F325 Equalibria, Energetic and Elements

Rates, Equalibria and PH

How fast?
The rate of reaction is the change in concentration in mol dm-3s-1
This is the rate of change of the concentration of the reactant. This can be worked
out from a concentration/time graph.

The rate of reaction is influenced by temperature, concentration and use of catalyst.

The collision theory explains all of these. Concentration, temperature and catalysts
increase the rate of reaction.

For A + B  C + D
rate = k [A]m [B]n
k is the rate constant and is affected by temperature.
A large k ⟹ fast rate of reaction and small k ⟹ slow rate of reaction.
m and n are the orders of the reaction with respect to reactant A and B.

Orders tell you how a reactant’s concentration affects the rate. Found from
experiments (i.e. doing the experiment twice with double of one reactant) or a rate of
reaction against concentration graph.
Initial Rates Method
1. If you double the reactant’s concentration and the rate stays the same, the
order with respect to that reactant is 0
2. If you double the reactant’s concentration and the rate doubles, the order
with respect to that reactant is 1. Orders of 1 have a constant half life.
3. If you double the reactant’s concentration and the rate quadruples, the
order with respect to that reactant is 2
Rate-Concentration Graph
If rate = k [A]m[B]n then
obviously the concentration
against time graphs will show
the following graphs for first,
second and third order
respectively.

Concentration-Time Graph

For 0 order, concentration

falls at a steady rate. The
half life decreases with
time. For 1st order, the half
life is constant. For 2nd
order, the half life
increases with time.
The rate-determining step is the slowest step in the reaction. The rate equation
can tell us about the reaction mechanism. The orders in the rate equation match the
number of species involved in the rate-determining step. E.g. in a 2 step mechanism,
the rate equation indicates the number of mols of each reactant involved in the slow
step. Slow + fast step = balanced equation.
e.g. for 2H2 + 2NO  2H2O + N2 the rate equation is rate = k[H2(g)][NO(g)]2 and this
tells us the rate-determining step is H2 + 2NO  H2O + N2 + O

How far?
A dynamic equilibrium is one which is reached when the rate of the forward reaction
equals the rate of the reverse reaction such that the composition of the mixture
remains constant by the reagents and products constantly changing.
Chatelier’s principle states that in a closed system in equilibrium, any change to the
equilibrium, forces it to move in such a way as to minimise the change.
➢ Temperature depends on whether the forward reaction is exothermic.
➢ Pressure depends on the number of moles on both sides of the equilibrium.
➢ Concentration moves the equilibrium to the side of which has had no change in
equilibrium.
➢ Catalysts speed up both sides by the same rate ⟹ no shift.

The exact position of the equilibrium is calculated; using Kc; the

in aA + bB ⇌ cC + dD
Kc= [C]c[D]d[A]a[B]b
The units depend on each specific case. If Kc is large the equilibrium favours the
forward reaction. If small, it favours the backward reaction.
• Kc is temperature dependant. In an exothermic reaction, Kc decreases with
increasing temperature and in endothermic, Kc increases with increasing
temperature.
• Kc is unaffected by changes in concentration (if the concentration of one
thing changes, the others must change to keep the value of Kc) or pressure
(changing the pressure on one side shifts the equilibrium to the side with more or fewer
gas molecules, restoring original pressure) or using a catalyst.

Acids
• An acid base reaction involves a proton transfer.
• A molecule of an acid contains a hydrogen that can be released as a positive
hydrogen ion or proton H+. Acids and bases are linked by H+ as conjugate
pairs such that the conjugate acid donates H+ and the conjugate base
accepts H+. By mixing an acid with a base, and equilibrium is set up between
two acid-base conjugate pairs.
(acid 1) CH3COOH (aq) + (base 1) H2O (l) ⇄ (acid 2) H3O+ + (base 2) CH3COO-(aq)

• The acid-base equilibrium of an acid, HA, in water is:

HA(aq) + H2O(l) ⇌ H3O+(aq) + A-(aq)
 Or to emphasise the loss of a proton by dissociation;
HA(aq) ⇌ H+(aq) + A-(aq)

A strong acid is one that is highly ionised in aqueous solution.

A weak acid is one that is only partially ionised in aqueous solution.

