Professional Documents
Culture Documents
AQA A2-LEVEL
Shared Areas
at:
Chemistry
Read
Mr Lunds Classes
A2 Chemistry
Unit 5
the enthalpy of
is the enthalpy change that occurs when one mole of
at 298K and 100 kPa (i.e. standard conditions)
formation (Hof,298)
combustion (oc,298)
Hesss Law: the enthalpy change for a reaction is dependent only on the initial and final
states of the system and is independent of the route taken.
Reactants
Products
1
Elements
Reactants
s
Products
1
Combustion
Products
Enthalpy Definitions
LUND 3 March 2015
2
note that once again in all these definitions you specify both the quantity and type of the
particles initially and finally
the enthalpy of
is the enthalpy change that occurs when one mole of
at 298K and 100 kPa (i.e. standard conditions)
atomisation
Hoat
note the differences between the enthalpies of formation, atomisation and bond dissociation
as these are often used incorrectly in calculations (think about the values for Iodine)
revise the trends (periods and groups) of first ionisation energies in addition to the changes in
magnitude (shells) and equations for successive ionisation energies of the same element
you should be able to write an equation for the gain of an electron by any given atom/ion
the first electron affinity is exothermic as the vacancy in the subshell is subject to an
attractive force from the nucleus that is not completely screened.
the second electron affinity is endothermic since an electron is being moved towards a
negative ion and mutual repulsion must be overcome (subsequent additions are increasingly
endothermic as the size of the negative charge increases)
EXOTHERMIC
ENDOTHERMIC
an ionic compound separates into gaseous ions
lattice enthalpy is higher if the charges are higher and/or the ions smaller as the electrostatic
force of attraction is greater see 169 (note its the same as lattice energy for A-level use)
Lattice enthalpy and enthalpy of formation are not the same thing:
Lattice enthalpy starts from gaseous ions.
Enthalpy of formation starts from elements in their normal states.
the value of the lattice energy can be derived theoretically using an electrostatic relationship
between charge sizes and distances but this makes two incorrect assumptions:
1
2
experimental values are higher than theoretically calculated values for HoL as there is in
reality a degree of covalency in all ionic compounds as the electrostatic attraction of the
cations will distort the valence electron cloud of the anions
in most cases (small ions that are singly charged) there is a reasonable agreement between
experimental and theoretical data (within 5%) i.e. the ionic model is adequate.
however, the deviation is more significant i.e. the degree of covalency increased if:
1
2
3
Summary Questions
Page 166
Page 174
13
2
Born-Haber Cycles
a Born-Haber Cycle for a simple ionic solid can be constructed using Hesss Law
(including ionisation energy, electron affinity, lattice energy, atomisation energy)
Note that, unlike the energy cycle diagrams met at AS-level, these are energy level diagrams in
that they are drawn with up = endothermic and down = exothermic change
Hosol
hydration
Hohyd
hydration involves ion-dipole electrostatic forces hence ionic solids can dissolve in polar
solvents such as water
the payback of hydration enthalpy is not available in non-polar solvents rendering the process
too endothermic overall to be possible
solubility is essentially a trade off between overcoming the enthalpy of lattice dissociation
enthalpy (endothermic in this direction) and enthalpies of hydration (always exothermic)
solubility is feasible if this is an exothermic outcome overall (e.g. NaOH(aq))
although ENTROPY (see later) will also have a say if the enthalpy of solution is only
slightly endothermic (e.g. NH4NO3(aq))
Hesss Law can be used to construct a solvation energy cycle (see 173)
Summary Questions
Page 172
1
Page 174
1
Pages 171 2 and Questions 1 - 4
Page 184
1
Page 248
5, 6 (read entropy for d(i))
164 173
Born Haber lattice
s-cool: Chemical Energetics
it seems reasonable that exothermic reactions can occur spontaneously, after all the products
are relatively more stable than the reactants (stronger bonds)
obviously the rate of the process will depend upon the kinetic barrier (EA) i.e. kinetic
feasibility and they could be slow e.g. iron rusting or extremely slow e.g diamond into
graphite
spontaneously thus means it will happen under a given set of conditions but not necessarily in
an instant and it could be almost infinitely slow
a small proportion of spontaneous reactions however are endothermic e.g. solvating
NH4NO3(s)
at first sight this seems counter intuitive as endothermic reactions require a transfer of heat
from their surrounding resulting in products that are relatively less stable (higher stored
chemical energy) in terms of enthalpy
so why doesnt NH4NO3(aq) spontaneously undissolve as this would be exothermic and also
be kinetically more feasible relative to the forward reaction (lower EA)
why does it only go one way (assuming the solubility limit has not been exceeded)
clearly there must be another factor in the viability of a chemical (and physical) process that
determines whether it will occur spontaneously or not
Entropy (S)
the greater the degree of disorder in a system the greater the entropy e.g.
state changes
solvation
diffusion
complexity of molecules increases way to distribute energy hence greater entropy
temperature entropy is increased if it is raised and visa-versa
the second law of thermodynamics states that all viable chemical and physical changes result
in an increase in the TOTAL entropy in the Universe
heat energy flowing into a system will increase its entropy more available energy levels
more available ways in which energy can be distributed between the particles
for an endothermic reaction lowering the temperature reduces entropy but the change from
reactants to products could increase entropy (e.g. solvation).
IF there is a NET increase in entropy the reaction may be spontaneous
like enthalpy, So is specified for 298K and 100 kPa
unlike H it is possible to quantify S (units are JK-1mol-1) since it can be extrapolated from a
value of zero at 0K
Look
!
it is possible to determine the entropy change in the system (the chemicals reacting)
S(system)
S(products)
S(reactants)
note that the overall entropy may only change slightly if all the chemicals are in the same phase
if entropy must increase how can water condense spontaneously given that it achieves a
more ordered state i.e. a decrease in entropy?
We must also consider the entropy change in the surroundings to complete the picture
remember it is the TOTAL entropy change that concerns us
the total entropy change is expressed by:
T S o surroundings
-Hosystem
energy is transferred from the steam (system) to the surface that it condenses on
(surroundings) increasing its entropy such that the overall entropy increases
the ligand displacement reactions that you will meet in transition metal chemistry can often
be attributable to favourable entropy changes where the total number of particles increases
entropy and enthalpy can be combined in a quantity called Gibbs free energy (G)
G o is the standard free energy change (kjmol-1) and quantifies the enthalpy and entropy
changes at a given temperature
for a reaction to be feasible it must be zero or negative i.e such that Sototal is positive
Go = - TSototal
Go = Hosystem - TSosystem
kjmol-1
Remember to
divide entropy
by a 1000
since its in J
not kJ !!!
