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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
+
Diagram Power
supply
Electron
e flow
Tin plating rod loses mass. A coating of tin forms around the can.
Tin nitrate solution (electrolyte)
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
(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
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
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.
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
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
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
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
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
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 +
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
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
+
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
form
2+ Ca(OH) into 2
its
a ions.
precipitate
(s)
3
Ca of (
3
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
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
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
4 of liquid
The water is left togas stan
2
Reaction + 3 type
Macid
2 After base ltering, )the clear water is us
2 4
of ethanoic acid, the 2
concentration of 3 4
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) +
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
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
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)
+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
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
4OOTH DECAY
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:
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
+
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
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
Water
W acid is base 9EAR
equivalence ispoint
Ammonia molecular compound in wate
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
1144
Water
4OOTH DECAY
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
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.
) =fluoride
metal carbonates. A salt istypes, produced these, together with
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
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
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
titrations, an indicator
themust be Magnesium
added
in thetoreaction
the reaction mixture to detect the bas
Acid +2HCl(aq)
reactive metal + hydrogen
saltionic
!
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
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
2
Hydrogen gas is produced from metals when
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
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
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
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.
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)
=
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
= 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
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+
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
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
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)
4.0
06
06
Figure 6.14
can
Peak
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
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
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
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.
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.
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
79 12.0 79
Tells you the69
H
environment of those protons (CH , NH ,solution
H
o
H C C H CH2 CH2
Wavelength (nm)
spectrographs. Low-resolution NMR
spectrographs dont have mini peaks.
06
06
5 4 3 2 1 0 5 4 3 2 1 0
+ 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
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
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 (%)
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:
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
member memberdiffers
bromo differs
by a iodo
CH by 2a CHol 2 oic acid
ane ane ane
evious
member.member. alkanes
saturated, all
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alkenes
unsaturated,
contains C=C
amines
NH chloroalkanes bromoalkanes
Cl group 2
Br group
iodoalkanes
I group
alkanols
OH group
carboxylic acids
COOH group
backbone backbone
ethane
hanepent pentane penteneethene ethene
pentamine chloropentane bromopentane iodopentane pentanol pentanoic
acid
5 carbons
3CH3 CH3CH3 CH2=CHCH 2 2=CH2
hex hexane hexene hexanamine chlorohexane bromohexane iodohexane 2.hexanol 2. hexanoic
Number Number
those t
6 carbons acid
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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general a general
test Htest for u
for unsaturatio
ermulae three examples
three examples
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H H 3 H of reaction
H
H to a singletobond.
double bond a sin
methyl hexyl H 1 H 1H 3 of reaction
H is known is
H known
H as H asH1 anreaction.
an addition additionC
H 1 reaction.
H
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
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In
presencethe
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ethene ethene
3
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CH (right) produces no reaction. The colour in HH gas toethane.
produce
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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
bond, H
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bond, converting the C=C doH th
C 3 carbons
Cimmediately8 because
carbons
C H in the C H Figure 8.20 H
H H
immediately
molecules Hin the
because moleculesH to a to
carboncarbona carboncarbon
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
anesstructure
are Figure
addition Properties
usually 8.21arewhen
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including
usually
addition Properties
usedequations
writing
Figure 8.21 when writing
molecular,
reactions so that theAlkenes
for equations for
structural
the position and
a fewof the
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
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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
to hexane to hexane In Addition InAddition
the presence thetoof
of hydrogen presence
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hydrogen aand
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alkanols (C n H OH),
(right)
2n+1 alkanoic
produces no acids
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(right) produces no reaction. The colour in The (C
colour in
n H COOH)
gas to produce
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gas toethane.
produce up to
A ethane. C10
hydrogen A atom
hydrogen atom has
has bonded tobonded
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H
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Add bromine solution C + Br C Br + Br
the(left)
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ower oil (left) disappears almost Br
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the sunflower oil almost C
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side of theside of the
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converting C C
the C=C the
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immediately because because
molecules 3 Reaction
3 Reaction with steam
with steam
molecules in the
in the
H
H
Figure 8.21
C backboneH the products formed when
C 3 Name 2 backbone
H
C ethene reacts with:
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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
the presence of a catalyst and on heating, 3 ethene reacts with hydrogen
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:
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C
CHEMISTRY
C
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Computed by WolframAlpha
added
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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
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
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
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
! 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
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
08
08
Two different forms of polyethene: high-density
bromine tothe
ethene. Addition of bromine to ethene.
polyethene (HDPE) and low-density polyethene
(LDPE).
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.
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
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.
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
+
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
Active Site
n bonds within
Bonds break in
these products the substrate
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
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
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. +
H+
Covalent bonds are responsible for producing the primary structure or C G of N N
N
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
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
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
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)
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)
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
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)
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
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
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:
20C
30C
proportion of
molecules with a 40C
particular kinetic
energy 50C Shaded area represents
number of particles with
enough energy to react
(>EA)
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)
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
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
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
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
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.
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
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
[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
[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)
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
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.
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
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
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
3
Assume:
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
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
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 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
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
+
coal cheap pollutes
natural gas efficient for heating homes pollutes (less than coal)
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.
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
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
by
Au
eachfrom
oxidant
fluorine
The
athis
important
chemical listed
Ions
sodium
neutral
Each
energy.
Zn
the
obtained
Sn
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
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
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
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
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
1166
ow of electrons. A zinc strip, dipping solution of zinc chloride, is also
corrosion
salt
thebridge
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+
+ 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
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
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
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
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
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.
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
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
!
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
Electrolyte
Hydrogen Oxygen
gas inlet gas inlet
Porous
Porous cathode
anode
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
+
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
2+ Sn2+(aq) + 2e Sn(s)
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.
mQ
ime (seconds)
1.0
e second law
500 1000 1500 2000
same graph is obtained as long as Charge (C)
Q = I an
telectrode,
Mass the
of silver formed
passage (g)
of one, 4
plating cell.
cathode
0.90 3
deposited
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
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+
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.