➢ Acids vary in the ease with which they release their hydrogen ions. HNO3(aq) ⇌ H+
+ NO3-(aq)
(aq)

Therefore strong acids like this undergo complete dissociation as in the

above equation.
The equilibrium position is far to the right.

➢ Weak acids, such as ethanoic acid, CH3COOH is a poor proton donor. Therefore
the equilibrium position is far to the left.

The acid dissociation constant, Ka

The usual way of indicating the strength of an acid is to use the equilibrium
constant for its ionisation in water; Ka. This is called the acid dissociation
constant.
For the reaction HA(aq) ⇌ H+(aq) + A-(aq);
Ka=H+aq[A-aq][HAaq] moldm-3
A large Ka shows the extent of the dissociation is large and the acid is a strong
acid. And vice versa.

Calculating pH for strong acids and weak aids

pH is defined by pH= -log10[H+aq]

• For a strong acid, we assume complete dissociation.

E.g. A strong acid, HA, has a concentration of 0.02 moldm-3. What is the pH. Strong
acid ⟹ complete dissociation so [H+aq]= 0.02 so pH = -log(0.02) = 1.7

• For a weak acid, we need the concentration of the acid and Ka.
Only a very small proportion of HA dissociates and hence the amount of undissociated
acid is the same as the initial concentration of HA.
Also there is a negligible proportion of H+(aq) from the ionisation of water such
that [H+(aq)] = [A-(aq)].

Using these approximations; Ka=H+aq[A-aq][HAaq] ≈[H+aq]2[HAaq]

E.g. A weak acid, HA, has a concentration of 0.2 moldm-3, and Ka=1.7 x10-
4
moldm-3 at 25oC. Find pH.
Ka=H+aq[A-aq][HAaq] ≈[H+aq]2[HAaq]= [H+aq]20.2= 1.7x10-4
∴H+aq= 0.00583 so pH=2.23

Ionic product of water, Kw

Water ionises very slightly, acting as both an acid and base. H2O(l) ⇌ H+(aq) + OH-(aq)
Only a very small proportion of molecules dissociates. Thus treating water as a weak
acid;
Ka = H+aq[OH-aq][H2O(l)] ⟹ Ka×H2Ol= H+aq[OH-aq]
This bit; Ka×H2Ol is a constant and is called Kw. It is temperature dependent.

Kw can be used to calculate the pH of water. At 25oC, Kw=1x10-14.

1x10-14= [H+(aq)][OH-(aq)]. Assume that [H+(aq)]=[OH-(aq)] and it follows that at 25oC, pH =
7.0
The pH is below 7 with high temperatures and above 7 with low temperatures.
Kw can be used to calculate the pH of strong Alkalis. At 25oC, Kw=1x10-14.
• A strong Alkali, KOH has a concentration of 0.5 moldm-3. What is the pH at 25oC?
KOH(aq) K+(aq) + OH-(aq) and since the alkali is strong, we assume [OH-] =
[KOH(aq)]=0.5 moldm-3.
Kw = [H+(aq)][OH-(aq)] = 1x10-14 and so [H+(aq)] = 10-14/0.5 and it follows that pH =
12.7

Buffer Solutions

A buffer solution is a system that minimises pH changes on addition of small

amounts of an acid or a base. The buffer solution maintains a near constant pH by
removing most of any acid or alkali that is added to the solution.

It is a mixture of a weak acid, HA and it’s conjugate base, A-;

HA(aq) ⇌ H+(aq) + A-(aq)
An example for a common buffer solution is a mixture of CH3COOH and CH3COO-Na+
(conjugate base). The pH at which the buffer operates depends on the Ka of the weak
acid and the relative concentrations of the weak acid and the conjugate base.

CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq) CH3COO-Na+(aq)  CH3COO-(aq) + Na+(aq)

The high [CH3COO-(aq)] forces the equilibrium back to the LHS and results in the buffer
solution containing very low [H+(aq)] and very high [CH3COOH(aq)] and [CH3COO-(aq)]. The
high concentrations of [CH3COOH(aq)] and [CH3COO-(aq)] resist any changes in pH.
Hence a buffer solutions cancels out the effect of any added acid or alkali and
minimises the change in pH.

Hence a buffer solution contains:

➢ High concentration of weak acid e.g. CH3COOH
➢ High concentrations of conjugate base e.g. CH3COO-
➢ Low concentration of H+

The pH of a buffer solution depends (and hence can be adjusted) by the acid
dissociation constant Ka, of the buffer system and the ratio of the weak acid to
conjugate base. Ka= SALT[H+][ACID]. Then pH= -log([H+]).