G o
always negative
Feasible at ALL temperatures
always positive
NOT feasible at ANY
temperature
Outcome
G
Change of State
=0
T S
if heat goes into the system then the entropy term must increase for G to remain zero
i.e. it melts to a more disordered state
visa-versa is true
the entropy change for evaporation is significantly higher than for melting as the increase in
randomness is more significant
Summary Questions
Exam Style Questions
Page 183
Page 185
Page 246
178 183
Entropy
1-3
24
1, 2
Periodicity
Elements of Period 3
Structure
Electrical
Conduction
Na
Mg
giant metallic
Al
Si
Giant
Covalent
P
S
Cl
Simple Molecular
Ar
Atoms
poor
higher,
strong
covalent
bonding
between
atoms
very
low
Mpt/oC
1410
44
-189
98
651
660
113
-101
silicon has a similar structure to diamond each silicon has 4 covalent bonds
silicon is important in the electronics industry
sodium is used in streetlights and as a coolant in nuclear reactors
magnesium and aluminium are important structural materials often used in alloys
chlorine is a product of the salt-alkali industry and has numerous uses
argon is used in lighting and lasers
sulphur is a raw material for the manufacture of sulphuric acid
Mg
Cl
Unit 2
revision
only
red phosphorus needs heating to react with oxygen but its allotrope, white phosphorus, is
stored under water as when dry it burns spontaneously in oxygen
the oxide formed contains the element in its highest oxidation state except for sulphur
Na
Mg
Al
initially vigorous
Si
slow
Summary Questions
A2 Chemistry AQA (Nelson Thornes)
Chemguide
Page 191
13
186 - 188
Period 3 elements
silicon(IV) oxide
Periodicity of Oxides
Period 3
Oxides
Physical State
(298K)
Mpt/oC
Structure
Na2O
Mg
Al2O3
SiO2
2852
2072 lower
higher size since
and charge of different
cation
structure
Giant Ionic Lattice
(Al2O3 has a degree of covalency small ion
+ large charge)
1275
Basic
Water
1610
Giant
Covalent
similar to
diamond
Amphoteric
Simple Molecular
Acidic
Acid
Alkali
Si
580 ?
SO3
(SO2)
liquid
(gas)
17 (-73)
inc. IMF
Al
P4O10
Solid
Nature of
Oxide
Reaction
of Oxide
Na
MgO
aluminium oxide acts as an abrasive (as corundum) due to the strong bonding
aluminium/magnesium oxides are used as a refractory material (furnace)
melting point silicon(IV) oxide > carbon dioxide (strong covalent bonding throughout the
structure rather than simple molecular lattice held together by weak intermolecular forces)
you should also be able to write a 3 step equation for phosphoric acid and water
Summary Questions
Exam Style Questions
Page 193
Page 194
Page 249
13
1-6
7
189 - 193
Period 3 oxides
Oxidation Numbers
LUND 3 March 2015
12
Oxidation State
this is a book keeping method of the effective control of electrons used in bonding
elements
=
0
oxidation state of elements in simple ions
=
charge on ion
oxidation state of elements in polyatomic ions
=
charge on ion
oxidation state of elements of a compound
=
0
the relatively more electronegative element is assigned the negative oxidation state
hydrogen
=
+1 (except in metal hydrides where it is -1)
oxygen
=
-2 (except in peroxide O22-) where it = -1)
group 1 metals
=
+1
group 2 metals
=
+2
fluorine
=
-1 (even with oxygen, which is +2 in OF2)
Aluminium
=
+3
metals are always positive in a compound or polyatomic ion
changes in oxidation numbers can be used to identify redox reactions in inorganic and
organic reactions e.g. metal or halogen displacement reactions
we specifically refer to an element in a species (e.g. the iron in Fe2O3 is reduced)
assume that multiple instances of an element in a species have the same value (e.g. both
carbons in ethene are -2)
OXIDATION
REDUCTION
196 - 197
oxidation number
I have written
some answers. Try
to find them and
do the bonus
STAR question
Fe3+(aq)/ Fe2+(aq)
MnO4-(aq)/Mn2+(aq)
Cr2O72-(aq)/Cr3+(aq)
S4O62- (aq)/ S2O32-(aq) (tetrathionate/thiosulphate)
CO2(g)/C2O42-(aq) (ethanedioate ion)
HSW: This titration can be used to investigate
the % of copper in a coin your teacher will
explain how if you ask
Summary Questions
Exam Style Questions
Page 199
Page
197 - 199
redox equation
writing half equations for redox reactions under alkaline conditions is a little more
tricky than under acidic conditions but here is a useful cheat
do it exactly as if it was in acidic conditions then cancel out the hydrogen ions by adding
hydroxide ions equally to both sides
you must know and use the formula of the species containing the atom(s) to be
oxidised/reduced as it exists in alkaline conditions
lets consider Fehlings (see Module 4) in which copper(II) ions are reduced to copper(I)
which exists as copper(I) oxide and an aldehyde is oxidised to a carboxylic acid (why would
you not smell this?)
using the correct species for alkaline conditions but as if in an acidic solution you should
arrive at:
try using it to derive the equations met in Periodicity of oxides reacting with alkali from the
known reactant and product
dynamic equilibrium exists between a metal and its ions in solution which results in a
potential on the metal
Mn+(aq) + ne-
M(s)
this potential depends upon the position of the equilibrium and cannot be measured
absolutely
it will be different for a more or less reactive metal so there will be a potential difference,
which is measurable, between the two pieces of metal (try chewing a piece of aluminium if
you have a metal filling youll get the idea)
the relatively more reactive a metal, the relatively more biased the above equilibria will be
to the LHS, the relatively more negative the potential on that metal will be
you should know the practical arrangement of a single cell made up of two half cells (see
figure 3 on page 200)
Zn2+(aq)|Zn(s) and
Cu2+(aq)|Cu(s)
Note: the relatively more oxidised form is shown on the LHS by convention (in practice
both reactions can go either way depending upon what they are combined with)
given that the copper is the +ve electrode (by + 1.10V in theory)
electrons flow to it so the reactions that are taking place in the two
half cells are:
Cu2+(aq) + 2e- Cu(s)
and
in effect the more reactive metal (better reducing agent) has displaced
the less reactive metal from its solution
200 - 201
redox equilibria, half cells
there are a huge number of different half cells that can be constructed (some of which dont
involve a metal in the redox reaction thus requiring an inert platinum electrode)
to have comparisons between them all would just be silly so we use an electrode potential
equivalent of sea level to which all are then compared
this works exactly like in geography where relative heights of mountains and depths of ocean
trenches are given allowing differences to be calculated
similarly, the standard electrode (reduction) potential Eo for each half cell is measured
relative to the standard hydrogen electrode (SHE), which is defined as 0V under standard
conditions:
25oC
100Kpa
1.0 moldm-3 H+(aq) CARE must be strong acid, and 0.5 moldm-3 if
H2SO4
a diagram of the standard hydrogen electrode (PRIMARY STANDARD) and how it is used
is shown in figure 6 on page 201 which you must be able to draw
a platinum electrode is used as this will not undergo a redox reaction thus will not alter the
potential of the hydrogen electrode
it is covered with finely divided platinum (termed platinized platinum) to increase surface
area and increase rate
all solutions will be 1.0 moldm-3 and 25oC as other values will alter the relative position
of the equilibria and therefore the absolute and hence measured potential difference
in practice the Calomel electrode A SECONDARY STANDARD is used for convenience
and is initially calibrated against the SHE at a value of +0.27V
Hg2Cl2(aq)
2e
2Hg(l) +
2Cl (aq)
the voltmeter used has a high resistance hence a low current is drawn so a true reading of the
potential difference is made
if a large current is drawn the concentrations of the ions in solution will change thus upsetting
the equilibria and consequentially changing the value being measured
200 - 1
hydrogen electrode,
non-metal systems, calomel
Electrochemical Series
thus relatively more reactive metals will have a relatively more ve electrode potential
lets use a familiar idea to reinforce this a more reactive metal can displace a less reactive
metal e.g. iron nails in copper(II) sulphate solution (not the other way around)
Cu2+(aq) + 2e-
Cu(s)
Eo = + 0.34V
Fe2+(aq) + 2e-
Fe(s)
Eo = - 0.44V
NOTES:
1.
