Chemistry notes on the specification June.

1) Explain and use the terms rate of reaction, order, rate constant, half-life
and rate determining step.
The rate of reaction is the time it equal to the products formed/time
The order with respect to a reactant is the power to which the
concentration of that reactant is raised to in the rate equation.
The rate constant, k, is the constant that links the concentration of the
reactants to the rate of the reactants. Its just a constant of
proportionality.
The half-life is the time taken for the concentration of a reactant to fall by
half.
The rate determining step is the slowest step in the reaction mechanism
of a multi-step reaction.
2) Deduce, from a concentration vs. Time graph the rate of reaction and the
half life of a first order reaction.
Concentration/time = rate. Therefore, we can find the rate by finding the
gradient of a concentration/time graph.
To find the half life of a reaction you just need to find the time on the
graph at which the concentration of the reactant has fallen by half.
3) State that the half-life of a first order reaction is independent of the
concentration.
4) Deduce, from a rate/concentration graph the order with respect to the
reactant.
For the zero order the graph will be a straight line. This is because the
concentration of a zero order element has no effect on the rate.
For a first order element the graph will be a straight line through the
origin. This is because as we double the concentration of a fist order
element we double the rate of reaction.
For a second order element the graph will curve upwards. This is because
if we double the concentration of a second order element we will
quadruple the rate.
5) Determine, using the initial-rates method, the order with respect to the
reactant.
There are three elements, 1,2 and 3. All of these elements have a
concentration of X and the rate of reaction is 1.
We increase the concentration of 1 by 5 times. The rate is still 1.
Therefore, the order of the first reaction is 0.
We cut the concentration of 2 by three times. The rate of reaction falls to
0.11. Element 2 is a second order element because the rate has fallen by
32 times.
We keep the concentration of 2 the same and we double the
concentration of 3. Our rate rises to 0.22. Three is therefore a first order
element.
6) Deduce the rate of a reaction using the equation rate = k[A] a[B]b.
7) Calculate the rate constant, k, from the rate equation.
8) Explain qualitatively the effect of temperature change on the rate constant
and hence the rate of reaction.

Increasing the temperature of a reaction will increase the value of K. In

turn, this increases the rate of reaction. Likewise, decreasing the
temperature will decrease the rate of reaction.
9) Propose a rate equation that is consistent with the rate-determining step.
The rate determining step is just the slowest step and therefore the step
that determines the rate. For instance, if you wanted to do a rate equation
from the data we used in point 5 then our rate equation would be rate =
k[2]2[3]1.
10)
Propose steps in a reaction mechanism from the rate equation and
the balanced equation for the overall reaction.
This will require practise. There are a few tips that can be followed.
If an element is to the second order it means that two of that element
plays a role in the rate-determining step.
Youll most likely split your mechanism into two equations, a fast and slow
one. If youve got any elements in the zero order those elements will be
seen in the fast equation.
11)
Calculate the concentration of quantities present at equilibrium.
There are two ways in which this question may be approached. One way is
that the value for Kc will be given as well as the concentrations of some
other quantities. You will then be left to calculate the concentration of the
remaining substances by simply rearranging the equation. Alternatively,
you may be given an equation, such as A+ B 2C and told that initially
you have 1 mol of A and 1.3 moles of B in a one dm 3 solution. After the
reaction, you are told that you have 0.1 moles of A and you need to work
out the concentrations of all the concentrations of quantities remaining at
equilibrium.
We know that 0.9 moles of A has been used. Therefore, 0.9 moles of B
must also have been used. A and B are in a 1:1 ratio but we know that for
every one mole of A (or B) there is two moles of C. Therefore, there must
be 1.8 moles of C.
Number of moles = concentration * volume. Therefore concentration =
number of moles/volume. As this reaction took place in a solution of 1 dm 3
the concentrations after the reaction are 0.1 mol dm -3, 0.4 mol dm-3 and
1.8 mol dm-3 for A, B and C respectively.
12)
Deduce from homogenous reactions, expressions for K c.
Using our example above Kc = [C]2/[A]1[B]1. The order with respect to the
reactant is based on the balancing number we put before the reactant in
the overall equation.
13)
Calculate the value of Kc and determine the units of Kc.
Calculating the value of Kc is fairly simple and just requires practise.
The units can be harder to determine. If we look at our above example
then we have:
Kc = [mol dm-3]2/[mol dm-3] * [mol dm-3]. In this case, all of the units cancel
out and this Kc would be unitless.
Consider Kc = [C]2[D]2/[A]1[B]1. Our units are ([mol dm-3]2 * [mol dm-3]2)/
[mol dm-3]2. In this case we can just cancel out one of the [mol dm -3]2 seen
in the equation. Our units for Kc are therefore equal to [mol dm-3]2 which is
mol2 dm-6.

