 CH3

1 chemical shift (ppm)


Tells you the environment of those carbons (CH , CH , etc) 2 3
CH3 CH2 OH
for calibration
cine in the form of magnetic resonance imaging (MRI). The MRIpurposes
an NMR machine; the patient takes the place of the sample and is
TMS
of the huge magnet.
bundant source of protons. MRI measures the amount of time it
ns to relax back to the lower energy state. This time is different for
tissue200and 180
bone. 160
Normal140tissue 120 gives
100a different
80 response
60 40 from
20 a 0
Chemical shift (ppm)
mputer is used to analyse the data and present a coloured image
The MRIFigure
scan7.50shows repeated sections through the body as the
Carbon-13 NMR spectrum for ethanol.
d deeper into the machine. MRI can be carried out on a patient who
eact to stimuli. This allows the technique to show a unique picture
as the patient is shown images, hears sounds, carries out mental
he like.
as a resultlt off proton
t andd Each
E h peakk in i an NMR spectrum
t represents
t a different
diff t chemical
h i l
have an overall spin when environment.
an odd number. principles andThe area under the peaks
applications indicates the proportion
of spectroscopic of atoms in(excluding features of instrumentation and operation), and interpretation of
techniques
field with the qualitative
magnetic andeach environment. data from: proton and carbon-13 nuclear magnetic resonance spectroscopy (NMR) including spin, the
quantitative
in nuclear magnetic
application of The frequency atto
carbon-13 which a nucleus absorbs
determine number radiation relative to
of equivalent carbon environments; and application of proton NMR to determine
he identity and structure the absorption of the TMS standard is called the chemical shift.
structure: chemical shift, areas under peak and peak
The chemical shift is characteristic of an atoms environment.
splitting patterns (excluding coupling constants), and application of n+1 rule to
simple
ei align with or against an compounds
The peaks in high resolution proton NMR spectra may be
e external field are at a split into a cluster of peaks. The amount of splitting provides
light that passes through the sample.
VCEasy
UV-Visible Spectroscopy
Narrow
beam VISUAL
CHEMISTRY
Two main uses: 3.1.6c
Identifying unknown compounds
Finding the concentration of a known
Lightcompound
source
Monochromator
(wavelength
selector) Sample
Worked example 7.4 Slit solution
TheAbsorbance
concentration of iron in a sample of dam water was determined by UV spectroscopy.
Iron present as Fe2+ ions was reacted to form anEach compound
orangeyellow
Figurecomplex,
7.15 has a unique UV-
iron(II)-1,10-
visible
phenanthroline. The absorbance of a series of standards absorption
and aEssential
sample of of aspectrum.
dam water
elements is shown
simple This
UVvisible spectrophotome
in Table 7.5. Determine the concentration of iron in the dam water in g mL (ppm).
1
example is chlorophyll.
TABLE 7.5 Usually the substance under investigati
spectrophotometer in a special cell made o
Concentration Fe2+ (g mL1) Absorbance
to ultraviolet and visible light. With a simp
Sample Because 0.38
green
reading is firstlight
takeniswith
not aabsorbed
cell containing
4.0 0.16
8.0
(it iscompensate
reflected),
0.31
forplants containing
any refl ection, scattering or
and the solvent.
chlorophyll The reference cell is then
12.0 0.47appear green.
solution of the sample. The absorbance by
16.0 0.63
300 400 500 600 700 the two readings. By measuring the abso
Wavelength (nm) graph, or spectrum, for the sample can be
Solution The characteristic spectrum of chlorop
The fiFigure is to construct a calibration graph with the dataModern
rst step7.16 from Table analytical laboratories now us
7.5. See Figure
7.18. Thespectrum
Visible concentration of iron isChlorophyll
of chlorophyll. plotted on the horizontalbeam
axis andscanning
the absorbance on the
spectrophotometer (Figu
vertical axis.strongly in the violet (420 nm) and red
absorbs beam of light is rapidly chopped and
(660 nm) regions of the spectrum, so it appears
reference and sample cells. of This
a compens
at a particular wavelength

green
0.7 in colour. To find the concentration
the radiation source and enables the absor
0.6
known compound, construct a
0.5
calibration graph then compare
Rotating mirror
(beam chopper)
your sample with that.
or
ot
Absorbance Absorbance

0.4
!
M

0.3
Unlike the example above, the
0.2
absorbance
Radiation at one particular
Monochromator Sampl
source
0.1 wavelength is measured.
Slit
0
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
Concentration Fe2+ g/mL
concentration
Mirror
Figure 7.18 Referen
Calibration graph for iron in a sample of dam water.
principles and applications of spectroscopic techniques (excluding features of instrumentation and
operation), and interpretation of qualitative and quantitative data
Figure from: visible and ultraviolet
7.17
spectroscopy (visible-UV) including electron transitionsEssential and use of calibration
elements graph
ofaahorizontal
double to determine
beam scanning spectropho
The observed
amount of analyte
absorbance of the sample is located on the vertical axis and
line drawn to intercept the calibration graph. A vertical line isthrough the to
dropped sample and the reference cells by the rotating
the concentration
Relative a
40 VCEasy
Mass Spectroscopy VISUAL
CHEMISTRY
20
Analyses m/z ratio of a molecule and its fragments
mass-to-charge ratio, which usually
corresponds to the relative molar
3.1.6e
mass of the molecule or fragment

10 20 30 40 50 60 70 80 90 100 110
Mass/charge

Fragmentation M + e M+ + 2e
Interpreting the mass spectrum sample + bombarding electron parent molecular ion + two electrons

43
100
CH3CO +
45
90 base peak COOH+
80 60
CH3COOH+
70
M+, parent
Relative intensity

60 molecular ion

50

40
30
20 15
CH3+ 42
10 29 CH2CO+
COH+

10 15 20 25 30 35 40 45 50 55 60 65 70
m/e

Figure 8.3
The most informative result from
Simplified mass spectrum of ethanoic acid.
mass spectroscopy graphs is the
relative molecular mass of the
The height of the peak in the massparent molecular
spectrum gives the ion.
relative concentration
of the ions present. In Figure 8.3, the highest peak, the base peak, has a
Also look for
fragment a peak
mass of 43at and
15, which
is assigned an intensity of 100%. The intensities of
indicates a
all other peaksCH group.
3 are measured relative to the base peak. In some spectra the

peak with the highest intensity is also the parent molecular ion. In other
spectra, such as that of dichloromethane, the peak corresponding to a smaller
fragment may be the base peak. Smaller ions formed by fragmentation are
usually present in smaller amounts.
The relative intensities of the ions depend on:
the energy of the bombarding electrons
the stability of the ion fragments formed
principles and applications of spectroscopic techniques (excluding features of instrumentation and
the ease
operation), andwith which of
interpretation ions can lose
qualitative atoms. data from: mass spectroscopy
and quantitative
including determination of molecular ion peak and relative molecular mass, and identification of
simple fragments
molecular ion

VCEasy
49
100
84

Analytical Techniques
80
CH2Cl+ CH2Cl2+

Relative abundance
TABLE 2.5 Solubilities of common ionic compounds 60

VISUAL
Weigh the peanut butter
sample, blend and filter.
High solubility Low solubility 40 VCEasy
Mass Spectroscopy
CHEMISTRY
Compounds containing the following ions Compounds containing the following ions VISUAL
Add an excess of silver CHEMISTRY
are generally soluble in water: are generally insoluble, unless combined 20

ed theNaorigin.
+
, K+, NH4+, The
NO3, CH3COO with Watchglass
Na+, K+ or NH4used
+
: as a cover
nitrateAnalyses m/z ratio,ratio
solution to precipitate of a molecule and its fragments 3.1.6e Figure 8.2

3.1.7
Cl ions as silvermass-to-charge
chloride. which usually Mass spectrum of dichloromethane.
corresponds to the relative molar
mass of the molecule or fragment

Cl, below
e plate Br, I (unless
the combined with Ag+ or CO32, PO43, S2, OH (unless combined 10 20 30 40 50 60 70 80 90 100 110
Mass/charge
Pb )
2+
with Ba or Sr ; Ca(OH)2 is slightly
2+ 2+
M + e M+ + 2e
e sample
SO42 spot, the and BaSO
(except PbSO ; Ag2SO4
Thin-layer soluble) Solvent front Fragmentation
Filter the white precipitate of
Interpreting the mass spectrum
silver chloride.
sample + bombarding electron parent molecular ion + two electrons
4 4
ransported
and CaSOup 4
are the
slightly soluble)plate 43
coated 100
milar technique is with Wash the90precipitate with a
1 2 CH3CO+
base peak
45
COOH+
1 2

er chromatography alumina
small volume
80 of water. O (m = 45)

Recorder response

Recorder response
60
CH3COOH+
(stationary 70
es up the plate the M+, parent +C Acid

Relative intensity
phase) Dry the precipitate in an
60
3
molecular ion
4
O H
3 4
50 Repeat
Origin oven at 100C. Loss of CH3
x x x 40 these 5 5
steps until +
A B C Solvent 30 Molecular ion
O

ayer and
the mass is
(mobile phase) Weigh
20 the 15
AgCl+
CH3 constant. 42 CH3 C Figure 6.11
precipitate.
10 29 CH2CO+
COH+ Gas
O chromatogram
H of a petrol sample.
m = 60
10 Flame20colour25
15 30 35 40 45 50 55 60 65 70 Flame colour
0 5 10 m/e 15 20 0 5 10 15 20
Figure 6.2 Figure 2.7 Sample adhering
Time (min) Loss of COOH
Sample adhering
Time (min)
ed on the plate in Vacuum pump
Thin-layer chromatography of three different NumberSteps in the
of carbon analysis
8.3 toofwire
atoms
Figure the chloride content in Number
Loss of OHof carbon atoms to wire
peanut Simplifi
butter.ed mass spectrum 5 The
4 of ethanoic acid. most informative result
6 from 7 4 5 6 7
matography.
Conical
food colours (A, B and C). A number of mass spectroscopy graphs is the CH3CO+ (m = 43) CH3+ (m = 15) flask
Indicator
chemicals once used as food colours are now relative molecular mass of the
e identified in two Loss of H
The height of the peak in the massparent molecular
gives the ion.
1 2 4 4 1 2
regarded as hazardous and can be detected by spectrum relative3concentration 3
CH2CO+ (m = 42)
of the ions present. In Figure 8.3, the highest peak, the base peak, has 5 a 1 Burette is 2 Pipette delivers a 5
this method. 1 butane
Recorder response
known volume of 1 butane3 Indicator has 4 The end point has

Recorder response
filled with
Also look for
fragment massa peak
an intensity of 100%. The intensities of at and
of 43 15, which
is assigned
romatogram as the
1 Weighing the sample 2 Forming a precipitate 3 Filtering the solution 4 Weighing the dry precipitate
indicates
all a CH3 group.
other peaks
2 2-methylbutane
Burner
are measured relative to the base peak. In some spectra the Figure 8.4
Burner one reactant. the other reactant
into flask.
been added.
2 2-methylbutane
been reached.

3 hexane Fragmentation of ethanoic acid. Only the 3 hexane


peak with the highest intensity is 4also the parent molecular ion. In other
benzene fragments corresponding to the major peaks of 4 benzene

Figure 2.6
+ Cheap High Conc. Needed Water Content spectra, such as that of dichloromethane, 5 2-methylhexane + Sensitive
the peak corresponding
fragment may be the base peak. Smaller ions formed by fragmentation are
Volatilesto a smaller
(e.g. flavours) the mass spectrum are shown. Figure 3.5
Figure
Expensive
Steps in an acidbase titration.
6.12
5 2-methylhexane Acids & Bases,
Oxidants & Reductants + Cheap High Conc. Needed
Key steps in gravimetric analysis. usually present in smaller amounts.
mical that you are
Gravimetric Analysis Mass Spectroscopy Volumetric Analysis
Chromatogram of a reference sample
The relative intensities of the ions depend on:

08
08
2 Th The other h solution
containing a mixture ofl butane, is d
dispensed d slowly
l l into the
2-methylbutane, h titration flask k from
f a
find out whether a ! principles
the energy of the bombarding electrons
the stability of the ion fragments formed hexane,
3 The
burette.
benzene and 2-methylhexane.
equivalence point is the point during the titration when the solutions
Worked example 2.4a
vitamin tablet can the
and applications of spectroscopic techniques (excluding features of instrumentation and
ease with which
Note that this analysis 5calculates only the
operation), and interpretation ions
of can lose
qualitative and atoms.
quantitative data from: mass spectroscopy have been mixed in the mole ratio shown by the reaction equation. The
0 including determination of molecular ion peak and 10relative molecular mass, and15identification of 20 0 volume of5 solution delivered by 10 the burette is known as15 the titre. 20
each of vitamins A
Infant cereals should not contain more than 0.3% sodium chloride (common salt). A 7.802 g amount
Figureof 7.5
chloride
simple present. Other tests would
fragments Time (min) Figure 7.5
4 To minimise
113 errors, thehas titration
Time (min)
Figure 7.4 ofPerforming
Numberbe required
carbon a fldemonstrate
to
Figure
atomsame
7.4 test. A moist
thatwire hasall
it was been Number
Combining and choosing ofPerforming
carbon
analytical a flame
atoms
techniques test. A moist wire been is repeated several times and the average
sample of baby cereal was blended with Solvent
water front
and filtered. The solution obtained was mixed
distance from the Metal ions incorporated in the fireworks are responsible for the colours in this display. dippedMetal
sodium in theions
chloride sample
and and
not theninplaced
4 potassium
incorporated in 5the are
the fichloride
reworks or responsible for the colours6in this display. 7
titre found.
dipped in the sample and 4 then placed in 5the 6 7
with excess silver nitrate solution, causing silver chloride to precipitate. The precipitate was flame. A fine spray of the solution from a spray some other salt. flame. AForfineexample,
spray of theinsolution
the reaction:
from a spray
samples, then
collected by thedried and weighed. A mass of 0.112 g was obtained. What is the
filtration, bottle could be used instead. bottle could be HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
used instead.
1 2 4 1 2 4
percentage of These
sodium shells,
chloridealso
in the babyenergy
called food, assuming thatelectrons
levels, and all the chloride is present
in these shells,asare These shells, also called energy levels, and electrons in these shells, are the equivalence point is reached when the reactants have been mixed in
the mole ratio given by the equation (the stoichiometic ratio). At this point
C is sodium
the same located at different distances from the nucleus. The negatively charged
green
chloride? located at different distances from the nucleus. The negatively charged
Recorder response

Recorder response
n(HCl) = n(NaOH) = 1.
electrons are attracted to the positively charged protons 10 cm in the nucleus by electrons are attracted to the positively charged protons in the nucleus by
ameSolution
distance from attraction.
electrostatic
chemfact
electrostatic attraction.
Similarly, in the reaction:
7 cm 2HCl(aq) + Ca(OH)2(aq) CaCl2(aq) + 2H2O(l) The
3 3
The full equationElectrons in energy
for the reaction is: levels close to the nucleus have the lowest energies Electrons
When a reaction occurs in inenergy
solution,levels close to the nucleus have the lowest energies
only ions
5 can jump the equivalence point is reached when the mole ratio n(HCl(aq) )5 : Figure 7.
AgNO3(aq) and
matogram
experience the strongest attraction to the nucleus. An electron can jump
+because
NaCl(aq) AgCl(s) + NaNO3(aq) that areandinvolved
experience the strongest
in the reaction Nucleus: inattraction
appearcontains
an to the nucleus. An electron
n(Ca(OH)2(aq) ) = 2 protons
Nucleus: contains
: 1. In this
and case, the equivalence point is reached when
to a higher energy level if it absorbs energy
Alternatively, this may be written as an ionic equation:
3 cm
that corresponds exactly to the ionic to a higher
equation. energy
Other protons and
level
ions present
neutrons
if
areitcalled
absorbs energy that corresponds exactly to the n(HCl(aq) ) = 2n(Ca(OH) neutrons (aq) ). all Awavele
Figure 3.6
pipette must
he distance moved
2
difference in energy between the lower energy level and the higher energy spectator ions andinare
difference energy
omitted. between the lower energy level and the higher energy Figure 6.13 those
pipette emi
filler. W
Ag+(aq) + Cllevel. AgCl(s)
(aq) When X
owed to travel, the electrons jump to a higher energy level they move to a higher
Origin To convert
level.a Whenfull equation to an1stionic
electrons jump
shell to a higher energy level they move to a higher PetrolIdentifying
sample spiked with the1st equivalence
shell
benzene. point the meniscus s
light that
Calculating the amount
energy in molinof aAgCl
subshell present
different in the For
shell. precipitate:
some metal atoms, the heat of a equation,
energy first rewrite
subshell it within the soluble
shell ionicshell. For some metal atoms, the heat of a
a2nddifferent 2nd shell
If the solutions being titrated are colourless, as is often the case in acidbase
tween the
n(AgCl) = spots.
m(AgCl)
Bunsen
=flame 0.112 g sufficient energy for this3to happen.
provides
= 0.000 781 mol
0 compounds
Bunsen dissociated into ions.
flame5 provides Ions
suffithat
3rd shell cient10energy for this to 15
happen. 20 0
titrations, an
5
indicator
3rd shell
must be
10
added to the reaction
15
mixture to detect the
20
1Rfare
(blue component) = 10 = 0.3 Time (min) Time (min)

UV-Visible Spectroscopy
Higher143.4
energy levels unstable so the excited electrons quickly return remain inHigher the solution and are
energy unchanged
levels at
are unstable so the excited electrons quickly return
fied by theM(AgCl)
distance g mol
to lower energy levels,Remitting the energy they
Number of carbon atoms
the Figure
end
to oflower
the reaction are then deleted fromthe energy they had
equivalence point (Chapter 4). The indicator must be chosen carefully to
Number of carbon atoms
= 7 had absorbed. If the energy energy 4 levels, emitting 6 absorbed. If the7 energy
7.6 5 Figureensure
7.6 that the 4 point during 5 the titration at which the indicator
6 changes 7
From
stance the equation,
travelled 1 mole of NaCl yields 1
(red mole of AgCl.
component) = 0.7
emitted by f 10
falls within the band of energies visible to the eye, it can be seen both
A sides
simplifi edof the equation.
representation of For
the the reaction
arrangement in
emitted falls within the band of energies visible to the eye, it can be seen A colour,
simplifi ed called
representationtheof end
the point,
arrangementclosely matches the equivalence point of the
n(NaCl) 1 of electrons
Worked Examplein a sodium
2.4a: atom. Higher energy reaction.
of electrons Withatom.
in a sodium redox reactions
Higher energy (Chapter 5), the end point can often be
mponent: = as coloured light (Figure
+ Cheap
7.7). Radiation emitted
Inaccurate
n(AgCl) 1electromagnetic spectrum, such as the ultravioletDyes,
from other
region,Amino
parts
Acids
is detected
of the
using
Example Agshells
+
as
(aq)
coloured
6.3
that
+ NO are not
electromagnetic
light
(aq)occupied
+ Na+(aq)
(Figure
by electrons
+ Cl(aq)
spectrum,
7.7).
are
Radiation emitted from other parts
+ Sensitive
Low-Molecular
such as the ultraviolet region,
of the
Mass usingExample 6.3
identifi
shells that edoccupied
are not by a colour changeare
by electrons in one of the reactants.
Expensive High-Molecular Mass
+ Sensitive Two main uses:
Expensive
not shown. (In3 Unit 1 you learned
AgCl(s) + Na+(aq) that electrons
+ NO (aq) OrganicisCompounds
detected not shown. To minimise
(In Unit the effect
1 you learned of errors, titrations are repeated several
that electrons Organictimes and
Compounds
= 0.000 781 mol Figure 6.3
instruments. instruments. Identifying unknown compounds

0
n(NaCl) = n(AgCl) The concentration of benzene in ainsample
a more 3of petrol was determined by gas chromatography. The concentration of benzene in Once
ainsample of petrolconcentration
was determined bydetermined
gas chromatography.

02
02
are now thought to be distributed are nowthe results
thought averaged.
to be distributed the unknown
a more has been
simplifi es to

TLC GC HPLC
m(NaCl) = n(NaCl)Theenergy
M(NaCl)of a photon Calculation
of lightof emitted
the Rf values
by anofexcited
components on ahas aA seriesAgofcomplex
electron The
fashionenergy
+ standards
than shown
with an of a photon
here.
accuratelyWithin eachof light emitted by an excited electron has a
known concentration of benzene were run under the
A series complexby
of standards
volumetric
fashion than shown
with an
analysis, the solution
here. Within
accurately each
known
can be used as a standard solution for
concentration of benzene were run under
fixed value, equal to the difference in energy between the higher energy shell, + Cl (aq)
(aq)electrons
fixed

are
value, AgCl(s)in energy levels
arranged
equal to the difference in energy between the higher energy other titrations.
shell, electrons are arranged in energy levels Lightthe Finding the concentration of a known com
chromatogram.
= 0.000 781 mol 58.5 g mol 1
= 0.0457 g same conditions as the sample.
called subshells.) same conditions as the sample.
called subshells.) source
level and the lower energy level to which it returns. The light consequently level and the lower energy level to which it returns. The light consequently
has a specific wavelength and colour. Electrons in an atom can be excited to The chromatogram
has a specifiofc the sample and
wavelength andthe standards
colour. is shown
Electrons in aninatom
Figurecan
6.14.
be excited to The chromatogram of the sample and the standards is shown in Figure 6.14.
Worked example 7.4
23 TheAbsorbance
concentration of iron in a sample of dam water was determined
onary phase moves Energy
emitted
Analysis by mass Energy
emitted Iron present as Fe2+ ions was reacted to form anEach compo
orangeyellow
Figurecom
7.
phenanthroline. The absorbance
ProtonofNuclear
a series of standards VCEasy
visible absor
and aEssential
sample of
ele
1H NMR Spectroscopy Magnetic
VISUAL
itions under which in Table 7.5. Determine the Resonance
concentration of iron in the dam water in g
Spectroscopy
example
CHEMISTRY is c
ues of components Analyses environments
TABLE 7.5 of hydrogen 3.1.6cUsuall
substances under The energy required to excite a nucleus to a higher spectroph
energy level (by
Concentration Fe2+ (g mL1) Absorban
can be identified. Figure 7.7 changing the nucleus
Figure 7.7 6.14 magnetic alignment) depends on the atoms
to ultravio

006
076
At high resolution theenvironment.
NMR spectrum Figure
ofEach
ethanol shows more detail.
environment hasThe
a unique
from nuclear shielding effect.

07
07 07
During a flame test, electrons jumping from During a flame test,Sample
electrons jumping
Because 0.38
greis
nd food dyes Energy
thefrom the flame promotes Chromatogram oflevel
standard samples of benzene
peak due to CH3 protons is split into three fi ne peaks, while the peak due
The electron quickly returns to a Energy
a high to a low from
energy thelose
level flame promotes
energy by The electron quickly returns to a
to CH2 protons is spit into four a fihigh to a low
ne peaks (Figureenergy
7.43b). lose energy by reading
an electron to a higher energy level. lower energy level, emitting light an electron to a higher energy level. lower energy level, emitting light Spectrograph and an unknown sample.
4.0 0.16
olourless and must of a particular colour. emitting coloured light.
0.2% 0.4% 0.8%
a
of a particular
1.2% colour.
Sample
Peak area 2 :
0.2%
ethanol
1 : 3
0.4%
8.0CH3
b emitting coloured light.
3 Things
0.8% to Look
1.2% Out CH
For H (it is reflecte
SampleH compensa
0.31 3H
3

and the so
C H

appear blue when 1 chemical shift (ppm) chlorophyll 0.47a


H
H OH O C

79 12.0 79
Tells you the69
H
environment of those protons (CH , NH ,solution
H

o
H C C H CH2 CH2

the chromatogram Spectroscopy


H
Ethanol
H
H O
16.0 Spectroscopy2 area under peak (e.g. 2H)
2H
etc)
0.63
for calibration
purposes
3 2

ured or fluorescent 300 Chromatography 400 500you how many


Tells 600 protons are in700
HO
that environment
1H
the two r TMS

3 mini peaks minus one graph, or Only visible on high-resolution

Wavelength (nm)
spectrographs. Low-resolution NMR
spectrographs dont have mini peaks.