2
the number of electrons lost or gained is not a factor in their relative availability
other factors, e.g. kinetics, may prevent a feasible reaction from occurring i.e
electrode potentials do not indicate the rate of a reaction, just its feasibility
(for example where a solid is involved, or where two ions of the same charge are the
reactants)
Representing Cells
convention for representing cells (with the relatively +ve half cell on the RHS):
O R
eZn(s)| Zn2+(aq)||Cu2+(aq)|Cu(s)
Eocell
EoRHS
e.g. for Zn2+(aq)|Zn(s) the electrons flow from the zinc half cell to the hydrogen half cell (Zn is
higher in the reactivity series than hydrogen):
Zn(s)| Zn2+(aq)||H+(aq)|H2(g)|Pt(s)
Eocell =
+0.76V
- EoLHS
zinc is 0.76V
i.e its ( - 0.76)
EoRHS - EoLHS
0.00V - Zn half cell
the standard electrode potentials of ions of the same element in different oxidation states
can be measured e.g. Eo Fe3+/Fe2+ = + 0.77V
1
2.
3.
Summary Questions
Exam Style Questions
12
4
Page 203
Page 213
203
Electrochemical
the feasibility of a reaction requires electrons to flow in the right direction the reverse
reaction is NOT feasible under standard conditions
Reducing agent provides
e- and is itself oxidised
R O
O R
ethe oxidising agent must have a relatively more positive electrode potential
the reducing agent must have a relatively more negative electrode potential
remember that the electrode potentials are quoted for unimolar concentrations under standard
conditions and will be modified through changes in:
concentration
pH
temperature
the effect of changes can be determined by applying LCP to the feasibility of a reaction
e.g. increasing the concentration of one of the reactants involved in the oxidising half will
increase its electrode potential thus feasibility i.e. the forward reaction is more favoured
similarly increasing the concentration of one of the reactants involved in the reducing half
will decrease its electrode potential thus the reverse reaction is favoured
our technician wishes to prepare chlorine gas based on the electrode potentials given below
and you need to suggest how this can be achieved
Cl2 + 2e-
2Cl-
Eo
+1.36 V
Mn2+ + 2H2O
Eo
+1.23 V
when you study the variable oxidation states of chromium later on you will note that alkaline
conditions are used during oxidation once again this modifies the associated electrode
potentials and hence reaction feasibility
consider the feasibility of coating a copper/nickel coin with zinc as a first step to making a
gold coin based on standard electrode potentials
during the operation of a battery the conditions change such that it goes flat
Summary Questions
Exam Style Questions
14
13
3
Page 207
Page 212
Page 246
204 - 7
Electrochemical, vanadium, reaction
feasibility
Learn the Daniel cell, zinc-carbon battery, lead acid battery and
hydrogen fuel cell. Develop an understanding of the rest. A2 Unit 5 Energetics, Redox and Inorganic Chemistry
Electrochemical Cells
Daniell Cell
THE CATHODE
THE ANODE
Zn(s)| Zn2+(aq)||Cu2+(aq)|Cu(s)
EoLHS
- 0.76
+1.10V
- ANODE: Eo = -0.8V
This means
the casing
gets thinner
in use
whilst zinc-carbon batteries are inexpensive they have very low power density so are only
useful in devices that draw very little current
the zinc container also becomes thinner when used as the zinc is oxidised
it also thins when not used as ammonium
chloride is acidic and slowly reacts with the zinc
NH4+(aq) + H2O(l) H3O+(aq) +
which may lead to leakage
NH3(aq)
hence the service/shelf life of the battery is relatively short
the terminals of the battery are made of tin plated steel or brass to prevent the exposure the
zinc, not allowing it to corrode as quickly, thus adding to the total battery life
the seal usually is made of asphalt pitch, wax, or plastic to allow the cathode mix (when the
battery gets warm) to expand without rupturing the casing
zinc chloride cells are an improvement on the original zinccarbon cell giving a longer life (about 50% due to a variation in
the chemical mix and greater mass)
electrolyte ZnCl2 paste (cf NH4Cl in standard Zn-C)
- ANODE:
+ CATHODE:
+4
+3
2MnO2(s) + H2O(l) + 2e- Mn2O3(s) + 2OH-(aq) Zn(s) Zn2+(aq) + 2eoverall reaction in a HEAVY DUTY zinc-chloride cell is:
Zn(s) + 2MnO2(s) + H2O(l) Mn2O3(s) + Zn2+(aq) + 2OH-(aq)
these were originally marketed around 50 years ago as "Heavy Duty batteries, but since this
term is not standardised it is a misleading as they are much inferior to alkaline batteries
which have since been introduced and are around 300% better
- ANODE:
+4
+3
2MnO2(s) + H2O(l) + 2e- Mn2O3(s) + 2OH-(aq)
R
overall reaction is:
Zn(s) + 2MnO2(s) Mn2O3(s) + ZnO(s)
no gases (which insulate the electrodes) are produced which is one reason why they dont
suffer from a voltage drop as do zinc-carbon batteries when worked hard
NOTE: Button batteries consist of a range of different types of system e.g. silver oxide,
alkaline and are a structural form, for a specific use (compact size/long life), rather than a
particular chemistry so are not described in this guide. At one time mercuric oxide was used
but this has ceased for obvious reasons.