Application of Buffers
In blood, the pH is about 7.4. If the pH becomes >7.8 or <7.0 the results are fatal.
Blood contains a mixture of buffering solutions, the major one being carbonic acid-
hydrogen carbonate (bicarbonate) system.
H2O(l) + CO2(g) ⇌ H2CO3 ⇌ HCO3- + H+
Carbonic acid Hydrogen Carbonate
 • Adding an acid to the system will increase the concentration of H+(aq) driving
the equilibrium to the LHS. This increases the concentration of the carbonic
acid, H2CO3, which is in turn decreased by an increased rate of breathing
such that more CO2(g) is exhaled resulting in H2CO3 moving further to the left to
replace it. The 2 equilibria together resist increase in acidity.

• Adding an alkali to the system will decrease the concentration of H+(aq), driving
the equilibrium to the RHS. This decreases the concentration of the carbonic
acid, H2CO3, which is in turn increased by a decreased rate of breathing
such that less CO2(g) is exhaled resulting in H2CO3 being replaced as the
equilibrium shifts to the H2CO3 side. The 2 equilibria together resist increase in
basicity.
PH changes and indicators

Indicators are substances that change colour with a change in pH. Many indicators
are weak acids (some are weak bases though) and can be represented by HIn. They
have many different colours.
HIn (aq) ⇌ H+(aq) + In-(aq)
e.g. for methyl orange RED

YELLOW

At the end point of a titration HIn and In-

are present in equal concentrations.
Using a methyl orange as indicator:
➢ At the end point [HIn] (red) = [In-]
(yellow)
➢ Hence the colour at the end point
is orange
➢ FYI, the pH of the end point is
called the pKIn of the indicator.

When the acid and base have completely

reacted this is known as the
equivalence point. Here there is a
sharp change in pH for a very small addition of acid or base.

Experiments to distinguish the strengths of acids and bases

➢ A pretty cool way is to test electrical conductivity. In solution, ions conduct

electricity. ;)
➢ The standard enthalpy of neutralisation is the enthalpy change that occurs
when 1 mole of water is produced in the reaction of an acid with an alkali
under std. conditions.
The reaction between all acids and alkalis is H+(aq) + OH-(aq)  H2O(l)
Since all strong acids and alkalis are completely dissociated, the enthalpy
change of neutralisation is the same. If the acids and alkalis are weak, then the
standard enthalpy of neutralisation will be less.
Energy
Lattice Enthalpy
Standard enthalpy changes are the enthalpy changes when 1 mole of a substance is
formed/burnt in their natural state/in excess oxygen under standard conditions of
298K and 100kPa. The average bond enthalpy is the breaking of 1 mole of a covalent
bond in a gaseous molecule under standard conditions. The enthalpy change of
formation of ethane and the combustion of ethane are:
2C(s)+3H2g⟶1C2H6(g) and 1C2H6(g)+312O2g⟶2CO2(g)+ 3H2O(l)
Bond enthalpies are averages and don’t take into account the chemical environment.

Activation energy is the minimum energy required in a collision between particles to

react. Breaking bonds is an endothermic process requiring energy. Hess’s law states
that the enthalpy change for a reaction is the same irrespective of the route taken
provided that the initial and final conditions are the same.

Lattice enthalpy indicates the strength of the ionic bonds in an ionic lattice.
The lattice enthalpy (∆HLEΘ) of an ionic compound is the enthalpy change that
accompanies the formation of 1 mole of an ionic compound from its
constituent gaseous ions. (∆HLEΘ is exothermic)
Na+(g) + Cl-(g) → Na+Cl-(s)
It is almost impossible to measure lattice enthalpy experimentally such that lattice
enthalpy is calculated using a Born-Haber cycle. A Born-Haber cycle is similar to a
Hess’s cycle and enables the calculation of changes that cannot be measured directly
by experiment. The lattice enthalpy of NaCl can be calculated by considering the
standard enthalpy of formation of NaCl(s). In order to form an ionic solid, both sodium
and chlorine have to undergo a number of changes;

All the changes in the cycle can be measured experimentally except the formation of
the Na+Cl-(s) lattice from the gaseous ions i.e. the lattice enthalpy. However all the
other steps in the cycle the lattice enthalpy can be calculated. The above cycle is
adapted with a Hess’s cycle to make the Born-
Haber cycle.