Solution Tells you how many neighbouring protons there are


The ch

06
06
5 4 3 2 1 0 5 4 3 2 1 0

s no longer critical Chemical shift (ppm) Chemical shift (ppm)

graphH withH the


Example

+ Sensitive Expensive MetalsVCEasy + Sensitive Expensive Metals + Easy The fiFigure rst step is to Conc.
construct a calibration Low-Molecular Mass
dataModer
from Ta
Interpretation
Figure 7.43 High
7.16 Needed
neighbouring
3 protons are in a CH3
Organic Compounds
(the Rf value) stays
environment and they
C H
IR Infra-Red
a Low resolution NMR spectrum of ethanol. b High resolution spectrum of ethanol showing peak splitting. 2 protons are in a CH2
Spectroscopy VISUAL 7.18. Thespectrum
Visible concentration of of iron
chlorophyll.
protons isChlorophyll
plottedHon the horizontalbeam
are bonded
environment and they axis andsca
have 2 neighbours
the

Atomic Emission Spec Atomic Absorption Spec UV-Visible


chemfact have 3 neighbours 1 proton is in an OH
O C
omatogram is run CHEMISTRY Peak splitting acts over small distances only.
The number of peaks caused by splitting equals vertical
n+ absorbs axis.
1, where nstrongly
is the to adjacent
in the violet (420
atoms.
carbonnm) and red
environment and it has
no neighbours
beam
H of this proton has

1 3.1.6b
number of H atoms on the neighbouring atoms, i.e.:
(660atoms nm)intoregions of the spectrum, so it appears H
s canacid
be compared
The interacting hydrogens must be bonded to two neighbours
CH splits the signal from hydrogens attached to adjacent two
reference
at a particular wavelength

the broad absorption band from 2700 cm to 3600 cm is due to


1 adjacent atoms. For example, CH OCH OCH
T peaks
7.10 Carbon-13 chemical C NMR spectroscopy
3 2 3

green in colour.
13
To find the c
63 1H NMR Spectroscopy
shows no spinspin coupling and peak ABLE

the OH bond. This broad absorption band partly masks the absorption splitting because the hydrogens are not shifts
VCEasy
CH splits the signal from hydrogens attached to adjacent 0.7 atoms into
Carbon-13 is a naturally occurring isotope of carbon that has nuclear spin. It
2
the radiat
Proton
joined Nuclear
to adjacent
by an oxygen atom.
atoms; theyMagnetic
are separated three peaks
13 Carbon type Chemical shift
(ppm)
VISUAL C NMR Spectroscopy
Carbon Nuclear Magnetic
is used in NMR spectroscopy to identify different carbon atom environments

known comp
due to CH bonds. The C=O stretch in propanoic acid produces a peak CH splits within
the signal froma molecule. The chemical
hydrogens attachedshift to
fromadjacent
the TMS reference
atoms isintodependent
Resonance Spectroscopy RCH3 3 827 on a carbon atoms environment within a molecule. Chemical shifts range
0.6 Resonance Spectroscopy
Chromatography RCH2R four peaks.
CHEMISTRY
2750 from 0 ppm to 200 ppm (Table 7.10). The peaks in the spectrum are a single
at a different wavenumber from the C=O stretch in methyl ethanoate.
Analyses environments of hydrogen
!
R3CH In summary:
RCH2(F,Cl,Br,I) chemical
The H in OH groups doesnt split the peaks of R CNH
3760

the hydrogen
3570 3.1.6c
line produced for each different carbon atom environment.
1278shift providesThe H NMR and
information
H is attached
1

1
about
13
C NMR
Analyses environments
spectra for agroup
the functional
0.5 of carbon
particular compound are
to which
different. The H NMR spectrum for ethanol, CH3CH2OH, was given in
calibration g
a your sample
3 2
adjacent H atoms, nor is its own peak split, for R CH OH Figure 7.43b; the 13C NMR spectrum is shown in Figure 7.50. The proton
100 3 2
5088
peak splitting gives information
NMR shows three about the
sets of neighbouring
peaks protons
representing the three different hydrogen
Fingerprint Region
reasons that are beyond this course.
The energy required to excite a nucleus to a higher energy level (by RCCR 7798
peak areas give information
environments. about the number
The carbon-13 of equivalent
NMR shows hydrogenthe two
two peaks respresenting
Absorbance Absorbance

CN 115133
90 carbon atom environments. 0.4
changing the nucleus magnetic alignment) depends on the atoms
At high resolution theenvironment.
NMR spectrum ofEach
ethanol shows more detail.
R2C=CR2
atoms. 108150 CH2 CH3 Just 1 Thing to Look Our For !
80 environment hasThea unique nuclearchemistry
shielding effect.
y in action
RCOOH 160220
peak due to CH3 protons is split into three fine peaks, while the peak due
0.3 chemical shift (ppm) Unlike , CH , etc)the ex
(%)

70
to CH2 protons is spit into four fine peaks (Figure 7.43b).
Spectrograph Magnetic resonance imaging 1
Transmittance (%)

Tells you the environment of those carbons (CH


3 Things to Look Out For
2 3
a Peak area 2 : 1 : 3 b CH3 CH3 CH2 OH
transmittance

0.2(MRI). The MRIpurposes


absorbance
60 CH3 ethanol H H 3H for calibration
NMR is used in medicine in the form of magnetic resonance imaging
H
C H
Radiation
chemical shift (ppm)
H OH O C scanner is effectively an NMR machine; the patient takes the place of the sample and is
50 H 1 rolled into the opening of the huge magnet. TMS
source
wavelength
!
broad H C C H
H H
CH2 CH2 H
Tells you the environment of those protons
Refer to the (CH 3,The
NH
VCE Chemistry body
Data , etc)
2Book is aan
for full abundant source of protons. MRI measures the 0.1
amount of time it
40 O H H O 2H

area under peak (e.g. 2H)


for calibration listing of C chemical shifts. 13
Ethanol purposes takes for excited protons to relax back to the lower energy state. This time is different for
HO 2 protons in fat, muscle, tissue200and 180 bone. 160
Normal140tissue 120 gives
100a different
80 response
60 40 from
20 a 0

30 tumour. A powerful computer is used to analyse the data and present a0coloured image
Chemical shift (ppm)
1H TMS Tells you how many protons are in that environment
scan7.50shows repeated sections through the0body as 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
20 3 mini peaks minus one ofspectrographs.
Onlythe
visiblepatients

patient
body. The MRIFigure
on high-resolution
Low-resolution NMR Carbon-13 NMR spectrum for ethanol.
the
is slowly moved deeper into the machine. MRI can be carried out on a patient who Concentration Fe2+ g/mL
spectrographs dont have mini peaks.

concentration
4 Noisy signal Tells you how many neighbouring protons there are 7.6
narrow 5 3 2 1 0 5 4 3 2 1 0 summaryis conscious and can react to stimuli. This allows the technique to show a unique picture
10 C H C O
Chemical shift (ppm) Chemical shift (ppm) of the working brain as the patient is shown images, hears sounds, carries out mental
Unique for every compound Interpretation
3 protons are in a CH3
Example
H H
arithmetic tasks, and the like.
0 Figure 7.43 environment and they neighbouring At
Atomici nuclei
l i produce
d a magnetic
ti field
ld as a resultlt off proton
t andd Each
E h peakk in
i an NMR spectrumt
Figure
represents
7.18
t a different
diff t chemical
h i l
4000 3000 2000 1500 1000 a Low resolution NMR spectrum2ofprotons
500 ethanol. are in a resolution
b High CH2 spectrum of ethanol showing
have peak splitting.
2 neighbours C spin. The nucleusHwill always have an overall spin when
neutron environment.
environment and they protons Figure bonded H
are 7.44 the number of protons plus neutrons is an odd number. principles andThe
Calibration
area under the peaks
applications
graph
indicates the proportion
of spectroscopic
for iron in a sample of dam water.
of atoms in(excluding features of instrumentation and operation), and interpretation of
techniques

07
07
chemfact have 3 neighbours 1 proton is in an OH
O The Cexternal magnetic field with the qualitative
interaction of an magnetic andeach environment. data from: proton and carbon-13 nuclear magnetic resonance spectroscopy (NMR) including spin, the
wavenumber (cm
Wavenumber (cm1
1
)) The number of peaks caused by
environment and it has
splitting equals n + 1, where n is the to adjacent carbon
An MRI scan of a human head.
field of the nucleus of an atom is used in nuclear magneticapplication of The
quantitative
frequency attowhich principles
a nucleus absorbs radiation and
relative to applications
carbon environments; of and spectroscopic
application of proton NMRtechniques (excludin
spectroscopy to H
Peak splitting acts over small distances only. no neighbours carbon-13 determine number of equivalent to determine
atoms. this resonance
proton has determine the identity and structure the absorption of the TMS standard is called the chemical shift.
b 100 The interacting hydrogens must be bonded to
adjacent atoms. For example, CH3OCH2OCH3
number of H atoms on the neighbouring atoms, i.e.:
CH splits the signal from hydrogens attached to adjacent atoms into two
two neighbours
of a compound. H structure: chemical
operation),
shift, areas under peak
The chemical shift is characteristic
The magnetic fields generated by nuclei align with orsimple
and interpretation of qualitative and quantitative data
and peak splitting patterns (excluding coupling constants), and application of n+1 rule to
of an atoms environment.
against ancompounds
The peaks in high resolution proton NMR spectra may be Figure 7.
peaks 13
C NMR spectroscopy 100 spectroscopy (visible-UV) including electron transitions and use
Essential
verticalelea
TABLE 7.10 Carbon-13 chemical external field. Nuclei aligned against the external field are at a split into a cluster of peaks. The amount of splitting provides
90 shows no spinspin coupling and peak
splitting because the hydrogens are not shifts CH2 splits the signal from hydrogens
Carbon-13 attached
is a naturally occurring to adjacent
isotope atoms
of carbon that into spin. It
has nuclear Chemical analysis
C
higher energy level than those aligned with the external field.
Electromagnetic radiation in the radio frequency range causes
The observed absorbance of the sample is located on the
information about the number of hydrogens attached to
amount of analyte
adjacent carbon atoms. The interaction between protons
80 RangeLook up the wavenumbers on page 7 of the data 13
Expensive +CSensitive
NMR Spectroscopy
Expensive
Carbon Nuclear Magnetic
+ Sensitive Expensive line isthrough the
joined to adjacent atoms; they are separatedCarbon type three peaks
Chemical shift
line drawn to intercept the calibration graph. A vertical
Organic Molecules dropped
booklet and find their correspondingOrganic Molecules Organic Molecules
is used in NMR spectroscopy to identify different carbon atom environments
+ Huge of Analytes by an oxygen atom. (ppm)
CH splits the signalwithin
froma molecule. The chemical
hydrogens shift to
attached fromadjacent
the TMS reference
atoms isinto
dependent
nuclei to move to a higher energy level. on adjacent atoms that causes the peaks to split is called

bonds RCH 827 3 on a carbon atoms environment within a molecule. Chemical shifts range Resonance Spectroscopy The external magnetic field experienced by an atom within a spinspin coupling.
four peaks.
axis and the concentration in the sample from the dam water is read fro
3
molecule is modified by the magnetic field of neighbouring Analysis of an NMR spectrum involves consideration of:
70 RCH R 2750 from 0 ppm to 200 ppm (Table 7.10). The peaks in the spectrum are a single the number of peak sets
Transmittance (%)

2 atoms.
In summary:

IR 1 of carbon H NMR 13C NMR


R3CH 3760 line produced for each different carbon atom environment.
! The energy required to excite a nucleus of an atom to a higher the chemical shift of each peak set
1278shift providesThe
Analyses environments The dam water was not diluted before being treated and analysed so
RCH2(F,Cl,Br,I) chemical 1
H NMR and
information about
13
C NMR spectra for agroup
the functional particular compound are
to which the relative area under each peak set
60 energy level depends on the arrangement of atoms within a

07
07
iron in the dam water was 9.9 g mL1 or 9.9 ppm Fe2+. Interpre
The H in OH groups doesnt split the peaks of R CNH different. The 1H NMR spectrum for ethanol, CH3CH2OH, was given in
3 2 the hydrogen
3570 H is attached
Figure 7.43b; the 13C NMR spectrum is shown in Figure 7.50. The proton
molecule or the atoms environment. peak splitting.
adjacent H atoms, nor is its own peak split, for R CH OH
50 C H reasons that are beyond this course. 3 2
5088
peak splitting gives information
NMR shows three about the
sets of neighbouring
peaks protons
representing the three different hydrogen
RCCR 7798
peak areas give information
environments.about the number
The carbon-13 of equivalent
NMR shows hydrogenthe two
two peaks respresenting
CN 115133 carbon atom environments. 104
atoms.
Just 1 Thing to Look Our For In ultravi

07
07
40 R2C=CR2 108150 CH2 CH3 Chemical analysis
C
RCOOH 160220
chemistryy in action
30
1 chemical shift (ppm) 7.4 light by a
20
Magnetic resonance imaging
CH3 CH2 OH
for calibration
Tells you the environment of those carbons (CH , CH , etc) 2 3 summary is drawn.
NMR is used in medicine in the form of magnetic resonance imaging (MRI). The MRIpurposes
10
C O scanner is effectively an NMR machine; the patient takes the place of the sample and is
rolled into the opening of the huge magnet. TMS
concentra
0 !
4000
3000
matching analytical technique/s to a particular task: single and combined
2000
Wavenumber (cm )
1500
1
1000
86 Th
The unique
i b techniques.
ti spectrum
t200 off compounds
180 d in
TheData
listing of 13C chemical shifts.

i the
160 th
body
500 abundant source of protons. MRI measures the amount of time it
Refer to the VCE Chemistry is aan
Book for full

takes for excited protons to relax back to the lower energy state. This time is different for
absorption
protons in fat, muscle, tissue and bone. Normal tissue gives a different response from a 0
140 120 100 80
Chemical shift (ppm)
60 40 20

tumour. A powerful computer is used to analyse the data and present a coloured image
of the patients body. The MRIFigure
scan7.50shows repeated sections through the body as the UVvisible
Chemicalregion
C can be used to identify unknown
analysis
Carbon-13 NMR spectrum for ethanol.

Figure 7.29
principles and applications of spectroscopic techniques (excluding features of
patient is slowly moved deeper into the machine. MRI can be carried out on a patient who
instrumentation and
7.6 substances.
summaryis conscious and can react to stimuli. This allows the technique to show a unique picture
operation), and interpretation of qualitative and quantitative data from: infrared spectroscopy (IR) brain as the patient is shown images, hears sounds, carries out mental
of the working
Infrared spectra of a propanoic acid and b methyl ethanoate.
including use of characteristic absorption bands to identify bonds arithmetic tasks, and the like.
At
Atomici nuclei
l i produce
d a magnetic
ti field
ld as a resultlt off proton
t andd Each
E h peakk in i an NMR spectrum
t represents
t a different
diff t chemical
h i l
neutron spin. The nucleus will always have an overall spin when environment.
Figure 7.44 the number of protons plus neutrons is an odd number. principles andThe area under the peaks
applications indicates the proportion
of spectroscopic of atoms in(excluding features of instrumentation and operation), and interpretation of
techniques
The interaction of an external magnetic field with the qualitative
magnetic andeach environment. data from: proton and carbon-13 nuclear magnetic resonance spectroscopy (NMR) including spin, the
quantitative
As the structure of a compound becomes more complex the number of
An MRI scan of a human head.
field of the nucleus of an atom is used in nuclear magnetic The frequency at which a nucleus absorbs
application of carbon-13 to determine number of equivalent radiation relative to carbon environments; and application of proton NMR to determine
resonance spectroscopy to determine the identity and structure the absorption of the TMS standard is called the chemical shift.
structure: chemical shift, areas under peak and peak splitting patterns (excluding coupling constants), and application of n+1 rule to
vibrational modes increases. Acrylonitrile (propenenitrile, Figure 7.30) is of a compound.
The magnetic fields generated by nuclei align with orsimple
The chemical shift is characteristic of an atoms environment.
against ancompounds
The peaks in high resolution proton NMR spectra may be
100 external field. Nuclei aligned against the external field are at a split into a cluster of peaks. The amount of splitting provides
A carbon backbone is the longest CC
anic Molecules
Molecules chain
chain in in a molecule.
a molecule. VIS
VISUAL
VCEasy
und Naming
is a compound
a compound
Organic Compounds
made mostly
made mostly from Cfrom
and C
H.and H. organic
Some Some organic CHEMISTRY
CHEM
CHEMISTR
VISUAL
have functional
nctional groupsgroups attached
attached (such
(such as OHasorOH
NHor
2).NH2). 3.2.1 1.2
1.2.3
aies is a series
series of organic
Backbone of organic
& Functional Groups compounds
compounds with similar
with similar chemical chemical
functional
onal group)group)
ane inand
and which
ene in which
each
amine eachchloro
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ane ane ane
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saturated, all
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alkenes
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contains C=C
amines
NH chloroalkanes bromoalkanes
Cl group 2
Br group
iodoalkanes
I group
alkanols
OH group
carboxylic acids
COOH group

meth methane doesnt methanamine chloromethane bromomethane iodomethane methanol methanoic


1 carbon exist acid
eth ethane ethene ethanamine chloroethane
Sidechainsethanol
Sidechains
bromoethane NamingNaming
Rules R
ethanoic
iodoethane
2 carbons acid
a.k.a. branching
a.k.a. branching
prop propane propene propanamine chloropropane bromopropane iodopropane propanol propanoic
3 carbons acid
methane
hane
H4 but
CH4
4 carbons
butane butene butanamine chlorobutane bromobutane iodobutane Find1.the
1.butanol Find
acid
the c
carbon
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backbone backbone
ethane
hanepent pentane penteneethene ethene
pentamine chloropentane bromopentane iodopentane pentanol pentanoic
acid
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3CH3 CH3CH3 CH2=CHCH 2 2=CH2
hex hexane hexene hexanamine chlorohexane bromohexane iodohexane 2.hexanol 2. hexanoic
Number Number
those t
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panepropane propenepropene carbonscarbons
hept
H2CH 33CH2CH3heptane CH2=CHCH
heptene CH23=CHCH
heptanamine 3
chloroheptane bromoheptane iodoheptane heptanol heptanoic
7 carbons acid
butane octane
taneoct octenebutene butene
octanamine chlorooctane
H H H
bromooctane
H
iodooctane
3.octanol
Label3.H sidechains
LabelH side
octanoic H
8 carbons acid
2 CH23CH32CH2CH3 CH2=CHCHCH22=CHCH
CH3 2CH3 H H
C C C + BrC Br + Br Br C C C
non DONE!
nonane nonene nonanamine chlorononane bromononane iodononane DONE!
nonanol nonanoic H
ntane9pentane
carbons pentenepentene H H H H Br
acid
Br Br
CH
H23CH 22CH32CH2CH
dec 3
decane CH
decene CHdecanamine
2=CHCH 22=CHCH CH2CH3
CH2CH32chlorodecane bromodecane iododecane decanol
decanoic
10 carbons acid
Figure 8.20 Figure 8.20
xane hexane hexene hexene Addition
Addition of bromine of bromine to ethene.
to ethene.
23 CH22CH22 CH32 CH 2CH CH22=CHCH
3 CH2=CHCH CH2CH22CH32CH2CH3
Sidechains Examples This in
This reaction, reaction, in which
which the the red-brown
red-brown colour of colour
bromine of disa
bro
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it reacts with with the
the alkene, is alkene,
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ermulae three examples
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H H 8.21). It involves conversion H
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methyl hexyl H 1 H 1H 3 of reaction
H is known is
H known
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an addition additionC
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C H H
1 carbon 6 carbon
C HC CH H
C H C C H H
Figure 8.21 Figure 8.21 2 CReaction 2 2
C with hydrogen gas H
H ethyl
H Testing forheptyl 2 Reaction with Chydrogen + Br C gasBr + Br Br
H
H C H
4
2 carbons 7
Testing forAdding
unsaturation.
carbons H unsaturation.
a few HCAdding a few C C 4 C 4 H C
H HC C C
drops ofbromine
drops of red-coloured
H red-coloured
to hexane 2
bromine to hexane In the
2H
In
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H presence
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heating, heating,
ethene ethene
3
reacts withre 3
CH (right) produces no reaction. The colour in HH gas toethane.
produce
H H A ethane. HH A hydrogen atom
atomHhas bonded C
C Br hastobondedofto
(right) produces
propyl octylno reaction. The colour in H gas to produce hydrogen each
Br Br t
5 the sunfl5ower the(left)
oil sunfldisappears
ower oil (left) disappears almost
almost atoms on either
atoms on either side of the double C side of the double C
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carbons
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H H
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molecules Hin the
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Figure 8.20
single bond. single H H H
bond.
butylsunflower oil
nonyl
sunfl ower oil contain carbon-to-carbon
contain carbon-to-carbon double double Addition of bromine to ethene.H H
H bonds which
4 carbons bonds which
9 carbons
undergo undergo
addition Hwith reactionsHwith
addition
reactions
Addition of bromine to ethene.
bromine (Br2). bromine (Br2). H H H H H H H
pentyl decyl Computed by WolframAlpha

2,2-dimethylpropan
Computed by WolframAlpha

e 5 carbons 10 carbons 2-methylbutane


2-methylbutane
Computed by
it reacts with
C
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WolframAlpha
the
reaction,
which the
alkene,
C C + HC is
in which
used H
2,2-dimethylpropane
red-brown
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Figure 8.21 when writing
molecular,
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for equations for
structural
the position and
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Alkenes 2 Reaction
2semi-structural
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withformulae,
hydrogen hydrogen
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International
Testing reactions
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so that
Testing
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the position
forAdding
for unsaturation. a fewof Adding
unsaturation.
Chemistry (IUPAC) Figure 8.22 Figure 8.22
nomenclature
added added atoms can be clearly shown. Hof alkanes, H alkenes,
H amines,
H haloalkanes, H H H
dropsatoms can be clearly
drops
of red-coloured shown.
ofbromine
red-coloured bromine
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the presence thetoof
of hydrogen presence
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ethenecatalyst
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reacts withre
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(right)
2n+1 alkanoic
produces no acids
reaction.
(right) produces no reaction. The colour in The (C
colour in
n H COOH)
gas to produce
2n+1 and esters
gas toethane.
produce up to
A ethane. C10
hydrogen A atom
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has bonded tobonded
Heach oftoth
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1. bromine
Add bromine solution C + Br C Br + Br
the(left)
sunfldisappears
ower oil (left) disappears almost Br
1. Add solution
the sunflower oil almost C
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side of theside of the
double double
bond, bond, converting
converting C C
the C=C the
dou
immediately
immediately because because
molecules 3 Reaction
3 Reaction with steam
with steam
molecules in the
in the
H
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Figure 8.21
C backboneH the products formed when
C 3 Name 2 backbone
H
C ethene reacts with:

VCEasy
ethene 2 Reaction with hydrogen gas H
+ Br Br
Testing for unsaturation. Adding a few C
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C 4 hydrogen C C
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H drops of red-coloured bromine to hexane
2 CH =CH
22 H

Organic Reactions
2. Numberatoms b thosechlorine 2. Number H the C=Cthose
(right) produces no reaction. The colour in H gas to produce
H ethane. H A hydrogen H atom has C Br to each Br
bonded of the carbon
the sunflower oil (left) disappears almost on either side of the double C H H
c water bond, converting double bond
H propene
immediately because moleculesHin the C H
carbons
CH =CHCH3 d Additionhydrogen
sunflower oil contain carbon-to-carbon double
to aFigure
carboncarbon
8.20 single bond.
of bromine to ethene. H
H H
carbons VISUAL
bromine (Br2).
2 Hwith
bonds which undergo addition reactions
4 Use structural H formulas H to write equations and H name the Hproducts for the reactions of:
for addition polymerisation are unsaturated molecules. The double bond
C
CHEMISTRY
C