14)
Explain the effect of changing temperature on the value of K c for
exothermic and endothermic reactions.
The higher the value of Kc the further to the right the position of
equilibrium will lie. If we increase the temperature of an endothermic
reaction then position of equilibrium will move towards the right. From this
we can deduce that the value of Kc increases.
If our forward reaction is exothermic and we increase the temperature
then the position of equilibrium will lie further to the left and therefore the
value of Kc will decrease.
While the above is a useful way to deduce the change in K c remember that
it is actually Kc that effects the position of equilibrium.
15)
State that the value of Kc is not affected by changes in
concentration or pressure or by the presence of a catalyst.
If we have a Kc ratio of 5 at a certain temperature, X, then the system
would only be in equilibrium at that temperature if the K c ratio remains at
5. If we change the concentrations we will change the K c ratio and thus the
system will no longer be in equilibrium. Changing the pressure will have a
similar effect.
The presence of a catalyst does nothing as this increases the rate of the
forward and reverse reactions by the same amount.
16)
Describe an acid as a species that can donate a proton and a base
as a species that can accept a proton.
17)
Illustrate via ionic equations the role of H+ in the reactions of acids
with metals, carbonates, bases and alkalis.
Carbonates:
2HCl (aq) + CaCO3 (s) CaCl2 (aq) + CO2(g) + H2O (l)
2H+ (aq) + CaCO3 (s) Ca+ (aq) + CO2 (g) + H2O (l)
If this carbonate was in solution, however, then we could write our ionic
equation as:
2H+ (aq)+ CO32-(aq) CO2 (g) + H2O (l)
Note that we dont bother putting Cl- (aq) in, because this ion remains the
same.
Metals:
This is actually a redox reaction, so be careful with this one. When you
react metals with acids use hydrochloric acid rather than sulphuric or
nitric as these two are powerful oxidising agents that can result in other
products being generated.
2HCl (aq) + Mg (s) MgCl2 (aq) + H2 (g)
2H+ (aq) + Mg (s) Mg2+ (aq) + H2 (g)
All other reactions have been covered in the past. The formula for writing
the ionic equations remains the same throughout.
18)
Describe and use the term conjugate acid-base pairs.
HA (aq) + H2O A- (aq) + H3O+ (aq)
On the right side of the reaction we have our acid, HA. This reacts with
water to form a hydronium ion and our negatively charged A ion. As the
acid is a weak acid this reaction is reversible. For the reverse reaction, the
hydronium ion donates a proton to the A- ion. This means that in the
reverse reaction the hydronium ion acts as the acid while the A - ion acts

as the base, accepting a proton.

A is therefore the conjugate base of HA, which acted as the acid in the
forward reaction.
H3O is therefore the conjugate acid of H2O which acted as the base in the
forward reaction.
19)
Explain in terms of dissociation the difference between a strong and
a weak acid.
H2SO4 + 2Na Na2SO4 + H2O.
HA H+ + AThe difference between a weak acid and a strong acid is that a strong acid
will dissociate completely whereas a weak acid will not. Instead, a weak
acid will form equilibria.
20)
Explain that the acid dissociation constant, K a, shows the extent of
acid dissociation.
Ka = [H+] [A-]/[HA]. The larger the value of Ka the greater the dissociation.
21)
For weak acids, deduce expressions of Ka and PKa.
Ka = [H+] [A-]/[HA].
PKa = -log[Ka]
Ka = 10-PKa.
22)
Define pH as pH = -[log(H+)] and [H+(aq)] = 10-pH.
23)
State and use the expression ionic product of water.
Water molecules will actually dissociate into H + and OH- ions. This happens
very rarely, but none the less happens. An expression for this is:
Kc = [H+(aq)][OH-(aq)]/[H2O(l)].
The concentration of water is always going to be 1000/18 = 55.6 mol dm -3.
We could write this expression as Kc * [H2O(l)] = [H+(aq)][OH-(aq)]
Kc and [H2O] are both constants that we can merge into one constant,
called the ionic product of water.
Kw = [H+(aq)][OH-(aq)]
The concentration of H+ and OH- ions at 25 C is 10-7. Therefore, the ionic
product of water = (10-7)2 = 10-14 mol dm-3.
24)
Calculate the pH from [H+(aq)] for strong acids monobasic acids.
pH = -[logH+(aq)]
25)
Calculate the pH from [H+(aq)] for weak monobasic acids.
Ka = [H+] [A-]/[HA]
The concentration of H and A will be the same. Therefore, we could write
this equation as...
Ka = [H+]2/[HA]
Therefore, [H+(aq)] = sqrt [HA] * Ka.
Then pH = -log[H+(aq)]
26)
Calculate the pH from [H+(aq)] for strong bases using Kw
[H+(aq)] = Kw/[OH-(aq)]
As our base is a strong base it will dissociate completely. Therefore, if
weve been given the concentration of our base, which is, for instance,
1mol dm-3, then the concentration of OH- ions will be the same.
From here we can find the value of H+ and then the pH.
Alternatively we can use the pOH. pOH = -log[OH -(aq)].

This will give us a number, for example, 1.3.

To find the pH simply do 14-1.3
Calculate the Ka of a weak acid using appropriate data.
You will be given the pH, most likely. From here use the pH to find the
concentration of H+ ions.
Then Ka = [H+]2/[HA].
27)
Describe a buffer solution as a system that minimises pH changes
on addition of small amounts of an acid or a base.
28)
State that a buffer solution can be made from a weak acid and a
salt of that weak acid. A good example being CH 3COOH and CH3COO-Na+.
29)
Explain the role of the conjugate acid/base pair in an acid buffer
solution.
We have two reactions going on here.
CH3COOH (aq) CH3COO-(aq) + H+ (aq)
CH3COO-Na+ (aq) CH3COO- (aq) + Na+ (aq)
The solution contains a large amount of CH 3COO- (aq) and CH3COOH. This
pushes the equilibrium position well to the left. This means the
concentration of H+ ions is very small.
If the solution becomes more alkali the OH- ions react with the H+ ions to
form H2O. This moves the position of equilibrium to the right.
If an acid is added then the H+ ions react with the CH3COO- and cause the
position of equilibrium to move to the left.
30)
Calculate the pH of a buffer solution from the K a value of a weak
acid and the equilibrium concentrations of the conjugate acid/base pair.
[H+(aq)] = Ka * [HA(aq)]/[A-(aq)]
This is the basic equation you use. From here you can work out the pH by
using the aforementioned equation. Were able to use this equation
because the position of equilibrium will lie very far to the left. Therefore, it
can be assumed that the concentration of HA remains approximately the
same.
31)
Explain the role of carbonic acid/hydrogencarbonate buffer in the
control of blood pH.
The equilibrium set up is the following:
H2CO3 H+ + HCO3-.
OH- ions will react with the H+ ions to produce H2O. This results in the
position of equilibrium moving towards the right.
H+ ions will react with the hydrogen carbonate ions. This will move the
position of equilibrium to the left.
32)
For acid/base titration pH curves for strong and weak acids and
bases, i) Interpret or sketch their shapes. Ii) Explain the choice of a
suitable indicator, given the pH ranges for the indicator.
The graphs are fairly easy to draw, but this will require practise. If youre
titrating a weak acid against a strong base then your graph will start at
around 3 or 4 pH and end at 13 pH and so on and so forth.
A good indicator will change colour during the straight line section of the
graph. In other words, somewhere around the equivalence point.
33)
Define the term enthalpy change of neutralisation and calculate
enthalpy changes from experimental results.
The standard enthalpy change of neutralisation is the enthalpy change

that accompanies the neutralisation of an aqueous acid by an aqueous

base to form one mole of H2O under standard conditions.
Firstly, you will need to work out the amount of heat gained by the
surroundings. Q = M * c * t.
You will then need to work out the amount in moles of substances that
have been reacted. Remember that the definition of neutralisation is
relative to one mole.
For instance, if youd worked out the energy change to be 1 KJ but you
were only using 0.5 moles of acid/base then youd double 1KJ to get the
enthalpy of neutralisation.
34)
Explain the term lattice enthalpy.
Lattice enthalpy is the change that accompanies the formation of one
mole of an ionic solid from its gaseous ions under standard conditions.
35)
Use the lattice enthalpy of simple ionic substances to construct
born-Haber cycles and carry out related calculations.
36)
Explain the terms enthalpy change of solution and enthalpy of
hydration.
When an ionic substance dissolves in water the ionic lattice gets broken
down and then the ions get hydrated.
In order to break down the ionic lattice the attractive forces binding the
ionic substance together must be overcome. This process is exactly the
opposite of that producing the lattice enthalpy.
The standard enthalpy change of solution is the enthalpy change that
takes place when one mole of a compound is completely dissolved in
water under standard conditions.
The standard enthalpy of hydration is the enthalpy change that takes
place when one mole of isolated gaseous ions is dissolved in water
forming one mole of aqueous ions under standard conditions.
37)
Use the enthalpy change of solution and hydration to construct
born-Haber cycles and carry out related calculations.
The energy that is required to break the ionic lattice is going to be equal
and opposite of the ionic lattice. The Born-Haber cycles youd draw for this
are actually a lot simpler than the more conventional kind. The lattice
enthalpy + the enthalpy change of solution = enthalpy of hydration of
both elements.
38)
Explain the effect of ionic charge and ionic radius on the exothermic
value of a lattice enthalpy and enthalpy change of hydration.
The greater the ionic charge the more negative the enthalpy change is for
both. The higher the charge the greater the attraction. Greater attractions
need more energy input to overcome them.
The greater the ionic radius the weaker the attraction between the ions,
resulting in less negative lattice/hydration enthalpies.
39)
Explain the entropy is a measure of disorder within a system and
that it becomes more energetically stable when it becomes more
disordered.
Alternatively, entropy can be thought of as the dispersal of energy within
a system.

40)
Explain the difference in magnitude of entropy in i) of a solid and a
gas, ii) when a solid lattice dissolves, iii) for a reaction in which there is a
change in the number of gaseous molecules.
Entropy increases as a substance changes from a solid to a gas. This is
because in a gas the positions of the particles are more random. Greater
randomness means more disorder and thus more entropy.
When a solid lattice dissolves we get more entropy as well, for the same
reason as above.
With more gaseous molecules we also get an increase in entropy.
41)
Calculate the entropy change for a reaction when given the
entropies of the reactants and products.
S = Sproducts - SReactants.
42)
Explain that the tendency for a process to take place depends on
the temperature, T, the entropy changes within the system, S and the
enthalpy change, H within the surroundings.
43)
Explain that the balance between entropy and enthalpy changes is
the free energy change, G, which determines the feasibility of a reaction.
A reaction is feasible when the change in free energy is less than zero.
I.e., it is a negative number.
44)
State and use the relationship G = H - TS.
45)
Explain, in terms of entropy and enthalpy, how endothermic
reactions are able to take place spontaneously.
If we have an exothermic reaction in which the products have a greater
entropy than the reactants the reaction will be feasible.
G = -1 1*1 would result in the free energy change being less than zero,
meaning the reaction would be feasible.
An exothermic reaction can also take place if the products have less
entropy than the reactants. However, such a reaction will only be feasible
at very low temperatures.
G = -1 (-1) * 0.001. This example would still give a negative value for
G, and thus this reaction would take place. Note that the numbers used
are just for example, and not realistic.
At this point it is worth noting that the units for enthalpy are KJ mol -1
whereas for entropy the units are J K-1 mol-1. When performing
calculations, either divide the entropy by 1000 or times the enthalpy by
1000 to give consistent units.
46)
Explain the following terms: Redox, oxidation number, half-reaction,
oxidising agent and reducing agent.
Redox reactions are reactions which involve the transfer of electrons to
oxidise one species and reduce another. Oxidation is loss and reduction is
gain (of electrons).
Oxidation number States the total number of electrons that have been
removed from an element (if its a positive oxidation state) or the total
number of electrons that have been added to an element (negative
oxidation state).
A half-reaction will show just the oxidation of a species or just the
reduction of a species. For instance, Fe Fe3+ + 3e-.

An oxidising agent is one that causes the oxidisation of a species, whereas

a reducing agent is an agent that causes the reduction of a species.
47)
Construct redox equations using relevant half-equations or oxidation
numbers.
You may be given two half equations, one for oxidation and one for
reduction:
A A4+ + 4eB + 2e- B2-.
The first step is to have the same number of electrons on both equations.
In this example its fairly simple, we just need to times the reduction halfequation by two. Our new equation for B is 2B + 4e - 2B2-.
Now we can add the two half equations together.
A + 2B + 4e- A4+ + 2B2- + 4e-. As we have equal amounts of electrons
on both sides we can remove them from the equation. Our final equation
is:
A + 2B A4+ + 2B2Consider another example in which hydrogen iodide is oxidised to iodine
by concentrated sulphuric acid.
Firstly write out the equation. Dont worry if its not balanced.
2HI + H2SO4 I2 + H2S
Now we need to see where the oxidation changes have been. Look at
sulphur in the sulphuric acid. It has an oxidation state of +6. We can tell
this because as H2SO4 is a neutral compound and the overall oxidation
state must be zero. Hydrogen has an oxidation state of +1, oxygen of -2
and therefore sulphur is +6.In HsS, however, sulphur has an oxidation
state of -2. This means that theres been a change in oxidation state of -8.
Now look at the iodine in 2HI. It has an oxidation state of (2 * -1).However,
as I2 iodine has an oxidation state of 0.
So, for the reduction side of this reaction we have a change in oxidation
state of -8. For the oxidation side we have a change of +2. The total
increase in oxidation number must be equal to the total decrease in
oxidation number. Therefore, we need to balance our equation so that we
have a change in oxidation state of +8 for the oxidation side of our
equation.
8HI + H2SO4 4I2 + H2S
Were still short of eight hydrogens and four oxygens. We can insert these
into the equation by adding water. Our final equation is:
8HI + H2SO4 4I2 + H2S + 4H2O.
48)
Interpret and make predictions for reactions involving electron
transfer.
49)
Define the standard electrode potential.
The standard electrode potential of a half cell is the e.m.f of a half cell
compared with a standard hydrogen half cell when measured at 298k with
solution concentrations of 1 mol dm-3 and a gas pressure of 100kPa.
50)
Describe how you would measure, using a hydrogen electrode, the
standard electrode potentials of metals or non-metals in contact with their
ions in aqueous solution or ions of the same element in different oxidation

states.
Firstly we will deal with metals in contact with their ions in aqueous
solution.
You will have two beakers. In one beaker youll have a zinc strip within a
solution of Zn2+ ions. Your other electrode will be your hydrogen electrode.
A hydrogen electrode contains a platinum electrode to connect the H 2 and
the H+ ions. It also contains Hydrogen gas within a container.
The platinum electrode will be connected to a wire which is then
connected to a zinc strip in the zinc half-cell. This wire allows the transfer
of electrons between the two half-cells. A voltmeter will be attached to the
wire to prevent current flow. On top of this, there will be a salt bridge
between the solutions of the two half cells. The solution will contain
hydrochloric acid of concentration 1 mol dm-3 as the source of H+ ions.
The resulting e.m.f recorded between the hydrogen half-cell and the metal
half cell (which in this case is zinc) is the standard electrode potential of
the cell. The standard electrode potential of the half cell is exactly zero.
For non-metals and half-cells containing the same element in two
oxidation states the process is exactly the same. I will, however, go over
the composition of a half-cell that contains two elements in different
oxidation states:
An example of such an electrode is Fe 3++ e- Fe2+. This will contain a
solution of the aforementioned ions that contains equal amounts of both
ions (equimolar) and an inert platinum electrode which allows electrons to
pass in and out of the half cell.
51)
Calculate the standard cell potential by combining two standard
electrode potentials.
If we have two half cells, A and B, with a standard electrode potential of
-0.4 V and -0.9V respectively, our cell potential would be equal to the
standard electrode potential of our positive terminal minus the standard
electrode potential of our negative terminal.
In this case, half cell A is the least negative half cell and is therefore our
positive terminal.
Cell potential = -0.4-(-0.9) = 0.5 V.
52)
Predict, using standard electrode potentials, the feasibility of a
reaction.
Lets take three examples of half-cells along with the standard electrode
potentials:
Fe2+ + 2e- Fe. -0.44
Cl2 + 2e- 2Cl-. +1.36
Br2 + 2e- 2Br-. +1.07.
The above is a conventional way of writing what we call the
electrochemical series. Out of the three half cells we have the iron one is
the most negative. This means it has the greatest tendency to release
electrons. Thus, Fe would react with every other species in our
electrochemical series on the left.
As a general rule, a reaction becomes more feasible as we increase the
size of the cell potential. A reaction is unlikely to go ahead if the cell
potential is less than 0.4 V.

53)
Consider the limitations of predictions made using standard cell
potentials in terms of kinetics and concentration.
Non-standard conditions will alter the value of an electrode potential. The
Le Chatelier principle states that a system in equilibrium will move in such
a way as to reduce the effect of any change.
A + 2e- B.
If we increase the concentration of A we will move the position of
equilibrium to the right. This means that there are fewer electrons in the
equilibrium and thus the electrode potential would become more positive.
This could affect the feasibility of the reaction.
Moreover, we can make predictions about the equilibrium position but we
cant make any judgements about the reaction rate, which could be very
slow or have high activation energy. Moreover, the actual conditions used
for such a reaction to take place may be different from standard
conditions. This could affect the position of equilibrium.
54)
Apply the principles of electrode potentials to modern storage cells.
55)
Explain that a fuel cell uses energy from the reaction of a fuel with
oxygen to create a voltage.
The fuel cell contains an alkali electrolyte, which is a conducting liquid, an
anode and a cathode
There are two redox equilibria at work here.
2H2O + 2e- H2 + 2OH- = E -0.83V
0.5O2 + H2O + 2e- 2OH- = E +0.4 V
The reactants will flow into the cell (the O 2 and the H2) while the products
(H2O) flow out.
The half equations for these are:
H2 + 2OH- 2H2O + 2e-. Oxidation.
0.5O2 +2H2O + 2e- 2OH-. Reduction.
We can cancel out the H2O, the electrons and the OH- to leave us with our
overall equation:
H2 + 0.5O2 H2O.
The hydrogen half cell, the anode, provides the electrons. These electrons
flow along a wire and in the process generate energy.
In more detail that isnt needed for the test:
The anode has a platinum catalyst which separates the hydrogen into
electrons and protons. The electrons will flow to the electrical circuit,
generating electrical power. The protons generated will flow through the
electrolyte to the cathode. Oxygen flows into the cathode and reacts with
the protons and remaining electrons to form water. This is more of a
physical explanation. In the test the chemical explanation should be given.
56)
Explain the changes that take place at each electrode in a
hydrogen-oxygen fuel cell.
57)
Outline that scientists in the car industry are developing fuel cell
vehicles fuelled by hydrogen gas and hydrogen-rich fuels.
Hydrogen rich-fuels include methanol, natural gas and petrol. These are
mixed with water and converted into hydrogen gas by a reformer. For
instance:
CH3OH + H2O 3 H2 + CO2.

58)
State the advantages of FCVs over conventional vehicles in terms of
i) Less pollution and less CO2 and ii) greater efficiency.
Hydrogen fuels only produce a small amount of CO 2. A petrol engine is
less than 20% efficient whereas hydrogen fuel cells are 40-60% efficient.
59)
Understand how hydrogen might be stored in FCVs.
We may store the hydrogen as a liquid under pressure. The problem with
this is that even under very high pressures we would need the
temperature to be very low to keep hydrogen in its liquid state.
Alternatively, we could adsorb the hydrogen onto a solid material or store
hydrogen by absorbing it within some solid materials.
60)
Consider the limitations of hydrogen fuel cells.
Storing and transporting hydrogen is currently very difficult, we need
some very large scale infrastructure before we can use FCVs on a huge
scale.
The adsorbers and absorbers mentioned for the previous point have a
very short lifespan.
On top of this, current fuel cells also have a limited lifespan.
Finally, we use toxic chemicals in the production of fuel cells.
61)
Comment on the idea that a hydrogen economy may contribute
largely to future energy needs. Also comment on the potential limitations
of such an economy.
One trouble to overcome is political acceptance. As has been mentioned
above, there are logistical problems with the storage and transport of
hydrogen. As has also been mentioned above we dont currently have the
infrastructure required to make the use of hydrogen as a fuel on a large
scale feasible.
62)
Deduce the electron configurations of atoms and ions within the dblock elements of period 4 (Sc-Zn) given the atomic number and charge.
[Ar] = 1s22s22p63s23p6.
All of the elements follow the standard rules for writing electron
configurations other than two elements, Chromium and Copper.
Chromium = [Ar] 4s1 3d5. This is strange when you consider that the
previous element, Vanadium, has an electron configuration of [Ar]4s 23d3.
Copper has an electron configuration of [Ar]4s13d10.
These exceptions can be explained by the extra energetic stability offered
by full or half-filled d orbitals.
63)
Describe the elements Ti-Cu as being transition elements. I.e., dblock elements that have an ion with an incomplete d sub-shell.
64)
Illustrate the existence of more than one oxidation state for each
element in its compounds.
Transition metal elements all form ions in the 2+ oxidation state. This is,
for the most part, due to losing the 4s2 electrons.
This seems odd, as the 3d orbital has a higher energy level that the 4s
orbital. However, the electrons within the 3d orbital repel the electrons in
the 4s orbital so that they are further from the nucleus. This gives the 4s
orbital a slightly higher energy, resulting in the 4s electrons being lost
first. Further oxidation states can be achieved by losing more 3d orbital
electrons.