Using Hess’s law; A+B+C+D+E=F

∆HatΘNa(g)+ ∆HatΘCl(g)+ ∆HIEΘNa(g)+ ∆HEAΘCl(g)
+ E= ∆HfΘNa+Cl-(s)
⇒ +107+122+496+-349+ E= -411
⟹Lattice enthalpy of Na+Cl-(s) E= -787 KJmol-1

• F; the std. enthalpy change of

formation; ∆HfΘ;
Formation of an ionic compound
the enthalpy change when 1 mole of the compound in its standard state is formed
from its constituent elements in their standard states under standard conditions.
Exothermic for an ionic compound.
 • A&B; the std. enthalpy change of atomisation; ∆HatΘ; Formation of
gaseous atoms
the enthalpy change that accompanies the formation of one mole of gaseous atoms
from the element in its standard state. The standard enthalpy change of atomisation
is always endothermic.
For gaseous molecules, this enthalpy change can be determined from the bond
dissociation enthalpy- the enthalpy required to break and separate one mole of
bonds so the resulting gaseous atoms exert no force on each other.

• C; the first ionisation energy; ∆HIEΘ; Formation of positive ions

the enthalpy change that accompanies the removal of one electron from each atom in
1 mole of gaseous atoms to form 1 mole of gaseous 1+ ions. Always endothermic.

• D; the first electron affinity; ∆HEAΘ; Formation of negative ions

the enthalpy change that accompanies the addition of one electron to each atom in 1
mole of gaseous atoms to form 1 mole of gaseous 1- ions. Always exothermic.

• C; the lattice enthalpy; ∆HLEΘ; Formation of ionic compounds

the enthalpy change that accompanies the formation of 1 mole of an ionic compound
from its constituent gaseous ions. Always exothermic.

For each different ionic lattice it may have to be adapted. E.g. for MgO(s) there has to
be a second electron affinity to form the O2- ion.

The strength of an ionic lattice and the value of it lattice enthalpy depends upon ionic
radius and ionic charge.
➢ The size of the halide ion effects the ionic radius. A smaller halide ion
decreases the (already negative) lattice enthalpy.
➢ The small, highly charged ions (greatest charge density) are the
strongest ionic lattices.

Enthalpy change of hydration

The concept of a Born-Haber cycle can be extended to provide a partial explanation of
the solubility of substances in water. The enthalpy of hydration is the enthalpy
change when 1 mol of gaseous ions is completely hydrated by water under
standard conditions. i.e. Xn+(g) ⟶ Xn+(aq)

In the case of hydration, the

attraction is either between a
positive ion and the oxygen atom of
the water molecule or a negative
ion and the hydrogen. This is
because of the dipoles due to
hydrogen bonding.

The enthalpy depends on the ionic

radius and the size of the charge on the ion. The greater charge density, the
greater attraction.
Values of lattice enthalpies and enthalpies of hydration relate to the enthalpy of
solution, which is the enthalpy change that occurs
when an ionic solid dissolves in water.

Applying Hess’s law, ∆H2+∆H1=∆H3 where ∆H1 is the

enthalpy of solution, ∆H2 is the lattice enthalpy of NaCl
and ∆H3 is the enthalpy of hydration of the Na+ ion + the enthalpy of hydration of the
Cl- ion. ∆H1 is endothermic. It may seem odd that dissolving sodium chloride is
endothermic. Another factor is encouraging dissolving to take place. It is an energy
term called entropy.

Entropy
Knowledge of enthalpy changes alone is insufficient to provide a certain answer as to
whether a reaction will take place or not. Another energy change, entropy, takes place
during a reaction.

When a reaction occurs, energy is absorbed (endo) or released (exo). In addition,

some is absorbed or released as a result of the re-distribution of the particles when
the products are formed. The extent of this energy relies on the physical state of the
substances and the temperature. Entropy (S) is used to measure this. It is a measure
of the disorder of a system.

Solids are more ordered than liquids and gases and so the most entropy/energy is
required to hold a solid in its ordered state. H2O(s) ⟶ H2O(l) ∆H= +6.02 kJ mol-1 at 0oc.
This endothermic reaction happens because the change in entropy, as melting occurs,
releases sufficient energy to counteract the positive enthalpy. The energy required to
hold the rigid structure of the ice in place is released as the less restrained molecules
of water are produced.

If enthalpy is released in a reaction, ∆H is negative. If entropy is released in a

reaction, ∆S is positive. The energy unit of enthalpy is kJ and entropy J.

Entropy always increases (∆S is positive) when there is a greater opportunity

for energy to be spread out as a result of change (e.g. ‘disorderness’).
Entropy increases when:
• A solid becomes a liquid. Entropy is released and ∆S is positive; more
disordered.
• A liquid becomes a gas. Entropy is released and ∆S is positive; more disordered
• A solid dissolves in a liquid to form a solution. Entropy is released and ∆S is
positive; more disordered.
• A reaction resulting in products with more movement so ∆S is positive; more
disordered.
• A reaction producing more particles of the same state; ∆S is positive and more
disordered.
• As temperature rises, entropy is released and ∆S is positive, more disordered.
∆S= Σentropy of products- Σ(entropy of reactants)
The change in the entropy of a reaction can be combined with the change in enthalpy
to provide an answer as to how a chemical reaction is feasible. Free energy (G)
relates to the enthalpy and entropy changes;
ΔG= ΔH-TΔS (T is temperature)
And ΔG provides a certain answer to whether a reaction is feasible. If ΔG<0 ⇒Reaction
is feasible
If ∆G>0 ⇒Reaction is not feasible (at least at this temperature)

At ∆G=0 the system will be at equilibrium and ∆H=T∆S. The enthalpy change for the
melting of ice to water at 0oc is

e.g. NH3(g)+ HCl(g) ⇌NH4Cl(s)

∆H∅r= -176 000 J mol-1 and ∆S∅ = -284.5 J mol-1 and so at 298K, ∆G= -176000-298-
284.5= -91.2 kJ mol-1 is the reaction would happen at 298K. This is not true at 500K.

Ionic Equations
➢ Ionic substances that are solid has no free-moving ions so their ions cannot
react independently of each other. Their complete formula must be given.
➢ Compounds of metals and strong acids in aquous solutions will be split into ions.
➢ Covalent compounds exist as complete molecules and are always shown as
complete entities in the ionic equation.
Acid + Base  Salt + Water MgO(s) + 2H+  Mg2+(aq) + H2O(l) (Ionic Equation)
Acid + base  Salt + carbon dioxide + water CO32-(aq) + 2H+(aq)  CO2(g) + H2O(l)
(Ionic Eqation)

Oxidation number identifies whether a substance has undergone oxidation or

reduction. All elements in their natural state have oxidation number 0. The oxidation
numbers of any molecules add up to 0 and ions add to their charge. Group 1, 2, 3, 4,
5, 6 are always +1, +2, +3, +4, +5, +6. Fluorine is always -1, Hydrogen is usually +1,
Oxygen is usually -2, Chlorine is usually -1.
e.g. Zn(s) + CuSO4(aq)  ZnSO4(aq) + Cu(s) . Cu goes from +2 to 0, Zn from 0 to +2
hence ;
Zn(s) Zn(aq)2+ + 2e- and Cu2+(aq) + 2e-  Cu(s)

Consider Cu(s) + AgNO3(aq)  Cu2+(aq) + Ag(s). Half equations are Cu(s)  Cu2+(aq) + 2e-
and Ag+(aq) + e-  Ag(s). Eliminating the electrons gives Cu(s) + 2Ag+(aq)  Cu2+(aq) +
2Ag(s)

Electrode Potentials
• The standard electrode potential E∅ is the potential difference between
one half-cell (e.g. metal in contact with its metal ions) and the standard
hydrogen electrode (when measured under
standard conditions).
• The standard cell potential is the voltage
formed when two half-cells are connected and
the voltage measured using a voltmeter (of
very high resistance under standard conditions).
The standard hydrogen electrode looks like:
To provide a better surface for the hydrogen, the platinum electrode is usually coated
with very finely divided platinum black. This cell is connected via an external circuit
and through a salt bridge to the other cell. The voltage measured then gives the
electrode potential of the cell on a scale with the half-reaction 2H+(aq) + 2e-  H2(g)
being given the arbitrary value of 0.

