THE OCEANS

Revision Booklet
James Smith

The chemical ideas in this module are:

1)
2)
3)
4)

Dissolving
Acid-base equilibria and pH
Entropy
Disposing of carbon dioxide

a) Explain the hydrogen bonding in water and explain the unusual

physical properties of water that arise from this
(i)
Anomalous boiling point among the hydrides of group 6
(ii)
Specific heat capacity
(iii) Enthalpy change of vaporization/evaporation
(iv) Density change on melting
(i) The group 6 hydrides have a strange boiling points pattern (group 6 hydrides are
H2O, H2S, H2Se and H2Te). The boiling point starts off really high at the top of the
group (H2O). There is then a MASSIVE drop in boiling point to H 2S. After this and as
you go down group 6 from here onwards, the boiling point slowly begins to increase
again. The abnormal start to this trend occurs due to the strength of the hydrogen
bonds in H20. The hydrogen bonds are the strongest type of intermolecular bond,
and therefore require the most energy to overcome. Below shows a graph of the
trend in boiling points of the group 6 hydrides:

(ii) The specific heat capacity tells you how many joules are required to raise the
temperature of 1g of a substance by 1K. Its units are J g -1 K-1. Water has a higher
specific heat capacity that most other substances as a result of its extensive
hydrogen bonding. A lot of energy is used in overcoming hydrogen bonds within
clusters of water molecules. So this energy is not available for increasing kinetic

energy of the molecules- it is not available for raising the temperature. In liquids
with no hydrogen bonds, more energy is used for increasing the kinetic energy;
hence the liquid is heated up with less energy.
(iii) The enthalpy change of vaporization is a measure of the energy we have to put
into a liquid to overcome the intermolecular bonds and turn one mole of molecules
from liquid to vapor. Waters enthalpy change of vaporization is generally much
higher than other liquids. This is because it can form many hydrogen bonds, which
are the strongest form of intermolecular bonds, and hence require the most energy
to overcome.
(iv)The density of water DECREASES as it freezes and turns to ice. As water is
cooled to 4oC, the water contracts and its volume decreases, hence the density is
increasing. However, as it approaches 0oC, the water expands and there is further
expansion as the water freezes, causing density to decrease. This is very unusual!
The diagram below shows the structure of ICE:

Thus arrangement of water molecules maximizes the hydrogen bonding between

them, but leads to a VAERY OPEN structure with large spaces in it. Therefore, the
density of Ice is less dense than that of liquid water. When the ice melts, the open
structure collapses and water molecules FALL into some of the open spaces, thus
giving water a greater density!
NOTE: This is bad for water pipes as if the water freezes in the pipe, it
expands and hence may cause the pipe to burst. However, it is good for
nature. If Ice was denser than water, it would sink to the bottom when
ponds and lakes freeze. However, it doesnt and the resulting layer of Ice
that covers the surface of the water provides some insulation and keeps
the water warmer, allowing the fish to stay warm and not freeze to death!

b) Explain the factors (including the intermolecular bonds and iondipole forces) determining the relative solubility of a solute in
aqueous and non-aqueous solvents and explain the hydration of
ions.
Hydration of ions: This is when an ion in solution is surrounded by water
molecules. Water is a polar molecule, as it has a partial positive charge on both
hydrogen atoms and a partial negative charge on the oxygen atom. The positive
ends on the water molecule (the hydrogens) are attracted to negative ions and the
negative end of the water molecule is attracted to positive ions. Each ion in solution
is surrounded by its own sphere of water molecules- this is hydration. It takes a lot
of energy to break the bonds within an ionic lattice, but hydration releases energy
to compensate for this. Therefore, hydration is an EXOTHERMIC process. This
applies to all ionic substances. As soon as they are dissolved, the positive and
negative ions separate and behave independently.

c) For the following terms: enthalpy change of solution, lattice

enthalpy, enthalpy change of solvation (hydration) of ions:
(i)
Explain and use these terms
(ii)
Describe the solution of an ionic solid in terms of an enthalpy
cycle involving this terms.
(iii) Use these enthalpy cycles to perform calculations.
NOTE: The enthalpy change of HYDRATION is when the solvent is water. If the
solvent is not water, we tend to call it the enthalpy change of SOLVATION.