3. byLabel H sidechains the red-brown 3. colourLabel H sidechains

3.2.2
Computed by WolframAlpha

2-methylbutane a This reaction,


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Addition Reactions of Alkenes


Polyethene: an addition polymer

!C CH 2=CHCH2CH b but-2-ene with hydrogen bromide


H 3 8.21). It involves conversion of the double bond to aHsingle bond. H
C
This type
Polyethene was discovered by accident in the laboratories of ICI in Cheshire,
England, in the 1930s when some oxygen entered a container of ethene by
chemfact
C + Br Br C C C C + Br Br C C
DONE! 5 Polyethenol H isis Husedas toanmake soluble hospital Hlaundry bags. H The structure of the
accident. At first, the white waxy solid produced was considered a failure.
of reaction known addition reaction.
DONE!
Then further testing found it to be chemically unreactive and an excellent Polythene is an ICI (UK) trademark.
Structural formulas of reactants and products H H
Figure 10.9
insulator. It was first used to make cables and insulate radar aerials during

Properties pentene Alkenes


World War II. The equation for the formation of polyethene is:
are Figure
usually 8.21
used when writing equations for
addition
monomer
2 Reaction ethenol
with is shown
hydrogen
The in
gasFigure 10.9. Draw the
nC2H4(g) (C2H4)n(s)
structure of a section
ethene molecule contains a double bond between two carbon atoms of Structure of ethenol.
Testing reactions so that Adding
the position
a fewof the
for addition polymerisation are unsaturated molecules. The double bond
H unsaturation.
for Br H Br
Figure 8.22 H Br Br
H3
andformed
so can undergo addition polymerisation. In the process of addition

can beCH 2=CHCH 2CH2CH3the


between the two carbon atoms reacts and new covalent bonds are

added
dropsatoms clearly
of red-coloured shown.
bromine to hexaneDefinitions
Polyethene: an addition polymer
polymer.
InAddition
the H
presence
of hydrogen toofethene
H
a catalyst and on
in the presence catalyst. VCEasy
between carbon atoms on nearby molecules, creating long chains.polymerisation, all of the atoms present in the monomer molecules are
of a heating,
H
ethene H
reacts with hydrogen
present in the polymer molecules. The empirical formula of the polymer
is the same as that of the monomer. The monomers simply add to the

In Chemistry, plasticgas to produce ethane. A hydrogen a property.atom has bonded HVISUAL to each of the carbon
!
20 (right) produces no reaction. The colour in Figure
= ductile
ever-growing chain until it reaches its final length in a fraction of a second
8.20 Plastic
+ malleable.
Polyethene was discovered by accident in the laboratories of ICI in Cheshire,
(Figure 8.24). is an adjective; When a covalent molecular solid such as
England, in the 1930s when some oxygen entered a container of ethene by
CHEMISTRY
1. Add bromine
hexene solution
chemfact have a backbone of carbon atoms with, on
+ Br PVC Brand Nylon.
the sunflower oil (left) disappears almost polymer is a type of material
accident. At first, the white waxy solid produced was considered a The
atoms on C that includes
C
polyethene molecules
either
failure.
side of polythene,
the double bond, converting Cthe C=C C
double
ice is heated, it changes from a solid to a
bond
romine to immediately
ethene. because molecules in the Addition of bromine to ethene.
liquid quite suddenly at 0C. The size of the

1.2.6a
Then further testing found it to be chemically unreactive and anaverage, 150 000 Polythene
carbonis atoms
an ICI (UK)in each molecular chain, although in any
H
3toareReaction with steam
excellent trademark. molecules prevents a polymer from undergoing
particular
insulator. It was first used to make cables and insulate radar aerials during sample of polyethene, the sizes of the molecules will vary.
Polymers made from repeating
a carboncarbon single bond. monomer units bonded
Brown covalently.
Polyethene is the simplest of polymers because only hydrogen atoms are
a similar change of state. The molecules are

CH
!
CH =CHCH CH CH CH
World War II. The equation for the formation of polyethene is: too entangled to move freely in the manner

3 sunflower oil contain2carbon-to-carbon2double2


nC2H4(g) (C2H4)n(s) bonded to the carbon atoms in the chain. It is a thermoplastic polymer, of water molecules. Polymers do not have a

2 Large 3 amounts
The ethene molecule contains a double bond between two carbon whichH Colourless of ethanol H are now made by the Br
means it can be heated again and reshaped. This is because the bonds
atoms
addition reaction
Colourless Br of steam
defined melting temperature. If they soften, they

bonds which undergo addition reactions with


and so can undergo addition polymerisation. In the process of additionthe non-polar chains are weak dispersion forces. As the polymer is do so over a broad temperature range. This
between
class of polymers is sometimes described as

eaction,bromine in which the red-brown Polymers colour of(H O(g))Hreaction,


bromine
This and ethene
disappears Husing
insugar asa phosphoric
which the acid
red-brown catalyst isHcolour (Figure 8.23).
of bromine disappears as
polymerisation, all of the atoms present in the monomer molecules heated,are the molecules gain kinetic energy and the polymer chains can slide thermosoftening or thermoplastic.
(Br2). =! 8.20
present in the polymer molecules. The empirical formula of the polymer
over 2
one another, breaking the weak dispersion forces. The strong covalent

10.3
is the same as that of the monomer. The monomers simply add to within
the H
Figurebonds
Fermentation
the polymer molecule are unaffected.
of(Figure
with the alkene, is used as a generalH test for it Addition
reacts
unsaturation with tothe alkene,to isproduce used asethanol a general still used
test fortounsaturation
make beer, (Figure
ever-growing chain until it reaches its final length in a fraction of a second

O(g) 2. Add hydrogen gas


(Figure 8.24).
of bromine ethene.
When a covalent molecular solid such as
H
2examples
The polyethene molecules have a backbone of carbon atoms with, on ice is heated, it changes from a solid to a

awine and other beverages that


ofcontain ethanol. Ethanol manufactured
H
nvolves conversion of the H Hdouble Hchange
4 structural features that

polymersbond
properties (see to 8.21). single It bond.
average, 150 000 carbon atoms in each molecular chain, although in any
a thermoplastic Monomer
particular sample of polyethene, the sizes of the molecules will vary. involves
C ThisC conversion
type
liquid quite suddenly at 0C. The size of the

+ H Polymer
H theHdouble
molecules prevents a polymer from undergoing
H bond C to C a single bond. This type
HsectionC H4) from
makes
1 1 an alkane
a similar change of state. The molecules are

Contains a ethene is used as a double


reagent for industrialsingle bonds purposes and as aHsolvent in
C H
Polyethene is the simplest of polymers because only hydrogen atoms are

! as 1
too entangled to move freely in the manner

n is known H an H
Haddition 3 next
reaction.
for number
H ofcarbon
carbon-
reaction
bonded to the carbon atoms in the chain. It is a thermoplastic polymer,
H His known
Those carbon-carbon
as an H
bonds become
addition
carbon-carbon
reaction.
of water molecules. Polymers do not have a

Reactions of functional
double bond
which means it can be heated again and reshaped. This is because the bonds Htogether
as the monomers link covalently to form a polymer
defined melting temperature. If they soften, they
H
Hproducts C H cosmetics, This reaction,
pharmaceuticals in which the red-brown
and inks. colour of bromine disappears as
H
do so over a broad temperature range. This
between the non-polar chains are weak dispersion forces. As the polymer is

C and H Hwith C
!
Structural formulas ofC reactants
heated, the molecules gain kinetic energy and the polymer chains can slide
H
class of polymers is sometimes described as
H H
12
thermosoftening or thermoplastic.
High-density polyethene (HDPE) is used

Figure 8.21
are usually used when writing equations Branching for it reactsLow Branchingthe alkene, is used
2
over one another, breaking the weak dispersion forces. The strong covalent
High as a general test for
for pipes, buckets, toys, containers and
Branching H unsaturation (Figure
Unbranched chains of polyethene can pack together quite closely to form

onC with Chydrogen gas H


2CReaction C with Chydrogen Brthegas
bonds within the polymer molecule are unaffected. freezer bags. HDPE. HDPE is stronger and less flexible than low-density polyethene.

Testing foraddition + Br
reactions
unsaturation.
H
so thatBr
Adding
H 4
the position C
a few C ofIllustrated
the by H C8.21). Figure ItCH involves
8.22 H
HDPE conversion
H + of
HHdouble
Br
3PO4
bond
LDPE C to H a single H bond.
C H This C type
H
esence of a atoms
catalyst and3 on heating, ethene InofAddition
reacts
the 3
presence
with hydrogen
of asa inancatalyst
presenceand on cling heating, ethene reacts with hydrogen

groups
polyethene
added can be clearly
2 shown. reaction is known theaddition reaction.
drops of red-coloured
his
duce ethane.
3. Add steam
A
bromine
hydrogen
to hexane
atom thehas CH
density, bonded
H of hydrogen pipes
to ethene ofcatalyst
a catalyst.
film Hhas bonded C Br C to each Br
H colour in Branching Br gasto toeach produce of
C the ethane.
Ccarbon HA + Hhydrogen H atom of the carbon
lowers
(right) produces no reaction. The 2O

makes an alcohol
Figure H8.21 H Br C
hardness and
2 Reaction with hydrogen gas 300C
the sunflower
either side
Testingoilof
(left)
for the disappears
double
unsaturation. almost
AddingCbond,
a few meltingconverting
point of a
H
High-density polyethene (HDPE) is used

atomsthe C=C on either double side bond of the double C bond, converting H the HC=C double bond
!
for pipes, buckets, toys, containers and

3
InReaction with of steam
Unbranched chains of polyethene can pack together quite
Low-density closely to(LDPE)
polyethene form is used for Highly branched chains of polyethene do not pack together as well and
polymer.
hexane HH H reacts with
freezer bags.

H to C
HDPE. HDPE is stronger and less flexiblecling
than low-density polyethene.
films, garbage bags, squeeze bottles, form a softer, more flexible and low-density form of polyethene.

immediatelydropsbecause molecules
of red-coloured in the
bromine the presence a catalyst and on heating, ethene
carry bags and insulating cables.
hydrogen
ncarbon
20
(right)single
produces bond.
no reaction. The colour
H in toLarge
gasa to carboncarbon
Figure H8.20
amounts
produce ethane. of ethanol single
H
arebond.
A hydrogen now made atom by the
has
H bonded
H
addition
OH
reaction
to each of theofcarbon
steam
Figure 8.29

sunflower oil contain carbon-to-carbonH double H

08
08
Two different forms of polyethene: high-density

bromine tothe
ethene. Addition of bromine to ethene.
polyethene (HDPE) and low-density polyethene
(LDPE).

bonds which sunfl


undergo 4. Addition polymerisation (see Unit 1.2.6)
ower oil (left) disappears
addition reactions
immediately because molecules in the
almost
H with The infl(H
atoms 2O(g))
uence
Figure on8.23
TheaFermentation
and ethene
either
of side of
functionalusingthe adouble
phosphoric
groups bond,acid on catalystthe
converting the
155
(Figure
C=C8.23).
chemistry double
of bond
organic molecules
bromine (Br 2). ower
H oil contain carbon-to-carbon double H to formation H ofHethanolof
carboncarbon fromsugar
single toundergoing
H bond.
ethene, produce ethanol
an addition is still
reaction used
with steam.
H to make beer,H
sunfl may be seen by studying their
the red-brown colour of bromine disappearshow
reactions. When we consider new
Low-density polyethene (LDPE) is used for Highly branched chains of polyethene do not pack together as well and Compounds of carbon

2
Computed by WolframAlpha cling films, garbage bags, squeeze bottles,
Computed by WolframAlpha
wine and other beverages that contain ethanol. Ethanol manufactured
form a softer, more flexible and low-density form of polyethene.

eaction,bonds in which
2,2-dimethylpropane
2-methylbutane
theaddition
red-brown
reactions withcolour of bromine This reaction, disappears in which as
2,2-dimethylpropane as
carry bags and insulating cables.

which undergo Large Side-Groups Monomer Polymer


Computed by WolframAlpha
Figure 8.29

substances
H from can
ethene very be
is used made,
as a we
reagent should think
for industrial H about
purposes H and how
as a theinstructure
solvent of its

08
08
Two different forms of polyethene: high-density

with C the Calkene,


bromine (Br ).
+isH usedHas a general test for
Illustrated by polystyrene
it reacts
unsaturationH with largethe(Figure
alkene, +isH usedHas a general test for unsaturation (Figure
polyethene (HDPE) and low-density polyethene
2 H Polystyrene: H
C
(LDPE).
C C C low density C C
nvolves conversion of
of the functional
double bond to a8.21). group
singleIt
bond. determines
involves
This thetheway
Large side-groups prevent dense
conversion
type 4cosmetics,
of aFormation of
a particular molecule
pharmaceuticals
reacts H polyethene
typeand the
and inks. H
! naming
atic alkanes and alkenes up to C6 of double bond to a single
packing and lowers the density
polymer. bond. This
An addition reaction of ethene is involved in making polyethene (Figure
155
Compounds of carbon
C C

+ H H
H
C C
nStructural
is known as an addition reaction.
formulas H of reaction
conditions H His known
needed as
H anreaction
forHthe addition to
reaction.
occur.
! H of reactants and products 8.24). As in the previous three examples, H PO
H
the double bond is converted to
H H H H

Properties Alkenes
3 4
are Figure
usuallyStructural
used when
8.21 writing equations for
formulas of reactants and products
on with hydrogen gas 2a carbon-carbon
Reaction H with
single hydrogen
H bond in thegas catalyst
reaction and H H a saturated productH forms.
addition
added
esence
reactions
are
atoms
of
usually
can
a H
so
be
that
used the
when
clearly
catalyst
position
22Testing for unsaturation. Adding a few
writing
shown.
and on
of the
equations
heating,
for
3
Arrangement of Side-Groups
ethene H In this case,
In reacts
the Reactions of chloroalkanes
H H
presence
with
C
hydrogen
of a H
+ H2O
Figure 8.22there is no other reactant to add to theCethene
C
catalyst and on heating, H
ethene
C
molecules.
H
reacts HThe
with hydrogen
H H

0088
addition reactions so that the position of the 300C
ydrogen to ethene in the presence of a catalyst.
drops of red-coloured bromine to hexane Illustrated by polypropene ethene Addition of hydrogen
Figuremolecules
8.22 to ethene in the presence
themselves join together to form of a catalyst.
Isotactic
polypropene:a long chain.
added atoms can be clearly shown.

1. Substitution Reactions of Alkanes


duce ethane. A hydrogen atom pack
(right) produces no reaction. The colour in has
Isotactic bonded
polymers
H andcan gas toto each
Addition produce
ofH of theethane.
hydrogen to carbonA hydrogen atom has bonded
ethene H in the presence of a catalyst. high H density
H to each of the carbon
OH
C C+
atacticOnce athemore C electronegative atom Br such as chlorine
bond, converting Cthehas Cbeen substituted for
more closely
H CI
Add bromine solution
theC sunflowerC oil (left)+ disappears
Br Br almost are are more dense C C C + BrIsotactic
either side of the double bond,thanconverting polymers. atoms C=Con
Atactic either
double side
bond of the double C=C double bond
on with steam
immediately because molecules 3to Figure 8.23 H
Reaction with steam H
ncarbon single bond. Brown in the a hydrogen 3The atom
a formation
carboncarbon
Reaction with in an
steam alkane,
single bond.
Brown the molecule becomes polar.
!
of ethanol from ethene, undergoing an addition reaction with steam.
sunfl
150
ounts ower oil contain
of ethanol carbon-to-carbon double
are now made by the Br addition
Large H H
Large amounts
reaction ofofethanol
steam
ethanol are are
nownow mademade theby the
areBraddition
reaction reaction of steam
Colourless H Colourless H BrColourless H Colourless Br
bonds which undergo addition reactions with Electrons amounts in the carbonchlorine bybond addition attracted towards
of steam the more
and ethene using a phosphoric acid catalyst
Materials
M (H(H(Figure
22O(g))
O(g))Hand and
8.23). ethene
ethene using
using a phosphoric
a phosphoric acid catalyst
acid catalyst (Figure (Figure 8.23).
8.23).
20
bromine (Br 2). H
ntation of sugar to produce ethanol is still
electronegative
H
Figure 8.20
Fermentation
used to make
Fermentation
4 Formation
H chlorine
of of ofsugar
H
beer,
sugar
polyethene
atom. This
to produce
to produce
makes
ethanol ethanol
the
is still is
carbon
H
stillto used
used
atom
make to
H
beer,
at the other
make beer,
end
) other
C C
2. Add hydrogen gas
bromine to ethene. Substitution
beverages + H
that H
of an
contain additionof
ethanol. thewine
H polymers
An
C
bond
Addition
wine
Ethanol and
and of susceptible
addition
- relationship
C
bromine
other tobeverages
manufactured
other
reaction
between
C
ethene.
beverages
of
structure,
+Cas Cl
to
ethene
attack
that contain
heat
that
properties
+ H is and
H
by
contain
involved
negatively
ethanol.
orapplications
light in Ethanol
ethanol.
making H charged
manufactured
Ethanol
polyethene
ions (anions). For
manufactured
(Figure
Figure 10.10
example, from chloromethane
ethene isais
Hused a in aisreagent
reagent converted
for industrial theto methanol
purposes andCisasconverted
when
C
a and asitato
solvent in + HCl
is reactedCl
in with Structural formula of chloroethane. Hydrogen
makes an alkane
2
ne!is used asalkane a reagent withforClindustrial
2 purposesfrom
8.24). and
ethene
As in as the solvent
used
previous as three examples, for industrial double purposes
bond Hsolvent
eaction, in which the
and red-brown colour cosmetics,
a carbon-carbon
ofcosmetics,
bromine
Thisions, pharmaceuticals
reaction,
disappears single bond
in which and
as Figurein inks.reaction and a saturated product forms.
the
the
and red-brown colour of bromine disappears as has electronegativity of 2.1, carbon 2.5 and
pharmaceuticals inks. hydroxide as shown
pharmaceuticals 10.11. The
inks. chlorine atom is substituted by
!
Structural formulasH of reactants and products H H Hthere H H Cl
H chlorine 3.2.
with the alkene,
used wheniswriting
usedequations
as a general an testOH itInreacts
for this case,
unsaturation
functional with the is alkene,
no other
(Figure
group
reactant
to isjoin
form
to aadd
used methanol.
as to the ethene
general test formolecules.
unsaturationThe (Figure

0088
are usually for H H H H
ethene molecules themselves together
H3PO4 to form a long chain.
nvolves conversion
22addition reactions H so that theof position
the doubleof the bond to H a8.21).
single
Figure Itbond.
Hinvolves
8.22H Thisconversion type H of the double bond to H a single bond. H This type
H3PO4 catalystH3PO4 H
nadded
is known
atoms as inbe
can anthe
clearly shown.
addition ofreaction. ofAddition
reaction Cis known as inan addition
presence ofreaction.
hydrogen
3.C Add
to ethene
+ H2O
steam
presence
catalyst a catalyst.
H HC + H2O 300C
of hydrogen
catalyst
H H H
toC ethene
H
+ the
H2O a catalyst. C C

on
CFigure 8.21
with
Testing
makes
hydrogen gas
Substitution

150 for unsaturation. an
of a
300C
Adding a few
alcohol 2
C C
Reaction
HH with
H
C
hydrogen
+ H
gas 300C H
C
OH
C
H H
on
ounts
withred-coloured
esence
drops of of
duce
steam
halogen
a catalyst
ethane.
M
of ethanol
(right) produces
H
!
group
andto on
bromine
Materials with
noAreaction.
hydrogen
hydroxyl The
a
heating,
hexane
are now
H O
atom
colour
group
3
ethene
made
Reaction
Inreacts
the
by the
in has
with with
+ presence C steam
hydrogen
of
addition
bonded Large
gastoto
The
Cl and on heating, ethene
a catalyst
Figure 8.23
reaction
eachamounts
produce
formationof theofof steam
O
ethanol
ethane.
of ethanolcarbon
reacts
H
are now
Aundergoing
from ethene, hydrogen
+ Cl
C with hydrogen
made
atom
an addition
by with
has
reaction
the
H OH
addition reaction of steam
bonded
steam. to each of the carbon
H H OH

see Unit
23and
the
4. 1.2.6)
Addition polymerisation (see Unit 1.2.6)
ethene
sunfl
immediately
ntation
ower
of ethanolof
nncarbon
using
oil (left)
because
sugar
single
from ethene,
a phosphoric
disappears
molecules
almost
either side of the double bond, convertingatoms
toundergoing
bond.produce
acid catalyst (H (Figure
the2O(g))
C=C
Figure
in the ethanol is still Fermentation
toThe
an addition reaction with aused
on
8.238.23).
and
H ethene
either
double
to ofmake
carboncarbon
steam.
formation
side
ethanolof
bond
beer,
using
of
sugar
single
from
the adouble
phosphoric
toundergoing
bond.
ethene, produce
bond,acid
ethanol
an addition
catalystthe
converting
is still
reaction
(Figure
C=CH8.23).
double bond
used to make beer,
with steam.
Figure 10.11
Reaction of chloromethane with hydroxide ions.
sunflower oil contain carbon-to-carbon double Chloromethane
other beverages that contain ethanol. wine
bonds which undergo addition reactions with
Ethanol andmanufactured
4 Formation other beverages that contain ethanol. Methanol
of polyethene Ethanol manufactured
ne is used
bromine (Br2). as
H a reagent for industrial purposes H from and
ethene
An addition HasH areaction
issolvent
usedofas in a reagent
Hethene for industrial
is involved in making purposes and(Figure
Hpolyethene asH a solvent in
, pharmaceuticals
tion of polyethene and inks. 4cosmetics,
8.24).
FormationAs inpharmaceuticals
the of previous threeand
polyethene inks. the double bond is converted to
examples,
naming
es up toof
C6alkanes
Substitution
onC reaction
of a and alkenes
of +ethene
H
up bond
a carbon-carbon single to C
in the
H C
His involved in making An addition
polyethene H C
C reaction
(Figure HH
of +ethene
H
6 reaction and a saturated product forms. H H C H
H
reactantistoinvolved
add to theinethene
making polyethene (Figure
C C C
halogen group with a In this case,
H H there
H is no other molecules.HThe
H
in !the previous three examples,
H H H H

0088
H3PO4 the double
8.24).
bond As is
inconverted
the previous
to three Catalyst
examples,
H3PO4 the double
ethene molecules themselves join together to form a long chain. bond is converted+ to
hydroxyl
Structuralsingle
formulas group
of reactants from
andcatalyst H
products and C CH + HO H H H C C + H (aq) + Cl(aq)
carbon H bond in the reaction H Ha saturated
a carbon-carbon
Hproduct
Clsingle
forms. bond in thecatalyst
reaction and a saturated product
H
OH forms.
when +writing
areC usually Cusedwater H2O equations for
(catalyst C C C C + H2O C C

10
10
e, there is no so other reactant to add to theInethene
this case,
molecules.
there
H is The
no other reactant to add to the ethene molecules.
H The

0088
300C 300C
22addition reactions that the position of the H Figure 8.22 H themselvesHjoin together to H H Figure 10.12
olecules can be required)
themselves clearlyjoin together to form ethene
150 to etheneHin the presence of a catalyst.
added atoms
hydrogen shown. a long chain.
molecules
H
form a long chain.
Addition ofHhydrogen
OH to etheneH in the presence of a catalyst. H OH Reaction of chloroethane with water.
Materials
M
Chloroethane Ethanol
23 Figure 8.23
onof ethanol
on with from
steam 3The
ethene, undergoing an addition reaction with Reaction
steam. with from
formation of ethanol steam
ethene, undergoing an addition reaction with steam.
ounts of ethanol are now made by the addition Large reaction
amountsofofsteam ethanol are now made by the addition reaction of steam 14
and
M ethene using a phosphoric acid catalyst (H(Figure
2O(g)) 8.23).
and ethene using a phosphoric acid catalyst (Figure 8.23).
3 Ways to Oxidise Alkanols Esterification Reaction
Materials
ntation Organic reactions: pathways to new products
tion of of sugar to produce ethanol is still
polyethene Fermentation
used to make
4 Formation of ofbeer,
sugar to produce ethanol is still used to make beer,
polyethene
onother beverages
reaction that iscontain
of ethene involvedethanol. wine
Ethanol
in making
An andmanufactured
polyethene
addition other beverages
reaction
(Figure that iscontain
of ethene involvedethanol. Ethanol
in making manufactured
polyethene (Figure
ne is used
in the as a reagent
previous for industrial
three examples, purposes
the doublefrom
8.24).and
bondethene
Asisasinathe
issolvent
used
converted as
in a reagent
previous
to for industrial
three examples, purposes
the double andisasconverted
bond a solvent to
in
,carbon
pharmaceuticals and inks. cosmetics,
single bond in the reaction and a saturated pharmaceuticals
Oproduct
2(g)
a carbon-carbon single and inks.
forms.bond in the reaction and a saturated product forms. RCOOH + ROH RCOOR + H2O
Inother
se, there is no reactant to OH
air, slowly add to theIn
ethene
this case,
molecules. noCOOH
there isThe other reactant to add to the ethene molecules. The