For metals the system to the left applies. For non-metals/ions of the same
element in different oxidation states the system to the right applies.

The salt bridge is made of porous material soaked in a saturated solution of

KNO3. It completes the circuit.

Half-Cell E∅ /V
F2(g) + 2e- ⇄ 2F-(aq) 2.87 Half cells with a positive E∅ favour the
Cl2(g) + 2e- ⇄ 2Cl-(aq) 1.36 forward reaction and gain electrons.
Cu2+(aq) + 2e- ⇄ Cu(s) 0.34
Half cells with a negative E∅ favour the
2H+(aq) + 2e- ⇄ H2(g) 0.00
K+(aq) + e- ⇄ K(s) -2.92 reverse reaction and lose electrons.

F2(g) has a high E∅ value and so readily gains electrons to form F-(aq) ions. F2 is a
powerful oxidising agent. K(s) has a low E∅ value and so readily loses electrons to
form K+(aq) and is a powerful reducing agent.

The standard electrode cell can be calculated by using any two half-cells.
Zn2+(aq) + 2e- ⇄ Zn(s) -0.76V Cu2+(aq) + 2e- ⇄ Cu(s) +0.34V
Which indicated the Cu2+(aq) moves in the forward reaction whilst the Zn(s) favours the
reverse reaction.
So hence we can write each half cell as:
Cu2+(aq) + 2e-  Cu(s) +0.34V Zn(s)  Zn2+(aq) + 2e- +0.76 Cell
potential +1.10 V

e.g. Acidified H+(aq)/MnO4-(aq) is a good oxidising agent and can be used to preare Cl2(g)
by the oxidation of
Cl-(aq) ions. Find the cell potential and deduce the balanced equation.
MnO4-(aq) + 8H+(aq) + 5e- ⇄ Mn2+ + 4H2O(l) +1.52V Cl2(g) + 2e- ⇄ 2Cl-(aq)
+1.36V
Both are positive but MnO4-(aq) is more, so moves to the right such that:
MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ + 4H2O(l) +1.52V 2Cl-(aq) ⇄ Cl2(g) + 2e-(aq) -1.36V
Cell potential +0.16V
We can eliminate the electrons by multiplying by 2 and 5 respectively to give;
2MnO4-(aq) + 16H+(aq) + 10Cl-  2Mn2+ + 8H2O(l) + 5Cl2(g)

A positive cell potential indicates the reaction is feasible but gives no indication to
its rate. On the example above, despite a low cell potential, this reaction happens
relatively quickly. Cell potentials are assumed under standard conditions. If they
are not, this may alter the reaction.
For Fe3+(aq) + e- ⇄ Fe2+(aq) (Ee=+0.77V) a lower concentration of Fe2+(aq) will cause the
equilibrium to shift to the RHS and cause the electrode potential to increase. And vice
versa. Any increase/decrease in concentration actually needs to be quite large to have
any effect on Ee.

Storage cells and fuel cells

Storage cells are batteries. Electrode potential can be used to predict the possible
voltage of a battery. Commercial batteries tend to avoid solutions that can leak and
use pastes that surround the electrode.

➢ An alkaline battery has a cathode (half cell that receives electrons) made
of graphite and manganese(IV) oxide and an anode (provides electrons)
made of zince or nickel-plated steel. Electrolyte is potassium hydroxide.
m

At the anode; 2MnO2 + H2O + 2e-  Mn2O3 + 2OH-

Zn + 2OH-  ZnO + H2O + 2e-
At the cathode;
By eliminating the electrons we have Zn + 2MnO2  ZnO + Mn2O3. The overall
voltage is about 1.5V. Both OH- and H2O are eliminated so their concentrations
should remain constant.

➢ Another battery is rechargeable nickel cadmium (Ni-Cd) cell. While it is

supplying electricity the reactions taking place are:

At the anode; 2NiO(OH) + 2H2O + 2e-  2Ni(OH)2 +

Cd + 2OH-  Cd(OH)2 + 2e- 2OH-
At the cathode;

The overall reaction is Cd + 2NiO(OH) + 2H2O  Cd(OH)2 + 2Ni(OH)2. The

batteries can be recharged by supplying an additional voltage which reverses
the reactions above. A disadvantage is that Caladium is toxic. Voltage of 1.2 V
is produced.