Term
Enthalpy change of solution
Enthalpy change of
solvation/hydration

Definition
The difference between the
The enthalpy change for the
formation of ions from 1 mole of
gaseous ions.
Lattice enthalpy
The enthalpy change when 1 mole
of solid is FORMED by the coming
together of the separate ions.
NOTE:
all lattice enthalpies are negative as the process is exothermic and the
(ii) Diagrams:
stronger the ionic bonding in the lattice, the more negative the value is. HOWEVER,
If we want to break down a lattice (as we do in dissolving) we need to put IN an
equal amount of energy to the lattice enthalpy. This now becomes a positive value
as you are putting energy IN to the system.

d) Explain entropy changes in a qualitative manner, interpreting

entropy as a measure of the number of ways that molecules and
their associated energy quanta can be arranged.
Entropy changes can explained and interpreted by looking at a number of different
factors:

1) NUMBER OF MOLECULES- the more molecules you have, the larger the
entropy, as there are more ways in which the system can be organized (there
is more disorder).
e.g. CaCO3 (s) CaO(s) +CO2

(g)

Here the entropy increases as there are more molecules on the products side of
the reaction.
2) PHYSICAL STATE- the more freely the molecules are to move, the larger the
entropy as the more disorder there will be! In a solid the molecules are not
very free to move, and so the structure is reasonably ordered and has a low
entropy. Liquids have a higher entropy and gases have the most entropy as
their molecules are free to move a lot.
E.g. CaCO3 (s) CaO (s) + CO2 (g)
Here the entropy increases as on the reactants side you only have a solid,
whereas on the products side you have an solid AND A GAS!
3) TEMPERATURE- the higher the temperature of the system, the larger the
entropy as the molecules all have more energy to move, hence there is more
disorder!
4) PRESSURE/CONCENTRATION- the larger the pressure/concentration, the larger
the entropy. This is because it means there are more molecules to be found in
a particular area, hence the amount of disorder has increased.
e) Recall the expressions:
(i)
Stot = Ssys + Ssurr
Ssurr = - H/T
(ii)
To be able to perform calculations using these expressions
(iii) Explain the tendency for a reaction to occur in terms of the sign
of Stot
These calculations are fairly straight forward and so I shall skip straight to
(iii)
iii) This comes from the 2nd law of thermodynamics: a reaction will be
SPONTANEOUS is the entropy of the universe (or total entropy changes) increases.
Therefore, if the sign for Stot is NEGATIVE, the reaction is unlikely to happen easily.
Whereas if the sign is POSITIVE then the reaction is likely to occur freely and
spontaneously!

f) Calculate the entropy change if a reaction given the entropies of

reactants and products
Add up the entropies on the products side and the reactants side separately.
Now, minus the total entropy of the reactants from the total entropy of the
products to find the change in entropy for the system.
g) Recall the meaning of the term Ionization enthalpy, write equations
for the successive ionizations of an element, and interpret periodic
and group trends in ionization enthalpy.
IONISATION ENTHALPY this is the energy required to remove one electron
from every atom in one mole of isolated gaseous atoms of the element. The 1 st
ionization enthalpy is the energy required to remove the 1 st outer electron, the
2nd is the energy to remove the 2nd outermost electron etc.
X

(gas)

X+ (gas) + e- (first ionization enthalpy Equation)

(gas)

X2+(gas) +e- (second ionization enthalpy Equation)

X2+(gas) X3+

(gas)

+ e- (3rd Ionization enthalpy equation)

Ionization enthalpy decreases as you go DOWN a group. This is due to a number

of factors, such as the electrons being further away (due to extra electron shells)
from the positive nucleus, meaning the attraction between the two is weaker, as
well as the effect of shielding by other shells of electrons, which block the
positive charge of the nucleus on the outermost electrons.
The 2nd Ionization enthalpy will be greater the 1 st, and the 3rd greater than the 2nd
etc. This is because once one electron is removed, the others become much
more attracted to the nucleus, hence this stronger attraction means more
energy is required to release the next electron etc.
h) Recall and explain the relationship between the position of an
element and the charge of its Ion.
The group 1 elements tend to form ions with a 1+ charge.
The group 2 elements tend to form ions with a 2+ charge.
The Halogens (group 7) form ions with a 1- charge.
The group 6 elements (including oxygen) form an 2- charge.
Transition elements have various oxidation states and therefore can form ions with
various charges!

i) Recall the names and formulae of NO3-, SO42-, CO32-, OH-, NH4+, HCO3-,
write formulae for compounds formed between these ions and other
anions and cations.
ION
-

NO3
SO42CO32OHNH4+
HCO3-

NAME
Nitrate ion
Sulphate ion
Carbonate ion
Hydroxide ion
Ammonium ion
Hydrogen carbonate ion

j) Describe acids in terms of the Bronsted-Lowry theory as proton

donors and bases as proton acceptors (synoptic) AND explain and
use the terms conjugate acid and conjugate base.
Acids are proton donators.
Bases are proton acceptors.
Once an acid has given away a proton, there is always the chance that it will
take it back again. The anion that an acid forms acts like a BASE as it can
reaccept a proton to reform the original acid. This means that the Acidic
reactants form a basic product. We think of these in pairs call CONJUGATE pairs.
The Acid has a conjugate base. Similarly a Basic reactant has a conjugate acid
on the products side of the reaction:

NOTE: water can act as a BASE or an ACID. It is AMPHOTERIC.