65)
Illustrate the formation of different coloured ions.
66)
Illustrate the catalytic behaviour of the elements and/or their
compounds.
The fact that transition metals have partially filled d sub-shells means that
the electron gaps can be filled by electrons from the reactants. The
transition metal thus provides a site for the reactants to come closer
together. This lowers the activation energy of such a reaction and thus
reduces the energy needed.
67)
Describe, including ionic equations, the simple precipitation
reactions and the accompanying colour changes of Cu 2+, Co2+, Fe2+ and
Fe3+ with aqueous sodium hydroxide.
A precipitate reaction is one where soluble ions are mixed together to
produce an insoluble compound.
CO2+(aq)+ 2OH(aq)- Co(OH)2 (s). This precipitate is pale blue.
Fe2+(aq) + 2OH-(aq) Fe(OH)2 (s). This precipitate is pale green. This is
also readily oxidised into Fe3+ and will turn a rusty brown in air.
Fe3+(aq) + 2OH-(aq) Fe(OH)3 (s). This precipitate is rusty brown.
68)
Explain the term ligand in terms of coordinate bonding.
A coordinate bond is a bond in which one of the bonded atoms provides
both of the electrons. In essence, its a dative covalent bond but in the
context of a transition metal complex ion. A ligand is a molecule or ion
that donates a pair of electrons to form a coordinate bond.
69)
State and use the terms complex ion and coordination number.
A complex ion is a transition metal ion that is bonded to one or more
ligands. The coordination number is the total number of coordinate bonds
formed between the central metal ion and its ligands.
70)
State and give examples of complexes with sixfold coordination with
an octahedral shape.
One such example is [Co(H2O)6]2+. The bond angles between the ligands
are 90 degrees. Another example of a complex ion with a coordination
number of six is [Ti(H2O)6]3+.
71)
Explain and use the term bidentate ligand. For example,
NH2CH2CH2NH2, en.
If a ligand is bidentate it means it can donate two pairs of electrons and
thus form two coordinate bonds. In our above example we have a sixfold
complex [Co(H2O)6]2+. An example of a complex that has a bidentate
ligand would be [Ni(en)3]2+. Notice that there is only three of our ligand,
but there are still 6 coordinate bonds.
72)
Describe the types of stereoisomerism shown by complexes,
included those associated with bidentate and multidentate ligands.
Complexes show both cis/trans and optical isomerism. For instance,
Ni(NH3)2Cl2 would be an example of a complex that shows cis/trans
isomerism.) The trans isomer has the Cl on opposite planes whereas the
cis isomer has the Cl molecules on the same plane.
Octahedral complexes can also show cis/trans isomerism. Consider the
complex [Co(NH3)4Cl2]+. The cis isomer has the chlorine molecules 90
degrees apart, whereas in the trans isomer the chlorine molecules are 180
degrees apart.