1859 - Gaston Plant - the lead-acid cell: the first rechargeable battery
Eo = +1.68V
- ANODE:
Eo = -0.36V
Eo = 2.04V
upon charging the reactions are reversed and this takes place when the car is running (using
the alternator) so that lead sulphate does not build up hence giving a flat battery
even when not in use, leakage of current takes place so there is a net usage of sulphuric acid
hence the need for it to be checked and topped up when the vehicle is serviced
given the emphasis on fuel economy the battery must not add too much weight to the vehicle
but must provide enough power to start the car even in cold weather
for most of the last century these batteries have become standard for starting cars as they can
produce short bursts of a high current for many decades and are easy and cheap to
manufacture
however they cannot be used to power a vehicle for longer journeys as they provide relatively
little energy per kilogram and suffer power loss as insulating lead sulphate builds up
why do you think a car battery could explode if it is overcharged
Eo = +0.52V
- ANODE:
Eo = -0.81V
Eo = 1.33V
the anode is made from an alloy of rare earth metals that can soak up hydrogen atoms with
the general formula AB5 where A can be lanthanum and B nickel
the electrolyte is potassium hydroxide
+ CATHODE:
Eo = +0.52V
- ANODE:
Eo = 1.35V
compared with NiMH and NiCd batteries of the same sizes or weights, Lithium Ion batteries
are designed to deliver the highest energy output
a single cell voltage is 3.7V, 3 times that of NiMH batteries so a simpler battery configuration
and better space utilization is achievable in devices such as cameras
they are relatively expensive as a computer chip is required to control charging and
discharging but do offer a high capacity (hence reducing mass/size)
Li Ion batteries contain no toxic heavy metals, such as mercury, cadmium or lead
1996, the lithium ion polymer battery was developed from the lithium ion battery
these batteries hold their electrolyte in a solid polymer composite which cant leak
the electrodes and separators are laminated to each other with the whole devices encased in a
flexible wrapping instead of a rigid metal casing, which means such batteries can be
specifically shaped to fit a particular device
Fuel Cells
The Hydrogen Economy
fossil fuels are at present the most economical way to power transportation
however, price rises commensurate with supply and demand, plus pollution issues such as the
greenhouse gas CO2 and acidic nitrous oxides (from atmospheric N2 + O2 in a hot engine) etc
are driving the need for an alternative
an alternative fuel is hydrogen which if combusted does not give the pollution problems
associated with hydrocarbons, the product is water
hydrogen can be obtained from the electrolysis of sea water in the longer term but at present
most hydrogen is still obtained from fossil fuels by steam methane reforming
this reacts steam with methane (natural gas) over a heated nickel catalyst to produce
hydrogen and carbon monoxide
energy is obviously required to obtain the hydrogen so fuel cells are not the free energy
from water that is often suggested
however, given that nuclear reactors cant be turned off, off peak generation could be one of
the means of generating less expensive hydrogen along with wind, hydro, solar and tidal
whichever, there may still be some pollution associated with hydrogen production
in a battery the chemical energy is stored within the electrodes and the solution
in a fuel cell hydrogen (fuel) and air (oxygen) are fed into the cell in a similar way that petrol
and air are fed into an internal combustion engine
the difference is that the chemicals are not combusted but react to produce electricity directly
this is more efficient than combusting the hydrogen (chemical heat kinetic electrical
energy)
since a continuous supply of hydrogen is provided the voltage output remains constant
Overall:
+
4H+(aq) + O2(g) + 4eH- 2(g)
2H
2H
2O(l)(aq) + 2e
2+
Zn(s) Zn (aq) + 2e-
Eo = 1.2V
Overview
batteries reduce the need for expensive cabling and can provide power supplies to remote
places
non-rechargeable batteries are cheap and can be manufactured in all sizes e.g. button batteries
for watches, larger batteries for torches etc
however, they are thrown away afterwards along with energy and resources used in their
manufacture
rechargeable batteries are more expensive initially but less resources are wasted in the longer
term
they are vital in solar powered devices (and similar devices intent on
storing power for future use)
the lead and nicads contain toxic chemicals thus there are disposal
issues they must not go to landfill sites and must be recycled
neither are suitable for vehicles as they add too much mass and
alternatives are being investigated
fuel cells only produce water (spacecraft can use fuel cells to provide drinking water) and
will eventually become the standard power source for vehicles which will reduce CO2
emissions IF the hydrogen can be produced cheaply without fossil fuels
they provide a more efficient means of converting chemical energy into electrical energy
since it is direct rather than by a turbine
there are however problems associated with the transportation and storage of hydrogen and
the means of refuelling the vehicle
you might be asked to calculate a voltage from electrode potentials but should be aware
that the actual value will be unlikely to be this as it will not be operating under standard
conditions e.g variation in temperature
Page 246
3
200 201, 208 - 211
tbd
Transition Metals
transition metal - d block elements that are able to form ions with a partially filled d sub shell
Sc is not a transition metal because its ion, Sc3+, is iso-electronic with Ar i.e. no d electrons
Zn is not a transition metal because its ion, Zn2+, has full d sub-shell
the electronic configuration for atoms and ions (remember to write 3d then 4s !) are written
left to right in order of increasing energy
whilst the 4s subshell is initially of a lower energy than an unoccupied 3d, hence filled first,
adding electrons to the 3d pushes the 4s electrons away from the nucleus thus raising their
energy
dont forget that copper and chromium are not systematic
note that 4s electrons are always lost first when ions are formed and so first series transition
metal ions never have any 4s electrons present so dont even show 4s (4s0 is incorrect)
if you are showing ions using the electrons in boxes nomenclature then note that paired d
electrons are lost first (check Fe3+ and Co2+ for example) as mutual repulsion makes these
easier to remove
Physical Properties
typical metals i.e. malleable; ductile; good electrical and thermal conductors; all explained
by the same ideas taught in Foundation Chemistry remind yourself of these.
melting point is higher than s block metals since there are more delocalised electrons holding
structure together which also explains their greater mechanical strength
Chemical Properties
Summary Questions
Page 215
1, 2
214 - 5
Transition
Complex Ions
ligands are molecules or ions which form dative (co-ordinate bonds) by donating electron
pair(s) - lone pair donor - to a central metal ion lone pair acceptor
the coordination number is the number of coordinate bonds formed with the central metal ion
NOT necessarily the number of ligands
Unidentate ligands
Neutral
NH3
Negative
OHSCNPr-
ammine
H2O
aqua
Cl-
hydroxo
thiocyanato
chloro
CN-
cyano
=
=
=
=
plumbate
vanadate
chromate
aluminate
NOT
3+
tetraamminedicyanocobalt(III) ion
number of each
[Co(NH3)4(CN)2]+
ligand
central metal ion and its oxidation
type of ligands
number
Bi-dentate ligands
1,2-diaminoethane (en)
benzene-1,2-diol
Negative
Multidentate ligands
EDTA complexes are very stable in effect a protective cage is formed around the transition
metal ion thus isolating it from a biological system
the replacement of unidentate with multidentate ligands is favoured by entropy since the total
number of particles increases (see the section on entropy)
Uses of
EDTA
1.
2.
3.
4.
Summary Questions
Page 219
216 - 8
complex
octahedral
tetrahedral
linear
(often in silver(1)
and copper(I)
complexes
e.g.
[Ag(NH3)2]+
Tollens reagent
[Cu(NH3)2]+
square planar
e.g.
cis-platin [Pt(NH3)2Cl2]
(more on this later)
Extra info:
Summary Questions
Exam Style Questions
Page 219
Page 233
1
3
217 - 8
Complex shape
light absorbed depends on the E of electronic transitions to the next vacant energy level
E = hh is Plancks constant
however, E(3d4s) in Ti3+ cannot account for lilac colour as E is too high (i.e. uv frequency)
in an isolated transition metal ion the d orbitals all have the same energy i.e. they are
degenerate
however, ligands split the 3d energy level so that E is of a lower value corresponding to the
energy of visible light
the reason for this is that the electrons donated by the ligand change the electronic
environment to different extents for different d-orbitals in different geometrical positions i.e
the are all raised in energy but to differing degrees
white light incident upon a transition metal solution or solid will have certain wavelengths
absorbed in accordance with the value of E when exciting an electron thus removing this
colour from the spectrum
Sc3+ and Zn2+ are not coloured as there are no partially filled 3d sub-shells which is
necessary for this to work i.e. to allow the promotion of d-electrons between d-ortbitals
oxidation state
e.g.
Fe(OH)2(s) Fe(OH)3(s)
Cr2O72-(aq) [Cr(H2O)6]3+(aq)
MnO4-(aq) Mn2+(aq)
[Co(NH3)6]2+(aq) [Co(NH3)6]3+(aq)
co-ordination number
[Co(H2O)6]2+(aq) [Co(Cl)4]2-(aq)
[Cu(H2O)6]2+(aq) [Cu(Cl)4]2-(aq)
[Cu(H2O)6]2+(aq) [Cu(NH3)4(H2O)2]2+(aq)
[Co(H2O)6]2+(aq) [Co(NH3)6]2+(aq)
[Co(H2O)6]2+(aq)
Pink
2[CoCl4] (aq)
Blue
cobalt chloride paper is a test for water
[Co(NH3)6]2+(aq)
Yellow
[Co(NH3)6]3+(aq)
[Fe(SCN)(H2O)5]2+(aq)
sensitive test for the presence of Fe3+(aq)
Brown
Blood
Red
Colorimetry
you should re-familiarise yourself with the nature of light and why we see colour
two ways in which chemicals can interact with light result in:
absorption spectra (star light through a
a planetary atmosphere, chlorophyll)
emission spectra (e.g. flame tests, street lights)
absorption in the visible light varies according to the complex ion present, path length and
concentration
absorption of aqua complexes is relatively weak so colours are not very intense
certain complexing agents (e.g. EDTA) increase colour intensity to aid detection and
determination
for example complexing [Fe(H2O)6]3+(aq) ions with colourless thiocyanate ions (SCN-) to
produce the more deeply coloured [Fe(SCN)(H2O)5]2+(aq) complex ion which can be used to
detect low concentrations of iron in substances like tea by comparing absorbance against a
calibration curve of known concentrations.
in a colorimeter interchangeable filters are used to illuminate the sample with its
complementary colour where absorption is greatest hence sensitivity optimised
it is also possible to determine the formula of a complex ion
as the complexing agent is added to separate batches of the transition metal sample the
intensity of the colour will increase until there is no more transition metal ions for it to
combine with (the volume would be kept constant using water)
this allows us to determine the number of complex ions that combine with a transition metal
where both concentrations are known (ideally the same value)
Summary Questions
Exam Style Questions
Page 222
Page 233
1, 2
3 (if not already done)
220 - 222
Colour
as the number of 4s/3d electrons increases from Ti to Mn so does the maximum oxidation
state (Sc=3, Ti = 4, V = 5, Cr = 6, Mn = 7).
thereafter the maximum declines as effective nuclear charge increases suggesting that the 4s
and unpaired 3d electrons only are involved
transition metals with charges > +3 cannot exist in aqueous solution where they exist as
oxoanions instead e.g. MnO4-, Cr2O72-(aq), CrO42-(aq) with covalent bonding between the
oxygen and the transition metal (can you suggest their shape?)
this can be explained in two ways a lot of energy would be required to form a 4+ ion, and
if it existed it would have a large charge density (thus be highly polarising) so would react
with water molecules and decompose them
+2 state tends to be reducing, as exemplified by Fe2+ in the manganate(VII) titration
some +2 ions are unstable in air due to aerial oxidation (where they are themselves reducing
agents)
this can be pH dependent and occurs more readily in alkaline conditions e.g. keeping
[Fe(H2O)6]2+(aq) in acidic solution helps it resist aerial oxidation to [Fe(H2O)6]3+(aq)
Redox Titrations
higher oxidation states (typically +4 and higher) are good oxidising agents
MnO4-(aq) and Cr2O72-(aq) are particularly good as oxidising agents in redox titrations
you will need to balance redox equations some revision may be necessary here
the titration procedure is pretty much the same as with acid-base titrations
acidic conditions are employed and you should be able to carry out a calculation to
determine the minimum amount of sulphuric acid required
sulphuric acid is preferred (can you explain why each of the following: hydrochloric,
nitric and ethanoic might not be suitable?)
Summary Questions
Exam Style Questions
Page 228
Page 233
2, 3
1(some extra reading will be needed)
223 - 226
Variable oxidation state, redox titration
Chromium
Cr2+(aq)
green
blue
2+
Zn (aq)
+
2e
Zn(s)
Eo
+1.33V
-0.41V
-0.76V
the +2 state is readily oxidised back to the +3 state by air unless preserved in a reducing
(e.g. H2) atmosphere
Ox State
+6
+3
+2
Chromium
CrrO72orange
2CrO4 (shape?)
yellow
[Cr(H2O)6]3+
Green
2+
[Cr(H2O)6]
Blue
6OH(aq)-
[Cr(OH)6]3-(aq)
6H2O(l)
ions (aka
writing half equations for redox reactions under alkaline conditions is a little more
tricky than under acidic conditions but here is a useful cheat
do it exactly as if it was in acidic conditions then cancel out the hydrogen ions by adding
hydroxide ions equally to both sides
i.e.
H2O2(aq)
2H+(aq)
2e-
2OH-(aq)
2H2O(l)
[Cr(OH)6]3-(aq)
H2O2(aq)
2e-
CrO42-(aq)
2H2O(l)
2H+(aq) + 3e-
CrO42-(aq)
4H2O(l)
2OH-(aq)
+3e-
3H2O2(aq)
2CrO42-(aq)
+ 2OH-(aq) + 8H2O(l)
Summary Questions
Page 228
1, 3
204 7, 226 228, 238
Chromium
catalysts enable a different mechanism with a different activation energy (hence different
rate) whilst being chemically unchanged at the end of a reaction
NOTE CATALYSTS CHANGE THE VALUE EA NOT THE SHAPE OF THE CURVE.
Heterogeneous Catalysis
adsorption must be strong enough to hold the reactant for long enough to promote a reaction
but must not be too strong (e.g. as with tungsten) otherwise regeneration of active sites is too
slow as the product undergoes desorption from the surface
in general the strength of adsorption decreases from left to right in the transition metals and
the desorption occurs more readily in the same direction hence Fe (Haber process) Co and Ni
(Hydrogenation) are commonly used since they offer a compromise
Catalytic Converters
Write equations
for these
poisoning can occur if impurities contaminate the active sites e.g. sulphur dioxide and lead
poisons catalytic converters hence unleaded low sulphur fuels must be used
in addition the finely coated Pt/Rh can be lost from the surface
this reduces efficiency and can result in an MOT failure and a large bill
Haber process
Methanol Production
Contact process
V2O5 used rather than faster Pt as lowers costs and less prone to poisoning
specific use of the variable oxidation states of transition metals is made
+5
V2O5(s)
+4
+
SO2(g)
+4
V2O4(s)
O2(g)
V2O4(s)
SO3(g)
+5
V2O5(s)
Reactants
Product
Homogeneous Catalysis
redox reaction between peroxodisulphate (S2O82-) and iodide ions is slow as both are
negatively charged
catalysed by iron(II) (or iron(III) either will do) note oppositely charged ions now react
+2
Fe2+(aq)
+3
2Fe3+(aq)
+3
+
S2O82-(aq)
2I-(aq)
2SO42-(aq)
I2(aq)
Reactants
Products
Fe3+(aq)
+2
Fe2+(aq)
Autocatalysis
Conc.
in all cases the reaction will eventually start to slow down as reactants are used up
e.g. manganate(VII) initially reacts slowly with ethanedioate ions (from oxalic acid)
2MnO4-(aq) + 5C2O42-(aq)
the Mn2+ ions produced autocatalyse the reaction, hence it actually speeds up once started
they change to Mn3+ initially but are changed back in the next step:
MnO4-(aq)
+ 16H+(aq)
+ 4Mn2+(aq)
+ 8H+(aq)
5Mn3+(aq)
4H2O(l)
2Mn3+(aq)
+ C2O42-(aq)
2Mn2+(aq)
2CO2(g)
Summary Questions
Exam Style Questions
Exam Style Questions
Page 232
Page 233
Page 247
1-4
1, 2, 4
4, 8
229 - 230
Heterogeneous catalysis
EDTA complexes are very stable in effect a protective cage is formed around the transition
metal ion thus isolating it from a biological system
the replacement of unidentate with multidentate ligands is favoured by entropy since the total
number of particles increases (see the section on entropy)
Uses of
EDTA
1.
2.
3.
4.
Haemoglobin
haem forms four co-ordinate bonds (tetradentate) with Fe2+ (a porphyrin structure)
N in globin a protein forms a fifth to form haemoglobin
O2 or H2O form the sixth bond in oxyhaemoglobin or deoxyhaemoglobin
as oxygen is a poor ligand it is easily released in cells
lack of iron in the blood can cause anaemia as insufficient oxygen is transported resulting in
tiredness and fatigue (or is that homework)
taking iron tablets which contain soluble iron(II) sulphate counteracts this
CO (which is a better ligand than oxygen) bonds with haemoglobin more strongly to form the
relatively stable carboxyhaemoglobin thus reducing the bloods capacity to transport oxygen
cyanide ions act in a similar way
similar structures are found in a range of biologically important substances such as vitamin
B12 (cobalt), and chlorophyll (magnesium)
Cis-platin
however, it does have side effects as it also effects normal cells e.g. renal toxicity, bone
marrow suppression (loss of white blood cells increases the risk of other infections), fatigue
and hearing loss and can also induce nausea and vomiting.
testing renal function, blood and hearing is recommended before each cycle of therapy. so a
cautious approach to dosage is necessary
http://www.cancerhelp.org.uk/about-cancer/treatment/cancer-drugs/cisplatin
geometrical isomerism possible the other form being trans-platin (which has no effect on
cancer for stereochemical reasons
Tollens Reagent
diamminesilver(I) ion
[Ag(NH3)2]+(aq)
formed in ammonical silver nitrate (Tollens reagent)
used in silver mirror test for aldehydes and distinguish them from ketones
[Ag(NH3)2]+(aq) is reduced to Ag the silver mirror - and NH3 is displaced
see if you can write a balanced redox equation under alkaline conditions
complexing prevents the precipitation of Ag2O in alkaline conditions which would otherwise
mask the test
[Ag(NH3)2]+(aq) is also formed when testing for silver chloride and silver bromide with the
addition of ammonia following the silver nitrate test
the ligand displacement allows the precipitate to be re-solvated
Metal-aqua Ions
Blue
Pink
Green
Green
Yellow
Colourless
water ligands have increased O-H + bond polarity which promotes the abstraction of a
hydrogen ion by another water molecule compared to that which takes place in the autoionisation of water (see Kw)
Note the charge !
[Fe(H2O)6]3+(aq)
Pale Lilac
ACID
[Fe(H2O)5OH]2+(aq) +
H3O+(aq)
Orange
oxonium ion
BASE
ACID
H2O(l)
BASE
this is hydrolysis (reaction with water) and makes the solution pH around 2 for a 1M solution
it would be wrong to assume that most populous species is the complex ion on the RHS as the
equilibria still lies strongly to the LHS, however it does result in an increased hydrogen ion
concentration
further deprotonation very limited as water is a relatively weak base and the charge on the
complex ion is less positive and so the O-H + bond polarity is less pronounced.
the solution appears yellow as the orange colour is more intense than the pale lilac
relative acidity of M3+ cf M2+ reflects the relative polarising power of the central transition
metal on the polarity of the O-H bond of the ligand
the chemistry of Al3+(aq) is similar to tri-positive transition metal ions
Summary Questions
How science works
Page 238
Page 243
Page 235
1, 2
1
Theories of acids
234 - 7
Acidity of hexaaqua
green
orange
white
Cu(OH)2(s)
Co(OH)2(s)
Fe(OH)2(s)
pale blue
blue
green
deprotonation reactions occur with the addition of basic hydroxide ions to a greater extent
than in aqueous solution and this eventually presents a neutral complex ion and thus
precipitation (hydroxide ions are a better base than water)
alternatively this reaction can be depicted as a reaction between a hydroxide ion and the
oxonium ion (based on the equation on page 45) with a consequential shift in equilibria
either is acceptable as the outcome is essentially the same, but direct abstraction by
OH-(aq) is easier to produce equations for.
[Cr(H2O)6]3+(aq)
OH-(aq)
[Cr(H2O)5OH]2+(aq) + H2O(l)
[Cr(H2O)5OH]2+(aq) +
OH-(aq)
[Cr(H2O)4(OH)2]+(aq) + H2O(l)
[Cr(H2O)4(OH)2]+(aq) +
OH-(aq)
[Cr(H2O)3(OH)3](s) + H2O(l)
here there is no repulsion since there is no charge and so the complexes can hydrogen bond
together producing a gelatinous precipitate.
all the hydroxide precipitates are solvated by the addition of acid which reverses the
equilibria (equations must be known acid + base salt + water).
precipitates insoluble in XS sodium hydroxide solution, but soluble in acid, are basic
Fe(OH)3(s)
Cu(OH)2(s)
Fe(OH)2(s)
Co(OH)2(s)
XS NaOH(aq)
XS sodium hydroxide can cause the precipitate to re-dissolve for amphoteric hydroxides due
to further deprotonation for:
Cr(OH)3(s)
Al(OH)3(s)
[Cr(H2O)3(OH)3](s)
OH-(aq)
[Cr(H2O)2(OH)4]-(aq) + H2O(l)
the charged particle created can now be solvated and if the sodium hydroxide solution is
concentrated enough then the hexahydroxo- complex can eventually be formed.
[Cr(H2O)2(OH)4]-(aq) +
OH-(aq)
[Cr(H2O)(OH)5]2-(aq) + H2O(l)
[Cr(H2O)(OH)5]2-(aq) +
OH-(aq)
[Cr(OH)6]3-(aq)
+ H2O(l)
carbonate ions react with oxonium ions to yield carbon dioxide gas
CO32-(aq)
2H3O+(aq)
CO2(g) +
3H2O(l)
the relatively high acidity of tri-positive transition metal results in their metal carbonates
being unstable
[Fe(H2O)6]3+(aq)
2H3O+(aq)
CO32-(aq)
[Fe(H2O)5OH]2+(aq) +
H2O(l)
CO2(g) +
H3O+(aq)
3H2O(l)
thus carbonate ions react with tri-positive transition metal ions to produce carbon dioxide gas
HENCE FIZZING in addition to a hydroxide precipitate
the deprotonation equilibrium is shifted to the RHS as the carbonate ion removes the
oxonium ion until the neutral triaquatrihydroxo- complex (the precipitate) is obtained
the overall equation should be known but can be derived on the basis of a shift in equilibrium
as the carbonate ion reacts with oxonium ion (it is slightly harder to work it out starting with
the carbonate ion abstracting a hydrogen ion directly, but is also acceptable)
2[M(H2O)6]3+(aq) +
Cr(OH)3(s)
green
3CO32-(aq)
Fe(OH)3(s)
orange
Al(OH)3(s)
di-positive transition metal carbonates are stable as the oxonium ion concentration is
relatively low
hence metal carbonate precipitates are produced and no CO2(g) is evolved
CoCO3(s)
mauve
CuCO3(s)
blue-green
237 - 8
aqua ions hydroxide,
aqua ions carbonate
FeCO3(s)
green
ammonia undergoes hydrolysis with water although it is only a weak alkali as the equilibria is
biased to the LHS
the hydroxide ion concentration is thus much lower than with fully ionised NaOH(aq)
NH3(aq)
BASE
H2O(l)
ACID
NH4+(aq)
ACID
OH-(aq)
BASE
as with sodium hydroxide a metal hydroxide precipitation can be assumed to occur by direct
deprotonation by the hydroxide ion.
alternatively this reaction can be depicted as a reaction between a hydroxide ion and the
oxonium ion (based on the equation on page 45) with a consequential shift in equilibria
or abstraction of a proton by an ammonia molecule either is acceptable as the outcome
is essentially the same, but direct abstraction by OH-(aq) is easier to produce equations
for and offers commonality with sodium hydroxide so less to remember.
Cr(OH)3(s)
Fe(OH)3(s)
Al(OH)3(s)
green
orange
white
Cu(OH)2(s)
Co(OH)2(s)
Fe(OH)2(s)
pale blue
blue
green
[Cu(H2O)4(OH)2](s) + 4NH3(aq)
pale blue
[Cu(NH3)4(H2O)2]2+(aq)
deep blue
+ 2OH-(aq)
however, ammonia is a better ligand than hydroxide ions and water as its lone pair are
less well held than for the relatively more electronegative oxygen hence ligand
displacement can occur once the concentration of ammonia is high enough to bias the
equilibria adequately
the geometry is still octahedral as the ammonia ligand is roughly the same size as the
water ligand but is slightly distorted as the Cu-O bonds are weaker (water is a poorer
ligand) therefore longer
similarly:
[Co(H2O)4(OH)2](s) + 6NH3(aq)
blue
[Co(NH3)6]2+(aq)
+
4H2O(l)
+ 2OH-(aq)
pale yellow
darkens on standing due to aerial oxidation
to brown [Co(NH3)6]3+(aq)
[Cr(H2O)3(OH)3](s)
green
[Cr(NH3)6]3+(aq)
purple
+ 6NH3(aq)
3H2O(l)
+ 3OH-(aq)
aluminium, iron(II) and (III) DO NOT undergo these ligand displacement reactions
hence their hydroxide precipitates are insoluble in xs ammonia
Summary Questions
Exam Style Questions
Page 243
Page 244-5
3, 4
2, 4, 5
239 240, 242 - 243
aqua ions ammonia
replacement is stepwise and is reversible this also means that it may be incomplete e.g. in
the example below whilst [Cu(Cl)4]2-(aq) is yellow what will be seen is a green solution,
implying that complete substitution has not occurred
some ligands form more stable complexes than others which will effect the equilibrium
position for a given set of conditions
there is a relationship between effectiveness as a ligand, base and nucleophile as all three are
essentially related to the availability of a lone pair e.g. cyanide ions are better than water/O2
see haemoglobin section
substitution by bidentate and multidentate ligands are also favoured by an increase in entropy
as there will be a consequential increase in the number of independent particles
moles of EDTA used = moles of T.M. ion and is useful for the analysis of the concentration
of a transition metal (by titration or colorimetry)
concentration and temperature will effect the position of equilibrium and hence the colour
e.g.
[Co(H2O)6]2+(aq)
pink
+ 4Cl-(aq)
[Co(Cl)4]2-(aq) +
blue
6H2O(l)
[Cu(H2O)6]2+(aq)
blue
+ 4Cl-(aq)
[Cu(Cl)4]2-(aq) +
yellow
6H2O(l)
the co-ordination number is changed as water is replaced by the far larger chloride ion
usually associated with a significant colour change
when water ligands are replaced by the similar sized ligands, e.g. ammonia, the octahedral
geometry is retained
the stability of the +II oxidation state can be altered by the ligand present e.g. yellow
[Co(NH3)6]2+(aq) is readily oxidised to brown [Co(NH3)6]3+(aq) by oxygen from the air
whereas [Co(H2O)6]2+ (aq) is not.
similarly alkaline conditions/hydroxyl ligands can also make oxidation easier e.g.
in case you wondered this is because the electrode potentials in your text book relate to the
hexaaqua complex and changing the ligand will modify its value
a similar change in relative electrode potentials occurs when alkaline rather than acidic
conditions are employed see the oxidation of chromium
Summary Questions
Exam Style Questions
Page 241
Page 244
1-4
1, 3
239 241, 242 243, 228
Ligand displacement, cobalt, iron hydroxide
Solution
NaOH(aq)
XS NaOH(aq)
NH3(aq)
XS NH3(aq)
Na2CO3(aq)
Other test
Result
Fe3+
Fe2(SO4)3
FeCl3
Yellow
Orange-brown
gelatinous ppt.