2nd NOTE: A strong acid has a WEAK conjugate base, and a strong base has
a WEAK conjugate acid. I.e. if an acid has a strong tendency to donate H+
ions, its conjugate base will have a weak tendency to accept them back!

k) Explain and use the terms strong acid, strong base, writing
equations of their ionization in water.
STRONG ACID: An acid that fully dissociates in water and tends to donate many
H+ ions. The equations for the dissociate of strong acids in water DOES NOT have a
reversible reaction sign. E.g:
HCl (aq) H+ (aq) + ClSTRONG BASE: a base that has a strong
tendency to accept H+ ions. Again,
(aq)
reactions involving strong bases do not have a reversible reaction sign.
l) Explain and use the terms weak acid (writing equations for their
dissociation in water) and acidity constant (dissociation constant)
Ka, PKa
WEAK ACID: A weak acid is one which does not fully dissociate in water i.e. the
dissociation process is reversible for that acid.
E.g.:
C2H5OH H+ +
C2H5OACIDITY CONSTANT: This is an equilibrium constant to show the position of
equilibrium for the dissociation of a weak acid.
Ka = [H+] [Anion]
[ACID]

[Products]
[Reactant]

m) Explain and use the term pH and use given data to calculate the pH
of:
(i)
Strong acids
(ii)
Strong bases, using Kw
(iii) Weak acids (including calculating any of the terms pH, Ka and
concentration from any two others, being aware of the
approximations and assumptions made in using a simple
equation.

pH= - log [H+]

(i)

(ii)
(iii)

For a strong acid: the concentration of the H+ ions will be the same as (if
a monoprotic acid) or 2 times (if a diprotic acid) the concentration of the
original acid. Therefore, just sub in this value to the above formula.
?
For weak acids, you may have to find the concentration of the H+ ions by
rearranging the Ka formula and subbing in given values. One this is done
you simply sub in the [H+] into the above formula for pH. The
assumptions you may have to make are:

n) For Buffer solutions based on solutions of weak acids and their salts:
(i)
Explain the meaning of the term Buffer
(ii)
Explain how a buffer solution works (including in everyday
applications)
(iii) Carry out buffer solution calculations
(i)
A buffer solution is a solution of a weak acid and their corresponding salts.
For example: a solution of Ethanoic acid and Sodium ethanoate. A buffer
solution is a solution which can resist small changes in pH i.e. its pH will
not change when a small amount of acid or base is added to the solution.
Natural buffer solutions include our saliva, stomach juices, blood and the
ocean. Living systems often use H2CO3 and HCO3-, or H2PO4- and HPO42- in
combination with proteins.
(ii)
The solution has an equilibrium established within it; the weak acid on the
reactants side and the corresponding salt on the products side e.g.

HA H+ + ANow Le Chateliers principle applies to this equilibrium. So when a small amount

of acid is added to the solution, the position of equilibrium shifts to counteract
the decrease in pH. To do this, the basic anion (A -) reacts with some of the
excess H+ ions to create HA and water (i.e. the position of equilibrium is shifted
further towards the left), preventing a significant change in pH. Similarly, when a
small amount of base is added to the buffer solution, the acid on the reactants
side dissociates further to provide more H+ ions free to react with the excess
base molecules, hence the position of equilibrium moves towards the products!
Again, this prevents a change in pH.
There are TWO assumptions you need to make when explaining buffer solutions
work.
1) That all the A- ions comes from the salt. The weak acid HA provides very
few A- ions compared to the fully ionized salt.
2) Almost all the HA molecules put into the buffer remain unchanged
(not many have dissociated). We make the same assumption when
calculating the pH of a weak acid, but it is an even better assumption for
buffer solutions because the high concentration of A - from the fully ionized
salt pushes the equilibrium even further to the left.
(iii)
If we make these assumptions above, we get an expression for K a for a
buffer solution:

Ka (buffer) = [H+] x [Salt]

[Acid]

o) Discuss the global influence of the dissolving of carbon dioxide in

water, discuss and explain the benefits and risks associated with
various approaches to reducing CO2 levels including: more
economical use of fuels, use of alternative fuels (including
hydrogen), capture and storage of CO2 and increased
photosynthesis
LOOK AT: STORING CO2 section and THE OCEAN AND CLIMATE section
under The oceans section on www.4college.co.uk for the first part of this
point on the spec. Print it out as it is very useful!
Method to reduce CO2
Levels

Benefits

Risks/inconvenience

More economical use of

fuels

Alternative fuels (e.g.

Hydrogen)

Capture and Storage of

CO2

Reduces dependence on
a non-renewable
substance (like oil and
fossil fuels).
.
Has less pollutants and
does not emit any CO2

All cars and machinery

needs to be modified to be
able to be powered by the
new fuel.
.
Hydrogen is difficult to
store and is extremely
flammable.

Increasing Photosynthesis

Look back to AS notes and AS storylines book and try to fill in this table: