Chemistry Of Natural Resources-Elements From The Sea

Formulae, equations and amount of substance

Use the concept of amount of substance to perform calculations involving:
molecular formulae, percentage yield, masses of reagants, volumes of gases and
concentrations of solutions; write and interpret any balanced chemical equations
required, including ionic equations*
A mole is 6.02x10^23 particles-known as Avogadros constant. We
compare the masses of atoms with each other using carbon as standard. An
elements relative atomic mass is the average mass of one atom of an element
for a twelfth of the mass of one atom of carbon-12.
The reactions of an ionic substance often involve only one of the two types
of ion. Because the other two ions are on both sides of the equation, they are
known as spectator ions and removed from the equation. This new equation is
now an ionic equation-it shows only the ions that take part in the reaction.
Recall and explain the procedure for carrying out an acid-alkali solution, and be
able to work out the results

Atomic structure
Use conventions for representing the distribution of electrons in atomic orbitals
It is more appropriate to talk about certain electron shells, as opposed to
energy levels, in chemistry. The shells are labelled by giving each a principle
quantum number, n; the higher the value of n, the further the shell is from the
nucleus, and the higher the energy associated with the shell. Each shell has a
limit to the number of electrons it can hold-a shell which contains its maximum
number of electrons is called a filled shell; electrons are arranged so that the
lowest energy levels are filled first.
Chemists can explain many of the properties of atoms without needing to
use a detailed theory of atomic structure. Much chemistry is decided only by the
outer shell electrons, and one very useful model treats the atom as being
composed of a core of the nucleus plus the inner electron shells, surrounded by
an outer shell (note: electron dot-cross diagrams)
Work out the electronic configuration of atoms from hydrogen to krypton, and
the outer sub-shell structures of other main group elements, in terms of main
energy levels and s-, p- and d-atomic orbitals and the elements positions in the
Periodic Table
When we come to look at elements other than hydrogen, we find their
spectra are much more complex-electron shells are not the whole story. The

shells themselves are split up into sub-shells. These are labelled s, p, d and f. The
n=1 shell only has an s sub-shell; the n=2 shell has two sub-shells, s and p; the
n=3 shell has sub-shells s, p and d; and the n=4 shell has four sub-shells, s, p, d
and f.
The sub-shells are themselves divided further into atomic orbitals: an s
sub-shell always contains one s atomic orbital; a p sub-shell always contains
three p atomic orbitals; a d sub-shell always contains five d atomic orbitals; an f
sub-shell always contains seven f atomic orbitals.
The energy level of the 3d sub-shell lies just above that of the 4s sub-shell,
but just below the 4p sub-shell. This means that once the 4s level is filled (in
calcium), the 3d sub-shell begins to be filled (in scandium). This sub-shell
continues to be filled across the period in the elements Sc to Zn. Once the 3d
orbitals are filled, subsequent electrons go into the 4p sub-shell.
Group 1 and 2 elements are known as s-block elements. In Groups 3-7 and
0, the outermost p sub-shell is being filled; these elements are known as p-block
elements. The elements where a d sub-shell is being filled, and those where an f
sub-shell is being filled are known as d-block and f-block elements respectively.

Bonding and structure

Draw and interpret simple electron dot-and-cross diagrams to show how atoms
bond through ionic, covalent and dative covalent bonds and be able to describe a
simple model of metallic bonding; use the electron pair repulsion principle to
predict and explain the shapes of simple molecules (e.g. CH, NH, HO and SF)
and ions (e.g. NH) with up to six outer pairs of electrons (any combination of
bonding pairs and lone pairs); recall the typical physical properties (melting
point, solubility in water, ability to conduct electricity) characteristic of giant
lattice (metallic, ionic, covalent network) and simple molecular structures
Metal atoms cannot achieve the stable electron arrangement of a noble
gas by sharing electrons with each other, or by transferring electrons from one to
the other-they dont have enough outer shell electrons to allow them to do this.
The metal atoms lose their outer electrons to form a lattice of regularly spaced
positive ions. The outer electrons from each atom contribute to a common pool
of electrons, which move randomly throughout the lattice of positive ions. Since
the electrons in the pool do not belong to any particular metal ion, they are
described as being delocalised or spread out over the lattice. Each positively
charged ion in the metal is attracted to the negatively charged delocalised
electrons, and vice versa. It is these electrostatic attractions that are the metallic
bonds. The strength of metallic bonding depends on several factors, including
the number of electrons per atom available for delocalisation in this way.
Dative covalent bonding is electron pair sharing where both electrons are
provided by the same atom-it is formed between non-metals where there is a
small difference in electronegativity.

The electron-pair repulsion principle states that lone pairs of electrons

repel more than bonding pairs. The shapes of covalent molecules are decided by
a simple rule-groups of electrons in the outer shell repel one another, and move
as far apart as possible.

Ionic lattice-High melting point, usually soluble in water, conductor when

molten/in solution
Giant covalent network-High melting point, insoluble in water, does not
conduct electricity (bar graphite)
Simple molecular-Low melting point, usually insoluble in water, wont
conduct electricity
Metallic lattice-High melting point, insoluble in water, good conductor of
electricity

Explain the term electronegativity; recall qualitatively the electronegativity

trends in the Periodic Table; use relative electronegativity values to predict bond
polarity in a covalent bond; decide where a molecule is polar or non-polar from
its shape and the polarity of its bonds
Electronegativity is the ability of an atom to attract a covalently bonded
electron pair-its pulling power. If two atoms sharing an electron pair in a
covalent molecule have different electronegativity values, the shared electron
pair will be closer to the more electronegative atom, and a polar covalent bond
will be formed. Fluorine is the most electronegative element.
Electronegativity increases across a period-This is because there is an
increased nuclear charge (greater number of protons), but no change in shielding
by inner electrons. This means that the nucleus has a stronger attraction to the
covalently bonded pair.
Electronegativity decreases down a group-This is because the size of the
atom increases, so there are more shells of electrons to shield the nucleus. This
means the nucleus has a weaker attraction on the covalently bonded pair.
Explain, give examples of, and recognise in given examples the following types
of intermolecular bonds: instantaneous dipole-induced dipole bonds (including
dependence in branching and chain length of organic molecules), permanent
dipole-permanent dipole bonds
ID-ID bonds (or Van Der Waals force) are temporary induced dipoles
formed when molecules get close together. These can exist between all
molecules-this is because all molecules can get close enough to induce a
temporary dipole.
As molecules approach each other, distortion of electric clouds on
molecules can lead to and charges forming. This causes the attraction and
repulsion of electrons in adjacent molecules-inducing dipoles. Larger molecules
will have increased molecular size and increased surface area, and therefore
more attraction can occur. ID-ID forces are therefore stronger in these molecules.

PD-PD bonds are the result of the attractive force between permanently
polarised molecules. These forces only occur in polar molecules, and are fairly
strong (e.g. HCl)
Describe the structure of an ionic lattice, and be able to draw the structure of
compounds that have the sodium chloride lattice

Redox
Calculate the oxidation state of specified atoms in formulae (including ions) and
explain which species have been oxidised and which reduced in a redox reaction;
use systematic nomenclature to name inorganic compounds
Atoms in elements are in oxidation state zero; in simple ions, the oxidation
state is the same as the charge on the ion. Since compounds have no overall
charge, the oxidation states of all the constituent elements must add up to zero.

F: -1
O: -2 (except in O and OF
H: +1 (except in H)
Cl: -1 (except when combined with O or F)

Oxidation states can help us to give systematic names to compounds and

ions that contain elements and ions that contain elements capable of existing in
more than one oxidation state. Roman numerals are used, and the number
shows the oxidation state of the preceding element. With ions, oxidation states
are used to help clarify the names of oxyanions-negative ions that contain
oxygen.
Describe redox reactions of s- and p-block elements and their compounds in
terms of electron transfer, using half-equations to represent the oxidation and
reduction reactions, and defining oxidation and reduction as loss and gain of
electrons
Halogens (p-block) tend to remove electrons from other elements; they
are oxidising elements. In all compounds formed by reactions with metals, the
halogen is in oxidation state -1. In most of the compounds formed by reactions
with non-metals, the halogen is again in oxidation state -1. Halogens also react
with one another to form interhalogen covalent compounds. The less reactive of
the two halogens is in a positive oxidation state in these compounds.
Group 5 elements (p-block) can form 3 covalent bonds by sharing their
three unpaired electrons. This gives compounds in which the oxidation state of
the Group 5 element is +3 or -3. Each atom also has a lone pair of electronsthese enable the atoms to form dative covalent bonds. When they do this, the
Group 5 elements can form some compounds in which their oxidation state is +5.
The s-block elements would form compounds having positive oxidation
states.

In a redox reaction, the equation can be thought of as two half-equations,

where one element is losing electrons in one half-equation and the other is
gaining them in the other.
An oxidising agent removes electrons from something else-a reducing
agent fives electrons to something else.