Insoluble
Orange-brown
gelatinous ppt.
Insoluble
Orange-brown
gelatinous ppt.
KMnO4
(acidified in
dilute H2SO4)
No reaction
occurs.
Fe2+
FeSO4
Green
Insoluble
Insoluble
KMnO4
(acidified in
dilute H2SO4)
Purple
MnO4decolourise
dFe2+ Fe3+
Cu2+
CuSO4
Pale blue
Insoluble
Green ppt.,
then, slowly
turning orange
due to aerial
[O]
Pale blue ppt.
Soluble (deep
blue solution)
Blue-green ppt.
Co2+
CoCl2
Pink
Insoluble
Blue ppt.
Mauve ppt.
Al3+
Al2(SO4)3
Colourless
White ppt.
Soluble
(colourless
solution)
White
gelatinous ppt.
Soluble (yellow
solution which
darkens on
standing due to
aerial [O])
Insoluble
Cr3+
CrCl3
Green
Grey-green ppt.
Soluble (green
solution)
Grey-green to
grey-blue
gelatinous ppt.
Soluble
(slightly) -in
excess a violet
or pink solution
formed.
Green ppt.
ION
White ppt.
Please note that the above colours are illustrative (it should be obvious that variables beyond control are concentration, colour on computer screen, colour of printer !!!)
Colour
Cr
Mn
Fe
Co
Cu
(all hexaaqua
unless
otherwise)
Mn2+ (almost)
Colourless
Lilac/Purple
Pink
Blue
Green
Yellow
Orange/Brown
[Cr(NH3)6]2+
MnO4-
CoCO3
[CoCl4]2-
Cr2+
Co(OH)2
Cu2+
Cu(OH)2
[Cu(NH3)4]2+
CuCO3
[Co(NH3)6]2+
[CuCl4]2-
Cr3+
Cr(OH)3
[Cr(OH)6]3CrO42_
Fe2+
Fe(OH)2
FeCO3
Fe3+
Cr2O72_
Fe(OH)3
Co(OH)3
[Co(NH3)6]3+
[Fe(SCN)]2+
Co2+
Red
Cu2O
A2 Module 5
Thermodynamics
Enthalpy change (H)
be able to define and apply the terms enthalpy of formation, ionisation enthalpy, enthalpy of atomisation of an element and of a compound, bond
dissociation enthalpy, electron affinity, lattice enthalpy (defined as either lattice dissociation or lattice formation), enthalpy of hydration and enthalpy of
solution.
be able to construct a Born.Haber cycle to calculate lattice enthalpies from experimental data
be able to calculate enthalpies of solution for ionic compounds from lattice enthalpies and enthalpies of hydration
be able to use mean bond enthalpies to calculate an approximate value of H for other reactions
be able to explain why values from mean bond enthalpy calculations differ from those determined from enthalpy cycles
Periodicity
Study of the reactions of Period 3 elements Na . Ar to illustrate periodic trends
be able to describe trends in the reactions of the elements with water, limited to Na and Mg.
be able to describe the trends in the reactions of the elements Na, Mg, Al, Si, P and S with oxygen, limited to the formation of Na 2O, MgO, Al2O3, SiO2,
P4O10 and SO2.
Redox Equilibria
Redox equations
be able to apply the electron transfer model of redox, including oxidation states and half equations to d-block elements
Electrode potentials
know the IUPAC convention for writing half-equations for electrode reactions.
know and be able to use the conventional representation of cells.
understand how cells are used to measure electrode potentials by reference to the standard hydrogen electrode
know the importance of the conditions when measuring the electrode potential, Eo (Nernst equation not required).
know that standard electrode potential, Eo , refers to conditions of 298 K, 100 kPa and 1.00 mol dm3 solution of ions.
Electrochemical series
know that standard electrode potentials can be listed as an electrochemical series.
be able to use Eo values to predict the direction of simple redox reactions and to calculate the e.m.f of a cell.
Electrochemical cells
appreciate that electrochemical cells can be used as a commercial source of electrical energy
appreciate that cells can be non-rechargeable (irreversible), rechargeable and fuel cells
be able to use given electrode data to deduce the reactions occurring in non-rechargeable and rechargeable cells and to
deduce the e.m.f. of a cell
understand the electrode reactions of a hydrogen-oxygen fuel cell and appreciate that a fuel cell does not need to be
electrically recharged
appreciate the benefits and risks to society associated with the use of these cells
Transition Metals
General properties of transition metals
know that transition metal characteristics of elements Ti - Cu arise from an incomplete d sub-level in atoms or ions.
know that these characteristics include complex formation, formation of coloured ions, variable oxidation state and catalytic activity.
Catalysis
know that transition metals and their compounds can act as heterogeneous and homogeneous catalysts.
Heterogeneous
know that a heterogeneous catalyst is in a different phase from the reactants and that the reaction occurs at the surface.
understand the use of a support medium to maximize the surface area and minimize the costs and that the reaction occurs at the surface
understand how V2O5 actsas a catalyst in the Contact Process.
know that a Cr2O3 catalyst is used in the manufacture of methanol from carbon monoxide and hydrogen.
Know that Fe is used as a catalyst in the Haber process
know that catalysts can become poisoned by impurities and consequently have reduced efficiency; know that this has a cost implication (e.g. poisoning
by sulphur in the Haber Process and by lead in catalytic converters in cars)
Homogeneous
know that when catalysts and reactants are in the same phase, the reaction proceeds through an intermediate species (e.g. the reaction
between I and S2O82- catalysed by Fe2+ and autocatalysis by Mn2+ in titrations of C2O42- with MnO4)
understand that Fe(II) in haemoglobin enables oxygen to be transported in the blood, and why CO is toxic
know that the Pt(II) complex cisplatin is used as an anticancer drug
understand that [Ag(NH3)2] + is used in Tollens reagent to distinguish between aldehydes and ketones
Metal-aqua ions
know that metal.aqua ions are formed in aqueous solution:
[M(H2O)6]2+, limited to M = Fe, Co and Cu
[M(H2O)6]3+, limited to M = Al, Cr and Fe
know that these aqua ions can be present in the solid state (e.g. FeSO4.7H2O and Co(NO3)2.6H2O).
Substitution reactions
understand that the ligands NH3 and H2O are similar in size and are uncharged, and that ligand exchange occurs without change of co-ordination
number (e.g. Co2+ and Cr3+).
know that substitution may be incomplete (e.g. the formation of [Cu(NH3)4(H2O)2]2+).
understand that the Cl ligand is larger than these uncharged ligands and that ligand exchange can involve a change of co-ordination
number (e.g. Co2+ and Cu2+).
know that substitution of unidentate ligand with a bidentate or a multidentate ligand leads to a more stable complex.
understand this chelate effect in terms of a positive entropy change in these reactions
AS Chemistry Unit 2
57
AS Chemistry Unit 2
58