We see optical isomerism in any molecule that doesnt have a line of

symmetry. Optical isomers are non-superimposable mirror images about
an organic chiral centre. An example of such an isomer is [Ni(en) 3]2.
73)
Describe the use of cis-platin as an anti-cancer drug that binds to
the DNA of cancer cells, preventing division.
Cis-platin has the formula PtCl2(NH3)2.
74)
Describe the process of ligand substitution and the accompanying
colour changes in the formation of i) [Cu(NH 3)4(H2O)2]2+ and [CuCl4]2- from
[Cu(H2O)6]2+ ii) [CoCl4]2- from [Co(H2O)6]2+.
A ligand substitution reaction, as the name suggests, is one in which one
ligand is replaced by another. In a lot of cases water molecules are
replaced.
[Cu(H2O)6]2 + 4NH3 [Cu(NH3)4(H2O)2]2+ + 4H2O. During the reaction, we
go from a pale blue solution to a deep blue solution.
[Cu(H2O)6]2 + 4Cl- [CuCl4]2- + 6H2O. During the reaction, we go from pale
blue solution to yellow solution. Weve also gone from a complex with six
ligands to one that has four. This is because the chlorine ligands are larger
than the water ligands and also have stronger repulsions. This ion,
therefore, has a tetrahedral shape with a bond angle of 109.5 degrees.
The chloride ions were provided by hydrochloric acid. Also remember that
you should add the chloride in excess. If you add an intermediate amount
youll see the solution go a green colour. The reaction isnt done, but we
get green as the blue of the initial solution and the yellow of the final
solution are mixing.
[Co(H2O)6]2+ + 4Cl- [CoCl4]2- + 6H2O. During the reaction we go from
pink to blue.
75)
Explain the biochemical importance of iron in haemoglobin,
including ligand substitution involving O2 and CO.
Haemoglobin is comprised of four polypeptide chains, two A chains and
two B chains. Haemoglobin has four haem groups, one for each chain,
with Fe2+ at the centre of the group. There are four coordinate bonds
between the nitrogen atoms in the haem structure and the iron ion. A
further coordinate bond is formed between the iron and the protein globin.
Finally, one last coordinate bond can form to an oxygen molecule which is
then transported around the body, giving a total of six coordinate bonds.
Carbon monoxide can also bind to the iron in the haem group; however,
the problem here is that CO binds more strongly to the iron than the
oxygen does. This is an irreversible reaction and leaves less haemoglobin
to which oxygen can bind. This reaction is an example of ligand
substitution as the CO molecules replace Oxygen.
76)
State the stability constant, Kstab, of a complex ion is the equilibrium
constant for the formation of the complex ion in a solvent from its
constituent ions.
Consider [Co(H2O)6]2+ + 4Cl- [CoCl4]2- + 6H2O. We write our expression
for the stability constant as we would write our expression for the
equilibrium constant.
Kstab = [CoCl42-]/[Co(H2O)62+][Cl-]4. Units = dm12 mol-4.

Notice that we dont include the H 2O into our expression. This is because
all of the species are dissolved in water, meaning that water is in excess.
It can be assumed that the concentration of water remains constant.
77)
Deduce expressions for the stability constant.
78)
Relate ligand substitution complexes to stability constants and
understand that a large Kstab results in the formation of a more stable
complex ion.
79)
Describe, using suitable examples, redox behaviour in transition
elements.
We know that transition metal elements form compounds that have
variable oxidation states, this means that they can undergo redox
reactions.
Fe2+ can be readily oxidised into Fe3+.
Fe2+ (aq) Fe3+ + e-.
Manganese, Mn, exists in a few oxidation states but the ones were most
concerned with are Mn2+ and Mn7+. MnO4- is a strong oxidising agent and it
can be reduced to form Mn2+
MnO4- (aq) + 8H+(aq) + 5e- Mn2+ (aq) + 4H2O (l)
Therefore, we can use MnO4- to oxidise Fe2+ like so:
MnO4-(aq) + 8H+ (aq) + 5Fe2+ Mn2+(aq) + 5Fe3+(aq) + H2O(l)
80)
Carry out redox titrations and carry out structured calculations,
involving MnO4- and I2/S2O32A student weighted out 2.950 g of hydrated iron (ii) sulphate, FeSO 4.XH2O
and dissolved it in 50 cm3 of sulphuric acid. This solution was then poured
into a 250 cm3 volumetric flask and made up to the mark using distilled
water. 25.0 cm3 of this solution was titrated, with 0.01 mol dm -3 of KMnO4.
21.20 cm3 of MnO4- was used.
a) Calculate the amount, in moles, of MnO 4- used.
Number of moles = concentration * volume. Remember that we measure
volume in decimetres cubed but in our question weve been given values
in cm cubed. We therefore need to divide our volume by 1000.
n = 0.0100 * (21.2/1000) = 2.12 * 10-4 moles.
b) Deduce the amount of iron (ii), in moles, in the 25 cm 3 solution.
We know from our equation that for every mole of MnO 4- theres five
moles of Fe2+. The number of moles is therefore (2.12 * 10 -4) * 5 = 1.06 *
10-3 moles.
c) Deduce the amount of Fe2+ in the 250 cm3 solution.
Just times the value you got for C by 10. Number of moles = 0.0106.
d) Determine the molar mass of the iron (ii) salt
Mass = molar mass * number of moles. Therefore, Molar mass = mass/no.
Moles.
Molar mass = 2.95/0.0106 = 278.3g.
e) determine the value of X and the formula for the hydrated iron (ii) salt.
The mass of one mole of FeSO4 = 151.9g.
This must mean that 278.3 151.9 gives us the mass, in grams, of water
within our salt.
Mass of water = 126.4 g.
n = 126.4/18 = 7. Therefore, our formula is FeSO 4.7H2O.

81)
Perform non-structured titration calculations based on experimental
results.
Follow the same route as you do in the structured calculations.