Inorganic chemistry and the Periodic Table

Recall that the Periodic Table lists elements in order of atomic number, and
groups elements together according to their properties; recall the classification
of elements into s-, p- and d-blocks
The s-block comprises groups 1 and 2; the d-block is the transition metals;
the p-block is groups 3-0

Recall and explain the relationship between the position of an element in

the Periodic Table and the charge on its ion
The group of an element refers to the number of outer shell
electrons in an atom of said element, which dictates how many
electrons it will lose/gan when forming an ion, and thus determining
its charge
Recall the names and formulae of NO, SO, CO, OH, NH, HCO;
write formulae for compounds formed between these ions and other given
anions and cations

Recall the meaning of the term ionisation enthalpy; write equations for the
successive ionisations of an element and explain periodic and group trends in the
properties of elements in terms of ionisation enthalpy
If sufficient energy is given to an atom, an electron is lost and the atom
becomes a positive ion-ionisation has taken place. An input of energy is needed
to remove electrons, because they are attracted to the nucleus.
When one electron is pulled out of an atom, the energy required is called
the first ionisation enthalpy. We define the first ionisation enthalpy of an element
as the energy needed to remove one electron every atom in one mole of isolated
gaseous atoms of the element-a mole of gaseous ions with one positive charge
are formed: X(g) -> X(g) + e
Group 0 elements have high first ionisation enthalpies-they are difficult to
ionise, and are very unreactive. The Group 1 elements (alkali metals) have low
ionisation enthalpies, due to their solitary outer shell electron.
On going down Group 7, the first ionisation enthalpies decrease. This is
because the attraction between the nucleus and the outermost electron
decreases. This is a result of there being more filled shells of electrons between
the nucleus and the outermost electron. These shield the positively charged

nucleus form the outermost electron, thus reducing its attraction to the electron.
It is therefore easier for the outermost electron to be removed.
Recall the following physical properties of the halogens: appearance and physical
state at room temperature, volatility, solubility in water and organic solvents;
explain physical sate and volatility of the halogens in terms of intermolecular
bonds

Fluorine-Pale yellow gas, low melting and boiling point, reacts with water
(cannot be soluble), most volatile
Chlorine-Green gas, pale green when dissolved in water and hexane,
higher melting and boiling point than fluorine, slightly soluble in water
Bromine-Dark red (volatile) liquid, red-brown when dissolved in water, red
when dissolved in hexane, again higher melting/boiling points, most
soluble in water
Iodine-Shiny black solid (purple vapour upon heating), brown when
dissolved in water, violet when dissolved in hexane, highest
melting/boiling points, least soluble in water (bar fluorine), least volatile
All halogens are more soluble in organic compounds (e.g. hexane) than
water

The strongest type of intermolecular bond that can form between two
halogen molecules is ID-ID dipole forces of attraction. Fluorine has the smallest
molecules, with the least number of electrons, and so forms the weakest bonds.
The molecules get bigger as the group is descended. With more electrons in each
molecule, the strength of the intermolecular bonds increases, accounting for the
change in physical state of the halogens.
Use given information to compare different methods of manufacturing chemicals
industrially, in terms of atom economy, percentage yield, batch versus
continuous process, siting the plant, cost of process and raw materials, waste
disposal, safety
In a batch process, the starting materials are put into a vessel and allowed
to react together. The reaction is monitored, and, when, complete, the reaction
phase is terminated. The product is then separated from the reaction mixture.
The process is repeated in an identical manner, batch by batch, until the required
amount of product is manufactured.
In a continuous process, the starting materials are fed in at one end of the
plant, and the product is withdrawn at the other end of the plant in a continuous
flow. The process may proceed through various unit operations in specifically
designed parts, each dedicated to a particular step in the sequence.
Explain and compare the relative reactivity of the halogens in terms of their
oxidising ability; describe and write half-equations for the redox changes which
take place:
See earlier notes

When chlorine, bromine and iodine react with other halide ions
Reactions of the halides with halide ions are displacement reactions.
They are also redox reactions, where the more reactive halogen is
the oxidising agent (displacing the less reactive halogen). We can
write two half-equations to express these reactions
At the electrodes on electrolysis of aqueous halide solutions
At the positive electrodes, chloride (halide) ions are oxidised, and at
the negative electrode, water is reduces to produce hydrogen and
hydroxide ions

Recall the reactions between halide ions (X) and silver ions (Ag), and write
ionic equations to represent these precipitation reactions
Silver halides are precipitated when a solution of silver ions is added to a
solution containing halide ions. Silver chloride is white, silver bromide is cream,
and silver iodide is white.
Explain the risks associated with the storage and transport of the halogens
(fluorine to iodine)
Chlorine has a poor public image. It is associated with pollution-pollution of
the land through pesticides that contain organochlorine compounds, and
pollution of the upper atmosphere through CFCs. Both chlorine and a compound
derived from it, phosgene (COCl) were used with deadly effect in the trenches in
the First World War.
Because it is the most reactive of the halogens, fluorine is extremely
dangerous to use. It is so reactive that it is almost impossible to store, because it
reacts with the chemical used to make the container. Instead, it is necessary to
generate the fluorine (made from mineral fluorite) and then use it immediately to
make the required product.

Bromine has a dense and choking vapour-the liquid produces painful sores
if spilled on the skin. Great care has to be taken when transporting bromine;
most of it is carried in lead-lined steel tanks, supported in strong metal frameseach tank holds several tonnes of the element. International regulations control
the design and construction of road and rail tanks.
Recall and describe some uses of halogen compounds which must be weighted
against these risks
About 50 million tonnes of chlorine are produced worldwide annually. The
best known use of this halogen is in water treatment, where it is added to the
water to kill bacteria and other pathogens. A large quantity is used to make
organic chemicals such as chloroethene, which is used to make
poly(chloroethene) or PVC. It is needed for the manufacture of polyurethanes and
is present in a wide variety of solvents (such as trichloroethene) used both in the
dry cleaning of clothes, and in industry to clean grease off metals.

Some fluorine is reacted with sodium to form sodium fluoride-this is added

to toothpaste and, in some cases, domestic water supplies, to help strengthen
tooth enamel, and prevent dental decay. Fluorine is also used to make a wide
range of organic compounds. These include hydrochlorofluorocarbons (HCFCs)
used for air conditioning and refrigeration, and the polymer PTFE, which can be
used to make non-stick cookware-it is also used in reconstructive and facial
surgery.
One of the most important uses of bromine is in the production of flame
retardanats, e.g. TBBA (tetrabromobisphenol A) can be incorporated into some
polymers, making them much less prone to combustion. Silver bromide was very
important in traditional photography. Bromine is also used as a reactant in the
synthesis of medicines, dyes and pestivides. Bromine compounds are used in
agriculture (e.g. bromomethane, CHBr is used as a fumigant).
Iodine is used as an antiseptic solution, which is produced by dissolving
iodine in ethanol, and for making medicines. Humans need iodine in order to
remain healthy, as it is used in our bodies to produce hormones in the thyroid
gland. We get iodine from our food-often from vegetables that have been grown
in soil containing iodide ions.

Organic functional groups

Recognise and write formulae for examples of members of the following
homologous series: halogenoalkanes, and those met in Chemsitry For Life
Halogenoalkanes are the simplest examples of organic halogen
compounds, where the halogen atom is attached to an alkane chain. They are
named after the parents alkanes, with the halogen atom being added as a prefix
to the name of the parents alkane. When there is more than one halogen atom,
the prefixed are listed in alphabetical order. The numbers that are used to show
the position of the halogen atoms are always the lowest possible
Use systematic nomenclature to name and interpret the names of
halogenoalkanes and compounds for which naming was required in Chemistry
For Life
See above

Organic reactions
Describe in outline the preparation of a chloroalkane from an alcohol using HCl
Reacting an alcohol with the appropriate hydrogen halide can make a
monosubstituted halogenoalkane. For example, chloromethane can be made by
reacting methanol with hydrogen chloride. This reaction is an example of a
substitution reaction. Most of the chloromethane manufactured industrially is

made by this method. The reaction can be carried out either by bubbling
hydrogen chloride gas through boiling methanol, or by passing a mixture of
methanol vapour and hydrogen chloride gas over a heated alumina catalyst.
Describe and explain the principal stages in purification of an organic liquid
product

Shaking with sodium hydrogencarbonate solution to remove acidic

impurities
This is only needed if acidic or alkaline impurities are present.
Sodium hydrogencarbonate is added and shaken well, removing
acidic impurities. If the crude product is alkaline and needs
neutralising, a dilute acid is added until the mixture is neutral
Separating from other immiscible liquids using a separating funnel
This is generally the first step, used to separate the impure organic
product from the reaction mixture. If the main product has been
obtained with another immiscible liquid, the two layers must be
separated; this can be done using a separating funnel. The layers
will separate, with the denser liquid forming the lower layer. The
layers should be allowed to settle, before the aqueous layer is
disposed of. The organic layer should then be run into a clean
conical flask
Drying with anhydrous sodium sulphate
Anydrous sodium sulphate should be added to the crude product,
and the mixture swirled
Simple distillation to allow collection of the pure product

Describe and explain the characteristic properties

comparing fluoro-, chloro-, bromo- and iodo- compounds

of

halogenoalkanes,

The carbon-halogen bond is polar, but not polar enough to make a big
difference to the physical properties of the compounds; for example, all
halogenoalkanes are immiscible with water