Fuel cells can produce electrical power from the chemical reaction of a fuel with
oxygen. They operate as storage cells except fuels are supplied as gases externally.
The hydrogen/oxygen fuel cell is widely used.
– Anode; the platinum catalyst splits the H2 into protons
and electrons.
– Polymer electrolyte membrane only allows the H+
across and this forces the e- to travel around the
circuit.
– An electric current is created in the circuit which is
used to power something.
– Cathode; O2 combines with the H+ from the anode and
the e- from the circuit to make H2O. This is the only
waste product.

Scientists in the car industry are making cars fuelled by hydrogen gas and hydrogen
rich fuels. They have less pollution and less CO2 and greater efficiency.
The hydrogen could be stored;
– As a liquid under pressure.
– Absorbed on the surface of a solid material.
– Absorbed within a solid material.
Limitations include
– Storing and transporting hydrogen. Safety, feasibility of a pressurised liquid and
the limited life cycle of a sold ‘absorber’ or ‘adsorber’ are disadvantages.
– The fuel cell has a limited lifetime.
– Toxic chemicals are used in production.

– Hydrogen economy may contribute to future energy but this requires public
acceptance of hydrogen as a fuel, handling and maintenance of hydrogen systems
and the initial manufacture of hydrogen which requires energy.
Transition Elements

Properties
A d-block element that forms one or more stable ions with an incomplete d-sub-shell.
The 4s sub shell is filled before the 3d sub shell as the 4s sub shell is at a lower
energy. The orbitals in the 3d-sub shell are first occupied singly to prevent any
repulsion caused by pairing.

Scandium and Zinc are not transition metals because Zinc forms one ion, Zn2+ with
[Ar] 3d10 and Scabdauan forms one ion, Sc3+ with [Ar] 3d0.

➢ Variable Oxidation States; transition elements have compounds with two or

more oxidation states. This is due to the fact that successive ionisation energies
of transition metals only increase gradually. All the transition metals can form
an ion of oxidation state +2, representing the loss of two 4s-electrons. The
maximum oxidation state possible cannot exceed the total number of 4s- and
the 3d-electrons in their electron configuration.
➢ Colour of compounds; transition elements have at least one oxidation state in
which their compounds and ions are coloured. The colours are often distinctive
and can be used as a means of identification. Cu2+ ions are blue; Cr3+ ions are
green; Cr2O72- are orange; MnO4- are purple.
➢ Catalysis; Transition metals are frequently used as heterogeneous catalysts.
This is a result of the use of their d-orbital’s to bind other molecules or ions to
their surface. E.g. Fe in Haber process
➢ Complex ions and ligands; Ions of transition elements form complex ions with
ligands.
➢ Other properties; Denser (due to smaller atoms); Higher melting and boiling
points due to stronger metallic bond due to smaller ions meaning greater free
electron density.

Simple precipitation reactions from transition metal hydroxides

Takes place between aqueous alkali e.g. NaOH and an aqueous solution of a metal.
Results in formation of precipitate of the metal hydroxide with a colour.
Cu2+(aq + 2OH- (aq)  Cu(OH)2(S) (Pale Blue)
Fe2+(aq) + 2OH-(aq)  Fe(OH)2(S) (Pale green gelatinous precipitate)
Fe3+(aq) + 3OH-(aq)  Fe(OH)3(S) (Orange-Brown gelatinous precipitate)
Co2+(aq) + 2OH-(aq)  Co(OH)2(s) (Blue precipitate)

Transition element complexes

Transition metal ions are small and densely charged and can strongly attract electron-
rich species called ligands forming complex ions.
➢ A ligand is a molecule or ion that bonds to a metal ion by forming a dative
covalent bond by donating a lone pair of electrons into a vacant d-orbital.
Common ligands are H2O: , :Cl- , :NH3 and :CN- all of which have
at least one lone pair of electrons.
➢ A complex ion is a central metal ion surrounded by ligands
 In [Cu(H2O)6]2+, the six electron pairs surrounding the Cu2+ ion repels one
another as far apart to create an octahedral shape around the complex ion.

In [CuCl4]2- the four electron pairs surrounding the Cu2+ ion repel
one another as far as possible to create a tetrahedral shape such
that the bond angles are 109.5o.

The coordination number is defined as the total number of coordinate bonds from
the ligands to the central transition metal ion in a complex ion. Complex ions with
ligands such as H2O and NH3 are usually 6 coordinate and octahedral in shape.
Complex ions with Cl- ligands are usually 4 coordinate and tetrahedral in shape.

Ligands that form two dative coordinate bonds with the central transition metal ion
are called bidendate ligands.
1,2-Diaminoethane is a common bidendate ligand. Each N has a
lone pair of electrons that can form a dative
bond. It is often drawn as:

And hence a nickel complex could be drawn as:

Stereoisomerism can occur in complex ions.

➢ The square planar structure of tetrahedral shapes allows cis-
trans isomerism.
➢ Optical isomerism is also possible in the case of complexes
coordinated by polydentate ligands. The
superimposable mirror image creates this
isomerism.

One particularly interesting use of a complex ion is of

the cis form of PtCl2(NH3)2. (The platinum is present as a
2+ ion so no overall charge)
It is known as cis-platin and is used during chemotherapy as an anti-cancer drug. A
colourless liquid that is put into the blood via a drip and it binds to the DNA of
cancerous cells preventing their division. The trans molecule is ineffective.

Ligands Substitution
A ligand substitution reaction takes place when a ligand in a complex ion exchanges
for another ligand. The colour of the solution changes as a different complex is
formed.

Exchange between H2O and NH3 ligands; Water and ammonia ligands have similar
sizes such that the coordination number does not change. Blue to Deep Blue
Exchange between H2O and Cl- ligands; Water molecules and chloride ions have
different sizes and the coordination number changes. Blue to Yellow

A similar reaction takes place when

Co2+ replaces Cu2+ such that
[Co(H2O)6]2+ (pink) forms [CoCl4]2-
(blue)

The strength of binding of a ligand to a cation can be represented quantitatively.

When a complex ion such as [Cu(NH3)4(H2O)2]2+ is made it exists in equilibrium with
the hydrated copper ion, [Cu(H2O)6]2+ from which it was made. The equation is:
[Cu(H2O)6]2+ + 4NH3 ⇌ [Cu(NH3)4(H2O)2]2+ + 2H2O
The equilibrium constant is KSTAB. The H2O are NOT included as the whole reaction is
done in water. The value of KSTAB is usually very high, indicating the reaction lies well
to the right so hence [Cu(NH3)4(H2O)2]2+ is much more stable than [Cu(H2O)6]2+.
When KSTAB is applied to a substitution reaction, a large KSTAB results in the
formation of a stable complex ion.

Haemoglobin contains Fe2+ ions. The globin bonds to a

protein. The sixth lone pair has a water molecule
attached to it.
In the lungs, the high oxygen concentration replaces
the water ligand for an oxygen ligand. This is carried
around the body until the oxygen molecule is exchanged
for water again.
If CO is inhaled, the strong CO ligand bonds and is not substituted. Therefore it cannot
carry oxygen any more.

Redox Reactions
The oxidation number can determine whether a substance has lost electrons
(oxidised) or gained electrons (reduced).

A common reaction is the iron(II)-manganate(VII) reaction. Fe2+(aq) and MnO4-(aq). Here is

the derivation.

Write a half-ionic equation for each transition metal

Fe2+ is oxidised to Fe3+ so Fe2+  Fe2+ + e-
Therefore MnO4- must be reduced. It is reduced to Mn2+. Therefore MnO4- + 5e- 
Mn2+ and so
MnO4- + 8H- + 5e-  Mn2+ + 4H2O

Rewrite the half-equations so that the number of electrons in both is the

same
In this case, we need to multiply equation (1) by 5 to get:
5Fe2+  5Fe3+ + 5e- and MnO4- + 8H- + 5e-  Mn2+ + 4H2O as before

Add the last half-equations together to cancel out the electrons.

5Fe2+ + MnO4- + 8H+  5Fe3+ + Mn2+ + 4H2O
Redox titrations involves the transfer of electrons from one species to another.
The colour change provides the end point without the need for an indicator. Potassium
manganate (VII) contains MnO4-(aq) and is often used to oxidise solutions containing
iron(II) ions.
MnO4-(aq) (purple)  Mn2+(aq) (colourless)

This reaction is carried out with potassium manganate (VII) solution in the burette and
the iron(II) solution in the conical flask. As the manganate(VII) solution is added to the
iron(II) solution, it decolourises. The end point indicates there are excess MnO4- ions
present.