0088
H H HH H H H
olecules themselves join together
H3PO4 to form aethene
long chain.
molecules themselves join together
H3PO4 to form a long chain. Ester functional group
catalyst H catalyst H
O
C C + H2O
With acidified300C C H+/MnO
C
4CH(aq)C
+ H2O H C C O
H
H H H
permanganate OH COOH300C H H
0 H+
H solution H H OH H H C C + HO
OH C C C O C + H2O
Materials
M H Catalyst H
23
on of ethanol fromWith
ethene,acidified
HFigure
undergoing an addition reaction withThe
+/Cr8.23
steam.
formation

2O7 (aq) H
of ethanol from ethene, undergoing an addition reaction with steam.
OH CH3 H CH3

dichromate soln
OH COOH
ethanoic acid + ethanol ethyl ethanoate + water
Ethyl ethanoate is commonly known as ethyl acetate. As well as being
the oate comes
from the oic acid
tion of polyethene 4 Formation of polyethene used as an artificial flavouring, it is used as a solvent in some paints, adhesives
on reaction of ethene is involved in making An polyethene
addition reaction
(Figureof ethene is involved in
andmaking polyethene (Figure
nail varnish.
in the previous three examples, the double 8.24).
bondAsis in
converted
the previous
to three examples, the double bond is equation
The general converted forto the esterification reaction involving a carboxylic
carbon single common reactions
bond in the reaction aof organic
and a saturated
carbon-carbon compounds
product single including
forms.bond in the reaction and equations:
acida and
saturated product
an alkanol
addition
is forms.
reactions of alkenes
shown in Figure 10.20.
se, there is no other reactant to add to theIn
ethene
this case,
molecules.
there is
The
no
(addition of hydrogen halides and water limited to Esters other reactant to add to the ethene
symmetricalmolecules. The
alkenes),
have two-part names, withsubstitution reactions
the first part derived of of
from the name
olecules themselves join together to form aethene
long chain.
molecules themselves join together to form a long chain.
alkanes and primary haloalkanes, oxidation of primary the alkanolalkanols,
from which itand is made, where yl replaces anol. The second part
esterification
comes from the carboxylic acid, where ic acid is replaced by the suffix ate.
Thus the ester formed from ethanol and ethanoic acid is ethyl ethanoate
0 (Figure 10.21).
VCEasy
Protein Structure VISUAL
CHEMISTRY
Examples of Proteins Skin 3.2.3a
Hormones
Enzymes
Antibodies
Toxins
HaemoglobinH O H O
chemfact
H2N C C OH + H N C C OH
During the synthesis of a protein in the body,
Primary Structure
the sequence of amino acids in the protein sequence ofH amino acids H CH3
is controlled by a complex polymer called Glycine Alanine
deoxyribonucleic acid (DNA) that is found condensation reaction
in the nuclei of cells. Sections called genes between two amino acids Amide or peptide linkage
along the DNA polymer chain contain the
Hinstructions
HO OHfor building
O all the thousands H HO O
H O H O H O
of different proteins found in any organism.
N H2NC H2N CC COH
C OH C OH
+ + H+ H N NC
H CN
C C
OH OH
C OH H2N C C N C C OH + H 2O
The structure and function of DNA are
Hdiscussed inH ChapterZ-group
13. H 3 Z-group
H HCH3 CH CH3 H CH3 Z-group
H H
Glycine
GlycineGlycine Alanine
AlanineAlanine Z-group A dipeptide Water

AmideAmide
or peptide
Amide
or peptide
linkage
or peptide
linkagelinkage
Figure 12.28
SecondaryH O Structure
H OH O
H HO H hydrogen
O O bonds
The condensation reactionbetween
between two aminoamino acids
acids. Note how that
the carboxyl and amine gro
forming the dipeptide and water.
H N H NC H N
2 2 C
C N
CC N
C
C2
CN
C OH form
C OH
C+ OH
+ H-helices
O+H O H O and -pleated sheets
2 2 2

H H H HCH3 CH
H 3 CH3

A dipeptide
A dipeptide
A dipeptide WaterHhydrogen
Water
OWater bonds
H between
O H O H O
chemfact amino acids
C C N C C N C C N C C N
FigureFigure
A shorthand notation is often used represent
12.28Figure
12.28 12.28
the
Thesequence
e condensation
The condensation of amino
condensation
reaction
reaction
between acids
reaction
between
two in aamino
between
amino
two polypeptide
acids.
two acids.
amino
Note how
Note
acids.
the
how
Note
carboxyl
thehow
carboxyl
(CH the
and carboxyl
amine
and amine
groups
andH groups
amine
react
CHgroups
react
in inreact
H in CH2 H CH3 H
3)2CH 2
ming
formingchain. The
the dipeptide
forming sequence
the dipeptide
the
anddipeptide
water. of
and water. amino
and water. acids (valine,
serine, cysteine, alanine) in the section of the OH SH
polypeptide chain shown in Figure 12.28 is
Tertiary Structure
represented as: interactions
Valine
between
Serine
Z-groups
Cysteine Alanine

H H
O OH H val
O HOser cys
OH alaOH HO OH OH HO O
H O
Figure 12.29
A section Nof
C a polypeptide chain, showing peptide linkages.
C C
C CN
C N
C
C C
NC CN N
CC C
NC C
C
N
dispersion forces between non-polar Z-groups
NCC N
CC C
N N

H3)2(CH CH HCH2 CH
(CH3)2H
CH3)2CH H 2 CH
H 2 HCH2 CH
H 2 CH
H 2 H CH3 H
CH3 CH
H 3 H H

OH OH OH SH SH SH
ionic-ionic interactions between NH & COOH Z-groups
Proteins are polymers formed by condensation reactions betw
3
+

ValineValine ValineSerineSerine Serine Cysteine


Cysteine
Cysteine covalent cross-links
acids; during
Alanine these reactions
AlanineAlanine the amino
between acids
cysteine join
amino and(SS)
acids form long u
chains. The amine group of one amino acid reacts with the carbox
FigureFigure
12.29Figure
12.29 12.29 hydrogen bonds
an adjacent amino acid. A covalent
between OH and/orbond is Z-groups
NH on formed and a molecu
section
A section
of aA polypeptide
section
of a polypeptide
of a chain,
polypeptide
chain,
showing
showing
chain,
peptide
showing
peptide
linkages.
peptide linkages. is eliminated, as shown in Figure 12.28.
linkages.
Molecules made from amino acids are often called peptides.
amino acid molecules react together a dipeptide is formed, and w
chemical bonding: primary, secondary and tertiary structures
molecules react of proteins
together a tripeptide is formed. A polymer m
Proteins
Proteins
Proteins
are polymers
are polymers
are polymers
formed
formed
by
formed
condensation
by condensation
by condensation
reactions
reactions
reactions
between
between
between
aminoaminoamino
ds;
acids;
during
acids;
during
these
during
these
reactions
these
reactions
reactions
the amino
the amino
the
acids
amino
acids
joinacids
joinamino
and and
form acids
joinform
and is
longform
longknown
unbranched
long as a
unbranched polypeptide,
unbranched and polypeptides built up
ains.
chains.
The
chains.
The
amineamine
The
group
amine
group
of group
one
of one
amino
ofamino
oneacid
amino
acid
reacts
reacts
acid than
with
reacts
with
the50with
amino
the acids
carboxyl
the carboxyl are
carboxyl
group ofusually
group group
of ofcalled proteins (Figure 12.29). Th
adjacent
an adjacent
an adjacent
amino
amino
acid.
amino
acid.
A covalent
acid.
A covalent
A covalent
bond bond
is formed
bond isatoms
is formed
and
formed
and CONH
a molecule
aand ofthat
molecule of links
a molecule
waterwaterthe constituent amino acids is an am
of water
VCEasy
Proteins as Enzymes VISUAL
CHEMISTRY

Enzymes are: 3.2.3b

biological catalysts
increase reaction rates
operate
catalyses at mild conditions
many a (e.g. inside cells)
selective
atalyses (with substrates)
the first Enzyme
E
due to the unique shape of its active site

ysis).sensitive
This is the
(to heat and pH changes)
an perform this
ymes, each one
How Enzymes Work: dispersion forces
dipole-dipole interactions
ing in size from ion-dipole interactions
hydrogen bonds
Substrate
molecules withenters active site ionic-ionic interactions
Substrate
Enzyme forms intermolecular bonds with substrate
rtiary structure.
Bonds within the substrate are weakened, lowering EA
der an enzyme The substrate enters the active
Substrate breaks into
site products
in the enzyme
xible hollow or
n-protein parts Enzyme forms
with the active b Bonds are formed
intermolecular bonds
withwith
thethe
enzyme
substrate

uvred into this


ion takes place.
12.32. They are Enzyme

Active Site
n bonds within
Bonds break in
these products the substrate

r second on an c The enzyme is


regenerated
se catalyses the
chemical bonding: the role of the tertiary structure of proteins in enzyme action

O3) into carbon


This selectivity arises because the shape and functional groups in the active Dispersion forces and dip
site of the enzyme allow it to bind only with certain substrates. The enzyme
VCEasy
enzymesubstrate compl

Denaturing Enzymes
and substrate are often described as fitting together like a lock and key.
Figure 12.33 shows some of the types of bond that can form between
enzyme and substrate:
VISUAL of
Denaturation
1 iondipole interactions (between Zn2+ and O=C)
+
CHEMISTRY
3.2.3c
2 hydrogen bonds (between NH and O=C)
3 ionic interactions (O and +NH3).
What Happens when Enzymes Denature
Dispersion forces and dipoledipole interactions may also be involved as an
enzymesubstrate complex forms.

Denaturation of enzymes
chains become entangled bonds in the tertiary structure break
and bond with each other

Dena

tertiary structure is changed


Denaturation Coagulation

heat or
unsuitable pH
active site is no longer the correct
shape to bond with the substrate

Figure 12.34
When a protein is denatured the chains unravel and then often clump together to form a solid mass. Figure 12.34
When a protein is denatured the c
High Temperature
We have seen that the structure of a protein e.g.is cooking
important toan
functioning. Since the bonds responsible for holding the protein chains in
its egg
correct

particular shapes are often relatively weak, slight changes in conditions can We have seen that the
disrupt the attractions between parts of the chain, causing the chain to unfold
and rendering the protein ineffective (Figure 12.34). A change that destroys functioning. Since the bo
enzym
the biological activity of a protein is called denaturation. Denaturation may e is d
enatu particular shapes are ofte
result because of increased temperature, a change in pH, or the addition of red
various chemicals. gy disrupt the attractions bet
er
Enzyme activity is dependent on temperature. As temperature increases, e n and rendering the protein
the rate of the reaction catalysed by the enzyme increases because of ticincreased excessive kinetic energy breaks the bonds
e the biological activity of a
Rate

n
collisions between enzyme and substrate, until an optimumkitemperature, that give rise to its tertiary structure
about 40C, is reached. As the temperature increases further g
n the enzyme is result because of increase
denatured and the reaction rate decreases rapidly (Figure si
a12.35).
e various chemicals.
Enzymes operate effectively within a small pH inrange cr (Figure 12.36). irreversible change in tertiary structure
Not all enzymes have the same optimum pH. Pepsin, an enzyme that breaks Enzyme activity is dep
down protein in the stomach, is most efficient at a pH of 1.5. The optimum
pH of salivary amylase, an enzyme that catalyses the hydrolysis of starch in the rate of the reaction cat
the mouth, is 7.4. Lipase, which breaks down fats in the small intestine, has collisions between enzym
an optimum pH of 89. You will recall that the ionisation 20of amino acids is 40
dependent on pH. The bonds that determine the tertiary structure of the
60 about 40C, is reached. A
Temperature
enzyme are altered as changes in pH alter the ionisation of the amino acid denatured and the reactio
residues in the protein.
Unsuitable pH e.g. addingFigure
vinegar to milk (it curdles)
12.35
Enzymes operate effe
Effect of temperature on enzyme activity. Not all enzymes have the
down protein in the stom
ed, the unfolded chains tend to form pH of salivary amylase, a
come into close contact. The chains the mouth, is 7.4. Lipase,
Salivary
ch other, often by disulfide bridges, so amylase Lipase
Pepsin an optimum pH of 89. Y

12
12
les are formed. This process is called
dependent on pH. The b
Rate

er of instances of denaturation: enzyme are altered as ch


umin protein in the egg white changes residues in the protein.
olid. Heating above 60C causes the
. 196
ed to it. Denaturation and coagulation Organic
O chemical
2 4 6 pathways8 10
used by the change in acidity. A similar pH
rs due to the production of lactic acid
at are present in the milk. Figure 12.36
Effect of effect
chemical bonding: denaturing of proteins: pH on enzyme activity.
of changes in pH and temperature on bonding
VCEasy
DNA VISUAL
CHEMISTRY
Primary Structure of DNA the phosphate group, bonded
to two deoxyriboses, is called
3.2.3d
a phosphodiester bond
OH O OH
O secondary
N H amine group
O P O condensation 1 N O P O
N H
N
O H H O O
aNH2 CH3 ++2H
2H22O
O
N N
Phosphate
CH2 O CH2 O
N NH2
OH H
there Guanine
are four types O N
5 5 H+ H
of bases; this one is
4 1 N
guanine N N 4 1 two water molecules
condensation 2 Bond to
H+ from the two
DNA chain N
3 2 3 2
N condensation
O
deoxyribose reactions
(five-carbon sugar)
OH OH N
or T A N
deoxyribose!
Deoxyribose Guanosine monophosphate nucleotide
Bond to
(five-carbon sugar) H
b DNA chain

N
Figure 13.6
Covalent
Formation of bonds are
a nucleotide. responsible
Skeletal formulas arefor
usedproducing
for simplicity. the primary structure of DNA. A covalent bond is formed
H +

between the 5-phosphate group on one nucleotide and the 3-hydroxy N group
N on the
O deoxyribose of another

Bond to
nucleotide. Nucleotides undergo condensation polymerisation DNA chain to form a single-stranded
H
N
DNA helix. +

Primary structure of the polymer O


N

H+
Covalent bonds are responsible for producing the primary structure or C G of N N
N

DNA. A covalent bond is formed between the 5-phosphate group on H


Bond to

Secondary Structure of DNA


DNA chain
one nucleotide and the 3-hydroxy group on the deoxyribose of another
nucleotide. One end of the DNA strand has a hydroxyl group and is called
Figure 13.7

All due to hydrogen bonding between base pairs


the 3 end. The end of the polymer with the phosphate group isbonding
Hydrogen called
end. In this way, nucleotides undergo condensation polymerisation to form
thea 5
between thymine and adenine, and b guanine and cytosine.

a long chain of nucleotides (Figure 13.5).


a A base CH
is also covalently bonded to the sugar group at the C1 site via a
3

condensation reaction
O (Figure 13.6). It is the sequence aof bases
along the
Phosphate group b
A T
sugarphosphate backbone that forms 2 hydrogen
the primary structure5 and is the basis
H H + Deoxyribose sugar group
N
for the genetic
N N code. P Nitrogen base 3
Bond to
DNA chain bonds form H+
N
N
Nucleotide
S
S
S
C G
A

Secondary structure ofbetween


O
the polymer
A::::T
N
P
P
G
G
C
C

or T A N S
S
As is the case in proteins, hydrogen Bondbonding
to is responsible for maintainingP
the T
H
b secondary structure of DNA. DNA chain P
Sugar-phosphate
Sugar-ph
backbone
S G
Erwin Chargaffs N
stoichiometric studies of the mole amounts Sof the four
H
3 hydrogen
+
P T A
bases in a wide variety ofO living things had led to the discovery that: G C
P T A
N N

1Bondfor
to
DNA chain
a given species,
H
the percentage
+
N
bonds form
of each of the four bases
3
is the
S same in S
C G

all cells Oand is characteristic


N of the organism T
A A

of thymine (a between purine) and G::::C


P 5
2 the mole amounts H + adenine (a pyrimidine) Hydrogen are
between
bonds
bases
N
equal or C G N N
Sugar-phosphate
3 the mole amounts H of cytosine DNA(a
Bond to
chainpyrimidine) and guanine (a purine) are
backbone chemfact
equal.
The bases in the hen are 29% each adenine
By considering the structures of the base pairs adenine
Figure 13.7
Figureand13.8 thymine, and thymine and 21% each cytosine and
Hydrogen bonding between a thymine and adenine, and b guanine and cytosine.
it can be seen that they are able to fit together, rather like the bonding
a Hydrogen pieces of complementary
between a bases produces a ladder-like structure. Note that the
guanine. In contrast, thea marine crab has
strands run in opposite directions. b The polynucleotide ladder twists to form right-handed double
jigsaw. It is possible for two hydrogen bonds to form between helix. the on approximately 47% each adenine and
nitrogen and oxygen atoms and the + on hydrogen atoms on the adjacent thymine and only 3% each cytosine and

13
13
a base (Figure 13.7). Similarly bwith the base pairs cytosine and guanine, three
Phosphate group guanine.
A T
hydrogen
Deoxyribosebonds can form between on nitrogen and oxygen atoms of one
sugar group
5
base
P the +
andNitrogen base on hydrogen 3
Nucleotide
atoms on the adjacent base (Figure 13.7).
S A
AsS shown in Figure
S
208 primary13.8, the secondary C G structure of DNA is a pair of
DNA
chemical
P
bonding:
polynucleotidePstrands held
and secondary
togetherG
structure of DNA
C by hydrogen bonding between the
Organic chemical pathways
O
basesS adeninethymine S and cytosineguanine.
T
G C
The structure twists around
to form a right-handed
P
P
double helixthe shape of a spiral staircasewhere
Sugar-phosphate
Sugar-ph
backbone
the sugarphosphate
S
S backbone forms G the handrails and the pairs of bases are

P T A
help to preserve the worlds resources.
help to preserve the worlds resources.
Figure 10.26 shows the main chemical reaction pathways that
Figure
Organic 10.26 shows the main chemical reaction pathways VCEasy
that
can be
can be
to formchemists are highly skilled at devising molecular structures
for otherthat
Making Esters from Alkenes
H
used
used have
alkanes
alkanes
to exactly
compounds
form compounds
can be constructed
can be
Cl
constructed
based on
by replacing
by
ethane
based on needed
the right properties ethane for
replacing
and ethene.
anda ethene.
OHa CH3 group in ethane
a CH group in
Pathways
particularPathways
purpose.
ethane
VISUAL
for other
They
O with another
withCHEMISTRY
another
then
alkyl have
group.to devise an efficient method for converting 3 a readily available starting
Comes
C
alkyl group.
Cl2(g)
up regularly
materialoften
C
an
NaOH(aq)
inalkene
exams
reaction pathway selected needs to
Cr2O72-(aq)
or an alkaneinto the product they want. The
C +(aq)
take intoHaccount theC
yield and purity
3.2.4a
H Learn CH3this
of the pathway!
products
H and
CH3also minimise
H any CH
unwanted
3 side-products
HO CH3and waste
H materials. TimeH and cost factors Halso need to be considered. There is a lot of
Ethane Chloroethane Ethanol Ethanoic acid
current interest in working out greener synthetic routesones that minimise
waste, use more environmentally Hfriendly solvents, requireHROH less energy and
H
Start
help to preserve
Cl
with
HCl(g) an alkene
the worlds resources.
OH
2O(g)
O
2SO4
H Cl OHH3PO4(s) O
Cl2(g) Figure 10.26 shows NaOH(aq)the main chemical Cr2O7reaction
2-
(aq)
2-
pathways
O that can be
Cl2(g) NaOH(aq) Cr O (aq)
C used to formC compounds based
H
C on ethane
H and ethene.
2 7
H++(aq) C Pathways for other
C C C H (aq)group inC ethane with another
CH3
alkanes
H
can be constructed
CH3 C C
H
by replacing
CH3
a CH 3 HO C CH
3
H
H
CH3 alkyl Hgroup.
H
CH3 H
H
CH3 HO CH3
R O CH3
H
Ethane H
Chloroethane H HH
Ethanol Ethanoic acid
Ethane Chloroethane Ethene Ethanol Alkyl ethanoate
Ethanoic acid
OH comes from this water ROH
(where R is an alkyl group, e.g. CH3)
HCl(g) H2O(g) HROH
2 SO 4
HCl(g) H2O(g) acid catalyst helps to separate H2SO4

0
H3PO 4 (s) +
H
from OH in water
Figure 10.26 H3PO4(s) O
O
Reaction pathways
H based on ethaneHand ethene.
H H alkanol carboxylic
H Cl OH C O acid
C C C
C C 2-
Cl2(g) NaOH(aq) R Cr2O7 O(aq) CH3
H H R O CH3
C + UV light HC Ethene H C +
H (aq) C
Alkyl ethanoate
ways Ethene (where RAlkyl
is anethanoate
alkyl group, e.g. CH3)
H CH3 H CH3 H CH3 (where R isHO an alkyl group,CH
e.g.
3 CH3)
H H H
Ethane Figure 10.26Chloroethane Ethanol Ethanoic acid
Figure 10.26separate this by
Reaction pathways based on ethane and ethene. ROH Add an
Reaction pathways based
fractional on ethane and ethene. H O(g)
distillation
HCl(g) H2SO4 alkanol here
2
H3PO4(s)
O
H H
ester

s C C C

R O CH3
H H
Ethene Alkyl ethanoate
(where R is an alkyl group, e.g. CH3)

0
Figure 10.26
Reaction pathways based on ethane and ethene.
Ester is produced
Naming rule for esters
oate is from the oic acid

ways

organic reaction pathways including appropriate equations and reagents: production


of esters from alkenes !
VCEasy
Triglycerides lipids are VISUAL
triglycerides CHEMISTRY
3.2.4b
Naming
Lipids

OH. The ester group, COO,


molecules. A water molecule,

single molecule of glycerol


Figure 12.3. Fatty
Fats Oils
solid at room
temperature
animals
single bonds (CC) saturated
all carbon-carbon
{
a carboxyl group, COOH, to be reacted with one with a hydroxyl group,
provides liquid

three molecules
acids contain a carboxylunsaturated
at room
a covalent
temperature
H2O, is also produced.
Most fats and oils are formed by a condensation reaction between a
fromand from of
link between the two

plants
fatty acids, as shown in
functional group
with the hydroxyl groups in the glycerol. The COO groups in fat are
containswhich reacts
carbon-carbon
double bonds (C=C)

ester functional groups or less healthy


ester linkages. Three healthier
molecules of water are also
produced in this reaction. Fats and oils formed from this process are called
triglycerides. Most fats have two or three different fatty acids attached to the
Esterification Reactions Produce Triglycerides
glycerol molecule. Triglycerides are large, non-polar molecules and therefore
insoluble in aqueous solutions. formula booklet says C H COOH 17 35

the COOH is here


O the C17H35 therefore Three
condensation 1
remains unchanged ester
H H three water
HO C C17H35 O linkages molecules from the
three condensation
H C OH O H C O C C17H35 reactions
condensation 2 O
H C OH + HO C C17H35 H C O C C17H35 + 3H2O
O
condensation 3 O
H C OH H C O C C17H35
still C17H35
HO C C17H35 the COOH groups have
H H formed ester linkages
1 Glycerol molecule 3 Stearic acid molecules Tristearin (a fat) 3 Water molecules
names of these long chain fatty
acids come from page 10 of the

1 of fats
Types : 3 : 1 : 3
formula booklet

Fats are distinguished on the basis of the fatty acids from which they are
Check the formula booklet on page 10 for how to name long chain fatty acids.
made (Table 12.1).
Tristearin is made from glycerol and 3 molecules of stearic acid, for example.