Boiling points
The boiling points of the halogenoalkanes depend on their size, and
number of halogen atoms present-the bigger the halogen atom, and
the more halogen atoms there are, the higher the boiling point.
Bromo and iodo compounds are fairly reactive, which makes them
useful as intermediates in synthesising other organic compounds.
Nucleophilic substitution with water and hydroxide ions to form alcohols,
and with ammonia to form amines
Substitution reactions are typical of halogenoalkanes-for example, a
substitution reaction takes place between a halogenoalkane and
hydroxide ions, in which the halogenoalkane is hydrolysed to form
an alcohol. For example, in bromobutane (CH-CH-CH-CH-BR), the
C-Br bond is polar, and the oxygen atom of the hydroxide ion is
negatively charged. The partial positive charge on the carbon atom
attracts the negatively charged oxygen of the hydroxide ion. A lone

pair of electrons on the O atom forms a bond with the C atom as the
C-BR bond breaks. This reaction involves heterolytic fission-ions are
formed, rather than radicals.
Halogenoalkanes perform substitution reactions with many different
reagents-what is needed is a group carrying a pair of electrons to
start forming a bond to the carbon atom. Attacking groups like
these, which can donate a pair of electrons to a positively charged
carbon atom to form a new covalent bond, are called nucleophiles.
Nucleophiles dont need to have a full negative charge-it is possible
for a neutral molecule to act as a nucleophile, provided it has a lone
pair of electrons which can be used to form a bond to a carbon
atom.
For example, the water molecule has a lone pair on the oxygen
atom, so water can act as a nucleophile and attack a
halogenoalkane molecule such as 1-bromobutane. This reaction
goes in two stages. First, the HO attacks the halogenoalkane. This
forms a halogen ion, and an organic ion. The latter then loses a H,
forming an alcohol. This type of reaction with water is also known as
a hydrolysis reaction.
Ammonia, NH, can act as a nucleophile in a similar way to water,
with the lone pair of electrons on the N atom attacking the
halogenoalkane. The product is an amine with an NH group.

Reaction mechanisms
Explain and use the terms: hydrolysis, substitution, nucleophile

Hydrolysis-The chemical breakdown of a compound dude to reaction with

water
Substitution-A reaction in which the functional group in a particular
chemical compound is replaced by another group
Nucleophile-A molecule or negatively charged ion with a lone pair of
electrons that it can donate to a positively charged atom to form a
covalent bond

Use the SN2 mechanism as a model to explain nucleophilic substitution in

halogenoalkanes using curly arrows
See earlier notes
Explain how bond enthalpy or bond polarity might affect the relative reactivities
of the halogenoalkanes, and explain how experimental evidence determines that
the bond enthalpy is more important
Whether homolytic or heterolytic fission occurs, all reactions of
halogenoalkanes involve breaking the C-Hal bond; the stronger the bond is, the
more difficult it is to break.

The great strength of the C-F bond makes it very difficult to break, so
fluoro compounds are very unreactive. As you go down the group, the C-Hal bond
gets weaker, so the compound becomes more reactive. Bromo and iodo
compounds are fairly reactive, which makes them useful as intermediates in
synthesising other organic compounds.
You might imagine that a large bond polarity in a C-X bond would result in
it breaking easily. However, it has been shown experimentally that bond enthalpy
is the overriding factor in determining reactivity.

Isomerism
Draw and interpret skeletal, structural and full structural formulae; use the
concept of repulsion of areas of electron density do deduce the bond angles in
organic molecules (including double bonds); relate molecular shape to structural
formulae, and use wedges and dotted lines to represent 3D shape
Because similar charges repel, the groups of electrons around an atom
arrange themselves so that they are as far apart as possible.
Bonds which lie in the plan of the paper are drawn as solid lines, in the
normal way. Bonds which go backwards are shown as dashed lines; those going
forwards are drawn as solid wedges.
Some molecules have lone pairs in the outer shells of individual atoms.
Those lone pairs repel the bonding pairs of electrons, in the same way the latter
repel themselves.
Linear molecules occur when there are two groups of electrons around the
central atom (s), and so the furthest apart the electrons can get is 180.
When there are three groups of electrons around the central atom, the
molecule is known as planar triangular. The angles between bonds in these
molecules are 120.
Four groups of electrons give rise to a tetrahedral shape (109).
In molecules with 5 groups of electrons, a trigonal bipyramidal shape is
formed, with bond angles of 90 and 120.
Octahedral-shape molecules occur when there are six groups of electrons

*Involves calculations that may need other revision sources