Saturated
Triarachidoninfats are from
is made made from
glycerol and fatty acids,
3 molecules such as palmitic
of arachidonic acid, that
acid, for example.
contain only single carboncarbon bonds. Saturated fats are generally
unreactive and
organic reaction occurincluding
pathways as waxy solids at
appropriate roomand
equations temperature.
reagents: condensation reactions
Mono-unsaturated
that produce lipids (limitedfats are made from fatty acids, such as oleic acid, that
to triglycerides)

contain one carboncarbon double bond.


disaccharide made by the condensation of galactose and glucose. It is not as
sweet as glucose. Lactose is synthesised in the mammary glands of mammals VCEasy
Condensation Polymerisation
and is the main carbohydrate present in milk.
In contrast, sucrose is widely used as a sweetener because of its
intense taste. It is formed from the condensation of fructose and glucose
VISUAL
CHEMISTRY
(Figure 12.13b). Sucrose is found in the sap of some trees and the juices
of many fruits. Table sugar is produced commercially by extracting sucrose
Polysaccharides
from sugarcane or sugarHbeet.O H O
3.2.4c
a H2N C C OH + H N C C OH water is
in in the body, HOCH2
H HOCH2
condensation
HOCH2 HOCH2 produced in a
condensation
O O O O
n the protein H H H H H reaction H H CHH3 H
H reaction
H + H H H + H2O
ymer called
Example 1
HO
OH H
OH Glycine HO
OH H
OH HO
OH Alanine
H OH H
OH
at is found O

called genes H OH H OH H OH
Amide or peptide linkage H OH
Glucose condensation Glucose Maltose glycosidic linkage
Glycosidic linkage Water water is
contain the (also an ether bond) produced in a
b H O H O condensation
thousands HOCH2
H HOCH2
glycosidic linkage
Glycosidic
(also an etherlinkage
bond) reaction

ny organism. O CH2 O condensation O H HOCH2 O


H H H2N CH N
C reaction C H C OH + H 2O H
DNA are H + H + H2O
Example 2 OH H H HO OH H H HO
HO OH HO CH2OH H CHHO CH2OH
H 3 O

H OH HO H H OH HO H
A dipeptide Water
Glucose condensation Fructose Sucrose Water

Figure 12.13
The condensation of a Figure 12.28 to form maltose, and b glucose and fructose molecules to form sucrose. Glycosidic linkages are highlighted.
glucose molecules
Proteins The condensation reaction between two amino acids. Note how the carboxyl and amine groups react in
forming the dipeptide and water.
amide links
Polysaccharides: the
(result complex
from condensationcarbohydrates
reactions between NH 2 & COOH groups)

As the name implies, polysaccharides are polymer carbohydrates made


by linking monosaccharides into a chain. Polysaccharides are polymers Monosaccharide Disaccharide
H O H O H O H O
of glucose molecules linked together in different ways by condensation
reactions. Polysaccharides are generally insoluble in water and have no taste.
C C N C C N C C N C C N
n used representThe three most important polysaccharides biologically are:
s in a polypeptide glycogen (CH ) CH H CH2 H CH2 H CH3 H
starch 32
no acids (valine, cellulose.
the section of the
Glycogen is found in animals, where OH it acts as a glucoseSH storage molecule.
Figure 12.28 is As glucose can beValineoxidised to produce
Serine energy more rapidly
Cysteinethan fat, all
Polysaccharides
Alanine
animals store some glucose for use when energy is required quickly. Excess
ala glucose is polymerised to form glycogen, which is stored in the liver and
in muscle tissue.Figure
When 12.29
no more glycogen can be stored in these places,
DNA additional glucose is converted
A section into fat. chain,
of a polypeptide As energy is required,
showing the glycogen
peptide linkages.
is hydrolysed to yield glucose for respiration. the phosphate group, bonded
to two deoxyriboses, is called

OH
Starch is the glucose storage molecule in plants;
O the plant equivalent
OH
of a phosphodiester bond
Figure 12.14
glycogen. The starch is stored and used at night to meet the plants ongoing Starch and glycogen are O polymers ofsecondary
glucose.
energy requirements when glucoseN production from Hphotosynthesis has The glucose molecules are joined together
Proteins are polymers formed by condensation reactions way, butbetween
glycogen is moreamino
amine group
O P O condensation 1 N O P O the same highly
ceased. N H
acids;
Figure 12.15 during
represents the these
digestionreactions
of starch andthe amino
glycogen acids
in the join and
body. form long unbranched
branched than starch. Hydrogen bonds
N
between parallel chains are formed in cellulose,
O H H O O
chains. The amine groupNof oneNHamino
During digestion, the polymers must be broken down to release acid reacts with
the glucose thestrong,
carboxyl group of22OO

12
12
producing water-insoluble fibres.++2H
2H
Phosphate monomers. The polymers are first N hydrolysed. This hydrolysis2 is catalysed
CH2 anO adjacent OH H
aminothere acid. A covalent bond isCHformed
Guanine
are four types 2 O and Na moleculeN ofNHwater
2
5 5
4
is eliminated,
1
as shown
of bases; in
this
guanine
Figure
one is 12.28. 4 1
condensation 2 two water molecules
Molecules made from amino acids are often called peptides. When two
from the two 185
3 2 3 2
amino acid molecules react together a
deoxyribose dipeptide is formed, and when three
condensation
Pathways to biomolecules
reactions
molecules react together a tripeptide is formed. A polymer made from
(five-carbon sugar)
OH OH
amino acids is known as a polypeptide, and polypeptides
deoxyribose!
Deoxyribose builtnucleotide
Guanosine monophosphate up from more
(five-carbon sugar)
than 50 amino acids are usually called proteins (Figure 12.29). The group of
Figure 13.6 atoms CONH that links the constituent amino acids is an amide group,
Formation of a nucleotide. Skeletal formulas are used for simplicity.
referred to as a peptide linkage in proteins.
organic reaction pathways Proteins differ from
including one another
appropriate equations in the number,
and reagents: type and sequence
condensation andof their
Primary
polymerisationstructure constituent
reactions ofthat
the polymer
amino
produce acids.
large Each proteinincluding
biomolecules has a precise chemicalproteins
carbohydrates, composition,
and
DNA
Covalent bonds are amino responsibleacidforsequence,
producingand thethree-dimensional
primary structure ofshape. There can be more than
DNA. A covalent bond is formed between the
500 amino acid units in a large protein. 5-phosphate group on
Determining the structure of these
carbon dioxide.
carbon dioxide.Research
Researchalso suggests
also that
suggests thethe
that useuse
of of
E10 petrol
E10 reduces
petrol reduces
thethe
quantity of of
quantity particles such
particles as as
such unburnt
unburntcarbon
carbonandand
gases such
gases as as
such VCEasy
oxides of of
oxides
Making Biochemical Fuels
nitrogen that
nitrogen areare
that emitted by by
emitted exhausts andand
exhausts that contribute
that contributeto to
airair VISUAL
pollution.
pollution.
CHEMISTRY
Biodiesel
Biodiesel
Ethanol 3.2.4d
Biodiesel
Biodiesel is is
a mix
a mix of ofesters
estersproduced
produced by by a chemical
a chemical reaction
reaction between
between
Crush
vegetable
vegetable the feedstock
oiloil
and andan an
alcohol
alcohol suchsuchas as
methanol.
methanol.
The The chemical
chemical andand physical
physical properties
properties of ofthethe esters
esters in inbiodiesel
biodiesel areare very very
Wet
similar
similar
& mix
to to
those
wet means add water to make it a slurry
thoseof ofdiesel
diesel(petrodiesel).
(petrodiesel). In InEurope,
Europe, biodiesel
biodiesel containing
containing 5%5%
Heat
esters
estershastohas
100C
beenbeen for
available 3 hours
available since
since with
1995. enzymes,
1995. It is thispossible
convertsto
It possible
is starch
runinto
to run glucose
dieseldiesel vehicles
vehicles onon
Cool
100%
100% toester
ester 32C
fuel.
fuel.
The The usual rawraw
usual material
material is fresh
is freshvegetable
vegetable oilStops
from
oil from
at sources
1020% sources such
ethanol, just likesuchasproduction
wine soybeans,
as soybeans,
because a
Ferment
canola
canola or or
palm
glucose
palmoil,oil,
into
butbut
ethanol
recycled
recycled
&
vegetable
CO
vegetable 2
oiloil
high concentration of ethanol renders the enzymes inactive.
or animal
or animal
Fermentation fats
is done cancan
fats
by genetically also alsobeE. be
engineered used.
coli.
used.
Steam
Fats andand
Fats distillation
oils areare
oils to extract
triglycerides
triglycerides withwith athe ethanol
molecular
a molecular structure
structure consisting
consisting of of three three
hydrocarbon
hydrocarbon chains
chains attached
attached by byester
esterfunctional
functional groups
groups to to a backbone
a backbone of of
Petrol is added to the ethanol in varying proportions (5%90%) to prevent people from drinking it.!
three
three
This carbon
is carbon
called atoms,
atoms,
denaturing as shown
as shown
or poisoninginthein
Figure
Figure
ethanol. 11.6.
11.6.
The The triglyceride
triglyceride is hydrolysed
is hydrolysed by bywarming
warming it with
it with methanol
methanol andand potassium
potassium
hydroxide
hydroxide solution.
solution. The Thepotassium
potassium hydroxide
hydroxide solution
solution acts acts as asa catalyst
a catalyst in in
this
this
hydrolysis
hydrolysis
Biodiesel reaction
reaction so so
that overall
that thethe
overall triglyceride
triglyceride breaksbreaks down down to to three three
molecules
molecules of of
fatty acid
fatty acid esters, plus
esters, glycerol
plus glycerol (Figure
(Figure 11.7).
11.7).
ester bonds
H H O O H H

H H C C O O C C (CH(CH warm KOH


2)14CH
2)143CH3 H H C C OH OH
(catalyst) ester bond
O O
+ 3CH
+ 3CH
3OH3OH + 3CH
+ 3CH
3OOC(CH
3OOC(CH2)14CH
2)143CH3
H H C C OH OH
H H C C O O C C (CH(CH
2)14CH
2)143CH3
C C H H C C OH OH

H H C C O O C C (CH(CH
2)14CH
2)143CH3
H H

H H

1
Triglyceride
Triglyceride
(palm oil)Vegetable
(palm oil) Oil +
3 Methanol
Methanol
Methanol 1Glycerol
Glycerol
Glycerol +
3
Fatty acidacid
Fatty methyl esters
methyl
Biodiesel
(biodiesel)
(biodiesel)
esters

(a triglyceride) (a Fatty Acid


Figure 11.711.7
Figure Methyl Ester)
TheThe
hydrolysis of triglycerides
hydrolysis to fatty
of triglycerides acids
to fatty andand
acids glycerol.
glycerol.

organic reaction pathways including appropriate equations and reagents: production of biochemical
fuels including the fermentation of sugars to produce ethanol
hydroxyl to group
drive in thereaction
OOH theHO
salicylic
OH HO
acid molecule
backwards. In anthat functions
alternative O
asO thepathway,
reaction alcohol whic
This reaction could be used to form acetylsalicylic acid. Interestingly, it isacid
the
in CH
aCHreaction
33 CC CH3with
faster and C
C ethanoic
+ produces acid
H2OCH3(acetic
CH3+C+ higher C yields,CH3acid)
the to Cform
CH3ethanoic CH3 acid acetylsalicylic
CCis replaced
CH3C+VCEasy
Hwith
2OCH3 etha+ H2O

Making Aspirin
hydroxyl
in aThis is
group
and water.anhydride
reaction
Ethanoica slow
O
in
with
the O
O
reaction.
Ethanoic
acid acid
salicylic
(acetic
ethanoic Also
O
Ethanoic Water
acid
anhydride).
acid
molecule
(acetic
the yield
Ethanoic acid
acid
Thisacid)
is
that
is the
low, to
Figureas
functions
preferred
form
the
14.3
as the
pathway for
acetylsalicylic
water formed
alcohol
VISUAL
the synth
acid
tends
CHEMISTRY
Water Wat
and water. of aspirin
O O(Figures 14.3, 14.4). O OO O
to driveEthanoic
Synthetic
This
was
faster and
the reaction
anhydridebackwards. In an alternativeEthanoic
Pathway
anisextract
a slow
produces reaction.
from Also the
coal tarthe
higher yields, yield
black,
the
Formation
is low,
sticky
ethanoic acid
of ethanoic
reaction
asisthe
substance water
anhydride.
pathway,
Ethanoic
anhydride
formed
that iswith
replaced
which is
anhydride
produced tends
ethanoic
3.2.4e
to when the
drive
anhydride coal is heated
reaction
(acetic in the absence
backwards.
OH
anhydride). HOThis ofthe
In isan air.preferred
Once hereaction
alternative had
pathway made salicylic
pathway,
for O acid is
which
the synthesis
he
faster replaced
O andOH
CH the OH
produces hydroxyl
C higher functional
+yields, C group
the
O ethanoic
CH withacidanOHis
ester
CH 3 functional
replacedC withgroup ethanoic
C CH3 + H2O
of aspirin
OH (Figures
O 3 14.3, 14.4). OH3O
to form (acetic
anhydride acetylsalicylic O acid (Figure
anhydride). O
This is 14.4).
the This is pathway
preferred the compound for theknown
synthesiswater is

C C CH
condensation
C as aspirin. O CH O C C
produced in a
commercially Ethanoic
3
acid
3
Ethanoic acid
condensation
Wat
ofO aspirin
C (Figures
CH
OH 14.3,
OH C
14.4).COH O C O CH C
O
CH
O reaction
OH O
The production
OH3
HOof a substance to SLOW
be used as a medicine
O usually requires 3 3
Ethanoic anhydride
a 3number
CH O C of ++ + CH3+
chemical steps,
O CC known
CHO3 as a synthetic
CH3 O pathway.
C +
You
O C 3 +3 recall
should
CHCH CHO3
+C H 2
C
that the general
OH
O chemical
HO
CO reaction
CO to form an !
ester is: O O O
CHEthanoic C acid +OH Ethanoic C acid CH3 CH C anhydride isC CH3by+combining
H2O
OEthanoic Oprepared
carboxylic acid + alcohol O Water
CH3ester + water
3 O 3 OH
O CHO3
O O
CH3
two molecules of ethanoic acid (Figure 14.3).
Ethanoic anhydride
This reaction C could be used to O acetylsalicylic
form C acid. Interestingly, it is the
Acetylsalicylic
Salicylic acidSalicylic
acid
Ethanoic acid acid Ethanoic
Ethanoic Ethanoic
Ethanoic acidacid A waterOmolecule isacid
Acetylsalicylic Acetylsalicylic
acid Ethanoic
also produced. acid
Water Ethanoic acid
O
hydroxyl group in
(aspirin) OHthe(acetic
anhydridesalicylic
C acid molecule
anhydride
acid) (aspirin) O
that functions
(aspirin) C CH
as the alcohol
3 (acetic acid)(acetic acid)O
Ethanoic anhydride
in Alkanol
a reaction with + ethanoic
+
Carboxylic acid
Acid O (acetic acid) to form Ester acetylsalicylic + + acid CH3
Water C
O OH O OH O
and water.
Figure 14.4Figure 14.4 O
C
CThisfrom
icylic acidStructural
(aspirin)
OH
is
Structural
equation CH3
asalicylic
slowforequationO forethanoic
reaction. Also
acidpreparation
the and the the yield
preparation isacid
low,
C of acetylsalicylic
of acetylsalicylic
OH
chemfact
as acid
(aspirin) the
from water
(aspirin) formed
salicylicfrom and tends
acidsalicylic acid and ethanoic
ethanoic
O OH O of water.CHO O
s converted to todrive
(acetic)ethanoic
(acetic)
the acid
anhydride. anhydride.
by the
Unreacted
reaction Unreacted
ethanoic
C addition
backwards. ethanoic
anhydride anhydride
In 3an isalternative
converted CH3 to
isCtoconverted
ethanoic
reaction ethanoic
acid
pathway, acid by the
by the addition
which isaddition of wate
ofOH
water.
CH O During World War I, Britain was unable to
faster
C and produces
+ acid3 higher
Salicylic O yields, the ethanoic
Ethanoic C acid is replaced
Acetylsalicylic + acidwith
CH3 ethanoic
C Ethanoic acid
Quicker Synthetic Pathway
anhydride OH (acetic anhydride).
C anhydride O obtain
This is the preferred
O aspirin
C pathway CH
(aspirin)
3
from its German manufacturer.
for the synthesis OH
F
(acetic acid)
C In 1915, the British government offered O a Feli
d andMake of
aceticaspirin
The Ethanoic +
(Figures
(ethanoic)
The
products,
Anhydride
14.3,
products,
acid, 14.4).
O have acetylsalicylic
acetylsalicylic to be
acid andacid O and
acetic
reward
Unreacted (ethanoic)
of acetic
20 000
ethanoic
+ (ethanoic)
acid,
CH
to anyone
anhydride 3 have
C
who acid,
could
water to
is be a ch
have t
Figure O 14.4 CH will react with water to
produced in a

beforeseparated
it can be separated
put
and into
the and
tablet
producttheformproduct
purifi and
ed purifi
before edit before
can be itputcanacid be
into put
tabletinto formtablet andform
3
C develop
produce aethanoic
workable manufacturing process
condensation
O
reaction
Salicylic acid Structural Ethanoic
equation for the preparationAcetylsalicylic
of acetylsalicylic
for aspirin Oso that the country could make ethanoic
acidacid (aspirin) from salicylic
Ethanoic acid
acid and
packagedpackaged for sale.
OH
OH O for
HO
(acetic) anhydride. sale.
HOCH
anhydrideUnreacted
3 ethanoic anhydride
(aspirin) is converted to ethanoic (acetic acid by acid)
the addition of wate
CH3 C + CH3its ownC supply. The reward
CH3 +was wonirritating
by athe to
steless and is much
Salicylic acid
Acetylsalicylic
Acetylsalicylic less
Ethanoic
isCvirtually
irritating
acid acidCH3
to is
the virtually
tasteless tasteless
andacid
Acetylsalicylic
andC isless
is much much H2O
less
irritating
Ethanoic
to
acid
O O Melbourne pharmacist, George Nicholas,
not until
stomach
Figureafterstomach
it
than has
14.4 acid passed
than
salicylic
anhydridesalicylic
through
acid acid
the
itself. It itself.
is not It is not
until
(aspirin) afteruntil after
it has it (acetic
passed hasWater
passed
acid) through
through the F
Ethanoic Ethanoic acid who Owent on to Omarket aspirin under the
hydrolyses)
Structuralin
stomach stomach
the
that
equationalkaline
The it the
for that
reacts conditions
itwith
reacts
preparation
products, with
ofwater in(hydrolyses)
water
acetylsalicylic
acetylsalicylic acid (hydrolyses)
(aspirin)
acid
name and in the
from inname
salicylic
acetic
Aspro. The theAspro
alkaline
acid alkaline
conditions
and
(ethanoic) ethanoic condition
acid,
comes in Form
have
from t
Ethanoic anhydride
e more the effective
small
(acetic)
Figure the
anhydride.
14.4 salicylic
small
intestine intestine
Unreacted acid.
and
ethanoic and
returns returns
to
anhydride the to
more
is converted
separated and the product purifiedNicholas theto more
effective
ethanoic effective
salicylic
acid
beforeProducts.
by the salicylic
acid.
addition of acid.
water.
it can be put into tablet form
React Ethanoic Anhydride with Salicylic Acid
Structural equation for the preparation of acetylsalicylic acid (aspirin) from salicylic acid and ethanoic
(acetic) packaged
anhydride. for sale.
O COOH OH Unreacted
COOH COOH ethanoic anhydride O is converted
OH to ethanoic
COOH acidCOOH by the addition of water.
OH
Acetylsalicylic
CH O acid is O virtually tasteless and is much less irritating to
OH (ethanoic) acid, have to be
TheCproducts,
stomach acetylsalicylic
OHO + than
O
3
salicylic acid
+ Hacid
and
COH
itself. acetic
OH
CHC 3COOH
O C 2O + HO 2O It C is notCHuntilOH after
+ CH it OH
has
3COOH +passed through
CH3COOH
smallseparated and the product C purifi
FAST ed before
in small it can
in smallbe put 3
into tablet form
OH and
estinepackaged
stomach
The products, + that itCH reacts
3
acetylsalicylic with
CH3 water (hydrolyses) in the alkaline condition
acid and acetic
intestine intestine(ethanoic)
+ CH acid, C have to be
for
the sale.
small
O
intestine and returns to theO
more effective salicylic
3
acid.

14
14
separated and the product
Acetylsalicylic acid purifiedtasteless
C is virtually before itand Figure
canisbe 14.5
put into
much less tablet Oform
irritating to and
the !
Acetylsalicylic acid is hydrolysed in the small
packaged
stomach
Salicylic acidfor
than sale.
salicylic
Acetylsalicylic
Acetylsalicylic acid acid
OEthanoic
acidCHaciditself. It is not until after
Salicylic it has
Salicylic
acid passed
acid through
Ethanoic the
Ethanoic
acid acid Etha
COOH 3 intestine to salicylic
COOHacid. two
(aspirin)
Acetylsalicylic (aspirin)
acid is virtually tasteless and is much less irritating to the
stomach that it reacts with water (hydrolyses)
Salicylic acid Ethanoic O Acetylsalicylic
OHin the alkaline conditions in
acid Ethanoic acid Aw
stomach
the smallthan salicylic
intestine andacid
anhydride itself.toItthe
returns
O C is not
+ H
more2until
(aspirin)
O after it salicylic
effective has passed (acetic through
acid)
acid.
OH + CH 3 the
COOH
stomach that it reacts with waterCH(hydrolyses) 3
in
in the alkaline conditions in 22
small
intestine
Figure 14.4
the small COOH intestine and returns to the more effective COOH salicylic acid.
Structural From organic molecules to medicines
equation for the preparation of acetylsalicylic acid (aspirin)
O
from salicylic acid and ethanoic
(acetic) anhydride. Unreacted ethanoic anhydride OH
is
converted to ethanoic acid by the addition of water.
Acetylsalicylic acid
C including
reactionOpathways
organicCOOH + appropriate
H2O equations COOH Salicylic acid
OH +function
and reagents: CH3COOH
of organic Ethanoic acid Dur
(aspirin)
molecules in the design and O in small including the production of aspirin from
synthesis of medicines obta
CH 3
salicylic acid. OH
intestine
O C + H2O OH + CH3COOH In 1
The products, acetylsalicylic
CH3
acid and
in small acetic (ethanoic) acid, have to be rew
VCEasy
Collision Theory VISUAL
CHEMISTRY
H
negative H positive H
4.1.1
Exothermic gives out energy Endothermic requires energy

EA! EA!
(activation energy)
VCEasy (activation energy)
Energy

Energy
Reactants Products
Kinetic molecular theory VISUAL
CHEMISTRY
5 big assumptions: H H
Products Reactants 2.2.3
random motion,
negligible volume
exert no forces on each other
4collide
Wayselastically
to Increase the Rate of A Reaction
with each other and the container walls
kinetic energy which is directly proportional to the absolute
temperature of the gas
increase surface area Remember this list by the acronym:

increase concentration SCaT, Cat!


Gases take up the shape and volume of any container
increase temperature
Pressure force exerted on a surface by gas particles as they collide with
eachadd
othera catalyst
and with the walls of the container
Partial Pressure the hypothetical pressure of that gas if it alone occupied the
volume of the mixture at the same temperature
Maxwell-Boltzmann Distribution
Kinetic Energy a small increase in temperature causes a large increase in the
vs temperature number of particles with kinetic energy above a certain level

20C
30C
proportion of
molecules with a 40C
particular kinetic
energy 50C Shaded area represents
number of particles with
enough energy to react
(>EA)

kinetic energy EA (activation energy)

collision
kinetic theory theory
molecular and factors
and itsthat
useaffect the rateproperties
in explaining of a reaction including temperature, pressure,
of gases
concentration and use of catalysts, excluding: a formal treatment of the Maxwell-Boltzmann
distribution, reaction mechanisms and rate laws
VCEasy
H VISUAL
CHEMISTRY
Calculating H 4.1.2
negative H
Exothermic gives out energy

EA!
Energy, H

(activation energy)

H = Hproducts Hreactants
Reactants

H
Products

Effects of a Catalyst

negative H
Exothermic gives out energy

EA is
decreased
EA!
(activation energy
Energy, H

without a catalyst)

Reactants EA with catalyst

H H stays
the same
Products

energy profile diagrams and the use of H notation including: activation energy; alternative
reaction pathways for catalysed reactions; and deduction of H for an overall reaction given
energy profiles or H of two related reactions
You may have heated blue-coloured hydrated NH3 copper(II)
You may sulfate
have heated blue
Equilibrium explained
(CuSO4.5H2O) in a test-tube. A white solid (CuSO
N2
H
+3 2 4
) forms
(CuSO
and droplets
.5H2O) We incan a test-tube.
the idea that pA
VCEasy
Equilibria of water appear on the walls of the test-tube.
3 When water
the white powder, the blue compound is re-formed.ofThis
is mixed
water
4 with
appear
use
on the VISUAL
walls of

H
reaction is reactions reach an equilibr

2N
Time
the
represented by the equilibrium equation: Equilibrium first the white powder, the blue c CHEMISTRY
forward and reverse rea

4.1.3
established Suppose nitrogen gas an
Figure
Reversible Reactions 16.2
CuSO4.5H2O(s) CuSO4(s) + 5H2O(l) represented byat athe constantequilibrium
temperature,
Figure 16.3 to react immediately, form
Nimetal
The reaction hydride between batteries are used toand
nitrogen power
hydrogen
The variation toof form
the rates ammonia,
of the forward anddescribed then occurs:
some reactions do not go to completion
thisabove,
digital camera. can alsoThebechemical regarded reaction
as a inreversible
the
back reactions with
hydrogen are mixed.
reaction, CuSO
since
time when nitrogen andammonia4
.5H2O(s) CuSO4(
As the forward reactio
batteries that provides
they use the symbol above
decomposes into nitrogenelectricityand is reversed
hydrogeninwhen it is heated. The equation for hydrogen decrease, so
orderthistoreaction rechargeisthem. written as: The reaction between N2(g) nitrogen
+ 3H2(g) an 2N
Example N2(g) + 3H2(g) 2NH3(g) Concentration (M) above, can alsoIn a be At
Dynamic regarded
the same time
Equilibrium
as as
am
react to re-form nitroge
3
decomposes into nitrogen reaction, 2NH and 3
(g)hyd

Rate Equilibrium explained
initially, the forward
H2
this reaction isconstant constant
writtenconcentrations
ammonia
temperatureas:increases.
reaction and reverse Eventually the forward
We reactionidea have that
different constant total gas pressure
2 + can use the processes can be reversed to understand why some (Figure 16.3). When
N

reactions 3H
reaction rates
reach an equilibrium. Chemists 2have shown that in these N2(g) + the
reactions3Hreaction
(g) 2NH (g)
is incomplete
2 (all substances are present in 3 rat
2 at exactly the same
the SCN forward2and NH3 reverse reactions occur simultaneously. ammonia,
mixture)nitrogen an

the equilibrium
Concentration

Fe
Suppose nitrogen gas and hydrogen gas were added to a sealed container equilibrium position n
3+

e
FeSCN
at a constant H2
+ 3 temperature,
2+

as in Figure
at equilibrium,
1
the 16.1. The
N 2
nitrogen and hydrogen start
Equilibrium explained
REMEMBER:
either the forward react
of Nimmediately,
2 forward and reverse a point of balancean
conctemppressureincomplete
to react forming ammonia. The following sequence of events
We can use the idea that16.4 processes
Time
k Initial reaction rates are equal NH3 Figure shows the c
then 3occurs:
equilibrium
ll
H

Dilution New equilibrium


Equilibrium is a dynamic st
reactions reach anceased.
equilibrium. Ch
2N

established
e
As the forward reaction proceeds, the concentrations of nitrogen Time and Instead they occur
Figure 16.14
Time
hydrogen
Graph showing
equilibrium
the effect of dilutiondecrease,
on the
Equilibrium first
so the rate of theN2 and ammonia
H2 theproduction,
forward
Equilibrium andis,reverse
that equilibrium: reactions oc
N (g) + 3H (g) 2NH (g), decreases. added to container established the amounts and conce
Fe (aq) + SCN2(aq)
established
Fe(SCN) 2(aq).
Suppose nitrogen gas and hydro
3+ 2+
3 Increased
m
At the same time as ammonia is being formed, some ammonia molecules
pressure the total
O gas pressure is 2
c. Figure 16.4

Concentration
g react to re-form nitrogen and hydrogen. Theinrate
Changes ofat thisa reverse
the concentrations
Small K (<104of
constant
) N2, H2 and
temperature,
(or back) the temperature
SO as inis Fig cons 2

Le Chateliers Principle
Large
the K (>104)
reaction is incom

6
n Figure For the
reaction,
chemfact 16.3 2NH3(g) N2(g) + 3H2(g),
equation aW + bX cY + dZ consists
at mostly
a ofparticu
NH3 asincreases
a mixture
to
of nitrogen
as
indicates
equilibrium
the react
thatand
the
mixture immediately,
hydrogen
K1 gas
concentration
[reactants]
of indicates
indicates that
forming
SOthat the
equilibrium
equilibrium mixturemixture).am 3

reacts. As indicated by the coeffi cients of the


e ammonia increases.
The variation of the rates of the forward and
FeSCN2+ has a dark red colour. It has been
consists mostly of [products]
SO molecules: 5 2 SO molecules: 1

then occurs:

16
1
2 Time
equation3for the reaction, for every amount of
then:
used in theatrical productions to make fake Initial
reactants products
tionback
aW + bX + dZ and
cY nitrogen at aand twice
particular temperature,
O molecules: O molecules: 1
Eventually the forward and back reactions proceed at the same rate
2 2 equilibrium
reactions with time when
blood, formed by breaking separate plastic N that reacts, three times as much H reacts 2 2 Pressure New equilibrium

As Total theis forward reaction proce


SO molecules: 1 SO molecules: 5
bags containing pale-coloured Fe3+ ions and as much NH is produced.
3 3 increase established

g (Figure
hydrogen 16.3). When this situation
are mixed.
colourless SCN ions together. Total is reached,
9 ammonia formed
7 3

y
Katis exactly
the c d
the same rate [Y] as it[Z] is breaking down. The hydrogen Figure
concentrationsdecrease,
16.11
so pressure
of The effect of increased theon the rat
K =A and
). Figure 16.10

] [Z]d equilibrium
ammonia, nitrogen hydrogen 264 willpressure
then on the remain constant. 2SOAt
(g). the equilibrium 2SO (g) + O (g)

2SO (g).
dc representation of the effect of increased
N
equilibrium 2SO (g)
(g)
+ O (g)
+ 3H (g) 2NH (g),
2 2 3

equilibrium position [W] [X]change


constant a b 2 2 3

no further n will chemistry


Industrial
In take place2 in the rate 2of 3
]a[X] b
Concentration
either the forward reaction or the back reaction. The
(M)
Atadjusts
reaction
The system the to thesame
has reached time
increased pressure as ammonia
by undergoing a net back reaction:i
KHeating
is anunique
Figure 16.15
for each
and N O formula and at each temperature.
favours where gas. is a constant. This is (Figure
(g) +known
the formation of brown NOK Note thatas the 3 ofequilibrium law
aequilibrium
point ofof NObalancean equilibrium, i.e. N 3H2(g) react 2NH
toconcentration
re-form (g). nitrogen
NO in the new equilbrium willand hy
mixture equilibrium moves in the direction that produces fewer particles and reduces the press
2 2 4 2 16.12). the be higher than
stant. This is known as the equilibrium law.
Figure 16.4 shows the changes
2
in the concentrations of the
reaction,
chemicals.
the initial equilibrium, but not as high If2NH
as it would be
(g)system
if there

had not been
Nequa
a net
(g)
to a +
back react
2
dilution (for equilibria in solution)

Factors
3Equilibrium
e equilibrium H Note that law that
is a Affect
dynamic
depends the
the
state, equilibrium
Position
since
upon the
the forward of an and
equation law
Equilibrium
back
(Figure depends
reactions
16.13).
used dynamic
have
for
change,notupon
the
the3system willthe
an equilibrium is subjected
adjust itself 2to
changing the temperature.
Let us consider the effect of each of these changes in turn.

ceased.2 Instead they occur simultaneously at the same rate. ammonia


During Adding increases.
partially oppose the effect of the change.
extra reactant or product
reaction. For example, thegases equilibrium O andbetween the gases
Concentration
(not to scale)

ample,equilibrium:
the equilibrium N2O4 between the N2O4
NEventually
2 4
NO the2Is thereforward a Catalyst? and b
Suppose a vessel contains an equilibrium mixture represented by t
equation:
Concentration

can be represented
and concentrationsby several equations, including:
N2
Concentration

the amounts of chemical substances remain constant


N2(g) + 3H2(g) 2NH3(g)

ed by several equations, including:


the total gas pressure is constant (if gases are involved)
NO2
NO2
(Figure 16.3).
H2

Catalysts When have no effect this sit


If extra nitrogen gas were added to the vessel without changing the volum
or temperature, the mixture would momentarily not be in equilibrium. T
following events occur as the composition of the mixture adjusts to retu
2 on equilibrium! They just
at exactly the allowsame rate to beas it i
to equilibrium:
the temperature is constant
[NO2] 2
[NO
equilibrium
] 2
NH3 the increased concentration of nitrogen gas causes the rate of the forwa
Time Time
reaction to increase and more ammonia is formed
e
the reaction
Initial
is incomplete (all of the substances
Initial
are present in reached
the faster.2
2NO2(g), forNwhich O4(g) K1 = 2NO (g), forammonia, which K1nitrogen = and hydro
equilibrium
as the concentration of ammonia increases, the rate of the back reacti
equilibrium Time
Temperature New equilibrium
Pressure New equilibrium BeforeInitialcompression
equilibrium Immediately
to re-form N2 and H2 increases At new
established
[N2O ] [N O ]
Nitrogen New equilibrium

equilibrium mixture). 2 2
increase increase established (initial equilibrium) added established ultimately
after the rates of the forward and backequilibrium
compression reaction become equal aga
and a new equilibrium is established (Figure 16.9).

Increase
Figure 16.16 Temperature Figure Increase
16.12 Pressure
4
Add16.13
Figure
equilibrium position
Reactants
Figure 16.9
Add 4 no furthe
2 Products
A representation of changes in concentrations
Note that when equilibrium is re-established the concentrations of
substances have changed. The overall effect of adding nitrogen is to increa

[N2NOshift
O4]
that occur when additional nitrogen gas is
The effect of heating on the equilibrium The effect of increased pressure on the the concentration of ammonia at equilibriuma net forward reactio

either the2NOforward reaction


then shift or th
When the pressure on an equilibrium mixture of N O and NO is increased, the colour of the gas initiall
added to the equilibrium
1 (g) NN 2O will
[N O will ]
For similar reasons,
2 4 adding 2extra amounts of the other reactant, H2, a
2NO (g). equilibrium N O will
(g) then 2 (g). slightly
N2(g) + 3H2(g) 2NH3(g).
Equilibrium then shift Equilibrium willfades
thenas theshift (g)Equilibrium
N O (g), for which K
Equilibrium
=
2 2 4 2 4 darkens but then
2 reaction N O (g) occurs. increases the concentration of ammonia. It is important to note, howev
2 2 4
2 4
K2balancean
that even though the concentration of the added reactant decreases as t

endothermic reaction2NO2 (g)moles 2 of gaseousN


]2O4(g), forwardfor a which = reaction2 equilib
slightly in favour of the reaction with
2 in 4favour of the slightly in favour of the slightly in favour of the
fewer [NOproduct reaction point of reverse
system moves to establish the new equilibrium, its final concentration

[NO ] theofcontainer
higher than in the original equilibrium.
n 2 2 chemfact Addition of more product, NH3, increases the rate of the back reactio
In general the effect of a change of pressure, by changing volum
ns
e
NH 3
[NO2] depends on Figure
the relative 16.4
number of gasshows
particles on the
2 sideschanges
The effect of adding more nitrogen can also
both
be predicted using the equilibrium law:
[NH3]2
the
When equilibrium is re-established the concentrations of the reactan
equation.
N2 and H2, are increased. The concentration of NH3, while decreasing
the system moves to the new equilibrium, is higher than at the origin

By Equilibrium gas is a dynamic ]state,


and sinc
K=
m
NO2(g), for
1 which K = [NO
[N2][H2]3 equilibrium.
CHEMICAL
equilibrium: EQUILIBRIUM RIUM
representation of reversible and non-reversible adding an inerthomogeneous
reactions: equilibria It is sometimes possible to arrange to remove a reactant or product fro

[N O ]
When extra nitrogen is added, the
3 1/2 2 an equilibrium mixture. As you would anticipate, this has the opposite effe

N(equilibrium
O4CHEMICAL
(g) expressions NO (g),The for of which Kof3the=they
Le Chateliers principletemperature concentration fraction will be momentarily
m Time to ceased. Instead occur simulta
on an equilibrium from addition of the substance.
the equilibrium law 2RIUM
EQUILIBRIUM 4 restricted use
total concentrations),
pressure of an equilibrium Le Chateliers
less than K. The mixture is then no longer in
mixture of gases may also be changeTo summarise:

2 [N O ]
equilibrium. A net forward reaction will occur,
y
Principle and factors 2which affect the position of 2 without
equilibrium changing the volume container, by adding
increasing the amount of products, until the 1/2a non-reacting g
addition of a reactant leads to the formation of more products (a n
Le Chateliers principlepressure concentration fraction again becomes equal forward reaction)

portantN2 that and H2the equation beprincipledilution


specified when
Le Chateliers principleinert gas
275 LeEquilibrium
Chateliers
equilibrium:
an ofequilibrium
such as helium, neon or argon.
The impact
to K. 2 4
this change is very different to the previous case whe
addition of a product leads to the formation of more reactants (a n
back reaction).
Notice that, in all cases, a net reaction occurs that acts to partially countera
!
the pressure is altered by changing
the theA containers
effect of the change. volume.
useful generalisation Despite
called Le Chateliers t
princip
oncentrated
In Unit 2 we [H
saw strong
O ][OH
that water] acids,
will react such
HCl(aq) + H2O(l)
with as in10
itself a M
pro
H3O+(aq) + Cl(aq)
+
Unit 2 we saw
s expression
equilibrium, can=
K that
alsowater will .react
be written as: with itself in a process
The expression for the equilibrium
3 VCEasy c
constant can be written as:

][OH ] waterpH: a convenie


change
Kw
ionisation:
isation: colour [H O] at specifi K=
c concentratio
[H3O+][Cl]
[HCl][H2O] VISUAL
CHEMISTRY
2
2

K = [H O
In aqueous solutions,
+
molecules
In this reaction, the Cl ion can be described as the conjugate base of HCl.
are usually far more abun
asure H O(l)
other the H+ H acidity
substance
O(l)
w
2
+
O(l) H O(l)
present. Hof
3

The solutions.
O (aq)H O (aq)
+ OH (aq)
concentration
conjugate 2acid of Cl .

+ OH
of
(aq)
water 3 in 4.1.4
In any acidbase reaction, the conjugate base is the substance+formed from
+ HCl 3is referred to as the
2 when it donates a2 proton (H+). Similarly,
the acid

ere K is called the ionisation constant of water. Thisaqueous equilib


The range of H O +
con
Since water is the solvent in aqueous solutions and its concentration is
w
irtually
plies to constant
both pure at about
water
[H O [H56
and
][OH O M.
all][OH
] We
aqueous ] solutions.
virtually constant, we can write the equilibrium+expression as:
therefore write the equilib +
At equilibrium,
equilibrium, K =
K = water as: [H O] . . [H3O+][Cl 3
3 ] = Ka
3
thepure
ionisation
water atof25C,
H: [Ha convenient way to me
K[H2O] = 2
In scale,
chemists have called
found thatthe pH
the concentratio sc
[HCl]
[H O]
The quantity Ka is known as the acidity constant.
2
2 The value of Ka for
2

O and +
In aqueousIn
OOH aqueous
][OH ions
solutions,solutions,
] = is
K 10+
[HM. water
O] The
hydrochloric
water

moleculesmolecules
value of
= a constant are
7
are
Kusually
acid is 10 M at7
of the hydrochloric
solutions, most
usually
at 25C far
can be mor
calc
25C. This means that in hydrochloric acid
far more abun
acid has2 been converted to H3O+ and Cl.

defi ned as:


3 2 ed as a strong acid. w
anysubstance
other other substancepresent. present.
The The concentration
concentration of waterof in
This is why hydrochloric acid is classifi
water in aq
aqueous
In contrast, ethanoic acid has an acidity constant of 1.75 105 M at
14 TABLE217.2 K a values for some
K = [H Ocan
s expression ][OHalso] =be+10written
10 as: = 1.0 10 M
25C. In a+solution of ethanoic
7 position of7
acid, the equilibrium favours the
is virtually constant at about 56 M. We therefore write the
range of H at Oaboutconcentrations in solutio
w 3 common acids at 25C
irtually constant 56 M. We therefore write the equilib
reactants and there is a relatively small amount of products.
Acid Ka (M)
Because K is a constant, an
CH3COOH(aq) + H2O(l) CH3COO(aq) + H3O+(aq)

thefor =the ionisation 3] of as:


waterofas:ions w
tice that the
Kionisation
[H O concentrations
][OH at 25C only
of water + [H (varies in pure
pH in=
with]temperature)
O ][CH COO
increase water
results inare
[H ]log
+
a [Hextrem
O +
+
Ethanoic acid 1.75 105

e, called the pH scale, has been develo


3 3
K= Citric acid* 7.2 104
w 3 [CH3COOH][H2O]
each HO ion present in a glass
+ decrease
of in [OHthere
water, 10
] and vice
[H O+][CH3COO]are versa
560 3 mil
Phosphoric acid* 7 103

ere K
[H O is [H
][OH O] ][OH
called =the
K
3 =K
][H [H
ionisation
+
O] = a O] = a constant
constant
constant
Ka = +3
3

of water.pure
[CH3COOH] This waterequilib 2 2
2 Nitric acid 2 101

lecules! There are ions there, though, so, although is Hydrochloric acid 107

ned as: 1Alternatively, this2expre


w
3 Ethanoic acid is classified as a weak2acid because at equilibrium only a small

pHpureFormula pH Formula
Sulfuric acid* 109
liesThis
toconductor
both
expression water
can and all it
aqueous solutions.
proportion of the acid has been ionised.

spoor
expression can of
also bealso be
electricity,
written written
as: as:
does conduct slightly.
The acidity constant can be used as a measure of an acids strength. The *In the case of the polyprotic acids citric

In pure water at 25C, chemists have found that the concentratio


acidity constants of several common acids are given in Table 17.2. From the acid, phosphoric acid and sulfuric acid,
table you can see, for example, that while phosphoric acid is stronger than the Ka value quoted involves the loss of the
KO = [H3O] ][OH + nitric acid.
citric acid, it is weaker than
] + first proton.
O+ and KpH w OH
= [H=
cidic and basic solutions log
w +][OH
3 ions
Calculations involving
is
10
10 [H7
M.acidity
3
O The ]
constants
value [H of K
3
O w
at !] =
+ 25C can
10 pH be calc
ere where KO ispHcalled the 7 ionisation constant M2 of water. This
Refer to the Acidity Constant table in the

KKww=is[H called the ionisation constant of water. This equilib


The following example shows how an acidity constant can be used to 14
][OH ] = 10 10 = 1.0 10
VCE Chemistry Data Book. This is available on
calculate w +the
of a solution of a weak acid.
7 the VCAA website.
3
applies toacidic both pure water and all+ aqueous solutions.
ernatively,
solutions
lies
tice
to
K
that a
both of
the(The
Worked pure K this
value,
example
concentrations
watersubstances,
17.2 or expression
and
dissociation all
of
H For
aqueous
ions
3
O constant in pure
ions
can are
solutions.
pure for water
an
water be
formed acid) rearran
are
by at
extrem 25
reacti
dInwith pureIn water, pure
water as atwater well
acid25C,
at
as 25C, from self-ionisation chemists have of
is 1.75 10 M.chemists have found that the concentratio
found water. that Sothe theconce
conc
Calculate the pH and percentage hydrolysis of a 0.50 M ethanoic acid solution, given that the

For acidic solutions,


K for ethanoic 5

H each
+O H +O H + O ion present
ions and
+
a

will OH
If two be
ions
ions 7inisyour
greater in10 acan
7glass of 7
than M.
equation The 10 have water,
value M a at
1:1 ofthere K
25C.
ratio, are
at
then 25C
Since560can
you mil
the
O 3 and K a OH
[Hone
3 From
Trick 3
O 1the
Solution
+ ions
equation
]can H=
is for
10 10the reaction
pH M. we The see value
that for of
every K
mole ofat 25C
ethanoic wacid can
that be
ionises, calc
lecules!
O+][OH There Themole of
3]Kremains
equation
are
for O treat
the +
ions
and
ionisation onethem
of
there,
mole
ethanoic
+constant,
acidofas
is:CH one. though,
COO
the will be formed.

7 concentration
so, Soalthough we can say: pure water is
w
of14 OH ions in
of 0.020 M HCl at
17
17
3 3

Kwat = 25C[H =
OoftheHmust
][OH [H O
CH3COOH(aq) + H2O(l)
]the][OH
=reaction
]10we can

] =
formed.
10 10
CH3COO (aq) + H3O+(aq)
= 1.010 7
= 1.0 10 M 2
s poor conductor of electricity, thatit does ofconduct10acid thatMionises, slightly.
w [H + O ] = [CH
+
3 for COO COO 7
] 7 14 2
ution be less bethan 10 M.
From the equation
[H for
O ][CH the reaction + we can see that for every mole of ethanoic
7 acid that ionises,
From
Old equation3From
one molethe
equation
equation Ka =3
O [CHand one for
+
3
molethe of CHreaction
COO will we
3 3 see
can= 1.75

see
for
105 M
So we
every
that
can say:
mole
for every
ethanoic
mole of ethanoic acid that ionises,
For only pure water at 25C, [H O ] = 10 M
COOH]
can + 7are
one mole of H O and one mole of CH COO will be formed. So we can say:
+

= 1.7.
3 3

n donateNotice that the concentrations of ions in pure water e


If we substitute this intoone themoleexpression for K will , webeget:
3
ds can
donate only
one mole of[H
3
HO O and of CH COO
3
formed. So we say:
The opposite is true for basic solutions. The concentration of
289
[H3O+] = [CH + COO]
tice
with water, itthat Ifthe concentrations of ions in pure
a
water are extrem
3
ith water, it is 3 + ] = [CH COO ] 3
ule.

3
Assume:

cidic and basic solutions


is
olyprotic acids can we substitute 3
[H O+ ]
+ 2 3
this into the expression for K , we get: Equilibria involving acids and bases

atonheach
basic For
on per molecule.
each
solution [H H [HOOO
+3
is]] =this [CH a
ion
greater COO present] for10K , we
than 10 in 7a glass of water, there
M and that of H O + are 5
ionsmil is
For to acidic solutions, [H O ] > 10 M, so
Polyprotic acids can If+we substitute into the =expression
1.75 Mget:
per molecule.H O ion present in a glass of water, there are 560
5
+ 7
+ 2

0.50 For basic so,solutions, [


3 3
s r molecule to New equation [CH3
3 [HCOOH]
= 1.75 105 M
a
nd H3PO4, with 3we substitute [CH 3 3 + 2
COOH] O ] 3
H POmolecules! There are ions in a there, ofthough, although pure is w
ds can
er molecule If 3
this into the expression for K , we get:
M.
acid. = 1.75 10 M
3
5
7and
lecules! There are ions there, though, inso, although pure water
, is a triprotic acid.
, with We Wealsoalso knowknow [CH
from theCOOH]
from the
equation equation
for the reaction forthatthe reactionM solution that a 0.50
ethanoic a
acid: M solution of ethanoic acid:
ule.
olutions of2Weacidic ]substances, Hweak in O ions are formed byat+reacti
3
3 4
[H +
know O
of 0.020 M is a HCl at itwe25C ionise tohas [H O ] =
+ 2
e, is a triprotic acid.
as K a poor
Trick You
conductor may assume of that
electricity, acids
solution ofdont
it does dissociate
conduct slightly. all!
of 0.300 M NaOH a
also [CH3COOH]
3 + [CH3COO ] = 0.50 M
from the equation for the reaction
Mthat 3 aM 0.50 M ethanoic acid:

In poor summary,a
conductor
However,[CH [CHat 25C:
COOH]
[CHCOOH] of electricity,
+ = 1.75
[CH COO 10 ] = 0.50 does it will onlyconduct

5
slightly.
dhacid.
with water, very small Foras a 0.5well
ethanoic
extent.
acid
COOH]
Mthe
As
3
solution
weak
3 3
as
small value
+acid
[CH
from
with
of a ofweak
COOa very ]small
acid (e.g.
K indicates self-ionisation
= 0.50
that
K , so
3
3 M
ethanoic
little CH COO
know
acid), we
is formed can
a
ionisation, of water. So
byassume
a
3 the conc
in pure water and solutions: [H O ]solution
= [OH only]ionise
=acid:10 M

However, ethanoic neutral


acid isaaweakweak acid with a. Therefore,
very , small K0.50
, so we+ know ittoof
will to a 7
=in31.7.
a 3

We wealso that
know
However,
can none
approximate oftheit above
from
ethanoic dissociates
theexpression
acid isequationintoto:CHfor
acid COO theaand
with H small
reaction
very
Kthat so [CHin7
we aCOO
know + ]itwill
0.
Monly ionise a ethanoic

H O ions verywill be the greater than


Since M and [H
that little10 isM
[OH3O
at 25C.
][OH Since
]
the
3 3
+
+ a

Acidic
and and basic solutions
3 a
very small extent.
small extent. AsAsthe small
small value
value of K of K
indicates indicates that
CH COOlittle CH
formed COO is formed
by ionisation, by ionisation,

cidic basic solutions


+acidicwesolutions: [H O ]for K>,to:we]10 M ] < 10 M
[CH3COOH] 0.50 M
we [CH
+ 7 a
a
3
7 3
Old equation COOH]
can approximate the + [CH
above COO
expression = 0.50
O ][OH [H]O ]remains If can
we substitute
[CH COOH]constant,
approximate this into the the
3 revised above
3
expression expression
the concentration
get:to:
3
of7OH ions in
For basic solutions, Mexpression[H O +
] +< ] 10 M; so
a

[H O 0.30 M
0.50 M
+
+ 2
However,=[CH 3
ethanoic
1.75 10 Macid is
COOH]
3 5
a weak
0.50 acid with a very small K , so we know it will only ionise to a
ution In
solutionsIfweweof at 25C
solutions
very
Assume:
0.50IfMwe substitute
[H small
acidic must
extent. of this
As
3
be
acidic
into the
substances,
the smallless
revised
value than
substances,
of K for
H
K 10
indicates, we
O3
7
get:
that
+ M.H
ions
little O CH are
COOions formed
is formedare by formed
a

by
ionisation, reacti
by
3
a
O ] = 8.75 + 2
10 6
a 3 3
substitute ] 10this into the revised expression3for K , we get:
[H] =O 2.96
3

of 0.300 M NaOH at 25C has [OH ] =


+ 2

The acid oppositewith can


[H O
M is
approximate true for
= 1.75 10theMabove expression to:
water, 10 ]as well basic
andas from solutions. self-ionisation The concentration
of water. Soofth
+ 3
3 5
3 a
d with water, 0.50
pH
as
= log
well
[2.96
as
= of
2.5
from self-ionisation of water. So the conc
3
pH as a measure
[H O We][Hcan + 2 of strength acids bases; K ,K for weak acids w a
measure
O ] = 8.75 the extent
10 0.50 M of the reaction by calculating the percentage hydrolysis (or
basic solution isbe greater bethan 10 10 M 7and10 that ofatH325C. O ionsSin is
+ 2 6
[CH COOH]
[H O ]
7 hydrolysis is given 7 +
of+ H O [Hwill O ions will greater than M
3
percentage+ = 1.75
3
ionisation), 10
the
3 M
fraction of the
5
acid that is ionised. Percentage +
H O ions
0.50
3by theMexpression:
] = 2.96 10
greater than M at 25C. Since the
Since +[H O[H O ][OH ] by = 1.0 10 M 3 ,
+ 3

7 3 If[H+
we substitutepH =
3
log this+
[2.96 into 10 ] = 2.5 3
the revised expression for K , we get: 14 2
M.
ding quantity,

O ][OH
measure the
mmonia as an 3
[CH][OH
O COO ] =We
+ 2

][CHremains
3 3
++2
COOH]
100
] 8.75
] 2.9610
can =measure remains
10
100 of the constant,
6 3

0.50 constant, the concentration of OH ions in


the extent
3
reaction calculating the
the concentration
percentage hydrolysis
a
(or of OH
VCEasy
Renewable Energy Sources VISUAL
CHEMISTRY
4.2.1

+
coal cheap pollutes

oil easy to transport limited supply

natural gas efficient for heating homes pollutes (less than coal)

nuclear fission high energy output radioactive waste

nuclear fusion high energy output unproven technology

solar cheap, clean dependent on weather

hydroelectricity cheap, clean dam destroys local habitat

wind cheap, clean dependent on weather

tidal/wave cheap, clean dependent on tides/waves

biomass (wood, biogas, ethanol,


cheap, clean, carbon-neutral low energy output
biodiesel)

comparison of the renewability of energy sources including coal, petroleum, natural gas, nuclear
fuels and biochemical fuels
Since the density of water is 1.00 g mL , the mass of 120 mL of water is 120 g.
this is:
Energy (J) = 4.184 mass of water (g) The energy required to raise the temperature of 120 g of water by 1C = 4.184 120
= 502.0 J. VCEasy
Calorimeters
temperature rise (C)
or Since the temperature rises by (100.0 20.0) = 80.0C, the total energy VISUAL
required
Energy (J) = 4.184 volume of water (mL) = 502.0 80 = 40 160 J.
density of water CHEMISTRY
The energy required to raise the temperature of the water to 100C is 40.2 kJ.
4.2.2
temperature rise (C).
Method Find out how much heat is being absorbed by the
The density of water varies with temperature.
The density of water at 5C is 1.0000 g mL1.
calorimeter.
25.3
Calibration Run an electric current through the calibration heater. Using E =
Measuring the heat
VIt, and by reading the thermometer, find the calibration factor.

Calibrationreleased during a reaction


VIt
Factor = Units: J C 1
T

Experiment Bomb
Energy Change and solution
= Calibration Factorcalorimetry
T Units: J
Enthalpy changes are measured directly using an instrument called a
calorimeter. Energy
Figure Change
25.7a shows the components of a bomb calorimeter
Hfor
used = reactions that involve gaseous reactants Units:orJproducts.
mol1 The reaction
vessel in a bomb calorimetern is designed to withstand the high pressures that
The exam could ask for either
H or Heat of Combustion may be created during reactions. A calorimeter employed for reactions in
Heat ofH =
aqueous Energy
solutions isChange
shown in Figure 25.7b. Both kJ g1
calorimeters are insulated
Combustion to reduce loss orgram
Units:
gain of energy to or from the outside
kJ L1
kJ environment.
mol1
When
High heat of combustion = better
Wood 18 kJ mol
1
fuel! a reaction takes place in a calorimeter, the heat change causes
2
a rise or fall in the temperature of the contents of the calorimeter. Before
H gas = 143 kJ
1 mol

the calorimeter can be of use, we must first determine how much energy
is required to change the temperature within a calorimeter by 1C. This is
known as the calibration factor of the calorimeter.
E = VIt E = VIt
Electric heater for Electric heater for
a calibrating the Electric heater
b calibrating the
calorimeter to ignite sample calorimeter
Stirrer Thermometer Stirrer
Thermometer

Pressurised vessel

Oxygen under
pressure

Water

Sample in crucible

Insulated container
Insulated Glass bulb Solution of
container containing one reactant
second reactant

25
Figure 25.7
Bomb Calorimeter
Calorimeters used for measuring energy changes in reactions. Solution Calorimeter
a A bomb calorimeter used for reactions that involve gases. b A solution calorimeter. Breaking the glass bulb starts the reaction.

6
Supplying
Su
u and using energy
application of calorimetry to measure energy changes in chemical reactions in solution calorimetry
and bomb calorimetry, including calibration of a calorimeter and the effects of heat loss
1166strong
energy
ndifference
Numbers
entify
Cl
Metal Reactivity
nergy converter
is
For

oxidants
/Cl
Figure
galvanometer
ctants

using
converted
sulfate
a metal to reduce
solution

16.7 the and


half
2 in a reaction
The apparatus
of
Electrochemical
into a solid, the

Galvanic
Potential differences
the E
salt bridge
into
This
3.7
Series
first

Writing
cell oxygen
used to demonstrate
e are Six Big Rules:
are spaced farhalfinCell
Series the electrons
that separates

It
the
the
(solid)
monoatomic

the

values
V
must be a stronger reductant than Two
neutral
=

electrons
2
number
Writing an overall redox equation
copper oxidant is connected
electrical
represents
freea elements
metal
number
metalis
silver
ions

electron flow during


in a molecule, sum
apart intotal
equations
WritingWhen
polyatomic
total
is
the
Mg
The
VCEasy
ion are

by
Au
eachfrom
oxidant

fluorine
The
athis

important
chemical listed
Ions
sodium
neutral
Each
energy.
Zn
the
obtained
Sn

an overall redox equation


metals = valency
reactions.
at
second (aqueous) metal
When standard
=
to
the
each
charge
atom.
Cu In
(oftenAg
each
of
device

an weoverall
ions,
=
charge
each
of
a
When

1
oxidation
sodium
copper

fiwhich
rst
reaction,
in of
Each
charge of
atoms
half
silver
sodium
present
the
+2)Na(s)
conditions.
weoxidationreduction
write
eachequations
Cl
has
2,reduction
reduction
Fezero
Each
the
(N(on
zinc+
stronger
He,
chlorine by
top) can
on
(aq)the
the atom that electrons
transferredthe
atom.
atom
this
AgOsolution
2(aq)
chloride

example
(g)
reduce
+ underneath
metals

copperatom
hydrogen
copper
2
reactions.
electrochemical
redox equation
Theasum
chlorine
multiplied
zinc
converted
Two
half
oxidation
by in
has
ion
ions

+
number
+and
Agchemical
oxidation on
(aq)
has
redox
strip chlorine
cells
Ag
2e
the
on
in
(Al
=
=
of
therefore
cell with
loses
3+the
connecting
The
is
must
of
Na
atom
therefore
4.2.3 the
then
ion
numbers
+1
0
half
energy
therefore
write equations for redox reactions,
from spontaneous we no
reaction

equations
Table
reactions.
each
transferredthe Cl
at
the
into+electrical
to (aq)
of
(g)
each
thereaction,

by
copper
been
one
+3)
a
ion that iswire
reaction.
reductants
etc)
molecule gains

that2Cl
that
been
series.
is oxidised
two
copper
(s)
reactions
for
+

product
thatadd
molecule
remember
element
oxidised.
strong
electron:
since
When

redox
e
a
+ therefore

and aeach
you
reduced
electrons
reactants.
(s)

standard
Cu:
26.2.
+
a
Mg
on top be
and
reaction
the
in
lost
connect

is oxidised.
is oxidised
oxidised.
on ion side
them
equation
is reduced.
is= been
charge reduced
reactant
fi
2e
factor
energy.
ions rst
(e.g.
must
These

atom
gains
and
to
Atoms
salt2+

electrons
loses
reductant.
bridge:
/Mg
in the
present
Agformion
any
gains two
+

reduced
solution
goes forwards
these
reactions,losesTo
NO3of
together
involving
gains
of
top
two
A
onehas
two
are
half
two we
CHEMISTRY
one
two
the
one
totals

two
electron
oxidation
in
half-cells

write
gets

1)to
the
conditions
thatside
2
therefore
then
2Cl
that standard

the
BOOK
potenti
gainedc
with
electron.
separate
to
of
VISUAL

equatio
a
conserv
celltake
silver
half
norman o
reduced
electron
get an
reductio
electron.
p
tou
cel
r

electronscombining
before
(s)
anof
add
islost
the
overall
be
them
tocan
reaction underneath goes backwards
oxidised.
inan
formbottom
reduced
half-cell
be
equation. twoone
equation
together
To
theoverall
oxidation
separate
it
to
gets oxidised
calculateChar
with
take
potentia
write
to get
anrea
c
th
d
u
o
g Redox Equations When Water wetowards Worked
It
wire write
Beaker
(to is
balance
allows important
B
flow of
2
example
equations
oxygens)
electrons to for 16.2b
remember redox thatreactions, we equation
norm
give a numerical
equations in this easythe order: measure
reduction Protons this of
electrons
The (to the
thereaction,
a dilute solution
positive
zincreaction.
balanceCu(s)
chlorine tendency
of
cathode
the
flow transferredthe
hydrogens)
has therefore half
Cu of2+beena(aq)half
equation cell
electrons
+reduced.
2e reaction
involving Corrosion
lost in the to oxidation
the occur
reductio as
half equations Electrons When (add
multiplied fi
chloride
electron
rst
aasstripmany and
ofascopper
by you
a then
need)
factor wire add
ofis 2 them
suspended
before together
in aoccur
combining to
solutioninofithalf get
silver
with an
nitr
th
reduction negative reaction.salt
In Reduction
saltthe
zinc
the
bridge example
strip
reduction
(Agreactions
+ reaction.
positive
of
(aq) +
copper e are and most Ag(s)) likely
the to
solution
2 of silver cel
ion
with
anode
high E It
values,is important bridge

such metal can


oxidation
allows movement of:

as In F to
the
be
(g)/F remember
of
e example
observed.
cathode
Cu:

(aq) The that
(E
of copper=solutionan
2.87 and V), overall
changes
the
to a equation
whereas
solution
pale blue
Water

oxidatio
of
colou
SEE silver
d
Worked example 16.2b
cations to the cathode; and O2
zinc K copper
Electrochemical
Rust
Series DATA
Mg each copper
ctivity Series electrons 2+ 2atom that is 2+oxidised loses two electrons
anions to the anode Fe2+
The
transferredthe
of Cu eoverall
(aq) ions. equation electrons is: lost in the oxidation
e BOOK
reaa Figure 16.16

reactions are most likely to each occur copper in half


atom cellsthat with
is low
oxidised Elosesvalues, two such
electro
Cathodic area Anodic area
+
These food cans are made from steel that

zinc+chlorideCu(s) Cu (aq) 2e

Zn When you connect any two half-cells with a
has been plated with tin to prevent them from

each AgWrite (aq) ion that +is reduced gains one electron.
e
half equations for this reaction and
2+ identify the substances o
At the cathode: At the anode:
corroding.
reduce a metale ion the reduction the stronger
When reaction.
reductants
aCu(s)
strip of copper wire isasuspended ingains
a+ solution oneofelectronsilver nitr
O2(aq) + 2H2O(l) + 4e 4OH(aq) Iron reacts Fe2+(aq) + 2e

Fe(s)
++
eLi first(aq)/Li(s)
+
(solid) metal (E Fe
= 3.05
(on top) V). each
solution
can reduce
(AgtheAg + (aq)
(aq) 2Ag
+ eion
(aq)
wire
that
and issaltreduced
Ag(s)) Cu
bridge:
(aq)
2
REDUCTION 2Ag(s) to form a pit
OXIDATION

Sn
Zn NOTwo Ag (aq) ions bemust therefore on top be reduced to(s)silver
take up
+ underneath
metals
ger reductant than In the metal
example
Two K+ can+(aq)
Ag of observed.
copper
ions mustTheand
reaction solution
thereforethegoes changes
solutionbe
forwards toFe(OH)
andreduced a of pale blue
tohalf colou
take ion
It is impossible Solution

nd (aqueous) metal Cu
3
to measure Remember the potential that in difference
both half
Fe(OH)
and of
The overall equation (s)
an isolated
2 can therefore be written
overall 3 as:
equations ce
fo
of CuCu +The (aq) overall
ions. equation is: VCEasy
by each copper atom that
OIL RIG is oxidised. To write an ov
Au 2+
Cu will be formed.top The
one latter
gets is
2Fe(s) + O2(aq) + 2H2O(l) 2Fe2+(aq) + 4OH(aq)
reduced
eachand by
copper each atom copper that atom is this that
oxidised is oxidised.
loses two To write
electrons an
since bothZnoxidation Zn +Redox reduction must take place for afor potential differenc
2
nstrate electron flow during oxidationreduction reactions.
the number ofanforatoms of each element present in form
theo
power source

red-brown coloured rust.


The iron(II) ions then react with the hydroxide ions to form a gree
The fi rst half equation for reaction is the copper metal
+

cat
Write half equations this reaction and identify
precipitate of iron(II) hydroxide:
the substances
2

athis
device reaction,
in which this chemical the
+Cu + reaction, energy
CuCu(s) half +thatthe
2Ag equation
+ half equation involving 2+ involving the
the
+either reduction
VISUAL
reducti
nic
to Cell exist. E values
Zn
from aeach for Ag
spontaneous halfredox (aq)
the
cells
+ 2

ion
number
2

reactionare present
ismeasured

is(aq) reduced
Oxidationin by the
Protect Cu gains
connecting(aq) by
reactants. one 2Ag(s)
Atoms
Fe2+(aq) + 2OH(aq) Fe(OH)2(s)
from
is Reduction
painting,
corrosion
alloying orisgiving the
electron.
the are
cells
CHEMISTRY conseto
multiplied multiplied
byreactions. Cu(s)
auphalffactor by aofHfactor2Cu 2+
+ before be
(aq)
of 2 + 2e
before
combining bottom
combining
Figure 16.15 summarises this process.
one gets
itequations
withoxidised
it with
Electrons flow from Znconverted
the zinc atomsinto electrical
to the energy.
copper(II) ions as these collide.loss of e
take the
metal a gain of
On exposure to more
negative e
moisture and oxygen, the iron(II)
charge.
Two Ag (aq) ions must therefore reduced overallto up

+
Solution
pipeline
+ hydroxide i
reference thishalf cell. A hydrogen cell, (aq)/H (g), at standard condition
2.1.4
+ Cu (aq) + 2e Cu(s)
Remember that in both half and fo
2
Zn(s) 2
(aq) + 2e further oxidised to iron(III) hydroxide, a red-brown precipitate: unreactive
Evidence forOXIDATION flowHALF-CELL
can be obtained byREDUCTION
setting an apparatus as shown
oxidation of Cu:

116 6
If one reactant is oxidised,
electrode

HALF-CELL reaction 2
underneath goes backwards
oxidation of
This Cu:
the total
represents charge
theof oxidation on the
reaction, product since side
each of the
copper atomequat has
4Fe(OH)2(s) + O2(aq) + 2H2O(l) 4Fe(OH) 3(s)

known as the by
standard each copper
hydrogen the atom
number electrode, that atoms is is usedofoxidised.
iseach
for element
this Topurpose write
present and an
in ovE
the
its
Figure 16.17
in Figure 16.6. another reduced.
The fi rst half equation for this reaction is for the copper metal form
This pipeline carries natural gas. A direct current
Figure 16.8 In air, the iron(III) hydroxide loses water from source isits structure
connected totheform
at intervals to give pipe a

An The zinc metal and


wiresolution ofcontaining copper(II)
reaction. ions are in separate2+
total charge on the reactant side of the equation. Ch
negative charge and so protect it from corrosion.

a solution
Cuthe ion.
Fe2O3.xH2O, the hydrated iron oxide known as rust. The porous rust easil
electrochemical cell demonstratingallows
a flowflow of electrons
electrons in a redox 2+
Cu(s)
number Cuis (aq) + 2e
valueAisredox arbitrarily this assigned
thereaction, as the zero.of half The 2+ present
standard
equation inbalanced
the reactants.
potentials
involving Corrosion Atoms
of
the other
forreductionare conse
cellsis ar
flakes off the surface of the iron, exposing the iron underneath to furthe
beakers. copper
byRedox
towards
strip,
reactions
a pieceHalf-Equations
dipping positive
in in the
aqueous
Cu(s) cathode

flow Thechemical
solution
Cu(s)
copper(II)
Cuincluding
(aq)
reactions.
ions,
Cu +
writing 2e
2+
(aq)
oxidation.
2. + The2e equations
electrochemical series Oxidation
connected oxidation of wire electron
to a galvanometera second
reactions. meter
(Agfor(aq)half
+ forequation
detecting
involves
a
+ e metal displacement the aqueous
Ag(s)) 2 reactions,
Cu is a
silver
reductant
ions forming
The wet corrosion of iron is a galvanic process. Galvanic cells
loss of e are set u

flthen measured asreduction


shown in+a in Figure 26.10.
and reactions, example
multiplied by a factor of 2 before combining itReduction withisthe
on the metal surface, where different regions act as anodes and cathodes:

1166
ow of electrons. A zinc strip, dipping solution of zinc chloride, is also
corrosion
salt
thebridge

salt bridge of ironby (Ag


Examples:
a pieceThis
positive
(aq) the +
represents e
total charge
the Ag(s))
oxidation
on the
reaction, 2
The cathode region, where oxygen gains electrons and is reduced, occur
product since side
each of
copper the atomequat has
+
at sites of high oxygen concentration.
The potential difference of Aga cell
+
(aq) at estandard

Ag(s) conditions is the differenc
16
1 6
connected to galvanometer of wire.
cathode The solutions in the two
beakers are connected oxidation of Cu:
n a silver nitrate solution
allows movement of:
cations to the cathode; and The overall equation is:
The anode region, where Ag is an oxidant
Wateriron loses electrons and is oxidised,
gain of e ofte
by a salt bridge. The total
salt bridgecharge contains on theto reactant side of the equation. Ch
an ionic O2 inRust
e a Cu ion.
2+
copper occurs an area of stress in the metal where the metal lattice has bee
anions to the anode
er crystals.Thethe
2+

between ions flE The


values e overall
of its twoequation half the cells, is: + i.e.
Fe
deformed, for example, at the tip of a nail.294
compound. ow through the salt bridge between solutions
complete theOverall Redox Equation

This
The represents
chemical
second Cu(s) half +the
reactions.
2Ag reduction
equation (aq) reaction,
In general,
Cathodic
involves theCu since
e Anodic
areathe anode region
2+
(aq)
aqueous each
is one where
2Ag(s)
silver Agions
Figure
area there
+
+
is 16.16
ionforming
a lower
Water
W
has gai
oxygen concentration

Cu (aq) + 2e
These food cans are made from steel that
circuit. The salt bridge Cu(s)
may be something as 2+
simple as a piece Corrosion is therefore greatest at the centre
At the
of cathode:
chipped paint
of plated
has been
where the oxygen concentration
a water
with tindrop
At the anode:
orthem
to prevent
is lowest. The cathod
under from a laye

neutral silver
Will+beatom. Will be
corroding.
(aq)
of filter paper soaked in a solution of potassium Example: nitrate. O2(aq) + 2H2O(l) + 4e 4OH Iron reacts 2+

region is at the edge of the water drop orFe(s) where Fe (aq) + 2e


cell potential difference
Cu(s) + =2Ag
Remember higher +(aq)
half-cell
that in E
Cuboth 2+lower
(aq)
halfOxidised+half-cell
and 2Ag(s)
to form a pit
overall E equations f
Reduced
the paint is missing as th

+ oxidised + reduced

oxygen concentration there is greatest.
This apparatus
n a silver nitrate solution
galvanic
is known
cell is an energy converter
as a (Ag
galvanic +
(aq)cell or Ag e (aq)
electrochemical
that separates the oxidant from the
e Ag(s))
cell. A Ag(s)
REDUCTION
2 OXIDATION
Wet corrosion, leading to the formation of rust, is accelerated by th
K+
presence of dissolved salts in the water coating the metal. This is particularl

into+the number of/Fe atoms of each element


as:present in the
er
For crystals.
theChemical
cell composed of Writing
Ag /Ag and an
Fe overall half Fe(OH) cells redox
2(s)
as shown equation
inAg Figure 26.6
NO 2+ The overall equation can and
thereforeFe(OH)
be written3(s)
noticeable near the coast. The dissolved ions from the salt promote corrosio
energy Remember that arein both O half and overall equations for
reductant.
3
is converted electrical energy. When this
This represents the(N ,reduction etc)willreaction, since each +
ion has gai
Cu +The overall equation is:
by increasing the conductivity 2+ of the water.
Oxidation Numbers Cu free elements zero He, 22Fe(s) + O2(aq) be formed. The
+ 2H2O(l) 2Fe (aq) + 4OH(aq)latter is
the number present in the +3)reactants. Atoms are cons
2

the Cell Potential


cell voltage oxidants attheDifference
2
standard number neutral
metals
The
conditions
monoatomic
of
= silver
valency
difference
ions
atoms
= charge
atom.
(often +2) canon between
of Thebered-brown
the iron(II)
ion (Al
each calculatedthe
is
element
E of the two
aspresent
follows:half-cells
3+Iron will rust more rapidly if it contains impurities
with a less reactive metal. For example, if iron andpower
ions then coloured
react with the rust.
hydroxide ions
in the p
to form
or if it is in contac
copper
a
source
green
+ are in contac
Zn + They help to identify and with each other, an electrochemical cell will be formed in which the les
2
galvanometer
When reactions.
oxygen = 2 we write
fluorine = 1equations

precipitate
hydrogen =2+ +1for redox reactions, we no
of iron(II) hydroxide:
reactive copper will act as a cathode and the iron as the anode. The iron wi

in a+
lower +half-cell
reductants Cu in a+ reaction
are Six the Cu(s)
number =2Ag present
+
(aq) in the Cu reactants.0 (aq) by 2Ag(s)
Atoms Eare conser

1166
2 + Fe2+(aq) +corrode
Protect 2OH(aq)
from more quickly than if2it
Fe(OH) (s)were on its own.
Cu molecule, sum of oxidation number
= corrosion either
2

cellThere potential Bigdifference


Rules:
half the total
equations higher
charge
fiofrst half-cell
andon the
then E product
add them side NO3of
together the 1)to equaget
Writing an overall redox equation
in polyatomic ions, sum painting,
oxidation
Figure alloying
numbers
16.15 summarises
Protecting =or giving
charge
this the
on ion
process.
against (e.g.
corrosion
totals

reactions.
Cu +(aq) + 2e Cu(s) = E (Ag (aq)/Ag(s)) metal a negative charge.
E
pipeline

to (Fe (aq)/Fe(s))
copper strip + On exposure to more moisture 2+ and oxygen, the iron(II) hydroxide is
Zn2+(aq) + 2e
total charge on the reactant side aof the equation. C
zinc strip
Remember that in both half and overall equations for
2

It is important to remember
further oxidised There are
that
several
iron(III) an
ways to protect
hydroxide, overall equation
iron and steel structures against corrosion
red-brown precipitate:
These depend on the environment in which the structure is located, the desig
unreactive
electrode

HALF-CELL REDUCTION saltHALF-CELL


bridge
= 0.80 on(0.41)
the total charge
chemical B the
reactions. product side ofinfromthe equatio
4Fe(OH)and + O (aq)use
(s) intended + 2Hof the and
structure the relative
(s) costs of various protectio
electrons Ions transferredthe electrons of lost the oxidation
O(l) 4Fe(OH)
Beaker A Balancing Redox
the number
Equations When of
we atoms
write of In each
equations element
for redox loses present
reactions, in the
we no p
2 2 2 Figure
3 16.17
Beaker measures. The simplest these measures rely on the creation of a barrie
This pipeline carries natural gas. A direct current
Water (to balance oxygens)air, the iron(III) hydroxide water its structure to form
source is connected at intervals to give the pipe a
a dilute solution of
copperBalance
onstrating asulfate redox equations
flow of electrons
total this easythe
in a redoxinreaction.
charge = 1.21
order:reduction
Protons
on theV
a dilute solution of
zincreaction.
(to balance
reactant
Fe hydrogens)
O .xH O, the
side
hydrated
of
iron
iron, the
oxide known
equation.
as rust. The porous
Cha
negative charge and so protect it from corrosion.
rust easily
copper strip the number half equations
present
Electrons (add
zinc fias
inrst
chloride
strip
flakesand
the
many asthe
off
2

you then
reactants.
3

need)
surface
2
of theadd them
Atoms
exposing the together
iron underneath toto
are conser get
further
eactions in aqueous solution including Inimportant
thevoltage writing
example balanced
ofwetcopper
oxidation. equations
and the for
solution of silver
nDifferent
andMetal reduction values chemical
for the
reactions.
reactions,
It example
for
isreactions.
cell metal
toondisplacement
areremember
The
obtained
corrosion of iron that under
is a galvanic
reactions,
anprocess.overall non-standar
Galvanic cellsequation
are set up
K Electrochemical Series SEE DATA
Mg each copper atom that is oxidised loses two electro
the metal surface, where different regions act as anodes and cathodes:
Reactivity Series electrons transferredthe electrons lost in the oxidation BOOK
on conditions.
of copper
iron a metal to reduce athe
sulfate
total Zn charge on the
The
at
cathode
sitesproduct
of high
region,
oxygen
where oxygen
you side
concentration.
gains electrons
oftwothe
and is reduced,
equatio
occurs

each Ag (aq)
zinc+chloride
ion Thethat isWhenreduced connect any
gains
electrons one
half-cells with a
electron

16
1 6
For
solution metal ion
into a solid, the first (solid) metal the
Fe reduction
the stronger
(on top) reaction.
reductants
solution
can reduce the
anode region,
wire where
and airon
salt loses
bridge: and is oxidised, often

must be a stronger reductant total thancharge Sn


Two
Cu InAg
on(aq)
+
metals
the theions
underneath
example reactant of copper
deformed, for side
reactionat
example,
andofon the
thetop
the
tip goes equation.
occurs in an area of stress in the metal where the metal lattice has been
must therefore be reduced
solution
forwards
of a nail. 294 of Cha
to silver
take
the second (aqueous) metal In general, the anode region is one where there is a lower oxygen concentration.
Figure 16.7
chemical by reactions.
Au
each copper copperatom atomispaint that is oxidised. To onewrite an
Water
W
top gets reduced
The apparatus used to demonstrate electron each
flow during oxidationreduction reactions.
of chippedthat
Corrosion therefore
isgreatest
where oxidised
the oxygen concentration loses
at the centre of a water
is two
drop or
electro
under
lowest. The
a layer
cathode
athis
device reaction,
in which chemical the half
energy equation
edge of the water involving the reducti
Galvanic Cell from aeach Ag+redox (aq) ion
oxygen that is reduced
there is greatest. gains one electron
region is at the drop or where the paint is missing as the
spontaneous reaction is
concentration
bottom one getsbyoxidis
multiplied
converted
Two Ag (aq) byions
into+electrical a factor
energy.
must of 2
therefore before be
Wet corrosion, leading to the formation of rust,
combining
reduced
presence of dissolved salts in the water coating the metal. This is
itparticularly
to
is accelerated
with
take the
reaction underneath goes backwards
use of the electrochemical series oxidation
by in predicting
each ofthe
copper Cu: noticeable
products
atom
by
ofnear the coast.
redox
that
increasing the
The dissolved
reactions
is
conductivity oxidised.and
of the water.
ions deducing
from the salt promote
To overall
write
corrosion
an
equations from redox half equations wire allows flow of electrons Iron will rust more rapidly if it contains impurities or if it is in contact
thistheelectron
towards reaction,
positive cathode thewith
Cu(s)
flow
withhalf Cu a less equation
(aq)
2+reactive
+ 2e example,
metal. For involving Corrosion
if iron and copper thearereducti
in contact
each other, an electrochemical cell will be formed in which the less
negative salt
salt bridge

bridge
multiplied (Ag+(aq) by a+ factor
positive reactive

ecorrode ofwill
copper 2actthan
Ag(s))
more quickly
before if itwere2oncombining
as a cathode and the iron as the anode. it
its own.
with
The iron will
VCEasy
VISUAL
CHEMISTRY
4.2.4

Limitations of Predictions Made Using the Electrochemical Series

Standard Conditions
Standard half cell potentials (E) are
measured under standard conditions. Under
different conditions, the potentials will be
different.

Rate
Electrochemical Series doesnt tell you the
rate at which these reactions occur. Some
redox reactions happen so slowly that they
appear not to be happening at all (e.g.
breakdown of H2O2(l) into H2O(l).

limitations of predictions made using the electrochemical series, including the determination of
maximum cell voltage under standard conditions
chloride electrolyte. Consequently the cell would Mercury and its compounds
Lithium button cells produce about last 3 volts
longer, during discharge, and silver At the cathode (+): are toxic, so
VCEasy
produce higher currents and be less the disposal of these mercury cells created
zinc cells give an almost constant 1.6 volts. A
susceptible tovariant of
polarisation. the
These lithium
heavy duty cell Manganese dioxide is reduced in a complicate
Figure 27.4 health and environmental safety concerns.

Primary Cells employing


When a lithium ion cell or batteryiodine as the oxidant is used dry
is recharged, to cells
power heartbeen
have largely pacemaker implants
replaced by alkaline to be:such as the silverzinc cell have
Cells
andfrom
the electrical energy the rechargerto last for fifteen years. cells.
is designed
forces the reverse reaction to regenerate the
replaced
2MnO mercury
2
(s) +cells. VISUAL
2NH4+(aq) + 2e
Mn O (s) + 2 3

reactants.
Worked example 27.2a A new cell produces aboutCHEMISTRY
1.5 volts, but this dimi
!
4.2.5
use. To maintain a net forward reaction, the solub
The overall reaction that occurs in the silverzincRemoval
buttonofcell
theis:
products of a reaction favours migrate away from the electrodes. During use, t
Alkaline Zn(s)
Cell+ Ag O(s) + H O(l) Zinc-Carbon
Zn(OH) (s) + 2Ag(s) Dry Cell
2 2
formation of a greater amount of productsan
application
2 of Le Chateliers principle.
around the electrodes slows and can even stop t
effect, known as polarisation, is more marked durin
Write equations for the anode and cathode reactions.
a cell is allowed to rest, the products migrate awa
Metal cap (+)
Solution Metal cap (+)
the cell recovers. Warming the cell with the hea
Oxidation occurs at the anode. Zinc is oxidised to Zn(OH)2: increase the rate of recovery. However, once the r
Cathode:
reaches equilibrium, the cell will be flat, and can
Button Cell
outer steel
Zn(s) + 2OH(aq) Zn(OH)2(s) + 2e case
Mixture of carbon You can still buy zinccarbon cells and batt
Silver oxide isand
reduced to silver at the cathode:
manganese improvements have been made to the cell, the te
dioxide Powdered
nt Ag2O(s) + H2O(l) + 2e 2Ag(s) + 2OH(aq) zinc same as it was in the first dry cells over a centu
ell cells now tend to be restricted to applications that
at The construction
Ammonium
of a lithium button cell is shown in Figure 27.7.
Mixture of The Metal cap ()
source of energy for infrequent low-drain use. Th
manganese dioxide
cts most common
chloride type
and of lithium button cell uses manganese dioxide
and carbon as high-drain, high-use applications has seen zinccar
Lithium metal
zinc chloride
ns the oxidant.
electrolyte by alkaline cells.
Potassium hydroxide
electrolyte
Worked example
Cathode:
27.2b Alkaline cells
Electrolyte
Anode: steel Cathode: outer
The followingcarbon rod occur in the lithium button cell:
reactions or brass
The alkaline cell was invented container in the lateof 1800s,
nickel or steel (+)
cal Li Li+ + e World War II (193945) that the basic idea was d
Anode:MnO Li+ + e LiMnO2
+() that time, an expanding range of
Manganese(IV) appliances has ap
oxide
on zinc case
2
Metal base ()
capacity, small power sources. With earlier types of
in At anode, zincapowder
Whichisreaction
oxidisedoccurs at the negative
At electrode?
anode, zinc casing is oxidised At anode, lithium (or silver) is oxidised
n.
m
!
Zn(s) Figure
+ 2OH27.5
At cathode,
b Zn(OH)
Write2(s)
an +overall
2e equation
The construction of a zinccarbon dry cell
is simple andSolution
manganese
has changeddioxide is reduced
little in the last
!
for the reaction occuring
Zn(s) (aq)in+the
Zn2+Figure 2elithium cell.
27.6
Construction of an alkaline cell.
At cathode, manganese dioxide is reduced
! Figure 27.7
demands,
Li Li+ +the
e alkaline cell appeared on the market
Construction ofthe
Although a lithium button cell.reaction that occurs
chemical
At cathode, manganese dioxide (or zinc) is reduced
in 2MnO hasMnO
much +in common with the zinccarbon dry
1002(s) + H2O(l) + 2e Mn2O3(s) + 2OH(aq) 2MnO2(s) + 2NH4+(aq) + 2e Mn2O3(s) + 2NH3(aq) + H2O(l) 2 + Li + e LiMnO2

years.
a Electrons are produced at the negative electrode. The oxidation of lithium metal to lithium completely different (Figure 27.6). The alkalin
ions produces electrons. The reaction is Li ! Li+ + e. performance and longevity.
b The equations must be combined in such a way that there
An alkaline are equal
cell needs numbersthan
less electrolyte of electrons
a At the anode ():
on both sides. In this case the equations can dry cell, allowing
simply be added:more reactant to be included.
also known as
Zinc powder around the central metal rod is ox

Secondary (Rechargeable) CellsOnce formed,

27
27
A typical D size alkaline cell contains about
Li + MnO2 + Li+ + e Li+ + e + 40
LiMnO
g of manganese dioxide, compared with Zn(s) Zn2+(aq) + 2e
accumulators
2
25 g in a dry cell of equivalent size.
This simplifies to: Zn reacts immediately with O
2+

Li + MnO2 LiMnO2
to form zinc hydroxide. The overall reaction
429 written as:
Car Batteries Cells and batteries
27.127.2
Nickel-Cadmium Cells
Zn(s) + 2OH (aq)
Zn(OH)2(s) + 2e
summary recharging process alsoAt the cathode (+):
reconstitutes the sulfuric
recharge e acid electrolyte. As the Manganese
density of dioxide
sulfuric is acid
reduced:
recharge e discharge e
(1.84 g mL ) is significantly
1 2MnOgreater
(s) + H than
O(l)that Mn2O3(s) + 2O
+ 2e of
G discharge
Galvanic
l i cells e t cannott be
ll that
th b recharged
h d are known
k as primary
i The
Th dry
d cell,
ll alkaline
lk li cellll andd the
2
th silverzinc
il
2
i andd lithium
lithi button
b tt
water, the level of charge carried by the battery
cells. cells are examples The technological
of primary cells. improvements incorporated
The products produced by the redox reactions
PbOin primary cells can be measured by construction
the density give of theit acid
about five times the life o
2 (+) electrolyte. To determineAlthoughwhether
alkaline a battery
cells is
are slightly more expensive

27 27
27
migrate away from the electrodes and are consumed
electrode by side
Pb () fully discharged or better
flat, avalue
device for money
that and
measures are especially cost-effi
reactions.

27
electrode and motorised toys, where high currents are neede
the specific gravity (density) of the electrolyte is
used; the greater the density, the more charge is
carried by the battery. 431
430 In theory, it should be possible to discharge
Cells andabatteries
Supplying
Su
u battery
and using energy and recharge it indefinitely. In practice,
H2SO4(aq)
however, this is not the case. One of the main
problems is that the lead(II) sulfate formed on the
electrodes becomes coarse in texture and drops
offAtthe electrode
anode, grids. Side
cadmium reactions,
is oxidised such as the
to cadmium hydroxide
Figure
At15.4.9 Discharge and is
recharge of a car battery.
anode, lead oxidised to lead(II) sulfate
!
production of hydrogen
gas from
Cd(s) + 2OH (aq) Cd(OH)2(s) + 2e the reduction

H+ ions, also limit the effectiveness of the battery.


of

!
Pb(s) + SO42(aq) PbSO4(s) + 2e
AsAta cathode,
result, mostnickel hydroxide
leadacid is reduced
accumulators from
have a +3 to +2
At cathode, lead(IV) sulfate is reduced to lead (II) sulfate
!
NiOOH(s)
life + H2O(l) +four
of approximately

e years.
Ni(OH)2(s) + OH (aq)

!
PbO2(s) + SO42(aq) + 4H+ + 2e PbSO4(s) + H2O(l)
Overall equation:
Overall
Given
Cd(s)
theequation:
number of cars on the road worldwide,
+ 2OH(aq)
the car battery + 2NiOOH(s)
market + 2H2O(l)
is an enormous one.
Pb(s) + PbO2(s) + SO42(aq) + 4H+ 2PbSO4(s) + H2O(l) 2Ni(OH) (s) +
Recent advertisements
2 2OH (aq) + Cd(OH) (s)
using words like
2

maintenance free and calcium suggest that


research into these batteries is alive and well.
the chemical principles, half-equations and overall Both of these
equations ofterms
simplerefer to improved
primary metal and
and secondary
galvanic cells metal oxide grids being used in the lead batteries.
Although the advertising may suggest otherwise,
the anode in modern calcium batteries is not in
fact calcium at all, but rather it is lead with a
VCEasy
Fuel Cells VISUAL
CHEMISTRY
+ 4.2.6

Electrolyte

Hydrogen Oxygen
gas inlet gas inlet

Porous
Porous cathode
anode

+ Convert chemical energy directly to electrical energy

+ Only by-product is clean water


Water
At anode, hydrogen gas is oxidised + Fuel cells generate electricity as long as fuel is supplied
outlet
H2(g) + 2OH(aq) 2H2O(l) + 2e
! + Can use a variety of fuels

At cathode, oxygen gas is reduced + Easy to generate electricity off-the-grid


ure 27.14
O2(g) + 2H2O(l) + 4e 4OH(aq) Requires a constant fuel supply
kaline! fuel cell. Expensive
Overall equation:
Can only produce direct current (DC)
2H2(g) + O2(g) 2H2O(l)
Impurities in the hydrogen fuel can affect performance

cell produces about one volt. Higher voltages are obtained by conn
mbertheofchemical
fuel principles,
cells in series to
half-equations and form a battery
overall equations or advantages
of fuel cells; fuel cell
andstack. The

roducts are water and heat. The nature of the electrodes is cruc
disadvantages of fuel cells compared to conventional energy sources

essful operation of the cell as they function as catalysts for the rea
aluminium from their
VCEasy
Electrolytic Cells
chlorine and hydrogen VISUAL
CHEMISTRY
e cells, such as lithium
Reactions are the OPPOSITE
on aluminium metal
OPPOSITE to those in the galvanic cell. 4.2.7
Reactions aretonon-spontaneous
Figure 28.2 and require energy.
Tin cans are used as packaging for a wide
Examples Galvanisation
range of products.
plating a thin film of The
metaltin
overcoating on the
another metal canit prettier or more resistant to corrosion
to make
preventsfrom
Extracting metals it fromorescorroding.
mining

Recharging rechargeable batteries including car batteries


Increasing the thickness of the surface oxide layer of aluminium e.g. cans

+
Diagram Power
supply
ey are used extensively Electron
e flow
eans, peaches and fish.
mposed of steel, with
AN OIL RIG CAT: Anode loses electrons & is oxidised
limetre thick that has
y and prevents contact
+
+
Tin rod

e
AN OIL RIG CAT: Cathode gains electrons & is reduced

At anode, tin is oxidised At cathode, tin is reduced


nts the iron rusting.
Sn(s) Sn (aq) + 2e

2+ Sn2+(aq) + 2e Sn(s)

ace ofAnode another


is POSITIVEmetal
in this cell Sn2+ Cathode is NEGATIVE in this cell
ng is performed in an e Object
tin plating shown in NO3 e being
a wire to the negative plated

the negative electrode


nitrateTinsolution,
plating rod loseswhich mass. A coating of tin forms around the can.
This solution is referred Tin nitrate solution (electrolyte)
metal is connected to
Figure 28.3
Electrolytes Allow charged ions
A cell used for to flow
electroplating tin. between the electrodes
as an electron pump,

28
8
moving electrons from
Molten Electrolytes Aqueous Electrolytes
Large amounts of energy are Little energy required.
required to melt the Cheaper than using molten
electrolyte electrolytes.
When producing H2 and Cl2, a selective

445
Examples Molten sodium electrolyte Examples Sodium chloride electrolyte membrane is placed in the middle of the
electrolyte to prevent the H2 and Cl2 from
reacting with each other.
Na3AlF6 (cryolite) electrolyte
Electrolysis: driving chemical reactions by electricity
Used in the electro-refining of copper.
Sulfuric acid electrolyte 98% pure blister copper is the anode;
99.999% pure copper is the cathode.

the chemical principles, half-equations and overall equations of simple electrolytic cells;
comparison of electrolytic cells using molten and aqueous electrolytes, and inert and non-inert
electrodes
f electrolysis,
Faradays Laws
after M VCEasy
VISUAL

olically as:
CHEMISTRY
First Law of Electrolysis 4.2.8
ed using theofunit
The mass produced atThe
metalcoulomb.

Mass of silver deposited at cathode (g)


the cathodefrom
be calculated is proportional the
measurements 2.5
quantity of electricity passed
me, through
t, for which the current flows.
the cell.
2.0

mQ
ime (seconds)

d from a silver-plating cell given


Mass
1.5

1.0

sing: the more charge thatCharge


is proportional to
passes
Charge = Current Time
0.5
d at the cathode. This relationshipQ=It
if we perform this experiment in
ions such as temperature, voltage,

e second law
500 1000 1500 2000
same graph is obtained as long as Charge (C)

Second Law of Electrolysis Figure 28.10


(mol)

-plating cellmole of a substance to be


For one The variation with charge of mass of silver
(mol)

deposited, evolved, or dissolved at formed at the cathode passing through a silver-


cathode

Q = I an
telectrode,
Mass the
of silver formed
passage (g)
of one, 4
plating cell.
cathode

two, three, or another


0.45whole number
of mole of electrons is required. Silver
at at

0.90 3
deposited

an repeat the previ


Ag+(aq) + 1e1.34
metaldeposited

Ag(s)
One electron reduces one1.79
Ag+ ion to silver metal 2 Copper, tin, lead
2.24 !
2+
Cu (aq) + 2e Cu(s)
Amountofofmetal

Michael Faraday (17911867) was an English


Two electrons reduce one Cu2+ ion to copper metal 1 chemist and physicist who, apart from working
mmarised by saying that the mass

than silver. Resu


Chromiumthe
out the laws of electrochemistry, discovered
Amount

Cr3+(aq) +to3ethe
ly proportional Cr(s)
quantity of connection between magnetism and electricity
onship is known as Faradays first
Three electrons reduce one Cr ion to chromium metal
3+

and devised the first electric


96 500 193 000
motor.289 500
o discovered it. It may be written =2 =3
96 500 96 500

ining Cu , Sn , Pb
2+ 2+ Charge (C)
ted at cathode (g)

2.5
Figure 28.12 Silver
ysis application of Faradays laws in electrochemistry.
Variation
2.0 with charge of amount of metalLead
(mol)
formed at the cathode for different metal-
ing electroplating cells for metals plating cells.

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